United States

Environmental Protection

Agency

OffIce of

Research and Development

Washmgton, DC 20460

EPAl600f4-79f020

March 1983

&EPA Methods for

Chemical Analysis of

Water and Wastes
MANUAL DISTRIBUTION RECORD

A Manual dIstnbutlOn record has been establtshed and wIll be mamtamed up to date so that

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EPA-600j4-79-020

METHODS FOR CHEMICAL ANALYSIS

OF WATER AND WASTES

March 1983

Second Pnntmg June 1982

ENVIRONMENTAL MONITORING AND SUPPORT

LABORATORY

OFFICE OF RESEARCH AND DEVELOPMENT

U S ENVIRONMENTAL PROTECTION AGENCY

CINCINNATI, OHIO 45268

@ Prmted on Recycled Paper _
DISCLAIMER

The mention oftrade names or commercIal products m thIs manual IS for IllustratIOn purposes, and

does not constItute endorsement or recommendatIon for use by the U S EnVironmental Protection

Agency

11
FOREWORD

th~ accomplishment of our objective m protectmg the enVIronment reqUIres a relIable assessment of

the present condition and a determmatlon of the effectiveness of corrective measures DecIsions

which must be made on the need for pollutIOn abatement and the most efficient means of achlevmg

environmental quahty depend upon the avatlabillty ofsound data Test procedures for measurement

ofthe presence and concentration ofsubstances hazardous to human health as well as an evaluation

ofthe qualIty ofthe environment are essential to satisfactory declSlon-makmg

This manual of chemical methods was prepared by the staff of the Environmental Momtonng and

Support Laboratory of the Environmental Research Laboratory, Cmcmnatl to prOVide procedures

for momtonng water supplIes, waste dIscharges, and the qualIty of ambIent waters These test

methods have been carefully selected to meet the needs of Federal LegIslatIOn and to prOVide

gUIdance to laboratones engaged m protectmg human health and the aquatic environment The

contnbuttons and counsel ofsCientists m other EPA laboratones are gratefully acknowledged

Test procedures contamed herem, that are approved for water and waste momtonng under the Safe

Dnnkmg Water Act (SDWA) and the NatIOnal Pollutant DIscharge Eltmmatton System (NPDES),

of PL 92-500 are so mdicated at the bottom of each tItle page These approved methods are also

recommended for ambient momtonng needs of Section 106 and 208 ofPL 92-500 Methods WIthout

thIS stated approval are presented for mformatton only Correspondence on these methods IS mVIted

Robert L Booth

Actmg DIrector, EnVIronmental Momtonng and

Support Laboratory, CmcmnatI, OhIO 45268

111
ABSTRACT

This manual provides test procedures approved for the mOnItonng of water supphes, waste

discharges, and ambient waters, under the Safe Drmkmg Water Act, the NatIOnal Pollutant

Discharge EhmmatlOn System, and Ambient MOnItonng ReqUIrements of SectIOn 106 and 208

of Pubhc Law 92-500 The test methods have been selected to meet the needs offederal legislatIOn

and to provide gUidance to laboratones engaged m the protectIOn of human health and the

aquatic environment

IV
CONTENrs , ,

Foreword 111

,

Abstract

IntroductIOn

Sample PreservatIon

EPA QualIty Assurance Coordmators

U 1 r j

IV

, X111

xv

xx

100 PhysIcal Properties

Color

Colonmetnc, ADMI

Coiorimetnc, PlatInum-Cobalt

Spectrophotometnc

Conductance

SpecIfic Conductance

Hardness, Total (mg/l as CaC03)

Colonmetnc, Automated EDTA

TItnmetnc, EDTA

Odor

Threshold Odor (ConSIstent Senes)

pH

Electrometnc

Electrometnc (Contmuous Momtonng)

ResIdue

FIlterable

Gravlmetnc, Dned at 180°C

Non-FIlterable

Gravimetnc, Dned at 103-105°C

Total

Gravimetnc, Dned at 103-105°C

VolatIle

Gravimetnc, IgnItIOn at 550°C

Settleable Matter

Volumetnc, Imhoff Cone

v

Method 110 1

Method 110 2

Method 110 3

Method 1201

Method 1301

Method 1302

Method 1401

Method 1501

Method 1502

Method 1601

Method 1602

Method 1603

Method 1604

Method 1605
Temperature

Thermometnc

TurbIdIty

Nephelometnc

200 Metals

AtomIC AbsorptIon Methods

InductIvely Coupled Plasma ..

Aluminum

AA, DIrect AspIratIon

AA, Furnace

Antimony

AA, DIrect AspiratIOn

AA, Furnace .....

Arsemc

AA, Furnace

AA, Hydnde

Spectrophotometnc. SDDC

DIgestion Method for Hydnde and SDDC

Banum

AA, DIrect AspiratIOn

AA, Furnace

Berylhum

AA, Direct AspIratIOn

AA, Furnace

Boron

Colonmetnc, Curcumm

CadmIUm

AA, DIrect AspIration

AA, Furnace .

CalcIUm

AA, DIrect AspIratIOn

TItnmetnc, EDTA

VI

Method 1701

Method 1801

SectIon 200 0

Method 2007

Method 2021

Method 2022

Method 2041

Method 2042

Method 2062

Method 2063

Method 2064

Method 2065

Method 2081

Method 2082

Method 210 1

Method 210 2

Method 2123

Method 213 1

Method 2132

Method 215 1

Method 2152
Chromium

AA, Direct AspiratIOn

AA, Furnace

ChelatlOn-Extraction

Hexavalent, Chelation-Extraction

Hexavalent, DIssolved

Cobalt

AA, Direct AspiratIOn

AA, Furnace

Copper

AA, Direct Aspiration

AA, Furnace

Gold

AA, Direct AspIratIOn

AA, Furnace

IndIUm

AA, Direct AspIratIOn

AA, Furnace

Iron

AA, Direct AspIration

AA, Furnace

Lead

AA, Direct AspiratIOn

AA, Furnace

MagnesIUm

AA, Direct Aspiration

Manganese

AA, Direct Aspiration

AA, Furnace

Mercury

Cold Vapor, Manual

Cold Vapor, Automated

Cold Vapor, Sediments

Vll

Method 2181

Method 2182

Method 2183

Method 2184

Method 2185

Method 2191

Method 2192

Method 2201

Method 2202

Method 2311

Method 2312

Method 2351

Method 2352

Method 2361

Method 2362

Method 2391

Method 2392

Method 2421

Method 2431

Method 2432

Method 2451

Method 2452

Method 2455
Molybdenum

AA, DIrect ASpIratIOn Method 2461

AA, Furnace Method 2462

NIckel

AA, DIrect ASpIratIOn Method 2491

AA, Furnace Method 2492

OsmIUm

AA, DIrect AspiratIOn Method 2521

AA, Furnace Method 2522

Palladium

AA, DIrect AspIration Method 253 1

AA, Furnace Method 2532

Platmum

AA, DIrect Aspiration Method 255 1

AA, Furnace Method 2552

PotassIUm

AA, Direct Asprration Method 258 1

RhenIUm

AA, DIrect AspIratIon Method 2641

AA, Furnace Method 2642

RhodIum

AA, DIrect Asprratlon Method 2651

AA, Furnace Method 2652

Ruthemum

AA, DIrect AspIratIon . Method 267 1

AA, Furnace Method 2672

Selemum

AA, Furnace Method 2702

AA, Hydnde Method 2703

StIver

AA, DIrect Aspiration Method 272 1

AA, Furnace Method 272 2

Vl1l
Sodmm

AA, DIrect ASpIratIOn

AA, Furnace

Thalhum

AA, DIrect ASpIratIOn

AA, Furnace

Tm

AA, DIrect AspIration

AA, Furnace

Titamum

AA, DIrect AspIratIOn

AA, Furnace

Vanadmm

AA, DIrect AspIratIOn

AA, Furnace

Zmc

AA, DIrect AspIratIon

AA, Furnace

300 Inorgamc, Non-metalllcs

ACIdIty

TItnmetnc

Tltnmetnc (aCId ram)

Alkallmty

TItnmetnc (pH 4 5)

Colonmetnc, Automated Methyl Orange

BromIde

TItnmetnc

Chlonde

Colonmetnc, Automated Ferncyamde, AA I

Colonmetnc, Automated Ferncyamde, A..~ II

TItnmetnc, Mercunc NItrate

Chlonne, Total ResIdual

TItnmetnc, Amperometnc

TItnmetnc, Back-Iodometnc

IX

Method 2731

Method 2732

Method 2791

Method 2792

Method 2821

Method 2822

Method 2831

Method 2832

Method 2861

Method 2862

Method 2891

Method 2892

Method 3051

Method 305 I

Method 310 1

Method 310 2

Method 320 I

Method 325 I

Method 3252

Method 3253

Method 330 I

Method 3302
'"

,

'.>

Method 350.2

Method 350.3

Method 350.1

Nitrogen

Ammonia

,Colorimetric, Automated Phenate ...............................•............

Colorimetric; Titrim~tric; Potentiometric -

Distillation Procedure .

Potentiometric, Ion Selective Electrode .

Kjeldahl, Total

Colorimetric, Automated Phenate ; 'Method 351.1

Colorimetric, Selpi-Automated

Block Digester AAII. Method 351.2 .

Colorimetric; Titrimetric; Potentiometric Method 351.3

Potentiometric, Ion Selective Electrode Method 351.4

Nitrate-Nitrite

Colorimetric, Automated Hydrazine

Reduction ~................. Method- 353.1

Colorimetric, Automated Cadmium Reduction Method 353.2

Colorimetric, Manual Cadmium Reduction Method 353.3

x

Titrimetric, Iodometric Method 3g0.3

Titrimetric, DPD-FAS ; 'Method 330.4

Spectrophotometric, DPD Method 330.5

Iodide

Titrimetric............................................................................................. Method 345.1

Nitrate

Colorimetric, Brucine................................................................. Method 352.1'

Fluoride

Colorimetric, SPADNS with Bellack

Distillation ;............. Method 340.1

Potentiometric, Ion Selective Electrode.......... Method 340.2

Colorimetric, Automated Complexone............................................... Method 340.3

Cyanide

Amenable to Chlorination

Titrimetric, Spectrophotometric.. Method 335.1

Total

Titrimetric, Spectrophotometric Method 335.2

Colorimetric, Automated UV ....•...............; ;; , ;~ .•.....Method 335.3
Nttrtte

Spectrophotometnc

Oxygen, Dtssolved

Membrane Electrode

Modified Wmkler (Full Bottle Techmque)

Phosphorus

All Forms

Colonmetnc, Automated, Ascorbic ACid

Colonmetnc, Ascorbtc Actd,

Smgle Reagent

Colonmetnc, Ascorbtc ACid,

Two Reagent

Total

Colonmetnc, Automated, Block Dtgestor, AA II

Stltca, Dtssolved

Colonmetnc

Sulfate

Colonmetnc, Automated Chloramlate

Colonmetnc, Automated Methyl Thymol Blue, AA II

Gravlmetnc

Turbldlmetnc

Sulfide

Tltnmetnc, Iodme

Colonmetnc, Methylene Blue

Sulfite

Tttnmetnc

400 Orgamcs

Btochemtcal Oxygen Demand

BOD (5 day, 20D

C)

Chemtcal Oxygen Demand

Tttnmetnc, Mtd-Level

Tttnmetnc, Low Level

Tttnmetnc, Htgh Level for Saltne Waters

Colonmetnc, Automated, Manual

Xl

. Method 354 1

Method 3601

Method 3602

Method 3651

Method 3652

Method 3653

Method 3654

• Method 370 1

Method 3751

Method 3752

Method 3753

Method 375.4

Method 3761

Method 3762

Method 3771

Method 405 I

Method 410.1

Method 410 2

Method 410 3

Method 4104
011 and Grease, Total Recoverable

Gravimetnc, Separatory Funnel ExtractIon

Spectrophotometnc, Infrared

OrganIc Carbon, Total

Combustion or OXidatIOn

UV Promoted, Persulfate OXidation.

Petroleum Hydrocarbons, Total, Recoverable

Spectrophotometnc, Infrared

PhenolIcs, Total Recoverable

Spectrophotometnc, Manual 4-AAP wIth DIstIllatIOn

Colonmetnc, Automated 4-AAP wIth DIstIllatIOn

Spectrophotometnc, MBTH wIth DIstIllatIOn

Methylene Blue Active Substances (MBAS)

Colonmetnc .

NTA

Colonmetnc, Manual, Zmc-Zmcon

Colonmetnc, Automated, Zmc-Zmcon,

XlI

Method 413 1

Method 413 2

Method 415 1

Method 4152

Method 418 1

Method 4201

Method 4202

Method 4203

Method 4251

Method 4301

Method 4302
INTRODUCTION

NOT£ Smce the fzrst przntmg of thzs edztwn m March 1979, varzousedztorzal errors have been

brought to our attentwn whzch have been corrected m thzs second prmtmg In

addztwn, zt has been found necessary to add to thzs przntmg an updated preservatzon

and holdmg tzmes table (Table 1), as well as szx new methods They are under-pH,

£leetrometrzcs (contmuous monztormg), Method 1502, under Metals, Inductzvely

Coupled Plasma, 2007, under MetalslChromzum Hexavalent, Dzssolved, Method

2185, under MetalslSodzum AA, Furnace, ,Method 2732, under Inorganzc, nonmetallzcslAczdzty Tztrzmetrzc(aczd ram), Method305 1, and under Organzcs, Organzc

Carbon, Total UV Promoted, Persulfate, Oxzdatzon, Method 415 2

These addztwns have been made so as to keep users of the manual current wzth the

procedures the Agency uses m determmmg complzance wzth applzcable water and

effluent standards zt has establzshed

Persons who already possess a copy of the 1979 edztwn of the manual and who wzsh to

update zt by mcludmg the czted addztwns need not request another copy The new

materzal zs avazlable as a separate volume, entztled, "Technzcal Addzt'wns to Methods

for Chemzcal Analyszs of Water and Wastes, £PA-60014-79-020," £PA-60014-82-055,

from ORD Publzcatwns, C£RI, us £nvzronmental Protectwn Agency, Cmcmnatz,

OH45268

Th1S th1rd ed1tlOn of "Methods for Chem1cal Analys1s ofWater and Wastes" contams the chem1cal

analytlCal procedures used m U S Env1ronmental ProtectlOn Agency (EPA) laboratones for the

exammatlOn of ground and surface waters, domest1c and mdustnal waste eftluents, and treatment

process samples Except where noted under "Scope and ApphcatlOn", the methods are-appllcable to

both water and wastewaters, and both fresh and sahne water samples The manual prov1des test

procedures for the measurement of physlCal, morgamc, and selected orgamc const1tuents and

parameters Methods for pestic1des, mdustnal orgamc waste matenals, and sludges are given mother

publlcatlOns of the Agency The methods were chosen through the combmed efforts of the EPA

Regional Quahty Assurance Coordmators, the staff ofthe PhyslCal and Chem1cal Methods Branch,

Env1ronmental Momtonng and Support Laboratory, and other semor chem1sts m both federal and

state laboratones Method selection was based on the foUowmg cntena

(1) The method should measure the des1red property or const1tuent w1th preclSlon,

accuracy, and spec1fic1ty suffic1ent to meet the data needs of EPA, m the presence ofthe

mterfenng matenals encountered m water and waste samples

(2) The procedure should utihze the eqUlpment and slalls aval1able m modem water

pollutlOn controllaboratones

(3) The selected method 1S muse m many laboratones or has been suffic1ently tested to

estabhsh 1tS vahd1ty

(4) The method should be rap1d enough to perm1t routme use for the exammation of a large

number ofsamples

Xlll
Instrumental methods have been selected m preference to manual procedures because of the

Improved speed, accuracy, and preCISIOn In keepmg wIth thIS polIcy, procedures for the Techmcon

AutoAnalyzer have been mcluded for laboratones havmg thIS eqUIpment avaIlable Other

contmuous flow automated systems usmg these IdentICal procedures are acceptable

Intralaboratory and Interlaboratory preCISIon and accuracy statements are prOVIded where such data

are avaIlable These Interlaboratory statements are denved from Interlaboratory studIes conducted

by the QUalIty Assurance Branch, EnVIronmental Momtonng and Support Laboratory, the

American SOCIety for TestIng Matenals, or the AnalytIcal Reference SerVIce ofthe US PublIc Health

ServIce, DHEW These methods may be used for measurIng both total and dIssolved constItuents of

the sample When the dIssolved concentratIOn IS to be determmed, the sample IS filtered through a

o45-mIcron membrane filter and the filtrate analyzed by the procedure speCIfied The sample should

be filtered as soon as pOSSIble after It IS collected, preferably m the field Where field filtratIOn IS not

practIcal, the sample should be filtered as soon as It IS receIved In the laboratory

Many water and waste samples are unstable In SItuatIons where the Interval between sample

collectIOn and analySIS IS long enough to produce changes m eIther the concentratIon or the phySIcal

state ofthe constItuent to be measured, the preservatIOn practIces m Table I are recommended

ThIS manual IS a baSIC reference for momtonng water and wastes m complIance WIth the

reqUIrements ofthe Federal Water PollutIOn Control Act Amendments of 1972 Although other test

procedures may be used, as prOVIded m the Federal RegIster Issue ofOctober 16, 1973 (38FR 28758)

and In subsequent amendments, the methods descnbed In thIS manual wIll be used by the

EnVIronmental ProtectIOn Agency m determmIng complIance WIth applIcable water and effluent

standards establIshed by the Agency

Although a SIncere effort has been made to select methods that are applIcable to the WIdest range of

sample types, sIgmficant mterferences may be encountered m certam Isolated samples In these

SItuatIons, the analyst WIll be provIdmg a valuable servIce to EPA by defimng the nature of the

mterference WIth the method and bnngIng thIS InfOrmatIon to the attentIOn of the DIrector,

EnVIronmental Momtonng and Support Laboratory, through the appropnate QualIty Assurance

CoordInator

xu'
SAMPLE PRESERVATION

Complete and uneqUIvocal preservatIOn of samples, eIther domestic sewage, mdustnal wastes, or

natural waters, IS a practlcallmposslblhty Regardless ofthe nature ofthe sample, complete stablhty

for every constItuent can never be achIeved At best, preservatIOn techmques can only retard the

chemIcal and bIOlogiCal changes that mevltably contmue after the sample IS removed from the parent

source The changes that take place m a sample are eIther chemIcal or bIOlogiCal In the former case,

certam changes occur m the chemIcal structure of the constituents that are a functIOn of phySIcal

condItIOns Metal catIOns may precIpItate as hydroxIdes or form complexes wIth other constituents,

catIons or amons may change valence states under certam reducmg or oXldlzmg condItIons, other

constItuents may dIssolve or volatlhze wIth the passage oftIme Metal catIOns may also adsorb onto

surfaces (glass, plastIc, quartz, etc), such as, Iron and lead BIologIcal changes takmg place m a

sample may change the valence of an element or a radIcal to a dIfferent valence Soluble constituents

may be converted to orgamcally bound matenals m cell structures, or cell lYSIS may result m release

of cellular matenal mto solutIOn The well known mtrogen and phosphorus cycles are examples of

bIologIcal mfluence on sample composItIon TherefOIe, as a general rule, It IS best to analyze the

samples as soon as possIble after collectIOn ThIS IS espeCIally true when the analyte concentratIOn IS

expected to be m the low ug/l range

Methods of preservatIOn are relatIvely hmlted and are mtended generally to (1) retard bIOlOgical

actIOn, (2) retard hydrolysIs of chemIcal compounds and complexes, (3) reduce volatlhty of

constItuents, and (4) reduce absorptIOn effects PreservatIOn methods are generally hmlted to pH

control, chemIcal addItion, refngeratlon, and freezmg

The recommended preservative for vanous constItuents IS gIven m Table 1 These chOIces are based

on the accompanymg references and on mformatton supphed by vanous Quahty Assurance

Coordmators As more data become avallable, these recommended holdmg tImes WIll be adjusted to

reflect new mformatton Other mformatlon provIded m the table IS an estImatIon of the volume of

sample reqUIred for the analysIs, the suggested type of contamer, and the maXImum recommended

holdmg tImes for samples properly preserved

xv
TABLE 1

RECOMMENDATION FOR SAMPLING AND PRESERVATION

OF SAMPLES ACCORDING TO MEASUREMENT(l)

Measurement

Vol

Req

(ml) Contalner 2 Preservatlve 3,4

HoldIng

Tlme5
TABLE 1 (CONT)

Vol

Req Holdmg

Measurement (ml) ContaIner2 Preservauve3,4 TIme5

ChromIum+6 200 P,G Cool,4°C 24 Hrs

Mercury

DIssolved 100 P,G FIlter , 28 Days

HN03 to pH<2

Total 100 P,G HN03 to pH<2 28 Days

300 Inorgamcs, Non-Metalhcs

ACIdIty 100 P,G Cool, 4°C 14 Days

Alkahmty 100 P,G Cool, 4°C 14 Days

BromIde 100 P,G NoneReq 28 Days

Chlonde 50 P,G None Req 28 Days

Chlonne 200 P,G NoneReq Analyze

ImmedIately

Cyamdes 500 P,G Cool, 4°C 14 Days7

NaOH to pH >12

o6g ascorbIc aCld6

Fluonde 300 P,G None Req 28 Days

IodIde 100 P,G Cool, 4°C 24 Hrs

NItrogen

Ammoma 400 P,G Cool,4°C 28 Days

H2S04 to pH<2

KJeldahl, Total 500 P,G Cool, 4°C 28 Days

H2S04 to pH<2

NItrate plus Nitnte 100 P,G Cool, 4°C 28 Days

H2S04 to pH <2

NItrate9 100 P,G Cool, 4°C 48 Hrs

Nitnte 50 P,G Cool, 4°C 48 Hrs

'XVll
TABLE 1 (CONT)

Vol

Req Holdmg

Measurement (ml) ContaIner2 34 TIme5 PreservatIve I

Dissolved Oxygen

Probe 300 G bottle and top None Req Analyze

ImmedIately

Wmkler 300 G bottle and top FIX on site 8 Hours

and store

Phosphorus mdark

Orthophosphate, 50 P,G Ftlter on sIte 48 Hrs

DIssolved Cool, 4°C

Hydrolyzable 50 P,G Cool, 4°C 28 Days

H2S04 to pH < 2

Total 50 P,G Cool, 4°C 28 Days

H2S04 to pH < 2

Total, 50 P,G FIlter on sIte 24 Hrs

DIssolved Cool, 4°C

H2S04 to pH<2

Stlica 50 P only Cool, 4°C 28 Days

Sulfate 50 P,G Cool, 4°C 28 Days

Sulfide 500 P,G Cool,4°C 7 Days

add 2 ml zmc

acetate plus NaOH

to pH >9

Sulfite 50 P,G None Req Analyze

ImmedIately

400 OrganIcs

BOD 1000 P,G Cool, 4°C 48 Hrs

COD 50 P,G Cool,4°C 28 Days

H2S04 to pH < 2

OIl & Grease 1000 G only Cool, 4°C 28 Days

H2S04 to pH < 2

OrganIc carbon 25 P,G Cool, 4°C 28 Days

H2S04 or HCI to pH <2

PhenolIcs 500 G only Cool,4°C 28 Days

H~04 to pH <2

XVUI
TABLE 1 (CONT)

Vol

Req Holdmg

Measurement (ml) ContaIner2 Preservanve3

,4 TIme5

MBAS 250 P,G Cool, 4°C 48 Hrs

NTA 50 P,G Cool, 4°C 24 Hrs

1 More specific mstructlOns for preservatIOn and samplIng are found With each procedure as

detalled m this manual A general discussIOn on samplIng water and mdustnal wastewater may

be found m ASTM, Part 31, P 72-82 (1976) Method D-3370

2 PlastIc (P) or Glass (G) For metals, polyethylene With a polypropylene cap (no Imer) IS

preferred

3 Sample preservation should be performed ImmedIately upon sample collection For

composite samples each alIquotshould be preserved at the time of collection When use of

an automated sampler makes ItImpOSSIble to preserve each alIquot, then samples may be

preserved by mamtammg at 4°C until composItmg and sample splIttmg IS completed

4 When any sample IS to be shIpped by common carner or sent through the United States

Malls, It must comply with the Department of Transportation Hazardous Matenals

Regulations (49 CFR Part 172) The person offermg such matenal for transportation IS

responsIble for enSUrIng such comphance For the preservatIOn reqUIrements of Table 1,

the OffIce of Hazardous Matenals, Matenals Transportation Bureau, Department of

TransportatIOn has determmed that the Hazardous Matenals Regulations do not apply to

the followmg matenals Hydrochlonc aCId (HC1) m water solutions at concentrations of

004% by weIght or less (pH about 1 96 or greater), NItncaCId(HN03) III watersolutIOns at

concentrations of 0 15% by weIght or less (pH about 1 62 or greater), Sulfunc aCId (H2S04)

m water solutIOns at concentrations of 035% by weIght or less (pH about 1 15 or greater),

SodIUm hydroXIde (NaOH) m water solutIOns at concentrations of 0 080% by weIght or

less (pH about 12 30 or less)

5 Samples should be analyzed as soon as pOSSIble after collectIOn The times lIsted are the

maXImum times that samples may be held before analySIS and still conSIdered valId

Samples may be held for longer penods only If the permittee, or momtonng laboratory,

has data on fIle to show that the speCIfIc types of sample under study are stable for the

longer time, and has receIved a vanance from the RegIOnal Admimstrator Some samples

may not be stable for the maXImum time penod gIven m the table A permittee, or

monItormg laboratory, IS oblIgated to hold the sample for a shorter time If knowledge

eXIsts to show thIS IS necessary to maIntaIn sample stabIlIty

6 Should only be used III the presence of reSIdual chlonne

XIX
7 Maximum holdmg time IS 24 hours when sulftde IS present OptlOnally, all samples may

be tested wtth lead acetate paper before the pH adjustment m order to determme If sulftde

IS present If sulfide IS present, H can be removed by the addition of cadmlUm mtrate

powder until a negative spot test IS obtamed The sample IS ftltered and then NaOH IS

added to pH 12

8 Sample!> should be fIltered Immediately on-SHe before addmg preservative for dissolved

metals

9 Forsamples flOm non-chlonnated dnnkmg water suppltes conc H 2S04 should be added

to lo,\'er sample pH to less than 2 The sample should be analyzed before 14 days

X.X
ENVIRONMENTAL PROTECTION AGENCY

REGIONAL QUALITY ASSURANCE COORDINATORS

REGION I

Warren H Oldaker

Central RegIOnal Laboratory

Environmental SerVices DiviSIOn

60 Westview Street

Lexmgton, MA 02173

FTS 671-6700

COML 617-671-6700

REGION II

Gerald F McKenna

Research and Quahty Assurance

Branch

Environmental Services DiViSIOn

Edison, NJ 08837

FTS 340-6645

COML 201-321-6645

REGION III

Charles Jones, J r

(3SA60)

Water Quahty Momtonng Branch

Environmental Services DivisIOn

6th & Walnut Streets, Curtis Bldg

Philadelphia, PA 19106

FTS 597-9162

COML 215-597-9162

REGION IV

Wade Kmght

Laboratory SerVices Branch

Environmental Services DiVIsIOn

College Station Road

Athens, GA 30613

FTS 250-3165

COML 404-546-3165

REGION V

DavId Payne

Quahty Assurance OffIce

EnVIronmental ServIces DIVISIOn

536 South Clark Street

ChIcago, IL 60605

FTS 353-7712

COML 312-353-7712

REGION VI

Eloy R Lozano

EnvIronmental ServIces DiVISIOn

1201 Elm St , FIrSt Int'l Bldg

Dallas, TX 75270

FTS 729-2697

COML 214-767-2697

REGION VII

Charles P Hensley

Laboratory Branch

Environmental ServIces DivisIOn

25 Funston Road

Kansas CIty, KS 66115

FTS 758-4285

COML 816-374-4285

REGION VIII

J uamta HIllman

Environmental Services DIViSIOn

Lmcoln Tower Bldg, Smte 900

1860 Lmcoln Street

Denver, CO 80295

FTS 327-4935

COML 303-837-4935

XXI

REGION IX

Ho Lee Young

OffIce of Quahty Assurance

and Momtonng Systems

215 Fremont Street

San FranCisco, CA 94105

FTS 454-8002

COML 415-556-8002

REGION X

Barry Townes

EnvIronmental SerVIces DiViSIOn

1200 Sixth Avenue

Seattle, WA 98101

FTS 399-1675

COML 206-442-1675
COLOR

Method 110.1 (Colorimetric, ADMI)

STORET NOS.

00082 at pH 7.6

00083 at ORIGINAL SAMPLE pH

1 Scope and ApphcatlOn

1 1 ThIs method IS apphcable to colored waters and waste that have color charactenstlcs

slgmficantly dIfferent from the yellow plattnum-cobaltstandard

1 2 A workmg range of25 to 250 color umts IS recommended Sample values above 250 umts

may be determmed by quantttatlve dtlutton

2 Summary ofMethod

2 1 ThIs method IS an extenslOn of the Tnstlmulus Ftlter Methodl Tnstlmulus values are

converted to an ADMI smgle number color dIfference, of the same magmtude assIgned

to platmum-cobaltstandards, usmg the Adams NIckerson Color DIfference (DE)

2 2 Tnstlmulus values obtamed by Spectrophotometnc Method 204Bl may be used to

calculate ADMI values as outhned m thIs procedure under CalculatIon 9 2

3 Interferences

3 1 Smce very shght amounts of turbIdIty mterfere wIth the determmatlon, turbId samples

must be filtered prlOr to analysIs The optImum filter medIa to remove turbIdIty wIthout

removmg color has not been found Membrane and glass fiber filters wIth functlOnal pore

sIzes of approxImately 0 45 u are convement to use Other techmques such as

centnfugmg and/or filter aIds may be used

4 Sample Handhng and PreservatIon

4 1 Smce blOlogical actIVIty may change the color charactenstics of a sample, the

determmatlOn should be made as soon as possIble Refngeration at 4°C IS recommended

5 CahbratlOn

5 1 Standard curves must be estabhshed (as outhned In Procedure 8 3) for each photometer

used, and are not Interchangeable For color values less than 250, a 5 cm cell path IS

recommended Less than 5 cm cell paths may be used If cahbratlOn IS performed wIth the

shorter cell

6 Apparatus

6 1 Spectrophotometer or filter photometer capable of transmiSSlOn measurements usmg

tnstImulus filters hsted below

Approved for NPDES

Issued 1978

110 1-1
Fdter number

1

2

3

Wavelen~h of maXImum

transmIttance In nm

590

540

438 , .

CornIng deSIgnatIon*

CS 3-107

CS 4-98

CS 5-70

·AvaIlable from CornIng Glass Works, OptIcal Products Department,

CornIng, NY 14830

7. Reagents

7 1 Standard chloroplatInate solutlOn DIssolve 1 246 g potaSSIUm chloroplatInate, K2PtCI6,

(eqwvalent to 0 500 g metallIc Pt) and 1 g crystallIne cobaltous chlonde, CoCl2·6H20, In

dIstIlled water contromng 100 ml of conc HCl DIlute to 1000 ml WIth dIstIlled water

ThIS standard SolutIon IS defined as 500 ADMI color umts

7.2 SulfuncacId, concentrated

7.3 SodIUm hydrOXide, 10 N DIssolve 40 g ofsodIUm hydroXIde In 80 ml of dIstIlled water

Cool to room temperature and dIlute to 100 ml WIth dIstIlled water

8. Procedure

8 1 Prepare two 100 ml volumes ofsample by maIntaInIng the ongtnal pH ofone alIquot and

adjustIng the second alIquot as necessary to pH 7 6 WIth sulfunc aCId (7 2) or sodIUm

hydroxIde (7 3)

8 2 FIlter samples to remove turbIdIty through a 0 45 u membrane filter, glass fiber filter or

otherswtable medIa (see Interferences 3 1)

83 Use dIstIlled water to set the transmIttance at 100% and then determIne the

transmIttance of the clanfied sample or standard WIth each o~ the three tnstimulus

fIlters CalIbratlOn standardsfrom 25 to 250 umts are recommended

9. CalculatIons

9.1 Catcl,llate IntermedIate tnstImulus values for samples and standards from the , . tran,stmttance data In 8 3 USIng the follOWIng equatIons

Xs = (T3 X 0 1899) + (TI X 0791)

Zs = T3 x 11835

where

T1 = transmIttance value In % USIng filter number 1

T2 = transmIttance value In % USIng filter number 2

110 1-2
T3 = transmittance value In % USing filter number 3

92 Convert tnstlmulus values to the corresponding Munsell values Vx, Vy and Vz by the use

ofpubltshed tables2

,3,4, or the equatIOn suggested by Bndgeman5

9 3 Calculate DE values for samples and standards, construct a caltbratlOn curve by plotting

DE against ADMI umts ofstandards and determine ADMI color umts ofsamples from

the caltbratlon curve

where Vxs> VyS and Vzs = the Munsell values for X s, Ys and Zs respectively and Vxc, VyC

and Vzc = the Munsell values for a blank solutIOn whose tnstlmulus values are Xc, Yc

and~ ,

NOTE 1: Ifthe photometer used IS set at 100% transmittance with dlsttlled water, the

tnstlmulus values for the blank are 9809, 10000 and 11835 for Xc, Yc and Zc

respectively If necessary, tnstlmulus values for the blank are determined as In

calculation (9 1)

9 4 Report ADMI color values at pH 7 6 and at the ongInal pH

NOTE 2: The Intermediate tnstlmulus values calculated under 9 1, USing the three

tnstImulus filters, are used only to calculate the ADMI color value They should not be

reported as tnstlmulus values or used to determine dominant wavelength, luminance and

punty

10 PrecIsIOn and Accuracy

10 I Accuracy data on actual samples cannotbe obtained

10 2 PrecIsion data are not avatlable at this time

BIblIography

1 Standard Methods for the ExaminatIon ofWater and Wastewater, 14th Edition (1975), p 64

2 J Soc Dyers and Colonsts, 86, No 8,354 (1970)

3 WysL.eckl and Sttles, Color SCience, Wtley, NY, 1967, Tables 64 A, Band C

4 Judd and Wyszeckt, Color In BUSiness, SCience and Industry, 2nd EditIon, Wtley, NY (1963)

Tables A, Band C In AppendiX

5 J Opt Soc Am, Volume 53, page 499, Apnl1963

6", Dyes and the EnVironment-Report on Selected Dyes and Their Effects, Volume 1, Sept 1973

AppendiX, Amencan Dye Manufacturers Institute, Inc

110 1-3
COLOR

Method 110.2 (Colorimetric-Platinum-Cobalt)

STORET NOS.

TRUE COLOR 00080

APPARENT COLOR 00081

1 Scope and ApphcatlOn

1 1 The Platmum-Cobalt method IS useful for measunng color of water denved from

naturally occurnng matenals, 1 e , vegetable resIdues such as leaves, barks, roots, humus

and peat matenals The method IS not apphcable to color measurement on waters

contammg hIghly colored mdustnal wastes See ADMI color method m thIS manual

NOTE 1. The Spectrophotometnc and Tnstlmulus methods are useful for detectmg

specIfic color problems The use of these methods, however, IS labonous and unless

determmatlOn ofthe hue, punty, and lummance IS desIred, they are ofhmlted value

2 Summary ofMethod

2 1 Color IS measured by vIsual companson of the sample wIth platmum-cobalt standards

One umt of color IS that produced by 1 mg/1 platmum m the form ofthe chloroplatmate

lOn

3 Interferences

3 I Smce very shght amounts ofturbIdIty mterfere wIth the determmatlOn, samples showmg

vIsible turbidity should be clarIfied by centnfugatlOn

3 2 Method IS pH dependent

4 Sample Handhng and PreservatIon

4 I Representative samples shall be taken m scrupulously clean glassware

4 2 Smce blOlogICal actIVity may change the color charactenstlcs of a sample, the

determmatlOn should be made as soon as possIble RefngeratlOn at 4°C IS recommended

5 Apparatus

5 I Nessler tubes Matched, tall form, 50 ml capacIty

6 Reagents

6 1 Standard chloroplatmate solutlOn DIssolve I 246 g potaSSIUm chloroplatmate, K2PtCI6,

(eqUIvalent to 0 500 g metalhc Pt) and 1 g crystalhne cobaltous chlonde, CoCI2-H20, m

dIstilled water contammg 100 ml of conc HCI Dilute to 1000 ml With dIstilled water

This standard solutlOn IS eqUIvalent to 500 color umts

7 Preparation ofStandards

7 1 Prepare standards m mcrements from 5 to 70 umts The followmg sene,s IS suggested

Approved for NPDES

Issued 1971

1102-1
MI of Standard SolutIon

DIluted to 50 0 rol

wIth DIstIlled Water

00

05

10

15

20

25

30

35

40

45

50

60

70

Color In

ChloroplatInate Umts

o

5

10

15

20

25

30

35

40

45

50

60

70

7.2 Protect these standards agamst evaporation and contammatlon by use of clean, mert

stoppers

NOTE 2: The standards also must be protected agamst the absorption of ammoma smce

an mcrease m color wdl result

8. Procedure

8 1 Apparent color Observe the color ofthe sample by filhng a matched Nessler tube to the

50 ml mark With the water and compare With standards ThiS companson IS made by

lookmg vertically downward through the tubes toward a white orspecularsurface placed

atsuch an angle that hght IS reflected upward through the columns of hqUld Ifturbidity

has not been removed by the procedure glVen In (82), report the color as "appalent

color" If the color exceeds 70 umts, ddute the sample With dlstl1led water m known

proportions untl1 the color IS wlthm the range ofthe standards

8.2 True color Remove turbidity by centnfugmg the sample untd the supernatant IS clear

The tlme reqUIred w111 depend upon the nature ofthe sample, the speed ofthe motor, and

the ramus ofthe centnfuge, but rarely WIll more than one hour be necessary Compare

the centnfuged sample WIth dIstl1led water to msure that turbIdIty has been removed If

the sample IS clear, then compare WIth standards as gIven m (8 1)

9. Calculation

9.1 Calculate the color umts by means ofthe followmg equatIon

Color umts = A X 50

V

where

A = estimated color ofdl1uted sample

V = mlsample taken for dl1utlOn

1102-2
9 2 Report the results m whole numbers as follows , .

Color Vmts

1-50

51-100

101-250

251-500

10 PreclSlon and Accuracy

10 1 PrecisIOn and accuracy data are not available at this time

BIblIography

Record to Nearest

1

5

10

20

1 Standard Methods for the Exammatton ofWater and Wastewater, 14th EdItion, p 64, Method

204A(1975)

- .;-

, .;

" ,

, l

1102-3
COLOR

Method 110.3 (Spectrophotometric)

STORET NO. 00080

1 Scope and ApphcatlOn

1 1 ThIS method IS apphcable to drInkIng, surface, and sahne waters, domestIc and Industnal

wastes It must be used for Industnal wastes that cannot be determIned by the PlatInumCobalt method

2 Summary ofMethod

2 1 Color charactenstIcs are measured at pH 7 6 and at the ongmal pH by obtaInIng the

VISIble absorptIOn spectrum of the sample on a spectrophotometer The percent

transmISSIOn at certam selected wavelengths IS used to calculate the results

2 2 The results are expressed m terms of dommant wavelength, hue, lumInance, and punty

3 Interferences

3 1 Smce very shght amounts ofturbIdIty mterfere wIth the determInatIOn, samples must be

filtered before analysIs

4 Sample Handhng and PreservatIon

4 1 Smce bIOlogICal actiVIty may change the color charactenstics of a sample, the

determmatlOn should be made as soon as possIble RefngeratIOn at 4°C IS recommended

5 Reference

5 1 The procedure to be used for thIS determmatlOn IS found m

Standard Methods for the ExammatlOn ofWater and Wastewater, 14th EdItIOn,

p 66, Method 204B (1975)

Approved for NPDES

Issued 1974

110 3-1
CONDUCfANCE

Method 120.1 (Specific Conductance, umhos at 25°C)

STORET NO. 00095

1 Scope and ApplIcatIon

1 1 This method IS applIcable to drmkmg, surface, and salIne wates, domestIc and mdustrial wastes and acid ram (atmosphenc depOSItIon)

2 Summary of Method

2 I The specIfIc conductance of a sample IS measured by use of a self-contamed conductIvity

meter, Wheatstone bndge-type, or equivalent

2 2 Samples are preferable analyzed at 25°C If not, temprature correctIons aremade and

results reported at 25°C

3 Comments

3 I Instrument must be standardized with KCI solutIon before dally use

32 ConductIvity cell must be kept clean

3 3 Field measurements with comparable mstruments are relIable

3 4 Temperature vanatlons and corrections represent the largest source of potential error

4 Sample HandlIng and Preservation

4 I Analyses can be performed either m the field or laboratory

4 2 If analysIs IS not completed wlthm 24 hours of sample collection, sample should be

filtered through a 0 45 micron fIlter and stored at 4°C FIlter and apparatus must be

washed with high qualIty distIlled water and pre-nnsed With sample before use

5 Apparatus

51 Conductivity bndge, range 1 to 1000 pmho per centimeter

5 2 Conductivity cell, cell constant 1 0 or micro dlppmg type cell with 1 0 constant YSI

#3403 or eqUivalent

5 4 Thermometer

6 Reagents

6 1 Standard potassIUm chlonde solutions, 001 M Dissolve 07456 gm of pre-dried (2 hour

at 105°q KCI m diStilled water and dIlute to 1 lIter at 25°C

7 Cell CalIbration

7 1 The analyst should use the standard potassIUm chlonde solutIon (6 1) and the table

below to check the accuracy of the cell constant and conductIVity bndge

Approved for NPDES

Issued 1971

Edltonal reVISion, 1982

1201-1
CondUCtiVIty 0 01 m KCI

°C

21

22

23

24

25

26

27

28

Micromhos/cm

1305

1332

1359

1386

1413

1441

1468

1496

8. Procedure

8.1 Follow the dIrection of the manufacturer for the operatIon of the mstrument

8 2 Allow samples to come to room temperature (23 to 27°C), If possIble

8.3 Determme the temperature of samples withm 0 5°C If the temperature of the samples

IS not 25°C, make temperature correctIon m accordance WIth the mstructIOn m SectIon

9 to convert readIng to 25°

9 Calculation

9 I These temperature correctIOns are based on the standard KCI solutIOn

9.1 I If the temperature of the sample IS below25°C, add 2% of the readmg per degree

9 I 2 If the temperature IS above 25°C, subtract 2% of the readmg per degree

9.2 Report results as SpecIfIc Conductance, J.lIllhos/cm at 25°

10. PreelSlon and Accuracy

10.1 Forty-one analysts m 17 laboratorIes analyzed SIX synthetIc water samples contammg

mcrements of morgamc salts, WIth the followmg results

Increment as PrecIsIon as Accuracy as

SpecIfic Conductance Standard DeVIatIon BIas, BIas,

% umhos/cm

100 755 -202 -20

106 814 -076 -08

808 661 -363 -293

848 796 -454 -385

1640 106 -536 -879

1710 119 -508 -869

(FWPCA Method Study 1, Mmeral and PhySIcal Analyses )

102 In a smgle laboratory (EMSL) usmg surface water samples WIth an aV,erage

condUCtIVIty of 536 J.lIllhos/cm at 25°C, the standard deVIatIOn was ±6

120 1-2
Bibliography

I The procedure to be used for thIs determmatlon IS found m

Annual Book of ASTM Standards Part 31, "Water," Standard D1125-64, p 120 (1976)

2 Standard Methods for the Exammatlon of Water and Wastewater, 14th EditIOn, p 71,

Method 205 (1975)

3 InstructIOn Manual for YSI Model 31 ConductiVIty Bndge

4 Peden, ME, and Skowron "lome StabIlIty of PreCIpItatIOn Samples," Atmosphenc

EnvIronment, Vol 12, p 2343-2344, 1978

120 1-3
HARDNESS, Total (mg/l as CaC03)

Method 130.1 (Colorimetric, Automated EDTA)

STORET NO. 00900

1 Scope and Apphcatton

1 1 ThIS automated method IS appltcable to dnnkIng, surface, and saltne waters The

apphcable range IS 10 to 400 mg/l as CaC03 ApproxImately 12 samples per hour can be

analyzed

2 Summary ofMethod

2 1 The magnesIUm EDTA exchanges magnesIum on an eqUIvalent baSIS for any calCIum

and/or other catIons to form a more stable EDTA chelate than magneSIUm rrhe free

magneSIUm reacts With calmagtte at a pH of 10 to gtve a red-Violet complex Thus, by

measunng only magneSIUm concentration In the final reaction stream, an accurate

measurement oftotal hardness IS pOSSible

3 Sample HandlIng and PreservatIOn

3 1 Cool to 4°C, HN03 to pH <2

4 Interferences

4 1 No SignificantInterferences

5 Apparatus

5 1 Techmcon AutoAnalyzer consistIng of

5 1 1 Sampler I

5 1 2 ContInuous Fl1ter

513 Mamfold

5 1 4 ProportIOnIng Pump

5 1 5 Colonmeter eqUIpped With 15 mm tubularflow cell and 520 nm filters

5 1 6 Recorder eqUIpped With range expander

6 Reagents

6 1 Buffer Dissolve 67 6 g NH4CI In 572 m1 of NH40H and dl1ute to 1 hter With distilled

water

6 2 Calmaglte IndIcator Dissolve 0 25 g In 500 ml of dlstl1led water by strrnng

approximately 30 mInutes on a magnetic strrrer Fl1ter

6 3 MonomagnesIUm ethylenedlamIne-tetraacetate (MgEDTA) Dissolve 0 2 g ofMgEDTA

In 1hter ofdlstdled water

6 4 Stock Solutton Weigh 1000 g of calCIUm carbonate (pre-dned at 105°e) Into 500 m1

Erlenmeyer flask, add 1 1 HCI untd all CaC03 has dissolved Add 200 ml of distilled

water and bod for a few mInutes Cool, add a few drops of methyl red Indicator, and

adjust to the orange color With 3N NH40H and ddute to 1000ml With distilled water 1 0

m1 = 10mgCaC03 •

Approved for NPDES

Issued 1971

130 1-1
6 4 I Dllute each of the followmg volumes ofstock solutlOns to 250 ml m a volumetnc

flask for appropnate standards

Stock SolutIon, ml

25

50

100

150

250

350

500

750

1000

CaC03, mg/l

100

200

400

600

1000

1400

2000

3000

4000

6 5 Ammomum Hydroxlde, IN Dllute 70 ml ofconc NH40H to I b.ter wlth dlstl1led water

7. Procedure

7 I Pretreatment

7 I I For dnnkmg waters, surface waters, sahne waters, and dl1utlOns thereof, no

pretreatmentsteps are necessary Proceed to 7 2

7 I 2 For most wastewaters, and hlghly polluted waters, the sample must be dlgested as

glven m the Atomlc AbsorptlOn Methods sectlOn of thls manual, paragraphs 4 I 3

and 4 I 4 Followmg thlS digestIon, proceed to 7 2

72 Neutrahze 500 m1 ofsample wlth IN ammomum hydroxIde (6 5) and note volume of

NH40Hused

7 3 Set up mamfold as shown m Flgure 1

7 4 Allow both colonmeter and recorder to warm up for 30 mmutes Run a basehne wIth all

reagents, feedmg dlstilled water through the sample hne Adjust dark current and

operatIve opemng on colonmeter to obtam stable baselme

7 5 Place dlstl1led water wash tubes m alternate opemngs m Sampler and set sample tlmmg

at 2 5mlnutes

7 6 Arrange workmg standards m Sampler m order of decreasmg concentratlOns Complete

loadmg ofSampler tray wIth unknown samples

7.7 SWItch sample hne from dIstilled water to Sampler and begm analysIs

8. CalculatlOn

8 1 Prepare standard curve by plottmg peak helghts of processed standards agamst

concentratlOn values Compute concentration of samples by companng sample peak

heIghts wIth standard curve Correct for amount ofNH40H used m 7 2 as follows

A mg/l = 50 x B

where;

A= Vol of sample plus volume of NH40H

B = ConcentratlOn from standard curve

1301-2
9 PrecIsIon and Accuracy

9 1 In a smgle laboratory (EMSL), usmg surface watersamples at concentratIOns of 19, 120,

385, and 366 mg/1 as CaC03, the standard devIatIons were ±1 5, ±1 5, ±4 5, and ±5 0,

respectIvely

92 In a smgle laboratory (EMSL), usmg surface water samples at concentratIons of 39 and

296 mg/1 as CaC03, recovenes were 89% and 93%, respectIvely

BiblIography

1 Techmcon AutoAnalyzer Methodology, Bulletm No 2, Techmcon Controls, Inc, Chauncey,

New York (July 1960)

2 Standard Methods for the Exammatlon of Water and Wastewater, 14th EdItIon, p 202,

Method 309B (1975)

1301-3
FILTER

(O)~'f

SMAlL MIXING I COIL (SM) 1III1/llIln

p W 390

t P W 3 90 1DISTILLED WATER

I I o80 SAMPLE

/fPO SAMPLER 1

~o0

°

nm °

P It 2 50 DISTILLED WATER

P P 2 58 All

t I I all SAMPLE

IUE ILIIE 1 60 Me:EDTA CONTINUO!

SM

0000 ILIIE ILIIE 1 &0 BUFFER

+ 'allCI ILACI a 32 IUICHOR

LARGE

MIXING WASTE COIL P P 2 50 WASTE

I PUPOITIONUlli PUP

I

I...

1'"""'11 r'

COLORIMETER 'V SAMPLING TIME 20MI'

15 •• TUBULAR f/c RECORDER WASH TUBES ONE

520 II. FILTERS

1/2 DELA

COIL

-

w

o

-

J:..

FIGURE 1. HARDNESS MANIFOLD AA-I
HARDNESS, Total (mg/l as CaC03)

Method 130.2 (Titrimetric, EDTA)

STORET NO. 00900

1 Scope and Apphcatlon

1 1 This method IS apphcable to dnnlang, surface, and sahne waters, domestic and mdustnal

wastes

12 The method IS sUltable for all concentratIOn ranges of hardness, however, m order to

avoid large titratIOn volumes, use a sample ahquot contammg not more than 25 mg

CaC03

1 3 Automated titratIOn may be used

2 Summary ofMethod

2 1 CalclUm and magneslUm Ions m the sample are sequestered upon the addition of

dlsodlUm ethylenedlamme tetraacetate (Na2EDTA) The end pomt of the reactIOn IS

detected by means of Enochrome Black T mdlcator, which has a red color m the

presence ofcalclUm and magneslUm and a blue color when the catIOns are sequestered

3 Sample Handhng and Preservation

3 1 Cool to 4°C, HN03 to pH < 2

4 Comments

4 1 Excessive amounts of heavy metals can mterfere ThiS IS usually overcome by

complexmg the metals With cyamde

4 1 1 Routme addition ofsodlUm cyamde solution (CautIOn deadly pOlson) to prevent

potential metalhc mterference IS recommended

5 Apparatus

5 1 Standard laboratory tItnmetnc eqUlpment

6 Reagents

6.1 Buffersolution

6 1 1 If ma$fieslUm EDTA IS avallable Dissolve, 169 g NH4Cl m 143 ml conc

NH40H m a 250 ml volumetnc, add 1 25 g ofmagneslUm salt ofEDTA and dllute

to the mark With dlst1lled water Then go to 6 1 3

612 IfmagneslUm EDTA IS unavallable Dissolve 1179 g dlsodlUm EDTA (analytIc~1

reagent grade) and 780 mg MgS04-7H20 (or 644 mg MgCI2-6H20) m 50 ml

dlstllied water Add thiS solutIOn to a 250 m1 volumetnc flask contammg 16 9 g

NH4Cl and 143 ml conc NH40H With mlxmg and dllute to the mark With

distilled water

6 1 3 Store m a tightly stoppered plastiC botHe, stable for approxlIDately one month

Dispense With bulb operated pipet Discard when 1or 2 ml added to sample falls to

produce a pH of 10 0 ±O 1at end pomt oftitratIOn

Approved for NPDES

Issued 1971

EditOrIal reVISIOn 1978 and 1982

1302-1
6 1 4 CommercIally avaIlable "odorless buffers" WhICh are more stable, may be used

6.2 InhIbItors For most waters InhIbItors are not necessary If Interfenng Ions are present

use one ofthe follOWIng

62 1 InhIbItor I NaCN powder (CautIon extremely pOIsonous) Flush solutIons or

sample contaImng thIs down draIn USIng large quantItIes of water Make sure no

aCIds are present whIch mIght lIberate HCN gas

6.22 InhIbItor II DIssolve 50 g Na2S-9 H20 or 3 7 g Na2S·5 H20 In 100 ml dIStilled

water Exclude aIr WIth tIghtly fitted rubber stopper ThIS gIves sulfide preCIpItates

whIch may obscure the end POInt If large quantIties of heavy metals are present

Detenorates rapIdly throllgh aIr oXIdatIOn

623 InhIbItor III DIssolve 45 g hydroxylamIne hydrochlonde m 100 m1 of 95%

ethanol or Isopropanol

63 IndIcator Use a commercIally avaIlable IndIcator such as Calmaglte IndIcator

(Mallmckrodt) or one ofthe formulatIOns descnbed below (63 1-6 3 3)

6.3 I MIX 0 5 g Enochrome Black T WIth 4 5 g hydroxylamIne hydrochlonde DIssolve

In 100 m1 of95% ethanol or Isopropanol

6 3 2 DIssolve 0 5 to 109 Enochrome Black T m an appropnate solvent such as

tnethanolamme or 2-methoxyethanol Stable approxImately one week

6 3 3 MIX together 0 5 g Enochrome Black T and 100 g NaCl

64 Standard EDTA tltrant, 002 N 'Place 3 723 g analytICal reagent grade dISodIUm

ethylenedIamme tetraacetate dIhydrate, Na2H2ClOH120gN2-2 H20 mal lIter volumetnc

flask and dIlute to the mark WIth dIstIlled water Check WIth standard calCIUm solution

(641) by tItratIOn (6 4 5) Store m polyethylene Check penodICally because of gradual

detenoratlon

64.1 Standard calcIUm solutlon 0 02 N Place 1 000 g anhydrous calcIUm carbonate

(pnmary standard low In metals) In a 500 ml flask Add, a lIttle at a tlme, 1+ 1

HCL (642) untll all of the CaC03 has dIssolved Add 200 ml dIstllled water

Boll for a few mInutes to expel CO2 Cool Add a few drops of methyl red

mdicator (643) and adjust to IntermedIate orange color by addIng 3N

NH40H (6 4 4) or 1 + 1 HCI (6 4 2) as reqUIred Quantltatlvely transfer to a

1 lIter volumetnc flask and dIlute to mark WIth dIstIlled water

6 4 2 Hydrochlonc aCId solutIOn, 1+1

643 Methyl red IndIcator DIssolve 0 10 g methyl red In dIstIlled water In a 100 ml

volumetnc flask and dIlute to the mark

6 4 4 AmmOnIum hydrOXide solutIOn, 3 N DIlute 210 ml ofconc NH40H to 1 hter WIth

dIstIlled water

645 StandardIZatlon tltratlon procedure Place 10 0 ml standard calcIUm solution

(641) m vessel contaInIng about 50 m1 dIstIlled water Add 1 m1 buffer SolutIon

(6 1) Add 1-2 drops mdICator (6 3) or small scoop of dry IndIcator (6 3 3) TItrate

slowly With contmuous stIrnng untIl the last reddIsq tmge dIsappears, addmg last

1302-2
few drops at 3-5 second mtervals At end pomt the color IS blue Total tItratIon

duratIon should be 5mmutes from the tIme ofbuffer addItIOn

02

N of EDTA ml of EDTA

6 5 Ammolllum HydroxIde, IN DIlute 70 ml ofconc NH40H to 1 lIter wIth dIstIlled water

Procedure

7 1 Pretreatment

7 1 1 For drmkmg waters, surface waters, salIne waters, and dIlutIons thereof, no

pretreatmentsteps are necessary Proceed to 7 2

7 1 2 For most wastewaters, and hIghly polluted waters, the sample must be dIgested as

gIven m the AtomIC AbsorptIOn Methods sectIon ofthIS manual, paragraphs 4 1 3

and 4 1 4 Followmg thIS dIgestIOn, proceed to 7 2

7 2 TItratIOn ofsample-normal to hIgh hardness

721 Sample should reqUire < 15 ml EDTA tItrant (64) and tItratIon should be

completed wlthm 5 mmutes ofbuffer addItIon

7 2 2 Place 250m1sample m tItratIon vessels, neutralIze WIth 1N ammOlllum hydrOXIde

(6 5) and dIlute to about 50 ml

723 Add 1to 2 ml buffersolutIOn (6 1)

724 If end pomt IS not sharp (as determmed by practIce run) add mhlbltor at thIS pomt

(see 74)

7 2 5 Add 1 to 2 drops mdlcator solutIOn (6 3 1 or 6 3 2) or small scoop of dned powder

mdlcator formulatIOn (6 3 3)

726 TItrate slowly WIth contmuous strrnng WIth standard EDTA tItrant (6 4) untIl last

reddIsh tmt dIsappears SolutIOn IS normally blue at end pomt

73 TItratIOn ofsample-low hardness (less than 5 mg/l)

731 Usealargersample(lOOml)

7 3 2 Use proportIonately larger amounts ofbuffer, mhibitor and mdlcator

7 3 3 Use a microburet and run a blank usmg redIstilled, dIstIlled or deIolllzed water

7 4 To correct for mterferences

7 4 1 Some metal Ions mterfere by causmg fadmg or mdIstmct end pomts InhIbItors

reduce thIS m accord WIth the scheme below for 250 ml samples dIluted to 50 ml

7

1302-3
Mwnmum ConcentratIOns of Interferences PermIssIble

wIth Vanous Inhibitorsa

Interfenng

Substance

Alummum

Banum

CadmIUm

Cobalt

Copper

Iron

Lead

Manganese (Mn2+)

NIckel

StrontIUm

Zmc

Polyphosphate

MaXImum Interference

ConcentratIon mgll

InhIbItor I InhIbItor II

20 20

b b

b 20

over 20 03

over 30 20

over 30 5

b 20

b 1

over 20 03

b b

b 200

10

Inhibitor III

20

b

b

oc

03

20

b

oc

b

b

a Based on 25-ml sample dIluted to 50 ml

b Titrates as hardness

c Inhibitor faIls If substance IS present

7 4 2 Inhlbltor I At step 7 2 4 add 250 mg NaCN Add sufficlent buffer to achleve pH

lO 0 ± 0 1to offset alkahmty resultmg from hydrolysls ofsodlUm cyamde

7.4 3 Inmbltor II At step 724 add 1ml ofmhlbltor II (6 2 2)

744 lnillbltor III Atstep 7 24 add 1ml ofInhlbltor III (6 2 3)

8 CalculatlOns

Hardness (EDTA) q

mgCaC03/1

A x N x 50,000

ml sample

where

A = ml EDTA titrant (6 4)

N = normahtyofEDTA titrant

1302-4
9 PreclSlon and Accuracy

9 1 Forty-three analysts m nmeteen laboratones analyzed SIX synthetic water samples

contammg exact mcrements of calcmm and magnesmm saits, with the followmg results

Increment as PreClSlon as Accuracy as

Total Hardness Standard Deviation Bias, Bias,

mg/hter, CaC03 mg!hter, CaC03 % mg!hter, CaC03

31 287 -087 -0003

33 252 -073 -024

182 487 -019 -04

194 298 -104 -20

417 965 -335 -13 0

444 973 -323 -143

(FWPCA Method Study 1, Mmeral and PhyslCal Analyses)

92 In a smgle laboratory (EMSL), usmg surface water samples at an average concentratlOn

of 194 mg CaC03!1, the standard devlatlOn was ±3

93 A synthetic unknown sample contammg 610 mg!1 total hardness as CaC03 contnbuted

by 108 mg!1 Ca and 82 mg!1 Mg, and the followmg supplementary substances 3 1mg!1

K, 199 mg!1 Na, 241 mg!1 chlonde, 0 25 mg!1 mtnte N, 11 mg!1 mtrate N, 259 mg!1

sulfate, and 42 5 mg!1 total alkahmty (contnbuted by NaHC03) m dlstliled water was

analyzed m 56 laboratones by the EDTA titnmetnc method with a relative standard

devlatlOn of2 9% and a relative error of0 8%

BiblIography

1 Standard Methods for the ExammatlOn of Water and Wastewater, 14th EdltlOn, p 202,

Method 309B (1975)

2 Annual Book of ASTM Standards, Part 31, "Wat.er", Standard D 1126-67, p 161, Method B

(1976)

1302-5
ODOR

Method 140.1 (Threshold Odor, Consistent Series)

STORET NO. 60°C: 00086

Room Temp: 00085

1 Scope and ApphcatIOn

1 1 This method IS apphcable to the determmatIOn of threshold odor of dnnkmg, surface,

and sahne waters, domestIc and mdustnal wastes

1 2 HIghly odorous samples are reduced m concentratIOn proportIOnately before bemg

tested Thus, the method IS apphcable to samples rangmg from nearly odorless natural

waters to mdustnal wastes WIth threshold odor numbers m the thousands

2 Summary ofMethod(l)

2 1 The sample of water IS diluted WIth odor-free water until a dilutIOn that IS of the least

defimtely perceptIble odor to each tester IS found The resultmg ratio by WhICh the

sample has been diluted IS called the "threshold odor number" (T 0 N )

2 2 People vary wIdely as to odor sensItIvIty, and even the same person WIll not be consIstent

m the concentratIOns they can detect from day to day Therefore, panels of not less than

five persons, and preferably 10 or more, are recommended to overcome the vanabIhty of

usmg one observer (2) As an absolute mmimum, two persons are necessary One to make

the sample dilutIons and one to determme the threshold odor

3 Sample Handhng and PreservatIOn

3 1 Water samples must be collected m glass bottles WIth glass or Teflon-hned closures

PlastIC contamers are not rehable for odorsamples and must not be used

3 2 Odor tests should be completed as soon as pOSSIble after collectIOn of the sample If

storage IS necessary, collect at least 1000 ml of sample m a bottle filled to the top

Refngerate, makmg sure no extraneous odors can be drawn mto the sample as the water

cools

4 Interferences

4 1 Most tap waters and some waste waters are chlonnated It IS often deSIrable to determme

the odor of the chlonnated sample as well as of the same sample after removal of

chlonne DechlonnatIon IS achIeved usmg sodIUm thIOsulfate m exact stOichIOmetnc

quantity

4 lIlt IS Important to check a blank to WhICh a SImilar amount of dechlonnatmg agent

has been added to determme If any odor has been Imparted Such odor usually

dIsappears upon standmg Ifexcess reagent has not been added

5 Apparatus

5 1 Odor-free glassware Glassware must be freshly cleaned shortly before use, WIth nonodorous soap and aCId cleamng solutIOn followed by nnsmg WIth odor-free water (61)

Issued 1971

140 1-1
Glassware used In odor testIng should be reserved for that purpose only Rubber, cork,

and plastIc stoppers must not be used

5 2 Constant temperature bath A water bath or electnc hotplate capable of maIntaInIng a

temperature control of ±1°C for performIng the odor test at 60°C The temperature bath

must not contnbute any odor to the odor flasks

53 Odor flasks Glass stoppered 500 ml (1'/32) Erlenmeyer flasks, or WIde-mouthed 500 ml

Erlenmeyer flasks eqUIpped wIth Petn dIshes a.s cover plates

NOTE: Narrow-mouth vessels are not sUItable for runmng odor tests PotentIal posItIve

bIas due to color and/or turbIdIty of water sample under observatIon can be elImInated

by wrappIng odor flasks In alumInum foIl, paIntIng flasks wIth non-odorous paInt, or by

usmg red actInIC Erlenmeyer flasks

5 4 Sample bottles Glass bottles wIth glass or Teflon-lIned closures

5.5 PIpets, measunng 100 and 1 0 m1 graduated In tenths

5.6 Graduated cylmders 250,200, 100, 50, and 25 ml

5 7 Thermometer 0-110°C (±1°C), chemIcal or metalstem dIal type

5.8 Odor-free water generator See FIgure 1

6. Reagents

6 1 Odor-free water Odor-free dIlutIOn water must be prepared as needed by filtratIon

through a bed of actIvated carbon Most tap waters are SUItable for preparatIon of odorfree waters, except that It IS necessary to check the filtered water for chlonne reSIdual,

unusual salt concentratIons, or unusually hIgh or low pH All these may affect some

odoroussamples

Where supplIes are adequate, dIstilled water aVOIds these problems as a source of odorfree water A convement odor-free water generator may be made as shown In FIgure 1

Pass tap or dIstIlled water through the odor-free water generator at a rate of 0 1

lIter/mInute When the generator IS first started, It should be flushed to remove carbon

fines before the odor-free water IS used

6 liThe qualIty of water obtaIned from the odor-free water generator should be

checked daIly at the temperature tests are to be conducted (room temperature

and/or 60°C) The lIfe of the carbon WIll vary WIth the condItIon and amount of

water filtered Subtle odors of bIOlogIcal ongIn are often found If mOIst carbon

filters are permItted to stand Idle between test penods DetectIon of odor In the

water comIng through the carbon IndIcates a change ofcarbon IS needed

7 Procedure

7 1 PrecautIon SelectIOn of persons to make odor tests should be carefully made Extreme

senSItIVIty IS not reqUIred, but InSenSItIve persons should not be used A good observer

has a smcere Interest In the test Extraneous odor stImulI such as those caused by

smokmg and eatIng pnor to the test or through the use ofscented soaps, perfumes, and

shavmg lotIons must be aVOIded The tester should be free from colds or allergtes that

affect odor-response Frequent rests In an odor-free atmosphere are recommended The

room m whIch the tests are to be conducted should be free from dIstractIOns, drafts, and

other odor In certaIn mdustnal atmospheres, a speCIal odor-free room may be reqUIred,

ventIlated by aIr filtered through actIvated carbon and maIntamed at a constant

1401-2
comfortable temperature and hum1d1ty For prec1se work a panel offive or more testers

should be used The persons makmg the odor measurements should not prepare the

samples and should not know the dllutlOn concentrat10ns bemg evaluated These persons

should have been made fam1har w1th the procedure before part1c1patmg m a panel test

Always start,w1th the most dllute sample to aVOld tmng the senses w1th the concentrated

sample The temperature ofthe samples dunng testmg should be kept w1thm 1 degree of

the spec1fied temperature for the test

7 2 Threshold measurement The ratio by wh1ch the odor-beanng sample has to be dlluted

w1th odor-free water for the odor to be Just detectable by the odor test 1S the "threshold

odor number" (T 0 N) The total volume of sample and odor-free water used m each

test 1S 200 ml The proper volume of odor-free water 1S put mto the flask first, the sample

1S then added to the water Table 1 g1ves the dllutlOns and correspondmg threshold

numbers

Table 1

Threshold Odor Number

Correspondmg to VarIOus Dilutions

Sample Volume (ml)

Dl1uted to 200 ml

200

100

50

25

125

63

3 1

16

08

Threshold Odor

Number

1

2

4

8

16

32

64

128

256

7 3 Determme the approx1mate range ofthe threshold odor by

73 1 Addmg 200 ml, 50 ml, 125 ml, and 3 1 ml ofthe sample to separate 500 ml glassstoppered Erlenmeyer flasks contammg odor-free water to make a total volume of

200 ml A separate flask contammg only odor-free water serves as the reference for

companson If run at 60~C, heat the dllutions and the reference m the constant

temperature bath at 60°C (± 1°C)

7 3 2 Shake the flask contammg the odor-free water, remove the stopper, and smff the

vapors Test the sample contammg the least amount of odor-beanng water m the

same way If odor can be detected m th1s dllutlOn, more dllute samples must be

prepared as descnbed m (733) If odor cannot be detected m the first dllutlOn,

repeat the above procedure usmg the sample contammg the next h1gher

concentration of the odor-beanng wate1, and contmue tills process untll odor 1S

clearly detected

140 1-3
I GAL

JUG

Ian t~ _!

2 HOLE

RUBBER STOPPER

GRANULAR

4 xIO-MESH

ACTIVATED

CARBON

PEA SIZE

E---GRAVEL

FI GURE 1. ODOR -FREE WATER GENERATOR

140 1-4
7 3 3 If the sample bemg tested reqUIres more extensIve dl1utlOn than IS provIded by

Table 1, an mtermed1ate d11utlOn IS prepared from 20 ml ofsample dl1uted to 200

ml wIth odor-free water Use thIs dl1utlOn for the threshold determmation

Multiply the TON obtamed by ten to correct for the mtermed1ate dl1utlOn In

rare cases more than one tenfold mtermed1ate dlIutlOn step may be reqUIred

7 4 Based on the results obtamed m the prehmlnary test, prepare a set of dl1utlOns usmg

Table 2 as a gUIde One or more blanks ale mserted m the senes, m the v1c1mty of the

expected threshold, but aVOld1ng any repeated pattern The observer does not know

whIch dl1utlOns are odorous and wmch are blanks He smells each flask m sequence,

begmmng wIth the least concentrated sample and companng wIth a known flask ofodorfree water, untl1 odor IS detected wIth utmost certamty

Table 2

DIlutions for Various Odor IntenSIties

- Sample Volume m WhICh Odor First Noted

200 ml 50 ml 12 5 ml 3 1 ml

Volume (ml) of Sample to be Dlluted to 200 ml

200

100

50

25

125

100

50

25

125

63

50

25

125

63

3 1

(mtermedlate

DIlutIOn

See 733)

7 5 Record the observatlOns of each tester by mdlCatmg whether odor IS noted (+ SIgn) m

each testflask

For example

ml sample

dIluted to 200 ml

Response

125 o 25

+

o 50

+

100

+

200

+

8 CalculatlOns

8 1 The threshold odor number IS the dl1utlOn ratIo at whIch odor IS Just detectable In the

example above (7 5), the first detectable odor occurred when 25 ml sample was dl1uted to

200 ml Thus, the threshold IS 200 dIVIded by 25, equals 8 Table 1 hststhe threshold odor

numbers that correspond to common dl1utlOns

8 2 Anomalous responses sometImes occur, a low concentratlOn may be called posItive and a

hIgher concentratlOn m the senes may be called negatIve In such a case, the threshold IS

deSIgnated as that pomt ofdetectlOn after whlCh no further anomahes occur

140 1-5
+

100

+

125 o 25 50

+

63

+

t Threshold

CalculatlOns of panel results to find the most probable average threshold are best

accomplIshed by appropnate statIstIcal methods For most purposes, the threshold of a

group can be expressed as the geometnc mean of the mdlVldual thresholds The

geometnc mean IS calculated m the followmg manner

8 3 1 Obtam odor response as outlmed m Procedure and record results

For example

Response

threshold

For lDstance

mt sample

dtluted to 200 m1

83

Table 3

Sample Odor Series

mt of Odor- ml of Observer Response·

free water Sample 1 2 3 4 5

188 125

175 25 EB + EB

200 0

150 50 EB + +

200 0

100 100 + + EB EB +

0 200 + + + + +

*CIrcled plus equals threshold level

8 3 2 Obtam mdividual threshold odor numbers from Table 1

Observer TON

1 4

2 8

3 2

4 2

5 8

8.3 3 The geometnc mean IS equal to the nth root of the product of n numbers

Therefore

4 x 8 x 2 x 2 x 8 = 1,024

and Y/ 1,024 = log 1,024 = 3 0103 = 06021

5 -Sand anti-log of 0 6021 = 4 = TON

140 1-6
9 PrecIsIon and Accuracy

9 1 PreCISIOn and accuracy data are not avaIlable at thIS time

92 A threshold number IS not a preCIse value In the case ofthe sIngle observer, It represents

a Judgment at the time of testIng Panel results are more meamngful because IndIVIdual

dIfferences have less Influence on the result One or two observers can develop useful data

If companson wIth larger panels has been made to check theIr sensItivIty Compansons

of data from tIme to time or place to place should not be attempted unless all test

condItions have been carefully standardIZed and some basIs for companson of observer

IntensIties eXIsts

BiblIography

1 Standard Methods for the EXamInatIOn ofWater and Wastewater, 14th EdItion, p 75, Method

206, (1975)

2 ASTM, Comm E-18, STP 433, "BasIc Pnnclples ofSensory EvaluatIOn", STP 434, Manual on

Sensory TestIng Methods, STP 440, "CorrelatIOn ofSubJectIve-ObJective Methods In the Study

ofOdors and Taste", PhIl, Pennsylvama (1968)

3 Baker, R A, "Cntlcal EvaluatIOn of Olfactory Measurement" Jour WPCF, 34, 582 (1962)

140 1-7
pH

Method 150.1 (Electrometric)

STORET NO.

Determined on site 00400

Laboratory 00403

1 Scope and ApphcatlOn

1 1 ThIS method IS appltcable to dnnktng, surface, and saltne waters, domestic and mdustnal

wastes and aCId ram (atmosphenc depOSItiOn)

2 Summary ofMethod

2 1 The pH of a sample IS determmed electrometncally usmg eIther a glass electrode m

combmatlOn wIth a reference potential or a combmatlOn electrode

3 Sample Handltng and Preservation

3 1 Samples should be analyzed as soon as pOSSIble preferably m the field at the tIme of

samplmg

3 2 High-punty waters and waters not at eqUIhbnum wIth the atmosphere are subject to

changes when exposed to the atmosphere, therefore the sample contamers should be

filled completely and kept sealed pnor to analysIs

4 Interferences

4 1 The glass electrode, m general, IS not subject to solution mterferences from color,

turbidity, collOidal matter, oXidants, reductants or high sahmty

4 2 SodIUm error at pH levels greater than 10 can be reduced or ehmmated by usmg a "low

sodIUm error" electrode

4 3 Coatings of otly matenal or particulate matter can Imparr electrode response These

coatmgs can usually be removed by gentle wtpmg or detergent washmg, followed by

dlsttlled water nnsmg An additional treatment wIth hydrochlonc aCid (1 + 9) may be

necessary to remove any remammg film

44 Temperature effects on the electrometnc measurement of pH anse from two sources

The first IS caused by the change m electrode output at vanous temperatures ThIS

mterference can be controlled with mstruments havmg temperature compensatlOn or by

cahbratmg the electrode-mstrument system at the temperature of the samples The

second source IS the change of pH mherent m the sample at vanous temperatures ThIS

error IS sample dependent and cannot be controlled, It should therefore be noted by

reportmg both the pH and temperature at the tIme ofanalySIS

5 Apparatus

5 1 pH Meter-laboratory or field model A WIde vanety of mstruments are commerCIally

avatlable wIth vanous speCIfications and optIonal eqUIpment

Approved for NPDES

Issued 1971

Edltonal reVlSlon 1978 and 1982

1501-1
5 2 Glass electrode

53 Reference electrode-a calomel, sl1ver-sl1ver chlonde or other reference electrode of

constant potential may be used

NOTE 1: CombmatIOn electrodes mcorporatIng both measuring and reference

functIons are convenient to use and are aval1able With sohd, gel type filhng matenals that

requIre minimal maintenance

5 4 MagnetiC stirrer and Teflon-coated stlrnng bar

5 5 Thermometer or temperature sensor for automatic compensation

6 Reagents

6 1 Pnmary standard buffer salts are aval1able from the NatIOnal Bureau of Standards and

should be used 10 SituatIOns where extreme accuracy IS necessary

6.1 1 PreparatIOn ofreference solutions from these salts reqmre some speCial precautions

and handlIng(l) such as low conductiVity dl1utIOn water, drymg ovens, and carbon

diOXide free purge gas These solutIons should be replaced at least once each

month

6 2 Secondary standard buffers may be prepared from NBS salts or purchased as a solutIOn

from commerCial vendors Use ofthese commercially aval1able solutIOns, that have been

vahdated by companson to NBS standards, are recommended for routme use.

7. CahbratIOn

7.1 Because ofthe Wide vanety of pH meters and accessones, detal1ed operatmg procedures

cannot be Incorporated Into thIs method Each analyst must be acquamted With the

operatIOn of each system and famlhar With all mstrument functions SpeCial attentIOn to

care ofthe electrodes IS recommended

7 2 Each mstrument/electrode system must be cahbrated at a mmlmum of two pomts that

bracket the expected pH of the samples and are approximately three pH Units or more

apart

7 2 1 Vanous mstrument designs may mvolve use of a "balance" or "standardize" dial

and/or a slope adjustment as outhned In the manufacturer's instructIOns Repeat

adjustments on successive portions of the two buffer solutIOns as outhned m

procedure 8 2 untl1 readings are wlthm 0 05 pH Units of the buffer solutIOn value

8 Procedure

8 1 Standardize the meter and electrode system as outhned In SectIOn 7

8.2 Place the sample or buffer solutIOn In a clean glass beaker usmg a suffiCient volume to

cover the sensmg elements of the electrodes and to give adequate clearance for the

magnetic stlmng bar

8 2 1 Iffield measurements are bemg made the electrodes may be Immersed directly m

the sample stream to an adequate depth and moved In a manner to msure suffiCient

sample movement across the electrode sensing element as mdlcated by dnft free

(<0 1pH) readings

8 3 Ifthe sample temperature dIffers by more than 2°e from the buffer solutIOn the measured

pH values must be corrected Instruments are eqmpped With automatic or manual ,

(I)NatIOnal Bureau of Standards SpeCial Pubhcatlon 260

1501-2
compensators that electromcally adjust for temperature differences Refer to

manufacturer's mstructlOns '

84 After nnsmg and gently wlpmg the electrodes, If necessary, Immerse them mto the

sample beaker or sample stream and stir at a constant rate to provide homogeneity and

suspenslOn ofsohds Rate ofstIffing should mmimize the air transfer rate at the aIr water

mterface of the sample Note and record sample pH and temperature Repeat

measurement on succeSSIve volumes of sample untll values differ by less than 0 1 pH

umts Two or three volume changes are usually sufficient

85 For aCId rain samples It IS most Important that the magnetic stirrer IS not used

Instead, sWIfI the sample gently for a few seconds after the mtroductIon of the

e1ectrode(s) Allow the electrode(s) to eqUIlIbrate The air-water mterface should

not be disturbed whtle measurement IS bemg made If the sample IS not m

equdlbnum with the atmosphere, pH values wdl change as the

dIssolved gases are either absorbed or desorbed Record sample pH and

temperature

9 CalculatIon

9 1 pH meters read dIrectly m pH umts Report pH to the nearest 0 1 umt and temperature

to the nearest °C

10 PrecIsIon and Accuracy

10 1 Forty-four analysts m twenty laboratorIes analyzed SIX synthetic water samples

contaImng exact mcrements ofhydrogen-hydroxyl Ions, WIth the followmg results

Accuracy as

pH UnIts Standard DeVIatiOn BIas, BIas,

pH UnIts % pH UnIts

35 010 -029 -001

35 011 -000

71 020 +101 +007

72 018 -003 -0002

80 013 -012 -001

80 012 +016 +001

(FWPCA Method Study 1, Mmeral and PhysIcal Analyses)

10 2 In a smgle laboratory (EMSL), usmg ~urface water samples at an average pH of7 7, the

standard deVIatIon was ±O 1

BIblIography

1 Standard Methods for the Exammation ofWater and Wastewater, 14th EditlOn, p 460, (1975)

2 Annual Book ofASTM Standards, Part 31, "Water", Standard DI293-65, p 178 (1976)

3 Peden, M E and Skowron, L M, Iomc StabIlIty of PreCIpItatIOn Samples,

Atmosphenc EnvIfonment, Vol 12, pp 2343-2349, 1978

1501-3
&EPA

United States

Environmental Protection

Agency

Research and Development

Test Method

Environmental Monitoring and

Support Laboratory

CinCinnati OH 45268

pH, Continuous Monitoring

(Electrometric)-Method 150.2

1 Scope and Application

1 1 ThiS method IS applicable to the

continuous pH measurement of

dnnkrng surface, and saline waters

domestic and rndustnal waste waters

2 Summary of Method

2 1 The pH of a sample IS determmed

electrometncally usrng a glass

electrode with a reference electrode

or a smgle combrnatlOn electrode

3 Sample Handlmg and

Preservation

3 1 The composition of the water or

waste contactmg the measunng

electrode system must be

representative of the total flow from

the water body

4 Interferences

4 1 The glass electrode rn general,

IS not subject to solution Interferences

from color turbidity colloidal matter

oXIdants reductants or high salinity

4 2 Sodium error at pH levels

greater than 10 can be reduced or

elimrnated by uSing a low sodium

error electrode

4 3 Manually mspect the conditions

of the electrodes every 30 days for

coatmg by Oily matenals or bUildup of

lIme If 011 and grease and/or scale

bUildup are not present, thiS time

mterval may be extended

4 3 1 Coatmgs of 011, grease and

very fine solids can Impair electrode

response These can usually be

removed by gentle Wiping and

detergent washrng The use of flowthrough electrode housings which

prOVide higher flow velOCity helps to

prevent the coatrng action

4 3 2 Heavy particulate matter such

as lime accumulation can be removed

by careful scrubbmg or ImmerSIOn In

dilute (1+9) hydrochlonc aCid

Continuous mOnitoring under these

conditions benefits from ultraSOnic or

other In-line contmuous cleaning

methods

4 4 Temperature effects on the

eJectrometrrc measurement of pH

anse from two sources The first IS

caused by the change In electrode

output at vanous temperatures ThiS

Interference can be controlled with

Instruments having temperature

compensation or by calibrating the

electrode-Instrument system at the

temperature of the samples For best

results meters having automatic

temperature compensation should be

calibrated with solutions within 5°C of

the temperature of the stream to be

measured The second source IS the

change of pH Inherent m the sample

at varrous temperatures ThIS error IS

sample dependent and cannot be

controlled, It should therefore be

noted by reportmg both the pH and

temperature at the time of analysIs

5 Apparatus

5 1 pH Monitor - A Wide vanety of

Instruments are commercially

available with vanous speCifications

and optional equipment For

unattended use, the monitor should

be eqUipped with automatic or fixed

1502 1 Dec 1982
temperature compensation and wIth a

recorder or alarm function

6 2 Glass electrode - with shielded

cable between electrode and monrtor

unless preampllflcatlon IS used

6.3 Reference electrode - a

reference electrode wIth a constant

potential and with eIther a vIsible

electrolyte or VISCOUS gel fill

NOTE 1 Combmation electrodes Incorporatmg both measuring and reference functions are convenrent to use

and are available wIth solid, gel-type filling matenals that require minimal

maintenance

6 4 Temperature sensor - for

automatic compensator covering

general ambient temperature range

6.6 Electrode mounting - to hold

electrodes, may be flow through (for

small flows), pipe mounted or

Immersion

6. Reagents

6.1 Primary standard buffer salts are

available from the National Bureau of

Standards and should be used In

situations where extreme accuracy IS

required

6 1 1 Preparation of reference

solutions from these salts require

some s~clal precautions and

handhng' such as low conductivity

dilution water, drying ovens, and

carbon dIoxide free purge gas These

solutions should be replaced at least

once each month

6.2 Secondary buffers may be

prepared from NBS salts or purchased

as a solution from commercIal

vendors. Use of these commercially

available solutIOns, whIch have been

validated by comparison to NBS

standards, IS recommended for

routine operatIOn These buffers may

be retamed for at least SIX months If

kept stoppered

7. Calibration

7.1 Immersion type electrodes -

easily removed from mountmg

7.1 1 The electrode should be

cahbrated at a mmlmum of two pomts

that bracket the expected pH of the

water/waste and are approxImately

three pH units or more apart

'Nallonll Bureau of Standards SpeclSl PublicatIon

260

7 1 2 Repeat calibration

adjustments on successive portions of

the two buffer solutIons until readings

are wlthm ±O 05 pH Units of the buffer

value If calibration problems occur,

see43

7 1 3 Because of the Wide vanety of

mstruments available, no detailed

operatmg mstructlons are prOVided

Instead, the analyst should refer to

the particular manufacturer s

mstructlons

7 1 4 Calibration against two buffers

should be carrred out at least dally If

the pH of the flUid being measured

fluctuates conSiderably, the calibration

should be carrred out more often

Calibration frequencIes may be

relaxed If hIstorical data supports a

longer penod between calibration

7 2 Immersion type electrodes -

not easily removed from mountmg

72 1 Collect a grab sample of the

flOWing matenal from a POint as close

to the electrode as pOSSible Measure

the pH of thiS grab sample as qUickly

as pOSSible With a laboratory - type pH

meter Adjust the calibration control

of the continuous monrtor to the

reading obtained

7 2 2 The temperature and condition

of the grab sample must remain

constant untIl ItS pH has been

measured by the laboratory pH meter

The temperature of the sample should

be measured and the temperature

compensator of the laboratory pH

meter adjusted

7 2 3 The laboratory - type pH meter

should be calibrated pnor to use

against two buffers as outlined In 7 1

7 2 4 The continuous pH monrtonng

system should be initially calibrated

against two buffers as outlined In 7 1

before being placed Into service

Recallbratlon (every 30 days) at two

POints IS recommended If at all

pOSSIble to ensure the measunng

electrode IS In working order If thiS IS

not pOSSible, the use of electrode

testing features for a broken or

malfunctioning electrode should be

conSidered when purchasing the

eqUipment

7 2 5 The indirect calibration should

be carrred out at least once a day If

the pH of the flUid being measured

fluctuates conSiderably, the calibration

should be carrred out more often

Calibration frequencies may be

relaxed If hlstoncal data support a

longer penod between calibration

7 2 6 If the electrode can be

removed from the system, but With

difficulty, It should be directly

calibrated as In 7 1 at least once a

month

7 3 Flow-through type electrode -

easily removed from ItS mounting

73 1 Calibrate uSing buffers as In

7 1 The buffers to be used may be

the plocess stream Itself as one

buffer and as a second buffer after

adjustment of pH by additIon of an

aCid or base ThiS Will prOVide the

larger volumes necessary to calibrate

thiS type electrode

73 2 Since the velOCIty of sample

flow-through a flow through electrode

can produce an offset error In pH

reading, the user must have data on

hand to show that the offset IS known

and compensation has been

accomplished

74 Flow-through type electrode·

not easily removed from ItS mounting

7 4 1 Calibrate as In 7 2

74 2 Quality control data must be

on hand to show the user IS aware of

pOSSible sample flow velOCity effects

8 Procedure

8 1 Calibrate the monitor and

electrode system as outlined In

SectIon 7

8 2 Follow the manufacturer's

recommendation for operation and

installation of the system

8 3 In wastewaters, the electrode

may require penodlc cleaning After

manual cleaning, the electrode should

be calibrated as In 7 1 or 7 2 before

returning to servICe

8 4 The electrode must be placed so

that the water or waste flOWing past

the electrode IS representative of the

system

9 Calculations

9 1 pH meters read directly In pH

Units Reports pH to the nearest 0 1

Unit and temperature to the nearest

°C

10 PrecIsion and Accuracy

10 1 Because of the Wide vanabillty

of eqUipment and conditions and the

changeable character of the pH of

many process waters and wastes, the

preCISion of thiS method IS probably

less than that of Method 150 1,

however, a preCISion of 0 1 pH unrt

Dec 1982 1502-2
snou\d be attamab\e In the range of

pH 6 0 to 8 0 Accuracy data for

contmuous monltormg equipment

are not avaIlable at this time

Bibliography

, Annual Book of ASTM

'Standards Part 31, Water

Standard 1293-78, Method D, p 226

(1981)

15023 Dec 1982
RESIDUE, FILTERABLE

Method 160.1 (Gravimetric, Dried at 180°C)

STORET NO. 70300

1 Scope and Apphcation

1 1 ThIS method IS applIcable to drInkIng, surface, and salIne waters, domestIc and IndustrIal

wastes

1 2 The practIcal range ofthe determInatIOn IS 10 mg/l to 20,000 mg/l

2 Summary ofMethod

2 1 A well-mIxed sample IS filtered through a standard glass fiber filter The filtrate IS

evaporated and drIed to constant weIght at 180°C

22 If ResIdue, Non-FIlterable IS beIng determIned, the filtrate from that method may be

used for ResIdue, FIlterable

3 DefimtIOns

3 1 FIlterable resIdue IS defined as those solIds capable of paSSIng through a glass fiber filter

and drIed to constant weIght at 180°C

4 Sample HandlIng and PreservatIOn

4 1 PreservatIOn of the sample IS not practIcal, analysIs should begIn as soon as pOSSIble

RefrIgeratIon or ICIng to 4°C, to mInImIZe mICrobIOlogIcal decomposItion of solIds, IS

recommended

5 Interferences

5 1 HIghly mIneralIzed waters contaInIng sIgmficant concentratIOns ofcalCIUm, magneSIUm,

chlOrIde and/or sulfate may be hygroscopIC and WIll requIre prolonged dryIng,

desIccation and rapId weIghIng

52 Samples contaInIng hIgh concentratIOns of bICarbonate wIll reqUIre careful and pOSSIbly

prolonged dryIng at 180°C to Insure that all the bIcarbonate IS converted to carbonate

5 3 Too much reSIdue In the evaporatIng dIsh wIll crust over and entrap water that wIll not

be dnven offdunng dryIng Total reSIdue should be hmited to about 200 mg

6 Apparatus

6 1 Glass fiber filter dISCS, 4 7 cm or 2 1 cm, wIthout orgamc bInder, Reeve Angel type 934-

AH, Gelman type AlE, or eqUIvalent

6 2 FIlter holder, membrane filter funnel or Gooch cruCIble adapter

6 3 SuctIon flask, 500 ml

6 4 Gooch cruCIbles, 25 ml (If 2 1cm filter IS used)

6 5 EvaporatIng dIshes, porcelaIn, 100 ml volume (Vycor or platInum dIshes may be

SubstItuted)

6 6 Steam bath

67 DryIng oven, 180°C ±2°C

6 8 DesIccator

Approved for NPDES

Issued 1971

160 1-1
69 AnalytICal balance, capable ofwelghmg to 0 1mg

7 Procedure

7 1 PreparatIon of glass fiber filter dISC Place the dISC on the membrane filter apparatus or

msert mto bottom of a sUltable Gooch cruCIble Whl1e vacuum IS apphed, wash the dISC

wIth three succeSSIve 20 ml volumes of dIstIlled water Remove all traces of water by

contlnumg to apply vacuum after water has passed through DIscard washmgs

7 2 PreparatIon of evaporatmg dIshes If Volatl1e ResIdue IS also to be measured heat the

clean dlSh to 550 ±50°C for one hour m a muffle furnace If only FIlterable ResIdue IS to

be measured heat the clean dISh to 180 ±2°C for one hour Cool m deSIccator and store

untl1 needed WeIgh Immediately before use

7 3 Assemble the filtenng apparatus and begm suctlOn Shake the sample vIgorously and

rapIdly transfer 100 ml to the funnel by means of a 100 ml graduated cyhnder If total

filterable reSIdue IS low, a larger volume may be filtered

7 4 Fl1ter the sample through the glass fiber filter, rmse wIth three 10 ml portions of dIstIlled

water and contmue to apply vacuum for about 3 mmutes after filtratIon IS complete to

remove as much water as pOSSIble

75 Transfer 100 ml (or a larger volume) of the filtrate to a weIghed evaporatmg dISh and

evaporate to dryness on a steam bath

7 6 Dry the evaporated sample for at least one hour at 180 ±2°C Cool m a deSIccator and

weIgh Repeat the drymg cycle untl1 a constant weIght IS obtamed or until weIght loss IS

less than 0 5 mg

8. CalculatlOn

8 1 Calculate filterable reSIdue as follows

Fl1terab1e reSIdue, mg/l = (A - B) X 1,000 C

where

A = weIght ofdned reSIdue + dISh m mg

B = weIght ofdISh m mg

C = volume ofsample used m ml

9 PreCISIon and Accuracy

9.1 PreCIsIon and accuracy are not aval1able at thIS tIme

BIblIography

1. Standard Methods for the ExammatlOn ofWater and Wastewater, 14th EditlOn, p 92, Method

208B, (1975)

1601-2
RESIDUE, NON-FILTERABLE

Method 160.2 (Gravimetric, Dried at 103-105°C)

STORET NO. 00530

1 Scope and ApphcatIOn

1 1 ThIS method IS apphcable to dnnkmg, surface, and sahne waters, domestic and mdustnal

wastes

1 2 The practical range ofthe determmation IS 4 mg/l to 20,000 mg/l

2 Summary ofMethod

2 1 A well-mIxed sample IS filtered through a glass fiber filter, and the reSIdue retamed on the

filter IS dned to constant weIght at 103-105°C

2 2 The filtrate from thIS method may be used for ResIdue, FIlterable

3 DefimtIOns

3 1 ResIdue, non-filterable, IS defined as those sohds WhICh are retamed by a glass fiber filter

and dned to constant weIght at 103-105°C

4 Sample Handhng and PreservatIon

41 Non-representatIve partIculates such as leaves, stIcks, fish, and lumps of fecal matter

should be excluded from the sample IfIt IS determmed that theIr mclusIOn 11> not desIred

m the final result

4 2 Preservation of the sample IS not practIcal, analysIs should begm as soon as pOSSIble

Refngeration or Icmg to 4°C, to mimmize mIcrobIOlogIcal decomposItIOn of sohds, IS

recommended

5 Interferences

5 1 Ftltratlon apparatus, filter matenal, pre-washmg, post-washmg, and drymg temperature

are speCIfied because these varIables have been shown to affect the results

52 Samples htgh m Ftlterable ReSIdue (dIssolved sohds), such as sahne waters, brmes and

some wastes, may be subject to a posItIve mterference Care must be taken m selectmg the

filtenng apparatus so that washmg ofthe filter and any dIssolved sohds m the filter (7 5)

mmimizes thts potential mterference

6 Apparatus

61 Glass fiber filter dISCS, wtthout orgamc bmder, such as MIlhpore AP-40, Reeves Angel

934-AH, Gelman type A/E, or eqUivalent

NOTE: Because ofthe physIcal nature of glass fiber filters, the absolute pore SIze cannot

be controlled or measured Terms such as "pore sIze", collectIOn efficIenCIes and effectIve

retentIon are used to define thIS property m glass fiber filters Values for these parameters

vary for the filters hsted above

62 Ftlter support filtenng apparatus wIth reserVOIr and a coarse (40-60 mIcrons) fntted

dISC as a filter support

Approved for NPDES

Issued 1971

1602-1
NOTE: Many funnel desIgns are available In glass or porcelaIn Some of the most

common are HIrsch or Buchner funnels, membrane filter holders and Gooch crucIbles

All are available wIth coaJ;:se fntted dISC

6 3 SuctIon flask

6 4 DryIng oven, 103-105°C

6 5 DesIccator

6 6 AnalytIcal balance, capable ofweIghIng to 0 1mg

7 Procedure

7.1 Preparation of glass fiber filter dISC Place the glass fiber filter on the membrane filter

apparatus or Insert Into bottom of a sUItable Gooch crucIble with wrInkled surface up

WhIle vacuum IS apphed, wash the diSC with three successive 20 ml volumes of distIlled

water Remove all traces ofwater by contInuIng to apply vacuum after water has passed

through Remove filter from membrane filter apparatus or both crucible and filter If

Gooch crucible IS used, and dry In an oven at 103-105°C for one hour Remove to

desiccator and store untIl needed Repeat the dryIng cycle untIl a constant weight IS

obtaIned (weight loss IS less than 05 mg) Weigh Immediately before use After weighIng,

handle the filter or crucible/filter with forceps or tongs only

72 SelectIOn ofSample Volume

For a 4.7 cm diameter filter, filter 100 m1 ofsample If weight of captured residue IS less

than 1 0 mg, the sample volume must be Increased to provide at least 1 0 mg ofresidue If

otherfilter diameters are used, start with a sample volume equal to 7 mllcm2 offilter area

and collect at least a weight ofresidue proportIOnal to the 1 0 mg stated above

NOTE: If dunng filtratIOn of this Initial volume the filtratIOn rate drops rapIdly, or If

filtratIOn time exceeds 5 to 10 mmutes, the followmg scheme IS recommended Use an

unwelghed glass fiber filter of chOIce affixed m the filter assembly Add a known volume

of sample to the filter funnel and record the time elapsed after selected volumes have

passed through the filter Twenty-five ml mcrements for tmung are suggested Contmue

to record the time and volume mcrements until fitratIon rate drops rapidly Add

additional sample If the filter funnel volume IS madequate to reach a reduced rate Plot

the observed ttrne versus volume filtered Select the proper filtratIOn volume as thatJust

short ofthe tIme a significant change m filtratIOn rate occurred

73 Assemble the filtenng apparatus and begIn suction Wet the filter With a small volume of

distilled water to seat It agamst the fntted support

7.4 Shake the sample vIgorously and quantitatively transfer the predetermmed sample

volume selected m 7 2 to the filter USIng a graduated cylInder Remove all traces ofwater

by contInumg to apply vacuum after sample has passed through

75 With suctIon on, wash the graduated cylInder, filter, non-filterable residue and filter

funnel wall With three portIOns of distilled water allowmg complete draInage between

washmg Remove all traces of water by contInuIng to apply vacuum after water has

passed through

NOTE: Total volume ofwash water used should equal approximately 2 ml per cm2 For a

4 7 cm filter the total volume IS 30 ml

1602-2
76 Carefully remove the filter from the filter support AlternatIvely, remove crucIble and

filter from crucIble adapter Dry at least one hour at 103-105°C Cool m a deSIccator and

weIgh Repeat the drymg cycle untIl a constant weIght IS obtamed (weIght loss IS less than

o5mg)

8 CalculatIOns

8 1 Calculate non-filterable resIdue as follows

(A - B)x1 000 Non-fl1terable resIdue, mg/l = C'-

where

A = weIght offilter (or filter and crucIble) + resIdue m mg

B = weIght offilter (or filter and crucIble) m mg

C = ml ofsample filtered

9 PreClSlon and Accuracy

9 1 PreclSlon data are not aVailable at thIS time

9 2 Accuracy data on actual samples cannot be obtamed

BIblIography

1 NCASI Techmcal'Bulletm No 291, March 1977 NatIOnal CouncIl ofthe Paper Industry for

AIr and Stream Improvement, Inc, 260 MadIson Ave, NY

1602-3
RESIDUE, TOTAL

Method 160.3 (Gravimetric, Dried at 103-105°C)

STORET NO. 00500

1 Scope and ApphcatIOn

1 1 ThIS method IS apphcable to dnnkmg, surface, and salIne waters, domestIc and mdustrIal

wastes

1 2 The practIcal range ofthe determmation IS from 10 mg/1 to 20,000 mg/1

2 Summary ofMethod

2 1 A well mIxed alIquot of the sample IS quantItatIvely transferred to a pre-weIghed

evaporatmg dISh and evaporated to dryness at 103-105°C

3 DefinItIOns

3 1 Total ReSIdue IS defined as the sum of the homogenous suspended and dIssolved

materIals m a sample

4 Sample HandlIng and PreservatIOn

4 1 PreservatIon of the sample IS not practIcal, analysIs should begm as soon as possIble

RefngeratIon or Icmg to 4°C, to mmimize mICrobIOlogIcal decomposItIon of sohds, IS

recommended

5 Interferences

5 1 Non-representatIve partIculates such as leaves, stIcks, fish and lumps of fecal matter

should be excluded from the sample IfIt IS determmed that their mclUSIOn IS not deSired

m the final result

5 2 Floatmg 011 and grease, If present, should be mcluded m the sample and dIspersed by a

blender deVice before alIquotmg

6 Apparatus

61 Evaporatmg dishes, porcelam, 90 mm, 100 ml capacity (Vycor or platmum dishes may

be substItuted and smallersize dishes may be used IfreqUIred)

7 Procedure

7 1 Heat the clean evaporatmg dish to 103-105°C for one hour, If Volatlle ReSIdue IS to be

measured, heat at 550 ±50°C for one hour m a muffle furnace Cool, deSIccate, weIgh and

store m desIccator untll ready for use

7 2 Transfer a measured alIquot ofsample to the pre-weIghed dIsh and evaporate to dryness

on a steam bath or m a drymg oven

7 2 1 Choose an alIquot of sample suffiCient to contam a reSIdue of at least 25 mg To

obtam a weIghable reSIdue, succeSSIve alIquots ofsample may be added to the same

dISh

7 2 2 Ifevaporation IS performed m a drymg oven, the temperature should be lowered to

approxImately 98°C to prevent bollmg and splattermg ofthe sample

Approved for NPDES

Issued 1971

1603-1
7 3 Dry the evaporated sample for at least 1 hour at 103-105°C Coolin a desiccator and

weigh Repeat the cycle ofdrying at 103-105°C, coohng, desiCcating and weighing untl1 a

constant weight IS obtained or untl1loss ofweight IS less than 4% ofthe prevIous weight,

or 0 5 mg, whlchevens less

8 CalculatIOn

8.1 Calculate total residue as follows

Total residue, mg/l =(A - ~Xl,OOO

where

A = weight ofsample + dish in mg

B = weight ofdish in mg

C = volume ofsample in ml

9. Precision and Accuracy

9.1 Precision and accuracy data are not aval1able at this time

BiblIography

1. Standard Methods for the ExaminatIOn ofWater and Wastewater, 14th EditIOn, p 91, Method

208A, (1975)

1603-2
RESIDUE, VOLATILE

Method 160.4 (Gravimetric, Ignition at 550°C)

STORET NO. Total 00505

Non-Filterable 00535

Filterable 00520

1 Scope and ApplicatIon

1 1 ThIS method determmes the weIght ofsolid matenal combustIble at 550°C

1 2 The test IS useful m obtammg a rough approxlffiatlOn of the amount of orgalllc matter

present m the solid fractlOn of sewage, actIvated sludge, mdustnal wastes, or bottom

sedIments

2 Summary ofMethod

2 1 The resIdue obtamed from the determmatlOn of total, filterable or non-filterable resIdue

IS 19l1lted at 550°C m a muffle furnace The loss ofweIght on 19l1ltlOn IS reported as mg!1

volatl1e resIdue

3 Comments

3 1 The test IS subject to many errors due to loss of water of crystallizatlOn, loss of vo1atl1e

orgalllc matter prIor to combustlOn, mcomp1ete oXldatlOn of certam complex orgalllcs,

and decomposltlon ofmmera1 salts dunng combustlOn

3 2 The results should not be conSIdered an accurate measure of orgalllc carbon m the

sample, but may be useful m the control ofplant operatlOns

3 3 The prmclpa1 source of error m the determmatlOn IS fallure to obtam a representatIve

sample

4 Sample Handhng and PreservatlOn

4 1 PreservatlOn of the sample IS not practiCal, analysIs should begm as soon as pOSSIble

RefngeratlOn or lcmg to 4°C, to mmlmlze miCroblOlogiCal decompostlOn of solids IS

recommended

5 PreclSlon and Accuracy

5 I A collaboratIve study mvolvmg three laboratones exammmg four samples by means of

ten replicates showed a standard devlatlOn of ±11 mg/l at 170 mg/l volatlle resIdue

concentratlOn

6 Reference

6 I The procedure to be used for thIS determmatlOn IS found m

Standard Methods for the ExammatlOn of Water and Wastewater, 14th EdltlOn, p 95,

Method 208E, (1975)

Approved for NPDES

Issued 1971

1604-1
SETILEABLE MATTER

Method 160.5 (Volumetric, Imhoff Cone)

STORET NO. 50086

1 Scope and ApplIcatiOn

1 1 ThIs method IS applIcable to surface and salIne waters, domestic and Industna1 wastes

1 2 The practIcal lowerlImIt ofthe determInatIon IS about 0 2 mllllhr

2 Summary ofMethod

2 1 Settleable matter IS measured volumetncally wIth an Imhoffcone

3 Comments

3 1 For some samples, a separation of settleable and floatIng matenals wIll occur, In such

cases the floatIng matenals are not measured

3 2 Many treatment plants, especIally plants eqUIpped to perform gravimetnc

measurements, determIne reSIdue non-filterable (suspended solIds), In preference to

settleable matter, to Insure that floatIng matter IS Included In the analysIs

4 PreCIsiOn and Accuracy

4 1 Data on thIs determmation are not avaIlable at thIS time

5 Fleferences

5 1 The procedure to be used for this determInatIon IS found In

Standard Methods for the EXamInatIon of Water and Wastewater, 14th Edition, p 95,

Method 208F, Procedure 3a (1975)

Approved for NPDES

Issued 1974

1605-1
TEMPERATURE

Method 170.1 (Thermometric)

STORET NO. 00010

1 Scope and Apphcanon

1 1 This method is apphcable to drmkmg, surface, and salme waters, domestic and mdustnal

wastes

2 Summary ofMethod

2 1 Temperature measurements may be made with any good grade ofmercury-filled or dial

type centigrade thermometer, or a thermistor

3 Comments

3 1 Measurement device should be routmely checked agamst a preCiSlOn thermometer

certified by the NatlOnal Bureau ofStandards

4 Precision and Accuracy

4 1 Precision and accuracy for this method have not been determmed

5 Reference

5 1 The procedure to be used for this determmation is found m

Standard Methods for the ExammatlOn of Water and Wastewater, 14th EditIon, p 125,

Method 212 (1975)

Approved for NPDES

Issued 1971

170 1-1
TURBIDITY

Method 180.1 (Nephelometric)

STORET NO. 00076

1 Scope and ApplIcatIOn

1 1 ThIS method IS applIcable to dnnkmg, surface, and salIne waters m the range ofturbIdIty

from 0 to 40 nephelometnc turbIdIty umts (NTU) HIgher values may be obtamed wIth

dIlutIOn ofthe sample

NOTE 1: NTU's are consIdered comparable to the prevIOusly reported Formazm

TurbIdity Umts (FTU) and Jackson TurbIdIty Umts (JTV)

2 Summary ofMethod

2.1 The method IS based upon a companson ofthe mtensity oflIght scattered by the sample

under defined condItIOns wIth the mtensity of lIght scattered by a standard reference

suspensIOn The hIgher the mtensity ofscattered lIght, the hIgher the turbIdIty Readmgs,

m NTU's, are made m a nephelometer desIgned accordmg to specIficatIOns outlIned m

Apparatus A standard suspensIOn of Formazm, prepared under closely defined

condItions, IS used to calIbrate the mstrument

2 1 1 Formazm polymer IS used as the turbIdIty reference suspensIOn for water because It

IS more reproducIble than other types of standards prevIously used for turbIdIty

standards

2 1 2 A commercIally avaIlable polymer standard IS also approved for use for the

NatIOnal InterIm Pnmary Dnnkmg Water RegulatIOns ThIS standard IS Identified

as AMCO-AEPA-1 avaIlable from Amco Standard InternatIOnal, Inc

3 Sample HandlIng and PreservatIOn

3 1 PreservatIOn of the sample IS not practICal, analySIS should begm as soon as pOSSIble

RefngeratIOn or Icmg to 4°C, to mimmize mIcrobIOlogICal decomposItion of solIds, IS

recommended

4 Interferences

4 1 The presence of floatmg debns and coarse sedIments WhICh settle out rapIdly wIll gIve

low readmgs Fmely dIVIded aIr bubbles wIll affect the results m a pOSItIve manner

4 2 The presence oftrue color, that IS the color ofwater WhICh IS due to dIssolved substances

WhICh absorb lIght, wIll cause turbIdIties to be low, although thIS effect IS generally not

sIgmficant WIth fimshed waters

5 Apparatus

5 1 The turbIdImeter shall conSIst of a nephelometer WIth lIght source for Illummatmg the

sample and one or more photo-electnc detectors WIth a readout deVIce to mdicate the

mtensity of lIght scattered at nght angles to the path of the mCIdent lIght The

turbIdImeter should be so deSIgned that little stray lIght reaches the detector m the

Approved for NPDES and SDWA

Issued 1971

Editonal reVISIon 1974

Editonal reVISIOn 1978

180 1-1
absence of turbidity and should be free from slgmficant dnft after a short warm-up

penod

5 2 The sensItivity ofthe mstrument should permit detectIOn of a turbidity difference of 0 02

umt or less m waters havmg turbidities less than 1 umt The mstrument should measure

from 0 to 40 umts turbidity Several ranges will be necessary to obtam both adequate

coverage and sufficientsensitivity for low turbidities

5 3 The sample tubes to be used with the available mstrument must be of clear, colorless

glass They should be kept scrupulously clean, both mSlde and out, and discarded when

they become scratched or etched They must not be handled at all where the hght stnkes

them, but should be provided with suffiCient extra length, or with a protective case, so

that they may be handled

5 4 Differences m physICal design ofturbldlmeters wIll cause differences m measured values

for turbidity even though the same suspensIOn IS used for cahbratlOn To mmlmlze such

dlfferen~s, the followmg design cntena should be observed

5 4 1 Light source Tungsten lamp operated at a color temperature between

22QO-3000oK

5 4 2 Distance traversed by mCldent hght and scattered hght wlthm the sample tube

Total not to exceed 10 cm

543 Detector Centered at 90° to the mCldent hght path and not to exceed ±30° from

90° The Detector, and filter system If used, shall have a spectral peak response

between 400 and 600nm

5 5 The Hach Turbidimeter, Model 2100 and 2100 A, IS m Wide use and has been found to be

rehable, however, other mstruments meetmg the above deSign cntena are acceptable

6 Reagents

6.1 Turbidity-free water Pass distilled water through a 0 45u pore size membrane filter If

such filtered watershows a lower turbidity than the distIlled water

6 2 Stock formazm turbidity suspenSIOn

Solution 1 Dissolve 1 00 g hydrazme sulfate, (NH2)2-H2S04, m distilled water and dilute

to 100ml m a volumetnc flask

Solution 2 DIssolve 10 00 g hexamethylenetetramme m dIstIlled water and dIlute to 100

ml m a volumetnc flask

In a 100 ml volumetnc flask, mIX 5 0 ml SolutIOn 1wIth 5 0 ml SolutIOn 2 Allow to stand

24 hours at 25 ±3°C, then dIlute to the mark and mIX

6 3 Standard formazm turbIdity suspension DIlute 10 00 ml stock turbIdIty suspensIOn to

100 ml with turbIdity-free water The turbIdIty of thIS suspensIOn IS defined as 40 umts

DIlute portions of the standard turbIdIty suspensIOn wIth turbIdIty-free water as

reqUIred

6 3 1 A new stock turbidity suspensIOn should be prepared each month The standard

turbidity suspensIOn and dIlute turbidIty standards should be prepared weekly by

dilutIOn ofthe stock turbIdity suspensIOn

6 4 The AMCO-AEPA-1 standard as supphed reqUIres no preparatIOn or dIlutIOn pnor to

use

180 1-2
7 Procedure

7 1 TurbIdImeter calIbratIOn The manufacturer's operatmg mstructions should be followed

Measure standards on the turbIdImeter covenng the range ofmterest Ifthe mstrument IS

already calIbrated m standard turbIdIty UnIts, thIS procedure wIll check the accuracy of

the calIbratIOn scales At least one standard should be run m each mstrument range to be

used Some mstruments permIt adjustments of sensItIvIty so that scale values wIll

correspond to turbIdIties RelIance on a manufacturer's solId scattermg standard for

settmg overallmstrument sensItIvIty for all ranges IS not an acceptable practIce unless the

turbIdImeter has been shown to be free of dnft on all ranges If a pre-calIbrated scale IS

not supplIed, then calIbratIOn curves should be prepared for each range of the

mstrument

7 2 TurbIdIties less than 40 UnIts Shake the sample to thoroughly dIsperse the solIds Wait

until air bubbles dIsappear then pour the sample mto the turbIdImeter tube Read the

turbIdIty dIrectly from the mstrument scale orfrom the appropnate calIbratIOn curve

73 TurbIdItIes exceedmg 40 umts Dilute the sample wIth one or more volumes ofturbidItyfree water untIl the turbIdIty falls below 40 UnIts The turbIdIty ofthe ongmal sample IS

then computed from the turbIdIty of the diluted sample and the dIlutIOn factor For

example, If 5 volumes of turbIdIty-free water were added to 1 volume ofsample, and the

dIluted sample showed a turbIdIty of 30 UnIts, then the turbIdIty of the ongmal sample

was 180 UnIts

73 1 The Hach Turbidimeters, Models 2100 and 2100A, are eqUIpped With 5 separate

scales 0-02,0-10,0-100, and 0-1000 NTU The upper scales are to be used only

as mdicators of reqUIred dilutIOn volumes to reduce readmgs to less than 40 NTU

NOTE 2: ComparatIve work performed m the MDQAR Laboratory mdICates a

progreSSIve error on sample turbIdIties m excess of40 UnIts

8 CalculatIOn

8 1 MultIply sample readmgs by appropnate dIlutIOn to obtam final readmg

8 2 Report results as follows

NTU

00 - 10

1 - 10

10 - 40

40 - 100

100 - 400

400 - 1000

> 1000

Record to Nearest

005

01

1

5

10

50

100

9 PrecIsIOn and Accuracy

9 1 In a smgle laboratory (EMSL), usmg surface water samples at levels of26, 41, 75 and 180

NTU, the standard deVIatIOns were ±O 60, ±O 94, ±1 2 and ±4 7 UnIts, respectIvely

9 2 Accuracy data are not avaIlable at thIS time

180 1-3
BIbhography

1 Annual Book ofASTM Standards, Part 31, "Water", Standard D1889-71, P 223 (1976)

2. Standard Methods for the ExammatlOn of Water and Wastewater, 14th EdItlOn, p 132,

Method 214A, (1975)

1801-4
METALS

(Atomic Absorption Methods)

1 Scope and ApplIcatIOn

1 1 Metals m solutIOn may be readl1y determmed by atomIC absorptIOn spectroscopy The

method IS sImple, rapId, and applIcable to a large number ofmetals m dnnkmg, surface,

and salme waters, and domestIc and mdustnal wastes Whl1e dnnkmg waters free of

particulate matter may be analyzed dIrectly, domestIc and mdustnal wastes reqUlre

processmg to solubIlIze suspended matenal Sludges, sedIments and other solId type

samples may also be analyzed after proper pretreatment

1 2 DetectIOn lImIts, sensItIvIty and optImum ranges ofthe metals w111 vary wIth the vanous

makes and models of satIsfactory atomIc absorptIOn spectrophotometers The data

shown m Table 1, however, prOVIde some mdlcatIOn of the actual concentratIOn ranges

measurable by dIrect aSpIratIOn and usmg furnace techmques In the ma]onty of

mstances the concentratIOn range shown m the table by dIrect aspIratIOn may be

extended much lower wIth scale expansIOn and conversely extended upwards by usmg a

less sensItive wavelength or by rotatmg the burner head Detection lImIts by dIrect

aspIratIOn may also be extended through concentratIOn of the sample and/or through

solvent extractIOn techmques Lower concentratIOns may also be determmed usmg the

furnace technIques The concentratIOn ranges gIven m Table 1 are somewhat dependent

on eqUlpment such as the type ofspectrophotometer and furnace accessory, the energy

source and the degree of electncal expanSIOn of the output SIgnal When usmg furnace

techmques, however, the analyst should be cautIOned as to pOSSIble chemlCal reactIOns

occurrmg at elevated temperatures WhICh may result m eIther suppressIOn or

enhancement of the analysIs element To msure valId data wIth furnace techmques, the

analyst must examme each matnx for mterference effects (see 5 2 1) and Ifdetected, treat

accordmgly usmg eIther succeSSIve dl1utIOn, matnx modIficatIOn or method ofstandard

addItions (see 8 5)

1 3 Where dIrect aspIratIOn atomlC absorptIOn techmques do not prOVIde adequate

sensItIvIty, m addItion to the furnace procedure, reference IS made to specIalIzed

procedures such as the gaseous hydnde method for arsemc and selemum, the cold vapor

techmque for mercury, and the chelatIOn-extractIOn procedure for selected metals

Reference to approved colonmetnc methods IS also made

1 4 AtomlC absorptIOn procedures are prOVIded as the methods of chOlce, however, other

mstrumental methods have also been shown to be capable of producmg precIse and

accurate analytIcal data These mstrumental techmques mc1ude emIssIon spectroscopy,

X-ray fluorescence, spark source mass spectroscopy, and anodIc stnppmg to name but a

few The analyst should be cautIOned that these methods are hIghly speclahzed

techmques requmng a hIgh degree of SkIll to mterpret results and obtam valId data

Approved for NPDES and SDWA

Issued 1969

Edltonal reVISIOn 1974 and 1978

METALS-l
These above mentlOned techmques are presently conSidered as alternate test procedures

and approval must be obtamed pnor to their use

2. Summary ofMethod

2.1 In direct asplratlOn atomic absorptlOn spectroscopy a sample IS aspirated and atomized

m a flame A 11ght beam from a hollow cathode lamp whose cathode IS made of the

element to be determmed IS drrected through the flame mto a monochromator, and onto

a detector that measures the amount of 11ght absorbed AbsorptlOn depends upon the

presence offree unexcited ground state atoms m the flame Smce the wavelength of the

11ght beam IS charactenstiC of only the metal bemg determmed, the 11ght energy absorbed

by the flame IS a measure ofthe concentration ofthat metal m the sample This prmclple

is the basIs ofatOmlC absorptlOn spectroscopy

2.2 Although methods have been reported for the analysIs of so11ds by atomic absorption

spectroscopy (Spectrochlm Acta, 24B 53, 1969) the techmque generally IS 11mlted to

metals m solutlOn orsolubl11zed through some form ofsample processmg

2 2 1 Pre11mmary treatment of wastewater and/or mdustnal effluents IS usually

necessary because of the complexity and vanabl11ty of the sample matnx

Suspended matenal must be subjected to a solublhzatlOn process before analysIs

This process may vary because ofthe metals to be detefmlned and the nature ofthe

sample bemg analyzed When the breakdown of orgamc matenal IS necessitated,

the process should mclude a wet dlgestlOn with mtnc aCid

222 In those mstances where complete charactenzatlOn of a sample IS desired, the

suspended matenal must be analyzed separately This may be accomphshed by

filtratlOn and aCid dlgestlOn ofthe suspended matenal Metalhc constituents m this

aCid digest are subsequently determmed and the sum of the dissolved plus

suspended concentratlOns w111 then provide the total concentratlOns present The

sample should be filtered as soon as possible after collection and the filtrate

aCldlfied lmmedlately

2 2 3 The total sample may also be treated with aCid without pnor filtratlOn to measure

what may be termed "total recoverable" concentratlOns

2 3 When usmg the furnace techmque m conJunctlOn with an atOmlC absorptlOn

spectrophotometer, a representative ahquot of a sample IS placed m the graphite tube m

the furnace, evaporated to dryness, charred, and atomized As a greater percentage of

avallable analyte atoms are vaponzed and dissociated for absorptlOn m the tube than the

flame, the use ofsmall sample volumes or detection oflow concentrations of elements IS

possible The pnnclple IS essentially the same as with direct asprratlOn atomic absorptlOn

except a furnace, rather than a flame, IS used to atomize the sample RadlatlOn from a

given excited element IS passed through the vapor contammg ground state atoms of that

element The mtenslty ofthe transmitted radlatlOn decreases m proportlOn to the amount

ofthe ground state element m the vapor .

METALS-2
TABLE 1

Atomic AbsorptIon Concentration Ranges(l)

DIrect Aspiration Furnace Procedure(4t S

)

Optimum Optimum

Detection Concentration Detection Concentration

Limit SensltlvJty Range Limit Range

Metal mg/l mg/l mg/I ug/l ug/l

Alummum 01 1 5 50 3 20 200

Antimony 02 05 1 40 3 20 300

Arsenlc(') 0002 0002 002 1 5 100

Banum(p) 01 04 1 20 2 10 200

BeryllIUm 0005 0025 005 2 02 1 30

CadmIUm 0005 0025 005 2 01 05 10

CalcIUm 001 008 02 7

ChromIUm 005 025 05 10 1 5 100

Cobalt 005 02 05 5 1 5 100

Copper 002 01 02 5 1 5 100

Gold 01 025 05 20 1 5 100

IndlUm(p) 3 8 20 500 30 100 1500

Iron 003 012 03 5 1 5 100

Lead 01 05 1 20 1 5 100

MagnesIUm 0001 0007 002 0,5

Manganese 001 005 01 3 02 30

Mercury(3l 00002 00002 - 001

MolYbdenum(p) 01 04 1 40 1 3 60

Nlckel(p) 004 015 03 5 I 5 50

OsmIUm 03 1 2 100 20 50 500

PalladlUm(p) 01 025 05 15 5 20 400

Platlnum(p) 02 2 5 75 20 100 2000

Potassium 001 004 01 2

Rhenlum(p) 5 15 50 - 1000 200 500 5000

RhodlUm(p) 005 03 1 30 5 20 400

Ruthenium 02 05 1 50 20 100 2000

Selenlum(') 0002 0002 002 2 5 100

Silver 001 006 01 4 02 1 25

SodIUm 0002 0015 003 1

Thallium 01 05 1 20 1 5 100

Tin 08 4 10 300 5 20 300

Titanium (p) 04 2 5 100 10 50 500

VanadIUm (p) 02 08 2 100 4 10 200

ZinC 0005 002 005 1 005 02 4

(1) The concentrations shown are not contnved values and should be obtainable with any satisfactory atomic absorption

spectrophotometer

(2) Gaseous hydnde method

(3) Cold vapor technique

(4) For furnace sensitivity values consult Instrument operating manual

(5) The listed furnace values are those expected when uSing a 20 ul injection and normal gas flow except In the case of arsenic and

selenium where gas Interrupt IS used The symbol (p) indicates the use ofpyrolytlc graphite with the furnace procedure

METALS-3
The metal atoms to be measured are placed m the beam ofradiatlOn by mcreasmg the temperature of

the furnace thereby causmg the mJected speCImen to be volatIhzed A monochromator Isolates the

charactenstIc radiatlOn from the hollow cathode lamp and a photosensItIve devIce measures the

attenuated transmItted radiatlOn

3 Definition ofTerms

3 1 Optlffium ConcentratlOn Range A range, defined by llffiItS expressed m concentratlOn,

below WhICh scale expanSlOn must be used and above whIch curve correctlOn should be

consIdered ThIS range wl1l vary wIth the senSItIvIty ofthe mstrument and the operatmg

condItIon employed

3 2 SensitIvIty The concentratlOn m ml1hgrams of metal per hter that produces an

absorptIon of 1%

3 3 Detection Llffilt DetectIon hmits can be expressed as eIther an mstrumental or method

parameter The hmItmg factor of the former usmg aCId water standards would be the

sIgnal to nOlse ratIo and degree ofscale expanSlOn used, whl1e the latter would be more

affected by the sample matnx and preparatlOn procedure used The SCIentlfic Apparatus

Makers AssociatlOn (SAMA) has approved the followmg defimtlOn for detectlOn hmit

that concentratIon of an element whIch would yIeld an absorbance equal to tWIce the

standard devIation ofa senes ofmeasurements ofa solutlOn, the concentraton ofWhICh IS

dIstmctly detectable above, but close to blank absorbance measurement The detectIon

hmit values hsted m Table I and on the mdividual analysIs sheets are to be consIdered

mmimum workmg hmits achIevable wIth the procedures gIven m thIS manual These

values may dIffer from the optImum detectlOn hmit reported by the vanous mstrument

manufacturers

34 DIssolved Metals Those constItuents (metals) whIch WIll pass through a 045 u

membrane fllter

3 5 Suspended Metals Those constItuents (metals) whIch are retamed by a 045 u membrane

fllter

3 6 Total Metals The concentratlOn ofmetals determmed on an unflltered sample followmg

VIgorous dIgestion (SectlOn 4 1 3), or the sum ofthe concentratlOns of metals m both the

mssolved and suspended fractIons

3 7 Total Recoverable Metals The concentratIon ofmetals m an unflltered sample followmg

treatment wIth hot dl1ute mmeral aCId (SectlOn 4 1 4)

4 Sample Handbng and PreservatlOn

4.1 Forthe determmatlOn oftrace metals, contammatlOn and loss are ofpnme concern Dust

m the laboratory envIronment, lffipuntIes m reagents and Impunties on laboratory

apparatus wmch the sample contacts are all sources of potentIal contammatlOn For

hqwd samples, contamers can mtroduce eIther posItive or negatIve errors m the

measurement of trace metals by (a) contnbutmg contammants through leachmg or

surface desorptlOn and (b) by depletmg concentratlOns through adsorptlOn Thus the

collectlOn and treatment ofthe sample pnor to analySIS reqwres partICular attentlOn The

sample bottle whether boroSIlIcate glass, polyethylene polypropylene or Teflon should

be thoroughly washed With detergent and tap water, nnsed wIth 1 1 mtnc aCid, tap

METALS-4
water, 1 1 hydrochlonc aCId, tap water and fmally deIOnIzed dIstIlled water m that

order

NOTE 1: ChromIc aCId may be useful to remove orgamc deposIts from glassware,

however, the analyst should be cautIOned that the glassware must be thoroughly rmsed

WIth water to remove the last traces of chromIUm ThIS IS espeCIally Important If

chromIUm IS to be mcluded m the analytical scheme A commercial productNOCHROMIX-available from Godax Laboratones, 6 Vanck St New York, NY

10013, may be used m place of chromic aCid [Chromic aCId should not be used With

plastic bottles ]

NOTE 2 IfIt can be documented through an active analytical quahty control program

usmg spiked samples, reagent and sample blanks, that certam steps m the cleamng

procedure are not reqUIred for routme samples, those steps may be ehmmated from the

procedure

Before collection ofthe sample a deCISion must be made as to the type ofdata deSired, Ie,

dissolved, suspended, total or total recoverable For contatner preference, maximum

holdmg time and sample preservation at time of collectIOn see Table 1m the front part of

thiS manual Dnnkmg water samples contammg suspended and setteable matenal should

be prepared usmg the total recoverable metal procedure (sectIOn 4 1 4)

4 1 1 For the determmatIOn of dissolved constituents the sample must be filtered

through a 045 u membrane filter as soon as practical after collectIOn (Glass or

plastiC filtenng apparatus usmg plam, non-gnd marked, membrane filters are

recommended to aVOId possible contammatIOn) Use the first 50-100 nil to nnse

the filter flask Discard thiS portion and collect the reqUIred volume of filtrate

ACidify the filtrate With 1 1 redistilled HN03 to a pH of <2 Normally, 3 nil of

(1 1) aCid per hter should be sufficIent to preserve the sample (See Note 3) If

hexavalent chromIUm IS to be mcluded In the analytical scheme, a portion of the

filtrate should be transferred before aCidificatIOn to a separate contamer and

analyzed as soon as possible usmg Method 218 4 Analyses performed on a sample

so treated shall be reported as "dissolved" concentratIOns

NOTE3 If a precipitate IS formed upon aCidification, the filtrate should be digested

usmg 4 1 3 Also, It has been suggested (InternatIOnal BIOlogICal Program, SympOSIUm

on Analytical Methods, Amsterdam, Oct 1966) that additional aCid, as much as 25 ml of

conc HClIhter, may be reqUIred to stabilize certam types of highly buffered samples IT

they are to be stored for any length of time Therefore, special precautions should be

observed for preservation and storage ofunusualsamples mtended for metal analySIS

4 1 2 For the deternunatIOn ofsuspended metals a representative volume ofunpreserved

sample must be filtered through a 0 45 u membrane filter When conSiderable

suspended matenalls present, as httle as 100 ml of a well mixed sample IS filtered

Record the volume filtered and transfer the membrane filter contammg the

msoluble matenal to 250 nil Gnffin beaker and add 3 ml conc redistilled HN03

Cover the beaker With a watch glass and heat gently The warm aCid Will soon

dissolve the membrane Increase the temperature of the hot plate and digest the

matenal When the aCid has nearly evaporated, cool the beaker and watch glass

and add another 3 ml of conc redistilled HN03 Cover and contmue heatmg until

METALS-S
the digestlOn IS complete, generally mdicated by a lIght colored digestate

Evaporate to near dryness (DO NOT BAKE), add 5 ml dIstIlled HCI (11) and

warm the beaker gently to dIssolve any soluble matenal (If the sample IS to be

analyzed by the furnace procedure, 1 ml of 1 1 dIstIlled HN03 per 100 ml dIlutlOn

should be substituted for the dIstilled 1 1 HCI) Wash down the watch glass and

beaker walls wIth deIomzed dIstIlled water and filter the sample to remove SIlIcates

and other msoluble matenal that could clog the atomIzer Adjust the volume to

some predetermmed value based on the expected concentratlOns ofmetals present

ThIS volume WIll vary dependmg on the metal to be determmed The sample IS now

ready for analySIS ConcentratlOns so determmed shall be reported as "suspended"

(See Note 4 )

NOTE 4: Certam metals such as antimony arsemc, gold, mdIUm, mercury,

osmIUm, palladIUm, platmIUm, rhemum, rhodIUm, ruthemum, selemum, sIlver,

thallIum, tm and tItamum requIre modificatlOn ofthe digestlOn procedure and the

tndividualsheetsfor these metals should be consulted

4 1 3 For the determmatlOn of total metals the sample IS aCIdIfied WIth 1 1 redIstilled

HN03 to a pH of less than 2 at the tIme of collectlOn The sample IS not filtered

before processmg Choose a volume ofsample appropnate for the expected level of

metals Ifmuch suspended matenaiis present, as lIttle as 50-100 ml of well mIxed

sample WIll most probably be suffiCIent (The sample volume reqUIred may also

vary proportIonally WIth the number ofmetals to be determmed )

Transfer a representatIve alIquot ofthe well mIxed sample to a Gnffin beaker and

add 3 ml of conc redIstIlled HN03 Place the beaker on a hot plate and evaporate

to near dryness cautlOusly, makmg certam that the sample does not boll (DO NOT

BAKE) Cool the beaker and add another 3 ml portlOn of conc redIstIlled HN03

Cover the beaker WIth a watch glass and return to the hot plate Increase the

temperature ofthe hot plate so that a gentle reflux actlOn occurs Contmue heatmg,

addmg addItIonal aCId as necessary, untIl the dIgestIon IS complete (generally

mdicated when the digestate IS lIght m color or does not change m appearance WIth

contmued refluxmg) Agam, evaporate to near dryness and cool the beaker Add a

small quantIty ofredIstIlled 11 HCI (5 m1/100 ml offmal solutlOn) and warm the

beaker to dIssolve any preCIpItate or reSIdue resultmg from evaporatlOn (If the

sample IS to be analyzed by the furnace procedure, SubstItute dIstilled HN03 for 1 1

HCI so that the final dilutlOn contams 05% (v/v) HN03 ) Wash down the beaker

walls and watch glass WIth dIstIlled water and filter the sample to remove SIlIcates

and other msoluble matenal that could clog the atomIzer Adjust the volume to

some predetermmed value based on the expected metal concentratlOns The sample

IS now ready for analySIS ConcentratlOns so determmed shall be reported as

"total" (see Note 4)

4 1.4 To determme total recoverable metals, aCIdIfy the entIre sample at the tIme of

collection WIth conc redIstIlled HN03, 5 mIll At the tIme of analYSIS a 100 ml

alIquot ofwell mIxed sample IS transferred to a beaker or flask FIve ml of dIstIlled

HCI (l 1) IS added and the sam~le heated on a steam bath or hot plate untIl the

METALS-6
volume has been reduced to 15-20 ml makIng certam the samples do not boll (If

the sample IS bemg prepared for furnace analYSIS, the same process should be

followed except HCl should be omItted) After thIS treatment the sample IS filtered

to remove sIhcates and other msoluble matenal that could clog the atomIzer and

the volume adjusted to 100 ml The sample IS then ready for analYSIS

ConcentratIOns so determmed shall be reported as "total" (See Notes 4, 5, and 6 )

NOTE 5: The analyst should be cautIOned that thIS dIgestIOn procedure may not be

suffiCIently VIgorous to destroy certam metal complexes Ifa colonmetnc procedure

IS to be employed for the final determmatIOn When thIS IS suspect, the more

VIgorous dIgestIOn gIven m 4 1 3 should be followed

NOTE 6: For dnnkmg water analyses by dIrect aspIratIOn, the final volume may be

reduced to effect up to a lOX concentratIon of the sample, provIded the total

dIssolved sohds m the ongmal sample do not exceed 500 mg/l, the determmatIOn

IS corrected for any non-specIfic absorbance and there IS no loss by preCIpItatIOn

5 Interferences

5 1 DIrect AspIratIOn

5 1 1 The most troublesome type of mterference m atomIC absorptIOn

spectrophotometry 18 usually termed "chemIcal" and IS caused by lack of

absorptIOn of atoms bound m molecular combmatIOn m the flame ThIS

phenomenon can occur when the flame IS not suffiCIently hot to dISSOCiate the

molecule, as m the case of phosphate mterference WIth magnesmm, or because the

dISSOCIated atom IS ImmedIately OXIdIzed to a compound that WIll not dISSOCIate

further at the temperature of the flame The addItIOn of lanthanum WIll overcome

the phosphate Interference In the magnesmm, calcmm and banum determInatIons

SImIlarly, sIhca mterference m the determmatIon of manganese can be ehmmated

by the addItIon ofcalcmm

5 1 2 ChemIcal mterferences may also be ehmmated by separatmg the metal from the

mterfenng matenal WhIle complexmg agents are pnmanly employed to mcrease

the senSItIVIty of the analYSIS, they may also be used to ehmmate or reduce

mterferences

5 1 3 The presence of hIgh dIssolved sohds m the sample may result m an mterference

from non-atomIC absorbance such as hght scattenng Ifbackground correctIOn IS

not avaIlable, a non-absorbmg wavelength should be checked Preferably, hIgh

sohds type samples should be extracted (see 5 1 1 and 9 2)

5 14 IOnIZatIOn Interferences occur where the flame temperature IS suffiCIently hIgh to

generate the removal of an electron from a neutral atom, gIvmg a pOSItIve charged

Ion ThIS type of Interference can generally be controlled by the addItion, to both

standard and sample SolutIons, ofa large excess ofan easIly IOnIzed element

5 1 5 Although qUIte rare, spectral mterference can occur when an absorbmg

wavelength of an element present In the sample but not bemg determmed falls

withm the WIdth ofthe absorptIon hne ofthe element ofmterest The results ofthe

determmatIon WIll then be erroneously hIgh, due to the contnbutIOn of the

mterfenng element to the atomIC absorptIOn SIgnal Also, mterference can occur

METALS-7
when resonant energy from another element m a multI-element lamp or a metal

Impunty m the lamp cathode falls withm the bandpass of the slIt settmg and that

metal IS present m the sample ThIs type ofmterference may sometimes be reduced

by narrowmg the slIt wIdth

5.2 Flameless AtomIzation

5 2 1 Although the problem of oXide formation IS greatly reduced wIth furnace

procedures because atomIzatIon occurs m an mert atmosphere, the technIque IS

still subject to chemIcal and matnx mterferences The composItion of the sample

matnx can have a major effect on the analysIs It IS those effects WhICh must be

determmed and taken mto consIderatIon m the analysIs of each dIfferent matrIx

encountered To help verIfy the absence of matnx or chemIcal mterference use the

followmg procedure WIthdraw from the sample two equal ahquots To one ofthe

alIquots add a known amount of analyte and dIlute both ahquots to the same

predetermmed volume [The dIlutIOn volume should be based on the analysIs ofthe

undIluted sample Preferably, the dIlutIon should be 1 4 whIle keepmg m mmd the

optImum concentratIon range ofthe analysIs Under no CIrcumstances should the

dIlutIon be less than 1 1] The dIluted alIquots should then be analyzed and the

unspiked results multIplIed by the dIlutIOn factor should be compared to the

ongmal determmation Agreement of the results (withm ±10%) mdicates the

absence of mterference ComparIson of the actual sIgnal from the spIke to the

expected response from the analyte m an aqueous standard should help confirm the

findmg from the dilution analysIs Those samples WhICh mdicate the presence of

mterference, should be treated m one or more ofthe followmg ways

a The samples should be successIvely dIluted and reanalyzed to

determme Ifthe mterference can be ehmmated

b The matrIX ofthe sample should be modIfied m the furnace Examples

are the addItIon of ammOnIum nItrate to remove alkalI chlOrIdes,

ammOnIum phosphate to retam cadmIum, and nIckel nItrate for

arsenIC and selenIum analyses [ATOMIC ABSORPTION

NEWSLETTER Vol 14, No 5, p 127, Sept-Oct 1975] The mIxmg of

hydrogen WIth the mert purge gas has also been used to suppress

chemIcal mterference The hydrogen acts as a reducmg agent and aIds

m molecular dIssocIation

c Analyze the sample by method ofstandard addItIons whIle notmg the

precautIons and lImItatIons ofItS use (See 8 5)

5 2 2 Gases generated m the furnace dunng atomIzatIon may have molecular absorptIon

bands encompassmg the analytIcal wavelength When thIS occurs, eIther the use of

background correctIon or choosmg an alternate wavelength outsIde the absorptIOn

band should elImmate thIs mterference Non-specIfic broad band absorptIon

mterference can also be compensated for WIth background correctIon

5 2 3 Interference from a smoke-producmg sample matnx can sometImes be reduced by

extendmg the charrIng time at a hIgher temperature or utuIzmg an ashmg cycle m

METALS-8
the presence of a1r Care must be taken, however, to prevent loss of the analys1s

element

5 2 4 Samples contammg large amounts of orgamc matenals should be oX1d1zed by

conventional aC1d d1gestlOn pnor to bemg placed m the furnace In th1S way broad

band absorptlOn wl1l be m1mm1zed

5 2 5 From amon mterference stud1es m the graph1te furnace 1t 1S generally accepted that

mtrate 1S the preferred amon Therefore mtnc aC1d 1S preferable for any d1gestlOn or

solub1hzatlOn step If another aC1d m add1tion to HN03 1S reqUlred a m1mmum I

amount should be used Th1S apphes part1cularly to hydrochlonc and to a lesser

extent to sulfunc and phosphonc aC1ds

5 2 6 Carb1de formatlOn resultmg from the chem1cal enVironment of the furnace has

been observed w1th certam elements that form carb1des at h1gh temperatures

Molybdenum may be c1ted as an example When th1S takes place, the met~l wl1l be

released very slowly from the carb1de as atom1zatlOn contmues For molybdenum,

one may be reqUlred to atom1ze for 30 seconds or more before the slgnal returns to

basehne levels Th1s problem 1S greatly reduced and the sens1t1v1ty mcreased w1th

the use ofpyrolytically-coated graph1te

5 2 7 Iomzation mterferences have to date not been reported w1th furnace techmques

5 2 8 For comments on spectral mterference see sectlOn 5 1 5

5 2 9 ContammatlOn ofthe sample can be a major source oferror because ofthe extreme

sens1t1v1ties ach1eved w1th the furnace The sample preparatlOn work area should

be kept scrupulously clean All glassware should be cleaned as d1rected m part 6 9

of the Atom1C AbsorptlOn Methods sectlOn of th1S manual P1pet tips have been

known to be a source of contammatlOn If suspected, they should be aC1d soaked

w1th 1 5 HN03 and nnsed thoroughly w1th tap and delOmzed water The use of a

better grade p1pet tip can greatly reduce th1S problem It 1S very 1mportant that

special attentlOn be glven to reagent blanks m both analys1s and the correctlOn of

analytlCal results Lastly, pyrolyt1c graph1te because ofthe productlOn process and

handlmg can become contammated As many as five to poss1bly ten h1gh

temperature burns may be reqUlred to clean the tube before use

6 Apparatus

6 1 Atom1c absorptlOn spectrophotometer Smgle or dual channel, smgle-or double-beam

mstrument havmg a gratmg monochromator, photomultipher detector, adjustable shts, a

wavelength range of 190 to 800 nm, and prov1s1ons for mterfacmg w1th a stnp chart

recorder

6 2 Burner The burner recommended by the partlCular mstrument manufacturer should be

used For certam elements the mtrous oX1de burner 1S reqUlred

6 3 Hollow cathode lamps Smgle element lamps are to be preferred but mult1-element lamps

may be used Electrodeless d1scharge lamps may also be used when aval1able

6 4 Graph1te furnace Any furnace deV1ce capable of reachmg the spec1fied temperatures 1S

sat1sfactory

METALS-9
6 5 Stnp chart recorder A recorder IS strongly recommended for furnace work so that there

wIll be a permanent record and any problems WIth the analysIs such as dnft, mcomplete

atomIzatIOn, losses durmg charnng, changes m sensItivIty, etc, can be easIly recognIzed

6 6 PIpets MICrolIter WIth dIsposable tIpS SIzes can range from 5 to 100 mICrolIters as

reqUIred NOTE 7 PIpet tips whIch are whIte m color, do not contam CdS, and have

been found SUItable for research work are avaIlable from Ulster SCIentIfic, Inc 53 Mam

St HIghland, NY 12528 (914) 691-7500

6.7 Pressure-reducmg valves The supplIes of fuel and OXIdant shall be mamtamed at

pressures somewhat hIgher than the controlled operatmg pressure of the mstrument by

SUItable valves

6 8 Separatory flasks 250 ml, or larger, for extractIOn WIth organIc solvents

6 9 Glassware All glassware, lmear polyethylene, polyproplyene or Teflon contamers,

mcludmg sample bottles, should be washed WIth detergent, rmsed WIth tap water, 1 1

nItric aCId, tap water, 1 1 hydrochlonc aCId, tap water and deIOnIZed dIstIlled water m

that order [See Notes 1 and 2 under (41) concernIng the use of chromIc acId and the

cleanIng procedure]

6 10 BorosIlIcate glass dIstIllatIOn apparatus

7. Reagents

7 1 DeIOnIZed dIstIlled water Prepare by passmg dIstilled water through a mIxed bed of

catIOn and anIon exchange resms Use deIOnIzed dIstilled water for the preparatIOn of all

reagents, calIbratIOn standards, and as dIlutIOn water

72 NItnc aCId (conc) If metal Impunties are found to be present, dIstIll reagent grade

nItnc aCId m a borOSIlIcate glass dIstIllatIOn apparatus or use a spectrograde aCId

CautIOn DIstillatIOn should be performed m hood WIth protectIve sash m place

721 NItnc ACId (11) Prepare all dIlutIOn WIth deIOnIZed, dIstIlled water by

addmg the conc aCId to an equal volume ofwater

7.3 Hydrochlonc aCId (11) Prepare all solutIOn ofreagent grade hydrochlonc aCId and

deIOnIzed dIstIlled water Ifmetal Impunties are found to be present, dIStIll thIS mIxture

from a borOSIlIcate glass dIstIllatIOn apparatus or use a spectrograde aCId

74 Stock standard metal solutIOns Prepare as dIrected m (8 1) and under the mdiVIdual

metal procedures CommerCIally avaIlable stock standard solutIOns may also be used

7 5 CalIbratIOn standards Prepare a senes of standards of the metal by dIlutIOn of the

appropnate stock metal solutIOn to cover the concentratIOn range deSIred

76 Fuel and OXIdant CommerCIal grade acetylene IS generally acceptable AIr may be

supplIed from a compressed aIr lIne, a laboratory compressor, or from a cylInder of

compressed arr Reagent grade nItrous OXIde IS also reqUIred for certam determmatIOns

Standard, commerCIally avaIlable argon and nItrogen are reqUIred for furnace work

7 7 SpecIal reagents for the extractIOn procedure

7 7 1 PyrrolIdme dithIOcarbamic aCId (PDCA) "see footnote" Prepare by addmg 18

m1 of analytical reagent grade pyrrolIdme to 500 ml of chloroform m a lIter flask

The name pyrrohdine dithlOcarbamic aCId (PDCA), although commonly referenced m the SCIentIfic

literature IS ambiguous From the chemIcal reaction of pyrrohdme and carbon dIsulfide a more

proper name would be I-pyrrohdme carbodithlO1C aCId, PCDA (CAS RegIstry No 25769-03-3)

METALS-lO
(See Note 8) Cool and add 15 ml of carbon dIsulfide m small portIOns and wIth

sWIrhng Dtlute to 1 hter wIth chloroform The solutIOn can be used for several

months Ifstored m a brown bottle m a refngerator

NOTE 8: An acceptable grade of pyrrohdme may be obtamed from the Aldnch

ChemIcal Co, 940 West St Paul Ave, Mtlwaukee, WI 53233 (414, 273-3850)

7 7 2 AmmOnIum hydroxIde, 2N DIlute 13 ml conc NH40H to 100 ml with

deIOnIzed dIstIlled water

773 Bromophenol blue mdicator(l glItter) DIssolve 0 1 g bromophenol blue m 100

ml of 50 percent ethanol or Isopropanol

774 HCI,2 5% vlv DIlute 2 ml redIstIlled HCI (6N) to 40 ml WIth deIOnIzed dIstIlled

water

8 PreparatIon ofStandards and CahbratIOn

8 1 Stock standard solutIOns are prepared from hIgh punty metals, OXIdes or nonhygroscopiC

reagent grade salts usmg deIOmzed dIstIlled water and redIstIlled mtnc or hydrochlonc

acIds (See mdividual analySIS sheets for speCIfic mstructIOn) Sulfunc or phosphonc

aCIds should be aVOIded as they produce an adverse effect on many elements The stock

SolutIons are prepared at concentratIOns of 1000 mg ofthe metal per hter CommercIally

avaIlable standard solutIOns may also be used

8 2 CahbratIOn standards are prepared by dilutmg the stock metal SolutIons at the tIme of

analySIS For best results, cahbratIOn standards should be prepared fresh each tIme an

analySIS IS to be made and dIscarded after use Prepare a blank and at least four

cahbration standards m graduated amounts m the appropnate range The cahbratIOn

standards should be prepared usmg the same type of aCId or combmatIOn of aCIds and at

the same concentratIon as WIll result m the samples followmg processmg As filtered

water samples are preserved WIth 1 1 redIstIlled HN03 (3 ml per hter), cahbratIOn

standards for these analyses should be sImtlarly prepared WIth HN03 Begmmng WIth

the blank and workmg toward the hIghest standard, aspIrate the solutIons and record the

readmgs Repeat the operatIOn WIth both the cahbration standards and the samples a

suffiCIent number of tImes to secure a rehable average readmg for each solutIOn

CahbratIOn standards for furnace procedures should be prepared as descnbed on the

mdividual sheets for that metal

8 3 Where the sample matnx IS so complex that VISCOSIty, surface tenSIon and components

cannot be accurately matched WIth standards, the method ofstandard addItIOn must be

used ThIS techmque rehes on the addItIon of small, known amounts of the analySIS

element to portIons of the sample-the absorbance dIfference between those and the

origmal solutIOn gIvmg the slope of the cahbratIOn curve The method of standard

addItIon IS descnbed m greater detaIl m (8 5)

METALS-II
8.4 For those Instruments WhICh do not read out dIrectly In concentratIOn, a calIbratiOn

curve IS prepared to cover the approprIate concentratIOn range Usually, thIS means the

preparatIOn of standards whIch produce an absorptIon of 0 to 80 percent The correct

method IS to convert the percent absorptIOn readIngs to absorbance and plot that value

agaInst concentratIon The folloWIng relatIOnshIp IS used to convert absorptiOn values to

absorbance

absorbance = log (lOO/%T) = 2-log % T

where % T = 100-% absorptIon

As the curves are frequently nonlInear, espeCIally at hIgh absorption values, the number

ofstandards should be Increased In that portIOn ofthe curve

8 5 Method ofStandard AddItiOns In thIS method, equal volumes ofsample are added to a

deIonIzed dIstIlled water blank and to three standards contaInIng dIfferent known

amounts of the test element The volume of the blank and the standards must be the

same The absorbance ofeach solutIOn IS determmed and then plotted on the vertICal aXIS

of a graph, WIth the concentratiOns of the known standards plotted on the hOrIzontal

axIS When the resultIng lIne IS extrapolated back to zero absorbance, the POInt of

InterceptiOn ofthe abSCIssa IS the concentratIon ofthe unknown The abscIssa on the left

ofthe ordInate IS scaled the same as on the rIght SIde, but In the OppOSIte dIrectiOn from

the ordInate An example ofa plotso obtaIned IS shown In FIg 1

G)

()

s::

c

.c

..

o

II)

.c

<C

Cone of

Sample

Addn 0

No Addn

Addn I

Addn of50%

of Expected

Amount

Concentration

Addn 2 Addn 3

Addn of 100% Addn of 150%

of Expflcted of Expected

Amount Amounf

FIGURE 1. STANDARD ADDITION PLOT

METALS-12
The method ofstandard addItIons can be very useful, however, for the results to be va11d

the followmg 11mItatIOns must be taken mto consIderatIOn

a) the absorbance plot of sample and standards must be 11near over the

concentratIOn range of concern For best results the slope of the plot should

be nearly the same as the slope of the aqueous standard curve Ifthe slope IS

sIgmficantly dIfferent (more than 20%) caution should be exercIsed

b) the effect of the mterference should not vary as the ratIO of analyte

concentratIOn to sample matnx changes and the standard addItIOn should

respond m a sImIlar manner as the analyte

c) the determmatIOn must be free ofspectral mterference and corrected for nonspecIfic background mterference

9 General Procedure for AnalysIs by AtomIc AbsorptIOn

9 1 DIrect AspIratIon DIfferences between the vanous makes and models of satIsfactory

atomIC absorptIon spectrophotometers prevent the formulatIOn of detaIled mstructIOns

apphcable to every mstrument The analyst should follow the manufacturer's operatmg

mstructIOns for hIS partIcular mstrument In general, after choosmg the proper hollow

cathode lamp for the analysIs, the lamp should be allowed to warm up for a mmimum of

15 mmutes unless operated m a double beam mode Dunng thIS penod, ahgn the

mstrument, posItIOn the monochromator at the correct wavelength, select the proper

monochromator s11t WIdth, and adjust the hollow cathode current accordmg to the

manufactuerer's recommendation Subsequently, 11ght the flame and regulate the flow of

fuel and oXIdant, adjust the burner and nebuhzer flow rate for maXImum percent

absorptIon and stabIhty, and balance the photometer Run a senes of standards of the

element under analysIs and construct a cahbratIOn curve by plottmg the concentratIOns

of the standards agamst the absorbance For those mstruments whIch read dIrectly m

concentratIOn set the curve corrector to read out the proper concentratIOn AspIrate the

samples and determme the concentratIOns eIther dIrectly or from the calIbratIon curve

Standards must be run each time a sample orsenes ofsamples are run

9 1 1 CalculatIOn - DIrect determmation of 11qUId samples Read the metal value m

mg/l from the cahbratIOn curve or dIrectly from the readout system of the

mstrument

9 1 1 1 IfdIlutIOn ofsample was reqUired

mg/l metal m sample = A (c B )

where

A = mg/l ofmetal mdIluted ahquot from calIbration curve

B = m1 ofdeIOlllzed dIstIlled water used for dIlutIOn

C = ml ofsample ahquot

METALS-13
9 1 2 Forsamples contaInIng particulates

mg/l metal In sample = A ( )

where

A = mg/l ofmetal In processed sample from cahbratIOn curve

V = final volume ofthe processed sample In m1

C = ml ofsample ahquot processed

9 1 3 Forsohd samples report all concentratIOns as mglkg dry weight

9 1 3 1 Dry sample:

AxV

mg metal/kg sample = D

where

A = mg/l ofmetal In processed sample from cahbratIOn curve

V = final volume ofthe processed sample In ml

D = weight ofdry sample In grams

9 1 32 Wet sample

AxV

mg metal/kg sample = W x P

where

A = mg/l ofmetal In processed sample from cahbratIOn curve

V = final volume ofthe processed sample In ml

W = weight ofwet sample In grams

P = %sohds

9 2 Special ExtractIOn Procedure When the concentratIOn of the metal IS not sufficiently

high to determIne directly, or when conSiderable dissolved sohds are present In the

sample, certaIn metals may be chelated and extracted with orgamc solvents Ammomum

pyrrohdIne dlthlocarbamate (APDC) (see footnote) In methyl Isobutyl ketone (MIBK) IS

widely used for thiS purpose and IS particularly useful for ZInC, cadmIUm, Iron,

manganese, copper, sliver, lead and chromlUm+6 Tn-valent chromIUm does not react

with APDC unless It has first been converted to the hexavalent form [AtomiC Absorption

Newsletter 6, p 128 (1967)] ThiS procedure IS descnbed under method 218 3

The name ammOnIum pyrrohdme dlthlOcarbamate (APDC) IS somewhat ambiguous and should more

properly becalledammomum, I-pyrrohdme carbodlthlOate (APCD), CAS RegIstry No 5108-96-3

METALS-14
AlumInum, berylhum, banum and strontmm also do not react wIth APDC While the

APDC·MIBK chelatmg-solvent system can be used satIsfactonly, It IS possIble to

expenence dIfficulties (See Note 9)

NOTE 9: CertaIn metal chelates, manganese-APDC In partlCular, are not stable In

MIBK and will redIssolve Into the aqueous phase on standIng The extractIOn of other

metals IS sensItive to both shakIng rate and time As wIth cadmmm, prolonged extractIOn

beyond 1 mInute, will reduce the extractIOn efficIency, whereas 3 mInutes of vIgorous

shakIng IS reqmred for chrommm

Also, when multIple metals are to be determIned eIther larger sample volumes must be

extracted or IndIVIdual extractIOns made for each metal beIng determIned The aCId form

of APDC-pyrrohdIne dlthIOcarbamlc aCId prepared dIrectly In chloroform as descnbed

by Lakanen, [AtomIc AbsorptIOn Newsletter 5, p 17 (1966)], (see 7 7 1) has been found

to be most advantageous In thIS procedure the more dense chloroform layer allows for

easy cOmbInatIOn of multiple extractIOns whlCh are carned out over a broader pH range

favorable to multielement extractIOns PyrrohdIne dlthIOcarbamlc aCId In chloroform IS

very stable and may be stored m a brown bottle In the refngerator for months Because

chloroform IS used as the solvent, It may not be aspIrated Into the flame The followmg

procedure IS suggested

9 2 1 ExtractIOn procedure wIth pyrrohdIne dlthIOcarbamlc aCId (PDCA) In

chloroform

9 2 1 1 Transfer 200 ml ofsample Into a 250 ml separatory funnel, add 2 drops

bromphenol blue IndlCator solutIOn (7 7 3) and mIX

9 2 1 2 Prepare a blank and sufficIent standards m the same manner and adjust

the volume of each to approxImately 200 ml wIth deIOnIzed dlstdled

water All of the metals to be determIned may be combIned Into SIngle

solutIOns at the appropnate concentratIOn levels '

9 2 1 3 Adjust the pH by addItIOn of 2N NH40H solutIOn (7 7 2) untd a blue

color persIsts Add HCI (774) dropWlse until the blue color Just

dIsappears, then add 2 0 ml Hel (7 7 4) m excess The pH at thIS pomt

should be 2 3 (The pH adjustment may be made WIth a pH meter

.nstead of USIng mdlCator )

9214 Add 5 ml of PDCA-chloroform reagent (7 7 1) and shake vIgorously

for 2 mInutes Allow the phases to separate and draIn the chloroform

layer Into a 100 m1 beaker (See NOTE 10 )

NOTE 10: If hexavalent chrommm IS to be extracted, the aqueous

phase must be readjusted back to a pH of 2 3 after the addItion of

PDCA-chloroform and maIntaIned at that pH throughout the

r extractIOn For multielement extractIOn, the pH may adjusted upward

after the chrommm has been extracted

METALS-IS
9.219

9.215

9216

9217

9218

Add a second portion of 5 ml PDCA-chloroform reagent (771) and

shake vigorously for 2 mmutes Allow the phases to separate and

combme the chloroform phase With that obtamed m step (9 2 1 4)

Determine the pH ofthe aqueous phase and adjust to 4 5

Repeat step (9 2 1 4) agam combmmg the solvent extracts

Readjust the pH to 5 5, and extract a fourth tlme Combme all extracts

and evaporate to dryness on a steam bath

Hold the beaker at a 45 degree angle, and slowly add 2 ml of conc

dlstl1led mtnc aCid, rotatmg the beaker to effect thorough contact of

the aCld With the residue

9 2 1 10 Place the beaker on a low temperature hotplate or steam bath and

evaporateJust to dryness

92 111 Add 2 m1 ofmtnc aCid (1 1) to the beaker and heat for 1 mmute Cool,

quantitatively transfer the solutlOn to a 10 ml volumetnc flask and

bnng to volume With dlstl1led water The sample IS now ready for

analySIS

9.22 Prepare a callbratlOn curve by plottmg absorbance versus the concentratlOn ofthe

metal standard (ug/l) m the 200 ml extracted standard solutlOn To calculate

sample concentratlOn read the metal value m ug/l from the callbratlOn curve or

directly from the readout system of the mstrument If dl1utlOn of the sample was

requITed use the followmg equatlOn

mg/l metal m sample = Z C (C+B)

where

Z = ug/l ofmetal m dl1uted allquot from callbration curve

B = ml ofdelOmzed distilled water used for dl1utlon

C = ml ofsample allquot

9 3 Furnace Procedure Furnace deVlces (flameless atomlzatlOn) are a most useful means of

extendmg detection llmlts Because of differences between vanous makes and models of

satisfactory mstruments, no detal1ed operatmg mstuctlOns can be given for each

mstrument Instead, the analyst should follow the mstructlOns provided by the

manufacturer of hiS particular mstrument and use as a gUIde the temperature settmgs

and other mstrument conditions llsted on the mdivldual analYSIS sheets which are

recommended for the Perkin-Elmer HGA-2100 In addition, the followmg pomts may be

helpful

93 1 With flameless atomization, background correctlOn becomes of high Importance

especially below 350 nm Tills IS because certam samples, when atomized, may

absorb or scatter llght from the hollow cathode lamp It can be caused by the

presence of gaseous molecular speCies, salt partlCules, or smoke m the sample

METALS-16
beam Ifno correctIOn IS made, sample absorbance wIll be greater than It should be,

and the analytIcal result wIll be erroneously hIgh

9 3 2 If dunng atomIzatIOn all the analyte IS not volatIlIzed and removed from the

furnace, memory effects wIll occur ThIS condItIOn IS dependent on several factors

such as the volatIlIty of the element and ItS chemIcal form, whether pyrolytIc

graphIte IS used, the rate of atomIzatIon and furnace desIgn If thIS sItuatIOn IS

detected through blank burns, the tube should be cleaned by operatIng the furnace

at full power for the reqUIred tIme penod as needed at regular Intervals In the

analytIcal scheme

9 3 3 Some ofthe smaller SIze furnace devIces, or newer furnaces eqUIpped wIth feedback

temperature control (InstrumentatIOn Laboratones MODEL 555, PerkIn-Elmer

MODELS HGA 2200 and HGA 76B, and VarIan MODEL CRA-90) emploYIng

faster rates of atOmIZatIOn, can be operated USIng lower atomIzatIon temperatures

for shorter tIme penodsthan those lIsted In thIS manual

9 3 4 Although pnor dIgestion of the sample In many cases IS not reqUIred provIdIng a

representative alIquot ofsample can be pipeted Into the furnace, It wIll provIde for a

more unIform matnx and possIbly lessen matnx effects

9 3 5 Inject a measured mICrolIter alIquot ofsample Into the furnace and atomIze Ifthe

concentratIOn found IS greater than the hIghest standard, the sample should be

dIluted In the same aCId matnx and reanalyzed The use of multiple Injections can

Improve accuracy and help detect furnace pipettIng errors

9 3 6 To venfy the absence ofInterference, follow the procedure as gIven In part 5 2 I

9 3 7 A check standard should be run approxImately after every 10 sample InjectIOns

Standards are run In part to mOnItor the lIfe and performance ofthe graphIte tube

Lack of reproducIbIlIty or sIgnIficant change In the sIgnal for the standard

IndIcates that the tube should be replaced Even though tube lIfe depends on

sample matnx and atomIzatIOn temperature, a conservatIve estImate would be that

a tube wIll last at least 50 fmngs A pyrolytIc-coatIng would extend that estimate

by a factor of3

9 3 8 CalculatIOn-For determInatIOn of metal concentratIOn by the furnace Read the

metal value In ug/l from the calIbratIOn curve or dIrectly from the readout system

ofthe Instrument

9 3 8 I IfdIfferent SIze furnace InjectIOn volumes are used for samples than for

standards

ug/l of metal In sample = Z ( )

where

Z = ug/l ofmetal read from calIbratIOn curve or readout system

S = ul volume standard Injected Into furnace for calIbratIon curve

U = ul volume ofsample Injected for analYSiS

METALS-I7
9382 IfdIlutIon ofsample was reqUIred but sample InjectIOn volume same as

for standard

( ug/l of metal In sample = Z c C+ B)

where

z = ug/l metal In dtluted ahquot from cahbratlon curve

B = ml ofdeIOnIzed dIstIlled water used for dIlutIon

C = ml ofsample ahquot

9 3 9 Forsample contaInIng partIculates

ug/l of metal In sample = Z (~)

where

z=

V=

C=

9310

ug/l ofmetal In processed sample from cahbratlon curve (See 9 3 8 1)

final volume ofprocessed sample In ml

ml ofsample ahquot processed

Forsohd samples Report all concentratIons as mglkg dry weIght

9 3 10 1 Dry sample

mg metal/kg sample = D

where

Z = ug/l ofmetal In processed sample from cahbratIOn curve (See 9 3 8 1)

V = final volume ofprocessed sample In ml

D = weIght ofdry sample In grams

93102 Wet sample

(I,~) V

mg metal/kg sample = W X P

where

Z = ug/l ofmetal In processed sample from cahbratIOn curve (See 9 3 8 1)

V = final volume ofprocessed sample In ml

W = weIght ofwetsample In grams

P = %sohds

METALS-I8
10 36

10 35

10 12

10 22

10 37

10 3 4

10 3 2

10 33

I

I

I

I

I

I QualIty Control For DnnkIng Water AnalysIs I

10 1 Mimmum reqmrements :

10 1 1 All qualIty control data should be maIntaIned and avaIlable for easy

reference or InSpectIon I

An unknown performance sample (when avaIlable) must be analyzed once

per year for the metals measure4 Results must be wIthIn the control lImIt

establIshed by EPA If problerrls anse, they should be corrected, and a

follow-up performance sample shbuld be analyzed

10 2 Mimmum Dally control I

10 2 1 After a calIbratlOn curve compo~ed of a mInImUm of a reagent blank and

three standards has been preparfd, subsequent calIbratlOn curves must be

verlfied by use of at least a reag?nt blank and one standard at or near the

MCL Dally checks must be wIthl!n ±10 percent ofongInal curve

If20 or more samples per day are ~nalyzed, the workIng standard curve must

be verlfied by runmng an addItlO;nal standard at or near the MCL every 20

samples Checks must be wIthIn :L 10 percent oforIgInal curve

10 3 OptlOnal Reqmrements I

10 3 1 A current serVIce contract shoul;d be In effect on balances and the atomIC

absorptlOn spectrophotometer i

Class S weIghts should be avallabU:l to make penodic checks on balances I

ChemIcals should be dated upon J-ecelpt ofshIpment and replaced as needed

or before shelflIfe has been excee~ed

A known reference sample (when avaIlable) should be analyzed once per

quarter for the metals measured :The measured value should be wIthIn the

control lImIts establIshed by EPA I

I

At least one duplIcate sample should be run every 10 samples, or wIth each

I

set ofsamples to venfy preCIsIon ofthe method Checks should be wIthIn the

control lImIt establIshed by EPA i

Standard devlatlOn should bl( obtaIned and documented for all

measurements beIng conducted I

QualIty Control charts or a tab;ulation of mean and standard devlatlOn

should be used to document vahdI1r

y ofdata on a dally basIs

10

METALS-19
&EPA

United States

Environmental Protection

Agency

Research and Development

Test Method

Environmental MOnltonng and

Support Laboratory

Cincinnati OH 45268

Inductively Coupled PlasmaAtomic Emission Spectrometric

Method for Trace Element

Analysis of Water and

Wastes-Method 200.7

1 Scope and ApplicatIon

1 1 This method may be used for

the determination of dissolved

suspended, or total elements In

drinking water, surface water

domestic and Industnal wastewaters

1 2 Dissolved elements are

determined In filtered and aCidified

samples Appropnate steps must be

taken In all analyses to ensure that

potential Interference are taken Into

account This IS especially true when

dissolved solids exceed 1500 mg/L

(See 5)

1 3 Total elements are determined

after appropnate digestion procedures

are performed Since digestion

techniques Increase the dissolved

solids content of the samples,

appropnate steps must be taken to

correct for potential Interference

effects (See 5 )

1 4 Table 1 lists elements for which

this method applies along with

recommended wavelengths and

typical estimated Instrumental

detection limits uSing conventional

pneumatic nebulization Actual

working detection limits are sample

dependent and as the sample matnx

vanes, these concentrations may also

vary In time, other elements may be

added as more information becomes

available and as required

1 5 Because of the differences

between vanous makes and models of

satisfactory Instruments, no detailed

Instrumental operating instructions

can be provided Instead, the analyst

IS referred to the instructions provided

by the manufacturer of the particular

Instrument

2 Summary of Method

2 1 The method descrrbes a

technique for the simultaneous or

sequential multielement

determination of trace elements In

solution The basIs of the method IS

the measurement of atomic emiSSion

by an optical spectroscopic technique

Samples are nebulized and the

aerosol that IS produced IS transported

to the plasma torch where excitation

occurs Charactenstlc atomic-line

emiSSion spectra are produced by a

radio-frequency inductively coupled

plasma (ICP) The spectra are

dispersed by a grating spectrometer

and the intensities of the lines are

mOnitored by photomultiplier tubes

The photocurrents from the

photomultiplier tubes are processed

and controlled by a computer system

A background correction technique IS

required to compensate for vanable

background contnbutlon to the

Metals-20 Dec 1982
determmatlon of trace elements

Background must be measured

adjacent to analyte Imes on samples

during analysIs The position selected

for the background intensity

measurement on either or both sides

of the analytical line, will be

determmed by the complexity of the

spectrum adjacent to the analyte line

The position used must be free of

spectral Interference and reflect the

same change In background

intensity as occurs at the analyte

wavelength measured Background

correction IS not required m cases of

line broadening where a background

correction measurement would

actually degrade the analytical result

The POSSibility of additional

Interferences named In 5 1 (and tests

for their presence as descnbed In 5 2)

should also be recognized and

appropnate corrections made

3 Definitions

3 1 Dissolved - Those elements

which will pass through a 045 pm

membrane filter

3 2 Suspended - Those elements

which are retained by a 045 pm

membrane filter

3 3 Total - The concentration

determined on an unfiltered sample

follOWing vigorous digestion (9 3) or

the sum of the dissolved plus

suspended concentrations (9 1 plus

92)

34 Total recoverable - The

concentration determined on an

unfiltered sample follOWing treatment

with hot dilute minerai aCid (9 4)

3 5 Instrumental detection limit -

The concentratIon equivalent to a

Signal, due to the analyte which IS

equal to three times the standard

deviation of a senes of ten rephcate

measurements of a reagent blank

Signal at the same wavelength

3 6 SensItivity - The slope of the

analytical curve, I e functional

relationship between emiSSIOn

intensity and concentratIOn

3 7 Instrument check standard - A

multielement standard of known

concentratIons prepared by the

analyst to mOnitor and venfy

Instrument performance on a dally

basIs (See 7 6 1)

3 8 Interference check sample - A

solution containing both Interfermg

and analyte elements of known

concentration that can be used to

venfy background and Interelement

correction factors (See 7 6 2)

3 9 Quahty control sample - A

solution obtained from an outSide

source having known, concentration

values to be used to venfy the

cahbratlon standards (See 7 6 3)

3 10 Cahbratlon standards - a

senes of know standard solutions

used by the analyst for calibration of

the Instrument (I e , preparation of the

analytical curve) (See 74)

3 11 Linear dynamic range - The

concentration range over which the

analytIcal curve remains linear

3 12 Reagent blank - A volume of

deionized distilled water containing

the same aCid matnx as the

cahbratlon standards carned through

the entire analytical scheme (See

752)

3 13 Calibration blank - A volume

of deionIzed distilled water aCidified

WIth HN03 and HCI (See 7 5 1)

3 14 Method of standard addition -

The standard addition technIque

Involves the use of the unknown and

the unknown plus a known amount of

standard (See 10 6 1)

4 Safety

4 1 The tOXICity or carclnogemclty of

each reagent used In thiS method has

not been precisely defined however

each chemical compound should be

treated as a potential health hazard

From thiS vlewpomt exposure to

these chemicals must be reduced to

the lowest pOSSIble level by whatever

means available The laboratory IS

responsible for maintaining a current

awareness file of OSHA regulations

regarding the safe handling of the

chemIcals specified In thiS method A

reference file of matenal data

handling sheets should also be made

available to all personnel Involved In

the chemical analySIS Additional

references to laboratory safety are

available and have been Identified

(147 148 and 149) for the

information of the analyst

5 Interferences

5 1 Several types of Interference

effects may contnbute to inaccuracies

In the determinatIOn of trace

elements They can be summanzed as

follows

5 1 1 Spectral mterferences can be

categonzed as 1) overlap of a spectral

hne from another element, 2)

unresolved overlap of molecular band

spectra, 3) background contnbutlon

from continuous or recombination

phenomena, and 4) background

contribution from stray hght from the

line emiSSion of high concentration

elements The first of these effects

can be compensated by utiliZing a

computer correction of the raw data,

requlnng the monltonng and

measurement of the Interfenng

element The second effect may

reqUire selectIOn of an alternate

wavelength The third and fourth

effects can usually be compensated by

a background correction adjacent to

the analyte line In addition, users of

Simultaneous multielement

instrumentation must assume the

responSibility of venfymg the absence

of spectral Interference from an

element that could occur In a sample

but for which there IS no channel In

the Instrument array Listed In Table 2

are some Interference effects for the

recommended wavelengths given In

Table 1 The data In Table 2 are

Intended for use only as a

rudimentary gUide for the indication of

potential spectral Interferences For

thiS purpose, linear relations between

concentration and intensIty for the

analytes and the Interferents can be

assumed

The Interference information which

was collected at the Ames Laboratory, 1

IS expressed at analyte concentration

eqlvalents (I e false analyte concentrations) anslng from 100 mg/L of the

Interferent element The suggested use

of thiS informatIon IS as follows

Assume that arsenic (at 193 696 nm)

IS to be determined In a sample

containing approXimately 10 mg/L of

aluminum Accordmg to Table 2,100

mg/L of aluminum would yield a false

SIgnal for arsenic eqUivalent to

approximately 1 3 mg/L Therefore,

10 mg/L of aluminum would result In

a false Signal for arsenic eqUivalent to

approximately 0 13 mg/L The reader

IS cautioned that other analytical

systems may exhibit somewhat

different levels of Interference than

those shown In Table 2, and that the

Interference effects must be evaluated

for each indiVidual system

Only those Interferents listed werp

investigated and the blank spaces In

Table 2 indicate that measurable interferences were not observed for the

Interferent concentrations listed In

Table 3 Generally Interferences were

discernible If they produced peaks or

background shifts correspondmg to

2-5% of the peaks generated by the

'Ames Laboratory USDOE Iowa State University

Ames Iowa 50011

Dec 1982 Metals-21
analyte concentrations also listed In

Table 3

At present, information on the listed

Silver and potassium wavelengths are

not available but It has been reported

that second order energy from the

magnesium 383 231 nm wavelength

Interferes with the listed potassium line

at 766491 nm

5.1.2 Physical mterferences are

generally considered to be effects

associated with the sample nebulization and transport processes Such

properties as change In VISCOSity and

surface tension can cause Significant

inaccuracies especially In samples

which may contain high dissolved

solids and/or acid concentrations The

use of a penstaltlc pump may lessen

these Interferences If these types of

Interferences are operative. they must

be reduced by dilution of the sample

and/or utilization of standard addition

techniques Another problem which

can occur from high dissolved solids

is salt bUildup at the tiP of the

nebulizer This affects aersol flow-rate

causing Instrumental dnft Wetting

the argon prior to nebulization, the

use of a tip washer, or sample dilution

have been used to control this

problem. Also. It has been reported

that better control of the argon flow

rate Improves instrument

performance This IS accomplished

with the use of mass flow controllers

5 1.3 ChemIcal Interferences are

charactenzed by molecular compound

formation, Ionization effects and

solute vaponzatlOn effects Normally

these effects are not pronounced With

the lCP technique, however, If

observed they can be minimized by

careful selection of operating

conditions (that IS, mCldent power,

observation pOSitIOn. and so forth). by

buffering of the sample, by matnx

matching, and by standard additIOn

procedures These types of

Interferences can be hIghly dependent

on matrix type and the speCifiC

analyte erement

6.2 It IS recommended that

whenever a new or unusual sample

matrix is encountered, a senes of

tests be performed pnor to reporting

concentration data for analyte

elements These tests. as outlined In

5 2 1 through 5 2 4, Will ensure the

analyst that neither POSitive nor

negatlve interference effects are

operative on any of the analyte elements thereby dIstorting the

accuracy of the reported values

52 1 Sertal dIlutIon-If the analyte

concentration IS suffiCiently high (mlnImally a factor of 10 above the instrumental detection limit after dilutIon),

an analySIS of a dilution should agree

Within 5 % of the onglnal determination (or Within some acceptable control limit (143) that has been established for that matnx) If not. a

chemical or phYSical Interference effect should be sl,lspected

5 2 2 Spike additIOn-The recovery

of a spike addition added at a

mInimum level of lOX the instrumental detectIOn limit (maximum

100X) to the onglnal determinatIOn

should be recovered to Within 90 to

110 percent or Within the established

control limit for that matnx If not, a

matnx effect should be suspected The

use of a standard addition analySIS

procedure can usually compensate for

thiS effect Caution The standard addition technique does not detect COinCident spectral overlap If suspected,

use of computenzed compensatIon, an

alternate wavelength, or companson

With an alternate method IS recommended (See 5 2 3)

5 2 3 Compaffson With alternate

method of analySis-When investigating a new sample matnx, companson tests may be performed With other

analytical techniques such as atomic

absorption spectrometry, or other

approved methodology

5 2 4 Wavelength scannmg of

analyte Ime region-If the appropnate

equIpment IS available, wavelength

scanning can be performed to detect

potential spectral Interferences

6 Apparatus

6 1 Inductively Coupled PlasmaAtomiC EmiSSion Spectrometer

6 1 1 Computer controlled atomic

emiSSion spectrometer With background

correction

6 1 2 Radlofrequency generator

6 1 3 Argon gas supply, welding

grade or better

6 2 Operating conditIons - Because

of the differences between vanous

makes and models of satisfactory

Instruments. no detailed operating

instructIOns can be prOVided Instead,

the analyst should follow the

instructions prOVided by the

manufacturer of the particular

Instrument Sensitivity. Instrumental

detection limit, preCISion, linear dynamIc range, and Interference effects

must be investigated and established

for each indIVIdual analyte line on that

particular Instrument It IS the

responsibility of the analyst to venfy

that the Instrument configuration and

operating conditions used satIsfy the

analytical reqUirements and to

maintain quality control data

confirming Instrument performance

and analytical results

7 Reagents and standards

7 1 ACids used In the preparation

of standards and for sample processing

must be ultra-high punty grade or

eqUivalent Redistilled aCids are

acceptable

7 1 1 AcetiC aCid, conc (sp gr 1 06)

7 1 2 Hydrochloflc aCid conc (sp gr

1 19)

7 1 3 Hydrochloflc aCId, (1+1) Add

500 mL conc HCI (sp gr 1 19) to 400

mL deiOnized, dlstnlled water and

dilute to 1 liter

7 1 4 NItric aCid conc (sp gr 1 41)

7 1 5 NltflC aCId, (1+1 ) Add 500 mL

conc HN03 (sp gr 1 41) to 400 mL

deiOnized, distilled water and dilute to

1 liter

7 2 Dlomzed distilled water Prepare

by passing distilled water through a

mixed bed of catIon and anion exchange resins Use deionized, distilled

water for the preparation of all

reagents, calibration standards and as

dilution water The punty of thiS water

must be eqUivalent to ASTM Type II

reagent water of SpeCification D 1193

(146)

7 3 Standard stock solutions may be

purchased or prepared from ultra high

punty grade chemicals or metals All

salts must be dned for 1 h at 105°C

unless otherWise speCified

(CAUTION Many metal salts are extremely tOXIC and may be fatal ,f swallowed Wash hands thoroughly after

handling) TYPical stock solution preparation procedures follow

7 3 1 Aluminum solutIOn, stock, 1

mL = 100 /1g AI Dissolve a 100 g of

aluminum metal In an aCid mixture of 4

mL of (1 +1) HCI and 1 mL of conc HN03

In a beaker Warm gently to effect

solution When solution IS complete,

transfer quantitatively to a liter flask,

add an additional 10 mL of (1+ 1) HCI

and dilute to 1 000 mL With deiOnized,

distilled water

7 3 2 Antimony solutIOn stock, 1 mL

= 100 /1g Sb Dissolve a 2669 g K(SbO)

C4H40 S In deionized distilled water,

add 10 mL (1+1) HCl and dilute

to 1000 mL With deionized, distilled

water

Metals-22 Dec 1982
733 Arsemc solution stock, 1 mL = 100 pg As Dissolve 0 1320 9 of AS203

In 100 mL of deionized, distilled water

containing a 4 9 NaOH ACidify the

solution with 2 mL conc HN03 and

dilute to 1,000 mL with deionized

distilled Water

734 Banum solution stock 1 mL

= 100 p.g Ba Dissolve a 1516 9 BaCb

(dried at 2500 C for 2 hrs) In 10 mL

deIOnized, distIlled water Wit'" 1 mL

(1+1) HCI Add 100 mL (1+1) HCI

and dilute to 1,000 mL wIth deionized,

distilled water

7 3 5 BeryllIUm solution stock 1

mL =100 f.1g Be Do not dry DIssolve 1 966 9 BeS04 4 4H20 In

deionized, distilled water add 100 mL

conc HN03 and dilute to 1 000 mL

with deIOnized, distilled water

73 6 Boron solution stock, 1 mL

= 100 f.1g B Do not dry Dissolve

05716 9 anhydrous H~B03 In deionized

distilled water dilute to 1,000 mL

Use a reagent meeting ACS speCif,catIOns, keep the bottle tightly stoppered

and store In a desiccator to prevent

the entrance of atmospheric mOisture

7 3 7 CadmIUm solution stock 1

mL =100 p.g Cd Dissolve a 1142 9

CdO In a minimum amount of (1+1)

HN03 Heat to Increase rate of dissolution Add 10 a mL conc HN03

and dilute to 1,000 mL with deIOnized,

distilled water

7 3 8 CalCIUm solution stock 1 mL

= 100 p.g Ca Suspend a 2498 9

CaC03 dried at 180°C for 1 h before

weighing In deionized distilled water

and dissolve cautiously with a minImum amount of (1+1) HN03 Add

10 a mL conc HN03 and dilute to

1,000 mL with deIOnized distilled

water

7 3 9 ChromIUm solution stock

mL =100 pg Cr Dissolve a 1923

9 of Cr03 In deionized, distilled

water When solution IS complete,

aCidify with 10 mL conc HN03 and

dilute to 1,000 mL with deIOnIzed

dIstilled water

7 3 10 Cobalt solution stock 1

mL = 100 f.1g Co Dissolve 01000 9

of cobalt metal In a minimum amount

of (1+1) HN03 Add 10 a mL (1+1) HCI

and dilute to 1,000 mL with deionized

dIstilled water

7 3 11 Copper solution stock 1

mL =100 pg Cu Dissolve a 1252 9

CuO In a minimum amount of (1 +1)

HN03 Add 100 mL conc HN03 and

dilute to 1 000 mL with deionized

distilled water

7 3 12 Iron solution stock 1 mL

= 100 f.1g Fe Dissolve a 1430 9

Fe203 In a warm mixture of 20 mL

(1 +1) HCI and 2 mL of conc HN03

Cool, add an addItional 5 mL of conc

HN03 and dilute to 1000 mL with

deionized, distilled water

73 13 Lead solution stock 1 mL

=100 f.1g Pb Dissolve a 1599 9

Pb(N03)2 In minimum amount of

(1+1) HN03 Add 100 mL conc HN03

and dilute to 1,000 mL with deionized,

distilled water

7 3 14 MagneSIUm solution stock

mL = 100 f.1g Mg Dissolve°1658 9

MgO In a minimum amount of (1+1)

HN03 Add 100 mL conc HN03 and

dilute to 1,000 mL with deionized,

distilled water

7 3 15 Manganese solution stock

mL = 100 f.1g Mn Dissolve a 1000 9

of manganese metal In the aCid mixture 10 mL conc HCI and 1 mL conc

HN03, and dilute to 1,000 mL with

deIOnIzed distilled water

7 3 16 Molybdenum solution stock

1 mL = 100 f.1g Mo Dissolve 02043 9

(NH4!2Mo04 In deionized distilled

water and dilute to 1 000 mL

7 3 17 Nickel solution stock 1

mL = 100 f.1g NI Dissolve a 1000 9

of nickel metal In 10 mL hot conc

HN03, cool and dilute to 1,000 mL

with deIOnized, distilled water

7 3 18 PotassIUm solution stock

mL = 100 f.1g K Dissolve a 1907 9

KCI, dried at 11 OOC In deionized

distIlled water dilute to 1 000 mL

7 3 19 Selenium solutIOn stock 1

mL = 100 J.l9 Se Do not dry Dissolve

a 1727 9 H2Se03 (actual assay 946%)

In deIOnized distilled water and dilute

to 1,000 mL

73 20 Silica solution stock 1 mL

= 100 f.1g SI02 Do not dry Dissolve

04730 9 Na2S,03 9H20 In deionized

distilled water Add 10 a mL conc

HN03 and dilute to 1,000 mL with

deionized distilled water

7 3 21 Silver solution stock 1

mL =100 pg Ag Dissolve°1575 9

AgN03 In 100 mL of deiOnized diStilled water and 10 mL conc HN03

Dilute to 1 000 mL with deIOnized

distilled water

7322 SodIUm solutIOn stock 1

mL = 100 pg Na Dissolve a 2542 9

NaCI In deiOnized distilled water

Add 100 mL conc HN03 and dilute

to 1 000 mL With deionized distilled

water

7323 ThallIUm solution stock 1

mL = 100 f.1g TI Dissolve a 1303 9

TlN03 Irl deionized, distilled water

Add 10 a mL conc HN03 and dIlute

to 1,000 mL With deiOnized, distilled

water

7 3 24 Vanadium solution stock, 1

mL =100 f.1g V Dissolve 02297

NHN03 In a minimum amount of

conc HN03 Heat to Increase rare

of diSSolution Add 100 mL conc

HN03 and dilute to 1,000 mL WIth

deionized dIstilled water

7325 Zmc solution stock 1 mL

= 100 f.1g Zn Dissolve°1245 9 ZnO

In a minimum amount of dilute HN03

Add 100 mL conc HN03 and dilute

to 1,000 mL With deiOnized, distilled

water

7 4 Mixed calibration standard solutions-Prepare mixed calibration

standard solutions by combining appropriate volumes of the stock solutions In volumetriC flasks (See 74 1

thru 745) Add 2 mL of (1+1)

HCI and dilute to 100 mL With

deionized, distilled water (See Notes

1 and 6) Prior to preparing the mixed

standards each stock solution should

be analyzed separately to determine

pOSSible spectral Interference or the

presence of ImpUrities Care should

be taken when preparing the mixed

standards that the elements are compatible and stable Transfer the mixed

standard solutions to a FEP fluorocarbon or unused polyethylene bottle

for storage Fresh mIxed standards

should be prepared as needed With

the realizatIOn that concentration can

change on aging Calibration standards must be initially verified uSing

a quality control sample and monitored weekly for stabIlity (See 7 6 3)

Although not speCifically reqUired,

some tYPical calibration standard combinations follow when uSing those

speCifiC wavelengths listed In Table

1

7 4 1 Mixed standard solution 1-

Manganese beryllium cadmium lead

and ZinC

7 4 2 Mixed standard solution 11-

Barium, copper, Iron vanadium and

cobalt

7 4 3 Mixed standard solution 11IMolybdenum silica arseniC, and

selenium

7 4 4 Mixed standard solution IVCalCium sodium potassium aluminum chromium and nickel

Dec 1982 Metals-23
7 4 5 MIxed standard solutIon VAntlmony, boron, magnesium, silver,

and thallium

NOTE 1 If the addition of silver

to the recommended aCid combination

results In an initial preCipitatIOn.

add 15 mL of deloOlzed distilled

water and warm the flask until the

so,lutlon clears Cool and dilute to 100

mL with delOOIzed, distilled water For

this acid combination the silver concentration should be limited to 2

mg/L Silver under these conditIOns

Is stable In a tap water matrix

for 30 days Higher concentrations

of silver require additional HCI

75 Two types of blanks are required

for the analysIs The calibration blank

(3 13) Is used In establishing the

analytical curve while the reagent

blank (3 12) IS used to correct for

pOSSible contamination resulting from

varying amounts of the aCIds used In

the sample processing

7 5.1 The calibration blank IS prepared by diluting 2 mL of (1 +1) HN03

and 10 mL of (1+1) HCI to 100 mL

with deionized. distilled water (See

Note 6) Prepare a sufficient quantity

to be used to flush the system between standards and samples

752 The reagent blank must concontain all the reagents and 10 the

same volumes as used In the processing of the samples The reagent

blank must be carned through the

complete procedure and contam the

same aCid concentration In the fmal

solution as the sample solution

used for analysIs

7.6 In addition to the calibratIOn

standards, an Instrument check standard (3 7), an Interference check

sample (38) and a quality control

sample (39) are also reqUired for the

analyses

7 6 1 The mstrument check standard

is prepared by the analyst by combining compatible elements at a concentration eqUivalent to the mIdpOint

of their respective calibration curves

(See 12 1 1)

7 6 2 The mterference check sample

is prepared by the analyst In the

follOWing manner Select a

representative sample which contains

minimal concentrations of the

analytes of Interest by known concentration of mterfenng elements that

Will prOVide an adequate test of the

correction factors Spike the sample

with the elements of Interest at the

approximate concentration of either

100 pg/L or 5 times the estimated

detection limits given In Table 1 (For

effluent samples of expected high

concentrations, spike at an

appropriate level) If the type of

samples analyzed are varied a

synthetically prepared sample may be

used If the above criteria and Intent

are met A limited supply of a

synthetiC Interference check sample

will be available from the Quality

Assurance Branch of EMSLCinCinnati (See 12 1 2)

7 6 3 The quality control sample

should be prepared In the same aCid

matrix as the calibratIOn standards

at a concentration near 1 mg/L and In

accordance With the instructions

prOVided by the supplier The Quality

Assurance Branch of EMSL-Clnclnnatl

Will either supply a quality control

sample or information where one of

equal quality can be procured (See

121 3)

8 Sample handling an

preservation

8 1 For the determination of trace

elements, contamination and loss are

of prime concern Dust In the laboratory environment ImpUrities In

reagents and ImpUrities on laboratory

apparatus which the sample contacts

are all sources of potential

contamination Sample containers can

Introduce either pOSItive or negative

errors In the measurement of trace

elements by (a) contributing contaminants through leaching or surface

desorption and (b) by depleting

concentrations th rough adsorption

Thus the collectIOn and treatment of

the sample prior to analYSIS reqUires

particular attention Laboratory

glassware including the sample bottle

(whether polyethylene, polyproplyene

or FEP-fluorocarbon) should be

thoroughly washed With detergent

and tap water. nnsed With (1+1) nrtrlc

aCid. tap water, (1 +1) hydrochlOriC

aCid. tap al'd finally deionized, distilled

water In that order (See Notes 2 and

3)

NOTE 2 ChromiC aCid may be useful to

remove organic depOSits from glassware. however. the analyst should be

be cautioned that the glassware must

be thoroughly nnsed With water to

remove the last traces of chromium

ThiS IS especially Important If chromium

IS to be Included In the analytical

scheme A commercial product, NOCHROMIX. available from Godax Laboratones. 6 Vanck St. New York. NY

10013. may be used In place of

chromiC aCid Chomlc aCid should not

be used With plastiC bottles

NOTE 3 Ifltcan be documented through

an active analytical quality control

p(ogram uSing spiked samples and reagent blanks. that certam steps 10 the

cleaning procedure are not reqUired for

routine samples, those steps may be

eliminated from the procedure

8 2 Before collection of the sample a

deCISion must be made as to the type

of data deSired, that IS dissolved,

suspended or total, so that the appropnate preservation and pretreatment

steps may be accomplished Filtration,

aCid preservation, etc, are to be performed at the time the sample IS

collected or as soon as pOSSible

thereafter

8 2 1 For the determination of diSsolved elements the sample must be

filtered through a o45-Jim membrane

filter as soon as practical after collection (Glass or plastIC flltenng apparatus are recommended to aVOid pOSSIble contamination) Use the first 50-

100 mL to rinse the filter flask DIScard thiS portIon and collect the

reqUired volume of filtrate ACidify the

filtrate With (1 +1) HN03 to a pH of 2

or less Normally,3 mL of (1+1) aCid

per liter should be suffiCient to preserve the sample

82 2 For the determrnatlon of suspended elements a measured volume

of unpreserved sample must be filtered through a o45-Jim membrane

filter as soon as practical after

collection The filter plus suspended

material should be transferred to a

SUitable container for storage and/or

shipment No preservative IS reqUired

82 3 For the determination of total

or total recoverable elements, the

sample IS aCidified WIth (1 +1) HN03

to pH 2 or less as soon as pOSSible,

preferable at the time of collection

The sample IS not filtered before

processing

9 Sample PreparatIon

9 1 For the determinations of diSsolved elements. the filtered,

preserved sample may often be

analyzed as received The aCid matrix

and concentration of the samples and

calibration standards must be the

same (See Note 6 ) If a preCipitate

formed upon aCidification of the

sample or during transit or storage. It

must be redissolved before the

analYSIS by adding additIOnal aCid

and/or by heat as deSCribed In 93

9 2 For the determination of suspended elements. transfer the membrane filter containing the Insoluble

material to a 150-mL Griffin beaker

and add 4 mL conc HN03 Cover the

Meta/s-24 Dec 1982
beaker with a watch glass and heat

gently The wam aCId will soon dissolve the membrane

Increase the temperature of the

hot plate and digest the material

When the aCId has nearly evaporated

cool the beaker and watch glass and

add another 3 mL of conc HNOa

Cover and continue heating untIl the

dIgestIon IS complete generally indicated by a lIght colored dlgestate

Evaporate to near dryness (2 mL), cool

add 10 mL HCI (1+1) and 15 mL

deIonIzed distIlled water per 100 mL

dilutIon and warm the beaker gently

for 15 min to dissolve any precipitated or reSidue material Allow to

cool, wash down the watch glass and

beaker walls wIth deIOnIzed dIstIlled

water and filter the sample to remove

Insoluble material that could clog the

nebulizer (See Note 4) Adjust the

volume based on the expected concentrations of elements present ThIS

volume wIll vary depending on the

elements to be determined (See Note

6) The sample IS now ready for

analysIs ConcentratIons so determined

shall be reported as suspended

NOTE 4 In place of fIltering, the

sample after diluting and mixing may

be centrifuged or allowed to settle by

gravIty overnight to remove Insoluble

material

9 3 For the determination of total

elements, choose a measured, volume

of the well mIxed aCId preserved

sample appropriate for the expected

level of elements and transfer to a

Griffin beaker (See Note 5) Add 3 mL

of conc HNOa Place the beaker on

a hot plate and evaporate to near dryness cautIously, making certain that

the sample does not bOIl and that no

area of the bottom of the beaker IS

allowed to go dry Cool the beaker and

add another 5 mL portion of conc

HNOa Cover the beaker With a watch

glass and return to the hot plate

Increase the temperature of the hot

plate so that a gentle reflux action

occurs Continue heating, adding addItIonal aCId as necessary, until the

digestIon IS complete (generally indIcated when the dlgestate IS light

In color or does not change In appearance With continued refluxlng ) Again

evaporate to near dryness and cool

the beaker Add 10 mL of 1+1 Hel

and 15 mL of deIonized distilled

water per 100 mL of fmal solutIon

and warm the beaker gently for 15

min to dIssolve any preCipItate or

reSIdue resulting from evaporation

Allow to cool, wash down the beaker

walls and watch glass WIth deionIzed

dIstilled water and filter the sample to

remove Insoluble material that could

clog the nebulizer (See Note 4) Adjust

the sample to a predetermined volume

based on the expected concentrations

of elements present The sample IS

now ready for analySIS (See Note 6)

ConcentratIons so determined shall be

reported as total

NOTE 5 If low determinations of

boron are CritIcal, quartz glassware

should be use

NOTE 6 If the sample analYSIS solution

has a dIfferent aCid concentratIon

from that given In 94, but does not

Introduce a phYSIcal Interference or

affect the analytical result the same

ca IIbratlon standards may be used

9 4 For the determination of total

recoverable elements choose a measured volume of a well mixed, aCId

preserved sample appropriate for the

expected level of elements and transfer to a Griffin beaker (See Note 5 )

Add 2 mL of (1+1) HNOa and 10 mL

of (1+1) HCI to the sample and heat

on a steam bath or hot plate until the

volume has been reduced to near 25

mL making certain the sample does

not boil After thiS treatment cool

the sample and filter to remove inSOluble matenal that could clog the

nebulizer (See Note 4 ) Adjust the

volume to 100 mL and mix The sample

IS now ready for analySIS ConcentratIons so determined shall be reported

as total

10 Procedure

10 1 Set up Instrument With proper

operating parameters established In

6 2 The Instrument must be allowed

to become thermally stable before beginning ThIS usually reqUIres at least

30 min of operatIon pnor to calibration

10 2 Initiate appropnate operating

configuratIon of computer

10 3 ProfIle and calibrate instrument according to Instrument

manufacturer s recommended

procedures, uSing the typical mIxed

calibratIon standard solutions

descnbed In 7 4 Flush the system

With the calibration blank (7 5 1)

between each standard (See Note 7 )

(The use of the average intensity of

multIple exposures for both

standardization and sample analYSIS

has been found to reduce random

error)

NOTE 7 For boron concentrations

greater than 500 pg/L extended flush

tImes of 1 to 2 min may be requIred

10 4 Before beginning the sample

run reanalyze the highest mIxed

calibration standard as If It were a

sample ConcentratIOn values obtamed

should not deViate from the actual

values by more than ± 5 percent

(or the established control limIts

whIchever IS lower) If they do, follow

the recommendatIons of the instrument manufacturer to correct for thIS

condition

10 5 Begm the sample run flushing

the system With the calibration blank

solutIon (75 1) between each sample

(See Note 7 ) Analyze the Instrument

check standard (76 1) and the calibratIon blank (7 5 1) each 10 samples

10 6 If It has been found that

method of standard addItion are

required, the follOWing procedure IS

recommended

10 6 1 The standard addition technique (142) Involves prepanng new

standards In the sample matnx by

adding known amounts of standard to

one or more allquots of the processed

sample solutIon ThiS technIque compensates for a sample constItuent that

enhances or depresses the analyte

SIgnal thus prodUCing a different slope

from that of the calibratIOn standards

It WIll not correct for additive interference which causes a baselme shIft

The SImplest version of thIS technique

IS the Single-addItion method The

procedure IS as follows Two Identical

allquots of the sample solution, each

of volume V., are taken To the

fIrst (labeled A) IS added a small

volume Vs of a standard analyte

solution of concentration Cs To the

second (labeled B) IS added the same

volume Vs of the solvent The analytical SIgnals of A and B are measured

and corrected for nonanalyte SIgnals

The unknown sample concentration

Cx IS calculated

Cx = SaVscs

(SA - Sa) V x

where SA and Sa are the analytIcal

Signals (corrected for the blank) of

solutIons A and B respectively Vs

and Cs should be chosen so that SA

IS roughly tWIce Sa on the average It

IS best If VS IS made much less than

Vx, and thus Cs IS much greater than

cx, to aVOId excess dIlutIOn of the

sample matrix If a separation or

concentratIon step IS used, the

additions are best made fIrst and

carned through the entire procedure

For the results from thiS technIque to

be valid, the followmg limitatIons

must be taken mto consIderatIOn

1 The analytical curve must be linear

2 The chemIcal form of the analyte

added must respond the same as the

analyte m the sample

Cee 1982 Metals-25
3 The Interference effect must be

constant over the working range of

concern

4 The signal must be corrected for

any additive Interference

11. Calculation

11.1 Reagent blanks (7 5 2) should

be subtracted from all samples This IS

particularly Important for digested

samples requiring large quantities of

acids to complete the digestion

11 2 If dilutIOns were performed.

the appropnate factor must be applied

to sample values

11 3 Data should be rounded to the

thousandth place and all results

should be reported In mg/L up to

three slgOlflcant figures

12. Quality Control

(Instrumental)

12.1 Check the Instrument

standardization by analyzing

appropriate quality control check

standards as follow

12.1.1 Analyze an appropnate

Instrument check standard (7 6 1)

conu'lInlng the elements of Interest at

a frequency of 10% ThiS check

standard IS used to determine

instrument dnft If agreement IS not

within ±5% of the expected values or

Within the established control limits.

whichever IS lower, the analySIS IS out

of control The analYSIS should be

terminated, the problem corrected.

and the Instrument recallbrated

Analyze the calibration blank (7 5 1)

at a frequency of 10% The result

should be Within the established

control limits of two standard deViations of the mean value If not. repeat

the analySIS two more times and

average the three results If the

average IS not Within the control limit.

termmate the analySIS. correct the

problem and recalibrate the

Instrument

12 1 2 To venfy anterelement and

background correction factors analyze

the Interference check sample (7 6 2)

8t the beglnnmg, end, and at penodlc

Intervals throughout the sample run

Results should fall wlthan the

established control limits of 1 5 times

the standard deViation of the mean

value If not, termmate the analySIS.

correct the problem and recallbrate

the Instrument

12.1.3 A quality control sample

(763) obtained from an outSide

source must first be used for the

100tlai venf/catlon of the calibration

standards A fresh dilution of thiS

sample shall be anlayzed every week

thereafter to mOnitor their stability If

the results are not Within ±5% of the

true value listed for the control

sample. prepare a new calibration

standard and recallbrate the

Instrument If thIS does not correct the

problem. prepare a new stock

standard and a new calibration

standard and repeat the calibratIon

PrecIsion and Accuracy

13 1 In an EPA round robrn phase 1

study. seven laboratorres applied the

ICP technique to aCId-distIlled water

matnces that had been dosed With

vanous metal concentrates Table 4

lists the true value. the mean reported

value and the mean % relative

standard deViation

References

1 Wrnge R K V J Peterson and

V A Fassel Inductively Coupled

Plasma-AtomIc EmiSSIOn

Spectroscopy Promrnent Lrnes EPA600/4-79-017

2 Wrnefordner J 0 Trace

AnalYSIS Spectroscopic Methods for

Elements, ChemIcal AnalYSIS Vol

46. pp 41-42

3 Handbook for Analytical Quality

Control 10 Water and Wastewater

Laboratones, EPA-600/4-79-019

4 Garbarrno. J R and Taylor H E

An InductIvely-Coupled Plasma

AtomIC EmiSSion Spectrometrrc

Method for Routrne Water Quality

Testmg Applied Spectroscopy 33,

No 3(1979)

5 Methods for Chemical AnalySIS of

Water and Wastes EPA-600/4-79-

020

6 Annual Book of ASTM Standards

Part 31

7 Carcrnogens - Workrng WIth

Carcinogens Department of Health.

Education and Welfare PublIc Health

SerVIce, Center for Disease Control,

National Institute for Occupational

Safety and Health Publication No 77-

206. Aug 1977

8 OSHA Safety and Health Standards General Industry (29 CFR

1910). Occupational Safety and Health

Admrnlstratlon OSHA 2206 (ReVised

January 1976)

9 Safety m AcademIC Chemistry

Laboratones Amencan Chemical SocIety PublIcation Committee on

Chemical Safety 3rd Edition 1979

Meta/s-26 Dec 1982
Table 7 Recommended Wavelengths 1 and Estlmi3ted Instrumental

DetectIon LImIts

EstImated detectIon

Element Wavelength nm limIt /19/L 2

Alummum 308215 45

Arsemc 193696 53

AntImony 206833 32

Banum 455403 2

BeryllIUm 313042 03

Boron 249773 5

CadmIum 226502 4

CalcIUm 317933 10

ChromIUm 267716 7

Cobalt 228616 7

Copper 324754 6

Iron 259940 7

Lead 220353 42

MagnesIUm 279079 30

Manganese 257610 2

Molybdenum 202030 8

NIckel 231604 15

Potasslvm 766491 see3

Selemum 196026 75

SilIca (S,02) 288158 58

Sliver 328 068 7

SodIUm _ 588995 29

ThallIUm 190 864 40

VanadIUm 292 402 8

Zmc 213856 2

1The wavelengths listed are recommended because of the" sensitIvity and

overall acceptance Other wavelengths may be substituted If they can

proVIde the needed sensItivIty and are treated WIth the same corrective

techmques for spectral Interference (See 5 1 1)

2The estimated Instrumental detectIon limits as shown are taken from

'InductIvely Coupled Plasma-Atomic EmIssIon Spectroscopy-Prominent

Lines EPA-600/4-79-017 They are given as a gUIde for an Instrumental

limIt The actual method detectIon limIts are sample dependent and may vary

as the sample matnx vanes

3Hlghly dependent on operating conditions and plasma position

Dec "982 Metals-27
Table 2 Analyte Concentration EqUivalents (mglL) Arlsmg From Interferents at the 100 mglL Level

Analyte Wavelength, nm Interferent

AI Ca Cr Cu Fe Mg Mn NI TI V

Alummum 308215 021 1 4

Antimony 206833 047 29 008 25 045

Arsemc 193696 13 044 1 1

BarIUm 455403

Beryllium 313042 004 005

Boron 249773 004 032

CadmIUm 226502 003 002

CalcIUm 317933 008 001 001 004 003 003

Chromium 267716 0003 004 004

Cobalt 228616 003 0005 003 015

Copper 324754 0003 005 002

Iron 259940 012

Lead 220353 017

Msgneslum 279079 002 011 013 025 007 012

Msnganese 257610 0005 001 0002 0002

Molybdenum 202030 005 003

Nickel 231604

Selemum 196026 023 009

Silicon 288158 007 001

SodIUm 588995 008

Thallium 190864 030

VanadIUm 292402 005 0005 002

Zmc ~13 856 014 029

Table 3. Interferent and Analyte Elemental Concentrations Used for Interference Measurements

In Table 2

Anolytes

AI

As

B

Ba

Be

Ca

Cd

Co

Cr

Cu

Fe

Mg

Mn

Mo

Na

NI

Pb

Sb

Se

S,

TI

V

Zn

(mglL)

10

10

10

1

1

1

10

1

1

1

1

1

1

10

10

10

10

10

10

1

10

1

10

Interferents

AI

Ca

Cr

Cu

Fe

Mg

Mn

NI

TI

V

Metals-28

(mglL)

1000

1000

200

200

1000

1000

200

200

200

200

Dec 1982
Table 4 ICP PrecIsion and Accuracy Data

Sample # 1 Sample #2 Sample #3

Mean Mean Mean

True Reported Mean True Reported Mean True Reported Mean

Value Value Percent Value Value Percent Value Value Percent

Element /19/L /19/L RSD /19/L /19/L RSD /19/L /19/L RSD

Be 750 733 62 20 20 98 180 176 52

Mn 350 345 27 15 15 67 100 99 33

V 750 749 18 70 69 29 170 169 1 1

As 200 208 75 22 19 23 60 63 17

Cr 150 149 38 10 10 18 50 50 33

Cu 250 235 51 11 11 40 70 67 79

Fe 600 594 30 20 19 15 180, 178 60

AI 700 ,696 56 60 62 33 160 161 13

Cd 50 48 12 25 29 16 14 13 16

Co 500 512 10 20 20 41 120 108 21

Nt 250 245 58 30 28 11 60 55 14

Pb 250 236 16 24 30 32 80 80 14

Zn 200 201 56 16 19 45 80 82 94

Se 40 32 219 6 85 42 10 85 83

Not all elements were analyzed by alllaboratortes

Dec 1982 Metals-29,
ALUMINUM

Method 202.1 (Atomic Absorption, direct aspiration)

STORET NO. Total 01105

Dissolved 01106

Suspended 01107

Optimum Concentration Range: 5-50 mg/l USIng a wavelength of 309 3 nm

SensitiVIty: 1mg/l

Detection LImit 0 1mg/l

Preparation of Standard Solution

1 Stock SolutIOn Carefully weIgh 1000 gram of alumInum metal (analytical reagent

grade) Add 15 ml of conc Hel and 5 ml conc HN03 to the metal, cover the beaker and

warm gently When solutIOn IS complete, transfer quantItatIvely to a 1 lIter volumetnc

flask and make up to volume With deIOnIZed dIstIlled water 1ml = I mg Al (1000 mg/l)

2 PotaSSIUm Chlonde SolutIOn DIssolve 95 g potaSSIUm chlonde (KCI) In deIomzed

dIstl1led water and make up to 1 hter

3 Prepare dl1utIOns ofthe stock SolutIon to be used as cahbratIOn standards at the tIme of

analySIS The cahbratIOn standards should be prepared USIng the same type ofaCId and at

the same concentratIOn as will result In the sample to be analyzed eIther dIrectly or after

processmg To each 100 ml ofstandard and sample ahke add 2 0 ml potaSSIUm chlonde

solutIOn

Sample PreservatIon

1 For sample handhng and preservatIon, see part 4.1 of the AtomIC AbsorptIOn Methods

sectIOn ofthIs manual

Sample PreparatIon

1 The procedures for the preparatIOn of the sample as gIven In part 4 1 1 through 4 1 4 of

the AtomIC AbsorptIOn Methods sectIOn of thIS manual have been found to be

satIsfactory

Instrumental Parameters (General)

1 AlumInum hollow cathode lamp

2 Wavelength 3093 nm

3 Fuel Acetylene

4 OXIdant NItroUS OXIde

Approved for NPDES

Issued 1971

Editonal reVISIon 1974 and 1978

202.1-1
5. Typeofflame Fuelnch

Analysis Procedure

1 For analysIs procedure and calculatIon, see "DIrect AspiratlOn", part 9 1 ofthe AtomIC

AbsorptlOn Methods sectlOn ofthIS manual

Interferences

1 Alummum IS partIally Iomzed m the mtrous oXIde-acetylene flame ThIs problem may be

controlled by the additlOn ofan alkall metal (potasslUm, 1000 ug/ml) to both sample and

standard solutlOns \

Notes

1

2

3

4

The followmg hnes may also be used

308 2 nm RelatIve SensItIvIty 1

396 2 nm Relative SensItIvIty 2

394 4 nm Relative SensItivIty 2 5

Data to be entered mto STORETmust be reported as ug/l

For concentratlOns of alummum below 0 3 mg/l, the furnace procedure (Method 202 2)

IS recommended

The Enochrome cyamne R colonmetnc method may also be used The optimum range

for tIns method hes between 20 and 300 ug/l (Standard Methods, 14th EdItion, p 171)

In the absence of fluondes and complex phosphates, a detectlOn 11mlt of 6 ug/l IS

pOSSIble

Precision and Accuracy

1 An mterlaboratory study on trace metal analyses by atomIC absorptlOn was conducted by

the Quahty Assurance and Laboratory EvaluatlOn Branch of EMSL SIX synthetIc

concentrates contammg varymg levels of alummum, cadmlUm, chromlUm, copper, Iron,

manganese, lead and zmc were added to natural water samples The statistical results for

alummum were asfollows

Number True values Mean Value DevIatIon Accuracy as

of Labs ug/hter ug/hter , ug/hter %BIas

38 1205 1281 299 63

38 1004 1003 391 -01

37 500 463 202 -74

37 625 582 272 ~6 8

22 35 96 108 175

21 15 109 168 626

2021-2
ALUMINUM

Method 202.2 (Atomic Absorption, furnace technique)

STORET NO. Total 01105

Dissolved 01106

Suspended 01107

Optimum Concentration Range: 20-200 ug/l

DetectIOn LimIt: 3 ug/l

Preparation ofStandard Solution

1 Stock solutlOn Prepare as descnbed under "dIrect aspiratlOn method"

2 Prepare dIlutIons of the stock solutIon to be used as cahbratlOn standards at the tIme of

analysIs These solutions are also to be used for "standard addItions"

3 The calibratlOn standard should be dIluted to contam0 5% (vIv) HN03

Sample Preservation

I For sample handlIng and preservatlOn, see part 4 1 of the AtomIC AbsorptlOn Methods

section ofthIS manual

- Sample Preparation

1 Prepare as descnbed under "dIrect aspiratlOn method" Sample SolutIons for analysIs

shouldcontamO 5% (v/v)HN03

Instrument Parameters (General)

1 Drymg TIme and Temp 30sec-125°C

2 AshmgTImeand Temp 30sec-1300°C

3 AtomIzmg TIme and Temp 10 sec-27oo°C

4 Purge Gas Atmmosphere Argon

5 Wavelength 309 3 nm

6 Other operatmg parameters should be set as specIfied by the particular mstrument

manufacturer

AnalysIS Procedure

1 For the analysIs procedure and the caculatlon, see "Furnace Procedure" part 9 3 of the

AtomIC AbsorptlOn Methods sectlOn ofthIS manual

Approved for NPDES

Issued 1978

2022-1
Notes

1.

2

3

4

5

6

The above concentratIOn values and mstrument condltlons are for a Perkm-Elmer HGA2100, based on the use of a 20 ul mJectlOn, contmuous flow purge gas and non-pyrolytlc

graplnte

Background correctIOn may be reqUired Ifthe sample contams hlgh dlssolved sohds

It has been reported that chlonde IOn and that mtrogen used as a purge gas suppress the

aluminum slgnal Therefore the use of hallde aClds and mtrogen as a purge gas should be

aVOided

For every sample matnx analyzed, venficatlOn IS necessary to determme that method of

standard addltlOn IS not reqUired (see part 5 2 1 of the Atomlc Absorptlon Methods

sectIOn OfthlS manual)

Ifmethod ofstandard addltlOn IS reqUired, follow the procedure glven earher m part 8 5

ofthe Atomlc AbsorptIOn Methods sectIOn ofthlS manual

Data to be entered mto STORET must be reported as ug/1

Precision and Accuracy

1 Preclslon and accuracy data are not avallable at thlS time

lI'

2022-2
ANTIMONY

Method 204.1 (Atomic absorption, direct aspiration)

STORET NO. Total 01097

Dissolved 01095

Suspended 01096

Optimum Concentration Range: 1-40 mg!l USIng a wavelength of217 6 nm

Sensitivity: 05 mg!l

Detection Limit: 0 2 mg!l

Preparation ofStandard Solution

1 Stock SolutIOn Carefully weIgh 2 7426 g of antImony potassmm tartrate

K(SbO)C4H40s- Y2H 20 (analytical reagent grade) and dIssolve In deIOnIZed dIstilled

water DIlute to I lIter wIth deIOnIzed dIstilled water I ml = I mg Sb (1000 mglII)

2 Prepare ddutIOns ofthe stock solutIOn to be used as calIbratIOn standards at the tIme of

analysIs The cahbratIOn standards should be prepared USIng the same type ofaCId and at

the same concentratIOn as wIll result In the sample to be analyzed eIther dIrectly or after

processIng

Sample Preservation

1 For sample handhng and preservatIOn, see part 4 1 of the AtomIC Absorption Methods

section ofthIs manual

Sample Preparation

1 The procedures for preparatIOn ofthe sample as gIven In parts 4 1 1 through 4 1 4 ofthe

AtomIC Absorption Methods section ofthIS manual have been found to be satIsfactory

Instrumental Parameters (General)

1 AntImony hollow cathode lamp

2 Wavelength 217 6 nm

3 Fuel Acetylene

4 OXIdant AIr

5 Type offlame Fuellean

Analysis Procedure

1 For analysIs procedure and calculatIOn, see "DIrect AspIratIOn", part 9 1 ofthe AtomIC

AbsorptIOn Methods sectIOn ofthIs manual

Approved for NPDES

Issued 1974

Editonal reVISIon 1978

2041-1
Interferences

1. In the presence of lead (1000 mg/1), a spectralmterference may occur at the 217 6 nm

resonance lme In thIS case the 231 1 nm antImony lme should be used

2 Increasmg aCId concentrations decrease antImony absorptIon To aVOid thIS effect, the

aCId concentratIon 10 the samples and 10 the standards should be matched

Notes

1

2

Data to be entered mto STORET must be reported as ug/1

For concentrations ofantlffiony below 0 35 mg/1, the furnace procedure (Method 204 2)

IS recommended

Precision and Accuracy

1 In a smgle laboratory (EMSL), usmg a mIXed mdustnal-domestIc waste effiuent at

concentratIOns of 5 0 and 15 mg Sbl1, the standard devIatIons were ±O 08 and ±O 1,

respectively Recovenes at these levels were 96% and 97%, respectIvely

2041-2
ANTIMONY

Method 204.2 (Atomic Absorption, furnace technique)

STORET NO. Total 01097

Dissolved 01095

Suspended 01096

Optimum Concentration Range· 20-300 ug/1

Detection LimIt: 3 ug/1

PreparatIOn ofStandard Solution

1 Stock solutlOn Prepare as descnbed under "dIrect aspIratlOn method"

2 Prepare dl1utlOns ofthe stock solutlOn to be used as cahbratlOn standards at the tIme of

analysIs These solutlOns are also to be used for "standard addItlOns"

3 The cahbratlOn standard should be dl1uted to contam 0 2% (vIv) HN03

Sample Preservation

1 For sample handhng and preservatlOn, see part 4 1 of the AtomIC AbsorptlOn Methods

section ofthIS manual

Sample Preparation

1 The procedures for preparatlOn of the sample as gIven m parts 4 1 1 thru 4 1 3 of the

AtomIC AbsorptlOn Methods section of thIS manual should be followed mcludmg the

addItlOn of sufficIent 1 1 HCl to dIssolve the dIgested resIdue for the analysIs of

suspended or total antImony The sample solutlOns used for analysIs should contam 2%

(v/v)HN03

Instrument Parameters (General)

1 DrymgTlmeand Temp 30sec-125°C

2 Ashmg TIme and Temp 30 sec-800°C

3 Atomlzmg TIme and Temp 10 sec-2700°C

4 Purge Gas Atmosphere Argon

5 Wavelength 2176 nm

6 Other operatmg parameters should be set as specIfied by the particular mstrument

manufacturer

AnalYSIS Procedure

1 For the analysIs procedure and the calculatlOn, see "Furnace Procedure" part 93 ofthe

AtomIc AbsorptlOn Methods sectlOn ofthIS manual

Approved for NPDES

Issued 1978

2042-1
Notes

1

2

3

4

5

6

7

1he above concentratIOn values and mstrument conditIOns are for a Perkm-Elmer HGA2100, based on the use of a 20 ul mJectIOn, contmuous flow purge gas and non-pyrolytlc

graphite Smaller size furnace devices or those employmg faster rates of atomization can

be operated usmg lower atomizatIOn temperatures for shorter time penods than the

above recommended settmgs

The use ofbackground correctIOn IS recommended

Nitrogen may also be used as the purge gas " If chlonde conceptratIOn presents a matnx problem or causes a loss prevIous to

atomizatIOn, add an excess of 5 mg of ammOnium nitrate to the furnace and ash usmg a

ramp accessory or with mcremental steps untl1 the recommended ashmg temperature IS

reached

For every sample matnx analyzed, venficatIOn IS necessary to determme that method of

standard additIOn IS not reqUlred (see part 5 2 1 of the Atomic AbsorptIOn Methods

section ofthis manual)

Ifmethod ofstandard additIOn IS reqUlred, follow the procedure given earher m part 8 5

ofthe Atomic AbsorptIOn Methods sectIOn ofthls manual

Data to be entered mto STORET must be reported as ug/l

Precision and Accuracy

1 PrecIsIOn and accuracy data are not aval1able at tills time

2042-2
ARSENIC

Method 206.2 (Atomic Absorption, furnace technique)

STORET NO. Total 01002

Dissolved 01000

Suspended 01001

Optimum Concentration Range: 5-100 ug/1

Detection LilDlt: 1 ug/1

PreparatIon ofStandard Solution

1 Stock solutIOn D1ssolve 1 320 g of arsemc tnox1de, As203 (analyt1cal reagent grade) m

100 ml ofde10mzed d1st1lled water contammg 4 g NaOH AC1dify the solutIOn w1th 20 ml

conc HN03and dllute to 1 hter 1ml = 1mg As (1000 mg/1)

2 N1ckel N1trate SolutIOn, 5% D1ssolve 24 780 g of ACS reagent grade N1(N03)2·6H20 m

deIOmzed d1st1lled water and make up to 100ml

3 N1ckel N1trate SolutIOn, 1% Dllute 20 ml of the 5% mckel mtrate to 100 ml w1th

de10mzed d1st1lled water

4 Workmg Arsemc SolutIOn Prepare dllut10ns of the stock solutIOn to be used as

cahbrat10n standards at the t1me of analys1s W1thdraw appropnate ahquots ofthe stock

solut10n, add 1 ml of conc RN03, 2ml of 30% R20 2and 2ml of the 5% mcke1 mtrate

solutIOn Dllute to 100 ml w1th deIOmzed d1sttlled water

Sample Preservation

1 For sample handlmg and preservat10n, see part 4 1 of the Atom1c Absorpt10n Methods

sectIOn ofth1s manual

Sample Preparation

1 Transfer 100 ml ofwell-m1xed sample to a 250 ml Gnffin beaker, add 2 ml of 30% H20 2

and suffic1ent conc HN03to result man aC1d concentration of 1%(vIv) Heat for 1 hour

at 95°C or untll the volume 1S shghtly less than 50 ml

2 Cool and brmg back to 50 ml w1th deIOmzed d1st1lled water

3 P1pet 5 ml of th1s d1gested solutIOn mto a lO-ml volumetnc flask, add 1 ml of the 1%

mckel mtrate solutIOn and dllute to 10 ml w1th de10mzed d1st1lled water The sample 1S

now ready for mJectIOn mto the furnace

Approved for NPDES and SDWA

Issued 1978

2062-1
,

NOTE: IfsolubilizatlOn or dIgestion IS not reqUIred, adjust the HN03 concentratIon of

the sample to 1% (v/v) and add 2 ml of 30%H20 2 and 2 m1 of 5% nIckel nItrate to each

100 ml of sample The volume of the calIbratlOn standard should be adjusted WIth

delOnIzed dIstIlled water to match the volume change ofthe sample

Instrument Parameters (General)

1. Drymg TIme and Temp 30 sec-125°C

2 AshmgTIme and Temp 30 sec-ll00°C

3 AtomIzmgTImeand Temp IOsec-2700°C

4 Purge Gas Atmosphere Argon

5. Wavelength 1937 nm

6 Other operatmg parameters should be set as specIfied by the partIcular mstrument

manufacturer

Analysis Procedure

1 For the analysIs procedure and the calculatIon, see "Furnace Procedure" part 9 3 ofthe

AtomIC Absorption Methods sectIon ofthIS manual

Notes

1

2

3

4

5.

6.

The above concentration values and mstrument condItIons are for a PerkIn-Elmer HGA2100, based on the use of a 20 ul InJection, purge gas Interrupt and non-pyrolytIc

graphtte Smaller SIze furnace deVIces or those etnploymg faster rates of atomIzatIon can

be operated usmg lower atomizatIon temperatures for shorter tIme penods than the

above recommended settmgs

The use ofbackground correction IS recommended

For every sample matnx analyzed, venfication IS necessary to determme that method of

standard addItlOn IS not reqUIred (see part 5 2 1 of the AtomIC Absorption Methods

section ofthts manual)

Ifmethod ofstandard addItion IS requIred, follow the procedure given earlIer m part 8 5

ofthe AtomIC AbsorptIon Methods sectIon ofthIS manual

For qualIty control requIrements and optlOnal recommendatIons for use m drinking

water analyses, see part 10 ofthe AtomIC AbsorptlOn Methods sectIon ofthIS manual

Data to be entered mto STORETmust be reported as ug/l

Precision and Accuracy

1 In a smgle laboratory (EMSL), usmg a mIxed mdustnal-domestic waste effiuent

contaming 15 ug/l and spiked WIth concentratlOns of 2, 10 and 25 ug/l, recovenes of

85%, 90% and 88% were obtamed respectIvely The relatIve standard deviatlOn at these

concentratIonslevels were ±8 8%, ±~ 2%, ±5 4% and ±8 7%, respectIvely

2 In a smgle laboratory (EMSL), usmg CmcmnatI, OhIO tap waterspIked at concentratlOns

of 20, 50 and 100 ug As/I, the standard deviatlOns were ±O 7, ±11 and ±1 6

respectIvely Recovenes at these levels were 105%, 106% and 101%, respectIvely

2062-2
ARSENIC

Method 206.3 (Atomic Absorption-gaseous hydride)

STORET NO. Total 01002

Dissolved 01000

Suspended 01001

1 Scope and ApphcatIOn

lIThe gaseous hydnde method determmes morgamc arsemc when present m

concentrations at or above 2 ug/l The method IS apphcable to dnnkmg water and most

fresh and sahne waters m the absence of high concentratIOns of chromIUm, cobalt,

copper, mercury, molybdenum, mckel and stIver

2 Summary ofMethod

2 1 Arsemc m the sample IS first reduced to the tnvalent form usmg SnCl2 and converted to

arsme, AsH3, usmg zmc metal The gaseous hydnde IS swept mto an argon-hydrogen

flame of an atomICabsorptlon spectrophotometer The workmg range of the method IS

2-20 ug/l The 193 7 nm wavelength lme IS used

3 Comments

3 1 In analyzmg dnnkmg water and most surface and ground waters, mterferences are rarely

encountered Industnal waste samples should be spIked with a known amount of arsemc

to estabhsh adequate recovery

3 2 Orgamc forms of arsemc must be converted to morgamc compounds and orgamc matter

must be oXidized before begmmng the analysIs The OXidatIOn procedure given m

Method 206 5 (Standard Methods, 14th Edition, Method 404B, p 285, Procedure 4 a)

has been found sUItable

3 3 For sample handhng and preservation, see part 4 1 of the AtomiC Absorption Methods

section ofthis manual

3 4 For quahty control reqUIrements and optional recommendations for use m dnnkmg

water analyses, see part 10 ofthe AtomiC AbsorptIOn Methods section ofthts manual

3 5 Data to be entered mto STORET must be reported as ug/l

4 PrecIsion and Accuracy

4 1 Ten rephcate solutions of o-arsemhc aCid at the 5, 10 and 20 ug/llevel were analyzed by

a smgle laboratory Standard deViations were ±O 3, ±O 9 and ±1 1with recovenes of 94,

93 and 85%, respectIvely (Caldwell, J S, Lishka, R J, and McFarren, E F,

"EvaluatIOn ofa Low Cost Arsemc and Selemum Determmatlon at Microgram per Liter

Levels", JA.WWA, vol 65, P 731, Nov, 1973 )

Approved for NPDES and SDWA

Issued 1974

206 3-1
5. References

5 I, Except for the perchlonc aCId step, the procedure to be used for thIS determmatIOn IS

found m Standard Methods for the ExammatIOn of Water and Wastewater, 14th

EdItIOn, p159, Method 301A(VII),(1975)

2063-2
ARSENIC,

Method 206.4 (Spectrophotometric-SDDC)

STORET NO. 01002

Inorganic, Di~_solv~~ 00095

Inorganic, Total 00997

Inorganic, Suspended 00996

1 Scope and ApplIcatlOn

lIThe sliver dlethyldlthlOcarbamate method determllles lllorgamc arsemc when present III

concentratlOns at or above 10 ug/1 The method lS applIcable to dnnklllg water and most

fresh and sahne waters III the absence of hlgh concentratlOns of chrommm, cobalt,

copper, mercury, molybdenum, mckel, and sliver Domestic and llldustnal wastes may

also be analyzed after dlgestlon (see 3 3)

1 2 Dlfficulties may be encountered wlth cerialll llldustnal waste matenals contallllllg

volatlie substances Hlgh sulfur content of wastes may exceed removal capaclty of the

lead acetate scrubber

2 Summary ofMethod

2 I Arsemc III the sample lS reduced to arSllle, AsH3, III aCld solutlOn III a hydrogen

generator The arSllle lS passed through a scrubber to remove sulfide and lS absorbed III a

solutlOn of slIver dlethyldlthlOcarbamate dlssolved III pyndllle The red complex thus

formed lS measured III a spectrophotometer at 535 nm

3 Comments

3 1 In analyzlllg dnnklllg water and most surface and ground waters, lllterferences are rarely

encountered Industnal waste samples should be splked wlth a known amount of arsemc

to establIsh adequate recovery

3 2 ItlS essential that the system be alrtlght dunng evolutlOn ofthe arSllle, to avold losses

3 3 If concentratlOn of the sample and/or oXldatlon of any orgamc matter lS reqUlred, refer

to Method 2065 [Standard Methods, 14th EdltlOn, Method 404B, p 284, Procedure 4 a

(1975)] For sample handlIng and preservatlOn, see part 4 1 of the AtomlC AbsorptlOn

Methods sectlon ofthls manual

3 3 1 Slllce mtnc aCld glves a negative lllterference III thlS test, use sulfunc aCld as a

preservative lfonly lllorgamc arsemc lS belllg measured

34 1-Ephednne III chloroform has been found to be a sUltable solvent for sliver

dlethyldlthlOcarbamate lf the analyst finds the odor of pyndllle objectlOnable [Anal

Chern 45, 1786 (1973)]

35 For qualIty control reqUlrements and optlOnal recommendatlOns for use III drmkmg

water analyses, see part 10 ofthe AtomlC AbsorptlOn Methods sectlOn ofthlS manual

Approved for NPDES and SDWA

Issued 1971

Editonal reV1Slon 1974

2064-1
4. PrecIsion and Accuracy

4 1 In a round-robIn study reported by Standard Methods a synthetic unknown sample

contaInIng 40 ug/l, as As, with other metals was analyzed In 46 laboratorIes Relative

standard deviatIOn was ±13 8% and relative error was 0%

5. Reference

5 1 The procedure to be used for this determInatIOn IS found In

Standard Methods for the ExamInation of Water and Wastewater, 14th Edition, p 283,

Method 404A (1975)

2064-2
ARSENIC

Method 206.5 (Sample Digestion Prior to Total Arsenic

Analysis by Silver Diethyldithiocarbamate or Hydride

Procedures)

1 Scope and ApphcatlOn

1 1 Both the sIlver diethyldithlOcarbamate spectrophotometnc method and the AA hydnde

procedure measure morgamc arsemc Therefore, If eIther of these procedures are bemg

employed for the purpose of measunng total arsemc (morgamc plus orgamc), all

orgamcally bound arsemc must first be converted to an morgamc form pnor to the

analytIcal determmatlOn ThIS may be accomphshed WIth H2S04-HN03

2 Procedure

2 1 To a SUItable sample contammg from 2 to 30 ug of arsemc, add 7 ml (1 +1) H2S04 and 5

ml conc HN03 Evaporate the sample to S03 fumes CautIOn Ifthe sample chars, stop

the dIgestIOn ImmedIately, cool and add addItIOnal conc HN03 Contmue dIgestIOn

addmg addItIOnal conc HN03as necessary

2 2 If the sample remams colorless, or straw-yellow dunng evolutIOn of S03 fumes, the

dIgestIOn IS complete

2 3 Cool the dIgested sample, add about 25 ml dIstIlled water, and agam evaporate to S03

fumes to expel OXIdes ofmtrogen

2 4 The sample IS now ready for analysIs usmg eIther the hydnde or spectrophotometnc

procedure

3 Interferences

3 1 All traces of mtnc aCId must be removed before eIther the spectrophotometnc or the

hydnde procedures are apphed OXIdes of mtrogen should be expelled by takmg the

sample to fumes ofS03

4 Notes

4 1 The dIgestIOn step may be carned out m a flask on a hot-plate or m a KJeldahl apparatus

ThIS dIgestIOn step may also be used, m effect, to concentrate the sample, masmuch as

any SIze volume may be processed

BIbliography

1 Standard Methods for the ExammatlOn ofWater and Wastewater, p285, method 404B, step 4a,

14th EdItIOn (1975)

Approved for NPDES and SDWA

Issued 1978

2065-1
BARIUM

Method 208.1 (Atomic Absorption, direct aspiration)

STORET NO. Total 01007

Dissolved 01005

Suspended 01006

OptImum Concentration Range: 1-20 mg/1 usmg a wavelength of553 6 nm

SensItIvity: 0 4 mg/1

DetectIon LImIt: 0 1mg/1

PreparatIOn ofStandard Solution

1 Stock SolutIOn Dissolve 1 7787 g barIUm chlonde (BaCI2·2H20, analytical reagent

grade) m deIOnIzed dlstdled water and dilute to lItter 1ml = 1mg Ba (1000 mg/1)

2 PotassIUm chlonde solutIOn Dissolve 95 g potassIUm chlonde, KCI, m deiOnIzed

dlstdled water and make up to lItter

3 Prepare dilutions of the stock banum solutIOn to be used as caltbratlon standards at the

time of analySIS To each 100 ml of standard and sample altke add 2 0 ml potassIUm

chlonde solutIOn The caItbratlOn standards should be prepared usmg the same type of

aCid and the same concentratIOn as Will result m the sample to be analyzed either directly

or after processmg

Sample PreservatIon

1 For sample handltng and preservation, see part 4 1 of the AtomiC AbsorptIOn Methods

sectIOn ofthis manual

Sample PreparatIon

1 The procedures for preparatIOn ofthe sample as given m parts 4 1 1 through 4 1 4 ofthe

AtomiC AbsorptIOn Methodssection ofthis manual have been found to be satisfactory

Instrumental Parameters (General)

1 Banum hollowcathode lamp

2 Wavelength 553 6 nm

3 Fuel Acetylene

4 OXidant Nitrous OXide

5 Type offlame Fuel nch

Approved for NPDES and SDWA

Issued 1974

208 1-1
Analysis Procedure

1 For analysIs procedure and calculation, see "DIrect AspIratIOn", part 9 1 of the AtomIC

AbsorptIOn Methods sectIOn ofthIS manual

Interferences

1 The use of a mtrous oXIde-acetylene flame vIrtually ehmmates chemlCalmterference,

however, banum IS easl1y IOmzed m thIS flame and potassmm must be added (1000 mg/1)

to standards and samples ahke to control thIS effect

2 Ifthe mtrous oXIde flame IS not aval1able and acetylene-aIr IS used, phosphate, s111con and

alummum w111 severely depress the banum absorbance Thts may be overcome by the

addItIon of2ooo mg/1lanthanum

Notes

1

2

3

Data to be entered mto STORET must be reported as ug/1

For concentratIOns ofbanum below 0 2 mg/1, the furnace procedure (Method 208 2) IS

recommended

For qUalIty control reqmrements and optIOnal recommendatIons for use m dnnkmg

water analyses, see part 10 ofthe AtomIC AbsorptIOn Methods section ofthIS manual

PreciSiOn and Accuracy

1 In a smgle laboratory (EMSL), usmg a mIxed mdustnal-domestic waste eftluent at

concentratIOns of 040 and 20 mg Ba/1, the standard deVIatIOns were ±O 043

and ±O 13, respectIvely Recovereis at these levels were 94% and 113%, respectIvely

2 In a round-robm study reported by Standard Methods (13th EdItion, p215, method

129A, 1971), three synthetIc samples contammg banum were analyzed by 13

laboratones At concentratIOns of 500, 1000 and 5000 ug Ba/1, the reported standard

deVIations were ±50, ±89 and ±185 ug, respectIvely The relatIve error at these

concentratIOns was 8 6%,2 7% and 1 4%, respectively

208 1-2
BARIUM

Method 208.2 (Atomic Absorption, furnace technique)

STORET NO. 01007

Dissolved 01005

Suspended 01006

OptImum ConcentratIOn Range: 10-200 ug/l

DetectIOn LImit: 2 ug/l

PreparatIOn ofStandard SolutIOn

1 Stock solutlOn Prepare as desCrIbed under "dIrect aspiratlOn method"

2 Prepare dllutlOns of the stock solutlOn to be used as calIbratlOn standards at the time of

analySIS These solutlOns are also to used for "standard addItions"

3 The cahbratlOn standard should be dlluted to contam 0 5% (vIv) HN03

Sample PreservatIon

1 For sample handlIng and preservatlOn, see part 4 1 of the AtomIC AbsorptlOn Methods

sectlOn OfthiS manual

Sample PreparatIon

1 Prepare as desCrIbed under "dl,fect aspiratlOn method" Sample solutlOns for analySIS

shouldcontamO 5% (v/v)HN03

Instrument Parameters (General)

1 Drymg TIme and Temp 30sec-125°C

2 Ashmg TIme and Temp 30sec-1200°C

3 AtomIzmg TIme and Temp 10 sec-28oo°C

4 Purge Gas Atmosphere Argon

5 Wavelength 553 6 nm

6 Other operatmg parameters should be set as speCIfied by the partIcular mstrument

manufacturer

AnalYSIS Procedure

1 For the analySIS procedure and the calculatlOn, see "Furnace Procedure" part 9 3 ofthe

AtomIC AbsorptlOn Methods sectlOn ofthIS manual

Notes

1 The above concentration values and mstrument condItions are for a Perkm-Elmer HGA2100, based on the use of a 20 ul mJectlOn, contmuous flow purge gas and pyrolytic

graphIte

Approved for NPDES and SDWA

Issued 1978

2082-1
2 The use ofhahde aCId should be aVOIded

3 Because ofpossIble chemIcal InteractIOn, mtrogen should not be used as a purge gas

4 For every sample matnx analyzed, venficatIOn IS necessary to determIne that method of

standard addItIon IS not reqUIred (see part 52 1 of the AtomIC AbsorptIOn Methods

sectIon ofthIS manual)

5 Ifmethod ofstandard addItIOn IS reqUIred, follow the procedure gIven earher In part 8 5

ofthe AtomIC AbsorptIon Methods sectIon ofthIS manual

6 For quahty control reqUIrements and optIOnal recommendatIOns for use In dnnkIng

water analyses, see part 10 ofthe AtomIC AbsorptIOn Methods sectIOn ofthIS manual

7 Data to be entered Into STORET must be reported as ug/1

Precision and Accuracy

1. In a SIngle laboratory (EMSL), USIng CInCInnatI, OhIO tap water spIked at concentratIOns

of 500 and 1000 ug Ball, the standard deVIatIOns were ±2 5 and ±2 2 ug, respectIvely

Recovenes at these levels were 96% and 102%, respectIvely A dIlutIOn of 110 was

reqUIred to bnng the spIkes WIthIn the analytICal range ofthe method

l'

III

I

2082-2
BERYLLIUM

Methods 210.1 (Atomic Absorption, direct aspiration)

STORET NO. Total 01012

Dissolved 01010

Suspended 01011

OptImum ConcentratIon Range: 005-2 mg/l usmg a wavelength of234 9 nm

SensitIvity: 0025 mg/l

DetectIon LImIt: 0 005 mg/l

PreparatIOn ofStandard SolutIon

I Stock solutlon DIssolve 196558 g beryllmm sulfate, BeSO.4H20, m deIOnized

dIstllled water contammg 2 ml conc nItnc aCid and dIlute to I lIter I mi = I mg Be

(1000 mg/I)

2 Prepare dllutIOns of the stock solutIon to be used as cahbratlon standards at the tIme of

analysIs The cahbratIOn standards should be prepared usmg the same type of aCId and at

the same concentratIOn as WIll result m the sample to be analyzed eIther dIrectly or after

processmg

Sample Preservation

1 For sample handhng and preservatIOn, see part 4 1 of the AtomIC Absorption Methods

sectIon ofthIS manual

Sample Preparation

1 The procedures for preparatIOn ofthe saJ;Ilple as given m parts 4 1 1 through 4 1 4 ofthe

AtomIC Absorption Methods section ofthIS manual have been found to be satIsfactory

Instrumental Parameters (General)

1 Berylhum hollow cathode lamp

2 Wavelength 234 9 nm

3 Fuel Acetylene

4 OXIdant NItrous oXIde

5 Type offlame Fuel rIch

AnalysIs Procedure

I For analySIS procedure and calculatIOn, see "DIrect AspIratIon", part 9 1 ofthe AtomIC

AbsorptIOn MethodssectIOn ofthIS manual

Approved for NPDES

Issued 1974

210 1-1
Interferences

1 SodiUm and sIlIcon at concentratIOns m excess of 1000 mg/1 have been found to severely

depress the berylhum absorbance

2 BIcarbonate Ion IS reported to mterfere, however, ItS effect IS ehmmated when samples

are aCIdified to a pH of 1 5

3. Alummum at concentratIOns of 500 ug/1 IS reported to depress the sens1tlVlty of

berylhum [Spectrocmm Acta 22,1325 (1966)]

Notes

1.

2

3

Data to be entered mto STORET must be reported as ug/1

The "alummon colonmetnc method" may also be used (Standard Methods, 14th

EdItion, p 177) The mm1mum detectable concentratIOn by thIS method IS 5 ug/1

For concentratIOns ofberylhum below 002 mg/1, the furnace procedure (Method 210 2)

IS recommended

Precision and Accuracy

1. In a smgle laboratory (EMSL), usmg a mIxed mdustnal-domest1c waste effluent at

concentratIons of 001, 005 and 025 mg Be/I, the standard deVIatIOns were ±O 001,

±O 001 and ±O 002, respectively Recovenes at these levels were 100%, 98% and 97%,

respectively

210 1-2
BERYLLIUM

Method 210.2 (Atomic Absorption, furnace technique)

STORET NO. 01012

Dissolved 01010

Suspended 01011

OptImum ConcentratIOn Range: 1-30 ug/1

DetectIon LImIt 0 2 ug/1

PreparatIOn of Standard SolutIOn

1 Stock solutIOn- Prepare as descnbed under "dIrect aspIratIOn method"

2 Prepare dl1utIOns of the stock solutIOn to be used as cahbratIOn standards at the tIme of

analysIs These solutIOns are also to be used for "standard addItIons"

3 The cahbratIOn standard should be dl1uted to contam 0 5% (vIv) HN03

Sample PreservatIon'

1 For sample handhng and preservatIon, see part 4 I of the AtomIc AbsorptIOn Methods

, sectIon ofthIS manual

Sample PreparatIOn

I Prepare as descnbed under "dIrect aspIratIOn method" Sample solutIOns for analysIs

should contam 0 5% (vIv) HN03

Instrument Parameters (General)

1 DrymgTIme and Temp 30sec-125°C

2 AshmgTImeand Temp 30 sec-1OO0°C

3 AtomIzmg TIme and Temp 10 sec-2800°C

4 Purge Gas Atmosphere Argon

5 Wavelength 234 9 nm

6 The operatmg parameters should be set as specIfied by the partIcular mstrument

manufacturer

AnalysIs Procedure

1 For the analysIs procedure and the calculatIOn see "Furnace Procedure" part 9 3 of the

AtomIC AbsorptIon methods sectIOn ofthIS manual

Notes

1 The above concentratIOn values and mstrument condItIOns are for a Perkm-Elmer HGA2100, based on the use of a 20 ul mJectIOn, contmuous flow purge gas and non-pyrolytIc

graphIte Smaller SIze furnace devIces or those employmg faster rates of atomIzatIOn can

Approved for NPDES

Issued 1978

210 2-1
be operated USIng lower atomIzatlOn temperatures for shorter tIme penods than the

above recommended settIngs

2. The use ofbackground correctlOn IS recommended

3 Because of possIble chemIcal InteractlOn and reported lower sensItIvIty, mtrogen should

not be used as the purge gas

4 For every sample matnx analyzed, venficatlOn IS necessary to determIne that method of

standard addItIon IS not reqUIred (see part 5 2 1 of the AtomIC AbsorptIOn Methods

sectIon OfthIS manual)

5 If method ofstandard addItIon IS reqUIred, follow the procedure gIven earlIer In part 8 5

ofthe AtomIC AbsorptIOn Methods sectlOn ofthIS manual

6 Data to be entered Into STORET must be reported as ug/l

Precision and Accuracy

1 PrecIsIon and Accuracy data are not avaIlable at thIS tIme

210 2-2
BORON

Method 212.3 (Colorimetric, Curcumin)

STORET NO. Total 01022

Dissolved 01020

Suspended 01021

1 Scope and Apphcatlon

11 ThIS colonmetnc method finds maXImum utlhty for waters whose boron content IS

below 1mg/l

12 The optImum range of the method on undtluted or unconcentrated samples IS 0 1-10

mg/lofboron

1 3 ThIS method IS apphcable to dr1Ok1Og, and surface waters, domestIc and 10dustnal

wastes

2 Summary ofMethod

2 1 When a sample of water conta101Og boron IS aCIdIfied and evaporated 10 the presence of

curcum1O, a red-colored product called rosocyamne IS formed The rosocyamne IS taken

up 10 a sUItable solvent, and the red color IS compared wIth standards photometncally

3 Comments

3 1 NItrate mtrogen concentratIons above 20 mg/l 10terfere

3 2 Slgmficantly hIgh results are possIble when the total ofcalcmm and magnesmm hardness

exceeds 100 mg/l as CaC03 Pass10g the sample through a catIon exchange resm

ehmmates thIS problem

3 3 Close control ofsuch vanables as volumes and concentratlOns ofreagents, as well as time

and temperature ofdry1Og, must be exerCIsed for maXImum accuracy

3 4 Data to be entered 1Oto STORET must be reported as ug/l

4 PrecIsIon and Accuracy

4 1 A synthetic sample prepared by the Analytlcal Reference ServIce, PHS, contam1Og 240

ug/l B, 40 ug/l As, 250 ug/l Be, 20 ug/l Se, and 6 ug/l V 10 dIstilled water, was

analyzed by the curcum10 method wIth a relative standard devIatIon of 228% and a

relatIve error of0% 10 30 laboratones

5 Reference

5 1 The procedure to be used for thIS determ1OatlOn IS found 10

Standard Methods for the Exammatlon of Water and Wastewater, 14th EdItIon, p 287,

Method 405A (1975)

Approved for NPDES

Issued 1974

2123-1
CADMIUM

Method 213.1 (Atomic Absorption, direct aspiration)

STORET NO. Total 01027

Dissolved 01025

Suspended 01026

Optimum Concentration Range: 005-2 mg!1 usmg a wavelength of228 8 nm

SensItivity: 0 025 mg!1

Detection Limit. 0 005 mg!1

Preparation ofStandard SolutIOn

1 Stock SolutiOn Carefully weigh 2 282 g of cadmIUm sulfate (3CdS04-8H20, analytical

reagent grade) and dIssolve In deIOnized dIStilled water make up to I liter with

deIOnized dIstIlled water I ml = 1 mg Cd (1000 mg/l)

2 Prepare dIlutiOns of the stock solutiOn to be used as calIbratiOn standards at the tIme of

analysIs The calIbratIon standards should be prepared usmg the same type of aCId and at

the same concentration as WIll result In the sample to be analyzed eIther dIrectly or after

processIng

Sample Preservation

1 For sample handlIng and preservatiOn, see part 4 1 of the AtomIC AbsorptiOn Methods

sectIon ofthIs manual

Sample Preparation

1 The procedures for prepanttion ofthe sample as given m parts 4 1 1 through 4 1 4 ofthe

AtomIC AbsorptiOn Methods sectIon ofthIs manual have been found to be satIsfactory

Instrumental Parameters(General)

1 CadmIUm hollow cathode lamp

2 Wavelength 2288 nm

3 Fuel Acetylene

4 OXIdant AIr

5 Type offlame OXIdIZIng

AnalYSIS Procedure

1 For analySIS procedure and calculatIon, see "DIrect ASpIratiOn", part 9 1 ofthe AtomIC

AbsorptIon Methods sectIon ofthIS manual

Approved for NPDES and SDWA

Issued 1971

EdItorIal reVISiOn 1974

213 1-1
Notes

1

2

3

For levels of cadmmm below 20 ug/l, eIther the SpecIal ExtractIOn Procedure gIven m

Part 9 2 of the AtomIc AbsorptIOn methods sectIOn as the furnace techmque, Method

213 2 IS recommended

Data to be entered mto STORET must be reported as\ug/l

For qualIty control reqUirements and optIOnal recommendatIOns for use m drinkuig

water analyses, see part 10 ofthe AtomIC Absorption Methods sectIOn ofthIS manual

Precision and Accuracy

1 An mterlaboratory study on trace metal analyses by atomIC absorptIOn was conducted by

the Quahty Assurance and Laboratory EvaluatIOn Branch of EMSL SIX synthetic

concentrates contammg varymg levels of alummum, cadmmm, chrommm, copper, Iron,

manganese, lead and zmc were added to natural water samples The statIstIcal results for

cadmmm were as follows

Standard

Number True Values Mean Value DevIatIOn Accuracy as

of Labs uglliter ug/hter uglliter % BIas -------

74 71 70 21 -22

73 78 74 18 -'5 1

63 14 168 110 198

68 18 183 103 19

55 14 33 50 135

51 28 29 28 47

213 1-2
CADMIUM

Method 213.2 (Atomic Absorption, furnace technique)

STORET NO. 01027

Dissolved 01025

Suspended 01026

Optimum ConcentratIOn Range: 0 5-10 ug/l

DetectIOn Lmllt: 0 1ug/l

PreparatIOn of Standard SolutIOn

1 Stock solution Prepare as descnbed under "direct aspIratIon method"

2 AmmonIum Phosphate solution (40%) DIssolve 40 grams of ammOnIum phosphate,

(NH4)2HP04(analytical reagent grade) III deIOnIZed dIstl1led water and dIlute to 100 ml

3 Prepare dI1utlOns ofthe stock cadmIUm solutIOn to be used as calIbratIOn standards at the

tIme of analysIs To each 100 ml of standard and sample alIke add 20 ml of the

ammOnIum phosphate solutIOn The calIbratIOn standards should be prepared to contam

05% (v/v) HN03

Sample Preservation

1 For sample handlIng and preservatIOn, see part 4 1 of the AtomIc AbsorptIon Methods

sectIOn ofthIS manual

Sample Preparation

1 Prepare as descnbed under "dIrect aspIratIOn method" Sample SolutIons for analysIs

should contam 05% (v/v) HN03

Instrument Parameters (General)

1 Drymg TIme and Temp 30 sec-125°e

2 Ashmg Time and Temp 30 sec-5oooe

3 AtomIzmg TIme and Temp 10 sec-19OO°C

4 Purge Gas Atmosphere Argon

5 Wavelength 228 8 nm

6 Other operatmg parameters should be set as specified by the partIcular mstrument

manufacturer

AnalYSIS Procedure

1 For the analysIs procedure and the calculatIOn, see "Furnace Procedure" part 93 ofthe

AtomIc AbsorptIOn Methods sectIOn ofthIS manual

Approved for NPDES and SDWA

Issued 1978

213 2-1
Notes

1

2

3.

4

5

6

7

The above concentratlOn values and Instrument condItions are for a PerkIn-Elmer HGA2100, based on the use of a 20 ul InJectlOn, continuous flow purge gas and non-pyrolytic IIIII

graphIte Smaller SIze furnace deVIces or those employing faster rates of atomizatlOn can

be operated uSing lower atomIzatIon temperatures for shorter tIme penods than the

above recommended settings

The use ofbackground correctlOn IS recommended

ContaminatIon from the work area IS cntIcal In cadmIUm analysIs Use of pIpet tIpS J I I I r'l

whIch are free of cadmIUm IS of particular Importance (See part 529 of the AtomIC

AbsorptIon Methods sectIon ofthIsmanual)' I

For every sample matnx analyzed, venficatlOn IS necessary to determine that method of

standard addItIon IS not reqUIred (see part 5 2 1 of the AtomIC AbsorptIon Methods

sectlOn ofthIS manual)

Ifmethod ofstandard addItIon IS reqUIred, follow the procedure gIven earlIer In part 8 5

ofthe AtomIC AbsorptIon Methods sectIon ofthIS ~anual

For qualIty control reqUIrements and optlOnal recommendatlOns for use In drInkIng

water analyses, see part 10 ofthe AtomIC AbsorptIon Methods sectIOn ofthIS manual

Data to be entered Into STORET must be reported as ug/l

Precision and Accuracy

1 In a Single laboratory (EMSL), USIng CinCInnatI, OhIO tap water spIked at concentratIons

of 2 5, 50 and 100 ug Cd/I, the standard deVIatIons were ±O 10, ±O 16 and ±O 33,

respectIvely Recovenes at these levels were 96%,99% and 98%, respectIvely

2132-2
CALCIUM

Method 215.1 (Atomic Absorption, direct aspiration)

STORET NO. Total 00916

Dissolved 00915

OptI~um Concentration Range: 0 2-7 mg;i usmg a wavelength,of422 7 nm

Sensitivity: 008 mg/l

Detec,tIOn LImIt: 001 mg/l

,

Preparation ofStandard SolutIOn

,1 Stock SolutIOn Suspend 1 250 g ofCaC03 (analytical reagent grade), dned at 180°C for 1

hour before weIghmg, m deIOnIZed dlstilled water and dIssolve cautIOusly wIth a

mmimum of dilute HCI Dilute t? 1000 ml wIth, deIOnIzed dIstilled water 1 ml = 0 5

mg Ca (500 mg/l)

2 Lanthanum chlonde solution DIssolve 29 g of La20 3, slowly and m small portIOns, m

250 ml conc HCI (CautIOn ReactIon IS VIOlent) and dilute to 500 ml wIth deIOnIZed

dIstIlled water

3 Prepare dIlutIOns ofthe stock calcIUm solutIOns to be used as calIbratIOn standards at the

tIme of analysIs To each 10 ml volume of calIbratIOn standard and sample alIke add 1 0

ml ofthe lanthanum chlonde solutIOn, 1 e , 20 ml of sta~dardor sample + 2 ml LaCl3 = 22ml

Sample Preservation

1 For sample handlIng and preservatIon, see part 4 1 of the AtomIC Absorption Methods

sectIOn ofthIS manual

Sample PreparatIon

1 For the analysIs oftotal calCIUm m domestIc and mdustnal effiuents, the procedures for

the determmatIOn of total metals as gIven m parts 4 1 3 and 4 1 4 of the AtomIC

Absorption Methods section ofthIs manual have been found to be satIsfactory

2 For ambIent waters, a representatIve alIquot ofa well-mIxed sample may be used dIrectly

for analysIs Ifsuspended solIds are present m suffiCIent amounts to clog the nebulIzer,

the sample may be allowed to settle and the supernatant lIqUId analyzed dIrectly

Instrumental Parameters (General)

1 CalCIUm hollow cathode lamp

2 Wavelength 422 7 nm

Approved for NPDES

Issued 1971

Editonal reVISIon 1974

215 1-1
3 Fuel Acetylene

4. OX1dant A1r

5 Type offlame Reducmg

Analysis Procedure

1. For analys1s procedure and calculatlOn, see "D1rect Asp1ratlOn", part 9 1 ofthe Atom1C

Absorpt1on Methods sectlOn ofth1S manual

Notes

1

2

3

4

5.

6

Phosphate, sulfate and alummum mterfere but are masked by the add1t1on oflanthanum

Smce low calcmm values result 1f the pH of the sample 1S above 7, both standards and

samples are prepared m dl1ute hydrochlonc aC1d solutlOn ConcentratlOns ofmagnesmm

greater than 1000 mg/1 also cause low calcmm values ConcentratlOns ofup to 500 mg/1

each ofsodmm, potassmm and mtrate cause no mterference

Amomc chem1cal mterferences can be expected 1flanthanum 1S not used m samples and

standards

The mtrous oX1de-acetylene flame w1ll prov1de two to five t1mes greater sens1t1v1ty and

freedom from chemlCal mterferences IomzatlOn mterferences should be controlled by

addmg a large amount of alkah to the sample and standards The analys1s appears to be

free from chem1cal suppreSSlOns m the mtrous oX1de-acetylene flame (Atom1c

AbsorptlOn Newsletter 14,29 [1975])

The 239 9 nm Ime may also be used Th1S hne has a re1at1ve sens1t1v1ty of 120

Data to be entered mto STORET must be reported as mg/1

The EDTA tltnmetnc method may also be used (Standard Methods, 14th Ed1tlOn, p

189)

Precision and Accuracy

1 In a smgle laboratory (EMSL), usmg d1st111ed water sp1ked at concentratlOns of 9 0 and

36 mgCa/1, the standard dev1atlOns were ±O 3 and ±O 6, respect1vely Recovenes at

both these levels were 99%

215 1-2
CALCIUM

Method 215.2 (Titrimetric, EDTA)

STORET NO. Calcium (mg/l CaC03) 00910

Calcium, Total (mg/l Ca) 00916

1 Scope and ApphcatlOn

1 1 ThIS method IS apphcable to dnnkmg and surface waters, domestIc and mdustnal wastes

1 2 The lower detectlOn hmlt ofthIS method IS approxImately 05 mg/1 as CaC03, the upper

hmlt can be extended to all concentratIons by sample dl1utlOn It IS recommended that a

sample ahquot contammg not more than 25 mg CaC03 be used

2 Summary ofMethod

2 1 Calcmm lOn IS sequestered upon the addItion of dlsodmm dlhydrogen ethylenedlamme

tetraacetate (EDTA) The tltratlOn end pomt IS detected by means of an mdlcator which

combmes wIth calcmm only

3 Interferences

3 1 Strontmm and banum mterfere and alkahmty m excess of 30 mg/1 may cause an

mdlstmct end pomt Magnesmm mterference IS reduced or ehmmated by ralsmg the pH

between 12-13 to precIpItate magnesmm hydroxIde

4 Apparatus

4 1 Routme laboratory tltnmetnc glassware

5 Reagents

5 1 Sodmmhydroxlde, NaOH, IN

5 2 IndICators

5 2 1 Many mdlcators are aval1able, both laboratory prepared and commercIal, and may

be used Two are descnbed here

522 MurexIde (ammomum purpurate) mdICator ThIS changes from pmk to purple

DIssolve 150 mg of the dye m 100 g absolute ethylene,glycol If a dry powder IS

preferred mIX 200 mg murexIde WIth 100 g sohd NaCI and gnnd to 40 to 50 mesh

Titrate ImmedIately after addmg mdlcator because It IS unstable under alkahne

condltlOns

523 Enochrome Blue Black R (sodmm-1-(2-hydroxy-1-naphthylazo)-2-naphthol-4-

sulfomc aCId) mdlcator This changes from red through purple to blmsh purple to a

pure blue WIthout any trace ofred or purple tmt The pH ofsome waters must be

raIsed to 14 (rather than 12-13) by the use of 8 N NaOH m order to get a good

color change Gnnd m a mortar 200 mg powdered dye and 100 g sohd NaCI to 40

to 50 mesh Store m tIghtly stoppered bottle Use 02 g ofthIS mIxture for tItratlOn

Approved for NPDES

Issued 1974

Edltonal reVlSlOn 1978

2152-1
5 3 Standard EDTA tltrant, 0 02 N Place 3 723 g analytical reagent grade disodIUm

ethylenedlamme tetraacetate dIhydrate, Na2H2ClQH120gN2-2 H20 mal lIter volumetnc

flask and dIlute to the mark wIth dIstIlled water Check wIth standard calcIUm solutIon

(5 3 1) by tItratIOn (5 3 5) Store m polyethylene Check penodICally becallse of gradual

detenoratIon

5 3 1 Standard calcIUm solution, 0 02 N Place 1 000 g anhydrous calcIUm carbonate

(pnmal y standard low m heavy metals, alkalIes and magnesIUm) m a 500 ml

flask Add, a lIttle at a tIme 1+1 HCI (5 3 2) untIl all of the CaC03 has dIssolved

Add 200 ml dlstllled water BOll f~r a few mmutes to expel CO2 Cool Add a few

drops of methyl red mdlcator (533) and adjust to mtermedIate orange color by

addmg 3N NH40H (5 3 4) or I + 1 HCI (5 3 2) as reqUIred Quantitatively

transfer to a I lIter volumetnc flask and dIlute to mark with dIstilled water

5 3 2 Hydroch10nc aCId solutIon, 1 + 1

5.33 Methyl red mdlcator DIssolve 0 10 g methyl red m dIstilled water m a 100 ml

volumetnc flask. and dIlute to mark

5 3 4 Ammomum hydrOXide solutIOn, 3 N

535 StandardIZatIOn tltratlon procedure Place 10 ml standard calcIUm solutIOn

(53 1) m a vessel contammg about 50 ml dIstIlled water Add 1ml buffer solutlon

(53 6) Add 1-2 drops mdICator (5 3 7) or small scoop of dry mdlcator (5 3 7)

TItrate slowly wIth contmuous stIrnng untIl the last reddIsh tmge dIsappears,

addmg last few drops at 3-5 second mtervals At end pomt the color IS blue Total

tItratIon duratIOn should be =::;; 5 mmutes from the tIme ofbuffer addItIOn

02

N of EDTA = ----

ml EDTA

536 Buffer solutIOn DIssolve 169 g ammomum chlonde m 143 ml conc ammomum

hydroxIde m a 250 ml volumetnc flask Add 1 25 g of magnesIUm salt of EDTA

(5 3 8) and dilute to the mark wIth dIstilled water Store m tIghtly stoppered plastIC

bottle

5 3 7 IndIcator CommerCIally available Enochrome Black T IS used m one ofthe three

methods descnbed AIl gradually detenorate

5 3 7 1 MIX 0 5 g dye wIth 4 5 g hydroxylamme hydrochlonde DIssolve m 100

ml of95% ethanol or Isopropanol

5 3 72 Place 0 5-1 0 g dye m 100 g of tnethanolamme or 2-methoxyethanol

5 3 7 3 MIX 0 5 g dye and 100 g NaCI for dry formulatIOn

5 3 8 EDTA MagnesIUm Salt CommerCIally available

6 Procedure

6 1 Pretreatment

6 1 1 For dnnkmg waters, surface waters, salIne waters, and dIlutIOns thereof, no

pretreatmentsteps are necessary Proceed to 6 2

6 1 2 For most wastewaters and hIghly polluted waters, the sample must be dIgested as

gIven m the AtomIC AbsorptIOn Methods sectIOn of thIS manual, paragraphs 4 1 3

and 4 1 4 Followmg thIS dIgestIOn, proceed to 6 2

6 2 Sample PreparatIon

62 1 The calCIUm content of the 50 ml alIquot to be tItrated should be 5-10 mg,

therefore dilutIon should be used for hIgh calCIUm concentratIons

2152-2
6 2 2 Ifthe alkahmty IS > 300 mg/1 CaC03 and cannot be reduced by dIlutIon because

of low calcIUm concentratIOn, the alkahmty must be decreased by aCIdIfyIng,

boIlIng one mInute and coohng

63 TItratIOn

63 1 Add 2 0 ml NaOH solutIOn (5 1), or a volume suffiCIent to produce pH 12 to 13, to

50 ml ofsample

632 StIr Add 01 to 0 2 g IndIcator (5 2 or 523) or 1-2 drops IfIndlCator SolutIon IS

used

6 3 3 ImmedIately tItrate WIth contInuous stIrnng Check to see that no further color

change occurs when USIng murexIde (5 2 2) by addIng 1 to 2 more drops oftItrant

after recordIng mIlhhters oftItrant at firstJudged end POInt

7 CalculatIons

7 1 Total calcIUm

mg/1 Ca = A x N x 20,040

ml of sample

mg/1 CaC03 =

where

A = ml tItrant

N = NormahtyofEDTAsolutIOn

7 2 CalcIUm hardness

A x N x 50,000

ml of sample

where A and N are the same as In 7 I

8 PreCIsIOn and Accuracy

81 A synthetIc unknown sample contaInIng 108 mg/1 Ca, 82 mg/1 Mg, 3 1 mg/1 K, 199

mg/1 Na, 241 mg/1 chlonde, 1 1 mg/1 mtrate N, 250 ug/1 mtnte N, 259 mg/1 sulfate,

and 42 5 mg/1 total alkahmty In dIstIlled water was determIned by thIS method wIth a

relatIve standard devIatIon of9 2% and a relatIve error of l' 9% In 44laboratones

Bibliography

1 Standard Methods for the ExamInatIon of Water and Wastewater, 14th EdItIOn, p 189,

Method 306C (1975)

2 Annual Book of ASTM Standards, Part 31, "Water", Standard D511-76, Method B, p 253

(1976)

2152-3
CHROMIUM

Method 218.1 (Atomic Absorption, direct aspiration)

STORET NO. Total 01034

Dissolved 01030

Suspended 01031

Optimum Concentration Range: 0 5-10 mg/l usmg a wavelength of357 9 nm

Sensitivity: 0 25 mg/l

Detection Limit: 0 05 mg/l

Preparation ofStandard Solution

1 Stock SolutIOn Dissolve 1 923 g ofchromIUm tnoxlde (Cr03, reagent grade) m deIOnIZed

dlstl1led water When solutIOn IS complete, aCidify with redlstdled HN03 and dllute to 1

hter with deIOnIZed dlstl1led water 1ml = 1mg Cr (1000 mg/l)

2 Prepare dl1utIOns of the stock solutIOn to be used as cahbratlon standards at the time of

analysIs The cahbratIOn standards should be prepared usmg the same type ofaCid and at

the same concentratIOn as Will result In the sample to be analyzed either directly or after

processmg

Sample Preservation

1 For sample handhng and preservatIOn, see part 4 1 of the AtomiC AbsorptIOn Methods

sectIOn ofthiS manual

Sample Preparation

1 The procedures for preparatIOn of the sample as given m parts 4 1 1 thru 4 1 4 of the

AtomiC AbsorptIOn Methods sectIOn ofthis manual have been found to be satisfactory

Instrumental Parameters (General)

1 ChromIUm hollow cathode lamp

2 Wavelength 3579nm

3 Fuel Acetylene

4 OXidant Nitrous OXide

5 Type offlame Fuel nch

AnalYSIS Procedure

1 For analySIS procedure and calculatIOn, see "Direct AspiratIOn", part 9 1 ofthe AtomiC

AbsorptIOn Methods section ofthiS manual

Approved for NPDES and SDWA

Issued 1971

Edltonal revIsion 1974 and 1978

218 1-1
Notes

1

2

3

4

5

6

The follow1Og wavelengths may also be used

359 3 nm Relative SensltlVlty 1 4

425 4 nm Relative SenSItiVity 2

427 5 nm Relative Sensitivity 3

428 9 nm Relative SensItivity 4

The fuel nch air-acetylene flame provides greater senSitiVity but IS subject to chemical

and matnx 10terference from Iron, mckel, and other metals Ifthe analySiS IS performed

10 a lean flame the 10terference can be lessened but the sensitivity Will also be reduced

The suppression of both Cr (III) and Cr (VI) absorptIOn by most 1Oterfer1Og Ions 10 fuel

nch aIr-acetylene flames is reportedly controlled by the additIOn of 1% ammomum

bifluonde 10 0 2% sodium sulfate [Talanta 20, 631 (1973)] A 1% ox1Oe solutIOn IS also

reported to be useful

For levels of chromIUm between 50 and 200 ug/1 where the air-acetylene flame can not

be used or for levels below 50 ug/1, either the furnace procedure or the extractIOn

procedure IS recommended See Method 218 2 for the furnace procedure and Method

218 3 for the chelatlOn-extractlOn procedure

For qUality control reqmrements and optIOnal recommendatIOns for use 10 dnnk10g

water analyses, see part 10 ofthe AtomiC AbsorptIOn Methods sectIOn ofthis manual

Data to be entered 1Oto STORET must be reported as ug/1

Precision and Accuracy

1 An 1Oterlaboratory study on trace metal analyses by atomiC absorptIOn was conducted by

the Quality Assurance and Laboratory EvaluatIOn Branch of EMSL SiX synthetiC

concentrates conta101Og vary10g levels of alum1Oum, cadmIUm, chromIUm, copper, Iron,

manganese, lead and z10c were added to natural water samples The statistical results for

chromIUm were as follows

Standard

Number True Values Mean Value DeViatiOn Accuracy as

of Labs ug/hter ug/hter ug/hter % Bias

74 370 353 105 -45

76 407 380 128 -65

72 74 72 29 -3 1

70 93 84 35 -102

47 74 102 78 377

47 150 160 90 68

218 1-2
CHROMIUM

Method 218.2 (Atomic Absorption, furnace technique)

STORET NO. 01034

Dissolved 01030

Suspended 01031

OptImum ConcentratIon Range: 5-100 ug/l

Detection LimIt: 1 ug/l

PreparatIon ofStandard SolutIon

1 Stock solutIOn Prepare as descnbed under "dIrect aspIratIon method"

2 Calcmm NItrate SolutIOn DIssolve 11 8 grams of calcmm mtrate, Ca(N03)2 • 4H20

(analytIcal reagent grade) m delOmzed mstl1led water and dIlute to 100 ml 1ml = 20 mg

Ca

3 Prepare ddutions of the stock chrommm solutIOn to be used as cahbratlOn standards at

the tIme ofanalysIs The cahbratlOn standards should be prepared to contam 05% (v/v)

HN03 To each 100 ml ofstandard and sample ahke, add 1 ml of 30% H20 2 and 1 ml of

the calcmm filtrate solutIOn

Sample PreservatIOn

1 For sample handhng and preservatIOn, see part 41 ofthe AtomIC AbsorptIon Methods

section of thIS manual

Sample PreparatIon

1 Prepare as descnbed under "dIrect aspIratIOn method" Sample SolutIons for analysIs

shou1dcontamO 5% v/vHN03

Instrument Parameters (General)

1 DrymgTImeand Temp 30sec-125°C

2 AshmgTImeand Temp 30sec-10oo°C

3 AtomIzmg TIme and Temp 10 sec-27oo°C

4 Purge Gas Atmosphere Argon

5 Wavelength 357 9 nm

6 Other operatmg parameters should be set as specIfied by the partIcular mstrument

manufacturer

AnalysIs Procedure

1 For the analysIs procedure and the calculatIOn, see "Furnace Procedure" part 9 3 ofthe

AtomIC AbsorptIOn Methods sectIon ofthIS manual

Approved for NPDES and SDWA

Issued 1978

2182-1
Notes

1

2

3

4

5

6

7

8.

9

The above concentratiOn values and mstrument cond1tiOns are for a Perkm-Elmer HGA2100, based on the use of a 20 ul mJecton, contmuous flow purge gas and non-pyrolyt1c

graph1te

Hydrogen perox1de 1S added to the aC1d1fied solutiOn to convert all chrommm to the

tnvalent state Calcmm 1S added to a level above 200 mg/l where 1tS suppreSS1ve effect

becomes constant up to 1000 mg/l

Background correctiOn may be reqmred 1fthe sample contams h1gh d1sso1ved sohds

N1trogen should not be used as a purge gas because ofposs1ble CN band mterference

P1pet t1pS have been reported to be a poss1ble source of contammatlon (See part 5 2 9 of

the Atom1c AbsorptiOn Methods sectiOn oft1us manual)

For every sample matnx analyzed, venficatiOn 1S necessary to determme that method of

standard add1tion 1S not reqmred (see part 52 1 of the Atom1c AbsorptiOn Methods

sectiOn oftms manual)

Ifmethod ofstandard add1tiOn 1S reqmred, follow the procedure glVen earher m part 8 5

ofthe Atom1c AbsorptiOn Methods sectiOn ofth1s manual

For quahty control reqmrements and optiOnal recommendatiOns for use m dnnkmg

water analyses, see part 10 ofthe Atoffilc AbsorptiOn Methods sectiOn ofth1s manual

Data to be entered mto STORET must be reported as ug/l

Precision and Accuracy

1 In a smgle laboratory (EMSL), usmg Cmcmnat1, OhiO tap water sp1ked at concentratiOns

of 19, 48, and 77 ug Cr/l, the standard dev1atiOns were ±O I, ±O 2, and ±O 8,

respect1vely Recovenes at these levels were 97%, 101%, and 102%, respectively

2182-2
CHROMIUM

Method 218.3 (Atomic Absorption, chelation-extraction)

STORET NO. 01034

1 Scope and Apphcatton

1 1 ThIs method covers the determmatton of total chromlUm m drmkmg, surface and sahne

waters The method may also be apphcable to certam domestIc and mdustnal wastes

provIded that no mterfenng substances are present (See 3 1)

1 2 The method may be used to analyze samples contammg from 1 0 to 25 ug of chromlUm

per hter

1 3 For sample handlmg and preservatlOn, see part 4 1 of the AtomIC Absorption Methods

sectlOn ofthIs manual

2 Summary ofthe Method

2 1 ThIs method IS based on the chelatlOn of hexavalent chromlUm wIth ammomum

pyrrohdme dithtocarbamate (APDC) followmg oXIdation of tnvalent chrommm The

chelate IS extracted wIth methyl Isobutyl ketone (MIBK) and aspIrated mto the flame of

the atomIC absorptIOn spectrophotometer

2 2 Hexavalent chrommm may also be chelated wIth pyrrohdme dlthlOcarbamlc aCId m

chloroform as descnbed m sectlOn 9 2 ofthe atomIC absorptlOn textfound m thIs manual

3 Interferences

3 1 HIgh concentratIOns of other reactIve metals, as may be found m wastewaters, may

mterfere The method IS free from mterferences from elements normally occurnng m

fresh water

4 Instrumental Parameters (General)

4 1 Chrommm hollow cathode lamp

42 Wavelength 3579 nm

4 3 Fuel Acetylene

4 4 OXIdant AIr

4 5 Type offlame Fuel nch (adjust for orgamc solvent)

5 Reagents

5 1 Ammomum pyrrohdme dlthlOcarbamate (APDC) solutlOn DIssolve 109 APDC m

demmerahzed water and dllute to 100 m 1 Prepare fresh dally

52 Bromophenol blue mdicator solutIOn DIssolve 0 1 g bromophenol blue m 100 ml

50-percent ethanol

53 Potassmm dIchromate standard solutlOn, 10 ml = 008 mg Cr DIssolve 02263 g dned

analytICal reagent grade K2Cr20 7 m demmerahzed water and make up to 1000 ml

54 Tnvalent chrommm stock solutlOn, 10 ml = 0002 mg Cr+3 PIpet 500 ml of the

potassmm dIchromate standard solutlOn (53) mto an Erlenmeyer flask Add

apprOXImately 15 mg Na2S03 and 05 ml concentrated HN03 Gently evaporate to

Approved for NPDES and SDWA

Issued 1978

2183-1
dryness, strong heatmg reoxIdIzes the chromnim Add 0 5 m1 concentrated HN03 and

agam evaporate to dryness to destroy any excess sulfite Take up mimi concentrated

HN03 wIth warmIng and dIlute to 200 0 m1 wIth demmeralIzed water

55 Trivalent chromIUm workIng solutIOn, 10 m1 = 0 005 ~g Cr~3 ImmedIately before

use, dIlute 250 m1 of tnvalent chromIUm stock solutIOn (54) to 1000 m1 wIth

demmeralIzed water

56 PotassIUm permanganate, 01 N DIssolve 032 g potassIUm permanganate m 100 m1

demIneralIzed water

57 SodIUm aZIde, 01% DIssolve 100 mg sodIum aZIde m demineralIzed water and dIlute to

100m1

5 8 Methyl Isobutyl ketone (MIBK)

5 9 SodIUm hydroxIde SolutIon, 1M DIssolve 40 g NaOH m demmeralIzed water and dIlute

to 1lIter

5.10 Sulfunc aCId, 0 12 M Slowly add 65 m1 concentrated H2S04 (sp gr 1 84) to

demIneralIzed water and dIlute to 1lIter

6. Procedure

6 1 PIpet a volume ofsample contaImg less than 2 5 ug chromIUm (100 m1 maxImum) mto a

200 m1 volumetnc flask, and adjust the volume to approxImately 100 m1 The pH must

be 2 0 or less Add concentrated HN03 Ifnecessary

62 ACIdIfy a lIter of demmeralIzed water wIth 1 5 m1 concentrated HN03 Prepare a blank

and suffiCIent standards usmg tnvalent chromIUm and adjust volumes to approxImately

100 m1 wIth the aCIdIfied demmeralIzed water

6 3 Add 0 1 N KMn04 dropwise to both standards and samples untIl a famt pInk color

persIsts

6 4 Heat on a steam bath for 20 mmutes If the color dIsappears, add addItIOnal KMn04

solutIon dropwise to maIntam a slIght excess

65 WhIle stIll on the steambath, add sodIUm aZIde solutIOn dropwise untIl the KMn04 color

Just disappears Heat for about 2 mm between each additIon and aVOid addmg any excess

Contmue heatmg for 5 mm after addIng the last drop ofsodIUm aZIde solutIOn

6 6 Transfer the flasks to a water bath and cool to room temperature

67 Remove from the water bath and filter (through Whatman No 40 filter paper or

eqUIvalent) any sample WhICh has a browmsh preCIpItate or coloratIon whIch may

mterfere wIth the pH adjustment

68 Add 2 0 ml of I 1\1 NaOH and 2 drops bromophenol blue IndICator solutIon ContInue

the addltlOn of I M NaOH dropwIse to all samples and standards In whIch the IndIcator

change from yellow to blue has not occurred Add 0 12 M H2S04dropWIse untIl the blue

colorJust disappears, then add 2 0 m1 m excess The pH at tills pomt Will be 24

6 9 The pH adjustment to 2 4 may also be made wIth a pH meter mstead of USIng an

mdIcator

6.10 Add 50 m1 APDC SolutIon and mIX The pH should then be approxImately 2 8

6 11 Add 10 0 m1 MIBK and shake vIgorously for 3 mmutes

6 12 Allow the layers to separate and add demIneralIzed water untIl the ketone layer IS

completely m the neck ofthe flask

2183-2
613 Aspirate the ketone layer, record the mstrument readmg for each sample and standard

agamst the blank Repeat, and average the duphcate results

7 CalculatlOns

7 1 Determme the ug/l Cr m each sample from a plot of the mstrument readmgs of

standards A workmg curve must be prepared with each set of samples Report Cr

concentratlOns as follows Less than 10 ug/l, nearest ug/l, 10 ug/l and above, two

slgmficant figures

8 PreclslOn and Accuracy

8 1 PrecIsion and accuracy data are not aval1able at this time

9 Reference

9 1 AtomiC AbsorptlOn Newsletter 6, p 128 (1967)

2183-3
CHROMIUM, HEXAVALENT

Method 218.4 (Atomic Absorption, chelation-extraction)

STORET NO. 01032

1 Scope and ApphcatlOn

1 1 ThIS method covers the determmatlOn of dIssolved hexavalent chromIUm m dnnkmg,

surface and salme waters The method may also be apphcable to certam domestIc and

mdustnal wastes after filtratIon prOVIded that no mterfernng substances are present (See

41)

12 The method may be used to analyze samples contammgfrom 10 to 250 ugof chromIum

perhter

2 Summary ofthe Method

2 1 ThIs method IS based on the chelatlOn of hexavalent chromIUm wIth ammOnIum

pyrrolIdme dithlOcarbamate (APDC) and extractlOn wIth methyl Isobutyl ketone

(MIBK) The extract IS aspIrated mto the flame of the atomIC absorptIon

spectrophotometer

2 2 Hexavalent chromIUm may also be chelated wIth pyrrolIdme dithtocarbamic aCId m

chloroform as descnbed m sectIOn 9 2 ofthe atomIC absorptIon text found m thIS manual

A pH of2 3 must be mamtamed throughout the extractIOn

23 The diphenylcarbazide colonmetnc procedure as found on p 192 of"Standard Methods

for the ExammatlOn ofWater and Wastewater", 14th edItIon, 1975, may also be used

3 Sample Handhng and PreservatIOn

3 1 StabIlIty of hexavalent chromIUm IS not completely understood at thIS tIme Therefore,

the chelatIon and extractIon should be carned out as soon as pOSSIble

3 2 To retard the chemIcal actIVIty of hexavalent chromIUm, the sample should be

transported and stored untIl tIme ofanlysis at 4°C

4 Interferences

41 HIgh concentratIons of other reactIve metals, as may be found m wastewaters, may

mterfere The method IS free from mterferences from elements normally occurnng m

fresh water

5 Instrumental Pat;ameters (General)

5 1 ChromIUm hollow cathode lamp

52 Wavelength 3579 nm

5 3 Fuel Acetylene

5 4 OXIdant AIr

5 5 Type ofFlame Fuel nch (adjust for orgamc solvent)

6 Reagents

6 1 AmmOnIum pyrrolIdme dlthIOcarbamate (APDC) solutIOn DIssolve 109 APDC m

\ demmeralIzed water and dIlute to 100 ml Prepare fresh dally

Approved for NPDES

Issued 1978

2184-1
62 Bromophenol blue mdlCator solution DIssolve 0 1 g bromophenol blue m 100 ml

50-percent ethanol

6 3 Chrommm standard solutlOn I, 1 0 ml = 100 ug Cr DIssolve 0 2829 g pure, drIed

K2Cr207 m demmeralIzed water and dIlute to 1000 ml

6 4 Chrommm standard solutlOn II, 1 0 m1 = 10 0 ug Cr DIlute 100 ml chrommm standard

solutlOn I to 1000 ml with demmeralIzed water

6 5 Chrommm standard solutlOn III, 1 0 ml = 0 10 ug Cr DIlute 10 0 ml chrommm

standard solution II to 1000 ml wIth demmeralIzed water

6 6 Methyl Isobutyl ketone (MIBK)

6 7 Sodmm hydrOXIde solutlOn, 1 M DIssolve 40 g NaOH m demmeralIzed water and dIlute

to 1 lIter

68 SulfurIC aCid, 012 M Slowly add 65 ml concentrated H2S04 (sp gr 1 84) to

demmeralIzed water and dIlute to 1 lIter

7 Procedure

71 Pipet a volume of sample contammg less than 25 ug chromIUm (100 ml maxImum)

mto a 200 ml volumetrIc flask, and adjust the volume to approxImately 100 ml

7 2 Prepare a blank and suffiCientstandards, and adjust the volume ofeach to approximately

lOOml

73 Add 2 drops bromophenol blue mdlCatorsolution (The pH adjustment to 24 may also

be made With a pH meter mstead of usmg an mdlcator )

74 Adjust the pH by addition of 1 M NaOH solution dropwlse untIl a blue color persists

Add 012 M H2S04 dropWlse untIl the blue color Just disappears m both the standards

and sample Then add 2 0 ml of 0 12 M H2S04 m excess The pH at thiS pomt should be

24

7 5 Add 5 0 ml APDC solution and mix The pH should then be approximately 2 8

7.6 Add 10 0 ml MIBK and shake vigorously for 3 mmutes

7 7 Allow the layers to separate and add demmeralIzed water untIl the ketone layer IS

completely m the neck ofthe flask

7 8 Aspirate the ketone layer and record the scale readmg for each sample and standard

agamst the blank Repeat, and average the duplIcate results

8. CalculatlOns

8 1 Determme the ug/l Cr+6 m each sample from a plot of scale readmgs of standards A

workmg curve must be prepared WIth each set ofsamples Report CrH concentratlOns as

follows Less than 10 ug/l, nearest ug/l, 10 ug/l and above, two slgmficant figures

9 PreCISion and Accuracy

9 1 In a smgle laboratory (EMSL), usmg the (PDCA) extraction procedure and Cm?mnatl

OhiO tap water spIked at a concentratlOn of 50 ug Cr+6/l the standard devlatlOn was

±2.6 WIth a mean recovery of96%

2184-2
& EPA

United States

Environmental Protection

Agency

Research and Development

Test Method

Environmental MOnitoring and

Support Laboratory

CinCinnati OH 45268

Chromium, Dissolved

Hexavalent (Atomic

Absorption, Furnace

Technique)-Method 218.5

1 Scope and ApplicatIon 3 Sample Handling and

PreservatIon

1 1 ThIs method covers the

determination of dIssolved hexavalent

chromium (Cr G+) In drinking and

surface waters The method may also

be applicable to certain domestic and

industrial wastes after fIltratIOn

provided that potential Interfernng

substances are taken Into account

(See 4 1 )

1 2 The method may be used to

analyze samples containing from 5 to

100 /1g of CrG+ per liter The range of

the method may be extended upward

by dilution

2 Summary of Method

2 1 The method IS based on the

separation of CrG+ from the sample by

copreclpltatlon of lead chromate wIth

lead sulfate In a solution of acetic

aCid After separation, the supernate

IS drawn off and the CrG precipitate

resolubllized In nitriC aCid as trivalent

chromium (Cr3+) and quantifIed by

furnace atomic absorption

22 Hexavalent chromium may also

be analyzed by the chelation I

extractIOn technique (see Method

218 4 or the procedure described In

9 2 of the Atomic AbsorptIon methods

found In thiS manual)

3 1 For sample handling cleaning

glassware and the filtration procedure

see part 4 1 of the AtomIc Absorption

Method section of thiS manual

3 2 The sample must not be

preserved by aCidification, but Instead

transported and stored until time of

analysIs atAOC

3 3 Stability of CrG+ In environmental

samples IS n ot completely understood

at thIS time The chemical nature of

the sample matrix can have a definite

affect on the chemistry of chromium

Therefore the analysIs should be

carned out as soon as possIble but no

longer than 24 hours after collection

4 Interferences

4 1 The possible Interference from

other elements which form stable

chromates IS not known at thIS tIme

4 2 Samples With eIther sulfate or

chlOride concentratIons above 1000

mg/llter should be diluted before

analYSIS

4 3 The potential reductIOn of CrG

+

from highly reductive substances

Increases as pH IS lowered When

sulfltes and sulfIdes are present the

2185-1 Dec 1982
sample aliquot taken for analysIs

should be neutralized and aerated

before beginning

5. Instrument Parameters

(General)

5.1 Drying Time and Temp 30 sec125°C

5.2 Ashlng Time and Temp 30 sec10000 C

5.3 Atomizing Time and Temp 10

sec-27oooC

5.4 Purge Gas Atmosphere Argon

5.5 Wavelength 367 9nm

5 6 Other operating parameters

should be as specified by the

particular Instrument manufacturer

6. Special Apparatus

6 1 Glassware

6.1 1 Filtering flask, heavy wall, 1

hter capaCIty

6.1 2 Centrifuge tubes, heavy duty,

oonlcal, graduated, glass stoppered,

10 mL capacity

6.1.3 Pasteur pIpets, borOSIlicate

glass, 6 Inches

6 2 Centrifuge any centnfuge

capable of reaching 2000 rpm and

acceptmg the centrifuge tubes

described In 6 1 2 may be used

6 3 pH Meter a Wide variety of

Instruments are commerCially

available and sUItable for this work

6 4 Test Tube Mixer any mixer

capable of thorough vortex IS

acceptable

7. Reagents

7.1 Lead Nitrate Solution Dissolve

33 1 grams of lead nitrate, Pb(N03}2

(analYtical reagent grade), In cfelonlzed

distllled water and dIlute to 100 mL

7.2 AmmoOlum Sulfate Solution

Dissolve 2 7 grams of ammonium

sulfate, (NH~}2S0~ (analytical reagent

grade), In deionized distilled water and

dilute to 100 mL

7 3 CalCium Nitrate Solution

Dissolve 11 8 grams of calcium

nitrate, Ca(NO.:J12 4H20 (analYtical

reagent grade), in deionized distilled

water and dilute to 100 mL 1 mL =

20 mg Ca.

7 4 Nltnc ACid, conc Distilled

reagent grade or eqUivalent to

spectrograde quality

75 AcetiC ACid, Glacial ACS

reagent grade

75 1 AcetiC ACid, 10% (v/v) Dilute

10 mL glacial acetic aCid to 100 mL

With deionized distilled water

7 6 AmmOnium HydrOXide, 10%

(v/v) Dilute 10 mL conc ammonium

hydrOXide, NH40H (analytical reagent

grade), to 100 mL With deiOnized

distilled water

7 7 Hydrogen PerOXide, 30% ACS

reagent grade

7 8 Potassium Dichromate Standard

Solution Dissolve 2 8286 grams of

dried potassium dichromate, K2Cr207

{analytical reagent grade}, In deionized

distIlled water and dilute to 1 liter 1

mL =1 mg Cr (1000 mg/L)

7 9 Trivalent Chromium Working

Stock Solution To 50 mL of the

potassium dichromate standard

solution (7 8) add 1 mL of 30% H202

(7 7) and 1 mL conc HN03 (7 4) and

dilute to 100 mL With deIOnized

distilled water 1 mL =0 5 mg Cr3+

Prepare fresh monthly or as needed

8 Calibration

8 1 At the time of analYSIS prepare a

blank and a series of at least four

calibration standards from the Cr3+

working stock (7 9) that Will

adequately bracket the sample The

normal working range covers a

concentration range of 5 to 100 ug

Cr/L Add to the blank and each

standard 1 mL 30% H20 2 (7 7), 5 mL

CONC HNOa (7 4), and 1 mL calCium

nitrate solution (73) for each 100 mL

of prepared solution before diluting to

final volume These calibratIOn

standard should be prepared fresh

weekly or as needed

8 2 The listed Instrumental

conditions (5 ) and the stated

calibration concentratIOn range are for

a Perkin-Eimer HGA-2100 based on

the use of a 20jJL injection, contlnous

flow purge gas and non-pyrolytlc

graphite The use of Simultaneous

background correction IS reqUired for

both calibration and sample analYSIS

9 Procedure

9 1 Transfer a 50 mL portion of the

filtered sample to a 1OOmL Gnffln

beaker and adjust to pH 3 5±0 3 by

adding 10% acetic aCid dropwlse

Record the volume of aCid added and

adjust the final result to account for

the dilution

Note Care must be exerCIsed not to

take the pH below 3 If the pH IS

Inadvertently lowered to < 3, 10%

NH40H (7 6) should be used to ialse

the pH to above 3

9 2 Pipet a 10 mL aliquot of the

adjusted sample Into a centnfuge tube

(6 1 2) Add 100jJL of the lead nitrate

solution (7 1), stopper the tube, mix the

sample and allow to stand for 3 min

9 3 After the formation of lead

chromate, retam the Cr3

+ complex In

solution by addition of 0 5 mL glaCial

acetic aCid (7 5) Stopper and mix

9 4 To prOVide adequate lead sulfate

for copreclpltatlon add 100 mL

ammonium sulfate solution (7 2),

stopper and mix

9 5 Place the stoppered centnfuge

tube In the centnfuge, making sure

that the tube IS properly

counterbalanced Start the centrifuge

and slowly Increase the speed to

2000 rpm In small Increments over a

penod of 5 min Centrifuge the sample at 2000 rpm for 10 min

Note 2 The speed of the centrifuge

must be Increased slowly to Insure

complete copreclpltatlon

9 6 After centrifuging remove the

tube and draw off the supernate uSing

the apparatus detailed In Figure 1 As

the pasteur pipet IS lowered Into the

tube the supernate IS sucked Into the

filtering flask With care the supernate

can be Withdrawn to Within

approximately 0 1 mL above the

preCipitate

9 7 To the remaining precipitate add

o 5 mL conc HN03 (7 4), 100jJL 30%

H2 0 2(7 7) and 100jJL calCium nitrate

solution (7 3) Stopper the tube and

mix uSing a vortex mixer to disrupt

the preCipitate and solubilize the lead

chromate Dilute to 10mL, mix and

analyze In the same manner as the

calibration standard (8 2)

9 8 For the general furnace

procedure and calculation, see

Furnace Procedure part 9 3 of the

AtomiC Absorption Methods section of

thiS manual

10 Verification

10 1 For every sample matrix

analyzed venflcatlon IS necessary to

determine that neither a redUCing

condition nor a chemical Interference

affecting preCipitation IS present ThiS

Dec 1982 2185-2
must be accomplished by analyzing a

second 10mL aliquot of the pH

adjusted filtrate (9 1) spiked wIth Cr 6+

(7 8) The amount of spIke added

should double the concentration found

In the original aliquot Under no

cIrcumstance should the Increase be

of less than 30,ug Cr6+/L To verify the

absence of an Interference the spIke

recovery should be between 85% and

115%

10 2 If the additIon of the spIke

extends the concentratIon beyond the

range of the calibratIOn curve, the

analYSIS solutIon should be dIluted

With blank solutIon and the calculated

results adjusted accordingly

10 3 If the VerifIcatIon indIcates a

suppressIve Interference, the sample

should be dIluted and reanalyzed

11 Analytical Notes

11 1 Nitrogen should not be used as

a purge gas because of possIble CN

band Interference

11 2 The use of pyrolytlc graphIte

should be avoIded when possIble

Generally, pyrolytlc graphIte resulted

In a more limIted analytIcal working

range and In some SItuatIOns an

enhancement effect

11 3 PIpet tIpS have been reported

to be a possIble source of

contaminatIOn (See part 5 2 9 of the

AtomIC AbsorptIon Methods sectIon of

thIs manual)

11 4 The method of standard

addItIon should not be requIred In as

much as the Cr6+ has been separated

from the original sample solutIon and

redIssolved In a uniform matrix haVIng

an absorptIon response cOincIdent to

the calibratIon curve

11 5 Data to be entered Into

STORET (No 01032) must be reported

as ,ug/L

12 PrecIsion and Accuracy

12 1 In a Single laboratory (EMSL)

uSing a mIxed industrial-domestIc

waste effluent containing 22 ,ug

Cr 6+/L and spIked WIth a

concentratIon of 50,ug Cr 6

+/L the

standard deVIatIons were ..t 1 0 and ±

27, respectIvely WIth a spike recovery

of 94%

12 2 Recoveries of a 40 ,ug Cr 6+/L

spIke In diluted tannery and platIng

waste effluents were 96% and 93%,

respectIvely

12 3 USing CinCinnatI, Ohio tap

water spiked at concentratIons of

5,10, and 50,ug Cr6+/L the standard

deVIatIons were ± 0 7, ±O 6, and

±O 6 respectIvely SpIke rec-overy at

all three levels was 102%

12 4 A 1000,ug Cr 3+/L standard

solutIon analyzed by thIS method

YIelded a result of 8,ug Cr6

+/L WIth a

relatIve standard deVIatIon of 19%

12 5 The data from 5 ,ug Cr6+/L tap

water spIke was used to calculate

method detectIon limIt (MOL) WIth

99% confIdence as deSCribed In

'Trace Analyses for Wastewater," J

Glaser, 0 Foers!, G McKee, S

Quave, W Budde, EnVironmental

SCIence and Technology Vol 15,

Number 12, page 1426, December

1981 The calculated MOL for

CinCinnati drinking water IS 2 3,ug/L

,

21853 Dec 1982
COBALT

Method 219.1 (Atomic Absorption, direct aspiration)

STORET NO. Total 01037

Dissolved 01035

Suspended 01036

Optimum ConcentratIOn Range:

SensitIvity. 02 mg/l

Detection Limit: 0 05 mg/l

05-5 mg/l usmg a wavelength of240 7 nm

Preparation of Standard SolutIOn

1 Stock SolutIOn DIssolve 4 307 g of cobaltous chlonde, CoClz-6HzO (analytIcal reagent

grade), m deIOlllzed dIstdled water Add 10 ml of concentrated llltnc aCId and ddute to I

hter wIth deIOlllzed dIstIlled water 1ml = I mg Co (1000 mg/l)

2 Prepare ddutions of the stock cobalt solutIOn to be used as cahbratIOn standards at the

tIme of analysIs The cahbratIOn standards should be prepared usmg the same type of

aCId and at the same concentratIOn as WIll result m the sample to be analyzed eIther

dIrectly or after processmg

Sample Preservation

I For sample handhng and preservatIon, see part 4 I of the AtomIC AbsorptIon Methods

sectIon ofthIS manual

Sample Preparation

1 The procedures for preparation of the sample as gIVen m parts 4 1 I thru 4 1 4 of the

AtomIC AbsorptIOn Methods sectIon ofthIS manual have been found to be satisfactory

Instrumental Parameters (General)

I Cobalt hollow cathode lamp

2 Wavelength 240 7 nm

3 Fuel Acetylene

4 OXIdant AIr

5 Type ofFlame OXIdIzmg

AnalysIs Procedure

I For analysIs procedure and calculatIOn, see "DIrect AspIratIOn", part 9 1 ofthe AtomIC

AbsorptIOn Methods sectIOn ofthis manual

Approved for NPDES

Issued 1974

Editonal reVISIon 1978

219 1-1
Notes

1

2

For levels of cobalt below 100 ug/1, eIther the SpecIal ExtractIOn Procedure, gIven m

part 9 2 of the AtomIC AbsorptIon Methods sectIOn or the furnace techmque, Method

219 2 IS recommended,

Data to be entered mto STORET must be reported as ug/1

Precision and Accuracy

1 In a smgle laboratory (EMSL), usmg a mIxed mdustrIal-domestic waste eftluent at

concentratIOns of0 20, 1 0 and 5 Omg Co/I, the standard deVIatIons were ±O 013, ±O 01

and ±O OS, respectIvely Recovenes at these levels were 98%, 98%, and 97%,

respectively

1 '

219 1-2
COBALT

Method 219.2 (Atomic Absorption, furnace technique)

STORET NO. Total 01037

Dissolved 01035

Suspended 01036

OptimumConcentration Range: 5-100 ug/l

DetectIOn LImit: 1 ug/l

Preparation ofStandard SolutIOn

1 Stock solutIOn Prepare as descnbed under "dIrect aSpIratIOn method"

2 Prepare dl1utlons of the stock solutIOn to be used as cahbration standards at the time of

analysIs These solutions are also to be used for "standard addItions"

3 The cahbratton standard should be dl1uted to contam 05% (v/v) HN03

Sample Preservation

1 For sample handlmg and preservatIOn, see part 4 1 of the AtomIC AbsorptIOn Methods

sectIOn ofthIS manual

Sample Preparation

1 Prepare as descrIbed under "dIrect aspIratIon method" Sample SolutIons for analysIs

should contam 05% (v/v) HN03

Instrument Parameters (General)

1 DrymgTImeandTemp 30sec-125°C

2 Ashmg TIme and Temp 30 sec-900°C

3 AtoIllizmg TIme and Temp 10 sec-27oo°C

4 Purge Gas Atmosphere Argon

5 Wavelength 2407 nm

6 Other operatmg parameters should be set as specIfied by the partIcular mstrument

manufacturer

AnalYSIS Procedure

1 For the analysIs procedure and the calculation, see "Furnace Procedure" part 9 3 ofthe

AtomIC AbsorptIon Methods SeGtlon ofthIS manual

Notes

1 The above concentratIOn vailles and lUstrument condItIOns are for a Perkm-Elmer HGA2100, based on the use of a 20 UllUJectlOn, contlUuous flow purge gas and non-pyrolytic

Approved for NPDES

Issued 1978

2192-1
graphIte Smaller SIze furnace devIces or those employmg faster rates of atomIzatIOn can

be operated usmg lower atomIzatIOn temperatures for shorter tIme penods than the

above recommended settmgs

2 The use ofbackground correctIon IS recommended

3. NItrogen may also be used as the purge gas but wIth reported lowersensItIvIty

4 For every sample matnx analyzed, venfication IS necessary to determme that method of

standard addItion IS not reqUIred (see part 5 2 I of the AtomIC AbsorptIon Methods

section ofthIS manual)

5 Ifmethod ofstandard addItIon IS requIred, follow the procedure gIven earlIer m part 8 5

ofthe AtomIC Absorption MethodssectIon ofthIS manual

6 Data to be entered mto STORETmust be reported as ug/l

Precision and Accuracy

1 PreclSlon and accuracy data are not avaIlable at thIs tIme

2192-2
. ,

'f CQPPER

Method 220.1 (Atomic Absorption, direct aspiration)

STORET NO. Total 01042

Dissolved 01040 ,

Suspended 01041

Optimum Concentration Range: ,0 2-5 mg/1 usmg a wavelength oQ24 7 nm

SensitivIty: 0 1mg/1 -

Detection LimIt: 0 02 mg/1

Preparation ofStandard SolutIOn

1 Stock SolutIOn Carefully weIgh 190 g of elec!rolyte copper (analytIcal reagent grade)

DIssolve m 5 ml redIstIlled HN03 and make up to 1 lIter wIth deIOnIzed dIstIlled water

Fmal concentratIOn IS 1mg Cu per m1 (1000 mg/1)

2 Prepare dIlutIOns of the stock solutIOn to be used as calIbratIOn standards at the time of

analysIs The calIbratIOn standards should be prepared usmg the same type of aCId and at

the same concentratIOn as wIll result tn the sample to be analyzed eIther dIrectly or after

processmg

Sample PreservatIOn

1 For sample handlIng and preservatIOn, see part 4 I of the AtomIc AbsorptIOn Methods

sectIOn ofthIS manual

Sample Preparation

1 The procedures for preparatIOn of the sample as gIven m parts 4 1 1 thru 4 1 4 of the

AtomIc AbsorptIOn Methods sectIOn ofthIS manual have been found to be satisfactory

Instrumental Parameters(General)

1 Copper hollow cathode lamp

2 Wavelength 324 7 nm

3 Fuel Acetylene

4 OXIdant AIr

5 Type offlame OXIdIzmg

AnalysIs Procedure

I For analysIs procedure and calculatIOn, see "DIrect AspiratIOn", part 9 1 ofthe AtomIc

AbsorptIOn Methods sectIOn ofthIs manual

Approved for NPDES

Issued 1971

EdItOrial reVISIOn 1974 and 1978

220 1-1 .".
Notes

1

2.

3

4

Forlevels ofcopper below 50 ug/1, elther the Speclal ExtractlOn Procedure, glven m part

9 2 ofthe Atomlc AbsorptlOn Methods sectlOn or the furnace techmque, Method 220 2,

isrecommended

Numerous absorptlon lmes are available for the determmatlon of copper By selectmg a

smtable absorptlOn wavelength, copper samples may be analyzed over a very wlde range

ofconcentratlOn The followmg lmes may be used

327.4 nm Relative Sensltivlty 2

216.5 nm Relatlve Sensltivlty 7

222.5 nm Relative SensltlVlty 20

Data to be entered mto STORET must be reported as ug/1

The 2,9-dlmethyl-1, lO-phenanthrohne colonmetnc method may also be used (Standard

Methods, 14th EdltlOn, p 196)

Precision and Accuracy

1. An mterlaboratory study on trace metal analyses by atomlC absorption was conducted by

the Quahty Assurance and Laboratory EvaluatlOn Branch of EMSL SlX synthetlc

concentrates contalmng varymg levels of alummum, cadmlUm, chromlum, copper, lron,

manganese, lead and zmc were added to natural water samples The statlstical results for

copper were as follows

Standard

Number True Values Mean Value Devlation Accuracy as

of Labs ug/hter ug/hter ug/hter % Blas

91 302 305 56 09

92 332 324 56 -24

86 60 64 23 70

84 75 76 22 13

66 75 97 61 297

66 120 139 97 155

2201-2
COPPER

Method 220.2 (Atomic Absorption, furnace technique)

STORET NO. 01042

Dissolved 01040

Suspended 01041

Optimum ConcentratIOn Range: 5-100 ug/l

Detection LImIt: 1 ug/l

PreparatIOn ofStandard SolutIOn

1 Stock solutlOn Prepare as descrIbed under "dIrect aspiratlOn method"

2 Prepare ddutlOns of the stock solutlOn to be used as cahbratlOn standards at the time of

analysIs These solutlOns are also to be used for "standard additlOns"

3 The cahbratlOn standard should be dIluted to contam 0 5% (vIv) HN03

Sample PreservatIon

1 For sample handlmg and preservatlOn, see part 4 1 of the AtomIC AbsorptlOn Methods

sectlOn ofthIS manual

Sample PreparatIOn

1 Prepare as descrIbed under "dIrect aspiratlOn method" Sample solutlOns for analysIs

should contam 0 5% (v/v)HN03

Instrument Parameters (General)

1 Drymg TIme and Temp 30 sec-125°C

2 Ashmg Time and Temp 30 sec-'90 O°C

3 AtomIzmg TIme and Temp 10 sec-2700°C

4 Purge Gas Atmosphere Argon

5 Wavelength 3247nm

6 Other operatmg parameters should be set as specIfied by the partIcular mstrument

manufacturer

AnalYSIS Procedure

1 For the analysIs procedure and the calculatlOn, see "Furnace Procedure" part 9 3 of the

AtomIc AbsorptlOn Methods sectlOn ofthIS manual

Notes

1 The above concentratlOn values and mstrument conditlOns are for a Perkm-Elmer HGA2100, based on the use of a 20 ul mJectlOn, contmuous flow purge gas and non-pyrolytIc

Approved for NPDES

Issued 1978

2202-1
graphite Smaller size furnace devices or those employmg faster rates of atomizatIOn can

be operated usmg lower atOmlzatlOn temperatures for shorter time penods than the

above recommended settmgs

2 Background correctIOn may be reqUIred Ifthe sample contams high dissolved sohds

3 Nitrogen may also be used as the purge gas

4 For every sample matnx analyzed, venficatlOn IS necessary to determme that method of

standard addition IS not reqUIred (see part 52 1 of the AtomiC Absorption Methods

sectIon ofthis manual)

5. Ifmethod ofstandard addition IS required, follow the procedure given earher m part 8 5

ofthe Atomlc Absorption Methods sectIOn ofthis manual

6 Data to be entered mto STORET must be reported as ug/l

Precision and Accuracy

1 PrecIsion and accuracy data are not avatlable at thiS time

2202-2
GOLD

Method 231.1 (Atomic Absorption, dire~t aspiration)

STORET NO. Total 71910

Optimum Concentration Range: 05-20 mg/1 usmg a wavelength of242 8 nm

SensitIvIty: 0 25 mg/1

Detection LImIt: 0 1mg/1

Preparation ofStandard Solution

1 Stock SolutlOn DIssolve 01000 g of gold metal m a mmimum volume of aqua reglat

Take to near dryness, cool, add 5 ml HCI, and dIlute to 100 ml wIth delOmzed water

Store m an amber glass bottle (1 ml = 1mg Au)

2 A standard AAS solutlOn of chloroaunc aCId, HAuCI4, 1000 mg/1 m aqueous matnx IS

avaIlable from Alfa Products, Beverly, Massachusetts 01915

Cat #88068

3 Prepare dIlutlOns of the stock solutlOn to be used as cahbratlOn standards at the tIme of

analysIs The cahbratlOn standards should be prepared to contam 0 5% (v/v) HN03

Sample Preservation

1 For sample handhng and preservatlOn, see part 4 1 of the AtomIc AbsorptlOn Methods

sectlOn ofthIs manual

Sample Preparation

1 Transfer a representatIve ahquot ofthe well mIxed sample to a Gnffin beaker and add 3

ml of conc dIstIlled HN03 Place the beaker on a steam bath and evaporate to near

dryness Cool the beaker and cautlOusly add a 5 ml portlOn of aqua regta (See below for

preparatlOn of aqua regia t) Cover the beaker wIth a watch glass and return to the steam

bath Contmue heatmg the covered beaker for 30 mmutes Remove cover and evaporate

to near dryness Cool and add 1 1 dIstIlled HN03 (1 ml per 100 m1 dIlutIon) Wash down

the beaker walls and watch glass wIth dIstIlled water and filter the sample to remove

sIhcates and other msoluble matenal that could clog the atomIzer Adjust the volume to

some predetermmed value based on the expected metal concentratlOn The sample IS now

ready for analysIs

tAqua regta-prepare ImmedIately before use by carefully addmg three volumes of

conc HCL to one volume of conc HN03

Approved for NPDES

Issued 1976

Techmcal reVISIon 1978

231 1-1
Instrumental Parameters (General)

1 Gold hollow cathode lamp

2 Wavelength 242 8 nm

3 Fuel Acetylene

4 OXIdant AIr

5. Type offlame OXIdIzmg

Analysis Procedure

1. For analysIs procedure and calculatiOn, see "Direct AspIratiOn", part 9 1 ofthe AtomIC

AbsorptiOn Methods sectIon ofthIS manual

Notes

1 For concentratIons of gold below 100 ug/l, the furnace procedure, Method 231 2, IS

recommended

Precision and Accuracy

1. PrecIsIon and accuracy data are not avallable at thIS tIme

231 1-2
GOLD

Method 231.2 (Atomic Absorption, furnace technique)

STORET NO. 71910

OptImum Concentration Range:

DetectIon Limit:

5-100 ug/l

1 ug/l

Preparation ofStandard SolutIOn

1 Stock solutiOn Prepare as descnbed under "direct aSpiratiOn method"

2 Prepare ddutiOns of the stock solutiOn to be used as cahbratlOn standards at the time of

analysIs These solutiOns are also to be used for "standard additiOns"

3 The cahbratiOn standard should be dduted to contam 05% (v/v) HN03

Sample PreservatIon

1 For sample handhng and preservatiOn, see part 4 1 of the AtomiC AbsorptiOn Methods

sectiOn ofthis manual

Sample PreparatIon

1 Prepare as descnbed under "direct aspiratiOn method" Sample solutiOns for analysIs

should contam 0 5% (vIv) HN03

Instrument Parameters (General)

1 Drymg Time and Temp 30 sec-125°C

2 Ashmg Time and Temp 30 sec-600°C

3 Atomlzmg Time and Temp 10 sec-2700°C

4 Purge Gas Atmosphere Argon

5 Wavelength 242 8 nm

6 Other operatmg parameters should be set as speCified by the partlCular mstrument

manufacturer

Analysis Procedure

1 For the analysIs procedure and the calculatiOn, see "Furnace Procedure" part 9 3 ofthe

AtomiC AbsorptiOn Methods sectiOn ofhis manual

Notes

1 The above concentratiOn values and mstrument conditions are for a Perkm-Elmer HGA2100, based on the use of a 20 ul mJectiOn, contmuous flow purge gas and non-pyrolytlc

graphite

Approved for NPDES

Issued 1978

231 2-1
2 The use ofbackground correctIOn IS recommended

3 For every sample matnx analyzed, venficatlOn IS necessary to determme that method of

standard addition IS not reqUlred (see part 5 2 1 of the AtomiC AbsorptIOn Methods

sectIOn oftms manual)

4 Ifmethod ofstandard addition IS reqUlred, follow the procedure given earlier m part 8 5

ofthe AtomiC AbsorptIOn Methods sectIOn ofthiS manual

5 Data to entered mto STORET must be reported as ug/l

Precision and Accuracy

1 PreciSion and accuracy data are not aval1able at thiS time

"t "

III I

2312-2
IRIDIUM

, '

Method 235.1 (Atomic Absorption, direct aspiration)

STORET NO. Total*

Optimum Concentration Range: 20-500 mg/1 usmg a wavelength of264 0 nm

SensitivIty: 8mg/1

Detection Limit· 3 mg/1

Preparation of Standard Solution

1 Stock SolutIOn DIssolve 1 147 g of ammomum chloromdate (NH4)2 IrCI6, m a mmimum

volume of 1% (vIv) HCI and dl1ute to 100 ml wIth 1% HCI (1 ml = 5mg Ir)

2 A standard AAS solutIOn of chioromdic aCId, HJrCI6, 1000 mg/1 m aqueous matnx IS

aval1able from Alfa Products, Beverly, Massachusetts 01915

Cat #88072

3 Prepare dl1utIOns of the stock solutIOn to be used as cahbratIOn standards at the tIme of

analysIs The cahbratIOn standards should be prepared to contam 05% (v/v) HN03

Sample Preservation

1 For sample handhng and preservatIOn, see part 4 1 of the AtomIC AbsorptIon Methods

sectIon ofthIS manual

Sample Preparation

1 Transfer a representatIve ahquot ofthe well mIxed sample to a Gnffin beaker and add 3

ml of cone dIstIlled HN03 Place the beaker on a steam bath and evaporate to near

dryness Cool the beaker and cautIOusly add a 5 ml portIOn of aqua regIa (See below for

preparatIon of aqua regIa t) Cover the beaker wIth a watch glass and return to the steam

bath Contmue heatmg the covered beaker for 30 mmutes Remove cover and evaporate

to near dryness Cool and add 1 1 dIstl1led HN03 (1 ml per 100 ml dtlutIon) Wash down

the beaker walls and watch glass wIth dIstl1led water and filter the sample to remove

sIhcates and other msoluble matenal that could clog the atomIzer Adjust the volume to

some predetermmed value based on the expected metal concentratIOn The sample IS now

ready for analysIs

tAqua regia-prepare ImmedIately before use by carefully addIng three volumes

cone Hel to one volume of cone HN03

*Not AssIgned

Approved for NPDES

Issued 1976

Techmcal reVISIon 1978

235 1-1
Instrumental Parameters (General)

1. Indmm hollow cathode lamp

2. Wavelength 2640 nm

3 Fuel Acetylene

4 OXIdant Atr

5. Type offlame Reducmg IIIII II ,,

AnalYSIS Procedure

1. For analysIs and calculatIOn, see "DIrect AspIratIOn", part 9 I ofthe AtomIc AbsorptIOn

MethodssectIOn ofthIS manual

Notes

1. For concentratIOns of tndmm below 3 mg/I, the furnace procedure, Method 235 2, IS

recommended

Precision and Accuracy

1. Precision and accuracy data are not avaIlable at this time

235 1-2
IRIDIUM

Method 235.2 (Atomic Absorption, furnace technique)

STORET NO. Total*

OptImum ConcentratIOn Range: 0 1-1 5 mg!1

Detection LImIt: 0 03 mgll

Preparation ofStandard Solution

1 Stock solutIOn Prepare as descnbed under "dtrect aSptratIOn method"

2 Prepare dtlutIOns ofthe stock solutIOn to be used as cahbratIOn standards at the tIme of

analysts These solutIOns are also to be used for "standard addttIOns"

3 The calculatIOn standard should be dIluted to contam 0 5% (vIv) HN03

Sample Preservation

1 For sample handhng and preservatIOn, see part 4 1 of the Atomtc AbsorptIOn Methods

sectIOn ofthts manual

Sample Preparation

1 Prepare as descnbed under "dtrect aSptratIOn method" Sample soluttons for analysts

should contam 0 5% (v/v) HN03

Instrument Parameters (General)

1 Drymg Ttme and Temp 30 sec-125°C

2 Ashmg Ttme and Temp 30 sec-600°C

3 Atomtzmg Ttme and Temp 10 sec-2800°C

4 Purge Gas Atmosphere Argon

5 Wavelength 264 0 nm

6 Other operatmg parameters should be set as spectfied by the parttcular mstrument

manufacturer

AnalYSIS Procedure

1 For the analysts procedure and the calculatIOn, see f'Furnace Procedure" part 9 3 ofthe

Atomtc Absorptton Methods sectIOn ofthts manual

*Not Asstgned

Approved for NPDES

Issued 1978

2352-1
I Notes

1

2

3

4

5

6

The above concentratIOn values and Instrument condItions are for a PerkIn-Elmer HGA2100, based on the use of a 20 ul InJectIOn, contInUOUS flow purge gas and pyrolytIc

graphIte

The use ofbackground correctIOn IS recommended

NItrogen may also be used as the purge gas

The 208 9 nm lIne IS a factor of 3X more senSItive than the 264 0 nm lIne, but reqUIres a

very narrow sht to be dlscnmInated from nearby non-absorbIng hnes

For every sample matnx analyzed, venficatlon IS necessary to determIne that method of

standard addItion IS not reqUIred (see part 5 2 1 of the AtomiC AbsorptIOn Methods

section ofthis manual)

Ifmethod ofstandard addItion IS reqUIred, follow the procedure gIven earher In part 8 5

ofthe AtomIC AbsorptIOn Methods sectIOn ofthIS manual

Precision and Accuracy

1 PreCISIon and accuracy data are not avaIlable at thIs tIme

"

2352-2
IRON

Method 236.1 (Atomic Absorption, direct aspiration)

STORET NO. Total 01045

Dissolved 01046

Suspended 01044

Optimum ConcentratIOn Range: 03-5 mg/l usmg a wavelength of248 3 nm

Sensitivity: 0 12 mg/l

Detection Limit 0 03 mg/l

Preparation ofStandard Solution

1 Stock SolutIOn Carefully weigh 1 000 g of pure Iron wire (analytical reagent grade) and

dissolve m 5 ml redistilled HN03, warmmg Ifnecessary When solutIOn IS complete make

up to 1hter With deIOnIzed distilled water 1ml = 1mg Fe (1000 mg/I)

2 Prepare dilutions of the stock solutIOn to be used as cahbratlon standards at the time of

analySIS The cahbratlOn standards should be prepared usmg the same type ofaCid and at

the same concentratIOn as Will result m the sample to be analyzed either directly or after

processmg

Sample Preservation

I For sample handhng and preservatIOn, see part 4 I of the Atomic Absorption Methods

sectIOn ofthis manual

Sample Preparation

1 The procedures for preparation of the sample as given m parts 4 1 I thru 4 I 4 of the

Atomic AbsorptIOn Methods sectIOn ofthis manual have been found to be satisfactory

Instrumental Parameters (General)

1 Iron hollow cathode lamp

2 Wavelength 248 3 nm

3 Fuel Acetylene

4 OXidant Air

5 Type offlame OXldlzmg

AnalYSIS Procedure

1 For analySIS procedure and calculatIOn, see "Direct AspIratIOn", part 9 1 ofthe Atomic

Absorption Methods sectIOn ofthis manual

Approved for NPDES

Issued 1971

Edltonal revIsion 1974 and 1978

236 1-1
Notes

1

2

3.

4.

The folloWIng hnes may also be used

248 8 nm Relative SensItivIty 2

271 9 nm Relative SensltlVlty 4

302 1nm Relative SensItivIty 5

252 7 nm Relative SensItIvIty 6

372 0 nm Relative SensItIvIty 10

Data to be reported Into STORET must be reported as ug/l

The 1)1O-phenanthrohne colonmetnc method may also be used (Standard Methods,

14th EdItion) p 208)

For concentratlOns of Iron below 005 mg/l) eIther the SpecIal ExtractIon Procedure

glVen In part 9 2 of the AtomIC AbsorptIon Methods sectIon or the furnace procedure,

Method 236 2) IS recommended

Precision and Accuracy

1 An Interlaboratory study on trace metal analyses by atomlC absorptlOn was conducted by

the Quahty Assurance and Laboratory EvaluatIon Branch of EMSL SIX synthetIC

concentrates contamIng varyIng levels of alumInum) cadmmm, chromJum, copp~r, lro~)

manganese) lead and ZInC were added to natural water samples The statistical results fOf

Iron were as follows

Standard

Number True Values Mean Value DevIatIOn Accuracy as

Of Labs ug/1Iter ug/bter ug/hter % BIas ,

82 840 855 173 1 8

85 700 680 178 -28

78 350 348 131 -0,5

79 438 435 183 -07

57 24 58 69 141

54 10 48 69 382

236 1-2
IRON

Method 236.2 (Atomic Absorption, furnace technique)

STORET NO. Total 01045

Dissolved 01046

Suspended 01044

Optimum Concentration Range: 5-100 ug/l

Detection Limit: 1 ug/l

Preparation ofStandard Solution

1 Stock SolutlOn Prepare as descnbed under "direct asplratlOn method"

2. Prepare dilutlOns of the stock solutlOn to be used as cahbratlOn standards at the time of

analysIs These solutlOns are also to be used for "standard additions"

3 the cahbratlOn standard should be diluted to contam 0 5% (vIv) HN03

Sample Preservation

1 For sample handlmg and preservation, see part 4 1 of the Atomic AbsorptlOn Methods

sectlOn ofthis manual

Sample Preparation

1 Prepare as descnbed under "direct asplratlOn method" Sample solutions for analysts

should contam 05% (v/v) HN03

Instrument Parameters (General)

1 DrymgTlmeand Temp 30sec-125°C

2 Ashmg Time and Temp 30 sec-lOOO°C

3 Atomlzmg Time and Temp 10 sec-2700°C

4 Purge Gas Atmosphere Argon

5 Wavelength 248 3 nm

6 Other operatmg parameters should be set as specified by the particular mstrument

manufacturer

AnalysIs Procedure

1 For the analysIs procedure and the calculation, see "Furnace Procedure" part 9 3 ofthe

Atomic AbsorptlOn Methods sectlOn ofthis manual

Notes

1 The above concentratlOn values and mstrument conditions are for a Perkm-Elmer HGA2100, based on the use of a 20 ul mJectlOn, contmuous flow purge gas and non-pyrolytic

Approved for NPDES

Issued 1978

2362-1
graphite Smallersize furnace devices or those employing faster rates of atomizatIOn can

be operated uSing lower atomizatIOn temperatures for shorter time penods than the

above recommended settings

2 The use ofbackground correctIOn IS recommended

3 Nitrogen may also be used as the purge gas

4 For every sample matnx analyzed, venficatlOn IS necessary to determine that method of

standard addition IS not reqUIred (see part 5 2 1 of the AtomiC Absorption Methods

sectIOn ofthis manual)

5 Ifmethod ofstandard additIOn IS reqUIred, follow the procedure given earlier In part 8 5

ofthe AtomiC Absorption Methods sectIOn ofthis manual

6 Data to be entered Into STORET must be reported as ug/l

Precision and Accuracy

1 Precision and accuracy data are not avadable at this time

2362-2
LEAD

Method 239.1 (Atomic Absorption, direct aspiration)

STORET NO. Total 01051

Dissolved 01049

Suspended 01050

Optimum Concentration Range: 1-20 mg/l USIng a wavelength of283 3 nm

SensItivIty: 0 5 mg/l

Detection LImit: 0 1mg/l

Preparation of Standard Solution

1 Stock SolutIOn Carefully weIgh 1 599 g of lead nItrate, Pb(N03)2 (analytical reagent

grade), and dIssolve In deIOnIZed dIstilled water When solutIOn IS complete aCIdIfy wIth

10 ml redIstIlled HN03 and dIlute to 1 lIter wIth deIOnIZed dIstIlled water 1ml = 1 mg

Pb (1000 mg/l)

2 Prepare dIlutIOns of the stock solutIOn to be used as calIbratIon standards at the tIme of

analysIs The calIbratIOn standards should be prepared USIng the same type of aCId and at

the same concentratIOn as wIll result In the sample to be analyzed eIther dIrectly or after

processIng

Sample Preservation

1 For sample handlIng and preservation, see part 4 1 of the AtomIC AbsorptIOn Methods

sectIOn OfthiS manual

Sample PreparatIOn

1 The procedures for preparatIOn of the sample as given In parts 4 1 1 thru 4 1 4 of the

AtomIC AbsorptIOn Methods sectIOn ofthIS manual have been found to be satisfactory

Instrumental Parameters(General)

1 Lead hollow cathode lamp

2 Wavelength 2833 nm

3 Fuel Acetylene

4 OXIdant AIr

5 Type offlame OXIdIZIng

AnalYSIS Procedure

1 For analysIs procedure and calculatIOn, see "DIrect AspIratIOn", part 9 1 ofthe AtomIC

AbsorptIOn Methods sectIOn ofthIS manual

Approved for NPDES and SDWA

Issued 1971

EdItorIal reVISIon 1974 and 1978

239 1-1
Notes

1.

2

3.

4

5

The analysIs ofthis metal IS exceptIOnally sensitive to turbulence and absorption bands In

the flame Therefore, some care should be taken to POSltl~~ the lIght beam In the most

stable, center portIOn of the flame To do this, first adjust the burner to maximize the

absorbance readIng with a lead standard Then, aspirate a water blank and make mInute

adjustments In the burner alIgnment to mlmmlze the signal

For levels oflead below 200 ug/l, either the Special ExtractIOn Procedure given In part

9 2 ofthe Atomic AbsorptIOn Methods sectIOn or the furnace techmque, Method 239 2,

IS recommended

The follOWIng lInes may also be used

2170 urn RelatIve Sensitivity 04

261 4 nm Relative SensItivity 10

For quality control reqUIrements and optIOnal recommendatIOns for use In dnnkIng

water analyses, see part 10 ofthe Atomic AbsorptIOn Methods section oftlus manual

Data to be entered Into STORET must be reported as ug/l

Precision and Accuracy

1 An Interlaboratory study on trace metal analyses by atomic absorptIOn was conducted by

the Quality Assurance and Laboratory EvaluatIOn Branch of EMSL SIX synthetic

concentrates contaInIng varyIng levels of alumInum, cadmIUm, chromIUm, copper, Iron,

manganese, lead and ZInC were added to natural water samples The statistical results for

lead were as follows

Standard

Number True Values Mean Value DevlatlOn Accuracy as

of Labs ug/ltter ug/ltter ug/ltter % BIas

74 367 377 128 29

74 334 340 111 18

64 101 101 46 -02

64 84 85 40 1 1

61 37 41 25 96

60 25 31 22 257

239 1-2
LEAD

Method 239.2 (Atomic Absorption, furnace technique)

STORET NO. Total 01051

Dissolved 01049

Suspended 01050

Optimum Concentration Range: 5-100 ug/l

Detection LImIt: 1ug/l

Preparation of Standard Solution

1 Stock solutIOn Prepare as descnbed under "dIrect aSpIratIOn method"

2 Lanthanum NItrate SolutIOn DIssolve 58 64 g of ACS reagent grade La203 m 100 ml

conc HN03and dIlute to 1000 ml wIth deIOnIZed dIstIlled water 1ml = 50 mg La

3 Workmg Lead SolutIOn Prepare dIlutIOns of the stock lead solutIOn to be used as

cahbratIOn standards at the tIme of analysIs Each cahbratIOn standard should contam

05% (v/v) HN03 To each 100 ml of dIluted standard add 10 ml of the lanthanum

nItrate solutIOn

Sample Preservation

1 For sample handhng and preservatIOn, see part 4 1 of the AtomIc AbsorptIOn Methods

sectIOn ofthIS manual

Sample Preparation

1 Prepare as descnbed under "direct aspIratIOn method" Sample solutIOns for analysIs

should contam 0 5% (vIv) HN03

2 To each 100 ml of prepared sample solutIOn add 10 ml ofthe lanthanum nItrate solutIOn

Instrument Parameters (General)

1 Drymg TIme and Temp 30 sec-125°C

2 Ashmg TIme and Temp 30 sec-500°C

3 AtomIzmg TIme and Temp 10 sec-2700°C

4 Purge Gas Atmosphere Argon

5 Wavelength 2833 nm

6 Other operatmg parameters should be set as specIfied by the partlCular mstrument

manufacturer

AnalysIs Procedure

1 For the analysIs procedure m the calculatIOn see "Furnace Procedure", part 9 3 of the

AtomIc AbsorptIOn Methods sectIOn ofthIS manual

Approved for NPDES and SDWA

Issued 1978

2392-1
Notes

1

2

3

4

5

6

7

8

9

The above concentratIon values and Instrument condItIOns are for a Perkin-Elmer HGA2100, based on the use ofa 20 ul inJectIon, continUous flow purge gas and non-pyrolytic

graphIte Smaller SIze furnace devIces or those employing faster rates of atomIzatIOn can

be operated USing lower atomIzatIOn temperatures for shorter tIme perIods than the

above recommended settings i'

The use ofbackground correctIOn IS recommended

Greater sensItIVIty can be achIeved USing the 2170 nm line, but the optImum

concentratIOn range IS reduced The use of a lead e1ectrodeless dIscharge lamp at thIS

lower wavelength has been found to be advantageous Also a lower atomIzatIOn

temperature (2400°C) may be preferred

To suppress sulfate Interference (up to 1500 ppm) lanthanum IS added as the nitrate to

both samples and calIbratIOn standards (AtomIc AbsorptIon Newsletter Vol 15, No 3,

p 71, May-June 1976 )

Since glassware contaminatIOn IS a severe problem In lead analYSIS, all glassware should

be cleaned ImmedIately prIor to use, and once cleaned, should not be open to the

atmosphere except when necessary

For every sample matrIX analyzed, verIficatIOn IS necessary to determine that method of

standard addItIOn IS not reqUIred (see part 5 2 1 of the AtomIC AbsorptIOn Methods

section OfthiS manual)

For qualIty control reqUIrements and optIOnal recommendatIons for use In drinking

water analyses, see part 10 ofthe AtOmIC AbsorptIOn Methods sectIOn ofthIS manual

Ifmethod ofstandard addItIon IS reqUIred, follow the procedure gIven earlIer In part 8 5

ofthe AtomIC AbsorptIon Methods sectIon ofthIS manual

Data to be entered Into STORET must be reported as ug/1

Precision and Accuracy

1 In a Single laboratory (EMSL), USing CinCinnatI, OhIO tap water spIked at concentratIons

of 25, 50, and 100 ug Pb/1, the standard deVIatIOns were ±1 3, ±1 6, and ±3 7,

respectIvely RecoverIes at these levels were 88%, 92%, and 95% respectIvely

2392-2
MAGNESIUM

Method 242.1 (Atomic Absorption, direct aspiration)

STORET NO. Total 00927

Dissolved 00925

Suspended 00926

Optimum Concentration Range: 002-0 5 mg/l usmg a wavelength of285 2 nm

SensItivity: 0007 mg/l

DetectIon Limit: 0 001mg/l

Preparation of Standard Solution

1 Stock SolutlOn D1ssolve 0829 g ofmagneslUm oX1de, MgO (analytlCal reagent grade), m

10 ml ofred1stl1led HN03and dl1ute to 1 hter w1th delOmzed d1stl1led water 1 ml = 050

mg Mg (500 mg/l)

2 Lanthanum chlonde solutlOn D1ssolve 29 g ofLa203, slowly and m small portlOns m 250

ml conc HCI, (CautlOn ReactlOn 1S vlOlent), and d1lute to 500 ml w1th delOmzed d1st1lled

water

3 Prepare dl1utlOns ofthe stock magneslUm solutlOn to be used as cahbratlOn standards at

the t1me of analys1s To each 10 ml volume of cahbratlOn standard and sample ahke add

1 0 ml ofthe lanthanum chlonde solutlOn, 1e , 20 ml ofstandard or sample +2 ml LaCl3

= 22ml

Sample Preservation

1 For sample handhng and preservatlOn, see part 4 1 of the Atom1C AbsorptlOn Methods

sectlOn ofth1s manual

Sample Preparation

1 For the analys1s oftotal magneslUm m domest1c and mdustna! effluents, the procedures

for the determmatlOn of total metals as glven m parts 4 1 3 and 4 1 4 of the AtomlC

AbsorptlOn Methods sectlOn ofth1s manual have been found to be satisfactory

2 For amb1ent waters, a representative ahquot of a well-m1xed sample may be used d1rectly

for analys1s If suspended sohds are present m suffic1ent amounts to clog the nebuhzer,

the sample may be allowed to settle and the supernatant hqUld analyzed d1rectly

3 Samplesshould be preserved w1th (1 1) mtnc aC1d to a pH of2 at the t1me ofcollectlOn

Instrumental Parameters (General)

1 MagneslUm hollow cathode lamp

2 Wavelength 2852nm

Approved for NPDES

Issued 1971

Ed1tonal reV1SlOn 1974 and 1978

2421-1
3.

4.

5

Notes

1.

2.

3

4

5

Fuel Acetylene

OXIdant Air

Type offlame OXldlzmg

The mterference caused by alummum at concentratIOns greater than 2 mg/l IS masked

by addition of lanthanum Sodmm, potassmm and calcIUm cause no mterference at

concentratIOns less than 400 mg/l

The followmg lme may also be used

202 5 nm Relative SensItivity 25

To cover the range of magnesmm values normally observed m surface waters (0 1-20

mg/l), It IS suggested that either the 2025 nm lme be used or the burner head be rotated

A 90' rotation of the burner head will produce approxtmately one-eighth the normal

sensitivity

Data to be entered mto STORET must be reported as mg/l

The gravlmetnc method may also be used (Standard Methods, 14th Edition, p 221)

Precision and Accuracy

1 In a smgle laboratory (EMSL), usmg dlsttlled water spiked at concentratIOns of 2 1 and

8 2 mg Mg/l the standard deviatIOns were ±O 1 and ±O 2, respectively Recovenes at

both ofthese levels were 100%

242 1-2
MANGANESE

Method 243.1 (Atomic Absorption, direct aspiration)

STORET NO. Total 01055

Dissolved 01056

Suspended 01054

Optimum Concentration Range: 0 1-3 mg!1 usmg a wavelength of279 5 nm

SensItIvity: 0 05 mg!1

Detection Limit: 001 mg!1

Preparation ofStandard SolutIon

1 Stock SolutIOn Carefully weigh I 000 g of manganese metal (analytlCal reagent grade)

and dissolve m 10 ml of redistilled HN03 When solutIOn IS complete, dllute to 1 hter

wlthl%(VIV)HCllml = ImgMn(1000mg!l)

2 Prepare dilutIOns of the stock solution to be used as cahbratlOn standards at the time of

analysIs The cahbratlOn standards should be prepared usmg the same type of aCid and at

the same concentratIOn as will result m the sample to be analyzed either directly or after

processmg

Sample Preservation

1 For sample handhng and preservatIOn, see part 4 1 of the Atomic AbsorptIOn Methods

sectIOn ofthis manual

Sample PreparatIon

1 The procedures for preparatIOn of the sample as given m parts 4 I 1 thru 4 1 4 of the

Atomic AbsorptIOn Methods sectIOn ofthis manual have been found to be satisfactory

Instrumental Parameters (General)

1 Manganese hollow cathode lamp

2 Wavelength 2795 nm

3 Fuel Acetylene

4 OXidant Air

5 Type offlame OXldlzmg

AnalysIs Procedure

1 For analysIs procedure and calculation, see "Direct AspiratIOn", part 9 I of the Atomic

AbsorptIOn Methods sectIOn ofthis manual

Approved for NPDES

Issued 1971

Edltonal reVISIOn 1974 and 1978

243 I-I
Notes

I

2

3

4

For levels of manganese below 25 ug/l, eIther the furnace procedure, Method 243 2, or

the Special ExtractIOn Procedure given m part 9 2 of the AtomIC AbsorptIOn Methods

sectIon IS recommended The extractIon IS carned out at a pH of4 5 to 5 The manganese

chelate IS very unstable and the analysIs must be made wIthout delay to prevent ItS resolutIon m the aqueous phase

The followmg lme may also be used

403.1 nm RelatIve SenSItIVIty 10

Data to be entered mto STORET must be reported as ug/l

The persulfate colonmetnc method may also be used (Standard Methods, 14th EdItIon,

p225)

Precision and Accuracy

1 An mterlaboratory study on trace metal analyses by atomIC absorptIOn was conducted by

the Quahty Assurance and Laboratory EvaluatIOn Branch of EMSL SIX synthetIc

concentrates contammg varymg levels of alummum, cadmIUm, chromIUm, copper, Iron,

manganese, lead and zmc were added to natural water samples The statIstICal results for

manganese were as follows

Standard

Number True Values Mean Value DeViation Accuracy as

of Labs ug/1lter ug/hter ug/hter % Bias

77 426 432 70 1 5

78 469 474 97 12

71 84 86 26 21

70 106 104 31 -21

55 11 21 27 93

55 17 21 20 22

243 1-2
MANGANESE

Method 243.2 (Atomic Absorption, furnace technique)

STORET NO. Total 01055

Dissolved 01056

Suspended 01054

Optimum Concentration Range

DetectIOn LImIt: 02 ug/l

1-30 ug/l,

PreparatIOn ofStandard SolutIOn

1 Stock solutIOn Prepare as descnbed under "dIrect aspIratIOn method"

2 Prepare dl1utIOns of the stock solutIOn to be used as cahbratIOn standards at the time of

analysIs These solutIOns are also to be used for "standard addItIOns"

3 The cahbratIOn standard should be dIluted to contam 0 5% (vIv) HN03

Sample Preservation

1 For sample handhng and preservatIOn, see part 4 I of the AtomIC AbsorptIOn Methods

sectIOn ofthIS manual

Sample Preparation

1 Prepare as descnbed under "dIrect aspIratIOn method" Sample solutIOns for analysIs

shouldcontamO 5% (v/v)HN03

Instrument Parameters (General)

1 Drymg TIme and Temp 30 sec-125°C

2 AshmgTlmeand Temp 30sec-1000°C

3 Atomlzmg TIme and Temp 10 sec-2700°C

4 Purge Gas Atmosphere Argon

5 Wavelength 279 5 nm

6 Other operatmg parameters should be set as speCIfied by the particular mstrument

manufacturer

AnalYSIS Procedure

1 For the analysIs procedure and the calculatlOn, see "Furnace Procedure" part 9 3 ofthe

AtomIC AbsorptIOn Methods sectIOn ofthIS manual

Notes

1 The above concentratIOn values and mstrument condItIOns are for a Perkm-Elmer HGA2100, based on the use of a 20 ul mJectIOn, contmuous flow purge gas and non-pyrolytIc

Approved for NPDES

Issued 1978

2432-1
graphIte Smaller SIze furnace devIces or those employmg faster rates of atomIzatIOn can

be operated usmg lower atOmlZatIOn temperatures for shorter tIme penods than the

above recommended settmgs

2 The use ofbackground correctIOn IS recommended

3 NItrogen may also be used as the purge gas

4 For every sample matnx analyzed, venficatIOn IS necessary to determme that method of

standard addItIOn IS not reqUlred (see part 5 2 1 of the AtomIC AbsorptIOn Methods

sectIOn OfthlS manual)

5 Ifmethod ofstandard addItIOn IS reqUlred, follow the procedure gIven earher m part 8 5

ofthe Atomlc AbsorptIOn Methods sectIOn ofthIS manual

6. Data to be entered mto STORET must be reported as ug/l

Precision and Accuracy

1 PrecIsIon and accuracy data are not aval1able at thIS tIme

2432-2
MERCURY

Method 245.1 (Manual Cold Vapor Technique)

STORET NO. Total 71900

Dissolved 71890

Suspended 71895

1 Scope and ApphcatlOn

1 1 ThIS method IS apphcable to dnnkmg, surface, and sahne waters, domestIc and mdustnal

wastes

1 2 In addItion to morgamc forms ofmercury, orgamc mercunals may also be present These

organo-mercury compounds WIll not respond to the cold vapor atomIC absorptIOn

techmque unless they are first broken down and converted to mercunc IOns Potassmm

permanganate oXIdIzes many of these compounds, but recent studIes have shown that a

number of orgamc mercunals, mcludmg phenyl mercunc acetate and methyl mercunc

chlonde, are only partially oXIdIzed by thIS reagent Potasssmm persulfate has been

found to gIve approxImately 100% recovery when used as the oXIdant wIth these

compounds Therefore, a persulfate oXIdatIOn step followmg the addItIon of the

permanganate has been mcluded to msure that organo-mercury compounds, If present,

WIll be oXIdIzed to the mercunc Ion before measurement A heat step IS reqmred for

methyl mercunc chlonde when present m or spIked to a natural system For dlst111ed

water the heat step IS not necessary

1 3 The range ofthe method may be vaned through mstrument and/or recorder expanSIOn

Usmg a 100 ml sample, a detectIOn hmlt of 0 2 ug Hg/l can be achIeved, concentratIOns

below thIS level should be reported as < 0 2 (see AppendIX 11 2)

2 Summary ofMethod

2 1 The flameless AA procedure IS a physIcal method based on the absorptIOn ofradIatIon at

253 7 nm by mercury vapor The mercury IS reduced to the elemental state and aerated

from solutIOn m a closed system The mercUlY vapor passes through a cell posItIoned m

the hght path of an atomIC absorptIOn spectrophotometer Absorbance (peak heIght) IS

measured as a functIOn ofmercury concentratIOn and recorded m the usual manner

3 Sample Handhng and PreservatIOn

3 1 Untll more conclUSIve data are obtamed, samples should be preserved by aCIdIficatIOn

wIth mtnc aCId to a pH of 2 or lower ImmedIately at the tIme of collectIOn If only

dIssolved mercury IS to be determmed, the sample should be filtered through an all glass

apparatus before the aCId IS added For total mercury the filtration IS omItted

4 Interference

4 1 POSSIble mterference from sulfide IS ehmmated by the addItion of potassmm

permanganate ConcentratIOns as hIgh as 20 mg/l of sulfide as sodmm sulfide do not

mterfere wIth the recovery ofadded morgamc mercury from dlst1l1ed water

Approved for NPDES and SDWA

Issued 1974

245 1-1
4 2 Copper has also been reported to mterfere, however, copper concentratiOns as high as 10

mg/l had no effect on recovery ofmercury from spiked samples

4 3 Sea waters, bnnes and mdustnal effluents high m chlondes reqUire additiOnal

permanganate (as much as 25 ml) Dunng the OXidation step, chlondes are converted to

free chlonne which w111 also absorb radiatiOn of 253 nm Care must be taken to assure

that free chlonne IS absent before the mercury IS reduced and swept mto the cell ThiS

may be accomphshed by usmg an excess of hydroxylamme sulfate reagent (25 ml) In

addition, the dead air space m the BOD bottle must be purged before the additiOn of

stannous sulfate Both morgamc and orgamc mercury spikes have been quantitatively

recovered from sea water usmg thiS techmque

4 4 Interference from certam volatl1e orgamc matenals which w111 absorb at thiS wavelength

IS also pOSSible A prehmmary run Without reagents should determme If thiS type of

mterference IS present (see AppendiX 11 1)

5. Apparatus

5 1 AtomiC AbsorptiOn Spectrophotometer (See Note 1) Any atomIC absorptiOn umt havmg

an open sample presentatIOn area m which to mount the absorptiOn cell IS SUitable

Instrument settmgs recommended by the partICular manufacturer should be followed

Note 1 Instruments designed speCifically for the measurement ofmercury usmg the cold

vapor techmque are commercially available and may be substituted for the atomic

absorptiOn spectrophotometer

5.2 Mercury Hollow Cathode Lamp Westmghouse WL-22847, argon filled, or eqUivalent

5 3 Recorder Any multi-range vanable speed recorder that IS compatible With the UV

detection system IS SUitable

5 4 Absorption Cell Standard spectrophotometer cells 10 cm long, havmg quartz end

wmdows may be used SUitable cells may be constructed from plexiglass tubmg, 1" 0 D

X 4-112" The ends are ground perpendicular to the longltudmal aXIs and quartz

wmdows (1" diameter X 1116" thickness) are cemented m place The cell IS strapped to a , burner for support and ahgned m the hght beam by use of two 2" by 2" cards One mch

diameter holes are cut m the middle ofeach card, the cards are then placed over each end

ofthe cell The cell IS then posItioned and adjusted vertically and honzontally to give the

maximum transmittance

5.5 Air Pump Any penstaltlc pump capable of dehvenng 1 hter of air per mmute may be

used A Masterflex pump With electromc speed control has been found to be satisfactory

5 6 Flowmeter Capable ofmeasunng an air flow of 1 hter per mmute

5 7 Aeration Tubmg A straight glass fnt havmg a coarse porosity Tygon tubmg IS used for

passage ofthe mercury vapor from the sample bottle to the absorptiOn cell and return

5 8 Drymg Tube 6" X 3/4" diameter tube contammg 20 g of magnesIUm perchlorate (see

Note 2) The apparatus IS assembled as shown m Figure 1

NOTE 2: In place ofthe magnesIUm perchlorate drymg tube, a small readmg lamp With

60W bulb may be used to prevent condensatiOn of mOisture mSlde the cell The lamp IS

posItioned to shme on the absorptiOn cell mamtammg the air temperature m the cell

about IOGC above ambient

245 1-2

II III
6 Reagents

6 1 Sulfunc AC1d, Conc Reagent grade

6 1 1 Sulfunc aC1d, 0 5 N Dl1ute 140 ml ofconc sulfunc aC1d to 1 0 hter

6 2 N1tnc AC1d, Conc Reagent grade oflow mercury content (See Note 3)

NOTE 3: If a h1gh reagent blank 1S obtamed, 1t may be necessary to d1st111 the mtnc aC1d

6 3 Stannous Sulfate Add 25 g stannous sulfate to 250 ml of 0 5 N sulfunc aC1d Th1S

m1xture 1S a suspensiOn and should be st1rred contmuously dunng use (Stannous

chlonde may be used m place ofstannous sulfate)

6 4 Sodmm Chlonde-Hydroxylamme Sulfate SolutiOn D1ssolve 12 g ofsodmm chlonde and

12 g of hydroxylamme sulfate m d1stl1led water and dl1ute to 100 ml (Hydroxylamme

hydrochlonde may be used m place ofhydroxylamme sulfate)

6 5 Potassmm Permanganate 5% solutiOn, wIv D1ssolve 5 g of potassmm permanganate m

100 ml ofd1stl1led water

66 Potassmm Persulfate 5% solutiOn, wlv D1ssolve 5 g ofpotassmm persulfate m 100 ml

ofd1stl1led water

67 Stock Mercury SolutiOn D1ssolve 0 1354 g of mercunc chlonde m 75 ml of d1stl1led

water Add 10 ml of conc mtnc aC1d and adjust the volume to 1000 ml 1 ml = 1 mg

Hg

AIR PUMP

DESICCANT rL..-I

ABSORPTION

BUBBLER CELL '-----'

SAMPLE SOLUTION

IN BOD BOTTLE

SCRUBBER

CONTAINING

A MERCURY

ABSORBING

MEDIA

FIGURE 1. APPARATUS FOR FlAMElESS

MERCURY 'DETERMINATION

245 1-3
6 8 Workmg Mercury SolutlOn Make succeSSIve dilutlOns of the stock mercury solutlOn to

obtam a workmg standard contammg 0 1 ug per ml ThIS workmg standard and the

dl1utlOns of the stock mercury solutlOn should be prepared fresh dally ACIdIty of the

workmg standard should be mamtamed at 015% mtnc aCId ThIS aCId should be added

to the flask as needed before the addItion ofthe ahquot

7. CalibratlOn

7 1 Transfer 0, 0 5, 1 0, 2 0, 5 0 and 10 0 ml ahquots of the workmg mercury SolutIon

contammg 0 to 1 0 ug ofmercury to a senes of 300 ml BOD bottles Add enough dIstIlled

water to each bottle to make a total volume of 100 ml MIX thoroughly and add 5 ml of

conc sulfunc aCId (6 1) and 2 5 ml of conc mtnc aCId (6 2) to each bottle Add 15 mlof

KMn04 (6 5) solutlOn to each bottle and allow to stand at least 15 mmutes Add 8 mlof

potassmm persulfate (6 6) to each bottle and heat for 2 ho~r~ m a water bath mamtmed at

95°C Cool and add 6 ml of sodmm ch1onde-hydroxyl~me sulfate SolutIon (64) to

reduce the excess permanganate When the SolutIon has been decolonzed walt 30

seconds, add 5 ml ofthe stannous sulfate solutlOn (63) and ImmedIately attach the bottle

to the aeratlOn apparatus fOrming a closed system At thIS pomt the sample IS allowed to

stand qUietly WIthout manual agitatiOn The clrculatmg pump, WhICh has prevIously

been adjusted to a rate of 1 hter per mmute, IS allowed to run contmuously (See Note 4)

The absorbance WIll mcrease and reach maXlffium wlthm 30 seconds As soon as the

recorder pen levels off, approXlffiately 1 mmute, open the bypass valve and contmue the

aeratlOn untll the absorbance returns to ItS mmlmum value (see Note 5) Close the bypass

valve, remove the stopper and fnt from the BOD bottle and contmue the aeration

Proceed WIth the standards and construct a standard curve by plottmg peak heIght

versus mIcrograms ofmercury

NOTE 4: An open system where the mercury vapor IS passed through the absorptlOn cell

only once may be used mstead ofthe closed system '

NOTE 5: Because ofthe tOXiC nature ofmercury"vapor precautlOn must be taken to aVOid

ItS mhalatlOn Therefore, a bypass has been mcluded m the system to eIther vent the

mercury vapor mto an exhaust hood or pass the vapor through some absorbmg medIa,

such as

a) equal volumes of0 1M KMn04 and 10% H2S04

b) 025% lOdme m a 3% KI solutlOn

A specIally treated charcoal that wlll adsorb mercury vapor IS also aval1able from

Bamebeyand Cheney, E 8th Ave and N CassIdy St , Columbus, OhlO 43219,

Cat #580-13 or #580-22

8 Procedure

8 1 Transfer 100 ml, or an ahquot dlluted to 100 ml, contammg not more than 10 ug of

mercury, to a 300 ml BOD bottle Add 5 ml of sulfunc aCId (6 1) and 25 ml of conc

mtnc aCId (62) mlxmg after each addItion Add 15 ml of potassmm permanganate

solution (6 5) to each sample bottle For sewage samples additlOnal permanganate may

be reqUired Shake and add addItIonal portlOns of potassmm permanganate SolutIon, If

nece~sary, untIl the purple color persIsts for at least 15 mmutes Add 8 ml ofpotassmm

persulfate (6 6) to each bottle and heat for 2 hours m a water bath at 95°C Cool and add 6

245 1-4
ml of sodmm chloflde-hydroxylamme sulfate (64) to reduce the excess permanganate

After a delay of at least 30 seconds add 5 ml ofstannous sulfate (6 3) and ImmedIately

attach the bottle to the aeratIon apparatus Contmue as descflbed under CalIbratIOn

9 CalculatIOn

9 I Determme the peak heIght of the unknown from the chart and read the mercury value

from the standard curve

9 2 Calculate the mercury concentratIOn m the sample by the formula

H /1 _ (UgHgm) ( 1,000 ) ug g - alIquot volume of alIquot m ml

93 Report mercury concentratIons as follows Below 02 ug/1, <02, between 1 and 10

ug/1, one decImal, above 10 ug/1, whole numbers

10 PrecIsIOn and Accuracy

10 1 In a smgle laboratory (EMSL), usmg an OhIO RIver composIte sample wIth a

background mercury concentratIOn of 0 35 ug/1, spIked wIth concentratIOns of 1 0, 3 0

and 40 ug/1, the standard devIatIons were ±O 14, ±O 10 and ±O 08, respectIvely

Standard devIatIOn at the 035 level was ±O 16 Percent recovefles at the three levels

were 89,87, and 87%, respectIvely

10 2 In a Jomt EPAIASTM mterlaboratory study of the cold vapor techmque for total

mercury m water, mcrements of organIc and morgamc mercury were added to natural

waters Recovefles were determmed by dIfference A statIstIcal summary of thIS study

follows

Standard

Number True Values Mean Value DeViatIOn Accuracy as

of Labs uglhter uglhter ug/hter % Bias

76 021 0349 0276 66

80 027 0414 0279 53

82 051 0674 0541 32

77 060 0709 0390 18

82 34 341 149 034

79 41 381 1 12 -71

79 88 877 369 -04

78 96 910 357 -52

11 AppendIX

11 1 WhIle the possIbIlIty ofabsorptIon from certam orgamc substances actually bemg present

m the sample does eXIst, EMSL has not encountered such samples ThIS IS mentIoned

only to cautIon the analyst ofthe possIbIlIty A SImple correctIOn that may be used IS as

follows If an mterference has been found to be present (44), the sample should be

analyzed both by usmg the regular procedure and agam under oXIdIzmg condItIOns only,

245 1-5
that IS wIthout the reducIng reagents The true mercury value can then be obtaIned by

subtractIng the two values

11 2 IfaddItIOnal sensItivIty IS reqUired, a 200 ml sample with recorder expansion may be used

prOVided the Instrument does not produce undue nOIse USIng a Coleman MAS-50 with a

dryIng tube ofmagnesIUm perchlorate and a vanable recorder, 2 mv was set to read full

scale. WIth these conditIOns, and distIlled water solutIOns of mercunc chlonde at

concentratIOns of 0 15, 0 10, 005 and 0025 ug/1 the standard deviations

were ±O 027, ±O 006, ±O 01 and ±O 004 Percent recovenes at these levels were 107,

83, 84 and 96%, respectively

11 3 DIrectIons for the disposal of mercury-contaInIng wastes are given In ASTM Standards,

Part 31, "Water", p 349, Method 03223 (1976)

BIbliography

1 Kopp, J F, Longbottom, M C and Lobnng, L B, "Cold Vapor Method for DetermInIng

Mercury", AWWA, vol 64, p 20, Jan, 1972

2 Annual Book ofASTMStandards, Part 31, "Water", Standard 03223-73, p 343 (1976)

3. Standard Methods for the ExamInatIOn ofWater and Wastewater, 14th EditIOn, 'p 156 (1975)

245 1-6
MERCURY

Method 245.2 (Automated Cold Vapor Technique)

STORET NO. Total 71900

Dissolved 71890

S~spended 71895

1 Scope and ApplIcatIOn

1 1 This method is applicable to surface waters It may be applicable to salIne waters,

wastewaters, effluents, and domestic sewages providmg potential mterferences are not

present (See Interference 4)

1 2 The workmg range is 0 2 to 20 0 ug Hg/1

2 Summary ofMethod

2 1 The flameless AA procedure is a physical method based on the absorptIOn ofradiatIOn at

253 7 nm by mercury vapor The mercury is reduced to the elemental state and aerated

from solutIOn The mercury vapor passes through a cell pOSitioned m the light path of an

atomiC absorptIOn spectrophotometer Absorbance (peak height) is measured as a

functIOn ofmercury concentratIOn and recorded m the usual manner

2 2 In addition to morgamc forms ofmercury, orgamc mercunals may also be present These

organo-mercury compounds w111 not respond to the flameless atomiC absorption

techmque unless they are first broken down and converted to mercunc IOns Potassmm

permanganate oXidizes many of these compounds but recent studies have shown that a

number of orgamc mercunals, mcludmg phenyl mercunc acetate and methyl mercunc

chlonde, are only partially oXidized by this reagent Potassmm persulfate has been found

to give approXimately 100% recovery when used as the oXidant with these compounds

Therefore, an automated persu1fate oXidatIOn step followmg the automated addition of

the permanganate has been mcluded to msure that organo-mercury compounds, if

present, w111 be oXidlZed to the mercunc ion before measurement

3 Sample Handlmg and PreservatIOn

3 1 Untl1 more conclusive data are obtamed, samples should be preserved by aCidificatIOn

with mtnc aCid to a pH of 2 or lower immediately at the time of collectiOn (1) If only

dissolved mercury is to be determmed, the sample should be filtered before the aCid is

added For total mercury the filtratIOn IS omitted

4 Interference (See NOTE 1)

4 1 Some sea waters and waste-waters high lIi chlondes have shown a positive mterference,

probably due to the formatIOn offree chlonne

4 2 Interference from certam volatile orgamc matenals which w111 absorb at this wavelength

is also possible A prelimmary run under oXidizmg conditIOns, without stannous sulfate,

would determme ifthis type ofmterference is present

Approved for NPDES and SDWA

Issued 1974

2452-1
4 3 Formation of a heavy preCIpItate, m some wastewaters and effluents, has been reported

upon addItion of concentrated sulfunc aCId If thIS IS encountered, the problem sample

cannot be analyzed by thIS method

4 4 Samples contammg sohds must be blended and then mIXed whlle bemg sampled If total

mercury vlaues are to be reported

NOTE 1: All the above mterferences can be overcome by use of the Manual Mercury

method m thIS manual

5. Apparatus

5 1 Techmcon Auto Analyzer conslstmg of

5 1 1 Sampler II WIth prOVIsIon for sample mlxmg

5 1 2 ManIfold

5.1 3 Proportlonmg Pump II or III

5 1 4 HIgh temperature heatmg bath WIth two dlstlllatlOn colIs (Techmcon Part

# 116-0163) m senes

5 2 Vapor-hqUld separator (FIgure 1)

5 3 AbsorptlOn cell, 100 mm long, 10 mm dIameter WIth quartz wmdows

5 4 AtomIC AbsorptlOn Spectrophotometer (See Note 2) Any atomIC absorption umt havmg

an open sample presentatlOn area m WhICh to mount the absorptlOn cell IS sUltable

Instrumentsettmgs recommended by the particular manufacturershould be followed

NOTE 2: Instruments deSIgned speCIfically for the measurement of mercury usmg the

cold vapor technIque are commercIally avallable and may be SubstItuted for the atomIC

absorptIon spectrophotometer

55 Mercury Hollow Cathode Lamp Westmghouse WL-22847, argon filled, or eqUlvalent

5.6 Recorder Any multI-range vanable speed recorder that IS compatible WIth the UV

detectIon system IS sUltable

5 7 Source ofcoohng water forJacketed mlxmg COlI and connector A-7

5 8 Heat lamp A small readmg lamp WIth 60W bulb may be used to prevent condensation of

mOlsture mSlde the cell The lamp IS posltlOned to shme on the absorption cell

maintammg the aIr temperature m the cell about 10°C above ambIent

6. Reagents

6 1 Sulfunc ACId, Conc Reagent grade

6 1 1 Sulfunc aCId, 2 N DIlute 56 ml of conc sulfunc aCId to 1 hter WIth dlstllied water

6 1 2 Sulfunc aCId, 10% Dllute 100 ml conc sulfunc 'aCId to 1 hter WIth dlstllied water

6 2 Nltnc aCId, Conc Reagent grade oflow mercury content

6 2 1 Nltnc ACId, 0 5% Wash SolutlOn DIlute 5 ml of conc mtnc aCId to 1 hter WIth

d1sttlled water

63 Stannous Sulfate Add 50 g stannous sulfate to 500 ml of 2 N sulfunc aCId (6 1 1) ThIS

mIxture IS a suspenslOn and should be stIrred contmuously durmg use

NOTE 3: Stannous chlonde may be used m place ofstannous sulfate

64 SodIum Chlonde-Hydroxylamme Sulfate SolutlOn DIssolve 30 g of sodiUm chlonde

and 30 g ofhydroxylamme sulfate m dlstllied water to I hter

2452-2
NOTE 4: Hydroxylamme hydrochlonde may be used m place of hydroxylamme sulfate

65 Potassmm Permanganate 05% solutlOn, w/v DIssolve 5 g ofpotassmm permanganate

m 1hter ofdIstIlled water

6 6 Potassmm Permanganate, 0 1 N DIssolve 3 16 g of potassmm permanganate m dIstIlled

water and dIlute to 1hter

6 7 Potassmm Persulfate 0 5% solutlOn, WIv DIssolve 5 g potassmm persulfate m 1 hter of

dIstIlled water

68 Stock Mercury SolutlOn DIssolve 0 1354 g of mercunc chlonde in 75 ml of dIstIlled

water Add 10 ml of conc mtnc aCId and adjust the volume to 1000 mIlO ml = 10

mgHg

6 9 Workmg Mercury SolutlOn Make succeSSIve dIlutIons of the stock mercury SolutIon

(68) to obtam a workmg standard contammg 01 ug per ml ThIS workmg standard and

the dIlutIons ofthe stock mercury SolutIon should be prepared fresh daIly ACIdIty ofthe

workmg standard should be mamtamed at 015% mtnc aCId ThIS aCId should be added

to the flask as needed before the addItIon of the ahquot From thIS solutlOn prepare

standards contammg 02,05, 1 0,20,50, 10 0, 150 and 20 0 ug Hg/1

6 10 AIr Scrubber SolutlOn MIX equal volumes of 0 1 N potassmm permanganate (6 6) and

10% sulfunc aCId (6 1 2)

7 Procedure

7 1 Set up mamfold as shown m FIgure 2

72 Feedmg all the reagents through the system wIth aCId wash solutIon (6 2 1) through the

sample hne, adjust heatmg bath to 105°C

73 Turn on atomIC absorptIon spectrophotometer, adjust mstrument settmgs as

recommended by the manufacturer, ahgn absorptlOn cell m hght path for maXImum

transmIttance and place heat lamp dIrectly over absorptlOn cell

7 4 Arrange workmg mercury standards from 0 2 to 20 0 ug Hg/1 m sampler and start

samphng Complete loadmg ofsample tray wIth unknown samples

7 5 Prepare standard curve by plottmg peak heIght of processed standards agamst

concentratIon values Determme concentratIOn of samples by comparmg sample peak

heIght wIth standard curve

NOTE 5: Because of the tOXIC nature of mercury vapor, precautIOn must be taken to

aVOId ItS mhalatlOn Ventmg the mercury vapor mto an exhaust hood or passmg the

vapor through some absorbmg medIa such as

a) equal volumes of0 1 N KMn04 (6 6) and 10% H2S04 (6 I 2)

b) 025% Iodme m a 3% KI solutIOn, IS recommended

A specIally treated charcoal that WIll adsorb mercury vapor IS also avaIlable from

Barnebey and Cheney, E 8th Ave and North CaSSIdy St ,Columbus, OhIO 43219,

Cat #580-13 or #580-22

7 6 After the analysIs IS complete put all hnes except the H2S04 hne m dIstIlled water to wash

out system After flushmg, wash out the H2S04 hne Also flush the COlIs m the hIgh

temperature heatmg bath by pumpmg stannous sulfate (63) through the sample hnes

followed by dIstIlled water ThIS WIll prevent buIld-up ofOXIdes ofmanganese

2452-3
8. PrecIsion and Accuracy

8 1 In a smgle laboratory (SEWL), usmg distIlled water standards at concentratIOns of 0 5,

10, 20, 50, 10 0 and 200 ug Hg/l, the standard deviations

were ±O 04, ±O 07, ±O 09, ±O 20, ±O 40 and ±O 84 ug/l, respectively

82 In a smgle laboratory (SEWL), usmg surface water samples spiked with ten orgamc

mercunals at the 10 ug/l level, recovenes ranged from 87 to 117% Recovenes of the

same ten orgamc mercunals m distIlled water at the 10 ug/llevel, ranged from 92% to

125%

Blbhography

1 Wallace, R A, Fulkerson, W , Shults, W D, and Lyon, W S, "Mercury m the EnVlfonmentThe Human Element", Oak Ridge NatIOnal Laboratory, ORNL-NSF-EP-l, p 31, (January,

1971)

2 Hatch, W R and Ott, W L, "Determmatlon of Sub-Microgram QuantIties of Mercury by

Atomic AbsorptIOn Spectrophotometry", Anal Chem 40,2085 (1968)

3 Brandenberger, H and Bader, H, "The Determmatlon of Nanogram Levels of Mercury m

Solution by a Flameless AtomiC Absorption Techmque", AtomiC AbsorptIOn Newsletter

101 (1967)

4 Brandenberger, H and Bader, H, "The DetermmatlOn of Mercury by Flameless AtomiC

Absorption II, A Static Vapor Method", Atomtc Absorption Newsletter 1.-53 (1968)

5. Goulden, P D and Afghan, B K, "An Automated Method for Determmmg Mercury m

Water", Techmcon, Adv mAuto Anal ~p 317 (1970)

2452-4

,

I' I "
AIR AND

SOLUTION

IN

04 em 10

7/25 'S'

07 em 10 14 em

SOLUTION

OUT

FIGURE 1. VAPOR LIQUID SEPARATOR

2452-5
20/hr SAMPLER II

5/l-Wash

Sam

ml/min

D

RECORDER

253.7nm

Vent

A A 110lllm Db

SPECTROPHOTOMETER lOOum fL.__ Long

,,"""_..

L~ Waste p W ':l on

p W 3 90 HN03 Wash

p W ':\ 90

~o G G 200JDO

P W 3 90

p:~f: P W

Dl i- P

P

W

W

390 3~r 'l 90 r4Air I

P W 3 90

DOUBLE MIXER

P W 390F AIR

P W 3 90 GO SCRUBBER

y y 1 20 10% SnS04

~nrp" 3% NaC1

+

P P 2 50 3% (NH20H)? H2SO4

'ETE0f'XER I*~ ""L Y y 1 20 .5% K2S20R & IpS3 + +

* JI--& P * W 2 76

P * W 2 76 (Con) H2SO4 ** p W 'lQO

8·.L~f[ -E P W 3 90 Sample

Dl H1 P W 3 95

PS4 G G

HEATING BATH I PS3 -- 2 00 AJ.r

.. y y 1 20 .5% KMn°lt

I;~

JAC

Ul

0\

Proportioning Pump III

FIGURE 2 MERCURY MANIFOLD AA-I

AIR * ACJ.d Flex SCRUBBER ** Teflon *** Glass
MERCURY IN SEDIMENT

Method 245.5 (Manual Cold Vapor Technique)

I Scope and ApphcatIOn

I I ThIS procedure(!) measures total mercury (organIc t InorganIc) In sOlIs, sedIments,

bottom depOSIts and sludge type materials

I 2 The range ofthe method IS 0 2 to 5 ug/g The range may be extended above or below the

normal range by IncreaSIng or decreaSIng sample SIze or through Instrument and

recorder control

2 Summary ofMethod

2 I A weIghed portIOn ofthe sample IS dIgested In aqua regIa for 2 mInutes at 95°C, followed

by oXIdatIOn wIth potaSSIUm permanganate Mercury In the dIgested sample IS then

measured by the conventIOnal cold vapor technIque

2 2 An alternate digestIOn(2) InvolVIng the use ofan autoclave IS descnbed In (8 2)

3 Sample Handhng and Preservation

3 I Because of the extreme senSItIVIty of the analytical procedure and the omnIpresence of

mercury, care must be taken to aVOId extraneous contamInatIOn Samphng deVIces and

sample contaIners should be ascertaIned to be free ofmercury, the sample should not be

exposed to any condItion In the laboratory that may result In contact or aIr-borne

mercury contamInatIOn

3 2 WhIle the sample may be analyzed WIthout dryIng, It has been found to be more

convenIent to analyze a dry sample MOIsture may be driven off In a dryIng oven at a

temperature of 60°C No mercury losses have been observed by USIng thIS drymg step

The dry sample should be pulverized and thoroughly mIxed before the ahquot IS

weIghed

4 Interferences

4 I The same types of Interferences that may occur In water samples are also pOSSIble WIth

sedIments, 1 e , sulfides, hIgh copper, hIgh chlOrides, etc

4 2 Volatile materials whIch absorb at 253 7 nm WIll cause a pOSItIve Interference In order to

remove any Interfenng volatIle materials, the dead aIr space In the BOD bottle should be

purged before the addItion ofstannous sulfate

5 Apparatus

5 1 AtomIC AbsorptIOn Spectrophotometer (See Note 1) Any atomIC absorptIOn UnIt

haVIng an open sample presentatIOn area In whIch to mount the absorptIOn cell IS

SUItable Instrument settIngs recommended by the partIcular manufacturer should be

followed

NOTE 1 Instruments deSIgned speCIfically for the measurement of mercury USIng the

cold vapor technIque are commerCIally avaIlable and may be substItuted for the atomIC

absorptIOn spectrophotometer

Issued 1974

2455-1
52 Mercury Hollow Cathode Lamp Westmghouse WL-22847, argon filled, or eqUivalent

53 Recorder' Any multi-range vanable speed recorder that' IS compatible wlth the UV

detectlOn system IS sUitable

5.4 Absorptlon Cell Standard spectrophotometer cells 10 cm long, havmg quartz end

wmdows may be used SUitable cells may be constructed from plexlglass tubmg, I" 0 D

X 4-1/2" The ends are ground perpendlcular to the longltudmal aXlS and quartz

wmdows (I" dlameter X 1/16" thickness) are cemented m place Gas mlet and outlet

ports (also of pieXlglass but 1/4" 0 D) are attached approxlmately 1/2" from each end

The cell IS strapped to a burner for support and ahgned m the hght beam to glve the

maXlmum transmlttance

NOTE 2: Two 2" X 2" cards wlth one mch dlameter holes may be placed over each end

ofthe cell to asS1St m posltionmg the cell for maXlmum transmlttance

5.5 Air Pump Any penstaltic pump capable of dehvermg 1 hter of alr per mmute may be

used A Masterflex pump wlth electromc speed control has been found to be satlsfactory

(Regulated compressed alr can be used m an open one-pass system)

5 6 Flowmeter Capable ofmeasunng an alr flow of 1 hter per mmute

5.7 Aeration Tubmg Tygon tubmg IS used for passage ofthe mercury vapor from the sample

bottle to the absorptlOn cell and return Stralght glass tubmg termmatmg m a coarse

porous fnt IS used for spargmg alr mto the sample

58 Drymg Tube 6" X 3/4" dlameter tube contammg 20 g ofmagneslUm perchlorate (See

Note 3) The apparatus IS assembled as shown m the accompanymg dlagram

NOTE 3: In place ofthe magneslUm perchlorate drymg tube, a small readmg lamp wlth

60W bulb may be used to prevent condensatlOn of mOlsture mSlde the cell The lamp IS

posltioned to shme on the absorptlOn cell mamta~mng the air temperature m the cell

about 10°C above amblent

6 Reagents

6 1 Aqua Regla Prepare Immedlately before use by carefully addmg three volumes of conc

HCI to one volume ofconc HN03

6 2 Sulfunc ACld, 0 5 N Dllute 14 0 ml ofconc sulfunc aCld to 1hter

6 3 Stannous Sulfate Add 25 g stannous sulfate to 250 ml of 0 5 N sulfurlC aCld (6 2) ThlS

mlxture IS a suspenslOn and should be stlrred contmuously durmg use

6.4 SodlUm Chlonde-Hydroxylamme Sulfate SolutlOn Dlssolve 12 g of sodlUm chlonde

and 12 g ofhydroxylamme sulfate m dlstllied water and dl1ute to 100 ml

NOTE 4: A 10% solutlOn of stannous chlonde may be Substltuted for (63) and

hydroxylamme hydrochlonde may be used m place ofhydroxylamme sulfate m (64)

65 Potassmm Permanganate 5% solutlOn, w/v Dlssolve 5 g of potasSlUm permanganate m

100 ml ofdlstllled water

66 Stock Mercury SolutlOn Dlssolve 0 1354 g of mercunc chlonde m 75 ml of dlstllied

water Add 10 ml of conc mtnc aCld and adjust the volume to 100 0 milO ml = 10

mgHg

6 7 Workmg Mercury SolutlOn Make succeSSlve dllutlOns of the stock mercury solutlOn

(6 6) to obtam a workmg standard contammg 0 1 ug/ml Thls workmg standard and the

dllutlOn of the stock mercury solutlOns should be prepared fresh dally ACldlty of the

2455-2
workmg standard should be mamtamed at 015% mtnc aCId ThIS aCId should be added

to the flask as needed before the addItIon ofthe ahquot

7 Cahbratton

71 Transfer 0, 05, 10, 20, 50 and 10 ml ahquots of the workmg mercury solutIon (67)

contammg 0 to 1 0 ug ofmercury to a senes of 300 ml BOD bottles Add enough dIstIlled

water to each bottle to make a total volume of 10 ml Add 5 ml of aqua regIa (6 1) and

heat 2 mmutes m a water bath at 95°C Allow the sample to cool and add 50 ml dIstIlled

water and 15 ml ofKMn04solutIOn (6 5) to each bottle and return to the water bath for

30 mmutes Cool and add 6 ml ofsodIUm chlonde-hydroxylamme sulfate solutIOn (6 4)

to reduce the excess permanganate Add 50 ml of dIstIlled water Treatmg each bottle

mdividually, add 5 ml of stannous sulfate solutIOn (63) and ImmedIately attach the

bottle to the aeratIOn apparatus At thIS pomt, the sample IS allowed to stand qUIetly

WIthout manual agItatIOn The circulatmg pump, WhICh has prevIously been adjusted to

rate of 1 hter per mmute, IS allowed to run contmuously The absorbance, as exhIbIted

eIther on the spectrophotometer or the recorder, wIll mcrease and reach maXImum

withm 30 seconds As soon as the recorder pen levels off, approxImately 1 mmute, open

the bypass value and contmue the aeratIon unttl the absorbance returns to Its mmimum

value (See Note 5) Close the bypass value, remove the fntted tubmg from the BOD

bottle and contmue the aeratIOn Proceed With the standards and construct a standard

curve by plottmg peak heIght versus mlCrogiams ofmercury

NOTE 5: Because ofthe tOXIC nature ofmercury vapor precautIOn must be taken to avoId

Its mhaiatton Therefore, a bypass has been mcluded m the system to eIther vent the

mercury vapor mto an exhaust hood or pass the vapor through some absorbmg medIa,

such as

a) equal volumes of0 1 N KMn04 and 10% H2S04

b) 025% IOdme m a 3% KI SolutIon

A specIally treated charcoal that wIll absorb mercury vapor IS also avatlable from

Barnebey and Cheney, E 8th Ave, and North CassIdy St , Columbus, OhIO 43219,

Cat #580-13 or #580-22

8 Procedure

8 1 WeIgh tnphcate 0 2 g portIOns ofdry sample and place m bottom ofa BOD bottle Add 5

ml of disttlied water and 5 ml of aqua regIa (6 1) Heat 2 mmutes m a water bath at 95°C

Cool, add 50 ml disttlied water and 15 ml potassIUm permanganate solutIOn (65) to each

sample bottle MIX thoroughly and place m the water bath for 30 mmutes at 95°C Cool

and add 6 ml of sodIUm chlonde-hydroxylamme sulfate (64) to reduce the excess

permanganate Add 55 ml of disttlied water Treatmg each bottle mdividually, add 5 m1

of stannous sulfate (63) and ImmedIately attach the bottle to the aeratIOn apparatus

Contmue as descnbed under (7 1)

82 An alternate dIgestIOn procedure employmg an autoclave may also be used In thIS

method 5 ml of conc H2S04and 2 ml of conc HN03 are added to the 0 2 g ofsample 5

ml of saturated KMn04 SolutIon IS added and the bottle covered WIth a pIece of

alummum fOil The samples are autoclaved at 121°C and 15 lbs for 15 mmutes Cool,

make up to a volume of 100 ml WIth disttlied water and add 6 ml of sodIUm chlonde2455-3
hydroxylamme sulfate solutIon (6 4) to reduce the excess permanganate Purge the dead

aIrspace and contmue as descnbed under (7 1)

9. CalculatIOn

9 1 Measure the peak height ofthe unknown from the chart and read the mercury value from

the standard curve

9 2 Calculate the mercury concentratIOn m the sample by the formula

ug Hg m the ahquot ugHg/g = wt of the aliquot in gms

9 3 Report mercury concentratIOns as follows Below 0 1 ug/gm, <0 1, between Oland 1

ug/gm, to the nearest 001 ug, between 1 and 10 ug/gm, to nearest 0 1 ug, above 10

ug/gm, to nearest ug

10 PrecIsIon and Accuracy

10.1 The followmg standard devIatIons on rephcate sediment samples were recorded at the

mdicated levels, 029 ug/g ±O 02 and 082 ug/g ±O 03 Recovery of mercury at these

levels, added as methyl mercunc chlOrIde, was 97% and 94%, respectIvely

Bibliography

1. Bishop, J N, "Mercury m SedIments", Ontano Water Resources Comm, Toronto, OntarIo,

Canada, 1971

2 SaIma, M , prIvate commumcatIOn"EPA CallNev Basm Office, Almeda, Cahforma

2455-4
MOLYBDENUM

Method 246.1 (Atomic Absorption, direct aspiration)

STORET No. Total 01062

Dissolved 01060

Suspended 01061

Optimum ConcentratIon Range: 1-40 mg/l usmg a wavelength of 313 3 nm

SensItIvIty: 0 4 mg/l

DetectIOn Limit: 0 1mg/l

PreparatIon ofStandard SolutIon

1 Stock SolutIOn Dissolve I 840 g of ammOnium molybdate (NH4)6M07024-4H20

(analytical reagent grade) m deIOnized dlstllled water and dllute to 1 hter 1 ml = 1 mg

Mo (1000 mg/l)

2 Alummum nitrate solutIOn Dissolve 139 g alummum nitrate, AI(N03)3-9H20, m 150 ml

ofdeIOnized dlstllled water, heat to effectsolutIOn Allow to cool and make up to 200 ml

3 Prepare dllutlons of the stock molybdenum solutIOn to be used as cahbratton standards

at the time of analysIs The cahbratton standards should be prepared usmg the same type

of aCid and at the same concentratIOn as will result m the sample to be analyzed either

directly or after processmg To each 100 ml ofstandard and sample ahke, add 2 ml ofthe

alummum nitrate solutIOn

Sample PreservatIOn

1 For sample handhng and preservation, see part 4 1 of the Atomic AbsorptIOn Methods

section ofthis manual

Sample PreparatIOn

1 The procedures for preparatIOn of the sample as given m parts 4 1 1 thru 4 1 4 of the

Atomic AbsorptIOn Methods sectIOn ofthis manual have been found to be satisfactory

Instrumental Parameters (General)

1 Molybdenum hollow cathode lamp

2 Wavelength 313 3 nm

3 Fuel Acetylene

4 OXidant Nitrous OXide

5 Type offlame Fuel nch

Approved for NPDES

Issued 1974

Edltonal reVISIOn 1978

2461-1
Analysis Procedure

1 For analysIs procedure and calculatIOn, see "DIrect AspIratIOn", part 9 1 of the AtomIC

AbsorptIOn Methods sectIOn ofthIs manual

Interferences

1 WIth the recommended mtrous oXIde-acetylene flame, Interferences ofcalCIUm and other I

Ions may be controlled by addIng 1000 mg/1 of a refractory metal such as alumInum

[Anal Chern Acta 44,437 (1969)] ThIS should be done to both samples and standards

alIke

Notes

1

2

Data to be entered Into STORET must be reported as ug/1

For concentratIons of molybdenum below 02 mg/1, the furnace procedure, Method

246 2, IS recommended

Precision and Accuracy

1 In a SIngle laboratory (EMSL), USIng a mIxed IndustrIal-domestIc waste effiuent at

concentratIOns of 0 30, 1 5 and 75 mg Moll, the standard deVIatIOns were ±O 007,

±O 02 and ±O 07, respectIvely Recovenes at these levels were 100%, 96% and 95%,

respectIvely

2461-2
MOLYBDENUM

Method 246.2 (Atomic Absorption, furnace technique)

STORET No. Total 01062

Dissolved 01060

Suspended 01061

Optimum Concentration Range: 3-60 ug/l

Detection LImit: 1ug/l

PreparatIOn of Standard SolutIOn

1 Stock solutIOn Prepare as descnbed under "dlrect asplratIOn method"

2 Prepare dl1utIOns of the stock solutIOn to be used as cahbratIOn standards at the time of

analysls These solutIOns are also to be useq for "standard addltIOns"

3 The cahbratIOn standard should be dl1uted to contam 0 5% (vIv) HN03

Sample Preservation

1 For sample handlmg and preservatIOn, see part 4 1 of the Atomlc AbsorptlOn Methods

sectIOn ofthls manual

Sample PreparatIOn

1 Prepare as descnbed under "dlrect asplratlOn method" Sample solutIOns for analysls

should contam 05% (v/v) HN03

Instrument Parameters (General)

1 Drymg Tlme and Temp 30 sec-125°C

2 AshmgTlme and Temp 30 sec-1400°C

3 Atomlzmg Tlme and Temp 15 sec-2800°C

4 Purge Gas Atmosphere Argon

5 Wavelength 313 3 nm

6 Other operatmg parameters should be set as speclfied by the partlcular mstrument

manufacturer

AnalYSIS Procedure

1 For the analysls procedure and the calculation, see "Furnace Procedure", part 9 3 ofthe

Atomlc AbsorptIOn Methods sectIOn ofthls manual

Approved for NPDES

Issued 1978

2462-1
Notes

1

2

3

4.

5

6

. The above concentratiOn values and Instrument conditiOns are for a Perkin-Elmer HGA2100, based on the use of a 20 ul mJectiOn, continUOUS flow purge gas and pyrolytic

graphite

Background correctiOn may be reqUlred Ifthe sample containS high dissolved sohds

The use ofmtrogen as a purge gas IS not recommended

For every sample matnx analyzed, verficatiOn IS necessary to determme that method of

standard addition IS not reqUlred (see part 5 2 1 of the AtOmlC AbsorptiOn Methods

section ofthls manual)

Ifmethod ofstandard addltion IS reqUlred, follow the procedure given earher In part 8 5

ofthe AtomiC AbsorptiOn Methods section ofthis manual

Data to be entered Into STORET must be reported as ug/l

Precision and Accuracy

1 PreCISion and accuracy data are not aval1able at thiS time

2462-2
NICKEL

Method 249.1 (Atomic Absorption, direct aspiration) >

STORET NO. Total 01067

Dissolved 01065

Suspended 01066

Optimum ConcentratIon Range: 03-5 mg/1 usmg a wavelength of232 0 nm

SensItivity. Q15 mg/1

DetectIOn LImIt: 0 04 mg/1

PreparatIOn ofStandard SolutIon

1 Stock SolutIOn DIssolve 4 953 g of nIckel nItrate, NI(N03)2-6H20 (analytical reagent

grade) m deIOnIzed wstI1led water Add 10 ml of conc nItnc aCId and dIlute to 1 lIter

WIth deIOnIzed dIstIlled water 1ml = I mg NI (1000 mg/1)

2 Prepare dIlutIOns of the stock nIckel solutIOn to be used as calIbratIOn standards at the

tIme of analySIS The calIbratIOn standards should be prepared usmg the same type of

aCId and at the same concentratIOn as wIll result m the sample to be analyzed eIther

dIrectly or after processmg

Sample PreservatIOn

1 For sample handlIng and preservation, see part 4 1 of the AtomIC Absorption Methods

sectIon ofthIS manual

Sample PreparatIon

1 The procedures for preparatIOn of the sample as gIven m parts 4 1 1 thru 4 1 4 of the

AtomIC AbsorptIOn Methods section ofthIS manual have been found to be satisfactory

Instrumentnl Parameters (General)

1 NIckel hollow cathode lamp

2 Wavelength 232 Qnm

3, Fuel Acetylene

4 OXIdant AIr

5 Type ofFlame OXIdIzmg

AnalYSIS Procedure

1 For analySIS procedure and calculatIOn, see "DIrect AspIratIOn", part 9 1 ofthe AtomIC

AbsorptIOn Methods sectIOn ofthIS manual

Approved for NPDES

Issued 1974

Editonal reVISIon 1978

249 1-1
Interferences

1 The 352 4 nm wavelength IS less susceptIble to spectral mterference and may be used

The calIbratIOn curve IS more lInear at thIS wavelength, however, there IS some loss of

sensItIvIty

Notes

" 1

2

3

For levels of mckel below 100 ug/1, eIther the SpecIal ExtractIOn Procedure, gIven m

part 9 2 of the Atomic AbsorptIOn Methods sectIOn or the furnace techmque, Method

249 2, IS recommended

Data to be entered mto STORET must be reported as ug/i

The heptoxime method may also be used (Standard Methods, 14th EdItIOn, p 232)

Precision and Accuracy

1 In a smgle laboratory (EMSL), usmg a mIxed mdustrIal-domestIc waste effluent at

concentratIOns of0 20, 1 0 and 50 mg NI/1, the standard devIatIons were ±O 011, ±O 02

and :1:004, respectIvely RecoverIes at these levels were 100%, 97% and 93%,

respectIvely

2491-2
NICKEL

Method 249.2 (Atomic Absorption, furnace technique)

STORET NO. Total 01067

Dissolved 01065

Suspended 01066

Optimum Concentration Range: 5-50 ug/l

Detection Limit: 1 ug/l

Preparation ofStandard Solution

1 Stock solutiOn Prepare as descnbed under "dIrect aspIratiOn method"

2 Prepare dIlutiOns of the stock solutiOn to be used as calIbratiOn standards at the tIme of

analysIs These SolutIons are also to used for "standard addItiOns"

. 3 The calIbratIon standard should be dIluted to contam 05% (v/v) HN03

Sample Preservation

1 For sample handlIng and preservation, see part 4 1 of the AtomIC AbsorptiOn Methods

sectiOn ofthis manual

Sample Preparation

1 Prepare as descnbed under "direct aSpIratiOn method" Sample solutions for analySIS

should contam 05% (v/v) HN03

Instrument Parameters (General)

1 Drymg Time and Temp 30sec-125°C

2 Ashmg TIme and Temp 30 sec-800oe

3 Atomlzmg Time and Temp 10 sec-27oo°C

4 Purge Gas Atmosphere Argon

5 Wavelength 2320nm

6 Other operating parameters should be set as speCified by the particular mstrument

manufacturer

AnalYSIS Procedure

1 For the analySIS procedure and the calculatiOn, see "Furnace Procedure" part 9 3 ofthe

AtomiC Absorption Methods section ofthI~ manual

Notes

1 The above concentratiOn values and mstrument conditions are for a Perkm-Elmer HGA2100, based on the use of a 20 ul mJectlon, continuous flow purge gas and pyrolytlc

Approved for NPDES

Issued 1978
graphIte Smaller SIze furnace devIces or those employIng faster rates of atomIzatIOn can

be operated USIng lower atomIzatIOn temperatures for shorter tIme penods than the

above recommended settIngs

2 The use ofbackground correctIOn IS recommended

3 NItrogen may also be used as the purge gas

4 For every sample matnx analyzed, venficatIOn IS necessary to determIne that method of

standard addItion IS not reqUIred (see part 52 1 of the AtomIC AbsorptIOn Methods

section ofthIS manual)

5 Ifmethod ofstandard addItIOn IS reqUIred, follow the procedure gIven earlIer In part 8 5

ofthe AtomIC Abs?rptlon Methods sectIOn ofthls manual

6 Data to be entered Into STORET must be reported as ug/l

Precision and Accuracy

1 PreCISIon and accuracy data are not aval1able at thIS tIme

II '

2492-2
OSMIUM

Method 252.1 (Atomic Absorption, direct aspiration)

STORET NO. Total*

Optimum ConcentratIon Range: 2-100 mg/l usmg a wavelength of290 9 nm

Sensitivity: 1mg/l

DetectIon LimIt: 0 3 mg/l

PreparatIon ofStandard SolutIon

1 Stock SolutlOn A standard AAS solution of osmIUm tetrox1de, OS04' 1000 mg/l m

aqueous matnx 1S aval1able from Alfa Products, Beverly, Massachusetts 01915

Cat #88084

2 Prepare dl1utlOns of the stock solutlOn to be used as cahbratlOn standards at the time of

analys1s The cahbratlOn standards should be prepared to contam 1% (v/v) HN03 and

1% (v/v) H2S04

Sample PreservatIon

1 For sample handhng and preservatlOn, see part 4 1 of the Atom1c Absorpt10n Methods

sectlOn ofth1s manual

Sample Preparation

1 Transfer a representative 100 ml ahquot ofthe well m1xed sample to a Gnffin beaker and

add 1ml ofconc dIstilled HN03 Place the beaker on a steam bath or hot plate and warm

for 15 mmutes Cool the beaker and filter to remove msoluble matenal that could clog

the atomIzer Add 1ml ofconc H2S04and adjust the volume back to 100 ml The sample

IS now ready for analysIs

Instrumental Parameters (General)

1 OsmIUm hollow cathode lamp

2 Wavelength 290 9 nm

3 Fuel Acetylene

4 OX1dant N1trous oXIde

5 Type offlame Fuel nch

AnalysIs Procedure

1 For the analysIs procedure and calculatlOn, see "DIrect Asp1ratlOn", part 9 1 of the

Atom1c AbsorptlOn Methods sectlOn ofth1s manual

*Not Ass1gned

Approved for NPDES

Issued 1976

Techmcal reVISIon 1978

252 1-1
Notes

1

2

,

Osmmm tetroxide, the usual commercial form, IS very volatl1e and highly tOXIC Care

should be exercised when workmg with this compound

For concentratlOns of osmmm below 0 5 mg/l the furnace procedure, Method 252 2, IS

recommended

Precision and Accuracy

1 PrecIsion and accuracy data are not aval1able at this time

252 1-2

" ,
OSMIUM

Method 252.2 (Atomic Absorption, furnace technique)

STORET NO Total*

OptImum ConcentratIon Range. 50-500 ug/l

DectectIOn Limit 20 ug/l

PreparatIon ofStandard SolutIon

1 Stock solutlOn Prepare as descnbed under "direct asplratlOn method"

2 Prepare dtlutlOns ofthe stock solutIon to be used as cahbratlOn standards at the time of

analysIs These solutlOns are also to be used for "standard additIons"

3 The cahbratlOn standard should be diluted to contam 1% (vIv) HN03

Sample PreservatIOn

1 For sample handhng and preservatlOn, see part 4 1 of the AtomIC AbsorptlOn Methods

sectIon OfthiS manual

Sample PreparatIon

I Prepare as descnbed under "dIrect aspiratlOn method", except omit the additlOn of

H2S04 on the final volume adjustment Sample SolutIons for analysIs should contam 1%

(v/v)HN03

Instrument Parameters(General)

1 DrymgTImeand Temp 30sec-105°C

2 Ashmg TIme and Temp See NOTE 3 below

3 AtomIzmg TIme and Temp 10 sec-2700°C

4 Purge Gas Atmosphere Argon

5 Wavelength 2909 nm

6 Other operatmg parameters should be set as specIfied by the particular mstrument

manufacturer

AnalysIs Procedure

1 For the analysIs procedure and the calculatIon, see "Furnace Procedure" part 9 3 ofthe

AtomIC AbsorptlOn Methods sectlOn ofthIS manual

Notes

1 OsmIUm tetrOXIde, the usual commerCIal form, IS very volattle and hIghly tOXIC Care

should be exercIsed when workmg WIth thIS compound

*Not ASSIgned

Approved for NPDES

Issued 1978

2522-1
2. The above concentration values and i'nstrument conditions are for a Perkm-Elmer HGA2100, based on the use of a 20 ul mJectiOn, contmuous flow purge gas and non-pyrolytic

graphite

3 Smce 0P4 volatilizes near 150·C, the allowable ashmg temperature must be venfied m

the sample matnx bemg analyzed

4. The use ofbackground correctiOn is recommended

5 For every sample matnx analyzed, venficatiOn is necessary to determme that method of

standard additiOn is not reqUired (see part 5 2 1 of the Atomic AbsorptiOn Methods

sectiOn ofthis manual)

6 Ifmethod ofstandard addition is reqUired, follow the procedure given earher m part 8 5

ofthe Atomic AbsorptiOn Methods sectiOn ofthis manual

Precision and Accuracy

1 PreCision and accuracy data are not available at this time

2522-2
PALLADIUM ,

Method 253.1 (Atomic Absorption, direct aspiration)

STORET NO. Total 01210

OptImum Concentration Range:

SensItiVIty. 0 25 mg!1

DetectIOn LImIt: 0 1mg/l

05-15 mg!1 usmg a wavelength of247 6 nm ,

PreparatIon ofStandard Solution

1 Stock SolutlOn Dissolve 0 1000 g of palladIUm Wire m a milllmum volume of aqua regia

and evaporate Just to dryness Add 5 ml conc RCI and 25 ml delOlllzed water and warm

until dissolutlOn IS complete Dilute to 100 ml with delOlllzed water (1 ml = 1mg Pd)

2 A standard AAS solution of palladous chlonde, PdC12, 1000 mg!l m aqueous matnx IS

available from Alfa Products, Beverly, Massachusetts 01915

Cat #88085

3 Prepare dilutIOns of the stock solutlOn to be used as cahbratlOn standards at the tIme of

analysis The calIbratlOn standards should be prepared to contam 05% (v!v) RN03

Sample PreservatIon

1 For sample handlIng and preservatlOn, see part 4 1 of the AtomiC AbsorptlOn Methods

sectlOn ofthis manual

Sample Preparation

1 Transfer a representative ahquot ofthe well mixed sample to a Gnffin beaker and add 3

ml of conc dIstilled RN03 Place the beaker on a steam bath and evaporate to near

dryness Cool the beaker and cautIously add a 5 ml portlOn of aqua regia (See below for

preparation of aqua regia t) Cover the beaker wIth a watch glass and return to the steam

bath Contmue heatmg the covered beaker for 30 mmutes Remove cover and evaporate

to near dryness Cool and add 1 1 redIstilled RN03 (1 ml per 100 ml dilutlOn) Wash

down the beaker walls and watch glass wIth distilled water and filter the sample to

remove sihcates and other msoluble matenal that could clog the atomizer Adjust the

volume to some predetermmed value based on the expected metal concentratlOn The

sample IS now ready for analysis

tAqua regia-prepare immediately before use by carefully addmg three volume of

cone Hel to one volume of cone HN03

Approved for NPDES

Issued 1976

Techlllcal reViSion 1978

253 I-I
Instrumental Parameters (General)

1 PalladIUm hollow cathode lamp

2 Wavelength 2476nm

3. Fuel Acetylene

4 OXIdant AIr

5 Type offlame OXIdIZIng

Analysis Procedure

1 For analysIs procedure and calculatIOn, see "DIrect AspIratIon", part 9 1 ofthe AtomIc

AbsorptIOn Methods sectIOn ofthIS manual

Notes

1 For concentratIOns ofpalladIUm below 0 25 mg/1, the furnace procedure, Method 253 2,

IS recommended

Precision and Accuracy

1 PrecIsIon and accuracy data are not avatlable at thIS tIme

253 1-2
PALLADIUM

Method 253.2 (Atomic Absorption, furnace technique)

STORET NO. Total 01210

Optimum Concentration Range: 20-400 ug/l

Detection LImIt: 5 ug/l

Preparation of Standard SolutIon

1 Stock solutIOn Prepare as descnbed under "dIrect aspIratIon method"

2 Prepare dIlutIOns of the stock solutIOn to be used as calIbratIOn standards at the time of

analysis These solutIOns are also to be used for "standard addItIons"

3 The calIbratIOn standard should be dIluted to contaIn 0 5% (vIv) HN03

Sample PreservatIon

1 For sample handlIng and preservatIOn, see part 4 1 ofthe AtomIC AbsorptIon Methods

sectIOn ofthIS manual

Sample PreparatIon

1 Prepare as descnbed under "dIrect aspIratIOn method" Sample solutIOn for analySIS

should contaIn 0 5%(v/v) HN03

Instrument Parameters (General)

1 DryIngTImeandTemp 30sec-125°C

2 Ashmg TIme and Temp 30 sec-1OOO°C

3 AtomIZIng TIme and Temp 10 sec-2800°C

4 Purge Gas Atmosphere Argon

5 Wavelength 247 6 nm

6 Other' operatIng parameters should be set as speCIfied by the partIcular Instrument

manufacturer

AnalYSIS Procedure

1 For the analySIS procedure and the calculatIOn, see "Furnace Procedure" part 9 3 of the

AtomiC AbsorptIOn Methods sectIOn ofthIS manual

Notes

1 The above concentratIOn values and Instrument conditIOns are for a PerkIn-Elmer HGA2100, based on the use of a 20 ul mJectIOn, contInUOUS flow purge gas and pyrolytIc

graphIte Smaller SIze furnace deVIces or those emplOyIng faster rates of atomIzatIOn can

be operated USIng lower atomIzatIon temperatures for shorter tIme penods than the

above recommended settIngs

Approved for NPDES

Issued 1978

2532-1
2 The use ofbackground cor~ectIOn IS recommended

3 NItrogen may also be used as the purge gas

4. For every sample matnx analyzed, venficatIOn IS necessary to determIne that method of

standard addItIOn IS not reqUIred (see part 5 2 1 of the AtomIC AbsorptIon Methods

sectIon ofthIS manual)

5 Ifmethod ofstandard addItIOn IS reqUIred, follow the procedure gIven earlIer In part 8 5

ofthe AtomIc AbsorptIOn MethodssectIOn OfthiS manual

Precision and Accuracy

1 PreCISIon and accuracy data are not avaIlable at thIS tIme

2532-2
PLATINUM

Method 255.1 (Atomic Absorption, direct aspiration)

STORET NO. Total*

Optimum Concentration Range: 5-75 mg/l usmg a wavelength of265 9 nm

SensItivity: 2 mg/l

Detection Limit: 0 2 mg/l

Preparation of Standard Solution

1 Stock SolutlOn Dissolve 0 1000 g of platmum metal m a minimum volume of aqua regia

and evaporate just to dryness Add 5 ml HCI and 01 g NaCI and agam evaporate just to

dryness Dissolve the residue m 20 ml of (1 1) HC! and dl1ute to 100 ml with delOnlzed

water (l ml = 1mg Pt)

2 A standard AAS solutlOn of chloroplatmlc aCid, H2PtCI6, 1000 mg/l m aqueous matnx

IS aval1able from Alfa Products, Beverly, Massachusetts 01915

Cat #88086

3 Prepare dl1utlOns of the stock solution to be used as cahbratlOn standards at the time of

analysIs The cahbratlOn standards should be prepared to contain a 5%(v/v) HN03

Sample Preservation

1 For sample handlIng and preservation, see part 4 1 of the AtomiC AbsorptlOn Methods

sectlOn ofthis manual

Sample Preparation

1 Transfer a representative ahquot ofthe well mixed sample to a Gnffin beaker and add 3

ml of conc distilled HN03 Place the beaker on a steam bath and evaporate to near

dryness Cool the beaker and cautlOusly add a 5 ml portion of aqua regia (See below for

preparation ofaqua regia t) Cover the beaker with a watch glass and return to the steam

bath Contmue heatmg the covered beaker for 30 mmutes Remove cover and evaporate

to near dryness Cool and add 1 1dlstl1led HN03 (1 m1 per 100 ml dl1utlOn) Wash down

the beaker walls and watch glass with dlstl1led water artd filter the sample to remove

sl1lcates and other msoluble material that could clog the atomizer Adjust the volume to

some predetermmed value based on the expected metal concentratlOn The sample IS now

ready for analysIs

tAqua regIa-prepare Immedtately before use by carefully addmg three volumes of conc Hel

to one volume of conc HN03

*Not ASSigned

Approved for NPDES

Issued 1976

Technical reVISion 1978

255 I-I
Instrumental Parameters (General)

I PlatInum hollow cathode lamp

2 Wavelength 265 9 nm

3 Fuel Acetylene

4 OXidant Air

5 Type offlame OXidizIng

Analysis Procedure

I For analysIs procedure and calculatIOn, see "Direct Aspiration", part 9 I ofthe Atomic

Absorption Methods section ofthis manual

Notes

I IFor concentrations ofplatInum. below 1.0 109/II the fl,lmace Brocedure, Method 255 2, IS

recommended

Precision and Accuracy I

I Precision and accuracy data are not avatlable at this time

, I

255 1-2

I I I IIIII 1 1

111111111 I 1 111111111 II II I I
PLATINUM

Method 255.2 (Atomic Absorption, furnace technique)

STORET NO. Total*

Optimum ConcentratIOn Range: 0 1-2 mgl1

Detection Limit: 0 02 mg/1

Preparation ofStandard SolutIOn

1 Stock solutIOn Prepare as descnbed under "direct aspiratIOn method"

2 Prepare dIlutIOns of the stock solutIOn to be used as calIbratIOn standards at the time of

analysIs These solutIOns are also to be used for "standard additIOns"

3 The calIbratIOn standard should be dIluted to contam 0 5% (vIv) HN03

Sample Preservation

1 For sample handlmg and preservation, see part 4: 1 of the AtomiC AbsorptIOn Methods

sectIOn ofthis manual

Sample PreparatIOn

1 Prepare as descnbed under "direct aspiratIOn method" Sample solutIOns for analysIs

shouldcontamO 5% (v/v)HN03

Instrument Parameters (General)

1 Drymg Time and Temp 30 sec-125°C

2 Ashmg Time and Temp 30sec-1300°C

3 Atomlzmg Time and Temp 10 sec-2800°C

4 Purge Gas Atmosphere Argon

5 Wavelength 265 9 nm

6 Other operatmg parameters should be set as speCified by the particular mstrument

manufacturer

AnalysIs Procedure

1 For the analysIs procedure and the calculatIOn, see "Furnace Procedure" part 9 3 ofthe

AtomIC Absorption Methods sectIOn ofthis manual

Notes

1 The above concentratIOn values and mstrument conditions are for a Perkm-Elmer HGA2100, based on the use of a 20 ul mJectIOn, contmuous flow purge gas and pyrolytIc

graphite Smaller size furnace deVices or those employmg faster rates of atomizatIOn can

*Not ASSigned

Approved for NPDES

Issued 1978

2552-1
be operated usmg lower atomIzatlOn temperatures for shorter tIme perIods than the

above recommended settmgs

2 The use ofbackground correctlOn IS recommended

3 NItrogen may also be used as the purge gas

4. For every sample matrIX analyzed, verIficatlOn IS necessary to determme that method of

standard addItIon IS not reqUIred (see part 5 2 1 of the AtomIC AbsorptIon Methods

sectlOn ofthIS manual)

5 Ifmethod ofstandard addItIon IS reqUIred, follow the procedure gIven earlter m part 8 5

ofthe AtomIc AbsorptIon Methods sectlOn ofthIS manual

Precision and Accuracy

1 PrecIsIon and accuracy data are not avatlable at thIs tIme

2552-2
POTASSIUM

Method 258.1 (Atomic Absorption, direct aspiration)

STORET NO. Total 00937

Dissolved 00935

Suspended 00936

OptImum ConcentratIOn Range: 0 1-2 mg!1 USIng a wavelength of766 5 nm

SensItivIty: 004 mg!1

Detection LImIt: 0 01 mg!l

Preparation ofStandard SolutIOn

1 Stock SolutlOn DIssolve 01907 g of KCI (analytIcal reagent grade), dned at 110°C, In

delOnIzed dlstllied water and make up to 1 hter I ml = 0 10 mg K (100 mg!l)

2 Prepare dllutlOns of the stock solutlOn to be used as cahbratlOn standards at the tIme of

analysIs The cahbratlOn standards should be prepared USIng the same type of aCId and at

the same concentratlOn as wIll result In the sample to be analyzed eIther dIrectly or after

processmg

Sample Preservation

1 For sample handhng and preservatlOn, see part 4 I of the Atomlc AbsorptIon Methods

sectlOn ofthIS manual

Sample Preparation

1 For the analysIs of total potassmm m domestIc and mdustnal effluents, the procedures

for the determInatlOn of total metals as gtven m parts 4 1 3 and 4 1 4 of the AtomIC

AbsorptlOn Methods sectlOn ofthIS manual have been found to be satIsfactory

2 For ambIent waters, a representatIve ahquot of a well mIxed sample may also be used

dIrectly for analysIs Ifsuspended sohds are present In sufficIent amounts to clog the

nebuhzer, the sample may be allowed to settle and the supernatant hqmd analyzed

dIrectly

Instrumental Parameters (General)

1 Potassmm hollow cathode lamp

2 Wavelength 7665 nm

3 Fuel Acetylene

4 OXIdant AIr

5 Type offlame Shghtly oXldlzmg

Approved for NPDES

Issued 1971

Edltonal reVlSlOn 1974

258 1-1
Analysis Procedure

1 For the analysIs procedure and the calculatIOn, see "DIrect AspiratIOn", part 9 1 of the

AtomIc AbsorptIon Methods sectIon ofthIs manual

Notes

1

2

3

4.

5

In aIr-acetylene or other hIgh temperature flames (> 2800°C), potassIum can experIence

partial IOnIZatIOn whIch mdirectly affects absorptIOn senSItIVIty The presence of other

alkalI salts m the sample can reduce this IOnIZatIon and thereby enhance analytIcal

results The IOnIZatIOn suppressIve effect of sodIUm is small If the ratIO of Na to K IS

under 10 Any enhancement due to sodIUm can be stabIlIzed by addmg excess sodIUm

(1000 ug/ml) to both sample and standard solutIOns If more strIngent control of

IOnIzatIon is reqUIred, the addItion of ceSIUm should be conSIdered Reagent blanks

should be analyzed to correct for potaSSIUm ImpUrIties m the buffer stock

The 404 4 nm lIne may also be used ThIS lIne has a relatIve sensItlVlty of 500

To cover the range of potaSSIUm values normally observed m surface waters (01-20

mg/l), It IS suggested that the burner head be rotated A 90° rotatIon of the burner head

prOVIdes approxImately one-eIghth the normal senSItiVIty

The flame photometrIc or colOrImetrIC methods may also be used (Standard Methods,

14th EdItIOn, p 234 & 235)

Data to be entered mto STORET must be reported as mgll

Precision and Accuracy

1 In a smgle laboratory (EMSL), usmg dIstIlled water samples spiked at concentrations of

1 6 and (5 3 mg Kll The standard deViatIOns were ±O 2 and ±O 5, respectively

Recovenes at these levels were 103% and 102%, respectively

258 1-2
RHENIUM

Method 264.1 (Atomic Absorption, direct aspiration)

STORET NO. Total*

OptImum ConcentratIon Range: 50-1000 mgl1 us10g a wavelength of346 Onm

SensItIvity: 15 mgl1

DetectIOn LImit: 5mg/1

PreparatIon of Standard SolutIon

1 Stock solution DIssolve 1 554 g of potassIUm perrhenate, KRe04' In 200 ml deIOmzed

water Dllute to 1 lIter wIth 1% (vIv) H2S04 (1 ml = 1mg Re)

2 A standard AAS solutIon of ammomum perrhenate, NH4Re04, 1000 mgl1 10 aqueous

matnx IS avallable from Alfa Products, Beverly, Massachussetts.01915

Cat #88089

3 Prepare dIlutIOns of the stock solutIOn to be used as calIbratIon standards at the tIme of

analysIs The calIbratIOn standards should be prepared us10g 1% (vIv) HN03

Sample PreservatIOn

1 For sample handl10g and preservatIOn, see part 4 1 of the AtomIC AbsorptIon Methods

sectIon ofthIS manual

Sample PreparatIon

1 Transfer a representative 100 ml alIquot ofthe well mIxed sample to a Gnffin beaker and

add 1 ml ofcone dIstIlled HN03 Place the beaker on a steam bath or hot plate and warm

for 15 mmutes Cool and filter to remove 1Osoluble matenal that could clog the atomIzer

Adjust the volume back to 100 ml The sample IS now ready for analysIs

Instrumental Parameters (General)

1 Rhemum hollow cathode lamp

2 Wavelength 3460 nm

3 Fuel Acetylene

4 OXIdant NItrous OXIde

5 Type offlame Fuel nch

AnalysIs Procedure

1 For the analysIs procedure and the calculation, see "dIrect aspIratIOn" part 9.1 of the

AtomIC AbsorptIOn Methods sectlOn ofthIS manual

*Not AssIgned

Issued 1976

Techmcal reVISIon 1978

264 1-1
Notes

I For concentratIOns ofrhemum below 10 mg/I, the furnace procedure, Method 264 2, IS

recommended

Precision and Accuracy

I PreCISIon and accuracy data are not aval1able at thIS tIme

I 1111

264 1-2
RHENIUM

Method 264.2 (Atomic Absorption, furnace technique)

STORET NO. Total*

OptImum ConcentratIOn Range 0 5-5 mg/l

Detection LImit o2mg/l

Preparation of Standard Solution

1 Stock solutIOn Prepare as deSCrIbed under "direct aspiratIOn method"

2 Prepare dllutIOns of the stock solutIOn to be used as cahbratIOn standards at the time of

analysIs These solutIOns are also to be used for "standard additIOns"

3 The cahbratlon standards should be dlluted to contam 1% (vIv) HN03

Sample Preservation

1 For sample handhng and preservatIOn, see part 4 1 of the AtomiC AbsorptIOn Methods

sectIOn ofthis manual

Sample Preparation

1 Prepare as deSCrIbed under "direct aspiratIOn method" Sample solutIOns for analysIs

should contam 1%(v/v) HN03

Instrument Parameters (General)

1 Drymg Time and Temp 30sec-125°C

2 Ashmg Time and Temp 30 sec-300°C

3 Atomlzmg Time and Temp 10 sec-2800°C

4 Purge Gas Atmosphere Argon

5 Wavelength 346 0 nm

6 Other operatmg parameters should be set as speCified by the particular mstrument

manufacturer

AnalySIS Procedure

1 For the analysIs procedure and the calculatIOn, see "Furnace Procedure" part 9 3 ofthe

AtomiC AbsorptIOn Methods sectIOn ofthis manual

*Not ASSigned

Issued 1978

2642-1
Notes

1

2

3

4

5

The above concentratiOn values and mstrument condItions are for a Perkm-Elmer HGA21~1 based on the use of a 20 ul mJectlon, contmuous ,flow purge gas and pyrolytic

graphIte

Background correctiOn may be reqUIred Ifthe sample contams hIgh dIssolved solIds

Smce many rhemum compounds volatIlIze near 300°C, the allowable ashmg temperature

should be venfied m the sample matnx bemg analyzed

For every sample matnx analyzed, venficatiOn IS necessary to determme that method of

standard add1tIon IS not reqUIred (see part 52 1 of the AtomIC AbsorptiOn Methods

section OfthiS manual)

Ifmethod ofstandard addItIon IS reqUIred, follow the procedure gIven earlIer m part 8 5

ofthe AtomIC AbsorptiOn Methods sectiOn ofthIS manual

Precision and Accuracy

1 PreCisIon and accuracy data are not avaIlable at thIS tIme

2642-2
RHODIUM

Method 265.1 (Atomic Absorption, direct aspiration)

STORET NO. Total*

Optimum Concentration Range: 1-30 mg/1 usmg a wavelength of 343 5 nm

SensitIvIty: 03 mg/1

Detection LImIt: 0 05 mg/1

Preparation ofStandard Solution

1 Stock SolutIOn DIssolve 0 3768 g of ammomum chlororhodIte, (NH4)3RhCI6-H20, m a

mmimum volume of 10% (v/v) HCI and dilute to 100 ml with 10% HCI (1 ml = 1mg

Rh)

2 A standard AAS solution ofrhodmm tnchlonde, RhCI3, 1000 mg/1 m aqueous matnx is

aval1able from Alfa Products, Beverly, Massachusetts 01915

Cat #88090

3 Prepare dl1utlOns of the stock solutIOn to be used as cahbratlOn standards at the time of

analysis The cahbratlOn standards should be prepared to contam 0 5% (v/v) HN03

Sample PreservatIon

1 For sample handhng and preservation, see part 4 1 of the Atomic AbsorptIOn Methods

section ofthis manual

Sample Preparation

1 Transfer a representative ahquot ofthe well mIXed sample to a Gnffin beaker and add 3

ml of cone distl1led HN03 Place the beaker on a steam bath and evaporate to near

dryness Cool the beaker and cautIOusly add a 5 ml portion of aqua regIa (See below for

preparation of aqua regia t) Cover the beaker with a watch glass and return to the steam

bath Contmue heatmg the covered beaker for 30 mmutes Remove cover and evaporate

to near dryness Cool and add 11 distl1led HN03(1 ml per 100 ml dl1utlQn) Wash down

the beaker walls and watch glass with distl1led water and filter the sample to remove

sl1icates and other msoluble matenal that could clog the atomizer Adjust the volume to

some predetermmed value based on the expected metal concentratIOn The sample is now

ready for analysis

tAqua regia-prepare ImmedIately before use by carefully addmg three volumes

of conc Hel to one volume of conc HN03

*Not ASSigned

Approved for NPDES

Issued 1976

Techmcal reViSion 1978

265 1-1
Instrumental Parameters (General)

1 RhodlUm hollow cathode lamp

2 Wavelength 343 5 nrn

3 Fuel Acetylene

4 OXidant Air

5. Type offlame OXldlzmg

Analysis Procedure

1 For the analysIs procedure and the calculatIOn, see "Drrect AspiratIOn", part 9 I of the

AtomiC Absorption Methods sectIOn ofthiS manual

Notes

1 For concentrations ofrhodlUm below 02 mg/I, the furnace procedure, Method 265 2, IS

recommended

Precision and Accuracy

1. Precision and accuracy data are not aval1able at this time

, ,

265 1-2
RHODIUM ,

Method 265.2 (Atomic Absorption, furnace technique)

STORET NO. Total*

Optimum ConcentratIon Range: 20-400 ug/l

Dete~tlOnLimit: 5 ug/l

PreparatIOn ofStandard SolutIon

1 Stock solution Prepare as descnbed under "dlrect asplratlOn method"

2 Prepare dllutlOns ofthe stock solutlOn to be used as cahbratlOn standards at the tlme of

analysls These solutlOns are also to be used for "standard addltlOns"

3 The cahbratlOn standard should be dlluted to contam 05% (v/v) HN03

Sample Preservation

1 For sample handhng and preservatlOn, see part 4 1 of the Atomlc AbsorptlOn Methods

sectlOn ofthls manual

Sample PreparatIon

1 Prepare as descnbed under "duect asplratlOn method" Sample solutlOns for analysls

should contam 05% (v/v) HN03

Instrument Parameters (General)

1 DrymgTlme and Temp 30 sec-125°C

2 AshmgTlmeand Temp 30sec-1200°C

3 Atomlzmg Tlme and Temp 10 sec-2800°C

4 Purge Gas Atmosphere Argon

5 Wavelength 3435 nm

6 Other operatmg parameters should be set as speclfied by the partlcular mstrument

manufacturer

Analysls Procedure

1 For the analysls procedure and the calculatlOn, see "Furnace Procedure" part 9 3 ofthe

Atomlc AbsorptlOn Methods sectlOn ofthls manual

*Not Asslgned

Approved for NPDES

Issued 1978

2652-1
Notes

1.

2.

3

4

5

The above concentratiOn values and mstrument conditions are for a Perkm-Elmer HGA2100, based on the use of a 20 ul mJectIon, contmuous flow purge gas and pyrolytlc

graphite

Background correction may be reqUIred Ifthe sample contams high dissolved sohds

The use ofmtrogen as a purge gas IS not recommended

For every sample matnx analyzed, venficatlOn IS necessary to determme that method of

standard additIOn IS not reqUIred (see part 5 2 1 of the AtomiC AbsorptiOn Methods

section ofthis manual)

Ifmethod ofstandard additiOn IS reqUIred, follow the procedure given earher m part 8 5

ofthe AtomiC AbsorptiOn Methods section ofthis manual

Precision and Accuracy

1. Precision and accuracy data are not aval1able at this time

, " .

2652-2
RUTHENIUM " t

Method 267.1 (Atomic ,Absorption, direct aspiration)

STORET NO. Total*

Optimum ConcentratIOn Range: I-50 mg/l usmg a wavelength of 349 9 um

_Sensitivity: 0 5 mg/l

Detection Limit: 0 2 mg/l

Preparation ofStandard Solution

I Stock SolutlOn DIssolve 02052 g ofruthemum chlonde, RuCI3, m a mmimum volume of

20% (vIv) HCI and dIlute to 100 ml wIth 20% HCI (1 ml = 1mg Ru)

2 Prepare dIlutlOns of the stock SolutlOU to be used as calIbratlOn standards at the tIme of

analysIs The calIbratlOn standards should be prepared usmg I % (vIv) HCI

Sample Preservation

1 For sample handlIng and preservatlOn, see part 4 1 of the AtomIC AbsorptlOn Methods

sectlOn ofthIS manual

Sample PreparatIOn

1 Transfer a representative 100 ml alIquot ofthe well mIxed sample to a Gnffin beaker and

add 2 ml of dIstIlled (1 1) HCI Place the beaker on a steam bath or hot plate and warm at

95°C for 15 mmutes Cool the beaker and filter the sample to remove msoluble matenal

that could clog the atomIzer Adjust the volume back to 100 ml The sample IS now ready

for analysIs

Instrumental Parameters (General)

1 Ruthemum hollow cathode lamp

2 Wavelength 349 9 nm

3 Fuel Acetylene

4 OXIdant AIr

5 Type offlame OXIdIzmg

AnalYSIS Procedure

1 For the analysIs procedure and the calculatIon, see "DIrect AspiratlOn", part 9 1 of the

AtomIC AbsorptlOn Methods sectlOn ofthIS manual

*Not ASSIgned

Approved for NPDES

Issued 1976

Techmcal reVlSlon 1978

267 1-1
Notes

1 For concentratlOns ofruthemum below 0 5 mg/l, the furnace procedure, Method 267 2,

1S recommended

Precision and Accuracy

1. Prec1s1on and accuracy data are not aVailable at th1s t1me

267 1-2
RUTHENIUM

Method 267.2 (Atomic Absorption, furnace technique)

STORET NO. Total*

OptImum ConcentratIon Range' 0 1-2 mg/l

DetectIOn LImit. 0 02 mg/l

PreparatIon ofStandard SolutIOn

1 Stock solutIOn Prepare as descnbed under "dIrect aspIratIOn method"

2 Prepare dtlutIOns of the stock solutIon to be used as cahbration standards at the tIme of

analysIs These SolutIons are also to be used for "standard addItIons"

3 Usmg dIstIlled (1 1) HCI, the cahbratIOn standardsshould be dtluted to contam 1% (v/v)

HCI

Sample PreservatIOn

1 For sample handhng and preservatIOn, see part 4 1 of the AtomIc AbsorptIon Methods

sectIon ofthIS manual

Sample Preparation

1 Prepare as descnbed under "dIrect aspIratIOn method" Sample solutIOns for analysIs

should contam 1% (v/v) Hel

Instrument Parameters (General)

1 Drymg TIme and Temp 30 sec-125°C

2 Ashmg TIme and Temp 30 sec-400°C

3 AtomIzmg TIme and Temp 10 sec-2800°C

4 Purge Gas Atmosphere Argon

5 Wavelength 349 9 nm

6 Other operatmg parameters should be set as specIfied by the partIcular mstrument

manufacturer

AnalYSIS Procedure

1 For the analysIs procedure and the calculatIon, see "Furnace Procedure" part 9 3 ofthe

AtomIc AbsorptIon Methods sectIOn ofthIs manual

*Not ASSIgned

Approved for NPDES

Issued 1978

2672-1
Notes

1

2

3.

4

5

The above concentratlOn values and mstrument conditlOns are for a Perkm-Elmer HGA2100, based on the use of a 20 ul mJectlOn, contmuous flow purge gas and non-pyrolytic

graphIte

Background correctlOn may be reqUIred Ifthe sample contams hIgh dIssolved solIds

NItrogen may also be used as the purge gas

For every sample matrIX analyzed, verIficatlOn IS necessary to determme that method of

standard additlOn IS not reqUIred (see part 5 2 1 of the AtomIC AbsorptlOn Methods

sectlOn ofthis manual)

Ifmethod ofstandard addItlO~ IS reqUIred, follow the procedure gIven earlIer m part 8 5

ofthe Atomic AbsorptIon Methods sectlOn ofthIS manual

Precision and Accuracy

1 PrecIsion and accuracy data are not avaIlable at thIS tIme

l' 1

2672-2
SELENIUM

Method 270.2 (Atomic Absorption, furnace technique)

STORET NO. Total 01147

Dissolved 01145

Suspended 01146

Optimum ConcentratIon Range: 5-100 ug/l

DetectIon LImIt: 2 ug/l

PreparatIon ofStandard Solution

1 Stock SeleDlum Solution DIssolve 0 3453 g ofselenous aCid (actual assay 946% H2Se03)

m deIODlzed distIlled water and make up to 200 ml 1ml = 1mg Se (1000 mg/l)

2 Nickel Nitrate SolutIOn, 5% Dissolve 24 780 g ofACS reagent grade NI(N03)2.6H20 m

deloDlzed distIlled water and make up to 100 ml

3 Nickel Nitrate SolutIOn, 1% DIlute 20 ml of the 5% Dlckel Dltrate to 100 ml with

deIODlzed distIlled water

4 Workmg SeleDlum SolutIOn Prepare dIlutIOns of the stock solutIOn to be used as

calIbratIOn standards at the time of analySIS Withdraw approprIate alIquots ofthe stock

solution, add 1 ml of conc HN03, 2 ml of 30% H20 2and 2 ml of the 5% Dlckel nItrate

solutIOn Dl1ute to 100 ml With deIOnIZed dlstl1led water

Sample PreservatIon

1 For sample handlIng and preservatIOn, see part 4 1 of the Atomic AbsorptIOn Methods

section ofthis manual

Sample PreparatIon

1 Transfer 100 ml ofwell-mIXed sample to a 250 ml GrIffin beaker, add 2 ml of 30% H20 2

and suffiCient conc HN03to result m an aCid concentration of 1% (v/v) Heat for 1 hour

at 95°C or until the volume IS slIghtly less than 50 ml

2 Cool and brmg back to 50 ml With deiOnIzed dlstl1led water

3 Pipet 5 ml of thiS digested solutIOn mto a lO-ml volumetrIC flask, add 1 ml of the 1%

nIckel nItrate solution and dIlute to 10 ml With deIOnIzed distIlled water The sample IS

now ready for mJectIOn mto the furnace NOTE If solubilIzatIOn or digestIOn IS not

reqUIred adjust the HN03concentratIOn ofthe sample to 1% (v/v) and add 2 ml of30%

H20 2 and 2 ml of 5% nIckel nItrate to each 100 ml of sample The volume of the

calIbratIOn standard should be adjusted With deiOnIzed distilled water to match the

volume change ofthe sample

Approved for NPDES and SDWA

Issued 1978

2702-1
Instrument Parameters

1 DryIng tune and temperature 30 sec @ 125°C

2 Charnng tIme and temperature 30 sec @ 1200°C

3. AtomIzIng tIme and temperature 10 sec @ 2700°C

4 Purge Gas Atmosphere Argon " "

5 Wavelength 1960nm

6 Other operatIng parameters should be set as speCIfied by the partICular Instrument

manufacturer

AnalysIs Procedure

1 For the analysIs procedure and the calculatIon see "Furnace Procedure" part 9 3 of the

AtomIC AbsorptIOn Methods sectIOn oftms manual

Notes

1.

2.

3

4

5

6

7

The above concentratIon values and Instrument condItIOns are for a PerkIn-Elmer HGA2100, based on the use of a 20 ul lUJecnon, purge gas lUterrupt and non-pyrolync

graphIte Smaller sIze furnace deVIces or those employIng faster rates of atomIzatIOn can

be operated USIng lower atoffilzatlOn temperatures for shorter tIme penods than the

above recommended settIngs

The use ofbackground correctIon IS recommended

Selemum analysIs suffers Interference from chlondes (> 800 mg/l) and sulfate (> 200

mg/l) For the analysIs ofIndustnal effiuents and samples wIth concentratIons ofsulfate

from 200 to 2000 mg/l, both samples and standards should be prepared to contaIn 1%

mckel

For every sample matnx analyzed, venficatlOn IS necessary to deterrmne that method of

standard addItIOn IS not reqUIred (see part 5 2 1 of the AtomIC AbsorptIOn Methods

sectIon ofthIS manual)

For qualIty control reqUIrements and optIOnal recommendatIons for use In dnnkIng

water analyses, see part 10 ofthe AtomIC AbsorptIOn Methods sectIOn ofthIs manual

Ifmethod ofstandard addItIOn IS reqUIred, follow the procedure given earlIer In part 8 5

ofthe AtomIC AbsorptIOn Methods sectIOn ofthIS manual

Data to entered Into STORET must be reported as ug/l

Precision and Accuracy

1 USIng a sewage treatment plant effiuent contaInIng < 2 ug/l and spIked wIth a

concentratIon of20 ug/l, a recovery of99% was obtaIned

2 USIng a senes of Industnal waste effiuents spIked at a 50 ug/l level, recovenes ranged

from 94 to 112%

3 USIng a 0 1% mckel mtrate solutIOn as a synthetIc matnx with selemum concentratIOns

of 5, 10,20,40, 50, and 100 ug/l, relative standard deVIatIOns of 14 2, 11 6, 9 3, 72, 64

and 4 1%, respectively, were obtaIned at the 95% confidence level

2702-2
4 In a smgle laboratory (EMSL), usmg CmcmnatI, OhIO tap water spIked at concentratIOns

of 5, 10, and 20 ug Sell, the standard devIatIons were ±O 6, ±O 4, and ±O 5,

respectIvely Recovenes at these levels were 92%,98%, and 100%, respectIvely

Reference:

"Deternumng Selemum m Water, Wastewater, SedIment and Sludge By Flameless AtomIC

AbsorptIon Spectroscopy", Martm, T D, Kopp, J F and EdIger, R D AtomIc AbsorptIOn

Newsletter 14, 109 (1975)

2702-3
SELENIUM

Method 270.3 (Atomic Absorption, gaseous hydride)

STORET NO. Total 01147

Dissolved 01145

Suspended 01146

1 Scope and ApphcatiOn

lIThe gaseous hydnde method determmes morgamc selemum when present m

concentratiOns at or above 2 ug/l The method IS apphcable to dnnkmg water and most

fresh and sahne waters, m the absence of hIgh concentratiOns of chromIUm, cobalt,

copper, mercury, molybdenum, mckel and sIlver

2 Summary ofMethod

2 1 Selemum m the sample IS reduced from the +6 oXIdatiOn state to the +4 oXIdatiOn state

by the addItiOn of SnClz Zmc IS added to the aCIdIfied sample, producmg hydrogen and

convertmg the selemum to the hydnde, SeHz The gaseous selemum hydnde IS swept mto

an argon-hydrogen flame of an atomIC absorptiOn spectrophotometer The workmg

range ofthe method IS 2-20 ug/l usmg the 196 0 nm wavelength

3 Comments

3 1 In analyzmg dnnkmg water and most surface and ground waters, mterferences are rarely

encountered Industnal waste samples should be spIked WIth a known amount of

selemum to estabhsh adequate recovery

3 2 Orgamc forms ofselemum must be converted to an morgamc form and orgamc matter

must be OXIdIzed before begmmng the analysIs The OXIdatiOn procedure gIven m method

206 5 (Standard Methods, 14th Ed 404B, p 285, Procedure 4 1) should be used

3 3 For sample handlmg and preservatIon, see part 4 1 of the AtomIC AbsorptiOn Methods

sectiOn ofthIS manual

34 For quahty control reqUIrements and optiOnal recommendatIons for use m dnnkmg

water analyses, see part 10 ofthe AtomIC AbsorptiOn Methods sectiOn ofthIS manual

3 5 Data to be entered mto STORET must be reported as ug/l

4 PreCIsiOn and Accuracy

4 1 Ten rephcate solutiOns ofselemum OXIde at the 5, 10 and 15 ug/l1evel were analyzed by

a smgle laboratory Standard deVIatIons at these levels were ±O 6, ±1 1 and ±2 9 WIth

recovenes of 100, 100 and 101% (Caldwell, J S, Lishka, R J, and McFarren, E F,

"EvaluatIon ofa Low-Cost Arsemc and Selemum DetermmatiOn at MIcrogram per LIter

Levels", JAWWA, vol 65, p 731, Nov 1973)

Approved for NPDES and SDWA

Issued 1974

2703-1
5. References

5.1 Except for the perchlonc aCId step, the procedure to be used for thIS determInatIOn IS

found In

Standard Methods for the EXamInatIOn of Water and Wastewater, 14th EdItIOn, p 159,

Method 301A(VII), (1975)

2703-2
SILVER

Method 272.1 (Atomic Absorption, direct aspiration)

STORET NO. Total 01077

Dissolved 01075

Suspended 01076

OptImum ConcentratIon Range: 0 1-4 mg/l usmg a wavelength of328 I nm

SensItivIty: 006 mg/l

Detection LImIt: 001 mg/l

PreparatIOn ofStandard SolutIon

1 Stock SolutlOn DIssolve 1 575 g of AgN03 (analytiCal reagent grade) m delOmzed

dlstl1led water, add 10 ml conc HN03 and make up to I hter 1 ml = 1 mg Ag (1000

mg/l)

2 Prepare dl1utlOns of the stock solutIon to be used as cahbratlOn standards at the time of

analysIs The cahbratlOn standards should be prepared usmg mtnc aCId and at the same

concentratlOn as wIll result m the sample to be analyzed eIther dIrectly or after

processmg

3 lodme SolutlOn, 1 N DIssolve 20 grams of potasslUm lOdlde, KI (analytIcal reagent

grade) m 50 ml of delomzed dIstilled water, add 127 grams of lOdme, 12 (analytIcal

reagent grade) and dilute to 100 ml Store m a brown bottle

4 Cyanogen IodIde (CNI) SolutIon To 50 ml of delomzed dlstl1led water add 4 0 ml conc

NH40H, 6 5 grams KCN, and 5 0 ml of ION 12 solutlOn MIX and dilute to 100 ml wIth

delOmzed dIstIlled water Fresh solutlOn should be prepared every two weeks (1)

Sample PreservatIon

1 For sample handhng and preservatlOn, see part 4 1 of the AtomIC AbsorptlOn Methods

section ofthIS manual

Sample PreparatIOn

1 The procedures for preparatlOn of the sample as gIven m parts 4 1 1 thru 4 1 3 of the

AtomIc AbsorptlOn Methods sectlOn of thIS manual have been found to be satIsfactory,

however, the resIdue must be taken up m dilute mtnc aCId rather than hydrochlorIc to

prevent preclpltatlOn ofAgCI

Approved for NPDES and SDWA

Issued 1971

Edltonal reVlSlOn 1974

Techmcal reVlSlOn 1978

272 1-1
Instrumental Parameters (General)

1. Silver hollow cathode lamp

2. Wavelength 328 1 nm

3 Fuel Acetylene

4 OXIdant AIr

5 Type offlame OXldIzmg

I 1

Analysis Procedure

1 For the analysIs procedure and the calculation, see "Direct AspiratIOn", part 9 1 of the

Atomic Absorption Methods sectIOn ofthis manual

Notes

1

2

3

4

5

For levels ofSilver below 30 ug/l, either the SpeCial ExtractIOn Procedure, given m part

92 ofthe Atomic Absorption Methods sectIOn o~ the furnace procedure, Method 272 2,

IS recommended

SIlver mtrate standards are hght sensitive Dilutions of the stock should be discarded

after use as concentrations below 10 mg/l are not stable over long penods oftime

If absorptIOn to contamer walls or the formation of AgClls suspected, make the sample

basIc usmg conc NH40H and add 1 ml of(CNI) solutIOn per 100 ml ofsample MIx the

sample and allow to stand for 1 hour before proceedmg wIth the analysIs (I) , , The 338 2 nm wavelength may also be used ThiS has a relatIve sensitivity of2

Data to be entered mto STORET must be reported as ug/l' , 1

Precision and Accuracy

1 In a round-robm study reported by Standard Methods, a synthetic sample contammg 50

ug Ag/l was analyzed by 50 laboratones With a reported standard deViatIon of ±8 8 and

a relative error 10 6% '

References

1. "The Use of Cyanogen IodIde (CNI) as a Stablhzmg Agent for StIver m Photographic

Processmg Effluent Sample", Owerbach, Damel, Photographic Technology DIVISion,

Eastman Kodak Company, Rochester, N Y 14650 ,

2 Standard Methods for Exammatlon of Water and Wastewater, 14th Edition, p 148,

Method301A

, ;

272 1-2
SILVER

Method 272.2 (Atomic Absorption, furnace technique)

STORET NO. Total 01077

Dissolved 01075

Suspended 01076

Optimum ConcentratIon Range: 1-25 ug/l

Detection Limit: 0 2 ug/l

Preparation ofStandard SolutIon

1 Stock Solution Prepare as descnbed under "direct aspIration method"

2 Prepare dIlutIOns of the stock solutIOn to be used as cahbratIOn standards at the time of

analysIs These solutIOns are also to be used for "standard addItIons"

3 The cahbratIOn standard should be dIluted to contam 05% (v/v) HN03

Sample Preservation

1 For sample handhng and preservatIon, see part 4 1 of the AtomIC AbsorptIOn Methods

sectIon ofthIS manual

Sample PreparatIon

1 Prepare as descnbed under "dIrect aspIratIOn method" Sample solutIOns for analysIs

shouldcontamO 5% (v/v)HN03

Instrument Parameters (General)

1 DrymgTImeand Temp 30sec-125°C

2 Ashmg TIme and Temp 30 sec-400°C

3 AtomIzmg TIme and Temp 10 sec-2700°C

4 Purge Gas Atmosphere Argon

5 Wavelength 328 1nm

6 Other operatmg parameters should be set as specIfied by the partICular mstrument

manufacturer

AnalysIs Procedure

1 For the analysIs procedure and the calculatIOn, see "Furnace Procedure" part 9 3 of the

AtomIC AbsorptIOn Methods sectIOn ofthIS manual

Approved for NPDES and SDWA

Issued 1978

272 2-1
Notes

1

2

3

4

5

6

7

8

The above con\.entratlon values and Instrument conditions are for a Perkin-Elmer HGA2100, based on the use of a 20 ul inJectiOn, continUOUS flow purge gas and non-pyrolytlc

graphite Smaller size furnace devices or those employing faster rates of atomizatiOn can

be operated USing lower atomization temperatures for shorter time penods than the

above recommended settings

Background correctiOn may be reqUIred Ifthe sample containS high dissolved sohds

The use ofhahde aCids should be aVOIded

If adsorption to container walls or formatiOn ofAgClls suspected, see NOTE 3 under the

Direct AspiratiOn Method 272 1

For every sample matnx analyzed, venficatIOn IS necessary to determine that method of

standard additiOn IS not reqUIred (see part 5 2 1 of the AtomiC AbsorptIOn Methods

section ofthis manual)

For quahty control reqUIrements and optional recommendatIOns for use In dnnkIng

water analyses, see part 10 ofthe AtomiC Absorption Methods sectIOn ofthis manual

Ifmethod ofstandard addition IS reqUIred, follow the procedure given earher In part 8 5

ofthe AtomiC AbsorptIOn Methods sectIOn ofthis manual

Data to be entered Into STORET must be reported as ug/l

PreciSIOn and Accuracy:

1. In a Single laboratory (EMSL), USing CinCinnati, OhiO tap water spiked at concentrations

of 25, 50, and 75 ug Ag/l, the standard deViatIOns were ±O 4, ±O 7, and +09,

respectively Recovenes at these levels were 94%, 100% and 104%, respectively I

I, ,

272 2-2
SODIUM

Method 273.1 (AtomIC Absorption, direct aspiration)

STORET NO. Total 00929

DIssolved 00930

Suspended 00928

Optimum ConcentratIOn Range 003-1 mg/1 usmg a wavelength of589 6 nm

SensItivIty 0015 mg/1

Detection LImIt 0 002 mg/1

PreparatIOn of Standard SolutIOns

1 Stock SolutIOn Dissolve 2 542 g of NaCl (analytical reagent grade), dned at 140°C, m

deIOnIzed distilled water and make up to 1 hter 1011 = 1mg Na (1000 mg/1)

2 Prepare dilutIOns of the stock solutIOn to be used as cahbratIOn standards at the time of

analySIS The cahbratIOn standards should be prepared usmg the same type of aCId and at

the same concentratIOn as wIll result m the sample to be analyzed either directly or after

processmg

Sample PreservatIOn

1 For sample handlmg and preservatIOn, see part 4 1 of the AtomIc Absorption Method.,

sectIOn ofthIS manual

Sample Preparation

1 For the analySIS of total sodmm m domestic and mdustnal effluents, the procedures for

the determmatIOn of total metals as gIven m parts 4 1 3 and 4 1 4 of the Atomll

AbsorptIOn Methods sectIOn ofthis manual have been found to be satisfactory

2 For ambient waters, a representattve ahquot of a well-mIxed sample may be used directly

for analySIS If suspended sohds are present III suffiCIent amounts to clog the nebuhzer,

the sample may be allowed to settle and the supernatant hqUld analyzed dIrectly

Instrumental Parameters (General)

1 Sodmm hollow cathode lamp

2 Wavelength 589 6 nm

3 Fuel Acetylene

4 OXIdant Air

5 Type offlame OXldlzmg

Approved for NPDES

Issued 1971

Editonal revIsion 1974

273 I-I
Anal)sls Procedure

1 For the analysIs procedure and the calculatIOn, see "Direct Aspiration", part 9 1 of the

Atomic Absorption Methodssection ofthis manual

Notes

1

2

3

4

The 3302 nm resonance lme ofsodlUm, which has a relative senSItIvity of 185, prOVides a

convenient way to aVOid the need to dilute more concentrated solutIOns ofsodlUm

Low-temperature flames mcrease sensitivIty by reducmg the extent of I011lZatIOn of thIS

easIly 1011lzed metal I011lZatIOn may also be controlled by addmg potasslUm (1000 mg/l)

to both standards and samples

Data to be entered mto STORET must be reported as mg/l

The flame photometnc method may also be used (Standard Methods, 14th EdItIOn, p

250)

Precision and Accuracy

1 In a smgle laboratory (EMSL), usmg dIstIlled water samples spIked at levels of 8 2 and 52

mgNa/l, the standard deViatIOns were ±O 1 and ±O 8, respectIvely Recovenes at these

le\els were 102% and 100%

273 1-2
&EPA

United States

Environmental Protection

Agency

Research and Development

Test Method

Environmental MOnltonng and

Support Laboratory

Cincinnati OH 45268

Sodium (Atomic

Absorption, furnace

technique)-Method 273.2

Optimum Concentration Range 1-30

tig/l

Detection limit 02 tig/l

PreparatIOn of Standard Solution

1 Stock solution Prepare as

described under direct

aspiratIOn method

2 Prepare dilutions of the stock

solutIOn to be used as calibration

standards at the time of analysIs

These solutions are also to be

used for standard additions

3 The calibration standard should

be diluted to contain 05% (v/v)

HN03

Sample Preservation

1 For sample handling and preservation see part 41 of the Atomic

Absorption Methods section of

this manual

Sample Preparation

1 Prepare as described under direct aspiration method Sample

solutions for analysIs should

contain 05% (v/v) HN03

Instrument Parameters (General)

1 Drying Time and Temp 30 sec @

125°C

2 Ashlng Time and Temp 30 sec @

250°C

3 Atomizing Time and Temp 10 sec

@ 2000°C

4 Purge Gas atmosphere Argon

5 Wavelength 589 6 nm

6 Other operating parameters

should be set as specified by the

particular Instrument

manufacturer

AnalysIs Procedure

1 For the analysIs procedure and

the calculation, see Furnace

Procedure 93 of the Atomic

Absorption method section of

thiS manual

Notes

1 The above concentration values

and Instrument conditions are

for a Perkin-Eimer HGA-2100

based on the use of a 20 til

injection continUOUS flow purge

gas and non-pyrolytlc graphite

Smaller size furnace devices or

those employing faster rates of

atomization can be operated

uSing lower atomizatIOn

temperatures for shorter time

periods than the above

recommended settmgs

2 Samples containing

concentrations higher than those

given In the optimum range

should be analyzed by either the

direct aspiration method (Method

273 1) or the flame photometric

method (Std Methods 14th

Edition p 250)

3 Nitrogen may also be used as

the purge gas

4 For every sample matrix

analyzed, verification IS

necessary to determine that

method of standard addition IS

not required (see 5 2 1 of

the Atomic Absorption method

section of thiS manual)

5 If method of standard addltl<ln IS

required follow the procedure

given earlier In 85 of the

Atomic AbsorptIOn methos

sectIOn of thiS manual

27321 Dec 1982
6 Data to be entered Into STORET

must be reported as pg/L

Precision and Accuracy

1 Precision and accuracy data are

not available at this time

Dec 1982 2732-2
THALLIUM

Method 279.1 (Atomic Absorption, direct aspiration)

STORET NO. Total 01059

DIssolved 01057

Suspended 01058

Optimum ConcentratIOn Range. 1-20 mg/l USing a wavelength of276 8 nm

SensItivity' 0 5 mg/l

DetectIOn Limit. 0 1mg/l

Preparation of Standal d SolutIOn

1 Stock Solution Dissolve 1 303 g ofthalhum mtrate, TINOJ (analytical reagent grade) In

delOmzed distilled water Add 10 ml of conc mtnc aCid and dtlute to 1 hter with

delOmzed distilled water 1ml = 1mgTl (1000 mg/l)

2 Prepare dilutIOns ofthe stock thallIum solutIOn to be used as cahbratton standards at the

time of analySIS The cahbratIon standards should be prepared USing mtnc aCid and at the

c;ame concentratIOn as Will result In the sample to be analyzed either directly or after

proceC;C;Ing

Sample Preservation

1 For sample handhng and preservation, see part 4 1 of the AtomiC Absorptton Methods

c;ectlOn ofthis manual

Sample PreparatIOn

1 The procedures for preparatIOn of the sample as given In parts 4 1 1 thru 4 1 4 of the

AtomiC Absorption Methods sectIOn of thiS manual have been found to be satisfactory If

HellS omitted

Instrumental Parameters (General)

1 Thalhum hollow cathode lamp

2 Wavelength 276 8 nm

3 Fuel Acetylene

4 OXidant Air

5 Type offlame OXidiZing

Approved for NPDES

Issued 1974

Techmcal reVlSlon 1978

279 I-I
Analysis Procedure

I For the analysIs procedure and the 'calculatIOn, see "DIrect AspIratIOn", part 9 1 of the

AtomIc AbsorptIOn Methods sectIon ofthIS manual

Notes

1

2

For concentratIons ofthalhum below 0 2 mg/l, the furnace procedure, Method 2792, IS

recommended

Data to be entered mto STORET must be reported as ug/l

Precision and Accuracy I ~, I r

1 In a SIngle laboratory (EMSL), USIng a mIxed Industnal-domestIc waste effluent at

concentratIons of 0 60,30 and 15 mg TIll, the standard deVIatIons were ±O 018, ±O 05

and ±O 2, respectIvely Recovenes at these levels were 100%, 98% and 98%,

respectIvely ,

I '

'I

2791-2
THALLIUM

Method 279.2 (Atomic Absorption, furnace technique)

STORET NO. Total 01059

Dissolved 01057

Suspended 01058

Optimum Concentration Range: 5-100 ug/l

Detection LImIt: 1 ug/l

PreparatIOn ofStandard SolutIOn

1 Stock solutIOn Prepare as descnbed under "dIrect aspIratIOn method"

2 Prepare dl1utIOns of the stock solutIOn to be used as calIbratIOn standards at the tIme of

analysIs These solutIOns are also to be used for "standard addItIOns"

3 The calIbratIOn standard should be dl1uted to contam 05% (v/v) HN03

Sample Preservation

1 For sample handhng and preservatIOn, see part 4 1 of the AtomIc AbsorptIOn Methods

sectIOn ofthIS manual

Sample Preparation

1 Prepare as descnbed under "dIrect aspIratIon method" Sample solutIOns for analySIS

should contam 05% (v/v) HN03

Instrument Parameters (General)

1 Drymg TIme and Temp 30 sec @ 125°C

2 Ashmg TIme and Temp 30 sec @ 400°C

3 AtomIzmg TIme and Temp 10 sec @ 2400°C

4 Purge Gas Atmosphere Argon

5 Wavelength 276 8 nm

6 Other operatmg parameters should be set as specIfied by the partIcular mstrument

manufacturer

AnalysIs Procedure

1 For the analysIs procedure and the calculatIOn, see "Furnace Procedure" part 9 3 ofthe

AtomIC AbsorptIon Methods sectIOn ofthIS manual

Approved for NPDES

Issued 1978

2792-1
Notes

1

2

3

4

5

6

The above concentratIOn values and mstrument cond1tlOns are for a, Perkm-Elmer HGA2100, based on the use ofa 20 ul mJection, contmuous flow purge g~s and non-pyrolyt1c

graph1te Smaller S1ze furnace devlCes or those employmg faster rates of atom1zatlOn can

be operated usmg lower atom1zatlOn temperatures for shorter time penods than the

above recommended settmgs

The use ofbackground correctIOn 1S recommended

N1trogen may also be used as the purge gas

For every sample matnx analyzed, venficatlOn 1S necessary to determme that method of

standard add1tion 1S not reqUlred (see part 5 2 1 of the Atom1c AbsorptlOn Methods

sectlOn ofth1s manual)

Ifmethod ofstandard add1tion 1S reqUlred, follow the procedure g1ven earher m part 8 5

ofthe Atom1c AbsorptIOn Methods sectlOn ofth1s manual

Data"to be entered mto STORET must be reported as ug/l

Precision and Accuracy

1 Prec1s10n and accuracy data are not avadable at th1s t1me

2792-2
TIN

Method 282.1 (Atomic Absorption, direct aspiration)

STORET NO. Total 01102

Dissolved 01100

Suspended 01101

OptImum ConcentratIOn Range: 10-300 mg/l usmg a wavelength of286 3 nm

SensitiVIty. 4 mg/l

DetectIon LImIt 0 8 mg/l

PreparatIon of Standard SolutIon

1 Stock Solution DIssolve 1 000 g oftm metal (analytical reagent grade) m 100 ml ofconc

Hel and dilute to 1 hter wIth deIOnIzed dIstllled water 1ml = 1mg Sn (1000 mg/l)

2 Prepare dllutIOns ofthe stock tm solutIOn to be used as calIbratIOn standards at the time

of analysIs The calIbratIOn standards should be prepared usmg the same type ofaCId and

at the same concentratIOn as w1l1 result m the sample to be analyzed eIther dIrectly or

after processmg

Sample PreservatIon

1 For sample handlIng and preservatIOn, see part 4 1 of the AtomIc AbsorptIOn Methods

sectIOn ofthIS manual

Sample PreparatIon

1 The procedures for preparatIon of the sample as gIven m parts 4 1 1 thru 4 1 4 of the

AtomIc AbsorptIOn Methods sectIOn ofthIS manual have been found to be satIsfactory

Instrumental Parameters (General)

1 Tm hollow cathode lamp

2 Wavelength 2863 nm

3 Fuel Acetylene

4 OXIdant NItrous OXIde

5 Type offlame Fuel nch

AnalysIs Procedure

1 For the analysIs procedure and the calculatIOn, see "DIrect ASpIratIOn", part 9 1 of the

AtomIc AbsorptIOn Methods sectIOn ofthIs manual

Approved for NPDES

Issued 1974

Editonal reVISIon 1978

282 I-I
Notes

1

2

For concentratiOns of tm below 2 mg/I, the furnace procedure, Method 2822, IS

recommended

Data to be entered mto STORET must be reported as ug/I

Precision and Accuracy

I In a smgle laboratory (EMSL), usmg a mixed mdustnal-domestlc waste etlluent spiked

at concentratiOns of 40, 20 and 60 mg Sn/l, the standard deviatiOns were ±O 25, ±O 5

and ±O 5, respectively Recovenes at these levels were 96%, 101%, and 101%,

respectively

2821-2
TIN

Method 282.2 (Atomic Absorption, furnace technique)

STORET NO. Total 01102

Dissolved 01100 ... 1..... ' 1

Suspended 01101

, , Optimum Concentration Range: 20-300 ug/l

Detection LImit: 5 ug/l

Preparation of Standard SolutIOn

1 Stock solutlOn Prepare as descnbed under "dIrect aspIratIon method"

2 Prepare dIlutlOns of the stock solutlOn to be used as cahbratlOn standards at the tIme of

analysIs These solutlOns are also to be used for "standard addItions"

3 The calIbratlOn standard should be dIluted to contam 2% (v/v) HN03

Sample Preservation

1 For sample handlIng and preservatlOn, see part 4 1 of the AtomIC AbsorptlOn Methods

sectlOn ofthIS manual

Sample PreparatIOn

1 The procedures for preparatlOn of the sample as gIven m parts 4 1 1 thru 4 1 3 of the

AtomIC AbsorptlOn Methods sectlOn of thIS manual should be followed mcludmg the

addItIon of suffiCIent 1 1 HCl to dIssolve the dIgested reSIdue for the analysIs of

suspended or total tm The sample solutlOns used for analysIs should contam 2% (v/v)

HN03

Instrument Parameters (General)

1 DrymgTImeand Temp 30sec-125°C

2 Ashmg TIme and Temp 30 sec-600°C

3 AtomIzmg TIme and Temp 10 sec-2700°C

4 Purge Gas Atmospere Argon

5 Wavelength 224 6 nm

6 Other operatmg parameters should be set as specIfied by the partIcular mstrument

manufacturer

AnalysIs Procedure

1 For the analysIs procedure and the calculatlOn, see "Furnace Procedure" part 9 3 ofthe

AtomIC AbsorptlOn Methods sectlOn ofthIS manual

Approved for NPDES

Issued 1978

2822-1
Notes

1

2

3

4

5.

6

7

The above concentratlOn values and mstrument cond1tlOns are for a Perkm-Elmer HGA2100, based on the use of a 20 ul mJectlOn, contmuous flow purge gas and non-pyrolytic

graph1te Smaller S1ze furnace dev1ces or those employmg faster rates of atom1zatlOn can

be operated usmg lower atom1zat10n temperatures for shorter t1me per10ds than the

above recommended settmgs

The use ofbackground correctlOn 1S recommended

N1trogen may also be used as the purge gas

Tm analys1s 1S sens1t1ve to chlonde concentratlOn If chlonde concentrat10n presents a

matnx problem or causes a loss preV10US to atom1zatlOn, add an excess of 5 mg of

ammomum mtrate to the furnace and ash usmg a ramp necessary or w1th mcremental

steps until the recommended ashmg temperature 1S reached Extended ashmg times have

been reported to 1mprove preClSlon

For every sample matnx analyzed, venficat10n 1S necessary to determme that method of

standard add1t10n 1S not reqmred (see part 5 2 1 of the Atom1c Absorption Methods

sect10n ofth1s manual)

Ifmethod ofstandard add1tion 1S reqmred, follow the procedure g1ven earlter m part 8 5

ofthe Atom1c Absorpt10n Methods sectlOn ofth1s manual

Data to be entered mto STORET must be reported as ug/l

Precision and Accuracy

1 PreC1S10n and accuracy data are not aval1able at th1s t1me

2822-2
TITANIUM

Method 283.1 (Atomic Absorption, direct aspiration)

STORET NO. Total 01152

Dissolved 01150

Suspended 01151

Optimum ConcentratIOn Range: 5-100 mg!l usmg a wavelength of 365 3 nm

SensItivity: 2 mg!l

Detection LImIt: 0 4 mg!l

Preparation of Standard Solution

I Stock solutIOn DIssolve 1 000 g of tItamum metal (powder or small pIeces) In 200 ml

6N HCI Heat to near lOoelc Ito effect dIssolution Cool and dIlute to 1 lIter wIth

deIOmzed dIstilled water (1 ml =I mg TI (1000 mg/l)

2 PotassIUm chlonde solutIOn DIssolve 95 g potassIUm chlorIde, KC1, m dIstIlled water

and make up to 1 lIter

3 Prepare dIlutIons ofthe stock titamum SolutIon to be used as calIbratIOn standards at the

time of analysIs The calIbratIon standards should be prepared usmg the same type of

aCId and at the same concentratIon as WIll result m the sample to be analyzed eIther

dIrectly or after processmg To each 100 ml of standard and sample alIke, add 2 ml of

potassIUm chlOrIde solutIOn

Sample Preservation

1 For sample handlIng and preservatIOn, see part 4 1 of the AtomIC AbsorptIOn Methods

sectIOn ofthIS manual

Sample PreparatIOn

1 The procedures for preparation of the sample as gIven m parts 4 1 1 thru 4 1 3 of the

AtomIC AbsorptIOn Methods sectIOn of thIS manual have been found to be satIsfactory

WIth the followmg modIficatIon For processmg total and suspended tItamum,

concentrated H2S04 (2 ml per 100 ml offinal dIlutIOn) must be added m addItIOn to the

mtnc aCId Reflux the sample addmg addItional mtnc aCId as needed When

solubIlIzatIOn IS complete, heat until the appearance of S03 fumes Cool and add

suffiCIent dIstIlled mtnc aCId so that the final dilutIOn contams 05% (v!v) HN03

Instrumental Parameters (General)

1 Titamum hollow cathode lamp

2 Wavelength 365 3 nm

3 Fuel Acetylene

Approved for NPDES

Issued 1974

283 1-1
4 OXIdant NItrous OXIde

5 Type offlame Fuel nch

AnalYSIS Procedure

1. For the analysIs procedure and the calculatIOn, see "DIrect AspIratIOn" part 9 I of the

AtomIC AbsorptIon Me*ods sectIOn ofthIS manual

Interferences

I A number of elements mcrease the senSItIvIty of tItamum To control thIS problem,

potaSSIUm (1000 mg/l) must be added to standards and samples alIke [AtomIC

AbsorptIon Newsletter ~p 86 (1967)]

Notes

1

2.

For concentratIOns oftitamum below 1 0 mg/l, the furnace procedure, Method 2832, IS

recommended

Data to be entered mto STORET must be reported as ug/l

Precision and Accuracy

1 In a smgle laboratory (EMSL), usmg a mIXed mdustnal-domestIc waste effluent spIked

at concentratIOns of 20, 10 and 50 mg TI/l, the standard deVIatIOns were ±O 07, ±O 1

and ±O 4, respectIvely Recovenes at these levels were 97%,91% and 88%, respectIvely

I

283 1-2
TITANIUM

Method 283.2 (Atomic Absorption, furnace technique)

STORET NO. Total 01152

Dissolved 01150

Suspended 01151

OptImum Concentration Range: 50-SOD ug/l

DetectIOn LImIt: 10 ug/l

PreparatIon ofStandard Solution

1 Stock solution Prepare as descnbed under "direct aspiratIOn method"

2 Prepare dilutIOns ofthe stock solutIOn to be used as cahbratlOn standards at the time of

analySIS

3 The cahbratlOn standards should be prepared usmg the same type ofaCid and at the same

concentratIOn as Will result m the sample to be analyzed either directly or after

processmg

Sample PreservatIon

1 For sample handlIng and preservatIOn, see part 4 1 of the AtomiC AbsorptIOn Methods

sectIOn ofthis manual

Sample PreparatIon

1 Prepare as descnbed under "direct aspiratIOn method" Sample solutIOns for analySIS

shouldcontamO 5% (v/v) HN03

Instrument Parameters (General)

1 Drymg Time and Temp 30 sec-125°C

2 AshmgTlmeand Temp 30sec-I400°C

3 Atomlzmg Time and Temp 15 sec-2800°C

4 Purge Gas Atmosphere Argon

5 Wavelength 3654 nm

6 Other operatmg parameters should be set as specified by the particular mstrument

manufacturer

AnalYSIS Procedure

1 For the analySIS procedure and the calculatIOn, see "Furnace Procedure" part 9 3 ofthe

AtomiC AbsorptIOn Methods sectIOn ofthis manual

Approved for NPDES

Issued 1978

2832-1
Notes

1

2

3

4

5

6.

The above concentratlOn values and mstrument conditlOns are for a Perkm-Elmer HGA2100, based on the use of a 20 ul mJectlOn, contmuous flow purge gas and pyrolytlc

graphIte

Background correctlOn may be reqUIred Ifthe sample contams hIgh dIssolved sohds

Because of possIble chemIcal mteractlOns, mtrogen should not be used as the purge gas

For every sample matrIX analyzed, venficatlOn IS necessary to determme that method of

standard additlon IS not reqUIred (see part 5 2 1 of the AtomIC AbsorptlOn Methods

sectlOn OfthIS manual)

Ifmethod ofstandard additlOn IS reqUIred, follow the procedure gIven earher m part 8 5

ofthe AtomIC AbsorptlOn Methods sectlOn ofthIS manual

Data to be entered mto STORET must be reported as ug/l

Precision and Accuracy

1 PreCISIon and accuracy data are not avaIlable at thIS tIme

2832-2
VANADIUM

Method 286.1 (Atomic Absorption, direct aspiration)

STORET NO. Total 01087

Dissolved 01085

Suspended 01086

Optimum Concentration Range: 2-100 mg/l USIng a wavelength of 318 4 nm

SensItivIty: 0 8 mg/l

Detection Limit' 0 2 mg/l

PreparatIOn ofStandard Solution

1 Stock SolutiOn DIssolve 1 7854 g of vanadIUm pentoxIde, V20 S (analytICal reagent

grade) In 10 ml of conc mtrIc aCId and dl1ute to 1 hter wIth deiOmzed dIstl1led water 1

ml = ImgV(I000mg/l)

2 AlumInum mtrate solutiOn DIssolve 139 g alumInum mtrate, AI(N03)3-9H20, In 150 ml

of deiOmzed dIstIlled water, heat to effect solutiOn Allow to cool and make up to 200 ml

3 Prepare dl1utiOns of the stock vanadIUm solutiOn to be used as cahbratiOn standards at

the tIme of analysIs The cahbratiOn standards should be prepared usmg the same type of

aCId and at the same concentratiOn as w111 result In the sample to be analyzed eIther

dIrectly or after processmg To each 100 ml ofstandard and sample ahke, add 2 ml ofthe

alummummtrate solutiOn

Sample Preservation

1 For sample handhng and preservatiOn, see part 4 1 of the AtomIC AbsorptIon Methods

sectiOn ofthIs manual

Sample Preparation

1 The procedures for preparatiOn of the sample as gIven m parts 4 1 1 thru 4 1 4 of the

AtomIC AbsorptiOn Methods sectiOn ofthIs manual have been found to be satIsfactory

Instrumental Parameters (General)

1 VanadIUm hollow cathode lamp

2 Wavelength 3184 nm

3 Fuel Acetylene

4 OXIdant NItrous OXIde

5 Type offlame Fuel rIch

Approved for NPDES

Issued 1974

286 1-1
Analysis Procedure

1 For the analysIs procedure and the calculatIOn, see "DIrect AspIratIon" part 9 I of the

AtomIc AbsorptIon Methods sectIon ofthIS manual

Interferences

1 It has been reported that hIgh concentratIons of alummum and tItamum 10crease the

sensItIvIty of vanadIUm ThIs 10terference can be controlled by add10g excess alummum

(1000 ppm) to both samples and standards [Talanta~, 871 (1968)]

Notes

1

2

3

For concentratIons of vanadIUm below 05 mgll, the furnace procedure, Method 286 2,

IS recommended

The galhc aCId colonmetnc method may also be used (Standard Methods, 14th EdItIOn,

p260)

Data to be entered 1Oto STORET must be reported as ug/l

Precision and Accuracy

1 In a s10gle laboratory (EMSL), us10g a mIxed 1Odustnal-domestic waste effiuent spIked

at concentratIOns of 20, 10 and 50 mg VII, the standard devIatIons were ±O 10, ±O 1

and ±O 2, respectIvely Recovenes at these levels were 100%, 95% and 97%,

respectIvely

2861-2
VANADIUM

, I ,

Method 286.2 (Ato~~c Absorption, furnace technique)

, I'

OptImum Concentration Range: 10-200 ug/l

Detection LimIt: 4 ug/1

STORET NO. Total 01087

Dissolved 01085

Suspended 01086

Preparation ofStandard SolutIOn

1 Stock solutiOn Prepare as descnbed under ,"dIrect aspIratIOn method"

2 Prepare dIlutiOns of the stock solutiOn to be used as calIbratiOn standards at the time of

analysIs These solutiOns are also to be used for "standard addItIons"

3 The calIbratIOn standard should be dIluted to contam05% (v/v) HN03 , '

Sample Preservation

1 For sample handlmg and preservation, see part 4 1 of the AtomIC AbsorptIon Methods

sectiOn ofthIs manual

Sample Preparation

1 Prepare as descnbed under "dIrect aspIration method" Sample solutiOn for analysIs

should contam 0 5% (v/v)HN03

Instrument Parameters (General)

1 DrymgTImeand Temp 30sec-125°C

2 Ashmg TIme and Temp 30 sec-1400°C

3 AtomIzmgTImeand Temp 15 sec-2800°C

4 Purge Gas Atmosphere Argon

5 Wavelength 318 4nm

6 Other operatmg parameters should be set as specIfied by the particular mstrument

manufacturer

AnalYSIS Procedure

1 For the analySIS procedure and the calculatiOn, see "Furnace Procedure" part 9 3 ofthe

AtomIc AbsorptiOn Methods sectiOn ofthIS manual

Approved for NPDES

Issued 1978

2862-1
Notes

1

2

3

4

5

6

The above concentratiOn values and Instrument cond1tiOns are for a Perkin-Elmer HGA2100, based on the use of a 20 ul inJectiOn, continUOUS flow purge gas and pyrolytic

graph1te Smaller S1ze furnace devlCes or those employing faster rates of atom1zatiOn can

be operated USing lower atom1zatiOn temperatures for shorter t1me penods than the

above recommended settings

Background correctiOn may be reqUlred 1fthe sample containS h1gh d1ssolved sohds

Because ofposs1ble chem1cal interactiOn, mtrogen should not be used as the purge gas

For every sample matnx analyzed, venficatiOn 1S necessary to determine that method of

standard add1tion 1S not reqUlred (see part 5 2 1 of the Atom1c AbsorptlOn Methods

sectiOn ofth1s manual)

Ifmethod ofstandard add1tiOn 1S reqUlred, follow the procedure g1ven earher In part 8 5

ofthe Atom1c AbsorptlOn Methods sectiOn ofth1s manual

Data to be entered Into STORET must be reported as ug/l

Precision and Accuracy

1 Prec1s10n and accuracy data are not aval1able at th1s t1me

2862-2
ZINC

Method 289.1 (Atomic Absorption, direct aspiration)

STORET NO. Total 01092

Dissolved 01090

Suspended 01091

Optimum Concentration Range: 005-1 mg/1 usmg a wavelength of213 9 nm

SensItivity: a02 mg/1

Detection Limit: 0 005 mg/1

Preparation of Standard Solution

1 Stock SolutlOn Carefully weIgh 100 g of zmc metal (analytIcal reagent grade) and

dissolve cautlOusly m 10 ml HN03 When solutlOn IS complete make up to 1 lIter with

delOnlZed distIlled water 1ml = 1mg Zn (1000 mg/1)

2 Prepare dIlutlOns of the stock solution to be used as calIbratlOn standards at the time of

analySIS The calIbratlOn standards should be prepared usmg the same type ofaCid and at

the same concentratlOn as Will result m the sample to be analyzed either directly or after

processmg

Sample Preservation

1 For sample handlmg and preservation, see part 4 1 of the AtomIC AbsorptlOn Methods

section ofthis manual

Sample Preparation

1 The procedures for preparatlOn of the sample as given m parts 4 1 1 thru 4 1 4 of the

AtomiC AbsorptlOn Methods sectlOn ofthis manual have been found to be satisfactory

Instrumental Parameters

1 Zmc hollow cathode lamp

2 Wavelength 2139 nm

3 Fuel Acetylene

4 OXidant Air

5 Type offlame OXldlzmg

AnalYSIS Procedure

1 For the analySIS procedure and the calculatlOn, see "direct asplratlOn" part 9 1 of the

AtomiC AbsorptlOn Methods sectlOn oftms manual

Approved for NPDES

Issued 1971

Edltonal revIsion 1974

2891-1
Notes

1

2

3

4

5

6

7

IIII I I

HIgh levels ofsIlIcon may mterfere

The aIr-acetylene flame absorbs about 25% ofthe energy at the 213 9 nm lIne

The sensItIvIty may be mcreased by the use oflow-temperature flames

Some sample contamer cap lIners can be a source of zmc contammatlOn To CIrcumvent

or aVOId thIS problem, the use ofpolypropylene caps IS recommended

Th,e dIthizone colorImetrIc method may also be used (Standard Methods, 14th EdItion, p

265)

For concentratIons of zmc below 001 mg/1, eIther the SpeCIal ExtractIon Procedure

gIven m part 9 2 of the AtomIc AbsorptIon Methods sec~lOn or the furnace procedure,

Method 289 2, IS recommended

Data to entered mto Storet must be reported as ug/1

Precision and Accuracy ,

1. An mterlaboratory study on trace metal analyses by atomIC absorptIon was conducted by I \ '

the QualIty Assurance and Laboratory Evaluation Branch of EMSL SIX synthetIc

concentrates contammg varymg levels of alumm~m, cadmIUm, chromIUm, copper, Iron,

manganese, lead and zmc were added to natural water samples The statIstIcal results for

zmc were as follows

Standard

Number True Values Mean Value DeVIatIon Accuracy as

of Labs ug/hter ug/hter ug/hter % BIas

86 281 284 97 12

89 310 308 114 -D7

82 56 62 28 113

81 70 75' 28 66

62 7 22 26 206

61 11 17 18 566

2891-2
ZINC

Method 289.2 (Atomic Absorption, furnace technique)

STORET NO. Total 01092

Dissolved 01090

Suspended 01091

Optimum Concentration Range: 0 2-4 ug/l

Detection Limit: 0 05 ug/l

Preparation of Standard Solution

1 Stock SolutIOn Prepare as descnbed under "direct aspiratIOn method"

2 Prepare dilutIOns of the stock solution to be used as calIbration standards at the time of

analysIs These solutIOns are also to be used for "standard additions"

3 The calIbratIOn standard should be diluted to contam 0 5% (vIv) HN03

Sample Preservation

1 For sample handlIng and preservatIOn, see part 4 1 of the Atomic Absorption Methods

section ofthis manual

Sample Preparation

1 Prepare as descnbed under "direct aspiratIOn method" Sample solutIOn for analysIs

should contam 0 5% (vIv) HN03

Instrument Parameters (General)

1 Drymg Time and Temp 30sec-125°C

2 Ashmg Time and Temp 30 sec-400°C

3 Atomlzmg Time and Temp 10 sec-2500°C

4 Purge Gas Atmosphere Argon

5 Wavelength 213 9 nm

6 Other opera.tmg parameters should be set as specified by the particular mstrument

manufacturer

AnalYSIS Procedure

1 For the analysIs procedure and the calculatIOn, see "Furnace Procedure" part 9 3 ofthe

AtomiC AbsorptIOn Methods section ofthis manual

Approved for NPDES

Issued 1978

2892-1
Notes

1

2

3

4.

5.

6

7

The above concentratlOn values and mstrument conditions are for a Perkm-Elmer HGA2100, based on the use ofa 20 ul mJectlOn, contmuous flow purge gas and non-pyrolyttc

graphite Smaller size furnace devices or those employmg faster rates of atomization can

be operated usmg lower atomlzatlOn temperatures for shorter time penods than the

above recommended settmgs

The use ofbackground correctlOn IS recommended

Nitrogen may also be used as the purge gas

The analysIs of zmc by the graphite furnace IS extremely sensitive and very subject to

contammatlOn from the work area, reagents, and pipet tips Smce all these factors affect

the precIsion and accuracy, zmc should be analyzed by the direct aspiratlOn procedure

whenever possible

For every sample matnx analyzed, venficatlOn IS necessary to determme that method of

standard addltlOn IS not reqUlred (see part 5 2 1 of the Atomic Absorptton Methods

sectlOn OfthlS manual)

Ifmethod ofstandard add1tlOn IS reqmred, follow the procedure given earher m part 8 5

ofthe Atomic AbsorptlOn Methods section ofthiS manual

Data to be entered mto STORET must be reported as ug/l

Precision and Accuracy

1 PrecIsion and accuracy data are not aval1able at thiS time

2892-2
ACIDITY

Method 305.1 (Titrimetric)

STORET NO. 70508

1 Scope and Apphcatl0n

1 1 ThIs method IS apphcab1e to surface waters, sewages and mdustna1 wastes, partlCularly

mme dramage and recelvmg streams, and other waters contammg ferrous Iron or other

polyvalent catlOns m a reduced state

1 2 The method covers the range from approxImately 10 mg/1 aCIdIty to approxImately

1000 mg/1 as CaC03, usmg a 50 ml sample

2 Summary ofMethod

2 1 The pH ofthe sample IS determmed and a measured amount ofstandard aCId IS added, as

needed, to lower the pH to 4 or less Hydrogen peroxIde IS added, the solutlOn bolled for

several mmutes, cooled, and titrated electrometncally WIth standard alkah to pH 8 2

3 DefimtlOns

3 1 ThIs method measures the mmeral aCIdIty of a sample plus the aCIdIty resultmg from

oXldatlOn and hydrolysIs ofpolyvalent catlOns, mc1udmg salts ofIron and alummum

4 Interferences

4 1 Suspended matter present m the sample, or precIpItates formed dunng the titratlOn may

cause a sluggIsh electrode response ThIS may be offset by allowmg a 15-20 second pause

between addItIons oftitrant or by slow dropWIse addItion oftitrant as the endpomt pH IS

approached

5 Apparatus

5 1 pH meter, smtable for electrometnc titratlOns

6 Reagents

6 1 Hydrogen peroxIde (H20 2, 30% solutlOn)

6 2 Standard sodmm hydroxIde, 0 02 N

6 3 Standard sulfunc aCId, 0 02 N

7 Procedure

7 1 PIpet 50 ml ofthe sample mto a 250 ml beaker

72 Measure the pH ofthe sample Ifthe pH IS above 4 0, add standard sulfunc aCId (6 3) m

50 mlmcrements to lower the pH to 4 0 or less Ifthe mltial pH ofthe sample IS less than

4 0, the mcremental addltlOn ofsulfunc aCId IS not reqmred

73 Add 5 drops ofhydrogen peroxIde (6 1)

7 4 Heat the sample to bOllmg and contmue bOlhng for 2 to 4 mmutes In some mstances, the

concentratlOn offerrous Iron m a sample IS such that an addItional amount of hydrogen

peroxIde and a shghtly longer bollmg tIme may be reqmred

Approved for NPDES

Issued 1971

Techmcal reVlSlOn 1974

305 1-1
7 5 Cool the sample to room temperature and tItrate electrometncally wIth standard sodIUm

hydroxIde (6 2) to pH 8 2

8. Calculations

8 1 ACidity, as mg/l CaC03 = [(A x B) - (C x D)] x 50,000 ml of sample

where

A = vol ofstandard sodIUm hydroxide used In tItratIon

B = normalIty ofstandard sodIUm hydroxIde

C = volume ofstandard sulfunc aCId used to reduce pH to 4 or less

D = normalIty ofstandard sulfunc aCId

82 IfIt IS desired to report aCidity In mllleqUlvalents per lIter, the reported values as CaC03

are diVIded by 50, as follows

ACIdity as meqll - mg/l CaC03

50

9. PrecIsIon

9 I On a round robIn conducted by ASTM on 4 aCId mIne waters, IncludIng concentratIOns

up to 2000 mg/I, the precIsion was found to be ±10 mg/l

BiblIography

1 Annual Book ofASTMStandards, Part 31, "Water", p 116, D 1067, Method E(1976)

2 Standard Methods for the EXamInatIOn of Water and Wastewater, 14th Edition, p 277,

Method 402(4d) (1975)

305 1-2
&EPA

United States

Environmental Protection

Agency

Research and Development

Test Method

Environmental Monitoring and

Support Laboratory

CinCinnati OH 45268

Acidity (Titrimetric)-

Method 305.2

1 Scope and Application

1 1 This method IS applicable to

rain, surface and other waters of pH

less than 83

1 2 This method IS a measure of the

concentration of strong and weak

aCids that react With hydroxyl IOns

This Includes the dissolved gases that

are present

1 3 The range of this method

depends on the volume of sample

titrated and upon the precIsion that

the Increments of titrant can be

measured If only 10 mL of sample IS

available for analYSIS It IS necessary

to use a 50 pL syrmge for dispenSing

the titrant In order to achieve a

precIsion of less than 10 peq/L

2 Summary of Method

2 1 Samples are titrated With 0 02 N

carbonate free NaOH solution The

end pornt IS determined With a pH

meter Results are reported as

mlcroeqUivalents (peq) per liter

3 Samplmg Handling and

Storage

3 1 The sample container must be

filled completely, sealed and stored at

4°C Care must be taken to minimIze

exposure of the sample to the

atmosphere Open the sample

container Immediately before analySIS

32 AnalYSIS should be performed as

soon as possible after collection

4 Comments

4 1 Samples With an initial pH

between 4 3 and 8 3 are subject to

error due to the loss or gam of

dissolved gases dunng sampling

storage and analyses

5 Apparatus

5 1 pH meter and electrode(s), see

Method 150 1 or 150 2

5 2 Micro buret or micro synngs

5 3 Teflon or glass magnetic stirring

bar

5 4 Magnetic stirrer

5 5 Beakers or flasks

6 Reagents

6 1 Standard sodium hydrOXide

solution, 1 N Dissolve 40g NaOH In

250 mL distilled water Cool and dIlute

to 1 liter With CO2 free distilled water

Store In a polyolefm bottle and fitted

With a soda lime tube or tight cap to

protect from atmosphenc CO2

6 2 Standard sodium hydroXide

titrant, 002 N Dilute 200 mL of 1 N

NaOH With CO2-free distilled water to

1 liter Store In rubber stoppered

bottle Protect from atmosphenc CO2

by uSing a soda lime tube

Standardize against an 0 02 N

potasSium aCid phthalate solution

prepared by dissolVing 4 085 g of

anhydrous KHCaH40 4 In CO2 free

distilled water and diluted to 1 1

7 Procedure

7 1 Pipet an appropnate aliquot of

sample Into beaker of flask containing

a small teflon on glass stirring bar

Use extreme care to minimiZe the

sample surface disturbance

30521 Dec 1982
7.2 Immerse pH electrode(s) Into

sample and stir at a rate that does not

cause sample surface disturbance

7.3 Titrate with 002 N NaOH (62)

to pH 8 3 Titration should be made as

quickly as possible to prevent

absorption of atmosphenc CO2

Reoord volume of titrant

8. Calculation

8 1 Acidity,peq/L ::'~ NB x 105

mLs

peq/L ::' mlcroeqUivalents

per liter

mLB =mL of NaOH titrant

mLs = mL of sample

NB = normality of titrant

9. Precision and Accuracy

9 1 PrecIsion and accuracy data are

not available

References

1, Seymour, MD. Scbubert, SA,

Clayton, J Wand Fernando, Q,

Variation In the ACid Content of

Ram Water In the Course of a

Sangle Precipitation, Water, Air

and Soli Pollution 10{2) 147-161,

Aug 1978

2 Peden, M E and Skowron, IOniC

StabilitY of Precipitation Samples,

Atmospheric EnVironment, Vol

12.pp 2343-2349 1978

3 USGS, Methods for Collection and

AnalysIs of Water Samples for

Dissolved Minerals and Gases, p

39, (1970)

4 Annual Book of ASTM Standards,

part 31, "Water, 'p 107, Dl067,

(1978)

6 Standard Methods for the

Examination of Water and

Wastewater, 14th Edition, p 273,

Method 402 (1975)

Dec 1982 3052-2
ALKALINITY

Method 310.1 (Titrimetric, pH 4.5)

STORET NO. 00410

1 Scope and ApphcatlOn

1 1 ThIS method IS apphcable to dnnkmg, surface, and sahne waters, domestIc and mdustnal

wastes

1 2 The method IS smtable for all concentratIOn ranges of alkahmty, however, appropnate

ahquots should be used to aVOId a tltratl0n volume greaterthan 50 ml

1 3 Automated tltnmetnc analysIs IS eqmvalent

2 Summary ofMethod

2 1 An unaltered sample IS tItrated to an electrometncally determmed end pomt of pH 4 5

The sample must not be filtered, dlluted, concentrated, or altered m any way

3 Comments

3 1 The sample should be refngerated at 4°C and run as soon as practICal Do not open

sample bottle before analysIs

3 2 Substances, such as salts of weak orgamc and morgamc aCIds present m large amounts,

may cause mterference m the electrometnc pH measurements

3 3 For samples havmg hIgh concentratlOns of mmeral aCIds, such as mme wastes and

assocIated recelvmg waters, titrate to an electrometnc endpomt of pH 39, usmg the

procedurem

Annual Book ofASTM Standards, Part 31, "Water", p 115, D-1067, Method D, (1976)

3 4 011 and grease, by coatmg the pH electrode, may also mterfere, causmg sluggIsh

response

4 Apparatus

4 1 pH meter or electncally operated tltrator that uses a glass electrode and can be read to

o05 pH UllltS StandardIze and cahbrate accordmg to manufacturer's mstructlOns If

automatIC temperature compensatlOn IS not prOVIded, make tItratlOn at 25 ±2° C

4 2 Use an appropnate SIzed vessel to keep the aIr space above the solutlOn at a ml111mum

Use a rubber stopper fitted WIth holes for the glass electrode, reference electrode (or

combmatlOn electrode) and buret

4 3 MagnetIC stIrrer, pIpets, flasks and otherstandard laboratory eqmpment

4 4 Burets, Pyrex 50, 25 and 10 ml

5 Reagents

5 1 Sodmm carbonate solutlOn, apprOXImately 0 05 N Place 2 5 ±O 2 g (to nearest mg)

Na2C03 (dned at 250°C for 4 hours and cooled m deSIccator) mto a 1 hter volumetnc

flask and dl1ute to the mark

Approved for NPDES

Issued 1971

Edltonal reVlSlOn 1978

310 1-1
5.2 Standard aCId (sulfunc or hydrochlonc), 0 1 N DIlute 3 0 ml conc H2S04 or 8 3 ml conc

HCl to 1 lIter wIth dIstIlled water StandardIze versus 400 ml of0 05 N Na2C03solutIOn

wIth about 60 ml distIlled water by tltratmg potentlOmetncally to pH of about 5 LIft

electrode and rmse mto beaker BOll solutIon gently for 3-5 mmutes under a watch glass

cover Cool to room temperature RInse cover glass mto beaker Contmue tItratIOn to the

pH mflectlOn pomt Calculate normahty usmg 11, ' \ t ,,,

N= AxB

5300 x C

where

A = g Na2C03weIghed mto 1 lIter

B = ml Na2C03 solutIOn

C == ml aOld used to mflectlon pomt

, .'

53 Standard aCId (sulfunc or hydrochlonc), 002 N DIlute 200 0 ml of 0 1000 N standard

aCId to 1 lIter wIth dIstilled water StandardIze by potentlometnc tItratIOn of 15 0 ml 0 05

N Na2C03SolutIon as above

6 Procedure

6.1 Sample SIze

6 1 1 Use a sufficIently large volume of tltr~nt'( > 20 ~l m a 50 ml buret) to obtam good

preciSIon whIle keepmg volume low enough to permIt sharp end pomt

6 1 2 For < 1000 mg CaCO/1 use 0 02 N titrant

6 1 3 For> 1000mg C~CO/l use 0 1 N tItrant \' . 6 1 4 A prelImmary titratIOn IS helpful

6 2 Potentlometnc tItratIon

6.2 1 Place sample m flask by plpettmg wIth pIpet tIp near bottom offlask

622 MeasurepHofsample

6 2 3 Add standard aCId (5 2 or 5 3), bemg careful to stIr thoroughly but gently to allow

needle to obtam equIlIbnum

1624 TItrate to pH4 5. Record volume pftltrant

6 3 PotentlOmetnc tItratIOn oflow alkalImty

63 1 For alkalmity of <20 mg!1 titrate 100-200 ml as above (6 2) usmg a 10 ml

microburet and 0 02 N aCId solutIOn (5 3)

632 Stop tItratIon at pH m range of 43-47, record volume and exact pH Very

If carefully add titrant to lower pH exactly 0 3 pH umts and record volume

7. CalculatIOns

7 1 PotentlOmetnctitratlOn to pH 45

Alkalmlty, mg!1 Caco3= A x N x 50,000 ml of sample

310 1-2
where

A = mlstandard aCid

N = normahty standard aCid

7 2 Potentlometnc titration oflow alkahmty

Total alkahmty mg/1 CaCO = (2B - C) X N >< 50,000 , 3 ml of sample

where

B = ml titrant to first recorded pH

C = total ml titrant to reach pH 0 3 umts lower

N = normahty ofaCld

8 PrecIsion and Accuracy

8 1 Forty analysts m seventeen laboratones analyzed syrtthetlc water samples contammg

mcrements ofbicarbonate, with the followmg results

Increment as PreC1Sl0n as Accuracy as

Alkahmty Standard DeviatIOn Blasj Bias,

mg/hter, CaCO; mglhter, CaC03 % mg/l, CaC03

- 8 127 +10.61 +085

9 1 14 +22.29 +20

113 528 ... 8.19 -93

119 536 - 7.42 ...88

(FWPCA Method Study 1, Mmeral and Physical Analyses)

8 2 In a smgle laboratory (EMSL) usmg surface water samples at an average concentratIOn

of 122 mg CaC03/1, the standard deviation was ±3

Bibliography

1 Standard Methods for the ExammatlOn of Water and Wastewater, 14th EditIOn, p 278,

Method 403, (1975)

2 Annual Book ofASTM Standards, Part31, "Watel", p 113,0·1067, Method B, (1976)

310 1-3
ALKALINITY

Method 310.2 (Colorimetric, Automated, Methyl Orange)

STORET NO. 00410

1 Scope and ApphcatIOn

1 1 ThIs automated method IS apphcable to dnnkmg, surface, and sahne waters, domestIc

and mdustnal wastes The apphcable range IS 10 to 200 mg/l as CaC03

1 2 ThIs method IS not an approved NPDES method as cIted m the Federal RegIster

December 1, 1976 for samples contammg tUlbldlty or color

2 Summary ofMethod

2 1 Methyl orange IS used as the mdlcator m thIS method because ItS pH range IS m the same

range as the eqUlvalence pomt for total alkahmty, and It has a dlstmct color change that

can be easIly measured The methyl orange IS dIssolved m a weak buffer at a pH of 3 1,

Just below the eqUlvalence pomt, so that any addItIon of alkahmty causes a loss of color

dIrectly proportIOnal to the amount ofalkahmty

3 Sample Handhng and PreservatIOn

3 1 Sample should be refngerated at 4°C and run as soon as practtcal Do not open sample

bottle before analysIs

4 Interferences

4 1 Sample turbIdIty and color may mterfere Wlth thIS method TurbIdIty must be removed

by filtratIon pnor to analysIs If sample IS filtered, thIS method IS not approved for

NPDES momtonng Sample color that absorbs m the photometnc range used WIll also

mterfere

5 Apparatus

5 1 Techmcon AutoAnalyzer conslstmg of

5 1 1 Sampler I

512 Mamfold

5 I 3 Proportl0mng pump

5 1 4 Colonmeter eqUlpped WIth 15 mm tubular flow cell and 550 nm filters

5 1 5 Recorder eqUlpped WIth range expander

6 Reagents

6 1 Methyl Orange DIssolve 0 125 g ofmethyl orange m lItter ofdlsttlled water

6 2 pH 3 1 Buffer DIssolve 5 1047 g of potassmm aCId phthalate m dIstIlled water and add

87 6 ml 0 1 N HCI and dIlute to 1 hter Stable for one week

6 3 Methyl Orange-Buffered IndIcator Add 1 hter of pH 3 1 buffer (6 2) to 200 ml methyl

orange solutIOn (6 1) and mIX well Stable for 24 hours

6 4 Stock SolutIon DIssolve 1 060 g ofanhydrous sodmm carbonate (oven-dned at 250°C for

4 hours) m dIstIlled water and dIlute to 1000milO ml = 1 00 mg CaC03

Approved for NPDES

Issued 1971

Edltonal reVISion 1974

310 2-1
6 4 1 Prepare a senes ofstandards by dilutmg sUItable volumes ofstock solutlOn to 100 0

ml wIth dIStilled water The followmg dIlutIons are suggested

ml of Stoek

SolutIOn

10

20

40

60

80

100

180

200

Cone, mg/l as CaC03

10

20

40

60

80

100

180

200

7. Procedure

7 1 No advance sample preparatIon IS reqUIred Set up mamfold as shown m FIgure 1

7 2 Allow both colonmeter and recorder to warm up for 30 mmutes Run a baselme wIth all

reagents, feedmg dIstIlled water through the sample lme Adjust dark current and

operatIve openmg on colonmeter to obtam stable baselme

7 3 Place dIstIlled water wash tubes m alternate opemngs on sampler and set sample tImmg

at20mmutes

7 4 Place workmg standards m sampler m order of decreasmg concentratlOn Complete

fillmg ofsampler tray wIth unknown samples

7 5 SWItch sample lme from dIstIlled water to sampler and begm analysIs

8. Calculation

8.1 Prepare standard curve by plottmg peak heIghts of processed standards agamst known

concentratlOns Compute concentratlOn of samples by companng sample peak heIghts

wIth standard curve

9 PreCIsIon and Accuracy

9 1 In a smgle laboratory (EMSL), usmg surface water samples at concentratlOns of 15,57,

154, and 193 mg/l as CaC03 the standard devIatIOn was ±O 5

9.2 In a smgle laboratory (EMSL), usmg surface water samples at concentratIons of 31 and

149 mg/l as CaC03 recovenes were 100% and 99%, respectIvely

BIblIography

1 Techmcon Auto Analyzer Methodology, Bulletm 1261, Techmcon Controls, Inc, Chauncey,

NY (1961)

2. Standard Methods for the ExammatIOn of Water and Wastewater, 14th EdItion, p 278,

Method 403 (1975)

3102-2
\,oJ

-

o

\,oJ

PURPLE

GREEN

LARGE MIXING COILS

RED

BlUE

112 DELAY COil

CONTINUOUS FILTER

080 AIR

IbO BtlFFER + INDICATOR

•

WASTE P BI 290 WASTE

COLORIMETER RECORDER

15mm TUBULAR flc

550 llm FILTERS

rJt

P---J

PROPORTIONING PUMP

[2J SAMPLING TIME 2 0 MINUTES

WASH TUBES ONE

FIGURE 1. ALKALINITY MANIFOLD AA·I
BROMIDE

Method 320.1 (Titl'imetric)

STORET NO. 71870

1 Scope and ApplIcatlOn

1 1 This method IS applIcable to drmkmg, surface, and salme waters, domestic and mdustnal

waste effluents

1 2 The concentratlOn range for this method IS 2-20 mg bromlde/l

2 Summary ofMethod

2 1 After pretreatment to remove mterferences, the sample IS divided mto two alIquots One

alIquot IS analyzed for Iodide by convertmg the Iodide to Iodate with bromme water and

tltratmg lOdometncally with phenylarsme oXide (PAO) or sodIUm thiosulfate The other

alIquot IS analyzed for lOdlde plus bromide by convertmg these hahdes to Iodate and

bromate with calcIUm hypochlonte and tltratmg lOdometncally with PAO or sodIUm

thiosulfate Bromide IS then calculated by difference

3 Sample Handhng and PreservatlOn

3 1 Store at 4°C and analyze as soon as possible

4 Interferences

41 Iron, manganese and orgamc matter can mterfere, however, the calCIUm OXide

pretreatment removes or reduces these to mSlgmficant concentratlOns

4 2 Color mterferes with the observatlOn ofmdlCator and bromme-water color changes ThiS

mterference IS elImmated by the use of a pH meter mstead of a pH mdlcator and the use

ofstandardized amounts ofoXidant and oXldant-quencher

5 Reagents

5 1 AcetiC ACid SolutlOn (1 8) MIX 100 ml of glaCial acetic aCid with 800 ml of distilled

water

5 2 Bromme Water In a fume hood, add a 2 ml bromme to 500 ml distilled water Stir with a

magnetic strrrer and a Teflon-coated stlrnng bar for several hours or untl1 the bromme

dissolves Store m a glass-stoppered, colored bottle

5 3 CalCIUm Carbonate (CaC03) Powdered

5 4 CalCIUm Hypochlonte SolutlOn (Ca(OCI)2)' Add 35 g of Ca(OCI)2 to approximately 800

ml of dlstl1led water mal lIter volumetnc flask Stir on a magnetic stirrer for

approximately 30 mmutes Dl1ute to 1 hter and filter Store m a glass-stoppered, colored

flask

5 5 CalcIUm OXide (CaO) Anhydrous, powdered

56 Hydrochlonc ACid SolutlOn (14) MIX 100 ml of HCI (sp gr 1 19) With 400 ml of

dlstl1led water

Approved for NPDES

Issued 1974

3201-1
5 7 Potassmm IodIde (KI) Crystals, ACS Reagent Grade

5 8 SodIUm Acetate SolutIOn (275 gil) DIssolve 275 g sodmm acetate tnhydrate

(NaC2H30 2-3H20) m dIstIlled water DIlute to 1 hter and filter

5 9 SodIUm Chlonde (NaC!) Crystals, ACS Reagent Grade

5.10 SodIUm Formate SolutIOn (500 gil) DIssolve 50 g sodmm formate (NaCH02) m hot

dlsttlled water and dIlute to 100 ml

5 11 SodIUm Molybdate SolutIOn (10 gil) DIssolve 1 g sodIum molybdate (NazMo04-2HzO)

m disttlled water and dtlute to 100 ml

5 12 Sulfunc ACId SolutIOn (14) Slowly add 200 ml H2S04 (sp gr 1 84) to 800 ml of dIstilled

water

5 13 Phenylarsme OXIde (00375N) Hach ChemIcal Co, or eq,Ulvalent StandardIze wIth

00375 N potassmm bllodate (5 19,523)

5 14 Phenylarsme OXIde Workmg Standard (00075 N) Transfer 100 ml of commerCIally

avallable 0 0375 N phenylarsme oXIde (5 13) to a 500 m1 volumetnc flask and dtlute to

the mark wIth dlstdled water ThIs solutIOn should be prepared fresh dady

5 15 Commercmll) <l\'aIbble starch mdlcator such as thyodene or eqmvalent may be used

5 16 SodIUm ThIosulfate, Stock SolutIOn, (0 75 N) DIssolve 186 14 g Na2S203-5H20 m boded

and cooled dlstdled water and ddute to 1 hter Preserve by addmg 5 ml chloroform

5 17 Sodmm ThIosulfate Standard TItrant, (00375 N) Prepare by ddutmg 500 ml of stock

solutIOn (5 16) to 10 hter Preserve by addmg 5 ml of chloroform StandardIze wIth

00375 N potassmm bllodate (5 19,5 23)

5.18 SodIUm ThIOsulfate Workmg Standard (00075 N) Transfer 100 ml of sodmm

thIosulfate standard titrant (5 17) to a 500 ml volumetnc flask and dIlute to the mark

wIth dIstIlled water ThIS SolutIon should be prepared fresh dady

5 19 Potassmm Bllodate Standard, (00375 N) DIssolve 4873 g potassmm bllodate,

prevIOusly dned 2 hours at 103°C, m dlstdled water an'd ddute to 1 0 hter Ddute 250 ml

to 1 0 hter for 00375 N bllodate solutIOn

5 20 Starch SolutIOn Prepare an emulSIOn of 10 g ofsoluble starch m a mortar or beaker wIth

a small quantIty of dlstdled water Pour thIS emulSIOn mto 1 hter ofbOlhng water, allow

to bOll a few mmutes, and let settle overnIght Use the clear supernate ThIS solution may

be preserved by the addItIOn of 5 ml per hter of chloroform and storage m a 10°C

refngerator CommerCIally avadable dry, powd~red starch mdlcators may be used m

place ofstarch solutIOn

521 NItrogen Gas Cylmder

5 22 Potassmm Fluonde (KF-2H20) ACS Reagent Grade

523 StandardIzatIOn of 00375 N Phenylarsme O~lde 'and 00375 N Sodmm ThIosulfate

DIssolve approxlllately 2 g (± 109) KI (57) m 100 to 150 ml dIstdled water, add 10 ml

H2S04 solutIOn (5 12) followed by 20 ml standard potassmm bllodate solutIOn (5 19)

Place m dark for 5 mmutes, ddute to 300 ml and tItrate WIth the phenylarsme OXIde

(5 13) or sodmm thIosulfate (5 17) to a pale straw color Add a small scoop of mdlcator

(5 15) Walt until homogeneous blue color develops and contmue the tItratIOn drop by

drop untd the color dIsappears Run m duphcate Duphcate determmatIOns should agree

wlthm ±O 05 ml

3201-2
6 Procedure

6 1 Pretreatment

6 1 1 Add a vIsIble excess of CaO (5 5) to 400 ml ofsample StIr or shake vIgorously for

approxImately 5 mmutes Fl1ter through a dry, moderately retentive filter paper,

dlscardmg the first 75 ml

6 2 Iodme DetermmatlOn

62 1 Place 100 ml ofpretreated sample (6 1) or a fractlOn thereofdIluted to that volume,

mto a 150 ml beaker Add a Teflon-coated stirnng bar and place on a magnetic

stIrrer Insert a pH electrode and adjust the pH to approxImately 7 or shghtly less

by the dropwlse addItion ofH2S04 solutlOn (5 12)

6 2 2 Transfer the sample to a 250 ml wIdemouthed comcal flask Wash beaker wIth

small amounts of dlst111ed water and add washmgs to the flask A 250 ml lOdme

flask would mcrease accuracy and preclSlon by preventmg possIble loss of the

Iodme generated upon additlOn ofpotassmm lOdide and sulfunc aCId (64 1)

623 Add 15 ml sodmm acetate solutlOn (5 8) and 5 ml acetIc aCId solutlOn (5 1) MIX

well Add 40 ml bromme water solutlOn (5 2), mIX well Walt 5 mmutes

624 Add 2 ml sodmm formate solutlOn (5 10), mIX well Walt 5 mmutes

625 Purge space above sample wIth gentle stream ofmtrogen (521) for approxImately

30 seconds to remove bromme fumes

6 2 6 If a precIpItate forms (Iron), add 0 5 g KFo2H20 (5 22)

6 2 7 A dlst111ed water blank must be run wIth each set of samples because of IodIde m

reagents If the blank IS consIstently shown to be zero for a partIcular "lot" of

chemIcals, It can be Ignored

6 2 8 TItrate as descnbed m 6 4

6 3 BromIde Plus IodIde DetermmatlOn

63 1 Place 100 ml ofpretreated sample (6 1) or a fractlOn thereofdl1uted to that volume,

m a 150 ml beaker Add 5 g NaCI and stir to d1ss01ve Neutrahze by dropwlse

add1tlOn ofHCl SolutIon (5 6) as m (6 2 1) Transfer as m (6 2 2)

6 3 2 Add 20 ml of calcmm hypochlonte solutlOn (5 4) Add 1 ml of HCI solutlOn (5 6)

and add approxImately 0 2 g calcmm carbonate (5 3)

6 3 3 Heat to bOllmg on a hot plate, mamtam bOlhng for 8 mmutes j

634 Remove from hot plate and carefully add 4 ml sodmm formate solutlOn (5 10)

CautlOn TOO RAPID ADDITION MAY CAUSE FOAMING Wash down

sIdes wIth dIstIlled water

6 3 5 Return to hot plate and mamtam bOlhng condItions for an additlOnal 8 mmutes

OccaslOnally wash down sIdes wIth dIstIlled water If resIdue IS deposIted from

bOlhng actlOn

6 3 6 Remove from hot plate Wash down sIdes and allow to cool

637 Ifa precIpItate forms (Iron), add 05 g KFe2H20 (522)

63 8 Add 3 drops sodmm molybdate solutlOn (5 11)

6 3 9 A dIstIlled water blank must be run wIth each set of samples because of lOdlde,

Iodate, bromIde, and/or bromate m reagents

6 3 10 TItrate as descnbed m 6 4

320 1-3
11IIII 11

6 4 TItratIOn

64 1 DIssolve approXImately 1 g potassmm IOdIde (57) In sample from (62 8 or 63 10)

Add 10 ml ofH2S04 solutIon (5 12) and place In dark for 5 mInutes

642 TItrate wIth standardIzed phenylarsIne oXIde workIng standard (5 14) or sodmm I ,

thIosulfate workIng standard (5 18), addIng IndIcator (5 15 or 520) as. end POInt IS

approached (lIght straw color) TItrate to colorless solutIOn DIsregard returnIng

blue color

7 CalculatIons

7 1 PnncIple IodIde IS determIned by the tItratIOn of the sample as oXIdIzed In (62)

bromIde plus IodIde IS determIned by the tItratIOn ofthe sample as OXIdIzed In (63) The

amount ofbronude IS then determIned by dIfference The number ofeqUIvalents ofIodIne

produced a constant of 13,320 as shown In the equatIOn In (72) ExperImental data IS

entered In the approprIate place and the equatIOn IS solved for mg/I bromIde

72 EquatIon

Br(mg/l) 13,320 [(A B ) _ ( D ; E ) ]

where

A = the number ofml ofPAO needed to tItrate the sample for bromIde plus IodIde

(WIth the number ofml ofPAO needed to tItrate the blank subtracted)

B = the normalIty of the PAO needed to tItrate the sample for bromIde plus

IodIde

C = the volume ofsample taken (100 ml or a fractIOn thereof) to be tItrated for

bromIde plus IodIde

D = the number of ml of PAO needed to tItrate the sample for IOdIde (WIth the

number of ml of PAO needed to tItrate the blank subtracted) The blank for

the IOdIde tItratIOn IS often zero

E = the normahty ofthe PAO used to tItrate the sample for IOdIde

F = the volume ofsample taken (100 ml or a fractIon thereof) to be tItrated for

IodIde

8. PreCISIon and Accuracy

8 1 In a SIngle laboratory (EMSL), USIng a mIxed domestIC and IndustrIal waste effluent, at

concentratIOns of 0 3,28,53, 10 3 and 20 3 mg/1 of bromIde, the standard deVIatIons

were ±O 13, ±O 37, ±O 38, ±O 44 and ±O 42 mg/I,-respectlvely

82 In a SIngle laboratory (EMSL), USIng a mIXed domestIC and industrml waste effluent, at

concentratIons of2 8, 5 3, 10 3 and 203 mg/l ofbronude, recoverIes were 96,83,97 and

99%, respectIvely

320 1-4
BIbhography

1 Annual Book of ASTM Standards, Part 31, "Water", Standard DI246-68, Method C, p 328

(1976)

2 Bender, D F, "ModIficatIOn of the Iodimetnc TItration Methods for the DetermInatIon of

BromIde and Its applIcatIOn to MIxed DomestIc-Industnal Waste Effluents", Analyst

(London), 100, P 400-404 (June 1975)

320 1-5
CHLORIDE

Method 325.1 (Colorimetric, Automated Ferricyanide AAI)

STORET NO. 00940

1 Scope and Apphcation

1 1 ThIs automated method IS apphcable to dnnkIng, surface, and sahne waters, domestIc

and Industnal wastes The apphcable range IS 1 to 250 mg ClIl ApproXImately 15

samples per hour can be analyzed

2 Summary ofMethod

2 1 ThIOcyanate IOn (SCN) IS hberated from mercurIC thIOcyanate'through sequestratIOn of

mercury by chlonde IOn to form un-IOmzed mercunc chlonde In the presence of fernc

lOn, the hberated SCN forms hIghly colored fernc thIOcyanate In concentratIon

proportIOnal to the ongInal chlonde concentratIOn

3 Sample Handhng and PreservatIOn

3 1 No speCIal reqUirements

4 Interferences

4 1 No sIgmficant Interferences

5 Apparatus

5 1 Techmcon AutoAnalyzer consIstIng of

5 1 1 Sampler I

5 1 2 Contmuous filter

5 1 3 Mamfold

5 1 4 ProportIOmng pump

5 1 5 Colonmeter eqUipped WIth 15 mm tubular flow cell and 480 nm filters

5 1 6 Recorder

6 Reagents

6 1 Fernc Ammomum Sulfate DIssolve 60 g of FeNHlS04)2-12H20 In approxImately 500

ml dIstIlled water Add 355 ml of conc HN03 and dIlute to 1 hter WIth dIstIlled water

FIlter

6 2 Saturated Mercunc ThIOcyanate DIssolve 5 g of Hg(SCN)2 In 1 hter of dIstIlled water

Decant and filter a portIon of the saturated supernatant hqUId to use as the reagent and

refill the bottle WIth dIstIlled water

63 Stock SolutIOn (0 0141 N NaCl) DIssolve 08241 g ofpre-dned (140°C) NaCI In dIstIlled

water DIlute to 1 hter In a volumetnc flask 1ml = 0 5 mg CI

63 1 Prepare a senes ofstandards by dIlutmg SUitable volumes ofstock solutIOn to 100 0

ml WIth dIstIlled water The follOWIng dIlutIOns are suggested

Approved for NPDES

Issued 1971

325 I-I
ml of Stock

Solution

10

20

40

80

15 a

200

300

400

500

Cone, mg/l

50

100

200

400

75 a

1000

1500

2000

2500

7 Procedure

7.1 No advance sample preparatIOn IS reqUlred Set up mamfold as shown 10 FIgure 1 For

watersamples known to be consIstently low 10 chlonde content, It IS adVIsable to use only

one dIstilled water 10take hne

7 2 Allow both colonmeter and recorder to warm up for 30 mmutes Run a basehne wIth all

reagents, feed10g dIstl1led water through the sample lme Adjust dark current and

operatIve opemng on colonmeter to obtam stable basehne

7 3 Place dIstl1led water wash tubes 10 alternate opemngs 10 sampler and setsample tIm10g at

20m1Outes

7 4 Place work1Og standards 10 sampler 10 order of decreas10g concentratIOns Complete

fill10g ofsampler tray wIth unknown samples

7 5 SWItch sample hne from dIstl1led water to sampler and begm analysIs

8 CalculatIOn

8 1 Prepare standard curve by plott1Og peak heIghts of processed standards agamst known

concentratIons Compute concentratIOn of samples by companng sample peak heIghts

wIth standard curve

9 PrecIsIon and Accuracy

9 1 In a s10gle laboratory (EMSL), us10g surface water samples at concentratIOns of 1, 100,

and 250 mg C1I1, the standard devIatIon was ±O 3

9 2 In a s10gle laboratory (EMSL), us10g surface water samples at concentratIons of 10 and

100 mg C1I1, recovenes were 97%' and 104%, respectIvely

Blbhography

1 J E O'Bnen, "AutomatIC AnalysIs of Chiondes 10 Sewage", Waste Engr, 33, 670-672 (Dec

1962)

2 Standard Methods for the Exam1Oation of Water and Wastewater, 14th EdItIon, p 613,

Method 602 (1975)

325 1-2
W

tv

Vl

..-

J

W

SMALL

MIXING

COILS

ISIII)

ml/mln

G1200 SAMtlE

y YI I 20 SAMItLE

II( <: rP pP 25 WATER DISTILLED I ::y : " I 20 AIR CONTINUOUS FILTER

I I~LUE :BLUE~ FeNH4(S04J2

I( / W 060 Hg ISCN)

2

WASTE p P~ 50 olI(

PROPORTIONING WASTE

PUMP

t

- I ,.J

15•• TUBULAR tiel" '0

480 •• FILTERS

IRECORDER

SAMPLING TIME 20MINUTES

WASH TUBES ONE

FIGURE 1. CHLORIDE MANIFOLD AA-I
CHLORIDE

Method 325.2 (Colorimetric, Automated Ferricyanide AAII)

STORET NO. 00940

1 Scope and ApphcatIOn

1 1 ThIS automated method IS apphcable to dnnkmg, surface, and sahne waters, domestIc

and mdustra1 wastes The apphcab1e range IS 1 to 200 mg ClIl ThIs range may be

extended by sample dIlutIOn ApproxImately 30 samples per hour can be analyzed

2 Summary ofMethod

2 1 ThIocyanate Ion (SCN) IS hberated from mercunc thIOcyanate through sequestratIOn of

mercury by chlonde Ion to form un-IOmzed mercunc chlonde In the presence of fernc

lon, the hberated SCN forms hIghly colored fernc thIOcyanate m concentratIOn

proportIOnal to the ongmal chlonde concentratIOn

3 Sample HandlIng and PreservatIOn

3 1 No specIal reqUIrements

4 Interferences

4 I No sIgmficant mterferences

5 Apparatus

5 1 Techmcon AutoAnalyzer conslstmg of

5 11 Sampler

5 1 2 Contmuous filter (optIOnal)

5 I 3 AnalytIcal cartndge

5 1 4 ProportIOmng pump

5 1 5 Co1onmeter eqUIpped wIth 15 mm tubular flow cell and 480 nm filters

5 1 6 Recorder

5 1 7 DIgItal pnnter (optIOnal)

6 Reagents

6 1 Mercunc thIOcyanate solutIOn DIssolve 4 17 gm of Hg(SCN)2 m 500 ml of methanol

DIlute to 1lIter wIth methanol, mIX and filter through filter paper

6 2 Fernc mtrate solutIOn, 20 2% DIssolve 202 gm ofFe(N03)3·9 H20 m 500 ml of dIstIlled

water Add 31 5 ml conc mtnc aCId, mIX and dIlute to 1lIter wIth dIstIlled water

63 Color reagent Add 150 ml of mercunc thIOcyanate solutIon (6 1) to 150 ml of fernc

mtrate solutIOn (6 2), mIX, and dIlute to 1 lIter wIth dIstIlled water

64 Stock SolutIOn (0 0141 N NaCl) DIssolve 08241 g ofpre-dned (140°C) NaCI m dIstIlled

water DIlute to I hter m a volumetnc flask 1ml = 0 5 mg CI

6 4 1 Prepare a senes ofstandards by dIlutmg SUItable volumes ofstock solutIOn to 100 0

ml wIth dIstIlled water The followmg dIlutIOns are suggested

Approved for NPDES

Issued 1978

3252-1
ml of Stoek

SolutIon

10

20

40

80

150

200

300

400

Cone, mg/l

50

100

200

400

750

1000

1500

2000

7 Procedure

7 1 Where partIculate matter IS present, the sample must be filtered pnor to the

determInatIOn ThIS can be accomplIshed by havIng the Techmcon contInUOUS filter as an

Integral part ofthe system The sample may be centnfuged In place offiltratIOn

7 2 Allow both colonmeter and recorder to warm up for 30 mInutes Run a baselIne wIth all

reagents, feedIng dIstIlled water through the sample lIne

7.3 Place workIng standards In sampler In order of decreasIng concentratIOns Complete

fillIng ofsampler tray WIth unknown samples

7.4 When a stable baselIne has been obtaIned, start the sampler

8 CalculatIOn

8 1 Prepare standard curve by plottIng peak heIghts of processed standards agaInst known

concentratIons Compute concentratIOn of samples by companng sample peak heIghts

WIth standard curve

9. PreCISion and Accuracy

9 1 Precision and accuracy data are not avaIlable at thiS time

Blbhography

1. J E. O'Bnen, "Automatic AnalySIS of ChIondes In Sewage", Waste Engr, 33, 670-672 (Dec

1962)

2. Techmcon AutoAnalyzer II, Industnal Method No 99-70W, Techmcon Industnal Systems,

Tarrytown, NY, 10591 (Sept 1973)

3252-2
OM F/C

MPLE WASTE

R

-SAMPLE

L WATER

LOR REAGENT

L WATER

R

L WATER

4

SAMPLE

R

TO FILTER

TO SAMPLER BLUE BLUE 160 01

BLK BLK o 32 Af

170-0103 noooooo t PUR PUR 2 50 01

5TURNS 4 ORG GRN o 10 AWASTE WASTE REO REO o 80 I

BLK BLK o 32 AI

TO WHT/WHT

WASTE TUBE BLK BLK o 32 AI

170-0103 r GRY GRY 1 00 RE 146-0152-02 nnonon

nnnnnnn 5 TU R N S4 ORG GRN o 10 01

14 TURNS. GRY GRY 1 00 CC

TO F/C

PUMP TUBE WHT WHT o 60 S/J COLORIMETER WASTE 480 N M

15 mm F/C GRY GRY 1 00 FR WASTE

W

IV

\.1\

W

PUMP

FIGURE 1

CHLORIDE MANIFOLD AA 11
CHLORIDE

Method 325.3 (Titrimetric, Mercuric Nitrate)

STORET NO. 00940

1 Scope and Application

1 1 This method IS applicable to dnnkmg, surface, and saline waters, domestic and mdustnal

wastes

1 2 The method IS sUItable for all concentratIOn ranges ofchlonde content, however, m order

to aVOId large tItratIon volume, a sample aliquot contammg not more than 10 to 20 mg CI

per 50 mIls used

1 3 Automated titratIOn may be used

2 Summary ofMethod

2 1 An aCidified sample IS titrated with mercunc mtrate m the presence of mixed

dlphenylcarbazone-bromophenol blue mdlcator The end pomt of the titration IS the

fonnatIOn ofthe blue-vIOlet mercury dlphenylcarbazone complex

3 Comments

3 1 Amons and cations at concentrations normally found m surface waters do not mterfere

3 2 Sulfite mterference can be elimmated by oXldlzmg the 50 ml ofsample solutIOn with 0 5

to 1mlofH20 2

4 Apparatus

4 1 Standard laboratory tItnmetnc eqUIpment mcludmg a 1ml or 5 ml mlcroburet with 0 01

ml graduatIOns

5 Reagents

5 1 Standard sodIUm chlonde, 0 025 N DIssolve 1 4613 g ± 0 0002 g sodIUm chlonde (dned

at 600°C for 1 hour) In chlonde-free water In a 1 lIter volumetnc flask and dIlute to the

mark I ml = 886 5 fJg Cl

5 2 Nltnc aCid, HN03solutIOn (3 + 997)

53 Sodmm hydroxide solutIOn, NaOH, (10 gil)

5 4 Hydrogen peroxide (30%), H20 2

55 Hydroqumone solutIOn (10 g/liter) Dissolve 1 g ofpunfied hydroqumone m water m a

100 ml volumetnc and dtlute to the mark

56 Mercunc mtrate titrant (0141 N) Dissolve 25 g Hg(N03)2-H20 m 900 ml of dlsttlled

water aCidified with 5 0 ml conc HN03mal liter volumetnc flask and dtlute to the

mark with distilled water Filter If necessary Standardize agamst standard sodmm

chlonde solutIOn (5 1) usmg procedure 6 Adjust to exactly 0 141 N and check Store m a

dark bottle A 1 00 ml aliquot IS eqUIvalent to 5 00 mg ofchlonde

5 7 Mercuric mtrate titrant (0 025 N) Dissolve 4 2830 g Hg(N03)2-H20 m 50 ml of dlsttlled

water aCidified with 0 5 m1 conc HN03 (sp gr 1 42) mal liter volumetnc flask and

dtlute to the mark with distilled water Filter If necessary Standardize agamst standard

Approved for NPDES

Issued 1971

EdItonal reVISIOn 1978 and 1982

3253-1
sodIum chlonde solutIOn (5 1) usmg procedure 6 Adjust to exactly 0 025 N and check

Storem a dark bottle

58 Mercunc filtrate tItrant (00141 N) DIssolve 24200 g Hg(N03)2eH20 m 25 ml of

dlst111ed water aCIdIfied wIth 0 25 ml of conc HN03(sp gr 1 42) mal hter volumetnc

flask and dl1ute to the mark wIth dlst111ed water FIlter If necessary StandardIze agamst

standard sodmm chlonde solutIOn (5 1) usmg procedure 6 Adjust to exactly 00141 N

and check Store m a dark bottle A 1ml ahquot IS eqmvalent to 500 ug ofchlonde

5 9 MIxed mdIcator reagent DIssolve 0 5 g crystallme dlphenylcarbazone and 0 05 g

bromophenol blue powder m 75 m195% ethanol m a 100 m1 volumetnc flask and dl1ute

to the mark wIth 95% ethanol Store m brown bottle and dIscard after 6 months

5 10 Xyleneqanole FF solutIOn DIssolve 0 005 g of xylene cyanole FF dye m 95% ethanol or

Isopropanol m a 100 ml volumetrIc and dIlute to the mark with 95% ethanol or

Isopropanol

6. Procedure ,

6.1 t:se50 ml ofsample oran ahquot ofsample dIluted t050 ml with dIstilled water, so that

the concentratIon of chlonde does not exceed 20 mg/ahquot If the sample or ahquot

contams more than 25 mg of chlonde, use 0 025N mercunc mtrate tItrant (5 7) m step

6.6 Ifthe sample or ahquot contams less than 25 mg of chlonde, use 0 014lN mercunc'

mtrate titrant (5 8) m step 66 Determme an mdicator blank on 50 ml chlonde-free

water usmg step 6 6 Ifthe sample contams less than 0 I mg/l of chlonde concentrate an

appropnate volume to 50 ml

62 Add 5 drops of mIxed mdicator reagent (59), shake or SWIrl solutIon

6.3 If a blue-VIolet or red color appears add HN03solutIon (5 2) dropwlse untl1 the color

changes to yellow

64 If a yellow or orange color forms ImmedIately on addItIOn of the mIxed mdlcator, add

NaOH solutIOn (5,3) dropwlse untl1 the color changes to blue-VIOlet, then add HN03

solutIon (5 2) dropwise untl1 the color changes to yellow

6 5 Add 1ml excess HN03solutIOn (5 2)

6 6 TItrate WIth 0 025 N mercunc mtrate tItrant (5 7) untl1 a blue-VIOlet color perSIsts

throughout the solutIOn See 6 1 for chOlce of titrant normahty !Xy,lene cyanollFF

SolutIon (5 10) may be added WIth the mdlcator to sharpen the end pomt ThIS WIll

change colorshades PractIce runs should be made

6.7 AddItional steps to ehmmate partIcular mterferences

6 7 1 If chromate IS present and Iron IS not present the end pomt may be dIffIcult to

detect

be an ohve-purple color

672 If chromate IS present at > 100 mg/1 and Iron IS 'not present, add 2 ml of fresh

hydroqumone SolutIon (5 5)

6 7 3 Iffernc Ion IS present use volume contammg no more than 2 5 mg offernc Ion or

fernc Ion plus chromate IOn Add 2 mlfresh hydroqu~none SolutIon (5 5)

674 Ifsulfite Ion IS present, add 05 ml ofH20 2SolutIon (54) to 50 ml sample and mIX

for 1mmute

3253-2
7 CalculatIOn

mg chlonde/l - (A - B)N x 35,450

ml of sample

where

A = ml tItrant for sample

B = ml tItrant for blank

N = normalIty mercunc mtrate tItrant

mg NaClil = mg chlonde/l x 1 65

8 PreCIsIOn and Accuracy

8 1 Forty two analysts m eIghteen 1aboratones analyzed synthetIc water samples contammg

exact mcrements ofch10nde, WIth the followmg results

Increment as PreCISIon as Accuracy as

Chlonde Standard DeviatlOn Bias, BIas,

mg/hter mg/hter % mg/hter

17 154 +216 +04

18 132 +350 +06

91 292 +011 +01

97 316 -051 -05

382 11 70 -061 -23

398 11 80 -1 19 -47

(FWPCA Method Study 1, Mmeral and PhYSICal Analyses)

8.2 In a smgle laboratory (EMSL), usmg surface water samples at an average concentratIOn

of 34 mg ClIl, the standard deVIatIOn was ± 1 0

8 3 A synthetIc unknown sample contammg 241 mg/1 chlonde, 108 mg/1 Ca, 82 mg/l Mg,

3 1 mg/1 K, 199 mg/1 Na, 1 1 mg/1 mtrate N, 025 mg/1 mtnte N, 259 mg/1 sulfate

and 425 mg/1 total alkalImty (contnbuted by NaHC03) m dIstIlled water was analyzed

m 10 laboratones by the mercunmetnc method, WIth a relatIve standard deVIatIOn of

33% and a relatIve error of2 9%

BIblIography

1 Annual Book of ASTM Standards, Part 31, "Water", Standard D512-67, Method A, p 270

(1976)

3253-3
CHLORINE, TOTAL RESIDUAL

Method 330.1 (Titrimetric, Amperometric)

STORET NO. 50060

1 Scope and ApphcatlOn

liThe amperometnc titratIOn method IS apphcable to all types ofwaters and wastes that do

not contam a substantIal amount oforgamc matter

2 Summary ofMethod

2 1 Chlonne (hypochlonte lon, hypochlorous aCId) and chlorammes stolcmometncally

hberate Iodme from potassIUm IodIde at pH 4 or less

2 2 The Iodme IS titrated wIth standard reducmg agent such as sodIUm thIOsulfate or

phenylarsme oXIde usmg an amperometer to determme the end pomt

2 3 The results are calculated as mg/l CI even though the actual measurement IS of total

oXldlzmg power because chlonne IS the dommant oXldlzmg agent present

3 Interferences

3 1 Manganese, mtnte and Iron do not mterfere

3 2 Stlmng can lower chlonne values by volatlhzatlOn

33 If dIlutIon IS necessary, It must be done wIth dIstIlled water WhICh IS free of chlonne,

chlonne-demand and ammoma

3 4 Copper and sIlver pOlson the electrode

4 Apparatus

4 1 An amperometer conslstmg of a mlcroammeter wIth necessary electncal accessones, a

cell umt wIth a salt bndge, reference electrode and an agItator CommercIally avaIlable

Ifthe entIre system (mcludmg tItrant dehvery system) IS to be used, make sure that the

volume read offthe pIpet or buret IS really bemg dehvered to the sample cell ReservOlrtype system sometImes back up, producmg false readmgs

4 2 A mlcroburet, 0-2 ml or 0-10 ml, dependmg on reqUIred precISIon, accuracy and range

5 Reagents

5 1 Phenylarsme OXIde solutIOn (0 00564N), commercIally avaIlable, Wallace and TIernan or

eqUIvalent StandardIze WIth potassIUm bllodate (5 8, 5 9)

5 2 PotassIUm IodIde, KI, crystals

5 3 PotassIUm IodIde SolutIon DIssolve 50 g KI m freshly boIled and cooled dIstilled water

and dIlute to 1 hter Store m colored, glass-stoppered bottle m refngerator DIscard when

yellow color develops

5 4 CommerCIally avaIlable starch mdIcators such as thyodene or eqUIvalent may be used

55 Acetate buffer solutIOn (pH 4) DIssolve 146g anhydrous NaC2H30 2 or 243g

NaC2H30 2-3H20 m 400 ml dIstIlled water, add 480g conc acetIc aCId and dIlute to 1 hter

WIth dIstilled water

Approved for NPDES

Issued 1974

Edltonal reVISIon 1978

3301-1
5 6 Sulfunc ACId (1 4) Slowly add 200 ml H2S04 (sp gr 1 84) to 800 ml ofdIstIlled water

5 7 PotaSSIUm bllodate (0 IN) DIssolve 3 249g potaSSIUm bllodate, preVIOusly dned 2 hours

at 103°C, In dIstIlled water and dIlute to 1 0 lIters Store m a glass stoppered bottle

58 PotaSSIUm bllodate (0 oo5N) DIlute 50 ml of0 IN potaSSIUm bllodate (57) to l-hter m a

volumetnc flask Store m a glass stoppered bottle

59 StandardIzatIon of 0 00564N phenylarsme OXIde DIssolve approXImately 2g (± 19) KI

(52) In 100 to 150 ml dIstIlled water, add 10 ml H2S04 SolutIon (56) followed by 20 ml

ooo5N potaSSIUm bllodate solutIOn (5 8) Place In dark for 5 mInutes, dIlute to 300 ml

and tItrate WIth 0 oo564N phenylarsme OXIde SolutIon (5 1) to a pale straw color Add a

small scoop ofIndtcator (54) Walt untIl homogeneous blue color develops and contmue

the titration drop by drop untIl the color disappears Run m duplIcate DuplIcate

determmattons should agree wlthm ±O 05 ml

N PAO - 20 x 0 005 - mlPAO

Adjust PAO solutIon Ifnecessary and recheck

6, Procedure

6 1 Place 200 ml ofsample In the sample contamer ThiS volume IS convement because the

buret readIng In millIlIters IS eqmvalent to mg/1 CI Up to 2 mg/1ls relIably titrated thiS

way Smallersample alIquots dIluted to 200 ml are used for concentratIOns greater than 2

mg/1 The constructIOn of the cell and electrode component usually reqmre 200 ml of

sample

6 2 Place on electrode assembly

6 3 Add 1 0 ml KI solutIOn (5 3)

6 4 Add 1ml acetate buffer (5 5)

6 5 TItrate With 0 oo564N PAO (5 1)

6 6 As each mcrement IS added the needle deflects toward rest When the needle no longer

deflects subtract the last drop added from the buret readmg to obtam the mg/l Cl Less

and/orslower deflectIOn SIgnals that the end POInt IS near

7 calculatIOns

7.1 For 0 oo564N PAO and a 200 ml sample there are no calculatIOns The buret readIng IS

In mg/l The last Increment, when the needle does not deflect toward rest, must be

subtracted

8 PrecIsion and Accuracy

8 1 More than 20 laboratones analyzed prepared samples of 0 64 and 1'83 mg/1 total CI

The relative standard deVIatIOns were 248% and 125% respectIvely and the relative

errors were 85% and 88% respectively

3301-2
In a smgle operator, smgle laboratory sItuatIOn the followmg results were obtamed

Sample Average Stand Dev ReI Stand Dev

Matnx mgll mg/l %

Distilled Water 038 002 61

350 001 02

Dnnkmg Water 097 003 26

River Water 057 002 30

Domestic Sewage 041 003 69

For these samples the results were compared to the iOdometnc titratiOn as a means ofobtammg a relative

accuracy -

Sample

Matnx

Dnnkmg Water

RiVer Water

Domestic Sewage

Iodometnc

TitratiOn mg/l

094

056

050

Amperometnc

TitratiOn mg/l

097

057

041

BIblIography

% Recovery

1032

1018

820

1 Standard Methods for the ExammatIOn of Water and Wastewater, 14th EdItIOn, p 322,

Method 409C (1975)

2 Annual Book of ASTM Standards, Part 31, "Water", Standard D 1253-76, P 277, Method A

(1976)

3 Bender, D F, "Companson of Methods for the DetermmatIOn of Total AvaIlable ResIdual

Chlonne m Vanous Sample Matnces", EPA Report-600/4-78-o19

330 1-3
CHLORINE, TOTAL RESIDUAL

Method 330.2 (Titrimetric, Back, Iodometric)

(Starch or Amperometric Endpoint)

STORET NO. 50060

1 Scope and Apphcat10n

lIThe lOdometnc backt1trat10n method IS apphcable to all types of waters but IS pnmanly

used for wastewater because It ehmmates any contact between the full concentratIon of

hberated 10dme and the wastewater

2 Summary ofMethod

2 1 Chlonne (hypochlonte lon, hypochlorous aCId) and chlorammes stOlchlOmetncally

hberate 10dme from potaSSIUm lOdlde at pH 4 or less

2 2 The lOdme ImmedIately quantitatIvely oXIdIzes a standardIzed reducmg agent such as

sodIUm thlOsulfate or phenylarsme OXIde

2 3 The excess reducmg agent IS then determmed by t1tratmg WIth a standard lOdme tItrant

The starch endpomt color change IS from clear to blue

2 4 A subtractlOn ofthe excess amount ofreducmg agent IS mcluded m the calculatlOns and

the results are reported as mg/l CI even though the actual measurement IS of total

oX1d1zmg power because chlonne IS the dommant oX1d1zmg agent present

3 Interferences

3 1 Manganese, Iron and mtnte mterference may be m1mm1zed by buffenng to pH 4 before

the addItion ofKI

3 2 HIgh concentratlOns oforgamcs may cause uncertamty m the endpomt ThIS uncertamty

can be reduced by aC1d1fymg to pH 1 0 Ifmanganese, Iron and mtnte are absent

3 3 TurbIdIty and color may make the endpomt dIfficult to detect PractIce runs WIth spIked

samples may be necessary

4 Apparatus

4 1 Standard laboratory glassware IS used A mlCroburet 0-2 ml or 0-10 ml IS used

dependmg on the deSIred range and accuracy

5 Reagents

5 1 Phenylarsme OXIde solutlOn (000564N) Wallace and T1erman or eqUivalent

StandardIze WIth potaSSIUm bllodate (5 6, 5 9)

52 Acetate buffer solutlOn (pH 4) DIssolve 146 g anhydrous NaCzH30 z or 243 g

NaCzH30 z·3HzO m 400 ml d1stl1led water, add 480 g conc acetIc aCId and dl1ute to 1 hter

WIth d1stl1led water

53 Standard lOdme solutlOn (0 IN) DIssolve 40 g KI m 25 ml d1stl1led water, add 13 g

resubhmed lOdme and stIr untl1 dIssolved Transfer to a 1hter volumetnc flask and dl1ute

to the mark Determme the exact normahty (5 11)

Approved for NPDES

Issued 1978

3302-1
5 4 Standard lodme tItrant (0 0282N) DIssolve 25 g KI m a httle dIstilled water mal hter

volumetnc flask Add the calculated amount of 0 IN standard lOdme (53) to produce a

0.0282N solutlOn StandardIze dally (5 12) Store m amber bottle or m dark, protect from

sunhght at all tImes and keep from contact wIth rubber

5.5 PotasslUm bllodate (0 IN) Dlssove 3 249g potasslUm bllodate, prevlOusly dned 2 hours

at 103°C, m dIstilled water and dIlute to 1 0 hter Store In a glass stoppered bottle

5.6 PotasslUm bllodate (0 oo5N) DIlute 50 ml of0 IN potasslUm bllodate (5 5) to 1 hter m a

volumetnc flask Store m glass stoppered bottle

5 7 CommercIally avaIlable starch mdlcators such as thyodene or eqUlvalent may be used

5.8 Sulfunc ACId SolutlOn (1 4) Slowly add 200 ml H2S04 (sp gr 1 84) to 800 ml ofdIstIlled

water

59 StandardlzatlOn of0 oo564N phenylarsme oXIde DIssolve approxImately 2g (± 19) KI m

100 to 150 ml dIstilled water, add 10 ml H2S04 solutlOn (5 8) followed by 20 m1 0 oo5N

potasslUm bllodate solutlOn (5 6) Place m dark for 5 mmutes, dIlute to 300 ml and tItrate

WIth 0 oo564N phenylarsme oXIde solutlOn (5 1) to a pale straw color Add a small scoop

ofmdlcator (57) Walt untIl homogenous blue color develops and contmue the tltratlOn

drop by drop untIl the color dIsappears Run m duphcate Duphcate determmatlOns

should agree WIthm ±O 05 ml

N PAO _ 20 XOOO5

mlPAO

Adjust PAO solutlOn If necessary and recheck

5 10 StandardIZation of 0 0375N phenylarsme oXlde DIssolve approxImately 2 g (± 19) KI m

100 to 150 ml dIstIlled water, add 10 ml H2S04 solutlOn (58) followed by 20 ml 0 IN

potasslUm bllodate solutlOn (5 5) Place m dark for 5 mmutes,' dIlute to 300 ml and tItrate

WIth 0 0375N phenylarsme OXIde solutlOn (5 10) to a pale straw color Add a small scoop

ofmdlcator (57) Walt untIl homogenous blue color develops and contmue the tltratlOn,

drop by drop untIl the color dIsappears Run m duphcate Duphcate determmatIon

should agree WIthm ±O 05 ml

N PAO- 20 XO 1

mlPAO

Adjust PAO solutlOn If necessary and recheck

5 11 StandardIZation of 0 IN Iodme solutlOn DIssolve approxImately 2g (± 1 g) KI m 100 to

150 ml dIstIlled water, add 20 ml Iodme SolutlOn (5 3) DIlute to 300 ml and tItrate WIth

o0375N phenylarsme oXlde solutlOn (5 10) to a pale straw color Add a small scoop of

mdlcator (57) Walt untIl homogenous blue color develops and contmue the titration

3302-2
drop by drop unttl the color disappears Run m duplIcate DuplIcate determmattons

should agree wlthm ±O 05 ml

ml PAO x 00375

20

Adjust lodme solution If necessary and recheck

5 12 StandardIzatIon of0 0282N Iodme solutIOn Dissolve approxImately 2 g (±1 g) KI m 100

to 150 ml dIstIlled water, add 20 ml Iodme solutIOn (5 4) Dtlute to 300 ml and tItrate

wIth 0 0375N phenylarsme oXIde solutIon (5 10) to a pale straw color Add a small scoop

ofmdlcator (57) Walt unttl homogenous blue color develops and contmue the tItratIOn

drop by drop untIl the color disappears Run m duplIcate DuplIcate determmattons

should agree wlthm ±O 05 ml

N _m1PAOx00375 12 - 20

Adjust Iodme solutIon Ifnecessary and recheck

6 Procedure

6 1 Starch-IodIde End Pomt

6 1 1 Place 5 00 ml of0 00564N PAO solutIOn (5 9) m a flask

6 1 2 Add approxImately 19 KI on a scoop

6 1 3 Add 4 ml acetate buffersolutIOn (5 2)

6 1 4 Add 200 ml ofsample For concentratIons above 10 mg/1, a sample ofless volume

may be dIluted to 200 ml wth chlonne-free, chlonne demand-free distIlled water

615 MIX well

6 1 6 Add approxImately 4 mg mdlcator (5 7)Just before tttratton

6 1 7 TItrate wIth 0 0282N IOdme solutIon (5 12) to the first appearance of a blue color

that perSIsts after mlxmg Record the ml oftitrant used

6 2 Amperometnc End Pomt

62 1 Perform steps 6 1 1-6 1 5 mcluslve or follow the dIrectIons ofthe manufacturer of

the amperometnc tltrator Prepackaged reagents should be checked

(restandardized)

6 2 2 Place the SolutIon m the proper posItIOn on the amperometnc tttrater

6 2 3 Titrate with 0 0282N Iodme SolutIOn (5 12) Observe the response of the meter

needle Imtlally the needle wIll remaIn statIOnary As the endpomt IS approached

the needle wIll temporanly deflect, then return to or near to ItS ongmal posItIon

Contmue dropwlse When the needle deflects and remams deflected the end pomt

has been exceeded by one drop Subtract 1I20th of an ml from the buret readmg

and record the result

3302-3
7. Calculations

mg/l CI = (A - 5B) x 200

C

where

A = mlOOO564NPAO

B = mlO 0282 N 12

C = mlsample

8 PreclSlon and Accuracy

8 1 Starch-Iodme Endpomt

8 1 1 PreCISIOn

In a smgle operator, smgle laboratory SituatIOn the followmg results were obtamed

Sample Average Stand Dev ReI Stand Dev

Matnx mg/1 ±mg/l %

Distilled Waters 041 005 122

351 012 33

Dnnkmg Water 084 004 43

RIver Water 084 002 27

Domestic Sewageb 087 007 76

Raw Sewage 055 009 160

aThreereplIcatesfor distIlledwater Seven replIcatesfor othersamplematrIces

bSecondarytreatment I "

8 1 2 Accuracy (Relative)

For four samples the results were compared to the lodometnc titratIOn as a means

ofobtalmng a relative accuracy

Iodometnc Starch IodIde

Sample TItratIOn Back TItratIOn %

Matnx mgll mg/I Recovery

Drmkmg Water 085 084 988

RIver Water 078 084 1077

DomestIc Sewage 100 087 870

Raw Sewage Approx 05 055 Approx 100 0

8 2 Amperometnc End Pomt

8 2 1 PreclSlon

In a smgle operator, smgle laboratory SituatIOn the followmg results were obtamed

3302-4
Sample Average Stand Dev ReI Stand

Matnx mgll ±mg/l Dev %

DIstl1led Watera 058 005 88

353 007 20

Dnnkmg Water 082 005 59

River Water 068 , 006 94

DomestIc Sewageb 110 009 83

aThree rephcatesfordIstl1led water Sevenrephcatesfor othersamplematnces

bSecondary treatment

8 2 2 Accuracy

For three samples the results were compared to the Iodometnc tItratIon as a means

ofobtammg a relatIve accuracy

Amperometnc

Iodometnc Back

Sample TItratIon TItration %

Matnx mgll mgll Recovery

Dnnkmg Water 083 082 988

River Water 066 068 1030

DomestIc Sewage 145 110 757

BIbliography

1 Standard Methods for the Exammation of Water and Wastewater, 14th Ed, p 318, Method

409B "Iodometric Method II", (1975)

2 ASTMStandards, Part 31 "Water", p 276, Method D1253-76 (1976)

3 Bender, D F, "Companson of Methods for the DetermmatlOn of Total AvaIlable ResIdual

Chlonne m Vanous Sa~ple Matnces", EPA Report-600/4-78-O19

3302-5
CHLORINE, TOTAL RESIDUAL

Method 330.3 (Titrimetric, Iodometric)

STORET NO. 50060

1 Scope and ApphcatIOn

lIThe 10dometnc titratIOn method IS apphcable to natural and treated waters at

concentratIOns greater than 0 1 mg/l

2 Summary ofMethod

2 1 Chlorme (hypochlonte lon, hypochlorous aCld) and chlorammes st01chIOmetncally

hberate IOdme from potassmm 10dlde at pH 4 or less

2 2 The IOdme IS tltrated wlth a standard reducmg agent such as sodmm thIOsulfate or

phenylarsme oXlde usmg a starch mdlcator

2 3 The results are calculated as mg/1 CI even though the actual measurement IS of total

oXldlzmg power because chlonne IS the dommant oXldlzmg agent present

3 Interferences

3 1 Femc, mangamc and mtnte 10ns mterfere, the neutral titratlOn mlmmlZeS these

mterferences

3 2 Acetlc aCld IS used for the aCld tltratIOn Sulfunc aCld may be used If no mterferences are

present Hydrochlonc aCld should never be used

3 3 Turbldlty and color may make the endpomt dlfficult to detect Practlce runs wlth splked

samples may be necessay

4 Apparatus

4 1 Standard laboratory glassware IS used A mlCroburet 0-2 m1 or 0-10 mils used

dependmg on the deslred range and accuracy

5 Reagents

5 1 Acetic aCld, conc (glaclal)

5 2 Potassmm 10dlde, KI, crystals

53 Phenylarsme oXlde (000564N) Wallace and Tleman or eqmvalent Standardize wlth

potassmm bllodate (5 8, 5 12)

5 4 Phenylarsme oXlde (00375N). Hach Chemlcal Co or eqmvalent Standardlze wlth

potassmm bllodate (57,5 13)

5 5 CommerCially avaIlable starch mdICators such as thyodene or eqUIvalent may be used

5 6 Potassmm bllodate (0 IN) Dlssolve 3 249 g potassmm bllodate, prevl0usly dned two

hours at 103°C, m dlstllled water and dllute to 1 0 hter Store m a glass stoppered bottle

5 7 Potassmm bllodate (0 05N) Dllute 500 ml of0 1 N potassmm bllodate (5 6) to 1 hter m a

volumetnc flask Store m glass stoppered bottle

5 8 Potassmm bllodate (0 005N) Dllute 50 ml of0 1 N potassmm bllodate (5 6) to 1 hter m a

volumetnc flask Store m glass stoppered bottle

Approved for NPDES

Issued 1978

3303-1
5.9 Standard IOdme solutIOn (0 IN) DIssolve 40 g KI m 25 ml dIstIlled water, add 13 g

resublImed Iodme and stIr untIl dIssolved Transfer to a I lIter volumetrIc flask and dIlute

tothemark Determmethe exactI10rmalIty(5 14)

5 10 Standard IOdme titrant (0 0282N) DIssolve 25 g KI m a lIttle dIstIlled water mal lIter

volumetrIc flask Add the calculated amount of 0 1 N standard Iodme to produce a

0.0282 N solutIon StandardIze daIly (5 15) Store m amber bottle or m dark, protect

from sunlIght at all tImes and keep from contact WIth rubber

5.11 SulfUrIC aCId solutIon (1 4) Slowly add 200 ml H2S04 (sp gr 1 84) to 800 ml of dIstIlled

water

512 StandardIzation of 0 00564N phenylarsme OXIde DIssolve approxImately 2 g (±1 g) KI

(5 2) m 100 to 150 ml dIstIlled water, add 10 ml H2S04 solutIon (5 11) followed by 20 ml

o005 N potassIUm bnodate SolutIon (5 8) Place m dark for 5 mmutes, dIlute to 300 ml

and titrate WIth 0 00564N phenylarsme OXIde solutIOn (5 3) to a pale straw color Add a

small scoop ofmdlcator (55) Walt untIl homogeneous blue color develops and contmue

the tItration drop by drop untIl the color dIsappears Run m duplIcate DuplIcate

determinatIOn should agree WIthin ±O 05 ml

NPAO = 20 x 0005

mlPAO

Adjust PAO SolutIon Ifnecessary and recheck

5 13 StandardIzatIon of 0 0375N phenylarsme OXIde DIssolve approxImately 2 g (± 1 g) KI

(52) m 100 to 150 ml dIstIlled water, add 10 ml H2S04 SolutIon (5 11) followed by 20 ml

o05 N potassIUm bnodate solutIon (5 7) Place m dark for 5 mmutes, dIlute to 300 ml and

titrate wth 0 0375 N phenylarsme OXide solutIOn (5 4) to a pale straw color Add a small

scoop of mdlcator (5 5) Walt untIl homogeneous blue color develops and contmue the

titratIon drop by drop untIl the color dlsappea,rs Run m duplIcate DuplIcate

determmatlons should agree WIthin ±O 05 ml

NPAO = 20 XO 1

mlPAO

Adjust PAO SolutIon Ifnecessary and recheck , I'

514 StandardIzatIon of 0 1 N IOdme SolutIon DIssolve approxImately 2 g (±1 g) KI (5 2) m

100 to 150 ml dIstIlled water, add 20 mllOdme solutIon (5 9) DIlute to 300 ml and tItrate

with 0 0375 N phenylarsme OXIde SolutIon (54) to a pale straw color Add a small scoop

ofmdlcator (55) Walt untIl homogeneous blue color develops and contmue the titratIon

drop by drop untIl the color dIsappears Run m duplIcate DuplIcate determmatlOns

should agree wlthm ±O 05 ml

N _ ml PAO x 0 0375 12 - 20

3303-2
Adjust lodme solutlOn Ifnecessary and recheck

515 StandardlzatlOn of 0 0282N lOdme solutlOn DIssolve approXImately 2 g (±1 g) KI (5 2)

m 100 to 150 ml dIstIlled water, add 20 mllodme solutlOn (5 10) Dtlute to 300 ml and

tItrate wIth 0 0375 N phenylarsme oXIde solutIOn (54) to a pale straw color Add a small

scoop of mdlcator (55) Walt unttl homogeneous blue color develops and contmue the

tltratlOn drop by drop unttl the color dIsappears Run m duphcate Duphcate

determmatIons should agree wlthm ±O 05 ml

-,..T _ rol PAa x 0 0375 J.,~I2 - 20

Adjust lodme solutIon Ifnecessary and recheck

6 Procedure

6 1 ThIS procedure gIVes a convement dIrect readmg (ml titrant = mg/l CI) m the range of

the mlcroburet (0 5 ml to 2,5 or 10 ml) The sample volume and reagent normahtles may

be vaned at the analyst's dlscretlOn

6 2 Place 5 ml acetIc aCId m an Erlenmeyer flask contammg a Teflon coated magnetIc

stlrrmgbar

6 3 Add about 1g KI (5 2) estImated on a spatula

6 4 Add 200 ml sample

6 5 Place on magnetIc stIrrer under buret

66 TItrate away from dIrect sunhght WIth 0 00564N PAO (53) to a pale straw color Add a

scoop of mdlcator (55) Walt untIl blue color IS homogeneously dlstnbuted, contmue

tltratmg unttl blue color IS dIscharged The ml of PAO IS equal to the mg/l CI plus or

, mmus the blank correctlOn (6 7) If any

6 7 Blank tItratlOn Usmg dlstl1led water m place ofthe sample perform steps 6 2-6 5, add a

scoop ofmdlcator Perform eIther 6 7 1or 6 7 2 dependmg on color development

6 7 1 Blank tItratlOn A If a blue color develops tItrate WIth 0 00564N PAO (5 3) to the

dIsappearance ofthe blue color and record the results

6 7 2 Blank tItratlOn B Ifno blue color develops titrate WIth 0 0282N lOdme (5 10) untl1

blue color appears Back tItrate WIth 000564N PAO (53) and record the

dIfference as titratIon B

7 CalculatlOns

7 1 The ml of PAO tItrant IS equal to mg/l Cl under the volumes and 'concentratlOns

descnbed The blank correctlOn A (67 1) can be dIrectly subtracted The blank

correctlOn B (672), WhICh IS added, mvolves a factor of 5 (unless one substitutes

o00564N lOdme for the 0 0282N lOdme) Normally the reagents are pure enough that the

blank correctlOn IS mSlgmficant and therefore unnecessary

3303-3
8 PreclSlon and Accuracy

ThIrty to thIrty two laboratones analyzed prepared samples of 0 64, 0 84 and 1 83 mg/1 The

relatIve standard deviations were 27 0%, 32 4% and 23 6% respectively and relatIve errors

were 23 6%, 18 5%, and 167% respectively

In a smgle operator, smgle laboratory, situatIon the followmg results were obtamed

Sample matnx

DIstIlled Watera

Dnnkmg Water

RIver water

Domestic Sewageb

Raw sewage

Average Standard ReI standard

mgll deVIation deViatIOn

±mgll %

025 0001 023

402 003 076

068 004 52

030 003 97

111 006 59

048 009 180

aThreerepJIcatesfor distilledwater Seven replIcatesfor othersamplematnces

bSecondarytreatment

BIbliography

1. Standard Methods for the ExammatlOn of Water and Wastewater, 14th ed p 316, Method

409A "Iodometnc Method I" (1975)

2. ASTM Standards, Part 31, "Water", p 276, Method D1253-76 (1976)

3 Bender, D F, "Companson of Methods for the DetermmatlOn of Total AvaIlable Residual

Chlonne In Vanous Sample Matnces", EPA Report~600/4-78-019

330 3~4
CHLORINE, TOTAL RESIDUAL

Method 330.4 (Titrimetric, DPD-FAS)

STORET NO. 50060

1 Scope and ApphcatiOn

11 The N,N-diethyl-p-phenylene diamme (DPD) - ferrous ammomum sulfate (FAS)

titration method IS appllcable to natural and treated waters at concentrations above 0 I

mg/l CI

2 Summary ofMethod

2 1 ChlorIne (hypochlorIte lOn, hypochlorous aCId) and chlorammes stOichIOmetrIcally

hberate iOdme from potasslUm IodIde at pH 4 or less

, 2 2 The IOdme IS titrated WIth FAS usmg DPD as the mdicator

23 The results are calculated as mg/1 CI even though the actual measurement IS of total

oXIdIzmg power because chlorme IS the dommant oXIdIzmg agent present

3 Intaferences

3 1 Bromme, bromamme and Iodme are mterferences WhICh are normally present m

mSIgmficant amounts

32 OXIdIzed manganese mterferes but can be corrected by subtractiOn after performmg a

titratiOn m the presence ofsodlUm arsemte (NaAs02)

33 Copper mterferes but IS accounted for (up to apprOXImately 10 mg!l copper) by

mcorporation ofEDTA The EDTA also retards deterIOratIOn ofDPD due to OXIdatIon

and completely suppresses dIssolved oxygen errors by preventmg trace metal catalySIS

3 4 TurbIdIty and color may make the endpomt dIfficult to detect PractIce runs WIth spIked

samples may be necessary

4 Apparatus

4 1 Standard laboratory glassware IS used A ffilcroburet, 0-2 ml or 0-10 ml, dependmg on

the concentration range expected, IS used

5 Reagents

5 1 Phosphate buffer solutIOn DIssolve 24 g anhydrous disodlUm hydrogen phosphate,

Na2HP04, and 46 g anhydrous potasslUm dihydrogen phosphate, KH2P04, m disttlied

water DIssolve 800 mg disodlUm ethyienediamme tetraacetate dIhydrate m 100 ml

dIstIlled water Combme these two solutiOns and dtlute to 1 hter WIth dIstIlled water

Add 20 mg HgCl2as a preservatIve

5 2 N,N-DIethyl-p-phenylenediamme (DPD) mdicator SolutIon DIssolve 1 g DPD oxalate

or 1 5 g p-ammo-N,N-diethylamhne sulfate m chlOrIne free disttlied water contammg 8

ml of 1+3 H2S04and 200 mg disodlUm ethyienediamme tetraacetate dIhydrate DIlute

to 1 hter, store m a colored, glass-stoppered bottle DIscard when dIscolored The buffer

and mdicator sulfate are avatlable as a combmed reagent m stable powder form

CAUTION The oxalate IS tOXIC, aVOid mgestlOn

Approved for NPDES

Issued 1978

3304-1
, I r

53 Standard ferrous ammomum sulfate (FAS) tItrant DIssolve 1 106g Mohr's salt

Fe(NH4)2(S04)2-6H20, m dlstllied water contammg 1 ml of 1 + 3 H2S04(54) and make

up to 1 hter wIth freshly bolled and cooled dlstllied water Stable for one month Check

WIth tltratlOn by standard potassmm dlchomate (5 5) The FAS tItrant IS eqmvalent to

100 ug ClI1 00 ml

54 Sulfunc aCId solutlOn (1+3) Slowly add one part ofH2S04(sp gr 1 84) to three parts of

dIstIlled water

5 5 PotasslUm dIchromate (0 1000N) DIssolve 4 904 g potasslUm dIchromate (K2Cr20~)In

dIstllled water and dllute to 1 hter

5 6 Potassmm IodIde, KI Crystals

57 Sodmm Arsemte SolutlOn Place 500 mg of sodmm arsemte (NaAs02) m a flask and

dllute to 100 ml WIth dlstllied water

6 Procedure

6 1 ThIS procedure gives a convement dIrect readmg (ml tItrant = mg!l CI) up to 4 mg!l

An ahquot should be dlluted to 100 mllfmgher concentratlOns are present

62 Place 5 ml ofphosphate buffer (5 1) m a tltratlOn flask

6 3 Add 5 ml ofDPD mdlcator (5 2)

64 Add approxlmately 1g ofKI (5 6) on a scoop

65 Add 100 ml ofsample

66 WaIt2mmutes

67 TItrate WIth FAS (53) until the red color IS dIscharged Record the volume of titrant

used

6 8 IfOXIdIzed manganese IS present

68 1 Place 5 ml ofphosphate buffer (5 1) m a tItration flask

6 8 2 Add one small crystaI ofpotassmm lOdlde (5 6)

6 8 3 Add 05 ml ofsodmm arsemte SolutIon (5 7)

6 8 4 Add 100 ml ofsample MIX

6 8 5 Add 5 ml DPD mdlcator (5 2) MIX

6.86 TItrate wth FAS (53) until the red color IS dIscharged Record the volume of

tItrant used

7 CalculatlOns

71 The ml of FAS tItrant IS equal to the mg!l CI If OXIdIzed manganese was present,

subtract the ·amount of tItrant used m 6 8 6 from the amount of tItrant used m 6 7 to

obtaIn the mg!l Cl

8. PreCIsIon and Accuracy

Nmeteen laboratones analyzed prepared samples of 0 64 and 1 83 mg!l CI The relatIve

standard deVIatIons were 192 and 94% respectIvely and the relative errors were 8 1 and 43%

respectIvely

3304-2
In a smgle operatorsmgle laboratory sItuatIon the followmg results were obtamed

Sample Average Stand Dev ReI Stnd Dev

Matnx mg/l ±mg/l %

DIstIlled Watera 034 002 56

065 0003 05

345 002 05

Dnnkmg Water 098 001 12

RIver Water 079 001 14

DomestIc Sewage 108 002 1 8

Raw Sewage 079 003 3 3

aThree replIcatesfor dIstIlledwater SevenreplIcatesfor othersamples

For four samples the results were compared to the IOdometnc tItratIOn as a means of obtammg a

relatIve accuracy

Iodometnc DPD

Sample TItratIOn FAS TItratIOn

Matnx mg/l mg/l % Recovery

Drmkmg Water 091 098 1077

RIver Water 073 079 1082

DomestIC Sewage 120 108 900

Raw Sewage 075 079 1053

BIbliography

1 Standard Methods for the ExammatIon ofWater and Wastewater, 14th Ed Page 329, Method

409E, "DPD Ferrous TItnmetic Method" (1975)

2 Bender, D F, "Companson of Methods for the DetermmatIOn of Total AVailable ResIdual

Chlonne m Vanous Sample Matnces", EPA Report-600/4-78-Q19

3304-3
CHLORINE, TOTAL RESIDUAL

Method 330.5 (Spectrophotometric, DPD)

STORET NO. 50060

1 Scope and ApphcatiOn

lIThe DPD-Colonmetnc method IS apphcable to natural and treated waters at

concentratiOnsfrom 0 2-4 mg/1

2 Summary ofMethod

2 1 Chlonne (hypochlonte lon, hypochlorous aCId) and chioramllles stoichiometncally

hberate IOdllle from potassmm IodIde at pH 4 or less

22 The hberated IOdllle reacts wIth N,N-diethyl-p-phenylene diamllle (DPD) to produce a

red colored solutIOn

2 3 The solutiOn IS spectrophotometncally compared to a senes ofstandards, USlllg a graph

or a regressiOn analysIs calculatIOn

2 4 The results are read or calculated llltO mg/1 CI

3 Interferences

3 1 Any oXIdIzmg agents, these are usually present at lllsIglllficant concentratIons compared

to the resIdual chlonne concentratIOns

3 2 TurbIdIty and color wIll essentIally prevent the colonmetnc analySIS

4 Apparatus

4 1 Spectrophotometer for use at 515 nm and cells ofhght path 1cm or longer

5 Reagents

5 1 Phosphate buffer solutiOn DIssolve 24 g anhydrous disodmm hydrogen phosphate,

Na2HP04, and 46 g anhydrous potassmm dihydrogen phosphate, KH2P04, III dIstIlled

water DIssolve 800 mg disodmm ethyienediamllle tetraacetate dihydrate III 100 ml

dIstIlled water Combllle these two solutIOns and dIlute to 1 lIter wIth dIstIlled water

Add 20 mg Hg Cl2 as a preservatIve

52 N,N-DIethyl-p-phenylenediamllle (DPD) llldicator solutIOn DIssolve 1 g DPD oxalate

or 1 5 g p-amlllo-N,N-diethYlallllIne sulfate III chlonne free disttlled water contallllllg 8

ml of 1 +3 H2S04 (5 3) and 200 mg disodmm ethyienediamllle tetraacetate dIhydrate

DIlute to litter, store III a colored, glass-stoppered bottle DIscard when dIscolored The

buffer and mdicator sulfate are avaIlable as a combllled reagent III stable powder form

CAUTION The oxalate IS tOXIC, aVOId lllgestiOn

53 Sulfunc aCId solutIOn (1 + 3) Slowly add one part of H2S04 (sp gr 1 84) to three parts

ofdIstIlled water

5 4 Potassmm IodIde, KI crystals

5 5 Stock Potassmm Permanganate SolutiOn Place 0891 g KMn04 111 a volumetnc flask and

dIlute to 1lIter

Approved for NPDES

Issued 1978

3305-1
5 6' Standard PotasslUm Permanganate SolutlOn Dllute 10 00 ml of stock potassiUm

permanganate splutlOn (55) to 100 ml wIth dIstIlled water In a volumetnc flask One

mIllthter ofthIS solutlOn dIluted to 100 ml wIth dIstIlled water IS eqUIvalent to 1 00 mg/l

CI

6. Procedure

6 1 Cahbration

6 1 1 Prepare a senes of permanganate standards coverIng the chlonne eqUIvalent range

of0 05 to 4 mg/l

6 1 2 Place 5 m1 phosphate buffer (5 1) In a flask

6 1 3 Add 5 ml DPD reagent (5 2)

6 1 4 Add 100 ml permanganate standard (6 1 1)

6 1 5 Read at 515 nm on a spectrophotometer and record the absorbance

6 1 6 Return the contents ofthe cell to the flask

6 1 7 TItrate the contents of the flask wIth standard ferrous ammOnIum sulfate (DPDFAS Method), untIl the red color IS dIscharged Record the result

6 2 SampleAnalysIs

62 1 Place 0 5 ml phosphate buffer (5 1) In flask

6 2 2 Add 0 5 ml DPD reagent (5 2)

6 2 3 Add approXImately 0 1g KI (5 4)

624 Add 10 ml ofsample

6 2 5 Letstand 2 mInutes

6 2 6 Read at 515 nm on a spectrophotometer, and record the absorbance

7. CalculatIons

7.1 CahbratlOn Curve Method

7 1 1 Plot the absorbance ofthe standard permanganate solutlOns (6 1 5) on the vertIcal

aXIS versus the tItrated concentration (6 1 7) on the honzontal aXIS

7 1 2 Draw the hne ofbest fit through the POInts

7 1 3 Locate the absorbance (6 2 6) ofthe sample on the vertIcal aXIS

7 1 4 Read the concentratIon on the honzontal aXIS at the Intersect of the absorbance

and the cahbratlOn hne

7.2 RegresslOn AnalysIs CalculatlOn-Computenzed

72 1 Enter the absorbance data of the standard permanganate solutlOns (6 1 5) and the

respect~ve tItrated concentratlOns (6 1 7) In the appropnate places In the program

7 2 2 Enter the absorbance data ofthe sample

7 2 3 The computer wIll then dIsplay the concentratlOn In mg/l CI

8 PrecIsIon and Accuracy

Twenty-five laboratones analyzed prepared samples of 0 66 mg/l CI The relatIve standard

devIation was 27 6% and the relatIve error was 15 6%

3305-2
In a smgle laboratory, smgle operatorsituatIOn the followmg results were obtamed

Sample Average Stnd Devd ReI Stnd Dev"

Matnx mg/l ±Img/l %

Distilled Watera 039 0012 3 1

361 011 32

Drmkmg Water 094 0008 08

River Water 086 002 19

Domestic Sewage 107 003 24

aThree repltcatesfor distilled wat~r Seven repltcatesfor othersamples

For three samples the results were compared to the lodometnc titratIOn as a means of obtalmng a

relative accuracy

Sample

Matnx

Dnnkmg Water

River Water

Domestic Sewage

Iodometnc

TitratIOn

mg/l

086

070

101

DPD

Colonmetnc mgll

094

086

107

Bibliography

%Recoyery

1093

1229

1060

1 Standard Methods for the ExammatIOn of Water and Wastewater, 14th Ed, Pg 332, Method

409F, "DPD ColonmetncMethod", (1975)

2 Bender, D F, "Companson of Methods for the Determination of Total Available Residual

Chlonne m Vanous Sample Matnces", EPA Report-600/4-78-O19

3305-3
CYANIDES, AMENABLE TO CHLORINATION

Method 335.1 (Titrimetric; Spectrophotometric)

STORET NO. 00722

1 Scope and ApplicatlOn

1 1 ThIS method IS applIcable to the determmatlOn of cyamdes amenable to chlormatlOn m

dnnkmg, surface and salIne waters, domestIc and mdustnal wastes

1 2 The titratlOn procedure IS used for measurmg concentratlOns of cyamde exceedIng 1

mg/l after removal of the cyamdes amenable to chlormatlOn Below th1s level the

colonmetnc determmatlOn IS used

2 Summary ofMethod

2 1 A portlOn of the sample IS chlonnated at a pH> 11 to decompose the cyamde CyanIde

levels m the chlonnated !>ample are then determmed by the method for Cyamde, Total, m

thIS manual Cyamdes amenable to chlormatlOn are then calculated by dIfference

3 Reagents

3 1 CalcIUm Hypochlonte SolutIon DIssolve 5 g of calcIUm hypochlonte (Ca(OC1)2) In 100

ml ofdIstIlled water

32 SodIUm HydroxIde SolutIon DIssolve 50 g of sodIUm hydroxIde (NaOH) m dIstIlled

water and dIlute to 1liter

3 3 AscorbIc aCId crystals

3 4 PotassIUm IodIde-starch test paper

4 Procedure

4 1 Two sample alIquots are reqUIred to determme cyamdes amenable to chlormatlOn To

one 500 ml alIquot or a volume dIluted to 500 ml, add calcIUm hypochlonte solutlOn (3 1)

dropwise whIle agItatIng and mamtammg the pH between 11 and 12 WIth sodIUm

hydroxIde (3 2)

CautlOn The mitIal reactlOn product of alkaline chlonnatlOn IS the very tOXiC gas

cyanogen chlonde, therefore, It IS recommended that thIS reaction be performed m a

hood For convemence, the sample may be agItated mal liter beaker by means of a

magnetIc stIrnng deVIce

42 Test for reSIdual chlonne WIth KI-starch paper (34) and mamtam thIS excess for one

hour, contmumg agitatlOn A dIstmct blue color on the test paper mdicates a suffiCIent

chlonne level Ifnecessary, add additlOnal hypochlonte solutlOn

43 After one hour, add 05 g portlOns of ascorbIC aCId (3 3) until KI-starch paper shows no

reSIdual chlonne Add an addItional 0 5 g of ascorbIc aCId to msure the presence ofexcess

reducmg agent

4 4 Test for total cyamde m both the chlormated and unchlormated alIquots as In the

method Cyamde, Total, m thIS manual

Approved for NPDES

Issued 1974

335 1-1
5. CalculatIOn

5.1 Calculate the cyamde amendable to chlonnatlOn as follows

CN,mg/l = A-B

where

A = mg/l total cyanIde In unchlonnated alIquot

B = mg/l total In chlonnated alIquot

BIblIography

1. Annual Book of ASTM Standards, Part 31, "Water", Standard D 2036-75, Method B, p 505

(1976)

2. Standard Methods for the ExamInatIOn ofWater and Wastewater, 14th EdItIOn, p 376 and 370,

Method 413F and D (1975)

335 1-2
CYANIDE, TOTAL

Method 335.2 (Titrimetric; Spectrophotometric)

STORET NO. 00720

1 Scope and ApphcatlOn

1 1 ThlS method IS apphcable to the determmatlOn of cyamde III dnnklllg, surface and salllle

waters, domestlc and llldustnal wastes

1 2 The titratlOn procedure uSlllg stlver mtrate wlth p-dlmethylamlllo-benzal-rhodamne

llldlcator IS used for measunng concentiatlOns of cyamde exceedlllg 1 mg/1 (025

mg/250 ml ofabsorblllg hqUld)

1 3 The colonmetnc procedure IS used for concentratlOns below 1 mg/1 of cyamde and IS

sensltlve to about 0 02 mg/1

2 Summary ofMethod

2 1 The cyamde as hydrocyamc aCld (HCN) IS released from cyamde complexes by means of

a reflux-dlstillatlOn operatlOn and absorbed III a scrubber contallllllg sodmm hydroxlde

Solutl0n The cyamde 10n III the absorblllg solutlOn IS then determllled by volumetnc

tltratl0n or colonmetncally

2 2 In the colonmetnc measurement the cyamde IS converted to cyanogen chlonde, CNCI,

by reaction wlth chioramllle-T at a pH less than 8 wlthout hydrolyzlllg to the cyanate

After the reactlOn IS complete, color IS formed on the addltlOn ofpyndllle-pyrazoione or

pyndllle-barbltunc aCld reagent The absorbance IS read at 620 nm when USlllg pyndlllepyrazolone or 578 nm for pyndllle-barbltunc aCld To obtalll colors of comparable

llltenslty, It IS essentlal to have the same salt content m both the sample and the

standards '

2 3 The tltnmetnc measurement uses a standard solutlOn ofstlver mtrate to tltrate cyamde m

the presence ofa stlversensltive llldlcator

3 DefimtlOns

3 1 Cyamde IS defined as cyamde lOn and complex cyamdes converted to hydrocyamc aCld

(HCN) by reactlOn m a reflux system of a mllleral aCld III the presence ofmagnesmm lOn

4 Sample Handl111g and PreservatlOn

4 1 The sample should be collected m plastlc or glass bottles of 1 hter or larger Slze All

bottles must be thoroughly cleansed and thoroughly rlllsed to remove soluble matenal

from contalllers

4 2 OXldlz111g agents such as chlonne decompose most of the cyanldes Test a drop of the

sample wlth potassmm lOdlde-starch test paper (KI-starch paper), a blue color mdlcates

the need for treatment Add ascorblc aCld, a few crystals at a time, unttl a drop ofsample

produces no color on the mdicator paper Then add an addltlonal 0 06 g of ascorbIc

aCId for each lIter of sample volume

Approved for NPDES

Issued 1974

Editonal reVISIon 1974 and 1978

Techmcal ReVISIOn 1980

3352-1
4 3 Samples must be preserved wIth 2 ml of 10 N sodmm hydroxIde per hter of sample

(pH 12) at the time ofcollectIOn

4 4 Samples should be analyzed as rapIdly as possIble after collectIOn Ifstorage IS reqUlred,

the samples should be stored m a refngerator or m an lCe chest filled wIth water and lCe to

mamtam temperature at 4°C

5. Interferences

5 1 Interferences are ellmmated or reduced by usmg the dlst111atIOn procedure descnbed

m Procedure 81,82 and 8 3

52 SulfIdes adversely affect the colonmetnc and tItraUon procedures Samples that

contam hydrogen sulfIde, metal sulfIdes or other compounds that may produce

hydrogen sulfIde durmg the dlst111auon should be dlsulled by the opuonal procedure

descnbed m Procedure 8 2 The apparatus for thIS procedure IS shown m FIgure 3

5 3 Fatty aCIds WIll dIstIll and form soaps under the alkahne tItratIOn condItIons, makmg the

end pomt almost ImpossIble to detect

5 3 1 ACIdIfy the sample WIth acetIc aCId (1 +9) to pH 6 0 to 7 0

CautIOn ThIS operatIOn must be performed m the hood and the sample left there

untliit can be made alkahne agam after the extractIOn has been performed

5 3 2 Extract WIth Iso-octane, hexane, or chloroform (preference m order named) WIth a

solvent volume equal to 20% of the sample volume One extractIOn IS usually

adequate to reduce the fatty aCIds below the mterference level AVOId multIple

extractIOns or a long contact time at low pH m order to keep the loss of HCN at a

mInImUm When the extractIOn IS completed, ImmedIately raIse the pH of the

sample to above 12 WIth NaOH solutIOn

5.4 HIgh results may be obtamed for samples that contam mtrate and/or mtnte Dunng

the disUllation mtrate and mtnte WIll form mtrous aCId whIch WIll react WIth some

orgamccompounds to form OXImes These compounds formed WIll decompose under

test COndItIOnS to generate HCN The mterference of mtrate and mtnte IS ehmmated

b) pretreatment WIth suifamic aCId

6. Apparatus

6 1 Reflux dIstIllatIOn apparatus such as shown m FIgure 1 or FIgure 2 The bOIhng flask

should be of 1 hter SIze WIth inlet tube and prOVISIon for condenser The gas absorber may

be a Fisher-MIlhgan scrubber

6 2 Microburet, 5 0 ml (for tItratIOn)

6 3 Spectrophotometer sUltable for measurements at 578 nm or 620 nm WIth a 1 0 cm cell or

larger

64 Reflux dlsullauon apparatus for sulfide removal as shown m Figure 3 The bOllmg

flask same as 6 1 The sulfIde scrubber may be a Wheaton Bubber #709682 With 29/42

Joints, size 100 ml The aIr mlet tube should not be fntted The cyamde absorptIOn

vessel should be the same as the sulfIde scrubber The aIr mlet tube should be frItted

65 Flow metel, such as Lab Crest with stamless steel float (FIsher 11-164-50)

7. Reagents

7.1 Sodmm hydrOXIde solutIOn, 1 25N DIssolve 50 g of NaOH m dIstIlled water, and dIlute

to 1 lIter WIth dIstIlled water

3352-2
72 Lead acetate DIssolve 30 g of Pb (C2H302)e3H20 m950 ml of dIstIlled water Adjust

the pH to 4 5 wIth acetIc aCId DIlute to 1 lIter

75 Sulfunc aCId, 18N Slowly add 500 ml of concentrated H2S04 to 500 ml of dIstIlled

water

7 6 SodIUm ~:hhydrogenphosphate, 1 M DIssolve 138 g of NaH2P04-H20 m 1 hter of

dIstilled water RefrIgerate thIs solutIOn

77 Stock cyamde solutIOn DIssolve 2 51 g of KCN and 2 g KOH m 900 ml of dIstIlled

water StandardIze wIth 00192 N AgN03 DIlute to appropnate concentratIon so that

I ml = 1 mgCN

7 8 Standard cyamde solutIOn, mtermedlate DIlute 1000 ml ofstock (l ml = 1mg CN) to

1000 ml wIth dIstIlled water (l ml = 100 0 ug) , , ,

79 Workmg standard cyamde solutIOn Prepare fresh daIly by dIlutmg 1000 ml of

IntermedIate cyamde solutIOn to 1000 ml wIth dIstIlled water and store m a glass

stoppered bottle 1 ml = 10 0 ug CN

7 10 Standard silver mtrate solutIOn, 00192 N Prepare by crushmg approxImately 5 g

AgN03 crystals and drymg to constant weIght at 40°C WeIgh out 32647 g of drIed

AgN03, dIssolve m dIstIlled water, and dIlute to 1000 ml (1 ml = 1mg CN)

7 11 Rhodamne mdicator DIssolve 20 mg of p-dimethyl-ammo-benzalrhodanme m 100 ml of

acetone

7 12 Chloramme T solutIOn DIssolve 109 ofwhIte, water soluble Chloramme T m 100 ml of

dIstIlled water and refngerate untIl ready to use Prepare fresh daIly

7 13 Color Reagent - One ofthe followmg may be used

7131 PyrIdme-BarbiturIc ACId Reagent Place 15 g of barbItUrIC aCId m a 250 ml

volumetrIC flask and add Just enough <hsttlled water to wash the SIdes of the

flask and wet the barbIturIc aCId Add 75 ml ofpyndme and mIX Add 15 ml

of conc HCI, mIX, and cool to room temperature DIlute to 250 ml wIth

dIstIlled water and mIX ThIS reagent IS stable for approxImately SIX months

If stored m a cool, dark place

7 13 2 PyrIdme-pyrazolone solutIOn

7 132 1 3-Methyl-l-phenyl-2-pyrazolm-5-one reagent, saturated solutIOn Add

025 g of 3-methyl-l-phenyl-2-pyrazohn-5-one to 50 ml of dIstilled

water, heat to 60°C WIth stIrnng Cool to room temperature

7 13 22 3,3'DImethyl-l, 1'-diphenyl-[4,4'-bI-2 -pyrazolme]-5,5'dIOllC (bispyrazolone) DIssolve 0 01 g ofbispyrazolone m 10 ml ofpyrIdme

7 13 2 3 Pour solutIOn (7 13 2 1) through non-acId-washed filter paper Collect

the filtrate Through the same filter paper pour solutIOn (7 13 2 2)

collectmg the filtrate m the same contamer as filtrate from (7 13 2 1)

MIX untIl the filtrates are homogeneous The mIxed reagent develops a

pmk color but thIS does not affect the color productIOn WIth cyanIde If

used withm 24 hours ofpreparatIon

7 14 MagneSIUm chlOrIde SolutIon WeIght 510 g ofMgCl2-6H20 mto a 1000 ml flask, dIssolve

and dtlute to 1 hter WIth dIstIlled water

7 15 Sulfamic aCId I

3352-3
8. Procedure

8 1 For samples wIthout sulfIde

8 I I Place 500 ml of sample, or an alIquot dIluted to 500 ml m the 1 lIter bOIlmg

flask PIpet 50 ml of sodIUm hydroxIde (7 1) mto the absorbmg tube If the

apparatus m FIgure 1 IS used, add dIstIlled water untIl the spIral IS covered

Connect the boIlmg flask, condenser, absorber and trap m the (ram (FIgure 1

or 2)

8 1 2 Start a slow stream of aIr entenng the bOIlIng flask by adJustmg the vacuum

source AdJ ust the vacuum so that approxImately two bubbles of aIr persecond

enters the bOIlmg flask through the aIr mlet tube Proceed to 8 4

82 For samples that contam sulfIde

8.2 1 Place 500 ml of sample, or an alIquot dIluted to 500 ml m the 1 lIter bOIlmg

flask Plpet50 ml ofsodIUm hydroXIde (7 1) to the absorbmg tube Add 25 ml of

lead acetate (7 2) to the sulfIde scrubber Connect the boIlmg flask, condenser,

scrubber and absorber m the tram (FIgure 3) The flo~ meter IS connected to the

outlet tube of the cyamde absorber

82 2 Start a stream of aIr entermg the bOIlmg flask by adJustmg the vacuum source

Adjust the vacuum so that approxImately 1 5 lIters per mmute enters the

bOIlmg flask through the aIr mlet tube The bubble rate may not remam

constant whIle heat IS bemg applIed to the flask It may be necessary to readjust

the aIr rate occasIOnally Proceed to 8 4

83 Ifsamples contam NOs and or N02 add 2 g of sulfamlc aCId solutIon (7 15) after the aIr

rate IS set through the aIr mlet tube MIX for 3 mmutes pnor to addltlon of H~04

8 4 Slowly add 50 ml l8N sulfunc aCId (7 5) through the au mlet tube Rmse the tube with

dIstIlled water and allow the aIrflow to mIX the flask contents for 3 mm Pour 20 ml of

magnesIUm chlonde (7 14) mto the aIr mlet and wash down with a stream of water

85 Heat the solutIon to bOIlmg Reflux for one hour Turn off heat and contmue the

anflow for at least 15 mmutes After coolmg the bOIlmg flask, dIsconnect absorber and

close off the vacuum source

86 Dram the solution from the absorber mto a 250 ml volumetrIc flask Wash the absorber

With dIstilled water and add the washmgs to the flask DIlute to the mark with dIstIlled

water

87 Withdraw 50 ml orless of the solution from the flask and transfer to a 100 ml volumetnc

flask If less than 50 mIlS taken, dIlute to 50 ml with 0 25N sodIUm hydroXIde SolutIon

(74) Add 150 ml of sodIUm phosphate solutIOn (7 6) and mix

871 Pyndme-barbltunc aCId method Add 2 ml of chloramme T (7 12) and mIX

See Note 1 After 1 to 2 mmutes, add 5 ml of pyndme-barbItunc aCId solution

(713 1) and mIX DIlute to mark WIth dIstIlled water and mIX agam Allow 8

mmutes for color development then read absorbance at 578 nm mal cm cell

wIthm 15 mmutes

8 7 2 Pyndme-pyrazolene method Add 0 5 ml of chloramme T (7 12) and mIX See

Note 1 and 2 After 1 to 2 mmutes add 5 ml of pyndme-pyrazolone solutIOn

3352-4
(7 13 1) and mIX DIlute to mark wIth dIstIlled water and mIX agam After 40

mmutes read absorbance at 620 nm mal cm cell

NOTE 1 Some dIstIllates may contam compounds that have a chlonne

demand One mmute after the addItIOn of chloramme T, test for

resIdual chlonne wIth KI-starch paper If the test IS negatIve, add an

addItIOnal 0 5 ml of chlormeT After one mmute, recheck the sample

NOTE 2 More than 05 ml of chloramme T WIll prevent the color from

developmg wIth pyndme-pyrazolone

88 Standard curve for samples WIthout sulfIde

8 8 1 Prepare a senes of standards by pipetmg sUItable volumes of standard solutIOn

(79) mto 250 ml volumetnc flasks To each standard add 50 ml of 125 N

sodIUm hydroxIde and dIlute to 250 ml wIth dIstIlled water Prepare as follows

ML of Work~ng Standard SolutIon

(l ml = 10 /-lg CN)

o

10

20

50

100

150

200

Cone. /-lg CN

per 250 ml

BLANK

10

20

50

100

150

200

8 8 2 It IS not ImperatIve that all standards be dIstIlled m the same manner as the

samples It IS recommended that at least two stqndards (a hIgh and low) be

dIstIlled and compared to sImIlar values on the curve to msure that the dIStIllatIon techmque IS rehable If dIstIlled standard~ do not agree withm ±1O%

of the undistIlled standards the analyst should fmd the cause of the apparent

error before proceedmg

8 8 3 Prepare a standard curve by plottmg absorbance of standard vs cyamde

concentratIons

884 To check the effIcIency of the sample dIstIllatIon, add an mcrement of cyamde

from eIther the mtermedlate standard (7 8) or the workmg standard (7 9) to

500 ml of sample to msure a level of 20 /-lg/l Proceed wIth the analysIs as m

Procedure (8 1 1)

89 Standard curve for samples WIth sulfIde

8 9 I It IS ImperatIve that all standards be dIstIlled m the same manner as the samples

Standards dIstIlled by thIS method wIll gIve a lInear curve, but as the concentration mcreases, the recovery decreases It IS recommended that at least 3

standards be dIstIlled

8 9 2 Prepare a standard curve by plottmg absorbance of standard vs cyamde concentratIons

3352-5
8 10 TItnmetnc method

810 1 If the sample contams more than 1 mg!l of eN, transfer the dIstIllate or a

SUItable alIquot dIluted to 250 ml, to a 500 ml Erlenmeyer flask Add 10-12 drops

of the benzalrhodanme mdlcator ,

8102 TItrate wIth standard sIlver mtrate to the fust change m color from yellow to

browmsh-pmk TItrate a dIstIlled water blank usmg the same amount ofsodIUm

hydroxIde and mdIcator as m the sample

8.10 3 The analystshould famllIanze hImself WIth the end pomt of the tItratIOn and the

amount of mdlcator to be used before actrally tItratmg the samples.

9 CalculatIOn

9 1 If the colonmetnc procedure IS used, calculate the cyantde, 10 ug/l, 10 the ongmal

sample asfollows

eN, ug/I = A x 1,000 x 50

B C

where

A = ug CN read from standard curve

B - ml of ongInal sample for dIstIllatIOn

C = ml taken for colonmetrIc analysIs

3352-6
92 Usmg the tItnmetnc procedure, calculate concentratiOn ofCN as follows

(A - B)l,OOO 250

eN, mg/l = mlong sample x ml of ahquot titrated

where

A = volume ofAgN03 for titratiOn ofsample

B = volume ofAgN03 for titration ofblank

10 Precision and Accuracy

10 1 In a smgle laboratory (EMSL), usmg mlXed industnal and domestic waste samples at

concentrations of 006, 0 13, 028 and 062 mg/l CN, the standard deViatiOns were

±O 005, ±O 007, ±O 031 and ±O 094, respectively.

102 In a smgle laboratory (EMSL), using mixed mdustnal and domestic waste samples at

concentratiOns of0 28 and 062 mg/l CN, recovenes were 85% and 102%, respectively

BIbliography

1 Bark, L S, and Higson, H G "InveStigatiOn ofReagents for the Colonmetnc DetermmatiOn

ofSmall Amounts ofCyamde", Talanta, 2 471-479 (1964)

2 Blly, C T "Recovery of Cyamdes by Modified Serfass DistillatiOn" Journal Water Pollution

Control FederatiOn 40 848-856 (1968)

3 Annual Book of ASTM Standards, Part 31, "Water", Standard D2036-75, Method A, p 503

(1976)

4 Standard Methods for the Exammation ofWater and Wastewater, 14th Edition, p 367 and 370,

Method 413B and D (1975)

5 Egekeze, J 0, and Oehne, F W, "DIrect PotentlOmetnc DetermmatlOn of Cyamde m

BIOlogIcal Matenals," J AnalytIcal TOXIcology, Vol 3, p 119, May/June 1979

6 Casey, J P ,Bnght, J W ,and Helms, B D, "NltrosatIon Interference m DIStillatIon Tests

for Cyamde," Gulf Coast Waste DIsposal Authonty, Houston, Texas

3352-7
ONE lITERBOILING FLASK

- CONNECTING TUBING

SUCTION

GAS ABSORBER

FIGURE 1

CYANIDE DISTILLATION APPARATUS

3352-8

I I II I I
COOLING WATER .-

OUT

I;:m:===~ '" TO LOW VACUUM

SOURCE

INLET TUBE,

- ABSORBER

\

CONDENSER

- DISTILLING FLASK

HEATER -

o

FIGURE 2

CY AN 10E OIST ILLATIO N AP PARAT US

3352-9
o

CO'OUN'G WATER

INLET TUBE

HEATER

II~

SULFIDE

SCRUBBER

CONDENSER \I 11 06>010

DIS'nWNG FLASK

,. I TO VACUUM

ABSORBER

u}U 0'00'

Figure 3.

Cyanide Distillation Apparatu8
CYANIDE, TOTAL

Method 335.3 (Colorimetric, Automated UV)

STORET NO. 00720

1 Scope and Apphcatlon

1 1 ThIS method IS apphcable to the determmatIOn ofcyanIde m dnnkmg and surface waters,

domestIc and mdustnal wastes

1 2 The apphcable range IS 5 to 500 ug/1

2 Summary ofMethods

2 1 The cyanIde as hydrocyanIc aCId (HCN), IS released from cyanIde complexes by means of

UV dIgestIOn and dIstIllatIOn CyanIdes are converted to cyanogen chlorIde by reactIons

WIth chloramme-T whIch subsequently reacts WIth pyrIdme and barbItUrIC aCId to gIve a

red-colored complex

3 Sample Handhng and PreservatIOn

3 1 The sample should be collected m plastIc bottles of 1 hter or larger SIze All bottles must

be thoroughly cleansed and thoroughly nnsed to remove soluble matenal from

contamers

3 2 Samples must be preserved WIth 2 m 1 of 10 N sodIUm hydroxIde per hter ofsample (pH

12) at the tIme ofcollectIOn

,,3 3 Samples should be analyzed as rapIdly as possIble after collectIOn Ifstorage IS reqUIred,

the samples should be stored m a refngerator or m an Ice chest filled WIth water and Ice to

, mamtam temperature at 4°C

3 4 OXldlzmg agents such as chlonne decompose most of the cyanIdes Test a drop of the

sample WIth potassIUm IodIde-starch test paper (KI starch paper), a blue color mdlcates

the need for treatment Add ascorbIc aCId, a few crystals at a tIme, untIl a drop ofsample

produces no color on the mdlcator paper Then add an addItIOnal 0 6 g of ascorbIc aCId

for each lIter ofsample volume

4 Interferences

4 1 ThIOcyanates are a pOSItIve mterference Dunng the UV dIgestIon thIOcyanates are

decomposed to cyanIde

4 2 Sulfides adversely affect the colonmetnc procedure If a drop of the sample on lead

acetate test paper mdlcates the presence of sulfide, treat 25 m1 more of the stablhzed

sample (pH 12) than that reqUIred for the cyanIde determmatIOn WIth powdered

cadmIUm carbonate Yellow cadmIUm sulfide preCIpItates If the sample contams sulfide

Repeat thIS operatIOn untIl a drop ofthe treated sample SolutIon does not darken the lead

acetate test paper FIlter the solutIon through a dry filter paper mto a dry beaker, and

from the filtrate, measure the sample to be used for analysIs AVOId a large excess of

Issued 1978

335 3-1
cadmIUm and a long contact tune m order to mmimize a loss by complexatlOn or

occluslOn ofcyamde on the precIpItated matenal

5. Apparatus

5 1 Techmcon AutoAnalyzer

5 1 1Sampler

5 1 2 Mamfold wIth UV digestor

5 1 3 ProportlOnmg pump

5 1 4 Heatmg bath wIth distillatlOn coll

5 1 5 DistillatlOn head

5 1 6 Colonmeter eqUlpped wIth a 15 mm flowcell and 570 nm filter

5 I 7 Recorder

6. Reagents

6 1 DIstl1latlOn reagent Carefully add 250 m1 of 85% phosphonc aCId and 50 ml of

hypophosphorus aCId to 700 m1 of dIstilled water, mIX and dllute to one hter wIth

dIstIlled water

62 Phosphate buffer, pH 52 DIssolve 13 6 g ofpotassIUm dihydrogen phosphate and 028 g

ofdisodlum phosphate m 900 m 1ofdIstllled water and dllute to one hter

6 3 Chloramme-T DIssolve 2 0 g ofchloramme-T m 500 m 1ofdIstllled water

64 Pyndme barbitunc aCId reagent Place 15 g ofbarbitunc aCId m a one lIter beaker Wash

the sIdes ofthe beaker wIth about 100 m1 ofdIst111ed water Add 75 ml ofpyndme and

mIX Add 15 ml of conc HC1 and mIX DIlute to about 900 ml wIth dIstllled water and

mIX until all the barbitunc aCId has dissolved Transfer the solutlOn to a one hter flask

and dilute to the mark

65 SodIUm hydroXIde, 1 N DIssolve 40 g ofNaOH m 500 ml ofdIstilled water and dilute to

onehter

66 Stock cyamde solutlOn DIssolve 251 g of KCN and 2 g KOH m 900 m1 of dIstilled

water and mix Dllute to one lIter Standardize with 00192 N AgN03 to appropnate

concentratlOn I m1 = 1mg CN

67 All workmg standards should contam 2 m1 of IN NaOH (65) per 100 ml

7. Procedure

7.1 Set up the mamfold as shown m FIgure 1m a hood or a well-ventIlated area

7 2 Set temperature ofthe heatmg bath at 150°C

7 3 Allow colonmeter and recorder to warm up for 30 mmutes Run a baselme WIth all

reagents, feedmg dlstllied water through the sample hne

7 4 Place appropnate standards m the sampler m order of decreasmg concentratlOn

Complete loadmg ofsampler tray WIth unknown samples

7 5 When the baselme becomessteady begin the analyses

8. CalculatIon

8 I Prepare standard curve by plottmg peak heIghts of standards agamst concentration

values Compute concentratlOns of samples by companng sample peak heights WIth

standards

9. PreciSIon and Accuracy

9 1 PrecISIon and accuracy data are not avallable at thIS time

3353-2
BIblIography

1 Techmcon AutoAna1yzer II Methodology, Industnal Method No 315-74 WCUV digestlOn

and distIllatlOn, Techmcon Industnal Systems, Tarrytown, NY, 10591, (1974)

2 Goulden, P D, Afghan, B K and Brooksbank, P ,Anal Chern 44,1845 (1972)

3353-3
183-13019-01

E-C-3

ON REAGENT

OM STILL. E WASTE

N E-T

BARBITURIC

GENT

x

o 34 POLYETHYLENE

PROPORTIONING

PUMP

RE-SAMPLE

~~ Ml/MIN C:J~ TO SAMPLER WASH ,

~?'.. RECEPTACLE PUR ORN 3 40 WATER rT .. TO WASTE TUBE

TO TOP OF PROBE BLK BLK o 32 AIR 194-B005-02

00 •••• A-10 PUR PUR 2 50 SAMPLE

J155°C

• ORN o 42 HEATING BATH UV DIGESTOR ORN DISTILLAT

WITH DISTILL COIL ORN ORN o 42 WASTE FR

WASTE YEL YEL 1 20 RE-SAMPL

15-7-0251 157-B089 BLK BLK o 32 AIR I,

.~ 170-0103 I GRY 1 00 000000 • 0 '0. 00 •• 0. GRY RE-SAMPL

10 TURNS 20 TURNS15 TURNS I ORN ORN o 42 BL

TO/F/C ORN ORN o 10 CH PUMP TUBE

GRY GRY 1 00 P'r

COLORIMETER

570 NM GRY GRY 1 00 FR 15 mm FIC x 2 0 MM 1D

199-B023-06 .

.. ...

r:

w

w

VI

W

I

"""

FIGURE 1 CYANIDE MANIFOLD AA11
FLUORIDE, TOTAL

Method 340.1 (Colorimetric, SPADNS with Bellack Distillation)

STORET NO. Total 00951

Dissolved 00950

1 Scope and Apphcatton

1 1 Tills method IS apphcable to the measurement offluonde m drmkmg, surface, and sahne

waters, domestic and mdustnal wastes

1 2 The method covers the range from 0 1 to about 1 4 mg/l F ThIS range may be extended

to 1000 mg/1 usmg the Fluonde Ion Selective Electrode Method (3402) after

d1stl1latton

2 Summary ofMethod

2 I Followmg d1stillatIon to remove mterferences, the sample IS treated with the SPADNS

reagent The loss of color resultmg from the reactIOn of fluonde with the zlrconylSPADNS dye IS a functIOn ofthe fluonde concentratIOn

3 Comments

3 1 The SPADNS reagent IS more tolerant of mterfenng matenals than other accepted

fluonde reagents Reference to Table 414 1, p 388, Standard Methods for the

Exammatton of Waters and Wastewaters, 14th Ed1tIOn, WIll help the analyst decide If

distillatIOn IS required The addItion of the highly colored SPADNS reagent must be

done with utmost accuracy because the fluonde concentratIOn IS measured as a difference

of absorbance m the blank and the sample A small error m reagent add1ton IS the most

prommentsource oferror m thIS test

3 2 Care must be taken to avoid overheatmg the flask above the level ofthe solutIOn ThiS IS

done by mamtammg an even flame entIrely under the boilmg flask

4 Apparatus

41 Distillation apparatus A 1-hter round-bottom, long-necked pyrex bOllmg flask,

connectmg tube, effiCIent condenser, thermometer adapter and thermometer readmg to

200°C All connectIOns should be ground glass Any apparatus equivalent to that shown

m FIgure liS acceptable

42 Colonmeter One ofthe followmg

4 2 1 Spectrophotometerfor use at 570 nm prov1dmg a hght path ofat least 1cm

4 2 2 Filter photometer eqUIpped WIth a greenIsh yellow filter havmg maxImum

transmIttance at 550 to 580 nm and a hght path ofat least I cm

5 Reagents

5 1 Sulfunc aCid, HzSO4' conc

Approved for NPDES and SDWA

Issued 1971

Ed1tonal revIsion 1974 and 1978

340 1-1
5 2 SIlversulfate, Ag2S04 crystals

53 Stock fluonde solutlOn DIssolve 0221 g anhydrous sodIUm fluonde, NaP, m dIstIlled

water In a I-lIter volumetnc flask and dIlute to the mark WIth dIstIlled water, 100 ml = oImgF

54 Standard fluonde solutlOn Place 100 ml stock fluorIde solutlOn (53) In a 1 lIter

volumetnc flask and dIlute to the mark WIth dIstIlled water, 1 00 ml = 0 010 mg F

55 SPADNS solutIon DIssolve 0958 g SPADNS, sodIUm 2-(parasulfophenylazo)-1,8-

dlhydroxy-3,6-naphthalene dlsulfonate, In dIstIlled water In a 500 ml volumetrIC flask

and dIlute to the mark Stable mdefimtely Ifprotected from dIrect sunlIght

56 Zirconyl-acid reagent DIssolve 0 133 g zIrconyl chlonde octahydrate, ZrOCI2-8H20 In

approXimately 25 ml distIlled water m a 500 ml volumetnc flask Add 350 ml conc HCI

and dIlute to the mark WIth dIstIlled water

5.7 ACld-Zlrconyl-SPADNS reagent MIX equal volumes of SPADNS solutlOn (55) and

zirconyl-acid reagent (5 6) The combIned reagent IS stable for at least 2 years

5 8 Reference solutlOn Add 10 ml SPADNS solutlOn (5 5) to 100 ml dIstIlled water DIlute 7

ml conc HCI to 10 ml and add to the dIlute SPADNS solutlOn ThIS solutlOn IS used for

zeromg the spectrophotometer or photometer It IS stable and may be used Indefimtely

59 SodIUm arsemte solutlOn Dissolve 50 g NaAs02 In dIstIlled water In a I-lIter volumetnc

flask and dIlute to the mark WIth dIstIlled water (CAUTION TOXIc-avoid IngestlOn)

6 Procedure

6 1 PrelImmary dlstIllatlOn

6 1 1 Place 400 ml distIlled water m the distIllmg flask

6 1 2 Carefully add 200 ml conc H2S04 and SWIrl untIl contents are homogeneous

6 1 3 Add 25 to 35 glass beads, connect the apparatus (FIgure 1) makmg sure all Jomts

are tIght

6 14 Heat slowly at first, then as rapIdly as the effiCIency of the condenser wIll permIt

(dIstIllate must be cool) untIl the temperature ofthe flask contents reaches exactly

180·C Discard the dIstIllate ThiS process removes fluonde contammatlOn and

adjusts the aCId-waterratlO for subsequent dlstillatlOns

6 1 5 Cool to 120·C or below

6 1 6 Add 300 ml sample, mIX thoroughly, dIstIll as In 6 1 4 untIl temperature reaches

180·C Do not heat above 180·C to preventsulfate carryover

6 1 7 Add Ag2S04 (5 2) at a rate of5 mg/mg CI when hIgh chlonde samples are dIstIlled

61 8 Use the sulfunc aCid solutlOn m the flask repeatedly untIl the contamInants from

the samples accumulate to such an extent that recovery IS affected or mterferences

appear In the distIllate Check penodically by distIllIng standard fluonde samples

6 1 9 High fluonde samples may reqUIre that the stIll be flushed by using dIstIlled water

and combInIng dIstIllates

6 2 Colonmetnc DetermInatlOn

6 2 1 Prepare fluonde standards In the range 0 to 1 40 mg/l by dIlutIng appropnate

quantitIes ofstandard fluonde solutlOn (54) to 50 ml WIth dIstIlled water

340 1-2
CONNECTING TUBE

THERMOMETER

THERMOMETER ADAPTER

l-liter

ROUND BOTTOM

FLASK

BURNER

l24/40

JOINT

CONDENSER

300-ml

VOLUMETRIC

FLASK

FIGURE 1 DIRECT DISTILLATION APPARATUS

FOR FLUORIDE.

340 1-3
6 2 2 PIpet 5 00 ml each of SPADNS solutIOn (5 5) and zirconyl-acid reagent (5 6) or

10 00 m1 of the mIxed aCId-zlrconyl-SPADNS reagent (57) to each standard and

mlXwell

623 Set photometer to zero wIth reference solutH;>n (58) and ImmedIately obtaIn

absorbance readIngs ofstandards

6 2 4 Plot absorbance versus concentratIon Prepare a new standard curve whenever

fresh reagent IS made

625 IfresIdual chlonne IS present pretreat the sample wIth I drop (005 ml) NaAsOz

solutIOn (59) per 01 mg reSIdual chlorIne and mIX SodIUm arsemte

concentratIOns of 1300 mg/1 produce an error of0 1mg/1 at 1 0 mg/1 F

6 2 6 Use a 50 ml sample or a portIon dIluted to 50 ml Adjust the temperature of the

sample to that used for the standard curve

6 2 7 Perform step 6 2 2 and 6 2 3

7. CalculatIons

7 1 Read the concentratIon In the 50 ml sample USIng the standard curve (6 2 4)

7 2 Calculate as follows

mgF x 1,000 mg/l F = ml sample

73 When a sample (ml sample) IS dIluted to a volume (B) and then a portIon (C) IS analyzed,

use

II F - mgF x 1,000 1!..

mg - ml sample X C

8. PreCISIon and Accuracy

8 1 On a sample contaInIng 0 83 mg/1 F WIth no Interferences, 53 analysts USIng the Bellack

dIstIllatIOn and the SPADNS reagent obtaIned a mean of 0 81 mg/1 F WIth a standard

deVIatIon of ±O 089 mg/1

82 On a sample contaInIng 057 mg/1 F (WIth 200 mg/1 804 and 10 mg/1 Al as

Interferences) 53 analysts USIng the Bellack dIstIllatIon obtaIned a mean of 060 mg/1F

WIth a standard deVIatIon of ±O 103 mg/1

83 On a sample contaInIng 068 mg/1 F (WIth 200 mg/1 S04, 2 mg/1 Al and 25 mg/1

[Na(P03)6] as Interferences), 53 analysts USIng the Bellack dIstIllatIOn obtaIned a mean of

0.72 mg/1 F WIth a standard deViatIon of ±O 092 mg/1 (AnalytIcal Reference SerVIce,

Sample 111-B water, Fluonde, August, 1961 )

BiblIography

1 Standard Methods for the EXamInatIOn of Water and Wastewater, p 389-390 (Method No

414A, PrelImInary DIstIllatIon Step) and p 393-394 (Method 414C SPADNS) 14th EdItion,

(1975)

2 Annual Book ofASTM Standards, Part 31, "Water", Standard D 1179-72, Method A, p 310

(1976)

3401-4
FLUORIDE

Method 340.2 (Potentiometric, Ion Selective Electrode)

STORET NO: Total 00951

Dissolved 00950

1 Scope and ApplIcatiOn

1 1 ThIS method IS applIcable to the measurement offluonde m dnnkmg, surface and sahne

waters, domestic and mdustnal wastes

1 2 ConcentratiOn offluonde from 0 1up to 1000 mg/lIter may be measured

1 3 For Total or Total DIssolved Fluonde, the Bellack dIstIllatiOn is reqUired for NPDES

momtonng but is not reqUired for SDWA momtonng

2 Summary ofMethod

2 1 The fluonde IS determmed potentiOmetncally usmg a fluonde electrode m conjUnctIon

WIth a standard smgle Junction sleeve-type reference electrode and a pH meter havmg an

expanded mIllIvolt scale or a selectIve Ion meter havmg a dIrect concentratiOn scale for

fluonde

2 2 The fluonde electrode conSIsts of a lanthanum fluonde crystal across whIch a potentIal IS

developed by fluonde Ions The cell may be represented by Ag/Ag Cl, ct(O 3),

F"(O 001) LaF/testsolutiOn/SCE/

3 Interferences

3 1 Extremes of pH mterfere, sample pH should be between 5 and 9 Polyvalent catiOns of

SI+4, Fe+3 and Al+3 mterfere by formmg complexes With fluonde The degree of

mterference depends upon the concentratiOn of the complexmg catIons, the

concentratIon of fluonde and the pH of the sample The addItIon of a pH 5 0 buffer

(descnbed below) contammg a strong chelatmg agent preferentIally complexes

alummum (the most common mterference), SIlIcon and iron and elImmates the pH

problem

4 SamplIng HandlIng and PreservatiOn

4 1 No specIal reqUirements

5 Apparatus

5 1 Electrometer (pH meter), WIth expanded mv scale, or a selectIve iOn meter such as the

Onon 400 Senes

52 Fluonde Ion ACtIVity Electrode, such as Onon No 94-09(1)

53 Reference electrode, smglejUnctlon, sleeve-type, such as Onon No 90-01, Beckman No

40454, or Cormng No 476010

5 4 Magnetic MIxer, Teflon-coated stlrnng bar

Approved for NPDES and SDWA

Issued 1971

Edltonal reViSIon 1974

3402-1
6 Reagents

6.1 BuffersolutIOn, pH 5 0-5 5 To approxImately 500 ml ofdIstIlled water In a 1 lIter beaker

add 57 ml of glacIal acetIc aCId, 58 g of sodIUm chlonde and 4 g of CDTA(2) StIr to

dIssolve and cool to room temperature Adjust pH ofsolutIOn to between 5 0 and 5 5 wIth

5 N sodIUm hydroxIde (about 150 ml will be reqUIred) Transfer solutIOn to a 1 lIter

volumetnc flask and dIlute to the mark wIth dIstilled water For work wIth bnnes,

addItIOnal NaCIshould be added to raIse the chlonde level to tWIce the hIghest expected

level ofchlonde In the sample

6.2 SodIUm fluonde, stock solutIOn 1 0 ml = 0 1mg F DIssolve 0 2210 g ofsodIUm fluonde

In dIstIlled water and dIlute to 1 lIter In a volumetnc flask Store In chemIcal-resIstant

glass or polyethylene

63 SodIUm fluonde, standard SolutIon 10 ml = 001 mg F DIlute 100 0 ml of sodIUm

fluonde stock solutIon (6 2) to 1000ml wIth dIstilled water

64 SodIUm hydrQxIde, 5N DIssolve 200 g sodIUm hydroxIde In dIstIlled water, cool and

dIlute to 1hter

7. CalIbratIOn

7.1 Prepare a senes ofstandards USIng the fluonde standard solutIOn (63) In the range of0 to

2 00 mg/l by dIlutIng appropnate volumes to 50 0 ml The follOWIng senes may be used

MIllImeters of Standard

(10 ml = 001 mg/F)

000

100

200

300

400

500

600

800

1000

Concentration when Dl1uted

to 50 ml, mg F/Itter

000

020

040

060

080

100

120

160

200

72 CalIbratIon ofElectrometer Proceed as descnbed III (8 1) USIng semIloganthmic graph

paper, plot the concentratIon of fluonde In mg/lIter on the log aXIS vs the electrode

potentIal developed In the standard on the lInear aXIS, startIng WIth the lowest

concentratIon at the bottom ofthe scale CalIbratIOn ofa selectIve Ion meter Follow the

dIrectIons ofthe manufacturerfor the operatIon ofthe Instrument

8 Procedure

8 1 Place 50 0 ml ofsample orstandard solutIOn and 50 0 ml ofbuffer (See Note) In a 150 ml

beaker Place on a magnetIC stIrrer and mIX at medIUm speed Immerse the electrodes In

the SolutIon and observe the meter readIng whIle mIXIng The electrodes must remaIn In

the solutIon for at least three mInutes or untIl the readIng has stabIlIzed At

concentrations under 0 5 mg/liter F, It may reqUIre as long as five mInutes to reach a

stable meter readIng, hIgh concentratIons stabIlIze more qUIckly If a pH meter IS used,

record the potentIal measurement for each unknown sample and convert the potential

340 2-2
readmg to the fluonde IOn concentratIOn of the unknown usmg the standard curve If a

selective Ion meter IS used, read the fluonde level m the unknown sample directly m

mg/1 on the fluonde scale

NOTE: For mdustnal waste samples, this amount of buffer may not be adequate

Analyst should check pH fitst IfhIghly basIc (>'9), add 1 N HCl to adjust pH to 8 3

9 PrecIsIon and Accuracy - "

9 1 A synthetIc sample prepared by'the Analytical Reference ServIce, PHS, contammg 085

mg/1 fluonde and no mterferences was analyzed by 111 analysts, a mean of 0 84 mg/1

wIth a standard deViatIOn of ±O 03 was obtamed

92 On the same study, a synthetIc sample contammg 075 mg/1 fluonde, 25 mg/1

polyphosphate and 300 mg/1 alkalImty, was analyzed by the same 111 analysts, a mean

of0 75 mg/1 fluonde wIth a standard devIatIOn of ±O 036 was obtamed

BIblIography

1 PatentNo 3,431,182 (March 4, 1969)

2 CDTA is the abbreViated deSignation of 1,2-cyc1ohexylene <hmtnlo tetraacetlc aCid (The

monohydrate form may also be used) Eastman Kodak 15411, Malhnckrodt2357, Sigma D

1383, Tndom-Fluka 32869-32870 or eqUivalent

3 Standard Methods for the Exammation ofWater and Wastewaters, p 389, Method No 414A,

PrelImmary DIstIllatIOn Step (Bellack), and p 391, Method N9 41~B, Electrode Method, 14th

EdItion (1975)

4 Annual Book of ASTM Standards, Part 31, "Water", Standard 01179-72, Method B, p 312

(1976)

3402-3
FLUORIDE

Method 340.3 (Colorimetric, Automated Complexone)

STORET NO. Total 00951

Dissolved 00950

1 Scope and ApplIcatIOn

1 1 ThIS method IS apphcable to drmkmg, surface and salIne waters, domestIc and mdustnal

wastes The apphcable range of the method IS 005 to 1 5 mg F/l Twelve samples per

hour can be analyzed

1 2 For Total or Total DIssolved Fluonde, the Bellack DIstillatIOn must be performed on the

samples pnor to analysIs by the complexone method

2 Summary ofMethod

2 1 Fluonde Ion reacts WIth the red cerous chelate of alIzarm complexone It IS unlIke other

fluonde procedures m that a posItIve color IS developed as contrasted to a bleachmg

actIOn m prevIous methods

3 Sample Handlmg and PreservatIon

3 1 No specIal reqUirements

4 Interferences

41 Method IS free from most amomc and catIOmc mterferences, except alummum, WhICh

forms an extremely stable fluoro compound, AIF6 -3 ThIS IS overcome by treatment

WIth 8-hydroxyqumohne to complex the alummum and by subsequent extractIOn WIth

chloroform At alummum levels below 02 mg/l, the extractIOn procedure IS not

reqUired

5 Apparatus

5 1 Techmcon AutoAnalyzer Umt cons1stmg of

5 1 1 Sampler I

512 Mamfold

5 1 3 ProportIOmng pump

5 1 4 Contmuous filter

5 1 5 Colonmeter eqUipped WIth 15 mm tubular flow cell and 650 nm filters

5 1 6 Recorder eqUipped WIth range expander

6 Reagents

6 1 Sodmm acetate solutIOn DIssolve 272 g (2 moles) ofsodmm acetate m d1stl1led water and

dl1ute to 1 hter

6 2 AcetIC aC1d-8-hydroxyqumohne solutIOn DIssolve 6 g of 8-hydroxyqumohne m 34 ml of

conc acetIC aCId, and dl1ute to 1hter WIth d1stl1led water

Approved for NPDES

Issued 1971

3403-1
6 3 Chloroform AnalytICal reagent grade

6.4 AmmonIum acetate solutlOn (67%) Dissolve 67 g of ammOnIum acetate m distilled

water and dl1ute to 11lter

6 5 Hydrochlonc aCId (2 N) Dilute 172 ml ofconc HCI to 1 liter

66 Lanthanum alizann fluonde blue solution(l) Dissolve 018 g ofalizann fluonde blue m a

solutlOn contammg 05 ml of conc ammOnIum hydroxide and 15 ml of67% ammOnIum

acetate (6 4) Add a solutlOn that contams 41 g ofanhydrous sodmm carbonate and 70 ml

ofglacIal acetic aCid m 300 ml ofwstl1led w~ter Add 250 ml of acetone Dissolve 0 2 g of

lanthanum OXide m 12 5 ml of 2 N hydrochlonc aCid (6 5) and miX With above solutlOn

Dilute to 1 liter J

67 Stock solutlOn Dissolve 2210 g ofsodmm fluonde m 100 ml ofdistilled water and dilute

to 1 liter m a volumetnc flask 1 0 ml = 1 0 mg F

6 8 Standard SolutlOn Dl1ute 10 0 ml of stock solutlOn to 1 liter m a volumetnc flask 1 0

ml = OOlmgF

68 1 Usmg standard solutlOn, prepare the followmg standards m 100 ml volumetnc

flask

mg F/I

005

010

020

040

060

080

100

120

150

ml Standard SolutlOn/100 ml

05

10

20

40

60

80

100

120

150

7 Procedure

7.1 Set up manIfold as shown m Figure 1

7 2 Allow both colonmeter and recorder to warm up for 30 mmutes Run a baselme With all

reagents, feedmg distilled water through the sample line Adjust dark current and

operative openmg on colonmeter to obtam stable baseline

7 3 Place distilled water wash tubes m alternate openmgs m Sampler and set sample timmg

at25mmutes

7 4 Arrange fluonde standards m Sampler m order of decreasmg concentratlOn Complete

loadmg ofSampler tray With unknown samples

7 5 SWitch sample line from distilled water to Sampler and begm analySiS

8 Calculation

8 1 Prepare standard curve by plottmg peak heights of processed fluonde standards agamst

concentration values Compute concentratlOn of samples by companng sample peak

heights With standard curve

3403-2
9 PrecIsion and Accuracy

9 1 In a SIngle laboratory (EMSL), USIng surface water samples at concentrations of 006,

o 15, and 1 08 mg F11, the standard deViatIOn was ±O 018

92 In a SIngle laboratory (EMSL), usmg surface water samples at concentrations of0 14 and

125 mg Fll, recovenes were 89% and 102%, respectively

BIblIography

1 J T Baker Laboratory ChemIcal No 1112 or eqUivalent

2 Greenhalgh, R, and RIley, J P, "The DetermInatIOn of Fluondes m Natural Waters, With

PartIcular Reference to Sea Water" Anal Chlm Acta, 25, 179 (1961)

3 Chan, K M, and Rtley, J P, "The AutomatIC DetermInation of Fluonde In Sea Water and

Other Natural Water" Anal Chim Acta, 35, 365 (1966)

4 Standard Methods for the Exammatton of Water and Wastewater, 14th EdItIOn, p 614,

Method 603, (1975)

3403-3
15mmTUBULAR flc *ACIDFLEX TUB ING

650 nM FILTERS

)

SMALL MIXING ,

LARGE MIXING COIL IDI/IJIIR

COIL ILm) 116·103 1 0 w o23 SODIUM ACETATE ......... ' , p w 3 90 SAMPLE

I IBLACK BLACK o32 ACETIC ACID 80

20' DELAY COIL

HYDROXYQUI g 0

NOLINE 00 00

000

* P P 1 71 CHLOROFORM SAMPLER 1

* P B 2 03 CHLOROFORM WASTE

LID EXTRACTION COIL R R o 80 DISTILLED WATER C0~ ILm WIBEADSj Y Y 1 20 FILTERED SAMPLE TJCf

IBLU E RUIF 1 60 AIR ~} 12" 0F

GLASS Y Y 1 20 LANTHANUM ALIZARIN REAGENT

TUBING Y LARGE GLASS T, Lm Y y 1 20 WASTE

I D 4mm, 80mm LONG

=F= L~WASTE PROPORTIONING PUMP

80' DELAY COIL:=i§ ;::=: /

1

:::I ,Jt ~V G:J

COLORIMETER RECORDER I.

w

"'"

o

w

./:>.

FIGURE 1. FLUORIDE MANIFOLD AA-I
IODIDE

Method 345.1 (Titrimetric)

STORET NO. 71865

1 Scope and ApplicatIon

I 1 ThIS method IS applicable to dnnkmg, surface and saline waters, sewage and mdustnal

waste effluents

1 2 The concentratIOn range for thIS method IS 2-20 mg/l ofIodIde

2 Summary ofMethod

2 1 After pretreatment to remove mterferences, the sample IS analyzed for IOdIde by

convertmg the IOdIde to Iodate wIth bromme water and tttratmg wIth phenylarsme oXIde

(PAO) orsodmm thIOsulfate

3 Sample Handling and PreservatIOn

3 I Store at 4°C and analyze as soon as pOSSIble

4 Interferences

A 1 Iron, manganese and orgamc matter can mterfere, however, the calcmm OXIde

pretreatment removes or reduces these to mSlgmficant concentratIOns

4 2 Color mterferes WIth the observatIOn ofmdlcator and bromme-water color changes ThIS

mterference IS ehmmated by the use of a pH meter mstead of a pH mdlcator and the use

of standardIzed amounts of bromme water and sodmm formate solutIOn mstead of

observmg the hght yellow color changes

5 Reagents

5 1 AcetIC ACId SolutIOn (1 8) MIX 100 ml of glaCIal acetIC aCId WIth 800 ml of dlsttlled

water

5 2 Bromme Water In a fume hood, add 0 2 ml bromme to 500 ml dlsttlled water Stir WIth

a magnetIC stIrrer and a Teflon-coated stlrnng bar for several hours or untl1 the bromme

dIssolves Store m a glass-stoppered colored bottle

5 3 Calcmm OXIde (CaO) Anhydrous, powdered

5 4 Potassmm IodIde (KI) Crystals, ACS Reagent Grade

5 5 Sodmm Acetate SolutIOn (275 gil) DIssolve 275 g of sodmm acetate tnhydrate

(NaC2H30 2-3H20) m dlstl1led water Dl1ute to 1 hter and filter

56 Sodmm Formate SolutIOn (500 gil) DIssolve 50 g ofsodmm formate (NaCH02) m hot

dlstl1led water and dl1ute to 100 ml

5 7 NItrogen Gas Cyhnder

58 Sulfunc ACId SolutIOn (14) Slowly add 200 ml of H2S04 (sp gr 1 84) to 800 ml of

dlstdled water

59 Phenylarsme OXIde (00375 N) Hach ChemIcal Co or eqUlvalent StandardIze With

00375 N potassmm buodate (5 15,5 18)

Issued 1974

345 1-1
5 10 Phenylarsme OXIde Worlang Standard (00075 N) Transfer 100 ml of commerCIally

avaIlable 00375 N phenylarsme OXIde (59) to a 500 ml volumetnc flask and dIlute to the

mark WIth dIstIlled water ThIS solutIOn should be prepared fresh dally

5 11 CommerCIally avaIlable starch mdicators such as thyodene or eqUIvalent may be used

5 12 SodIUm ThIOsulfate, Stock SolutIOn, 075 N DIssolve 186 15 g (Na2S203-5H20) m

boiled and cooled dIstilled water and dIlute to 1 0 lIter Preserve by addmg 5 ml

chloroform

5 13 SodIUm ThIOsulfate Standard TItrant, 00375 N Prepare by dIlutmg 500 ml ofstock

SolutIon to 1 0 lIter Preserve by addmg 5 ml of chloroform StandardIze WIth 0 0375 N

potasSIUm bllodate (5 15,5 18)

5.14 SodIUm ThIosulfate Workmg Standard (00075 N) Transfer 100 ml of sodIUm

thIOsulfate standard tItrant (5 13) to a 500 m1 volumetnc flask and dIlute to the mark

WIth dIstI11ed water Tills solutIOn should be prepared fresh dally

5 15 PotasSIUm Bllodate Standard, 00375 N DIssolve 4873 g potassIUm bllodate,

preVIOusly dned 2 hours at 103°C, m dIstIlled water and dI1ute to 1 0 lIter DI1ute 250 ml

to 1 0 lIter for 00375 N bllodate solutIOn

5.16 Starch SolutIon Prepare an emulSIon of 10 g of soluble starch m a mortar or beaker

WIth a small quantIty of dIstIlled water Pour thIS emulSIOn mto 1 lIter of bOIlIng water,

allow to boll a few mmutes, and let settle overnIght Use the clear supernate ThIS

SolutIon may be preserved by the addItIon of 5 ml per lIter of chloroform and storage m a

10°C refngerator CommerCIally avaIlable, powdered starch mdicators may be used m

place ofstarch solutIOn

5.17 PotasSIUm Fluonde (KP-2H20) ACS Reagent Grade

518 StandardIzatIon of 00375 N Pheny1arsme OXIde and 00375 N sodIUm

thIosulfate. DIssolve approxImately 2 g (± 109) KI (54) m 100 to 150 ml dIstIlled

water, add 10 ml H2S04 solutIon (5 8) followed by 20 ml standard potaSSIUm bllodate

solutIOn (5 15) Place m dark for 5 mmutes, dI1ute to 300 ml and tItrate WIth phenylarsme

OXIde (5 9) or sodIUm thIOsulfate standard tItrant (5 13) to a pale straw color Add a

small scoop ofmdIcator (5 11) Walt untIl homogeneous color develops and contmue the

tItratIOn drop by drop untIl the blue color dIsappears Run m duplIcate DuplIcate

determmationsshould agree Wlthm ±O 05 ml

6 Procedure

6 1 Pretreatment

6 1 1 Add a VISIble excess of CaO (5 3) to 400 ml ofsample Stir or shake vIgorously for

apprOXImately 5 mmutes PIlter through a dry, moderately retentIve filter paper,

dlscardmg the first 75 ml

6 2 IodIde DetermmatIon

62 1 Place 100 ml ofpretreated sample (6 1) or a fractIOn thereofdI1uted to that volume,

mto a 150 ml beaker Add a Teflon-coated stIrnng bar and place on a magnetIc

stIrrer Insert a pH electrode and adjust the pH to approxImately 7 or slIghtly less

by the dropwise addItIOn ofH2S04 SolutIon (5 8)

622 Transfer the sample to a 250 ml WIde-mouthed corncal flask Wash beaker WIth

small amounts ofdIstI11ed water and add washmgs to the flask

3451-2
NOTE A 250 ml lodme flask would mcrease accuracy and preClSl0n by

preventmg possIble loss ofthe lOdme generated upon addItion of potasslUm lOdlde

and sulfunc aCId (63 1)

623 Add 15 ml sodlUm acetate solutlOn (5 5) and 5 ml acetic aCId solutlOn (5 1) MIX

well Add 40 ml bromme water solutlOn (5 2), mIX well Walt 5 mmutes

624 Add 2 ml sodlUm formate solutlOn (56), mIX well Walt 5 mmutes

625 Purge the space above the sample WIth a gentle stream of mtrogen (57) for

apprOXImately 30 seconds to remove bromme fumes

6 2 6 Ifa preCIpItate forms (Iron), add 0 5 g KP·2H20 (5 17)

6 2 7 A dIstIlled water blank must be run WIth each set ofsamples because of IodIde m

reagents If a blank IS conSIstently shown to be zero for a partIcular "lot" of

chemIcals It can then be Ignored

6 3 TttratlOn

63 1 DIssolve approXImately 1 g potasslUm lOdlde (5 4) m sample Add 10 ml of H2S04

solutlOn (5 8) and place m dark for 5 mmutes

6 3 2 TItrate WIth phenylarsme OXIde workmg standard (5 10) or sodlUm thlOsulfate

workmg standard solutlOn (5 14) addmg mdlcator (5 11 or 5 15) as end pomt IS

approached (hght straw color) TItrate to colorless solutlOn DIsregard returnmg

blue color

7 CalculatlOns

I-(mg/l) = 21,150 ( ml N)

where

ml = the number ofml ofPAO needed to tItrate the sample

N = the normahty ofthe PAO used to tItrate the sample

V = the volume ofsample taken (100 ml or a fractIon thereof)

21,150 was calculated from the number of eqUlvalents oflOdme produced when the potasslUm

lOdlde was added and from the rearrangement ofthe equatlOn to produce the value m terms of

mg/I

8 PreclslOn and Accuracy

8 1 In a smgle laboratory (EMSL), usmg a mIxed domestIC and mdustnal waste effluent, at

concentratlOns of 1 6, 4 1, 66, 11 6 and 21 6 mg/l of lOdlde, the standard devlatlOns

were ±O 23, ±O 17, ±O 10, ±O 06 and ±O 50 mg/I, respectively

82 In a smgle laboratory (EMSL), usmg a mlXed domestIC and mdustnal waste effluent at

concentratIons of 41,66, 11 6 and 216 mg/I oflOdlde, recovenes were 80, 97, 97 and

92%, respectIvely

345.1-3
BiblIography

1 Annual Book of ASTM Standards, Part 31",Water", Standard D1246-68, p 328, Method C

(1976)

2. Bender, D F, "ModIficatIOn of the Iodlmetnc TItratIon Method for the DetermmatIOn of

BromIde and Its Apphcatlon to MIxed Domestlc-Industnal Waste Effluent", Analyst

(London) 100, p400-404 (June 1975)

345-1-4
NITROGEN, AMMONIA

Method 350.1 (Colorimetric, Automated Phenate)

STORET NO. Total 00610

Dissolved 00608

1 Scope and ApphcatlOn

1 1 Th1s method covers the determmatlOn of ammoma m drmkmg, surface, and sahne

waters, domest1c and mdustnal wastes m the range of 0 01 to 20 mg/l NH3 as N Th1s

range 1S for photometnc measurements made at 630-660 nm m a 15 mm or 50 mm

tubular flow cell H1gher concentratIOns can be determmed by sample dl1utlOn

ApproX1mately 20 to 60 samples per hour can be analyzed

2 Summary ofMethod

2 1 Alkahne phenol and hypochlonte react w1th ammoma to form mdophenol blue that 1S

proportIOnal to the ammoma concentratIOn The blue color formed 1S mtens1fied w1th

sodmm mtropruss1de

3 Sample Handhng and PreservatIOn

3 1 PreservatIOn by add1tlOn of2 ml conc H2S04 per hter and refr1geratIOn at 4°C

4 Interferences

41 Calcmm and magnesmm IOns may be present m concentratIOn suffic1ent to cause

prec1p1tatIOn problems durmg analys1s A 5% EDTA solutIOn 1S used to prevent the

prec1p1tatIOn of calcmm and magnesmm 10ns from nver water and mdustr1al waste For

sea water a sodmm potassmm tartrate solutIOn 1S used

4 2 Sample turb1d1ty and color may mterfere w1th th1S method Turb1d1ty must be removed

by filtratIOn pnor to analys1s Sample color that absorbs m the photometnc range used

wl1l also mterfere

5 Apparatus

5 1 Techmcon AutoAnalyzer Vmt (AAI or AAII) cons1stmg of

5 1 1 Sampler

5 1 2 Mamfold (AAI) or Analytical Cartndge (AAII)

5 1 3 ProportlOmng pump

5 1 4 Heatmg bath w1th double delay coll (AAI)

5 1 5 Colonmeter eqUipped w1th 15 mm tubular flow cell and 630-660 nm filters

5 1 6 Recorder

5 1 7 D1g1tal pnnter for AAII (optIOnal)

Approved for NPDES followmg prehmmary d1stlllatlOn, Method 3502

Issued 1974

Ed1tonal reV1S10n 1978

350 1-1
6 Reagents

6 1 Dlstllied water Special precaution must be taken to msure that distilled water IS free of

ammoma Such water IS prepared by passage of distilled water through an Ion exchange

column compnsed of a mixture of both strongly aCidic catlOn and strongly basIc amon

exchange resms The regeneratlOn of the Ion exchange column should be carned out

accordmg to the mstructlOn ofthe manufacturer

NOTE 1: AllsolutlOns must be made usmg ammoma-free water

6 2 Sulfunc aCid 5N Air scrubber solution Carefully add 139 ml of conc sulfunc aCid to

approximately 500 ml of ammoma-free distilled water Cool to room temperature and

dtlute to 1hter with ammoma-free dlsttlled water

6 3 Sodmm phenolate Usmg a 1 hter Erlenmeyer flask, dissolve 83 g phenol m 500 ml of

distilled water In small mcrements, cautlOusly add With agltatlOn, 32 g of NaOH

PenodIcally cool flask under water faucet When cool, dilute to 1 hter With distilled

water

64 Sodmm hypochlonte solutlOn Dl1ute 250 ml of a bleach solutlOn contammg 525%

NaOCI (such as "Clorox") to 500 ml With distilled water Avatlable chlonne level should

approxImate 2 to 3% Smce "Clorox" IS a propnetary product, ItS formulatlOn IS subject

to change The analyst must remam alert to detectmg any vanatlOn m this product

slgmficant to ItS use m this procedure Due to the mstablhty ofthis product, storage over

an extended penod should be aVOIded

65 Dlsodmm ethylenedlamme-tetraacetate (EDTA) (5%) Dissolve 50 g of EDTA

(dIsodmm salt) and approximately SIX pellets ofNaOH m 1hter ofdistilled water

NOTE 2: On salt water samples where EDTA solution does not prevent preCipitation of

cations, sodmm potassmm tartrate solutlOn may be used to advantage It IS prepared as

follows

6 5 1 Sodmm potassmm tartrate solutlOn 10% NaKC4H40 6e4H20 To 900 ml of

distilled water add 100 g sodmm potassmm tartrate Add 2 pellets of NaOH and a

few bollmg chips, boll gently for 45 mmutes Cover, cool, and dl1ute to 1 hter With

ammoma-free distilled water Adjust pH to 5 2 ± 05 With H2S04 After allowmg to

settle overmght m a cool place, filter to remove preCipitate Then add 1/2 ml BnJ35(4) (avatlable from Techmcon CorpOl:atlon) solution and store m stoppered bottle

66 Sodmm mtroprusslde (005%) Dissolve 05 g of sodium mtroprusslde m 1 hter of

dlsttlled water

67 Stock solution Dissolve 3819 g of anhydrous ammomum chlonde, NH4Cl, dned at

105°C, m distilled water, and dl1ute to 1000milO ml = 1 0 mg NH3-N

6.8 Standard SolutlOn A Dllute 10 0 ml of stock solutlOn (6 7) to 1000 ml With distilled

water 1 0 ml = 001 mg NHrN

69 Standard solution B Dllute 10 0 ml of standard solution A (68) to 100 0 ml With

dIstilled water 1 0 ml = 0001 mg NH3-N

350 1-2
610 Usmg standard solutIOns A and B, prepare the followmg standards m 100 ml volumetnc

flasks (prepare fresh dally)

NHrN, mg/l

001

002

005

010

020

050

080

100

150

200

ml Standard SolutIOnllOO ml

SolutIOn B

10

20

50

100

SolutIOn A

20

50

80

100

150

200

NOTE 3: When salme water samples are ap-'lyzed, SubstItute Ocean Water (SOW)

should be used for prepanng the above standards used for the cahbratIOn curve,

otherwiSe, dIstIlled water IS used IfSOW IS used, subtract ItS blank background response

from the standards before prepanng the standard curve

Substitute Ocean Water (SOW)

NaCI

MgCl2

Na2S04

CaCl2

KCI

2453 gil

520 gil

409 gil

116 gil

070 gil

NaHC03

KBr

H 3B03

SrCl2

NaF

020 gil

010 gil

003 gil

003 gil

0003 gil

7 Procedure

7 1 Smce the mtenslty of the color used to quantIfy the concentratIOn IS pH dependent, the

aCId concentratIOn of the wash water and the standard ammoma solutIOns should

approXImate that ofthe samples For example, Ifthe samples have been preserved wIth 2

ml cone H2S04/hter, the wash water and standards should also contam 2 ml cone

H2S04/hter

72 For a workmg range of0 01 to 200 mg NH3-N/l (AAI), set up the mamfold as shown m

FIgure 1 For a workmg range of 01 to 10 mg NH3-N/l (AAII), set up the mamfold as

shown m FIgure 2 HIgher concentratIOns may be accommodated by sample dIlutIOn

7 3 Allow both colonmeter and recorder to warm up for 30 mmutes Obtam a stable basehne

wIth all reagents, feedmg dIStilled water through sample hne

7 4 For the AAI system, sample at a rate of 20/hr, 1 1 For the AAII use a 60/hr 6 1 cam

wIth a common wash

3501-3
7 5 Arrange ammoma standards IIIsampler III order of decreaslllg concentration ofmtrogen

Complete loadlllg ofsampler tray with unknown samples

7 6 SWitch sample hne from distilled water to sampler and beglll analysIs

8 Calculations

8 1 Prepare appropnate standard curve denved from processlllg ammoma standards

through mamfold Compute concentratIOn ofsamples by comparlllg sample peak heights

with standard curve

9 PrecIsion and Accuracy

9 1 In a slllgle laboratory (EMSL), USlllg surface water samples at concentratlOI1S of 1 41,

o77,0 59 and 0 43 mg NH3-N/l, the standard deViatIOn was ±O 005

9.2 In a slllgle laboratory (EMSL), USlllg surface watersamples at concentrations of0 16 and

1 44 mg NH3-N/l, recovenes were 107% and 99%, respectively

BiblIography

1. Hl1ler, A , and Van Slyke, D , "DetermlllatlOn of Ammoma III Blood", J BIOI Chern 102, p

499 (1933)

2. O'Connor, B , Dobbs, R, Vl1hers, B , and Dean, R, "Laboratory Dlst111atlOn of Mumclpal

Waste Effiuents", JWPCF 39, R 25 (1967)

3. FlOre, I., and O'Bnen, J E, "Ammoma DetermlllatlOn by Automatic AnalysIs", Wastes

Engllleenng 33, p 352 (1962)

4 A wettlllg agent recommended and supphed by the Techmcon CorporatIOn for use III

AutoAnalyzers

5. ASTM "Manual on Industnal Water and Industnal Waste Water", 2nd Ed, 1966 prllltlllg, p

418

6. Booth, R L, and Lobnng, L B, "EvaluatIOn of the AutoAnalyzer II A Progress Report" III

Advances III Automated AnalySIS 1972 Techmcon InternatIOnal Congress, Vol 8, p 7-10,

Mediad Incorporated, Tarrytown, NY, (1973)

7 Standard Methods for the ExamlllatlOn of Water and Wastewater, 14th EditIOn, p 616,

Method 604 (1975)

3501-4

, II , ,I
w

VI

o

-I

VI

SM= SMALL fy,IXING C

LM= LARGE MIXING

HEATING

BATH 37°C

PROPORTIONIN G

PUMP

ml/mln

WASH WATER .... P B 29 WASH

TO SAMPLER -- G G 20 SAMPLE 0 - )IL SM SAMPLER ~OIL ססoo - R R 08 EDTA 20/hr

-- I I LM

G G 20 ALR~

.1.

W W 0.6 PHENOLATE

- W W 06 HYPOCHLORITE

LM

SM ססoo t R R 06 NITROPRUSSIDE ~,

P P 2.5

:D

r-- WASTE IWASTE ,. . j~ I

.... 1:'1 ;l

·v D RECORDER

~SCRUBB~D THROUGH

COLORIMETER

15 mm FLOW CELL

650- 660 nm FILTER

FIGURE 1 AMMONIA MANIFOLD AA I

5N H

2

S04
SAMPLER

601 hr.

61

SCRUBBED THROUGH

5N H2 S04

IIml

PROPORTIONI~G

PUMP

COLORIMETER

50 mm FLOW CELL

650-6601l'lm FILTER

.........n.

WASH WATER G G 20 WASH

TO SAMPLER

0 W 0.23 AIR*: 0

nrm 0 0 042 SAMPLE

R R 0.8 EDTA

0 0 042 PHENOLATE

BLACK 032 HYPOCHLORITE

0 0 042 NITROPRUSSI DE

C

i""'" WASTE BLUE 1.6 WASTE

j RECORDER .... D l:J DIGITAL PRINTER

c:::J

I

HEATING

BATH

50° C

l.H

VI

o

-I

0\

-

FIGURE 2. AMMONIA MANIFOLD AA II
NITROGEN, AMMONIA

Method 350.2 (Colorimetric; Titrimetric; Potentiometric

Distillation Procedure)

STORET NO. Total 00610

Dissolved 00608

1 Scope and ApphcatlOn

1 1 ThIS dlstl1latlOn method covers the determmatlOn of ammonIa-nItrogen exclusIve oftotal

Kjeldahl nItrogen, m drmkmg, surface and sahne waters, domestic and mdustnal wastes

It IS the method of chOIce where economICS and sample load do not warrant the use of

automated eqUIpment

1 2 The method covers the range from about 0 05 to 1 0 mg NH3-N/l for the colonmetnc

procedure, from 10 to 25 mg/l for the tltnmetnc procedure, and from 005 to 1400

mg/l for the electrode method

1 3 ThIS method IS descnbed for macro gla~sware, however, mIcro dlstl1latlOn eqUIpment

may also be used

2 Summary ofMethod

2 1 The sample IS buffered at a pH of 9 5 wIth a borate buffer m order to decrease hydrolysIs

of cyanates and organIC nItrogen compounds, and IS then dIstilled mto a solutlOn ofbonc

aCId The ammOnIa m the dIstillate can be determmed colonmetncally by nesslenzatlOn,

tItnmetncally wIth standard sulfunc aCId wIth the use of a mIXed mdlcator, or

potentlOmetncally by the ammOnIa electrode The chOIce between the first two

procedures depends on the concentratlOn ofthe ammOnIa

3 Sample Handlmg and PreservatlOn

3 1 Samples may be preserved wIth 2 ml ofconc H2S04 per hter and stored at 4°C

4 Interferences

4 1 A number of aromatIC and ahphatlc ammes, as well as other compounds, both orgamc

and morganIc, WIll cause turbIdIty upon the addItion of Nes"ler reagent, so dIrect

nesslenzatlOn (1 e , wIthout dlstl1latlOn), has been dIscarded as an offiCIal method

4 2 Cyanate, WhICh may be encountered m certam mdustnal effluents, WIll hydrolyze to

some extent even at the pH of 9 5 at WhICh dlstl1latlOn IS carned out Volatl1e alkahne

compounds, such as certam ketones, aldehydes, and alcohols, may cause an off-color

upon nesslenzatlOn m the dlstlllatlOn method Some ofthese, such as formaldehyde, may

be ehmmated by bOIhng off at a low pH (approxImately 2 to 3) pnor to dlstl1latlOn and

nesslenzatlOn

4 3 ReSIdual chlonne must also be removed by pretreatment of the sample wIth sodmm

thlOsulfate before dlstIllatlOn

Approved for NPDES

Issued 1971

Edltonal reVlSlOn 1974

3502-1
5. Apparatus

5.1 An all-glass distilhng apparatus wIth an 800-1000 ml flask

5 2 Spectrophotometer or filter photometer for use at 425 nm and provIdIng a hght path of 1

cmormore

5 3 Nessler tubes Matched Nessler tubes (APHA Standard) about 300 mm long, 17 mm

InsIde dIameter, and marked at 225 mm ±1 5mm InsIde measurement from bottom

5.4 Erlenmeyer flasks The dIstillate IS collected In 500 ml glass-stoppered flasks These

flasks should be marked at the 350 and the 500 ml volumes WIth such markIng, It IS not

necessary to transfer the dIstIllate to volumetnc flasks

6 Reagents

6 1 DIstilled water should be free of ammoma Such water IS best prepared by passage

through an Ion exchange column contaInIng a strongly aCIdIC catIOn exchange reSIn

mIxed wIth a strongly baSIC amon exchange reSIn RegeneratIOn ofthe column should be

earned out accordIng to the manufacturer's InstructIOns

NOTE 1: All solutIOns must be made WIth ammoma-free water

62 Ammomum chlonde, stock solutIOn 10 ml = 10 mg NH3-N DIssolve 3819 g NH4C1

In dIstilled water and bnng to volume In a 1hter volumetnc flask

6.3 Ammomum chlonde, standard solutIOn 10 ml = 001 mg Dl1ute 10 0 ml of stock

SolutIon (6 2) to 1hter In a volumetnc flask

64 Bonc aCId solutIOn (20 gil) DIssolve 20 g H3B03 In dIstIlled water and dl1ute to 1 hter

65 MIXed IndIcator MIX 2 volumes of 0 2% methyl red In 95% ethyl alcohol WIth 1 volume

of 02% methylene blue In 95% ethyl alcohol ThIS solutIOn should be prepared fresh

every 30 days

NOTE 2: SpeCIally denatured ethyl alcohol conformIng to Formula 3A or 30 ofthe US

Bureau ofInternal Revenue may be SubstItuted for 95% ethanol

66 Nessler reagent DIssolve 100 g ofmercunc IOdIde and 70 g ofpotassmm IOdIde In a small

amount of water Add thIS mIxture slowly, WIth stIrnng, to a cooled solutIOn of 160 g of

NaOH In 500 ml ofwater Dl1ute the mIxture to 1hter IfthIs reagent IS stored In a Pyrex

bottle out ofdIrect sunlIght, It w111 remaIn stable for a penod ofup to 1year

NOTE 3: ThIS reagent should gIve the charactenstIc color WIth ammoma WIthIn 10

mInutes after addItIOn, and should not produce a preCIpItate WIth small amounts of

ammoma (004 mg In a 50 m1 volume)

6 7 Borate buffer Add 88 ml of 0 1 N NaOH solutIOn to 500 m1 of 0 025 M sodmm

tetraborate solutIOn (5 0 g anhydrous Na2B40 7 or 9 5 g Na2B40 7-lOH20 per hter) and

dIlute to 1hter

68 Sulfunc aCId, standard solutIOn (002 N, 1 ml = 028 mg NH3-N) Prepare a stock

solutIon of approXimately 0 1 N aCId by dl1utIng 3 ml of conc H2S04 (sp gr 1 84) to 1

liter WIth CO2-free dIstIlled water Dl1ute 200 ml ofthIS solutIOn to 1 hter WIth CO2-free

dlstl1led water

NOTE 4: An alternate and perhaps preferable method IS to standardIze the

approxImately 0 1 N H2S04 solutIOn agaInst a 0 100 N Na2C03 solutIOn By proper

dIlutIOn the 0 02 N aCId can then be prepared

3502-2
6 8 I StandardIze the approxImately 002 N aCId agamst 00200 N Na2C03 solutIOn

ThIs last solutIOn IS prepared by dissolvmg I 060 g anhydrous Na2C03, oven-dned

at 140°C, and dilutmg to 1000 ml wIth CO2-free dIstl1led water

6 9 SodIUm hydroxIde, I N DIssolve 40 g NaOH m ammoma-free water and dl1ute to I hter

6 10 Dechlonnatmg reagents A number of dechlormatmg reagents may be used to remove

resIdual chlonne pnor to dIstIllatIOn These mclude

a SodIUm thIosulfate (1/70 N) DIssolve 35 g Na2S20 3-5H20 m dIstl1led water and

dl1ute to I hter One ml of thIS solutIOn wIll remove I mg/I ofresIdual chlorme m

500 ml ofsample

b SodIUm arsemte (1/70 N) DIssolve 109 NaAs02 m dIstl1led water and dl1ute to I

hter

7 Procedure

7 I PreparatIon of eqmpment Add 500 ml of dIstIlled water to an 800 ml KJeldahl flask The

addItion of bOllmg ChIpS WhICh have been prevIOusly treated wIth dl1ute NaOH wIll

prevent bumpmg Steam out the dIstIllatIOn apparatus untl1 the dIstIllate shows no trace

ofammoma wIth Nessler reagent

7 2 Sample preparatIOn Remove the resIdual chlonne m the sample by addmg

dechlormatmg agent eqmvalent to the chlonne resIdual To 400 ml of sample add I N

NaOH (6 9), until the pH is 95, checkmg the pH durmg addItIOn wIth a pH meter or by

use ofa short range pH paper

7 3 Distl1latIOn Transfer the sample, the pH of which has been adjusted to 9 5, to an 800 ml

KJeldahl flask and add 25 ml ofthe borate buffer (6 7) DIStill 300 ml at the rate of 6-10

mllmm mto 50 ml of2% bonc aCid (64) contamed m a 500 ml Erlenmeyer flask

NOTE 5: The condenser tip or an extensIOn of the condenser tiP must extend below the

level ofthe bonc aCId solutIOn

Dilute the distl1late to 500 ml with distilled water and nesslenze an ahquot to obtam an

approximate value of the ammoma-mtrogen concentratIOn For concentratIOns above I

mg/I the ammoma should be determmed tItnmetncally For concentrations below thIS

value it is determmed colonmetncally The electrode method may also be used

7 4 DetermmatIOn of ammoma m distillate Determme the ammoma content ofthe distl1late

tItnmetncally, colonmetncally or potentIOmetncally as descnbed below

7 4 I TItnmetnc determmatIOn Add 3 drops ofthe mixed mdicator to the distl1late and

titrate the ammoma with the 002 N H2S04, matchmg the end pomt agamst a blank

contammg the same volume ofdistl1led water and H3B03 SOI)ltIOn

3502-3
742 Colonmetnc determInatIOn Prepare a senes of Nessler tube standards as follows

ml of Standard

10 ml = 001 mg NH3-N

00

05

10

20

30

40

50

80

100

mg NH3-N/50 0 ml

00

0005

001

002

003

004

005

008

010

Dl1ute each tube to 50 ml wIth dIstIlled water, add 2 0 ml of Nessler reagent (6 6)

and mIX After 20 mInutes read the absorbance at 425 nm agaInst the blank From

the values obtaIned plot absorbance vs mg NH3-N for the standard curve

DetermIne the ammOnIa In the dIstIllate by nesslenzIng 50 ml or an allquot dl1uted

to 50 ml and readIng the absorbance at 425 nm as descnbed above for the

standards AmmonIa-nItrogen content IS read from the standard curve

743 PotentIOmetnc determInatIOn Consult the method entItled NItrogen, AmmOnIa

Selective Ion Electrode Method (Method 350 3) In thIS manual

7 5 It IS not ImperatIve that all standards be dIstl1led In the same manner as the samples It IS

recommended that at least two standards (a hIgh and low) be dIstl1led and compared to

sIml1ar values on the curve to Insure that the dIstIllatIOn technIque IS rellable If dIstl1led

standards do not agree WIth undistIlled standards the operator should find the cause of

the apparent error before proceedIng

8 CalculatIOns .

8 1 TItnmetnc

mg/lNH1 _ N = A x 02~ x 1,000

where

A = mlO 02 N H2S04 used

S = mlsample

8 2 Spectrophotometnc

mg/l NH1 - N = A x ri ,000 x

where

A = mg NH3-N read from standard curve

B = ml total dIstIllate collected, IncludIng bone aCId and dIlutIOn

C = ml dIstIllate taken for nesslenzatIOn

D = ml ofongInalsample taken

3502-4
8 3 PotentlOmetnc

500 mg/1NH3 - N = - xA

D

where

A = mg NH3-N/1 from electrode method standard curve

D = ml ofongmalsample taken

9 PrecIsIon and Accuracy

9 1 Twenty-four analysts m sIxteen laboratones analyzed natural water samples contammg

exact Increments ofan ammomum salt, wIth the followmg results

Increment as

NItrogen, Ammoma

mg N/hter

021

026

1 71

192

PreCISiOn as

Standard DevIatIOn

mgN/hter

0122

0070

0244

0279

BIas,

%

-554

-1812

+046

-201

Accuracy as

Bias,

mg N/hter

-001

-005

+001

-004

(FWPCA Method Study 2, Nutnent Analyses)

BIblIography

1 Standard Methods for the ExammatlOn of Water and Wastewater, 14th EdltlOn, p 410,

Method 418A and 418B (1975)

2 Annual Book of ASTM Standards, Part 31, "Water", Standard D1426-74, Method A, p 237

(1976)

3502-5
NITROGEN, AMMONIA

Method 350.3 (Potentiometric, Ion Selective Electrode)

STORET NO. Total 00610

Dissolved 00608

1 Scope and ApphcatIOn

1 I ThIS method IS apphcable to the measurement of ammoma-mtrogen m dnnkmg, surface

and sahne waters, domestIc and mdustnal wastes

I 2 ThIS method covers the range from 0 03 to 1400 mg NH3-N/I Color and turbIdIty have

ItO effect on the measurements, thus, dIstIllatIOn may not be necessary

2 Summary ofMethod

2 I The ammoma IS determmed potentIOmetncally usmg an Ion selectIve ammoma electrode

and a pH meter havmg an expanded mIlhvoltscale or a specIfic Ion meter

2 2 The ammoma electrode uses a hydrophobIc gas-permeable membrane to separate the

sample solutIOn from an ammomum chlonde mternal solutIOn AmmonIa m the sample

dIffuses through the membrane and alters the pH ofthe mternal solutIOn, whIch IS sensed

by a pH electrode The constant level of chlonde m the mternal solution IS sensed by a

chlonde selectIve IOn electrode whIch acts as the reference electrode

3 Sample Handhng and PreservatIOn

3 I Samples may be preserved WIth 2 m1 ofconc H2S04 per hter and stored at 4°C

4 Interferences

4 I VolatIle ammes act as a pOSItive mterference

4 2 Mercury mterferes by formmg a strong complex WIth ammoma Thus the samples cannot

be preserved WIth mercunc chlonde

5 Apparatus

5 I Electrometer (pH meter) WIth expanded mV scale or a specIfic Ion meter

5 2 AmmOnIa selective electrode, such as Onon Model 95-10 or ElL Model 8002-2

5 3 MagnetIc htIrrer, thermally msulated, and Teflon-coated stlrnng bar

6 Reagents

6 1 DIstIlled water SpeCIal precautIOns must be taken to msure that the dIstIlled water IS free

of ammOnIa ThIS IS accomphshed by passmg dIstIlled water through an IOn exchange

column contammg a strongly aCIdIC catIon exchange resm mIxed WIth a strongly baSIC

anIon exchange resm

6 2 SodIUm hydrOXIde, ION DIssolve 400 g ofsodIUm hydroXIde m 800 ml ofdIstIlled water

Cool and dIlute to 1 hter WIth dIstIlled water (6 I)

63 AmmOnIum chlonde, stock solutIOn 10 ml = 10 mg NH3-N DIssolve 3819 g NH4CI

m water and bnng to volume m a I hter volumetnc flask usmg dIstIlled water (6 I)

Issued 1974

Approved for NPDES followmg prehmmary chsullatlOn (Method 350 2)

3503-1
64 Ammomum chlonde, standard solutIon 1 0 ml = 001 mg NHrN DIlute 10 0 ml ofthe

stock solutIOn (63) to 1 lIter wIth dIstilled water (6 1) m a volumetnc flask

NOTE 1: When analyzmg salme waters, standards must be made up m synthetIc ocean

water (SOW), found m NItrogen, Ammoma Colonmetnc, Automated Phenate Method

(3501)

7 Procedure

7 1 Preparation of standards Prepare a senes of standard solutIons covenng the

concentratIon range of the samples by dIlutmg eIther the stock or standard solutIons of

ammomum chlonde

7 2 CalIbratIOn of electrometer Place 100 ml of each standard solutIOn In clean 150 ml

beakers Immerse electrode mto standard of lowest concentratIOn and a,dd 1 m1 of lON

sodIUm hydroXIde solution whIle mIXIng Keep electrode m the solutIOn untIl a stable

readIng IS obtaIned

NOTE 2: The pH ofthe solutIOn after the addItIOn ofNaOH must be above 11

CautIon SodIUm hydroXIde must not be added pnor to electrode ImmerSIOn, for

ammoma may be lost from a baSIC solutIOn

7 3 Repeat thIS procedure WIth the remaInIng standards, gOIng from lowest to hIghest

concentratIOn USIng semIloganthmic graph paper, plot the concentratIOn ofammoma In

mg NH3-N/1 on the log aXIS vs the electrode potentIal developed In the standard on the

Imear axIS, startmg WIth the lowest concentratIOn at the bottom ofthe scale

7.4 CalIbratIOn of a speCIfic IOn meter Follow the dIrectIOns of the manufacturer for the

operatIon ofthe mstrument

75 Sample measurement Follow the procedure In (72) for 100 ml of sample In 150 ml

beakers Record the stabIlIzed potentIal of each unknown sample and convert the

potentIal readIng to the ammoma concentratIOn usmg the standard curve If a speCIfic

Ion meter IS used, read the ammoma level dIrectly m mg NH3-N/1

8. PreCISIon and Accuracy

8 1 In a SIngle laboratory (EMSL), usmg surface water samples at concentratIOns of 1 00,

077,019, and 013 mg NH3-N/1, standard deVIatIOns were ±O 038, ±O 017, ±O 007,

and ±O 003, respectIvely

8 2 In a SIngle laboratory (EMSL), USIng surface water samples at concentratIOns of0 19 and

o13 mg NHr N/1, recovenes were 96% and 91 %, respectively

BIblIography

1. Booth, R L, and Thomas, R F, "SelectIve Electrode DetermInatron of Ammoma In Water

and Wastes", EnVIr SCI Technology, 7, p 523-526 (1973)

2. Banwart, W L, Bremner, J M, and TabatabaI, M A, "DetermInatIOn ofAmmomum m SoIl

Extracts and Water Samples by an Ammoma Electrode", Comm SoIl SCI Plant ,3,p 449

(1952)

3. MIdgley, D, and Torrance, K, "The DetermmatIOn of Ammoma In Condensed Steam and

BoIler Feed-Water WIth a PotentIOmetnc Ammoma Probe", Analyst, 97 p 626-633 (1972)

3503-2
NITROGEN, KJELDAHL, TOTAL

Method 351.1 (Colorimetric, Automated Phenate)

STORET NO. 00625

1 Scope and ApplicatIOn

1 1 ThIS automated method may be used to determIne Kjeldahl mtrogen In surface and

saline waters The applicable range IS 0 05 to 2 0 mg Nil ApprOXImately 20 samples per

hour can be analyzed

2 Summary ofMethod

2 1 The sample IS automatIcally dIgested wIth a sulfunc aCId solutIon contaInIng potassIUm

sulfate and mercunc sulfate as a catalyst to convert orgamc mtrogen to ammomum

sulfate The solutIOn IS then automatIcally neutralized wIth sodIUm hydroxIde solutIOn

and treated wIth alkaline phenol reagent and sodIUm hypochlonte reagent ThIs

treatment forms a blue color deSignated as Indophenol SodIUm mtroprusslde, WhICh

Increases the IntenSIty of the color, IS added to obtaIn necessary senSItIVIty for

measurement oflow level mtrogen

3 Defimtlons

3 1 Total Kjeldahl mtrogen IS defined as the sum of free-ammoma and of orgamc mtrogen

compounds whIch are converted to (NH4)2S04 under the condItIons of dIgestIon WhIch

are speCIfied below

3 2 Orgamc Kjeldahl mtrogen IS defined as the dIfference obtaIned by subtractIng the freeammoma value from the total Kjeldahl mtrogen value Also, orgamc Kjeldahl mtrogen

may be determIned dIrectly by removal ofammoma before dIgestIon

4 Sample HandlIng and PreservatIon

4,1 Samples may be preserved by addItIon of 2 ml of conc H2S04per lIter and refngeratIOn

at 4°C Even when preserved In this manner, converSIOn of orgamc mtrogen to ammoma

may occur Therefore, samples should be analyzed as soon as pOSSIble

5 Interferences

5 1 Iron and chromIUm IOns tend to catalyze whl1e copper Ions tend to InhIbIt the Indophenol

color reactIon

6 Apparatus

6 1 Techmcon AutoAnalyzer conSIstIng of

6 1 1 Sampler II, eqmpped WIth contInuous mixer

6 1 2 Two proportIOmng pumps

6 1 3 Mamfold I

6 I 4 Mamfold II

6 1 5 Contmuous digester

6 1 6 Planetary pump

Approved for NPDES, pendmg approval for SectIon 304(h), CWA

Issued 1971

Edltonal reVISIon 1974 and 1978

351 1-1
6 1 7 Flve-gallon Carboy fume-trap

6 1 880°C Heatmg bath

6 1 9 Colonmeter eqUlpped wlth 50 mm tubular flow cell and 630 nm filters

6 1 10 Recorder eqUlpped wlth range expander

6 1 11 Vacuum pump

7. Reagents

7 1 Dlstl1led water Speclal precautlOn must be taken to msure that dlstl1led water IS free of

ammOnIa Such water IS prepared by passage of dlstl1led water through an lOn exchange

column compnsed of a mlxture of both strongly aCldlC cation and strongly baSiC anIon

exchange resms Furthermore, smce organIC contammatlOn may mterfere with thlS

analysls, use ofthe resm Dowex XE-75 or eqUlvalent whlCh also tends to remove organIc

Impunties IS advlsed The regeneratlOn ofthe 10n exchange column should be carned out

accordmg to the mstructlOn ofthe manufacturer

NOTE 1: All solutlOns must be made usmg ammonIa-free water

7 2 Sulfunc aCid As It readl1y absorbs ammOnIa, special precautlOn must also be taken wlth

respect to ItS use Do not store bottles reserved for thls determmatlOn m areas of potential

ammOnIa contammatlOn

73 EDTA (2% solutlOn) Dlssolve 20 g dlsodiUm ethylenedlamme tetraacetate m 1 hter of

distilled water Adjust pH to 10 5-11 wlth NaOH (74)

74 SodiUm hydrOXide (30% solutlOn) Dlssolve 300 g NaOH m 1 hter ofdlstilled water

NOTE 2: The 30% sodiUm hydroxlde should be sufficlent to neutrahze the dlgestate In

rare cases It may be necessary to mcrease the concentratlOn ofsodiUm hydroxlde m thlS

solutlOn to msure neutrahzatlOn of the dlgested sample m the manIfold at the water

Jacketed mlxmg colI

7 S SodiUm nItroprusslde, (005% solutlOn) Dlssolve 0 5 g Na2Fe(CN)sN0-2H20 m 1 hter

dlstllled water

7.6 Alkahne phenol reagent Pour 550 ml hqUld phenol (88-90%) slowly wlth mlxmg mto 1

hter of40% (400 g per hter) NaOH Cool and dllute to 2 hters wlth distl1led water

77 Sodmm hypochlonte (1 % solutlOn) Dl1ute commercial "Clorox"-200 ml to 1 hter wlth

dlstilled water Avallable chlonne level should be approxlmately 1% Due to the

mstab111ty ofthls product, storage over an extended penod should be aVOlded

7 8 Dlgestant mlxture Place 2 g red HgO m a 2 hter contamer Slowly add, wlth stirnng, 300

ml ofacld water (100 ml H2S04 + 200 ml H20) and stir untl1 cool Add 100 mllO% (10

g per 100 ml) K2S04 Dl1ute to 2 hters wlth conc sulfunc aCld (approxlmately 500 ml at a

time, allowmg time for coolmg) Allow 4 hours for the preclpitate to settle or filter

through glass fiber filter

7 9 Stock solution Dlssolve 4 7193 g of pre-dned (1 hour at 105°C) ammOnIum sulfate m

dlstl1led water and dl1ute to 1 0 hter m a volumetnc flask 1 0 ml = 1 0 mg N

7 10 Standard solutlOn Dl1ute 100 ml ofstock solutlOn (79) to 1000 milO ml = 001 mg N

7 11 Usmg the standard solutlOn (7 10), prepare the followmg standards m 100 ml volumetnc

flasks

351 1-2
Cone, mg N/l

000

005

010

020

040

060

080

100

150

200

ml Standard Solutl0n/100 ml

00

05

10

20

40

60

80

100

150

200

8 Procedure

8 1 Set up mamfolds as shown m FIgures 1, 2, and 3

8 1 1 In the operatlOn of mamfold No 1, the control of four key factors IS reqUlred to

enable mamfold No 2 to receIve the mandatory representatIve feed FIrst, the

dIgestant flowmg mto the pulse chamber (PC-1) must be bubble free, otherWIse, aIr

WIll accumulate m A-7, thus altenng the ratlO of sample to dIgestant m dlgestor

Second, m mamtammg even flow from the dlgestor hehx, the penstaltlc pump must

be adjusted to cope WIth dIfferences m denSIty ofthe dlgestate and the wash water

ThIrd, the sample pIck-up rate from the hehx must be precIsely adjusted to msure

that the entIre sample IS aspIrated mto the mlxmg chamber And finally, the

contents of the "Mlxmg Chamber" must be kept homogeneous by the proper

adjustment ofthe atr bubbhng rate

8 12 In the operatlOn of mamfold No 2, It IS Important m the neutrahzatlOn of the

dIgested sample to adjust the concentratlOn ofthe NaOH so that the waste from the

C-3 debubbler IS shghtly aCId to Hydnon B paper

8 1 3 The dlgestor temperature IS 390°C for the first stage and 360°C for the second and

thIrd stages

8 2 Allow both colonmeter and recorder to warm up for 30 mmutes Run a baselme WIth all

reagents, feedmg dIstIlled water through the sample hne Adjust dark current and

operatIve openmg on colonmeter to obtam stable basehne

83 Set samphng rate of Sampler II at 20 samples per hour, usmg a sample to wash ratIO of 1

to 2 (1 mmute sample, 2 mmute wash)

84 Arrange vanous standards m sampler cups tn order of mcreasmg concentratlOn

Complete loadmg ofsampler tray WIth unknown samples

8 5 SWItch sample hne from dIstIlled water to sampler and begm analySIS

9 CalculatlOn

9 1 Prepare standard curve by plottmg peak heIghts of processed standards agamst

concentratlOn values Compute concentratIon of samples by comparmg sample peak

heIghts WIth standard curve

9 2 Any sample that has a computed concentratIon that IS less than 10% of the sample run

ImmedIately pnor to It must be rerun

351 1-3
10 PreCISIon and Accuracy

10 I SIX laboratones analyzed four natural water samples contaInIng exact Increments of

organIc mtrogen compounds, wIth the follOWIng results

Increment as

KJeldahl-NItrogen

mg Nlllter

189

2 18

509

581

PreCISIOn as

Standard DeViatIOn

Kjeldahl-N mg N/hter

054

061

125

185

BIblIography

Bias,

%

-246

-283

-238

-219

Accuracy as

Bias,

fig N/hter

-046

-062

-121

-127

1. Kammerer, P A, Rodel, M G, Hughes, R A, and Lee, G F , "Low Level KJeldahl NItrogen

DetermInatIon on the Techmcon AutoAnalyzer" EnVIronmental SCIence and Technology,.1

340 (1967)

2 McDanIel, W H, HemphIll, R N, Donaldson, W T, "AutomatIc DetermInatIOn of Total

KJeldahl NItrogen In Estuanne Waters" Presented at Techmcon SympOSIUm on AutomatIOn

m AnalytIcal ChemIstry, New York, October 3,1967

3 B O'Connor, Dobbs, VIlhers, and Dean, "Laboratory DIstIllatIOn of Mumcipal Waste

Effluents" JWPCF 39, R 25, 1967

351 1-4
WASH WATER ITO SAMPLER 2)

*AIR IS SCRUBBED THRU 5N H2S04

* *TEFLOII TUBING OR GLASS

* **FOR FRESH WATER SAMPLES USE

I

IIIXIIIG CUIIEI PIOPOITIOIIIMli 'UIIP

All

mljmln

SMALL 1'" MIXING COIL 2 00 WASH WATER FOR SUT

1 60 SAMPLE WATER

2 00 DISTILLElI WATER SAMPLES

1 60 AIR *

COOLlIIG WATEI=:::I P B 2 03 DIGESTANT

} ACIDFLEX TUBING P B 2 03 DIGEST ANT

VACUUII PUll' -

COIL

\.»

~I' P W 3 90 DISTILLED WATER VI * * -- P W _390 DISTILLED WATER I

VI

Itt N

CI P B 2 90 WASH WATER z:

Q P P 2 50 SAMPLE ......

CI

... G G 2 00 DISTILLED WATER

Y 1 20 AIR * - y CI A. z: I- :2: c ::) :2: en CI

CI I- FIGURE 1 KJELDAHL NITROGEN - MANIFOLD 1 AA·I I-
CONTINUOUS DIGESTER & MIXING CHAMBER ASSEMBLY

(BtowtE~

1 OXIDIZED SAMPLE

2 AIR AGITATION

3 MIXIIiG CHAMBER OVERflOW

4 WASTE

5 FEED TO MANIFOLD NO 2

LINE DESIGNATION

@

TO SUMP t

t

- AI.

@

®

ADUISTABLE flOW

'RUIN' PLAIIAUU I :: :: '""-q

PUMP

DILUTION WATE. t

5 GAlLON

FUME CARBON TRAP

HAlF FillED WITH

40% NaOH

CONNECTED TO

ASPIRATOR

TO ASPIRATOR c::it=-f4f~

w

Ul

--I

0\

TO ASPIRATOR

l

TO MAIIIFOLD 110 2

f

FI'GURE 2. KJELDAHL NITROGEN AA-I
C3

WASTE

",I/lllin

r "\ BLUE BLUE 1 60 SAMPLE FROM MIXING CHAMBER

\ .J l G G 2 00 MaOH ISH IAIUFOLD 1 J

JACKETED IIXER + • • D 10 DISTILLED WATEI

y y 1 20 All

LARGE MIXIIIG COILS ILl]

" • 2U SAIPLE

+ y y 1 2. EDTA

I I III All

L. I I III DISTILLED WATEI

Y Y 1 21 ALL "HEMOL

Y Y 1 21 IhIlCL

y y 1 21 NITu.pnSSIDE

lUTE. p I 341 lASH

IALL IIXIIiG COIL

"1O"UTlUIItG "II"

) 2x40 ' COIL LI

.... rlt

~"'J D IECORDEI

8

V>

VI

-

-I

-.I

638 II. FILTERS

FIGURE 3. KJELDAHL NITROGEN MANIFOLD 2. AA-I
NITROGEN, KJELDAHL, TOTAL

Method 351.2 (Colorimetric, Semi-Automated Block Digester, AAII)

STORET NO. 00625

1 Scope and ApplIcatlOn

11 Thts method covers the determmatlOn ofto1..al Kjeldahl mtrogen m dnnkmg and surface

waters, domestIc and mdustnal wastes The procedure converts mtrogen components of

bIologIcal ongIn such as ammo aCIds, protems and peptides to ammoma, but may not

convert the mtrogeneous compounds of some mdustnal wastes such as ammes, mtro

compounds, hydrazones, OXImes, semicarbazones and some refractory tertIary ammes

The applIcable range ofthIS method IS 01 to 20 mg/l TKN The range may be extended

WIth sample dilutlOn

2 Summary ofMethod

21 The sample IS heated m the presence ofsulfunc aCId, K2S04and HgS04for two and one

half hours The reSIdue IS cooled, dIluted to 25 ml and placed on the AutoAnalyzer for

ammoma determmation ThIS dIgested sample may also be used for phosphorus

determmatlOn

3 DefimtlOns

3 1 Total Kjeldahl mtrogen IS defined as the sum of free-ammoma and orgamc mtrogen

compounds WhICh are converted to ammomum sulfate (NH4)2S04, under the condItIons

ofdigestlOn deSCrIbed below

32 Orgamc Kjeldahl mtrogen IS defined as the dIfference obtamed by subtractmg the freeammoma value (Method 3502, NItrogen, Ammoma, thIS manual) from the total

Kjeldahl mtrogen value

4 Sample HandlIng and PreservatlOn

4 1 Samples may be preserved by addItIon of 2 ml of conc H2S04per lIter and stored at 4°C

Even when preserved m thIS manner, converSIon of orgamc mtrogen to ammoma may

occur Therefore, samplesshould be analyzed as soon as pOSSIble

5 Apparatus

5 1 Block Digestor-40

5 2 Techmcon Mamfold for Ammoma (FIgure 1)

53 Chemware TFE (Teflon bOllmg stones), Markson SCIence, Inc, Box 767, Delmar, CA

92014)

6 Reagents

6 1 MerCUrIC Sulfate DIssolve 8 g red merCUrIC OXIde (HgO) m 50 ml of 1 4 sulfUrIC aCId (10

ml conc H2S04 40 ml dIstIlled water) and dIlute to 100 ml WIth dIstIlled water

6 2 DigestlOn SolutlOn (SulfUrIC aCId-merCUrIc sulfate-potaSSIUm sulfate solutlOn) DIssolve

133 g of K2S04m 700 ml of dIstIlled water and 200 ml of conc H2S04 Add 25 ml of

merCUrIC sulfate solutlOn and dIlute to 1lIter

Pendmg approval for NPDES

Issued 1978

3512-1
6.3 Sulfunc ACId SolutIOn (4%) Add 40 ml of conc sulfunc aCId to 800 ml ofammOnIa free

dIStl1led water, cool and dIlute to 1lIter

6 4 Stock SodIUm HydroXide (20%) DIssolve 200 g of sodIUm hydroxIde In 900 ml of

ammonIa-free dIStilled water and dIlute to 1lIter

65 Stock SodIUm PotaSSIUm Tartrate Solution (20%) DIssolve 200 g sodIUm potaSSIUm

tartrate In about 800 ml of ammoma-free dIstIlled water and dIlute to I lIter

66 Stock Buffer SolutIon DIssolve 1340 g of sodIUm phosphate, dibaslC (Na2HP04) In

about 800 ml of ammOnIa free water Add 20 g ofsodIUm hydrOXIde and dIlute to 1 lIter

6.7 WorkIng Buffer SolutIOn CombIne the reagents In the stated order, add 250 ml ofstock

sodIUm potaSSIUm tartrate SolutIon (6 5) to 200 ml ofstock buffer solutIOn (6 6) and mIX

Add xx ml sodIUm hydroxIde SolutIon (64) and dIlute to 1 lIter See concentratIOn

ranges, Table I, for compOSItIon ofworkIng buffer

6.8 SodIUm Sahcylate/SodIUm NItroprussIde SolutIon DIssolve 150 g of sodIUm salIcylate

and 0 3 g ofsodIum nItroprussIde In about 600 ml of ammOnIa free water and dIlute to 1

lIter.

6 9 SodIUm Hypochlonte SolutIon DIlute 6 0 ml sodIum hypochlonte solutIOn (clorox) to

100 ml WIth ammOnIa free dIstilled water

6 10 AmmonIum chlonde, stock solutIOn DIssolve 3 819 g NH4CIIn dIstIlled water and bnng

to volume In a 1lIter volumetnc flask 1ml= 1 0 mg NH3-N

7. Procedure

DIgestiOn

7 1 To 20 or 25 ml of sample, add 5 ml of dIgestIon solutIOn (62) and mIX (use a vortex

mIxer)

72 Add (4-8) Teflon boIlIng stones (5 3) Too many boIlIng chIps wIll cause the sample to

bOIl over

73 WIth Block Digestor In manual mode set low and hIgh temperature at 160°C and preheat

UnIt to 160°C Place tubes In digestor and SWItch to automatIc mode Set low temperature

timer for 1 hour Reset hIgh temperature to 380°C and set tImer for 2 1/2 hours

7 4 Coolsample and dIlute to 25 ml With ammOnIa free water

Colonmetnc AnalySIS

7.5 Check the level ofall reagent contaIners to ensure an adequate supply

7 6 Excludmg the salIcylate lme, place all reagent lInes m theIr respectIve contamers, connect

the sample probe to the Sampler IV and start the proportIOnmg pump

77 Flush the Sampler IV wash receptacle WIth about 25 ml of40% sulfunc aCId (6 3)

7 8 When reagents have been pumpmg for at least five mmutes, place the salIcylate lIne m ItS

respective contamer and allow the system to equIlIbrate If a preCIpItate forms after the

addItIOn ofsalIcylate, the pH IS too low ImmedIately stop the proportIOnIng pump and

flush the colls WIth water usmg a synnge Before restartmg the system, check the

concentratIon ofthe sulfunc aCId solutIOns and/or the workIng buffer solution

3512-2
TABLE 1

CONCENTRATION RANGES

(NITROGEN)

ml stock NaOH

DilutIOn loops Approx Range per hter

Imtlal sample Resample std cal PPM N working buffer

No Sample 1me Dl1uent line Resample line Dl1uent Ime settmg (±1O%) solutIOn

w

u.

-

N

I

w 1 80 (REDIRED) 80 (REDIRED) 32 (BLKlBLK) 80 (REDIRED) 700 0-05 250

2 80 (REDIRED) 80 (REDIRED) 32 (BLK/BLK) 80 (REDfRED) 100 0-15 250

3 16 (ORNIYEL) 80 (RED/RED) 32 (BLK/BLK) 80 (REDIRED) 700 0-1 120

4 16 (ORNIYEL) 80 (REDfRED) 32 (BLKIBLK) 80 (REDIRED) 100 0-5 120

5 16 (ORNIYEL) 80 (REDIRED) 16 (ORNIYEL) 80 (REDIRED) 700 0-2 80

6 16 (ORNIYEL) 80 (REDIRED) 16 (ORNIYEL) 80 (REDIRED) 100 {}-10 80
· 7 9 To prevent preCIpItatIOn ofsodlUm sahcylate m the waste tray, whlCh can clog the tray

outlet, keep the mtrogen flowcell pump tube and the mtrogen Colonmeter "To Waste"

tube separate from all other lmes or keep tap water flowmg m the waste tray

7 10 After a stable baselme has been obtamed start the Sampler

8 CalculatIons 1

8 1 Prepare standard curve by plottmg peak heIghts of processed standards agamst

concentratIOn values Compute concentratHms ?y companng sample peak heIghts wIth

standard curve

9 PreCISIon and Accuracy

9 1 In a smgle laboratory (EMSL), usmg sewage samples of concentratIOns of 1 2, 26, and

1 7 mg Nil, the preCISIOn was ±O 07, ±O 03 and ±O 15, respectIvely

9.2 In a smgle laboratory (EMSL), usmg sewage , samples of concentratIOns of 47 and 8 74

mg Nil, the recovenes were 99 and 99%, respectIvely

I ,

Bibliography .

McDamel, W H , HemphIll, R N and Donaldson, W T , "Autqm~tlC DetermmatIOn of Total

K]eldahl NItrogen m Estuanne Water", Techmcon SymposIa, pp 362-367, Vol 1, 1967

2 Gales, ME, and Booth, R L, "EvaluatIOn of Organic NItrogen Methods", EPA Office of ,

Research and Momtonng, June, 1972

3 Gales, M E and Booth, R L, "SImultaneous and Automated DetermmatIOn of Total

Phosphorus and Total KJeldahl NItrogen", Methods Development and Quahty Assurance

Research Laboratory, May, 1974

4. Techmcon "Total Kjeldahl NItrogen and Total 'Phosphorus BD-40 DIge~tIOn Procedure for

Water", August, 1974 . ,

5 Gales, ME. and Booth, R L, "EvaluatIOn of the Block DIgestIOn System for the

Measurement of Total KJeldahl Nitrogen and Total Phosphorus", EPA-600/4-78-015,

EnvIronmental Momtonng and Support Laborat~ry, Cmncmnatl, OhIO

3512-4
E

HORUS

NE

ml/mrn

GRY GRY 10 4% H2SO4

BLK BLK 032 AIR

10 TURNS I TO PHOSP

0000 RED RED 080 DILUENT WATER SAMPLE LI

116-0489-01 ORN YEL *SAMPLE PT2

116-BOOO

BLK BLK 032 AIR

37°C 157-B089

I 5 TURNS 157-B273-03 10 TURNS 20 TURNS

ftftM I 110M I 0000 nl6n RED RED 080 WORKING BUFFER

T J

I ORN YEL *RESAMPLE

BLK BlK 032 SALlCYLATE-NIT~OPRUSSlDE I

ORN YEL 016 HYPOCHLORITE WAST

GRY GRY 10 WASTE

\.II

W

\.II

-

TO PUMP TUBE t3]

COLORIMETER

660nm

50mm FIC x 15mm 10

FIGURE 1 AMMONIA MANIFOLD AAII
NITROGEN, KJELDAHL, TOTAL

Method 351.3 (Colorimetric; Titrimetric; Potentiometric)

STORET NO. 00625

1 Scope and AppltcatlOn

1 1 Th1s method covers the determmatlOn oftotal KJeldahl mtrogen m dnnkmg, surface and

sahne waters, domest1c and mdustnal wastes The procedure converts mtrogen

components of blOloglCal ongm such as ammo aC1ds, protems and pepttdes to ammoma,

but may not convert the mtrogenous compounds of some mdustnal wastes such as

ammes, mtro compounds, hydrazones, OX1mes, sem1carbazones and some refractory

tert1ary ammes

12 Three alternattves are ltsted for the determmatlOn of ammoma after d1stl1latlOn the

titnmetnc method wh1ch 1S appltcable to concentratIOns above 1 mg N/ltter, the

NesslenzatlOn method whlCh 1S appltcable to concentratIOns below 1 mg Nll1ter, and the

potentlOmetnc method appltcable to the range 005 to 1400 mg/1

1 3 Th1s method 1S descnbed for macro and mlCro glassware systems

2 DefimtlOns

2 1 Total KJeldahl mtrogen 1S defined as the sum of free-ammoma and orgamc mtrogen

compounds wh1ch are converted to ammomum sulfate (NH4)2S04, under the cond1tions

ofd1gestlOn descnbed below

2 2 Orgamc KJeldahl mtrogen 1S defined as the d1fference obtamed by subtractmg the freeammoma value (Method 3502, N1trogen, Ammoma, th1s manual) from the total

KJeldahl mtrogen value Th1s may be determmed d1rectly by removal of ammoma before

d1gestlOn

3 Summary ofMethod

3 1 The sample 1S heated m the presence of cone sulfunc aC1d, K2S04 and HgS04 and

evaporated untl1 S03 fumes are obtamed and the solutIOn becomes colorless or pale

yellow The res1due 1S cooled, dl1uted, and 1S treated and made alkahne w1th a hydrox1dethIOsulfate solutIOn The ammoma 1S d1stl1led and determmed after d1stl1lat10n by

NesslenzatlOn, titratIOn or potentlOmetry

4 Sample Handhng and PreservatlOn

4 1 Samples may be preserved by add1tion of 2 ml of conc H2S04per hter and stored at 4°C

Even when preserved m th1s manner, converS10n of orgamc mtrogen to ammoma may

occur Preserved samples should be analyzed as soon as poss1ble

5 Interference

5 1 H1gh mtrate concentratIOns (lOX or more than the TKN level) result In low TKN

values The reactIOn between mtrate and ammoma can be prevented by the use of an

amon exchange resm (chlonde form) to remove the mtrate pnor to the TKN analys1s

Approved for NPDES

Issued 1971

Ed1tonal reV1SlOn 1974 and 1978

3513-1
6. Apparatus

6.1 DigestlOn apparatus A Kjeldahl digestlOn apparatus wIth 800 or 100 ml flasks and

suctIon takeoffto remove S03 fumes and water

6 2 DisttllatIon apparatus The macro Kjeldahl flask IS connected to a condenser and an

adaptor so that the dIstl1late can be collected MIcro Kjeldahl steam disttllatlOn

apparatus IS commercIally aval1able

6 3 Spectrophotometer for use at 400 to 425 nm wIth a hght path of 1 cm or longer

7 Reagents ,

7.1 DIstl1led water should be free of ammoma Such water IS best prepared by the passage of

disttlled water through an Ion exchange column contammg a strongly aCIdIc catton

exchange resm miXed wIth a strongly basIc amon exchange resm RegeneratlOn of the

column should be carned out accordmg to the manufacturer's mstructiOns

NOTE 1: All solutlOns must be made WIth ammoma-free water

7 2 Mercunc sulfate solutIon DIssolve 8 g red mercunc oXIde (HgO) m 50 ml of 1 4 sulfunc

aCId (10 0 ml conc H2S04 40 ml dIstl1led water) and dIlute to 100 ml wIth dIstl1led

water

73 Sulfunc aCId-mercunc sulfate-potassIUm sulfate SolutIon DIssolve 267 g K2S04 m 1300

ml dIstl1led water and 400 ml conc H2S04 Add 50 ml mercunc sulfate SolutIon (7 2) and

dilute to 2 hters wIth dlstl1led water

74 SodIUm hydroxIde-sodIUm thIosulfate solutton DIssolve 500 g NaOH and 25 g

Na2S203-5H20 ill dIst111ed water and dl1ute to 1hter

7 5 MiXed mdicator MiX 2 volumes of 02% methyl red m 95% ethanol wIth 1 volume of

o2% methylene blue m ethanol Prepare fresh every 30 days

7 6 Bonc aCId solutlOn DIssolve 20 g bonc aCId, H3B03, m water and dl1ute to 1 hter wIth

dIstIlled water

7 7 Sulfunc aCId, standard solutiOn (0 02 N) 1 ml = 0 28 mg NH3-N Prepare a stock

solutIon of approxImately 0 1 N aCId by dl1utmg 3 ml of conc H2S04 (sp gr 1 84) to 1

hter wIth CO2-free dIstilled water Dl1ute 200 ml of thIS solutlOn to 1 hter wIth CO2-free

disttlled water StandardIze the approxImately 0 02 N aCId so prepared agamst 0 0200 N

Na2C03 solutIon ThIs last solutiOn IS prepared by dissolvmg 1 060 g anhydrous Na2C03,

oven-dned at 1400C, and dl1utmg to 1 hter wIth CO2-free dIstl1led water

NOTE 2: An alternate and perhaps preferable method IS to standardIze the

approxImately 0 1 N H2S04 SolutIon agamst a 0 100 N Na2C03 SolutIon By proper

dl1utlOn the 0 02 N aCId can the be prepared

7.8 Ammomum chlonde, stock solutIon 10 ml = 10 mg NH3-N DIssolve 3819 g NH4CI

In water and make up to 1 hter m a volumetnc flask wIth dIstIlled water

7 9 Ammomum chlonde, standard SolutIon 1 0 ml = 001 mg NH3-N DIlute 10 0 ml ofthe

stock solutlOn (7 8) wIth dIstilled water to 1 hter m a volumetnc flask

710 Nessler reagent DIssolve 100 g ofmercunc lOdide and 70 g potaSSIUm lOdide m a small

volume of dIstl1led water Add thIS mIxture slowly, wIth sttrnng; to a cooled SolutIon of

160 g of NaOH m 500 ml of dIstl1led water Dl1ute the mIxture to 1 hter The solutiOn IS

stable for at least one year Ifstored m a pyrex bottle out ofdIrectsunlIght

3513-2
NOTE 3. Reagents 7 7, 78, 79, and 7 10 are IdentlCal to reagents 6 8, 62,63, and 66

descnbed under NItrogen, Ammoma (Colonmetnc, Tltnmetnc, PotentIOmetncDIstIllatIOn Procedure, Method 350 2)

8 Procedure

8 1 The dlst1l1atIOn apparatus should be pre-steamed before use by dlstlllIng all mIxture of

dlst1l1ed water and sodmm hydroxlde-sodmm thIOsulfate solutIOn (74) untll the dlst1l1ate

IS ammoma-free ThIS operatIOn should be repeated each time the apparatus IS out of

serVIce long enough to accumulate ammoma (usually 4 hours or more)

8 2 Macro KJeldahl system

8 2 1 Place a measured sample or the resIdue from the dIstIllatIOn m the ammoma

determmatlOn (for Orgamc KJeldahl only) mto an 800 ml KJeldahl flask The

sample SIze can be determmed from the followmg table

KJeldahl NItrogen

m Sample, mg/l

0-5

5-10

10-20

20-50

50-500

Sample SIze

ml

500

250

100

500

250

Dllute the sample, If reqUlred, to 500 ml WIth dlst1l1ed water, and add 100 ml

sulfunc aCld-mercunc sulfate-potassmm sulfate solutlOn (7 3) Evaporate the

mIxture m the KJeldahl apparatus untll S03 fumes are gIven off and the solutlOn

turns colorless or pale yellow Contmue heatmg for 30 addltlOnal mmutes Cool the

reSIdue and add 300 ml dlst1l1ed water

8 2 2 Make the dlgestate alkalme by careful addltlOn of 100 ml of sodmm hydroxIde -

thlOsulfate solutIOn (7 4) WIthout mlxmg

NOTE 5' Slow addltlOn of the heavy caustIc solutlOn down the tllted neck of the

dlgestlOn flask WIll cause heaVIer solutlOn to underlay the aqueous sulfunc aCId

solutlOn WIthout loss of free-ammoma Do not mIX untll the dlgestlOn flask has

been connected to the dlst1l1atlOn apparatus

8 2 3 Connect the KJeldahl flask to the condenser WIth the tip of condenser or an

extenslOn ofthe condenser tIp below the level ofthe bonc aCId solutlOn (7 6) m the

recelvmg flask

824 DISt1l1 300 ml at the rate of 6-10 mllmm, mto 50 ml of 2% bonc aCId (76)

contamed m a 500 ml Erlenmeyer flask

8 2 5 DIlute the dlst1l1ate to 500 ml m the flask These flasks should be marked at the 350

and the 500 ml volumes WIth such markmg, It IS not necessary to transfer the

dlst1l1ate to volumetnc flasks For concentratlOns above I mg/I, the ammoma can

be determmed tItnmetncally For concentratlOns below thIS value, It IS determmed

colonmetncally The potentlOmetnc method IS applIcable to the range 005 to 1400

mg/I

351 3-3
8.3 MIcro KJeldahlsystem

8.3 1 Place 500 ml ofsample or an ahquot dIluted to 50 ml m a 100 ml KJeldahl flask

and add 10 ml sulfunc aCId-mercunc sulfate-potassIUm sulfate solutIOn (7 3)

Evaporate the mIxture m the KJeldahl apparatus untIl S03 fumes are gIven off and

the SolutIon turns colorless or pale yellow Then digest for an addItional 30

mmutes Cool the resIdue and add 30 ml distIlled water

8 3 2 Make the digestate alkahne by careful addItion of 10 ml of sodIUm hydroxIdethIosulfate solution (7 4) Without mIxmg Do not mIX untIl the dIgestIOn flask has

been connected to the dIstillatIOn apparatus

8 3 3 Connect the KJeldahl flask to the condenser with the tIp of condenser or an

extension ofthe condenser tiP below the level ofthe bonc aCId SolutIon (76) m the

receIvmg flask or 50 ml short-form Nessler tube

8.34 Steam dIStill 30ml at the rate of6-10 mllmm ,mto 5 mlof2% boncacid (76)

8 3 5 DIlute the dIstillate to 50 ml For concentratIons above 1mg!l the ammoma can be

determtned tItnmetncally For concentratIons below thIS value, It IS determmed

colonmetncally The potentiometnc method IS apphcable to the range 005 to 1400

mg/1

8.4 DetermtnatIOn of ammoma m dIstIllate Determme the ammoma content ofthe dIstIllate

tItnmetncally, colonmetncally, or potentiometncally, as descnbed below

84 1 Tltnmetnc determmatIOn Add 3 drops ofthe mIxed mdicator (7 5) to the dIstIllate

and tItrate the ammoma with the 002 N H2S04 (77), matchmg the endpomt

agamst a blank contammg the same volume of dIstIlled water and H3B03 (7 6)

solution

8 4 2 Colonmetnc determmatIOn Prepare a senes of Nessler tube standards as follows

ml of Standard

10 ml = 001 mg NH3-N

00

05

10

20

40

50

80

100

mg NH3-N!50 0 ml

00

0005

0010

0020

0040

0050

0080

010

DIlute each tube to 50 ml with ammoma free water, add 1 ml of Nessler Reagent

(7 10) and mIX After 20 mmutes read the absorbance at 425 nm agamst the blank

From the values obtamed for the standards plot absorbance vs mg NH3-N for the

standard curve Develop color m the 50 ml dIluted dIstIllate m exactly the same

manner and read mg NH3-N from the standard curve

8 4.3 Potentiometnc determmatIOn Consult the method entItled NItrogen, Ammoma

PotentIOmetnc, Ion SelectIve Electrode Method, (Method 350 3) m thIS manual

8 4 4 It IS not ImperatIve that all standards be treated m the same manner as the samples

It IS recommended that at least 2 standards (a hIgh and low) be dIgested, dIstIlled,

351 3-4
and compared to similar values on the curve to lllsure that the dIgestIon-distIllatiOn

techmque IS relIable Iftreated standards do not agree wIth untreated standards the

operator should find the cause ofthe apparent error before proceedlllg

9 CalculatiOn

9 I If the tltnmetric procedure IS used, calculate Total KJeldahl NItrogen, III mg/I, III the

onglllalsample as follows

(A - B)N x F x 1,000 TKN, mg/l = S

where

A = mIllIlIters ofstandard 0 020 N H2S04 solutiOn used III tltratlllg sample

B = mIllIlIters ofstandard 0 020 N H2S04 solutiOn used III titratmg blank

N = normalIty ofsulfunc aCId solutiOn

F = mIllIeqUIvalent weIght ofmtrogen (14 mg)

S = mIllIlIters ofsample dIgested

Ifthe sulfunc aCId IS exactly 0 02 N the formula IS shortened to

TKN II _ (A - B) x 280

,mg - S

92 Ifthe Nessler procedure IS used, calculate the Total KJeldahl NItrogen, m mg/l, III the

onglllalsample as follows

TKN, mg/l = A xri'OOO x

where

A = mg NH3-N read from curve

B = ml total dIstIllate collected lllcludlllg the H3B03

C = ml dIstIllate taken for NesslenzatiOn

D = ml ofonglllal sample taken

9 3 Calculate Orgamc K]eldahl NItrogen III mg/I, as follows

Orgamc KJeldahl NItrogen = TKN -(NH3-N )

3513-5
94 PotentlOmetnc determmatlOn Calculate Total KJeldahl NItrogen, m mg/1, m the

ongmalsample asfollows

B TKN, mg/l = D x A

where

A = mg NH3-N/1 from electrode method standard curve

B = volume ofdl1uted d1stlllate m ml

D = ml ofongmalsample taken

10. PrecisIon

10 1 Thtrty-one analysts m twenty laboratones analyzed natural water samples contalmng

exact mcrements oforgamc mtrogen, wIth the followmg results

Increment as

NItrogen, KJeldahl

mg N/hter

020

031

410

461

PreCISion as

Standard DevIatIOn

mg N/hter

0197

0247

1056

1 191

Bias,

%

+1554

+ 545

+ 103

- 167

Accuracy as

Bias,

fig N/hter

+003

+002

+004

-008

(FWPCA Method Study 2, Nutnent Analyses)

BIbliography

1. Standard Methods for the ExammatlOn of Water and Wastewater, 14th EdItion, p 437,

Method 421 (1975)

2. Schlueter, Albert, "Nitrate Interference In Total KJeldahl NItrogen DetermmatlOns and Its

Removal by Amon Exchange Resms", EPA Report 600/7-77-017

" '

3513-6
NITROGEN, KJELDAHL, TOTAL

Method 351.4 (Potentiometric, Ion Selective Electrode)

STORET NO. 00625

1 Scope and ApplicatiOn

1 1 ThIS method IS applicable to the measurement of TKN III dnnklllg and surface water,

domestIc and llldustnal wastes

1 2 ThIS method covers the range from 0 03 to 25 mg TKN/1

2 Summary ofMethod

2 1 FolloWlllg dIgestiOn and cooling, dlstl1led water IS added to the dIgestiOn flask and the

pH adjusted to between 3 and 4 5 by the addItiOn of 10 N NaOH The sample IS cooled

and transferred to a 100 ml beaker After lllsertlllgthe electrode llltO the sample, NaOHNaI-EDTA IS added and the ammoma measured (Ethylene diamllle tetraacetIc aCId

(EDTA) IS added to the alkaline reagent (NaOH-NaI) to prevent precIpItatiOn of I

hydroXIdes, thereby aVOldlllg deposItiOn on the electrode membrane)

3 Sample Handling and PreservatiOn

3 1 Samples may be preserved by addItiOn of 2 ml of conc H2S04 per liter and stored at 4°C

Even when preserved III thIS manner, converSiOn of orgamc mtrogen to ammoma may

occur Preserved samples should be analyzed as soon as possIble

4 Interferences

4 1 Interference from metals IS elimlllated WIth the addItion ofNaI

42 HIgh mtrate concentratiOns (lOX or more than the TKN level) result III low TKN

values The reactiOn between mtrate and ammoma can be prevented by the use of an

amon exchange reSlll (chlonde form) to remove the mtrate pnor to the TKN analysIs

5 Apparatus

5 1 Electrometer (pH meter) wIth expanded mV scale

52 Ammoma selectIve electrode, such as Onon Model 95-10

53 MagnetIc stIrrer, thermally lllsulated and Teflon-coated stIrrlllgbar

5 4 DIgestiOn apparatus A Kjeldahl dIgestiOn apparatus wIth 800 or 100 m1 flasks and

suction take offto remove S03 fumes and water

5 5 Techmcon Block Dlgestor BD-40

6 Reagents

6 1 Dlstl1led water should be free of ammoma Such water IS best prepared by passlllg

dlstl1led water through an IOn exchange column contallllllg a strongly aCIdIC catIOn

exchange reSlll mIxed wIth a strongly basIc amon exchange reSlll RegeneratIOn of the

column should be carned out accordlllg to the manufacturer's lllstructl0ns

NOTE 1: All solutiOns must be made wIth ammoma-free water

6 2 Mercunc sulfate solutIOn DIssolve 8 g red mercunc oXIde (HgO) III 50 ml of 1 4 sulfunc

aCId (10 0 m1 conc H2S04 40 ml dIstilled water) and dl1ute to 100 ml wIth dlstl1led water

Pendmg approval for NPDES

Issued 1978

3514-1
63 Sulfunc aCId-mercunc sulfate-potassIUm sulfate solutIOn DIssolve 267 g K2S04 In 1300

ml dIstIlled water and 400 ml conc H2S04 Add 50 ml merCUrIC sulfate solutIOn (6 2) and

dIlute to 2 lIters WIth dIstIlled water

6.4 SodIUm hydroxIde 10N DIssolve 400 g NaOH In 600 ml of ammoma-free water, cool

and dIlute to 1lIter ' "

6.5 SodIUm HydroxIde, SodIUm IodIde and EDTA Solution DIssolve 400 g of NaOH, 300 g

NaI and 2 g ofEDTA In 700 ml ofammoma-free water, cool and dIlute to 1lIter

66 Ammomum chlonde, stock solutIOn 10 ml = 10 mg NH3-N DIssolve 3819 g NH4CI

m water and make up to 1lIter In a volumetrIc flask WIth dIstIlled water

6.7 Ammomum chlorIde, standard solutIOn 10 ml = 001 mg NH3-N DIlute 10 0 ml ofthe

stock solutIOn (6 6) to 1 lIter WIth dIStilled water In a volumetn:c flask

7 Procedure

7.1 Macro KJeldahl system

77.1 Place a measured sample or the reSIdue from the dIstIllatIon In the ammoma

determInatI,on (for Orgamc KJe1dahl only) Into an 800 ml KJeldahl flask The

sample SIze can be determmed from the follOWIng table ' ,

Kjedahl Nitrogen

III Sample, mgll

0-5

5-10

10-20

20-50

50-500

Sample Size

ml

500

250

100

500

250

DIlute the sample, If reqUIred, to 500 ml WIth dIstIlled water, and add 100 ml

sulfUrIC aCId-merCUrIC sulfate-potassIUm sulfate solutIOn (63) and evaporate the

mIxture In the KJeldahl apparatus untIl S03 fumes are' gIven off and the solution

turns colorless or pale yellow ContInue heatIng for 30 addItional mInutes Cool the

resIdue and add 500 ml dIstIlled water and mIX

7 2 MIcro KJeldahl system

721 Place 50 0 ml ofsample, or an ahquot dIluted to 50 ml, In a 100 ml KJeldahl flask

and add 10 ml sulfUrIC aCId-merCUrIC sulfate-potassIUm sulfate solutIOn (63)

Evaporate the mIxture In the KJeldahl apparatus untIl S03 fumes are gIven off and

the SolutIon turns colorless or pale yellow Then dIgest for an addItional 30

mInutes Cool the reSIdue, add 44 ml dIStilled water and mIX

7 3 Block Digestor

7 3 1 Place 20 ml ofsample, or an ahquot dIluted to 20 ml, In the dIgestIOn tube Add 5

ml ofsulfUrIC aCId-merCUrIC sulfate-potasSIUm sulfate solutIOn (6 3) and mIX Add

4-8 Teflon bOlhng stones

7 3 2 Place tubes In wgestor that has been preheated to 200°C

733 Set low temperature at 200°C for 1 hour, the hIgh temperature at 380°C and total

time for two and one halfhours

3514-2

1

11 1111
7 3 4 After the temperature ofthe block has reached 380°C, the time should be set for 30

mInutes Longer tIme and hIgher temperature may result In complete loss of the

aCId

7 3 5 Cool, add 25 ml ofammoma-free water and mIX

7 4 Electrode analysIs

7 4 1 All standards should be treated as the samples and should contaIn the same

concentratIOn ofsulfunc aCId-mercunc sulfate-potassIUm sulfate solutlOn (6 3)

7 4 2 Macro Kjeldahl system -

To a 100 ml alIquot, add 15 ml of 10 N NaOH (64), mIX and cool to room

temperature Immerse the electrode In the sample solutlOn and add 4 ml ofNaOHNaI-EDTA reagent (65) while mIXIng Allow the electrode to remaIn immersed In

the solutlOn until a stable readIng IS obtaIned

7 4 3 Micro KJeldahl system

Add 6 ml of 10 N NaOH solutIOn (6 4), cool to room temperature and transfer the

sample to a 100 ml beaker Immerse the electrode In the sample solutlOn and add 4

ml ofNaOH-NaI-EDTA reagent (65) whIle mIXIng Allow the electrode to remaIn

Immersed In the solutIOn untIl a stable readIng is obtaIned

7 4 4 Block Digestor

Add 3 mlof 10 N NaOH (64), cool to room temperature, dIlute to 50 ml and

transfer to a 100 ml beaker Immerse the electrode In the sample and add 2 ml of

NaOH-NaI-EDTA reagent (65) while mIXIng Allow the electrode to remaIn

Immersed In the solutlOn until a stable readIng is obtaIned

8 CalculatIOn

USIng semiloganthmic graph paper, plot the concentratlOn of ammoma In mg NHrN on the

log aXiS vs the electrode potential developed In the standard on the lInear aXIS, startIng WIth the

lowest concentration at the bottom ofthe scale

mg TKN/1 = (A - Bbx 1,000

where

A = mg NH3-N read from standard curve

B = mg NH3-N In blank

C = ml ofongInal sample taken

9 Precision and Accuracy

9 1 PreCISlOn and accuracy data are not available at this time

BIblIography

1 Schlueter, A, "Nitrate Interference In Total KJeldahl Nitrogen DetermInatlOns and itS

Removal by Amon Exchange ResIn", EPA-600/7-77-Q17

3514-3
NITROGEN, NITRATE

Method 352.1 (Colorimetric, Brucine)

STORET NO. Total 00620

I Scope and Apphcatton

I I Thls method lS apphcable to the analysls of dnnkmg, surface and sahne waters, domestlc

and mdustnal wastes Modlficatton can be made to remove or correct for turbldlty, color,

sahmty, or dlssolved orgamc compounds m the sample

1 2 The apphcable range ofconcentratlOns lS 0 1 to 2 mg N03-N/hter

2 Summary ofMethod

2 1 ThlS method lS based upon the reactIOn ofthe mtrate lon wlth brucme sulfate m a 13 N

H2S04 solutlOn at a temperature of 100°C The color ofthe resultmg complex lS measured

at 410 nm Temperature control ofthe color reactlon lS extremely cntical

3 Sample Handhng and Preservation

3 1 Analysls should be made as soon as posslble If analysls can be made wlthm 24 hours, the

sample should be preserved by refngeratlOn at 4°C When samples must be stored for

more than 24 hours, they should be preserved wlth sulfunc aCld (2 ml conc H2S04 per

hter) and refngeratlOn

4 Interferences

4 1 Dlssolved orgamc matter w111 cause an off color m 13 N H2S04 and must be compensated

for by addlttonS of all reagents except the brucme-sulfamhc aCld reagent Thls also

apphes to natural color present not due to dlssolved orgamcs

4 2 The effect ofsahmty lS ehmmated by addltion ofsodlUm chlonde to the blanks, standards

and samples

4 3 All strong oXldlZmg or reducmg agents mterfere The presence of oXldlzmg agents may

be determmed wlth a total resldual chlonne test klt

4 4 Resldual chlonne mterference lS ehmmated by the addltlOn ofsodmm arsemte

4 5 Ferrous and fernc lron and quadnvalent manganese glVe shght posltlve mterferences, but

m concentratlOns less than I mg/1 these are neghglble

46 Uneven heatmg of the samples and standards dunng the reactlOn time w111 result m

erratlc values The necesslty for absolute control oftemperature durmg the cntical color

development penod cannot be too strongly emphaslzed

5 Apparatus

5 1 Spectrophotometer or filter photometersUltable for measunng absorbance at 410 nm

52 Sufficlent number of 40-50 ml glass sample tubes for reagent blanks, standards and

samples

5 3 Neoprene coated Wlre racks to hold sample tubes

5 4 Water bath sUltable for use at 100°C Thls bath should contam a stunng mechamsm so

that all tubes are at the same temperature and should be ofsufficlent capaclty to accept

Approved for NPDES and SDWA

Issued 1971

352 1-1
the reqUIred number oftubes wIthout slgmficant drop m temperature when the tubes are

Immersed

5 5 Water bath sUItable for use at 10-15°C

6 Reagents

6 1 DIstIlled water free of mtrIte and mtrate IS to be used m preparatIOn of all reagents and

standards

62 SodIUm chloride solutIOn (30%) DIssolve 300 g NaCI m dIStilled water and dIlute to 1

lIter

63 SulfUriC aCId SolutIon Carefully add 500 ml conc H2S04to 125 ml dIstIlled water Cool

and keep tIghtly stoppered to prevent absorptIOn ofatmospheric mOIsture

6 4 Brucme-sulfamlIc aCId reagent DIssolve 1 g brucme sulfate

[(C23H26N204)2eH2S04e7H20] and 0 1 g sulfamhc aCId (NH2C6H4S03HeH20) m 70 ml

hot dIstIlled water Add 3 ml conc HCI, cool, mIX and dIlute to 100 ml WIth dIstIlled

water Store m a dark bottle at 5°C ThIS solutIOn IS stable for several months, the pmk

color that develops slowly does not effect ItS usefulness Mark bottle WIth warmng

CAUTION Brucme Sulfate IS tOXIC, take care to aVOId mgestIOn

65 PotaSSIUm mtrate stock solutIOn 10 ml = 0 1mg NOrN DIssolve 07218 g anhydrous

potaSSIUm mtrate (KN03) m dIstIlled water and dIlute to 1 hter m a volumetriC flask

Preserve WIth 2 ml chloroform per hter ThIS SolutIon IS stable for at least 6 months

6 6 PotaSSIUm mtrate standard solutIOn 1 0 ml = 0001 mg N03-N DIlute 10 0 ml of the

stock SolutIon (65) to 1 hter m a volumetriC flask ThIS standard solutIOn should be

prepared fresh weekly

6 7 Acetic aCId (1 + 3) DIlute 1 volume glaCIal acetIC aCId (CH3COOH) WIth 3 volumes of

dIstIlled water

6 8 SodIUm hydrOXIde (IN) DIssolve 40 g of NaOH m dIstIlled water Cool and dIlute to 1

hter

7 Procedure

7.1 Adjust the pH of the samples to approxImately 7 WIth acetIC aCId (6 7) or sodlUm

hydrOXIde (6 8) Ifnecessary, filter to remove turbIdIty

7 2 Set up the reqUIred number of sample tubes m the rack to handle reagent blank,

standards and samples Space tubes evenly throughout the rack to aI10w for even flow of

bath water between the tubes ThIS should aSSIst m achIevmg umform heatmg of all

tubes

7 3 IfIt IS necessary to correct for color or dIssolved orgamc matter whIch wIll cause color on

heatmg, a set of duphcate samples must be run to WhICh all reagents except the brucmesulfamhc aCId have been added

74 PIpette 100 ml ofstandards and samples or an ahquot of the samples dIluted to 10 0 ml

mto the sample tubes

75 If the samples are sahne, add 2 ml of the 30% sodlUm chlOride solutIOn (62) to the

reagent blank, standards and samples For fresh water samples, sodlUm chlOride solutIOn

may be omItted MIX contents of tubes by sWIrlmg and place rack m cold water bath

(O-lO°C)

352 1-2
76 Pipette 10 0 ml ofsulfunc aCid solutIOn (6 3) mto each tube and mix by sWlr1mg Allow

tubes to come to thermal eqUlhbnum m the cold bath Be sure that temperatures have

eqUlhbrated m all tubes before contmumg

77 Add 05 ml brucme-sulfamhc aCid reagent (64) to each tube (except the mterference

control tubes, 7 3) and carefully mix by sWlrhng, then place the rack oftubes m the 100°C

water bath for exactly 25 mmutes

Caution Immersion ofthe tube rack mto the bath should not decrease the temperature of

the bath more than 1 to 2°C In order to keep this temperature decrease to an absolute

mmlmum, flow ofbath water between the tubes should not be restncted by crowdmg too

many tubes mto the rack If color development m the standards reveals discrepancies m

the procedure, the operator should repeat the procedure after revlewmg the temperature

controlsteps

7 8 Remove rack of tubes from the hot water bath and Immerse m the cold water bath and

allow to reach thermal eqUlhbnum (20-25°C)

7 9 Read absorbance agamst the reagent blank at 410 nm usmg a 1cm or longer cell

8 CalculatIOn

8 1 Obtam a standard curve by plottmg the absorbance of standards run by the above

procedure agamst mg NOr N/1 (The color reactIOn does not always follow Beer's law)

8 2 Subtract the absorbance of the sample without the brucme-sulfamhc reagent from the

absorbance of the sample contammg brucme-sulfamhc aCid and determme mg

N03-N/l Multiply by an appropnate dl1utlon factor If less than 10 ml of sample IS

taken

9 PrecIsIOn and Accuracy

9 1 Twenty-seven analysts m fifteen laboratones analyzed natural water samples contammg

exact mcrements ofmorgamc mtrate, with the followmg results

Increment as

Nitrogen, Nitrate

mg N/hter

016

019

108

124

PreCISIOn as

Standard DevI~tlQn

mg N/hter

0092

0083

0245

0214

Bias,

%

-679

+830

+412

+282

Accuracy as

BlaS,

mg Nlllter

-001

+002

+004

+004

(FWPCA Method Study 2, Nutnent Analyses)

BIbliography

1 Standard Methods for the Exammatton of Water and Wastewater, 14th EditIOn, p 427,

Method 419D (1975)

2 Annual Book ofASTM Standards, Part 31, "Water", Standard D 992-71, P 363 (1976)

3 Jenkms, D, and Medsken, L, "A Brucme Method for the Determmatton of Nitrate m Ocean,

Estuarine, and Fresh Waters", Anal Chem , 36, P 610, (1964)

352 1-3
NITROGEN, NITRATE-NITRITE

Method 353.1 (Colorimetric, Automated, Hydrazine Reduction)

STORET NO. Total 00630

1 Scope and ApplicatlOn

1 1 ThIS method IS apphcable to dnnkmg and surface water, and domestIc and mdustnal

wastes The applicable range of thIS method IS 001-10 mg/l mtrate-mtnte mtrogen

ApproXImately 20 samples per hour can be analyzed

2 Summary ofMethod

2 1 NItrate IS reduced to mtnte WIth hydrazme sulfate and the mtnte (that ongmally present

plus reduced mtrate) IS determmed by dlazotlzmg WIth sulfamlamlde and coupling WIth

N-(l-naphthyl)-ethylenedlamme dihydrochionde to form a hIghly colored azo dye

WhICh IS measured colonmetncally

3 Sample Handhng and PreservatlOn

3 1 AnalysIs should be made as soon as possIble If analysIs can be made wlthm 24 hours,

samples should be preserved by refngeratlOn at 4°C When samples must be stored for

more than 24 hours, they should be preserved WIth 2 ml ofsulfunc aCId (H2S04) per hter

and refngerated

4 Interferences

4 1 Sample color that absorbs m the photometnc range used for analysIs WIll mterfere

42 The apparent N03 and N02 concentratlOns vaned ±10 percent WIth concentratlOns of

sulfide lOn up to 10 mg/l

5 Apparatus

5 1 Sampler

5 2 Mamfold AAI or AAII

5 3 Proportlomng Pump

5 4 Heatmg bath 32°C AAI or 37°C AAII

5 5 Contmuousfilter

5 6 Colonmeter eqUipped WIth an 8 mm, 15 mm or 50 mm flow cell and 529 nm filters

6 Reagents

6 1 Color developmg reagent To approxImately 500 ml of dlstl1led water add 200 ml

concentrated phosphonc aCId (sp gr I 834), 10 g sulfamiamide (H2NCJI~02NH2)

followed by 08 g N (I-Naphthyl) ethylenedlamme dihydrochionde Dl1ute the solutlOn

to 1 hter WIth dIstl1led water and store m a dark bottle m the refngerator ThIS solutlOn IS

stable for approxImately 1month

6 2 Copper sulfate stock solutlOn DIssolve 2 5 g of copper sulfate (CuS04-SH20) m

dIst111ed water and dl1ute to 1hter

Approved for NPDES and SDWA

Issued 1971

ReIssued WIth reVISIon 1978

353 1-1
6 3 Coppersulfate dIlute solutIOn DIlute 20 ml ofstock solutIOn (6 2) to 2 hters with distilled

water

6.4 SodIUm hydroxide stock solutIOn, (ION) Dissolve 400 g NaOH m 750 ml dlstl1led water,

cool and dIlute to 1 hter

65 SodIUm hydroxide (1 ON) Dilute 100 ml ofstock NaOH solutIOn (64) to 1 hter

6 6 Hydrazme sulfate stock solutIOn Dissolve 27 5 g of hydrazme sulfate (NzH4-HzS04) m

900 ml of dtstIlled water and dtlute to 1 hter ThiS solutton IS stable for approXimately 6

months CAUTION TOXIC tfmgested Mark contamer with appropnate warnmg

6 7 Hydrazme sulfate dtlute solution

671 AAI Dtlute 55 ml ofstock solution (66) to lItter

672 AAII DIlute 22 ml ofstock solutIOn (66) to 1 lIter

68 Stock mtrate solution (100 mg/1 N03-N) Dtssolve 07218 g of KN03, oven dned at

100-105°C for 2 hours, m distIlled water and dIlute to 1 hter Add 1 ml chloroform as a

preservattve Stable for 6 months 1ml = 0 1mg N

6.9 Stock nitnte solutton (100 mg/1 NOz-N) Dtssolve 0 6072 g KNOz m 500 ml of distIlled

water and dtlute to 1 hter Preserve with 2 ml ofchloroform and keep under refngeratlon

1ml =0 1mgN

6 10 Standard mtrate solutIOn Dilute 100 ml ofstock mtrate solutton (6 8) to 1 hter 1 ml =

001 mgN

6 11 Usmg the stock mtrate solution (68), prepare the followmg standards m 100 ml

volumetnc flasks At least one mtnte standard should be compared to a mtrate standard

at the concentratIOn to venfy the effiCiency ofthe reductIOn

Cone, mg N03-NII

05

10

20

30

40

50

80

100

ml of stock solutIon/100 ml

05

10

20

30

40

50

80

100

Forstandards m the range of0 01 mg/1 use the standard mtrate solutIOn

7. Procedure

7.1 Set up the mamfold as shown m Ftgure 1 (AAI) or Figure 2 (AAII) The contmuous

filter must be used to remove the precipitate

7 2 Allow both colonmeter and recorder to warm up for 30 mmutes Obtam a stable basehne

with all reagents, feedmg dIstilled water through the sample hne

7 3 Run a 2 0 mg/1 N03-N and a 20 mg/1 NOz-N standard through the system to check for

100% reduction ofmtrate to mtnte The two peaks should be of equal height Ifthey are

not, the concentratIOn ofthe hydrazme sulfate solutIOn must be adjusted as follows Ifthe

N03 peak IS lower than that of the NOz peak the concentration of hydrazme sulfate

should be mcreased unttl they are equal If the N03 peak IS hlgher than the mtnte, the

concentration of the hydrazme sulfate should be reduced When the correct

353 1-2
concentratiOn of hydrazme sulfate has been determmed, no further adjustment should be

necessary

7 4 Place appropnate mtrate standards m the sampler m order of decreasmg concentratiOn

ofmtrogen Complete loadmg tray wIth unknown samples

7 5 For both the AAI and theAAII use a 2 mmute samphng rate

8 CalculatiOn

8 1 Prepare a standard curve by plottmg peak heIghts ofprocessed standards agamst known

concentratiOns Compute concentratiOns ofsamples by companng sample peak heIghts

wIth the standard curve

9 PreclSlon and Accuracy

9 1 In a smgle laboratory usmg dnnkmg water, surface water and mdustnal waste at

concentratiOns of 039, 1 15, 1 76 and 475 ug NOr N/l, the standard devIations

were ±O 02, ±O 01, ±O 02 and ±O 03, respectIvely In a smgle laboratory usmg dnnkmg

water at concentratiOns of0 75 and 297 the recovenes were 99% and 101%

BIblIography

1 Kamphake, L , Hannah, S , and Cohen, J , "Automated AnalysIs For NItrate by Hydrazme

ReductiOn", Water Research 1,205 (1967)

353 1-3
AI

ER

MI/Min ,I

YEllOW 1.2 OIST. H20 TO SAMPL

SMC GREEN 2.0 OIST H2O

txx> GRAY 10 SAMPLE

GREEN 20 OIST H2O

YELLOW 1 2 AIR

BLACK 032 lN NoOH

I--

BLUE 16 SAMPLE WASTE a::

w 10ft ./ WASTE I-

....

" ORANGE 042 I SAMPLE u.

18 SMC

-()(X) BLUE 16 OIST H2O

BLACK 032 Cu REAGENT

YELLOW 12 AIR

HEATING BATH BLACK 032 HYORAZINE REAGENT

BLACK o 32 COLOR REAGENT

§ BLUE 16 WASTE

PROPORTIONING

PUMP

,Jt D 2 MIN SAMPLE

FIGURE 1 AUTOMATED HYDRAZINE +0 1-6' REDUCTION METHOD, MANIFOLD 1 A

u

=E....

lH

VI

lH

.-

J

.j>,.

COLORIMETER RECORDER

...!...mm TUBULAR fie

520 nm FILTERS
I:ll:

LU

MPLER

GENT

T

AA II

MI/Mm I

GRAY 10 OIST H20 TO SA

20 TURNS 116-0489 BLACK 032 AIR

157-B089 I REO 080 1N NoOH -XX- Xx... I ORANGE WHITE 023 SAMPLE

GRAY 10 OIST H2O

YELLOW 12 SAMPLE WASTE

20 TURNS 116-0489 BLACK 032 AIR ATING

.ATH 157-BO!.9_ A 10 I BLACK 032 Cu REAGENT

~:3 -XY:' J..JJ I BLACK 032 SAMPLE

BLACK 032 HYORAZINE RI

ORANGE 032 OIST H2O

ORANGE WHITE

A-10 032 COLOR REAGE

>< GRAY 10 WASTE

PROPORTIONING

PUMP

.Jt 0 SAMPLE 20/hr 21

*GLASS TUBING

t~ 11 FIGURE 2 AUTOMATED HYDRAZINI

REDUCTION METHOD, MANIFOLD 2

COLORIMETER RECORDER

15mm FLOW CELL_mm TUBULAR f/c

520nm FILTER_m,u FILTERS

H

w

Ul

W

-I

Ul
NITROGEN, NITRATE-NITRITE

Method 353.2 (Colorimetric, Automated, Cadmium Reduction)

STORET NO. Total 00630

1 Scope and ApphcatIOn

1 1 ThIS method pertains to the determinatIOn of nItnte singly, or nItnte and nItrate

combined in surface and sahne waters, and domestIC and industnal wastes The

apphcable range of thIS method IS 0 05 to 10 0 mg/l nItrate-nItnte nItrogen The range

may be extended wIth sample dIlutIOn

2 Summary ofMethod

2 1 A filtered sample IS passed through a column contaming granulated copper-cadmIUm to

reduce nItrate to nItnte The nItnte (that onginally present plus reduced nItrate) IS

determmed by dIaZOtiZing wIth sulfanIlamIde and couphng wIth N-(1-naphthyl)-

ethylenedIamine dihydrochionde to form a hIghly colored azo dye whIch IS measured

colonmetncally Separate, rather than combmed nItrate-nItnte, values are readIly

obtained by carrymg out the procedure first wIth, and then without, the Cu-Cd reductIOn

step

3 Sample Handhng and PreservatIOn

3 1 AnalysIs should be made as soon as pOSSible IfanalySIS can be made withm 24 hours, the /

sample should be preserved by refngeratIOn at 4°C When samples must be stored for

more than 24 hours, they should be preserved wIth sulfunc aCId (2 ml conc H2S04 per

hter) and refngeratIOn

CautIOn Samplesfor reductIOn column must not be preserved wIth mercunc chlonde

4 Interferences

4 1 BuIld up of suspended matter m the reductIOn column WIll restnct sample flow Smce

nItrate-nItrogen IS found in a soluble state, the sample may be pre-filtered

4 2 Low results might be obtained for samples that contam hIgh concentratIOns of Iron,

copper or other metals EDTA IS added to the samples to ehmmate thIS mterference

4 3 Samples that contain large concentratIons of oIl and grease WIll coat the surface of the

cadmIUm ThIs mterference IS ehmmated by pre-extracting the sample wIth an organIc

solvent

5 Apparatus

5 1 TechnIcon AutoAnalyzer (AAI or AAII) conSIsting ofthe fohowing components

5 11 Sampler

5 1 2 ManIfold (AAI) or analytIcal cartndge (AAII)

5 1 3 ProportionIng Pump

5 1 4 Colonmeter eqUIpped wIth a 15 mm or 50 mm tubular flow cell and 540 nm filters

5 1 5 Recorder

Approved for NPDES and SDWA

Issued 1971

Editonal reVISIon 1974 and 1978

3532-1
5 I 6 DIgItal pnnter for AAII (OptIOnal)

6. Reagents

6 I Granulated cadmIUm 40-60 mesh (MCB Reagents)

6 2 Copper-cadmIUm The cadmIUm granules (new or used) are cleaned wIth dIlute HCI

(67) and coppenzed wIth 2% solutIOn ofcoppersulfate (6 8) In the follOWIng manner

621 Wash the cadmIUm wIth HCI (6 7) and nnse wIth dIstIlled water The color ofthe

cadmIum so treated should be sIlver

622 SWlr1lO g cadmIUm In 100 ml portIOns of 2% solutIOn of copper sulfate (6 8) for

five mInutes or untIl blue color partIally fades, decant and repeat WIth fresh copper

sulfate untIl a brown collOIdal preCIpItate forms J. J..r "

623 Wash the cadmIUm-copper WIth dI~tIlled water (at least 10 times) to remove all the

precipItated copper The color ofthe ~admIUm so treated should be black

6.3 PreparatIOn ofreductIOn column AAI The reductIOn column IS an 8 by 50 mm glass tube

With the ends reduced In diameter to permIt InSertIOn Into the system Copper-cadmIUm

granules (6 2) are placed In the column between glass wool plugs The packed reductIOn

column IS placed In an up-flow 20° InclIne to mInlIIllZe channelIng See Figure 1

64 PreparatIon of reductIOn column AAII The red~ction column IS a V-shaped, 35 cm ,'li' Ij. I " I' G

length, 2 mm I D glass ~ube (NQte 1) Fill the reductIOn column WIth dIstIlled water to

prevent entrapment of air bubbles dunng the fillIng operatIons Transfer the coppercadmIUm granules (6 2) t~ the reductIon column and place a glass wool plug In each end

To prevent ent"rapment ofair bubbles In the reductIOn column be sure that all pump tubes

are filled With reagents before puttIng the column Into the analytIcal system

NOTEi: A 0081 I D pump tube (purple) can be used In place ofthe 2 mm glass tube

6 5 DIstIlled water Because of pOSSible contamInatIOn, thIS should be prepared by passage

through an IOn exchange column compnsed of a mIxture of both strongly aCIdIc-catIon

and strongly baslc-amon exchange reSInS The regeneratIOn of the IOn'exchange column

should be carned out accordIng to the manufacturer's InstructIons

6.6 Color reagent To apprOXImately 800 ml of dIstIlled water, add, whIle stlrnng, 100 ml

conc phosphonc aCid, 40 g sulfamlamlde, and 2 g N-1- naphthylethylenediamIne

dlhydrochlonde St~pP-,tIl dlssolyed and dIlute to 1 lIter Store In brown bottle and keep

In the dark when not In use ThIS solutIon IS stable for several months

6.7 DIlute hydrochlonc aCId, 6N DIlute 50 ml ofconc HCI to 100 ml WIth distIlled water

68 Copper sulfate solutIon, 2% DIssolve 20 g of CuS04-5HzO In 500 ml of distIlled water

and ddute to 1 lIter

6 9 Wash solution Vse distIlled water for unpreserved samples For samples preserved With

H2S04, use 2 m1 HzSO.4 pel'lIter ofwash water

6 10 AmmonIUm: ~hionde-Eb"~A ~,plutI~~ PI~solye, 85 i of reagent grade ammomum

chlonde and 0 1 g of dlsodIUm ethylenedIamIne tetracetate In 900 ml of distIlled water

Adjust the pH to 8 5 WIth conc ammomum hydroxIde and dIlute to 1 lIter Add 1/2 ml

BnJ-35 (avaIlable from Techmcon CorporatIon)

I

3532-2
FLOW

INDENTATIONS FOR

SUPPORTING CATALYST

~/

GLASS WOOL

Cd·TURNINGS

TILT COLUMN TO 20° POSTION

FIGURE 1. COPPER CADMIUM REDUCTION COLUMN

(1 1/2 ACTUAL SIZE]

3532-3
6 II, Stock mtrate solutIOn DIssolve 7 218 g KN03 and dIlute to 1 lIter m a volumetnc flask

wIth dIstilled water Preserve wIth 2 ml of chloroform per lIter SolutIon IS stable for 6

months 1ml = 1 0 mg N03-N

6 12 Stock mtnte SolutIon DIssolve 6 072 g KN02 m 500 ml of dIstilled water and dIlute to 1

lIter m a volumetnc flask Preserve wIth 2 ml ofchloroform and keep under refngeratIOn

1 OmI = 10mgN02-N

6 13 Standard mtrate SolutIon DIlute 10 0 ml ofstock mtrate solutIOn (6 11) to 1000 ml

10 ml = 001 mg NOrN Preserve wIth 2 ml ofchloroform per hter SolutIOn IS stable

for 6 months

6 14 Standard mtnte SolutIon DIlute 100 ml ofstock mtnte (6 12) solution to 1000 ml

10m! = 001 mg N02-N SolutIOn IS unstable, prepare as reqUIred

6 15 Usmg standard mtrate SolutIon (6 13), prepare the followmg standards m 1000 ml

volumetnc flasks At least one mtnte standard should be compared to a mtrate standard

at the same concentratIon to venfy the effiCIency ofthe reductIOn column

00

005

010

020

050

100

200

400

600

ml Standard SolutIOnllOO ml

o

05

10

20

50

100

200

400

600

NOTE 2' When the samples to be analyzed are salIne waters, Substitute Ocean Water

(SOW).should be used for prepanng the standards, otherWIse, dIstilled water IS used A

tabulatIOn ofSOW compOSItion follows

NaCI - 24 53 gil

CaCl2 - 116 gil

KBr - 010 gil

NaF - 0 003 gil

MgCl2 - 5 20 gil

KCI - 070 gil

H3B03 - 0 03 gil

Na2S04 - 409 gil

NaHC03 - 0 20 gil

SrCl2 - 0 03 gil

7 Procedure

7 1 Ifthe pH ofthe sample IS below 5 or above 9, adjust to between 5 and 9 WIth eIther conc

HClorconc NH40H

7 2 Set up the mamfold as shown m FIgure 2 (AAI) or FIgure 3 (AAII) Note that reductant

column should be m 200mclme pOSItIOn (AAI) Care should be taken not to mtroduce aIr

mto reductIOn column on the AAII

7 3 Allow both colonmeter and recorder to warm up for 30 mmutes Obtam a stable baselIne

WIth all reagents, feedmg dIstilled water through the sample lme

NOTE 3: CondItIon column by runnmg 1 mgll standard for 10 mmutes If a new

reductIon column IS bemg used Subsequently wash the column WIth reagents for 20

mmutes

3532-4
7 4 Place appropnate mtrate and/or mtnte standards m sampler m order of decreasmg

concentratiOn ofmtrogen Complete loadmg ofsampler tray wIth unknown samples

7 5 For the AAI system, sample at a rate of 30/hr, 1 1 For the AAII, use a 4O/hr, 4 1 cam

and a common wash

7 6 SWItch sample hne to sampler and start analysIs

8 Calculations

8 1 Prepare appropnate standard curve or curves denved from processlllg NOz and/or N03

standards through mamfold Compute concentratiOn of samples by companng sample

peak heIghts wIth standard curve

9 PrecISiOn and Accuracy

9 1 Three laboratones partlcipatlllg III an EPA Method Study, analyzed four natural water

samples contallllllg exact lllcrements ofmorgamc mtrate, wIth the followlllg results

Increment as

NItrate NItrogen

mg N/hter

029

035

231

248

PreCiSIOn as

Standard DeViatIOn

mg N/hter

0012

0092

0318

0176

Blbhography

BIas,

%

+ 575

+1810

+ 447 - 269

Accuracy as

BIas,

mg N/hter

+0017

+0063

+0103

-0067

1 Flore, J , and O'Bnen, J E, "AutomatiOn III Samtary ChemIstry - parts 1 & 2 DetermlllatiOn

ofNItrates and Nitntes", Wastes Engllleenng 33, 128 & 238 (1962)

2 Armstrong, FA, Steams, C R, and Stnckland, J D, "The Measurement of Upwelhng and

Subsequent BiOlogIcal Processes by Means of the Techmcon AutoAnalyzer and ASSOCIated

EqUlpment", Deep Sea Research 14, p 381-389 (1967)

3 Annual Book ofASTMStandards, Part 31, "Water", Standard D1254, p 366 (1976)

4 ChemIcal Analyses for Water Quahty Manual, Department of the Intenor, FWPCA, R A

Taft Samtary Engllleenng Center Trallllllg Program, Cmclllnatl, OhIO 45226 (January, 1966)

5 Annual Book of ASTM Standards, Part 31, "Water", Standard D 1141-75, SubstItute Ocean

Water, p48 (1976)

3532-5
w

Ul

W

0\

Run EXPANDER

FIGURE 2. NITRATE - NITRITE MANIFOLD AA-I

FnLtl ,'-

AMPLER 2

30 PER HR

USE

E TUBING

COLUMN

POSITION
TO SAMPLER

WASTE TO 0.6 ml/mm

032 AIR

-...-

BLACk

-- A2 1fVVY\ Y Y 12 AMMONIUM

CHLORIDE

BLACK 032 SAMPLE _ .'ION.

0

.~--- , COLUMN

.

-

J

032 AIR

ASTE ,

SAMPLER

BLACK

40/hr

1

D 41 ;> nrvvYI(J- .......

'""--WASTE TOLD

BLACK 0.32 COLOR

hs

REAGENT

0 .... DIIUD TilDE

W 06

WASTE

W

GREY 10. WASTE

- G G 20 WASH

--

w

VI

W

tv D

p

PROPORTIONING

PUMP

FI GURE 3 NITRATE-NITRITE MANI FOLD AA II
NITROGEN, NITRATE-NITRITE

Method 353.3 (Spectrophotometric, Cadmium Reduction)

STORET NO. Total 00630

1 Scope and ApphcatlOn

1 1 Th1s method 1S apphcable to the determmatlOn of mtnte smgly, or mtnte and mtrate

combmed m drmkmg, surface and sahne waters, domest1c and mdustnal wastes The I

apphcable range of th1s method 1S 001 to 10 mg/l mtrate-mtnte mtrogen The range

may be extended w1th sample dl1utlOn

2 Summary ofMethod

2 1 A filtered sample 1S passed through a column contam~ng granulated copper-cadmmm to

reduce mtrate to mtnte The mtnte (that ongmally present plus reduced mtrate) 1S

determmed by d1azot1zmg w1th sulfamlam1de and couphng w1th N-(l-naphthyl)-

ethylened1amme d1hydrochlonde to form a h1ghly colored azo dye wh1ch 1S measured

spectrophotometncally Separate, rather than combmed mtrate-mtnte, values are readl1y

obtamed by carrymg out the procedure first w1th, and then w1thout, the Cu-Cd reductlOn

step

3 Sample Handlmg and PreservatlOn

3 1 Analys1s should be made as soon as poss1ble If analys1s can be made w1thm 24 hours, the

sample should be preserved by refngeratlOn at 4°C When samples must be stored for

more than 24 hours, they should be preserved w1th sulfunc aC1d (2 ml H2S04 per hter)

and refngeratlOn

CautlOn Samples for reduct10n column must not be preserved w1th mercunc chlor1de

4 Interferences

4 1 Bul1d up of suspended matter m the reductlOn column w1ll restnct sample flow Smce

mtrate-mtrogen 1S found m a soluble state, the sample may be pre-filtered through a glass

fiber filter or a 0 45u membrane filter H1ghly turb1d samples may be pretreated w1th zmc

sulfate before filtratlOn to remove the bulk ofpart1culate matter present m the sample

4 2 Low results m1ght be obtamed for samples that contam h1gh concentratlOns of 1ron,

copper or other metals EDTA 1S added to the samples to ehmmate th1s mterference

4 3 Samples that contam large concentrat10ns of 011 and grease w1ll coat the surface of the

cadmmm Th1s mterference 1S ehmmated by pre-extractmg the sample w1th an orgamc

solvent

4 4 Th1s procedure determmes both mtrate and mtnte If only mtrate 1S des1red, a separate

determmatlOn must be made for mtnte and subsequent correctlOns made The mtnte

may be determmed by the procedure below w1thout the reductlOn step

Approved for NPDES and SDWA

Issued 1974

353 3-1
5. Apparatus

5 1 ReductIOn column The column m FIgure I was constructed from a 100 ml pIpet by

removmg the top portIon ThIS column may also be constructed from two pIeces of

tubmg Jomed end to end A 10 mm length of 3 cm I D tubmg IS Jomed to a 25 cm length

of3 5 mm I D tubmg

5 2 Spectrophotometer for use at 540 nm, provIdmg a lIght path of 1 cm or longer

6. Reagents

6.1 Granulated cadmIUm 40-60 mesh (MCB Reagents)

6 2 Copper-CadmIUm The cadmIUm granules (new or used) are cleaned wIth dIlute HCl and

coppenzed wIth 2% solutIOn ofcopper sulfate m the followmg manner

62 1 Wash the cadmIUm wIth dIlute HCl (6 10) and nnse wIth dlstIlled water The color

ofthe cadmIUm should be sIlver

6 2 2 SWIrl 25 g cadmIUm m 100 ml portIOns ofa 2% solutIOn ofcopper sulfate (6 11) for

5 mmutes or untIl blue color partIally fades, decant and repeat wIth fresh copper

sulfate untIl a brown collOIdal preCIpItate forms

623 Wash the copper-cadmIUm WIth dIstIlled water (at least 10 tImes) to remove all the

precIpItated copper The color ofthe cadmIUm so treated should be black

63 PreparatIon ofreactIOn column Insert a glass wool plug mto the bottom ofthe reductIOn

column and fill WIth dIstIlled water Add suffiCIent copper-cadmIUm granules to produce

a column 18 5 cm m length Mamtam a level of dIstIlled water above the coppercadmIum granules to elImmate entrapment ofaIr Wash the column WIth 200 ml ofdIlute

ammOnIum chlonde solutIOn (65) The column IS then actIvated by passmg through the

column 100 ml ofa solutlOn composed of 25 m1 of a 1 0 mg/l N03-N standard and 75 ml

of ammOnIum chlonde - EDTA solutIOn (6 4) Use a flow rate between 7 and 10 ml per

minute

6.4 AmmOnIum chlonde - EDTA solutIon DIssolve 13 g ammOnIum chlonde and 1 7 g

disodIUm ethyienediamme tetracetate m 900 ml of dIstIlled water Adjust the pH to 8 5

with cone ammOnIum hydroxIde (6 9) and dIlute to 1lIter

65 DIlute ammOnIum chlonde-EDTA solutIOn DIlute 300 ml ,of ammonIUm chlondeEDTA solutIOn (6 4) to 500 ml WIth dIstIlled water

66 Color reagent DIssolve 10 g suifamiamide and 1 g N(l-naphthyl)-ethylene-diamme

dlhydrochlonde m a mixture of 100 ml conc phosphonc aCid and 800 m1 of distIlled

water and dIlute to 1lIter With distilled water

67 Zmc sulfate solution Dissolve 100 g ZnS04-7H20 m distIlled water and dIlute to 1 lIter

6 8 Sodium hydroxide sohitIOn, 6N Dissolve 240 g NaOH m 500 ml distIlled water, cool and

dIlute to 1 lIter

6 9 AmmonIum hydroxide, conc

6 10 DIlute hydrochlonc aCid, 6N Dilute 50 JIll ofconc HCI to 100 ml WIth distIlled water

6 11 Copper sulfate solutlOn, 2% DIssolve 20 g of CuS04-5H20 m 500 ml of distIlled water

and dIlute to 1 lIter

6 12 Stock mtrate solution Dissolve 7 218 g KN03 m distilled water and dIlute to 1000 ml

Preserve With 2 ml of chloroform per lIter ThiS solutlOn IS stable for at least 6 months I

1 Oml = l00mgN03-N '

3533-2
80-85 ml

~3cm 10

IDem

2cm"

+

25cm

185cm

o(+--Cu/cd

FIGURE 1. REDUCTION COLUMN

3533-3
6.13 Standard nItrate solutlOn DIlute 10 0 ml of nItrate stock solutlOn (612) to 1000 ml wIth

dIstilled water 1 0 ml = 001 mg N03-N

6.14 Stock nItrIte solutIon DISsolve 6072 g KN02 In 500 ml of dIstilled water and dIlute to

1000 ml Preserve wIth 2 ml of chloroform and keep under refngeratlOn Stable for

approXlmately 3 months 1 0 ml = 1 00 mg N02-N

6 15 Standard nItnte solutlOn DIlute 10 0 ml ofstockpitnte solutlOn (6 14) to 1000 ml wIth

dIstilled water 1 0 ml = 001 mg N02-N

6 16 USing standard nItrate solutlOn (613) prepare the followmg standards m 100 ml

volumetnc flasks

Cone, mg-N03-NII

000

005

010

020

050

100

ml of Standard SolutlOn/100 0 ml

00

05

10

20

50

100

7 Procedure

7 1 TurbIdIty removal One of the followmg methods may be used to remove suspended

matter

7 1 1 FIltersample through a glass fiber filter or a 0 45u membrane filter

71.2 Add 1 ml ZinC sulfate solutlOn (6 7) to 100 ml ofsample and mIX thoroughly Add

04-05 ml sodIUm hydroXide solutlOn (6 8) to obtain a pH of 10 5 as determined

WIth a pH meter Let the treated sample stand a few minutes to allow the heavy

flocculent preCIpItate to settle Clanfy by filtenng through a glass fiber filter or a

o45u membrane filter

72 Oil and grease removal Adjust the pH of 100 ml of filtered sample to 2 by addItion of

cone HCI Extract the oil and grease from the aqueous solution WIth two 25 ml portlOns

ofa non-polarsolvent (Freon, chloroform or eqUIvalent)

7.3 Ifthe pH ofthe sample IS below 5 or above 9, adjust to between 5 and 9 WIth eIther cone

HCI or conc NRtOH ThIS IS done to Insure a sample pH of 8 5 after step 7 4

7.4 To 25 0 ml ofsample or an ahquot diluted to 25 0 ml, add 75 ml of ammOnIum chlondeEDTA solutlOn (6 4) and mIX

7.5 Poursample Into column and collectsample at a rate of7-10 ml per mmute

7 6 DIscard the first 25 ml, collect the rest of the sample (approxImately 70 ml) m the

ongmal sample flask Reduced samples should not be allowed to stand longer than 15

mmutes before addItIon ofcolor reagent, step 7 7

77 Add 20 ml of color reagent (66) to 500 ml of sample Allow 10 mmutes for color

development Withm 2 hours measure the absorbance at 540 nm agamst a reagent blank

NOTE: Ifthe concentratlOn ofsample exceeds 1 0 mg N03-N/1, the remamder of the

reduced sample may be used to make an appropnate dilutlOn before proceedmg WIth step

77

3533-4
7 8 Standards Carry out the reductlOn ofstandards exactly as descnbed for the samples At

least one mtnte standard should be compared to a reduced mtrate standard at the same

concentratlOn to venfy the efficIency ofthe reductIon column

8 CalculatlOn

8 1 Obtam a standard curve by plottmg the absorbance of standards run by the above

procedure agamst NOrN mg/l Compute concentratlOn of samples by companng

sample absorbance wIth standard curve

8 2 Ifless than 25 ml ofsample IS used for the analysIs the followmg equatIon should be used

A x 25

mgN02 + N03 - Nil = ml sample used

where

A = ConcentratlOn ofmtrate from standard curve

9 PrecIslOn and Accuracy

9 1 In a smgle laboratory (EMSL), usmg sewage samples at concentratlOns of0 04, 0 24, 055

and 1 04 mg N03 + N02-N/l, the standard devIatlOns were ±O 005, ±O 004, ±O 005

and _±O 01, respectIvely

92 In a smgle laboratory (EMSL), usmg sewage samples at concentratIons of0 24, 055, and

1 05 mg N03 + N02-N/l, the recovenes were 100%, 102% and 100%, respectIvely

BIblIography

1 Standard Methods for the ExammatlOn of Water and Wastewater, 14th EdItIon, p 423,

Method 419C (1975)

2 Hennkson, A , and Selmer-Olsen, "AutomatIc Methods for Determmmg NItrate and Nitnte m

Water and SOlI Extracts" Analyst, May 1970, Vol 95, P 514-518

3 Grasshoff, K, "A SImultaneous Multiple Channel System for Nutnent AnalysIs m Sea Water

wIth Analog and DIgItal Data Record", "Advances m Automated AnalysIs", Techmcon

InternatlOnal Congress, 1969, Vol 11, P 133-145

4 Brewer, P G, RIley, J P, "The AutomatIc DetermmatlOn ofNItrate m Sea Water", Deep Sea

Research, 1965, Vol 12, p 765-772

3533-5
NITROGEN, NITRITE

Method 354.1 (Spectrophotometric)

STORET NO. Total 00615

1 Scope and ApplIcatIOn

1 1 This method is applIcable to the determmatIOn of mtnte m dnnkmg, surface and salIne

waters, domestic and mdustnal wastes

1 2 The method is applIcable m the range from 0 01 to 1 0 mg N02-N/1

2 Summary ofMethod

2 1 The diazomum compound formed by diazotatIOn of sulfamlamide by mtnte m water

under aCid conditions is coupled with N-(l-naphthyl)-ethylenediamme dihydrochlonde

to produce a reddish-purple color which is read m a spectrophotometer at 540 nm

3 Sample HandlIng and PreservatIOn

3 1 Samples should be analyzed as soon as possible They may be stored for 24 to 48 hours at

4°C

4 Interferences

4 1 There are very few known mterferences at concentratIOns less than 1,000 times that of

the mtnte, however, the presence of strong oXidants or reductants ill the samples w111

readily affect the mtnte concentratIOns High alkalImty (> 600 mg/1) will give low

results due to a shift m pH

5 Apparatus

5 1 Spectrophotometer eqUipped with 1 cm or larger cells for use at 540 nm

5 2 Nessler tubes, 50 ml or volumetnc flasks, 50 ml

6 Reagents

6 1 Distl1led water free of mtnte and mtrate is to be used m preparatIOn of all reagents and

standards

6 2 Buffer-color reagent To 250 ml of distilled water, add 105 ml conc hydrochlonc aCid,

50 g sulfamlamide and 05 g N-(1-naphthyl) ethylenediamme dihydrochlonde Stir untl1

dissolved Add 136 g of sodmm acetate (CH3COONa-3H20) and agam stir untl1

dissolved Dl1ute to 500 ml with distl1led water ThiS solutIOn is stable for several weeks if

stored m the dark

6 3 Nitnte stock solutIOn 1 0 ml = 0 10 mg N02-N Dissolve 0 1493 g of dned anhydrous

sodmm mtnte (24 hours m deSiccator) m distilled water and dl1ute to 1000 ml Preserve

with 2 ml chloroform per lIter

6 4 Nitnte standard solutIOn 1 0 ml = 0001 mg N02-N Dl1ute 10 0 ml of the stock

solutIOn (6 3) to 1000 ml

7 Procedure

7 1 Ifthe sample has a pH greater than 10 or a total alkalImty m excess of 600 mg/1, adjust

to approximately pH 6 with 1 3 HCI

Approved for NPDES

Issued 1971

354 1-1
7.2 If necessary, filter the sample through a 0 45 u pore SIze filter USing the first portlOn of

filtrate to nnse the filter flask

7 3 Place 50 ml ofsample, or an ahquot dl1uted to 50 ml, in a 50 ml Nessler tube, hold untIl

preparatlOn ofstandards IS completed

7 4 At the same tIme prepare a senes ofstandards in 50 ml Nessler tubes as follows

ml of Standard SolutiOn

10 ml = 0001 mg N02-N

00

05

10

15

20

30

40

50

100

Cone, When Dtluted to

50 ml, mg/l of N02-N

(Blank)

001

002

003

004

006

008

010

020

75 Add 2 ml ofbuffer-color reagent (6 2) to each standard and sample, mIX and allow color

to develop for at least 15 minutes The color reactlOn medmm should be between pH 1 5 '

and 2 0

7.6 Read the color in the spectrophotometer at 540 nm agamst the blank and plot

concentratlOn ofN02-Nagamst absorbance

8. CalculatIon

8 1 Read the concentratlOn ofN02-N duectly from the curve

82 Ifless than 50 0 ml ofsample IS taken, calculate mg/l as follows

NO N II _ mg/l from std curve X 50 2 - ,mg - ml sample used

9 PreCISIon and Accuracy

9 1 PrecIsIon and Accuracy data are not aval1able at thIS time

BIblIography

1 Standard Methods for the ExammatlOn for Water and Wastewater, 14th EditlOn, p 434,

Method 420, (1975)

3541-2
OXYGEN, DISSOLVED

Method 360.1 (Membrane Electrode)

STORET NO. 00299

1 Scope and ApphcatlOn

lIThe probe method for dIssolved oxygen IS lecommended for those samples contammg

materIals WhICh mterfere wIth the modlfied Wmkler procedure such as sulfite,

thIosulfate, polythlOnate, mercaptans, free chlorme or hypochlorIte, orgamc substances

readl1y hydrolyzed m alkahne solutIOns, free IOdme, mtense color or turbIdIty and

bIOlogIcal flocs

1 2 The probe method IS recommended as a substltute for the modIfied Wmkler procedure m

momtormg of streams, lakes, outfalls, etc, where It IS desIred to obtam a contmuous

record ofthe dIssolved oxygen content ofthe water under observatIOn

1 3 The probe method may be used as a SubstItute for the modIfied Wmkler procedure m

BOD determmatlOns where It IS deslred to perform nondestructIve DO measurements on

a sample

1 4 The probe method may be used under any CIrcumstances as a SubstItute for the modIfied

Wmkler procedure provIded that the probe Itself IS standardIzed agamst the Wmkler

method on samples free ofmterfermg materIals

1 5 The e1ectromc readout meter for the output from dIssolved oxygen probes IS normally

cahbrated m convement scale (0 to 10, 0 to 15, 0 to 20 mg/1 for example) wIth a

sensItIvIty ofapproxImately 0 05 mg/hter

2 Summary ofMethod

2 1 The most common mstrumenta1 probes for determmatlOn of dIssolved oxygen m water

are dependent upon electrochemIcal reactIons Under steady-state condItIOns, the

current or potentIal can be correlated With DO concentratIOns InterfacIal dynamIcs at

the probe-sample Interface are a factor m probe response and a sIgmficant degree of

InterfacIal turbulence IS necessary For preClSlon performance, turbulence should be

constant

3 Sample Handlmg and PreservatIOn

3 1 See 4 1,4 2, 4 3,44 under ModIfied Wmkler Method (3602)

4 Interferences

4 1 DIssolved orgamc materIals are not known to Interfere m the output from dIssolved

oxygen probes

4 2 Dlssolved morgamc salts are a factor m the performance ofdIssolved oxygen probe

4 2 1 Probes WIth membranes respond to partial pressure of oxygen whIch m turn IS a

functIOn of dIssolved morgamc salts ConversIOn factors for seawater and brackIsh

waters may be calculated from dIssolved oxygen saturatIOn versus sahmty data

ConversIOn factors for specIfic morgamc salts may be developed experImentally

Approved for NPDES

Issued 1971

3601-1
Broad vanatlOns m the kmds and concentrations ofsalts m samples can make the

use ofa membrane probe dIfficult

4 3 ReactIve compounds can mterfere wIth the output or the performance of dIssolved

oxygen probes

4 3 1 Reactive gases whIch pass through the membrane probes may mterfere For

example, chlonne WIll depolanze the cathode and cause a hIgh probe-output

Long-term exposures to chlonne WIll coat the anode wIth the chlonde ofthe anode

metal and eventually desenSItIze the probe Alkalme samples m WhICh free chlonne

does not eXIst WIll not mterfere Hydrogen sulfide wIll mterfere wIth membrane

probes Ifthe apphed potentIal IS greater than the half-wave potential ofthe sulfide

Ion If the apphed potentIal IS less than the half-wave potentIal, an interfermg

reactIon wIll not occur, but coatmg ofthe anode wIth the sulfide ofthe anode metal

can take place

44 DIssolved oxygen probes are temperature sensItive, and temperature compensatlOn IS

normally proVIded by the manufacturer Membrane probes have a temperature

coeffiCIent of4 to 6 percentl'C dependent upon the membrane employed

5 Apparatus

5 1 No speCIfic probe or accessory IS especIally recommended as supenor However, probes

WhICh have been evaluated or are m use and found to be relIable are the Weston & Stack

DO Analyzer Model 30, the Yellow Spnngs Instrument (YSI) Model 54, and the

Beckman Fleldlab Oxygen Analyzer

6. CalIbration

Follow manufacturer mstructlOns

7. Procedure

Follow manufacturer mstructIons

8. CalculatIon

Follow manufacturer mstructlons

9. PrecISIon and Accuracy

Manufacturer'sspecificatlOn claIm

°1mg!1 repeatabIlIty WIth ±1% accuracy

BIblIography

1 Standard Methods for the ExammatlOn of Watet and Wastewater, 14th EdItion, p 450,

Method 422F (1975)

360 1-2
OXYGEN, DISSOLVED

Method 360.2 (Modified Winklei', Full-Bottle Technique)

STORET NO. 00300

1 Scope and ApplIcatiOn

1 1 This method is applIcable for use with most wastewaters and streams that contam mtrate

mtrogen and not more than 1mg/l offerrous iron Other reducmg Of oXidlZlng matenals

should be absent If 1 ml of fluonde solutiOn IS added before aCidifymg the sample and

there is no delay m titratiOn, the method is also applIcable m the presence of 100-200

mg/l fernc iron

12 The Dissolved Oxygen (DO) Probe techmque gives comparable results on all samples

types

1 3 The aZide modificatiOn is not applIcable under the followmg conditiOns (a) samples

contammg sulfite, thiOsulfate, polythiOnate, appreCiable quantities of free chlorme or

hypochlonte, (b) samples high m suspended solIds, (c) samples contammg orgamc

substances which are readl1y oXidized m a highly alkalme solutiOn, or which are oXidized

by free iOdme m an aCid solutiOn, (d) untreated domestic sewage, (e) biOloglCal flocs, and

(f) where sample color mterferes with endpomt detectiOn In mstances where the aZide

modificatiOn is not apphcable, the DO probe should be used

2 Summary ofMethod

2 1 The sample is treated with manganous sulfate, potasslUm hydrOXide, and potasslUm

iOdide (the latter two reagents combmed m one solutiOn) and finally sulfunc aCid The

mitial preCipitate of manganous hydrOXide, Mn(OH)2' combmes with the dissolved

oxygen m the sample to form a brown preCipitate, manganic hydrOXide, MnO(OH)2

Upon aCidificatiOn, the mangamc hydrOXide forms mangamc sulfate which acts as an

oXidizmg agent to release free iOdme from the potasslUm iOdide The iOdme, which is

stOlchiOmetncally eqUlvalent to the dissolved oxygen m the sample is then titrated with

sodlUm thiOsulfate or phenylarsme oXide (PAO)

3 Interferences

3 1 There are a number ofmterferences to the dIssolved oxygen test, mcludmg oXldlzmg and

reducmg agents, mtrate iOn, ferrous iron, and orgamc matter

32 Vanous modificatiOns of the ongmal Wmkler procedure for dissolved oxygen have been

developed to compensate for or elImmate mterferences The Alsterberg modification is

commonly used to successfully elImmate the mtnte mterference, the Rideal-Stewart

modificatiOn is deSigned to elImmate ferrous iron mterference, and the Thenault

procedure is used to compensate for high concentratiOn oforgamc matenals

3 3 Most of the common mterferences m the Wmkler procedure may be overcome by use of

the dissolved oxygen probe

Approved for NPDES

Issued 1971

3602-1
4. Sample Handlmg and Preservation

4 1 Where possible, collect the sample m a 300 ml BOD mcubatlon bottle Special

precautions are reqUIred to aVOld entramment or solution of atmosphenc oxygen or loss

ofdissolved oxygen

42 Where samples are collected from shallow depths (less than 5 feet), use ofan APHA-type

sampler IS recommended Use of a Kemmerer type sampler IS recommended for samples

collected from depths ofgreater than 5 feet

4 3 When a Kemmerer sampler IS used, the BOD sample bottle should be filled to

overflowmg (overflow for approximately 10 seconds) Outlet tube of Kemmerer should

be mserted to bottom ofBOD bottle Care must be taken to prevent turbulence and the

formation ofbubbles when ftI1mg bottle

4.4 At time ofsamplmg, the sample temperature should be recorded as preCisely as reqUIred

4.5 Do not delay the determmatlOn of dissolved oxygen m samples havmg an appreCiable

lodme demand or contammg ferrous Iron Ifsamples must be preserved either method

(45 1) or(452) below, may be employed

4.5 1 Add 2 ml ofmanganous sulfate solution (6 1) and then 2 ml ofalkahne lOdlde-azlde

solution (62) to the sample contamed m the BOD bottle Both reagents must be

added well below the surface ofthe hqUld Stopper the bottle Immediately and mix

the contents thoroughly The sample should be stored at the temperature of the

collection water, or water sealed and kept at a temperature of 10 to 20°C, 10 the

dark Complete the procedure by addmg 2 ml H2S04(see 7 1) at time of analYSIS

4.52 Add 0 7 ml of conc H2S04(6 3) and 1 ml sodmm aZide solution (2 g NaN3 10 100

ml dlsttlled water) to sample 10 the BOD bottle Store sample as 10 (45 1)

Complete the procedure us10g 2 ml of manganous sulfate solutlOn (6 1), 3 ml

alkahne Iodide-azide solution (62), and 2 ml of conc H2S04 (63) at time of

analYSIS

4 6 Ifeither preservation techmque IS employed, complete the analySIS wlthm 4-8 hours after

samphng

5. Apparatus

5 1 Sample bottles-300 ml ±3 ml capacity BOD 1Ocubatlon bottles With tapered ground

glass pomted stoppers and flared mouths

5.2 Pipets-with elongated tiPS capable ofdehvermg 2 0 ml ±O 10 ml ofreagent

6 Reagents

6 1 Manganous sulfate solution Dissolve 480 g manganous sulfate (MnS04-4H20 m distilled

water and dtlute to 1hter

6 I 1 Alternatively, use 400 g of MnS04-2H20 or 364 g of MnS04-H20 per hter When

uncertamty eXists regardmg the water of crystalhzatlOn, a solutlOn of eqUIvalent

strength may be obtamed by adJustmg the speCific gravity of the solutlOn to 1 270

at 20°C

6 2 Alkalme lOdlde-azlde solution Dissolve 500 g ofsodmm hydrOXide (NaOH) or 700 g of

potassIUm hydrOXide (KOH) and 135 g of sodmm lOdlde (Nat) or 150 g of potassmm

Iodide (KI) 10 distilled water and dtlute to 1 hter To thiS solutlOn add 10 g ofsolutlOn

aZide (NaN3) dissolved m 40 ml ofdistilled water

3602-2
6 3 Sulfunc aCId concentrated

6 4 Starch solutlOn Prepare an emulslOn of 10 g soluble starch m a mortar or beaker wIth a

small quantlty of dIstllled water Pour thIS emulslOn mto 1 hter ofbOllmg water, allow to

boll a few mmutes, and let settle overmght Use the clear supernate ThIS solutlOn may be

preserved by the additlOn of 5 ml per hter of chloroform and storage m a woe

refngerator

64 1 Dry, powdered starch mdicators such as "thyodene" may be used m place ofstarch

solutlOn

65 PotassIUm fluonde solutlOn DIssolve 40 g KF82H20 m dIstl1led water and dl1ute to 100

ml

66 SodIUm thlOsulfate, stock solutlOn, 075 N DIssolve 186 15 g Na2S20385H20 m bolled

and cooled dIstIlled water and dIlute to 1 hter Preserve by addmg 5 ml chloroform

67 SodIUm thlOsulfate standard tltrant, 00375 N Prepare by dllutmg 500 ml of stock

solutlOn to 1 hter Preserve by addmg 5 ml of chloroform Standard sodIUm thlOsulfate,

exactly 00375 N IS eqUIvalent to 0300 mg ofDO per 1 00 ml StandardIze WIth 00375 N

potassIUm bllodate

68 PotassIUm bllodate standard, 0 0375 N For stock solutlOn, dIssolve 4873 g of potassIUm

bllodate, prevlOusly dned 2 hours at 103°C, m 1000 ml of dIstilled water To prepare

workmg standard, dllute 250 ml to 1000 ml for 00375 N bllodate solutlOn

6 9 StandardizatlOn of 0 0375 N sodIUm thIosulfate DIssolve apprOXImately 2 g (± 109) KI

m 100 to 150 ml dIstIlled water, add 10 ml of 10% H2S04 followed by 20 0 ml standard

potaSSIUm bllodate (6 8) Place m dark for 5 mmutes, dl1ute to 300 ml, and tItrate WIth

the standard sodIUm thlOsulfate (6 7) to a pale straw color Add 1-2 ml starch solutlOn

and contmue the tltratlOn drop by drop untll the blue color dIsappears Run m duphcate

Duphcate determmatlOns should agree withm ±O 05 ml

6 10 As an alternatIve to the sodIUm thlOsulfate, phenylarsme OXIde (PAO) may be used ThIS

IS avallable, already standardIzed, from commerCIalsources

7 Procedure

7 I To the sample collected m the BOD mcubatlOn bottle, add 2 ml ofthe manganous sulfate

solutlOn (6 1) followed by 2 ml of the alkahne lOdide-azide solutlOn (6 2), well below the

surface of the hqUId, stopper WIth care to exclude aIr bubbles, and mIX well by mvertmg

the bottle several tlmes When the preCIpItate settles, leavmg a clear supernatant above

the manganese hydroxIde floc, shake agam When setthng has produced at least 200 ml

of clear supernatant, carefully remove the stopper and Immediately add 2 ml of conc

H2S04 (6 3) (suifamic aCId packets, 3 g may be SubstItuted for H2SOS1

) by allowmg the

aCId to run down the neck of the bottle, re-stopper, and mIX by gentle mverSlOn untll the

lOdme IS umformly dIstnbuted throughout the bottle Complete the analySIS withm 45

mmutes

7 2 Transfer the entIre bottle contents by mverSlOn mto a 500 ml WIde mouth flask and tItrate

WIth 00375 N thlOsulfate solutlOn (6 7) (00375 N phenyarsme OXIde (PAO) may be

substItuted as tItrant) to pale straw color Add 1-2 ml ofstarch solutlOn (6 4) or 01 g of

powdered mdicator and contmue to tItrate to the first dIsappearance ofthe blue color

3602-3
73 If femc Iron IS present (100 to 200 mg/1), add 10 ml of KF (65) solutIOn before

aCIdIficatIOn

74 OccasIonally, a dark brown or black precIpItate persIsts In the bottle after aCIdicatlOn

ThIS preCIpItate w111 dIssolve lithe solutIOn IS kept for a few mInutes longer than usual or,

Ifpartlcularly persIstent, a few more drops ofH2S04 wIll effect dISsolutIOn

8. CalculatIon

8.1 Each ml of 0 0375N sodIUm thIOsulfate (or PAO) tItrant IS eqUIvalent to 1 mg DO when

the entIre bottle contents are tItrated I

82 lfthe results are desIred In mIllIlIters of oxygen gas per lIter at O°C and 760 mm pressure

multIply mg/1 DO by 0 698

83 To express the results as percent saturatIon at 760 mm atmosphenc pressure, the

solubIlIty data In Table 4221 (WhIpple & WhIpple, p 446-447, Standard Methods, 14th

EdItIOn) may be used EquatIOns for correctIng the solubIlItIes to barometrIc pressures

other than mean sea level are given below the table

8 4 The solubIlIty of DO In dIStl1led water at any barometrIc pressure, p (mm Hg),

temperature, TOC, and saturated vapor pressure, u (mm Hg), for the gIven T, may be

calculated between the temperature of0° and 30°Cby

mIll DO = (P - u) x 0 678

35 + T

and between 30° and 50°C by

mIll DO = (P - u) x 0 827

49 + T

9 PrecISIon and Accuracy

9 1 Exact data are unavaIlable on the preCISIOn and accuracy of thIS techmque, however,

reprodUCIbIlIty IS approXImately 0 2 mg/l of DO at the 7 5 mg/1 level due to eqUIpment

tolerances and uncompensated dIsplacement errors

BIbliography

1 Kroner, R C, Longbottom, J E, Gorman, R A, "A ComparIson of VarIOUS Reagents

Proposed for Use In the WInkler Procedure for DIssolved Oxygen", PHS Water PollutIon

SurveIllance System ApplIcatIOns and Development, Report # 12, Water QUalIty SectIOn,

BaSIC Data Branch, July 1964

2. Annual Book of ASTM Standards, Part 31, "Water", Standard 01589-60, Method A, p 373

(1976)

3. Standard Methods for the ExamInatIOn ofWater and Wastewater, 14th EdItIOn, p 443, method

422 B(1975)

3602-4
PHOSPHORUS, ALL FORMS

Method 365.1 (Colorimetric, Automated, Ascorbic Acid)

STORET NO. See Section 4

1 Scope and ApphcatlOn

1 1 These methods cover the determmatlOn of specIfied forms of phosphorus m drmkmg,

surface and sahne waters, domestIc and mdustnal wastes

1 2 The methods are based on reactIOns that are specIfic for the orthophosphate IOn Thus,

dependmg on the prescnbed pre-treatment of the sample, the vanous forms of

phosphorus gIven m FIgure 1 may be determmed These forms are defined m SectIOn 4

1 2 1 Except for m-depth and detatled studIes, the most commonly measured forms are

phosphorus and dIssolved phosphorus, and orthophosphate and dIssolved

orthophosphate Hydrolyzable phosphorus IS normally found only m sewage-type

samples Insoluble forms ofphosphorus are determmed by calculatIOn

1 3 The methods are usable III the 0 01 to 1 0 mg P/1 range ApproxImately 20-30 samples

per hour can be analyzed

2 Summary ofMethod

2 1 Ammomum molybdate and antImony potassmm tartrate react m an aCId medmm WIth

dIlute solutIOns of phosphorus to form an antlmony-phospho-molybdate complex ThIS

complex IS reduced to an mtensely blue-colored complex by ascorbIc aCId The color IS

proportIonal to the phosphorus concentratIOn

2 2 Only orthophosphate forms a blue color m thIS test Polyphosphates (and some orgamc

phosphorus compounds) may be converted to the orthophosphate form by manual

sulfunc aCId hydrolySIS Orgamc phosphorus compounds may be converted to the

orthophosphate form by manual persulfate dlgestlOn(2) The developed color IS measured

automatIcally on the AutoAnalyzer

3 Sample Handhng and PreservatIOn

3 1 If benthIc depOSIts are present m the area bemg sampled, great care should be taken not

to mclude these depOSIts

3 2 Sample contamers may be ofplastIc matenal, such as cubltamers, or ofPyrex glass

33 If the analysIs cannot be performed the same day of collectIOn, the sample should be

preserved by the addItIon of2 ml conc H2S04 per hter and refngeratlOn at 4°C

4 DefimtlOns and Storet Numbers

4 1 Total Phosphorus (P) - aU ofthe phosphorus present m the sample regardless ofform, as

measured by the persulfate dIgestIOn procedure (00665)

4 1 1 Total Orthophosphate (P-ortho)-morgamc phosphorus [(P04t 3

] m the sample as

measured by the dIrect colonmetnc analysIs procedure (70507)

Approved for NPDES, pendmg approval for SectIOn 304(h), CWA

Issued 1971

EdItona1 reVISIOn 1974 and 1978

365 1-1
W

0\

VI

-I

N

IRe~due I

Total Sample (No rlltratl0n)

SAJ.lPLE J, - -

Dlrect H2

SO4 Persulfate

\/ Colonmetry \/ ~~?rOlysls & '\

V DiLgestlon

r.ol IOrthophosphate I I

Hydrolyzable &

Orthophosphate I I I Phosphorus

Fllter (through 0 45 J.l membrane fllter)

\ V

'\V

F1ltrate t

Jt

Dlrect H2

SO4 Persulfate

Colonmetry Hydrolysls & Dlgestlon &

\ V \ V Colonmetry \

/ Colorlmetry

Dlssolved D1SS Hydrolyzable Dlssolved

Orthophosphate & Orthophosphate Phosphorus

FIGURE 1. ANALYTICAL SCHEME FOR DIFFERENTIATION

OF PHOSPHORUS FORMS
4 1 2 Total Hydrolyzable Phosphorus (P-hydro)-phosphorus m the sample as measured

by the sulfunc aCId hydrolysIs procedure, and mmus predetermmed

orthophosphates ThIs hydrolyzable phosphorus mc1udes polyphosphates

[(P20 7)-4, (P3olOyS, etc] plus some orgamc phosphorus (00669)

4 1 3 Total Orgamc Phosphorus (P-org)-phosphorus (morgamc plus oXIdIzable orgamc)

m the sample as measured by the persulfate dIgestIOn procedure, and mmus

hydrolyzable phosphorus and orthophosphate (00670)

4 2 DIssolved Phosphorus (P-D) - all of the phosphorus present m the flltrate of a sample

filtered through a phosphorus-free fllter of 0 45 mICron pore SIze and measured by the

persulfate dIgestIOn procedure (00666)

421 DIssolved Orthophosphate (P-D, ortho) - as measured by the dIrect colonmetnc

analySIS procedure (00671)

422 DIssolved Hydrolyzable Phosphorus (P-D, hydro) - as measured by the sulfurIC

aCId hydrolysIs procedure and mmus predetermmed dIssolved orthophosphates

(00672)

423 DIssolved Orgamc Phosphorus (P-D, org) - as measured by the persulfate

dIgestIOn procedUJ.:e, and mmus dIssolved hydrolyzable phosphorus and

orthophosphate (00673)

4 3 The followmg forms, when sufficIent amounts of phosphorus are present m the sample to

warrant such consIderatIOn, may be calculated

431 Insoluble Phosphorus (P-I)=(P)-(P-D) (00667)

43 1 1 Insoluble orthophosphate (P-I, ortho)=(P, ortho) - (P-D, ortho)

(00674)

43 12 Insoluble Hydrolyzable Phosphorus (P-I, hydro) = (P, hydro) - (PD, hydro) (00675)

43 I 3 Insoluble Orgamc Phosphorus (P-I, org) = (P, org) - (P-D, org)

(00676)

44 All phosphorus forms shall be reported as P, mg/l, to the thIrd place

5 Interferences

5 1 No mterference IS caused by copper, Iron, or sIhcate at concentratIOns many times

greater than theIr reported concentratIOn m sea water However, hIgh Iron

concentratIOns can cause preCIpItatIOn of and subsequent loss ofphosphorus

5 2 The salt error for samples rangmg from 5 to 20% salt content was found to be less than

1%

5 3 Arsenate IS determmed sIml1arly to phosphorus and should be conSIdered when present

m concentratIOns hIgher than phosphorus However, at concentratIOns found m sea

water, It does not mterfere

5 4 Sample turbIdIty must be removed by flltration pnor to analySIS for orthophosphate

Samples for total or total hydrolyzable phosphorus should be flltered only after

dIgestIon Sample color that absorbs m the photometnc range used for analySIS WIll also

mterfere

6 Apparatus

6 1 Techmcon AutoAnalyzer consIstmg of

365 1-3
611 Sampler

6 1 2 Mamfold (AAI) or AnalytIcal Cartndge (AAII)

6 1 3 ProportlOnmg pump

6 1 4 Heatmg bath, 50°C

6.1 5 Colonmeter equIpped wIth 15 or 50 mm tubular flow cell

6 1 6 650-660 or 880 nm filter

6 1 7 Recorder

6 1 8 DIgital pnnter for AAII (optlOnal)

6 2 Hot plate or autoclave

6.3 ACId-washed glassware All glassware used m the determmation should be washed wIth

hot 1 1 HCI and nnsed wIth dIstilled water The aCId-washed glassware should be filled

wIth dIstIlled water and treated wIth all the reagents to remove the last traces of

phosphorus that mIght be adsorbed on the glassware Preferably, thIS glassware should

be used only for the determmation of phosphorus and after use It should be rmsed wIth

dtstilled water and kept covered until needed agam IfthIS IS done, the treatment wIth 1 1

HCI and reagents IS only reqUlred occaslOnally CommercIal detergent should never be

used

7 Reagents

7 1 Sulfunc aCId solutlOn, 5N Slowly add 70 ml of conc H2S04to approxImately 400 ml of

dIstilled water Cool to room temperature and dIlute to 500 ml wIth dIstilled water

72 Antimony potassmm tartrate SolutIon WeIgh 03 g K(SbO)C4H40 6-1/2H20, dIssolve m

50 ml dIStilled water m 100 ml volumetnc flask, dilute to volume Store at 4°C m a dark,

glass-stoppered bottle

73 Ammomum molybdate SolutIon DIssolve 4 g (NH4)6Mo7024-4H20 m 100 ml dIstilled

water Store m a plastIc bottle at 4°C

74 AscorbIc aCId, 0 1M DIssolve 1 8 g of ascorbIC aCId m 100 ml of dIstilled water The

solution IS stable for about a week If prepared wIth water contammg no more than trace

amounts ofheavy metals and stored at 4°C

7.5 Combmed reagent (AAI) MIX the above reagents m the followmg proportions for 100 ml

of the IDlXed reagent 50 ml of 5N H2S04 (7 1), 5 ml of antimony potassmm tartrate

solution (7 2), 15 ml of ammomum molybdate solutlOn (7 3), and 30 ml of ascorbIC aCId

solution (7 4) MIX after addItIon of each reagent All reagents must reach room

temperature before they are mIxed and must be mIxed m the order gIven If turbIdIty

forms m the combmed reagent, shake and let stand for a few mmutes untIl the turbIdIty

dIsappears before processmg ThIS volume IS suffiCIent for 4 hours operatlOn Smce the

stabIhty ofthIS solutlOn IS hmited, It must be freshly prepared for each run.

NOTE 1: A stable solutlOn can be prepared by not mcludmg the ascorbIC aCId m the

combmed reagent If thIS 18 done, the mIxed reagent (molybdate, tartrate, and aCId) IS

pumped through the dIstilled water hne and the ascorbIC aCId solutlOn (30 ml of 7 4

dtluted to 100 ml wIth dIstIlled water) through the ongmal mIXed reagent hne

7 6 Sulfunc aCId solutlOn, 11 N Slowly add 310 ml conc H2S04 to 600 ml dIstIlled water

When cool, dIlute to 1hter

365 1-4
7 7 Ammomum persulfate

7 8 AC1d wash water Add 40 ml ofsulfunc aC1d solutlOn (7 6) to I hter ofd1stilled water and

dllute to 2 hters (Not to be used when only orthophosphate 1S bemg determmed)

79 Phenolphthalem mdlCator solutlOn (5 gil) D1ssolve 05 g of phenolphthalem m a

solutlOn of 50 ml ofethyl or 1sopropyl alcohol and 50 ml ofd1stilled water

7 10 Stock phosphorus solutlOn D1ssolve 04393 g ofpre-dned (105°C for 1 hour) KH2P04 m

d1stllied water and dllute to 1000 milO ml = 0 1mg P

7 11 Standard phosphorus solutlOn D1lute 100 0 ml ofstock solutlOn (7 10) to 1000 ml With

d1stllied water 1 0 ml = 0 01 mg P I

7 12 Standard phosphorus solutlOn Dllute 1000 ml of standard solutlOn (7 11) to 1000 ml

w1th d1stilled water 1 0 ml = 0 001 mg P

7 13 Prepare a senes of standards by d1lutmg sUitable volumes of standard solutlOns (7 11)

and (7 12) to 1000 ml w1th d1stllied water The followmg dllutlOns are suggested

ml of Standard

Phosphorus SolutIOn (7 12)

00

20

50

100

ml of Standard

Phosphorus Solution (7 11)

20

50

80

100

Cone,

mg PII

000

002

005

010

mg Pl1

020

050

080

100

8 Procedure

8 1 Phosphorus

8 1 1 Add 1 ml ofsulfunc aC1d solutlOn (7 6) to a 50 ml sample andlor standard ill a 125

ml Erlenmeyer flask

8 1 2 Add 0 4 g ofammomum persulfate

8 1 3 Boll gently on a pre-heated hot plate for approx1mately 30-40 mmutes or untll a

final volume of about 10 ml 1S reached Do not allow sample to go to dryn~ss

Alternately, heat for 30 mmutes m an autoclave at 121°C (15-20 pS1)

8 1 4 Cool and dllute the sample to 50 ml Ifsample 1S not clear at th1s pomt, filter

8 1 5 Determme phosphorus as outlmed m (8 3 2) w1th aC1d wash water (7 8) m wash

tubes

8 2 Hydrolyzable Phosphorus

821 Add 1 ml ofsulfunc aC1d solutlOn (76) to a 50 ml sample andlor standard m a 125

ml Erlenmeyer flask

365 1-5
I III

8 2 2 Boll gently on a pre-heated hot plate for 30-40 mInutes or untll a final volume of

about 10 mIls reached Do not allow sample to-go to dryness Alternatively, heat

for 30 mInutes In an autoclave at 121°C (15-20 pSI)

8 2 3 Cool and dllute the sample to 50 ml Ifsample IS not clear at thIS POInt, filter,

8 2 4 DetermIne phosphorus as outhned In (8 3 2) wIth aCId wash water (7 8) In wash

tubes

8 3 Orthophosphate

8 3 1 Add 1 drop of phenolphthaleIn IndIcator solutIOn (7 9) to approxImately 50 ml of

sample If a red color develops, add sulfunc aCId solutIOn (7 6) drop-WIse to Just

dIscharge the color ACId samples must be neutrahzed wIth 1 N sodmm hydroXide

(40 g NaOH/l)

8 3 2 Set up mamfold as shown In FIgure 2, AAI or FIgure 3, AAII

8 3 3 Allow both colonmeter and recorder to warm up for 30 mInutes ObtaIn a stable

basehne wIth all reagents, feedIng dlstllied water through the sample hne

8 3 4 For the AAI system, sample at a rate of 201hr, 1 mInute sample, 2 mInute wash

For the AAII system, use a 301hr, 2 1cam, and a common wash

8 3 5 Place standards In Sampler In order of decreaSIng concentratIOn Complete filhng

ofsampler tray wIth unknown samples

8 3 6 SWItch sample hne from dIstilled water to Sampler and begIn analySIS

9 Calculation

9 1 Prepare a standard curve by plottIng peak heIghts of processed standards agaInst known

concentratIOns Compute concentrations of samples by companng sample peak heIghts

with standard curve Any sample whose computed value IS less than 5% ofItS ImmedIate

predecessor must be rerun

10 PrecISIon and Accuracy (AAI system)

10 1 SIX laboratones partICIpatIng In an EPA Method Study, analyzed four natural water

samples contaInIng exact Increments oforthophosphate, wIth the follOWIng results

Increment as PreCISIon as Accuracy as

Orthophosphate Standard DevIatIon BIas, BIas,

mg P/hter mg P/hter % mg P/hter

004 0019 +167 +0007

004 0014 - 83 -0003

029 0087 -155 -005

030 0066 -128 -004

102 In a single laboratory (EMSL), USing surface water samples at concentratIOns of 0 04,

019, 035, and 084 mg P/l, standard devIatIOns were ±O 005, ±O 000, ±O 003, and

±0 000, respectIvely

10 3 In a single laboratory (EMSL), USing surface water samples at concentratIons of0 07 and

076 mg p/l, recovenes were 99% and 100%, respectively

365 1-6

III I I 1111 II
BIblIography

1 Murphy, J and RIley, J , "A ModIfied Smgle SolutIOn for the DetermmatIOn of Phosphate lh

Natural Waters" Anal Chlm Acta, 27,31 (1962)

2 Gales, M, Jr, Juhan, E, and Kroner, R, "Method for Quantitative Determmatlon of Total

Phosphorus m Water" Jour AWWA, 58, No 10,1363 (1966)

3 Lobnng, L B and Booth, R L, "EvaluatIOn of the AutoAnalyzer II; A Progress Report",

Techmcon InternatlOnal SymposlUm, June, 1972 New York, N Y

4 Annual Book ofASTM Standards, Part 31, "Water", Standard D515-72, p 388 (1976)

5 Standard Methods for the ExammatIOn of Water and Wastewater, 14th EdltlOn, p 624,

Method 606, (1975)

365 1-7
IN

0\

Ul

lI

00

SM = SMALL MIXIN

LM= LARGE MIXIN

50°C

HEATING

BATH

, COIL mUmln

COIL WASH WATER P B 29 WASH

TO SAMPLER

P B 2.9 SAMPLE 0

-§.~- SAMPLER

I""VYY' R R 08 AIR 20/ hr

21 LM fV.V Y Y 1.2 DISTILL.ED

WATER

- - 0 0 042 MIXED

REAGENT

.D WASTE G G 200 WASTE

. .. PROPORTIONINC3 .. PUMP - I

0 :::J

I

OLORIMETER V r--.. RECORDER

50mm FLOW CELL

650-660 or 880nm FILTER

FIGURE 2 PHOSPHORUS MANIFOLD AA I
w

0\

VI

-I

\0

milmin

WASH WAk.ER G G 20 WlSH

TO SAMPLER ,

. 0 0 042 SAMPLE 0

SAMPLER

nnnn BLACK 0.32 AIR 30/hr ... - 2:1

0000 . BLACK o 32 DISTfLLED ...- WATER ,

0 W 0.23 MIXED

REAGENT

HEATING WASTE BATH W W 06

31° C .. WASTE

AI. PPOPORT!ON!NG

PUMP

RECORDER

D DIGITAL

PRINTER

c=J I-

,-... A r-.... ...

COLORIMETER

50mm FLOW CELL

650- 660 nm or

880nm FILTER

FIGURE 3 PHOSPHORUS MANIFOLD AA II
PHOSPHORUS, ALL FORMS

Method 365.2 (Colorimetric, Ascorbic Acid, Single Reagent)

STORET NO. See Section 4

1 Scope and ApphcatlOn

1 1 These methods cover the determmatlOn of specIfied forms of phosphorus m dnnkmg,

surface and sahne waters, domestIC and mdustnal wastes

1 2 The methods are based on reactIons that are specIfic for the orthophosphate lOn Thus,

dependmg on the preSCrIbed pre-treatment of the sample, the varIOUS forms of

phosphorus gIven m FIgure 1may be determmed These forms are defined m Section 4

1 2 1 Except for m-depth and detaIled studIes, the most commonly measured forms are

phosphorus and mssolved phosphorus, and orthophosphate and dIssolved

orthophosphate Hydrolyzable phosphorus IS normally found only m sewage-type

samples and msoluble forms ofphosphorus are determmed by calculatlOn

1 3 The methods are usable m the 001 to 0 5 mg P/1 range

2 Summary ofMethod

2 1 Ammomum molybdate and antimony potaSSIUm tartrate react m an aCId medIUm wIth

dIlute solutlOns of phosphorus to form an antlmony-phospho-molybdate complex ThIS

complex IS reduced to an mtensely blue-colored complex by ascorbIC aCId The color IS

proportlOnal to the phosphorus concentratlOn

2 2 Only orthophosphate forms a blue color m thIS test Polyphosphates (and some orgamc

phosphorus compounds) may be converted to the orthophosphate form by sulfurIC aCId

hydrolysIs Orgamc phosphorus compounds may be converted to the orthophosphate

form by persulfate digestIon(2)

3 Sample Handhng and PreservatlOn

3 1 If benthIC depOSIts are present m the area bemg sampled, great care should be taken not

to mclude these depOSIts

3 2 Sample contamers may be ofplastIC matenal, such as cubitamers, or ofPyrex glass

3 3 Ifthe analySIS cannot be performed the day of collectlOn, the sample should be preserved

by the additlOn of2 ml conc H2S04 per hter and refrIgeratlOn at 4°C

4 DefimtlOns and Storet Numbers

4 1 Total Phosphorus (P) - all ofthe phosphorus present In the sample, regardless ofform,

as measured by the persulfate digestlOn procedure (00665)

41 1 Total Orthophosphate (P, ortho) - Inorgamc phosphorus [(P04y3] m the sample

as measured by the dIrect colOrImetrIc analySIS procedure (70507)

412 Total Hydrolyzable Phosphorus (P, hydro) - phosphorus m the sample as

measured by the sulfurIC aCId hydrolySIS procedure, and mInUS pre-determmed

orthophosphates ThIS hydrolyzable phosphorus Includes polyphosphorus

[(P20 7)-4, (P30 1Oy5, etc] plus some orgamc phosphorus (00669)

Approved for NPDES

Issued 1971

3652-1
SAMPLE

Total Sample (No FIltratIon)

j;

H2S04

d.l HydrolysIs 1\

"\V Colorlmer-rv

L'ers ulfate

DIgestIon

.. Co!orlIDetIY

I I J Phosphorus I

DIrect

Colonmetry

Orthophosphate

\JI I I I Hydrolyzable &

Orthophosphate

".I'

FIlter (through 0 45 u membrane fIlter)

W

0\

Ul

tv

\11 IResIdue 1 w

F,;ate I

Dlrect H2SO4

ColorImetry HydrolysIs &

ColorImetry I

Persulfate

DIgestIon &

Colonmetry

DIssolved

Orthophosphate

DISS Hydrolyzable

&Orthophosphate

DIssolved

Phosphorus

FIGURE 1. ANALYTICAL SCHEME FOR DIFFERENTIATION

OF PHOSPHORUS FORMS
4 1 3 Total Orgamc Phosphorus (P, org) - phosphorus (morgamc plus oXidizable

orgamc) m the sample measured by the persulfate digestiOn procedure, and mmus

hydrolyzable phosphorus and orthophosphate (00670)

4 2 Dissolved Phosphorus (P-D) - all ofthe phosphorus present In the filtrate of a sample

filtered through a phosphorus-free filter of 0 45 micron pore Size and measured by the

persulfate digestiOn procedure (00666)

42 1 Dissolved Orthophosphate (P-D, ortho) - as measured by the direct colonmetnc

analysis procedure (00671)

422 Dissolved Hydrolyzable Phosphorus (P-D, hydro) - as measured by the sulfunc

aCid hydrolysIs procedure and mmus pre-determmed dissolved orthophosphates

(00672)

4 2 3 Dissolved Orgamc Phosphorus (P-D, org) - as measured by the persulfate

digestiOn procedure, and mmus dissolved hydrolyzable phosphorus and

orthophosphate (00673)

4 3 The folloWIng forms, when suffiCient amounts ofphosphorus are present m the sample to

warrant such consideratiOn, may be calculated

43 1 Insoluble Phosphorus (P-I)=(P)-(P-D) (00667)

43 1 1 Insoluble orthophosphate (P-I, ortho)=(P, ortho)-(P-D, ortho)

(00674)

43 1 2 Insoluble Hydrolyzable Phosphorus (P-I, hydro)=(P, hydro)-(P-D,

hydro) (00675)

43 1 3 Insoluble Orgamc Phosphorus (P-I, org)=(P, org) - (P-D, org)

(00676)

44 All phosphorus forms shall be reported as P, mg/l, to the thud place

5 Interferences

5 1 No Interference IS caused by copper, Iron, orsihcate at concentratiOns many times

greater than their reported concentratiOn In sea water However, high iron

concentratiOns can cause precipitatiOn ofand subsequent loss ofphosphorus

5 2 The salt error for samples rangIng from 5 to 20% salt content was found to be less than

1%

5 3 Arsenate is determIned siml1arly to phosphorus and should be considered when present

In concentratiOns higher than phosphorus However, at concentrations found In sea

water, it does not mterfere

6 Apparatus

6 1 Photometer - A spectrophotometer or filter photometer sUitable for measurements at

650 or 880 nm With a hght path of 1cm or longer

6 2 ACid-washed glassware All glassware used should be washed With hot 1 1 Hel and

rmsed With distilled water The aCid-washed glassware should be filled With dist111ed

water and treated With all the reagents to remove the last traces ofphosphorus that might

be adsorbed on the glassware Preferably, thIS glassware should be used only for the

determmatiOn of phosphorus and after use It should be nnsed WIth dlst111ed water and

3652-3
kept covered untIl needed agaIn IfthIS IS done, the treatment WIth 1 1 HCl and reagents

IS only reqUired occasIOnally CommercIal detergents should never be used

7. Reagents

7 1 SulfUrIC aCId solutIOn, 5N DIlute 70 ml ofconc H2S04WIth dIstilled water to 500 ml

72 Antimony potasSIUm tartrate solutIOn WeIgh 1 3715 g K(SbO)C4H40 6-1/2H20,

dIssolve In 400 ml dIstIlled water In 500 ml volumetnc flask, dIlute to volume Store at

4°C In a dark, glass-stoppered bottle

7 3 AmmOnIum molybdate solutIOn DIssolve 20 g(NH4)6Mo7024-4H20 In 500 m1 of dIstIlled

water Store In a plastic bottle at 4°C

74 AscorbIc aCId, 0 1M DIssolve 1 76 g of ascorbIC aCId In 100 ml of dIStilled water The

solutIon IS stable for about a week Ifstored at 4°C

75 CombIned reagent MIX the above reagents In the follOWIng proportions for 100 ml ofthe

mIxed reagent 50 ml of 5N H2S04, (7 1), 5 ml of antimony potassIUm tartrate solutIOn

(7 2), 15 ml of ammOnIum molybdate solutIOn (7 3), and 30 ml of ascorbIc aCId solutIOn

(74) MIX after addItion of each reagent All reagents must reach room temperature

before they are mIxed and must be mIxed In the order gIven If turbIdIty forms In the

combIned reagent, shake and let stand for a few mInutes untIl the turbIdIty dIsappears

before proceedIng SInce the stabIlIty of thIS solutIOn IS lImIted, It must be freshly

prepared for each run

7 6 Sulfunc aCId solutIOn, 11 N Slowly add 310 ml conc H2S04 to 600 ml dIstIlled water

When cool, dIlute to 1lIter

7 7 AmmOnIum persulfate

7 8 Stock phosphorus solutIOn DIssolve In dIstIlled water 0 2197 g of potassIUm dihydrogen

phosphate, KH2P04, whIch has been dned In an oven at 105°C DIlute the solutIOn to

lOOOml, 1 Oml = 005 mgP

7 9 Standard phosphorus solutIOn DIlute 10 0 ml ofstock phosphorus solutIOn (7 8) to 1000

ml WIth dIStilled water, 1 0 ml = 0 5 ug P

7 9 1 USIng standard solutIOn, prepare the follOWIng standards In 50 0 ml volumetnc

flasks

ml of Standard

Phosphorus SolutIOn (7 9)

o

10

30

50

100

200

300

400

500

Cone, mg/1

000

001

003

005

010

020

030

040

050

7 10 SodIUm hydroxIde, 1 N DIssolve 40 g NaOH In 600 ml dIStilled water Cool and dIlute

to 1 lIter

3652-4
8 Procedure

8 1 Phosphorus

8 1 1 Add 1ml ofHzS04 solutIOn (7 6) to a 50 ml sample m a 125 ml Erlenmeyer flask

8 1 2 Add 0 4 g ofammomum persulfate

8 1 3 BoIl gently on a pre-heated hot plate for approximately 30-40 mInutes or untll a

final volume of about 10 mIlS reached Do not allow sample to go to dryness

Alternatively, heat for 30 mInutes In an autoclave at 121°C (15-20 pSI)

8 1 4 Cool and dilute the sample to about 30 ml and adjust the pH of the sample to 7 0

±O 2 With 1 N NaOH (7 10) usmg a pH meter Ifsample IS not clear at thiS pomt,

add 2-3 drops ofaCid (7 6) and filter DIlute to 50 ml

Alternatively, Ifautoclaved see NOTE 1

8 1 5 Determme phosphorus as outhned m 8 J 2 Orthophosphate

8 2 Hydrolyzable Phosphorus

82 1 Add 1ml ofHzS04 solutIOn (76) to a 50 ml sample m a 125 ml Erlenmeyer flask

8 2 2 Boll gently on a pre-heated hot plate for 30-40 mInutes or untll a final volume of

about 10 mIlS reached Do not allow sample to go to dryness AlternatIvely, heat

for 30mmutesIn an autoclave at 121°C (15-20 pSI)

8 2 3 Cool and dllute the sample to about 30 ml and adjust the pH of the sample to 7 0

±O 2 With NaOH (7 10) usmg a pH meter Ifsample IS not clear at thiS POInt, add

2-3 drops ofaCid (7 6) and filter Dllute to 50 ml

Alternatively, If autoclaved see NOTE 1

8 2 4 The sample IS now ready for determmatlOn of phosphorus as outhned In 8 3 2

Orthophosphate

8 3 Orthophosphate

8 3 1 The pH ofthe sample must be adjusted to 7±O 2 usmg a pH meter

8 3 2 Add 8 0 ml of combmed reagent (7 5) to sample and mix thoroughly After a

mmlmum of ten mInutes, but no longer than thirty mmutes, measure the color

absorbance of each sample at 650 or 880 nm With a spectrophotometer, usmg the

reagent blank as the reference solutIOn

NOTE 1: Ifthe same volume ofsodmm hydrOXide solutIOn IS not used to adjust the

pH ofthe standards and samples, a volume correctIOn has to be employed

9 CalculatIOn

9 1 Prepare a standard curve by plottmg the absorbance values of standards versus the

correspondIng phosphorus concentratIOns

9 1 1 Process standards and blank exactly as the samples Run at least a blank and two

standards With each senes ofsamples Ifthe standards do not agree wlthm ±2% of

the true value, prepare a new cahbratlOn curve

9 2 Obtam concentratIOn value of sample directly from prepared standard curve Report

results as P, mg!1 SEE NOTE 1.

3652-5
10 PrecIsion and Accuracy

10 1 Thirty-three analysts m nmeteen laboratorIes analyzed natural water samples contammg

exact mcrements oforgamc phosphate, with the followmg results

Increment as

Total Phosphorus

mg P/Itter

PreCISIon as

Standard DeVIatIOn

mg P/Itter

Bias,

%

Accuracy as

BIas

mg P/hter

0110

0132

0772

0882

0033

0051

0130

0128

+309

+1199

+296

-092

+0003

+0016

+0023

-0008

(FWPCA Method Study 2, NutrIent Analyses)

102 Tv.enty-slx analysts m SIXteen laboratOrIes analyzed natural water samples contamIng

exact Increments oforthophosphate, WIth the followmg results

Increment as

Orthophosphate

mg Plliter

0029

0038

0335

0383

PreCISIon as

Standard DeVIatIOn

mg Plliter

0010

0008

0018

0023

BIas,

%

-495

-600

-275

-176

Accuracy as

Bias,

mg Plliter

-0001

-0002

-0009

-0007

(FWPCA Method Study 2, NutrIent Analyses)

BIblIography

1 Murphy, J , and RIley, J , "A modified SIngle SolutIOn for the DetermInatIOn of Phosphate In

Natural Waters", Anal Chim Acta, 27, 31 (1962)

2. Gales, M, Jr, Juhan, E, and Kroner, R, "Method for QuantItatIve Determmatton of Total

Phosphorus In Water", Jour AWWA, 58, No 10,1363 (1966)

3. Annual Book of ASTM Standards, Part 31, "Water", Standard 0515-72, Method A, p 389

(1976)

4 Standard Methods for the EXamInatIOn ofWater and Wastewater, 14th EdItIOn, p 476 and 481,

(1975)

3652-6
PHOSPHORUS, ALL FORMS

Method 365.3 (Colorimetric, Ascorbic Acid, Two Reagent)

STORET NO. See Section 4

1 Scope and ApplicatlOn

1 1 These methods cover the determmatlOn of specified forms of phosphorus m dnnkmg,

surface and saline waters, domestic and mdustnal wastes

1 2 The methods are based on reactlOns that are specific for the orthophosphate lOn Thus,

dependmg on the prescnbed pretreatment of the sample, the vanous forms may be

determmed

1 2 1 Except for m-depth and detal1ed studies, the most commonly measured forms are

phosphorus and dissolved phosphorus, and orthophosphate and dissolved

orthophosphate Hydrolyzable phosphorus IS normally found only m sewage-type

samples and msoluble forms ofphosphorus are determmed by calculatlOn

1 3 The methods are usable m the 001 to 1 2 mg P/1 range

2 Summary ofMethod

2 1 Ammomum molybdate and antimony potassmm tartrate react m an aCid medmm with

dl1ute solutions of phosphorus to form an antlmony-phospho-molybdate complex This

complex IS reduced to an mtensely blue-colored complex by ascorbic aCid The color IS

proportlOnal to the phosphorus concentr~tlOn

2 2 Only orthophosphate forms a blue color m this test Polyphosphates (and some orgamc

phosphorus compounds) may be converted to the orthophosphate form by sulfunc-acldhydrolYSIS Orgamc phosphorus compounds may be converted to the orthophosphate

form by persulfate dlgestlOn

3 Sample Handling and PreservatlOn

3 1 If benthiC depOSits are present m the area bemg sampled, great care should be taken not

to mc1ude these depOSits

3 2 Sample contamers may be ofplastic matenal, such as cubltamers, or ofPyrex glass

3 3 Ifthe analySIS cannot be performed the day of collectlOn, the sample should be preserved

by the addltlOn of2 ml conc H2S04 per liter and refngeratlOn at 4°C

4 Defimttons and Storet Numbers ,

4 1 Total Phosphorus (P) - all ofthe phosphorus present m the sample, regardless oHorm,

as measured by the persulfate digestion procedure (00665)

41 1 Total Orthophosphate (P, ortho) - morgamc phosphorus [(P04t 3

] m the sample

as measured by the direct colonmetnc analySIS procedure (70507)

412 Total Hydrolyzable Phosphorus (P, hydro) - phosphorus m the sample as

measured by the sulfunc aCid hydrolysIs procedure, and mmus pre-determmed

orthophosphates ThiS hydrolyzable phosphorus mc1udes polyphosphorus

[(P20 7)-4, (P30 1Ot 5

, etc] plus some orgamc phosphorus (00669)

Approved for NPDES

Issued 1978

3653-1
413 Total Orgamc Phosphorus (P, org) - phosphorus (Inorgamc plus oXidizable

orgamc) In the sample measured by the persulfate digestiOn procedure, and mInUS

hydrolyzable phosphorus and orthophosphate (00670)

4 2 Dissolved Phosphorus (P-D) - all of the phosphorus present In the filtrate of a sample

filtered through a phosphorus-free filter of 0 45 miCron pore Size and measured by the

persulfate digestiOn procedure (00666)

42 1 Dissolved Orthophosphate (P-D, ortho) - as measured by the direct colonmetnc

analysis procedure (00671)

422 Dissolved Hydrolyzable Phosphorus (P-D, hydro) - as measured by the sulfunc

aCid hydrolysis procedure and mInUS pre-determIned dissolved orthophosphates

(00672)

4 2 3 Dissolved OrganIc Phosphorus (P-D, org) - as measured by the persulfate

digestiOn procedure, and mInUS dissolved hydrolyzable phosphorus and

orthophosphate (00673)

4 3 The follOWIng forms, when suffiCient amounts ofphosphorus are present In the sample to

warrant such conSideratiOn, may be calculated

4.3 1 lnsolublePhosphorus (P-I)=(P)-(P-D) (00667)

43 1 1 Insoluble orthophosphate (P-I, ortho)= (P, ortho) - (P-D, ortho)

(00674)

43 12 Insoluble Hydrolyzable Phosphorus (P-I, hydro)=(P, hydro) - (P-D,

hydro) (00675)

43 13 Insoluble Orgamc Phosphorus (P-I, org)=(P, org) - (P-D, org)

(00676)

44 All phosphorus forms shall be reported as P, mg/l, to the third place

5. Interferences

5.1 Arsenate is determIned siml1anly to phosphorus and should be conSidered when present

ThiS Interference may be ehmInated by redUCIng the arsemc aCid to arsemous aCid With

SodIUm bisulfite (7 4)

5 2 When high concentratiOns of iron are present low recovery of phosphorus w111 be

obtaIned because it w111 use some ofthe redUCIng agent The bisulfite treatment w111 also

ehIDlnate thiS Interference

6. Apparatus

6.1 Photometer-A spectrophotometer or filter photometer SUitable for measurements at 660

or 880 nm With a 11ght path of! cm or longer

6 2 AC1d-washed glassware All glassware used should be washed With hot 1 1 HCI and

nnsed With distl1led water The aCid-washed glassware should be filled With distilled

water and treated w1th all the reagents to remove the last traces ofphosphorus that IDlght

be absorbed on the glassware Preferably, thiS glassware should be used only for the

determInatiOn of phosphorus and after use it should be rInsed With distl1led water and

kept covered untl1 needed agaIn Ifthis is done, the treatment With 1 1 HCI and reagents

1S only reqUired occaSiOnally Commercial detergents should never be used

6.3 Water bath, 95°C

3653-2
7 Reagents

7 1 Ammomum molybdate-antimony potassmm tartrate solutIOn DIssolve 8 g of

ammomum molybdate and 0 2 g antImony potassIUm tartrate m 800 ml ofdIstilled water

and dIlute to 1 lIter

7 2 AscorbIc aCId solutIOn DIssolve 60 g of ascorbIc aCId in 800 ml of dIstIlled water and

dIlute to 1hter Add 2 ml ofacetone ThIS SolutIon IS stable for two weeks

7 3 Sulfunc aCId, 11 N Slowly add 310 ml of conc H2S04 to approxImately 600 ml dIstIlled

water Cool and dIlute to 1000 ml

74 SodIUm bIsulfite (NaHS03) solutIOn DIssolve 52 g of NaHS03 m 100 ml of ION

H2S04

7 5 Ammomum persulfate

7 6 Stock phosphorus solutIOn DIssolve 04393 g of predned (105°C for one hour) KH2P04

m dIstIlled water and dIlute to 1000milO ml = 0 1mg P

7 7 Standard phosphorus solutIOn Dilute 100 ml of stock phosphorus solutIOn to 1000 ml

wIth dIstilled water 1 0 ml = 001 mg P Prepare an appropnate senes ofstandards by

dIlutmg sUItable volumes ofstandard or stock solutIOns to 100 ml wIth dIstIlled water

8 Procedure

8 1 Total Phosphorus

8 1 1 Transfer 50 ml ofsample or an alIquot dIluted to 50 ml mto a 125 ml Erlenmeyer

flask and add 1ml of 11 N sulfunc aCId (7 3)

8 1 2 Add 0 4 g ammomum persulfate (7 5), mIX and boll gently for approxImately

30-40 mmutes or untIl a final volume of about 10 mIlS reached Alternatively heat

for 30 mmutes m an autoclave at 121°C (15-20 pSI) Cool, dIlute to approxImately

40 ml and filter

8 1 3 For samples contammg arsemc or hIgh levels of Iron, add 5 ml ofsodIUm bIsulfite

(7 4), mIX and place m a 95°C water bath for 30 mmutes (20 mmutes after the

temperature ofthe sample reaches 95°C) Cool and dIlute to 50 ml

8 1 4 Determme phosphorus as outlIned m (8 3) orthophosphate

8 2 Hydrolyzable Phosphorus

8 2 1 Add 1ml ofH2S04 solutIOn (8 3) to a 50 ml sample m a 125 ml Erlenmeyer flask

822 Boll gently on a pre-heated hot plate for 30-40 mmutes or untIl a final volume of

about 10 mIlS reached Do not allow sample to go to dryness Alternatively, heat

for 30 mmutes m an autoclave at 121°C (15-20 pSI) Cool, dIlute to apprOXImately

40 ml and filter

8 2 3 Treat the samples as m 8 1 3

8 2 4 Determme phosphorus as outlmed m (8 3) orthophosphate

8 3 Orthophosphate

8 3 1 To 50 ml ofsample and/or standards, add 1ml of 11 N sulfunc aCId (7 3) and 4 ml

of ammomum molybdate-antimony potaSSIUm tartrate (7 1) and mIX

NOTE: If sample has been dIgested for total or hydrolyzable phosphorus do not

add aCId

8 3 2 Add 2 ml ofascorbIC aCId solutIOn (7 2) and mIX

3653-3
8 3 3 After 5 mmutes, measure the absorbance at 650 nm wIth a spectrophotometer and

determme the phosphorus concentratlOn from the standard curve The color IS

stable for at least one hour For concentratlOns m the range of0 01 to 03 mg PII, a

5 cm cell should be used A one cm ceil should be used for concentratlOns m the

range of0 3 to 1 2 mg PI1

9 CalculatlOn

9 1 Prepare a standard curve by plottmg the absorbance values of standards versus the

correspondmg phosphorus concentratlOns on lmear graph paper

9 2 Obtam concentratlOn value of sample dIrectly from prepared standard curve Report

results as P, mgll

10 PreclslOn and Accuracy

10 1 Precision data IS not aval1able at thIS tIme

10 2 In a smgle laboratory (EMSL) usmg mdustnal waste and sewage samples at

concentratlOns of7 6 and 055 mg PII, recovenes were 99 and 100%, respectively

3653-4
PHOSPHORUS, TOTAL

Method 365.4 (Colorimetric, Automated, Block Digest()r AA II)

STORET NO. 00665

1 Scope and ApplicatlOn

1 1 ThIs method covers the determmatlOn of tOial phosphorus m drInkmg water, surface

water and domestIc and mdustnal wastes The applicable range ofthis method IS 0 01 to

20 mgP/1

2 Summary ofMethod

2 1 The sample IS heated m the presence ofsulfuric aCId, K2S04 and HgS04 for two and one

half hours The resIdue IS cooled, dIluted to 25 ml and placed on the AutoAnalyzer for

phosphorus determmatlOn

3 Sample HandlIng and PreservatlOn

3 1 Sample contamers may be ofplastIc material, such as a cubitamer, Qr ofPyrex glass

3 2 Ifthe analysIs cannot be performed the day of collectlOn, the sample should be preserved

by the addItion of2 m1 ofconc H2S04 per lIter and refrIgeratlOn at 4°C

4 Apparatus

4 1 Block Digestor BD-40

42 Techmcon Method No 327-74W for Phosphorus

5 Reagents

5 1 MerCUriC sulfate DIssolve 8 g red merCUriC oXIde (HgO) m 50 ml of 1 4 sulfurIc aCId

(10 conc H2S04 40 ml dIStilled water) and dIlute to 100 ml wIth dIstIlled water

5 2 DigestlOn solution (SulfUriC aCId-mercuriC sulfate-potassmm sulfate solutlOn) DIssolve

133 g of K2S04 m 600 ml of dIstIlled water and 200 ml of conc H2S04 Add 25 ml of

mercunc st'lfate SOl1,ltlOn (5 1) and dIlute to 1lIter

53 SulfuncaCldsolutlOn(0 72N) Add 20 ml ofconc sulfuncaCldt08000fdIstI1ledwater,

mIX and dIlute to 1lIter

5 4 Molybdate/antimony solutlOn DIssolve 8 g of ammomum molybdate and 0 2 g of

antImony potassmm tartrate m about 800 ml ofdIstIlled water and dIlute to 1lIter

5 5 AscorbIc aCId solutlOn DIssolve 60 g of ascorbIc aCId m about 600 ml of dIstIlled water

Add 2 ml ofacetone and dIlute to 1lIter

5 6 DIluent water DIssolve 40 g of NaCl m about 600 ml of dIstIlled water and dIlute to 1

lIter

5 7 Sulfuric aCId solutlOn, 4% Add 40 ml of conc sulfuric aCId to 800 ml of ammoma-free

dIstIlled water, cool and dIlute to 1 lIter

6 Procedure

Digestion

6 1 To 20 or 25 ml ofsample, add 5 ml ofdigestlOn SolutIon and mIX (Use a vortex mIxer)

6 2 Add 4--8 Teflon boIlmg chips Too many boIlmg ChIpS WIll cause the sample to boll over

Pendmg approval for NPDES and Section 304(h), CWA

Issued 1974

3654-1
63 With Block Dlgestor In manual mode set low and high temperature at 160°C and preheat

umt to 160°C Place tubes In dlgestor and sWitch to automatic mode Set low temperature

timer for 1hour Reset high temperature to 380°C and set timer for 2112 hours

6 4 Cool sample and dilute to 25 ml with distilled water IfTKN IS determmed the sample

should be diluted with ammoma-free water

Colonmetnc AnalysIs

6 4 1 Check the level ofall reagent contamers to ensure an adequate supply

642 Excludmg the molybdate/antimony hne, place all reagent hnes m their respectIve

contaIners, connect the sample probe to the Sampler IV and start the proportlOmng

pump

643 Flush the Sampler IV wash receptacle with about 25 ml of 4% sulfunc aCid (5 7)

6 44 When reagents have been pumpmg for at least five mmutes, place the

molybdate/antimony hne In ItS contamer and allow the system to eqUlhbrate

6 4 5 After a stable baselIne has been obtamed, start the sampler

7 CalculatIons

7 1 Prepare a standard curve by plottIng peak heights of processed standards agamst

concentratIOn values Compute concentratIOns by companng sample peak heights with

the standard curve

8. PreCIsion and Accuracy

8 1 In a sIngle laboratory (EMSL) usmg sewage sample contammg total P at levels of 0 23,

1 33, and 20, the precISion was ±O 01, ±O 04, and ±O 06, respectively

82 In a smgle laboratory (EMSL) usmg sewage samples of concentratIOn 1 84 and 1 89, the

recovenes were 95 and 98%, respectively

Blbbography

1 McDamel, W H, Hemphill, R N and Donaldson, W T , "Automatic Determmatlon of Total

Kjeldahl Nitrogen m Estuanne Water", Techmcon Symposia, pp 362-367, Vol 1,1967

2 Gales, M.E and Booth, R L, "EvaluatIOn of Orgamc NItrogen Methods", EPA Office of

Research and Momtonng, June, 1972

3 Gales, M E and Booth, R L, "Simultaneous and Automated DetermmatlOn of Total

Phosphorus and Total Kjeldahl Nitrogen", Methods Development and Quahty Assurance

Research Laboratory, May, 1974

4. Techmcon "Total Kjeldahl Nitrogen and Total Phosphorus BD-40 DigestIOn Procedure for

Water", August, 1974

5 Gales, ME, and Booth, R L, "Evaluation of the Techmcon Block Dlgestor System for the

Measurement of Total KJeldahl Nitrogen and Total Phosphorus", EPA-600 /4-78-015,

EnVironmental Momtonng and Support Laboratory, Cmcmnatl, OhIO

3654-2
W

0\

VI

1"

w

TO PUMP TU

ml/mln

BLK BLK 032 AIR

10 TURNS I WHT WHT 060 NeCI SOLUTION

1116-0489-01 ORN ORN 042 SAMPLE

5 TURNS 37°C 10 TURNS 20 TURNS BLK BLK 032 AIR

157-13273-03 157-B089

0000 /I 1lO0 I 0000 OMO I WHT WHT 060 ACID SOLUTION

J -

I ORN YEL 016 RESAMPLE TO WASTE

BLK BLK 032 MOLYBDATE-ANTIMONY

BLK BLK 032 ASCORBIC ACID

WASTE

,

YEL YEL 12 WASTE

aE I~

COLORIMETER

660nm

50mm FIC x 1 5mm ID

FIGURE 1 PHOSPHORUS MANIFOLD AA11
SILICA, DISSOLVED

Method 370.1 (Colorimetric)

STORET NO. Dissolved 00955

1 Scope and ApphcatlOn

1 1 ThIS method IS apphcable to dnnkmg, surface and salme waters, domestic and mdustnal

wastes

1 2 The workmg range of the method IS approXImately 2 to 25 mg slhca/1 The upper range

can be extended by takmg sUltable ahquots, the lower range can be extended by the

addltlOn ofammo-naphthol-sulfomc aCId solutlOn, as descnbed m (6 8)

2 Summary ofMethod

2 1 A well-mIxed sample IS filtered through a 0 45 u membrane filter The filtrate, upon the

addltlOn of molybdate lOn m aCIdIC solutlOn, forms a greemsh-yellow color complex

proportlOnal to the dIssolved slhca m the sample The color complex IS then measured

spectrophotometncally

22 In the low concentratlOn modlficatlOn the yellow (410 nm) molybdoslhclC aCId color IS

reduced by 1-ammo-2-naphthol-4-sulfomc aCId to a more mtense heteropoly blue (815

nmor650nm)

3 Interferences

3 1 ExceSSIve color and/or turbIdIty mterfere Correct by runmng blanks prepared wIthout

addItion ofthe ammomum molybdate solutlOn See (6 7)

32 Tanmn mterference may be ehmmated and phosphate mterferences may be decreased

wIth oxahc aCId

3 3 Large amounts ofIron and sulfide mterfere

3 4 Contact wIth glass should be mlmmlzed, slhca free reagents should be used as much as

possIble A blank should be run

4 Apparatus

4 1 Platmum dIshes, 100 ml

4 2 Colonmetnc eqUlpment-one ofthe followmg

4 2 1 Spectrophotometer for use at 410 nm, 650 nm and/or 815 nm wIth a 1 cm or longer

cell

422 FIlter photometer wIth a vlOlet filter havmg maXImum transmIttance as near 410

nm as possIble and a 1 cm or longer cell

4 2 3 Nessler tubes, matched, 50 ml, tall form

5 Reagents

5 1 Use chemIcals low m slhca and store m plastIc contamers

52 Sodmm bIcarbonate, NaHC03, powder

53 Sulfunc aCId, H2S04, 1 N

Approved for NPDES

Issued 1971

Edltonal reVlSlOn 1978

370 I-I
5 4 Hydrochlonc aCId, HCI, 1 + 1

5 5 Ammomum molybdate reagent Place 10 g (NH4)6M07024·4H20 m dIstilled water m a

100 ml volumetnc DIssolve by stIrnng and gently warmmg Dilute to the mark FIlter If

necessary Adjust to pH 7 to 8 WIth sIhca free NH40H or NaOH Store in plastIC bottle

56 Oxahc aCId solutiOn DIssolve 10 g H2C20 4·2H20 m dIstilled water m a 100 ml

volumetnc flask, dilute to the mark Store m plastIC

57 Stock silIca solutiOn DIssolve 4 73 g sodiUm metasilICate nonahydrate, Na2SI03·9H20,

m recently boiled and cooled dIstilled water Dilute to approxImately 900 ml Analyze

100 0 ml portiOns by graVImetry (ref 1, p 484) Adjust concentratiOn to 1000 mg/1

8102 Store m tIghtly stoppered plastIC bottle

5.8 Standard slhca solutiOn DIlute 10 0 ml stock solutiOn to 1 hter WIth recently boiled and

cooled dIstilled water ThIS IS 10 mg/1 S102(1 00 ml = 10 0 ug SI02) Store m a tIghtly

stoppered plastICbottle

5.9 Permanent colorsolutiOns

591 PotassiUm chromate solution DIssolve 630 mg K2Cr04 m dIstilled water mal

hter volumetnc flask and dilute to the mark

. 592 Borax solution DIssolve 10 g sodiUm borate decahydrate, (Na2B407·lOH20) m

d1stilled water mal hter volumetnc flask and dIlute to the mark

5.10 Reducmg agent DIssolve 500 mg of 1-ammo-2-naphthol-4-sulfomc aCId and 1 g Na2S03

m 50 ml dIstIlled water WIth gentle warmIng If necessary DIssolve 30 g NaHS03m 150

m1 dIstIlled water MIX these two solutiOns FIlter mto a plastic bottle Refngerate and

aVOId exposure to hght DIscard when It darkens If there IS mcomplete solubIhty or

ImmedIate darkemng ofthe ammonaphthosulfomc aCId solutiOn do not use

6 Procedure

6 1 FIltersample through a 0 45 u membrane filter

6 2 DIgestIon If molybdate unreactive SIlIca IS present and ItS mc1usiOn m the analySIS IS

deSIred, mclude thIS step, otherWIse proceed to 6 3

62 1 Place 50 ml, or a smaller portiOn dIluted to 50 ml, offiltered (6 1) sample m a 100

ml platmum dISh

622 Add 200 mg sIhca-free NaHC03(52) and dIgest on a steam bath for 1 hour Cool

62 3 Add slowly and WIth stlrrmg 24 ml H2S04 (5 3)

624 ImmedIately transfer to a 50 ml Nessler tube, dIlute to the mark WIth dIStilled

water and proceed to 6 3 WIthout delay

6 3 Color development

63 1 Place 50 ml sample m a Nessler tube

6 3 2 Add rapIdly 1 0 ml of 1+1 HCI (5 4) and 2 0 ml ammOnium molybdate reagent

(55)

6 3 3 MIX by mvertmg at least 6 tImes

6 3 4 Letstand 5 to 10 mmutes

63 5 Add 1 5 ml oxahc aCId solutiOn (5 6) and mIX thoroughly

636 Read color (spectrophotometncally or VIsually) after 2 mmutes but before 15

mmutes from the addItiOn ofoxalIc aCid

370 1-2
64 PreparatIon ofStandards

641 If dIgestIOn (62) was used add 200 mg NaHC03 (52) and 24 ml H2S04 (5 3) to

standards to compensate for sIhca Introduced by these reagents and for effect ofthe

salt on the color IntensIty

6 5 Photometnc measurement

6 5 1 Prepare a cahbration curve USIng approxImately SIX standards to span the range

shown below wIth the selected hght path

Se1ection of LIght Path Length for Vanous

SIhca ConcentratIons

LIght Path

cm

1

2

5

10

SIhca In 54 5 ml

final volume (ug)

200-1300

100-700

40-250

20-130

6 5 2 Carry out the steps In 6 3 USIng dIstilled water as the reference Read a blank

6 5 3 Plot photometnc readIng versus ug ofsIhca In the final solutIOn of 54 5 ml Run a

reagent blank and at least one standard wIth each group ofsamples

66 VIsual ComparIson

6 6 1 Prepare a set of permanent artIfiCIal color standards accordIng to the table Use

well stoppered, properly labelled 50 ml Nessler tubes

PotaSSiUm

SIhca chromate Borax DIstIlled

value solutIOn solutIOn water

mg (591) ml (592) ml ml

000 00 25 30

010 10 25 29

020 20 25 28

040 40 25 26

050 50 25 25

075 75 25 22

100 100 25 20

662 Venfy permanent standards by companson to color developed by standard sII1ca

solutIOns

6 6 3 These permanent artifiCIal color standards are only for color companson

i>rocedure, not for photometnc procedure

6 7 Correction for color or turbIdIty

6 7 1 A speCIal blank IS run USIng a portion ofthe sample and carryIng out the procedure

m6 1,6 2 If used, and 63 except for the addItion of ammomum molybdate:6 J 2)

370 1-3
6 7 2 Zero the photometer wIth thIS blank before readIng the samples

6.8 Procedure for low concentratIOn ( < 1000 ug/l)

6 8 1 Perform steps 6 1 and 6 21fneeded

6 8 2 Place 50 ml sample In a Nessler tube

6 8 3 In rapid succeSSIon add 1 0 ml of 1+1Hel (5 4)

6 8 4 Add 2 0 ml ammOnIum molybdate reagent (5 5)

6 8 5 MIx by InvertIng at least SIX tImes

6.8 6 Letstand 5 to 10 mInutes

6 8 7 Add 1 5 ml oxalIc aCId solutIOn (5 6)

6 8.8 MIX thoroughly

6 8.9 At least 2, but not more than 15 mInutes after oxalIc aCId addItIon, add 2 0 ml

reducIng agent (5 10)

6 8 10 MIx thoroughly

6 8 11 Walt 5 mInutes, read photometncally or Visually

6 8 12 IfdIgestIOn (6 2) was used see (64)

6 8 13 Photometnc measurement

68 13 1 Prepare a calIbratIOn curve USIng approxImately 6 standards and a

reagent blank to span the range shown below WIth the selected lIght

path

SelectlOn of LIght Path Length for

VarIous Siltca ConcentratIons

LIght Path

em

Siltea In 56 5 ml FInal volume, ug

650 nm 815 nm

1

2

5

10

40-300

20-150

7-50

4-30

20-100

10-50

4-20

2-10

6 8 13 2 Read versus distIlled water

6 8 13 3 Plot photometnc readIng at 650 nm or at 815 nm versus ug of SIlIca In

565 ml.

6 8 13 4 For turbIdIty correctIOn use 6 1, 62 If used and 6 8 2-6 8 11 omIttIng

68 4and6 8 9

68 135 Run a reagent blank and at least one standard (to check calIbratIon

curve dnft) WIth each group ofsamples

68 14 VIsual companson

6 8 14 1 Prepare not less than 12 standards covenng the range of 0 to 120 ug

8102 by plaCIng the calculated volumes ofstandard SIlIca (5 8) In 50 ml

Nessler tubes, dl1utIng to the mark and develop the calor as In

682-6811

370 1-4
7 Calculatlons

7 1 Read ug SI02from cahbratton curve or by vIsual companson

7 2 mg/l SI02= Ug/SI02

ml sample

7 3 Report whether NaHC03 dIgestIOn (6 2) was used

8 PrecISIOn and Accuracy

8 1 A synthetlc unknown sample contammg 5 0 mg/l SI02' 10 mg/l chlonde, 0 200 mg/l

ammoma N, 10 mg/l mtrate N, 15 mg/l orgamc N, and 10 0 mg/l phosphate m

dIstIlled water was analyzed m 19 laboratones by the molybdosIhcate method, wIth a

relatlve standard devIatIOn of 143% and a relative error of7 8%

82 Another synthetIc unknown sample contammg 150 mg/l SI02, 200 mg/l chlonde,

0800 mg/l ammoma N, 10 mg/l mtrate N, 0800 mg/l orgamc N, and 50 mg/l

phosphate m dIstIlled water was analyzed m 19 laboratones by the molybdosIhcate

method, wIth a relative standard devIatIOn of8 4% and a relative error of4 2%

83 A thIrd synthetlc unknown sample contammg 300 mg/l SI02, 400 mg/l chlonde, 1 50

mg/l ammoma N, 10 mg/l mtrate N, 0200 mg/l orgamc N, and 0500 mg/l

phosphate m dIstIlled water was analyzed m 20 laboratones by the molybdosIhcate

method, wIth a relatIve standard devIatIOn of 7 7% and a relative error of 9 8% All

results were obtamed after sample dIgestIOn wIth NaHC03

8 4 Photometnc evaluatIons by the ammo-naphthol-sulfomc aCId procedure have an

estImated precIsIOn of ±O 10 mg/l m the range from 0 to 2 mg/l (ASTM)

8 5 Photometnc evaluatIOns of the sIhco-molybdate color m the range from 2 to 50 mg/l

have an estImated precIsIOn of approXImately 4% of the quantlty of sIhca measured

(ASTM)

BIblIography

1 Annual Book ofASTM Standards, Part 31, "Water", Standard D859-68, p 401 (1976)

2 Standard Methods for the Exammation of Water and Wastewater, 14th EdItIon, p 487,

Method 426B, (1975)

370 1-5
SULFATE

Method 375.1 (Colorimetric, Automated, Chloranilate)

STORET NO. Total 00945

1 Scope and ApphcatiOn

1 1 ThIs automated method IS apphcable to dnnkmg and surface waters, domestic and

mdustnal wastes, m the range of 10 to 400 mg S04/1 ApproXImately 15 samples per

hour can be analyzed

2 Summary ofMethod

2 1 When soItd banum chloramlate IS added to a solutiOn contammg sulfate, banum sulfate

IS preCIpItated, releasmg the hIghly colored aCId chloramlate Ion The color mtenslty m

the resultmg chloramhc aCId IS proportiOnal to the amount ofsulfate present

3 Sample Handhng and PreservatiOn

3 1 RefngeratiOn at 4°C

4 Interferences

4 1 Cations, such as calcIUm, alummum, and Iron, mterfere by preclpltatmg the chloramlate

These iOns are removed automatically by passage through an Ion exchange column

5 Apparatus

5 1 Techmcon AutoAnalyzer conslstmg of

5 1 1 Sampler I

5 1 2 Contmuousfilter

513 Mamfold

5 1 4 ProportiOmng pump

5 1 5 Colonmeter eqUIpped WIth 15 mm tubular flow cell and 520 nm filters

5 1 6 Recorder

5 1 7 Heatmg bath, 45°C

5 2 MagnetIc stirrer

6 Reagents

6 1 Banum chloramlate Add 9 g of banum chloramlate (BaC6CI20 4) to 333 ml of ethyl

alcohol and dIlute to lItter WIth dlsttlled water

6 2 Acetate buffer, pH 4 63 DIssolve 13 6 g ofsodIUm acetate m dIstIlled water Add 6 4 ml

ofacetIc aCId and dtlute to lItter WIth dlsttlled water Make fresh weekly

63 NaOH-EDTA solutIon DIssolve 65 g ofNaOH and 6 g ofEDTA m dlsttlled water and

dtlute to lItter

NOTE 1: ThiS solutiOn IS also used to clean out mamfold system at end ofsampItng run

64 Ion exchange resm Dowex-50 W-X8, lomc form-H+

NOTE 2: Column IS prepared by suckmg a slurry ofthe resm mto 12 mches of 3/16-mch

OD sleevmg ThiS may be convemently done by usmg a pipette and a loose-fittmg glass

wool plug m the sleeve The column, upon exhaustiOn, turns red.

Issued 1971

375 1-1
65 Stock solution DIs!>olve 14790 g of oven-dned (105°C) Na2S04 m dIstIlled water and

dIlute to 1lIter m a volumetrIc flask 1 0 ml = 1 0 mg

6 5 1 Prepare a senes ofstandards by dIlutmg smtable volumes ofstock solutIOn to 100 0

ml WIth dIstIlled water The followmg dIlutIOns are suggested

ml of Stock SolutIOn Cone, mg/l

10 10

20 20

40 40

60 60

80 80

100 100

150 150

200 200

300 300

400 400

7. Procedure

7.1 Set up mamfold as shown m FIgure 1 (Note that any preCIpItated BaS04and the unused

banum chloramlate are removed by filtratIon If any BaS04 should come through the

filter, It IS complexed by the NaOH-EDTA reagent)

7 2 Allow both colonmeter and recorder to warm up for 30 mmutes Run a baselIne WIth all

reagents, feedmg dIstIlled water through the sample lme Adjust dark current and

operatlve opemng on colonmeter to obtam smtable baselIne

7 3 Place dIstIlled water wash tubes m alternate opemngs m sampler and set sample tImmg at

20mmutes

7 4 Place workmg standards In sampler m order of decreasmg concentratIOn Complete

fillmg ofsampler tray WIth unknown samples

7 5 SWItch sample lIne from dIstIlled water to sampler and begm analysIs

8. CalculatIon

8 1 Prepare standard curve by plottmg peak heIghts of processed standards agamst known

concentratIOns Compute concentratIon of samples by companng sample peak heIghts

WIth standard curve

9. PreCIsIon and Accuracy

9.1 In a smgle laboratory (EMSL), usmg surface water samples at concentratIOns of39, 111,

188 and 294 mg S04/1, the standard deVIatIons were ±O 6, ±10, ±22 and ±O 8,

respectIvely _

92 In a smgle laboratory (EMSL), usmg surface water samples at concentratIOns of 82 and

295 mg S04/1, recoverIes were 99% and 102%, respectIvely

BiblIography

1 Barney, J E, and BertolocmI, R J , Anal Chern, 29, 283 (1957)

2 Gales, ME, Jr, Kaylor, W H and Longbottom, J E, "DetermmatIOn of Sulphate by

Automatlc ColorImetnc AnalYSIS", Analyst, 93, 97 (1968)

375 1-2
LM

80'

DELAY

COIL --=0.:::;

LM

w

-..l

Ul

-I

w OLAIGE 6 IXING

COIL

ILM]

SM

10M EXCHAItGE

o

P

P

y

BLUE

R

1II1/lftln

VI 1 20

!!JW.l..!0

RI 0 80

WI G23

f:QJ r STInER

BARIUM

CHLORAN ILAT E

AIR CONTINUOUSIFILTER

BU HER

SAMPLE

WASTE" IP .. pI250 I WASTE

ItROPOITIOMUIG PUMP

SMALL

MIXIIIG

COIL

ISMj

COLORIMETER

15 •• lUUURf/cl I

521 n. FILTERS

o

I I RECOIDER

SAMPLlIIG TIME 2 MIN

WASH lUBES ONE

FIGURE 1 . SULFATE MANIFOLD AA·I
SULFATE

Method 375.2 (Colorimetric, Automated, Methylthymol Blue, AA II)

STORET NO. 00945

1 Scope and ApplicatIOn

1 1 This automated method IS applicable to dnnkmg and surface waters, domestic and

mdustnal wastes

1 2 Samples m the range of 3 to 300 mg S04/1 can be analyzed The sensitIvity ofthe method

can be mcreased by a mmor modIficatIOn to analyze samples m the range of 0 5 to 30 mg

S04/1 Approximately 30 samples per hour can be analyzed

2 Summary ofMethod

2 1 The sample IS first passed through a sodmm form cation-exchange column to remove

multivalent metal Ions The sample contammg sulfate IS then reacted With an alcohol

solutIOn of banum chlonde and methylthymol blue (MTB) at a pH of 2 5-3 0 to form

banum sulfate The combined solutIOn IS raised to a pH of 125-130 so that excess

banum reacts With MTB The uncomplexed MTB color IS gray, IfIt IS all chelated With

banum, the color IS blue Imtlally, the banum and MTB are eqUlmolar and eqUlvalent to

300 mg S04/1, thus the amount ofuncompiexed MTB IS equal to the sulfate present

3 Sample Handlmg and Preservation

3 1 Refngeratlon at 4°C

4 Interferences

4 1 The Ion exchange column elimmates mterferences from multivalent cations A mid-scale

sulfate standard contammg Ca++ should be analyzed penod1cally to msure that the

column IS functlOmng properly

4 2 Samples With pH below 2 should be neutrahzed because high aCid concentratIOns elute

catIOns from the IOn exchange resm

4 3 Turbid samples should be filtered or centnfuged

5 Apparatus

5 1 Techmcon Auto Analyzer cons1stmg of

5 11 Sampler

5 1 2 Mamfold-h1gh or low level (FIgure I)

5 1 3 ProportlOmng pump

5 1 4 Colonmeter eqUlpped With 15 mm flow cell and 460 nm mterference filters

5 1 5 Recorder

5 1 6 Digital Pnnter for AAII (optIOnal)

6 Reagents

6 1 Barmlh chlonde Dissolve 1 526 g ofbanum chlonde dihydrate (BaCI2-2H20) m 500 ml

of distilled water and dilute to 1 liter

Pendmg approval for NPDES

Issued 1978

3752-1
62 Methylthymol blue DIssolve 0 1182 g of methylthymol blue (3'3"-bIS-N,N-biS

carboxymethyl)-ammo methylthymolsulfone-phthalem pentasodmm salt) m 25 ml of

banum chlonde solutIon (6 1) Add 4 ml of ION hydroch10nc aCid whIch changes the

color to bnght orange Add 71 ml of water and dtlute to 500 ml wIth ethanol The pH of

thts solution IS 2 6 ThIS reagent should be prepared the day before and stored m a brown

plastic bottle m the refngerator

6 3 Buffer, pH 10 5 ± 0 5 Dissolve 6 75 g of ammOnium chlonde m 500 ml of disttlied

water Add 57 m1 of concentrated ammOnium hydroxide and dtlute to one hter wIth

disttlied water

64 Buffered EDTA DIssolve 40 g oftetrasodmm EDTA m pH 10 5 buffer (63), and dtlute

to one hter wIth buffer

65 Sodmm hydrOXIde solutIOn, (50%) DIssolve 500 g NaOH m 600 ml of disttlied water,

cool, and dtlute to 1hter

66 Sodmm hydroxIde, 0 18N Dtlute 144 ml ofsodmm hydroxIde solutiOn (65) to 1hter

67 Ion exchange resm BIO-Rex 70, 20-50 mesh, sodmm form, Bio-Rad LaboratorIes,

RIchmond, Cahfornia Free from fines by stIfnng wIth several portiOns of deiOnized

water and decant the supernate before settlmg IS complete

68 Ddution Water Add 0 75 ml ofsulfate stock solutIOn (69) and 3 drops of BnJ-35 to 2

hters ofdisttlied water

69 Sulfate stock solutIOn, 1 ml = 1 mg 804 Dissolve 1479 g of dned (l05°C) NaZS04 m

dlsttlled water and dtlute to 1hter

6 10 DIlute sulfate solutiOn, 1 ml = 0 1 mg SO4 Dtlute 100 ml ofsulfate stock SolutIon (6 9)

to 1hter

6 11 HIgh level workmg standards, 10-300 mg/1 Prepare htgh level workmg standards by

dtlutmg the followmg volumes ofstock standard (6 9) to 100 ml

ml stock mg/l 804

1 10

5 50

10 100

15 150

25 250

30 300

612 Low level workmg standards, 1-30 mg/1 Prepare low level workmg standards by

dtlutmg the followmg volumes ofdtlute sulfate SolutIon (6 10) to 100 ml

ml stock mg/l 804

1 10

5 50

10 100

15 150

25 250

30 300

3752-2
7 Procedure

7 1 Set up the mamfold for hIgh (0-300 mg S04/1) or low (0-30 mg S04/1) level samples as

descnbed m FIgure I

7 2 The Ion exchange column IS prepared by pulhng a slurry ofthe resm mto a pIece of glass

tubmg 7 5 mches long, 2 0 mm ID and 3 6 mm OD ThIS IS convemently done by usmg a

pIpet and a loose fittmg glass wool plug m the tubmg Care should be taken to aVOid

allowmg aIr bubbles to enter the column If aIr bubbles become trapped, the column

should be prepared over agam The column can exchange the eqUlvalent of 35 mg of

calcmm For the hIgh level mamfold thIS corresponds to about 900 samples wIth 200

mg/l Ca The column should be prepared as often as necessary to assure that no more

than 50% ofItS capaCIty IS used up

7 3 Allow the colonmeter, recorder and pnnter to warm up for 30 mmutes Pump all

reagents untl1 a stable basehne IS achIeved

7 4 Analyze all workmg standards m duphcate at the begmmng of a run to develop a

standard curve The A and B control standards are analyzed every hour to assure that the

system remams properly cahbrated Smce the chemIstry IS non-hnear the 180 mg/l

standard IS set at 50% on the recorder usmg the standard cahbratIOn control on the

colonmeter

75 At the end of each day, the system should be washed WIth the buffered EDTA solutIOn

(64) ThIS IS done by placmg the methylthymol blue hne and the sodmm hydroxIde hne

m water for a few mmutes and then m the buffered EDTA solutIOn for 10 mmutes Wash

the system WIth water for 15 mmutes before shuttmg down

8 CalculatIOn

8 1 Prepare a standard curve by plottmg peak heIghts of processed standards agamst known

concentratIOns Compute concentratIOn of samples by comparmg sample peak heIghts

WIth the standard curve

9 PreCIsIon and Accuracy

9 1 In a smgle laboratory the estImated standard deVIatIOn, calculated from duphcate

analyses of 26 surface and wastewaters at a mean concentratIOn of 110 mg/l was ±1 6

mg/l

9 2 The mean recovery from 24 surface and wastewaters was 102%

BIblIography

1 Lazrus, A L, Hl1l, K C and Lodge, J P , "AutomatIOn m AnalytICal ChemIstry", Techmcon

Symposia, 1965

2 Coloros, E, Panesar, M R and Parry, F P, "Lmeanzmg the CahbratIOn Curve m

DetermmatIOn ofSulfate by the Methylthymol Blue Method", Anal Chern 48, 1693 (1976)

3752-3
TO WASTE (GRY.·GRY.)

E

TION WATER

PLE

YLTHYMOL BLUE

UM HYDROXIDE

M FIC

GRATE 30/hr. 61

OLYETHYLENE

**SILICONE RUBBER

gl

AND SAMPLE TUBES TO GRY/GRY (1.00)

TO SAMPLER Ml/MIN

WASH RECEPTACLE GRN GRN I 20

ION EXCHANGE 170-0103 01 BLK 8LK 032 AIR

COLUMN 116-GOO6·01 A 2 I GRN. GRN. 200 DILU -"'"""

[ 5 TURNS I 116-0489-01 ORN. GRN 0,10 SAM

o 110 STANDARD

WASTES SLEEVING GRY, GRY 7,00 WASJ, * 157 B095- 157-0370 1* BLK. BLK 0,32 AIR

nODDnnD 10000"" I I

20 22 I 116-0489 01 RED RED 0,70 METH

TURNS TURNS ORN ORN. 042 ** SODll

GRN GRN 200 FRm

** PROPORTIONING

~MPLES IN THE PUMP SAMPLlII

HANGE THE WATER * OJ)':lll

W

-..J

VI

ljJ

,J>.

FIGURE 1 SULFATE MANIFOLD AA11
SULFATE

Method 375.3 (Gravimetric)

STORET NO. Total 00945

1 Scope and ApphcatlOn

1 1 ThIS method 1<; apphcab1e to dnnkmg, surface and sahne water, domestic and mdustnal

wastes

1 2 ThIS method IS the most accurate method for sulfate concentratlOns above 10 mg/l

Therefore, It should be used whenever results ofthe greatest accuracy are reqUired

2 Summary ofMethod

2 1 Sulfate IS preCIpItated as banum sulfate m a hydrochlonc aCId mediUm by the addItion of

banum chlonde After a penod of digestlOn, the preCIpItate IS filtered, washed WIth hot

water until free ofchlonde, Igmted, and weIghed as BaS04

2 2 Preserve by refngeratlOn at 4°C

3 Interferences

3 1 HIgh results may be obtamed for samples that contam suspended matter, mtrate, sulfite

andsIhca

3 2 Alkah metal sulfates frequently yIeld low results ThIS IS espeCIally true of alkah

hydrogen sulfates OccluslOn of alkah sulfate WIth banum sulfate causes the SubstItutIon

of an element oflower atomIC weIght than bariUm m the preCIpItate Hydrogen sulfate of

alkah metal acts SImIlarly and decomposes when heated Heavy metals such as

chromiUm and Iron, cause low results by mterfenng WIth complete preCIpItatIOn and by

formatIOn ofheavy metal sulfates

4 Apparatus

4 1 Steam bath

4 2 Drymg oven, eqUIpped WIth thermostatic control

4 3 Muffie furnace WIth heat mdicator

4 4 DeSICcator

4 5 Analytical balance, capable ofweIghmg to a1 mg

46 FIlter paper, aCId-washed, ashless hard-fimsh filter paper suffiCIently retentive for fine

preCIpItates

5 Reagents

5 1 Methyl red mdicator solutIOn DIssolve 100 mg methyl red sodiUm salt m dIstIlled water

m a 100 ml volumetnc flask and dIlute to the mark WIth dIstIlled water

5 2 Hydrochlonc aCId, HCI, 1+1

5 3 Banum chlonde solutIOn DIssolve 100 g BaCI2-2H20 m 1 hter of dIstIlled water FIlter

through a membrane filter or hard-fimsh filter paper One ml ofthIS reagent IS capable of

precipitatmg approxImately 40 mg S04

Approved for NPDES

Issued 1974

Editonal reVISlOn 1978

3753-1
5 4 StIver mtrate-mtnc aCid reagent Dissolve 8 5 g AgN03 and 0 5 ml conc HN03 m 500 ml

distilled water

6. Procedure

6 1 Removal ofslhca Ifslhca concentratiOn IS greater than 25 mg/l

6 1 1 Evaporate sample nearly to dryness m a platmum dish on a steam bath

6 1 2 Add 1 ml HCI solutiOn (5 2), tilt dish and rotate unttI acid contacts all of the

residue

6 1 3 ContInue evaporatiOn to dryness

6 1 4 Complete drymg m an oven at 180°C

6 1 5 Iforgamc matter present, char over a flame

6 1 6 MOisten with 2 ml dlsttlled water and 1 ml HCI solutiOn (5 2)

6 1 7 Evaporate to dryness on a steam bath

6 1 8 Add 2 ml HCI solutiOn (5 2)

6.1 9 Take up soluble residue m hot dlsttIled water and filter

6 1 10 Wash the msoluble stIlca With several small portiOns ofhot dlsttIled water

6.1 11 Combme filtrate and washmgs

6 2 PreCipitation ofbanurn sulfate

62 1 Ifnecessary, treat clanfied sample to remove mterfenng agents

62 2 Adjust to contam approximately 50 mg S04iOn m a 250 ml volume

6 2 3 Adjust aCidity With HCI solutiOn (5 2) to pH 4 5 to 5 0, usmg pH meter or orange

color ofmethyl red mdlcator (5 1)

6 2 4 Add an addltiOnall to 2 ml HCI solutiOn (5 2)

6.2 5 Forlower concentratiOns ofsulfate Ion fix the total volume at 150 ml

62.6 Heat to botImg and, whtIe stIrnng gently, add warm BaCl2 solutiOn (5 3) slowly,

unttI precipitatiOn appears to be complete, then add approximately 2 ml m excess

627 Ifamount ofprecipitate IS small, add a total of5 ml BaCl2 solutiOn (53)

6 2 8 Digest the precipitate at 80 to 90°C preferably overnight but for not less than 2

hours

6 3 FtItratiOn and Welghmg

63 1 MiX a httle ashless filter paper pulp w1th the BaS04 and filter at room temperature

63 2 Wash the precipitate With small portiOns ofwarm dlstllied water untll the washmgs

are free of chlonde as mdiCated by testmg With sliver mtrate-mtnc aCid reagent

(5 4)

6 3 3 Dry the filter and precipitate

6 3 4 Igmte at 800°C for 1 hour DO NOT LET THE FILTER PAPER FLAME

6 3 5 Cool m a deSiCcator and weigh

7 Calculation

mg/l S04 = mg BaS04 x 411 5

ml sample

3753-2
8 PrecIsIOn and Accuracy

8 1 A synthetIc unknown sample contammg 259 mg/l sulfate, 108 mg/l Ca, 82 mg/l Mg,

3 1 mg/l K, 19 9 mg/l Na, 241 mg/l chlonde, 250 ug/l mtnte N, 1 1 mg/l mtrate N

and 42 5 mg/l alkahmty (contnbuted by NaHC03), was analyzed m 32laboratones by

the gravimetnc method, wIth a relatIve standard devIatIOn of4 7% and a relative error of

19%

BIblIography

1 Annual Book of ASTM Standards, Part 31, "Water", Standard D516-68, Method A, p 429

(1976)

2 Standard Methods for the ExammatIOn of Water and Wastewater, 14th EdItion, p 493,

Method 427A, (1975)

3753-3
SULFATE

Method 375.4 (Turbidimetric)

STORET NO. Total 00945

1 Scope and ApphcatlOn

1 1 ThIS method IS apphcable to dnnkmg and surface waters, domestIc and Industnal wastes

1 2 The method IS sUItable for all concentratIon ranges ofsulfate, however, In order to obtaIn

rehable readIngs, use a sample alIquot contaInIng not more than 40 mg S04/1

1 3 The mInImUm detectable hmlt IS approxImately 1mg/1 sulfate

2 Summary ofMethod

2 1 Sulfate Ion IS converted to a banum sulfate suspensIon under controlled condltlOns The

resultmg turbIdIty IS determIned by a nephelometer, filter photometer or

spectrophotometer and compared to a curve prepared from standard sulfate solutIons

2 2 Suspended matter and color mterfere Correct by runnIng blanks from WhICh the barIUm

chlonde has been omItted

2 3 SIlIca In concentratIons over 500 mg/1 WIll Interfere

3 Comments

3 1 Propnetary reagents, such as Hach Sulfaver or eqUIvalent, are acceptable

3 2 Preserve by refngeratlOn at 4°C

4 Apparatus

4 1 MagnetIc stIrrer, vanable speed so that It can be held constantJust below splashIng Use

IdentIcalshape and SIze magnetIc stlrrmg bars

4 2 Photometer one ofthe followmg WhICh are gIven In order ofpreference

4 2 1 Nephelometer

4 2 2 Spectrophotometerfor use at 420 nm wIth hght path of4 to 5 cm

4 2 3 FIlter photometer wIth a vlOlet filter haVIng a maXImum near 420 nm and a hght

path of4 to 5 cm.

4 3 Stopwatch, Ifthe magnetIc stIrrer IS not eqUIpped WIth an accurate tImer

4 4 MeasurIng spoon, capacIty 0 2 to 0 3 ml

5 Reagents

5 1 CondltlOnmg reagent Place 30 ml conc HCI, 300 ml dIstIlled water, 100 m195% ethanol

or Isopropanol and 75 g NaCI m solutlOn In a contamer Add 50 ml glycerol and mIX

5 2 Banum chlonde, BaCI2, crystals, 20 to 30 mesh

5 3 SodIUm carbonate SolutIon (approxImately 0 05N) Dry 3 to 5 g pnmary standard

Na2C03 at 250°C for 4 hours and cool m a deSIccator WeIgh 2 5 ±O 2 g (to the nearest

mg), transfer to a 1hter volumetnc flask and fill to the mark wIth dIstIlled water

Approved for NPDES

Issued 1971

Edltonal reVISIon 1978

3754-1
5 4 Standard sulfate solutlOn (1 00 tnl == lob ug S04) Prepare by eIther 5 4 1or 5 42

54. f Standard sulfate solutlOn from H2S04 '

5 4 1 I Standard sulfunc aCId, a IN dtlute 3 a ml conc H2S04 to 1 hter wIth

dIstdled water StandardIze versus 40 00 ml ofa 05 N Na2C03solution

(5 ~) wIth about 60 ml dIstilled water by titratmg potentlOmetrlcally to , . 'pH about 5 LIft electrodes and rmse mto beaker Bod gently for 3-5

mmutes under a watch glass cover Cool to room temperature Rmse

cover glass mto beaker Contmue tItratlOn to the pH mflectlOn pomt

Calculate normahty usmg

AxB

N:::: 53 00 x C

where

A ' gNa2C03 weIghed mto 1 hter

, B = ml Na2C03solutlOn ' "

C = ml aCId used to mflectlOn pomt ,

5 4 1 2 Standard aCId, a 02 N Ddute appropnate amount ofstandard aCId, a 1

N (541 1) to 1 hter (200 00 mlifO 1000 N) Check by standardizatlOn

15 ml ofa 05 N Na2C03solutlOn (5 3)

5413 Place 10 41 ml standard sulfunc aCId, 002 N (54 12) m a 100 ml

volumetnc and ddute to the mark

542 Standard sulfate solutlOn from Na2S04 DIssolve 1479 mg anhydrous Na2S04 m

dIstIlled water I'n a 1 hter volumetrIC flask and ddute to the mark wIth dIstdled

water

6 Procedure

6 1 FormatIon ofbanum sulfate turbIdIty I ' 6 1 1 Place 100 ~1 sample, or a SUItable portIon dIluted to 100 mI, mto a 250 Erlenmeyer

flask

6 1 2 Add exactly 5 ami conCiitlOnmg reagent (5 1).

613 MIX in the'sttrnngapparatus .,

6 1 4 Whde the solutlOn IS bemg stIrred, add a measunng spoonful ofBaCl2 crystals (5 2)

and begm tImmg ImmedIately ,

6 1 5 Stir exactly 1 a mmutes at constant speed

6 2 Measurement ofbanum sulfate turbIdIty Ilo rill I '!'

62 1 ImmedIately after the stlrnng penod has ended, pour solutlOn mto absorbance cell

6 2,2 Measure turbIdIty at 30 second mtervals ror;l- mmutes

6 2 3 Record the maXImum reading obtamed m the 4 mmute perIod

6 3 PreparatIon ofcahbratlOn curve

6 3 1 Prepare cahbratlOn curve usmg standard sulfate solutlOn (5 4)

6 3 2 Space standards at 5 mg/l mcrements m the 0-40 mg/l sulfate range

3754-2
6 3 3 Above 50 mg/l the accuracy decreases and the suspensions lose stability.

6 3 4 Check rehablhty of cahbratiOn curve by runmng a standard with every 3 or 4

samples

6 4 Correction for sample color and turbidity

64 1 Run a sample blank usmg the proceduIe 6 1 and 6.2 without the addition ofbanum

chlonde(614)

7 CalculatiOns

7 1 Read mg SO4from cahbratlon curve

mg S04/1 = mg S04 X 1,000

ml sample

8 PrecIsIon and Accuracy

8 1 ThIrty-four analysts m 16 laboratories analyzed six synthetic water samples contammg

exact mcrements ofmorgamc sulfate With the following results'

Increment as PrecisIon as Accuracy as

Sulfate Standard DeVIatIOn BIas, BIas

mg/hter mglhter % mg/hter

86 230 -372 -03

92 178 -8.26 -08

110 786 -301 -33

122 750 -337 -41

188 958 +004 +01

199 118 -170 -34

(FWPCA Method Study 1, Mmeral and Physical Analyses)

8 2 A synthetIc unknown sample contammg 259 mg/l sulfate, 108 tng/l Ca, 82 mg/l Mg,

3 1 mg/l K, 199 mg/l Na, 241 mg/l chlonde, 0250 mg/l mtnte N, 1 1 mg/l mtrate

N, and 425 mg/l total alkahmty (cont11.buted by NaHC03) was analyzed m 19

laboratones by the turbldlmetnc method, With a relatIve standard deViation of 9 1% and

a relatIve error of 1 2%

Bibliography

1 Annual Book of ASTM Standards, Part 31, "Water", Standard D516-68, Method B, p 430

(1976)

2 Standard Methods for the Exammatlon of Water and Wastewater, 14th EditiOn, p 496,

Method 427C, (1975)

375.4-3
SULFIDE

Method 376.1 (Titrimetric, Iodine)

STORET NO. Total 00745

Dissolved 00746

1 Scope and ApphcatlOn

1 1 Th1s method 1S apphcable to the measurement oftotal and d1ssolved sulfides m dnnkmg,

surface and sahne waters, domestic and mdustnal wastes

I 2 AC1d msoluble sulfides are not measured by the use ofth1s test (Copper sulfide 1S the only

common sulfide m th1s class)

1 3 Th1s method 1S smtable for the measurement ofsulfide m concentratlOns above 1 mg/l

2 Summary ofMethod

2 1 Excess lOdme 1S added to a sample wh1ch mayor may not have been treated w1th zmc

acetate to produce zmc sulfide The lOdme oX1d1zes the sulfide to sulfur under aC1d1c

cond1tlOns The excess lOdme 1S backt1trated w1th sodmm thlOsulfate or phenylarsme

oX1de

3 Comments

3 1 Reduced sulfur compounds, such as sulfite, thlOsulfate and hydrosulfite, wh1ch

decompose m aC1d may y1eld erratic results Also, volatile lOdme-consummg substances

wdl give h1gh results

3 2 Samples must be taken w1th a m1mmum of aeratlOn Sulfide may be volatthzed by

aeratlOn and any oxygen madvertently added to the sample may convert the sulfide to an

unmeasurable form

3 3 If the sample 1S not preserved wlth zmc acetate and NaOH, the analys1s must be started

1mmed1ately S1m1larly, the measurement of d1ssolved sulhdes mut also be commenced

1mmed1ately

4 Apparatus Ordmary laboratory glassware

5 Reagents

5 1 Hydrochlonc aC1d, H CI, 6 N

5 2 Standard 10dme solutlOn, 0 0250 N D1ssolve 20 to 25 g KI m a httle water in a hter

volumetnc and add 3 2 g 10dme Allow to d1ssolve Ddute to 1 hter and standard1ze

agamst 0 0250 N sodmm thlOsulfate or phenylarsme oX1de usmg a starch md1cator

5 3 Phenylarsme oX1de 0 0250 N commerc1ally avadable

5 4 Starch md1cator commerCially avadable

55 Procedure for standard1zation (see Res1dual Chlonne-lOdometnc titration Method

3303, sectlOn 5 15)

Approved for NPDES

Issued 1971

Ed1tonal reV1S1on 1978

376 1-1
" I

6 Procedure

6 1 Unpreclpltated sample

6 1 1 Place a known amount of standard IOdIne solutIOn (5 2) Into a 500 ml flask The

amountshould be estimated to be In excess ofthe amount ofsulfide expected

6 1 2 Add distIlled water, Ifnecessary, to bnng the volume to approximately 20 ml

613 Add 2 ml of6 NHCl (5 1)

6 1 4 Pipet 200 ml ofsample Into the flask, keepIng the tiP ofthe pipet below the surface

ofthe sample

6 1 5 Ifthe IOdIne color disappears, add more IOdIne untl1 the color remaInS Record the

total number of ml1hhters of standard IOdIne used In performIng steps 6 1 1 and

615

6 1 6 Titrate With the redUCIng solutIOn (0 0250 N sodIUm thIOsulfate or 0 0250 N

phenylarsIne OXide solutIOn (5 3» USIng a starch Indicator (5 4) untl1 the blue color

disappears Record the number ofml1hhters used

6 2 Precipitated samples

62 1 Add the reagents to the sample In the ongtnal bottle Perform steps 6 1 1, 6 1 3,

615, and 616

6 3 Dewatered samples

6 3 1 Return the glass fibre filter paper which contaInS the sample to the ongInal bottle

Add 200 ml dlst111ed water Perform steps 6 1 1,6 1 3,6 1 5, and 6 1 6

6 3 2 The calculatIOns (7) should be based on the volume of ongtnal sample put through

the filter

7 CalculatIOns

7.1 One ml of0 0250 N standard IOdIne solutIOn (52) reacts With 04 mg ofsulfide present In

the titratIOn vessel

7 2 Use the formula

mg/l sulfide = 400 (A - B)

ml sample

where

A = ml of0 0250 N standard IodIne solutIOn (5 2)

B = ml of0 0250N standard redUCIng sodIUm thosulfate or phenylarsIne OXide)

solutIOn (5 3)

8. Precision and Accuracy

8 1 PreCISIOn and accuracy for this method have not been determIned

BIblIography

1 Standard Methods for the ExamInatIon of Water and Wastewater, 14th EditIon, p 505,

Method 428D, (1975)

3761-2
SULFIDE

Method 376.2 (Colorimetric, Methylene Blue)

STORET NO. Total 00745

Dissolved 00746

1 Scope and ApphcatIOn

1 1 ThIS method IS apphcable to the measurement oftotal and dIssolved sulfides m dnnkmg,

surface and sahne waters, domestIc and mdustnal wastes

1 2 ACId msoluble sulfides are not measured by thIS method Copper sulfide IS the only

common sulfide m thIs class

1 3 The method IS sUitable for the measurement ofsulfide m concentratIOns up to 20 mg/1

2 Summary ofMethod

2 1 Sulfide reacts wIth dimethyl-p-phenylenediamme (p-ammodimethyl amhne) m the

presence of fernc chlonde to produce methylene blue, a dye WhICh IS measured at a

wavelength maXImum of625 nm,

3 Comments

3 1 Samples must be taken wIth a mmimum of aeratIOn Sulfide may be volatIhzed by

aeratIOn and any oxygen madvertently added to the sample may convert the sulfide to an

unmeasurable form DIssolved oxygen should not be present m any water used to dilute

standards

3 2 The analysIs must be started ImmedIately

3 3 Color and turbIdIty may mterfere wIth observatIons of color or wIth photometnc

readmgs

4 Apparatus

4 1 Matched test tubes, approXImately 125 mm long and 15 mm

°D

4 2 Droppers, dehvenng 20 drops/ml To obtam umform drops, hold dropper m vertiCal

posItIOn and allow drops to form slowly

4 3 Photometer, use eIther 4 3 1or 4 3 2

4 3 1 Spectrophotometer, for use at 625 nm wIth cells of 1 cm and 10 cm hght path

4 3 2 Filter photometer, wIth filter provIdmg transmIttance near 625 nm

5 Reagents

5 1 Ammo-sulfunc aCId stock solutIOn DIssolve 27 g N,N-dimethyl-p-phenyienediamme

oxalate (p-ammodimethylamhne) m a cold mIxture of 50 ml conc H2S04 and 20 ml

dIstilled water m a 100 ml volumetnc flask Cool and dilute to the mark If dark dIscard

and purchase fresh reagent Store m dark glass bottle

5 2 Ammo-sulfunc aCId reagent DIssolve 25 ml ammo-sulfunc aCId stock solutIOn (5 1) wIth

975 ml of 1+1H2S04 (5 4) Store m a dark glass bottle ThIS SolutIon should be clear

5 3 Fernc ch10nde solutIOn DiSsolve 100 g FeCl3-6H20 in 40 ml dIstilled water

Approved for NPDES

Issued 1978

3762-1
5 4 Sulfunc aCId solutIon, H2S04, 1+1

5.5 Diammomum hydrogen phosphate solutIon DIssolve 400 g (NH4)zHP04 m 800 ml

dIstilled water

5 6 Methylene blue solutIOn I DIssolve 109 ofmethylene blue m dIstIlled water mal lIter

volumetnc flask and dIlute to the mark Use U S P grade or one certIfied by the

BIOlogIcal Stam CommISSIOn The dye content reported on the label should be 84% or

more StandardIze (5 8) agaInst sulfide solutIOns of known strength and adjust

concentratIon so that 0 05 ml (1 drop) equals 1 0 mg/l sulfide

5 7 Methylene blue solutIOn II DIlute 10 00 ml ofadjusted methylene blue solutIOn I (5 6) to

100ml wIth dIstilled water m a volumetnc flask

5 8 StandardIzatIOn ofmethylene blue I solutIOn

5 8 1 Place several grams of clean, washed crystals of sodIum sulfide NazS·9HzO m a

small beaker

5 8 2 Add somewhat less than enough water to cover the crystals

5 8 3 StIr occasIOnally for a few mmutes Pour the solutIOn mto another vessel ThIS

reacts slowly wIth oxygen but the change IS mSlgmficnat over a few hours Make

the SolutIon daIly

5.8 4 To 1lIter ofdIstilled water add 1drop ofsolutIOn and mIX

5.8 5 ImmedIately dete11I1Ule the sulfide concentratIOn by the methylene blue procedure

(6) and by the tttnmetnc IOdIde procedure (Method 376 1, thIS manual)

5 8 6 Repeat usmg more than one drop ofsulfide solutIOn or less water untIl at least five

tests have been made m the range of 1 to 8 mg/l sulfide

587 Calculate the average percent error of the methylene blue procedure (6) as

compared to the tltnmetnc IOdIde procedure (Method 376 1)

5 8 8 Adjust by dIlutIon or by addmg more dye to methylene blue solutIOn I (5 6)

6 Procedure

6 1 Color development

6.1 1 Transfer 7 5 ml of sample to each of two matched test tubes usmg a specIal WIde

tIpped pIpet or fIllmg to a mark on the test tubes

6 1 2 To tube A add 0 5 ml amme-sulfurIc aCId reagent (5 2) and 0 15 ml (3 drops) FeCl3

SolutIon (5 3)

6 1 3 MIX ImmedIately by mvertmg the tube only once

6 1 4 To tube B add 05 mIl+1 H2S04 (5 4) and 0 15 ml (3 drops) FeCl3 solutIOn (5 3)

andmlX

6.1 5 Color WIll develop m tube A m the presence of sulfide Color development IS

usually complete m about 1 mmute, but a longer time IS often reqUIred for the

fadmg ofthe InItIal pmk color

6.16 Walt 3 to 5 mmutes

6 1 7 Add 1 6 ml (NH4)zHP04 SolutIon (5 5) to each tube

6 1.8 Walt 3 to 5 mmutes and make color comparIsons If zmc acetate was used walt at

least 10 mmutes before makmg comparIson

3762-2
6 2 Color companson

621 VIsual

62 1 1 Add methylene blue solutiOn I (56) and/or II (57) (dependmg on

sulfide concentratiOn and accuracy desIred) dropwise to tube B (6 14)

untIl the color matches that developed m the first tube

62 1 2 Ifthe concentratiOn exceeds 20 mg/1, repeat 6 2 11 usmg a portiOn of

the sample dl1uted to one tenth

6 2 2 Photometnc

6 2 2 1 Use a 1 cm cell for 0 1 to 2 0 mg/1 Use a 10 cm cell for up to 20 mg/1

6 2 2 2 Zero mstrument wIth portiOn ofsample from tube B(6 1 4)

6 2 2 3 Prepare calibratiOn curve from data obtamed m methylene blue

standardIzatiOn (5 8), plottmg concentraton obtamed from tItnmetnc

iOdIde procedure (Method 376 1) versus absorbance A straIght hne

relatiOnshIp can be assumed from 0 to 1.0 mg/1

6 2 2 4 Read the sulfide concentratiOn from the calibratiOn curve

7 CalculatiOns

7 1 VIsual comparIson WIth methylene blue solutiOn I (56), adjusted so that 005 ml (1

drop) = 1 0 mg/1 sulfide and a 7 5 ml sample

mg/1 sulfide = number drops methy:lene blue solutiOn I (5 6) + 0 1 x [number of drops

methylene blue solutiOn II (5 7)]

7 2 PhotometrIc see 6 2 2 4

8 PrecIsIon and Accuracy

8 1 The precIsIon has not been determmed The accuracy IS about ±10%

BIbliography

1 Standard Methods for he ExammatiOn ofWater and Wastewater, 14th edItiOn, p 503, Method

428C(1975)

3762-3
SULFITE

Method 377.1 (Titrimetric)

STORET NO. 00740

1 Scope and Apphcatton

1 1 ThIS method IS apphcable to dnnkmg and swface waters, sewage and mdustnal wastes

The pnmary apphcatton has been to coohng, process and dlstnbutton water systems and

boller feedwaters to WhICh sulfide IS added m order to reduce dISsolved oxygen and

ehmmate corrOSIOn

1 2 The mInImUm detectable hmlt IS 2-3 mg/l S03

2 Summary ofMethod

2 1 An aCldrned sample contammg a starch mdlcator IS tItrated wIth a standard potassIUm

IOdIde-IOdate tItrant to a famt permanent blue end pomt WhICh appears when the

reducmg power ofthe sample ha~ been completely exhausted

3 Interferences

3 1 The temperature ofthe sample must be below 50°C

3 2 Care must be taken to allow as httle contact wIth aIr as pOSSIble For example, do not

filter the sample Keep the buret tIp below the surface ofthe sample

3 3 Other oXidIzable substances, such as organIC compounds, ferrous Iron and sulfide are

posItIve mterferences. Sulfide may be removed by addmg 0 5g of zmc acetate and

analyzmg the supernatant ofthe settled sample

3 4 Nltnte gIves a negatIve mterference by oXldlzmg sulfite when the sample IS aCIdIfied, thIS

IS corrected by eIther usmg a propnetary mdlcator whIch ehmmates nItnte or by addmg

sulfamlc aCId

3 5 Copper and pOSSIbly other heavy metals catalyze the oXIdatIon ofsulfite, EDTA IS used

to complex metals

3 6 A blank must be run to correct for mterferences present m the reagents

4 Apparatus

4 1 Standard laboratory glassware IS used

5 Reagents

5 1 Sulfunc aCId, H2S04, 1+1

5 2 Starch mdlcator Amylose, Malhnckrodt ChemIcal Works, Thyodene, Magnus

ChemIcal Co or eqwvalent

53 Dual-Purpose Sulfite IndIcator Powder a propnetary formulation contammg sulfamlc

aCId to destroy nItnte

54 Standard potaSSIUm IOdIde-IOdate titrant, OOl25N DIS&olve 4458 mg anhydrous

potaSSIUm IOdate, KI03(pnmary standard grade dned for several hours at 120°C), 4 25g

Approved for NPDES

Issued 1974

Edltonal reVISIOn 1978

377 1-1
KI and 310 mg NaHC03m distilled water and dilute to 1 hter ThiS titrant IS eqmvalent

to 500 ug S03/1 00 ml

5 5 Sulfamlc ACid Crystalhne

5 6 EDTA Reagent Dissolve 2 5g EDTA m 100 ml dlstl1led water

6 Procedure

61 Samphng

Contact with air must be mlmmlzed If the sample temperature IS greater than 50·C, It

must be cooled m a special apparatus descnbed elswhere (see Blbhography)

Immediately add 1ml ofEDTA SolutIOn (56) per 100 ml ofsample

6 2 Starch Indicator

62 1 Place 1ml H2S04 (5 1) m titratIOn vessel

622 Add a 1 g sulfamlC aCid crystals (5 5)

6 2 3 Add 50 ml sample

6 2 4 Add approximately a 1 g starch mdlCator (5 2)

625 Titrate with potassIUm IOdide-IOdate titrant (54) untl1 a famt permanent blue color

develops Keep the pipet tip below the surface ofthe sample View the color change

agamst a white background Record the ml titrant

626 Run a reagent blank usmg dlstl1led water mstead ofsample (623)

6 3 Dual Purpose Sulfite IndlCator Powder

6 3 1 Place 50 ml sample m a titratIOn vessel

6 3 2 Add 3-4 drops phenolphthalem mdlcator

633 Add suffiCientscoops (lg) ofmdlCator (53) to discharge the red color

6 3 4 Titrate with potassIUm IOdide-IOdate titrant (5 4) untl1 a famt permanent blue color

develops View the color change agamst a white background Record the ml

titrant

6 3 5 Run a reagent blank usmg distilled water mstead ofsample (6 3 1)

7 CalculatIOns

7 I Use the formula

m /1 SO = A x N x 40,000

g J ml sample

where

A = ml titrant (6 2 5 or 6 3 4) B = ml

B = ml titrant for the blank (6 2 6 or 6 3 5) and

N = normahty ofKI-KI03titrant (5 4)

7 2 To calculate as Na2S03

mg/l Na2SOJ = mg/l S03 X 1 57

8 PrecIsion and Accuracy

8 1 PrecIsion and accuracy data are not aval1able at thiS time
BIblIography

1 Annual Book of ASTM Standards, Part 31, "Water", Standard DI339-72, Method C, p 440

(1976)

2 Standard Methods for the ExammatlOn of Water and Wastewater, 14th EdItion, p 508,

Method 429, (1975)

377 1-3
BIOCHEMICAL OXYGEN DEMAND

Method 405.1 (5 Days, 20°C)

STORET NO. 00310

Carbonaceous 80082

1 Scope and AppllcatlOn

liThe blOchemlcal oxygen demand (BOD) test IS used for determmmg the relative oxygen

reqmrements of mumclpal and mdustnal wastewaters AppllcatlOn ofthe test to orgamc

waste discharges allows calculatlOn of the effect of the discharges. on the oxygen

resources of the recelvmg water Data from BOD tests are used for the development of

engmeenng cntena for the design ofwastewater treatment plants

1 2 The BOD test IS an empmcal bioassay-type procedure which measures the dissolved

oxygen consumed by microbial hfe whl1e asslml1atmg and oXldlzmg the orgamc matter

present The standard test conditions mc1ude dark mcubatlOn at 20°C for a specified time

penod (often 5 days) The actual environmental conditions of temperature, blOloglcal

populatlOn, water movement, sunhght, and oxygen concentratlOn cannot be accurately

reproduced m the laboratory Results obtamed must take mto account the above factors

when relatmg BOD results to stream oxygen demands

2 Summary ofMethod

2 1 The sample of waste, or an appropnate dl1utlOn, IS mcubated for 5 days at 20°C m the

dark The reductlOn m dissolved oxygen concentratlOn dunng the mcubatlOn penod

yields a measure ofthe blOchemlcal oxygen demand

3 Comments

3 1 DetermmatlOn of dissolved oxygen m the BOD test may be made by use of either the

Modified Wmkler with Full-Bottle Techmque or the Probe Method m this manual

3 2 AddltlOnal mformatlon relatmg to oxygen demandmg charactenstlcs of wastewaters can

be gamed by applymg the Total Orgamc Carbon and Chemical Oxygen Demand tests

(also found m this manual)

3 3 The use of 60 ml mcubatlOn bottles m place of the usual 300 m1 mcubatlOn bottles, m

conjunction With the probe, IS often convement

4 PrecISion and Accuracy

4 1 Eighty-SIX analysts m fifty-eight laboratones analyzed natural water samples plus an

exact mcrement of blOdegradable orgamc compounds At a mean value of 2 1 and 175

mg/l BOD, the standard devlatlOn was ±O 7 and ±26 mg/l, respectively (EPA Method

Research Study 3)

4 2 There IS no acceptable procedure for determmmg the accuracy ofthe BOD test

Approved for NPDES CBOD pendmg approval for Section 304(h), CWA

Issued 1971

Edltonal revIsion 1974

405 1-1
5 References

5 I The procedure to be used for thIS determInation IS found In

Standard Methods for the ExamInation of Water and Wastewater, 15th

Edmon, p 483, Method 507 (1980)

52 Young, J C, "ChemIcal Methods for NItnfIcatIOn Control," J Water

Poll Control Fed, 45, p 637 (1973)

405 1-2
CHEMICAL OXYGEN DEMAND

Method 410.1 (Titrimetric, Mid·Level)

STORET NO. 00340

1 Scope and ApphcatlOn

1 1 The ChemlCal Oxygen Demand (COD) method determInes the quantIty of oxygen

requIred to oXIdIze the orgamc matter In a waste sample, under specIfic condItions of

OXIdIZIng agent, temperature, and time

1 2 SInce the test utlhzes a specIfic chemIcal oXldatlOn the result has no defimte relatlOnshlp

to the BlOchemlCal Oxygen Demand (BOD) ofthe waste or to the Total Orgamc Carbon

(TOe) level The test result should be consIdered as an Independent measurement of

orgamc matter In the sample, rather than as a SubstItute for the BOD or TOC test

1 3 The method can be apphed to domestic and Industnal waste samples havIng an orgamc

carbon concentratlOn greater than 50 mg/1 For lower concentratlOns of carbon such as

In surface water samples, the Low Level ModlficatlOn should be used When the chlonde

concentratlOn of the sample exceeds 2000 mg/1, the modlficatlOn for salIne waters IS

reqUIred

2 Summary ofMethod

2 1 Orgamc and oXIdIzable Inorgamc substances In,the sample are oXIdIzed by potassIUm

dIchromate In 50% sulfunc aCId solutlOn at reflux temperature SlIver sulfate IS used as a

catalyst and mercunc sulfate IS added to remove chlonde Interference The excess

dIchromate IS titrated wIth standard ferrous ammomum sulfate, USIng

orthophenanthrohne ferrous complex as an IndIcator

3 Samphng and PreservatlOn

3 1 Collect the samples In glass bottles, If possIble Use ofplastic contaIners IS permIssIble IfIt

IS known that no organic contamInants are present In the contaIners

3 2 BlOloglCally active samples should be tested as soon as possIble Samples contaInIng

settleable matenal should b~ well mIxed, preferably homogemzed, to permIt removal of

representatIve ahquots

3 3 Samples should be preserved WIth sulfunc aCId to a pH < 2 and maIntamed at 4°C until

analysIs

4 Interferences

4 1 Traces of orgamc matenal eIther from the glassware or atmosphere may cause a gross,

pOSItive error

4 1 1 Extreme care should be exercIsed to aVOid mcluslOn of orgamc matenals 10 the

dlstlIled water used for reagent preparatlOn orsample dlIutlOn

4 1 2 Glassware used In the test should be condltlOned by runmng blank procedures to

ehmInate traces oforgamc matenal

Approved for NPDES

Issued 1971

Edltonal reVlSlOn 1978

410 I-I
Iill 1111 III I II I11 I II1 I I II

4 2 VolatIle matenals may be lost when the sample temperature nses durmg the sulfunc aCId

addItIon step To mlmmlze thIS loss the flask should be cooled durmg additlOn of the

sulfunc aCId solutlOn

4 3 Chlondes are quantitatively oXIdIzed by dIchromate and represent a posItive

mterference Mercuric sulfate IS added to the digestlOn flask to complex the chlorides,

thereby effectively ehmmatmg the mterference on all but brine and estuarine samples

5. Apparatus

5 1 Reflux apparatus Glassware should consIst of a 500 ml Erlenmeyer flask or a 300 ml

round bottom flask made of heat-resIstant glass connected to a 12 mch Alhhn condenser

by means of a ground glass Jomt Any eqmvalent reflex apparatus may be substituted

provIded that a ground-glass connectlOn IS used between the flask and the condenser

6 Reagents

6.1 DIstIlled water SpecIal precautlOns should be taken to msure that dIstIlled water used m

thIS test be low m orgamc matter

62 Standard potassIUm dIchromate solutiOn (0 250 N) DIssolve 12259 g K2Cr207, primary

standard grade, previOusly dried at 103°C for two hours, m dIstIlled water and dIlute to

lOOOml

63 Sulfuric aCId reagent Conc H2S04 contammg 23 5g sIlver sulfate, Ag2S04, per 409kg

bottle WIth contmuous stIrnng, the sIlver sulfate may be dIssolved m about 30 mmutes

6.4 Standard ferrous ammomum sulfate (025 N) DIssolve 98 0 g of Fe(NH4)2(S04)2.6H20

In dIstIlled water Add 20 ml ofconc H2S04(6 8), cool and dIlute to 1 hter ThIS solutiOn

must be standardIzed dally agamst standard K2Cr207 solutiOn (6 2)

64 1 StandardIzatiOn To approXImately 200 ml of dIstIlled water add 250 ml of 0 25 N

K2Cr207 (62) solutiOn Add 20 ml of H2S04 (6 8) and cool TItrate wIth ferrous

ammOnIum sulfate (6 4) usmg 3 drops offerrom mdlcator (6 6) The color change

IS sharp, gomg from blue-green to redillsh-brown

Normahty = (ml K,Cr,O¥O 25)

ml Fe (NH.h (SO.),

6.5 Mercuric sulfate Powdered HgS04

6.6 Phenanthrohne ferrous sulfate (ferrom) mdlCator solutiOn DIssolve 148 g of 1-10

(ortho) phenanthrohne monohydrate, together wIth 0 70 g of FeS04·7H20 m 100 ml of

water ThIS mdlcator may be purchased already prepared

6 7 SIlversulfate Powdered Ag2S04

6.8 Sulfuric aCId (sp gr 1 84) Concentrated H2S04

7 Procedure

7 1 Place several bOllmg stones m the reflux flask, followed by 50 0 ml of sample or an

alIquot dIluted to 500 ml and 1 g of HgS04 (6 5) Add 50 ml conc H2S04 (6 8), SWIrl

untIl the merCUriC sulfate has dIssolved Place reflux flask 1ll an Ice bath and slowly add,

wIth sWlrhng, 250 ml of 025 N K2Cr207 (62) Now add 70 ml of sulfuric aCId-sIlver

410 1-2
sulfate solutlOn (6 3) to the cooled reflux flask, agam usmg slow addItiOn WIth sWIrlmg

motiOn

CautiOn Care must be taken to assure that the contents ofthe flask are well mIxed Ifnot,

superheatmg may result, and the mIxture may be blown out of the open end of the

condenser

7 1 1 If voiatlie orgamcs are present m the sample, use an alhhn condenser and add the

sulfunc aCId-sliver sulfate solutiOn through the condenser, whIle coohng the flask,

to reduce loss by volatihzatiOn

7 2 Apply heat to the flask and reflux for 2 hours For some waste waters, the 2-hour reflux

penod IS not necessary The tIme reqUlred to gIve the maXImum oXIdatlOn for a

wastewater ofconstant or known composItion may be determmed and a shorter penod of

refluxmg may be permISSIble

7 3 Allow the flask to cool and wash down the condenser WIth about 25 ml of distliled water

If a round bottom flask has been used, transfer the mIxture to a 500 ml Erlenmeyer flask,

washmg out the reflux flask 3 or 4 times WIth dIStilled water Dliute the aCId solutiOn to

about 300 ml WIth dIStilled water and allow the solutlOn to cool to about room

temperature Add 8 to 10 drops of ferrom mdicator (6 6) to the solution and tItrate the

excess dIchromate WIth 025 N ferrous ammomum sulfate (64) solutlOn to the end pomt

The color change WIll be sharp, changmg from a blue-green to a reddIsh hue

74 Blank-SImultaneously run a blank determmatiOn followmg the detalis gIven m (7 1) and

(7 2), but usmg low COD water m place ofsample

8 CalculatlOn

8 1 Calculate the COD m the sample m mg/l as follows

COD, mg/hter = (A - B)N x 8,000

S

where

A = mlIhhters ofFe(NH4)z(S04)2 solutlOn reqUlred for titratiOn ofthe blank,

B = mlIhhters ofFe(NH4)2 (S04)2 solutiOn reqUlred for titratiOn ofthe sample,

N = normahty ofthe Fe(NH4MS04)2 solutiOn, and

S = mIlhhters ofsample used for the test

9 PreCIsIon and Accuracy

9 1 EIghty-SIX analysts m fifty-eIght laboratones analyzed a dist1I1ed water solutiOn

contammg OXIdIzable orgamc matenal eqUlvalent to 270 mg/l COD The standard

deVIatiOn was ±1776 mg/l COD With an accuracy as percent relative error (bIas) of

-4 7% (EPA Method Research Study 3)

BIblIography

1 Standard Methods for the ExammatiOn of Water and Wastewater, 14th EditlOn, p 550,

Method 508 (1975)

2 Annual Book ofASTM Standards, Part 31, "Water", Standard D1252-67, p 473 (1976)

410 1-3
CHEMICAL OXYGEN DEMAND

Method 410.2 (Titrimetric, Low Level)

STORET NO. 00335

1 Scope and ApplicatIOn

lIThe scope ofthIS modIficatIOn ofthe ChemICal Oxygen Demand (COD) test IS the same

as for the hIgh level test It IS apphcable to the analySIS ofsurface waters, domestIc and

Industnal wastes wIth low demand charactenstlcs

1 2 ThIS method (low level) IS apphcable f01 samples havIng a COD In the range of 5-50

mg/1COD

2 Summary ofMethod

2 1 Orgamc and OXIdIzable Inorgamc substances In an aqueous sample are OXIdIzed by

potaSSIUm dIchromate solutIOn In 50 percent (by volume) sulfunc aCId In solutIOn The

excess d1chromate IS tItrated WIth standard ferrous ammomum sulfate USIng

orthophenanthroline ferrous complex (ferroIn) as an IndIcator

3 Sampling and PreservatIOn

3 1 Collect the samples In glass bottles, IfpossIble Use ofplastic contaIners IS permISSIble IfIt

IS known that no orgamc contamInants are present In the contaIners

32 BIOlogICally actIve samples should be tested as soon as possIble Samples contaInIng

settleable matenal should be well mIXed, preferably homogemzed, to permIt removal of

representative ahquots

3 3 Samples should be preserved WIth sulfunc aCId to a pH <2 and maIntaIned at 4°C untIl

analysIs

4 Interferences

4 1 Traces of orgamc matenal eIther from the glassware or atmosphere may cause a gross,

pOSItIve error

4 1 1 Extreme care should be exerCIsed to aVOId InclUSIOn of orgamc matenah. In the

dIstIlled water used for reagent preparatIOn orsample dIlutIOn

4 1 2 Glassware used In the test should be condItioned by runmng blank procedures to

elImInate traces oforgamc matenal

4 2 VolatIle matenals may be lost when the sample temperature nses dunng the sulfunc aCId

addItIOn step

43 Chlondes are quantItatIvely OXIdIzed by dIchromate and represent a pOSItive

Interference Mercunc sulfate IS added to the dIgestIOn flask to complex the chlondes,

thereby effectIvely elImInatIng the Interference on all but bnne and estuanne samples

5 Apparatus

5 1 Reflux apparatus Glassware should conSIst of a 500 ml Erlenmeyer flask or a 300 ml

round bottom flask made of heat-resIstant glass connected to a 12 Inch AllIhn condenser

Issued 1971

Edltonal reVISIOn 1974 and 1978

410 2-1
I I II I

I I II II

I,

by means of a ground glass Jomt Any eqmvalent reflux apparatus may be substituted

provided that a ground-glass connectIOn IS used between the flask and the condenser

6 Reagents

6 1 Distilled water Special precautions should be taken to msure that distIlled water used m

this test be low m orgamc matter

6 2 Standard potassIUm dichromate solutIOn (0 025 N) Dissolve 12 259 g K2Cr207, pnmary

standard grade, preVIOusly dned at 103°C for two hou~s, m distIlled water and dilute to

1000 ml MIx thiS solutIOn thoroughly then dllute 100 0 ml to 1000 ml With distilled I I I III

water.

63 Sulfunc aCid reagent Conc H2S04 contamlng 23 5g sli~er ~ulfate, Ag2S04> per 409kg

bottle (With contmuous stlfrmg, the sIlver sulfate may be dissolved m about 30

mtnut~s ) I I II

64 Standard ferrous ammomum sulfate (0 025 N) Dissolve 98 g ofFe(NH4)z(S04)2-6H20 m

distdled water Add 20 ml ofconc H2S04(6 8), cool and dllute to 1 hter Dilute 100 ml of

thiS solutIOn to 1 hter With distilled water ThiS solution "Ifl:yst ~,~ stap.,Hardlzed dally

agamst K2Cr207 solutIOn

64 1 Standardization To approximately 200 ml ofdistIlled water add 25 0 ml of0 025 N

K2Cr207 (62) solutIOn Add 20 ml of H2S04 (68) and cool Titrate With ferrous

ammomum sulfate (64) usmg 3 drops offerrom mdlcator (6 6) The color change

IS sharp, gomg from blue-green to reddish-brown

6 5 Mercunc sulfate Powdered HgS04

66 Phenanthrolme ferrous sulfate (ferrom) mdlcator solution Dissolve 148 g of 1-10

(ortho)phenanthrohne monohydrate, together With 070 g of FeS04-7H20 m 100 ml of

water ThiS mdlcator may be purchased already prepared

6 7 Silversulfate Powdered Ag2S04

6.8 Sulfunc aCid (sp gr 1 84) Concentrated H2S04

7 Procedure

7 1 Place several bOllmg stones m the reflux flask, followed by 50 0 ml of sample or an

aliquot d11uted to 500 m1 and 1 g of HgS04(6 5) Add 50 ml conc H2S04 (6 8), SWirl

until the mercunc sulfate has dissolved Place reflux flask m an Ice bath and slowly add,

With sWlrlmg, 25 0 ml of 0025 N K2Cr207 (6 2) Now add 70 ml ofsulfunc aCid-sliver

sulfate solution (6 3) to the cooled reflux flask, agam usmg slow addition With sWlrhng

motIOn

Caution Care must be taken to assure that the contents ofthe flask are well mixed Ifnot,

superheatmg may result, and the mixture may be blown out of the open end of the

condenser

4102-2
7 1.1 If volattle orgamcs are present m the sample, use an AllIhn condenser and add the

sulfunc aCid-stlver sulfate solutIOn through the condenser, whtle coolIng the flask,

to reduce loss by volatilIzatIOn

7 2 Apply heat to the flask and reflux for 2 ho~rs For some waste waters, the 2-hour reflux

penod is not necessary The time reqmred to give the maXimum oXidatIOn for a

wastewater of constant or known compOSitIOn may be determmed and a shorter penod of

refluxmg may be permissible

7 3 Allow the flask to cool and wash down the condenser with about 25 ml of disttlled water

If a round bottom flask has been used, transfer the mixture to a 500 ml Erlenmeyer flask,

washmg out the reflux flask 3 or 4 times With disttlled water Dtlute the aCid solutIOn to

about 300 ml with disttlled water and allow the solutIOn to cool to about room

temperature Add 8 to 10 drops of ferrom mdicator (6 6) to the solutIOn and titrate the

excess dichromate with 0025 N ferrous ammomum sulfate (64) solutIOn to the end

pomt The color change Will be sharp, changmg from a blue-green to a reddish hue

74 Blank-Simultaneously run a blank determmatIOn followmg the detatls given m (7 1)

and (7 2), but usmg low COD water m place ofsample

8 Calculation

8 1 Calculate the COD m the sample m mg/l as follows

COD, mg/l = (A - B)~ x 8,000

where

A = mtllIlIters ofFe(NH4)iS04)2 solutIOn reqmred for titration ofthe blank,

B = mtllIlIters ofFe(NH4)iS04)2 solutiOn reqmred for titratIOn ofthe sample,

N = normalIty ofthe Fe(NH4)lS04)2 solutIOn, and

S = mtllIlIters ofsample used for the test

9 PreCiSIOn and Accuracy

9 1 Eighty-six analysts m fifty-eIght laboratones analyzed a distilled water solutIOn

contammg OXidizable orgamc matenal eqmvalent to 123 mg/l COD The standard

deViatIOn was ±4 15 mg/l COD With an accuracy as percent relative error (bias) of

o3% (EPA Method Research Study 3 )

4102-3
CHEMICAL OXYGEN DEMAND

Method 410.3 (Titrimetric, High Level for Saline Waters)

STORET NO. 00340

1 Scope and Apphcat10n

1 1 When the chlonde level exceeds 1000 mg/1 the mmtmum accepted value for the COD

w1ll be 250 mg/1 COD levels whlCh fall below th1S value are h1ghly questlOnable because

ofthe h1gh chlonde correct1on Wh1Ch must be made

2 Summary ofMethod

2 1 Orgalllc and oX1d1zable morgalllc substances m an aqueous sample are oX1d1zed by

potasslUm d1chromate solutlOn m 50 percent (by volume) sulfunc aC1d solutlOn The

excess d1chromate 1S tltrated w1th standard ferrous ammomum sulfate usmg

orthophenanthrolme ferrous complex (ferrom) as an md1cator

3 Sample Handlmg and Preservatlon

3 1 Collect the samples m glass bottles, 1fposs1ble Use ofplastlc contamers 1S perm1ss1ble 1f1t

1S known that no orgalllc contammants are present m the contamers

3 2 B1ologlCally act1ve samples should be tested as soon as poss1ble Samples contammg

settleable matenal should be well m1xed, preferably homogemzed, to perm1t removal of

representat1ve ahquots

3 3 Samples should be preserved w1th sulfunc aC1d to a pH <2 and mamtamed at 4°C untl1

analys1s

4 Interferences

4 1 Traces of orgalllc matenal e1ther from the glassware or atmosphere may cause a gross,

pos1tlve error

4 1 1 Extreme care should be exerc1sed to aVOld mcluslOn of orgamc matenals m the

d1stl1led water used for reagent preparation orsample d1lutlOn

4 1 2 Glassware used m the test should be cond1tloned by runnmg blank procedures to

ehmmate traces oforgalllc matenal

4 2 Volatl1e matenals may be lost when the sample temperature nses dunng the sulfunc aC1d

add1tlon step

4 3 Chlondes are quantltat1vely oX1d1zed by d1chromate and represent a pos1tlve

mterference A chlonde correctlOn 1S made usmg the procedure outhned m 77 of th1S

method

5 Apparatus

5 1 Reflux apparatus Glassware should conS1st of a 500 ml Erlenmeyer flask or a 300 m1

round bottom flask made of heat-res1Stant glass connected to a 12 mch Alhhn condenser

by means of a ground glass Jomt Any eqmvalent reflux apparatus may be Subst1tuted

prov1ded that a ground-glass connectlOn 1S used between the flask and the condenser

Issued 1971

Ed1tonal reVlSlon 1978

410 3-1
6 Reagents

6 1 Standard potasslUm dIchromate solutIon, (025 N) DIssolve 122588 g of K2Cr20 7,

pnmary standard grade, prevIously dned for 2 hours at 103°C In water and dIlute to 1000

ml

62 Sulfunc aCId reagent Conc H2S04containing 235 g sIlver sulfate, Ag2S04, per 4 09kg

bottle (WIth continuous stirnng, the sIlver sulfate may be dIssolved In about 30

minutes )

63 Standard ferrous ammOnIum sulfate, 0 250 N DIssolve 98 g of Fe(NH4)iS04)2-6H20 In

dIStilled water Add 20 ml of conc H2S04, (67), cool and dIlute to 1 lIter ThIS solutIOn

must be standardIzed against the standard potasslUm dIchromate solutIOn (6 1) dally

6 3 1 StandardIzatIon DIlute 25 0 ml ofstandard dIchromate solutIOn (6 1) to about 250

ml wIth dIstIlled water Add 20 ml conc sulfunc aCId (6 7) Cool, then tItrate WIth

ferrous ammomum sulfate titrant (6 3), usmg 10 drops offerroIn indIcator (6 5)

64 Mercunc sulfate Powdered HgS04

6 5 PhenanthrolIne ferrous sulfate (ferroIn) indIcator SolutIon DIssolve 1 48 g of 1-10-

(ortho) phenanthrolme monohydrate, together wIth 0 70 g of FeS04-7H20 In 100 ml of

water ThIS indIcator may be purchased already prepared

6 6 SIlversulfate Powdered Ag2S04

6 7 Sulfunc aCId (sp gr 1 84) Concentrated H2S04

7. Procedure

71 PIpet a 500 ml alIquot of sample not to exceed 800 mg/1 of COD Into a 500 ml, flat

bottom, Erlenmeyer flask Add HgS04(6 4) In the ratIo of 10 mg to 1mg chlonde, based

upon the mg of chlonde In the sample alIquot and 5 ml ofsulfunc aCId (6 7) SWIrl until

all the mercunc sulfate has dIssolved Add 25 0 m1 of0 25N K2Cr20 7 (6 1) Carefully add

70 ml of sulfunc aCId-sIlver sulfate solutIOn (62) and gently SWIrl untIl the SolutIon IS

thoroughly mIxed Glass beads should be added to the reflux mIxture to prevent

bumping, WhICh can be severe and dangerous

CautIon The reflux mIxture must be thoroughly mIxed before heat IS applIed If thIS IS

not done, local heating occurs In the bottom of the flask, and the mIxture may be blown

out ofthe condenser

7 1 1 If volatIle orgamcs are present In the sample, use an AllIhn condenser and add the

sulfunc aCId-sI1ver sulfate solutIon through the condenser, whIle coolIng the flask,

to reduce loss by volatIlIzation

7 2 Attach the flask to the condenser and reflux the mIxture for two hours

7 3 Cool, and wash down the interIor of the condenser WIth 25 ml of dIstilled water

DIsconnect the condenser and wash the flask and condenserJOint WIth 25 ml of dIstIlled

waterso that the total volume IS 350 ml Cool to room temperature

4103-2
74 Titrate with standard ferrous ammomum sulfate (63) usmg 10 drops of ferrom (65)

mdlcator (This amount must not vary from blank, sample and standardizatIOn) The

color change IS sharp, gomg from blue-green to reddish-brown and should be taken as the

end pomt although the blue-green color may reappear wlthm mmutes

7 5 Run a blank, usmg 50 ml of dlstl1led water m place of the sample together With all

reagents and subsequent treatment

76 For COD values greater than 800 mg/l, a smaller ahquot of sample should be taken,

however, the volume should be readjusted to 50 ml With dlstl1led water havmg a chlonde

concentratIOn equal to the sample

77 Chlonde correctIOn(l) Prepare a standard curve of COD versus mg/I of chlonde, usmg

sodIUm chlonde solutIOns of varymg concentratIOns followmg exactly the procedure

outhned The chlonde mterval, as a mlmmum should be 4000 mg/I up to 20,000 mg/I

chlonde Lesser mtervals of greater concentratIOns must be run as per the reqUIrements

ofthe data, but m no case must extrapolatIOn be used

8 CalculatIOn

mg/l COD = [(A - B)C x 8,000] - SOD x 1 2

ml of sample

where

A = ml Fe(NH4)2(S04)2 for blank,

B = ml Fe(NH4)lS04)2 for sample,

C = normahty ofFe(NH4)lS04)2,

D = chlonde correctIOn from curve (step 7 7)

I 2 = compensatIOn factor to account for the extent ofchlonde OXidatIOn which IS dlsslml1ar m

systems contammg orgamc and non-orgamc matenal

9 PrecIsion and Accuracy

9 1 PrecIsion and accuracy data are not aval1able at thiS time

BIblIography

1 Burns, E R, Marshall, C, Journal WPCF, Vol 37, P 1716-1721 (1965)

410 3-3
CHEMICAL OXYGEN DEMAND

Method 410.4 (Colorimetric, Automated; Manual)

STORET NO. 00340

1 Scope and ApphcatIOn

1 1 ThIS method covers the determmatIOn ofCOD m surface waters, domestic and mdustnal

wastes

1 2 The apphcable range of the automated method IS 3-900 mg/1 and the range of the

manual method IS 20 to 900 mg/l

2 Summary ofMethod

2 1 Sample, blanks and standards m sealed tubes are heated m an oven or block dlgestor m

the presence of dIchromate at 150°C Aftel two hours, the tubes are removed from the

oven or dlgestor, cooled and measured spectrophotometncally at 600 nm

3 Sample Handhng and PreservatIOn

3 1 Collect the samples m glass bottles If possIble Use ofplastIc contamers IS permIssIble IfIt

IS known that no orgamc contammants are present m the contamers

3 2 Samples should be preserved With sulfunc aCId to a pH < 2 and mamtamed at 4°C untl1

analysIs

4 Interferences

4 1 Chlondes are quantitatively oXIdized by dIchromate and repres~nt a posItive

mterference Mercunc sulfate IS added to the dIgestIOn tubes to complex the chlondes

5 Apparatus

5 1 Drymg oven or block dlgestor, 150°C

5 2 Cormng culture tubes, 16 x 100 mm or 25 x 150 mm wIth Teflon hned screw cap

5 3 Spectrophotometer or Techmcon AutoAnalyzer

5 4 Muffle furnace, 500°C

6 Reagents

6 1 DIgestIOn solutIOn Add 10 2 g K2Cr207, 167 ml conc H2S04 and 33 3 g HgS04 to 500 ml

ofdlstl1led water, cool and dIlute to 1 hter

62 Catalyst solutIOn Add 22 g Ag2S04 to a 409kg bottle of conc H2S04 Stir unttl

d1ssolved

6 3 Sampler wash solutIOn Add 500 ml ofconc H2S04 to 500 ml ofdlstl1led water

6 4 Stock potassiUm aCId phthalate Dissolve 0 850 g m 800 ml of dlsttlled water and dtlute to

1 hter 1ml = 1mg COD

6 4 1 Prepare a senes of standard solutIOns that cover the expected sample

concentratIOns by dllutmg appropnate volumes ofthe stock standard

7 Procedure

7 1 Wash all cultuie tubes and screw caps wIth 20% H2S04 before their first use to prevent

contammatIOn Trace contammatIOn may be removed from the tubes by igmtmg them m

a muffle oven at 500°Cfor 1 hour

Pendmg approval for Section 304(h), CWA

Issued 1978

4104-1
7 2· Automated

721 Add 25 ml ofsample to the 16 x 100 mm tubes

7 2 2 Add 1 5 ml ofdIgestIOn solution (6 1) and mix

7 2 3 Add 3 5 ml ofcatalyst solution (6 2) carefully down the side ofthe culture tube

7 2 4 Cap tightly and shake to mix layers

7 2 5 Process standards and blanks exactly as the samples

7 2 6 Place In oven or block dlgestor at 150°C for two hours

7 2 7 Cool, and place standards In sampler In order of decreasmg concentration

Complete fillIng sampler tray with unknown samples

7 2 8 Measure color mtenslty on AutoAnalyzer at 600 nm

73 Manual

7 3 1 The followmg procedure may be used If a larger sample IS deSired or a

spectrophotometer IS used In place ofan AutoAnalyzer

73 2 Add 10 ml ofsample to 25 x 150 mm culture tube

7.3 3 Add 6 ml ofdigestion solution (6 1) and mix

734 Add 14 ml of catalyst solutIOn (62) down the SIde of culture tube

7 3 5 Cap tightly and shake to mix layers

7 3 6 Place m oven or block dlgestor at 150°C for 2 hours

7 3 7 Cool, .tHow any precipItate to settle and measure IntensIty In spectrophotometer at

600 nm Use only optIcally matched culture tubes or a sIngle cell for ~pectrophotometnc measurement

8. Calculation

8 1 Prepare a standard curve by plottmg peak heIght or percent transmittance agamst known

concentrations ofstandards

8 2 Compute concentratIOn ofsamples by companng sample response to standard curve

9 Precision and Accuracy

9 1 PrecIsion and accuracy data are not avaIlable at this tIme

BIblIography

1 Jlrka, AM, and M J Carter, "Micro-SemI-Automated AnalySIS of Surface and Wastewaters

for Chenllcdl Oxygen Demand" Anal Chern 47 1397, (1975)

410 4-2
SMISSION TUBING

AMPLE

PLE WASH

M Fie

PLE

LLED WATER

"" RESAMPLE

TO SAMPLER

WASH RECEPTACLE GRN GRN 2 00 SAM

BLK BLK o 32 AIR

116 0246 01 ....... t BLUE BLUE 1 60 SAMf

10 TLJRr'J~ 4 116 0489 01 BLUE BLUE 1 60 OISTI

WASTE

BLK BLK o 32 AIR

+ BLUE BLUE 1 60 RE S

116 04 92 01

LORIMETER WASTE RED RED 070 FRO

o NM

MM FIC

TO FIC PUMP

TUBE GLASS TRAN

PROPORTIONING

PUMP

co

60

50

of"

w

FIGURE 1 COD MANIFOLD AA1 OR AA 11
OIL AND GREASE, TOTAL~ RECOVERABLE

Method 413.1 (Gravimetric, Separatory Funnel Extraction)

STORET NO. 00556

1 Scope and ApphcatlOn

1 1 ThIS method mcludes the measurement of fluorocarbon-l13 extractable matter from

surface and sahne waters, mdustnal and domestIc wastes It IS apphcable to the

determmatlOn ofrelatIvely non-volatIle hydrocarbons, vegetable Oils, ammal fats, waxes,

soaps, greases and related matter

1 2 The method IS not apphcable to measurement of hght hydrocarbons that volatIhze at

temperatures below 70°C Petroleum fuels from gasolme through #2 fuel Oils are

completely or partIally lost m the solvent removal operatlOn

1 3 Some crude oIls and heavy fuel Oils contam a sIgmficant percentage of resIdue-type

matenals that are not soluble m fluorocarbon-l13 Accordmgly, recovenes of these

matenals WIll be low

1 4 The method covers the range from 5 to 1000 mg/1 ofextractable matenal

2 Summary ofMethod

2 1 The sample IS aCIdIfied to a low pH ( < 2) and senally extracted wIth fluorocarbon-113 m

a separatory funnel The solvent IS evaporated from the extract and the resIdue weIghed

3 DefimtlOns

3 1 The defimtlOn of 011 and grease IS based on the procedure used The nature of the 011

and/or grease, and the presence ofextractable non-Oily matter WIll mfluence the matenal

measured and mterpretatlOn ofresults

4 Samphng and Storage

4 1 A representatIve sample of 1 hter volume should be collected m a glass bottle If analysIs

IS to be delayed for more than a few hours, the sample IS preserved by the additlOn of 5 ml

HCl (6 1) at the time ofcollectIon and refngelated at 4°C

4 2 Because losses of grease WIll occur on samphng eqmpment, the collectlOn ofa composIte

sample IS Impractical IndIVIdual portlOns collected at prescnbed time mtervals must be

analyzed separately to obtam the average concentration over an extended penod

5 Apparatus

5 1 Separatory funnel, 2000 ml, WIth Teflon stopcock

5 2 Vacuum pump, or othersource ofvacuum

5 3 Flask, b01hng, 125 ml (Cormng No 4100 or equIvalent)

5 4 DistIlhng head, Cialsen or eqmvalent

5 5 FIlter paper, Whatman No 40, 11 cm

6 Reagents

6 1 Hydrochlonc aCId, 1 1 MIX equal volumes ofconc HCl and dIstIlled water

Approved for NPDES

Issued 1974

Editonal reVISIon 1978

413 I-I
62 Flurocarbon-1l3,(1,1,2-tnchloro-1,2,2-tnfluoroethane), b p 48°C

6 3 SodIUm sulfate, anhydrous crystal

7. Procedure

7 1 Mark the sample bottle at the water memscus for later determInatlOn ofsample volume

Ifthe sample was not aCIdIfied at time of collectlOn, add 5 ml hydrochlonc aCId (6 1) to

the sample bottle Mter mIXIng the sample, check the pH by touchIng pH-sensItive paper

to the cap to Insure that the pH IS 2 or lower Add more aCId Ifnecessary

7 2 Pour the sample Into a separatory funnel

7 3 Tare a bOIlIng flask (pre-dned In an oven at 103°C and stored In a deSIccator)

74 Add 30 ml fluorocarbon-113 (62) to the sample bottle and rotate the bottle to rInse the

sIdes Transfer the solvent Into the separatory funnel Extract by shakIng vIgorously for 2

. mmutes Allow the layers to separate, and ftlter the solvent layer Into the flask through a

funnel contaInIng solvent mOIstened ftlter paper

NOTE: An emulslOn that faIls to dIssIpate can be broken by pounng about 1 g sodIUm

sulfate (6 3) mto the ftlter paper cone and slowly draInIng the emulsIon through the salt

AdditlOnal 1g portlOns can be added to the cone as requIred

7 5 Repeat (7 4) tWIce more, WIth additlOnal portlOns offresh solvent, combInIng all solvent

In the bOIlIng flask

76 RInse the tip ofthe separatory funnel, the ftlter paper, and then the funnel WIth a total of

10-20 ml solvent and collect the nnSIngs In the flask

7.7 Connect the bOIlIng flask to the dIstIllIng head and evaporate the solvent by ImmerSIng

the lower half ofthe flask In water at 70°C Collect the solvent for reuse A solvent blank

should accompany each set ofsamples

7 8 When the temperature In the dIstIllIng head reaches 50°C or the flask appears dry remove

the dIStillIng head Sweep out the flask for 15 seconds WIth aIr to remove solvent vapor by

InsertIng a glass tube connected to a vacuum source ImmedIately remove the flask from

the heatsource and WIpe the outsIde to remove excess mOIsture and fingerpnnts

7 9 Cool the bOIlIng flask In a deSIccator for 30 mInutes and weIgh

8 CalculatIon

8.1 mg/1 total oIl and grease = R VB

where

R = reSIdue, gross weIght ofextractlOn flask mInUS the tare weIght, In mIllIgrams

B = blank determInatlOn, reSIdue of eqUIvalent volume of extractlOn solvent, III

mIllIgrams

V = volume of sample, determIned by reftllIng sample bottle to calIbratlOn lIne and

correctIng for aCId addItIon Ifnecessary, In lIters

413 1-2
9 PrecIsIon and Accuracy

9 1 The two 011 and grease methods m thIS manual were tested by a smgle laboratory (EMSL)

on sewage ThIS method determined the 011 and grease level in the sewage to be 12 6

mg/1 When 1 liter portiOns of the sewage were dosed wIth 140 mg of a mIxture of #2

fuel 011 and Wesson 011, the recovery was 93% wIth a standard devIatiOn of ±O 9 mg/1

Blbhography

1 Standard Methods for the ExaminatiOn of Water and Wastewater, 14th EdItiOn, pSIS,

Method 502A, (1975)

2 Blum, K A, and Taras, M J, "DeterminatiOn of EmulsIfymg all m Industnal Wastewater",

JWPCF Research Suppl 40, R404 (1968)

413 1-3
OIL AND GREASE, TOTAL RECOVERABLE

Method 413.2 (Spectrophotometric, Infrared)

STORET NO. 00560

1 Scope and ApplIcatIOn

1 1 Th1s method mc1udes the measurement of fluorocarbon-l 13 extractable matter from

surface and salIne wdters, mdustnal and domestic wastes It 1S applIcable to the

determmatIOn of hydrocarbons, vegetable ol1s, ammal fats, waxes, soaps, greases and

related matter

1 2 The method 1S applIcable to measurement of most lIght petroleum fuels, although loss of

about half of any gasohne present dunng the extractIOn mampulatIOns can be expected

1 3 The method covers the range from 0 2 to 1000 mg/l ofextractable matenal

1 4 Wh1le th1s method can be used to obtam an estimate ofthe 011 and grease that would be

measured grav1metncally, m many cases the est1mate more accurately descnbes the

parameter, as 1t w111 measure volatiles more effectively and 1S not suscept1ble to

mterferences such as extractable sulfur It can be used w1th the Petroleum Hydrocarbon

procedure to obtam an 011 and grease value and a petroleum hydrocarbon value on the

same sample

2 Summary ofMethod

2 1 The sample 1S aC1d1fied to a low pH ( <2) and extracted w1th fluorocarbon-l 13 The 011

and grease 1S determmed by companson ofthe mfrared absorbance ofthe sample extract

w1th standards

3 DefimtIOns

3 1 The defimtIOn of 011 and grease 1S based on the procedure used The source of the oil

and/or grease, and the presence ofextractable non-OIly matter w111 mfluence the matenal

measured and mterpretatIOn ofresults

4 SamplIng dnd Storage

4 1 A representative sample of 1 hter volume should be collected m a glass bottle Ifanalys1s

1S to be delayed for more than a few hours, the sample 1S preserved by the add1tIOn of 5 ml

HCl (6 1) at the time ofcollectIOn and refngerated at 4°C

4 2 Because losses of grease w111 occur on samphng eqUlpment, the collectIOn of a compos1te

sample 1S 1mpractiCal Ind1v1dual portIOns collected at prescnbed time mtervals must be

analyzed separately to obtam the average concentratlOn over an extended penod

5 Apparatus

5 1 Separatory funnel, 2000 ml, w1th Teflon stopcock

52 Infrared spectrophotometer, scannmg Non-scannmg mstruments may also be used but

can be subject to pos1tive mterferences 1n complex chem1cal wastewaters

5 3 Cells, 10 mm, 50 mm, and 100 mm path length, sodmm chlonde or mfrared grade glass

5 4 Filter paper, Whatman No 40, 11 cm

Issued 1974

Ed1tonal reV1S10n 1978

413 2-1
6 Reagents

6 I Hydrochlonc aCId, I I MIX equal volumes ofconc HCl and dIstilled water

6 2 Fluorocarbon-113, (1, 1,2-tnchloro-l,2,2-tnfluoroethane), b p 48°C

6 3 SodlUm sulfate, anhydrous crystal

6 4 CahbratiOn mIxtures

641 Reference Oil PIpet 150 ml n-hexadecane, 150 ml Isooctane, and 10 0 ml

chlorobenzene mto a 50 ml glass stoppered bottle 'Mamtam the 'mtegnty of the

mIxture by keepmg stoppered except when withdrawmg ahquots

642 Stock standard PIpet 1 0 ml reference Oil (6 41) mto a tared 200 ml volumetnc

flask and ImmedIately stopper WeIgh and dl1ute to volume wIth fluorocarbon-113

643 Workmg standards PIpet appropnate volumes ofstock standard (6 4 2) mto 100

ml volumetnc flasks accordmg to the cell pathlength to be used Dl1ute to volume

wIth fluorocarbon-113 Calculate concentratiOn of standards from the stock

standard

7. Procedure

7 1 Mark the sample bottle at the water memscus for later determmatiOn ofsample volume

Ifthe sample was not aCImfied at time of collectiOn, add 5 ml hydrochlonc aCId (6 1) to

the sample bottle After mlXlng the sample, check the pH by touchmg pH-senSItIve paper

to the cap to msure that the pH IS 2 or lower Add more aCId Ifnecessary

7 2 Pourthe sample mto a separatory funnel

7.3 Add 30 ml fluorocarbon-113 (62) to the sample bottle and rotate the bottle to nnse the

SIdes Transfer the solvent mto the separatory funnel Extract by shakmg vIgorously for 2

mmutes Allow the layers to separate

74 FIlter the solvent layer mto a 100 ml volumetnc flask through a funnel contammg

solvent-m01stened filter paper

NOTE: An emulsiOn that falls to dIssIpate can be broken by pounng about 1g sodlUm

sulfate (6 3) mto the filter paper cone and slowly drammg the emulSIon through the salt

AddItional 1g portiOns can be added to the cone as reqUIred

75 Repeat (73 and 74) tWIce more WIth 30 ml portIons of fresh solvent, combmmg all

solvent m the volumetnc flask

76 Rmse the tIp ofthe separatory funnel, filter paper, and the funnel WIth a total of 5-10 ml

fluorocarbon-113 and collect the nnsmgs m the flask DIlute the extract to 100 ml, and

stopper the flask '

7 7 Select appropnate workmg standards and cell pathlength accordmg to the followmg

table ofapprOXImate workmg ranges

Pathlength

10 mm

50 mm

100 mm

Range

2-40 mg

04-8 mg

01-4 mg

78 Scan standards and samples from 3200 cm-1 to 2700 cm-1 WIth fluorocarbon-113 m the

reference beam and record the results on absorbance paper The absorbances ofsamples

413 2-2
and standards are measured by constructmg a straight baseline over the range ofthe scan

and measunng the absorbance of the peak maXimum at 2930 cm-I and subtractmg the

baseline absorbance at that pomt For an example of a typiCal 011 spectrum and baseline

constructlOn, see Gruenfeld(3) Non-scanmng mstruments should be operated accordmg

to manufacturer's mstructiOns, although cahbratiOn must be performed usmg the

standards descnbed above (64) If the absorbance exceeds 08 for a sample, select a

shorter pathlength or dilute as reqUired

7 9 Use a cahbratiOn plot of absorbance vs mg 011 prepared from the standards to determme

the mg 011 m the sample solutiOn

8 CalculatiOn

8 1 RxD mg/l total 011 and grease = V

where

R = 011 m solutiOn, determmed from cahbratiOn plot, m mllhgrams

D = extract dllutlOn factor, ifused

V = volume of sample, determmed by refilhng sample bottle to cahbratlOn Ime and

correctmg for aCid addition ifnecessary, m hters

9 PrecisiOn and Accuracy

9 1 The two 011 and grease methods m this manual were tested by a smgle laboratory (EMSL)

on sewage This method determmed the 011 and grease level m the sewage to be 17 5

mg/l When 1 hter portiOns ofthe sewage were dosed With 140 mg ofa mixture of #2

fuel 011 and Wesson 011, the recovery was 99% With a standard deviatlOn of ±14 mg/l

Blbbograpily

1 Standard Methods for the ExammatiOn of Water and Wastewater, 14th Edition, p 516,

Method 502B, (1975)

2 Amencan Petroleum Institute, "Manual on Disposal of Refinery Wastes", Vol IV, Method

733-58 (1958)

3 Gruenfeld, M, "ExtractlOn of Dispersed 011s from Water for Quantitative AnalySiS by

Infrared Spectroscopy", EnViron SCi Technol L...636 (1973)

413 2-3
ORGANIC CARBON, TOTAL

Method 415.1 (Combustion or Oxidation)

STORET NO. Total 00680

Dissolved 00681

1 Scope and ApphcatIOn

1 1 Th1s method mcludes the measurement of orgamc carbon m drmkmg, surface and saline

waters, domest1c and mdustnal wastes ExclusIOns are noted under DefimtIOns and

Interferences

1 2 The method 1S most apphcable to measurement oforgamc carbon above 1mg!1

2 Summary ofMethod

2 1 Orgamc carbon m a sample 1S converted to carbon dIOx1de (C02) by catalytiC combustIOn

or wet chem1cal oX1datIOn The CO2 formed can be measured d1rectly by an mfrared

detector or converted to methane (CH4) and measured by a flame IOmzatIOn detector

The amount ofCO2 or CH4 is d1rectly proportIOnal to the concentratIOn of carbonaceous

matenal m the sample

3 DefimtIOns

3 1 The carbonaceous analyzer measures all of the carbon m a sample Because of vanous

properties of carbon-contammg compounds m hqUld samples, prehmmary treatment of

the sample pnor to analysis d1ctates the defimtIOn ofthe carbon as 1t 1S measured Forms

ofcarbon that are measured by the method are

A) soluble, nonvolatl1e orgamc carbon, for mstance, natural sugars

B) soluble, volatl1e orgamc carbon, for mstance, mercaptans

C) msoluble, partially volatl1e carbon, for mstance, O1ls

D) msoluble, partlCulate carbonaceous matenals, for mstance, cellulose fibers

E) soluble or msoluble carbonaceous matenals adsorbed or entrapped on msoluble

morgamc suspended matter, for mstance, Olly matter adsorbed on Sllt particles

3 2 The final usefulness of the carbon measurement 1S m assessmg the potential oxygendemandmg load of orgamc matenal on rece1vmg stream Th1s statement apphes

whether the carbon measurement 1S made on a sewage plant effiuent, mdustnal waste, or

on water taken d1rectly from the stream In th1s hght, carbonate and b1carbonate carbon

are not a part ofthe oxygen demand m the stream and therefore should be discounted m

the final calculatIOn or removed pnor to analys1s The manner of prehmmary treatment

of the sample and mstrument settmgs defines the types of carbon whlCh are measured

Instrument manufacturer's mstructIOns should be followed

Approved for NPDES

Issued 1971

Ed1tonal reV1S10n 1974

415 I-I
4. Sample Handlmg and PreservatIon

4 I Samplmg and storage ofsamples m glass bottles IS preferable Samphng and storage m

plastIc bottles such as conventiOnal polyethylene and cubitamers IS permISSIble If It IS

estabhshed that the contamers do not contnbute contammatmg orgamcs to the samples

NOTE 1: A bnefstudy performed m the EPA Laboratory mdicated that dIst111ed water

stored m new, one quart cubitamers dId not show any mcrease m orgamc carbon after

two weeks exposure

4 2 Because ofthe possIbIhty ofoXIdatiOn or bactenal decomposItiOn ofsome components of

aqueous samples, the lapse of time between collectiOn of samples and start of analySIS

should be kept to a IrlJmmum Also, samples should be kept cool (4°C) and protected

from sunhght and atmosphenc oxygen

4 3 In mstances where analySIS cannot be performed withm two hours (2 hours) from time of

samplmg, the sample IS aCIdIfied (pH s 2) wIth HCl or H2S04

5 Interferences

5 1 Carbonate and bIcarbonate carbon represent an mterference under the terms of thIS test

and must be removed or accounted for m the final calculation

5 2 ThIS procedure IS apphcable only to homogeneous samples whIch can be mJected mto the

apparatus reproducIbly by means of a mICrohter type synnge or pIpette The opemngs of

the synnge or pIpette hmit the maXImum SIze of partICles whIch may be mcluded m the

sample

6 Apparatus

6 1 Apparatus for blendmg or homogemzmg samples Generally, a Wanng-type blender IS

satIsfactory

6 2 Apparatus for total and dIssolved orgamc carbon

6 2 1 A number of compames manufacture systems for measurmg carbonaceous

matenal m hqUld samples ConsIderatiOns should be made as to the types of

samples to be analyzed, the expected concentratiOn range, and forms of carbon to

be measured

6 2 2 No specIfic analyzer IS recommended as supenor

7. Reagents

7 1 DIstl1led water used m preparatiOn of standards and for dIlutIon of samples should be

ultra pure to reduce the carbon concentratiOn of the blank Carbon diOXIde-free, double

dIstIlled water IS recommended Ion exchanged waters are not recommended because of

the pOSSIbIhtIes ofcontammatiOn wIth organIC materIals from the resms

72 PotaSSIUm hydrogen phthalate, stock solutiOn, 1000 mg carbon/hter DIssolve 0 2128 g

of potassIUm hydrogen phthalate (Pnmary Standard Grade) m dIstIlled water and dIlute

to 100 Oml

NOTE 2' SodIUm oxalate and acetic aCId are not recommended as stock solutiOns

7 3 PotaSSIUm hydrogen phthalate, standard solutiOns Prepare standard solutiOns from the

stock solution by dl1utiOn WIth dIStilled water

74 Carbonate-bIcarbonate, stock solutiOn, 1000 mg carbon/hter WeIgh 03500 g ofsodIUm

bIcarbonate and 04418 g of sodIUm carbonate and transfer both to the same 100 ml

volumetnc flask DIssolve WIth dIStIlled water

415 1-2
7 5 Carbonate-biCarbonate, standard solutIOn Prepare a senes of standards slmllar to step

73

NOTE 3: ThIS standard IS not reqUlred by some mstruments

76 Blank solutIOn Use the same dlstllled water (or slmllar quahty water) used for the

preparatIOn ofthe standard solutIOns

8 Procedure

8 I Follow mstrument manufacturer's mstructIOns for cahbratIOn, procedure, and

calculatIOns

8 2 For calIbratIOn of the mstrument, It IS recommended that a senes of standards

encompassmg the expected concentratIOn range ofthe samples be used

9 PreclSlon and Accuracy

9 1 Twenty-eIght analysts m twenty-one laboratones analyzed dlstllled water solutIOns

contammg exact mcrements ofoXIdIzable orgamc compounds, wIth the followmg results

Increment as

TOe

mg/lIter

49

107

PrecIsion as

Standard DeviatIOn

TOe, mg/lIter

393

832

BiaS,

%

+1527

+ 101

Accuracy as

BiaS,

mg/lIter

+075

+108

(FWPCA Method Study 3, Demand Analyses)

BIblIography

1 Annual Book ofASTM Standards, Part 31, "Water", StandardD 2574-79, p469 (1976)

2 Standard Methods for the ExammatIOn of Water and Wastewater, 14th EdItIOn, p 532,

Method 505, (1975)

415 1-3
&EPA

United States

Environmental Protection

Agency

Research and Development

Test Method

Environmental MOnitoring and

Support Laboratory

Cmcmnatl OH 45268

Organic C;arbon, Total

(low level)

(UV promoted, persulfate

oxidation)-Method 41 q.2

1 Scope and ApplicatIon

1 1 This method covers the

determination of total organic carbon

In drinking water and other waters

subject to the limitations In 1 3 and

51

1 2 This Instrument IS designed for

a two-step operation to distingUish

between purgeable and nonpurgeable

organic carbon These separate values

are not pertinent to this method

1 3 This method IS applicable only to

the carbonaceous matter which IS

either soluble or has a partIcle size of

02 mm or less

1 4 The applicable range IS from

approximately 50 Jlg/L to 10 mg /L

Higher concentrations may be

determined by sample dilution

2 Summary of Method

A sample IS combined with 1 mL of

aCidified persulfate reagent and

placed In a sparger The sample IS

purged with helium which transfers

Inorganic CO2 and purgeable organics

to a CO2 scrubber The CO2 IS

removed with at least 99 9%

effiCiency with a 2 5-mlnute purge

The purgeable organics proceed

through a reduction system where the

gas stream IS JOined by hydrogen and

passed over a nickel catalyst which

converts the purgeable organic carbon

to methane The methane IS

measured by a flame Ionization

detector The detector signal IS

Integrated and dIsplayed as the

concentration of purgeable organic

carbon

The sample IS then transferred to a

quartz ultraviolet reacflon cOil where

the nonpurgeable organIcs are

subjected to Intense ultravIolet

Illumination In the presence of the

aCidifIed persulfate reagent The

nonpurgeables are converted to CO2

and transferred to a second sparger

where a helium purge transfers the

C02 to the reduction system and Into

the detector The signal IS Integrated,

added to the purgeable organic carbon

value and displayed as the

concentration of total organic carbon

3 DefinItIons

3 1 Total organic carbon measured

by this procedure IS the sum of the

purgeable organic carbon and the

nonpurgeable organic carbon as

defined In 3 2 and 3 3

3 2 Purgeable organic carbon IS the

organic carbon matter that IS

transferred to the gas phase when the

sample IS purged with helium and

which passes through the CO2

scrubber The definition IS InstrumentconditIon dependent

3 3 Nonpurgeable organic carbon IS

defined as that which remains after

removal of the purgeable organic

carbon from the sample contamlng

aCIdifIed persulfate reagent and which

4152-1 Dec 1982
IS converted to C02 under the

Instrument conditions

3.4 The system blank IS the value

obtained 10 8 2 fpr an Irradiated,

recirculated reagent distilled water

sample

4. Sample Handling and

'Preservation

4.1 Sampling and storage of

samples must be clone In glass

bottles Caution Do not leave any

headspace 10 the sample bottle as

thiS may contribute to loss of

purgeable organics

4 2 Because of the POSSibility of

OXidation or bactenal decomposition of

some components of aqueous

samples, the lapse of tIme between

collection of samples and start of

analysIs should be kept to a minImum

Also, samples should be kept cool

(4°C) and protected from sunlight and

atmosphenc oxygen

4 3 When analYSis cannot be

performed within two hours from time

of sampling. the sample should be

acidlfled to pH 2 with H2S04 Note

HCr should not be used because It IS

converted to chlorine dunng the

analysIs This causes damage to the

Instrument

6. Interferences

6.1 If a sample IS homogenized to

reduce the size of the particulate

matter, the homogenizing may cause

loss of purgeable organic carbon, thus

yielding erroneously low results

6. Apparatus

6.1 Apparatus for blending or

homogeniZing samples A household

blender or similar deVice that Will

reduce particles in the sample to less

than 02 mm

6.2 Apparatus for Total Organic

Carbon' The essential components for

the apparatus used In thiS method

are A sparge assembly, flow

SWitching valves. a pyrolYSIS furnace,

quartz ultraviolet reactor cOil, redUCing

column, flame Ionization detector,

electrometer and Integrator ThiS

method IS based on the Dohrmann

Envlrotech DC-54 Carbon Analyzer

Other Instruments having Similar

performance characterrstlcs may be

used

6 3 Sampling DeVices Any

apparatus that Will reliably transfer

10 mL of sample to the sparger A 50

mL glass syrmge IS recommended

when analyzmg samples with eaSily

purgeable organics so as to minimiZe

losses

7 Reagents

7 1 Reagent Distilled Water

Distilled water used In preparation of

standards and for dilution of samples

should be ultra-pure to reduce the

magnrtude of the blank Carbon

diOXide-free, double distilled water IS

recommended The water should be

distilled from permanganate or be

obtamed from a system mvolvmg

distillation and carbon treatment The

reagent distilled water value must be

compared to a system blank

determmed on a recirculated distilled

water sample The total organic

carbon value of the reagent distilled

water should be less than 60 tlg/L

Purgeable organrc carbon values of

the reagent distilled water should be

less than 4 tlglL

72 Potassium hydrogen phthalate,

stock solution 500 mg carbon/liter

Dissolve 1 063 g of potassIum

hydrogen phthalate (Primary Standard

Grade) 10 reagent distIlled water (7 1)

and dilute to 1 liter

7 3 Potassium hydrogen phthalate (2

mg/L) Pipet 4 mL of potassIUm

hydrogen phthalate stock solutIOn

(7 2) mto a one liter volumetnc flask

and dilute to the mark With reagent

distilled water (7 1}

74 Potassium hydrogen phthalate (5

mg/L) Pipet 1 mL of potassium

hydrogen phthalate stock solution

(72) mto a 100 mL volumetnc flask

and dilute to the mark With reagent

distilled water (7 1)

7 5 Potassium hydrogen phthalate

(10 mg/L) Pipet 2 mL of potassium

hydrogen phthalate stock solution

(7 2) mto a 100 mL volumetnc flask

and dilute to the mark With reagent

distIlled water (7 1)

7 6 ACidified Persulfate Reagent

Place 100 mL of reagent distilled

water (7 1) In a container Add 5 g of

potassium persulfate Add 5 g (3 mL)

of concentrated (85%) phosphoriC

aCid

7 7 Carbonate-bicarbonate, stock

solution, 1000 mg carbon/liter Place

a 3500 g of sodium bicarbonate and

04418 g of sodium carbonate 10 a

100 mL volumetrrc flask Dissolve With

reagent distilled water (7 1) and dilute

to the mark

7 8 Carbonate-bicarbonate, standard

solution 50 mg/L Place 5 ml of the

carbonate-bicarbonate stock solution

10 a 100 mL volumetrrc flask and

dilute to the mark With reagent

distilled water (7 1)

8 Procedure

8 1 Allow at least 30 mmutes

warm-up time Leave mstrument

console on continuously when In dally

use, except for the ultraviolet light

source, which should be turned off

when not 10 use for more than a few

hours

8 2 Adjust all gas flows,

temperatures and cycle times to

manufacturer s speCifications Perform

the System Cleanup and Calibration

procedure In the manufacturer s

speCifications each day ReCirculate a

sample of Irradiated distilled water

until two consecutive readings wlthm

10% of each other are obtained

Record the last value for the system

blank ThiS value IS a function of the

total Instrument operation and should

not vary Significantly from preViOUS

runs Reasons for Significant changes

In the value should be Identified

8 3 Check the effectiveness of the

CO2 scrubber by analyZing the

carbonate-bicarbonate standard

solutlon(7 8) Add 1 mL of aCidified

persulfate reagent (7 6) to 50 mL of

the solution Transfer 10 mL of the

solutlon-wlth-reagent to the first

sparger and start the analYSIS cycle

No response, or a very minor reading,

should be obtained from thiS solution

8 4 Add 1 mL of aCidified persulfate

reagent (7 6) to 50 mL of reagent

distilled water (7 1) blank, standards

7 3, 74, and 7 5 and the samples

8 5 Calibrate the analyzer as

follows

85 1 Run the reagent distilled water

(7 1) and 5 a mg/L standard (74)

Transfer 10 mL of the solutlon-wlthreagent to the first sparger and start

analyzer cycle

Ignore the meter reading for the first

cycle

Transfer a second 10 mL of the

solution-with-reagent to the first

sparger and start the analYSIS cycle

Record the meter reading (see 9 1) of

the final carbon value for each of the

reagent distilled water (7 1) and the

standard (7 4)

If the meter read109 IS more than 25%

above or below the calculated value of

standard 7 4, reanalyze the standard

Dec 1982 4152-2
and set the calIbratIOn wlthm 25%

\?> '5 4) reana\yze the system blank

and then begm 85 1 agarn If the

meter readrng (see 9 1) IS wIthin 25%

of the calculated value, continue to

next step The calculated value IS

defined In 8 5 2

852 Calculate the factor for the

deviation of the mstrument reading

(see 9 1) for the standard (7 4) from

the calculated value by

standard readrng -

calculated value - FACTOR

calculated value

where the calculated value IS that

value obtained by uSing the weight of

potassium hydrogen phthalate and

does not rnclude the carbon

contributed by the reagent dIstilled

water (7 1) wIth which It has been

dIluted

85 3 Calculate the adjusted reading

by

calculated value + (RDW - (FACTOR X

RDW));::: ADJUSTED READING

where RDW = mean reagent distilled

water (7 1) value

854 Push In CALIBRATE button

after READY light comes on and

adjust the SPAN control to the

ADJUSTED READING calculated In

853

8 6 Analyze the standards 7 3 and 7 5

rn order to check the linearity of the

rnstrument at least once each day

Transfer 10 mL of the solutlon-wIthreagent to the first sparger and start

analyzer cycle

Ignore the meter readrng for the first

cycle

Transfer a second 10 mL of the

solutIOn-wIth-reagent to the first

sparger and start the analyzer cycle

Record the meter readrng (see 9 1) of

the frnal carbon value for each of the

standards 73 and 7 5

The range of concentratIon used for

callbratrng the rnstrument and

checkrng the linearity of the

Instrument should be ascertained

from a knowledge of the ra nge of

concentrations expected from the

samples Standards for lower ranges

can be prepared by diluting standards

7 2, 7 3, and 7 4

87 Analyze the samples Transfer

10 mL of sample with reagent to the

first sparger and start the analysIs

cycle

Transfer 10 ml of the solutlon-wlthreagent to the first sparger and start

analyzer cycle

Ignore the meter reading for the fIrst

cycle

Transfer a second 10 mL of the

soJutlon-wlth-reagent to the fIrst

sparger and start the analyzer cycle

Record the meter readrng (see 9 1) of

the frnal carbon value for each of the

samples

9 Calculations

9 1 The values are read off the frnal

digital readout In /lg/L The system

blank readrng obtarned rn 8 2 must be

subtracted from all reagent dIstilled

water, standard and sample readrngs

10 PrecIsion and Accuracy

10 1 In a single laboratory (MERL)

usrng raw river water centrifuged

river wa+er drlnkrng water and the

effluent from a carbon column which

had concentratIOns of 3 11, 3 10

1 79 and 0 07 mg/L total organIc

carbon respectively the standard

devIatIons from ten replicates were

±O 13, ±O 03 ±o 02 and ±O 02

mg/L respectively

10 2 In a single laboratory (MERL)

uSing potassium hydrogen phthalate

rn distilled water at concentrations of

50 and 1 0 mg/L total organIc carbon,

recovenes were 80% and 91 %

respectIvely

Bibliography

1 Proposed Standard Method for

Purgeable and Nonpurgeable OrganIc

Carbon rn Water (UV-promoted,

persulfate OXIdatIon method) ASTM

Committee D-19, Task Group

19060203 (Chairman R J Joyce),

January 1978

2 Operating InstructIOn Dohrmann

Envlrotech 3420 Scott Boulevard

Santa Clara California 95050

3 Takahashi, Y Ultra Low Level

TOC AnalYSIS of Potable Waters

Presented at Water Quality

Technology Conference AWWA Dec

5-8 1976

4152-3 Dec 1982
PETROLEUM HYDROCARBONS, TOTAL RECOVERABLE

Method 418.1 (Spectrophotometric, Infrared)

STORET NO. 45501

1 Scope and Apphcat10n

1 1 Th1s method 1S for the measurement of fluorocarbon-113 extractable petroleum

hydrocarbons from surface and sahne waters, mdustnal and domest1c wastes

1 2 The method 1S apphcable to measurement ofhght fuels, although loss ofabout halfofany

gasohne present dunng the extractlOn mampulatlOns can be expected

1 3 The method 1S sens1tIve to levels of 1 mg/l and less, and may be extended to amb1ent

momtormg

2 Summary ofMethod

2 1 The sample 1S aC1d1fied to a low pH ( <2) and senally extracted w1th fluorocarbon-113 m

a separatory funnel Interferences are removed w1th s1hca gel adsorbant Infrared

analys1s ofthe extract 1S performed by d1rect companson w1th standards

3 Defimt10ns

3 1 As m the case of011 and Grease, the parameter ofPetroleum Hydrocarbons 1S defined by

the method The measurement may be subject to mterferences and the results should be

evaluated accordmgly

3 2 011 and Grease 1S a measure of blOdegradable ammal greases and vegetable olls along

w1th the relative non-blOdegradable mmeral olls Petroleum hydrocarbons 1S the measure

of only the mmeral olls Max1mum mformatlOn may be obtamed usmg both methods to

measure and charactenze 011 and grease ofall sources

4 Samphng and Storage

4 1 A representatIve sample of 1 hter volume should be collected m a glass bottle Because

losses of grease w111 occur on samphng eqUlpment, the collectlOn ofa compos1te sample 1S

1mpractlCai The ent1re sample 1S consumed by th1s test, no other analyses may be

performed usmg ahquots ofthe sample

4 2 A delay between samplmg and analys1s of greater than 4 hours reqUlres sample

preservatlOn by the add1tlOn of 5 ml HCl (6 1) A delay of greater than 48 hours also

reqUlres refngeratlOn for sample preservatlOn

5 Apparatus

5 1 Separatory funnel, 2000 ml, w1th Teflon stopcock

5 2 Fllter paper, Whatman No 40, 11 cm

5 3 Infrared spectrophotometer, scanmng or fixed wavelength, for measurement around

2950cm-1

5 4 Cells, 10 mm, 50 mm, and 100 mm pathlength, sodlUm chlonde or mfrared grade glass

5 5 MagnetIc st1rrer, w1th Teflon coated st1rrmg bars

6 Reagents

6 1 Hydrochlonc aC1d, 1 1 M1x equal volumes ofconc HCl and d1stllied water

Issued 1978

418 1-1
I 11111111 II 111111111 I 1111

62 Fluorocarbon-1l3,(I,I,2-tnchloro-l,2,2-tnfluroethane), b p 48°C

6 3· Sodmm sulfate, anhydrous crystal

64 Sdlca gel, 60-200 mesh, Davidson Grade 950 or eqmvalent Should contam 1-2% water

as defined by residue test at 130°C Adjust by overmght eqmlIbratlOn Ifneeded

6 5 CalIbratIOn mixtures

65 1 Reference 011 PIpet 150 ml n-hexadecane, 150 ml Isooctane, and 10 0 ml

chlorobenzene mto a 50 ml glass stoppered bottle Mamtam the mtegnty of the

mixture by keepmg stoppered except when withdrawmg alIquots

652 Stock standard PIpet 10 ml reference 011 (6 5 1) mto a tared 200 ml volumetnc

flask and Immediately stopper WeIgh and dilute to volume WIth fluorocarbon-I 13

653 Workmg standards Pipet appropnate volumes ofstock standard (652) mto 100

ml volum,etnc flasks accordmg to the cell pathlength to be used DIlute to volume

WIth fluorocarbon-113 Calculate concentratIOn of standards from the stock

standard

7 Procedure

7 1 Mark the sample bottle at the water memscus for later determmatlOn ofsample volume

Ifthe sample was not aCidified at tIme of collectIOn, add 5 ml hydrochlonc aCId (6 1) to

the sample bottle After mlxmg the sample, check the pH by touchmg pH-senSitive paper

to the cap to msure that,the pH IS 2 or lower Add more aCId Ifnecessary

7 2 Pour the sample mto a separatory funnel

73 Add 30 ml fluorocarbon-l13 (62) to the sample bottle and rotate the bottle to nnse the

Sides Transfer the solvent mto the separatory funnel Extract by shakmg vIgorously for 2

minutes Allow the layers to separate

7 4 Ftlter the solvent layer through a funnel contammg solvent-mOIstened filter paper mto a

100 ml volumetnc flask

NOTE 1 An emulSIon that fads to dISSIpate can be broken by pourmg about I g sodmm

sulfate (6 3) mto the filter paper cone and slowly drammg the emulSIOn through the salt

Additional 1g portIons can be added to the cone as reqmred

7.5 Repeat (73 and 74) tWice more WIth 30 ml portIons of fresh solvent, combmlng all

solvent mto the volumetnc flask

76 Rinse the tIp ofthe separatory funnel, filter paper, and the funnel WIth a total of 5-10 ml

solvent and collect the nnsmgs m the flask DIlute the extract to 100 ml Ifthe extract IS

known to contam greater than 100 mg of non-hydrocarbon orgamc matenal, pipet an

appropnate portIon ofthe sample to a 100 ml volumetnc and dilute to volume

77 Discard about 5-10 ml solutIOn from the volumetnc flask Add 3 g SIlIca gel (6 4) and a

stlrrmg bar, stopper the volu~etnc flask, and stIr the solutIOn for a mmlmum of 5 mm on

a magnetIc stIrrer

418 1-2
7 8 Select appropnate workmg standards and cell pathlength accordmg to the followmg

table ofapproximate workmg ranges

Path1ength

10 mm

50 mm

100 mm

Range

2-40 mg

05-8 mg

01-4 mg

Cahbrate the mstrument for the appropnate cells usmg a senes of workmg standards

(653) It IS not necessary to add slIlCa gel to the standards Determme absorbance

directly for each solutIOn at the absorbance maximum at about 2930 cm-1 Prepare a

cahbratlOn plot of absorbance vs mg petroleum hydrocarbons per 100 ml solutIOn

7 9 After the slhca gel has settled m the sample extract, fill a clean cell With solutIOn and

determme the absorbance of the extract If the absorbance exceeds 0 8 prepare an

appropnate dlIution

NOTE 2: The posslblhty that the absorptive capacity ofthe s1I1ca gel has been exceeded

can be tested at thiS pomt by addmg another 3 0 g slhca gel to the extract and repeatmg

the treatment and determmatlon

7 10 Determme the concentratIOn ofpetroleum hydrocarbons m the extract by companng the

response agamst the cahbratlOn plot

8 CalculatIOns

8 1 Calculate the petroleum hydrocarbons m the sample usmg the formula

RxD mg/l Petroleum Hydrocarbons = V

where

R = mg ofPetroleum Hydrocarbons as determmed from the cahbratwn plot (7 10)

D = extract dlIutwn factor, Ifused

V = volume ofsample, m hters

9 PrecIsion and Accuracy

9 1 PreCISIOn and accuracy data are not avalIable at thiS time

418 1-3
PHENOLICS, TOTAL RECOVERABLE

Method 420.1 (Spectrophotometric, Manual 4·AAP with Distillation)

STORET NO. 32730

1 Scope and ApphcatIOn

1 1 ThIs method IS apphcable to the analysIs ofdnnkmg, surface and sahne waters, domestic

and mdustrIal wastes

1 2 The method IS capable of measunng phenohc matenals at the 5 ug/1 level when the

colored end product IS extracted and concentrated m a solvent phase usmg phenol as a

standard

1 3 The method IS capable of measurmg phenohc matenals that contam more than 50 ug/1

m the aqueous phase (wIthout solvent extractIOn) usmg phenol as a standard

1 4 It IS not possIble to use thIS method to dIfferentIate between dIfferent kmds ofphenols

2 Summary ofMethod

2 1 Phenohc matenals react wIth 4-ammoantIpynne m the presence of potassIUm

ferncyamde at a pH of 10 to form a stable reddIsh-brown colored antIpynne dye The

amount ofcolor produced IS a functIon ofthe concentratIon ofphenohc matenal

3 Comments

3 1 For most samples a prehmmary dIstl1latIon IS reqUIred to remove mterfermg materials

3 2 Color response of phenohc matenals wIth 4-ammo antipyrme IS not the same for all

compounds Because phenohc type wastes usually contaIn a vanety of'phenols, It IS not

pOSSIble to duphcate a mIxture ofphenols to be used as a standard For thIS reason phenol

has been selected as a standard and any color produced by the reactIOn of other phenohc

compounds IS reported as phenol ThIs value WIll represent the mimmum concentratIOn

ofphenohc compounds present In the sample

4 Sample Handhng and PreservatIon

4 1 BIOlogICal degradation IS mhIbited by the addItIOn of 1 gil of copper sulfate to the

sample and aCIdIficatIOn to a pH ofless than 4 wIth phosphonc aCId The sample should

be kept at 4°C and analyzed withm 24 hours after collectIOn

5 Interference

5 1 Interferences from sulfur compounds are ehmmated by aCIdIfymg the sample to a pH of

less than 4 wIth H3P04and aeratIng bnefly by stIrnng and addmg CUS04

5 2 OXIdIZIng agents such as chlonne, detected by the hberation ofIOdme upon aCIdIficatIOn

m the presence of potaSSIUm IodIde, are removed ImmedIately after samphng by the

addItIOn of an excess of ferrous ammOnIum sulfate (7 10) If chlonne IS not removed,

the phenohc compounds may be partIally oXIdIzed and the results may be low

Approved for NPDES

Issued 1971

Editonal reVISIon 1978

420 I-I
6. Apparatus

6 1 DistillatIOn apparatus, all glass conslstmg of a 1 hter pyrex dlstIlhng apparatus with

Graham condenser

62 pH meter

6 3 Spectrophotometer, for use at 460 or 510 nm

64 Funnels

6 5 FIlter paper

6 6 Membrane filters

6 7 Separatory funnels, 500 or 1,000 ml

6 8 Nessler tubes, short or long form

7 Reagents

7 1 Phosphonc aCid solution, 1 + 9 DIlute 10 m1 of 85% H3P04 to 100 m1 With distilled

water

72 Copper sulfate solution Dissolve 100 g CuS04-5H20 m distIlled water and dIlute to 1

hter

7.3 Buffer solutIOn Dissolve 169 g NH4Cl m 143 ml cone NH40H and dIlute to 250 ml

With distilled water Two ml should adjust 100 ml ofdistIllate to pH 10

74 Ammoantlpynne solution Dissolve 2 g of 4AAP m distIlled water and dIlute to 100 ml

7 5 PotassIUm ferncyamde solution Dissolve 8 g of K3Fe(CN)6 m distilled water and dIlute

to 100ml

7.6 Stock phenol solution Dissolve 109 phenol m freshly boIled and cooled distilled water

and dIlute to 1 hter 1ml = 1mg phenol

77 Workmg solution A Dilute 10 ml stock phenol solutIOn to 1 hter With distilled water

1 ml = 10 ug phenol

78 Workmg solutIOn B DIlute 100 ml ofworkmg solutIOn A to 1000 ml With distIlled water

1ml = 1 ug phenol

7 9 Chloroform

7.10 Ferrous ammomum sulfate Dissolve 1 1 g ferrous ammomum sulfate In 500 ml distilled

water comammg 1 ml cone H~04 and dIlute to 1 hter With freshly boIled and cooled

distilled water

8 Procedure

8 1 DistIllatIOn

8 1 1 Measure 500 mlsample mto a beaker Lower the pH to approXimately 4 With 1 + 9

H3P04 (7 1), add 5 ml CuS04 solutIOn (72) and traq.sfer to the distillation

apparatus Omit addmg H 2P04 and CuS04 1fsampie was preserved as descnbed m

41

8 1 2 DistIll 450 ml ofsample, stop the distIllatIOn, and when bOlhng ceases add 50 ml of

warm distilled water to the flask and resume distillatIon untIl 500 ml have been

collected

8 1 3 Ifthe distillate IS turbid, filter through a prewashed membrane filter

8 2 Direct photometnc method

821 Usmg workmg solutIOn A (77), prepare the followmg standards m 100 m1

volumetnc flasks

4201-2
fil of workmg solutlOn A

o

05

10

20

50

80

100

Cone ug/l

00

500

1000

2000

5000

8000

10000

8 2 2 To 100 ml ofdIstIllate or an ahquot dIluted to 100 ml and/or standards, add 2 ml of

buffer solutIOn (7 3) and mIX The pH of the sample and standards should be

10 ±02

8 2 3 Add 2 0 ml ammoantlpynne solutIOn (7 4) and mIX

8 2 4 Add 2 0 ml potassIUm ferncYamde solutIOn (7 5) and mIX

8 2 5 After 15 mmutes read absorbance at 510 nm

8 3 Chloroform extractIOn method

8 3 1 Usmg workmg solutIOn B (7 8), prepare the followmg standards Standards may be

prepared by plpettmg the reqUIred volumes lUtO the separatory funnels and

dIlutmg to 500 ml WIth dIstIlled water

fil of workmg solutton B

00

30

50

100

200

250

Cone ug/l

00

60

100

200

400

500

8 3 2 Place 500 ml of dIstIllate or an ahquot dIluted to 500 ml m a separatory funnel The

sample should not contam more than 25 ug phenol

8 3 3 To sample and standards add 10 ml of buffer solutIOn (7 3) and mIX The pH

should be 10 ±O 2

8 3 4 Add 3 0 ml ammoantlpynne solutIOn (7 4) and mIX

8 3 5 Add 3 0 ml potassIUm ferncyamde solutIOn (7 5) and mIX

8 3 6 After three mmutes, extract WIth 25 ml of chloroform (7 9) Shake the separatory

funnel at least 10 tlmes, let CHCl3 settle, shake agam 10 tImes and let chloroform

settle agam Vent chloroform fumes mto hood

8 3 7 FIlter chloroform extracts through fIlter paper Do not add more chloroform

Carryout fIltratIOn m a hood 'DIspose of chloroform m envIronmentally

acceptable manner

8 3 8 Read the absorbance ofthe samples and standards agamst the blank at 460 nm

9 CalculatIOn

9 1 Prepare a standard curve by plottmg the absorbance value of standards versus the

correspondmg phenol concentratIOns

9 2 Obtam concentratIOn value ofsample dIrectly from standard curve.

4201-3
10 PrecIsIon and Accuracy

10 1 USIng the extractIOn procedure for concentratIOn of color, SIX laboratorIes analyzed

samples at concentratIOns of 9 6, 48 3, and 93 5 ug/l Standard devIatIOns were

±O 99, ±3 1and ±4 2 ug/l, respectIvely

102 USIng the dIrect photometrIc procedure, SIX laboratorIes analyzed samples at

concentratIons of 47,482 and 97 0 mg/l Standard devIations were ±O 18, ±O 48 and

±1 58 mg/l, respectIvely

Bibliography

1 Annual Book ofASTM Standards, Part 31, "":ater", Standard DI783-70, p553 (1976)

2. Standard Methods for the EXamInatIOn of Water and Wastewater, 14th EdItIOn, p574-581,

Method 510 through 51Oe, (1975)

4201-4
PHENOLICS, TOTAL RECOVERABLE

Method 420.2 (Colorimetric, Automated 4-AAP with Distillation)

STORET NO. 32730

1 Scope and ApphcatlOn

1 1 ThIS method IS apphcable to the analysIs of dnnkmg, surface and sahne waters, domestic

and mdustnal wastes

1 2 The method IS capable of measurmg phenohc matenals from 2 to 500 ug/1 m the

aqueous phase usmg phenol as a standard The workmg ranges are 2 to 200 ug/1 and 10

to 500 ug/1

2 Summary ofMethod

2 1 ThIS automated method IS based on the distIllatlOn of phenol and subsequent reactlOn of

the dIstillate wIth alkalme ferncyamde and 4-ammoantipyrme to form a red complex

whIch IS measured at 505 or 520 nm The same mamfold IS used wIth the AAI or AAII

3 Sample Handhng and PreservatlOn

3 1 BlOlogICal degradatlOn IS mhibited by the additlOn of 1 gil of copper sulfate to the

sample and aCIdificatlOn to a pH ofless than 4 wIth phosphonc aCId The sample should

be kept at 4°C and analyzed Wlthm 24 hours after collectlOn

4 Interference

4 1 Interferences from sulfur compounds are ehmmated by aCIdIfymg the sample to a pH of

less than 40 wIth H3P04and aeratmg bnefly by stIrnng and addmg CUS04

4 2 OXIdIzmg agents such as chlonne, detected by the hberatlOn oflOdme upon aCIdificatlOn

m the presence of potaSSIUm IOdIde, are removed ImmedIately after samplmg by the

addItion of an excess offerrous ammomum sulfate (6 5) If chlorme IS not removed, the

phenohc compounds may be partIally OXIdIzed and the results may be low

43 Background contammatIOn from plastIc tubmg and sample contamers IS ehmmated by

fillmg the wash receptacle by SIphon (usmg Kel-F tubmg) and usmg glass tubes for the

samples and standards

5 Apparatus

5 1 Techmcon AutoAnalyzer (lor II)

5 1 I Sampler eqUIpped WIth contmuous mIxer

512 Mamfold

5 1 3 ProportIOmng pump II or III

5 1 4 Heatmg bath WIth dIstIllatIOn coIl

5 1 5 DIstIllatIOn head

5 1 6 Colonmeter eqUIpped WIth a 50 mm flow cell and 505 or 520 nm filter

5 1 7 Recorder

6 Reagents ,

6 1 DIstIllatIOn reagent Add 100 ml of conc phosphonc aCId (85% H3P04) to 800 ml of

dIstIlled water, cool and dIlute to 1 hter

Issued 1974

4202-1
6 2 Buffered potassIUm ferncyamde DIssolve 2 0 g potassIUm ferncyamde, 3 1 g bonc aCId

and 3 75 g potassIUm chlonde m 800 ml ofdIStilled water Adjust to pH of 10 3 WIth 1 N

sodIUm hydroxide (6 3) and dIlute to 1 lIter Add 0 5 ml ofBnJ-35 Prepare fresh weekly

6 3 SodIUm hydroxIde (IN) DIssolve 40 g NaOH m 500 ml ofdIStilled water, cool and dIlute

to 1 lIter

6 4 4-AmmoantIpynne Dissolve 0 65 g of4-ammoantlpynne m 800 ml ofdistIlled water and

dIlute to 1 lIter Prepare fresh each day

6 5 Ferrous ammomum sulfate DIssolve 1 1 g ferrous ammomum sulfate m 500 ml distIlled

water contammg 1ml H2S04and dIlute to 1 lIter With freshly boIled and cooled distIlled

water

6 6 Stock phenol Dissolve 1 00 g phenol m 500 ml of distilled water and dIlute to 1000 ml

Add 1g CUS04 and 0 5 ml conc H3P04as preservative 1 0 ml = 1 0 mg phenol

67 Standard phenol solution A DIlute 10 0 ml of stock phenol solutIOn (66) to 1000 ml

10 ml = 001 mgphenol

68 Standard phenol solution B DIlute 100 0 ml ofstandard phenol solution A (6 7) to 1000

ml With distIlled water 1 0 ml = 0001 mg phenol

6 9 Standard solutIOn C DIlute 100 0 ml ofstandard phenol solutIOn B (6 8) to 1000 ml With

distilled water 1 0 ml = 00001 mg phenol

6 10 Usmg standard solutIOn A, B or C prepare the followmg standards m 100 ml volumetnc

flasks Each standard should be preserved by addmg 0 1 g CuSO4and 2 drops of conc

H3P04 to 100 0 ml

ml of Standard Solution

SolutIOn C

10

20

30

50

SolutlOn B

10

20

50

100

SolutlOn A

2

3

5

Cone ug/l

10

20

30

50

100

200

500

1000

200

300

500

7 Procedure

7 1 Set up the mamfold as shown m Figures 1 or 2

72 Fill the wash receptacle by Siphon Use Kel-F tubmg With a fast flow (1 lIter/hr)

7 3 Allow colonmeter and recorder to warm up for 30 mmutes Run a baselIne With all

reagents, feedmg distIlled water through the sample lme Use polyethylene tubmg for

4202-2
sample hne When new tubIng is used, about 2 hours may be reqmred to obtaIn a stable

baseltne ThIS two hour time penod may b~ necessary to remove the resIdual phenol from

the tubIng

74 Place appropnate phenol standards In sampler In order of decreasIng concentratIon

Complete loadIng pfsampler tray with unknown samples, USIng glass tubes

NOTE 1: Ifsamples have not been preserved as Instructed In (3 1), add 01 g CUS04 and

2 drops ofconc H3P04 to 100 ml ofsample

7 5 SWItch sample hne from distdled water to sampler and begIn analysJs

8 CalculatIOn

8 1 Prepare standard Cllrve by plottIng peak heIghts of standards agamst concentratIon

values Compute concentration of samples by comparIng sample peak heIghts wIth

standards

9 PreCISIOn and Accuracy

9 1 In a smgle laboratory (EMSL), USIng sewage samples at concentrations of 3 8, 15, 43 and

89 ug/l, the standard devIations were ±0,5, ±O 6, ±O 6 and ±1.0 ug(l, respectively At

concentrations of 73, 146, 299 and 447 tIg/1, the standard deviatIons were ±10,

±1 8, ±4 2 and ±5 3 ugfl, respectively

9 2 In a smgle laboratory (EMSL), usmg sewage samples at concentratIOns of 5 3 and 82

ug/l, the recovenes were 78% and 98% At concentratIons of 168 and 489 ug/l, the

recovenes were 97% and 98%, respectively

Bibliography

1 Techmcon AutoAnalyzer II Methodology, Industnal Method No 127-71W, AAII

2 Standard Methods for the EXamInation of Water and Wastewater, 14th EditIOn, p 574,

Method 510 (1975)

3 Gales, M E and Booth, R.L , "Automated 4 AAP Phenoltc Method", AWWA 68,540 (1976)
E::Y

To Waste ***

./ SAMPLEI

/ \ MI/mrn

r t RESAMPLE BLACK _ BLACK 032 AIR @~ . _ ... WASTE TO PUMP .. ,..n'9J.

.....-_........ **

0000 __ *G G 200 SAMPLE'

S M'" to: 0 0 42 DISTILLING SOL ,,***

EATING BATH WITH 0 0 0 42 WASTE FROM

ISTILLATION COIL - .... STILL

__ GRAY __ GRAY 10 RESAMPLE WASTE A-2 .. .. BLACK - BLACK 032 AIR

0000 'It Y: Y I 2 RESAMPLE

S M I '" 0 W 0 23 4 A AP

o __ W 0 23 BUFFERED POTASSIUM

.. FERR I CYANIDE

_--..i!-~ GRAY -- GRAY 1.0 WASTE FROM FIC ...... ..

PROPORTIONING

PUMP

\/ SAMPLE RATE 20/hr 12

t * Kel-f

.... -+c::Jl.... ** 100 ACIDFLEX

505jJm fIlters ,-U0 *** POLYETHYLENE

50 mm Tubular f Ie ~'-__""

H

D

COLORIMETER RECORDER

FI GURE 1. PHENOL AUTO ANALYZER I
To Waste

T RESAMPLE .... BLACK __ BLACKII 0 32 AIR

..

MI/mlO

SAMPLER

G II 2 00 SAMPLE

o 0 42 DISTILLING SOL

o 0 42 WASTE FROM

STILL

....

Eo

-Eo

Eo

G

-

o

-

o Eo

+

~**"

*"

11\

Eo ,j>.

N

o

Vo

GRAY GRAY 10 RESAMPLE WASTE A-2

157-B089 BLACK BLACK 032 AIR

()()()() Y Y I 2 RESAMPLE

11\ 1 ~o : w~o 23 4AAP

o W 0 23 BUFFERED POTASSIUM

FERR I CYANIDE

... .. Eo GRAY <; GRAYRJ... 0 WASTE FROM F/ C

PROPORTIONING

PUMP

SAMPLE RATE 20/hr 12

*Kel-f

** 100 ACIDFLEX B *** POLYETHYLENE

COLORIMETER RECORDER

\II

50 ~...JI 50 5}Jm fll~1 r _ mm Tubular flc . V ~,__----II

FIGURE 2. PHENOL AUTO ANALYZER II
PHENOLICS, TOTAL RECOVERABLE

Method 420.3 (Spectrophotometric, MBTH with Distillation)

STORET NO. 32730

1 Scope and ApphcatlOn

1 1 This method IS apphcable to the analysIs of dnnkmg, surface and sahne waters, domestic

and mdustnal wastes

1 2 The method IS capable of measunng phenohc matenals at the 2 ug/l level when the

colored end product IS extracted and concentrated m a solvent phase usmg phenol as a

standard

1 3 The method IS capable of measunng phenohc matenals that contam from 50 to 1000

ug/l m the aqueous phase (withoutsolvent extractlOn) usmg phenol as a standard

1 4 It IS not possible to use this method to differentiate between different kmds ofphenols

2 Summary ofMethod

2 1 This method IS based on the couphng of phenol With MBTH m an aCid medmm usmg

cenc ammomum sulfate as an OXidant The couphng takes place m the p-posl!10n, If this

posltlOn IS occupied, the MBTH reagent will react at a free O-posltl0n The colors

obtamed have maximum absorbance from 460-595 nm For phenol and most phenohc

IDlXtures the absorbance IS 520 and 490 nm

3 Comments

3 1 For most samples a prehmmary dlsttllatloll1s reqmred to remove mterfenng matenals

3 2 Color response of phenohc matenals With MBTH IS not the same for all compounds

Because phenohc type wastes usually contam a vanety of phenols, It IS not possible to

duphcate a mixture of phenols to be used as a standard For this reason phenol has been

selected as a standard and any color produced by the reaction of other phenohc

compounds IS reported as phenol This value will represent the mmlmum concentration

ofphenohc compounds present m the sample

4 Sample Handlmg and PreservatlOn

41 Biological degradatlOn IS mhlblted by the addltlOn of 1 gil of copper sulfate to the

sample and aCldlficatlOn to a pH of less than 4 With sulfunc aCid The sample should be

kept at 4°C and analyzed wlthm 24 hours after collection

5 Interference

5 1 Interferences from sulfur compounds are ehmmated by aCldlfymg the sample to a pH of

less than 40 With H2S04and aeratmg bnefly by stlrnng and addmg CUS04

5 2 OXldlzmg agents such as chlonne, detected by the hberatlOn of 10dme upon aCidification

m the presence of potassmm lOdlde, are removed Immediately after samphng by the

addltlOn of an excess of ferrous ammomum sulfate (6 5) If chlonne IS not removed, the

phenohc compounds may be partially oXidized and the results may be low

5 3 Phosphate causes a precipitate to form, therefore, phosphonc aCid should not be used for

preservatlOn All glassware should be phosphate free

Issued 1978

4203-1
5 4 HIgh concentrations of aldehydes may be an mterference

6. Apparatus

6 1 DIstIllation apparatus All glass consIstmg of a 1 hter pyrex distilhng apparatus wIth

Graham condensor

62 pH meter

6 3 Spectrophotometer

64 Funnels

6 5 FIlter paper

6 6 Membrane filters

6 7 Separatory funnels

7. Reagents

71 Copper sulfate solutIOn DIssolve 100 g CuS04-5 H20 m dIstIlled water and dIlute to 1

hter

72 Sulfunc aCId, 1 N Add 28 ml of conc H2S04to 900 ml of dIstdled water, mIX and dIlute

to 1hter

7 3 MBTH solutIOn, 005% DIssolve 0 1 g of 3-methyl-2-benzothiazohnone hydrazone

hydrochlonde m 200 ml ofdIstIlled water

74 Cenc ammomum sulfate solutIon Add 2 0 g of Ce(S04)2-2(NH4)2S04-2H20 and 2 0 ml

ofconc H2S04to 150 ml of dIStilled water After the sohd has dIssolved dIlute to 200 ml

wIth dIstIlled water

75 Buffer solutIOn DIssolve m the followmg order, 8 g of sodmm hydroxIde, 2 g EDTA

(disodium salt) and 8 g bonc aCId m 200 ml of dIstIlled water DIlute to 250 ml wIth

dIstIlled water

7.6 Workmg buffer solutIOn Make a workmg solutIOn by mlxmg an appropnate volume of

buffersolutIOn (7 5) wIth an equal volume ofethanol

7 7 Chloroform

7 8 Stock phenol DIssolve 1 00 g phenol m 500 ml of dIstIlled water and dIlute to 1000 ml

Add 1g CUS04and 0 5 ml conc H2S04as preservatIve 1 0 ml = 1 0 mg phenol

7.9 Standard phenol solutIon A Dtlute 10 0 ml ofstock phenol SolutIon (78) to 1000 milO

ml = 001 mg phenol

7.10 Standard phenol solutIOn B DIlute 100 0 ml ofstandard phenol solutIOn A (79) to 1000

ml wIth disttlied water 1 0 ml = 0001 mg phenol

8 Procedure

8 1 DIstIllatIOn

8 lITo 500 m1 ofsample add 5 m1 of copper sulfate SolutIon (7 1) and adjust the pH to

approxImately 4 wIth 1 N sulfunc aCId SolutIon (7 2)

8.1 2 DIstIll over 450 m1 of sample, add 50 ml of warm dIstIlled water to flask, and

resume dIstIllatIOn unttl500 ml has been collected

8 1 3 Ifthe disttliate IS turbId, filter though a prewashed membrane filter

82 ConcentratIon above 50 ug/1

8 2 1 To 100 ml of disttliate or an ahquot dIluted to 100 ml, add 4 ml of MBTH SolutIon

(7 3)

8 2 2 After 5 mmutes, add 2 5 m1 ofcenc amIhomu~sulfat~ solutIOn (7 4)

4203-2
8 2 3 Walt another 5 mInutes and add 7ml ofworkIng buffersolution (7 6)

8 2 4 After 15 mInutes, read the absorbance at 520 nm agaInst a reagent blank The color

IS stable for 4 hours

83 Concentration below 50 ug/1

8 3 1 To 500 ml ofdIstIllate In a separately funnel, add 4 ml ofMBTH solutIOn (7 3)

8 3 2 After 5 mInutes, add 2 5 ml ofcenc ammoma sulfate solutIOn (7 4)

8 3 3 After an addItIOnal 5 mInutes, add 7 ml ofworkIng buffersolutIOn (7 6)

8 3 4 After 15 mInutes, add 25 ml of chloroform Shake the separatory funnel at least 20

tImes Allow the layer to separate, and pass the chloroform layer through filter

paper

8 3 5 Read the absorbance at 490 nm agaInst a reagent blank

9 CalculatIon

9 1 Prepare a standard curve by plottmg absorbance agaInst concentratIOn values

9 2 ObtaIn concentratIOn value ofsample dIrectly from prepared standard curve

10 PreCIsIon and Accuracy

10 1 PreCISIOn and accuracy data are not avaIlable at thIS time

Bibliography

1 Fnestad, H 0 , Ott, E E , and Gunther, FA, "Automated Colonmetnc MICro DetermmatIOn

ofPhenol by OXIdatIve CouplIng wIth 3-Methyl-2-benzothlazohnone Hydrazone", Techmcon

InternatIOnal Congress (1969)

2 Gales, ME, "An EvaluatIOn ofthe 3-Methyl-2 benzothIazolmone Hydrazone Method for the

Determmatlon ofPhenols m Water and Wastewater", Analyst, 100, No 1197,841 (1975)

4203-3
METHYLENE BLUE ACTIVE SUBSTANCES (MBAS)

Method 425.1 (Co~orimetric)

STORET NO. 38260

1 Scope and ApphcatlOn

1 1 ThIS method IS apphcable to the measurement of methylene blue actIve substances

(MBAS) m dnnkmg waters, surface waters, domestIc and mdustnal wastes It IS not

apphcable to measurement ofsurfactant-type matena1s m sahne waters

1 2 It IS not possIble to dIfferentIate between hnear alkyl sulfonate (LAS) and alkyl benzene

sulfonate (ABS) or other Isomers of these types of compounds However, LAS has

essentlally replaced ABS on the surfactant market so that measurable surfactant

matenals WIll probably be LAS type matenals

1 3 The method IS apphcable over the range of0 025 to 100 mg!l LAS

2 Summary ofMethod

2 1 The dye, methylene blue, m aqueous solutlOn reacts wIth amomc-type surface actIve

matenals to form a blue colored salt The salt IS extractable wIth chloroform and the

IntenSIty ofcolor produced IS proportIonal to the concentratlOn ofMBAS

3 Comments

3 1 Matenals other than man-made surface actIve agents WhIch react With methylene blue

are orgamcally bound sulfates, sulfonates, carboxylates, phosphates, phenols, cyanates,

thiocyanates and some morganlc Ions such as mtrates and chlondes However, the

occurrence of these matenals at Interference levels IS relatIvely rare and WIth the

exceptlOn ofchlofldes may generally be dIsregarded

32 Chlondes at concentratlOn of about 1000 mg!l show a pOSItIve mterference but the

degree of mterference has not been quantIfied For thIS reason the method IS not

apphcable to bnne samples

33 Naturally occurnng orgamc matenals that react WIth methylene blue are relatIvely

InsIgmficant Except under hIghly unusual CIrcumstances, measurements of MBAS In

fimshed waters, surface waters and domestIc sewages may be assumed to be accurate

measurements ofman-made surface actIve agents

4 PreCISIon and Accuracy

4 1 On a sample offiltered flver water, spIked WIth 294 mg LAS!hter, 110 analysts obtaIned

a mean of2 98 mg!l WIth a standard deviatlOn of ±O 272

42 On a sample oftap water spIked WIth 048 mg LAS/hter, 110 analysts obtaIned a mean of

a 49 mg!l WIth a standard devIatlOn of ±O 048

4 3 On a sample of dIstIlled water spIked WIth 0 27 mg LAS!hter, 110 analysts obtamed a

mean of0 24 mg!l WIth a standard deVIatIOn of ±O 036

44 AnalytIcal Reference SerVIce, Water Surfactant No 3, Study No 32, (1968)

Approved for NPDES

Issued 1971

425 1-1
5 References

5.1 The procedure to be used for thIS determinatIOn IS found In

Standard Methods for the EXaminatIon ofWater and Wastewaters, 14th EdItion, p 600,

Method No 512A (1975)

Annual Book ofASTM Standards, Part 31, "Water", Standard D 2330-68, Method A, p

494(1976)

425 1-2

I IIII
NTA

Method 430.1 (Colorimetric, Manual, Zinc-Zincon)

STORET NO. 00695

1 Scope and ApplIcatlOn

1 1 In thIS method NTA refers to the tn-sodIUm salt of mtnlotnacetlc aCId,

N(CH2COONa)3

1 2 ThIs method IS applIcable to surface waters In the range of0 5-10 0 mg/l NTA

2 Summary ofMethod<l)

2 1 Zmc forms a blue-colored complex wIth 2 carboxy-2'-hydroxy-5'-sulfoformazylbenzene

(ZIncon) In a solutlOn buffered to pH 9 2 When NTA IS added, the ZInc-ZIncon complex

IS broken whIch reduces the absorbance In plOportlOn to the amount ofNTA present

3 Sample HandlIng and PreservatlOn

3 1 Samples should be analyzed as soon as possIble, as NTA has been shown to be

blOdegradable(2)

4 Interferences

4 1 CatlOns, such as calcIUm, magnesIUm, ZInC, copper, Iron, and manganese, complex wIth

NTA and gIve a negatIve Interference These lOns are removed by batch treatIng samples

wIth lon-exchange reSIn At concentratlOns hIgher than expected In typIcal nver waters(3),

only ZInC, copper, and Iron were not completely removed wIth lOn-exchange treatment

Results are summanzed In Table 1

Table 1

Interference of Common Metals

Metal

Blank

ZInc

Boron

Iron

Molybdenum

Manganese

Alummum

Copper

Strontmm

mg/I

added

00

20

50

50

20

40

30

05

50

10 mg/I

NTA

Recovenes

1 I

<05

1 1

095

10

1 1

085

<05

10

50 mg/I

NTA

55

06

55

46

55

56

52

34

54

4 2 ThIS method has not been found apphcable to salt waters

Issued 1971

430 I-I
5. Apparatus

5 1 Shakmg machme, tray type, for stIrnng sample-resm mIxtures m 125 ml Erlenmeyer

flasks

5 2 Photometer, sUitable for measurements at 620 nm

6 Reagents

6 1 SodiUm hydroxIde, 6N DIssolve 120 g NaOH m distIlled water and dIlute to 500 ml

6.2 Buffer DIssolve 31 g bonc aCId and 37 g potassiUm chlonde m 800 ml dIstIlled water

Adjust pH to 9 2 wIth 6N NaOH (6 1) DIlute to 1 lIter

6 3 Hydrochlonc aCId, 2N DIlute 83 ml conc HCl to 500 ml wIth dIstIlled water

64 Zmc DIssolve 044 g ZnS04-7H20 m 100 ml 2N HCl (63) and dIlute to 1 lIter wIth

dIStIlled water

6 5 SodiUm hydroxIde, IN DIssolve 4 g NaOH m dIstIlled water and dIlute to 100 ml

66 Zmc-Zmcon DIssolve 0 13 g Zmcon (2-carboxy-2'-hydroxy-5'-sulfoformazyl benzene)

m 2 mllN NaOH (65) Add 300 ml buffer (62) WhIle stlrnng, add 15 ml Zmc SolutIon

(6 4) and dIlute to 1 lIter wIth dIstIlled water

6 7 Ion-exchange resm Dowex 50W-X8, 50-100 mesh, Na+ form (or eqUivalent)

68 Stock NTA solutIOn DIssolve 10700 g N(CH2COONa)3-H20 m dIstIlled water and

dIlute to l000ml 1 Oml = 10mgNTA

7. Procedure

7.1 FIlter approxImately 50 ml ofwell-mIxed sample through a 0 45u membrane filter

72 Prepare a senes of standards from 0 5 to 10 mg/l NTA, Includmg a blank of dIstIlled

water Treat standards and blank In same manner as filtered samples

7 3 To a 25 ml sample m a 125 ml Erlenmeyer flask add approXImately 2 5 g lon-exchange

resm (67) Agttate sample for at least 15 mmutes

7 4 FIlter through coarse filter paper to remove resm PIpette 15 0 ml offiltrate Into a 50 ml

beaker Add 25 0 ml Zmc-Zmcon (6 6) by pIpette

7 5 Read absorbance agamst dIstIlled water at 620 nm In a 1 cm or 2 cm cell

8. CalculatIon

8.1 Prepare standard curve by plottmg absorbance of standards vs NTA concentratIons

Calculate concentratIons ofNTA, mg/l, dIrectly from thIS curve

9 PrecISIon and Accuracy

9 1 In a smgle laboratory (MDQARL), USIng spIked surface water samples at concentratIons

of0 5, 2, 6, and 10 mg/l NTA, standard devIatIOns were ±O 17, ±O 14, ±O 1, and ±O 16,

respectIvely

9 2 In a smgle laboratory (MDQARL), usmg spIked surface water samples at concentratIons

ofl 0 and 75 mg/l NTA, recovenes were 120% and 103%, respectIvely

BiblIography

1 Thompson, J E, and DuthIe, J R, "The BIOdegradabIlIty and Treatment of NTA", Jour

WPCF, 40, No 2,306 (1968).

2 Shumate, K S et aI, "NTA Removal by ActIvated Sludge - FIeld Study", IbId, 42, No 4, 631

(1970)

4301-2
3 Kopp, J F, and Kroner, R C" "Trace Metals m Waters of the Umted States", USDI,

FWPCA, DPS, 1014 Broadway, Cmcmnatl, OhlO 45202

4301-3
NTA

Method 430.2 (Colorimetric, Automated, Zinc-Zincon)

STORET NO. 00695

1 Scope and ApphcatlOn ,

1 1 In thIS method, NTA refers to the tn-sodium salt of mtnlotnacetIc aCId,

N(CH2COONa)3 ,

1 2 ThIS method IS apphcable to surface waters In the range of 0 04 to 1 0 mg/l and 0 5 to

10 0 mg/l NTA, dependIng on WhICh manIfold syst~m IS used It does not apply to sahne

waters, a posItIve Interference of0 5 to 1 0 mg/lls present In sewage-type samples.

1 3 ApproXImately 13 samples per hour can be analyzed

2 Summary ofMethod(l)

2 1 ZInC forms a blue-colored complex wIth 2-carboxy-2'-hydroxy-5'-sulfoformazylbenzene

(ZIncon) In a solutIOn buffered to pH 9 2 When NTA IS addd, the ZInc-Zmcon complex

IS broken WhICh reduces the absorbance In proportIon to the amount ofthe NTA present

3 Sample Handhng and PreservatIOn I

3 1 Samples should be analyzed as soon as pOSSIble, as NTA has been shown to be

bIodegradable (2)

4 Interferences

4 1 CatIons, such as calCIUm, n1a~neSlUm, ZInC, copper,' Iron, and manganese, complex wIth

NTA and gIve a negatIve Interference These Ions are removed automatIcally by pasSIng

the sample through an lOn-exchange column At concentratIOns hIgher than expected In

typICal nver waters,(3) only Iron was not completely; removed by thIS column treatment

Results, summanzed In Tables 1 and 2, show that 'Iron gIves a negatIve Interference In

concentratIOns above 30 mg/l NTA

TABLE 1

Interference of Common Metals

Recovenes

mg/l 10 mg/l 50 mg/l

Metal added NTA

Blank 00 10 50

Zmc 20 09 49

Iron 50 08 38

Manganese 40 10 49

Copper 05 12 49

Issued 1971

4302-1
TABLE 2

Effect of Iron on NTA Recovery m RIver Water

Iron Added

mgll

00

05

10

20

30

40

50

NTA Recovered, mg/l

(0 5 mg/l added)

052

052

052

052

048

045

039

, "

5

6

42 At concentratlOn levels below 005 mg/1 NTA, negative peakmg may occur durmg

analyses

Apparatus

5.1 Techmcon AutoAnalyzer conslstmg of

5 1 1 Sampler I or II

512 Mamfold

5 1 3 ProportlOmng pump

5 1 4 Colonmeter eqUIpped WIth 15 mm tubular flow cell and 600 or 625 nm filter

5 1 5 Recorder

Reagents

6.1 Sodmm hydroxIde, 6N DIssolve 120 g NaOH m dlstl1led water and dIlute to 500 ml

6 2 Buffer DIssolve 31 g bonc aCId and 37 g potassmm chlonde m 800 ml dlst111ed water

AdJustpHofsolutlOn to 92 WIth 6NNaOH (6 1) Dl1ute to 1 hter

6 3 Hydrochlonc aCId, 2N Dl1ute 83 ml conc HCl to 500 ml WIth dlst111ed water

64 Zmc DIssolve 044 g ZnS04-7H20 m 100 ml2N HCI (6 3) DIlute to 1 hter WIth dlstl1led

water

6 5 Sodmm hydroxIde, IN DIssolve 4 g NaOH m dlst111ed water and dl1ute to 100 ml

66 Zmc-Zmcon reagent A (004-10 mg/I NTA) DIssolve 0065 g Zmcon powder (2-

carboxy-2'-hydroxy-5'-sulfoformazyl benzene) m 2 ml of 1 N NaOH (6 5) Add 300 ml

buffer (6 2) StIr on a magnetIc stIrrer and add 7 5 ml zmc solutlOn (6 4) Dl1ute to I hter

WIth dIstilled water ThIs solutlOn IS stable for 12 hours -- --- 67 Zmc-Zmcon reagent B (0 5-10 mg/I NTA) DIssolve 013 g Zmcon m 2 mil N NaOH

(65). Stir on magnetic stirrer and add 300 ml buffer (6 2) and 15 ml zmc solutlOn (6 4)

Dl1ute to I hter WIth dlst111ed water Stable for 1 week --- 68 Ion-exchange resm, H+ form 20-50 mesh or 30-80 mesh, Dowex 50W-XB or

eqUIvalent

NOTE: Column IS prepared by suckmg a water slurry ofthe resm mto 12 mches of3/16-

mch OD sleevmg ThIS may be convemently done by usmg a pIpette and a loose-fittmg

glass wool plug m the sleeve

6.9 Stock NTA solutlOn DIssolve I 0700 g of N(CH2COONa)3-H20 m 500 ml of dIstilled

water and dl1ute to 1000milO ml = 1 0 mg NTA

4302-2
6 10 Worlang solutlOn A DIlute 10 0 ml of stock NTA solutlOn to 100 0 ml with distIlled

water 1 0 ml = 0 1mg NTA Prepare dally

6 11 Working solutlOn B DIlute 10 0 ml of SolutlOn A to 100 0 ml with distIlled water 1 0 ml

= 001 mgNTA Preparedally

6 12 Working solutlOn C DIlute 10 0 ml ofSolutlOn B to 100 0 ml with distIlled water 10 ml

= 0 001 mg NTA Prepare dally

6 13 Prepare a senes ofstandards by dIluting sUItable volumes of worlang solutlOns to 100 0

ml with distilled water ,The following dIlutlOns are suggested

ml of SolutIOn C/100 ml

2

4

6

8

10

ml of SolutIon B/100 ml

2

4

6

8

10

ml of Solution A/100 ml

2

4

6

8

10

Cone, mg NTA/I

002

004

006

008

010

020

040

060

080

100

20

40

60

80

100

7 Procedure

7 1 Set up manifold as shown In Flg\lre 1

7 2 Allow both colonmeter and recorder to warm up for 30 minutes Run a basehne with all

reagents, feeding distilled water through the sample hne Adjust dark current and

operative opemng on colonmeter to obtam sUItable baseline

73 Place wash water tubes In sampler In sets oftwo, leaVing every third posItion vacant Set

samphng time at 1 5 minutes

7 4 Place NTA standards In sampler Complete filling ofsample tray with unknown samples

7 5' SWitch sample line from diStilled water to sampler and begin an~lysls

8 CalculatlOn

8 1 Prepare standard curve by plotting peak heights of processed NTA standards against

known concentratlOns Compute concentratlOn of samples by companng sample peak

heIghts wIth standard curve

4302-3
1111I1

9 PrecIsion and Accuracy

9.1 In a single laboratory (EMSL), uSing surface water samples at concentratIOns of 0 1,

o18, 027, and 044 mg/l, the standard deviatIOns were ±O 01, ±O 004, ±O 004, and

±O 005, respectively At concentratIOns of 1 3, 40, 58, and 74 mg/l, the standard

deViatIOns were ±O OS, ±O OS, ±O 07, and ±O 1, respectively

92 In a Single laboratory (EMSL), uSing surface water samples at concentratIOns of0 18 and

027 mg/l, recovenes were 101% and 106%, respectively At concentratIOns of 40 and

5 8 mg/l, the recovenes were 98% and 96%, respectively

BiblIography

1 Thompson, J E, and Duthie, J R, "The BlOdegradablhty and Treatment of NTA", Jour

WPCF, 40, No 2,306 (1968)

2 Shumate, K S et aI, "NTA Removal by Activated Sludge - Field Study", Ibid, 42, No 4, 631

(1970)

3. Kopp, J F and Kroner, R C, "Trace Metals In Waters of the Umted States", USDI,

FWPCA, DPS, 1014 Broadway, Cincinnati, OhIO 45202

4302-4
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