NBSIR 79-1953

Simulated Precipitation Reference

Materials, III

E.R. Deardorff, T C. Rains, and W.F. Koch

Inorganic Analytical Research Division

National Measurement Laboratory

National Bureau of Standards

J.S Department of Commerce

Washington, D C. 20234

April 1980

Issued Sepiember 1980

Prepared for U.S. Environmental Protection Agency

Environmental Research Center

Research Triangle Park. NC 2771

iPepartment of the Interior

fcal Survey

[25046. MS 204C

tr. CO 80226

National Bureau of Standards

Library, E-OI Admin. Bldg.

FEB 2 7 1981

NBSIR 79-1953 pc^ CLCC . - SIMULATED PRECIPITATION REFERENCE

MATERIALS, III

E.R. Deardorff, T.C. Rains, and W.F. Koch

Inorganic Analytical Research Division

National Measurement Laboratory

National Bureau of Standards

U.S. Department of Commerce

Washington, D.C. 20234

April 1980

Issued September 1 980

Prepared for U.S. Environmental Protection Agency

Environmental Research Center

Research Triangle Park, NC 2771

U.S. Department of the Interior

Geological Survey

Box 25046, MS 204C

Denver, CO 80226

U.S. DEPARTMENT OF COMMERCE, Philip M. Klutznick, Secretary

Luther H. Hodges, Jr., Deputy Secretary

Jordan J. Baruch, Assistant Secretary for Productivity. Technology, and Innovation

NATIONAL BUREAU OF STANDARDS, Ernest Ambler, Director

nt>. n^s-nss

and

TABLE OF CONTENTS

Page

1. INTRODUCTION 1

2. EXPERIMENTAL DETAILS 2

2.1 General Considerations

2.2 Preparation of Reference Materials

2.3 Ampouling

2.4 Numbering Sequence

2.5 Analysis of Ampoules

2.5.1 pH Measurements

2.5.2 Conductivity Measurements

2.5.3 Acidity Measurements

2.5.4 Determination of Anions

2.5.5 Analysis for Cations

2. 5. 5.1 Measurement for Ammonium Ion . . 2. 5. 5.

Metals by Atomic Absorption

and Flame Emission

3. ANALYTICAL RESULTS

4. DISCUSSION

5. RE-EXAMINATION OF 1975 SAMPLES

6. RE-EXAMINATION OF 1977 SAMPLES

7. INSTRUCTIONS FOR USE

7.1 Series 910000 and Series 920000. . . . 7.2 Series 930000 and Series 940000. . . . 7.2.1 Acidity Measurement

7.2.2 Conductivity and pH Measurements

8 . ACKNOWLEDGEMENTS 8

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Simulated Precipitation Reference Materials, III

E. R. Deardorff, T. C. Rains, and W. F. Koch

ABSTRACT

This report describes the preparation of a third

series of reference materials for the chemical analysis of

natural precipitation samples. These materials were prepared by the National Bureau of Standards (NBS) , under the

joint sponsorship of the Environmental Protection Agency

(EPA) , and the U. S. Geological Survey (USGS) , and will be

used as a means of intercalibrating atmospheric monitoring

stations. These materials consist of high and low concentrates which upon dilution simulate the range of anion and

cation concentrations typically found in natural rainwater.

Two separate reference samples which are to be used undiluted

are provided for evaluation of acidity measurements. The

analytical methods used to establish the composition of the

samples are also described.

1. INTRODUCTION

The analysis of the composition of rainfall and other

forms of precipitation is an excellent means to monitor

global atmospheric pollution. Such measurements must

necessarily be made at widely spaced geographical locations, over extended periods of time, and by many independent investigators. It is imperative that the measuring

stations be intercalibrated if the data obtained are to be

correlated and combined for environmental interpretation.

The measurement of a series of substantially identical

samples by stations in a measurement system is an accepted

method of evaluating laboratory performance for intercalibration purposes.

This report describes work done at the National Bureau

of Standards under the sponsorship of EPA to prepare and

establish the composition of a series of reference materials

intended to be used for the intercalibration of precipitation measurement stations^. The materials consist of

^This work was performed at the National Bureau of Standards

for the Environmental Protection Agency and the U. S.

Geological Survey under Interagency Agreement EPA- 79 -D-F0666

and Purchase Order 84312, respectively.

CONTRIBUTION OF THE NATIONAL BUREAU OF STANDARDS. NOT

SUBJECT TO COPYRIGHT.
ampoules containing aqueous concentrates that simulate

natural precipitation when accurately diluted. Two multicomponent solutions and two solutions specifically designated for acidity measurement were prepared.

This is the third series of solutions prepared for EPA

to be used by the World Meteorological Organization (WMO)

stations. The details of the first and second series are

contained in NBSIR 75-958, "Simulated Precipitation Reference Materials", October 1975, and NBSIR 77-1315 "Simulated

Precipitation Reference Materials II", September 1977.

2. EXPERIMENTAL DETAILS

2.1 General Considerations

These reference materials are similar in concept to

those prepared previously. Two reference solutions, low

concentrations (Series 910000) , and the other high concentrations (Series 920000) were prepared of specified components at levels similar to those expected in natural

samples (Table 1). In addition, two reference materials

(Series 930000, and Series 940000) containing 3 microequivalents (yeq) and 5 yeq of sulfuric acid, respectively,

per ampoule are included specifically for the measurement of

acidity

2 . 2 Preparation of Reference Materials

The reference materials were prepared using distilled

water whose specific conductance does not exceed 1 micro

siemens per centimeter (1 yS/cm) at 25 °C and reagent grade

chemicals. Distilled water in this report refers to this

quality of water. The chemicals used and their sources are

listed in Table 2. The quantities of chemicals are listed

in Table 3.

The instructions for the preparation of Series 910000

and Series 920000 are as follows:

Ten liters of the required solutions can be prepared

using the quantities of reagents set forth in the instructions supplied by EPA (Table 3) . The procedure is as

follows: Transfer the reagents with the exception of

sodium fluoride and lead acetate using distilled water to a one liter volumetric flask and make up nearly to volume

with distilled water. Because of its low solubility, add

the sodium fluoride at this point and dilute to calibrated

volume, Solution A. Transfer the lead acetate to another

one liter volumetric flask and dilute to 800 mL . Add 100

mL of Solution A by pipet to the lead acetate solution and

dilute to calibrated volume. Solution B.

2
Transfer by pipet 400 mL of Solution A to each of two

volumetric flasks, four liter capacity, and make up to

volume. Filter both four liter solutions and the one liter

containing the lead acetate, Solution B, through a Whatman

40 filter paper into a ten liter ground glass stoppered

bottle

Series 930000 and Series 940000 were prepared by the

dilution of an appropriate volume of 0.06N sulfuric acid to

a final volume of 30 liters. The sulfuric acid solution

was standardized using two different procedures. In the

first, the acid was titrated against THAM (Tris (hydroxymethyl)

aminomethane) SRM 723. In addition, the acid was also

titrated against a 0.05N sodium hydroxide solution that had

been previously standardized with potassium acid phthalate,

SRM 84h.

2 . 3 Ampouling

The bulk solutions were transferred to ampoules using

an automatic dispensing and sealing machine belonging to

the Office of Standard Reference Materials. The ampoules

used (Wheaton Cat. No. 176780) were made from borosilicate

glass formulated to prevent a change of pH and to maintain

the purity of the contents. They were prescored to eliminate the need for filing.

The dispensing equipment pumps the solution from the

storage vessel and reproducibly injects a pre-set volume

into the ampoules, and automatically flame seals the ampoules.

Ampoules randomly selected for analysis were also weighed

to verify the reproducibility of the filling operation. No

significant changes in weight were detected in the four

solutions during the filling operation.

The ampoules used for Series 910000 and 920000 were of

10 mL capacity while 20 mL ampoules were used for the

Series 930000 and Series 940000 samples. The dispensing

equipment was adjusted to deliver 10 mL in the first group.

But only about 18.4 mL could be dispensed into the 20 mL

ampoules because delivery of a greater volume resulted in

the liquid splashing up onto the neck of the ampoule.

The precision of the ampouling operation is shown by

the data in Table 4.

2 . 4 Numbering Sequence

The ampoules are labeled and numbered in the following

sequences

3
Series 910000

Series 920000

Series 930000

Series 940000

910001 to 910600

920001 to 920600

930001 to 931200

940001 to 941200

The rationale of the following sequence is illustrated

as follows:

910001

First digit: Fiscal Year 1979

Second digit: Sample type 1, 2, 3, or 4

Remaining digits: Sample serial number, e.g., 0001

The samples were replaced in the individually compartmented boxes in which the ampoules were received from the

manufacturer. Care was exercised to replace them in the

boxes in the order in which they were filled. Samples for

measurement were selected from these by a random number

process. Altogether, 76 ampoules were selected from each

of Series 910000, and Series 920000 for this purpose, while

30 were selected from the Series 930000, and Series 940000.

No differences were found in either mass content or composition that could be attributed to sequence of preparation.

Accordingly, it is believed that the samples in each series

are substantially uniform with respect to composition and

total content. See Table 4.

The samples delivered to EPA and USGS were numbered

sequentially, ignoring the gaps resulting from removal of

the test samples. However, the actual production sequence

could be ascertained should the need arise.

2 . 5 Analysis of Ampoules

Essentially seven ampoules were analyzed for each specific determination. However, for purposes of convenience,

all measurements were not made on the same ampoule. The

measurement data are summarized in Tables 5, 6, 7 and 8.

The methods used for measurement are summarized in the

following subsections.

2.5.1. pH Measurements

The pH measurements were made on diluted samples of the

concentrate. The combination pH electrode was calibrated

with pH 4.01 and 7.00 buffers and the sample readings were

taken directly from the digital pH meter display.

4
2.5.2.

Conductivity Measurements

The conductivity measurements were made with a dip type

conductivity cell in the A.C. mode at a frequency of 1 kHz.

The cell constant was determined using a 0.01 demal solution

[Jones and Bradshaw, J. Am. Chem. Soc. 1780 (1933)].

Appropriate temperature corrections were made. The values

reported were made at 23 ®C.

2.5.3. Acidity Measurements

The acidity content of each ampoule was determined by

coulometric titration of hydrogen ion to the designated

pH = 8.3.

2.5.4. Determination of Anions

The anions fluoride, chloride, nitrate, and sulfate

were determined by ion-chromatography. All four anions were

done sequentially with a single injection. Chromatographic

conditions were as follows: eluent 0.003 mol/L NaHC03 and

0.0018 mol/L Na 2 C 03 ; flow-rate 2 mL/minute; sample loop 100

yL; anion columns 3 x 500 mm plus 3 x 150 mm pre-column;

suppressor column 6 x 250 mm. Baseline resolution was

obtained for all four anions with a total elution time of 32

minutes. Three calibration standards containing the four

anions were prepared encompassing the range of the samples.

Quantitation was performed by interpolation of the first

order least squares fit of the calibration standards' peakheight response versus concentration. Each ampoule of

series 910000 was diluted to 50 mL, and each ampoule of

series 920000 to 140 mL. Results have been normalized to a dilution of 500 mL per ampoule.

2.5.5. Analysis for Cations

2. 5. 5.1. Measurement of Ammonium Ions

The chosen technique consisted of chemical measurement

according to the procedure given in the following reference:

C. 0. Willits, and C. L. Ogg, "1949 Report of Standardization

of Microchemical Methods, Micro Kjeldahl Nitrogen Determinations", USDA Eastern Regional Research Laboratory, Philadelphia, PA. A micro-Kj eldahl steam distillation apparatus

was used to separate the ammonia, released by sodium hydroxide, which was trapped in boric acid. The ammonia was

titrated with standardized O.OIN hydrochloric acid using

methyl purple indicator.

5
2. 5. 5. 2. Metals by Atomic Absorption and Flame Emission

Spectrometry

All o£ the metallic cations were measured by atomic

absorption or flame emission spectrometry. Measurements

were made both on the bulk solution and on the ampoules.

The contents of an ampoule were quantitatively transferred

to a 100 mL volumetric flask. After addition of 1 mL of NBS

purified hydrochloric acid, the solution was diluted to the

calibrated volume. Emission or absorption measurements were

made in duplicate. Calibration standards were made by

dissolution of pure salts or pure metals.

3. ANALYTICAL RESULTS

The analytical results for Series 910000 and Series

920000 are summarized in Tables 5, and 6. The symbols used

are as follows:

n = number of samples analyzed

s 'n|x2-(E^\

^ n(n - 1) j

The values listed under x are the best estimates of

various compositional parameters of the solution measured

after the contents of each ampoule has been diluted to 500 mL.

The compositional data for Series 930000 and Series

940000 are given in Tables 7, and 8. The values reported

here have been determined directly on the samples contained

in the 20 mL ampoules without further dilution. The acidity

values are based upon combining the contents of two ampoules.

The pH and conductivity values are for undiluted samples but

of course are independent of the volume of sample measured.

4. DISCUSSION

The samples in each series are believed to be uniform

in composition. Every ampoule in each series contains the

same amount of liquid within narrow limits. The dilution

of the contents should not introduce any errors, provided

distilled water is used. The samples can be used to determine the between- laboratories variability within the requirements for precipitation analysis.

6
5.

RE-EXAMINATION OF 1975 SAMPLES

Table 9 shows that there have been no significant

changes in the concentrations of the anions.

Most of the cations have remained relatively stable.

Copper and lead have decreased significantly, however, as a

result of interaction with the walls of the ampoules.

Although iron was proposed for the 1975 samples, it was

found that it could not be retained at pH 6 ; it therefore

was omitted from this preparation.

In Table 9 under Sample B it is seen that no values for

pH and ammonium ion are reported under the 1979 column. In

addition, the acidity measurements are missing for this same

year. Unfortunately the supply of ampoules retained from

1975 had been exhausted before these measurements could be

obtained.

In the re-examination of 1975 samples, the data reported

in Table 9 for 1979 were derived from the analysis of at least

two ampoules.

6

.

RE-EXAMINATION OF 1977 SAMPLES

Table 10 shows very few changes in the constituents of

the 1977 samples. SO 4 and Ca have increased. Sample 730000

ampoule was rinsed with hydrochloric acid to dissolve the

precipitate before analysis of the cations. This resulted

in the recovery of the iron that was originally added to

the solution, 0.18 mg/L.

! The acidity standard Series 740000 has decreased in

yeq of acid by 15 percent.

A minimum of two ampoules was used for each determination in 1979 for the re-examination of the 1977 samples.

7.

INSTRUCTIONS FOR USE

7 . 1 Series 910000 and Series 920000

The samples consist of ampoules of concentrations which

simulate rainwater, when diluted to 500 mL. The ampoules

are pre-scored to facilitate breaking off the top. Glassware

should be thoroughly cleaned and rinsed with distilled water

before use. The recommended procedure for preparation of

the test sample is as follows:

1. Rinse the outside of the ampoule to remove dust

and allow to air dry.

7
2. Hold ampoule in a vertical position, tip over

and back, and gently tap to transfer any liquid

from the top to the body of the ampoule.

3. Hold ampoule with a paper towel (a precaution to

prevent injury to hand) and snap off the top at

the scored constriction.

4. Place a clean funnel in the neck of a clean 500 mL

volumetric flask and transfer the contents of the

ampoule, with gentle shaking as required to facilitate removal of liquid.

5. Rinse the ampoule two times with distilled water

and transfer the rinsings to the flask.

6. Add distilled water to the flask to dilute to the

calibrated volume and mix contents thoroughly.

7. Treat the resulting solution with the same care

and in the same manner as a sample of natural

rainwater

7.2. Series 950000 and Series 940000

The solutions are intended for use without additional

dilution

7.2.1. Acidity Measurement

Empty the contents of two ampoules into a clean 100 mL

beaker, according to instructions 1, 2, and 3 in Section

6.1. Hold the inverted ampoule over the beaker until contents

have drained as much as possible. Check for visible inclusions of solution in the ampoule and shake again, if required.

Any film of solution remaining in the ampoule will not cause

significant error.

7.2.2. Conductivity and pH Measurements

Empty the contents of one ampoule into a clean 30 mL

beaker. Remove substantially all the contents by shaking.

However, the measurements are not influenced by the quantity

of sample used, hence quantitative delivery is not required.

It is convenient to measure sample conductivity, followed by

measurement of pH on the same sample.

8.

ACKNOWLEDGEMENTS

The participation of the following members of the Staff

of the Inorganic Analytical Research Division in the analysis

8
of these reference materials is gratefully acknowledged:

T. A. Rush, and G. Marinenko. Mr. R. K. Kirby of the NBS

Office of Standard Reference Materials was responsible for

overseeing the ampouling and labeling of the samples.

The work was performed for the Environmental Protection

Agency under Interagency Agreement EPA- lAG- 79-DF0666

Informative discussions with Mr. Vance R. Highsmith, EPA,

Project Officer, and Dr. Richard J. Thompson, EMD/EMSL/EPA

are gratefully acknowledged.
Table 1. Target Compositions.

Unit of Concentration mg/L

Constituent Series 910000 Series 92000i

pH

Conductivity

Acidity

SO

4

. 73* 2.23*

CO 0 .24 . 74

N03 .816 2.138

NOj (N) . 182 .483

NH

4

. 208 .651

NH^ (N) .161 . 506

Cl .810 3.020

F .143 . 238

Ca . 200 .545

Cd . 049 . 225

Cu . 070 .287

K .146 .488

Mg .050 .200

Mn .037 .151

Na .226 .455

Ni .059 .176

Pb .062 . 207

Zn .065 . 392

Fe .032 .072

*The values shown were adjusted

conversation between Dr. Robert

and Dr. R. J. Thompson, EPA.

after a telephone

W. Burke, NBS,

10
Table 2. Chemicals

Materials.

Chemical

Calcium Chloride

Magnesium Sulfate

Zinc Nitrate

Cadmium Nitrate

Cupric Chloride

Cupric Nitrate

Nickel Nitrate

Lead Acetate

Manganese Chloride

Ammonium Chloride

Sodium Chloride

Sodium Fluoride

Sodium Nitrate

Potassium Nitrate

Ferric Ammonium Citrate

Citric Acid Monohydrate

Used for Preparation

Formula

CaCl2*2H20

MgSO^*

ZnCN02)2*6H20

CdCNO^) 2*4H20

CuCl2*2H20

Cu(N02)2’3H20

Ni(NO^) 2*6^2^

Pb(Ac)2*3H20

MnCl2*4H20

NH^Cl

NaCl

NaF

NaNO^

KNO

3

of Reference

Source

Mallinckrodt Analytical

Reagent

E 5 A Tested Purity

Baker Analyzed

Fisher Analyzed

B § A Reagent

Baker Analyzed

Mallinckrodt Analytical

Reagent

Baker Analyzed

B 5 A Reagent

Baker Analyzed

Mallinckrodt Analytical

Reagent

Fisher Certified

Baker Analyzed

Baker Ultrex

Fisher Purified

Baker Analyzed
Table 3. Recipe for NBS Precipitation Reference Materials,

III.

Preparation of Stock Solutions (10 liters)

Chemical 910000 920000

H2SO4 Cvieq) 5,600 15,000

NH^Cl (gra) . 3080 .9650

CaCl2*2H20 (gm) . 3676 1.0000

NaCl (gm) . 2150

NaNOj (gm) . 1000

NaF (gm) .1575 . 2625

Cd(NOj)2-''H20 (gm) .0675 . 3084

Cu(N03) 2* 3H2O (gm) . 1335

CuCl2-2H20 (gm) . 3850

KNOj (gm) . 1894 .6315

MgSO^.yH^O (gm) . 2520 1.0086

MnCl2*4H20 (gm) . 0660 . 2720

Ni(N03) 2*6H20 (gm) .1450 .4366

Pb(Ac)2*3H20 (gm) . 0570 . 1896

Zn (NOj) 2 • 6H2O (gm) .1480 .8926

Ferric Ammonium Citrate (gm) . 0923 . 2076

Citric Acid Monohydrate (gm) . 8406 3.3622

12
Table 4. Precision o£ Ampouling.

Series n x,g s 910000 12 9.962 0.018

920000 12 9.972 0.018

930000 12 18.30 0.022

940000 10 18.39 0.016

To demonstrate that there is no systematic trend in

the sampling operations , randomly selected ampoules and the

weights of liquid obtained for the 920000

below:

Series are given

Random Ampoules Weight

Ampoules in Order of

Listed of Weighing Liquid

,

Numerically grams

1 1 9.9986

80 11 9.9988

145 5 9.9612

240 4 9.9600

289 9 9.9518

368 7 9.9578

433 10 9.9605

528 3 9.9572

577 2 9.9537

672 8 9.9824

721 6 9.9825

816 12 9.9948

Compositional results in Tables 5 and 6 likewise show

no systematic trend.

13
Table 5. Analytical Data for Series 910000.

Constituent Unit n X s pH 7 5.03 0.24

Conductivity c -1

y S . cm 7 13.20 . 08

Acidity yeq/amp* 7 17.38 .45

SO4 mg/L 7 . 779 . 008

SO^ (S) mg/L 7 . 260 .003

N03 mg/L 7 .826 .002

NO

3 (N) mg/L 7 .186 .0005

NH

4 mg/L 7 . 214 .010

NH^ (N) mg/L 7 . 166 .008

Cl mg/L 7 .908 .008

F mg/L 7 .154 .002

Ca mg/L 7 . 248 .0014

Cd mg/L 7 .051 .0004

Cu mg/L 7 .073 .0003

K mg/L 7 .156 .001

Mg mg/L 7 .056 .0006

Mn mg/L 7 .038 .0006

Na mg/L 7 .284 .0050

Ni mg/L 7 .061 .0003

Pb mg/L 7 .070 .0006

Zn mg/L 7 .066 .0006

Fe mg/L 7 .030 .0006

n ampoule

14
Table 6 . Analytical Data. for Series 920000.

Constituent Unit n X s pH 7 4.35 0.12

Conductivity c -1

y S • cm 7 43.49 .08

Acidity yeq/amp* 7 66.02 .75

SO

4 mg/L 7 2.349 .024

SO

4 (S) mg/L 7 . 776 . 008

NO3 mg/L 7 2.147 .006

NOj (N) mg/L 7 .485 . 001

NH

4 mg/L 7 .660 .013

NH^ (n;) mg/L 7 . 514 .010

Cl mg/L 7 3.274 .014

F mg/L 7 . 256 .003

Ca mg/L 7 .654 .0048

Cd mg/L 7 .224 .0034

Cu mg/L 7 .294 .0019

K mg/L 7 . 506 . 0074

Mg mg/L 7 .226 .0026

Mn mg/L 7 .154 .0006

Na mg/L 7 . 558 .0078

Ni mg/L 7 .185 .0010

Pb mg/L 7 . 214 .0070

Zn mg/L 7 .402 .0042

Fe mg/L 7 .071 .0019

^ ampoule

15
Table 7. Compositional Data for Series 930000.

Constituent Unit n X s pH 9 3.91 .025

Conductivity y S* cm*^^ 7 69.12 .20

Acidity yeq/2 amp* 7 5.90 .24

n ampoules
Table 8. Compositional Data for Series 940000

Constituent Unit n X s pH 10 3.62 0.015

Conductivity ViS«cm“^ 7 121.44 .22

Acidity ueq/2 amp* 7 9.98 .40

IE ampoules

17
Table 9. Re-examination of 1975 Samples.

- - - - A - - - - - - - - B - - - - - Constituent Unit 1975 1977 1979 1975 1977 1979

pH 6.18 6.15

Conductivity c -1yS • cm 5.8 5.10 18.3 17.15

Acidity yeq/ amp* 4.9 5.0

SO4 mg/L 1.08 1.09 1.12 3.57 3.81 3.77

SO4 (S) mg/L . 361 . 365 . 373 1.19 1.27 1.26

NO3 mg/L .115 .146 .111 .664 . 700 .674

NOj (N) mg/L .026 .033 . 025 .150 .158 .152

NH4 mg/L .109 .08 .49

NH^ (N3 mg/L .089 .06 . 38

Cl mg/L .106 .128 1.25 1.08

F mg/L .102 . 108 .096 .097

Ca mg/L .099 .084 . 100 .442 .370 . 388

Cd mg/L . 030 . 030 .032 . 116 .115 .096

Cu mg/L .052 . 040 .033 .088 .035 .020

K mg/L .063 . 066 .067 .102 . 107 .103

Mg mg/L . 086 .086 .087 .456 .454 .396

Mn mg/L . 052 .054 .052 . 081 .085 .070

Na mg/L .153 . 166 .166 .51,6 . 546 .488

Ni mg/L .021 .022 .021 .104 . 113 .087

Pb mg/L .018 . 009 .010 .088 .058 .070

Zn mg/L .021 . 020 .020 . 095 .089 .064

Fe mg/L — — — — — —

K

ampoule

18
Table 9. Re-examination of 1975 Samples.

(continued)

- - - - c - - - - - - - - D - - - - -

Constituent Unit 1975 1977 1979 1975 1977 1979

pH 6.20 5.75 6.07 5.78

Conductivity yS*cm ^ 59.8 57.02 117 112

Acidity y eq/amp* 25 47

SO

4 mg/L 5.01 5.01 4.79 10.0 9.90 9.80

SO

4

(S) mg/L 1.67 1.67 1.60 3.33 3.30 3.27

N03 mg/L 6.64 6.64 6.64 10.89 10.89 10.95

NOj (N) mg/L 1.50 1.50 1.50 2.46 2.46 2.47

NH

4 mg/L 2.46 2.48 4.63 4.61

NH^ (N) mg/L 1.91 1.93 3.60 3.59

Cl mg/L 7.63 7.69 17.79 18.96

F mg/L .195 .184 .296 .289

Ca mg/L 1.23 1.04 1.21 2.84 2.42 2.80

Cd mg/L .578 . 576 .564 1.01 0.99 .99

Cu mg/L .200 .104 .088 . 393 .174 .157

K mg/L 1.01 1.01 1.04 3.06 2.92 3.24

Mg mg/L .729 .712 .720 .922 .936 .906

Mn mg/L .100 .103 .098 . 200 .204 .202

Na mg/L 2.46 2.54 2.58 5.44 5.46 5.72

Ni mg/L . 506 .560 .522 1.01 1.03 1.05

Pb mg/L .152 .105 .124 .110 .062 .074

Zn mg/L . 307 .284 .304 .610 .626 .612

Fe mg/L — — — — — —

n ampoule

1 19
Table 10. Re-examination of 1977 Samples.

710000 720000 730000

Constituent

Unit 1977 1979 1977 1979 1977 1979

pH 4.48 4.25 4.08 4.07 5.98 5.86

Conductivity

c -1

y S* cm 28.84 30.89 77.9 84.4 190.5 205.2

Acidity y eq/amp* 37.57 30.06 59.94 53.69 52.5 39.80

SO

4 mg/L 2.66 3.25 7.90 9.96 9.94 10.0

so^ (S3 mg/L . 89 1.08 2.64 3.32 3.32 3.33

NO3 mg/L . 503 .53 3.02 3.18 14.50 15.3

NO

3

(N) mg/L .114 . 120 .68 .72 3.27 3.45

NH

4 mg/L .107 .115 1.07 1.08 10.18 10.14

NH^ (N) mg/L .084 .089 .82 .82 7.93 7.89

Cl mg/L 1.35 .961 7.22 7.75 42.4 48.72

F mg/L .046 .039 .0997 .087 . 103 .093

Ca mg/L . 0766 .089 .766 .844 5.98 7.14

Cd mg/L . 0230 .022 .0572 .056 .114 .113

Cu mg/L .0360 .034 . 192 . 204 1.012 1.02

K mg/L .199 . 206 .994 1.016 4 . 94 5.18

Mg mg/L . 110 .111 1.12 1.14

Mn mg/L .0296 .029 .0586 .058 .0846 .083

Na mg/L .151 .169 2.86 2.82 9.66 10.1

Ni mg/L .0338 .031 .0948 .091 . 518 . 518

Pb mg/L .0232 . 023 . 0988 . 101 1.04 1.14

Zn mg/L .0344 .034 .198 . 202 1.05 1.04

Fe mg/L . 0214 . 022 .0612 .068 .076 .163

n ampoule

20
Table 10 . Re-examination of 1977 Samples.

(continued)

740000

Constituent

Unit 1977 1979

pH 3.81 4.02

Conductivity

c -1

y S» cm 80.0

Acidity y eq/amp* 9.32 7.96

ampoule

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(1.1
NBS-114A (REV. 9.78)

U.S. DEPT. OF COMM. 1. PUBLICATION OR REPORT NO. BIBLIOGRAPHIC DATA

NBSIR 79-1953 SHEET

4. TITLE AND SUBTITLE

Simulated Precipitation Reference Materials, III

5. Publication Date October 1980

7. AUTHOR(S)

E. R. Deardorff, T. C. Rains, and W. F. Koch

8. Performing Organ. Report No.

9. PERFORMING ORGANIZATION NAME AND ADDRESS

NATIONAL BUREAU OF STANDARDS

DEPARTMENT OF COMMERCE

WASHINGTON, DC 20234

11. Contract/Grant No.

12. SPONSORING ORGANIZATION NAME AND COMPLETE ADDRESS csfreer. City. stat*. ziP)

U.S. Environmental Protection Agency

Environmental Research Center

Research Triangle Park, NC 27711

and

13. Type of Report & Period Covered

15. SUPPLEMENTARY NOTES U.S. Department of the Interior

Geological Survey, Box 25046, MS 204C, Denver, CO 80226

I I Document describes a computer program; SF-185, FIPS Software Summary, is attached.

16. ABSTRACT (A 200-word or leas factual summary of moat significant information. If document includes a significant bibliography or

literature survey, mention it here.)

This report describes the preparation of a third series of reference

materials for the chemical analysis of natural precipitation samples. These

materials were prepared by the National Bureau of Standards (NBS), under the

joint sponsorship of the Environmental Protection Agency (EPA), and the U. S.

Geological Survey (USGS), and will be used as a means of intercalibrating atmospheric monitoring stations. These materials consist of high and low concentrates which upon dilution simulate the range of anion and cation concentrations

typically found in natural rainwater. Two separate reference samples which are

to be used undiluted are provided for evaluation of acidity measurements. The

analytical methods used to establish the composition of the samples are also

described.

17. KEY WORDS (six to twelve antriee; alphabetical order; capitalize only the first letter of the first key word unless a proper name;

separated by semicolons)

Chemical analysis; rainwater analysis; reference materials

18. AVAILABILITY |X] Unlimited

I j For Official Distribution. Do Not Release to NTIS

I

i Order From Sup. of Doc., U.S. Government Printing Office, Washington, DC

20402, SD Stock No. SN003-003-

[Xj Order From National Technical Information Service (NTIS), Springfield,

VA. 22161

19. SECURITY CLASS

(THIS REPORT)

UNCLASSIFIED

20. SECURITY CLASS

(THIS PAGE)

UNCLASSIFIED

21. NO. OF

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24

22. Price

$5.00

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