525.2-1

METHOD 525.2

DETERMINATION OF ORGANIC COMPOUNDS IN DRINKING WATER BY

LIQUID-SOLID EXTRACTION AND CAPILLARY COLUMN GAS

CHROMATOGRAPHY/MASS SPECTROMETRY

Revision 2.0

J.W. Eichelberger, T.D. Behymer, W.L. Budde - Method 525, 

Revision 1.0, 2.0, 2.1 (1988)

J.W. Eichelberger, T.D. Behymer, and W.L. Budde - Method 525.1

Revision 2.2 (July 1991)

J.W. Eichelberger, J.W. Munch, and J.A. Shoemaker

Method 525.2 Revision 1.0 (February, 1994)

J.W. Munch - Method 525.2, Revision 2.0 (1995)

NATIONAL EXPOSURE RESEARCH LABORATORY

OFFICE OF RESEARCH AND DEVELOPMENT

U.S. ENVIRONMENTAL PROTECTION AGENCY

CINCINNATI, OHIO 45268
525.2-2

METHOD 525.2

DETERMINATION OF ORGANIC COMPOUNDS IN DRINKING WATER

BY LIQUID-SOLID EXTRACTION AND CAPILLARY COLUMN

GAS CHROMATOGRAPHY/MASS SPECTROMETRY

1.0 SCOPE AND APPLICATION

1.1 This is a general purpose method that provides procedures for determination of organic

compounds in finished drinking water, source water, or drinking water in any treatment

stage. The method is applicable to a wide range of organic compounds that are efficiently

partitioned from the water sample onto a C18 organic phase chemically bonded to a solid

matrix in a disk or cartridge, and sufficiently volatile and thermally stable for gas

chromatog-raphy. Single-laboratory accuracy and precision data have been determined

with two instrument systems using both disks and cartridges for most of the following

compounds:

Analyte MW Registry Number 1

Chemical Abstract Services

Acenaphthylene 152 208-96-8

Alachlor 269 15972-60-8

Aldrin 362 309-00-2

Ametryn 227 834-12-8

Anthracene 178 120-12-7

Atraton 211 1610-17-9

Atrazine 215 1912-24-9

Benz[a]anthracene 228 56-55-3

Benzo[b]fluoranthene 252 205-82-3

Benzo[k]fluoranthene 252 207-08-9

Benzo[a]pyrene 252 50-32-8

Benzo[g,h,i]perylene 276 191-24-2

Bromacil 260 314-40-9

Butachlor 311 23184-66-9

Butylate 317 2008-41-5

Butylbenzylphthalate 312 85-68-7

Carboxin 235 5234-68-4 2

Chlordane components

alpha-Chlordane 406 5103-71-9

gamma-Chlordane 406 5103-74-2

trans-Nonachlor 440 39765-80-5

Chlorneb 206 2675-77-6

Chlorobenzilate 324 510-15-6

Chlorpropham 213 101-21-3

Chlorothalonil 264 1897-45-6
Analyte MW Registry Number 1

Chemical Abstract Services

525.2-3

Chlorpyrifos 349 2921-88-2

2-Chlorobiphenyl 188 2051-60-7

Chrysene 228 218-01-9

Cyanazine 240 21725-46-2

Cycloate 215 1134-23-2

Dacthal (DCPA) 330 1861-32-1

4,4'-DDD 318 72-54-8

4,4'-DDE 316 72-55-9

4,4'-DDT 352 50-29-3

Diazinon 304 333-41-5 2

Dibenz[a,h]anthracene 278 53-70-3

Di-n-Butylphthalate 278 84-74-2

2,3-Dichlorobiphenyl 222 16605-91-7

Dichlorvos 220 62-73-7

Dieldrin 378 60-57-1

Diethylphthalate 222 84-66-2

Di(2-ethylhexyl)adipate 370 103-23-1

Di(2-ethylhexyl)phthalate 390 117-81-7

Dimethylphthalate 194 131-11-3

2,4-Dinitrotoluene 182 121-14-2

2,6-Dinitrotoluene 182 606-20-2

Diphenamid 239 957-51-7

Disulfoton 274 298-04-4 2

Disulfoton Sulfoxide 290 2497-07-6 2

Disulfoton Sulfone 306 2497-06-5

Endosulfan I 404 959-98-8

Endosulfan II 404 33213-65-9

Endosulfan Sulfate 420 1031-07-8

Endrin 378 72-20-8

Endrin Aldehyde 378 7421-93-4

EPTC 189 759-94-4

Ethoprop 242 13194-48-4

Etridiazole 246 2593-15-9

Fenamiphos 303 22224-92-6 2

Fenarimol 330 60168-88-9

Fluorene 166 86-73-7

Fluridone 328 59756-60-4

Heptachlor 370 76-44-8

Heptachlor Epoxide 386 1024-57-3

2,2', 3,3', 4,4', 6-Heptachloro-

 biphenyl 392 52663-71-5

Hexachlorobenzene 282 118-74-1

2,2', 4,4', 5,6'-Hexachloro-

 biphenyl 358 60145-22-4
Analyte MW Registry Number 1

Chemical Abstract Services

525.2-4

Hexachlorocyclohexane, alpha 288 319-84-6

Hexachlorocyclohexane, beta 288 319-85-7

Hexachlorocyclohexane, delta 288 319-86-8

Hexachlorocyclopentadiene 270 77-47-4

Hexazinone 252 51235-04-2

Indeno[1,2,3,c,d]pyrene 276 193-39-5

Isophorone 138 78-59-1

Lindane 288 58-89-9

Merphos 298 150-50-5 2

Methoxychlor 344 72-43-5

Methyl Paraoxon 247 950-35-6

Metolachlor 283 51218-45-2

Metribuzin 214 21087-64-9

Mevinphos 224 7786-34-7

MGK 264 275 113-48-4

Molinate 187 2212-67-1

Napropamide 271 15299-99-7

Norflurazon 303 27314-13-2

2,2', 3,3', 4,5', 6,6'-Octachloro-

 biphenyl 426 40186-71-8

Pebulate 203 1114-71-2

2,2', 3', 4,6'-Pentachlorobiphenyl 324 60233-25-2

Pentachlorophenol 264 87-86-5

Phenanthrene 178 85-01-8

cis-Permethrin 390 54774-45-7

trans-Permethrin 390 51877-74-8

Prometon 225 1610-18-0

Prometryn 241 7287-19-6

Pronamide 255 23950-58-5

Propachlor 211 1918-16-7

Propazine 229 139-40-2

Pyrene 202 129-00-0

Simazine 201 122-34-9

Simetryn 213 1014-70-6

Stirofos 364 22248-79-9

Tebuthiuron 228 34014-18-1

Terbacil 216 5902-51-2

Terbufos2 288 13071-79-9

Terbutryn 241 886-50-0

2,2', 4,4'-Tetrachlorobiphenyl 290 2437-79-8

Toxaphene 8001-35-2

Triademefon 293 43121-43-3

2,4,5-Trichlorobiphenyl 256 15862-07-4

Tricyclazole 189 41814-78-2
Analyte MW Registry Number 1

Chemical Abstract Services

525.2-5

Trifluralin 335 1582-09-8

Vernolate 203 1929-77-7

Aroclor 1016 12674-11-2

Aroclor 1221 11104-28-2

Aroclor 1232 11141-16-5

Aroclor 1242 53469-21-9

Aroclor 1248 12672-29-6

Aroclor 1254 11097-69-1

Aroclor 1260 11096-82-5

Monoisotopic molecular weight calculated from the atomic masses of the isotopes 1

with the smallest masses.

Only qualitative identification of these analytes is possible because of their instability 2

in aqueous matrices. Merphos, carboxin, disulfoton, and disulfoton sulfoxide showed

instability within 1 h of fortification. Diazinon, fenamiphos, and terbufos showed

significant losses within seven days under the sample storage conditions specified in

this method.

Attempting to determine all of the above analytes in all samples is not practical

and not necessary in most cases. If all the analytes must be determined,

multiple calibration mixtures will be required.

1.2 Method detection limit (MDL) is defined as the statistically calculated

minimum amount that can be measured with 99% confidence that the reported

value is greater than zero . The MDL is compound dependent and is 1

particularly dependent on extraction efficiency and sample matrix. MDLs for all

method analytes are listed in Tables 3 through 6. The concentration calibration

range demonstrated in this method is 0.1-10 μg/L for most analytes.

2.0 SUMMARY OF METHOD

Organic compound analytes, internal standards, and surrogates are extracted from a

water sample by passing 1 L of sample water through a cartridge or disk containing a

solid matrix with a chemically bonded C organic phase (liquid-solid extraction, LSE). 18

The organic compounds are eluted from the LSE cartridge or disk with small quantities

of ethyl acetate followed by methylene chloride, and this extract is concentrated further

by evaporation of some of the solvent. The sample components are separated,

identified, and measured by injecting an aliquot of the concentrated extract into a high

resolution fused silica capillary column of a gas chromatography/mass spectrometry

(GC/MS) system. Compounds eluting from the GC column are identified by comparing

their measured mass spectra and retention times to reference spectra and retention

times in a data base. Reference spectra and retention times for analytes are obtained by

the measurement of calibration standards under the same conditions used for samples. 
525.2-6

The concentration of each identified component is measured by relating the MS

response of the quantitation ion produced by that compound to the MS response of the

quantitation ion produced by a compound that is used as an internal standard. 

Surrogate analytes, whose concentrations are known in every sample, are measured with

the same internal standard calibration procedure.

3.0 DEFINITIONS

3.1 Internal Standard (IS) -- A pure analyte(s) added to a sample, extract, or

standard solution in known amount(s) and used to measure the relative

responses of other method analytes and surrogates that are components of the

same solution. The internal standard must be an analyte that is not a sample

component.

3.2 Surrogate Analyte (SA) -- A pure analyte(s), which is extremely unlikely to be

found in any sample, and which is added to a sample aliquot in known

amount(s) before extraction or other processing, and is measured with the same

procedures used to measure other sample components. The purpose of the SA is

to monitor method performance with each sample.

3.3 Laboratory Duplicates (LD1 and LD2) -- Two aliquots of the same sample taken

in the laboratory and analyzed separately with identical procedures. Analyses of

LD1 and LD2 indicate precision associated with laboratory procedures, but not

with sample collection, preservation, or storage procedures.

3.4 Field Duplicates (FD1 and FD2) -- Two separate samples collected at the same

time and place under identical circumstances, and treated exactly the same

throughout field and laboratory procedures. Analyses of FD1 and FD2 give a

measure of the precision associated with sample collection, preservation, and

storage, as well as with laboratory procedures.

3.5 Laboratory Reagent Blank (LRB) -- An aliquot of reagent water or other blank

matrix that is treated exactly as a sample including exposure to all glassware,

equipment, solvents, reagents, internal standards, and surrogates that are used

with other samples. The LRB is used to determine if method analytes or other

interferences are present in the laboratory environment, the reagents, or the

apparatus.

3.6 Field Reagent Blank (FRB) -- An aliquot of reagent water or other blank matrix

that is placed in a sample container in the laboratory and treated as a sample in

all respects, including shipment to the sampling site, exposure to sampling site

conditions, storage, preservation, and all analytical procedures. The purpose of

the FRB is to determine if method analytes or other interferences are present in

the field environment.
525.2-7

3.7 Instrument Performance Check Solution (IPC) -- A solution of one or more

method analytes, surrogates, internal standards, or other test substances used to

evaluate the performance of the instrument system with respect to a defined set

of method criteria.

3.8 Laboratory Fortified Blank (LFB) -- An aliquot of reagent water or other blank

matrix to which known quantities of the method analytes are added in the

laboratory. The LFB is analyzed exactly like a sample, and its purpose is to

determine whether the methodology is in control, and whether the laboratory is

capable of making accurate and precise measurements.

3.9 Laboratory Fortified Sample Matrix (LFM) -- An aliquot of an environmental

sample to which known quantities of the method analytes are added in the

laboratory. The LFM is analyzed exactly like a sample, and its purpose is to

determine whether the sample matrix contributes bias to the analytical results. 

The background concentrations of the analytes in the sample matrix must be

determined in a separate aliquot and the measured values in the LFM corrected

for background concentrations.

3.10 Stock Standard Solution (SSS) -- A concentrated solution containing one or

more method analytes prepared in the laboratory using assayed reference

materials or purchased from a reputable commercial source.

3.11 Primary Dilution Standard Solution (PDS) -- A solution of several analytes

prepared in the laboratory from stock standard solutions and diluted as needed

to prepare calibration solutions and other needed analyte solutions.

3.12 Calibration Standard (CAL) -- A solution prepared from the primary dilution

standard solution or stock standard solutions and the internal standards and

surrogate analytes. The CAL solutions are used to calibrate the instrument

response with respect to analyte concentration.

3.13 Quality Control Sample (QCS) -- A solution of method analytes of known

concentrations which is used to fortify an aliquot of LRB or sample matrix. The

QCS is obtained from a source external to the laboratory and different from the

source of calibration standards. It is used to check laboratory performance with

externally prepared test materials.

4.0 INTERFERENCES

4.1 During analysis, major contaminant sources are reagents and liquid- solid

extraction devices. Analyses of field and laboratory reagent blanks provide

information about the presence of contaminants.
525.2-8

4.2 Interfering contamination may occur when a sample containing low

concentrations of compounds is analyzed immediately after a sample containing

relatively high concentrations of compounds. Syringes and splitless injection

port liners must be cleaned carefully or replaced as needed. After analysis of a

sample containing high concentrations of compounds, a laboratory reagent blank

should be analyzed to ensure that accurate values are obtained for the next

sample.

5.0 SAFETY

5.1 The toxicity or carcinogenicity of chemicals used in this method has not been

precisely defined; each chemical should be treated as a potential health hazard,

and exposure to these chemicals should be minimized. Each laboratory is

responsible for maintaining awareness of OSHA regulations regarding safe

handling of chemicals used in this method. Additional references to laboratory

safety are cited .

2-4

5.2 Some method analytes have been tentatively classified as known or suspected

human or mammalian carcinogens. Pure standard materials and stock standard

solutions of these compounds should be handled with suitable protection to skin,

eyes, etc.

6.0 EQUIPMENT AND SUPPLIES (All specifications are suggested. Catalog numbers are

included for illustration only.)

6.1 All glassware must be meticulously cleaned. This may be accomplished by

washing with detergent and water, rinsing with water, distilled water, or

solvents, air-drying, and heating (where appropriate) in a muffle furnace. 

Volumetric glassware should never be heated to the temperatures obtained in a

muffle furnace.

6.2 Sample Containers -- 1 L or 1 qt amber glass bottles fitted with Teflon-lined

screw caps. Amber bottles are highly recommended since some of the method

analytes are very sensitive to light and are oxidized or decomposed upon

exposure.

6.3 Volumetric Flasks -- Various sizes.

6.4 Laboratory or Aspirator Vacuum System -- Sufficient capacity to maintain a

minimum vacuum of approximately 13 cm (5 in.) of mercury for cartridges. A

greater vacuum (66 cm [26 in.] of mercury) may be used with disks.

6.5 Micro Syringes -- Various sizes.
525.2-9

6.6 Vials -- Various sizes of amber vials with Teflon-lined screw caps.

6.7 Drying Column -- The drying tube should contain about 5-7 g of anhydrous

sodium sulfate to prohibit residual water from contaminating the extract. Any

small tube may be used, such as a syringe barrel, a glass dropper, etc. as long as

no sodium sulfate passes through the column into the extract.

6.8 Analytical Balance -- Capable of weighing 0.0001 g accurately. 

6.9 Fused Silica Capillary Gas Chromatography Column -- Any capillary column

that provides adequate resolution, capacity, accuracy, and precision

(Section 10.0) can be used. Medium polar, low bleed columns are

recommended for use with this method to provide adequate chromatography

and minimize column bleed. A 30 m X 0.25 mm id fused silica capillary column

coated with a 0.25 μm bonded film of polyphenylmethylsilicone (J&W

DB-5.MS) was used to develop this method. Any column which provides

analyte separations equivalent to or better than this column may be used.

6.10 Gas Chromatograph/Mass Spectrometer/Data System (GC/MS/DS)

6.10.1 The GC must be capable of temperature programming and be equipped

for splitless/split injection. On-column capillary injection is acceptable if

all the quality control specifications in Section 9.0 and Section 10.0 are

met. The injection tube liner should be quartz and about 3 mm in

diameter. The injection system must not allow the analytes to contact

hot stainless steel or other metal surfaces that promote decomposition.

6.10.2 The GC/MS interface should allow the capillary column or transfer line

exit to be placed within a few mm of the ion source. Other interfaces, for

example the open split interface, are acceptable as long as the system has

adequate sensitivity (see Section 10.0 for calibration requirements).

6.10.3 The mass spectrometer must be capable of electron ionization at a

nominal electron energy of 70 eV to produce positive ions. The

spectrometer must be capable of scanning at a minimum from

45-450 amu with a complete scan cycle time (including scan overhead)

of 1.0 second or less. (Scan cycle time = total MS data acquisition time

in seconds divided by number of scans in the chromatogram). The

spectrometer must produce a mass spectrum that meets all criteria in

Table 1 when an injection of approximately 5 ng of DFTPP is introduced

into the GC. An average spectrum across the DFTPP GC peak may be

used to test instrument performance. The scan time should be set so that

all analytes have a minimum of five scans across the chromatographic

peak.
525.2-10

6.10.4 An interfaced data system is required to acquire, store, reduce, and

output mass spectral data. The computer software must have the

capability of processing stored GC/MS data by recognizing a GC peak

within any given retention time window, comparing the mass spectrum

from the GC peak with spectral data in a user-created data base, and

generating a list of tentatively identified compounds with their retention

times and scan numbers. The software must also allow integration of the

ion abundance of any specific ion between specified time or scan number

limits, calculation of response factors as defined in Section 10.2.6 (or

construction of a linear regression calibration curve), calculation of

response factor statistics (mean and standard deviation), and calculation

of concentrations of analytes using either the calibration curve or the

equation in Section 12.0.

6.11 Standard Filter Apparatus, All Glass or Teflon Lined -- These should be used to

carry out disk extractions when no automatic system or manifold is utilized.

6.12 A manifold system or an automatic or robotic commercially available sample

preparation system designed for either cartridges or disks may be utilized in this

method if all quality control requirements discussed in Section 9.0 are met.

7.0 REAGENTS AND STANDARDS

7.1 Helium Carrier Gas -- As contaminant free as possible.

7.2 Liquid-Solid Extraction (LSE) Cartridges -- Cartridges are inert non-leaching

plastic, for example polypropylene, or glass, and must not contain plasticizers,

such as phthalate esters or adipates, that leach into the ethyl acetate and

methylene chloride eluant. The cartridges are packed with about 1 g of silica, or

other inert inorganic support, whose surface is modified by chemically bonded

octadecyl (C18) groups. The packing must have a narrow size distribution and

must not leach organic compounds into the eluting solvent. One liter of water

should pass through the cartridge in about two hours with the assistance of a

slight vacuum of about 13 cm (5 in.) of mercury. Section 9.0 provides criteria

for acceptable LSE cartridges which are available from several commercial

suppliers.

The extraction disks contain octadecyl bonded silica uniformly enmeshed in an

inert matrix. The disks used to generate the data in this method were 47 mm in

diameter and 0.5 mm in thickness. Other disk sizes are acceptable and larger

disks may be used for special problems or when sample compositing is carried

out. As with cartridges, the disks should not contain any organic compounds,

either from the matrix or the bonded silica, which will leach into the ethyl

acetate and methylene chloride eluant. One L of reagent water should pass
525.2-11

through the disks in five to 20 minutes using a vacuum of about 66 cm (26 in.)

of mercury. Section 9.0 provides criteria for acceptable LSE disks which are

available commercially.

7.3 Solvents

7.3.1 Methylene Chloride, Ethyl Acetate, Acetone, Toluene, and Methanol --

High purity pesticide quality or equivalent. 

7.3.2 Reagent Water -- Water in which an interference is not observed at the

method detection limit of the compound of interest. Prepare reagent

water by passing tap water through a filter bed containing about 0.5 kg of

activated carbon or by using a water purification system. Store in clean,

narrow-mouth bottles with Teflon-lined septa and screw caps.

7.4 Hydrochloric Acid -- 6N.

7.5 Sodium Sulfate, Anhydrous -- (Soxhlet extracted with methylene chloride for a

minimum of four hours or heated to 400 C for two hours in a muffle furnace.)

7.6 Stock Standard Solutions (SSS) -- Individual solutions of surrogates, internal

standards, and analytes, or mixtures of analytes, may be purchased from

commercial suppliers or prepared from pure materials. To prepare, add 10 mg

(weighed on an analytical balance to 0.1 mg) of the pure material to 1.9 mL of

methanol, ethyl acetate, or acetone in a 2 mL volumetric flask, dilute to the

mark, and transfer the solution to an amber glass vial. If the analytical standard

is available only in quantities smaller than 10 mg, reduce the volume of solvent

accordingly. Some polycyclic aromatic hydrocarbons are not soluble in

methanol, ethyl acetate, or acetone, and their stock standard solutions are

prepared in toluene. Methylene chloride should be avoided as a solvent for

standards because its high vapor pressure leads to rapid evaporation and

concentration changes. Methanol, ethyl acetate, and acetone are not as volatile

as methylene chloride, but their solutions must also be handled with care to

avoid evaporation. If compound purity is confirmed by the supplier at >96%,

the weighed amount can be used without correction to calculate the

concentration of the solution (5 μg/μL). Store the amber vials at 4 C or less.

7.7 Primary Dilution Standard Solution (PDS) -- The stock standard solutions are

used to prepare a primary dilution standard solution that contains multiple

analytes. Mixtures of these analytes to be used as primary dilution standards

may be purchased from commercial suppliers. Do not put every method analyte

in a single primary dilution standard because chromatographic separation will be

extremely difficult, if not impossible. Two or three primary dilution standards

would be more appropriate. The recommended solvent for these standards is
525.2-12

acetone or ethyl acetate. Aliquots of each of the stock standard solutions are

combined to produce the primary dilution in which the concentration of the

analytes is at least equal to the concentration of the most concentrated

calibration solution, that is, 10 ng/μL. Store the primary dilution standard

solution in an amber vial at 4 C or less, and check frequently for signs of

degradation or evaporation, especially just before preparing calibration solutions.

7.8 Fortification Solution of Internal Standards and Surrogates -- Prepare an internal

standard solution of acenaphthene-D10, phenanthrene-D10, and chrysene-D12, in

methanol, ethyl acetate, or acetone at a concentration of 500 μg/mL of each. 

This solution is used in the preparation of the calibration solutions. Dilute a

portion of this solution by 10 to a concentration of 50 μg/mL and use this

solution to fortify the actual water samples (see Section 11.1.3 and Section

11.2.3). Similarly, prepare both surrogate compound solutions (500 μg/mL for

calibration, 50 μg/mL for fortification). Surrogate compounds used in

developing this method are 1,3-dimethyl-2-nitrobenzene, perylene-D12, and

triphenylphosphate. Other surrogates, for example pyrene-D10 may be used in

this solution as needed (a 100 μL aliquot of this 50 μg/mL solution added to 1 L

of water gives a concentration of 5 μg/L of each internal standard or surrogate). 

Store these solutions in an amber vial at 4 C or less. These two solutions may

be combined or made as a single solution.

7.9 GC/MS Performance Check Solution -- Prepare a solution in methylene chloride

of the following compounds at 5 ng/μL of each: DFTPP and endrin, and 4,4'-

DDT. Store this solution in an amber vial at 4 C or less. DFTPP is less stable

in acetone or ethyl acetate than it is in methylene chloride.

7.10 Calibration Solutions (CAL1 through CAL6) -- Prepare a series of six

concentration calibration solutions in ethyl acetate which contain analytes of

interest (except pentachlorophenol, toxaphene, and the Aroclor compounds) at

suggested concentrations of 10, 5, 2, 1, 0.5, and 0.1 ng/μL, with a constant

concentration of 5 ng/μL of each internal standard and surrogate in each CAL

solution. It should be noted that CAL1 through CAL6 are prepared by

combining appropriate aliquots of a primary dilution standard solution

(Section 7.7) and the fortification solution (500 μg/mL) of internal standards

and surrogates (Section 7.8). All calibration solutions should contain at least

80% ethyl acetate to avoid gas chromatographic problems. IF ALL METHOD

ANALYTES ARE TO BE DETERMINED, TWO OR THREE SETS OF

CALIBRATION SOLUTIONS WILL LIKELY BE REQUIRED. 

Pentachlorophenol is included in this solution at a concentration four times the

other analytes. Toxaphene CAL solutions should be prepared as separate

solutions at concentrations of 250, 200, 100, 50, 25, and 10 ng/μL. Aroclor

CAL solutions should be prepared individually at concentrations of 25, 10, 5,

2.5, 1.0, 0.5, and 0.2 ng/μL. Store these solutions in amber vials in a dark cool
525.2-13

place. Check these solutions regularly for signs of degradation, for example, the

appearance of anthraquinone from the oxidation of anthracene.

7.11 Reducing Agent, Sodium Sulfite, Anhydrous -- Sodium thiosulfate is not

recommended as it may produce a residue of elemental sulfur that can interfere

with some analytes.

7.12 Fortification Solution for Recovery Standard -- Prepare a solution of

terphenyl-D at a concentration of 500 μg/mL in methylene chloride or ethyl 14

acetate. These solutions are also commercially available. An aliquot of this

solution should be added to each extract to check on the recovery of the internal

standards in the extraction process.

8.0 SAMPLE COLLECTION, PRESERVATION, AND STORAGE

8.1 Sample Collection -- When sampling from a water tap, open the tap and allow

the system to flush until the water temperature has stabilized (usually about two

minutes). Adjust the flow to about 500 mL/min. and collect samples from the

flowing stream. Keep samples sealed from collection time until analysis. When

sampling from an open body of water, fill the sample container with water from

a representative area. Sampling equipment, including automatic samplers, must

be free of plastic tubing, gaskets, and other parts that may leach interfering

analytes into the water sample. Automatic samplers that composite samples

over time should use refrigerated glass sample containers if possible.

8.2 Sample Dechlorination and Preservation -- All samples should be iced or

refrigerated at 4 C and kept in the dark from the time of collection until

extraction. Residual chlorine should be reduced at the sampling site by addition

of 40-50 mg of sodium sulfite (this may be added as a solid with stirring or

shaking until dissolved) to each water sample. It is very important that the

sample be dechlorinated prior to adding acid to lower the pH of the sample. 

Adding sodium sulfite and HCl to the sample bottles prior to shipping to the

sampling site is not permitted. Hydrochloric acid should be used at the sampling

site to retard the microbiological degradation of some analytes in water. The

sample pH is adjusted to <2 with 6 N hydrochloric acid. This is the same pH

used in the extraction, and is required to support the recovery of acidic

compounds like pentachlorophenol.

8.2.1 If cyanizine is to be determined, a separate sample must be collected. 

Cyanazine degrades in the sample when it is stored under acidic

conditions or when sodium sulfite is present in the stored sample. 

Samples collected for cyanazine determination MUST NOT be

dechlorinated or acidified when collected. They should be iced or

refrigerated as described above and analyzed within 14 days. However,
525.2-14

these samples MUST be dechlorinated and acidified immediately prior to

fortification with internal standards and surrogates, and extraction using

the same quantities of acid and sodium sulfite described above.

8.2.2 Atraton and prometon are not efficiently extracted from water at pH 2

due to what appears to be their ionization in solution under acidic

conditions. In order to determine these analytes accurately, a separate

sample must be collected and dechlorinated with sodium sulfite, but no

acid should be added. At neutral pH, these two compounds are

recovered from water with efficiencies greater than 90%. The data in

Tables 3, 4, 5, 6, and 8 are from samples extracted at pH 2.

8.3 Holding Time -- Results of the time/storage study of all method analytes showed

that all but six compounds are stable for 14 days in water samples when the

samples are dechlorinated, preserved, and stored as described in Section 8.2. 

Therefore, samples must be extracted within 14 days. If the following analytes

are to be determined, the samples cannot be held for 14 days but must be

extracted immediately after collection and preservation: carboxin, diazinon,

disulfoton, disulfoton sulfoxide, fenamiphos, and terbufos. Sample extracts may

be stored at 4 C for up to 30 days after sample extraction.

8.4 Field Blanks

8.4.1 Processing of a field reagent blank (FRB) is recommended along with

each sample set, which is composed of the samples collected from the

same general sample site at approximately the same time. At the

laboratory, fill a sample container with reagent water, seal, and ship to

the sampling site along with the empty sample containers. Return the

FRB to the laboratory with the filled sample bottles.

8.4.2 When sodium sulfite and hydrochloric acid are added to samples, use the

same procedure to add the same amounts to the FRB.

9.0 QUALITY CONTROL

9.1 Quality control (QC) requirements are the initial demonstration of laboratory

capability followed by regular analyses of laboratory reagent blanks, laboratory

fortified blanks, and laboratory fortified matrix samples. A MDL should be

determined for each analyte of interest. The laboratory must maintain records

to document the quality of the data generated. Additional quality control

practices are recommended.

9.2 Initial Demonstration of Low Disk or Cartridge System Background -- Before

any samples are analyzed, or any time a new supply of cartridges or disks is
525.2-15

received from a supplier, it must be demonstrated that a laboratory reagent

blank (LRB) is reasonably free of contamination that would prevent the

determination of any analyte of concern. In this same experiment, it must be

demonstrated that the particle size and packing of the LSE cartridges or the

preparation of the disks are acceptable. Consistent flow rate with all samples is

an indication of acceptable particle size distribution, packing, and proper

preparation.

9.2.1 A source of potential contamination is the liquid-solid extraction (LSE)

cartridge or disk which could contain phthalate esters, silicon

compounds, and other contaminants that could prevent the

determination of method analytes . Although disks are generally made of 5

an inert matrix, they may still contain phthalate material. Generally,

phthalate esters can be leached from the cartridges into ethyl acetate and

methylene chloride and produce a variable background in the water

sample. If the background contamination is sufficient to prevent

accurate and precise measurements, the condition must be corrected

before proceeding with the initial demonstration.

9.2.2 Other sources of background contamination are solvents, reagents, and

glassware. Background contamination must be reduced to an acceptable

level before proceeding with the next section. In general, background

from method analytes should be below the method detection limits.

9.2.3 One L of water should pass through a cartridge in about two hours with a

partial vacuum of about 13 cm (5 in.) of mercury. Using full aspirator or

pump vacuum, approximately five to 20 minutes will normally be

required to pass one liter of drinking water through a disk. The

extraction time should not vary unreasonably among LSE cartridges or

disks.

9.3 Initial Demonstration of Laboratory Accuracy and Precision -- Analyze four to

seven replicates of a laboratory fortified blank containing each analyte of

concern at a suggested concentration in the range of 2-5 μg/L. This

concentration should be approximately in the middle of the calibration range,

and will be dependent on the sensitivity of the instrumentation used. 

9.3.1 Prepare each replicate by adding sodium sulfite and HCl according to

Section 8.2, then adding an appropriate aliquot of the primary dilution

standard solution, or certified quality control sample, to reagent water. 

Analyze each replicate according to the procedures described in

Section 11.0.
525.2-16

9.3.2 Calculate the measured concentration of each analyte in each replicate,

the mean concentration of each analyte in all replicates, and mean

accuracy (as mean percentage of true value) for each analyte, and the

precision (as relative standard deviation, RSD) of the measurements for

each analyte.

9.3.3 For each analyte and surrogate, the mean accuracy, expressed as a

percentage of the true value, should be 70-130% and the RSD should be

<30%. If these criteria are not met, locate the source of the problem,

and repeat with freshly prepared LFBs.

9.3.4 Analyze seven replicate laboratory fortified blanks which have been

fortified with all analytes of interest at approximately 0.5 μg/L. Calculate

the MDL of each analyte using the procedure described in Section

13.1.2 . It is recommended that these analyses be performed over a 1

period of three or four days to produce more realistic method detection

limits.

9.3.5 Develop and maintain a system of control charts to plot the precision

and accuracy of analyte and surrogate measurements as a function of

time. Charting of surrogate recoveries is an especially valuable activity

since these are present in every sample and the analytical results will

form a significant record of data quality.

9.4 Monitor the integrated areas of the quantitation ions of the internal standards

and surrogates in continuing calibration checks (see Section 10.3). In laboratory

fortified blanks or samples, the integrated areas of internal standards and

surrogates will not be constant because the volume of the extract will vary (and

is difficult to keep constant). But the ratios of the areas should be reasonably

constant in laboratory fortified blanks and samples. The addition of 10 μL of

the recovery standard, terphenyl-D (500 μg/mL), to the extract is 14

recommended to be used to monitor the recovery of the internal standards in

laboratory fortified blanks and samples. Internal standard recovery should be in

excess of 70%.

9.5 With each batch of samples processed as a group within a 12-hour work shift,

analyze a laboratory reagent blank to determine the background system

contamination. Any time a new batch of LSE cartridges or disks is received, or

new supplies of other reagents are used, repeat the demonstration of low

background described in Section 9.2.

9.6 With each batch of samples processed as a group within a work shift, analyze a

single laboratory fortified blank (LFB) containing each analyte of concern at a

concentration as determined in Section 9.3. If more than 20 samples are
525.2-17

included in a batch, analyze a LFB for every 20 samples. Use the procedures

described in Section 9.3.3 to evaluate the accuracy of the measurements. If

acceptable accuracy cannot be achieved, the problem must be located and

corrected before additional samples are analyzed. Add the results to the

on-going control charts to document data quality.

Note: If the LFB for each batch of samples contains the individual PCB

congeners listed in Section 1.0, then a LFB for each Aroclor is not required. At

least one LFB containing toxaphene should be extracted for each 24 hour period

during which extractions are performed. Toxaphene should be fortified in a

separate LFB from other method analytes.

If individual PCB congeners are not part of the LFB, then it is suggested that one

multi-component analyte (toxaphene, chlordane or an Aroclor) LFB be analyzed

with each sample set. By selecting a different multi-component analyte for this

LFB each work shift, LFB data can be obtained for all of these analytes over the

course of several days. 

9.7 Determine that the sample matrix does not contain materials that adversely

affect method performance. This is accomplished by analyzing replicates of

laboratory fortified matrix samples and ascertaining that the precision, accuracy,

and method detection limits of analytes are in the same range as obtained with

laboratory fortified blanks. If a variety of different sample matrices are analyzed

regularly, for example, drinking water from groundwater and surface water

sources, matrix independence should be established for each. Over time, LFM

data should be documented for all routine sample sources for the laboratory. A

laboratory fortified sample matrix should be analyzed for every 20 samples

processed in the same batch. If the recovery data for a LFM does not meet the

criteria in Section 9.3.3., and LFBs show the laboratory to be in control , then

the samples from that matrix (sample location) are documented as suspect due

to matrix effects.

9.8 With each set of samples, a FRB should be analyzed. The results of this analysis

will help define contamination resulting from field sampling and transportation

activities.

9.9 At least quarterly, analyze a quality control sample from an external source. If

measured analyte concentrations are not of acceptable accuracy (Section 9.3.3),

check the entire analytical procedure to locate and correct the problem source.

9.10 Numerous other quality control measures are incorporated into other parts of

this procedure, and serve to alert the analyst to potential problems.
TIC area of DDT degradation peaks (DDE DDD)

TIC area of total DDT peaks (DDT DDE DDD)

x 100

525.2-18

10.0 CALIBRATION AND STANDARDIZATION

10.1 Demonstration and documentation of acceptable initial calibration is required

before any samples are analyzed and is required intermittently throughout

sample analysis as dictated by results of continuing calibration checks. After

initial calibration is successful, a continuing calibration check is required each

day or at the beginning of each period in which analyses are performed not to

exceed 12 hours. Additional periodic calibration checks are good laboratory

practice. It is recommended that an additional calibration check be performed

at the end of each period of continuous instrument operation, so that all field

sample analyses are bracketed by a calibration check standard.

10.2 Initial Calibration

10.2.1 Calibrate the mass and abundance scales of the MS with calibration

compounds and procedures prescribed by the manufacturer with any

modifications necessary to meet the requirements in Section 10.2.2.

10.2.2 Inject into the GC/MS system a 1 μL aliquot of the 5 ng/μL solution of

DFTPP, endrin and 4,4'-DDT. If desired, the endrin and DDT

degradation checks may be performed simultaneously with the DFTPP

check or in a separate injection. Acquire a mass spectrum that includes

data for m/z 45-450. Use GC conditions that produce a narrow (at least

five scans per peak) symmetrical peak for each compound

(Section 10.2.3.1 and Section 10.2.3.2). If the DFTPP mass spectrum

does not meet all criteria in Table 1, the MS must be retuned and

adjusted to meet all criteria before proceeding with calibration. A single

spectrum or an average spectrum across the GC peak may be used to

evaluate the performance of the system. Locate any degradation

products of endrin (endrin ketone [EK] and endrin aldehyde [EA]) and

4,4'-DDT (4,4'-DDE and 4,4'-DDD) at their appropriate retention times

and quantitation ions (Table 2). Endrin ketone can be located at 1.1 to

1.2 times the endrin retention time with prominent m/z 67 and 317 ions

in the mass spectrum. If degradation of either endrin or DDT exceeds

20%, maintenance is required on the GC injection port and possibly

other areas of the system before proceeding with the calibration. 

Calculate percent breakdown using peak areas based on total ion current

(TIC) as follows:

% 4,4'-DDT breakdown =
TIC area of endrin degradation peaks (EA EK)

TIC area of total endrin peaks (endrin EA EK)

x 100

525.2-19

% endrin breakdown=

10.2.3 Inject a 1 μL aliquot of a medium concentration calibration solution, for

example 0.5-2 μg/L, and acquire and store data from m/z 45-450 with a

total cycle time (including scan overhead time) of 1.0 second or less. 

Cycle time should be adjusted to measure at least five or more spectra

during the elution of each GC peak. Calibration standards for toxaphene

and Aroclors must be injected individually.

10.2.3.1 The following are suggested multi-ramp temperature

program GC conditions. Adjust the helium carrier gas

flow rate to about 33 cm/sec. Inject at 45 C and hold in

splitless mode for one minute. Heat rapidly to 130 C. At

three minutes start the temperature program: 130-180 C

at 12 /min.; 180-240 C at 7 /min.; 240-320 C at

12 /min. Start data acquisition at four minutes.

10.2.3.2 Single ramp linear temperature program suggested GC

conditions. Adjust the helium carrier gas flow rate to

about 33 cm/sec. Inject at 40 C and hold in splitless

mode for one minute. Heat rapidly to 160 C. At

three minutes start the temperature program: 160-320 C

at 6 /min.; hold at 320 C for two minutes. Start data

acquisition at three minutes.

10.2.4 Performance Criteria for the Calibration Standards -- Examine the stored

GC/MS data with the data system software.

10.2.4.1 GC Performance -- Anthracene and phenanthrene should

be separated by baseline. Benz[a]anthracene and

chrysene should be separated by a valley whose height is

less than 25% of the average peak height of these two

compounds. If the valley between benz[a]anthracene and

chrysene exceeds 25%, the GC column requires

maintenance. See Section 10.3.6. 

10.2.4.2 MS Sensitivity -- The GC/MS/DS peak identification

software should be able to recognize a GC peak in the

appropriate retention time window for each of the

compounds in the calibration solution, and make correct
RF

(Ax) (Qis)

(Ais) (Qx)

525.2-20

identifications. If fewer than 99% of the compounds are

recognized, system maintenance is required. See

Section 10.3.6.

10.2.5 If all performance criteria are met, inject a 1 μL aliquot of each of the

other CAL solutions using the same GC/MS conditions. Calibration

standards of toxaphene and Aroclors must be injected individually.

10.2.5.1 Some GC/MS systems may not be sensitive enough to

detect some of the analytes in the two lowest

concentration CAL solutions. In this case, the analyst

should prepare additional CAL solutions at slightly higher

concentrations to obtain at least five calibration points

that bracket the expected analyte concentration range.

10.2.6 Calculate a response factor (RF) for each analyte of interest and surrogate

for each CAL solution using the internal standard whose retention time is

nearest the retention time of the analyte or surrogate. Table 2 contains

suggested internal standards for each analyte and surrogate, and

quantitation ions for all compounds. This calculation is supported in

acceptable GC/MS data system software (Section 6.10.4), and many

other software programs. The RF is a unitless number, but units used to

express quantities of analyte and internal standard must be equivalent.

Note: To calibrate for multi-component analytes (toxaphene and

Aroclors), one of the following methods should be used.

Option 1 - Calculate an average response factor or linear regression

equation for each multi-component analyte from the combined area of all

its component peaks identified in the calibration standard

chromatogram, using two to three of the suggested quantitation ions in

Table 2.

Option 2 - Calculate an average response factor or linear regression

equation for each multi-component analyte using the combined areas of

three to six of the most intense and reproducible peaks in each of the

calibration standard chromatograms. Use an appropriate quantitation

ion for each peak.
525.2-21

where: A = integrated abundance of the quantitation ion of the analyte x

A = integrated abundance of the quantitation ion internal is

 standard

Q = quantity of analyte injected in ng or concentration units x

Q = quantity of internal standard injected in ng or is

 concentration units.

10.2.6.1 For each analyte and surrogate, calculate the mean RF

from the analyses of the six CAL solutions. Calculate the

standard deviation (SD) and the relative standard

deviation (RSD) from each mean: RSD = 100 (SD/M). 

If the RSD of any analyte or surrogate mean RF exceeds

30%, either analyze additional aliquots of appropriate

CAL solutions to obtain an acceptable RSD of RFs over

the entire concentration range, or take action to improve

GC/MS performance. See Section 10.3.6.

10.2.7 As an alternative to calculating mean response factors, use the GC/MS

data system software or other available software to generate a linear

regression calibration by plotting A /A vs. Q .

x is x

10.3 Continuing Calibration Check -- Verify the MS tune and initial calibration at

the beginning of each 12-hour work shift during which analyses are performed

using the following procedure.

10.3.1 Inject a 1 μL aliquot of the 5 ng/μL solution of DFTPP, endrin, and

4,4'-DDT. Acquire a mass spectrum for DFTPP that includes data for

m/z 45-450. Ensure that all criteria in Section 10.2.2 are met.

10.3.2 Inject a 1 μL aliquot of a calibration solution and analyze with the same

conditions used during the initial calibration. It is recommended that the

concentration of calibration solution be varied, so that the calibration

can be verified at more than one point.

Note: If the continuing calibration check standard contains the PCB

congeners listed in Section 1.0, calibration verification is not required for

each Aroclor. Calibration verification of toxaphene should be performed

at least once each 24 hour period.

10.3.3 Demonstrate acceptable performance for the criteria shown in

Section 10.2.4.

10.3.4 Determine that the absolute areas of the quantitation ions of the internal

standards and surrogate(s) have not changed by more than 30% from the
525.2-22

areas measured in the most recent continuing calibration check, or by

more than 50% from the areas measured during initial calibration. If

these areas have decreased by more than these amounts, adjustments

must be made to restore system sensitivity. These adjustments may

require cleaning of the MS ion source, or other maintenance as indicated

in Section 10.3.6, and recalibration. Control charts are useful aids in

documenting system sensitivity changes.

10.3.5 Calculate the RF for each analyte and surrogate from the data measured

in the continuing calibration check. The RF for each analyte and

surrogate must be within 30% of the mean value measured in the initial

calibration. Alternatively, if a linear regression is used, the calculated

amount for each analyte must be ±30% of the true value. If these

conditions do not exist, remedial action should be taken which may

require recalibration. Any field sample extracts that have been analyzed

since the last acceptable calibration verification should be reanalyzed

after adequate calibration has been restored.

10.3.5.1 Because of the large number of compounds on the analyte

list, it is possible for a few analytes of interest to be outside

the continuing calibration criteria. If analytes that missed

the calibration check are detected in samples, they may be

quantified using a single point calibration. The single

point standards should be prepared at concentrations that

produce responses close (±20%) to those of the

unknowns. If the same analyte misses the continuing

calibration check on three consecutive work shifts,

remedial action MUST be taken. If more than 10% of the

analytes of interest miss the continuing calibration check

on a single day, remedial action MUST be taken.

10.3.6 Some Possible Remedial Actions -- Major maintenance such as cleaning

an ion source, cleaning quadrupole rods, replacing filament assemblies,

etc. require returning to the initial calibration step.

10.3.6.1 Check and adjust GC and/or MS operating conditions;

check the MS resolution, and calibrate the mass scale.

10.3.6.2 Clean or replace the splitless injection liner; silanize a new

injection liner.

10.3.6.3 Flush the GC column with solvent according to

manufacturer's instructions.
525.2-23

10.3.6.4 Break off a short portion (about 1 m) of the column from

the end near the injector; or replace GC column. This

action will cause a change in retention times. 

10.3.6.5 Prepare fresh CAL solutions, and repeat the initial

calibration step. 

10.3.6.6 Clean the MS ion source and rods (if a quadrupole).

10.3.6.7 Replace any components that allow analytes to come into

contact with hot metal surfaces.

10.3.6.8 Replace the MS electron multiplier, or any other faulty

components.

11.0 PROCEDURE

11.1 Cartridge Extraction

11.1.1 This procedure may be carried out in the manual mode or in the

automated mode (Section 6.12) using a robotic or automatic sample

preparation device. If an automatic system is used to prepare samples,

follow the manufacturer's operating instructions, but follow this

procedure. If the manual mode is used, a suggested setup of the

extraction apparatus is shown in Figure 1A. The reservoir is not required,

but recommended for convenient operation. Water drains from the

reservoir through the LSE cartridge and into a syringe needle which is

inserted through a rubber stopper into the suction flask. A slight vacuum

of approximately 13 cm (5 in.) of mercury is used during all operations

with the apparatus. About two hours should be required to draw a liter

of water through the cartridge.

11.1.2 Elute each cartridge with a 5 mL aliquot of ethyl acetate followed by a 5

mL aliquot of methylene chloride. Let the cartridge drain dry after each

flush. Then elute the cartridge with a 10 mL aliquot of methanol, but

DO NOT allow the methanol to elute below the top of the cartridge

packing. From this point, do not allow the cartridge to go dry. Add

10 mL of reagent water to the cartridge, but before the reagent water

level drops below the top edge of the packing, begin adding sample to the

solvent reservoir. 

11.1.3 Pour the water sample into the 2 L separatory funnel with the stopcock

closed, add 5 mL methanol, and mix well. If a vacuum manifold is used

instead of the separatory funnel, the sample may be transferred directly
525.2-24

to the cartridge after the methanol is added to the sample. (Residual

chlorine should not be present as a reducing agent should have been

added at the time of sampling. Also the pH of the sample should be

about 2. If residual chlorine is present and/or the pH is >2, the sample

may be invalid.) Add a 100 μL aliquot of the fortification solution (50

μg/mL) for internal standards and surrogates, and mix immediately until

homogeneous. The resulting concentration of these compounds in the

water should be 5 μg/L.

11.1.4 Periodically transfer a portion of the sample into the solvent reservoir. 

The water sample will drain into the cartridge, and from the exit into the

suction flask. Maintain the packing material in the cartridge immersed in

water at all times. After all of the sample has passed through the LSE

cartridge, draw air or nitrogen through the cartridge for 10 minutes.

11.1.5 Transfer the 125 mL solvent reservoir and LSE cartridge (from

Figure 1A) to the elution apparatus if used (Figure 1B). The same

125 mL solvent reservoir is used for both apparatus. Rinse the inside of

the 2 L separatory funnel and the sample jar with 5 mL of ethyl acetate

and elute the cartridge with this rinse into the collection tube. Wash the

inside of the separatory funnel and the sample jar with 5 mL methylene

chloride and elute the cartridge, collecting the rinse in the same

collection tube. Small amounts of residual water from the sample

container and the LSE cartridge may form an immiscible layer with the

eluate. Pass the eluate through the drying column (Section 6.7) which is

packed with approximately 5-7 g of anhydrous sodium sulfate and collect

in a second vial. Wash the sodium sulfate with at least 2 mL methylene

chloride and collect in the same vial. Concentrate the extract in a warm

water bath under a gentle stream of nitrogen. Do not concentrate the

extract to less than 0.5 mL, as this will result in losses of analytes. Make

any volume adjustments with ethyl acetate. It is recommended that an

aliquot of the recovery standard be added to the concentrated extract to

check the recovery of the internal standards (see Section 7.12).

11.2 Disk Extraction

 

11.2.1 This procedure was developed using the standard 47 mm diameter disks. 

Larger disks (90 mm diameter) may be used if sample compositing is

being done or special matrix problems are encountered. If larger disks are

used, the washing solvent volume is 15 mL, the conditioning solvent

volume is 15 mL, and the elution solvent volume is two 15 mL aliquots. 

11.2.1.1 Extractions using the disks may be carried out either in the

manual or automatic mode (Section 6.12) using an
525.2-25

automatic sample preparation device. If an automatic

system is used to prepare samples, follow the

manufacturer's operating instructions, but follow this

procedure. Insert the disk into the filter apparatus (Figure

2) or sample preparation unit. Wash the disk with 5 mL

of a 1:1 mixture of ethyl acetate (EtAc) and methylene

chloride (MeCl2) by adding the solvent to the disk,

drawing about half through the disk, allowing it to soak

the disk for about a minute, then drawing the remaining

solvent through the disk.

Note: Soaking the disk may not be desirable when disks

other than Teflon are used. Instead, apply a constant, low

vacuum in this Section and Section 11.2.1.2 to ensure

adequate contact time between solvent and disk.

11.2.1.2 Pre-wet the disk with 5 mL methanol (MeOH) by adding

the MeOH to the disk and allowing it to soak for about a

minute, then drawing most of the remaining MeOH

through. A layer of MeOH must be left on the surface of

the disk, which should not be allowed to go dry from this

point until the end of the sample extraction. THIS IS A

CRITICAL STEP FOR A UNIFORM FLOW AND GOOD

RECOVERY.

11.2.1.3 Rinse the disk with 5 mL reagent water by adding the

water to the disk and drawing most through, again leaving

a layer on the surface of the disk.

11.2.2 Add 5 mL MeOH per liter of water to the sample. Mix well. (Residual

chlorine should not be present as a reducing agent should have been

added at the time of sampling. Also the pH of the sample should be

about 2. If residual chlorine is present and/or the pH is >2, the sample

may be invalid.)

11.2.3 Add 100 μL of the internal standard and surrogate compound

fortification solution (50 μg/mL) to the sample and shake or mix until the

sample is homogeneous. The resulting concentration of these compounds

in the water should be 5 μg/L.

11.2.4 Add the water sample to the reservoir and apply full vacuum to begin the

extraction. Particulate-free water may pass through the disk in as little as

five minutes without reducing analyte recoveries. Extract the entire

sample, draining as much water from the sample container as possible. 

Dry the disk by maintaining vacuum for about 10 minutes.
525.2-26

11.2.5 Remove the filtration top, but do not disassemble the reservoir and

fritted base. If a suction flask is being used, empty the water from the

flask, and insert a suitable collection tube to contain the eluant. The

only constraint on the sample tube is that it fit around the drip tip of the

fritted base. Reassemble the apparatus.

11.2.6 Add 5 mL of ethyl acetate to the sample bottle, and rinse the inside walls

thoroughly. Allow the solvent to settle to the bottom of the bottle, then

transfer it to the disk. A disposable pipet or syringe may be used to do

this, rinsing the sides of the glass filtration reservoir in the process. Draw

about half of the solvent through the disk, release the vacuum, and allow

the disk to soak for a minute. Draw the remaining solvent through the

disk.

Note: Soaking the disk may not be desirable if disks other than Teflon

are used. Instead, apply a constant, low vacuum in this Section and

Section 11.2.7 to ensure adequate contact time between solvent and

disk.

11.2.7 Repeat the above step (Section 11.2.6) with methylene chloride.

11.2.8 Using a syringe or disposable pipet, rinse the filtration reservoir with two

3 mL portions of 1:1 EtAc:MeCl2. Draw the solvent through the disk

and into the collector tube. Pour the combined eluates (Section 11.2.6

through Section 11.2.8) through the drying tube (Section 6.7) containing

about 5-7 g of anhydrous sodium sulfate. Rinse the drying tube and

sodium sulfate with two 3 mL portions of 1:1 EtAc:MeCl2 mixture. 

Collect all the extract and washings in a concentrator tube.

11.2.9 While gently heating the extract in a water bath or a heating block,

concentrate to between 0.5 mL and 1 mL under a gentle stream of

nitrogen. Do not concentrate the extract to less than 0.5 mL, since this

will result in losses of analytes. Make any volume adjustments with ethyl

acetate. It is recommended that an aliquot of the recovery standard be

added to the concentrated extract to check the recovery of the internal

standards (see Section 7.12).

11.3 Analyze a 1 μL aliquot with the GC/MS system under the same conditions used

for the initial and continuing calibrations (Section 10.2.3).

11.4 At the conclusion of data acquisition, use the same software that was used in the

calibration procedure to tentatively identify peaks in predetermined retention

time windows of interest. Use the data system software to examine the ion

abundances of components of the chromatogram. 
525.2-27

11.5 Identification of Analytes -- Identify a sample component by comparison of its

mass spectrum (after background subtraction) to a reference spectrum in the

user-created data base. The GC retention time of the sample component should

be within five seconds of the retention time observed for that same compound in

the most recently analyzed continuing calibration check standard.

11.5.1 In general, all ions that are present above 10% relative abundance in the

mass spectrum of the standard should be present in the mass spectrum of

the sample component and should agree within absolute 20%. For

example, if an ion has a relative abundance of 30% in the standard

spectrum, its abundance in the sample spectrum should be in the range of

10-50%. Some ions, particularly the molecular ion, are of special

importance, and should be evaluated even if they are below 10% relative

abundance.

11.5.2 Identification is hampered when sample components are not resolved

chromatographically and produce mass spectra containing ions

contributed by more than one analyte. When GC peaks obviously

represent more than one sample component (i.e., broadened peak with

shoulder(s) or valley between two or more maxima), appropriate analyte

spectra and background spectra can be selected by examining plots of

characteristic ions for tentatively identified components. When analytes

coelute (i.e., only one GC peak is apparent), the identification criteria

can be met but each analyte spectrum will contain extraneous ions

contributed by the coeluting compound.

11.5.3 Structural isomers that produce very similar mass spectra can be

explicitly identified only if they have sufficiently different GC retention

times. See Section 10.2.4.1. Acceptable resolution is achieved if the

height of the valley between two isomer peaks is less than 25% of the

average height of the two peak heights. Otherwise, structural isomers are

identified as isomeric pairs. Benzo[b] and benzo[k]fluoranthene may be

measured as an isomeric pair. MGK 264 is made up of two structural

isomers. These are listed separately in the data tables.

11.5.4 Each multi-component analyte can be identified by the presence of its

individual components in a characteristic pattern based on the relative

amounts of each component present. Chromatograms of standard

materials of multi-component analytes should be carefully evaluated, so

that these patterns can be recognized by the analyst.
Cx

(Ax) (Qis)

(Ais) RF V

525.2-28

12.0 DATA ANALYSIS AND CALCULATIONS

12.1 Complete chromatographic resolution is not necessary for accurate and precise

measurements of analyte concentrations if unique ions with adequate intensities

are available for quantitation. In validating this method, concentrations were

calculated by measuring the characteristic ions listed in Table 2. If the response

of any analyte exceeds the calibration rage established in Section 10.0, dilute the

extract and reanalyze.

12.1.1 Calculate analyte and surrogate concentrations, using the multipoint

calibration established in Section 10.0. Do not use daily calibration

verification data to quantitate analytes in samples.

where: C = concentration of analyte or surrogate in μg/L in the water x

 sample

A = integrated abundance of the quantitation ion of the analyte x

 in the sample

A = integrated abundance of the quantitation ion of the internal is

 standard in the sample

Qis = total quantity (in micrograms) of internal standard added

 to the water sample

V = original water sample volume in liters

RF = mean response factor of analyte from the initial calibration.

 RF is a unitless value

12.1.2 Alternatively, use the GC/MS system software or other available proven

software to compute the concentrations of the analytes and surrogates

from the linear regression established in Section 10.0. Do not use daily

calibration verification data to quantitate analytes in samples. 

12.1.3 Calculations should utilize all available digits of precision, but final

reported concentrations should be rounded to an appropriate number of

significant figures (one digit of uncertainty). Experience indicates that

three significant figures may be used for concentrations above 99 μg/L,

two significant figures for concentrations between 1-99 μg/L, and one

significant figure for lower concentrations.

12.2 To quantitate multi-component analytes (toxaphene and Aroclors), one of the

following methods should be used.
MDL S t

(n 1, 1 alpha 0.99)

525.2-29

Option 1 - Calculate an average RF or linear regression equation for each multicomponent analyte from the combined area of all its component peaks identified

in the calibration standard chromatogram, using two to three of the suggested

quantitation ions in Table 2.

Option 2 - Calculate an average response factor or linear regression equation for

each multi-component analyte using the combined areas of three to six of the

most intense and reproducible peaks in each of the calibration standard

chromatograms.

When quantifying multi-component analytes in samples, the analyst should use

caution to include only those peaks from the sample that are attributable to the

multi-component analyte. Option 1 should not be used if there are significant

interference peaks within the Aroclor or toxaphene pattern. Option 2 was used

to generate the data in Table 6.

13.0 METHOD PERFORMANCE

13.1 Single laboratory accuracy and precision data (Tables 3-6) for each listed analyte

(except multi-component analytes) were obtained at a concentration of 0.5 μg/L

and/or 5 μg/L in reagent water utilizing both the disk and the cartridge

technology and two different GC/MS systems, an ion trap and a quadrupole

mass spectrometer. Table 8 lists accuracy and precision data from replicate

determinations of method analytes in tap water using liquid-solid cartridge

extractions and the ion trap mass spectrometer. Any type of GC/MS system

may be used to perform this method if it meets the requirement in Sect. 6.10

and the quality control criteria in Section 9.0. The multi-component analytes

(i.e., toxaphene and Aroclors) are presented in Tables 5 and 6. The average

recoveries in the tables represent six to eight replicate analyses done over a

minimum of a two-day period. 

13.1.2 With these data, the method detection limits (MDL) in the tables were

calculated using the formula:

where: t = Student's t value for the 99% confidence level (n-1,1-alpha = 0.99)

 with n-1 degrees of freedom

n = number of replicates

S = standard deviation of replicate analyses

13.2 Problem Compounds
525.2-30

13.2.1 Some polycyclic aromatic hydrocarbons (PAH), including the labeled

PAHs used in this method as internal standards, are rapidly oxidized

and/or chlorinated in water containing residual chlorine. Therefore,

residual chlorine must be reduced at the time of sampling. These same

types of compounds, especially anthracene, benz[a]anthracene, and

benzo[a]pyrene, are susceptible to photodegradation. Therefore, care

should be taken to avoid exposing standards, samples, and extracts to

direct light. Low recoveries of some PAH compounds have been observed

when the cartridge or disk was air dried longer than 10 minutes (Section

11.1.4 and Section 11.2.4). Drying times longer than 10 minutes should

be avoided, or nitrogen may be used to dry the cartridge or disk to

minimize the possible oxidation of these analytes during the drying step.

13.2.2 Merphos is partially converted to DEF in aqueous matrices, and also

when introduced into a hot gas chromatographic injection system. The

efficiency of this conversion appears to be unpredictable and not

reproducible. Therefore, merphos cannot be quantified and can only be

identified by the presence of DEF in the sample.

13.2.3 Several of the nitrogen and/or phosphorus containing pesticides listed as

method analytes are difficult to chromatograph and appear as broad,

asymmetrical peaks. These analytes, whose peak shapes are typically

poor, are listed in Table 7. The method performance for these analytes is

strongly dependent on chromatographic efficiency and performance. 

Poor peak shapes will affect the linearity of the calibration curves and

result in poor accuracy at low concentrations. Also listed in Table 7 are

data generated at a mid-concentration level for these analytes. In most

cases, the data at this concentration meet the quality control criteria

requirements of the method.

13.2.4 Phthalate esters and other background components appear in variable

quantities in laboratory and field reagent blanks, and generally cannot be

accurately measured at levels below about 2 μg/L. Subtraction of the

concentration in the blank from the concentration in the sample at or

below the 2 μg/L level is not recommended because the concentration of

the background in the blank is highly variable.

13.2.5 Atraton and prometon are not efficiently extracted from the water at pH

2 due to what appears to be their ionization occurring in solution under

acidic conditions. In order to determine these analytes accurately, a

separate sample must be collected and dechlorinated with sodium sulfite,

but no HCl should be added at the time of collection. At neutral pH,

these two compounds are recovered from water with efficiencies greater
525.2-31

than 90%. The data in Tables 3, 4, 5, 6, and 8 are from samples

extracted at pH 2.

13.2.6 Carboxin, disulfoton, and disulfoton sulfoxide were found to be unstable

in water and began to degrade almost immediately. These analytes may

be identified by this method but not accurately measured.

13.2.7 Low recoveries of metribuzin were observed in samples fortified with

relatively high concentrations of additional method analytes. In samples

fortified with approximately 80 analytes at 5 μg/L each, metribuzin was

recovered at about 50% efficiency. This suggests that metribuzin may

break through the C-18 phase in highly contaminated samples resulting

in low recoveries.

13.2.8 If cyanazine is to be determined, a separate sample must be collected. 

Cyanazine degrades in the sample when it is stored under acidic

conditions or when sodium sulfite is present in the stored sample. 

Samples collected for cyanazine determination MUST NOT be

dechlorinated or acidified when collected. They should be iced or

refrigerated and analyzed within 14 days. However, these samples

MUST be dechlorinated and acidified immediately prior to fortification

with internal standards and surrogates, and extraction using the same

quantities of acid and sodium sulfite described in Section 8.0.

14.0 POLLUTION PREVENTION

14.1 This method utilizes liquid-solid extraction (LSE) technology to remove the

analytes from water. It requires the use of very small volumes of organic solvent

and very small quantities of pure analytes, thereby eliminating the potential

hazards to both the analyst and the environment involved with the use of large

volumes of organic solvents in conventional liquid-liquid extractions.

14.2 For information about pollution prevention that may be applicable to laboratory

operations, consult "Less Is Better: Laboratory Chemical Management for

Waste Reduction" available from the American Chemical Society's Department

of Government Relations and Science Policy, 1155 16th Street N.W.,

Washington, D.C. 20036.

15.0 WASTE MANAGEMENT

15.1 It is the laboratory's responsibility to comply with all federal, state, and local

regulations governing waste management, particu-larly the hazardous waste

identification rules and land disposal restrictions. The laboratory using this

method has the respons-ibility to protect the air, water, and land by minimizing

and controlling all releases from fume hoods and bench operations. Compliance
525.2-32

is also required with any sewage discharge permits and regulations. For further

information on waste management, see "The Waste Management Manual for

Laboratory Personnel", also avail-able from the American Chemical Society at

the address in Section 14.2.

16.0 REFERENCES

1. Glaser, J. A., D. L. Foerst, G. D. McKee, S. A. Quave, and W. L. Budde. "Trace

Analyses for Wastewaters", Environ. Sci. Technol. 1981 15, 1426-1435. or 40 CFR,

Part 136, Appendix B.

2. "Carcinogens - Working 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, August 1977.

3. "OSHA Safety and Health Standards, General Industry", (29CFR1910), Occupational

Safety and Health Administration, OSHA 2206, (Revised, January 1976).

4. "Safety in Academic Chemistry Laboratories", American Chemical Society Publication,

Committee on Chemical Safety, 3rd Edition, 1979.

5. Junk, G. A., M. J. Avery, J. J. Richard. "Interferences in Solid-Phase Extraction Using

C-18 Bonded Porous Silica Cartridges", Anal. Chem. 1988, 60, 1347.
525.2-33

17.0 TABLES, DIAGRAMS, FLOWCHARTS, AND VALIDATION DATA

TABLE 1. ION ABUNDANCE CRITERIA FOR BIS(PERFLUOROPHENYL)PHENYL PHOSPHINE (DECAFLUOROTRIPHENYLPHOSPHINE, DFTPP)

Mass Relative Abundance

(M/z) Criteria Purpose of Checkpoint1

51 10-80% of the base peak Low-mass sensitivity

68 <2% of Mass 69 Low-mass resolution

70 <2% of Mass 69 Low-mass resolution

127 10-80% of the base peak Low- to mid-mass sensitivity

197 <2% of Mass 198 Mid-mass resolution

198 Base peak or >50% of Mass 442 Mid-mass resolution and sensitivity

199 5-9% of Mass 198 Mid-mass resolution and isotope ratio

275 10-60% of the base peak Mid- to high-mass sensitivity

365 >1% of the base peak Baseline threshold

441 Present and < Mass 443 High-mass resolution

442 Base peak or >50% of Mass 198 High-mass resolution and sensitivity

443 15-24% of Mass 442 High-mass resolution and isotope ratio

All ions are used primarily to check the mass measuring accuracy of the mass 1

spectrometer and data system, and this is the most important part of the performance

test. The three resolution checks, which include natural abundance isotope ratios,

constitute the next most important part of the performance test. The correct setting of

the baseline threshold, as indicated by the presence of low intensity ions, is the next

most important part of the performance test. Finally, the ion abundance ranges are

designed to encourage some standardization to fragmentation patterns.
525.2-34

TABLE 2. RETENTION TIME DATA, QUANTITATION IONS, AND

INTERNAL STANDARD REFERENCES FOR METHOD ANALYTES

Compound Ion Reference #

Retention

Time (min:sec) Quantitation IS

A B

a b

Internal Standards

Acenaphthene-d10 (#1) 7:47 7:01 164

Chrysene-d12 (#2) 21:33 18:09 240

Phenanthrene-d10 (#3) 11:37 10:13 188

Surrogates

1,3-Dimethyl-2-Nitrobenzene 5:16 4:33 134 1

Perylene-d12 26:60 21:31 264 3

Triphenylphosphate 20:25 17:25 326/325 3

Target Analytes

Acenaphthylene 7:30 6:46 152 1

Alachlor 12:59 11:24 160 2

Aldrin 14:24 12:31 66 2

Ametryn 13:11 11:35 227/170 2

Anthracene 11:50 10:24 178 2

Aroclor 1016 7:30-14:00 152/256/292 2

Aroclor 1221 6:38-11:25 152/222/256 2

Aroclor 1232 6:38-13:54 152/256/292 2

Aroclor 1242 6:38-15:00 152/256/292 2

Aroclor 1248 8:47-15:00 152/256/292 2

Aroclor 1254 11:00- 220/326/360 2

18:00

Aroclor 1260 13:10- 326/360/394 2

21:00

Atraton 10:31 9:25 196/169 1

Atrazine 10:49 9:38 200/215 1/2

Benz[a]anthracene 21:31 18:08 228 3

Benzo[b]fluoranthene 25:33 20:44 252 3

Benzo[k]fluoranthene 25:45 20:48 252 3

Benzo[g,h,i]perylene 31:16 24:18 276 3

Benzo[a]pyrene 25:24 21:25 252 3

Bromacil 13:46 12:03 205 2

Butachlor 16:25 14:16 176/160 2

Butylate 6:60 6:23 57/146 1

Butylbenzylphthalate 19:39 16:53 149 2/3

Carboxin 17:37 15:13 143 2

Chlordane, (alpha-Chlordane) 16:43 14:28 375/373 2/3
TABLE 2. RETENTION TIME DATA, QUANTITATION IONS, AND

INTERNAL STANDARD REFERENCES FOR METHOD ANALYTES

Compound Ion Reference #

Retention

Time (min:sec) Quantitation IS

A B

a b

525.2-35

Chlordane, (gamma-Chlordane) 16:19 14:05 373 2/3

Chlordane, (trans-Nonachlor) 16:47 14:30 409 2/3

Chlorneb 7:47 7:05 191 1

Chlorobenzilate 18:22 15:52 139 2

2-Chlorobiphenyl 7:53 7:08 188 1

Chlorpropham 9:33 8:36 127 1

Chlorpyrifos 14:10 12:23 197/97 2

Chlorothalonil 11:38 10:15 266 2

Chrysene 21:39 18:13 228 3

Cyanazine 14:14 12:28 225/68 2

Cycloate 9:23 8:26 83/154 1

DCPA 14:20 12:30 301 2

4,4'-DDD 18:40 16:05 235/165 2

4,4'-DDE 17:20 14:59 246 2

4,4'-DDT 19:52 17:00 235/165 2

DEF 17:24 15:05 57/169 2

Diazinon 11:19 10:05 137/179 2

Dibenz[a,h]anthracene 30:32 23:47 278 3

Di-n-Butylphthalate 13:49 12:07 149 2

2,3-Dichlorobiphenyl 10:20 9:12 222/152 1

Dichlorvos 5:31 4:52 109 1

Dieldrin 17:35 15:09 79 2

Di(2-Ethylhexyl)adipate 20:11 17:19 129 2/3

Di(2-Ethylhexyl)phthalate 22:11 18:39 149 2/3

Diethylphthalate 8:68 7:53 149 1

Dimethylphthalate 7:13 6:34 163 1

2,4-Dinitrotoluene 8:08 7:22 165 1

2,6-Dinitrotoluene 7:19 6:40 165 1

Diphenamid 14:52 12:58 72/167 2

Disulfoton 11:43 10:22 88 2

Disulfoton Sulfone 16:28 14:17 213/153 2

Disulfoton Sulfoxide 6:09 5:31 97 1

Endosulfan I 16:44 14:26 195 2

Endosulfan II 18:35 15:59 195 2

Endosulfan Sulfate 19:47 16:54 272 2

Endrin 18:15 15:42 67/81 2

Endrin Aldehyde 19:02 16:20 67 2

EPTC 6:23 5:46 128 1

Ethoprop 9:19 8:23 158 1
TABLE 2. RETENTION TIME DATA, QUANTITATION IONS, AND

INTERNAL STANDARD REFERENCES FOR METHOD ANALYTES

Compound Ion Reference #

Retention

Time (min:sec) Quantitation IS

A B

a b

525.2-36

Etridiazole 7:14 6:37 211/183 1

Fenamiphos 16:48 14:34 303/154 2

Fenarimol 23:26 19:24 139 3

Fluorene 8:59 8:03 166 1

Fluridone 26:51 21:26 328 3

HCH, alpha 10:19 9:10 181 1

HCH, beta 10:57 9:41 181 2

HCH, delta 11:57 10:32 181 2

HCH, gamma (Lindane) 11:13 9:54 181 2

Heptachlor 13:19 11:37 100 2

Heptachlor epoxide 15:34 13:29 81 2

2,2',3,3',4,4',6-Heptachlorobiphen 21:23 18:04 394/396 3

yl

Hexachlorobenzene 10:27 9:15 284 1

2,2',4,4',5,6'-Hexachlorobiphenyl 17:32 15:09 360 2

Hexachlorocyclopentadiene 5:16 5:38 237 1

Hexazinone 20:00 17:06 171 2

Indeno[1,2,3-cd]pyrene 30:26 23:43 276 3

Isophorone 4:54 4:10 82 1

Merphos 15:38 13:35 209/153 2

Methoxychlor 21:36 18:14 227 3

Methyl Paraoxon 11:57 10:22 109 2

Metolachlor 14:07 12:20 162 2

Metribuzin 12:46 11:13 198 2

Mevinphos 5:54 6:19 127 1

MGK 264 - Isomer a 15:18 13:00 164/66 2

MGK 264 - Isomer b 14:55 13:19 164 2

Molinate 8:19 7:30 126 1

Napropamide 16:53 14:37 72 2

Norflurazon 19:31 16:46 145 2

2,2',3,3',4,5',6,6'-Octachlorobiphen 21:33 18:11 430/428 3

yl

Pebulate 7:18 6:40 128 1

2,2',3',4,6-Pentachlorobiphenyl 15:37 13:33 326 2

Pentachlorophenol 11:01 9:45 266 2

Permethrin, cis 24:25 20:01 183 3

Permethrin, trans 24:39 20:10 183 3

Phenanthrene 11:41 10:16 178 2

Prometon 10:39 9:32 225/168 2
TABLE 2. RETENTION TIME DATA, QUANTITATION IONS, AND

INTERNAL STANDARD REFERENCES FOR METHOD ANALYTES

Compound Ion Reference #

Retention

Time (min:sec) Quantitation IS

A B

a b

525.2-37

Prometryn 13:15 11:39 241/184 2

Pronamide 11:19 10:02 173 2

Propachlor 9:00 8:07 120 1

Propazine 10:54 9:43 214/172 2

Pyrene 16:41 14:24 202 2

Simazine 10:41 9:33 201/186 2

Simetryn 13:04 11:29 213 2

Stirofos 16:20 14:11 109 2

Tebuthiuron 8:00 7:16 156 1

Terbacil 11:44 10:24 161 2

Terbufos 11:14 9:58 57 2

Terbutryn 13:39 11:58 226/185 2

2,2',4,4'-Tetrachlorobiphenyl 14:02 12:14 292 2

Toxaphene 13:00- 159 2

21:00

Triademefon 14:30 12:40 57 2

2,4,5-Trichlorobiphenyl 12:44 10:53 256 2

Tricyclazole 17:15 14:51 189 2

Trifluralin 9:31 8:37 306 1

Vernolate 7:10 6:32 128 1

Single-ramp linear temperature program conditions (Section 10.2.3.2). a

Multi-ramp linear temperature program conditions (Section 10.2.3.1). b
525.2-38

TABLE 3. ACCURACY AND PRECISION DATA FROM EIGHT

DETERMINATIONS OF THE METHOD ANALYTES IN REAGENT WATER

USING LIQUID-SOLID C-18 CARTRIDGE EXTRACTION AND THE

QUADRUPOLE MASS SPECTROMETER

Compound (μg/L) (μg/L) (%) Conc.) (μg/L)

True Observed Deviatio (% of

Conc. Conc. n True MDL

Mean Standard Accuracy

Relative Method

Mean

Surrogates

1,3-Dimethyl-2-Nitrobenzene 5.0 4.7 3.9 94

Perylene-d12 5.0 4.9 4.8 98

Triphenylphosphate 5.0 5.5 6.3 110

Target Analytes

Acenaphthylene 0.50 0.45 8.2 91 0.11

Alachlor 0.50 0.47 12 93 0.16

Aldrin 0.50 0.40 9.3 80 0.11

Ametryn 0.50 0.44 6.9 88 0.092

Anthracene 0.50 0.53 4.3 106 0.068

Aroclor 1016 ND ND ND ND ND

Aroclor 1221 ND ND ND ND ND

Aroclor 1232 ND ND ND ND ND

Aroclor 1242 ND ND ND ND ND

Aroclor 1448 ND ND ND ND ND

Aroclor 1254 ND ND ND ND ND

Aroclor 1260 ND ND ND ND ND

Atraton 0.50 0.35 15 70 0.16 a

Atrazine 0.50 0.54 4.8 109 0.078

Benz[a]anthracene 0.50 0.41 16 82 0.20

Benzo[b]fluoranthene 0.50 0.49 20 98 0.30

Benzo[k]fluoranthene 0.50 0.51 35 102 0.54

Benzo[g,h,i]perylene 0.50 0.72 2.2 144 0.047

Benzo[a]pyrene 0.50 0.58 1.9 116 0.032

Bromacil 0.50 0.54 6.4 108 0.10

Butachlor 0.50 0.62 4.1 124 0.076

Butylate 0.50 0.52 4.1 105 0.064

Butylbenzylphthalate 0.50 0.77 11 154 0.25

Carboxin 5.0 3.8 12 76 1.4

Chlordane (alpha-Chlordane) 0.50 0.36 11 72 0.12

Chlordane (gamma-Chlordane) 0.50 0.40 8.8 80 0.11

Chlordane (trans-Nonachlor) 0.50 0.43 17 87 0.22
TABLE 3. ACCURACY AND PRECISION DATA FROM EIGHT

DETERMINATIONS OF THE METHOD ANALYTES IN REAGENT WATER

USING LIQUID-SOLID C-18 CARTRIDGE EXTRACTION AND THE

QUADRUPOLE MASS SPECTROMETER

Compound (μg/L) (μg/L) (%) Conc.) (μg/L)

True Observed Deviatio (% of

Conc. Conc. n True MDL

Mean Standard Accuracy

Relative Method

Mean

525.2-39

Chlorneb 0.50 0.51 5.7 102 0.088

Chlorobenzilate 5.0 6.5 6.9 130 1.3

2-Chlorobiphenyl 0.50 0.40 7.2 80 0.086

Chlorpropham 0.50 0.61 6.2 121 0.11

Chlorpyrifos 0.50 0.55 2.7 110 0.044

Chlorothalonil 0.50 0.57 6.9 113 0.12

Chrysene 0.50 0.39 7.0 78 0.082

Cyanazine 0.50 0.71 8.0 141 0.17

Cycloate 0.50 0.52 6.1 104 0.095

DCPA 0.50 0.55 5.8 109 0.094

4,4'-DDD 0.50 0.54 4.4 107 0.071

4,4'-DDE 0.50 0.40 6.3 80 0.075

4,4'-DDT 0.50 0.79 3.5 159 0.083

Diazinon 0.50 0.41 8.8 83 0.11

Dibenz[a,h]anthracene 0.50 0.53 0.5 106 0.010

Di-n-butylphthalate ND ND ND ND ND

2,3-Dichlorobiphenyl 0.50 0.40 11 80 0.14

Dichlorvos 0.50 0.55 9.1 110 0.15

Dieldrin 0.50 0.48 3.7 96 0.053

Di(2-ethylhexyl)adipate 0.50 0.42 7.1 84 0.090

Di(2-ethylhexyl)phthalate ND ND ND ND ND

Diethylphthalate 0.50 0.59 9.6 118 0.17

Dimethylphthalate 0.50 0.60 3.2 120 0.058

2,4-Dinitrotoluene 0.50 0.60 5.6 119 0.099

2,6-Dinitrotoluene 0.50 0.60 8.8 121 0.16

Diphenamid 0.50 0.54 2.5 107 0.041

Disulfoton 5.0 3.99 5.1 80 0.62

Disulfoton Sulfone 0.50 0.74 3.2 148 0.070

Disulfoton Sulfoxide 0.50 0.58 12 116 0.20

Endosulfan I 0.50 0.55 18 110 0.30

Endosulfan II 0.50 0.50 29 99 0.44

Endosulfan Sulfate 0.50 0.62 7.2 124 0.13

Endrin 0.50 0.54 18 108 0.29

Endrin Aldehyde 0.50 0.43 15 87 0.19
TABLE 3. ACCURACY AND PRECISION DATA FROM EIGHT

DETERMINATIONS OF THE METHOD ANALYTES IN REAGENT WATER

USING LIQUID-SOLID C-18 CARTRIDGE EXTRACTION AND THE

QUADRUPOLE MASS SPECTROMETER

Compound (μg/L) (μg/L) (%) Conc.) (μg/L)

True Observed Deviatio (% of

Conc. Conc. n True MDL

Mean Standard Accuracy

Relative Method

Mean

525.2-40

EPTC 0.50 0.50 7.2 100 0.11

Ethoprop 0.50 0.62 6.1 123 0.11

Etridiazole 0.50 0.69 7.6 139 0.16

Fenamiphos 5.0 5.2 6.1 103 0.95

Fenarimol 5.0 6.3 6.5 126 1.2

Fluorene 0.50 0.46 4.2 93 0.059

Fluridone 5.0 5.1 3.6 102 0.55

HCH, alpha 0.50 0.51 13 102 0.20

HCH, beta 0.50 0.51 20 102 0.31

HCH, delta 0.50 0.56 13 112 0.21

HCH, gamma (Lindane) 0.50 0.63 8.0 126 0.15

Heptachlor 0.50 0.41 12 83 0.15

Heptachlor Epoxide 0.50 0.35 5.5 70 0.058

2,2',3,3',4,4',6-Heptachlorobiphenyl 0.50 0.35 10 71 0.11

Hexachlorobenzene 0.50 0.39 11 78 0.13

2,2',4,4',5,6'-Hexachlorobiphenyl 0.50 0.37 9.6 73 0.11

Hexachlorocyclopentadiene 0.50 0.43 5.6 86 0.072

Hexazinone 0.50 0.70 5.0 140 0.11

Indeno[1,2,3-cd]pyrene 0.50 0.69 2.7 139 0.057

Isophorone 0.50 0.44 3.2 88 0.042

Methoxychlor 0.50 0.62 4.2 123 0.077

Methyl Paraoxon 0.50 0.57 10 115 0.17

Metolachlor 0.50 0.37 8.0 75 0.090

Metribuzin 0.50 0.49 11 97 0.16

Mevinphos 0.50 0.57 12 114 0.20

MGK 264 - Isomer a 0.33 0.39 3.4 116 0.040

MGK 264 - Isomer b 0.17 0.16 6.4 96 0.030

Molinate 0.50 0.53 5.5 105 0.087

Napropamide 0.50 0.58 3.5 116 0.060

Norflurazon 0.50 0.63 7.1 126 0.13

2,2',3,3',4,5',6,6'-Octachlorobipheny 0.50 0.50 8.7 101 0.13

l

Pebulate 0.50 0.49 5.4 98 0.080

2,2',3',4,6-Pentachlorobiphenyl 0.50 0.30 16 61 0.15
TABLE 3. ACCURACY AND PRECISION DATA FROM EIGHT

DETERMINATIONS OF THE METHOD ANALYTES IN REAGENT WATER

USING LIQUID-SOLID C-18 CARTRIDGE EXTRACTION AND THE

QUADRUPOLE MASS SPECTROMETER

Compound (μg/L) (μg/L) (%) Conc.) (μg/L)

True Observed Deviatio (% of

Conc. Conc. n True MDL

Mean Standard Accuracy

Relative Method

Mean

525.2-41

Pentachlorophenol ND ND ND ND ND

Permethrin, cis 0.25 0.30 3.7 121 0.034

Permethrin, trans 0.75 0.82 2.7 109 0.067

Phenathrene 0.50 0.46 4.3 92 0.059

Prometon 0.50 0.30 42 60 0.38 a

Prometryn 0.50 0.46 5.6 92 0.078

Pronamide 0.50 0.54 5.9 108 0.095

Propachlor 0.50 0.49 7.5 98 0.11

Propazine 0.50 0.54 7.1 108 0.12

Pyrene 0.50 0.38 5.7 77 0.066

Simazine 0.50 0.55 9.1 109 0.15

Simetryn 0.50 0.52 8.2 105 0.13

Stirofos 0.50 0.75 5.8 149 0.13

Tebuthiuron 5.0 6.8 14 136 2.8

Terbacil 5.0 4.9 14 97 2.1

Terbufos 0.50 0.53 6.1 106 0.096

Terbutryn 0.50 0.47 7.6 95 0.11

2,2',4,4'-Tetrachlorobiphenyl 0.50 0.36 4.1 71 0.044

Toxaphene ND ND ND ND ND

Triademefon 0.50 0.57 20 113 0.33

2,4,5-Trichlorobiphenyl 0.50 0.38 6.7 75 0.075

Tricyclazole 5.0 4.6 19 92 2.6

Trifluralin 0.50 0.63 5.1 127 0.096

Vernolate 0.50 0.51 5.5 102 0.084

ND = Not determined.

Data from samples extracted at pH 2 - for accurate determination of this analyte, a a

separate sample must be extracted at ambient pH.
525.2-42

TABLE 4. ACCURACY AND PRECISION DATA FROM EIGHT

DETERMINATIONS OF THE METHOD ANALYTES IN REAGENT WATER

USING LIQUID-SOLID C-18 DISK EXTRACTION AND THE QUADRUPOLE

MASS SPECTROMETER

Compound (μg/L) (μg/L) (%) Conc.) (μg/L)

True Observed Deviatio Accuracy

Conc. Conc. n (% of True MDL

Mean Standard Method

Relative Mean

Surrogates

1,3-Dimethyl-2-Nitrobenzene 5.0 4.6 2.6 93

Perylene-d12 5.0 4.8 1.6 95

Triphenylphosphate 5.0 5.0 2.5 101

Target Analytes

Acenaphthylene 0.50 0.47 8.4 94 0.12

Alachlor 0.50 0.50 5.8 100 0.087

Aldrin 0.50 0.39 13 78 0.16

Ametryn 0.50 0.38 28 76 0.32

Anthracene 0.50 0.49 13 98 0.18

Aroclor 1016 ND ND ND ND ND

Aroclor 1221 ND ND ND ND ND

Aroclor 1232 ND ND ND ND ND

Aroclor 1242 ND ND ND ND ND

Aroclor 1248 ND ND ND ND ND

Aroclor 1254 ND ND ND ND ND

Aroclor 1260 ND ND ND ND ND

Atraton 0.50 0.07 139 19 0.29 a

Atrazine 0.50 0.60 3.7 119 0.065

Benz[a]anthracene 0.50 0.38 6.1 76 0.070

Benzo[b]fluoranthene 0.50 0.61 2.5 121 0.046

Benzo[k]fluoranthene 0.50 0.61 27 122 0.50

Benzo[g,h,i]perylene 0.50 0.69 1.4 138 0.029

Benzo[a]pyrene 0.50 0.58 6.1 116 0.11

Bromacil 0.50 0.49 23 99 0.34

Butachlor 0.50 0.63 2.1 127 0.039

Butylate 0.50 0.50 4.9 99 0.073

Butylbenzylphthalate 0.50 0.78 5.5 156 0.13

Carboxin 5.0 2.7 12 54 0.98

Chlordane (alpha-Chlordane) 0.50 0.37 5.5 74 0.061

Chlordane (gamma-Chlordane) 0.50 0.40 4.2 80 0.050

Chlordane (trans-Nonachlor) 0.50 0.45 7.8 90 0.11

Chlorneb 0.50 0.51 7.3 100 0.11

Chlorobenzilate 5.0 7.9 8.4 156 2.0
TABLE 4. ACCURACY AND PRECISION DATA FROM EIGHT

DETERMINATIONS OF THE METHOD ANALYTES IN REAGENT WATER

USING LIQUID-SOLID C-18 DISK EXTRACTION AND THE QUADRUPOLE

MASS SPECTROMETER

Compound (μg/L) (μg/L) (%) Conc.) (μg/L)

True Observed Deviatio Accuracy

Conc. Conc. n (% of True MDL

Mean Standard Method

Relative Mean

525.2-43

2-Chlorobiphenyl 0.50 0.42 1.9 84 0.023

Chlorpropham 0.50 0.68 5.4 134 0.11

Chlorpyrifos 0.50 0.61 6.5 119 0.12

Chlorothalonil 0.50 0.59 6.5 116 0.11

Chrysene 0.50 0.35 3.6 71 0.038

Cyanazine 0.50 0.68 15 136 0.31

Cycloate 0.50 0.53 4.9 106 0.077

DCPA 0.50 0.55 4.5 110 0.073

4,4'-DDD 0.50 0.67 14 137 0.28

4,4'-DDE 0.50 0.48 4.9 96 0.070

4,4'-DDT 0.50 0.93 3.2 187 0.090

Diazinon 0.50 0.56 6.8 109 0.11

Dibenz[a,h]anthracene 0.50 0.61 15 122 0.28

Di-n-Butylphthalate ND ND ND ND ND

2,3-Dichlorobiphenyl 0.50 0.46 8.1 93 0.11

Dichlorvos 0.50 0.54 5.6 108 0.092

Dieldrin 0.50 0.52 7.8 104 0.12

Di-(2-ethylhexyl)adipate ND ND ND ND ND

Di(2-ethylhexyl)phthalate ND ND ND ND ND

Diethylphthalate 0.50 0.66 10 132 0.20

Dimethylphthalate 0.50 0.57 8.3 114 0.14

2,4-Dinitrotoluene 0.50 0.54 5.7 109 0.093

2,6-Dinitrotoluene 0.50 0.48 4.9 96 0.071

Diphenamid 0.50 0.60 3.8 118 0.067

Disulfoton 5.0 4.8 9.4 96 1.3

Disulfoton Sulfone 0.50 0.82 2.8 164 0.070

Disulfoton Sulfoxide 0.50 0.68 8.9 136 0.18

Endosulfan I 0.50 0.65 10 132 0.20

Endosulfan II 0.50 0.60 21 122 0.38

Endosulfan Sulfate 0.50 0.67 6.1 133 0.12

Endrin 0.50 0.58 18 116 0.31

Endrin Aldehyde 0.50 0.51 16 101 0.24

EPTC 0.50 0.50 3.8 100 0.056

Ethoprop 0.50 0.69 2.3 138 0.048

Etridiazole 0.50 0.74 4.0 149 0.090
TABLE 4. ACCURACY AND PRECISION DATA FROM EIGHT

DETERMINATIONS OF THE METHOD ANALYTES IN REAGENT WATER

USING LIQUID-SOLID C-18 DISK EXTRACTION AND THE QUADRUPOLE

MASS SPECTROMETER

Compound (μg/L) (μg/L) (%) Conc.) (μg/L)

True Observed Deviatio Accuracy

Conc. Conc. n (% of True MDL

Mean Standard Method

Relative Mean

525.2-44

Fenamiphos 5.0 6.3 8.8 124 1.6

Fenarimol 5.0 7.5 5.5 150 1.2

Fluorene 0.50 0.47 8.1 94 0.11

Fluridone 5.0 5.7 4.5 114 0.77

HCH, alpha 0.50 0.54 12 107 0.20

HCH, beta 0.50 0.57 17 112 0.28

HCH, delta 0.50 0.61 8.2 120 0.15

HCH, gamma (Lindane) 0.50 0.62 6.6 124 0.12

Heptachlor 0.50 0.40 12 80 0.14

Heptachlor Epoxide 0.50 0.36 8.7 71 0.093

2,2',3,3',4,4',6-Heptachlorobiphen 0.50 0.36 13 71 0.14

yl

Hexachlorobenzene 0.50 0.47 8.3 95 0.12

2,2',4,4',5,6'-Hexachlorobiphenyl 0.50 0.41 11 83 0.13

Hexachlorocyclopentadiene 0.50 0.42 12 84 0.16

Hexazinone 0.50 0.85 5.6 169 0.14

Indeno[1,2,3-cd]pyrene 0.50 0.69 2.4 138 0.050

Isophorone 0.50 0.41 4.2 83 0.052

Methoxychlor 0.50 0.58 1.9 117 0.033

Methyl Paraoxon 0.50 0.62 14 122 0.25

Metolachlor 0.50 0.38 7.5 75 0.084

Metribuzin 0.50 0.54 3.9 107 0.062

Mevinphos 0.50 0.72 3.7 143 0.079

MGK 264 - Isomer a 0.33 0.40 8.8 119 0.10

MGK 264 - Isomer b 0.17 0.17 5.9 103 0.030

Molinate 0.50 0.53 3.2 105 0.050

Napropamide 0.50 0.64 5.9 126 0.11

Norflurazon 0.50 0.70 4.2 141 0.089

2,2',3,3',4,5',6,6'-Octachloro- 0.50 0.51 4.2 102 0.064

 biphenyl

Pebulate 0.50 0.48 5.8 96 0.084

2,2',3',4,6-Pentachlorobiphenyl 0.50 0.35 4.2 70 0.044

Pentachlorophenol 2.0 1.9 16 95 .89

Permethrin,cis 0.25 0.32 3.3 126 0.031

Permethrin,trans 0.75 0.89 1.9 118 0.051
TABLE 4. ACCURACY AND PRECISION DATA FROM EIGHT

DETERMINATIONS OF THE METHOD ANALYTES IN REAGENT WATER

USING LIQUID-SOLID C-18 DISK EXTRACTION AND THE QUADRUPOLE

MASS SPECTROMETER

Compound (μg/L) (μg/L) (%) Conc.) (μg/L)

True Observed Deviatio Accuracy

Conc. Conc. n (% of True MDL

Mean Standard Method

Relative Mean

525.2-45

Phenathrene 0.50 0.48 5.0 95 0.071

Prometon 0.50 0.21 66 45 0.44 a

Prometryn 0.50 0.46 24 93 0.33

Pronamide 0.50 0.58 7.1 113 0.12

Propachlor 0.50 0.49 5.4 98 0.079

Propazine 0.50 0.59 5.0 117 0.088

Pyrene 0.50 0.40 3.2 79 0.038

Simazine 0.50 0.60 10 120 0.18

Simetryn 0.50 0.41 15 83 0.19

Stirofos 0.50 0.84 3.2 168 0.081

Tebuthiuron 5.0 9.3 8.6 187 2.4

Terbacil 5.0 5.0 11 100 1.7

Terbufos 0.50 0.62 4.2 123 0.077

Terbutryn 0.50 0.46 23 94 0.32

2,2',4,4'-Tetrachlorobiphenyl 0.50 0.40 7.4 79 0.088

Toxaphene ND ND ND ND ND

Triademefon 0.50 0.73 7.2 145 0.16

2,4,5-Trichlorobiphenyl 0.50 0.44 5.3 89 0.071

Tricyclazole 5.0 6.8 12 137 2.4

Trifluralin 0.50 0.62 2.6 124 0.048

Vernolate 0.50 0.51 3.4 100 0.051

ND = Not determined.

Data from samples extracted at ph 2 - for accurate determination of this analyte, a a

separate sample must be extracted at ambient pH.
525.2-46

TABLE 5. ACCURACY AND PRECISION DATA FROM EIGHT

DETERMINATIONS OF THE METHOD ANALYTES IN REAGENT WATER

USING LIQUID-SOLID C-18 CARTRIDGE EXTRACTION AND THE ION

TRAP MASS SPECTROMETER

Compound (μg/L) (μg/L) (%) Conc.) (μg/L)

True Observed Deviatio Accuracy

Conc. Conc. n (% of True MDL

Mean Standard Method

Relative Mean

Surrogates

1,3-Dimethyl-2-Nitrobenzene 5.0 4.9 8.4 98

Perylene-d12 5.0 4.3 18 86

Triphenylphosphate 5.0 4.8 13 96

Target Analytes

Acenaphthylene 0.50 0.50 8.8 100 0.13

Alachlor 0.50 0.58 4.0 115 0.069

Aldrin 0.50 0.42 3.5 85 0.045

Ametryn 0.50 0.46 3.3 91 0.045

Anthracene 0.50 0.42 3.8 84 0.048

Aroclor 1016 1.0 1.1 4.4 113 0.15

Aroclor 1221 ND ND ND ND ND

Aroclor 1232 ND ND ND ND ND

Aroclor 1242 ND ND ND ND ND

Aroclor 1248 ND ND ND ND ND

Aroclor 1254 1.0 1.1 17 110 0.56 a

Aroclor 1260 1.0 0.96 9.3 96 0.27

Atraton 0.50 0.35 11 70 0.12 c

Atrazine 0.50 0.55 5.0 109 0.081

Benz[a]anthracene 0.50 0.43 7.3 85 0.093

Benzo[b]fluoranthene 0.50 0.44 16 88 0.21

Benzo[k]fluoranthene 0.50 0.34 22 68 0.23

Benzo[g,h,i]perylene 0.50 0.38 31 76 0.35

Benzo[a]pyrene 0.50 0.36 21 73 0.23

Bromacil 0.50 0.45 9.1 90 0.12

Butachlor 0.50 0.67 12 133 0.24

Butylate 0.50 0.52 5.2 104 0.082

Butylbenzylphthalate 5.0 5.7 7.7 114 1.4 b

Carboxin 0.50 0.58 22 117 0.38

Chlordane, (alpha-Chlordane) 0.50 0.47 12 95 0.17

Chlordane, (gamma- 0.50 0.50 10 99 0.16

 Chlordane)

Chlordane, (trans-Nonachlor) 0.50 0.48 11 96 0.16
TABLE 5. ACCURACY AND PRECISION DATA FROM EIGHT

DETERMINATIONS OF THE METHOD ANALYTES IN REAGENT WATER

USING LIQUID-SOLID C-18 CARTRIDGE EXTRACTION AND THE ION

TRAP MASS SPECTROMETER

Compound (μg/L) (μg/L) (%) Conc.) (μg/L)

True Observed Deviatio Accuracy

Conc. Conc. n (% of True MDL

Mean Standard Method

Relative Mean

525.2-47

Chlorneb 0.50 0.51 8.1 103 0.13

Chlorobenzilate 0.50 0.61 9.7 123 0.17

2-Chlorobiphenyl 0.50 0.47 4.8 94 0.068

Chlorpropham 0.50 0.55 8.1 109 0.13

Chlorpyrifos 0.50 0.50 2.4 99 0.035

Chlorothalonil 0.50 0.62 5.3 123 0.098

Chrysene 0.50 0.50 9.2 99 0.14

Cyanazine 0.50 0.49 13 97 0.19

Cycloate 0.50 0.52 7.6 103 0.12

DCPA 0.50 0.55 7.2 109 0.12

4,4'-DDD 0.50 0.52 3.6 103 0.055

4,4'-DDE 0.50 0.41 5.8 81 0.070

4,4'-DDT 0.50 0.54 2.4 108 0.039

Diazinon 0.50 0.37 2.7 75 0.030

Dibenz[a,h]anthracene 0.50 0.37 29 74 0.32

Di-n-Butylphthalate 5.0 6.2 4.6 124 0.89 b

2,3-Dichlorobiphenyl 0.50 0.45 5.8 90 0.079

Dichlorvos 0.50 0.53 8.0 106 0.13

Dieldrin 0.50 0.50 10 100 0.15

Di(2-Ethylhexyl)adipate 0.50 0.59 18 117 0.31

Di(2-Ethylhexyl)phthalate 5.0 6.5 6.6 130 1.3 b

Diethylphthalate 0.50 0.63 15 126 0.28

Dimethylphthalate 0.50 0.51 9.5 102 0.14

2,4-Dinitrotoluene 0.50 0.45 18 91 0.24

2,6-Dinitrotoluene 0.50 0.40 17 80 0.20

Diphenamid 0.50 0.55 6.5 111 0.11

Disulfoton 0.50 0.62 9.8 124 0.18

Disulfoton Sulfone 0.50 0.64 3.5 128 0.068

Disulfoton Sulfoxide 0.50 0.57 8.6 114 0.15

Endosulfan I 0.50 0.60 6.1 121 0.11

Endosulfan II 0.50 0.64 3.9 128 0.074

Endosulfan Sulfate 0.50 0.58 5.4 116 0.093

Endrin 0.50 0.62 18 124 0.34

Endrin Aldehyde 0.50 0.58 8.7 116 0.15

EPTC 0.50 0.53 7.7 105 0.12
TABLE 5. ACCURACY AND PRECISION DATA FROM EIGHT

DETERMINATIONS OF THE METHOD ANALYTES IN REAGENT WATER

USING LIQUID-SOLID C-18 CARTRIDGE EXTRACTION AND THE ION

TRAP MASS SPECTROMETER

Compound (μg/L) (μg/L) (%) Conc.) (μg/L)

True Observed Deviatio Accuracy

Conc. Conc. n (% of True MDL

Mean Standard Method

Relative Mean

525.2-48

Ethoprop 0.50 0.62 10 124 0.19

Etridiazole 0.50 0.61 6.5 122 0.12

Fenamiphos 0.50 0.67 12 133 0.24

Fenarimol 0.50 0.74 11 148 0.25

Fluorene 0.50 0.49 9.0 98 0.13

Fluridone 5.0 5.2 2.5 105 0.39

HCH, alpha 0.50 0.55 6.8 109 0.11

HCH, beta 0.50 0.54 5.3 107 0.085

HCH, delta 0.50 0.52 3.1 105 0.049

HCH, gamma (Lindane) 0.50 0.53 5.3 105 0.084

Heptachlor 0.50 0.50 4.1 100 0.061

Heptachlor Epoxide 0.50 0.54 8.2 108 0.13

2,2',3,3',4,4',6-Heptachloro- 0.50 0.45 11 90 0.15

 biphenyl

Hexachlorobenzene 0.50 0.41 6.0 82 0.074

2,2',4,4',5,6'-Hexachloro- 0.50 0.40 15 80 0.18

 biphenyl

Hexachlorocyclopentadiene 0.50 0.34 13 68 0.13

Hexazinone 0.50 0.80 5.6 159 0.14

Indeno[1,2,3-cd]pyrene 0.50 0.36 28 71 0.30

Isophorone 0.50 0.54 7.9 107 0.13

Methoxychlor 0.50 0.58 7.7 115 0.13

Methyl Paraoxon 0.50 0.85 3.7 170 0.094

Metolachlor 0.50 0.58 4.8 117 0.085

Metribuzin 0.50 0.54 14 108 0.22

Mevinphos 0.50 0.47 12 95 0.17

MGK 264 - Isomer a 0.33 0.38 9.5 113 0.11

MGK 264 - Isomer b 0.16 0.18 5.4 105 0.029

Molinate 0.50 0.55 5.2 111 0.086

Napropamide 0.50 0.63 10 127 0.20

Norflurazon 0.50 0.82 3.8 165 0.093

2,2',3,3',4,5',6,6'-Octachloro- 0.50 0.49 19 99 0.28

 biphenyl

Pebulate 0.50 0.56 6.1 112 0.10
TABLE 5. ACCURACY AND PRECISION DATA FROM EIGHT

DETERMINATIONS OF THE METHOD ANALYTES IN REAGENT WATER

USING LIQUID-SOLID C-18 CARTRIDGE EXTRACTION AND THE ION

TRAP MASS SPECTROMETER

Compound (μg/L) (μg/L) (%) Conc.) (μg/L)

True Observed Deviatio Accuracy

Conc. Conc. n (% of True MDL

Mean Standard Method

Relative Mean

525.2-49

2,2',3',4,6-Pentachlorobiphen 0.50 0.43 8.7 86 0.11

yl

Pentachlorophenol 2.0 2.4 10 119 0.72

Permethrin,cis 0.25 0.45 3.2 179 0.043

Permethrin,trans 0.75 1.1 2.2 153 0.074

Phenanthrene 0.50 0.48 4.8 96 0.069

Prometon 0.50 0.24 27 48 0.20 c

Prometryn 0.50 0.46 3.0 92 0.041

Pronamide 0.50 0.56 5.3 113 0.089

Propachlor 0.50 0.56 8.6 112 0.14

Propazine 0.50 0.52 4.3 103 0.066

Pyrene 0.50 0.47 11 95 0.16

Simazine 0.50 0.48 8.8 96 0.13

Simetryn 0.50 0.48 2.9 96 0.042

Stirofos 0.50 0.80 3.9 160 0.093

Tebuthiuron 0.50 0.67 7.4 134 0.15

Terbacil 0.50 0.59 12 119 0.22

Terbufos 0.50 0.46 11 92 0.15

Terbutryn 0.50 0.48 2.6 97 0.038

2,2',4,4'-Tetrachlorobiphenyl 0.50 0.40 6.4 81 0.077

Toxaphene 10 11 4.9 118 1.7

Triademefon 0.50 0.73 6.4 146 0.14

2,4,5-Trichlorobiphenyl 0.50 0.44 3.3 88 0.043

Tricyclazole 0.50 0.63 16 127 0.31

Trifluralin 0.50 0.62 13 124 0.24

Vernolate 0.50 0.50 9.3 101 0.14

Seven replicates. a

Seven replicates in fortified tap water. b

Data from samples extracted at pH 2 - for accurate determination of this analyte, a c

separate sample must be extracted at ambient pH.
525.2-50

TABLE 6. ACCURACY AND PRECISION DATA FROM EIGHT

DETERMINATIONS OF THE METHOD ANALYTES IN REAGENT WATER

USING LIQUID-SOLID C-18 DISK EXTRACTION AND THE ION TRAP

MASS SPECTROMETER

Compound (μg/L) (μg/L) (%) Conc.) (μg/L)

True Observed Deviatio Accuracy

Conc. Conc. n (% of True MDL

Mean Standard Method

Relative Mean

Surrogates

1,3-dimethyl-2-nitrobenzene 5.0 4.9 10 98

perylene-d12 5.0 4.9 4.5 98

triphenylphosphate 5.0 5.9 8.1 117

Target Analytes

Acenaphthylene 0.50 0.51 4.5 102 0.068

Alachlor 0.50 0.54 6.6 108 0.11

Aldrin 0.50 0.45 6.3 90 0.085

Ametryn 0.50 0.41 23 82 0.29

Anthracene 0.50 0.39 15 79 0.18

Aroclor 1016 0.20 0.25 4.7 123 0.040

Aroclor 1221 0.20 0.26 6.1 130 0.054

Aroclor 1232 0.20 0.24 4.7 121 0.042

Aroclor 1242 0.20 0.26 4.9 129 0.043

Aroclor 1248 0.20 0.24 4.1 118 0.038

Aroclor 1254 0.20 0.22 3.7 110 0.028

Aroclor 1260 0.20 0.21 2.2 108 0.018 a

Atraton 0.50 0.10 46 21 0.14 d

Atrazine 0.50 0.56 4.6 111 0.076

Benz[a]anthracene 0.50 0.44 7.4 88 0.098

Benzo[b]fluoranthene 0.50 0.50 9.1 100 0.14

Benzo[k]fluoranthene 0.50 0.46 2.2 91 0.031

Benzo[g,h,i]perylene 0.50 0.47 7.9 95 0.11

Benzo[a]pyrene 0.50 0.44 12 89 0.16

Bromacil 0.50 0.49 4.4 99 0.066

Butachlor 0.50 0.66 5.1 132 0.10

Butylate 0.50 0.50 5.4 100 0.082

Butylbenzylphthalate 5.0 5.7 7.7 114 1.4 b

Carboxin 0.50 0.40 38.1 79 0.45

Chlordane, (alpha-Chlordane) 0.50 0.50 4.3 101 0.065

Chlordane, (gamma-Chlordane) 0.50 0.51 7.2 102 0.11

Chlordane, (trans-Nonachlor) 0.50 0.52 6.2 104 0.097

Chlorneb 0.50 0.54 6.3 108 0.10
TABLE 6. ACCURACY AND PRECISION DATA FROM EIGHT

DETERMINATIONS OF THE METHOD ANALYTES IN REAGENT WATER

USING LIQUID-SOLID C-18 DISK EXTRACTION AND THE ION TRAP

MASS SPECTROMETER

Compound (μg/L) (μg/L) (%) Conc.) (μg/L)

True Observed Deviatio Accuracy

Conc. Conc. n (% of True MDL

Mean Standard Method

Relative Mean

525.2-51

Chlorobenzilate 0.50 0.59 9.7 117 0.17

2-Chlorobiphenyl 0.50 0.50 4.7 100 0.070

Chlorpropham 0.50 0.55 4.7 111 0.079

Chlorpyrifos 0.50 0.54 11 109 0.18

Chlorothalonil 0.50 0.59 4.4 119 0.079

Chrysene 0.50 0.48 6.1 96 0.088

Cyanazine 0.50 0.52 8.3 105 0.13

Cycloate 0.50 0.51 4.1 102 0.063

DCPA 0.50 0.53 3.2 105 0.051

4,4'-DDD 0.50 0.63 16 127 0.31

4,4'-DDE 0.50 0.48 3.7 96 0.054

4,4'-DDT 0.50 0.58 7.2 117 0.13

Diazinon 0.50 0.50 4.5 101 0.068

Dibenz[a,h]anthracene 0.50 0.47 9.9 94 0.14

Di-n-Butylphthalate 5.0 5.7 3.3 115 0.59 b

2,3-Dichlorobiphenyl 0.50 0.50 2.6 100 0.039

Dichlorvos 0.50 0.50 8.7 99 0.13

Dieldrin 0.50 0.53 7.0 106 0.11

Di(2-Ethylhexyl)adipate 5.0 5.4 7.5 107 1.3 b

Di(2-Ethylhexyl)phthalate 5.0 5.7 2.6 114 0.46 b

Diethylphthalate 0.50 0.68 5.0 137 0.10

Dimethylphthalate 0.50 0.51 5.0 102 0.077

2,4-Dinitrotoluene 0.50 0.30 8.1 59 0.072

2,6-Dinitrotoluene 0.50 0.28 6.4 56 0.054

Diphenamid 0.50 0.56 6.4 112 0.11

Disulfoton 0.50 0.70 5.3 139 0.11

Disulfoton Sulfone 0.50 0.64 5.9 128 0.11

Disulfoton Sulfoxide 0.50 0.60 3.8 119 0.068

Endosulfan I 0.50 0.61 4.9 122 0.089

Endosulfan II 0.50 0.66 6.1 131 0.12

Endosulfan Sulfate 0.50 0.57 9.0 115 0.16

Endrin 0.50 0.68 7.9 137 0.16

Endrin Aldehyde 0.50 0.57 2.8 114 0.048

EPTC 0.50 0.48 5.2 97 0.076

Ethoprop 0.50 0.61 7.5 122 0.14
TABLE 6. ACCURACY AND PRECISION DATA FROM EIGHT

DETERMINATIONS OF THE METHOD ANALYTES IN REAGENT WATER

USING LIQUID-SOLID C-18 DISK EXTRACTION AND THE ION TRAP

MASS SPECTROMETER

Compound (μg/L) (μg/L) (%) Conc.) (μg/L)

True Observed Deviatio Accuracy

Conc. Conc. n (% of True MDL

Mean Standard Method

Relative Mean

525.2-52

Etridiazole 0.50 0.54 4.2 108 0.067

Fenamiphos 0.50 0.67 10 133 0.20

Fenarimol 0.50 0.59 5.8 118 0.10

Fluorene 0.50 0.53 3.4 106 0.054

Fluridone 5.0 5.2 2.3 104 0.16

HCH, alpha 0.50 0.55 5.0 110 0.083

HCH, beta 0.50 0.54 4.1 109 0.068

HCH, delta 0.50 0.53 3.6 106 0.058

HCH, gamma (Lindane) 0.50 0.50 3.2 100 0.047

Heptachlor 0.50 0.49 4.0 98 0.059

Heptachlor Epoxide 0.50 0.50 3.2 100 0.048

2,2',3,3',4,4',6-Heptachloro- 0.50 0.46 7.3 92 0.10

 biphenyl

Hexachlorobenzene 0.50 0.49 3.4 97 0.049

2,2',4,4',5,6'-Hexachlorobiphenyl 0.50 0.50 5.3 99 0.079

Hexachlorocyclopentadiene 0.50 0.37 9.3 73 0.10

Hexazinone 0.50 0.75 4.2 150 0.094

Indeno[1,2,3-cd]pyrene 0.50 0.48 7.3 96 0.10

Isophorone 0.50 0.51 4.3 102 0.066

Methoxychlor 0.50 0.52 6.7 104 0.10

Methyl Paraoxon 0.50 0.75 4.5 151 0.10

Metolachlor 0.50 0.57 3.2 114 0.054

Metribuzin 0.50 0.53 5.7 107 0.090

Mevinphos 0.50 0.56 6.2 112 0.10

MGK 264 - Isomer a 0.33 0.38 6.7 113 0.076

MGK 264 - Isomer b 0.16 0.18 5.3 110 0.029

Molinate 0.50 0.53 3.8 105 0.060

Napropamide 0.50 0.58 7.9 116 0.14

Norflurazon 0.50 0.71 4.3 142 0.091

2,2',3,3',4,5',6,6'- 0.50 0.47 5.3 94 0.076

Octachlorobiphenyl

Pebulate 0.50 0.56 7.1 112 0.11

2,2',3',4,6-Pentachlorobiphenyl 0.50 0.49 4.0 97 0.059

Pentachlorophenol 2.0 2.2 15 111 1.0

Permethrin,cis 0.25 0.37 3.1 149 0.035
TABLE 6. ACCURACY AND PRECISION DATA FROM EIGHT

DETERMINATIONS OF THE METHOD ANALYTES IN REAGENT WATER

USING LIQUID-SOLID C-18 DISK EXTRACTION AND THE ION TRAP

MASS SPECTROMETER

Compound (μg/L) (μg/L) (%) Conc.) (μg/L)

True Observed Deviatio Accuracy

Conc. Conc. n (% of True MDL

Mean Standard Method

Relative Mean

525.2-53

Permethrin,trans 0.75 0.84 1.6 112 0.039

Phenanthrene 0.50 0.49 6.3 97 0.092

Prometon 0.50 0.16 63 32 0.30 d

Prometryn 0.50 0.46 23 91 0.32

Pronamide 0.50 0.56 3.9 111 0.064

Propachlor 0.50 0.58 5.7 115 0.098

Propazine 0.50 0.53 4.7 106 0.074

Pyrene 0.50 0.52 5.2 104 0.080

Simazine 0.50 0.54 2.8 107 0.045

Simetryn 0.50 0.36 20 71 0.22

Stirofos 0.50 0.72 3.7 144 0.080

Tebuthiuron 0.50 0.67 7.9 133 0.16

Terbacil 0.50 0.64 12 129 0.23

Terbufos 0.50 0.57 6.8 113 0.11

Terbutryn 0.50 0.46 24 93 0.34

2,2',4,4'-Tetrachlorobiphenyl 0.50 0.46 7.4 91 0.10

Toxaphene 10 12 2.7 122 1.0 c

Triademefon 0.50 0.71 7.3 142 0.16

2,4,5-Trichlorobiphenyl 0.50 0.48 4.5 97 0.066

Tricyclazole 0.50 0.65 14 130 0.27

Trifluralin 0.50 0.59 7.8 117 0.14

Vernolate 0.50 0.50 3.2 99 0.047

Six replicates. a

Seven replicates in fortified tap water. b

Seven replicates. c

Data from samples extracted at pH 2 - for accurate determination of this analyte, a d

separate sample must be extracted at ambient pH.
525.2-54

TABLE 7. ACCURACY AND PRECISION DATA FROM EIGHT DETERMINATIONS AT 5 μg/L IN REAGENT

WATER OF POORLY CHROMATOGRAPHED NITROGEN AND PHOSPHOROUS CONTAINING PESTICIDES

Compound

Ion Trap Mass Spectrometer Quadrupole Mass Spectrometer

Cartridge Disk Cartridge Disk

Relative

Standard

Deviatio

n

(%)

Mean

Method

Accuracy

(% of True

Conc.)

Relative

Standard

Deviatio

n (%)

Mean

Method

Accuracy

(% of True

Conc.)

Relative

Standard

Deviatio

n (%)

Mean

Method

Accuracy

(% of True

Conc.)

Relative

Standard

Deviation

(%)

Mean Method

Accuracy

(% of True

Conc.)

Fenamiphos 7.7 99 4.5 108 6.1 103 8.8 124Fenarimol 2.0 104 10 110 6.5 126 5.5 150Fluridone 2.5 105 2.3 104 3.6 102 4.5 114Hexazinone 4.2 106 9.7 116 5.3 104 8.3 127Norflurazon 4.1 111 9.6 119 3.2 98 11.1 113Stirofos 8.2 114 12 124 4.1 110 11.1 125Tebuthiuron 9.5 119 5.3 145 13 136 8.6 182Triademeton 7.8 113 10 128 3.7 100 9.8 118Tricyclazole 16 81 9.5 99 19 92 12 137
525.2-55

TABLE 8. ACCURACY AND PRECISION DATA FROM SEVEN

DETERMINATIONS OF THE METHOD ANALYTES IN TAP WATER USING

LIQUID-SOLID C-18 CARTRIDGE EXTRACTION AND THE ION TRAP

MASS SPECTROMETER

Compound Conc. Mean % RSD % REC

True

Acenaphthylene 5.0 5.2 5.3 104

Alachlor 5.0 5.5 6.9 110

Aldrin 5.0 4.4 14 88

Ametryn 5.0 4.2 3.4 83

Anthracene 5.0 4.3 5.2 87

Aroclor 1016 ND ND ND ND

Aroclor 1221 ND ND ND ND

Aroclor 1232 ND ND ND ND

Aroclor 1242 ND ND ND ND

Aroclor 1248 ND ND ND ND

Aroclor 1254 ND ND ND ND

Aroclor 1260 ND ND ND ND

Atraton 5.0 2.2 28 43 a

Atrazine 5.0 5.6 6.2 111

Benz[a]anthracene 5.0 4.9 8.8 97

Benzo[b]fluoranthene 5.0 5.7 7.5 114

Benzo[k]fluoranthene 5.0 5.7 2.9 113

Benzo[g,h,i]perylene 5.0 5.6 7.1 113

Benzo[a]pyrene 5.0 6.1 4.6 121

Bromacil 5.0 3.5 5.1 69

Butachlor 5.0 5.4 7.5 109

Butylate 5.0 5.1 4.5 102

Butylbenzylphthalate 5.0 7.2 8.3 144

Carboxin 5.0 1.0 23 20

Chlordane, (alpha-Chlordane) 5.0 5.2 8.9 104

Chlordane, (gamma-Chlordane) 5.0 5.1 8.0 102

Chlordane, (trans-Nonachlor) 5.0 5.6 7.4 111

Chlorneb 5.0 5.2 3.0 105

Chlorobenzilate 5.0 5.7 4.4 114

2-Cchlorobiphenyl 5.0 5.8 5.4 115

Chlorpropham 5.0 6.3 4.9 127

Chlorpyrifos 5.0 5.3 7.2 107

Chlorthalonil 5.0 5.4 9.9 108

Chrysene 5.0 5.5 3.9 110

Cyanazine 5.0 6.1 13 122

Cycloate 5.0 5.6 1.5 112

DCPA 5.0 5.4 5.0 107

4,4'-DDD 5.0 5.3 6.5 105
TABLE 8. ACCURACY AND PRECISION DATA FROM SEVEN

DETERMINATIONS OF THE METHOD ANALYTES IN TAP WATER USING

LIQUID-SOLID C-18 CARTRIDGE EXTRACTION AND THE ION TRAP

MASS SPECTROMETER

Compound Conc. Mean % RSD % REC

True

525.2-56

4,4'-DDE 5.0 5.2 6.6 104

4,4'-DDT 5.0 5.6 9.6 111

Diazinon 5.0 4.9 8.7 98

Dibenz[a,h]anthracene 5.0 5.9 7.5 118

Di-n-Butylphthalate 5.0 6.2 4.6 124

2,3-Dichlorobiphenyl 5.0 5.3 7.4 106

Dichlorvos 5.0 2.8 7.3 56

Dieldrin 5.0 5.3 7.2 105

Di(2-Ethylhexyl)adipate 5.0 6.7 10 134

Di(2-Ethylhexyl)phthalate 5.0 6.5 6.6 130

Diethylphthalate 5.0 6.4 7.4 127

Dimethylphthalate 5.0 5.8 7.1 116

2,4-Dinitrotoluene 5.0 4.2 8.7 84

2,6-Dinitrotoluene 5.0 4.1 8.5 82

Diphenamid 5.0 5.2 7.7 104

Disulfoton 5.0 2.5 33 50

Disulfoton Sulfone 5.0 5.5 7.4 110

Disulfoton Sulfoxide 5.0 9.4 11 188

Endosulfan I 5.0 5.5 11 109

Endosulfan II 5.0 5.3 9.6 106

Endosulfan Sulfate 5.0 5.3 7.8 106

Endrin 5.0 6.1 3.9 121

Endrin Aldehyde 5.0 5.1 9.1 102

EPTC 5.0 5.1 2.1 102

Ethoprop 5.0 6.3 4.2 125

Etridiazole 5.0 5.8 7.5 117

Fenamiphos 5.0 5.9 22 119

Fenarimol 5.0 7.1 3.3 141

Fluorene 5.0 5.7 5.2 114

Fluridone 5.0 6.2 9.0 125

HCH, alpha 5.0 5.9 2.6 118

HCH, beta 5.0 5.3 8.4 106

HCH, delta 5.0 5.3 5.2 106

HCH, gamma (Lindane) 5.0 5.3 6.9 107

Heptachlor 5.0 4.7 8.7 93

Heptachlor Epoxide 5.0 5.2 7.7 105

2,2',3,3',4,4',6-Heptachlorobiphenyl 5.0 5.1 6.9 103

Hexachlorobenzene 5.0 4.6 7.4 93
TABLE 8. ACCURACY AND PRECISION DATA FROM SEVEN

DETERMINATIONS OF THE METHOD ANALYTES IN TAP WATER USING

LIQUID-SOLID C-18 CARTRIDGE EXTRACTION AND THE ION TRAP

MASS SPECTROMETER

Compound Conc. Mean % RSD % REC

True

525.2-57

2,2',4,4',5,6'-Hexachlorobiphenyl 5.0 5.6 8.1 112

Hexachlorocyclopentadiene 5.0 6.0 4.8 120

Hexazinone 5.0 6.9 6.3 138

Indeno[1,2,3-cd]pyrene 5.0 6.8 7.7 135

Isophorone 5.0 4.9 12 99

Methoxychlor 5.0 5.6 4.9 112

Methyl Paraoxon 5.0 5.6 11 111

Metolachlor 5.0 5.6 7.7 111

Metribuzin 5.0 2.1 5.8 42

Mevinphos 5.0 3.3 1.6 67

MGK 264 - Isomer a 3.3 3.6 6.2 107

MGK 264 - Isomer b 1.7 1.8 7.6 110

Molinate 5.0 5.5 1.5 110

Napropamide 5.0 5.3 8.9 106

Norflurazon 5.0 6.7 7.2 135

2,2',3,3',4,5',6,6'-Octaclorobiphenyl 5.0 4.9 6.9 97

Pebulate 5.0 5.3 3.1 106

2,2',3',4,6-Pentachlorobiphenyl 5.0 5.3 8.1 107

Pentachlorophenol 20. 33 4.9 162

Permethrin, cis 5.0 3.3 3.5 130

Permethrin, trans 5.0 8.5 2.2 113

Phenanthrene 5.0 5.5 4.0 109

Prometona 5.0 2.0 25 40 a

Prometryn 5.0 4.5 4.3 89

Pronamide 5.0 5.7 5.3 115

Propachlor 5.0 6.2 4.0 124

Propazine 5.0 5.6 4.9 113

Pyrene 5.0 5.2 6.7 104

Simazine 5.0 6.0 9.0 120

Simetryn 5.0 3.9 7.0 78

Stirofos 5.0 6.1 12 121

Tebuthiuron 5.0 6.5 9.7 130

Terbacil 5.0 4.0 5.5 79

Terbufos 5.0 4.5 8.4 90

Terbutryn 5.0 4.3 6.5 86

2,2',4,4'-Tetrachlorobiphenyl 5.0 5.3 4.3 106

Toxaphene ND ND ND ND

Triademefon 5.0 6.0 12 121
TABLE 8. ACCURACY AND PRECISION DATA FROM SEVEN

DETERMINATIONS OF THE METHOD ANALYTES IN TAP WATER USING

LIQUID-SOLID C-18 CARTRIDGE EXTRACTION AND THE ION TRAP

MASS SPECTROMETER

Compound Conc. Mean % RSD % REC

True

525.2-58

2,4,5-Trichlorobiphenyl 5.0 5.2 5.1 103

Tricyclazole 5.0 4.8 5.2 96

Trifluralin 5.0 5.9 7.8 119

Vernolate 5.0 5.4 3.3 108

Data from samples extracted at pH 2 - for accurate determination of this analyte, a a

separate sample must be extracted at ambient pH.
525.2-59
525.2-60