Analytical Chemistry Methods Manuals _ Microbiological and Chemical Exposure

Analytical Chemistry Methods Manuals | Microbiological and Chemical Exposure Assessment Research | US EPA

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Analytical Chemistry Methods Manuals:Manual of ManualsSummaries and Ordering Information for Eight Laboratory Analytical Chemistry MethodsManuals Published by the EPA between 1988 and 1995. - Prepared by William L. Budde

This document contains the titles, publication numbers, dates of publication, ordering information,abstracts, tables of contents, analyte-method cross reference lists, and Introductions to eightlaboratory analytical chemistry methods manuals published between 1988 and 1995. The completemanuals may be ordered from the National Technical Information Service (NTIS) at the address ortelephone numbers below:

National Technical Information Service5285 Port Royal RoadSpringfield, VA 22161

Voice: 703-487-4650 or 800-553-6847Fax: 703-321-8547

The shipping charge per order is $3.00.

On this page:

Organics Manual of 1988Organics Supplement I of 1990Organics Supplement II of 1992Organic Supplement III of 1995Metals Manual of 1991Metals Supplement I of 1994Inorganic Non-Metals of 1993Marine & Estuarine of 1992

Methods for the Determination of Organic Compounds inDrinking Water

Environmental Monitoring Systems LaboratoryOffice of Research and Development

U.S. Environmental Protection AgencyCincinnati, Ohio 45268

EPA-600/4-88/039December 1988

(Revised July 1991)

This manual is available from NTIS and contains Methods 502.1, 502.2, 503.1, 504, 505, 507,508, 508A, 515.1, 524.1, 524.2, 525.1 and 531.1. Note that all of these methods except 502.1,503.1, 508A and 524.1 have been revised and published in one of the three organics supplementsthat are described in this document. Address your request for this manual to NTIS and ask for theirorder number PB91-231480; the cost is $61.50.

Abstract

Thirteen analytical methods for the identification and measurement of organic compounds indrinking water are described in detail. Six of the methods are for volatile organic compounds(VOCs) and certain disinfection by-products, and these methods were cited in the FederalRegister of July 8, 1987, under the National Primary Drinking Water Regulations. The other sevenmethods are designed for the determination of a variety of synthetic organic compounds andpesticides, and these methods were cited in proposed drinking water regulations in the FederalRegister of May 22, 1989. Five of the methods utilize the inert gas purge-and-trap extraction



procedure for VOCs, six methods employ a classical liquid-liquid extraction, one method uses anew liquid-solid extraction technique, and one method is for direct aqueous analysis. Of the 13methods, 12 use either packed or capillary gas chromatography column separations followed bydetection with mass spectrometry or a selective gas chromatography detector. One method isbased on a high performance liquid chromatography separation.

Table of Contents

MethodNumber

Title Revision Page

- Foreword - iii

- Abstract - iv

- Analyte - Method Cross Reference - vii

- Acknowledgement - xii

- Introduction - 1

502.1Volatile Halogenated Organic Compounds inWater by Purge and Trap GasChromatography

2.0 5

502.2

Volatile Organic Compounds in Water ByPurge and Trap Capillary Column GasChromatography with Photoionization andElectrolytic Conductivity Detectors in Series

2.0 31

503.1Volatile Aromatic and Unsaturated OrganicCompounds in Water by Purge and Trap GasChromatography

2.0 63

5041,2-Dibromoethane (EDB) and 1,2-Dibromo-3-Chloropropane (DBCP) in Water byMicroextraction and Gas Chromatography

2.0 89

505

Analysis of Organohalide Pesticides andCommerical Polychlorinated BiphenylProducts in Water by Micro-Extraction andGas Chromatography

2.0 109

507

Determination of Nitrogen- and Phosphorus-Containing Pesticides in Water by GasChromatography with a Nitrogen-PhosphorusDetector

2.0 143

508Determination of Chlorinated Pesticides inWater by Gas Chromatography with AnElectron Capture Detector

3.0 171

508A Screening for Polychlorinated Biphenyls byPerchlorination and Gas Chromatography

1.0 199

515.1Determination of Chlorinated Acids in Waterby Gas Chromatography with an ElectronCapture Detector

4.0 221



524.1Measurement of Purgeable OrganicCompounds in Water by Packed ColumnGasChromatography/Mass Spectrometry

3.0 253

524.2Measurement of Purgeable OrganicCompounds in Water by Capillary ColumnGas Chromatography/Mass Spectrometry

3.0 283

525.1

Determination of Organic Compounds inDrinking Water by Liquid-Solid Extractionand Capillary Column GasChromatography/Mass Spectrometry

2.2 323

531.1

Measurement of N-Methylcarbamoyloximesand N-Methylcarbamates in Water by DirectAqueous Injection HPLC with Post ColumnDerivatization

3.0 361

Analyte-Method Cross Reference

Analyte Method No.

Acifluorfen 515.1

Acenaphthylene 525.1

Alachlor 505, 507, 525.1

Aldicarb 531.1

Aldicarb sulfone 531.1

Aldicarb sulfoxide 531.1

Aldrin 505, 508, 525.1

Ametryn 507

Anthracene 525.1

Aroclor 1016 505, 508, 525.1

Aroclor 1221 505, 508, 525.1

Aroclor 1232 505, 508, 525.1

Aroclor 1242 505, 508, 525.1

Aroclor 1248 505, 508, 525.1

Aroclor 1254 505, 508, 525.1

Aroclor 1260 505, 508, 525.1

Aroclor (General screen) 508A, 525.1

Atraton 507

Atrazine 505, 507, 525.1

Baygon 531.1



Bentazon 515.1

Benz[a]anthracene 525.1

Benzene 502.2, 503.1, 524.1,524.2

Benzo[b]fluoranthene 525.1

Benzo[k]fluorathene 525.1

Benzo[g,h,i]perylene 525.1

Benzo[a]pyrene 525.1

Bromacil 507

Bromobenzene 502.1, 502.2, 503.1,524.1, 524.2

Bromochloromethane 502.1, 502.2, 524.1,524.2

Bromodichloromethane 502.1, 502.2, 524.1,524.2

Bromoform 502.1, 502.2, 524.1,524.2

Bromomethane 502.1, 502.2, 524.1,524.2

Butachlor 507

Butylate 507

n-Butylbenzene 502.2, 503.1, 524.2

sec-Butylbenzene 502.2, 503.1, 524.2

tert-Butylbenzene 502.2, 503.1, 524.2

Butylbenzylphthalate 525.1

Carbaryl 531.1

Carbofuran 531.1

Carbon tetrachloride 502.1, 502.2, 524.1,524.2

Carboxin 507

Chloramben 515.1

Chlordane (Technical) 505, 508

Chlordane-alpha 505, 508, 525.1

Chlordane-gamma 505, 508, 525.1

Chlorneb 508



Chlorobenzene 502.1, 502.2, 503.1,524.1, 524.2

Chlorobenzilate 508

2-Chlorobiphenyl 525.1

Chloroethane 502.1, 502.2, 524.1,524.2

Chloroform 502.1, 502.2, 524.1,524.2

Chloromethane 502.1, 502.2, 524.1,524.2

Chlorothalonil 508

2-Chlorotoluene 502.1, 502.2, 503.1,524.1, 524.2

4-Chlorotoluene 502.1, 502.2, 503.1,524.1, 524.2

Chlorpropham 507

Chrysene 525.1

Cycloate 507

Dalapon 515.1

Dimethyl-2,3,5,6-tetrachloroterephthalate(DCPA) (Dacthal)

508

DCPA mono and diacidmetabolites

515.1

2,4-Dichlorophenoxyaceticacid (2,4-D)

515.1

4-(2,4-Dichlorophenoxy)butyricacid (2,4-DB)

515.1

4,4'-DDD[1,1-dichloro-2,2-bis(p-chlorophenyl)ethane]

508

4,4'-DDE[1,1-dichloro-2,2-bis(p-chlorophenyl)ethylene]

508

4,4'-DDT[1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane]

508

Diazinon 507



Dibenz[a,h]anthracene 525.1

Dibromochloromethane 502.1, 502.2, 524.1,524.2

1,2-Dibromo-3-chloropropane

502.2, 504, 524.1,524.2

Dibromomethane 502.1, 502.2, 524.1,524.2

1,2-Dibromoethane 502.1, 502.2, 504,524.1, 524.2

Di-n-butylphthalate 525.1

Dicamba 515.1

1,2-Dichlorobenzene 502.1, 502.2, 503.1,524.1, 524.2



3,5-Dichlorobenzoic acid 515.1

2,3-Dichlorobiphenyl 525.1

1,1-Dichloroethane 502.1, 502.2, 524.1,524.2

1,2-Dichloroethane 502.1, 502.2, 524.1,524.2

1,1-Dichloroethene 502.1, 502.2, 524.1,524.2

cis-1,2-Dichloroethene 502.1, 502.2, 524.1,524.2

trans-1,2-Dichloroethene 502.1, 502.2, 524.1,524.2

1,2-Dichloropropane 502.1, 502.2, 524.1,524.2



1,1-Dichloropropene 502.1, 502.2, 524.1,524.2

cis-1,3-Dichloropropene 502.1, 502.2, 524.1,



524.2

trans-1,3-Dichloropropene 502.1, 502.2, 524.1,524.2

Dichlorodifluoromethane 502.1, 502.2, 524.1,524.2

Dichlorprop 515.1

Dichlorvos 507

Dieldrin 505, 508

Diethylphthalate 525.1

Dimethylphthalate 525.1

Dinoseb 515.1

Diphenamid 507

Disulfoton sulfoxide 507

Disulfoton sulfone 507

Disulfoton 507

Endosulfan sulfate 508

Endosulfan I 508

Endosulfan II 508

Endrin aldehyde 508

Endrin 505, 508, 525.1

S-Ethyldipropylthiocarbamate(EPTC)

507

n-(2-Ethylhexyl)bicyclo[2.2.1]-5-heptene-2,3-dicarboximide (MGK-264)

507

Ethoprop 507

Ethylbenzene 502.2, 503.1, 524.1,524.2

bis(2-Ethylhexyl)adipate 525.1

bis(2-Ethylhexyl)phthalate 525.1

Etridiazole 508

Fenamiphos 507

Fenarimol 507



Fluorene 525.1

Fluridone 507

alphaHexachlorocyclohexane(alpha BHC)(HCH-alpha)

508

betaHexachlorocyclohexane(beta BHC)(HCH-beta)

508

deltaHexachlorocyclohexane(delta BHC)(HCH-delta)

508

gammaHexachlorocyclohexane(Lindane)(gammaBHC)(HCH-gamma)

505, 508, 525.1

Heptachlor 505, 508, 525.1

Heptachlor Epoxide 505, 508, 525.1

2,2',3,3',4,4',6-Heptachlorobiphenyl

525.1

Hexachlorobenzene 505, 508,525.1

2,2',4,4',5,6'-Hexachlorobiphenyl

525.1

Hexachlorobutadiene 502.2, 503.1, 524.2

Hexachlorocyclopentadiene 505, 525.1

Hexazinone 507

3-Hydroxycarbofuran 531.1

5-Hydroxydicamba 515.1

Indeno[1,2,3,c,d]pyrene 525.1

Isopropylbenzene 502.2, 503.1, 524.2

4-Isopropyltoluene 502.2, 503.1, 524.2

Merphos 507

Methiocarb 531.1

Methomyl 531.1

Methoxychlor 505, 508, 525.1

Methyl paraoxon 507

Methylene chloride 502.1, 502.2, 524.1,524.2



Metolachlor 507

Metribuzin 507

Mevinphos 507

Molinate 507

Naphthalene 502.2, 503.1, 524.2

Napropamide 507

4-Nitrophenol 515.1

cis-Nonachlor 505

trans-nonachlor 505, 525.1

Norflurazon 507

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

525.1

Oxamyl 531.1

Pentachlorophenol (PCP) 515.1, 525.1

Pebulate 507

2,2',3',4,6-Pentachlorobiphenyl

525.1

cis-Permethrin 508

trans-Permethrin 508

Phenanthrene 525.1

Picloram 515.1

Polychlorobiphenyls(General screen)

508A

Prometon 507

Prometryn 507

Pronamide 507

Propachlor 508

Propazine 507

Propylbenzene 502.2

n-Propylbenzene 503.1,524.2

Pyrene 525.1

Simazine 505, 507, 525.1

Simetryn 507



Stirofos 507

Styrene 502.2,503.1,524.1,524.2

2,2',4,4'-Tetrachlorobiphenyl

525.1

2,4,5-Trichlorophenoxyaceticacid (2,4,5-T)

515.1

2-(2,4,5-Trichlorophenoxy)propionicacid (2,4,5-TP)(Silvex)

515.1

Tebuthiuron 507

Terbacil 507

Terbufos 507

Terbutryn 507

Tetrachloroethene 502.1, 502.2, 503.1,524.1, 524.2

1,1,1,2-Tetrachloroethane 502.1, 502.2, 524.1,524.2

1,1,2,2-Tetrachloroethane 502.1, 502.2, 524.1,524.2

Toluene 502.2, 503.1, 524.1,524.2

Toxaphene (Technical) 505, 508, 525.1

Triademefon 507

1,2,3-Trichlorobenzene 502.2, 503.1, 524.2

1,2,4-Trichlorobenzene 502.2, 503.1, 524.2

2,4,5-Trichlorobiphenyl 525.1

Trichloroethene 502.1, 502.2, 503.1,524.1, 524.2

1,1,1-Trichloroethane 502.1, 502.2, 524.1,524.2

1,1,2-Trichloroethane 502.1, 502.2, 524.1,524.2

Trichlorofluoromethane 502.1, 502.2, 524.1,524.2

1,2,3-Trichloropropane 502.1, 502.2, 524.1,524.2



Tricyclazole 507

Trifluralin 508

1,2,4-Trimethylbenzene 502.2, 503.1, 524.2

1,3,5-Trimethylbenzene 502.2, 503.1, 524.2

Vernolate 507

Vinyl chloride 502.1, 502.2, 524.1,524.2

m-Xylene 502.2, 503.1, 524.1,524.2

o-Xylene 502.2, 503.1, 524.1,524.2

p-Xylene 502.2, 503.1, 524.1,524.2

Introduction

William L. Budde U. S. Environmental Protection Agency

Many of the nearly 200 organic analytes included in this manual may be identified and measured indrinking water using two or more of the documented analytical methods. For example, nearly 50compounds are listed as analytes in four different methods. This approach of multiple methods formany analytes was selected to provide the maximum flexibility to method users from small andlarge laboratories. Some methods require relatively modest equipment, and others requiresophisticated instrumentation. This flexible approach should meet the needs and requirements ofnearly all laboratories.

General Method Features

Each of the methods in the manual was written to stand-alone, that is, each method may beremoved from the manual, photocopied, inserted into another binder, and used without loss ofinformation. Revisions of these methods will be made available in a similar stand-alone format tofacilitate the replacement of existing methods as new technical developments occur. This flexibilitycomes at the cost of some duplication of material, for example, the definitions of terms section ofeach method is nearly identical. The authors believe that the added bulk of the manual is a smallprice to pay for the flexibility of the format.

An important feature of the methods in this manual is the consistent use of terminology, and thisfeature is especially helpful in the quality control sections where standardized terminology is not yetavailable. The terms were carefully selected to be meaningful without extensive definition, andtherefore should be easy to understand and use. The names of authors of the methods areprovided to assist users in obtaining direct telephone support when required.

Sample Matrices

All methods were developed for relatively clean water matrices, that is, drinking water and someground and surface waters. Some methods have been tested only in reagent water and/or drinkingwater. While some of these methods may provide reliable results with more complex watermatrices, for example, industrial wastewaters and beverages, techniques for dealing with morecomplex matrices have not been included in the methods in order to keep them as simple and briefas possible. Therefore caution is needed when applying these methods to matrices other thanrelatively clean water.

Methods developed for drinking water include provisions for removal of free chlorine



(dechlorination) which is assumed to be present in all samples. Dechlorination is necessary to stopthe formation of trichloromethanes and other disinfection by-products, or to prevent the formationof method interferences and analytes generated from chlorination of impurities in reagents andsolvents.

Similarly, pH adjustments are included in some of the methods for several reasons: (a) to retardgrowth in dechlorinated water of bacteria that can decompose some analytes; (b) to prevent acidor base catalyzed decomposition of analytes; and (c) to improve the extraction efficiency of certainanalytes.

Detection Limits

Most methods include either a method detection limit (MDL) or an estimated detection limit (EDL)for each analyte. These limits are intended to provide an indication of the capability of the method,but they may not be of regulatory significance.

The MDL is calculated from the standard deviation of replicate measurements, and is defined asthe minimum concentration of a substance that can be identified, measured, and reported with99% confidence that the analyte concentration is greater than zero. The EDL is either the MDL, ora concentration of compound in a clean water matrix that gives a peak in the final extract with asignal-to-noise ratio of about 5.

If the replicate measurements needed to calculate an MDL are obtained under ideal conditions, forexample, during a short period of time within a work shift, the resulting standard deviation may besmall and give an unrealistically low MDL. The data acquired for measurement of an MDL should beobtained over a period of time (several days or more). Obtained in this way, the standard deviationincludes normal day-to-day variations, and the MDL will be more realistic.

Calibration Standards and Quality Control Samples

The methods contain separate calibration and quality control sections, and accurate calibrationstandards and quality control samples are needed to implement the methods. Calibration standardsand quality control samples should be obtained from different sources so that the quality controlsample can provide an independent check on the calibration and the other method variables.

Calibration standards and quality control samples may be available commercially, or may beavailable on a limited basis from the Quality Assurance Research Division, EnvironmentalMonitoring Systems Laboratory - Cincinnati, 26 W. Martin Luther King Drive, Cincinnati, OH, 45268.

Methods for Volatile Organic Compounds (VOCS)

Six of the methods in the manual are for the determination of VOCs and certain disinfection by-products. These methods were cited in the Federal Register of July 8, 1987 under the NationalPrimary Drinking Water Regulations. These are Methods 502.1, 502.2, 503.1, 504, 524.1 and524.2.

The six VOC methods have been distributed in the form of photocopied documents by EMSL-Cincinnati to several hundred laboratories in the last two years. Five of these methods utilize thesame basic purge-and-trap extraction technique, but, depending on the specific method selected,the user has a choice of a packed or capillary column gas chromatography (GC) separation and amass spectrometer (MS) or conventional GC detector. The other method (Method 504) is amicroextraction procedure for two compounds of special interest, ethylene dibromide (EDB) and1,2-dibromo-3-chloropropane (DBCP).

Solicited and unsolicited written and telephoned comments have been received from some of thelaboratories using the VOC methods, and some of these users suggested certain technical andeditorial changes. In addition, the staff of the Chemistry Research Division recognized that somechanges were needed to make the methods easier to understand and use, and bring them up-to-date. The revisions of the six VOC methods contained in the manual incorporate a few technicaland many editorial changes which are summarized below.

Few technical changes were made to the six VOC methods. The use of ascorbic acid as adechlorinating agent is described. Ascorbic acid has been extensively tested as a dechlorinating



agent, and has been found to be as effective as sodium thiosulfate, but without the undesirablegeneration of sulfur dioxide at low pH.

The open split interface between the GC and the MS was incorporated into Method 524.2, but theinterfaces previously mentioned were retained. Data is presented in the method to show that theopen split interface can provide acceptable precision, accuracy, and detection limits. The previousrevision of Method 524.2 allowed any interface that could meet the precision and accuracyrequirements of the method. Many laboratories will find the open split interface to be the mosteconomical for this method.

Changes were made in the recommended chromatographic conditions and internal standards inMethod 502.2. These changes allow the measurement of all 60 VOCs in a single calibrationsolution.

Extensive editorial changes were made in all six VOC methods. These editorial changes werenecessary to provide an organized, consistent, and much more complete presentation of themyriad details needed by laboratories to successfully implement the methods. The addition of thesedetails, the consistent use of terminology, and the uniform organization of all the methods shouldsubstantially reduce the number of questions received and provide the user community with theinformation needed to obtain high quality results.

Methods for Synthetic Organic Compounds (SOCS)

Four of the SOC methods were developed for a national pesticides survey conducted by EPA during1987-1989, and these are designated Methods 507, 508, 515.1, and 531.1. One screening method(Method 508A) for polychlorinated biphenyls (PCBs) was developed as a result of a specific requestfrom the Office of Drinking Water (ODW). Method 505, a relatively simple microextractionprocedure patterned after Method 504, was developed to provide a rapid method for thedetermination of chlorinated hydrocarbon pesticides and commercial PCB mixtures (Aroclors) indrinking water. Method 525.1 is a broad spectrum GC/MS method for a variety of compounds underconsideration for regulation, and it was developed specifically to utilize the new liquid-solidextraction technology and minimize use of the solvent methylene chloride.

Three of the methods used in the national pesticides survey utilize a liquid-liquid extraction of theSOCs from water followed by a high resolution capillary column GC separation and detection withan electron capture or other selective detector (Methods 507, 508, and 515.1). One of the methods(531.1) employs the direct analysis of a water sample with a high performance liquidchromatography (HPLC) separation and post-column derivatization to a compound detected with afluorescence detector.

Method 508A was designed as a screening procedure for polychlorinated biphenyls (PCBs). Themethod uses the powerful chlorinating agent antimony pentachloride to convert all the PCBcongeners in a sample extract to decachlorobiphenyl which is separated with either packed orcapillary column gas chromatography, and detected with an electron capture detector.

Method 505 provides a rapid procedure for chlorinated hydrocarbon pesticides and commercial PCBmixtures (Aroclors). This method uses a high resolution capillary column GC separation anddetection with an electron capture detector.

The broad spectrum GC/MS method (Method 525.1) uses a liquid-solid extraction (LSE) procedurebased on commercial LSE cartridges or disks. The cartridges are small (about 0.5 in. x 3 in.) plasticor glass tubes packed with reverse phase liquid chromatography packing materials. The disks aremade of Teflon containing silica which is coated with a chemically bonded C-18 organic phase.Water samples are passed through the cartridges or disks and some organic compounds are sorbedon the solid phase. After air drying, the organic compounds are eluted using a very small volumeof an organic solvent. Cartridges from six suppliers were used in the methods research, and aquality control procedure was developed to permit selection of cartridges with acceptableperformance characteristics. The disks are manufactured by a single company, so only one typewas evaluated.

The LSE procedure is attractive because it greatly reduces the use and worker exposure tomethylene chloride and similar solvents. The compounds in the cartridge extract are separated,identified, and measured with a high resolution capillary column GC/MS procedure. This allows thesimultaneous determination of 42 SOCs including chlorinated hydrocarbon pesticides, polycyclic



aromatic hydrocarbons, phthalate and adipate esters, individual PCB congeners, several triazinepesticides, and pentachlorophenol. Laboratories will find this method attractive because of itspotential economy of operation when a wide variety of analytes are to be determined.

To the:Chemical Exposure Research Branch

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Methods for the Determination of Organic Compounds inDrinking WaterSupplement Ik



EPA-600/4-90/020July 1990

This manual is available from NTIS and contains Methods 506, 513, 547, 548, 549, 550, 550.1,551 and 552. Please note that Methods 506, 548, 549, 551, and 552 have been revised and therevised versions are published in Supplement II or III. Address your request for this manual to toNTIS and ask for their order number PB91-146027; the cost is $51.50.

Abstract

Nine analytical methods covering 54 organic contaminants which may be present in drinking wateror drinking water sources are described in detail. Seven of these methods cover compoundsdesignated for regulation under the Safe Drinking Water Act Amendments of 1986. Regulations forthis group are in the proposal stages with promulgation scheduled for June 1992. The other twomethods are for chlorination disinfection byproducts and may be regulated as part of EPA'sdisinfectants and disinfectant byproducts rule scheduled for proposal early in 1992. Most of theanalytes may be classified as non-volatile and three of the methods entail separations by highperformance liquid chromatography. The remainder employ capillary column gas chromatography.One of these requires detection of a potentially very toxic contaminant, 2,3,7,8-tetrachlorodibenzo-p-dioxin, at the low parts per trillion level. Labeled isotopes of this analyte are employed as tracersand high resolution mass spectrometry is required for detection and unambiguous identification.Three of the methods herein offer new and simplified liquid-solid extraction procedures, a trendwhich is likely to become even more pronounced in the future.

Table of Contents

MethodNumber

Title Page

- Foreword iii

- Abstract iv

- Acknowledgment vi

- Analyte - Method Cross Reference vii

- Introduction 1

506

Determination of Phthalate and Adipate Esters inDrinking Water by Liquid-Liquid Extraction or Liquid-Solid Extraction and Gas Chromatography with

5

http://www.epa.gov/nerlcwww/cerb.html



Photoionization Detection

513

Determination of 2,3,7,8-Tetrachloro-dibenzo-p-dioxinin Drinking Water by Liquid-Liquid Extraction and GasChromatography with High-Resolution MassSpectrometry

33

547Determination of Glyphosate in Drinking Water byDirect-Aqueous-Injection HPLC, Post-ColumnDerivatization, and Fluorescence Detection

63

548Determination of Endothall in Drinking Water byAqueous Derivatization, Liquid-Solid Extraction, andGas Chromatography with Electron-Capture Detection

81

549Determination of Diquat and Paraquat in DrinkingWater by Liquid-Solid Extraction and HPLC withUltraviolet Detection

101

550Determination of Polycyclic Aromatic Hydrocarbons inDrinking Water by Liquid-Liquid Extraction and HPLCwith Coupled Ultraviolet and Fluorescence Detection

121

550.1Determination of Polycyclic Aromatic Hydrocarbons inDrinking Water by Liquid-Solid Extraction and HPLCwith Coupled Ultraviolet and Fluorescence Detection

143

551

Determination of Chlorination Disinfection Byproductsand Chlorinated Solvents in Drinking Water by Liquid-Liquid Extraction and Gas Chromatography withElectron-CaptureDetection

169

552Determination of Haloacetic Acids in Drinking Water byLiquid-Liquid Extraction, Derivatization, and GasChromatography with Electron Capture Detection

201

Analyte-Method Cross Reference

Analyte MethodNo.

Acenaphthene 550,550.1

Acenaphthylene 550,550.1

Anthracene 550,550.1

Benz(a)anthracene 550,550.1

Benzo(b)fluoranthene 550,550.1

550,



Benzo(k)fluoranthene550.1

Benzo(g,h,i)perylene 550,550.1

Benzo(a)pyrene 550,550.1

Bis(2-ethylhexyl)adipate 506

Bis(2-ethylhexyl)phthalate

506

Bromochloroacetic Acid 552

Bromochloroacetonitrile 551

Bromodichloromethane 551

Bromoform 551

Butylbenzyl phthalate 506

Carbon Tetrachloride 551

Chloral Hydrate 551

Chloroform 551

Chloropicrin 551

Chrysene 550,550.1

Dibenz(a,h)anthracene 550,550.1

Dibromoacetic Acid 552

Dibromoacetonitrile 551

Dibromochloromethane 551

1,2-Dibromo-3-chloropropane(DBCP)

551

1,2-Dibromoethane(EDB) 551

Dichloroacetic Acid 552

Dichloroacetonitrile 551

2,4-Dichlorophenol 552

1,1-Dichloropropanone-2 551

Diethyl phthalate 506

Dimethyl phthalate 506

Di-n-butyl phthalate 506



Di-n-octyl phthalate 506

Diquat 549

Endothall 548

Fluoranthene 550,550.1

Fluorene 550,550.1

Glyphosate 547

Indeno(1,2,3-cd)pyrene 550,550.1

Monobromoacetic Acid 552

Monochloroacetic Acid 552

Naphthalene 550,550.1

Paraquat 549

Phenanthrene 550,550.1

Pyrene 550,550.1

2,3,7,8-Tetrachlorodibenzo-p-dioxin

513

Tetrachloroethylene 551

Trichloroacetic Acid 552

Trichloroacetonitrile 551

1,1,1-Trichloroethane 551

Trichloroethylene 551

2,4,6-Trichlorophenol 552

1,1,1-Trichloropropanone-2

551

Introduction

James W. Eichelberger

U. S. Environmental Protection Agency

An integral component of the role of the Environmental Protection Agency (EPA) in protecting thequality of the Nation's water resources is the provision of means for monitoring water quality. Inkeeping with this role, EPA develops and disseminates analytical methods for measuring chemicaland physical parameters affecting water quality, including chemical contaminants which may have



potential adverse effects upon human health. This manual provides nine, analytical methods for 54organic contaminants, which may be present in drinking water or drinking water sources. InDecember 1988, EPA published "METHODS FOR THE DETERMINATION OF ORGANIC COMPOUNDSIN DRINKING WATER", EPA/600/4-88/039, a manual containing 13 methods for approximately 200potential drinking water contaminants. The current manual is a supplement to the earlier version,providing, for the most part, methods for analytes which appear at a later time in the regulatoryframework. Efforts have been made herein to provide a manual and methods format, which isconsistent with the earlier version.

Regulatory Background

Analytical methodology for monitoring water quality serves a number of related purposes, includingoccurrence studies in community water systems, health effects studies, and the determination ofthe efficacy of various water treatment approaches. These activities, in turn, form the supportingbases for water quality regulations, and the support of these regulations is the ultimate purpose ofthe analytical methods. Limitations on the levels of specific contaminants are codified in proposedand promulgated Federal regulations developed in response to the Safe Drinking Water Act (SDWA)of 1974 and the SDWA amendments of 1986. The Act requires EPA to promulgate regulations forcontaminants in drinking water which may cause adverse health effects and which are known oranticipated to occur in public water systems. The 1986 amendments require regulations to includeMaximum Contaminant Levels (MCL's) with compliance determined by regulatory monitoring or bythe application of an appropriate treatment, when adequate analytical methodology is notavailable. In addition, the 1986 amendments specified 83 contaminants, originally scheduled forregulation by June 19, 1989. The amended Act also required EPA to develop a priority list ofadditional contaminants, to propose 25 more of these by January of 1988 for subsequentregulation and to continue this process by the addition of 25 from the priority list on a triennialbasis thereafter.

Of the original 83 pollutants, regulations for eight volatile organic chemicals (VOC) werepromulgated in June 1987 (see 52 FR 25690 and 51 FR 11396). Analytical methods for these eightas well as other unregulated VOC's were published in the December 1988 manual (EPA Methods502.1, 502.2, 503.1, 524.1 and 524.2). Regulations for thirty synthetic organic chemicals (SOC's)were proposed May 22, 1989 (54 FR 22062) and scheduled for promulgation by December 1990.Note that this group included six SOC's which, by authority of provisions in the 1986 amendments,were substituted into the original list of 83 in January 1988 (53 FR 1892) - namely aldicarbsulfoxide, aldicarb sulfone, ethylbenzene, heptachlor, heptachlor epoxide and styrene. With theexception of lindane, analytical methods for all thirty compounds are by the VOC methods above orSOC methods also included in the 1988 manual.

The current manual provides analytical methods for many of the remaining contaminants on theoriginal list of 83 - namely adipates, diquat, endothall, glyphosate, polycyclic aromatichydrocarbons (PAH's), phthalates and dioxin. Phase V of EPA regulations for these and eleven otherremaining SOC's from the list of 83 is scheduled for proposal in June 1990 and promulgation inMarch 1992. Analytical methods for the latter eleven were included in the December 1988 manual.Methods 551 and 552 of this manual cover the most important classes of organic chlorinationdisinfection byproducts. These contaminants were included in the first EPA priority list of additionalsubstances, which may require regulation under the Act (see 53 FR 1892). At least some of thesewill be regulated by EPA's phase IV disinfectants and disinfectant byproducts rule scheduled forproposal early in 1992.

General Comments

The current manual provides methods, which are in the same format and cast in the sameterminology as the December 1988 manual. The introduction to the earlier manual discussesgeneral method features on format, sample matrices, method detection limits, and calibration andquality control samples. These same comments apply herein. In particular, these methods arewritten in standardized terminology in a stand-alone format, requiring no other source material forapplication. The methods are designed for drinking water and drinking water sources and not formore complex matrices such as waste water, hazardous waste effluents or biological fluids. Themethod detection limits provided were determined by replicate analyses of fortified reagent waterover a relatively short period of time. As such, these are somewhat idealized limits, butnevertheless provide a useful index of method performance. Reporting limits for reliablequantitative data may be considerably higher.



The quality assurance sections are uniform and contain minimum requirements for operating areliable monitoring program - initial demonstration of performance, routine analyses of reagentblanks, analyses of fortified reagent blanks and fortified matrix samples, and analyses of qualitycontrol (QC) samples. Other quality control practices are recommended and may be adopted tomeet the particular needs of monitoring programs - e. g., the analyses of field reagent blanks,instrument control samples and performance evaluation samples. Where feasible, surrogateanalytes have been included in the methods as well as internal standards for calibration. Surrogaterecoveries and the internal standard response should be routinely monitored as continuing checkson instrument performance, calibration curves and overall method performance.

The Analytical Methods

This manual includes seven methods for synthetic organic chemicals and two methods forchlorination disinfection byproducts. In general, the analytes may by classified as nonvolatile andthree of the methods employ separation by high performance liquid chromatography (HPLC). Theremainder utilize capillary column gas chromatography (GC). Two of the methods use convenientliquid-solid extraction (LSE) methods for analyte isolation, and two others offer LSE as an option.By contrast to the original manual, four of the methods are for single analytes - 2,3,7,8-tetrachlorobenzo-p-dioxin, glyphosate, endothall and diquat. These analytes are not readilyamenable to generic methods. Each method provides an adequate summary statement. Someadditional comments are germane here.

Method 506 for phthalates and adipates offers both liquid-liquid extraction (LLE) and LSE options.After capillary column GC separation, a photoionization detector is required for detection and MDL'sare limited to approximately 10 g/L. Phthalates and adipates are among the most commoncontaminants encountered in the laboratory and extreme care must be taken to ensure cleanreagent blanks.

Dioxin may be an extremely toxic chemical and water concentrations of a few parts per trillion(pg/L) are of concern. In addition to extreme sensitivity, unambiguous identification is an analyticalrequirement. Thus, Method 513 is an inherently complex method, which employs LLE or LSE,extract cleanup, a sample concentration factor of 105, capillary column GC separation and analysisby high resolution mass spectrometry. In addition, labeled isotopes of dioxin are employed assurrogate analyte and internal standard to aid in identification and quantitation and to compensatefor analyte losses during the complex sample handling procedure.

Methods 547, 548 and 549 are single analyte procedures for glyphosate, endothall and diquat.Paraquat is a non-regulated ionic herbicide quite similar to diquat and may be analyzedsimultaneously. These may be characterized as difficult analytes because of their high watersolubility and low volatility. In addition, glyphosate and endothall require derivatization prior todetection. Glyphosate is analyzed by direct aqueous HPLC injection and undergoes post-columnderivatization prior to fluorescence detection. Endothall must be transferred from the aqueousphase to an acetic acid matrix for derivatization, followed by analysis by GC with electron capturedetection (ECD). As with glyphosate, no preconcentration factor is involved. Method 549 providesfor the extraction and concentration of diquat and paraquat in the base forms by LSE with a C-8cartridge, preconditioned to operate in the reverse phase mode. The analytes are eluted with anacidic solvent and, after addition of ion-pairing reagent, are separated by HPLC. The analytes aredetected by ultraviolet absorption (UV) with confirmation provided by a photodiode arrayspectrometer.

Methods 550 and 550.1 provide HPLC alternatives for polycyclic aromatic hydrocarbons. Method550 employs a conventional serial LLE approach while 550.1 uses a LSE procedure similar toMethod 525. Dual UV and fluorescence detectors are employed, with considerably lower MDL'sreported for the latter.

Halogenated organic byproducts, other than the regulated trihalomethanes, account for most of thetotal organic halogen formed by the chlorination of water supplies. The most important classes interms of occurrence are the neutral analytes of Method 551 and the haloacetic acids of Method552. Method 551 is quite similar to Method 504, employing a simple one step LLE and directinjection of the extract into a capillary GC with ECD detection. The haloacetic method is a serialLLE with analysis by GC-ECD and is quite similar to, but simpler than, Method 515.1 for acidherbicides. Both employ diazomethane for methylation with a micromolar generation procedure,which avoids the hazards associated with handling concentrated diazomethane. These two methodsare unique in that significant background concentrations will always be present in chlorinated



supplies. When determining fortified matrix recoveries as required in the quality assurance (QA)section, these background levels must be taken into account when deciding upon fortificationconcentrations. In addition, the uncertainty in measuring the background level should beconsidered when establishing control limits, as called for in the quality assurance section.


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Methods for the Determination of Organic Compounds inDrinking WaterSupplement II



EPA-600/R-92/129AUGUST 1992

This manual is available from NTIS and contains Methods 515.2, 524.2, 548.1, 549.1, 552.1, 553,554 and 555. Please note that revised versions of Methods 515.2 and 524.2 and Method 552.2 arepublished in Supplement III which is described below. Address your request for this manual toNTIS and ask for their order number PB92-207703; the cost is $55.00.

Abstract

Eight analytical methods covering 133 organic contaminants which may be present in drinkingwater or drinking water sources are described in detail. These methods will give the laboratoryanalyst the capability to accurately and precisely determine organic compounds that are currentlyregulated in drinking water, designated for regulation by the Office of Ground Water and DrinkingWater in the near future, or potential candidates for regulation. Five of the methods in this manual,Methods 515.2, 524.2 Revision 4.0, 548.1, 549.1, and 552.1, replace older versions of thesemethods. The older versions were numbered 515.1, 524.2 Revision 3.0, 548, 549, and 552,respectively, and appeared in either of two previous organic methods manuals. The new versionsemploy new analytical techniques, such as liquid-solid extraction, to improve method performanceand reduce the use of organic solvents. Three are new methods for the determination ofsemivolatile compounds: Method 554 for ozonation disinfection by-products, Method 555 forphenoxyacid herbicides using the novel approach of in-line extraction/high performance liquidchromatography (HPLC), and Method 553 for nonvolatile compounds using particle beam HPLC/MS.

Table of Contents

MethodNumber

Title Revision Page

- Foreword - iii

- Abstract - iv

- Acknowledgment - vi

- Analyte - Method Cross Reference - vii

- Introduction - 1

524.2Measurement of Purgeable OrganicCompounds in Water by Capillary Column 4.0 5




Gas Chromatography/Mass Spectrometry

515.2

Determination of Chlorinated Acids in WaterUsing Liquid-Solid Extraction and GasChromatography With an Electron CaptureDetector

1.0 51

548.1

Determination of Endothall in Drinking Waterby Ion Exchange Extraction, Acidic Methanol,Methylation Gas Chromatography/MassSpectrometry

1.0 89

549.1Determination of Diquat and Paraquat inDrinking Water by Liquid-Solid Extractionand HPLC with Ultraviolet Detection

1.0 119

552.1

Determination of Haloacetic Acids andDalapon in Drinking Water by Ion ExchangeLiquid-Solid Extraction and GasChromatography With Electron CaptureDetection

1.0 143

553

Determination of Benzidines and Nitrogen-Containing Pesticides in Water by Liquid-Liquid Extraction or Liquid-Solid Extractionand Reverse Phase High Performance LiquidChromatography/Particle Beam/MassSpectrometry

1.1 173

554Determination of Carbonyl Compounds inDrinking Water by DNPH Derivatization andHigh Performance Liquid Chromatography

1.0 213

555Determination of Chlorinated Acids in Waterby High Performance Liquid ChromatographyWith a Photodiode Array Ultraviolet Detector

1.0 237

Analyte - Method CrossReference

Analyte MethodNo.

Acetaldehyde 554

Acetone 524.2

Acifluorofen 515.2,555

Acrylonitrile 524.2

Allyl chloride 524.2

Bentazon 515.2,555



Benzene 524.2

Benzidine 553

Benzoylprop ethyl 553

Bromobenzene 524.2

Bromochloroacetic acid 552.1

Bromochloromethane 524.2

Bromodichlorobenzene 524.2

Bromoform 524.2

Bromomethane 524.2

Butanal 554

2-Butanone 524.2

n-Butylbenzene 524.2

sec-Butylbenzene 524.2

tert-Butylbenzene 524.2

Carbaryl 553

Carbon disulfide 524.2

Carbon tetrachloride 524.2

Chloramben 515.2,555

Chloroacetonitrile 524.2

Chlorobenzene 524.2

1-Chlorobutane 524.2

Chloroethane 524.2

Chloroform 524.2

Chloromethane 524.2

2-Chlorotoluene 524.2

4-Chlorotoluene 524.2

Crotonaldehyde 554

Cyclohexanone 554

Dalapon 552.1

DCPA (Dacthal) andmetabolites

515.2,555

Decanal 554



Dibromoacetic acid 552.1

Dibromochloromethane 524.2


524.2

1,2-Dibromoethane 524.2

Dibromomethane 524.2

Dicamba 515.2,555

Dichloroacetic acid 552.1

1,2-Dichlorobenzene 524.2



3,3'-Dichlorobenzidine 553

3,5-Dichlorobenzoic acid 515.2,555

2,4-DB (2,4-dichlorobutanoic acid)

515.2,555

trans-1,4-Dichloro-2-butene

524.2

Dichlorodifluoromethane 524.2

1,1-Dichloroethane 524.2

1,2-Dichloroethane 524.2

1,1-Dichloroethene 524.2

cis-1,2-Dichloroethene 524.2

trans-1,2-Dichloroethene 524.2

2,4-D (2,4-dichlorophenoxyaceticacid)

515.2,555

1,2-Dichloropropane 524.2



1,1-Dichloropropene 524.2

1,1-Dichloropropanone 524.2

cis-1,3-Dichloropropene 524.2

trans-1,3- 524.2



Dichloropropene

Dichlorprop 515.2,555

Diethyl ether 524.2

3,3'-Dimethoxybenzidine 553

3,3'-Dimethylbenzidine 553

Dinoseb 515.2,555

Diquat 549.1

Diuron 553

Endothall 548.1

Ethylbenzene 524.2

Ethyl methacrylate 524.2

Formaldehyde 554

Heptanal 554

Hexachlorobutadiene 524.2

Hexachloroethane 524.2

Hexanal 554

2-Hexanone 524.2

5-Hydroxydicamba 515.2,555

Isopropylbenzene 524.2

4-Isopropyltoluene 524.2

Linuron (Lorox) 553

Methacrylonitrile 524.2

Methylacrylate 524.2

Methylene chloride 524.2

Methyl iodide 524.2

Methylmethacrylate 524.2

4-Methyl-2-pentanone 524.2

Methyl-t-butyl ether 524.2

Monobromoacetic acid 552.1

Monochloroacetic acid 552.1



Monuron 553

Naphthalene 524.2

Nitrobenzene 524.2

4-Nitrophenol 515.2,555

2-Nitropropane 524.2

Nonanal 554

Octanal 554

Paraquat 549.1

Pentachloroethane 524.2

Pentachlorophenol (PCP) 515.2,555

Pentanal 554

Picloram 515.2,555

Propanal 554

Propionitrile 524.2

n-Propylbenzene 524.2

Rotenone 553

Siduron 553

2,4,5-TP (silvex) 515.2,555

Styrene 524.2

Tetrachloroethene 524.2

1,1,1,2-Tetrachloroethane 524.2

1,1,2,2-Tetrachloroethane 524.2

Tetrahydrofuran 524.2

Toluene 524.2

Trichloroacetic acid 552.1

1,2,3-Trichlorobenzene 524.2

1,2,4-Trichlorobenzene 524.2

Trichloroethene 524.2

1,1,1-Trichloroethane 524.2

1,1,2-Trichloroethane 524.2



Trichlorofluoromethane 524.2

2,4,5-T (2,4,5-trichlorophenoxyaceticacid)

515.2,555

1,2,3-Trichloropropane 524.2

1,2,4-Trimethylbenzene 524.2

1,3,5-Trimethylbenzene 524.2

Vinyl chloride 524.2

m-Xylene 524.2

o-Xylene 524.2

p-Xylene 524.2

Introduction

James W. Eichelberger


An integral component of the role of the Environmental Protection Agency (EPA) in protecting thequality of the Nation's water resources is the provision of means for monitoring water quality. Inkeeping with this role, EPA develops and disseminates analytical methods for measuring chemicaland physical parameters affecting water quality, including chemical contaminants that may havepotential adverse effects upon human health. This manual provides eight analytical methods for133 organic contaminants, which may be present in drinking water or drinking water sources. InDecember 1988, EPA published "METHODS FOR THE DETERMINATION OF ORGANIC COMPOUNDSIN DRINKING WATER," EPA/600/4-88/039, a manual containing 13 methods for approximately 200potential drinking water contaminants. This original manual was revised and reprinted in July 1991.Supplement I, containing nine methods to determine 54 compounds, was published in July 1990.

This manual is a second supplement to the July 1991 revision of the earlier 1988 manual. Thismanual provides methods to determine analytes that appear at a later time in the regulatoryframework, and technology that supports the EPA Pollution Prevention Policy. Efforts have beenmade to provide a manual that is consistent with the earlier versions.

Regulatory Background

Analytical methodology for monitoring water quality serves a number of related purposes, includingoccurrence studies in community water systems, health effects studies, and the determination ofthe efficacy of various water treatment approaches. These activities, in turn, form the supportingbasis for water quality regulations, and the support of these regulations is the ultimate purpose ofthe analytical methods. Limitations on the levels of specific contaminants are codified in proposedand promulgated Federal regulations developed in response to the Safe Drinking Water Act (SDWA)of 1974 and the SDWA amendments of 1986. The Act requires EPA to promulgate regulations fordrinking water contaminants that may cause adverse health effects and which are known oranticipated to occur in public water systems. The 1986 amendments require regulations to includeMaximum Contaminant Levels (MCLs) with compliance determined by regulatory monitoring or bythe application of an appropriate treatment, when adequate analytical methodology is notavailable. In addition, the 1986 amendments specified 83 contaminants, originally scheduled forregulation by June 19, 1989. The amended Act also required EPA to develop a priority list ofadditional contaminants, to propose 25 more of these by January 1988 for subsequent regulation,and to continue this process by the addition of 25 from the priority list on a triennial basisthereafter.



Of the original 83 pollutants, regulations for eight volatile organic chemicals (VOCs) werepromulgated in June 1987 (see 52 FR 25690 and 51 FR 11396). Analytical methods for these eightas well as other unregulated VOCs were published in the December 1988 manual (EPA Methods502.1, 502.2, 503.1, 524.1 and 524.2). Regulations for 30 organic chemicals, 10 volatilecompounds and 20 pesticide and related compounds, were finalized and published in January 1991.This group included six compounds which, by authority of provisions in the 1986 amendments,were substituted into the original list of 83 in January 1988 (53 FR 1892): namely, aldicarbsulfoxide, aldicarb sulfone, ethylbenzene, heptachlor, heptachlor epoxide and styrene. With theexception of lindane, analytical methods for all 30 compounds are by the VOC methods above orSOC methods also included in the 1988 manual.

Supplement I provides analytical methods for many of the remaining contaminants on the originallist of 83: namely, adipates, diquat, endothall, glyphosate, polycyclic aromatic hydrocarbons(PAHs), phthalates and dioxin. Phase V of EPA regulations for 3 volatile compounds, 9 pesticides,and 6 other organics from the list of 83 was promulgated on July 17, 1992.

General Comments

Supplement II provides methods, which are cast in the same terminology as the December 1988manual, the July 1991 revision, and Supplement I. The introductions to the earlier manuals discussgeneral method features on format, sample matrices, method detection limits (MDLs), andcalibration and quality control samples. These same comments apply herein. In particular, thesemethods are written in standardized terminology in a stand-alone format, requiring no other sourcematerial for application. The methods in this manual, unlike previous manuals, are assembled inthe format recommended by the Agency's Environmental Monitoring Management Council (EMMC).The methods are designed primarily for drinking water and drinking water sources. However, someperformance data are included for more complex matrices such as wastewater. The MDLs providedwere determined by replicate analyses of fortified reagent water over a relatively short period oftime. As such, these are somewhat idealized limits; nevertheless, provide a useful index of methodperformance. Reporting limits for reliable quantitative data may be considerably higher.

The quality control sections are uniform and contain minimum requirements for operating a reliablemonitoring program -- initial demonstration of performance, routine analyses of reagent blanks,analyses of fortified reagent blanks and fortified matrix samples, and analyses of quality control(QC) samples. Other QC practices are recommended and may be adopted to meet the particularneeds of monitoring programs; e.g., the analyses of field reagent blanks, instrument controlsamples and performance evaluation samples. Where feasible, surrogate analytes have beenincluded in the methods as well as internal standards for calibration. Surrogate recoveries and theinternal standard response should be routinely monitored as continuing checks on instrumentperformance, calibration curves and overall method performance.

The Analytical Methods

This manual contains eight methods. These methods utilize new sample preparation technologysuch as disk or cartridge liquid-solid extraction, or use new relatively harmless methylatingreagents; therefore, directly support the Environmental Protection Agency's Policy on PollutionPrevention. Methods 515.2, 524.2 Revision 4.0, 548.1, 549.1, and 552.1 replace older versions ofthese methods. The older versions were numbered 515.1, 524.2 Revision 3.0, 548, 549, and 552respectively, and appeared in either of the two previously published organic methods manuals("Methods for the Determination of Organic Compounds in Drinking Water," EPA/600/4-88/039,December 1988, revised July 1991, or "Methods for the Determination of Organic Compounds inDrinking Water - Supplement I," EPA/600/4-90/020, July 1990; Environmental Monitoring SystemsLaboratory - Cincinnati). The Environmental Protection Agency's Office of Ground Water andDrinking Water believes that only one version of any analytical method should be approved forcompliance with drinking water regulations. Thus, EPA will quickly approve the new versions ofthese five methods. Until these methods are promulgated by EPA, the older versions should beretained for compliance purposes. The remaining three are new methods for the determination ofsemivolatile or nonvolatile compounds: Method 553 for nonvolatile organics using a highperformance liquid chromatograph interfaced to a mass spectrometer through a particle beaminterface, Method 554 for ozonation disinfection by-products, and Method 555 for phenoxyaceticacid herbicides using the novel approach of in-line liquid-solid extraction and high performanceliquid chromatography.



Method 524.2, Revision 4.0 contains 24 new target analytes, which are marked in the analyte listwith an asterisk, bringing the total number of method analytes to 84 compounds. Initial studieswere conducted to evaluate 48 candidate VOCs of environmental interest for possible inclusion intothis method. These candidate compounds included many polar, water soluble compounds which arevery difficult to remove from the water matrix. Results indicated that only 24 of these candidateswere stable in water over a 14-day holding time and could be efficiently purged and trapped fromwater with acceptable accuracy and precision. MDLs for these newly added compounds aregenerally 1 g/L or lower.

Method 515.2 is an improved method to determine chlorinated herbicides in water. This methodutilizes a new liquid-solid disk extraction procedure. Some of the phenolic herbicides are verydifficult to derivatize, and still require the use of the stronger reagent, diazomethane. The diskextraction replaces the cumbersome liquid-liquid extraction and the Florisil cleanup in Method515.2. Dalapon, a method analyte in Method 515.1, is no longer a method analyte in this newmethod. This compound is now determined using Method 552.1.

Method 548.1 is an improved method for the determination of endothall and is intended to replacethe older Method 548. This method utilizes an intermediate strength amine anion exchange sorbentto extract the endothall from a 100 mL sample aliquot, and forms the dimethyl derivative quicklyand easily using acidic methanol as the methylating reagent. Dimethyl endothall is then identifiedand measured with gas chromatography/mass spectrometry (GC/MS). A flame ionization detectormay be used if a second dissimilar column is used for corroboration. Method 548.1 has a MDLapproximately ten times lower than the older 548.

Method 549.1 is an improvement over the existing Method 549 in that it now utilizes liquid-soliddisk extractions in addition to the cartridges. The expanded liquid-solid extraction technologysignificantly reduces the amount of organic solvent required to carry out the extraction. Using lesspotentially harmful solvents directly supports the Environmental Protection Agency's Policy onPollution Prevention in the laboratory. Comparable MDLs below a part per billion are achieved withboth disks and cartridges.

Method 552.1 is a liquid-solid extraction method to determine haloacetic acid disinfection by-products and the chemically similar chlorinated herbicide, dalapon, in water. This method wasdesigned as a simplified alternative to the cumbersome Method 552 which employs liquid-liquidextraction. This method provides a much superior technique for Dalapon over the complexherbicide procedure described in Method 515.1. The sample is extracted with a miniature anionexchange column, and the analytes are methylated directly in the eluant using acidic methanolinstead of diazomethane. MDLs using this method for matrices which pose no analyte losses due tomatrix effects are generally 1 g/L or lower.

Method 553 is a new method for the determination of nonvolatile organic compounds, includingbenzidines and nitrogen containing pesticides, in water. This method employs reverse phase highperformance liquid chromatography (HPLC) interfaced to a mass spectrometer through a particlebeam interface. This new technology provides the analyst the ability to determine a large, newscope of nonvolatiles heretofore extremely difficult or impossible to determine in a water matrix.Among the compounds on the analyte list for this method are two regulated compounds, aldicarbsulfone regulated in January 1991 and carbofuran regulated in May 1992.

Method 554 is a new HPLC method optimized for the determination of selected carbonyl compoundsin finished drinking water and raw source water. These carbonyl compounds are either known orsuspected disinfection by-products from the ozonation disinfecting process. This method alsoutilizes cartridge liquid-solid extraction technology in support of the Agency's Pollution PreventionPolicy. MDLs for the analytes in this method range from 3 to 69 g/L.

Method 555 is a new method utilizing HPLC with a conventional photodiode array HPLC detector todetermine the same chlorinated herbicides on the analyte lists in Methods 515.1 and 515.2. Thismethod requires no derivatization procedure which completely eliminates the need fordiazomethane or even acidic methanol. This method utilizes a new extraction approach, in-lineconcentration of the analytes on a concentrator column, which requires only the HPLC mobilephase as the extracting solvent. The entire amount of herbicide contained in a 20-mL samplealiquot is introduced into the analytical system giving the method the needed sensitivity. Thismethod directly supports the Pollution Prevention Policy, and completely eliminates the possibleexposure of the analyst to harmful extracting solvent vapors, and to the possibility of adiazomethane explosion.




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Methods for the Determination of Organic Compounds inDrinking WaterSupplement III

National Exposure Research LaboratoryOffice of Research and Development


EPA-600/R-95/131August 1995

This manual is available from NTIS and contains Methods 502.2, 504.1, 505, 506, 507, 508,508.1, 509, 515.1, 515.2, 524.2, 525.2, 531.1, 551.1 and 552.2. Address your request for thismanual to NTIS and ask for their order number PB95-261616; the cost is $67.00.

Abstract

Fifteen analytical methods for organic compounds in drinking water are documented in detail. Mostof these methods were published as prior versions in other methods manuals in this series. Theversions in Supplement III provide corrections, minor technical enhancements, and editorialimprovements to the previously published analytical methods. Several previously distributed butnot formally published methods are also included. Fourteen of the fifteen methods utilize highresolution gas chromatography (GC) for separation of analytes from each other and from othersubstances in the water sample. One method employs high performance reverse phase liquidchromatography for the separation. Two methods utilize a mass spectrometer for the unambiguousidentification and measurement of the compounds separated by high resolution GC. These twomethods are extremely versatile and have been single-laboratory validated for a total of 194individual compounds and 8 commercial product mixtures. Most methods have also been multi-laboratory validated although not all possible analytes have been included in these studies.Essentially all of the major chlorine disinfection by-products that have been identified in drinkingwater are included in the methods in this manual.

Table of Contents

MethodNumber

Title Revision Page

- Foreword - iii

- Abstract - iv

- Acknowledgment - vii

- Analyte - Method Cross Reference - viii

- Introduction - 1

502.2

Volatile Organic Compounds in Water byPurge and Trap Capillary Column GasChromatography with Photoionization andElectrolytic Conductivity Detectors in Series

2.1




504.1

1,2-Dibromoethane (EDB), 1,2-Dibromo-3-Chloro-propane (DBCP), and 1,2,3-Trichloropropane (123TCP) in Water byMicroextraction and Gas Chromatography

1.1

505

Analysis of Organohalide Pesticides andCommercial Polychlorinated Biphenyl (PCB)Products in Water by Microextraction andGas Chromatography

2.1

506

Determination of Phthalate and AdipateEsters in Drinking Water by Liquid-LiquidExtraction or Liquid-Solid Extraction and GasChromatography with PhotoionizationDetection

1.1

507

Determination of Nitrogen- and Phosphorus-Containing Pesticides in Water by GasChromatography with a Nitrogen-PhosphorusDetector

2.1

508Determination of Chlorinated Pesticides inWater by Gas Chromatography with anElectron Capture Detector

3.1

508.1

Determination of Chlorinated Pesticides,Herbicides, and Organohalides by Liquid-Solid Extraction and Electron Capture GasChromatography

2.0

509Determination of Ethylene Thiourea (ETU) inWater using Gas Chromatography with aNitrogen-Phosphorus Detector

1.1

515.1Determination of Chlorinated Acids in Waterby Gas Chromatography with an ElectronCapture Detector

4.1

515.2

Determination of Chlorinated Acids in Waterusing Liquid-Solid Extraction and GasChromatography with an Electron CaptureDetector

1.1

524.2Measurement of Purgeable OrganicCompounds in Water by Capillary ColumnGas Chromatography/Mass Spectrometry

4.1

525.2

Determination of Organic Compounds inDrinking Water by Liquid-Solid Extractionand Capillary Column GasChromatography/Mass Spectrometry

2.0

531.1

Measurement of N-Methylcarbamoyloximesand N-Methylcarbamates in Water by DirectAqueous Injection HPLC with Post Column

3.1



Derivatization

551.1

Determination of Chlorination DisinfectionByproducts, Chlorinated Solvents, andHalogenated Pesticides/Herbicides inDrinking Water by Liquid-Liquid Extractionand Gas Chromatography with Electron-Capture Detection

1.0

552.2

Determination of Haloacetic Acids andDalapon in Drinking Water by Liquid-LiquidExtraction, Derivatization and GasChromatography with Electron CaptureDetection

1.0

Analyte - Method Cross Reference

Analyte MethodNo.

Acenaphthylene 525.2

Acetone 524.2

Acifluorfen 515.1,515.2

Acrylonitrile 524.2

Alachlor

505, 507,508.1,525.2,551.1

Aldicarb 531.1

Aldicarb sulfone 531.1

Aldicarb sulfoxide 531.1

Aldrin505, 508,508.1,525.2

Allyl chloride 524.2

Ametryn 507,525.2

Anthracene 525.2

Atraton 507,525.2

Atrazine

505, 507,508.1,525.2,551.1



Baygon 531.1

Bentazon 515.1,515.2

Benzene 502.2,524.2

Benz[a]anthracene 525.2

Benzo[b]fluoranthene 525.2

Benzo[k]fluoranthene 525.2

Benzo[a]pyrene 525.2

Benzo[g,h,i]perylene 525.2

Bis (2-ethylhexyl)phthalate

506

Bis (2-ethylhexyl) adipate 506

Bromobenzene 502.2,524.2

Bromacil507,525.2,551.1

Bromochloroacetic acid 552.2

Bromochloroacetonitrile 551.1

Bromochloromethane502.2,524.2,551.1

Bromodichloroacetic acid 552.2

Bromodichloromethane 502.2,524.2

Bromoform502.2,524.2,551.1

Bromomethane 502.2,524.2

Butachlor507,508.1,525.2

2-Butanone 524.2

Butylate 507,525.2

Butylbenzylphthalate 506,



525.2

n-Butylbenzene 502.2,524.2

sec-Butylbenzene 502.2,524.2

tert-Butylbenzene 502.2,524.2

Carbaryl 531.1

Carboxin 507,525.2

Carbofuran 531.1

Carbon disulfide 524.2

Carbon tetrachloride502.2,524.2,551.1

Chloramben 515.1

Chloral Hydrate 551.1

Chlordane 505, 508

Alpha-chlordane505, 508,508.1,525.2

Gamma-chlordane505, 508,508.1,525.2

Trans nonachlor 525.2

Chloroacetonitrile 524.2

Chlorobenzene 502.2,524.2

Chlorobenzilate508,508.1,525.2

2-Chlorobiphenyl 525.2

Chlorodibromoacetic acid 552.2

1-Chlorobutane 524.2

Chloroethane 502.2,524.2

Chloroform502.2,524.2,



551.1

Chloromethane 502.2,524.2

Chloroneb508,508.1,525.2

Chloropicrin 551.1

Chlorothalonil508,508.1,525.2

2-Chlorotoluene 502.2,524.2

4-Chlorotoluene 502.2,524.2

Chlorpropham 507,525.2

Chlorpyrifos 525.2

Chrysene 525.2

Cyanazine508.1,525.2,551.1

Cycloate 507,525.2

Dacthal(DCPA) 525.2

2,4-D 515.1,515.2

Dalapon515.1,515.2,552.2

2,4-DB 515.1,515.2

DCPA acid metabolites508,508.1,515.1

4,4'-DDD508,508.1,525.2

4,4'-DDE508,508.1,525.2



4,4'-DDT508,508.1,525.2

Diazinon 507,525.2

Dibenz[a,h]anthracene 525.2

Dibromoacetic acid 552.2

Dibromoacetonitrile 551.1

Dibromochloromethane502.2,524.2,551.1


502.2,504.1,524.2,551.1

1,2-Dibromoethane

502.2,504.1,524.2,551.1

Dibromomethane 502.2,524.2

Dicamba 515.1,515.2

Dichloroacetic acid 552.2

Dichloroacetonitrile 551.1

1,2-Dichlorobenzene 502.2,524.2



3,5-Dichlorobenzoic acid 515.1,515.2

trans-1,4-Dichloro-2-butene

524.2

1,1-Dichloroethane 502.2,524.2

1,2-Dichloroethane 502.2,524.2

502.2,



1,1-Dichloroethene524.2

cis-1,2-Dichloroethene 502.2,524.2

trans-1,2-Dichloroethene 502.2,524.2

Dichlorodifluoromethane 502.2,524.2

1,2-Dichloropropane 502.2,524.2



1,1-Dichloropropene 502.2,524.2

1,1-Dichloropropanone 524.2

cis-1,3-Dichloropropene 502.2,524.2

trans-1,3-Dichloropropene 502.2,524.2

1,1-Dichloro-2-propanone 551.1

Dichloroprop 515.1,515.2

Di-n-butyl phthalate 506,525.2

Di-n-octyl phthalate 506

2,3-Dichlorobiphenyl 525.2

Dichlorvos 507,525.2

Dieldrin505, 508,508.1,525.2

Diethyl ether 524.2

Diethyl phthalate 506,525.2

Di(2-ethylhexyl)adipate 525.2

Di(2-ethylhexyl)phthalate 525.2

506,



Dimethyl phthalate525.2

2,4-Dinitrotoluene 525.2

2,6-Dinitrotoluene 525.2

Dinoseb 515.1,515.2

Diphenamid 507,525.2

Disulfoton 507,525.2

Disulfoton sulfone 507,525.2

Disulfoton sulfoxide 507,525.2

Endosulfan I508,508.1,525.2

Endosulfan II508,508.1,525.2

Endosulfan sulfate508,508.1,525.2

Endrin

505, 508,508.1,525.2,551.1

Endrin aldehyde

508,508.1,525.2,551.1

Endrin ketone 551.1

EPTC 507,525.2

Ethoprop 507,525.2

Ethylbenzene 502.2,524.2

Ethyl methacrylate 524.2

Ethylene thiourea 509



Etridiazole508,508.1,525.2

Fenamiphos 507,525.2

Fenarimol 507,525.2

Fluorene 525.2

Fluridone 507,525.2

Heptachlor

505, 508,508.1,525.2,551.1

Heptachlor Epoxide

505, 508,508.1,525.2,551.1

2,2',3,3',4,4',6-Heptachlorobiphenyl

525.2

Hexachlorobenzene

505, 508,508.1,525.2,551.1

Hexachlorobutadiene 502.2,524.2

Hexachlorocyclopentadiene505,508.1,551.1

2,2',4,4',5,6'-Hexachlorobiphenyl

525.2

Hexachlorocyclohexane,alpha

525.2

Hexachlorocyclohexane,beta

525.2

Hexachlorocyclohexane,delta

525.2

Hexachlorocyclopentadiene 525.2

Hexachloroethane 524.2

2-Hexanone 524.2



Hexazinone 507,525.2

HCH-alpha 508,508.1

HCH-beta 508,508.1

HCH-delta 508,508.1

HCH-gamma (lindane) 508,508.1

3-Hydroxycarbofuran 531.1

5-Hydroxydicamba 515.1,515.2

Indeno[1,2,3,c,d]pyrene 525.2

Isophorone 525.2

Isopropylbenzene 502.2,524.2

4-Isopropyltoluene 524.2

Lindane (gamma-BHC)505,525.2,551.1

Merphos 507,525.2

Methacrylonitrile 524.2

Methiocarb 531.1

Methomyl 531.1

Methoxychlor

505, 508,508.1,525.2,551.1

Methylacrylate 524.2

Methylene chloride 502.2,524.2

Methyl iodide 524.2

Methylmethacrylate 524.2

Methyl paraoxon 507,525.2

4-Methyl-2-pentanone 524.2



Methyl-t-butyl-ether 524.2

Metolachlor

507,508.1,525.2,551.1

Metribuzin

507,508.1,525.2,551.1

Mevinphos 507,525.2

MGK 264 507,525.2

Molinate 507,525.2

Monobromoacetic acid 552.2

Monochloroacetic acid 552.2

Naphthalene 502.2,524.2

Napropamide 507,525.2

Nitrobenzene 524.2

4-Nitrophenol 515.1

2-Nitropropane 524.2

cis-Nonachlor 505

Norflurazon 507,525.2

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

525.2

Oxamyl 531.1

Pebulate 507,525.2

2,2',3',4,6-Pentachlorobiphenyl

525.2

Pentachloroethane 524.2

Pentachlorophenol515.1,515.2,525.2

508,



cis-Permethrin 508.1,525.2

Trans-Permethrin508,508.1,525.2

Phenanthrene 525.2

Picloram 515.1,515.2

Prometon 507,525.2

Prometryn 507,525.2

Pronamide 507,525.2

Propachlor508,508.1,525.2

Propazine 507,525.2

Propionitrile 524.2

Propylbenzene 502.2

n-Propylbenzene 524.2

Pyrene 525.2

Simazine505, 507,508.1,525.2

Simetryn 507,525.2

Stirofos 507,525.2

Styrene 502.2,524.2

2,4,5-T 515.1,515.2

2,4,5-TP 515.1,515.2

Tebuthiuron 507,525.2

Terbacil 507,



525.2

Terbufos 507,525.2

Terbutryn 507,525.2

2,2',4,4'-Tetrachlorobiphenyl

525.2

1,1,1,2-Tetrachloroethane 502.2,524.2

1,1,2,2-Tetrachloroethane 502.2,524.2

Tetrachloroethene 502.2,524.2

Tetrachloroethylene 551.1

Tetrahydrofuran 524.2

Toluene 502.2,524.2

Toxaphene505, 508,508.1,525.2

Triademefon 507,525.2

Tribromoacetic acid 552.2

Trichloroacetic acid 552.2

Trichloroacetonitrile 551.1

1,2,3-Trichlorobenzene 505.2,524.2

1,2,4-Trichlorobenzene 505.2,524.2

1,1,1-Trichloroethane502.2,524.2,551.1

1,1,2-Trichloroethane502.2,524.2,551.1

Trichloroethene 505.2,524.2

Trichloroethylene 551.1

502.2,



Trichlorofluoromethane524.2

1,1,1-Trichloro-2-propanone

551.1

1,2,3-Trichloropropane504.1,524.2,551.1

2,4,5-Trichlorobiphenyl 502.2,525.2

Tricyclazole 507,525.2

Trifluralin

508,508.1,525.2,551.1

1,2,4-Trimethylbenzene 502.2,524.2

1,3,5-Trimethylbenzene 502.2,524.2

Vernolate 507,525.2

Vinyl chloride 502.2,524.2

0-Xylene 505.2,524.2

m-Xylene 502.2,524.2

p-Xylene 502.2,524.2

Aroclor 1016505, 508,508.1,525.2

Aroclor 1221505, 508,508.1,525.2

Aroclor 1232505, 508,508.1,525.2

Aroclor 1242505, 508,508.1,525.2



Aroclor 1248505, 508,508.1,525.2

Aroclor 1254505, 508,508.1,525.2

Aroclor 1260505, 508,508.1,525.2

Introduction

William L. Budde and Jean W. Munch


The purpose of this third supplement to "Methods for the Determination of Organic Compounds inDrinking Water" is to provide corrections, minor technical enhancements, and editorialimprovements to some previously published analytical methods and to document severalsignificantly enhanced or previously unpublished methods. Some of these modifications weredescribed in "Technical Notes on Drinking Water Methods", EPA/600/R-94/173, October, 1994 andthese method changes have been incorporated into the body of the methods in this supplement. Allmethods in this supplement are written in a format specified by the United States EnvironmentalProtection Agency's Environmental Monitoring Management Council.

As in other manuals in this series, each of the methods in Supplement III was intended to standalone, that is, each method may be removed from the manual, photocopied, inserted into anotherbinder, and used without loss of information. The stand-alone character of the methods comes atsome cost of duplication of material, but the authors believe that the added bulk of the methods isa small price to pay for the flexibility of the format.

All the methods in supplement III have been given new dates and version numbers or slightlymodified method numbers to distinguish them from pre-viously published versions. A change in therevision number indicates a relatively small modification to the method and a change in themethod number usually indicates a relatively larger change in the method. The cover page of eachmethod gives the title, method number, revision, and date, and also lists the previous versions,previous authors, and dates if they are known. The purpose of this very brief method history is toassist users who may have older versions in their files in understanding the chronologicalrelationship of methods as technical improvements were made over the years. It also gives duecredit to previous authors who contributed to the development of the methods in this and previousmanuals in this series. Unless otherwise indicated, all authors were direct Federal employees of theU. S. Environmental Protection Agency at the time of their contributions.

Some methods in supplement III utilize the liquid-solid extraction technology which was pioneeredby the USEPA in the original Method 525 in 1988. The scientifically correct term liquid-solidextraction (LSE), in which both phases of the equilibrium partition process are named, is usedthroughout the manual in place of the misleading commercial term "solid phase extraction".Colloquial lab terms such as "clean-up" and "spike" are replaced by "sample preparation" or"interference separation" and "fortified" respectively.

While the title of supplement III, and previous manuals in this series, specifies drinking water,these methods will very likely be applicable to other aqueous matrices including surface water,ground water, beverages, and waste water. However since some methods have been tested withonly reagent water and/or drinking water, caution is needed when applying these methods tomatrices other than reagent or drinking water. One exception is Method 524.2 which has beentested in a large multi-laboratory validation study with a variety of aqueous matrices.



During 1992 the USEPA and the American Society for Testing and Materials (ASTM) Committee D-19 on Water jointly conducted a multi-laboratory study of an ASTM version of Method 524.2,revision 3.0 using 68 of the volatile organic compound analytes. Over 40 volunteer laboratoriesparticipated in the study to characterize the performance of Method 524.2 in terms of accuracy,precision, and detection limits. Analyses were conducted using fortified reagent water, drinkingwater, ground water, several industrial waste waters, and a simulated hazardous waste siteaqueous leachate. Fortified analyte concentrations ranged from 0.2 g/L to 80 g/L and generallyexcellent accuracy and precision was reported. Full details of that study will be published by theASTM.

The methods in supplement III are listed below along with a comment for each that gives theprevious version of the method, the citation and date of publication of the previous version, andthe highlights of the changes in the version in supplement III.

Methodin

Supp.III

Comments

502.2rev. 2.1

Rev. 2.0 was published in EPA/600/4-88/039 in Dec. 1988 andJuly 1991. Rev. 2.1 is modified to specify conditions underwhich alternative trapping materials may be used andinstructions are clarified for sample preservation anddechlorination. Conditions which do not require aphotoionization detector are specified.

504.1rev. 1.1

Method 504.1 improves Method 504 rev. 2.0 which waspublished in EPA/600/4-88/03s, the holding time, and thecompound 1,2,3-trichloropropane is added to the analyte list.Cautions are included on the frequent coelution of ethylenedibromide and bromodichloromethane.

505rev. 2.1

Rev. 2.0 was published in EPA/600/4-88/039 in Dec. 1988 andJuly 1991. Rev. 2.1 is modified to remove alternative detectorsexcept mass spectrometry for qualitative confirmation and toprovide additional instructions on the measurement of multi-component mixtures.

506rev. 1.1

Rev. 1.0 was published in EPA/600/4-90/020 (Supp. I) in July,1990. Rev. 1.1 is modified to correct errors in themethodsummary.

507rev. 2.1

Rev. 2.0 was published in EPA/600/4-88/039 in Dec. 1988 andJuly 1991. Rev. 2.1 is modified to remove mercuric chloride asa preservative. Data tables are reorganized for clarity andaddition of method detection limits. Alternative detectors areeliminated except mass spectrometry for qualitativeconfirmation.

508rev. 3.1

Rev 3.0 was published in EPA/600/4-88/039 in Dec. 1988 andJuly 1991. Rev. 3.1 is modified to remove mercuric chloride asa preservative. Data tables are reorganized for clarity andaddition of method detection limits. Alternative detectors areeliminated except mass spectrometry for qualitative



confirmation.

508.1rev. 2.0

Method 508.1 is a significant improvement to Method 508. Itemploys the liquid-solid extraction technology of Method 525.2and has an analyte list consisting of many Method 507 andMethod 508 substances including the former commercialAroclor mixtures.

509rev. 1.1

Method 509 is a single analyte method for the pesticidemetabolite ethylenethiourea. This method is derived fromnational pesticide survey Method 6.

515.1rev. 4.1

Rev. 4.0 was published in EPA/600/4-88/039 in Dec. 1988 andJuly 1991. Rev. 4.1 is modified to remove mercuric chloride asa preservative. Data tables are reorganized for clarity andaddition of method detection limits. Trimethylsilyldiazomethane(TMSD) is added as an alternative methylating agent.

515.2rev. 1.1

Rev. 1.0 was published in EPA/600/R-92/129 (Supp. II) inAugust, 1992. Rev. 1.1 is modified to includetrimethylsilyldiazomethane (TMSD) as an alternativemethylating agent.

524.2rev. 4.1

Rev. 4.0 was published in EPA/600/R-92/129 (Supp. II) inAugust, 1992. Rev. 4.1 is modified to specify conditions underwhich alternative trapping materials may be used andinstructions are clarified for sample preservation anddechlorination. The quality assurance section is clarified anddata for two analytes are added.

525.2rev. 2.0

Method 525.2, rev. 2.0 is an improvement to Method 525.1,rev. 2.2 which was published in EPA/600/4-88/039 inJuly,1991. Method 525.2 includes criteria for judging theequivalency of alternative liquid-solid extraction cartridges anddisks. The elution solvent is modified and data are included foradditional analytes including all former commercial Aroclormixtures.

531.1rev. 3.1

Rev. 3.0 was published in EPA/600/4-88/039 in Dec. 1988 andJuly 1991. Rev. 3.1 is modified to remove the requirement tofreeze the samples. Data tables are revised for clarity andmethod detection limits are included.

551.1rev. 1.0

Method 551.1 is an improvement to Method 551 which waspublished in EPA/600/4-90/020 (Supp. I) in July 1990.Pentane is included as an alternative solvent for someanalytes, the analyte list is expanded, and a new samplepreservation technique is used.

552.2rev. 1.0

Method 552.2 is similar to Method 552 which was published inEPA/600/4-90/020 (Supp. I) in July, 1990. Method 552.2 usesacidic methanol for methylation instead of diazomethane andexpands the analyte list.




Top of page

Methods for the Determination of Inorganic Substancesin Environmental Samples



EPA/600/R-93/100August 1993

This manual is available from NTIS and contains Methods 180.1, 300.0, 335.4, 350.1, 351.2,353.2, 365.1, 375.2, 410.4 and 420.4. Address your request for this manual to NTIS and ask fortheir order number PB94-120821; the cost is $31.00.

Abstract

This manual contains ten updated and revised automated, semi-automated or manual methodsamenable to automation for the determination of a variety of inorganic substances in water andwastewater. These methods include and address, in an expanded form, information concerning

safety, quality control, pollution prevention, and waste management. Methods were selected whichminimize the amount of hazardous reagents required and maximize sample throughput to allowexpanded quality control. Automated methods are included for nitrate-nitrite, phosphorus, and

sulfate. Semi-automated methods cover cyanide, ammonia, total kjeldahl nitrogen (TKN), chemicaloxygen demand (COD) and generic phenolics. Methods amenable to automation include turbidity

and inorganic anions by ion chromatography.

Table of Contents

MethodNumber

Title Revision Date Page

- Disclaimer - - ii

- Foreword - - iii

- Abstract - - iv

- Acknowledgment - - vi

- Introduction - - 1

180.1 Determination of Turbidity 2.0 8/93

300.0 Determination of Inorganic Anions byIon Chromatography

2.1 8/93

335.4 Determination of Total Cyanide bySemi-Automated Colorimetry

1.0 8/93

350.1 Determination of Ammonia Nitrogenby Semi-Automated Colorimetry

2.0 8/93

351.2Determination of Total KjeldahlNitrogen by Semi-AutomatedColorimetry

2.0 8/93




353.2 Determination of Nitrate-Nitrite byAutomated Colorimetry

2.0 8/93

365.1 Determination of Phosphorus byAutomated Colorimetry

2.0 8/93

375.2 Determination of Sulfate byAutomated Colorimetry

2.0 8/93

410.4Determination of Chemical OxygenDemand by Semi-AutomatedColorimetry

2.0 8/93

420.4 Determination of Total RecoverableSemi-Automated Colorimetry

1.0 8/93

Introduction

James W. O'Dell, John D. Pfaff, William L. Budde


The original version of this manual was issued in November 1969 by the Federal Water PollutionControl Administration as "FWPCA Methods for Chemical Analysis of Water and Wastes." With thecreation of the United States Environmental Protection Agency (USEPA) in 1970 came "Methods forChemical Analysis of Water and Wastes 1971" Publication No. 16020---07/71. The second editionwas issued in 1974 as EPA 625/6-74-003, and the third edition in 1979 as EPA 600/4/79-020. Themost recently published version, an updated second printing of the third edition, was revised andissued in March 1983. The methods contained in the 1983 manual form the basis for most of themethodology approved for compliance monitoring of inorganic parameters specified under theClean Water Act (NPDES) and contaminants regulated under the Safe Drinking Water Act.

In 1991, a number of new and revised metals methods were incorporated into a new publicationentitled, "Methods for the Determination of Metals in Environmental Samples." Concurrently, thedecision was made to revise and update selected non-metal methods to be issued under the name"Methods for the Determination of Inorganic Substances in Environmental Samples."

For both the metals and non-metals manuals, several important features were adopted:

Consistent use of terminology, a feature especially helpful in the quality control sectionswhere standardized terminology is not yet available. The terms were carefully selected tobe meaningful without extensive definition, and therefore should be easy to understandand use.New sections are included with expanded useful coverage of safety, quality control,pollution prevention and waste management.All methods are presented in the new EPA standard Environmental Monitoring ManagementCouncil (EMMC) format.

Although a number of other methods included the 1983 edition of USEPA "Methods for ChemicalAnalysis of Water and Wastes", Standard Methods for the Examination of Water and Wastewater,and American Society for Testing and Materials Annual Book of Standards (ASTM) are acceptablefor compliance monitoring, the revised methods contained in this publication are considered to bethe most useful in terms of future regulatory requirements. They represent a selection of airsegmented automated, semi-automated, or amenable to automation methodology that providesthe following advantages over their manual counterparts:

Higher sample throughput for faster analysis and improved precision.Faster analysis allows more time to perform the updated quality control required to insurevalid results.



Lower per analysis reagent consumption to reduce waste production and minimize disposalcosts.The inclusion of multi-laboratory data generated from USEPA performance evaluationstudies.

The following methods are included with specific features and improvements:

A revised version of EPA turbidity Method 180.1 that minimizes the direct use of hydrazinesulfate.An updated version of EPA Method 300.0 for anions by ion chromatography.A new stand alone semi-automated revision of EPA cyanide Method 335.2 that specifiesthe use of the downsized midi-distillation procedure.A new semi-automated version of the EPA phenolics Method 420.2.The optional use of a non-mercury catalyst in EPA TKN Method 351.2.

All methods allow the optional use of reduced reagent and distillation-digestion volumes.

Most of the methods include the option of limited performance-based modifications orimprovements.


Top of page

Methods for the Determination of Metals inEnvironmental Samples



EPA-600/4-91-010June 1991

This manual is available from NTIS and contains Methods 200.1, 200.2, 200.3, 200.7, 200.8,200.9, 200.10, 200.11, 218.6, 245.1, 245.3, 245.5 and 245.6. Please note that revised versions ofMethods 200.2, 200.7, 200.8, 200.9, 218.6, and 245.1 are contained in Supplement I (May, 1994)of the Metals manual. Address your request for this manual to NTIS and request their ordernumber PB91-231498; the cost is $61.50.

Abstract

Thirteen analytical methods covering 35 analytes which may be present in a variety ofenvironmental sample types are described in detail. Three of these methods are samplepreparation procedures that require a separate determinative step found in other methods in thismanual or elsewhere. The 10 complete methods involve a wide range of analytical instrumentationincluding inductively coupled plasma (ICP)/atomic emission spectroscopy (AES), ICP/massspectroscopy (MS), atomic absorption (AA) spectroscopy, ion chromatography (IC), and highperformance liquid chromatography (HPLC). Application of these techniques to a diverse group ofsample types is a somewhat unique feature of this manual. Sample types include waters rangingfrom drinking water to marine water as well as industrial and municipal wastewater, groundwaterand landfill leachate. Also included are methods that will accommodate biological tissues,sediments, and soils.

Table of Contents

MethodNumber





- Disclaimer - - ii

- Foreword - - iii

- Abstract - - iv

- Analyte - Method Cross Reference - - vii

- Acknowledgement - - ix

- Introduction and General Comments - - 1

200.1 Determination of Acid Soluble Metals 2.0 4/91 3

200.2 Sample Preparation Procedure forTotal Recoverable Elements

2.3 4/91 13

200.3

Sample Preparation Procedure forSpectrochemical Determination ofTotal Recoverable Elements inBiological Tissues

1.0 4/91 23

200.7

Determination of Metals and TraceElements in Water and Wastes byInductively Coupled Plasma-AtomicEmission Spectrometry

3.3 4/91 31

200.8Determination of Trace Elements inWater and Wastes by InductivelyCoupled Plasma - Mass Spectrometry

4.4 4/91 83

200.9

Determination of Trace Elements byStabilized Temperature GraphiteFurnace Atomic AbsorptionSpectrometry

1.2 4/91 123

200.10

Determination of Trace Elements inMarine Waters by On-Line ChelationPreconcentration and InductivelyCoupled Plasma - Mass Spectrometry

1.4 4/91 153

200.11Determination of Metals in Fish Tissueby Inductively Coupled Plasma-AtomicEmission Spectrometry

2.1 4/91 177

218.6

Determination of Dissolved HexavalentChromium in Drinking Water,Groundwater, and IndustrialWastewater Effluents by IonChromatography

3.2 4/91 211

245.1Determination of Mercury in Water byCold Vapor Atomic AbsorptionSpectrometry

2.3 4/91 227

Determination of Inorganic Mercury(II) and Selected Organomercurials inDrinking and Ground Water by High



245.3Performance LiquidChromatography(HPLC) withElectrochemical Detection (ECD)

1.1 4/91 241

245.5Determination of Mercury in Sedimentby Cold Vapor Atomic AbsorptionSpectrometry

2.3 4/91 267

245.6Determination of Mercury in TissuesbyCold Vapor Atomic AbsorptionSpectrometry

2.3 4/91 281


Analyte Method No.

Aluminum 200.2, 200.3, 200.7,200.8, 200.9, 200.11

Antimony 200.2, 200.3, 200.7,200.8, 200.9, 200.11

Arsenic200.1, 200.2, 200.3,200.7, 200.8, 200.9,200.11

Barium 200.2, 200.3, 200.7,200.8

Beryllium 200.2, 200.3, 200.7,200.8, 200.11

Boron 200.7

Cadmium200.1, 200.2, 200.3,200.7, 200.8, 200.9,200.10, 200.11

Calcium 200.2, 200.3, 200.7,200.11

Chromium200.1, 200.2, 200.3,200.7, 200.8, 200.9,200.11

ChromiumVI

218.6

Cobalt 200.2, 200.3, 200.7,200.8, 200.10

Copper200.1, 200.2, 200.3,200.7, 200.8, 200.9,200.10, 200.11

200.2, 200.3, 200.7,



Iron200.9, 200.11

Lead200.1, 200.2, 200.3,200.7, 200.8, 200.9,200.10, 200.11

Lithium 200.2, 200.3, 200.7

Magnesium 200.2, 200.3, 200.7,200.11

Manganese 200.2, 200.3, 200.7,200.8, 200.9

Mercury,Total

200.2, 200.3, 245.1,245.5, 245.6

Mercury,Organic

245.3

Mercury II 245.3

Molybdenum 200.2, 200.3, 200.7,200.8

Nickel200.2, 200.3, 200.7,200.8, 200.9,200.10, 200.11

Phosphorus 200.2, 200.3, 200.7,200.11

Potassium 200.2, 200.3, 200.7,200.11

Selenium 200.2, 200.3, 200.7,200.8, 200.9, 200.11

Silica 200.2, 200.3, 200.7

Silver 200.2, 200.3, 200.7,200.8, 200.9

Sodium 200.2, 200.3, 200.7,200.11

Strontium 200.2, 200.3, 200.7

Thallium 200.2, 200.3, 200.7,200.8, 200.9, 200.11

Thorium 200.2, 200.3, 200.8

Tin 200.2, 200.7, 200.9

Uranium 200.2, 200.3, 200.8,200.10

Vanadium 200.2, 200.3, 200.7,



200.8, 200.10

Zinc 200.2, 200.3, 200.7,200.8, 200.9, 200.11

Introduction

Larry B. Lobring


An integral component of the role of the Environmental Protection Agency (EPA) in assessing andprotecting the quality of the environment is the provision of means for monitoring environmentalquality. In keeping with this role, EPA develops and disseminates analytical methods for measuringchemical and physical parameters affecting this most important resource, including contaminantswhich may have potential adverse effects upon the health of our environment. This manualprovides 13 analytical methods for 35 analytes which may be present in a variety of environmentalsample types. Three of the methods are sample preparation procedures that refer to instrumentaltechniques in other methods for multi-analyte or single-analyte quantitation. The remaining 10analytical methods were written to stand-alone, that is, each method may be removed from themanual, photocopied, inserted into another binder, and used without loss of information. Revisionsof these methods will be made available in a similar stand-alone format to facilitate thereplacement of existing methods as new technical developments occur. This flexibility comes at thecost of some duplication of material, for example, the definitions of terms section of each methodis nearly identical. The authors believe that the added bulk of the manual is a small price to pay forthe format flexibility.

An important feature of the methods in this manual is the consistent use of terminology, and thisfeature is especially helpful in the quality control sections where standardized terminology is not yetavailable. The terms were carefully selected to be meaningful without extensive definition, andtherefore should be easy to understand and use. The names of authors of the methods areprovided to assist users in obtaining direct telephone support when required.

General Comments

The methods in this manual are not intended to be specific for any single EPA regulation,compliance monitoring program, or specific study. In the past, manuals have been developed andpublished that respond to specific regulations, such as the Safe Drinking Water Act (SDWA) or tospecial studies such as the Environmental Monitoring and Assessment Program (EMAP) NearCoastal Demonstration Project. These methods are, however, available for incorporation intoseveral regulatory programs due to their applicability to such diverse sample types. The ICP/AES,ICP/MS and AA methods have been or will be approved for use in the drinking water and thepermit programs. The methods applicable for use in marine and estuary waters will be available foruse in the Agency's National Estuary Program and subsequent EMAP studies that may involve thedetermination of toxic metals in the water column.

The quality assurance sections are uniform and contain minimum requirements for operating areliable monitoring program: initial demonstration of performance, routine analyses of reagentblanks, analyses of fortified reagent blanks and fortified matrix samples, and analyses of qualitycontrol (QC) samples. Other QC practices are recommended and may be adopted to meet theparticular needs of monitoring programs e.g., analyses of field reagent blanks, instrument controlsamples and performance evaluation samples.


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Methods for the Determination of Metals in




Environmental SamplesSupplement I

Environmental Momitoring Systems LaboratoryOffice of Research and Development


EPA-600/R-94/111May 1994

This manual is available from NTIS and contains new versions of Methods 200.2, 200.7, 200.8,200.9, 218.6 and 245.1 and new Method 200.15,. Address your request for this manual to NTISand request their order number PB95-125472; the cost is $44.00.

Abstract

This manual includes seven analytical methods four of which are considered multi-analytemethods, two are single analyte methods, and the total recoverable sample preparation procedureis given as a separate method write up. These methods utilize inductively coupled plasma(ICP)/atomic emission spectrometry (AES), ICP/mass spectrometry (MS), graphite furnace atomicabsorption (GFAA), cold vapor atomic absorption (CVAA), and ion chromatography (IC). Applicationof these methods is directed primarily toward aqueous samples such as wastewater, drinking andambient waters. However, procedures for the analysis of solid samples such sludges and soils alsoare included in the multi-analyte methods 200.7, 200.8, and 200.9.

Table of Contents

MethodNumber


- Disclaimer - - ii

- Foreword - - iii

- Abstract - - iv

- Acknowledgement - - vi

- Introduction - - vii

200.2Sample Preparation Procedure forSpectrochemical Determination ofTotal Recoverable Elements

2.8 5/94

200.7

Determination of Metals and TraceElements in Water and Wastes byInductively Coupled Plasma-AtomicEmission Spectrometry

4.4 5/94

200.8Determination of Trace Elements inWater and Wastes by InductivelyCoupled Plasma - Mass Spectrometry

5.3 5/94

200.9

Determination of Trace Elements byStabilized Temperature GraphiteFurnace Atomic AbsorptionSpectrometry

2.2 5/94

Determination of Metals and TraceElements in Water by Ultrasonic



200.15Nebulization Inductively CoupledPlasma-Atomic Emission Spectrometry

1.2 5/94

218.6

Determination of Dissolved HexavalentChromium in Drinking Water,Groundwater, and IndustrialWastewater Effluents by IonChromatography

3.3 5/94

245.1Determination of Mercury in Water byCold Vapor Atomic AbsorptionSpectrometry

3.0 5/94


Analyte Method No.

Aluminum 200.2, 200.7, 200.8,200.9, 200.15

Antimony 200.2, 200.7, 200.8,200.9, 200.15

Arsenic 200.2, 200.7, 200.8,200.9, 200.15

Barium 200.2, 200.7, 200.8,200.15

Beryllium 200.2, 200.7, 200.8,200.15

Boron 200.7, 200.15

Cadmium 200.2, 200.7, 200.8,200.9, 200.15

Calcium 200.2, 200.7, 200.15

Chromium 200.2, 200.7, 200.8,200.9, 200.15

ChromiumVI

218.6

Cobalt 200.2, 200.7, 200.8,200.15

Copper 200.2, 200.7, 200.8,200.9, 200.15

Iron 200.2, 200.7, 200.9,200.15

Lead 200.2, 200.7, 200.8,200.9, 200.15



Lithium 200.2, 200.7, 200.15

Magnesium 200.2, 200.7, 200.15

Manganese 200.2, 200.7, 200.8,200.9, 200.15

Mercury,Total

200.2, 245.1, 200.8,200.15

Molybdenum 200.2, 200.7, 200.8,200.15

Nickel 200.2, 200.7, 200.8,200.9, 200.15

Phosphorus 200.2, 200.7

Potassium 200.2, 200.7, 200.15

Selenium 200.2, 200.7, 200.8,200.9, 200.15

Silica 200.2, 200.7, 200.15

Silver 200.2, 200.7, 200.8,200.9, 200.15

Sodium 200.2, 200.7, 200.15

Strontium 200.2, 200.7, 200.15

Thallium 200.2, 200.7, 200.8,200.9, 200.15

Thorium 200.2, 200.8

Tin 200.2, 200.7, 200.9,200.15

Titanium 200.7, 200.15

Uranium 200.2, 200.8

Vanadium 200.2, 200.7, 200.8,200.15

Zinc 200.2, 200.7, 200.8,200.15

Introduction

Theodore D. Martin


Six of the seven methods appearing in this supplement were included in the first publication of themanual "Determination of Metals in Environmental Samples", EPA 600 4-91/010, June, 1991. Theone new method appearing in this supplement is Method 200.15, Determination of Metals andTrace Elements in Water by Ultrasonic Nebulization Inductively Coupled Plasma-Atomic EmissionSpectrometry. Method 200.15 was developed to extend the analytical range of the ICP-AES



technique to lower concentrations. Its usefulness for the analysis of drinking water is evident bythe performance data included in the method.

Unlike the 1991 manual (EPA 600 4-91/010) which contains 13 methods for avariety of samplematrices, this supplement is focused more on the analysis of water and wastes. Its purpose is foruse in compliance monitoring of National Pollution Discharge Elimination System (NPDES) effluentsas required under the Clean Water Act and compliance monitoring of drinking water as requiredunder the Safe Drinking Water Act. These methods are also useful for the analysis of ambientwaters with the exclusion of marine water.

The methods included in this supplement have been prepared in the format adopted by theEnvironmental Monitoring Management Council (EMMC). In this format method sections are orderedin a specific manner and purpose with the addition of two new sections on pollution prevention andwaste management.

All methods have the same approach to analytical quality control in that initial demonstration ofperformance is required prior to method use, and assessing ongoing laboratory performance ismandatory. However, the required frequency of demonstration has been lessened and theacceptance control limits have been widened. Also, the required limits used in assessing recoverydata from fortified matrices have been widened. Where available multi-laboratory data andregression equations have been included in the methods.

The multi-analyte methods (200.7, 200.8, 200.9, and 200.15) all utilize the same total recoverablesample digestion procedure that is described in Method 200.2 as a stand-alone procedure. Thisprocedure also is applicable to flame atomic absorption determinations. Using a common samplepreparation for all spectrochemical techniques is convenient and can reduce cost of analyses.

Changes to previous versions of specific methods are as follows:

Cerium has been added to Method 200.7 for correction of potential spectral interferencesTitanium has been added as an analyte to Method 200.7Mercury has been added to Method 200.8 for the analysis of drinking water with turbidityof < 1 NTUZinc has been deleted from Method 200.9 because its determination by the graphitefurnace technique is impracticalDigestion of Method 245.1 mercury calibration standards is no longer required


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Methods for the Determination of Chemical Substancesin Marine and EstuarineEnvironmental Samples



EPA/600/R-92/121November 1992

This manual is available from NTIS and contains Methods 200.10, 200.12, 200.13, 353.4, 365.5,440.0 and 445.0. Address your request for this manual to NTIS and request their order numberPB93-182913; the cost is $21.50.

Abstract

This manual contains seven methods for determination of nutrients, metals and chlorophyll.




Methods 353.4, revision 1.2, and 365.5, revision 1.3, for the measurement of nitrite+nitrate andorthophosphate, respectively, appeared in the 1991 interim manual. Since then they haveundergone multilaboratory validation studies. Method 365.5 performed well in the study andmultilaboratory data are presented in the revision of the method that appears here. Theperformance of Method 353.4 in the study indicated that the cadmium reduction column chemistryand maintenance requires further investigation. The method has been retained in this manual sothat further testing can continue using a standardized method description. Method 440.0 formeasurement of total particulate carbon and nitrogen is based upon a well established combustiontechnique. Procedures for partitioning the organic and inorganic fractions of carbon are alsopresented. A multilaboratory study is in progress, and the results will be included in a subsequentrevision of the method. The three metals methods represent current state-of-the-science in metalsmeasurements. Two of the methods are graphite furnace atomic absorption techniques and thethird uses inductively coupled plasma mass spectrometry. Single laboratory performance data areincluded in the methods. Although few laboratories currently have the instrumentation capabilitiesto perform all of these methods, it is extremely important to present them in order to stimulatethe development of laboratory capability before multilaboratorystudies can be conducted. Method445.0 is for the determination of chlorophyll a and the phaeopigments using fluorescencedetection. This method has been used for many years for low level measurement of chlorophyll.The method was evaluated using two natural water samples of primarily green and blue-greenalgae. The numbering of methods was correlated with previous EMSL-Cincinnati methods wheneverpossible. The metals methods are 200 series, the nutrients nitrite+nitrate and orthophosphate are300 series, and the particulate carbon and nitrogen, and chlorophyll methods are 400 series.

Table of Contents

MethodNumber


- Disclaimer - - ii

- Foreword - - iii

- Abstract - - iv

- Acknowledgment. - - vi

- Introduction - - 1

200.10

Determination of Trace Elements inMarine Waters by On-Line ChelationPreconcentration and InductivelyCoupled Plasma - Mass Spectrometry

1.6 11/92

200.12

Determination of Trace Elements inMarine Waters by StabilizedTemperature Graphite FurnaceAtomic Absorption

1.0 11/92

200.13

Determination of Trace Elements inMarine Waters by Off-Line ChelationPreconcentration with GraphiteFurnace Atomic Absorption

1.0 11/92

353.4Determination of Nitrite+ Nitrate inEstuarine and Coastal Waters byAutomated Colorimetric Analysis

1.3 11/92

365.5Determination of Orthophosphate inEstuarine and Coastal Waters byAutomated Colorimetric Analysis

1.4 11/92



440.0

Determination of Carbon andNitrogen in Sediments andParticulates of Estuarine/CoastalWaters Using Elemental Analysis

1.4 11/92

445.0

In Vitro Determination of Chlorophylla and Phaeophytin a in Marine andFreshwater Phytoplankton byFluorescence

1.1 11/92

Introduction

Elizabeth J. Arar, William L. Budde, Larry B. Lobring


The principal aim of this manual is to bring together under one cover a suite of analytical methodsspecifically adapted or developed for the examination of marine and estuarine environmentalsamples. Three of the methods presented here are adaptations of analytical techniques which, formany years, have been used routinely by the marine community. Hallmarks of the methods whichappear in this manual, however, are the integrated quality control/quality assurance requirements,the use of standardized terminology, and the use of the Environmental Monitoring ManagementCouncil (EMMC) methods format. The mandatory demonstration of laboratory capability and thecontinuing checks on method performance ensure the quality and comparability of data reported bydifferent laboratories and programs. Another distinction of this manual is the eventualmultilaboratory validation study of each method.

Multilaboratory validation studies test the ruggedness of methods, provide single-analyst andmultilaboratory precision and accuracy statements and method detection limits that are "typical" ofwhat most laboratories can achieve. Methods that reach this level of evaluation have beenthoroughly investigated by a single laboratory and have usually been informally adopted asstandard methods by the analytical community. Method 365.5, "Determination of Orthophosphatein Estuarine and Coastal Waters by Automated Colorimetric Analysis", a widely accepted method inthe marine community, performed quite well in a multilaboratory study. A table has been added tothe method to summarize single-analyst and multilaboratory precision and accuracy of the methodfor three water matrices. As a result of the study, pooled method detection limits fororthophosphate in a wide range of water salinities have also been added to the method.

On the other hand, Method 353.4, "Determination of Nitrite+Nitrate in Estuarine and CoastalWaters by Automated Colorimetric Analysis", did not give acceptable multilaboratory results, and itmust return to the development phase. Method 353.4, despite its wide acceptance and routine usein the marine community, failed the ruggedness test when 50% of the participating laboratories inthe multilaboratory study returned unacceptable data. Their data suggest that the cadmiumreduction column chemistry and maintenance require further investigation. The method,nonetheless, appears in this manual with appropriate caveats for the user so that further testingcan continue using a standardized method description.

Method 440.0, for particulate carbon and nitrogen uses a well established combustion techniqueand is currently undergoing multilaboratory validation. The results from that study will beincorporated into the next revision of this manual.

Method 445.0 for the in vitro determination of chlorophyll a and the phaeopigments usingfluorescence detection was evaluated using primarily freshwaterphytoplankton samples. We do notbelieve this prohibits its inclusion in a marine methods manual since the analytical steps are thesame regardless of algae classification. An effort has been made to include a review of the currentpertinent literature on chlorophyll measurement. A visible spectrophotometric method forchlorophyll a, b, and c and the carotenoids is not included in this edition of the manual becausemore research is required for a thorough evaluation of this method.

The three metals methods presented here represent current state-of-the-science in metalsmeasurement and are suitable for low-level concentrations in high salinity waters. The twomethods that use the chelation preconcentration chromatography system offer detection limits



roughly an order of magnitude lower than their conventional counterpart methods. As theinstrumentation for these techniques becomes more prevalent in analytical laboratories, themethods will undergo multilaboratory validation studies.

This manual should be viewed as a living document, with methods for organics, nutrients andmetals continually being added, updated, revised and validated. There is also much work to bedone in assuring the provision of SRMs and quality control samples to the marine monitoringcommunity. We encourage users of the methods in this manual to share their experiences with usand to obtain new editions of the manual as they become available.

The methods in this manual are not intended to be specific for any single USEPA regulation,compliance monitoring program, or specific study. In the past, manuals have been developed andpublished that respond to specific regulations, such as the Safe Drinking Water Act (SDWA), or tospecial studies, such as the Environmental Monitoring and Assessment Program (EMAP) NearCoastal Demonstration Project. These methods are, however, available for incorporation intoregulatory programs that require the measurement of nutrients and metals in marine waters.


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Microbiological and Chemical Exposure Research

EPA Microbiology | Exposure Research


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Analytical Chemistry Methods Manuals _ Microbiological and Chemical Exposure