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Manual of Manuals

Summaries and Ordering Information for Eight Laboratory Analytical Chemistry Methods Manuals Published by the former Environmental Monitoring Systems Laboratory-Cincinnati (EMSL-Cincinnati) 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 eight laboratory analytical chemistry methods manuals published by the former Environmental Monitoring Systems Laboratory-Cincinnati (EMSL-Cincinnati) between 1988 and 1995. The complete manuals may be ordered from the National Technical Information Service (NTIS) at the address or telephone numbers below:

National Technical Information Service
5285 Port Royal Road
Springfield, VA 22161

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

The shipping charge per order is $3.00.


To jump to the section of this document described in the short titles below, click on the highlighted text:

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


OdometerAccesses since July 26, 1996


Methods for the Determination of Organic Compounds in Drinking Water

Environmental Monitoring Systems Laboratory
Office of Research and Development
U.S. Environmental Protection Agency
Cincinnati, Ohio 45268
EPA-600/4-88/039
December 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 supplements that are described in this document. Address your request for this manual to NTIS and ask for their order number PB91-231480; the cost is $61.50.

ABSTRACT Thirteen analytical methods for the identification and measurement of organic compounds in drinking 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 Federal Register of July 8, 1987, under the National Primary Drinking Water Regulations. The other seven methods are designed for the determination of a variety of synthetic organic compounds and pesticides, and these methods were cited in proposed drinking water regulations in the Federal Register 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 a new liquid-solid extraction technique, and one method is for direct aqueous analysis. Of the 13 methods, 12 use either packed or capillary gas chromatography column separations followed by detection with mass spectrometry or a selective gas chromatography detector. One method is based on a high performance liquid chromatography separation.



TABLE OF CONTENTS
Method Number Title Revision Page
- Foreword - iii
- Abstract - iv
- Analyte - Method Cross Reference - vii
- Acknowledgement - xii
- Introduction - 1
502.1 Volatile Halogenated Organic Compounds in Water by Purge and Trap Gas Chromatography 2.0 5
502.2 Volatile Organic Compounds in Water By Purge and Trap Capillary Column Gas Chromatography with Photoionization and Electrolytic Conductivity Detectors in Series 2.0 31
503.1 Volatile Aromatic and Unsaturated Organic Compounds in Water by Purge and Trap Gas Chromatography 2.0 63
504 1,2-Dibromoethane (EDB) and 1,2-Dibromo-3-Chloropropane (DBCP) in Water by Microextraction and Gas Chromatography 2.0 89
505 Analysis of Organohalide Pesticides and Commerical Polychlorinated Biphenyl Products in Water by Micro-Extraction and Gas Chromatography 2.0 109
507 Determination of Nitrogen- and Phosphorus-Containing Pesticides in Water by Gas Chromatography with a Nitrogen-Phosphorus Detector 2.0 143
508 Determination of Chlorinated Pesticides in Water by Gas Chromatography with An Electron Capture Detector 3.0 171
508A Screening for Polychlorinated Biphenyls by Perchlorination and Gas Chromatography 1.0 199
515.1 Determination of Chlorinated Acids in Water by Gas Chromatography with an Electron Capture Detector 4.0 221
524.1 Measurement of Purgeable Organic Compounds in Water by Packed Column GasChromatography/Mass Spectrometry 3.0 253
524.2 Measurement of Purgeable Organic Compounds in Water by Capillary Column Gas Chromatography/Mass Spectrometry 3.0 283
525.1 Determination of Organic Compounds in Drinking Water by Liquid-Solid Extraction and Capillary Column Gas Chromatography/Mass Spectrometry 2.2 323
531.1 Measurement of N-Methylcarbamoyloximes and N-Methylcarbamates in Water by Direct Aqueous Injection HPLC with Post Column Derivatization 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 diacid metabolites 515.1
2,4-Dichlorophenoxyacetic acid (2,4-D) 515.1
4-(2,4-Dichlorophenoxy)butyric acid (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
1,3-Dichlorobenzene 502.1, 502.2, 503.1, 524.1, 524.2
1,4-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
1,3-Dichloropropane 502.1, 502.2, 524.1, 524.2
2,2-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-Ethyl dipropylthiocarbamate (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
alpha Hexachlorocyclohexane (alpha BHC)(HCH-alpha) 508
beta Hexachlorocyclohexane (beta BHC)(HCH-beta) 508
delta Hexachlorocyclohexane (delta BHC)(HCH-delta) 508
gamma Hexachlorocyclohexane (Lindane)(gamma BHC)(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-Trichlorophenoxyacetic acid (2,4,5-T) 515.1
2-(2,4,5-Trichlorophenoxy)propionic acid (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 in drinking water using two or more of the documented analytical methods. For example, nearly 50 compounds are listed as analytes in four different methods. This approach of multiple methods for many analytes was selected to provide the maximum flexibility to method users from small and large laboratories. Some methods require relatively modest equipment, and others require sophisticated instrumentation. This flexible approach should meet the needs and requirements of nearly all laboratories.

GENERAL METHOD FEATURES

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

An important feature of the methods in this manual is the consistent use of terminology, and this feature is especially helpful in the quality control sections where standardized terminology is not yet available. The terms were carefully selected to be meaningful without extensive definition, and therefore should be easy to understand and use. The names of authors of the methods are provided 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 some ground and surface waters. Some methods have been tested only in reagent water and/or drinking water. While some of these methods may provide reliable results with more complex water matrices, for example, industrial wastewaters and beverages, techniques for dealing with more complex matrices have not been included in the methods in order to keep them as simple and brief as possible. Therefore caution is needed when applying these methods to matrices other than relatively 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 stop the formation of trichloromethanes and other disinfection by-products, or to prevent the formation of method interferences and analytes generated from chlorination of impurities in reagents and solvents.

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

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 as the minimum concentration of a substance that can be identified, measured, and reported with 99% confidence that the analyte concentration is greater than zero. The EDL is either the MDL, or a concentration of compound in a clean water matrix that gives a peak in the final extract with a signal-to-noise ratio of about 5.

If the replicate measurements needed to calculate an MDL are obtained under ideal conditions, for example, during a short period of time within a work shift, the resulting standard deviation may be small and give an unrealistically low MDL. The data acquired for measurement of an MDL should be obtained over a period of time (several days or more). Obtained in this way, the standard deviation includes 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 calibration standards and quality control samples are needed to implement the methods. Calibration standards and quality control samples should be obtained from different sources so that the quality control sample 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 be available on a limited basis from the Quality Assurance Research Division, Environmental Monitoring 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 National Primary Drinking Water Regulations. These are Methods 502.1, 502.2, 503.1, 504, 524.1 and 524.2.

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 the same 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 a mass spectrometer (MS) or conventional GC detector. The other method (Method 504) is a microextraction procedure for two compounds of special interest, ethylene dibromide (EDB) and 1,2-dibromo-3-chloropropane (DBCP).

Solicited and unsolicited written and telephoned comments have been received from some of the laboratories using the VOC methods, and some of these users suggested certain technical and editorial changes. In addition, the staff of the Chemistry Research Division recognized that some changes 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 technical and many editorial changes which are summarized below.

Few technical changes were made to the six VOC methods. The use of ascorbic acid as a dechlorinating 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 undesirable generation of sulfur dioxide at low pH.

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

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

Extensive editorial changes were made in all six VOC methods. These editorial changes were necessary to provide an organized, consistent, and much more complete presentation of the myriad details needed by laboratories to successfully implement the methods. The addition of these details, the consistent use of terminology, and the uniform organization of all the methods should substantially reduce the number of questions received and provide the user community with the information 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 during 1987-1989, 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 request from the Office of Drinking Water (ODW). Method 505, a relatively simple microextraction procedure patterned after Method 504, was developed to provide a rapid method for the determination of chlorinated hydrocarbon pesticides and commercial PCB mixtures (Aroclors) in drinking water. Method 525.1 is a broad spectrum GC/MS method for a variety of compounds under consideration for regulation, and it was developed specifically to utilize the new liquid-solid extraction 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 the SOCs from water followed by a high resolution capillary column GC separation and detection with an 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 liquid chromatography (HPLC) separation and post-column derivatization to a compound detected with a fluorescence detector.

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

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

The broad spectrum GC/MS method (Method 525.1) uses a liquid-solid extraction (LSE) procedure based on commercial LSE cartridges or disks. The cartridges are small (about 0.5 in. x 3 in.) plastic or glass tubes packed with reverse phase liquid chromatography packing materials. The disks are made 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 sorbed on the solid phase. After air drying, the organic compounds are eluted using a very small volume of an organic solvent. Cartridges from six suppliers were used in the methods research, and a quality control procedure was developed to permit selection of cartridges with acceptable performance characteristics. The disks are manufactured by a single company, so only one type was evaluated.

The LSE procedure is attractive because it greatly reduces the use and worker exposure to methylene 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 the simultaneous determination of 42 SOCs including chlorinated hydrocarbon pesticides, polycyclic aromatic hydrocarbons, phthalate and adipate esters, individual PCB congeners, several triazine pesticides, and pentachlorophenol. Laboratories will find this method attractive because of its potential economy of operation when a wide variety of analytes are to be determined.


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Methods for the Determination of Organic Compounds in Drinking Water
Supplement I

Environmental Monitoring Systems Laboratory
Office of Research and Development
U.S. Environmental Protection Agency
Cincinnati, Ohio 45268
EPA-600/4-90/020
July 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 the revised versions are published in Supplement II or III. Address your request for this manual to to NTIS 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 water or drinking water sources are described in detail. Seven of these methods cover compounds designated for regulation under the Safe Drinking Water Act Amendments of 1986. Regulations for this group are in the proposal stages with promulgation scheduled for June 1992. The other two methods are for chlorination disinfection byproducts and may be regulated as part of EPA's disinfectants and disinfectant byproducts rule scheduled for proposal early in 1992. Most of the analytes may be classified as non-volatile and three of the methods entail separations by high performance 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 tracers and 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 trend which is likely to become even more pronounced in the future.



TABLE OF CONTENTS
Method Number Title Page
- Foreword iii
- Abstract iv
- Acknowledgment vi
- Analyte - Method Cross Reference vii
- Introduction 1
506 Determination of Phthalate and Adipate Esters in Drinking Water by Liquid-Liquid Extraction or Liquid-Solid Extraction and Gas Chromatography with Photoionization Detection 5
513 Determination of 2,3,7,8-Tetrachloro-dibenzo-p-dioxin in Drinking Water by Liquid-Liquid Extraction and Gas Chromatography with High-Resolution Mass Spectrometry 33
547 Determination of Glyphosate in Drinking Water by Direct-Aqueous-Injection HPLC, Post-Column Derivatization, and Fluorescence Detection 63
548 Determination of Endothall in Drinking Water by Aqueous Derivatization, Liquid-Solid Extraction, and Gas Chromatography with Electron-Capture Detection 81
549 Determination of Diquat and Paraquat in Drinking Water by Liquid-Solid Extraction and HPLC with Ultraviolet Detection 101
550 Determination of Polycyclic Aromatic Hydrocarbons in Drinking Water by Liquid-Liquid Extraction and HPLC with Coupled Ultraviolet and Fluorescence Detection 121
550.1 Determination of Polycyclic Aromatic Hydrocarbons in Drinking Water by Liquid-Solid Extraction and HPLC with Coupled Ultraviolet and Fluorescence Detection 143
551 Determination of Chlorination Disinfection Byproducts and Chlorinated Solvents in Drinking Water by Liquid-Liquid Extraction and Gas Chromatography with Electron-CaptureDetection 169
552 Determination of Haloacetic Acids in Drinking Water by Liquid-Liquid Extraction, Derivatization, and Gas Chromatography with Electron Capture Detection 201



ANALYTE-METHOD CROSS REFERENCE
Analyte Method No.
Acenaphthene 550, 550.1
Acenaphthylene 550, 550.1
Anthracene 550, 550.1
Benz(a)anthracene 550, 550.1
Benzo(b)fluoranthene 550, 550.1
Benzo(k)fluoranthene 550, 550.1
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 the quality of the Nation's water resources is the provision of means for monitoring water quality. In keeping with this role, EPA develops and disseminates analytical methods for measuring chemical and physical parameters affecting water quality, including chemical contaminants which may have potential adverse effects upon human health. This manual provides nine, analytical methods for 54 organic contaminants, which may be present in drinking water or drinking water sources. In December 1988, EPA published "METHODS FOR THE DETERMINATION OF ORGANIC COMPOUNDS IN DRINKING WATER", EPA/600/4-88/039, a manual containing 13 methods for approximately 200 potential 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 regulatory framework. Efforts have been made herein to provide a manual and methods format, which is consistent with the earlier version.

REGULATORY BACKGROUND

Analytical methodology for monitoring water quality serves a number of related purposes, including occurrence studies in community water systems, health effects studies, and the determination of the efficacy of various water treatment approaches. These activities, in turn, form the supporting bases for water quality regulations, and the support of these regulations is the ultimate purpose of the analytical methods. Limitations on the levels of specific contaminants are codified in proposed and 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 for contaminants in drinking water which may cause adverse health effects and which are known or anticipated to occur in public water systems. The 1986 amendments require regulations to include Maximum Contaminant Levels (MCL's) with compliance determined by regulatory monitoring or by the application of an appropriate treatment, when adequate analytical methodology is not available. In addition, the 1986 amendments specified 83 contaminants, originally scheduled for regulation by June 19, 1989. The amended Act also required EPA to develop a priority list of additional contaminants, to propose 25 more of these by January of 1988 for subsequent regulation and to continue this process by the addition of 25 from the priority list on a triennial basis thereafter.

Of the original 83 pollutants, regulations for eight volatile organic chemicals (VOC) were promulgated in June 1987 (see 52 FR 25690 and 51 FR 11396). Analytical methods for these eight as well as other unregulated VOC's were published in the December 1988 manual (EPA Methods 502.1, 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 aldicarb sulfoxide, aldicarb sulfone, ethylbenzene, heptachlor, heptachlor epoxide and styrene. With the exception of lindane, analytical methods for all thirty compounds are by the VOC methods above or SOC methods also included in the 1988 manual.

The current manual provides analytical methods for many of the remaining contaminants on the original list of 83 - namely adipates, diquat, endothall, glyphosate, polycyclic aromatic hydrocarbons (PAH's), phthalates and dioxin. Phase V of EPA regulations for these and eleven other remaining SOC's from the list of 83 is scheduled for proposal in June 1990 and promulgation in March 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 chlorination disinfection byproducts. These contaminants were included in the first EPA priority list of additional substances, which may require regulation under the Act (see 53 FR 1892). At least some of these will be regulated by EPA's phase IV disinfectants and disinfectant byproducts rule scheduled for proposal early in 1992.

GENERAL COMMENTS

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

The quality assurance sections are uniform and contain minimum requirements for operating a reliable monitoring 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 quality control practices are recommended and may be adopted to meet the particular needs of monitoring programs - e. g., the analyses of field reagent blanks, instrument control samples and performance evaluation samples. Where feasible, surrogate analytes have been included in the methods as well as internal standards for calibration. Surrogate recoveries and the internal standard response should be routinely monitored as continuing checks on instrument performance, calibration curves and overall method performance.

THE ANALYTICAL METHODS

This manual includes seven methods for synthetic organic chemicals and two methods for chlorination disinfection byproducts. In general, the analytes may by classified as nonvolatile and three of the methods employ separation by high performance liquid chromatography (HPLC). The remainder utilize capillary column gas chromatography (GC). Two of the methods use convenient liquid-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 readily amenable to generic methods. Each method provides an adequate summary statement. Some additional 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's are limited to approximately 10 g/L. Phthalates and adipates are among the most common contaminants encountered in the laboratory and extreme care must be taken to ensure clean reagent 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 analytical requirement. 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 analysis by high resolution mass spectrometry. In addition, labeled isotopes of dioxin are employed as surrogate analyte and internal standard to aid in identification and quantitation and to compensate for 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 analyzed simultaneously. These may be characterized as difficult analytes because of their high water solubility and low volatility. In addition, glyphosate and endothall require derivatization prior to detection. Glyphosate is analyzed by direct aqueous HPLC injection and undergoes post-column derivatization prior to fluorescence detection. Endothall must be transferred from the aqueous phase to an acetic acid matrix for derivatization, followed by analysis by GC with electron capture detection (ECD). As with glyphosate, no preconcentration factor is involved. Method 549 provides for the extraction and concentration of diquat and paraquat in the base forms by LSE with a C-8 cartridge, preconditioned to operate in the reverse phase mode. The analytes are eluted with an acidic solvent and, after addition of ion-pairing reagent, are separated by HPLC. The analytes are detected by ultraviolet absorption (UV) with confirmation provided by a photodiode array spectrometer.

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

Halogenated organic byproducts, other than the regulated trihalomethanes, account for most of the total organic halogen formed by the chlorination of water supplies. The most important classes in terms of occurrence are the neutral analytes of Method 551 and the haloacetic acids of Method 552. Method 551 is quite similar to Method 504, employing a simple one step LLE and direct injection of the extract into a capillary GC with ECD detection. The haloacetic method is a serial LLE with analysis by GC-ECD and is quite similar to, but simpler than, Method 515.1 for acid herbicides. Both employ diazomethane for methylation with a micromolar generation procedure, which avoids the hazards associated with handling concentrated diazomethane. These two methods are 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 fortification concentrations. In addition, the uncertainty in measuring the background level should be considered when establishing control limits, as called for in the quality assurance section.


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Methods for the Determination of Organic Compounds in Drinking Water
Supplement II

Environmental Monitoring Systems Laboratory
Office of Research and Development
U.S. Environmental Protection Agency
Cincinnati, Ohio 45268
EPA-600/R-92/129
AUGUST 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 are published in Supplement III which is described below. Address your request for this manual to NTIS 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 drinking water or drinking water sources are described in detail. These methods will give the laboratory analyst the capability to accurately and precisely determine organic compounds that are currently regulated in drinking water, designated for regulation by the Office of Ground Water and Drinking Water 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 these methods. 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 versions employ new analytical techniques, such as liquid-solid extraction, to improve method performance and reduce the use of organic solvents. Three are new methods for the determination of semivolatile compounds: Method 554 for ozonation disinfection by-products, Method 555 for phenoxyacid herbicides using the novel approach of in-line extraction/high performance liquid chromatography (HPLC), and Method 553 for nonvolatile compounds using particle beam HPLC/MS.



TABLE OF CONTENTS
Method Number Title Revision Page
- Foreword - iii
- Abstract - iv
- Acknowledgment - vi
- Analyte - Method Cross Reference - vii
- Introduction - 1
524.2 Measurement of Purgeable Organic Compounds in Water by Capillary Column Gas Chromatography/Mass Spectrometry 4.0 5
515.2 Determination of Chlorinated Acids in Water Using Liquid-Solid Extraction and Gas Chromatography With an Electron Capture Detector 1.0 51
548.1 Determination of Endothall in Drinking Water by Ion Exchange Extraction, Acidic Methanol, Methylation Gas Chromatography/Mass Spectrometry 1.0 89
549.1 Determination of Diquat and Paraquat in Drinking Water by Liquid-Solid Extraction and HPLC with Ultraviolet Detection 1.0 119
552.1 Determination of Haloacetic Acids and Dalapon in Drinking Water by Ion Exchange Liquid-Solid Extraction and Gas Chromatography With Electron Capture Detection 1.0 143
553 Determination of Benzidines and Nitrogen-Containing Pesticides in Water by Liquid-Liquid Extraction or Liquid-Solid Extraction and Reverse Phase High Performance Liquid Chromatography/Particle Beam/Mass Spectrometry 1.1 173
554 Determination of Carbonyl Compounds in Drinking Water by DNPH Derivatization and High Performance Liquid Chromatography 1.0 213
555 Determination of Chlorinated Acids in Water by High Performance Liquid Chromatography With a Photodiode Array Ultraviolet Detector 1.0 237



ANALYTE - METHOD CROSS REFERENCE
Analyte Method No.
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) and metabolites 515.2, 555
Decanal 554
Dibromoacetic acid 552.1
Dibromochloromethane 524.2
1,2-Dibromo-3-chloropropane 524.2
1,2-Dibromoethane 524.2
Dibromomethane 524.2
Dicamba 515.2, 555
Dichloroacetic acid 552.1
1,2-Dichlorobenzene 524.2
1,3-Dichlorobenzene 524.2
1,4-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-dichlorophenoxyacetic acid) 515.2, 555
1,2-Dichloropropane 524.2
1,3-Dichloropropane 524.2
2,2-Dichloropropane 524.2
1,1-Dichloropropene 524.2
1,1-Dichloropropanone 524.2
cis-1,3-Dichloropropene 524.2
trans-1,3-Dichloropropene 524.2
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-trichlorophenoxyacetic acid) 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

U. S. Environmental Protection Agency

An integral component of the role of the Environmental Protection Agency (EPA) in protecting the quality of the Nation's water resources is the provision of means for monitoring water quality. In keeping with this role, EPA develops and disseminates analytical methods for measuring chemical and physical parameters affecting water quality, including chemical contaminants that may have potential adverse effects upon human health. This manual provides eight analytical methods for 133 organic contaminants, which may be present in drinking water or drinking water sources. In December 1988, EPA published "METHODS FOR THE DETERMINATION OF ORGANIC COMPOUNDS IN DRINKING WATER," EPA/600/4-88/039, a manual containing 13 methods for approximately 200 potential 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. This manual provides methods to determine analytes that appear at a later time in the regulatory framework, and technology that supports the EPA Pollution Prevention Policy. Efforts have been made to provide a manual that is consistent with the earlier versions.

REGULATORY BACKGROUND

nalytical methodology for monitoring water quality serves a number of related purposes, including occurrence studies in community water systems, health effects studies, and the determination of the efficacy of various water treatment approaches. These activities, in turn, form the supporting basis for water quality regulations, and the support of these regulations is the ultimate purpose of the analytical methods. Limitations on the levels of specific contaminants are codified in proposed and 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 for drinking water contaminants that may cause adverse health effects and which are known or anticipated to occur in public water systems. The 1986 amendments require regulations to include Maximum Contaminant Levels (MCLs) with compliance determined by regulatory monitoring or by the application of an appropriate treatment, when adequate analytical methodology is not available. In addition, the 1986 amendments specified 83 contaminants, originally scheduled for regulation by June 19, 1989. The amended Act also required EPA to develop a priority list of additional 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 basis thereafter.

Of the original 83 pollutants, regulations for eight volatile organic chemicals (VOCs) were promulgated in June 1987 (see 52 FR 25690 and 51 FR 11396). Analytical methods for these eight as well as other unregulated VOCs were published in the December 1988 manual (EPA Methods 502.1, 502.2, 503.1, 524.1 and 524.2). Regulations for 30 organic chemicals, 10 volatile compounds 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, aldicarb sulfoxide, aldicarb sulfone, ethylbenzene, heptachlor, heptachlor epoxide and styrene. With the exception of lindane, analytical methods for all 30 compounds are by the VOC methods above or SOC methods also included in the 1988 manual.

Supplement I provides analytical methods for many of the remaining contaminants on the original list 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 1988 manual, the July 1991 revision, and Supplement I. The introductions to the earlier manuals discuss general method features on format, sample matrices, method detection limits (MDLs), and calibration and quality control samples. These same comments apply herein. In particular, these methods are written in standardized terminology in a stand-alone format, requiring no other source material for application. The methods in this manual, unlike previous manuals, are assembled in the format recommended by the Agency's Environmental Monitoring Management Council (EMMC). The methods are designed primarily for drinking water and drinking water sources. However, some performance data are included for more complex matrices such as wastewater. The MDLs provided were determined by replicate analyses of fortified reagent water over a relatively short period of time. As such, these are somewhat idealized limits; nevertheless, provide a useful index of method performance. Reporting limits for reliable quantitative data may be considerably higher.

The quality control sections are uniform and contain minimum requirements for operating a reliable monitoring 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 particular needs of monitoring programs; e.g., the analyses of field reagent blanks, instrument control samples and performance evaluation samples. Where feasible, surrogate analytes have been included in the methods as well as internal standards for calibration. Surrogate recoveries and the internal standard response should be routinely monitored as continuing checks on instrument performance, calibration curves and overall method performance.

THE ANALYTICAL METHODS

This manual contains eight methods. These methods utilize new sample preparation technology such as disk or cartridge liquid-solid extraction, or use new relatively harmless methylating reagents; therefore, directly support the Environmental Protection Agency's Policy on Pollution Prevention. Methods 515.2, 524.2 Revision 4.0, 548.1, 549.1, and 552.1 replace older versions of these methods. The older versions were numbered 515.1, 524.2 Revision 3.0, 548, 549, and 552 respectively, 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 in Drinking Water - Supplement I," EPA/600/4-90/020, July 1990; Environmental Monitoring Systems Laboratory - Cincinnati). The Environmental Protection Agency's Office of Ground Water and Drinking Water believes that only one version of any analytical method should be approved for compliance with drinking water regulations. Thus, EPA will quickly approve the new versions of these five methods. Until these methods are promulgated by EPA, the older versions should be retained for compliance purposes. The remaining three are new methods for the determination of semivolatile or nonvolatile compounds: Method 553 for nonvolatile organics using a high performance liquid chromatograph interfaced to a mass spectrometer through a particle beam interface, Method 554 for ozonation disinfection by-products, and Method 555 for phenoxyacetic acid herbicides using the novel approach of in-line liquid-solid extraction and high performance liquid chromatography.

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

Method 515.2 is an improved method to determine chlorinated herbicides in water. This method utilizes a new liquid-solid disk extraction procedure. Some of the phenolic herbicides are very difficult to derivatize, and still require the use of the stronger reagent, diazomethane. The disk extraction replaces the cumbersome liquid-liquid extraction and the Florisil cleanup in Method 515.2. Dalapon, a method analyte in Method 515.1, is no longer a method analyte in this new method. 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 replace the older Method 548. This method utilizes an intermediate strength amine anion exchange sorbent to extract the endothall from a 100 mL sample aliquot, and forms the dimethyl derivative quickly and easily using acidic methanol as the methylating reagent. Dimethyl endothall is then identified and measured with gas chromatography/mass spectrometry (GC/MS). A flame ionization detector may be used if a second dissimilar column is used for corroboration. Method 548.1 has a MDL approximately ten times lower than the older 548.

Method 549.1 is an improvement over the existing Method 549 in that it now utilizes liquid-solid disk extractions in addition to the cartridges. The expanded liquid-solid extraction technology significantly reduces the amount of organic solvent required to carry out the extraction. Using less potentially harmful solvents directly supports the Environmental Protection Agency's Policy on Pollution Prevention in the laboratory. Comparable MDLs below a part per billion are achieved with both 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 was designed as a simplified alternative to the cumbersome Method 552 which employs liquid-liquid extraction. This method provides a much superior technique for Dalapon over the complex herbicide procedure described in Method 515.1. The sample is extracted with a miniature anion exchange column, and the analytes are methylated directly in the eluant using acidic methanol instead of diazomethane. MDLs using this method for matrices which pose no analyte losses due to matrix effects are generally 1 g/L or lower.

Method 553 is a new method for the determination of nonvolatile organic compounds, including benzidines and nitrogen containing pesticides, in water. This method employs reverse phase high performance liquid chromatography (HPLC) interfaced to a mass spectrometer through a particle beam interface. This new technology provides the analyst the ability to determine a large, new scope 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, aldicarb sulfone regulated in January 1991 and carbofuran regulated in May 1992.

Method 554 is a new HPLC method optimized for the determination of selected carbonyl compounds in finished drinking water and raw source water. These carbonyl compounds are either known or suspected disinfection by-products from the ozonation disinfecting process. This method also utilizes cartridge liquid-solid extraction technology in support of the Agency's Pollution Prevention Policy. 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 to determine the same chlorinated herbicides on the analyte lists in Methods 515.1 and 515.2. This method requires no derivatization procedure which completely eliminates the need for diazomethane or even acidic methanol. This method utilizes a new extraction approach, in-line concentration of the analytes on a concentrator column, which requires only the HPLC mobile phase as the extracting solvent. The entire amount of herbicide contained in a 20-mL sample aliquot is introduced into the analytical system giving the method the needed sensitivity. This method directly supports the Pollution Prevention Policy, and completely eliminates the possible exposure of the analyst to harmful extracting solvent vapors, and to the possibility of a diazomethane explosion.


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Methods for the Determination of Organic Compounds in Drinking Water
Supplement III

National Exposure Research Laboratory
Office of Research and Development
U.S. Environmental Protection Agency
Cincinnati, Ohio 45268
EPA-600/R-95/131
August 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 this manual 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. Most of these methods were published as prior versions in other methods manuals in this series. The versions in Supplement III provide corrections, minor technical enhancements, and editorial improvements to the previously published analytical methods. Several previously distributed but not formally published methods are also included. Fourteen of the fifteen methods utilize high resolution gas chromatography (GC) for separation of analytes from each other and from other substances in the water sample. One method employs high performance reverse phase liquid chromatography for the separation. Two methods utilize a mass spectrometer for the unambiguous identification and measurement of the compounds separated by high resolution GC. These two methods are extremely versatile and have been single-laboratory validated for a total of 194 individual 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 drinking water are included in the methods in this manual.


TABLE OF CONTENTS
Method Number Title Revision Page
- Foreword - iii
- Abstract - iv
- Acknowledgment - vii
- Analyte - Method Cross Reference - viii
- Introduction - 1
502.2 Volatile Organic Compounds in Water by Purge and Trap Capillary Column Gas Chromatography with Photoionization and Electrolytic 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 by Microextraction and Gas Chromatography 1.1  
505 Analysis of Organohalide Pesticides and Commercial Polychlorinated Biphenyl (PCB) Products in Water by Microextraction and Gas Chromatography 2.1  
506 Determination of Phthalate and Adipate Esters in Drinking Water by Liquid-Liquid Extraction or Liquid-Solid Extraction and Gas Chromatography with Photoionization Detection 1.1  
507 Determination of Nitrogen- and Phosphorus-Containing Pesticides in Water by Gas Chromatography with a Nitrogen-Phosphorus Detector 2.1  
508 Determination of Chlorinated Pesticides in Water by Gas Chromatography with an Electron Capture Detector 3.1  
508.1 Determination of Chlorinated Pesticides, Herbicides, and Organohalides by Liquid-Solid Extraction and Electron Capture Gas Chromatography 2.0  
509 Determination of Ethylene Thiourea (ETU) in Water using Gas Chromatography with a Nitrogen-Phosphorus Detector 1.1  
515.1 Determination of Chlorinated Acids in Water by Gas Chromatography with an Electron Capture Detector 4.1  
515.2 Determination of Chlorinated Acids in Water using Liquid-Solid Extraction and Gas Chromatography with an Electron Capture Detector 1.1  
524.2 Measurement of Purgeable Organic Compounds in Water by Capillary Column Gas Chromatography/Mass Spectrometry 4.1  
525.2 Determination of Organic Compounds in Drinking Water by Liquid-Solid Extraction and Capillary Column Gas Chromatography/Mass Spectrometry 2.0  
531.1 Measurement of N-Methylcarbamoyloximes and N-Methylcarbamates in Water by Direct Aqueous Injection HPLC with Post Column Derivatization 3.1  
551.1 Determination of Chlorination Disinfection Byproducts, Chlorinated Solvents, and Halogenated Pesticides/Herbicides in Drinking Water by Liquid-Liquid Extraction and Gas Chromatography with Electron-Capture Detection 1.0  
552.2 Determination of Haloacetic Acids and Dalapon in Drinking Water by Liquid-Liquid Extraction, Derivatization and Gas Chromatography with Electron Capture Detection 1.0  



ANALYTE - METHOD CROSS REFERENCE
ANALYTE METHOD NO.
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
Aldrin 505, 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
Bromacil 507, 525.2, 551.1
Bromochloroacetic acid 552.2
Bromochloroacetonitrile 551.1
Bromochloromethane 502.2, 524.2, 551.1
Bromodichloroacetic acid 552.2
Bromodichloromethane 502.2, 524.2
Bromoform 502.2, 524.2, 551.1
Bromomethane 502.2, 524.2
Butachlor 507, 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 tetrachloride 502.2, 524.2, 551.1
Chloramben 515.1
Chloral Hydrate 551.1
Chlordane 505, 508
Alpha-chlordane 505, 508, 508.1, 525.2
Gamma-chlordane 505, 508, 508.1, 525.2
Trans nonachlor 525.2
Chloroacetonitrile 524.2
Chlorobenzene 502.2, 524.2
Chlorobenzilate 508, 508.1, 525.2
2-Chlorobiphenyl 525.2
Chlorodibromoacetic acid 552.2
1-Chlorobutane 524.2
Chloroethane 502.2, 524.2
Chloroform 502.2, 524.2, 551.1
Chloromethane 502.2, 524.2
Chloroneb 508, 508.1, 525.2
Chloropicrin 551.1
Chlorothalonil 508, 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
Cyanazine 508.1, 525.2, 551.1
Cycloate 507, 525.2
Dacthal(DCPA) 525.2
2,4-D 515.1, 515.2
Dalapon 515.1, 515.2, 552.2
2,4-DB 515.1, 515.2
DCPA acid metabolites 508, 508.1, 515.1
4,4'-DDD 508, 508.1, 525.2
4,4'-DDE 508, 508.1, 525.2
4,4'-DDT 508, 508.1, 525.2
Diazinon 507, 525.2
Dibenz[a,h]anthracene 525.2
Dibromoacetic acid 552.2
Dibromoacetonitrile 551.1
Dibromochloromethane 502.2, 524.2, 551.1
1,2-Dibromo-3-chloropropane 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
1,3-Dichlorobenzene 502.2, 524.2
1,4-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
1,1-Dichloroethene 502.2, 524.2
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
1,3-Dichloropropane 502.2, 524.2
2,2-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
Dieldrin 505, 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
Dimethyl phthalate 506, 525.2
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 I 508, 508.1, 525.2
Endosulfan II 508, 508.1, 525.2
Endosulfan sulfate 508, 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
Etridiazole 508, 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
Hexachlorocyclopentadiene 505, 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
Pentachlorophenol 515.1, 515.2, 525.2
cis-Permethrin 508, 508.1, 525.2
Trans-Permethrin 508, 508.1, 525.2
Phenanthrene 525.2
Picloram 515.1, 515.2
Prometon 507, 525.2
Prometryn 507, 525.2
Pronamide 507, 525.2
Propachlor 508, 508.1, 525.2
Propazine 507, 525.2
Propionitrile 524.2
Propylbenzene 502.2
n-Propylbenzene 524.2
Pyrene 525.2
Simazine 505, 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
Toxaphene 505, 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-Trichloroethane 502.2, 524.2, 551.1
1,1,2-Trichloroethane 502.2, 524.2, 551.1
Trichloroethene 505.2, 524.2
Trichloroethylene 551.1
Trichlorofluoromethane 502.2, 524.2
1,1,1-Trichloro-2-propanone 551.1
1,2,3-Trichloropropane 504.1, 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 1016 505, 508, 508.1, 525.2
Aroclor 1221 505, 508, 508.1, 525.2
Aroclor 1232 505, 508, 508.1, 525.2
Aroclor 1242 505, 508, 508.1, 525.2
Aroclor 1248 505, 508, 508.1, 525.2
Aroclor 1254 505, 508, 508.1, 525.2
Aroclor 1260 505, 508, 508.1, 525.2



INTRODUCTION

William L. Budde and Jean W. Munch

U. S. Environmental Protection Agency

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

As in other manuals in this series, each of the methods in Supplement III was intended to stand alone, that is, each method may be removed from the manual, photocopied, inserted into another binder, and used without loss of information. The stand-alone character of the methods comes at some cost of duplication of material, but the authors believe that the added bulk of the methods is a 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 slightly modified method numbers to distinguish them from pre-viously published versions. A change in the revision number indicates a relatively small modification to the method and a change in the method number usually indicates a relatively larger change in the method. The cover page of each method 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 to assist users who may have older versions in their files in understanding the chronological relationship of methods as technical improvements were made over the years. It also gives due credit to previous authors who contributed to the development of the methods in this and previous manuals in this series. Unless otherwise indicated, all authors were direct Federal employees of the U. S. Environmental Protection Agency at the time of their contributions.

Some methods in supplement III utilize the liquid-solid extraction technology which was pioneered by the USEPA in the original Method 525 in 1988. The scientifically correct term liquid-solid extraction (LSE), in which both phases of the equilibrium partition process are named, is used throughout 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 with only reagent water and/or drinking water, caution is needed when applying these methods to matrices other than reagent or drinking water. One exception is Method 524.2 which has been tested 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 laboratories participated 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, drinking water, ground water, several industrial waste waters, and a simulated hazardous waste site aqueous leachate. Fortified analyte concentrations ranged from 0.2 g/L to 80 g/L and generally excellent accuracy and precision was reported. Full details of that study will be published by the ASTM.

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


Method in Supp. III Comments
502.2
rev. 2.1
Rev. 2.0 was published in EPA/600/4-88/039 in Dec. 1988 and July 1991. Rev. 2.1 is modified to specify conditions under which alternative trapping materials may be used and instructions are clarified for sample preservation and dechlorination. Conditions which do not require a photoionization detector are specified.
504.1
rev. 1.1
Method 504.1 improves Method 504 rev. 2.0 which was published in EPA/600/4-88/03s, the holding time, and the compound 1,2,3-trichloropropane is added to the analyte list. Cautions are included on the frequent coelution of ethylene dibromide and bromodichloromethane.
505
rev. 2.1
Rev. 2.0 was published in EPA/600/4-88/039 in Dec. 1988 and July 1991. Rev. 2.1 is modified to remove alternative detectors except mass spectrometry for qualitative confirmation and to provide additional instructions on the measurement of multi-component mixtures.
506
rev. 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 themethod summary.
507
rev. 2.1
Rev. 2.0 was published in EPA/600/4-88/039 in Dec. 1988 and July 1991. Rev. 2.1 is modified to remove mercuric chloride as a preservative. Data tables are reorganized for clarity and addition of method detection limits. Alternative detectors are eliminated except mass spectrometry for qualitative confirmation.
508
rev. 3.1
Rev 3.0 was published in EPA/600/4-88/039 in Dec. 1988 and July 1991. Rev. 3.1 is modified to remove mercuric chloride as a preservative. Data tables are reorganized for clarity and addition of method detection limits. Alternative detectors are eliminated except mass spectrometry for qualitative confirmation.
508.1
rev. 2.0
Method 508.1 is a significant improvement to Method 508. It employs the liquid-solid extraction technology of Method 525.2 and has an analyte list consisting of many Method 507 and Method 508 substances including the former commercial Aroclor mixtures.
509
rev. 1.1
Method 509 is a single analyte method for the pesticide metabolite ethylenethiourea. This method is derived from national pesticide survey Method 6.
515.1
rev. 4.1
Rev. 4.0 was published in EPA/600/4-88/039 in Dec. 1988 and July 1991. Rev. 4.1 is modified to remove mercuric chloride as a preservative. Data tables are reorganized for clarity and addition of method detection limits. Trimethylsilyldiazomethane (TMSD) is added as an alternative methylating agent.
515.2
rev. 1.1
Rev. 1.0 was published in EPA/600/R-92/129 (Supp. II) in August, 1992. Rev. 1.1 is modified to include trimethylsilyldiazomethane (TMSD) as an alternative methylating agent.
524.2
rev. 4.1
Rev. 4.0 was published in EPA/600/R-92/129 (Supp. II) in August, 1992. Rev. 4.1 is modified to specify conditions under which alternative trapping materials may be used and instructions are clarified for sample preservation and dechlorination. The quality assurance section is clarified and data for two analytes are added.
525.2
rev. 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 in July,1991. Method 525.2 includes criteria for judging the equivalency of alternative liquid-solid extraction cartridges and disks. The elution solvent is modified and data are included for additional analytes including all former commercial Aroclor mixtures.
531.1
rev. 3.1
Rev. 3.0 was published in EPA/600/4-88/039 in Dec. 1988 and July 1991. Rev. 3.1 is modified to remove the requirement to freeze the samples. Data tables are revised for clarity and method detection limits are included.
551.1
rev. 1.0
Method 551.1 is an improvement to Method 551 which was published in EPA/600/4-90/020 (Supp. I) in July 1990. Pentane is included as an alternative solvent for some analytes, the analyte list is expanded, and a new sample preservation technique is used.
552.2
rev. 1.0
Method 552.2 is similar to Method 552 which was published in EPA/600/4-90/020 (Supp. I) in July, 1990. Method 552.2 uses acidic methanol for methylation instead of diazomethane and expands the analyte list.


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Methods for the Determination of Inorganic Substances in Environmental Samples

Environmental Monitoring Systems Laboratory
Office of Research and Development
U.S. Environmental Protection Agency
Cincinnati, Ohio 45268
EPA/600/R-93/100
August 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 for their order number PB94-120821; the cost is $31.00.

ABSTRACT

This manual contains ten updated and revised automated, semi-automated or manual methods amenable to automation for the determination of a variety of inorganic substances in water and wastewater. These methods include and address, in an expanded form, information concerning safety, quality control, pollution prevention, and waste management. Methods were selected which minimize the amount of hazardous reagents required and maximize sample throughput to allow expanded quality control. Automated methods are included for nitrate-nitrite, phosphorus, and sulfate. Semi-automated methods cover cyanide, ammonia, total kjeldahl nitrogen (TKN), chemical oxygen demand (COD) and generic phenolics. Methods amenable to automation include turbidity and inorganic anions by ion chromatography.

TABLE OF CONTENTS
Method Number 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 by Ion Chromatography 2.1 8/93  
335.4 Determination of Total Cyanide by Semi-Automated Colorimetry 1.0 8/93  
350.1 Determination of Ammonia Nitrogen by Semi-Automated Colorimetry 2.0 8/93  
351.2 Determination of Total Kjeldahl Nitrogen by Semi-Automated Colorimetry 2.0 8/93  
353.2 Determination of Nitrate-Nitrite by Automated Colorimetry 2.0 8/93  
365.1 Determination of Phosphorus by Automated Colorimetry 2.0 8/93  
375.2 Determination of Sulfate by Automated Colorimetry 2.0 8/93  
410.4 Determination of Chemical Oxygen Demand by Semi-Automated Colorimetry 2.0 8/93  
         
420.4 Determination of Total Recoverable Semi-Automated Colorimetry 1.0 8/93  



INTRODUCTION

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

U. S. Environmental Protection Agency

The original version of this manual was issued in November 1969 by the Federal Water Pollution Control Administration as "FWPCA Methods for Chemical Analysis of Water and Wastes." With the creation of the United States Environmental Protection Agency (USEPA) in 1970 came "Methods for Chemical Analysis of Water and Wastes 1971" Publication No. 16020---07/71. The second edition was issued in 1974 as EPA 625/6-74-003, and the third edition in 1979 as EPA 600/4/79-020. The most recently published version, an updated second printing of the third edition, was revised and issued in March 1983. The methods contained in the 1983 manual form the basis for most of the methodology approved for compliance monitoring of inorganic parameters specified under the Clean 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 publication entitled, "Methods for the Determination of Metals in Environmental Samples." Concurrently, the decision 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 sections where standardized terminology is not yet available. The terms were carefully selected to be meaningful without extensive definition, and therefore should be easy to understand and 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 Management Council (EMMC) format.

Although a number of other methods included the 1983 edition of USEPA "Methods for Chemical Analysis 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 acceptable for compliance monitoring, the revised methods contained in this publication are considered to be the most useful in terms of future regulatory requirements. They represent a selection of air segmented automated, semi-automated, or amenable to automation methodology that provides the 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 insure valid results.
  • Lower per analysis reagent consumption to reduce waste production and minimize disposal costs.
  • The inclusion of multi-laboratory data generated from USEPA performance evaluation studies.

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 hydrazine sulfate.
  • 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 specifies the 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 or improvements.


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Methods for the Determination of Metals in Environmental Samples

Environmental Monitoring Systems Laboratory
Office of Research and Development
U.S. Environmental Protection Agency
Cincinnati, Ohio 45268
EPA-600/4-91-010
June 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 of Methods 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 order number PB91-231498; the cost is $61.50.

ABSTRACT

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

TABLE OF CONTENTS
Method Number Title Revision Date Page
- 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 for Total Recoverable Elements 2.3 4/91 13
200.3 Sample Preparation Procedure for Spectrochemical Determination of Total Recoverable Elements in Biological Tissues 1.0 4/91 23
200.7 Determination of Metals and Trace Elements in Water and Wastes by Inductively Coupled Plasma-Atomic Emission Spectrometry 3.3 4/91 31
200.8 Determination of Trace Elements in Water and Wastes by Inductively Coupled Plasma - Mass Spectrometry 4.4 4/91 83
200.9 Determination of Trace Elements by Stabilized Temperature Graphite Furnace Atomic Absorption Spectrometry 1.2 4/91 123
200.10 Determination of Trace Elements in Marine Waters by On-Line Chelation Preconcentration and Inductively Coupled Plasma - Mass Spectrometry 1.4 4/91 153
200.11 Determination of Metals in Fish Tissue by Inductively Coupled Plasma-Atomic Emission Spectrometry 2.1 4/91 177
218.6 Determination of Dissolved Hexavalent Chromium in Drinking Water, Groundwater, and Industrial Wastewater Effluents by Ion Chromatography 3.2 4/91 211
245.1 Determination of Mercury in Water by Cold Vapor Atomic Absorption Spectrometry 2.3 4/91 227
245.3 Determination of Inorganic Mercury (II) and Selected Organomercurials in Drinking and Ground Water by High Performance Liquid Chromatography(HPLC) with Electrochemical Detection (ECD) 1.1 4/91 241
245.5 Determination of Mercury in Sediment by Cold Vapor Atomic Absorption Spectrometry 2.3 4/91 267
245.6 Determination of Mercury in Tissuesby Cold Vapor Atomic Absorption Spectrometry 2.3 4/91 281



ANALYTE - METHOD CROSS REFERENCE
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
Arsenic 200.1, 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
Cadmium 200.1, 200.2, 200.3, 200.7, 200.8, 200.9, 200.10, 200.11
Calcium 200.2, 200.3, 200.7, 200.11
Chromium 200.1, 200.2, 200.3, 200.7, 200.8, 200.9, 200.11
Chromium VI 218.6
Cobalt 200.2, 200.3, 200.7, 200.8, 200.10
Copper 200.1, 200.2, 200.3, 200.7, 200.8, 200.9, 200.10, 200.11
Iron 200.2, 200.3, 200.7, 200.9, 200.11
Lead 200.1, 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
Nickel 200.2, 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

U. S. Environmental Protection Agency

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

An important feature of the methods in this manual is the consistent use of terminology, and this feature is especially helpful in the quality control sections where standardized terminology is not yet available. The terms were carefully selected to be meaningful without extensive definition, and therefore should be easy to understand and use. The names of authors of the methods are provided 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 and published that respond to specific regulations, such as the Safe Drinking Water Act (SDWA) or to special studies such as the Environmental Monitoring and Assessment Program (EMAP) Near Coastal Demonstration Project. These methods are, however, available for incorporation into several 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 the permit programs. The methods applicable for use in marine and estuary waters will be available for use in the Agency's National Estuary Program and subsequent EMAP studies that may involve the determination of toxic metals in the water column.

The quality assurance sections are uniform and contain minimum requirements for operating a reliable monitoring 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 particular needs of monitoring programs e.g., analyses of field reagent blanks, instrument control samples and performance evaluation samples.


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Methods for the Determination of Metals in Environmental Samples
Supplement I

Environmental Momitoring Systems Laboratory
Office of Research and Development
U.S. Environmental Protection Agency
Cincinnati, Ohio 45268
EPA-600/R-94/111
May 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 NTIS and request their order number PB95-125472; the cost is $44.00.

ABSTRACT

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

TABLE OF CONTENTS
Method Number Title Revision Date Page
- Disclaimer - - ii
- Foreword - - iii
- Abstract - - iv
- Acknowledgement - - vi
- Introduction - - vii
200.2 Sample Preparation Procedure for Spectrochemical Determination of Total Recoverable Elements 2.8 5/94  
200.7 Determination of Metals and Trace Elements in Water and Wastes by Inductively Coupled Plasma-Atomic Emission Spectrometry 4.4 5/94  
200.8 Determination of Trace Elements in Water and Wastes by Inductively Coupled Plasma - Mass Spectrometry 5.3 5/94  
200.9 Determination of Trace Elements by Stabilized Temperature Graphite Furnace Atomic Absorption Spectrometry 2.2 5/94  
200.15 Determination of Metals and Trace Elements in Water by Ultrasonic Nebulization Inductively Coupled Plasma-Atomic Emission Spectrometry 1.2 5/94  
218.6 Determination of Dissolved Hexavalent Chromium in Drinking Water, Groundwater, and Industrial Wastewater Effluents by Ion Chromatography 3.3 5/94  
245.1 Determination of Mercury in Water by Cold Vapor Atomic Absorption Spectrometry 3.0 5/94  



ANALYTE - METHOD CROSS REFERENCE
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
Chromium VI 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

U. S. Environmental Protection Agency

Six of the seven methods appearing in this supplement were included in the first publication of the manual "Determination of Metals in Environmental Samples", EPA 600 4-91/010, June, 1991. The one new method appearing in this supplement is Method 200.15, Determination of Metals and Trace Elements in Water by Ultrasonic Nebulization Inductively Coupled Plasma-Atomic Emission Spectrometry. 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 by the performance data included in the method.

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

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

All methods have the same approach to analytical quality control in that initial demonstration of performance is required prior to method use, and assessing ongoing laboratory performance is mandatory. However, the required frequency of demonstration has been lessened and the acceptance control limits have been widened. Also, the required limits used in assessing recovery data from fortified matrices have been widened. Where available multi-laboratory data and regression 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 recoverable sample digestion procedure that is described in Method 200.2 as a stand-alone procedure. This procedure also is applicable to flame atomic absorption determinations. Using a common sample preparation 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 interferences
  • Titanium has been added as an analyte to Method 200.7
  • Mercury has been added to Method 200.8 for the analysis of drinking water with turbidity of < 1 NTU
  • Zinc has been deleted from Method 200.9 because its determination by the graphite furnace technique is impractical
  • Digestion of Method 245.1 mercury calibration standards is no longer required


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Methods for the Determination of Chemical Substances in Marine and Estuarine
Environmental Samples

Environmental Monitoring Systems Laboratory
Office of Research and Development
U.S. Environmental Protection Agency
Cincinnati, Ohio 45268
EPA/600/R-92/121
November 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 number PB93-182913; 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 and orthophosphate, respectively, appeared in the 1991 interim manual. Since then they have undergone multilaboratory validation studies. Method 365.5 performed well in the study and multilaboratory data are presented in the revision of the method that appears here. The performance of Method 353.4 in the study indicated that the cadmium reduction column chemistry and maintenance requires further investigation. The method has been retained in this manual so that further testing can continue using a standardized method description. Method 440.0 for measurement of total particulate carbon and nitrogen is based upon a well established combustion technique. Procedures for partitioning the organic and inorganic fractions of carbon are also presented. A multilaboratory study is in progress, and the results will be included in a subsequent revision of the method. The three metals methods represent current state-of-the-science in metals measurements. Two of the methods are graphite furnace atomic absorption techniques and the third uses inductively coupled plasma mass spectrometry. Single laboratory performance data are included in the methods. Although few laboratories currently have the instrumentation capabilities to perform all of these methods, it is extremely important to present them in order to stimulate the development of laboratory capability before multilaboratorystudies can be conducted. Method 445.0 is for the determination of chlorophyll a and the phaeopigments using fluorescence detection. 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-green algae. The numbering of methods was correlated with previous EMSL-Cincinnati methods whenever possible. The metals methods are 200 series, the nutrients nitrite+nitrate and orthophosphate are 300 series, and the particulate carbon and nitrogen, and chlorophyll methods are 400 series.


TABLE OF CONTENTS
Method Number Title Revision Date Page
- Disclaimer - - ii
- Foreword - - iii
- Abstract - - iv
- Acknowledgment. - - vi
- Introduction - - 1
200.10 Determination of Trace Elements in Marine Waters by On-Line Chelation Preconcentration and Inductively Coupled Plasma - Mass Spectrometry 1.6 11/92  
200.12 Determination of Trace Elements in Marine Waters by Stabilized Temperature Graphite Furnace Atomic Absorption 1.0 11/92  
200.13 Determination of Trace Elements in Marine Waters by Off-Line Chelation Preconcentration with Graphite Furnace Atomic Absorption 1.0 11/92  
353.4 Determination of Nitrite+ Nitrate in Estuarine and Coastal Waters by Automated Colorimetric Analysis 1.3 11/92  
365.5 Determination of Orthophosphate in Estuarine and Coastal Waters by Automated Colorimetric Analysis 1.4 11/92  
440.0 Determination of Carbon and Nitrogen in Sediments and Particulates of Estuarine/Coastal Waters Using Elemental Analysis 1.4 11/92  
445.0 In Vitro Determination of Chlorophyll a and Phaeophytin a in Marine and Freshwater Phytoplankton by Fluorescence 1.1 11/92  



INTRODUCTION

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

U. S. Environmental Protection Agency

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

Multilaboratory validation studies test the ruggedness of methods, provide single-analyst and multilaboratory precision and accuracy statements and method detection limits that are "typical" of what most laboratories can achieve. Methods that reach this level of evaluation have been thoroughly investigated by a single laboratory and have usually been informally adopted as standard methods by the analytical community. Method 365.5, "Determination of Orthophosphate in Estuarine and Coastal Waters by Automated Colorimetric Analysis", a widely accepted method in the marine community, performed quite well in a multilaboratory study. A table has been added to the method to summarize single-analyst and multilaboratory precision and accuracy of the method for three water matrices. As a result of the study, pooled method detection limits for orthophosphate 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 Coastal Waters by Automated Colorimetric Analysis", did not give acceptable multilaboratory results, and it must return to the development phase. Method 353.4, despite its wide acceptance and routine use in the marine community, failed the ruggedness test when 50% of the participating laboratories in the multilaboratory study returned unacceptable data. Their data suggest that the cadmium reduction column chemistry and maintenance require further investigation. The method, nonetheless, appears in this manual with appropriate caveats for the user so that further testing can continue using a standardized method description.

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

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

The three metals methods presented here represent current state-of-the-science in metals measurement and are suitable for low-level concentrations in high salinity waters. The two methods that use the chelation preconcentration chromatography system offer detection limits roughly an order of magnitude lower than their conventional counterpart methods. As the instrumentation for these techniques becomes more prevalent in analytical laboratories, the methods will undergo multilaboratory validation studies.

This manual should be viewed as a living document, with methods for organics, nutrients and metals continually being added, updated, revised and validated. There is also much work to be done in assuring the provision of SRMs and quality control samples to the marine monitoring community. We encourage users of the methods in this manual to share their experiences with us and 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 and published that respond to specific regulations, such as the Safe Drinking Water Act (SDWA), or to special studies, such as the Environmental Monitoring and Assessment Program (EMAP) Near Coastal Demonstration Project. These methods are, however, available for incorporation into regulatory programs that require the measurement of nutrients and metals in marine waters.


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