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Manual of Manuals
Summaries and Ordering Information for Eight Laboratory Analytical Chemistry Methods Manuals Published by the EPA between 1988 and 1995. - Prepared by William L. BuddeThis 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 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
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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
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.
| 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 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.
To the:
List of Manuals
EPA Methods page
Chemical Exposure Research Branch
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.
| 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 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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Chemical Exposure Research Branch
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.
| 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 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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Chemical Exposure Research Branch
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.
| 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 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 |