Techniques of Water-Resources Investigations of the United States Geological Survey Chapter A3 METHODS FOR ANALYSIS OF ORGANIC SUBSTANCES IN WATER By Donald F. Goerlitz and Eugene Brown Book 5 LABORATORY ANALYSIS DEPARTMENT OF THE INTERIOR WILLIAM P. CLARK, Secretary U.S. GEOLOGICAL SURVEY Dallas L. Peck, Director First printing 1972 Second printing 1972 Third printing 1984 UNITED STATES GOVERNMENT PRINTING OFFICE, WASHINGTON : 1984 For sale by the Distribution Branch, U.S. Geological Survey 604 South Pickert Street, Alexandria, VA 22304 PREFACE The series of manuals on techniques describes procedures for planning and executing specialized work in water-resources investigations. The material is grouped under major subject headings called books and further subdivided into sections and chapters. The unit of publication, the chapter, is limited to a narrow field of subject matter. This format permits flexibility in revision and publication as the need arises. Section A of Book 5 presents techniques used in water analysis. Provisional drafts of chapters are distributed to field offices of the U.S. Geological Survey for their use. These drafts are subject to revision because of experience in use or because of advancement in knowledge, techniques, or equipment. After the technique described in a chapter is sufficiently developed, the chapter is published and is for sale by the U.S. Geological Survey, 604 South Pickett Street, Alexandria, VA 22304. in CONTENTS Page Page Preface..,-.-----..- - ______________________ III Part II, Ar Abstract. ____________________________________ 1 NitrogNitrogen, nitrate—Continued 1 RReferences. __ _ __________ 17 Nitrog 17 Part I, Sampling- __ ____________ _____________ 2 DDiazotization method- 17 Sample preservation _,____.___ ___.___.__._ 3 RReferences. __________ 18 References- __________-._______,-_-___--_-- 4 Nitrog 18 4 KKjeldahl method _ 18 Carbon, all forms. ____-________---____.____ 4 Reference- ______ 20 References..-,. __._ _________________ 6 OxygeOxygen demand, chemical (COD). 20 Chlorophylls- .__-__ __._„____,_____._____ 6 Dichromate oxidation method- 20 Extractive spectrophotometric method. __ 6 HReferences-, ________________ 22 References. ______..„__________________ 8 Phenc 22 Color. ___---_-_._____. __---__-_-_-__-__. 8 EReferences. 24 Comparison method _ _ _ _ _ ______ ______ 8 Pesticides—gasPestic chromatographic analysis. 24 9 References.Ii -__.____.__.________.___ 29 Extractable organic matter. _.-_._-__-____„_ 9 Insecl 30 Oils and waxes. ______ _________________ 9 CGas chromatographic method ___________ 30 References _, _ _ _ _ _ _ _ _.„_„____ _ .. _ 11 References.I _ __________________________ 32 Methylene blue active substances- ___________ 11 ChlorChlorinated hydrocarbon insecticides in sus­ Synthetic anionic detergents ____________ 11 penpended sediment and bottom material _____ 33 13 CGas chromatographic method ___________ 33 Nitrogen, ammonia. __________ ____________ 13 Distillation method. __________________ 13 ChlorChlorinated phenoxy acid herbicides in water. 35 References. _ . - ______________________ 15 (Gas chromatographic method ___________ 35 IReference _____________________________ 39 Nitrogen, nitrate, _______ __-___.___,___.,- 15 Brucine method. ________ _ _ __________ 15 ChloiChlorinated phenoxy acid herbicides in sedi­ Reduction method. _ _ _ ________________ 17 mement (tentative) ________________________ 39 (Gas chromatographic method ___________ 39 TABLES Page 1. Retention values for chlorinated hydrocarbon insecticides,.________________ 25 2. Retention values for phosphorothioate insecticides.________________________ 26 3. Retention values for methyl esters of chlorinated phenoxy acid herbicides. 26 4. Insecticides in water: recovery of compounds added to surface-water samples. 32 METHODS FOR ANALYSIS OF ORGANIC SUBSTANCES IN WATER By Donald F. Goerlirz and Eugene Brown Abstract Because of the myriad of sources from both This manual contains methods used by the U.S. Geo­ pollution and natural processes, organic matter logical Survey for the determination of organic substances is present in almost all surface and ground waters in water. Procedures are included for the following cate­ and directly influences the water quality. gories of organic substances: Organic carbon, chlorophylls, In reviewing water-quality reports, one may color, detergents, nitrogen, oils and waxes, oxygen demand observe that although color, oxygen consumed (chemical), phenolic materials, herbicides, and insecti­ cides. Procedures are also given for the determination of (chemical oxygen demand), and other criteria for chlorinated hydrocarbon insecticides, as well as chlorinated the analysis of organic substances are described phenoxy acid herbicides, in sediment and bottom materials. in the introductory remarks, seldom are such data included in the tables of the report. These data Introduction are noticeably absent from past reports because such crude measurements did not appear to serve The yellow or brown color commonly associated any meaningful purpose in explaining most water with natural water is often the result of the de­ processes. The value of even the most primitive composition of naturally occurring organic matter. measurements of organic substances in water is The most abundant sources of this material in­ apparent, considering the general awareness of clude decaying vegetation, algae, and microscopic man's effect on the environment and the imple­ organisms. These substances are produced mostly mentation of programs to stem the tide of water on land and during runoff are flushed into the pollution, lake eutrophication, and similar prob­ water, where complex biological processes con­ lems. tinue. The role of natural organic substances in The purpose of this manual is to provide direc­ water processes is not very well understood. tions for collection and analysis of water samples These compounds are known to aid in transport­ containing organic substances as required by the ing and solubilizing many trace elements and are Geological Survey in making water-quality in­ important in weathering. Further, natural or­ vestigations. This manual is an updating and ganic substances interact with both organic and compositing of the organic analytical methods inorganic pollutants. contained in Geological Survey Water-Supply In addition to organic matter from natural Paper 1454, "Methods for Collection and Analysis sources, increasing amounts are entering water of Water Samples" (Rainwater and Thatcher, as a direct and (or) indirect result of man's 1960). The intense activity in the field of organic activities. Leading sources of this material are analysis is providing new and improved methods, industrial and domestic waste, agriculture, urban and as appropriate methods become available runoff, mining, and watercraft. Foaming deter­ they will be added to this manual. All methods as gents have been observed in water supplies. Fish written may be subjected to revision from time kills have been caused by toxic chemicals and to time. Methods labeled as tentative are as­ have been linked to nutrient-induced algae sumed to be adequate but need further testing blooms, which deplete the dissolved oxygen. before final acceptance. TECHNIQUES OF WATER-RESOURCES INVESTIGATIONS Part I. Sampling Organic substances on the water surface or incorporated in the bed material present very Refer to Part I, Chapter Al of Book 5, for difficult sampling problems. Surface films may information on site selection, frequency, field appear chronically or intermittently and most safety, and first aid. Before a proper sampling often come from accidental spills or seepage. program can be initiated, the nature of the Samples taken from the surface of a body of organic compounds sought must be considered. water, especially moving water, are almost im­ As a general rule, organic compounds having less possible to evaluate. Quite often the samples than six carbon atoms are water soluble, whereas must be related to the total volume of water, compounds with more than six carbons are not. surface area, film area, and film thickness. At This generalization must be applied with care, present, no universally acceptable surface sam­ however, because the presence of hydroxyl or plers are available, and investigators are required other polar sites on a molecule increases its to fabricate their own. Floating hoops or rec­ solubility. Even very soluble compounds, how­ tangles covered with clean metal foil which ever, may prefer to reside on organic-layered delineate an area and allow skimming a surface sediment. Further, some insoluble compounds sample from calm water have been used with may be suspended on the water surface. In sum­ limited success. Other methods for collecting mary, organic matter in a body of water may be films and slicks from surface waters, such as distributed on the surface, in suspension, ad­ "dustpan skimmers," absorbent cloths, and floor sorbed on suspended sediment, in bed materials, mops, have been used, but none have been and (or) in solution. satisfactory for general application. The method Because of this wide and generally unpre­ most often used for describing a problem area dictable distribution of organic material in a when surface films are involved is identification body of water, the collection of a truly repre­ of the material, locating the source, and then sentative sample requires a great deal of care estimating the amount entering the water. and often requires the use of specialized sampling