1、- American Petroleum Institute IDENTIFICATION OF ORGANIC TOXICANTS IN TREATED REFINERY EFFLUENTS Health and Environmental Sciences Department Publication Number DR 148 Decem ber 1 997 STD.API/PETRO DR Lq8-ENGL 1997 0732290 0604b00 577 9 - I American Petroleum P Institute American Petroleum Institute
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10、f Organic Toxicants in Treated Refinery Effluents Health and Environmental Sciences Department API PUBLICATION NUMBER DR 148 PREPARED UNDER CONTRACT BY: ASCI CORPORATION/ASCI-DULUTH ENVIRONMENTAL TESTING DIVISION 112 EAST SECOND STREET DULUTH, MINNESOTA 55805 DECEMBER 1997 American Petroleum I Insti
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15、05. Copyright Q 1997 American Petroleum institute iii ACKNOWLEDGMENTS THE FOLLOWING PEOPLE ARE RECOGNIZED FOR THEIR CONTRIBUTIONS OF TIME AND EXPERTISE DURING THIS STUDY AND IN THE PREPARATION OF THIS REPORT: API STAFF CONTACT Alexis Steen, Health and Environmental Sciences Department MEMBERS OF THE
16、 BIOMONITORING TASK FORCE Philip B. Dorn, Ph.D., Shell Development Company (Chairman) W. Raymond Arnold, Ph.D., Exxon Biomedical Sciences, Inc. Marie T. Benkinney, Mobil Oil Corporation Janis M. Farmer, BP America R Clean Water Act) in 1972, refinery wastewater treatment systems were diverse in desi
17、gn and treatment effectiveness. Engineering- and technology-based treatment standards, initially developed under the Act to achieve prescribed effluent concentrations resulted in treatment system upgrades and improved wastewater quality. A subsequent EPA initiative to implement water- quality-based
18、effluent limitations (49 Federal Register 9016), as measured by effluent and receiving water aquatic toxicity tests, substantiaily expanded and enhanced aquatic toxicity testing capabilities. During this same period, advancements in analytical chemistry and toxicity identification procedures helped
19、identi refinery wastewater constituents and treatment processes which were responsible for observed toxicity. Treatment system upgrades designed to achieve these water-quality-based objectives further improved effluent quality. This investigation represents the next level of sophistication in efflue
20、nt quality assessments and similarly reflects a substantial change in the nature and magnitude of refinery effluent toxicity. The focus of this study was the isolation and identification of nonpolar, organic wastewater constituents causing measurable, chronic toxicity in treated refinery effluent. N
21、onpolar organic toxicants were operationally defined as those adsorbed by cl8 solid phase extraction (SPE) columns. Effluents from five refineries were selected for screening-level toxicity assessments. Isolation and identification of the organic compounds responsible for the observed toxicity were
22、accomplished after modifications were made to existing toxicity characterization and identification guidance. Specifically, effluent extraction and elution conditions were modified to reduce the complexity of the organic fraction and to increase recovery efficiency of the chronically toxic fraction.
23、 One avenue examined was adjustment of effluent pH before extraction using cl8 columns. Another avenue was modification of the standard Phase II cl8 column elution scheme suggested by the U.S. EPA guidance for performing Toxicity Identification Evaluations (TIES). ES- - STD.API/PETRO DR 148-ENGL 199
24、7 m 0732290 ObO4b11 352 m The toxicants were neither derived from crude oil or refined product nor were they conventional pollutants associated with refinery wastewater treatment systems. The identified toxicants were a phenol associated with a jet fuel additive and two aromatic brominated organics,
25、 believed to be reaction products of cooling tower water treatment chemicals. These compounds exhibited variable, intermittent, and low concentration toxicity and their identification required enhanced fractionation procedures. None of the effluents tested had sufficient concentrations of total diss
26、olved solids, ammonia, or hydrogen sulfide to be of concern for causing chronic toxicity or interfering with examination of the contribution by nonpolar compounds. Only one of five refinery effluents exhibited organic toxicity of sufficient magnitude to allow subsequent attempts at toxicant isolatio
27、n and identification. Additionally, levels of chronic toxicity were generally found to be low. These results constitute a broader demonstration of the significant progress during the last 20+ years in refinery wastewater treatment as well as effluent toxicity characterization and identification. Imp
28、rovements in refinery effluent quality have been accomplished through treatment enhancements and through better housekeeping practices. Substances such as total dissolved solids, ammonia and hydrogen sulfide, formerly recognized as causing toxicity in refinery effluents, have been largely brought un
29、der control. Thus, acute toxicity in refinery effluents is often absent. Chronic toxicity often occurs only at higher effluent concentrations, as demonstrated in this study. Which levels of toxicity are considered of importance in the receiving water depends on the amount and rate of dilution that o
30、ccurs in the receiving stream. Dilution allowance in the receiving water is usually recognized by regulatory authorities. The type and amount of toxicity identified in this study would be of concern only where available dilution was very low. ES-2 STD.API/PETRO DR L4-ENGL 1997 m 0732290 Ob04bL2 299
31、m Section 1 INTRODUCTION BACKGROUND The convergent evolution of aquatic toxicity testing, analytical chemistry, and refinery wastewater engineering has progressed through several levels over the years. Whole effluent aquatic toxicity tests conducted early in this evolutionary process found acute tox
32、icity at relatively low effluent concentrations. These discharges were, and continue to be, complex in chemical composition, and the nature and extent of their toxicity are variable. Prominent inorganic and organic constituents previously identified as responsible for acute andor chronic toxicity we
33、re ammonia, total dissolved solids (TDS), and napthenic acids. Combinations of test species selection and test conditions, treatment system operations and refinery wastewater stream characteristics all played roles in affecting effluent quality. As influences of these conditions were more clearly un
34、derstood and appropriate enhancements made, the incidence and extent of acute effluent toxicity have generally declined. More sensitive subacute tests were developed to identify effluent toxicity, which was usually observed at higher effluent concentrations. Treatment system design and operation wer
35、e also improved to reduce or eliminate sporadic toxicity (e.g., ammonia excursions). Experience illustrated that attention to treatment system operational details and wastewater stream quality (i.e., refinery unit operation) could reduce whole effluent toxicity. Even after the many improvements that
36、 have been made, the more sensitive toxicity tests (largely chronic tests) sometimes reveal measurable chronic toxicity at higher effluent concentrations. The importance of this toxicity to natural receiving systems depends on the degree of dilution occurring. In most situations, sufficient dilution
37、 is available in the receiving water. When dilution in the receiving water is very low, regulatory authorities may insist on further toxicity reduction. It was anticipated that nonpolar organic compounds from refinery processes were in the final effluent and would be frequently contributing to obser
38、vations of chronic toxicity. Information about such toxicants was desired to provide a 1-1 STD.API/PETRO DR 148-ENGL 1997 m 0732290 0604613 125 = better understanding of their contribution to refinery effluent toxicity and to direct efforts towards control andor reduction. The EPA TIE procedures wer
39、e used and modified to identi the small amounts of toxicity caused by nonpolar organic compounds in refinery effluents. OBJECTIVES AND SCOPE Toxicity characterization procedures with either larval fathead minnow (Pimephales promelus) or (Mysidopsis bahia) were performed with effluents from five refi
40、neries to identi6 nonpolar organics responsible for chronic toxicity. Test species selected for this study are also commonly used for determining compliance with effluent discharge toxicity limits. Any toxicity caused by more easily recognized substances, such as ammonia, was not of concern. Charact
41、eristics of selected refinery effluents were initially examined to determine suitable effluents for identification of nonpolar organic toxicants. Nonpolar organic toxicants were operationally defined as those adsorbed by C, SPE columns. Desirable effluent characteristics were: 1) consistent presence
42、 of measurable chronic toxicity due to nonpolar organic compounds; and 2) a lack of toxicity from compounds other than nonpolar organics. Samples with these characteristics were preferred to minimize difficulties in tracking effluent toxicity through sample manipulations and to reduce the possibilit
43、y of artifacts from the multiple treatments required to address toxicants belonging to more than one class of compounds. Historically, several common difficulties have been encountered during identification of nonpolar organic toxicants in refinery effluents. Past problems included: 1) poor recovery
44、 of toxicity from C, solid phase extraction (SPE) columns, 2) poor resolution of toxicity during separative steps, 3) failure to recover toxicity following high performance liquid chromatography (HPLC) separation, and 4) inability to adequately simplifi effluent fractions containing the nonpolar org
45、anic toxicants. Procedures were employed to: 1) simplify the toxic nonpolar organic effluent fraction, 2) achieve sufficient toxicant concentration to allow analytical measurement, and 3) remove water from the fraction to allow analysis by gas 1-2 STD.API/PETRO DR 148-ENGL 1977 m 0732270 ObOLibL4 Ob
46、L m chromatography/mass spectroscopy (GUMS). GC analyses are often not definitive because of the hydrocarbon content of refinery effluents. To overcome these difficulties, modifications of the U.S. EPAs suggested guidance for Phase II Toxicity Identification Evaluation (TIE) procedures (U.S. EPA 199
47、3) for nonpolar organic compounds were developed and tried. 1-3 STD.API/PETRO DR 148-ENGL 1997 0732290 Ob04615 TT8 Section 2 METHODS GENERAL APPROACH The initial approach used to screen five refinery effluents for nonpolar chronic toxicity was the U.S. EPA Phase I procedures (U.S. EPA 1991a). The ef
48、fluent with the most nonpolar chronic toxicity (and the least toxicity from toxicants other than nonpolar toxicants) was selected for detailed toxicant identification using Phase II U.S. EPA procedures (U.S. EPA 1993). Modifications to resolve past TIE performance problems with refinery effluents we
49、re made. The modifications are described here and in the Results Section. If an organic compound seemed likely to be a contributor to observed toxicity, additional information was gathered by literature searches, single chemical toxicity exposures, and location of possible sources of the suspect toxicant within the refinery. INITIAL TOXICITY SCREENS Initial toxicity screens were performed immediately following sample receipt with each effluent sample using only one of the selected TIE species - either mysids, Mysidopsis bahia, or
