Api dr 148 1997 scan (american petroleum institute)

- ~~ - American Petroleum Institute IDENTIFICATION OF ORGANIC TOXICANTS IN TREATED REFINERY EFFLUENTS Health and Environmental Sciences Department Publication Number DR 148 December 1997 `,,-`-`,,`,,`,`,,` - Copyright American Petroleum Institute Provided by IHS under license with API No reproduction or networking permitted without license from IHS STD.API/PETRO ~ DR L q - E N G L 1997 Not for Resale ~~ 0732290 b 0 7 ~~ ~ P American Petroleum Institute American Petroleum Institute Environmental, Health, and Safety Mission and Guiding Principles MISSION PRINCIPLES The members of the American Petroleum Institute are dedicated to continuous efforts to i m p m e the compatibility of our opemtwns with the envimnment while economically developing energy resoutres anà supplying high quality pmducrs and services to consumers We recognize our responsibility to work with the public, the government, and others to develop and to use natural resources in an envimnmentally sound manner while pmtecting the health and safety of our employees and the public To meet these responsibilities, API members pledge to manage our businesses according to -the following principles using sound science to prioritize risks and to implement cost-Mective management practices: o o To recognize and to respond to community concerns about our raw materials, products and operations To operate our plants and facilities,and to handie our raw materials and products in a manner that protects the environment, and the safety and health of our employees and the public To make safety, health and environmental considerations a priority in our planning, and our development of new products and processes I To advise promptly, appropriate officials, employees, customers and the public of information on significant industry-related safety, health and environmental hazards, and to recommend protective measures o To counsel customers, transporters and others in the safe use, transportation and disposal of our raw materials, products and waste materiais o To economically develop and produce naturai resources and to conserve those resources by using energy efficiently o To extend knowledge by conducting or supporting research on the safety, health and environmental effects of our raw materials, products, processes and waste materials o To commit to reduce overail emission and waste generation o To work with others to resolve problems created by handling and disposal of hazardous substances from our operations o To participate with government and others in creating responsible laws, regulations and standards to safeguard the community, workplace and environment o To promote these principles and practices by sharing experiences and offering assistance to others who produce, handle, use, transport or dispose of similar raw materiais, petroleum products and wastes `,,-`-`,,`,,`,`,,` - Copyright American Petroleum Institute Provided by IHS under license with API No reproduction or networking permitted without license from IHS Not for Resale Identification of Organic Toxicants in Treated Refinery Effluents Health and Environmental Sciences Department API PUBLICATION NUMBER DR 148 PREPARED UNDER CONTRACT BY: ASCICORPORATION/ASCI-DULUTH ENVIRONMENTAL TESTINGDIVISION 112 EASTSECOND STREET 55805 DULUTH, MINNESOTA DECEMBER 1997 I `,,-`-`,,`,,`,`,,` - Copyright American Petroleum Institute Provided by IHS under license with API No reproduction or networking permitted without license from IHS Not for Resale American Petroleum Institute ~- ~ ~ ~~~ ~ S T D - A P I / P E T R O DR 148-ENGL 1997 ~ 0732290 6 286 W FOREWORD API PUBLICATIONS NECESSARILY ADDRESS PROBLEMS OF A GENERAL NATLTRE WITH RESPECT TO PARTICULAR CIRCUMSTANCES, LOCAL, STATE, AND FEDERAL LAWS AND REGULATIONS SHOULD BE REVIEWED API IS NOT UNDERTmG TO MEET THE DUTIES OF EMPLOYEiRS, W A C TURERS, OR SUPPLIERSTO WARN AND PROPERLY TRAIN AND EQUIP THEIR EMPLOYEES, AND OTHERS EXPOSED, CONCERNING HEALTH AND SAFETY RISKS AND PRECAUTIONS, NOR UNDERTAKING THEIR OBLIGATIONSUNDER LOCAL, STATE, OR FEDERAL LAWS NOTHING CONTAINED IN ANY API PUBLICATION IS TO BE CONSTRUED AS GRANTING ANY RIGHT, BY IMPLICATION OR OTHERWISE, FOR THE MANUFACTURE, SALE, OR USE OF ANY METHOD, APPARATUS, OR PRODUCT COVERED BY LETTERS PATENT NEITHER SHOULD ANYTHING CONTAINED IN THE PUBLICATION BE CONSTRUED AS INSURING ANYONE AGAINST LIABILITY FOR INFRINGEMENT OF LETTERS PATENT AI1 righrs reserved No part of this work may be reproduced, stored in a retrieval system, or transmitted by any means,electmnic, mechanical, photocopying, recording, or otherwise without priÒr written permission from the publisher Contact the publisher API Publishing Services, 1220 L Street, N W ,Washington, D.C 20005 Copyright Q 1997 American Petroleum institute iii `,,-`-`,,`,,`,`,,` - Copyright American Petroleum Institute Provided by IHS under license with API No reproduction or networking permitted without license from IHS Not for Resale 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 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&D William R Gala, Ph.D., Chevron Research and Technology Company Jerry F Hail, Ph.D., Texaco Research Michael D Harrass, Ph.D., Amoco Corporation Denise J Jett, Phillips Petroleum Company Eugene R Mancini, Ph.D., ARCO James E O’Reilly, Exxon Production Research Company Lawrence A Reitsema, Ph.D., Marathon Oil Company C Michael Swindoll, Dupont Environmental Remediation Svc Michael E Tucker, Occidental Chemical Company Carl Venzke, Citgo Petroleum Corporation The Biomonitoring Task Force also acknowledges the editorial support from Karen Inman, Pamela Greene, and Suzanne Covello at API `,,-`-`,,`,,`,`,,` - Copyright American Petroleum Institute Provided by IHS under license with API No reproduction or networking permitted without license from IHS Not for Resale ~~~ ~ ~~ STD.API/PETRO DR L48-ENGL 1997 0732270 Ob04b05 057 ABSTRACT In this study, effluents from five oil refineries were examined for the presence of nonpolar, organic chronic toxicity following suggested U.S EPA guidelines for Phase I Toxicity Characterization procedures The refinery effluent containing the most toxicity from nonpolar organic toxicants was selected for more detailed analyses and identification of these toxicants using Phase II procedures Extraction and elution conditions were modified to increase chronic toxicity recovery and also reduce the complexiv of the nonpolar organic effluent fraction containing toxicity Results showed that simple modifications of U.S EPA guidance for C,, solid phase extraction (SPE) procedures combined with proper toxicity testing conditions successfully tracked and, to an acceptable degree, isolated toxicity in an effluent fraction amenable for identification of suspected nonpolar organic toxicants Toxicity was observed only in 100% effluent concentrations, not in dilutions of the effluents Further chronic toxicity was not consistently Findings from this study indicated that sources of refinery effluent toxicants were a phenol associated with a jet fuel additive and two brominated organics believed to be reaction products of cooling tower water treatment chemicals, rather than from crude oil constituents Copyright American Petroleum Institute Provided by IHS under license with API No reproduction or networking permitted without license from IHS Not for Resale `,,-`-`,,`,,`,`,,` - observed in the effluent fractions ~~~ ~~ ~ STDDAPIIPETRO DR 148-ENGL 1997 0732290 ObOYbOb T95 = TABLE OF CONTENTS pane Section e5-1 INTRODUCTION 1-1 BACKGROUND 1-1 OBJECTIVES AND SCOPE 1-2 METHODS 2-1 GENERAL APPROACH 2-1 INITIAL TOXICITY SCREENS 2-1 Fathead Minnow Tests 2-1 Mysid Tests 2-2 EXECUTIVE SUMMARY PHASE II cl8 SPE METHODS C SPE Sorption and Elution Concentration of Toxic Phase II Fractions HPLC Separation Techniques GCMS Methods RESULTS PHASE I RESULTS FOR SELECTED REFINERY EFFLUENTS PHASE II NONPOLAR ORGANIC TOXICITY IDENTIFICATION PHASE I METHODS pH Modifications of the Effluent Prior to cl8 2-2 2-2 2-3 2-3 2-4 2-5 3-1 3-1 3-6 Sorption 3-7 Modification of the Standard Phase II Elution Sequence 3-9 PHASE III TOXICITY CONFIRMATION SUMMARY REFERENCES Toxicant Variability Copyright American Petroleum Institute Provided by IHS under license with API No reproduction or networking permitted without license from IHS Not for Resale 3-16 3-22 4-1 R-1 `,,-`-`,,`,,`,`,,` - ~~ STD.API/PETRO DR - E N G L 2997 m 0732290 Ob04607 921 m LIST OF FIGURES Figure 3-1 GCMS Scans of pHi, pH 3.0, and pH 9.0 100% Methanol Toxic Phase II Fraction Concentrates, Refinery #1 - Sample I 3-8 3-2 Comparison of U.S EPA and Modified Scheme Used in This Study for Identification of Nonpolar Toxicants 3-10 3-3 GCMS Total Ion Chromatogram of Toxic 100% Methanol Fraction Concentrate, Refinery #1 - Sample I 3-13 3-4 GC/MS Total Ion Chromatogram for the First Toxic 100% Methanol Fraction Concentrate, Refinery #1 - Sample I 3-14 3-5 GC/MS Total Ion Chromatogram for the Second Toxic 100% Methanol Fraction Concentrate, Refinery #1 - Sample I 3-15 3-6 GCMS Chromatogram for 58 mg/L 2,4 ditert-butyl phenol and Toxic Fraction Concentrate, Refinery #1 - Sample I 3-17 3-7 HPLC Chromatogram for 58 mg/L 2,4 ditert-butyl phenol and Toxic Fraction Concentrate, Refinery #1 - Sample I 3-18 3-8 G C N S Total Ion Chromatogram of the 90% Methanol Fraction Concentrate of Jet Fuel Additive A and Identified Peaks 3-19 3-10 G C N S Total Ion Chromatogram of the Combined 95% and 100% Methanol Fraction Concentrate of Jet Fuel Additive B and Tentatively Identified Peaks 3-21 3-1 GCMS Total Ion Chromatogram of Simplified Toxic C,, SPE Fraction Concentrate, Refinery #1 - Sample II 3-23 3-12 G C N S Total Ion Chromatogram of Simplified Toxic C,, SPE Fraction Concentrate, Refinery #1 - Sample III 3-24 3-13 GC/MS Total Ion Chromatogram of Toxic Eluates Before and After Phase II Separation, Refinery #1 - Sample I 3-25 3-14 GC/MS Total Ion Chromatogram of Toxic Eluates Before and After Phase II Separation, Refinery #1 Copyright American Petroleum Institute Provided by IHS under license with API No reproduction or networking permitted without license from IHS - Sample II Not for Resale 3-26 `,,-`-`,,`,,`,`,,` - 3-9 GCMS Total Ion Chromatogram of the 95% Methanol Fraction Concentrate of Jet Fuel Additive A and Identified Peaks 3-20 -~ ~- STD.API/PETRO DR 148-ENGL 1377 = 0732270 Ob04608 ~- 868 3-15 GC/MS Total Ion Chromatogram of the Concentrated Toxic HPLC Fraction Concentrate Refinery #1 Sample IV 3-27 Sample IV 3-28 3-29 3-18 Mass Spectrum of Peak at 31.066 Minutes Refinery #1 Sample IV 3-30 3-19 Mass Spectrum of Peak at 31.835 Minutes Refinery #1 Sample IV 3-31 3-20 Mass Spectrum of Peak at 44.587 Minutes Refinery #1 Sample IV 3-32 3-16 Mass Spectrum of Peak at 25.301 Minutes Refinery #1 3-17 Mass Spectrum of Peak at 26.350 Minutes Refinery #1 Sample IV 3-21 GCMS Total Ion Chromatogram of HPLC Fraction #11 Refinery #1 SampleV 3-34 3-22 GCMS Total Ion Chromatogram of HPLC Fraction #12 Refinery #1 SampleV 3-35 3-23 Mass Spectrum of Peak at 25.384 Minutes with Breakdown of Chemical Components 3-36 3-24 Mass Spectrum of Peak at 31 042 Minutes with Breakdown of Chemical Components 3-37 3-25 Structures of Brominated Compounds in Refinery #1 Samples IV and V `,,-`-`,,`,,`,`,,` - Copyright American Petroleum Institute Provided by IHS under license with API No reproduction or networking permitted without license from IHS Not for Resale 3-38 LIST OF TABLES Table 3- Chronic Phase I Toxicity Characterization Results for Fathead Minnows Exposed to Refinery #1 Final EMuent 3-2 -2 Chronic Phase I Toxicity Characterization Results for Fathead Minnows Exposed to Refinery #2 Final EMuent 3-3 3-3 Chronic Phase I Toxicity Characterization Results for Mysids Exposed to Refinery #3 Final EMuent 3-4 3-4 Chronic Phase I Toxicity Characterization Results for Mysids Exposed to Refinery #4 Final Effluent 3-5 3-5 Percentage Survival of Fathead Minnows in cl8 Concentrate Made from Effluent That Had Aged for 12 and 19 Days 3-6 3-6 Refinery #1, Fathead Minnow Survival from cl8 SPE Tests Employing pH Adjustment Before Extraction 3-7 3-7 Refinery #3, Mysid Percent Survival in C,, Eluate Employing pH Adjustment Before Elution 3-7 3-8 Mysid Percent Survival in Eight Fractions Eluated from C,, SPE Columns Using Effluent from Refinery #3 3-9 `,,-`-`,,`,,`,`,,` - 3-9 Fathead Minnow Percent Survival in Eight Eluates from C,, SPE Columns Using EMuent from Refinery #3 3-1 3-10 Fathead Minnow Percent Survival in Five Eluates from a C,, SPE Column That Had Previously Been Eluted with 25 and 50% Methanol Using Refinery #1 Copyright American Petroleum Institute Provided by IHS under license with API No reproduction or networking permitted without license from IHS Not for Resale 3-1 ~~ STD.API/PETRO DR L - E N G L 1997 0732290 0604648 4 m I!! 3- -=! `,,-`-`,,`,,`,`,,` - Copyright American Petroleum Institute Provided by IHS under license with API No reproduction or networking permitted without license from IHS 3-28 Not for Resale ~~ STD-API/PETRO ~~ ~ DR - E N G L 1997 0732290 ObO4b49 380 -I * Y o l n :I': % f ct `,,-`-`,,`,,`,`,,` - O a C Q O Copyright American Petroleum Institute Provided by IHS under license with API No reproduction or networking permitted without license from IHS 3-29 Not for Resale > U I $; n P E v; a p3 C E U m ci cd a 5: ' .- I I , I " i r-! -r-T -r - `,,-`-`,,`,,`,`,,` - Copyright American Petroleum Institute Provided by IHS under license with API No reproduction or networking permitted without license from IHS 3-30 Not for Resale : , I ~ ~ S T D - A P I / P E T R O DR 148-ENGL 1997 _ 0732290 06046.51 T39 -._._- `,,-`-`,,`,,`,`,,` - cri ~~ +I O a E o; d I m co J Copyright American Petroleum Institute Provided by IHS under license with API No reproduction or networking permitted without license from IHS 3-3 Not for Resale ~~~~ ~~ ~~ ~ S T D - A P I I P E T R O D R LLiLI-ENGL 1997 0732290 6 975 I i `,,-`-`,,`,,`,`,,` - r i t i Lt 5; i cc L o i a O -.L i c E Copyright American Petroleum Institute Provided by IHS under license with API No reproduction or networking permitted without license from IHS 3-32 Not for Resale The apparent change in toxicants warranted further work to determine variability, and also to reduce the number of compounds associated with toxicity Effluent toxicity characteristics in a fifth sample were the same as for the preceding sample and nonpolar toxicity was retained through the C,, SPE concentration step A small portion of the toxic concentrate was injected on HPLC and a preliminary UV scan was performed to determine peak retention times The remaining concentrate was then separated by peak retention times into 15 fractions Fractions #11 and #12 in the sequence contained a majority of the toxicity recovered after HPLC separation These fractions were concentrated separately and analyzed by GUMS following confirmation of toxicity (Figures 3-21 and 3-22) Both chromatograms show the presence of brominated aromatic compounds at retention times of 25.2 and 26.2 minutes These compounds appeared similar to those present in the previous sample The phenolic compounds initially identified in Refinery #1 samples were not detected in the toxic HPLC concentrates The polarity of the C18extractable toxicants was increased, and the appearance of suspect brominated aromatic toxicants was noted A possible structure of this compound was constructed from the mass spectra for the four unidentified peaks (Figures 3-23 and 3-24) The molecular formula is CJ-IJVBr, for the peaks at 25 and 26 minutes The peaks at 31 minutes have one additional Br, the molecular formula is C&I,NBr, The two peaks for each compound are likely isomers, but the bromides and nitrogen-containing component locations on the benzene ring are not and (w,x,y , tribromo- 1-ethylene-z-methylamine)benzene (Figure 3-25) Additional testing would be required to positively identify the brominated aromatic compounds, and to gather evidence to further link them to effluent toxicity Toxicity to fish and the Phase I characteristics of the pure compounds would need to be determined but were not completed in this study The objective to develop an approach for separating toxicants from non-toxicants in the nonpolar fraction was achieved in spite of the unanswered questions regarding the toxic concentrations Since the phenolic disappeared from the refiery effluent over the course of the study, a complete resolution of the toxic concentration issue could not be completed 3-33 Copyright American Petroleum Institute Provided by IHS under license with API No reproduction or networking permitted without license from IHS Not for Resale `,,-`-`,,`,,`,`,,` - clear In IUPAC nomenclature the compounds are (x, y dibromo- 1-ethylene-z-methylamine) benzene ~~ ~~ ~~ S T D - A P I / P E T R O D R 148-ENGL 1997 ~ = 0732290 0604b54 ~ 748 FIGURE 3-21 G C / M S Total Ion Chromatogram of HPLC Fraction #11, Refinery #1 - Sample V `,,-`-`,,`,,`,`,,` - 3-34 Copyright American Petroleum Institute Provided by IHS under license with API No reproduction or networking permitted without license from IHS Not for Resale ~~ ~ STD.API/PETRO ~ ~ ~ DR 148-ENGL I1977 0732290 Ob04655 684 FIGURE 3-22 GCMS Total Ion Chromatogram of HPLC Fraction #12, Refinery #1 `,,-`-`,,`,,`,`,,` - 3-35 Copyright American Petroleum Institute Provided by IHS under license with API No reproduction or networking permitted without license from IHS Not for Resale ~~ - Sample V t rci O i i - " `,,-`-`,,`,,`,`,,` - 23 rA a C E i vj = i Y