Api publ 4654 1997 scan (american petroleum institute)

FIELDSTUDIES OF BTEX AND MTBE INTRINSIC BIOREMEDIATION `,,-`-`,,`,,`,`,,` - H aith and Envir mental Scie PublicationNumber 4654 October 1997 Copyright American Petroleum Institute Provided by IHS under license with API No reproduction or networking permitted without license from IHS Not for Resale s Department Q American Petroleum Institute American Petroleum Institute Environmental, Health, and Safety Mission and Guiding Principles MISSION The members of the American Pemleum Institute are dedicated to continuous efforts to improve the compatibility of our operations with the environment while economically developing energy resources and supplying high quality products 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 protecting the health and safety of our employees and the public To meet these responsìbiZities, API members pledge to manage our businesses according to thefollowing principles using sound science to pnorinze rish and to implement cost-effectivemanagement practices: ~ PRINCIPLES ~~~ ~ To recognize and to respond to comunity concerns about our raw materiais, products and operations o To operate our plants and facilities, and to handle our raw materiais and products in a manner that protects the environment, and the safety and health of our employees and the public o To make safety, health and environmental considerations a priority in planning, and our development of new products and processes o To advise promptly, appropriate officiais, employees, customers and the public of information on significant industry-related safety, health and environmental hazards, and to recommend protective measures To counsel customers, transporters and others in the safe use, transportation and disposai of our raw materiais, products and waste materials o To economically develop and produce naturai resources and to conserve those resources by using energy efficiently OUI To extend knowledge by conducting or supporting research on the safety, health and environmental effects of our raw materiais, products, processes and waste materiais o To commit to reduce overail emission and waste generation o To work with others to resolve problems created by handling and disposai 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 STD.API/PETRO PUBL 4b54-ENGL 1997 = 2 0 b l i 73T I Field Studies of BTEX and MTBE Intrinsic Bioremediation Health and Environmental Sciences Department API PUBLICATION NUMBER 4654 PREPARED UNDER CONTRACT BY: ROBERT C BORDEN, ROBERTA DANIEL, AND LOUIS E LEBRUN, IV DEPARTMENT OF CIVIL ENGINEERING NORTHCAROLINA STATEUNIVERSITY OCTOBER 1997 American Petroleum Institute `,,-`-`,,`,,`,`,,` - Copyright American Petroleum Institute Provided by IHS under license with API No reproduction or networking permitted without license from IHS Not for Resale FOREWORD API PUBLICATIONS NECESSARILY ADDRESS PROBLEMS OF A GENERAL NATURE WITH RESPECT TO PARTICULAR CIRCUMSTANCES, LOCAL, STATE, AND FEDERAL,LAWS AND REGULATIONS SHOULD BE REVIEWED API IS NOT UNDERTAKING TO MEET THE DUTIES OF EMPLOYERS, MANUFACTURERS, 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 LE"ERS PATENT NEITHER SHOULD ANYTHING CONTAINED IN THE PUBLICATION BE CONSTRUEDAS INSURING ANYONE AGAINST LIABIL ITY FOR INFRINGEMENT OF LETTERS PATENT All rights reserved No part of this work may be mpnniwed, stored in a retrieval system, or transmitted by any means, electronic, mechanical,phorocopying,recording, or otherwise without prior written permissionfrom the publisher Contact the publisher,API Publishing Services, 1220 L Street, N.U!, Washington,D.C 20005 Copyright Q 1997 American Pemleum 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 RECOGNIZEDFOR THEIR CONTRIBUTIONS OF TIME AND EXPERTISE DURING THIS STUDY AND IN THE PREPARATION OF THIS W O R E RS OF THF, SOIL & GROUNDWT E C l m A L TASK FORCE Tim Buscheck, Chevron Research and Technology Company Chen Chiang, Shell Development Company Lesley Hay Wilson, BP Exploration & Oil, Inc Paul Hildebrandt, Chevron Research & Technology Company Bob Hockman, Amoco corporation Minoo Javamardian, Amoco Research Center Dorothy Keech, Keech Associates, Inc Ai Liguori, Exxon Research Engineering Company Eugene Mancini, ARCO R.Edward Payne, Mobil Business Resources Corporation Joseph P Salanitro, Shell Development Company Michael Scott, Exxon Production Research Company Patrick J Shevlin, OXYCHEM Pipeline Operations Curtis Stanley, Shell Development Company C Michael Swindoil,Dupont Environmentai Services Terry Waiden, BP Oil - Europe iv Copyright American Petroleum Institute Provided by IHS under license with API No reproduction or networking permitted without license from IHS Not for Resale `,,-`-`,,`,,`,`,,` - Bruce Bauman, Health and Environmentai Sciences Department -~~ ~ ~- ~- S T D - A P I / P E T R O PUBL 4b54-ENGL 7 7 2 0 b 4 111 ABSTRACT In the last several years, there has been considerable interest in confirming the biodegradation of soluble gasoline constituents in groundwater Recent acceptance of risk-based approaches to corrective action has accelerated the need to better understand the role biodegradation can play in limiting the transport of and possible exposure to dissolved hydrocarbons in groundwater This study was initiated to document the in situ naturai biodegradation (commonly referred to as intrinsic bioremediation) of benzene; ethylbenzene; toluene; o-, m-, and p-xylene; and methyl tert `,,-`-`,,`,,`,`,,` - butyl ether A rural North Carolina underground storage tank release site was selected for study The site was insüumented with more than 50 observation wells monitored for several years to allow quantitative characterization of the downgradient mass transport of the dissolved compounds Companion laboratory and modeling studies were conducted to facilitate interpretation of the field data Three dimensional field monitoring of the dissolved gasoline plume showed rapid decay of toluene and ethylbenzene during downgradient transport with slower decay of xylenes, benzene, and MTBE under mixed aerobic-denitrifying conditions Background dissolved oxygen concentrations range from to m a , and nitrate concentrations range from to 17 m g L as Nitrogen (N) because of extensive fertilization of fields surrounding the spill Sampling results indicate that the plume is not growing and has reached a pseudo-steady-state Field-scale decay rates were determined by estimating the mass flux of contaminants across four plume cross-sections First-order decay rates for all compounds were highest near the source and lower farther downgradient Effective fmt-order decay rates vaned from O to 0.0010 d" for MTBE; 0.0006 to 0.0014 d-' for benzene; 0.0005 to 0.0063 d-' for toluene; 0.0008 to 0.0058 d-' for ethylbenzene; 0.0012 to 0.0035 6' form-, p-xylene; and 0.0007 to 0.0017 d-' for o-xylene In a companion study, laboratory microcosm studies confirmed MTBE biodegradation under aerobic conditions; however, the extent of biodegradation was limited Copyright American Petroleum Institute Provided by IHS under license with API No reproduction or networking permitted without license from IHS Not for Resale S T D A P I / P E T R O P U B L 4h54-ENGL 9 0732270 05712bB 385 R BIOPLUME II and a 3-Danalytical model were evaluated for thek,abiíity to simulate the transport and biodegradation of MTBE and BTEX at the site Neither model could accurately `,,-`-`,,`,,`,`,,` - simulate contaminant concentrations throughout the length of the plume Copyright American Petroleum Institute Provided by IHS under license with API No reproduction or networking permitted without license from IHS Not for Resale ~ ~ ~~ ~~~ S T D - A P I / P E T R O PUBL h - E N G L L797 0732270 057LZb7 L L TABLE OF CONTENTS m ChaDter EXECUTIVE SUMMARY e5-1 INTRODUCTION 1-1 1.1 INTRODUCTION 1-1 1.2 BTEX BIODEGRADATION 1-1 1.3 MTBE BIODEGRADATION 1-4 1.4 RESEARCH OBJECIIVES 1-5 SITE DESCRIPTION 2-1 2.1 BACKGROUND 2-1 2.2 GEOLOGIC SETI?NG 2-4 2.3 SlTE HYDROGEOLOGY 2-4 ANALYTICAL AND FIELD METHODS 3-1 3.1 MONITORING WELL CONSTRUCTION 3-1 3.2 MONITORING WELL LOCATIONS 3-1 3.3 GROUNDWATER SAMPLING 3-3 3.4 LABORATORY ANALYTICAL METHODS 3-5 `,,-`-`,,`,,`,`,,` - SPATIAL DISTRIBUTION OF BTEX AND INDICATOR PARAMETERS 4-1 4.1 GEOCHEMICAL INDICATOR PARAMETERS 4.2 VARIATION OF BTEX WITH TIME 4-2 4.3 HORIZONTAL AND VERTICAL DISTRIBUTION OF CHLOF2DE OXYGEN "TRATE AND INORGANIC CARBON 4-4 4.4 HORIZONTAL AND VERTICAL DISTRIBUTION OF MTBE AND BTEX 4-11 4.5 DISCUSSION OF FELD MONITORING RESULTS 4-19 MASS FLUX ESTIMATION OF CONTAMINANT DEGRADATION RATES 5-1 5.1 MASS FLUX ESTIMATION 5-1 5.2 VARIATION IN MTBE AND BTEX MASS FLUX WITH TIME 5-4 Copyright American Petroleum Institute Provided by IHS under license with API No reproduction or networking permitted without license from IHS Not for Resale m ~~ ~~~ S T D A P E / P E T R O PUBL b - E N G L 1977 2 0 7 T33 5.3 VARIATION IN MTBE AND BTEX MASS FLUX WITH DISTANCE 5-8 5.4 DISCUSSION OF MASS FLUX RESULTS MODELING STUDIES 6.1 MODEL DESCRIPTIONS 5-15 6-1 6.2 SIMULATION OFMTBE TRANSPORT AND BIODEGRADATION .6-3 `,,-`-`,,`,,`,`,,` - 6.2.1 BIOPLUME II Results 6.2.2 3-D Analytical Solution 6.3.1 BIOPLUME II Results For Total BTEX 6-3 Results 6-8 6.2.3 Comparison of MTBE Simulation Results Using Bioplume II And The 3-DAnalytical Solution 6-11 6.3 SIMULATION OF BTEX TRANSPORT AND BIODEGRADATION .6-11 6.3.2 6-11 3-DAnalytical Solution Results For Total BTEX And Individual Compounds 14 6.4 MODEL COMPARISON 6-16 SUMMARY AND CONCLUSIONS REFERENCES 7-1 R- APPENDICES A HYDROGEOLOGIC DATA A-1 B FIELD SAMPLING DATA B-1 C MODELING WITH BIOPLUME II C-1 D MODELING WITH THE ANALYTICAL SOLUTION D- Copyright American Petroleum Institute Provided by IHS under license with API No reproduction or networking permitted without license from IHS Not for Resale _ _ - - - _~ ~~ ~~ ~~ S T D - A P I I P E T R O P U B L b - E N G L 9 S 2 0 7 ỵ T II LIST OF FIGURES Fipure ES-1 Schematic Representation of Part of the Site’s Monitoring Well 2-1 Site Map Showing Major Features, Monitoring Well Locations, and Approximate Horizontal Plume Centerline (A-A’) ES-3 2-2 2-2 Cross Section along Line A-A’ from Figure 2-1 Showing Screened intervals and Approximate Vertical Plume Centerline (B-B’) .2-3 2-3 MTBE Breakthrough at the Most Downgradient Wells for Various Groundwater Velocities 2-7 3-1 Monitoring Well Location Map 3-2 4-1 Variation in Totai BTEX Concentration with Time and Water Table Elevation in (A) MW-3s and in (B) MW-1 lm and MW-12m (Julian Day O = 1/1/92) 4-3 Variation in MTBE and BTEX Components with Time in MW-17m (Julian Day O = 1/1/92) 4-5 4-2 4-3 April 1,1995, Chloride Concentration Distribution (mg/L): Plan and Profile Views 4-6 4-4 April 1,1995, Dissolved Oxygen Concentration Distribution (mgL): Plan and Profile Views ~7 4-5 April 1,1995, Nitrate Concentration Distribution (mg/L): Plan and Profile Views 4-8 4-6 April 1,1995, Carbon Dioxide Concentration Distribution ( m a ) : Plan and Profile Views 4-9 4-7 April 1,1995, MTBE Concentration Distribution (pg/L): Plan and Profile Views 4-12 4-8 April 1,1995, Benzene Concentration Distribution (& I ): Plan and Profile Views 4-13 4-9 April 1,1995, Toluene Concentration Distribution (pa): Pian and Profile Views 4-14 `,,-`-`,,`,,`,`,,` - Copyright American Petroleum Institute Provided by IHS under license with API No reproduction or networking permitted without license from IHS Not for Resale ~ ~~ S T D A P I / P E T R O P U S L 4b.54-ENGL `,,-`-`,,`,,`,`,,` - B D-15 Copyright American Petroleum Institute Provided by IHS under license with API No reproduction or networking permitted without license from IHS Not for Resale ~ ~ 1997 H 0732290 0573473 504 STD.API/PETRO PUBL 4b54-ENGL 2997 `,,-`-`,,`,,`,`,,` - D-16 Copyright American Petroleum Institute Provided by IHS under license with API No reproduction or networking permitted without license from IHS Not for Resale 2 0 7 4 11111 ~ S T D - A P I / P E T R O P U B L b - E N G L 1797 D-17 Copyright American Petroleum Institute Provided by IHS under license with API No reproduction or networking permitted without license from IHS 0732270 0571475 `,,-`-`,,`,,`,`,,` - Not for Resale e ~~ S T D A P I / P E T R O P U B L LIbSY-ENGL 7 @M0732210 7 b 213 `,,-`-`,,`,,`,`,,` - e jt’ D-18 Copyright American Petroleum Institute Provided by IHS under license with API No reproduction or networking permitted without license from IHS Not for Resale PUBL 4b54-ENGL L777 f l 2 0573477 T `,,-`-`,,`,,`,`,,` - STD.API/PETRO D-19 Copyright American Petroleum Institute Provided by IHS under license with API No reproduction or networking permitted without license from IHS Not for Resale `,,-`-`,,`,,`,`,,` - D-20 Copyright American Petroleum Institute Provided by IHS under license with API No reproduction or networking permitted without license from IHS Not for Resale S T D A P I / P E T R O P U B L 4654-ENGL 7 I 2 0573477 T 2 H o `,,-`-`,,`,,`,`,,` - %d D-2 Copyright American Petroleum Institute Provided by IHS under license with API No reproduction or networking permitted without license from IHS Not for Resale `,,-`-`,,`,,`,`,,` - D-22 Copyright American Petroleum Institute Provided by IHS under license with API No reproduction or networking permitted without license from IHS Not for Resale S T D A P I / P E T R O P U B L L ( b - E N G t 1947 I I D-23 `,,-`-`,,`,,`,`,,` - Copyright American Petroleum Institute Provided by IHS under license with API No reproduction or networking permitted without license from IHS Not for Resale 2 U57L48L LBO U ~~ ~ STD.API/PETRO P U B L 4b54-ENGL 9 `,,-`-`,,`,,`,`,,` - u D-24 Copyright American Petroleum Institute Provided by IHS under license with API No reproduction or networking permitted without license from IHS Not for Resale 2 0571482 517 ~ ~ ~~ ~ ~ ~ S T D A P I / P E T R O P U B L b - E N G L i797 m 2 U57L4P13 Al `,,-`-`,,`,,`,`,,` - D-25 Copyright American Petroleum Institute Provided by IHS under license with API No reproduction or networking permitted without license from IHS Not for Resale `,,-`-`,,`,,`,`,,` - D-26 Copyright American Petroleum Institute Provided by IHS under license with API No reproduction or networking permitted without license from IHS Not for Resale ~ S T D - A P I I P E T R O PUBL 4b54-ENGL 1797 ~ 2 057LL/85 2 b a - A c r! O P t L7 ei' `,,-`-`,,`,,`,`,,` - Copyright American Petroleum Institute Provided by IHS under license with API No reproduction or networking permitted without license from IHS Not for Resale c $ O O O `,,-`-`,,`,,`,`,,` - D-28 Copyright American Petroleum Institute Provided by IHS under license with API No reproduction or networking permitted without license from IHS Not for Resale 1220 L Street, Northwest Washington, D.C.20005 202-682-8oOo hỵtphww.api.org Order No.146540 Copyright American Petroleum Institute Provided by IHS under license with API No reproduction or networking permitted without license from IHS Not for Resale `,,-`-`,,`,,`,`,,` - Amencan Petroleum Institute