1、 STD.API/PETRO PUBL 4671-ENGL 1996 = 0732290 0610566 690 = American Petroleum Institute TECHNICAL BULLETIN Y ON OXYGEN RELEASING MATERIALS FOR IN SIRI GROUNDWATER REMEDIATION Q 7 HEALTH AND ENVIRONMENTAL SCIENCES DEPARTMENT JULY 1998 PUBLICATION NUMBER 4671 STD=API/PETRO PUBL 4b7L-ENGL 1998 0732290
2、ObL05b9 527 . American Petroleum 4 Institute American Petroleum Institute Environmental, Health, and Safety Mission and Guiding Principles MISSION The members of the American Petroleum institute are dedicated to continuous efforts to improve the compatibility of our operations with the envikonment w
3、hile 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 environmentally sound manner while protecting the health and
4、safety of our employees and the public. To meet these responsibilities. API members pledge to prioritize risks and to implement cos +effective management practices: . manage our businesses accordink to the following principles using sound science to PRINCIPLES o e To recognize and to respond to comm
5、unity concerns about our raw materiais, products and operations. To operate our plants and facilities, and to handle 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 eqvironmental considera
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7、el customers, transporters and others in the safe use, transportation and disposal of our raw materials, products and waste materiais. To economically develop and produce natural resources and to conserve those resources by using energy efficiently. To extend knowledge by conducting or supporting re
8、search on the safety, health and environmental effects of our raw materials, products, processes and waste materials. To commit to reduce overall emission and waste generation. To work with others to resolve problems created by handling and disposal of hazardous substances from our operations. To pa
9、rticipate with government and others in creating responsible laws, regulations and standards to safeguard the community, workplace and environment. To promote these principles and practices by sharing experiences and offering assistance to others who produce, handle, use, transport or dispose of sim
10、ilar raw materiais, petroleum products and wastes. Technical Bulletin on Oxygen Releasing Materials for In Sfu Groundwater Remediation Health and Environmental Sciences Department API PUBLICATION NUMBER 4671 PREPARED UNDER CONTRACT BY: J.D. ISTOK DEPARTMENT OF CIVIL ENGINEERING CORVALLIS, OR 97331 O
11、REGON STATE UNIVERSITY JULY 1998 American Petroleum Institute FOREWORD API PUBLICATIONS NECESSARILY ADDRESS PROBLEMS OF A GENERAL NATURE. WITH RESPECT TO PARTICULAR CIRCUMSTANCES, LOCAL, STATE, AND FEDERAL LAWS AND REGULATIONS SHOULD BE REWEWED. API IS NOT UNDERTAKING TO MEET THE DUTIES OF EMPLOYERS
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14、ved. No part of this work may be reproduced, stored in a retrieval system, or transmitted by any means. electronic. mechanical, photocopying, recording, or otherwise, without prior written permission from the publishex Contact the publishel; API Publishing Services, I220 L Street, N. W, Washington,
15、D.C. 20005. Copyright O 1998 American Petroleum institute iii Previous page is blank STDmAPIlPETRO PUBL 467L-ENGL I778 0732270 Ob30572 O31 = ACKNOWLEDGMENTS THE FOLLOWING PEOPLE ARE RECOGMZED FOR THEIR CONTRIBUTIONS OF TIME AND EXPERTISE DURING THIS STUDY AND IN THE PREPARATION OF THIS REPORT: API S
16、TAFF CONTACT Harley Hopkins, Health and Environmental Sciences Department MEMBERS OF THE SOIL AND GROUNDWATER TECHNICAL TASK FORCE Phil Bartholomae, BP Oil Company Brian Bean, Phillips Pipeline Company Vaughn Berkheiser, Amoco Corporation Ren Bernier, Texaco Corporation Tim Buscheck, Chevron Researc
17、h and Technology Company Victor Kremesec, Amoco Corporation A.E. Liguori, Exxon Research and Engineering Company Johnathan Miller, Shell Development Company Kirk O Reilly, Chevron Research and Technology Company R. Edward Payne, Mobil Business Resources Corporation Terry Walden, BP Oil Company API t
18、hanks Stephen S. Koenigsberg of Regenesis Bioremediation Products for many helpful comments during the preparation of this report. V Previous page is blank STD-APIIPETRO PUBL 4671-ENGL 1998 = 0732290 Ob30573 T58 m ABSTRACT Oxygen Releasing Materials (ORMs) are commercially available materials that a
19、re being used to treat petroleum hydrocarbon contaminated groundwater aquifers. ORMs release oxygen to groundwater, which stimulates the growth and activity of native microorganisms. The principle questions that must be answered when evaluating a proposed ORM installation are: 1. How much OW is requ
20、ired and how much will it cost?; 2. What method of ORM installation will distribute oxygen most effectively across the site?; and 3. What type of monitoring will be used to evaluate the effectiveness of the ORM installation in meeting site cleanup goals? This technical bulletin addresses these quest
21、ions using a step-by-step design approach intended for practitioners who are evaluating the use of Oms. The scientific basis for ORMs is discussed and the current state of knowledge of ORM-based technology is reviewed. A systematic approach is presented for evaluating the utility of ORM treatment fo
22、r a site and for use in designing ORM installations. Example design calculations are used to illustrate the principles discussed and an annotated bibliography of the technical literature is presented. STD.API/PETRO PUBL 4671-ENGL 1998 m 0732290 0630574 994 m TABLE OF CONTENTS Section 1. INTRODUCTION
23、-. 1-1 SCIE“IFIC BASIS FOR THE TECHNOLOGY 2- 1 BIOREMEDIATION OF PETROLEUM HYDROCARBONS. . 2- 1 OXYGEN REQUIREMENT FOR AEROBIC RESPIRATION 2-2 ROLE OF OXYGEN IN NATURAL ATTENUATION-. 2-4 ROLE OF OXYGEN IN ENHANCED BIOREMEDIATION 2-7 2. THE ROLE OF OXYGEN IN IN SITU NAnJRAL SOURCES OF OXYGEN. . 2-5 3
24、- OXYGEN RELEASING MATERIALS- . 3-1 WHAT OXYGEN RELEASING MATERIALS ?- . 3- 1 COMMON MODES OF ORM APPLICATION . 3- 1 MECHANISM OF OXYGEN FwxASE FROM ORM . 3-4 TIMING OF OXYGEN RELEASE 3-5 FACTORS AFFECTING OXYGEN TRANSPORT 3 -6 AND DISTRIBUTION 3-6 Advection Dispersion 3-6 3-8 Diffusion. Remdation-.
25、 3-8 Checal al-ld microbiologic Reactions.- . 3-9 . . . 4. DESIGN APPROACH 4- 1 ON-SITE TREATMENT OF CONTAMINANT PLUME 4- 1 . 4- 1 step 2 4-2 step I-.- step 3.- 4-2 step 4. 4-3 step 5 4-4 PREVENTION OF OFF-SITE PLUME MIGRATION 4-5 . . . step 1 4-6 4-6 step 3 4-6 . step 2 . . TABLE OF CONTENTS (conti
26、nued) Section pag;e_ MONITORING PROGRAM. . 4-7 COST ESTIMATES FOR om INSTALLATIONS 4-6 5. EXAMPLE DESIGN CALCULATIC“ 5- 1 EXAMPLE CALCULATION NO- 1 5-1 EXAMPLE CALCULATION NO- 2 . 5-2 EXAMPLE CAJ#CULATION NO- 3 5-3 EXAMPLE CALCULATION NO- 4 54 6. A“OTATED BIBLIOGWHY 6- 1 7. ADDn-IONAL REFERENCES-.-
27、7- 1 . Section 2-1. 3-1. 3-2. 5-1. Section 1-1. LIST OF FIGURES Parre “S teady-state” contaminant plume created by balance among several factors: contaminant release from source zone, groundwater flow and transport, and aerobic and anaerobic respiratio n. 2-5 Some ORM application methods: (a) ORM so
28、cks in wells, (b) ORM slurry injection in direct-push and augered boreholes, (c) powder in interceptor trench, and (d) “funnel and gate” with removable ORM socks or 3-2 Gb casettes.- . Effect of ratio of longitudinal to transverse dispersivity (aL/%) on length 3-7 and width of 02 Plume downgradient
29、of om source. . Schematic of contaminated site showing overall dimensions of petroleum hydrocarbon plume- 5- 1 . Section 1 INTRODUCTION The purpose of this technical manual is to provide an introduction to the use of oxygen releasing materials (Oms) as a method for providing supplementai oxygen to d
30、issolved petroleum hydrocarbon plumes to increase in situ bioremediation rates. OMS are a very new technology, having been commercially available for only the last five years. Nevertheless? ORMs are currently being used at many sites under a wide range of conditions and their use is increasing. Alth
31、ough only limited research data are currently available, the experience of practitioners and researchers with these compounds is growing rapidly. This manual summarizes the current state of understanding of this technology and provides guidance for site managers considering the use of ORMs. Section
32、2 provides a review of the scientific basis for ORM technology intended for those unfamiliar with the basic principles underlying intrinsic and enhanced bioremediation processes. Section 3 summarizes the current state of knowledge on ORMs including methods of application? mechanisms and timing of ox
33、ygen release, and factors affecting oxygen transport and distribution in contaminated aquifers. Section 4 presents an example design approach to assist practitioners in performing a feasibility assessment for the use of ORMs at a particular site, developing a set of alternate designs for ORM install
34、ations, and developing preliminary cost estimates. Section 5 presents a set of example design calculations that illustrate the design approach presented in Section 4. Section 6 contains an annotated bibliography of the technical literature, and Section 7 presents additional references cited in this
35、bulletin. Please note that the information contained in this report is not necessarily intended to supplant any existing practices and that API encourages further development of the ideas presented. In no way should the following information be considered standard practice. However, the information
36、contained herein should provide practical guidance. 1-1 - STD.API/PETRO PUBL 4671-ENGL 1998 0732290 Ob10578 53T Section 2 SCIENTIFIC BASIS FOR THE TECHNOLOGY THE ROLE OF OXYGEN IN IN SITU BIOREMEDIATION OF PETROLEUM HYDROCARBONS Bioremediation relies on the use of microorganisms to degrade petroleum
37、 hydrocarbons ultimately to carbon dioxide and water. Degradation occurs as a consequence of microbial growth and reproduction, which requires a source of organic carbon and nutrients (such as nitrogen, phosphorus, and sulfur). Organic carbon is present in the subsurface as naturally occurring organ
38、ic matter and as petroleum hydrocarbons and their breakdown products. Energy for microbial growth and hydrocarbon degradation is obtained through oxidation-reduction reactions, which the microorganisms facilitate using specific enzyme systems. In these reactions, electrons are transferred from an el
39、ectron donor (which is oxidized) to an electron acceptor (which is reduced). A wide variety of compounds may serve as electron donors. These include naturally occurring organic matter in aquifer sedments and the wide range of organic compounds in petroleum-based fuels and lubricants and their interm
40、ediate breakdown products. Substantially fewer compounds can serve as electron acceptors. The most energetically favorable electron acceptor is molecular oxygen (OJ and, if it is present, microorganisms will preferentially use O2 as the electron acceptor in a process called aerobic respiration. The
41、energy derived from this process is used for growth and petroleum hydrocarbon degradation. Once the supply of O, is depleted, rates of growth and degradation will decrease as organisms use less favorable electron acceptors such as NO3-, Fe3+, SO,Z-, or CO, in a variety of additional metabolic proces
42、ses. It is generally accepted that petroleum hydrocarbons are degradable under either aerobic or anaerobic conditions. However, under anaerobic conditions, contaminant degradation rates decrease 10 to more than 100 times compared to degradation rates under aerobic conditions. Thus, increasing dissol
43、ved 0, concentrations in contaminated, anaerobic groundwaters will create conditions favorable for aerobic respiration and therefore increase degradation rates. - STD*API/PETRO PUBL 4b7L-ENGL 1778 0732290 Ob30579 47b w OXYGEN REQUIREMENT FOR AEROBIC RESPIRATION To use an aerobic respiration pathway
44、to degrade organic contaminants requires a minimum quantity of O, which can be computed by representing the degradation process as a balanced chemical reaction. For example, the degradation of benzene (C total petroleum hydrocarbon-diesel (TPH-D), which represents the combined concentrations of the
45、Cl0 to Cl, hydrocarbons contained in diesel; biological oxygen demand (BOD), which directly measures 0, consumption by added “seed” microorganisms as they degrade soluble organic compounds in an oxygen-saturated groundwater sample; chemical oxygen demand (COD), which measures the amount of chemical
46、oxidizing agent consumed (expressed as equivalent 09 when it is added to a water sample; and total organic carbon (TOC), which measures the combined concentration of all organic carbon containing compounds by burning a sample to produce CO2. The presence of nonaqueous phase liquids (NAPLs) can compl
47、icate O2 demand calculations because reliable information on the O2 demand exerted by NAPLs cannot be readily determined. Determining the presence or absence of residual NAPL in the treatment area (Feenstra et aE., 1991) is important in determining O2 demand. NAPL, as either “free product” or residu
48、al liquid, may serve as a long-term source of dissolved hydrocarbons (Huntley and Beckett, 1997) and cause long-term oxygen demand. The goals of the remediation project may dictate how the O2 demand of the NAPL is addressed. If residual NAPL is present within the treatment zone of an ORM installatio
49、n and the goal is to degrade the available NAPL, it will be necessary to estimate an approximate O, demand by converting estimated NAPL volumes to mass and using a simple stoichiometry for NAPL mineralization based on composition (e.g., equation 1). If the objective is to reduce concentrations within a dissolved plume, the longevity and strength of any upgradient or adjacent NAPL source must be considered when determining the 0, requirements needed to reach the project remediation goal. It should be noted that naturally occurri
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