1、 STD.AP/PETRO PUBL 4b58-ENGL 1997 0732290 DbOib53 914 0 American L- Petroleum Ins titute METHODS FOR MEASURING INDICATORS OF INTRINSIC B IOREMEDIATION: GUIDANCE MANUAL Health and Environmental Sciences Department Publication Number 4658 November 1997 STD.API/PETRO PUBL LibSB-ENGL L777 0732270 Ub03b5
2、Li 850 = American Petroleum Institute American Petroleum Institute Environmental, Health, and Safety Mission and Guiding Principles MISSION The members of the American Petroleum Institute are dedicated to continuous eforts to improve the compatibility of our operations with the environment while eco
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10、materials, petroleum products and wastes. ! Methods for Measuring Indicators of Intrinsic Bioremediation: Guidance Manual Health and Environmental Sciences Department API PUBLICATION NUMBER 4658 PREPARED UNDER CONTRACT BY: CH2M-HILL ST. LOUIS, MO 63102 10 SOUTH BROADWAY NOVEMBER 1997 American Petrol
11、eum Institute STD.API/PETRO PUBL 4b58-ENGL 1777 = 0732270 Ob03b5b b23 FOREWORD API PUBLICATIONS NECESSARILY ADDRESS PROBLEMS OF A GENERAL NATURE. WITH RESPECT TO PARTICULAR CIRCUMSTANCES, LOCAL, STATE, AND FBDERAL LAWS AND REGULATIONS SHOULD BE REVIEWED. API IS NOT UNDERTAKING TO MEET THE DUTIES OF
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14、ts reserved. 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 permissionfrom the publishel: Contact the publisher, API Publishing Services, i220 L Street, NW, Washin
15、gton, D.C. 2OS. Copyright O 1997 American Petroleum Institute iii STD.API/PETRO PUBL 4b5-ENGL L997 = 0732270 Ob03b57 5bT 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 CONTACTS Bruce
16、Bauman, Health and Environmental Sciences Department Roger Claff, Health and Environmental Sciences Department and 2) in many cases, the cost of conventional groundwater remediation approaches far outweighs the benefits in terms of protection of human health and the environment. / Various technical
17、articles and protocols offer guidance on the groundwater parameters and properties that should be measured to characterize intrinsic bioremediation of petroleum hydrocarbons. These include dissolved oxygen (DO), nitrate, sulfate, ferrous iron, methane, carbon dioxide, alkalinity, oxidation/reduction
18、 potential (OW), pH, conductance, and temperature. These parameters are being measured at an increasing number of petroleum hydrocarbon contaminated sites. However, there is generally a lack of specific guidance on appropriate sampling and analytical procedures to ensure that these intrinsic bioreme
19、diation measurements generate quality data. This lack of guidance is 1-1 STD-APIIPETRO PUBL LibSB-ENGL 1997 0732270 Ob03bb4 7TT W of concern because the extent to which intrinsic bioremediation is ultimately embraced will depend, to a large degree, on the valid characterization of site conditions. T
20、herefore, API initiated a study to evaluate and compare the methods used to characterize intrinsic bioremediation, with the ultimate objective of providing this guidance document on sampling methods and analytical procedures. The laboratory and field studies conducted to support the guidance are des
21、cribed in a companion document (CH2M HILL, 1997). OBJECTIVES AND USE OF THIS MANUAL This guidance manual is intended to be a resource for practitioners of intrinsic bioremediation in the following areas: Scoine field investigations: Allowing selection of sampling and analytical methods that meet pro
22、ject-specific and site-specific needs. Performing field investig;ations: Allowing field staff implementing field investigations to understand how sampling and field analytical techniques can affect the data collected. Provides procedures that will improve the representative quality of the collected
23、data. Evaluation of field investigation data: Allowing those responsible for evaluation of geochemical indicators of intrinsic bioremediation to consider potential biases introduced into data through the sampling and analytical techniques employed in the site investigation. This document is not inte
24、nded to serve as guidance on the broader issues of how to assess intrinsic bioremediation and what parameters to measure. These issues are addressed in other documents, including the Air Forces Technical Protocol for Implementing Intrinsic Remediation with Long-Term Monitoring for Natural Attenuatio
25、n of Fuel contamination Dissolved in Groundwater (Weidemeier et al., 1995), an upcoming ASTM guide for remediation by natural attenuation at petroleum release sites (in preparation), Mobil Oil Corporations A Practical Approach to Evaluating Intrinsic 1-2 Bioremediation of Petroleum Hydvocarbons in G
26、round Water (Mobil Oil Corporation, 1995), and Chevrons Protocol for Monitoring Intrinsic Bioremediation in Groundwater (Buscheck and OReilly, 1995), among others. Site data on geochemical indicators of intrinsic bioremediation can be used in a variety of ways, ranging from very qualitative uses (e.
27、g., comparison to background data) to very quantitative uses (e.g., input parameters to numerical fate and transport models). The ultimate data use dictates the data quality objectives. The data quality that can be expected from the various sampling and analytical methods and impacts on data use, ar
28、e discussed in this report. This report should not be interpreted as providing ! I ! endorsement of any particular data use. This guidance document focuses on collection of representative intrinsic bioremediation data at petroleum hydrocarbon sites. However, the observations and findings presented h
29、ere will generally be applicable to any site where biodegradable organic constituents occur. REPORT ORGANIZATION This report is organized in four sections: 1. Introduction to report purpose and organization. 2. Overview of sampling and method selection. Information is presented on how sampling and a
30、nalytical methodology can affect intrinsic bioremediation data. The general factors that should be considered in selecting sampling and analytical methods are reviewed. 3. Discussion of sampling methodology. Four different groundwater sampling methods are described. The manner in which the sampling
31、method may affect data quality is discussed, advantages and disadvantages of the methods are presented, and 1-3 recommendations to improve the representative quality of geochemical data collected using the method are offered. 4. Comparison of measurement methods. The merits of using field methods ve
32、rsus commercial laboratory services are evaluated. Methods for determination of individual geochemical indicators are presented. For each of these parameters, the purpose of measuring the geochemical parameter is discussed, available test methods are summarized, and important considerations in test
33、method selection and use are presented. i 1-4 I i Section 2 SAMPLING AND ANALYTICAL METHOD SELECTION OVERVIEW This section presents an overview of the key considerations in sampling and analytical . methodology. Information is presented on how sampling and analytical methodology can alter data on ge
34、ochemical indicators of intrinsic remediation. The general factors that should be considered in selecting sampling and analytical methods are reviewed. ! ! j WHY BE CONCERNED WITH SAMPLING AND ANALYTICAL METHODOLOGY? The characterization of key geochemical parameters of groundwater is a tool that ha
35、s emerged in recent years for evaluating intrinsic bioremediation. Microbial metabolism of petroleum hydrocarbons has predictable geochemical consequences (Wilson et al., 1994). For example, respiration of hydrocarbons may result in the loss of oxygen, nitrate, and sulfate, and the conversion of iro
36、n from the ferric to ferrous oxidation state. Petroleum hydrocarbons may also be biodegraded by an anaerobic process that results in the production of methane (i.e., methanogenesis). Measuring the trends in the distribution and concentration of these and other parameters can help to qualitatively es
37、tablish hydrocarbon biodegradation activity. Data on the spatial distribution of these parameters, together with hydrogeologic and stoichiometric data, are also sometimes used to support the quantitative estimation of contaminant biodegradation rates and the prediction of plume migration. I Why be c
38、oncerned with sampling and analytical methodology? The uses of geochemical data previously described will be valid only to the extent that measurements of these parameters are representative of geochemical conditions in the groundwater system sampled. Sampling and analytical methodology can signific
39、antly affect measurements of key geochemical indicators of intrinsic bioremediation, as described below. I STD=AQI/PETRO PUBL qbSB-ENGL I777 9 0732270 Ob03bbB 345 Geochemical Considerations To understand how sampling and analytical methods may impact results, one must first have a basic understandin
40、g of the geochemistry of the groundwater being sampled, and recognize that the geochemical condition of groundwater from biologically active zones is typically not stable during and after extraction from the subsurface. In recent years, it has become widely recognized that microorganisms can have pr
41、ofound effects on groundwater quality. This is particularly true where large masses of biodegradable organic compounds, such as petroleum hydrocarbons, are present in the vadose and groundwater zones. Hydrocarbon biodegradation involves microbiologically mediated oxidation coupled with reduction of
42、an electron acceptor through the biological process of respiration. The reduction of highly oxidized electron acceptors (e.g., DO) results in an overall decrease in the oxidizing potential of the groundwater. As species with the highest oxidizing potential are exhausted, the oxidizing potential of t
43、he groundwater system is progressively reduced, and the next most highly oxidized electron acceptor is used. Thus, a general sequence of electron acceptor utilization and lowering of the oxidizing potential of the groundwater is as follows: 1. Consumption of DO through aerobic respiration; 2. Nitrat
44、e reduction; 3. Reduction of ferric iron and corresponding production of ferrous iron; 4. Sulfate reduction; and 5. Methanogenesis, in which carbon dioxide is used as an electron acceptor and produces methane, and/or acetate is cleaved to carbon dioxide and methane. The above is a generalized and si
45、mplistic presentation of the progressive lowering of the oxidizing potential of a groundwater system through biodegradation of petroleum hydrocarbons. More complete descriptions of this process may be found in a variety of technical references (e.g., Wiedemeier et aZ., 1995; Atlas, 1984; Chapelle, 1
46、993). 2-2 STD.API/PETRO PUBL 4b5-ENGL 1777 I0732270 Oh03bb7 281 Water in equilibrium with the atmosphere will contain approximately 8 mg/L DO. This is the upper bound of oxidizing conditions within natural groundwater systems. As described earlier, biodegradation of petroleum hydrocarbons results in
47、 the consumption of this DO. At many petroleum hydrocarbon sites, the oxidizing potential of the groundwater is lowered to the extent that sulfate is reduced and ferrous iron and methane are produced (Admire et al., 1995; Borden et al., 1995). When the oxidizing potential has been reduced to this po
48、int, the groundwater is in considerable nonequilibrium with the atmosphere. When groundwater from subsurface zones of low oxidizing potential is brought to the surface and exposed to the atmosphere, fairly rapid changes in the oxidizing potential and concentrations of certain geochemical parameters
49、can occur as the water begins to equilibrate with the atmosphere (See Figure 2-1). A common example of this phenomenon is the formation of rust colored solids in water samples containing nonaqueous phase petroleum hydrocarbons. This is a visible manifestation of the transfer of oxygen from the atmosphere into the aqueous phase, subsequent oxidation of soluble ferrous iron to ferric iron, and the ultimate precipitation of the relatively 1 , insoluble ferric oxyhydroxide. 2-3 STD-APIIPETRO PUBL YbSB-ENGL 1997 0732290 Ub03b70 TT3 I
