1、HEALTH AND ENVIRONMENTAL SCIENCES DEPARTMENT API PUBLICATION NUMBER 461 1 APRIL 1995 Interlaboratory Study of EPA Methods 1662,165444, and 1663 for the Determination of Diesel, Mineral and Crude Oils in Drilling Muds from Offshore Oil and Gas Industry Discharges American Petroleum Institute *P Struf
2、tgigrer for Todnyr Enmrmmrntal Parinmbtp I Stratepu for Todnyt Enfnmnrnental Parinenhip One of the most significant long-term trends affecting the future vitality of the petroleum industry is the publics concerns about the environment. Recognizing this trend, API member companies have developed a po
3、sitive, forward-looking strategy called STEP: Strategies for Todays Environmental Partnership. This program aims to address public concerns by improving our industrys environmental, health and safety performance; documenting performance improvements; and communicating them to the public. The foundat
4、ion of STEP is the API Environmental Mission and Guiding Environmental Principles. API ENVIRONMENTAL MISSION AND GUIDING ENVIRONMENTAL PRINCIPLES The members of the American Petroleum Institute are dedicated to continuous efforts to improve the compatibility of our operations with the environment wh
5、ile economically developing energy resources and supplying high quality products and services to consumers. The members recognize the importance of efficiently meeting societys needs and our responsibility to work with the public, the government, and others to develop and to use natural resources in
6、 an environmentally sound manner while protecting the health and safety of our employees and the public. To meet these responsibilities, API members pledge to manage our businesses according to these principles: To recognize and to respond to community concerns about our raw materials, products and
7、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 environmental considerations a priority in our planning, and our development
8、 of new products and processes. 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. To counsel customers, transporters and others in the safe use,
9、 transportation and disposal of our raw materials, products and waste materials. To economically develop and produce natural resources and to conserve those resources by using energy efficiently. To extend knowledge by conducting or supporting research on the safety, health and environmental effects
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11、nsible 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 similar raw materials, petroleum products and wastes. Int
12、erlaboratory Study of EPA Methods l662,1654A, and 1663 for the Determination of Diesel, Mineral and Crude Oils in Drilling Muds from Offshore Oil and Gas Industry Discharges Health and Environmental Sciences Department API PUBLICATION NUMBER 461 1 PREPARED BY: J.C. RAIA CONSULTING SERVICES 15402 PAR
13、K ESTATES LANE HOUSTON, TEXAS 77062 APRIL 1994 American Petroleum Institute - API PUBL*4bLL 95 = 0732290 0545378 07T = FOREWORD API PUBLICATIONS NECESSARILY ADDRESS PROBLEMS OF A GENERAL NATURE. WiTH RESPECT TO PARTICULAR CIRCUMSTANCES, LOCAL, STATE, AND FEDERAL LAWS AND REGULATIONS SHOULD BE REVIEW
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16、TRUED AS INSURING ANYONE AGAINST LIABIL- Copyright Q 1995 American Petroleum Institute i ACKNOWLEDGMENTS The following participants in this work are recognized for their contributions of time and expertise during the course of this study: API STAFF CONTACTS Alexis E. Steen, Health and Environmental
17、Sciences Department MEMBERS OF THE API TECHNOLOGY/DIESEL ANALYSIS TASK FORCE Dan Caudle, Conoco, Inc.a) Joseph C. Raia, Shell Development Thomas M. Randolph, Shell Offshore, Inc.) George H. Stanko, Shell Development Co. Michael T. Stephenson, Texaco, Inc. EPA STAFF AND EPA CONTRACT PERSONNEL Carrie
18、Buswell, DynCorp-Viar, Inc. Dale Rushneck, Interface, Inc. William A. Telliard, U.S. EPA API CONTRACT PERSONNEL Ronald Benjamin, Southern Petroleum Laboratories Marc Churan, M-l Drilling Fluids Co. Larry Scott, Core Laboratories Donald Weintritt, Weintritt Consulting Services Presently with: a) Soun
19、d Environmental Solutions, Houston, Texas b) J. C. Raia Consulting Services, Houston, Texas c) Randolph Consulting Services, Baton Rouge, Louisiana API PUBL*4bLL 95 = 0732290 0545380 728 ABSTRACT The effluent limitation guidelines being promulgated by the United States Environmental Protection Agenc
20、y (EPA) for the offshore oil and gas industry include the prohibition of the discharge of diesel oil in drilling muds and drill cuttings from offshore oil and gas platforms. Analytical test procedures have been developed by the EPA to allow monitoring for diesel oil in drilling fluids whenever neces
21、sary to ensure compliance with the regulation. In the development of these analytical techniques, the EPA and the Technology/Diesel Analysis Work Group of the American Petroleum Institute (API) conducted studies to evaluate various extraction and analytical measurement techniques for reliable determ
22、ination of diesel, mineral, and crude oils in drilling muds. The resulting Method 1662 (SoxhleDean-Stark Extraction and Gravimetry for Total Extractable Material in Drilling Mud), Method 1654A (HPLC/UV for Polynuclear Aromatic Hydrocarbons Content of Oil), and Method 1663 (GC/FID for differentiation
23、 of Diesel and Crude Oil). This report describes the methods and presents the results of the interlaboratory validation study of the methods. The large volume of raw data of this interlaboratory study, which includes calibration documentation, chromatograms, and EPA report forms are not included in
24、this report, but are available in retrievable record from the American Petroleum Institute, Washington, D.C. API PUBLJ4611 75 = 0732270 054.5381 664 TABLE OF CONTENTS Section Page Executive Summary ES-1 1 . Introduction 1 2 . Method Development and Discussion . 5 Drilling Mud Discharge Monitoring fo
25、r Oil and Toxicity . 5 Development of EPA Methods 1662. 1654A. and 1663 5 Differentiation of Diesel. Mineral. and Crude Oils . 7 3 . Interlaboratory Study of Methods 1662. 1654A. and 1663 9 Preparation of Drilling Mud Samples . 10 Initial Precision and Recovery QA Results 10 Results for Oil Spiked D
26、rilling Mud Samples . 12 Comments Offered by Study Participants . 17 4 . Conclusions and Recommendations . 19 Reference List . 21 Interlaboratory Test Design 9 Appendix A Preparation of Drilling Mud Samples Memorandum A-1 Sample Number and Laboratory Assignments A-7 . A-1 1 API Lab Selection Memoran
27、dum A-25 EPA Interlaboratory Study Request Memorandum A-29 EPA Analytical Services Request Form Appendix B Results Summary by DynCorp-Viar . B-1 Appendix C Narrative Comments by Lab Participants C-1 DynCorp-Viar Technical Issues Memorandum . C-17 API PUBL+4bLL 95 = 0732290 0545382 STO LIST OF FIGURE
28、S Figure Page 1 . Tiered Analysis by Methods 1662. 1654A. and 1663 . 7 2 . Recovery Results Method 1662 . 13 3 . PAH in Oil by Method 1654A . 15 4 . C,.C, in Oil by Method 1663 17 LIST OF TABLES Table Page 1 . Survey of Extractables in Drilling Muds. PAH in Mineral Oils. and C.C in Diesel Oils . 6 2
29、 . Interlaboratory Study Plan of Methods 1662. 1654A. and 1663 9 3 . Initial Precision and Recovery Results . 11 4 . Initial Precision and Recovery Results of Method 1662 11 5 . Initial Precision and Recovery Results of Method 1654A . 11 6 . Initial Precision and Recovery Results of Method 1663 11 7
30、 . Results for Spiked Drilling Mud Samples . 12 8 . Duplicate Results of Spiked Drilling Muds for Method 1662 . 13 9 . Duplicate Results of Spiked Drilling Muds for Method 1654A 15 10 . Duplicate Results of Spiked Drilling Muds for Method 1663 . 16 EXECUTIVE SUMMARY This report presents the results
31、of the interlaboratory validation study of EPA Methods 1662, 1654A, and 1663, which was conducted with participation from the U.S. Environmental Protection Agency (EPA) and the American Petroleum Institute (API). The report discusses the development work conducted by EPA and API which resulted in th
32、ese EPA methods, the interlaboratory validation study, and the method revisions required as a result of the validation study. Although this report shows that the methods developed were not perfect in their initial application, it is believed that the minor modifications to the methods as discussed l
33、ater in this report will result in the reliable determination of diesel oil in drilling mud. DEVELOPMENT OF EPA METHODS l662,1654A, AND 1663 EPA Methods 1662, 1654A, and 1663 are analytical test procedures, which have been issued by the EPA, to allow monitoring for diesel oil in drilling fluids when
34、ever necessary to ensure regulatory compliance to the EPA Effluent Limitation Guidelines for the Offshore Oil and Gas Industry. The regulation includes a ban on the discharge of diesel oil in drilling muds and drill cuttings. The methods were developed from work conducted by the EPA and the API Tech
35、nology/Diesel Analysis Work Group. Various extraction methods were evaluated, and analytical measurement techniques were tested for the measurement of diesel oil. Because of the potential presence of mineral oil and/or crude oil in drilling muds, the analysis requires diesel oil to be distinguished
36、from mineral oil and crude oil. Since no single analytical technique was found adequate, this method development effort has resulted in a tiered analysis approach for determining diesel oil in drilling muds using Methods 1662, 1654A, and 1663. With this approach, the analytical method required is gu
37、ided by the results and decision criteria at each tier in the procedure. Method 1662 for Total Extractable Material in Drilling Mud uses a SoxhleVDean-Stark (SDS) extractor to remove oil from the drilling mud for weighing and further analysis. Method 1654A for Polynuclear Aromatic Hydrocarbons (PAH)
38、 Content of Oil measures the PAH content of the extracted oil by high performance liquid chromatography with ES-1 ultraviolet detection (HPLCNV). If the PAH content is less than 0.35 weight percent, the oil is mineral oil. If the PAH content is equal to or greater than 0.35 weight percent, the oil i
39、s diesel oil or crude oil. Method 1663 for Differentiation of Diesel and Crude Oil uses gas chromatography with flame ionization detection (GC-FID) to measure the presence and distribution of hydrocarbons in the extracted oil. The presence of n-alkanes in the C,-C, range indicates the presence of di
40、esel or crude oil. The oil is crude oil if the C, Benjamin, 1992; Weintritt, 1989). This work has resulted in Method 1662 (SoxhleVDean-Stark Extraction and Gravimetry for Total Extractable Material in Drilling Mud), Method 1654A (HPLC/UV for Polynuclear Aromatic Hydrocarbons Content of Oil), and Met
41、hod 1663 (GC/FID for differentiation of Diesel and Crude Oil). 2 API PUBLx4hLL 95 = 0732270 0545388 TL9 W The member companies of the API Technology/Diesel Analysis Work Group and individuals working under the auspices of API and the EPA are to be commended for their perseverance in resolution of th
42、e technical challenges presented by what started out as a task seeking a simple means to reliably measure diesel oil. Although this report shows that the methods developed were not perfect in their initial application in this interlaboratory study, it is believed that the minor modifications to the
43、methods as discussed in this report will result in the reliable determination of diesel oil in drilling mud. This report will discuss these methods and the results of the interlaboratory validation study of the methods, which has been conducted by EPA and the API. 3 API PUBL*4bLl 95 0732290 0545389
44、955 W Section 2 METHOD DEVELOPMENT AND DISCUSSION DRILLING MUD DISCHARGE MONITORING FOR OIL AND TOXICITY The discharge of drilling muds from offshore platforms requires environmental compliance monitoring for oil and toxicity. Regulatory requirements are: no free oil can be present, as measured by t
45、he static sheen test (the visual sheen test is allowed in EPA Region Vi); a toxicity limitation in the suspended particulate phase of the mud to mysids as measured by the 96-h LC50 = 30,000 ppm; no diesel can be present as documented by the well inventory record, and verified by confirmatory analyti
46、cal testing when required. For confirmatory analysis of diesel, EPA Methods 1662, 1654A, and 1663 are used in a tiered analysis approach as discussed below. DEVELOPMENT OF EPA METHODS l662,1654A, AND 1663 In the development of Methods 1662, 1654A, and 1663, work conducted by EPA and the API Technolo
47、gy/Diesel Analysis Work Group was aimed at obtaining a good alternative extraction procedure to the retort, and a measurement finish that would allow diesel to be distinguished from mineral oil and crude oil. The extraction techniques evaluated in addition to the retort were: Soxhlet/Dean-Stark (SDS
48、); sonication with acetone/methylene chloride (1 :1 VN); and supercritical fluid extraction (SFE) with carbon dioxide. Laboratory prepared hot-rolled muds were spiked at two concentration levels of diesel. One level was at 0.2% and the other at 2.0%. Similarly, other mud samples were spiked with min
49、eral oil and with crude. Based on the recovery data from these extraction studies, SDS was selected as the best extraction procedure for diesel in drilling muds Raia, 19921. SFE gave lower recoveries for diesel than did the other techniques tested in this study. This may have been due in part to problems caused from the relatively high water contents of drilling muds. 5 API PUBL*4bLL 95 = 0732290 0545370 677 N Mean S.D. Mean + 2SD In the analytical measurement of diesel in drilling muds, definitive techniques are required that allow diesel to be distinguished
