1、 American Petroleum Institut e Compilation of Field Analytical Methods for Assessing Petroleum Product Releases Health and Environmental Sciences Department Publication Number 4635 December 1996 One of the most significant long-term trends affecting the future vitality of the petroleum industry is t
2、he publics concerns about the environment, heath and safety. Recognizing this trend, API member companies have developed a positive, forward-looking strategy called STEP: Strategies for Todays Environmental Partnership. This initiative aims to build understanding and credibility with stakeholders by
3、 continually improving our industrys environmental, health and safety performance; documenting performance; and communicating with the public. API ENVIRONMENTAL MISSION AND GUIDING ENVIRONMENTAL PRINCIPLES The members of the American Petroleum Institute are dedicated to continuous efforts to improve
4、 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 en
5、vironmentally 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 the following principles using sound science to prioritize risks and to implement cost-effective management prac
6、tices: 9 To recognize and to respond to community concerns about our raw materials, products and operations. 4 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. 4 To
7、 make safety, health and environmental considerations a priority in our planning, and our development of new products and processes. 4 To advise promptiy, appropriate officials, employees, customers and the public of information on significant industry-related safety, heaith and environmental hazard
8、s, and to recommend protective measures. 4 To counsel customers, transporters and others in the safe use, transportation and disposal of our raw materials, products and waste materials. 4 To economically develop and produce natural resources and to conserve those resources by using energy efficientl
9、y. 4 To extend knowledge by conducting or supporting research on the safety, health and environmental effects of our raw materials, products, processes and waste materials. 4 To commit to reduce overall emission and waste generation. 4 To work with others to resolve problems created by handling and
10、disposal of hazardous substances from our operations. + To participate with government and others in creating responsible laws, regulations and standards to safeguard the community, workplace and environment. 4 To promote these principies and practices by sharing experiences and offering assistance
11、to others who produce, handle, use, transport or dispose of similar raw materials, petroleum products and wastes. STD.API/PETRO PUBL 4b35-ENGL L99b m 0732290 05b2915 40b m Compilation of Field Analytical Methods for Assessing Petroleum Product Releases Health and Environmental Sciences Department AP
12、I PUBLICATION NUMBER 4635 PREPARED UNDER CONTRACT BY: IT CORPORATION CINCINNATI, OHIO 45246 LAND TECH REMEDIAL, INC. MONROE, CONNECTICUT 06468 TARGET/TEG COLUMBIA, MARYLAND 21 045 DECEMBER 1996 American Petroleum Institute STD.API/PETRO PUBL Lib35-ENGL 199b m 0732290 O5b291b 342 m FOREWORD API PUBLI
13、CATIONS 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, MANUFAC- TURERS, OR SUPPLIERS TO WARN AND PROPERLY TRAIN AND EQUIP THEIR EMP
14、LOYEES, AND OTHERS EXPOSED, CONCERNING HEALTH AND SAFETY RISKS AND PRECAUTIONS, NOR UNDERTAKING THEIR OBLIGATIONS UNDER 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 MANU- FACTURE, SALE, OR USE O
15、F ANY METHOD, APPARATUS, OR PRODUCT COV- ERED BY LETTERS PATENT. NEITHER SHOULD ANYTHING CONTAINED IN ITY FOR INFRINGEMENT OF LETERS PATENT. THE PUBLICATION BE CONSTRUED AS INSURING ANYONE AGAINST LIABIL- Copyright O 1996 American Petroleum Institute iii STD-API/PETRO PUBL Lib35-ENGL L99b m 0732290
16、05b2917 289 m 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 Roger Claff, Health and Environmental Sciences Department Bruce Bauman, Health and Environmental Sciences Departme
17、nt MEMBERS OF THE FIELD ANALYTICAL METHODS PROJECT TEAM Dominic Deangelis, Project Team Chairman, Mobil Oil Corporation Albert O. Learned, Marathon Oil Company A.E. Liguori, Exxon Research and Engineering Company Karl Loos, Shell Development Company Adolfo E. Silva, Petro-Canada, Inc. iv STD.API/PET
18、RO PUBL 4b35-ENGL L77b m 0732290 O5b29LB 115 m ABSTRACT A variety of improved field-based methods are available to perform on-site analyses of organic compounds in soil and groundwater samples. The appropriate use of these field analytical methods can increase spatial site information in less time a
19、nd with fewer assessment phases than conventional sampling methodologies using offsite laboratories. This report presents a compilation of the most widely used field analytical methods, including total organic vapor analyzers, field gas chromatograph, immunoassay, infrared analyzers, and dissolved o
20、xygedoxidation-reduction potential electrodes. Practical applications and limitations of each method are discussed and an objective-oriented Data Quality Classification scheme is presented to assist in selecting the appropriate method for the task. There is a chapter surveying other field analytical
21、 techniques not as widely used but showing promise for future application. This publication is the first of two documents, designed to fill the gaps that now appear to exist in the application of certain field technologies for the analysis of petroleum hydrocarbon contamination. The second report wi
22、ll address technology selection, QNQC protocols, and recommendations for training and recordkeeping. STD.API/PETRO PUBL Lib35-ENGL L77b 0732290 05b2719 051 M TABLE OF CONTENTS Section PaJg EXECUTIVESUMMARY . e5-1 1 . INTRODUCTION 1-1 BACKGROUND 1-1 PURPOSE AND SCOPE 1-3 2 . DATA QUALITI CLASSIFICATI
23、ONS . 2-1 DATA QUALITY LEVEL IA 2-3 DATA QUALITY LEVEL 1B 2-3 DATA QUALITY LEVEL 2 . 2-4 DATA QUALITY LEVEL 3 . 2-4 DATA QUALITY LEVEL 4 . 2-4 3 . TOTAL ORGANIC VAPOR DETECTORS AND HEADSPACE ANALYSIS 3-1 SUMMARY . 3-1 METHOD OVERVIEW . 3-2 Applications and Advantages 3-2 INTERFERENCES AND LIMITATION
24、S 3-2 OPERATING PRINCIPLES/INSTRUMENTATION . 3-5 Flame Ionization Detectors . 3-5 Photoionization Detectors 3-6 METHOD REQUIREMENTS . 3-8 Initial Setup 3-8 Sampling and Analysis Procedures 3-9 3-10 4 . FIELD GAS CHROMATOGRAPHS . 4-1 SUMMARY . 4-1 METHOD OVERVIEW . 4-1 Applications and Advantages 4-1
25、 INTERFERENCES AND LIMITATIONS 4-2 OPERATING PRINCIPLES/INSTRUMENTATION . 4-3 Detectors 4-4 Field Gas Chromatographs . 4-4 METHOD REQUIREMENTS . 4-5 QUALITY ASSURANCWQUALITY CONTROL REQUIREMENT . Comparative Sample Preparation and Analysis Procedures . 4-5 STD.API/PETRO PUBL Lib35-ENGL L79b m 073229
26、13 05b2720 873 m TABLE OF CONTENTS (CONTINUED) . Section therefore, use of the compilation document in combination with the manufacturers literature will provide the best basis for an overall evaluation of the effective use of a particular field analytical method. A brief summary of each method is p
27、resented which (1) describes the method; (2) identifies the appropriate application and limitations for evaluating hydrocarbon contaminantdconstituents of concern; and (3) specifies quality control checks that should be included in the field analysis quality assurance program. A general scheme is pr
28、esented in the compilation document for field analytical methods of different data quality. The quality of the data generated by a particular method is referred to as the data quality level (DQL). DQLs are based on data quality classifications for site investigations that were developed by the New J
29、ersey Department of Environmental Protection and were modified for use in this compilation document based on a review of method operation and reported use. ES-2 STD.API/PETRO PUBL Lib35-ENGL 177b 0732270 05b2725 355 TOTAL ORGANIC VAPOR (TOV) DETECTORS TOV detectors and headspace analysis are discuss
30、ed in Section 3. TOV headspace analysis is widely used to provide relatively low-cost screening of soil and groundwater for volatile hydrocarbons. The primary applications for which this method is best suited include: . Qualitative “hot spot“ or source area screening of volatile hydrocarbons in soil
31、; Selecting soil boring, soil vapor monitoring, and soil vapor extraction locations; and Identifying potential vapor pathways and infiltration in underground structures. TOV headspace analysis is less suited for screening of groundwater and less volatile contaminants found in heavier fuels such as d
32、iesel fuel and weathered gasoline. The total volatile organic concentrations measured are indicative of the total fraction of the vapor entering the detection instrument. The TOV concentrations are therefore general, qualitative measurements and TOV instruments are not suitable for analysis of speci
33、fic constituents or samples containing low (e.g., lo0 ppm), and open air environments with high background concentrations. Samples with high concentrations may need to be diluted and reanalyzed in order to bring concentrations into the calibration range of the instrument and to discriminate the indi
34、vidual peaks on a chromatogram. If many peaks are present, the separation of peaks may not be adequate to resolve specific constituents. In this case, integration of the total chromatogram can be used to determine total volatiles or contaminant indicators, depending on whether a headspace sample was
35、 taken (for volatiles only) or a solvent extraction was performed (for contaminant indicators). Field Gcs can discriminate and quantify specific constituents and generate a high level of data. Often, the regulatory agency overseeing an investigation requires the analysis and reporting of individual
36、constituents of concern to determine the potential risk of exposure. This is especially the case for benzene or BTEX constituents. By resolving specific constituents, the location of the source areas and delineation of the magnitude and extent of contamination in soil and groundwater can be evaluate
37、d. The approximate cost of analysis ranges from $50 to $70 per sample. Analytical time per sample is 10 to 40 minutes. IMMUNOASSAYS Section 5 discusses the application of Immunoassay test kits for on-site measurement of petroleum product releases. immunoassay field tests measure a target constituent
38、 or analyte using antibody- antigen reactions where an antibody is developed to have a high degree of selectivity and sensitivity to that target constituent. Immunoassay testing has been successfully used in the medical industry for years, and is currently being used as a field analytical method for
39、 hydrocarbons, pesticides, and PCBs. Contaminants are extracted from soil samples using a solvent (e.g., methanol); water samples are analyzed directly. The extract or water is placed in a reaction vessel (e.g., test tube) that contains the antibodies. Reagents which behave as tracers (e.g., enzyme
40、conjugates) are added in a series of steps with appropriate incubation periods. The target analyte “competes“ with an enzyme conjugate for a limited number of antibody binding sites. A substrate solution is then added and reacts with the enzyme conjugate to produce a color. The intensity of the colo
41、r is inversely proportional to the contaminant concentration of the target analyte in the sample. The absenceipresence or relative concentration is made by comparing the color developed from the unknown sample with a reference standard, or measured directly on a small portable colorimeter. ES-5 STD.
42、API/PETRO PUBL qb35-ENGL L77b m 0732290 05b2928 Obll m Depending on the biochemical design, a particular test kit will measure a specific constituent (e.g., benzene), a set of constituents (e.g., BTEX), or a general assay range (total petroleum hydrocarbons). Depending on the manufacturer, immunoass
43、ay test kits are designed for either semiquantitative or quantitative analyses. For semiquantitative analyses, an action level is set and the assay will indicate if the sample concentrations are above or below that level. Alternatively, multiple action levels can be set to place the sample in a disc
44、rete range (e.g., above 100 ppm but below loo0 ppm). For quantitative analyses, multipoint calibration curves are used that are usually internal to the colorimetric detector. The selection of the most appropriate kit is related to (1) the design of the kit (Le., action level, concentration range, or
45、 specific concentration); (2) what parameter needs to be measured; and (3) the objective of the assessment. Immunoassay test kits can provide high quality data that can be used to meet a wide range of assessment objectives. The primary applications for which immunoassays are best suited include: Det
46、ection of a wide range of fuels; BTEXhenzene or Ti” in soil; and Source aredzone of contamination mapping in soil. Immunoassay test kits are least suited for BTEX or TPH analysis at low concentrations (e.g., 70“C); Detection of relatively higher hydrocarbon concentrations; and Source aredzone of con
47、tamination mapping in soil. Portable IR detectors are least suited for evaluating “fresh“ unweathered volatile gasoline and hydrocarbons in clay or organic-rich soil. Although the method is applicable to the measurement of light fuels, approximately half of any gasoline present may be lost during th
48、e extraction process. The extraction process itself is potentially a significant limitation for using this method. The solvent currently being used for extraction (fluorocarbon-1 13) will likely be phased out in the near future. Other solvents are being examined; however, there is no equivalent solv
49、ent for this method at this time, and continued use of this method will likely require that a new solvent be found. In addition, volatile constituents may be lost by evaporation during the extraction process. No simple method exists for directly comparing the portable IR results for different fuel types which have different volatile constituent compositions. The estimated cost of analysis ranges from $5 to $31 per sample and the estimated analytical time per sample varies from 5 to 20 minutes. DISSOLVED OXYGEN AND OXIDATION POTENTIAL DETECTORS Secti
