1、API PUBL*4641 96 0732290 0557426 335 American % Petroleum Institute Summary of Produced Water Toxicity Identification Evaluation Research Health and Environmental Sciences Department Publication Number 4641 June 1996 API PUBL*4641 96 = 0732290 0557427 271 Envirairmental Parfiabtp One of the most sig
2、nificant 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 positive, forward-looking strategy called STEP: Strategies for Todays Environmental Partnership. This program
3、 aims to address public concerns by improving our industrys environmental, health and safety performance; documenting performance improvements; and communicating them to the public. The foundation of STEP is the API Environmental Mission and Guiding Environmental Principles. API ENVIRONMENTAL MISSIO
4、N 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 while economically developing energy resources and supplying high quality products and services to consumers.
5、 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 an environmentally sound manner while protecting the health and safety of our employees and the public. To
6、 meet these responsibilities, API members pledge to manage our businesses according to these principles: 9 To recognize and to respond to community concerns about our raw materials, products and operations. 9 To operate our plants and facilities, and to handle our raw materials and products in a man
7、ner that protects the environment, and the safety and health of our employees and the public. 9 To make safety, health and environmental considerations a priority in our planning, and our development of new products and processes. 9 To advise promptly, appropriate officials, employees, customers and
8、 the public of information on significant industry-related safety, health and environmental hazards, 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. 9 To economicall
9、y develop and produce natural resources and to conserve those resources by using energy efficiently. 9 To extend knowledge by conducting or supporting research on the safety, health and environmental effects of our raw materials, products, processes and waste materials. O To commit to reduce overall
10、 emission and waste generation. C. To work with others to resolve problems created by handling and 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 envir
11、onment. 9 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. API PUBL+4b4L b m 0732290 0557428 LO8 m Summary of Produced Water Toxicity Identificati
12、on Evaluation Research Health and Environmental Sciences Department API PUBLICATION NUMBER 4641 PREPARED UNDER CONTRACT BY: JOHN S. BROWN HELDER J. COSTA ACORN PARK CAMBRIDGE, MASSACHUSETTS 021 40 ARTHUR D. LITTLE, INC. THEODOR SAUER DUXBURY, MASSACHUSETTS 02332 BAITELLE OCEAN SCIENCES JANUARY 1996
13、American Petroleum Institute API PUBLr4641 96 0732290 0557429 044 FOREWORD API PUBLICATIONS NECESSARILY ADDRESS PROBLEMS OF A GENERAL NATURE. WITH RESPECT TO PARTICULAR CIRCUMSTANCES, LOCAL, STATE, AND FEDERAL LAWS AND REGULAmONS SHOULD BE REVIEWED. API IS NOT UNDERTAKING To MEET THE DUTIES OF EMPLO
14、YERS, MANUFAC- TURERS, OR SUPPLERS TO WARN AND PROPERLY TRAIN AND EQUIP THEIR EMPLOYEES, AND OTHERS EXPOSED, CONCERNING HEALTH AND SAFETY RISKS AND PRECAUTIONS, NOR UNDERTAKING THEIR OBLIGATIONS UNDER LOCAL, STATE, OR FEDERAL LAWS. NOTHING CONTAINED IN ANY MI PUBLICATION IS TO BE CONSTRUED AS GRANTI
15、NG ANY RIGHT, BY IMPLICATION OR OTHERWISE, FOR THE MANU- FACTURE, SALE, OR USE OF ANY METHOD, APPARATUS, OR PRODUCT COV- ERED BY LETERS PATENT. NEITHER SHOULD ANYTHING CONTAINED IN THE PUBLICATION BE CONSTRUED AS INSURING ANYONE AGAINST LIABIL- ITY FOR I“GEMENT OF LETIERS PATENT. Copyright O 19% Ame
16、rican Pclewn nstiMe . iii API PUBL*464L 96 0732290 0557430 866 ACKNOWLEDGMENTS THE FOLLOWING PEOPLE ARE RECOGNIZED FOR THEIR CONTRIBUTIONS OF TIME AND EXPERTISE DURING THIS STUDY AND IN THE PREPARATION OF THIS REPRT - Alexis E. Steen, Health and Environmental Sciences Department Joseph P. Smith, Cha
17、irman, Exxon Production Research Company Kris Bansal, Conoco inc. Lewis M. Cook, Chevron Research Particulates removed by filtration at pH1 1; Ionic imbalance or excess (e.g., excess calcium or potassium); Ammonia; Hydrocarbons; Hydrogen sulfide; Material removed by pH change; and Volatile compounds
18、. ES-2 API PUBL*4641 76 m 0732270 0557436 284 m Section 1 INTRODUCTION The toxicity of produced water (PW) that may be dischargecl ,it0 the offshore waters oi the Western Gulf of Mexico is limited by a National Pollutant Discharge Elimination System (NPDES) permit (58 FR 63964-63986). This permit re
19、quires operators to determine the threshold concentration for toxicity in a 7-day toxicity test conducted according to an EPA protocol and to show that the threshold concentration is higher than the predicted concentration 100 m from the discharge point. Operators with effluents failing to meet the
20、toxicity limit can either cease discharging, modify the outfalls to increase dispersion, or treat the effluent to reduce its toxicity. In an effort to improve understanding of the origin of toxicity in PW from U.S. facilities, the American Petroleum Institute (NI) has sponsored research involving ap
21、plication of toxicity identification evaluation (TIE) procedures to a wide range of PW effluents. This report sumarizes the results and lessons learned from NIS TIE research program. Produced waters can exhibit both acute and chronic toxicity in laboratory tests (Neff, 1987). Traditionally, sources
22、of toxicity in effluents have been identified by performing a series of chemical analyses in order to generate an inventory of potential toxicants. The toxicity of the individual components is then evaluated, typically using information in the scientific literature. There are several limitations ass
23、ociated with this approach: 1) chemical analyses may not identify all potential toxicants; 2) toxicants may behave differently in combination than they do individually (Le., additive, synergistic, and antagonistic effects are not considered); and 3) the toxicity of all components may not be well und
24、erstood. These limitations become magnified when considering PWs, which are complex mixtures of organic and inorganic constituents. This toxicity-based approach consists of subdividing the test effluent into various fractions and experimentally determining the toxicity of each fraction. This divisio
25、n reflects the need to select toxicity testing protocols and species as a function of the salinity of the effluent and receiving waters. By relating any reduction of toxicity to the class of chemicals that was removed from the sample, it is theoretically possible to determine a cause-and-effect 1-1
26、API PUBL*Yb1iL 7b W O732270 0557437 LLO relationship. This procedure forms the basis of what EPA describes as a toxicity identification evaluation or TIE (Burkhard and Ankley, 1989; Mount and Anderson-Carnahan, 1989). There are two major types of fractionation schemes in TIEs: reduction type and iso
27、lation type. The reduction type involves removing a particular class of compounds by some physical manipulation, and then conducting toxicity tests on the remaining effluent. The isolation type involves isolating a particular class of compounds by some manipulation, and then conducting toxicity test
28、s on the isolated fraction. Most of the fractionations involve performing a manipulation at different pHs in which the pH of the whole effluent is adjusted to acidic or basic conditions before performing the manipulations. The state of organic and inorganic compounds (ionic or un-ionized form) is in
29、fluenced by the pH of the solution and the equilibrium constant (k) of the compound. When the pH of the solution is equal to the pK, (-log, if the pH c p Mysidopsis bahia substituted for Arbacia punctulata two oil, two gas, and one gadoil PW samples from offshore Louisiana production facilities eigh
30、t fractionationadjustment procedures (EDTA chelation dropped) developed NWACEBCE fractionation procedures toxicity tests with two seawater species in iplicate (two samples) and single seawater species in duplicate (three samples) salinity tolerance of Mysidopsis hahin tested API PUBL*464L 96 0732290
31、 0557439 T93 Phase 1 The EPA TIE procedures do not address effluents with high salinities. The objectives of the first phase (Phase 1) were to: 1) evaluate the use of standard EPA TIE methods on representative high- and low-salinity PW; 2) to test the newly developed fractionation procedures; and 3)
32、 to test the performance of alternative toxicity test organisms in TIES on PWs with high salinities. Three low-salinity (e3 ppt) PWs were analyzed by EPA TIE procedures. Two higher-salinity (35 ppt) PWs were analyzed by TIE procedures modified for use on high-salinity effluents. The modifications in
33、cluded new extraction procedures that isolated neutral, acidic, and basic organic compounds (NE, ACE, and BCE fractionations) for direct toxicity testing. The invertebrates Mysidopsis buhiu and Arbaciu punctulatu, and the fish Cyprinodon variegatus were evaluated as toxicity test species for high-sa
34、linity PWs. Phase 2 Based on the results of Phase 1, additional TIEs were performed with the fractionations and toxicity test organisms that appeared to be best suited for PW TIEs. Toxicity tests using Arbuciu were dropped and extraction fractionations (NCE, ACE, and BCE) were substituted for the so
35、lid-phase extraction (SPE) fractionation in the EPA procedure. One low-salinity sample was analyzed using the freshwater TIE procedures, and four higher-salinity PW samples were analyzed by the modified procedures. Phase 3 Additional TIEs were performed on five high-salinity PWs to further document
36、the toxicity characteristics of PWs and to evaluate aspects of the testing procedure. Mysidopsis was used as the toxicity test species for all fractions. Cyprindon was also used as the test species for whole PWs only. The variability of the toxicity tests was evaluated by conducting the tests with d
37、uplicate or triplicate samples at each concentration. The salinity tolerance of Mysidopsis was evaluated to help interpret toxicity test results for PW with very high salinity. The chemical oxygen demand (COD) of the PWs was tested in this phase after it was observed that dissolved oxygen concentrat
38、ions decreased in test media for some PW samples. This report summarizes the objectives, methods, and results of this research on the toxicity of PW. Section 2 of this report summarizes the fractionation procedures and toxicity tests used 1-4 API PUBL*LIb41 96 0732290 0557440 705 and developed durin
39、g the three phases of research. The method summaries in Section 2 are supplemented by a set of standard operating procedures (SOPS) for the new methods that were developed (Appendices A through C); established methods are summarized and cited in the text of Section 2. The primary implications of the
40、se experimental results are discussed in Section 3 with conclusions and lessons learned resulting from this research presented in Section 4. A series of tables and supporting text summarizing important experimental conditions, observations, and results for the three sets of experiments are included
41、in Appendix D. 1-5 API PUBL*464L b = 0732290 0557441 641 = Section 2 METHODS This section summarizes the TIE procedures employed in this study. These procedures are modifications of EPA methods (Norberg-King et al., 1991; Burgess et al., 1993). The specific standard operating procedures (SOPS) used
42、for sample collection, fractionation, and toxicity testing of PWs are presented in Appendices A through C. SAMPLING Toxicity identification evaluations were conducted on 14 PW samples with salinity concentrations ranging from c3 parts per thousand (ppt) to lo0 ppt. In selecting samples, a mix of sam
43、ples from gas and oil production operations in different areas of the United States at various salinity ranges was desired. Background information on the 14 samples used for the study is summarized in Table 2- 1. Sixteen liters (four 4-L bottles) of PW were collected from participating facilities us
44、ing the sampling kit provided and following SOP MI-TIEPW3 (Appendix C). Samples were taken at a discharge point immediately downstream from the last conventional water-treating vessel. The bottles were filled slowly from the bottom in order to completely remove any airspace, and minimize loss of vol
45、atile compounds. The samples were transported from the field in coolers packed in ice and shipped to the TIE laboratory for next-day delivery. INITIAL PROCESSING On the day of receipt (Day i), a whole sample was tested for toxicity and fractionated for further toxicity testing the next day (Day 2).
46、On Day 1, the contents of the four 4-L bottles were combined in a 20-L polycarbonate container and gently mixed for 30 seconds. Each container was tightly capped and the sample aliquoted from the container by positive pressure decanting, to minimize agitation. After mixing, sample aliquots underwent
47、 initial toxicity testing and preliminary chemical analysis. This initial processing followed the procedures in Norberg-King et al. (1991). 2- 1 API PUBLa464L 9b M 0732290 0557442 588 M Table 2- 1. Types of Produced Water Samples Tested Sample ID Origin salinity Type of Production (PPt) Production A
48、dditives Phase 1 - Low TDS PWF-wY1 PWF-Tx1 PWF-wy2 Phase 1- High TDS PWS-LA3 PWS-CA1 Phase 2 - Low TDS PWF-LA5 PWF-LA4“ Phase 2 - High TDS PWS-CA2 PWS-LA6 PWS-LA7 PWS-LASb Phase 3 - High TDS PWS-LA1 1 PWS-LA13 PWS-LA9 PWS-LA10 PWS-LA12 Wyoming Coastal Texas Wyoming OffshodLouisiana Coastal Californi
49、a Coastal Louisiana Offshore Louisiana Coastal California Offshore Louisiana Coastal Louisiana Coastal Louisiana Louisiana Louisiana Louisiana Louisiana lo0 59 82 5 6 98 lo0 lo0 oil oil oil oil oil oil oil gas gas oil gas gadoil oil gas oil EB,CI,REB,SI,GT C CI CB EB,REB,SI,GTC EB,CI,REB,SI,C, F.GTC CI None EB ,CIW,REB ,F, SI,AC,CI EB,PCC,GTC CI EB,CIWP,PCC GTC CI,GTC,WC EB,C,F,SI B,AC,GTC,WC EB.WC Louisiana Results not evaluated because PW salinity was too high for tests with freshwater species. bResults not evaluated because PW toxicity was too low. EB = Emulsion Breaker CI
