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22) OECD 209-OPPTS 850.6800, Modified activated sludge respiration inhibition test, 454E102A PFBS: AN ACTIVATED SLUDGE, RESPIRATION INHIBITION TEST SANITIZED WILDLIFE INTERNATIONAL, LTD. PROJECT NUMBER: 454E-102A 3M ENVIRONMENTAL LAB PROJECT NO. E00-1429 Organisation for Economic Cooperation and Development OECD Guideline 209 and Council of European Communities Directive 67/548/EEC Annex V, Guideline C.11 DEC 0 9 2003 AUTHORS : Edward C. Schaefer Abul I. Sidchqui STUDY INITIATION DATE: November 17,2000 STUDY COMPLETION DATE: March 14,2001 SUBMITTED TO: 3M Corporation Environmental Laboratory 935 Bush Avenue St. Paul, Minnesota 55144 Wildlife International, Ltd. 8598 Commerce Drive Easton, Maryland 2 1601 (410) 822-8600 Page 1 of 44 WILDLIFE INTERNATIONAL,LTD. -L- PROJECT NO.: 454E-102A SANITIZED DEC O 9 2003 GOOD LABORATORY PRACTICE COMPLIANCE STATEMENT SPONSOR: 3M Corporation TITLE: PFBS: An Activated Sludge, Respiration Inhibition Test 3M ENVIRONMENTAL LAB PROJECT NO. E00-1429 WILDLIFE INTERNATIONAL, LTD. PROJECT NUMBER: 454E-102A STUDY COMPLETION: March 14,2001 This study was conducted in compliance with Good Laboratory Practice Standards as published by the U.S. Environmental Protection Agency in EPA 40 CFR Part 160, 17 August 1989; OECD Principles of Good Laboratory Practices (ENV/MC/CHEM (98) 17), and Japan MAFF 59 NohSan, Notlfication No, 3850, Agricultural Production Bureau, with the following exceptions: The reference substance, obtained from Aldrich Chemical Company (Mrlwaukee, WI), was not characterized in compliance with Good Laboratory Practice Standards. Stability, homogeneity and verification of the test and reference substances in the mixtures were not determined. The stability of the test and reference substances under conditions of storage at the test site was not determined in accordance with Good Laboratory Practice Standards. STUDY DIRECTOR: -~ Edward C. Schaefer Manager, Biodegradation SPONSOR: DATE WILDLIFE INTERNATIONAL,LTD. PROJECT NO.: 454E-102A -3- QUALITY ASSURANCE STATEMENT This study was examined for compliance with Good Laboratory Practice as published by the U.S. Environmental Protection Agency in EPA 40 CFR Part 160, 17 August 1989; OECD Principles of Good Laboratory Practices (ENV/MC/CHEM (98) 17); and Japan MAFF 59 NohSan, Notification No, 3850, Agricultural Production Bureau; Wildlife International, Ltd. Standard Operating Procedures and the study protocol. The dates of all inspections and audits and the dates that any findings were reported to the Study Director and Laboratory Management were as follows: ACTIVITY: . Initial Trial: 454E-102 Test SubstancePreparation D.O. Measurements Definitive Trial: 454E-102A D.O. Measurements Data and Draft Report Final Report DATE CONDUCTED: November 28,2000 November 28,2000 November 30,2000 January 5 & 8,2001 March 14,2001 DATE REPORTED TO: STUDY DIRECTOR: MANAGEMENT November 28,2000 November 28,2000 December 6,2000 November 29,2000 November 30, 2000 January 8,2001 March 14,2001 January 5,2001 January 12,2001 March 14,2001 Quality Assurance Representative DATE / y . 2-1 ~ WILDLIFE INTERNATIONALLT,D. -4- REPORT APPROVAL, SPONSOR: 3M Corporation TITLE: PFBS: An Activated Sludge, Respiration Irhbition Test 3M ENVIRONMENTAL LAB PROJECT NO. E00-1429 WILDLIFE INTERNATIONAL, LTD. PROJECT NUMBER 454E-102A PROJECT NO.: 454E-102A STUDY DIRECTOR: Edward C. Schaefer, B.S. Manager, Biodegradation DATE MANAGEMENT: Director, Aquatic Toxicology and Non-Target Plants WILDLIFE INTERNATIONAL,LTD. -5STUDY INFORMATION Study Initiation Date: Experimental Start Date: Experimental Termination Date: Study Completion Date: November 17,2000 November 27,2000 November 30,2000 March 14,2001 PROJECT NO.: 454E-102A DEC 09 SANITIZED Study Director: Edward C. Schaefer B.S. Sponsor: 3M Corporation Environmental Laboratory 935 Bush Avenue St. Paul, Minnesota 55 144 Sponsor's Representative: Study Personnel: Edward C. Schaefer, l3.S., Manager, Biodegradation Henry 0.Krueger, Ph.D., Director, Aquatic Toxicology and Non-Target Plants Abul Siddqui, B.A., Scientist, Biodegradation R. Scott Flags, B.S., Biologist, Biodegradation Rebecca Bryan, B.S., Biologist, Aquatics WILDLIFE INTERNATIONAL.LTD. -6- TABLE OF CONTENTS PROJECT NO.. 454E-102A Title Page ................................................. .................................................................... Page 1 Good Laboratory Practice Compliance Statement ................... .............. Quality Assurance Statement .................................................... Report Approval .......................................................................................................................... ..Page 4 Study Information ...........:. ............................................................................................................ Page 5 Table of Contents .......................................................................................................................... Page 6 Abstract ......................................................................................................................................... Page 8 Introduction.............1.. ................................................................................................................... Page 9 Objective....................................................................................................................................... Page 9 Experimental Design .................................................................................................................... ..Page 9 Materials and Methods .................................................................................................................. Page 9 Test Substance ................................................................................................................ Page 10 Reference Substance ....................................................................................................... Page 10 Test Conhtions and Apparatus................................. !....................................................... Page 11 Test Inoculum ................................................................................................................. Page 11 Procedure ........................................................................................................................ Page 11 Sample Analysis .............................................................................................................. Page 12 Calculations .................................................................................................................. ..Page 12 Statistical Analyses ......................................................................................................... Page 12 Results and Discussion ................................................................................................................ Page 13 Conclusion .................................................................................................................................. Page 13 References................................................................................................................................... Page 14 WILDLIFE INTERNATIONALL,TD. PROJECT NO.: 454E-102A -7- TABLE OF CONTENTS - Continued - TABLE Table 1. Respiration Rates and Percent Inhibitions .............................................,......................Page 15 FIGURES Figure 1. Figure 2. Figure 3. Figure 4. Figure 5. Figure 6. Figure 7. Figure 8. Figure 9. Figure 10. Figure 11. Figure 12. Dissolved Oxygen Concentration Over Time, Control 1............................................ Page 16 Dissolved Oxygen Concentration Over Time, Control 2 ............................................Page 17 Dissolved Oxygen Concentration Over Time, 3,5-Dichlorophenol, 3 mg/L ...............Page 18 Dissolved Oxygen Concentration Over Time, 3,5-Dichloropheno1715 mg/L .............Page 19 Dissolved Oxygen Concentration Over Time, 3,5-Dichloropheno1750 mg/L .............Page 20 Dissolved Oxygen Concentration Over Time, Perfluorobutanesulfonate (PFBS), 1.0 mg a.i./L................ ..................................................... Page 21 Dissolved Oxygen Concentrati uorobutanesulfonate (PFBS), 3.0 mg a.i./L .................................................................................. "....,.......P. age 22 Dissolved Oxygen Concentration Over Time, Perfluorobutanesulfonate (PFBS), 10.0 mg a.i./L .............................................................................................. Page 23 Dissolved Oxygen Concentration Over Time, Perfluorobutanesulfonate (PFBS), 30.0 mg a.i./L ...................................... ................................................... Page 24 Dissolved Oxygen Concentration Over Time, Perfluorobutanesulfonate (PFBS), 100.0 mg a.i./L ............................................................................................ Page 25 Dissolved Oxygen Concentration Over Time, Perfluorobutanesulfonate (PFBS), 300.0 mg a.i./L __.......................................................................................Page 26 Dissolved Oxygen Concentration Over Time, Perfluorobutanesulfonate (PFBS), 1000.0mg a.i./L .......................................................................................... Page 27 APPENDICES Appendix I. Measured Dissolved Oxygen (DO) Concentrations (mg Oz/L) ............................Page 28 Appendix 11. Graphical Presentation of Percent Inhibition and PFBS Concentration ................Page 30 Appendix III. Protocol and Protocol Amendments ....................................................................Page 31 WILDLIFE INTERNATIONALL,TD. PROJECT NO.: 454E-102A -8- ABSTRACT The effect of the test substance on activated sludge microorganisms was assessed by the Activated Sludge Respiration Inhibition Test Method (OECD Guideline 209). The test contained a control, reference and treatment groups. The control group was used to determine the background respiration rate of the sludge and was not dosed with the test or reference substance. The reference group was dosed with 3,5-dichlorophenol, a known mhlbitor of respiration, at concentrations of 3, 15 and 50 mg/L. The test substance was dosed at concentrations of 1, 3, 10, 30, 100, 300 and 1000 mg a.i./L. m e r an exposure period of three hours, the respiration rates of the test solutions were measured using a dissolved oxygen meter. The respiration rates in the two controls were 43.6 and 45.9 mg 02/L/hr,or a hfference of 5.0%. The difference in control respiration rates was with the 15% difference limit established for the test. The validity of the test was further supported by the results from the 3,5-dichlorophenol reference group, which resulted in an EC50 of 15.6 mg L. The EC50 was with the 5 to 30 mg/L range considered acceptable for the test. The EC50 for the test substance was over 1000 mg a.i./L. Differences in O2 respiration rates between the control group and test substance treatments were not observed at all test substance concentrations. Following is a summary of the results. TreatmentNominal Concentration Control 1 Control 2 3,5d1chlorophenol 3 mg/L 3,5dchlorophenol 15 mg/L 3,5dichlorophenol 50 mg/L Perfluorobutanesulfonate (PFBS) Perfluorobutanesulfonate (PFBS) Perfluorobutanesulfonate (PFBS) Perfluorobutanesulfonate (PFBS) Perfluorobutanesulfonate (PFBS) Perfluorobutanesulfonate (PFBS) Perfluorobutanesulfonate (PFBS) 1 mg a.i./L 3 mg a.i./L 10 mg a.i./L 30 mg a.i./L 100 mg a.i./L 300 mg a.i./L 1000 mg a.i.L Respiration Rate mg O2/L/hour 43.6 45.9 42.4 24.4 4.3 45.8 45.0 40.0 37.9 47.6 36.9 41.1 Percent Inhibition NA NA 5.3 45.5 90.4 -2.3 -0.6 11.0 15.3 -6.4 17.5 8.2 WILDLIFE INTERNATIONAL, LTD. PROJECT NO.: 454E-102A -9- INTRODUCTION The purpose of t h s test .is to provide a screening method to identify substances that may adversely affect aerobic microbial treatment plants and to indicate suitable non-hbitory test substance concentrations for use in biodegradability tests. l h s study was conducted by Wildlife International, Ltd. for 3M Corporation at the Wildlife International, Ltd. biodegradation facility in Easton, Maryland. Original raw data generated by Wildlife International, Ltd. and the original final report are filed under Project Number 454E-102A in the archives located on the Wildlife International, Ltd. site. OBJECTIVE The objective of this study was to assess the effects of PFBS on activated sludge microorganisms by measuring the respiration rate. EXPERIMENTAL DESIGN The test contained control, reference, and treatment groups. The control group was used to determine the background respiration rate of the sludge and was not exposed to the test or reference substances. The reference group was dosed with 3,5-dichlorophenol, a known inhibitor of respiration, at concentrations of 3, 15 and 50 mg/L. The test substance was tested at 1, 3, 10, 30, 100, 300 and 1000 mg a.i./L. MATERIALS AND METHODS Thls study was conducted according to the procedures outlined in the protocol, "PFBS: An Activated Sludge, Respiration Inhibition Test," (Appenhx III). The protocol was based on the procedures specified in the OECD Guideline for Testing of Chemicals, Method 209 (l), Council of the European Communities, Guideline C.11, Activated Sludge, Respiration Inhibition Test (2) and Fate, Transport and Transformation Test Guidelines, OPPTS 850.6800 (3). Wi LDLI FE INTERNATIoNAL, LTD. PROJECT NO.: 454E-102A Test Substance The test substance, PFBS, was received fiom 3M Corporation at Wildlife International, Ltd. on June 28, 2000 and was assigned Wildlife International, Ltd. identification number 5292. The test substance was stored at ambient conditions. Following is a description of the test substance used in this study: Name: Lot Number: CAS Number: Physical Description: Expiration Date: Purity: Water Solubility: Storage Conditions: Potassium, Perfluorobutane sulfonate (PFBS) 2 29420-49-3 White powder March 20 10 97.9% Moderate Ambient room temperature On the day of administration, stock solutions of the test substance were prepared in NANOpure@at nominal concentrations of 1000 and 2000 mg a.i./L. The test substance was administered by volumetric addition. .. Reference Substance A stock solution of the reference substance, 3,5-dichlorophenol was prepared by dmolving 500 mg in 10 mL of 1N NaOH and then diluting to 30 mL with NANOpure@water. While stirring, enough 1N HzS04 was added to reach the point of incipient precipitation. The solution of 3,5-&chlorophenol then was diluted to 1 L with NANOpure@water. The reference substance was admhstered by volumetric adhtion. Following is a description of the reference substance used in this study. Name: Manufacturer: Lot Number: Physical Description: Handling Precautions: Date Received: 3,5 -dichlorophenol Aldrich Chemical Co., Milwaukee, WI 026 11ES White solid Standard laboratory precautions January 24,2000 WILDLIFE INTERNATIONALTLD,. - 11 - PROJECT NO. 454E-102A Expiration Date: Purity: Storage Conditions: CAS Number: Wildlife International Ltd. ID: January 24,2005 99.1% Ambient 591-35-5 5 179 Test Condltions and Apparatus Control, reference, and treatment test mixtures were incubated at 20 f 2C and aerated for three hours at a rate sufficient to provide aerobic condhons and maintain solids in suspension. The mixtures were prepared and aerated in 500 mL plastic Erlenmeyer flasks and athen transferred into 300 mL biochemical oxygen demand (BOD) bottles to conduct the dissolved oxygen (DO) measurements. Test Inoculum Activated sludge was collected from the Denton Wastewater Treatment Plant Denton Maryland on November 27, 2000. The Denton facility receives wastes from predominately domestic sources. The sludge was sieved using a 2 mm screen and the total suspended solids (TSS) concentration of the sieved sludge was determined. The solids concentration of sludge was adjusted to 4000 mp/L (* 10%) by settling the sludge for approximately 30 minutes and then removing supernatant from above the settled sludge solids. The sludge was maintained in the laboratory for 3 days prior to use. Approximately 50 mL of synthetic sewage (Protocol, Appendix I) was added to each liter of activated sludge and the sludge was continuously aerated. Before use, the pH and total suspended solids concentration of the activated sludge were determined. Procedure Test mixtures were prepared at 15 minute intervals starting with the first control. The control contained 9.6 mL of synthetic sewage, 120 mL of inoculum, and enough NANOpure@water to bring the total volume up to 300 mL. The mixture was promptly aerated at a rate sufficient to provide aerobic conditions and keep the solids in suspension. Subsequent mixtures contained 9.6 mL. of synthetic sewage, 120 mL of inoculum, the appropriate amount of test substance or volume of reference substance stock ~ ~ ~~ WILDLIFE INTERNATIONALLT,D PROJECT NO.: 454E-102A - 12- solution, and enough NANOpure@water to bring the total volume up to 300 mL. Finally, a second control was prepared. All mixtures were aerated for three hours. Sample Analysis M e r three hours of aeration, the contents of the first vessel were transferred to a BOD bottle and the respiration rate was measured over a period of up to 10 minutes. Dissolved oxygen readings were recorded every 10 seconds for 10 minutes or until the DO dropped below 1.0 mg/L, whichever came first using a YSI Model 50B Dissolved Oxygen Meter. The respiration rate in subsequent vessels was determined in an identical manner at 15 minute intervals so that the contact time of the test substance with the activated sludge was three hours. Calculations A respiration rate was calculated for each test mixture and expressed in mg 02/L/hour. The rate was calculated using DO values between approximately 6.5 mg 02/Land 2.5 mg OzL, or over a 10 minute period if the DO did not reach approximately 2.5 mg O&. The respiration rate was calculated using the following equation: Respiration Rate = (initial DO -final DO)/Cfinal time - initial time) _. The percent inhibition for each test substance concentration was calculated using the following equation and plotted against the logarithm of test substance concentration (Appendix III): Percent Inhibition = 1 - 2Rs XlOO RC, + R C , where: R = oxygen consumption rate at a given concentration of the test substance RCI = oxygen consumption rate, Control 1 RC2 = oxygen consumption rate, Control 2 Statistical Analvses When the dose response pattern allows for the calculation of an EC5O value, the data are analyzed using the computer program of C.E. Stephan (4). The program was designed to calculate the EC50 value WILDLIFE INTERNATIONAL,LTD. - 13 - PROJECT NO.: 454E-102A and the 95% confidence interval by probit analysis, the moving average, or binomial probability with nonlinear interpolation (5, 6, 7). In t h s study, the probit method was used to calculate the EC50 for the reference group. RESULTS AND DISCUSSION Respiration rates and percent lnhibitions are presented in Table 1. Dissolved oxygen readmgs recorded during the test are presented in tabular and graphical forms in Appendices I and 11, respectively. The temperature recorded during the maintenance of the sludge prior to the test was 21C. The temperature range recorded the day of the test was 21-22C and was within the limits specified in the test guideline. The measured total suspended solids (TSS) concentration and pH of the sludge on the day of ' testing was 3647 mg/L and 7.7, respectively. The respiration rates in the two controls were 43.6 and 45.9 mg 02/L/hr,or a difference of 5.0%. The validity of the test was further supported by the results from the 3,5-dichlorophenol reference group, whch resulted in an EC50 of 15.6 m a . The EC50 was within the 5 to 30 m a range considered acceptable for the test. The 95% confidence limits for the EC50 were 13.1 and 18.5 mgL. The inhibitory effects upon respiration at the test substance concentrations analyzed (1, 3, 10, 30, 100, 300 and 1000 mg a.i./L) ranged from -6.4% to 17.5%. Respiration rates of the test substance -- concentrations evaluated ranged from 36.9 mg 02/L/hr(at 300 mg a.i./L) to 47.6 mg 02/L/hr(at 100 mg ai.&). CONCLUSION The maximum inhibitory effect upon respiration from PFBS was observed at the test substance concentration of 300 mg a.i./L, but only reached 17.5%. The EC50 is therefore greater than 1000 mg a.i./L. WILDLIFE INTERNATIONALLTD, . - 14 - REFERENCES PROJECT NO.: 454E-102A 1. Organisation for Economic Cooperation and Development. 1989. Activnted Sludge Respiration Inhibition Test. OECD Guideline 209. 2. Council of the European Communities. Directive 67/548EEC. Annex V. Guideline C.11, Activated Sludge Respiration Inhibition Test. 3. Fate, Transport and Transformation Guidelines. 1996. OPPTS 850-6800, Modified Activated Sludge, Respiration Inhibition Test for Sparingly Soluble Chemicals. 4. Stephan, C.E. 1978. U.S.EPA, Environmental Research Laboratory, Duluth, Minnesota. Personal communication. 5 . Finney, D.J. 1971. Statistical Methods in Biological Assay, second edltion. Griffin Press, London. 6. Thompson, W.R. 1947. Bacteriological Reviews, Vol. 11, No. 2: 115-145 7. Stephan, C.E. 1977. "Methods for Calculating an LC50," Aquatic Toxicology and Hazard Evaluations. American Society for Testing and Materials. Publication Number STP 634, pp 65-84. WILDLIFE INTERNATIONALL,TD. PROJECT NO.: 454E-102A - 15 - Table 1 Respiration Rates and Percent Mubitions Treatment/Nominal Concentration Control 1 Control 2 3,5-&chlorophenol 3 mg/L 3,5-&chlorophenol 15 mg/L 3,5-dichlorophenol 50 mg/L Perfluorobutanesulfonate (PFBS) Perfluorobutanesulfonate (PFBS) Perfluorobutanesulfonate (PFBS) Perfluorobutanesulfonate (PFBS) Perfluorobutanesulfonate (PFBS) Perfluorobutanesulfonate (PFBS) Perfluorobutanesulfonate (PFBS) 1 mg a.i./L 3 mg a.i./L 50 mg a.i./L 30 mg a.i./L 100 mg a . i L 300 mg a.i./L 1000 mg a.i./L Respiration Rate m i Oz/L/hour 43.6 45.9 42.4 24.4 4.3 45.8 45.0 40.0 37.9 47.6 36.9 41.1 Percent Mubition NA NA 5.3 45.5 90.4 -2.3 -0.6 11.0 15.3 -6.4 17.5 8.2 - 16- PROJECT NO.: 454E-102A 10.0 8.0 6.0 4.0 2.0 0.0 0 Control 1 50 100 150 200 250 300 350 400 450 500 550 600 Time (seconds) Figure 1 . Dissolved Oxygen Concentration Over Time, Control 1. Arrows indicate measured dissolved oxygen concentrations used to calculate respiration rate - 17- PROJECT NO.: 454E-102A Control 2 10.0 8.0 fi \ M E W K 6.0 a, sEU a>, 4.0 -.-0 In In n 2.0 0.0 0 50 100 150 200 250 300 350 400 450 500 550 600 Time (seconds) Figure 2. Dissolved Oxygen Concentration Over Time, Control 1. Arrows indicate measured dissolved oxygen concentrations used to calculate respiration rate - 18 - PROJECT NO.: 454E-102A 3,5-Dichlorophenol 3mg/L 10.0 8.0 6.0 4.0 2.0 0.0 0 50 100 150 200 250 300 3 50 400 450 500 5 50 600 Time (seconds) . Figure 3. Dissolved Oxygen Concentration Over Time, 3,5-Dichlorophenol, 3 m g L Arrows indicate measured dissolved oxygen concentrations used to calculate respiration rate - 19- PROJECT NO.: 454E-102A 3,5-Dichlorophenol 15rng/L 10.0 8.0 6.0 4.0 2.0 0.0 0 I I I I I I I I I I I I I I I 50 100 150 200 250 300 350 400 450 500 5 50 600 Time (seconds) Figure 4. Dissolved Oxygen Concentration Over Time, 3,5-Dichlorophenol, 15 mg/L. Arrows indicate measured dissolved oxygen concentrations used to calculate respiration rate - 20 - PROJECT NO.: 454E-102A 3,5-Dichlorophenol 50mg/L 10.0 8.0 2.0 -- 0.0 1 1 I I , I I I I I I I I I Figure 5. Dissolved Oxygen Concentration Over Time, 3,5-Dichlorophenol, 50 mgL. Arrows indicate measured dissolved oxygen concentrations used to calculate respiration rate -21 - PROJECT NO.: 454E-102A PFBS l m g a.i./L 10.0 8.0 6.0 4.0 2.0 0.0 0 50 100 150 200 250 300 350 400 450 500 550 600 Time (seconds) Figure 6. Dissolved Oxygen Concentration Over Time, Perfluorobutanesulfonate (PFBS), 1.O mg a.i./L. Arrows indicate measured dissolved oxygen concentrations used to calculate respiration rate - 22 - PROJECT NO.: 454E-102A PFBS 3 mg a.i./L 10.0 8.0 6.0 4.0 2.0 0.0 0 50 100 150 200 250 300 350 400 450 500 550 600 Time (seconds) Figure 7. Dissolved Oxygen Concentration Over Time, Perfluorobutanesulfonate (PFBS), 3 .O mg a.i./L. Arrows indicate measured dissolved oxygen concentrations used to calculate respiration rate - 23 - PROJECT NO.: 454E-102A PFBS 10 mg a.i./L 10.0 8.0 3 \ M E W K 6.0 FQ) 0 - U Q>) 4.0 .-0 VI VI n 2.0 0.0 0 50 100 150 200 250 300 350 400 450 500 550 600 Time (seconds) Figure 8. Dissolved Oxygen Concentration Over Time, Perfluorobutanesulfonate (PFBS), 10 mg a.i./L. Arrows indicate measured dissolved oxygen concentrations used to calculate respiration rate - 24 - PROJECT NO.: 454E-102A 10.0 8.0 1 6.0 PFBS 30 mg a.i./L 4.0 2.0 0.0 0 I 1 I I I I. I I 0 I f I I 50 100 150 200 250 300 350 400 450 500 550 600 Time (seconds) Figure 9. Dissolved Oxygen Concentration Over Time, Perfluorobutanesulfonate (PFBS), 30 mg a.i./L. Arrows indicate measured dissolved oxygen concentrations used to calculate respiration rate - 25 - PROJECT NO.: 454E-102A 10.0 8.0 1 6.0 PFBS 100 mg a.i./L 4.0 2.0 0.0 0 4 I 1 1 50 100 150 200 250 300 350 400 450 500 550 600 Time (seconds) Figure 10. Dissolved Oxygen Concentration Over Time, Perfluorobutanesulfonate (PFBS), 100 mg a.i./L. Arrows indicate measured dissolved oxygen concentrations used to calculate respiration rate -26- PROJECT NO.: 454E-102A PFBS 300 mg a.i./L 10.0 8.0 6.0 4.0 2.0 0.0 0 f I I I t I I I I I I I I I i 50 100 150 200 250 300 3 50 400 450 500 550 600 Time (seconds) Figure 11. Dissolved Oxygen Concentration Over Time, Perfluorobutanesulfonate (PFBS), 300 mg a.i./L. Arrows indicate measured dissolved oxygen concentrations used to calculate respiration rate - 27 - PROJECT NO.: 454E-102A 10.0 8.0 1 6.0 PFBS 1000 rng a.i./L 4.0 2.0 0.0 0 50 100 150 200 2 50 300 350 400 450 500 550 , 600 Time (seconds) Figure 12. Dissolved Oxygen Concentration Over Time, Perfluorobutanesulfonate (PFBS), 1000 mg a.i./L. Arrows indicate measured dissolved oxygen ' concentrations used to calculate respiration rate WILDLIFE INTERNATIONAL, LTD. PROJECT NO.: 454E-102A - 28 - APPENDIX I Measured Dissolved Oxygen (DO) Concentrations (mg 02/L) Time (h~sec.) E%00:30 00:40 0050 01:oo 01:lO 01.20 01.30 0 1.40 0150 02:oo 02:lO 02:20 02:30 02:40 0250 03:OO 03:lO 03:20 03:30 03:40 0350 04:OO 04:lO 04:20 04:30 04:40 0450 05:OO 05:lO 05:20 05:30 05:40 0550 06:OO 06:lO 06:20 06:30 06:40 0650 07:OO 07.10 07.20 07.30 07:40 0750 08:OO 08:lO 08:20 08:30 08:40 09 50 10 00 Bold numbers control 1.5 7.5 7.4 7.3 7.1 7.0 6.9 6.8 6.7 6.6 6.5 6.5 6.4 6.2 6.1 6.0 5.9 5.8 5.7 5.6 5.4 5.3 5.2 5.1 4.9 4.8 4.7 4.6 4.5 4.3 4.2 4.0 3.9 3.8 3.7 3.5 3.4 3.3 3.2 3.1 2.9 2.8 2.7 2.6 2.5 2.4 2.2 2.1 2.0 1.9 1.7 1.6 1.5 1.4 1.3 11..o1 0.9 mdicate Treatment Dissolved Oxygen (ma) ,5 -lhcIdorophenoI 3,5-0 1 3 mg/L 7.4 8.1 8.7 7.3 8.2 9.1 7.2 8.3 9.2 7.1 7.0 6.9 6.8 6.7 6.6 6.6 7.9 9.1 6.5 7.8 9.1 6.3 7.7 9.1 6.1 7.7 9.1 6.0 7.6 9.0 5.9 7.5 9.0 5.8 7.5 9.0 5.7 7.4 9.0 5.6 7.3 9.0 5.5 7.3 9.0 5.4 7.2 8.9 5.3 7.1 8.9 5.2 7.0 8.9 5.0 7.0 8.9 4.9 6.9 8.9 4.8 6.8 8.8 4.7 6.8 8.8 4.6 6.7 8.8 4.5 6.6 8.8 4.4 6.5 8.8 4.3 6.5 8.7 4.1 6.4 8.7 4.0 6.3 8.7 3.9 6.2 8.7 3.8 6.1 8.6 3.7 6.1 8.6 3.6 6.0 8.6 3.5 5.9 8.6 3.4 5.8 8.6 3.2 5.7 8.5 3.1 5.7 8.5 3.0 5.6 8.5 2.9 5.5 8.5 2.8 5.4 8.5 2.6 5.4 8.4 2.5 5.3 8.4 2.4 5.2 8.4 2.3 5.1 8.4 2.2 5.0 8.3 2.1 5.0 8.3 2.0 4.9 8.3 1.8 4.8 8.3 1.7 4.7 8.3 1.6 4.6 8.2 1.5 4.6 8.2 1.4 4.5 8.2 1.3 4.4 8.1 11..o2 4.3 4.3 8.1 8.1 09 4.2 81 4.1 8.0 dissolved oxygen concentrations used to calculate resplration rates s---pFBs- 1 mg a.i./L 3 mg a.i./L 6.6 7.2 6.3 7.1 6.2 7.0 6.1 6.9 5.9 6.8 5.3 6.7 5.7 6.5 5.6 6.4 5.5 6.3 5.4 6.2 5.3 6.1 5.1 5.9 5.0 5.8 4.9 5.7 4.8 5.6 4.7 5.4 4.6 5.3 4.5 5.2 4.3 5.0 4.2 4.9 4.1 4.8 3.9 4.7 3.5 4.5 3.7 4.4 3.6 4.3 3.4 4.2 3.3 4.0 3.2 3.9 3.1 3.8 3.0 3.6 2.8 3.5 2.7 3.4 2.6 3.2 2.4 3.1 2.3 3.0 2.2 2.9 2.1 2.7 1.9 2.6 1.8 2.5 1.7 2.3 1.5 2.2 1.4 2.1 1.3 2.0 1.2 1.8 1 .o 1.7 0.9 1.6 1.5 1.3 1.2 1.1 0.9 WILDLIFE INTERNATIONAL, LTD. PROJECT NO.: 454E- 102A -29- APPENDIX I (Continued) Measured Dissolved Oxygen (DO) Concentrations (mg O Z L ) Time h h Treatment Dissolved 0 en (mu 10 mg a.i./L 30 mg a.i./L 100 mp a.i.lL 300 mg a.i./L 00:10 1.3 6.8 6.6 7.1 00:20 7.1 6.7 6.2 7.0 00:30 7.1 6.6 6.1 6.9 7.0 6.5 6.0 6.9 6.9 6.4 5.9 6.8 6.8 6.3 5.8 6.7 01:lO 6.7 6.2 5.7 6.5 01.20 6.6 6.1 5.5 6.4 01.30 6.5 6.0 5.4 6.3 01.40 6.4 5.9 5.3 6.2 01:50 6.3 5.8 5.2 6.1 02:oo 6.2 5.7 5.1 02:lO 6.1 5.6 4.9 02:20 6.0 5.5 4.8 02:30 5.9 5.4 4.7 02:40 5.7 5.3 4.6 02:50 5.6 5.2 4.4 03:OO 5.5 5.1 4.3 03:lO 5.4 5.0 4.2 5.3 03:20 5.3 4.8 4.1 5.2 03:30 5.2 4.7 3.9 5.0 03:40 5.1 4.7 3.8 4.9 03:50 5.0 4.5 3.7 4.8 04:OO 4.9 4.4 3.6 4.7 04: 10 4.8 4.3 3.4 4.6 04:20 4.7 4.2 3.3 4.6 04:30 4.5 4.1 3.2 4.5 04:40 4.4 4.0 3.0 4.4 04:50 4.3 3.9 2.9 4.3 05:OO 4.2 3.8 2.8 4.2 05:lO 4.1 3.7 2.7 4.1 05:20 4.0 3.6 2.5 4.0 _. 05:30 3.9 3.5 2.4 3.9 05:40 3.8 3.4 2.3 3.8 05:50 3.7 3.3 2.2 3.6 06:OO 3.6 3.2 2.0 3.5 06:lO 3.4 3.0 1.9 3.4 0620 3.3 3.0 1.8 3.3 06:30 3.2 2.8 1.6 3.2 06:40 3.1 2.7 1.5 3.1 06:50 3.0 2.6 1.4 3.0 07:OO 2.9 2.5 1.3 2.9 07.10 2.8 2.4 07.20 2.7 2.3 11..o1 2.8 2.7 2.5 2.2 0.9 2.6 2.4 2.1 2.5 2.3 2.0 2.4 2.2 1.9 2.3 2.1 1.8 2.2 2.0 1.7 2.1 1.9 1.6 2.0 1.8 1.5 1.9 1.7 1.4 1.8 1.5 1.2 1.7 09: 10 1.4 1.1 1.6 09:20 1.3 1.o 1.5 1.2 0.9 1.4 11..o1 1.3 1.2 1o:oo 09 11 Bold numbers mdicate dissolved oxvgen concenrrations used to calculate respration rates 1000 mg a . i L 6.'l 6.5 6.4 6.3 6.2 6.1 6.0 5.9 5.8 5.7 5.6 5.4 5.3 5.2 5.1 5.0 4.9 4.8 4.6 4.5 4.4 4.3 4.2 4.1 3.9 3.8 3.7 3.6 3.5 3.3 3.2 3.1 3.0 2.9 2.7 2.6 2.5 2.4 2.3 2.2 2.0 1.9 1.8 1.7 1.6 1.4 1.3 1.2 11..o1 0.9 Control 2 6.2 6.0 5.9 5.8 5.7 5.6 5.5 5.3 5.2 5.1 5.0 4.8 4.7 4.6 4.4 4.3 4.2 4.0 3.9 3.8 3.7 3.5 3.4 3.3 3.2 3.0 2.9 2.8 2.6 2.5 2.4 2.3 2.1 2.0 1.9 1.8 1.6 1.5 1.4 1.2 11..o1 0.9 WILDLIFE INTERNATIONAL,LTD. PROJECT NO.: 454E-102A - 30 - APPENDIX LI Graphcal Presentation of Percent Inhibition and PFBS Concentration Percent Inhibition versus PFBS Concentration 100 60 .2_Y .I ca.I 40 E s H 10 100 -20 Concentration (mg a.i./L) Figure 1. Percent Inhibition versus PFBS Concentration WILDLIFE INTERNATIONALL,TD. -31 - APPENDIX111 . Protocol and Protocol Amendments PROJECT NO.: 454E-102A WILDLIFE INTERNATIONALLTD, . - 32 - PROJECT NO.:454E-102A PROTOCOL PFBS: AN ACTIVATED SLUDGE, RESPIRATION INHlBITION TEST Organisation for Economic Cooperation and Development OECD Guideline 209 and Council of European Communities Directive 67/548/EEC h e x V, Guideline C.11 ! 3M Environmental Lab Project No. E00-1429 Submitted to 3M Corporation Environmental Laboratory 935 Bush Avenue St. Pad, Minnesota 55 144 Wildlqe International, Ltd. 8598 Commerce Drive Easton, Maryland 21601 (410) 822-8600 October 19,2000 WILDLIFE INTERNATIONAL, LTD. - 33 - PROJECT NO.: 454E-102A SANITIZED wildlife International, Ltd. DEC 0 9 2003 PFBS. AN ACTIVATED SLUDGE, RESPIRATION WIIBITION TEST SPONSOk SPONSOR'S REPRESENTATIVE: TESTING FACILITY: STUDY DIRECTOR: LABORATORY MANAGEMENT: 3M Corporation Environmental Laboratory P.O. Box 3333 1 St Paul, k e s o t a 55133 Wildlife Intcmational Ltd. 8598 Commerce Drive Easton, Maryland 21601 Ed Schaefcr Henry 0. Kruegcr, Ph.D. Manager of Aquatic Toxicology & Non-Target Plants Test Concentrations: PROTOCOL APPROVAL PROTOCOL NO.: 454/10 1900L209aSUB454 /0/30/0u DATE' 3M LAB PROJECT NO. E00-1429 WILDLIFE INTERNATIONALL,TD. - 34 - PROJECT NO.: 454E-102A wildlife International, Ltd. -3- INTRODUCTION The purpose of this test is to provide a screening method to identify substances that may adversely affect aerobicmicrobialtreatment plants and to indicate suitablenon-inhibitory testsubstanceCoKentrationS for use in biodegradability tests. OBJECTIVE The objective of the study will be to assess the effects of Perfluorobutanesulfonate,potassium salt (hereafter referred to as PFBS) on activatedsludgemicroorganisms by measuring the respirationrate. An EC50 will be calculated, if possible. EXPERIMENTAL DESIGN The test willcontain a control, reference, and treatmentgroup. The control group isused to detamine the background respirationrate of the sludge and will not be exposed to the test substance. The reference groupwill be dosed with 3,5dichlorophenol, a known inhibitorof respiration,at concentrationsof 3,15, and 50 m a . The test substance willbe tested at 1,3,10,30,100,300, and 1000m a . M A T E W AND METHODS Test methods are based on the procedures specifiedin the OECD GuidelineforTestingof Chemicals, Method 209 (1) and Councilofthe EuropeanCommunitis. GuidelineC. 11. Activated Sludge, kpiration Inhibition Test (2). Test Substance The test substancewill be PFBS. Information on the characterization of tat, control or nfaence substances is reqrurcd by Good Laboratory Practice Standards (GLP). The Sponsor is responsible for providing Wildlife Jntcmational, Ltd written verification that the test substance has bcen charactcrizcd according to GLPs prior to initiation of the study. If written verification of GLP test substance characterizationis not provided to Wildlife International,Ltd., it will be noted in thecompliancestatementof the final report. The Sponsor is responsible for all information related to the test substance and agrees to accept any unused test substance andor test substancecontainers remaining at the end of the study. PROTOCOL NO.: 454/101900/209aSUB454 3M LAB PROJECT NO. E00-1429 WILDLIFE INTERNATIONALL,TD. - 35 - PROJECT NO.: 454E-102A 'Wildlife International, Ltd. -4- Stock Solution Preparation A stocksolutionof the test substancewill be prepared at a nominal concentrationof 1000mg active'l in high quality water (e.g. NanopureO). In addition, a stocksolutionof 3,5-dichlorophenol will preparedby dissolving500 mg in.10 m!.,of 1NNaOH and then dilutingto 30 mL with high quality wa& While stirring, enough 1N H2S04(approximately 8 mL) will be added to reach the point of hcipient precipitation. The solution of 3,5-dichlorophenol then will be diluted to 1 L with high quality water. Test Conditions and Apparatus Control,reference, and treatment test mixtureswill be incubated at 20 i 2C and aerated for 3 hours at a rate s a c i e n t to maintain solidsin suspension. The mixtures will be prepared and aerated in 500 mL plastic Erlenmeyer flasks and then transferred into a 300 mL Biochemical Oxygen Demand (BOD) bottle to the conduct dissolved oxygen (DO) measurements. Test Inoculum Activatedsludge fromthe ProspectBay WastewaterTreahent Plant will be used asthe inoculumfor the test. The Prospect Bay Facility receives wastcs fiom predominantly domesticsources.?hesludgewillbe sievedusing a 2 mm screen and then settledfor approximately30 minutes. The supematant abovethesealed solids will be drained and the total s u s p d e d solids (TSS) ConcentTation of the settled sludge will be. determined. Based on the result,the concentration of the sludgewill be adjustedto 4000 mg/L (t 10%)by diluting with NanopureO water. If the sludge cannot be uscd on the day of coUection or if the same batch is required to be used on subsequentdays (maximumfour days), 50 mL of syntheticsewage (AppendixI) willbc addedtoeach literof ! activated sludge at the end of each working day. The sludge will be aerated overnight at 20 i 2C. Before use, the pH and total suspended solids concentration of the activated sludge will be determined and, if necessary,adjusted to pH 6.0 - 8.0 and a solids concentrationof 4000 mg/L (i 10%). Procedure Test mixtures will be prepared at 15 minute intervalsstarting with the fvstcontrol. The control will contain 9.6 mL of syntheticsewage, 120mL of inoculum and enough Nanopurea water to bring the total PROTOCOL NO.: 454/101900/209aSUB454 3M LAB PROJECT NO. E00-1429 WILDLIFE INTERNATIONALL,TD. - 36 - PROJECT NO.: 454E-102A Wildlye International, Ltd. -5- volume up to 300 mL. The mixture will be promptly aerated at a rate sufficient to keep the solids in suspension Subsequent mixtures will contain 9.6 mL of synthetic sewage, 120 mL of inoculum, the appropriatevolume of test or reference substancestock solution, and enou&.Nanopure@water to bring the total volume up to 300 mL. Finally, a second control will be prepared. All mixtures will be aerated for three hours. Sample Analysis After three hours of aeration, the contents of the first vessel will be transferred to a BOD bottle and the respiration rate will be measured over a period of up to 10 minutes. Dissolvedoxygen readingswill be recorded every 10secondsfor 10minutes or until the DO drops below 1.O mg/L, whichever wmes first The respirationrate in subsequentvessels willbe determined inan identicalmanner at 15minute intenalsso that the contact time of the test substance with the activated sludge is three hours. Calculations A respirationrate willbe calculated for eachtest mixture and expressedinmg -our. Theratewill be calculated using DO values between approximately6.5 mg O,/L and 2.5 mg O& or over a 10minute period if the DO does not reach approximately2.5 mg 0,L. The percent inhibition for each kst substance concentration will be calculatedusing the following equation and plotted against concentrationon log paper: - x Percent Inhibition = I 2Ra 100 RCIf RC2 where R, = RC, = RCI = oxygen consumption rate at a gwen concentrationof the test substance oxygen consumption rate, Control 1 oxygen consumption rate, Control 2 PROTOCOL NO.: 454110 1900/209aSUB454 3M LAB PROJECT NO. E00-1429 WILDLIFE INTERNATIONAL,LTD. - 37 - PROJECT NO.: 454E-OOAA 'wildlife International, Ltd. -6- An EC50 value will be derived, if possible, based on the percent inhibition versus test substance concentration. Confidence limits (95%) for the EC50 will be determinedusingstandardstatisticalprocedures (3). Quality Control . The test is considered valid only if the following criteria are met: - the two control respiration rates are within 15% of each other; - the EC50 (3 hours) of 3,5dichlorophenoI is in the accepted range of 5 to 30 m a . RECORDSTO BE MAINTAINED Records to be maintained will include, but not limited to, the following: 1. A copy of the signed protocol. 2. Identificationand characterizationof the test substance as provided by Sponsor 3. Test initiation and terminationdates. 4. Experimental initiation and termination dam. 5. Stock solutionconcentrationcalculationsand solution preparation. 6 . Activated sludge source and pretreatmentdetails. 7. Test temperature and duration. 8. Reference substance results. 9. All dissolvedoxygenmcasunments. 10. Temperaturerange recorded during tcst period. 11. Inhibitioncurve and method for calculationof EC50. 12. If calculated, EC50 and 95% confidence limits. 13. A copy of the final report. FINAL REPORT A final report of the resultsof the studywill be prepared by WildlifeInternational, Ltd.The report is to include, but is not limited to, the following when applicable: 1. Name and addressof facility performingthe study. 2. Dates on which the study was initiated and completed. PROTOCOL NO.: 454/101900/209aSUB454 3M LAB PROJECTNO. E00-1429 WILDLIFE INTERNATIONALL,TD. - 38 - c PROJECT NO.: 454E-102A Wildlife Xnternational, Ltd. -7- 3. A statement of compliance signed by the Study Dxector addressing any excephons to Good Laboratory Practice Standards. 4. Objectives and procedures stated in the approved protocol, including any changes in the original protocol. 5 . Identificationand characterizationof the test substanceas providedby Sponsormcludingname, CAS number, p e r m t active, and other characteristm, if provided by the Sponsor. 6. A description of the transformations and calculationsperformed on the data. 7. A description of the methodsused and reference to any standard method cmploycd 8. A description of the test system. 9. A description of the preparation of the test solutions. the testing concentration(s), the route of administration, and the duration of the test. 10. A description of all circ~~~~tanthcaetsmay of afected the quality or integrity of the data. 11. The name of the study director, the names of other scientists or professionals, and the names of all supervisory personnel, involved in the study. 12. Thesigned and datedrcportsof eachof the individualscientists or otherprofessionalsinvolved mthe study, if applicable. 13. The location where the raw data and find report are to be stored. 14. A statement prepared by the Quality AssuranceUnitlistingthe dates that the study inspectionsand audits weremade and thedates of any findingswere reportedto the Study Director and Management 15. If it is necessaryto make correctionsor additions to.a final report after it has been acceptd,such changeswillbe made in the formof an amendment issued by the Study Diredor. The amendmentwill clearly identrfy the part of the final report that is bcmg amendedand the reasonsfor the amendment, and will be signed by the Study Director. CHANGING OF PROTOCOL Planned changes to the protocol will be in the form of written amendments signed by the Study Director and the Sponsor'sRepresentative. Amendments willbe consideredas part of the protocol and will be attached to the final protocol. Any other changeswill be in the form of writtendeviations signed by the Study Director and filed with the raw data. All changes to the protocol will be indicated in the find report. PROTOCOL NO.: 454/101900/209aSUB454 3M LAB PROJECT NO. E00-1429 WILDLIFE INTERNATIONAL, LTD. - 39 - PROJECT NO.: 454E-102A wildlife International, Ltd. -8- GOOD LABORATORY P R A ~ I C E S This study will be conducted in accordance with Good Laboratory Practice Standards for EPA (40 CFR Part 160); OECD Principles of Good Laboratory Practices (ENVIMCICHEM (98) 17); and Japan MAFF (59 NohSan, NotificationNo. 3850,Agricultural production Bureau). Each study conducted by WildlifeInternational, Ltd. is routinely examinedby the WildlifeInternational,Ltd. QualityAssuranceUnit for compliancewith Good LaboratoryPractices, StandardOperatingProcedures and the specified protocol. . A statement of compliance with Good Laboratory Practices will be prepared for all portions of the study conductedby WildlifeInternational, Ltd. Raw data for all work performed at WildlifeInternational,Ltd and a copyof the finalreport will be filed by projectnumber in archiveslocated on theWildlife Interna!iod, Ltd site, or at an alternativelocation to be specifiedin the finalreport. PROTOCOL NO.: 454/101900/209aSUB454 3M LAB PROJECT NO. E00-1429 WILDLIFE INTERNATIONALLTD, . '-40- PROJECT NO.: 454E-102A wildlye International, Ltd. -9REFERENCES 1 Organisation for Economic Cooperation and Development. 1989. ActivatedSIudgeRespiration Inhibition Test. OECD Guideline 209. 2 Council of the European Communities. Directive 67/548/EEC. Annex V. Guideline C.1 1 , Activated Sludge Respiration Inhibition Test. 3 Stephan, C.E. 1977. "Methods for Calculating an LC50," Aquatic Toxicology and Hazard Evaluations. American Society for Testingand Materials. PublicationNumber STP 634, pp 65-84. PROTOCOLNO.: 454/10 1900M09aSUB454 3M LAB PROJECT NO. E00-1429 WILDLIFE INTERNATIONALL,TD. -41 - PROJECT NO.: 454E-102A wildlife International, Ltd. -10- APPENDIX I. SYNTHETIC SEWAGE The synthetic sewage provides the necessary nutrients required for bacterial metabolism. It is prepared by dissolving the. following amounts of substances in 1 liter ofNanopur& water: . , 16.0 g peptone 11.0 g meat extract 3.0 g urea 0.7g NaCl 0.4g CaCll 2H20 0.2g MgS04 7H2O 2.8g K2HP04 Reagent grade chemicals or better will be used when available. The constituents of the synthetic sewageare not knownto contain any Contaminantsthat are reasonableexpectedto be presentand areknown to be capable of interferingwith the study. . .. PROTOCOL NO.: 454/101900/209aSUB454 3M LAB PROJECT NO. E00-1429 WILDLIFE INTERNATIONAL, LTD. - 42 - PROJECT NO.: 454E-IOAA WILDLIFE INTERNATIONAL LID. PROJECT NO.: 454E-102 Page 1 of 1 STUDY TITLE: AMENDMENT TO STUDY PROTOCOL PFBS: AN ACTIVATED SLUDGE, RESPIRATION INHIBITION TEST PROTOCOL NO.: 454/10 1900/209aSUB454 SPONSOR 3M Corporation EFFECTIVE DATE: November 27,2000 AMENDMENT: Test Inoculum, page 4- AMENDMENT NO.: 1 PROJECT NO.: 454E-102 DELETE: Activated sludge from the Prospect Bay Wastewater Trcahnent Plant will beused as the inoculum for the test. The Prospect Bay Facility receives wastes from predominantly domestic sources. ADD: Activated sludge from the De-ntonWastewater Treatment Plant willbe used as the inoculum for the test. The Denton Facility receives wastes kern predominantly domestic sources. REASON: Prospect Bay Wastewater Treatment Facility, Grasonville, Maryland has been closcd STUDY D E C T O R DATE WILDLIFE INTERNATIONAL,LTD. - 42 - PROJECT NO.: 454E-102A . . . WILDLIFE INTERNATIONALLTD. PROJECT NO.: 454E-102 Page 1 of 1 STUDY TITLE: AMENDMENT TO STUDY PROTOCOL PFBS: AN ACTIVATED SLUDGE, RESPIRATION INHIBITION TEST PROTOCOL NO.: 454/10 1900/209aSUB454 SPONSOR 3M Corporation EFFECTIVE DATE: November 27,2000 AMENDMENT: Test Inoculum,page -4- AMENDMENT NO.: 1 PROJECT NO.: 454E-102 DELETE: Activated sludge fiom the Prospect Bay Wastewater Treatment Plant willbeused as the inoculum for the test. The Prospect Bay Facility receives wastes fiom predominantlydomestic sources. ADD: Activated sludgefiom the Denton WastewaterTreatmentPlant willbe used asthe inoculum for the test. The Denton Facility receives wastes fiom predominantly domestic sources. 8,. . REASON Prospect Bay Wastewater Treatment Facility, Grasonville, Maryland has been closed. WILDLIFE INTERNATIONAL,LTD. - 43 - .. WILDLIFE INTERNATIONALLTD. PROJECT NO.: 454E-102A DEC 0 9 2003 SANITIZED PROJECT NO.: 454E-102 Page 1 of 1 STUDY TITLE: AhlENDMENT TO STUDY PROTOCOL PFBS:AN ACTIVATED SLUDGE, RESPIRATION INHIBITION TEST PROTOCOL NO.: 454/101900/209aSUB454 SPONSOR: 3M Corporation EFFECTIVE DATE: November 27,2000 AMENDMENT: Stock Solution Preparation, page -4- AMENDMENT NO.: 2 PROJECT NO.: 454E-102 DELETE: A stock solutionof the test substancewill be prepared at a nominal concentration of 1000 mg activefL in high quality water (e.g. Nanopur&). ADD: Test substancestock solutionswillbe prepared at nominalconcentrationsof I000 and 2000 mg activdL in high quality water (e.g. Nanopur&). REASON: A more concentrated stock solution is needed to dose the 1000 mg activdL treahnent WILDLIFE INTERNATIONAL, Lm. - 44 - W I L D L I F E INTERNATIONAL LTD. DEC 0 9 2003 PROJECT NO.:454E-102A SANITIZED PROJECT NO.: 454E-102 Page 1 of 1 STUDY TITLE: AMENDMENT TO STUDY PROTOCOL PFBS: AN ACTIVATED SLUDGE, RESPIRATION INHIBITION TEST PROTOCOL KO.: 454/101900/209aSUB454 SPONSOR.3M Corporation EFFECIWE DATE: January 09,2001 AMENDhlENT: Test Concentrations,page -2- AMENDMENT NO.: 3 PROJECT NO.: 454E-102 DELETE: Test Concentration: 1.3. 10.30. 100. 300. 1000 melL ADD: Test Concentration: 1. 3. 10. 30. 100.300. 1000 me A/L REASON: Entry error by Study Director , AMENDMENT.: Calculations,page -- ADD. The respiration rate will calculated using the following equation: Respiration Rate = (initial DO - f i n d oO)/@na! time - initial time) REASON: Protocol did not contain the equation used to calculate the respiration rate m TORY MANAGEMENT .L