Document jBQ5apd5O4poMmZvXKbk6b6Op

CO AR226-2618 103-DuET-?? AR226-2618 Distribution on last page DuPont Engineering Technologies Wastewater Group Brandywine DuPont Company Analysis of Perfluorooctanoic Acid (PFOA) In Samples From The Chambers Works Wastewater Treatment Facility Final Report Work Done By: Report Written By: Previous Related Reports: Project Code: Period Covered: Notebook Numbers: Date of Issue: Reviewed by: Approved by: Stephen Constable, Lynn Dekleva, Barbara Larsen, Stan Bachmura, R. K. Bell, Mark E Reeder, Mark Richmond Stephen Constable, Lynn Dekleva, Barbara Larsen Carbon Adsorption Isotherm Evaluation for Perfluorooctanoic Acid (PFOA) , Validation of Liquid Chromatography Tandem Mass Spectrometry (LC/MS/MS) For Analysis of Perfluorooctanoic Acid (PFOA) In Samples From Chambers Works Wastewater Treatment Facility 06/2003-09/2003 E93384FC 1/31/04 Maria Angelo, Mark Richmond, Irene Legeic, Bob Reich, Paul Jann, Charlie Zarzecki, Steve Breske, Bill Berti, John Gannon, Mary Kaiser, Carl Camp N/A [Enter PIP Class] MM/DD/YYYY 1997-SBU-?? iformation in this report is proprietary and should be handled according to the designated Proprietary brmation Protection (PIP) classification listed below. Abstract : Perfluorooctanoic acid (PFOA) containing wastewaters are discharged into the wastewater treatment system at Chambers Works (CW). This report describes the results of analyses for PFOA in samples taken from various locations at the CW site wastewater treatment system. Keywords liquid chromatography tandem mass spectrometry (LC/MS/MS), Perfluorooctanoic acid (PFOA), high performance liquid chromatography (HPLC), Chambers Works Secure Environmental Treatment, C8, Powdered Activated Carbon Treatment, PACT biological treatment, primary clarification [Enter PIP Class] MM/DD/YYYY 1997-SBU-?? Table of Contents TABLE OF CONTENTS INTRODUCTION AND OBJECTIVES.....................................................................................................................................................................4 SUMMARY AND CONCLUSIONS.........................................................................................................................................................................4 HIGHLY TREATED WASTEWATER TO THE DELAWARE RIVER. DURING THE SEVEN-DAY STUDY PERIOD, IT IS ESTIMATED THAT A TOTAL OF ABOUT 220-240 POUNDS OF PFOA WAS DISCHARGED TO THE TREATMENT SYSTEM AND ABOUT 190 POUNDS OF PFOA (TYPICALLY BETWEEN 140 AND 380 MICROGRAMS PER LITER) WAS DISCHARGED FROM THE TREATMENT PLANT. OF THE TOTAL PFOA LOAD TO THE SYSTEM, 150 POUNDS WAS DISCHARGED AS A SPIKE LOAD ON THE LAST DAY OF SAMPLING. THE SOURCE OF THE APPARENT SPIKE IS UNKNOWN.....................................................................................................................................................................................................4 PATENT SITUATION ..........................................................................................................................................................................................4 PROGRAM ........................................................................................................................................................................................................4 PUBLICATION STATUS ......................................................................................................................................................................................4 PERSONNEL......................................................................................................................................................................................................4 SAFETY AND WASTE DISPOSAL........................................................................................................................................................................5 ENVIRONMENTAL CONSIDERATIONS ................................................................................................................................................................5 ACKNOWLEDGMENT.........................................................................................................................................................................................5 SIGNATURES.....................................................................................................................................................................................................5 EXPERIMENTAL................................................................................................................................................................................................5 DISCUSSION OF RESULTS..................................................................................................................................................................................8 ,||yPENDIXES "^Si/ APPENDDC A: SUGGESTED PROTOCOL FOR SAMPLING APPENDIX B: LIQUID CHROMATOGRAPHY AND LIQUID CHROMATOGRAPHY TANDEM MASS SPECTROMETRY FOR PERFLUOROOCTANOIC ACID (PFOA) QUANTITATION APPENDIX C: EXPERIMENTAL RESULTS FOR CHAMBERS WORKS SAMPLING DISTRIBUTION FOR COMPANY PROGRESS REPORTS [Enter PIP Class] MM/DD/YYYY 1997-SBU-?? Analysis ofPerfluorooctanoic Acid (PFOA) In Samples From The Chambers Works Wastewater Treatment Facility Final report Introduction and Objectives Perfluorooctanoic Acid (PFOA) is a compound that is used for the production of fluoropolymers in DuPont. PFOA containing wastewaters are discharged to the Chambers Works (CW) site wastewater treatment system, which is operated by Secure Environmental Treatment (SET). In order to better understand the fate of PFOA in the treatment system, samples were taken over seven consecutive days in June 2003 from various locations in the CW wastewater treatment system and analyzed for compounds of interest. Summary and Conclusions The CW site wastewater treatment plant typically discharges between ten and twelve million gallons per day of highly treated wastewater to the Delaware River. During the seven-day study period, it is estimated that a total of about 220240 pounds of PFOA was discharged to the treatment system and about 190 pounds of PFOA (typically between 140 and 380 micrograms per liter) was discharged from the treatment plant. Of the total PFOA load to the system, 150 pounds was discharged as a spike load on the last day of sampling. The source of the apparent spike is unknown. Sl^atent Situation N/A Program The program is described elsewhere below. PFOA discharged to the CW system. Additional sampling and analysis may further help identify all sources of Publication Status N/A Personnel Name(s) Stephen Constable Lynn DeKleva Barbara Larsen R. K. Bell Location(s) B9248 G300/208 E228/120A DCSE-CW [Enter PIP Class] MM/DD/YYYY 1997-SBU-?? EirkRichmond an Bachmura DCSE-CW E228/141 Safety and Waste Disposal N/A Environmental Considerations N/A Acknowledgment Signatures Signature(s) of the author(s) should appear here. Experimental Description of the Chambers Works Wastewater Treatment System The Chambers Works Wastewater Treatment System consists of multiple treatment units, but the unit operations of interest to this work include primary, secondary and tertiary treatment. Primary treatment (excluding unit ops not of interest to this work) consists of lime neutralization ofon-site wastewaters followed by clarification in rectangular gravity clarifiers. Off-site wastes are typically added after primary clarification at spot 529. The primary clarifier effluent is then introduced into secondary treatment, which consists of activated sludge biological treatment that has been augmented with powdered activated carbon. This mixed powdered activated carbon and biological treatment treatment is termed PACT and takes place in large aerated tanks. After aeration in the secondary tanks, the secondary clarifiers settle out the PACT solids, which form a thick slurry termed underflow. The secondary underflow is mostly recirculated back to the secondary aeration tanks but a small sidestream is purged from the system for dewatering and disposal in the on-site landfill. Clarified secondary effluent is introduced into a tertiary PACT treatment system, which has unit operations (i.e., aeration tanks and clarifiers) similar to the secondary system. Tertiary clarifier iderflow solids are mostly recirculated to tertiary aerators, but a small stream is purged into the secondary treatment item. Supplemental Powdered Activated Carbon (PAC) is added to both tertiary and secondary treatment, with the 5 [Enter PIP Class] MM/DD/YYYY 1997-SBU-?? lounts varying with the seasons and treatment goals. Effluent from the tertiary treatment system is mixed with ler site waters before discharge to the Delaware River. Figure 1 shows the unit operations and sampling spots of interest to the work discussed in this report. Figure 1: C^amb^sM^tsAtef^^HazarcbusTrcafmenf^^^ [Enter PIP Class] To Belt Press < Dewatering MM/DD/YYYY 1997-SBU-?? fampling All samples were collected between June 16 and June 23, 2003 in accordance with the principles explained in Appendix A from the following locations: Location Sampling Spot Sampling Type Wastewater Treatment Plant Effluent Primary Influent Secondary Influent Parkersburg Rail cars Non-hazardous Primary Underflow Secondary MLSS Tertiary MLSS Secondary clarifier underflow 662 510 529 CF64 627 628 649 composite composite composite grab grab grab grab grab 24 hour composite samples were taken at the locations in the chart above using an ISCO sampler model 3710. Equal volume aliquots were taken every hour and composited at the end of 24 hours of samples. All other samples were grab samples. When samples were taken from sampling ports (such as underflow samples), the lines were allowed to flush for 30 seconds and then the grab sample was taken. Tertiary MLSS samples were taken by dipping a clean sample jar into the well and Parkersburg tanker samples were grab sampled from the dome using a sample thief before unloading. Equipment blank samples were collected by running analyte free water supplied by the lab through the sampler tubing, jar and strainer at one location, with a different location sampled each day before composite sampling began. Field blanks were collected by bottle to bottle transfer at the end of each day's sampling event at a separate location from equipment blanks. A duplicate sample was generated on each day of sampling for still a separate sample taken from a location other than that used for the field or equipment blanks. Experimental and Analytical Protocols: To determine soluble parameters, samples were centrifuged for 10 minutes at 6000 RPM (Sorvall RC-5 HS-4 Rotor) and supematants filtered (Pall Gelman 4190) prior to analysis. Total PFOA was determined by sonicating the sample with equal parts methanol for 1-hr. Analytical samples were refrigerated or frozen until analysis. One each of the primary underflow, secondary MLSS and tertiary MLSS sample aliquots was spiked with 1 ppm of PFOA and analyzed on both a total and soluble PFOA basis to test the extraction efficiency and spike recovery. After |j||fiking, samples were mixed using an end-over-end rotator (Glas-Col Rotator Model 099A RD4512) at 30-35 RPM [Enter PIP Class] MM/DD/YYYY 1997-SBU-?? A an ambient temperature of 19-25C. The temperature was monitored using a Dickson THDx Temperature recorder, pitch had a resolution of 0.5 "C and accuracy of+/-1 C. Following incubation, the samples were centrifuged for 10 minutes at 6000 RPM (Sorvall RC-5 HS-4 Rotor) and supematants were transferred to 50-mL polypropylene tubes using a disposable pipette (VWR 53283-706). Aliquots (5mL) of the supematants were filtered (Pall Gelman 4190) in 14-mL polypropylene tubes (Falcon 35 2059) using a 10-mL disposable syringe (BD 309695). Samples were diluted (if required) and submitted for analysis in polypropylene vials (Agilent 5182-0567) sealed with a natural rubber crimp seal (Agilent 5182-1210). Analytical samples were refrigerated or frozen until analysis. All samples except for the Parkersburg rail car samples were analyzed for PFOA using LC/MS/MS in accordance with the methodology shown in Appendix B. The Parkersburg samples were filtered as described above then shipped to Parkersburg for analysis via Liquid Chromatography as described in Appendix B. The total solids and total suspended solids of the primary underflow and MLSS samples were determined according to methods 2540B or 2540D, as outlined in Standard Methods for the Examination of Water and Wastewater, 20th Edition (1998), American Public Health Association, Washington, DC. Discussion of Results Mass flow data were obtained from SET for all rail car deliveries, treatment plant influent flow at 510 spot and treatment plant effluent flow during the seven-day consecutive period beginning June 16th, 2003. Rail car deliveries from Parkersburg were made only once during the weeklong sampling period and were added to the treatment system on June 18thjust after primary clarification but prior to spot 529. The previous addition from rail cars occurred June jiffith. PFOA concentrations in the Parkersburg rail car grab samples were determined using LC. The results determined from the LC/MS/MS method differed from historical results from Parkersburg for similar samples. The analysis of these samples by the LC/MS/MS method required significant dilution (5000-lOOOOOx), and the presence of Triton may have interfered with the analysis. Therefore, only these LC results are reported for the Parkersburg railcar samples. The results of the analyses of the treatment plant samples are included in Appendix C. Table 1 and Figure 2 show the mass balance for the treatment system for soluble PFOA over the 7 day sampling period. Based on mass estimates from the grab samples, the Parkersburg rail cars added about 62 pounds of PFOA to the treatment system during one day of the study period. The data from 529 spot composite sampling support this estimate. The 529 spot samples were taken after the rail car addition point and show an estimated total of 72 pounds of soluble PFOA. By comparison, summing 510 spot composite and railcar grab sampling results shows an estimated 89 pounds. On-site sources added about 4-6 pounds per day to the treatment system. There were about 150 pounds of soluble PFOA observed as a one-time spike load to treatment on 6/23. The source of the observed spike was unidentified. A concentration spike was observed in the secondary MLSS sample on 6/23. Reanalysis of selected samples from 6/22 and 6/23 corroborated the results. The soluble PFOA results for the original and reanalysis samples can not be directly compared since time passed before reanalysis, allowing for a new equilibrium to be established between liquid and solid phases in the stored samples. [Enter PIP Class] MM/DD/YYYY 1997-SBU-?? Figure 2: Mass of Soluble PFOA Prim ary influent 5 1 0 (ppd) Primary effluent 529 (ppd) -WWTP effluent 662 (ppd) ,, ,^-.1 the average over the seven-day sampling period, 32 pounds per day of soluble PFOA were discharged to the treatment system and 28 pounds per day of soluble PFOA were discharged from the treatment system. Excluding the results from the last day of sampling, there were between 70-90 pounds of soluble PFOA discharged to the treatment system while about 170 pounds exited the system. Since the hydraulic retention time of the treatment system is almost 3 days, the last day's spike load was excluded from mass balance considerations. Date Table 1: Mass Balance For Soluble PFOA 6/17 6/18 6/19 6/20 6/21 6/22 6/23 Average Std Dev i/17-6/23 Sum 6/176/22 803 (primary plant flows) mgd 7.7 662 (WWTP effluent flow) mgd 7.7 8.0 8.0 7.4 9.6 7.7 7.5 8 0.8 10.9 11.6 12.6 11.0 16.9 12.0 11.9 12.4 2 Railcar 1 grab sample* (ppd) 9 Railcar 2 grab sample*(ppd) 21 Railcar 3 grab sample* (ppd) 32 Primary influent 510 (ppd) 4 5 ,6 5 3 6 6 5 1 34 Primary effluent 529 (ppd) 15 37 5 5 3 6 150 32 54 72 total from railcar grab sampling + Primary 4 67 6 5 3 6 6 89 infl.510 WWTP effluent 662 (ppd) 24 14 31 35 44 25 20 28 10 173 All samples are composite except as indicated Duplicate samples were averaged for the mass balance. Note that 803 flows do NOT account for all of primary influent or effluent flows but were used in calculating the [Enter PIP Class] MM/DD/YYYY 1997-SBU-?? approximate preliminary mass balances above *as analyzed by Parkersburg's LC, converted to acid form ppd= pounds per day; mgd = million gallons per day 21583 = approximate gallons per railcar Appendixes Appendix A: Suggested Protocol For Sampling Appendix B: Liquid Chromatographv and Liquid Chromatographv Tandem Mass Spectrometrv for Perfluorooctanoic Acid (PFOA) Quantisation Appendix C: Experimental Results for Chambers Works Sampling [Enter PIP Class] MM/DD/YYYY 1997-SBU-?? distribution for Company Progress Reports Copy of Reports Sent To: Author(s): Additional recipients: Documentation Clerk: Director(s): Associate Directors): Supervisors): Managers): Manager-Patent Section: CR&D Technical Records Center: [Enter PIP Class] MM/DD/YYYY 1997-SBU-??