Document 8V6eadDX77D34Qq1rxKEQEy8Z

AR226-2694 16 AR226-2694 DuPont EMSE Report No. 17-03 Study Title ADSORPTION/DESORPTION OF AMMONIUM PERFLUOROOCTANOATE TO SOIL (OECD 106) Test Guideline(s) OECD 106 Guidelines for the Testing of Chemicals; Adsorption-Desorption Using a Batch Equilibrium Method (January 21,2000) Author Lynn Ann Dekleva Study Completion Date 17-April-2003 Test Facility E.I. du Pont de Nemours and Company Central Research & Development Corporate Center for Engineering Research Environmental and Microbiological Sciences & Glasgow Building 300, P.O. Box 6101 Newark, DE 19714-6101 USA Engineering Sponsor Association of Plastics Manufacturers in Europe Avenue E. Van Nieuwenhuyse, 4 / Box 3 B-l 160 Brussels Belgium EMSE Study /Project Number EMSERT01 II/14107 Report Number EMSER 17-03 T01II/14107 Page 1 of 55 DuPont EMSE Report No. 17-03 PAGE RESERVED FOR SPECIFIC COUNTRY REQUIREMENTS T01II/14107 Page 2 of 55 DuPont EMSE Report No. 17-03 GOOD LABORATORY PRACTICE COMPLIANCE STATEMENT The study described in this report was conducted in compliance with the United States Environmental Protection Agency, (FIFRA), Title 40 Code of Federal Regulations Part 160 (effective October 16, 1989), and TSCA Title 40 Code of Federal Regulations Part 792 which are consistent with the OECD Principles on Good Laboratory Practice (ENV/MC/CHEM(98)17) (Paris, 1998). The test substance is a commercially available material. The certificate of analysis (COA) was provided by the supplier and the accuracy of the data was considered sufficient for the purposes of this study. Analysis to confirm concentration and uniformity of the stock solutions was not performed. is believed not to affect the validity of the study because the test substance was accurately measured and added to the test vessels, and the concentration of test substance in the CaClz controls (test solutions, no soil) was determined throughout the study. This Study Director ^d^^^ff: William R. Berti, Ph.D. Senior Research Biologist DuPont Central Research & Development ;7-Q^;)-a^iu Date Sponsor/SubmiUer Date T01 II/14107 Page 3 of 55 DuPont EMSE Report No. 17-03 QUALITY ASSURANCE STATEMENT Study Number EMSER 17-03 /14107 Study Title Adsorption/Desorption of Ammonium Perfluorooctanoate to Soil (OECD 106) The conduct of this study, or studies of the same type, was inspected periodically. Audit dates are given below: Study Phase Inspected Study Protocol Study Conduct Report Inspection/Audit Dates 15-Jul-2002 02-Jan-2003 5,7,10-Feb-2003 Dates Findings Reported to Study Director 15-Jul-2002 02-Jan-2003 lO-Feb-2003 Dates Findings Reported to Management Not Applicable 02-Jan-2003 17-Apr-2003 These inspections confirm that the methods, procedures, and observations are accurately and completely described in this report, and the reported results accurately and completely reflect-there >'- ;:r raw data of this study. " ^LmJb^AlulS-/;h^^ KimberiyB. Brebne^/ QA Auditor DuPont Co. n-^p^-^os u, Date T01II/14107 Page 4 of 55 DuPont EMSE Report No. 17-03 CERTIFICATION OF AUTHENTICITY ADSORPTION/DESORPTION OF AMMONIUM PERFLUOROOCTANOATE TO SOIL (OECD106) a We, the undersigned, declare that the work described in this report was performed under our supervision, and that this report provides an accurate record of the procedures and results. Report by: ^urYl^O/rm. DabJU, LyniyAnn Dekleva Staff Engineer n'l\p^L -Aon?, Date Reviewed by: ^Ww^ ^ ^ ^ William R. Berti, Ph.D. Senior Reseaseh Biologist P-0^l-3oa3 Date .. <,,',tfS'aCS'i t"iii,*;{f- Approved by: f .^/^^~o^\ i T. Gannon, Ph.D. tesearch Manager l^/^^L^W Date Study Initiation Date: 26-July-2002 Date Study Completed: 17-Apr-2003 Sponsor: Association of Plastics Manufacturers in Europe Avenue E. Van Nieuwenhuyse, 4 / Box 3 B-1160 Brussels Belgium T01 II/14107 Page 5 of 55 DuPont EMSE Report No. 17-03 TABLE OF CONTENTS Title Page.........................................................................................................................................1 Page Reserved for Specific Country Requirements.........................................................................! Good Laboratory Practice Compliance Statement.................................................................^....... .3 Quality Assurance Statement..........................................................................................................^ Certification of Authenticity............................................................................................................5 Table of Contents............................................................................................................................^ General Study Information..............................................................................................................9 1.0 Summary ...............................................................................................................................11 2.0 Introduction...........................................................................................................................13 2.1 Study Purpose..................................................................................................................l3 2.2 Study Objectives .............................................................................................................13 2.3 Test Guidelines................................................................................................................l3 3.0 Materials and Methods..........................................................................................................13 3.1 Test Substance.................................................................................................................13 3.2 Reagents and Solvents.....................................................................................................14 3.3 Application Information..................................................................................................14 3.4 Test System..............................................................................................................;;.....14 3.5 Test Soils and Sludge ......................................................................................................15 3.6 Analytical Methods.........................................................................................................15 3.7 Experimental Design.......................................................................................................15 3.7.1 Phase 1 Preliminary Studies................................................................................15 Validation of the Analytical Method ..................................................................15 Adsorption to Test Vessel Containers ................................................................16 Determining the SoihSolution Ratio and Equilibration Time ............................16 Determination of Test Substance Stability .........................................................17 3.7.2 Phase 2 Definitive Studies...................................................................................l7 Adsorption Experiments.....................................................................................17 Desorption Experiments.....................................................................................18 3.8 Data Analysis..................................................................................................................18 3.8.1 Equilibration Time and Percent Adsorption........................................................18 3.8.2 Adsorption...........................................................................................................19 3.8.3 Desorption...........................................................................................................19 3.8.4 Material Balance from Adsorption/Desorption Experiments..............................20 3.8.5 Adsorption Isotherms ..........................................................................................21 3.9 Statistical Methods and Control ofBias..........................................................................21 3.10 Deviations from Test Protocol ......................................................................................22 T0111/14107 . Page 6 of 55 DuPont EMSE Report No. 17-03 4.0 Results and Discussion............................................................................................................22 4.1 Preliminary Studies.........................................................................................................22 Validation of the Analytical Method ............................................................................22 Adsorption to Test Vessel.....................................................................................,......^ Soil Solution Ratio and Equilibration Time .................................................................23 Mass Balance Determinations......................................................................................24 4.2 Definitive Studies...........................................................................................................^ Adsorption and Desorption Studies..............................................................................24 5.0 Conclusions.............................................................................................................................^ 6.0 Retention of Records ...............................................................................................................26 7.0 Disposal of Test Substance......................................................................................................27 8.0 References................................................................................................................................27 Tables Table 1 Chemical and Physical Properties of Test Materials ...............................................28 Table 2 Determination of Test Substance in CaCk Solutions (No Soil) ..............................29 Table 3 Determination of Test Substance in CaClz Soil Extracts.........................................30 Table 4 Adsorption to Test Vessel ........................................................................................31 Table 5 Adsorption in Percent as a Function ofSoil-.Solution Ratio and Equilibration Time ...............................................................................................................32 Table 6 Mass Balance Calculations of Drummer and Hidalgo Soils Performed at 1:1 Soil Solution Ratio after 24 Mixing ......................................................................................33 Table 7 Definitive Adsorption Study; Percent Adsorption and Linear Adsorption Isotherm Parameters..............................................................................................................34 Table 8 Definitive Adsorption Study; Freundlich Adsorption Isotherm Parameters............35 Table 9 Desorption of Test Substance from Test Soils.........................................................36 Figures Figure 1 Analytical Method Validation ofCaCl2 Controls (No Soil) and Extracts from Drummer and Cape Fear Soils .....................................................................................37 Figure 2 Adsorption of Test Substance as a Function ofSoil:Solution Ratio and Equilibration Time with Drummer Soil ................................................................................38 Figure 3 Adsorption of Test Substance as a Function ofSoil:Solution Ratio and Equilibration Time with Hidalgo Soil.........................,.........................................................39 Figure 4 Average Kd vs Fraction of Organic Carbon for Drummer, Hidalgo, Cape Fear and Keyport Soils..........................................................................................................40 Figure 5 Average Kom vs Fraction of Organic Carbon for Drummer, Hidalgo, Cape Fear and Keyport Soils.................................'.........................................................................41 Figure 6 Average Koc vs Fraction of Organic Carbon for Drummer, Hidalgo, Cape Fear and Keyport Soils..........................................................................................................42 Figure 7 Linear Adsorption Isotherm of the Test Substance in Drummer Soil ....................43 Figure 8 Linear Adsorption Isotherm of the Test Substance in Hidalgo Soil.......................44 Figure 9 Linear Adsorption Isotherm of the Test Substance in Cape Fear Soil ...................45 T01II/14107Page 7of55 DuPont EMSE Report No. 17-03 Figure 10 Linear Adsorption Isotherm of the Test Substance in Keyport Soil.....................46 Figure 11 Linear Adsorption Isotherm of the Test Substance in Wilmington Sludge..........47 Figure 12 Freundlich Adsorption Isotherm of the Test Substance in Drummer Soil ...........48 Figure 13 Freundlich Adsorption Isotherm of the Test Substance in Hidalgo Soil..............49 Figure 14 Freundlich Adsorption Isotherm of the Test Substance in Cape Fear Soil...........50 Figure 15 Freundlich Adsorption Isotherm of the Test Substance in Keyport Soil..............51 Figure 16 Freundlich Adsorption Isotherm of the Test Substance in Wilmington Sludge....................................................................................................................................52 Figure 17 Total Desorption vs Fraction of Organic Carbon for Drummer, Keyport and Cape Fear Soils...............................................................................................................53 Appendices Appendix 1 Ammonium Perfluorooctanoate Analytical Method.........................................54 Appendix 2 Certificate of Analysis of Test Substance .........................................................55 ;i ;s '.ostt T01II/14107 Page 8 of 55 DuPont EMSE Report No. 17-03 ADSORPTION/DESORPTION OF AMMONIUM PERFLUOROOCTANOATE TO SOIL (OECD 106) GENERAL STUDY INFORMATION Study Purpose The purpose of this study was to test the adsorption behavior of the test substance on four soil samples and one activated sludge sample to determine a sorption value that can be used to predict partitioning of the test substance in the environment. Study Objectives Study the sorption behavior of test substance in soils with varying soil characteristics. Provide data for determining the leaching and runoff potential of the test substance in soil including determinations of the following parameters: adsorption coefficient, Kd adsorption coefficient as a function of organic matter, Kom adsorption coefficient as a function of organic carbon, Koc percent desorbed Freundlich adsorption isotherms in all test soils with greater than 10% adsorption Test System Justification The test system is outlined by the U.S. EPA and OECD and was requested by the sponsor. Study Personnel Management: Study Director: Additional Study Personnel: John T. Gannon, Ph.D. William R. Berti, Ph.D. Stanley F. Bachmura, Jr. Lynn Ann Dekleva Barbara S. Larsen, Ph.D. Testing Facility E.I. du Pont de Nemours and Company Central Research & Development Corporate Center for Engineering Research Environmental and Microbiological Sciences & Glasgow Building 300, P.O. Box 6101 Newark, DE 19714-6101 USA Engineering T01 II/14107 Page 9 of 55 DuPont EMSE Report No. 17-03 Analytical Facility E.I. du Pont de Nemours and Company Central Research & Development Corporate Center for Analytical Services Experimental Station Laboratory Building 228 Wilmington, DE 19808 USA Study Execution Dates Study Initiation Date: Experimental Start Date: Experimental Completion Date: Study Completion Date: 26-July-2002 22-Aug-2002 03-Feb-2003 17-Apr-2003 T01II/14107 Page 10 of 55 DuPont EMSE Report No. 17-03 ADSORPTION/DESORPTION OF AMMONIUM PERFLUOROOCTANOATE TO SOIL (OECD 106) 1.0 SUMMARY The adsorption and desorption properties of ammonium perfluorooctanoate were investigated in four soil and one activated sludge samples. The adsorption coefficient (Kd), adsorption coefficient as a function of organic matter (Kom), adsorption coefficient as a function of organic carbon (Koc), and Freundlich isotherm parameters (Kp and 1/n) were determined. The adsorption of ammonium perfluorooctanoate was evaluated according to "OECD Guidelines for Testing of Chemicals 106" and was performed in two phases. Phase 1 consisted of screening studies to determine the optimal soil to solution ratio, the equilibrium time for .adsorption, potential for adsorption on the surfaces of the test vessels, and the stability of the test substance during the test. Phase 2 utilized a batch equilibrium soil slurry method to determine the linear and Freundlich adsorption isotherm parameters and evaluate desorption of the test substance. The table below summarizes the results from this study. Adsorption (%) Kd(mL/g) K,,,(mL/g) K.^(mL/g) KF(^lgl'l/Il(mL)l/>gl) 1/n Wilmington Drummer___Hidalgo____Sludge___Cape Fear Keyport 79.3-88.9 4.25-8.86 73.8-111 42.8-89.2 5.64 0.994 27.8-43.8 0.41-0.83 53.0-108 30.8-62.6 0.59 1.00 69.5-87.3 12.6-36.8 20.5-59.6 11.9-34.6 3.90 1.36 54.1-73.7 1.19-2.84 95.9-229 55.6-133 3.23 0.885 64.5-80.8 1.82-4.26 48.9-115 28.4-66.5 1.64 1.11 Soils tested at 1:1 soil:solution ratio; Wilmington sludge tested at 1:5 soiids:solution ratio 24 hour equilibration time "s*' yaw wi^mw The average adsorption of ammonium perfluorooctanoate during a 24-hour equilibration time at a 1:1 soil:solution ratio ranged from 40.8% for the Hidalgo to 81.8% for the Drummer soil. The test soils yielded Kd values of 4.25 to 8.86 mL/g for the Drummer soil, 1.82 to 4.26 mL/g for the Keyport soil, 1.19 to 2.84 mL/g for the Cape Fear soil, and 0.41 to 0.83 mL/g for the Hidalgo soil. The Wilmington sludge sample had the highest average Kd value of 22.5 mL/g, with Kd values that ranged from 12.6 to 36.8 mL/g. T01 II/14107 Page 11 of 55 DuPont EMSE Report No. 17-03 The Koc values of the soils ranged from 48.8 mL/g in the Keyport soil to 229 mL/g in the Cape Fear soil and the Kom values ranged from 28.4 mL/g for the Keyport soil to 133 mL/g for the Cape Fear soil. The Wilmington sludge sample had an average Koc value of 36.5 mL/g and average Kom value of 21.2 mL/g. There was a strong linear correlation (1B2=0.9465) between the fraction of organic carbon and average Kd values (Figure 4). The Freundlich adsorption coefficient (Kp) and the constant (1/n) were determined from the linear form of the Freundlich equation for all test materials. Freundlich adsorption coefficients ranged from 0.59 for the Hidalgo soil to 5.64 ^ig l-l/n (ml)17"g"' for the Drummer soil. The Kpoc values ranged from 44.2 to 261 pg 1-1/" (ml)17"g"1and the Kpom values ranged from 25.6 to 151 p,g l-l/n (ml)1''"g"1for the Keyport and Cape Fear soils, respectively. There was a strong inverse relationship (R^O.8665) between the fraction of organic carbon (foe) and the total % desorption of the test compound in the Drummer, Keyport and Cape Fear soils. < The Drummer soil which had the highest foe of the soils used in this study (5.76%) had a 36,0% ;> average total desorption. Cape Fear with a foe of 1.24% had an average desorption of 53.0%. is wn.h s to The desorption results for the Hidalgo soil and the Wilmington Sludge sample were highly variable and ranged from 41.6 to 121 % and 14.9 to 101 %, respectively. T0111/14107 Page 12 of 55 2.0 2.1 2.2 2.3 3.0 3.1 DuPont EMSE Report No. 17-03 INTRODUCTION Study Purpose The purpose of this study was to test the adsorption behavior of the test substance on four soil samples and one activated sludge sample to determine a sorption value that can be used to predict partitioning of the test substance in the environment. Study Objectives The major objectives of this study were to Study the sorptive behaviour of ammonium perfluorooctanoate in soils with varying soil characteristics Provide data for determining the leaching and runoff potential of the test substance in soil including determinations of the following parameters: adsorption coefficient, Kd adsorption coefficient as a function of organic matter, Kom adsorption coefficient as a function of organic carbon, Koc percent desorbed Freundlich adsorption isotherms in all test soils with greater than 10% adsorption Test Guidelines The study design met the data requirements specified in the OECD Guideline for Testing of Chemicals, "Adsorption-Desorption Using a Batch Equilibrium Method", Guideline 106, January 2000 and U.S. Environmental Protection Agency, Pesticide Assessment Guidelines (1982). MATERIALS AND METHODS Test Substance Name: Synonyms: Active substance: CAS Name: Ammonium perfluorooctanoate Ammonium pentadecafluorooctanoate; Ammonium perfluorocaprylate; DS 101; Fluorad FC 143; Perflurorooctanoic acid ammonium salt; UnidyneDS 101;APFO Octanoic acid, pentadecafluoro-, ammonium salt ' Octanoic acid, pentadecafluoro-, ammonium salt T01 II/14107 Page 13 of 55 DuPont EMSE Report No. 17-03 CAS Number: Supplier: Product Number: Lot Number: Molecular Formula: Formula Weight: Concentration ofa.s., nominal: Certificate of Analysis Date: Solubility: Appearance: Date Received: 3825-26-1 Pluka Chemical Company 1001 West St. Paul Milwaukee, WI 53233 USA 77262 421207/1 CgHLtFisNOa 431.1 g/mole >98.0% 24-Jan-Ol 1 g/10 ml White Powder 22-August-02 3.2 Reagents and Solvents All chemicals and solvents were of reagent grade or purer and were purchased from the following suppliers: Calcium chloride dihydrate (Mallinckrodt); Methanol used for extractions (Burdick & Jackson), Methanol HPLC grade (EM Science), and Ammonium Acetate ACS grade (EM Science). . 3.3 Application Information wf^<&??. The test substance was administered from a 1000 mg/L stock sohitibiiiin0.01M CaCl-z prepared in a polypropylene volumetric flask (Nalgene 4000-0050). The stock solution was prepared the day of testing and stored at room temperature until use. 3.4 Test System The test system employed in this study consisted of individually capped 50-mL polypropylene conical tubes (Falcon BD 35 2070), uniquely identified, containing 0.01M CaClz solution with and without test soils or sludge. The tubes were mixed using an end-over-end rotator (Glas-Col Rotator Model 099A RD4512) at 30-35 RPM at an ambient temperature of 19-25C. The temperature was monitored using a Dickson THDx Temperature recorder, which'had a resolution of0.5C and accuracy oflC. Following incubation, the samples were centrifuged for 30 minutes at 6000 RPM (Sorvall RC-5 HS-4 Rotor) and supematants were transferred to 50-mL polypropylene tubes ( Falcon BD 35 2070) using a disposable pipette (VWR 53283-706). Aliquots (5 mL) of the supematants were filtered (Pall Gelman 4190) in 14-mL polypropylene tubes (Falcon 35 2059) using a 10-mL disposable syringe (BD 309695) and refrigerated or frozen until analysis. All experiments were conducted in duplicate. T01 II/14107 Page 14 of 55 DuPont EMSE Report No. 17-03 3.5 Test Soils and Sludge Four soil samples and one activated sludge sample were used in this study. The characterization of the soils and sludge was performed at MDS Harris Laboratories (Lincoln, Nebraska) and is presented in Table 1. The pH of the soils ranged from 5.4 to 7.8 and organic carbon ranged from 0.77 to 5.76 %. Prior to use, the test soils were air-dried and sieved though a 2-mm mesh sieve. The activated sludge sample was collected from the dewatering facility of the Wilmington Wastewater Treatment facility. Sludge samples were washed twice with distilled water, freeze-dried, pooled, and gamma irradiated. The moisture content of the test materials was determined on three aliquots (Ohaus AP 210-0) by heating at 100-105C (Yamato drying oven DX 300) for a minimum of 12 hours. The moisture content was determined by the equation: .. (wet Weight - Dry Weight) o% / M^ o i s t*u, r e = ------------------------- x ,100 Dry Weight 3.6 Analytical Methods Ammonium perfluorooctanoate (APFO) was quantitated by liquid chromatography (LC) (Agilent 1090 Liquid Chromatograph) combined with tandem mass spectrometry (MS/MS) (Micromass Quatro). Negative ion electrospray was used to produce the molecular anion for the perfluorooctanoic acid, which was then subjected to collision-induced dissociation producing the decarboxylated anion. The MS/MS transition was specific to perfluorooctanoic acid and the area of the chromatogram was proportional to the concentration of APFO. The standard operating conditions for the method are provided in Appendix huSamplestiwere diluted (if required) with 0.01M CaCk and submitted for analysis in polypropylenemals (Agilent 5182-0567) sealed with a natural rubber crimp seal (Agilent 51.82r-1.2l0). Samples were refrigerated or frozen until analysis. - Samples were analysed by duplicate injections and quantified using a calibration curve generated the day of analysis. Sample concentrations were reported at or above the limit ofquantitation (LOO) for this study. 3.7 Experimental Design 3.7.1 Phase 1 Preliminary Studies Validation of the Analytical Method The solubility of the test substance was reported by the manufacturer to be 0.1 g/mL in HzO. The solubility of the compound was not determined in this study because the highest test concentration used in this study, 2500 |J.g/L, was significantly below the solubility limit for the compound reported by the manufacturer. T01 II/14107 Page 15 of 55 DuPont EMSE Report No. 17-03 The test substance was administered to the test systems by means of diluting a 1000 mg/L stock solution with 0.01M CaCl2 solution (prepared using deionized water). Aliquots of the test substance were added to polypropylene tubes containing 0.01M CaCb to achieve final test concentrations of 100, 500,1000 and 2500 u,g/L. Blank tubes were included and contained only the 0.01M CaClz solution. Aliquots (5 mL) of the samples were filtered (Gelman Pall 4190) into 14 mL polypropylene tubes (Falcon 35 2059) using a 10 mL disposable syringe (BD 309695) and refrigerated or frozen until analysis. All experiments were conducted in duplicate. Analytical samples were diluted with 0.01M CaCIa solution prior to submission to achieve an analytical concentration in the range of 10 to 150 Hg/L. The analytical method was validated on two soils. Soil extracts from Drummer (5.76% organic carbon) and Cape Fear (1.24% organic carbon) soils were prepared by mixing 20 g of soil with 20 mL 0.01M CaCk solution for 48 hours at 30-35 RPM at ambient temperature. The extracts were recovered after centrifugation (Sorvall RC-5B HS-4 rotor, 6000 RPM, 30 minutes). The test compound was added to the soil extracts, which were then filtered (Gelman Pall 4190) and submitted for analysis. Soil and CaCl2 blanks and CaCl2 controls at the four test concentrations (100, 500, 1000 and 2500 p,g/L) were included in the study. Replicate concentration measurements were done on two separate days. Adsorption to Test Vessel Containers The potential for adsorption of the test substance to the test vessel was assessed by analyzing the test substance solutions contaimng.the. highest and lowest concentrations in the validation >i.;(; u>;: experiments (100 and 2500 ng/L). The test substance was added to 50 mL polypropylene;''? centrifuge tubes containing 20 mL of 0.01M CaClz solution. The tubes were placed on a rotator for 24 hours at 30 to 35 RPM at ambient room temperature. The concentration of the solution at 24 hours was compared to aliquots taken at set-up to determine the potential for adsorption of the test substance to the test vessel. Determining the Soil:Solution Ratio and Equilibration Time The Soil:Solution Ratio and Equilibration Time experiment was conducted with two soil types, Drummer and Hidalgo, and three soil-solution ratios (20 g soil:20 mL, 5 g soil:25 mL, and 1 g soil:25 mL). Soil samples were pre-equilibrated with the 0.01M CaCIa solution using an end-over-end rotator at 30-35 RPM. Following pre-incubation (12 hr), the test substance was added to the test vessels to yield a final test concentration of 1000 (Ag/L. Control tubes (test substance in CaCk), CaCl2 blanks and soil blanks were prepared and processed with the adsorption samples. T01 II/14107 Page 16 of 55 DuPontEMSE Report No. 17-03 The test vessels were placed on the end-over-end rotator at 30-35 RPM at ambient room temperature. Duplicate test vessels for each soil:solution ratio, including control and blank tubes were collected at 2,6,24 and 72 hours and were centrifuged. The supernatants were transferred to 50 mL polypropylene tubes, aliquots were filtered and submitted for determination of the test compound. The percent adsorption was calculated at each time point on the basis of the nominal initial concentration and the measured concentration at the sampling time. Soil tubes and supernatants were frozen for approximately one month until the extraction procedure was performed for determination of test substance stability and mass balance calculations. Determination of Test Substance Stability A mass balance was performed after the soil:solution ratio experiment. The 1:1 soil solution ratio tubes from the 72-hour time point, were used for this experiment. Test and blank soil tubes were thawed at room temperature for approximately one hour before addition of 20 mL of methanol (Burdick & Jackson 232-1). The pellets were disrupted using a polystyrene weighing spoon (Bel Art H36940-000) and resuspended by vortexing. The tubes were mixed for a minimum of 2 hours before centrimgation (6000 RPM, 30 minutes) and recovery of the methanol. A second extraction was immediately performed. Aliquots (5 mL) were filtered (Gelman Pall 4190) to remove any particulate material. Aliquots of the filtered methanol extracts (1 mL of the first and 3 mL of the second) were transferred to 5 mL polypropylene test tubes and evaporated completely using a Pierce Reacti-Vap Evaporating Unit (Model 18780) with a Nitrogen purge (1 psi). The residue in the tubes was resuspended in one mL 0.01M CaCliand submitted for analysis; 3.7.2 Phase 2 Definitive Studies Adsorption Experiments The adsorption experiment was conducted on four soils and one sludge sample. The experiment was conducted, in duplicate, at a 1:1 soil: solution for the test soils and 1:5 soil:solution ratio for the sludge sample at 4 test concentrations (100, 500,1000 and 2500 ng/L). The samples were pre-equilibrated with 0.01M CaCk solution overnight (12 hours) before addition of the test substance. The tubes were mechanically agitated using an end-over-end rotator (30-35 RPM, ambient temperature) for 24 hours before the supernatants were recovered by centrimgation. Control tubes (test substance in CaCk), CaCb blanks and soil blanks were prepared and processed with the adsorption samples. An aliquot (5 mL) of the supernatants was filtered (Gelman Pall 4190), diluted (if required), and refrigerated or frozen until analysis. The percent adsorbed was determined by comparing the amount of test substance in the aqueous phase at equilibrium to the amount of test substance added to the system (based on calculated concentration). 'irogun ; uhwtred T01 II/14107 Page 17 of 55 DuPont EMSE Report No. 17-03 Desorption Experiments Desorption experiments were conducted on all test soils immediately following the adsorption study. The soil pellets from the adsorption study were resuspended in 20 mL ofO.OlM CaClz solution (sludge tubes received 25 mL). The pellets were disrupted via a polystyrene weighing spoon (Bel Art H36940-000) and vortexed to ensure complete mixing. The samples were agitated using an end-over-end rotator for 24 hours at ambient temperature, centrifaged and supematants recovered. A second desorption step was conducted immediately. Aliquots of the desorption supematants were filtered and submitted for analysis. The percent test substance desorbed was determined by comparing the amount of test substance in the aqueous phase following a given desorption interval to the amount of test substance associated with the soil phases at the adsorption equilibrium. The total amount of test substance desorbed was obtained by summing the percent desorption at each desorption interval. 3.8 Data Analysis 3.8.1 Equilibration Time and Percent Adsorption Equilibration time can be determined from plots of the concentration of the test substance in the aqueous phase versus time or from plots of percent adsorption (A) against time. The values of adsorption (A) were calculated according to the following equations. A msoil mo Co Vo Cw Vw m soi.,l xlOO A==- "O where mo=CoxVo = msoii mo - (Cw x Vw) Definition___________________ percent adsorption mass of test substance adsorbed to soil at equilibrium mass of test substance applied to test vessel initial concentration of test solution volume of test solution added to test vessel concentration of test substance in aqueous phase at adsorption equilibrium volume of aqueous phase in the adsorption test at equilibrium (test solution, Vo, plus water present in the soil) Unit % p,g pg ng/mL mL pg/mL mL T01 II/14107 Page 18 of 55 DuPont EMSE Report No. 17-03 3.8.2 Adsorption The adsorption coefficient, Kd, for each test solution concentration were calculated for each test soil using the following equation. The Kd value will also be used to calculate Kom and Koc values. K ^'-w ^ ^om om ^ ^c oc Definition_____________________ Unit Kd adsorption coefficient niL/g Cs concentration of the test substance in the soil phase ).ig/g at adsorption equilibrium Kom Koc oc adsorption coefficient based on organic matter adsorption coefficient based on organic carbon fraction of organic carbon (foe) = % organic carbon/I 00 mL/g mL/g na om fraction of organic matter na =fraction of organic carbon * 1.724 3.8.3 Desorption The percent desorbed, D, was calculated according to the following equations. m^xlOO 1 ----------------- "soil ,, ^Dl^00 "2-----m-------- soil DT = Dl + D2 where = mw,Di = mw,D2 Cw,Di x Vw,Di - (Cw x Vret) Cw,D2 X Vw,D2 - (Cw,Dl X Vret,Dl) T01 II/14107 Page 19 of 55 DuPont EMSE Report No. 17-03 Di D2 DT nisoil mw,Di Cw,Di Vw,Di v-^w V,et niw,D2 Cw;D2 Vw,D2 VrefaDI Definition percent of test substance desorbed after first desorption interval percent of test substance desorbed after second desorption interval total percent of test substance desorbed after both desorption intervals mass of test substance adsorbed to soil at equilibrium mass of test substance in aqueous phase after first desorption interval concentration of test substance in aqueous phase after first desorption interval total volume of aqueous phase (added solution plus volume of water retained in soil) after first desorption interval concentration of test substance in aqueous phase at adsorption equilibrium volume of water retained in soil at adsorption equilibrium mass of test substance in aqueous phase after second desorption interval concentration of test substance in aqueous phase after second desorption interval total volume of aqueous phase (added solution plus volume of water retained in soil) after second desorption interval volume of water retained after first desorption interval 3.8.4 Material Balance from Adsorption/Desorption Experiments V ^ (C xV ) + m + m -., -- MB=-^-^------w^1----^xlOO^ Definition____________________ MB material balance Cw concentration of test substance in aqueous phase at adsorption equilibrium Vw total volume of the aqueous phase (added solution plus volume of water present in the soil) Units % % % ^g ^g Hg/mL mL ug/mL mL ^g pg/mL mL mL Units % Hg/mL mL T0111/14107 Page 20 of 55 DuPont EMSE Report No. 17-03 mw,Di mw,D2 Vo Co mass of test substance in aqueous phase following first desorption interval mass of test substance in aqueous phase following second desorption interval volume of solution added to test vessel concentration of test solution added to test vessel p,g u,g mL u,g/mL 3.8.5 Adsorption Isotherms Linear and Freundlich adsorption isotherms were constructed for each soil in which adsorption exceeded >10%. Linear isotherms were constructed by plotting Cs (y-axis) and Cw (x-axis) for each soil tested. The Freundlich adsorption coefficient (Kp) and the exponential constant (1/n), were determined from linear regression analysis of the Freundlich equation: Cg= Kp x Cw The linear form of this equation is shown below. log(Cs) - log(Kp) + (1/n x log(Cw)) Plotting the linear form of the Freundlich equation with log (Cs) on the y-axis and log (Cw) on the x-axis will yield a line with a slope of 1/n and a y-intercept of log (Kp). The KF value was used to calculate Kpom and Kpoc values. K = Fom K-TF-. om ^ KFOC=^ 3.9 Statistical Methods and Control of Bias Statistical methods including means, standard deviations, and regression lines were used as appropriate. Bias was effectively controlled through duplicate sampling, replicate analysis, sample spiking, and maintenance of material balance. Microsoft Excel 2000 was used in all calculations and in the statistical t-Test. T0111/14107 Page 21 of 55 DuPont EMSE Report No. 17-03 3.10 Deviations from Test Protocol The mass balance determinations from the preliminary study were not immediately performed after the completion of the soil:solution ratio and equilibrium time study. The analysis of the substance extracted from the solid phase (mass balance) studies was not completed until after the adsorption-desorption experiments were completed. This is not believed to have affected the definitive study and is discussed in more detail in the Results and Discussion section of this report. One of the soil types for the soil:solution ratio was recommended to have an organic carbon content less than 2.0% and pH of less than 4.8. The measured pH from the original characterization of the Cape Fear soil (8-Dec-97) had a reported value of 4.9. The accuracy of the equipment utilized by Agvise laboratories for this analysis is unknown. The soil was re-characterized by Harris laboratories and had a reported pH of 5.4. The pH deviation is not believed to have affected the results from soil:solution ratio or definitive studies. 4.0 RESULTS AND DISCUSSION 4.1 Preliminary Studies Validation of the Analytical Method Ammonium perfluorooctanoate (APFO) in CaClz solutions was quantified as the perfluorooctanoate anion using liquid chromatography (LC) combined with tandem mass spectrometry (MS/MS). Liquid chromatography was used to separate the analyte of interest using a linear gradient ofMethanol (Appendix 1). The flow was diverted to waste for the first 3 minutes of the run and then directed to the mass spectrometer. The MS/MS transition 423 > 369 was specific to perfluorooctanoic acid and the area of the chromatogram was proportional to the concentration of ammonium perfluorooctanoate. Calibration standards were prepared fresh each day by dilution of a refrigerated stock solution of 1000 mg/L APFO. The instrument was calibrated using a 5-point calibration ranging from 10 to 150 [-ig/L. The calibration standards were run in duplicate followed by a low (20 p,g/L) check standard, high (100 p,g/L) check standard, and a blank injection. The standard injection volume for the method was 25 pL. The calibrations curves had correlation coefficients (R2)of greater than 0.985 and the check standards were 10% the test concentration. The samples were analyzed from duplicate injections and the mean test concentration was reported. The limit ofquantitation (LOQ) (Reference 7) for this method was 10 p,g/L with the method of detection limit (MDL) at 5 ppb. The coefficient of variation on 5 replicates was determined to be < 15%. The accuracy was determined to be 15% of the mean value of 5 replicates except at the LOQ where the accuracy was 20%. T01 II/14107 Page 22 of 55 DuPont EMSE Report No. 17-03 The analytical method was validated using filtered CaClz solutions and extracts prepared from Drummer and Cape Fear soils. The measured concentration for the CaClz tubes was < 20% of the expected value except for one of the 2500 p.g/L Control tubes, which had a deviation of 25.4% from the nominal test concentration (Table 2). This deviation from the expected concentration was not observed in subsequent testing ofCaCl2 control solutions, which had less than 20% difference from mean control tube measured values at all four test concentrations (Table 3). The CaCl2 blanks in this preliminary study resulted in measured concentrations of 15.5 and 15.6 |j,g/L for the test compound (Table 2) and were isolated to this experiment. CaCk in all subsequent testing resulted in measured concentrations of less than the limit ofquantitation (LOQ)oflOHg/L. The soil extracts did not interfere with the detection of the test compound. The measured concentrations for the soil extracts were generally < 15% that of the CaClz controls (no soil) prepared during the study and had similar linear correlations (Table 3, Figure 1). One of the Cape Fear soil extracts prepared at a test concentration of 100 ng/L had a 33.1% difference from the mean value for the Cada 100 |j,g/L controls. Since this discrepancy was isolated to one tube and was detected in only one soil extract it was attributed to experimental serror during the preparation of the sample. Adsorption to Test Vessel The test compound did not adsorb to the test vessel during the 24-hour study. The difference between the measured concentrations at the initial and 24-hour time point-were not significant (p=0.05) and averaged 1.36% for the 100 |^g/L tubes and 16.3% for thQ<2.5QO^glL tubes (Table 4). Soil Solution Ratio and Equilibration Time The soil solution ratio and equilibration time investigation was conducted at a test concentration of 1000 |-ig/L on two soil types. Drummer and Hidalgo, and at three soil solution ratios. The adsorption was calculated (Table 5) based on the nominal test concentration and was plotted against incubation time for the both soils (Figures 2 and 3). At 24 hours, the adsorption ranged from 29.3% for the 1:25 soil:solution ratio to 83.9% for the 1:1 soil solution ratio with the Drummer soil, and 20.1 % for the 1:25 soil:solution ratio to 42.2% for the 1:1 soil solution ratio with the Hidalgo soil. These values remained essentially unchanged or decreased slightly after 72 hours, and 24 hours was selected as the equilibration time for subsequent studies. To achieve adsorption values of greater than 20% and preferably greater than 50% for all test soils, a 1:1 soil:solution ratio was selected for adsorption studies for the test soils. The low density of the sludge sample required that the adsorption-desorption studies be performed at a 1:5 soil:solution ratio. However, this ratio met the desired adsorption of greater than 50% (Table 7). T01 II/14107 Page 23 of 55 DuPont EMSE Report No. 17-03 Mass Balance Determinations The mass balance for the Drummer and Hidalgo soil tubes was lower than the CaCk control tubes (Table 6) based on the nominal test concentration from the soil:solution ratio study. The Hidalgo soil had an average mass balance of 84.4% and a range of 79.0 to 89.8%. The mass balance was 68.6% determined from the one Drummer soil tube available from the soil:solution ratio equilibrium time experiment. The CaClz control tubes, which contained no soil, were included in the mass balance determinations. The supematants recovered at the end of the soil:solution ratio equilibrium time experiment accounted for an average of 98.9% of the added test compound. The methanol extraction in the control tubes (no soil, with test substance) resulted in an average mass balance of 110% with a range of 100 to 119%. The less than 90% recovery of the test substance from the soil pellets may be the result of the difficulty in resuspending the soil pellets in the extraction solvent. This disruption step required the mechanical manipulation of the soil pellets which inadvertently led to some soil loss. The pellets were vigorously vortexed after disruption but because of the soil matrix it was difficult to establish whether the slurry had a uniform particle dispersion or if there was some residual clumping. The Drummer soil pellet was extremely difficult to resuspend during the extraction phase and required more mechanical disruption than the Hidalgo soil pellets. This may account for the lower mass balance determinations between the two soils. The methanol extracts were not directly analyzed for the test compound but evaporated completely and resuspended in 0.01M CaCb solution before analysis. The evaporation step may, however, not account for the lower recovery of the test compound in the soil extracts. The efficiency of methanol'. in extracting the test substance from the soils was not determined in this study, but was* assumed to be a suitable extraction solvent for this compound. The effect of the time lag between the soil:solution ratio experiment and the extraction of the soil pellets on the recovery of the test compound is unknown. The soil:solution ratio experiment was concluded approximately one month before the extraction of the soil pellets. This storage may have had some effect on the recovery of the test compound from the soil pellets or on the nature of the interaction between the test compound and the soil matrix. Although the recovery of the compound was < 90% in this experiment, the definitive adsorption desorption experiments are descriptive of the test compound's behavior in the presence of soil matricies. The difficulties in pellet resuspension during extraction and subsequent evaporation of the extraction solvent suggest that alternative experimental approaches may need to be developed and validated for subsequent mass balance studies. 4.2 Definitive Studies Adsorption and Desorption Studies ' The aqueous phase analysis of the adsorption experiment agreed well with the 24-hour results from the preliminary soil:solution ratio and equilibrium time phase of the study for the Drummer and Hidalgo soils. After 24 hours, the Drummer soil had adsorbed an average of 83.6% and Hidalgo soil had adsorbed an average of 38.1%, based on nominal initial concentrations, when tested at 1000 ng/L (Table 7). T01II/14107Page 24of55 DuPont EMSE Report No. 17-03 Linear isotherms were constructed by plotting Cw (concentration of the aqueous solution at equilibrium) vs Cs (mass adsorbed to soil/test soil dry weight) for the four test soils and the activated sludge sample (Figures 7-11). The linear adsorption isotherms had correlation coefficients, which ranged from 0.926 for the Hidalgo soil to 0.977 for the Drummer soil. The values for the adsorption coefficient, Kd, were calculated for all four test soils and the one activated sludge sample (Table 7). The average Kd values ranged from an average of 0.61 mL/g for the Hidalgo soil to an average of 5.63 mL/g for the Drummer soil. The test soils yielded Kd values of 4.25 to 8.86 mL/g for the Drummer soil, 1.82 to 4.26 mL/g for the Keyport soil, 1.19 to 2.84 mL/g for the Cape Fear soil, and 0.41 to 0.83 mL/g for the Hidalgo soil. The Wilmington sludge sample had the highest average Kd value of 22.5 mL/g, with Kd values that ranged from 12.6 to 36.8 mL/g. There was a strong linear correlation (R2^ 0.947) between the fraction of organic carbon and average Kd values (Figure 4). The adsorption coefficients were corrected for organic carbon and organic material content of the test materials to calculate the soil sorption coefficients Koc and Kom (Table 7). The fraction of organic carbon (foe) of the test materials was determined by the Walkley-Black method and the fraction of organic matter was calculated based on the assumption that soil organic matter contains 58% carbon. The average Koc values ranged from 79.0 mL/g in the Hidalgo soil to 148 mL/g in the Cape Fear soil and the average Kom values ranged from 45.8 mL/g for the Hidalgo soil to 56.7 mL/g for the Drummer soil. The Wilmington sludge sample had an average Koc value of 36.5 mL/g and average Kom value of 21.2 mL/g. The Freundlich adsorption coefficient (Kp) and the constant (1/n) were determined from the linear form of the Freundlich equation for all test materials. Adsorption isotherms were constructed for all test materials (Table 8, Figures 12-16) and resulted in Freundlich adsorption coefficients, which ranged from 0.59 for the Hidalgo soil to 5.64 ^ig 1-1/" (ml)17"g'' for the Drummer soil. The adsorption coefficients were corrected for organic carbon and organic material content for each test material (Table 8). The Kpoc values ranged from 44.2 to 261 ng l-l/n (ml)17"g-' and the Kpom values ranged from 25.6 to 151 ug 1-17" (ml)17"g-' for the Keyport and Cape Fear soils, respectively. There was a strong inverse relationship (R^O.8665) between the fraction of organic carbon (foe) in the Drummer, Keyport and Cape Fear soils and the total desorption of the test compound (Figure 17). The Drummer soil with a foe of 5.76% had an average of 36.0% total desorption while Cape Fear with a foe of 1.24% had an average desorption of 61.7%. The Keyport soil with an intermediate foe of 3.72% desorbed an average of 43.3% of the test compound, a result that is between the Drummer and Cape Fear soil. The amount of test compound recovered in the second stage of desorption is generally comparable to that recovered in the first stage. There was no evidence of "tailing off" which suggests that if farther desorptions were performed more of the test compound would be recovered. T01 II/14107 Page 25 of 55 DuPontEMSE Report No. 17-03 The desorption results for the Hidalgo soil and the Wilmington Sludge sample were highly variable and ranged from 41.6 to 141% and 14.9 to 101%, respectively. In addition, the amount of test substance recovered varied between desorption steps 1 and 2 with the Hidalgo and Wilmington Sludge samples while the test substance recovery was more uniform with the other test soils. The total desorption values were inversely related to the test concentration in the Wilmington Sludge samples and decreased from an average of 98.9% at 100 |j.g/L to 14.9% at the 2500 p,g/L test concentration. This behavior was isolated to the sludge materials and remains unexplained in the current study. The variability seen in both the desorption experiments and the mass balance experiments of this study may be attributed to the difficulty in resuspending the soil pellets. The desorption and extraction phases required two sequential steps that required the mechanical disruption of the pellet to ensure complete suspension. Although there were unquantifiable soils losses with this procedure the solid losses and variability were present in all test materials and did not affect the overall behaviour of the test compound. 5.0 CONCLUSIONS The adsorption of the test compound ranged from 36.0 to 83.0% for a soihsolution ratio of Ig/mL for the five test materials. The average adsorption coefficient values, Kd, ranged from 0.61 mL/g for the Hidalgo soil to 5.63 mL/g for the Drummer soil. The activated sludge sample had the highest average Kd of 22.5 mL/g. The Freundlich adsorption coefficients (Kp) ranged from 0.59 |j,g 1-1/" (ml)17"g-1 for the Hidalgo soil to 5.64 p,g '"'^ (ml)17"g"1for the Drummer soil. The two sequential desorption steps, at a soihsolution ratio of 1 g/mL, recovered an average of 36.0 to 90.6% of the adsorbed test compound. 6.0 RETENTION OF RECORDS r's For the periods required by GLP guidelines and specific country requirements, study documents and materials will be stored in the archives ofDuPont CR&D Environmental & Microbiological Sciences and Engineering (EMSE) and/or Iron Mountain, Wilmington, Delaware USA, including but not limited to: study protocol; any protocol and/or report amendments or addenda or SOP deviations; all raw data; one original signed copy of the final report; laboratory-specific or site-specific raw data such as personnel files, instrument, equipment, refrigerator, and/or freezer raw data. T01 II/14107 Page 26 of 55 DuPont EMSE Report No. 17-03 Documents and materials are archived according to the principles of Good Laboratory Practice in the organization of the testing facility. 7.0 DISPOSAL OF TEST SUBSTANCE After issuance of the final report, the remaining test substance will be stored at the DuPont EMSE laboratory until its expiration date and then destroyed by burning, unless other arrangements are made between the facility supplying the test substance and the Test Facility. 8.0 REFERENCES 1. U.S. Environmental Protection Agency, Pesticide Assessment Guidelines, Subdivision N, EPA 540/9-82-021, pp. 64-71, 1982. 2. Organization for Economic and Cooperative Development (OECD) Guideline for the Testing of Chemicals 106, Adsorption/Desorption (January 21, 2000). 3. U.S. Environmental Protection Agency, Office of Prevention, Pesticides, and Toxic Substances (OPPTS), Fate, Transport and Transformation Test Guidelines, OPPTS 835.1110 Activated Sludge Sorption Isotherm, EPA 712-C-98-298, January 1998. 4. U.S. Environmental Protection Agency. 1989. Good Laboratory Practice Standards, 40 CFR, Part 160, Final Rule. EPA, Washington, D.C. 5. OECD Principles of Good Laboratory Practice published in ENV7MC/CHEM(98)17, OECD, Paris, France. 6. DuPont Central Research & Development, Environmental and Microbiological Science and Engineering Standard Operating Procedure. Adsorption-Desorption Using a Batch Equilibrium Method: EMSE067-P (June 2002). 7. U.S. Department of Health and Human Services, Food and Drug Administration. Guidance for Industry Bioanalytical Method Validation, May 2001. T01II/14107 Page 27 of 55 DuPont EMSE Report No. 17-03 TABLE 1 CHEMICAL AND PHYSICAL PROPERTIES OF TEST MATERIALS Site Soil Location Description Depth Drummer Rochelle, Illinois Fallow Top 20 cm Hidalgo Wilmington Sludge Cape Fear Donna, Texas Wilmington, Delaware Cooper River, South Carolina Bedded Fallow Top 20 cm Grass, walking path 20 - 30 cm Keyport Newark, Delaware Fallow Top 20 cm Texture Classification t Pa rtide Size Anal)'sis Zmm-SOum (Sand) 50-2um (Silt) <2mn (Clay) (%) (%) (%) Silt Clay Loam 12.0 60.0 28.0 Sandy Clay Loam 52.0 20.0 28.0 Sandy Loam 68.0 16.0 16.0 Sandy Loam 68.0 16.0 16.0 Loam 48.0 36.0 16.0 Soil Drummer Hidalgo Wilmington Sludge Cape Fear Keyport Bulk Density (g/mL) 1.1 1.3 0.4 1.4 1.2 foe Walldey- PH BIack % Moisture (%) (%) 7.6 5.76 7.8 0.77 6.7 61.7 5.4 1.24 5.5 3.72 5.95 3.32 8.14 0.93 1.91 Soil Drummer Hidalgo Wilmington Sludge Cape Fear Keyport Cation Exchange Capacity (nieq/lOOg) Hydrogen (% ofCEC) 36.6 25.7 10.2 3.1 9.5 0 0 0 12.8 31.5 Potassium (%ofCEC) 0.7 3.8 3.4 1.7 2.2 Magnesium (% ofCEC) 12.8 10.2 22.7 11.7 10.5 Calcium (%ofCEC) Sodium (% ofCEC) 86.2 0.2 83.4 2.6 69.5 4.4 71.8 2.1 55.2 0.6 >-&^-< ' *? Iwi t USDA system (sand: 2mm-50(im, silt: 50-2|jm, clay: <2|jm) T01II/14107 Page 28 of 55 DuPont EMSE Report No. 17-03 TABLE 2 DETERMINATK3N OF TEST SUBiSTANCE IN CACl.2; SOLUTIONS$ (No SOIL) Sample Description CaC12 Blank CaC12 Blank 100-1 100-2 500-1 500-2 1000-1 1000-2 2500-1 2500-2 Nominal Concentration Hg/L Measured Concentration f pg/L Deviation from Expected Value ^ % 0 0 100 100 500 500 1.00E+03 1.00E+03 2.50E+03 2.50E+03 15.5 15.6 96.7 103 566 587 876 972 1.86E+03 2.03E+03 ND0 ND -3.30 2.90 13.1 17.4 -12.4 -2.79 -25.4 -18.7 f Limit of Quantification (LOQ) = 10 p.g/L ^ Deviation from Expected Value = (Measured-Nominal)/Nominal x 100 Not Determined T01 II/14107 Page 29 of 55 DuPont EMSE Report No. 17-03 TABLE 3 DETERMINATION OF TEST SUBSTANCE IN CACLz SOIL EXTRACTS Sample Description CaC12 Blank CaC12 Blank Drummer Soil Blank 1 Drummer Soil Blank 2 Cape Fear Soil Blank 1 Cape Fear Soil Blank 2 CaClz Controls (No Soil) 100 ppb 100 ppb 500 ppb 500 ppb 1000 ppb 1000 ppb 2500 ppb 2500 ppb Drummer Soil Extract 100 ppb 100 ppb 500 ppb 500 ppb 1000 ppb 1000 ppb 2500 ppb 2500 ppb Cape Fear Soil Extract 100 ppb 100 ppb 500 ppb 500 ppb 1000 ppb 1000 ppb 2500 ppb 2500 ppb Measured Concentratiou ug/L <LOQf <LOQ <LOQ <LOQ <LOQ <LOQ 104 101 521 572 889 826 2.01E+03 2.51E+03 97.3 99.8 464 558 874 951 2.22E+03 2.19E+03 136 118 551 622 985 943 1.97E+03 2.34E+03 Deviation from Expected Value t % Dev iation from Mean Control Tube Measured Value 0 % 4.44 0.550 4.20 14.5 -11.1 -17.4 -19.4 0.516 -2.69 -0.200 -7.16 11.5 -12.6 -4.89 -11.3 -12.5 36.4 18.4 10.2 24.3 -1.46 -5.72 -21.1 -6.50 -5.06 -2.63 -15.1 1.99 1.91 10.9 -2.05 -3.41 33.1 15.5 0.805 13.7 14.9 9.90 -12.9 3.26 tLOQ=10u.g/L $ Deviation from Expected Value = (Measured-Nominal)/ Nominal x 100 <t>Deviation from CaC12 Mean Control Tube Value = (Measured-Mean CaC12 Control)/Mean CaC12 Control x 100 T0111/ 14107 Page 30 of 55 DuPont EMSE Report No. 17-03 TABLE 4 ADSORPTION TO TEST VESSEL Sample Description CaC12 Blank-1 Start CaC12 Blank-2 Start CaC12 Blank-1 24 hour CaC12 Blank-2 24 hour 100 ppb-1 Initial 100 ppb-2 Initial 100 ppb-1 24hr 100 ppb-2 24 hr 2500 ppb-1 Initial 2500 ppb-2 Initial 2500 ppb-1 24 hr 2500 ppb-2 24 hr Measured Concentration ug/L <LOQf <LOQ <LOQ <LOQ 93.2 98.1 90.8 98.3 1.64E+03 1.62E+03 1.19E+03 1.54E+03 Devi;ation from Initial Value f % NDO ND 5.07 -2.77 26.9 5.58 f LOQ Limit ofQuantitation = 10 |j.g/L ^ Deviation from Initial Value = (Average Initial Measured Concentration-Measured Concentration at 24hr)/ Average Initial Measured Concentration* 100 0 ND= Not Determined T01II/14107 Page 31 of 55 DuPont EMSE Report No. 17-03 TABLE 5 ADSORPTION IN PERCENT AS A FUNCTION OF SOIL:SOLUTION RATIO AND EQUILIBRATION TIME Time, hours 2 2 6 6 24 24 72 72 Drummer 1:1 65.3 72.4 75.7 73.3 83.9 79.8 78.8 NDf Drummer 1:5 29.9 36.6 32.9 37.7 39.3 51.2 48.1 ND Drummer 1:25 24.8 27.7 4.1 If 25.4 33.0 29.3 23.4 33.3 Hidalgo 1:1 21.1 9.28 30.5 22.5 42.2 39.3 27.7 35.8 Hidalgo 1:5 7.84 6.38 16.6 16.5 24.4 24.2 29.7 23.9 Hidalgo 1:25 -0.01 -1.61 6.84 18.7 20.1 25.9 12.3 3.17 f ND = Not Determined; Sample was lost ^ Result was an outlier and not reported in range of adsorption values T0111/14107 Page 32 of 55 DuPont EMSE Report No. 17-03 TABLE 6 MASS BALANCE CALCULATIONS OF DRUMMER AND HIDALGO SOILS PERFORMED AT 1:1 SOIL SOLUTION RATIO AFTER 24 MIXING Sample Description MEOH Blank MEOH Blank-2 Control Control Drominer Soil Blank 1 Drummer Soil Blank 2 Drummer 1000 ppb Test 1 Hidalgo Blank 1 Hidalgo Blank 2 Hidalgo 1000 ppb Test 1 Hidalgo 1000 ppb Test 2 Soil Dry Wt 8 19.3 18.9 19,1 19.8 19.2 19.6 19.5 Measured Concentration of Aqueous Phase at Equilibrium (19-Dec-02) (ig/L 1.14E+03 972 <LOQ <LOQ 224 <LOQ <LOQ 763 678 Test Substance iu Aqueous Phase at Equilibrium W 23.2 19,6 <LOQ <LOQ 2.92 <LOQ <LOQ 10.4 9.29 Measured Concentration of MEOH Extraction 1 (Ol-Feb-03) W!/I. <LOQt <LOQ 12.7 11.4 <LOQ <LOQ 323 <LOQ <LOQ 262 218 Test Substance in MEOH Extraction 1 W, 0.245 0.223 6.69 5.45 4.52 Measured Concentration of MEOH Extraction 2 (Ol-Feb-03) WS/L <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ 146 <LOQ <LOQ 72.3 70.0 Test Substance in MEOH Extraction 2 Test Substance in Void Volume m <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ 2.83 <LOQ <LOQ 1.41 1.38 n, <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ 1.11 <LOQ <LOQ 0.451 0.430 Total Test Compound Recovered "g <LOQ <LOQ 23.5 19.8 <LOQ <LOQ 13.6 <LOQ <LOQ 17.7 15.6 Mass Balance % NCf NC 119 100 NC NC 68.6 NC NC 89.8 79.0 f LOQ Limit ofQuantitation = 10 (ig/L } NC = Not Calculated, Mass Balance could not be determined because samples <LOQ T01 II/14107 Page 33 of 55 DuPont EMSE Report No. 17-03 TABLE 7 DEFINITIVE ADSORPTION STUDY; PERCENT ADSORPTION AND LINEAR ADSORPTION ISOTHERM PARAMETERS Sample ID Soil 1 100 ppb Soil 1 100 ppb Soill 500 ppb Soil 1 500 ppb Soil 1 1000 ppb Soil 1 1000 ppb Soil 1 2500 ppb Soil 1 2500 ppb Soil 2 100 ppb Soil 2 100 ppb Soil 2 500 ppb Soil 2 500 ppb Soil 2 1000 ppb Soil 2 1000 ppb Soil 2 2500 ppb Soil 2 2500 ppb Soil 3 100 ppb Soil 3 100 ppb Soil 3 500 ppb Soil 3 500 ppb Soil 3 1000 ppb Soil 3 1000 ppb Soil 3 2500 ppb Soil 3 2500 ppb Soil 4 100 ppb Soil 4 100 ppb Soil 4 500 ppb Soil 4 500 ppb Soil 4 1000 ppb Soil 4 1000 ppb Soil 4 2500 ppb Soil 4 2500 ppb Soil 5 100 ppb Soil 5 100 ppb Soil 5 500 ppb Soil 5 500 ppb Soil 5 1000 ppb Soil 5 1000 ppb Soil 5 2500 ppb Soil 5 2500 ppb Test Soil % Adsorption + Cs Cw logCs logCw Kd Koc Kom Drummer VS/S pg/L ftg/g tg/L mUs mL/g mL/g 82.2 0.08 16.4 -1.07 1.21 5.17 89.7 52.0 Drummer 79.3 0.08 18.9 -1.09 1.28 4.25 73.8 42.8 Drummer Drummer Drummer Drummer Drummer Drummer 82.7 88.9 82.0 85.3 82.9 80.6 0.39 0.45 0.83 0.86 2.01 1.95 73.4 50.3 164 135 374 425 -0.41 -0.35 -0.08 -0.07 0.30 0.29 1.87 1.70 2.22 2.13 2.57 2.63 5.35 8.86 5.04 6.39 5.38 4.60 92.9 154 87.6 111 93.5 79.8 53.9 89.2 50.8 64.3 54.2 46.3 Mean Hidalgo Hidalgo Hidalgo Hidalgo Hidalgo Hidalgo Hidalgo Hidalgo Mean 83.0 33.4 29.5 41.2 43.8 39.7 36.6 27.8 36.0 36.0 0.03 0.03 0.20 0.21 0.38 0.35 0.65 0.84 60.4 64.3 267 253 545 574 1.60E+03 1.42E+03 -1.49 -1.54 -0.70 -0.68 -0.42 -0.46 -0.18 -0.07 1.78 1.81 2.43 2.40 2.74 2.76 3.21 3.15 5.63 0.53 0.45 0.75 0.83 0.70 0.61 0.41 0.59 0.61 97.7 j 68.9 58.2 97.1 108 90.4 79.0 53.0 77.2 79.0 56.7 40.0 33.8 56.3 62.6 52.5 45.8 30.8 44.8 45.8 Witmington Sludge Wilmington Sludge Wilmington Sludge Wilmington Sludge Wilmington Sludge Wilmington Sludge Wilmington Sludge Wilmington Sludge Mean Cape Fear Cape Fear Cape Fear Cape Fear Cape Fear Cape Fear 69.5 70.8 74.6 77.7 83.4 82.7 87.3 83.4 78.7 64.8 63.3 70.8 73.7 60.3 59.3 0.35 0.37 1.95 1.91 4.40 4.27 10.7 10.9 0.06 0.06 0.33 0.34 0.52 0.55 28.1 26.8 119 106 155 161 291 390 32.5 33.7 134 121 348 372 -0.45 -0.44 0.29 0.28 0.64 0.63 1.03 1.04 -1.22 -1.23 -0.49 -0.46 -0.28 -0.26 1.45 1.43 2.08 2.02 2.19 2.21 2.46 2.59 1.51 1.53 2.13 2.08 2.54 2.57 12.6 13.7 16.3 18.1 28.3 26.4 36.8 27.9 22.53 1.87 1.73 2.43 2.84 1.51 1.48 20.5 22.2 26.5 29.3 45.9 42.9 59.6 45.3 36.5 151 140 196 229 121 119 11.9 12.9 15.4 17.0 26.7 24.9 34.6 26.3 21.2 | 87.5 80.9 114 133 70.4 69.1 Cape Fear Cape Fear Mean 54.1 61.4 63.5 1.22 1.02E+03 0.09 1.36 847 0.13 3.01 2.93 1.19 95.9 55.6 1.61 1.83 130 147.8 75.3 85.7 | Keyport 64.5 0.06 33.7 -1.21 1.53 1.82 48.9 28.4 Keyport Keyport Keyport Keyport Keyport Keyport Keyport 68.9 77.2 73.7 76.7 80.8 75.8 70.6 0.07 0.37 0.30 0.73 0.75 1.74 1.64 28.7 107 105 215 175 550 655 -1.19 -0.43 -0.52 -0.14 -0.13 0.24 0.21 1.46 2.03 2.02 2.33 2.24 2.74 2.82 2.27 3.48 2.90 3.39 4.26 3.17 2.50 61.1 93.4 77.9 91.0 115 85.1 67.2 35.4 54.2 45.2 52.8 66.5 49.4 39.0 Mean 63.1 2.85 90.7 52.6 t Adsorption determined on 1:1 (soils) and 1:5 (sludge) soil:solution ratio 24 hr equilibration time T0111/14107 Page 34 of 55 DuPont EMSE Report No. 17-03 TABLE 8 DEFINITIVE ADSORPTION STUDY; FREUNDLICH ADSORPTION ISOTHERM PARAMETERS Test Soil____ Slope (1/n) Drununer Hidalgo 0.994 1.00 Cape Fear Keyport Wilmington Sludge 0.885 1.11 1.36 Intercept (logK,) -2.25 -3.23 -2.49 -2.78 -2.41 R2 Kp (^'-"(niL)1'"^1_) ___(m_1_-_1"K- (p,n,L_)_1"_-g_-1_)___(n_g_l-Kl/ny(pm^L)1'- g-1) 0.97 0.96 0.96 0.97 5.64 0.59 3.23 1.64 98.0 76.2 261 44.2 56.8 44.2 151 25.6 0.98 3.90 6.3 3.7 T0111/14107 Page 35 of 55 DuPont EMSE Report No. 17-03 TABLE 9 DESORPTION OF TEST SUBSTANCE FROM TEST SOILS Sample Description Drummer 100 ppb Drummer 100 ppb Drummer 500 ppb Dntnimer 500 ppb Dnmuner 1000 ppb Drummer 1000 ppb Drummer 2500 ppb Drummer 2500 ppb Hidalgo 100 ppb Hidalgo 100 ppb Hidalgo 500 ppb Hidalgo 500 ppb Hidalgo 1000 ppb Hidalgo 1000 ppb Hidalgo 2500 ppb Hidago 2500 ppb Wilmington Sludge 100 ppb Wilmington Sludge 100 ppb Wilmington Sludge 500 ppb Witmington Sludge 500 ppb Wilmington Sludge 1000 ppb Wilminglon Sludge 1000 ppb Wilmington Sludge 2500 ppb Wilmington Sludge 2500 ppb Cape Fear 100 ppb Cape Fear 100 ppb Cape Fear 500 ppb Cape Fear 500 ppb Cape Fear 1000 ppb Cape Fear 1000 ppb Cape Fear 2500 ppb Cape Fear 2500 ppb KeyportlOOppb Keyport 100 ppb Keyport 500 ppb Keyport 500 ppb Keyport 1000 ppb Keyport 1000 ppb Keyport 2500 ppb Keyport 2500 ppb Measured Concentration Desorp 1 Soln Cpd Recovered in Desorp 1 Dcsurbed Stage 1 Measured Concentration Desorp 2 Soln Cpd Recovered in Desorp 2 Desorbed Stage 2 Total Cpd Recovered 1*9"13.3 12.9 73.9 93.0 211.5 166.8 397.8 367.4 28.3 29.7 124.3 125.1 148.9 138.3 426.4 158.5 52.7 49.4 142.2 139.1 112.9 121.5 129.7 174.7 18.4 20.8 162.1 113.3 173.9 169.4 439.0 447.2 23.5 22.0 35.5 30.5 162.8 100.5 227.5 412.2 pa 0.26 0.24 1.39 1.77 3.97 3.17 7.68 6.96 0.53 0.57 2.33 2.31 2.79 2.62 7.99 3.02 1.27 1.19 3.45 3.25 2.70 2.90 4.03 4.25 0.36 0.40 3.04 2.16 3.26 3.23 8.19 8.25 0.44 0.41 0.66 0.58 3.10 1.90 4.15 7.76 % 16.0 15.4 18.9 20.7 25.2 19.2 20.0 18.7 85.5 102.2 60.6 57.0 37.7 38.5 62.4 18.4 78.1 72.3 38,8 35.0 13.6 14.9 8.0 8.6 29.8 34.1 46.5 31.7 31.0 29.7 33.8 30.5 37.1 31.8 9.1 9.8 21.8 12.8 11.8 24.3 "a'i- 9.53 11.6 53.8 48.0 113 75.8 182 190 7.99 7.86 45.1 43.3 89.6 102 137 141 11.4 12.6 53.2 29.3 70.7 45.9 66.8 96.8 10.2 10.4 70.6 64.6 161 145 221 197 7.66 10.2 61.7 68.0 152 143 221 201 M 0.27 0.33 1.51 1.33 3.09 2.11 5.10 5.27 0.22 0.21 1.24 1.18 2.47 2.81 3.74 3.84 0.37 0.40 1.71 0.96 2.24 1.48 2.17 3.12 0.28 0.28 1.93 1.76 4.45 3.99 6.09 5.41 0.21 0.29 1.71 1.92 4.28 3.97 6.28 5.64 % 16.8 21.4 20.4 15.6 19.6 12.8 13.3 14.2 35.3 38.8 32.3 29.1 33.4 41.2 29.2 23.5 22.6 24.5 19.2 10.4 11.3 7.60 4.30 6.33 23.2 23.9 29.6 25.8 42.2 36.7 25.1 20-0 17.5 22.4 23.6 32.4 30.1 26.7 17.9 17.7 pg 0.53 0.56 2.90 3.09 7.06 5.27 12.8 12.2 0.75 0.78 3.57 3.49 5.26 5.43 11.7 6.86 1.64 1.60 5.16 4.21 4.94 4.39 6.20 7.37 0.64 0.68 4.97 3.92 7.71 7.22 14.3 13.7 0.65 0.69 2.37 2.50 7.38 5.87 10.4 13.4 Desorption Total % 32.9 36.7 39.3 36.3 44.7 32.0 33.3 32.9 121 141 92,9 86.0 71.2 79.7 91.6 41.9 101 96.8 58.0 45.4t 25.0 22.5 12.3t 14.9 53.0 57.9 76.1 57.5 73.2 66.5 58.9 50.5 54.7 54.2 32.7 42.2 51.9 39.5 29.8T 41.9 f Soil tube spilled during processing; not included in average calculations t Adsorption supernatant added to soil tube during processing; not included T01 II/14107 Page 36 of 55 DuPont EMSE Report No. 17-03 FIGURE 1 ANALYTICAL METHOD VALIDATION OF CACLz CONTROLS (NO SOIL) AND EXTRACTS FROM DRUMMER AND CAPE FEAR SOILS CaCl2f Drummer f A Cape Fear $ 0 1000 2000 3000 Target concentration, (Ag/L f y==0.8928x+23.403, R^ 0.978 fy=0.8749x+27.432, R2 = 0.998 Oy=0.8463x+73.34, R2 = 0.983 T01 II/14107 Page 37 of 55 DuPont EMSE Report No. 17-03 FIGURE 2 ADSORPTION OF TEST SUBSTANCE AS A FUNCTION OF SOIL:SOLUTION RATIO AND EQUILIBRATION TIME WITH DRUMMER SOIL 1AA tW -------------------------------------------------------------------------------------------------------------------------------- l:l SoiLSolution Ratio A 1:5 SoihSolution Ratio 6U s 0 n U^ o 6rru\ "" 1:25 Soil:Solution Ratio 0 A a' t 0 AH - ^^--------------------^--------------------------------------------------------^-------- .ff -rtj 0. A 0 4 m 'O <^ ! 2^<nJ n - 10 20 30 40 50 60 70 80 Ecjuilibration Time, Hours '' "rMsfHi T01 II/14107 Page 38 of 55 DuPont EMSE Report No. 17-03 FIGURE 3 ADSORPTION OF TEST SUBSTANCE AS A FUNCTION OF SOIL:SOLUTION RATIO AND EQUILIBRATION TIME WITH HIDALGO SOIL 1UU - 1:1 Soil:Solution Ratio -- oU S 0 n '--o i f6iUo A 1:5 Soil:Solution Ratio 1:25 Soil:Solution Ratio e? . : : -^--------*----------------------.-- ft Q 4A1f)\ sa & * * wi '0 i^nU "<! n - 10 20 30 40 50 60 70 80 Equilibration Time, Hours T01II/14107 Page 39 of 55 DuPont EMSE Report No. 17-03 FIGURE 4 AVERAGE KoVS FRACTION OF ORGANIC CARBON FOR DRUMMER, HIDALGO, CAPE FEAR AND KEYPORT SOILS 2 3 4 5 6 Fraction of organic carbon, % T01II/14107 Page 40 of 55 DuPont EMSE Report No. 17-03 FIGURE 5 AVERAGE KOMVS FRACTION OF ORGANIC CARBON FOR DRUMMER, HIDALGO, CAPE FEAR AND KEYPORT SOILS 90 80 70 60 I 50 | 40 s 30 20 10 y=-1,1945x+64556- R^ 0.0651 4 6 10 Fraction of organic matter, % T01 II/14107 Page 41 of 55 DuPont EMSE Report No. 17-03 FIGURE 6 AVERAGE KocVS FRACTION OF ORGANIC CARBON FOR DRUMMER, HIDALGO, CAPE FEAR AND KEYPORT SOILS 160 140 120 ^S 100 S 80 C3 I 60 40 20 0 y=-3.5502x+111.29 R =0.0651 2Fra 3ction of 4organic5carbon6, % T01II/14107 Page 42 of 55 DuPont EMSE Report No. 17-03 FIGURE 7 LINEAR ADSORPTION ISOTHERM OF THE TEST SUBSTANCE IN DRUMMER SOIL 3.U - 4.5 - 4.0 - 6C -33 i3-5< - --------------------------------------------------y=0.00'18x+0.0825---- 1ca 30 .0f\ - 2 -2).<5 - R2 = 0.9766 u S 2.0 - ----------------------------------------------------^^-^---------- 3 1.5- ^^^^ 1.0 ^ ^ ^ ^ e ^ ^ 0.5 nn - 100 200 300 400 500 Cw, nucrograms/L "-'^.irMa- T01 II/14107 Page 43 of 55 DuPont EMSE Report No. 17-03 FIGURE 8 LINEAR ADSORPTION ISOTHERM OF THE TEST SUBSTANCE IN HIDALGO SOIL 500 1000 1500 Cw, micrograms/L 2000 T01 II/14107 Page 44 of 55 DuPont EMSE Report No. 17-03 FIGURE 9 LINEAR ADSORPTION ISOTHERM OF THE TEST SUBSTANCE IN CAPE FEAR SOIL 200 400 600 800 1000 1200 Cw micrograms/L T01 II/14107 Page 45 of 55 DuPont EMSE Report No. 17-03 FIGURE 10 LINEAR ADSORPTION ISOTHERM OF THE TEST SUBSTANCE IN KEYPORT SOIL J.U - 4.5 - 4.0 - 6J) i c % 3-5 .,, s ca 3.0 - I?CD 2.5- u "a 2.0 - ^VI 1.5 - 1.0 0.5 nn - y= 0.0027x4-0.0747 R^ 0.9532 ^^^^^^ ^-^^^ ^r^ 200 400 600 800 1000 Cw niicrograms/L T0111/14107 Page 46 of 55 DuPontEMSE Report No. 17-03 FIGURE 11 LINEAR ADSORPTION ISOTHERM OF THE TEST SUBSTANCE IN WILMINGTON SLUDGE 0 100 200 300 400 500 Cw micrograms/L T01 II/14107 Page 47 of 55 DuPont EMSE Report No. 17-03 FIGURE 12 FREUNDLICH ADSORPTION ISOTHERM OF THE TEST SUBSTANCE IN DRUMMER SOIL Z.U - 1.5 01) 1.0 CB s VS BJO 0.5 0 u y=0.994x-2.2485 ^^ ^= 0.967 ^^ s < 1 Kl 3 4 : U -0.5 - ------------------""----------------------------------------------l 6D 0 1-1 -1.0 .V ^ -1.5 - on - Log Cw micrograms/L T01 II/14107 Page 48 of 5 5 DuPontEMSE Report No. 17-03 FIGURE 13 FREUNDLICH ADSORPTION ISOTHERM OF THE TEST SUBSTANCE IN HIDALGO SOIL Z.U - 1.5 OJO '33 1.0 s C3 0.5 - 6X) 2 u S 0.0 ^ -0.5 - bfi 0 -) -1.0 -1.5 - '7 n - y =1.0016x-3.2314 R^ 0.9625 1 2 t^3 4 : .>- ^ Log Cw micrograms/L T01 II/14107 Page 49 of 55 . DuPont EMSE Report No. 17-03 FIGURE 14 FREUNDLICH ADSORPTION ISOTHERM OF THE TEST SUBSTANCE IN CAPE FEAR SOIL z.u - 1.5 - w '33 1.0 s a L> 0.5 - bj) o u 's 0.0 3 i> -0.5 - -1.0 -1.5 - '> n - y=0.8853x-2.4902 V2= 0.961 ^ /^' ^ 1 ^^^ 3 4 ^ Log Cw mierograms/L T01II/14107 Page 50 of 55 DuPontEMSE Report No. 17-03 FIGURE 15 FREUNDUCH ADSORPTION ISOTHERM OF THE TEST SUBSTANCE IN KEYPORT SOIL z.u - 1.5 - ^OJU 1Lof\ s y= 1.1137x-2.7844 R2^ 0.9666 ffi ^ f ^ 0.5 - &c 0 ^ s s 0.0- --------------,--------------,--^--^------,--------------r-..., ( > 1 Q -0.5 3 4 : / I/ BD 0 ^ -- -li .uf\ ^ -1.5 - in - Ijog Cw micrograms/L T01 II/14107 Page 51 of 55 DuPont EMSE Report No. 17-03 FIGURE 16 FREUNDLICH ADSORPTION ISOTHERM OF THE TEST SUBSTANCE IN WILMINGTON SLUDGE A U 1.5 - --------------/~^ ^BJU 1Lof\ S 0.5 /\ cQ ^ fc" - &o y=1.3571x-2.409 R2^ 0.9827 0 1 5 o.o-------------y^ ./ ------1-r" 3 0 1 2 -0.5 -------------------- ------- -------- 3-J------------J w 0 h^j 1 n -l.u - -1.5 --^\/lfl\ Log Cw inicrograms/L T01 II/14107 Page 52 of 55 DuPont EMSE Report No. 17-03 FIGURE 17 TOTAL DESORPTION VS FRACTION OF ORGANIC CARBON FOR DRUMMER, KEYPORT AND CAPE FEAR SOILS 100 90 a o 80 Io & 70 60 Q o> bfi es u ^ 20 i 10 0 E-i y=-2.0131x+ 48.727 R ==08665 2 4 Fraction of Organic Carbon, % T01 II/14107 Page 53 of 55 DuPont EMSE Report No. 17-03 APPENDIX 1 AMMONIUM PERFLUOROOCTANOATE ANALYTICAL METHOD Operating Conditions The LC column is equilibrated with 95% Solvent A (5% Methanol in 2mM Ammonium Acetate) and Solvent B (100% Methanol). The method utilizes a linear gradient with the following conditions: Time (min) 0 1 6 8 9 13 Solvent B % 5 5 100 100 5 5 Flow (ml/min) 0.25 0.25 0.25 0.25 0.25 0.25 The flow is diverted to waste between 0-3 minutes and directed to the mass spectrometer between 3 to 12.5 minutes. The injection volume is 25 microliters. The mass spectrometer is optimized for the molecular anion at 413 m/z with the Capillary Voltage set at 3.0kV, Cone Voltage set at 10V, the source block temperature is set at 150C and desolvation temperature is set at 200C. The collision cell is maintained at a pressure of argon 1.0 E-3 and nitrogen flow is maintained at 100 psi. The mass spectrometer monitors the transition 423 > 369. T01II/14107 Page 54 of 55 DuPont EMSE Report No. 17-03 APPENDIX 2 CERTIFICATE OF ANALYSIS OF TEST SUBSTANCE SiffsiSfAWch Gsrtifastie ofAaatyMS fay 1 t>f2 LOT ysssarH} RESULTS PenlacaCtiBuorogdanoic sctd artOTionrjm salt 77268 M25281 G,H,F.,NO, toiMllWi^it UlRAIION (W{>HCLO* MM ^TOEAHASCt! sot.uoa.iTy (cos-ousi 431.1 mjs% WHITE powoea COLOURLESS soi.it.H<iuBetB(y! S-3LUBeltY((Ha-J) MHTiR (a;sau6on;<iitinort IKfRAREn SPECTRUM CLEAR (-0.6 TE(F5> 1QJN10MH20 B.1% <0.1% CORRES?ONOS tIAIZWW-ftfLEAK a4fJA?ff01 Fluka guaranteaa the 'Salst-SpBCtfcation' vatuw ort^, non-Speaiieil Se*s. may ba IrKautted as additional InfonBalton. Tha suirent 'Satet-Spsclitealianis' sheel te wallaya n Mtfu9^.. Ferfcirthar inqriiSes, pte BgnlaelourTfidinica] SarsaCBFluka wairaels. that Ite |iroifuels conroan te tils tflfomiaUan Clitslametl in (his anrf other Fluka publications- Purchaser must daiennaia tha suiiabiHy of the pro&fct lor iis particalar use. Sae tevisse sitte ef invi^CB te atitlltional tenns and creiifiHtMis of Bal. Tha vatutts giyen en Ihe 'Certificate ol Ana^'sis* ara the restilis iSelarminadi at tte tea of analysis. ^^-^ Dr. 6. van Lioafc &l^/ifow.MM"aldriA.e<m^<si-bin/^<!gUAwiei<?COrAlnft.R^ ia)flTO T01 II/14107 Page 55 of 55