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AR226-1030A041 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 Study Title Screening Studies on the Aqueous Photolytic Degradation of Potassium Perfluorooctane Sulfonate (PFOS) Data Requirement Consistent With: OPPTS: 835.5270 "Indirect Photolysis Screening Test" -and- OECD Draft Document "Phototransformation of Chemicals in Water - Direct and Indirect Photolysis", August 2000 Author Thomas L. Hatfield, Ph.D. Study Completion Date April 23rd, 2001 Performing Laboratory 3M Environmental Laboratory Building 2-3E-09, 935 Bush Avenue St. Paul, MN 55106 Project Identification 3M Laboratory Report No: W2775 Total Number of Pages 158 Page 1 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 This page has been reserved for specific country requirements. Page 2 of 158 BACK TO MAIN 3M Environmental Report No. W2775 Non - Compliance Statement Study Title: Screening Studies on the Aqueous Photolytic Degradation of Potassium Perfluorooctone Sulfonate (PFOS) Study Identification Number: W2775 By design, this study does not comply with the requirements of the US EPA Good Laboratory Practices Standards at 40 CFR Part 792 (TSCA). However, the 3M Environmental Laboratory Quality Assurance Unit has performed audits of all data, related documentation and final report. Test and reference substance receipt and use, dosing and incubation of the test system, and analyses were conducted and documented according to procedures developed by 3M, based on references 1 and 2. Page 3 of 156 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 Quality Assurance Statement Study Title: Screening Studies on the Aqueous Photolytic Degradation of Potassium Perfluorooctane Sulfonate (PFOS) Study Identification Number: W2775 This study has been inspected by the 3M Laboratory Quality Assurance Unit as indicated in the following table Inspection Dates 03/30/01 - 04/2/01 04/19/01-04/20/01 Phase Data Draft Report Date Reported to Management Study Director 04/02/01 04/02/01 04/20/01 04/20/01 Quality Assurance Unit 4* tL Date ol Page 4 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 Table of Contents Non - Compliance Statement..................................................................................................3 Quality Assurance Statement................................................................................................. 4 Table of Contents.................................................................................................................... 5 Study Personnel and Contributors..........................................................................................7 Study Personnel and Contributors..........................................................................................7 Summary..................................................................................................................................8 Introduction...............................................................................................................................9 Materials and Methods............................................................................................................ 11 Chemical Characterization.................................................................................................11 Method Summaries............................................................................................................ 11 Results and Discussion..........................................................................................................13 Data Quality Objectives......................................................................................................13 Analytical Results............................................................................................................... 14 Data Summary and Discussion........................................................................................ 14 Conclusions............................................................................................................................ 17 References.............................................................................................................................. 18 Signatures................................................................................................................................19 Appendix A: Analytical Methods............................................................................................... 20 Appendix B: Chemical Characterization................................................................................. 104 Appendix C: Kinetics Model and Kinetic Calculations................ ............................................108 Appendix D: Individual Sample Data........................................................................................118 Appendix E: Representative Chromatograms........................................................................ 130 Appendix F: Soil Types and Characterizations....................................................................... 148 Appendix G: Light Intensity Measurements at 45 South Latitude (Miami FL)........................150 Appendix H: Characteristics of the Spectral Output of the SuntestInstruments..................152 Page 5 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 List of Tables Table 1. Typical Sample Preparation Scheme Used in the Study.......... ............................. 12 Table 2. Observed Products and Mass Balance Determinations for Water, Synthetic Humic Water and Iron Oxide Containing Water..................................................................15 List of Figures Figure 1. Structures of the Compounds Targeted by LC/MS Analysis.................................9 Figure 2. Pooled Concentration Data from the Iron Oxide Rich Matrix................................ 16 Page 6 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 Study Personnel and Contributors Study Director Thomas L. Hatfield, Ph.D. 3M Environmental Laboratory Building 2-3E-09 935 Bush Avenue St. Paul, MN 55106 (651) 778-7863 Sponsor 3M Corporation 3M Environmental Laboratory Contributing Personnel Kent Lindstrom Anh Dao Vo 3M Environmental Laboratory Professional Services Contributing Personnel Anthony (Tony) Scales Debra Wright Jan Schutz Rufat Mischiev (Pace Analytical Services, Inc., 1700 Elm St., Minneapolis, MN 55144) Kristin Terrell Jill Maloney Karen Johnson (Braun Intertec Corporation, 6875 Washington Ave. South, Minneapolis, MN 55439) Location of Archives Digital copies of original data, and all original paper data have been archived and will be retained in the 3M Environmental Laboratory archives for at least 10 years Page 7 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 Summary We report here the results of studies performed to determine the aqueous photolytic behavior of potassium perfluorooctane sulfonate (PFOS) and to identify its primary degradation products, if any. Our techniques are based on both EPA and OECD guidance documents.1,2 In this study, both direct photolysis (the interaction of light with the target molecule leading to a chemical change) and indirect photolysis (the Interaction of light with the sample matrix to produce radical species that subsequently react with the target material) were studied using an artificial light source. Neither direct nor indirect photolytic decomposition of PFOS was observed based on loss of starting material nor were any of the predicted degradation products detected above their limits of quantitation. The rates of photolytic degradation are highly dependent on the experimental conditions. However, using an iron oxide (Fe203) photoinitiator matrix model, we estimate the environmental half-life of PFOS to be greater than 3.7 years. Page 8 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 Introduction Photolysis reactions, hydrolysis reactions and biodegradation are the primary routes of degradation of chemical compounds in the environment. Studies of photo-induced reactions yield information on the persistence of the parent material as well as information on the identity and stability of products formed. Photolytic reactions occur by two types of mechanisms. The first mechanism, direct photolysis, can be defined as the direct absorption of a photon by the target species that leads to a chemical change. The second mechanism, indirect photolysis, can be defined as a chemical or electronic excitation transfer from a light absorbing species to the test substance, which then undergoes some type of chemical change. In the present investigation, an artificial light source was used to study both the direct and indirect photolysis reactions of PFOS. The test material, PFOS, was dissolved in an aqueous solution and then exposed to simulated sunlight to test for direct photolytic decomposition.3,4 To test for indirect photolysis, PFOS was dissolved into three separate matrices and exposed to simulated sunlight for periods of time from 67 to 167 hours. These exposures tested how each particular matrix would affect the photolytic decomposition of PFOS. The first test matrix was an aqueous solution to which H2O2 was added as a well characterized source of OH radicals.5,8 This matrix was used to test for the propensity of PFOS to undergo indirect photolytic decomposition. The second matrix contained Fe203 in water, a matrix that has been shown to generate hydroxyl radicals via a Fenton-type reaction in the presence of both natural and artificial sunlight.7,8 The third matrix contained a standard humic material, which was diluted to levels that have been shown to be environmentally relevant.1,2 To effectively determine photolytic decomposition, the concentration of parent material must be monitored over time. Further, it is also important to understand what the degradation products are and how much, if any, of each are formed. The present investigation quantified the parent material and the predicted degradation product perfluorooctanoic acid (PFOA) by LC/MS. Structures of the two pertinent compounds are illustrated in Figure 1. Figure 1. Structures of the Compounds Targeted by LC/MS Analysis PFOA H t -- H l PFOS Because it was possible that volatile degradation products could be produced, it was decided to monitor for selected C2 through C8 1- or 2- substituted perfluoronated olefins (e.g. C8Fi6) and 1- or 2- substituted hydrides (e.g. C8Fi 7H) in both the iron-rich matrix and the aqueous matrix by dynamic purge and trap gas chromatography/mass spectrometry. The selected target compounds are representative of the types of volatile compounds that could be generated in the photolysis of PFOS. Page 9 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 Determination of a maximum kinetic rate constant (k P) was based on the data from the iron rich matrix (as the experimental error was lowest in this matrix) using the following first order kinetics equation. (See Appendix C for a complete kinetic derivation and the exact mathematical solution. This equation is valid for essentially constant parent concentrations with a mean value Pp and a standard deviation of ap.) k- s ( k , ) _ = pP A t (C38) Page 10 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 Materials and Methods Chemical Characterization Information on the chemical characterization of both reference substances and control substances is presented in Appendix B. Method Summaries Copies of all analytical methods used in this investigation are attached in Appendix A. Equipment settings, conditions and complete quality control parameters are listed in the pertinent methods. UVA/isible analysis was performed following 3M Environmental Laboratory Method ETS-946.0 "Operation and Maintenance of the Hewlett Packard 8453 UV-Visible Spectrophotometer" An aqueous saturated solution of PFOS was prepared and an initial UVA/IS spectrum recorded. No absorbance above baseline over the range 190-1100 nm was detected. Sample preparation for this analysis followed 3M Environmental Laboratory Method ETS-8177.0 "Indirect Photolysis Screening Tests in Synthetic Humic Water" or ETS-8-176.0 "Preparation of Samples for Photolytic Exposure Studies in Aqueous Matrices". A typical sample preparation table for an indirect photolysis screening test is shown in table 1 on the following page. The general method of sample preparation is as follows. For each time point under each condition shown in table 1, ten 40-mL sample screw cap VOA vials were prepared: sample, duplicate, triplicate, sample spike, matrix blank, matrix blank spike (assured no accidental contamination of matrix by target compounds), direct photolysis sample, direct photolysis sample spike (assured that degradation observed was due to indirect photolysis and not another process), control blank and control blank spike (assured no accidental contamination of the blank had occurred). All vials contained 5 mL of appropriate matrix: pH 7 buffer, Fe+3 at a 24X molar excess in water, or H2C>2 at 1:1 molar equivalent, added every 24 hours. Aliquots of PFOS were added to the vials as indicated in table 1. The initial time point vials (labeled as 'Time Zero" on the sample analysis sheets in Appendix D) were then refrigerated at 42C. Th ese sam ples served as controls with which to determine what change, if any, occurred during the time the remaining vials were in the photo-reactor. Exposed samples were placed upside down in a custom built holder in the photo-reactor. Unexposed samples were wrapped in aluminum foil, sealed in a plastic bag and placed under the sample rack inside the photo-reactor to assure that any degradation or difference in degradation was due to photolysis and not some other process. During the course of the exposure, a water bath held the temperature of the water surrounding the bottom of the vials (which contained the aqueous samples) at 25 3C. The temperature of the chamber itself was allowed to drift to 70 +10C. After exposure, the samples were removed for analysis. Selected portions of the sample setup were modified to accommodate additional samples and controls, to improve the quality control of the analysis or out of experimental necessity. Specifics of these modifications are shown on individual sample data sheets shown in Appendix D. For example, the portion of the study employing iron oxide as a radical generating species was set up with both triplicate samples and duplicate sample spikes. Page 11 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 The artificial light chamber used in this analysis was either a Suntest CPS+ or Suntest XLS+, the operation of which followed 3M Environmental Laboratory Method ETS-9-44.0 "Operation and Maintenance of the Sunlight Exposure System, Immersion Unit, and Recirculating Water Chiller System". The output intensity was held at the desired level (680 w/m2) by a continuous feed back loop between an internal radiometer and the variable light source. Table 1. Typical Sample Preparation Scheme Used in the Study Description Ind. Photo. Sample Rep 1 Ind. Photo. Sample Rep 2 Ind. Photo. Sample Rep 3 Ind. Photo. Sample Spike Matrix Blank Matrix Blank Spike Direct Photo. Sample Direct Photo. Spike Control Blank Control Blank Spike Test Matrix (e.g. Fe20 3 in water) + + + + + + 0 0 0 0 Control Matrix (e.g. water) 0 0 0 0 0 0 + + + + Test Substance (PFOA) + + + + 0 0 + + 0 0 Post Photolysis Target Analyte spike 0 0 0 + 0 + 0 + 0 + Sample Type (Conditions) Initial Initial Initial Initial Initial Initial Initial Initial Initial Initial L C /M S * With W/out HA HA XX XX XX XX XX XX XX XX XX XX GC/MS* With W/out HA HA XX XX XX XX XX XX XX XX XX XX Ind. Photo. Sample Rep 1 Ind. Photo. Sample Rep 2 Ind. Photo. Sample Rep 3 Ind. Photo. Sample Spike Matrix Blank Matrix Blank Spike Direct Photo. Sample Direct Photo. Spike Control Blank Control Blank Spike + + + + + + 0 0 0 0 0+ 0+ 0+ 0+ 00 00 ++ ++ +0 +0 0 Light X X X X 0 Light X X X X 0 Light XXX X + Light XXX X 0 Light X X X X + Light X X X X 0 Light X X X X + Light X X X X 0 Light XXX X + Light X X X X Ind. Photo. Sample Rep 1 Ind. Photo. Sample Rep 2 Ind. Photo. S am ple R ep 3 Ind. Photo. Sample Spike Matrix Blank Matrix Blank Spike Direct Photo. Sample Direct Photo. Spike Control Blank Control Blank Spike + + + + + + 0 0 0 0 0+ 0+ 0+ 0+ 00 00 ++ ++ +0 +0 0 No Light X X X 0 N o Light X X X 0 No Light X X X + No Light X X X 0 No Light X X X + No Light X X X 0 No Light X X X + No Light X X X 0 No Light X X X + No Light X X X + = added to test vial; 0 = NOT added to test vial; 'Duplicate sets, one with H A , one without (excludes the Humic material test where H20 2was not added) X X X X X X X X X X GC/MS analysis followed 3M Environmental Laboratory Method ETS-8-182.0 "Analysis of Fluorochemicals by Archon Purge and Trap Autosampler, Tekmar Purge and Trap Concentrator and Agilent Gas Chromatograph/Mass Spectrometer". Equipment settings, separation conditions and ions monitored are presented in this method. Equipment procedures for the GC/MS system followed 3M Environmental Laboratory SOP ETS-9-49.0 "Routine Maintenance Page 12 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W 2775 of Archon Purge and Trap Autosampler, Tekmar Purge and Trap Concentrator and Agilent Gas Chromatograph/Mass Spectrometer". The HPLC/MS analysis followed 3M Environmental Laboratory Method ETS-8-181.0 "Analysis of Photolysis Samples for Fluorochemicals by High Performance Liquid Chromatography With Mass Spectrometry Detection". Equipment settings, separation conditions and ions monitored are presented in this method. Results and Discussion Data Quality Objectives The following data quality objectives are summaries of those found in the methods from Appendix A. Calibration curves. An acceptable coefficient of determination (R2) for linear curves is 0.990 or greater. Curve linearity, intercept, and quantitation accuracy should be verified, particularly at upper and lower calibration limits. Residuals generated in curve-fitting must be within 25% of the known standard value. Alternative methods of curve-fitting (e.g., quadratic) require a correlation coefficient (r) of 0.990 or greater. Reasons for the use of quadratic curve-fitting must be documented in the raw data. Solvent blanks, Matrix blanks, Control blanks. Blanks should show no more than 5% of the level of a high standard or CCV and should show less than 25% of the lowest point of the calibration curve. If solvent blanks show more than a 5% carryover, it may be necessary to rule out instrument contamination using duplicate solvent blank injections. If, after duplicate solvent blanks, there is still more than 5% carry-over, or the LOQ is adversely affected, the run should be stopped. This indicates that the instrument is contaminated and should be thoroughly cleaned. Sample spikes, Matrix spikes, Control spikes. Acceptable spike recoveries must be between 75 and 125% for LC/MS and GC/MS analysis. Values outside these ranges must be documented and evaluated by the Team Leader or designated supervisor. Sample triplicates. All samples are prepared in triplicate (unless otherwise noted). Acceptable RSD precision values are less than or equal to 25%. Values above 25% must be documented and evaluated by the Team Leader or designated supervisor. Continuing calibration verification (CCV). The analyte concentrations must not vary by more than 25% of their expected values, relative to the initial calibration curve. Accept only those samples analyzed before the most recently accepted calibration verification. Reanalyze remaining samples with a new calibration curve. Limit of Quantitation. The limit of quantitation (LOQ) is equal to the concentration of lowest standard in the calibration curve that has an area greater than or equal to four times the solvent blanks and possessing a residual less than 25% of the actual value. Control Samples. Control samples must be within 25% of the nominal concentration. Page 13 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 Analytical Results Data quality objectives for this study, outlined in the 3M laboratory method for this study (see Appendix A), were met, with the exceptions noted in the Deviations section in Appendix D. Calibration curves. Calibration curves were prepared for each target compound at various levels; please see Appendices A and D for details. Using appropriate standards, calibration curves were run before and after every analytical sequence. A correlation coefficient (r) of 0.990 or greater was achieved for all curves. Solvent blanks. All solvent blanks (MeOH) were less than 25% of the method LOQ except where noted in Appendix D. Sample spikes. All spike recoveries for the LC/MS and GC/MS analysis of the study investigation were between 25%, except where noted in Appendix D. Sample triplicates. All sample RSD values were 25% or less except where noted in Appendix D. Continuing calibration verification. All CCV samples were within 25% of the expected value. Limit of Quantitation. The LOQ varied dependant upon target and was set equal to the lowest point in the calibration curve. Method Blanks. All method blanks were below 25% of the LOQ. Control Samples. All control samples were within 25%. Data Sum mary and Discussion Direct and indirect photolytic decomposition of PFOS was tested in three separate matrices: an aqueous matrix, a synthetic humic water and an iron rich water. The samples were exposed to 680 w/m2 over the wavelength range of 290-800 nm and for time periods of 67-167 hours. Results for the quantitation of the parent material and the potential degradation products over time, as well as mass balance determinations, are shown in table 2. While setting up additional studies on the photochemical behavior of other compounds in synthetic humic material, it was determined that the commercial humic material (Aldrich) did not contain the appropriate amount of dissolved organic carbon when the solution is prepared as recommend in reference 1. The study director believes that this may have inhibited any possible photodegradation of PFOS in this matrix and that these data should therefore be considered of screening quality only. Further, the samples from this matrix showed high levels of background ions with the same charge to mass ratio as that of the targeted materials and the manual integration of some peaks was therefore required. Page 14 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 Table 2. Observed Products and Mass Balance Determinations for Water, Synthetic Humic Water and Iron Oxide Containing Water 2a. Matrix: Water, With and Without H2O2 Sam ple C o n d itio n s 167 hour Exposure Ind. Photo. S am p le1 Dir. Photo. S am ple2 Initial Tim e Point Initial Tim e Point Ind. Photo. S am p le1 Dir. Photo. Sam ple2 Exp. to Light Exp. to Light Ind. Photo. S am p le1 Dir. Photo. S am ple2 Not Exposed Not Exposed D etection Lim its PFOS nanom oles 97.9 95.7 96.3 94.3 93.3 96.3 3.75 PFOA nanom oles ND ND ND ND ND ND 0.023 V o la tile s nanom oles ND ND ND ND ND ND 0.0095* Mass Balance (p e rc e n t) 104% 102% 102% 100% 99.2% 102% Vials initially contained 94.1 nMoles PFOS. 1. Indirect Photloysis Sample: These samples had H20 2added as a radical source, results are from triplicate samples. 2. Direct Photolysis Sample: These samples did not have H20 2 added, results are from triplicate samples. *Sum total of all volatiles. ND = non detect. 2b. Matrix: Fe203 in Water, With and Without H2O2 Sam ple C o n d itio n s 167 hour Exposure F e20 3 W / H A 1 F e A W O /H A 2 Initial Tim e Point Initial Tim e Point F e A W /H A 1 Fb 20 3 w o / h a 2 F e20 3 W / H A 1 Exp. to Light Exp. to Light Not Exposed F e A W O /H A 2 Not Exposed D etection Lim its PFOS nanom oles 97.4 95.2 96.9 95.9 94.3 96.9 3.75 PFOA nanom oles ND ND ND ND ND ND 0.023 V o la tile s nanom oles ND ND ND ND ND ND 0.0095* Mass Balance (p e rc e n t) 103% 101% 103% 102% 100% 103% Vials initially contained 94.1 nMoles PFOS. 1. Samples had H20 2and Fe20 3added as a radical generating species, results are from triplicate samples. 2. Samples contained just Fe20 3as a radical generating species, results are from triplicate samples. *Sum total of all volatiles. ND = non detect. 2c. Matrix: Synthetic Humic Water Sam ple C o n d itio n s 67 hour Exposure Hum ic W ater1 Initial Tim e Point W ater2 Initial Tim e Point Hum ic W ater1 Exp. to Light W ater2 Exp. to Light Hum ic W ater1 Not Exposed W ater2 Not Exposed D etection Lim its PFOS nanom oles 6.52 6.63 6.51 6.32 6.69 6.50 0.037 PFOA nanom oles ND ND ND ND ND ND 0.046 Mass Balance (p e rc e n t) 92.5% 94.1% 92.3% 89.7% 95.0% 92.3% Vials initially contained 7.05 nMoles PFOS. 1. Samples contained Humic Materials, samples are from triplicate analysis. 2. Samples were plain water, results are from a single replicate. ND = non detect. As observed in table 2a, direct photolytic decomposition of PFOS could not be detected within experimental error - either by loss of the parent material or by appearance of predicted degradation products. Indirect photolysis was not observed in any of the three matrices (the Page 15 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 H2O2 rich aqueous matrix - table 2a, the Fe+3 containing matrix - table 2b and the humic containing matrix - table 2c). The Fe20 3 data were used as an environmental model to generate a half-life estimate for the degradation of PFOS. Because no degradation was observed, data from table 2b, Fe20 3 with and without H2O2, was pooled to determine the experimental error of the analysis. This data, shown graphically in figure 2, yielded an estimated environmental half-life of > 3.7 years. The exact mathematical solution is shown in Appendix C. Figure 2. Pooled Concentration Data from the Iron Oxide Rich Matrix. Page 16 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 Conclusions A quantitative preliminary investigation was undertaken to determine the photolytic activity of potassium periluorooctone sulfonate (PFOS) and to identify the primary degradation products, if any. The investigation included experimental conditions that addressed both direct and indirect photolysis. To test for direct photolysis, samples of PFOS in an aqueous matrix were exposed to a synthetic light source for selected periods of time. Direct photolytic decomposition of PFOS was not observed based on loss of starting material nor were any of the predicted degradation products detected above their limit of quantitation. To test for indirect photolysis, a synthetic light source was used to initiate radical formation in three separate matrices: a synthetic humic matrix, a hydrogen peroxide rich matrix and an iron containing matrix (as Fe203). Degradation of PFOS was not observed in any matrix outside of the experimental precision of the analytical methodology. Mass balance for the degradation study was 100+11% under all experimental conditions. Using the Fe20 3 photoinitiator matrix model, we estimate the environmental photolytic half-life of PFOS to be greater than 3.7 years. Page 17 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 References 1. Fate, Transport and Transformation Test Guidelines, OPPTS 835.5270 Indirect Photolysis Screening Test, EPA712-C-98-099; United States Environmental Protection Agency, U.S. Government Printing Office: Washington, DC, 1998, pp. 1-22. 2. OECD Guideline for Testing of Chemicals, Phototransformation of Chemicals in Water--Direct and Indirect Photoysis, (Draft Document); OECD, 2000, pp. 1-- 59. 3. Serano, L.; Bufo, S. A.; Perucci, P.; Meallier, P.; Mansour, M. Photolysis and Hydrolysis of Rimsulfuron. Pestic. Sci. 1999, Vol. 55, pp. 955-961. 4. Nubbe, M. E.; Adams, V. D.; Moore, W. M. The Direct and Sensitized Photooxidation of Hexachlorocyclopentadiene. Wat. Res. 1995, Vol. 29, No. 5, pp. 1287-1293. 5. Ogata, Y.; Tomizawa, K.; Furuta, K. Chemistry of Peroxides, in S. Patal (ed.). The Chemistry of Peroxides 1983, p. 720. 6. Lunk, S.; Sedlk, P. Photoinitiated Reactions of Hydrogen Peroxide in the Liquid Phase. J. Photochem. Photobiol. A.: Chem. 1992, Vol. 68, pp. 1-33. 7. Kachanova, Z. P.; Kozlov, J. N. Zh. Fiz. Khim. 1973, Vol. 47, p. 2107. 8. Behar, B.; Stein, G. Science 1966, Vol. 154, p. 1012. 9. Takahashi, N.; Ito, M.; Mikami, N.; Matsuda, T.; Miyamoto, J. Identification of Reactive Oxygen Species Generated by Irradiation of Aqueous Humic Acid Solution. J. Pesticide Sci. 1988, Vol. 13, pp. 429-435. Page 18 of 158 BACK TO MAIN 3M Environmental Report No. W2775 Signatures The final draft of this report is a true representation of the data developed in this study. It has been issued by: Thomas L. Hatfield, P t f f f i Special Projects Team Leader Dat William K. Reagen, Ph. D., Laboratory Management Date Page 19 of 156 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 Appendix A: Analytical Methods This appendix presents the analytical methods and Standard Operating Procedures used in the present study. ETS-9-46.0 Operation and Maintenance of the Hewlett Packard 8453 UV-Visible Spectrophotometer ETS-9-44.0 Operation and Maintenance of the Sunlight Exposure System, Immersion Unit, and Recirculating Water Chiller System ETS-9-49.0 Routine Maintenance of Archon Purge and Trap Autosampler, Tekmar Purge and Trap Concentrator and Agilent Gas Chromatograph/Mass Spectrometer ETS-8-182.0 Analysis of Fluorochemicals by Archon Purge and Trap Autosampler, Tekmar Purge and Trap Concentrator and Agilent Gas Chromatograph/Mass Spectrometer ETS-8-177.0 Indirect Photolysis Screening Tests in Synthetic Humic Water ETS-8-176.0 Preparation of Samples for Photolytic Exposure Studies in Aqueous Matrices ETS-8-181.0 Analysis of Photolysis Samples for Fluorochemicals by High Performance Liquid Chromatography With Mass Spectrometry Detection Page 20 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 3M Environmental Laboratory M ethod Analysis of Photolysis samples for fluorochemicals by High Performance Liquid Chromatography with Mass Spectrometry Detection Method Number: ETS-8-181.0 Exact Copy of Orig'nal Initial Approved by: D a t0 Laboratory Management Team Leader Adoption Date: \ o j t J 3O Effective Revision Date: Date Dater^ Page 21 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 1.0 Scope and Application_____________________________________________________ 1.1 This procedure defines the steps for analysis of fluorochemicals in photolysis study samples by high performance liquid chromatography (HPLC) with mass spectrometry (MS) detection and quantification. Refer to the HP 1100 HPLC/MSD Standard Operating Procedure ETS-9-34.0 for operating and maintenance procedures related to the instrument. Refer to Standard Operating Procedures ETS-8-176 and ETS-8-177 for information involving sample preparation and photolytic exposure procedures. 1.2 Compatible analytes. Test substance and degradation products for fluorochemicals or other fluormated compounds, or other ionizable compounds, which includes but is not limited to: Compound Acronvm Perfluorooctanoic acid Perfluorooctanesulfonate PFOA PFOS Perfluorooctanesulfonamide FOSA N-methylperfluorooctanesuIfonamide N-MeFOSA N-ethylperfluorooctanesulfonamide N-EtFOSA 2-(Nmethylperfluorooctanesulfonamido) N-MeFOSE-OH ethyl alcohol 2-(N-ethy]perfluorooctanesulfonamido) N-EtFOSE-OH ethyl alcohol Compound Acronym Perfluorobutanoic acid PFBA Perfluorobutanesulfonate PFBS Perfluorobutanesulfonamide FBSA N-methylperfluorobutanesulfonamide N-MeFBSA N-ethylperfluorobutanesuifonamide N-EtFBSA 2-(N-methylperfluorobutanesulfonamido) N-MeFBSE-OH ethyl alcohol 2-(N-ethylperfluorobutanesulfonamido) N-EtFBSE-OH ethyl alcohol ... and other C* thru Cio homologues, and polymeric materials based on the above aforementioned compounds. 1.3 Compatible matrices for analysis. Aqueous (Millipore ASTM Type I water), buffered water, lake water, sea water and metal slurries (Ti0 2 , FejOj, etc.) that have been diluted with an appropriate analytical solvent such as acetone or methanol. 2.0 Summary of Method_______________________________________________________ 2.1 This method describes the analysis of fluorochemicals in a specified matrix, using HPLC electrospray mass spectrometry for chemical separation and detection/quantification. The analysis is performed by separating target analytes on an HPLC analytical column such as a Dionex NG1 (35x 4.6mm, 10pm particle), Betasil C l8 column (50X2 mm, 5 pm particle) or equivalent using an ammonium acetate/MeOH solvent gradient. Detection by electrospray ionization mass spectrometery in either the positive or negative mode is utilized to quantify data. The MSD may be run in Selected Ion Monitoring (SIM) mode, looking for specific, pre-selected and set analyte ions (i.e. m/z 499 for PFOS (deprotonated)), or SCAN mode which collects and stores data for all ions in a specified mass range. Data quantification is then performed using either HP ChemStation or Target Software. ETS-8-181.0 Analysis o f Photolysis Samples for Fluorochemicals by HPLC/MS Page 2 o f 15 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 3.0 DEFINITIONS__________________________________________________________________ 3.1 Calibration Standard. A dilution of various amounts of a stock, intermediate or purchased standard to achieve standard solutions in a concentration range of interest. 3.2 Calibration Curve. The graphical relationship between known values, such as concentration of a series of calibration standards and their instrumental response. 3.3 Internal Standard Quantification. Process of establishing a relationship between the ratio of the target analyte(s) response to internal standard or surrogate response and a known concentration of the target analyte(s). The ratio of analyte to internal standard response is used to generate the calibration curve and determine unknown concentrations. 3.4 External Standard Quantification. Process of establishing the concentration of a target analyte by plotting the theoretical amount (in units of ppb or ppm, etc.) versus the response o f the target analyte(s) on column. The resultant curve(s) shall be used to determine unknown concentrations by comparing the area response of target analyte(s) to the area response and corresponding analyte amount on the appropriate analyte's calibration curve. Differences in sample mass/volume analyzed, if noted, must be compensated for by a factor applied to the value. 3.5 Correlation Coefficient (r). A measure of the degree o f correlation between two variables. This term is generally used to evaluate the linearity of a Least Squares Linear regression. An r value of 0.98 is at the lower bounds of what is considered linear. Values of r may range from -1 to +1. A value o f +1 denotes perfect direct functional relationship between two variables. A value o f-1 also denotes a perfect inverse relationship. When r = 0, there is no effect o f one variable upon the other variable. 3.6 Coefficient of Determination (r2). The square of the correlation coefficient. It is the proportion o f the variation in the dependent variable that is accounted for by the independent variable. 3.7 Internal standard. A known amount of a compound or element similar in analytical behavior to the compound(s) or elements) of interest, added to all samples and standards, and carried through the entire measurement process (post-photolysis, after solvent dilution). It provides a reference for evaluating and controlling the precision and bias of the applied analytical method. Samples are to be quantified using the internal standard. 3.8 Surrogate. An organic compound similar to the target analyte(s) in chemical composition and behavior in the analytical process but is not normally found in the sample(s). A surrogate may be added to samples along with the test analyte (pre and/or post photolysis) to monitor the sample integrity (leaks or matrix effects). The surrogate may be added to the calibration standards to serve as a qualitative reference for the samples. 3.9 Continuing Calibration Verification (CCV). Standards analyzed during an analytical run to verify the continued accuracy of the calibration curve. This solution may or may not be prepared from a different source or lot number than the calibration curve standards. ETS-8-181.0 Analysis o f Photolysis Samples for Fluorochemicals by HPLC/MS Page 3 o f 15 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 3.10 Solvent Blank. A sample o f analyte-free medium (for example, methanol, 1:7 diluted buffer:methanol) that is not taken through the sample preparation process. This blank is used to evaluate instrument contamination. 3.11 Blank. For photolysis studies, there are multiple blanks to adequately represent the variables of the study (Exposed, Unexposed and Day 0 samples with/without peroxide addition). These blanks are carried through the sample preparation, photolytic and analytical procedures to monitor for contamination during any step. It is also used to establish a chromatographic baseline/background and monitor for analytical interference or suppression o f target analyte(s) from the matrix. 3.11.1 M atrix Blank: An analyte-free matrix (buffered water, lake water, etc.) to which all reagents are added in the same volumes or proportions as used in sample processing. It is used to document the test system without test analyte present. 3.11.2 Control Blank: An analyte-free matrix (ASTM Type II water) to which all reagents are added in the same volumes or proportions as used in sample processing. It serves as a control for the test matrix to monitor background levels, interferences or suppression of target analyte(s) from the test matrix. 3.12 Limit of Quantitation (LOQ). The lowest concentration that can be reliably measured within specified limits of accuracy during routine laboratory operating conditions. The LOQ is generally 5 to 10 times the minimum concentration with a 99% confidence limit that the concentration is greater than zero. However, it may be nominally chosen within these guidelines to simplify data reporting. For many analytes, the LOQ is selected as the lowest non-zero standard in the calibration curve that is greater than 4 times the level of the matrix blank. Sample LOQ are highly matrix-dependent. 3.13 Sample Triplicates. Three samples taken from and representative of the same sample source and separately carried through all steps of the extraction, photolysis and analytical procedures in an identical manner. There are multiple sets of triplicate samples to adequately represent the photolytic variables o f the study (Exposed, Unexposed and Day 0 w ith /w ith o u t p eroxide addition). T riplicate sam ples are used to assess v arian ce o f the photolytic method, including sample preparation, photolysis, and analysis. 3.14 Control Sample. A known matrix (ASTM Type n water) containing the test analyte(s) carried throughout the entire sample preparation, photolytic and analytical procedure. There are multiple sets of triplicate samples to adequately represent the photolytic variables o f the study (Exposed, Unexposed and Day 0 with/without peroxide addition). This is used to document method performance and matrix effects by comparing recoveries from the different matrices and sample types. 3.15 Relative Standard Deviation (RSD). A measure of precision defined as the standard deviation of three or more values divided by the average of the values and multiplied by 100. (Also reported as Coefficient of Variation (CV)). 3.16 Analytical Spike (AS). Prepared by adding a known mass of target analyte(s) to a specified amount of a sample or control matrix prior to analysis. This assumes that an independent estimate of target analyte concentration is available. Analytical spikes are used to determine the effect of the matrix on recovery efficiency. There are multiple ETS-8-181.0 Analysis o f Photolysis Samples for Fluorochemicals by HPLC/MS Page 4 o f 15 Page 24 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 types of spiked samples to adequately represent the photolytic variables of the study (Exposed, Unexposed and Day 0 ; with/without peroxide addition.) 3.16.1 M atrix Spike. The test matrix (buffered water, lake water) sample containing the test analyte or blank to which a known mass of target analyte(s) is added prior to analysis. 3.16.2 Control Spike. The control matrix (ASTM Type n water) sample containing the test analyte or blank to which a known mass of target analyte(s) is added prior to analysis. 3.17 Accuracy. The closeness o f agreement between an experimentally determined value and an accepted reference value. When applied to a set of observed values, accuracy is a combination of a random (precision) and a common systematic (bias) component. For purposes of the study, the acceptance criterion is 75% to 125% of the nominal value. 3.18 Dilution. A step in the sample preparation procedure in which a solvent (i.e. methanol, acetone) is added to the test analyte/sample matrix (i.e. water, buffer, etc.) to prepare it for instrumental analysis. 3.19 Atmospheric Pressure Ionization (API): The Agilent Technologies HPLC 1100/MSD system allows for ionization of incoming liquid sample from the analytical column to the mass spectrometer interface by utilizing a source, probe, hot gas, and specific voltages. 3.20 Electrospray Ionization (ES, ESI): A method of ionization performed at atmospheric pressure, whereby ions in solution are transferred to the gas phase via tiny charge droplets. These charged droplets are produced by the application o f a strong electrical field. 3.21 Mass Spectrometry, Mass Spectrometer (MS), Mass Spectrometer Detector (MSD): The API HP 1100 MSD system equipped with a quadrupole mass selective detector. Ions are selectively discriminated by mass to charge ratio (m/z) and subsequently detected. 3.22 Geometric Mean of the calibration curve: The square root o f the product of the high standard concentration and the low calibration curve standard. When preparing calibration curve standards, the number of calibration standards below the g e o m e tric mean shall equal the number of calibration standards above the geometric mean. Having equal distribution of calibration standards above and below the geometric mean when analyzing and reprocessing data, effectively weights the curve such that both the high and low ends of the curve are given equivalent significance. 4.0 Warnings and Cautions_______ _____________________________________________ 4.1 Health and safety warnings 4.1.1 Wear the proper lab attire for all parts of this procedure. Wear gloves and proper eyewear when performing sample preparation in the laboratory at all times. Wear proper eyewear when working at the instrument in the laboratory. ETS-8-181.0 Analysis o f Photolysis Samples for Fluorochemicals by HPLC/MS Page 5 o f 15 Page 25 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 4.1.2 Handle all solvents in a hood for all parts of the described sample preparation procedure. Whenever possible and practical, dilute samples with solvent in a hood. 4.13 For potential hazards of each chemical used, refer to material safety data sheets, packing materials, and the 3M Environmental Laboratory Chemical Hazard Review. 4.2 Cautions 4.2.1 All glassware in which standards are prepared should be rinsed with acetone and methanol to reduce the possibility of contamination. 4.2.2 Ensure that the HPLC mobile phases are prepared prior to beginning a run sequence, and that there is sufficient quantity to complete the run. Do not allow the pump to run dry. 4.2.3 Ensure that before starting the run sequence there is ample hard disk space on the computer to save all run data. 4.2.4 Ensure that there is enough nitrogen in the supply tank to complete sequence runs. 5.0 Interference_______________________________________________________________ 5.1 Contaminants in solvents, reagents, glassware, and other sample processing or analysis hardware may cause interference. Use the routine analysis of laboratory method blanks to demonstrate that there is no such interference. 5.2 Contamination from columns, HPLC tubing, and detector components may cause interference at low detection levels. The routine analysis of solvent blanks must be used to demonstrate that there is no such interference. 6.0 Equipment_________________________________________________________________ 6.1 Analytical balance sensitive to 0.1 mg. 6.2 Hewlett-Packard (HP) 1100 HPLC System, or equivalent. 6.2.1 Pump, binary, Model G1312; Quaternary, Model G1311A; or equivalent. 6.2.2 Solvent degasser, Model G1322A or equivalent. 6.2.3 Autosampler, ALS Model G1313A, variable injection volume or equivalent. 6.2.4 Column heater, Model G1316A, or equivalent. 6.3 Betasil C 18,50 x 2 mm; Dionex IonPac NG1 Guard column, 4 x 35 mm; or equivalent. 6.4 Mass spectrometer. Hewlett-Packard MSD Model G1946A, or equivalent. 6.5 Refrigerator capable of maintaining 4 3 C. 6.6 Data system. A personal computer capable of controlling the HPLC system as well as recording and processing signals from the detector. ETS-8-181.0 Analysis o f Photolysis Samples for Fluorochemicals by HPLC/MS Page 6 o f 15 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 6.7 System control/data analysis software: Hewlett Packard ChemStation, Version A.6.03 or later. 6.8 Data reprocessing software: Thru-Put Systems Target NT, Revision 4.03, Build 157 or later. Hewlett Packard ChemStation, Version A.6.03 or later. 7.0 Supplies and Materials____________________________________________________ 7.1 Vials, 40 mL, VOA (I-Chem or equivalent) 7.2 Crimp cap autovials, 1.8 mL 7.3 Labels 7.4 Graduated pipets, glass, disposable, 1 mL to 10 mL 7.5 Pasteur pipets, glass, disposable 7.6 Hamilton Gastight syringes (precision 1% of total volume), 10 pL~1000 pL 7.7 Volumetric flasks, various sizes 7.8 Beakers, glass, various sizes 7.9 Automatic pipettor, capable of dispensing 10-5000 pL 8.0 Reagents and Standards________________________________________________ 8.1 Methanol (MeOH). HPLC/SPEC/GC grade from EM Science, or equivalent 8.2 Acetone. HPLC/SPEC/GC grade from EM Science, or equivalent 8.3 ASTM Type II Water. Water with lower resistance must not be used. 8.4 Ammonium acetate, 2 mM in water. This solution is chromatographic solvent A (see Section 12.2.1). (Example: An acceptable eluent solution is made by adding 0.15 g ammonium acetate crystals to a 1-L volumetric flask containing about 500 mL water, a d d in g 10 m L o f m eth a n o l, d ilu tin g to th e m ark w ith 18.0 MC2 w a ter a n d m ix in g .) 8.5 Stock, internal standard, surrogate, post-photolysis spike and calibration solutions All weights should be recorded to the nearest 0.0001 g in a standards preparation log: 8.5.1 Fluorochemical or target analyte prepared in acetonitrile (or suitable analytical solvent). (Example: A stock solution is prepared at a concentration of approximately 30,000 pg/mL by weighing 0.3 g of target analyte in a 10-mL volumetric flask and bringing to the mark with suitable analytical solvent. This solution is diluted in solvent to make additional, appropriate standards. Follow specified guidelines for documenting removal of test analyte and target analyte(s), use of balance, preparation of diluted solutions and calibration standards in the appropriate log books. Maintain photocopies of the preparation pages and worksheets in a raw data file. ETS-8-181.0 Analysis o f Photolysis Samples for Fluorochemicals by HPLC/MS Page 7 o f 15 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 9.0 Sample Ha n d l i n g __________________________________ _ 9.1 Standards and diluted samples are stored in capped autovials or capped 40 mL VOA vials until analysis. 9.2 If analysis will be delayed, standards and sample extracts may be stored at 4 C 3 C or room temperature, until analysis can be performed. Document storage conditions on sample prep worksheet with date and initials. 10.0 Quality Control___________________________________________________________ 10.1 Calibration Standards. Calibration standards (Section 11) used to generate a calibration curve should be prepared in the same type of solvent or matrix as in the study samples. The number of calibration standards and the concentration levels should be sufficient to encompass the expected concentrations of the study samples. In general, a minimum of five calibration standards is required for fit of linear regression. Broad calibration ranges (greater than three orders of magnitude between low and high standards), may require use of a quadratic fit of the data and requires more points to adequately represent the calibration range. 10.2 Continuing Calibration Verification (CCV). Analyze a mid-range calibration standard after a maximum of every fifteen samples. 10.3 Solvent blank. Solvent blanks are run before and after every calibration curve, CCV, matrix and control blank (if contamination is noted), and after batches of no more than 30 injections. Acceptable values for the blanks are values below 25% of the limit of quantitation (LOQ) of the instrument. If analyte carryover is a problem, use back-to-back solvent blanks. 10.4 Sample Triplicates. Analyze all sets of triplicate samples to provide a measure of the precision of analysis. Study samples will be analyzed in batches of no more than 30 samples. Multiple batches in an analytical sequence will be bracketed by calibration standards at the beginning and end of each study sample batch. All samples (matrix and control samples, blanks and spikes) from a specified exposure type or time maybe analyzed within the same analytical batch. 10.5 A nalytical spikes. P repare analytical spike sam ple for each sam p le type as ap p licab le to determine the matrix effect on the recovery efficiency. Concentrations of the spike should be approximately equal to a mid-range calibration standard. The matrix spike sample should be analyzed periodically to measure the precision associated with the analysis. The analyst shall accept percent spike recoveries of 100 25%. Spike recoveries outside of this range should be noted and used with other criteria to evaluate the condition of the analytical run or necessity for repeat analysis. Consult with the Team Leader or designee for direction and final acceptance or rejection of the analytical run. Samples may be spiked at two different concentrations to ensure that the resulting levels o f target analyte(s) are within the viable range of the calibration curve. ETS-8-181.0 Analysis o f Photolysis Samples for Fluorochemicals by HPLC/MS Page 8 o f 15 Page 28 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 11.0 Calibration and Standardization__________________________________ __ 11.1 Analyze standards prior to and following each set of samples. The linear regression will be calculated from the plot of all individual calibration points, including but not forced through zero, using HP ChemStation or Target NT Software. A minimum of five calibration standards is required to generate linear regression for target analyte(s). If the calibration curve residuals are greater than 25% deviation from the theoretical value, quadratic curve fitting and/or dropping low/high curve points may be required if data review shows this to be a consistent and more accurate representation of the instrument response. Document in the raw data the technical justification for any deviation and consult with the team leader or designee for direction and for final acceptance or rejection of the data. 11.1.1 Use the following documentation/footnotes may be used to justify dropping high/low curve points. 1) "High/low calibration points (list points) were excluded to provide a better fit over the linear range appropriate to the measured data." 2) "Low level calibration point(s) were not 4x higher than the extraction blank; these points were excluded from the curve to disqualify a data range that may have been significantly affected by background levels of the analyte." 3) "High/low calibration point(s) (list points) were excluded as they were not within the +/-25% accuracy requirements of the method when the curves were evaluated over a linear range appropriate to the data.' 11.2 If the curve does not meet requirements perform routine maintenance or prepare a new standard curve (if necessary) and reanalyze. 12.0 Procedures_____________________________________________ .___________________ 12.1 Instrument set up. Within "Method and Run Control" in the HP ChemStation Software window, turn the system "on" to: turn on the drying gas flow; initiate solvent flow through th e colum n and nebulizing needle; equilibrate the colum n com partm ent; and equilibrate the MSD spray chamber temperatures and conditions. The system module displays should turn a green color to indicate the instrument is "ready" for analysis. A yellow color indicates that the system is not ready, but is working to "get ready." A red colored module icon indicates a type of systematic failure and should be corrected prior to proceeding. Check the run log for error messages and error codes if the problem is not apparent. 12.2 MSD set-up. Turn the MSD "on" in the software to equilibrate the system. 12.2.1 Check the level o f nitrogen in the tank and ensure there is enough to complete the impending run. 12.2.2 Clean the MSD according to the Equipment Procedure ETS-9-34.0 Operation and Maintenance of HP LC/MS System. ETS-8-181.0 Analysis o f Photolysis Samples for Fluorochemicals by HPLC/MS Page 9 o f 15 Page 29 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 12.2.3 Perform a Check Tune or Autotune to ensure system operational qualification and performance verification of the MSD. Log the Tune results and keep a copy with the analytical raw data. 12.2.4 Load the method file and ensure that the following parameters are appropriately set for the target analyte(s): Example mass spectrometer set up*: MSD: Ionization mode API-ES (or API-APCI) Polarity Negative (or Positive) Acquisition mode SIM (or SCAN) Gain Fragmentor 1.0 (up to 7.0) 70 (may be set to one voltage, or ramped for each ion) Dwell time 183 msec (time is a function o f the amount of ions). Capillary voltage Drying gas 3500, or equivalent Nitrogen, or equivalent Nebulizer pressure 30 psig, or equivalent Drying gas flow 8 L/min, or equivalent Drying gas temp 300* C , or equivalent Example conditions are applicable to HP1100 LC/MSD equipment only. 12.3 LC Check 12.3.1 Check that the appropriate HPLC column is in the instrument for analysis. 12.3.2 Check that the correct eluent solutions are in bottles to be used and that enough is available to complete the sequence run. Adjust the solvent bottle level electronically within the method and run control window. 12.3.3 Ensure that the method file has the appropriate LC p u m p p a ra m e te rs for s o lv e n t flow/gradient program, column I.D/temperature, injection volume and stop time. Solvent A: Ammonium Acetate 2mM in water (with 1% MeOH) (or equivalent). Solvent B: Methanol (or equivalent). Example Solvent Gradient: T ime (min) % A %B Flow Rath 0.0 80 40 0.3 mL/min 1.0 60 40 0.3 mL/min 4.0 5 95 0.3 mL/min 11.0 5 Post time: 6 minutes, column temperature: 35C. 95 0.3 mL/min The initial solvent composition is set to a higher amount of aqueous solvent so as to achieve sufficient sample retention on the column. The gradient composition ETS-8-181.0 Analysis o f Photolysis Samples for Fluorochemicals by HPLC/MS Page 10 o f 15 Page 30 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 increases to a higher organic content over time to separate the analytes, and elute them off the column in a timely fashion. After all analytes have eluted, the solvent ratio is then switched back to "initial conditions" and held until the column pressure has stabilized ( indicating re-equilibration to initial conditions) prior to the next injection. 12.3.4 Auto-sampler setup: Auto-sampler: Auto-sampler Program: ALS Model G1313A None Injection volume: 5.0 pL, or equivalent ^Example conditions are applicable to Hewlett Packard 1100 LC/MSD only 12.3.5 Place the samples in the autosampler tray and construct a sequence table with appropriate calibration standards, calibration check standards and solvent blanks. 12.3.5.1 Verify that all samples and standards are positioned correctly. 12.3.5.2 Enter the identification code for each standard and samples. For solvent blanks, identify the solvent and the traceability number. 12.3.5.3 Use one injection per sample. 12.3.5.4 Ensure the method file is correctly entered for all samples. 12.4 Sequence and electronic storage of data files. 12.4.1 Within the sequence parameters, enter sequence information (brief sample population description and instrument name). 12.4.2 Set post-sequence command macro to shut down system after the run is completed (Example: "STANDBY" on HP1100/MSD systems). 12.4.3 Save all data to a subdirectory labeled with instrument and analysis date (e.g. H100200 for analysis on "Hillary," on 2 October, 2000). 12.4.4 Name data within the subdirectory with instrument EDand injection/run number (e.g. fo r sam ples acquired on "H illary", data files shrill be "H ILL0001" -- "HILLOO##'0. DO NOT exceed five identification characters for analysis o f more than 99 samples since eight characters total are available for sample ID, and the last three digits are for sample numbering purposes (leaving the first five characters for data file identification). 12.4.5 Save sequence as analysis date and instrument letter (e.g. For analysis on instrument "Hillary" on October 2 ,2 0 0 0 save sequence table as H100200.S). 12.5 Sample analysis 12.5.1 Enter the standard, sample, blank identification into the sequence table. Analyze calibration standards first, then up to 30 injections, followed by the calibration standards re-injected. Multiple sets of samples can be set up in the sequence table with each set bracketed by calibration standards. Analyze a single continuing calibration standard (CCV) after a maximum of 15 injections. Solvent blanks shall be analyzed before and after the CCV and before method and control blanks, if ETS-8-181.0 Analysis o f Photolysis Samples for Fluorochemicals by HPLC/MS Page 11 o f 15 Page 31 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 necessary. Two solvent blanks shall be analyzed at the end of the calibration standards to ensure that there is no carry over from the highest standard concentration. Solvent blanks may also be used to separate groups o f samples and evaluate for carry over problems from actual samples. Ensure standards, blanks, samples, and matrix spikes in the auto-sampler tray vials are in same order as listed in the sequence. 12.5.2 Print a copy of the tune results, method and sequence to be stored with raw data. 12.5.3 Start the sequence. 12.6 Post Analysis. Prepare a folder identified specifically to the project and save data, method and sequence files. This will be considered the raw electronic data to be archived. 13.0 Data Analysis and Calculations____________________________________________ 13.1 Peak Evaluation. Peaks must be symmetric in shape and identified by extracting compound-specific ions. Peaks considered for quantification must have peak heights greater than 4 times any baseline level for that region of the chromatogram. Peak area integration is from baseline to baseline using automatic or manual integration. Manual integration is not acceptable for calibration standards and should only be used in extreme cases as designated by the Team Leader. Samples and standards that may need to be manually integrated must be documented in the raw data as to why the peak was manually integrated. 13.2 Integration Codes. The following integration codes may be utilized to document what type o f manual integration was performed. A: Adjust Left Anchor B: Adjust Right Anchor C: Delete Integration D: Add Integration Additionally, QAU encourages the data reviewer to write comments directly on the chromatogram if there is anything unusual. Date and initial all documentation. 13.3 M atrix spikes. Calculate the percent recovery for each o f the matrix spikes. Calculate the matrix spike percent recoveries using the following equation: % Recovery = (observed spiked sample result - observed sample result! x 100 Nominal amount spiked Using the observed matrix spike recoveries, calculate the average spike recovery. 13.4 Accuracy. Calculate the accuracy of each calculated calibration standard and CCV samples using the following equation. Accuracy = (Measured Conc.l x 100 Nominal Cone. ETS-8-181.0 Analysis o f Photolysis Samples for Fluorochemicals by HPLC/MS Page 12 o f 15 Page 32 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 13.5 Sample Triplicates. Calculate the relative standard deviation (%RSD) for the triplicate samples: RSD = Standard Deviation of Sample Set x 100 Average of Sample Set 14.0 M e t h o d p e r f o r m a n c e ______________________________________________________ ______ 14.1 Coefficient of Determination (r2). The coefficient of determination (r2) for the calibration curves should be 0.990 or greater. The curves should be examined closely for linearity and intercept, particularly for accuracy of quantitation at the low and high ends o f the curve. The accuracy of all standards used for calibration must be within 75-125%. It may be necessary to use quadratic fits of the data, usually when broad range curves (greater than 3 orders of magnitude between the low and high concentration standards) are used. Document in the raw data the technical justification for using quadratic equations. Consult with the Team Leader or designee for direction and for final acceptance or rejection for the data. 14.2 Calibration Standards. The acceptance criterion for the calibration standards is that the accuracy of each standard is 75% to 125% ( 25 % difference) of the nominal value. Calibration standards outside this range are to be noted. Document in the raw data the technical justification for deviations. Consult with the Team Leader or designee for direction and for final acceptance or rejection for the data. 14.3 Internal Standard (IS) and Surrogate. Review of the internal standard and surrogate performance is performed by averaging the area response throughout the analytical run and calculating %RSD. Inconsistencies in the internal standard peak area may indicate instrumental changes over time. Inconsistencies in the surrogate peak area may indicate instrumental changes, injection error, or changes in the test-system. Consult with the Team Leader or designee for direction and final acceptance or rejection of the analytical run. 14.4 Continuing Calibration Verification. If the accuracy for the amount of measured analyte is greater than 25% from the nominal value relative to the initial standard curve, the Team Leader should be consulted. Only those samples analyzed before the last acceptable calibration check standard may be used. Consult with the Team Leader or designee for direction and for final acceptance or rejection for the data. 14.5 Solvent Blanks. Solvent blanks should show no more than a 5% carryover from a high standard or calibration check standard. If so, two solvent blanks may be necessary to rule out instrumental contamination. If peaks greater than 25% of the peak area of the designated LOQ value are observed in sequential solvent blanks, this is indicative of instrument contamination. The instrument shall be serviced by thoroughly cleaning the electrospray source, and replacing/cleaning columns, tubing, etc. (as designated in the Equipment Procedure, ETS-9-34.0) and the analysis restarted. Consult with the Team Leader or designee for direction and final acceptance or rejection of the analytical run. 14.6 M atrix Blanks. Matrix blanks are the basis for determining the LOQ and are monitored at various times in the analytical run. Samples with greater than 25% o f the peak area of the designated LOQ value observed in matrix blanks are indicative of matrix effect, ETS-8-181.0 Analysis o f Photolysis Samples for Fluorochemicals by HPLC/MS Page 13 o f 15 Page 33 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 sample contamination or instrument contamination. Evaluation of the solvent and control blanks may be necessaiy to determine these effects. Use of solvent blanks prior to the matrix blank may be necessaiy to rule out instrumental or sample contamination. 14.7 Control Blanks. Control blanks are the basis for determining matrix effect (interference or suppression) and also to monitor for instrumental or sample contamination. Use of solvent blanks prior to the matrix blank may be necessary to rule out instrumental or sample contamination. 14.8 Limit of Quantitation (LOQ). The LOQ is equal to the lowest acceptable standard (i.e. % accuracy is < 25 % nominal value) in the calibration curve that is greater than 4 times the level o f the matrix blanks. 14.9 Sample Triplicates. The analyst shall accept %RSD values < 25%. %RSD values > 25% should be noted. Data used in the final report that is deemed out of control will be required to have technical justification for why the data is used, documented in the final report and raw data. Consult with the Team Leader or designee for direction, and for final acceptance or rejection of the data. 14.10 Control Samples. The acceptance criterion for the control samples is that the accuracy is 75% to 125% of the nominal value. These will be used as a reference for matrix effect and overall method performance. Control samples outside this range are to be noted. Consult with the Team Leader or designee for direction and for final acceptance or rejection for the data. Data used in final report that is deemed out of control will be required to have a technical justification for why the data are being used, documented in the final report and raw data. 14.11 Analytical Spikes. The analyst shall accept percent spike recovery values of 100 25%. Spike recoveries outside of this range should be noted. Consult with the Team Leader or designee for direction, and for final acceptance or rejection of the data. Data used in final report that is deemed out of control will be required to have a technical justification for why the data are being used, documented in the final report and raw data. 14.12 System Suitability. Without performing a method validation, system suitability can be dem onstrated by acceptable instrum ental checks (e.g. abbreviated m /z check-tune, or full auto-tune routines. Consult the appropriate instrumental manuals (Reference 18.2). Furthermore, overlaying calibration curves and implementing check standards (CCV), the method shall be self-validating if all data quality objectives are satisfied. 15.0 Pollution Prevention and Waste Management_____________________________ 15.1 Dispose of sample waste by placing in high or low BTU containers as appropriate. Use broken glass containers to dispose of glass pipettes. 15.2 Collect HPLC solvent waste in the satellite accumulation can. Empty into the flammable storage drum in the hazardous waste collection area on the 2nd floor. 15.3 Use smaller bore columns when possible to minimize waste generation. ETS-8-181.0 Analysis o f Photolysis Samples for Fluorochemicals by HPLC/MS Page 14 o f IS Page 34 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 16.0 R e c o r d s ___________________________________________________________________________ 16.1 Print hard copies of all graphics and data analysis summaries for archiving. 16.2 Sign and date all graphics and label with instrument ID. 16.3 Fill out appropriate preparation worksheets completely, making sure to include all initials and dates, along with the study number and sample identification. 16.4 Print out the sample acquisition sequence table, reduce the size with photocopying and tape the photocopy into the instrument log. Keep the original copy for the raw data files. 16.5 Print chromatograms, reprocessing sequence and batch reports for all analyses. 16.6 Print calibration tables and curve information and store in the raw data file. 16.7 Enter all standard preparation information in the standards preparation logbook. Make a photocopy of the logbook page and include the copy in the raw data file. 16.8 Archive electronic data to appropriate media when necessary. 17.0 A t t a c h m e n t s ___________________________________________________________ 17.1 None. 18.0 R e f e r e n c e s _______________________________________________________________________ 18.1 ETS-9-34.0, Hewlett Packard 1100/MSD Equipment Procedure. 18.2 Hewlett Packard 1100/MSD instruction CD/ROM. 19.0 A f f e c t e d D o c u m e n t s____________________________________________________ 19.1 None. 20.0 R e v is io n s ______________________________ _________________________________________________________ Revision number Reason for revision Date of Revision ETS-8-181.0 Analysis o f Photolysis Samples for Fluorochemicals by HPLC/MS Page 15 o f 15 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 3M Environmental Laboratory Method Preparation o f Samples for Photolytic Exposure Studies in Aqueous Matrices Method Number; ETS-8-176.0 Adoption Date; Approved By: Laboratory Manager CopV o \ O n 9 'na' -- C .1 -- - D a te \p \tia \ ETS-8-176.0P rep a ra tio n o f Sam ples f o r P hotolysis Studies in Aqueous M atrices Method Page 1 o f 18 Page 36 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 1.0 S c o p e and A ppl ic a t io n 1.1 Purpose. Chemicals dissolved in aqueous solutions are subject to two types of photoreaction. The first type (direct photolysis) occurs when the chemical of interest absorbs sunlight directly and is transformed to products when unstable, excited states of the molecule lead to decomposition. The second type is indirect photolysis, where degradation of the dissolved chemical is the result of chemical or electronic excitation transfer from light-absorbing species in the water. The simplest reaction involves the absorption of UV energy by hydrogen peroxide (H2O2) to produce 2 hydroxl radicals. These may react with any species in the water, including solvent, buffer, dissolved organic material and target material. Use of water and H2O2 is very controlled and predictable. Other sources in other matrices are not as controlled or predicable, but are more environmentally relevant. Natural waters such as lake and sea water can be used for the photolytic reaction matrix because it may contain dissolved organic material that absorbs sunlight and produces reactive intermediates that include singlet oxygen (1C>2) which may promote indirect photolysis of the test substance. Another transient species photochemically produced by the reaction of UV light and dissolved organic materials (humic) is hydrogen peroxide (H2O2) which may react further to form the hydroxyl radical. The addition of H2O2 to test solutions may be utilized as a free radical source to initiate indirect photolytic reactions in controlled test solutions such as MilliQ water or buffers. Further studies involving the use of either naturally occurring metal complexes such as Fe(III) which undergo photoreduction to Fe(II) and free radicals or addition o f TO2 as a catalytic surface for indirect photolysis may also be evaluated within this method. 1.2 Compatible analytes. Test substance and degradation products for photolytic exposure include but are not limited to: Comnound Acronvm Compound Acronvm Perfluorooctanoic acid PFOA Perfluorobutanoic acid PFBA Pcrfluorooctanesulfonatc Perfluorooctanesulfonamide N -m cthylpcrfluorooctancsulfonam idc PFOS FOSA N -M eF O SA Perfluorobutan esulfonate Perfluorobutanesulfonamide N-methylperfluorobutanesulfonamide PFBS FBSA N-M eFBSA N-ethylperfluorooctanesulfonamide N-EtFOSA N-ethylperfluorobutanesulfonamide N -E tF B S A 2-(N-methylperfluoro octanesulfonamido) ethyl alcohol N-MeFOSE-OH 2-(N-methylperfluorobutanesulfonamido) ethyl N-MeFBSE- alcohol OH 2-(N-ethylperfluorooctanesulfonamido) N-EtFOSE-OH 2-(N.ethylperfluoFobutanesulfonamido)ethyl ethyl alcohol alcohol N-EtFBSE-OH 1-perfluorooctene -- 1-perfluorobutene -- Perfluorooctanehydride 1H, C8-hydride Perfluorobutanehydride 1H, C4-hydride ... and other C4 thru C]0homologues, and polymeric materials based on the aforementioned compounds. ETS-8-176.0P reparation o f Sam plesf o r P hotolysis Studies in Aqueous M atrices Method Page 2 o f 18 Page 37 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 Other possible degradation products include, but are not limited to: c, 1H -p erflu o ro eth an e (lH -p fC 2 ) 1H -p erflu o ro eth an e (lH -p fC 2 ) C3 1H -p erflu o ro p ro p an e ( lH -p fC 3 ) 2H-perfluotopropane (2H-pfC3) perfluoro-1-propene (pfC 3-lenc) C< p erflu o ro -1 -b u ten e ( p fC 4 -le n e ) Periluoro-2-butene (pfC4-2ene) 2H -perfluorobutane (2H -pfC4) C5 2M -perflu o ro rp en tan e (2 H -p fC 5 ) C, p e rflu o ro -2 -h e x en e (p fC 6 -2 en e) perfluoro-1 -pentene (pfC S-lene) periluoro-2-pentene (pfC5-2ene) 1H -p erflu o ro h ex a n e ( 1H -p (C 6 ) p erflu o ro -1 -h e x en e (p fC 6 -le n e ) 2H -perfluorohexene (2H-pfC6) C7 2 H -p erflu o ro h ep tan e (2 H -p fC 5 ) Periluoro- 1-heptene (ptC 7-lene) lH -perfluoroheptane (lH -pfC 7) C, p e rflu o ro -1 -o c ten e (p fC 8 -lc n e ) 2H-perfluorooctane (2H-pfC8) Periluoro-2-octene (pfC8-2ene) I H -p e rilu o ro b u ta n e ( 1H -p fC 4 ) lH -periluorohexane (IH -pfC 6) lH -perfluorooctane (lH -pfC 8) 1.3 Acceptable matrices. Aqueous solution of test substance including but not limited to the following matrices: pH 7 phosphate buffer, 18.2 M il resistivity water, seawater and metal solutions. 2.0 Sum m ary o f M etho d 2T The objective of the photolytic exposure study is to determine whether the test substance undergoes degradation by either direct or indirect photolysis, and to identify and quantify degradation products formed in the test matrix under these conditions. Study samples (5 mL aqueous matrix) are prepared in 40 mL glass VOA vials equipped with screw-top caps with septa. Study sets are prepared in duplicate for separate analysis by LC/MS and dynamic purge and trap GC/MS. When required, the addition of 30% H2O2 solution to initiate radical formation is performed prior to the photolytic exposure and at specified intervals throughout the exposure study. Vials are placed in the photo-reactor and immersed in a water bath controlled at 23-26 C. Samples are exposed to approximately 261 W/m2of 310-800 nm photo-irradiance for a specified number of 8-hour periods. An 8-hour period of irradiance is defined as one day's worth of sunlight. Other parameters are acceptable, with the time and settings noted for each study. The number o f days to expose samples is determined by the Team Leader. The amount of irradiation received by the samples may be monitored in one o f the follow ing three w ays: 1) calculating the total wattage per length o f exposure 2) use of a radiometer to measure irradiance output, and/or 3) use of a quinine monohydrochloride dihydrate (QMD) actinometer solution exposed along with the samples and monitored for change in UV absorption over time. The use of the radiometer provides an accurate measurement at specified time-points; whereas calculating the total wattage per exposure length and use of the QMD actinometer provide time-averaged total integrated energies. Suntest instruments contain an internal radiometer for maintenance of constant irradiance. A second radiometer may be used as a check for consistency. At the end of the exposure time, samples are removed from the photoreactor and either subsequently analyzed or stored at 1-5 C. Study samples to be analyzed by LC/MS are prepared for analysis by diluting the 5 mL sample volume with 30 mL of suitable analytical solvent (e.g. methanol) containing internal standard. The GC/MS study samples are stored inverted prior to purge and trap GC/MS analysis. E T S -S -\1 6 .0 P rep a ra tio n o f Sam plesf o r P hotolysis Studies in Aqueous M atrices Method Page 3 o f 18 Page 38 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 2.2 An example of samples to be prepared for each study is shown in the table below. Exact lists may vary, dependent upon the test specifics for each study and will be noted in individual study reports. Typically, there are extra control samples for certain matrices such as Fe2C>3. LC/MS GC/MS Description Sample Rep 1 Sample Rep 2 Sample Rep 3 Sample Spike Matrix Blank Matrix Blank Spike Control Sample Control Spike Control Blank Control Blank Spike Test Matrix + + ++ + + 0 0 0 0 Control Test Matrix Substance 0+ 0 0 0 0 +++0 00 ++ ++ +0 +0 Post Photolysis Target Analyte spike 0 0 +0 0 + 0 + 0 + Sample Type Time 0 TimeO TimeO TimeO TimeO Time 0 TimeO TimeO TimeO Time 0 I With HA X X X X X X X X X X Without With HA HA XX XX XX XX XX XX XX XX XX XX Whithaout X X X X X X X X X X Sample Rep 1 Sample Rep 2 Sample Rep 3 Sample Spike Matrix Blank Matrix Blank Spike Control Sample Control Spite Control Blank Control Blank Spike ++ ++++ 0 0 0 0 0 0 0 0 0 ++++0 +++ + 0 ++0 0 0 0 Exposed X XX X 0 Exposed X XX X +0 Exposed X XX X Exposed X XX X 0 Exposed X XX X + Exposed X XX X +0 Exposed X XX X Exposed X XX X +0 Exposed X XX X Exposed X XX x1 Sample Rep 1 Sample Rep 2 Sample Rep 3 Sample Spike Matrix Blank Matrix Blank Spike Control Sample Control Spike Control Blank Control Blank Spike ++ + + + + 0 0 0 0 0 0 0 0 0 0 + + + + + + 0 0 + + 0 0 * Unexposed XX X 0 0 + Unexposed Unexposed Xx XX XX X X Unexposed X XX X 0 Unexposed X XX X + Unexposed X XX X 0 Unexposed X XX X + Unexposed X XX X 0 Unexposed X XX X + Unexposed X XX X + = added to test vial; 0 = NOT added to test vial; X = One set W/H2O2, One set w/o H2O2 3.0 Q u a l it y C o n t r o i.- D e f in it io n / F r f .q u e n c y /P e r f o r m a n c e C r it e r ia 371 Blanks 3.1.1 D efinition: M atrix Blank. An analyte-free matrix to which all reagents are added in the same volumes or proportions as used in the sample processing. For photolysis studies, there are multiple matrix blanks to adequately represent the variables within the study in reference to the matrix (e.g. Exposed, Unexposed, Time 0; with peroxide, without peroxide). The matrix blanks are carried through the complete sample preparation, experimental treatment and analytical procedure. The matrix blank is used to document contamination resulting from the experimental treatment and analytical process. Refer to the table below for an example of matrix blank types. The matrix blank is used to document the actual test system without the test substance. The control blank is used to control the test matrix and trace any background levels of target analyte that may be matrix- specific. The table below shows an example of a control blank E T S -i-\1 6 .Q P re p a ra tio n o f S am ples f o r P hotolysis Studies in A queous M atrices Method Page 4 o f 18 Page 39 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 3.1.2 Performance Criteria: The frequency of use and the performance specifications for each of the above defined method blank types shall be as follows: Matrix ID Matrix Blank Control Blank Matrix descrintion Example: 0.01 M Phosphate Buffer, pH 7 Example: ASTM Type II Water Frequency 1 Replicate per light and dark exposure, for each time point and for each analytical methodology. Performance Criteria Any background level of target analyte shall be less than 25% die area counts of the LOQ. 3.2 Limit of Quantitation (LOQ) 3.2.1 Definition: The lowest concentration that can be reliably measured within specified limits of accuracy during routine laboratory operating conditions. Sample LOQs are highly matrix-dependent. 3.2.2 Quality Control andPerformance Criteria: The LOQ is generally 5 to 10 times the minimum concentration with a 99% confidence limit that the concentration is greater than zero. However, it may be nominally chosen within these guidelines to simplify data reporting. For many analytes, the LOQ is selected as die lowest non-zero standard in the calibration curve that is greater than 4 times the level of the solvent blanks and indicates good accuracy ( 25%) of the nominal calibration standard concentration. 3.3 Sample Triplicate 3.3.1 Definition: Three aliquots prepared as representatives of the same sample source (i.e. test substance) and carried through all steps of the photolytic study process and analytical procedures in an identical manner. The results from triplicate analyses are used to evaluate variability of the total method, including sample preparation, photolytic process and analysis. 3.3.2 Performance Criteria: The samples in the test matrix will be prepared in triplicate. Each replicate will be prepared for each treatment type: light and dark exposures, with and without hydrogen peroxide, for EACH time-point, and for each analytical methodology (e.g. LC/MS and/or GC/MS). See the following table: Matrix Descrintion Test Matrix containing test analyte(s) Frequency of Use 3 Replicates per light AND dark exposure, with AND without H2O2, for each time-point, and for each analytical methodology (i.e. LC/MS and/or GC/MS). Performance Criteria The analyst shall accept %RSD <25%. Precision values not meeting specification must be documented and justified (if possible). 3.4 Control Sample 3.4.1 Definition: A known matrix containing the test analyte(s) carried throughout the entire analytical procedure. This is used to document laboratory performance (i.e. precision of sample preparation by comparing spike recoveries from the different matrices and sample types). A control sample consists of a control matrix spiked with test analyte(s). A control sample should be analyzed with each batch of samples processed to verify that the precision and bias of the analytical process E T S -i-\1 6 .0 P r e p a r a tio n o f Sam ples f o r P hotolysis Studies in Aqueous M atrices Method Page 5 o f 18 Page 40 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 3.4.2 are within control limits. The results of control sample analyses are compared to control limits established for both precision and bias to determine usability of the data. Performance Criteria. One control sample will be prepared per matrix, per treatment type. See the following table: Matrix Description Control matrix with test analyte(s) added Freauencv of Use 1 Replicate per light AND dark exposure, with AND without H2C>2, for each time-point, and for each analytical methodology (i.e. LC/MS and/or GC/MS). Performance Criteria The analyst shall accept recovery values of 100 25%. Accuracy values not meeting specification must be documented and justified (if possible). 3.5 Analytical Spike (AS) 3.5.1 Definition: Prepared by adding a known mass of target analyte(s) to a specified amount of a diluted and/or aliquoted sample. This assumes that an independent estimate of target analyte concentration is available. Analytical spikes are used to evaluate the recovery efficiency of the analyte and the effect of the matrix on the measurements. 3.5.2 Quality Control and Performance Criteria: One sample spike will be prepared in the actual test matrix sample, and one control spike in the control matrix will be prepared. Each replicate will be prepared per treatment type: for light and dark exposures, with and without hydrogen peroxide, for each time-point, and for each analytical methodology (i.e. LC/MS and/or GC/MS). In addition, one matrix blank spike and one control blank spike will be prepared. See the following table: Matrix Description Test Matrix a n d test substance, spiked with target analyte(s) just prior to analysis Control Matrix a n d test substance, spiked with target analyte(s) just prior to analysis Test Matrix without test substance, spiked with target analyte(s) just prior to analysis Control Matrix without test substance, spiked with target analyte(s) just prior to analysis Freouency of Use 1 Replicate per treatment type. 1 Replicate per treatment type. 1 Replicate per treatment type. 1 Replicate per treatment type. Performance Criteria The analyst shall accept spike recovery values of 100 25% . If spike recoveries are greater than 125% or less than 75%, document that the spike sample is out of the specifications and justify, if possible, the reason. 3.6 Internal Standard/Surrogate 3.6.1 Internal Standard Definition (applies to LC/MS and GC/MS samples): A known amount of a compound similar in analytical behavior to the target analyte(s) of interest, added to all samples and standards (post-irradiation), and carried through the entire analytical process. It provides a reference for evaluating and controlling the precision and bias of the applied analytical method. Samples are ETS-8-11 6 .0P reparation o f Sam ples f o r P hotolysis Studies in A queous M atrices Method Page 6 o f 18 Page 41 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 3.6.2 to be quantified using the internal standard providing that the response o f the internal standard is consistent ( 5% relative). Use of external calibration methodology requires written justification by the Team Leader. Surrogate Definition (applies to LC/MS and GC/MSsamples): A known amount of a compound similar in analytical behavior to the target analyte(s) of interest may be added to all samples and standards (pre- or post-irradiation, at the discretion of the Team Leader) and carried through the remaining sample preparation and analytical process. If added before exposure, it monitors the presence of vial leaks during photolysis, as well as the performance of the purge and trap auto-sampler and concentrator. Surrogate analysis is used to evaluate and control the precision and bias of the analytical method. Surrogates are not used for quantitation. Note: Internal standards are used in a ll experiments. The use o fsurrogate standards may or may not be used 3.6.3 Quality Control and Performance Criteria: M atrix DescriDtion Freauencv of Use Performance Criteria Sample diluted with 30 mL of internal standard compound dissolved in a suitable analytical solvent Sample with surrogate compound spiked into it Every LC/MS sample analyzed Every GC/MS sample analyzed The Coefficient of Variation, or %RSD shall be calculated for the area response of all appropriate samples per analytical batch. The analyst shall accept %RSD values o f <15%. The recovery and precision of the surrogates should be 100 25% and <15%, respectively. Unacceptable values shall be documented and justified, if possible. 3.7 Other Definitions. 3.7.1 Test Analyte/Substance: Any substance (mixture or controlled compound) added or administered to the test system for the purpose of chemical analysis. 3.7.2 Degradation Produces): Secondary analytes of interest produced as a result of chemical reactions during the photolysis and monitored (qualitatively or quantitatively) during the sample analysis procedure. 3.7.3 Target Analyte(s): The analyte(s) singled out in the analytical phase of the study is the target analyte. The target analyte may be identical to the test substance used in the experimental phase of the study, a by-product or degradation product that is monitored (qualitatively or quantitatively) during the sample analysis procedure. 3.7.4 Test Matrix: The physical matrix in which the study will be conducted. Also referred to as the test system. 3.7.5 Control Matrix: A known physical matrix to be included with the study for comparison with the test matrix. 3.7.6 Relative Standard Deviation (RSD): A measure of relative precision for three or more sample replicates; defined as the sample standard deviation divided by the sample average and multiplied by 100. This is expressed as percent (%RSD). 3.7.7 Accuracy: The closeness of agreement between an experimentally determined value and an accepted reference value; defined as the measured value divided by the nominal value and multiplied by 100. ETS-8-176.0P reparation o fS a m p lesf o r P hotolysis Studies in Aqueous M atrices Method Page 7 o f 18 Page 42 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 4.0 H e a l t h a n d Sa f e t y W a r n in g s 471 Safety " ' ' '' ' " 4.1.1 Wear the proper lab attire, gloves and eye protection for all parts of these procedures. 4.1.2 Handle all solvents in a hood for all parts of the described sample preparation procedure. 4.13 For potential hazards of each chemical used, refer to material safety data sheets, packing materials, and 3M Environmental Laboratory's Chemical Hazard Review. 4.1.4 No mouth pipetting is allowed 4.2 Cautions 4.2.1 Glassware in which standards are prepared should be rinsed with solvent to reduce the possibility of accidental contamination. 4.2.2 The photoreactors are equipped with a continuous flow of cooling water, which poses a threat of electrocution during the handling o f the photoreactor during irradiation sequences. To avoid possible injury, inspect the units frequently for water leakage and electrical outlets and wiring for wear and tear. Replace any worn parts immediately. 4.2.3 Wear dark protective eyewear when operating the reactor. Do not look directly at the activated lamp. Use caution when handling samples in the reactor; the interior walls of the reactor and exposed glass vials become extremely hot. 5.0 Interference 571 Solvents, water and matrix components could interfere with detection thereby decreasing sensitivity in the sample analysis. Care must be taken to prevent all possible contaminants by using fresh reagents, analytical grade solvents and clean glassware during the sample preparation processes. 6.0 E q u ipm en t 671 Analytical balance sensitive to 0.1 mg 6.2 Photoreactor: Suntest CPS+, XLS+, or equivalent, equipped with a xenon arc-lamp and capable o f producing integrated irradiance values from 100-680 W/m2 over the wavelength range of 290-800 nm. Lamp output must be filtered to allow only 290-800 nm wavelengths. A flowing water bath with circulating pump is required. Consult the appropriate 3M SOP for instructions. 6.3 Water recirculating cooler capable of maintaining temperature at 25 C 5 C, from Poly Science, Model 1177-P or equivalent. 6.4 Agilent Technologies UV-visible Spectrophotometer, equipped with tungsten and deuterium lamps, Model 8453, or equivalent. Consult the appropriate 3M SOP for instructions. 6.4.1 Autosampler equipped with eight sample cell holders: Agilent Technologies Model G1120A, Thermostatted Cell Holder: Model 08451-60104, or equivalent. 6.4.1.1 1.0-cm path length quartz spectrophotometer cell from Hewlett Packard, or equivalent. 6.4.2 Long Path-Length Cell Holder, Hewlett Packard (# 89076C) or equivalent. ETS-8-176.Q Preparation o fS a m p les f o r P hotolysis Studies in Aqueous M atrices Method Page 8 o f 18 Page 43 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 6.4.2.1 10-cm path length quartz cell equipped with stopcocks, Hewlett Packard Part # 5061-3392, or equivalent. 6.4.3 Data acquisition and analysis software, HP ChemStation for UV-Visible Spectroscopy, G1116AA, Rev. B.01.02, or later. 6.4.4 PC Computer capable of running appropriate analysis software to acquire and report data. 6.5 Centrifuge capable of maintaining > 2000 ipm for 10 minutes at ambient temperature. 6.6 Radiometer (optional) capable of monitoring the energy from a xenon source from 290 to 480 nm over time. Model PMA2100, Version 1.16, Solar Light Company, Inc., or equivalent. Consult the appropriate 3M SOP for instructions. 7.0 S u p p l ie s a n d M a t e r ia l s 7ll 40 mL amber and clear glass VOA vials with screw caps with septa. 7.2 Crimp cap autovials-1.5 mL, caps, crimper, and decapper. 7.3 Adhesive-backed labels (return address size) for labeling quartz vials and autovials. 7.4 Disposable glass graduated pipettes, 1 mL to 10 mL. 7.5 Disposable glass Pasteur pipettes and rubber bulbs. 7.6 Glass beakers, various sizes. 7.7 Volumetric flasks, from 10 mL to 1000 mL. 7.8 Hamilton Gastight syringes (precision 1% of the total volume), 5 pL to 1000 pL. 7.9 10 mL Bottle-top dispenser, Calibrex, Model # 511, or equivalent. 7.10 Adjustable repeater pipette, Wheaton Step-pette 411, or equivalent, equipped with the appropriate volumetric range pipette tips. 7.11 Ziploc plastic bags, or equivalent. 8.0 R e a g e n t s a n d S ta n d a r d s________ 8 J Methanol (MeOH). HPLC/SPEC/GC and/or purge and trap grade (EM Science, or equivalent. 8.2 Acetonitrile (ACN). HPLC/SPEC/GC and/or purge and trap grad from EM Science, or equivalent. 8.3 Aqueous Matrix, includes but is not limited to the following matrix types: 8.3.1 ASTM Type I water. Milli-Q or equivalent, with a measured resistivity >18.0 Mfl-cm. 8.3.2 0.01 M pH 7.0 Phosphate Buffer. Example: Weigh 1.36 g KH2PO4 into a 2 L volumetric flask and dissolve into 1 L of Type I water. Add 600 mL of 0.1% NaOH. Adjust to pH 7.0 0.1% with 0.1% NaOH or dilute H2SO4 and dilute to the mark with Type I water for a final cone, of 10 mM. 8.3.3 Lake Surface water. Collected from a known source, with known specifications for Dissolved Organic Carbon (DOC) and Total Organic Carbon (TOC). 8.3.4 Sea water. Collected from a known source, with known DOC and TOC specifications. 8.3.5 Aqueous metal solutions and slurries (e.g. T1O2, FejOj). Example: Dilute 0.015 g o f Ti02 (Aldrich Chemical or equivalent) to 500 mL with Milli-Q water. 8.3.6 Aqueous solutions containing soil. Example: Prepare samples containing 0.7g of characterized soil or sediment in 5 mL of Milli-Q water. ETS-8-116.0P reparation o f Sam ples fo r P hotolysis Studies in Aqueous M atrices Method Page 9 o f 18 Page 44 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 8.4 Hydrogen Peroxide (H2O2). 30% aqueous solution from EM Science, or equivalent. 8.5 Potassium phosphate. Reagent grade from JT Baker or equivalent. 8.6 Stock Solutions 8.6.1 Stock solutions for the test analyte, target analytes, internal standard are prepared in an organic solvent (e.g. methanol, acetonitrile) at concentrations of approximately 10,000 pg/ml by weighting approximately O.lg of the appropriate substance into a 10-mL volumetric flask and diluting to the mark with solvent. This solution is then diluted to make appropriate working solutions. 8.7 Test Analyte Solution: 8.7.1 Example for water soluble analvteCsl: Example: A 1 pg/mL test substance solution in the test matrix (Section 8.3) is prepared by diluting 0.050 mL of stock solution (Section 8.6.1) to 500 mL with test matrix. Aliquots (5 mL) of this solution will transferred to VOA vials for subsequent photolysis. 8.7.2 Example for poor water soluble analvteisi or those with adsorption difficulties: Prepare a solution of the test substance in acetonitrile (Example: A 500 pg/mL test analyte solution is prepared by diluting 500 pi of stock solution (Section 8.6.1) into a 10 mL volumetric flask and diluting to mark with acetonitrile). Calculate the test analyte concentration such that the organic content in the test vial is no more than 1% of the total sample matrix volume. Example: A 1 pg/mL test analyte in the test matrix (Section 8.3) is prepared by injecting 10 pL of a 500 pg/mL test substance stock (Section 8.6.1) into a VOA vial containing 5 mL of the test matrix. *Acetonitrile is currently the preferred solvent to use when introducing the test substance to the test matrix because it does not interfere. Methanol is a radical scavenger, which canphotooxidize during the exposure and decrease the indirect photolysis o fthe intended test substance. Evidence o fthis phenomenon (approximately 10% decrease in the concentrations o fthefin a l products) has been observed in a study here at 3 M (EtFOSE-OHphotolysis in p H 7 buffer, with and withoutpresence ofM eO H). 8.8 Target Analyte(s) Spiking solution: Example: A spike solution of test analyte and target analyte(s) (e.g. projected degradation products) in methanol or acetonitrile is prepared by diluting 500 pL o f test analyte stock solution and 100 pL of target analyte(s) stock solution (Section 8.6.1) into 10 mL with MeOH. The final concentration is approximately 500 pg/mL test substance/ 100 pg/mL target analytes. Addition of 10 pL of this target analyte spiking solution into the 35-mL diluted sample volume will result in approximately 140 ng/ml and 30 ng/ml concentrations for the test analyte and target analyte(s), respectively.* *Pre-estimation o fthe degradation potential o fthe test analyte and subsequent degradation products is not always possible. I f possible, an analyticalpre screening o frepresentative samples should beperform edfor accurate spiking. General rule o fthumb has been that the test analyte spike amount be ETS-8- n 6 .0 P re p a ra tio n o f S am plesf o r P hotolysis Studies in Aqueous M atrices Method Page 10 o f 18 Page 45 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 approximately 25% - 50% o fthe in itial concentration. The target analyte(s) spike amount has been 10-100 ng/ml, depending on expected levels under specific conditions. M ore than one spike solution may be utilized to adequately represent the levels in the samples. Example: A test analyte that undergoes significant degradation during photolysis w ill require a lower spike concentration in the Exposed sample set due to less test analyte remaining. The D ay 0 and Unexposed sample sets, which have not degraded, may require higher test analyte spike concentrations. 8.9 Dilution Solution containing Internal Standard: The diluting solution shall contain internal standard at an area response level equivalent to approximately half the are response of the test analyte's high standard in the calibration curve. Enough dilution solution shall be prepared for use in all the study samples and in preparation of the calibration curve samples. Example: Internal standard solution is prepared by diluting 100 pL of stock solution (Section 8.6.1) to 4.0 L with MeOH to a concentration of 250 ng/mL. 8.10 Quinine monohydrochloride dihydrate (QMD). 90% from Aldrich Chemical. 8.11 QMD solution: A 2% (w/v) solution of quinine monohydrochloride dihydrate solution is prepared by weighing approximately 2.0 g into a weigh boat, transferring to a 100 mL . flask and diluting to volume with Milli-Q water. 9.0 Sa m p l e H a n d l in g 9T Record times of initial preparation, reference numbers of reagents used and the amounts, appropriate dates, times and initials on the photolysis sample preparation worksheet. Record photolysis reactor used, radiometer ( if applicable), computer for data collection, photolysis start and end on the sample preparation sheet and in the photolysis reactor log books. Record times, dates and initials of sample treatment post-photolysis, reference numbers of reagents used, and storage conditions. 9.2 Upon addition of the test substance solution, invert the 40 mL VOA sample vials (cap side down) to prevent loss of any potential volatile target analytes during the rest of the procedure. This is particularly important for the GC/MS samples. GC/MS samples may only be turned upright immediately before being loaded onto the purge and trap autosampler. The LC/MS samples may be turned upright after the photolysis process has been completed. The exception to this being the need to briefly turn the samples upright fo r H 2O2 injection through the septa o fthe appropriate VOA sample vials at specified time intervals (See Section 12.6 and Section 12.11.7). 9.3 The completed photolysis samples remain inverted and refrigerated at 1-5 C prior to analysis by LC/MS or sample purge and trap GC/MS. 9.4 Sample preparation prior to LC/MS analysis requires the addition of 30 mL of diluting solvent containing internal standard to the 5-mL photolysis samples. This is to ensure complete recovery of the target analytes from the glass VOA vial surface and to dilute the samples into a working analytical range. Day 0 study samples stored at 1-5 C during the time of photolytic exposure are removed and prepared for analysis at the same time as the exposed and unexposed samples. ETS-8-116.0P reparation o f S am plesf o r P hotolysis Studies in A queous M atrices Method Page 11 o f 18 Page 46 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 10.0 Q u a lity C o n t r o l 10.1 Refer to the definitions section for the quality control specified for each respective sample type. 11.0 C a libr a tio n and Standardization 11.1 The compounds of interest must be characterized according to laboratory specifications. 11.2 All equipment used, such as the analytical balance, radiometer, etc. should be calibrated prior to use (daily, weekly, etc.) as specified in the standard operating procedure(s). 11.3 All samples analyzed will be run against a standard curve containing varying amounts of target analytes, and a fixed amount of internal standard or surrogate compound. Refer to the appropriate LC/MS and GC/MS methodologies for further analytical information. 12.0 P ro c ed u r e 12.1 Obtain the absorbance spectra of the test compound in aqueous solution using a UVVisible Spectrophotometer (ETS-9-46.0). 12.1.1 Using a 10-cm quartz spectrophotometer cell, obtain a blank water absorbance reading over the range 290-800 nm to determine a background or baseline reading. 12.1.2 Aliquot a solution of water containing test substance, at a concentration less than half the solubility limit, into a 10 cm quartz spectrophotometer cell and obtain an absorbance reading over the range 290-800 nm. A positive absorbance may indicate the potential of the analyte to undergo direct photolysis. Non-absorbing analytes would be more likely to undergo indirect photolysis as the potential degradation pathway. 12.2 Obtain the appropriate number of clear and amber 40-mL glass vials with caps and cardboard boxes. Label the vial caps using a black permanent pen to distinctly identify samples. Paper labels will be applied post-hydrolysis as they don't stick in water. 12.3 Prepare appropriate sample preparation worksheets and create labels for each sample to affix to the 40 mL VOA vials and the autovials for analysis after photolysis. The labels should include the study number, sample number, test compound, matrix, exposure type (exposed/ unexposed/ Day 0), date and initials of the analyst. 12.4 Aliquot 5 mL of the following solutions into clear (for EXPOSED samples) and amber (for UNEXPOSED and DAY 0 samples) 40 mL glass VOA vials: 12.4.1 Matrix with test substance (sample reps 1,2,3, and sample spike). 12.4.2 Matrix without test substance (matrix blank and matrix blank spike). 12.4.3 Control matrix with test substance (control sample and control spike). 12.4.4 Control matrix without test substance (control blank and control blank spike). ( When appropriate, test substance may be added after 5mL aliquots o fmatrix have been added to the vials. See Section 8.7) 12.5 All exposed, unexposed, and day 0 samples will contain sample sets with and without peroxide and prepared for LC/MS and GC/MS analyses according to the following table: ETS-8-1Ks.QPreparation o f Sam ples f o r Photolysis Studies in Aqueous M atrices Method Page 12 o f 18 Page 47 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 Sample Treatment/Type Matrix with test substance Matrix without test substance Control matrix with test substance # of Samples 6 + H A (3LC/MS.3GC/MS) 6 - H A (3LC/MS .3GC/MS) 2+H A 0L C /M S.1G C /M S) 2 - H A (11LC/MS, 1GC/MS) 2 + H A (1LC/MS.1GC/MS) 2 - H A (11LC/MS.1GC/MS) Control matrix without test substance 2 + H A (1LC/MS, 1GC/MS) 2 - H A (11LC/MS, 1GC/MS) EXPOSED, UNEXPOSED, & DAY 0 24 x 3 per exp type = 72 Total Samples per compound per study 120 (60 for LC/MS, 60 for GC/MS) # of Spikes 2 + H A (1LC/MS, 1GC/MS) 2 - H A (1LC/MS.1 GC/MS) 2 + H A (1LC/MS, 1GC/MS) 2 - H A (1LC/MS.1GC/MS) 2 + H A ( 1LC/MS, 1GC/MS) 2 - H A (11LC/MS, 1GC/MS) 2 +H20 2(1LC/MS, 1GC/MS) 2 - H A (11LC/MS, 1GC/MS) 16x3=48 12.6 Separate the vials into three boxes labeled "Day 0," "Exposed," and "Unexposed." Initial addition o f peroxide (Section 8.4) is done at this time by removing the cap and injecting the appropriate amount (e.g. 1 0 -5 0 pL) into the vial. (Subsequent additions of peroxide shall be injected through the septa of the VOA vials.) 12.7 For use of quinine actinometer (Optional): Prepare a batch of quinine irradiation control samples by aliquoting 5 mL of the 2% aqueous solution (Section 8.8) into the appropriate number of clear and amber 40 mL I-CHEM vials. Prepare one clear and one amber vial per reactor, per day of exposure. Store the vials at 1-5 C and protected from light prior to use. Place one clear vial in the reactor per day, while removing exposed quinine controls. Exposed quinine controls need to be wrapped in foil upon removal to protect from further exposure. Store at 1-5 C prior to measuring the absorbance via UV-Vis Spectrophotometer. The absorbance measurement should be performed as soon as possible, as the absorbance increase rate after light source removal m ay be 20% o f the rate o f when light is present. (Reference 18.5). 12.8 Place all the "Day 0" samples immediately in a cooler at 1-5 C or freeze at a continuos temperature of less than 0 C, inverted and protected from light. 12.9 Place "Unexposed" sample vials (amber) into Ziploc bags separated and labeled as "with peroxide" and " without peroxide", respectively. Place the bags in the bottom of the water bath, under the photoreactor tray that holds the exposed samples. The "unexposed" samples will remain immersed in the 23-26 C water bath under the exposed samples for the duration of the exposure. Include one quinine control sample in an amber vial with the unexposed sample set. 13.0 P h o t o r e a c t o r s e t u p ETS-8-11(>.(Preparation o f Sam ples f o r P hotolysis Studies in Aqueous M atrices Method Page 13 o f 18 Page 48 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 13.1 Set the irradiation intensity at the desired output. For most experimental conditions, an intensity of 261 W/m5is chosen because it yields the equivalent average optimum natural daylight radiation for 300-400 nm at known latitude, (see the table below): Irradiance Source Average Optimum Natural Daylight1 Atlas Photoreactor with integrated irradiance output of 261 W/m*300-800 nm using the IR Reflecting and 290 cuton filters 'M easured, M iami, Florida (18.3) Anoroximate Integrated and Individual Irradiances in W/m1 250-300 nm 300-400 nm 400-800 nm 340 nm 420 nm 0.0 27.8 259.0 0.30 0.67 0.08 27.8 234.36 0.24 0.71 13.2 For all "Exposed" samples, invert the vials cap-side down and vertical in the photoreactor tray holders to a depth that ensures that half the VOA vial is submersed in the 23-26 C water bath. Include one quinine control sample (Section 12.8) in a clear vial with the exposedsampleset. 13.3 Close the door to the photoreactor and turn the door knob completely so the sensor detects that the door is completely shut. 13.4 Turn on the water cooler bath, ensure that it is set between 23-26 C. 13.5 Turn on the photoreactor pump and the power to the reactor. 13.6 Set the irradiation program using the following parameters in the table below: Photoreactor conditions Parameter Setting Program #, # of Phases 1,1 Flowing Water ("FW") ON Irradiation intensity Example: 261 watts/m2 Duration of exposure Example: 8 hours 13.7 After entering the appropriate parameters within the menu, select program #1 to run and start the irradiation program. Upon lamp ignition, the water bath begins to fill and circulate. Visually check for both lamp and water bath activation as an indication of proper initiation of the photoreactor. When removing samples during the exposure period, select "stop" from the photoreactor keypad. Open the door and carefidly remove the sample rack. Caution: The walls o fthe chamber are hot and sensitive to scratching. To restart the program, close the door, ensure that the door knob is turned all the way in and press "start" on the reactor module. Visually inspect for proper lamp ignition and water bath circulation. 13.8 At the specified time, spike appropriately labeled sample types with a known volume (e.g. 10-50 pL) of 30% H2O2 solution (Section 8.4) and swirl to ensure adequate mixing. Maintain the inverted position of samples removed for spiking pre- and post- the actual peroxide injection. Return samples to their designated locations (bottom of reactor pan ETS-8-176.0P reparation o f Sam ples f o r P hotolysis Studies in Aqueous M atrices Method Page 14 o f 18 Page 49 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 for the unexposed samples, reactor tray holder for the exposed samples, or the cooler for the Day 0 samples). Note: Don 7forget to addperoxide to appropriate Day 0 samples! 13.9 Remove the exposed quinine control sample from the reactor tray and visually confirm a color change as an indicator of photoreactor performance. The solution should be a gray/brown color after irradiation. Record the total time exposure o f the sample, wrap the sample in foil to protect from light and analyze the quinine sample. Place a new quinine solution vial into the photoreactor tray with the exposed samples. Note: Quinine samples do NOT receiveperoxide. 13.10 Record the chamber temperature daily on the sample prep sheets. 13.11 Upon completion of the photolytic exposure, samples are removed, labeled with adhesive-backed labels and the study sets (Exposed, Unexposed and Day 0) organized for LC/MS or GC/MS analysis. If subsequent analysis can not be performed immediately, store samples in a cooler at 1-5 C. 13.12 Pertinent information regarding start and stop times of photoreactor exposure study, water bath and chamber temperatures, addition of peroxide, and an explanation of unexpected occurrences shall be documented on the sample preparation worksheets, with appropriate dates, times and initials. 14.0 Sa m p l e p r e p a r a t io n f o r a n a l y sis.________________________________________________ 14.1 LC/MS sample extraction and prep. 14.1.1 Dilute all 5 mL samples by a factor of 1:7 v/v by adding 30 mL of an appropriate analytical solvent containing internal standard (Section 8.6.2) to all vials. 14.1.2 Add spike solution (Section 8.6) containing the target analytes to the appropriate samples. 14.1.3 Ensure the sample vials are inverted several times to ensure adequate mixing. 14.1.4 If samples appear cloudy, and/or the sample matrix appears unclear, it may be necessary to centrifuge the samples, at an appropriate speed and duration (e.g. 2000 rpm for 10 minutes), until no noticeable particulate matter is suspended in the sample. 14.1.5 Aliquot approximately 1 mL into autovials and tightly cap. 14.2 GC/MS sample preparation. 14.2.1 Set up autosampler and concentrator methods. If samples have been kept in cold storage, bring samples to room temperature (approximately 23-26 C). 14.2.2 Spike vials through the septa and place in the autosampler. 15.0 D a t a A n a l y sis a n d C a l c u l a t io n s ________________________________________________ 15.1 The amount of target analytes in the sample will be quantified against a standard curve regression. 15.2 Means will be calculated by adding the individual entities and dividing the resultant sum by the number of individual entities. 15.3 Standard deviations will be calculated using either Microsoft Excel or Microsoft Access to calculate standard deviation. The built in function contains the following equation which is based on the individual entities (n) being less than 30: l,,Zx2 - ( Z x )2 \ n (n -1) ETS-8-176.0Pre/waf/w o f Sam plesf o r P hotolysis Studies in Aqueous M atrices Method Page 15 o f 18 Page 50 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 15.4 Sample precision will be reported as % relative standard deviation (% RSD). Sample % RSD will be calculated using the following equation: where: A/B X 100 = Sample % RSD A= standard deviation of averaged samples B= average of samples 16.0 M e t h o d P e r f o r m a n c e 16.1 Refer to the definitions section for the method performance specifications/criteria for each respective sample type. 17.0 Pollution Prevention and Waste Management_____________________________ 17.1 Dispose o f sample waste by placing in high or low BTU containers as appropriate. Use broken glass containers to dispose of glass pipettes. 18.0 R e c o r d s 18.1 Fill out the photolysis sample preparation worksheet documents completely, making sure to include all initials and dates. Store photolysis sample preparation worksheets in the raw data file. 18.2 Enter all standard, stock, solutions, etc. preparation information in the proper preparation logbook(s). Make a photocopy of the logbook pages used, and include the copy in the raw data file. Photocopied logbook pages will be included in the final data packet. 18.3 Archive electronic data to compact disc media. 19.0 A t t a c h m e n t s ________________________ . 19.1 Attachment A: Example Photolysis Prep sheet. 20.0 R e f e r e n c e s _____________________________ ______________________________________ 20.1 Crosby, Helz, and Zepp. Aquatic Surface Photochemistry, p 480 20.2 Interpersonal conversation with Carrie O'Connor, Optical Systems Engineer, Atlas Electric Devices. 20.3 "Suntest CPS/CPS+ Spectral Irradiance Distribution," table distributed by Atlas Electric Devices Company, sent via fax by Richard Sherwin, Sales Representative, 26 July, 2000. 20.4 "Atlas Xenon Filter Combination and Sunlight Measurements," information generated by Atlas Electric Devices Company sent via fax by Richard Sherwin, Sales Representative, 26 July, 2000. ETS-8-176.0P reparation o f Sam plesf o r P hotolysis Studies in Aqueous M atrices Method Page 16 o f 18 Page 51 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 20.5 Bergstrom, David H., Thomas C. Kester, and Shangdong Zhan. "Quinine Chemical Actinometry Studies Under Two Light Sources Specified by the ICH Guideline on Photostability Testing." 21.0 A f f e c t e d D o c u m e n t s 21.1 None 22.0 R e v is io n s Revision Number. Reason For Revision Revision Date ETS-8-176.0P reparatian o f Sam ples f o r Photolysis Studies in Aqueous M atrices Method Page 17 o f 18 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 Attachment A - Photolysis Sample Prep Sheet Fluorochemical Degradation (Photolysis) Analysis Sample Prep Sheet T u t Analyte: _________ ________________________ Project/Lab Request Num ber E x p o re T y p e :________________________ __________ *F o llo w in g in itia l sa m p le p r e p a ll sa m p le s w ill b e p la c e d c a p -sid e d ow n a n d ve rtic a l. N o m in a l Expos .................................... A n a ly s is : LC /M S ~ F o llo w in g p h o to ly sis, D a y 0 sa m p le s w ill b e p u lle d a n d e x tra c te d w ith E x p o se d a n d U n c xp a sed sa m p le s _______________________________________________________________________ Sam la M a trix : C ontrol M a trix : Sample No. D e s c rip tio n Rep 1 Rep 2 Rep 3 Sample M a trix V o lu m e : Date: T im e: In itia ls : am ple Type Solution .D . D tyO DayO DayO Test Analyte Soiutfait LD . Peroxide Solution LD. In te rn a r S pike Evolution Solution 1.0. Solution .D . C om m ents: Com m ents: Spike M atrix B lm k DyO DayO M a trix Blank Spike DayO Control Rep 1 Control Spike Control Blank C ontrol Blank Spike DayO DayO DayO DayO Rep 1 Rep 2 Rep 3 Spike M atrix Blank M a trix Blank Spike C ontrol Rep 1 Control Spike Control Blank Control Blank Spike Exposed Exposed Exposed Exposed Exposed Exposed Exposed Exposed Exposed Exposed Rep 1 Unexposed Rep 2 Unexposed Rep 3 Unexposed Spike Unexposed M atrix Blank Unexposed M a trix Blank Spike Unexposed Control Rep 1 Unexposed Control Spike Unexposed Control Blank Unexposed Control lank Spike Unexposed do m ponenti) and Solution Concentration Photolysis R eattori. .: Start Date: Time: Initials F re e ze r/R e frife ra to r Storage LD S an Due: Time: Stop Date: Time: Initials Stop Date: Time: T o ta l E x p o s u re :__________ day________ . boor_________ m in Initials Initials General Pintea; C h e c k m a r k - Indicates the solution added. n / i * not applicable P S S J S H fiS S " " t " " * " W * ID. |u require no addition o f solution C om m enta: ETS-8-11 6 .0P reparation o f Sam ples f o r P hotolysis Studies in A queous M atrices Method Page 18 o f 18 Page 53 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 3M Environmental Laboratory E q u ip m e n t Pr o c e d u r e O p e r a t io n a n d M a in t e n a n c e o f t h e Su n l ig h t E x p o s u r e Sy s t e m , I m m e r s io n u n it , a n d R e c ir c u l a t in g W a t e r C h il l e r Sy s t e m Procedure Number: ETS-9-44.0 Exact Copy of Original t f h i-tr-c o Initial D ate Approved by: Laboratory Management Adoption Date: Revision Effective Date: Date a * - /? z? Date ^ ETS-9-44.0 Equipment Procedurefo r the A tlas SUNTEST Sunlight Exposure System Page 1 of 8 Page 54 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 1.0 S c o p e a n d A p p l ic a t io n ________________________________________________ _ 1.1 This equipment procedure describes the regular operation and maintenance of the Atlas SUNTEST Sunlight Exposure System equipped with an immersion unit and recirculating water chiller. 2.0 Definitions __________________________________________________ 2.1 Photon energy: U = hv = hc/A, where h is Planck's constant, c is the speed of light, and v and X are the frequency and wavelength of light. Therefore, the energy of a photon, U, is inversely proportionate to the wavelength. 2.2 Irradiance: The energy output ("U" in the above equation for energy of a photon) in Watts/m2 specific to a wavelength or wavelength range. The irradiance output specific to the types of Atlas wavelength filters available (Reference 14.9) should be used as a guide to calculating the global irradiance (in units of W/(m2nm) needed to give a specific energy over a desired wavelength range. 3.0 D e s c r ip t io n __________________________________________________________ ____ ________ 3.1 The Atlas SUNTEST Sunlight Exposure System (CPS+ or XLS+) produces visible and ultraviolet light (250-765 W/m2). Light produced is filtered with a filter or combination of filters to allow specific wavelength ranges. Samples are exposed to the light in a reflecting chamber. An immersion unit with water recirculation through a chiller provides a cooled, constant sample temperature. 4.0 I d e n t if ic a t io n _____________________________________________________________________ 4.1 Atlas SUNTEST XLS+, equipped with a xenon arclamp, lamp filter(s) available from Atlas to allow specific irradiance ranges, and immersion unit. 4.2 Atlas SUNTEST CPS+, equipped with a xenon arclamp, lamp filter(s) available from Atlas to allow specific irradiance ranges, and immersion unit. 4.3 Neslab CFT-33 Refrigerated recirculator or equivalent 5.0 W a r n in g s a n d C a u t io n s ________________________________;___________________________ 5.1 Health and Safety Warnings: 5.1.1 Wear appropriate laboratory safety personal protective equipment. 5.1.2 The xenon lamp emits ultraviolet light which can cause bums to the skin and permanent damage to the eyes. Never attempt to operate the unit with the test chamber door open. 5.1.3 When filling the sample immersion unit with water, always shut off all power to the SUNTEST device and the immersion unit to prevent electrical shock. 5.2 Cautions: 5.2.1 Handle optical parts carefully, fingerprints on the lamp, filter or quartz dish can result in altered spectral output or early lamp failure. 5.2.2 The reflective coating of the test chamber walls is sensitive to scratches. Do not use any abrasives or harsh cleaning agents that may cause scratches and non uniform illumination of the test chamber. ETS-9-44.0 Equipment Procedurefo r the A tlas SUNTEST Sunlight Exposure System Page 2 of 8 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 5.2.3 5.2.4 5.2.5 Keep SUNTESTunit clear of obstructions that would block vents; overheating may cause blown fuses, shortened lamp life or other damage. After beginning the experiment, always make sure that the sample vials are sufficiently submerged. Excessive heat may affect the results of the experiment. Manually drain the immersion tank on the XLS+ models after stopping the run; otherwise, the water will overflow. 6.0 Special Instructions__________________________________________________ 6.1 None. 7.0 Responsibility__________________________________________________________ 7.1 The analytical group of personnel who routinely operates the equipment is collectively responsible for the instrument operation as described in this document. The person responsible for maintenance and calibration (and an alternate) will be identified in the front o f the equipment logbook. 8.0 S u p p l ie s a n d M a t e r ia l s _______________________________ ________________________ 8.1 Xenon lamp for XLS+, Atlas PN 56077798 8.2 Xenon lamp for CPS+, Atlas PN 56001794 8.3 Hand-tools as required 8.4 Kim-WipesTM 8.5 Optional radiation filters) for lamp available from Atlas: Filter/ Atlas Part Number Q uartz Dish w/ 1R reflective coating, PN 56052388 Q uartz Dish, PN 56052373 UV Special Suprax* Filter, PN 56052371 Window Glass Filter, PN 56052372 Window Glass Solar ID 65 Filter, PN 56077769 Solar Standard Filter, PN 56077759 ProDerties IR reflective coating (supplied standard with unit) Uncoated (to allow higher black standard temperatures) Cut-on at 290 nm, sim ulates outdoor solar radiation. Cut-on at 310 nm, simulates exposure behind 3 mm (0.118 in.) window glass. Cut-on at 320 nm, simulates exposure behind 6 mm (0.236 in.) window glass. (Must be used with Window Glass Filter above.) Cut-on at 290 nm, simulates outdoor solar radiation at optimal UV intensity. ETS-9-44.0 Equipment Proceduref o r the A tlas SUNTEST Sunlight Exposure System Page 3 of 8 Page 56 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 9.0 C l e a n in g P r o c e d u r e s _____________________________________________________________ All routine and non-routine cleaning procedures will be performed by person(s) designated in the front of the instrument logbook; see Section 12). 9.1 Routine cleaning 9.1.1 Clean the inlet air filters at the back of the SUNTEST unit every 6 months with a mild soap solution. Rinse in clean water. When more severe contamination is present, vacuum the filters or replace them. 9.1.2 Clean the reflector in the test chamber when it is dirty, using a soft cloth and mild soap solution. DO NOT use any abrasive cleaning materials or the reflector may be permanently damaged and irradiance uniformity will be altered. 9.1.3 Clean and/or flush the water tank and water lines on the immersion unit monthly to prevent build up of residue in the circulating water system. 10.0 M a in t e n a n c e P r o c e d u r e s _________________________________________________________ 10.1 Routine maintenance will be performed by the person(s) designated in the front of the equipment log (see Section 12): 10.1.1 Replace the xenon lamp after 1500 hours or when the required irradiance level cannot be achieved (e.g. error message reads "E MAX Power reached; CHANGE XENON LAMP") Refer to the SUNTEST instruction manual for details on how to replace the lamp. 10.1.2 If the temperature near the lamp becomes too high, the fuse blows to interrupt power and save the lamp (indicated by the error message "DOOR OPEN or TEMPERATURE FUSE"). Refer to the SUNTEST instruction manual for details on how to replace the fuse. 10.1.3 Record routine maintenance in the equipment log (see Section 12). 10.2 Non-routine maintenance will be performed by the person(s) designated in the front of the equipment log (see Section 12): 10.2.1 If the equipment fails to operate, refer to the equipment manual for further instructions, if necessary. Contact the Team Leader for instructions if the equipment cannot be made operational. 10.2.2 If an abnormal operating situation occurs or if calibration verification fails, contact the responsible individual identified in the equipment log. Label the equipment as "out of service" if it cannot be immediately repaired. 10.2.3 Record non-routine maintenance in the equipment log (see Section 12). 11.0 I n s t r u m e n t C a l ib r a t io n _________________________________________________________ 11.1 The photoreactor is set to maintain a specified integrated energy output. The amount of energy output from the lamp may be monitored with the use of a radiometer. The radiometer system will provide and record instantaneous energy output. Refer to ETS-950.0 Operation and Maintenance of Radiometer and Detector. 11.2 Calibration of SUNTEST systems will be performed two times each year by Atlas Electric Devices Company. ETS-9-44.0 Equipment Procedurefo r the A tlas SUNTEST Sunlight Exposure System Page 4 of 8 Page 57 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 12.0 O p e r a t in g P r o c e d u r e s ______________________________________________________ _ 12.1 For more detailed operating instructions refer to the equipment operating manuals. 12.2 Immersion Unit 12.2.1 To begin operation, fill the tank with water until the level indicator is up to the full mark. 12.2.2 Turn the power on. 12.3 Chiller 12.3.1 Turn the power on. Set water temperature knob to desired set point. Allow temperature to equilibrate before igniting the SUNTEST lamps. 12.4 SUNTEST XLS+ or SUNTEST CPS+ unit set-up 12.4.1 Select the desired wavelength filter from the parts listed under Section 8.4 to achieve the proper irradiation specified in the program, and program the photoreactor with the filter type information: With the photoreactor menu in the "Program" mode, select the appropriate filter combination type: ________________________ Optical Filter System Designations A: Coated quartz glass only______________________________ B: Coated quartz glass with UV special glass_________________ C: Coated quartz glass with window glass____________________ D: Uncoated quartz glass only ___________________________ E: Uncoated quartz glass with UV special glass_______________ F: Uncoated quartz glass with window glass 12.4.2 Selection/determination of energy output (W/m2) 12.4.2.1 Irradiance control and display is between 250-765 W/m2(nominally 300 800 nm). The irradiance is determined by the settings of the test program [including type of filter(s) used]. The selectable range is from 250 W/m2 to 765 W/m2 (page 12, XLS+ Instruction manual). The total (integrated) energy output (300-800 nm) is directly dependent on the type of lamp filter(s) used. E.g. if the filter has a narrow range such as a cut-on at 400 nm, all irradiance energy coming from wavelengths <400 nm will not reach the samples, and die total integrated irradiance will be less than if the filter's cut-on was at, for example, 290 nm. 12.4.2.2 Once the proper filter(s) is/are designated, the photoreactor will base the energy output on what type of wavelengths are being allowed to pass through the filter system to reach the samples. To calculate the energy output to program into the system, refer to References 14.7,14.8 and 14.9 as guides to calculate the desired spectral irradiance. Reference 14.7 may be used to calculate the programmed global irradiance necessary to achieve desired irradiances at specific wavelengths or wavelength ranges. Reference 14.8 maybe used to reference sunlight measurements and to correlate natural sunlight to the Atlas Suntest photoreactors. Reference 14.9 is a useful reference for determining irradiances at a specific ETS-9-44.0 Equipment P rocedurefo r the A tlas SUNTEST Sunlight Exposure System Page 5 of 8 Page 58 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 wavelength or a wavelength range using specific filter combinations at specified global irradiances o f 250,500, and 765 W/(m2nm). 12.5 Photoreactor Analysis set up 12.5.1 Place VOA (volatile organic analysis) vials containing samples (see the appropriate analytical method) into the test chamber. Sample vials to be exposed must be cap side down to allow light to enter the vial. Tighten caps securely to prevent leakage. Secure the vials in the chamber to prevent floating once the water begins to circulate. 12.5.2 Close the chamber door and turn the power on. 12.5.3 From the initial LCD display, use the arrow keys to select Program. Press "Enter". 12.5.4 If programming a new method is necessary, use the arrow key to select Programming. Press "Enter". 12.5.5 Input program number, number of phases, desired irradiance, immersion function, phase time and switch off criteria. Each entry is followed by the "Enter" key. 12.5.6 To start the program, select "Program Start" and press the "Enter" key. 12.5.7 Press "Escape" for the next screens if the filter has not been changed and no printout is desired. Input program number and press "Start" 12.5.8 Program will begin with lamp ignition. Note: Due to the modified sample chamber in the SUNTEST XLS+ models, the water initially present in the immersion tank is not sufficient to fill the sample chamber once a program has started. Refill the immersion unit as the water level drops below the fill line. Once a program has finished, drain the immersion tank so that it does not overflow when water from the sample chamber drains back down into the immersion unit. Failure to do so may result in remote flooding. 12.5.9 To interrupt operation (e.g. to add peroxide reagent)Press "Stop". If it is necessary to turn the power off (to exchange the lamp, for example) wait until the fan turns off in 1-3 minutes before turning power switch to "Off" and unplugging the power cord. When ready to continue operation, turn power "On". 12.5.10 To resume operation, press "Start". The program will continue at the point o f interruption. 12.5.11 To read parameters during the program run, scroll through the parameters of the running program by using the arrow keys. This is helpful to see how many more hours are remaining in the running program. 12.5.12 The SUNTEST will shut off automatically when the switch-off criteria are reached. To display the total time and irradiance, press "Enter". Record exposure time in instrument run log. Then turn power "Off". 12.5.13 To manually stop the program, press "Stop". Wait until lamp is cooled, then press "Escape". Power can then be turned "Off". ETS-9-44.0 Equipment Proceduref o r the Atlas SUNTEST Sunlight Exposure System Page 6 o f 8 Page 59 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 13.0 Records____________________________________________________________ _ 13.1 Instrument logbooks 13.1.1 Equipment Log: The person(s) designated at the front of the equipment log will record all cleaning and maintenance activities in the appropriate log for each SUNTEST system. Records for routine maintenance of equipment must include the dates of the operation, whether the operations followed the SOP, and the initials of the person performing the operation. Records for non-routine repairs performed as a result of instrument failure or malfunction must include the nature of the defect, how and when the defect was discovered, any remedial action taken in response to the defect, and the date and initials of the person performing the maintenance. Maintenance by outside contractors should include their name and company affiliation. 13.1.2 Run Log: Record each experiment in the appropriate instrument logbook. Enter the operators initials, time and date of exposure, lamp intensity and water temperature as the samples are placed in the chamber. When samples are finished, record the time and date when samples came out, the ending chamber temperature and the actual hours of exposure. All entries made in the run log should be initialed and dated. 13.1.3 SUNTEST Data Output Log: XENOVIEW 2.2 Storage Software will receive and record the measurement data transferred from the SUNTEST system to a computer or printer, while a program is in progress. The measurement data recorded includes: number of phases, phase time, chamber temperature, radiant exposure, irradiance, running time, date and time data is recorded. Refer to XENOVIEW software instruction manual for details on how to operate software. Any printouts of program or other data should be initialed and dated prior to adding to the study file. 13.2 Identification records for each system include equipment ID, manufacturer, model number, and serial number of each individual component. In addition, if components are removed or added, the above information must be written in the logbook including the date the change was made and initials of the analyst completing the change. 14.0 R e f e r e n c e s ________________________________________________________________________ 14.1 SUNTEST XLS/XLS+ Instruction Manual, Doc. No. 20-8036-00 Rev. 0 12/98 Atlas Electric Devices Company. 14.2 SUNTEST CPS/CPS+ Operating Manual, 6/97 Atlas Company. 14.3 SUNTEST XLS+ Immersion Device Operating Manual, 2/99 Atlas Company. 14.4 SUNTEST CPS+/XLS+ Software Documentation 1.4 Atlas Company. 14.5 XENOVIEW 2.2 Storage Software Operating Instructions. 14.6 ETS-9-50.0, Operation and Maintenance of Radiometer and Detector. 14.7 "SUNTESTIrradiance in W/m2*nm". Tables furnished by Atlas Company. 14.8 "Atlas Xenon Filter Combination". Table furnished by Atlas Company. 14.9 "SUNTEST CPS/CPS+ Spectral Irradiance Distribution". Table furnished by Atlas Company. ETS-9-44.0 Equipm ent Proceduref o r the Atlas SUNTEST Sunlight Exposure System Page 7 o f 8 Page 60 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 15.0 Affected Documents 15.1 None. 16.0 Revisions Revision Number. Reason For Revision Revision Date ETS-9-44.0 Equipment Proceduref o r the A tlas SUNTEST, Sunlight Exposure System Page 8 of 8 Page 61 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 3M Environmental Laboratory A n a l y s is o f F l u o r o c h e m ic a l s b y A r c h o n P u r g e a n d T r a p A u t o s a m p l e r , T e k m a r Pu r g e a n d T rap C o n c e n tr a to r a n d A g il e n t G as C h r o m a t o g r a p h /M ass Sp e c t r o m e t e r Procedure Number: ETS-8-182.0 Exact Copy of Original ------ Q &L______ _ Initial D ate ' Approved by: Laboratory Manager learn Leader Adoption Date: Revision Date: Date Date ETS-8-182.0 Analysis o f FCs by Purge & Trap Autosampler/Concentrator/GC/M S BACK TO MAIN 3M Environmental Laboratory Report No. W2775 1.0 Scope and Application T l Scope. This method is used for the analysis of selected hydrolysis and photolysis samples for the presence of degradation products such as olefins and hydrides using gas chromatography/mass spectrometry in a full scan mode. An Archon autosampler and Tekmar Purge and Trap concentrator (or an equivalent system) is coupled to a GC for purging analytes from the liquid matrix and concentrating them on the trap column before injecting on to the GC. 1.2 Applicable compounds. Compounds that may be analyzed by this method are listed below. Other fluorochemicals may be detected by monitoring mass spectra and running library comparison. Compounds that are detected but do not have appropriate standards, will be quantified relative to structurally similar standard compounds listed below. 1.2.1 lH-perfluoroethane (lH-pfC2) 1.2.2 Perfluro-2-butene (pfC4-2ene) 1.2.3 lH-perfluropropane (lH-pfC3) 1.2.4 lH-perfluorobutane (lH-pfC4) 1.2.5 Perfluoro-2-heptene (pfC7-2ene) 1.2.6 Perfluoro-1-heptene (pfC7-l ene) 1.2.7 lH-perfluorohexane (lH-pfC6) 1.2.8 Perfluoro-2-octene (pfC8-2ene) 1.2.9 lH-perfluoroheptane (lH-pfC7) 1.2.10 2H-perfluorooctane (2H-pfC8) 1.2.11 lH-perfluorooctane (lH-pfC8) 1.3 Instrum ent Surrogate compounds. Added at the time of analysis and used to monitor performance of purge and trap autosampler and concentrator. 1.3.1 Dibromofluoromethane 1.3.2 Toluene-d8 1.3.3 4-Bromofluorobenzene 1.3.4 Pentafluorobenzene 1.3.5 1,4-Difluorobenzene 1.3.6 Chlorobenzene-d5 1.3.7 1,4'Dichlorobenzene-d4 1.4 Sample Surrogate compounds. M ay be added at the tim e o f sam ple preparation. 1.4.1 Perfluorocyclohexane 2.0 Summary op Method________________________________________________________ 2.1 A dynamic purge and trap system (autosampler and concentrator) is coupled to a temperature programmed GC for analyte separation and subsequent mass spectrometer detection and quanitation. The liquid sample is purged for 20 min. in the sample vial, and the volatile components are swept onto a chemical trap in the concentrator. In the subsequent desorption mode, gas flows in opposite direction and temperature o f the chemical trap increases to 250 C. The trapped analytes are transferred onto the GC column for GC/MS separation, detection, and quanitation. Through this process, a high volume of sample is injected and most of the non-volatile matrix components stay in the sample vial, allowing low level detection of fluorochemicals. ETS-8-182.0 Analysis ofF C s by Purge & Trap Autosampler/Concentrator/GOM S Page 2 o f 12 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 3.0 Defin itio n s 3.1 Calibration Standard. A dilution of various amounts of a stock, intermediate or purchased standard to achieve standard solutions in a concentration range of interest. 3.2 Calibration Curve. The graphical relationship between known values, such as concentration of a series of calibration standards and their instrumental response. 3.3 External Standard Quantification. Process of establishing the concentration of a target analyte by plotting the theoretical amount (in units of ng/mL or pg/mL, etc.) versus the response of the target analyte(s) on column. The resultant curve(s) shall be used to determine unknown concentrations by comparing the area response of target analyte(s) to the area response and corresponding analyte amount on the appropriate analyte's calibration curve. 3.4 Coefficient of Determination (r2). The square of the correlation coefficient. It is the proportion of the variation in the dependent variable that is accounted for by the independent variable. 3.5 Instrument Surrogate. An organic compound similar to the target analyte(s) in behavior in the analytical process, but is not normally found in the sample(s). A surrogate may be added to sample vial during instrument analysis. 3.6 Sample Surrogate. An organic compound similar to the target analyte(s) in chemical composition and behavior in the analytical process, but is not normally found in the sample(s). A surrogate may be added to sample triplicates and matrix spike samples along with the test analyte (pre-photolysis). 3.7 Continuing Calibration Verification (CCV). Standards analyzed during an analytical run to verify the continued accuracy of the calibration curve. This solution may or may not be prepared from a different source or lot number than the calibration curve standards. 3.8 Solvent Blank. A sample of analyte-free medium that is not taken through the sample preparation process. This blank is used to evaluate instrument contamination. 3.9 Blank. For photolysis studies, there are multiple blanks to adequately represent the variables of thestudy (Exposed, UnexposedandDay 0 samples with/without peroxide addition). The blank is carried through the sample preparation, photolytic and analytical procedures to monitor for contamination during any step. It is also used to establish a chromatographic baseline/background and monitor for analytical interference or suppression of target analyte(s) from the matrix. 3.9.1 3.9.2 M atrix Blank: A sample of analyte-free matrix (buffered water, lake water, etc.) to which all reagents are added in the same volumes or proportions as used in sample processing. It is used to document the test system without test analyte. Control Blank: A sample of analyte-free matrix (Milli-Q water) to which all reagents are added in the same volumes or proportions as used in sample processing. It is used to control the test matrix and monitor matrix specific ETS-8-182.0 Analysis o f FCs by Purge & Trap Autosampler/Concentrator/GC/M S Page 3 o f 12 Page 64 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 background levels, interferences or suppression of target analyte(s) from the matrix. 3.10 Lim it of Quantitation (LOQ). The lowest concentration that can be reliably measured within specified limits o f accuracy during routine laboratory operating conditions. The LOQ is generally 5 to 10 times the minimum concentration with a 99% confidence limit that the concentration is greater than zero. However, it may be nominally chosen within these guidelines to simplify data reporting. For many analytes, the LOQ is selected as the lowest non-zero standard in the calibration curve that is greater than 4 times the level of the matrix blank. 3.11 Sample Triplicates. Three samples taken from and representative of the same sample source. These are prepared separately and carried through all steps of the exposure, extraction and analytical procedures in an identical manner. There are multiple sets of triplicate samples to adequately represent the photolytic variables of the study (Exposed, Unexposed and Day 0 with/without peroxide addition). Triplicate samples are used to assess variance of the photolytic method, including sample preparation, photolysis exposure, and analysis. 3.12 Relative Standard Deviation (RSD). A measure of precision defined as the standard deviation of three or more values divided by the average of the values and multiplied by 100. (Also reported as Coefficient of Variation (CV))- 3.13 Analytical Spike. Prepared by adding a known mass of target analyte(s) to a specified amount o f a sample or control matrix prior to analysis. This assumes that an independent estimate of target analyte concentration is available. Matrix spikes are used to determine the effect o f the matrix on method recovery efficiency. 3.14 Accuracy. The closeness of agreement between an experimentally determined value and an accepted reference value. When applied to a set of observed values, accuracy is a combination of a random (precision) and a common systematic (bias) component. For purposes of the study, the acceptance criterion is 75% to 125% of the nominal value. 3.15 Geometric Mean of the calibration curve: The square root of the product of the high standard concentration and the low calibration curve standard. When preparing calibration curve standards, the number o f calibration standards below the geometric mean shall equal the number of calibration standards above the geometric mean. Having equal distribution of calibration standards above and below the geometric mean when analyzing and reprocessing data, effectively weights the curve such that both the high and low ends o f the curve are given equivalent significance. 4.0 Warnings and Cautions________________________________________________ 4.1 Health and Safety Warnings: 4.1.1 The operator must be familiar with the purge and trap autosampler/concentrator/GC/MS system and associated hazards, such as high temperature, effluent venting, solvent use, and low-pressure vacuum system. See instrument manuals ETS-8-182.0 Analysis ofF C s by Purge & Trap Autosampler/Concentrator/GC/M S Page 4 o f 12 Page 65 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 4.1.2 All exhaust vents, including the GC oven vent, Tekmar concentrator purge vent, split vent and mass spectrometer pump exhaust must be connected to the laboratory vent system to keep potentially hazardous effluent from mixing with laboratory air. 4.2 Cautions: 4.2.1 It is recommended that a grounded antistatic wrist strap be worn while disconnecting all wires, contacts, or cables which are connected to printed circuit boards within the Archon autosampler, Tekmar concentrator or MS analyzer. 4.2.2 To prevent the breakage of the Standard Vial on the Archon autosampler, do not use any tool and do not overtighten the thumbnut. 5.0 I n ter fer e n c e 5.1 Methanol, water and other co-extracted matrix components could interfere with detection decreasing sensitivity. 6.0 Equipment _______________________________________________________ 6.1 System: "Rufus", or equivalent: 6.1.1 Autosampler: Varian, Archon 6.1.2 Concentrator: LSC2000, Tekmar 6.1.3 GC: 6890, Agilent 6.1.4 MS: 5973N, Agilent 6.1.5 Column, GS-GASPRO 60m x 0.23mm, J&W 7.0 Supplies and Materials______________________________________________ 7.1 Helium, ultra-high-purity 7.2 40ml VOA vials, e.g. I-Chem, S236-0040 8.0 R eagents and Standard__________________________ 8.1 Methanol, Purge and Trap grade or equivalent 8.2 Standards. Typically a minimum of five calibration standards, ranging from 1 ng/ml to 20 ng/ml are prepared. This concentration range should bracket the concentration of samples and matrix spikes; if the analyte concentration exceeds this range, then the calibration range should be increased. 8.3 Instrument Surrogates. Used only to monitor performance of purge and trap autosampler and concentrator and not for quantitation. 8.4 Sample Surrogates. May be used to monitor sample preparation, photolytic exposure and analytical performance. 9.0 Sample Handling________________________________ 9-1 Store standards and samples in the refrigerator at 4 0 C + 3 flC until analysis time. ETS-8-182.0 Analysis o f FCs by Purge & Trap Autosampler/Concentrator/GC/M S Page 5 o f 12 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 9.2 For the analysis, pull samples and standards out of the freezer and bring them to room temperature. 10.0 Q u a lity C o n tro l 10.1 Calibration Standards. Calibration standards (Section 11) used to generate a calibration curve. The number of calibration standards and the concentration levels should be sufficient to encompass the expected concentrations of the study samples. In general, a minimum of five calibration standards is required for fit of linear regression. 10.2 Continuing Calibration Verification (CCV). Analyze a mid-range calibration standard after a maximum o f every fifteen samples. 10.3 Solvent blank. Solvent blanks are run before and after every calibration curve, CCV, matrix and control blank (see 3.9.2), and after batches of no more than 30 injections. Acceptable values for the blanks are values below 25% of the limit of quantitation (LOQ) of the instrument. If analyte carryover is a problem, use back-to-back solvent blanks. 10.4 Sample Triplicates. Prepare and analyze all samples in triplicate to provide a measure o f the precision o f analysis. 10.5 Analytical Spikes. Prepare a matrix spike sample for each sample type as applicable to determine the matrix effect on the recovery efficiency. Concentrations of the spike should be approximately equal to a mid-range calibration standard. The matrix spike sample should be analyzed periodically to measure the precision associated with the analysis. The analyst shall accept percent spike recoveries of 100 25%. Spike recoveries outside of this range should be noted and used with other criteria to evaluate the condition of the analytical run. Consult with the Team Leader or designee for direction and final acceptance or rejection of the analytical run. 11.0 C a libra tio n and Standardization 11.1 Analyze standards prior to each set of samples. The linear regression will be calculated from the plot of all individual calibration points, without including or not forcing through zero, using Target NT Software. A minimum o f five calibration standards is required to generate linear regression for target analyte(s). If the calibration curve residuals are greater than 25% deviation from the theoretical value, quadratic curve fitting and/or dropping low/high curve points may be required if data review shows this to be a consistent and more accurate representation of the instrument response. Document in the raw data the technical justification for any deviation and consult with the team leader or designee for direction and for final acceptance or rejection of the data. 11.2 If the curve does not meet requirements perform routine maintenance or prepare a new standard curve (if necessary) and reanalyze ETS-8-182.0 Analysis o f FCs by Purge & Trap Autosampler/Concentrator/GC/M S Page 6 of 12 Page 67 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 12.0 Pro cedur es 12.1 Set Archon autosampler 12.1.1 Archon System Settings US Probe Temp 180 Xfer line Temp 180 US Valve Temp 105 Gripper Open 750 Gripper Closed 999 Standby Pol CLOSED DesDm Pol CLOSED STOP Pol. CLOSED Equilb. Count 0 Equilb. Time 0 12.1.2 Archon System Options Barcode Scanner NO Needle Sparge? YES Ign. Vial Type? YES Ignore No Vial? NO HotWater Rinse? NO Vial Checks? YES Beep on Error? YES 12.1.3 Archon Method Sample Type Soil First Vial 1 Last Vial up to 51 Sample Volume 10 Standard 1 (luL) YES Standard 2 NO SJPreHeat Stir NO Stir Syring Flushes NO 0 PreHeat PreHeat Temp YES 35 PreHeat Time 1.0 Purge Time 20.0 Desorb Time(m) 0.5 Oper. Mode Remote Cycle Timer 0.0 Aux. Timer 0.0 Link to Method 0.0 Soil Purge Flow 40ml/min Soil Purge Pressure 20psi ETS-8-182.0 Analysis ofF C s by Purge & Trap Autosampler/Cancentrator/GC/M S Page 7 o f 12 Page 68 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 12.2 Set Tekmar options Standby 40C (30C by purge) Purge 20.00min Dry Purge 2.00min Desorb Preheat 245C Desorb 0.50min at 250C Bake lO.OOmin at 260C BGB OFF BGB Delay Osec Auto Drain ON Valve 180C Line 180C Mount 100C Runs per Sample 1 Purge Flow Purge Pressure Trap 40mL/min 20psi VOCARB 3000 Containing: Carbopack B Carboxen 1000 Carboxen 1001 12.3 Set GC conditions 12.3.1 Oven: Initial temp: 40 C Initial time: 4.00min Ramp at 15.00 C/min to 280 C Final time: lO.OOmin 12.3.2 Front Inlet: Mode: Split Initial temp: 180C Pressure: 8.50psi (on) Split ratio: 10.7 : 1 Split flow: 16.1 ml/min Total flow: 20.6 ml/min 12.4 Set MS conditions 12.4.1 Adjust conditions as needed to optimize system performance and document operating conditions in the instrument run log. Acquisition mode: Scan (from 10 m/z to 650 m/z) MS source temp: 230 C MS quadruple temp: 150C Interface temp: 260 C Multiplier voltage: adjust to give required low standard sensitivity ETS-8-182.0 Analysis o f FCs by Purge & Trap Autosampler/Concentrator/GC/M S Page 8 o f 12 Page 69 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 12.5 Set up the instrument acquisition method. Name the sequence. The sequence includes a sample list documenting the method used and datafiles created. The sequence should be documented n the run files. 12.6 Sample analysis. 12.6.1 Set up autosampler and concentrator methods. Bring samples to room temperature (~22 C), spike them and place them on autosampler. Generate a mass spectrometer tune report and review. Operating conditions provided above are recommended and may be adjusted to optimize system performance. Analyze all standard, samples, and spiked samples using the same analytical conditions. Document the conditions in the run log. 12.6.2 When data acquisition is complete, data files should be transferred to Target version 4.0 for processing. 13.0 D a t a A n a l y sis a n d C a l c u l a t io n _________________________________________________ 13.1 Each batch of data should be processed using Target Genie integrator. Integration parameters should be set to minimize the number of manual integrations required yet still result in uniform integration of peaks at all concentration levels. If manual integrations are required, a review code should be assigned to indicate the reason. Review Codes are listed below. Review Code Explanation Peak was not automatically integrated by Target, therefore, integrated Ml manually Peak was automatically integrated; was reintegrated manually to M2 improve sample-to-sample integration consistency. Incorrect quantification ion peak was integrated; manual integration M3 was done to select the correct peak. Incorrect monitor ion peak was integrated; manual integration was M4 done to select the correct peak. M5 Others (specify) 13.2 When data processing is complete, summarize the data using an appropriate form. Formula is provided below for some of the calculations that may be required. 13.2.1 Calculate matrix spike percent recoveries using the following equation: %Recovery = (observed concentration - background concentration) x100 expected concentration 14.0 M eth o d P erfo rm an ce 14.1 Coefficient of Determination (r2). The coefficient of determination (r2) for the initial calibration curves should be 0.990 or greater. The curves should be examined closely for ETS-8-182.0 A nalysis o fF C s by Purge & Trap Autosam pler/Concentrator/G OM S Page 9 o f 12 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 linearity and intercept, particularly for accuracy of quantitation at the low and high ends o f the curve. Consult with the Team Leader or designee for direction and for final acceptance or rejection for the data. 14.2 Calibration Standards. The acceptance criterion for the calibration standards is that the accuracy of each standard is 75% to 125% ( 25 % difference) of the nominal value. Calibration standards outside this range are to be noted. Document in the raw data the technical justification for deviations. Consult with the Team Leader or designee for direction and for final acceptance or rejection for the data. 14.3 Instrument Surrogate. Review of the instrument surrogate performance is performed by monitoring instrument surrogate recoveries throughout the run. Inconsistencies in the recoveries may be the result o f instrumental changes, or injection error. Consult with the Team Leader or designee for direction and final acceptance or rejection of the analytical run. 14.4 Sample Surrogate. Sample surrogate performance is evaluated by averaging the area response throughout the analytical run and calculating %RSD. Inconsistencies in the surrogate peak area may indicate instrumental changes, injection error, or changes in the test-system. Consult with the Team Leader or designee for direction and final acceptance or rejection of the analytical run. 14.5 Continuing Calibration Verification. If the accuracy for the amount of quantified analyte is greater than 25% from the nominal value relative to the initial standard curve, the Team Leader should be consulted. Only those samples analyzed before the last acceptable calibration check standard will be used. Consult with the Team Leader or designee for direction and for final acceptance or rejection for the data. 14.6 Solvent Blanks. Solvent blanks should show no more than a 5% carryover from a high standard or calibration check standard. If so, two sequential solvent blanks may be necessary to rule out instrumental contamination 14.7 Matrix Blanks. Matrix blanks are the basis for determining the LOQ and are monitored at various times in the analytical run. Peaks with greater than 25% of the peak area of th designatedLOQvalueobservedin matrixblanks areindicativeofeithermatrix effect, sample contam ination or instrument contamination. Use o f solvent blanks prior to the matrix blank may be necessary to ruleoutinstrumental contaminationor sample contamination. 14.8 Control Blanks. Control blanks are the basis for determining matrix effect (interference or suppression). Peaks with greater than 25% of the peak area of the designated LOQ value observed in control blanks are indicative of either matrix effect, sample contamination or instrument contamination. 14.9 Limit of Quantitation (LOQ). The LOQ is equal to the lowest acceptable standard (i.e. % accuracy is 25 % nominal value) in the calibration curve that is greater than 4 times the level of the matrix blanks. 14.10 Sample Triplicates. The analyst shall accept %RSD values < 25%. %RSD values > 25% should be noted. Data used in the final report that is deemed out of control will be ETS-8-182.0 Analysis ofF C s by Purge & Trap Autosampler/Concentrator/GC/M S Page 10 of 12 Page 71 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 required to have technical justification for why the data is used, documented in the final report and raw data. Consult with the Team Leader or designee for direction, and for final acceptance or rejection of the data. 14.11 Analytical Spikes. The analyst shall accept percent spike recovery values of 100 25%. Spike recoveries outside o f this range should be noted. Consult with the Team Leader or designee for direction, and for final acceptance or rejection of the data. Data that are used in final report that is deemed out of control will be required to have a technical justification for why the data are being used, documented in the final report and raw data. 14.12 System Suitability. 14.12.1 Tuning: A mass spectrometer tune report shall be generated before starting each analytical sequence. If the tune parameters do not meet the criteria suggested by the mass spectrometer manual, then the mass spectrometer should be re-tuned. If mass 28 is present in the tune report at >10% relative to mass 69 then an air leak is present in the system. The source of the leak should be isolated and fixed before the sequence is stated; however if a slight air leak is detected, data can be collected, analyzed, and used as long as the data quality objectives are met. 15.0 P o l l u t io n P r e v e n t io n and W a st e M a n a g e m e n t _________________________________ 15.1 Dispose of sample vials in low BTU and flammable solvent in high BTU containers. Dispose of glass pipette waste in broken glass containers located in the laboratory. 16.0 R eco rd s 16.1 Store chromatograms in the study folder that is labeled with the study number. Include the following information on each chromatogram either in the header or hand written on the chromatogram: injection date, analyst's initial, sample unique number, sample name, preparation date, incubation period, dilution factor (if applicable), and instrument name. Store a copy of the acquisition conditions with the chromatogram packet. 16.2 Plot the calibration curve by non-weighted linear regression and store in the study/project folder. 16.3 Print the sequence and MS tune report from HP Chemstation. The sequence should be initialed and dated, and stored in the run log binder. The MS tune report should be stored in the tune report file. Copy of the sequence and MS tune report should be placed in appropriate study/project folder. 16.4 Summarize data using suitable software and store in the study/project folder. 16.5 Back up electronic data to appropriate medium (primarily CD). Record in the study/project folder the filename and location of backup electronic data. 16.6 List the documents and records generated when performing this method and where they are to be archived. ETS-8-182.0 Analysis o f PC s by Purge & Trap Autosampler/Concentrator/GC/M S Page 11 of 12 Page 72 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 17.0 Attachment 1Z _ _ 18.0 References____________________________________ ^____________ 18.1 Archon Purge and Trap Autosampler System Operator's Manual, 1996, Varian. 18.2 Tekmar LSC200 Instruction Manual, 1996, Tekmar. 18.3 Agilent MSD Hardware Manual for 5973N, 1999, Agilent. 18.4 Agilent 6890 Series Gas Chromatograph, volumes 1-3,1999, Agilent 19.0 Affected Documents 19.1 None. 20.0 Revisions Revision Number. Reason For Revision Revision Date ETS-8-182.0 Analysis ofF C s by P urge & Trap Aulosampler/Concentrator/GC/M S Page 12 o f 12 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 3M Environmental Laboratory Method Indirect Photolysis Screening Test in Synthetic Humic Water Method Number: ETS-8-177.0 Approved By: Laboratory Management Adoption Date: Revision Effective Date: k) Date ETS-8-177.0 Indirect Photolysis Screening Tests in Synthetic Humic Water P a g e t o f 16 Page 74 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 1.0 S c o p e a n d A p p l ic a t io n _______________________________________________________ 1.1 Purpose. Chemicals dissolved in natural waters are subject to two types of photoreaction. In the first case, the chemical of interest absorbs sunlight directly and is transformed to products when unstable excited states o f the molecule lead to decomposition. In the second case, reaction of dissolved chemical is the result of chemical or electronic excitation transfer from light-absorbing species in the water. Synthetic humic water (SHW) is used for the photolytic reaction matrix because it contains dissolved organic material that absorbs sunlight and produces reactive intermediates that include singlet oxygen (10 2) that promotes indirect photolysis of the test substance. 1.2 The method is divided into two phases. Phase one includes the preparation of SHW. Phase Two provides a procedure to calculate solar photolysis rate constants and half lives of test chemicals in pure water (PW) and SHW. This phase also includes parallel solar irradiation o f a radiometer to calculate k,0 (the indirect photolysis rate in the test vessel, e.g. 40 mL glass VOA vial) and kpE(the near-surface photolysis rate constant in natural water bodies). 1.3 Compatible Analytes. Chemicals that will be subjected to this indirect photolysis screening and testing method include but are not limited to the following compounds: Compound Perfluorooctanoic acid Perfluorooctanesulfonate Perfluorooctanesulfonamide N-methylperfluorooctanesulfonamide N-ethylperfluorooctanesulfonamide 2 -(N-methylperfluorooctane sulfonamido) ethyl alcohol 2-(N-ethylperfIuorooctane sulfonamido)ethyl alcohol i -pcrfluorooctenc Perfluorooctanehydride Acronvm PFOA PFOS FOSA N-MeFOSA N-EtFOSA N-MeFOSE-OH N-EtFOSE-OH -- 1H, Cj-hydride Compound Perfluorobutanoic acid Perfluorobutanesulfonate Perfluorobutanesulfonamide N-methylperfluorobutanesulfonamide N-ethylperfluorobutanesulfonamide 2-(N-methylperfluorobutanesulfonamido) ethyl alcohol Acronvm PFBA PFBS FBSA N-MeFBSA N-EtFBSA N-MeFBSEOH 2-{N-cthyIperfluorobutflnesulfonamido)ethyl alcohol N-EtFBSE-OH 1-perfluorobutene Perfluorobutanehydride -- 1H, C4-hydride ... and other C4 through C iq homologues, and polymeric materials based on the above aforementioned compounds. 1.4 Acceptable matrix. Synthetic humic water (SHW), 0.005 M pH 7.0 Phosphate Buffer. ETS-8-177.0 In direct P hotolysis Screening Tests in Synthetic H um ic W ater Page 2 o f 16 Page 75 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 2.0 Summary of Method___________________________________________ 2.1 Phase One: A solution of standardized synthetic humic water is prepared by water extraction of commercial humic material. The SHW is buffered at pH 7 with 0.005 M Phosphate buffer to maintain pH and pre-aged in the photoreactor to produce predictable bleaching behavior. It is then diluted at the time of use to a UV-visible absorbance typical o f most surface fresh waters (approximately 0.5 AU at 370 nm). 2.2 Phase Two: Study samples (5mL aqueous matrix) are prepared in 40 mL glass VOA vials equipped with screw-top caps with septa. Test substance is added to the vials where indicated. (See table below.) Vials are placed in the photoreactor and immersed in a water bath controlled at 25 5 C. Samples to be exposed are photolyzed in the photoreactor at 261 W/m2(300-800 nm) for designated time intervals. A suggested set of time intervals is listed below. Additional timepoints may be added, if necessary, or as assigned by the Team Leader. Time 0 samples will be refrigerated at 1-5 C. until all timepoints have been completed. Dark controls (unexposed) will also be prepared for each timepoint. Absorbance controls will be used to monitor photo-bleaching of the SHW. Exposed and unexposed absorbance controls will be prepared per timepoint. 2.2.1 Samples to be prepared for each timepoint and for each exposure type: 1 Description Sample Rep I Sample Rep 2 Sample Rep 3 Sample Spike 1 Sample Spike 2 Matrix Blank Matrix Blank Spike Control M atrix(#l) blank Control M atrix(#l)sample Control M atrix(#l) spike Control Matrix(#2) blank Control M trix<W 2) sample Control Matrix(#2) spike Absorbance Control A bsorbance C ontrol dup Test Matrix (Buffer /SHW) + + + + + + 0 0 0 0 0 0 + 4- Control Matrix 1 (Buffer/ PW) 0 0 0 0 0 0 0 + + + 0 O 0 0 0 Control Matrix 2 (PW) 0 0 0 0 0 0 0 0 0 0 + + 0 0 Test Substance + + + + + 0 0 0 + + 0 + 4- 0 0 Post Photolysis Target Analyte Spike 0 0 0 + ,+ 0 + 0 0 + 0 0 + 0 0 LC/MS Analysis A A A A A A A A A A A A A NA NA GC/MS A nalysis UV/Vts Analysis at 370 nm A NA A NA A NA A NA A NA A NA A NA A NA A NA A NA A NA A NA A NA NA A NA A 1 Where "+" = addition of solution or test substance and "0" = NO addition, A= analysis performed, and NA = no analysis. Time Point 0 8hr 16 hr 32 hr 64 hr 128 hr # of Exposed Samples 0 30 30 30 30 30 # of Unexposed Samples 30 (Time 0) 30 30 30 30 30 # of samples for LC/MS Analysis ( Exp + Unexp) 13 26 26 26 26 26 # o f samples for GC/MS Analysis (Exp + Unexp) 13 26 26 26 26 26 # o f samples for UV/Vis Analysis (Exp + Unexp) 4 8 8 8 8 8 Total # o f Samples 150 180 143 143 44 ETS-8-177.0 Indirect Photolysis Screening Tests in Synthetic Humic Water Page 3 o f 16 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 3.0 Q u a l it y c o n t r o l - d e f in it io n /f r e q u e n c y /P e r f o r m a n c e c r it e r ia ________________ _ _ gjajjj-g '~ 3.1.1 3.1.2 Definitions: M atrix Blank. A sample of analyte-free matrix (e.g. SHW/buffer) to which all reagents are added in the same volumes or proportions as used in sample processing. For photolysis studies, there are multiple matrix blanks to adequately represent the variables of the study with reference to the matrix (e.g. Exposed, Unexposed and Time 0). The matrix blank is carried through the sample preparation, photolytic and analytical procedures to monitor for contamination dining any step. It is also used to establish a chromatographic baseline and monitor for interference or suppression of target analyte(s) from the matrix. Control Blank. A sample of analyte-free control matrix (such as buffer or ASTM Type II water) to which all reagents are added in the same volumes or proportions as used in sample processing. The control matrix serves as a monitor of the effect of the matrix on the test substance, test analytes and chromatographic behavior. For photolysis studies, there are multiple control blanks to adequately represent the variables of the study with reference to the matrix (e.g. Exposed, Unexposed and Time 0 samples). The control blank is carried through the sample preparation, photolytic and analytical procedures to monitor for contamination during any step. It is also used to establish a chromatographic baseline and monitor for interference or suppression of target analyte(s) from the control matrix. Frequency/Performance Criteria: Listed in the following table: Matrix ID Matrix Blank (Buffer/SHW) Control Blank #1 (B uffer/P W ) Control Blank #2 (PW) Matrix descriotion Freauencv 0.01 M Phosphate Buffer, pH 7: Synthetic Humic Water 0.01 M Phosphate Buffer, pH 7 : ASTM Type H Water ASTM Type II Water 1 Replicate per light and dark exposure, for each time point and for each analytical methodology. Performance Criteria Any background level of target analyte shall be less than 25% the area counts of the LOQ. 3.2 Sample Triplicate 3.2.1 Definition: Three aliquots prepared as representatives of the same sample source (e.g. test substance) and carried through all steps of the photolytic study process and analytical procedures in an identical manner. The results from triplicate analyses are used to evaluate variance of the total method, including sample preparation, photolytic process and analysis. ETS-8-177.0 Indirect Photolysis Screening Tests in Synthetic Humic Water Page 4 o f 16 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 3.2.2 Frequency/Performance Criteria: Listed in the following table: Matrix Descrintion Freauencv Test Matrix and test 3 Replicates per substance treatment type Performance Criteria The analyst shall accept %RSDs <25%. Precision values >25% must be documented and justified (if possible). 3.3 Analytical Spike (AS) 3.3.1 Definition: A known mass of target analyte(s) in a specified amount o f a diluted and/or aliquotted sample. This assumes that an independent estimate o f target analyte concentration is available. Analytical spikes are used to evaluate the recovery efficiency of the analyte and the matrix effect. 33.2 Frequency/Performance Criteria: Listed in the following table: Matrix Description Test Matrix a n d test substance, spiked with target analyte(s) just prior to analysis Test Matrix w ith N O test substance, spiked with target analyte(s) just prior to analysis Control Matrix (#1) and test substance, spiked with target analyte(s) just prior to analysis Control Matrix (#2) an d test substance, spiked with target analyte(s) just prior to analysis Frequency . 2 spiked samples per treatment type (one in lower half of die calibration range, and one in the upper half of the calibration range) 1 Replicate per treatment type (mid-range spike concentration) Performance Criteria The analyst shall accept accuracy of 100 25%. If accuracy is outside of this range, document and justify, if possible, the reason for the deviation. 3.4 Control Sample 3.4.1 Definition: A known matrix containing the test substance carried through the entire sample preparation, photolytic and analytical procedure. This is used to document laboratory performance by comparing recoveries and matrix effects from the different matrices and sample types. 3.4.2 Frequency/Performance Criteria: Listed in the following table: Matrix Description Control Matrix (#1) and test substance Buffer/PW Control Matrix (#2) and test substance PW Frequency Performance Criteria 1 Replicate per light and dark exposure, for each time point, and for each analytical methodology The analyst shall accept accuracy of 100 25%. If accuracy is outside of this range, document and justify, if possible, the reason for the deviation. ETS-8-177.0 Indirect Photolysis Screening Tests in Synthetic Humic Water Page 5 o f 16 Page 78 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 3.5 Absorbance Control 3.5.1 Definition: An analyte-free matrix that is carried through the sample processing procedure and analyzed by absorption spectroscopy at 370 nm. It is used to monitor the photo-bleaching rate of the SHW during the testing phase. 3.5.2 Frequency/Performance Criteria: Listed in the table below. Matrix Description Control Matrix (#1) Buffcr/SHW only Frequency Performance Criteria 2 Replicates per light and dark exposure, for each time point Absorbance measured at 370 nm is between 0.01AU-0.05 AU (1 cm pathlength cell) 3.6 Internal Standard/Surrogate 3.6.1 Internal Standard Definition (applies to LC/MS samples): A known amount o f a compound similar in analytical behavior to the target analyte(s) o f interest (e.g. 3 ,3 ,4 ,4 ,5 ,5 ,6 ,6 ,7 ,7 , 8,8, 8-tridecafluorooctane sulfonic acid (THPFOS) if perfluorooctane sulfonate (PFOS) were to be the target analyte), added to all samples and standards (post-irradiation), and carried through the entire analytical process. It provides a reference for evaluating and controlling the precision and bias of the applied analytical method. Samples are to be quantified using the internal standard. 3.6.2 Surrogate Definition (applies to LC/MS and GC/MS samples): A known amount of a compound similar in analytical behavior to the target analyte(s) that may be added to all samples (pre- or post-irradiation, at the discretion o f the Team Leader), and carried through the remaining sample preparation and/or analytical process. If added before exposure, it monitors the presence of vial leaks during photolysis, as well as the performance of the purge and trap autosampler and concentrator. Surrogate analysis is used to evaluate the precision and bias of the applied analytical method. Surrogates are not used for quantitation. 3.6.3 Frequency/Performance Criteria: Listed in the following table: Matrix Descrintion Freauencv of Use Sample diluted with 30 mL of internal standard compound dissolved in a suitable analytical solvent Every LC/MS sample analyzed Sample with surrogate compound spiked into it. May be added to every LC/MS and GC/MS sample analyzed Performance Criteria The %RSD for internal standards shall be calculated for the area response of all appropriate samples per analytical batch. The analyst shall accept %RSD values of <15%. %RSD values >15% shall be documented and justified, if possible. The % recovery of internal standards should be 100 25%. .Surrogates are examined for qualitative information only (i.e., area response should be relatively constant). ETS-8-177.0 Indirect Photolysis Screening Tests in Synthetic Humic Water Page 6 o f 16 Page 79 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 3.7 Other Definitions. 3.7.1 Test Substance/Test Analyte: Any substance (mixture or controlled compound) added or administered to the test system for the purpose of chemical analysis. 3.7.2 Degradation Produces): Secondary analytes of interest produced as a result of chemical reactions during the photolysis and monitored (qualitatively or quantitatively) during the sample analysis procedure. 3.7.3 Target Analyte(s): The analyte(s) singled out in the analytical phase o f the study is the target analyte. The target analyte may be identical to the test substance used in the experimental phase of the study, a by-product or degradation product that is monitored (qualitatively or quantitatively) during the sample analysis procedure. 3.7.4 Test Matrix: The physical matrix in which the study will be conducted. 3.7.5 Relative Percent Difference (RPD): A measure o f precision defined as the absolute value o f the difference of the two values divided by the average of the two values and multiplied by 100. 3.7.6 Relative Standard Deviation (RSD): A measure of relative precision for three or more sample replicates; defined as the sample standard deviation divided by the sample average and multiplied by 100. This is expressed as a percent (%RSD). 3.7.7 Limit of Quantitation (LOQ): The lowest concentration that can be reliably achieved within specified limits of precision and accuracy during routine laboratory operating conditions. The LOQ can be estimated as 10 times the background level in the blank samples. However, it may be nominally chosen within these guidelines to simplify data reporting. For many analytes, the LOQ analyte concentration is selected as the lowest non-zero standard in the calibration curve that is over four times the background level in the blanks. Sample LOQs are highly matrix-dependent. 4.0 Warnings and Ca u t i o n s ________________________________________ 4.1 H ealth and Safety W arnings 4.1.1 Wear the proper lab attire for all parts o f these procedures. Wear gloves a n d eye protection at all times. 4.1.2 Handle all solvents in a hood for all parts of the described sample preparation procedure. 4.1.3 For potential hazards of each chemical used, refer to material safety data sheets, packing materials, and 3M Environmental Laboratory's Chemical Hazard Review. 4.1.4 No mouth pipetting is allowed. 4.2 Cautions 4.2.1 The photoreactors are equipped with a continuous flow of cooling water that poses a threat of electrocution when handling the photoreactor during irradiation sequences. ETS-8-177.0 Indirect Photolysis Screening Tests in Synthetic Humic Water Page 7 o f 16 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 4.2.2 Wear dark protective eyewear when operating the reactor. Do not look directly at the activated lamp. Use caution when handling samples in the reactor; the interior walls of the reactor and exposed glass vials become extremely hot. 5.0 Interference____________________________________________________ 5.1 Contaminants in solvents, reagents, glassware and other sample processing or analysis hardware may cause interference. To reduce the possibility of interference, glassware in which standards are prepared should be pre-rinsed with methanol and allowed to dry before use. The routine analysis of laboratory method blanks must be used to demonstrate that there is no interference under the conditions of the analysis. 6.0 Equipment___________________________________________________________ 6.1 Analytical balance sensitive to 0.1 mg 6.2 Photoreactor: Suntest CPS+, XLS+, or equivalent, capable of producing 250-765 Watts/m2, equipped with a xenon arclamp (e.g. 2200 W Xenon Lamp) and the appropriate filters to allow the desired wavelength (e.g. UV Special Suprax with cut-on at 290 nm, and Quartz dish with IR reflective coating), and a flowing water bath circulating pump or equivalent. 6.3 Water cooler/recirculator capable of maintaining temperature at 25 C 5 C . 6.4 UV-Visible Spectrophotometer (UV-VIS), equipped with tungsten and deuterium lamps, model 8453, or equivalent 6.4.1 Autosampler: Model G1120A, or 1-cm pathlength cell holder: Model 08451 60104, or equivalent. 6.4.1.1 1-cm pathlength quartz spectrophotometer cell, or equivalent. 6.4.2 Long Path-Length Cell Holder, Hewlett Packard part number 89076C, or equivalent 6.4.2.1 10-cm path length quartz cell equipped with stopcocks, Hewlett Packard Part # 5061-3392, or equivalent. 6.4.3 Data acquisition and analysis software, HP ChemStation for UV-Visible Spectroscopy, G1116AA Rev. B.01.02, or later. 6.5 D ata System : A PC capable o f controlling the U V-Visible Spectrophotometer system. 6.6 Centrifuge capable of maintaining >2000 rpm for 10 minutes at ambient temperature (22 26 C). 6.7 Radiometer, capable of detecting and recording irradiation output of the photoreactor for the duration o f the study. 6.8 Lab Oven, capable of maintaining 70-80 C. 7.0 S u p p l ie s a n d M a t e r ia l s ___________________________________________________________ 7.1 40-mL amber and clear glass vials (VOA) with screw caps. 7.2 Crimp cap autovials: 1.5-mL, caps, crimper, and decapper. 7.3 Adhesive-backed labels (return address size) for labeling quartz vials and autovials. 7.4 Disposable glass graduated pipettes, 1 mL to 10 mL. ETS-8-177.0 Indirect Photolysis Screening Tests in Synthetic Humic Water Page 8 o f 16 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 7.5 Disposable glass Pasteur pipettes and rubber bulbs. 7.6 Glass beakers, various sizes. 7.7 Volumetric flasks, from 10 mL to 1000 mL. 7.8 Hamilton Gastight syringes (precision 1% of the total volume), 5 pL to 1000 pL. 7.9 10-mL Bottle-top dispenser. 7.10 Teflon filters filter holder apparatus: 0.4 pm pore-size and 0.2 pm pore-size filters (47 mm diameter, GelmanTM or equivalent. 7.11 500-mL glass screw-top containers. 8.0 Reagents and Standards____________________________________________ 8.1 Water/Pure water (PW), ASTM Type 13water at a minimum 8.2 Methanol (MeOH), HPLC/SPEC/GC grade from EM Science or equivalent. 8.3 Acetone, HPLC/SPEC/GC grade from EM Science or equivalent. 8.4 Acetonitrile, HPLC/SPEC/GC grade from EM Science or equivalent. 8.5 Humic acid, sodium salt, from Aldrich or equivalent. 8.6 NaOH, reagent grade from EM ScienceTM or equivalent. 8.7 0.1 % NaOH solution Example: Weigh approximately 1.0 g sodium hydroxide into a weigh boat and transfer quantitatively to a 1 L volumetric flask and dilute to the mark with PW or equivalent. 8.8 Sulfuric Acid (H2S 0 4), reagent grade from Fisher or equivalent. 8.9 Potassium phosphate, reagent grade from JT Baker or equivalent. 8.9.1 0.005 M, pH 7.0 Phosphate Buffer. Example: Weigh 1.36 g KH2P 0 4into a weigh boat and transfer to a 1 L volumetric flask using PW and dilute to the mark. Transfer the 1 L of solution to a 2 L volumetric flask. Add 600 mL of 0.1% NaOH, adjust the pH to 7.0 0.1 with 0.1% NaOH or dilute H2S 04, and dilute to the mark with PW. 8.10 Method Blank Solutions: Method Blank Type Matrix ID Test Matrix Buffer/SHW Control Matrix (#1) Buffer/PW Control Matrix (#2) P W Matrix description Example: 1:10 Solution: D ilu te 50 m L Synthetic H um ic W ater w ith 0.01 M pH 7.0 Phosphate Buffer solution to 500 mL. Example: 1:10 Solution: Dilute 50 mL Pure Water (ASTM Type II) with 0.01 M pH 7.0 Phosphate Buffer solution to 500 mL. Pure Water (ASTM Type II) 8.11 Stock Solutions. Stock solutions for internal standards and spiking solutions are prepared in MeOH at concentrations of approximately 10,000 pg/mL by weighing approximately 0.1 g of the appropriate substance into a 10-mL volumetric flask and bringing to the mark with MeOH. Dilute to make appropriate working solutions. 8.11.1 Diluting Solution with Internal Standard: The diluting solution shall contain internal standard at an area response level equivalent to approximately half the ETS-8-177.0 Indirect Photolysis Screening Tests in Synthetic Humic W ater Page 9 o f 16 Page 82 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 area response of the test substance's high standard in the calibration curve. Example: Internal standard solution in MeOH is prepared by diluting 50pL of internal standard stock solution (Section 8.11) to 1 L with MeOH to a nominal concentration of 0.5 AU pg/mL. 8.12 Test Solutions 8.12.1 Test Substance: Prepare a solution of the test substance in acetonitrile. Calculate the concentration so that after the test substance is added to the test vial, no more than 1% of the volume in the test vial will be solvent, (e.g. 50pL added to 5 mL of matrix = 1% v/v) Then measure the absorbance of the test substance solution diluted with buffer/water matrix to the desired concentration. The maximum absorbance at any wavelength greater than 290nm must be < 0.05, when measured in a standard 1-cm pathlength cell. Example: A 900 pg/mL solution o f test substance in acetonitrile is prepared by weighing 90 mg o f test substance into a 100 mL volumetric flask and diluting to the mark with acetonitrile. 9.0 Sa m p l e H a n d l in g 9.1 Record times of initial preparation and dilution on the fluorochemical degradation (photolysis) analysis sample prep sheet (Attachment A). 9.2 Once the test substance solution has been added, the 40 mL VOA sample vials shall be stored and handled cap-side down to minimize loss of any potential volatile analytes. After the exposure period, the LC/MS samples may be turned upright and stored in a cooler at 1-5 C. After the exposure period, GC/MS samples shall be maintained in an inverted position in a cooler at 1-5 C until they are loaded onto the autosampler. 9.3 Once the 30-mL aliquot of diluting solvent has been added to the LC/MS photolysis samples, (see Section 12.0), the samples should be analyzed as soon as possible. Alternatively, the samples may be stored at 1-5 C. Day 0 samples are to be stored at 1-5 C during the time of sample exposure, and then diluted along with the exposed and unexposed samples just prior to analysis. 1 0.0 Q u a l it y C o n t r o l ____________________________________________ 10.1 Quality control parameters (and the frequency o f use) are included in Section 3.0. 1 1 .0 C a l ib r a t io n a n d St a n d a r d iz a t io n ___________________________________________ 11.1 The analytes of interest must be standardized according to laboratory specifications. 11.2 All equipment used, such as the analytical balance, photoreactors, etc. should be calibrated prior to use (daily, weekly, etc.) as specified in its standard operating procedure. 11.3 All samples analyzed will be run against a standard curve containing varying amounts of test substance, and a fixed amount of internal standard or surrogate compound. ETS-8-177.0 Indirect P hotolysis Screening Tests in Synthetic Humic Water Page 10 o f 16 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 12.0 P r o c ed u r es 12.1 Phase One-Preparation and standardization of synthetic humic water. 12.1.1 Weigh approximately 2.5 g humic acid into a tared 250 mL centrifuge tube. 12.1.2 Add 0.1% NaOH solution to 250 mL. 12.1.3 Screw-cap shut and tape the tube and place horizontally on an orbital shaker. Shake vigorously (e.g. 100-250 rpm) at room temperature for approximately one hour. 12.1.4 Centrifuge the 250 mL of solution at approximately 2000 rpm for 10 minutes or until solution has cleared, and then filter the supernatant through a 0.4pm filter into a clean 500-mL glass screw-top container. 12.1.5 Adjust the pH of the solution to 7.0 with dilute H2S 04or 0.1 % NaOH. 12.1.6 Filter-sterilize the solution through a 0.2pm diameter pore-size filter into a clean 500-mL glass screw-top container. 12.1.7 Seal the container and place cap-side down in the photoreactor chamber. 12.1.8 Expose the SHW 24 hours at 261 W/m2to pre-age the solution (equivalent to three day's worth o f Miami, Florida sunlight). The EPA's definition o f " 1 Day" o f irradiation is "eight hours." The irradiation intensity o f 261 W/m2was chosen because it yields the equivalent average optimum natural daylight radiation for 300-400 mn (see the table below): Aunroximate Intecrated and Individual Irradiances in W/m2 Irradiance Source 250-300 nm 300-400 nm 400-800 nm 340 nm 420 nm Average Optimum Natural Daylight1 0.0 27.8 259.0 0.30 0.67 Atlas Photoreactor with integrated irradiance output of 261 W/m2300-800 nm using the IR Reflecting and 290 cuton filters 0.08 27.8 'M easured --25 N, M iami, Florida (See Reference 18.4) 234.36 0.24 0.71 12.1.9 A liquot the SHW into a 1-cm quartz UV-VIS cuvette and analyze the absorbance at 370 nm. 12.1.10 Check the pH of the solution using pH paper or a pH probe. Adjust the pH if necessary to 7.0 + 0.1 using a dilute H2S04solution or 0.1% NaOH solution. 12.1.11 Calculate the dilution factor necessary to decrease the absorbance to approximately 0.5 AU (in a 1-cm pathlength cell) in 1 L of SHW: where: 1L x the measured absorbance of the SHW at 370 nm x = the volume of SHW needed to dilute to 1 L with water. 12.1.12 Bring the solution to the exact dilution calculated in 12.1.11 withPW. ETS-8-177.0 Indirect Photolysis Screening Tests in Synthetic Humic Water Page 11 o f 16 Page 84 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 12.1.13 Verify that the absorbance is approximately 0.5 AU by aliquoting the diluted SHW into a 1-cm UV-VIS cuvette and taking the absorbance reading at 370 nm. 12.1.14 Transfer the SHW stock solution into an amber, or clear foil-wrapped 1 L glass storage bottle, tightly cap and refrigerate. 12.2 Phase Two 12.2.1 Fill out the `Tluorochemical Degradation (Photolysis) Sample Prep Sheet" (Attachment A) as much as possible, assigning sequential unique ID numbers to each sample to be prepared. 12.2.2 Obtain the appropriate number of clear and amber 40-mL glass vials with caps and cardboard boxes. Label the vial caps using a black permanent marker to distinctly identify samples. 12.2.3 Create labels for each sample to be affixed to the 40-mL vials and the autosampler vials after photolysis is completed. The labels should include the sample number, test substance, matrix, exposure type (e.g. exposed/unexposed/Time 0), date and initials of the analyst. 12.2.4 Aliquot 5.0 mL of Buffer/SHW, Buffer/PW and PW solutions into clear (for exposed samples) and amber (for unexposed and Time 0 samples) 40-mL glass VOA vials. Add test substance to the appropriate vials. See the table below for list of vials, replicates, and sample types. If pre-hydrolysis surrogates are to be used, add them also at this point. 12.2.5 Create one set of samples (listed below) per time point and for each analytical methodology. (LC/MS and GC/MS): Description Sample Rep 1 Sample Rep 2 Sample Rep 3 Sample Spike 1 Sample Spike 2 Matrix Blank Matrix Blank Spike C ontrol M a trix (# l) blank Control Matrix!# 1) sample Control M atrix(#l) spike C ontrol M atrix(#2) blank Control Matrix(#2) sample Control Matrix(#2) spike Test Matrix (Buffer/SHW) + + + + + + + 0 0 0 0 0 0 Control Matrix 1 (Buffer/PW) 0 0 0 0 0 0 0 + + + O 0 0 Control Matrix 2 (PW) 0 0 0 0 0 0 0 0 0 0 -I- + Test Substance + + + + + 0 0 O + + 0 + + Sample Rep 1 Sample Rep 2 Sample Rep 3 Sample Spike 1 Sample Spike 2 Test Matrix Blank Test Matrix Blank Spike Control M atrix(#l) blank Control Matrix!# 1) sample Control Matrix!# 1) spike Control Matrix(#2) blank Control Matrix(32) sample Control Matrix(32) spike + + + + -F + 0 0 0 0 0 0 0 0 0 0 0 0 0 + + + 0 0 0 0 0 0 0 0 0 0 0 0 0 + + Where "+" = addition of solution or test substance and "0" = NO addition + + + + + 0 0 0 + + 0 + + ETS-8-177.0 Indirect P hotolysis Screening Tests in Synthetic Humic Vater Vial Type/Exposure Clear/Exposed Clear/Exposed Clear/Exposed Clear/Exposed Clear/Exposed Clear/Exposed Clear/Exposed C lear/E xposed Clear/Exposed C lear/E xposed Clear/Exposed Clear/Exposed Clear/Exposed Amber/Unexposed Amber/Unexposcd Amber/Unexposed Amber/Unexposed Amber/Unexposed Amber/Unexposed Amber/Unexposed Amber/Unexposed Amber/Unexposed Amber/Unexposed Amber/Unexposed Amber/Unexposed Amber/Unexposed Page 12 o f 16 Page 85 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 Control Matrix(#l)= SHW/Buffer 1:9 v/v Control Matrix(#2)= PW/BufFer 1:9 v/v Create one set of samples (listed below) for each time point for UV/VIS analysis: Description Absorbance Control Light Absorbance Control - Dark Test Matrix (Buffer/SHW) + + Control Matrix 1 (Buffer/PW) 0 0 Control Matrix 2 (PW) 0 0 Test Substance 0 0 Vial Type/Exposure Clear/Exposed Ambcr/Unexposed 12.2.6 Store the "Time 0" vials in a labeled box at 1-5 C. 12.2.7 Place all the vials that will go into the photoreactor into an oven set to 70-80 C. for 5-10 minutes to acclimate the vials, liquid and headspace to photoreactor conditions. Upon removing the vials from the oven, immediately re-tighten the caps and proceed to load the reactor. 12.2.8 Place the amber "unexposed" vials in plastic bags and arrange on the bottom of the photolysis tray (make sure that they don't float once the tray is filled with water). The "unexposed" vials will remain submerged in the cooling water (25 5 C) during the exposure. (The vials are exposure- and temperature-controlled.) 12.2.9 Place the clear "exposed" vials in the rack in the photoreactor tray cap-side down, and install the rack so that the VOA vial caps will be submerged throughout the duration of exposure. 12.2.10 Prepare the radiometer to read intensity of irradiance over the duration o f the exposure. See SOP ETS-9-50.0 for operation of radiometer. 12.2.11 Expose the samples for the designated time intervals at 261 W/m2. See SOP ETS-9-44.0 for operation of the photoreactor. 12.2.12 Following each exposure interval, remove vials from the photoreactor and store inverted in a cooler at 1-5 C. After all exposures have been completed, remove all sample vials as well as the `Time 0" vials from the cooler and analyze as a single batch for each instrument. 12.2.13 UV-VIS absorbance control analysis 12.2.13.1 Analyze the pH 7.0 SHW/buffer absorbance controls by UV/Visible absorbance spectroscopy at 370 nm by aliquoting the test solution directly into a 1-cm or greater pathlength quartz cuvette and obtaining the spectra. See SOP ETS-9-46.0 for operation of the UV/VIS instrument. The resultant peak at 370 nm will be analyzed to determine the change in absorbance between the Time 0, exposed and unexposed samples. 12.2.14 LC/MS sample analysis 12.2.15 Dilute the exposed and unexposed samples for all timepoints with 30 mL internal standard solution in methanol (Section 8.11.1). Add spiking solution to the appropriate vials. Invert each vial several times to mix. 12.2.16 Transfer aliquots of LC/MS samples into autovials and then place them in the autosampler for analysis of the parent compound and possible degradation products. Analyze according to ETS-8-181.0. 12.2.17 GC/MS sample analysis ETS-8-177.0 Indirect Photolysis Screening Tests in Synthetic Humic Water Page 13 o f 16 Page 86 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 12.2.17.1 Analyze the exposed and unexposed samples for all timepoints as-is by purge and trap GC/MS. Add spiking and surrogate solutions, as required, to the appropriate vials. Analyze according to ETS-8-182.0. 12.2.17.2 Important: Maintain vials in the inverted position until they can be placed in the autosampler. 13.0 D ata Analysis and C alculations 13.1 Not applicable, as this is a sample preparation and analysis method. Consult the appropriate analytical protocol for guidance regarding data analysis and calculations. 14.0 M eth o d P er fo rm a n ce 14.1 Not applicable. 15.0 P o llu tio n P rev en tio n and W aste M anagem ent 15.1 Dispose of sample waste by placing in high or low BTU (British Thermal Unit) waste containers as appropriate. Use broken glass containers to dispose of glass pipettes. 16.0 R e c o r d s ___________________________________________________________________________ 16.1 Print out hard copies of all graphics and data analysis summaries for archiving. 16.2 Sign and date all graphics and label with instrument ID. 16.3 Fill out the sample preparation worksheets) documents completely, making sure to include all initials and dates. 16.4 Archive electronic data to compact disc media. 17.0 A t t a c h m e n t s ___________________________________________________________ 17.1 "Fluorochemical Degradation (Photolysis) Sample Prep Sheet" 18.0 R e f e r e n c e s ________________________________________________________________________ 18.1 Interpersonal conversation with Carrie O'Connor, Optical Systems Engineer, Atlas Electric Devices. 18.2 "Suntest CPS/CPS+ Spectral Irradiance Distribution," table distributed by Atlas Electric Devices Company, sent via fax by Richard Sherwin, Sales Representative, 26 July, 2000. 18.3 "Atlas Xenon Filter Combination and Sunlight Measurements," information generated by Atlas Electric Devices Company sent via fax by Richard Sherwin, Sales Representative, 26 July, 2000. 18.4 OPPTS 835.5270, Indirect Photolysis Screening Test: Sunlight photolysis in water containing dissolved humic substances. ETS-8-177.0 Indirect Photolysis Screening Tests in Synthetic Humic Water Page 14 o f 16 Page 87 of 158 19.0 A ffec ted D ocum ents 19.1 None 20.0 Revisions Revision Number. Reason For Revision BACK TO MAIN 3M Environmental Laboratory Report No. W2775 Revision --^ ETS-8-177.0 Indirect Photolysis Screening Tests in Synthetic Humic Water Page 15 o f 16 Page 88 of 158 BACK TO MAIN JM tnvironmental Laboratory Report No. W2775 Attachment A- Photolysis Sample Prep Sheet TEST ANALYTE: Lab Request Number: N om inal Tim e Interval: R eactor Tem perature: F lu a ro c h s ie lc a f D e g ra d a tio n (P h o to ly s is ) S a m p le P re p S h e e t P hotoreaelorlD S tart Date Slop Oate Total R eactor Tim e C ooler Storage ID: __ D a t e 4 T im e ln _ Dale S Tlm e O ut Initials C o o le r S to ra g e ID: D ate IT im e In _ Date Tim e O ut Initials NOTE; O ar* shaded areas raqu/rm NO additions NA * n o t ap plicable C om m ents: ETS-8-177.0 In direct P hotolysis Screening Tests in Synthetic H um ic W ater Page 16 of 16 Page 89 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 3 M E n v ir o n m e n t a l L a b o r a t o r y ______ E q uipm ent Procedure O pera tio n and M aintenance o f th e H ew lett P ackard 8453 UV -V isible Spectrophotom eter Procedure Number: ETS-9-46.0 Exact Copy ot Original Approved by: Laboratory Management Team Leader ,/ Adoption Date: o jz o / o D Revision Effective Date: Date ' Date ETS-9-46.0 Operation and Maintenance of the HP8453 UV-Vis Spectrophotometer Page 1 o f 9 Page 90 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 1.0 Sc o p e a n d A ppl ic a t io n 1.1 This equipment procedure describes the operation, cleaning, and maintenance of the Hewlett-Packard 8453 UV-Visible Spectroscopy System. 2.0 D efin itio n s 2.1 Absorbance: Measure of concentration of material present: expressed as product of molar extinction coefficient (e), pathlength (b), and concentration (c), written as A = e b c (also known as Beer's Law). 2.2 Cuvette or flow cell: Transparent receptacle in which sample solutions are introduced into the light path of spectrometers. Usually, two sides are equal (e.g. 1 cm x 1 cm) while the third dimension is elongated, possibly as long as 15 cm. For UV work, the material is quartz. Visible work permits the use of glass or plastic cuvettes. 2.3 Pathlength: The distance the light passes through the sample in its holder. In practical terms, the inside dimension of the cuvette (usually 1 cm). 2.4 Slit width: Size of opening through which light from cuvette emerges. Choice o f slit width depends on wavelength range, separation ability of wavelength selector, and desired isolation of specific wavelength. Slit width is often fixed or automatically programmed. 2.5 Solvent Cutoff: The wavelength at which the solvent absorbs a significant portion of the light, causing a loss of signal. In other words, the solvent becomes opaque to the wavelengths being used. This is common in the ultraviolet, rare in the visible. 2.6 Transmittance: Ratio of the radiant power transmitted by a sample to the radiant power transmitted by a blank in an equivalent cell or by some other means of compensation for solvent absorption, reflection losses, etc. 2.7 Visible: The portion of the electromagnetic spectrum, from 400 to 800 nm, detectable by human eyes. 2.8 Ultra-violet (UV): The portion of the invisisble electromagnetic spectrum composed of wavelengths of 10-400 nm. In UV spectrometry we are primarily interested in the nearUV (quartz) region extending from 200 to 380 nm. 2.9 UV Spectrum: a plot of wavelength (or frequency) of absorption versus the absorption intensity (absorbance or transmittance). 3.0 D escriptio n 3.1 The HP 8453 spectrophotometer is a single-beam, microprocessor-controlled, UV-visible spectrophotometer with collimating optics. The ChemStation for UV-Visible spectroscopy software running on a PC with Microsoft NT operating system provides instrument control, data acquisition, and data evaluation. 4.0 I d en tific a tio n 4.1 Hewlett Packard G1103A Serial No. CN93500458 4.2 Hewlett Packard 89090A Serial No. DE14300757 5.0 W a r n in g s a n d C a u t io n s__________________________________________________________ 5.1 Health and Safety Warnings: ETS-9-46.0 Operation and Maintenance o f the HP8453 UV-Vis Spectrophotometer Page 2 o f 9 Page 91 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 5.1.1 Eye damage may result from directly viewing light produced by deuterium lamps used in detectors and spectrophotometers. Always turn off the deuterium lamp before opening the lamp door on the instrument. 5.1.2 Some adjustments described in the service manual are made with power supplied to the instrument, and protective covers removed. Electricity and heat available at many points may, if contacted, result in personal injury. 5.1.3 Capacitors inside the instrument may still be charged, even though the instrument has been disconnected from its source of supply. Dangerous voltages, capable of causing serious personal injury, are present in this instrument. Use extreme caution when handling, testing, and adjusting. 5.2 Cautions: 5.2.1 Never touch the quartz envelope of the deuterium lamp with your fingers. Fingerprints absorb UV light and may be burnt in, thus reducing lifetime of the lamp. 5.2.2 Quartz sample cells or sample cells with quartz faceplates are required if you want to use the full 190 to 1100 nm wavelength range of the spectrophotometer. Good quality glass cells may be used when working above 350 nm. Disposable plastic sample cells are not recommended for use. 5.2.3 For high precision measurements, wait until the spectrophotometer and the lamps have reached thermal equilibrium. The time required is a function of environmental conditions but the instrument should be ready after 45 minutes. To determine if the spectrophotometer is in stable working condition, the HP 8453 Self- test may be performed. (See section 13.1) 5.2.4 Ensure cell windows are free of fingerprints and other contamination. 5.2.5 Avoid the use of alkaline solutions (pH > 9.5) which can attack quartz and thus impair the optical properties of the flow cells. 5.2.6 Solution in cell should be free of floating particles. 5.2.7 Solution in cell and cell walls should be free of bubbles. 5.2.8 Ensure that solution in cell is homogeneous by thoroughly mixing before measurement. 5.2.9 Blank is measured on the same solvent as sample. 5.2.10 Blank measurement should show a flat baseline. 5.2.11 Cell orientation of blank and sample measurements should be the same. 5.2.12 Ideally, the cell is not removed between sample measurements, which means the cell is filled/rinsed using a pipette or a flow cell is used. 5.2.13 Time between blank and sample measurements should be short. 6.0 S p e c ia l I n st r u c t io n s ______________________________________________________________ 6.1 None. 7.0 R e s p o n s ib il it y _____________________________________________________________________ 7.1 The operator is responsible for routine maintenance and cleaning. ETS-946.0 Operation and Maintenance o f the HP8453 UV-Vis Spectrophotometer Page 3 o f9 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 7.2 The person responsible for the equipment (and an alternate) will be identified in the front of the equipment logbook, and are responsible for all routine and non-routine maintenance and associated documentation. 8.0 S u p p l ie s a n d M a t e r ia l s 8T Pozidriv screwdriver 8.2 Isopropanol, reagent grade 8.3 Canister of compressed oil-free air. 8.4 Surgical cotton swabs, lint-free. 8.5 Deuterium lamp assembly, Agilent 8453 (Part No. 2140-0605). 8.6 Lamp, Tungsten G1315A, Agilent 8453A (Part No. G1103-60001). ' 9.0 I n s t r u m e n t C l e a n in g P r o c e d u r e s _____________________________________________ iTl Cleaning the Stray Light Filter. (Recommended at one-yearly intervals or more frequently when operating the spectrophotometer in a particularly dirty environment.) 9.1.1 Turn off the instrument and disconnect the power cord. Take the plastic and sheet metal rear covers off, see "Removing and Replacing Covers" on page 109 of the HP 8453 Service Manual. 9.1.2 Remove any accessory board or MIO board that may be plugged in from the rear side of the instrument. 9.1.3 Remove the upper rear foam block. 9.1.4 Disconnect the shutter cable from the SPM board. Open the screw that fixes the shutter assembly to the optical unit and remove the shutter assembly. 9.1.5 Dampen a lint-free, surgical cotton swab with reagent grade isopropanol and gently swab the surface of the stray light filter. Repeat severed times with clean swabs and alcohol each time. 9.1.6 Use a canister of compressed oil-free air to further clean the stray light filter. 9.1.7 Position the shutter assembly above the source lens and fix the screw that holds it at the optical unit, see Figure 39 on page 124 of the Service manual. Connect the shutter cable to the SPM board. 9.1.8 Replace the upper rear and upper front foam blocks. 9.1.9 If available, replace any accessory board or MIO board (plugged in from the rear side o f the instrument). 9.1.10 Replace the plastic and sheet metal rear covers. Push the plastic rear cover down so that it locates on both sides, see "Removing and Replacing Covers" on page 109 of the HP 8453 Service Manual. 9.1.11 Reconnect the line power and turn on the instrument. Check that the spectrophotometer passes the self-test, this means that the green light on the front panel comes on and that you can do a blank measurement from the software. 9.2 Cleaning the Source Lens from die Sample Compartment Side. (Recommended at oneyearly intervals or more frequently when operating the spectrophotometer in a particularly dirty environment.) 9.2.1 Turn off the instrument and disconnect the power cord. 9.2.2 Remove any cuvette holder from the sample compartment. ETS-9-46.0 Operation and Maintenance o f the HP8453 UV-Vis Spectrophotometer Page 4 o f 9 Page 93 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 9.2.3 To have better access you may want to take the plastic and sheet metal rear covers off, see "Removing and Replacing Covers" on page 109 of the HP 8453 Service Manual. 9.2.4 Dampen a lint-free, surgical cotton swab with reagent grade isopropanol and gently swab the surface of the source lens. Repeat several times with clean swabs and alcohol each time. 9.2.5 Use a canister of compressed oil-free air to further clean the source lens. 9.2.6 If you have taken the covers off, replace them. 9.2.7 Replace the cuvette holder: Reconnect line power and turn on the instrument. Check that the spectrophotometer passes the self-test, this means that the green light on the front panel comes on and that you can do a blank measurement from the software. 9.3 Cleaning the Spectrograph Lens. (Recommended at one-yearly intervals or more frequently when operating the spectrophotometer in a particularly dirty environment.) 9.3.1 Turn off the instrument and disconnect the power cord. 9.3.2 Remove any cuvette holder from the sample compartment. 93.3 To have better access you may want to take the plastic and sheet metal rear covers off, see "Removing and Replacing Covers" on page 109 of the HP 8453 Service Manual. 9.3.4 Dampen a lint-free, surgical cotton swab with reagent grade isopropanol and gently swab the surface of the spectrograph lens. Repeat several times with clean swabs and alcohol each time. 93.5 Use a canister of compressed oil-free air to further clean the spectrograph lens. 9.3.6 If you have taken the covers off, replace them. Replace the cell holder in the sample compartment. 93.7 Reconnect line power and turn on the instrument. Check that the spectrophotometer passes the self-test, this means that the green light on the front panel comes on and that you can do a blank measurement from the software. 10.0 M a in t e n a n c e P r o c e d u r e s ________________________________________________________ 10.1 Routine maintenance. 10.1.1 Cleaning the stray light filter. Indicators for a dirty stray light filter include: 10.1.1.1 After exchanging the lamps, the intensity test executed by the ChemStation software still falls below the specified level. 10.1.1.2 One of the stray light tests fails. 10.1.13 The photometric accuracy test fails. 10.1.2 Cleaning the lenses that are accessible from the sample compartment side. An indication for dirty lenses is when, after exchanging the lamps, the intensity test executed by the ChemStation software still falls below the specified level. 10.2 Non-routine: Document any non-routine maintenance. 10.2.1 Exchange the deuterium or the tungsten lamp when the intensity test, which is executed through the ChemStation software, falls below the specified level or when one of the lamps no longer ignites. See HP 8453 Service Manual for lamp replacement procedure (p.96). ETS-9-46.0 Operation and Maintenance of the HP8453 UV-Vis Spectrophotometer Page 5 o f 9 Page 94 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 11.0 O p e r a t in g P r o c e d u r e s 11.1 Powering Up the HP 8453 UV-Visible Spectrophotometer and PC controller. 11.1.1 Switch on the PC and boot the PC operating system. 11.1.2 Switch on the spectrophotometer and wait until the spectrophotometer's indicator light turns green. This process includes the spectrophotometer's self test and takes about one minute. 11.1.3 Launch a measurement session by pressing the operating system's "Start" button and select "Programs", "HP UV-Visible ChemStations", "spectrometer 1 online" 11.1.4 The system is ready to use if the blue "busy " status display on the system's bottom message line turns off. Note: For high precision measurements wait until the spectrophotometer and the lamps have reached thermal equilibrium. The time required is a function of environmental conditions but should be ready after 45 minutes. 11.1.5 The first measurement to perform is a reference measurement. After this alignment you are ready to measure absorbance data and spectra. 11.2 Inserting a Cell. 11.2.1 The HP 8453 is shipped with the standard single-cell holder which accommodates standard cells or flow cells. 11.2.2 Move the locking lever to its up position. 11.2.3 Insert the sample cell, making sure you orient it correctly. The frosted (non-clear) sides of the sample cell should not be in the path of the light beam. 11.2.4 Lock the sample cell in place by pushing the locking lever back down. 11.2.5 Small volume flow cells and particularly any cells with less than a 2 mm aperture may require use of the optional adjustable cell holder. This device helps you ensure the cells are properly centered in the light path. 11.3 Entering a Cell's Path Length. 11.3.1 Click "Setup" on the Instrument Panel. 11.3.2 Type the path length in cm in the "Setup Manual" dialog box. 11.3.3 Click "OK" to set the specified path length. 11.4 Starting a Measurement Session. 11.4.1 Start a measurement session by selecting Instrument 1 online from the menu. 11.4.2 Perform a reference measurement. Typically the cell containing the solvent used with your samples is put in the measurement position and a blank measurement performed. To start this measurement, click the "Blank" button on the Instrument Panel or press the spectrophotometer's "Blank" button. 11.4.3 Perform a sample measurement. To get the most precise results, use the same cell in the same orientation to the measurement beam. Flush the cell about three times with the sample solution and start the measurement by clicking the Instrument Panel's "Sample" button or by pressing the spectrophotometer's "Sample" button. 11.5 Setting up a Method for Single Component Analysis. 11.5.1 Choose the "Quantification" task from the data analysis panel. 11.5.2 Enter the used wavelength in the input fields. ETS-9-46.0 Operation and Maintenance o f the HP8453 UV-Vis Spectrophotometer Page 6 o f9 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 11.5.3 If background correction is desired, select "Single Reference Wavelength", "Subtract Average Over a Range" or "Three-point Drop Line" from the background correction combo box. 11.5.3.1 "Single Reference Wavelength" requires the input of one wavelength in the adjacent wavelength edit field on the right side of the combo box. 11.5.3.2 For "Subtract Average Over a Range" or "Three-point Drop Line" you must define the range/baseline by entering the start and end wavelengths in the two adjacent wavelength edit field on the right side of the combo box. 11.5.4 Specify a name for the analyte. 11.5.5 Choose "Concentration" to enter the analyte concentration directly or "Weight & Volume" to have the ChemStation calculate the concentration. Enter the units for the concentration or the weight and volume. 11.5.6 If you want to be prompted for the concentration of the standards during measurement, select "Prompt for Standard Information". In the combo box you can select whether the prompt asks you for the concentration, or calculates the concentration based on volume, weight and purity. 11.5.7 If you have diluted samples and want to correct for dilution, select "Prompt for Dilution Factor" of sample. 11.5.8 Choose the desired calibration curve type. 11.5.9 Select the desired data type and display range of the spectra in the graphical window. 11.5.10 Choose "OK" to close the dialog box. 11.5.11 Perform the following steps if you want to calibrate the method. 11.5.11.1 Measure a blank on the solvent if necessary using the "Blank" button in the instrument panel. 11.5.11.2 Measure the standards using the "Standard" button in the instrument panel. If you have selected one of the prompts, the appropriate values will be requested in a dialog box. The spectrum is displayed automatically in the "Standard Spectra" window as they are measured. Note: There is no fixed limit to the number of calibration standards that can be incorporated into a calibration. However, each o f the calibration curve types requires a minimum number of standards of different concentrations, which can be found in Table 7, page 45 of the HP Manual: Understanding Your UVVisible Spectroscopy System. The ChemStation software calibrates automatically when at least the minimum number of standards has been measured. A table with the used standards and values as well as calibration curve is displayed. 11.5.11.3 If the calibration is successful, the calibration curve icon of the data analysis panel changes from red to green. 11.6 Measuring and Displaying an Absorbance Spectrum 11.6.1 Select the "Clear" icon using the Toolbar, to delete any spectral data that you do not wish to keep. 11.6.2 Select the "Spectrum/Peaks" task from the Method menu or data analysis panel. 11.6.3 Select the boxes for "Peak/Valley Find" if necessary. ETS-9-46.0 Operation and Maintenance o f the HP8453 UV-Vis Spectrophotometer Page 7 of 9 Page 96 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 11.6.4 Select "Absorbance" as data type. 11.6.5 Set the display range you want to see in the graphical window. 11.6.6 Choose "OK" to close the "Spectrum/Peaks Parameters" dialog box. 11.6.7 Measure a Blank on the solvent if necessary using the "Blank" button in the instrument panel. 11.6.8 Measure all the samples using the "Sample" button in the instrument panel. The spectra are displayed automatically in the "Sample Spectra" window as they are measured and depending on the selected parameters you will get a table o f results. 11.7 Loading Spectra: 11.7.1 Choose "Load" from the "File" menu, then choose the type of spectra that you want to load (Samples or Standards) from the submenu to display the "Load Spectra" dialog box. 11.7.2 If the spectra you wish to load are not in the "File Name" list, select a different directory from the "Directories" list. 11.73 Select the spectra you wish to load from the File Name list and choose OK to close the dialog box. 11.8 Saving Spectra: 11.8.1 Choose "Save" from the "File" menu, then choose the type of spectra that you want to save (Samples, Standards or Selected Spectra) from the submenu to display the "Save Spectra As" dialog box. 11.8.2 If you wish to save the spectra in a directory other than the current one, select the new directory from the "Directories" list. 11.8.3 Type the name you wish to save the spectra as in the "File Name" field and choose "OK" to close the dialog box. 11.83.1 A valid file name consist of eight alphanumeric characters and the file extension .sd or .std. Usually, the extension .std is used for standards only. 11.8.4 You can also save spectra using the ToolBar. 12.0 Records 12.1 Document all cleaning and maintenance performed on the instrument in the maintenance or run/maintenance logbook. Include a description of the procedure(s) performed, name of person who performed procedure(s), any unusual observations, parts replaced or needing replacement, and whether the procedure was routine or non-routine. Logbooks are archived when complete. 13.0 TO 13.2 T estin g , C alibration and/o r Standardization P rocedures HP 8453 Self-Test: 13.1.1 Make sure that you are in the "Verification and Diagnostics" mode. The mode is indicated on the tool bar of the HP ChemStation session. 13.1.2 Select the "Self-Test" task in the analysis panel's selection box. 13.1.3 Choose "Self-Test". Start from the "Task" menu or click "Start" to start the self test. 13.1.4 The self-test results will be displayed in a window with pass/fail criteria. Calibrating for a single component analysis. ETS-9-46.0 Operation and Maintenance o f the HP8453 UV-Vis Spectrophotometer Page 8 of 9 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 13.2.1 Calibration for single component analysis is based on the measurement of standard samples with known concentrations. During the calibration process, the software calculates the calibration coefficients, which are then used for the quantification of unknown samples. 13.2.2 The status for calibration can be seen in the data analysis panel: 13.2.2.1 Uncalibrated: RED dashed calibration curve icon. 13.2.2.2 Calibrated: GREEN continuous calibration curve icon. 13.2.3 To calibrate for single component analysis: 13.2.3.1 Load or set up a method for the "Quantification" task. 13.2.3.2 If the "Standard" spectra window is not displayed, choose "Show" standards in the data analysis panel. 13.2.3.3 You can either load the standards from file or measure them. 13.2.3.4 To measure standards: 13.2.3.4.1 Measure a bank on the solvent if necessary using the "Blank" button in the instrument panel. 13.2.3.4.2 Measure the standards using the "Standard" button in the instrument panel. If you have selected one of the prompts in the method, the appropriate values will be requested in a dialog box. 13.2.4 The spectra are displayed automatically in the "Standard Spectra" window as the standards are measured. A minimum number of standards is required, depending on the selected calibration curve. The ChemStation software calibrates automatically when at least the minimum number of standards have been measured. A table with the used standards and values as well as a calibration curve is displayed. 13.2.5 If the calibration is successful, the calibration curve icon of the data analysis panel changes from red to green. 14.0 References__________________________________________________________ 14.1 Definitions obtained from www.spectroscopymag.com. 14.2 HP Manual: Understanding Your UV-Visible Spectroscopy System, Hewlett-Packard: Wilmington, DE, 1997. Part No. Gl 115-90005. 14.3 HP 8453 UV-Visible Spectrophotometer Operator's Manual, Hewlett-Packard: Wilmington, DE, 2000. Part No. Gl 115-90012. 14.4 HP 8453 UV-Visible Spectrophotometer Service Manual, Hewlett-Packard: Wilmington, DE, 1998. Part No. Gl 115-90003. 15.0 Affected Documents 15.1 None. 16.0 Revisions Revision Number. Reason For Revision Revision Date ETS-9-46.0 Operation and Maintenance o f the HP8453 UV-Vis Spectrophotometer Page 9 of 9 Page 98 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 3M Environmental Laboratory E quipm ent Procedure R o u tin e M aintenance o f Arch o n Pu rg e and T rap Au to sa m pler , T ekm ar P urge and Trap C oncentrator and A gilent G as Ch ro m atograph/M ass Spectr o m eter Procedure Number: ETS-9-49.D 0\ Approved by: Laboratory Manager Revision Date: Date Date ETS-9-49.0 Routine Maintenance o f the Purge & Trap Autosampler/Concentrator/GC/M S Page 99 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 1.0 Scope and Application (Use Numbered Tier I ) ________ ____ 1.1 This equipment procedure describes the maintenance required for optimal operation of the Archon Purge and Trap Autosampler, Tekmar Purge and Trap Concentrator and Agilent gas chromatograph / mass spectrometer (GC/MS) system. Specific items requiring routine maintenance include occasional tightening vial escalator's nuts and refilling the Standard Vial and water bottle in the Archon autosampler and periodic cleaning of the mass spectrometer ion source. 2.0 Definitions________________________________________________________ 2.1 None. 3.0 Description 3.1 Archon purge and trap autosampler equipped with Tekmar purge and trap concentrator and Agilent gas chromatograph and mass spectrometer. 4.0 Identification_____________________________________ 4.1 System : "Rufus". (An equivalent system may be used). 4.1.1 Autosampler: serial number 13006, Varian, Archon 4.1.2 Concentrator: serial number 90297002, LSC2000, Tekmar 4.1.3 GC: serial number US00034972,6890 G1530A, Agilent 4.1.4 MS: serial number US01180105,5973N G2589A, Agilent 4.1.5 PC: serial number US94850812, D6720T, HP Kayak XA 5.0 Warnings and Cautions_______________________________________________ 5.1 Health and Safety Warnings: 5.1.1 Cooling the Tekmar before removing the side cover for maintenance prevents contact bums. 5.1.2 Turning off power source for Tekmar before removing the side cover will prevent electric shock. 5.2 Cautions: 5.2.1 It is recommended that a grounded antistatic wrist strap be worn while disconnecting all wires, contacts, or cables which are connected to printed circuit boards within Archon autosampler, Tekmar concentrator or MS analyzer. 5.2.2 To prevent the breakage of the Standard Vial on Archon autosampler, during the refill, do not use any tool and do not overtighten the thumbnut. 5.2.3 Never add oil while the foreline pump is on. 6.0 Sp e c ia l I nstruc tio n s 6.1 Not applicable. ETS-9-49.0 Routine Maintenance o f the Purge & Trap Autosampler/Concentrator/GC/M S Page 2 of 5 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 7.0 R e s p o n s ib il it y 7.1 Routine maintenance procedures may be performed by a primary custodian, and by any analyst who has been trained to perform these maintenance procedures by a primary custodian. 8.0 Supplies and Materials____________________________________________ 8.1 Graphite Ferrules, 0.4 mm ID . for 0.25 mm columns 8.2 Abrasive paper, Hewlett-Packard, part no. 5061-5896 8.3 Alumina abrasive powder, Hewlett-Packard, part no. 8660-0791 8.4 Acetone, reagent grade 8.5 Dichloromethane, reagent grade 8.6 Methanol, purge and trap grade 8.7 Gloves (clean, lint-free, cotton), Hewlett-Packard, part no. 8650-0030 (large); 8650-0029 (small) 8.8 Cotton swabs 8.9 Chem-wipes 8.10 Glass beakers 8.11 Sonicator 8.12 Base deactivated 2 mm ID gooseneck splitless injection port liners, Restek Corporation, part #20796-210.5, or equivalent 8.13 11 mm diameter Thermogreen LB2 septa, Supelco, part #23163, or equivalent 8.14 Viton injection port o-rings, Restek Corporation, part #20377, or equivalent 8.15 Septum wrench, Hewlett-Packard, part #19251-00100 8.16 Tweezers 9.0 C l e a n in g P r o c e d u r e s /X 10.0 M a in te n a n c e Procedures 10.1 Routine: Tighten the elevator's assem bly nuts when Archon autosam pler displays error message" Elevatornothomedposition". 10.1.1 Stop autosampler run by pressing STOP button on the front display twice. 10.1.2 Open the back cover of autosampler 10.1.3 Tighten top and bottom nuts on the elevator's assembly, do not over tighten them. 10.1.4 Close the back cover of autosampler 10.2 Routine: Fill the water bottle, empty the waste bottle. 10.3 Routine: If internal standards or surrogates are to be used, be certain the Standard Vial is filled with the required internal standard or surrogate. 10.3.1 Turn the helium gas "OFF" with the toggle switch. 10.3.2 Push "System" key, choose Maintenance, Standard Control, Front Park. 10.3.3 Grasp the vial and loosen the black thumbnut. Slide the vial down. ETS-9-49.0 Routine M aintenance o f the Purge & Trap Autosampler/Concentrator/GC/M S Page 3 of 5 Page 101 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 10.3.4 Clean the vial with methanol, diy it thoroughly and fill the vial with approximately 5 ml of standard or surrogate 10.3.5 Slide the vial back up into standard mount. Finger-tighten thumbnut until it is snug. Do not use any tool and do not overthighten. 10.3.6 Turn the helium gas into ON position. Prime Standard Loop. 10.4 Routine: GC/MS foreline pump maintenance. 10.4.1 Examine the oil level window daily. If the oil level is near or below the lower line then add foreline pump oil. Never add oil while the foreline pump is on. 10.4.1.1 Vent the MSD according to the MSD Hardware Manual. 10.4.1.2 Remove the fill cap. 10.4.1.3 Add pump fluid until the oil level in the window is near, but not above, the upper line. 10.4.1.4 Reinstall the fill cap. 10.4.1.5 Pump down the MSD according to the MSD Hardware Manual 10.4.2 Change foreline pump oil every 6-12 months according to the MSD Hardware manual. 10.5 Nonroutine: Document any nonroutine maintenance in the instrument's maintenance logbook. 11.0 Operating Procedures 11.1 For operating procedures, refer to an appropriate analytical method, or to the Archon Purge and Trap Autosampler System Operator's Manual, Tekmar LSC200 Instruction Manual and the Hewlett-Packard MSD Hardware Manual for HP 5973N & HP 6890 Series Mass Selective Detectors. 12.0 Records____________________________________________________________ 12.1 Document any maintenance performed on the instrument in the maintenance or run/maintenance logbook. Include a description of the procedure(s) performed, any unusual observations, parts replaced or needing replacement, and whether the procedure w^s routine or non-routine. Be sure to date and initial the entry. Logbooks are archived when complete. 13.0 Testing, Calibration and/or Standardization Procedures________________ 13.1 After cleaning the source and allowing sufficient time for the vacuum to pump down and the mass spectrometer to equilibrate to operation temperature, run an autotime; check for improved performance and for the presence or absence of air leaks. A tune report can also be used to check for leaks after performing injection port maintenance. 14.0 References 14.1 Archon Purge and Trap Autosampler System Operator's Manual 14.2 Tekmar LSC200 Instruction Manual ETS-9-49.0 Routine M aintenance o f the P urge & Trap Autosampler/Concentrator/GC/M S Page 4 of 5 Page 102 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 14.3 Hewlett-Packard MSD Hardware Manual for HP 5973N & HP 6890 Series Mass Selective Detectors. 15.0 Affected Documents m None. 16.0 R e v is io n s Revision Number. Reason For Revision Revision Date ETS-9-49.0 Routine M aintenance o f the Purge & Trap Autosampler/Concentrator/GC/M S Page 5 of 5 Page 103 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 Appendix B: Chemical Characterization This appendix includes chemical characterization information for both reference substances and control substances. Page 104 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 Chemical Characterization Substance IUPAC Name Chemical Formula Identifier Source Expiration Date Storage Conditions Chemical Lot Number Physical Description Purity Substance C 7 Perfluoroheptenes (90/10 mix) IUPAC Name Chemical Formula Identifier Source Expiration Date Storage Conditions Chemical Lot Number Physical Description Purity 10% 2-Perfluoroheptene, 90% Perfluoroheptene c 4f 9c f = c 2f 5, C5F u CF=C F2 355-63-5* Lancaster Synthesis 2005 Frozen 90004250, TNA 3025 Clear ambient liquid 100% PFOA Perfluorooctanoic acid, ammonium salt C8F 150 2N H 4 3825-26-1* 3M Specialty Chemicals 2002 Frozen 332 White powder 97%< C 7 Hydride 1, 1,2 ,2 ,3,3,4,4,5,5,6 ,6 ,7,7,7 pentadecafluoroheptane c 7f 15h 27213-61-2* Lancaster Synthesis 2005 Frozen 9005911, TNA-3026 Clear ambient liquid 97% PFO S K Salt Potassium perfluorooctanesulfonate c 8f 17s o 3k 2795-39-3* 3M Specialty Chemicals 8/31/2001 Frozen 171SD009 White powder 86.4 C 6 Hydride 1,1,2,2,3,3,4,4,5,5,6 ,6 ,6 tridecafluorohexane c 6f 15h 355-37-3* Lancaster Synthesis 2005 Frozen 90005941, TNA-3027 Clear ambient liquid 98% Page 105 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 Reference Substances (continued) Reference Substance IUPAC Name Chemical Formula Identifier Source Expiration Date Storage Conditions Chemical Lot Number Physical Description Purity Reference Substance IUPAC Name Chemical Formula Identifier Source Expiration Date Storage Conditions Chemical Lot Number Physical Description Purity C8 Hydride/Olefin Mix 1,1,1,2,23,3,4,4,5,5,6,6,7,8,8,8 pentadecafluorooctane, 2 - perfluorooctene C6F 13CFH C F3'C 6F 13CF=CF2 TCR-99030-18 3M Specialty Chemicals 6/6/99 Frozen 1 Clear ambient liquid 85% C8 Hydride, 15% C 8 Olefin C4Interior Olefin 2-Perfluorobutene c 4f 8 360-89-4* Lancaster Synthesis 2002 Frozen GOO195, TNA-4298 Clear ambient liquid 97% C8Terminal Hydride 1,1,2,2,33,4,4,5,5,6,6,7,7,8,8,8 heptadecafluorooctane C8F 17H 335-65-9* Aldrich Chemical 2002 Frozen 04307PN, TNA-2983 Clear ambient liquid 99% C3Terminal Hydride 1,1,2,23,3,3 heptafluoropropane C 3F 7H 2252-84-4* Lancaster Synthesis 2010 Flammable G0062B, TNA-4294 Gas 97% C4Terminal Hydride 1,1,1,23,3,4,4,4 nonafluorobutane C4F9H 375-17-7* Crescent Chemical 2002 Frozen 6A-46, TNA-3997 Clear ambient liquid 99% C2Terminal Hydride 1, 1,2 ,2 ,2 pentafluoroethane C2F 5H 354-33-6* Lancaster Synthesis 2010 Flammable G00492, TNA-3021 Gas 99% Page 106 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 Chemical Characterization (Control Substances)* Control Substances Structure IUPAC Name Use Source Expiration Date Storage Conditions Chemical Lot Number Physical Description Purity Control Substances Structure IUPAC Name Use Source Expiration Date Storage Conditions Chemical Lot Number Physical Description P u rity Control Substances Structure IUPAC Name Use Source Expiration Date Storage Conditions Chemical Lot Number Physical Description Purity *CAS Number PFCH c 6F12 Perfluorocyclo-hexane Surrogate Standard For GC/MS analysis Aldrich Chemical 2005 Frozen 01911AU Colorless Moist Solid 97% Chlorobenzene-d; c 6c i d 3 Chlorobenzene-d5 Instrumental Surrogate Standard For GC/MS analysis Restek Corp. 6/2002 Frozen A013256 Methanol solution 99% (2500 pg/mL + 0.2%) 1,4 Difluorobenzene c 6 h ,,f 2 1,4 Difluorobenzene Instrumental Surrogate Standard For GC/MS analysis Restek Corp. 6/2002 Frozen A 013256 Methanol solution 99% (2500 pg/mL + 0.2%) PFBS Perfluorobutane-sulfonate, potassium salt c 4f 9s o 2k Internal Standard for LC/MS analysis 3M Specialty Chemicals 2002 Frozen TCR-99030-028 White Powder 97%< Toluene-dg C7D8 Toluene-dg Instrumental Surrogate Standard For GC/MS analysis Restek Corp. 2/2002 Frozen A 012973 Methanol solution 99% (2500 pg/mL + 0.2%) 4-Bromofluoro-benzene C6H 4BrF 4-Bromofluoro-benzene Instrumental Surrogate Standard For GC/MS analysis Restek Corp. 2/2002 Frozen A012973 Methanol solution 99% (2500 pg/mL 0.2%) Pentafluorobenzene c 6h f 5 Pentafluorobenzene Instrumental Surrogate Standard For GC/MS analysis Restek Corp. 6/2002 Frozen A013256 Methanol solution 99% (2500 pg/mL j_0.2%) Dibromofluoromethane CH Br2F Dibromofluoromethane Instrumental Surrogate Standard For GC/MS analysis Restek Corp. 2/2002 Frozen A 0 12973 Methanol solution 99% (2500 pg/mL + 0.2%) 1,4-Dichlorobenzene-dt C6C12D 4 1,4 -D ic h lo ro b e n z e n e -d 4 Instrumental Surrogate Standard For GC/MS analysis Restek Corp. 6/2002 Frozen A 013256 Methanol solution 99% (2500 pg/mL 0.2%) Page 107 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 Appendix C: Kinetics Model and Kinetic Calculations This appendix presents the mathematical description of the kinetics model employed in this study and the application of this model in the determination of the estimated half-lives presented. Page 108 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 Kinetics Model C1. Reaction Components and Rates The arguments below are based on the following idealized set of reactions representing the photodegradation of a parent compound P and its products A m, which number N. The actual reactions that occur are subsumed in these equations, and are assumed to proceed with pseudo-first order rates k Pm(forthe parent) and k Am(forthe products). P + photon -- nmA m+ Y ^ (m= ltoN) (C1) A m+ photon -> Ym2 (m = 1 to N) (C2) where "photon may either represent a photon of light or it may represent some other species in solution that reacted with a photon to produce a new reactive species and the general symbols Yml and Ym2 represent all the other hydrolysis products. C2. Parent Compound Concentrations Equation C1 indicates that the pseudo-first order differential change in the parent concentration P at a constant flux of light or a constant concentration of radicals is given by (C3) which is equivalent to the separable differential equation dP / N n m k Pm d t P y Equation C4 may be directly integrated to obtain the general solution With the initial condition P(t = 0) = P0, the specific solution to Equation C4 is (C4) (C5) ^ m=l / (C6) Page 109 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 using the additional definition of the total parent photolysis rate N k P s n m k Pm . m-1 (C7) Equation C6 can be re-written in a form that allows a least-squares estimate of the total parent hydrolysis rate: k pt = -In (C8) Using the initial (t = 0 ) measured value of the parent concentration P0and later values P measured at later times t , one can calculate and plot the (linear) quantity [ - In (P/P0)] versus time and obtain a least -squares estimate of the slope of the line. The resulting slope is the least-squares estimate k p of the total parent photolysis rate. Equation C6 indicates that over a period of time T 1^ (the parent half-life) the parent concentration P is reduced through hydrolysis by a factor of two, where rpi/2 ln( 2) p= k 7 (C9) A least squares estimate T ^ of the parent photolysis half-life is therefore available from f V2_ H2) (C10) C3. Product Compound Concentrations The pseudo-first order differential changes in the product concentrations An (using Equations C2 and C6) are d A m= ( n mk PmP - k AmA m)dt = ( nmk PmP0 e~kp ` - k AmA m)dt (C11) and the (first order, non-separable) differential equation governing the product concentrations is dA - ^ + k AmA m = n mk PmP0 e~kpt . (C12) Page 110 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 The "standard form" of Equation C12 is A,,+S(t)A.=Q (t) where the "function" S (t) is actually a constant: S(t) = fcAm and Q W 'i'A .P .e -1'1 The general solution A mto Equation C12 is contained in (C13) (C14) (C15) A m eiS(t)dt = j Q ( t ) e is(t',dt' dt + C (C16) where e /s(t)dt = e ls(`')dt' = e kM,/d` _ e i w (C17) and JJ*Q(t) eJS(t )dt' dt + C = n mk PmP0 ek- ` e 'kp,dt + C (C18) There are two cases of Equation C18 to consider. In the circumstance that k Ani = k p , which occurs only when the rate of the mth product is identical to the total parent photolysis rate, the general solution to Equation B18 is (f o r k Am = k P > A m e kpt = n mk PmP0 t + C (C19) and, using the initial condition A m(t = 0 ) = A ^ , the specific solution to Equation18 is (f o r k A m = k p ) A m = (n mk P,nP0 t + A n0)e 'k' ` (C20) Page 111 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 We note that when = k p = 0 (that is, when both the parent and potential product are photolytically stable), Equation C7 requires (also) that k Pm= 0, so Equation C20 becomes (C21) indicating, as required, that the product concentration does not change with time. The circumstance k Am = k P is highly improbable, and is neglected in the remainder of this discussion. However, the reader should bear in mind that the expressions derived below do not hold when the parent photolysis rate k pand the product photolysis r a te k ^ approach each other. In the more probable case, for which k Am* k P (i.e. that the rate of the mth product is different from the total parent rate), the general solution to Equation C18 is (C22) and the specific solution to Equation C18 with the initial condition A m(t = 0) = A m0 is (C23) Of greatest interest here is the case in which the product compounds are known to be photolytically stable, that is, when k ^ = 0 for all m. In this case, Equation C23 becomes (for stable products) (C24) C4. Relationships Between the Parent and Compound Concentrations Equations C7 and C24 can be combined to obtain (for stable products) (C25) Page 112 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 so that or - V n k _ k p Y (Am ~ Am) ~ 2 L n - kpm m=l \ ` \2 -i / im--=!1 P0 (for stable products) c- i c p t j _ ^ (Am - A nio) T Po (for stable products) (C26) k pt = - In 1 ^ (A m - A m0) . m=l P0 (C27) If the changes in the product concentrations are all small compared to the original parent concentration, that is, if ^ Am ~ A m0 1 m-l P 0 we may use the expression (valid for -1 < X < 1 ) (C28) ln(l + X ) = X - - X 2 + - X 3 - - X 4 + 234 and Equation B23 becomes (for stable products and r k \ or (C29) (C30) Page 113 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 (for stable products and k p Po) (C31) C5. Parent Half-Life Estimates Based on Limits of Quantification of the Products In every experimental determination of k p, there is some set of values A " 0 (the "limits of quantitation") below which the product concentrations A mcannot be reliably measured. If during an experiment carried out over the period of timeA t all the product concentrations A mremain below their limits of quantitation, then the maximum possible value of the rate k p is obtained by assuming (for all the products) that 1) A m0 = 0 and 2) at time t = A t , the product concentrations have increased to the values A m= A " . With these assumptions, the experimental data indicate that the reaction rate k pis less than some maximum value (kp)max as follows: (for photolytically stable products at concentrations below the limits of quantitation) k p ^ (k p L x (C32) Under the same circumstances and assumptions, the experimental data indicate that the parent half-life T 1^ (see Equation C9) is greater than the value (T ^j) as follows: (for photolytically stable products at concentrations below the limits of quantitation) VK P /max a lq m=l (C33) The reader should note that Equations C32 and C33 are valid only when both 1) the products are stable and 2) the concentrations of all the potential products are measured. Otherwise, the quantity ( k p ) ^ in Equation C32 may not actually represent the maximum possible value of the rate constant k p, and the related result in Equation C33 for (t ^ ) is also questionable. Page 114 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 C6. Parent Half-Life Estimates Based on Limits of Quantification and Experimental Precision of Product Concentrations In certain experiments, some products are present at quantifiable but essentially constant concentrations over the time (A t ) of the experiment. In this case, it is the experimental precision of the measured product concentrations, rather than the limits of quantitation, which contribute to the estimate of the maximum value of the parent hydrolysis rate k p. If the set of concentrations measured for the mth product have the mean value p mand standard deviation o m, the data do not exclude the possibility that the product concentration increased from the initial value a m - p mto the value a m + p ra at time t = A t . Taking this possibility to be the actual case for the measured products, the maximum value of the quantity (A m- A m0) is 2 o m. This reasoning suggests that the following estimate of the maximum parent photolysis rate is appropriate: (for stable products at either 1) constant measured concentrations with standard deviation omor 2) concentrations below the limits of quantitation) (C34) Under these circumstances and assumptions, the experimental data indicate that the parent half-life T 1^ is greater than the value (t ^ ) as follows: " v P'min (for stable products at either 1) constant measured concentrations with standard deviation amor 2) concentrations below the limits of quantitation) (C35) The reader should note that Equations C34 and C35 are valid only when both 1) the products are photolytically Stable and 2) the concentrations of all the potential products are measured. C7. Parent Half-Life Estimates Based on the Experimental Precision of Parent Concentrations In certain experiments, the concentration of the parent remains essentially constant over the time (A t) of the experiment. In this case, it is the experimental precision of the measured parent concentrations that determines the maximum value of the parent hydrolysis rate k P. If the set of concentrations measured for the parent have the mean value p pand standard deviation o P, the data do not exclude the possibility that the product concentration increased Page 115 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 from the initial value p p - c p to the value p p + c P at time t = A t . This reasoning suggests that the following estimate of the maximum parent photolysis rate is appropriate: (for essentially constant parent concentrations with mean value p p and standard deviation C P) k p < ( k P)max 2op pP A t (C36) Under these circumstances and assumptions, the experimental data indicate that the parent half-life T Vp is greater than the value (t ^ ) ^ as follows: (for essentially constant parent concentrations with mean value p Pand standard deviation G p) T 1/2 > p -- VA p /, ln( 2) _ pp A t ln( 2) (^p)inax 2 ctp (C37) References to Above: B1 I. N Levine, "Physical Chemistry," McGraw-Hill (New York), pp. 498-501 (1978). 82 F. Daniels, et al., "Experimental Physical Chemistry", McGraw Hill (New York), p.131 (1962). Kinetic Calculations Indirect Photolysis Only two values of the parent concentration (P0 and P,) were recorded: these data reflect the time before and after the exposure period of length A t . In this case, no least squares regression is possible to determine the rate k P in Equation C8: k Pt - I n (C8) However, the two measured for P, and P0 are with in experimental error (1427 ng/m initial vs. 1432 ng/ml final), thus, equation C36 is used Page 116 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 kp < (kp), 2qp (4-p A t (C38) Solving for the observed rate using 167 hours for At, 1479 for and 20.71 for Gpgives a value of 1.68 x 10'4 h r1. The rate of photolysis in the reactor k p is related to the actinic rate of photolysis k ACT by k ACT (C39) where I ACT = 261 w/m2 is the actinic solar intensity (at 45 south latitude) and the measured reactor intensity is I R = 680 w/m2. This gives / 261 w /m 2 ^ k ACT 1 . 6 8x l 0" 4 hr 680 w / m 2 6.4 4 x 1 O'5 hr"1 (C40) For samples under constant illumination, the reaction rate and half-life are related by Equation C9: Ti/2_ fa(2) p k*-ACT (C41) However, the actinic half-life is three times larger, according the standard eight-hour exposure day. This leads to (indirect photolysis) t A P APT - 3hl( 2) . _37 ^ * years 'ACT (C42) Page 117 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 Appendix D: Individual Sample Data This appendix includes individual sample data and quality control data. Page 118 of 158 PHOTODEGRADATION STUDY: PFOS in Fe20 3 Acquisition Method: H608PFOS.m Instrument: Hillary HP1100 MSD Acquisition Sequence: H060800.S Directory: H060800 SAMPLES AND SPIKES 'Vial leaked in photoreactor Batch H060800 H060800 H060800 H060800 H060800 H060800 H060800 H060800 H060800 H060800 File Sample ID# HILL0023.D 053100PFOSfe-01 HILL0024.D 053100PFOSfe-02* HILL0025.D 053100PFOSfe-03 HILL0026.D 053100PFOSfe-04 HILL0027.D 053100PFOSfe-05* HILL0028.D 053100PFOSfe-06* HILL0029 D 053100PFOSfe-07 HILL0030 D 053100PFOSfe-08 HILL0031.D 053100PFOSfe-09 HILL0032.D 053100PFOSfe-10 Exposure Exposed: with H2O2 Exposed; with Exposed: with H2O2 Exposed; with Exposed; with H2 0 2 Exposed; with H2O2 Exposed; with H2O2 Exposed; with H2 0 2 Exposed; with H2 0 2 Exposed; with H2O2 Sample Description Matrix blank Matrix blankspike Sample Sample dup Sample trip Sample spike Sample spikedup Control - noFe203 Control dup- noFe20 3 Control Spike- noFe2Oa RT 7.343 7.345 7.343 7.345 7.345 7.344 7.346 7.344 7.346 7.343 PFBS Area 729810 753675 719217 726380 761694 750871 729311 726355 726725 740834 Amount 47.4 47.4 47.4 47.4 47.4 47.4 47.4 47.4 47.4 47.4 RT 0 8.244 8.246 8.252 8.248 8.243 8.245 8.245 8.247 8.242 H060800 H060800 H060800 H060800 H060800 H060800 H060800 H060800 H060800 H060800 HILL0036.D 053100PFOSfe-11 HILL0037.D 053100PFOSfe-12 HILL0038.D 053100PFOSfe-13 HILL0039.D 053100PFOSfe*14 HILL0040.D 053100PFOSfe-15 HILL0041.D 053100PFOSfe-16 HILL0042.D 053100PFOSfe-17 HILL0043.D 053100PFOSfe-18 HILL0044.D 053100PFOSfe-19 HILL0045.D 053100PFOSfe-20 Exposed; no H2O2 Exposed; no H20 2 Exposed; no H2O2 Exposed; no H20 2 Exposed; no H2O2 Exposed; no H20 2 Exposed; no H202 Exposed; no H20 2 Exposed; no H202 Exposed; no H20 2 Matrix blank Matrix blank spike Sample Sample dup Sample trip Sample spike Sample spike dup Control - no Fe2C>3 Control dup- noFe^s Control Spike- noFe2Os 7.345 7.345 7.365 7.346 7.346 7.364 7.345 7.345 7.343 7.343 734378 741709 732696 730153 741327 734472 726774 739618 724800 733894 47.4 47.4 47.4 47.4 47.4 47.4 47.4 47.4 47.4 47.4 0 8.244 8.25 8.25 8.246 8.245 6.245 8.246 8.246 8.241 H060800b HILL0057.D 053100PFOSfe-21 H060800b HILL0058.D 053100PFOSfe-22 H060800b HILL0059.D 053100PFOSfe-23 H060800b HILL0060.D 053100PFOSfe-24 H060800b HILL0061.O 053100PFOSfe-25 H060800b HILL0062.D 053100PFOSfe-26 H060800b HILL0063.D 0S3100PFOSfe-27 H060800b HI.0064.D 053100PFOSfe>28 H060800b HILL0065.D 053100PFOSfe-29 H060800b HILL0069.D 053100PFOSfe-30 Unexposed; with Unexposed; with H2O2 Unexposed; with H2O2 Unexposed; with H2 0 2 Unexposed; with H2O2 Unexposed; with Unexposed; with H2O2 Unexposed; with H2O2 Matrix blank Matrix blank spike Sample Sample dup Sample trip Sample spike Sample spikedup Control - no FbjOs Unexposed; with Control dup- n o F e ^ Unexposed; with H2 0 2 Control Spike- noFe203 7.344 7.343 7.345 7.345 7 344 7.344 7.345 7.343 7.344 7.344 704168 707032 708468 706537 704183 703871 692984 709370 692624 689918 47.4 47.4 47.4 47.4 47.4 47.4 47.4 47.4 47.4 47.4 0 8.242 8.249 8.261 8.245 8.242 8.244 8.263 8.247 8.242 H060800b HILL0070.D 053100PFOSfe-31 H06G800b HILL0071.D 053100PFOSfe-32 H060800b HILL0072.D 053100PFOSfe-33 H060800b HILL0073.D 053100PFOSfe-34 H060800b HILL0Q74.D 053100PFOSfe-35 H060800b HILL0075.D 053100PFOSfe-36 H060800b HILL0076.D 053100PFOSfe-37 H060800b HILL0077.D 053100PFOSfe-38 H060800b HILL0078.D 053100PFOSfe-39 H060800b HILL0079.D 053100PFOSfe-40 Unexposed; no H20 2 Unexposed; no H20 2 Unexposed; no H2O2 Unexposed; no H20 2 Unexposed; no H2O2 Unexposed; no H20 2 Unexposed; no 82 0 2 Unexposed; no H20 2 Unexposed; no H20 2 Unexposed; no H2O2 Matrix blank Matrix blank spike Sample Sample dup Sample trip Sample spike Sample spike dup Control - no F e ^ Control dup- noFe20 3 Control Spike- noFe20 3 7.343 7.344 7.345 7.344 7.344 7.343 7.344 7.343 7.341 7.343 694542 684028 686076 682590 680004 677433 683247 679703 683750 685250 47.4 47.4 47.4 47.4 47.4 47.4 47.4 47.4 47.4 47.4 8.275 8.243 8.263 8.267 8.25 8.243 8.244 6.262 8.263 8.245 H060800C HILL0091.D 053100PFOSfe-41 H060800C HILL0092.D 053100PFOSfe-42 H060800C HILL0093.D 053100PFOSfe-43 H060800C HILL0094.D 053100PFOSfe-44 Time 0; with H2O2 Time 0; with H2O2 Time 0; with Time 0; with H20 2 Matrix blank Matrix blank spike Sample Sample dup 7.342 7.344 7.344 7.344 676778 681087 673430 680293 47.4 47.4 47.4 47.4 0 8 244 8.265 8.267 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 PFOA PFOS Area 0 132365 6633 6990 5719 131115 132486 7194 7137 133299 Amount 0.00 21.37 0.79 0.84 0.58 21.25 22.12 0.88 0.86 21.91 Spike Mean/ STDEV / RSD %Recov. or Mean/RPD 100% 96% 100% 98% 0.74 0.14 19% 21.7 4.0% 0.87 1.3% RT 0 8.519 8.515 8.518 8.517 8.516 8.519 8.517 8.518 8.516 Area 0 6102337 21622604 21818917 17116866 22711441 24620798 21725089 21706453 25125316 Amount 0.00 308.80 1491.38 1489.64 1030.32 1503.49 1748.55 1481.19 1478.49 1760.03 Spike Mean/ STDEV / RSD %Recov. or Mean/RPD % of Oriqinal 102% 1490.5 0.1% 103% 4% 85% 92% 1626.0 15% 1479.8 0.2% 102% 0 127980 6535 6906 6598 131561 130272 7631 6529 127509 0.00 20.99 0.75 0.82 0.75 21.81 21.82 0.93 0.76 21.14 98% 98% 98% 95% 0.77 0.04 5.0% 21.8 0 .1 % 0.85 19% 0 8.518 8.519 8.519 8.519 8.518 8.51B 8.518 8.516 8.516 0 5902627 21923392 21796225 21951807 25042879 24818706 21509510 21587730 24604500 0.00 302.51 1481.96 1477.36 1461.61 1773.47 1777.38 1427.21 1472.94 1731.50 100% 99% 100% 93% 1473.6 10.67 0.7% 1775.4 02% 1450.1 32% 102% 100% 0 121651 7630 7130 8334 126515 126780 9013 7811 125407 0.00 20.66 0.77 0.68 0.90 21.61 22.00 1.01 0.83 21.86 97% 97% 99% 98% 0.78 0.11 13.9% 21.8 1.8% 0.92 19.2% 0 8.516 8.518 8.518 8.517 8.516 8.517 8.516 8.515 8.497 0 5620726 20357271 20484573 20490608 23185904 23333090 19880149 20334305 23193684 0.00 303.53 1436.48 1453.89 1461.02 1736.79 1793.25 1389.39 1478.69 1789.14 100% 94% 113% 117% 1450.5 12.62 0.9% 1765.0 32% 1434.0 62% 100% 99% 4425 121206 8157 8493 7922 123536 124606 8793 8559 126016 0.22 21.29 0.91 0.97 0.88 21.93 21.93 1.03 0.98 22.12 100% 98% 98% 99% 0.92 0.05 5.5% 21.9 0.0% 1.01 5% 0 8.517 8.518 8.518 8.517 8.517 8.518 8.516 8.514 8,517 0 5546976 20126127 20089121 20246479 22967407 22905768 20074759 19980022 23026136 0.00 310.87 1477.11 1483.63 1507.21 1811.60 1781.87 1490.74 1469.36 1787.93 102% 106% 96% 101% 1489.3 15.84 1.1% 1796.7 1.7% 1480.0 1% 103% 102% 0 120883 9154 9010 0.00 21.33 0.85 0.81 100% 0.89 0.11 0 8.517 8.517 8.518 0 5445566 19903977 19918812 0.00 305.65 1518.97 1499.45 101% 1496.8 23.54 104% Page 119 of 158 PHOTODEGRADATION STUDY: PFOS in Fe2Oj Acquisition Method: H608PFOS.m Instrument: HillaryHPUOOMSD Acquisition Sequence: H060800.S Directory: H060800 SAMPLES AND SPIKES *Vial leaked in photoreactor Batch File Sample ID# H06080C HILL0095.D 053lOOPFOSfe-45 H060800C HILL0096.D 053100PFOSfe-46 H060800 HILL0097.D 053100PFOSfe47 H060300c HILL0098.D 05310OPFOSfe-48 H060800C HILL0099.D 0531 OOPFOSfe-49 H060800C HILL0103.D 053100PFOSfe-50 Exposure Time 0; with H2O2 Time 0; with H2O2 Time 0; with HjOj Time 0; with l-^C^ Time 0; with H2O2 Time 0; with H2O2 PFBS Sample Description Sample trip Sample spike Sample spikedup Control no Fe203 Control dup- noF e ^ Control Spike- noFe203 RT 7.344 7.345 7.344 7.347 7.366 7.368 Area 685687 673611 676858 664950 673105 674644 Amount 47.4 47.4 47,4 47.4 47.4 47.4 RT 6.265 8.246 8.247 8.268 8.266 8.266 H060800C HILL0104D 0531Q0PFOSfe-51 H060800C HILL0105.D 05310OPFOSfe-52 H060600C HILL0106.D 0531 OOPFOSfe-53 H060800C HILL0107.D 053100PF0Sfe-54 H060800c HILL0108.D 0531OOPFOSfe-55 H06080C HILL0109.D 05310OPFOSfe-56 H060800C HILL0110.D 0531OOPFOSfe-57 H060600C HILL0111.D 053100PFOSfe-58 H060800C HILL0112.D 053100PFOSfe*59 H060800c HILL0113.D 053100PFOSfe-60 Time 0; no HjOj Time 0; no H2 0 2 Time 0; no H20 2 Time 0; no HjOj Time 0; no H20 2 Time 0; no H20 2 Time 0; no H2O2 Time 0; no H20 2 Time 0; no H20 2 Time 0; no H20 2 Matrix biank Matrix biank spike Sample Sample dup Sample trip Sample spike Sample spike dup Control no Fej03 Control dup- noFejO Control Spike- noFe20 3 7.368 7.37 7.368 7.37 7.37 7.368 7.368 7.368 7.368 7.369 675398 675769 682028 679727 676568 673047 669696 671884 672974 662559 Wean: 7.350 STDEV: 0.010 701009 27118 47.4 47.4 47.4 47.4 47.4 47.4 47.4 47.4 47.4 47.4 0 8.267 8.288 8.288 8.287 8.266 8.268 8.269 8.288 8.266 BACK TO MAIN 3M tnvironmental Laboratory Report No. W2775 PFOA PFOS Area 10206 119509 122929 9626 9332 121264 Amount 1.01 21.32 21.85 0.96 0.89 21.61 Spike Mean/STDEV/ RSD %Recov. o r Mean/RPD 12% 95% 21.6 98% 2.4% 0.92 97% 8.2% RT 8.518 8.518 8.517 8.52 8.519 8.541 Area 19808521 22630822 22709847 19586256 19693182 22287121 Amount 1472.10 1825.69 1822.07 1511.83 1497.87 1780.39 Spike Mean/ STDEV / RSD %Recov. or Mean/RPD % o f Oriqinal 1.6% 108% 1823.9 107% 02% 1504.B 104% 0.9% 91% 0 120129 9113 8159 8982 124840 122011 8496 8167 122255 0.00 21.37 0.82 0.65 0.81 22.33 21.92 0.73 0.67 22.21 100% 101% 99% 101% 0.76 0.10 12% 22.1 1.9% 0.70 9.0% 0 8.522 8.541 8.543 8.543 8.54 8.541 8.541 8.54 B.54 0 5433257 19694996 19502085 19442468 22424057 22002669 19373620 19461929 21972361 0.00 307.74 1471.30 1458.41 1461.58 1803.03 1766.01 1468.36 1474.24 1790.60 101% 112% 100% 105% 1463.8 6.72 0.5% 1784.5 2.1% 1471.3 0.4% 101% 102% 98% 1.6% 1.6% 97% 21.1% 22% Page 120 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 PHOTODEGRADATION STUDY: PFOS in Fe20 3 Acquisition Method: H608PFOS.m Instrument: Hillary HP 1100 MSD Acquisition Sequence: H060800.S Directory: H060800 Ini Date 6/8/2000 22:36 6/8/2000 22:58 6/8/2000 23:19 6/8/2000 23:41 6/9/2000 0.02 6/9/2000 0:24 6/9/2000 0:45 6/9/2000 1:07 6/9/2000 1:28 6/9/2000 10:49 6/9/2000 11:10 6/9/200011:32 6/9/2000 11:53 6/9/2000 12:15 6/9/2000 12:37 6/9/2000 12:58 6/9/2000 13:20 6/9/2000 13:41 6/9/2000 10:49 6/9/2000 11:10 6/9/2000 11:32 6/9/2000 11:53 6/9/2000 12:15 6/9/2000 12:37 6/9/2000 12:58 6/9/2000 13:20 6/9/200013:41 6/9/2000 23:02 6/9/2000 23:24 6/9/2000 23:45 6/10/2000 0:07 6/10/2000 0:28 6/10/2000 0:50 6/10/2000 1:11 6/10/2000 1:33 6/10/2000 1:54 6/9/2000 23:24 6/9/2000 23:45 PFBS PFOA Batch H060800 H060800 H060800 H060800 H060800 H060800 H060800 H060800 H060800 File HILL0012.D HILL0013.D HILL0014.D HILL0015.D HILL0016.D HILL0017.D HILL0018.D HILL0019.D HILL0020.D Sample Name 00028-42-00 00028-42-01 00028-42-02 00028-42-03 00028-42-04 00028-42-05 00028-42-06 00028-42-07 00028-42-08 RT 7.342 7.343 7.343 7.344 7.344 7.344 7.343 7.345 7.344 Area 702865 725209 709056 719276 714894 712779 714669 700939 698369 CONC., ng/mL 47.4 47.4 47.4 47.4 47.4 47.4 47.4 47.4 47.4 RT 0 8.243 8.243 8.242 8.242 8.243 8.242 8.243 8.241 Area 0 7620 13972 23922 37019 46031 71600 115065 171633 H060800 H060800 H060800 H060800 H060800 H060800 H060800 H060800 H060800 HILL0046.D HILL0047.D HILL0048.D HILL0049.D HILL0050.D HILL0051.D HILL0052.D HILL0053.D HILL0054.D 00028-42-00 00028-42-01 00028-42-02 00028-42-03 00028-42-04 00028-42-05 00028-42-06 00028-42-07 00028-42-08 7.343 7.344 7.345 7.344 7.345 7.366 7.345 7.345 7.344 715946 718911 706237 708786 705879 699550 704070 695313 692825 47.4 47.4 47.4 47.4 47.4 47.4 47.4 47.4 47.4 7.893 8.239 8.243 8.242 8.245 8.246 8.244 8.243 8.243 2301 8369 13944 25711 36558 46576 70559 116203 169085 H060800b H060800b H060800b H060800b H060800b H060800b H060800b H060800b H060800b HILL0046.D HILL0047.D HILL0048.D HILL0049.D HILL0050.D HILL0051.D HILL0052.D HILL0053.D HILL0054.D 00028-42-00 00028-42-01 00028-42-02 00028-42-03 00028-42-04 00028-42-05 00028-42-06 00028-42-07 00028-42-08 7.345 7.344 7.345 7.344 7.345 7.366 7.345 7.345 7.344 706580 718911 706237 708786 705879 699550 704070 695313 692825 47.4 47.4 47.4 47.4 47.4 47.4 47.4 47.4 47.4 0 8.239 8.243 8.242 8.245 8.246 8.244 8.243 8.243 0 8369 13944 25711 36558 46576 70559 116203 169085 H060800b H060800b H060800b H060800b H060800b H060800b H060800b H060800b H060800b HILL0080.D HILL0081.D HILL0082.D HILL0083.D HILL0084.D HILL0085.D HILL0086.D HILL0087.D HILL0088.D 00028-42-00 00028-42-01 00028-42-02 00028-42-03 00028-42-04 00028-42-05 00028-42-06 00028-42-07 00028-42-08 7.343 7.342 7.344 7.343 7.343 7.342 7.345 7.344 7.341 659881 674740 672211 668276 665928 672097 660541 667169 658291 47.4 47.4 47.4 47.4 47.4 47.4 47.4 47.4 47.4 8.273 8.244 8.25 8.244 8.244 8.243 8.244 8.243 8.241 4987 10410 15587 27492 35743 44448 67333 111348 166510 H060800C HILL0081.D 00028-42-01 H060800C HILL0082.D 00028-42-02 7.342 674740 7.344 672211 47.4 47.4 8.244 8.25 10415 15587 Measured CONC., ng/mL 0.00 0.95 2.09 3.76 6.06 7.64 12.04 19.96 30.05 Target CONC., nq/mL 0.0 1.0 2.0 4.0 6.0 8.0 12.0 20.0 30.0 % Recovery 95% 104% 94% 101% 95% 100% 100% 100% PFOS RT Area 00 8.513 3943772 8.515 9148149 8.517 13409846 8.517 17231633 8.517 19548066 8.516 21969761 8.518 23842895 8.516 25717031 Measured CONC., nq/mL 0.00 190.00 533.59 822.50 1123.34 1322.35 1536.55 1767.48 1985.77 Target CONC., nq/mL % Recovery 202 506 810 1113 1316 1518 1720 1923 94% 105% 102% 101% 100% 101% 103% 103% 0.05 1.09 2.09 4.14 6.06 7.89 12.05 20.32 29.84 0.0 1.0 2.0 4.0 6.0 8.0 12.0 20.0 30.0 109% 105% 103% 101% 99% 100% 102% 99% 8.518 24058 8.516 3879532 8.517 8929180 8.517 13045408 8.518 16535546 8.519 18881956 8.518 21030863 8.517 22787153 8.517 24622440 0.00 188.17 521.14 810.00 1084.32 1295.57 1478.60 1677.19 1883.19 202 506 810 1113 1316 1518 1720 1923 93% 103% 100% 97% 98% 97% 98% 98% 0.00 0.87 1.87 3.91 5.83 7.65 11.80 20.05 29.54 0.0 1.0 2.0 4.0 6.0 8.0 12.0 20.0 30.0 87% 94% 98% 97% 96% 98% 100% 98% 8.518 19350 8.516 3879532 8.517 8929180 8.517 13045408 8.518 16535546 8.519 18881956 8.518 21030863 8.517 22787153 8.517 24622440 0.00 188.12 525.96 820.91 1103.13 1322.30 1513.87 1723.99 1945.22 202 506 810 1113 1316 1518 1720 1923 93% 104% 101% 99% 100% 100% 100% 101% 0.37 1.34 2.30 4.51 6.06 7.60 12.01 20.02 30.64 0.0 1.0 2.0 4.0 6.0 8.0 12.0 20.0 30.0 134% 115% 113% 101% 95% 100% 100% 102% 8.519 22614 8.515 3724312 8.517 8423870 8.517 12233477 8.516 15625838 8.516 17778972 8.517 19856313 8.517 21572553 8.514 23298549 0.00 193.61 520.50 815.59 1105.45 1288.02 1527.08 1691.00 1932.87 202 506 810 1113 1316 1518 1720 1923 96% 103% 101% 99% 98% 101% 98% 101% 1.08 2.05 1.0 108% 8.515 3724687 192.02 202 2.0 103% 8.517 8423870 523.95 506 95% 104% Page 121 of 158 PHOTODEGRADATION STUDY: PFOS in Fe20 3 Acquisition Method: H608PFOS.m Instrument: Hillary HP1100 MSD Acquisition Sequence: H060800.S Directory: H060800 Ini Date 6/10/2000 0:07 6/10/2000 0:28 6/10/2000 0:50 6/10/20001:11 6/10/2000 1:33 6/10/20001:54 PFBS PFOA Batch H060800C H060800C H060800C H060800C H060800C H060800C File HILL0083.D HILL0084.D HILL0085.D HILL0086.D HILL0087.D HILL0088.D Sample Name 00028-42-03 00028-42-04 00028-42-05 00028-42-06 00028-42-07 00028-42-08 RT 7.343 7.343 7.342 7.345 7.344 7.341 Area 668276 665928 672097 660541 667169 658291 CONC., ng/mL 47.4 47.4 47.4 47.4 47.4 47.4 RT 8.244 8.244 8.243 8.244 8.243 8.241 Area 27492 35743 44448 67333 111348 166510 Measured CONC., nq/mL 4.29 5.86 7.42 11.89 20.01 30.76 6/10/2000 11:15 6/10/200011:37 6/10/2000 11:58 6/10/2000 12:20 6/10/2000 12:41 6/10/2000 13:03 6/10/2000 13:24 6/10/2000 13:46 6/10/2000 14:07 H060800C H060800C H060800C H060800C H060800C H060800C H060800C H060800C H060800C HILL0114.D HILL0115.D HILL0116.D HILL0117.D HILL0118.D HILL0119.D HILL0120.D HILL0121.D HILL0122.D 00028-42-00 00028-42-01 00028-42-02 00028-42-03 00028-42-04 00028-42-05 00028-42-06 00028-42-07 00028-42-08 Curves: PFOS=quadratic, ignore origin, IS calc PFOA=linear, Ignore origin, IS calc 7.37 7.37 7.368 7.367 7.369 7.369 7.367 7.369 7.369 7.349 0.010 0.1% 648481 659850 654534 651852 656141 645838 648666 663314 642005 684770 24348 3.6% 47.4 47.4 47.4 47.4 47.4 47.4 47.4 47.4 47.4 00 0.00 8.275 10552 1.15 8.273 15559 2.12 8.268 25641 4.07 8.269 36410 6.09 8.269 46413 8.13 8.268 66399 11.94 8.269 106948 8.269 157620 19.30 29.83 Batch 1: r2=0.9980 Batch 2: r2 =0.9989 Batch 3: r2 =0.9988 CCV Standards: Ini Date 6/9/2000 6:30 6/9/2000 18:22 6/10/2000 6:35 Batch H060800 H060800b H060800C PFBS File HILL0034.D HILL0067.D HILL0101.D Sample Name 00028-42-05 00028-42-05 00028-42-05 RT 7.345 7.344 7.364 Area 722173 679595 671958 CONC., ng/mL 47.4 47.4 47.4 RT 8.243 8.242 8.262 PFOA Area 46842 45748 45521 Measured CONC., ng/mL 7.67 7.74 7.62 BACK TO MAIN j m tnvironmental Laboratory Report No. W2775 Target CONC., ng/mL 4.0 6.0 8.0 12.0 zo.o 30.0 PFOS Measured % Recovery 107% 98% 93% 99% 100% 103% RT 8.517 8.516 8.516 8.517 8.517 8.514 Area 12233477 15625838 17778972 19856313 21572553 23298549 CONC., ng/mL 824.54 1120.95 1308.40 1555.04 1725.14 1978.13 o CO Target CONC., ng/mL 1113 1316 1518 1720 1923 % Recovery 102% 101% 99% 102% 100% 103% 0.0 1.0 2.0 4.0 6.0 8.0 12.0 20.0 30.0 115% 106% 102% 101% 102% 100% 97% 99% 8.544 23104 0.00 8.541 3610404 189.83 8.54 8157669 520.56 8.538 11805802 813.91 8.542 15046876 1088.88 8.541 17005557 1300.48 8.541 19043147 1504.92 8.542 20821672 1652.91 8.542 22293131 1920.01 Batch 1: r2=0.9997 Batch 2: r2==0.9994 Batch 3: r2==0.9985 202 506 810 1113 1316 1518 1720 1923 94% 103% 100% 98% 99% 99% 96% 100% Target CONC., ng/mL 8.0 8.00 8.00 PFOS Measured % Recovery 96% 97% 95% RT 8.517 8.517 8.517 Area 19569171 18214719 17443139 CONC., ng/mL 1302.09 1310.20 1276.45 Target CONC., ng/mL 1316 1316 1316 % Recovery 99% 100% 97% Page 122 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 PHOTODEGRADATION STUDY: PFOS in Fe20 3 Acquisition Method: H608PFOS.m Instrument: Hillary HP1100 MSD Acquisition Sequence: H060800.S Directory: H060800 SOLVENT BLANKS Inj Date 6/8/2000 21:53 6/8/2000 22:15 6/9/2000 1:50 6/9/2000 2:11 6/9/2000 6:09 6/9/2000 6:52 6/9/2000 14:03 6/9/2000 14:24 6/9/2000 18:00 6/9/2000 18:43 6/10/2000 2:16 6/10/2000 2:16 6/10/2000 2:37 6/10/2000 6:13 6/10/2000 6:56 6/10/2000 14:29 Batch H060800 H060800 H060800 H060800 H060800 H060800 H060800b H060800b H060800b H060800b H060800b H060800C H060800C H060800C H060800C H060800C File HILL0010.D HILL0011.D HILL0021.D HILL0022.D HILL0033.D HILL0035.D HILL0055.D HILL0056.D HILL0066.D HILL0068.D HILL0089.D HILL0089.D HILL0090.D HILL0100.D HILL0102.D HILL0123.D Sample Name Meoh Blk 7:1 Meoh: H20 7:1 Meoh: H20 7:1 Meoh: H20 7:1 Meoh: H20 7:1 Meoh: H20 7:1 Meoh: H20 7:1 Meoh: H20 7:1 Meoh: H20 7:1 Meoh: H20 7:1 Meoh: H20 7:1 Meoh: H20 7:1 Meoh: H20 7:1 Meoh: H20 7:1 Meoh: H20 7:1 Meoh: H20 PFBS PFOA Average Area of LOQ RT Area Area of IS RT Area std RT 0 693337 8.271 2021 7620 0 0 693337 8.288 1559 7620 0 0 693337 8.265 1525 7620 0 0 693337 8.321 1723 7620 0 0 693337 8.272 1112 7620 8.522 0 693337 8.253 2112 7620 0 0 693337 8.244 2690 8369 0 0 693337 8.265 2379 8369 0 0 693337 8.266 3261 8369 8.518 0 693337 8.264 4117 8369 8.517 0 693337 8.273 4119 8369 8.517 0 693337 8.273 4119 10415 8.517 0 693337 8.271 4828 10415 8.519 0 693337 8.286 4536 10415 8.516 0 693337 8.29 3838 10415 8.542 0 693337 8.297 3481 10415 8.541 PFOS Area 0 0 0 0 20277 0 0 0 21641 21052 18503 18503 23079 23085 20791 20802 Area of LOQ std 3610404 3610404 3610404 3610404 3610404 3610404 3610404 3610404 3610404 3610404 3610404 3610404 3610404 3610404 3610404 3610404 SOLVENT BLANKS (WITH I.S.) Inj Date 6/8/2000 22:36 6/9/2000 10:49 6/9/2000 23:02 6/10/2000 11:15 Batch H060800 H060800 H060800b H060800C File HILL0012.D HILL0046.D HILL0080.D HILL0114.D Sample Name 00028-42-00 00028-42-00 00028-42-00 00028-42-00 PFBS RT 7.342 7.343 7.343 7.37 Area 702865 715946 659881 648481 47.4 47.4 47.4 47.4 PFOA RT 0 7.893 8.273 0 Area 0 2301 4987 0 Measured CONC., ng/mL 0.00 0.05 0.37 0.00 RT 0 8.518 8.519 8.544 PFOS Area 0 24058 22614 23104 Measured CONC., ng/mL 0.00 0.00 0.00 0.00 METHOD BLANKS PFBS Inj Date 6/9/2000 2:33 6/9/2000 7:13 6/9/2000 14:46 6/9/2000 19:26 6/10/2000 2:59 6/10/2000 7:40 Batch H060800 H060800 H060800b H060800b H060800C H060800C File HILL0023.D HILL0036.D HILL0057.D HILL0070.D HILL0091.D HILL0104.D Sample Name 053100PFOSfe-01 053100PFOSfe-11 05310OPFOSfe-21 053100PFOSfe-31 053100PFOSfe-41 053100PFOSfe-51 RT 7.343 7.345 7.344 7.343 7.342 7.368 Area 729810 734378 704168 694542 676778 675398 47.4 47.4 47.4 47.4 47.4 47.4 PFOA RT 0 0 0 8.275 0 0 Area 0 0 0 4425 0 0 Measured CONC., nq/mL 0.00 0.00 0.00 0.22 0.00 0.00 RT 0 0 0 0 0 0 PFOS Area 0 0 0 0 0 0 Measured CONC., nq/mL 0.00 0.00 0.00 0.00 0.00 0.00 Page 123 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 Analysis of PFOS Photodegradation Study in Synthetic Humic Water Photolysis - 4-24-00 Analysis - 4-27-00 instrument - Hillary Technicians - JAM/JGS Sample I.D. 042400-PFOS-01 042400-P FOS-02 042400-PFOS-03 Q424QQ-PFOS-04 Sample Description Day 0 Sam ples Sample 26 Sample duplicate 27 Sample triplicate 28 Sample Spike 29 Reprocessing Method H0428SHW.M H 0 4 2 8 S H W .M H0428SHW.M H0428SHW.M Data File hshwO026.D hshwO027.D hshwO028.D hshw0029.D 042400-PFOS-05 042400-PFOS-06 042400-PFOS-07 Matrix Blank Matrix Blank Spike Matrix Blank Spike 30 H0428SHW.M 31 H0428SHW.M 32 H0428SHW.M hshw0030.D hshw0031.D hshw0032.D Q42400-PFOS-08 MilliQ Sample 042400-PFOS-09 MilliQ Sample #2 33 H0428SHW.M 34 H0428SHW.M hshw0033.D hshwO034.D 042400-PFOS-10 MilliQ Spike 042400-PFOS-11 MilliQ Spike #2 35 H0428SHW.M 36 H0428SHW.M hshwO035.D hshw0036.D 99122-149-05 042400-PFOS-12 042400-PFOS-13 042400-PFOS-14 042400-PFOS-15 std - 20 ng/ml 38 H0428SHW.M Exposed Sam ples Sample 40 H042BSHW.M Sample duplicate 41 H0428SHW.M Sample triplicate Sample Spike 42 H0428SHW.M 43 H0428SHW.M hshw0038.D hshw0040.D hshw0041.0 hshw0042.D hshw0043.D 042400-PFOS-16 042400-PFOS-17 042400-PFOS-18 Matrix Blank Matrix Blank Spike Matrix Blank Spike 44 H0428SHW.M 45 H0428SHW.M 46 H0428SHW.M hshw0044.D hshwO045.D hshw0046.D 042400-PFOS-19 MilliQ Sample 042400-PFOS-20 MilliQ Sample #2 47 H042SSHW.M 48 H0428SHW.M hshw0047.D hshw0048.0 042400-PFOS-21 042400-PFOS-22 MilliQ Spike MilliQ Spike #2 49 H0428SHW.M 50 H0428SHW.M hshw0049.D hshw0050.D 99122-149-05 042400-PFOS-23 042400-PFOS-24 042400-PF OS-25 042400-PFOS-26 std - 20 ng/ml 52 H0428SHW.M Unexposed Sam ples Sample 54 H0428SHW.M Sample duplicate 55 H0428SHW.M Sample triplicate 56 H0428SHW.M Sample Spike 57 H0428SHW.M hshw0052.D hshw0054.D hshw0055.D hshw0056.D hshw0057.D O42400-PFOS-27 042400-PFOS-28 042400-PFOS-29 Matrix Blank Matrix Blank Spike Matrix Blank Spike 58 H0428SHW.M 59 H0428SHW.M 60 H0428SHW.M hshw0058.D hshw0059.D hshw0060.D PFBS Retention Time (Minutes) Peak Area Mean S.D. V.RSD N> 5.15 5 .1 6 5.15 5 .1 5 5.15 5.15 5.16 5 .1 6 5.16 5.16 5 .1 6 5.16 5.16 5.16 5 .1 6 5.16 5 .1 6 5 .1 6 5 .1 6 5 .1 6 5 .1 6 5 .1 6 5 .1 6 5.17 642072 647618 645518 650712 629451 636531 631042 640761 637293 643595 635745 633597 625154 640042 619735 648201 609204 621745 625536 636439 641755 641605 636055 635249 5 .1 6 5.16 5.16 5 .1 6 5.16 5.16 5 .1 6 649465 657111 640505 629825 632209 62Q603 702066 PFOA Retention Time (Minutes) Peak Area Concentration (nmi) (ppn) Accuracy (M u cured/ Nominal) Mean S.D. %RSD PFOS Retention Time (Minutes) Peak Area Accuracy Concentration (Me*cured/ (ng/ml) (ppb) Nominal) Mean S.D. %RSD 5.71 5.71 5.71 5.71 5.71 5.71 5.72 5,71 5.71 5.71 5.71 5.72 32436 30491 30738 497826 21518 475137 482332 32042 30456 485342 488523 396048 BQL BQL BQL 25.31 BQL 24.14 24.51 BQL BQL 24.67 24.83 20,05 97.4% 92.8% 94.3% 94.9% 95.5% 100.2% 5 .8 7 5.87 5.87 5.87 5 .8 6 5.87 5 ,8 7 5.87 5.87 5.87 5 .8 7 5 .8 7 2834363 2842217 2792380 3598527 3815 689426 685595 28346Q3 2905258 3554759 3539849 535836 190.62 100.90 99.14 127.61 BQL 24.86 24.73 1QQ.63 103.12 126.0 125.54 19.44 93.2% 93.4% 91.8% 105.4% 1 0 0 .2 2 0.95 0.9% 95.6% 95.1% 24,79 0 .1 0 93.2% 95.5% 1 0 1 .8 8 1 .7 6 93.0% 91.0% 125.80 0,37 97.2% 5.71 5.71 5.71 5.71 5.71 5.71 5.71 5.71 5.71 5.71 5.71 5.72 30110 29721 30826 500170 BQL BQL BQL 25.44 23082 484021 492545 BQL 24.60 - 25.04 30015 30021 BQL BQL 496314 497959 25.24 25.32 402857 20,40 97.8% 94.6% 96.3% 97.1% 97.4% 102.0% 5 .8 7 5 ,8 7 5 .8 7 5.87 5 .8 3 5.87 5 .8 7 5.87 5 .8 7 5 .8 7 5 .8 7 5.87 2855272 2816350 2779726 3527102 3989 699807 697911 2791391 2681452 3489470 3536618 543565 101.36 99.98 98.69 125.09 BQL 25.23 25.16 99.10 95.22 123.76 125.42 19.71 93.9% 92.6% 91.4% 96.4% 100.01 1.33 1.3% 97.0% 96.8% 25.20 0.05 91.8% 88.2% 97.16 2 .7 5 102.3% 108.7% 124.59 1.18 98.6% 5.71 5.71 5.71 5.71 5.71 5.71 5.71 31169 30972 31017 510519 20952 490378 492894 BQL BQL BQL 25.97 BQL 24,33 25.06 99.9% 95.9% 96.4% 5 .8 7 5 .8 7 5 .8 7 5 .8 7 5 .8 5 5.87 5.87 2902100 2897273 2896100 3576627 5085 683248 713930 103.01 102.84 102.80 126.S4 BQL 24.64 25.73 95.4% 95.2% 95.2% 92.1% 102.89 0.11 0 .1% 94.8% 99.0% 25.19 0.77 Page 124 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 Analysis of PFOS Photodegradation Study in Synthetic Humic Water Photolysis - 4-24-00 Analysis - 4-27-00 Instrument - Hillary Technicians - JAM/JGS Sample I.D. Sample Description Reprocessing Method Data File 042400-PFOS-30 MilliQ Sample Q42400-PFOS-31 MilliQ Sample #2 61 H0428SHW.M 62 H0428SHW.M hshw0061.D hshw0062.D 042400-PFOS-32 MilliQ Spike 042400-PFOS-33 MilliQ Spike #2 63 H0428SHW.M 64 H0428SHW.M hshw0063.D hshw0064.D 99122-149-00 99122-149-01 99122-149-02 99122-149-03 99122-149-04 99122-149-05 99122-149-06 99122-149-07 99122-149-08 99122-149-00 99122-149-01 99122-149-02 99122-149-03 99122-149-04 99122-149-05 99122-149-06 99122-149-07 99122-149-08 99122-149-00 99122-149-01 99122-149-02 99122-149-03 99122-149-04 99122-149-05 99122-149-06 99122-149-07 99122-149-08 Calibration Standards std - 0 ng/ml 4 H0428SHW.M std -1 ng/ml 5 H0428SHW.M std - 2 ng/ml 6 H0428SHW.M std - 5 ng/ml 7 H0428SHW.M std - 10 ng/ml 8 H0428SHW.M std - 20 ng/ml 9 H0428SHW.M std - 50 ng/ml 10 H0428SHW.M std - 100 ng/ml 11 H0428SHW.M std - 150 ng/ml 12 H0428SHW.M hshw0004.D hshwOOOS.D hshw0006.D hshw0007.D hshw0008.D hshw0009.D hshwOOIO.D hshwOOH.D hshw0O12.D std - 0 ng/ml std -1 ng/ml std - 2 ng/ml std - 5 ng/ml std -1 0 ng/ml std - 20 ng/ml std - 50 ng/ml std - 100 ng/ml std - 150 ng/ml 16 H0428SHW.M 17 H0428SHW.M 18 H0428SHW.M 19 H0428SHW.M 20 H0428SHW.M 21 H0428SHW.M 22 H0428SHW.M 23 H0428SHW.M 24 H0428SHW.M hshw0016.D hshw0017.D hshw0018.D hshwQ019.D h$hwOO20.D hshw0021.D hshw0022.D hshw0023.0 hshw0024.D std - 0 ng/ml std - 1 ng/ml std - 2 ng/ml std - 5 ng/ml std -1 0 ng/ml std - 20 ng/ml std - 50 ng/ml std - 100 ng/ml std - 150 ng/ml 67 H0428SHW.M 68 H0428SHW.M 69 H0428SHW.M 70 H0428SHW.M 71 H0428SHW.M 72 H0428SHW.M 73 H0428SHW.M 74 H0428SHW.M 75 H042BSHW.M hshw0067.D hshw0068.D hshw0O69.D hshw0070.D hshw0O71.D hshw0072.D hshw0073.D hshw0074.D hshw0075.0 PFBS Retention Time (Minutes) Peak Area Mean S.D. %RSD N> PFOA Retention Time (Minutes) Peak Area Concentration (ng/ml) (ppbl Accuracy (IfeMured/ Nominal) Mean S.D. %RSD PFOS Retention Time (Minutes) Accuracy Concentration (M un nd / Peak Area (ng/ml) (ppb) Nominal) Mean S.D. %RSD 5.16 5.16 5 .1 6 5.16 622097 639895 652034 649424 638568 15334 2.4% 35 Regression rv a lu e range LOQ 5.71 30924 5.71 30066 BQL BQL 5.71 502917 5.71 513718 25.58 26.14 98.4% 100.5% Linear; inciude zero: equal w eight!; external quant 0.9998 2-1C ppte " e xcluding Sppb 2ppfa 5.87 5.87 2812873 2818267 99.88 100.05 92.5% 92.6% 99.96 0.13 5.B7 5.87 3590904 3683800 127,34 130.82 105.3% 117.9% 128.98 2.32 Linear: include zero: equal weight!; external quant 0,9337 2-150 ppta 2ppi> 5 .1 6 5.16 5.16 5.15 5.15 5.16 5.15 5.15 5.15 639959 636720 636471 645599 638302 645676 640047 645546 635013 5.14 5.14 5.14 5.14 5,15 5.15 5.15 5.15 5.15 625083 626331 613117 627035 634860 648510 649121 660067 638789 5.16 5.16 5.16 5.16 5 .1 6 5.16 5 .1 6 5.16 5.16 Mean S.D. %RSD 631240 632928 599675 660438 631303 649589 617252 643813 627944 637586 14458 2.3% 636312 13416 2.1% 27 5.72 5.72 5.71 5.71 5.71 5.72 5.71 5.72 5.71 5.70 5.70 5.70 5.70 5.71 5.71 5.70 5.71 5.71 5.71 5.72 5.71 5.71 5.72 5.71 5.71 5.71 5.72 22452 65747 53619 145291 203131 383606 980772 1865416 2704150 23431 65432 52613 143961 197967 387210 989287 1921181 2749173 22791 65648 52107 152237 204874 398507 982510 1951819 2767056 0 ,7 2 2.96 2 .3 4 7.08 10.67 19.41 50,30 96.06 139.45 -0.44 0 .7 7 2.9 S 2.28 7.01 9.80 19.59 50.74 38,95 141.78 -0.44 0.74 2.96 2 .2 6 7 .4 4 10.16 20.18 50.39 1 0 0 .5 3 1 4 2 .7 0 I 296.3% 116.8% I 141.6% 100.7% 97.0% 100.6% 96.1% I 93.0% excluded excluded excluded I 294.7% 114.2% I 140.2% 98.0% 98.0% 101.5% 98.9% 94,5% excluded excluded excluded 295.9% 112.9% 148.7% 101.6% 100.9% 100.8% 100.5% 95.1% excluded excluded excluded 5.85 5.88 5.87 5.87 5.87 5.87 5.87 5.88 5.87 5-86 5.86 5.86 5.86 5 ,8 7 5.87 5.86 5.87 5.87 5.84 5.87 5.87 5.87 5.87 5.87 5.87 5.87 5.87 2376 28229 46442 120908 248212 519011 1396851 2822711 4083177 2361 28453 46259 116643 245418 528991 1392427 2844469 4182790 4456 30602 48387 127948 262753 541223 1401576 2883426 4228607 0.60 1.51 2.15 4.78 9.28 18.84 49.85 100.21 144,73 0.51 G.60 1.52 2,15 4.63 9.1$ 19.20 49.89 100.98 148.25 0.51 0.6? 1.53 2.22 5.03 9 .7 9 19.63 50.02 102.35 149.86 151-0% 107.6% 95.7% 92.8% 94.2% 99.7% 100.2% 96.5% excluded 151,7% 107.3% 92.6% 91.8% 96.0% 99.4% 101.0% 98.8% excluded 159.3% 111.1% 100.6% 9 7 .9 % 98.1% 100.0% 102.4% 99.9% excluded Page 125 of 158 BACK TO MAIN j m hnvironmental Laboratory Report No. W2775 Analysis of PFOS Photodegradation Study in Synthetic Humic Water Photolysis - 4-24-00 Analysis - 4-27-00 Instrument - Hillary Technicians - JAM/JGS S a m p le I.O. MeOH blank MeOH blank Matrix blank Matrix blank MeOH blank Matrix blank Matrix blank Matrix blank Matrix blank Matrix blank M atrix blank MeOH blank Matrix blank Matrix blank MeOH blank Sam ple Description R e p ro c e s s in g Method Data File Blank Sam ples 1 2 3 13 14 15 25 37 39 51 53 65 66 76 77 H 04 2 8 S H W .M H0428SHW.M H0428SHW.M H0428SHW.M H0428SHW.M H0428SHW.M H 0 4 2 8 S H W .M H0428SHW.M H0428SHW.M H0428SHW.M H 0 4 2 8 S H W .M H0428SHW.M H 0 4 2 8 S H W .M H 0 4 2 8 S H W .M H0428SHW.M hshw0001,D hshw0002.D hshw0003.D hshwOOl3.D hshw0014.D h sh w 0 0 l5 .D hshw0025.D hshw0037.D hshw0039.D hshw0051.D hshw0053.D hshw0065.D hshw0066.D hshw0076.D hshw0O77.D PFBS Retention Tim e (Minutes) P e a k A rea n 62 Mean S.D . %RSD N* 0.00 5.17 5.16 5.16 5.17 5.16 5.16 5.18 5.16 5 .1 6 5.17 5 .1 6 5.17 5,17 5.18 0 4895 4679 3537 4290 3534 4350 3463 4279 4361 5126 4788 4068 4058 3405 4202 560 13.3% 14 PFOA PFOS Retention Tim e (Minutes) Peak Area C o n cen tra tio n (ng/ml) (ppb) Accuracy (Measured/ N o m in al) Mean S.D. %RSD R e ten tio n T im e (Minutes) Peak Area C oncentration (ng/m l) (ppb) A ccu racy (Measured/ N o m in al) Mean S .D . % RSD 5.71 5.72 5.71 5.71 5.71 5.71 5.71 5.72 5.72 5.71 5.72 5.71 5 .7 2 5.71 5.72 119554 24126 23128 23209 22035 23390 24870 24065 22997 22045 22710 22888 23499 24088 23859 4.65 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 O.oo 0.00 0.00 0.00 0.00 23352 810 3.5% 14 5 .8 6 5.88 5 .8 6 5.87 5.B7 5.87 5 .8 4 5.86 5 .8 7 5.86 5.87 5.84 5 .8 6 5 .8 5 5 .8 6 . 6853 3254 3126 3314 4952 3572 3738 4668 4354 5070 5019 6774 5142 7109 6573 0.81 0.69 0.68 0.69 0.75 0.70 0.70 0.74 0.73 0 .7 5 0.75 0.81 0.75 0.82 0.60 Page 126 of 158 RM(061600) PFO S (Fe203) F ie Semple Name R0616001.D blank R0618D02.D blank R0616003.D 1til 09038*38*01 In 5ml R0816004.D 2u1 99038-38-01 In W R0616005.D 5ul 09038-38-01 m 5ml R0616006.D 6uf 99038-39-01 In 5ml R0816007.D lOul 99038-39-01 in Sml R0816008.D blank R0616009.D 051500-PFOSfe-101 matrix Wk R0618010.D 051500*PFOSfs-102 matrix bfcspk R0616011.O 051500-PFOSfe*103 sample R0618012.D 051500-PFO$fe-104 dup R061B013.D 0S1500-PFOSle-105lnp RD615014.D 051500-PFOSfe-106 spk R0616015 0 051500-PFOSfs>107 spk dup R0616016.D 051500-PFOSIe-108 control R0616017.D 051500-PFOSfe-109 control (hip R0016018.D 051500-PFOSte-110 control spk R0616019.D blank R0616Q20.D 8ul 99038-39-01 inSfrt R0616021.0 blank R0616Q22.O 051500-PFOSte-111 matrix tatk R0618023.D 0$150Q-PFOSIe-112maliixblkspk R0616024.D 051500-P fO S fe-113 sample R061602S.D 051SOO-PFOSR-114 Oup R0616026.0 051500-PFO Sle-1l5 trip R0616027.D 051500-PFOSfe-116spk R0616Q28.Q 051500-PFOSfe-117lpkdup R0616029.0 05150q- p f o s - i i b control R0616030.D 0515Q0-PFOSfe-119 control dup R0616031.O 051500-PFOSfe-120 control spk R0616032.0 blank R0616033.0 8ol 99038-39-01 in 5frt R0616034.0 blank R0616035.D 050900-EIFOSE-1S5 GC sample R0616036.D 050900-EtFOSE-156 GC spice R0616037.0 blank R061603B.D D50900.EtFOS6-167 GC sample R0616039.D 050900-EIFOSE-168 GC sample R0616040.D blank R0616041.D 050900-EtFOSE-179 GC sample R0616042.D 050900-EtFOSE-180 GC Spike R0616043.D blank R0816044.D 8ul 99038-39-01 in Sml R0618045.D blank BACK TO MAIN oivi environmental Laboratory Report No. W2775 co 3 1 o i & 0.00 I f I o i 8. 0.00 c 2 I o & X 0.00 = I 8. 5 0.00 S p ik e A m o u n t (ng/rml) s 0 So oI 1 ci Ei & 3 & O.X 0.00 o x Spike Recovery {% ) a 1 ?5 i f c S. e E. 1 5 f 1 2 e 1 I 3 E E J j e !S ai Ies e0 1 j i i f o 5g fSV. S. cv !J 1 ? 1 & X I s. I e 8. 3 1 & 8. [& Ci i I 3 !L I S S i J I!I o x 0.00 0.00 O X n/a n/a n/a n/a n/a (V* n/a n/a n/a n/a nta 0.00 0.00 0.00 0.00 O.X 0.00 0. x o x O .X o x o x rVi n/a n/a n/a n/a n/a n/a n/a n/a n/a n/a 0.97 1.01 1.00 0.05 1.20 1.25 1.08 1.42 0.15 0.10 o x 4 94 102 97 101 118 103 91 0 0 0 1.94 2.02 2.00 1.70 2.40 2.50 2.17 2.8$ 0.30 020 1.80 103 105 X 107 06 100 100 102 07 139 93 4.04 5.04 5.00 4.25 6 .X 6,25 5.42 7.12 D.75 0.50 4.50 102 X 103 X 101 X 100 103 107 101 105 7.74 0.00 6.00 6.00 9.00 10.X 8.67 11.39 1.20 0.80 720 98 104 97 96 102 90 98 99 103 98 100 9.60 10.06 10.00 8.50 12.X 12.X 10.84 1454 1.50 1.00 9.00 101 98 101 102 99 102 101 I X 97 101 99 0.00 0.00 0.00 0.00 O X O .X O .X O X 0.00 O X O X n/a n/a n/a n/a n/a n/a n/a n/a n/a n/a n/a 0.00 0.00 0.00 0.00 O.X O .X o x O X 0.00 000 o x n/a n/a n/a n/a n/a n/a n/a n/a n/a n/a n/a 7.74 0.06 8.00 6.80 9.60 10.00 8.67 11.39 1.20 0.80 7.20 89 92 93 93 97 78 94 100 82 104 59 0.00 0.00 0.00 0.00 O .X O .X O .X O X 0.00 0.00 O X iVa n/a n/a n/a n/a n/a n/a n/a n/a n/a n/a 0.00 0.00 0.00 0.00 O .X O .X O X O X 0.00 0.00 O X n/a n/a n/a n/a n/a n/a n/a n/a n/a n/a n/a 0.00 0.00 0.00 0.00 O .X O .X 0.00 0.00 0.00 o x o x rVa n/a n/a n/a n/a n/m n/a n/ n/a n/a n/a 7.74 0.06 8.00 6.80 9.60 10.00 8.67 11.39 1.20 0.80 720 91 103 102 ee X 04 101 102 95 102 64 7.74 0.06 8.00 6.80 9 .X 10.00 867 11.39 1.20 0.60 720 97 90 107 95 100 104 98 X 91 X 46 0.00 0.00 0.00 0.00 O.X O .X 0.00 O X O .X O X 0.00 n/a n/a n/a n/a n/a n/a n/a n/a n/a n/a n/a o.oo 0.00 0.00 0,00 O .X o x o x O X O .X o.oo o x n/a n/a n/a n/a n/a n/a n/a n/a n/a n/a n/a 7.74 8.06 8.00 6.80 9.60 10. x 6.67 11.39 1.20 0.80 720 70 60 95 05 94 91 89 94 79 75 40 0.00 0.00 0.00 0.00 O .X O.X 0.00 O X O .X 0.00 0.00 n/a n/a n/a n/a n/a n/a n/a n/a n/a n/a n/a 7.74 0.06 8.00 6.80 9.60 10. x 8.67 11.39 120 0.80 720 94 94 93 95 93 89 X 92 X 100 93 0.00 0.00 0.00 0.00 O .X O.X O.X O X O .X 0.00 O X n/a n/a n/a n/a n/a n/a n/a n/a n/a n/a n/a 0.00 0.00 0.00 O X O .X O .X O.X O X O .X o x O X n/a n/a n/a n/a n/a n /i n/t n/a n/a n/a n/a 7.74 8.06 8.00 6.60 9.60 10.00 8.67 11.39 1.20 0.80 7.20 X X 104 93 104 111 X 97 64 94 97 0.00 0.00 0.00 0.00 O.X O .X O X 0.00 O X O X O X n/a n/a n/a n/a n/a n/a n/a n/a n/a n/a n/a 0.00 0.00 0.00 0.00 O .X O .X o x O X 0.00 o x O X n/a n/a n/a n/a n/a n/a n/a n/a n/a n/a n/a 0.00 0.00 0.00 0.00 O .X 0.00 o x o x O X 0.00 O X rVa n/a n/a n/a n/a n/a n/a n/a n/a n/a n/a 7.74 8.06 8.00 6.80 9.60 10.X 887 11.39 1.20 o.eo 720 88 97 X 91 109 82 97 97 92 X 94 7.74 8.06 8.00 6.80 9.60 10.00 8.67 11.39 1.20 0.80 7.20 93 94 99 93 X 83 97 100 95 89 X 0.00 0.00 0.00 0.00 O .X O .X O X O X O X 0.00 O X n/a n/a n/a n/a n/a n/a n/a n/a n/a n/a n/a 0.00 0.00 0.00 O .X O .X o x O X O X o x o x 0.00 n/a n/a n/a n/a n/a n/a n/a n/a n/a n/a n/a 7.74 8.06 8.00 6.80 9 60 10. x 0.67 11.39 120 0.80 720 80 X 95 93 93 81 95 X S3 10 X 0.00 Q.00 0.00 0.00 0.00 o x O .X O X O .X 000 O X n/a n/a n/a n/a n/a n/a n/a n/a n/a n/a n/a 7.74 8.06 8.00 6.80 9.60 1 0 X 8.67 11.39 120 0.80 720 04 06 07 67 04 72 63 61 04 05 X 0.00 0.00 0.00 0.00 O X o x O X O X O .X 0.00 0.00 n/a n/a n/a n/a n/a n/a n/a n/a n/a n/a n/a 0.00 0.00 0.00 O .X O.X o x O.X O X o x 0.00 o x n/a n/a n/a n/a n/a n/a n/a n/a n/a n/a n/a 7.74 6.06 8.00 6.80 9.60 1 0 X 8.67 11.39 I X 0.80 7.20 93 110 65 S3 93 86 92 106 102 105 105 0.00 0.00 0.00 O .X O.X O.X O.X O X O .X 0.00 O X n/a n/a n/a n/a n/a n/a n/a n/a n/a n/a n/a 0.00 0.00 0.00 0.00 0.00 D X O X O X 0.00 O X 0.00 n/a n/a n/a n/a n/a n/a n/a n/a n/a n/a n/a 7.74 8.06 8.00 6.80 9 .X 10.X 8.67 11.39 1.20 0.80 720 92 93 X 95 93 84 101 100 88 96 77 0.00 Q.00 0.00 Q.00 O X o x O X O X O .X O X O X n/a n/a n/a n/a n/a n/a n/a n/a n/a n/a n/a 0.00 0.00 0.00 O .X O.X o x 0.00 O X o x O X o x n/a n/a n/a n/a n/a n/a n/a n/a n/a n/a n/a 7.74 8.06 8.00 6.6Q 9 .X 1 0 X 8.67 11.39 1.20 0.80 7.20 102 97 94 123 97 81 X X 100 89 79 0.00 0.00 0.00 O .X O.X O.X 0.00 O X 0.00 O X 0.00 n/a n/a n/a n /t nla n/a n/a n/a n/a n/a n/a 7.74 6.06 8.00 6.80 9 .X 10.00 8.67 11.39 1.20 0.80 7.20 88 93 99 65 86 97 90 91 90 104 92 0.00 0.00 0.00 0.00 O.X o x 0.00 O X 0 00 O X O X n/a n/a n/a n/a n/a n/a n/a n/a n/a n/a n/a Page 127 of 158 RM(061600) PFOS (Fe203) F8e Sampie Name R0616001.D biank R0615002.D biank RO616OO3.0 lu i 99038-38-01 klSml R0616004.D 2ul 99038-34-01 in 5fnt R061600S.D Sul 99038-38-01 in 5ml R061600S.D Sul 99038-30-01 in 5m) ROSI0007.0 lOul 99038-39-01 In Sml R0616008 0 biank R0616009.D 051500-PFOSfe-101 matrtx Wk R0616010.0 051500-PFOSfe*102 matrix bfc spk R0616011.0 051S00-PFOSC-103 sampte R0616012.0 051500-PFOSfe*104 dup R0616013.0 051S00-PFOSfe-105tnp R0816014.D 051S00-PFOSfe-106 spk R 06I6015 D 051SOO-PFOSfe-107 spk dup R0616018.0 051500-PFOSfe-108 control R0016017.D 051500-PFOSfe-109 control dup R0616018.0 0515QO-PFOSf-110 control spk R0816019.D biank R0616020.D 8ut 99038-39-01 in 5ml R0616021.0 biank R0616022.D 051500-PFOSfe-111 matrix bfc R0616023.0 051500-PFOSte-112 matrtx blk spk RQ616Q24.0 051500-PFO Sa-1l3s*npte R0616025.D 051500-PFOSfe-1l4dup R0616026.0 051500-PFOSfe-11S (rtp R0616027.D 051500-PFOSfe-H6spk R0616028.D 0S1500-PFOSfe-1l7spkdup R0616029.0 0515QO-PFOSfe*118 control R0616030.0 051500-PFOSfe-119 control dup R0616031,D 051S00-PFOSfe-120 control spk R0616032.0 biank R0616033.D Sul 99038-39-01 In 5ml R0616034.D biank R0616035.0 050900-EtFOSE-155 GC sampte R0616036.D 050900-EtFOSE-156 GC spike R0816037.0 biank R0616038.D 050900-EtFOSE-167 GC sampte R0616039.D 050900-EIFOSE-168GC sampte R0616040.0 biank R0S16041.0 050900-EIFOSE-179GC sampl R0616042.D 050900-EtFOSE-180GC spike R0616043.0 biank R0616044.D Sul 9038-39-01 In 5ml R0616045.0 biank BACK TO MAIN 3M Environmental Laboratory Report No. W2775 I 0.00 Q.00 0.91 1.99 4.93 7.59 9.75 0.00 0.00 6.92 0.00 0.00 0.00 7.05 7.54 0.00 0.00 6.03 0.00 7.26 0.00 0.00 6.96 O.QO 0.00 0.00 6.83 7.23 0.00 0.00 6.80 0.00 8.50 0.00 0.25 7.21 0.00 0.26 7.16 0.00 0.00 7.91 0.00 6.79 0.00 c a 2 e i r 0.00 o.oo 0.95 2.13 4.86 5.36 9.92 0.18 0.00 7.42 0.11 0.00 0.00 8.29 7.94 0.31 0.20 7.13 0.12 7.56 0.00 0.06 7.71 0.00 o .x o .x 7.83 7.62 0.31 0.23 7.47 O .X 6.91 0.00 o .x 8.83 O .X O .X 7.53 O .X O.X 7.79 O.X 7.47 Q .X | 1 I 1 004 0.Q2 1.02 1.93 5.17 7.78 10.11 0.19 O.X 7.4 0.10 o .x 0.11 8.13 6.54 o .x 0.03 7.5 o .x 7.4 O.X O .X 6.31 O.X O .X O .X 7.94 7.89 O.X O .X 7.57 O.X 6.96 O.X O.X 5.19 O.X O.X 7.70 O .X O.X 7.4 O.X 7.69 O.X Amount Detected (ng/ml) s I t O.X Q.X 0.83 1.81 4.17 6.X 8.64 0.02 0.05 6.32 0.02 0.01 0.02 6.54 6.45 O.X O.X 5.75 0.03 6.43 0.04 0.04 6.31 O.X 0.07 0.03 6.22 5.35 O.X 0.03 6.34 O.X 5.90 O.X 0.23 6.35 O.X 0 . 6.48 O.X O.X 6.39 0.01 5.79 O.X 2 3 | K 0.00 Q.00 1.21 2.32 6.03 9.82 11.83 O.X O .X 9.33 0.X o .x O.X 926 9.56 O.X o .x 9.00 O.X 9.97 OX OX 9.X OX 0.00 OX 10.46 921 O.X OX 8.69 OX 6.0 OX O .X 8.89 OX OX 8.95 O.X O .X 923 OX 8.47 O.X 0 C 8. | ox 0.00 1.47 2.49 5.95 9.79 12.80 O .X OX 7.77 0.00 0.00 ox 6.42 10.40 O .X O .X 9.15 O .X 8.88 0.00 ox 11.11 ox ox 0.00 6.17 6.28 ox 0.00 6.08 OX 7.20 OX OX 6.62 OX OX 8.40 OX O.X 8.13 OX 9.73 OX ! 1 N t 2 Sr 0.00 ox 1.12 2.16 5.42 8.54 10.95 O.X 0.00 8.14 O.X O.X 0.00 8.77 6.46 O.X O.X 7.69 O.X 8.05 O.X OX 6.56 OX o .x o .x 8.42 6.44 O.X O.X 825 OX 7.19 O.X O.X 7.95 O.X O.X 8.72 O.X OX 8.56 O.X 7.84 O.X 3 s ! si a a1 |a z rV A Eo3= i i 2 O 2 1 E s. M a o .x o .x o x o .x 106 Q X Q.X O.OQ Q .X 99 129 O.X 0.00 O .X 102 2.90 026 028 1.67 96 7.33 O.X 0.51 4.71 101 11.27 124 0.79 7.19 100 1424 1.45 1.01 8.93 100 O X O.X 0.00 0.00 96 0.00 o x O X 0.00 97 11.33 0.99 0.83 424 97 Q X O X 0.00 0.00 96 O.X OX 11.65 11.19 ox QX 1.14 1.10 0.00 Q.00 0.82 0.76 0.00 O.QO 4.59 3.33 95 96 95 91 O X O X 0.00 O .X 95 O X O X 0.00 O .X 85 10.66 0.95 O X 3.49 91 O X O X 0.00 O .X 100 10.45 1.08 0.80 8.72 97 O X O X 0.00 O .X 95 0.00 O X 0.00 0.00 98 11.00 1.13 0.75 8 .X 102 0.00 O X 0.00 0.00 101 O X o x 0.00 0.00 103 O X o x 0.00 0.00 104 11.09 1.10 0.77 6.79 98 11.41 1.14 0.71 6.21 101 O X o x 0.00 0.00 96 O X o x 0.00 0.00 96 10.92 1.11 0.80 6.18 103 0.00 o x 0.00 0.00 96 9.27 1.00 0.66 8.21 97 O X 0.00 0.00 0.00 109 O X o x 0.00 0.00 95 12.03 123 0.84 7.57 85 O X O X O X O.X 94 o x O X 0.00 0.00 97 11.38 1.06 0.78 5.55 104 O X O X O X O .X 101 O X o x 0.00 O X 93 10.69 120 0.71 5.69 93 O X O X 0.00 0.00 96 10.37 1,06 0.83 6.65 104 X O X 0.00 O X 97 Surrogate Recovery (%) > * 0 s N i c C c 1 1 E i E 3 s E s a 1c 8 | |a o 4 3 1 1 I X 103 I X 102 103 98 94 104 96 94 100 100 93 101 101 98 96 90 1 X 99 102 102 98 102 101 99 96 104 98 9 t 101 101 115 1 X I X 99 99 92 99 65 100 93 104 95 95 98 95 101 96 96 66 91 87 96 97 94 90 86 83 84 96 89 85 94 97 63 86 82 94 96 90 84 73 92 93 96 92 91 65 95 88 81 84 84 84 91 85 68 87 89 96 99 113 98 96 96 97 89 97 96 94 93 98 93 92 101 99 106 99 98 100 96 93 100 99 103 103 110 102 102 107 96 76 104 105 104 101 112 102 102 100 96 89 99 101 100 98 107 1C0 101 99 95 94 99 101 98 97 93 98 99 98 100 105 101 101 94 94 70 94 93 97 96 105 96 95 112 106 122 107 105 92 96 100 93 89 84 92 51 I X 66 93 64 107 92 91 102 99 112 98 95 103 103 94 103 99 101 96 90 99 96 65 95 96 93 91 93 95 96 96 94 94 95 64 94 95 102 101 80 102 102 96 92 91 95 94 , I I O 102 95 101 99 103 98 100 100 93 96 94 92 93 91 89 94 83 87 99 97 94 100 100 102 102 101 97 98 98 7 101 95 96 107 94 107 93 96 104 99 65 95 94 102 95 Page 128 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 Sample Deviations Individual samples that failed specific analytical criteria are shown in the table below. Sample ID. Description Failed Criteria Analyte PFOS photolysis in SHW LC/MS 99122-149-03 Cal Std 3-5 ppb 75 - 125% recovery PFOA PFOS photolysis in Fe20 3 LC/MS 00028-42-01 053100PFOSfe-05 053100PFOSfe-06 Cal Std 1-1 ppb 75 - 125% recovery Sample Triplicate >15% mean Sample Spike 75 - 125% recovery PFOA PFOS PFOS GC/MS R0614001.D R0614002.D R0614008.D R0614019.D R0614021.D Blank Blank Blank Blank Blank 75 - 125% recovery Surrogate Spike analytes 75 - 125% recovery Surrogate Spike analytes 75 - 125% recovery Surrogate Spike analytes 75- 125% recovery Surrogate Spike analytes 75 - 125% recovery Surrogate Spike analytes LOQ< 1-H perfluoroheptane <LOQ perfluoro-2-octene 051500-PFOSfe-073 Sample <LOQ volatiles 051500-PFOSfe-074 Duplicate <LOQ volatiles 051500-PFOSfe-061 Matrix Blank <LOQ volatiles 051500-PFOSfe-067 051500-PFOSfe-070 051500-PFOSfe-086 051500-P F O S fe-089 051500-PFOSfe-090 051500-PFOSfe-092 99038-38-01 99038-38-02 051500-PFOSfe-082 Dup Spike Control Spike Spike Dup Control Control Spike Blank Spike Cal std 1 Cal std 2 Matrix Blank 75 - 125% recovery 75 - 125% recovery 75 - 125% recovery 75- 125% recovery 75- 125% recovery 75- 125% recovery 75 - 125% recovery 75 - 125% recovery 75 - 125% recovery volatiles volatiles volatiles volatiles volatiles volatiles volatiles volatiles volatiles 051500-PFOSfe-086 Spike 75 - 125% recovery volatiles 051500-PFOSfe-087 Dup Spike 75 - 125% recovery volatiles 051500-PFOSfe-090 Spike 75 - 125% recovery volatiles 051500-PFOSfe-092 051500-PFOSfe-096 051500-PFOSfe-097 051500-PFOSfe-100 Blank Spike Spike Dup Spike Control Spike 99038-39-01 Cal check 75 - 125% recovery volatiles 75- 125% recovery volatiles 75 - 125% recovery volatiles 75 - 125% recovery volatiles 75 - 125% recovery All perfluorinated analytes Value Comments 142%, 140%,149% failed 3/3 injections 134% 1030 ppb 1503 ppb failed 1/4 injections vial leaked vial leaked Solvent interference Solvent interference Solvent interference Solvent interference Solvent interference 25-50 ppb 0.90ppb 0.18ppb 0.35ppb 0.04ppb 74% 74% 73, 74% 66, 74% 67, 70, 72, 74% 74% 128% -22% 69,73,71,38% 59,69, 72, 69% 71, 60, 34% 73, 61,32% 64, 70, 61% 73, 68, 38% 73, 70% 71, 70, 70,61% 72, 73% 69, 71% failed 6/7 spiked analytes failed 7/7 spiked analytes failed 6/7 spiked analytes failed 7/7 spiked analytes failed 7/7 spiked analytes blank greater than LOQ Referred to as "non detected" Referred to as "non detected" Referred to as "non detected" Referred to as "non detected" failed 1/7 spiked analytes failed 1/7 spiked analytes failed 3/7 spiked analytes failed 2/7 spiked analytes failed 4/7 spiked analytes failed 1/7 spiked analytes failed 1/11 spiked analytes failed 1/11 spiked analytes failed 4/11 spiked analytes failed 7/11 spiked analytes failed 3/11 spiked analytes failed 6/11 spiked analytes failed 2/11 spiked analytes failed 4/11 spiked analytes failed 2/11 spiked analytes failed 2/11 spiked analytes 62 - 74% failed 8/11 spiked analytes Page 129 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 Appendix E: Representative Chromatograms Chromatograms from the present study are included in this appendix. Page 130 of 158 Bti Fil} SSETSWflCNERMMMTflSHOOSOOSHILLOOlO.D BACK TO MAIN 3M Environmental Laboratory Report No. W2775 Pa$* 2 2 P F OA Page 131 of 158 Data Fila: SSETSkAGMERM)MlflTflSH06oa00\HILL0011.D BACK TO MAIN 3M Environmental Laboratory Report No. W2775 Pat* 2 Page 132 of 158 Data F11*S \\ETSWAGHER\DSDATA\H060800\HILL0012.D BACK TO MAIN 3M Environmental Laboratory Report No. W2775 Page 2 M 1 PFBS Page 133 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 Dita File: Y\ETSWACNERM)SDATA\H060800SHILL0014.D S\ETSWAGNER\DSDATA\H060800\HILL0014*D PlE# 2 M i PFBS 3 PFOS Page 134 of 158 Data Filai SSETSUGNERMMMTSH060800\HILL20.S BACK TO MAIN 3M Environmental Laboratory Report No. W2775 Pata 2 1 PFBS ' 3 prog Page 135 of 158 D a ta F i l e t SSETSWACHERSDSDATASH060800SHILL0036*D BACK TO MAIN 3M Environmental Laboratory Report No. W2775 Pace 2 * 1 PFBS Page 136 of 158 Data Filai SSETSHACNERSDSLATASH060800\HILL0037,D BACK TO MAIN 3M Environmental Laboratory Report No. W2775 Paca 2 Page 137 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 Dt* File: VxETSWACNERSDSDATANH060800SHILL0038.D 1.9 1.8 1.7 1.6- 1.5*1 1.4*1 1.3*1 1*2-i 1.1 1.0 % *5 > 0.8 0.7: o.6: 0.5: 0.4-: 0.3 0 .2 0.1 Exposed -167iirs Sample Fe203 N o Peroxide SSETSWAGNERSDSDATA\H060800\HILL0038.D x 1 PFBS Hin 3 PFOS 2 10 11 Page 138 of 158 Data Fil#J SSHTSWAGNER\D\DATASH060800SHILL0043*D BACK TO MAIN 3M Environmental Laboratory Report No. W2775 Pa** 2 Page 139 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 D*t File} SSETSWACNERSCSHPCHEMMSDATASH060800\H060800bSHILL070D Page 140 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 D*ta Fil} \\ETSHACNERSC\HPCHEH\l\DATASH0608OSH060800to\HILL0071.D p,, 2 Page 141 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 Data Fila: \\ETStMGNERSC\HPCHEH\l\DATA\H060800\H060800bSHILL0072.D Page 2 1.8- 1.7 1.6-i I.-; 1.4-; 1 .3 1.2-; i.ii A l.O'j, M> * 0 .9 : w 0.8 >- 0 .7^ O.fii 0.5 0.4-; 0.3-; 0.2-; O.li SSETSHACNtRSCNHrCHEHSISDATASH060800SH060800bSH1LL0072.D llnexposed -167hrs Sample Fe203 No Peroxide ,...........1.11 12 A . v_______________ i 10 11 M 1 PFBS 3 PFOS Page 142 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 D U Fil! SSETSWAGNER\CSHPCHEHSlMWTASH060800SH060800b\HILL0077.D 1.8 1 .7 1.6 i.B 1.4 1.3 1.2 1.1 1.0 t 0.9 > 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0,1 SSETSWACHERSCNHPCHEHMMWTftSH060800NH060800to'sHILL0077*D U n c x p o s d -l6 7 h rs C ontrol M illiQ N o Peroxide Pat 2 11 Page 143 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 Data File; S'sETSWAGNERSCSHPCHEHS1SDATASH060800'sH06<>800o \HILL0104<D Ptg* 2 Page 144 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 D ita F ila} S\ETSWACNH^CSHPCHBi\lMMTASH0W80<AH06080o\HIlX0108.II Paga 2 Page 145 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 Data Fil*J SSETSWAGNERSCSHPCHEH\lMTftSH060800\H060800cSHlU0106tD Pata 2 * 1 PFBS ____________________ 3 PFOS Page 146 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 Data Flit: SNETSWACHERNCSHPCHEMSlM)flTflSH060800\H060800oSHILL0111.D Pat* 2 Page 147 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 Appendix F: Soil Types and Characterizations This appendix presents the physical descriptions and chemical characterizations of the three soils used in the present investigation Page 148 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 STANDARD LABORATORY SO ILS param eter s t c r o ix c o ,v y i METALS Ag, mg/Kg (triad basis <3 A). mg/Kg dried basis 22000 As, mg/Kg dried basis Ba, mg/Kg dried basis Be, mg/Kg drted basis' 10 210 as Ca, mg/Kg dried basis Cd. mg/Kg dried basis Co, mg/Kg dried basis 3000 0.5 8 . Cr, mg/Kg dried basis 3 Cu, mg/Kg dried basis . 12 Fe, mg/Kg dried basis Hg. mg/Kg dried basts 20000 0.04 ' Mg, mg/Kg dried besls 2800 Mn, mg/Kg dried basis 800 Mo. mg/Kg dried basis 52 Na, mg/Kg dried basis 120 NL mg/Kg dried basis 18 P, mg/Kg dried basis 620 Pb, mg/Kg dried basis 30 ' Se, mg/Kg dried basis Zn, mg/Kg dried basis 200 48 EXCHANGE ACTIVITY Extractable Ca, meq/IOOg 8.14 Extractable P, meqfiOOg 0.68 Extractable Mg. meq/IOOg 2.97 Extractable Na, meq/iOOg Base Saturation % CEC. meg/IOOg ESP, % 0.03 42 28.3 0.11 SAR, unis 0.04 NUTRIENTS Available P, mg/L 61 N H 3-N ,m g/L 2.00 N03-N, mg/L . 84 KJeldahl N, mg/Kg 1470 ORGANIC MATTER ' TOC, % O M , 1.79 3.0 PHYSIOCHEMICAL Rekf Capacity, % 19.1 pHw, unis pHs, unis 5.7 5.7 Ume-req. Tons/Acre Soluble Salts, mmhos/Cm 1.8 0.98 CLASSIFICATION A Clay %sm % Sand 22 44 34 Soil Type LOAM BASE NEUTRAL PESTICIDES ACID PESTICIDES BDL BOL BDL a Below Detection Limits MORGAN C O , ALA EPA-SSM <3 40000 <10 97 <0.5 1000 <0.5 5 41 8.5 22000 0.11 1500 120 84 73 14 150 <30 <200 47 <3 46000 <10 100 0.6 86000 <0.5 6 25 13 18000 0.02 30000 710 ' 92 220 13 ' 710 <30 <200 47 3.50 0.10 0.43 0.02 18 22.0 0.09 O.OS 26.1 0.18 3.58 0.06 100 21.3 0.2B 0.05 ' 5 , 0.25 14 280 15 1.80 6.0 250 0.277 0.478 22.3 4.6 4.5 1.8 0.32 0.467 0.805 16.0 7.7 7.5 NONE 0.66 26 38 38 CLAY LOAM BDL BDL 22 26 52 SANDY CLAY LOAM BDL BDL Page 149 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 Appendix G: Light Intensity Measurements at 45 South Latitude (Miami FL) Page 150 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 F itter C om bination* Outer Filter Glaaa Filter GIm * typ*- Tyjj*-ft*''' BorMUieaia Boraafflcat tvpo-s- BerMlHeate . Sod* Urn* ' Atarte . S^BoRMiaotar, CIRA ORA StateDm*.' .. Typ*-sv BonwHctt* SodaLima Atlas Xenon Filter Combination T *at C ondition* ` Irradiane* R ang* WAn* Wfttega 250-300 300-400 400-800 ' ftaak Natural Daylight ' PtaJc Natural . . DayRghl SttndaW 1 *Small variations a n possible, depending on condition o f lamp andfilters. Page 151 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 Appendix H: Characteristics of the Spectral Output of the Suntest Instruments This appendix contains an Excel spreadsheet of the characteristics of the spectral output of the Suntest Photoreactors used in the present investigation. Page 152 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 Suntest Irradiance in W /m A2*nm Assuming the use of 300-800nm Global Sensor Only Filters Used Wavelength nm 250 252 254 256 258 260 262 264 266 268 270 272 274 276 278 280 282 284 286 288 290 292 294 296 298 300 302 304 306 308 310 312 314 316 318 320 322 324 326 328 IR Q/Suprax (UV) 0.001 0 0 0 0.001 0 0 0 0 0 0 0 0 0 0 0 0 0 0.003 0.005 0.009 0.014 0.021 0.028 0.045 0.054 0.07 0.085 0.116 0.138 0.151 0.175 0.21 0.24 0.263 0.279 0.329 0.352 0.369 0.4 Irradiances factored to yield 680 W/mA2 In 300-800nm band IR Q/Suprax (UV) 0.001119 0 0 0 0.001119 0 0 0 0 0 0 0 0 0 0 0 0 0 0.003357 0.005595 0.010071 0.015666 0.023499 0.031332 0.050355 0.060426 0.07833 0.095115 0.129804 0.154422 0.168969 0.195825 0.23499 0.26856 0.294297 0.312201 0.368151 0.393888 0.412911 0.4476 Page 153 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 330 0.431 0.482289 332 0.449 0.502431 334 0.475 0.531525 336 0.495 0.553905 338 0.525 0.587475 340 0.549 0.614331 342 0.565 0.632235 344 0.566 0.633354 346 0.587 0.656853 348 0.614 0.687066 350 0.61 0.68259 352 0.635 0.710565 354 0.656 0.734064 356 0.685 0.766515 358 0.662 0.740778 360 0.675 0.755325 362 0.719 0.804561 364 0.714 0.798966 366 0.73 0.81687 368 0.813 0.909747 370 0.858 0.960102 372 0.767 0.858273 374 0.8 0.8952 376 0.827 0.925413 378 0.864 0.966816 380 0.962 1.076478 382 0.992 1.110048 384 0.974 1.089906 386 0.996 1.114524 388 1.028 1.150332 390 1.111 1.243209 392 1.126 1.259994 394 1.227 1.373013 396 1.642 1.837398 398 1.552 1.736688 400 1.243 1.390917 402 1.228 1.374132 404 1.241 1.388679 406 1.284 1.436796 408 1.473 1.648287 410 1.395 1.561005 412 1.551 1.735569 414 1.416 1.584504 416 1.369 1.531911 418 1.426 1.595694 420 1.644 1.839636 422 1.453 1.625907 424 1.472 1.647168 426 1.462 1.635978 428 1.466 1.640454 Page 154 of 158 430 432 434 436 438 440 442 444 446 448 450 452 454 456 458 460 462 464 466 468 470 472 474 476 478 480 482 484 486 488 490 492 494 496 498 500 502 504 506 508 510 512 514 516 518 520 522 524 526 528 1.466 1.487 1.5 1.566 1.714 1.616 1.616 1.57 1.563 1.573 2.267 2.031 1.796 1.811 2.127 1.835 3.267 2.476 2.541 5.277 2.487 1.922 2.924 1.837 1.813 2.289 2.516 2.651 1.952 1.842 1.898 3.012 2.089 1.871 1.888 1.898 1.973 2.005 1.94 1.927 1.934 1.963 2.013 2.031 2.021 1.995 1.971 1.98 1.966 1.978 1.640454 1.663953 1.6785 1.752354 1.917966 1.808304 1.808304 1.75683 1.748997 1.760187 2.536773 2.272689 2.009724 2.026509 2.380113 2.053365 3.655773 2.770644 2.843379 5.904963 2.782953 2.150718 3.271956 2.055603 2.028747 2.561391 2.815404 2.966469 2.184288 2.061198 2.123862 3.370428 2.337591 2.093649 2 .1 1 2 6 7 2 2.123862 2.207787 2.243595 2.17086 2.156313 2.164146 2.196597 2.252547 2.272689 2.261499 2.232405 2.205549 2.21562 2.199954 2.213382 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 Page 155 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 530 1.954 2.186526 532 1.932 2.161908 534 1.942 2.173098 536 2.008 2.246952 538 2.014 2.253666 540 2.113 2.364447 542 1.996 2.233524 544 1.977 2.212263 546 1.962 2.195478 548 1.921 2.149599 550 1.876 2.099244 552 1.84 2.05896 554 1.938 2.168622 556 2.17 2.42823 558 2.106 2.356614 560 1.936 2.166384 562 1.912 2.139528 564 1.749 1.957131 566 1.706 1.909014 568 1.77 1.98063 570 1.997 2.234643 572 2.032 2.273808 574 1.802 2.016438 576 1.624 1.817256 578 1.572 1.759068 580 1.654 1.850826 582 2.215 2.478585 584 2.034 2.276046 586 1.738 1.944822 588 2.118 2.370042 590 2.159 2.415921 592 1.996 2.233524 594 2.185 2.445015 596 1.607 1.798233 598 1.492 1.669548 600 1.471 1.646049 602 1.37 1.53303 604 1.263 1.413297 606 1.207 1.350633 608 1.184 1.324896 610 1.292 1.445748 612 1.494 1.671786 614 1.31 1.46589 616 1.631 1.825089 618 2.672 2.989968 620 2.172 2.430468 622 1.416 1.584504 624 1.181 1.321539 626 1.256 1.405464 628 1.251 1.399869 Page 156 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 630 1.51 1.68969 632 2.325 2.601675 634 1.246 1.394274 636 0.959 1.073121 638 0.927 1.037313 640 0.834 0.933246 642 0.856 0.957864 644 0.876 0.980244 646 1.013 1.133547 648 1.571 1.757949 650 1.431 1.601289 652 1.12 1.25328 654 1.071 1.198449 656 0.86 0.96234 658 0.801 0.896319 660 1.103 1.234257 662 0.763 0.853797 664 0.762 0.852678 666 0.855 0.956745 668 1.037 1.160403 670 0.575 0.643425 672 0.682 0.763158 674 0.912 1.020528 676 0.526 0.588594 678 0.567 0.634473 680 0.514 0.575166 682 0.738 0.825822 684 1.065 1.191735 686 1.214 1.358466 688 2.331 2.608389 690 1.16 1.29804 692 0.73 0.81687 694 0.603 0.674757 696 0.432 0.483408 698 0.688 0.769872 700 0.347 0.388293 702 0.327 0.365913 704 0.298 0.333462 706 0.31 0.34689 708 0.275 0.307725 710 0.424 0.474456 712 2.069 2.315211 714 0.594 0.664686 716 0.302 0.337938 718 0.289 0.323391 720 0.254 0.284226 722 0.297 0.332343 724 0.384 0.429696 726 0.592 0.662448 728 0.817 0.914223 Page 157 of 158 730 0.593 732 0.634 734 0.472 736 0.316 738 0.375 740 1.097 742 0.368 744 0.272 746 0.264 748 0.439 750 0.356 752 0.231 754 0.273 756 0.406 758 0.823 760 1.344 762 0.554 764 1.555 766 1.114 768 0.388 770 0.194 772 0.152 774 0.188 776 0.21 778 0.247 780 0.388 782 0.327 784 0.225 786 0.171 788 0.335 790 0.693 792 0.137 794 0.18 796 0.326 798 0.632 800 0.233 Total Integrated Irradiance in 300-800nm Wavelength Band 607.6 W/mA2 0.663567 0.709446 0.528168 0.353604 0.419625 1.227543 0.411792 0.304368 0.295416 0.491241 0.398364 0.258489 0.305487 0.454314 0.920937 1.503936 0.619926 1.740045 1.246566 0.434172 0.217086 0.170088 0.210372 0.23499 0.276393 0.434172 0.365913 0.251775 0.191349 0.374865 0.775467 0.153303 0.20142 0.364794 0.707208 0.260727 680.0 W/mA2 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 Page 158 of 158