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3M Environmental BACK TO MAIN 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 23', 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 Perfluorooctone Sulfonate (PFOS) Study Identification Number: W2775 of Potassium 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. `Date / Page 3 of 156 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 Quality Assurance Statement Study Title: Screening Studies on the Aqueous Photolytic Perfluorooctane Sulfonate (PFOS) Study identification Number: W2775 Degradation of Potassium This study has been inspected by the 3M Laboratory Quality Assurance Unit as indicated in the following table Inspection Dates 03/30/O 1 - 04/2/O 1 04/l 9/01-04/20/01 Phase Data Draft Report Date Reported to Management Study Director 04/02/O 1 04/02/O 1 04/20/01 04/20/01 Page 4 of 158 - BACK TO MAIN 3M Environmental Laboratory Report No. W2775 Table of Contents Non - Compliance Statement.. .............................................................................................. Quality Assurance Statement.. ............................................................................................. Table of Contents.. ................................................................................................................ Study Personnel and Contributors.. ...................................................................................... Study Personnel and Contributors.. ...................................................................................... Summary ................................................................................................................................ Introduction ............................................................................................................................. Materials and Methods .......................................................................................................... Chemical Characterization.. ............................................................................................. Method Summaries ........................................................................................................... Results and Discussion.. ...................................................................................................... Data Quality Objectives ..................................................................................................... Analytical Results .............................................................................................................. Data Summary and Discussion ........................................................................................ Conclusions ........................................................................................................................... References ............................................................................................................................. Signatures .............................................................................................................................. Appendix A: Analytical Methods .............................................................................................. Appendix B: Chemical Characterization ............................................................................... Appendix C: Kinetics Model and Kinetic Calculations.. ......................................................... Appendix D: Individual Sample Data ..................................................................................... Appendix E: Representative Chromatograms ....................................................................... Appendix F: Soil Types and Characterizations ...................................................................... Appendix G: Light intensity Measurements at 45" South Latitude (Miami FL). ..................... Appendix H: Characteristics of the Spectral Output of the Suntest Instruments ................ .3 .4 .5 .7 .7 8 9 .I1 .l 1 11 .I3 13 14 14 17 18 19 20 .I04 .I08 .I18 130 148 .150 ..I5 2 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.. .............................. .I6 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 Anthony (Tony) Debra Wright Jan Schutz Rufat Mischiev Scales Professional Services Contributing Personnel (Pace Analytical Kristin Terre11 Jill Maloney Karen Johnson Services, Inc., 1700 Elm St., Minneapolis, MN 55144) (Braun lntertec Corporation, 6875 Washington Ave. South, Minneapolis, MN 56439) Location of Archives Digital copies of original data, and all original paper data have been archived in the 3M Environmental Laboratory archives for at least 10 years and will be retained 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.`*' 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 Hz02 was added as a well characterized source of *OH radicals?V6 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.`~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 LCIMS. Structures of the two pertinent compounds are illustrated in Figure 1. Figure 1. Structures of the Compounds Targeted by LC/MS Analysis PFOS Because it was possible that volatile degradation products could be produced, it was decided to monitor for selected C2 through C8 l- or 2- substituted perfluoronated olefins (e.g. CSFIS) and I- or 2- substituted hydrides (e.g. C8F17H) 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 (kp)- 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 CLI,and a standard deviation of op.) k, 5 (kp)max= 20, ClP At Page 10 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 Materials and Methods Chem'kal 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. UVAIisible analysis was performed following 3M Environmental Laboratory Method ETS-B 46.0 "Operation and Maintenance of the Hewlett Packard 8453 W-Visible Spectrophotometer" An aqueous saturated solution of PFOS was prepared and an initial UVNIS spectrum recorded. No absorbance above baseline over the range 190-I 100 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-6-176.0 "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 paw. 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 Hz02 at I: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 4+2"C. These samples 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 flO"C. 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. Fe203 in water) + Control Matrix (e.g. water) 0 Test Substance (PFOA) + + Post Photolysis Target Analyte spike 0 Sample Type (Conditions) Initial Initial lnitial Initial Initial Initial Initial Initial Initial Initial LC/MS* With W/out %Q Y4 X X X X X X X X X X X X x x X X X X GUMS* With W/out YOZ YOZ X X X X X X X X X X X X X X X X X X 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 0 Direct Photo. Spike 0 Control Blank 0 Control Blank Spike 0 0 + 0 + 0 + 0 + 0 0 0 0 + + + + + 0 + 0 0 Light x X X X 0 Light X X X 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 X X X X + Light X X X X 0 Light X X X X + Light 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 0 Direct Photo. Spike 0 Control Blank 0 Control Blank Spike 0 + + + 0 No Light xx X X No Light No Light x" x" x" II No Light X X X X No Light x x X X No Light X X X X No Lght x x X X No Light X X X X No Light x x X X + No Light 11 X X X X + = added to test vial; 0 = NOT added to test vial; *Duplicate material test where H20s was not added) sets, one with H202, one without (excludes D Humic 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. W2775 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-8481.0 "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 GUMS 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 ti5% 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 ti5% 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 LClMS and GC/MS analysis of the study investigation were between &25%, except where noted in Appendix D. Sample triplicates. Appendix D. All sample RSD values were 25% or less except where noted in Continuing value. calibration verification. All CCV samples were within 25% of the expected 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 Summary 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 3M Environmental BACK TO MAIN Laboratory Report No. W2775 Table 2. Observed Products and Mass Balance Determinations Humic Water and Iron Oxide Containing Water for Water, Synthetic 2a. Matrix: Water, With and Without H202 Sample Ind. Photo. Dir. Photo. Ind. Photo. Dir. Photo. Ind. Photo. Dir. Photo. Sample' Sample' Sample' Sample' Sample' Sample' Detection Conditions 167 hour Exposure Initial Time Point Initial Time Point Exp. to Light Exp. to Light Not Exposed Not Exposed Limits PFOS nanomoles 97.9 95.7 96.3 94.3 93.3 96.3 3.75 PFOA nanomoles No ND ND ND ND ND 0.023 Volatiles nanomoles ND ND ND ND ND ND 0.0095' Mass Balance (percent) 104% 102% 102% 100% 99.2% 102% Vials initially contained 94.1 nMoles PFOS. 1. Indirect Photloysis Sample: These samples had H202 added as a radical source, results are from triplicate samples. 2. Direct Photolysis Sample: These samples did not have H202 added, results are from triplicate samples. *Sum total of all volatiles. ND = non detect. 2b. Matrix: Fe203 in Water, With and Without Hz02 Sample b4 Fe24 b4 Fe*03 Fe203 Fe,4 WN4' wo/yo~* wm?z' wo/yo*2 w/l+o* wo/yo*2 Detection Conditions 167 hour Exposure Initial Time Point initial Time Point Exp. to Light Exp. to Light Not Exposed Not Exposed Limits PFOS nanomoles 97.4 95.2 96.9 95.9 94.3 96.9 3.75 PFOA nanomoles ND ND ND ND ND ND 0.023 Volatlles nanomoles ND ND ND ND ND ND 0.0095* Mass Balance (percent) 103% 101% 103% 102% 100% 103% Vials initially contained 94.1 nMoles PFOS. 1. Samples had H202 and FezOOaadded as a radical generating species, results are from triplicate samples. 2. Samples contained just Fe203 as a radical generating species, results are from triplicate samples. *Sum total of all volatiles. ND = non detect. 2c. Matrix: Synthetic Humic Water Sample Humic Water' WaterZ Humlc Water' WaterZ Humlc Water' WaterZ Detectlon'Limits Conditions 67 hour Exposure Initial Time Point initial Time Point Exp. to Light Exp. to Light Not Exposed Not Exposed PFOS nanomoles 6.52 6.63 6.51 6.32 6.69 6.50 0.037 PFOA nanomoles ND ND ND ND ND ND 0.046 Mass Balance (percent) 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 15of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 Hz02 rich aqueous matrix - table 2a, the Fe+3 containing matrix - table 2b and the humic containing matrix - table 2~). The Fe203 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, Fep03 with and without &Oz, was pooled to determine the experimental error of the analysis. This data, shown graphically in figure 2, yielded an estimated environmental half-life of 13.7 years. The exact mathematical solution is shown in Appendix C. Figure 2. Pooled Concentration Data from the Iron Oxide Rich Matrix. Dashed lines indicate the lo limits. 90 time (hours) 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 perfluorooctone 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 1OOfl 1% under all experimental conditions. Using the Fe203 photoinitiator matrix model, we estimate the environmental photolytic half-life of PFOS to be greater than 3.7 years. Page 170f 158 3M Environmental BACK TO MAIN Laboratory Report No. W2775 References 1. Fate, Transport and Transformation Test Guidelines, OPPTS 835.5270 Indirect Phofolysis Screening Tesf; EPA712-G96-099; United States Environmental Protection Agency, U.S. Government Printing Office: Washington, DC, 1998, pp. l-22. 2. OECD Guideline for Testing of Chemicals, Phofofransformafion of Chemicals in Wafer-Direct and Indirect Phofoysis, (Draff Document); OECD, 2000, pp. l-59. 3. Scrano, L.; Bufo, S. A.; Perucci, P.; Meallier, P.; Mansour, M. Photolysis and Hydrolysis of Rimsulfuron. Pesfic. Sci. 1999, Vol. 55, pp. 955-961. 4. Nubbe, M. E.; Adams, V. D.; Moore, W. M. The Direct and Sensitized Photo-oxidation of Hexachlorocyclopentadiene. Waf. Res. 1995, Vol. 29, No. 5, pp. 1287-1293. 5. Ogata, Y.; Tomizawa, K.; Furuta, K. Chemistry Peroxides 1983, p. 720. of Peroxides, in S. Patai (ed.). The Chemistry of 6. Lunak, S.; Sedlak, P. Photoinitiated Reactions of Hydrogen Peroxide in the Liquid Phase. J. Phofochem. Phofobiol. A.: Chem. 1992, Vol. 68, pp. l-33. 7. Kachanova, Z. P.; Kozlov, J. N. Zh. Fiz. Khim. 1973, Vol. 47, p. 2107. a. 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 laof 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: Projects Team Leader ' /2!%GizH&- Wll~am L Reagen, Ph. D., Laboratory Management 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 ChromatographlMass 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 .O 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 ENVIRONMENTALLABORATORY &4LYSISOF~OTOLYSISSAMl'LESFORFLUOROCKEMICALS BY HIGH PERFORMANCE LIQUID CHROMATOGRAPHY WITHMASSSPECTROMETRYDETECTION Method Number: ETS-8-181.0 Approved by: Laboratory Management Adoption Date: Effective Revision Date: L'cT--"lr, UJ Date Page 21 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 1.0 SCOPE AND APIUCATI~N 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 HPLUMSD Standard operating Procedure ETS-9-34.0 for operating and maintenance procedures related to the instrument. Refer to Standard Operating Procedures ETS-8-I 76 -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 fluorinated compounds, or other ionizable compounds, which includes but is not limited to: Comuound Pertluorooctanoic acid Pertluorooctanesulfonate Pertluorooctancsulfonamide N-methylpertluorooctanelforurmide N-ethylpertluomoctaneulfonamide 2-(Nmcthylperfluorooctanesulfonamido) ethyl alcohol i+cw!m PFOA PFOS FOSA N-MeFOSA N-EtFOSA N-MeFOSE-OH Comwoad Pertluorobutanoic acid Pertluorobutanesulfonate Perfluombutanesulfonamide N-methylpertluorobutanaulfonamide N-ethylperfluorobutanesulfonamide 2-(N-methylperEuorobmanesulfonamido) ethyl alcohol Acmnvm PFBA PFBS FBSA N-MeFESA N-EtFBSA N-MeFBSE-OH 2-(N-ethy1pertluorooctanesu1fonamido) ethyl alcohol N-EtFOSE-OH 2-(N-ethylperfluorobutanesulfonamido) ethyl alcohol N-EtFBSE-OH . . . and other C, thru Cl0 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 (TiOz, Fe203, etc.) that have been diluted with an appropriate analytical solvent such as acetone or methanol. 2.0 SUMMARYOFMETHOD 2.1 This method describes the analysis of fluorochemicals in a specified matrix, using HPLC electrospray mass specttometry for chemical separation and detection/quantification. The analysis is performed by separating target analytes on an HPLC analytical column such as a Dionex NGl(35x 4.6mm, 1Opm particle), Betasil Cl8 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. El-S-8-181.0 Analysisof PhotolysisSamplesfor FluorochemicalbsyHPLCYMS Page 2 of 15 Page 22 of 158 3M Environmental BACK TO MAIN 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 Quantiiication. Process of establishing a relationship betieen 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 of the target analyte(s) on column. The resultant curve(s) shall be used to determine unknownconcentrationbsy comparingthesrearesponsoef targetanalyte(st)o the area response and correspondinagnalyteamounton the appropriate snalyte'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 Coeffkient (r). A measure of the degree of 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 +l. A value of +l denotes perfect direct functional relationship between two variables. A value of -1 also denotes a perfect inverse relationship. When r = 0, there is no effect of one variable upon the other variable. 3.6 Coeffhient of Determination (r*). The square of the correlation coeffkient. It is the proportion of 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 element(s) 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 runto verify thecontinuedaccuracoyf thecalibrationcurve.This solutionmayor may notbepreparedfromadifferentsourceor lot numberthanthecalibrationcurvestandards. ETS-8-181.0 Analysis of Photolysis Samples for Fluorochemicals by HPLCMS Page 3 of 15 Page 23 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 3.10 Solvent Blank. A sample of 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 of target analyte(s) f?om the matrix. 3.11.1 3.11.2, Matrix 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. 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 Iimits 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 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, and analysis. 3.14 Control Sample. A known matrix (ASTM Type II water) containing the test analyte(s) canied throughout the entire sample preparation, photolytic and analytical procedure. 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). 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 analyt&) 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-S-181.0 Analysis of Photolysis Samples for Fluorochemicals by HPLCMS Page 4 of 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 3.16.2 Matrix 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. Control Spike. The control matrix (ASTM Type II 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 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. 3.18 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 I-PLC 1lOO/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 of a strong electrical field. 3.21 Mass Spectrometry, Mass Spectrometer (MS), Mass Spectrometer Detector (MSD): The API HP1 100 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 of 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 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 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-I-181.0 Analysis of Photolysis Samples for Fluorochemicals by HPLCYMS Page 5 of 15 Page 25 of 158 3M Environmental BACK TO MAIN 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 Cl 312; Quaternary, Model G13 11A, 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 Betas@ C18,50 x 2 mm; Dionex IonPace' NGl Guard column, 4 x 35 mm; or equivalent. 6.4 Mass spectrometer. Hewlett-Packard MSD Model G1946A, or equivalent. 6.5 Retiigerator capable of maintaining 4 f 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 of Photolysis Samples for Fluorochemicals by HPLCYMS Page 6 of 15 Page 26 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 6.7 System control/data analysis software: Hewlett Packard ChemStationQ 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 Sup~~ms m 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 f 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 Corn 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, adding 10 mL. of methanol, diluting to the mark with 18.0 MX2 water and mixing.) 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-n& 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 tbe appropriate log books. Maintain photocopies of the preparation pages and worksheets in a raw data file. ETs-8-181.0 Analysis of Photolysis Samples for Fluorochemicals by HPLCIMS Page7oflS Page 27 of 158 3M Environmental BACK TO MAIN Laboratory Report No. W2775 9.0 SAMPLE HANDLING 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 OCf 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. 103 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 may be analyzed witbin the same analytical batch. 10.5 Analytical spikes. Prepare analytical spike sample for each sample type as appIicablc 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 f 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 of target analyte(s) are within the viable range of the calibration curve. ETS-S-181.0 Analysis of Photolysis Samples for Fluorochemicals by HPLCIMS Pagc8of15 Page 28 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 11.0 CALIBRATIONANDSTANDARDIZATION 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 the column and nebulizing needle; equilibrate the column compartment; and equilibrate tbe 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 of 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 AnaQsis of Photolysis Samples for Fluorochemicals by HPLCIMS Page 9 of 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 theMSD. LogtheTuneresultsandkeepacopywith theanalytical raw data. 12.2.4 Load the method file and ensure that the following parameters are appropriately set for the target analytc(s): Example mass spectrometer set up*: I MSD: 1 Ionization mode 1API-ES (or API-APCI) I Polarity Negative (or Positive) Aoqulsltion mode SIM (or SCAN) Gain I .o (up to 7.0) Fragmentor Dwell time 70 (may be set to one voltage, or ramped for each ion) 183 msec (time is a function of the amount of Ions). Capillary voltage Drying gas 3560, or equivalent Nitrogen, or equivalent Nebuker pressure 30 psig, or equivalent Drying gas flow 8 Umin. or equivalent Drying gas temp 300' C, or equivalent *ExampIe conditions are applicnblc to HP1 100 LCIMSD 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 nm. 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 pump parameters for solvent 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 SolventGradient: TIME (MN) nA %B FLOW RATE 0.0 60 40 0.3 mUmin 1.0 60 40 0.3 mUmin 4.0 5 95 0.3 mUmin 11.0 5 Post time: 6 minutes, column ternpcfatu~ 3YC. 95 0.3 mUmin 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 Analysisof PhotolysisSamplesfor Fluomchemicalsby HPf.C/MS Page10of IS Page 30 of 158 3M Environmental BACK TO MAIN Laboratory Report No. W2775 . 12.3.4 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. Auto-sampler setup: I AUTO-SAMPLER: I ALS Model 01313A I AUWSAMPLER PROCRAM: None l~~t3370N voLuhw 5.0 &, or equivalent *Example conditions are applicable to Hewlett Packard 1100 LCYMSD only 12.35 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 12.4.2 12.4.3 12.4.4 12.4.5 Within the sequence parameters, enter sequence information (brief sample population description and instrument name). Set post-sequence command macro to shut down system after the run is completed (Example: "STANDBY" on HE1 1OO/MSD systems). Save all data to a subdirectory labeled with instrument and analysis date (e.g. H100200 for analysis on "Hillary," on 2 October, 2000). Name data within the subdirectory with instrument ID and injection/run number (e.g. for samples acquired on "Hi&try", data files shall be "HILL000 1". . . . "HILLOO##"). DO NOT exceed five identification characters for analysis of 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). Save sequence as analysis date and instrument letter (e.g. For analysis on instrument "Hillary" on October 2,200O save sequence table as Hl00200.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 of Photolysis Samples for Fluorochemicals by HPLC/MS Page 11 of 15 Page 31 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 12.5.2 12.53 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 of samples and evaluate for carry over problems Erom actual samples. Ensure standards, blanks, samples, and matrix spikes in the auto-sampler tray vials are in same order as listed in the sequence. Print a copy of the tune results, method and sequence to be stored with raw data. 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 qua&ication must have peak hei&ts 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 of manual integration was performed. A: Adjust Left Anchor B: Adjust Right Anchor C: Delete Integration D: Add Integration Additionally, QAU encourages th& data reviewer to write comments directly on the chromatogram if there is anything unusual. Date and initial all documentation. 13.3 Matrix spikes. Calculate the percent recovery for each of the matrix spikes. Calculate the matrix spike percent recoveries using the following equation: % Recovery = (observed spiked samole result - observed samole 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 Cont.) x 100 Nominal Cont. ETS-8-181.0 Analysisof Photolysis Samples for Fluorochemicals by HPLCiIvfS Page12 of 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 Samnle Set x 100 Average of Sample Set 14.0 METHOD PERFORMANCE 14.1 Coefficient of Determination (2). The coefficient of determination (2) 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 of the curve. The accuracy of all standards used for calibration must be within 75125%. 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 tinal 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 tinal acceptance or rejection of the analytical run. 14.6 Matrix 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% of the peak area of the designated LOQ value observed in matrix blanks are indicative of matrix effect, ETS-8-181.0 Analysis of Photolysis Samples for Fluorochemicais by HF'LUMS Page 13 of 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 necessary to determine these effects. Use of solvent blanks prior to the matrix blank may be necessary 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 instnnnental 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 5 25 % nominal value) in the calibration curve that is greater than 4 times the level of 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 shah accept percent spike recovery values of 100 f 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 demonstrated by acceptable instrumental checks (e.g. abbreviated m/z check-tie, or fill 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-S-181.0 Analysis of Photolysis Samples for Fluorochemicals by HPLC/MS Page 14 of 15 Page 34 of 158 3M Environmental BACK TO MAIN Laboratory Report No. W2775 , 16.0 RECORDS 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 tile. 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 ATTACHMENTS 17.1 None. 18.0 REFERENCES 18.1 ETS-9-34.0, Hewlett Packard 1lOO/MSD Fxptipment Procedure. 18.2 Hewlett Packard 1lOO/MSD instruction CD/ROM. 19.0 AFFECTED Documims 19.1 None. 20.0 ~VISIONS Revision number Reason for revision Date of Revision ETS-8-181.0 Analysisof PhotolysisSamplesfor Fluorochemicaibsy HPLClMS Page 15 of 15 Page 35 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 3M ENVIRONMENTAL LABORATORY Method Preparation of Samplesfor PhotolyticExposureStudiesin AqueousMatrices Method Number: ETS-g-176.0 Adoption Date: ApprovedBy: LaboratoryManager ' ETS-8-176.OPreparation of Samples for Photolysis Studies in Aqueous Matrices Method Page1of 18 Page 36 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 1.0 SCOPEANDAPPLICATION 1.1 Purpose. Chemicals dissoIved 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 (I&02) 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 Hz02 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 (`9) which may promote indirect photolysis of the test substance. Another transient species photochemically produced by the reaction of UV light and dissolved organic materials (hunk) is hydrogen peroxide (I&02) which may react further to form the hydroxyl radical. The addition of Hz02 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(II1) which undergo photoreduction to Fe@) and free radicals or addition of TiOz 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: Comoound Acronvm COIUDOund Acronvm Pefluorooctanoic acid PFOA Petiluorobutaooic acid PFBA PcrfhIorooctanesulfona Peffluorooctanesulfonamide N-mcthylp~uorooctancsulfonamide PFOS FOSA N-MeFOSA Perfluor&utmlcsulfonate Perfluorobutanesulfonamide N-methyIpcrfluorobutencsulfonamide PFBS FBSA N-MeFBSA N&ylperfluorooctenesulfonamide N-EtFOSA N-ahylperfiuombutanesulfonamide N-EtFBSA 2-(N-methylpertluof0 octancsulfonamido) ethyl alcohol N-McFOSE-OH 2-(N-methylpcrfluorobutancsulfonamido) akohol ethyl N-McFBSEOH 2-(N-ethylpcriluorooctenesulfonamido) ethyl alcohol I-pertluomoctene N-EtFOSE-OH - 2-(N-ethylperfluombutanesulfomunido)ethyl alcohol 1 -pcrfluorobutenc N-EtFBSE-OH - Pcrfiuomoctanehydride IH, Q-hydride Perfluombutanehydride lH, Q-hydride . . . end other C, thro Cl0 homologucs, end polymeric materiels based on the afonmentioncd compounds. ETS-I(- 176.0Preparation of Samples for Photo& Studies in Aqueous Matrices Method Page2 of 18 Page 37 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 Other possible degradation products include, but are not limited to: c2 II-I-pcrfhiomcthanc(1H-pfC2) IH-perflwrccthane (lH-@2) C, IHpcrflwmpmpane (IH-pK3) 2H-perfh~otopmpane (2H-pC3) pertlwmd -pmpcnc (pfC3-lene) C, pdluom-l-butcne (pfC4-lene) Pefflwm-2-butene (pfc4-2ene) 2H-pcrtlwmbutanc (ZH-pfU) C, 2H-pcrfluororpentMe (2H-pfC5) pcmu0ro-b~tenc @ES-la) pcmww2-pmtefle @CS-~CW) cs pemwm-2-hexenc (pts2cm) ZH-pcmwmhexent (2HgE6) C, ZH-pcrflwmbcptanc (2H-pfC5) IH-pduomhexanc (lH-pfC6) Rmwm-h0pttm @ttXkw) pertluom-l-hexene (pRX-he) IH-perflwmhcptme (IH-pC?) C8 pduom-l-octane (pfCklme) ZH-pertluom~cta~~e (2HqE8) Perflwm-2atene (pKS2ene) IH-perfl~~mb~~time (lHpfC4) IH-perflwmhexane (IHpfC6) 1Kpertlwmodane (IH-pfCS) 1.3 Acceptable matrices. Aqueous solution of test substance including but not limited to the following matrices: pH 7 phosphate buffer, 18.2 M resistivity water, seawater and metal solutions. 2.0 SUMMARY OF METHOD 2.1 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 quantifjr 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 GCYMS. When required, the addition of 30% Hz02 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/m2 of 3 lo-800 run photo-irradiance for a specified number of g-hour periods. An &hour period of irradiauce is defined as one day's worth of sunlight. Other parameters are acceptable, with the time and settings noted for each study. The number of days to expose samples is determined by the Team Leader. The amount of irradiation received by the samples may be monitored in one of the following three ways: 1) calculating the total wattage per length of exposure 2) use of a radiometer to measure h-radiance 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 GUMS analysis. ETS-8-176,OPreparation ofsampks for Photolysis Studies in Aqueous Matrices Method Page 3 of 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 FezOs. GUMS slunplc RqI 1 semjJ1eti 2 Sample Rep 3 hit&ix Sub&xc I I I + 0 + + + Sample Spike + Matrix Blank + Matrix Blank Spike + control smllplc comol spike 0" Conbol Blank 0 Control Blwk Spike 0 + 0 Target Analytc 1 -spike 0 + Time 0 Time 0 Time 0 Time 0 Time 0 Time 0 TiiO ThCO Time 0 With WithOut With Without Hlo, Hz01 Hz% Hao, I Sample Rep 1 + Sample RI$ 2 + Sample Rep 3 + Sample Spike + Matrix Blank + Matrix Blank Spike + control Sample Control Spike 8 Control Blank 0 + 0 Dosed Sample Rep 1 Sample Rep 2 Sample Rep 3 Sample Spike Matrbt Blatk Meix Blmdc spike Control Sample Contml Spike Caatml Blank X X t7?cCZG X X t w/o Hz02 3.0 QUALITYCONTROL-DEFINITIONWREQUEN~Y~EWO~ANCECRZTERIA 3.1 Blanks 3.1.1 Definition: Matrix 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 fi-om the experimental treatment and analytical process. Refer to the table below for an example of matrixblanktypes.Thematrixblankis usedto documentheactual 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 matrixspecific. The table below shows an example of a control blank ETS-8-176.OPreparution of Samples for PhotoJysis Studies in Aqueous Matrices Method Page 4 of 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 description Example: 0.01M PhosphateBuffer, pH 7 Example: ASTM TypeII Water Freauency 1 Replicate perlight and darkexposuref,or each time point andfw each analyticaml ethodology. targetanalyteshallbe less than 25% the areacountsof the LOQ. 3.2 Limit of Qusntitation (LOQ) 3.2.1 Definition: The lowest concentration that can be reliably measured within specified liits of accuracy during routine laboratory operating conditions. Sample LOQs are highly matrixdependent. 3.2.2 Quality Control and Perjhmance 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 the lowest non-zero standard in the calibration curve that is greater than 4 times the level of the solvent blanks and indicates good accuracy (iz 25%) of the nominal calibration standard concentration. 3.3 Sample Triplicate 33.1 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 repIicate 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 GUMS). See the following table: 3.4 Control Sample 3 Replicates perlight AND dark Theanalystshallaccept%RSD documentedandjustified (if I 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 veritj that the precision and bias of the analytical process ETS-8-176.OPrepararioonf Samples for Photolysis Studies in Aqueous Matrices Method Page5 of 18 Page 40 of 15% BACK TO MAIN 3M Environmental Laboratory Report No. W2775 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. 3.4.2 Performance Criteria. One control sample will be prepared per matrix, per treatment type. See the following table: Matrix Description Control matrix with test aualyte(s)added Freanencvof Use 1Replicateperlight AND dark exposurew, ith AND without HzOh for eachtime-point,andfor each analyticalmethodology(i.e. LclMS and/orGUMS). Performance Criteria 1 `Ike analystshallacceptrecovery valuesof 100f 25%. Accuracy valuesnot meetingspecification mustbedocumentedandjustified (if possible). Analytical Spike (AS) 3.5.1 Definition: Prepared by adding a known mass of target anaIyte(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 GUMS). In addition, one matrix blank spike and one control blank spike will be prepared. See the following table: Matrix hscrhtion Freauencvof Use TestMatrix andtestsubstances.,piked 1Replicatepertreatmenttype. with targetaualyte(sj)ustprior to analysis ControlMatrix andtestsubstance, 1 Replicatepertreatmeuttype. spikedwith targetanalyte(sj)ust prior to analysis TestMatrix withouttestsubstance, spikedwith targetaualyte(sj)ust prior to analysis 1 Replicatepertreatmentype. , ControlMatrix withouttestsubstance, 1 Replicatepertreatmenttype. spikedwith targetanalyte(sj)ust prior to analysis Performance Criteria The analystshallaccept spike recovery values of 100+ 25%. If spike recoveries are greater than 125%or lessthan 75%,documentthat the spikesampleis out of the specificationsand justify, if possible,the reason. 3.6 Internal Standard/Surrogate 3.6.1 InternalStandard Definition (applies to LUMS and GCKiMSsamples): 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-8-176.OPreparatioonf Samples for Phorolysis Studies in Aqueous Matrices Method Page6 of 18 Page 41 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 to be quantified using the internal standard providing that the response of the internal standard is consistent (3~5% relative). Use of external calibration methodology requires written justification by the Team Leader. 3.62 Surrogate Definition (appIies to LCBtLS 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 anaIytical 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. Sunogates are not used for quantitation. Note: Internal standarc& are used in all experiments. The use of surrogate standark may or may not be used 3.6.3 Quality Control and Performance Matrix Description Freuuenw of Use Sampledilutedwith 30 mL of internal standard compound dissolvedin a suitable analyticalsolvent EveryLCYMS sampleanalyzed Samplewith surrogate EveryGCilW compoundspikedinto it. sampleanalyzed riteria: PerformanceCriteria TheCoefficientof Variation,or %RSDshall becalculatedfor the arearesponseof all appropriatesamplesper analyticalbatch. The analystshallaccept%RSDvaluesof ~15%. Therecoveryandprecisionof the surrogates shouldbe 1005125%and<IS%,respectively. Unacceptablevaluesshallbe documentedand justified,if possible. 3.7 Other Definitions. 3.7.1 Test AnalyteBubstance: Any substance (mixture or controlled compound) added or administered to the test system for the purpose of chemical analysis. 3.7.2 Degradation Product(s): 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 he 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-I76.OPreparation of Samples for Photolysis Studies in Aqueous Matrices MethodPage7 of 18 Page 42 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 4.0 HEALTH AND SAFETYWARNINGS 4.1 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 of 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 5.1 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 EQUIPMENT 6.1 analytical balance sensitive to 0.1 rng 6.2 Photoreactor: Suntest CPS+, XLS+, or equivalent, equipped with a xenon arc-lamp and capable of producing integrated irradiance values fkom loo-680 W/m2 over the wavelength range of 290-800 run. Lamp output must be filtered to allow only 290-800 mn 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 OCf 5 "C, from Poly Science, Model 1177-P or equivalent. 6.4 Agilent Technologies W-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 G112OA, Thermostatted Cell Holder: Model 0845 l-601 04, or equivalent. 6.4.1.1 1.O-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-I- 176.0Preparation of Samples for Photo&s Studies in Aqueous Matrices Method Page 8 of 18 Page 43 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 6.4.2.1 1O-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,orlater. 6.4.4 PC Computer capable of running appropriate analysis software to acquire and report data. 6.5 Centrifugecapableof maintaining> 2000rpmfor 10minutesatambientemperature. 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 SUPPLIES AND h'bERIAIS 7.1 40 mL amber and clear glass VOA vials with screw caps with septa. 7.2 Crimp cap autovials- .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 rnL. 7.8 Hamilton Gastight@ syringes (precision jc 1% of the total volume), 5 pL to 1000 pL. 7.9 10 mL Bottle-top dispenser, Calibrex, Model # 5 11, or equivalent. 7.10 Adjustable repeater pipette, Wheaton Step-pette 411, or equivalent, equipped with the appropriate volumetric range pipette tips. 7.11 Ziploce plastic bags, or equivalent. 8.0 REAGENTSAND STANDARDS 8.1 Methanol (MeOH). HPLCYSPECIGC and/or purge and trap grade (EM Science, or equivalent. 8.2 Acetonitile (ACN). HPLC/SPEC/GC and/or purge and trap grad from EM Science, or equivalent. 8.3 Aqueous Matrix, includes but is not liited to the following matrix types: 8.3.1 ASTM Type I water. Milli-QQ or equivalent, with a measured resistivity > 18.0 MR-cm. 8.3.2 0.01 M pH 7.0 Phosphate Buffer. Example: Weigh 1.36 g RI&PO4 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 f 0.1% with 0.1% NaOH or dilute H2SO4 and dilute to the mark with Type I water for a final cont. 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. Ti02, FsO$. Example: Dilute 0.015 g of TiO2 (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-I 76,OPreparation ofSampZresfor Photoiysis Studies in Aqueous Matrices MethodPage9 of 18 Page 44 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 8.4 Hydrogen Peroxide (H202). 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 @ml by weighting approximately 0.1 g of the appropriate substance into a IO-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 ExamDle for water soluble analvtecs): 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-l) to 500 mL with test matrix. Aliquots (5 mL) of this solution will transferred to VOA vials for subsequent photolysis. 8.7.2 ExamDIe for Door water soluble analvteW or those with adsorntion difficulties: Prepare a solution of the test substance in acetonitrile (Example: A 500 &mL test analyte solution is prepared by diluting 500 ~1 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 of the intended test substance. Evidence of this phenomenon (approximately 10% decrease in the concentrations of the final products) has been observed in a stu& here at 3M (EtFOSE-OHphotolysis in pH 7 bufler, with and without presence of Meow. 8.8 Target Analyte(s) Spiking solution: Example: A spike solution of test analyte &nd target analyte(s) (e.g. projected degradation products) in methanol or acetonitrile is prepared by diluting 500 pL of 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 @ILL target analytes. Addition of 10 pL of this target analyte spiking solution into the 35-n& diluted sample volume will result in approximately 140 rig/ml and 30 rig/ml concentrations for the test analyte and target analyte(s), respectively. *Pre-estimation of the degradation potential of the test analyte and subsequent degradation products is not always possible. Ifpossible, an analyticalprescreening of representative samples should be performedfor accurate spiking. General rule of thumb has been that the test anabte spike amount be ETS-I- 176.OPreparaGon of Samplesfor Photo&is StudiesinAqueousMatrices Method Page 10 of 18 Page 45 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 approximately 25% 50% of the initial concentration The target analyte(s) spike amount has been 1O-l00 rig/ml, depending on expected levels under specz@c conditions. More 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 will require a lower spike concentration in the Exposed sample set due to less test analyte remaining. The Day 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/m.L. 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 SAMPLEHANDL~G 9.1 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 (capside 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. GCYMS samples may only be turned upright immediately before being loaded onto the purge and trap autosampler. The LC/MS samples may be tumed upright after the photolysis process has been completed. The exception to this beingthe need to briefly turn the samples upright for Hz02 injection through the septa of the appropriate VOA sample vials at specij?ed time intervals (SeeSection 12.6 and Section 12. I I. 7). 93 The completed photolysis samples remain inverted and refrigerated at l-5 "C prior to analysis by LC/MS or sample purge and trap CXYMS. 9.4 Sample preparation prior to LC/Ms analysis requires the addition of 30 mL of diluting solvent containing internal standard to the S-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 l-5 `CTduring the time of photolytic exposure are removed and prepared for analysis at the same time as the exposed and unexposed samples. ETS-I- 176.OPreparation of Samples for Photo&is Studies in Aqueous Matrices Method Page 11 of 18 Page 46 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 1O.f-J QUALITY CONTROL 10.1 Refer to the definitions section for the quality control specified for each respective sample type. 11.0 CALIBRATION 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/h4S methodologies for further analytical information. 12.0 PROCEDURE 12.1 Obtain the absorbance spectra of the test compound in aqueous solution using a W- Visible Spcctrophotometer (ETS-g-46.0). 12.1.1 Using a IO-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 run. A positive absorbance may indicate the potential of the anaIyte to undergo direct photolysis. Non-absorbing anaIytes would be more likely to undergo indirect photolysis as the potential degradation pathway. 12.2 Obtain the appropriate number of clear and amber 40-n& 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 m.L. 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 of matrix have been added to the vials. SeeSection 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-8-176.OPrepurution of Samples for Photolysis Studies in Aqueous Matrices Method Page 12 of 18 Page 47 of 158 3M Environmental BACK TO MAIN Laboratory Report No. W2775 Sample TreatmeaVType Matrix with testsubstance Matrix without test substauce Controlmatrixwith testsubstance # of Samples 6 +H20z(3LC/MS,3GC/MS) 6 -Hz4 (3LCiMS ,3GC/MS) 2 +HzOz (ILCiMS,lGC/MS) 2-H& (IlLCIMS,IGCMS) 2 +Hz02 (ILCIMS,lGC/MS) 2-H202 (IILChlS,lGC/MS) Control matrix without test substance 2 +Hz02 (1LC/MS, 1GCiMS) 2-Hz4 (llLC/MS,lGUMS) EXPOSED, UNEXPOSED, & DAY 0 24x 3perexptype=72 Total Samplesper compound per study = 120 (60for LCYMS6, 0 for GC/MS) # of Spikes 2 +H20z (I LC/MS, 1GC/Ms) 2 -Hz02 (1LC/MS,1GUMS) 2 +HzOz(ILCIMS,IGC/MS) 2 -Hz02 (ILCIMS,IGC/MS) 2 +HzO, (1 LC/MS, lGC/MS) 2-Hz02 (llLC/MS,IGC/MS) 2 +HzOz (lLC/MS, 1GUMS) 2-Hz4 (llLC/MS,IGC/?+4S) ! 16x3=48 12.6 Separate tbe vials into three boxes labeled "Day 0," "Exposed," and "Unexposed." Initial addition of peroxide (Section 8.4) is done at this time by removing the cap and injecting the appropriate amount (e.g. 10 - 50 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 OCand 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 fhther exposure. Store at l-5 "C prior to measuring the absorbance via W-Vis Spectrophotometer. The absorbance measurement should be performed as soon as possible, as the absorbance increase rate after light source removal may be 20% of the rate of when light is present. (Reference 18.5). 12.8 Place all the "Day 0" samples immediately in a cooler at l-5 "C or freeze at a continues temperature of less than 0 OC,inverted and protected fi-om 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 PHOTORJZA~ORSETUP ETS-8-176.OPreparation of Samples for Photolysis Studies in Aqueous Matrices Method Page 13 of 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/m2 is chosen because it yields the equivalent average optimum natural daylight radiation for 300-400 run at known latitude. (see the table below): h-radiance Source Average Optimum Natural Daylight' Atlas Pbotoreactor with integrated irradiance output of 261 W/m 300-800 nm using the IR Reflecting and 290 cuton filters `Measwed Miami, Non& (18.3) Atmroximate 250-3001~11 0.0 Intcerated and Individual Irradiances 300-400nm 400-8OOnm 34Onm 27.8 259.0 0.30 in W/m* 42Onm 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 OC water bath. Include one quinine control sample (Section 12.8) in a clear vial with the exposed sample set. 133 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 191 Flowing Water ("FW") ON Irradiation intensity Example: 261 watts/m* Duration of exposure Example: 8 hours 13.7 After entering the appropriate parameters within the menu, select program #l 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 carefully remove the sample rack. Caution: The walls of the 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. lo-50 FL) of 30% H202 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.OPreparation of Samplesfor Photo@& Studies in Aqueous Matrices Method Page 14 of 18 Page 49 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 13.9 13.10 13.11 13.12 14.0 14.1 14.2 for the unexposed samples, reactor tray holder for the exposed samples, or the cooler for the Day 0 samples). Note: Don'tforget to addperoxide to appropriate Day 0 samples! 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 of 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 receive peroxide. Record the chamber temperature daily on the sample prep sheets. 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 LCh4S or GC/MS analysis. If subsequent analysis can not be performed immediately, store samples in a cooler at l-5 OC. 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. . . SAMPLEPREPARATIONFORANALYSIS. LCYMS 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. CC/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 DATAANALYSISANDCALCULATIONS 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: ET!+!& 176.0Preparation n& 2- (%)2 I-- W-1) of Samples for Phoiolysis Studies in Aqueous Matrices Method Page 15 of 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 XlOO=Sample%RSD A= standard deviation of averaged samples B= average of samples 16.0 METHOD PERFORMANCE 16.1 each respective sample type. 17.0 POLLUTION PREVENTIONANDWASI-E MANAGEMENT 17.1 . Dispose of sample waste by placing in high or low BTU containers as appropriate. Use broken glass containers to dispose of glass pipettes. 18.0 REcolzLx3 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 fmal data packet. 18.3 Archive electronic data to compact disc media. 19.0 ATTACHMENTS 19.1 Attachment A: Example Photolysis Prep sheet, 20.0 REFERENCES 20.1 Crosby, Helz, and Zepp. Aauatic Surface Photochemistrv. 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, SalesRepresentative, 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.OPreparation ofSamples for Photolysis Studies in Aqueous Ma&ices Method Page 16 of 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 AFFECTEDDOCUMENTS 21.1 None 22.0 RFA'ISIONS Revision N- umber Reason For Revision Revision Date ETS-S-176.OPreparcztion ofSamples for Photolysis Studies in Aqueous Matrices Method Page 17 of 18 Page 52 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 Attachment A - Photo@& Sample Prep Sheet Fluorocbemical Dqredntion (Photolysis) Analysis Sample Prep Sheet Total Lrpwun: , I I I -mm I I I ETS-8-176.OPreparation of Samples for Photoiysis Studies in Aqueous Matrices Method Page18of I8 Page 53 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 3M ENVIRONMENTALLABORATORY EQUIPMENTPROCEDURE OPERATIONAND~VIMNTENANCEOFTHE SUNLIGHTEXPOSURESYSTEM, IMMERSIONUNIT,ANDRECIRCULATINGWATER CHILLER SYSTEM ProcedureNumber: ETS-9-44.0 Exact Copy of Original Qv y-zy-q Initial Date Approved by: Adoption Date: RevisionEffective Date: Laboratory Management Date ETS-9-44.0 k?quipment Procedure for the Atlas SWTESTSunlight Exposure System Page 1 of 8 Page 54 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 1.0 SCOPEAND APPLICATION 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 Photonenergy: U = hv = hclh 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/(m*nm) needed to give a specific energy over a desired wavelength range. 3.0 DESCRIPTION 3.1 The Atlas SuNTEST@ Sunlight Exposure System (CPS+ or XI%-) produces visible and ultraviolet light (250-765 W/m'). 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 IDENTIFICA~~N 4.1 Atlas SUNTEST@ XLS+, equipped with a xenon arclamp, lamp filter(s) available from Atlas to allow specific it-radiance 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 (XT-33 Refrigerated recirculator or equivalent 5.0 WARNINCA~ND CAUTIONS 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 burns 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 SUNTES~ device and the immersion unit to prevent electrical shock. 5.2 Cautions: 52.1 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 nonuniform illumination of the test chamber. ETS-944.0 EquipmentProcedurefor theAtlosSUNTESTSunlightExposureSystem Page 2 of 8 Page 55 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 5.2.3 Keep SUNTEST@ unit clear of obstructions that would block vents; overheating may cause blown f&s, shortened lamp life or other damage. 5.2.4 After beginning the experiment, always make sure that the sample vials are sufficiently submerged. Excessive heat may affect the results of the experiment. 5.2.5 Manually drain the immersion tank on the XLs+ models tier stopping the run; otherwise, the water will overflow. 6.0 SPECIALINSTRUCTIONS 6.1 None. 7.0 ~SPONSIBILITY 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 of the equipment logbook. 8.0 SIJPPLIESANDbtWEIUALS 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 filter(s) for lamp available from Atlas: Filter/ Atlas Part Number Quartz Dish wl IR reflective coating, PN 56052388 Quartz Dish, PN 56052373 W Special Suprax* F'ilter, PN 56052371 Window Glass Filter, PN 56052372 Window Glass Solar ID 65 Filter, PN 56077769 Solar Standard Filter, PN 56077759 Properties IR reflective coating (supplied standard with unit) Uncoated (to allow higher black standard temperatures) Cut-on at 290 mn, simulates outdoor solar radiation. Cut-on at 3 10 run, simulates exposure behind 3 mm (0.118 in.) window glass. Cut-on at 320 mn, simulates exposure behind 6 mm (0.236 in.) window glass. (Must be used with Window Glass Filter above.) Cut-on at 290 mn, simulates outdoor solar radiation at optimal UV intensity. m-s-9-44.0 Equipment Procedure for the Atlas SUNTEST Sunlight Exposure System Page 3 of 8 Page 56 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 9.0 CLEANING PRCMTEDURES 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 MAINTENANCE PROCEDURES 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 WIVESI? details on how to replace the lamp. instruction manual for 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 SUNTESP 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 Ifm 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 INSTRUMENT CAL~ATION 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. ET!%9-44.0 Equipment Procedure for the Atlas SiNTEST Sunlight Exposure System Page 4 of 8 Page 57 of 158 - BACK TO MAIN 3M Environmental Laboratory Report No. W2775 12.0 OPERATING PROCEDURES 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 corn 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: 12.4.2 Selection/determination of energy output (W/m') 12.4.2.1 Irradiance control and display is between 250-765 W/m2 (nominally 300800 nm). The h-radiance 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/m* (page 12, XLS+ Instruction manual). The total (integrated) energy output (300-800 nm) is directly dependent on the Me of lamp filter@) 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 mn will not reach the samples, and the 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 may be used to reference sunlight measurements and to correlate natural sunlight to the Atlas Sunteste photoreactors. Reference 14.9 is a usefut reference for determining irradiances at a specific ETS-944.0 Equipment Procedure for the Atlas SUNTESTSunlight Exposure System Page 5 of 8 Page 58 of 158 3M Environmental BACK TO MAIN Laboratory Report No. W2775 12.5 . wavelength or a wavelength range using specific filter combinations at specified global irradiances of 250,500, and 765 W/(m2nm). 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 oncethewaterbeginsto circulate. 12.5.2 Close the chamber dwr 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 Ifprogramming 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 till 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 immerkionunit. Failuretodosomayresultin remoteflooding. 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 cordinu~ at the point of 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 STJNTES'I@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-94.0 Equipment Procedure for the Atlas SUNTEST Sunlight Exposure System Page 6 of 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: XENOVIEWe 2.2 Storage So&are 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 XENOVIEWd 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 tile. 13.2 Identificationrecords 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 RE~RI~NCES 14.1 SUNTEST' XL.S/XLS+ Instruction Manual, Dot. No. 20-8036-00 Rev. 0 12/98 Atlas Electric Devices Company. 14.2 SUNTEST@ CPS/CPS+ Operating Manual, 6197 Atlas Company. 14.3 SUNTEST@ XLS+ Immersion Device Operating Manual, 2/99 Atlas Company. 14.4 SUNTESP CPS+/XLS+ Software Documentation 1.4 Atlas Company. 14.5 XENOVlEW@ 2.2 Storage SofIware Operating Instructions. 14.6 ETS-9-50.0, Operation and Maintenance of Radiometer and Detector. 14.7 "SUNTEST'%radiance 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 EquipmentProcedurefor the AtlasSUNTESTSunlightExposureSystem Page 7 of 8 Page 60 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 15.0 AFFECTED 15.1 None. DOCUMENTS 16.0 RJWISIONS Revision Number. Reason For Revision Revision Q& ETS-9-44.0 EquipmentProcedurefor theAtlasSWTESTSunlightExposureSystem Page 8 of 8 Page 61 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 3M ENVIRONMENTALLABORATORY ANALYSISOF FLUOROCHEMICALS BY ARCHON PURGE ANDTRAPAUTOSAMPLER, TEKMAR PURGE AND TRAP CONCENTRATOR AND AGILENT GAS CHROMATOGRAPWMASS SPECTROMETER Procedure Number: ETS-8-1820 Exact Copy of Original A Initial 2ifis~-9 Date ' Approved by: Laboratory Manager Adoption Date: Revision Date: ,+!!&d Date ETS-8-182.0 Analysk ofFCs by Purge & Trap AutosampIer/Concentrator/GUMS Page 62 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 1.0 S~~~EANDAPPLICATION 15 Scope. This method is used fortheanalysisof selectedhydrolysis and photolysis samples for the presence of degradation products such as olefins and hydrides-using gas chromatography/mass spectrometry in a ml1 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 IH-perfluorobutane (lH-pfC4) 1.2.5 Pertluoro-Zheptene @fC7-2ene) 1.2.6 Perfhroro- 1-heptene (pfC7-1 ene) 1.2.7 lH-perfluorohexane (lH-pE6) 1.2.8 Perfhroro-Zoctene (pfW2ene) 1.2.9 IH-pertluoroheptane (lH-pfC7) 1.2.10 2H-perfluorooctane (2H-pfC8) 1.2.11 IH-perfluorooctane (IH-pfC8) 1.3 Instrument 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 Toluened8 1.3.3 4-Bromofluorobenzene 1.3.4 Pentafhtorobenzene 1.3.5 1,4-Difluorobenzene 1.3.6 ChlorobenzenedS 1.3.7 l+Dichlorobenzene-d4 1.4 Sample Surrogate compounds. May be added at the time of sample preparation. 1A.1 Perfkorocyclohexane 2.0 SIJMMARYOPMETHOD 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 of the chemical trap increases to 250 `C!. The trapped analytes are transferred onto the GC column for GUMS 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 of Ft3 by Purge & Trap Autosampler/Concentrator/GCYMS Page 2 of 12 Page 63 of 158 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 External Standard Quantification. Process of establishing the concentration of a target analyte by plotting the theoretical amount (in units of ng/mL or l.&riL, 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 anaIyte(s) to the area response and corresponding analyte amount on the appropriate analyte's calibration curve. 3.4 Coemcient of Determination (8). 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 @t-e-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-f&e 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 the study (Exposed, Unexposed and Day 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 anaIyte(s) from the matrix. 3.9.1 Matrix 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. 3.9.2 Control Blank: A sample of ana.lyte&ee matrix (Mini-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 of FCr by Purge & Trap Autosampler/ConcentratorKKYhfS Page3 of 12 Page 64 of 156 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 background levels, interferences or suppression of target analyte(s) from the matrix. 3.10 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. 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). TripIicate samples are used to assessvariance of the photolytic method, including sample preparation, photolysis exposure, and analysis. 3.12 Relative Standard Deviation @SD). 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 of 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 of 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 of 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 of 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-g-182.0 Analysir of FCS by Purge & Trap Autosampler/ConcentratodGC/MS Page4 of 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 INTERFERENCE 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: 671.1 Autosampler: Ovarian,Archon 6.X.2 Concentrator: LSC2000, Tekmar 6.1.3 GC: 6890, Agilent 6.1.4 MS: 5973N, Agilent 6.1.5 Column, GS-GASPRO 6Om x 0.23mr1.1,J&W 7.0 SUPPLIESANDMATE~ULS 7.1 Helium, ultra-high-purity 7.2 401111VOA vials, e.g. I-Chem, S236-0040 8.0 REACENTSAND~TANDARD 8.1 Methanol, Purge and Trap grade or equivalent 8.2 Standards. Typically a minimum of five calibration standards, ranging from 1 rig/ml to 20 &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 SmPLE HANDLING 9.1 Store standards and samples in the refrigerator at 4 ' C + 3 ' C until analysis time. ETS-8-182.0 Analysis of FCr by Purge % Trap Autosampler/Concentrator/GCXMS PageS of 12 Page 66 of 158 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 QUALITYCONTROL 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 of every fifteen sampIes. 10.3 Solvent blank. SoIvent 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 of the precision of 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 f 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 CALIBRATIONANDSTANDARDIZATION 1Ll 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 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. 11.2 If the curve does not meet requirements perform routine maintenance or prepare a new standard curve (if necessary) and reanalyze Analysis E-B-8-182.0 of FCs by Purge & Trap Autosampler/Concenttor/GUMS Page6 of 12 Page 67 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 PROCEDURES 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 PoI CLOSED De&n Pol STOPPol. Equilb. Count CLOSED CLOSED 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 BeeponEnor? YES 12.1.3 Archon Method Sample Type Soil First Vial 1 Last Vial upto Sample Volume Standard 1 (1uL) :S standard 2 NO S.PreHeat Stir NO Stir NO Syring Flushes 0 PreHcat YES PreHeat Temp 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 4OmVrnin SoilPurgePressure 20psi ETS-8-182.0 Analysir of FCr by Purge & Trap Autosampler/Concentrator/GC/MS Page7ofl2 Page 68 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 12.2 Set Tekmar options Standby 40C (30C by purge) Purge 2o.oomin Dry Purge 2.0Omin Desorb Preheat 245C Desorb 0.5Omin at 250C Bake lO.OOmin at 260C BGB OFF BGB Delay Osec Auto Drain ON VaIve 180C Line 18O"C Mount 100C Runs per Sample 1 Purge Flow Purge Pressure Trap 4Omvmin 20psi vocARE3 3000 Containing: Carbopack B Carboxen 1000 carboxeu 1001 12.3 Set GC conditions 12.3.1 Oven: Initial temp: 40' C Initial time: 4.OOmin Ramp at 15.00 o Clmin to 280C Final time: lO.OOmin 12.3.2 Front Inlet: Mode: Split Initial temp: 180C Pressure: 8.5Opsi (on) split ratio: 10.7 : 1 Split flow: 16.1 ml/min Total flow: 20.6 mlhnin 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 o C MS quadruple temp: 150' C Interface temp: 260 oC Multiplier voltage: adjust to give required low standard sensitivity ETS-g-182.0 Analysis of FCS by Purge & i?ap Autosampler/Concentrator/GC/MS Page8 of 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 datatiles created. The sequence should be documented n the run files. 12.6 Sample analysis. 12.611 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 DATA ANALYSIS AND CALCULATION 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 Ml M2 M3 M4 MS Explanation Peak was not automatically integrated by Target, therefore, integrated manually Peak was automatically integrated; was reintegrated manually to improve sample-to-sample integration consistency. Incorrect quantification ion peak was integrated; manual integration was done to select the correct peak. Incorrect monitor ion peak was integrated; manual integration was done to select the correct peak. 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) xl 00 expected concentration 14.0 METHOD PERFORMANCE 14.1 Coefficient of Determination (r'). The coefficient of determination (?) for the initial calibration curves should be 0.990 or greater. The curves should be examined closely for E7-S8-182.0 Analysis ofFCs by Purge & Trap Autosampler/Concentrator/GC/MS Page9 of 12 Page 70 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 linearity and intercept, particularly for accuracy of quantitation at the low and high ends of 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% (k 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 of 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 aualytical run. Peaks with greater than 25% of the peak area of the designated LOQ value observed in matrix blanks are indicative of either matrix effect, sample contamination or instrument contamination. Use of solvent blanks prior to the matrix blank may be necessary to rule out instnunental contamination or 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 5 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 ET-S-8-I 82.0 Analysir ofFCr by Purge & Trap Autosampfer/Concentrator/GCYMS 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 i 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 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 POLLIJTIONPREVENTIONAND WASTE MANAGEMENT 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 RECORDS 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. El%8-l 82.0 Analysis of FCs by Purge & Trap Aulosampler/Concentraraior/GUMS Page11of 12 Page 72 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 . . 17.0 ATTACHMENT 17.1 None. 18.0 REFERENCES 18.1 Archon Purge and Trap Autosampler System Operator's Manual, 1996, Varian. 18.2 Tekmar LX200 Instruction Manual, 1996, Tekmar. 18.3 Agilent MSD Hardware Manual for 5973N, 1999, Agilent. 18.4 Agilent 6890 Series Gas Chrornatograph, volumes 1-3, 1999, Agilent 19.0 AFFECTEDDOCUMENTS 19.1 None. 20.0 REVISIONS Revision Number. Reason For Revision Revision Q& El-S-S-182.0 Analysi of FCk by Purge & Trap AutosampIer/Concentrator/GC/MS Page12of 12 Page 73 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 3M ENVIRONMENTALLABORATORY Method Indirect PhotolysisScreeningTestin SyntheticHumic Water Method Number: ETS-8-177.0 Approved By: Adoption Date: Revision Effective Date: Em-8-l 77.0 Indirect Photolysis Screening Tests in Synthetic Humic Water Page 1 of 16 Page 74 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 1.0 ScoPE AND APPIxATI~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 of 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 (`0,) 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 halflives of test chemicals in pure water (PW) and SHW. This phase also includes parallel solar irradiation of a radiometer to calculate k, (the indirect photolysis rate in the test vessel, e.g. 40 mL glass VOA vial) and krs (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: ComDoand Acronvm Comuoaad Acroavm Perfiuomoctanoic acid PernuorooctancsuIfonate PFOA PFOS Pertluorobutanoic acid Perfluombutanesulfonate PFBA PFBS PerSuomoctanesulfonamide N-methylperfluomoctanesulfonamide FOSA N-MeFOSA Pertluombutanesulfonamide N-mahyl~uombutanesulfonamide FBSA N-MeFBSA N-ethylpetfluorooctanesulfomtmide N-EtFOSA N-ethylperfhtombutanesulfonarnidc N-EtFBSA 2-(N-methylperfhromoctane sulfonamide) ethyl alcohol N-MeFOSE-OH 2-(N-methylpeffluorobutanesulfonamido) ethyl N-MeFBSE &OhOl OH z-(N-cthylpeduorooctanc sulfonamido)ethyl alcohol I-prrfluorooctene N-EtFOSE-OH -- 2-(N-cthyIperfluombu~n~ulfonamido)efhyl alcohol I-perfhtombutene N-ECFBSE-OH -- Pctiuomoctanehydridc 1H, Cs-hydride Pertluombutanehydride lH, C,-hydride .. . and other C4 through Cl0 homologues,and polymeric materialsbasedon the aboveaforementioned compounds. 1.4 Acceptable matrix. Synthetic humic water (SHIV), 0.005 M pH 7.0 Phosphate Buffer. ETS-8-177.0 Indirect Photo&s Screening Tests in Synthetic Humic Water Page 2 of 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 of most surface fresh waters (approximately 0.5 AU at 370 run). 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 f 5 OC. Samples to be exposed are photolyzed in the photoreactor at 261 W/m' (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 l-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 uuexposed'absorbance controls will be prepared per timepoint. 2.2.1 Samples to be prepared for each timepoint and for each exposure type: =7ftz= oc/Ms Analysis Analysis SampleRep I SampleRep2 SampleRep3 Sample Spike I Samplo Spiko 2 Matrix Blank Matrix Blank Spiko + 0 8 + 0 + 8 + 0 + 0 + 0 + 0 0 + + + 0 0 + .+ + 0 0 0 0 + 0 0 0 + Control Malrix(#l) blank 0 + 0 0 0 Control MatAx tamp10 0 + 0 + 0 Contml hImix spike 0 + 0 + + Control Matrix(K!) blank 0 0 + 0 0 Contml b&tix(e2) rsmplo + + 0 Control Mabix(#Z) spike 0" 0" + + + Absorbance ConId + 0 0 0 Absorbsncc Conlml dup + 0 0 0 8 j$qlcnJ ".+" = additionof solutionor test substance and"0" = NO addition, analysis. Timo Point 0 8hr 16hr 32 hr 64 hr 17R hr # of Exposed Samples 0 30 30 30 30 311 # of Unexposed Samples 30 (Time 0) `30 ' 30 30 30 # of samplesfor LUMS Analysis ( Exp + Unexp) 13 26 26 26 26 26 13-l IRO 143 A A A A A A A A A A A A A A A A A A A A A A 2 A^ NA NA NA "analysis perfomd, NA NA NA NA NA NA NA NA NA NA NA E A and NA = no # of samplesfor GCMS Analysis (Exp + Unexp) 13 26 26 26 26 26 143 # of samplesfor UVNis Analysis (Exp + Unoxp) 4 8 8 8 8 R 44 Indirect Photolysis ETS-8-177.0 Screening Tests in Synthetic Humic Water Page 3 of 16 Page 76 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 3.0 QUALITYCONTROL-DEFINITION/FREQUENCY/PERFOCRRITEMRIAANCE 3.1 Blanks 3.1.1 Definitions: Matrix Blank, A sample of analyte-iize 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 Tie 0). The matrix 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 matrix. Control Blank. A sample of analyte-fkee 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 v,tiables 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, 3.1.2 Freqaency/PerformancCeriteria: Listed in the following table: Matrix ID Matrix Blank (BufferISHW) Control Blank #l (BuffcdPW) Control Blank #2 0 Matrix descriotioa Frequency 0.01 M Phosphate Buffer, pH 7: Synthetic Humic Water 0.01 M Phosphate Buffer, pH 7 : ASTM Typo II Water ASTM Type II Water 1 Replicate per light and dark exposure, for each time point ar,d for each analytic'al 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 Defmition: 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 Photolysir Screening Tests in Synthetic Humic Water Page4of16 Page 77 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 3.2.2 Frequency/Performance Criteria: Listed in the following table: Matrix Description 1Freauency Performance Criteria The analystshallaccept%RSD.s~25%. Precision values>25%mustbe documentedandjustified (if 3.3 Analytical Spike (AS) 3.3.1 Definition: A known mass of target analyte(s) in a specified amount of a diluted and/or aliquotted 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 matrix effect. 3.3.2 Frequency/Performance Criteria: Listed in the following table: Matrix Description 1Frequency . 1Performance Criteria TestMatrix and testsubstances,piked 12 spikedsamplesper I with targetanalyte(s)justprior to treatmenttype(onein lower analysis half of the calibrationrange, andonein theupperhalf of The analystshallaccept 1 the calibration riige) accuracyof 100f 25%. If ITestMatrix with NO test substance, 1 accuracyisoutsideof this spikedwith targetanalyte(sj)ust prior range,documentandjustify, if to analvsis possible,thereasonfor the tCcmtro1Matrix (#l) and test 1Replicatepertreatmenttype 1beviation. ) substances, pike>with target ] (mid-rangespike analyte(s)just prior to analysis concentration) Control Matrix (#2) and test substances, pikedwith target aualyte(s)just prior to analysis 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 Descriptton Control Matrix (#l) und test substance 1 Frequency I 1 Replicateper light anddark exposure,for each Performance Criteria The analystshallacceptaccuracyof 100f 25%. If accuracyis outsideof thisrange, documentandjusti@,if possible,the reason for thedeviation. ETS-8-177.0 Indirect Photolysis Screening Tests in Synthetic Humic Water PageSof Page 78 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 3.5 Absorbance Control 3.5.1 Defmition: An analytefree 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/PerformancCeriteria: Listed in the table below. Matrix Descrtpttoa 1 Frequency 1 Performance Criteria I I 1 Control Matrix (#l) Buffer/SHW only 2 Replicates per light and dark exposure, for each time point Absorbance measured at 370 run is between 0.01 AU-O.05 AU (1 cm pathlength cell) 3.6 Internal Standard/Surrogate 3.6.1 Internal StandardDefinition(appliesto LC/MS samples):A known amount of a compound similar in analytical behavior to the target analyte(s) of interest (e.g. 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctane suIfonic 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 SurrogateDefinition (appliesto LC/MS andGC/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 of 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, aswell 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/PerformancCeriteria: Listed in the following table: Math DeacriDtion Frwuencv of Use Sample diluted with 30 rnL of Internal standard compound dissolved in a suitable analytical solvent Sample with surrogate compound spiked into it. Evcly I.aMs sample analyzed 1 May be added to every LClMs and CC/MS sample analyzed Performance Criteria The %RSD for internal standards shall be calculated for the area response of all 1appropriate 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-g-177.0 indirect Photolysis Screening Tests in Synthetic Humic Water Page6of16 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 Product(s): 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. 3.7.5 Relative Percent Difference (RPD): A measure of precision defined as the absolute value of 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 asthe 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 CAUTIONS 4.1 Health and Safety Warnings 4.1.1 Wear the proper lab attire for all parts of these procedures. protection at all times. Wear gloves and eye 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. Indirect Photolysis ETS-8-177.0 Screening Tests in Synthetic Humic Water Page 7 of 16 Page 80 of 158 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. xi-5.0 INTERFERENCE Contaminants in solvents, reagents, glassware aud 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. a--6.0 EQUIPMENT Analytical balance sensitive to 0.1 mg 6.2 Phot&eactor: Suntest CPS+, XLS+, ir equivalent, capable of producing 250~765 Watts/m2, equibped 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 f 5 "C . 6.4 W-Visible Spectrophotometer (UV-VIS), equipped with tungsten and deuterium lamps, model 8453, or equivalent 6.4.1 Autosampler: Model G112OA, or l-cm pathlength cell holder: Model 08451- 60104, or equivalent. 6.4.1.1 l-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 1O-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 Data System: A PC capable of controlling the W-Visible Spectrophotometer system. 6.6 Centritige capable of maintaining >2000 rpm for 10 minutes at ambient temperature (2226C). 6.7 Radiometer, capable of detecting and recording irradiation output of the photoreactor for the duration of the study. 6.8 Lab Oven, capable of maintaining 70-80 "C. 7.0 7.1 40-mL amber and clear glass vials (VOA) with screw caps. 7.2 Crimp cap autovials: 1.5-n& 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. El-S-8-l 77.0 Indirect Photolysis Screening Tests in Synthetic Humic Water Page 8 of 16 Page 81 of 158 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 f 1% of the total volume), 5 pL to 1000 FL. 7.9 1O-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, GehnanlU or equivalent. 7.11 500~mL. glass screw-top containers. 8.0 REAGENTS AND STANDARDS 8.1 Water/Pure water (PW), ASTM Type II water at a minimum 8.2 Methanol (MeOH), HPLUSPECYGC 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, tirn Aldrich OFequivalent. 8.6 NaOH, reagent grade tirn EM ScienceTMor equivalent. 8.7 0.1% NaOH solution Example: Weigh approximately 1.Og 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 (I&SO,), 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 KH,PO, into 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 f 0.1 with 0.1% NaOH or dilute H,SO,, and dilute to the mark with PW. 8.10 Method Blank Solutions: Method Blank Tows Matrix ID Test Matrix BufferASHW ControlMatrix (#I) Bufer/PW ControlMatrix (#2)PW I Matrix descrfDtion Example: I:10 Solution: Dilute 50mL SyntheticHumic Waterwith 0.01 M pH 7.0 PhosphateBuffer solutionto 500mL. Example: 1:lOSolution:Dilute SOmL PureWater(ASTM TypeII) with 0.01M pH 7.0PhosphateBuffer solutionto 500 mL. PureWater(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/rnL 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 Testsin Synthetic Humic Water Page9 of 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 5OpL of internal standard stock solution (Section 8.11) to 1 L with MeOH to a nom&d concentration of 0.5 AU pg/mL. 8.12 Test Solutions 8.12.1 Test SubstanceP: repare 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. 5OpL added to 5 mL ofmatrix = 1% v/v) Then measure the absorbance of the test substance solution dihrted with buffer/water matrix to the desired concentration. The maximum absorbance at any wavelength greater than 29Onm must be < 0.05, when measured in a standard l-cm pathlength cell. Example: A 900 pg/mL solution of test substance in acetonitrile is prepared by weighing 90 mg of test substance into a 100 mL volumetric flask.and diluting to the mark with acetonitrile. 9.0 SAMPLEHANDLING 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 l-5 "C!. After the exposure period, CC/MS samples shall be maintained in an inverted position in a cooler at l-5 "C until they are loaded onto the autosampler. 9.3 Once the 30-mL aliquot of diluting solvent has been added to the LCYMS photolysis samples, (see Section 12.0), the samples should be analyzed as soon as possible. Alternatively, the samples may be stored at l-5 "C. Day 0 samples are to be stored at l-5 "C during the time of sample exposure, and then diluted along with the exposed and unexposed samples just prior to analysis. 10.0 QUALITYCONTROL 10.1 Quality control parameters (and the fiequemcy of use) are included in Section 3.0. 11.O CALIBRATION AND STANDARDIZATION 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, weekIy, 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 Photolysis Screening Testsin Synthetic Humic Water Page 10 of 16 Page 83 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 12.0 PROCEDURES 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. loo-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 supematant 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 H,SO., or 0.1 % NaOH. 12.1.6 Filter-sterilize the solution through a 0.2pm diameter poresize 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 26 1 W/m' to pre-age the solution (equivalent to three day's worth of Miami, Florida sunlight). The EPA's definition of "1 Day" of irradiation is "eight hours." The irradiation intensity of 26 1 W/m* was chosen because it yields the equivalent average optimum natural daylight radiation for 300-400 mu (see the table below): Amwoximrte Intearated and Individual Irrndiances in W/m' Irradiance Source 250-300 um 300-400 nm 400-800 ml 340 nm 420 nm AverageOptimumNatural o o Daylight' 27.8 259.0 0.30 0.67 Atlas Photoreactor with integrated irradiance output of 261 W/m* 300-800 am using 0.08 the lR Reflecting on filters and 290 cut- `Measured - 25 "N. Miami, Florida (See Reference 27.8 18.4) 234.36 0.24 0.71 12.1.9 12.1.10 12.1.11 Aliquot the SHW into a l-cm quartz W-VI.9 cuvette and analyze tbe absorbance at 370 nm. 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 H2S0, solution or 0.1% NaOH solution. Calculate the dilution factor necessary to decrease the absorbance to approximately 0.5 AU (in a l-cm pathlength cell) in 1 L of SHW: where: 0.5 = &ml 1L x A,,,,0 = 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 with PW. ETS-8-177.0 Indirect Photolysis Screening Testsin Synthetic Humic Water Page 11 of 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 l-cm W-VIS cuvette and taking the absorbance reading at 370 mn. 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 "Fluorochemical 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-n& 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. &C/MS and GC/MS): Lhcription Sample Rep 1 Sample Rep 2 Sample Rep 3 Sample Spike I Sample Spike 2 Maeix Blank Matrix Blank Spike hdml M&ixMI~ 3drol Mauix(#l) Control Matrix(#l) Control MaMx(#Z) Control Matrix(#Z) Control Matrix(#2) blank sample spike blank sample spike Sample Rep 1 K$i: Sample Spike 1 Sample Spike 2 Test Mabix Blank Test Matrix Blank Control Matrbt(#l) Control Matrix(#l) Control Matrlx(#I) Control Matrix(#?) Control Matrixf32) Spike blank sample spike blank sample Test Matrix (ButTer/sHw) + + + + + + + 0 0 0 0 0 0 Control Matrix 1 (Buffcrmv) 0 0 8 0 0 0 + + + 0 0 0 0 0 0 0 0 0 0 + + + 0 0 Control Matrix 2 (PY 0 0 0 0 0 0 0 0 0 0 + + + 0 0 0 0 0 0 0 0 0 0 + + Test Substance + + + + + 0 0 0 + + + + + 0 0 0 + + 0 t Where "+`I = addition of solution or test substance and "0" = NO addition ETS-8-177.0 Indirect Photolysis Screening Tests in Synthetic Humic Water Vial TypeIExposure CIearExposed Clear/Exposed Clear&posed Clear/Exposed CledBXpOXd ClearfExwsed Clear/E&d Clcar/E?xpmd Clcar/Exboscd Clesr/Expored Clear/Exposed Cl.%dEXpOSCd ClCdEXpOSCd Amber/Unexposed AmbarhJnexposed Ambedhexposed AmbcrRmCXpoSCd Amber/Unexposed AmberKJnexposed Amber/Unexposed Amber/Unexposed Amber/Unexposed Amber/Unexposed Amber/Unexposed Ambcr/UnexDosed Page12 of 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 I:9 v/v Create one set of samples (listed below) for each time point for WMS analysis: 12.2.6 12.2.7 Store the "Time 0" vials in a labeled box at l-5 "C. Place all the vials that will go into the photoreactor into au 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 12.2.8 caps and proceed to load the reactor. 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 f 5 "C) during the exposure. (The vials are exposure- and temperature-controlled.) 12.2.9 Place the clear "exposed" vials iu 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 of 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/m'. See SOP 12.2.12 ETS-944.0 for operation of the photoreactor. Following each exposure interval, remove vials from the photoreactor and store inverted in a cooler at l-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 W-VIS absorbance control analysis 12.2.13.1 Analyze the pH 7.0 SHIV/buffer absorbance controls by W/Visible absorbance spectroscopy at 370 nm by aliquoting the test solution directly 12.2.14 12.2.15 12.2.16 into a 1-cm or greater pathlength quartz cuvette and obtaining the spectra. See SOP ETS-9-46.0 for operation of the WMS instrument. The resultant peak at 370 mn will be analyzed to determine the change in absorbance between the Time 0, exposed and unexposed samples. LCIMS sample analysis Dilute the exposed and unexposed samples for all timepoints with 30 mL internal standard solution in methanol (Section 8.11 .l). Add spiking solution to the appropriate vials. Invert each vial several times to mix. 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-t-18 1.O. 12.2.17 GCNS sample analysis ETS-8-177.0 Indirect Photolysis Screening Testsin Synthetic Humic Water Page 13 of 16 Page 86 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 12.2.17.1 12.2.17.2 Analyze the exposed and unexposed samples for all timepoints as-is by purge and trap CC/MS. Add spiking and surrogate solutions, as required, to the appropriate vials. Analyze according to ETS-8-I 82.0. Important: Maintain vials in the inverted position until they can be placed in the autosampler. 13.0 DATAANALYSISANDCALCIJLATIONS 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 METHODPERFORMANCE 14.1 Not applicable. 15.0 POLLUTIONPREVENTIONANDWASTEMANAGEMENT 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 RECORDS 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 worksheet(s) documents completely, making sure to include all initials and dates. 16.4 Archive electronic data to compact disc media. 17.0 ATTACHMENTS 17.1 "Fluorochemical Degradation (Photolysis) Sample Prep Sheet" 18.0 REFERENCES 18.1 Interpersonal conversation with Carrie O'Connor, Optical Systems Engineer, Atlas Electric Devices. 18.2 "Suntest CPS/CPS+ Spectral Jrradiance 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 Testsin Synthetic Humic Water Page14 of 16 Page 87 of 158 , . 19.0 AFFJETED DOCUMENTS 19.1 None 20.0 Revisions Revision Number. Reason For Revision BACK TO MAIN 3M Environmental Laboratory Report No. W2775 Revision j&e ETS-g-177.0 Indirect Photolysis Screening Tesrsin Synthetic Humic Water Page 15 of 16 Page 88 of 158 Attachment A- Photolysis Sample Prep Sheet BACK TO MAIN 3M Environmental Laboratory Report No. W2775 . ETS-B-177.0 Indirect Photolysti Screening Tese in Synthetic ffumic Water Page 16of 16 Page 89 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 3M ENVIRONMENTALLABORATORY EQUIPMENT PROCEDURE OPERATIONAND MAINTENANCE OFTHE HEWLETT PACKARD8453 W-VISIBLE SPECTROPHOTOMJZTER ProcedureNumber: ETS-9-46.0 Approved by: Laboratory Management Adoption Date: lc3/23 / 32 RevisionEffective Date: ETS-9-46.0 Operationand Maintenance of the HP8453 UV-Vis Spectrophotometer Page 1 of 9 Page 90 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 1.0 SCOPEAND APPLICATION 1.1 This equipment procedure describes the operation, cleaning, and maintenance of the Hewlett-Packard 8453 IJV-Visible Spectroscopy System. 2.0 DEFINITIONS 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 Pathiength: The distance the light passesthrough 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 of 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 Cutoffz 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 run, detectable by human eyes. 2.8 Ultra-violet (UV): The portion of the invisisble electromagnetic spectrum composed of wavelengths of 10400 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 DESCRIPTION 3.1 The HP 8453 spectrophotometer is a single-beam, microprocessor-controlled, UV-visible spectrophotometer with collimating optics. The ChemStation@ for W-Visible spectroscopy software running on a PC with Microsoft@ NT operating system provides instrument control, data acquisition, and data evaluation. 4.0 IDEN~FICATI~N 4.1 Hewlett Packard G1103A Serial No. CN93500458 4.2 Hewlett Packard 89090A Serial No. DE14300757 5.0 WARNINGS AND CAUTIONS 5.1 Health and Safety Warnings: ETS-9-46.0 Operation and Maintenance of the HP8453 UV-Vis Spectrophotometer Page 2 of 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 cpltages, 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 run. 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 diction 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. 52.9 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 SPECIALINSTRUCTIONS 6.1 None. 7.0 REsP0NsIBILIn 7.1 The operator is responsible for routine maintenance and cleaning. ETS-946.0 Operation and Maintenanceof the HP8453UV-Vis Spectrophotometer Page 3 of 9 Page 92 of 158 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 SUPPLIESANDMATERIALS 8.r 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 G13 15A, Agilent 8453A (Part No. G1103-60001). 9.0 INSTRUMENT CLEANING PROCEDURES 9.1 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 instrumentand 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 MI0 board that may be plugged in from the rear side of the instrument. 9.13 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 several 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 fur 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 MI0 board (plugged in from the rear side of 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 the Sample Compartment Side. (Recommended at oneyearly intervals or more frequently when operating the spectrophotometer in a particularly dirty environment.) 9.2.1 Turnoff theinstrumenat nddisconnectht epowercord. 9.2.2 Remove any cuvette holder from the sample compartment. ETS-9-46.0 Operation and Maintenance of the HP8453 UV-Vis Spectrophotometer Page 4 of 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 MAINTENANCE PROCEDURES 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. 10.1.1.3 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 OperationandMaintenanceof theHP8453UV-Vis Spectrophotometer Page5 of 9 Page 94 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 11.0 OPERATING PROCEDURES 11.1 Powering Up the HP 8453 W-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 W-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 thesample 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 cli&ng 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 OperationandMaintenanceof the HP8453UV-VisSpectrophotometer Page6 of 9 Page 95 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 11.53 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 whetherthe 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 of 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 UV- Visible 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 "PeakiValley Find" if necessary. ETS-9-46.0 Operationand Maintenanceof theHP8453UV-VisSpectrophotometer Page7 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 Measurea 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 of 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 Sp&ra: 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. 11.8.3.1 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 TESTING, CALIBRATION AND/OR STANDARDIZATION PROCEDURES 13.1 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 selftest. 13.1.4 Theself-tesrtesults will be displayed in a window with pass/fail criteria. 13.2 Calibrating for a single component analysis. ETS-9-46.0 Operationand Maintenance of the HP8453 UV-Vis Spectrophotometer Page 8 of 9 Page 97 of 158 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 Deftitions obtained from www.spectroscopymag.com. 14.2 HP Manual: Understanding Your W-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 W-Visible Spectrophotometer Service Manual, Hewlett-Packard: Wilmington, DE, 1998. Part No. G1115-90003. 15.0 AFFECTED DOCUMENTS 15.1 None. 16.0 REVISIONS Revision Number. Reason For Revision Revision pa& El-S-9-46.0 Operation and Maintenance of the HP8453 UV-Vis Spectrophotometer Page 9 of 9 Page 98 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 c 3M ENVIRONMENTALLABORATOR_Y_ EQUIPMENTPROCEDURE ROUTINEMAINTENANCE OFARCIION PURGEANDTRAP AUTOSAMPLER, TEKIUR FWRGEANDTRAP CONCENTRATORANDAGILENT GAS CHROMATOGRAPIUMASSSPECTROMETER ProcedureNumber: ETS-9-49.0 Approved by: Laboratory Manager Adoption Date: RevisionDate: ETS-9-49.0 Routine Maintenance of the Purge & Trap AutosampletKoncenfraradWMS Page 99 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 1.0 SCOPEANDAPPLICATION (USENUMBEREDTIER 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 I mass spectrometer @C/MS) system. Specific items requiring routine maintensnce 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 DESCRPTION 3.1 Archon purge and trap autosampler equipped with Tekmar purge and trap concentrator and Agilent gas chromatograph and mass spectrometer. 4.0 IDEN~~CATI~N 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 USOOO34972,6890 G1530A, Agilent 4.1.4 MS: serial number US01 180105,5973N G2589A, Agilent 4.1.5 PC: serial number US94850812, D6720T, HP Kayak XA 5.0 WARNINGS AM) CAUTIONS 5.1 Health and Safety Warnings: 51.1 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 SPECIAL INSTRUCTIONS 6.1 Not applicable. ETS-9-49.0 Routine Maintenance of the Purge & Trap Autosampler/Concentrator/GUMS Page 2 of 5 Page 100 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 7.0 ~SPONSIFIILITY 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 SUPPLIESANDhtATEIUALS 8.1 Graphite Fermles, 0.4 mm I.D. for 0.25 mm columns 8.2 Abrasive paper, Hewlett-Packard, part no. 5061-5896 8.3 Alumina abrasive powder, Hewlett-Packard, part no. 8660-079 1 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 mw 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 Thennogreen LB2 septa, Supelco, part #23 163, 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 CLEANING PROCEDURES N/A lo.0 MAWi'ENANCE~ROCEDURES 10.1 Routine: Tighten the elevator's assembly nuts when Archon autosampler displays error messag" eElevatonrothomepdositio"n. 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 Maintenance of the Purge & Trap Autosampler/Concentrator/GC/MS 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, dry 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: GUMS 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-l 2 months according to the MSD Hardware manual. 10.5 Nonroutine: Document any nonroutine maintenance in the instrument's maintenance logbook. 11.0 OPERATING PR~CEDIJRES 11.1 For operating procedures, refer to an appropriate analytical method, or to the Archon Purge and Trap Autosampler System Operator's Manual, Telanar LSC200 Instruction Manual and the Hewlett-Packard MSD Hardware Manual for HP 5973N & HP 6890 Series Mass Selective Dete$ors. 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 was routine or non-routine. Be sure to date and initial the entry. Logbooks are archived when complete. 13.0 TESTING, CALIBRATION AND/ORSTANDARDIZATIONPROCEDURES 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 autotune; check for improved performance and for the presence or absence of air leaks. A tune report can also be used to check for leaks a&r performing injection port maintenance. 14.0 IUWEREN~ES 14.1 Archon Purge and Trap Autosampler System Operator's Manual 14.2 Tekmar LSC200 Instruction Manual ETS-9-49.0 Routine Maintenance of the Purge & Trap Autosampler/Concentrator/GUhfS 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 15.1 None. 16.0 REVISIONS Revision Number. Reason For Revision Revision l&g ETS-g-49.0 Routine Maintenance of the Purge & Trap Autosampler/C'oncentrator/GC/IUS 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 control substances. information for both reference substances and Page 104 of 158 Chemical Characterization IUPAC Name BACK TO MAIN 3M Environmental Laboratory Report No. W2775 Page 105 of 158 3M Environmental BACK TO MAIN Laboratory Report No. W2775 Reference Substances (continued) I Reference Substance IUPAC Name Chemical Formula I Identifier I Source Expiration Date Storage Conditions Chemical Lot Number Physical Description Purity Reference Substance IUPAC Name Chemical Formula I Identifier Source Expiration Date Storage Conditions Chemical Lot Number I Physical Description Purity Cs HydrideIOlefin Mix 171~1~22~3~3~4,94,5,,5,6,,6,,7888 pentadecafluorooctane, Z- pertluorooctene CsF,,CFHCFsZCsF,sCF=CF2 I TCR-99030-18 1 3M Specialty Chemicals 616199 Frozen 1 Clear ambient liquid 85% Cs Hydride, 15% C8 Oletin Cq Interior Olefin 2-Perfluorobutene C4F8 I 360-89-4* Lancaster Synthesis 2002 Frozen I G00195, TNA-4298 I Clear ambient liauid 97% Cn Terminal Hvdride 1'12'23' 3'44'55' 6'67'78' 8',8' ' ' ' ' heptadecafluorooctane CBFITH I 335-65-9* 1 Aldrich Chemical 2002 Frozen 04307PN. TNA-2983 Clear ambient liquid 99% C, Terminal Hvdride 1,1,2,2,3,3,3 heptafluoropropane C&H I 2252-84-4* Lancaster Synthesis 2010 Flammable G0062B. TNA-4294 I GaS 97% Ca Terminal Hvdride 1121,,2,,3>3,3444 nonafluorobutane GF& I 375-17-7* I I Crescent Chemical 1 2002 Frozen 6A-46. TNA-3997 Clear ambient liquid 99% C, Terminal Hvdride 1,1,2,2,2 pentafluoroethane GF<H I 354-33-6* I Lancaster Synthesis 2010 Flammable G00492. TNA-302 1 I GFIS I 99% I 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 PFCH GF12 Perfluorocyclo-hexane Surrogate Standard For GC/MS analysis Aldrich Chemical 2005 Frozen PFBS Perfluorobutane-sulfonate, potassium salt C4F9S02K Internal Standard for LC/MS analysis 3M Specialty Chemicals 2002 Frozen Pentafluorobenzene CtsHFs Pentafluorobenzene Instrumental Surrogate Standard For GCYMS analysis Restek Corp. 612002 Frozen Use Source Instrumental Surrogate Standard For GCIMS analysis Restek Corp. instrumental Surrogate Standard For GC/MS analysis Restek Corp. Instrumental Surrogate Standard For GC/MS analysis Restek Corp. Expiration Date Storage Conditions Chemical Lot Number Physical Description Purity *CAS Number 612002 Frozen A013256 Methanol solution 99% (2500 pghL + 0.2%) 212002 Frozen A012973 Methanol solution 99% (2500 pg/mL 2 0.2%) 612002 Frozen A013256 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 application of this model in the determination of the estimated halFlives presented. in this study and the Page 108 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 Kinetics Model Cl. 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,, which number N. The actual reactions that occur are subsumed in these equations, and are assumed to proceed with pseudo-first order rates k,, (for the parent) and k,, (for the products). k,m P + photon + n, A,,, +Yd (m=ltoN) (Cl) A,,, + photon % Ym2 (m=ltoN) (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 Y,, and Ym2 represent all the other hydrolysis products. C2. Parent Compound Concentrations Equation Cl 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 -d=P- (W P Equation C4 may be directly integrated to obtain the general solution ldPl=(-2 "mk,, t),c (C5) With the initial condition P(t = 0) = P,,, the specific solution to Equation C4 is P = PO exp (-g n,,, k,, t]=Po eekpt VW Page 109 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 using the additional definition of the total parent photolysis rate k, = 2 n,,, k,, . (C7) m=l Equation C6 can be r-e-written in a form that allows a least-squares estimate of the total parent hydrolysis rate: Using the initial (t = 0) measured value of the parent concentration POand later values P measured at later times t , one can calculate and plot the (linear) quantity [- ln (P/P,)] versus time and obtain a least -squares estimate of the slope of the line. The resulting slope is the least-squares estimate c,, of the total parent photolysis rate. Equation C6 indicates that over a period of time T": (the parent half-life) the parent concentration P is reduced through hydrolysis by a factor of two, where T1/P2- q2) W) kP A least squares estimate ? `$ of the parent photolysis half-life is therefore available from C3. Product Compound Concentrations The pseudo-first order differential changes in the product concentrations A, (using Equations C2 and C6) are dA, = ( n,kp,,,P - k,,A,)dt = (n,k,,P,, eekpt - k.,A,)dt WI) and the (frrst order, non-separable) differential equation governing the product concentrations is Ad+A k,A, = nmkPmPeOmkpt. VW dt Page IlOof 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 The "standard form" of Equation Cl2 is A;+S(t)A, =Q(t) (Cl31 where the "function"S (t) is actually a constant: s6)=Ll (C14) and Q(t) = n,k,,P,, emkpt. (Cl3 The general solution A, to Equation Cl2 is contained in A els(f)dt In = Q(t) el'(")* J & +C W6) where and Q(t)elsb')dt' dt + C = nmkPmPOekht eMkptd+t C WV s I There are two cases of Equation Cl8 to consider. In the circumstance that k,, = k, , 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 (for k, = k, ) W9) A, ekpt= nmkPmPt,,+ C and, using the initial conditionA,(t = 0) = A, , the specific solution to Equation18 is (for k, = k, ) G33 A,,, = (n,k,,P, t +A,)eekp' . Page 111 of 158 3M Environmental BACK TO MAIN Laboratory Report No. W2775 We note that when k, = k, = 0 (that is, when both the parent and potential product are photolytically stable), Equation C7 requires (also) that k,, = 0, so Equation C20 becomes A,=A, (C21) indicating, as required, that the product concentration does not change with time. The circumstance k,, = k, 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, and the product photolysis ratek, approach each other. In the more probable case, for which k, f k, (i.e. that the rate of the mth product is different from the total parent rate), the general solution to Equation Cl 8 is A,e k,t,,,-_t nmk~mPe~(k,-kp)t + c (cm k4ln- k, and the specific solution to Equation Cl8 with the initial condition A,(t = 0) = A,, is ?llkPmpO e-k, t _ %nk~,Po e-k, t w3) k, -km k,-kvn * 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) A, =AmO + %Jb,po (l-e-q . (c24) b C4. Relationships Between the Parent and Compound Equations C7 and C24 can be combined to obtain Concentrations (for stable products) w5) Page112of158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 so that N k, = c nm kPm= m=l (for stable products) ( l---k, I)= 2 (*tn -*trio) W6) m=l PO or (for stable products) If the changes concentration, k,t =-ln l- N 6% -A,,) c m=l PO 1 in the product concentrations are all small compared that is, if cNk-*m<o<I m-l PO (c27) to the original parent GW we may use the expression (valid for -1 5 X I 1 ) ln(l+X)=X- +x2 +$x3 - ix4 + ..... and Equation B23 becomes (for stable products and c *m -*td , <<PO) kptz{-~`m--;mo] or (C29) (C30) Page 1130f 158 3M Environmental BACK TO MAIN Laboratory Report No. W2775 (for stable products and c A, -4-n,, m c< PO) (C31) CS. Parent Half-Life Estimates Based on Limits of Quantification of the Products In every experimental determination of k, , there is some set of values AfQ (the "limits of quantitation") below which the product concentrations A, cannot be reliably measured. If during an experiment carried out over the period of timeA t all the product concentrations A,,, remain below their limits of quantitation, then the maximum possible value of the rate k, is obtained by assuming (for all the products) that 1) A,,,,, = 0 and 2) at time t = A t , the product concentrations have increased to the values A,,, = ArQ. With these assumptions, the experimental data indicate that the reaction rate k, is less than some maximum value (k,)- as follows: (for photolytically stable products at concentrations below the limits of quantitation) k, 5 (kP)- = &-tArQ. (~32) 0 m=l Under the same circumstances and assumptions, the experimental data indicate that the parent half-life T'$ (see Equation C9) is greater than the value (TV:),, as follows: (for photolytically stable products at concentrations below the limits of quantitation) (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 a// the potential products are measured. Otherwise, the quantity (kp)- in Equation C32 may not actually represent the maximum possible value of the rate constant k, , and the related result in Equation C33 for (TV:),, 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 Precision of Product Concentrations and Experimental 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, . If the set of concentrations measured for the mth product have the mean value u, and standard deviation (3, , the data do not exclude the possibility that the product concentration increased from the initial value 6, -u, to the value (3, + u, at time t = A t . Taking this possibility to be the actual case for the measured products, the maximum value of the quantity (A, -A,,) is 20,. 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 o,,,or 2) concentrations below the limits of quantitation) k,< k,),,x,=x &0 P34) Under these circumstances and assumptions, the experimental half-life T'/t is greater than the value (T f ),. as follows: data indicate that the parent (for stable products at either 1) constant measured concentrations with standard deviation o,,,or 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 Concentrations Estimates Based on the Experimental Precision of Parent 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, . If the set of concentrations measured for the parent have the mean value ).L~and standard deviation (3, , the data do not exclude the possibility that the product concentration increased Page 115of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 from the initial value pp -q, to the value pp + (3, 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 pp and standard deviation cJT), k, I (kp)ma=f&. (C36) P Under these circumstances and assumptions, the experimental half-life T": is greater than the value (TVi ),, as follows: data indicate that the parent (for essentially constant parent concentrations with mean value &, and standard deviation CT~) (C37) References to Above: B' I. N Levine, "Physical Chemistry," McGraw-Hill (New York), pp. 498-501 (1978). B2 F. Daniels, et al., "Experimental Physical Chemistry", McGraw Hill (New York), p.131 (1962). Kinetic Calculations Indirect Photolysis Only two and after determine values of the the exposure the rate k, parent concentration (POand period of length A t . In this in Equation C8: P,) were case, no recorded: these data reflect least squares regression is the time possible before to k,t=-ln ; V) (1 0 However, the two measured for PI and PO are with in experimental final), thus, equation C36 is used error (1427 rig/m initial vs. 1432 rig/ml Page 116 of 158 -- BACK TO MAIN 3M Environmental Laboratory Report No. W2775 k, I (kP),, = 20, (C38) I+ A t Solving for the observed rate using 167 hours for At, 1479 for CLpand 20.71 for 0, gives a value of 1.68 x 10m4hi'. The rate of photolysis in the reactor k, is related to the actinic rate of photolysis k, by k ACT (CW where I ACT= 261 w/m2 is the actinic solar intensity intensity is I, = 680 w/m*. This gives (at 45" south latitude) and the measured reactor k ACT= 1.68x1o-4 ll-' = 6.44~10-~ hr-I For samples under constant illumination, the reaction rate and half-life are related by Equation C9: However, the actinic halClife is three times larger, according the standard eight-hour leads to exposure day. This (indirectphotolysis)T A:;= y = 3.7 years Pw ACT Page 1170f 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 1180f 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 PHOTODEGRADATION STUDY: Acquisllion In*tNme"t: Method: H606PFOS.m Hlllary HP1100 MSD Acquisition Sequence: HO60900.s Diredoy HO60600 PFOS in Fe203 SAMPLES AND SPIKES -ha leakedI" photoreactor Batch HO608W HOW600 HOW600 HO606W HOWBOO HOW600 HO60600 HO60800 HO60600 HOW8W File HILLW23.D Sample IDS 053,OO?FDSfw,l HlLLO024.D 053,WPFDS,e-O2' HILLO025.D 053,OWFD%-O3 HILLW26.D 0531wPFDSf&4 HILLW27 0 0531ooPF0%-05' HlLLO026.D 0531WPFDSfeo6 HILLO029.D 053,OOPFDS,e-O7 HILLW30 D 053,wPFDS+O6 HILLm1.D 053,wPFDSf&,9 HILLW32.D 0531OC+`FDSfe-,O Exposun, Expaed: with k02 Sample Oescdp(ion Mab-ix blank HO60600 HOM)BW HO60800 HOM)66) HO60800 H060600 HO60600 HO606OO HO60600 HO-50600 HILLO936.D HILL0937.D HlLLOtIX5.D HILLO039.D HlLL@MO.D HILLOO41.D HILLO042.D HILLOO43.D HILL0044.D HlUOO45.D 053,OOPFDSfe-1, 053,OO+`FDS`e-12 oS31wPFDSfe,3 0531WPFDSfe-14 O531OW'FOSfel5 0531OOPFO%-,6 O531ooPFOSfe17 053,WPFOS`e16 053,OOPFOSfe19 0531WPFOS`e-20 HOW6Wb HO60600b HO606Wb HO@,BWb H0606Wb HO608Wb HO606Wb HOWBWb H0606OOb H0606Wb HILLOO57.0 O531OOPFOSf%21 HILLW56.D 053,OC+`FOS`e22 HtLLMH9.D 053,wPFOSfe23 HILLN5O.D 0531wPFD%-24 H9J.0061 .D O531ooPFOSfe-25 HlLLOC62.D 0531wPFDSfe26 HILL0063 D 053,WPFDS,e27 HlUON4.D 0531O+PFOSfe-26 HILLCC65.D 0531OCi=FOS`e-29 HlLL0069.D O531OOPFOSfe-3O HOM)6Wb HOMl9OOb HC606OOb H0606Wb HC606OOb "0606Wb HO606Wb HO+OBM)b HOM)BC",b HO@,BM)b HtLL0070.D HILLO071.D HILL0072.D HlLLW73.D HILC0074.D HILLW75.D HILLW76.D HILL0077.D HlLL0076.D HILLW79.D 0531WF'FDS,e-31 053,WPFOS`e-32 053,ooPFOSfe-33 0531OOPFOSfe3-l 053,wPFO%-35 053,OtIPFOSfe36 0531wPFDSfe37 053,wPFOS,s36 0531OOPFDSfe-39 0531OCi=FOSfe-,O HO60600c H06~,800c HO+O60Oc HO6OK"X HILLOW1.D 0531OOPFOS`%41 HlLLOO92 D 0531wPFOSfe-42 HILLO093.D 053,OoPFO%-43 HILLOG94.D 0531OCPFOSfs44 PFBS RT 7.343 7.345 7.343 7.345 7.345 7.344 7.246 7.344 7.346 7.343 7.345 7.346 7.365 7.346 7.346 73-l 7.345 7.346 7.343 7.343 7.344 7.343 7.345 7.345 7344 7.344 7.345 7.343 7.344 7.344 7.343 7.344 7.345 7.344 7.344 7.343 7.344 7.343 7.34, 7.343 7.342 7.344 7.344 7.344 Area 729810 753475 719217 726369 761694 750671 729311 726356 726725 740934 Amount 47.4 474 47.4 47.4 47.4 47.4 47.4 47.4 47.4 47.4 73=x376 47.4 741709 47.4 732696 47.4 730153 47.4 741327 47.4 734472 47.4 726774 47.4 739616 47.4 724600 47.4 733694 47.4 70416% 47.4 707032 47.4 706466 47.4 706537 47.4 704183 47.4 70387, 47.4 692964 47.4 709370 47.4 692624 47.4 669916 47.4 694542 47.4 694026 47.4 666076 47.4 662590 47.4 69Mo4 47.4 677433 47.4 663247 47.4 679703 47.4 663760 47.4 665250 474 676776 47.4 681087 47.4 673430 47.4 660293 47.4 RT 0 6.244 6.246 6.252 6.246 9.243 6.245 9.245 6.247 6.242 0 6.244 6.26 6.25 6.246 6.245 6.245 6.246 6.246 6.24, 0 6.242 6.249 6.26, 6.245 6.242 6.244 6.263 6.247 6.242 6.275 6.243 6.263 6.267 625 6.243 6.244 6.262 6.263 6.245 0 9244 6.265 6.267 PFOA Area 0 132365 6633 6990 5719 13,115 132466 7194 7137 133299 0 127960 6535 6906 6596 13,561 130272 763, 6529 127509 0 12166, 7630 7130 6334 126515 126760 9013 76H 126407 Amaunt 0.00 21.37 0.79 0.64 0.56 21.25 22.12 0.66 0.66 21.91 Spke %Recov. 100% 96% lW% 96% Mm& STDEVl RSD or MeaMRPD 0.74 0.14 19% 21.7 4.0% 0.17 1.3% 0.w 20.99 96% 0.75 0.77 0.92 0.04 0.75 5.0% 21.61 96% 21.6 2182 96% 0.1% 0.93 0.85 0.76 19% 21.14 95% 000 20.66 97% 0.77 0.66 0.90 21.6, 97% 22.00 93% 1.01 0.83 21.66 96% 0.70 0.11 13.9% 211) 1.6% 9.92 19.2% PFOS RT 0 6.619 8.515 6.516 8.517 6.516 6 519 6.517 6.516 6.516 Area 0 6102337 21622604 21616917 171,6866 227,144, 24620799 21725069 21706653 25125316 0 8.516 8.519 6.519 6.519 9.518 6.516 6.516 6.516 6.616 0 5902627 21923392 21796225 2195,907 25042679 24618706 21509510 21567730 24604500 0 6.516 9.516 6.516 6.517 6.516 6517 9.516 6.515 6.497 0 5620726 20357271 20464573 20490608 23165904 23333090 19660149 20334305 2319366-l Amount 0.00 306.60 1491.36 1469.64 1030.32 1503.49 1749.55 1461.19 1476.49 1760.03 Spike %Recov. 102% 4% 65% 92% 0.00 302.51 lW% 1481.96 1477.36 1461.61 1773.47 99% 1777.38 lcm 1427.21 1472.94 1731.50 93% 0.W 303.53 1436.46 1453.69 1461.02 1736.79 1793.25 1369.39 1478.69 1769.14 100% 94% 113% 117% Mean/ STDEV I RSD .~ .o, Mean/RPD % Of Original 1490.5 0.1% 1626.0 15% ,4*9.* 02% 103% 102% 1473.6 10.67 0.7% 1775.4 02% 14.50.1 32% 102% 100% 1450.5 12.52 0.9% 1765.0 32% 1434.0 62% 100% 99% 4425 022 12,206 21.29 100% 6157 0.91 0.92 6493 097 0.05 7922 0.66 5.5% 123536 2193 96% 21.9 124606 21.93 96% 0.0% 6793 1.03 1.01 65.59 0.98 5% 126016 2212 93% 0 6.517 6.519 6.516 8.517 6.517 8.516 6.516 6 514 6.517 0 5546976 20126127 2W6912, 20246479 22967407 22905766 20074759 23026136 0.00 310.67 1477.1, 1463.63 1507.21 1611.64 1761.67 ,490 74 1469.36 1787.93 102% 106% 96% 101% Mug.3 15.64 ,.,% 1796.7 17% 14uo.o 1% 103% 102% 0 0.w 0 0 0.00 120583 21.33 100% 6.517 5445566 305 65 101% 9154 0.65 0.89 6.517 19903977 1516.97 1496.8 9010 0.61 0.11 6.518 19916612 1499.45 23.54 104% Page 119of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 PHOTODEGRADATION STUDY: Acq"db" Melhod: HemPFDS.rn Inrtrument: Hilky HPIIM) MS0 Acq"1Sitionseq"em: Hoem00.s Dlredory: tmom PFOS in Fe,4 SAMPLES AND SPIKES -VP, leaked1" phDtorea*r Bach File H06080c.2HIuw95 HOM)80oc "ILLoces.0 SampleD# D 0531oopF0sfE.45 o531owFosfe46 H0608Wc HIUoo97.D 0531owF0sf~7 H060800c HLLoo98.D 053,owF0%-48 HowJB00c HILLoa93.D 05310ofF0.%-49 HOwxWc HlLL0103.D o531ocPFosf*5n EXpol"n, iha 0: wilh t&O2 Sample Dsscnpl~wr sampleblp HOM)800c H0608DC.z HoeoBo& "mm tiOM)BWc H0608ooc "0608m HowBrn "060SOC.z Ho6oBm HIUOlcM D o531ooPFosfe-51 HlLL0105.D O531OOPFOSfe-52 HIUO1OG.D o531owFosfe53 HlLL0,07.D o53,wFosfe-54 HILLO,OSD O531OWFOSfe-55 HIu0109.D o531ooPFosfe56 HIu0,10.D 0531owF0sf.3.57 HIuO111 .D o531ooPFosc5E HU0112.D 0531OCf'FOSfe59 HILl.O113.D 05310oPF0.%-60 PFBS RT 7.344 7.345 7.344 7.347 7.266 7.268 Area 685687 67361, 676850 664950 673105 674644 7368 7.37 7.368 7.37 7.37 7.368 7.368 7.368 7.368 7.369 675398 675769 682028 679727 676568 673347 671884 672374 7.350 0.010 0.1% 701Oc9 27118 3.9% Amount 474 47.4 47.4 47.4 47.4 47.4 RT 8.265 8.248 8.247 8.268 8.266 8.258 47.4 0 47.4 8267 47.4 8.288 47.4 8.288 47.4 8.287 474 8266 47.4 8.268 47.4 8.289 47.4 8.288 47.4 8.255 PFOA Ama 10206 119509 122929 9626 9332 12,264 0 lM129 9113 8159 8982 124840 1POll e-496 8167 12255 &ncunt 1.0, 21.32 21.95 0.96 0.89 21.61 spike %Reco". 95% 98% 97% Mmd STDEV, RSD or MeardRPD 12% 21.5 2.4% 0.92 8.2% RT 8.518 8.518 8.517 8.52 8.519 8.541 0.03 0 21.37 100% 8.522 0.82 9.76 8.541 0.65 0.10 8.543 0.8, 12% 8.543 22.33 101% 22.1 8.54 2,92 99% 1.9% 8.541 0.73 0.70 8.541 0.67 9.0% 8.54 22.2, 101% 8.54 98% 1.6% 1.6% PFOS Area 19308521 22630822 22709847 19586256 196931.92 222S712, Amount 1472.10 1825.69 Iw2.07 1511.83 1497.87 1780.39 SPkn %Recm. 108% 107% 91% Mmn/ STOW / or MeanmPD 1.6% 1823.9 02% 1504.8 0.9% RSD % Of ongim 104% 0 5433257 19694996 ,9502085 19442468 22424057 22002669 19373620 19461929 21972361 0.00 307.74 1471.30 1458.4, 1461.58 1803.03 1766.0, 1468.36 1474.24 1790.60 101% 112% 100% 105% 1463.0 6.72 0.5% 1784.5 2.1% 1471.3 0.4% 101% 102% 97% 21.1% Page 120 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 PHOTODEGRADATION Acquisition Method: H608PFOS.m Instrument: Hillaty HP1100 MSD Acquisition Sequence: H060800.s Directory: HO60800 STUDY: PFOS in Fe,03 Inj Date 6/a/2000 6/8/2000 6/8/2000 6/8/2000 6/9/2WO 6/g/2000 6/9/2OW 6/9/2OW 6/g/2000 22:36 2258 23:19 23:41 0:02 0:24 0:45 1:07 1:28 6/g/2000 6/9/2OW 6/g/2000 6/g/2000 6/g/2000 6/g/2000 6/9/2OW 6/g/2000 6/g/2000 IO:49 1l:lO 11:32 11:53 12:15 12:37 12:58 13:20 13:41 6/g/2000 6/g/2000 6/g/2000 6/9/2OW 6/g/2000 6/g/2000 6/9/2000 6/g/2000 6/9/2OW lo:49 11:lO 11:32 11:53 12:15 12:37 12~58 13:20 13:41 6/g/2000 23:02 6/9/2OW 23:24 6/g/2000 23:45 6/10/2000 0:07 6/10/2000 0:28 6/10/2000 0:50 611012WO I:11 6/10/2000 I:33 6/10/2000 154 6/9/2000 23:24 6/g/2000 23:45 PFBS PFOA Batch HO60800 HO60800 HO60800 HO60800 HO60800 HO60800 HO60800 HO60800 HO60800 File HILL0012.D HlLLOO13.D HILL0014.D HlLLOO15.D HlLLW16.D HILL0017.D HILL0018.D HILL0019.D HILL0020.D SampleName 0002842-00 00028-42-01 0002842-02 00028-42-03 0002842-04 00028-42-05 00028-42-06 00028-42-07 00028-42-08 H060800 HO60800 HO60800 HO60800 H060800 HO60800 H060800 HO60800 H0608Wb HO60800b H0606OOb HO60800b H060800b H060800b H060800b H0608OOb HO60800b H060800b HO608OOb HO608OOb H0608Wb H060800b H060800b H060800b H060800b HILL0046.D HILL0047.D HILL0048.D HILL0049.D HILLO050.D HILL0051.D HILLO052.D HILL0053.D HILLO054.D 00028-42~DO 0002842-01 0002842-02 00028-42-03 00028-42-04 0002842-05 00028-42-06 0002842-07 00028-42-08 HILL0046.D HILL0047.D HlLLO048.D HILL0049.D HILL0050.D HILL0051.D HILL0052.D HILL0053.D HlLL0054.D 0002a42-00 00028-42-01 0002842-02 00028-42-03 0002842-04 0002842-05 0002842-06 00028-42-07 0002&42-08 HILL0080.D HlLLO081.D HILL0082.D HILL0083.D HILL0084.D HILL0085.D HILL0086.D HILL0087.D HILL0088.D 0002842-00 0002842-01 0002842-02 0002642-03 0002842-04 0002842-05 0002842-06 0002842-07 0002842-06 H060800c H06080Oc HILLO081.D HILL0082.D 0002642-01 0002842-02 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 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 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 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 7.342 7.344 674740 672211 CONC., nglmL 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 a.241 Area 0 7620 13972 23922 37019 46031 71600 115065 171633 47.4 7.693 2301 47.4 8.239 8369 47.4 8.243 13944 47.4 8.242 25711 47.4 8.245 36556 47.4 8.246 46576 47.4 a.244 70559 47.4 8.243 116203 47.4 8.243 47.4 0 0 47.4 8.239 8369 47.4 8.243 13944 47.4 8.242 25711 47.4 6.245 36558 47.4 a.246 46576 47.4 8.244 70559 47.4 8.243 116203 47.4 8.243. 169085 47.4 8.273 4987 47.4 8.244 10410 47.4 8.25 15587 47.4 a.244 27492 47.4 8.244 35743 47.4 8.243 44448 47.4 a.244 67333 47.4 8.243 111348 47.4 8.241 166510 47.4 8.244 10415 47.4 8.25 15587 Measured CONC., nglmL 0.00 0.95 2.09 3.76 6.06 7.64 12.04 19.96 30.05 0.05 1.09 2.09 4.14 6.06 7.89 12.05 20.32 29.84 0.00 0.87 I.87 3.91 5.83 7.65 11.80 29.54 0.37 1.34 2.30 4.51 6.06 7.60 12.01 20.02 30.64 1.08 2.05 Target CONC., nglmL 0.0 1.0 2.0 4.0 6.0 8.0 12.0 20.0 30.0 0.0 1.0 2.0 4.0 6.0 8.0 12.0 20.0 30.0 0.0 1.0 2.0 4.0 6.0 8.0 12.0 20.0 30.0 0.0 1.0 2.0 4.0 6.0 8.0 12.0 20.0 30.0 1.0 2.0 % Recovery 95% 104% 94% 101% 95% 100% 100% 100% PFOS RT 0 8.513 8.515 8.517 6.517 8.517 8.516 8.518 8.516 Area 0 3943772 9148149 13409846 17231633 19548066 21969761 23842895 25717031 109% 105% 103% 101% 99% 100% 102% 99% 8.518 8.516 6.517 8.517 8.518 8.519 8.518 6.517 8.517 24058 3879532 6929180 13045408 16535546 18881956 21030863 22787153 24622440 87% 94% 98% 97% 96% 98% 100% 98% 8.518 8.516 8.517 8.517 8.518 8.519 8.518 8.517 8.517 19350 3879532 8929180 13045408 16535546 16881956 21030863 22787153 24622440 134% 115% 113% 101% 95% 100% 100% 102% 8.519 8.515 8.517 8.517 8.516 8.516 8.517 8.517 a.514 22614 3724312 a423870 12233477 15625838 17778972 19858313 21572553 23298549 108% 103% 8.515 8.517 3724687 8423870 CONC.. ng/mL 0.00 190.00 533.59 822.50 1123.34 1322.35 1536.55 1767.48 1985.77 0.00 188.17 521.14 810.00 1084.32 1295.57 1478.60 1677.19 1883.19 0.00 188.12 525.96 620.91 1103.13 1322.30 1513.87 1723.99 1945.22 0.00 193.61 520.50 815.59 1105.45 1288.02 1527.08 1691.00 1932.87 192.02 523.95 Target CONC.. nglmL 202 506 810 1113 1316 1518 1720 1923 % Recovey 94% 105% 102% 101% 100% 202 506 810 1113 1316 1518 1720 1923 202 506 810 1113 1316 1518 1720 1923 97% 98% 97% 96% 98% 101% 202 506 810 1113 1316 1518 1720 1923 202 506 96% 103% 101% 99% 98% 101% 98% 101% 95% 104% Page 121 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 PHOTODEGRADATION Acquisition Method: H608PFOS.m Instrument: Hillaty HP1100 MS0 Acquisition Sequence: HO60800.s Directory: HO60800 STUDY: PFOS in Fe203 PFBS Inj Date 6/10/2WO 0:07 6/l O/2000 0:28 6/10/2000 050 6/10/2000 I:11 6/10/2066 I:33 6/I O/2000 I:54 Batch H06080Oc H060800c HO6080Oc H060800c HO6080Oc H06080Oc File HILLO083.D HILLO084.D HILL0085.D HILL0086.D HILL0087.D HILLO088.D Sample Name RT 00028-42-03 7.343 0002842-04 7.343 0002842-05 7.342 00026-42-06 7.345 00028-42-07 7.344 0002842-08 7.341 6/10/2000 11:15 HO6680Cc HILLO114.D 00028-42~DO 7.37 6/10/2000 11:37 H060800c HILL01 15.D 0002842-01 7.37 6/10/2000 1158 HO6080Oc HILL01 16.D 00028-42-02 7.368 6/10/2000 12:20 HO6080Oc HILL0117.D 0002842-03 7.367 6/10/2000 12:41 H060800c HILLOl18.D 0002842D4 7.369 6/10/2000 13:03 H06080Oc HILLO119.D 0002642-05 7.369 6/10/2000 13:24 H06080Oc HILL0120.D 0002842-06 7.367 6/10/2006 13:46 HO6080Oc HILL0121.D 0602842-07 7.369 6/10/2000 14:07 H06080Oc HlLLO122.D 0002842-08 7.369 7.349 Curves: PFOS=quadratic. ignore origin, IS talc 0.010 PFOA=linear, ignore origin, IS talc 0.1% Area 668276 672097 660541 667169 658291 648481 654534 651852 656141 645838 848666 663314 642005 684770 24348 3.6% CONC., ng/mL 47.4 47.4 47.4 47.4 47.4 47.4 47.4 47.4 47.4 47.4 47.4 47.4 47.4 47.4 47.4 PFOA RT 8.244 8.244 8.243 8.244 8.243 8.241 Area 27492 35743 44448 67333 111348 166510 Measured CONC., nglmL 4.29 5.86 7.42 11.89 20.01 30.76 0 0 0.00 8.275 10552 1.15 8.273 15559 2.12 8.288 25641 4.07 8.269 36410 6.09 8.289 46413 8.13 8.268 88399 11.94 8.269 106948 19.30 8.289 157620 29.83 Batch 1: r2=0.9980 Batch 2: r2=0.9989 Batch 3: r2=0.9988 Target CONC.. nglmL 4.0 8.0 8.0 12.0 20.0 30.0 0.0 1.0 2.0 4.0 6.0 8.0 12.0 20.0 30.0 % Recovery 107% 98% 93% 99% 100% 103% 115% 106% 102% 101% 102% 100% 97% 99% PFOS RT Area 8.517 12233477 8.516 15625838 8.516 17778972 8.517 19866313 8.517 21572553 8.514 23298549 Measured CONC.. nglmL 824.54 1120.95 1308.40 1555.04 1725.14 1978.13 8.644 23104 0.00 8.541 3810404 189.83 8.54 8157669 520.56 8.538 11805802 813.91 8.542 15046876 1088.88 8.541 17005557 1300.48 8.541 19943147 1504.92 8.542 20821672 1652.91 8.542 22293131 1920.01 Batch 1: r2=0.9997 Batch 2: r-2=0.9994 Batch 3: r2=0.9985 Target CONC., ng/mL 810 1113 1316 1518 1720 1923 % Recovery 102% 101% 99% 102% 100% 103% 202 94% 506 103% 810 100% 1113 98% 1316 99% 1518 99% 1720 96% 1923 100% PFBS PFOA CCV Standards: lni Data 6/g/2000 630 6/g/2000 18:22 8/10/2009 6:35 CONC.. Batch File Sample Name RT Area nglmL RT Area HO60800 HILLO034.D 0002842-05 7.345 722173 47.4 8.243 46842 HO608OOb HILL0067.D 0002842-05 7.344 679595 47.4 8.242 45748 H06080Oc HILLO1Ol.D 0002842-05 7.384 671958 47.4 8.262 45521 Measured CONC.. nglmL 7.67 7.74 7.62 Target CONC.. nglmL 8.0 8.00 8.00 % Recovery 96% 97% 95% PFOS RT Area 8.517 19569171 8.517 18214719 8.517 17443139 Measured CONC., nglmL 1302.09 1310.20 1276.45 Target CONC.. nglmL 1316 1316 1316 % Recovery 99% 100% 97% Page 122 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 PHOTODEGRADATION Acquisition Method: H608PFOS.m Instrument: Hillaty HP1 100 MSD Acquisition Sequence: H060800.s Directory: HO60800 STUDY: SOLVENT BLANKS PFOS in Fez03 Inj Date 6/8/2000 2153 6/8/2000 22: 15 6/Q/2000 1:50 61912000 2:ll 6/Q/2000 6:OQ 6/Q/2000 652 6/Q/2000 14:03 6/Q/2000 14:24 6/Q/2000 l&O0 6/Q/2000 18:43 6/l O/2000 2: 16 6/l O/2000 2: I6 6/10/2000 2:37 6/l 012000 6: 13 6/10/2000 656 6/10/2000 14:29 Batch HO60600 HO60800 HO60800 HO60800 HO60800 HO60800 H0608OOb H060800b H060800b H060800b H060800b HO60800c HO60800c HO60800c HO60800c HO60800c File HILLOO1O.D HILLOOll.D HILL0021.D HILL0022.D HILL0033.D HILL0035.D HILL0055.D HILL0056.D HILL0066.D HILL0068.D HILL0089.D HILL0089.D HILL0090.D HILLO1OO.D HILL0102.D HILL0123.D Sample Name Meoh Blk 7:l Meoh: H20 7:l Meoh: H20 711 Meoh: H20 7:l Meoh: H20 7:l Meoh: H20 7~1 Meoh: H20 7:l Meoh: H20 7:l Meoh: H20 7:l Meoh: H20 7:l Meoh: H20 7:l Meoh: H20 7:l Meoh: H20 7:l Meoh: H20 7:l Meoh: H20 7:l Meoh: H20 PFBS PFOA Average Area of LOQ RT Area Areaof IS RT Area std RT 0 693337 8.271 2021 7620 0 0 693337 8.288 1559 0 0 693337 8.265 1525 7620 0 0 693337 8.321 I723 7620 0 0 693337 8.272 1112 7620 8.522 0 693337 8.253 2112 7620 0 0 693337 6.244 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 6.273 4119 8369 0.517 0 693337 8.273 4119 10415 8.517 0 693337 8.271 4020 10415 8.519 0 693337 8.286 4536 10415 8.516 0 693337 8.29 3830 10415 8.542 0 693337 8.297 3481 10415 8.541 SOLVENT BLANKS (WITH I.S.) Inj Date 6/8/2000 6/Q/2000 6/Q/2000 6/10/2000 22:36 lo:49 23:02 II:15 Batch HO60800 HO60800 H060800b HO60800c 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 PFOA RT Area 47.4 0 0 47.4 7.893 2301 47.4 0.273 4987 47.4 0 0 Measured CONC., nglmL 0.00 0.05 0.37 0.00 RT 0 8.518 8.519 8.544 METHOD BLANKS PFBS PFOA Measured CONC., Inj Date Batch File Sample Name RT Area RT Area ng/mL RT 6/Q/2000 2:33 HO60800 HILL0023.D 0531OOPFOSfe-01 7.343 729810 47.4 0 0 0.00 0 6/Q/2000 7: 13 HO60800 HILL0036.D 0531OOPFOSfe-11 7.345 734370 47.4 0 0 0.00 0 6/g/2000 14:46 H060800b HILL0057.D 0531OOPFOSfe-21 7.344 704168 47.4 0 0 0.00 0 6/Q/2000 IQ:26 H060800b HILL0070.D 0531OOPFOSfe-31 7.343 694542 47.4 0.275 4425 0.22 0 6/10/2000 2:59 HO60800c HILL0091.D 0531OOPFOSfe-41 7.342 676778 47.4 0 0 0.00 0 6/10/2000 7:40 HO60800c HILL0104.D 053IOOPFOSfe-51 7.368 675398 47.4 0 0 0.00 0 PFOS Area 0 0 0 0 20277 0 0 0 21641 21052 18503 18503 23079 23085 20791 20802 Area of LOCI std 3610404 3610404 3610404 3610404 3610404 3610404 3610404 3610404 3610404 3610404 3610404 3610404 3610404 3610404 3610404 3610404 PFOS Area 0 24058 22614 23104 Measured CONC.. ng/mL 0.00 0.00 0.00 0.00 PFOS Area CONC., ng/mL 0 0.00 0 0.00 0 0.00 0 0.00 0 0.00 0 0.00 Page 123 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 Analysis of PFOS Photodegradation Study in Synthetic Humic Water PFBS samp* I.D. O424wpFClSdl D8sedp4bn Day 0 Samples Sample - 28 HO42ZBS"W.M 27 H0428SHW.M 28 HO42ZBSHW.M 29 H0428SHW.M Dab Rk hshwm28.0 hshwoo27.0 hshwo428.0 hthwOO29.0 3etmttloll mm (M,m,"s) PeakArea 3.15 642072 5.16 647618 5.15 645518 5.15 aso,, o424o(FPFos-o5 042400.PFclsa o424oGPFos47 Matrix Blank hiabix Blank Spike Matrix BlankSpike 30 H0428SHW.M 31 H0428SHW.M 32 H0428SHW.M hrhwoo30 0 hshw3o31.o hshwJo3*.0 5.13 629451 5.15 638531 5.18 631042 04*400-PFclS-08 04.2400.PFOS.09 MiUlQ Sample M~lliQ Sample X2 33 H0428SHW.M 34 Ho426S"W.M hshwQo33Jz hshwooY.o 3.16 840761 5.16 637293 042400.PFOS-10 o424wPFos-ll ham Spike Milli(l Spike m 35 H0428SHW.M 38 H0428S"W.M hshwoo33.0 twhw0038 0 5.16 643696 5.16 636745 99122-14905 o4*4oo-PFos-12 042400-PFOS-13 042400-PFOS.14 042406PFOS.18 S,d - 20 "g/ml 36 Exposed Samples Sampls 40 Sample dupkcate 4, Sample triplicate 42 SampleSpike 43 H0428SHW.M Ho428SHW.M HO4ZBSHW.M H0428SHW.M "0428SHw.M hshwo038.0 hsilwoo40.0 hshw041 0 h*hwoo42.0 hShw0043 0 516 633697 5.16 625154 6.16 640042 5.16 619735 5.16 646201 O424M1PFoS.la 042400.PFOS-17 042400-PFOS-18 Matrix Blank MakixSlankSpiks MabixBlankSplke 44 "0428S"W.M 48 Ho428SHW.M 46 H0428SHW.M hShWO044.0 h*hwoo45.0 hShWO048.0 6.16 609204 5.16 621745 6.16 625536 04240+PFOS-19 0424OSPFOS-20 M~lliOSample MilhP Sample #2 47 H0428SHW.M 48 H0428SHW.M hshwo047.0 hShw0048.0 5.16 636439 5.16 841755 0424OWFOS-21 M24owFOS.22 MilliQ Spike MIIIP Spike e* 49 H0428SHW.M 50 H0428SHW.M hshwoo49.0 hshwo030 0 6.16 641805 5.16 636055 99122-149-05 Ski - 20 nghll 32 H0426SHW.M hshwW52.0 5.1, Unexposed Samples 0424MPFOSd3 Sample 54 H042aSHW.M hshw005.i 0 5.16 042400-PFOSSa-m24pdlueplicate35 H0428SHWh.MehwW35.0 5.16 o424mPFcls-23 Sample trlpkcale 54 H042aSHW.M hshw0056.0 5.16 042400.PFOS-28 Sample Splks 57 H042aSHW.M hshvao37.0 5.16 635249 649465 65,111 640505 629625 0424~~PFOS-27 0424OC-PFOS-28 042400.PFOS-29 MatrixBlank MatnxBlankSp~ke M&wxSlankSpike 38 H0428SHW.M 59 H042aSHW.M 60 H042aSHW.M h*hvm58.0 hShw0059.C h*hWOO60.0 6.16 632209 5.16 620603 5.16 702086 Mun S.D. %RSD N= PFOA Wmtlcm mm :MindQs) PeakArea consntntkn (twq (@A) Accuncy (Muun.j/ Ncdid) Men S.D. Y.RSD 5.71 32436 5.71 30491 3.71 30736 5.71 49,826 5.71 21518 3.71 47513, 6.72 482332 5.71 32042 5.71 30456 5.71 485342 5.71 486523 5.72 396048 SaL ecx. BaL 25.31 eat. 24.14 24.51 tx& BQL 24.67 24.83 20.05 97.4% 92.6% 94.3% 94.9% 96.5% lW.2% 5.71 30110 6.71 29721 5.71 30626 6.71 300170 sex. SaL ea. 23.44 5.71 23062 SOL 5.71 484021 X6" 5 71 492545 . 25.04 5.71 3oQ15 v.x 5.71 30021 @a 5.71 496314 3.71 49,959 23.24 28.32 5.72 402657 20.40 97.6% 94.6% 96.3% 97.1% 97.4% 1020% 5.71 31169 3.71 30972 5.71 31017 3.71 510519 5.71 20952 5.7, 490376 3.71 492894 6aL Bat. BPL 23.9, SaL 24.93 zs.06 99.9% 95.9% 96.4% PFOS 3.87 5.8, 6.6, 5.67 5.86 6.6, 5.67 667 5.6, 6.87 5.6, 5.67 2834363 2842217 2792380 3696527 3615 669426 685595 2834603 2905256 3554759 3339849 535636 5.67 2865272 5.67 2818350 5.87 2779726 3.87 352,102 5.83 3969 567 699807 6.87 897911 6.87 2791391 587 2861452 5.8, 3469470 6.67 3538816 5.8, 543565 5.67 2902100 6.87 2897273 5.87 26Q8100 5.67 3576627 5.65 5oa5 3.87 683248 5.67 713930 'IO0.62 100.90 99.14 127.6, aal. 24.86 24.73 100.83 103.12 126.06 125.54 r9.44 101.36 QQ.QR 98.69 '15.09 ml. 23.23 25.16 m.,c! 98.22 12X,6 125.42 19.7, ~03.0, 102.84 w2.80 126.84 ml. 24.64 23.73 93.2% 93.4% 91.6% 105.4% 100.22 0.95 0.9% 96.6% 93.1% 93.2% 95.5% 93.0% 91.0% 97.2% 93.9% 92.6% 91.4% 96.4% 24.79 0.10 101.88 1.76 125.80 0.37 100.01 1.33 1.3% 97.0% 96.6% 91.8% a8.2% 102.3% 106.7% 96.6% 26.20 0.03 97.18 2.75 124.59 1.18 95.4% 95.2% 95.2% 92.1% 102.89 8.11 0.1% 94.8% 2519 99.0% 0.77 Page 124 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 Analysis of PFOS Photodegradation Study in Synthetic Humic Water sample LD. sampi. De~criptk.. 042400-PFOS-30 Mw2 Sample 0&24w-PFOS31 MooiaSample#2 o424oo-PFos-32 0424O+PFOS-33 Milwaspike MilkO Spike #2 R*pKlC.SSi"p k4h.d 61 "0426SHW.M 62 H0428SHW.M 63 H0428SHW.M 64 HO4ZBSHW.M Data Fn. hshwD0610 hshww62.0 hrhwm63.0 hshwoo64.0 t.t.ntbl lhl. -, PFBS Pdc Are. Men S.D. XRSD a= 5.16 5.16 5.16 5.16 622097 639696 652034 649424 63L156d 15334 24% 35 R.gnr.l.n , "al". PFOA R.9.lltk.l h fWwtes) P*rkAr*a 5.71 5.7, 30924 30066 1 Acc"m - Conmba6cm (anslna S.D. (@ml) (ppb) womkul) KRSD SQL BaL 5.7, 502917 5.71 513718 26.58 26.14 98.4% 100.5% Linear: include 2wo: equal weigmn; 0.9999 *xtwmI quant PFOS 99122-149-w 99122-149-0, 99122-14902 99122-149-m S!312*-14904 99122-149-05 99122.14966 99122-149-07 99122-14946 99122-149-w 99122-14941 991222-149-02 SQ,22-14903 99122-149-04 93122-149-06 99122-149-X 99122-14907 99122-14966 99122-149-w 99122-14901 99122-14942 99122-14943 99122-149-04 99122-14946 99122-14906 99122.14947 99122-14949 Calibration Standards 67 H0426SHW.M 66 H0426SHW.M 69 H0426SHW.M 70 H0426SHW.M 71 H0426SHW.M 72 H0426SHW.M 73 H0426SHW.M 74 H0426SHW.M 75 H0428SHW.M hrhvdo67.D hShw0DM).O hShw0069.0 hrhti070.D hshti71.D hshwW72.D hshw0073.0 hrhwW74 D hthwCO76.D 5.16 6.16 5.16 5.15 5.15 5.16 5.15 5.15 5.15 5 14 5.14 5.14 6.14 5.15 5.15 5.15 5.15 5.15 5.16 5.16 5.16 5.16 5.16 5.16 5.16 5.16 5.16 Mean S.D. XRSD 639959 636720 63647, 646599 636302 646676 640047 645546 635013 625063 626331 6,311, 62,035 634660 646610 646121 660067 636769 631240 632926 599675 660436 631303 649569 617262 643613 627944 63,666 14459 2.3% 636312 13416 21% 27 5.72 22452 5.72 6574, 5.71 53619 6.71 145261 5.71 203131 6.72 363606 5.71 960772 5.72 1665416 6.71 2704150 5.70 23431 5.70 66432 5.70 52613 5.70 143961 6.71 197967 5.7, 36,210 5.70 969267 6.7, 192,161 6.7, 2749173 6.7, 22791 5.72 65646 5.7, 52107 5.71 152237 5.72 204674 5.71 396507 6.7, 962510 5.7, 1951619 5.72 276,056 0.x 2.96 2.34 7.08 10.0, WI, 56.30 SS.OG 139.46 -0.44 0.:; 2.95 2.26 7.01 9.8" 18.59 50.74 56.95 141.18 -0.44 0.74 2.96 2.26 7.44 'lx,6 20.18 50.39 100.53 142.70 [ 296.3% 116.6% 1 ;4w& ..xdud.d .Xd"d.d 97.0% 100.6% 96.1% 1 93.0% .XCl"d.d 1 29;; excluded 1 140.2% .XdYd.cl 96.0% 66.0% 101.5% SS.S% I 94.5% .XCl"d.d 265.6% 112.9% 148 7% 101.6% 10.9% lW.B% 100.5% 95 I% excluded .xcl"d.d excluded 5.65 5.66 5.9, 5.9, 5.67 6.9, 5.67 5.66 5.6, 5.66 6.66 5.66 5.66 6.67 5.67 5.66 5.67 5.67 5.64 5 67 5.67 5.87 5.6, 5.6, 5.67 5.67 5.67 2376 26229 46442 120906 246212 51901, 139665, 26227?1 4063177 2361 26453 46259 lW643 245418 526991 1392427 2644469 4182790 4456 30602 4636, 12,946 262753 641223 1401576 2663426 4226607 0.60 1.61 2.15 4.iG 9 28 18.84 49.95 10*.21 144.73 8.51 0.60 7.52 2.35 4.63 9.t9 19.2" 49.68 100.98 148.25 0.51 0.87 1.50 2.22 5.03 9.79 19.63 60.02 '102.35 140.86 15*.0x 107.6% 95.7% 62.6% 94.2% 99.7% 100.2% 96.6% excludsc 151.7% 107.3% 92.6% 91.6% 96.0% 99.4% 101.0% 96.6% .xd"d.~ 159.3% ,1,.1x 100.6% 97.9% 96.1% 100.0% 102.4% 99.9% .xchd.c Page 125 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 Analysis of PFOS Photodegradation Study in Synthetic Humic Water PFBS Mun Page 126 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 RM(o6lSW) PFDS 6%203) Fk R6616Wl.D R6616WZD RMI16603.D Fz6616w4.D R6616WS.D R6616605.D R6616oo7.D R6616w5.D R66.160w.D RO616010.D RW16011.D R08166l2.D R66lWlJ.D ~w1W14.D ~66166150 RO6lWl6.D RC616617.D RW16616.D Rwl6619.D RWlW20.D RwlW21.0 RO616022.D RwlM23.D RwlWZ4.D RHW25.D Rwlw26.D RWlW27.D RO6lw260 RwlW29.D RO616630.D RWlW31.D RO616632.D RWlw33.0 RO6lWY.D RO616035.D RWlW35.D RO616637.D RO616035.D Ro616039.D R0616640.0 RW16641.D RO616642.D lW616MI.D Ro616o44.D RO616O45.D amp*kink blank lul99036.36.01 In 5f1I M 660365Ml1 h knl 5ul CWW4bOl h 5nI W 99636-36-91 h 5ml IM 99oS5-39.01 h 5nd &Ilk OSIMO-PFOW-101 mblx ML O6lMO-PFOSR1OZnmblxa(rlxblJp(r 0515OO.PFDSfa-103nmple~mpk1 OSlSWJ'FOSk-lOrdup . OSlWO-PF'OSlC-105q OSlW&PFDS+Z-166Ipk 0515W.PFDSfa-107s~kdu~ 051500PFDSk-lwwrdml 0515OlLPFOS%10@mn(roldup 651509PFDSlb110 cc+lfol sPL blank WI 99w699-61 Ill knl blank 051600PF~111 t?Mtxbtk 051506.PF0Sl4-1121TM1L~blkSpk G5lWO-FfOSf+ll3satTVk OSlWO-PFOSls-114duP 05156O-PFOSk-115k+6 051500.PFOSrs-116Vk 05lWO-PFOSle-117 %`Ad"D 05lYM-PFOSfe-115 EontrOi 0515W-pFOSk.119 wn(ml dup 051506-PF0SM-120~Mrolrpk bfank 6111WOW-39.01 in 6t~I blank 05090&ElFOSE-155 GC sample WWW-EIFOS&Y 56 GC s6S.Z blank 05wWEtFOS6167 GCr"@e WaWO-EtFOS&l66 GC umpb blank WWOO-EIFOSE-176GCsrmpb 0509W-ElF0SE-166 GC spik6 blmk 6ul wa36.2.%01 In !M #mk 0.00 0.00 0.00 0.00 0.w 0.00 0.97 1.01 I.W 045 120 12s 1.84 202 2.W 1.70 240 2.56 4.64 5.01 6.00 425 6.W 625 7.74 aw a.00 6.60 9.w 10.00 9.65 1o.m 1o.w a50 12.w 12.50 0.00 0.00 0.00 0.00 0.00 0.00 0.W 0.w 0.w 0.w 0.00 0.w 7.74 a.06 8.W 6.66 9.60 10.00 0.w 0.w 0.w 0.w 0.w 0.w 0.00 0.00 0.00 0.w 0.w 0.00 0.00 0.06 0.00 0.00 0.w 0.00 7.74 a.00 6.00 6.00 0.60 10.00 7.74 8.08 1.00 6.66 9.66 10 00 0.00 0.00 0.w 0.w 0.00 0.w 0.w 0.00 0.w 0.00 0.00 0.00 7.74 a.06 8.00 6.66 9.60 1O.W 0.00 0.00 0.w 0.w 0.w 0.w 7.74 6.W 6.W 6.66 3.60 1O.W 0.00 0.00 0.w 0.w 0.00 0.w 0.w a.66 0.06 0.w 0.w 0.w 7.74 6.W 6.00 6.66 9.66 IO.00 0.00 0.w 0.w 0.w 0.00 0.00 0.00 0.w 0.w 0.w 0.00 0.00 0.00 0x4 0.00 0.00 0.00 0.00 7.74 a.w 6.W 6.56 9.W IO.00 7.74 a.w 6.W 6.110 9.60 10.00 0.w 0.00 0.w 0.w 0.00 0.w 0.w 0.00 0.0 0.w 0.00 0.w 7.74 6.W a.00 6.56 9.60 1O.W 0.w a.00 0.00 0.w 0.00 0.00 7.74 6.06 a.00 6.60 8.80 10.w 0.00 0.00 0.00 0.w 0.w 0.w 0.w 0.00 0.00 0.w 0.w 0.00 7.74 a.06 a.00 .6.60 9.64 1o.w 0.w 0.00 0.00 0.w 0.00 0.w 0.00 0.00 0.00 0.00 0.w D.W 7.74 6.W 0.0 6.60 a60 IO.00 0.w 0.00 0.00 0.~0 0.w 0.00 0.w 0.00 0.00 0.00 0.w 0.00 7.74 6.W 6.00 640 0.66 1O.W 0.00 0.00 0.00 0.w 0.w 0.w ;:74 6.W 8.W 6.60 9.66 1O.W 0.00 0.w 0.00 0.00 0.w 0.00 0.00 0.w o.co ia0 lioc I.08 1.42 0.15 0.10 0% 2.17 2.55 0.30 020 1.M 5.42 7.12 0.76 0.50 4% a.67 11.38 1.20 0.w 7.z la.64 1424 1.50 1.W 0.M 0.w 0.w 0.w 0.w 0.K 0.w 0.w 0.00 0.00 0.w 8.67 II.39 1.20 0.80 7.x 0.00 0.w 0.00 0.w OS4 0.W 0.W 0.W 0.00 0.K 0.w 0.00 0.00 0.00 0.w 6.67 ll.JS 1.20 0.Q 7.X 6.67 11.39 1.20 0.66 7Zt 0.w 0.w 0.w 0.00 0-a 0.00 0.w 0.00 0.w 0.w 6.67 Il.39 1.20 0.80 72C 0.w 0.w 0.00 0.00 0.w 6.67 11.39 120 024 72C 0.w 0.00 0.00 0.00 o.oc 0.w 0.w 0.w 0.w o.oc 6.67 11.39 120 0.86 7.2l 0.00 0.w 0.w 0.00 o.ol 0.00 0.w 0.00 0.w 0.u 0.00 0.w 0.00 0.w OS4 6.67 11.39 1.20 0.66 7.2f 6.67 113 1.20 0.60 7.X 0.00 0.w 0.00 0.00 o.oc 0.w 0.w 0.w 0.w o.oc 6.67 11.39 120 0.60 71( 0.00 0.w 0.w 0.w 0.0x a.67 11.39 1.26 0.56 7.2c 0.w 0.w 0.w 0.00 o.oe 0.w 0.w 0.w 0.w o.oc 6.67 11.39 1.20 0.60 7.8 0.w 0-w 0.00 0.w 0.w 0.00 0.w 0.w 0.w 0.w l.67 11.39 IZG 0.66 72c 0.00 0.w 0.w a.00 0.w 0.00 0.00 0.w 0.00 0.w 6.67 11.W 1.20 0.w 7.20 0.00 0-w 0.w 0.w 0.01) 6.67 11.39 1.20 0.60 7.20 0.00 0.~ a.00 0.00 0.00 0.3 105 06 a2 9a la3 107 w 35 iof loo IW 102 67 130 63 95 fop 103 107 101 iaz Page 127 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 RMQ6IWO) PFOS (Fe2031 FRO Ro8lemI.o RM16002.0 Rrnlew3.0 Rml66M.D A~16003.0 mmom.~ RMlI)W7.D Ro6Iwm 0 RmlBQD9.D Rm16010.D RMiWl I.0 RmlWl2.0 RC616013.0 Rml6614.D RmlWI3.0 RWlWl6D RWIW17.D Rm1WlS.D RWlW1e.D Ro3lw2o.D RWIW21.D RmIw22.D RmlW23.0 RmlW24.0 RWlW23.D RmlW260 RMlW27.0 RWlW28.D RffiIW29.0 RC61WM.0 RWlW31.0 RmlW22.0 RmlW0p.D RmlW34.D RmlW33.0 RWlW26.D RmlW37.D RmlW36.D RmlW39.D RwIW46.0 RmIW41 .O RmlW42.0 RmlBM3.0 RmlW44D RW16043.0 San@t Name bhh b!mk I* 99w0-36-01 h SK4 2ul99O38-23.61 h 3fd 3ul WW&31101 h Sd 6ul9903b39-01 h snd Ioul SW363901 In M blank 03130&PFOSfs-101 r&=bf #r O313DQPFOSR-102mtrix blr SPk O3l3C+PFOSfe-lo3 VmPk 03136+PF0Sf~16464P O3lWO.!=FOsCe-lO3l!b O31300?FCSfb1006~6 O3IWO.F'FOSfe-lO7~plrdup 05130O.FF~XIe-1O3mNd 0313ObPFC~Sfe-108~~lroldu~ O3150O-FFCSI~-lIOrmtmlS~k blank 3u199033-39-01 in 5ml b!ank 05150t~PF066111 n!dIk bh 03160CPFC~Sle-112NlrlrMkrpk 63lSOGPFoSfc-lI3snwk O3130CPF06fe-114 duP O3lWO.PFOSte-ll3l1@ 0515oOPFOSfe-116 SPk 0515CGPFOSIc-II7 rPkdun 0515~PFOSb-1 I8 C&k O513oQPFOSIe-119 mnIr0l dup O5l3OO-PFOSC-l2Ocmdml~@ blank Cl WWb39-01 I" Lid blati MWOO-EFOSE-135 CX SamrIb 05090&EtF0SE-136 SC Spike blank OSWOO-EIFOSE-167 GC ssmpk 036960EIFOSE-169 Cc tampI9 blrnL 05696O.EIFOSE-179GCIanple 050900.EtF0SE-IQ SC rp(k9 Wnk 6ulWw839-01 h Hnl MM9 1 d B e ii i Ii 3 1" OtmmanCI i % t i g I 0.i 033 2 0.i 0%.00 a 102 I 61120.00 0.00 0.w 0.00 01.m 0.00 0.m 0.00 en ea 94 101 93 94 95 0.91 0.95 1.02 0.63 1.21 1.47 1.12 129 0.66 0.00 0.00 102 100 loo 93 101 101 101 I .ee 2.13 1.83 tat 2.32 2.49 2.16 2.90 026 028 1.67 S6 SB 98 SO 100 $9 9s 4.93 4.W 3.17 4.17 a.03 3.63 3.42 7.33 0.60 0.51 4.7I 101 102 102 63 IO2 101 103 7.59 a.38 7.73 aas e.a2 9.79 a.34 1127 1.24 0.78 7.19 too 99 ea 104 m 98 90 9.73 9.02 10.11 8.64 11.83 12.60 10.93 1424 1.43 1.01 6.93 100 101 101 113 loo la0 100 0.00 0.11 0.19 0.02 0.W 0.w 0.00 0.w 0.w 0.03 0.W 0.w 0.00 0.m 0.00 0.m 0.00 ea es 99 92 69 en 100 0.00 0.00 0.00 0x4 0.00 97 100 63 104 OS es 93 6.92 7.42 7.46 6.32 0.33 7.77 6.14 Il.33 0% 0.83 424 97 96 $5 101 W W a8 0.00 0.11 0.10 0.02 0.00 0.m 0.w 0.00 0.w 0.m 0.00 98 en 91 87 96 97 M 0.00 0.w 0.w 0.01 0.w 0.w 0-w 0.m 0.w 0.m 0.00 93 94 90 w 62 94 92 0.00 0.00 0.11 0.62 0.w 0.w 0110 0.00 0.W 0.W 0.00 I 96 PI 89 83 94 97 93 I 7.06 6.29 6.13 6.34 $20 6.42 8.77 11.65 1.14 0.82 4.39 93 93 aa a2 94 w 91 7.54 7.94 a.54 6.45 9.3a IO.49 8.W 11.1e 1.10 0.76 3.33 81 90 64 73 02 93 60 0.00 0.31 0.00 0.00 0.w 0.W 0.~0 0.m 0.00 0.w 0.w 93 96 92 vi 95 93 m 0.00 020 0.03 0.00 0.W 0.w 0.00 0.m 0.00 0.00 0.00 85 95 81 94 a4 94 a3 a.03 7.13 7.36 5.73 8.00 0.11 7.69 10.1 0.95 0.W 3.49 01 91 65 M 17 M 87 0.00 0.12 0.w 0.03 0.w 0.W 0.00 0.m 0.w 0.m 0.00 100 06 ee 113 ed w 98 726 7.36 7.46 6.43 8.97 6-W 6.05 10.45 l.w 0.w a.72 97 PI 07 89 97 w $7 0.w 0.00 0.w 0x4 0.m 0.00 0.m 0.00 0.00 0.w 0.00 a3 94 93 08 93 92 $4 I O.OO 0.08 0.w 0.04 0.00 0.00 0.00 0.00 0.w 0.w 0.00 08 101 $0 1m 99 *a 100 6.96 7.71 8.31 0.31 9.m 11.11 a.38 ii.00 1.13 0.75 6.96 I 102 100 $8 s3 IW em 100 0.00 0.w 0.00 0.00 0.w 0.w 0.00 0.00 0.w 0.m 0.00 101 103 103 110 102 102 102 0.00 0.00 0.w 0.07 0.00 0.W 0.m 0.00 0.w 0.00 0.00 I 103 107 98 73 104 103 I02 I 0.00 0.w 0.00 0.03 0.00 0.W 6.03 7.33 7.64 6.22 10.46 a.17 80.4020 110.090 01.w10 0.7m7 0a.0709 I 10S4I 1040 10S1U 19192 toS2S 1021 10917 I 1.23 7.62 7.66 6.33 921 6.21) 6.44 11.41 1.14 0.71 6.21 101 160 $6 107 IW 101 $6 0.00 0.31 0.00 0.00 0.00 0.W 0.00 0.23 0.w 0.0) 0.00 0.W 0.w 0.00 0.w 0-w 0.00 se se 9s a4 ee 101 98 0.00 0.00 0.00 0.m 0.00 96 93 97 93 9.3 se 97 6.60 7.47 7.37 6.34 &II9 u.w 0.23 10.92 1.11 0.w 6.16 103 91) IW 105 101 101 101 0.00 0.w 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 se 94 s4 70 94 93 93 0.30 6.61 6.96 5.90 8.08 7.26 0.00 0.00 0.w 0.m 0.w 0.00 07.0109 00-.m27 01-.0w0 0.w68 60.2010 I 10997 11927 1096 12025 19067 19033 10978 I 0.25 0.00 0.m 0.23 0.00 0.m 7.21 8.63 5.10 (1.33 8.09 8.62 70.8030 102..m03 01.2w3 00..m64 07..0307 I 8a3 a24 Met 15010 la93 696 19047I 0.00 0.00 0.00 0.w 0.00 0.04 0.W 0.w I I 026 0.w 0.00 046 0.00 0.m 0a.mm 00-.w00 0.wm 00..0w0 9974 lU923 9991 11027 6982 0931 930 8.40 7.16 7 .s3 1.70 Ma 8.93 6.72 li.26 1.w 0.78 3.35 101 103 103 94 103 S@ 101 0.00 0.W 0.00 0.00 0.m 0.m 0.W 0.m 0.00 0.00 0.w 101 101 96 90 99 ea 89 0.00 0.00 0.00 0.00 0.w 0.W 0.W 0.00 0.00 0.00 0.00 93 es 93 w 93 ei 93 7.91 7.78 7.46 me 0.23 a.13 0.36 1049 120 0.71 3.6Q 93 93 B3 $1 SE 04 93 0.00 0.00 0.w 0.01 0.00 0.00 0.m 0.00 0.w 0.00 0.00 63 94 95 64 94 93 94 6.76 7.47 7.66 3.79 3.47 9.73 7.84 10.37 1.W 0.83 8.63 104 102 101 W IO2 102 102 0.00 0.W 0.00 0.00 0110 0.00 0.m 0.00 0.00 0.m 0.00 97 w 92 01 95 94 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. PFOS photolysis LClMS 99122-149-03 PFOS photolysis LClMS 00028-42-01 0531OOPFOSfeO5 0531OOPFOSfeO6 GClMS R0614001.D R0614002.D R0614008.D R0614019.D R0614021.D 051500-PFOSfeO73 051500-PFOSfeO74 [ Description in SHW [ Failed Criteria 1 Cal Std 3-5 ppb 75 - 125% recovery in Fe203 Cal Std 1 - 1 oob rr Sample Triplicate Sample Spike 75 - 125% recovery >I 5% mean 75 - 125% recovery Analyte PFOA PFOA PFDS PFDS Blank Blank Blank Blank Blank Sample Duplicate 75 - 125% recovery 75 - 125% recovery 75 - 125% recovery 75 - 125% recovery 75 - 125% recovery LoQ< <LOCI <LOQ <LW Surrogate Spike analytes Surrogate Spike analytes Sanuarrlogatees Spike Surrogate Spike analytes Surrogate Spike analytes I-H perfluoroheptane perfluoro-2-octene volatiles volatiles I Value I Comments 142%, 140%,149% failed 3/3 injections 134% 1030 ppb 1503 ppb Solvent interference Solvent interference Solvent interference Solvent interference Solvent interference 25-50 ppb 0.9Oppb 0.18ppb 0.35ppb failed l/4 injections vial leaked vial leaked failed 6/7 spiked analytes failed 7/7 spiked analytes failed 6/7 spiked analytes failed 7i7 spiked analytes failed 7/7 spiked analytes blank greater than LOQ Referred detected" to as "non- Referred detected" to as "non- Referred to as "nondntecttadi" 051500-PFOSfeO86 051500-PFOSfeO87 051500-PFOSfeO90 051500-PFOSfeO92 051500-PFOSfeO96 051500-PFOSfeO97 051500-PFOSfelOO 99038-39-01 Spike Dup Spike Spike Blank Spike Spike Dup Spike Control Spike Cal check 75 - 125% 75 - 125% recovery recovery 75 - 125% 75 - 125% 75 - 125% 75 - 125% 75 - 125% recovery recovery recovery recovery recovery 75 - 125% recovery volatiles volattles volatiles volatiles volatiles volatiles volatiles All perftuorinated analvter; 59,69, 72, 69% -l,la,uu,sn+.-7. o nrnr failec f 7/l 1 spiked analytes 7361 I 32% ,?.A -r,-s ,.I", 1.3, ou, .sul/o failed 3111 spiked !d 6/l 1 spiked analytes analytes 73,70% failed 2/l 1 spiked analytes ' 71, 70, 70.61% failed 4/l 1 spiked analytes 72,73% failed 2/i 1 spiked analytes 69,71% failed 2/l 1 spiked analytes 62 - 74% failed 8/l 1 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 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 Data File: \\ETSWRCNERWRTAOOWILLOOlO.D 1.08: 1.04; i-00: 0.96; 0.92; 0.88; 0.84:: o.eoj 0.76: 0.72: 0.66: : 0.64; ,0.60: i 0.06; .0.52: 0.42 0.44; 0.40; MeOH Solvent Blank \VTSUX;EERU)\DATII\HOM)800WILLOOiO.D Page 2 1 1 2 3 4 6 6 7 8 9 10 11 nin Page 131 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 Data File: \\ET -DATAWO6O80OUlILLOOli.D Ll- \\ETSWACNER\MDIITAWO606OOWIU~.D i.0: 0.9: 0.8: 0.7: ; . ) 0.6: ! . . 0.6 Paz* 2 2PFoR Ion 413.00 \ i.20; i.10; 1.00; F; 0.90; 3 0.80; * 0.70; o&o-: 0.60; ., . ( . . , . . . , . . . . , . . . . 7.0 7.5 8.5 9.0 I%: Page 132 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 Data File: \\ETsuFIGNER\D \D13TA\H060@00W1LL0012.D Pace 2 \XETSWCtEPAmWTA~OOWILLOOi2.D 7.01 6.E: 6.S; 6.3; Mabix Blank 6.0; s.64 5.8; 5.3; 6.0; 4.0; 4.6: 4.3: 4.0: 3.G 3.ai: 3.3; 3.0; 2s; 2.6; 2.3: 2.0; i.& 1.5; 1.3; l.O! 0.8: O& 0.3-i , , I IIs,,, ~....,....I,...,....,....,....,....,,...,....(....~....,.... 1 2 3 4 6 6 7 8 9 10 11 in 6.0; 6.0: 3 4.0; 2 3.0; v p 2.0: 1.0: . , . , I, . , . I , . . . , 6.5 7.0 7.5 8.0 8.5 Hin Page 133 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 Data File: \~ETSWFICNanD\DCIT~WO608~WILLOOl4.D \\ETSWACNERU)\DIIT~V~EOOWIU~l4.D 8.0: 7.8; 7.6; Calibration Std Z 7.3: 7.0: 6.8i 6.5; 6.33 6.0: 5.8: as! 5.3; 6.0; 4.8; 4.6: ; 4.3: I 4.0; 1 3.8;' 3.q 3.3j 3.0: 2.8: 2.5; 2.3; 2.03 1.8; i.s{ 1.34 i,Oi 0.8; O.Sj 0.3; J. 1. .11. I. . . . .II . . . II. . . . . . . . . . . . . . . . . . . . ..)...........~. 1 2 3 4 5 6 7 in in 8 9 3 PFOS Ion 499.00 8.0: 3 7.0; ai Page 2 .I. .. . . . . . 10 Ii IOn 413.00 I.74 P 1.61 m' 1.6: 1.3: 1.2; 1.1: i.0: 0.9i 0.8i 0.7: 0.6; ~...;....,....,....,.... 7.0 7.5 8.0 8.6 9.0 ..,... , 1, , . . , . . , I . 7.6 8.0 8.5 9.0 9.5 nin Page 134 of 158 3M Environmental BACK TO MAIN Laboratory Report No. W2775 Data File: \\ETSIYIGHDnD\I#TFI\HO~~ILLOO2O.D 2.1; 2.0; Calibration Std 8 1.9; 1.8; i.7; 1.6; 1.5: 1.4; 1.33 1.2:; i.lj 1.0: 0.9; 0,s; 0.7; 0.6: 03: 0.41 0.3; 0.2; 0.i; .,..,....,..I..,..I..,....,....,....,.1..,.,~ I I 1 2 3 Y 1 PFBS 6.0; Ion 299.00 f-3 J \xsTsuhc~mrdwio6osoow ILLO020.D 4 5 . 6 7 s --. 3 PFOS - - -.---' Ion 499.00 2.0: pi3 (D' ii 1.6: 1.4: f ;:;j u 0,s; w 4+ 0.4: 0.2: 2 PFOh Pir(Q 2 Page 135 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 Data File: \\ETSUCICHER\D\DATA\H060840WILL0036.D 7.3; 7.0; 6.5 6.5+ 6.31 6.0: 6.6; 5.5; 6.3: 6.0; 4.84 4.6; 4.3; ; 4.oi Expored -167hrr Blank Fe203 No Peroxide ~\ETSWRCNER\mDClTR\HO608~WILLOO~.D f 3::; 3:o; 2.8; 2.5; 2.3; 2.0; 1.8; 1.6; 1.3; 1.0; 0.8; 0.5: 0.3; , ,, - ,, , I I . . . . . . . . . . . . . . . . . ..)................ 1 2 3 4 6 6 * I PFBS 7.0: 6.0: Ion 299.00m i: r: . . . . . . . . . . . ..`....I.... 7 8 9 10 6.0; ; ::' " .r > 2.0; 1.0: .,..,....,....,....`...., I, I 6.6 7.0 7.6 8.0 8.6 n Pilcc 2 11 Page 136 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 Data Filet \\ETSUACHERMDATRW~~~~WILLOOJ~.D 6.44 6.2; 6.01: 4.0; Exposed -167hR Blank Spiked Fe203 No Peroxide \`JZT6WXtER\fiIYITAVIO6O~OOXHILLOO37.D 4.6; 4.4; 4.2; 4.0; 3.8:: 3.6; 3.4; 3.2: 3.0: ; 2.& I 2.6; 2.4; 2.2j 2.03: 1.8; 1.6j 1.4; 1.2; i.0: I\ f 0.8; A 0.6: 0.4r 0.2j `.I..,,.,..,I....,...I.I,....,.~..,... III 2 II 3 4 6 6 .i.""`...I`L..-.2 8 k 9 .io. " Y IPFBS 7.0: 6.0; km 2vv.oom l-8 F: - 3PPDs 6.0: * * 4.0,: 6 2 3.0, r 2.0; 1.0; . , 6.5 2 PFOA 1.2j i.li 1.0; 0.9; 0.8i 3 o.r-; 6 0.6i 3 0.5; . I , I. . . , 7.0 7.1 n I . ,.. , 8.0 8.6 Ion 413.00 x co' K II . , . . . , .I .I , . , . .I ( 7.5 8.0 8.5 9.0 9.5 Hill Pace 2 I J `ii.. Page 137 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 1.7; Sample Fe203 No Peroxide i.6; 1.5: 1.4: i.3; i.2; 1.1; ; i.0: 0.91 0.8.: 0.7: 0.6: 0.6; 0.4j 0.3: 0.2: 0.1; . I . II , . I III . , . . II , 2 3 . . ., . 4 * I Fms I 7.0: 6.0; Ion 299.00 R r! . , . 5 . , . , 6 7 3 PFOS 1.2: 1.6: i.4; 1.2: T i.0: fj 0.8; > 0.6: 0.4J . ., 8 . I. 9 Ion 499&O* e ;: ao' Hin 2FFMI I Ion 413.00 710 7;5 e;o . `e:i. . $14.. . Hin Page 138 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 Data File: \\ETSWKNER\MPATIW06O~WIU~43.D 1.8; 1.7; Exposed -I 67hn Control MilliQ No Peroxide 1.6; 1.5; 1.4: 1.3; 12; 1.1: 1.0: 0,9j 0.8; 0.7; 0.6; 0.5; 0.4; 0.3; 0.2: 0.i; . . .,I....,...I.,....,.I.l.L.,I.,.,..,....)....,....,..I..,....I(.... 1 2 3 4 w IPFBS Ion 299.00 * 2.0: 1.0: . . . . (. . . .,....IJ,....,...., I 6.5 7.0 7.5 8.0 8.6 2 PFOA Paw 2 `8 :: f 8, u{ 5 6 7 n 3 PFOS 8 9 10 11 -- Ion 499.00 1s; i3 1.6; ci 1.4: 1.2; f ;;! l - ; 0.6; 0.4; 0.2: . , 7.5 ., I .. , . . , 8.0 8.6 9.0 Hin .I. 1 9.5 Page 139 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 Data File: \WfSLVr;NE U)ATA~O8OOwi0608Oobvl1LL0070.D Page 2 \\ETSLIAGNER\C~CHEMiU)LTIIW060800W0608,D 7.01 6.8; 2 6.6; Unexposed -167hm Hank Fe.203 No Pemxids 6.3; 6.0;: 0.8: 6.0; 6.3; 5.0; 4.8; 4,s; 4.3: 4.0; 3.8; 3.5; 3.3: 3.0: 2.8: 2.5; 2.3: 2.0-i i.8; 1.5; 1.3; 1.0; 0.8: 08; 0.3j, . , . . , . .. . I. . I. . III. . . . . . . . . . . . . . . . . . . . . . . I ,....I....,....,....,.... 1 2 3 4 6 6 7 8 9 10 ll n * lPF28 7.0: 6.0; Ion299&O,, et-4 r: . . I.. . i'o..II ., La . .a'6. . . , 6.8 e 7.6 . 8.5 " 1.20; 1.10; Loo: F; 0.90; 54 0.80~ 5 0.70: a- 0.60; 0.80; O.JOL7/-:Jd Ion 413.00 ;I$. . .+. . 8I6 * . iId.. . Nltl Page 140 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 Data File: \\ETWWACNER'.CWPCHEHU\lWHO6OaOO WM6WOObWILL007l.D \\ETSWK;KR\CVIPCHM\l\~TR~~~O6~WILL~7l.D 6.2: 8.0: Unexposed-167bn 4.8; BlankSpiked Fe203 NoPeroxide 4.6: 4.4j 4.2; 4.0; 3.8: 3.6; 3.4: 3.2; 3.0; P-e 2 0.6: 0.4: 0.2: . I. . II. . . . . III . . . . III. . . . . . . . . . . . . . . . . . . . . . . . . ..`................... I 2 3 4 6 6 7 8 9 10 11 in w 1PFBs 3.PPOS - Ion 299.00 rrn f 6.0: r: Ion 499.00 6.04 i 4.5; 0' 6.0: - 4.0; g ;1 3.0; " z- 2.0: 1.0: ;;, . ;;$' ;*; * `. iId e;e Hin 4.0; 3.5: p ;:;f " 2.0; * 1.5; 1.0; 0.11; . . j'e. . $; !!a.&, L . .& . . j;; . . 2 PFOR 1.2: 1.14 1.0; 0.9: 0.8; $ 0.71 b 0.6; z 0.6, : > 0.4; 0.3; 0.2; 0.1: ( 7.0 Ion 413.00m tx m' ., . . . , 7.5 8.0 Hln \I / .. , . . ,. . 8.5 9.0 Page 141 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 Data Fib: \XETSWACNER~HPCHDN\D~TWHOM8OO~ WIUO072.D Page 2 1.8- 1.7; 1.6: 1.6,: i.4; 1.3; 1.2, l.lj 1.0; 0.9: 0.8; 0.7: 0.6; 0.5: 0.4; 0.3; 0.2; 0.1; a . . . . I . . . . .111. . I . . I . I. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1 2 3 4 6 "in6 7 8 9 10 ii Ion 299.00m l-8 6'5 h' 6.0; ; 4.0; 6 d 3.0: a- 2.0; 1.0; . 9 . . , . . , , I., . , . , . . I. . , . . . , 6.6 7.0 7.6 8.0 8.6 2 PFOR 1.30; 1.20; 1.10: 1.00; ,0.90: 0.80; 0.70; O,SOj 0.60; o.*o+ . . 7.0 . . ( . 9.0 Page 142 of 158 - BACK TO MAIN 3M Environmental Laboratory Report No. W2775 Unexposed - 167hrs Contml MilliQ No Pemxide , 0.9; I : 0.8; 0.7; 0.6: 0.5; 0.4; 0.3j 0.2;. 0.1; . I . .I . I . . . . I . I . . II . . I.I . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..~...~~ 1 2 3 4 5 6 7 8 9 10 11 in Ion 299.00*, ti% 6.0; r: 6.0, ., . I, I 6.5 7.'0 . i'd, . . 8. .'6 ' i:6 Hin 3 PFOS t i.8. 1.61 i.4; i.2; - i.+ % 1 0.0; ; 0.6; 0.4; 0.2-3 Ion 499.00, 4-23 d 2.3; *.2: 1.1; i.0: Q 0.9; 3 0.8: ; 0.7; 0.6; 0.6; 0.4: ,.... 7.0 Iul 413.00 4 I . . . . . . . .. .. . . . .. . . . 7.6 8.0 8.1 9.0 "4.. Page 143 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 Data File: \\ETSWfXhER\CWPCH\DhWfWO6OWO WO6O800e\HILL0104.D Page 2 \\ETSWK;NER\CWCHEH\l\DCltCIV1060800\H06004.D ?.Ol 6.81 6.6; Day 0 6.3; Blank Fe203 No Pcmxidc 6.01 5.8; 5.5; 1.3; 5.Oj 4.0; 4.6; 4.3-i 4.0; : 3.8; ' 3.5; 1I 3.3; - 3.0: 2.8; 2.5; 2.3; 2.0-i 1.8: i.si 1.3; i.0; 0.8; 0.5; 0.3; `. . . I.I,-....,.,,.,....,....I,I....,....,I.,.,..,....,....,.I.I..,.... 1 2 3 4 6 6 7 8 9 10 11 n Y 1PFBs 7.0: 6.0; Ion 299.00 t# c 6.0; $ ;z " .: t 2&i 1.0: . . ( , . , .IJ . , . I . , , 6.5 7.0 7.11 8.0 8.6 Hin Page 144 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 Data File: \ETSwu;-IVT#WObOWO\ H0608000WILLOi05.D 1.2, \\ESSUACNR\C\HPmM\i~T~~O~~~WIU~OS.D 54..02: Day 0 Blmk Spiked Fe203 No Pcmxidc 4.6; 4.4: 4.2; 4.0: 3.8< 3.6: 3.4; 3.2: 3.01 ; 2.8:: , 2.6: j 2.4; - 2.2: 2.0: 1.8: 1.6: 1.4: 1.2: 1.0; 0.8; 0.6: 0.4: 0.2: . I . . I,. , . . I, . . ( I,,, . . . , 1 2 3 Y 1 PFBS ...,. . 4 - ,. . . . , . . . 6 6 - Hh ~~ 3Ffos % 0 ,. . . . ). . 7 8 . , . . . ., . 9 10 P*(* 2 , . .. ii b.0; 1.0; :,/ .. .. ,, 6.6 ,, .I.I .. ,, 1.8. .. .. ,, .. .. ,, 7.0 7.5 8.0 8.1 I Hin 2PFw Ion 413.00~ 1.2. hiti 1.1; w' 1.0; 0.9: 0.8; 3 0.7; 6 0.6; 2 0.5; > 0.4; 0.3;: 0.2: 0.1; , . . . , .. 7.0 7.8 8.'0""i'i' . n x0 . . . Page 145 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 Data File: \WTSUMNER\CVPCNEN~V\WTC) WO6O6OOWMOROOoWIUOiO6.D Page 2 0.7i 0.6: 0.5; 0.4: 0.3; 0.2; 1. I . II. , . . . ( II . . . I. , . . . , . . . , 1 2 3 4 6 * 1PFBs c [\ , ,. . ., . . . . ,. . . , .. . , . . 6 7 8 9 10 ii n ----. - -- 3PFos l.0; Ion 499.00d i.5 `?I 8' i.4: 1.2:: i.0: f 0.0: = 0.6: 0.4: , . . , I . . , I ,....,...., 0.2; 6.6 7.0 7.5 8.0 0.5 n 2 Pm I Ion 415.00 Page 146 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 \\ETSbXNERWWFtEtNV . 1.6; my0 Conml MilliQ No Pmxidc W060800W060800e\HILLOkU.D I-Y? Ion 299.00 r! 6.0; r: 1.0: 6.5 I, . . . , . . , . . . .) . .. . , .. .. , 7.0 7.5 8.0 6.6 tan 2 PFM 1.30; %?01 1.i0; i.00~ 2 0.90: 6F( 0.80; - 0.70; t 0.60; 0.60:: 0.40; 7:6 . Ion 413.00 b ;ia' . . e.d . . .&. nin . Vi . . . Ion 499.00 ii 1.6; 0' i.4: 1.2i i.Oi 0.8; 0.6: 0.4: 0.2; , . .. ., I . I . ., . . . . , . . . . , . . 1 7.5 8.0 8.5 9.0 9.5 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 IAEORATORY SOILS ST CROIX cc, byl MOMAN cc, AU Cf, mon<o dfbd huh Cu. m@Kg dad bad FO,IT@KfJdhdb99h *nglKo&*db=* Mg,mgMgdhdkrb Mh mgMgddadbasls MO. mgKg dded butr N&w%-Nl, mglKg dded bari P, mg/lQ dtiod bprlr Pb,mgtKgdthdbasb EXCHANSE -.ndKg-zn.mgn<g-hpr* ACTlVilY ExImcIabIs co. meqiDo0 ExIradab* P. mqmog -~wJ.meqnoos Exwwabh No, mqnOOg Bass BaIufauon x CEO. maw% ESP. x SAA, WIIIS NUiRIENTS AvaIlable P, rr~L NH3-N. mMNO%N. mQ/lm Kjeldahl H mvW ORaANlC MATTER TOG% oh%% PHYSIOCHEMICAL Fkm CapaoiIy, x pHw,unH8 pIis,unllr lhlweq. 1ollJAon SdubleSaksm. mhodcm ClA!3SlFlCATtON %clay %SllI %Smd Soil Typ9 BASE NEUTRAL PESTUDES ACID PESTICIDES BDL I Wow D91onion Lhnilr Q 22ooo *lO 210 :-iii 3ooQ do.5 8 35 12 20000 0.04 ** 28M coo 52 120 18 620 430 do0 49 a.14 0.60 2.97 0.03 42 28.3 0.11 0.04 61 2.00 84 1470 1.m 3.09 19.1 5.7 5.7 1.0 0.98 22 U 34 LOAM BDL BOL 4 40000 <lO p7 a.5 loo0 .a5 5 41 s.5 no00 0.11 1500 120 64 73 14 150 QO 300 47 3.50 0.10 0.43 0.02 10 22.0 0.09 0.05 5 0.25 14 280 on 0.478 33.3 .4.0 4.5 2 26 36 38 CUY LOAM BDL BDL EPA-BBM 4 48000 40 loo 0.6 .8Moo 4.5 6 25 13 18000 - 0.02 30000 710 02 =. 13 710 80 Qoo 47 26.1 0.18 3.58 0.00 . 100 21.3 0.28 0.05 15 1.80 6.0 250 047 0.005 16.6 7.7 7.5 NONE 0.66 SANDY 22 25 52 CLAY LOAiM BDL BDL t Page 149 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 Appendix G: Light Intensity Measurements (Miami FL) at 45" South Latitude Page 150 of 158 3M Environmental BACK TO MAIN Laboratory Report No. W2775 PME 83 Atlas Xenon Filter Combination .,. Futmr Gfrrt ' .: &&*:,. ...:. -- . ' . . . . ml nm nm nr .' . Z'. ,. 11.. :. : .a &daLlma `Small varktbms arc pod& dqwntiing on conditionof lamp andjWem. Page 151 of 158 BACK TO MAIN 3M Environmental Laboratory Report No. W2775 Appendix H: Characteristics Instruments of the Spectral Output of the Suntest 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 3M Environmental BACK TO MAIN Laboratory Report No. W2775 Suntest h-radiance in W/mA2*nm Assuming the use of300-800nm 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 QlSuprax (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 lrradiances factored to yield 680 W/mA2 in 300-800nm band IR QlSuprax (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 Page153of158 3M Environmental BACK TO MAIN Laboratory Report No.W2775 330 0.431 0.482289 332 0.449 0.502431 334 0.475 0.531525 336 0.495 0.553905 33% 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 I.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 Page154of158 3M Environmental BACK TO MAIN Laboratory Report No.W2775 430 1.466 1.640454 432 1.487 1.663953 434 1.5 1.6785 436 1.566 1.752354 438 1.714 1.917966 440 1.616 1.808304 442 1.616 1.808304 444 1.57 1.75683 446 1.563 1.748997 448 1.573 1.760187 450 2.267 2.536773 452 2.031 2.272689 454 1.796 2.009724 456 1.811 2.026509 458 2.127 2.380113 460 1.835 2.053365 462 3.267 3.655773 464 2.476 2.770644 466 2.541 2.843379 468 5.277 5.904963 470 2.487 2.782953 472 1.922 2.150718 474 2.924 3.271956 476 1.837 2.055603 478 1.813 2.028747 480 2.289 2.561391 482 2.516 2.815404 484 2.651 2.966469 486 1.952 2.184288 488 1.842 2.061198 490 1.898 2.123862 492 3.012 3.370428 494 2.089 2.337591 496 1.871 2.093649 498 1.888 2.112672 500 1.898 2.123862 502 1.973 2.207787 504 2.005 2.243595 506 1.94 2.17086 508 1.927 2.156313 510 1.934 2.164146 512 1.963 2.196597 514 2.013 2.252547 516 2.031 2.272689 518 2.021 2.261499 520 1.995 2.232405 522 1.971 2.205549 524 1.98 2.21562 526 1.966 2.199954 528 1.978 2.213382 Page155of158 3M Environmental BACK TO MAIN 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 1.669546 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 3M Environmental BACK TO MAIN 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 .I91735 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 0.68% 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 Page157of158 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 lrradiance 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 680.0W/mA2 3M Environmental BACK TO MAIN Laboratory Report No.W2775 Page158of158