Document 1g5O73GaRnJepa87QpNwMQ67X

BACK TO MAIN 3M Environmental LaboratoryReport No.W2783 Study Title Screening Studies on the Aqueous Photolytic Degradation of 2-(NEthylperfluoroctanesuIfonamido)-ethyal lcohol (N-EtFOSE Alcohol) Dafa 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 lgth,2001 Performing Laboratory 3M Environmental Laboratory Building 2-3E-09,935 Bush Avenue St. Paul, MN 55106 Project Identification 3M Laboratory Report No: W2783 Total Number of Pages 165 Page 1 of 165 , - t BACK TO MAIN 3M EnvironmentalLaboratory Report No. W2783 This page has been reserved for specific country requirements. Page 2 of 165 BACK TO MAIN 3M EnvironmentalLaboratory Report No.W2783 Compliance Statement Study Title: Screening Studies on the Aqueous Photolytic Degradation of 2-(NEthylperfluorooctanesu1fonamido)-ethylalcohol (N-EtFOSE Alcohol) Study Identification Number: W2783 This study was not designed to be performed in accordance with the GLPs. Thus, it does not comply with the requirements of the US EPA Good Laboratory Practices Standards at 40 CFR Part 792 (TSCA). However, all raw data and the final report have been audited. 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 upon on OPPTS: 835.5270 "Indirect Photolysis Screening Test" and OECD Draft Document "Phototransformationof Chemicals in Water - Direct and Indirect Photolysis", August 2000, and documented according to GLP procedures. All raw data and the final report are maintained in the 3M Environmental Laboratory archives. Sponsor Representative Date Page 3 of 165 BACK TO MAIN 3M Environmental LaboratoryReport No. W2783 Quality Assurance Statement Study Title: Screening Studies on the Aqueous Photolytic Degradationof N-(Ethylperfluoro- octanesu1fonamido)-ethyl alcohol (N-EtFOSE Alcohol) Study Identification Number: W2783 This study has been inspected by the 3M Laboratory Quality Assurance Unit as indicated in the following table. The findings were reported to the study director and laboratory management. Inspection Dates 03/30/01-04/05/01 03/30/01-04/05/01 Phase Data Draft Report Date Reported to Management Study Director 04/06/0 1 04/06/01 04/16/01 04/16/0 I Quality Assurance Unit Date Page 4 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 Table of Contents Compliance Statement .......................................................................................................... 3 Quality Assurance Statement ................................................................................................ 4 Table of Contents ................................................................................................................... 5 List of Tables .......................................................................................................................... 6 List of Figures......................................................................................................................... 6 Study Personneland Contributors......................................................................................... 7 Study Personnel and Contributors......................................................................................... 7 Location of Archives ............................................................................................................... 7 Summary................................................................................................................................ 8 Introduction............................................................................................................................. 9 Materials and Methods ........................................................................................................... 11 Chemical Characterization................................................................................................ 11 Method Summaries ........................................................................................................... 11 Study Deviations................................................................................................................ 13 Results and Discussion......................................................................................................... 14 Data Quality Objectives..................................................................................................... 14 Analytical Results .............................................................................................................. 14 Data Summary and Discussion........................................................................................ 15 Conclusions .............................................................................................. :............................ 21 References............................................................................................................................. 22 Signatures .............................................................................................................................. 23 Appendix A: Analytical Methods.............................................................................................. 24 Appendix B: Chemical Characterization................................................................................ 108 Appendix C: Kinetics Model and Kinetic Calculations............................................................ 112 Appendix D: Individual Sample Data ...................................................................................... 122 Appendix E: RepresentativeChromatograms....................................................................... 125 Appendix F: Soil Types and Characterizations...................................................................... 155 Appendix G: Light Intensity Measurementsat 45"South Latitude (Miami FL)....................... 157 Appendix H: Characteristics of the Spectral Output of the Suntest Instruments ..................159 Page 5 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 List of Tables Table I.Typical Sample Preparation Scheme Used in the Present Investigation...............12 Table 2. Observed Products and Mass Balance Determinationsfor Direct and Indirect Photolysis in Water, Iron Oxide Containing Water and Synthetic Humic Water...................... 16 Table 3. Observed Products and Mass Balance Determinationsfor Photolytic Decompositionof N-EtFOSE alcohol in the Presence of Three Soil Types........................................ 19 List of Figures Figure 1. Structures of the Compounds Observed by LC/MS Analysis ............................... 10 Figure 2. Proposed Degradation Route of NEtFOSE Alcohol by Indirect Aqueous Photolysis ................................................................................................................................. 18 Page 6 of 165 BACK TO MAIN 3M EnvironmentalLaboratory Report No. W2783 Study Personnel and Contributors Study Director Thomas L. Hatfield, Ph.D. 3M Environmental Laboratory Building 2-3E-09 935 Bush Avenue St. Paul, MN 55106 (651) 778-7863 Sponsor 3M Corporation 3M Environmental Laboratory Contributing Personnel Kent Lindstrom Anh Dao Vo 3M Environmental Laboratory Professional Services Contributing Personnel Anthony (Tony) Scales Debra Wright Jan Schutz Rufat Mischiev (Pace Analytical Services, Inc., 1700 Elm St., Minneapolis, MN 55144) Kristin Terrell Jill Maloney Karen Johnson (Braun lntertec Corporation, 6875 Washington Ave. South, Minneapolis, MN 55439) Location of Archives Digital copies of original data, and all original paper data have been archived and will be retained in the 3M Environmental Laboratory archives for at least 10 years. Page 7 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 Summary We report here the results of studies to determine the aqueous photolytic stability of 2- (N-ethylperfluorooctanesu1fonamido)-ethyal lcohol (N-EtFOSE alcohol) and to identify the primary degradation products. 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 a synthetic light source. The primary findings established that the rate of photodegradation by direct photolysis is negligible and the primary products of indirect photolysis are perfluorooctanoicacid, N- ethylperfluorooctane sulfonamide and perfluorooctane sulfonamide. Rates of indirect photolytic degradation are highly dependent on experimental conditions however, using an iron oxide (Fe203) photoinitiator matrix model an environmental half-life estimate of 40 days was determined. Page 8 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 Introduction Photolysis reactions are primary routes of degradation of chemical compounds in the environment (hydrolysis and biodegradationare two others). A study of photo-induced reactions will yield information on the persistence of the parent material and 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 loosely 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, photons from a light source were used to either induce a direct chemical change in N-EtFOSE alcohol or to induce the formation of radicals from the sample matrix, which then produced a chemical change in the test substance. The test material, N-EtFOSE alcohol was dissolved in an aqueous solution that was exposed to simulated sunlight to test for direct photolysisJS2To test for indirect photolysis, N-EtFOSE alcohol in four separate aqueous photoinitiator matrices were exposed to simulated sunlight for periods of time from 69.5 to 72 hours. These exposures tested how each particular matrix affected both the overall rate of decomposition as well as the observed product distribution. The first test matrix was an a ueous solution to which l+02 was added as a well characterized source of .OH radicals?? This was used to test for the propensity of N-EtFOSE alcohol for indirect photolytic decomposition. The second matrix contained a dilute aqueous CaCh solution and a well-characterized soil. This matrix was used to test the effects that adsorption-desorption equilibria, surface induced reactions and "*OH q~enching"c~ould have on indirect photolytic decomposition. The third matrix contained Fe203in water, as this matrix has been shown to generate hydroxyl radicals via a Fenton-type reaction in the presence of both natural and artificial sunlight.677The fourth matrix was a standard humic material8and was consistent with a modified procedure based on the US EPA methodology,OPPTS 835.5270 "Indirect Photolysis - Screening Testfgas well as OECD Draft Document "Phototransformationof Chemicals in Water Direct and Indirect Photolysis", August 2O0O1O. To effectively determine photolytic decomposition, the concentration of parent material must be monitored over time. While this will determine the rate, it is also important to understand what the degradation products are and how much of each are formed. The present investigation quantified the parent material and the four predicteddegradation products by LClMS as shown in Figure Iwere EtFOSA is N-ethylpetfluorooctanesulfonamide,PFOA is ammoniumperfluorooctanoicacid, FOSA is perlfluorooctanesulfonamideand PFOS is potassiumperfluorooctanesulfonate. Because of the possibility of volatile degradation products, it was decided to monitor for selected C2through C8 2- or 3- substituted petfluoronated olefins (e.g. c8F16) and 1- or 2substituted hydrides (e.g. C ~ F I ~ Hin)the iron-rich matrix by dynamic purge and trap gas chromatography/mass spectrometry. Page 9 of 165 BACK TO MAIN 3M EnvironmentalLaboratory Report No. W2783 Figure 1. Structures of the Compounds Observed by LC/MS Analysis N-EtFOSE Alcohol EtFOSA FOSA PFOA PFOS Determinationof the kinetic rate constant (k,,)was based only upon the data from the iron rich matrix using the following equation under the assumption that the kinetics was first order. (See Appendix C for complete kinetic derivations and exact mathematics for half-life calculations.) k,t =-In [t) Where t represents elapsed time, P represents the measured concentration of the parent after exposure and POrepresents the initial concentration. The half-life of NEtFOSE alcohol ( T?$ ) is relatedto the determined rate constant by the following equation. Page 10 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 Materials and Methods Chemical Characterization Information on the chemical characterization of both reference substances and control substances is presented in Appendix B. Method Summaries Copies of all analytical methods used in this investigationare attached in Appendix A "Analytical Methods". Equipment settings, conditions and complete quality control parameters are listed within those specific methods. UVNisible analysis were performedfollowing 3M EnvironmentalLaboratory Method ETS-946.0 "Operation and Maintenance of the Hewlett Packard 8453 UV-Visible Spectrophotometer" An aqueous saturated solution of NEtFOSE alcohol was prepared and an initial UVNIS spectrum recorded. Absorbance over the range 190-1100 nm was recorded. No absorbance over baseline was detected. Sample preparation for this analysis followed 3M Environmental Laboratory Method ETS-8177.0 "Indirect Photolysis Screening Tests in Synthetic Humic Water" or ETS-8-176.0 "Preparation of Samples for Photolytic Exposure Studies in Aqueous Matrices". A typical sample preparation table for an indirect photolysis screening test is shown in table 1 on the following page. The general method of sample preparation is as follows. For each time point under each condition shown in table I,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: water, soil in water at 0.70XX g in 5 mL, Fe'3 at a 24X molar excess in water, and H202 was at 1:l molar equivalent, added every 24 hours. Aliquots of NEtFOSE alcohol were added to the vials as indicated in table 1. The initial time point vials (labeled as 'Time Zero" on the sample preparation sheets in Appendix B) were then refrigerated at 452C. These samples served as controls with which to determine what change, if any, occurred during the time the remaining vials were in the photoreactor. Exposed samples were placed upside down in a custom built holder in the photoreactor. Unexposed samples were wrapped in aluminum foil, sealed in a plastic bag and placed under the sample rack inside the photo-reactor (these samples assured 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 k 3C. The temperature of the chamber itself was allowed to drift to 70 +lOC. When required, the H202 was added at each 24-hour interval by gas-tight syringe, through the VOA septa during the exposure period. After exposure, the samples were removed for analysis. Page 11 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 Selected portions of the sample setup were modified to accommodate additional samples, controls etc. to improve the quality control of the analysis or were modified in other ways out of experimental necessity. Details of these modifications are shown on the sample preparation sheets and the individual sample data sheets shown in Appendix D. For example, the sample setup for the soil rich matrix used quartz tubes (in quadruplicate rather than triplicate) as opposed to VOA vials. The portion of the study that used iron oxide as a radical generating species was set up with triplicate samples and duplicate sample spikes while the aqueous study was set up using duplicate samples rather than triplicate due to space limitations. The artificial light source 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 of light from this equipment was set at the desired intensity and held constant by a continuos internal feed back loop between an internal radiometer and the variable light source. Intensity was set at 680 w/m2. Table I.Typical Sample Preparation Scheme Used in the Present Investigation 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 Matrix + + + + 0 0 0 0 Matrix 0 0 0 0 0 0 + + + + Substance + + 0 0 + + 0 0 Target Analyte spike 0 0 0 + 0 + 0 + 0 + Initial Time Point Initial Time Point Initial Time Point Initial Time Point Initial Time Point Initial Time Point Initial Time Point Initial Time Point Initial Time Point Initial Time Point LC/MS* X X X X X X X X X X X X X X X X X X X (GCIMS* X X X X X X X X Ind. Photo. Sample Rep 1 + 0 + Ind. Photo. Sample Rep 2 + 0 + Ind. Photo. Sample Rep 3 + 0 + Ind. Photo. Sample Spike + 0 + Matrix Blank + 0 0 Matrix Blank Spike + 0 0 Direct Photo. Sample 0 + + Direct Photo. Spike 0 + + Control Blank 0 + 0 Control Blank Spike 0 + 0 I Ind. Photo. Sarrple Rep 1 + 0 + Ind. Photo. Sample Rep 2 + 0 + Ind. Photo. Sample Rep 3 + 0 + Ind. Photo. Sample Spike + 0 + Matrix Blank + 0 0 Matrix Blank Spike + 0 0 Direct Photo. Sample 0 + + Direct Photo. Spike 0 + + Control Blank 0 + 0 Control Blank Spike 0 + 0 0 Exposed to Light X X 0 Exposed to Light X 0 Exposed to Light X + Exposed to Light X X 0 Exposed to Light X X + Exposed to Light X X 0 Exposedto Light X X + Exposed to Light X X 0 Exposed to Light X X X + Exposed to Light - X X X X 0 Not Exp. to Light X X X X 0 Not Exp. to Light X X X X 0 Not Exp. to Light X X X X + Not Exp. to Light X X X X 0 Not Exp. to Light X X X X + Not Exp. to Light X X X X 0 Not Exp. to Light X X X X + Not Exp. to Light X X X X 0 + Not EXD.to Liaht X Not Exp. to Light X X X 11 X X X X Page 12 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 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 present in this method. Equipment procedures for the GC/MS system followed 3M Environmental Laboratory SOP ETS-9-49.0 "Routine Maintenanceof Archon Purge and Trap Autosampler, Tekmar Purge and Trap Concentrator and Agilent Gas Chromatograph/Mass Spectrometer". The HPLC/MS analysis followed 3M Environmental Laboratory Method ETS-8-181.O "Analysis of Photolysis Samples for Fluorochemicals by High Performance Liquid Chromatography With Mass Spectrometry Detection". Equipment settings, separation conditions and ions monitored are present in this method. Studv Deviations Gas chromatography/mass spectrometry (GC/MS) was used for the analysis of volatile degradation products in the indirect photolysis test, the Fe+3matrix and the H202 rich matrix. GUMS analysis of the humic material matrix and the soil rich matrix were not performed. During the time course of that portion of the investigation,the instrumentationwas unavailable. The LC/MS analysis of the samples from the soil containing matrices showed low levels of background PFOS contamination. The sample preparation sheets that contained the soil weights (0.70XX grams, where X is unknown) were misplaced. Further, the control samples, or those without soil, showed poorer than expected mass balance. Due to these three factors, the data should be treated as semi-quantitative. If more definitive information is desired, additional studies are recommended. The matrix containing the synthetic humic material showed unexpectedly slow photolytic decomposition of N-EtFOSE alcohol. This may have been due to excessive bleaching of the material. A second possible problem was that while setting up additional experiments in this matrix, the commercial humic material (Aldrich) was determined to contain the approximately 1 ppm dissolved organic carbon when the solution was prepared as recommend in reference 9 rather than the specified 6 ppm. The study director believes that the second explanation is the most probable and that the reaction was slower due to the lack of available radical generating species. Specific samples that failed data quality objectives are shown in Appendix D. Page 13 of 165 BACK TO MAIN 3M Environmental Laboratory Report No.W2783 Results and Discussion DataQualityO b j e d i The following data quality objectives are from the method used in the present study. 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, particularlyat upper and lower calibration limits. Residualsgenerated in curve-fitting must be within f 25% of true value. Alternative methods of curve-fitting (e.g., quadratic) require a correlation coefficient (r) of 0.990 or greater. Record the reason(s) for using quadratic curvefitting, 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 are greater than 75% or less than 125%. Values outside this range must be documented and evaluated by the Team Leader or designated supervisor. Sample duplicates, triplicates or quadruplicates. All samples are prepared with multiple replicates. Acceptable deviation or 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). Analyte concentration must not vary by more than +25% of its expected value, 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 lowest standard in the calibration curve that has an area greater than or equal to four times the solvent blanks and shows a residual less than 25% of the actual value. Control Samples. Control samples were required to be within 525% of the nominal concentration. 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. Calibration curves. Calibration curves were prepared according to the particulartarget at the required levels. For example, calibration curves for N-EtFOSE alcohol typically ranged from 25 to 1000 ppb. Calibration curves for degradation products for analysis by LClMS typically ranged from 5-200 ppb. Calibration curves for GC/MS analysis of degradation products ranged from 1 ppb to 20 ppb. Using these standards, calibration curves were run Page 14 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 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. In certain cases, as noted in the Deviations section, the LOQ was raised so that the solvent blanks met this criteria. Sample spikes. All spike recoveries were between 75 and 125%, except where noted in Appendix D. Sample duplicates, triplicates or quadruplicates. All sample RSD values were 25% or less except those noted in Appendix D. Continuing calibration verification. All CCV samples were within 25% of the expected value. Method Blanks. All method blanks were below 25% of the LOQ except those from the soil rich matrix (see deviations section for discussion). Control Samples. All control samples were within 25% except were noted in Appendix D. Limit of Quantitation. The LOQ varied dependant upon target. In some cases, the LOQ was adjusted to a higher level to meet criteria by deleting the lowest standard. In certain instances, numbers are reported below LOQ. This was allowed when the compound was clearly present in the sample. The numbers are tagged and labeled as being below LOQ. Data Summary and Discussion Direct and indirect photolytic decomposition of N-EtFOSE alcohol was tested in four separate matrices. These matrices were exposed to 680 w/m2 of light over the wavelength range of 290-800 nm for time periods of 69.5-72 hours. Products observed and mass balance determinations for synthetic humic water, hydrogen peroxide in water and iron oxide containing water are shown in table 2. The purity of N-EtFOSE alcohol was 97.8%, thus 2.2% of the material by weight was unknown. In portions of the indirect photolysis experiments, volatile materials, mainly C8F17H, were detected at levels less than 0.25% by mass. Thus, it is difficult to determine if these materials were the result of degradation of the parent material or the impurities. As is the case with the volatiles, PFOS was detected in certain portions of the study at levels less than 0.4% by mass. Again, it is difficult to ascribe the appearance of the materialto degradation of the parent or the impurity. Direct photolytic decomposition of N-EtFOSE alcohol could not be determined as two separate exposures gave two different results. The data from table 2a "direct photolysis sample" showed levels of N-EtFOSE alcohol within experimental error both before and after exposure. At the same time, the appearance of low levels of EtFOSA representing 0.54% by mass of the original mass of N-EtFOSE alcohol was detected. However, data from table 2c (water only) showed a similar trend for N-EtFOSE alcohol and no appearance of any degradation product. Because the NEtFOSE alcohol used in this study was 97.8% pure, the appearance of the low levels of EtFOSA may represent degradation of an unknown impurity rather than degradation of the parent material. However, it can be stated that direct photolytic decomposition of N-EtFOSE alcohol (or impurities) is a very slow reaction. The UVNis spectrum of the test material showed Page 15 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 no measurable absorbance but is also inconclusive in supporting direct photolysis due to the low solubility of N-EtFOSE alcohol (-150 ppbv) in water. Table 2. Observed Products and Mass Balance Determinations for Direct and Indirect Photolysis in Water, Iron Oxide Containing Water and Synthetic Humic Water 2a. Matrix: Water, With and Without Hz 3 2 Time of exposure was 69.5 hours Sample Condition EtFOS5OH PFOA PFOS FOSA nMoles InMoles)nMole I nMole Balance Dir. Photo. Sample' Ind. Photo. Sample' Dir. Photo. Sample' Initial Time Point Exposed t o Light Exposed t o Light I Dir. Photo. Sample' Not Exposed to Light I Detection Limits 94.19 57.39 77.71 91.62 1.59 ND ND ND 5.53 ND 0.53 ND ND ND I I I 4.09 ND 0.48 ND ND ND I 0.24 I 0.20 I 0.21 3.36 I II ND 101% 0.2 0.0095" Vials initially contained 90.35 nMoles N-EtFOSE alcohol. 1. Indirect Photloysis Sample: These samples had H202added (1:l molar equivalance) as a radical source every 24 hours they were in the reactor, results are from duplicate samples. 2. Direct Photolysis Sample: These samples did not have H202added, results are from duplicate samples. *Sum total of all volatiles. ND = non detect. 2b. Matrix: Fe203in Water, With and Without H202 Time of exposure was 69.5 hours Sample Condition Fe2Q W/YO; Initial Time Point Fe203W0/&,4' Initial Time Point Fe2o3w/YQ' Exposed to Light Fe203WO/yO: Exposed to Light Fez03W/&O; Not Exposed to Light Fez& WO/l+02' Not Exposed to Light Detection Limits EtFOSE-OH nMoles 79.30 93.61 ND 59.53 61.34 90.01 1.59 PFOA PFOS FOSA EtFOSA nMole nMole nMole nMoles S S S 2.64 ND ND 3.27 ND ND ND ND 41.35 0.41 20.98 0.36 7.54 0.33 0.39 4.33 I I I I 5.36 ND 0.87 4.20 ND ND ND 0.23 I 0.24 I 0.20 I 0.21 I 0.2 Volatiles nMoles ND ND 0.14 ND I ND ND I 0.0095* BaIance (percent 94% 104% 70% 100% Vials initially contained 90.35 nMoles N-EtFOSE alcohol. 1. Samples had H202 (1:Imolar equivalance) as a radical source every 24 hours and Fe203added (24 F d 3 : I N-EtFOSE-OH molar equivalance) as a radical generating species, results are from quadripulate samples. 2. Samples contained just Fe203(24 Fe'3:l NEtFOSE-OH molar equivalance) as a radical generating species, results are from quadripulate samples. *Sum total of all volatiles. ND = non detect. 2c. Matrix: Synthetic Humic Water I 1 Time of exposure was 72.0 hours I I I I I I Sample Conditions I I Humic Water' 18.2 Ma Water' Initial Time Point Initial Time Point I EtFOSE-OH1 PFOA I PFOS I FOSA I EtFOSA I nMoles nMoles nMoles nMoles nMoles 7.55 I ND I ND I ND I ND 7.40 ND ND ND ND Mass Balance (percent) 111% 109% Humic Water' Exposedto Light 6.51 0.25 ND ND ND 99% 18.2 M a Water* Exposed to Light 6.39 ND ND ND ND 94% Humic Water' Not Exposed to Light 7.39 ND ND ND I I I I II I I I I I 18.2 M a Water' Not Exposed to Liiht 7.52 Detection Limits 0.17 ND ND ND 0.20 0.16 0.18 ND ND 0.17 I 109% 111% Vials initially contained 6.80 nMoles N-EtFOSE alcohol. 1. Samples contained Humic Materials, samples are from triplicate analysis. 2. Samples were plain water, results are from duplicate samples. ND = non detect. Page 16 of I 6 5 BACK TO MAIN 3M EnvironmentalLaboratory Report No.W2783 As was noted in the introductory section, the addition of hydrogen peroxide to water was done to determine the propensity of NEtFOSE alcohol to undergo indirect photolytic reactions with the hydroxyl radical. The results from table 2a show that N-EtFOSE alcohol will react with .OH radicals to form new products and establishes what the products are: PFOA, EtFOSA and FOSA. However, those samples that were not exposed to light showed a very similar loss of parent and distribution of products. It is believed that the loss of N-EtFOSE alcohol in the dark control samples that also contained H202was due to the equilibrium reaction between H202and the hydroxyl radical, the end result of which was decomposition of the parent material. Indirect photolysis in the synthetic humic materialwas observed as forming PFOA (3.7% by mass PFOA formation) from the data in table 2c. As noted in the deviations section of this report, this matrix, when mixed according to prescribed procedures, did not contain the appropriate amount of dissolved organic carbon. Thus, the conclusion from this test is simply that indirect photolysis of N-EtFOSE alcohol does occur in matrices that contain humic materials but at an undetermined rate. As observed in table 2b, the reaction between iron oxide, hydrogen peroxide and light with NEtFOSE alcohol resulted in complete loss of the alcohol (Fez03 with H202data). As with the reaction between N-EtFOSE alcohol and H202, the degradation products PFOA, FOSA and EtFOSA were observed and accounted for a sum total of 69.4% of the starting material by mass. However, trace levels of two new degradation products were observed: PFOS and volatiles. Because these two materials represent a combined total of only 0.61% of the original starting material, it is undetermined if these materials were degradation products from N-EtFOSE alcohol or degradation products from the impurities. The reaction between light, FepO3 and N-EtFOSE alcohol is perhaps the most environmentally relevant reaction of those shown in table 2. The products of this reaction were PFOA, EtFOSA, PFOS and FOSA. As with that portion of the test utilizing & 0 2 , only a small amount of PFOS was observed (0.36% by mass) and it is difficult to establish if this is from the parent material or low levels of impurities. Because Fe+3is ubiquitous in the environment, this test has direct relevance as an environmental model. Solving for the half-life (as shown in Appendix C), yielded an environmental half-life of 40 days at 45" south latitude in clear water and a cloudless sky. Based on the above results, the degradation pathway shown in figure 2 is proposed. Preliminary 3M data has shown that NEtFOSE alcohol has a high soil adsorption coefficient. To test for the effect that adsorption/desorption equilibria might have as well as possible surface induced photolytic reactions and possible hydroxyl radical quenching, N-EtFOSE alcohol was studied in the presence of three soil types. The first was an EPA synthetic soil mix representing a sandy clay loam, the second was a soil from Morgan County AL (USA) representing a soil with a high clay content and the third was a soil from St. Croix County WI (USA) representing a loam. Characterization data for these soils is shown in appendix F. Soil equilibration followed OECD method 106 "Adsorption - Desorption Using a Batch Equilibrium Method." The results of this study are shown on the following page in table 3. From the data in table 3 it is apparent that the soil-light combination can induce indirect photolytic decomposition of NEtFOSE alcohol, both in the presence and absence of added H202. The data shows that the addition of H 2 0 2 speeds up the reaction when compared to those samples without H202. When the data is compared against that from the direct photolytic test (Table 2a and c), it is concluded that something in the soil acts as a radical source for the Page 17 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 indirect photolytic decomposition of NEtFOSE alcohol. The data from the three sample sets in table 3 which all contained H 2 0 2 supports the hypothesisthat soils will slow the reaction, probably by some type of *OHquenching. Because the soil itself can act to promote indirect photolysis, the role of adsorption-desorptionequilibria remains unclear. As seen in table 3, the initial time point data and the data from those samples that were not exposed to light all showed levels of EtFOSA near the quantitation limit and represented less than 1% of the total EtFOSE concentration. This could be expected, as the starting material was only 97.8% pure. The compound PFOS was detected in all samples and controls of the Morgan County soil and probably reflects soil contamination rather than a chemical production. All indirect photolysis soil samples showed PFOS at low levels that were just above the quantitation limit. PFOS was also detected in all samples that were exposed to light that contained both soil and & 0 2 . Because of these low levels and detection of PFOS in control samples, it is questionable if the production of PFOS is due to photolytic activity of the parent material or some unknown impurity. The Fe203data was used as an environmentalmodel to generate a half-life estimate for the degradation of NEtFOSE alcohol by indirect aqueous photolysis. The additional parameters tested support the proposed mechanism and add to the conditions where the alcohol would be expected to degrade but confuse the rate issue. It is concluded that while the rate is possibly centered around the number of 40 days from the iron oxide data, conditions in the environment could change this rate considerably, possibly by as much as an order of magnitude or more in either direction. Figure 2. Proposed Degradation Route of N-EtFOSE Alcohol by Indirect Aqueous Photolysis FOSA OFFFFFFFF H-0 N-EtFOSEAlcohol CHI OFFFFFFFF H N-.II !!I!!!F!! Et FOSA PFOA Page 18 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 Table 3. Observed Products and Mass Balance Determinations for Photolytic Decomposition of N-EtFOSE alcohol in the Presence of Three Soil Types. 3a. Morgan County - High Clay Time of exposure was 72.0 hours ETFOSE-OH PFOA PFOS FOSA EtFOSA Sample Soil W/&&' Soil WO/&O: Soil W/&O: Soil WO/&O: Soil W/&02' Soil WO/&O,' Condition Initial Time Point Initial Time Point Exposedto Light Exposed to Light Not Exposedto Light Not Exposedto Light nanomoles A 26.35 27.21 5.22 23.38 25.50 nanomoles 1 ND ND 7.24 0.84' ND (nanomoles 1 0.22 0.23 0.48 0.29 0.26 (nanomoles 1 ND ND 8.16 0.78 ND (nanomoles 1 ND ND 1.75 ND ND 25.85 ND 0.22 ND ND I Mass Balance (percent) 87% 90% 75% 83% 86% 84% - Vials initially contained 30.65 nMoles N-EtFOSE alcohol. 1. Samples contained soil (0.70XX grams in 5 ml water) and H202(1:1molar equivalance H202:N-EtFOSE alcohol added every 24 hours), results are from triplicate analysis. 2. Samples contained only soil and analyte, results are from one replicate. *Estimated value ND = non detect. 3b. St. Croix County - Loam Time of exposure was 72.0 hours ETFOSE-OH PFOA PFOS Sample Soil W/&&' Soil wofio,' Soil W/&02' Soil WO/&O,' Soil W/I+O: Soil WO/&O$ Condition (nanomoles Initial Time Point 1 25.04 Initial Time Point 24.16 Exposedto Light 8.99 Exposed to Light 19.26 I Not Exposedto Light Not Exposedto Light 23.60 19.62 :nanomoles 1 ND ND 4.81 2.21 ND ND nanomole! 1 ND ND 0.63 0.55 0.26 0.56 FOSA EtFOSA nanomoles 1 ND ND I.a5 0.72 ND ND (nanomoles 1 ND ND 5.03 1.55 0.43 ND Mass Balance (percent) 82% 79% 70% 79% 79% 66% - Vials initially contained 30.65 nMoles N-EtFOSE alcohol. 1. Samples contained Soil (0.70XX grams in 5 ml water) and H202(3:1molar equivalance H202:N-EtFOSEalcohol added every 24 hours), results are from triplicate analysis. 2. Samples contained only soil and analyte, results are from one replicate. ND = non detect Page 19 of 165 BACK TO MAIN 3M EnvironmentalLaboratory Report No.W2783 Time of exposure w a s 72.0 hours ETFOSE-OH PFOA PFOS FOSA EtFOSA Sample Condition Soil W/&@' Initial Time Point Soil WO/&O2 Initial Time Point Soil W/l-&O,' Soil WO/l-&@' Exposed to Light Exposed to Light Soil W/bO,' Not Exposed to Light Soil WO/yQ2 Not Exposedto Light Detection Limits (nanomoles 1 26.17 27.82 17.66 25.54 27.36 14.72 0.92 (nanomoles ) ND ND 3.02 1.02* ND ND 1.21 (nanornoles 1 ND ND 0.72 0.25 ND ND 0.20 (nanomoles ) ND ND 2.82 0.68 ND ND 0.21 (nanomoles 1 ND ND 2.70 0.47 ND ND 0.47 Mass Balance (percent) 85% 91 % 88% 89% 89% 48% Page 20 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 ~ ~~ Conclusions Phototransformationsof compounds in the environment not only depend upon such factors as latitude, season, clouds, water clarity etc. but also depend upon the concentrations of other species in the water such as nitrate, iron, and dissolved organics. Photons from a synthetic light source were used to study the photolytic transformations of EtFOSE alcohol. We report here the results of studies to determine the aqueous photolytic stability of 2-(Nethylperfluorooctanesu1fonamido)-ethylalcohol (N-EtFOSE alcohol) and to identify the primary degradation products. Our techniques are based on both EPA and OECD guidance documents?*'0In this study, both direct photolysis (the interaction of light with the target molecule leading to a chemical change) and indirect photolysis (the interactionof light with the sample matrix to produce radical species that subsequently react with the target material) were studied using a synthetic light source. The main findings are that the rate of photodegradationby direct photolysis is negligible, and that the primary products of indirect photolysis are perfluorooctanoic acid, Nethylperfluorooctane sulfonamide and perfluoroctane sulfonamide. Rates of indirect photolytic degradation are highly dependent on experimentalconditions however, using an iron oxide (FesOs) photoinitiator matrix model an environmental half-life estimate of 40 davs was derived. . Dependant upon specific environmental factors, the half-life may vary by at least an order of magnitude in either direction. Direct photolysis could not be conclusively demonstrated. The indirect light source was used to induce the formation of radicals from the four separate sample matrices (a synthetic humic matrix, a hydrogen peroxide rich matrix, an iron containing matrix and a soil rich matrix). These radical species then reacted with the target to produce new chemical species. Degradation of N-EtFOSE alcohol was observed in each matrix, although the observed rates and product distribution varied from matrix to matrix. Three primary degradation products were observed: PFOA, EtFOSA and FOSA. In several studies, trace levels of additional degradation products were observed, mainly heptadecafluoroctanesand perfluorooctane sulfonate (PFOS). These were detected at trace levels that were close to the quantitation limit. However, it is unclear that either PFOS or the volatiles were the result of degradation of N-EtFOSE alcohol or the result of degradation of low levels (>3%total) of impurities. Mass balancefor the degradation of N-EtFOSE alcohol to form the primary products PFOA, EtFOSA and FOSA was within 100f30% for most experimental conditions Page 21 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 References 1. Scrano, L.; Bufo, S. A.; Perucci, P.;Meallier, P.; Mansour, M. Photolysis and Hydrolysis of Rimsulfuron. Pesfic. Sci. 1999, Vol. 55, pp. 955-961. 2. Nubbe, M.E.; Adams, V. D.; Moore, W. M. The Direct and Sensitized Photeoxidation of Hexachlorocyclopentadiene.Waf. Res. 1995, Vol. 29, No. 5, pp. 1287-1293. 3. Ogata, Y.; Tomizawa, K.; Furuta, K. Chemistry of Peroxides, in S. Patai (ed.). The Chemistry of Peroxides 1983, p. 720. 4. Lunak, S.; Sedlak, P. Photoinitiated Reactionsof Hydrogen Peroxide in the Liquid Phase, J. Photochem. Photobiol. A.: Chem. 1992, Vol. 68, pp. 1-33. 5. Haag, W. R.; Hoigne, J. PhoteSensitized Oxidation in Natural Water Via `OH Radicals. Chemosphere 1985, Vol. 14, No. 11/12, pp. 1659-1671. 6. Kachanova, Z. P.; Kozlov, J. N. Zh. Fiz. Khim. 1973, Vol. 47, p. 2107. 7. Behar, B.; Stein, G. Science1966, Vol. 154, p. 1012. 8. Takahashi, N.; Ito, M.;Mikami, N.; Matsuda, T.; Miyamoto,J. Identification of ReactiveOxygen Species Generated by Irradiation of Aqueous Humic Acid Solution. J. Pesticide Sci. 1988, Vol. 13, pp. 429-435. 9. Fate, Transportand Transformation Test Guidelines, OPPTS 835.5270 Indirect Photolysis Screening Test; EPA712-C-98-099; United States EnvironmentalProtection Agency, U.S. Government Printing Office: Washington, DC, 1998, pp. 1-22. 10. OECD Guideline for Testing of Chemicals, Phototransformationof Chemicalsin Wafer-Direct and Indirect Photoysis, (Draff Document); OECD,2000, pp. 1-59. 11. OECD Guideline for Testing of Chemicals, Adsorption - Desorption Usinb a Batch Equilibrium Method. OECD 106,2000, pp. 5 6 Page 22 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 Signatures The final draft of this report is a true representationof the data developed in this study. It has been issued by: Page 23 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 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 Maintenanceof the Hewlett Packard 8453 UV-Visible Spectrophotometer ETS-9-44.0 Operation and Maintenance of the Sunlight Exposure System, Immersion Unit, and Recirculating Water Chiller System ETS-9-49.0 Routine Maintenance of Archon Purge and Trap Autosampler, Tekmar Purge and Trap Concentrator and Agilent Gas Chromatograph/Mass Spectrometer ETS-8-177.0 Indirect Photolysis Screening Tests in Synthetic Humic Water ETS-8-176.0 Preparation of Samples for Photolytic Exposure Studies in Aqueous Matrices ETS-8-182.0 Analysis of Fluorochemicalsby Archon Purge and Trap Autosampler, Tekmar Purge and Trap Concentrator and Agilent Gas Chromatograph/Mass Spectrometer ETS-8-181.O Analysis of Photolysis Samples for Fluorochemicals by High Performance Liquid ChromatographyWith Mass Spectrometry Detection Page 24 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 3M ENVIRONMENT.LAALBORATORY METaOD ANALYSIS OF PHOTOLYSIS SAMPLESFOR FLUOROCHEMICALS BY HIGHPERFORMANCE LIQUIDCHlROMATOGRAPHy WITH MASSPECTROMETDREYTECTION Method Number: ETS-8-181.0 Adoption Date: 4-1 iG,/L 3 Effective Revision Date: Approved by: Laboratory Management ow-&, LC/ Date Page 25 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 Comuound Acronvm Perffuorooctanoic acid PFOA Perfluorooctanesul fonate PFOS Pduorooctanesulfonamide FOSA N-methylpertluorooctanesulfonamide N-MeFOSA N-ethylpertluorooctanesulfonamide N-EtFOSA Z-(NmethyIperfluorooctanesulfonamido) N-MeFOSE-OH ethyl alcohol 2-~-ethylperfluorooctanesulfonamido) N-EtFOSE-OH ethyl alcohol Gomooand Perfluorobutanoic acid Perfluorobutanesulfonate Pduorobutanesulfonamide N-methylperfluorobutanesulfonamide N-ethylperfluorobutanesulfonamide 2-(N-methylperfluorobutanesulfonamido) ethyl alcohol 2-(N-ethylpertluorobutanesulfonamido) ethyl alcohol Acronvm PFBA PFBS FBSA N-MeFBSA N-EtFBSA N-MeFBSE-OH N-EtFBSE-OH 1.3 . Compatible matrices for analysis.Aqueous (MilliporeASTM Type I water), buffered water, lake water, sea water and metal slurries (TiOz, FezO3, etc.) that have been diluted with an appropriateanalyticalsolvent such as acetone or methanol. 2.0 SUMMARY OF METHOD 2.1 This method describesthe analysis of fluorochemicalsin a specifiedmatrix, using HPLC electrospraymass spectrometryfor chemical separation and detectiodquantification. The analysis is performed by separating target analytes on an HPLC analytical column such as a Dionex NGI (35x 4.6mm, lOpm particle), Betasil C18 column (50x2mm, 5 pm particle) or equivalent using an ammonium acetateh4eOH solvent gradient. Detection by electrosprayionizationmass spectrometeryin either the positive or negative mode is utilized to quantifydata. The MSD may be runin SelectedIon Monitoring (SIM) mode, lookingfor specific, pre-selectedand set analyte ions (ie. d z 499 for PFOS (deprotonated)),or SCAN mode which collects and stores data for all ions in a specified mass range. Data quantificationis then performedusing either HP ChemStationor Target Sohare. ETS-8-181.O Analysis of Photolysis Samples for Fluorochemicals by WLC/MS Page 2 of 15 Page 26 of 165 BACK TO MAIN 3M EnvironmentalLaboratory Report No.W2783 3.0 DEFINITIONS 3.1 CalibrationStandard. A dilutionof various amounts of a stock. intermediateo_ _r purchased standardto achieve standard solutionsin a concentrationrange of interest. 3.2 CaIibration Curve. The graphical relationship between known values, such as concentrationof a series of calibration standardsand their instrumentalresponse. 3.3 Internal Standard Quantification. Processof establishinga relationship between the ratio of the target analyte(s) response to internal standardor surrogateresponse and a known concentrationof the target analyte(s). The ratio of analyte to internal standard responseis used to generatethe calibrationcurve and determineunknownconcentrations. 3.4 External Standard Quantification. Process of establishingthe concentrationof a target analyteby plotting the theoretical amount (inunits of ppb or pprn, etc.) versus the response of the target analyte(s)on column. The resultant curve(s) shall be used to determine unknown concentrations by comparing the area response of target analyte(s) to the area response and correspondinganalyte amount on the appropriate analyte's calibrationcurve. Diffences in sample mass/volwne analyzed, if noted, must be compensated for by a factor applied to the value. 3.5 Correlation Coefficient (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 f?om -1 to +l. A value of +1 denotesperfect direct functionalrelationship 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 Coefficientof Determination (r'). The square of the correlationcoefficient. 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@)of interest, added to all samples and standards, and carried through the entiremeasurementprocess (post-photolysis, after solvent dilution). It provides a reference for evaluating and controllingthe precision and bias of the applied analyticalmethod. Samples are to be quantified ushgthe internal standard. 3.8 Surrogate. An organic compoundsimilarto the target analyte(s) in chemical composition and behavior in the analytical process but is not nonnally found in the sample(s). A surrogatemay be added to samples along with the test analyte (pre andlor 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 the continuedaccuracyof the calibration curve. This solution may or may not be prepared from a different source or lot number than the calibration curve standards. ms-8-181.o Analysis of Photolysis Samples for Fluorochemicalsby HPLCMS Page 3 of 15 Page 27 of 165 BACK TO MAIN 3M EnvironmentalLaboratory Report No.W2783 3.10 Solvent Blank. A sampleof analyte-&e medium (for example, methanol, 1:7 diluted buffer:methanol) that is not taken through the sample preparation process. ThisbIank is used to evaluate instrument contamination. 3..11 Blank. For photolysis studies, there are multiple blanks to adequatelyrepresent the variables of the study (Exposed,Unexposed and Day 0 sampleswitwwithout peroxide addition). These blanks are carried through the sample preparation, photolytic and analyticalproceduresto monitor for contamination during any step. It is also used to establish a chromatographic baselinehackground and monitor for analytical interference or suppression of target analyte(s) from the matrix. 3.11.1 Matrix Blank: An analyte-freematrix (bufferedwater, lake water, etc.) to which all reagents are added in the same volumes or proportions as used in sample processing. It is used to documentthe test systemwithout test analytepresent. 3.11.2, ControlBlank An analyte-free matrix (ASTM TypeIIwater) 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, interferencesor suppressionof target analyte(s) from the test matrix. 3.12 Limit of Quantitation(LOQ).The lowest concentrationthat can be reliably measured within specified limits of accuracyduringroutine Iaboratoryoperating conditions. The LOQ is generally5 to 10times the minimumconcentrationwith a 99% confidence limit that the concentrationis greater than zero. However, it may be nominallychosen within these guidelinesto simplifydatareporting. For many malytes, the LOQ is selected as the lowest non-zerostandard 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 b m and representative of the same sample source and separatelycarried throughall steps of the extraction, photolysis and analytical procedures in an identical manner. There are multiple sets of triplicate samples to adequatelyrepresent the photolyticvariablesofthe study (Exposed, Unexposed and Day 0 with/without peroxideaddition). Triplicatesamples are used to assess variance ofthe photolytic method, including sample preparation, photolysis, and analysis. 3.14 Control Sample. A known matrix (ASTM Type IIwater) containingthe test anaIyte(s) carriedthroughoutthe entire samplepreparation, photolytic and analyticalprocedure. There are multiple sets of triplicate samples to adequatelyrepresent the photolytic variables of the study (Exposed,Unexposed and Day 0 witWwithoutperoxide addition). Thisis used to document method performanceand matrix effectsby comparing recoveries from the different matrices and sample types. 3.15 Relative StandardDeviation (RSD).A measure of precision defined as the standard deviationof three or more values dividedby the averageof the values and multiplied by 100. (Also reported as Coefficient ofvariation (CV)). 3.16 Analytical Spike (AS). Prepared by adding a known mass of target analyte(s) to a specified amount of a sample or control matrix prior to analysis. This assumes that an independent estimate of target analyte concentration is available. Analytical spikes are used to determinethe effect of the matrix on recovery efficiency. There are multiple ETS-8-181 .O Analysis of Photolysis Samplesfor Fluorochemicalsby HPLC/MS Page 4 of 15 Page 28 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 types of spiked samples to adequatelyrepresent the photolytic variables of the study (Exposed, Unexposed and Day 0 ;WiWwithoutperoxide addition.) 3.16.1 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. 3.16.2 Control Spike. The control matrix (ASTM Type Il 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 closenessof agreement between an experimentallydeterminedvalue 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 samplepreparation procedure in which a solvent (Le. methanol, acetone) is added to the test analyte/samplematrix (Le. water, b a e r , etc.) to prepare it for instrumental analysis. 3.19 Atmospheric Pressure Ionization (MI):The Agilent TechnologiesHPLC 1100/MSD system allowsfor ionizationof incoming liquid sample fromthe analyticalcolumn to the mass spectrometerinterfaceby utilizing a source, probe, hot gas, and specific voltages. 3.20 Electrospray Ionization @S, ESI): A method of ionizationperformed at atmospheric pressure, whereby ions in solution are transferred to the gas phase via tiny charge droplets. These charged droplets are producedby the applicationof a strong electrical field. 3.21 Mass Spectrometry, Mass Spectrometer(MS),Mass Spectrometer Detector (MSD): The MI HPl 100MSD system equippedwith a quadrupolemass selective detector. Ions are selectivelydiscriminatedby mass to charge ratio ( d z ) and subsequentlydetected. 3.22 Geometric Mean of the calibration curve: The square root ofthe product of the high standard concentrationand the low calibration curve standard. When preparing calibrationcurve standards, the number of calibration standards below the geometric mean shalt equal the number ofcalibrationstandardsabove the geometricmean. Having equal distributionof calibrationstandards above and below the geometric mean when analyzingand reprocessingdata, effectivelyweights 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 safetywaning 4.1.1 Wear the proper lab attire for all parts of this procedure. Wear gloves and proper eyewearwhen performing samplepreparation in the laboratory at all times. Wear proper eyewearwhen working at the instrument in the laboratory. ETS-8-181.O Analysis ofPhotolysis Samplesfor Ftuorochemicals by HPLCMS Page 5 of 15 Page 29 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 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 Forpotential hazards of each chemicalused,refer to material safety data sheets, packing materids, and the 3M Environmental Laboratory Chemical Hazard Review. 4.2 Cautions 4.2.1 All glasswarein which standardsare prepared should be rinsedwith acetone and methanol to reduce the possibilityof contamination. 4.2.2 Ensure that the HPLC mobile phases are prepared prior to beginning a run sequence, and that there is sufficientquantityto completethe run. Do not allow the pump to rundry. 4.23 Ensure that before startingthe 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 Contaminantsin 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&om coIumns,HPLC tubing, and detector componentsmay 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) 1100HPLC System, or equivalent. 6.2.1 Pump, binary, Model G1312; Quaternary,Model G1311A; or equivalent. 6.2.2 Solvent degasser, Model G1322A or equivalent. 6.2.3 Autosampler, ALS Model G1313k variable injection volume or equivalent. 6.2.4 Column heater, Model G1316A, or equivalent. 6.3 Betasil@C18,50 x 2 mm; Dionex IonPac@NG1 Guard column, 4 x 35 mm; or equivalent. 6.4 Mass spectrometer. Hewlett-Packard MSD Model G1946A, or equivalent. 6.5 Refiigerator capable of maintaining 4 5 3 OC. 6.6 Data system. A personal computer capableof controllingthe HPLC system as well as recording and processing signals from the detector. ETS-8-181.0 Analysis of Photolysis Samplesfor Fluorochemicals by HPLCMS Page 6 of 15 Page 30 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 6.7 System control/dataanalysis software: Hewlett Packard ChemStation@,Version A.6.03 or later. 6.8 Data reprocessingsoftware: Thru-Put SystemsTargetNT, Revision 4.03,Build 157 or later. HewIett Packard ChemStationa, Version A.6.03 or later. 7.0 SUPPLIES AND MATERIALS 7.1 Vials, 40 mL,VOA (I-Chem or equivalent) 7.2 Crimp cap autovials, 1.8 mL 7.3 Labels 7.4 Graduatedpipets, glass, disposable, 1mLto 10mL 7.5 Pasteur pipets, glass, disposable 7.6 Hamilton Gastight@syringes(precisionf 1%of total volume), 10 pL-1000 pL 7.7 Volumetric flasks,various sizes 7.8 Beakers, glass, various sizes 7.9 Automatic pipettor, capabIe of dispensing 10-5000 pL 8.0 REAGENTASND STANDARDS 8.1 Methanol (MeOH). HPLC/SPEC/GCgrade from EM Science, or equivalent 8.2 Acetone. HPLC/SPEC/GC grade fiom EM Science, or equivalent 8.3 ASTM Type II Water. Water with lower resistancemust not be used. 8.4 Ammonium acetate, 2 mM in water. This solutionis chromatographicsolvent A (see Section 12.2.1). (Example:An acceptable eluent solution is made by adding 0.15 g ammonium acetate crystals to a l-L volumetric flask containing about 500 mL water, adding 10mLof methanol, diluting to the mark with 18.0 MQ water and mixing.) 8.5 Stock, internal standard, surrogate,post-photolysisspike and calibration solutions All weights should be recorded to the nearest 0.0001 g in a standardspreparation log: 8.5.1 Fluorochemical or target analyteprepared in acetonitrile(or suitable analytical solvent). (Example: A stock solutionis prepared at a concentrationof approximately30,000 p g / d by weighing 0.3 g of target analyte in a 10-mL volumetric flask and bringing to the mark with suitable analytical solvent. This soIutionis dilutedin solventto make additional, appropriatestandards. Follow specifiedguidelinesfor documentingremoval of test analyte and target analyte(s), use of balance, preparation of diluted solutions and calibration standards in the appropriatelogbooks. Maintain photocopies of the preparation pages and worksheets in a raw data file. ETS-8-181 .O Analysis of Photolysis Samples for Fluorochemicals by HPLClMS Page 7 of 15 Page 31 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 9.0 SAMPLEHANDLING 9.1 Standards and diluted samples are stored in capped autovials or capped 40 mL VOA vials until analysis. 9.2 If analysiswill be delayed, standards and sample extractsmay be stored at 4OC f3 "Cor room temperature, until analysis can be performed. Document storage conditions on sample prep worksheet with date and initials. 10.0 QUALITCYONTROL 10.1 CalibrationStandards.Calibrationstandards(Section 11)used to generate a calibration curve should be prepared inthe same type of solvent or matrix as inthe study samples. The number of calibrationstandardsand 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 thanthree orders of magnitudebetween low and high standards),may require use of a quadratic fit of the data and requires more points to adequately represent the calibration range. 10.2 Continuing Calibration Verification (CCV). Analyze a mid-range calibration standard after a maximum of every fifteen samples. 10.3 Solvent blank. Solventblanks are runbefore and after every calibration curve, CCV, matrix and control blank (if contaminationis noted), and afterbatches of no more than30 injections. Acceptablevdues for the blanks are values below 25% of the limit of quantitation (LOQ)of the instrument. If analyte carryoveris a problem, use back-to-back solvent blanks. 10.4 SampleTriplicates. Analyze all sets of triplicate samplesto provide a measure of the precision of analysis. Studysampleswill be analyzedin 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) froma specified exposure type or time may be analyzed within the same analytical batch. 10.5 Analytical spikes. Prepare analytical spike sample for each sample type as applicable to determine the matrix effect on the recoveryefficiency. Concentrationsof the spike should be approximateIyequalto 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 100k 25%. Spike recoveries outside of this range should be noted and used with other criteria to evaluate the condition of the analyticalrun or necessityfor repeat analysis. Consult with the Team Leader or designee for direction and final acceptance or rejection of the analytical run. Samplesmay be spiked at two different concentrationsto ensurethat the resulting levels of target analyte(s)are within the viablem g e of the calibration curve. ETS-8-181 .O Analysis of Photolysis Samples for Fluorochemicalsby HPLCiMS Page 8 of 15 Page 32 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 11.0 CALIBRATION AND STANDARDIZATION 11.1 Analyze standards prior to and following each set of samples. The linear regression will be calculated h m the pIot of all individual calibration points, including but not forced through zero, using HP ChemStation or Target NT Software. A minimum of five calibrationstandards 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 lowhgh 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 documentatiodfootnotesmay be used to justify dropping highnow curve points. 1) "HighAow 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($ 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 malyre." 3) "HighAow calibration point(s) (list points) were excluded as they were not within the +/-25% accuracyrequirementsof the method when the curveswere 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 ChemStationSoftware window, turnthe system "on" to: turnon the drying gas flow; initiate solvent flow through the column and nebulizing needle; equilibrate the column compartment; and equilibratethe 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 softwareto 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 Analysis of PhotolysisSamplesfor Fluorochemicalsby HPLCMS Page 9 of 15 Page 33 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 12.2.3 Perform a Check Tune or Autotune to ensure system operational qualificationand performance verificationof the MSD.Log the Tune results and keep a copy with the analytical raw data. 12.2.4 Load the method file and ensure that the folIowing parameters are a-p-pro.priately set for the target analyte(s): Example mass spectrometer set up*: MSD Ionization mode API-ES (or API-APCI) Polarity Negative (or Positive) Acquisition mode SIM (or SCAN) Gain 1.O (up to 7.O) Fragmentor I Dwell time I Capillary voltage I Dryinggas Nebulizer pressure 70 (may be set to one voltage, of ramped for each ion) 183 msec (time is a function of the amount of ~ I ions). I 3500, or equivalent I Nitrogen, or equivalent ~~ 30 psig, or equivalent Drying gas flow 8 Urnin, or equivalent Drying gas temp 300' C,or equivalent 12.3 LCCheck TIME(MIN) 0.0 1 .o I 4.0 11.0 *%A %0 FLOWRATE 60 40 0.3 rnUmin 60 40 0.3 mumin I I 5 I 95 1 0.3rnUrnin 1 5 95 0.3 mUrnin Page 34 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 increases to a higher organic content over time to separate the analytes, and elute them off the column in a timely fahion. After all analytes have eluted, the solvent ratio is then switchedback to "initial conditions" and held until the column pressure has stabilized ( indicating re-equilibration to initial conditions) prior to the next injection. 12.3.4 Auto-sampler setup: I AUIO-SAMPLER: 1 ALS ModelG I313A I AUTO-SAMPLER PROGRAM: None INJECTION VOLUME: 5.0 pL, or equivalent 12.4.1 12.4.2 12.4.3 12.4.4 12.4.5 Wilhin the sequenceparameters, 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 HP1100/MSD systems). Save all data to a subdirectorylabeled with instrument and analysisdate (e.g. H100200 for analysis on "Hillary,)' on 2 October, 2000). Name datawithin the subdirectorywith instrument ID and injectiodrun number (e.g. for samples acquired on "Hillary", data files shall be `cI-IILLOOO1".... "HILLOOW). 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 2,2000 save sequencetable as H100200.s). 12.5 Sample analysis 12.5.1 Enter the standard, sample, blank identification into the sequence table. Analyze calibration standards first, then up to 30 injections, followed by the calibration standardsre-injected. Multiple sets of samples can be set up in the sequencetable 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 AnalysisofPhotolysis Samples for Fluorochemkalsby HPLCMS Page 11 of 15 Page 35 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 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. Solventblanks may also be used to separate groups of samples and evaluate for carry over problems fkom 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 specificallyto the project and save data, method and sequence files. This will be considered the raw electronic data to be archived. 13.0 DATAANALYSISAND CALCULATIONS 13.1 Peak Evaluation. Peaks must be symmetric in shape and identified by extracting compound-specificions. Peaks considered for quantificationmust have peak heights greater than4 times any baseline level for that region of the chromatogram. Peak area integration is fkom 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 designatedby the Team Leader. Samplesand standardsthat 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 integrationcodesmay be utilized to document what type of manualintegrationwasperformed. A: Adjust Left Anchor B: Adjust Right Anchor C: Delete Integration D: Add Integration Additionally, QAU encouragesthe datareviewerto write commentsdirectly on the chromatogramif there is anythingunusual. Date and initial all documentation. 13.3 Matrix spikes. Calculatethe percent recovery for each of the matrix spikes. Calculate the matrix spike percent recoveries using the following equation: % Recovery = (observed spiked samule result - observed samule resulQ x 100 Nominal amount spiked Using the observedmatrix spike recoveries, calculatethe average spike recovery. ' 13.4 Accuracy, Calculatethe accuracyof each calculated calibrationstandard and CCV samplesusing the followingequation. Accuracy=measured Conc.) x 100 Nominal Conc. ETS-8-181.0 Analysis of Photolysis Samples for Fluorochemicalsby HPLClMS Page 12 of 15 Page 36 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 . 13.5 Sample Triplicates. Calculatethe relative standarddeviation (%RSD) for the triplicate sampIes: RSD = Standard Deviation of Satntde Set x 100 Average of Sample Set 14.0 METHODPJCRFORMANCE 14.1 Coefficient of Determination (8).The coefficient of determination(r2)for the calibration curves should be 0.990 or greater. The curves should be examined closely for linearity and intercept,particularlyfor accuracyof quantitationat the low and high ends of the m e . The accuracyof all standardsused for calibrationmust be within 75125%. It may be necessaryto use quadraticfits of the data, usudly when broad range curves (greater than 3 orders of magnitudebetween the low and high concentrationstandards) are used. Document in the raw data the technicaljustificationfor 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 far 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 technicaljustificationfor deviations. Consult with the Team Leader or designee for direction and for find acceptanceor 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. Inconsistenciesin the internal standardpeak area may indicate instrumental changes over time. Inconsistencies in the surrogatepeak area may indicate instrumental changes, injection m r , or changes in the test-system. Consultwith the Team Leader or designee for directionand final acceptance or rejection of the analytical run. 14.4 continuing Calibration Verification. If the accuracy for the amount ofmeasured analyte is greater than 25% from the nominal value relativeto the initial standardcurve, the Team Leader should be consulted. Only those samples analyzed before the last acceptablecalibrationcheck standardmay be used. Consult with the Team Leader or designee for direction and for final acceptance or rejection for the data. 14.5 Solvent Blanks. Solvent blanks should show no more than a 5% carryover fbrn a high standard or calibrationcheck standard. If so, two solvent blanks may be necessary to rule out instrumentalcontamination. If peaks greater than25% of the peak area of the designatedLOQ value are observed in sequential solvent blanks, this is indicativeof instrument contamination. The instrument shall be serviced by thoroughly cleaning the electrospraysource, and replacing/cleaningcolumns, tubing, etc. (as designated in the Equipment Procedure, ETS-9-34.0)and the analysisrestarted. Consult with the Team Leader or designee for direction and final 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 analyticalrun. Sampleswith 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 Analysisof PhotolysisSamples forFluorochemicahby HPLCMS Page 13 of 15 Page 37 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 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 determiningmatrix effect (interference or suppression) and also to monitor for instrumental or sample contamination. Use of solvent blanks prior to the matrix blank may be necessary to rule out instrumental or sample Contamination. 14.8 Limit of Quantitation (LOQ).The LOQ is equal to the lowest acceptablestandard (i.e. % accuracyis S 25 %nominal value) in the calibration curve that is greater than 4 times the level of the matrix blanks. . 14.9 SampleTriplicates. The analyst shall accept %RSD values <25%. %RSD values z 25% should be noted Data used in the final report that is deemed out of control will be required to have technicaljustification for why the data is used, documented in the final report and raw data. Consultwith the T e e Leader or designee for direction, and for final acceptanceor rejection of the data. 14.10 Control Samples. The acceptancecriterionfor the control samplesis that the accuracyis 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 usedin final report that is deemed out of control will be required to have a technical justification for why the data are being used, documented in the final report and raw data. 14.11 Analytical Spikes. The analyst shall accept percent spike recovery values of 100f25%. 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 technicaljustification 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 demonstratedby acceptable instrumental checks (e.g. abbreviatedd z check-tune, or full auto-tune routines. Consult the appropriate instrumental manuals (Reference 18.2). Furthermore, overlaying calibration curves and implementing check standards (CCV), the method shall be self-validatingif all data qualityobjectivesare satisfied. 15.0 POLLUTIONPREVENTION AND WASTE MANAGEMENT 15.1 Dispose of samplewaste by placingin high or low BTU containersas 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 storagedrum in the hazardous waste collection area on the 2nd floor. 15.3 Use smaller bore columns when possible to minimize waste generation. ETS-8-181 .O Analysis ofPhotolysis Samplesfor Fluorochemicals by HPLC/MS Page 14 of 15 Page 38 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 , - 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 withinstrument ID. 16.3 Fill out appropriatepreparation worksheets completely,making sure to include all initials and dates, along with the study number and sample identification. 16.4 Print out the sampleacquisition sequencetable, reduce the size with photocopyingand tape the photocopy into the instrument log. Keep the original copy for the raw data files. 16.5 Print chromatograms,reprocessingsequenceand batch reports for all analyses. 16.6 Print calibration tables and curve information and store in the raw data file. 16.7 Enter all standardpreparation idormationin the standards preparationlogbook. Make a photocopy of the logbookpage and include the copy in the raw data file. 16.8 Archive electronicdata to appmpriatemedia when necessary. 17.0 ATTACHMENTS 17.1 None. 18.0 REFERENCES 18.1 ETS-9-34.0H,ewlett Packard 1100/MSDEquipmentProcedure. 18.2 Hewlett Packard llOO/MSD instruction CDROM. 19.0 AFFECTEDDOCUMENTS 19.1 None. 20.0 REVISIONS Revision number Reason for revision Date of Revision ETS-8-181 .O Analysis of PhotolysisSamplesfor Fluomchemicals by HPLCMS Page 15 of 15 Page 39 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 3M ENVIRONMENTLAALBORATORY Method Preparation of Samples for Photolytic Exposure Studies in Aqueous Matrices Method Number: ETS-8-176.0 Adoption Date: Approved By: Laboratory Manager Date ETS-S-176.OPrepurationof Samplesfor PhotolysisStudies in Aqueous Mutrices Method Page 1 of 18 Page 40 of 165 1.0 SCOPE AND APPLICATION BACK TO MAIN 3M Environmental Laboratory Report No.W2783 Comoound Perfiuomoctanoic acid Acronym PFOA Comnound I Perfluorobutanoicacid Perfluorooctanesulfonate PFOS Perfluorobutanesulfonate Perfluorooctanesulfonatnide FOSA Perfluorobutanesulfonamide N-methylperfluorooctanmIfonamide N-MeFOSA N-methylperfluorobutanesulfonamide N-ethylperfluorooctanesulfonamide N-EtFOSA +' 2o-c(tNan-emsuetlhfoynlpaemrfilduoo)reothyl alcohol N-MeFOSE-OH 2-OJ-methylperfluorobutanesulfonamidoe)thyl I alcohol I I I 1 Z-~-ethylpefluorooct~~ulfonamidoN) -EtFOSEOH Z-(N-ethylperfYuorobutanesulfonamido)ethyl ethyl alcohol alcohol Acronvm I PFBA ~ ~~ PFBS I FBSA N-MeFBSA N-MeFBSE- 1I OH I N-EtFBSE-OH 1-perfluorobutene I Perfluorooctanehydride 1H,C8-hydride Pefluorohtanehydride lH, Cq-hydride I ... and other C4thru CIOhomologues, and polymericmaterialsbased on the aforementionedcompounds. I ETS-8-176,OPreparationof Samplesfor PhotolysisStudies in Aqueous Matrices Method Page 2 of 18 Page 41 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 Other possible degradation products include, but are not limited to: C2 IH-pefluoroelhme (IH-pE2) 1H-perfluomthane (1H-pKZ) C3 1H-pernuompropane(lH-pfC3) 2H-pefluotopropane (2H-pC3) peffluoro-1-propene (pE3-lene) C, perfluoro-1-butene (pf(34-lene) Pduom-2-butene @fcQ-2ene) W-perflwmbutane (2H-ptU) C, ZH-perf7uororpentiu1e(2H-pfC5) cs pemu~o-2-hexenc(pK6-2ene) 2H-pcrfluorohactnc (2H-pE6) C, 2H-perfluorohcptane(2H-pES) cs perfluom-l-octene (PES-lene) perfluom4-pentenc @KS-lenc) 1H-perfluorohexane (1H-pfC6) perfluom-2-penknc (pK5-2ene) pduom-l-hcxene (pfCdlene) Perfluom-l-hepttne @fC'I-lene) 2H-perfluoroome (2H-pE8) lH-perfluomheptane ( 1 H - p W Peflwm-2-octene (pE8-2ene) 1 1H-perflwmbutane( I H - P ~ c ~ ) IH-pefluorohexane (IH-pm) 1H-pduorooctsno (IH-pE8) 1.3 Acceptable matrices. Aqueous solution of test substance including but not limited to the followingmatrices: pH 7 phosphate buffer, 18.2MSL resistivitywater, 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 degradationby either direct or indirect photolysis, and to identify and quantify degradationproducts 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 duplicatefor separateanalysisby LCMS and dynamicpurge and trap GCMS. When required, the addition of 30% H 2 0 2 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 controlIedat 23-26 "C.Samplesare exposed to approximately 261 W/m2of 310-800nm photo-irradiance for a specifiednumber of &hour periods. An 8-hour period of irradianceis definedas 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 determinedby the Team Leader. The amount of irradiation received by the samplesmay be monitored in one of the following three ways: 1) calculating the totalwattageper length of exposure2) use of a radiometerto measure irradiance output, andor 3) use of a quininemonohydrochloridedihydrate (QMD)actinometersolution exposed along with the samplesand monitored for change in UV absorptionover time. The use of the radiometer provides an accurate measurement at specified time-points; whereas calculatingthe total wattage per exposure length and use of the QMD actinometerprovide time-averagedtotal integrated energies. Suntestinstruments 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 samplesto be analyzedby LC/MS are prepared for analysisby dilutingthe 5 mL sample volume with 30 mL of suitable analytical solvent (e.g. methanol) containing internal standard. The GCMS study samples are stored invertedprior to purge and trap G C M S analysis. ETS-8-176.OPreparaiionofSamplesfor PhotolysisStudies in Aqueous Matrices Method Page 3 of 18 Page 42 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 2.2 An example of samplesto 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 Fe203. -LC/MS With Without Hzo2 Ha01 GCMS 75zFmET WOz MOz + SampleRep 2 + 0 f SampleRep 3 + 0 + Sample Spike + 0 + Matrix Blank + 0 0 Matrix Blank Spike + 0 0 Control Sample Control Spikc 0 0 -+P + Contml Blank 0 + 0 Control Blank Spike 0 + 0 + - Sample Rep 2 + 0 0 + Sample Rep 3 + 0 + Sample Spike + 0 + Matrix Blank + 0 0 Matrix Blank Spike + 0 0 Control Sample 0 -P + Control Spike 0 4- + ControlBlank 0 + 0 X X X X 0 Time 0 X X X X + 0 Time 0 X X X X Time 0 X X X X 0 + Time 0 X X X X Time. 0 X X X X + 0 Time 0 X X X X Time 0 X X X X 0 - + Time 0 X X X X Time 0 _ X . X X X 7 0 Exposed X 0 Exposed X X 0 Exposed X X + Exposed X X + 0 Exposed X X Exposed X X 0 Exposed X X + Exposed X X 0 Exposed X X X X a Samp e Rep 1 + 0 + Sample Rep 2 Sample Rep 3 + 0 + Sample Spike + 0 + Matrix Blank + 0 0 MaaixBIankSpikc + 0 0 Control Sample 0 + + Control Spike 0 + + control Dlank 0 + 0 Control Dlank Spike 0 + 0 0 Unexposed 0 Unexposed 0 + Unexposed Unexposed 0 Unexposed + Unexposed 0 Unexposed 4- Unexposed 0 + Unataosed Unexbsed = ) one se r/H202, One set w/o H z G 3.0 QUALITCYONTROL-DEFINITION/FREQUENCY/PERFCORRIITMEARNICAE I__ 3.1 Blanks 3.1.1 Defmirion: Matrix Blank. An aalyte-free matrix to which all reagents are added in the same voIumes 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 documentcontaminationresulting from the experimentaltreatment and analytical process. Refer to the table below for an example of matrix blank types. The matrix blank is used to document the actual test system without the test substance. The control blank is used to control the test matrix and trace any background levels oftarget analytethat may be matrixspecific. The table below shows an example of a control blank ETS-8-176.0Preporationof Samplesfor Photolysis Studies in Aqueous Matrices Method Page 4 of 18 Page 43 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 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 Malrix Blank Control Blank Matrix descriotion Example: 0.01 M PhosphateBuffer, pH 7 Example: ASTM Type I1 Water Frequency ' 1 Replicate per light and dark exposure, for each time point and for each analytical methodoIogy. Performance Criteria Any background level of analfie shall be less than 25% the area counts of *e LOQ. 3.2 Limit of Quantitation (LOQ) 33.1 Definition: The lowest concentrationthat can be reliably measured within specified limits of accuracy during routine laboratory operating conditions. Sample LOQs are highly matrix-dependent. 3.23 Qual@ Controland Perfontance Criteria: The LOQ is generally 5 to 10times the minimumconcentrationwith a 99% confidence limit that the concentrationis greater thanzero. 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 (rt 25%) of the nominal calibration standard concentration. 3.3 Sample Triplicate 3.3.1 Definition: Three aliquotsprepared as representatives of the same sample s o m e (i.e. test substance) and carried through all steps of the photolytic study process and analyticalprocedures in an identical manner. The results from triplicate analysesare used to evaluatevariabilityof the total method, including sample preparation, photolytic process and analysis. 3.33 Performnce Criteria:The samples in the test matrix will be prepared in triplicate. Each replicate will be prepared for each treatment type: light and dark exposures, with and without hydrogen peroxide, for EACH time-point, and for each analytical methodology(e.g. LC/MS and/orGCMS). See the following table: test analyte(s) 3.4 Control Sample 3.4.1 Definition: A known matrix containing the test analyte(s) carried throughout the entire analytical procedure. This is used to document laboratoryperformance (Le. 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 samplesprocessed to veri@that the precision and bias of the analytical process ETS-8-176,OPreparationof Sampiesjbr Photolysis Studies in Aqueous Matrices Method Page 5 of 18 Page 44 of 165 BACK TO MAIN 3M EnvironmentalLaboratory Report No. W2783 are within control limits. The results of control sample analyses are compared to control limits established for both precision and bias to determine usabiIity of the data. 3.4.2 Perfomrance Criteria One control sample will be prepared per matrix, per treatment type. See the following table: Matrix Description Freauencv of Use 1Replicate per light AND dark Performance Criteria -~ The analyst shall accept recoverv I I 3.5 Analytical Spike (AS) 3.5.1 Deflnitiun: Prepared by adding a known mass of target analyte(s) to a specified amount of a dilutedmdor aliquoted sample. This assumes that an independent estimate of target analyte concentrationis available. Analytical spikes are used to evaluatethe recovery efficiency of the analyte and the effect of the matrix on the measurements. 3.5.2 Quality Control and Performance Criteria: One sample spikewill 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 timepoint, and for each -+ analyticalmethodology (i.e. LCMS andor GCMS). In addition, one matrix blank spike and one control blank spike will be prepared. See the following table: Matrix DescriDtion Freauencv of Use Performance Criteria with target analyte(s) just prior to The analystshall accept spike recovery values spikedwith target analyte(s)just prior to analysis of 100 2 25%. If spike recoveries are greater than 125% or less than 75%, document that the spiked with target analyte(s)just prior spike sample is out of the specifications and justify, if possible, the spiked with target analyte(s)just prior reason. I 3.6 Internal Standard/Surroeate 3.6.1 Internal StandardDefinition (appliestu L W S and G W Ssamples): A known amount of a compound similarin analyticalbehavior to the target analyte(s) of interest,added to all samples and standards (post-irradiation),and carried through the entire analyticalprocess. It provides a reference for evaluating and controlling the precision and bias of the applied analytical method. Samples are ETS-8-176.OPreparaionof Samplesfor Photolysis Studies in Aqueous MatricesMethod Page 6of 18 Page 45 of 165 BACK TO MAIN 3M EnvironmentalLaboratory Report No. W2783 to be quantified using the internal standard providing that the response of the internal standard is consistent (k 5% relative). Use of external calibration methodologyrequireswrittenjustification by the Team Leader. 3.6.2 SurrogateDefinition (appliesto L W S and GGZWSsumples): 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 analyticalprocess. 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. Surrogateanalysis is used to evaluate and control the precision and bias of the anaIytical method. Surrogates are not used for quantitation. Note: Internal standarch are used in all experiments. The use of surrogate standarc& may or may not be used 3.6.3 Q-ualily Control and Performance Criteria: Matrix Description Frequencyof Use. PerformanceCriteria I Sample diluted with 30 Every LC/MS The Coefficientof Variation, or %RSD shall mL of internal sample analyzed be calculated for the area response of all standard compound appropriate samples per analytical batch. The dissolved in a suitable analyst shall accept%RSD values of 4 5 % . analytical solvent The recovery and precision of the surrogates Sample with surrogate Every G C M compound spiked into it. sample analyzed shouldbe 100 S S % and 4 5 % , respectively. Unacceptable values shall be documented and justified, if possible. 3.7 Other Definitions. 3.7.1 Test AnalyteBubstance:Any substance (mixture or controlledcompound) added or administered to the test system for the purpose of chemical analysis. 3.7.2 DegradationProduct@):Secondaryanalytes of interestproduced as a result of chemical reactions during the photolysis and monitored (qualitativelyor 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 d y t e may be identical to the test substance used in the experimentalphase of the study, a by-product or degradationproduct that is monitored (qualitatively or quantitatively) during the sample analysis procedure. 3.7.4 Test Matrix: The physical matrix in which the study will be conducted. Also referred to as the test system. 3.7.5 Control Matrix: A known physical matrix to be included with the study for comparison with the test matrix. 3.7.6 Relative Standard Deviation (RSD):A measure of relative precision for three or more sample replicates; defined as the sample standard deviation divided by the sample average and multiplied by 100. This is expressed as percent (OARSD). 3.7.7 Accuracy: The closenessof agreementbetween an experimentallydetermined value and an accepted reference value; defined as the measured value divided by the nominal value and multiplied by 100. ETS-8-I76.OPreparationof Samplarfor PhotolysisStudies in Aqueous Matrices MethodPage 7 of 18 Page 46 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 4.0 HEALTHAND 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. 4.1.3 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 Glassware in which standards are prepared should be rinsed with solvent to reduce the possibility of accidental contamination. 4.2.2 The photoreactorsare 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 electricaloutlets 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 samplesin 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 sampleanalysis. Care must be taken to prevent alI possible contaminantsby using fresh reagents, analyticalgrade solvents and clean glassware during the sample preparation processes. 6.0 EQUIPMENT 6.1 Analytical balance sensitiveto 0.1 m g 6.2 Photoreactor: Suntest CPS+,X S + ,or equivalent, equippedwith axenon arc-lamp and capable of producing integrated irradiance values from 100-680 W/m2 over the wavelengthrange of 290-800 nm. Lamp output must be filtered to allow only 290-800 nm wavelengths. A flowing water bath with circulating pump is required. Consult the appropriate 3M SOP for instructions. 6.3 Water recirculatingcooler capable of maintaining temperature at 25 OC f 5 'C, from Poly Science, Model 1177-Por 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, Thennostatted Cell Holder: Model 08451-60104, or equivalent. 6.4.1.1 1.O-cm path lengthquartz spectrophotometer cell from Hewlett Packard, or equivalent. 6.4.2 Long Path-Length Cell Holder, HewIett Packard (# 89076C) or equivalent. ETS-8-176.OPreparationof Samplesfor PhutulysisStudies in Aqueous Matrices Method Page 8 of 18 Page 47 of 165 BACK TO MAIN 3M EnvironmentalLaboratory Report No. W2783 6.4.2.1 10-cmpath length quartz cell equipped with stopcocks,Hewlett Packard Part # 5061-3392, or equivalent. 6.4.3 Data acquisitionand analysis software, HP ChemStationfor W-Visible Spectroscopy,G1116A4, Rev. B.01.02,or later. 6.4.4 PC Computer capable of running appropriate analysis software to acquire and report data. 6.5 Centrifuge capable of maintaining >2000 rpm for 10minutes at ambient temperature. 6.6 Radiometer (optional) capable of monitoring the energy from a xenon source from 290 to 480 nrn over time. Model PMA2100, Version 1.16, Solar Light Company, Inc., or equivalent. Consult the appropriate 3M SOP for instructions. 7.0 SUPPLIESAND MATERIALS 7.1 40 mL amber and clear glass VOA vials with screw caps with septa. 7.2 Crimp cap autovials-1.5 mL, caps, crimper, and decapper. 7.3 Adhesive-backed labels (return address size) for labeling quartz vials and autovials. 7.4 Disposable glass graduated pipettes, 1 mL to 10 mL. 7.5 Disposable glass Pasteur pipettes and rubber bulbs. 7.6 Glass beakers, various sizes. 7.7 Volumetric flasks,from 10mL to 1000mL. 7.8 Hamilton Gastight@syringes(precision-k 1%of the total volume), 5 pL to 1000pL. 7.9 10 mL Bottle-top dispenser, Calibrex, Model # 51 1, or equivalent. 7.10 Adjustablerepeater pipette, Wheaton Step-pette411, or equivalent, equippedwith the appropriatevolumetricrange pipette tips, 7.11 Ziploc@plastic bags, or equivalent. 8.0 REAGENTS AND STANDARDS 8.1 Methanol (MeOH). HPLC/SPEC/GC and/or purge and trap grade (EM Science, or equivalent. 8.2 Acetonitrile(ACN). HPLC/SPEC/GCand/orpurge and trap grad fiom EM Science, or equivalent. 8.3 Aqueous Matrix, includes but is not limitedto the followingmatrix types: 8.3.1 ASTM Type I water. Mili-Q@' or equivalent, with a measured resistivity >18.0 Mn-cm. 8.3.2 0.01 M pH 7.0 PhosphateBuffer.Example: Weigh 1.36 g mZP04 into a 2 L volumetric flask and dissolve into 1L of Type I water. Add 600 mL of 0.1% NaOH. Adjust to pH 7.0 f0.1% with 0.1% NaOH or dilute H$O4 and dilute to the mark with Type I water for a finalconc. of 10mM. 8.3.3 Lake Surface water. Collected fiom a known source, with known specifications for Dissolved Organic Carbon (DOC) and Total Organic Carbon (TOC). 8.3.4 Sea water. Collected fiom a known source, with known DOC and TOC specifications. 8.3.5 Aqueous metal solutions and slurries (e.g. TiO2, Fez03). Example: Dilute 0.015 g of Ti02 (Aldrich Chemicalor 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-8-176.OPreparationof SamplesfoT PhotolysisStudies in Aqueous Matrices Method Page 9 of 18 Page 48 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 8.4 Hydrogen Peroxide (3202). 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 solutionsfor the test mlyte, target analytes, internal standard are prepared in an organic solvent (e,g. methanol, acetonitrile) at concentrations of approximately 10,000pg/ml by weighting approximately 0.1g of the appropriate substance into a 10-mL volumetric flask and diluting to the mark with solvent. This solution is then diluted to make appropriate working solutions. 8.7 Test Analyte Solution: 8.7.1 Examde for water soluble andyte(sk Example: A 1 pg/mL test substance solution in the test matrix (Section8.3) is prepared by diluting 0.050 mL of stock solution (Section 8.6.1) to 500 mL, with test matrix. Aliquots (5 mL) of this solution will transferred to VOA vials for subsequent photolysis. 8.7.2 Exmule for poor water soluble analvte(s) or those with adsomtion difficulties: Prepare a solution of the test substance in acetonitrile (Example: A 500 pg/mL test d y t e solution is prepared by diluting 500 pl 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/nd., test substancestock (Section 8.6.1) into a VOA vial containing 5 mL of the test matrix. *Acetonitrileis currentlythepreferred solvent to use when introducingthe 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 photoa'ysis of the intended test substance. Evidence of thisphenomenon (approximately IO% decrease in the concentrationsof thefinal products) has been observed in a study here at 3M (EtFOSE-OHphotolysisinpH 7 buffer,with and withoutpresence of M e o w . 8.8 Target Analyte(s) Spiking solution: Example: A spike soIution of test analyte and 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 10mL with MeOH. The fmal concentration is approximately 500 pg/mL test substance/I00 pg/mL target analytes. Addition of 10 pL of this targetanalyte spiking solution into the 35-mL diluted sample volume will result in approximateiy 140ng/ml and 30 ng/ml concentrationsfor the test analyte and target analyte(s), respectively. *Pre-estimationof the degradationpotential of the test anaQte and subsequent degradationproducts is not alwayspossible. Ifpossible, an aplalyticalprescreening of representative samples should beperformedfor accurate spiking. Generalrule of thumb has been that the test anabte spike amount be ETS-8-176.OPreparation of Samplesfor Photo!& Studies in Aqueous MatricesMethod Page 10 of 18 Page 49 of 165 BACK TO MAIN 3M EnvironmentalLaboratory Report No.W2783 approximately25%- 50% of the initial concentration. The target analyte(s)spike amount has been 10-100 nglml, depending on expected levels under specific conditions. More than one spike solution may be utilized to adequatelyrepresentthe levels in the samples. Example: A test analyte that undergoessignificantdegradation duringphotolysiswill require a lower spike concentrationin the Exposed sample set due to less test analyte remaining. TheDay 0 and Unexposedsample 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 equivalentto approximatelyhalf the are response of the test analyte's high standard in the calibrationcurve. Enough dilutionsolution shall be prepared for use in all the study samplesand in preparation of the calibrationcurve samples. ExampIe: Internal standard solutionis prepared by diluting 100pL of stock solution (Section 8.6.1) to 4.0 L withMeOH to a concentrationof 250 ng/mL. 8.10 'Quininemonohydrochloridedihydrate (QMD). 90% from Aldrich Chemical. 8.11 QMD solution: A 2% (wh)solutionof quininemonohydrochloridedihydrate solution is prepared by weighing approximately2.0g into a weigh boat, transferringto a 100mL, . flask and diluting to volume with Milli-Qa water. 9.0 SAMPLHEANDLING 9.1 Record times of initial preparation, reference numbers of reagents wed 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 G C M S samples. G C M S 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 exceptionto this being the need to brieflyturn the samples upright for Ha02 injectionthroughthe septa of the appropriate VOAsample vials at speciJed time intervals (See Section 12.6 and Section 12.1I. 7). 9.3 The completed photolysis samples remain inverted and refrigerated at 1-5 OC prior to analysis by LC/MS or sample purge and trap GC/MS. 9.4 Samplepreparation prior to LC/MS analysisrequires the additionof 30 mL, of diluting solvent containing internal standardto the 5-mL photolysis samples. This is to ensure completerecovery of the target analytesfrom the glass VOA vial surface and to dilute the samples into a working analytical range. Day 0 study samples stored at 1-5 OC during the time of photolytic exposure are removed and prepared for analysis at the Same time as the exposed and unexposed samples. ETS-8- 176OPreparation of Samplesfor Photolysis Studies in Aqueous Matrices Method Page 11 o f 18 Page 50 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 10.0 QUALITCYONTROL 10.1 Refer to the defiaitions section for the quality control specified for each respective sample type. 11.0 CALIBRATIAONND STANDARDIZATION 11.1 The compounds of interestmust be characterized accordingto laboratoryspecifications. 11.2 All equipmentused, such as the analyticalbalance, radiometer, etc. should be calibrated prior to use (daily, weekly, etc.) as specified in the staudard operatingprocedure(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 appropriateLCMS and GC/MSmethodologiesfor further analyticalinformation. 12.0 PROCEDURE 12.1 Obtain the absorbance spectra of the test compound in aqueous solution using a UV- Visible Spectrophotometer(ETS-9-46.0). 12.1.1 Using a IO-cm quartz spectrophotometercell, obtain a blank water absorbance reading over the range 290-800 nm to determine a background or baseline reading. 12.1.2 Aliquot a solutionof water containingtest substance, at a concentrationless than half the solubilitylimit, into a 10cm quartz spectrophotometercell and obtain an absorbance reading over the range 290-800 nm. A positive absorbance may indicate the potential of the analyte to undergo direct photolysis. Non-absorbing d y t e s would be more likely to undergo indirectphotolysisas the potential degradation pathway. 12.2 Obtain the appropriate number of clear and amber 40-mL glass vids with caps and cardboardboxes. Label the vid caps using a black permanent pen to distinctly identifjr samples. Paper labels will be applied post-hydrolysis as they don't stick in water. 12.3 Prepare appropriatesamplepreparation worksheets and create labels for each sampleto affix to the 40 mL VOA vials and the autovials for analysis after photolysis. The labels should include the study number, Sample number, test compound, matrix, exposure type (exposedlunexposed Day 0), date and initialsof the analyst. 12.4 Aliquot 5 mL of the following solutions into clear (for EXPOSED samples) and amber (for UNEXPOSEDand DAY 0 samples)40 mL glass VOA vials: 12.4.1 Matrix with test substance (sample reps 1,2,3,and samplespike). 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). (Whenappropriate,test substance may be added afrr 5mL aliguots of matrix have been added to the vials. See Section 8.7) 12.5 All exposed, unexposed, and day 0 samples will contain sample sets with and without peroxide and prepared for LCMS and GCMS analyses according to the followingtable: ETS-8-176.OPreparationofsamplesfor Photo&sis Studies inAqueous Matrices Method Page 12 of 18 Page 51 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 Sample Treatmenflype Matrix with test substance Matrix without test substance Control matrix with test substance Control matrix without test substance EXPOSED,UNEXPOSED,& DAY 0 I # of Samples 6 +HZ02(3LC/MS,3GC/MS) 6-H2Oz(3LCIMS ,3GC/MS) 2 +H202 (lLCIMS,lGC/MS) 2-HzO2 (lILCIMS,IGCIMS) 2 +Hz02(iLC/MS,lGC/MS) 2 -HZ02 (1I LCIMS, IGCMS) 2 +H202(lLC/MS,lGC/MS) 2-HZ02 (11LCIMS,IGCIMS) 24 x 3 per exp type =72 # of Spikes 2 +HZ02 (1 LCiMS, 1GCMS) 2 -Hz& (ILCIMS,lGC/MS) 2 +H20z (lLC/MS, 1GC/MS) 2 -H202(1LCiMS, IGCMS) 2 +H202(lLC%S,lGCiMS) 2 -H202 (1 lLC/MS,lGC/MS) 2 +H202 (lLC/MS,lGC/MS) 2 -HZ02 (1 lLC/MS.IGC/MS) 16x3=48 12.6 Separatethe 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 appropriateamount (e.g. 10 50 pL) into the vial. (Subsequent additionsof peroxide shall be injectedthrough the septa of the VOA vials.) 12.7 For use of quinine actinometer (Optional): Prepare a batch of quinine irradiation control samplesby aliquoting5 mL of the 2% aqueoussolution (Section 8.8) into the appropriatenumber of clear and amber 40 mL I-CHEM vials. Prepare one clear and one amber vial per reactor, per day ofexposure. Storethe vials at 1-5 *C and protected from light prior to use. Place one clear vial in the reactor per day, while removing exposed quinine controls. Exposed quinine controlsneed to be wrapped in foil upon removal to protect fromfurther exposure. Store at 1-5 O C prior to measuring the absorbancevia W-Vis Spectrophotometer. The absorbancemeasurement should be performed as soon as possible, as the absorbance increaserate 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" samplesimmediatelyin a cooler at 1-5 OC or freeze at a continuos temperatureof less than 0 "Cyinverted and protected from light. 12.9 Place "Unexposed" sample vials (amber) into Ziploc" bags separated and labeIed 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" sampleswill remain immersed in the 23-26 OC 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 PHOTOREACTOR SET UP ETS-8-176.OPreparationofSamplesfor PhotolysisStudies in Aqumus Matrices Method Page 13 of 18 Page 52 of 165 BACK TO MAIN 3M Environmental Laboratory Report No.W2783 13.1 Set the irradiationintensityat the desired output. For most experimentalconditions, an intensity of 261 W/m2 is chosen because it yields the equivalent average optimum natural daylight radiation for 300-400 nm at known latitude. (see the table below): Irradiance Source Average optimum Natural Daylight' P Atlas Photoreactorwith inte ted irradiance output of 261 W/m 300-800 nm using the IR Reflecting and 290 cuton filters ADDroximate Integrated and Individual Irradiances in W/m2 250-300 nm 300400 nm 0.0 I 27.8 400-800 nm 259.0 340 m 0.30 ~ 420 m 0.67 0.08 27.8 234.36 0.24 0.71 Parameter Program #, # of Phases - Flowing Water ("FW") Irradiation intensity Duration of exposure Setting 191 ON Example: 261 wattshn2 Example: 8 hours 13.7 After enteringthe appropriateparameters within the menu, select program #1 to run and start the irradiationprogram. Upon Iamp 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. 10-50 pL) of 30% HzOz solution (Section 8.4) and swirlto ensureadequate mixing. Maintainthe inverted position of samplesremoved for spikingpre- and post- the actual peroxide injection. Return samples to their designated locations (bottom of reactor pan ETS-8-176.OPreparationof Sampfesfor Photolysis Studies in Aqueous Matrices Method Page 14 of 18 Page 53 of 165 BACK TO MAIN 3M EnvironmentalLaboratory Report No. W2783 13.9 13.10 13.11 13.12 for the unexposed samples, reactor tray holder for the exposed samples, or the cooler for the Day 0 samples). Note: Don't forget to addperoxide to appropriateDay 0 samples! Remove the exposed quinine control sample from the reactor tray and visually confirm a color change as an indicatorof photoreactor performance. The solution should be a grayhrown color after irradiation. Record the total time exposure of the sample, wrap the sample in foil to protect fiom light and analyze the quinine sample. Place a new quinine solution vial into the photoreactor tray with the exposed samples. Note: Quininesamples doNOT receiveperoxide. Record the chamber temperaturedaily on the sampleprep sheets. Upon completion of the photoIytic exposure, samplesare removed, labeled with adhesive-backed labels and the study sets (Exposed, Unexposed and Day 0) organized for LC/MS or GCMS analysis. If subsequentanaIysis can not be performed immediately, store samples in a cooler at 1-5 'C. Pertinent informationregarding start and stoptimes of photoreactor exposure study, water bath and chamber temperatures, addition of peroxide, and an explanation of unexpected occurrencesshall be documentedon the sample preparationworksheets, with appropriatedates, times and initials. 14.0 SAMPLE PREPARATION FOR ANALYSIS. 14.1 LCIMS sample extraction and prep. 14.1.1 Dilute all 5 mL samples by a factor of I :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 samplesappear cloudy, and/or the sample matrix appearsunclear, it may be necessaryto centrifugethe samples, at an appropriate speed and duration (e.g. 2000 rpm for 10minutes), untilno noticeableparticdate matter is suspended in the sample. 14.1.5 Aliquot approximately 1 mL into autovials and tightly cap. 14.2 GC/MS sample preparation. 14.2.1 Set up autosampler and concentratormethods. If samples'havebeen kept in cold storage, bring samplesto room temperature (approximately23-26"C). 1 4 3 3 Spike vials throughthe septa and place in the autosampler. 15.0 DATAANALYSIS AND CALCULATIONS 15.1 The amount of target analytes in the sample will be quantified against a standard curve regression. 15.2 Means will be calculatedby addingthe individual entities and dividing the resultant sum by the number of individual entities. 15.3 Standard deviationswill be calculated using either Microsoft Excel@or Microsoft Access@to calculate standarddeviation. The built in functioncontainsthe following equation which is based on the individual entities (n) being less than 30: J - n Z x 2 ('CX)~ n(rr-1) ETS-8-176,OPreparationof Samplesfor PhoiolysisStudies in Aqueous Matrices Method Page 15 of 18 Page 54 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 15.4 Sample precision will be reported as % relative standard deviation (% RSD). Sample % RSD will be calculated using the followingequation: where: Ah3 X 100= Sample % RSD A= standard deviation of averaged samples B= average of samples 16.0 METHODPERFORMANCE 16.1 Refer to the definitionssection for the method performance specificationdcriteriafor each respective sample type. 17.0 POLLUTSOPNREVENTIOANM) WASTMEANAGEMENT ~ 17.1 ~ Dispose of samplewaste by placing in high or low BTU containersas appropriate. Use broken glass containersto dispose of glass pipettes. 18.0 RECORDS 18.1 Fill out the photolysis sample preparation worksheet documents completely, making sure to include all initials and dates. Storephotolysissamplepreparationworksheets 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 Photochemistry.p 480 20.2 Interpersonalconversationwith Canie 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 S h e d , SalesRepresentative,26 July, 2000. 20.4 "Atlas Xenon Filter Combination and Sunlight Measurements," information generated by AtIas Electric Devices Company sent via fax by Richard Sherwin, Sales Representative, 26 July, 2000. ETS-8-176.OPreparation ofSamplesfor Photolysis Studies in Aqueous MatricesMethod Page 16 of 18 Page 55 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 20.5 Bergstrom, David H., Thomas C. Kester, and Shangdong Zhan. "Quinine Chemical Actinometry Studies Under Two Light Sources Specifiedby the ICHGuidelineon Photostability Testing." 21.0 AFFECTEDOCUMENTS 21.1 None 22.0 REVISIONS Revision Number. Reason For Revision -- Revision Date ETS-8-176.OPreparation of Samplesfor Photolysis Studies in Aqueous Mgtrices Method Page 17 o f 18 Page 56 of 165 BACK TO MAIN 3M Environmental,Laboratory Report No. W2783 - Attachment A PhotolysisSamplePrep Sheet Tat Anal* Fluororbemica1Degradation(Photolysis) Analysis Sample Prep Sheet Commmb: t I I I I I I diffonu solutionID. no additionof~olutim ETS-8-176.OPreparationof SampIesfor PhotolysisShrdies in Aqueous Matrices Method Page 18 of 18 Page 57 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 3M ENVIRONMENTLAALBORATORY EQUIPMENPTROCEDURE OPERATIONAND MAINTENANCE OF THE SUMLIGHTEXPOSURE SYSTEM, &WMI3FtSION UNIT, AND RECIRCULATINGWATER CHILLER SYSTEM Procedure Number: ETS-9-44.0 Exact Copy of Original & ,7-2f-1/) Initial Date Approved by: Adoption Date: ./U/.. Revision Effective Date: ETS-9-44.0 Rquipment Procedurefor the Atlas SUNTESTSunlight Exposure System Page 1of 8 Page 58 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 1.0 SCOPEAND APPLICATION 1.1 This equipmentprocedure describes the regular operation and maintenanceof the Atlas SUNTEST" Sunlight Exposure System equipped with an immersion unit and recirculating water chiller. 2.0 DEFINITIONS 2.1 Photon energy: U =hv =hc/k where h is Planck's constant, c is the speed of light, and v and 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/m2specific to a wavelength or wavelengthrange. The irradianceoutput specific to the types of Atlas wavelength filters available (Reference 14.9) should be used as a guide to calculatingthe globalirradiance(in units of W/(m2nm) needed to give a specific energy over a desired wavelength range. 3.0 DESCRIPTION 3.1 The Atlas SUNTEST@SunlinhtExposure System (CPS+or XU+)produces visible and ultraviolet light (250-765 WL2). Light produced is filtered with a-fi-Iteror combinationof filters to allow specificwavelengthranges. Samplesare 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 IDENTIFICATION 4.1 Atlas SUNTEST"XLS+, equippedwith a xenon arclamp, lamp fiIter(s) available from Atlas to allow specificirradianceranges, and immersionunit. 4.2 Atlas SUNTEST" CPS+, equipped with a xenon arclamp, lamp filter@)availablefrom Atlas to allow specific irradianceranges, and immersion unit. 4.3 Neslab CFT-33 Refiigerated recirculator or equivalent 5.0 WARNINGASND CAUTIONS 5.1 Health and SafetyWarnings: 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 immersionunit with water, always shut off all power to the SUNTEST@device and the immersionunit to prevent electrical shock. 5.2 Cautions: 5.2.1 Handle opticalparts carefbUy, fingerprintson 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-94.0 Equipment Procedurefor thei4tIa.s SUNTESTSuniightExposure System Page 2 of 8 Page 59 of 165 BACK TO MAIN 3M EnvironmentalLaboratory Report No.W2783 5.2.3 Keep SUNTEST@unit clear of obstructions that would block vents; overheating may cause blown fises, shortened lamp life or other damage. 5.2.4 After beginning the experiment, always make sure that the sample vials are sufficientlysubmerged. Excessive heat may affectthe results of the experiment. 5.2.5 Manually drain the immersion tank on the XLS+ models after stopping the run; otherwise, the water will overflow. 6.0 SPECIAILNSTRUCTIONS 6.1 None. 7.0 RESPONSIBILITY 7.1 The analyticalgroup of personnelwho routinelyoperates the equipment is collectively responsible for the instrumentoperationas described in this document. The person responsible for maintenance and calibration(and an alternate) will be identified in the fiont of the equipment logbook. 8.0 SUPPLIES AND MATERIALS 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 --WipesTM 8.5 Optionalradiation filter@)for lamp available from Atlas: Filter/ Atlas Part Number QuartzDish w/IR reflectivecoating, PN 56052388 Quartz Dish, PN 56052373 Prooerties IR reflective coating (supplied standard with unit) Uncoated (to allow higher black standard W Special SupraxQFilter,PN 56052371 Window Glass Filter, PN 56052372 Window Glass Solar ID 65 Filter, PN 56077769 Solar StandardFilter, PN 56077759 Cut-on at 290 nm, simulates outdoor solar radiation. Cut-on at 310 nm, simulates exposure behind 3 mm (0.118 in.) window glass. Cut-on at 320 nm, simulates exposurebehind 6 mm (0.236 in.) window glass. (Must be used withWindow Glass Filter above.) I Cut-on at 290 nm, simulates outdoor solar radiation at optimal w intensity. ETS-9-44.0 Equipment Procedurefor the Atlas SUNTESTSun&ht Exposure System Page 3 o f 8 Page 60 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 9.0 CLEANINPGROCEDURES All routine and non-routine cleaningprocedures will be performed by person@)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,cleaningmaterids or the reflector may be permanentlydamaged and irradianceuniformitywill 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 residuein the circulatingwater 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 1500hours or when the required irradiancelevel cannot be achieved (e.g. error message reads "E MAX Power reached; CHANGEXENON LAMP") Refer to the SUNTESP instructionmanual for details on how to replace the lamp. 10.1.2 If the temperaturenear the lamp becomestoo high, the fuse blows to interrupt power and save the lamp (indicated by the error message "DOOR OPEN or TEMPERATURE FUSE"). Refer to the SUNTEST" instruction manual for details on how to replace the fuse. 10.1.3 Record routine maintenance in the equipment log (see Section 12). 10.2 Non-routinemaintenancewill be performed by the person(s) designated in the front of the equipment log (see Section 12): 10.2.1 If the equipment fails to operate, refer to the equipment manual for further instructions, if necessary. Contact the Team Leader for instructions if the equipment cannot be made operational. 10.2.2 If an abnormal operating situationoccurs or if calibrationverification fails, contact the responsibIe 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 CALIBRATION 11.1 The photoreactor is set to maintain a specified integrated energy output. The amount of energy output fkom 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@systemswill be performedtwo times each year by Atlas Electric Devices Company. ETS-944.0 Equipment Procedurefor the Atlas SiJhTEST Sunlight Exposure System Page 4 of 8 Page 61 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 12.0 OPERATINPGROCEDURES 12.1 For more detailed operating instructionsrefer to the equipmentoperatingmanuals. 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 temperatureknob to desired set point. Allow temperature to equilibrate before igniting the SUNTEST" lamps. 12.4 SUNTEST" X L S + or SUNTEST"CPS+ unit set-up 12.4.1 Select the desired wavelength filter from the parts listed under Section 8.4 to achieve the proper irradiation specified in the program, and program the photoreactorwith the filtertype information: With the photoreactor menu in the "Program" mode, select the appropriate filter combination type: ODtical Filter Svstem Designations A: Coated quartz @ass only B: Coated quartz glass with UV special glass C: Coated quartz glass with window glass D: Uncoated quartz glass only E: Uncoated quartz glass with UV special glass F: Uncoated quartz glass with window glass 12.4.2 Selectioddeterminationof energy output (Wlm2) 12.4.2.1 Irradiancecontrol and displayisbetween 250-765 W/m2(nominally 300800nm).The irradianceis determined by the settings of the test program [including type of filter(s) used]. The selectable range is from 250 W/m2 to 765 W/m2 (page 12, XLS+ Instruction manual). The total (integrated) energy output (300-800 nm) is directly dependent on the type of lamp filter@)used. E.g. if the filterhas a narrow range such as a cut-on at 400 nm,all irradiance energy coming from waveIengths 400 nm will not reach the samples, and the total integrated irradiancewill be less than if the filter's cut-on was at, for example, 290 nm. 12.4.2.2 Once the proper filter(s) idare designated, the photoreactorwill base the energyoutput on what type of wavelengths arebeing 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 calculatethe desired spectral irradiance. Reference 14.7may be used to calculatethe programmed global irradiancenecessary 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 Suntest@photoreactors. Reference 14.9 is a usefiiI reference for determiningirradiancesat a specific ETS-9-44.0 Equipment Procedurefor the Atlas SLINTEST Stinlight Exposure System Page 5 of 8 Page 62 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 wavelength or a wavelengthrange using specific filter combinationsat specified global irradiances of 250,500, and 765 W/(m2nm). 12.5 Photoreactor Anabis set up 12.5.1 Place VOA (volatile organic analysis) vids containingsamples (see the appropriateanalyticalmethod) into the test chamber. Sample vials to be exposed must be cap side down to allow light to enter the vial. Tighten caps securelyto prevent leakage. Securethe vials in the chamberto prevent floating once the water beginsto circulate. 12.5.2 Close the chamber door and turn the power on. 12.5.3 From the initial LCD display, use the arrow keys to select Program. Press "Enter". 12.5.4 Ifprogramminga 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 followedby 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 initiallypresent in the immersiontank is not sufficientto fill the samplechamber once a program has started. Refill the immersion unit as the water level drops below the fill line. Once a progam has finished,&ah the immersion tank so that it does not overflow when water fiom the sample chamber drains back down into the inlmersionunit. Failureto do so may result in remote flooding. 12.5.9 To intempt operation(e.g. to add peroxide reagent)Press "Stop". If it is necessaryto turn the power off (to exchange the lamp, for example) wait until the fan turnsoff in 1-3 minutes before turning power switch to "Off and unpluggingthe power cord. When ready to continue operation,turn power "On". 12.5.10 To resume operation, press "Start?'. The program will continue at the point 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 remainingin the running program. 12.5.12 The SUNTEST@will shut off automaticallywhen the switch-offcriteria are reached, To display the total time and irradiance, press "Enter". Record exposuretime in instrument runlog. Then turn power "Off". 12.5.13 To manually stop the program, press "Stop". Wait untiI lamp is cooled, then press "Escape". Power canthen be turned "Off '. ETS-9-44.0 Equipment Procedurefor the Atlas SUNTESTSimlight Exposure System Page 6 of 8 Page 63 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 13.0 RECORDS 13.1 Instrument logbooks 13.1.1 Equipment Log: The person(@designated at the front of the equipment log will record all cleaningand maintenance activitiesin the appropriatelog for each SUNTEST" system. Records for routine maintenance of equipment must include the dates of the operation, whether the operations followedthe SOP,and the initids 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 experimentin the appropriateinstrument 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: XENOVEW" 2.2 Storage S o h a r e will receive and record the measurement data transferred from the SUNTEST" systemto 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 XENOVE?W@softwareinstructionmanual for details on how to operate software. Any printouts of program or other data should be initialed and dated prior to adding to the study file. 13.2 Identification.recordsfor each systeminclude equipmentID, 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 REFERENCES 14.1 SUNTEST"XLS/XLS+ Instruction Manual, Doc. No. 20-8036-00Rev. 0 12/98 AtIas Electric Devices Company. 14.2 SUNTEST@CPS/CPS+OperatingManual,6/97 Atlas Company. 14.3 SUNTEST@XLS+ ImmersionDevice OperatingManual, 2/99 Atlas Company. 14.4 SUNTEST" CPSt%XLs+ SoftwareDocumentation 1.4Atlas Company. 14.5 XENOVIEW@2.2 StorageSoftwareOperatingInstructions. 14.6 ETS-9-50.0, Operation and Maintenance of Radiometer and Detector. 14.7 "SUNTESl?Irradiance in W/m2*nm". Tables furnished by Atlas Company. 14.8 "AtIas Xenon Filter Combination". Table furnished by Atlas Company. 14.9 "SUNTEST"CPS/CPS+SpectralIrradiance Distribution". Table furnished by Atlas Company. ETS-9-44.0 Eqttipment Procedurefor the Atlas SUNTEST Sunlight ExposureSystem Page 7 of 8 Page 64 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 15.0 AFFECTEDDOCUMENTS 15.1 None. 16.0 REVISIONS Revision Number. Reason For Revision Revision c Da_ te ETS-944.0 EquipmentProcedurefor the AtIas SUNTEST Stinlight Exposure System Page 8 of 8 Page 65 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 3M ENVIRONMENTLAALBORATORY ANALYSISOF FLUOROCHEMICABYLASRCHONPURGEAM) TRAP AUTOSAMPLER, TEKMAPRURGEAND TRAP CONCENTRATORAND AGILENTGAS, CHROMATOGFUPWMSAPSESCTROMETER Procedure Number: ETS-3-1820 - Exact Copy of Original -2Zz- Initial "35L-9-9 Date Approved by: - Laboratory' Manager Adoption Date: I /23 00 Revision Date: ,>/&-& Date ETS-8-182.0 AnaIysis of FCs by Purge & TrapAutosarnpler/Concentrator/WMS Page 66 of 165 BACK TO MAIN 3M Environmental Laboratory Report No.W2783 1.0 SCOPE AND APPLK!ATION 1.1 Scope. This method is used for the analysis of selected hydrolysis and photolysis samples for the presence of degradationproducts such as olefins and hydrides using gas chromatographylmassspectrometry in a full scan mode. An Archon autosampler and Tekmar Purge and Trap concentrator (or an equivalent system) is coupled to a GC for purging analytes from the liquid matrix and concentrating them on the trap column before injecting on to the GC. 1.2 Applicable compounds. Compoundsthat may be analyzed by this method are listed below. Other fluorochemicalsmay be detected by monitoringmass spectra and running library comparison. Compoundsthat are detectedbut do not have appropriate standards, will be quantifiedrelative to structurallysimilar standard compounds listed below. 1.2.1 1H-perfluomethane(1H-pfC2) 1.2.2 Perfluro-2-butene (pfC4-2ene) 1.2.3 1H-perfluropropane(1H-pK3) 1.2.4 1H-perfluorobutane(1H-pf 1.2.5 Perfluoro-2-heptene (pfC7-2ene) 1.2.6 Perfluoro-l-heptene (pE7-lene) 1.2.7 1H-perfluorohexane(1H-pfC6) 1.2.8 Perfluoro-2-octene (pfC8-2ene) 1.2.9 IH-perfluoroheptane (1H-pK7) 1.2.10 2H-perfluorooctane(2H-pK8) 1.2.11 1H-perfluorooctane(1H-pfC8) 1.3 Instrument Surrogate compounds.Added at the time of analysis and used to monitor perfonnance of purge and trap autosampler and concentrator. 1.3.1 Dibromofluoromethane 1.3.2 Toluened8 1.3.3 4-Bromofluorobenzene 1.3.4 Pentafluorobenzene 1.3.5 1,4-Difluorobenzene 1.3.6 Chlorobenzene-d5 1.3.7 1,4-Dichlorobenzene-d4 1.4 Sample Surrogate compounds. May be added at the time of sample preparation. 1.4.1 Perfluorocyclohexane 2.0 SUMMARY OF METHOD 2.1 A dynamic purge and trap system (autosampler and concentrator) is coupled to a temperatureprogrammed GC for analyteseparation 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 subsequentdesorptionmode, gas flows in opposite direction and temperature of the chemical trap increasesto 250OC. The trapped analytes are transferred onto the GC column for G U M S 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 FCs by Purge & TrapAutosampler/Concentrator/GCYMS Page 2 of 12 Page 67 of 165 BACK TO MAIN 3M EnvironmentalLaboratory Report No.W2783 3.0 DEFINITIONS 3.1 Calibration Standard. A dilution of various amounts of a stock, intermediateor purchased standard to achieve standard solutions in a concentration range of interest. 3.2 Calibration Curve. The graphical relationship between known values, such as concentrationof a series of calibration standardsand their instrumentalresponse. 3.3 External Standard Quantification. Process of establishing the concentrationof a target analyte by plotting the theoretical amount (in units of ng/mL or pg/niL, etc.) versus the response of the target analyte(s) on column. The resultant curve(s) shall be used to determineunknownconcentrationsby comparingthe area response of target analyte(s) to the area response and correspondinganalyte amount on the appropriateanalyte's calibration curve. 3.4 Coefficient of Determination(8).The squareof the correlationcoefficient. It is the proportion of the variation in the dependentvariable that is accounted forby the independent variable. 3.5 Instrument Surrogate. An organic compound similar to the target analyte(s) in behavior in the analyticalprocess, 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 similarto the target analyte(s)in chemical composition and behavior in the analyticalprocess, but is not normally found in the sample(s). A surrogatemay be added to sampletriplicates and matrix spike samples along with the test analyte (pre-photolysis). 3.7 ContinuingCalibrationVerification (CCV). Standardsanalyzed during an analytical run to verify the continued accuracy of the calibration curve. This solution may or may not be prepared h m a differentsource or lot number than the calibrationcurve standards. 3.8 Sohent Biank. A sample of analyte-fiee medium that is not taken through the sample preparation process. This blank is used to evaluate instrument contamination. 3.9 Blank. For photolysisstudies, there are multiple blanks to adequately represent the variables of the study @posed, Unexposed and Day 0 sampleswith/without peroxide addition). The blank is carried through the sample preparation, photolytic and analyticd procedures to monitor for contamination during any step. It is also used to establish a chromatographicbaselinehackground and monitor for analyticalinterferenceor suppressionof target analyte(s) from the matrix. 3.9.1 3.9.2 Matrix Blank A sample of analyte-freematrix (buffered water, lake water, etc.) to which all reagents are added in the same volumes or proportions as used in sample processing. It is used to document the test system without test analyte. Control Blank: A sample of analyte-fiee matrix (Milli-Q water) to which all reagents are added in the same volumes or proportions as used in sample processing. It is used to control the test matrix and monitor matrix specific ETS-8-182.0 Analysis of FCr by Purge & TrapAutosampIer/Concentrator/GC/MS Page 3 of 12 Page 68 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 background levels, interferences or suppressionof 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 10times the minimum concentrationwith a 99% confidence limit that the concentrationis greater than zero. However, it may be nominally chosen within these guidelines to simplifydata reporting. For many analytes, the LOQ is selected as the lowest non-zero standard in the calibrationcurve that is greater than 4 times the level of the matrix blank. 3.11 Sample Triplicates. Three samplestaken from and representativeof the same sample source. These are prepared separatelyand carried through all steps of the exposure, extraction and analytical procedures in an identical manner. There are multiple sets of triplicate samples to adequatelyrepresent the photolytic variables of the study (Exposed, Unexposed and Day 0 WiWwithout peroxide addition). Triplicate samples are used to assess variance of the photolytic method, including sample preparation, photolysis exposure, and analysis. 3.12 Relative Standard Deviation (RSD). A measure of precision defined as the standard deviation of three or more values dividedby the average of the values and multipliedby 100.(Alsoreported as Coefficientof 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 concentrationis 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 experimentallydetermined value and an accepted reference value. When applied to a set of observed values, accuracy is a combination ofarandom (precision) and a common systematic(bias) component. For purposes of the study, the acceptancecriterion 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 calibrationcurve standards,the number of calibrationstandardsbelow the geometric mean shall equal the number of calibrationstandardsabove the geometricmean. Having equal distribution of calibration standardsabove and below the geometricmean when analyzing and reprocessingdata,effectivelyweights the curve such that both the high and low ends of the curve are given equivalentsignificance. 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/concmtrator/GC/MSsystem and associated hazards, such as high temperature, effluent venting, solvent use, and low-pressure vacuum system. See instrument manuals ETS-8-182.0 Analysis of FCh by Purge & TrapAutosampler/Concentrafor/GC/MS Page 4 of 12 Page 69 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 4.1.2 All exhaust vents, including the GC oven vent, Tekmar concentrator purge vent, split vent and mass spectrometerpump exhaust must be connected to the laboratoryvent system to keep potentially hazardous effluent from mixing with laboratory air. 4.2 Cautions: 4.2.1 It is recommendedthat a grounded antistaticwrist strap be worn while disconnectingall 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-extractedmatrix componentscould interferewith detection decreasing sensitivity. 6.0 EQUIPMENT 6.1 System: "Rufus", or equivalent: 6.1.1 Autosampler: Varian, Archon 6.1.2 Concentrator: LSCZOOO, Telanar 6.1.3 GC:6890, Agilent 6.1.4 MS: 5973N,Agilent 6.1.5 Column,GS-GASPRO 60m x 0.23mm,J&W 7.0 SUPPLIES AND MATERIALS 7.1 Helium, ultra-high-purity 7.2 4Oml VOA vials, e.g. 1-Chem, S236-0040 8.0 REAGENTSAND STANDARD 8.1 Methanol, Purge and Trap grade or equivalent 8.2 Standards. Typically a minimum of five calibration standards, ranging from 1 n g / d to 20 nglml are prepared. This concentrationrange should bracket the concentration of samples and matrix spikes; if the analyte concentrationexceeds this range, then the calibration range should be increased. 8.3 Instrnment Surrogates. Used only to monitor performance of purge and trap autosampler and concentrator and not for quantitation. 8.4 SampleSurrogates.May be used to monitor samplepreparation, photolytic exposure and analyticalperformance. 9.0 SAMPLHEANDLING 9.1 Store standardsand samples in the refiigeratorat 4 C 5 3 C until analysis time. ETS-8-182.0 AnalysiF ofFCs by Purge & TrapAutosampler/Concen~aior/GC/MS Page 5 of 12 Page 70 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 9.2 For the analysis, pull samples and standards out of the freezer and bring them to room temperature. 10.0 QUALITCYONTROL 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 sufficientto encompass the expectedconcentrationsof the study samples. In general, a minimum of five calibration standardsis required for fit of linear regression. 10.2 Continuing CalibrationVerification (CCV). Analyze a mid-range calibration standard after a maximum of every fifteen samples. 10.3 Solvent blank. Solvent blanks are run before and after every calibration curve, CCV, matrix and control blank (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 analytecarryover is aproblem, useback-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 shouldbe approximately equalto a mid-range calibration standard. The matrix spike sampleshould be analyzedperiodicallyto measure the precision associatedwith the analysis. The analyst shall accept percent spikerecoveries of 100f 25%. Spike recoveries outside of this range should be noted and used with other criteria to evaluate the condition of the analyticalrun. Consult with the Team Leader or designee for direction and find acceptanceor rejection of the analyticalrun. 11.0 CALJBRATIONAND STANDARDIZATION 11.1 Analyze standardsprior to each set of samples. The linear regressionwill 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% deviationfrom the theoreticalvalue, quadraticcurve fitting and/or dropping low&& 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 technicaljustification for any deviation and consult with the team leader or designee for directionand for final acceptanceor rejection of the data. 11.2 If the curve does not meet requirements perform routine maintenance or prepare a new standard curve (if necessary) and reanalyze ETS-8-182.0 Analysis of FCs by Purge & Trap Autosampler/Concentrator/GC/MS Page 6 of 12 Page 71 of 165 BACK TO MAIN 3M EnvironmentalLaboratoryReport No.W2783 12.0 PROCEDURES 12.1 Set Archon autosampler 12.1.1 Archon System Settings US Probe Temp 180 Xfer line Temp 180 US Valve Temp 105 Gripper Open 750 Gripper Closed 999 Standby Pol CLOSED DesDrn Pol CLOSED STOP Pol. CLOSED Equilb. Count 0 Equilb. Time 0 12.1.2 Archon System Options BmodeScanner NO Needle Sparge? YES Ign.Vial Type? YES Ignore No Vial? NO HotWater Rinse? NO Vial Checks? YES Beep on Error? YES 12.1.3 Archon Method Sample Type Soil First Vial 1 Last vial up to 51 Sample Volume 10 Standard1 (luL) YES standard 2 NO S.PreHeat Stir NO Stir NO Syring Flushes 0 PreHeat YES PreHeat Temp 35 PreHeat Time 1 .o Purge Time 20.0 Desorb Tme(m) 0.5 Oper. Mode Remote Cycle Timer 0.0 Am. Timer 0.0 Link to Method 0.0 Soil Purge Flow 4OmYmin Soil Purge Pressure 2Opsi Em-8-182.0 Anobsk o f F G by Purge & TmpAufosampler/Concenfra~or/GU~S Page 7 of 12 Page 72of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 12.2 Set Tekmar options Standby 40C (3OOC by purge) Purge 20.00min Dry Purge 2.00min Desorb Preheat 245C Desorb 0.5Omin at 25OOC Bake 10.00min at 26OOC BGB OFF BGB Delay Osec Auto Drain ON Valve 180C Line 180C Mount 100C Runs per Sample 1 Purge Flow Purge Pressure Trap 4omL/min 2Opsi VOCARB 3000 Containing: Carbopack B Carboxen 1000 Carboxen 1001 12.3 Set GC conditions 12.3.1 Oven: Initial temp: 40 C Initial time: 4.00min Ramp at 15.00 C h i n to 28OoC Final time: 1O.OOmin 12.3.2 Front Inlet: Mode: Split Initial temp: 180OC Pressure: 8.5Opsi (on) Split ratio: 10.7 : 1 Split ffow:16.I mumin Totalflow: 20.6mVmin 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 10m/z to 650 d z ) MS source temp: 230 C MS quadruple temp: 150 C Interface temp: 260 C MultipIier voltage: adjust to give required low standard sensitivity ETS-8-182.0 Analysis of FCS by Purge & TrapAuiosampler/Concenttor/GC/MS Page 8 of 12 Page 73 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 12.5 Set up the instrument acquisition method. Name the sequence. The sequence includes a ' sample list documentingthe method used and datafilescreated. The sequence should be documented n the run files. 12.6 Sample analysis. 12.6.1 Set up autosampler and concentratormethods. Bring samples to room temperature (-22' C), spike them and place them on autosampler. Generate a mass spectrometertune report and review. Operating conditionsprovided above are recommended and may be adjusted to optimize system performance. Analyze all standard,samples, and spiked samplesusing the same analyticalconditions. 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 DATAANALYSISAND CALCULATION 13.1 Each batch of data shouldbe processed using Target Genie integrator. Integration parameters should be set to minimize the number of manual integrationsrequired yet still result in uniform integrationof peaks at all concentrationlevels. If manual integrations are required, a review code should be assigned to indicate the reason. Review codes are listed below. Review Code Explanation Peak was not automatically integrated by Target, therefore, integrated M1 manuallv Peak was automatically integrated; was reintegrated manually to M2 improve sample-to-sampleintegrationconsistency. Incorrect quantification ion peak was integrated; manual integration M3 was done to select the correct beak. ~ ~ - l % c o s s moni& ion peak was integrated;manual integrationwas I I I M4 Idone to select the correct De&. I 1 M5 lothers (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 = (observedconcentration backgroundconcentration)xl00 expected concentration 14.0 METHODPERFORMANCE 14.1 Coefficient of Determination (3).The coefficient of determination(3)for the initial calibration curves should be 0.990 or greater. The curves should be examined closely for ETS-8-182.0 Analysis ofFCS by Purge & TrapAutosumpler/Concentrator/GC/MS Page 9 of 12 Page 74 of 165 BACK TO MAIN 3M EnvironmentalLaboratory Report No. W2783 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 acceptanceor rejection for the data. 14.2 Calibration Standards. The acceptancecriterion for the calibration standardsis that the accuracyof each standard is 75% to 125% (& 25 % difference) of the nominal value. Calibrationstandardsoutsidethis range are to be noted. Document in the raw data the technicaljustificationfor deviations. Consultwith the Team Leader or designee for direction and for final acceptanceor rejection for the data. 14.3 Instrument Surrogate. Review of the instrument surrogate performance is performed by monitoring instrument surrogaterecoveries throughout the run. Inconsistenciesin the recoveries may be the result of instrumental changes, or injection mor. Consult with the Team Leader or designee for direction and final acceptanceor rejection ofthe analytical m. 14.4 Sample Surrogate. Sample surrogate performance is evaluated by averaging the area response throughout the analyticalrun and calculating %RSD. Inconsistenciesin 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 analyticalrun. 14.5 Continuing CalibrationVerification. If the accuracy for the amount of quantified analyte is greater than 25% from the nominal value relativeto 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 acceptanceor rejection for the data. 14.6 Solvent Blanks. Solvent blanks should show no more than a 5% carryover from a high standard or calibrationcheck standard. If so, two sequential solvent blanks may be necessary to rule out instrumental contamination 14.7 Matrix Blanks. Matrix blanks are the basis for determining the LOQ and are monitored at various times in the analytical run. Peaks with greater than 25% ofthe peak area ofthe designated LOQ value observed in matrix blanks are indicativeof eithermatrix effect, sample contamination or instrument contamination. Use of solvent blanks prior to the matrix blank may be necessary to rule out instrumental contamination or sample contamination. 14.8 Control Blanks. Control blanks are the basis for determiningmatrix 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 contaminationor 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 %RSDvalues < 25%. %RSDvalues > 25% should be noted. Data used in the find report that is deemed out of control will be ETS-8-182.0 Analysis of FCs by Purge & Trap Autosampler/Concentrator/GC/MS Page 10 of 12 Page 75 of 165 BACK TO MAIN 3M EnvironmentalLaboratory Report No. W2783 required to have technicaljustification 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 acceptanceor rejection of the data. 14.11 Analytical Spikes. The analyst shall accept percent spike recovery values of 100rfr 25%. Spikerecoveries outsideof this range shouldbe noted. Consultwith the Team Leader or designee for direction,and for final acceptanceor 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 spectrometertune report shall be generated before startingeach analyticalsequence. If the tune parametersdo not meet the criteria suggestedby the mass spectrometer manual, then the mass spectrometer should be re-tuned. If mass 28 is present in the tune report at >I 0% 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 POLLUTIONPREVENTION AND WASTE MANAGEMENT 15.1 Dispose of samplevials in low BTU and flammablesolvent 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, .preparationdate, incubationperiod, dilution factor (if applicable), and instrumentname. 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 runlog 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 electronicdata to appropriatemedium (primarily CD). Record in the study/projectfolder the filenameand location of backup electronic data. 16.6 List the documents and records generated when performing this method and where they are to be archived. ETS-8-182.0 Analysis of FCs by Purge & TrapAutosampler/Concentratar/GUMS Page 11 of 12 Page 76 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 17.0 ATTACHMENT 17.1 None. 18.0 REFERENCES 18.1 Archon Purge and Trap AutosamplerSystem Operator'sManual, 1996,Varian. 18.2 TekmarLSCZOO IastructionManual,1996,Tekmar. 18.3 Agilent MSD Hardware Manual for 5973N, 1999, Agilent. 18.4 Agilent 6890 Series Gas Chromatograph,volumes 1-3, 1999,Agilent 19.0 AFFECTEDDOCUMENTS 19.1 None. 20.0 REVISIONS Revision Number. Reason For Revision - Revision Date ETS-8-182.0 Analysis of FCS by Purge & Trap Autosampler./Concenttor/GC/MS Page 12 of 12 Page 77of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 I 3M ENVIRONMENTLAALBORATORY Method Indirect Photolysis Screening Test in Synthetic Humic Water Method Number: ETS-8-177.0 Approved By: AdoptionDate: vi-iDc Revision Effective Date: ETS-8- 177.0 Indirect Photolysis Screening Tests in Synthetic Humic Water Page 1 of 16 Page 78 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 1.0 SCOPE ANI) APPLICATION 1.1 Purpose. Chemicals dissolved in natural waters are subject to two types of photoreaction. In the fmt 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 photolyticreaction matrix because it contains dissolved organic materid that absorbs sunlight and produces reactive intermediates that include singlet oxygen ('03that promotes indirectphotolysis of the test substance. 1.2 The method is divided into two phases. Phase one includes the preparation of S H W . Phase Two provides a procedure to calculatesolarphotolysisrate constants and halflives of test chemicalsin pure water (PW) and SHW.This phase also includes parallel solar irradiation of a radiometer to calculate kIo(the indirectphotolysis rate in the test vessel, e.g. 40mL glass VOA vial) and (the near-surfacephotolysis rate constant in natural water bodies). 1.3 CompatibleAnalytes. Chemicalsthat will be subjected to this indirect photolysis screening and testing method include but are not limited to the following compounds: Comuound Acronvm Comaound Acronvm Perfluorooctanoic acid __ Pdumoctanesulfonate PFOA PFOS Perfluorobutanoic acid Perfluorobumesul fonate Perfluorooctanesul fonamide FOSA N-MeFOSA Pemuorobutanesulfonaide N-methyl perfluorbutanesulfonamide FBSA I N-MeFBSA N-ethylperfluorooctanesulfonamide N-EtFOSA N-ethylperfluoro butanesulfonamide N-EtFBSA 2-(N-methyIperfluorooctane sulfonamide) ethyl alcohol N-MeFOSE-OH 2-(N-methyIperfluombutanesulfonamido)ethyl N-MeFBSE- alcohol OH Z-(N-ethyIprrfluorooctane N-EtFOSE-OH Z-(N-ethylperfluorobutfmesulfonamido)ethyl N-EtFBSB-OH , su1fonamido)ethyl alcohol I 1-pduomoctene alcohol -- 1-perfluorobutene I - 1 Perfluorooctanehydride 1 I H, C8-hydride Pduorobutanehydride I IH,C4-hydride I ...and other Cdthrough C ~ (hIomologues, and polymeric materialsbased on the above aforementioned compounds. I ~ ~~ ~ 1.4 Acceptable matrix. Synthetic humic water (SHW), 0.005 M pH 7.0 Phosphate Buffer. ETS-8-177.0 IndirectPhorolysisScreening Tests in Synthetic Humic Water Page 2 of 16 Page 79 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 2.0 SUMMARY OF METHOD 2.1 Phase One: A solution of standardizedsynthetichumic water is prepared by water extraction of commercialhumic 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 thendiluted at the time of use to a W-visible absorbance typical of most surfacefresh waters (approximately 0.5 AU at 370 nm), 2.2 Phase Two:Study samples (5mL aqueousmatrix) are prepared in 40 mL glass VOA vials equippedwithscrew-top caps with septa. Test substanceis 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 "C. Samples to be exposed are photolyzed in the photoreactor at 261 W/m2 (300-800 am)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 sampleswill be refrigerated at 1-5 OC.until all timepoints have been completed. Dark controIs (unexposed) will also be prepared for each timepoint. Absorbancecontrolswill be used to monitor photo-bleachingof the SHW. Exposed and unexposed'absorbmcecontrot will be prepared per timepoint. - - 2.2.1 Samplesto be prepared for each timepoint and for each exposuretype: LCIMS GUMS Analysis Analysis at 370 nm I Sample Rep I + 0 0 i 0 I sample R C2~ + 0 0 + 0 Sample Rep 3 + 0 0 + 0 Sample Spike I + 0 0 + + Sample Spike 2 + 0 0 + .+ Matrix Blank + 0 0 0 0 MaCrix Blank Spike + 0 0 0 + Control Matrix(#l) blank 0 + 0 0 0 Control Matrix(#l)sample 0 + 0 + 0 ~ + ControlMatrix(#$)spike 0 4. 0 + + Control Matrix(#2)blank 0 0 0 0 Contmt Maaix(#Z) sample 0 0 + + 0 ControI Matri%(#Z) spike 0 0 + + + Absorbance Control + 0 0 0 0 Absnrhancc Cnnhnl dun + n n n Where "+" =addition of solutionor test substance and "0"=NO addition. analysis. A A NA A A NA A A NA A A NA A A NA A A NA A A NA A A ' NA A A NA A A NA A A NA A A NA -- A A NA NA NA NA I. analysis performed, an NA A A \TA = no y Time Point a m p ~ efor s 0 8hr 16 hr 32 hr 64 hr 128 hr Samples 0 30 30 30 30 30 Samples 30 (Time 0) 30 30 30 30 30 Analysis ( Exp + Unexp) 13 26 26 26 26 26 G U M S Analysis (Exp + Unexp) 13 26 26 26 26 26 UVNis Analysis (Exp + Unexp) 4 8 Total # of Samples 150 I80 143 I43 44 ETS-8-177.0 Indirect Photdysis Screening Tests in Synthetic Humic Water Page 3 of 16 Page 80 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 3.0 QUALITCYONTROL-DEFINITION/FREQUENCY~ERFORMANCECRITERIA 3.1 Blanks 3.1.1 Definitions: Matrix Blank. A sampleof analyte-freematrix (e.g. SHWhffer) to which all reagents are added in the same volumes or proportions as used in sample processing. For photolysis studies, there are multiple matrix blanks to adequately represent the variables of the study with reference to the matrix (e.g. Exposed, Unexposed and Time 0). The matrix blank is carried through the sample preparation, photolytic and analytical procedures to monitor for contamination during any step. It is also used to establisha chromatographicbaseline and monitor for interferenceor suppressionof target analyte(s) from the matrix. Control Blank. A sampleof analyte-freecontrol matrix (such as buffer or ASTM Type 11water) to which all reagents are added in the same volumes or proportions as used in sampleprocessing. The control matrix serves as a monitor of the eff'ect of the matrix on the test substance, test analytes and chromatographicbehavior. For photolysis studies, there are multiple control blanks to adequatelyrepresent the v,ariablesof the study withreference to the matrix (e.g. Exposed, Unexposed and Time 0 samples). The control blank is carried through the sample preparation,photolytic and analyticalprocedures to monitor for contamination during any step. It is also used to establish a chromatographic baseline and monitor for interferenceor suppressionof target anaIyte(s) from the control matrix. + I 3.1.2 FreqnencyPerformanceCriteria: Listed in the folIoWing table: Matrix ID Matrix descrbtion Frequencv Matrix Blank (BufferISHW) ControlBlank #I (BufferiPW) 0.01 M Phosphate Buffer, pH 7: Synthetic Humic Water 0.01 M Phosphate Buffer, pH 7 : A S T M Type IIWater 1 Replicateper light and dark exposure, for each time point and for each analytical methodology. ControlBlank #2 ASTM Type IIWater ~~ Performance Criteria Any background level of targel analyte shall be less than 25% the area counts of the LOQ. (Pw) 3.2 Sample Triplicate 3.2.1 Definition: Three aliquotsprepared as representatives of the same sample source (e.g. test substance) and carried through all steps of the photolytic study process and analyticalprocedures 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 IndirectPhotolysis Screening Tests in Synthetic Humic Water Page 4 of 16 Page 81 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 3.2.2 Frequency/PerformanceCriteria: Listed in the following table: Matrix Description Freauency T a t Matrix and test substance Performance Criteria The analyst shallaccept%RSDs 4 5 % . Precision must be documented andjustified (if 3.3 Analytical Spike (AS) 3.3.1. Defmition: A known mass of target analyte(s) in a specified amount of a diluted andor aliquotted sample. This assumes that an independentestimate of target analyte concentrationis available. Analytical spikes are used to evaluate the recovery efficiency of the analyte and the matrix effect. 33.2 FrequencyfferformanceCriteria: Listed in the followingtable: Matrix Description Test Matrix and test substance, spiked with target anaIyte(s) just prior to analysis Test Matrix with NO test substance, spikedwith target analyte(s) just prior to analysis Control Matrix (#1) and test substance,spiked with target analyte(s) just prior to analysis Control Matrix (#2) and test substance,spiked with target analyte(s) just prior to analysis II Frequency I 2 spiked samples per treatment type (one in lower halfof the calibrationrange, and one in the upper half of the cdibration range) 1 Replicate per treatment type (mid-range spike concentration) Performance Criteria The analyst shall accept accuracyof 100 2 25%. If accuracyis outside of this range, document and justify, if possible, the reason for the deviation. 3.4 Control Sample 3.4.1 Defmition: A known matrix containing the test substance carried through the entiresamplepreparation, photolytic and analyticalprocedure. This is used to document Iaboratoryperformanceby comparing recoveriesand matrix effects from the different matrices and sample types. 3.4.2 Frequency/PerformanceCriteria: Listed in the following table: Matrix Description ControlMatrix (#I) and test substance BufferPW ControlMatrix (#2) and test substance PW Frequency Performance Criteria 1 Replicate per light-and dark exposure, for we and for each me~odology The analyst shall accept accuracy of 100 f 25%. If accuracy is outside of this range, document and justify, if possible, the reason for the deviation. ETS-8-177.0 Indirect PhotoIysG Screening Tests in Synthetic Humic Water Page 5 of 16 Page 82 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 3.5 Absorbance Control 3.5.1 Definition: An analyte-fiee matrix that is carried through the sample processing procedure and analyzed by absorption spectroscopy at 370 nm. It is used to monitor the photo-bleachingrate of the S H W during the testing phase. 3.5.2 FrequencyPerformanceCriteria: Listed in the table below. Matrix Description Frequency Performance Criteria Control Matrix (#1) BuEedSHW only 2Replicatesper lightand dark exposure, for each time point Absorbance measuredat 370nm is between 0.01AU-0.05AU (1 cm pathlength cell) I 3.6 Internal StandardSmogate 3.6.1 Internal Standard Definition(applies to LC/MS samples): A known amount of a compound similarin analyticalbehavior to the target analytets) of interest (e.g. 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctanesulfonic acid (THPFOS) if pexfluorooctanesulfonate(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 controllingthe precision and bias of the applied analyticalmethod. Samplesare to be quantified using the internal standard. 3.6.2 SurrogateDefinition (applies to LC/MS and GCMS samples): A hown 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 throughthe remaining samplepreparation and/or analyticalprocess. If added before exposure, it monitorsthe presence of vid leaks during photolysis, as well as the performance of the purge and trap autosamplerand concentrator. Surrogateanalysis is used to evaluate the precision and bias of the applied analytical method. Surrogates are not used for quantitation. 3.6.3 FrequencylPerformanceCriteria: Listed in the following table: 1 Matrix DescriDtion Sample muted with 30 mL of internal standard compound dissolved in a suitable analytical solvent 1 Frwuencv of Use Every Lcrms sample analyzed I performanceCriteria The % M D for internal standards shall be calculated for the area response of all appropriate samples per analyticalbatch. The analyst shall accept %RSD values of 45%. %RSDvalues >15% shall be documented and justified, if possible. The % recovery of internal standards should be 100& 25%. .surrogates am for information only (ie., area response should be relatively constant). ETS-8- 177.0 Indirect PhotolysisScreening Tests in Synthetic Humic Water Page 6of 16 Page 83 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 3.7 Other Definitions. 3.7.1 Test Substancmest Analyte: Any substance(mixtureor controlled compound) added or administered to the test system for the purpose of chemical analysis. 3.7.2 Degradation Product@): Secondary analytes of interest produced as a result of chemicalreactionsduringthe photolysisand monitored (qualitativelyor quantitatively) during the sample analysis procedure. 3.7.3 Target Analyte(s): The analyte(s) singled out in the analytical phase ofthe study is the target analyte. The target analyte may be identical to the test substanceused in the experimentalphase of the study, a by-product or degradation product that is monitored (qualitatively or quantitatively)during the sample analysisprocedure. 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 absolutevalue of the difference of the two values divided by the average ofthe two values and multiplied by 100. 3.7.6 Relative StandardDeviation (RSD): A measure of relative precision for three or more samplereplicates; 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 Qnantitation(LOQ): The lowest concentrationthat 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 analyteconcentrationis selected asthe lowest non-zero standardin 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. Wear gloves and eye protection at all times. 4.1.2 Handle all solvents in a hood for all parts of the described sample preparation procedure. 4.1.3 For potential hazards of each chemical used, refer to material safety data sheets, packing materials, and 3M Environmental Laboratory's Chemical Hazard Review. 4.1.4 No mouth pipetting is allowed. 4.2 Cautions 4.2.1 The photoreactors are equipped with a continuous flow of cooling water that poses a threat of electrocution when handling the photoreactor during irradiation sequences. ETS-8-177.0 Indirect Photolysis Screening Tes& in Synthetic Humic Water Page 7 of 16 Page 84 of 165 BACK TO MAIN 3M EnvironmentalLaboratory Report No.W2783 4.2.2 Wear dark protective eyewearwhen operating the reactor. Do not look directlyat 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 Contaminantsin solvents,reagents, glassware and other sampleprocessing or analysis hardware may cause interference. To reduce the possibility of interference, glassware in which standardsare prepared should be pre-rinsed with methanol and allowed to dry beforeuse. The routine analysisof laboratorymethod blanks must be used to demonstrate that there is no interference under the conditions of the analysis, - 6.0 6.1 6.2 6.3 6.4 6.5 6.6 6.7 6.8 EQUIPMENT Analytical balance sensitiveto 0.1 mg Photoreactor: Suntest CPS+, XLS+, or equivalent, capable of producing 250-765 Wattdm', equipped with a xenon arclamp (e.g. 2200 W Xenon Lamp) and the appropriate filtersto allow the desiredwavelength (e.g. W Special Suprax@with cut-on at 290 nm, and Quartz dish with IR reflective coating), and a flowing water bath circulatingpump or . equivalent. Water cooler/recirculatorcapable of maintainingtemperature at 25 "C k 5 OC W-Visible Spectrophotometer(W-VIS), equipped with tungsten and deuterium lamps, model 8453, or equivalent 6.4.1 Autosampler: Model G1120A, or l-cm pathlength cell holder: Model 08451- 60104,or equivalent. 6.4.1.1 l-cm pathlength quartz spectrophotometercell, or equivalent. 6.4.2 Long Path-Length Cell Holder, Rewlett Packard part number 89076C,or equivalent 6.4.2.1 10-cmpath length quartz cell equipped with stopcocks, Hewlett Packard Part # 5061-3392, or equivalent. 6.4.3 Data acquisition and analysis software,HP ChemStation for W-Visible Spectroscopy, G1116AA Rev. B.01.02, or later. Data System: A PC capable of controllingthe W-Visible Spectrophotometersystem. Centrifuge capableofmaintaining >2000rpm for 10minutes at ambient temperature (2226 "C). Radiometer, capableof detectingand recordingirradiationoutput of the photoreactor for the duration of the study. Lab Oven, capable of maintaining 70-80 "C. 7.0 SUPPLIES AND MATERIALS 7.1 40-mL amber and clear glass vials (VOA) with screw caps. 7.2 Crimp cap autovials: 1S-mL,caps, crimper, and decapper. 7.3 Adhesive-backedlabels (return address size) for labeling quartzvials and autovials. 7.4 Disposable glass graduatedpipettes, 1mL to 10mL. ETS-8-177.0 Indirect Photolysis Screening TesB in Synthetic Humic Water Page 8 of 16 Page 85 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 7.5 Disposable glass Pasteur pipettes and rubber bulbs. 7.6 Glass beakers, various sizes. 7.7 7.8 * Volumetric flasks, from 10mL to I000mL. Hamilton Gastight" syringes (precision 1% of the total volume), 5 pL to 1000 pL. 7.9 10-mL Bottle-top dispenser. 7.10 Teflon* filters filter holder apparatus: 0.4 pm pore-size and 0.2 pm pore-size filters (47 mm diameter, Gelmarim or equivalent. 7.11 500-mL glass screw-top containers. 8.0 REAGENTSAND STANDARDS 8.1 WaterRure water (PW),ASTM Type IIwater at a minimum 8.2 Methanol (MeOH), HPLC/SPEC/Gc grade from EM Scienceor equivalent. 8.3 Acetone, HPLC/SPEC/GC grade from EM Science or equivalent. 8.4 Acetonitrile, HPLC/SPEC/GC grade from EM Science or equivdent. 8.5. Humic acid, sodium salt, from Aldrich or equivalent. 8.6 NaOH, reagent grade from EM Sciencem or equivalent. 8.7 0.1% NaOH solution Example: Weigh approximately 1.0 g sodium hydroxide into a weigh boat and transfer quantitativelyto a 1 L volumetric flask and dilute to the mark withPW or equivalent. 8.8 Sulfaric Acid (H,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 KHzP04into a weigh boat and transfer to a 1L volumetric flask using PW and dilute to the mark. Transferthe 1 L of solutionto a 2 L volumetric flask. Add 600 mL of 0.1% NaOH, adjust the pH to 7.0 k 0.1 with 0.1%NaOH or dilute HzS04,and dilute to the mark with PW. 8.10 Method Blank Solutions: -Method BlankTmes 1 Matrix ID TestMatrix BuflwBHW I Matrix description Example: 1:lO Solution: Dilute 50 mL. Synthetic Humic Water with 0.01 I I M pH 7.0PhosphateBuffer solutionto 500 mL. Control Matrix (#1) Bufer/PW Example: 1:lO Solution: Dilute 50 mLPure Water (ASTM Type 11) with 0.01 M pH 7.0PhosphateBuffer solution to 500mL. ControlMatrix (aP)W h e Water (ASTM Type 11) 8.11 Stock Solutions. Stock solutions for internal standards and spiking solutions are prepared in MeOH at concentrations of approximately 10,000 pg/mL by weighing approximately0.1 g ofthe appropriatesubstance into a 10-mL volumetric flask and bringing to the mark withMeOH. Dilute to make appropriateworking solutions. 8.11.1 Diluting Solutionwith Internal Standard: The diluting solution shall contain internal standardat an area response level equivalent to approximatelyhalf the ETS-8-177.0 Indirect Photolysis Screening Tests in Synthetic Humic Wuter Page 9 of 16 Page 86 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 area response of the test substance's high standard in the caIibrationcurve. Example: Internal standard solution inMeOH is prepared by diluting 5OpL of internal standard stock solution (Section 8.1 1) to 1 L with MeOH to a nominal concentrationof 0.5 AU pg/mL. 8.12 Test Solutions 8.12.1 Test Substance: Prepare a solution of the test substance in acetonitrile. Calculate the concentration so that after the test substance is added to the test vial, no more than 1% of the volume in the test vial will be solvent. (e.g. 5OpL added to 5 mL of matrix = 1% v/v) Then measure the absorbance of the test substance solutiondilutedwith buffedwatermatrix to the desired concentration. The maximum absorbance at any wavelength greater than 290nm must be < 0.05, when measured in a standard l-cm pathlength cell. Example: A 900 pg/mL solution of test substancein acetonitrileis prepared by weighing 90 mg of test substance into a 100mL voIumetric flask and diluting to the mark with acetonitrile. 9.0 SAMPLEHANDLING 9.1 Record times of initial preparation and dilution on the fluorochemicaldegradation (photolysis) analysis sample prep sheet (Attachment A). 9.2 Once the test substancesolutionhas been added, the 40mL VOA sample vials shall be stored and handled cap-side down to minimize loss of any potential volatile analytes. After the exposure period, the LC/MS samples may be turned upright and stored in a cooler at 1-5 "C. After the exposureperiod, GCMS samplesshall be maintained in an inverted position in a cooler at 1-5 "C until they are loaded onto the autosampler. 9.3 Once the 30-mL aliquot of diluting solvent has been added to the LC/MS photolysis samples, (see Section 12.0), the samples should be analyzed as soon as possible. ' Alternatively, the samplesmay be stored at 1-5 OC. Day 0 samples are to be stored at 1-5 "Cduring the time of sample exposurerand then diluted along with the exposed and unexposed samplesjust prior to analysis. 10.0 QUALITY CONTROL 10.1 Quality control parameters (and the fiequency of use) are included in Section 3.0. 11.0 CALIBRATIONAND STANDARDIZATION 11.1 The analytes of interest must be standardized according to laboratory specifications. 11.2 All equipmentused,such as the analyticalbalance, photoreactors, etc. should be calibrated prior to use (daily, weekly, etc.) as specified in its standard operating procedure. 11.3 All samples analyzed will be run against a standard curve containing varying amounts of test substance, and a fixed amount of internal standard or surrogate compound. ETS-8-177.0 Indirect Photolysb Screening Tests in Synthetic Humic Water Page 10 of 16 Page 87 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 12.0 PROCEDURES 12.1 Phase One-PreDarationand standardizationof synthetichumic water. 12.1.1 Weigh approximately2.5 g humic acid &to a tared 250 mL centrifugetube. 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. Shakevigorously(e.g. 100-250rpm) at room temperature for approximatelyone hour. 12.1.4 Centrifige the 250 mL of solutionat approximately2000 rpm for 10minutes or until solutionhas cleared, and then filter the supernatantthrough a 0.4pm filter into a clean 500-mLglass screw-top container. 12.1.5 Adjust the pH of the solutionto 7.0 with dilute H2S04or 0.1 % NaOH. 12.1.6 Filter-sterilizethe solutionthrougha 0.2pmdiameter pore-size filter into a clean 500-mL glass screw-top container. 12.1.7 Seal the containerand place cap-side down in the photoreactor chamber. 12.1.8 Expose the S H W 24 hours at 261 W/m2to pre-age the solution (equivalent to three day's worth of Miami,Florida sunlight)., The EPA's definition of "1 Day'' of irradiationis "eight hours." The irradiationintensityof 261 Wlm2was chosen because it yields the equivalent average optimum natural daylight radiation for 300-400 nm (see the table below): AmroximateIntePrated and IndividualIrradiancesin W/m2 Irradiance Source 250-300 IW 300-400IUII 400-800IIIII 340 IUXI 420 Average Optimum Natural o.o Daylight' 27.8 259.0 0.30 0.67 Atlas Photoreactorwith integrated irradiance output of 261 W/mz 300-800nm using 0.08 the IRReflecting and 290cut- on filters 27.8 234.36 0.24 0.71 where: 0.5 =L 3 7 0 IL x the measured absorbance of the SHW at 370 nm x = the volume of S H W needed to dilute to 1 L with water. 12.1.12 Bring the solutionto the exact dilution calculated in 12.1.11with PW. ETS-8- 177.0 IndirectPhotolysisScreening Testsin Synthetic Humic Water Page 11 of 16 Page 88 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 12.1.13 Verify that the absorbance is approximately 0.5 AU by aliquoting the diluted S H W into a I-cm W - V I Scuvette and taking the absorbancereading at 370 nm. 12.1.14 Transferthe S H W stock solution into an amber, or clear foil-wrapped 1 L glass storagebottle, tightly cap and refiigerate. 12.2 Phase Two 12.2.1 Fill out the "FluorochemicalDegradation (Photolysis)SamplePrep Sheet" (Attachment A) as much as possible, assigning sequential unique ID numbers to each sample to be prepared. 12.2.2 Obtain the appropriatenumber of clear and amber 40-mL glass vials with caps and cardboard boxes. Label the vial caps using a black permanent marker to distinctly identifjr samples. 12.2.3 Create labels for each sampleto be affixed to the 40-mL vials and the autosamplervials 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 BuffedSHW, BufferRW and PW solutions into clear (for exposed samples) and amber (for unexposed and Time 0 samples) 40-mL glass VOA vials. Add test substanceto the appropriate vials. See the table below for list of vials, replicates, and sampletypes. 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. (LCMS and GUMS): + Sample Rep 1 0 + Sample Rep 2 Sample Rq,3 SampleSpike 1 Sample Spike 2 0 + 0 + 0 + 0 + Matrix Blank Matrix Blank Spike + 0 0 Control Matrix(#l) blank 0 + Control hdatrix(#l) sample 0 + Control Matrix(#l) spike 0 + Control Matrix(K2) blank 0 0 Control Matrix(#Z) sample 0 0 Control h4atrix(#2) spike 0 0 Sample Rep 1 + 0 Sample Rep 2 + 0 Sample Rep 3 + 0 Sample Spike 1 + 0 SampleSprk 2 + 0 Test Matrix Blank + 0 Test Matrix Blank Spike + 0 Control Matrix(#I) blank 0 + ControlMatrix(#l) sample 0 + Control Matrix(#l) spike 0 + Control Matrix(#2)blank 0 0 0 + 0 + 0 t 0 + 0 + 0 0 0 0 0 0 + 0 0 + + 0 + f + + 0 + 0 + 0 f 0 + 0 + 0 0 0 0 0 0 + 0 0 + + 0 i + Where "+" = addition of solutionor test substance and "0"=NO addition ETS-8-177.0 IndirectPhotolysisScreening Testsin anthetic Humic Water Clear/Exposed ClearlExposed CleadExposed ClearlExposed ClearlExposcd CleadExposcd ClearlExposed Clcar/Exposcd CleadExposed CledExposed CleadExposcd CleadExposed CleadExposed AmberNnexposed AmberNnexposed Amber/Unexposed AmberNnexposed Amber/Unexposed AmberNnexposed AmberNnexposed Ambw/Unexposed AmberNnexposed AmberNnexposed AmberNnexuosed AmbedUmxposed Page 12 of 16 Page 89 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 Control Matrix(#l)= SHWBuffer 1:9 v/v Control Matrix(#2)=PWBuffer 1:9v/v Create one set of samples (listed below) for each time point for WNIS analysis: r - - x z 1 Description (Buffer/sIW) (Buffer/PW) 12.2.6 Store the "Time 0" vials in a labeled box at 1-5 "C. 12.2.7 Place all the vials that will go into the photoreactor into an oven set to 70-80 "C. for 5-10 minutes to acclimatethe vials, liquid and headspace to photoreactor conditions. Upon removing the vials fiom the oven, immediatelyre-tighten the caps and proceed to load the reactor. 12.2.8 Place the amber "unexposed" vials in plastic bags and arrange on the bottom of the photolysis tray (make sure that they don't float once the tray is filled with water). The "unexposed"vials will remain submerged in the cooling water (25 rfr 5 "C) during the exposure. (The vials are exposure- and temperature-controlled.) 12.2.9 Place the clear ''exposed" vials in the rack in the photoreactor tray cap-side down, and install the rack so that the VOA vial caps will be submerged throughout the duration of exposure. 12.2.10 Prepare the radiometer to read intensity of irradiance over the duration of the exposure. See SOP ETS-9-50.0 for operation of radiometer. 12.2.11 Expose the samplesfor the designated t h e intervals at 261 W/m2. See SOP ETS-9-44.0 for operationof the photoreactor. 12.2.12 Following each exposure interval, remove vials fiom the photoreactor and store inverted in a cooler at 1-5 "C.After all exposures have been completed, remove all samplevials as well as the "Time 0" vials h m the cooler and analyze as a single batch for each instrument. 12.2.13 W - V I S absorbance control analysis 12.2.13.1 Analyzethe pH 7.0 SHWhufferabsorbance controls by UVNisibIe absorbance spectroscopyat 370nm by aliquotingthe test solutiondirectly into a 1-cm or greater pathlengthquartz cuvette and obtaining the spectra. , See SOP ETS-9-46.0 for operation of the WMS instrument. The resultant peak at 370 nm will be analyzed to detemine the change in absorbancebetween the Time 0, exposed and unexposed samples. 12.2.14 LC/MS sample analysis 12.2.15 Dilute the exposed and unexposed samples for all timepoints with 30 mL internal standardsolutionin methanol (Section 8.11.I). Add spiking solutionto the appropriatevials. Invert each vial several times to mix. 12.2.16 Transfer aliquots of LCMS samples into autovials and then place them in the autosampler for analysisof the parent compound and possible degradation products. Analyze according to ETS-8-181.0. 12.2.17 GCMS sample analysis ETS-8-177.0 Indirect Photolysis Screening Tests in Synthetic Humic Water Page 13 of 16 Page 90 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 12.2.17.1 12.2.17.2 Analyze the exposed and unexposed samples for all timepoints as-is by purge and trap GCMS. Add spiking and surrogate solutions, as required, to the appropriatevials. Analyze according to ETS-8-182.0. Important: Maintain vials in the inverted position until they can be placed in the autosampler. 13.0 DATAANALYSISAND CALCULATIONS 13.1 Not applicable, as this is a sample preparation and analysis method. Consult the appropriate analyticalprotocol for guidanceregarding data analysis and calculations. 14.0 METHODPERFORMANCE 14.1 Not applicable. 15.0 POLLUTIOPRNEVENTIOANND WASTEMANAGEMENT 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'analysissummaries 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 discmedia. 17.0 ATTACHMENTS 17.1 "FluorochemicalDegradation(Photolysis) SamplePrep Sheet" 18.0 R~FERENCES 18.1 Interpersonalconversationwith Carrie O'Connor, Optical SystemsEngineer, Atlas Electric Devices. 18.2 "Suntest CPS/CPS+ SpectralIrradiance Distribution," table distributedby Atlas Electric Devices Company, sent via fax by Richard Sherwin, Sales Representative, 26 July, 2000. 18.3 "Atlas Xenon Filter Combinationand SunlightMeasurements," infomation generated by Atlas Electric Devices Company sent via fax by Richard Sherwin, Sales Representative, 26 July, 2000. 18.4 OPPTS 835.5270, Indirect PhotolysisScreeningTest: Sunlightphotolysis in water containing dissoIved humic substances. ETS-8-I77.O IndirectPhoto2ysisScreening Tests in Synthetic Humic Water Page 14 of 16 Page 91 of 165 , 19.0 AFFECTEDDOCUMENTS 19.1 None 20.0 Revisions Revision Number. Reason For Revision BACK TO MAIN 3M Environmental Laboratory Report No.W2783 Revision ETS-8-177.0 Indirect PhotoIysisScreening Tests in Synthetic Humic Water Page 15 of 16 Page 92 of 165 6 Z . BACK TO MAIN u0 m 0) wa, h Iul BACK TO MAIN 3M EnvironmentalLaboratoryReport No. W2783 3M ENVIRONMENTLAALBORATORY EQUIPMENPTROCEDURE OPERATIONAND MAINTENANCOFETHE HEWLETPTACKARD 8453 W-VISIBLE SPECTROPHOTOMETER Procedure Number: ETS-9-46.0 Approved by: Laboratory Management Adoption Date: Revision Effective Date: /A/*/& Date ETS-9-46.0 Operationand Maintenance of the HP8453 UV-VisSpectrophotometer Page 1 of 9 Page 94 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 1.0 SCOPE AND APPLICATION 1.1 This equipment procedure describes the operation, cleaning, and maintenance of the Hewlett-Packard 8453 W-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 ceI1: Transparentreceptacle in which sample solutionsare introduced into the light path of spectrometers.Usually, two sides are equal (e.g. 1 cm x 1cm) while the third dimension is elongated, possibly as long as 15 cm. For W work, the material is quartz. Visible work permits the use of glass or plastic cuvettes. 2.3 Pathlength: The distance the light passes through the sample in its holder, In practical terms, the inside dimension of the cuvette (usually 1 cm). 2.4 Slitwidth: 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 Cutoff: The wavelength at which the solvent absorbs a significantportion 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 electromagneticspectrum, fiom 400to 800 nm, detectable by human eyes, 2.8 Ultra-violet (UV): The portion of the invisisbleelectromagneticspectrum composed of wavelengthsof 10-400m.In UV spectrometrywe are primarily interestedin the nearUV (quartz) region extending from 200 to 380 nm. 2.9 UV Spectrum: a plot of wavelength (or frequency) of absorptionversus the absorption intensity (absorbance or transmittance). 3.0 DESCRIPTION 3.1 The HF' 8453 spectrophotometeris a single-beam,microprocessor-controlled,UV-visible spectrophotometerwith collimatingoptics. The ChemStationa for W-Visible spectroscopysofhvarerunning on a PC with Microsoft@NT operating system provides instrument control, data acquisition, and data evaluation. 4.0 IDENTIFICATION 4.1 Hewlett Packard G1103A SerialNo. CN93500458 4.2 Hewlett Packard 89090A SerialNo. DE14300757 5.0 WARNINGS AND CAUTIONS 5.1 Health and Safety Warnings: ETS-9-46.0 Operation and Maintenance of the HP8453 UV-VisSpectrophotometer Page 2 of 9 Page 95 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 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 adjustmentsdescribedin the servicemanual 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 Capacitorsinsidethe instrumentmay still be charged, even though the instrument has been disconnected f b m its source of supply. Dangerousvoltages, 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. Fingerprintsabsorb W 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 190to 1100nm wavelength range of the spectrophotometer.Good quality glass cells may be used when working above 350 nm. Disposable plastic sample cells are not recommended for use. 5.2.3 For high precision measurements, wait until the spectrophotometerand the lamps have reached thermal equilibrium. The time required is a function of environmental conditions but the instrument should be ready after 45 minutes. To determine if the spectrophotometeris in stableworking condition, the HP 8453 Self- test may be performed. (See section 13.1) 5.2.4 Ensure cell windows are fiee of fmgerprints 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 h e of floatingparticles. 5.2.7 Solution in cell and ceil walls should be free of bubbles. 5.2.8 Ensure that solution in cell is homogeneousby thoroughlymixing before measurement. 5.2.9 Blank is measured on the same solvent as sample. 5.2.10 Blank measurement should show a flat baseline. 5.2.11 Cell orientation of blank and sample measurements should be the same. 5.2.12 Ideally, the cell is not removed between sample measurements, which means the cell is filledrinsed using a pipette or a flow cell is used. 5.2.13 Time between blank and sample measurements should be short. 6.0 SPECIAL INSTRUCTIONS 6.1 None. 7.0 RESPONSIBILITY 7.1 ' The operator is responsible for routine maintenance and cleaning. ETS-9-46.0 Operation and Maintenance of the HP8453 UV-VisSpectrophotometer Page 3 of 9 Page 96 of 165 BACK TO MAIN 3M EnvironmentalLaboratory Report No.W2783 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 SUPPLIEASND MATERIALS 8.1 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 (PartNo. 2140-0605). 8.6 Lamp, Tungsten G1315A, Agilent 8453A (PartNo. G1103-60001). 9.0 INSTRUMENT CLEANING PROCEDURES 9.1 Cleaning the Stray Light Filter. (Recommended at one-yearly iritervals or more frequentlywhen operating the spectrophotometerin a particularly dirty environment.) 9.1.1 Turn off the instrumentand disconnectthe 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. 9.1.3 Remove the upper rear foam block. 9.1.4 Disconnect the shutter cable from the SPM board. Open the screw that fixes the shutter assembly to the optical unit and remove the shutter assembly. 9.1.5 Dampen a lint-fiee, 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 cornpressed oil-free air to further clean the stray light filter. 9.1.7 Position the shutter assembly above the source lens and fix the screw that holds it at the optical unit, see Figure 39 on page 124of the Servicemanual. Connect the shuttercable 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 109of the HP 8453 ServiceManual. 9.1.11 Reconnect the line power and turn on the instrument. Check that the spectrophotometerpasses 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 Cleaningthe SourceLens from the SampleCompartment Side. (Recommended at oneyearly intervalsor more frequently when operating the spectrophotometerin a particularly dirty environment.) 9.2.1 Turn off the instnunent and disconnect the power cord. 9.2.2 Remove any cuvette holder fromthe sample compartment. ETS-9-46.0 Operation and Maintenance of the HP8453 UV-Vis Spectrophotometer Page 4 of 9 Page 97 of 165 BACK TO MAIN 3M Environmental Laboratory Report No.W2783 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 surfaceof the source lens. Repeat several times with dean 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 spectrophotometerpasses the self-test, this means that the green light on the fiont panel comes on and that you can do a blank measurement from the software. 9.3 Cleaning the SpectrographLens. (Recommendedat one-yearly intervalsor more fiequentlywhen operating the spectrophotometerin a particularlydirty environment.) 9.3.1 Turn off the instrumentand disconnectthe power cord. 9.3.2 Remove any cuvetteholder h m the sample compartment. 9.3.3 To have better access you may want to take the plastic and sheet metal rear covers off, see "Removing and Replacing Covers" on page 109of 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 spectrographlens. Repeat several times with clean swabs and alcohol each time. 9.3.5 Use a canister ofcompressedoil-freeair to furthercleanthe spectrograph`lens. 9.3.6 If you have taken the covers off, replace them. Replace the cell holder in the sample compartment. 9.3.7 Reconnect line power and turn on the instrument. Check that the spectrophotometerpasses the seIf-test,this means that the green light on the front panel comes on and that you can do a blank measurement fiom the software. 10.0 MAINTENANCPEROCEDURES 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 exchangingthe lamps, the intensity test executedby 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 indicationfor dirty lenses is when, afbr 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 executedthroughthe ChemStationsoftware,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-946.0 Operationand Maintenance of the HP8453 UV-Vis Spectrophotom&er Page 5 of 9 Page 98 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 11.0 OPERATING PROCEDURES 11.1 Powering Up the HP 8453 UV-Visible Spectrophotometerand 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 sessionby pressing the operating system's "Start"button and select "Programsy',"HP W-Visible ChemStations", "spectrometer 1 onIine" 11.1.4 The system is ready to use if the blue "busy" status display on the system's bottom message line turnsoff. Note: For high precisionmeasurementswait until the spectrophotometer and the lamps have reached thermal equilibrium. The time required is a function of environmental conditionsbut 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 standardsingle-cellholder which accommodates standard cells or flow cells. 11.2.2 Move the Iocking lever to its up position. 11.2.3 Insert the sample cell, making sure you orient it correctly.The frosted (non-clear) sides of the sample cell should not be in the path of the light beam. 11.2.4 Lock the sample cell in place by pushing the locking lever back down. 11.25 Small volume flow cells and particularly any cells with less than a 2 mm aperture may require use of the optional adjustablecell 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 InstrumentPanel. 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 I online from the menu, 11.4.2 Perform a reference measurement. Typically the cell containingthe 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 orientationto the measurement beam. Flush the cell about three times with the sample solution and start the measurement by clicking the Instrument Panel's "Sample" button or by pressing the spectrophotometer's "Sample" button. 11.5 Setting up a Method for Single Component Analysis. 11.5.1 Choose the "Quantification" task from the data analysis panel. 11.5.2 Enter the used wavelength in the input fields. ETS-9-46.0 Operationand Maintenanceof the HP8453 W-Vis Spectrophotometer Page 6 of 9 Page 99 of 165 BACK TO MAIN 3M EnvironmentalLaboratory Report No.W2783 11.5.3 If background correctionis desired, select "Single ReferenceWavelength", "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 fieId 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 definethe rangehaselhe by enteringthe 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 analyteconcentrationdirectly or "Weight & Volume" to have the ChemStation calculate the concentration. Enter the units for the concentrationor the weight and volume. 11.5.6 If you want to be prompted for the concentrationof the standardsduring measurement, select "Prompt for StandardInformation". In the combo box you can select whetherthe prompt asks you for the concentration,or calculates the concentrationbased 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 stepsif you want to calibratethe method. 11.5.11.1 Measure a blank on the solvent if necessary using the "Blank" button in the instrumentpanel. 11.5.11.2 Measure the standardsushg the "Standard" button in the instrument panel. If you have selected one of the prompts, the appropriatevalues will be requested in a dialog box. The spectrum is displayed automatically in the "Standard Spectra" window as they axe measured. Note: There is no fixed limit to the number of calibrationstandardsthat can be incorporated into a calibration.However, each of the calibrationcurve types requires a minimum number of standards of different concentrations, which can be found in Table 7, page 45 of the HP Manual: UnderstandingYour UV- Visible Spectroscopy System. The ChemStationBs o h a r e calibrates automaticallywhen at least the minimum number of standards has been measured. A table with the used standardsand values as well as calibration curve is displayed. 11.5.11.3 If the cdibration is successfbl, 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 "PeakNalley Find" if necessary. ETS-9-46.0 Operationand Maintenanceof the HP8453 UV-Vis Spectrophotometer Page 7 of 9 Page 100 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 116.4 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 "Spectnun/PeaksParameters" dialogbox. 11.6.7 Measure a Bhnk on the solvent if necessary using the "Blank"button in the instnunent 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 (Samplesor Standards)from the submenuto display the "Load Spectra" dialog box. 11.7.2 If the spectrayou wish to load are not in the "File Name"list, select a different directory fKm the "Directories" list. 11.7.3 Select the spectra you wish to load from the File Name list and choose OK to close the dialog box. 11.8 Saving Spectra: 11.8.1 Choose "Save" from the "File" menu, then choose the type of spectra that you want to save (Samples, Standards or Selected Spectra) from the submenu to display the "Save SpectraAs" dialog box. 11.8.2 If you wish to save the spectra in a directory other than the current one, seIect the new directory from the "Directories" list. 11.8.3 Type the name you wish to save the spectra as in the "File Name" field and choose "OK" to close the dialog box. 11.83.1 A valid file name consist of eight alphanumeric characters and the file extension .sd or std. Usually, the extension .std is used for standards only. 11.8.4 You can also save spectra using the ToolBar. 12.0 RECORDS 12.1 Document all cleaning and maintenance performed on the instrument in the maintenance or run/maintenance logbook.Include a descriptionofthe 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 TESTINGC,ALIBRATIAONND/OR STANDARDIZAPTRIOOCNEDURES 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 ChemStationBsession. 13.1.2 Select the "Self-Test" task in the analysispanel's selectionbox. 13.1.3 Choose "Self-Test". Start from the "Task" menu or click "Start" to start the self- test. 13.1.4 The self-test results will be displayed in a window with pasdfail criteria. 13.2 Calibrating for a single component analysis. ETS-9-46.0 Operation and Maintenance of the HP8453 UV-VisSpectrophotometer Page 8 of 9 Page 101 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 . cc 13.2.1 Calibration for single component analysis is based on the measurement of standard sampleswith known concentrations. During the calibrationprocess, the software calcuIatesthe calibrationcoefficients,which are then used for the quantificationof 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 continuouscalibration 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 standardsfrom file or meaure them. 13.2.3.4 To measure! standards: 13.2.3.4.1 Measure a bank on the solventif necessaryusing the "Blank" button in the instrumentpanel. 13.2.3.4.2 Measure the standardsusing the LcStandardb"utton in the instrument panel. If you have selected one of the prompts in the method, the appropriatevalues will be requested in a dialog box. 13.2.4 The spectra are displayedautomaticallyin the "Standard Spectra"window as the standardsare measured. A minimum number of standardsis required, depending on the selected calibrationcurve. The ChemStationm s o h a r e calibrates automaticallywhen at least the minimum number of standardshave been measured. A table with the used standards and values as well as a calibration curve is displayed. 13.2.5 If the calibrationis successfid, the calibrationcurve icon of the data analysispanel changes fkom red to green. 14.0 REFERENCES 14.1 Definitions obtained from www.spectroscopymag.com. 14.2 Hp Manual:Understanding Your W-Visible Spectroscopy System, Hewlett-Packard: Wilmington, DE, 1997. Part No. G1115-90005. 14.3 HP 8453 UV-Visible Spectrophotometer Operator's Manual, Hewlett-Packard: Wilmington, DE, 2000. Part No.G1115-90012. 14.4 HP 8453 UV-Visible SpectrophotometerService Manual,Hewlett-Packard: Wilmington, DE,1998. Part NO.G1115-90003. 15.0 AFFECTEDDOCUMENTS 15.1 None. 16.0 RJWISIONS ~~ Revision Number. ~ Reason For Revision - ~~~ - Revision Date ETS-9-46.0 Operationand Maintenance of the HP8453 UV-VisSpectrophotometer Page 9 of 9 Page 102 of 165 BACK TO MAIN 3M Environmental Laboratory Report No.W2783 3M ENVIRONMENTLAALBORATORY EQUIPMENPTROCEDURE MAINTENANCOEF ARCHON PURGEAND TRAP AUTOSAMPLER, TEW PURGE AND TRAPCONCENTRATAOMR, AGILENTGAS CHROMATOGRAPH/MASSSPECTROMETER Procedure Number: ETS-9-49.0 Adoption Date: ci++ Approved by: . r?c? Date ETS-949.0 Routine Maintenance of the Purge & Trap Autosampier/Concentrator/GC/MS Page 103 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 1.0 SCOPE AND APPLICATION(USE NUMBEREDTIER 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 chromatographI mass spectrometer(GUMS) system. Specific items requiring routine maintenance include occasional tightening vial escalator's nuts and refilling the StandardVial and water bottle in the Archon autosampler and periodic cleaning of the mass spectrometer ion source. 2.0 DEFINITIONS 2.1 None. 3.0 DESCRIPTION 3.1 Archon purge and trap autosampler equippedwith Tekmarpurge and trap concentrator and AgiIent gas chromatograph and mass spectrometer. 4.0 IDENTIFICATION 4.1 System : " R u ~ s "(.Anequivalent systemmay be used). 4.1.1 Autosampler: serialnumber 13006,Varian, Archon 4.1.2 Concentrator: serial number 90297002, LSC2000,Tekmar 4.1.3 GC: serialnumber US00034972,6890 G1530A,Agilent 4.1.4 MS:serial number US01180105,5973N G2589A, Agilent 4.1.5 PC: serialnumberUS94850822,D6720T,HP Kayak XA 5.0 WARNINGSAND CAUTIONS 5.1 Health and Safety Warnings: 5.1.1 Cooling the Tekmar before removingthe side cover for maintenanceprevents 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 recommendedthat a grounded antistaticwrist 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 Au~osample-/Concentrator/GC/MS Page 2 of 5 Page 104 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 7.0 RESPONSIBILITY 7.1 Routine maintenance procedures may be performed by a primary custodian, and by any analystwho has been trained to perform these maintenanceprocedures by a primary custodian. 8.0 SUPPLIES AND MATERIALS 8.1 GraphiteFerrules, 0.4mm I.D. for 0.25 mm columns 8.2 Abrasive paper, Hewlett-Packard,part no. 5061-5896 8.3 Alumina abrasivepowder, Hewlett-Packard,part no. 8660-0791 8.4 Acetone, reagent grade 8.5 Dichloromethane, reagent grade 8.6 Methanol, purge and trap grade 8.7 Gloves (clean, lint-free, cotton), Hewlett-Packard,part no. 8650-0030(large); 8650-0029 (small) 8.8 Cotton swabs 8.9 Chem-wipes 8.10 Glass beakers 8.11 Sonicator 8.12 Base deactivated2 mm ID gooseneck splitlessinjectionport liners, Restek Corporation, part #20796-210.5, or equivalent 8.13 11mm diameter ThermogreenLB2 septa, Supelco,part #23163, or equivalent 8.14 Viton injectionport O-rings, Restek Corporation,part #20377, or equivalent 8.15 Septum wrench, Hewlett-Packard,part #19251-00100 8.16 Tweezers 9.0 CLEANINPGROCEDURES N/A 10.0 MAINTENAPNROCCEEDURES 10.1 Routine: Tighten the elevator's assembly nuts when Archon autosampler displays error message I' Elevator not homed position 'I. 10.1.1 Stop autosamplerrunby 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, empv 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 Mainfenance of ihe Purge & Trap Autosamplor/Concentrator/GU~S Page 3 of 5 Page 105 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 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: GCMS forelinepump maintenance. 10.4.1 Examine the oil level window daily. If the oil level is near or below the lower line then add forelinepump oil. Never add oil while the foreline pump is on. 10.4.1.1 Vent the MSD accordingto the MSD HardwareManual. 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 Reinstallthe fill cap. 10.4.1.5 Pump down the MSD according to the MSD Hardware Manual 10.4.2 Change forelinepump oil every 6-12 months accordingto the MSD Hardware manual. 10.5 Nonroutine: Document any nonroutinemaintenancein the instrument's maintenance logbook. 11.0 OPERATINPGROCEDURES 11.1 For operatingprocedures, refer to an appropriateanalytical method, or to the Archon Purge and Trap Autosampler System Operator's Manual, Telanar LSC200 Instruction Manual and the Hewlett-PackardMSD HardwareManual for HP S973N & HP 6890 SeriesMass SelectiveDetectors. 12.0 RECORDS 12.1 Document any maintenance performed on the instrument in the maintenance or runtmaintenatice logbook. Include a description of the procedure(s) performed, any unusual observations,parts replaced or needingreplacement,and whether the procedure was routine or non-routine. Be sure to date and initial the entry. Logbooks are archived when complete. 13.0 TESTINGCA, LIBRATION AND/OR STANDARDIZATION PROCEDURES 13.1 After cleaning the source and allowing sufficient time for the vacuum to pump down and the mass spectrometerto equilibrateto operationtemperature,runan autotune; check for improved perfomrance and for the presence or absence of air leaks. A tune report can also be used to check for leaks after performing injection port maintenance. 14.0 REFERENCES 14.1 Archon Purge and Trap Autosampler SystemOperator'sManual 14.2 Tekmar LSC200InstructionManual ETS-9-49.0 Routine Maintenanceof the Purge & TrapAutosampler/Concenttor/GUMS Page 4 of 5 Page 106 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 14.3 Hewlett-PackardMSD Hardware Manual for HP 5973N & HP 6890 Series Mass Selective Detectors, 15.0 AFFECTEDDOCUMENTS 15.1 None. 16.0 REMsIONS Revision NUmber. Reason For Revision Revision ETS-9-49.0 Routine Maintenance of the Purge & TrapAutosampler/Concentrator/GC/MS Page 5 of 5 Page 107 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 ~~ Appendix B: Chemical Characterization This appendix includes chemical characterization information for both reference substances and control substances. Page 108 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 Chemical Characterization (Reference Substances) Substance IWAC Name N-EtFOSE alcohol 2-(N-ethylperfluorooctanesu1fonamido)ethyl alcohol PFOS K Salt Potassium perfluorooctanesulfonate FOSA Perfluoroctane-sulfonamide Chemical Formula Identifier source Expiration Date Storage Conditions Chemical Lot Number Physical Description Purity Substance IUPAC Name Chemical Formula Identifier source Expiration Date Storage Conditions Chemical Lot Number Physical Description Purity Substance IUPAC Name Chemical Formula Identifier source Expiration Date ~ Storage Conditions Chemical Lot Number Physical Description Purity CsF 17SOzN(CzH5)CHzCH20H 1691-99-2* 3M Specialty Chemicals 2002 Frozen sEo35 White wax 97.8% N-EtFOSA N-ethylperfluorooctanesulfonamide C~F~~SOZNHCH~CH~ 4151-50-2* 3M Specialty Chemicals 2002 Frozen SD012 White wax 95%$ C7 Perfluoroheptenes(90/10 mix) 10% 2-Perfluoroheptene, 90% Perfluoroheptene C~F&F=CZFC~5,F1iCF=CF* 355-63-5* Lancaster Synthesis 2005 ~ Frozen 90004250, TNA 3025 Clear ambient liquid 100% CsF l7S03K 2795-39-3* 3M Specialty Chemicals 2001 Frozen SD009 White powder 86.4 PFOA Perfluorooctonic acid, Ammonium Salt C7F isCOzNH4 2395-00-8 * 3M Specialty Chemicals 2002 Frozen 1 White powder 97%1 CSFI~SOZNH~ 754-91-6* 3M Specialty Chemicals 2002 Frozen SE027 White wax 95%S Cs Terminal Hydride 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8, 8 heptadecafluorooctane c8F 17H 335-65-9* Aldrich Chemical 2002 Frozen 04307PN, TNA-2983 Clear ambient liquid 99% C, Hydride Cs Hydride 1,1,2,2,3,3,4,4,5,5,6,6,7,7,7 pentadecafluoroheptane WISH 27213-6 1-2* Lancaster Synthesis 2005 Frozen 9005911, TNA-3026 Clear ambient liquid 97% 1,1,2,2,3,3,4,4,5,5,6,6,6 tridecafluorohexane C8i& 355-37-3* Lancaster Synthesis 2005 Frozen 90005941, TNA-3027 Clear ambient liquid 98% Page 109 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 Reference Substances (continued) I Reference Substance I W A C Name I Chemical Formula Identifier C8Hydride/Olefin Mix PFBS C4Terminal Hydride ~ - 1,1,1,2,2,3,3,4,4,5,5,6,6,7,8,8,8 pentadecafluorooctane, 2pertluorooctene Perfluorobutanesulfonate, potassium salt 1,1,2,2,3,3,4,4,4 nonafluorobutane I CsFi&FHCFqSCnFiqCF=CF2 I CdFsSOqK I CAFOH I TCR-99030-18 29420-49-3* 375-17-7* Source 3M Specialty Chemicals 3M Specialty Chemicals Crescent Chemical Expiration Date I StoraEe Conditions Chemical Lot Number 6/6/99 I Frozen I 2002 2002 I Frozen I Frozen ~ I ~ ~ TCR-99030-028 6A-46, TNA-3997 Physical Description Clear ambient liquid White Powder Clear ambient liquid Purity 85% CSHydride, 15%Cs Olefin 97%1 99% Reference Substance I IUPAC Name I Chemical Formula Identifier source Exviration Date I Storage Conditions ~ ~ Chemical Lot Number Physical Description Purity C4 Interior Olefin C3Terminal Hydride Cz Terminal Hydride I I I I 2-Perfluorobutene 1,1,2,2,3,3,3 heata fluorovrovane 1,1,2,2,2 pentafluoroethane I CAFR I C?F.;H I GFqH I 360-89-4* 2252-84-4* 354-33-6* Lancaster Synthesis Lancaster Synthesis Lancaster Synthesis 2002 I Frozen I G00195,TNA-4298 2010 Flammable G0062B, TNA-4294 2010 I ~ Flammable I ~ G00492, TNA-3021 Clear ambient liquid Gas Gas 97% 97% 99% Page 110 of 165 BACK TO MAIN 3M EnvironmentalLaboratory Report No. W2783 Control Substances Structure I IUPAC Name Use source Expiration Date Storage Conditions Chemical Lot Number Physical Description , Purity Control Substances i Structure I IUPACName Use Source I ExDiration Date Storage Conditions Chemical Lot Number Physical Descriation Purity Control Substances Structure I IUPACName Use Source Expiration Date Storage Conditions Chemical Lot Number I Physical Descriation Purity C812 PFCH Perfluorocyclohexane THPFOS CBFI~H~SO~K Potassium 3,3,4,4,5,5,6,6,7,7,8,8,8 tridecafluorosulfonate Pentafluorobenzene C6HF5 Pentafluorobenzene U L / l V 1 3 allalyblb Aldrich Chemical 2005 I Frozen 01911AU Colorless Moist Solid 97% SynQuest Labs 2003 I Frozen 99022-31, TNA-4154 White powder 95% < analysis Restek Corp. 612002 I Frozen ~~ A013256 Methanol solution 99% (2500 p g l d 20.2%) Chlorobenzene-& Toluene-& Dibromoflnoromethane I Chlorobenzene-d< Instrumental Surrogate Standard For GUMS analysis Restek Corp. I 612002 Frozen I A013256 I Methanol solution 99% (2500 p g l d2 0.2%) Ci Dx 1 Toluene-da CHBr2F I Dibromofluoromethane ~ ~ Instrumental Surrogate StandardFor GC/MS analysis Instrumental Surrogate Standard For GCIMS analysis Restek Corp. I 212002 ~~ Restek Corn. I 212002 ~~ Frozen I A012973 I Methanol solution 99% (2500 p g h L 2 0.2%) 1 Frozen A012973 I Methanol solution ~ ~~ 99% (2500 pglmL 2 0.2%) 1,4 Difluorobenzene 4-Bromofluoro-benzene 1,4-Dichlorobenzene-c& Ch H4Fz I 1.4 Difluorobenzene Instrumental Surrogate Standard For GCIMS analysis Restek Corn. 612002 Frozen A013256 II Methanol solution 99% (2500 pg/mL 2 0.2%) ChHaBrF CACIDA I 4-Bromofluoro-benzene ~ I 1 .4-Dichlorobenzene-dA Instrumental Surrogate Standard For GUMS analysis Instrumental Surrogate Standard For GUMS analysis Restek Corn. Restek Corn. 212002 612002 Frozen Frozen A012973 II Methanol solution 99% (2500 pglmL 2 0.2%) A013256 I Methanol solution I 99% (2500 p g l d 2 0.2%) Page 111 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 Appendix C: Kinetics Model and Kinetic Calculations This appendix presentsthe mathematicaldescriptionof the kinetics model employed in this study and the application of this model in the determination of the estimated half-lives presented. Page 112 of 165 BACK TO MAIN 3M EnvironmentalLaboratory Report No. W2783 Kinetics Model C1. Reaction Components and Rates The arguments below are based on the following idealized set of reactions representing the photodegradation of a parent compound P and its products A,, which number N. The actual reactionsthat 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). P + photon +kprn n, A, +Yd (m=ltoN) A, +photon +k h Ym2 (m= 1toN) 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 Ym2represent all the other photolysis products. C2. Parent Compound Concentrations Equation C1 indicates that the pseudo-first order differential change in the parent concentration P at a constant flux of light or a constant concentration of radicals is given bY dP=-P [ n, k,, ]dt which is equivalent to the separable differential equation gP = - ( gn, kp,)dt Equation C4 may be directly integratedto obtain the general solution (-c j In[P]= n, k,, t + C rnI ; With the initial condition P(t = 0) E Po,the specific solution to EquationC4 is P = Po exp [-$n, k,, t)- Po e-kpt Page 113 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 =z using the additional definition of the total parent photolysis rate N k, n, k,, . m =I Equation C6 can be re-written in a form that allows a least-squares estimate of the total parent hydrolysis rate: Using the initial(t =0) measured value of the parent concentration Poand later values P measured at later times t , one can calculate and plot the (linear) quantity [- In (P/Po)] versus time and obtain a least -squares estimate of the slope of the line. The resulting slope is the least-squares estimate L p of the total parent photolysis rate. Equation C6 indicates that over a period of time TI$ (the parent half-life) the parent concentration P is reduced through hydrolysis by a factor of two, where 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,kPmP- k,,A,) dt = ( nmkPmPeO-ke - k,,A, )dt and the (first order, non-separable) differential equation governing the product concentrations is %+ k,A, = n,k,,P0 e-kpt. dt Page 114 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 The "standard form" of Equation C12 is A: + S (t) A, = Q(t) where the "function"S (t)is actually a constant: and Q(t) =n,kp,Po e-kpt. The general solution A, to Equation C12 is contained in where and There are two cases of Equation C18 to consider. In the circumstance that k, = k, which occurs only when the rate of the mthproduct is identical to the total parent photolysis rate, the general solution to Equation B18 is (for k, = k, ) A, ekpt= nmkpmPtO+ C and, using the initial conditionA,(t = 0 )= A, , the specific solution to Equation18 is (for ,k = k,) A, =(nmkPmPtO+A,)e4Pt . We note that when k, = k, = 0 (that is, when both the parent and potential product are photolyticallystable), Equation C7 requires (also) that k,, =0, so Equation C20 becomes Page 115 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 indicating, as required, that the product concentration does not change with time. The circumstance k,, = kp 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, # k, (i.e. that the rate of the mthproduct is different from the total parent rate), the general solutionto Equation C18 is and the specific solution to Equation C18 with the initialcondition A,(t = 0)= A,, is 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 nmkPmPO kP ( 1- e-kp t ) C4. Relationships Between the Parent and Compound Concentrations Equations C7 and C24 can be combined to obtain (for stable products) so that Page 116 of 165 (for stable products) BACK TO MAIN 3M Environmental Laboratory Report No. W2783 or (for stable products) If the changes in the product concentrations are all small compared to the original parent concentration, that is, if we may use the expression (valid for -1 5 X 5 1 ) In(l+X)=X- -1x2 + -1 x 3 - -1x 4 + ..... L3 . 3 4 and Equation C23 becomes (for stable products and m I or (for stable products and cm A, -Amo << Po) Page 117 of 165 BACK TO MAIN 3M Environmental Laboratory Report No.W2783 C5. Parent Half-Life Estimates Based on Limits of Quantificationof the Products In every experimentaldeterminationof 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, = A r Q . 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) Under the same circumstances and assumptions, the experimental data indicate that the parent half-life TI': (see Equation C9) is greater than the value (T$) . as follows: mm (for photolytically stable products at concentrations below the limits of quantitation) The reader should note that Equations C32 and C33 are valid only when both 1) the products are stable and 2) the concentrations of all the potential products are measured. Otherwise, the quantity (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 (TI;) mm, is also questionable. C6. Parent Half-Life Estimates Based on Limits of Quantification and Experimental Precision of Product Concentrations In certain experiments, some products are present at quantifiable but essentially constant concentrationsover 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 contributeto the estimate of the maximumvalue of the parent hydrolysis rate k, . If the set of concentrations measured for the mthproduct have the mean value pmand Page 118 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 standard deviation O, , the data do not exclude the possibility that the product concentration increased from the initial value O, -pmto the value 6, +p, 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 omor 2) concentrations below the limits of quantitation) k, 5 (kp),, -1 *1 = 0 ' BelowLO' AQ: X~ +Constant O,]. Under these circumstances and assumptions, the experimental data indicate that the parent half-life TI'; is greater than the value (T f ) , as follows: mm (for stable products at either 1) constant measured concentrations with standard deviation omor 2) concentrations below the limits of quantitation) TYi 2 (Tq;) . ---= y2) (kP r 1-1 A t Po ln(2) AEQ+z20,l. Below LOQ Constant (c35) The reader should note that Equations C34 and C35 are valid only when both I)the products are photolytically stable and 2) the concentrations of all the potential products are measured. C7. Parent Half-Life Estimates Based on the Experimental Precision of Parent Concentrations In certain experiments, the concentration of the parent remains essentially constant over the time ( A t) of the experiment. In this case, it is the experimental precision of the measured parent concentrations that determines the maximum value of the parent hydrolysis rate k, . If the set of concentrations measuredfor the parent have the mean value ppand standard deviation O, ,the data do not exclude the possibilitythat the product concentration increased from the initialvalue pp -oPto the value + pp O, 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 ppand standard deviation Op ) Page 119 of 165 BACK TO MAIN 3M EnvironmentalLaboratory Report No.W2783 v E ) Under these circumstances and assumptions, the experimental data indicatethat the parent half-life TI': is greater than the value (T . as follows: nun (for essentially constant parent concentrations with mean value ppand standard deviation 6, ) References to Above: B1 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). Kinetics Calculations Only two values of the parent concentration were recorded; Poand P, which reflect before and after the exposure period of length ( t l - t o ) . In this case, no least squares regression is possible to determine the rate k, in Equation C8: k,t =-h [$) (A) In this circumstance,the only available estimate is =-.[?)=- k, 1 t, -to 70.15hrs [III 5889.*15n%',)=g /ml 0.0559 IT-'. The rate of photolysis in the reactor k, is related to the actinic rate of photolysis k,, by Page 120 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 where I,, = 261 w/m2is the actinic solar intensity (at 45"south latitude) and the measured reactor intensity is I, = 680 w/m2. This gives For samples under constant illumination,the reaction rate and half-life are related by Equation C9: However, the actinic half-life is three times larger, according the standard eight-hour exposure day. This leads to - (indirect photolysis) TA1C/2- T-3 W 2 ) = 969 hrs = 40.4days (F) k ACT Page 121 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 Appendix D: Individual Sample Data This appendix includes individual sample data, quality control data and a table summarizing which samples failed to meet the quality control parameters. Page 122 of 165 BACK TO MAIN 3 M Environmental Laboratory Report No. W2783 Samples, Blanks and Standards from the LC/MS portion of the investigation that did not meet Data Quality Objectives. Sample ID. I Description I EtFOSE-OH photolysis in Soils 99039-267-01 3ppb std 032200-MC-44 Matrix Spike 032200-MC-50 No Soil Spike Failed Criteria I 75 -125% accuracy 75 -125% recovery 75 -125% recovery 75 -125% recovery 032200-MC-04 032200-MC-10 I 032200-ST-44 032200-ST-50 032200-ST-24 032200-ST-04 032200-ST-10 032200-EPA-44 032200-EPA-50 Matrix Spike No Soil Spike Matrix Spike No Soil Spike Matrix Spike Matrix Spike No Soil Spike Matrix Spike No Soil Spike 75 -125% recovery 75 -125% recovery 75 -125% recovery 75 -125% recovery 75 -125% recovery 75 -125% recovery 75 -125% recovery 75 -125% recovery 75 -125% recovery 032200-EPA-24 032200-EPA-IO Matrix Spike No Soil Spike 75 -125% recovery 75 -125% recovery Analyte EtFOSA PFOA EtFOSE-OH PFOA FOSA EtFOSA EtFOSE-OH EtFOSE-OH EtFOSE-OH FOSA EtFOSA Et FOSE-OH EtFOSA EtFOSE-OH EtFOSE-OH EtFOSE-OH EtFOSA EtFOSE-OH PFOA FOSA EtFOSE-OH EtFOSE-OH I Value I Comments 137% 37% 26% 14% 15% 127% 150% 48% -79% 132% 52 % -81% 166% 329% 3% 0% 61% -4 % 69% 36% 133%; failed 116 total 3ppb stds failed 2/5 analytes spiked failed 4/5 analytes spiked failed 115 analytes spiked failed 115 analytes spiked failed 3/5 analytes spiked failed 1/5 analytes spiked failed 115 analytes spiked failed 1/5 analytes spiked failed 115 analytes spiked failed 2/5 analytes spiked failed 315 analytes spiked - failed 1/5analvtes sDI ike- d1 Page 123 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 Samples, Blanks and Standards from the LC/MS portion of the investigation that did not meet Data Quality Objectives (continued). EtFOSE-OH photolysis in Fe203 LClMS 0508-EtFOSFe-10 Control Spike 75 -125% recovery EtFOSE-OH 13% failed 115 analytes spiked 0508-EtFOSFe-16 Matrix Spike 75 -125% recovery EtFOSE-OH 52% failed 115 analytes spiked 0508-EtFOSFe-50 Control Spike 75 -125% recovery EtFOSE-OH 138% failed 1/5 analytes spiked 0508-EtFOSFe-56 Matrix Spike 75 -125% recovery EtFOSE-OH 126% failed 1/51analytes spiked I GC/MS 0508-EtFOSFe-96 Control Spike Detected; LOQ (12ppb) IH-perfluoropropane 13.64ppb Data questionable. Retention 0508-EtFOSFe-91 Matrix Spike Detected;LOQ (l2ppb) 1H-perfluoropropane 11.21ppb time change due to organic 0508-EtFOSFe-102 Matrix Spike Detected;LOQ (12ppb) 1H-perfluoropropane 12.53ppb solvent in samples. 0508-EtFOSFe-106 Matrix Spike Detected; LOQ (12ppb) 1H-perfluoropropane 14.76ppb ~ ~~ 0508-EtFOSFe-107 Matrix Spike Detected; LOQ (12ppb) 1H-perfhoropropane 12.36ppb 0508-EtFOSFe-61 Matrix Blank Detected; LOQ (12ppb) 1H-perfluoropropane 16.07ppb 1 1 0508-EtFOSFe-62 Matrix Spike Detected;LOQ (12ppb) 1H-perfluoropropane 16.07ppb failed 1/8 analytes spiked failed 2/8 analytes spiked 0508-EtFOSFe-67 IH-perfluorohexane 126% 0508-EtFOSFe-70 Control Spike 75 -125% recovery 1H-perfluorooctane 66% failed 1/8 analytes spiked 0508-EtFOSEfe-71through 96 75125% recovery see data sheet O-OK failed multiple analytes spiked 0508-EtFOSFe-99 Matrix Spike 75 -125% recovery see data sheet 146% failed 718 analytes spiked 0508-EtFOSEfe100 Control Spike 75125% recovery see data sheet 64,61 failed 618 analytes spiked 0508-EtFOSEfel16 Matrix Spike 75125% recovery 1H-Cs, 2H-Cs 64,61 failed 218 analytes spiked 0508-EtFOSEfel17 Matrix Spike 75125% recovery 1H-Ca, 2H-Cs 5535 failed 218 analytes spiked Page 124 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 Appendix E: Representative Chromatograms Chromatograms from the present study are included in this appendix. Page 125 of 165 BACK TO MAIN 3M EnvironmentalLaboratory Report No. W2783 tch Run # 53 of 62 ta File C:\HPCHEM\l\DATA\RO51100\rushOO53.D Sample Name: 00028-32-00 ...................................................................... Injection Date : 5/12/00 11:28:33 AM Seq. Line : 53 Sample Name : 00028-32-00 Vial : 1 Acq. Operator : kej Inj : 1 Acq. Instrument : Rush Inj Volume : 5 1.11 Acq. Method ,: C:\HPCHEM\l\METHODS\ETFOSll.M Last changed : 5/11/00 6:44:10 PM by kej Analysis Method : C:\HPCHFM\l\METHODS\RO511Al.M Last changed : 5/24/00 12:42:54 PM by kej (modified after loading) S I M Analysis (ES-) for PFOS/PFBS/PFOA using Dionex IonPac NGl column, 4x351r.m. MSD1 299, EiC=2%.7299.7 (R051100RUSH0053.D) API-ES Negative 75000 Mamx Blank 5oM)O 25000 0 I - " I ~ " I ~ ' * l ~ ' - l ~ ' 0 2 4 6 8 10 mlr MSDl 413, ElC412.7413.7 (RO51l~RlJ.SHOO53.D)A P E S Negative BOOM) 40000 Zoo00 Ot,,,,.,.,.,.,... 0 2 4 6 MSQ1 498, ElC=497.7:498.7 (RE1 100\RUSH0053.D) API-ES Negative ----- ------- I , , , I . . 8 10 mlr l1400 1200 0MSDI 499, r p ElC=498.7:2499.7(RC51100\RUSH00453.D)API-ES Negative 8 P 8 v 10 bmin 0 2 4 6 8 10 mir MSD1 528, EIC=525.7:526.7 (R051100\RUSH0053D) A P E S Negative r 0 2 4 6 8 70 MSDl 630, ElC=629.7:630.7(R051lOORUSHoo53.D) API-ES Negative , J-' mln -.--.-/---- _-_I_ -,(- 0 I " 2 ' I ~ " 4 " " 1 6 ' ' ' aI " ----. lo miq _. . Page 126 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 tch Run # 54 of 62 ta File C:\HPCHEM\1\DATA\RO5llOO\rushOO54.D Sample Name: 00028-32-01 3====111=pr=======5==P=======~====E== Injection Date : 5/12/00 11:47:59 AM Seq. Line : 54 Sample Name : 00028-32-01 Vial : 2 Acq. Operator : kej Inj : 1 Acq. Instrument : Rush Inj Volume : 5 pl Acq. Method : C:\HPCHEM\l\METHODS\ETFO511.M Last changed : 5/11/00 6:44:10 PM by kej Analysis Method : C:\HPCHEM\1\METHODS\R0511Al.M Last changed : 5/24/00 12:42:54 PM by kej (modified after loading) SIM Analysis (ES-) for PFOS/PFBS/PFOA using Dionex IonPac NG1 column, 4x35mm. I MSDI 299, ElC=298.7:299.7(RE1100WUSHW54.D) API-ES Negative Calibration SId I I " r l " ' l ' ' * l ' ~ 0 2 4 6 8 10 mir MSDI 413, ElC=412.7:413.7 (RG51100WUSH0054.D) API-ES Negative 60000 40000 20000 or,, , 0 2 - 4 9 n 1 - " 1 ~ * ' I * ' . l ' ' 4 6 0 10 mlr MSDl 498, ElC=497.7:498.7(ROW lCOWUSHOO54.0) API-ES Negative I " ' " " I " ' I 0 2 4 6 MSDI 499,ElC=498.7:499.7(R051IOOWUSHWS4.D) API-ES Negative 4000 3000 2000 0 2 4 6 - MSDl 526, EiC=525.7526.7(RE1looWUSH~54.D)API-ES Negathre 4000 - 2000 7 f * " 1 ' " 1 " ' l ' ' 0 2 4 6 MSDl 630, ElC=629.7:630.7(R051100WUSH0054.D) APCES Negative 3oooO 2woo loo00 0 ' ~ ' I ~ ' 8 10 mi -4-/---.-4-\ 0 10 "in ----.-J- ' l ' ~ ~ , ~ ~ - 8 10 min Page 127 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 Batch Run # 55 of 62 Data File C:\HPCHEM\1\DATA\RO511OO\rushOO55.D Sample Name: 00028-32-02 .................................................................... Injection Date : 5/12/00 12:07:21 PM Seq. Line : 55 Sample Name : 00028-32-02 Vial : 3 Acq. Operator : kej Inj : 1 Acq. Instrument : Rush Inj Volume : 5 p l Acq. Method : C:\HPCHEM\l\METHODS\ETFO511.M Last changed : 5/11/00 6:44:10 PM by kej Analysis Method : C:\HPCHEM\l\METHODS\RO511Al.M Last changed : 5/24/00 12:42:54 PM by kej (modified after loading) SIM Analysis (ES-) f o r PFOS/PFBS/PFOA using Dionex IonPac N G l column, 4x35mm. MSD1 299.EICE298.7:298.7 (ROSll(X1\RUSHW55.D)API-ES Neewe --- I ' . . I ' ' . I ' " , ' ' . I ' ~ 0 2 4 6 8 10 min MSDl 413, ElC=412.7:413.7(RffiIlWWUSHW55.D) API-ES NWdlve ...... d Un . . + . I 0 2 4 6 8 10 min MSDl 498, EIC47.7498.7 (RffillW\RUSH0055.D) API-ES Negativa .. :.: ..........i. \ - I ' . " " ' /Lm 0MSD1499, ElC498.7:4299.7 (RE1lWV3USHWS45.0) API-ES N W I b?6 I', 8 vL/7 Mw 10 mil 0 2 4 0 8 10 rnin MSDI 520, ElC=525.7:528.7 (ROW iWWUSHm56.D) API-ES Nesative - - - I ~ ' " ' ' 1 " , ' " , ~ ~ 0 2 4 6 8 10 min MSDl 630,EICm9.7m.7 (RffillWRUSHCW55.D) APES Negative -, 0 , , 2 , , , , , , , , , I . , 4 6 8 , , I , , 10 mi4 Instrument 1 5/24/00 12:46:55 PM kej Page 1 of 2 Page 128 of 165 BACK TO MAIN 3M EnvironmentalLaboratory Report No.W2783 Batch Run # 3 of 62 Data File C:\HPCHEM\l\DATA\R0511OO\rushO003.D Sample ----===iPt===ii==P================-=-===-=============-=========-------- Name: 1:7 Injection Date : 5/11/00 7:24:17 PM Seq. Line : 3 Sample Name : 1:7 MilliQ/MeOH Vial : 98 Acq. Operator : kej Inj : 1 Acq. Instrument : Rush Inj Volume : 5 pl Acq. Method : C:\HPCHEN\l\METHODS\ETFOSll.M Last changed : 5/11/00 6:44:10 PM by kej Analysis Method : C:\HPCHEM\1\METHODS\R0511Al.M Last changed : 5/24/00 12:42:54 PM by kej (modified after loading) SIM Analysis (ES-) for PFOS/PFBS/PFOA using Dionex IonPac NG1 column, MilliQ/MeOH 4~35m. ' MSD1 299. EICGS8.7:299.7(RMllW'RUSHW03.D) API-ES Matbe lmj Control Blank A I I " . , I I 0 2 4 6 MSDl 413, ElC=412.7:413.7 (R051 loo\RUsHOOD3.D) AWES Negative I BOODO Mow or,. , 0 2 4 6 MSD1 498,ElC=497.7:498.7(R05llW'RUSHooo3.D) API-ES Negative . , . . . ) . , . 8 10 mi il/J I 8 10 min I ' . . I ' t . 1 1 1 0 2 4 6 8 MSD1 498.EICW98.7:498.7 (RE1 lW\RUSHW03.D) APCES Negative I " 10 min , ' . . , . . . I . . . ( . . . 0 2 4 6 8 10 min MSD1 526. EIC=525.7 528.7 (R05llWWJSHwaj.D) AWES Negntive Instrument 1 5/24/00 12:43:06 PM kej Page 1 of 2 Page 129 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 Batch Run # 2 of 62 Data File C:\HPCHEM\1\DATA\R0511OO\~ushOOO2.D Sample Name: MeOH blank =IC*=====fPC-F=II=I=============-==~====================~===~==~==-----. Injection 'Date : 5/11/00 7:04:58 PM Sample Name : MeOH blank Seq. Line : Vial : Acq. Operator : kej Inj : Acq. Instrument : Rush Acq. Method : C:\HPCHEM\l\METHODS\ETFO511.M Last changed : 5/11/00 6:44:10 PM by k e j Analysis Method : C:\HPCHEM\1\METHODS\RO5llAl.M Last changed : 5/24/00 12:42:54 PM by kej (modified after loading) (Results are f r o m SIM Analysis (ES-) for PFOS/PFBS/PFOA using Dionex IonPac NG1 2 99 1 a previously saved column, 4x35mm. I . * . , . ~ l , l l . / I . . I . . 0 2 4 8 8 10 mir MSDl 413, ElC=412.7:413.7 (RffiIIaO\RUSH0002D) API-ES Negalive n 4ooM) 20000 . , --- O I , , , , , , ' . . I . . . 0 2 4 6 a MSD1498.EICt497.7:498.7 (RffiIlWUSHOW2.D) API-ES N~patIve , .... ':"' '" I I MSOl 499,EIC=498.7:499.7 (RffillOO~USnoooZO] API-ES Negative 1 A I 30m -i-- 4cv'n_J-nl . . . , . . . " , . . . , . . . , . . -a/--+- 1"'l 2 4 8 8 MSDl 526, ElCt525.7526.7 (RffilIWUSHOW2.D) MI-ES Negatlve io mi ----------- A- , ' - . " ' - , . . . I 0 MSD1 630, EICC629.7:6230.7 (ROSliWIRUSHOW4 2.D) API-ES Negative 6 8 10 mln I " ~ , ' . , , . . . , . . . , . . 0 2 4 6 8 10 mir\ Instrument 1 5/24/00 12:43:01 PM kej Page 1 of 2 Page 130 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 s Batch Run # 13 of 62 Data File C:\KPCHEM\1\DATA\RO511OO\rushOOl3.D SampLe Name: 00028-32-09 *=l=PP=iil=S;-CilPe=-~===~==-===~~=====~======~=-===*~====~==============~ Injection Date : 5/11/00 10:37:01 PM Seq. Line : 13 Sample Name : 00028-32-09 Vial : 10 Acq. Operator : kej Inj : 1 Acq. Instrument : Rush Inj Volume : 5 pl Acq. Method : C:\HPCHEM\l\METI30DS\ETFOSll.M Last changed : 5/11/00 6:44:10 PM by kej Analysis Method : C:\HPCHEM\l\METHODS\R0511Al.M Last changed : 5/24/00 12:42:54 PM by kej (modified after loading) SIM Analysis (ES-) for PFOS/PFBS/PFOA using Dionex IonPac NG1 column, 4x35m. MSOl 299. ElCL298.7:299.7(RSllWMUSH0013.0) API-ES Negative I " ' t ' . " " I ~ ' . , ' ~ 0 2 4 MSD1 413,EIC'412.7:413.7 (RSllOONUSHNJl3.0)API-ES NqaUw 10 mir 260000 0 , " ' , " ' I * ' " " ' , " 0 2 4 6 8 MSDl 498.ElC~497.7:498.7(RSllWMUSHWl3.0) API-ES Negative , 10 rnir 1500000 1OOOOOO 500000 0 , ~ " , " ~ l " ' 1 ' ' ~ , ' ~ 0 2 4 6 8 10 miq MSDl 499.EIC.4SB.7:499.7 (R0511001RUSHW13.D)API-ES NegaUw o,, , , I " ' t " ' I " ' 1 ' . 3 0 2 4 E 10 mi I T I ' . ' . ' . k , " , ' ", ' 1 , I , , I , : 2 4 6 8 10 min MSDl 530, ElC~629.7~.7(RWIlW\RUSHW13.DA)PI-ES NepUve , , , , , , , , , , . , , ,, : , .'. , : , , Instrument 15/24/00 12:43:50 PM k e j Page 1 of 2 Page 131 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 Batch Run # 29 of 62 Data File C:\HPCHEM\l\DATA\RO51100\rushOO29.D Sample Name: 0508-EtFOSfe-11 ........................................................................ Injection Date : 5/12/00 3:45:32 AM Seq. Line : 29 Sample Name : 0508-EtFOSfe-11 Vial : 21 Acq. Operator : kej Inj : 1 Acq. Instrument : Rush Inj Volume : 5 pl Acq. Method : C:\HPCHEM\l\METHODS\ETF051l.M Last changed : 5/11/00 6:44:10 PM by kej Analysis Method : C:\HPCHEM\1\METHODS\RO5llAl.M Last changed : 5/24/00 12:42:54 PM by kej (modified after loading) SIM Analysis (ES-) for PFOS/PFBS/PFOA using Dionex IonPac NG1 column, 4x35mm. MSD1 299.EICGS7:299.7 (R051100\RUSHW29.D) APES Negatlrre 0,. , 0 . 2 /------ I ' ' ~ l ' ~ ' I ~ ' ' 1 ' ~ 4 E 8 10 IT MSD1413, EIC=412.7413.7(RE1 lW\RUSHoMs.D) APCES Negative Im uxxx) ZOMX) 0, . , , , , , . , . . . , . . . , . . . , . . 0 2 4 6 8 10 n MSDl 488,ElC497.7488.7 (R051loo\RUSHCOB.D) API-ES Nsgatlvs . .... : . . . . . " I 1400 I ' 0 2 4 b " 1 1 MSDl 499, EIC=498.7:499.7(R051100iRUSHOM9 0) APCES Negative 2Mx) 1500 0 2 4 8 $0 n ;10 MSDl 528, ElC-525.7526.7 (R051lOOiRUSHW29.D) APES Negative A 2000 1 ~ " ' " 1 ' " 1 ' ~ ' 1 ~ ~ 0 2 4 8 8 10 n MSDl 630, EIC*629.7:630.7 (R0511WUiUSH0029.D) API-ES NWIk fnstrument 1 5/24/00 12:45:01 PM kej Page 1 of 2 Page 132 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 Batch Run # 30 of 62 Data File C:\HPCHEM\1\DATA\R0511OO\rushOO3O.D Sample Name: 0508-EtFOSfe-12 ....................................................................... rnjection Date : 5/12/00 4:04:47 AM Seq. Line : 30 Sample Name : 05 08-Et FOSfe-12 Vial : 22 Acq. Operator : kej Inj : 1 Acq. Instrument : Rush Inj Volume : 5 1.11 Acq. Method : C:\HPCHEM\l\METHODS\ETFO511.M Last changed : 51/11/006:44:10 PM by kej Analysis Method : C:\HPCHEM\l\METHODS\ROsllAl.M Last changed : 5/24/00 12:42:54 PM by kej (modified after loading) SIM Analysis (ES-) for PFOS/PFBS/PFOA using Dionex IonPac NG1 column, 4x35mm. MSD1 299,ElC=29B.7:299.7(R0511WUlUSH0030.D) APCES Nqlatii I - Exposed 72hS Blank Spiked Fez03 No Peroxide rjooo 0 I " ' l ' ' ' l ' ' ' ' I ' ' ~ ~ ' ~ 0 2 4 MSDl 413. EIC=412.7:413.7 (R051lWvtUSHOOX.D) APCES Negative 8 10 mi IOOMX) 0 -. 1 l " ' l " ' l * ' ~ I " ' ~ ~ ' 0 2 MSD1498. EICY197.ZW8.7 (RE11WvtUsHW3O.D) APCES NylaUve 8 10 mln MMXX, o,.,.l..,,,..,. 0 2 4 8 MSD1 489. EIC=498.7:499.7(R0511WvtUSUW3O.D1 APES NwsUw I .,: 8 B 10 mlr MSDl 525, EIC=S25.7:526.7 (R051lWRUSH0030.D) APCES Nylltive 10 mln B I 2 4 MSDl 830. EIC*629.%630.7(ROJHWWUSH0030.D) &PI-ES NegaUve 8 10 mlr Z0 L 1 " ~ I " ~ I ' " I ' ' ' I ~ ' 0 2 4 8 10 mi Instrument 1 5/24/00 12:45:05 PM kej Page 1 of 2 Page 133 of 165 BACK TO MAIN 3M Environmental Laboratory Report No.W2783 Batch Run # 31 of 62 Data File C:\HPCHEM\1\DATA\RO51100\rush0031.D Sample Name: 0508-EtFOSfe-1: .......................................... Injection Date : 5/12/00 4:24:02 AM Seq. Line : 31 Sample Name : 0508-EtFOSfe-13 Vial : 23 Acq. Operator : kej Inj : 1 Acq. Instrument : Rush Inj Volume : 5 pl Acq. Method : C:\HPCHEM\1\METHODS\ETFOSll.M Last changed : 5/11/00 6:44:10 PM by kej Analysis Method : C:\HPCHEM\l\METHODS\R05llAl.M Last changed : 5/24/00 12:42:54 PM by kej (modified after loading) SIM Analysis (ES-) f o r PFOS/PFBS/PFOA using Dionex IonPac N G 1 column, 4x35m. i .....i . . , . ' SOW0 - Exposed 72hn Sample FetO3 No Peroxide 25Mx) 0 I"'I"'I 0 2 8 MSOl 413, ElC=412.7413.7(RE1lflOlRUSHW31.D) API-ES Negallve 2woo 0 I ' , . I 0 2 4 8 MSDl 498,EIC=497.7:498.7 (R051100vlUSH0031.D) API-ES Negaliva 0 2 I " , I "4 ' I ' 8 MSD1 499, EIC=498.7:4S9.7 (RWllWvlUSHOO3l.D) API-ES NegaUvs / I " 8 10 mil R i /--A . . . I ' ) . / . . 8 10 rnlr -A7 8 10 mir 1 I " ' I " . I ' ~ 0 2 4 E MSD1526, ElC=525.7528.7(R051100RUSHW31.D) API-ES NWtiM 1 - 1 . . ' I ' . 8 10 mu ,I \- o j , , , , I " ~ I " ' l ' - . I ~ , 0 2 4 8 : 8 10 mlr MSD1 630,EIC=829.7:Q0.7(R0511~USHW31.D) API-ES NegaIva f . . . I ~ . . I . . . I . . . , t - 0 2 4 6 8 10 rnlr Instrument 1 5/24/00 12:45:09 PM kej Page 1 of 2 Page 134 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 Batch Run # 36 of 62 Data File C:\HPCHEM\1\DATA\RO511OO\rush0036.D Sample Name: 0508-EtFOSfe-18 *====i===~IJiii======t==============f= Injection Date : 5/12/00 6:00:26 AM Seq. Line : 36 Sample Name : 0508-EtFOSfe-18 Vial : 28 Acq. Operator : kej Inj : 1 Acq. Instrument : Rush I n j Volume : 5 pl Acq. Method : C:\HPCHEM\l\METHODS\ETFO511.M Last changed : 5/11/00 6:44:10 PM by kej Analysis Method : C:\HPCHEM\l\METHODS\R0511Al.M Last changed : 5/24/00 12:42:54 PM by kej (modified after loading) SIM Analysis (ES-) fox PFOS/PFBS/PFOA using Dionex IonPac NG1 column, 4 ~ 3 5 m . 1 zj Exposed ~ nhrs Control MilliQ NoPemxide 25ooo 0 I . . ' I ' . ' I 0 2 4 MSDl 413, EIC=412.7:413.7 (R051100WUSHW36.D)API-ES Negative I I(,' , , 8 4 - I . ' 10 nmir 0 2 4 6 8 10 m I MSDI 498,EIC497.7:498.7(Rffi1100WUSHW36.D) API-ES Negative 25004 I ' " I ' ~ ~ I ' ' ' I ' ' ~ I ~ ' 0 2 4 6 8 10 mi MSD1499, ElG498.73499.7(ROSllOO!RUSH0038.D) APGES Negative MSDI 526, ElC=S26.7:526.7 (R05llWWUSH0038.0) API-ES Negative :E\ ' 5ooo I ' . . I ' ' . I " ' l ' " I ' ' 0 2 6 8 10 MSDl g30, ElC=629.7:630.7(R051100WUSHW3E.D) API-ES Negathre _c mi! Instrument 15/24/00 12:45:32 PM kej Page 1 of 2 Page 135 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 Batch Run # 14 of 61 Data File C:\HPCHEM\1\DATA\R05llOO\rushOO65.D Sample Name: 0508-EtFOSfe-31 ..................................................................... Injection Date : 5/12/00 3:20:38 PM Seq. Line : 65 Sample Name : 0508-EtFOSfe-31 Acq. Operator : kej Vial : 41 Inj : 1 Acq. Instrument : Rush Inj Volume : 5 pl Acq. Method : C:\HPCHEM\l\METHODS\ETM511.M Last changed : 5/11/00 6:44:10 PM by kej Analysis Method : C:\HPCHEM\1\METHODS\RO5llBl.M Last changed : 5/24/00 2:14:48 PM by kej (modified after loading) SIM Analysis (ES-) f o r PFOS/PFBS/PFOA using Dionex IonPac NG1 column, 4x35m. 1 MSDl286, EICm298.7299.7(RC511WWSHLhX5.D) APCES Negatfve - Unexposed 72hrs Blank Fez03 NoPemxide I 0 2 MSD1413. EICr4127:413.7 (RO511WWJSHo0ss.D) APCES NegaUva I . . ~ , . . . I . . . / . . 2 4 6 8 10 min OMS01 498,EIC&'.7496.7 (RC511WWUSHWB6.D) AWES Nagnb I 1wO 0 2 4 6 MSDl499. ElC5498.7:499.7(Rffil 1WWUSHoosS.D) API-ES Negativa a 10 mi A I 1 . - . , . . . ~ ", . . . , . . . , . . . 4 6 8 10 mi MSD1 526, EICdZ5.7:528.7 (ROSllWRUSH~5.D) APCES Naga(ive ~ 0 2 4 6 M S D l 8 0 , EIC=S29.7:S30.7(ROSllWWUSH0065.D)API-ES Negative WMI: 4Mx)- Moo- (I I...,...,.. 2 4 6 - 1 ' . a 10 mln I , . . , . . - 6 10 mw Instrument 15/24/00 2:15:52 PM kej Page I of 2 Page 136 of 165 BACK TO MAIN 3M EnvironmentalLaboratory Report No.W2783 1 Batch Run # 15 of 61 Data File C:\HPCHEM\l\DATA\RO5llOO\rushOO66.D Sample Naae: 0508-EtFOSfe-32 ...................................................................... Injection Date : 5/12/00 3:39:56 PM Seq. Line : 66 Sample Name : 0508-EtFOSfe-32 Vial : 42 Acq. Operator : kej Inj : 1 Acq. Instrument : Rush Inj Volume : 5 pl Acq. Method : C:\HPCHEM\l\METHODS\ETFOSll.M Last changed : 5/11/00 6:44:10 PM by kej Analysis Method : C:\HPCHF.M\l\METHODS\ROSllBl.M Last changed : 5/24/00 2:14:48 PM by kej (modified after loading) SIM Analysis (ES-) for PFOS/PFES/PFOA using Dionex IonPac NG1 column, 4x35mm 1r 1 soaoo MSDl 299, E10=298.7:299.7(R05llOMRUSHOOSS.D)API-ES N o g M Unexposed-72hn Blank Spiked Fez03 No Peroxide Instrument 1 5/24/00 2:15:56 PM kej Page 1 of 2 Page 137 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 Batch Run # 16 of 61 Data File C:\HPCHEM\1\DATA\R0511OO\rushOO67.D Sample Name: 0508-EtFOSfe-33 PPI====5===I==-==ICI5==E=ESP====I=131=1E===-====-=====~===*====~===== Injection Date : 5/12/00 3:59:13 PM Seq. Line : 67 Sample Name : 0508-EtFOSfe-33 Vial : 43 Acq. Operator : kej Inj : 1 Acq. Instrument : Rush Inj Volume : 5 pl Acq. Method : C:\HPCHEM\l\METKODS\ETFO511.M Last changed : 5/11/00 6:44:10 PM by kej Analysis Method : C:\HPCHEM\l\METHODS\RO51lfll.M Last changed : 5/24/00 2:14:48 PM by kej (modified after loading) SIM Analysis (ES-) f o r PFOS/PFBS/PFOA using Dionex IonPac NG1 column, 4x35in I 7m4 - 1 5owo MSDl 299, ElC=298.7:299.7(R051lOO\RUSH00gl.D)APCES N@w Unexposed 72hB Sample Pe203 NoPeroxidc .,.I,..I/,,I.:~,l...,,. 0 2 4 6 8 10 mh MSDI 498,EIC=4!37.74B8.7 (R051lOOWUSHwtn.O) API-ES Nagalive 1'"~"'I'''I'-~ 0 2 4 6 MSDI 499,EIC=49&7:498.7 (Rffil lOO\RUSHWW.D) A P E S Negative 4wo 3MJo 20 I ' . ' , ' " I ' ' ' 0 2 MSDI 526, EIC=S25.'1526.7(RROSllW\RUSHOOB7.D)API-ES NegaW ~I'"I'' 8 10 mi l ' ~ ' 8 ' ' 10 rmn - -__J__v_ f I ~ ~ ' I " I " ' I ' ' ' 1 ' ' 0 2 4 6 8 10 mlQ MSD1 630, ElC429.7630.7 (RROSIlOORUSHOOB7.D) API-ES Negalhm 1 " ' " " I " ' I ' ' 0 2 4 8 10 mi Instrument 15/24/00 2:16:01 PM k e j Page I of 2 Page 138 of 165 BACK TO MAIN 3M EnvironmentalLaboratory Report No.W2783 Batch Run # 21 of 61 Data File C:\HPCHEM\1\DATA\RO511OO\rushO07Z.D Sample Name: 0508-EtFOSfe-38 ..................................................................... Injection Date : 5/12/00 5:35:37 PM Seq. Line : 7 2 Sample Name : 0508-EtFOSfe-38 Vial : 48 Acq. Operator : kej Inj : 1 Acq. Instrument : Rush Inj Volume : 5 pl Acq. Method : C:\HPCHEM\l\METHODS\ETFO511.M Last changed : 5/11/00 6:44:10 PM by kej Analysis Method : C:\HPCHEM\l\METHODS\RO511Bl.M Last changed : 5/24/00 2:14:48 PM by kej (modified after loading) SIM Analysis (ES-) for PFOS/PFBS/PFOA using Dionex IonPac NG1 column, 4x35mm. - MSD1 299,ElC-298.7:299.7(ROS1lowtUSHW7Z.D) AWES N q a m unexposed 72hrs conhol MilliQ No PemXide ,.,,.., ,.,, 0 2 4 6 MSD1 413, ElCa4127:413.7(RffillM11RUSHW72.0) AWES Negatrve , .-, , I , , a , , 10 , mi! 0 2 4 6 MSD1 499,ElC.498.7:499.7 (RC5llWWJSH0072.D) API-ES Nq&W 10 min -3 A 3wo - - " ' 1 ' - , , I-. ' . I " ' I ' ' ' I ' ' ' I io mlr MSDI 526, EIC=525.7:526.7(R051lWRUSH0072.D) API-ES Negative . t , ' I,. ' I I , ' ' + ' ' 0 2 4 6 8 10 mln MSD1 630,EIC=6'&.7:630.7 (ROSllWWJSwmZ.0) AWES NegaUw 15owoo 1WWW 5OM100 01 , . , , , , , , L Instrument 15/24/00 2:16:24 PM kej Page 1 of 2 Page 139 of 165 BACK TO MAIN 3M EnvironmentalLaboratory Report No. W2783 Batch Run # 40 of 61 Data File C:\HPCHEM\1\DATA\RO511OO\rushOO9l.D Sample Name: 0508-EtFOSfe-51 ====i=====E===I=E===iS==e===========~==~=====================~=====~===== Injection Date : 5/12/00 11:42:33 PM Seq. Line : 91 Sample Name : 0508-EtFOSfe-51 Vial : 61 Acq. Operator : kej Acq. Instrument : Rush Inj : 1 Inj Volume : 5 pl Acq. Method : c:\HPCHEM\1\METHODs\ETFOSll.M Last changed : 5/11/00 6:44:10 PM by kej Analysis Method : C:\HPCHEM\1\METHODs\RO5llBl.M Last changed : 5/24/00 2:14:48 PM by kej (modified after loading) SIM Analysis (ES-) f o r PFOS/PFBS/PFOA using Dionex IonPac NG1 column, 4x35mm. MSDl m,EICz2987:289.7(ROSl100\RUSHOODl.D) API-ES Negative 75m 5woo 25000 0 - Day 0 B I Fe~203 No Peroxide , ' , . , . ' . \ , I . / . . . , . . 0 2 4 6 8 10 m MSDl 413, EICa412.7:413.7(RC611~USHW91.D)APKS NegaWe .,.I...,... 0 2 4 6 MSDl 498, EIC=487.7@8.7(RC6llWWUSHOODl.D) API-ES NOgauVa I " . , " a 10 m 1600 1600 1400 1200 I ' " I ' ' ' I ' ~ ' 1 ~ ~ . 1 ~ ~ 0 2 4 6 8 10 m MSDl 499.ElC498.7499.7 (ROS11WWUSHWOl.D) API-ES Negative 3ml A Instrument 1 5/24/00 2:17:49 PM kej Page 1 of 2 Page 140 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 Batch Run # 41 of 61 Data File C:\HPCHEM\1\DATA\R05110O\rushOO92.D Sample Name: 0508-EtFOSfe-52 ...................................................................... Injection Date Sample Name Acq. Operator - : 5/13/00 12:01:50 AM : 0508-Et FOSf e 52 : kej Seq. Line : 92 Vial : 62 Inj : 1 Acq. Instrument : Rush Inj Volume : 5 pl Acq. Method : C:\HPCHEN\l\METHODS\ETFO511.M Last changed : 5/11/00 6:44:10 PM by kej Analysis Method : C:\HPCHEM\l\METHODS\RO511Bl.M Last changed : 5/24/00 2:14:48 PM by kej (modified after loading) SIM Analysis (ES-) for PFOS/PFBS/PFOA using Dionex IonPac NG1 column, 4x351~1. MSDl 299.EIC*248.7:299.7(R051lMW(USHMB2.D) API-ES N-atfvs Day 0 Blank Spiked Fez03 No Peroxide w I Instrument 1 5/24/00 2:17:54 PM kej Page 1 of 2 Page 141 of 165 BACK TO MAIN 3M EnvironmentalLaboratory Report No. W2783 Batch Run # 42 of 61 Data File C:\HPCHEM\1\DATA\RO511OO\rushOO93.D Sample Name: 0508-EtFOSfe-53 =r~==L=l-L==il==*=======~======-=~==~-==~=======i~=--===~==~=======-==== Injection Date : 5/13/00 12:21:06 AM Seq. Line : 93 Sample Name : 0508-EtFOSfe-53 Vial : 63 Acq. Operator : kej Inj : 1 Acq. Instrument : Rush Inj Volume : 5 pl Acq. Method : C:\HPCHEM\l\METHODS\ETFO511.M Last changed : 5/11/00 6:44:10 PM by kej Analysis Method : C:\HPCHEM\l\METHODS\ROSllBl.M Last changed : 5/24/00 2:14:48 PM by kej (modified after loading) SIM Analysis (ES-) f o r PFOS/PFBS/PFOA using Dionex IonPac NG1 column, 4x35mm. I MSDI 299,810=298.7:299.7(RO5IlawtUSnaosJ.D)APl-ES Negative 1 0 ' ' 0 2 4 6 a 10 mlr MSDI 413, EIC=412.7:4i3.7(RO511 WWUSHwS3.D) AWES Negative 0~...,..,,..,,..,,,..,.. 0 2 4 6 a 10 mln MSDl498, EIC=497.7:498.7 (ROSllWWUSHoo93.D) API-ESNegative 0 2 4 6 a 10 mi MSDl 499.EIC498.7499.7 (ROW lOOlRUSHW9J.D) API-ES Negative b 2 i 6 MSD1 528,ElC=525.?:526.7 (RffillawtUSHoo93.D) API-ES Negath I w rb mi I * " I " ' l " ' I ' ' ' , ' ' - 0 2 4 6 a 10 mil MSOl 63,EIC=629.7:63.7 (RffillWWUSH0093.D) API-ESNegative a I " ~ I ~ " l " ' l " ~ , " 0 2 4 6 10 mi Instrument 1 5/24/00 2:17:58 PM kej Page 1 of 2 Page 142 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 Batch Run # 47 of 61 Data File C:\HPCHEM\1\DATA\R051100\rush0098.D Sample Name: 0508-EtFOSfe-58 ======I===========i===P======II==f===l=S============================= Injection Date : 5/13/00 1:57:42 AM Seq. Line : 98 Sample Name : 0508-EtFOSfe-58 Vial : 68 Acq. Operator : kej Inj : 1 Acq. Instrument : Rush Inj Volume : 5 p 1 Acq, Method : C:\HPCHEM\l\METHODS\ETF0511.M Last changed : 5/11/00 6:44:10 PM by kej Analysis Method : C:\HPCHEM\l\METHODS\RO511Bl.M Last changed : 5/24/00 2:14:48 PM by kej (modified after loading) SIM Analysis (ES-) for PFOS/PFBS/PFOA using Dionex IonPac NG1 column, 4x35mm. I MSDl2S9, EIC-298.7:298.7 (R05llOaWUSHooSe.O) APCES Negathn Ucdoy 0n ~MlilliQ No POmXidC 0 2 4 6 MSDl 413, EIC*412.7413.7 (RE1 lOaWUSHw9e.D) A P E S NegatIW ' . , , ,'7 - 8 10 mlr ' . ' I , ' . I . . I , . . . ) , . ' , . . 0 2 4 8 8 10 mir MSDl 498.ElC=407.7:498.7 (RC5110MRUSHw9e.D) AWES N W l v e I 1"'I 2 " ' 1 ' ~ - ' I " ' ' " - ' " 10 4 6 MSDl459, EIC=498.7:459.7 (RDJ11MIWUSHooSe.D) A P E S Nsgativs mi I m.-{ MSD1830,IC-829.7B230.7 (R05llMWUSHoo4se.D) APCES' Nega'tive 6I ' T ' - . 8 .R+10 .-/ mi 1wQMK) 5oooM) or, 0 , , 2 J Y I ' ' ' ~ ~ ' ' I ~ ' ' , ' ' 4 6 8 10 mi4 Instrument 1 5/24/00 2:18:21 PM kej Page 1 of 2 Page 143 of 165 BACK TO MAIN z 0 BACK TO MAIN L 1 BACK TO MAIN 4-0 3 93 BACK TO MAIN z 0 .. A E$.- BACK TO MAIN c i c BACK TO MAIN .. .. . . . .& 3? 1 i BACK TO MAIN z 0 BACK TO MAIN z 0 BACK TO MAIN z m Y- O z 0 BACK TO MAIN 0 Z BACK TO MAIN | Ad o) i ok ihy : iz a CoarT TT BACK TO MAIN 3M Environmental Laboratory Report No. W2783 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 155 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 STANDARD LABORATORYSOILS PARAMETER METALS Ag, fngn(gdried bark AI. mgMg dried bask As. mon<~&led bask Ba, mgMgdried bas$. Be, m$Kg adid b k Ca nrglK0df&dbasis Cd,mon<s drled basis Co, drlsd barlo Cf, mdKg dded bask, Cu,mgR<gdried basis Fe, mgMg drled bast6 Hg. mgMg dried bas* Mg, mon<gdrledbash MR m g M g ddedbask Mo,mgNg drfedbasis Na, mon<s dried basis e NI,m$Kg drledbaJb P, drled bask Pb,mgMg Modbask Se,~d#W&& 2n.mgKgdrledbaClo EXcHANaE ACMrrY Ertractabta ca. meqnooe ExtradableP,meqmog ErlrectableMg. ~~~ Ewvaaable Na,meqn0Og Base SaturaUm.k CEC, meqllOOg ESP, IL SAR, units NUTRIENTS Avallable P.mpn NH3-N W- NO3-N. Iqebhl N. mon<o ORQANIC M A m TOC. X OM, X PHYSOCHEMJCAL Field Capacty, K PHW. units pHs. unlls Lime-req. TondAcn Soluble Salls, mmhodcm CLASS1FICATlON X Cfay *A sm % Sand Soil Type -BASE NEUTRALPESTICIDES ACID PESTICIDES BDL Below Delectlon Umiis 4 22000 <lo 210 ..+ 3 : ' 0.6 3000 425 8 36 12 20000 0.04 IS 2800 800 52 120 18 62.0 40 400 49 8.14 0.68 297 0.03 42 28.3 0.11 0.04 61 2.00 84 1470 3.m 3.09 19.1 5.7 5.7 1-8 0.98 22 44 34 LOW BDL BOL 43 40000 <lo p 4.g loo0 <os 5 41 8.5 22OOo 0.1 1 1500 '?o 84 73 14 150 40 400 47 3.50 0.10 0.43 0.02 $8 220 0.09 0.05 5 0.25 14 280 0.m 0.478 22.3 .4.6 4.5 f.B 0.32 26 36 38 CLAY LOAM BDL BDL EPkssY 4 46000 ' no 100 0.6 , 86000 4.5 , 8 25 13 . l8WO 0.02 3OOOO 710 . 92 220 13 710 40 c200 47 26.1 0.18 3.58 0.06 . 100 21.3 0.28 0.05 75 1.80 8.0 250 0.467 0.805 16.0 7.7 7.5 NONE 0.86 22 2s 52 SANDY CLAY LOAM BDL BM Page 156 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 -~-~ Appendix G: Light Intensity Measurements at 45" South Latitude (Miami FL) Page 157 of 165 BACK TO MAIN 3M EnvironmentalLaboratory Report No.W2783 PAGE 03 Atlas Xenon Filter Comblnatfon ... t Page 158 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 ~-~ ~ Appendix H: Characteristics of the Spectral Output of the Suntest Instruments This appendix contains an Excel spreadsheet of the characteristics of the spectral output of the Suntest Photoreactors used in the present investigation. Page 159 of 165 BACK TO MAIN 3M EnvironmentalLaboratory Report No. W2783 Suntest Irradiance in W/mA2*nm Assuming the use of 300-800nm Global Sensor Only Filters Used Wavelength nm 250 252 254 256 258 260 262 264 266 268 270 272 274 276 278 280 282 284 286 288 290 292 294 296 298 300 302 304 306 308 310 312 314 316 318 320 322 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 Irradiances factored to yield 680 W/mA2in 300-800nm band IR QlSuprax (UV) 0.001 119 0 0 0 0.001I 1 9 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 0.0951 15 0.129804 0.154422 0.168969 0.195825 0.23499 0.26856 0.294297 0.312201 0.3681 51 ..bi c Page 160 of 165 324 0.352 326 0.369 328 0.4 330 0.431 332 0.449 334 0.475 336 0.495 338 0.525 340 0.549 342 0.565 344 0.566 346 0.587 348 0.614 350 0.61 352 0.635 354 0.656 356 0.685 358 0.662 360 0.675 362 0.719 364 0.714 366 0.73 368 0.813 370 0.858 372 0.767 374 0.8 376 0.827 378 0.864 380 0.962 382 0.992 384 0.974 386 0.996 388 1.028 390 1.111 392 1.126 394 1.227 396 1.642 398 1.552 400 1.243 402 1.228 404 I.241 406 1.284 408 1.473 41 0 1.395 412 1.551 414 1.416 416 1.369 41 8 1.426 420 1.644 422 1.453 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 0.393888 0.41291 I 0.4476 0.482289 0.502431 0.531525 0.553905 0.587475 0.614331 0.632235 0.633354 0.656853 0.687066 0.68259 0.710565 0.734064 0.766515 0.740778 0.755325 0.804561 0.798966 0.81 687 0.909747 0.960102 0.858273 0.8952 0.925413 0.966816 1.076478 I.I10048 I.089906 1.114524 1.150332 1.243209 1.259994 1.37301 3 1.837398 1.736688 1.390917 1.374132 1.388679 1.436796 I.e48287 1.561005 1.735569 1.584504 1.53191I 1.595694 1.839636 1.625907 Page 161 of 165 424 1.472 426 1.462 428 1.466 430 1.466 432 1.487 434 1.5 436 1.566 438 1.714 440 1.616 442 1.616 444 1.57 446 1.563 448 1.573 450 2.267 452 2.031 454 1.796 456 1.81 I 458 2.127 460 1.835 462 3.267 464 2.476 466 2.541 468 5.277 470 2.487 472 1.922 474 2.924 476 1.837 478 1.813 480 2.289 482 2.516 484 2.651 486 1.952 488 1.a42 490 1.898 492 3.012 494 2.089 496 1.871 498 1.888 500 1.898 502 1.973 504 2.005 506 1.94 508 1.927 510 1.934 512 1.963 514 2.013 516 2.031 518 2.021 520 1.995 522 1.971 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 1.647168 1.635978 1.640454 1.640454 1.663953 1.6785 1.752354 1.917966 I.808304 1.808304 1.75683 I.748997 1.760187 2.536773 2.272689 2.009724 2.026509 2.3801 13 2.053365 3.655773 2.770644 2.843379 5.904963 2.782953 2.150718 3.271956 , 2.055603 2.028747 2.561391 2.81 5404 2.966469 2.184288 2.061198 2.123862 3.370428 2.337591 2.093649 2.112672 2.123862 2.207787 2.243595 2.17086 2.156313 2.164146 2.196597 2.252547 2.272689 2.261 499 2.232405 2.205549 Page 162 of 165 524 1.98 526 1.966 528 1.978 530 1.954 532 1.932 534 1.942 536 2.008 538 2.014 540 2.113 542 1.996 544 1.977 546 1.962 548 I.921 550 1.876 552 1.84 554 1.938 556 2.17 558 2.106 560 1.936 562 I.912 564 1.749 566 1.706 568 1.77 570 1.997 572 2.032 574 1.802 576 1.624 578 1.572 580 1.654 582 2.215 584 2.034 586 1.738 588 2.118 590 2.159 592 1.996 594 2.185 596 I.607 598 1.492 600 1.471 602 1.37 604 1.263 606 1.207 608 1.I84 610 1.292 612 1.494 614 1.31 616 I.631 618 2.672 620 2.172 622 1.416 BACK TO MAIN 3M EnvironmentalLaboratory Report No. W2783 2.21562 2.199954 2.2I3382 2.186526 2.1 61908 2.1 73098 2.246952 2.253666 2.364447 2.233524 2.21 2263 2.1 95478 2.149599 2.099244 2.05896 2.168622 2.42823 2.356614 2.166384 2.139528 1.957131 1.909014 1.98063 2.234643 2.273808 2.OI6438 1.817256 I.759068 1.850826 2.478585 2.276046 1.944822 2.370042 2.41 5921 2.233524 2.445015 I.798233 1.669548 1.646049 1.53303 I-413297 1.350633 1.324896 1.445748 1.671786 1.46589 1.825089 2.989968 2.430468 1.584504 Page 163 of 165 624 1.181 626 I.256 628 1.251 630 1.51 632 2.325 634 1.246 636 0.959 638 0.927 640 0.834 642 0.856 644 0.876 646 1.013 648 1.571 650 1.431 652 1. I 2 654 1.071 656 0.86 658 0.801 660 1.103 662 0.763 664 0.762 666 0.855 668 1.037 670 0.575 672 0.682 674 0.912 676 0.526 678 0.567 680 0.514 682 0.738 684 1.065 686 1.214 688 2.331 690 1.16 692 0.73 694 0.603 696 0.432 698 0.688 700 0.347 702 0.327 704 0.298 706 0.31 708 0.275 710 0.424 712 2.069 714 0.594 716 0.302 718 0.289 720 0.254 722 0.297 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 1.321539 1.405464 1.399869 1.68969 2.60 1675 1.394274 1.073121 1.037313 0.933246 0.957864 0.980244 1.133547 1.757949 1.601289 1.25328 1.198449 0.96234 0.896319 1.234257 0.853797 0.852678 0.956745 1.160403 0.643425 0.763158 1.020528 0.588594 0.634473 0.575166 0.825822 1.I91735 1.358466 2.608389 I.29804 0.81687 0.674757 0.483408 0.769872 0.388293 0.365913 0.333462 0.34689 0.307725 0.474456 2.315211 0.664686 0.337938 0.323391 0.284226 0.332343 Page 164 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 724 0.384 726 0.592 728 0.817 730 0.593 732 0.634 734 0.472 736 0.316 738 0.375 740 1.097 742 0.368 744 0.272 746 0.264 748 0.439 750 0.356 752 0.231 754 0.273 756 0.406 758 0.823 760 1.344 762 0.554 764 1.555 766 1.114 768 0.388 770 0.194 772 0.152 774 0.188 776 0.21 778 0.247 780 0.388 782 0.327 784 0.225 786 0.171 788 0.335 790 0.693 792 0.137 794 0.18 796 0.326 798 0.632 800 0.233 Total Integrated Irradiance in 300-800nm Wavelength Band 607.6 WlmY 0.429696 0.662448 0.9 14223 0.663567 0.709446 0.5281 68 0.353604 0.419625 1.227543 0.41 1792 0.304368 0.29541 6 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 0.4341 72 0.365913 0.251775 0.191349 0.374865 0.775467 0.153303 0.20142 0.364794 0.707208 0.260727 680.0 WlmA2 Page 165 of 165