Document nvXobg4Rg97Dey7p6rjYbZOa

BACK TO MAIN 3M Environmental Laboratory Report No. W2783 Study Title Screening Studies on the Aqueous Photolytic Degradation of 2-(NEthylperfluoroctanesulfonamido)-ethyl alcohol (N-EtFOSE Alcohol) Data Requirement Consistent With: OPPTS: 835.5270 "Indirect Photolysis Screening Test" -and- OECD Draft Document "Phototransformation of Chemicals in Water - Direct and Indirect Photolysis", August 2000 Author Thomas L. Hatfield, Ph.D. Study Completion Date April 19th, 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 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 This page has been reserved for specific country requirements. Page 2 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 Compliance Statement Study Title: Screening Studies on the Aqueous Photolytic Degradation of 2-(NEthylperfluorooctanesulfonamido)-ethyl alcohol (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 "Phototransformation of 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. Page 3 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 Quality Assurance Statement Study Title: Screening Studies on the Aqueous Photolytic Degradation of A/-(Ethylperfluorooctanesulfonamido)-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 04/06/01 04/06/01 04/16/01 04/16/01 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 Personnel and 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: Representative Chromatograms......................................................................125 Appendix F: Soil Types and Characterizations.....................................................................155 Appendix G: Light Intensity Measurements at 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 1. Typical Sample Preparation Scheme Used in the Present Investigation.............. 12 Table 2. Observed Products and Mass Balance Determinations for Direct and Indirect Photolysis in Water, Iron Oxide Containing Water and Synthetic Humic Water.....................16 Table 3. Observed Products and Mass Balance Determinations for Photolytic Decomposition of 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 N-EtFOSE Alcohol by Indirect Aqueous Photolysis .............................................................................................................................. 18 Page 6 of 165 BACK TO MAIN 3M Environmental Laboratory 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 Intertec Corporation, 6875 Washington Ave. South, Minneapolis, MN 55439) Location of Archives Digital copies of original data, and all original paper data have been archived and will be retained in the 3M Environmental Laboratory archives for at least 10 years. Page 7 of 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(/V-ethylperfluorooctanesulfonamido)-ethyl alcohol (N-EtFOSE alcohol) and to identify the primary degradation products. Our techniques are based on both EPA and OECD guidance documents.9,10 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 perfluorooctanoic acid, Nethylperfluorooctane sulfonamide and perfluorooctane sulfonamide. Rates of indirect photolytic degradation are highly dependent on experimental conditions however, using an iron oxide (Fe2C>3) 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 biodegradation are 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 photolysis.1,2 To 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 aqueous solution to which H2O2 was added as a well characterized source of .OH radicals.3"1 This was used to test for the propensity of N-EtFOSE alcohol for Indirect photolytic decomposition. The second matrix contained a dilute aqueous CaCk solution and a well-characterized soil. This matrix was used to test the effects that adsorption-desorption equilibria, surface induced reactions and "OH quenching1'5 could have on indirect photolytic decomposition. The third matrix contained Fe203 in 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.6'7 The fourth matrix was a standard humic material8 and was consistent with a modified procedure based on the US EPA methodology, OPPTS 835.5270 "Indirect Photolysis Screening Test"9 as well as OECD Draft Document "Phototransformation of Chemicals in Water - Direct and Indirect Photolysis", August 20001. To effectively determine photolytic decomposition, the concentration of parent material must be monitored overtime. 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 predicted degradation products by LC/MS as shown in Figure 1 were EtFOSA is A/-ethylperfluorooctanesulfonamide, PFOA is ammoniumperfluorooctanoic acid, FOSA is perlfluorooctanesulfonamide and PFOS is potassiumperfluorooctanesulfonate. Because of the possibility of volatile degradation products, it was decided to monitor for selected C2 through Cg 2- or 3- substituted perfluoronated olefins (e.g. CsF16) and 1- or 2substituted hydrides (e.g. CsF17H) in the iron-rich matrix by dynamic purge and trap gas chromatography/mass spectrometry. Page 9 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 Figure 1. Structures of the Compounds Observed by LC/MS Analysis A/-EtFOSE Alcohol E tF O S A FOSA PFOA 44-H4 -O' K FFFFFFFFO PFOS Determination of the kinetic rate constant (kp) 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 Pt = - l n ( 2 2 (C8) Where t represents elapsed time, P represents the measured concentration of the parent after exposure and P0 represents the initial concentration. The half-life of N-EtFOSE alcohol ( T ^ ) is related to the determined rate constant by the following equation. t i/2= fo(2) p kp (Q9) 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 investigation are attached in Appendix A "Analytical Methods". Equipment settings, conditions and complete quality control parameters are listed within those specific methods. UVA/isible analysis were performed following 3M Environmental Laboratory Method ETS-946.0 "Operation and Maintenance of the Hewlett Packard 8453 UV-Visible Spectrophotometer" An aqueous saturated solution of N-EtFOSE alcohol was prepared and an initial UVA/IS 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 1, ten 40-mL sample screw cap VOA vials were prepared: sample, duplicate, triplicate, sample spike, matrix blank, matrix blank spike (assured no accidental contamination of matrix by target compounds), direct photolysis sample, direct photolysis sample spike (assured that degradation observed was due to indirect photolysis and not another process), control blank and control blank spike (assured no accidental contamination of the blank had occurred). All vials contained 5 mL of appropriate matrix: water, soil in water at 0.70XX g in 5 mL, Fe+3 at a 24X molar excess in water, and H20 2 was at 1:1 molar equivalent, added every 24 hours. Aliquots of N-EtFOSE 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 42C. 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 photo reactor. 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 3C. The temperature of the chamber itself was allowed to drift to 70 10C. 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 1. 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 Test Matrix + + + + + + 0 0 0 0 Control Matrix 0 0 0 0 0 0 + + + + Test Substance + + + + 0 0 + + 0 0 Post Photolysis Target Analyte spike 0 0 0 + 0 + 0 + 0 + Sample Type 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* With HA W/out HA GC/MS* With HA W/out H20 2 XXXX XXXX XXXX XX XX XXXX XXXX XXXX XXXX XXXX XXXX Ind. Photo. Sample Rep 1 Ind. Photo. Sample Rep 2 Ind. Photo. Sample Rep 3 Ind. Photo. Sample Spike Matrix Blank Matrix Blank Spike Direct Photo. Sample Direct Photo. Spike Control Blank Control Blank Spike +0 +0 +0 +0 +0 +0 0+ 0+ 0+ 0+ + + -f + 0 0 + + 0 0 0 Exposed to Light X X X X 0 Exposed to Light X X X X 0 Exposed to Light X X X X + Exposed to Light X X X X 0 Exposed to Light X X X X + Exposed to Light X X X X 0 Exposed to Light X X X X + Exposed to Light X X X X 0 Exposed to Light X X X X + Exposed to Light X X X X Ind. Photo. Sample Rep 1 Ind. Photo. Sample Rep 2 Ind. Photo. Sample Rep 3 Ind. Photo. Sample Spike Matrix Blank Matrix Blank Spike Direct Photo. Sample Direct Photo. Spike Control Blank Control Blank Spike +0 +0 +0 +0 +0 +0 0+ 0+ 0+ 0+ + + + + 0 0 + + 0 0 0 Not Exp. to Light X X X 0 Not Exp. to Light X X X 0 Not Exp. to Light X X X + Not Exp. to Light X X X 0 Not Exp. to Light X X X + Not Exp. to Light X X X 0 Not Exp. to Light X X X + Not Exp. to Light X X X 0 Not Exp. to Light X X X + Not Exp. to Light X X X + = added to test vial; 0 = NOT added to test vial; ` Duplicate sets, one with h t0 2, one without (excludes the Humic material test where H2C>2 was not added) X X X X X X 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 Maintenance of Archon Purge and Trap Autosampler, Tekmar Purge and Trap Concentrator and Agilent Gas Chromatograph/Mass Spectrometer". The HPLC/MS analysis followed 3M Environmental Laboratory Method ETS-8-181.0 "Analysis of Photolysis Samples for Fluorochemicals by High Performance Liquid Chromatography With Mass Spectrometry Detection". Equipment settings, separation conditions and ions monitored are present in this method. Study Deviations Gas chromatography/mass spectrometry (GC/MS) was used for the analysis of volatile degradation products in the indirect photolysis test, the Fe+3 matrix and the H2O2 rich matrix. GC/MS 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 instrumentation was unavailable. The LC/MS analysis of the samples from the soil containing matrices showed low levels of back ground 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 Data Quality Objectives 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, particularly at upper and lower calibration limits. Residuals generated in curve-fitting must be within 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 curve fitting, 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 25% 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 particular target 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 LC/MS 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 C8F i7H, 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 material to 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 N-EtFOSE 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 UV/Vis 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 H2O2 Tim e o f exposure w as 69.5 hours S am ple Condition Ind. Photo. Sam ple1 Initial Tim e Point Dir. Photo. Sam ple2 Initial Tim e Point Ind. Photo. Sam ple1 Exposed to Light Dir. Photo. Sam ple2 Exposed to Light Ind. Photo. Sam ple1 Not Exposed to Light Dir. Photo. Sam ple2 Not Exposed to Light Detection Limits EtFOSE-OH PFOA PFOS nM oles 93.86 94.19 57.39 77.71 63.03 91.62 1.59 nM oles nMole s ND ND ND ND 5.53 ND ND ND 4.09 ND ND ND 0.24 0.20 FOSA n M o le s ND ND 0.53 ND 0.48 ND 0.21 EtFOSA V o latiles M ass Balance nMoles nM oles (percent 0.37 ND 3.33 0.49 3.36 ND 0.2 ND ND 0.075 ND ND ND 0.0095* ) 104% 104% 74% 87% 78% 101% Vials initially contained 90.35 nMoles N-EtFOSE alcohol. 1. Indirect Photloysis Sample: These samples had H20 2added (1:1 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 H20 2added, results are from duplicate samples. *Sum total of all volatiles. ND = non detect. 2b. Matrix: Fe20 3 in Water, With and Without H2O2 Tim e of exposure was 69.5 hours S am ple Condition FejOa W / 4 A 1 Initial Tim e Point Fe20 3 W O /H A 2 Initial Tim e Point Fe20 3 W / H A 1 Exposed to Light F e A W O /H A 2 Exposed to Light Fe A W /H A 1 F e A W O /H A 2 Not Exposed to Light Not Exposed to Light Detection Limits EtFOSE-OH n M o les 79.30 93.61 ND 59.53 61.34 90.01 1.59 PFOA PFOS FOSA n M o le s 2.64 ND 41.35 7.54 5.36 ND 0.24 n M o le s ND ND 0.41 0.33 ND ND 0.20 n M o le s Id ND 20.98 0.39 0.87 ND 0.21 EtFOSA nM oles 3.27 ND 0.36 4.33 4.20 0.23 0.2 Volatiles M ass Balance nM oles (percent ND ND 0.14 ND ND ND 0.0095* ) 94% 104% 70% 80% 79% 100% Vials initially contained 90.35 nMoles N-EtFOSE alcohol. 1. Samples had H20 2(1:1 molar equivalance) as a radical source every 24 hours and Fe20 3added (24 Fe+3:1 N-EtFOSE-OH molar equivalance) as a radical generating species, results are from quadripulate samples. 2. Samples contained just Fe20 3(24 Fe+3:1 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 Tim e o f exposure was 72.0 hours S am ple Conditions Humic W ater1 Initial Tim e Point 18.2 M O W ater2 Initial Tim e Point Humic W ater1 Exposed to Light 18.2 M O W ater2 Exposed to Light Humic W ater1 Not Exposed to Light 18.2 M O W ater2 Not Exposed to Light Detection Limits EtFOSE-OH PFOA nMoles nMoles 7.55 ND 7.40 ND 6.51 0.25 6.39 ND 7.39 ND 7.52 ND 0.17 0.20 PFOS n M o les ND ND ND ND ND ND 0.16 FOSA n M o les ND ND ND ND ND ND 0.18 EtFOSA nM oles ND ND ND ND ND ND 0.17 Mass Balance (percent) 111% 109% 99% 94% 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 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 As was noted in the introductory section, the addition of hydrogen peroxide to water was done to determine the propensity of N-EtFOSE 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 H2O2 was due to the equilibrium reaction between H2O2 and the hydroxyl radical, the end result of which was decomposition of the parent material. Indirect photolysis in the synthetic humic material was 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 (Fe20 3 with H20 2 data). As with the reaction between N-EtFOSE alcohol and H20 2, 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, Fe203 and A/-EtFOSE alcohol is perhaps the most environ mentally 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 H2O2, 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+3 is 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 N-EtFOSE 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 Wl (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.11 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 N-EtFOSE alcohol, both in the presence and absence of added H2O2. The data shows that the addition of H2O2 speeds up the reaction when compared to those samples without H20 2. 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 N-EtFOSE alcohol. The data from the three sample sets in table 3 which all contained H2O2 supports the hypothesis that soils will slow the reaction, probably by some type of OH quenching. Because the soil itself can act to promote indirect photolysis, the role of adsorption-desorption equilibria 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 H2O2. 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 Fe203 data was used as an environmental model to generate a half-life estimate for the degradation of N-EtFOSE 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 E tF O S A 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 T im e o f e x p o s u re w a s 72 .0 h ou rs ETFOSE-OH PFOA PFOS FOSA EtFOSA S am ple Condition Soil W /H A 1 Initial Tim e Point Soil W O /H A 2 Initial Tim e Point Soil W /H A 1 Exposed to Light Soil w o /h a 2 Exposed to Light Soil W /H A 1 Not Exposed to Light Soil W O /H A 2 Not Exposed to Light Detection Limits (nanom oles (nanom oles (nanom oles (nanom oles (nanom oles ))) 26.35 ND 0.22 27.21 ND 0.23 ) ND ND ) ND ND 5.22 7.24 0.48 8.16 1.75 23.38 0.84* 0.29 0.78 ND 25.50 ND 0.26 ND ND 25.85 ND 0.22 ND ND 0.92 1.21 0.20 0.21 0.47 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 H20 2(1:1 molar equivalance H20 2:N-EtF0SE 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 T im e o f e x p o s u re w a s 7 2 .0 hours ETFOSE-OH PFOA PFOS FOSA EtFOSA S am ple Condition Soil W /H A 1 Soil W O /H A 2 Soil W /H A 1 Soil W O /H A 2 Soil W /H A 1 Soil W O /H A 2 Initial Tim e Point Initial Tim e Point Exposed to Light Exposed to Light Not Exposed to Light Not Exposed to Light Detection Limits (nanom oles (nanom oles (nanom oles (nanom oles (nanom oles ))) ) ) 25.04 ND ND ND ND 24.16 ND ND ND ND 8.99 4.81 0.63 1.85 5.03 19.26 2.21 0.55 0.72 1.55 23.60 ND 0.26 ND 0.43 19.62 ND 0.56 ND ND 0.92 1.21 0.20 0.21 0.47 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 H20 2(3:1 molar equivalance H20 2:N-EtF0SE alcohol - 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 Environmental Laboratory Report No. W2783 3c. EPA Synthetic Soil Mix - Sandy Clay Loam T im e o f e x p o s u re w a s 7 2 .0 hours ETFOSE-OH PFOA PFOS FOSA EtFOSA S am ple Condition Soil W /H A 1 Soil W O /H A 2 Initial Tim e Point Initial Tim e Point Soil W H O ;,1 Soil W O /H A 2 Soil W /H A 1 Exposed to Light Exposed to Light Not Exposed to Light Soil W O /H A 2 Not Exposed to Light Detection Limits (nanom oles (nanom oles (nanom oles (nanom oles (nanom oles )))) ) 26.17 ND ND ND ND 27.82 ND ND ND ND 17.66 25.54 3.02 1.02* 0.72 0.25 2.82 0.68 2.70 0.47 27.36 ND ND ND ND 14.72 ND ND ND ND 0.92 1.21 0.20 0.21 0.47 Mass Balance (percent) 85% 91% 88% 89% 89% 48% Vials initially contained 30.65 nMoles N-EtFOSE alcohol. 1. Samples contained Soil (0.70XX grams In 5 ml water) and H2C>2(3:1 molar equivalance H20 2:N-EtF0SE 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. Page 20 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 Conclusions Phototransformations of 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-(Nethylperfluorooctanesulfonamido)-ethyl alcohol (A/-EtFOSE alcohol) and to identify the primary degradation products. Our techniques are based on both EPA and OECD guidance documents.9,10 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 main findings are that the rate of photodegradation by 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 experimental conditions however, using an iron oxide (Fe203) photoinitiator matrix model an environmental half-life estimate of 40 days 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 heptadecafluoroctanes and 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 balance for the degradation of N-EtFOSE alcohol to form the primary products PFOA, EtFOSA and FOSA was within 100+30% 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. Pestic. Sei. 1999, Vol. 55, pp. 955-961. 2. Nubbe, M. E.; Adams, V. D.; Moore, W. M. The Direct and Sensitized Photo-oxidation of Hexachlorocyclopentadiene. Wat. 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.; Sedlk, P. Photoinitiated Reactions of Hydrogen Peroxide in the Liquid Phase. J. Photochem. Photobiol. A.: Chem. 1992, Vol. 68, pp. 1-33. 5. Haag, W. R.; Hoigne, J. Photo-Sensitized 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. Science 1966, Vol. 154, p. 1012. 8. Takahashi, N.; Ito, M.; Mikami, N.; Matsuda, T.; Miyamoto, J. Identification of Reactive Oxygen Species Generated by Irradiation of Aqueous Humic Acid Solution. J. Pesticide Sei. 1988, Vol. 13, pp. 429-435. 9. Fate, Transport and Transformation Test Guidelines, OPPTS 835.5270 Indirect Photolysis Screening Test, EPA 712-C -98-099; United States Environmental Protection Agency, U.S. Government Printing Office: Washington, DC, 1998, pp. 1-22. 10. OECD Guideline for Testing o f Chemicals, Phototransformation o f Chemicals in Water--Direct and Indirect Photoysis, (Draft Document); OECD, 2000, pp. 1-- 59. 11. OECD Guideline for Testing o f 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 representation of the data developed in this study. It has been issued by: Thomas LHatfefSfP pedal Projects Team Leader 5ate William K. Reagen, Ph'. D., Laboratory Management Date 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 Maintenance of the Hewlett Packard 8453 UV-Visible Spectrophotometer ETS-9-44,0 Operation and Maintenance of the Sunlight Exposure System, Immersion Unit, and Recirculating Water Chiller System ETS-9-49.0 Routine Maintenance of Archon Purge and Trap Autosampler, Tekmar Purge and Trap Concentrator and Agilent Gas Chromatograph/Mass Spectrometer ETS-8-177.0 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 Fluorochemicals by Archon Purge and Trap Autosampler, Tekmar Purge and Trap Concentrator and Agilent Gas Chromatograph/Mass Spectrometer ETS-8-181.0 Analysis of Photolysis Samples for Fluorochemicals by High Performance Liquid Chromatography With Mass Spectrometry Detection Page 24 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 3M Environmental Laboratory M ethod Analysis of Photolysis samples for fluorochemicals by High Performance Liquid Chromatography w ith Mass Spectrometry Detection Method Number: ETS-8-181.0 Exact Copy of Original Q p y __ N ta i D a te Approved by: Adoption Date: Effective Revision Date: OC7~ Date Page 25 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 1.0 Scope and Application_________________________________________ _____________ 1.1 This procedure defines the steps for analysis of fluorochemicals in photolysis study samples by high performance liquid chromatography (HPLC) with mass spectrometry (MS) detection and quantification. Refer to the HP 1100 HPLC/MSD Standard Operating Procedure ETS-9-34.0 for operating and maintenance procedures related to the instrument. Refer to Standard Operating Procedures ETS-8-176 and ETS-8-177 for information involving sample preparation and photolytic exposure procedures. 1.2 Compatible analytes. Test substance and degradation products for fluorochemicals or other fluorinated compounds, or other ionizable compounds, which includes but is not limited to: C om nound A cronym Periluorooctanoic acid PFOA Perfluorooctanesulfbnate PFOS Perfluorooctanesulfonam ide FOSA N -m ethylperfluorooctanesulfonam ide N -M eFO SA N -ethylperfluorooctanesulfonantide N -E tF O S A 2-(N m ethylperfluorooctanesulfonamido) N-M eFOSE-OH ethyl alcohol Comoonnd A cronym Perfluorobutanoic acid PFBA Perfluorobutanesulfonate Perfluorobutanesulfon amide PFBS FBSA N -m ethylperfluorobutanesulfonam ide N-M eFBSA N -ethylp erflu o ro b u tan esu lfo n am id e N -E tF B S A 2-(N -m ethylperfluorobutanesulfonam ido) ethyl alcohol N-M eFBSE-OH 2-(N-ethylperfluorooctanesulfonam ido) ethyl alcohol N -E tF O S E -O H 2-(N -ethylperfluorobutanesulfonam ido) ethyl alcohol N -E tF B S E -O H ... and other C4 thru C ,0 homologues, and polymeric materials based on the above aforementioned compounds. 1.3 Compatible matrices for analysis. Aqueous (Millipore ASTM Type I water), buffered water, lake water, sea water and metal slurries (TiCh, Fe203, etc.) that have been diluted with an appropriate analytical solvent such as acetone or methanol. 2.0 Summary of Method________________________________________________________ 2.1 This method describes the analysis o f fluorochemicals in a specified matrix, using HPLC electrospray mass spectrometry for chemical separation and detection/quantification. The analysis is performed by separating target analytes on an HPLC analytical column such as a Dionex NG1 (35x 4.6mm, 10pm particle), Betasil C18 column (50X2 mm, 5 pm particle) or equivalent using an ammonium acetate/MeOH solvent gradient. Detection by electrospray ionization mass spectrometery in either the positive or negative mode is utilized to quantify data. The MSD may be run in Selected Ion Monitoring (SIM) mode, looking for specific, pre-selected and set analyte ions (i.e. m/z 499 for PFOS (deprotonated)), or SCAN mode which collects and stores data for all ions in a specified mass range. Data quantification is then performed using either HP ChemStation or Target Software. ETS-8-181.0 Analysis o f Photolysis Samples for Fluorochemicals by HPLC/MS Page 2 of 15 Page 26 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 3.0 Definitions________________________________ _____ 3.1 Calibration Standard. A dilution of various amounts o f a stock, intermediate or purchased standard to achieve standard solutions in a concentration range of interest. 3.2 Calibration Curve. The graphical relationship between known values, such as concentration o f a series of calibration standards and their instrumental response. 3.3 Internal Standard Quantification. Process o f establishing a relationship between the ratio o f the target analyte(s) response to internal standard or surrogate response and a known concentration of the target analyte(s). The ratio of analyte to internal standard response is used to generate the calibration curve and determine unknown concentrations. 3.4 External Standard Quantification. Process o f establishing the concentration o f a target analyte by plotting the theoretical amount (in units of ppb or ppm, etc.) versus the response o f the target analyte(s) on column. The resultant curve(s) shall be used to determine unknown concentrations by comparing the area response o f target analyte(s) to the area response and corresponding analyte amount on the appropriate analyte's calibration curve. Differences in sample mass/volume analyzed, if noted, must be compensated for by a factor applied to the value. 3.5 Correlation Coefficient (r). A measure of the degree o f correlation between two variables. This term is generally used to evaluate the linearity o f a Least Squares Linear regression. An r value of 0.98 is at the lower bounds of what is considered linear. Values o f r may range from -1 to +1. A value o f +1 denotes perfect direct functional relationship between two variables. A value o f -1 also denotes a perfect inverse relationship. When r = 0, there is no effect of one variable upon the other variable. 3.6 Coefficient of Determination (r2). The square o f the correlation coefficient. It is the proportion of the variation in the dependent variable that is accounted for by the independent variable. 3.7 Internal standard. A known amount of a compound or element similar in analytical behavior to the compound(s) or element(s) of interest, added to all samples and standards, and carried through the entire measurement process (post-photolysis, after solvent dilution). It provides a reference for evaluating and controlling the precision and bias of the applied analytical method. Samples are to be quantified using the internal standard. 3.8 Surrogate. An organic compound similar to the target analyte(s) in chemical composition and behavior in the analytical process but is not normally found in the sample(s). A surrogate may be added to samples along with the test analyte (pre and/or post photolysis) to monitor the sample integrity (leaks or matrix effects). The surrogate may be added to the calibration standards to serve as a qualitative reference for the samples. 3.9 Continuing Calibration Verification (CCV). Standards analyzed during an analytical run to verify the continued accuracy of the calibration curve. This solution may or may not be prepared from a different source or lot number than the calibration curve standards. ETS-8-181.0 Analysis o f Photolysis Samples for Fluorochemicals by HPLC/MS Page 3 o f 15 Page 27 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 3.10 Solvent Blank. A sample o f analyte-free medium (for example, methanol, 1:7 diluted buffenmethanol) that is not taken through the sample preparation process. This blank is used to evaluate instrument contamination. 3.11 Blank. For photolysis studies, there are multiple blanks to adequately represent the variables of the study (Exposed, Unexposed and Day 0 samples with/without peroxide addition). These blanks are carried through the sample preparation, photolytic and analytical procedures to monitor for contamination during any step. It is also used to establish a chromatographic baseline/background and monitor for analytical interference or suppression o f target analyte(s) from the matrix. 3.11.1 M atrix Blank: An analyte-free matrix (buffered water, lake water, etc.) to which all reagents are added in the same volumes or proportions as used in sample processing. It is used to document the test system without test analyte present. 3.11.2. Control Blank: An analyte-free matrix (ASTM Type II water) to which all reagents are added in the same volumes or proportions as used in sample processing. It serves as a control for the test matrix to monitor background levels, interferences or suppression of target analyte(s) from the test matrix. 3.12 Lim it of Quantitation (LOQ). The lowest concentration that can be reliably measured within specified limits o f accuracy during routine laboratory operating conditions. The LOQ is generally 5 to 10 times the minimum concentration with a 99% confidence limit that the concentration is greater than zero. However, it may be nominally chosen within these guidelines to simplify data reporting. For many analytes, the LOQ is selected as the lowest non-zero standard in the calibration curve that is greater than 4 times the level of the matrix blank. Sample LOQ are highly matrix-dependent. 3.13 Sample Triplicates. Three samples taken from and representative o f the same sample source and separately carried through all steps of the extraction, photolysis and analytical procedures in an identical manner. There are multiple sets o f triplicate samples to adequately represent the photolytic variables o f the study (Exposed, Unexposed and Day 0 with/without peroxide addition). Triplicate samples are used to assess variance o f the photolytic method, including sample preparation, photolysis, and analysis. 3.14 Control Sample. A known matrix (ASTM Type II water) containing the test analyte(s) carried throughout the entire sample preparation, photolytic and analytical procedure. There are multiple sets o f triplicate samples to adequately represent the photolytic variables o f the study (Exposed, Unexposed and Day 0 with/without peroxide addition). This is used to document method performance and matrix effects by comparing recoveries from the different matrices and sample types. 3.15 Relative Standard Deviation (RSD). A measure of precision defined as the standard deviation o f three or more values divided by the average of the values and multiplied by 100. (Also reported as Coefficient of Variation (CV)). 3.16 Analytical Spike (AS). Prepared by adding a known mass of target analyte(s) to a specified amount o f a sample or control matrix prior to analysis. This assumes that an independent estimate of target analyte concentration is available. Analytical spikes are used to determine the effect o f the matrix on recovery efficiency. There are multiple ETS-8-181.0 Analysis o f Photolysis Samples for Fluorochemicals by HPLC/MS Page 4 o f 15 Page 28 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 types of spiked samples to adequately represent the photolytic variables of the study (Exposed, Unexposed and Day 0 ; with/without peroxide addition.) 3.16.1 M atrix Spike. The test matrix (buffered water, lake water) sample containing the test analyte or blank to which a known mass of target analyte(s) is added prior to analysis. 3.16.2 Control Spike. The control matrix (ASTM Type n water) sample containing the test analyte or blank to which a known mass of target analyte(s) is added prior to analysis. 3.17 Accuracy. The closeness o f agreement between an experimentally determined value and an accepted reference value. When applied to a set of observed values, accuracy is a combination of a random (precision) and a common systematic (bias) component. For puiposes of the study, the acceptance criterion is 75% to 125% o f the nominal value. 3.18 Dilution. A step in the sample preparation procedure in which a solvent (i.e. methanol, acetone) is added to the test analyte/sample matrix (i.e. water, buffer, etc.) to prepare it for instrumental analysis. 3.19 Atmospheric Pressure Ionization (API): The Agilent Technologies HPLC 1100/MSD system allows for ionization o f incoming liquid sample from the analytical column to the mass spectrometer interface by utilizing a source, probe, hot gas, and specific voltages. 3.20 Electrospray Ionization (ES, ESI): A method of ionization performed at atmospheric pressure, whereby ions in solution are transferred to the gas phase via tiny charge droplets. These charged droplets are produced by the application o f a strong electrical field. 3.21 Mass Spectrometry, Mass Spectrometer (MS), Mass Spectrometer Detector (MSD): The API HP 1100 MSD system equipped with a quadrupole mass selective detector. Ions are selectively discriminated by mass to charge ratio (m/z) and subsequently detected. 3.22 Geometric Mean of the calibration curve: The square root o f the product o f the high standard concentration and the low calibration curve standard. When preparing calibration curve standards, the number of calibration standards below the geometric mean shall equal the number of calibration standards above the geometric mean. Having equal distribution o f calibration standards above and below the geometric mean when analyzing and reprocessing data, effectively weights the curve such that both the high and low ends of the curve are given equivalent significance. 4.0 Warnings and Cautions_____________________________________________________ 4.1 Health and safety warnings 4.1.1 Wear the proper lab attire for all parts of this procedure. Wear gloves and proper eyewear when performing sample preparation in the laboratory at all times. Wear proper eyewear when working at the instrument in the laboratory. ETS-8-181.0 Analysis o f Photolysis Samples for Fluorochemicals by HPLC/MS Page 5 o f 15 Page 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. 4.1.3 For potential hazards of each chemical used, refer to material safety data sheets, packing materials, and the 3M Environmental Laboratory Chemical Hazard Review. 4.2 Cautions 4.2.1 All glassware in which standards are prepared should be rinsed with acetone and methanol to reduce the possibility of contamination. 4.2.2 Ensure that the HPLC mobile phases are prepared prior to beginning a run sequence, and that there is sufficient quantity to complete the run. Do not allow the pump to run dry. 4.23 Ensure that before starting the run sequence there is ample hard disk space on the computer to save all run data. 4.2.4 Ensure that there is enough nitrogen in the supply tank to complete sequence runs. 5.0 Interference________________________________________________________________ 5.1 Contaminants in solvents, reagents, glassware, and other sample processing or analysis hardware may cause interference. Use the routine analysis of laboratory method blanks to demonstrate that there is no such interference. 5.2 Contamination from columns, HPLC tubing, and detector components may cause interference at low detection levels. The routine analysis of solvent blanks must be used to demonstrate that there is no such interference. 6.0 Equipment_________________________ ._________________________________________ 6.1 Analytical balance sensitive to 0.1 mg. 6.2 Hewlett-Packard (HP) 1100 HPLC System, or equivalent. 6.2.1 Pump, binary, Model G1312; Quaternary, Model G1311A; or equivalent. 6.2.2 Solvent degasser, Model G l322A or equivalent. 6.2.3 Autosampler, ALS Model G l 313A, variable injection volume or equivalent. 6.2.4 Column heater, Model G1316A, or equivalent. 6.3 Betasil C 18,50 x 2 mm; Dionex IonPac NG1 Guard column, 4 x 35 mm; or equivalent. 6.4 Mass spectrometer. Hewlett-Packard MSD Model G1946A, or equivalent. 6.5 Refrigerator capable of maintaining 4 3 C. 6.6 Data system. A personal computer capable of controlling the HPLC system as well as recording and processing signals from the detector. ETS-8-181.0 Analysis o f Photolysis Samples for Fluorochemicals by HPLC/MS Page 6 o f 15 Page 30 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 6.7 System control/data analysis software: Hewlett Packard ChemStation, Version A.6.03 or later. 6.8 Data reprocessing software: Thru-Put Systems Target NT, Revision 4.03, Build 157 or later. Hewlett Packard ChemStation, Version A.6.03 or later. 7.0 Supplies and materials___________________________________________________ __ 7.1 Vials, 40 mL, VOA (I-Chem or equivalent) 7.2 Crimp cap autovials, 1.8 mL 7.3 Labels 7.4 Graduated pipets, glass, disposable, 1 mL to 10 mL 7.5 Pasteur pipets, glass, disposable 7.6 Hamilton Gastight syringes (precision 1% of total volume), 10 p L -1000 pL 7.7 Volumetric flasks, various sizes 7.8 Beakers, glass, various sizes 7.9 Automatic pipettor, capable of dispensing 10-5000 pL 8.0 Reagents and Standards____________________________________________________ 8.1 Methanol (MeOH). HPLC/SPEC/GC grade from EM Science, or equivalent 8.2 Acetone. HPLC/SPEC/GC grade from EM Science, or equivalent 8.3 ASTM Type II Water. Water with lower resistance must not be used. 8.4 Ammonium acetate, 2 mM in water. This solution is chromatographic solvent A (see Section 12.2.1). (Example: An acceptable eluent solution is made by adding 0.15 g ammonium acetate crystals to a 1-L volumetric flask containing about 500 mL water, adding 10 mL of methanol, diluting to the mark with 18.0 M il water and mixing.) 8.5 Stock, internal standard, surrogate, post-photolysis spike and calibration solutions All weights should be recorded to the nearest 0.0001 g in a standards preparation log: 8.5.1 Fluorochemical or target analyte prepared in acetonitrile (or suitable analytical solvent). (Example: A stock solution is prepared at a concentration of approximately 30,000 pg/mL by weighing 0.3 g of target analyte in a 10-mL volumetric flask and bringing to the mark with suitable analytical solvent. This solution is diluted in solvent to make additional, appropriate standards. Follow specified guidelines for documenting removal of test analyte and target analyte(s), use of balance, preparation of diluted solutions and calibration standards in the appropriate log books. Maintain photocopies of the preparation pages and worksheets in a raw data file. ETS-8-181.0 Analysis o f Photolysis Samples for Fluorochemicals by HPLC/MS Page 7 o f 15 Page 31 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 9.0 Sample Handling__________________________________' _______________ 9.1 Standards and diluted samples are stored in capped autovials or capped 40 mL VOA vials until analysis. 9.2 If analysis will be delayed, standards and sample extracts may be stored at 4 C 3 C or room temperature, until analysis can be performed. Document storage conditions on sample prep worksheet with date and initials. 10.0 Quality Control________________________________________ ___________________ 10.1 Calibration Standards. Calibration standards (Section 11) used to generate a calibration curve should be prepared in the same type of solvent or matrix as in the study samples. The number o f calibration standards and the concentration levels should be sufficient to encompass the expected concentrations of the study samples. In general, a m inim um of five calibration standards is required for fit o f linear regression. Broad calibration ranges (greater than three Orders of magnitude between low and high standards), may require use o f a quadratic fit o f 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 o f every fifteen samples. 10.3 Solvent blank. Solvent blanks are run before and after every calibration curve, CCV, matrix and control blank (if contamination is noted), and after batches o f no more than 30 injections. Acceptable values for the blanks are values below 25% o f the limit of quantitation (LOQ) of the instrument. If analyte carryover is a problem, use back-to-back solvent blanks. 10.4 Sample Triplicates. Analyze all sets of triplicate samples to provide a measure of the precision of analysis. Study samples will be analyzed in batches of no more than 30 samples. Multiple batches in an analytical sequence will be bracketed by calibration standards at the beginning and end o f each study sample batch. All samples (matrix and control samples, blanks and spikes) from a 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 recovery efficiency. Concentrations of the spike should be approximately equal to a mid-range calibration standard. The matrix spike sample should be analyzed periodically to measure the precision associated with the analysis. The analyst shall accept percent spike recoveries o f 100 25%. Spike recoveries outside o f this range should be noted and used with other criteria to evaluate the condition of the analytical run or necessity for repeat analysis. Consult with the Team Leader or designee for direction and final acceptance or rejection of the analytical run. Samples may be spiked at two different concentrations to ensure that the resulting levels o f target analyte(s) are within the viable range of the calibration curve. ETS-8-181.0 Analysis o f Photolysis Samples for Fluorochemicals by HPLC/MS Page 8 o f 15 Page 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 from the plot of all individual calibration points, including but not forced through zero, using HP ChemStation or Target NT Software. A minimum of five calibration standards is required to generate linear regression for target analyte(s). If the calibration curve residuals are greater than 25% deviation from the theoretical value, quadratic curve fitting and/or dropping low/high curve points may be required if data review shows this to be a consistent and more accurate representation o f the instrument response. Document in the raw data the technical justification for any deviation and consult with the team leader or designee for direction and for final acceptance or rejection of the data. 11.1.1 Use the following documentation/footnotes maybe used to justify dropping high/low curve points. 1) "High/low calibration points (list points) were excluded to provide a better fit over the linear range appropriate to the measured data." 2) "Low level calibration point(s) were not 4x higher than the extraction blank; these points were excluded from the curve to disqualify a data range that may have been significantly affected by background levels of the analyte." 3) "High/low calibration point(s) (list points) were excluded as they were not within the +/-25% accuracy requirements of the method when the curves were evaluated over a linear range appropriate to the data.' 11.2 If the curve does not meet requirements perform routine maintenance or prepare a new standard curve (if necessary) and reanalyze. 12.0 Procedures___________________________________________________________ 12.1 Instrum ent set up. Within "Method and Run Control" in the HP ChemStation Software window, turn the system "on" to: turn on the drying gas flow; initiate solvent flow through the column and nebulizing needle; equilibrate the column compartment; and equilibrate the MSD spray chamber temperatures and conditions. The system module displays should turn a green color to indicate the instrument is "ready" for analysis. A yellow color indicates that the system is not ready, but is working to "get ready." A red colored module icon indicates a type of systematic failure and should be corrected prior to proceeding. Check the run log for error messages and error codes if the problem is not apparent. 12.2 MSD set-up. Turn the MSD "on" in the software to equilibrate the system. 12.2.1 Check the level 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 o f Photolysis Samples for Fluorochemicals by HPLC/MS Page 9 o f 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 qualification and performance verification of the MSD. Log the Tune results and keep a copy with the analytical raw data. 12.2.4 Load the method file and ensure that the following parameters are appropriately set for the target analyte(s): Example mass spectrometer set up*: MSD: Ionization mode APt-ES (or API-APCI) Polarity Negative (or Positive) Acquisition mode SIM (or SCAN) Gain 1.0 (up to 7.0) Fragmenter 70 (may be set to one voltage, or ramped for each ion) Dwell time 183 msec (time Is a function of the amount of Ions). Capillary voltage 3500, or equivalent Drying gas Nitrogen, or equivalent Nebulizer pressure 30 psig, or equivalent Drying gas flow 8 L/min, or equivalent Drying gas temp 300 C, or equivalent ExampleconditionsareapplicabletoHPl100LC/MSDequipmentonly. 12.3 LC Check 12.3.1 Check that the appropriate HPLC column is in the instrument for analysis. 12.3.2 Check that the correct eluent solutions are in bottles to be used and that enough is available to complete the sequence run. Adjust the solvent bottle level electronically within the method and run control window. 12.3.3 Ensure that the method file has the appropriate LC pump parameters for solvent flow/gradient program, column LD/temperature, injection volume and stop time. Solvent A: Ammonium Acetate 2mM in water (with 1% MeOH) (or equivalent). Solvent B: Methanol (or equivalent). Example Solvent Gradient: T ime (min) %A %B Flow Rate 0.0 60 40 0.3 mL/min 1.0 60 40 0.3 mL/min 4.0 5 95 0.3 mL/min 11.0 5 Posttime: 6minutes, columntemperature: 3SC. 95 0.3 mL/min The initial solvent composition is set to a higher amount of aqueous solvent so as to achieve sufficient sample retention on the column. The gradient composition ETS-8-181.0 Analysis o f Photolysis Samples for Fluorochemicals by HPLC/MS Page 10 o f 15 Page 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 fashion. After all analytes have eluted, the solvent ratio is then switched back to "initial conditions" and held until the column pressure has stabilized ( indicating re-equilibration to initial conditions) prior to the next injection. 12.3.4 Auto-sampler setup: A uto-sam pler: ALS Model G1313A A uto-sam pler Program: None In j e c t io n v o l u m e : 5.0 pL, or equivalent * Exam ple conditions are applicable to Hew lett Packard 1100 LC/MSD only 12.3.5 Place the samples in the autosampler tray and construct a sequence table with appropriate calibration standards, calibration check standards and solvent blanks. 12.3.5.1 Verify that all samples and standards are positioned correctly. 12.3.5.2 Enter the identification code for each standard and samples. For solvent blanks, identify the solvent and the traceability number. 12.3.5.3 Use one injection per sample. 12.3.5.4 Ensure the method file is correctly entered for all samples. 12.4 Sequence and electronic storage of data files. 12.4.1 Within the sequence parameters, enter sequence information (brief sample population description and instrument name). 12.4.2 Set post-sequence command macro to shut down system after the run is completed (Example: "STANDBY" on HP1100/MSD systems). 12.4.3 Save all data to a subdirectory labeled with instrument and analysis date (e.g. H100200 for analysis on "Hillary," on 2 October, 2000). 12.4.4 Name data within the subdirectory with instrument ID and injection/run number (e.g. for samples acquired on "Hillary", data files shall be "HILL0001".... "HILL00##"). DO NOT exceed five identification characters for analysis o f more than 99 samples since eight characters total are available for sample ID, and the last three digits are for sample numbering purposes (leaving the first five characters for data file identification). 12.4.5 Save sequence as analysis date and instrument letter (e.g. For analysis on instrument "Hillary" on October 2,2000 save sequence table as H100200.S). 12.5 Sample analysis 12.5.1 Enter the standard, sample, blank identification into the sequence table. Analyze calibration standards first, then up to 30 injections, followed by the calibration standards re-injected. Multiple sets o f samples can be set up in the sequence table with each set bracketed by calibration standards. Analyze a single continuing calibration standard (CCV) after a maximum of 15 injections. Solvent blanks shall be analyzed before and after the CCV and before method and control blanks, if ETS-8-181.0 Analysis o f Photolysis Samples for Fluorochemicals by HPLC/MS Page 11 o f 15 Page 35 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 necessary. Two solvent blanks shall be analyzed at the end o f the calibration standards to ensure that there is no cany over from the highest standard concentration. Solvent blanks may also be used to separate groups o f samples and evaluate for carry over problems from actual samples. Ensure standards, blanks, samples, and matrix spikes in the auto-sampler tray vials are in same order as listed in the sequence. 12.5.2 Print a copy of the tune results, method and sequence to be stored with raw data. 12.53 Start the sequence. 12.6 Post Analysis. Prepare a folder identified specifically to the project and save data, method and sequence files. This will be considered the raw electronic data to be archived. 13.0 Data Analysis and Calculations_________ ;_______________________________ 13.1 Peak Evaluation. Peaks must be symmetric in shape and identified by extracting compound-specific ions. Peaks considered for quantification must have peak heights greater than 4 times any baseline level for that region of the chromatogram. Peak area integration is from baseline to baseline using automatic or manual integration. Manual integration is not acceptable for calibration standards and should only be used in extreme cases as designated by the Team Leader. Samples and standards that may need to be manually integrated must be documented in the raw data as to why the peak was manually integrated. 13.2 Integration Codes. The following integration codes may be utilized to document what type o f manual integration was performed. A: Adjust Left Anchor B: Adjust Right Anchor C: Delete Integration D: Add Integration Additionally, QAU encourages th data reviewer to write comments directly on the chromatogram if there is anything unusual. Date and initial all documentation. 13.3 M atrix spikes. Calculate the percent recovery for each of the matrix spikes. Calculate the matrix spike percent recoveries using the following equation: % Recovery = (observed spiked sample result - observed sample result! x 100 Nominal amount spiked Using the observed matrix spike recoveries, calculate the average spike recovery. 13.4 Accuracy. Calculate the accuracy o f each calculated calibration standard and CCV samples using the following equation. Accuracy =>(Measured Conc.1 x 100 Nominal Cone. ETS-8-181.0 Analysis o f Photolysis Samples for Fluorochemicals by HPLC/MS P ag e 12 o f 15 Page 36 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 13.5 Sample Triplicates. Calculate the relative standard deviation (%RSD) for the triplicate samples: RSD = Standard Deviation of Sample Set x 100 Average o f Sample Set 14.0 Method Performance________________________________________ _ 14.1 Coefficient of Determination (r2). The coefficient of determination (r2) for the calibration curves should be 0.990 or greater. The curves should be examined closely for linearity and intercept, particularly for accuracy o f quantitation at the low and high ends o f the curve. The accuracy of all standards used for calibration must be within 75-125%. It may be necessary to use quadratic fits of the data, usually when broad range curves (greater than 3 orders of magnitude between the low and high concentration standards) are used. Document in the raw data the technical justification for using quadratic equations. Consult with the Team Leader or designee for direction and for final acceptance or rejection for the data. 14.2 Calibration Standards. The acceptance criterion for the calibration standards is that the accuracy of each standard is 75% to 125% ( 25 % difference) of the nominal value. Calibration standards outside this range are to be noted. Document in the raw data the technical justification for deviations. Consult with the Team Leader or designee for direction and for final acceptance or rejection for the data. 14.3 Internal Standard (IS) and Surrogate. Review of the internal standard and surrogate performance is performed by averaging the area response throughout the analytical run and calculating %RSD. Inconsistencies in the internal standard peak area may indicate instrumental changes over time. Inconsistencies in the surrogate peak area may indicate instrumental changes, injection error, or changes in the test-system. Consult with the Team Leader or designee for direction and final acceptance or rejection of the analytical run. 14.4 Continuing Calibration Verification. If the accuracy for the amount o f measured analyte is greater than 25% from the nominal value relative to the initial standard curve, the Team Leader should be consulted. Only those samples analyzed before the last acceptable calibration check standard may be used. Consult with the Team Leader or designee for direction and for final acceptance or rejection for the data. 14.5 Solvent Blanks. Solvent blanks should show no more than a 5% carryover from a high standard or calibration check standard. If so, two solvent blanks may be necessary to rule out instrumental contamination. If peaks greater than 25% o f the peak area o f the designated LOQ value are observed in sequential solvent blanks, this is indicative o f instrument contamination. The instrument shall be serviced by thoroughly cleaning the electrospray source, and replacing/cleaning columns, tubing, etc. (as designated in the Equipment Procedure, ETS-9-34.0) and the analysis restarted. Consult with the Team Leader or designee for direction and final acceptance or rejection of the analytical run. 14.6 M atrix Blanks. Matrix blanks are the basis for determining the LOQ and are monitored at various times in the analytical run. Samples with greater than 25% of the peak area of the designated LOQ value observed in matrix blanks are indicative of matrix effect, ETS-8-181.0 Analysis o f Photolysis Samples for Fluorochemicals by HPLC/MS Page 13 o f 15 Page 37 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 sample contamination or instrument contamination. Evaluation o f the solvent and control blanks may be necessary to determine these effects. Use of solvent blanks prior to the matrix blank may be necessary to rule out instrumental or sample contamination. 14.7 Control Blanks. Control blanks are the basis for determining matrix effect (interference or suppression) and also to monitor for instrumental or sample contamination. Use o f solvent blanks prior to the matrix blank may be necessary to rule out instrumental or sample contamination. 14.8 Lim it of Quantitation (LOQ). The LOQ is equal to the lowest acceptable standard (i.e. % accuracy is < 25 % nominal value) in the calibration curve that is greater than 4 times the level of the matrix blanks. 14.9 Sample Triplicates. The analyst shall accept %RSD values < 25%. %RSD values > 25% should be noted. Data used in the final report that is deemed out of control will be required to have technical justification for why the data is used, documented in the final report and raw data. Consult with the Team Leader or designee for direction, and for final acceptance or rejection of the data. 14.10 Control Samples. The acceptance criterion for the control samples is that the accuracy is 75% to 125% o f the nominal value. These will be used as a reference for matrix effect and overall method performance. Control samples outside this range are to be noted. Consult with the Team Leader or designee for direction and for final acceptance or rejection for the data. Data used in final report that is deemed out of control will be required to have a technical justification for why the data are being used, documented in the final report and raw data. 14.11 Analytical Spikes. The analyst shall accept percent spike recovery values of 100 25%. Spike recoveries outside o f this range should be noted. Consult with the Team Leader or designee for direction, and for final acceptance or rejection of the data. Data used in final report that is deemed out o f control will be required to have a technical justification for why the data are being used, documented in the final report and raw data. 14.12 System Suitability. Without performing a method validation, system suitability can be demonstrated by acceptable instrumental checks (e.g. abbreviated m /z check-tune, or full auto-tune routines. Consult the appropriate instrumental manuals (Reference 18.2). Furthermore, overlaying calibration curves and implementing check standards (CCV), the method shall be self-validating if all data quality objectives are satisfied. 15.0 Pollution Prevention and Waste Management___________________________ 15.1 Dispose of sample waste by placing in high or low BTU containers as appropriate. Use broken glass containers to dispose of glass pipettes. 15.2 Collect HPLC solvent waste in the satellite accumulation can. Empty into the flammable storage drum in the hazardous waste collection area on the 2nd floor. 15.3 Use smaller bore columns when possible to minimize waste generation. ETS-8-181.0 Analysis o f Photolysis Samples for Fluorochemicals by HPLC/MS P ag e 14 o f 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 with instrument ID. 16.3 Fill out appropriate preparation worksheets completely, making sure to include all initials and dates, along with the study number and sample identification. 16.4 Print out the sample acquisition sequence table, reduce the size with photocopying and tape the photocopy into the instrument log. Keep the original copy for the raw data files. 16.5 Print chromatograms, reprocessing sequence and batch reports for all analyses. 16.6 Print calibration tables and curve information and store in the raw data file. 16.7 Enter all standard preparation information in the standards preparation logbook. Make a photocopy o f the logbook page and include the copy in the raw data file. 16.8 Archive electronic data to appropriate media when necessary. 17.0 Attachments_________________________________________________________ 17.1 None. 18.0 References___________________________________________________________ 18.1 ETS-9-34.0, Hewlett Packard 1100/MSD Equipment Procedure. 18.2 Hewlett Packard 1100/MSD instruction CD/ROM. 19.0 Affected Documents__________________________________________________ 19.1 None. 20.0 Revisions____________________________________________________________ Revision number Reason for revision Date of Revision ETS-8-181.0 Analysis o f Photolysis Samples for Fluorochemicals by HPLC/MS Page 15 o f 15 Page 39 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 3M Environmental Laboratory Method Preparation of Samples for Photolytic Exposure Studies in Aqueous Matrices Method Number: ETS-8-176.0 Adoption Date: Approved By: Exact CopV -- \n& a* D ate -- ETS-8-176.QPreparation o f Sam ples f o r P hotolysis Studies in Aqueous M atrices Method Page 1 o f i 8 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 1.0 Scope and Application 1.1 Purpose. Chemicals dissolved in aqueous solutions are subject to two types of photoreaction. The first type (direct photolysis) occurs when the chemical of interest absorbs sunlight directly and is transformed to products when unstable, excited states of the molecule lead to decomposition. The second type is indirect photolysis, where degradation of the dissolved chemical is the result of chemical or electronic excitation transfer from light-absorbing species in the water. The simplest reaction involves the absorption o f UV energy by hydrogen peroxide (H2O2) to produce 2 hydroxl radicals. These may react with any species in the water, including solvent, buffer, dissolved organic material and target material. Use of water and H2O2 is very controlled and predictable. Other sources in other matrices are not as controlled or predicable, but are more environmentally relevant. Natural waters such as lake and sea water can be used for the photolytic reaction matrix because it may contain dissolved organic material that absorbs sunlight and produces reactive intermediates that include singlet oxygen (10 2) which may promote indirect photolysis o f the test substance. Another transient species photochemically produced by the reaction of UV light and dissolved organic materials (humic) is hydrogen peroxide (H2 O2) which may react further to form the hydroxyl radical. The addition of H2O2 to test solutions may be utilized as a free radicad source to initiate indirect photolytic reactions in controlled test solutions such as MilliQ water or buffers. Further studies involving the use of either naturally occurring metal complexes such as Fe(III) which undergo photoreduction to Fe(II) and free radicals or addition o f TO2 as a catalytic surface for indirect photolysis may also be evaluated within this method. 1.2 Compatible analytes. Test substance and degradation products for photolytic exposure include but are not limited to: C om pound A cronym Compound A cronym Perfluorooctanoic acid Perfluorooctanesulfonate PFOA PFOS Perfluorobutanoic acid Perfluorobutanesulfonate PFBA PFBS P erfluoiooctanesulfonam ide FOSA P erfluorobutanesulfonam ide FBSA N-m ethylperfluorooctanesulfonam ide N-M eFOSA N -m ethylperfluorobutanesulfonam ide N-M eFBSA N -ethylperfluorooctanesulfonam ide N -E tF O S A N -ethylp erflu o ro b u tan esu lfo n am id e N -E tF B S A 2-(N -m ethylperfluoro octanesulfonam ido) ethyl alcohol N-MeFOSE-OH 2-(N-methylperfluorobutanesulfonamido) ethyl N -M eFB SE- alcohol OH 2-(N-ethyiperfluorooctanesulfonam ido) N-EtFOSE-OH ethyl alcohol 2 -(N -ethylperfluorobutanesulfonam ido)ethyl alcohol N -E tF B S E -O H 1-perfluorooctene -- 1-perfluorobutene Perfluorooctanehydride 1H, Cs-hydrlde Perfluorobutanehydride 1H, C^-hydtide ... an d o th er C4 th ru C 10 hom ologues, and polym eric m aterials b ased on th e aforem entioned com pounds. ETS-8-176.0P rep a ra tio n o f Sam ples f a r P h otolysis Studies in A queous M a trices Method Page 2 o f 18 Page 41 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 Other possible degradation products include, but are not limited to: C: IH-perfluoroethane(!H-pfC2) lH-ptrfluoroethane(lH-piC2) c3 1H-perfluoropropane(lH-pfC3) 2H-perfluotopropane(2H-pfC3) perfluoro-1-propene(plC3-lene) perfluoro-l-butene(pfC4-lene) Perfluoro-2-butene(pfC4-2ene) 2H-perfluorobutane(2H-pfC4) 1H-perfluorobutane(1H-pJC4) C5 2H-perfluororpentane(2H-pfCS) perfluoro-l-pentene(pfC5-lene) perfIuoro-2-penienc(pfC5-2ene) ce perfluoro-2-hexene(pfC6-2ene) lH-perfluorohexane(lH-pfC6) perfluoro-1-hexene(pfC6-1ene) IH-perfluorohexane(IH-pfC6) 2H-perfluorohexene(2H-pfC6) C7 2H-perfluoroheptane(2H-pfC5) Periluoro-l-heptene(pfC7-lene) lH-perfluoroheptane(lH-pfC7) C perfluoro-l-octene(piC8-lene) 2H-perfluorooctane(2H-pO) Perfluoro-2-octene(pfC8-2ene) lH-perfluorooctanc(IH-piC8) 1.3 Acceptable matrices. Aqueous solution of test substance including but not limited to the following matrices: pH 7 phosphate buffer, 18.2 MCI resistivity water, seawater and metal solutions. 2.0 Summary of Method 2il The objective of the photolytic exposure study is to determine whether the test substance undergoes degradation by either direct or indirect photolysis, and to identify and quantify degradation products formed in the test matrix under these conditions. Study samples (5 mL aqueous matrix) are prepared in 40 mL glass VOA vials equipped with screw-top caps with septa. Study sets are prepared in duplicate for separate analysis by LC/MS and dynamic purge and trap GC/MS. When required, the addition of 30% H2O2 solution to initiate radical formation is performed prior to the photolytic exposure and at specified intervals throughout the exposure study. Vials are placed in the photo-reactor and immersed in a water bath controlled at 23-26 C. Samples are exposed to approximately 261 W/m2o f 310-800 nm photo-irradiance for a specified number of 8-hour periods. An 8-hour period of irradiance is defined as one day's worth of sunlight. Other parameters are acceptable, with the time and settings noted for each study. The number o f days to expose samples is determined by the Team Leader. The amount of irradiation received by the samples may be monitored in one o f the following three ways: 1) calculating the total wattage per length of exposure 2) use o f a radiometer to measure irradiance output, and/or 3) use of a quinine monohydrochloride dihydrate (QMD) actinometer solution exposed along with the samples and monitored for change in UV absorption over time. The use of the radiometer provides an accurate measurement at specified time-points; whereas calculating the total wattage per exposure length and use o f the QMD actinometer provide time-averaged total integrated energies. Suntest instruments contain an internal radiometer for maintenance of constant irradiance. A second radiometer may be used as a check for consistency. At the end of the exposure time, samples are removed from the photoreactor and either subsequently analyzed or stored at 1-5 C. Study samples to be analyzed by LC/MS are prepared for analysis by diluting the 5 mL sample volume with 30 mL of suitable analytical solvent (e.g. methanol) containing internal standard. The GC/MS study samples are stored inverted prior to purge and trap GC/MS analysis. ETS-8-176.0Preporaiion o f S am ples f o r P h o to lysis S tu dies in A queous M atrices Method Page 3 o f 18 Page 42 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 2.2 An example of samples to be prepared for each study is shown in the table below. Exact lists may vary, dependent upon the test specifics for each study and will be noted in individual study reports. Typically, there are extra control samples for certain matrices such as FezO}. Description Test Matrix SampleRep1 SampleRep2 SampleRep3 SampleSpike MatrixBlank MatrixBlankSpike ControlSample ControlSpike ControlBlank ControlBlankSpike + + + + + + 0 0 0 0 Control Test Matrix Substance 0+ 0 0+ 0+ 00 00 + + ++ + + 0 0 PostPhotolysis TargetAnalyte spike 0 0 0 + +0 +0 +0 Sample Type TimeO Time0 Time0 TTiimmeeOO Time0 Time0 TimeO TimeO TimeO LC/MS With Without H2Oj H,Oj XX X X XX XX X X XX X X X X X X XX GC/MS With HaO, WHit2h0o2ut XX XX XX XX XX XX XX XX XX X x1 SampleRep1 SampleRep2 SampleRep3 SampleSpike MatrixBlank CMoantrtrixolBSlaamnkplSepike ControlSpike ControlBlank ControlBlankSpike + + + + + + 0 0 0 0 0 0 0 0 0 0 + + + + + + 0 0 + + 0 0 0 0 0 + 0 Exposed Exposed Exposed Exposed Exposed X X X X X xX 11 X X XX XX XX X XX X X + 0 EExxppoosseedd X X XX X X XX + Exposed X X X X 0 + EExxppoosseedd X X XX XX X X SampleRep1 SampleRep2 SampleRep3 SampleSpike MatrixBlank MatrixBlankSpike ControlSample ControlSpike Control Blank ControlBlankSpike + + + + + + 0 0 0 0 0 0 0 0 0 +0 + + + + + + + 0 +0 + 0 0 0 Unexposed X X 1 X X 0 Unexposed X X X X 0 Unexposed X X X X + Unexposed X X X X 0 Unexposed X X X X + Unexposed X X X X 0 Unexposed X X X X + Unexposed X X X X 0+ Unexposed X X X X Unexposed X x 1 X X + = added to test vial; 0 = NOT added to test vial; X = One set W/H2O2, One set w/o H2O2 3.0 Quality Control-Definition/Frequency/Performance Criteria _ _ Q]anlcg ' 3.1.1 D efin ition : M atrix Blank. An analyte-free matrix to which all reagents are added in the same volumes or proportions as used in the sample processing. For photolysis studies, there are multiple matrix blanks to adequately represent the variables within the study in reference to the matrix (e.g. Exposed, Unexposed, Time 0; with peroxide, without peroxide). The matrix blanks are carried through the complete sample preparation, experimental treatment and analytical procedure. The matrix blank is used to document contamination resulting from the experimental treatment and analytical process. Refer to the table below for an example of matrix blank types. The matrix blank is used to document the actual test system without the test substance. The control blank is used to control the test matrix and trace any background levels o f target analyte that may be matrixspecific. The table below shows an example of a control blank ETS-8-116.0 P rep a ra tio n o fS a m p le s f o r P h o to lysis Stu dies in A queous M atrices Method Page 4 o f 18 Page 43 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 3.1.2 P erform an ce C riteria: The frequency of use and the performance specifications for each of the above defined method blank types shall be as follows: Matrix ID Matrix Blank Control Blank Matrix descrintion Example: 0.01 M Phosphate Buffer, pH 7 Example: ASTM Type II Water Freauencv 1 Replicate per light and dark exposure, for each time point and for each analytical methodology. Performance Criteria Any background level of target analyte shall be less than 25% the area counts of the LOQ. 3.2 Limit of Quantitation (LOQ) 3.2.1 Definition: The lowest concentration that can be reliably measured within specified limits of accuracy during routine laboratory operating conditions. Sample LOQs are highly matrix-dependent. 3.2.2 Q u a lity C o n tro l a n d P erform an ce C riteria : The LOQ is generally 5 to 10 times the minimum concentration with a 99% confidence limit that the concentration is greater than zero. However, it may be nominally chosen within these guidelines to simplify data reporting. For many analytes, the LOQ is selected as the lowest non-zero standard in the calibration curve that is greater than 4 times the level of the solvent blanks and indicates good accuracy ( 25%) o f the nominal calibration standard concentration. 3.3 Sample Triplicate 3.3.1 D efin itio n : Three aliquots prepared as representatives of the same sample source (i.e. test substance) and carried through all steps o f the photolytic study process and analytical procedures in an identical manner. The results from triplicate analyses are used to evaluate variability o f the total method, including sample preparation, photolytic process and analysis. 3.3.2 P erfo rm a n ce C riteria : The samples in die test matrix will be prepared in triplicate. Each replicate will be prepared for each treatment type: light and dark exposures, with and without hydrogen peroxide, for EACH time-point, and for each analytical methodology (e.g. LC/MS and/or GC/MS). See the following table: M atrix Descrintion Freauencv of Use Performance Criteria Test Matrix containing test analyte(s) 3 Replicates per light AND dark exposure, with AND without H20 2, for each time-point, and for each analytical methodology (i.e. LC/MS and/or GC/MS). The analyst shall accept %RSD <25%. Precision values not meeting specification must be documented and justified (if possible). 3.4 Control Sample 3.4.1 D efin itio n : A known matrix containing the test analyte(s) carried throughout the entire analytical procedure. This is used to document laboratory performance (i.e. precision of sample preparation by comparing spike recoveries from the different matrices and sample types). A control sample consists of a control matrix spiked with test analyte(s). A control sample should be analyzed with each batch of samples processed to verify that the precision and bias of the analytical process ETS-8-176.0P rep a ra tio n o fS a m p les f o r P hotolysis Studies in A queous M atrices Method Page 5 o f 18 Page 44 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 3.4.2 are within control limits. The results of control sample analyses are compared to control limits established for both precision and bias to determine usability o f the data. P erfo rm a n ce C riteria. One control sample will be prepared per matrix, per treatment type. See the following table: Matrix Description Control matrix with test analyte(s) added Freauencv of Use 1 Replicate per light AND dark exposure, with AND without H20 2, for each time-point, and for each analytical methodology (i.e. LC/MS and/or GC/MS). Performance Criteria The analyst shall accept recovery values o f 100 25%. Accuracy values not meeting specification must be documented and justified (if possible). 3.5 Analytical Spike (AS) 3.5.1 D efin itio n : Prepared by adding a known mass of target analyte(s) to a specified amount o f a diluted and/or aliquoted sample. This assumes that an independent estimate of target analyte concentration is available. Analytical spikes are used to evaluate the recovery efficiency of the analyte and the effect o f the matrix on the measurements. 3.5.2 Quality Control and Performance Criteria; One sample spike will be prepared in the actual test matrix sample, and one control spike in the control matrix will be prepared. Each replicate will be prepared per treatment type: for light and dark exposures, with and without hydrogen peroxide, for each time-point, and for each analytical methodology (i.e. LC/MS and/or GC/MS). In addition, one matrix blank spike and one control blank spike will be prepared. See the following table: Matrix Description Test Matrix a n d te st substance, spiked with target analyte(s) just prior to analysis Control Matrix a n d test substance, spiked with target analyte(s) just prior to analysis Test Matrix w ithout test substance, spiked with target analyte(s)just prior to analysis Control Matrix w ithout test substance, spiked with target analyte(s) just prior to analysis Freouency of Use 1 Replicate per treatment type. 1 Replicate per treatment type. 1 Replicate per treatment type. 1 Replicate per treatment type. Performance Criteria The analyst shall accept spike recovery values of 100 25% . If spike recoveries are greater than 125% or less than 75%, document that the spike sample is out of the specifications and justify, if possible, the reason. 3.6 Internal Standard/Surrogate 3,6.1 In te rn a l S ta n d a rd D efin itio n (a p p lies to L C /M S a n d G C /M S sa m p le s): A known amount of a compound similar in analytical behavior to the target analyte(s) of interest, added to all samples and standards (post-irradiation), and carried through the entire analytical process. It provides a reference for evaluating and controlling the precision and bias of the applied analytical method. Samples are ETS-8-176.^P reparation o f S am ples f o r Photolysis Studies in Aqueous M atrices Method Page 6 o f 18 Page 45 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 3.6.2 to be quantified using the internal standard providing that the response of the internal standard is consistent ( 5% relative). Use o f external calibration methodology requires written justification by the Team Leader. S u rrogate D efin ition (applies to L C /M S a n d G C /M S sam ples): A known amount of a compound similar in analytical behavior to the target analyte(s) of interest may be added to all samples and standards (pre- or post-irradiation, at the discretion of the Team Leader) and carried through the remaining sample preparation and analytical process. If added before exposure, it monitors the presence of vial leaks during photolysis, as well as the performance of the purge and trap auto-sampler and concentrator. Surrogate analysis is used to evaluate and control the precision and bias of the analytical method. Surrogates are not used for quantitation. N o te: In tern a l sta n d a rd s are u sed in a ll experim ents. The use o f su rro g a te sta n d a rd s m ay or m ay n ot be used. 3.6.3 Quality Control and Performance Criteria: Matrix DescriDtion Freauencv of Use Performance Criteria Sample diluted with 30 mL of internal standard compound dissolved in a suitable analytical solvent Every LC/MS sample analyzed Sample with surrogate Every GC/MS compound spiked into it. sample analyzed The Coefficient of Variation, or %RSD shall be calculated for the area response o f all appropriate samples per analytical batch. The analyst shall accept %RSD values of <15%. The recovery and precision o f the surrogates should be 100 25% and <15%, respectively. Unacceptable values shall be documented and justified, if possible. 3.7 Other Definitions. 3.7.1 Test Analyte/Substance: Any substance (mixture or controlled compound) added or administered to the test system for the purpose of chemical analysis. 3.7.2 Degradation Produces): Secondary analytes of interest produced as a result o f chemical reactions during the photolysis and monitored (qualitatively or quantitatively) during the sample analysis procedure. 3.7.3 Target Analyte($): The analyte(s) singled out in the analytical phase o f the study is the target analyte. The target analyte may be identical to the test substance used in the experimental phase o f the study, a by-product or degradation product that is monitored (qualitatively or quantitatively) during the sample analysis procedure. 3.7.4 Test M atrix: The physical matrix in which the study will be conducted. Also referred to as the test system. 3.7.5 Control M atrix: A known physical matrix to be included with the study for comparison with the test matrix. 3.7.6 Relative Standard Deviation (RSD): A measure of relative precision for three or more sample replicates; defined as the sample standard deviation divided by the sample average and multiplied by 100. This is expressed as percent (%RSD). 3.7.7 Accuracy: The closeness of agreement between an experimentally determined value and an accepted reference value; defined as the measured value divided by the nominal value and multiplied by 100. ETS-8-176.0P rep a ra tio n o fS a m p le s f o r P h o to lysis S tu dies in Aqueous M atrices Method Page 7 o f 18 Page 46 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 4.0 Health and Safety Warnings -- _____ - --- 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 photoreactors are equipped with a continuous flow of cooling water, which poses a threat of electrocution during the handling of the photoreactor during irradiation sequences. To avoid possible injury, inspect die units frequently for water leakage and electrical outlets and wiring for wear and tear. Replace any worn parts immediately. 4.2.3 Wear dark protective eyewear when operating the reactor. Do not look directly at the activated lamp. Use caution when handling samples in the reactor; the interior walls of the reactor and exposed glass vials become extremely hot. 5.0 Interference 5TI Solvents, water and matrix components could interfere with detection thereby decreasing" sensitivity in the sample analysis. Care must be taken to prevent all possible contaminants by using fresh reagents, analytical grade solvents and clean glassware during the sample preparation processes. 6.0 Equipment 6 ll Analytical balance sensitive to 0.1 mg 6.2 Photoreactor. Suntest CPS+, XLS+, or equivalent, equipped with a xenon arc-lamp and capable of producing integrated irradiance values from 100-680 W/m2 over the wavelength range of 290-800 nm. Lamp output must be filtered to allow only 290-800 nm wavelengths. A flowing water bath with circulating pump is required. Consult the appropriate 3M SOP for instructions. 6.3 Water recirculating cooler capable of maintaining temperature at 25 C 5 C, from Poly Science, Model 1177-P or equivalent. 6.4 Agilent Technologies UV-visible Spectrophotometer, equipped with tungsten and deuterium lamps, Model 8453, or equivalent. Consult the appropriate 3M SOP for instructions. 6.4.1 Autosampler equipped with eight sample cell holders: Agilent Technologies Model G1120A, Thermostatted Cell Holder: Model 08451-60104, or equivalent. 6.4.1.1 1.0-cm path length quartz spectrophotometer cell from Hewlett Packard, or equivalent. 6.4.2 Long Path-Length Cell Holder, Hewlett Packard (# 89076C) or equivalent. ETS-8-1IS .Q P reparation o fS a m p le s f o r P h o to lysis S tu dies in A queous M atrices Method Page 8 o f 18 Page 47 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 6.4.2.1 10-cm path length quartz cell equipped with stopcocks, Hewlett Packard Part # 5061-3392, or equivalent. . 6.4.3 Data acquisition and analysis software, HP ChemStation for UV-Visible Spectroscopy, G1116AA, Rev. B.01.02, or later. 6.4.4 PC Computer capable of running appropriate analysis software to acquire and report data. 6.5 Centrifiige capable o f maintaining > 2000 rpm for 10 minutes at ambient temperature. 6 . 6 Radiometer (optional) capable of monitoring the energy from a xenon source from 290 to 480 nm over time. Model PMA2100, Version 1.16, Solar Light Company, Inc., or equivalent. Consult the appropriate 3M SOP for instructions. . 7.0 Supplies and 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 10 mL to 1000 mL. 7.8 Hamilton Gastight syringes (precision 1% of the total volume), 5 pL to 1000 pL. 7.9 10 mL Bottle-top dispenser, Calibrex, Model # 511, or equivalent. 7.10 Adjustable repeater pipette, Wheaton Step-pette 411, or equivalent, equipped with the appropriate volumetric range pipette tips. 7.11 Ziploc plastic bags, or equivalent. 8.0 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/GC and/or purge and trap grad from EM Science, or equivalent. 8.3 Aqueous Matrix, includes but is not limited to the following matrix types: 8.3.1 ASTM Type I water. Milli-Q or equivalent, with a measured resistivity >18.0 MQ-cm. 8.3.2 0.01 M pH 7.0 Phosphate Buffer. Example: Weigh 1.36 g KH2PO4 into a 2 L volumetric flask and dissolve into 1 L of Type I water. Add 600 mL of 0.1% NaOH. Adjust to pH 7.0 0.1% with 0.1% NaOH or dilute H2 SO4 and dilute to the mark with Type I water for a final cone, of 10 mM. 8.3.3 Lake Surface water. Collected from a known source, with known specifications for Dissolved Organic Carbon (DOC) and Total Organic Carbon (TOC). 8.3.4 Sea water. Collected from a known source, with known DOC and TOC specifications. 8.3.5 Aqueous metal solutions and slurries (e.g. TK>2, FezOj). Example: Dilute 0.015 g of Ti02 (Aldrich Chemical or equivalent) to 500 mL with Milli-Q water. 8.3.6 Aqueous solutions containing soil. Example: Prepare samples containing 0.7g o f characterized soil or sediment in 5 mL of Milli-Q water. ETS-8-176.^P reparation o f Sam ples f o r P h o to lysis S tu dies in A queous M atrices Method Page 9 o f 18 Page 48 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 8.4 Hydrogen Peroxide (H2O2). 30% aqueous solution from EM Science, or equivalent. 8.5 Potassium phosphate. Reagent grade from JT Baker or equivalent. 8.6 Stock Solutions 8.6.1 Stock solutions for the test analyte, target analytes, internal standard are prepared in an organic solvent (e.g. methanol, acetonitrile) at concentrations of approximately 10,000 pg/ml by weighting approximately O.lg o f the appropriate substance into a 10-mL volumetric flask and diluting to the mark with solvent. This solution is then diluted to make appropriate working solutions. 8.7 Test Analyte Solution: 8.7.1 Example for water soluble analvtefs'): Example: A 1 pg/mL test substance solution in the test matrix (Section 8.3) is prepared by diluting 0.050 mL of stock solution (Section 8.6.1) to 500 mL with test matrix. Aliquots (5 mL) of this solution will transferred to VOA vials for subsequent photolysis. 8.7.2 Example for poor water soluble analvtefsi or those with adsorption difficulties: Prepare a solution of the test substance in acetonitrile (Example: A 500 pg/mL test analyte solution is prepared by diluting 500 pi of stock solution (Section 8.6.1) into a 10 mL volumetric flask and diluting to mark with acetonitrile). Calculate the test analyte concentration such that the organic content in the test vial is no more than 1% of the total sample matrix volume. Example: A 1 pg/mL test analyte in the test matrix (Section 8.3) is prepared by injecting 10 pL of a 500 pg/mL test substance stock (Section 8.6.1) into a VOA vial containing 5 mL of the test matrix. *Acetonitrile is currently the preferred solvent to use when introducing the test substance to the test m atrix because it does not interfere. M ethanol is a ra dical scavenger, which canphotooxidize during the exposure and decrease the indirect photolysis ofth e intended test substance. Evidence o f this phenomenon (approxim ately 10% decrease in the concentrations o fthefin a l products) has been observed in a study here at 3M (EtFOSE-OHphotolysis in p H 7 buffer, w ith and withoutpresence ofMeOH). 8.8 Target Analyte(s) Spiking solution: Example: A spike solution of test analyte and target analyte(s) (e.g. projected degradation products) in methanol or acetonitrile is prepared by diluting 500 pL o f test analyte stock solution and 100 pL of target analyte(s) stock solution (Section 8.6.1) into 10 mL with MeOH. The final concentration is approximately 500 pg/mL test substance/100 pg/mL target analytes. Addition of 10 pL of this target analyte spiking solution into the 35-mL diluted sample volume will result in approximately 140 ng/ml and 30 ng/ml concentrations for the test analyte and target analyte(s), respectively.* *Pre-estimation o fthe degradation potential o fthe test analyte and subsequent degradation products is not always possible. I f possible, an analyticalpre screening ofrepresentative samples should beperform edfo r accurate spiking. General rule o f thumb has been that the test analyte spike amount be E T S -& -l7 6 .0 P rep a ra tio n o f S a m ples f o r P h o to lysis Studies in A queous M atrices Method Page 10 o f 18 Page 49 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 approxim ately 25%- 50% o fthe in itia l concentration. The target analyte(s) spike amount has been 10-100 ng/ml, depending on expected levels under specific conditions. M ore than one spike solution may be utilized to adequately represent the levels in the samples. Example: A test analyte that undergoes significant degradation during photolysis w ill require a low er spike concentration in the Exposed sample set due to less test analyte remaining. The D ay 0 and Unexposed sample sets, which have not degraded, may require higher test analyte spike concentrations. 8.9 Dilution Solution containing Internal Standard: The diluting solution shall contain internal standard at an area response level equivalent to approximately half the are response of the test analyte's high standard in the calibration curve. Enough dilution solution shall be prepared for use in all the study samples and in preparation o f the calibration curve samples. Example: Internal standard solution is prepared by diluting 100 pL of stock solution (Section 8.6.1) to 4.0 L with MeOH to a concentration o f 250 ng/mL. 8.10 Quinine monohydrochloride dihydrate (QMD). 90% from Aldrich Chemical. 8.11 QMD solution: A 2% (w/v) solution of quinine monohydrochloride dihydrate solution is prepared by weighing approximately 2.0 g into a weigh boat, transferring to a 100 mL . flask and diluting to volume with Milli-Q water. 9.0 Sample H andling____________________________________________________________ 9.1 Record times of initial preparation, reference numbers o f reagents used and the amounts, appropriate dates, times and initials on the photolysis sample preparation worksheet.. Record photolysis reactor used, radiometer ( if applicable), computer for data collection, photolysis start and end on the sample preparation sheet and in the photolysis reactor log books. Record times, dates and initials of sample treatment post-photolysis, reference numbers of reagents used, and storage conditions. 9.2 Upon addition of the test substance solution, invert the 40 mL VOA sample vials (cap side down) to prevent loss of any potential volatile target analytes during the rest o f the procedure. This is particularly important for the GC/MS samples. GC/MS samples may only be turned upright immediately before being loaded onto the purge and trap autosampler. The LC/MS samples may be turned upright after the photolysis process has been completed. The exception to this being the need to b riefly turn the samples upright fo r H 2O2 injection through the septa o fthe appropriate VOA sample vials a t specified time intervals (See Section 12.6 and Section 12.11.7). 9.3 The completed photolysis samples remain inverted and refrigerated at 1-5 C prior to analysis by LC/MS or sample purge and trap GC/MS. 9.4 Sample preparation prior to LC/MS analysis requires the addition o f 30 mL o f diluting solvent containing internal standard to the 5-mL photolysis samples. This is to ensure complete recovery of the target analytes from the glass VOA vial surface and to dilute the samples into a working analytical range. Day 0 study samples stored at 1-5 C during the time o f photolytic exposure are removed and prepared for analysis at the same time as the exposed and unexposed samples. ETS-8-17 6 .0 P rep a ra tio n o f S a m ples f o r P h otolysis S tu dies in A queous M atrices Method Page 11 o f 18 Page 50 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 10.0 Quality Control 10.1 Refer to the definitions section for the quality control specified for each respective sample type. 11.0 Calibration and Standardization___________________________________________ 11.1 The compounds of interest must be characterized according to laboratory specifications. 11.2 All equipment used, such as the analytical balance, radiometer, etc. should be calibrated prior to use (daily, weekly, etc.) as specified in the standard operating procedure(s). 11.3 All samples analyzed will be run against a standard curve containing varying amounts of target analytes, and a fixed amount of internal standard or surrogate compound. Refer to the appropriate LC/MS and GC/MS methodologies for further analytical information. 12.0 12.1 12.2 12.3 12.4 12.5 Procedure__________________________________________________________________ Obtain the absorbance spectra of the test compound in aqueous solution using a UVVisible Spectrophotometer (ETS-9-46.0). 12.1.1 Using a 10-cm quartz spectrophotometer cell, obtain a blank water absorbance reading over the range 290-800 nm to determine a background or baseline reading. 12.1.2 Aliquot a solution o f water containing test substance, at a concentration less than half the solubility limit, into a 10 cm quartz spectrophotometer cell and obtain an absorbance reading over the range 290-800 nm. A positive absorbance may indicate the potential of the analyte to undergo direct photolysis. Non-absorbing analytes would be more likely to undergo indirect photolysis as the potential degradation pathway. Obtain the appropriate number of clear and amber 40-mL glass vials with caps and cardboard boxes. Label the vial caps using a black permanent pen to distinctly identify samples. Paper labels will be applied post-hydrolysis as they don't stick in water. Prepare appropriate sample preparation worksheets and create labels for each sample to affix to the 40 mL VOA vials and the autovials for analysis after photolysis. The labels should include the study number, sample number, test compound, matrix, exposure type (exposed/ unexposed/ Day 0), date and initials of the analyst. Aliquot 5 mL of the following solutions into clear (for EXPOSED samples) and amber (for UNEXPOSED and DAY 0 samples) 40 mL glass VOA vials: 12.4.1 Matrix with test substance (sample reps 1,2,3, and sample spike). 12.4.2 Matrix without test substance (matrix blank and matrix blank spike). 12.4.3 Control matrix with test substance (control sample and control spike). 12.4.4 Control matrix without test substance (control blank and control blank spike). ( When appropriate, test substance may be added after 5mL aliquots o fm atrix have been added to the vials. See Section 8.7) All exposed, unexposed, and day 0 samples will contain sample sets with and without peroxide and prepared for LC/MS and GC/MS analyses according to the following table: ETS-8-176.O Preparation o f Sam ples f o r P h otolysis Stu dies in A queous M a trices Method Page 12 o f 18 Page 51 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 Sample Treatment/Type Matrix with test substance Matrix without test substance Control matrix with test substance # of Samples 6 +H20 2 (3LC/MS.3GC/MS) 6 -H20 2 (3LC/MS ,3GC/MS) 2 +H20 2(1LC/MS.1GC/MS) 2 -H 20 2 (ULC/MS.1GC/MS) 2 +H20 2(1LC/MS, 1GC/MS) 2 -H 20 2 (11LC/MS, 1GC/MS) # of Spikes 2 +H20 2(1LC/MS, 1GC/MS) 2 -H20 2 (1LC/MS, 1GC/MS) 2 +H20 2(1LC/MS.1GC/MS) 2 -H20 2 (1LC/MS, 1GC/MS) 2 +H20 2(1LC/MS, 1GC/MS) 2 -H 20 2 (11LC/MS, 1GC/MS) Control matrix without test substance 2 +H20 2(1LC/MS,1GC/MS) 2 -H 20 2 (11LC/MS, 1GC/MS) EXPOSED, UNEXPOSED, & DAY 0 24 x 3 per exp type = 72 Total Samples per compound per study = 120 (60 for LC/MS, 60 for GC/MS) 2 +H20 2(1LC/MS.1GC/MS) 2 --H20 2 (11LC/MS.1GC/MS) 16x3=48 12.6 Separate the vials into three boxes labeled "Day 0," "Exposed," and "Unexposed." Initial addition of peroxide (Section 8.4) is done at this time by removing the cap and injecting the appropriate amount (e.g. 1 0 -5 0 pL) into the vial. (Subsequent additions o f peroxide shall be injected through the septa of the VOA vials.) 12.7 F or use of quinine actinometer (Optional): Prepare a batch of quinine irradiation control samples by aliquoting 5 mL o f the 2% aqueous solution (Section 8.8) into the appropriate number of clear and amber 40 mL I-CHEM vials. Prepare one clear and one amber vial per reactor, per day o f exposure. Store the vials at 1-5 C and protected from light prior to use. Place one clear vial in the reactor per day, while removing exposed quinine controls. Exposed quinine controls need to be wrapped in foil upon removal to protect from further exposure. Store at 1--5 C prior to measuring the absorbance via UV-Vis Spectrophotometer. The absorbance measurement should be performed as soon as possible, as the absorbance increase rate after light source removal may be 20% of the rate o f when light is present. (Reference 18.5). 12.8 Place all the "Day 0" samples immediately in a cooler at 1-5 C or freeze at a continuos temperature of less than 0 C, inverted and protected from light. 12.9 Place "Unexposed" sample vials (amber) into Ziploc bags separated and labeled as "with peroxide" and " without peroxide", respectively. Place the bags in the bottom of the water bath, under the photoreactor tray that holds the exposed samples. The "unexposed" samples will remain immersed in the 23-26 C water bath under the exposed samples for the duration of the exposure. Include one quinine control sample in an amber vial with the unexposed sample set. 13.0 Photoreactor set up ETS-8-176.0/Veparaft'oK o f S a m ples f o r P h o to lysis Stu dies in Aqueous M atrices Method Page 13 o f 18 Page 52 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 13.1 Set the irradiation intensity at the desired output. For most experimental conditions, an intensity of 261 W/m2 is chosen because it yields the equivalent average optimum natural daylight radiation for 300-400 nm at known latitude, (see the table below): Irradiance Source Average Optimum Natural Daylight1 Atlas Photoreactor with integrated irradiance output o f 261 W /nr 300-800 nm using the IR Reflecting and 290 cuton filters `Measured, Miami, Florida (18.3) ADDroximate Intearated and Individual Irradiances in W/m2 250-300 nm 300-400 nm 400-800 nm 340 nm 420 nm 0.0 27.8 259.0 0.30 0.67 0.08 27.8 234.36 0.24 0.71 13.2 , For all "Exposed" samples, invert the vials cap-side down and vertical in the photoreactor tray holders to a depth that ensures that half the VOA vial is submersed in the 23-26 C water bath. Include one quinine control sample (Section 12.8) in a clear vial with the exposed sample set. 13.3 Close the door to the photoreactor and turn the door knob completely so the sensor detects that the door is completely shut. 13.4 Turn on the water cooler bath, ensure that it is set between 23-26 C. 13.5 Turn on the photoreactor pump and the power to the reactor. 13.6 Set the irradiation program using the following parameters in the table below: Photoreactor conditions Parameter Setting Program #, # of Phases Flowing Water ("FW") U ON Irradiation intensity Duration of exposure Exam ple: 261 watts/m 2 Example: 8 hours 13.7 After entering the appropriate parameters within the menu, select program #1 to run and start the irradiation program. Upon lamp ignition, the water bath begins to fill and circulate. Visually check for both lamp and water bath activation as an indication of proper initiation o f the photoreactor. When removing samples during the exposure period, select "stop" from the photoreactor keypad. Open the door and careftilly remove the sample rack. C au tion : T he w a lls o f th e ch a m b er a re h o t a n d s e n sitiv e to scra tch in g . 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% H20 2 solution (Section 8.4) and swirl to ensure adequate mixing. Maintain the inverted position of samples removed for spiking pre- and post- the actual peroxide injection. Return samples to their designated locations (bottom of reactor pan ETS-8-176.0P rep a ra tio n o f Sam ples f o r P h otolysis Studies in A queous M atrices Method Page 14 o f 18 Page 53 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 for the unexposed samples, reactor tray holder for the exposed samples, or the cooler for the Day 0 samples). N o te: D o it'tfo r g e t to a d d p e ro x id e to a p p ro p ria te D a y 0 sa m p les! 13.9 Remove the exposed quinine control sample from the reactor tray and visually confirm a color change as an indicator of photoreactor performance. The solution should be a gray/brown color after irradiation. Record the total time exposure of the sample, wrap the sample in foil to protect from light and analyze the quinine sample. Place a new quinine solution vial into the photoreactor tray with the exposed samples. N o te: Q u inin e sam ples do N O T receive peroxide. 13.10 Record the chamber temperature daily on the sample prep sheets. 13.11 Upon completion of the photolytic exposure, samples are removed, labeled with adhesive-backed labels and the study sets (Exposed, Unexposed and Day 0) organized for LC/MS or GC/MS analysis. If subsequent analysis can not be performed immediately, store samples in a cooler at 1-5 C. 13.12 Pertinent information regarding start and stop times of photoreactor exposure study, water bath and chamber temperatures, addition of peroxide, and an explanation of unexpected occurrences shall be documented on the sample preparation worksheets, with appropriate dates, times and initials. 14.0 SAMPLE PREPARATION FOR ANALYSIS. _________________ .____________ ._______ 14.1 LC/MS sample extraction and prep. 14.1.1 Dilute all 5 mL samples by a factor of 1:7 v/v by adding 30 mL of an appropriate analytical solvent containing internal standard (Section 8.6.2) to all vials. 14.1.2 Add spike solution (Section 8.6) containing the target analytes to the appropriate samples. 14.1.3 Ensure the sample vials are inverted several times to ensure adequate mixing. 14.1.4 If samples appear cloudy, and/or the sample matrix appears unclear, it may be necessary to centrifuge the samples, at an appropriate speed and duration (e.g. 2000 rpm for 10 minutes), until no noticeable particulate matter is suspended in the sample. 14.1.5 Aliquot approximately 1 mL into autovials and tightly cap. 14.2 GC/MS sample preparation. 14.2.1 Set up autosampler and concentrator methods. If samples have been kept in cold storage, bring samples to room temperature (approximately 23-26 C). 14.2.2 Spike vials through the septa and place in the autosampler. 15.0 Data Analysis 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 calculated by adding the individual entities and dividing the resultant sum by the number of individual entities. 15.3 Standard deviations will be calculated using either Microsoft Excel or Microsoft Access to calculate standard deviation. The built in function contains the following equation which is based on the individual entities (n) being less than 30: | S r 2- ( S *)2 y n(n-l) ETS-8-176.0P rep a ra tio n o f Sam ples f o r P h otolysis Stu dies in Aqueous M atrices Method Page 15 o f 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 following equation: where: A/B X 100 = Sample % RSD A= standard deviation of averaged samples B= average of samples 16.0 M ethod Performance 16.1 Refer to the definitions section for the method performance specifications/criteria for each respective sample type. 17.0 Pollution Prevention and Waste M anagement____________________________ 17.1 Dispose o f sample waste by placing in high or low BTU containers as appropriate. Use broken glass containers to dispose of glass pipettes. 18.0 Records____________________________________________________________________ 18.1 Fill out the photolysis sample preparation worksheet documents completely, making sure to include all initials and dates. Store photolysis sample preparation worksheets in the raw data file. 18.2 Enter all standard, stock, solutions, etc. preparation information in the proper preparation logbook(s). Make a photocopy of the logbook pages used, and include the copy in the raw data file. Photocopied logbook pages will be included in the final data packet. 18.3 Archive electronic data to compact disc media. 19.0 Attachments______________________ ._________________________________________ 19.1 Attachment A: Example Photolysis Prep sheet. 20.0 References_________________________________________________________________ 20.1 Crosby, Helz, and Zepp. Aquatic Surface Photochemistry, o 480 20.2 Interpersonal conversation with Carrie O'Connor, Optical Systems Engineer, Atlas Electric Devices. ' 20.3 "Suntest CPS/CPS+ Spectral Irradiance Distribution," table distributed by Atlas Electric Devices Company, sent via fax by Richard Sherwin, Sales Representative, 26 July, 2000. 20.4 "Atlas Xenon Filter Combination and Sunlight Measurements," information generated by Atlas Electric Devices Company sent via fax by Richard Sherwin, Sales Representative, 26 July, 2000. ETS-8-t76.0fVeparwiicM o f Sam ples f o r P hotolysis Studies in Aqueous M atrices Method Page 16 o f 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 Actinometiy Studies Under Two Light Sources Specified by the ICH Guideline on Photostability Testing." 21.0 A f f e c t e d D o c u m e n t s 21.1 None 22.0 R e v is io n s __________._____________________________ Revision N um ber. Reason For Revision Revision Date ETS-8-176.^ P reparation o f Sam ples f o r P hotolysis Studies in Aqueous M atrices Method Page 17 o f 18 Page 56 of 165 BACK TO MAIN 3M Environmental, Laboratory Report No. W2783 Attachment A --Photolysis Sample Prep Sheet Test Analyte: Fluorocbemical Degradation (Photolysis) Analysis Sample Prep Sheet Project/Lab Request Number Exposure Type: _________________ ______________ 'Following initial sample prep, all samples will be placed cap-side down and vertical. Nomina! Expo .. Followingphotolysis, Day 0 samples wflt be pulled and extracted with Exposed and Unexposedsamples Sample Matrix:_ Control M atrix: Sample No. Description Rep 1 Rep 2 Rep 3 Spike Matrix Blank Matrix Blank Spike Control Rep 1 Control Spike Control. Blank Control Blank Spike Sample Matrix t est Analyte .....K r a i B T " Volume: Date: Time: Initials: Sample Type Solution I.D. Solution LD. Solution .D. DtyO DayO DayO DvO DayO DtyO H H DayO r? r - ' j DayO ___________________ DayQ v - .. DtyO internal Spike Solution | Comments: Solution I . . Solution I.D. I Comments: -V --------------------- 1 Rep 1 Rep 2 Rep 3 Spike Matrix Blank Matrix Blank Spike Control Rep 1 ___________________ I Control Spike Control Blank Exposed Exposed Exposed Exposed Exposed Exposed Exposed Exposed Exposed B O K IH H H ; ------------------ 1 * -- Rep I Unexposed Rep 2 Unexposed Rep 3 Unexposed Spike Unexposed Matrix Blank Unexposed Matrix Blank Spike Uncxposed Control Rep 1 Unexposed Control Spike Unexposed Control Blank Unexposed Control Blank Spike Unexposed Component and Solution Concentration , : 1 1 1 1 ---------------,- " -1 ,-- - * ...i Photolysis Reactor I.D.: Start Date: | Time: Stop Date: 1 Time: Total Exposure: __________ day Initials Freezer/Refriferator- Storage I.D.: Start Date: Time: Initials Stop Date: Time: h o u rs________ min Initials Initials General Note: Check m ark - Indicates the solution added. n/a **not applicable K H f W S S S " n q i K different solution ID, require no addition o f solution Commenti: ETS-8-116.Q P reparation o f S a m ples f o r P h o to ly sis S tu dies in A queous M a tric es Method Page 18 o f 18 Page 57 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 3M Environmental Laboratory E q uipm en t Procedure O p e r a t io n and M a intena nce o f t h e Su n l ig h t E x po su re Sy st e m , I m m er sio n unit, and R ecirc u la tin g W a ter C h il le r Sy stem Procedure Number: ETS-9-44.0 Exact Copy of Original Initial Date Approved by: Adoption Date: i oj2j?jo Revision Effective Date: Laboratory Management Date Date ETS-9-44.0 Equipm ent P rocedure fo r the A tlas SUNTEST Sunlight Exposure System Page 1 of 8 Page 58 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 1.0 Scope and Application____________________________________________________ 1.1 This equipment procedure describes the regular operation and maintenance o f the Atlas SUNTEST Sunlight Exposure System equipped with an immersion unit and recirculating water chiller. ' 2.0 DEFINITIONS__________________________;____________________________________________ 2.1 Photon energy: U = hv = hc/A, where h is Planck's constant, c is the speed o f light, and v and X are the frequency and wavelength o f 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 o f a photon) in Watts/m2 specific to a wavelength or wavelength range. The irradiance output specific to the types o f Atlas wavelength filters available (Reference 14.9) should be used as a guide to calculating the global irradiance (in units of W/(m2nm) needed to give a specific energy over a desired wavelength range. 3.0 Description_________________________________________________________________ 3.1 The Atlas SUNTEST Sunlight Exposure System (CPS+ or XLS+) produces visible and ultraviolet light (250-765 W/m2). Light produced is filtered with a filter or combination of filters to allow specific wavelength ranges. Samples are exposed to the light in a reflecting chamber. An immersion unit with water recirculation through a chiller provides a cooled, constant sample temperature. 4.0 I d e n t if ic a t io n ______________________________________________________________________ 4.1 Atlas SUNTEST XLS+, equipped with a xenon arclamp, lamp filters) available from Atlas to allow specific irradiance ranges, and immersion unit. 4.2 Atlas SUNTEST CPS+, equipped with a xenon arclamp, lamp filter(s) available from Atlas to allow specific irradiance ranges, and immersion unit. 4.3 Neslab CFT-33 Refrigerated recirculator or equivalent 5.0 W arnings and Cautions________ ___________________________________________ 5.1 Health and Safety Warnings: 5.1.1 Wear appropriate laboratory safety personal protective equipment. 5.1.2 The xenon lamp emits ultraviolet light which can cause bums to the skin and permanent damage to the eyes. Never attempt to operate the unit with the test chamber door open. 5.1.3 When filling the sample immersion unit with water, always shut off all power to the SUNTEST device and the immersion unit to prevent electrical shock. 5.2 Cautions: 5.2.1 Handle optical parts carefully, fingerprints on the lamp, filter or quartz dish can result in altered spectral output or early lamp failure. 5.2.2 The reflective coating of the test chamber walls is sensitive to scratches. Do not use any abrasives or harsh cleaning agents that may cause scratches and non uniform illumination of the test chamber. ETS-9-44.0 Equipm ent Proceduref o r the A tlas SUNTEST Sunlight Exposure System Page 2 of 8 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 5.2.3 5.2.4 5.2.5 Keep SUNTEST unit clear o f obstructions that would block vents; overheating may cause blown fuses, shortened lamp life or other damage. After beginning the experiment, always make sure that the sample vials are sufficiently submerged. Excessive heat may affect the results o f the experiment. Manually drain the immersion tank on the XLS+ models after stopping the run; otherwise, the water will overflow. 6.0 S p e c ia l I n s t r u c t io n s _________________________________________________________ _ 6.1 None. 7.0 R e s p o n s ib il it y _________________________________________ ^_________________________ 7.1 The analytical group of personnel who routinely operates the equipment is collectively responsible for the instrument operation as described in this document. The person responsible for maintenance and calibration (and an alternate) will be identified in the front o f the equipment logbook. 8.0 S u p p l ie s a n d M a t e r ia l s ______________________________________ ;__________________ 8.1 Xenon lamp for XLS+, Atlas PN 56077798 8.2 Xenon lamp for CPS+, Atlas PN 56001794 8.3 Hand-tools as required 8.4 Kim-WipesTM 8.5 Optional radiation filter(s) for lamp available from Atlas: Filter/ Atlas Part Number Q uartz Dish w/ fll reflective coating, PN 56052388 Q uartz Dish, PN 56052373 UV Special Suprax Filter, PN 56052371 Window Glass Filter, PN 56052372 Window Glass Solar ID 65 Filter, PN 56077769 Solar Standard Filter, PN 56077759 Pronerties IR reflective coating (supplied standard with unit) Uncoated (to allow higher black standard temperatures) 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 exposure behind 6 mm (0.236 in.) window glass. (Must be used with Window Glass Filter above.) Cut-on at 290 nm, simulates outdoor solar radiation at optimal UV intensity. ETS-9-44.0 Equipm ent Proceduref o r the A tlas SUNTEST Sunlight Exposure System Page 3 of 8 Page 60 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 9.0 C l e a n in g P r o c e d u r e s _________________________________ _______ All routine and non-routine cleaning procedures will be performed by person(s) designated in the front o f the instrument logbook; see Section 12). 9.1 Routine cleaning 9.1.1 Clean the inlet air filters at the back of the SUNTEST unit every 6 months with a mild soap solution. Rinse in clean water. When more severe contamination is present, vacuum the filters or replace them. 9.1.2 Clean the reflector in the test chamber when it is dirty, using a soft cloth and mild soap solution. DO NOT use any abrasive cleaning materials or the reflector may be permanently damaged and irradiance uniformity will be altered. 9.1.3 Clean and/or flush the water tank and water lines on the immersion unit monthly to prevent build up o f residue in the circulating water system. 10.0 M a in t e n a n c e P r o c e d u r e s __________________________________________________________ 10.1 Routine maintenance will be performed by the person(s) designated in the front o f the equipment log (see Section 12): 10.1.1 Replace the xenon lamp after 1500 hours or when the required irradiance level cannot be achieved (e.g. error message reads "E MAX Power reached; CHANGE XENON LAMP") Refer to the SUNTEST instruction manual for details on how to replace the lamp. 10.1.2 If the temperature near the lamp becomes too high, the fuse blows to interrupt power and save the lamp (indicated by the error message "DOOR OPEN or TEMPERATURE FUSE"). Refer to the SUNTEST instruction manual for details on how to replace the fuse. 10.1.3 Record routine maintenance in the equipment log (see Section 12). 10.2 Non-routine maintenance will be performed by the person(s) designated in the front o f the equipment log (see Section 12): 10.2.1 If the equipment fails to operate, refer to the equipment manual for further instructions, if necessary. Contact the Team Leader for instructions if the equipment cannot be made operational. 10.2.2 If an abnormal operating situation occurs or if calibration verification fails, contact the responsible individual identified in the equipment log. Label the equipment as "out of service" if it cannot be immediately repaired. 10.2.3 Record non-routine maintenance in the equipment log (see Section 12). 11.0 I n s t r u m e n t C a l ib r a t io n __________________________________________________________ 11.1 The photoreactor is set to maintain a specified integrated energy output. The amount o f energy output from the lamp may be monitored with the use of a radiometer. The radiometer system will provide and record instantaneous energy output. Refer to ETS-950.0 Operation and Maintenance of Radiometer and Detector. 11.2 Calibration of SUNTEST systems will be performed two times each year by Atlas Electric Devices Company. ETS-9-44.0 Equipm ent Proceduref o r the A tlas SUNTEST Sunlight Exposure System Page 4 of 8 Page 61 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W 2783 12.0 O p e r a t in g P r o c e d u r e s ____________________________________________________ __ 12.1 For more detailed operating instructions refer to the equipment operating manuals. 12.2 Immersion Unit 12.2.1 To begin operation, fill the tank with water until the level indicator is up to the full mark. 12.2.2 Turn the power on. 12.3 Chiller 12.3.1 Turn the power on. Set water temperature knob to desired set point. Allow temperature to equilibrate before igniting the SUNTEST lamps. 12.4 SUNTEST XLS+ or SUNTEST CPS+ unit set-up 12.4.1 Select the desired wavelength filter from the parts listed under Section 8.4 to achieve the proper irradiation specified in the program, and program the photoreactor with the filter type information: With the photoreactor menu in the "Program" mode, select the appropriate filter combination type: _________________________Optical Filter System Designations A: Coated quartz glass only________________ ;______________ B: Coated quartz glass with UV special glass__________ ;_______ C: Coated quartz glass with window glass____________________ D: Uncoated quartz glass only_____________________________ E: Uncoated quartz glass with UV special glass_______________ F: Uncoated quartz glass with window glass 12.4.2 Selection/determination of energy output (W/m2) 12.4.2.1 Irradiance control and display is between 250-765 W/m2 (nominally 300 800 nm). The irradiance is determined by the settings o f the test program [including type o f 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 o f lamp filter(s) used. E.g. if the filter has a narrow range such as a cut-on at 400 nm, all irradiance energy coming from wavelengths <400 nm will not reach the samples, and the total integrated irradiance will be less than if the filter's cut-on was at, for example, 290 nm. 12.4.2.2 Once the proper filteifs) is/are designated, the photoreactor will base the energy output on what type o f wavelengths are being allowed to pass through the filter system to reach the samples. To calculate the energy output to program into the system, refer to References 14.7,14.8 and 14.9 as guides to calculate the desired spectral irradiance. Reference 14.7 may be used to calculate the programmed global irradiance necessary to achieve desired irradiances at specific wavelengths or wavelength ranges. Reference 14.8 maybe used to reference sunlight measurements and to correlate natural sunlight to the Atlas Suntest photoreactors. Reference 14.9 is a useful reference for determining irradiances at a specific . ETS-9-44.0 Equipm ent P rocedurefo r the Atlas SUNTEST Sunlight Exposure System Page 5 of 8 Page 62 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 wavelength or a wavelength range using specific filter combinations at specified global irradiances o f 250,500, and 765 W/(m2nm). 12.5 Photoreactor Analysis set up 12.5.1 Place VOA (volatile organic analysis) vials containing samples (see the appropriate analytical method) into the test chamber. Sample vials to be exposed must be cap side down to allow light to enter the vial. Tighten caps securely to prevent leakage. Secure the vials in the chamber to prevent floating once the water begins to circulate. 12.5.2 Close the chamber door and turn the power on. 12.5.3 From the initial LCD display, use the arrow keys to select Program. Press "Enter". 12.5.4 If programming a new method is necessary, use the arrow key to select Programming. Press "Enter". 12.5.5 Input program number, number of phases, desired irradiance, immersion function, phase time and switch off criteria. Each entry is followed by the "Enter" key. 12.5.6 To start the program, select "Program Start" and press the "Enter" key. 12.5.7 Press "Escape" for the next screens if the filter has not been changed and no printout is desired. Input program number and press "Start" 12.5.8 Program will begin with lamp ignition. Note: Due to the modified sample chamber in the SUNTEST XLS+ models, the water initially present in the immersion tank is not sufficient to fill the sample chamber once a program has started. Refill the immersion unit as the water level drops below the fill line. Once a program has finished, drain the immersion tank so that it does not overflow when water from the sample chamber drains back down into the immersion unit. Failure to do so may result in remote flooding. 12.5.9 To interrupt operation (e.g. to add peroxide reagent)Press "Stop". If it is necessary to turn the power off (to exchange the lamp, for example) wait until the fan turns off in 1-3 minutes before turning power switch to "O ff' and unplugging the power cord. When ready to continue operation, turn power "On". 12.5.10 To resume operation, press "Start". The program will continue at the point of interruption. 12.5.11 To read parameters during the program run, scroll through the parameters o f the running program by using the arrow keys. This is helpful to see how many more hours are remaining in the running program, 12.5.12 The SUNTEST will shut off automatically when the switch-off criteria are reached. To display the total time and irradiance, press "Enter". Record exposure time in instrument run log. Then turn power "Off". 12.5.13 To manually stop the program, press "Stop". Wait until lamp is cooled, then press "Escape". Power can then be turned "O ff'. ETS-9-44.0 Equipm ent Procedurefo r the A tlas SUNTEST Sunlight 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(s) designated at the front o f the equipment log will record all cleaning and maintenance activities in the appropriate log for each SUNTEST system. Records for routine maintenance of equipment must include the dates of the operation, whether the operations followed the SOP, and the initials of the person performing the operation. Records for non-routine repairs performed as a result o f instrument failure or malfunction must include the nature o f the defect, how and when the defect was discovered, any remedial action taken in response to the defect, and the date and initials of the person performing the maintenance. Maintenance by outside contractors should include their name and company affiliation. 13.1.2 Run Log: Record each experiment in the appropriate instrument logbook. Enter the operators initials, time and date of exposure, lamp intensity and water temperature as the samples are placed in the chamber. When samples are finished, record the time and date when samples came out, the ending chamber temperature and the actual hours of exposure. All entries made in the run log should be initialed and dated. 13.1.3 SUNTEST Data Output Log: XENOVIEW 2.2 Storage Software will receive and record the measurement data transferred from the SUNTEST system to a computer or printer, while a program is in progress. The measurement data recorded includes: number of phases, phase time, chamber temperature, radiant exposure, irradiance, running time, date and time data is recorded. Refer to XENOVETW software instruction manual for details on how to operate software. Any printouts of program or other data should be initialed and dated prior to adding to the study file. 13.2 Identification records for each system include equipment ID, manufacturer, model number, and serial number of each individual component. In addition, if components are removed or added, the above information must be written in the logbook including the date the change was made and initials of the analyst completing the change. 14.0 R e f e r e n c e s ________________________________________________________________ ______ 14.1 SUNTEST XLS/XLS+ Instruction Manual, Doc. No. 20-8036-00 Rev. 0 12/98 Atlas Electric Devices Company. 14.2 SUNTEST CPS/CPS+ Operating Manual, 6/97 Atlas Company. 14.3 SUNTEST XLS+ Immersion Device Operating Manual, 2/99 Atlas Company. 14.4 SUNTEST CPS+/XLS+ Software Documentation 1.4 Atlas Company. 14.5 XENOVIEW 2.2 Storage Software Operating Instructions. 14.6 ETS-9-50.0, Operation and Maintenance of Radiometer and Detector. 14.7 "SUNTESTIrradiance in W/m2*nm". Tables furnished by Atlas Company. 14.8 "Atlas Xenon Filter Combination". Table furnished by Atlas Company. 14.9 "SUNTEST CPS/CPS+ Spectral Irradiance Distribution". Table furnished by Atlas Company. ETS-9-44.0 Equipm ent Procedurefo r the Atlas SUNTEST Sunlight Exposure System Page 7 of 8 Page 64 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 15.0 Affected Documents 15.1 None. 16.0 Revisions Revision Number. Reason For Revision Revision Date ETS-9-44.0 Equipm ent P roceduref o r the A tlas SUNTEST Sunlight Exposure System Page 8 o f 8 Page 65 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 3M Environmental Laboratory Analysis of Fluorochemicals by A rchon Purge and Trap A utosampler, Tekmar Purge and Trap Concentrator and Agilent Gas Chromatograph/M ass Spectrometer Procedure Num ber: ETS-8-18ZD Exact Copy of Original ____Q&* Initial Date ,, Approved by: Laboratory Manager Adoption Date: Revision Date: Date Date E T S - 8 - 182.0 Analysis o f FCs by Purge & Trap AutosampIer/Concentrator/GC/M S Page 66 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 1.0 Scope and Application 1.1 Scope. This method is used for the analysis of selected hydrolysis and photolysis samples for the presence of degradation products such as olefins and hydrides using gas chromatography/mass spectrometry in a full scan mode. An Archon autosampler and Tekmar Purge and Trap concentrator (or an equivalent system) is coupled to a GC for purging analytes from the liquid matrix and concentrating them on the trap column before injecting on to the GC. 1.2 Applicable compounds. Compounds that may be analyzed by this method are listed below. Other fluorochemicals may be detected by monitoring mass spectra and running library comparison. Compounds that are detected but do not have appropriate standards, will be quantified relative to structurally similar standard compounds listed below. 1.2.1 lH-perfluoroethane (lH-pfC2) 1.2.2 Perfluro-2-butene (pfC4-2ene) 1.2.3 lH-perfluropropane (lH-pfC3) 1.2.4 lH-perfluorobutane (lH-pfC4) 1.2.5 Perfluoro-2-heptene (pfC7-2ene) 1.2.6 Perfluoro-l-heptene(pfC7-lene) 1.2.7 lH-perfluorohexane (lH-pfC6) 1.2.8 Perfluoro-2-octene (pfC8-2ene) 1.2.9 IH-perfluoroheptane (lH-pfC7) 1.2.10 2H-perfluorooctane (2H-pfC8) 1.2.11 lH-perfluorooctane (lH-pfC8) 1.3 Instrument Surrogate compounds. Added at the time of analysis and used to monitor performance of purge and trap autosampler and concentrator. 1.3.1 Dibromofluoromethane 1.3.2 Toluene-d8 1.3.3 4-Bromofluorobenzene 1.3.4 Pentafluorobenzene 1.3.5 1,4-Difluorobenzene 1.3.6 Chlorobenzene-d5 1.3.7 l,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 temperature programmed GC for analyte separation and subsequent mass spectrometer detection and quanitation. The liquid sample is purged for 20 min. in the sample vial, and the volatile components are swept onto a chemical trap in the concentrator. In the subsequent desorption mode, gas flows in opposite direction and temperature o f the chemical trap increases to 250 C. The trapped analytes are transferred onto the GC column for GC/MS separation, detection, and quanitation. Through this process, a high volume of sample is injected and most o f the non-volatile matrix components stay in the sample vial, allowing low level detection o f fluorochemicals. ETS-8-182.0 Analysis o f FCs b y P urge & Trap Autosampler/Concentrator/GC/M S Page 2 o f 12 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 3.0 Definitions___________________________________________________________ Xl Calibration Standard. A dilution of various amounts of a stock, intermediate or purchased standard to achieve standard solutions in a concentration range o f interest. 3.2 Calibration Curve. The graphical relationship between known values, such as concentration of a series o f calibration standards and their instrumental response. 3.3 External Standard Quantification. Process of establishing the concentration of a target analyte by plotting the theoretical amount (in units of ng/mL or pg/mL, etc.) versus the response o f the target analyte(s) on column. The resultant curve(s) shall be used to determine unknown concentrations by comparing the area response o f target analyte(s) to the area response and corresponding analyte amount on the appropriate analyte's calibration curve. 3.4 Coefficient of Determination (r*). The square o f the correlation coefficient. It is the proportion of the variation in the dependent variable that is accounted for by the independent variable. 3.5 Instrument Surrogate. An organic compound similar to the target analyte(s) in behavior in the analytical process, but is not normally found in the sample(s). A surrogate may be added to sample vial during instrument analysis. 3.6 Sample Surrogate. An organic compound similar to the target analyte(s) in chemical composition and behavior in the analytical process, but is not normally found in the sample(s). A surrogate may be added to sample triplicates and matrix spike samples along with the test analyte (pre-photolysis). 3.7 Continuing Calibration Verification (CCV). Standards analyzed during an analytical run to verify the continued accuracy of the calibration curve. This solution may or may not be prepared from a different source or lot number than the calibration curve standards. 3.8 Solvent Blank. A sample o f analyte-free medium that is not taken through the sample preparation process. This blank is used to evaluate instrument contamination. 3.9 Blank. For photolysis studies, there are multiple blanks to adequately represent the variables of the study (Exposed, Unexposed and Day 0 samples with/without peroxide addition). The blank is carried through the sample preparation, photolytic and analytical procedures to monitor for contamination during any step. It is also used to establish a chromatographic baseline/background and monitor for analytical interference or suppression o f target analyte(s) from the matrix. 3.9.1 3.9.2 Matrix Blank: A sample of analyte-free matrix (buffered water, lake water, etc.) to which all reagents are added in the same volumes or proportions as used in sample processing. It is used to document the test system without test analyte. Control Blank: A sample of analyte-free matrix (Milli-Q water) to which all reagents are added in the same volumes or proportions as used in sample processing. It is used to control the test matrix and monitor matrix specific ETS-8-182.0 Analysis o f FCs by Purge & Trap Autosampler/Concentrator/GC/M S Page 3 o f 12 Page 68 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 background levels, interferences or suppression of target analyte(s) from the matrix. 3.10 Lim it of Quantitation (LOQ). The lowest concentration that can be reliably measured within specified limits o f accuracy during routine laboratory operating conditions. The LOQ is generally 5 to 10 times the minimum concentration with a 99% confidence limit that the concentration is greater than zero. However, it may be nominally chosen within these guidelines to simplify data reporting. For many analytes, the LOQ is selected as the lowest non-zero standard in the calibration curve that is greater than 4 times the level o f the matrix blank. 3.11 Sample Triplicates. Three samples taken from and representative of the same sample source. These are prepared separately and carried through all steps o f the exposure, extraction and analytical procedures in an identical manner. There are multiple sets of triplicate samples to adequately represent the photolytic variables of the study (Exposed, Unexposed and Day 0 with/without peroxide addition). Triplicate samples are used to assess variance of the photolytic method, including sample preparation, photolysis exposure, and analysis. 3.12 Relative Standard Deviation (RSD). A measure of precision defined as the standard deviation of three or more values divided by the average of the values and multiplied by 100. (Also reported as Coefficient o f Variation (CV)). 3.13 Analytical Spike. Prepared by adding a known mass of target analyte(s) to a specified amount o f a sample or control matrix prior to analysis. This assumes that an independent estimate o f target analyte concentration is available. Matrix spikes are used to determine the effect o f the matrix on method recovery efficiency. ' 3.14 Accuracy. The closeness o f agreement between an experimentally determined value and an accepted reference value. When applied to a set of observed values, accuracy is a combination o f a random (precision) and a common systematic (bias) component. For purposes o f the study, the acceptance criterion is 75% to 125% of the nominal value. 3.15 Geometric M ean of the calibration curve: The square root of the product o f the high standard concentration and the low calibration curve standard. When preparing calibration curve standards, the number of calibration standards below the geometric mean shall equal the number o f calibration standards above the geometric mean. Having equal distribution of calibration standards above and below the geometric mean when analyzing and reprocessing data, effectively weights the curve such that both the high and low ends o f the curve are given equivalent significance. 4.0 Warnings and Cautions_________________________________________________ 4.1 Health and Safety Warnings: 4.1.1 The operator must be familiar with the purge and trap autosampler/concentrator/GC/MS system and associated hazards, such as high temperature, effluent venting, solvent use, and low-pressure vacuum system. See instrument manuals E T S - 8 - 182.0 A nalysis o fF C s by P urge & Trap Autosampler/Concentrator/GC/M S Page 4 o f 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 spectrometer pump exhaust must be connected to the laboratory vent system to keep potentially hazardous effluent from mixing with laboratory air. 4.2 Cautions: 4.2.1 It is recommended that a grounded antistatic wrist strap be worn while disconnecting all wires, contacts, or cables which are connected to printed circuit boards within the Archon autosampler, Tekmar concentrator or MS analyzer. 4.2.2 To prevent the breakage o f the Standard Vial on the Archon autosampler, do not use any tool and do not overtighten the thumbnut. 5.0 Interference_________________________________________________________ 5.1 Methanol, water and other co-extracted matrix components could interfere with detection decreasing sensitivity. 6.0 Equipment ___________________________________ '___________ _________ 6.1 System: "Rufus", or equivalent: 6.1.1 Autosampler: Varian, Archon 6.1.2 Concentrator: LSC2000, Tekmar 6.1.3 GC: 6890, Agilent 6.1.4 MS: 5973N, Agilent 6.1.5 Column, GS-GASPRO 60m x 0.23mm, J&W 7.0 Supplies and Materials_______________________________________________ 7.1 Helium, ultra-high-purity 7.2 40ml VOA vials, e.g. I-Chem, S236-0040 8 .0 R eagents and Standard_______________________________________________________ 8.1 Methanol, Purge and Trap grade or equivalent 8.2 Standards. Typically a minimum of five calibration standards, ranging from 1 ng/ml to 20 ng/ml are prepared. This concentration range should bracket the concentration o f samples and matrix spikes; if the analyte concentration exceeds this range, then the calibration range should be increased. 8.3 Instrum ent Surrogates. Used only to monitor performance of purge and trap autosampler and concentrator and not for quantitation. 8.4 Sample Surrogates. May be used to monitor sample preparation, photolytic exposure and analytical performance. 9.0 Sample Handling_______________________ ______________________ SU Store standards and samples in the refrigerator at 4 C + 3 0 C until analysis time ETS-8-182.0 Analysis o f FCs by Purge & Trap Autosampler/Concentrator/GC/M S Page 5 o f 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 Quality Control_____________________________________ 10.1 Calibration Standards. Calibration standards (Section 11) used to generate a calibration curve. The number o f calibration standards and the concentration levels should be sufficient to encompass the expected concentrations of the study samples. In general, a minimum of five calibration standards is required for fit o f linear regression. 10.2 Continuing Calibration Verification (CCV). Analyze a mid-range calibration standard after a maximum of every fifteen samples. 10.3 Solvent blank. Solvent blanks are run before and after every calibration curve, CCV, matrix and control blank (see 3.9.2), and after batches of no more than 30 injections. Acceptable values for the blanks are values below 25% o f the limit of quantitation (LOQ) of the instrument. If analyte carryover is a problem, use back-to-back solvent blanks. 10.4 Sample Triplicates. Prepare and analyze all samples in triplicate to provide a measure o f the precision o f analysis. 10.5 Analytical Spikes. Prepare a matrix spike sample for each sample type as applicable to determine the matrix effect on the recovery efficiency. Concentrations o f the spike should be approximately equal to a mid-range calibration standard. The matrix spike sample should be analyzed periodically to measure the precision associated with the analysis. The analyst shall accept percent spike recoveries o f 100125% . Spike recoveries outside of this range should be noted and used with other criteria to evaluate the condition of the analytical run. Consult with the Team Leader or designee for direction and final acceptance or rejection of the analytical run. 11.0 Calibration anb Standardization 11,1 Analyze standards prior to each set of samples. The linear regression will be calculated from the plot o f all individual calibration points, without including or not forcing through zero, using Target NT Software. A minimum o f five calibration standards is required to generate linear regression for target analyte(s). If the calibration curve residuals are greater than 25% deviation from the theoretical value, quadratic curve fitting and/or dropping low/high curve points may be required if data review shows this to be a consistent and more accurate representation of the instrument response. Document in the raw data the technical justification for any deviation and consult with the team leader or designee for direction and for final acceptance or rejection o f the data, 11.2 If the curve does not meet requirements perform routine maintenance or prepare a new standard curve (if necessary) and reanalyze ETS-8-182.0 Analysis o f FCs b y Purge & Trap Autosampler/Concentrator/GC/M S Page 6 o f 12 Page 71 of 165 BACK TO MAIN 3M Environmental Laboratory Report 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 DesDm Pol CLOSED STOP Pol. CLOSED Equilb. Count 0 Equilb. Time 0 12.1.2 Archon System Options Barcode Scanner NO Needle Sparge? YES Ign. Vial Type? YES Ignore No Vial? NO HotWater Rinse? NO Vial Checks? YES Beep on Error? YES 12.1.3 Archon Method Sample Type Soil First Vial 1 Last Vial up to 51 Sample Volume 10 Standard 1 (luL) YES Standard 2 NO S.PreHeat Stir NO Stir Syring Flushes NO 0 PreHeat YES PreHeat Temp 35 PreHeat Time 1.0 Purge Time 20.0 Desorb Time(m) 0.5 Oper. Mode Remote Cycle Timer 0.0 Aux. Timer 0.0 Link to Method 0.0 Soil Purge Flow 40ml/min Soil Purge Pressure 20psi ETS-8-182.0 Analysis o f FC s by Purge & Trap Autosampler/Concentrator/GC/M S Page 7 o f 12 Page 72 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 12-2 Set Tekmar options Standby 40C (30C by purge) Purge 20.00min Dry Purge 2.00min Desorb Preheat 245C Desorb 0.50min at 250C Bake lO.OOmin at 260C BGB OFF BGB Delay Osec Auto Drain ON Valve 180C Line 180C Mount 100C Runs per Sample 1 Purge Flow Purge Pressure Trap 40mL/min 20psi VOCARB 3000 Containing: Carbopack B Carboxen 1000 Carboxen 1001 12.3 Set GC conditions 12.3.1 Oven: Initial temp: 40 C Initial time: 4.00min Ramp at 15.00 C/min to 280 C Final time: lO.OOmin 12.3.2 Front Inlet: Mode: Split Initial temp: 180C Pressure: 8.50psi (on) Split ratio: 10.7 :1 Split flow: 16.1 ml/min Total flow: 20.6 ml/min 12.4 Set MS conditions 12.4.1 Adjust conditions as needed to optimize system performance and document operating conditions in the instrument run log. Acquisition mode: Scan (from 10 m/z to 650 m/z) MS source temp: 230 C MS quadruple temp: 150 C Interface temp: 260 C Multiplier voltage: adjust to give required low standard sensitivity ETS-8-182.0 Analysis o f F C s by P urge & Trap Autosampler/Concentrator/GC/M S Page 8 o f 12 Page 73 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 12.5 * 12.6 ' Set up the instrument acquisition method. Name the sequence. The sequence includes a sample list documenting the method used and datafiles created. The sequence should be documented n the run files. Sample analysis. 12.6.1 Set up autosampler and concentrator methods. Bring samples to room temperature (~22C), spike them and place them on autosampler. Generate a mass spectrometer tune report and review. Operating conditions provided above are recommended and may be adjusted to optimize system performance. Analyze all standard, samples, and spiked samples using the same analytical conditions. Document the conditions in the run log. 12.6.2 When data acquisition is complete, data files should be transferred to Target version 4.0 for processing. 13.0 Data Analysis and Calculation________________________________________ 13.1 Each batch o f data should be processed using Target Genie integrator. Integration parameters should be set to minimize the number of manual integrations required yet still result in uniform integration of peaks at all concentration levels. If manual integrations are required, a review code should be assigned to indicate the reason. Review Codes are listed below. Review Code Explanation Peak was not automatically integrated by Target, therefore, integrated M l manually Peak was automatically integrated; was reintegrated manually to M2 improve sample-to-sample integration consistency. Incorrect quantification ion peak was integrated; manual integration M3 was done to select the correct peak. Incorrect monitor ion peak was integrated; manual integration was M4 done to select the correct peak. M5 Others (specify) 13.2 When data processing is complete, summarize the data using an appropriate form. Formula is provided below for some of the calculations that may be required. 13.2.1 Calculate matrix spike percent recoveries using the following equation: (observed concentration - background concentration) x 100 %Recovery = expected concentration 14.0 Method Performance_________________________________________________ 14. Coefficient of Determination (r2). The coefficient of determination (r2) for the initial calibration curves should be 0.990 or greater. The curves should be examined closely for ETS-8-182.0 A nalysis o f P C s by Purge & Trap Autosam pler/Concentrator/G C/M S Page 9 o f 12 Page 74 of 165 BACK TO MAIN 3M Environmental Laboratory 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 acceptance or rejection for the data. 14.2 Calibration Standards. The acceptance criterion for the calibration standards is that the accuracy o f each standard is 75% to 125% (+ 25 % difference) of the nominal value. Calibration standards outside this range are to be noted. Document in the raw data the technical justification for deviations. Consult with the Team Leader or designee for direction and for final acceptance or rejection for the data. 14.3 Instrument Surrogate. Review of the instrument surrogate performance is performed by monitoring instrument surrogate recoveries throughout the run. Inconsistencies in the recoveries may be the result of instrumental changes, or injection error. Consult with the Team Leader or designee for direction and final acceptance or rejection of the analytical run. 14.4 Sample Surrogate. Sample surrogate performance is evaluated by averaging the area response throughout the analytical run and calculating %RSD. Inconsistencies in the surrogate peak area may indicate instrumental changes, injection error, or changes in the test-system. Consult with the Team Leader or designee for direction and final acceptance or rejection o f the analytical run. 14.5 Continuing Calibration Verification. If the accuracy for the amount of quantified analyte is greater than 25% from the nominal value relative to the initial standard curve, the Team Leader should be consulted. Only those samples analyzed before the last acceptable calibration check standard will be used. Consult with the Team Leader or designee for direction and for final acceptance or rejection for the data. 14.6 Solvent Blanks. Solvent blanks should show no more than a 5% carryover from a high standard or calibration check standard. If so, two sequential solvent blanks may be necessary to rule out instrumental contamination 14.7 Matrix Blanks. Matrix blanks are the basis for determining the LOQ and are monitored at various times in the analytical run. Peaks with greater than 25% o f the peak area o f th designated LOQ value observed in matrix blanks are indicative of either matrix effect, sample contamination or instrument contamination. Use o f 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 determining matrix effect (interference or suppression). Peaks with greater than 25% of the peak area of the designated LOQ value observed in control blanks are indicative of either matrix effect, sample contamination or instrument contamination. 14.9 Limit of Quantitation (LOQ). The LOQ is equal to the lowest acceptable standard (i.e. % accuracy is < 25 % nominal value) in the calibration curve that is greater than 4 times the level of the matrix blanks. 14.10 Sample Triplicates. The analyst shall accept %RSD values < 25%. %RSD values > 25% should be noted. Data used in the final report that is deemed out of control will be ETS-8-182.0 Analysis ofF C s by Purge & Trap Autosampler/Concentrator/GC/M S Page 10 o f 12 Page 75 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 required to have technical justification for why the data is used, documented in the final report and raw data. Consult with the Team Leader or designee for direction, and for final acceptance or rejection of the data. 14.11 Analytical Spikes. The analyst shall accept percent spike recovery values o f 100 25%. Spike recoveries outside o f this range should be noted. Consult with the Team Leader or designee for direction, and for final acceptance or rejection of the data. Data that are used in final report that is deemed out of control will be required to have a technical justification for why the data are being used, documented in the final report and raw data. 14.12 System Suitability. 14.12.1 Tuning: A mass spectrometer tune report shall be generated before starting each analytical sequence. If the tune parameters do not meet the criteria suggested by the mass spectrometer manual, then the mass spectrometer should be re-tuned. If mass 28 is present in the tune report at >10% relative to mass 69 then an air leak is present in the system. The source o f 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 Pollution Prevention and Waste Management___________________________ 15.1 Dispose o f sample vials in low BTU and flammable solvent in high BTU containers. Dispose o f glass pipette waste in broken glass containers located in the laboratoiy. 16.0 Records_____________________________________________ _______________ 16.1 Store chromatograms in the study folder that is labeled with the study number. Include the following information on each chromatogram either in the header or hand written on the chromatogram: injection date, analyst's initial, sample unique number, sample name, preparation date, incubation period, dilution factor (if applicable), and instrument name. Store a copy o f the acquisition conditions with the chromatogram packet. 16.2 Plot the calibration curve by non-weighted linear regression and store in the study/project folder. 16.3 Print the sequence and MS tune report from HP Chemstation. The sequence should be initialed and dated, and stored in the run log binder. The MS tune report should be stored in the tune report file. Copy o f the sequence and MS tune report should be placed in appropriate study/project folder. 16.4 Summarize data using suitable software and store in the study/project folder. 16.5 Back up electronic data to appropriate medium (primarily CD). Record in the study/project folder the filename and location of backup electronic data. 16.6 List the documents and records generated when performing this method and where they are to be archived. ETS-8-182.0 Analysis o fF C s by Purge & Trap Autosampler/Concentrator/GC/M S Page 11 o f 12 Page 76 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 _17.0 _At_tachment : 18.0 References__________________________________________________ 18.1 Archon Purge and Trap Autosampler System Operator's Manual, 1996, Varian. 18.2 Tekmar LSC200 Instruction Manual, 1996, Tekmar. 18.3 Agilent MSD Hardware Manual for 5973N, 1999, Agilent. 18.4 Agilent 6890 Series Gas Chromatograph, volumes 1-3,1999, Agilent 19.0 Affected Documents 19.1 None. 20.0 Revisions Revision Number. Reason For Revision Revision Date ETS-8-182.0 Analysis o f FCs by Purge & Trap Autosampler/Concentrator/GC/M S Page 12 o f 12 Page 77 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 -3M Environmental Laboratory Method Indirect Photolysis Screening Test in Synthetic Humic Water M ethod N um ber: ETS-8-177.0 Approved By: Laboratory Management Adoption Date: Revision Effective Date: Date D ate --' ETS-8-177.0 Indirect Photolysis Screening Tests in Synthetic Humic Water Page 1 o f 16 Page 78 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 1.0 Scope and Application_______________________________________________ 1.1 Purpose. Chemicals dissolved in natural waters are subject to two types o f photoreaction. In the first case, the chemical o f interest absorbs sunlight directly and is transformed to products when unstable excited states o f the molecule lead to decomposition. In the second case, reaction o f dissolved chemical is the result of chemical or electronic excitation transfer from light-absorbing species in the water. Synthetic humic water (SHW) is used for the photolytic reaction matrix because it contains dissolved organic material that absorbs sunlight and produces reactive intermediates that include singlet oxygen (10 2) that promotes indirect photolysis o f the test substance. 1.2 The method is divided into two phases. Phase one includes the preparation o f SHW. Phase Two provides a procedure to calculate solar photolysis rate constants and half lives o f test chemicals in pure water (PW) and SHW. This phase also includes parallel solar irradiation of a radiometer to calculate kI0 (the indirect photolysis rate in the test vessel, e.g. 40 mL glass VOA vial) and kpE(the near-surface photolysis rate constant in natural water bodies). 1.3 Compatible Analytes. Chemicals that will be subjected to this indirect photolysis screening and testing method include but are not limited to the following compounds: Com pound Perfluorooctanoic acid Perfluorooctanesulfonate Perfluorooctanesulfonam ide N -m ethylperfluorooctanesuIfonam ide N-ethylperfluorooctanesulfonam ide 2-(N-m ethylperfluorooctane sulfonam ido) ethyl alcohol 2-(N -ethy!perfIuorooctane su!fonam ido)ethyl alcohol 1-p erfluorooctene Perfluorooctanehydride A cronvm PFOA PFOS FOSA N -M eFO SA N -E tF O S A N -M eFO SE -O H N -E tF O S E -O H -- 1H, C j-hydride C om pound Perfluorobutanoic acid Perfluorobutanesulfonate Perfluorobutanesulfonam ide N -m ethylperfluorobutanesulfonam ide N -eth ylperfluorobutanesulfonam ide 2-(N-methylperfluorobutanesulfonam ido) ethyl alcohol A cronvm PFBA PFBS FBSA N-M eFBSA N -EtFBSA N-M eFBSEOH 2-C N -ethylperfl u oro bu tanesu lfo n a m id o )e th y 1 alcohol N -E tF B S E -O H 1- p e r f l u o r o b u te n e Perfluorobutanehydride -- 1H, C4-hydride ... and other C4 through C 10 hom ologues, and polym eric m aterials based on the above aforem entioned com pounds. 1.4 Acceptable matrix. Synthetic humic water (SHW), 0.005 M pH 7.0 Phosphate Buffer. ETS-8-177.0 In direct P hotolysis Screening Tests in Synthetic Hum ic W ater Page 2 o f 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 standardized synthetic humic water is prepared by water extraction of commercial humic material. The SHW is buffered at pH 7 with 0.005 M Phosphate buffer to maintain pH and pre-aged in the photoreactor to produce predictable bleaching behavior. It is then diluted at the time of use to a UV-visible absorbance typical o f most surface fresh waters (approximately 0.5 AU at 370 nm). 2.2 Phase Two: Study samples (5mL aqueous matrix) are prepared in 40 mL glass VOA vials equipped with screw-top caps with septa. Test substance is added to the vials where indicated. (See table below.) Vials are placed in the photoreactor and immersed in a water bath controlled at 25 5 C. Samples to be exposed are photolyzed in the photoreactor at 261 W/m2(300-800 nm) for designated time intervals. A suggested set of time intervals is listed below. Additional timepoints may be added, if necessary, or as assigned by the Team Leader. Time 0 samples will be refrigerated at 1-5 C. until all timepoints have been completed. Dark controls (unexposed) will also be prepared for each timepoint. Absorbance controls will be used to monitor photo-bleaching of the SHW. Exposed and unexposed'absorbance controls will be prepared per timepoint. 2.2.1 Samples to be prepared for each timepoint and for each exposure type: Description SampleRep1 SampleRep2 SampleRep3 SampleSpikel SampleSpike2 MatrixBlank MatrixBlankSpike Control Matrix(#l)blank Control Matrix(#l}sample ControlMatrix(#l)spike ControlMatrix(#2)blank Control M a trix (# 2 ) sample ControlMatrix(#2)spike AbsorbanceControl AbsorbanceControl dup Test Matrix (Buffer /SHW) + + + + + + 0 0 0 0 0 0 + f Control Matrix1 (Buffer/ PW) 0 0 0 0 0 0 0 + + + 0 0 0 0 0 Control Matrix2 (PW) 0 0 0 0 0 0 0 0 0 0 + + 0 0 Test Substance + + + + + 0 0 0 + + +0 4- 0 0 Post Photolysis Target AnalyteSpike 0 0 0 + .+ 0 + 0 0+ +00 0 0 LC/MS I GC/MS Analysis Analysis AA AA AA AA AA AA AA A A A A AA AA A A A A NA NA NA NA UV/VtsAnalysis at370nm NA NA NA NA NA NA NA ' NA NA NA NA NA NA A A| Where "+" = addition of solution or test substance and "0" = NO addition, A= analysis performed, and NA = no analysis. Tim e Point 0 8h r 16 hr 32 hr 64 hr 128 hr if o f E xposed S am ples 0 30 30 30 30 30 # o f Unexposed S am ples 30 (Time 0) 30 30 30 30 30 # o f samples for LC/MS A nalysis ( Exp + Unexp) 13 26 26 26 26 26 # o f samples for GC/M S Analysis (Exp + Unexp) 13 26 26 26 26 26 # o f sam ples for UV/V is Analysis (Exp + Unexp) 4 S 8 8 8 8 Total # o f Samples 150 ISO 143 143 44 ETS-8-177.0 In direct P hotolysis Screening Tests in Synthetic Hum ic W ater Page 3 o f 16 Page 80 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 3.0 Q u a l it y c o n t r o l - d e f in it io n / f r e q u e n c y /P e r f o r m a n c e c r it e r ia IT! Blanks "~ ' ~ 3.1.1 Definitions: M atrix Blank. A sample of analyte-free matrix (e.g. SHW/buffer) to which all reagents are added in the same volumes or proportions as used in sample processing. For photolysis studies, there are multiple matrix blanks to adequately represent the variables of the study with reference to the matrix (e.g. Exposed, Unexposed and Time 0). The matrix blank is carried through the sample preparation, photolytic and analytical procedures to monitor for contamination during any step. It is also used to establish a chromatographic baseline and monitor for interference or suppression o f target analyte(s) from the matrix. Control Blank. A sample of analyte-free control matrix (such as buffer or ASTM Type II water) to which all reagents are added in the same volumes or proportions as used in sample processing. The control matrix serves as a monitor o f the effect of the matrix on the test substance, test analytes and chromatographic behavior. For photolysis studies, there are multiple control blanks to adequately represent the variables o f the study with reference to the matrix (e.g. Exposed, Unexposed and Time 0 samples). The control blank is carried through the sample preparation, photolytic and analytical procedures to monitor for contamination during any step. It is also used to establish a chromatographic baseline and monitor for interference or suppression o f target analyte(s) from the control matrix. 3.1.2 Frequency/Performance Criteria: Listed in the following table: Matrix ID Matrix Blank (Buffer/SHW) Control Blank #1 (Buffer/PW ) Control Blank #2 (PW) M atrix descriDtion Freauencv 0.01 M Phosphate Buffer, pH 7: Synthetic Humic Water 0.01 M Phosphate Buffer, pH 7 : A STM Type n W ater ASTM TypeH Water 1 Replicate per light and dark exposure, for each tune point and for each analytical methodology. Performance Criteria Any background level of target analyte shall be less than 25% the area counts of the LOQ. 3.2 Sample Triplicate 3.2.1 Definition: Three aliquots prepared as representatives o f the same sample source (e.g. test substance) and carried through all steps of the photolytic study process and analytical procedures in an identical manner. The results from triplicate analyses are used to evaluate variance of the total method, including sample preparation, photolytic process and analysis. ETS-8-177.0 In direct P hotolysis Screening Tests in Synthetic Humic W ater Page 4 o f 16 Page 81 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 3.2.2 Frequency/Performance Criteria: Listed in the following table: M atrix Descrintion Freouencv Test Matrix a n d test 3 Replicates per substance treatment type Performance Criteria The analyst shall accept %RSDs <25%. Precision values >25% must be documented and justified (if possible). 3.3 Analytical Spike (AS) 3.3.1 Definition: A known mass of target analyte(s) in a specified amount o f a diluted and/or aliquotted sample. This assumes that an independent estimate o f target analyte concentration is available. Analytical spikes are used to evaluate the recovery efficiency of the analyte and the matrix effect. 3.3.2 Frequency/Performance Criteria; Listed in the following table: Matrix Description Test Matrix a n d test substance, spiked with target analyte(s) just prior to analysis Test Matrix w ith N O test substance, spiked with target analyte(s) just prior to analysis Control Matrix (#1) and test substance, spiked with target analyte(s) just prior to analysis Control Matrix (#2) a n d test substance, spiked with target analyte(s) just prior to analysis Frequency . 2 spiked samples per treatment type (one in lower half of the calibration range, and one in the upper half of the calibration range) 1 Replicate per treatment type (mid-range spike concentration) Performance Criteria The analyst shall accept accuracy of 100 + 25%. If accuracy is outside o f this range, document and justify, if possible, the reason for the deviation. 3.4 Control Sample 3.4.1 Definition: A known matrix containing the test substance carried through the entire sample preparation, photolytic and analytical procedure. This is used to document laboratory performance by comparing recoveries and matrix effects from the different matrices and sample types. 3.4.2 Frequency/Performance Criteria: Listed in the following table: M atrix Description Control Matrix (#1) a n d test substance Buffer/PW Control Matrix (#2) a n d test substance PW Frequency Performance Criteria 1 Replicate per light and dark exposure, for each time point, and for each analytical methodology The analyst shall accept accuracy of 100 25%. If accuracy is outside of this range, document and justify, if possible, the reason for the deviation. In direct P hotolysis Screening Tests in Synthetic Humic W ater Page 82 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 3.5 Absorbance Control 3.5.1 Definition: An analyte-free matrix that is carried through the sample processing procedure and analyzed by absorption spectroscopy at 370 nm. It is used to monitor the photo-bleaching rate of the SHW during the testing phase. 3.5.2 Frequency/Performance Criteria: Listed in the table below. Matrix Description Control Matrix (#1) Buffer/SHW only Frequency 2 Replicates per light and dark exposure, for each time point Performance Criteria Absorbance measured at 370 nm is between 0.01AU-0.05 AU (1 cm pathlength cell) 3.6 Internal Standard/Surrogate 3.6.1 Internal Standard Definition (applies to LC/MS samples); A known amount o f a compound similar in analytical behavior to the target analyte(s) of interest (e.g. 3, 3,4, 4, 5, 5, 6,6, 7, 7, 8,8, 8-tridecafluorooctane sulfonic acid (THPFOS) if perfluorooctane sulfonate (PFOS) were to be the target analyte), added to all samples and standards (post-irradiation), and carried through the entire analytical process. It provides a reference for evaluating and controlling the precision and bias o f the applied analytical method. Samples are to be quantified using the internal standard. 3.6.2 Surrogate Definition (applies to LC/MS and GC/MS samples): A known amount o f a compound similar in analytical behavior to the target analyte(s) that may be added to all samples (pre- or post-irradiation, at the discretion o f the Team Leader), and carried through the remaining sample preparation and/or analytical process. If added before exposure, it monitors the presence o f vial leaks during photolysis, as well as the performance of the purge and trap autosampler and concentrator. Surrogate analysis is used to evaluate the precision and bias of the applied analytical method. Surrogates are not used for quantitation. 3.6.3 Frequency/Performance Criteria: Listed in the following table: M atrix Descriution Freauencv of Use Sample diluted with 30 mL of internal standard compound dissolved in a suitable analytical solvent Every LC/MS sample analyzed Sample with surrogate compound spiked into it. May be added to every LC/MS and GC/MS sample analyzed Performance Criteria The %RSD for internal standards shall be calculated for the area response of all appropriate samples per analytical batch. The analyst shall accept %RSD values o f <15%. %RSD values >15% shall be documented and justified, if possible. The % recovery of internal standards should be 100 25%. .Surrogates are examined for qualitative information only (i.e., area response should be relatively constant). . ETS-8-177.0 Indirect P hotolysis Screening Tests in Synthetic H umic W ater Page 6 o f 16 Page 83 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 3.7 Other Definitions. 3.7.1 Test Substance/Test Analyte: Any substance (mixture or controlled compound) added or administered to the test system for the purpose of chemical analysis. 3.7.2 Degradation Produces): Secondary analytes of interest produced as a result of chemical reactions during the photolysis and monitored (qualitatively or quantitatively) during the sample analysis procedure. 3.7.3 Target Analyte(s): The analyte(s) singled out in the analytical phase o f the study is the target analyte. The target analyte may be identical to the test substance used in the experimental phase of the study, a by-product or degradation product that is monitored (qualitatively or quantitatively) during the sample analysis procedure. 3.7.4 Test M atrix: The physical matrix in which the study will be conducted. 3.7.5 Relative Percent Difference (RPD): A measure of precision defined as the absolute value o f the difference o f the two values divided by the average of the two values and multiplied by 100. 3.7.6 Relative Standard Deviation (RSD): A measure o f relative precision for three or more sample replicates; defined as the sample standard deviation divided by the sample average and multiplied by 100. This is expressed as a percent (%RSD). 3.7.7 Limit of Quantitation (LOQ): The lowest concentration that can be reliably achieved within specified limits of precision and accuracy during routine laboratory operating conditions. The LOQ can be estimated as 10 times the background level in the blank samples. However, it may be nominally chosen within these guidelines to simplify data reporting. For many analytes, the LOQ analyte concentration is selected as the lowest non-zero standard in the calibration curve that is over four times the background level in the blanks. Sample LOQs are highly matrix-dependent. 4.0 Warnings and Cautions 4.1 Health and Safety Warnings 4.1.1 Wear the proper lab attire for all parts o f 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 o f cooling water that poses a threat of electrocution when handling the photoreactor during irradiation sequences. ETS-8-I77.0 In direct P hotolysis Screening Tests in Synthetic H um ic W ater Page 7 o f 16 Page 84 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 4.2.2 Wear dark protective eyewear when operating the reactor. Do not look directly at the activated lamp. Use caution when handling samples in the reactor; the interior walls o f the reactor and exposed glass vials become extremely hot. 5.0 I n t e r f e r e n c e ____________________________________________________________________ 5 J Contaminants in solvents, reagents, glassware and other sample processing or analysis hardware may cause interference. To reduce the possibility of interference, glassware in which standards are prepared should be pre-rinsed with methanol and allowed to dry before use. The routine analysis of laboratory method blanks must be used to demonstrate that there is no interference under the conditions of the analysis. 6.0 Equipment___________________________________________________________________ 6.1 Analytical balance sensitive to 0.1 mg 6.2 Photoreactor: Suntest CPS+, XLS+, or equivalent, capable of producing 250-765 Watts/m2, equipped with a xenon arclamp (e.g. 2200 W Xenon Lamp) and the appropriate filters to allow the desired wavelength (e.g. UV Special Suprax with cut-on at 290 nm, and Quartz dish with IR reflective coating), and a flowing water bath circulating pump or equivalent. 6.3 Water cooler/recirculator capable of maintaining temperature at 25 C 5 C . 6.4 UV-Visible Spectrophotometer (UV-VIS), equipped with tungsten and deuterium lamps, model 8453, or equivalent 6.4.1 Autosampler: Model G1120A, or 1-cm pathlength cell holder: Model 08451 - 60104, or equivalent. 6.4.1.1 1-cm pathlength quartz spectrophotometer cell, or equivalent. 6.4.2 Long Path-Length Cell Holder, Hewlett Packard part number 89076C, or equivalent 6.4.2.1 10-cm path length quartz cell equipped with stopcocks, Hewlett Packard Part # 5061-3392, or equivalent. 6.4.3 Data acquisition and analysis software, HP ChemStation for UV-Visible Spectroscopy, G1116AA Rev. B.01.02, or later. 6.5 Data System: A PC capable o f controlling the UV-Visible Spectrophotometer system. 6.6 Centrifuge capable o f maintaining >2000 rpm for 10 minutes at ambient temperature (22 26 C). 6.7 Radiometer, capable o f detecting and recording irradiation output of the photoreactor for the duration o f the study. 6.8 Lab Oven, capable o f maintaining 70-80 C. 7.0 S u p p l ie s a n d M a t e r ia l s ____________________________________________________________ 7.1 40-mL amber and clear glass vials (VOA) with screw caps. 7.2 Crimp cap autovials: 1.5-mL, caps, crimper, and decapper. 7.3 Adhesive-backed labels (return address size) for labeling quartz vials and autovials. 7.4 Disposable glass graduated pipettes, 1 mL to 10 mL. ETS-8-177.0 Indirect P hotolysis Screening Tests in Synthetic Humic W ater Page g jg 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 Volumetric flasks, from 10 mL to 1000 mL. 7.8 Hamilton Gastight syringes (precision 1% of the total volume), 5 jaL to 1000 pL. 7.9 10-mL Bottle-top dispenser, 7.10 Teflon filters filter holder apparatus: 0.4 pm pore-size and 0.2 pm pore-size filters (47 mm diameter, GelmanTM or equivalent. 7.11 500-mL glass screw-top containers. 8.0 Reagents and Standards______________ ________.___________________________ 8.1 Water/Pure water (PW), ASTM Type II water at a minimum 8.2 Methanol (MeOH), HPLC/SPEC/GC grade from EM Science or equivalent. 8.3 Acetone, HPLC/SPEC/GC grade from EM Science or equivalent. 8.4 Acetonitrile, HPLC/SPEC/GC grade from EM Science or equivalent. 8.5. Humic acid, sodium salt, from Aldrich or equivalent. 8.6 NaOH, reagent grade from EM ScienceTM or equivalent. 8.7 0.1% NaOH solution Example: Weigh approximately 1.0 g sodium hydroxide into a weigh boat and transfer quantitatively to a 1 L volumetric flask and dilute to the mark with PW or equivalent. 8.8 Sulfuric Acid (H2S 0 4), reagent grade from Fisher or equivalent. 8.9 Potassium phosphate, reagent grade from JT Baker or equivalent. 8.9.1 0.005 M, pH 7.0 Phosphate Buffer. Example: Weigh 1.36 g KH2P 0 4into a weigh boat and transfer to a 1 L volumetric flask using PW and dilute to the mark. Transfer the 1 L o f solution to a 2 L volumetric flask. Add 600 mL of 0.1% NaOH, adjust the pH to 7.0 0.1 with 0.1% NaOH or dilute H2S 0 4, and dilute to the mark with PW. 8.10 Method Blank Solutions: Method Blank Tvnes Matrix ID Test Matrix Buffer/SH W Control Matrix (#1) B uffer/PW Control Matrix (#2) P W Matrix description Example: 1:10 Solution: Dilute 50 mL Synthetic Humic Water with 0.01 M pH 7.0 Phosphate Buffer solution to 500 mL. Example: 1:10 Solution: Dilute 50 mL Pure Water (ASTM Type II) with 0.01 M pH 7.0 Phosphate Buffer solution to 500 mL. Pure Water (ASTM Type II) 8.11 Stock Solutions. Stock solutions for internal standards and spiking solutions are prepared in MeOH at concentrations of approximately 10,000 pg/mL by weighing approximately 0.1 g of the appropriate substance into a 10-mL volumetric flask and bringing to the mark with MeOH. Dilute to make appropriate working solutions. 8.11.1 Diluting Solution with Internal Standard: The diluting solution shall contain internal standard at an area response level equivalent to approximately half the ETS-8-177.0 Indirect P hotolysis Screening Tests in Synthetic Humic W ater Page 9 o f 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 calibration curve. Example: Internal standard solution in MeOH is prepared by diluting 50pL o f internal standard stock solution (Section 8.11) to 1 L with MeOH to a nominal concentration o f 0.5 AU gg/mL. 8.12 Test Solutions 8.12.1 Test Substance: Prepare a solution of the test substance in acetonitrile. Calculate the concentration so that after the test substance is added to the test vial, no more than 1% of the volume in the test vial will be solvent, (e.g. 50pL added to 5 mL o f matrix = 1 % v/v) Then measure the absorbance o f the test substance solution diluted with buffer/water matrix to the desired concentration. The maximum absorbance at any wavelength greater than 290nm must be < 0.05, when measured in a standard 1-cm pathlength cell. Example: A 900 pg/mL solution o f test substance in acetonitrile is prepared by weighing 90 mg o f test substance into a 100 mL volumetric flask and diluting to the mark with acetonitrile. 9.0 Sample Handling 9.1 Record times o f initial preparation and dilution on the fluorochemical degradation (photolysis) analysis sample prep sheet (Attachment A). 9.2 Once the test substance solution has been added, the 40 mL VOA sample vials shall be stored and handled cap-side down to minimize loss of any potential volatile analytes. After the exposure period, the LC/MS samples may be turned upright and stored in a cooler at 1-5 C. After the exposure period, GC/MS samples shall be maintained in an inverted position in a cooler at 1-5 C until they are loaded onto the autosampler. 9.3 Once the 30-mL aliquot o f diluting solvent has been added to the LC/MS photolysis samples, (see Section 12.0), the samples should be analyzed as soon as possible. Alternatively, the samples may be stored at 1-5 C. Day 0 samples are to be stored at 1-5 C during the time of sample exposure, and then diluted along with the exposed and unexposed samples just prior to analysis. 10.0 Quality Control______________________________________________________ 10.1 Quality control parameters (and the frequency o f use) are included in Section 3.0. 11.0 Calibration and Standardization_______________________________________ 11.1 The analytes of interest must be standardized according to laboratory specifications. 11.2 All equipment used, such as the analytical balance, photoreactors, etc. should be calibrated prior to use (daily, 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 Photolysis Screening Tests in Synthetic Humic W ater Page 10 o f 16 Page 87 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 12.0 Procedures__________________________________________________________ 12.1 Phase One-Preparation and standardization of synthetic humic water. 12.1.1 Weigh approximately 2.5 g humic acid into a tared 250 mL centrifuge tube. 12.1.2 Add 0.1% NaOH solution to 250 mL. 12.1.3 Screw-cap shut and tape the tube and place horizontally on an orbital shaker. Shake vigorously (e.g. 100-250 rpm) at room temperature for approximately one hour. 12.1.4 Centrifuge the 250 mL o f solution at approximately 2000 rpm for 10 minutes or until solution has cleared, and then filter the supernatant through a 0.4pm filter into a clean 500-mL glass screw-top container. 12.1.5 Adjust the pH o f the solution to 7.0 with dilute H2S04or 0.1 % NaOH. 12.1.6 Filter-sterilize the solution through a 0.2pm diameter pore-size filter into a clean 500-mL glass screw-top container. 12.1.7 Seal the container and place cap-side down in the photoreactor chamber. 12.1.8 Expose the SHW 24 hours at 261 W/m2to pre-age the solution (equivalent to three day's worth o f Miami, Florida sunlight). The EPA's definition o f " 1 Day" o f irradiation is "eight hours." The irradiation intensity o f 261 W/m2was chosen because it yields the equivalent average optimum natural daylight radiation for 300-400 nm (see the table below): Annroximate Intearated and Individual Irradiances in W/m2 Irradiance Source 250-300 nm 300-400 nm 400-800 nm 340 nm 420 nm Average Optimum Natural Daylight1 0.0 27.8 259.0 0.30 0.67 Atlas Photoreactor with integrated irradiance output of 261 W/m2300-800 nm using the IR Reflecting and 290 cuton filters 0.08 27.8 'M e a su re d --2 5 N , M ia m i, F lo rid a (S e e R e fe re n c e 18.4) 234.36 0.24 0.71 12.1.9 Aliquot the SHW into a 1-cm quartz UV-VIS cuvette and analyze the absorbance at 370 nm. 12.1.10 Check the pH o f the solution using pH paper or a pH probe. Adjust the pH if necessary to 7.0 + 0.1 using a dilute H2S 04solution or 0.1% NaOH solution. 12.1.11 Calculate the dilution factor necessary to decrease the absorbance to approximately 0.5 AU (in a 1-cm pathlength cell) in 1 L of SHW: where: Q t.? = A jxwo 1L X Ax. 370= the measured absorbance o f the SHW at 370 nm x = the volume o f SHW needed to dilute to 1 L with water. 12.1.12 Bring the solution to the exact dilution calculated in 12.1.11 with PW. ETS-8-177.0 In direct P hotolysis Screening Tests in Synthetic Humic W ater Page 11 o f 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 SHW into a 1-cm UV-VIS cuvette and taking the absorbance reading at 370 nm. 12.1.14 Transfer the SHW stock solution into an amber, or clear foil-wrapped 1 L glass storage bottle, tightly cap and refrigerate. 12.2 Phase Two 12.2.1 Fill out the "Fluorochemical Degradation (Photolysis) Sample Prep Sheet" (Attachment A) as much as possible, assigning sequential unique ID numbers to each sample to be prepared. 12.2.2 Obtain the appropriate number of clear and amber 40-mL glass vials with caps and cardboard boxes. Label the vial caps using a black permanent marker to distinctly identify samples. 12.2.3 Create labels for each sample to be affixed to the 40-mL vials and the autosampler vials after photolysis is completed. The labels should include the sample number, test substance, matrix, exposure type (e.g. exposed/unexposed/Time 0), date and initials of the analyst. 12.2.4 Aliquot 5.0 mL of Buffer/SHW, Buffer/PW and PW solutions into clear (for exposed samples) and amber (for unexposed and Time 0 samples) 40-mL glass VOA vials. Add test substance to the appropriate vials. See the table below for list of vials, replicates, and sample types. If pre-hydrolysis surrogates are to be used, add them also at this point. 12.2.5 Create one set o f samples (listed below) per time point and for each analytical methodology. (LC/MS and GC/MS): Description SampleRep1 SampleRep2 SampleRep3 SampleSpike1 SampleSpike2 MatrixBlank MatrixBlankSpike CCoonnttrroollMMaattrriixx((##ll))bsalamnpkle Control Matrix(#l)spike ControlMatrix(#2)blank Control Matrix(#2)sample Control Matrix(#2)spike TestMatrix (Buffer/SHW) + + 4* + + + + 0 0 0 0 0 0 ControlMatrix1 (Buffer/PW) 0 0 0 0 0 0 0 + + + 0 0 0 Control Matrix2 (PW) 0 0 0 0 0 0 0 0 0 0 + 4- SampleRep1 SampleRep2 SampleRep3 SampleSpike1 SampleSpike2 TestMatrixBlank TestMatrixBlankSpike ControlMatrix(#I) blank ControlMatrix(#l)sample Control Matrix(#l)spike Control Matrix(#2)blank ControlMatrix(32)sample Control Matrix(32)spike + + 44+ + 4* 0 0 0 0 0 0 0 0 0 0 0 0 0 + 440 0 0 0 0 0 0 0 0 0 0 0 0 4+ + Where "+" = addition o f solution or test substance and "0" = NO addition TestSubstance + + + + + 0 0 0 + + 0 + 4* + + + + + 0 0 0 + + 0 + + ETS-8-177.0 In direct P hotolysis Screening Tests in Synthetic Hum ic W ater Vial Type/Exposure Clear/Exposed Clear/Exposed Clear/Exposed Clear/Exposed Clear/Exposed Clear/Exposed Clear/Exposed C lear/Exposed Clear/Exposed Clear/Exposed Clear/Exposed Clear/Exposed Clear/Exposed Amber/Unexposed Amber/Unexposed Amber/Unexposed Amber/Unexposed Amber/Unexposed Amber/Unexposed Amber/Unexposed Amber/Unexposed Amber/Unexposed Amber/Unexposed Amber/Unexposed Amber/Unexposed Amber/Unexposed Page 12 o f 16 Page 89 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 Control Matrix(#l)= SHW/Buffer 1:9 v/v Control Matrix(#2)= PW/Buffer 1:9 v/v Create one set o f samples (listed below) for each time point for UV/VIS analysis: Description TestMatrix ControlMatrix1 ControlMatrix2 (Buffer/SHW) (Buffer/PW) <PW) AbsorbanceControl - Light + 0 0 AbsorbanceControl - Dark + 0 0 TestSubstance 0 0 VialType/Exposure Clear/Exposed Amber/Unexposed 12.2.6 Store the "Time 0" vials in a labeled box at 1-5 C. 12.2.7 Place all the vials that will go into the photoreactor into an oven set to 70-80 C. for 5-10 minutes to acclimate the vials, liquid and headspace to photoreactor conditions. Upon removing the vials from the oven, immediately re-tighten the caps and proceed to load the reactor. 12.2.8 Place the amber "unexposed" vials in plastic bags and arrange on the bottom of the photolysis tray (make sure that they don't float once the tray is filled with water). The "unexposed" vials will remain submerged in the cooling water (25 5 C) during the exposure. (The vials are exposure- and temperature-controlled.) 12.2.9 Place the clear "exposed" vials in the rack in the photoreactor tray cap-side down, and install the rack so that the VOA vial caps will be submerged throughout the duration of exposure. 12.2.10 Prepare the radiometer to read intensity of irradiance over the duration of the exposure. See SOP ETS-9-50.0 for operation of radiometer. 12.2.11 Expose the samples for the designated time intervals at 261 W/m2. See SOP ETS-9-44.0 for operation o f the photoreactor. 12.2.12 Following each exposure interval, remove vials from the photoreactor and store inverted in a cooler at 1-5 C. After all exposures have been completed, remove all sample vials as well as the "Time 0" vials from the cooler and analyze as a single batch for each instrument. 12.2.13 UV-VIS absorbance control analysis 12.2.13.1 Analyze the pH 7.0 SHW/buffer absorbance controls by UV/Visible absorbance spectroscopy at 370 nm by aliquoting the test solution directly into a 1-cm or greater pathlength quartz cuvette and obtaining the spectra. See SOP ETS-9-46.0 for operation of the UV/VIS instrument. The resultant peak at 370 nm will be analyzed to determine the change in absorbance between the Time 0, exposed and unexposed samples. 12.2.14 LC/MS sample analysis 12.2.15 Dilute the exposed and unexposed samples for all timepoints with 30 mL internal standard solution in methanol (Section 8.11.1). Add spiking solution to the appropriate vials. Invert each vial several times to mix. 12.2.16 Transfer aliquots o f LC/MS samples into autovials and then place them in the autosampler for analysis o f the parent compound and possible degradation products. Analyze according to ETS-8-181.0. 12.2.17 GC/MS sample analysis ETS-8-177.0 Indirect P hotolysis Screening Tests in Synthetic Humic W ater Page 13 o f 16 Page 90 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 12.2.17.1 Analyze the exposed and unexposed samples for all timepoints as-is by purge and trap GC/MS. Add spiking and surrogate solutions, as required, to the appropriate vials. Analyze according to ETS-8-182.0. 12.2.17.2 Im portant: Maintain vials in the inverted position until they can be placed in the autosampler. 13.0 Data Analysis and Calculations_________________________________________ __ 13.1 Not applicable, as this is a sample preparation and analysis method. Consult the appropriate analytical protocol for guidance regarding data analysis and calculations. 14.0 M e t h o d P e r f o r m a n c e __________________________________________________________ 14.1 Not applicable. 15.0 P o l l u t io n P r e v e n t io n a n d W a s t e M a n a g e m e n t ______________________ ;________ 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 o f glass pipettes. 16.0 R e c o r d s _________________________________________________________________________ 16.1 Print out hard copies of all graphics and data analysis summaries for archiving. 16.2 Sign and date all graphics and label with instrument ID. 16.3 Fill out the sample preparation worksheet(s) documents completely, making sure to include all initials and dates. 16.4 Archive electronic data to compact disc media. 17.0 A t t a c h m e n t s __________________________________________________________________ _ 17.1 "Fluorochemical Degradation (Photolysis) Sample Prep Sheet" 18.0 References_________________________________________________________________ 18.1 Interpersonal conversation with Carrie O'Connor, Optical Systems Engineer, Atlas Electric Devices. 18.2 "Suntest CPS/CPS+ Spectral Irradiance Distribution," table distributed by Atlas Electric Devices Company, sent via fax by Richard Sherwin, Sales Representative, 26 July, 2000. 18.3 "Atlas Xenon Filter Combination and Sunlight Measurements," information generated by Atlas Electric Devices Company sent via fax by Richard Sherwin, Sales Representative, 26 July, 2000. 18.4 OPPTS 835.5270, Indirect Photolysis Screening Test: Sunlight photolysis in water containing dissolved humic substances. ETS-8-I77.0 Indirect P h otolysis Screening Tests in Synthetic Humic W ater Page 14 o f 16 Page 91 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 19.0 Affected Documents 19.1 None 20.0 Revisions________________________________________ _________________________ Revision Revision Number. Reason For Revision ETS-8-177.0 Indirect Photolysis Screening Tests in Synthetic Humic W ater Page 15 o f 16 Page 92 of 165 3M Environmental Laboratory Report No. W2783 Attachment A- Photolysis Sample Prep Sheet TEST ANALYTE: Lab Request Number: Nom inai Tim e Interval: Reactor Tem perature: Fluorochentlcal D egradation (P ho to ly s is ) S am ple Prep S heet P holoreaetor ID: _______ S ta rt D a te :___________T im e :___________ Stop D ate: Tim e: Total R eactor T im e: d a y s _______ hou rs _ C o lr S torage ID: D ate Trme In Date &Tim e O ut Initials C o oler S torage ID: D ate & T im e In Date Tim e O ut Initials BACK TO MAIN NO TE: Dark shaded areas re q u ire NO a d d itio n s UA = n o t ap p H a b t * Com m ents: ETS-8-177.0 In direct P hotolysis Screening Tests in Synthetic H um ic W ater Page 16 o f 16 Page 93 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 3M Environmental Laboratory Equipment Procedure O peratio n and M aintenance of th e H ew lett Packard 8453 UV-V isible Spectrophotometer Procedure Number: ETS-9-46.0 Exact Copy of Origina* Approved by: Laboratory Management ,/ Adoption Date: ^o j 7.0j o D Revision Effective Date: Date ' Date ETS-9-46.0 Operation and Maintenance o f the HP8453 UV-Vis Spectrophotometer Page 1 of 9 Page 94 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 1.0 S c o p e a n d A p p l ic a t io n 1.1 This equipment procedure describes the operation, cleaning, and maintenance of the Hewlett-Packard 8453 UV-Visible Spectroscopy System. 2.0 D e f in it io n s _____________________________________________________________ 2.1 Absorbance: Measure of concentration o f material present: expressed as product of molar extinction coefficient (s), pathlength (b), and concentration (c), written as A = s b c (also known as Beer's Law). 2.2 Cuvette o r flow cell: Transparent receptacle in which sample solutions are introduced into the light path of spectrometers. Usually, two sides are equal (e.g. 1 cm x 1 cm) while the third dimension is elongated, possibly as long as 15 cm. For UV work, the material is quartz. Visible work permits the use of glass or plastic cuvettes. 2.3 Pathlength: The distance the light passes through the sample in its holder. In practical terms, the inside dimension of the cuvette (usually 1 cm). 2.4 Slit width: Size o f opening through which light from cuvette emerges. Choice o f slit width depends on wavelength range, separation ability of wavelength selector, and desired isolation of specific wavelength. Slit width is often fixed or automatically programmed. 2.5 Solvent Cutoff: The wavelength at which the solvent absorbs a significant portion of the light, causing a loss of signal. In other words, the solvent becomes opaque to the wavelengths being used. This is common in the ultraviolet, rare in the visible. 2.6 Transmittance: Ratio of the radiant power transmitted by a sample to the radiant power transmitted by a blank in an equivalent cell or by some other means of compensation for solvent absorption, reflection losses, etc. 2.7 Visible: The portion of the electromagnetic spectrum, from 400 to 800 nm, detectable by human eyes. 2.8 Ultra-violet (UV): The portion of the invisisble electromagnetic spectrum composed of wavelengths o f 10-400 nm. In UV spectrometry we are primarily interested in the nearUV (quartz) region extending from 200 to 380 nm. 2.9 UV Spectrum: a plot of wavelength (or frequency) o f absorption versus the absorption intensity (absorbance or transmittance). 3.0 D e s c r ip t io n ___________________________________________________ 3.1 The HP 8453 spectrophotometer is a single-beam, microprocessor-controlled, UV-visible spectrophotometer with collimating optics. The ChemStation for UV-Visible spectroscopy software running on a PC with Microsoft NT operating system provides instrument control, data acquisition, and data evaluation. 4.0 I d e n t if ic a t io n 41 Hewlett Packard G1103A Serial No. CN93500458 4.2 Hewlett Packard 89090A Serial No. DE14300757 5.0 W a r n in g s a n d C a u t io n s _____________________________________________ ______________ 5.1 Health and Safety Warnings: ETS-9-46.0 Operation and Maintenance o f the HP8453 UVrVis Spectrophotometer Page 2 o f 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 adjustments described in the service manual are made with power supplied to the instrument, and protective covers removed. Electricity and heat available at many points may, if contacted, result in personal injury. 5.1.3 Capacitors inside the instrument may still be charged, even though the instrument has been disconnected from its source o f supply. Dangerous voltages, capable of causing serious personal injury, are present in this instrument. Use extreme caution when handling, testing, and adjusting. 5.2 Cautions: 5.2.1 Never touch the quartz envelope of the deuterium lamp with your fingers. Fingerprints absorb UV light and may be burnt in, thus reducing lifetime of the lamp. 5.2.2 Quartz sample cells or sample cells with quartz faceplates are required if you want to use the full 190 to 1100 nm wavelength range of the spectrophotometer. Good quality glass cells may be used when working above 350 nm. Disposable plastic sample cells are not recommended for use. 5.2.3 For high precision measurements, wait until the spectrophotometer and the lamps have reached thermal equilibrium. The time required is a function of environmental conditions but the instrument should be ready after 45 minutes. To determine if the spectrophotometer is in stable working condition, the HP 8453 Self- test may be performed. (See section 13.1) 5.2.4 Ensure cell windows are free of fingerprints and other contamination. 5.2.5 Avoid the use o f alkaline solutions (pH > 9.5) which can attack quartz and thus impair the optical properties of the flow cells. . 5.2.6 Solution in cell should be free of floating particles. 5.2.7 Solution in cell and cell walls should be free of bubbles. 5.2.8 Ensure that solution in cell is homogeneous by thoroughly mixing before measurement. 5.2.9 Blank is measured on the same solvent as sample. 5.2.10 Blank measurement should show a flat baseline. 5.2.11 Cell orientation of blank and sample measurements should be the same. 5.2.12 Ideally, the cell is not removed between sample measurements, which means the cell is filled/rinsed using a pipette or a flow cell is used. 5.2.13 Time between blank and sample measurements should be short. 6.0 Sp e c ia l I n s t r u c t io n s _______________________________________________________________ 6.1 None. 7.0 R e s p o n s ib il it y ______________________________________________________________________ 7.1 The operator is responsible for routine maintenance and cleaning. ETS-9-46.0 Operation and Maintenance o f the HP8453 UV-Vis Spectrophotometer Page 3 of 9 Page 96 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 7.2 The person responsible for the equipment (and an alternate) will be identified in the front o f the equipment logbook, and are responsible for all routine and non-routine maintenance and associated documentation. 8.0 Su p p l ie s a n d M a t e r ia l s _____________________________________________________________ 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 (Part No. 2140-0605). 8.6 Lamp, Tungsten G1315A, Agilent 8453A (Part No. G1103-60001). 9.0 Instrument Cleaning Procedures____________________________________________ 9.1 Cleaning the Stray Light Filter. (Recommended at one-yearly intervals or more frequently when operating the spectrophotometer in a particularly dirty environment.) 9.1.1 Turn off the instrument and disconnect the power cord. Take the plastic and sheet metal rear covers off, see "Removing and Replacing Covers" on page 109 of the HP 8453 Service Manual. 9.1.2 Remove any accessory board or MIO board that may be plugged in from the rear side of the instrument. 9.1.3 Remove the upper rear foam block. 9.1.4 Disconnect the shutter cable from the SPM board. Open the screw that fixes the shutter assembly to the optical unit and remove the shutter assembly. 9.1.5 Dampen a lint-free, surgical cotton swab with reagent grade isopropanol and gently swab the surface of the stray light filter. Repeat several times with clean swabs and alcohol each time. 9.1.6 Use a canister of compressed oil-free air to further clean the stray light filter. 9.1.7 Position the shutter assembly above the source lens and fix the screw that holds it at the optical unit, see Figure 39 on page 124 of the Service manual. Connect the shutter cable to the SPM board. 9.1.8 Replace the upper rear and upper front foam blocks. 9.1.9 If available, replace any accessory board or MIO board (plugged in from the rear side of the instrument). 9.1.10 Replace the plastic and sheet metal rear covers. Push the plastic rear cover down so that it locates on both sides, see "Removing and Replacing Covers" on page 109 o f the HP 8453 Service Manual. 9.1.11 Reconnect the line power and turn on the instrument. Check that the spectrophotometer passes the self-test, this means that the green light on the front panel comes on and that you can do a blank measurement from the software. 9.2 Cleaning the Source Lens from the Sample Compartment Side. (Recommended at oneyearly intervals or more frequently when operating the spectrophotometer in a particularly dirty environment.) 9.2.1 Turn off the instrument and disconnect the power cord. 9.2.2 Remove any cuvette holder from the sample compartment. ETS-9-46.0 Operation and Maintenance o f the HP8453 UV-Vis Spectrophotometer Page 4 of 9 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 surface of the source lens. Repeat several times with clean swabs and alcohol each time. 9.2.5 Use a canister of compressed oil-free air to further clean the source lens. 9.2.6 If you have taken the covers off, replace them. 9.2.7 Replace the cuvette holder: Reconnect line power and turn on the instrument. Check that the spectrophotometer passes the self-test, this means that the green light on the front panel comes on and that you can do a blank measurement from the software. 9.3 Cleaning the Spectrograph Lens. (Recommended at one-yearly intervals or more frequently when operating the spectrophotometer in a particularly dirty environment.) 9.3.1 Turn off the instrument and disconnect the power cord. 9.3.2 Remove any cuvette holder from the sample compartment. 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 109 of the HP 8453 Service Manual. 9.3.4 Dampen a lint-free, surgical cotton swab with reagent grade isopropanol and gently swab the surface of the spectrograph lens. Repeat several times with clean swabs and alcohol each time. 9.3.5 Use a canister of compressed oil-free air to further clean the spectrograph lens. 9.3.6 If you have taken the covers off, replace them. Replace the cell holder in the sample compartment. 9.3.7 Reconnect line power and turn on the instrument. Check that the spectrophotometer passes the self-test, this means that the green light on the front panel comes on and that you can do a blank measurement from the software. 10.0 Maintenance Procedures_________________________________________________ 10.1 Routine maintenance. 10.1.1 Cleaning the stray light filter. Indicators for a dirty stray light filter include: 10.1.1.1 After exchanging the lamps, the intensity test executed by the ChemStation software still falls below the specified level. 10.1.1.2 One o f the stray light tests fails. 10.1.1.3 The photometric accuracy test fails. 10.1.2 Cleaning the lenses that are accessible from the sample compartment side. An indication for dirty lenses is when, after exchanging the lamps, the intensity test executed by the ChemStation software still falls below the specified level. 10.2 Non-routine: Document any non-routine maintenance. 10.2.1 Exchange the deuterium or the tungsten lamp when the intensity test, which is executed through the ChemStation software, falls below the specified level or when one of the lamps no longer ignites. See HP 8453 Service Manual for lamp replacement procedure (p.96). ETS-9-46.0 Operation and Maintenance of the HP8453 UV-Vis Spectrophotometer Page 5 of 9 Page 98 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 11.0 11.1 11.2 11.3 11.4 11.5 Operating Procedures___________________________________________ Powering Up the HP 8453 UV-Visible Spectrophotometer and PC controller. 11.1.1 Switch on the PC and boot the PC operating system. 11.1.2 Switch on the spectrophotometer and wait until the spectrophotometer's indicator light turns green. This process includes the spectrophotometer's self test and takes about one minute. 11.1.3 Launch a measurement session by pressing the operating system's "Start" button and select "Programs", "HP UV-Visible ChemStations", "spectrometer 1 online" 11.1.4 The system is ready to use if the blue "busy" status display on the system's bottom message line turns off. Note: For high precision measurements wait until the spectrophotometer and the lamps have reached thermal equilibrium. The time required is a function of environmental conditions but should be ready after 45 minutes. 11.1.5 The first measurement to perform is a reference measurement. After this alignment you are ready to measure absorbance data and spectra. Inserting a Cell. 11.2.1 The HP 8453 is shipped with the standard single-cell holder which accommodates standard cells or flow cells. 11.2.2 Move the locking lever to its up position. 11.2.3 Insert the sample cell, making sure you orient it correctly. The frosted (non-clear) sides o f the sample cell sh ou ld not be in the path o f the light beam. 11.2.4 Lock the sample cell in place by pushing the locking lever back down. 11.2.5 Small volume flow cells and particularly any cells with less than a 2 mm aperture may require use o f the optional adjustable cell holder. This device helps you ensure the cells are properly centered in the light path. Entering a Cell's Path Length. 11.3.1 Click "Setup" on the Instrument Panel. 11.3.2 Type the path length in cm in the "Setup Manual" dialog box. 11.3.3 Click "OK" to set the specified path length. 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 containing the solvent used with your samples is put in the measurement position and a blank measurement performed. To start this measurement, click the "Blank" button on the Instrument Panel or press the spectrophotometer's "Blank" button. 11.4.3 Perform a sample measurement. To get the most precise results, use the same cell in the same orientation to the measurement beam. Flush the cell about three times with the sample solution and start the measurement by clicking the Instrument Panel's "Sample" button or by pressing the spectrophotometer's "Sample" button. Setting up a Method for Single Component Analysis. 11.5.1 Choose the "Quantification" task from the data analysis panel. 11.5.2 Enter the used wavelength in the input fields. ETS-9-46.0 Operation and Maintenance of the HP8453 UV-Vis Spectrophotometer Page 6 of 9 Page 99 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 11.5.3 If background correction is desired, select "Single Reference Wavelength", "Subtract Average Over a Range" or "Three-point Drop Line" from the background correction combo box. 11.5.3.1 "Single Reference Wavelength" requires the input of one wavelength in the adjacent wavelength edit field on the right side o f the combo box. 11.5.3.2 For "Subtract Average Over a Range" or "Three-point Drop Line" you must define the range/baseline by entering the start and end wavelengths in the two adjacent wavelength edit field on the right side of the combo box. 11.5.4 Specify a name for the analyte. 11.5.5 Choose "Concentration" to enter the analyte concentration directly or "Weight & Volume" to have the ChemStation calculate the concentration. Enter the units for the concentration or the weight and volume. 11.5.6 If you want to be prompted for the concentration of the standards during measurement, select "Prompt for Standard Information". In the combo box you can select whether the prompt asks you for the concentration, or calculates the concentration based on volume, weight and purity. 11.5.7 If you have diluted samples and want to correct for dilution, select "Prompt for Dilution Factor" of sample. 11.5.8 Choose the desired calibration curve type. 11.5.9 Select the desired data type and display range of the spectra in the graphical window. 11.5.10 Choose "OK" to close the dialog box. 11.5.11 Perform the following steps if you want to calibrate the method. 11.5.11.1 Measure a blank on the solvent if necessary using the "Blank" button in the instrument panel. 11.5.11.2 Measure the standards using the "Standard" button in the instrument panel. If you have selected one of the prompts, the appropriate values will be requested in a dialog box. The spectrum is displayed automatically in the "Standard Spectra" window as they are measured. Note: There is no fixed limit to the number of calibration standards that can be incorporated into a calibration. However, each of the calibration curve types requires a minimum number of standards of different concentrations, which can be found in Table 7, page 45 o f the HP Manual: Understanding Your UVVisible Spectroscopy System. The ChemStation software calibrates automatically when at least the minimum number of standards has been measured. A table with the used standards and values as well as calibration curve is displayed. 11.5.11.3 If the calibration is successful, the calibration curve icon o f the data analysis panel changes from red to green. 11.6 Measuring and Displaying an Absorbance Spectrum 11.6.1 Select the "Clear" icon using the Toolbar, to delete any spectral data that you do not wish to keep. 11.6.2 Select the "Spectrum/Peaks" task from the Method menu or data analysis panel. 11.6.3 Select the boxes for "Peak/Valley Find" if necessary. ETS-9-46.0 Operation and Maintenance o f the HP8453 UV-Vis Spectrophotometer page 7 of 9 Page 100 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 11.6.4 Select "Absorbance" as data type. 11.6.5 Set the display range you want to see in the graphical window. 11.6.6 Choose "OK" to close the "Spectrum/Peaks Parameters" dialog box. 11.6.7 Measure a Blank on the solvent if necessary using the "Blank" button in the instrument panel. 11.6.8 Measure all the samples using the "Sample" button in the instrument panel. The spectra are displayed automatically in the "Sample Spectra" window as they are measured and depending on the selected parameters you will get a table o f results. 11.7 Loading Spectra: 11.7.1 Choose "Load" from the "File" menu, then choose the type of spectra that you want to load (Samples or Standards) from the submenu to display the "Load Spectra" dialog box. 11.7.2 If the spectra you wish to load are not in the "File Name" list, select a different directory from the "Directories" list. 11.7.3 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 o f spectra that you want to save (Samples, Standards or Selected Spectra) from the submenu to display the "Save Spectra As" dialog box. 11.8.2 If you wish to save the spectra in a directory other than the current one, select the new directory from the "Directories" list. 11.8.3 Type the name you wish to save the spectra as in the "File Name" field and choose "OK" to close the dialog box. 11.8.3.1 A valid file name consist of eight alphanumeric characters and the file extension .sd or .std. Usually, the extension .std is used for standards only. 11.8.4 You can also save spectra using the ToolBar. 12.0 Records____________________________________________________________________ 12.1 Document all cleaning and maintenance performed on the instrument in the maintenance or run/maintenance logbook. Include a description of the procedure(s) performed, name of person who performed procedure(s), any unusual observations, parts replaced or needing replacement, and whether the procedure was routine or non-routine. Logbooks are archived when complete. 13.0 Testing, C alibration and/or Standardization Procedures 13.1 HP 8453 Self-Test: 13.1.1 Make sure that you are in the "Verification and Diagnostics" mode. The mode is indicated on the tool bar of the HP ChemStation session. 13.1.2 Select the "Self-Test" task in the analysis panel's selection box. 13.1.3 Choose "Self-Test". Start from the "Task" menu or click "Start" to start the self test. 13.1.4 The self-test results will be displayed in a window with pass/fail criteria, 13.2 Calibrating for a single component analysis. ETS-9-46.0 Operation and Maintenance of the HP8453 UV-Vis Spectrophotometer Page 8 of 9 Page 101 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 13.2.1 Calibration for single component analysis is based on the measurement of standard samples with known concentrations. During the calibration process, the software calculates the calibration coefficients, which are then used for the quantification o f unknown samples. 13.2.2 The status for calibration can be seen in the data analysis panel: 13.2.2.1 Uncalibrated: RED dashed calibration curve icon. 13.2.2.2 Calibrated: GREEN continuous calibration curve icon. 13.2.3 To calibrate for single component analysis: 13.2.3.1 Load or set up a method for the "Quantification" task. 13.2.3.2 If the "Standard" spectra window is not displayed, choose "Show" standards in the data analysis panel. 13.2.3.3 You can either load the standards from file or measure them. 13.2.3.4 To measure standards: 13.2.3.4.1 Measure a bank on the solvent if necessary using the "Blank" button in the instrument panel. 13.2.3.4.2 Measure the standards using the "Standard" button in the instrument panel. If you have selected one of the prompts in the method, the appropriate values will be requested in a dialog box. 13.2.4 The spectra are displayed automatically in the "Standard Spectra" window as the standards are measured. A minimum number of standards is required, depending on the selected calibration curve. The ChemStation software calibrates automatically when at least the minimum number of standards have been measured. A table with the used standards and values as well as a calibration curve is displayed. 13.2.5 If the calibration is successful, the calibration curve icon o f the data analysis panel changes from red to green. 14.0 R eferences__________________________________________________________________ 14.1 Definitions obtained from www.spectroscopymag.com. 14.2 HP Manual: Understanding Your UV-Visible Spectroscopy System, Hewlett-Packard: Wilmington, DE, 1997. Part No. Gl 115-90005. 14.3 HP 8453 UV-Visible Spectrophotometer Operator's Manual, Hewlett-Packard: Wilmington, DE, 2000. Part No. G l 115-90012. 14.4 HP 8453 UV-Visible Spectrophotometer Service Manual, Hewlett-Packard: Wilmington, DE, 1998. Part No. Gl 115-90003. 15.0 Affected Documents 15.1 None. 16.0 Revisions Revision Number. Reason For Revision Revision Date ETS-9-46.0 Operation and Maintenance o f the HP8453 UV-Vis Spectrophotometer Page 9 of 9 Page 102 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 3M Environmental Laboratory E quipm ent P rocedure R o u tin e M aintenance o f Ar ch o n P u rg e and T r a p Au to sa m pler , T ek m a r P urge and T rap C oncentrator and A g ilen t G as C hrom atograph/M ass Spectro m eter Procedure Number: ETS-9-49.0 rit o n e 13-' Revision Date: Approved by: Laboratory Manager / y c y 'O Date Date ETS-9-49.0 Routine M aintenance o f the Purge & Trap Autosampler/Concentrator/GC/M S Page 103 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 1.0 Scope and Application (Use Numbered Tier I)__________________________ 1.1 This equipment procedure describes the maintenance required for optimal operation of the Archon Purge and Trap Autosampler, Tekmar Purge and Trap Concentrator and Agilent gas chromatograph / mass spectrometer (GC/MS) system. Specific items requiring routine maintenance include occasional tightening vial escalator's nuts and refilling the Standard Vial and water bottle in the Archon autosampler and periodic cleaning o f the mass spectrometer ion source. 2.0 Definitions___________________________________________________ _ _ jona 1' ~ 3.0 Description______________________________________________________________ 3.1 Archon purge and trap autosampler equipped with Tekmar purge and trap concentrator and Agilent gas chromatograph and mass spectrometer. 4.0 Identification______________________________________________________________ 4.1 System : "Rufus". (An equivalent system may be used). 4.1.1 Autosampler: serial number 13006, Varan, Archon 4.1.2 Concentrator: serial number 90297002, LSC2000, Tekmar 4.1.3 GC: serial number US00034972,6890 G1530A, Agilent 4.1.4 MS: serial number US01180105,5973NG2589A, Agilent 4.1.5 PC: serial number US94850812, D6720T, HP Kayak XA 5.0 W arnings and Cautions_____________________________________________________ 5.1 Health and Safety Warnings: 5.1.1 Cooling the Tekmar before removing the side cover for maintenance prevents contact bums. 5.1.2 Turning off power source for Tekmar before removing the side cover will prevent electric shock. 5.2 Cautions: 5.2.1 It is recommended that a grounded antistatic wrist strap be worn while disconnecting all wires, contacts, or cables which are connected to printed circuit boards within Archon autosampler, Tekmar concentrator or MS analyzer. 5.2.2 To prevent the breakage of the Standard Vial on Archon autosampler, during the refill, do not use any tool and do not overtighten the thumbnut. 5.2.3 Never add oil while the foreline pump is on. 6.0 Special Instructions 6 J Not applicable. ETS-9-49.0 Routine M aintenance o f the Purge & Trap Autosampler/Concentrator/GC/M S Page 2 o f 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 analyst who has been trained to perform these maintenance procedures by a primary custodian. 8.0 Supplies and Materials_____________________________________________________ 8.1 Graphite Ferrules, 0.4 mm I.D. for 0.25 mm columns 8.2 Abrasive paper, Hewlett-Packard, part no. 5061-5896 8.3 Alumina abrasive powder, Hewlett-Packard, part no. 8660-0791 8.4 Acetone, reagent grade 8.5 Dichloromethane, reagent grade 8.6 Methanol, purge and trap grade 8.7 Gloves (clean, lint-free, cotton), Hewlett-Packard, part no. 8650-0030 (large); 8650-0029 (small) 8.8 Cotton swabs 8.9 Chem-wipes 8.10 Glass beakers 8.11 Sonicator 8.12 Base deactivated 2 mm ID gooseneck splitless injection port liners, Restek Corporation, part #20796-210.5, or equivalent 8.13 11 mm diameter Thermogreen LB2 septa, Supelco, part #23163, or equivalent 8.14 Viton injection port o-rings, Restek Corporation, part #20377, or equivalent 8.15 Septum wrench, Hewlett-Packard, part #19251-00100 8.16 Tweezers 9.0 C l e a n in g P r o c e d u r e s N/A 10.0 Maintenance Procedures ___________________________________________ 10.1 Routine: Tighten the elevator's assembly nuts when Archon autosampler displays error message " Elevator not homed position 10.1.1 Stop autosampler run by pressing STOP button on the front display twice. 10.1.2 Open the back cover of autosampler 10.1.3 Tighten top and bottom nuts on the elevator's assembly, do not over tighten them. 10.1.4 Close the back cover of autosampler 10.2 Routine: Fill the water bottle, empty the waste bottle. 10.3 Routine: If internal standards or surrogates are to be used, be certain the Standard Vial is filled with the required internal standard or surrogate. 10.3.1 Turn the helium gas "OFF" with the toggle switch. 10.3.2 Push "System" key, choose Maintenance, Standard Control, Front Park. 10.3.3 Grasp the vial and loosen the black thumbnut. Slide the vial down. ETS-9-49.0 Routine M aintenance o f the Purge & Trap Autosampler/Concentrator/GC/M S Page 3 of 5 Page 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 o f 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 foreline pump maintenance. 10.4.1 Examine the oil level window daily. If the oil level is near or below the lower line then add foreline pump oil. Never add oil while the foreline pump is on. 10.4.1.1 Vent the MSD according to the MSD Hardware Manual. 10.4.1.2 Remove the fill cap. 10.4.1.3 Add pump fluid until the oil level in the window is near, but not above, the upper line. 10.4.1.4 Reinstall the fill cap. 10.4.1.5 Pump down the MSD according to the MSD Hardware Manual 10.4.2 Change foreline pump oil every 6-12 months according to the MSD Hardware manual. 10.5 Nonroutine: Document any nonroutine maintenance in the instrument's maintenance logbook. 11.0 O perating Procedures____________________________ _________________________ 11.1 For operating procedures, refer to an appropriate analytical method, or to the Archon Purge and Trap Autosampler System Operator's Manual, Tekmar LSC200 Instruction Manual and the Hewlett-Packard MSD Hardware Manual for HP 5973N & HP 6890 Series Mass Selective Detectors. 12.0 Records_____________________________________________________________ 12.1 Document any maintenance performed on the instrument in the maintenance or run/maintenance logbook. Include a description of the procedure(s) performed, any unusual observations, parts replaced or needing replacement, and whether the procedure was routine or non-routine. Be sure to date and initial the entry. Logbooks are archived when complete. 13.0 Testing, Calibration and/or Standardization Procedures________________ 13.1 After cleaning the source and allowing sufficient time for the vacuum to pump down and the mass spectrometer to equilibrate to operation temperature, run an autotime; check for improved performance and for the presence or absence of air leaks. A tune report can also be used to check for leaks after performing injection port maintenance. 14.0 References 14.1 Archon Purge and Trap Autosampler System Operator's Manual 14.2 Tekmar LSC200 Instruction Manual ETS-9-49.0 Routine M aintenance o f the P urge & Trap AutosampIer/Concentrator/GC/M S Page 4 of 5 Page 106 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 14.3 Hewlett-Packard MSD Hardware Manual for HP 5973N & HP 6890 Series Mass Selective Detectors. 15.0 A ffected Documents 15.1 None. 16.0 R e v is io n s Revision Number. Reason For Revision Revision Date ETS-9-49.0 Routine M aintenance o f the Purge & Trap Autosampler/Concentrator/GC/M S Page 5 of 5 BACK TO MAIN 3M Environmental Laboratory Report No. W 2783 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) S ubstance IU PA C N am e C hem ical Form ula Id e n tifie r Source E xpiration D ate Storage C onditions C hem ical L ot N um ber Physical D escription P urity S ubstance IU PA C N am e C hem ical Form ula Id e n tifie r Source E xpiration D ate Storage C onditions C hem ical L ot N um ber Physical D escription P urity S ubstance IU PA C N am e C hem ical Form ula Id e n tifie r Source E xpiration D ate Storage C onditions C hem ical L ot N um ber P hysical D escription P urity N -E tF O S E alcohol 2-(jV -ethylperfluorooctanesulfonam ido)ethyl alcohol C 8F 17S 0 2N ( C 2H 5) C H 2C H 20 H 1691-99-2* 3 M S pecialty C hem icals 2002 F ro z en SE035 W hite w ax 9 7 .8 % N -E tF O S A A '-ethylperfluorooctanesulfonam ide C 8F 17S 0 2N H C H 2C H 3 4151-50-2* 3 M Specialty C hem icals 2002 F ro z en SD012 W hite w ax 95% < C 7 P e rflu o ro h e p te n e s (90/10 m ix) 10% 2-Perfluoroheptene, 90% Perfluoroheptene C 4F 9C F = C 2F 5, C 5F ,, C F = C F 2 355-63-5* L ancaster Synthesis 2005 F ro z e n 90004250, TNA 3025 C lear am bient liquid 100% P F O S K S alt P o ta ssiu m p e rflu o ro o c ta n e s u lfo n a te C 8F I7S 0 3K 2795-39-3* 3M Specialty C hem icals 2001 F ro z e n SD009 W hite pow der 8 6 .4 PFOA Perfluorooctonic acid, A m m onium Salt C 7F 15C 0 2N H 4 2395-00-8 * 3M Specialty C hem icals 2002 F ro z e n 1 W hite pow der 97% < FO SA Perfluoroctane-sulfonam ide c 8f 17s o 2n h 2 754-91-6* 3M S pecialty C hem icals 2002 F ro z en SE027 W hite w ax 95% < C s T erm in al H y d rid e 1 ,1 ,2 ,2 ,3 ,3 ,4 ,4 ,5 ,5 ,6 ,6 ,7 ,7 ,8,8, 8 heptadecafluorooctane C 8F 17H 335-65-9* A ldrich C hem ical 2002 F ro z en 04307PN , T N A -2983 C lear am bient liquid 99% C 7 H ydride C 6 H ydride 1, 1,2 ,2 ,3 ,3 ,4 ,4 ,5 ,5 ,6 ,6 ,7 ,7 ,7 p e n ta d e c a flu o ro h e p ta n e c 7f 15h 27213-61-2* L ancaster Synthesis 2005 F ro z en 900591 l.T N A -3026 C lear am bient liquid 97% 1, 1,2 ,2 ,3 ,3 ,4 ,4 ,5 ,5 ,6 ,6,6 trid e c a flu o ro h e x a n e c 6f 13h 355-37-3* L ancaster Synthesis 2005 F ro z en 90005941, T N A -3027 C lear am bient liquid 98% Page 109 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 Reference Substances (continued) Reference Substance IU PA C N am e C hem ical Form ula Id e n tifie r Source E xpiration D ate Storage Conditions C hem ical L ot N um ber Physical D escription P urity Reference Substance IU PA C N am e C hem ical Form ula Id e n tifie r Source E xpiration D ate Storage Conditions C hem ical L ot N um ber P hysical D escription P urity *CAS Number Cg Hydride/Olefin Mix PFBS 1 ,1 ,1 ,2 ,2 ,3 ,3 ,4 ,4 ,5 ,5 ,6,6 ,7 ,8,8,8 pentadecafluorooctane, 2perfluorooctene C 6F 13C F H C F 3' C 6F I3C F = C F 2 T C R -9 9 0 3 0 -1 8 3 M S pecialty C hem icals 6/6/99 F ro z e n 1 C lear am bient liquid 85% C 8 H ydride, 15% C 8 O lefin C4Interior Olefin P e rflu o ro b u ta n e su lfo n a te , potassiu m salt c 4f 9s o 3k 29420-49-3* 3M Specialty C hem icals 2002 F ro z e n T C R -9 9 0 3 0 -0 2 8 W hite Pow der 97% < C3Terminal Hydride 2 -P e rflu o ro b u te n e c 4f 8 360-89-4* L ancaster Synthesis 2002 F ro z e n G 00195, T N A -4298 C lear am bient liquid 97% 1, 1,2 ,2 ,3 ,3 ,3 h e p ta flu o ro p ro p a n e c 3f 7h 2252-84-4* L an caster Synthesis 2010 Flam m able G 0062B , TN A -4294 G as 97% C4Terminal Hydride 1, 1,2 ,2 ,3 ,3 ,4 ,4 ,4 n o n a flu o ro b u ta n e C 4F 9H 375-17-7* C rescent C hem ical 2002 F ro z e n 6A -46, TN A -3997 C lear am bient liquid 99% C2Terminal Hydride 1, 1,2 ,2 ,2 p e n ta f lu o r o e th a n e c 2f 5h 354-33-6* L ancaster Synthesis 2010 Flam m able G 00492, T N A -3021 Gas 99% Page 110 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 Chemical Characterization (Control Substances) Control Substances S tru c tu re IU PA C N am e U se Source E xpiration D ate Storage C onditions C hem ical L ot N um ber Physical D escription P urity Control Substances PFCH cF12 P e rflu o ro c y c lo h e x a n e THPFOS c 8f 13h 4s o 3k P o ta ssiu m 3 ,3 ,4 ,4 ,5 ,5 ,6,6,7 ,7 ,8,8,8 trid e c a flu o ro s u lfo n a te Surrogate Standard For G C /M S analysis Internal Standard for L C /M S analysis A ldrich Chem ical 2005 F ro z en 01911A U C olorless M oist Solid 97% SynQ uest Labs 2003 F ro z en 99022-31, T N A -4154 W hite pow der 95% < Chlorobenzene-ds Toluene-cL Pentafluorobenzene C 6H F 5 P e n ta flu o ro b e n z e n e Instrum ental Surrogate Standard For G C /M S analysis R estek C orp. 6/2002 F ro z en A 013256 M ethanol solution 99% (2500 pg/m L + 0.2% ) Dibromofluoromethane S tru c tu re IU PA C N am e U se Source E xpiration D ate Storage C onditions C hem ical L ot N um ber Physical D escription P urity Control Substances S tru c tu re IU PA C N am e U se Source E xpiration D ate Storage C onditions C hem ical L ot N um ber Physical D escription P urity C 6C 1D 5 C hlorobenzene-d5 Instrum ental Surrogate Standard F or G C /M S analysis R estek C orp. 6/2002 F ro z en AO 13256 M ethanol solution 99% (2500 pg/m L + 0.2% ) 1,4 Difluorobenzene C 6 H 4F 2 1,4 D iflu o ro b en ze n e Instrum ental Surrogate Standard F or G C /M S analysis R estek C orp. 6/2002 F ro z en A 0 13256 M ethanol solution 99% (2500 pg/m L 0.2% ) C7d 8 T oluene-ds Instrum ental Surrogate Standard F o r G C /M S analysis R estek Corp. 2/2002 F ro z en A 0 12973 M ethanol solution 99% (2500 pg/m L + 0.2% ) 4-Bromofluoro-benzene C H B r 2F D ibrom ofluorom ethane Instrum ental Surrogate Standard For G C /M S analysis R estek C orp. 2/2002 F ro z en A 0 12973 M ethanol solution 99% (2500 p g /m L 0.2% ) l,4-Dichlorobenzene-d4 C 6H 4B r F 4-B rom ofluoro-benzene Instrum ental Surrogate Standard F or G C /M S analysis R estek C orp. 2/2002 F ro z e n A 0 12973 . M ethanol solution 99% (2500 pg/m L + 0.2% ) C 6C12D 4 1,4-D ichlorobenzene-d4 Instrum ental Surrogate Standard For G C /M S analysis R estek C orp. 6/2002 F ro z e n A 0 13256 M ethanol solution 99% (2500 pg/m L + 0.2% ) Page 111 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 Appendix C: Kinetics Model and Kinetic Calculations This appendix presents the mathematical description of the kinetics model employed in this study and the application of this model in the determination of the estimated half-lives presented. Page 112 of 165 BACK TO MAIN 3M Environmental Laboratory 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 m, which number N. The actual reactions that occur are subsumed in these equations, and are assumed to proceed with pseudo-first order rates k Pm(forthe parent) and k Aln(forthe products). P + photon - ^ n mA m+ Y ml (m= ltoN ) (C1) A m+ photon -> Ym2 (m = 1 to N ) (C2) where "photon may either represent a photon of light or it may represent some other species in solution that reacted with a photon to produce a new reactive species and the general symbols Yml and Ym2 represent all the other 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 (C3) which is equivalent to the separable differential equation (C4) Equation C4 may be directly integrated to obtain the general solution /N \ to[p]= nm kPmt +c With the initial condition p (t = 0) s P0, the specific solution to Equation C4 is P = P 0 exp N n m k Pmt = P0 e "kpt (C5) (C6) Page 113 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 using the additional definition of the total parent photolysis rate N m=l (C7) Equation C6 can be re-written in a form that allows a least-squares estimate of the total parent hydrolysis rate: (C8) Using the initial (t = 0) measured value of the parent concentration P0and later values P measured at later times t , one can calculate and plot the (linear) quantity [- In (P/P0)] versus time and obtain a least -squares estimate of the slope of the line. The resulting slope is the least-squares estimate k p of the total parent photolysis rate. Equation C6 indicates that over a period of time T 1^ (the parent half-life) the parent concentration P is reduced through hydrolysis by a factor of two, where A least squares estimate f ^ of the parent photolysis half-life Is therefore available from (C10) C3. Product Compound Concentrations The pseudo-first order differential changes in the product concentrations An (using Equations C2 and C6) are d A m= ( n mk Pmp - k AmA ra) dt = ( n mk PmP0 e"kp ` - k AmA m) dt (C11) and the (first order, non-separable) differential equation governing the product concentrations is dA (012) dt Page 114 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 The "standard form" of Equation C12 is A m+ S (t)A ra=Q (t) where the "function" S (t) is actually a constant: s(t)=k*,, and Q (t) = n mk PmP0 e -k>` . The general solution A mto Equation C12 is contained in (C13) (C14) (C15) A e<s(t)dt = jQ ( t) e 's(t')dt' dt + C (C16) where g js ( t) d t _ e JS(t')dt' -- g k t o / d t _ g k ^ t (C17) and j Q ( t ) e JS(t')dt'd t + C = n mk PmP0J ek^ ` e kptdt + C (C18) There are two cases of Equation C18 to consider. In the circumstance that k Atn = k p , which occurs only when the rate of the mth product is identical to the total parent photolysis rate, the general solution to Equation B18 is (for = k P) A me p = n mk PmP0 1+ C (C19) and, using the initial condition A m(t = 0 ) = A ^ , the specific solution to Equation18 is ( f o r k ^ = k P) k. t A m = k k r / o t + A n ) e (C20) We note that when k ^ = k P= 0 (that is, when both the parent and potential product are photolytically stable), Equation C7 requires (also) that k Pm= 0, so Equation C20 becomes Page 115 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 A ,, = A,, (C21) indicating, as required, that the product concentration does not change with time. The circumstance k Am = k p is highly improbable, and is neglected in the remainder of this discussion. However, the reader should bear in mind that the expressions derived below do not hold when the parent photolysis rate k pand the product photolysis rate k ^ approach each other. In the more probable case, for which k Aln * kp (i.e. that the rate of the mth product is different from the total parent rate), the general solution to Equation C18 is A mekA*"` r i i - e 11* '- 1' 11+C k Am - k p (C2; and the specific solution to Equation C18 with the initial condition A m(t = 0 )= A m0 is \ A m + n mkPmP0 k p -- k Am / n m k PmP 0 g -k P t k P -- k Ara (C23) Of greatest interest here is the case in which the product compounds are known to be photolytically stable, that is, when k ^ = 0 for all m. In this case, Equation C23 becomes (for stable products) A m - A m0 + n mk PmP0 ( l - e " kpt) . (C24) C4. Relationships Between the Parent and Compound Concentrations Equations C7 and C24 can be combined to obtain (for stable products) so that kp k P Y ( A m- A m0) k Pm ( l - e ' kpt) Po (C25) Page 116 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 (for stable products) t1 m=l P 0 or (for stable products) (C26) k pt = - ln 1 ^ (A m ~ A mo) . m=l P0 (C27) If the changes in the product concentrations are all small compared to the original parent concentration, that is, if ^ A m - A m0 1, n-l P 0 we may use the expression (valid for -1 < X < 1 ) (C28) ln(l + X ) = X - - X 2 + - X 3 - - X 4 +. 234 and Equation C23 becomes (for stable products and A m0 < < P 0) k pt = ' ^ A m- A m/ - r_ p V ,u=1 0J or (for stable products and ^ A m A m0 < < P 0) k pt = ^ - Am A" p0 (C29) (C30) (C31) Page 117 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 C5. Parent Half-Life Estimates Based on Limits of Quantification of the Products In every experimental determination of k p, there is some set of values A ^0Q (the "limits of quantitation") below which the product concentrations A mcannot be reliably measured. If during an experiment carried out over the period of timeA t all the product concentrations A mremain below their limits of quantitation, then the maximum possible value of the rate k p Is obtained by assuming (for all the products) that 1) A m0 = 0 and 2) at time t = A t , the product concentrations have increased to the values A m= A ^0Q. With these assumptions, the experimental data indicate that the reaction rate k pis less than some maximum value (kp)maxas follows: (for photolytically stable products at concentrations below the limits of quantitation) k r * (kPL * = 0 m=l (C32) Under the same circumstances and assumptions, the experimental data indicate that the parent half-life T 1^ (see Equation C9) is greater than the value (t ^ )mmas follows: (for photolytically stable products at concentrations below the limits of quantitation) T V2 > (t t 2 ) --__H__2 ) = A t P0 b (2 ) a loq p " V pjTM"~(kP) L m=l (C33) The reader should note that Equations C32 and C33 are valid only when both 1) the products are stable and 2) the concentrations of all the potential products are measured. Otherwise, the quantity (k p )^ in Equation C32 may not actually represent the maximum possible value of the rate constant k p, and the related result in Equation C33 for (t Vp),, 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 concentrations over the time (A t ) of the experiment. In this case, it is the experimental precision of the measured product concentrations, rather than the limits of quantitation, which contribute to the estimate of the maximum value of the parent hydrolysis rate k p. If the set of concentrations measured for the mth product have the mean value p mand Page 118 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 standard deviation a m, the data do not exclude the possibility that the product concentration increased from the initial value c m- p mto the value c m+ |xmat time t = A t . Taking this possibility to be the actual case for the measured products, the maximum value of the quantity (A m- A m0) is 2am. 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 amor 2) concentrations below the limits of quantitation) 1 kP (kp)^ = So P0 A t Below LOQ * 20, Cons tan t (C34) Under these circumstances and assumptions, the experimental data indicate that the parent half-life T 1^ is greater than the value (t ^ ) as follows: P ' P 7min (for stable products at either 1) constant measured concentrations with standard deviation crmor 2) concentrations below the limits of quantitation) T172 P 2) (' Tl/nP )Anm = = A t P0 ln(2) A" + 2 0 , ( k p )max Below LOQ Constan t (C35) The reader should note that Equations C34 and C35 are valid only when both 1) the products are photolytically stable and 2) the concentrations of all the potential products are measured. C7. Parent Half-Life Estimates Based on the Experimental Precision of Parent Concentrations In certain experiments, the concentration of the parent remains essentially constant over the time (A t) of the experiment. In this case, it is the experimental precision of the measured parent concentrations that determines the maximum value of the parent hydrolysis rate k p . If the set of concentrations measured for the parent have the mean value (xpand standard deviation a P, the data do not exclude the possibility that the product concentration increased from the initial value pp -< jP to the value p p + a p at time t = A t . This reasoning suggests that the following estimate of the maximum parent photolysis rate is appropriate: (for essentially constant parent concentrations with mean value jxpand standard deviation G P) (C36) Page 119 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W 2783 k "p < \( k Fp/) max 2cp JLip A t ' Under these circumstances and assumptions, the experimental data indicate that the parent half-life T 1^ is greater than the value (t )minas follows: (for essentially constant parent concentrations with mean value ( i pand standard deviation C P) rp|/2 v;, _ ln(2) _ M-p A t ln( 2) 1 ' - ^ P.U - ( k p ) ^ - 2Gp (C37) References to Above: B1 I. N Levine, "Physical Chemistry," McGraw-Hill (New York), pp. 498-501 (1978). 62 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; P 0and P, which reflect before and after the exposure period of length ( t [ - t 0). In this case, no least squares regression is possible to determine the rate k p in Equation C8: k pt - I n In this circumstance, the only available estimate is kp = -- 1 In M - 1 In ^59.5 ng/ml ^ = 0.0559 hr -1 1-1 to l PoJ 70.15 hrs 88 .1 n g /m l (A) (B) The rate of photolysis in the reactor k P is related to the actinic rate of photolysis k ACT by (I ^ * ACTV ^ act --kp V 1 7 (C) Page 120 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 where I ACT = 261 w/m2 is the actinic solar intensity (at 45 south latitude) and the measured reactor intensity is I R = 680 w/m2. This gives , - l ( 261w / m k act = 0.0559 hr -- - -- --- r- =0.00215 hr -1 ACT 680 w / m 2 (D) For samples under constant illumination, the reaction rate and half-life are related by Equation C9: ji/2 - H2) Pk (E) However, the actinic half-life is three times larger, according the standard eight-hour exposure day. This leads to (indirect photolysis) T 1/ 2 . ACT" 3h(2) = 969 hrs = 40.4 days LACT (F) 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 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. Sam ple ID. Description EtFOSE-OH p h o tolysis in Soils 99039-267-01 032200-MC-44 3ppb std Matrix Spike 032200-MC-50 No Soil Spike Failed Criteria 75 -125% accuracy 75 -125% recovery 75 -125% recovery 75 -125% recovery 032200-MC-04 032200-MC-10 032200-ST-44 Matrix Spike No Soil Spike Matrix Spike 75 -125% recovery 75 -125% recovery 75 -125% recovery 032200-ST-50 032200-ST-24 032200-ST-04 032200-ST-10 032200-EPA-44 No Soil Spike Matrix Spike Matrix Spike No Soil Spike Matrix Spike 75 -125% recovery 75 -125% recovery 75 -125% recovery 75 -125% recovery 75 -125% recovery 032200-EPA-50 No Soil Spike 75 -125% recovery 032200-EPA-24 032200-EPA-10 032200-EPA-30 Matrix Spike No Soil Spike No Soil Spike 75 -125% recovery 75 -125% recovery 75 -125% recovery Analyte EtFOSA PFOA EtFOSE-OH PFOA FOSA EtFOSA EtFOSE-OH EtFOSE-OH EtFOSE-OH FOSA EtFOSA EtFOSE-OH EtFOSA EtFOSE-OH EtFOSE-OH EtFOSE-OH EtFOSA EtFOSE-OH PFOA FOSA EtFOSE-OH EtFOSE-OH EtFOSE-OH EtFOSE-OH V a lu e 137% 37% 26% 14% 15% 127% 150% 48% -79% 132% 52% -81% 166% 329% 3% 0% 61% -4% 69% 36% 41% 133% 288% 158% C om m ents failed 1/6 total 3ppb stds failed 2/5 analytes spiked failed 4/5 analytes spiked failed 1/5 analytes spiked failed 1/5 analytes spiked failed 3/5 analytes spiked failed 1/5 analytes spiked failed 1/5 analytes spiked failed 1/5 analytes spiked failed 1/5 analytes spiked failed 2/5 analytes spiked failed 3/5 analytes spiked failed 1/5 analytes spiked failed 1/5 analytes spiked failed 1/5 analytes spiked 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 F e 20 3 LC/MS 0508-EtFOSFe-10 Control Spike 0508-EtFOSFe-16 Matrix Spike 0508-EtFOSFe-50 Control Spike 0508-EtFOSFe-56 Matrix Spike GC/MS 0508-EtFOSFe-96 Control Spike 75 -125% recovery 75 -125% recovery 75 -125% recovery 75 -125% recovery EtFOSE-OH EtFOSE-OH EtFOSE-OH EtFOSE-OH 13% 52% 138% 126% Detected; LOQ (12ppb) 1H-perfluoropropane 13.64ppb 0508-EtFOSFe-91 Matrix Spike Detected; LOQ (12ppb) 1H-perfluoropropane 11.21ppb 0508-EtFOSFe-102 Matrix Spike Detected; LOQ (I2ppb) 1H-perfluoropropane 12.53ppb 0508-EtFOSFe-106 Matrix Spike Detected; LOQ (12ppb) 1H-perfluoropropane 14.76ppb 0508-EtFOSFe-107 Matrix Spike Detected; LOQ(12ppb) 1H-perfluoropropane 12.36ppb 0508-EtFOSFe-61 Matrix Blank Detected; LOQ (12ppb) 1H-perfluoropropane 16.07ppb 0508-EtFOSFe-62 Matrix Spike Detected; LOQ (12ppb) 1H-perfluoropropane 16.07ppb 0508-EtFOSFe-66 Matrix Spike Detected; LOQ (12ppb) 1H-perfluoropropane 13.32ppb 0508-EtFOSFe-72 Matrix Spike Detected; LOQ (12ppb) 1H-perfluoropropane 14.44ppb 0508-EtFOSFe-66 Matrix Spike 75 -125% recovery 1H-perfluoroheptane 133% 0508-EtFOSFe-67 Matrix Spike 75 -125% recovery 1H-perfluoroheptane 146% 0508-EtFOSFe-67 1H-perfluorohexane 126% 0508-EtFOSFe-70 Control Spike 75 -125% recovery 1H-perfluorooctane 66% 0508-EtFOSEfe-71 through 96 75-125% recovery see data sheet O-OK 0508-EtFOSFe-99 0508-EtFOSEfe100 0508-EtFOSEfe116 0508-EtFOSEfe117 Matrix Spike Control Spike Matrix Spike Matrix Spike 75 -125% recovery 75-125% recovery 75-125% recovery 75-125% recovery see data sheet see data sheet 1H-Cs, 2H-Cr 1H-Cr, 2H-Cr 146% 64,61 64,61 55,55 failed 1/5 analytes spiked failed 1/5 analytes spiked failed 1/5 analytes spiked failed 1/5 analytes spiked Data questionable. Retention time change due to organic solvent in samples. failed 1/8 analytes spiked failed 2/8 analytes spiked failed 1/8 analytes spiked failed multiple analytes spiked failed 7/8 analytes spiked failed 6/8 analytes spiked failed 2/8 analytes spiked failed 2/8 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 Environmental Laboratory Report No. W 2783 tch Run # 53 of 62 ta File C:\HPCHEM\l\DATA\R051100\rush0053.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 pi Acq. Method : C:\HPCHEM\1\METH0DS\ETF0511.M Last changed : 5/11/00 6:44:10 PM by kej Analysis Method : C :\HPCHEM\1\METHODS\R0511A1 .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. Page 126 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 tch Run # 54 of 62 ta File C:\HPCHEM\l\DATA\R051100\rush0054.D Sample Name: 00028-32-01 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 pi Acq. Method : C :\HPCHEM\1\METH0DS\ETF0511.M Last changed : 5/11/00 6:44:10 PM by kej Analysis Method : C :\HPCHEM\1\METHODS\R0511A1.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, EIC-298.7:299.7 (R05110Q\RUSH54.D) API-ES Negative 75000 Calibraron Std 1 50000 j 25000-j 0 J .......1-- * * .................... ...... A -- i..........' ........1 -- 1 ......r ............. '....... ... i 246 MSD1 413, EIC=412.7:413.7 (R051100\RSH0054.D) API-ES Negative S ________________________________________ - ' 1...... i .... ........ 1 ' 1 11 i .......1......... *-- 8 10 min 60000 40000-j < LL.20000- oZ .................... ......... .... ........................................ ........_ 1' 1 r O ..............................................1-------E-L---- -------- - ------ _ *1i * * ' * * ' 2 46 8 MSD1 498, EIC=497,7:498.7 (R0S1100\RUSH0054.D) API-ES Negative _-----__/ -------------i 1 10 min 4000 -i 3000 -i 2000- ..... 1........ 1..........T 1 - T ......'......... '........ f........ -------24 1 1 '........` ------ 1------- ' 68 MSD1 499, EIC=498.7:499.7(R051100\RUSH0054.D) API-ES Negative 4000 3000 2000- r 1 r-------1 * 1 i 1 ` 1 ' r 32 4 6 MSD1 526, EIC=525.7:526.7 (R051100\RUSH0054.D) API-ES Negative *' Ti 8 ' ' 1 ' 1........' ' 10 min 1' i ' 10 1 min 4000 2000- 1" -- > -- n r" " 1 t * ^ -------' 1i 1 "* 1 i 1' 1 i" 1 0__________________ 2__________________ 4__________________ 6__________________ 8______ ___________ 10___________min MSD1 630, EIC=629.7:630.7(R051100\RUSH0054.D) API-ES Negative 30000^ 20000- 10000 -j oZ " " ' 1..........' -- j-----1 r t "i ' J-- ' * 11 246 ...." i .................. ' 8 p\ J UJ(u .\ \ ' 1 .... T... ..... 10 min c / o a / r\r\ i ------ Page 127 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 Batch Run # 55 of 62 Data File C:\HPCHEM\l\DATA\R051100\rush0055.D Sample Name: 00023-32-02 Injection Date : 5/12/00 12:07:21 PM Seq. Line : 55 Sample Name : 00028-32-02 1 Vial : 3 Acq. Operator : kej Inj : 1 Acq. Instrument : Rush Inj Volume : 5 pi Acq. Method : C:\HPCHEM\1\METH0DS\ETF0511.M Last changed : 5/11/00 6:44:10 PM by kej Analysis Method : C:\HPCHEM\1\METHODS\R0511A1.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 NGX column, 4x35mm. MSD1 299, EIC298.7:299.7 (R051100\RUSH0055.D) API-ES Negative 75000 -I 50000 -i 25000 j 0- Calibration Std 2 MSD1 413, EIC=42,7:413.7 (R051100iRUSH0055.D) API-ES Negative 10 MSD1 498, EIC=497.7:498.7 (R051100\RUSH0055.D) API-ES Negative 8000 -i 6000 -i 4000 10 .................... r ........ ..... .......... ------1............ 1........" *........... i ...... 1....... 1 > 246 MSD1 499, EIC = 4 98.7:49 9.7 {R 05 1100\R U SH 00S5.D ) A P I-E S Negative I 8 ' -' i 10 ' .......... H mi n 6000 4000 2000- ............ 1.......... " -> "i................. ' ---------------- ..........r........ 32 4 1 .............. ........i......... >.............. 6 MSD1 526, EIC = 5 25.7:52 6.7(R 05 110 0\RU SH 0055 .D ) A P I-E S Negative ....... n ------- 1------- -- ----------- r ~ -- 1------ t ~ 8 10 min 10000 7500 H 5000 2500 - 246 MSD1 630, EIC = 6 29.7 ^ 30.7 (R051100\RU SH 0055.D ) A P I-E S Negative JK . i J 1 --i-- j-- i-- -- 8 10 min 60000 40000 20000o - " 3 r' ................. 2 ........... --'i -- r......... -........................ ..................................r ' ..............'" 46 8 1 j 10 min Instrument 1 5/24/00 12:46:55 PM kej Page 1 of 2 Page 128 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 Batch Run # 3 of 62 Data File C:\HPCHEM\l\DATA\R051100\rush0003.D Sample Name: 1:7 MilliQ/MeOH 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 pi Acq. Method : C:\HPCHEM\l\METH0DS\ETFO511.M Last changed : 5/11/00 6:44:10 PM by kej Analysis Method : C:\HPCHEM\1\METHODS\R0511A1.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. 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\l\DATA\R051100\rush0002.D Sample Name: MeOH blank Injection Date : 5/11/00 7:04:58 FM Sample Name : MeOH blank Acq. Operator : kej Acq. Instrument : Rush Acq. Method : C :\HPCHEM\1\METH0DS\ETF0511.M Last changed : 5/11/00 6:44:10 PM by kej Analysis Method : C :\HPCHEM\1\METHODS\R0511A1.M Last changed : 5/24/00 12:42:54 PM by kej Seq. Line : 2 Vial : 99 Inj : 1 (modified after loading) (Results are from a previously saved SIM Analysis (ES-) for PFOS/PFBS/PFOA using Dionex IonPac NG1 column, 4x35mm. 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 Batch Run # 13 of 62 Data File C:\KPCHEM\l\DATA\R051100\rush0013.D Sample Name: 00028-32-09 Injection Date 5/11/00 10:37:01 PM Seq. Line 13 Sample Name Acq. Operator 00028-32-09 kej Vial Inj 10 1 Acq. Instrument Rush Inj Volume 5 pi Acq. Method C :\HPCHEM\1\METH0DS\ETF0511 .M Last changed 5/11/00 6:44:10 PM by kej Analysis Method C :\HPCHEM\1\METHODS\R0511A1.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. El0*298.7:299.7 (R051100\RUSH0013.D) API-ES Negative 75000i C a lib ra tion Std 9 j 50000 - ..25000 H 0 J ........ -- ................ i ........ ..... .........."...." ' T ` 1,11 24 J ......" -- '"T .......' " 6 MSD1 413, EIC=412.7:413.7 (R0511001RUSH0013. D) API-ES Negative __________________________________________________ .' i .' 8 10 min 600000 - 4 00000- 200000 -I 0 ^ l-- i t i 24 6 MSD1 498, EIC=497.7:498.7<R051100'RUSH0013.0) API-ES Negative k ___________________________________________ -- ' l ' ' 8 10 rnirj 1500000 H 1000000 500000 i 0 - ---_--_--_-_--_-_--_-_-_,_--_-_--_--_-_-_--_-_--_--_1_--_--_-_--_-_'-_--_--_-_--_r_--____-,_--_-_--_--_-_j-_--_-_--_--_._--_--_-_--_-_>-_--_-_--_-_-_--_--_-_--_-_[-_--_-_--_--_>_" ________________l _ 24 6 8 MSD1 499. 10*496.7:499.7 (RO5110OV?USH00t3.D) API-ES Negative J ' 1 i ' 10 mir 1000000 500000 0- i i ' ( )24 6 MSD1 526, E1C525.7:528.7<R051100\RUSH0013.D) API-ES Negative , IL 8 i -- ..... 1500000 - 1000000 500000 I A0 - ---_-_-_--_-_-_____--__l ______'________--_-_-_--_-_-_--_-_-_--_-_-_-_*-_-_-_--_-_-_-_--_--_-_-_--_-_J_--_-_-_--_-_-_-_--_-_-_--_-_-_'-_-_-------------_-_-_1-_-_--_-_-_--_-_--_________________--___I_--_-_-_--_-_-_-___ , 32 4 6 8 MSD1 630, EIC*629.7:630.7(R051100\RUSH013.D) API-ES Negative I - ____|_____________,______ 2000000 1000000 0- ' k 1-1 ( . . . 2 4 6 8 10 mir Instrument 1 5/24/00 12:43:50 PM kej Page 1 of 2 Page 131 of 165 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 Batch Run # 29 of 52 Data File C:\HPCHEM\l\DATA\R051100\rush0029.D Sample Name: 0508-EtFOSfe-ll Injection Date : 5/12/00 3:45:32 AM Seq. Line : 29 Sample Name : 0508-EtFOSfe-ll Vial : 21 Acq. Operator : kej Inj : 1 Acq. Instrument : Rush Inj Volume : 5 pi Acq. Method : C:\HPCHEM\1\METH0DS\ETF0511.M Last changed : 5/11/00 6:44:10 PM by kej Analysis Method : C:\HPCHEM\1\METHODS\R0511A1.M Last changed : 5/24/00 12:42:54 PM by kej (modified after loading) SIM Analysis (ES-) for PFOS/PFBS/PFOA using Dionex IonFac NG1 column, 4x35mm. Instrument 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\l\DATA\R051100\rush0030.D Sample Name: 0508-EtFOSfe-12 Injection Date : 5/12/00 4:04:47 AM Seq. Line : 30 Sample Name : 0508-EtFOSfe-12 Vial : 22 Acq. Operator : kej inj : 1 Acq. Instrument : Rush Inj Volume : 5 pi Acq. Method : C:\HPCHEM\1\METH0DS\ETF0511.M Last changed : 5/11/00 6:44:10 PM by kej Analysis Method : C :\HPCHEM\1\METHODS\R0511A1.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, E1C29B.7;299.7{R051100\RUSH0030.D) API-ES Negative 75000i 5 0 0 0 0 -i Exposed - 72hrs 25000 -= -~ -z ~ . , i | . . , , . ' ( c2 A B MSD1 413, EfC*412.7:413.7 (R051100\RUSH0030.D) API-ES Negative 5 J --___________________________________________________ -------- ---------1------------- ---------8 1 0 miri 200000 100000 0- _____,___.___,____ ___ ___- __j___ ____ _____1"_i"_' __1 ____ J V i 2 46 8 MSD1 498, E!C=497.7:498.7{R051100\RUSH0030.D) APi-ES Negative . . ______ -- -- ^ ( i iMi 10 min 400000 200000 0- ' i J ' i' >246 MSD1 489, EIC488.7:499.7 (R051100\RUSM0030.D) API-ES Negative .1 i 1 ' t 1 '' 8 10 mi n 300000 200000 --_-_______________ _______... ___ ,, --P---100000o- ------ - , --------:------- |---------------,------- ----- " |------- *---------------- ------- 1---_-_--_-_-_-________ :__ >246 8 MSD1 526, E1C=525.7;526.7 (R051100\RUSH0030.D) API-ES Negative 10 mi n 400000 200000 0 - __'___'___`___i___1___1____` ___i ___1 ___ ___' ___i. ___ _________1___'_-_-_<-_----K---------- 1--------*----------------0 2 4 6 8 10 min MSD1 630, EIC*629.7:630.7 (R051100\RUSH0030.D) AP-ES Negative 400000 200000 0 - ..-- * ' 0 .....................i ..............- ............r-- i......... ................. - T" ' 1 r ' 24 6 A_ ...... " -- r k --------8 10 min Instrument 1 5/24/00 12:45:05 PM kej Page 1 of 2 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 Batch Run # 31 of 62 Data File C:\HPCHEM\l\DATA\R051100\rush0031.D Sample Name: 0508-EtFOSfe-i: Injection Date Sample Name Acq. Operator Acq. Instrument Acq. Method 5/12/00 4:24:02 AM Seq. Line 0508-EtFOSfe-13 Vial kej Inj Rush Inj Volume C :\HPCHEM\1\METH0DS\ETF0511.M 31 23 1 5 pi Last changed 5/11/00 6:44:10 PM by kej Analysis Method C :\HPCHEM\1\METHODS\R0511A1.M Last changed 5/24/00 12:42:54 PM by kej (modified after loading) SIM Analysis (ES-) for PFOS/PFBS/FFOA using Dionex IonPac NG1 column, 4x35mm. 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\l\DATA\R051100\rush0036.D Sample Name: 0508-EtFOSfe-18 Injection Date Sample Name Acq. Operator Acq. Instrument Acq. Method 5/12/00 6:00:26 AM Seq. Line : 36 0508-EtFOSfe~18 Vial : 28 kej Inj : 1 Rush Inj Volume : 5 pi C :\HPCHEM\1\METH0DS\ETF0511. M Last changed 5/11/00 6:44:10 PM by kej Analysis Method C :\HPCHEM\1\METH0DS\R0511A1.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. Instrument 1 5/24/00 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\l\DATA\R051100\rush0065.D Sample Name: 0508-EtFOSfe-31 Injection Date 5/12/00 3:20:38 PM Seq. Line : 65 Sample Name 0508-EtFOSfe-31 Vial : 41 Acq. Operator kej Inj : 1 Acq. Instrument Rush Inj Volume : 5 pi Acq. Method C :\HPCHEMM\METH0DS\ETF0511 .M Last changed 5/11/00 6:44:10 PM by kej Analysis Method C:\HPCHEM\1\METHODS\R0511B1.M Last changed 5/24/00 2:14:48 PM by kej (modified after loading) SIM Analysis (ES-) fox PFOS/PFBS/PFOA using Dionex IonPac NG1 column, 4x35mm. Instrument 1 5/24/00 2:15:52 PM kej Page 1 of 2 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 Batch Run # 15 of 61 Data File C:\HPCHEM\l\DATA\R051100\rush0066,D Sample Name: 0508-EtFOSfe-32 :*==sat^=s 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 pi Acq. Method : C:\HPCHEM\1\METH0DS\ETF0511.M Last changed : 5/11/00 6:44:10 PM by kej Analysis Method : C:\HPCHEM\1\METHODS\R0511B1.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. Instrument 1 5/24/00 2:15:56 PM kej Page 1 of 2 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 Batch Run # 16 of 61 Data File C:\HPCHEM\l\DATA\R051100\rush0067.D Sample Name: 0508-EtFOSfe-33 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 pi Acq. Method : C :\HPCHEM\1\METH0DS\ETF0511 .M Last changed : 5/11/00 6:44:10 PM by kej Analysis Method : C :\HPCHEM\1\METHODS\R0511B1.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. Instrument 1 5/24/00 2:16:01 PM kej Page 1 of 2 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 Batch Run # 21 of 61 Data File C:\HPCHEM\l\DATA\R051100\rush0072.D Sample Name: 0508-EtFOSfe-38 Injection Date : 5/12/00 5:35:37 PM Seq. Line :: 72 Sample Name : 0508-EtFOSfe-38 Vial :: 48 Acq. Operator : kej Inj :; 1 Acq. Instrument : Rush Inj Volume :: 5 pi Acq. Method : C:\HPCHEM\1\METH0DS\ETF0511.M Last changed : 5/11/00 6:44:10 PM by kej Analysis Method : C:\HPCHEM\1\METHODS\R0511B1.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. Instrument 1 5/24/00 2:16:24 PM kej Page 1 of 2 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 Batch Run # 40 of 61 Data File C:\HPCHEM\l\DATA\R051100\rush0091.D Sample Name: 0508-EtFOSfe-51 Injection Date : 5/12/00 11:42:33 PM Seq. Line : 91 Sample Name : 0508-EtFOSfe-51 Vial : 61 Acq. Operator : kej Inj : 1 Acq. Instrument : Rush Inj Volume : 5 pi Acq. Method : C:\HPCHEM\1\METH0DS\ETF0511.M Last changed : 5/11/00 6:44:10 PM b y kej Analysis Method : C:\HPCHEM\1\METHODS\R0511B1.M Last changed : 5/24/00 2:14:48 PM b y kej (modified after loading) SIM Analysis (ES-) for PFOS/PFBS/PFOA using Dionex IonPac NG1 column, 4x35mm. 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\l\DATA\R051100\rush0092.D Sample Name: 0508-EtFOSfe-52 Injection Date 5/13/00 12:01:50 AM Seq. Line : 92 Sample Name 0508-EtFOSfe-52 Vial : 62 Acq. Operator kej Inj : 1 Acq. Instrument Rush Inj Volume : 5 pi Acq. Method C:\HPCHEM\1\METH0DS\ETF0511.M Last changed 5/11/00 6:44:10 PM by kej Analysis Method C :\HPCHEM\1\METHODS\R0511B1.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 MSD1 299, EIC*298.7:299.7 (R051100V*USH0092.D) API-ES Negative Day 0 Blank Spiked Fe203 No Peroxide to 9 .i l ili...l. . i ln _Jlliu A -------- r - ... .............................. . r- " T .... ..........,...... ...A - . r 1 246 MSD1 413, EIC412.7:413.7 (RO511OO\RUSHOO02.D) API-ES Negative 100000i 75000 -i 50000 25000 H a- 1 t 1 *' i .. 11i 2 46 MSD1 498, EICb497.7:498.7 (R051100\RUSH0092.D) API-ES Negative _ 200000 i 1 5 0 0 0 0 -t 100000 50000 oJ 246 MS Dl 499, EIC=498.7:499.7 (R051100WUSH0092.D) API-ES Negative 150000 100000 50000 0- ' ' I ' ' ' 1 T r l ' ' 24 e MSD1 526, E10*525.7:528.7 (R051100\RUSH0092.D) API-ES Negative (~ ......-----_-_-_r__'____r -____-_|___'"_>_r_-_-_--_-_--_-_--_-_-_ 8 10 mir 1 i 1 * i ... 8 10 mir A .. 8 10 mir f\ '! 8 . '. 1 . . 1 ', '' r 10 . min 200000 100000 0- ............. .. n i .................................................................... K ' i i. i t .............2 4 6 8 MSD1 630, El0=629.7:030.7 (R051100\RUSH0092.D) API-ES Negative i 1 i 10 "min 400000 200000 - 0 D ....... - ... i 1 - 2 _ .... . 1 i ' i....... 4 .....................................6 ........... i 8 k 1 i" ...-t~'---------------10 mir Instrument 1 5/24/00 2:17:54 PM kej Page 1 of 2 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 Batch Run # 42 of 61 Data File C:\HPCHEM\l\DATA\R051100\rush0093.D Sample Name: 0508-EtFOSfe-53 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 pi Acq. Method : C:\HPCHEMU\METH0DS\ETF0511.M Last changed : 5/11/00 6:44:10 PM by kej Analysis Method : C:\HPCHEM\l\METHODS\R0511Bl.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. Instrument 1 5/24/00 2:17:58 PM kej Page 1 of 2 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 Batch Run # 47 of 61 Data File C:\HPCHEM\l\DATA\R051100\rush0098.D Sample Name: 0508-EtFOSfe-58 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 pi Acq. Method : C:\HPCHEM\1\METH0DS\ETP0511.M Last changed : 5/11/00 6:44:10 PM by kej Analysis Method : C:\HPCHEM\1\METHODS\R0511B1.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. Instrument 1 5/24/00 2:18:21 PM kej Page 1 of 2 Page 143 of 165 File :E:\R051700\R0517015-D Operator :RM Acquired : 17 May2000 21:08 usingAcqMethod V0A_FC2 instrument: Rufus Sample Name: 050800-EtFOSfe-068 control exp Misclnfo : Vial Number: 15 3M Environmental Laboratory Report No. W2783 BACK TO MAIN Page 144 of 165 File : EAR051700\R0517015.D Operator : RM Acquired : 17 May 2000 21:08 using AcqMethod VOA FC2 instrument: Rufus ~ Sample Name: 050800-EtFOSfe-068 control exp Miscinfo : Vial Number 15 3M Environmental Laboratory Report No. W2783 BACK TO MAIN Page 145 of 165 File : E:\R051700\R0517015.D Operator : RM Acquired : 17 May 2000 21:08 using AcqMethod V0A_FC2 Instrument: Rufus Sample Name: 050800-EtFOSfe-068 control exp Misc Info : Vial Number 15 3M Environmental Laboratory Report No. W2783 BACK TO MAIN Page 146 of 16E File : E:\R051700\R0517015.D Operator :RM Acquired : 17 May 2000 21:08 using AcqMethod V0A_FC2 instrument: Rufus Sample Name: 050800-EtFOSfe-068 control exp Misclnfo : Vial Number: 15 3M Environmental Laboratory Report No. W2783 BACK TO MAIN Page 147 of 165 File : E:\R051700\R0517008.D Operator :RM Acquired : 17 May 2000 16:36 using AcqMethod VOA_FC2 instrument: Rufus Sample Name: 050800-EtFOSfe-061 matrix blk exp Misclnfo : Vial Number: 8 Abundance 3M Environmental Laboratory Report No. W2783 TC: BC617CC5.D V a U l V ' TIC:R0517009.0 Dlfay . lu .0 BACK TO MAIN >-- i ^ w ;: AVJ \ V^ ~ J \ A1 18.50 19.00 19.50 20.50 21.001 ~l 1 1 1 1 I ' r 1 H ` 1 1 1 I I I ' | " ' " I ' 1 | ' ' 20.00 21.50 l-- r - 22.00r - 1 -- i-- r 22.50 Page 148 of 165 3M Environmental Laboratory Report No. W2783 File : E:\R05t700\R0517008.D Operator :RM Acquired : 17 May 2000 16:36 using AcqMethod VOA_FC2 Instrument: Rufus Sample Name: 050800-EtFOSfe-061 matrix blk exp Misclnfo : Vial Number: 8 Abundance 340000 320000 300000 280000 260000 240000 TIC: R0517008.D TIC:R0517009.D 220000 200000 180000 160000 ; 140000 ; 120000 ; 100000 80000 60000 40000 20000 0 Time-> 10*.501 ' '1H.00* 1 ' 1' .5101 1 12'.0I 0 2.510 3.0I 0 3.5I 0 4.010 4.5I 0 5.0I 0 55I 0 6.0I 0 6.5I 0 7.0f 0 .7,5I 0' .' 81.0I 01 ' '81.51Q 191.0| 0 9.510 10I.00 10I50 11I.00 111.50 1M250 12i.5`0` i13i .j0i0i '1r3j.5n0 Page 149 of 165 BACK TO MAIN File : E:\R051700\R0517008.D Operator : RM Acquired : 17 May 2000 16:36 using AcqMethod V0A_FC2 Instrument: Rufus Sample Name: 050800-EtFOSfe-061 matrix blk exp Misclnfo : Vial Number 8 Abundance TIC:R0517008.D 3M Environmental Laboratory Report No. W2783 BACK TO MAIN Page 150 of 165 File : E:\R051700\R0517010.D Operator : RM Acquired : 17 May 2000 17:54 using AcqMethod VOA_FC2 instrument : Rufus Sample Name: 050800-EtFOSfe-063 sample exp Mise Info : Vial Number 10 Abundance . 2600000 2400000 : 2200000 2000000 1800000 1600000 , 1400000 1200000 ' 1000000 800000 600000 400000 200000 Time-> tt rp* T 1.00 2.00 3M Environmental Laboratory Report No. W2783 Page 151 of 165 BACK TO MAIN File : E:\R051700\R0517012.D Operator : RM Acquired : 17 May 2000 19:12 using AcqMethod VOA_FC2 Instrument: Rufus ~ Sample Name: 050S00-EtFOSfe-065 trip exp Miscfnfo : Vial Number 12 3M Environmental Laboratory Report No. W2783 BACK TO MAIN Page 152 of 165 File : E:\R051700\R0517Q12.D Operator : RM Acquired : 17 May 2000 19:12 using AcqMethod V0A_FC2 Instrument: Rufus Sample Name: 050800-EfFOSfe-065 trip exp Misclnfo : Vial Number: 12 3M Environmental Laboratory Report No. W2783 BACK TO MAIN Page 153 of 165 File : E:\R051700IR0517012.D Operator : RM Acquired : 17 May 2000 19:12 using AcqMethod V0A_FC2 Instrument: Rufus Sample Name: 050800-EtFOSfe-065 trip exp Misclnfo : Vial Number 12 Abundance TIC: R05i'7012.D 3M Environmental Laboratory Report No. W2783 BACK TO MAIN Page 154 of 16. 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. W 2783 STANDARD LABORATORYSOILS PARAMETER STCHOIXCO.,vyi MORGANCO,ALA METALS Ag, mg/Kgdriedbasis <3 <3 Al, mg/Kgdriedbasis 22000 40000 As, mg/Kgdriedbasis Ba, mg/Kgdriedbasis Be. mg/Kgdribdbasis' <10 210 0.6 <10 97 <b.S Ca, mg/Kgdriedbasis Cd, mg/Kgdriedbasis 3000 <0.5 1000 <0.5 Co, mg/Kgdriedbasis 8 5 . Cr, mg/Kgdriedbasis 36 41 Cu, mg/Kgdriedbasts . 12 8.5 Fe, mg/Kgdriedbasis 20000 22000 . Hg. mg/Kgdriedbasis 0.04 ' 0.11 Mg. mg/Kgdriedbasis 2800 1500 Mn, mg/Kgdriedbasis 800 120 Mo. mg/Kgdriedbasis 52 84 Na, mg/Kgdriedbasis 120 73 Ni, mg/Kgdriedbasis 18 14 P, mg/Kgdriedbasis 620 150 Pb, mg/Kgdriedbasis <30 <30 Se, mg/Kgdriedbasis <200 <200 Zn, mg/Kgdriedbasis 49 47 EXCHANGEACTIVITY ExtractableCa, meq/IOOg 8.14 3.50 Extractable P, meq/100g 0.68 0.10 ExtractableMg, meq/100g 2.97 0.43 ExtractableNa, meq/IOOg 0.03 0.02 Base Saturation% 42 18 CEC, meq/100g 28.3 22.0 ESP, % 0.11 0.09 SAR, unis 0.04 0.05 NUTRIENTS Available P,mg/L 61 5 NH3-N, mg/L 2.00 .- 0.25 N03-N, mg/L . 84 14 KfeldatilN, mg/Kg 1470 280 ORGANICMATTER ' TOC,% OM> 1.79 3.09 0.277 0.478 PHY3I0CHEMICAL ReidCapacity, % 19.1 22.3 pHw, units 5.7 4.6 pHs. units 5.7 4.5 . Ume-req. Tons/Acre 1.8 1.B SolubleSalts, mmhos/cm 0.98 0.32 CLASSIFICATION %Clay 22 26 /.Silt 44 36 %Sand 34 38 Soil Type LOAM CLAYLOAM BASENEUTRALPESTICIDES BDL BDL ACIDPESTICIDES BOL BDL BDLm BelowDetection Limits EPA-SSM <3 46000 <10 100 0.6 86000 <0.5 6 25 13 18000 0.02 30000 710 92 220 13 ' 710 <30 <200 47 26.1 0.16 3.58 0.06 100 ' 21.3 0.26 0.05 15 1.80 6.0 250 0467 0.805 16.0 7.7 7.5 NONE 0.66 22 26 52 SANDYCLAYLOAM BDL BDL r ' ... ...... . ----- Z L 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 Environmental Laboratory Report No. W 2783 PASE 03 A filia wfi CIMA Lmii Onici Ii;tcr\ yS Miami Pauk uiilniiit. 26 Smili t'*fl'iiri rtl-:-^.,3f V V 1. .{ -f UU i:`,t ot V;lr!0US *'* KoniWnalions (O.SS W-W -''340(1TM) vs Sunhijhl. ?fi' South Exposure, Filter Com bination Inner Filter Glass Type's? Boroatiicate O uter Filter Glass Trite'S". ' Borasincue Typ "3" Borotftlcata Sod Lima *';i ..V : *.;'Typo ,, 'r .. 7W_Borq!*5lUkc4^>!, 'e m * Typ*'. SoroattlMt cm * ` Sotte U n e . .. Typa-sy BorosRicat Sode Um Atlas Xenon Filter Combination Toot Condition ' Irradian e* Ranga* W /m * WsAage 250-300 300-400 4OO-SOO Sunlight Measurements - v^ t- TtaMlDayfigbt ' ' ' Paak Nettimi Daylight ' ' Peak Natural 1 DayBght SUndaM ` *Small variations a n possible, depending on condition oflamp andfitters. , 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 Environmental Laboratory Report No. W2783 Suntest Irradiance in W /m A2*nm Assuming the use of 300-800nm Global Sensor Only Filters Used W avelength 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 Q /Suprax (UV) 0.001 0 0 0 0.001 0 0 0 0 0 0 0 0 0 0 0 0 0 0.003 0.005 0.009 0.014 0.021 0.028 0.045 0.054 0.07 0.085 0.116 0.138 0.151 0.175 0.21 0.24 0.263 0.279 0.329 Irradiances factored to yield 680 W /m A2 In 300-800nm band IR Q /Suprax (UV) 0.001119 0 0 0 0.001119 0 0 0 0 0 0 0. 0 0 0 0 0 0 0.003357 0.005595 0.010071 0.015666 0.023499 0.031332 0.050355 0.060426 0.07833 0.095115 0.129804 0.154422 0.168969 0.195825 0.23499 0.26856 0.294297 0.312201 0.368151 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 1.241 406 1.284 408 1.473 410 1.395 412 1.551 414 1.416 416 1.369 418 1.426 420 1.644 422 1.453 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 0.393888 ' 0.412911 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 0.81687 0.909747 0.960102 0.858273 0.8952 0.925413 0.966816 1.076478 1.110048 1.089906 1.114524 1.150332 1.243209 1.259994 1.373013 1.837398 1.736688 1.390917 1.374132 1.388679 1.436796 1.648287 1.561005 1.735569 1.584504 1.531911 1.595694 1.839636 1.625907 Page 161 of 165 424 426 428 430 432 434 436 438 440 442 444 446 448 450 452 454 456 458 460 462 464 466 468 470 472 474 476 478 480 482 484 486 488 490 492 494 496 498 500 502 504 506 508 510 512 514 516 518 520 522 1.472 1.462 1.466 1.466 1.487 1.5 1.566 1.714 1.616 1.616 1.57 1.563 1.573 2.267 2.031 1.796 1.811 2.127 1.835 3.267 2.476 2.541 5.277 2.487 1.922 2.924 1.837 1.813 2.289 2.516 2.651 1.952 1.842 1.898 3.012 2.089 1.871 1.888 1.898 1.973 2.005 1.94 1.927 1.934 1.963 2.013 2.031 2.021 1.995 1.971 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 1.808304 1.808304 1.75683 1.748997 1.760187 2.536773 2.272689 2.009724 2.026509 2.380113 2.053365 3.655773 2.770644 2.843379 5.904963 2.782953 2.150718 3.271956 2.055603 2.028747 2.561391 2.815404 2.966469 2.184288 2.061198 2.123862 3.370428 2.337591 2.093649 2.112672 2.123862 2.207787 2.243595 2.17086 2.156313 2.164146 2.196597 2.252547 2.272689 2.261499 2.232405 2.205549 Page 162 of 165 524 526 528 530 532 534 536 538 540 542 544 546 548 550 552 554 556 558 560 562 564 566 568 570 572 574 576 578 580 582 584 586 588 590 592 594 596 598 600 602 604 606 608 610 612 614 616 618 620 622 1.98 1.966 1.978 1.954 1.932 1.942 2.008 2.014 2.113 1.996 1.977 1.962 1.921 1.876 1.84 1.938 2.17 2.106 1.936 1.912 1.749 1.706 1.77 1.997 2.032 1.802 1.624 1.572 1.654 2.215 2.034 1.738 2.118 2.159 1.996 2.185 1.607 1.492 1.471 1.37 1.263 1.207 1.184 1.292 1.494 1.31 1.631 2.672 2.172 1.416 BACK TO MAIN 3M Environmental Laboratory Report No. W2783 2.21562 2.199954 2.213382 2.186526 2.161908 2.173098 2.246952 2.253666 2.364447 2.233524 2.212263 2.195478 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 2.016438 1.817256 1.759068 1.850826 2.478585 2.276046 1.944822 2.370042 2.415921 2.233524 2.445015 1.798233 1.669548 1.646049 1.53303 1.413297 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 1.256 628 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 1.12 654 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 2.601675 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 1.191735 1.358466 2.608389 1.29804 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 W/mA2 0.429696 0.662448 0.914223 0.663567 0.709446 0.528168 0.353604 0.419625 1.227543 0.411792 0.304368 0.295416 0.491241 0.398364 0.258489 0.305487 0.454314 0.920937 1.503936 0.619926 1.740045 1.246566 0.434172 0.217086 0.170088 0.210372 0.23499 0.276393 0.434172 0.365913 0.251775 0.191349 0.374865 0.775467 0.153303 0.20142 0.364794 0.707208 0.260727 680.0 W/mA2 Page 165 of 165