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3M Environmental Laboratory Report No. W1878
Study Title Hydrolysis Reactions of Perfluorooctane Sulfonate
(PFOS)
Data Requirement: Based on OPPTS: 835.2110
Author Thomas L. Hatfield, Ph.D.
Study Completion Date March 27, 2001
Performing Laboratory 3M Environmental Laboratory Building 2-3E-09,935 Bush Avenue
St. Paul, MN 55106
Project Identification 3M Laboratory Report No: W1878
Total Number of Pages 71
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3M Environmental Laboratory Report No. W1878 This page has been reserved for specific country requirements.
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3M Environmental Laboratory Report No. W1878
Statement of Non-Compliance
Study Title: Hydrolysis Reactions of Perfluorooctane Sulfonate (PFOS). Study Identification Number: W1878 This study does not comply with the requirements of the US EPA Good Laboratory Practices Standards at 40 CFR Part 792 (TSCA). However, many GLP standards were used in the development of the analytical method (Appendix A), and the quality assurance procedures followed in this study were based on the practices described in the GLP documentation.
____________"
Sponsor Representative
Dfe y ? Date
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3M Environmental Laboratory Report No. W1878
Quality Assurance Statement
Study Title: Hydrolysis Reactions of Perfluorooctane Sulfonate (PFOS). Study Identification Number: W1878
The following table provides details of the audits performed by the 3M Environmental Laboratory Quality Assurance Unit (QAU).
Inspection Dates
8/11/00,8/16-17/00 9/7, 8 ,11/00 3/13-14/01
Phase Data and Draft Report
Date Re ported to
Management Study Director
8/18/00
8/18/00
Data and Draft Report
9/11/00
9/11/00
Draft Report
3/14/01
3/14/01
. lio -^ P X
QAU Representative
2l. O o\
Date
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3M Environmental Laboratory Report No. W1878
Table of Contents
Statement of Non-Compliance............................................................................................... 3
Quality Assurance Statement................................................................................................. 4
List of Tables............................................................................................................................ 6
List of Figures........................................................................................................................... 6
Study Personnel and Contributors.......................................................................................... 6
Location of Archives.................................................................................................................7
S u m m a ry ...................................................................................................................................8
Introduction.............................................................................................................................. 9
Summary of Kinetics Model...................................................................................................10
Materials and Methods........................................................................................................... 11 Chemical Characterizations............................................................................................. 11 Sample Preparation..........................................................................................................11 Sample Analysis................................................................................................................ 12 Deviations...........................................................................................................................12
Results and Discussion.........................................................................................................14 Data Quality Objectives (DQO's)..................................................................................... 14 Anomalous Analytical Results......... ................................................................................ 14 Statistical Methods and Calculations...............................................................................15 Data Summary and Discussion........................................................................................ 15
Conclusions.............................................................................................................................19
References............................................................................................................................. 20
Signatures.............................................................................................................................. 21
Appendix A: Analytical Method...............................................................................
22
Appendix B: Kinetics Model......................................................................
38
Appendix C: Selected Analytical and Kinetics Results.......................................................48
Appendix D: Selected Chromatograms................................................................................59
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3M Environmental Laboratory Report No. W1878
List of Tables
Table 1. Summary of Results Based on PFOS Concentrations.........................................8 Table 2. Summary of Results Based on the Mean and Precision of PFOS
M e a s u re m e n ts ..........................................................................................................8 Table 3. Characterizations of Test and Reference Substances.......................................11 Table 4. Observed (50 C) Slopes of PFOS Concentrations in Aqueous Buffered
Solution for Various pH Levels.............................................................................. 15 Table 5. Calculated Slope of PFOS Concentrations in Aqueous Buffered Solutions
Using Data Pooled Over All pH Levels................................................................ 16 Table 6. Degradation Rate and Half Life of PFOS in Aqueous Buffered Solutions Based
on the Concentration Mean and Standard Deviation.......................................... 18
List of Figures
Figure 1. Structure of the Potassium Salt of PFOS.............................................................9 Figure 2. Observed PFOS Degradation for Various pH levels......................................... 16 Figure 3. Pooled PFOS Data and Slope Regression.........................................................17
Study Personnel and Contributors
TSthuodmyaDs iLre. cHtoatrfield, Ph.D.
3M Environmental Laboratory Building 2-3E-09 935 Bush Avenue St. Paul, MN 55106 (651) 778-7863
S3MpoCnosroproration
Professional Services Contributing Personnel
Kuruppu Dharmasiri, Ph.D. Kevin Macklin Mark T. McCann Anthony E. Scales Angela Schuler Joseph J. S. Tokos, Ph.D. (Pace Analytical Services, Inc., 1700 Elm St., Minneapolis, MN 55144)
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3M Environmental Laboratory Report No. W1878
Location of Archives
The 3M Environmental Laboratory will retain the original data documents and digital copies of the original data related to this work for at least 10 years following the effective date of any related final ruling. Information may obtained through written inquiry addressed as follows: 3M Environmental Laboratory Building 2-3E-09 935 Bush Avenue St. Paul, MN 55106
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3M Environmental Laboratory Report No. W1878
Summary
We report here the results of our study of the hydrolysis of perfluorooctane sulfonate (hereafter, PFOS). Our methods are described below and in Appendix A to this work; our results are based on the observed concentrations of PFOS in buffered aqueous solutions as a function of time. 3M's Environmental Laboratory staff developed the study procedures; they are based on EPA's OPPTS Guideline Document 835.21101but do not fulfill all the requirements of the guideline. The chosen analytical technique was high performance liquid chromatography with mass spectrometry detection (HPLC/MS). Table 1 summarizes the results of the study.
During this study, we prepared and examined samples at six different pH levels between 1.5 and 11.0 over a period of 49 days, and our results indicate no dependence of the degradation rate of PFOS on the sample pH level. We have excluded the "Day 0" samples because they were improperly stored before analysis; see the "Deviations" section below. Our observations of the PFOS concentrations for the 42 day incubation period ("Day 7" through "Day 49"), pooled over the six observed pH levels, are presented in Table 1.
Table 1. Summary of Results Based on PFOS Concentrations.
Calculated slope (d ay1)
2.98 x 1(T
Calculated slope upper limit (2o)
(day'1)
5.30x1 O'4
Calculated slope lower limit (2<y)
( d a y 1)
6.66x10'
These results indicate no degradation of PFOS; the derived positive slope does not provide a half-life estimate.
The mean value and precision of PFOS concentrations do provide an estimate of the PFOS half-life, presented in Table 2.
Table 2. Summary of Results Based on the Mean and Precision of PFOS Measurements
Maximum Possible Rate at
50 C ( d a y 1)
4 .6 4 x 1 0'4
Maximum Calculated Rate at 25 C
( d a y 1)
4.64 x 10'
Calculated Half Life at 25 C (years)
>41
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3M Environmental Laboratory Report No. W1878
Introduction
Three primary chemical routes of environmental degradation are hydrolysis, photolysis, and biodegradation. Studies of these routes provide information on the environmental persistence of both the "parent" compounds and their reaction products, and are ideally carried out over the range of chemical conditions pertinent to both environmental and metabolic processes. The hydrolysis of the potassium salt of PFOS (or, more generally, its degradation in the presence of H20 ) is addressed in this report. The structure of the PFOS salt is illustrated in Figure 1.
Figure 1. Structure of the Potassium Salt of PFOS
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3M Environmental Laboratory Report No. W1878
Summary of Kinetics Model
A full mathematical description of the kinetics model employed in this study is presented in Appendix B. The data in similar studies typically allow two independent estimates of the hydrolytic half-life, but only one estimate is available from our PFOS data.
A first estimate is usually based on the observed degradation of the compound in dilute, appropriately buffered aqueous solutions. Equation B10 describes the estimated half life (t ^ in terms of the estimated total hydrolysis rate k p:
Eq. 1
We attempted to determine the quantity k pfrom the experimental data as described in
Appendix B. The data corresponding to "Day 7" were used to determine the relative concentration ratios (see the "Deviations" section below; see also Equations B8 and B9). The derived rates, both at various pH levels and when pooled over all pH levels, were poorly determined, and indicate only that PFOS does not degrade in aqueous solution.
A half-life second estimate (see Equation B37) is available from the mean p and standard deviation o of the observed PFOS concentrations, assuming that they were essentially constant over the experimental portion of the study. This estimate is
H2)
)h > (\t 1P/2/)mi.n = (kp)max
p A t ln( 2)
2o
Eq.2
where A t represents the sample incubation period.
All the samples used in this study were maintained a reaction temperature of 50 ( 3) C. The quoted results, valid for the reaction temperature 25 C, were calculated from our experimental results according to methods described in Appendix B (Eq. B38 and B39).
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3M Environmental Laboratory Report No. W1878
Materials and Methods
Details of the characteristics of the test materials, sample preparation techniques, and analytical methods are presented in Appendix A (ETS-8-13.0, "Hydrolysis of Perfluorooctane sulfonate (PFOS) and Analysis by High Performance Liquid Chromatography with Mass Spectrometry Detection"). A summary of these items is provided below, as well as a description the known deviations from the procedures of Appendix A. 3M prepared and analyzed the samples included in this study between May 24 and July 12,1999.
Chemical Characterizations
Table 3 describes the sources and properties of the materials used in this work. These materials were used to prepare both the samples and the quantitative standards used to quantify them. For this reason, and because Equation 1 involves only ratios of the parent and product concentrations, the resulting rate and half-life estimates are largely independent of the material purity levels.
Table 3. Characterizations of Test and Reference Substances
Source
Chemical Lot Number
Physical Description Molecular Weight (gm mole'1)
PFOS (Potassium Salt) 3M ICP/PCP Division Batch# 171
Light colored powder
538
THPFOS ICN Biomedicals Batch # 53406
Brown waxy solid
428
Sample Preparation
We prepared four 1.0-mL aqueous buffer samples (a sample, a duplicate, a triplicate, and a matrix spike at each of six pH levels (1.5,3, 5,7, 9 and 11) for analysis at eight time intervals (0, 7, 14, 21,28, 35, 42 and 49 days). Buffered solutions containing 501.5 ng/mL of the potassium salt of PFOS and 368 ng/mL of THPFOS (3, 3,4, 4, 5, 5, 6, 6, 7, 7, 8, 8, 8-tridecafluorooctane sulfonic acid), the latter serving as a surrogate for the compound PFOS, formed the basis of all these samples. The chosen buffer solutions are described fully in Appendix A.
All the samples were prepared simultaneously, and all but the "Day 0" samples were placed in an orbital incubator/shaker maintained at 50 ( 3) C. After the appropriate incubation times, subsets of the sample vials were removed from the incubator; they were then spiked (as required) with the PFOS solution, diluted 10:1 with methanol containing the internal standard THPFOS, and refrigerated at -4 C. Similar treatment of the "Day 0" samples is prescribed by the analytical method (see Appendix A); they are
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to be agitated for a minimum of three minutes, diluted and spiked as described immediately above, and then refrigerated rather than incubated. In this study, the "Day 0" samples were not refrigerated; see the "deviations" section below. Except during the relatively short periods of time required to prepare them, all the samples were shielded from light.
Eight calibration standards containing PFOS (301 to 802 ng/ml) served as the quantitative basis of the study. All these standards were prepared at the appropriate pH levels using the buffer solutions described in Appendix A.
Sample Analysis
The equipment we used for the HPLC/MS analysis was a Hewlett Packard model 1100 equipped with a Dionex lonPac NG-1 HPLC column (aqueous ammonium acetate/methanol solvent gradient) and an ALS Model G1322A degassing module. An ALS Model G1315A column heater maintained the column temperature at 40C, a quaternary pump supplied a column flow rate of 0.3 mL/min, and an ALS Model G1313A auto-sampler provided 5 pL sample injections. The detector was a Hewlett Packard MSD mass spectrometer, operated in negative-mode electrospray ionization mode; anions of PFOS and THPFOS were detected at the mass-to-charge (m/z) ratios 499, 427, respectively. We processed the resulting data using the computer program HP ChemStation for LC (Rev.A.06.0). Further analytical details, including the gradient elution program, instrument and detector parameters, and performance specifications, are presented in Appendix A.
Deviations
After incubation and prior to analysis, all samples were stored at temperatures (-4 C or -20 C) rather than at the prescribed temperature of 4 C prescribed in the Method. The pH meter calibration was performed with only two standards (at pH = 7.0 and 10.0) rather than at the three Method-prescribed pH levels (4.0, 7.0, and 10.0). Only three ions were monitored in the analysis, instead of the seven specified in the Method.
tThwanotshaempprelesscr(iPbFedO9Sm-1L57, aannddthPeFcOoSn-c1e1n3tr)awtioenrereqsuuelntschweedrewciothrr1e8ctmedLtoorfeMfleecOtHthirsatfhaectr. TtlTttgiaaeehhndmehwmddeednemiotpeicPcotbroeiaoFaaournetndOtaenfvicidftdoauSaeueinlpntmrnridreotooosereroanaffsamgclotuaftuireirilloelatotteiasssnadnoe,est"arentuvwoDtassriestfoeaoainoptonbyfhhlrdslueesrae0atpoaavi"ysPtmoafeoesranFEslpeepnuOwqldxardteuiiSncasfoo"aldosnuwrDdtrisdh5etoeauoeaganrmysdlernsfeaB7M-dptpdlha"i8iraaksefe.rrdteipat"in"a;ioFtaDDfgthtniarohceaewa.reiirydynTatit"hlta0hh0ltDheyhn"ea"seaPdnrersdyaFefaatai"ishOm7snrtDueeas"aSlptdalt2fdlyssyrtetazeeomhostev0smeafwtdM"et"aanhteaaDrnhressendaeesapadouleyeydysrs"ctitaase0ogeDi.tddf"ariidaaneeOicsniydandtoedlnil7anottiyhnpttu"cnhereriastroneonhelcectotdebaa-eremrlnaanmstcutasodsuinileioeslyenstandhs,sgotsetotif.i.fhosodmtneTr,haoahetnseifsed
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tvheerisfiacmatpiloeninsajemcptiloenawlsaose1x0ce|ieLderdatthheerathllaonwtehde 1sp5e%ciffoierdth1e0se|iLre;-rthuenscosnamtinpuleinsg. calibration
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Results and Discussion
Data Quality Objectives (GOO'S)
We briefly describe the data quality objectives applied in this study below. Appendix A describes them in greater detail. With the exceptions of the anomalous results noted below, all the DQO's were met. Appendix C presents the results for each sample set, organized by pH level.
Calibrations. The minimum acceptable coefficient of determination (r2) for linear fits to calibration data is 0.990. The acceptance criterion for individual calibration points is that their values fall within 25% of the linear fit value; data outside this range are excluded and the linear fit is recalculated. No more than two points may be rejected from a calibration data set. Data for the high or low calibration standards may be rejected, though this results in a smaller effective calibration range. The average results of calibrations performed before and after the analytical procedures are used to calculate the analyte concentrations.
Continuing Calibration Verification (CCV). Selected calibration samples are examined at the beginning of, during, and at the end of each analytical procedure. The results may not deviate by more than 15% of the known values.
Matrix Spikes. The acceptable percent spike recovery range is 70% to 130%; recoveries outside this range % place the analysis out of control, and require intervention by the Team Leader or designee. Analyte specificity is demonstrated by acceptable analyte spike recoveries.
Identically Prepared Samples. Triplicate sample results with relative standard deviations (RSDs) greater than 25% place the analysis out of control, and require intervention by the Team Leader or designee.
Solvent Blanks. Concentration results for solvent blanks exceed neither 5% of the highest calibration standard nor 25% of the lowest calibration level.
System Suitability. Suitability was demonstrated by either an abbreviated mass-to-
charge (m/z) check-tune or performance of a full auto-tune routine.
y
Anomalous Analytical Results
With the following exceptions, our analytical results met or exceeded the data quality objectives of Appendix A.
Spike Recoveries. The triplicate samples PFOS-157 through 159 (pH = 7.0) failed to meet this DQO and were rejected.
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Statistical Methods and Calculations
Using functions provided in Microsoft Excel software, we calculated means, standard deviations, and first-order rate constants (see Appendix B, Equation B8) for various subsets of the acquired data. Our linear regressions included the determination of constant terms, that is, the regression fits were not forced to pass through the origin.
As described in Appendix B (Equations B38 and B39), rates measured at 50C were extrapolated to 25C by dividing by a factor of 10; this approximation is valid for reactions, such as these, with Arrhenius heats of activation near 18 Kcal/mole.2
Data Summary and Discussion
The LOQ is defined as the concentration of the lowest (accepted) standard in the calibration set for which the known concentration exceeds 400% of the indicated solvent blank level (see Appendix A). During this study, the LOQ for PFOS was 308 ng/mL.
Results for the surrogate compound THPFOS were very consistent throughout the study. The percent relative standard deviations of the measured values, calculated for each pH level, ranged from 1.2 % to 3.4%.
Table 4 presents the results of the slope determinations (see Equation B8) at six pH levels and 50C.
Table 4. Observed (50 C) Slopes of PFOS Concentrations in Aqueous Buffered Solution for Various pH Levels.
pH Observed Slope (day'1) Percent (2a) Rate Uncertainty (day1)
1.5 0.00025 3.0 0.00032 5.0 0.00011 7.0 0.00015 9.0 0.00057 11 0.00030
111 73 618 253 89 161
Figure 3 illustrates these values, which are all positive, and the fact that they are generally only poorly determined; their percent relative 2a (95% confidence)
uncertainties range from 73% to 618%. The data do not indicate degradation of PFOS at any of the six pH levels.
In the absence of a clear trend relating the degradation rate to sample pH, it is appropriate to "pool" the data over pH level and determine the concentration slope using the entire data set. Figure 3 illustrates the results of this pooled analysis according to Equation 1, and Table 5 summarizes the results of the analysis. It also indicates no degradation of PFOS, and the positive slope does not provide a half-life estimate.
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Table 5. Calculated Slope of PFOS Concentrations in
Aqueous Buffered Solutions Using Data Pooled Over All pH Levels.
Calculated slope (d ay1)
2.98 x 1 a 4
Calculated slope upper limit (2a )
( d a y 1)
5 . 3 0 x 1 O'4
Calculated slope lower limit (2o)
( d a y 1)
6.66 x 1045
Figure 2. Observed PFOS Degradation for Various pH levels.
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Figure 3. Pooled PFOS Data and Slope Regression.
The mean and standard deviation of the PFOS data do provide a useful estimate of its half-life. Details of the related calculations are presented in below (see Appendix B, Equations B36 and B37). The maximum degradation rate is given in Equation 3:
2aP k F ( k p L x Up A t
Eq. 3
and the minimum half-life is given in Equation 4
j i / 2 -> fnni/2 \ _ h ( 2 ) _ p.p A t l n ( 2 )
p - V pAnin (Vk r )/max
2 a pr
Eq.4
We note that in both Equations 3 and 4, the mean PFOS concentration (jxP) and standard deviation ( a p) can be either molar or mass quantities. Table 6 presents the results of the calculation.
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Table 6. Degradation Rate and Half Life of PFOS in Aqueous Buffered Solutions Based on the Concentration Mean and Standard Deviation
At (days)
42
M-P (ng/ml)
512
aP (ng/ml) 5.00
Maximum Observed Rate at
50 C (day'1)
4.64 x 10'4
Maximum Calculated Rate at 25 C
(day'1)
4.64 x 10'*3
Calculated Half Life at 25 C (years)
>41
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Conclusions
We have performed a study of the aqueous hydrolysis of perfluorooctane sulfonate (PFOS). Six different pH levels were Included in the study, which were carried out at 50C and extrapolated to 25C. Our results based on direct observation of the PFOS concentration indicate no hydrolytic degradation at any individual pH, nor do the data pooled over all six pH levels. From the mean value and precision of PFOS concentrations, we estimate the hydrolytic half-life of PFOS to be greater than 41 years.
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3M Environmental Laboratory Report No. W1878
References
1. "Fate, Transport and Transformation Test Guidelines: 835.2110: Hydrolysis as a Function of pH," U.S. EPA Office of Prevention, Pesticides and Toxic Substances, publication number 712-C-98-057, January 1998. 2. Experimental Physical Chemistry", F. Daniels, et al., McGraw Hill Book Co. (New York), p. 131,1962.
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Signatures
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3M Environmental Laboratory Report No. W1878
William K. Reagen, Ph.D., Laboratory Management
Date
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3M Environmental Laboratory Report No. W1878
Appendix A: Analytical Method
Method ETS-8-13.0, "Hydrolysis of Perfluorooctane Sulfonate (PFOS) and Analysis by High Performance Liquid Chromatography with Mass Spectrometry Detection." This Appendix presents the analytical method employed in this study.
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3M Environmental Laboratory
Method
H y d r o ly sis o f P erflu o r o o c ta n e sulfonate (PFOS) and A n aly sis by
H ig h Performance Liquid Chromatography w ith M ass Spectrometry Detection
Method Number: ETS-8-13.0
Adoption Date: ^ q j0 o
Effective Date:
Approved by:
Laboratory Manager
Date
Team Leader
Bate ^
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1.0 Scope and Application____________________________________________________
1.1 1.2
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11..34 ATtrR(eeRhetccreifcoasfeevhermpeyrttrdoteaiortebohSsSl(oee(tecdr1cmit0diitosi0eaoncdtnrae1i)f13c4fi0e0lnufs%efooodfrr)rootaahrtoshrecaeeptnqeuaqaurnsuflaeeoyaldrislstmiiufytsyola.farncosAeconsaeunqicc-rtubhraaeoanscolscaiuepedmdsae.(rpsTvaolTameHllauumPertatigFaeoteOitrnotrssiSnaxt)aon.cttaorbvliyeteaetvraeriainooalauurflsayostzbureeurtrmhdfofibesgetyramhettoedehdtmpihspHoamedstrr..efi)oxthrsmopdai.knece.
2.0 2.1
ASulimqumoatsr
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of Method____________________________________________ f PFOS stock solution are added to vials that contain buffers at pH
1.5,3.0,
5.0,
7.0,9.0, and 11.0. The vials are then placed in an orbital incubator/shaker set at 50 3
C. Sets of vials are removed at designated intervals and the date and time recorded. The
aqueous sample from the hydrolysis of PFOS is diluted 1 to 10 with methanol (MeOH)
containing internal standard. PFOS, incubated in one ofthe several buffers is separated
oacneatarteev/MereseOpHhasoselvDeniot ngeraxdIioennPt,acwitNh Gde-1teHctPioLnCbycoelluemctnrousspirnagy aionnaimzamtioonnimumass
spectrometry in the negative mode.
3.0 3.1
3.2 3.3 3.4
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the method's recovery efficiency.
PFOS HydrolysiEs TanSd-8A-1n3a.l0ysis by HPLC/MS
Page 2 of 15
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3.5 3.6 3.7
IarsppHrrCsCenautntruayafoatontareinnedlcncloridtydrrehtebsooantisaanirnarlsrvacsacyd.dnueaelettssdildiris,nocfiubtnfaosgnasyhenotrenahacsdttednldahtaavf.dcaveal-baaainlirslbiocrrdudvordorraielaanet(uttsrotIoidttidniSreontetag.)hhunns.ceraeuuAhvoAndlmciuteeddoiarbvgnkimiccleehgnfucoripostutscfnohiwtr.ratoaoueartnnnTomnciedolydhaonlantimetforohnirdv(rfrgoeeCeastfuesthoerComnlhieerolteaVeumeucno,pat)asaierfs.rolelneuaaiynsbtcSrmsusceirotesloaoamistfitnnmusoiieadonnnadnprantteotoseacrcdprunocnoeusrndanofsorldcattvbacc,endeueoinasaa.selrtdtlassopryeTdt.acoeelzethekndfeIidmi,oSddtsbhntieooarndseenrsnotuaaseaetlrpntlrupdishlmnogitpesoimgneleoanipsdmnieoaeluidanafsamprnritiaalpneataeinnyrnltysoayoeaolrrltavoyiyefnicrtstdtdiaitmhcec.laeaaally
3.8 3.9
nDavuaILSnnoisiiae(admtllsudlbs)ymtieiaittmsoeirpox/enambrefy.erudiqepsbf.AumcafeeairIboesrfnitnvldtsetehceiopftodwelrauirotfdinptmitriihoootolhurnmnataethitdt(eneihoLnidgyftcOpefdisuersnQroerbtoteploaa)vlna.tyneittrsoahneTsilnestoyhiitudtaseserftniu/collndbuoedroutwbyniiofnnee-frpgsmfesrlotrtoorsirucssotceocomelntvilndhubueecumeltnneeirtotnes,ba,nataeliirm,nrfaaltittndphwqihaeoleuaehlsnynsidiidrcstiaeth-ilhhrslduaie.e.atqtiauncTcsnaigoahdalnliislvbseyobexrzslenavttertterediaepion.cslntiotaIaiicocfdbscuntdlmuhyreivresedmsersptaeesooefltalrytavtsefhnoueardernrdtmaehttdrdeeeedsddst..
3.10 wSibRss1sitl0eimaeagtcnsnthrtpiidkieimdlonasaiunfe.rtsydeasp1rSldties4thnaac.h.me3ittafaTh)mnipeehrdledizeeucnperalLpioriimlonemOribt.rguiciQrntmHerasgontao.iouctrowaoeftFnignaenhoecccveirucegedlmunrrhiav,frtlbafraeyieaontctrtrmyymhieaoanta(aanotsctnyrereiwaiysebxlbiyeg-oStedthrpeenteewecsoapa,rtmeteai9teoenth9irinndnen%tseahtgLhnla1clcOatn4y.oot.Q1n4cnafhdctaiiotiidsnumtseidsaeoneelnncs1lksee4wtn.ch.l2otiieTetm)whdhlaieinenantvscdtLtehhotlOphaenortesQcefeteclhtonighiesswtuericgoiaesdoetnsoienntol(lcevninsenreoeanieennnltslt-ryzaatoet5irootno
scfotuarrnvtdheae'rsdrle,isnviedearusraurlessgtahrreeesrseios2un5l%ftoo.rbmtauilnae. dFforor mthethpeubrpaocksecsaolcfuthlaetisotnuduys,inthgethaeccceaplitbarnacteiocnriteria
Residual = known conek.n--owcanlccuolnaete. d cone, x 100
4.0 4.1
WH44..1e1a.a.12rltnhinagnWpHphsdrroaooeaonscpadnadere.fdldrteehuetCeayryelaeplw.uwrsoaWtoerpilanvoehriernenannlstgate_sabsv_lile_anrt_tita_pmir_ohee_sos_fso.oi_bdr_l_afeo_llar_np_ada_llr_ptp_sra_aor_ctf_tsit_cho_aif_sl,t_phd_re_iol_duc_etee_sd_cus_rari_emb_.ep_dW_le_ssae_maw_r_pi_gtlh_leo_spv_or_ele_svp_eaa_nnr_tad_it_nio_an___
PFOS HydrolysiEs TanSd-8A-1n3a.l0ysis by HPLC/MS
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4.1.3 pRFaoecvrkipeionwtge.nmtiaatlerhiaazlsa,rdansdof3eMacEhncvhireomnimcaelnutasledL,arbeofrearttoorimesatCehrieaml sicaafeltHyadzaatradsheets,
4.2 C44..a22u..12tionstREsthhenieeqnsnuspueedurnermacyltelpht,goataoltranteshrddusewutnhHcadaerPtreytLthh.iCneerpwmeohiossibscisihblueifslftipaithcyniadeosanefrtscdqoasunraeatranpemtripteiyrnpeaatptoriaeocrdneo.dfmrwepslihethtper1ti:ho1eratrcouenbt.oengDein/oMnnienoOgt Haal,lrouwn
4.2.3 4.2.4
EtrEhunnenssscuu.orreemttphhuaatttebtrheteforoerseaisvseteanarotlilunrgguhnthndeiatrrtoau.gnesneqinuethnecesuthpeprleyitsanamk tpolechomarpdldetiesksesqpuaceencoen
5.0 Interference
5.1 5.2
htCtiCoonaootrdednndreettwfaammemmarooreiinennnnsscamattenrtriaaatoasyttetneiclnttfoahhrwuosaaosmtteldttvhheiceneteonertrleceteusrt,miiifossernnernnesaooln,gecHessveuuneP.cctlssLhhU,.CiigsnnTletttahueetsebrrhsffiweerenorrgraeeuor,nnteuiacc,ntneeiaen.d.neaddnaeaontlteayhclseytiorssrisosacfomosmfpollpalevboeponnrreotantbctoeslrasmynsikmansygemctohaurousadstnebbalelayunsskisesd
6.0 Equipment_______________________________________________________________
666...123 AHShneawakllyeetrti,tc-iaPnlacbcuakblaaartndocr(eHcsaPepn)asb1ilt1ei0vo0efHtmoPa0Li.n1CtamSingyisntegmte,mopr eerqautuivraeleant t50 3 C
666...333...123 PASuoumltvoepsn,atmqdupealgteearrs,nsAaerrLy,S,MMMoododedelelGlGG11313231211A3AAo,,roveraqeruiqaiuvbialvelaeilnnetjnetction volume capable
6.3.4 Column heater, Model G1316A
66..45 DMiaosnsesxpIeocntrPoamcetNerG. -Hl ecwolluemtt-nP,a3c5kamrdmLxC4/M.0SmDm, ,o1r0eqpumivpalaecnkt,incgap, aobrleeqoufivoapleernatting in the
6.6 sCelloecckte,dd-iigointa-ml. oOnintloyrionngemcloodcek should be used, to insure unambiguous documentation of
66..78 tpChHeenmctroierftrueegrc.et pcCeaorpfmaobirnlmegaoMnfcmoedaoeiflnpt3ar0io8nciepndHgu/rT3e0es.m00prepramtufroerM5 emteinr with 3-in-l gel filled combination
66..910 6.11
ReDDreleeaacfcttoraatrirgdasoeyindnrsaeagtlety(oampsrniH,.sdc/sArpaoerpffoPaetcwbCreelaesncrscoeoie:nmf/gHtmpeesumaiwtigepnlnreetaarctaltiasn-tpPuifanrarbeogc)lmke,4aoorthrdfe2ec-qodCunCehittvereoacmllteloSinrntatgtitohneH, VPLerCsisoynsAte.m6.a0s3woerllmaosre recent.
PFOS HydrolysisEaTnSd-8A-n13a.l0ysis by HPLC/MS
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7.0 Supplies and Materials___________________________________________________
77777.....12345 PCVLGaariraisbamtldeselup,usa-4rct0pea-dipmppeaLitupstV,eotgvOsli,aaAsglssl(,a,Isd-1sCi.,s5Hpd-moiEsspMLaobsloaerbeleq,u1iv-maleLntto) 10-mL
7777....7689
VHBAeoauamltuokimmelrteaos,ttnrigciGclpaafsilspsat,eisgtvkthasot,rri,vocasuyarsiproisanuibzgsleeesssioz(efpsdreiscpiseinosning
1% oftotal volume), 10-5000 pL
10-pL
to
1000-pL
8.0 888...123 8.4
RMAt1gtSACrh8reaemlaeae.cnla0lmttmswmihigbfMosaeeaoernrnoiranngirkotf1liihtinuawl2owtsgmms.(ni3aaMttsm.hton1ahaee)nodco1ar.Onde.u8S1itEHl.uaW0dtS-xLtm)atMbea:aanvemtHna(edoiacrpdlPrlaepeulawwLcetrpmrao:CariddtrtoeAte/hsdeStxSe(rnrlPiritdomaceoaEwnatccfoaCgdlckeatee/rtemsGShnprlketyeotiC.axsglnAb2uirtgselathdtemriadaooadrbnedMreno)uc1esseuft)0iffn.g0rmemtho.orT0lumLsy0haso0.itoEwsl1unfMietoMsgiitogcSebnhhcOeribioseHuomnmsaceaataedstad,o.aneogdprrbarteyephqshewueniricevvqisgaauoltheailivvnnneettgi,ntdaottiuAilvut et(0esl.ye1teo5
8.5
8.6 8.7
88I8B7gPBHn....4u4r5uu0ate.i..efn1,fd2p1ffrdaeaeennblrrriaedosnslobefocP1ispT0MnTSiTokasounsolo0r.eFnHHfuhtfr1feelon.eapafaOr0uati0pOcPdcePforsinlt0a1yoeear(eSFi1mCFHdsMr0o0psnndls0OoeOaihin.apto.s,msbFdglr)are0Sr.lurSairdfleaTmu0Leasoltatotdptii0ihtppetf(iidnoorrvisioTa,tarTeicnsnpoothonleTrrpHkcgHunlysweysopaauror/toPddPaomfearooimnalclernFddFaurfcnfloioLdeespttnOOedppbniliptdponnyiorHTHecSoSMnPrirtnseMciHorru)hienMn=iatM/exsinsyfPqDttesaOielMirsseu1FOamnoaeaddiitOiHs.OdclnttuvieHa5k1uieflsHdoOa.tuSoTo0r,teal(3ntiy.rt.freHol(Rnmnes.a.yEtnoa0Pdtgd(hen.moLtpxEfP,1uf)esiSbc7pea.a(ax0nrfrvkrfErrom.eopcka,ii0oeoM0phlnrpnxemsnpvlx,m0aatgraau9claaeeipo0rsmliemma.edneOnnelx0:MtepddptdgeiiabH1,A:omgailtteu8pteatreanr/ioOia.tf:mdHnPlo2cofTytTAdtFnHe)e(LhfH.mceSralO1l1yeasPTladbse0Pa1StlsorsmicHy,4ikF.le0kGbt0lt0useaOupiPa0wrtoua0tnuaatr0oaFiSniniekdstordnocdOideiipanoikd8ggwnennrgStnbl.ih/godsh4ttiio/mrienitmsosfse.inogfhr2ettnLlsangnpoauLub)sMgasnaacHitub0mii(diblldknnnfRyoe.eyf1saepts5gOnsloeetdrte0l.ioawarfdet0Hnidi0o2enlnslssseeueu0ur..ddops5dtpietotsahgailgirT.nrfifourn)LreehnircdhdpnotogopigeimisnoHrofmassi1gsftorna1Pao0e4sM8lsrFCud0k..0Oi1Rtenaipw,)OoSCt.L1inaHt-hL.
PFOS HydrolysiEs aTnSd-8A-n13a.l0ysis by HPLC/MS
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qsbbc8touu.ua7naffn.ffnc1deeetarrintsrsitdeoirnsaslpau.tosi)HtoefiConap2anl1sHel0.sia5db7r4oregm.fal0gtpaLe,isH7vsao.e0c1pfn,o.o05bnar.1,etnt3aaldoNi.bn0wl1e,eH0.r5ps.C0..RH01,,e/a(tc7neroe.md0radm,pg9eefe.rin0anat,satguualrrrnpaeedHdmteh1)mee1t.epe0arHasuutosraifenmmaglblepinbeutnurstfcofrheofarosasemloldlbtupeutHmfiofepncreassr.l.aibtPSurrarteoetpi.roaenrTehe b) 125 mL of 0.2 M KC1 (reagent grade) c) Adjust pH to 1.5 with additional 1N HC1 d) Bring to a final volume of 1L with 18.0 MQ water
8.7.2 ap)H13108.0..20g pMoQtaswsiautmerbiphthalate (reagent grade) dissolved in approx. 600 mL b) pH adjusted with 1N HC1 to 3.0 c) Bring to a final volume of 1 L with 18.0 MQ water
8.7.3 ap)H Am5.pL0pr1o8x.0imMaQtelwy a3t.e8r777 g ammonium acetate (reagent grade) added to 250 b) Add 250 mL 0.052 M acetic acid (reagent grade) c) Add 18.0 MQ water to about 900 mL d) Add to glacial acetic acid (about 0.5 mL) to adjust to pH 5.0 e) Bring to a final volume of 1 L with 18.0 MQ water
8.7.4 pa)H 570.00 mL 0.1 M KH2P04buffer (reagent grade) b) 291 mL 0.1 N NaOH (reagent grade) c) Adjust pH to 7.0 with either 1N HC1 or 1N NaOH d) Bring to a final volume of 1L with 18.0 MQ water.
8.7.5 pa)H 496.0mL of 0.1 N HC1 b) 125 mL of 0.1 M borax (Na^BO^HjO) (reagent grade) c) Adjust pH to 9.0 with either 1N HC1 or 1N NaOH d) Bring to a final volume of 1 L with 18.0 MQ water.
8.7.6 pa)H 51010.0mL 0.05 M NaHC02(reagent grade) b) 227 mL 0.1 N NaOH
PFOS HydrolysiEs TanSd-8A-1n3a.l0ysis by HPLC/MS
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3M Environmental Laboratory Report No. W1878
c) Add water to 950 mL d) Adjust pH to 11.0 with 1N NaOH e) Bring to a final volume of 1 L with 18.0 Mfi water 8.8 T88..e88s..1t2AnaPpolcovaaS11yorpdoF0f2fpetnpdl-t.aeOipu1hmkcrinat.moaieSi1iLsrnaxonn1eeptsgitndvd)temropr]oassoi.lbSratclutoofiyupttoalxeftmiuihalnnolikaytmdeenaieosdotlkas1rfiysinspit0noaacte.i0etgpnllkhfuypd[ensl0etEarogi1n.(dos5oxl/S0kixumanal,emiud0tmsamcLit0d:nLotipi0eandnooldtoge.pfend:ftlpPtio[yAo1l1mFEu2051tOtxs.h,i0P10apnmSe0.Fm0ig1]kLm0O.n2ptigon)Slbape/graugtm:kshnf/stAmfLedwaoennlLmrMiaudt(afthaaPSetinreorOMFeakdrncOlHMywe(tiiSSOtsoiedeetpHnsOihcslrtot.uae1HMinltpo2uiFdaeno.dt1irOainin.8eolr5aHudd.(n)4lSt,.ib(.oceo1rSyofcAen)entsPatci(ucooFd1tSleind0Otoaenii-ncn1Sntp1rtg2gLia80io.tsi.-10in4nmao...l111naiL1q)maf)utifonoiLtseatarl
9.0 9.1
RSaemcoprldetiHmaesn dofliinnigti_a_l_p_r_e_p_a_ra_t_i_o_n_a_n_d__d_i_lu_t_i_o_n_o_n__t_h_e_f_l_u_o_ro__c_h_e_m_i_c_a_l_d_e_g_r_a_d_a_t_io_n________
9.2 (Ohnycderothlyesi9s.)0amnaLlyosfisdsilaumtipnlgesporlevpeanrta(tiSoenctsihoene8t .(5A.1tt)ahcahsmbeenetnBa)d. ded to the hydrolysis
mshioxutuldrebse, tshteorseadmaptl4ess2houCldbbefeoarneadliylzuetidown withitihn M24ehOoHurasn. dAulntetirlnaantiavleylsyi,stchaensbame ples
performed.
1100..10 QInutearlniatlySCtaonndtarrodsl.__I_S_(_s_) _a_re__a_d_d_e_d__in__a_c_o_n__st_a_n_t_c_o_n_c_e_n_t_r_a_ti_o_n_t_o__a_ll__st_a_n_d_a_r_d_s_,________ samples, and matrix spikes.
10.2 Sample triplicates. Prepare and analyze all samples in triplicate to provide a measure of t2h5e%proercgisrieoanteorfsahnoaullydsibse. nTohteeda.naAlypsptroshparilal taecscteepptsRmSuDstvbaeluteaske<n25to%c.orRreScDt tvhaeluperosbolfem bCeofnosruelatnwailtyhsitsheisTaellaomwLedeatodeprroorcedeedsi(gen.ge.esfaomr dpilreercet-irounnasn, dadfdinitailoancaclebplatannkcse, eotrcr.)e.jection
10.3 oMstfuatdhtyre.ixaCnsoapnliyckteiencsat.rlaPrtuironenp. saroefathpeosspt-ihkyedsrhoolyusldisbmeaatpripxrosxpiikmeafteolryeeaqcuhaolftothae mpHids-ruasnegdein the cthaelibsaramtipolne tsrtiapnldicaardte.s Ttohewmhiacthriixt csoprikreespsaomndpsl.e sThhoeualdnableysatnsahlyazlleadcicmepmtepdeiracteenlyt sfoplilkoewing recoveries of 100 30%. Spike recoveries outside of this range should be noted. Appropriate steps must be taken to correct the problem before analysis is allowed to proceed (e.g. reruns, additional blanks or spikes, etc.). Before the analysis is allowed to proceed, consult with the Team Leader or designee for direction and final acceptance or rejection of the analytical run.
PFOS HydrolysiEs aTnSd-8A-1n3a.l0ysis by HPLC/MS
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10.4 SCboevoCleloVvrwei,snatthanBedplrlaaoifmnbtekliert.mnoSof,oqumlusvoeaernnbettaittcbhakltaai-nontonk2sb0(LasichnOkojQeuscl)odtiloovbfneetnshr.teubAnilnacbsncetkerfsupo.mtraebeanlentdv(Saaelfucteetirsoefnvoe3rr.t9yh)ec. abIllifabanrnakatailoyrentevccuaalrurvreeys,
11.0 Calibration and Standardization____________________________________________
11.1 11.2
rpSSsrCaLueomrtteavnaoalauloni,gnidetudrbadiewaoanfrratmratnesrdotrrhdsisrafohoeotdfpivownrroeroeulssesrifmlinytpdrgaaoean2aapnmarepl0rdraseopotatribhrifnerooolcegjdexeonrrsmicien.dn.mtstitiAwasrePoaeiirnnrtonicneetsanthalpa,ilyloypacathsrznap3neteler0dapcoa0ndiurapntidilntoretalaieegertarsrian/dttonemoesd.ntatLclpsooEsoesiffttxxnotroctatfchecaonr8eerelardnin0mllbraait0aubrrrtilaadnenrnstta.ggiitattoohUa/nitmonnnehassndleeLasyaotnsetsarPthafxidansleFttndy.hecOddataereCnraalSdiirtaponbadsalentrsrreaacaseeroatktundilrtfoliahaeutbPnrlcecwreFotsmabaiitOmottaeiarhnonSgmaydnttishiniebaoonmnenerfddviMteTunw.eetseghderaeasOo.rodmuedHfTsoitfh.tlhhodiesegayta.
12.0 Procedures__________________________________________________________________
12.1
S12a.m1.p1le 12.1.2
12.1.3
atmBhDO"Obnhasoedeniebpvnxftetioeesseiakmorrvpsieamen.lii"tiuakzsit.lPltnehepeiaroeeaiptetknhsptarietheentpaaoferpgpeocenrfaahuwfouanrrelpapimecvtartphvtiiuibsraaeotaoeltolonesnrpvwfyrfonieioiauafolvlrltmtfaeiaebmptbnahesocdeaeerlhrmaacpsobtpatpoioefHpolilcen4ne,ikt0tpdsmf.-rrsUmtaoetuhaspmlsLantae"itdrpssVwtaaatlhtoriOmiiiedlcosdlAspkns,blbmestvweryo"iaaoaa,ltnlunlrh"lsskteadeifsrlowueynhnvrpizuestolaeehmi.lpdctuscap.bmatreaeEpoern"sxado,ficaotfmchrnrpirdapetsHitalpmecisticlaekyeaaridltnnpa1ebagob"molei,ytanlooLzrsterdwaodn.fildl
12.1.4 12.1.5 12.1.6 12.1.7 12.1.8
12.1.9
RaaTsawFsMtRtPdtRhohfnefaoeeolfiteeemldemaateimtucrmhxeackrcipitoprleoenniaotaal"merolovcirdtnevTrostnhd1ueaiiuysetfnit0abebht,trmthut-leotaoheaehccspherddateeao.eeatevooLtdrhbslnicZidrvofliecmaayattGtitnaoetliicepahisoentsaratnfmlht.e,ehnsoussohttettoe,ehp"eaiefTfte.goraeencmtcahosohshdroaapamaeamtnppedlnpmmrytreldiuetVeas1nhtroppi-srht-ba0tialOe.ylwlimeatesseeorRupbdAelaisinibsprLnecnaezreseromlgtvicsec,eeileohonoeiuoypadeenaf.olrfbnnavdlyddtvuftardhaR,hauii1ltaitrpaednnoperhre2tmoliiardcrceP.snioer1toulno.aeagFxanpy.cbctrt7dpOHAdoieltastt.odehuihhteSfgltrondeoewhdeis1hr.emtefehe/datetmtseeantoeeytshh(niaktntLssmAiaesceiirtankrgeh.deotesnegcetnapfabaiaCr.toanmicltluntfoyfhaochTefdopctnueanfmdehrleedbpte.aei1tpresdalnthpan2onhrttsiuepeiectu.olteo1ieurmsemloaBno.ceutt1pntip.p)atobtho1p.ieprtfeoenRi.mriorrmaonia,sre(mFta.ptaSeepcuenrom.meoHairubarcercpuae,tdthaelliifdtelsoliftiyvltmhesnaiiroemtmabee8tlael.h.opy8c.neok.1riitni)ontr
PFOS HydrolysisEaTnSd-8A-1n3a.l0ysis by HPLC/MS
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12.2
12.1.10
12.1.11 12.1.12 12.1.13 I111n222s...212tr...112u4m 12.2.3
12.2.4 12.2.5 12.2.6
eavRAUU4P8aCCPiabViS0Snsnpiu0.pll3elasslehha8etaapfat0iapm1iivtlooeer.qnccnnrsvs2r4iepccrovnekueeooggfa)m9kkaoixygtsosvpitta9ttaas.lhe/ihuattetrolat.mmt4hhqi.ehSte2-apb1atitaausaL)paho5hl0vtsCe.tteeettpne--aeiqettn2Taapmar:mthhcSluvcpo"ollLyHaeesslLaeiespxlaaCtcvpnPsi1ilGiachamlgboeneamics5FpoeskirsmmarepprftdOafaaemsavhrirlrdascpptt"tenneSoioeeiioitouallcoganamlvpeeltolmaHtyilnhhuussitrnyttraeeitteeoPttmts1aasailslehedsottsuLitnnatsahameayrse.aneuddCpnnnertnssncdHLtoiIiaddusomdpnansatalaatPbrseasegtomvsaursaroeeaqrdLtoeendettfr,domaoaui,lkC(drasetrucamneseto,aIenaaprdt.atDndedcrccgchdoilbmddtcoaaetdaoh.,eeoepercrnstll9pmomodirsubl1hstqbrlayanarm0moeuep(srurcaavmrStletMhnaeeryepiLnt.ahterae.uopnpLbioaiaalciotmlMcnoietsderntnsnduholiscedrieoentoreiohbfnacovtedOnadwcicfPohe.otm1tokwtHtehF8rnahhn4tAnasctee.lOeiee.4,lseskct,a1ldyhi.tsStatomn2oAr9iselspnuctmaa)nsttr9soelpaoetctnnteltp9nareenrmrootaabuiiiosrridaklwntssenemyepidatcai(icvjsoansrunEruaveteteeiicdhglgstcsaenxsmqlyehsee.ytttas.ua.idesdia,vmovofepexlaEonyrianilqnptapeuanrtdenucrlhlpflltt.eaodeeseries(eeoaib:xenortgtrtcnc.eoaihclgsemshovlbeae(.reacnelSatqaadma0oentttneuees3oeetpwnacen1llltltnoyteh4iyifsctuo.o9es.hegnir9sh)..
12.3 H12P.3L.1C Isne'Ast'StunaTlpalAl:ythNseiDscBoolYfuP"mFonOn: SDHiPSoansmeyxsptelIeomsnsPf)r.aocmNpHG-sl,14.5.0,3x.03,55m.0m,7,.01,09p.0maonrdeq11u.i0v.alent.
Solvent A: 2mM Ammonium Acetate in 1% MeOH (Section 8.3)
Solvent B: MeOH
Solvent Gradient:
Time,041m...000inutes 8.0
%60A 6550
%B 44990505
0F.3lomwLR/matien 000...333 mmmLLL///mmmiiinnn
Post time: 5.0 minutes; Column Temperature: 40 C
12.4 R12e.c4o.1mmeAndneadlysMisaossf PSFpeOcStroamt petHerss1e.t5u,p3;.0*,5.0,7.0,9.0 and 11.0.
AIPDoorcnlyqiaizurnaiigttsyiioGtinoasMnFMoldooewde Nebulizer Pressure
SEelelectcrtoesdpIraoyn (SIM) N8 eLg/amtiivne 30 psig
PFOS HydrolysiEs aTnSd-8A-1n3a.l0ysis by HPLC/MS
Page 9 of 15
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3M Environmental Laboratory Report No. W1878
Drying Gas Temp 300 C Capillary Voltage 3500 V
Example conditions are applicable to Hewlett Packard HP 1100 equipment only.
Tim e SIM Identity (m in) Ions 5.6 399 PFHS2 (M -H), quantitation ion 5 .6 4 0 0 PFH S 13C , (M -H ) qualitative ion 5.9 427 THPFOS (M -H ), quantitation ion 6.2 499 PFOS quantitation ion (M -H)
1-"6Q.2upaenrftl"uoiorno5hf0eo0xraTnHesPuFlPfOoFSnO;amS i1d3eC"Q,uaqnut"ailoitnatfiovrePiFoOnS 2- perfluorohexanesulfonate 3- perfluorooctanesulfonamide
G ain (EM V) 1.0 1.0 1.0 1.0 1.0
Fragm enter (V ) 70 70 70 70 70
D w ell (m sec) 210 210 210 210 210
12.5 Autosampler set up*
AAuuttoossaammpplleerr:Program: Injection volume:
ANLonSeModel G1313A 5.0 pL
Example conditions are applicable to Hewlett Packard HP1100 equipment only.
12.6
S12a.m6.p1le 12.6.2
aEaoAsbIcntdgaefnaanraeftltnaronhiyeydnlrretsyoa.eiitfzvrsshyaedIeeenfqtrc(hd.msuCateelaaoCinenfbrtcVledreeeaa)rct.trhttiadrhoaRfo,enntunesCs2ranictm0eCasavnopiVcendllqrv,ejayeuearacdnni2ntsstdi0id,otbiaunaloQfapnsntnCdeatkfrorriisetlun2heantfs0eoofttwrsihebmnerieejttaethcrohtcuaieaftonlinisonh,baniaarimgsnapnh,ttppaioearlolsyenonttszhpdceserttoatihaaasleincetcbehqdocrpueaaancrretltdiiekniobnsfcfinruexaoai.sgtrntitaaoagaDbinnnnlcodyeasa.antlatraionbdtnhta,rdaelaytrietodennsd
12.6.3 12.6.4 12.6.5
PeaiSSsxulataactDvocreeteeseacttdthhmeheefmeipvssblseeeeteqqarrcnuuth1redeaan,nar1ycrca9deeac9s.ctt,e8carso,bsarslmideafivpwntehlgeiettshth,oseeaatqnshneudeaqemQounreecCdnecec(coremortnhraaestetsaryi1pixn2oas0rnsep1dmi9ilknio8segr.ts)eetdoathnitandondtsha9aeym9'sslpiendlqeaeutbsee.ln.acn(eek..gs).
into the if today
1133..01 DPctiinhnoeatatmeaentggkpa5rroEaaAu(ttviifnnooiavdannleu.lsi)aspyCtteifsimocroioismnfemias:pcnotPbihduoeaennasCekdbs.lassaisnlmwPeeceliuiuttansohkltesbiabsnacteoosoimseionsyleesnimnrisdsfemo_ept_rrhere_tetrhd_rosi_aecfut_nogi_rtrneh_acg_sasaih_olap_ainbe_psra_ehoak_ofta_iuutno_hlsdn_dein_eimcd_grhe_uoarn_srou_ttmiat_hfos_iaame_avtdo_aedg_btiipr_yscae_cmoae_rekx_r.t_tmehr_Paes_aecien_gatci_ukhno_atgn_sl_dg_pr_ee_aa_tke_r_
PFOS HydrolysiEs aTnSd-8A-1n3a.l0ysis by HPLC/MS
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3M Environmental Laboratory Report No. W1878
13.2 psatCckhhrariaeenioloileubcccrtlauruidtaclrolctsvabiupetoaeliesnaorirtonanfmeotbtdeeoartgamuyfcirsoknaibinn:etneegsdgCdtaatfacThwrnlcoeHcteimut(epPhklxtaF)atttthOhbeceerleaSentnchp.aaaealblsCriecPebtoaFhndrlnaeOtiesbttciiuSeronoalrnttmmcteiswoorpinnanniotcanehumelddnntsethbdtthtaryehauenotTpndiidollnaeoeonrtastedlmstsori.nnigonLagHytlh:e.eoseaawtrdcawheenrvidoseoaefrrr,tdnhde.oeextseAtpiedgHsr.nnsuemaQemlausfittaonrainrgnctdediftisiaarrreutsdictso-tioninorgddnaetra
Ln f If-p--r-n- c-4l -N versus minus elapsed time (-t). The subscripts t and 0 refer to analyte
concejnPtFraOtSioJons)determined at some elapsed time t and at t = 0, respectively. The slope of
13.3 13.4
t0CMomoh.bba8eaatsl0tacertr0ierurinxiv,slxeuaecsdtldospetipnfimntrkishogkeuaemeltlptrsPiien.ttxFhhrecOCeesiepsSaTcnilakkteccl.aeruioebmlTnrcarecohatLceetveoineetovrahtr2nredieasevretipsaiareoelnusounr,dsrcesicendtfaihngeonletcsrteiurihtgeanlhencactietoehsferoevpnotleflhalfroooleytrtwh(afsodeiovhnirprerogeerHuexcaealttgdqimecoeurhbnanaseot.atprilf>iio)cktnhe0se:ste.ar8venm0ced0oara.stvrrudeiFsx.roytsr.uprsiC2kivnaeaglsc.lutuheUleasstcelienutsgrhsvetethhsean
V Recovery - (kserve<*spiked saacmtupallearmesouulntt-sopbikseerdved sample result) _ 13.5 sSaammppleles:triplicates. Calculate the relative standard deviation (RSD) for the triplicate
RSD = StanMdaerdanDCeovniaet.ion x 100%
Tofhtihsepamraeamne.ter is also known as the coefficient of variation, a measure of the confidence
14.0 14.1
MClininoteeeetrafchrfeicocpuidter,nvPpetaesorrtififscDou0erl.a9tmer9lr0aymnofciornregaa_rtce_ioca__tune_rra(_.rc_2y_T)_.ho_eAf__qcn_uu_aar_cvn_cet_eist_pas_tth_aioo_b_nule_lad_ct_obt_hee_fe_ef_ixlc_oai_wem_n_iatn_no_ed_fd_hdc_iel_got_ehs_ree_ml_nyi_dn_fsao_to_ri_ofl_intn_he(_era_2cr_)iu_tf_yrov_ra_en_. _d
The acceptance criteria for curve-fitting residuals (Section 3.10) is 25%. Alternative
14.2 mtcMmhoeeeratarrhteseroluiaadxrstesiosomnopnsefikcncfoeotusserr.fvoufefisPcipfeniieertgfrtnoicqtneru(gmnra)t(adesfnr.opacgrite.kiqcqebuuaeraaseqddecurdroaaavttwtiieioccarn)ycrsnum.firrnavogyemsabnimesdna0cte.ro9cinx9est0srsopaolirrkylgeimirnseiaatsmtsoeapmr.rleeeRsrc.eeaccsToeohsmre.dmaiAnnenanthldayeecsdctreasfpwhotaradlblaltea
rapacrnocgbeepletpmplaebcrceeeftonhrteesapannikaaellyyrsseiicssooivsuetarloylofvwcaoelundetrtsoool.pfrAo10cpe0perdo.p3r0Ci%aot.nessSutpletipktsheemreTucseotavbmeerLiteaeskaeodnuetrtsooidrceodreorsfeitcghtnitesheefor
direction.
PFOS HydrolysisEaTnSd-8A-1n3a.l0ysis by HPLC/MS
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3M Environmental Laboratory Report No. W1878
14.3 14.4
SafcadmCocolealoercsnomaniemtwgsrptpounieetlnleradeR.euesdTtuS.iAonrDraepgipnpmprvacolraleioacyclnpleutaiteerebstidesairos.sat<fe.tgBir2rsoeeeP5tlnefaaeop%ttrveisrfveer.omertraiRhmfpunaiSesaacntrDlnacybc1tesieve5onias%tbtnlaiuad.ksfseierfIeasofnfdlemolttorwhofewet2nahce5crpoende%eritrrtnorceouogfecerprtnaergvttnopharddcleeliiueafccpefteaoeerd,tonrre,rebtepcrnslllooaeacalmnmtecilsevipfumboetllehertitsfetottos.hhartaeehTenreTaaheamleeniyrnaeaosaimclitnuysoianasmLollitysueosmstaitftsadeosnnefhdrdaaeolrldrd
14.5 cLcuhiremvceikt, sosttfaonQpdutaharednrtwiutnial.ltiboOennu.lysTetdhh.eosRliemesaiantmaolpfylqzeeusaranenmtaitlaayitznioeindngbisseaefmoqrupealtlehsteowltahitseht laaocnwceeewpsttacsbatalleinbdcraaalrtiidborinnacttiuhorenve.
14.6 cSsosicnttaluoaaedltlnniaivbicddnneraaiaasnntrrttetdgdrisoubovtnmihlnaraeclescnuutnaekrertlluvsaieabm.lecrrtceetarSohnotooinatsoblttpvcnasiroemesacnnryghivttnareesbeamcodlatakuiitionnernscnkartesa.tstie,hnosqIadanhfunna.opedru4denTrla.ttdehikiapmIesslflhaiewssnocosoisiwlt,nttvhhrtgenuwegnomoolrteremebvsacnlotoelateellrnvsraeohkenttfhasnihn,tlathaltgnbhnbel2ceeasao5norml5%ukluv%ansmeitmnshnnchtetasaao,rbyipurntleyuableadnbedokkibvnnbsaeeeg.yrrcs,etetfaehorstooposcrmap.foreayudagl.tohohwiTlgryhuhilse
1155..10 15.2 15.3
PbUDCstrooosioserllkplaleesogcmunsetetagHdilolrolaPuefsnLrmssabCPcmoironsrpneeotltvhleacveeiowennlhneuatatrmsziswtoaentarnosbdsdaytoweiunphsisdplenawonWctshaipenesaogtosesssfaticintgebeolhllalMellisiegtstaceohptnaimoioacprnciegnlutoaetimermwmesuai.eBzlanoeTtntiwUotnahcsecotea2nnntga.de_inn_Efee_lmorr_asop_trait_.oys_n_ai.np_tp_or_ot_hp_erifaltaem. mUasbele
16.0 16.1 1166.32
RFPSriieglilncnotoauorntuddtthshd_eaa_hrt_dey_dac_rlo_lop_gliy_resa_sip_soh_sf_iaca_msl_lap_gnl_reda_ppl_ahr_bei_cpe_sla_rwaa_nit_tdih_od_nia_nwt_sato_rar_ukn_msa_hle_yen_set_itsI_Dcs_ou._mm_p_ml_ea_tre_il_ey_s,_fm_o_ra_ka_irnc_hg_i_sv_uin_reg_._to__in_c_l_u_d_e_
11116666....4567 16.8
PaPEpSAlrhrtnlrioiocntnirenthtteoriicctcvhaihaoaeyllrllpdioesbsyrmltraoeaaonclantyftdtidroostoahidgnsnreardtiastacleampobsmdrg.lseaebppatsolanaeaordtnpoakditrpniaeocpatpenugparrerrinvnoaaaetpflinoroisdinrnatmfaitownnearcdtommilarourkaenddtdseiihiornaeetnhpetwheatoshnerctediossnntpsafttynohnoerdeircneaarelratisldhnwsaseatnrhpdrayreaal.eywtrpasaaefdwrisala.etdta.iaoftnialelfo.ilgeb. ook. Make a
111777...012 AAAttttttaaccahhcmmheemnnettnABt..s_HR_ey_pd_rr_eo_sley_ns_it_sa_tSi_va_em_C_p_lhe_e_mL_oi_cg_as_lh_Se_etr_tu_c_tu_r_e_s_______________________________
PFOS HydrolysiEs TanSd-8A-1n3a.l0ysis by HPLC/MS
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3M Environmental Laboratory Report No. W1878
18.0 Bibliography
18.1 18.2
TFC0O5aoRpt7xeeC,ir,cJaTHatinrSaoauunnnabdasrslbpytooDa1ornet9kcfa9eionn8sifd.(tCiOTohPnreasPmnTosisfSfotp)rrHym83a,a"5ntR.id2oo1Pnb1hTe0yersHtsictCysG.d,Wru1oisdletyeaSslsiittsnu,edaPssehnOa.DtfFEf.,uidcn1ietc9ioto8ifo8n,Pn, p"roeB.fvDupef-nHf8te7,iro.EnSP,oAPluet7si1oti2nc-siCde-s98a-nd
19.0 Affected Documents None.
20.0 Revisions Revision Number
Reason for Revision
PFOS HydrolysiEs TaSnd-8A-1n3a.l0ysis by HPLC/MS
Page 13 of 15
Page 35 of 71
Attachment A. Representative Chemical Structures
1. PFOS (Perfluorooctane sulfonate, C8FwS03)
MW (anion) = 499
F
3M Environmental Laboratory Report No. W1878
R+ R = K*in this study, but may also be Li+, Ca+2, or DEA (diethanolamine)
2. THPFOS (1,1,2,2-tctrahydro(trideca)fluoro sulfonic acid) MW (anion) = 427
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ETS-8-13.0 Analysis ofPFOS Hydrolysis Products by HPLC/MS
Page 14of 15
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3M Environmental Laboratory Report No. W1878
Attachment B. Hydrolysis Sample Logsheet
TEST AKAYLTE:
Lab Roquas! Humben D o m in a) Intensa):
Nomina) T em p e ra tu re;.
C
Sample No.
Time: initials; Irrt Temp pH
1.5
1.5
bik 1.5
Buffer
Fluorochemlcal Degradation (Hydrolysis) Analysis
Test Analyte
_ Incubator ID: _ Start Date: _ Stop Date: _
Incubation Interval: ,
Spike Solution
_Jays.
Time: _ Time: p hours.
Dilution Solvent
SoluflcnTO
Amount (m l)
Solution 10
WOAmount
Solution IP
Amount jp U
Solution P
Amount <mU
Freezer )D: _ Start Date: Slop Date:
Internal Standard
Solution ID
Amount (I*.)
Tima: _ lim e;
Comment
blk
bik Comments:
Component
Cone. Component
(MCoBn/meL. ) Component
Cone.
(uo/mL) Component
Conci
C>o*O
E T S -8 -1 3 .0 Analysis o fPFOS Hydrolysis Products by HPLC/MS
Page 15 o f 15
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3M Environmental Laboratory Report No. W1878
Appendix B: Kinetics Model
This Appendix includes a mathematical description of the kinetics model employed in the study.Appendix
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3M Environmental Laboratory Report No. W1878
Kinetics Model
B1. Reaction Components and Rates
The arguments below are based on the following idealized set of reactions representing the hydrolysis of a parent compound P and its hydrolysis products A m, which number N. The actual hydrolysis reactions that occur under neutral, acidic, and basic conditions are subsumed in these equations, and are assumed to proceed with pseudo-first order rates k Pm(forthe parent) and k Am(forthe parent's hydrolysis products).
P + H 20 <=>nm A m+ Y ml (m= l to N)
(B1)
A ra + H 20
Y,
(m= 1toN)
(B2)
where the general symbols Y ml and Ym2 represent all the other hydrolysis products.
B2. Parent Compound Concentrations
Equation B1 indicates that the pseudo-first order differential change in the parent concentration P is given by
(B3)
which is equivalent to the separable differential equation
(B4)
Equation B4 may be directly integrated to obtain the general solution
ln[p]= " XN nmkPmt +C m=l
W ith the initial condition P (t = 0 )s P 0, the specific solution to Equation B4 is
(B5)
using the additional definition of the total parent hydrolysis rate
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3M Environmental Laboratory Report No. W1878
N'
kp= X nmkpra m=l
(B7)
Equation B6 can be re-written in a form that allows a least-squares estimate of the total
parent hydrolysis rate:
/p \
k pt -In
vV
(B8)
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 hydrolysis rate.
Equation B6 indicates that over a period of time T 1^ (the parent hydrolysis half-life) the parent concentration P is reduced through hydrolysis by a factor of two, where
(B9)
A least squares estimate
of the parent hydrolysis half-life is therefore available from
,l/2_ 2 )
(B10)
B3. Product Compound Concentrations
The pseudo-first order differential changes in the product concentrations Am (using Equations B2 and B6) are
d A m= ( n mk PmP - k AmA m)d t = ( n mk PmP0 e"kp ` - k AmA m)d t
(B11)
and the (first order, non-separable) differential equation governing the product concentrations is
dt + k AmA m = nmk PmP0 e,-k p t The "standard form" of Equation B12 is
(B12)
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3M Environmental Laboratory Report No. W1878
A m+ S ( t ) A m = Q ( t ) where the "function" S (t) is actually a constant:
S (t) = k Am and
Q (t) = nmk PmP0 e~M . The general solution A mto Equation B12 is contained in
A m eJS(t)dt = J.Q (t)e JS(,')dt' dt + C
(B13) (B14)
(B15) (B16)
where
gJS(t)dt _ e JS(t')dt' ,, g k ^ J d t _
(B17)
and
dt + CjQ ( t) e 's(t')d*'d t + C = nmk PmP0J ekAm` e'kpt
(B18)
There are two cases of Equation B18 to consider. In the circumstance that k Am = k p ,
which occurs only when the hydrolysis rate of the m`hproduct is identical to the total parent hydrolysis rate, the general solution to Equation B18 is
(f o r k Am = k p )
Amekpt= nmkpmP0t + C
(B19)
and, using the initial condition A m(t = 0 ) = A ^ , the specific solution to Equation18 is
(f o r k Am= k P) A m= (nmk PmP0 t + A m0)e'kpt .
(B20)
We note that when k ^ = k p = 0 (that is, when both the parent and potential product
are hydrolytically stable), Equation B7 requires (also) that k Pm= 0, so Equation B20 becomes
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3M Environmental Laboratory Report No. W1878
A ,, = A,,
(B21)
indicating, as required, that the product concentration does not change with time.
The circum stance 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 hydrolysis rate k pand the product hydrolysis ra te k ^ approach each other.
In the more probable case, for which k Am ^ k p (i.e. that the hydrolysis rate of the mth
product is different from the total parent hydrolysis rate), the general solution to Equation B18 is
A ,, e`Am1
^m^Pm^O (k^-kpjt kAm-kP
(B22)
and the specific solution to Equation B18 with the initial condition A m(t = 0 )= A m0 is
Am
A m0+
knpmk--Pkm*Pm0
\ /
t __ n mk Pm P 0 g-kp t k P ~ k Am
(B23)
Of greatest interest here is the case in which the product compounds are known to be hydrolytically stable, that is, when k ^ = 0 for all m. In this case, Equation B23 becomes
(for hydrolytically stable products)
A,,=A- + ^ = A (l-e * '') . Kp
(B24)
B4. Relationships Between the Parent and Compound Concentrations Equations B7 and B24 can be combined to obtain
(for hydrolytically stable products)
N V ( Am" A m0)
(B25)
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3M Environmental Laboratory Report No. W1878
so that
(for hydrolytically stable products)
( l-e " kpl)= ^
^no)
m=l P 0
or
(B26)
(for hydrolytically stable products)
kpt = -In "1- r ( A ,, - A n,,,)
m=l P 0
(B27)
If the changes in the product concentrations are ail small compared to the original parent concentration, that is, if
Y Am -A m0 m-1 P0
1,
(B28)
we may use the expression (valid for -1 < X < 1 )
ln(l + X) = X ---2X 2 + -3X 3- -4X 4+.
(B29)
and Equation B23 becomes
(for hydrolytically stable products and
Lm0 <<Po)
t AV A -A-^mO^
k p t= -
77 po
(B30)
Page 43 of 71
or (for hydrolytically stable products and
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3M Environmental Laboratory Report No. W1878
(B31)
B5. 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 " *3 (the "limits of quantitation") below which the product concentrations A mcannot be reliably measured. If during an experiment carried out over the period of tim eA 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 ra0 = 0 and 2) at tim e 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^ as follows:
(for hydrolytically stable products at concentrations below the limits of quantitation)
k P < (k PL , = Tr 0 ra r 1r mS=l A TMQ
(B32)
Under the same circumstances and assumptions, the experimental data indicate that the parent half-life T 1^ (see Equation B9) is greater than the value (t ^ ) . as follows:
(for hydrolytically stable products at concentrations below the limits of quantitation)
-1
T 'p
M Tl L
=
7VK Pr /mfax- =
At
p1* 2) X Ar _ m=l
(B33)
The reader should note that Equations B32 and B33 are valid only when both 1) the products are hydrolytically stable and 2) the concentrations of all the potential products are measured. Otherwise, the quantity (k p)maxin Equation B32 may not actually
represent the maximum possible value of the rate constant k P, and the related result in
Equation B33 for (t ^ ) is also questionable.
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3M Environmental Laboratory Report No. W1878
B6. Parent Half-Life Estimates Based on Limits of Quantification and Experimental Precision of Product Concentrations
In certain experiments, some hydrolysis products are present at quantifiable but essentially constant concentrations over the time (A t ) of the experiment. In this case, it is the experimental precision of the measured product concentrations, rather than the limits of quantitation, which contribute to the estimate of the maximum value of the parent hydrolysis rate k p. If the set of concentrations measured for the mth product have the mean value p.mand standard deviation o m, the data do not exclude the possibility that the product concentration increased from the initial value o m - p mto the value o m + p mat time t = A t . Taking this possibility to be the actual case for the measured products, the maximum value of the quantity (A m- A m0) is 2 o m. This reasoning suggests that the following estimate of the maximum parent hydrolysis rate is appropriate:
(for hydrolytically stable products at either 1) constant measured concentrations with standard deviation amor 2) concentrations below the limits of quantitation)
k P^ (kpL =
LOQ + X 2* ,
Below LOQ
Cons tan t
(B34)
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 hydrolytically stable products at either 1) constant measured concentrations with standard deviation crm or 2) concentrations below the limits of quantitation)
~y2 p
>~
V(t 1/P2) 'min
2)
= A t P0 2 )
( k p )max
Below LOQ
Constant
(B35)
The reader should note that Equations B34 and B35 are valid only when both 1) the products are hydrolytically stable and 2) the concentrations of all the potential products are measured.
B6. Parent Half-Life Estimates Based on the Experimental Precision of Parent Concentrations
In certain experiments, the hydrolytic parent remains at an essentially constant concentration over the time (A t) of the experiment. In this case, it is the experimental precision of the measured parent concentrations that determines the maximum value of the parent hydrolysis rate k p. If the set of concentrations measured for the parent have the mean value p pand standard deviation o P, the data do not exclude the possibility
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3M Environmental Laboratory Report No. W1878
that the product concentration increased from the initial value p P - g p to the value p P + c P at tim e t = A t . This reasoning suggests that the following estimate of the maximum parent hydrolysis rate is appropriate:
(for essentially constant parent concentrations with mean value p Pand standard deviation GP)
k P < (k p)max ^ p A t `
(B 36)
Under these circumstances and assumptions, the experimental data indicate that the parent half-life T 1^ is greater than the value (T ^ ) as follows:
(for essentially constant parent concentrations with mean value p Pand standard deviation 0 P)
t !/2p
( ^ )t\ pP/r'min
ln(2) _ pP A tln(2)
(k p)max
2G p
(B37)
B8. Temperature Dependence of the Reaction Rate and Half-Life
In order to increase the speed of the reactions of interest, we conducted this experimental study using samples maintained at the temperature 50C = 323 K. Of greater interest are the corresponding results for the environmentally important temperature 25C = 298 K.
When the Arrhenius activation energy for a reaction is A H a, Equation B38 B1 provides the following relationship between the hydrolysis rates (Iq and k2) for that reaction at two different absolute temperatures ( T and T2):
k , ____ [AHa ' 1 1 " [ R LTA2 TJ
(B38)
where R = 1.99 x 10'3 Kcal mole'1K'1is the ideal gas constant. Using the value82 A H a=18 Kcal/mole, the rate ratio k , / k 2 at the corresponding temperatures T, =298 K and T 2=323 K is
ki _ _
18 1.9 9 X 1 0 '3
'1 .3 2 3
-
2 91 8 1J J1
exp(-2.35) = 0.095
(B39)
i
___1/
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3M Environmental Laboratory Report No. W1878 Equation B39 indicates that the hydrolysis reactions of interest proceed approximately ten tim es more slowly at 25C than at the chosen experimental temperature of 50C. Accordingly, the rate reactions reported here for the temperature 25C are ten times lower than those measured at 50C, and the hydrolysis half-life estimates reported here for 25C samples are ten times longer than those calculated from the 50C experimental data. References to Appendix B: 811. N Levine, "Physical Chemistry," McGraw-Hill (New York), pp. 498-501 (1978). 82 F. Daniels, et al., "Experimental Physical Chemistry", McGraw Hill (New York), p.131 (1962).
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3M Environmental Laboratory Report No. W1878
Appendix C: Selected Analytical and Kinetics Results
This Appendix includes selected sample data and their related kinetics results. For brevity, some solvent blank and continuing calibration verification results that did meet the data quality objectives have been excluded from the following tables. However, all data failing to meet the data quality objectives are included below.
Page 48 of 71
PFOS Buffer Hydrolysis Study at 50 C.
3M Environmental Laboratory Report No. W1878
All cpo1.nH5centratiToinmsein7(Dnagy/sm) l. 111111......555555 223441185294
Cone. 508 551100 555510115473
In [P]t7[P]o 00..000050 00..000152
-0.001
00..001114
pH 1.5,PRFaOteSc@onSsOtaCnt graph
0.05 0.00
-----*----- ----------- ---- --
EI --00..0150
" -0.15
y = 2.5R02E=-034.9X3E- -50.315E-04
" - 0.20
-0.25
0 20 40
Time (days)
60
p3.H0 Time 7(Days) C5o0n4e. In0[P.0M00Plo 333333......000000 442231129854 555555111110120409 000000......000000111211152007
PFOS @50 C
Time (days)
SUMMARY OUTPUT
Regression Statistics Multiple R R Square Adjusted R Square Standard Error Observations
0.62682 0.39291 0.27149 0.00515
7
ANOVA
Regression Residual Total
df 1 5 6
SS 0.00009 0.00013 0.00022
Intercept X Variable 1
Coefficients -0.00053 0.00025
Standard Error 0.00435 0.00014
% 2a Slope Uncertainty 111%
SUMMARY OUTPUT
Regression Statistics Multiple R R Square Adjusted R Square Standard Error Observations
0.77640 0.60279 0.52335 0.00431
7
ANOVA
Regression Residual Total
df 1 5 6
SS 0.00014 0.00009 0.00023
Intercept X Variable 1
Coefficients 0.00313 0.00032
Standard Error 0.00364 0.00012
% 2a Slope Uncertainty 73%
BACK TO MAIN
Page 49 of 71
PFOS Buffer Hydrolysis Study at 50 C.
3M Environmental Laboratory Report No. W1878
All cpoHncentratiToinmsein(Dnagy/sm) l. 5.0 7 55..00 2114 5555....0000 44235298
Cone. 515 555555000112388800
In [P]t/[P]o 0.000 ----000000......000000001211594440
0 .1 0 -i o 0.05 -
-S ' 0-00
1- 0.05 - - 0.10
- 0.15 0
pH 5.0,PRFaOteSc@on5st0aCnt graph
y=* 1.1R128=E-20.045x4-E9-.08267E-03
-- -- --- ~
20 Time (d4a0ys)
60
pH Time (Days) Cone. In [P]t/[P]o
777...000 77..00 77..00
41724 24231589
455711484 551152 552109
0.000
---00000.....000000010024286
0.10 I 00..0005
-0.05 - - 0.10
-0.15
0
pH 7,0,PRFaOteSc@on5s0taCnt graph
_______y_=__!.5R122-E-U045x4-E7-0.414_2_E_-0_3__ 20 Time (d4a0ys)
60
SUMMARY OUTPUT
Regression Statistics Multiple R R Square Adjusted R Square Standard Error Observations
0.14332 0.02054 -0.17535 0.01279
7
ANOVA
Regression Residual Total
df 1 5 6
SS 0.00002 0.00082 0.00084
Intercept X Variable 1
Coefficients -0.00987 0.00011
Standard Error 0.01081 0.00035
% 2a Slope Uncertainty 618%
SUMMARY OUTPUT
Regression Statistics Multiple R R Square Adjusted R Square Standard Error Observations
0.36797 0.13540 -0.08075 0.00646
6
ANOVA
Regression Residual Total
df 1 4 5
SS 0.00003 0.00017 0.00019
Intercept X Variable 1
Coefficients -0.00744 0.00015
Standard Error 0.00557 0.00019
% 2a Slope Uncertainty 253%
(A) Data in Italics have been rejected from the fits on the basis of the data quality objectives (see text).
BACK TO MAIN
Page 50 of 71
3M Environmental Laboratory Report No. W1878
PFOS Buffer Hydrolysis Study at 50 C
9.0 999999.....0.00000
174 507 00..000040
2234418529 555550012152202 -0000....000013104055
pH 9.0,PRFaOteSc@on5s0taCnt graph
SUMMARY OUTPUT
Regression Statistics
Multiple R R Square Adjusted R Square Standard Error Observations
0.70888 0.50251 0.40301 0.00942
7
y =5.713E-04X- 7.766E-03 R2= 5.025E-01
20
30 40 50
Time (days)
60
Time (Days) 7 14 223185 4429
C5o1n4c^ 555555100111195876
In 0rP.0W00[P]o
---0000....000000019967 00..000075
PFOSatSOC
Intercept
-0.00777 0.00057
% 2cr Slope Uncertainty 89%
SUMMARY OUTPUT
Multiple R R Square Adjusted R Square
Standard Error Observations__________________
0.48645 0.23663 0.08396 0.00902
7
0.00025
BACK TO MAIN
Page 51 of '
PFOS Hydrolysis Analysis Results
HP LC/MSD 1100 PFOS Hydrolysis Study
50 C .; pH 1.5 All concentrations in ng/ml
PF0S
MeOH Blank L1 Std, 300.90 L2 Std, 401.20 L3 Std, 451.35 L4 Std, 501.50 L5 Std, 541.62 L6 Std. 601.80 L7 Std, 702.10 L8 Std, 802.40 MeOH Blank MeOH Blank
PFOS-001A PFOS-002A PFOS-003A PFOS-004A PFOS-025 PFOS-026 PFOS-027 PFOS-028 PFOS-049 PFOS-050 PFOS-051 PFOS-052 PFOS-073 PFOS-074 PFOS-075 PFOS-076 MeOH Blank CCV1.5, 501.5 MeOH Blank PFOS-097 PFOS-098 PFOS-099 PFOS-100 PFOS-121 PFOS-122 PFOS-123 PFOS-124 PFOS-145 PFOS-146 PFOS-147 PFOS-148 PFOS-169 PFOS-170 PFOS-171 PFOS-172 MeOH Blank MeOH Blank L1 Std, 300.90 L2 Std, 401.20 L3 Std, 451.35 L4 Std, 501.50 L5 Std, 541.62 L6 Std, 601.80 L7 Std, 702.10 L8 Std, 802.40
External Standard quant r^O.999 Linear, include origin Calibration range: 300-800ng/mL
V ial# 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40
41 42 43 44 45 46 47 48 49 50 - 51 52 53 54 55 56 57 58
!/ PFOS0003.D
RT 0.0
PFOS0004.D
6.2
PFOS0005.D PFOS0006.D PFOS0007.D
6.2 6.2 6.2
PFOS0008.D
6.2
PFOS0009.D PFOS0010.D
6.2 6.2
PFOS0011.D PFOS0012.D
6.2 0.0
PFOS0013.D
0.0
PFOS0014.D PFOS0015.D
6.2 6.2
PFOS0016.D PFOS0017.D
6.2 6.2
PFOS0018.D PFOS0019.D
6.2 6.2
PFOS0020.D PFOS0021.D
6.2 6.2
PFOS0022.D PFOS0023.D
6.2 6.2
PFOS0024.D PFOS0025.D
6.2 6.2
PFOS0026.D PFOS0027.D PFOS0028.D PFOS0029.D
6.2 6.2 6.2 6.2
PFOS0030.D PFOS0031.D PFOS0032.D PFOS0033.D
0.0 6.2 0.0 6.2
PFOS0034.D PFOS0035.D
6.2 6.2
PFOS0036.D PFOS0037.D
6.2 6.2
PFOS0038.D
6.2
PFOS0039.D PFOS0040.D
6.2 6.2
PFOS0041.D
6.2
PFOS0042.D
6.2
PFOS0043.D
6.2
PFOS0044.D PFOS0045.D PFOS0046.D PFOS0047.D
6.2 6.2 6.2 6.2
PFOS0048.D PFOS0049.D PFOS0050.D
6.2 0.0 0.0
PFOS0051.D
6.2
PFOS0052.D PFOS0053.D PFOS0054.D
6.2 6.2 6.2
PFOS0055.D PFOS0056.D
6.2 6.2
PFOS0057.D PFOS0058.D
6.2 6.2
Spike Amount =
Original Amount=
AREA 0
904650 1174066 1319550 1498940 1621894 1761605 2049253 2315618
0 0 1610328 1615948 1614464 1911799 1492442 1523548 1503439 1761706 1501472 1498384 1539735 1825238 1506431 1516998 1519482 1805033 0 1486941 0 1586882 1477990 1506268 1783638 1489526 1525801 1497479 1796727 1515386 1522659 1530943 1859840 1526048 1531093 1525693 1812642 0 0 911389 1197270 1329980 1569355 1654212 1791298 2086339 2356392
100.30 510.50
CONC. 0.00 300.8 393.4 443.4 505.0 547.3 595.3 694.1 785.6 0.0 0.0 543.3 545.2 544.7 646.9 502.8 513.5 506.6 595.3 505.9 504.8 519.0 617.1 507.6 511.2 512.1 610.2 0.0 500.9 0.0 535.2 497.8 507.5 602.8 501.8 514.2
504.5 607.3 510.7 513.2 516.0 629.0 514.3 516.1 514.2 612.8
0.0 0.0 303.1 401.4 447.0 529.2 558.4 605.5 706.8 799.6
ng/mL ng/mL
or VcRSD
100% 98% 98% 101% 101% 99% 99% 98%
%Spike Recovery
0% 102%
1% 87%
2% 107%
0% 100%
4%
1%
1%
0%
101% 100% 99% 106% 103% 101% 101% 100%
89% 100% 115% 98%
3M Environmental Laboratory Report No. W1878
THPFOS
Day
Day 0 Day 0 Day 0 DayO Day 7 Day 7 Day 7 Day 7 Day 14 Day 14 Day 14 Day 14 Day 21 Day 21 Day 21 Day 21
Day 28 Day 28 Day 28 Day 28 Day 35 Day 35 Day 35 Day 35 Day 42 Day 42 Day 42 Day 42 Day 49 Day 49 Day 49 Day 49
Mean STDEV %STDEV
RT
AREA
CONC.
5.9
444137
367.9
5.9
439597
367.9
5.9
428929
367.9
5.9
448527
367.9
5.9
445358
367.9
5.9
457122
367.9
5.9
442512
367.9
5.9
450877
367.9
5.9
445707
367.9
5.9
442993
367.9
5.9
447797
367.9
5.9
449355
367.9
5.9
438799
367.9
5.9
443628
367.9
5.9
447460
367.9
5.9
436481
367.9
5.9
441226
367.9
5.9
444754
367.9
5.9
449044
367.9
5.9
453987
367.9
5.9
454803
367.9
5.9
448561
367.9
5.9
448125
367.9
5.9
445533
367.9
5.9
445695
367.9
5.9
476345
367.9
5.9
445579
367.9
5.9
449198
367.9
5.9
442980
367.9
5.9
445723
367.9
5.9
449841
367.9
5.9
445467
367.9
5.9
459061
367.9
5.9
451623
367.9
5.9
454163
367.9
5.9
447915
367.9
5.9
458757
367.9
5.9
455665
367.9
5.9
458353
367.9
5.9
457178
367.9
5.9
458383
367.9
5.9 5.9 5.9 5.9 5.9 5.9 5.9 5.9
5.938 0.008 0.13%
468259 463704 454923 471691 470565 459784 462734 464047
451285 9527 2.1%
367.9 367.9 367.9 367.9 367.9 367.9 367.9 367.9
BACK TO MAIN
Page 52 of 71
3M Environmental Laboratory Report No. W1878
HPLC/MSD 1100 PFOS Hydrolysis Study 50 C .; pH 3.0 AH concentrations in ng/ml
PFOS Hydrolysis Analysis Results
PFOS
. ' SSsuMiJfe-1\ MeOH Blank L1 Std, 300.90 L2 Std, 401.20 L3 Std, 451.35 L4 Std, 501.50 L5 Std, 541.62 L6 Std, 601.80 L7 Std, 702.10 L8 Std, 802.40 MeOH Blank MeOH Blank PFOS-005A PFOS-006A PFOS-007A PFOS-008A
PFOS-029 PFOS-030 PFOS-031 PFOS-032 PFOS-053 PFOS-054 PFOS-055 PFOS-056 PFOS-077 PFOS-078 PFOS-079 PFOS-080 MeOH Blank CCV3.0, 501.5 MeOH Blank PFOS-101 PFOS-102 PFOS-103 PFOS-104 PFOS-125 PFOS-126 PFOS-127 PFOS-128 PFOS-149 PFOS-150 PFOS-151 PFOS-152 PFOS-173 PFOS-174 PFOS-175 PFOS-176 MeOH Blank MeOH Blank L1 Std, 300.90 L2 Std, 401.20 L3 Std, 451.35 L4 Std, 501.50 L5 Std, 541.62 L6 Std, 601.80 L7 Std, 702.10 L8 Std. 802.40
External Standard quant: ^=0.998 Linear, include origin Calibration range: 300-800ng/mL
Vial# 91 1 2 3 4 5 6 7 8 91 91 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65 66 91 83 91 67 68 69 70 71 72 73 74 75 76 77 78 79 80 81 82 91 91 1 2 3 4 5 6 7 8
FILE#
RT
PFOS0050.D
PFOS0051.D PFOS0052.D
6.2 6.2
PFOS0053.D
6.2
PFOS0054.D
6.2
PFOS0055.D
6.2
PFOS0056.D
6.2
PFOS0057.D
6.2
PFOS0058.D
6.2
PFOS0059.D
PFOS0060.D
PFOS0061.D
6.2
PFOS0062.D
6.2
PFOS0063.D
6.2
PFOS0064.D
6.2
PFOS0065.D
6.2
PFOS0066.D
6.2
PFOS0067.D
6.2
PFOS0068.D
6.2
PFOS0069.D
6.2
PFOS0070.D
6.2
PFOS0071.D
6.2
PFOS0072.D
6.2
PFOS0073.D
6.2
PFOS0074.D
6.2
PFOS0075.D
6.2
PFOS0076.D
6.2
PFOS0077.D
PFOS0078.D
6.2
PFOS0079.D
PFOS0080.D
6.2
PFOS0081.D
6.2
PFOS0082.D
6.2
PFOS083.D
6.2
PFOS0084.D
6.2
PFOS0085.D
6.2
PFOS0086.D
6.2
PFOS0087.D
6.2
PFOS0088.D
6.2
PFOS0089.D
6.2
PFOS0090.D
6.2
PFOS0091.D
6.2
PFOS0092.D
6.2
PFOS0093.D
6.2
PFOS0094.D
6.2
PFOS0095.D
6.2
PFOS0096.D
PFOS0097.D
PFOS0098.D
6.2
PFOS0099.D
6.2
PFOS0100.D
6.2
PFOS0101.D
6.2
PFOS0102.D
6.2
PFOS0103.D
6.2
PFOS0104.D
6.2
PFOS0105.D
6.2
Spike Amount =
Original Amount=
"'r e a
911389 1197270 1329980 1569355 1654212 1791298 2086339 2356392
1614579 1630018 1615096 1913128 1482241 1508691 1512531 1788783 1524174 1535721 1493221 1832061 1536518 1509305 1502071 1806145
1514429
1522352 1535855 1518633 1803572 1511584 1523640 1523080 1815571 1530536 1513422 1545677 1838657 1526013 1520230 1521742 1818700
928344 1190154 1340916 1535521 1642704 1755846 2041833 2301233 100.30 510.50
; ~ /o ot otaridarci
CONC.
or %RSD
299.8 398.8 444.7 527.5 556.9 604.3 706.4 799.9
100% 99% 99% 105% 103% 100% 101% 100%
Recovery
543.2 548.5 543.3 646.5 497.4 506.5 507.9 603.5 511.9 515.9 501.2 618.4 516.2 506.7 504.2 609.5
508.5
511.3 515.9 510.0 608.6 507.5 511.7 511.5 612.7 514.1 508.2 519.3 620.7 512.5 510.5 511.0 613.8
1% 1% 1% 1%
1% 0% 1% 0%
101% 99% 108% 100%
96% 102% 107% 102%
305.7 396.3 448.5 515.8 552.9 592.1 691.0 780.8
ng/mL ng/mL
102% 99% 99% 103% 102% 98% 98% 97%
THPFOS
Day
DayO Day 0 Day 0 DayO Day 7 Day 7 Day 7 Day 7 Day 14 Day 14 Day 14 Day 14 Day 21 Day 21 Day 21 Day 21
Day 28 Day 28 Day 28 Day 28 Day 35 Day 35 Day 35 Day 35 Day 42 Day 42 Day 42 Day 42 Day 49 Day 49 Day 49 Day 49
Mean STDEV %STDEV
RT
AREA
CONC.
5.9
468259
367.9
5.9
463704
367.9
5.9
454923
367.9
5.9
471691
367.9
5.9
470565
367.9
5.9
459784
367.9
5.9
462734
367.9
5.9
464047
367.9
5.9
461517
367.9
5.9
464987
367.9
5.9
451634
367.9
5.9
448685
367.9
5.9
440387
367.9
5.9
440863
367.9
5.9
448559
367.9
5.9
444912
367.9
5.9
448819
367.9
5.9
450797
367.9
5.9
443601
367.9
5.9
449371
367.9
5.9
441970
367.9
5.9
449535
367.9
5.9
449151
367.9
5.9
439038
367.9
5.9
439801
367.9
5.9
446475
367.9
5.9
444351
367.9
5.9
442297
367.9
5.9
438219
367.9
5.9
438608
367.9
5.9
451702
367.9
5.9
435628
367.9
5.9
439283
367.9
5.9
440005
367.9
5.9
438938
367.9
5.9
446735
367.9
5.9
444873
367.9
5.9
442251
367.9
5.9
446017
367.9
5.9
443867
367.9
5.9
445836
367.9
5.9 5.9 5.9 5.9 5.9 5.9 5.9 5.9
5.938 0.006 0.10%
462115 457623 454403 468438 465895 452965 449514 456062
450641 9918 2.2%
367.9 367.9 367.9 367.9 367.9 367.9 367.9 367.9
Page 53 of 71
BACK TO MAIN
3M Environmental Laboratory Report No. W1878
PFOS Hydrolysis Study 50 C .; pH 5.0 All concentrations in ng/ml
Sample MeOH Blank L1 Std, 300.90 L2 Std, 401.20 L3 Std, 451.35 L4 Std, 501.50 L5 Std, 541.62 L6 Std, 601.80 L7 Std, 702.10 L8 Std, 802.40 MeOH Blank PFOS-009A PFOS-010A PFOS-011A PFOS-012A PFOS-033 PFOS-034 PFOS-035 PFOS-036 PFOS-057 PFOS-058 PFOS-059 PFOS-060 PFOS-081 PFOS-082 PFOS-083 PFOS-084 MeOH Blank CCV5.0, 501.5 MeOH Blank PFOS-105 PFOS-106 PFOS-107 PFOS-108 PFOS-129 PFOS-130 PFOS-131 PFOS-132 PFOS-153 PFOS-154 PFOS-155 PFOS-156 PFOS-177 PFOS-178 PFOS-179 PFOS-180 MeOH Blank MeOH Blank L1 Std, 300.90 L2 Std, 401.20 L3 Std, 451.35 L4 Std, 501.50 L5 Std, 541.62 L6 Std, 601.80 L7 Std, 702.10 L8 Std, 802.40 External Standard quant: ^=0.999 Linear, include origin Calibration range: 300-800ng/mL
PFOS HydrolysisAnalysis Results
PFOS
Vial # 91 1 2 3 4 5 6 7 8 91 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 91 43 91 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 91 91 1 2 3 4 5 6 7 8
FILE#
PFOS0002.D PFOS0003.D
0.0 6.2
PFOS0004.D PFOS0005.D
6.2 6.2
PFOS0006.D
6.2
PFOS0007.D
6.2
PFOS0008.D PFOS0009.D
6.2 6.2
PFOS0010.D PFOS0011.D PFOS0012.D
6.2 0.0 6.2
PFOS0013.D PFOS0014.D
6.2 6.2
PFOS0015.D PFOS0016.D
6.2 6.2
PFOS0017.D PFOS0018.D
6.2 6.2
PFOS0019.D
6.2
PFOS0020.D PFOS0021.D
6.2 6.2
PFOS0022.D
6.2
PFOS0023.D PFOS0024.D
6.2 6.2
PFOS0025.D
6.2
PFOS0026.D PFOS0027.D
6.2 6.2
PFOS0028.D PFOS0029.D PFOS0030.D
0.0 6.2 0.0
PFOS0031.D PFOS0032.D
6.2 6.2
PFOS0033.D
6.2
PFOS0034.D
6.2
PFOS0035.D
6.2
PFOS0036.D
6.2
PFOS0037.D PFOS0038.D
6.2 6.2
PFOS0039.D
6.2
PFOS0040.D
6.2
PFOS0041.D
6.2
PFOS0042.D PFOS0043.D
6.2 6.2
PFOS0044.D PFOS0045.D PFOS0046.D
6.2 6.2 6.2
PFOS0047.D
0.0
PFOS0052.D
0.0
PFOS0053.D
6.2
PFOS0054.D
6.2
PFOS0055.D PFOS0056.D
6.2 6.2
PFOS0057.D
6.2
PFOS0058.D
6.2
PFOS0059.D PFOS0060.D
6.2 6.2
Spike Amount -
Original Amount^
ARE 0
920859 1213792 1322391 1567941 1636007 1762987 2035774 2318415
0 1599697 1620745 1609628 1905791 1536180 1514846 1551056 1898623 1518639 1486225 1554591 1827548 1505528 1475788 1514395 1780324
0 1404658
0 1511241 1525099 1505194 1808328 1552671 1542978 1545524 1802633 1554103 1530315 1540760 1828799 1493355 1516484 1532381 1832744
0 0 924706 1224849 1344452 1517149 1636681 1791592 2077403 2347306
100.30 510.50
dNC. 0.0
302.1 403.9 441.6 526.9 550.6 594.7 689.4 787.6
0.0 537.9 545.3 541.4 644.3 515.9 508.5 521.0 641.8 509.8 498.5 522.3 617.1 505.2 494.9 508.3 600.7 0.0 470.2 0.0 507.2 512.0 505.1 610.4 521.6 518.2 519.1 608.4 522.1 513.8 517.5 617.5 501.0 509.0 514.6 618.9 0.0 0.0 303.5 407.7 449.3 509.3 550.8 604.6 703.9 797.6
ng/m l ng/mL
% of Standard or /cRSD
100% 101% 98% 105% 102% 99% 98% 98%
%Spike Recovery
1% 102%
1% 126%
2% 107%
1% 98%
1%
0%
1%
1%
101% 102% 100% 102% 102% 100% 100% 99%
102% 89% 99% 110%
THPFOS
Day 0 Day 0 DayO Day 0 Day 7 Day 7 Day 7 Day 7 Day 14 Day 14 Day 14 Day 14 Day 21 Day 21 Day 21 Day 21
Day 28 Day 28 Day 28 Day 28 Day 35 Day 35 Day 35 Day 35 Day 42 Day 42 Day 42 Day 42 Day 49 Day 49 Day 49 Day 49
Mean STDEV %STDEV
R
' AREA"
CONC.
5.9
473070
367.9
5.9
460726
367.9
5.9
439572
367.9
5.9
490981
367.9
5.9
467449
367.9
5.9
457579
367.9
5.9
435372
367.9
5.9
452504
367.9
5.9
452903
367.9
5.9
458464
367.9
5.9
457729
367.9
5.9
446683
367.9
5.9
452315
367.9
5.9
451206
367.9
5.9
447136
367.9
5.9
461076
367.9
5.9
454800
367.9
5.9
455213
367.9
5.9
470258
367.9
5.9
457698
367.9
5.9
451840
367.9
5.9
454891
367.9
5.9
453183
367.9
5.9
448199
367.9
5.9
435070
367.9
5.9
449803
367.9
5.9
448098
367.9
5.9
439229
367.9
5.9
453428
367.9
5.9
446110
367.9
5.9
448727
367.9
5.9
449347
367.9
5.9
444454
367.9
5.9
458675
367.9
5.9
446514
367.9
5.9
449537
367.9
5.9
460270
367.9
5.9
450174
367.9
5.9
448540
367.9
5.9
452518
367.9
5.9
447058
367.9
5.9 5.9 5.9 5.9 5.9 5.9 5.9 5.9
5.934 0.011 0.18%
461022 461213 453927 455268 457342 452098 456825 452021
453601 9576 2.1%
367.9 367.9 367.9 367.9 367.9 367.9 367.9 367.9
Page 54 of 71
BACK TO MAIN
3M Environmental Laboratory Report No. W1878
HP LC/MSD 1100 PFOS Hydrolysis Study 50 C .; pH 7.0 All concentrations in ng/ml
PFOS Hydrolysis Analysis Resuits
f?FOS
THPFOS
Vial #
FILE#
:.:v ,:RT; "'AREA
MeOH Blank
91 PFOS0052.D
0.0
0
L1 Std, 300.90 L2 Std, 401.20
1 PFOS0053.D 6.2 2 PFOS0054.D 6.2
924706 1224849
L3 Std, 451.35
3 PFOS0055.D 6.2
1344452
L4 Std, 501.50
4 PFOS0056.D 6.2
1517149
L5 Std, 541.62
5 PFOS0057.D 6.2
1636681
L6 Std, 601.80
6 PFOS0058.D 6.2
1791592
L7 Std, 702.10
7 PFOS0059.D 6.2
2077403
L8 Std, 802.40 MeOH Blank PFOS-013A
8 PFOS0060.D 91 PFOS0061.D 51 PFOS0062.D
6.2 0.0 6.2
2347306 0
1614386
PFOS-014A
52 PFOS0063.D
6.2
1625352
PFOS-015A
53 PFOS0064.D
6.2
1643727
PFOS-016A
54 PFOS0065.D
6.2
1996185
PFOS-037 PFOS-038
55 PFOS0066.D 56 PFOS0067.D
6.2 6.2
1536161 1539901
PFOS-039
57 PFOS0068.D
6.2
1573828
PFOS-040
58 PFOS0069.D
6.2
1847467
PFOS-061
59 PFOS0070.D
6.2
1546353
PFOS-062
60 PFOS0071.D
6.2
1525687
PFOS-063
61 PFOS0072.D
6.2
829055
PFOS-064 PFOS-085 PFOS-086
62 PFOS0073.D 63 PFOS0074.D 64 PFOS0075.D
6.2 6.2 6.2
1869928 1561583 1519208
PFOS-087
65 PFOS0076.D
6.2
1540515
PFOS-088
66 PFOS0077.D
6.2
1841934
MeOH Blank CCV7.0, 501.5
91 PFOS0078.D 83 PFOS0079.D
0.0 6.2
0 1498004
MeOH Blank
91 PFOS0080.D
0.0
0
PFOS-109 PFOS-110
67 PFOS0081.D 68 PFOS0082.D
6.2 6.2
1536776 1558166
PFOS-111 PFOS-112
69 PFOS0083.D 70 PFOS0084.D
6.2 6.2
1501554 1871247
PFOS-133 PFOS-134
71 PFOS0085.D 72 PFOS0086.D
6.2 6.2
1569507 1536293
PFOS-135
73 PFOS0087.D
6.2
1560610
PFOS-136
74 PFOS0088.D-
6.2
1911482
PFOS-157
75 PFOS0089.D
6.2
1070252
PFOS-158 PFOS-159
76 PFOS0090.D 77 PFOS0091.D
6.2 6.2
1572360 1624806
PFOS-160
78 PFOS0092.D
6.2
1930723
PFOS-181
79 PFOS0093.D
6.2
1569774
PFOS-182
80 PFOS0094.D
6.2
1540069
PFOS-183
81 PFOS0095.D
6.2
1547540
PFOS-184
82 PFOS0096.D
6.2
1852935
MeOH Blank
91 PFOS0097.D
0.0
0
MeOH Blank
91 PFOS0102.D
0.0
0
L1 Std, 300.90 L2 Std, 401.20
1 PFOS0103.D 2 PFOS0104.D
6.2 6.2
940355 1209946
L3 Std, 451.35
3 PFOS0105.D 6.2
1336484
L4 Std, 501.50
4 PFOS0106.D 6.2
1521050
L5 Std, 541.62
5 PFOS0107.D 6.2
1688557
L6 Std, 601.80
6 PFOS0108.D 6.2
1775771
L7 Std, 702.10
7 PFOS0109.D 6.2
2061130
L8 Std, 802.40
8 PFOS0110.D 6.2
2350847
External Standard quant: ^=0.9989 Linear, include origin
Spike Amount = 100.30 Original Amount= 510.50
Calibration range: 300-800ng/mL
(A) Excluded on the basis of data quality ojectives; see text.
CONC. 0.0
302.8 406.3 447.5 507.1 548.3 601.7 700.3 793.4
0.0 540.6 544.4 550.7 672.3 513.7 514.9 526.6 621.0 517.2 510.0 515.0 628.7 522.4 507.8 515.2 619.1 0.0 500.5 0.0 513.9 521.2 501.7 629.2 525.2 513.7 522.1 643.1 353.0 526.1 544.2 649.7 525.2 515.0 517.6 622.9 0.0 0.0 308.2 401.2 444.8 508.4 566.2 596.3 694.7 794.6
ng/mL ng/mL
or%RSD 101% 101% 99% 101% 101% 100% 100% 99%
1%
1%
1%
1%
2%
1%
22%
1%
102% 100% 99% 101% 105% 99% 99% 99%
Recovery
(A) 102% 114% 104%
117% 122%
(A) 103%
- D is iv i^
Day 0 Day 0 DayO Day 0 Day 7 Day 7 Day 7 Day 7 Day 14 Day 14 Day 14 Day 14 Day 21 Day 21 Day 21 Day 21
Day 28 Day 28 Day 28 Day 28 Day 35 Day 35 Day 35 Day 35 Day 42 Day 42 Day 42 Day 42 Day 49 Day 49 Day 49 Day 49
5.9 5.9 5.9 5.9 5.9 5.9 5.9 5.9
5.9 5.9 5.9 5.9 5.9 5.9 5.9 5.9 5.9 5.9 5.9 5.9 5.9 5.9 5.9 5.9
5.9
5.9 5.9 5.9 5.9 5.9 5.9 5.9 5.9 5.9 5.9 5.9 6.0 5.9 6.0 5.9 5.9
AREA
461022 461213 453927 455268 457342 452098 456825 452021
455718 469425 459640 470701 455495 451192 457439 458953 463196 457566 486012 458974 456902 461554 464677 462077
452456
454292 461071 461556 458235 460375 468735 460087 471402 459110 460919 473396 467274 463144 460801 460690 464364
CONC.
367.9 367.9 367.9 367.9 367.9 367.9 367.9 367.9
367.9 367.9 367.9 367.9 367.9 367.9 367.9 367.9 367.9 367.9 367.9 367.9 367.9 367.9 367.9 367.9
367.9
367.9 367.9 367.9 367.9 367.9 367.9 367.9 367.9 367.9 367.9 367.9 367.9 367.9 367.9 367.9 367.9
Mean STDEV %STDEV
5.9 5.9 5.9 5.9 5.9 5.9 5.9 5.9
5.940 0.009 0.15%
476762 460494 455558 474146 476733 459538 453813 468450
461710 7335 1.6%
367.9 367.9 367.9 367.9 367.9 367.9 367.9 367.9
Page 55 of 71
BACK TO MAIN
3M Environmental Laboratory Report No. W1878
PFOS Hydrolysis Analysis Results
PFOS Hydrolysis Study 50 C .; pH 9.0 All concentrations in ng/ml
PFOS
THPFOS
* v Sample TM *".' MeOH Blank L1 Std, 300.90 L2 Std, 401.20 L3 Std, 451.35 L4 Std, 501.50 L5 Std, 541.62 L6 Std, 601.80 L7 Std, 702.10 L8 Std, 802.40 MeOH Blank PFOS-017A PFOS-018A PFOS-019A PFOS-020A PFOS-041 PFOS-042 PFOS-043 PFOS-044 PFOS-065 PFOS-066 PFOS-067 PFOS-068 PFOS-089 PFOS-090 PFOS-091 PFOS-092 MeOH Blank
CCV9.0, 501.5 MeOH Blank PFOS-113 PFOS-114 PFOS-115 PFOS-116 PFOS-137 PFOS-138 PFOS-139 PFOS-140 PFOS-161 PFOS-162 PFOS-163 PFOS-164 PFOS-185 PFOS-186 PFOS-187 PFOS-188 MeOH Blank MeOH Blank L1 Std, 300.90 L2 Std, 401.20 L3 Std, 451.35 L4 Std, 501.50
L5 Std, 541.62 L6 Std, 601.80 L7 Std, 702.10 L8 Std. 802.40
External Standard quant: ^=0.9985 Linear, include origin Calibration range: 300-800ng/mL
Vial#. 91 1 2 3 4 5 6 7 8 91 11 12 13 14 15 16 17 18 19 20
` 21 22 23 24 25 26 91 43 91 27 28 29 30 31 32 33 34 35 36 37
38 39 40 41 42 91 91 1 2 3 4 5 6 7 8
FILE#
RT
PFOS0002.D
0.0
PFOS0003.D
6.2
PFOS0004.D
6.2
PFOS0005.D
6.2
PFOS0006.D
6.2
PFOS0007.D
6.2
PFOS0008.D
6.2
PFOS0009.D
6.2
PFOS0010.D
6.2
PFOS0011-D
0.0
PFOS0012.D
6.2
PFOS0013.D
6.2
PFOS0014.D
6.2
PFOS0015.D
6.2
PFOS0016.D
6.2
PFOS0017.D
6.2
PFOS0018.D
6.2
PFOS0019.D
6.2
PFOS0020.D
6.2
PFOS0021.D
6.2
PFOS0022.D
6.2
PFOS0023.D
6.2
PFOS0024.D
6.2
PFOS0025.D
6.2
PFOS0026.D
6.2
PFOS0027.D
6.2
PFOS0028.D
0.0
PFOS0029.D
6.2
PFOS0030.D
0.0
PFOS0031.D
6.2
PFOS0032.D
6.2
PFOS0033.D
6.2
PFOS0034.D
6.2
PFOS0035.D
6.2
PFOS0O36.D
6.2
PFOS0037.D
6.2
PFOS0038.D
6.2
PFOS0039.D
6.2
PFOS0040.D
6.2
PFOS0041.D
6.2
PFOS0042.D
6.2
PFOS0043.D
6.2
PFOS0044.D
6.2
PFOS0045.D
6.2
PFOS0046.D
6.2
PFOS0047.D
0.0
PFOS0052.D
0.0
PFOS0053.D
6.2
PFOS0054.D
6.2
PFOS0055.D
6.2
PFOS0056.D
6.2
PFOS0057.D
6.2
PFOS0058.D
6.2
PFOS0059.D
6.2
PFOS0060.D
6.2
Spike Amount =
Original Amount^
REA 0
953102 1218775 1367918 1551173 1677402 1769358 2089069 2378629
0 1616062 1624393 1653756 1957832 1501590 1526483 1505235 1824064 1500355 1514313 1535649 1836909 1516350 1500761 1515632 1814578
0 1484761
0 788677 1543909 1521618 1826663 1543536 1534697 1515054 1813976 1581877 1550129 1535004 1846288 1508950 1554719 1536965 1844447
0 0 933689 1203251 1330908 1508612 1614221 1790279 2072483 2304052
100.30 510.50
cerne.
0.0 311.6 403.6 455.2 518.6 562.2 594.1 704.7 804.9
0.0 541.0 543.9 554.1 659.3 501.4 510.0 502.7 613.0 501.0 505.8 513.2 617.4 506.5 501.1 506.3 609.7
0.0 495.6
0.0 482.0 516.1 508.3 613.9 515.9 512.9 506.1 609.5 529.2 518.2 513.0 620.7 504.0 519.8 513.7 620.0
0.0 0.0 304.9 398.2 442.4 503.8 540.4 601.3 698.9 779.1
ng/mL ng/m l
Standard^ Rpyery .: r Day
104% 101% 101% 103% 104% 99% 100% 100%
DayO
DayO
1% DayO
113%
DayO
Day 7
Day 7
1% Day 7
108%
Day 7
Day 14
Day 14
1% Day 14
110%
Day 14
Day 21
Day 21
1% Day 21
105%
Day 21
4%
1%
2%
2%
101% 99% 98% 100% 100% 100% 100% 97%
111% 98% 100% 107%
Day 28 Day 28 Day 28 Day 28 Day 35 Day 35 Day 35 Day 35 Day 42 Day 42 Day 42 Day 42 Day 49 Day 49 Day 49 Day 49
Mean STDEV %STDEV
RT
REA
CONC.
5.9
473117
367.9
5.9
464785
367.9
5.9
457051
367.9
5.9
467730
367.9
5.9
465651
367.9
5.9
451964
367.9
5.9
453078
367.9
5.9
458733
367.9
5.9
452326
367.9
5.9
456282
367.9
5.9
443496
367.9
5.9
454976
367.9
5.9
435799
367.9
5.9
433949
367.9
5.9
435077
367.9
5.9
428602
367.9
5.9
426103
367.9
5.9
430148
367.9
5.9
428441
367.9
5.9
428754
367.9
5.9
429907
367.9
5.9
436263
367.9
5.9
420444
367.9
5.9
428401
367.9
5.9
425257
367.9
5.9
457837
367.9
5.9
439145
367.9
5.9
427872
367.9
5.9
427362
367.9
5.9
427211
367.9
5.9
430577
367.9
5.9
421647
367.9
5.9
423606
367.9
5.9
437492
367.9
5.9
422229
367.9
5.9
419751
367.9
5.9
425829
367.9
5.9
434632
367.9
5.9
429837
367.9
5.9
424155
367.9
5.9
426168
367.9
5.9 5.9 5.9 5.9 5.9 5.9 5.9 5.9
5.937 0.005 0.08%
462354 444905 450015 454336 444002 446180 456637 444952
439648 14909 3.4%
367.9 367.9 367.9 367.9 367.9 367.9 367.9 367.9
Page 56 of 71
BACK TO MAIN
HP LC/MSD 1100 PFOS Hydrolysis Study 50 C .; pH 11.0 All concentrations in ng/ml
PFOS
Sample MeOH Blank L I Std, 300.90 L2 Std, 401.20 L3 Std, 451.35 L4Std, 501.50 L5 Std, 541.62 L6 Std, 601.80 L7 Std, 702.10 L8 Std, 802.40 MeOH Blank PFOS-021A PFOS-022A PFOS-023A PFOS-024A
PFOS-045 PFOS-046 PFOS-047 PFOS-048 PFOS-069 PFOS-070 PFOS-071 PFOS-072 PFOS-093 PFOS-094 PFOS-095 PFOS-096 MeOH Blank CCV 11.0,501.5 MeOH Blank PFOS-117 PFOS-118 PFOS-119 PFOS-120 PFOS-14! PFOS-142 PFOS-143 PFOS-144 PFOS-165 PFOS-166 PFOS-167 PFOS-168 PFOS-189 PFOS-190 PFOS-191 PFOS-192 MeOH Blank MeOH Blank L I Std, 300.90 L2 Std, 401.20 L3 Std, 451.35 L4 Std, 501.50 L5 Std, 541.62
L6 Std, 601.80 L7 Std, 702.10 L8 Std, 802.40
External Standard quant: ^ 0.998 28 Linear, include origin Calibration range: 300-800ng/mL
Vial# 91 1 2 3 4 5 6 7 8 91 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65 66 91 83 91 67 68 69 70 71 72 73 74 75 76 77 78 79 80 81 82 91 91 1 2 3 4 5 6 7 8
FILE# PFOS0052.D PFOS0053.D PFOS0054.D PFOS0055.D PFOS0056.D PFOS0057.D PFOS0058.D PFOS0059.D PFOS0060.D PFOS0061.D PFOS0062.D PFOS0063.D PFOS0064.D PFOS0065.D PFOS0066.D PFOS0067.D PFOS0068.D PFOS0069.D PFOS0070.D PFOS0071.D PFOS0072.D PFOS0073.D PFOS0074.D PFOS0075.D PFOS0076.D PFOS0077.D PFOS0078.D PFOS0079.D PFOS0080.D PFOS0081.D PFOS0082.D PFOS0083.D PFOS0084.D PFOS0085.D PFOS0086.D PFOS0087.D PFOS0088.D PFOS0089.D PFOS0090.D PFOS0091.D PFOS0092.D PFOS0093.D PFOS0094.D PFOS0095.D PFOS0096.D PFOS0097.D PFOS0102.D PFOS0103.D PFOS0104.O PFOS0105.D PFOS0106.D PFOS0107.D
PFOS0108.D PFOS0109.D PFOS0110.D
RT AREA 0.0 0 6.2 933689 6.2 1203251 6.2 1330908 6.2 1508612 6.2 1614221 6.2 1790279 6.2 2072483 6.2 2304052 0.0 0 6.2 1625471 6.2 1647280 6.2 1603495 6.2 1904433 6.2 1538330 6.2 1511423 6.2 1483037 6.2 1796882 6.2 1507576 6.2 1500671 6.2 1487086 6.2 1768167 6.2 1518917 6.2 1495375 6.2 1494143 6.2 1787696 0.0 0 6.2 1458881 0.0 0 6.2 1480462 6.2 1488646 6.2 1488485 6.2 1761594 6.2 1514752 6.2 1564763 6.2 1492116 6.2 1792043 6.2 1526086 6.2 1517939 6.2 1518383 6.2 1827982 6.2 1547114 6.2 1489819 6.2 1516923 6.2 1786004 0.0 0 0.0 0 0.0 0 6.2 1186168 6.2 1335526 6.2 1512496 6.2 1630388 6.2 1738164 6.2 1999778 6.2 2277544
Spike Amount = Original Cone., pg/mL =
CONC. 0.0 310.8
405.6 450.5 513.1 550.2 612.2 711.5 793.0 0.0 554.2 561.9 546.5 652.4 523.5 514.1 504.1 614.5 512.7 510.3 505.5 604.4 516.7 508.4 508.0 611.3 0.0 495.6 0.0 503.2 506.0 506.0 602.1 515.2 532.8 507.3 612.8 519.2 516.4 516.5 625.5 526.6 506.5 516.0 610.7 0.0 0.0 0.0 399.6 452.2 514.4 555.9 593.9 685.9 783.7
100.30 100.30
3M Environmental Laboratory Report No. W1878
o r/R S D 101% 100% 102% 102% 102% 101% 99%
1%
2%
1%
1%
0%
3%
0%
2%
. .. %Spike Recovery
111% 112% 109%
104% 103% 101%
102% 102% 101%
103% 101% 101%
99%
100% 101% 101%
103% 106% 101%
104% 103% 103%
105% 101% 103%
; -S B DayP-^'
THPFOS
RT
5.9 5.9 5.9 5.9 5.9 5.9 5.9 5.9
DayO DayO DayO DayO Day 7 Day 7 Day 7 Day 7 Day 14 Day 14 Day 14 Day 14 Day 21 Day 21 Day 21 Day 21
5.9 5.9 5.9 5.9 5.9 5.9 5.9 5.9 5.9 5.9 5.9 5.9 5.9 5.9 5.9 5.9
5.9
Day 28 Day 28 Day 28 Day 28 Day 35 Day 35 Day 35 Day 35 Day 42 Day 42 Day 42 Day 42 Day 49 Day 49 Day 49 Day 49
5.9 5.9 5.9 5.9 5.9 5.9 5.9 5.9 5.9 5.9 5.9 5.9 5.9 5.9 5.9 5.9
V?. v y-:-:-
AREA
462354 444905 450015 454336 444002 446180 456637 444952
454432 456158 454644 453156 451881 449709 443583 446222 446631 448105 453359 456369 460494 448780 452682 440280
439032
444445 444672 451687 445630 451864 448317 451377 447168 452262 445268 450919 448199 452866 443889 453467 447050
CONC.
376.7 362.5 366.7 370.2 361.8 363.5 372.1 362.5
370.3 371.7 370.4 369.2 368.2 366.4 361.4 363.6 363.9 365.1 369.4 371.8 375.2 365.7 368.8 358.7
357.7
362.1 362.3 368.0 363.1 368.2 365.3 367.8 364.4 368.5 362.8 367.4 365.2 369.0 361.7 369.5 364.3
100% 100% 103% 103% 99% 98% 98%
ng/mL Mg/mL
5.9 5.9 5.9 5.9 5.9 5.9 5.9
5.937 0.005 0.09%
459975 450262 461681 459085 447599 450097 451922
450360 5537 1.2%
374.8 366.9 376.2 374.1 364.7 366.7 368.2
Page 57 of 71
BACK TO MAIN
BACK TO MAIN
3M Environmental Laboratory Report No. W1878
Figure 3. Pooled PFOS Data and Slope Regression
0 10 20 30 40 50 60 time (days)
SUMMARYOUTPUT
R e p re ssio n S ta tistics
Multiple R
0.384852267
R Square
0.148111267
Adjusted R Square
0.126267966
Standard Error
0.010265446
Observations
41
ANOVA
Regression Residual Total
d f SS 1 0.000714538
39 0.004109796 40 0.004824334
MS 0.000714538 0.000105379
Intercept X Variable 1
C o efficie n ts
S tandard E rror
tS ta t
-0.005616288 0.003550759 -1.581714762
0.000298279 0.000114548 2.603963638
F S ignificance F
6.780626626
0.0129706
P -value 0.121791782
Low er 95% -0.012798369
0.0129706
6.65838E-5
U pper 95%
L o w e r 95.0% p p e r 95.0%
0.001565793 -0.012798369 0.0015658
0.000529973
6.65838E-05 6.66E-05
0.00053 5.3QE-04
Page 58 of 71
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3M Environmental Laboratory Report No. W1878
Appendix D: Selected Chromatograms
A representative set of chromatograms from the present study is included in this Appendix.
Page 59 of 71
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3M Environmental Laboratory Report No. W1878
Method C :\HPCHEM\l\METHODS\0922_50 .M Calibrtion Table
Calib. Data Modified :
Calculate Based on
'
: :
Rel. Reference Window Abs. Reference Window Rel. Non-ref. Window Abs. Non-ref.'Window Multiplier Dilution Sample Amount Uncalibrated Peaks Partial Calibration Correct All Ret. Times
9/24/1999 10:08:51 AM
External Standard Peak Area
5.000 % 0.000 min 5.00.0 %
101.0..000.000000000000m0in
O rnam i /h it s p H g o Gffi'JOffo
not reported Yes, identified peaks are recalibrated No, only for identified peaks
Curve Type Origin Weight '
Linear Included " Equal
Recalibration Settings:
Average Response
:
Average Retention Time:
Average all calibrations Floating Average New 75%
Calibration Report Options :
Printout of recalibrations within a sequence:
Calibration Table after Recalibration
Normal Report after Recailibration
'
If the sequence is done with bracketing:
Results of first cycle (ending previous bracket)
Signal 1: MSD1 427, EIC=426.7:427.7 Signal 2: MSD1 499, EIC=498.7:499.7 Signal 3: MSD1 399, EIC=398.7:399.7
'
RetTime Lvl Amount
Area
[min] Sig
[ppb] (
II__II_I_ I--------- 1
5.642 3 1 300.90000 3.78048e4
11 300.90000 3.80593e4
. 2 401.20000 4.74013e4
22 401.20000 5.i4873e4
3 451.35000 5.60681e4
33 451.35000 5.86619e4
4 501.50000 6.94725e4
44 501.50000 6.86155e4
. 5 541.62000 6.91006e4
55 541.62000 6.74844e4
6 601.80000 7.89434e4
66 601.80000 7.90989e4
7 .702,10000 8.70628e4
77 702.10000 9.13195e4
' 8 802.40000 1.00442e5
Amt/Area Ref Grp Name
7.95930e-3 7.90609e-3 8.46390e-3 7.79221e-3 8.Q5003e-3 7.69409e-3 7.21869e-3 7.30884e-3 7.83813e-3 8.02586e-3 7.62318e-3 7.60820e-3 8.06430e-3 7.68839e-3 7.98866e-3
PFHS
Page 60 of 71
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3M Environmental Laboratory Report No. W1878
Method C:\HPCHEM\l\METHODS\0922__50.M
5.931
6.222
Lvl Amount
Area
Amt/Area
3, ( tPPb] (
l1
1
88 802.40000 1.00128e5 '8.01373e-3'
1 1 367.92000 4.73070e5 7.77729e-4
2 367.92000 4.60726e5 -7.98565e-4
3 367.92000 4.39572e5 8.36996e-4
4 367.92000 4.90981e5 7.49357e-4
5 367.92000 4.67449e5 7.87080e-4
6 367.92000 4.57579e5 8.04058e-4
7 367.92000 4.3S372e5 8.45071e-4
8 367.92000 4.52504e5 8.13075e-4
11 367.92000 4.61022e5 7.98052e-4
22 367.92000 4.61213e5 7.97722e-4
33 367.92000 4.53927e5 8.10526e-4
44 367.92000 4.55268e5 8.08140e-4
55 367.92000 4.57342e5 8.04475e-4
_...66 ,367.92000 4.52098e5 8.13806e-4
77 367.92000 4.56825e5 8.05384e-4
88 367.92000 4.52021e5 8.13945e-4
21 11 2 22
300.90000 9.20859e5 300.90000 9.24706e5 401.20000 1.21379e6 401.20000 1.22485e6
3.26760e-4 3.25401e-4 3.30534e-4 3.27551e-4
3 . 451.35000 1.32239e6 3.41314e-4 33 451.35000 1.34445e6 3.35713e-4
4 501.50000 1.56794e6 3.19846e-4
44 501.50000 1.51715e6 3.30554e-4 5 541.62000 1.63601e6 3. 31062e-4
55 541.62000 1.63668e6 3.30926e-4
6 601.80000 1.76299e6 3.41353e-4 66 601.80000 1.79159e6 3 .35902e-4
7 702.10000 2.03577e6 3.44881e-4
77 702.10000 2.07740e6 3.37970e-4
8 802.40000 .2.31841e6 3.46099e-4
88 802.40000 2.34731e6 3.41839e-4
Peak Sum Table
TfiPFOS PFOS
***No Entries in table***
'
Calibration Curves
PFHS at exp. RT: 5.642
MSD1 399, EIC=398.7:399.7
Correlation:
0.99520
Residual Std. Dev.: 2578.76545
Formula: y = trnc + b
m: 126.82582
b: 571.81435
x : Amount[ppb]
y : Area
Page 61 of 71
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3M Environmental Laboratory Report No. W1878
Method C :\HPCHEM\1\METHODS\0922_50.M
THPFOS at exp. RT: 5.931
MSD1 427, EIC=426.7:427.7
Correlation:
-0.99395
Residual Std. Dev.: 12673.93S65
Formula: y = mx + b '
m: 1244.66095
b: -3.54902e-10
x : Amount[ppb]
.
y : Area
PFOS at exp. RT: 6.222
MSD1 499, EIC=498.7:499.7
Correlation:
0.99860
Residual Std. Dev.: 31589.73759
Formula: y = mx + b
m: 2878.88299
b: 51022.56267
x: Amount[ppb]
y : Area
Page 62 of 71
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3M Environmental Laboratory Report No. W1878
Batch Run # 1 of 60 Data File D:\DATA\092399\PFOS0001.D
Sample Name: MeOH Blank
Injection Date 9/23/1999 9:53:01 AM
Seq. Line : 1
Sample Name
MeOH Blank
Vial : 91
Acq. Operator
Acq.' Method Last changed
MTM I n j V o luImnje :? 5 11 1_
C:\HPCHEM\l\METH0DS\PF0S_NG2.M 9/23/1999 9:50:00 AM by MTM
-Oaio,/w)i fwQ'ii'.
Analysis Method Last changed
C :\HPCHEM\1\METHODS\0922_50.M 9/24/1999 10:12:55 AM by MTM
(Results are from a previously saved Batch)
J[J7 r?~/TS^/Itco
NGa- eolutnn,SIM Analysis (ES-) for THPFOS, PFOS, and PFHS using 4rnmx35mm Dionex IonPac S/N 12879.
MTM
External Standard Report
359 52--C s S S S C S J S S S S S
S
Sorted By Calib. Data Modified Multiplier Dilution
Signal
.191./.00200400/001999 10:08:51 AM
Signal 1: MSD1 427, EIC=426.7:427.7
RetTime Type [min]
Area
Amt/Area .
Amount Grp Name [ppb]
5.931 Totals :
THPFOS
0.00000
Signal 2: MSD1 499, EIC=498.7:499.7
RetTime Type [min]
Area
Arat/Area
Totals :
Amount Grp Name
-[.p.p..b..]... -------------------- PFOS
0.00000
Page 63 of 71
BACK TO MAIN
3M Environmental Laboratory Report No. W1878
Batch Run # 1 of 0 Data File D:\DATA\092399\PFQS0001.D
Sample Name: MeOH Blank
Signal 3: MSDl 399, EIC=398.7:399.7
~
RetTime Type [min]
Area
Amt/Area Amount .. Grp Name , " Ippb]
5.642 . -
- .-
PFHS
Totals :
0.00000
1 Warnings or Errors :
.
Warning : Calibrated compound(s) not found
Area Percent Report
Sorted By
:
Calib. Data Modified :
.. .-Multiplier
:
Dilution
:
Signal 9/24/1999 10:08:51 AM
1.0000 1.0000
Signal 1: MSD1 427, EIC=426.7:427.7
Peak RetTime Type Width
# [min]
[min]
Area
1 5.931 .
0.0000 0.00000
Totals :
0.00000
Area %
Name
0.0000 THPFOS
"
.
signal 2: MSDl 499, EIC=498.7 :499.7
Peak RetTime Type Width
Area
Area Name
# [min]
[min]
%
1___ 11_______ |i______ |______ | _________ |._______ j
1 6.222
0.0000
o . o o o o o o . o o o o ' PFOS
Totals :
0.00000
'
Signal 3: MSDl 399, EIC=398.,7:399.7
Peak RetTime Type Width
# [min] ___ 11_______Ii___
1 5.642
[min] 1
. o.oooo'
Area
Area Name
%. 1 |____________________ 0.00000 0.0000 PFHS
Totals :
0.00000
Page 64 of 71
BACK TO MAIN
3M Environmental Laboratory Report No. W1878
Batch Run # 1 of 60 Data File D:\DATA\092399\PFOS0001.D
1 Warnings or Errors :
Warning : Calibrated compound (s) not found
'-
, *** End of Report ***
. Sample Name: MeOH BlanJ<
.. '
Page 65 of 71
BACK TO MAIN
3M Environmental Laboratory Report No. W1878
Batch Run I 6 of 60 Data File D:\DATA\092399\PFOS0006.D
/
Sample Name: L4 Std, 501.50
Injection Date 9/23/1999 11:04:05 AM
Seq. Line
6
Sample Name Acq. Operator
L4 Std, 501.50 MTM
Vial Inj
41
A c q . Method Last changed Analysis Method Last changed
C ;\HPCHEM\l\METHOD"S\PFOS_NG2.MIinj/ *
M U S S9/23/1999 9:50:00 AM by MTM f l) D - lwC:\HPCHEM\1\METHODS\0922_50.M
J_ p
V)Unolu um,Me
l
O
%rr%K&f)nC><93//2244 // 119< 39999 I1f0l :f I1J2. :R5i5! AA MM bh yv MM TT MM _/ 9
5 pi
(Results are from a previously saved Batch)
SIM Analysis (ES-) for THPFOS, PFOS, and PFHS'using 4mmx35mm Dionex IonPac
NGl column, S/N 12879. MTM T iiStyR /, fclt=426-/:42/:/(Liy2'JSiaTP'FO'SOOBXiy-PR:S'Negative
^ 2/
MSDTSSa, LKJ=4ya./':4yy./ (OS23SS\PFOSOOU.U)" AiJl-fcS Negative
1
1
i
4
MtiL)T3aa, hlu^aats.r.aa.c (UBZ3\PFOS06.)'VM-ta Negative
2500
/V
' 1 ' ' ' ' ' 1 i
Jy
Z
3
\V
' ' ' ' '
'
_min
a a s = a sssB sa s:= H 3 :s= B S S s:a ts sssa a ^ sa ssss:sse = s 5 S ssa e sa :a s= 3 B :s a s a is:
External Standard Report
s te s s a
Sorted By Calib. Data Modified Multiplier Dilution
Signal
119/..00200400/001999 10:08:51 AM
Signal 1: MSD1 427, EIC=426.7:427.7
RetTime Type : Area
Amt/Area Amount Grp Name
- [.m.i..n..]....! - .......... I----------------1----------------1......[..p..p.--b] - I - - I ............-
5.920 BB
4.90981e5 8.03432e-4 394.46965 THPFOS
Totals :
394.46965
Signal 2: MSD1 499, EIC=498.7:499,7
RetTime Type
Area
Amt/Area Amount Grp Name
[min] ..........- I -- .............. I---------------- 1-- [-p.p..b..]........1 - 1 -----------
6.216 PB
1.56794e6 3.36054e-4 526.91202 PFOS
Totals :
526.91202
Page 66 of 71
BACK TO MAIN
3M Environmental Laboratory Report No. W1878
Batch Run # 6 of 60 Data File D:\DATA\092399\PFOS0006.D
. Sample Name: L4 Std, 501.50
Signal 3: MSD1 399, EIC=398.7:399.7
'
-
RetTime Type
Area
Amt/Area Amount , Grp Name
[min]
.. - [ppbj "
------ j------|..........|------------- ------ ..........
5.628 BB
6.94725e4" 7.81993e-3 543.26994 PFHS
jTotals-- ---
543.. 26994
* * * End of Report ***
Page 67 of 71
BACK TO MAIN
3M Environmental Laboratory Report No. W1878
Batch Run # 18 of SO Data File D:\DATA\092399\PFOS0018.D
Sample Name: PFOS-03E
Injection Date 9/23/1999 1:54:44 PM
Seq. Line 18
Sample Name
PFOS-035
Vial 17
Acq. Operator
MTM
inj Inj Volume
5 p1i
Acq. Method
C :\HPCHEM\1\METH0DS\PF0S_NG2.M
Last changed
9/23/1999 9:50:00 AM by MTM
Analysis Method C:\HPCHEM\1\METHODS\0922 50.M
Last changed
9/24/1999 10:12:55 AM by"MTM
1
(Results are from a previously saved Batch)
SIM Analysis (ES-) for THPFOS, PFOS, and PFHS using 4mmx35mm Dionex lonPac
NG1 column, S/N 12879.
MTM
External Standard Report
Sorted By
:
Calib. Data Modified
Multiplier
Dilution
Signal
911/..00200400/001999 10:08:51 AM
Signal 1: MSD1 427, EIC=426.7:427.7
C)y7i?ihj4L
p H S S firyim
(yu
RetTime Type (min]
Area
Amt/Area
Amount Grp Name [ppb]
5.940 BB
4.4713Se5 8.03432e-4 359.24296 THPFOS
yr / Sr/^o/oe?
Totals :
359.24296
Signal 2: MSD1 499, EIC=498.7:499.7
RetTime Type
Area
Amt/Area Amount Grp Name
- .[..m..i.n..]....i ----------1----------------I----------------I - ....[..p..p..b.]........ I" l ---------
6.227 BB
1,55106e6 3.35931e-4 521.04708 PFOS
Totals :
521.04708
Page 68 of 71
BACK TO MAIN
3M Environmental Laboratory Report No. W1878
Batch Run # 18 of 60 Data File D:\DATA\092399\PFQS0018.D
Sample Name: PFOS-035
Signal 3: MSD1 399, EIC=398.7 :399.7
RetTime Type [rain]
Area
Amt/Area
Amount Grp Name [ppb] "
5.653 PB
6.61458e4- 7.81667e-3 517.03982 PFHS
Totals :
517.03982
*** End of Report ***
BACK TO MAIN
3M Environmental Laboratory Report No. W1878
Batch Run # 19 of SO Data File D:\DATA\092399\PFOS0019.D
Sample Name: PFOS-036
Injection Date 9/23/1999 2:08:58 PM
Seq. Line : 19
Sample Name ! PFOS-036
Vial : 18
Acq. Operator;
MTM
" Inj
Inj Volume
: :
5 .(1xl
Acq. Method j C:\HPCHEM\1\METHODS\PFOS_NG2.M
Last changed ! 9/23/1999 9:50:00 AM by MTM
Analysis Method C :\HPCHEM\1\METH0DS\0922_5 0.M
Last changed I 9/24/1999 10:12:55 AM by MTM
(Results are from a previously saved Batch)
SIM Analysis (ES-) for THPFOS, PFOS, and PFHS using 4mmx35mm Dionex IonPac
NG1 column, S/N 12879.
MTM
External Standard Report
Sorted By
Calib. Data Modified Multiplier Dilution
Signal
911/..00200400/001999 10:08:51 AM
-fOrti&iKwc /htM&S
tJ /f,,t7lf'ia''jrii spirit:
Signal 1: MSD1 427, EIC=426.7 :427.7
RetTime Type [min]
Area
Amt/Area
Amount [ppb]
1 sS 4 M P &
Grp Name
yr
5.944 BB
4.61076e5 8.03432e-4 370.44323 THPFOS
Totals :
370.44323
Signal 2: MSD1 499, EIC=498.7:499.7
RetTime Type [min]
Area
Amt/Area
Amount Grp Name [ppb]
6.231 BB
1 ! ! 1i" 1 1.89862e6 3.38022e-4 641.77689 PFOS
Totals
641.77689
Page 70 of 71
BACK TO MAIN
3M Environmental Laboratory Report No. W1878
Batch Run # 19 of 60 Data File D:\DATA\092399\PFOS0019.D
Sample Name: PFOS-036
Signal 3: MSD1 399, EIC=398.7:399.7
-
RetTime Type
Area Amt/Area Amount Grp Name
---[-m-i--n-]-- i----------_.-------------1.-.---------!...............[.p..|.)..b.]..... -'| - l ............ -
5.656 BB
8.69266e4- 7.83296e-3 680.89256 PFHS
Totals *.
680.89256
>
*** End of Report ***
Page 71 of 71
