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3M. ENVIRONMENTAL LABORATORY REPORT NO. E06-0199
Subreport
Analysis of PFOA, PFOS, PFHS, and PFBS in Aqueous
Samples : 3M Decatur Offsite Sampling Event
(BPP Sample Sites) ~ -
`
Laboratory Request Number: ~06-0199
Method Requirement: 3M Method ETS-8-154.1 (modified)
Testing Laboratory
3M EHS Operations
3M Environmental Laboratory
building 2.-3E-09
,..,
935 Bush Avenue
St. Paul, MN 55106
Requester
Gary Hohenstein
3M Building 42-02-E-27
`Ptv
PO Box 3331
Saint Paul, MN 55133-3331
Phone: (651) 778-5150
Fax: (651) 778-7203
111"d IN" ACCREDITED
The testing reported herein meet the requirements of ISOIIEC 17025-1999 "General
Requirements for the Competence of Testing and Calibration. Laboratories", in accordance with
~e A~ ~~~~ ~52-01 . Testdng that complies with this International Standard also
operate In accordance with ISO 9001RS0 9002 (1994).
-
Certificate #2052-01
PAGE 1 OF 21
000003
3M ENVIRONMENTAL LABORATORY REPORT NO. E06-0199
3M Environmental Laboratory 3M Environmental Laboratory Manager: 'rrSl11arn K. Reagen, Ph .D . 3M Technical Lead : Michelle fllalinsky, Pti.D . Report Author: Michelle Malinsky, Ph .D .
Analytical Subreport E06-0199
Surface Water Samples BPP01, BPPd2, and BPP03; Ground Water Sample BPWell Decatur Offsite Sampling Event Report Date: May 1, 2006
Introduction/Summary
The 3M Environmental Laboratory extracted and analyzed ground water and surface water samples collected by Weston Solutions personnel on April 12 and 13, 2036 near the 3M Decatur facility. Samples were returned to the 3M Environmental Laboratory for analysis of perfiuorooctanoate (PFOA), perfluorooctane sulfonate (PFOS), perfluorohexane sulfonate (PFF1ti) and perfluorobutane sulfonate (PFBS) under laboratory project number E06-0199 using modified 3M Environmental Laboratory Method ETS 8-154.1 "Determination of PerAuorinated Acids, Aicohols, Amides, and Sulfonates in Water by Solid Phase Extraction and High Performance Liquid Chromatography/Mass Spectrometry" . Per the client's request, an initial subreport is being issued for the -following four sample locations only:
" DAL SWS BPP01 " DAL SWS BPP02 " DAL SAG BPP03 " DAL GWS BPWELL This report will contain information relevant to these four sample collection points only. These results will be reissued in a comprehensive final project report that includes results for all samples collected under E06-0199 . The 3M,~Environmental Laboratory prepared sets of sample containers for*thirty-two separate sampling locations. At a minimum, each sample set consisted of a field sample, field sample duplicate, low field spike and high field spike . For some locatiorns, a third mid-levelk field spike was prepared . Each empty container was marked with a "fill to here" line which corresponded to a final volume of450 mL. Containers reserved for field matrix spikes were fortified with an appropriate matrix spike solution containing the four target analytes prior to being sent ".o the field for sample collection . The spike amounts prepared for each ofthe four locations presented here will be provided later in this report .
ACCREDITED
Certificate #2052-01
The testing reported herein meet the requirements of ISO/IEC 17025-1999 "General Requirements for the Competence of Testing and Calibration Laboratories", in accordance with the A21-&. Certificate #2052-01 . Testing that complies with this International Standard also operate in accordance with ISO
PAGE 2 OF 21
00
3M ENVIRONMENTAL LABORATORY REPORT NO. EO('r0199
Samples were initially extracted and analyzed on April 19, 2006. Samples were dilutedi,reextracted,
and analyzed on April 21, 2006. Laboratory matrix spikes were, prepared, diluted, extracted, and
analyzed on April 25, 2006 in the analytical batch initiated on April 24; 2Q06:., -
. ,
.. Table 1 below summarizes the sample results . All results for quality control samples prepared and ' analyzed with the samples will be reported and discussed elsewhere in this report . All samples were diluted 1 :50 in ASTM Type I water prior to extraction. .
Table 1 . Sample Results Summary.
3M LIMS ID E06-0199-055 E06-0199-056
E06-0199-060 E06-0199-061
E06-0199-065 E06-0199-066
E06-0199-070 E06-0199-071
Sampie Descfi tion
.rnPFOA " ~
concentratiorl~ n mL
14PFOS Concentration
mL
DAL SINS BPP01 0 060413 DAL SINS BPP01 DB 060413
293
'4>423 ,~
307
14>380
?Av~rage
300
(2)>402
%RPDSm IeSarn eD
1 . 4.7- . ^
NA .
DAL SWS BPP02 0 060413, ~ ti
206
(4>295 .
DAL SWS BPP02 DB 06U413' .~=' '
219
'#>314
" 'AveYa~: e ' 212 _
M>304
%RPD Sam eiSain ie Du 1
r B.1 '
' NA
DAL SWS BPP03 0 060413
219
~>272
DAL SINS BPP03 DB-060413~ '
214
~14>256
Average
216
>264
%RPD Sam Ie3am e Du
23
NA
DAL GINS BPINELL 0 060413 DAL GWS BPWELL DB 060413
12'>774
"'ti779
0>1460 ' (T)>1170
Average
(2)>776
14>1320
%RPD'Sain' le%Sam~,! "'Du '' . . . N .~ NA
I
MPFHS Concenbation
n m1
533- , 54.3 3,8
1 .8 38 .2 39 .8 39.0 ' 4.1 39 .1 40.1 39.4 " : .,
2.5 ', . ~ 12'51146 ,' (')>145
(2)>145 NA
rnPFBS concentration
n ml
6 .98 7.17 I . .7.O,B
. 27 4 .50 4 .72 4.66 2.6 4 .69 5 .05 4.87 7.4
17.2 17.6 17. 4 ~ _ 2.3
(1)
The analytical method uncertainty, for PFOA, PFHS, and PFBS was 100t11%, 100t5.8%, and 100t8.8%,
.rreessppeeccttiivvely based on method accu'acy, ~and preci'sion . 'Se6'Se~ction 3.7 for additional explanation. The limit of
(LOQ) lorthesesamples only was 2.50 ng/mL (PFOA) and 1 .25 nglmL (PFHS and PFBS). Results
and average values arp rounded to three signifigant figures accordingto EPA rounding rules. Percent relative
difference (%RPD) values .are Tgunded to two significant, figures. . Because of rounding, .values may vary slightly
from those listed' In therawd'ata:
(2)
All PFOS sample results presen*dfierd shAtdd be considered estimated minimum values as quality
control samples (field matrix,spikes and lab matrix spikgs) associated with these four samples didnot
demonstrate adequate method performance. The accuracy of the PFOS results could be within an order
of magnitude. %RPD values not calculated. Smellresults for PFOA andPFHS should also be
considered estimated minimums as field matrix spikerecoveries didnotmeet method acceptance criteria
of 100t30%. The analytical accuracy of the PFOA and PFHS estimated values for this sample only could
be within an order of magnitude. Y.RPD values not.calculateaG
.
PAl. ~athods - ~nalytfcajand Pre0arato
2.1 Sample Collection
Samples were collected in NalgeneT"'' (low-density polyethylene) bottles prepared at the 3M Environmental Laboratory . Prior to sample collection, bottles designated for field matrix spikes were spiked in the laboratory with a known volume of an appropriate matrix spiking solution containing the
PAGE 3 OF 21
000005
3M ENVIRONMENTAL LABORATORY REPORT NO. E06-0199
four analytes of interest (PFfJA; PFOS, PF.HS a~td I:'FBS) . ~ Collected sample bottles were received at the laboratory at ambient conditions on April 19, 2006 . Table 2. below details the samples collected and
spikes added to each bottle .
'
Table 2. Sample CaiJection and Spike Information.
3M LIMS IUN
Weston EM/e Descri Son
E06-0199-055 DAL S'JVS BPP01 0 060413
E06-0199-056 DAL SWS BPP01 DB 060A13
E06-0199-^57 DAL SINS BPP^1 LS 1?00413
E06-0199-058 DAL SWS BPP01 MS 060sl13
E06-0199-059 DAL SWS BPP01 HS 060413
E06-0199-060 DAL SWS BPP02 0 060413
E06-0199-061 DAL SWS BPP02 DB 060413
E06-0199-062 DAL SWS BPP02 LS 060413
E06-0199-063 DAL SWS BPP02 MS 060413
E06-0199-064 DAL SINS BPP02 HS 060413
E06-0199-065 DAL S1Ib5 BPP03 0 060413
E06-0199-066 DAL SWS BPP03 DB 060413
E06-0199-067 DAL SWS BPP03 LS 060413
E06-0199-068 DAL SWS BPP03 MS 060413
E06-0199-069 DAL SWS BPP03 HS 060413
E06-0199-070 DAL GWS BPINELL 0 060413
E06-0199-071 DAL GWS BPWELL DB 063413
E06-0199-072 E06-0199-073
DAL GINS BPWELL LS 060413 DAL GWS BPWELL MS 06041 :t
E06-0199-074 DAL GWS BhWELL KS 060413 DAL = Decatur, AL SWS = Surface Water Sample GWS = Ground Water Sample 0 = Sample DB = Duplicate
LS = Low Spike MS = Mid Spike
HS = High Spike
` 3M ` Botife Number
I 109 110 111
? 12 ~ 113 1 ?9 120 121 . 122 123
'14 ~ 115 ~ 116 117 '. 13 7'c ~ 73 ( 74 I '5 73
Botue Designation
Sample Sample Dup FMS Low
FMS Mid FMS High Sample Sample Dup FMS Low FMS Mid FMS High Sample Sample Dup FMS LaN FMS Mid FMS High
Sample Sample Dup
FMS Low FMS MM FMS Hi g h
Nominal Spike Level n mL
NA
NA 1 .0 10 100 NA NA 1 .0 10 100
NA
NA
1 .0
10
100
NA
I
NA
10
100
1000
GPO Location Comment ,
FSIA Drainage FSIA Drainage FSIA Drainage FSiA Drainage FSIA Drainag e FSIA Drainage FSIA Drainage FSIA Drainage FSIA Drainage FSIA Drainage FSIA Drainage FSIA Drainage FSIA Drainage FSI.4 Drainage FSIA Draina ge
BF Property BP Property BP Property BP Property BP Pro
2.2 Extraction
All samples, calibration standards, and associated quality control samples were extracted using a modified procedure of ETS-8-154.1 "Determination of Perfluorinated Acids, Alcohols, Amides, and Sulfonates in Water by Solid Phase Extraction and High Performance Liquid Chromatography/Mass Spectrometry" . Briefly, 40 mL of sample were loaded onto a pre-conditioned Waters C18 solid phase extraction (SPE) cartridge (Sep-Pak, 1 .0 g, 6 cc) using a vacuum manifold . The loaded SPE cartridges were then eluted with 5 mL of methanol . This extraction procedure concentrates the samples by a factor of eight. (Initial volume = 40 mL, final volume = 5 mL). Lab control spikes extracted in the same manner cross-validate all the method modifications/deviations from ETS-8-154.1 . See Section 3.6 for additional information .
PAGE 40F21 001000G. "
3M ENVIRONMENTAL LABORATORY REPORT NO. E06-0199
The samples and sample duplicates for BPP01, BPP02, and BPP03 were initially extracted undiluted on April 19, 2006 . Initial analysis of the,undHuted saf*les exceeded the upper limitof quantiation (25 ng/mL nominal) for PFOA and PFOS . Likewise, the sample and sample duplicate for BPWELL were initially extracted on April 19, 2006 . The final extracts were diluted 1 :10 prior to analysis . Analysis of these diluted extracts also exceeded the upperlimit ofquantitation . ,AjI the samples, sample duplicates, and field matrix spikes were reextracted on April 21, 2006 . For BPP01, BPP02, and BPP03, the samples and associated QC were diluted 1 :50 using, ASTM Type I water prior to extraction . For BPWELL, the sample, sample duplicatelow spike ario,mid spike were diluted 1 :50, whi)e the high spike was diluted 1 :500.
2 .3 Analysis All sample and quality control extracts were analyzed t`or PFOA, PF6S, PFHS, and 0FBS using 'high performance liquid chromatography/ tandem mass 60ectrometry (HPLC/MS/MS)'.' Pertinent instrument parameters, the liquid chromatography gradient program, and the specific mass transitions-analyzed are described in the tables below . Table 3. Instrument Parameters .
Instrument Name -Li q uid Chromato ra h
Guard column Ana lyti cal column In ection Volume Mass Spect rometer Ion Source Electrode -Polarity Software
'
ETSStan
A ilent 1100
Betasil C18 2.1 mrp.X100 mm), 5 m Betasil C18 2 .1 mm X 100 mm) , 5 m
5~L
lied Bios stems API 4000
Turbo Sp ray
~
Z-s .ra
Negqbw Analyst 1 .4 .1
Table 4. Liquid Chromatography Gradient Program.
Step Number
0 1 2 3 4 5
Total Time (min)
0 1 .0 14.5 15 .5 16 .5 20 .0
Flow Rate (IrL/min) -
300 300 300 300 300 300
Pereent A 2 mM ammonium acetate
80 .0 80 .0 10 .0 10 .0 80 .0 80.0
PerGent B
'
ethano
20.0
20.0
I
90.0
90.0
20.0
20 .0
;-,*t 'Fl,( a + P"-
PAGE 50F21 000001
3M ENVIRONMENTAL LABORATORY REPORT NO . E06-0199
Table 5. Mass Ti'ansitictns.
Arralyte "IPFBS "IPFHS "IPFOS
"'PFOA _
Mass Transiflon ~
Q1%Q3
299/80
299/99
399/80
, 399/99
499/130 '
499/99 '
499180
i ~
413/369'~
r.
41M19
~ __ 413/1 9
I; DNVeIf Time (msec)
125
125
125
125
125
1-2'5 -
125
'
k
125
125__
~125
(1) The individual transiSions were summed to produoe a "total im chromatograirr"_(TP . The TICs were used for quantitaBon.
-
,~ ,
. .
~ .. ,
.
Data Analysis
3.1 Calibration
Calibration standards were prepared by.spikirlg known amounts of stock solutions containing the target
anaiytes into 40 mL of ASTM type I water, Each spiked water standard was then, extracted in the same
mar,ner as the,,sol!ected sampl,es, A total oftwelve spiked standards ranging from 0.02,5 ng/mL to 25
ng/mL,(nominaE) were prepared . A quadratic, 1/x weighted, calibration curve was used to fit the data
for each analyte. The data were not forced through zero during the fitting process. Calculating the -
standard concentration using the peak area counts and the resultant calibration curve confirmed
,
accuracy of each curve point. Each extracted calibration standard used to, generate the final calibration
curve met the method calibration accuracy requirement of 100t25% . The correlation coefficients (r)
were greater than 0.999 for all analytes .
3.2 l_imit of Quantitation (LOQ) The LOQ for this analysis, as defined in ETS-8-154 .1, is the lowest non-zero calibration standard in the curve in which the area counts are at least twice those of the method and solvent blank(s) . The LOQs for PFOA, PFOS, PFHS, and PFSS were 0.050C ng/mL., 0.0999~ ng/mL; 0.0250 ng/mL, and 0.0250 ng/mL, respectively. Note: these LnQvalues have not been corrected for. sample specific dilution factors. Area count comparison for the method blanks and the lowest calibration standard will be provided in Section 3.5.1 .
3.3 Systecn .Suitability
Replicate injections of the 1 ng/mL extracted-calibrat;on standard were analyzed at the beginning and end of the analytical sequence to demonstrate overall system suitability . All analytes met method acceptance criteria of less than 5% relativa standard deviation (R.SD) for, peak area and less than 2% RSD for retention time for both opening and closirg system suitability.injections. -
3.4 Continuing Calibration
During the course of the ana!ytical sequence, several continuing calibration verification samples ' (CC'Js) ware analyzed to c6ntirm that the~ instrument response and the initial calibration curve were still in control. One PFOS CCV (139%) and one PFHS CCV (153%) exceeded method acceptance criteria of 10025% for accuracy . Both of these fion-compliant CCVs followed a contaminated solvent blank and the high recovery is most likely carryover from the'previous injection. A method deviation has been
PAGE 60F21
QooQO8"
3M ENVIRONMENTAL LABORATORY REPORT N0 . E0fr0199
issued . The overall impact to the data quality objectives for the sample results is considered minimal as all sample injections and sample related QC injections were bracketed by compliant CCVs.
3.5 Blanks Three types of blanks were prepared and analyzed with the samples : method blanks, solvent blanks, and field/trip blanks . Each blank type is described below.
3.5.1 Method Blanks
Several method blanks were prepared by loading 40 mL of ASTM Type f water onto a C18 SPE cartridge and eluting with 5 mL of methanol using .the same extraction procedure as the samples. Method blanks were prepared to evaluate the levels of background contamination in the overall extraction process (reagent water, glassware, SPE cartridges, etc.) The.calibration curve was prepared on a separate day as the samples. (Calibration standards: April 10, 2006 ; diluted samples: April 21, 2006). The method blanks prepared with the calibration standards as well as with the samples were both analyzed during the April 21, 2006 analysis . Additional lab matrix spikes were prepared and analyzed in a separate analytical run initiated on April 24, 2006 . Again, the method blanks prepared with the calibration curve and the method blanks prepared with the spikes were analyzed. Method blank area count comparisons to the LOQ standard are provided in the Attachments section at the end of this report . 3.5.2 Solvent Blanks
Several methanol solvent blanks were analyzed to assess system contamination and/or instrument
carryover. For the April 21, 2006 ariarysis,-three separate viais'of methanol solvent blanks were- :
contaminated and produced area counts of the target analytes greater than,one-half those of the LOQ
standard . A method deviation has been-issued . The solvent blank area count comparison for the April
21, 2006 is provided in the Attachments section at tha end of this report. For the lab matrix spikes `~
analyzed on April 24, 2006, only the initial solvent blanks injected before the, opening system ~'
suitabilities ano the solvent blanks analyzed after the highest calibration standard exhibited area count,
greater than one-half the LOQ standard .'!' ' '
~
. .
3.5.3 FiekllTrip Blanks
Prior to sample collection, seven sets oftrip/field blanks were prepared : A trip blankconsists of a sample container filled with 450 mL of ASTM Type I water, sealed, and shipped to the sample collection site along with the empty containers. The trip blank serves as an additional method blank that accounts for any storage conditions and/or holding tirne issues that the samples may .experienGe . Results of the trip blank analyses will be provided in the final comprehensive report . 3.6 Lab Control Spikes (LCSs) Lab control spikes at nominal concentrations of 0.050 nglmL, 5.0 ng/mL, 100 ng/mL, and 1000 ng/mL spikes were prepared and analyzed each day samples were extracted and analyzed ., The 0.050 ng/mL and 5.0 ng/rnL LCSs were prepared by spiking known amounts of the analytes into 40 mL of ASTM Type I water to produce the desired concentration. The spiked water samples were then extracted and analyzed in the same manner as the samples, . For the 100 ng1mL and 1000 ng/mL LCSs, target analytes were added to 450 mL of ASTM Type I water to produce the final desired concentration. An aliquot of the LCS was then diluted 1 :50 or 1 :500 with ASTM Type I water prior to extraction, .in the same manner as the diluted samples. This technique was done to demonstrate that the dilution procedure used for the samples was able to produce accurate results . Analysis of replicate LCSs at the various levels cross-validates the analytical method, as used here, for any modifications/deviations from ETS 8-154.1 . Additionally, LCS results will be used to determine overall method uncertainty in Section 3.7. Table 6 summarizes the LCS recovery results.
PAGE 7 OF 21
000009
3M ENVIRONMENTAL LABORATORY REPORT NO . E06-0199
LCS Percent Recovery = Calculated Concentration , 100% Spike Concentration
LCS% RSD = standard deviation LCS replicates , 100% average LCS recovery
PAGE 80F21
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3M ENVIRONMENTAL LABORATORY REPORT NO . E06-0199
3.7 Analytical Method Uncertainty
Both the accuracy (percent recovery) and precision (%RSD) of the lab control spikes were used to
estimate the overall method's analytical uncertainty for a given analyte . For example, the overall
accuracy and precision for PFOA based on LCS results was 101 %9 .7%. The measured precision
(%RSD) is then used to determine the range of the accuracy.
'
Example:
101-(0 .097) = 9.84 101+9.84=111 .1 ; 101-9.84=91 .45
Thus, LCS accuracy results range from 91 .45% to 111 .1 %. The absolute difference of the low and high ends of this range, when compared to 100%, are then calculated .
111 .1%-100= 11 .1% 100%-91 .45 = 8.54% .
The most conservative (largest) absolute difference is then used as the analytical uncertainty for the given analyte. Therefore, the analytical uncertainty for PFOA is given as 100t11 % (two significant figures) forthese results. For PFOS, PFHS, and PFBS, the analytical method uncertainty is 10016%, 1005.8%, and 1008.8%, respectively . It should be emphasized that the analytical method uncertainty described above only applies to the method and the procedures performed within . Additional quality control samples specific to the sample matrix, in the form of fieid matrix spikes and lab matrix spikes, demonstrate that the individual sample results are accurate to within 10030%, the targeted data quality objectives .
3.8 Field Matrix Spikes (FMS)
At a minimum, low and high field matrix spikes were collected at each sampling point to verify that the analytical method is applicable to the collected matrix. For some locations, a mid-level spike was also collected. Field matrix spike recoveries within method acceptance criteria of 100t30% confirm that "unknown" components in the sample matrix do not interfere with the extraction and analysis of the analytes of interest . Field matrix spikes will be presented in the next section with the sample data . The field matrix spike should be at least 50% of the endogenous sample concentration to be considerea an appropriate spike level for the given sample matrix .
FMS Recovery = (Sample Concentration of FMS-Average Concentration : Field Sample & Field Sample Dup.) .100% Spike Concentraton
3 .9 Lab Matrix Spikes (LMS) If the sample and sample duplicate produced concentrations where none of the associated field matrix spikes were at least 50% of the endogenous concentration, then laboratory matrix spikes (LMS) were prepared . LMSs were prepared by spiking a known amount oftarget analytes into a measured aliquot of the sample matrix. The spiked matrix was then diluted, if necessary, and extracted in the same manner as the samples. LMS recoveries within 10030% demonstrated that the anaiytical method was appropriate for the given sample matrix only in the absence of an appropriate field matrix spike.
Data Summary
The data tables below summarize the sample results, field matrix spike recoveries, and laboratory matrix spike recoveries for the four locations (BPP01, BPP02, BPP03, and BPWell). Each table provides the average concentration and the relative percent difference (RPD) of the sample and sample duplicate.
PAGE 11 OF 21
000013
3M ENVIRONMENTAL LABORATORY REPORT NO. E06-0199
BPP01 The endogenous concentration for 13131301 was at least twice the spike concentration for the low spike (1 ng/mL), mid spike (10 ng/mL) and high spike (100 ng/mL) for both PFOA and PFOS. A laboratory matrix spike at 500 ng/mL was prepared and analyzed. The LMS recovery met method acceptance criteria of 10030% for PFOA (79.6%), but not for PFOS (60.6%) . Therefore, the sample results for PFOS should be considered estimated minimums with a sample analytical accuracy within an order of magnitude as the analytical method has not been demonstrated to be suitable for the given sample matrix. FMS and/or LMS recoveries within 10030% for PFOA, PFHS, and PFBS demonstrate that the analytical method is appropriate forthe given sample matrix for these analytes . BPP02 The endogenous concentration for BPP02 was at least twice the spike concentration for the low spike (1 ng/mL) and mid spike (10 ng/mL) for both PFOA and PFOS as well as the high spike (100 ng/mL) for PFOS only. A laboratory matrix spike at 250 ng/mL was prepared and analyzed. The LMS recovery met method acceptance criteria of 100301/6 for PFOA (75.0%), but not PFOS (59.8%) . Therefore, the sample results for PFOS should be considered estimated minimums with a sample analytical accuracy within an order of magnitude as the analytical method has not been demonstrated to be suitable for the given sample matrix . FMS and/or LMS recoveries within 10030% for PFOA, PFHS, and PFBS demonstrate that the analytical method is appropriate for the given sample matrix for these analytes. BPP03 The endogenous concentration for BPP03 was at !east twice the spike concentration for the low spike (1 ng/mL) and mid spike (10 ng/mL) for both PFOA and PFOS as well as the high spike (100 ng/mL) for PFOS only. A laboratory matrix spike at 250 ng/mL was prepared and analyzed. The LMS recovery met method acceptance criteria of 100t30lo for PFOA (73.8%), but not PFOS (60.8%). Therefore, the sample results for PFOS should be considered estimated minimums with a sample analytical accuracy within an order of magnitude as the analytical method has not been demonstrated to be suitable for the given sample matrix. The high level PFBS FMS exceeded method acceptance criteria of 10030% (134%) . However, the PFBS results for this sample are still considered accurate within 10030% because the criteria exceedence was minimal (within 4%) and mid level FMS and LMS recoveries were excellent, 101% and 90.2%, respectively. High level FMS and LMS recoveries within 10030% for PFOA and PFHS also demonstrate that the analytical method is appropriate for the given sample matrix for these two analytes as well. BPWell The endogenous concentration for BPWell was at least twice the spike concentration for the low spike (10 ng/mL) for PFOA, PFOS, PHFS, and PFBS as well as the mid spike for PFOA, PFOS, and PFHS . Although the high level spike (1000 ng/mL) was an appropriate level for all four analytes, the recoveries were consistently less than 30% for all anafytes, with PFOS showing no measuring recovery. The high FMS was reextracted to rule out a potential preparatory error during the extraction process. The second extraction produced similar recoveries as the first . A laboratory matrix spike at 1000 ng/mL was also prepared . The LMS recovery met method acceptance criteria of 100t30% for PFOA (85.4%), PFHS(93.5%), and PFBS(97.2%) but not for PFOS (13.5%) . Therefore, the sample results for PFOS should be considered estimated minimums with a sample analytical accuracy within an order of magnitude as the analytical method has not been demonstrated to be suitable for the given sample matrix. Although the LMS produces acceptable recoveries for PFOA and PFHS, the sample results should be considered estimated minimums as no appropriate supplementary FMS recovery was available. Low and mid level FMS and LMS recoveries within
10030% for PFBS demonstrate that the analytical method is appropriate for the given sample matrix for this analyte only . Further method development for the BP Well sample matrix will be performed to see if improved PFOA, PFOS, and PFHS recoveries can be achieved.
PAGE 12 OF 21 ' 00014
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3M ENVIRONMENTAL LABORATORY REPORT NO . E0fr0199
Sample matrix QC samples for the four samples reported herein did not meet method acceptance criteria of 10030% for PFOS . Therefore, the values-fistedin Table ,1, and Tables 7-101brPFOS should be considered estimated minimums. Thi6saniple analytical accuracy,is arbitrarily estimated to be within an orider,ofmagnitude. Further: method development is needed for this matrix as the QC results demonstrated that unknown matrix c. omponents preclude accurate analysis with the method as performed here . Field matrix spikes yielding recoveries within 1030% demonstrated that the analytical method was suitable for the given sample matrices for PFOA, PFHS, and PFBS for BPP01, BPP02, and BPP03. The analytical method uncertainty forthese analytes was presented in Table1 . PFOA andPFHS results forBPWeNshould also be considered estimated minimums with a sample analytical accuracy within an erder of magnitude as no acceptable held matrix spikes recoveries were produced.
Data / Sample Retention All remaining sample and associated project data (hardcopy and electronic) will be archived according to 3M Environmental Laboratory standard operating~procedures .
PAGE 17 OF 21
000019
p. 18
3M ENVIRONMENTAL LABORATORY REPORT N0. E0G-0199
Mich ile D. Malinsky, Ptf:U,
R. Lindstrom,3M Technical Reviewer -11
William K. Raagen, Pn.D., Environmental LaborGto;y Management
. Date
The 3M Environmental Laboratory's Quality Assurance Unit has audited the data and report for this project.
Quality As nce Representative
Date
3M CONFIDENTIAL
PAGE 1 S OF 21 0 0 0020
p. 19
3M ENVIRONMENTAL LABORATORY REPORT NO. E0fr0199
8.1 Method BIankILOQ Area Count Comparison. Table 11 . Method BIank/LOQ Area Count Comparison : April 21, 2006.
Anal cal Run: 7 21 200B
Ares Counts
Dataflle
Sam le Descri tion Sam le Name
PFOA
PFOS
PFHS
Method Blanks
wlEh the Extracted Curve
s060421a025 s060421a026 s060421a027 s060421a028 s060421a029 s060421a030 s060421a031 s060421 a032 Method Blanks
Method Blank-1
MB-060410-1
Method Blank-2
MB-060410-2
Method Blank-3
MB-060410-3
Method Blank-4
MB-060410-4
Method Blank-5
MB-060410-5
Method Blank-6
MB-060410-6
Method Blank-7
MB-060410-7
Method Blank-8
IviB-060410-8
aied wfth the Extracted Sam les
55982 18376 16127 22714 21587 25928 21060 16383
3413 1082 1718 1116 792 4338 2143 1776
1591 668 1970 639 1686 2077 2436 1660
s060421a045
Method Blank-1
MB-060421-1
12933
1437
('1121128
s060421a046
Method Blank-2
MB-060421-2
12809
1446
"'129379
s060421a047 s060421a048 s060421a049 s060421a050 s060421a051 s060421a052
Method Blank-3 Method Blank-4 Method Blank-5 Method Blank-6 Method Blank-7 Method Blank-8
MB-060421-3 MB-060421-4 MB-060421-5 MB-060421-6 MB-060421-7 MB-060421-8
13875 22242 19675 17774 13843 14073
2228
(1)66834
2053
('142902
1762
"133923
1568
('43105
1084
6059
1492
,5570
Area Counts of the LOQ standard Area Counts of the LOQ standard*0.5
163373 81686.5
14600 7300
13176 6588
Concentration of LOQ standard n mL
0.0500
0.0999
0 .025
(1) Meth od blanks ii qeded immediately after a highly contaminated solvent blank. Carryover present .
when establishing the LOQ for PFHS .
PFBS
2760 2001 2336 1305 2109 5711 3561 4235
277 715 595 1052 826 2071 M19419 _ 450 25766 12883 0.025 Values excluded
(2) Method blank determined to be a statistical ouflier at the 99% confidence level using Dixon's Q-test. Value excluded when establishing the LOO for PFBS.
PAGE 19 OF 21
000021
p. 20
3M ENVIRONMENTAL LABORATORY REPORT NO . E06-0199
Table 12. Method BIankILOQ Area Count Comparison :% _ April 24, 2006.
Analytical Run: Datafle
7 24 2006 S le Deisrf on
Sample Name
PFOA
Method alanks pre pared with the Extracted Curve
s060424a025
Method Blank-1
M13-06000-1 ~ ('136625
s060424a026
Method Blank-2
MB-060410-2
('142239
s060424a027
Method Blank-3
MB-060410-3 ~ 25302
s060424a028
Method Blank-4
MB-060410-4
22151
s060424a029
Method Blank-5
MB-060410-5 ~ 30401 ,
s060424a030
Method Blank-6
M13-080410-6 j 17458
s060424aU31
Method Blank-7
MB-060410-7 ' 23074
s060424a032
Method Blank-8
MB-060414-8 ~ 22049
Mefhod Blanks pared wiM the Extracted Lab
Malrfx Spikes
s060424a090
Method Blank-1
MB-350425-9 j 30448
s060424a091 s060424a092
Method Blank-2 Method Blank-3
MB-060425-2
15006
MB-080425-3 ~ 11262
s060424a093
Method Blank-4
MB-060425-4
11867
s060424a094
Method Blank-5
MB-060425-5 , 16236
s060424a095
Method Blank-6
MB-060425-6
15924
s060424a096 s060424a097
Method Blank-7 Method Blank-8
M13-060425-7 i 2275LI M13-060425-8 ' 192&1
j4rea Counts of the LOO standard
~ 36G60
Area Counts of the LOO standard"0.5 Concentrat(on of LO{l standard n L
~ 18030 0 .025
Area Counts
PFOS
PFHS
3514 2274 2950 804 2565 827 1195 1192
2301 1266 991 836 1024
1107
1530 1071 6724 3362 0 .04
2029 2890 1147 1197 1955 1275 1974 1512
1778 1311 1039 707 717
589
1038
1135 12166 6083 0 .025
PFBS
3078 3938 2248 1638 2593 5242 3516 4294
1906 2990 1703 6142 2723 5446 4359 1677 27032 i 13516 0 .025
(1)
Value excluded for the analysis of this extract
LOQ determination for the demonstrated area counts
given below
set. Area counts are very dose to one-half the LOQ value one-half the 25 ppt standard . LMSs analyzed on this day
. Prior are
well above the LOQ .
PAGE 20 OF 21
000022
p. 21
3M ENVIRONMENTAL LABORATORY REPORT NO. E06-0199
8.2 Solvent BIank/LOQ Comparison . Table 13. Area Counts of Solvent Blank.
,
Area Counts
-
File
Vial Position
PF?A
PFOS
PFHS
s060421a001 s060421a002 s060421a003 s060421a009 s060421a010 s060421a023 s060421a024 s060421a035 s060421a037 s060421a042 s060421a044 s060421 a055 s060421a057 s060421a068 s060421a070 s060421a081 s060421a083 s060421a094 s060421a096 s060421a107 s060421a109 s060421a120 s060421a122 s060421a127 s060421a129 s060421a135
LOQ Standard
91 91 91 91 92 92 92 93 ; . 93 93 94 94 94 95 95 95 95 96 96 97 97 97 98 98 ' 99 99
70233 16249 18222 48287 ")84762 48308 ,
"1162166, 23806, . 15939 , 49109, . 126&15, 47071 . 536918 74125 . 62139 68329 76799 77269, 14824 19120, 9918. 24599 37573' ' ' 18673 31743 163373
3067 - I
1853
2196
1851
I
,1642
- , ,567, . .
4524 ,
, 1505
5006
2424
' , f4192
4524 , ,
4738
('~283547 .
(1)52950
~'~8904, , `
2706
12135
1693
(')274~54_
,1141+~ 1 . ~
('>328841
338~, . . .,
(')257946
2525 ,
5237
, .5907
6588
2124
3945
3139
3951
4192
3512
3358
3905
1166
852
1763
1499
1028
, .1024
`
1589
2321
1905
' 6127
1'10ti
1909
1944
1472
14600
13176
Yz" LOQ
Standard e~ea counts
of
the
solvent
81687 blank were
greater
7300 than'/*the
LOQ
6588 standard area
counts.
PFB_ S
192 563 . 471. . 447 889
6609 7007 "'1582 235 1823 1118, . 547 . 1 946 1137 975 1225 1149 1054~'= 1173 335 ;, 1289 698 3275 2190 937 632 25766
12883
PAGE 21 OF 21
000023