Document wm2KpXoEO05GkNxV7VbNdL9o
- 3M ENVIRONMENTAL LABORA TORY REPORT NO. E06-0199
Subreport
Analysis of PFOA, PFOS, PFHSI, 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 EH S Operations 3M Environmental Laboratory
Building 2-3E-09 935 Bush Avenue St. Paul, MN 55106
Requester
Gary Hohenstein 3M Building 42-02-E-27
PO Box 3331 Saint Paul, MN 55133-3331
Phone: (651)778-5150 Fax: (651) 778-7203
U CCW tD rfED l
The tasting reported herein meet the requirements of ISO/IEC 17025-1999 "General
Requirements for the Competence of Testing and Calibration Laboratories", in accordance with the A2LA Certificate *2052-01. Testing that compiles with this International Standard also operate In accordance with ISO 9001/ISO 9002 (1994).
Certificate #2052-01
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3MENVIRONMENTAL LABORATORY REPORT NO. 06-0199
3M E nvironm ental Laboratory 3M Environmental Laboratory Manager: William K. Reagen, Ph.D. 3M Technical Lead: Michelle Malinsky, Ph.D. Report Author: Michelle Malinsky, Ph D.
Analytical Subreport E06-0199
Surface Water Samples BPP01, BPP02, and BPP03; Ground Water Sampile BPWell
Decatur Offsite Sampling Event Report Date: May 1,2006
I lntroductibn/Summatyi
The 3M Environmental Laboratory extracted a id analyzed ground water and surface w ater samples collected by W eston Solutions personnel on April 12 and 13,2036 near the 3M Decatur facility. Samples were returned to the 3M Environmental .aboratory for analysis of perfluorooctanoate (PFOA), perfluorooctane sulfonate (PFOS), perfluorohexane sulfonate (PFMS) and perfluorobutane sulfonate (PFBS) under laboratory project number E06-0199 using modified 3M Environmental Laboratory Method ETS 8-154.1 "Determination of Perfluorinated Adds, Alcohols, Amides, and Sulfonates in W ater by Solid Phase Extraction and High Performance Liquid Cnromatography/Mass Spectrometry".
Per the dient's request, an initial subreport is being issued for the following four sample locations only: . DAL SWS BPP01 . DAL SWS BPP02 . DAL SWS BPP03 . DAL GWS BPWELL
This report will contain information relevant to these four sample collection points only. These results w ill be reissued in a comprehensive final project report that indudes 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 locations, a third mid-levei field spike was prepared. Each empty container was marked with a "fill to here' line which corresponded to a final volume o f 450 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 of the four locations presented here will be provided later in this report.
C ertificate #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 w th the A2LA Certificate #2052-01. Testing that complies with this International Standard also operate in accordance with ISO
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3M ENVIRONMENTAL LABORATORY REPORT NO. 06-0199
Samples were initially extracted and analyzed on April 19, 2006. Samples were diluted,, 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 24,2006.,
. . .
Table 1 below summarizes the sample results. All results for quality control samples prepared and ' analyzed with the samples w ill be reported and discussed elsewhere in this report. All samples were diluted 1:50 in ASTM Type I water prior to extraction.
Table 1. Sam ple Results Summary. -
3 M IM S ID E06-0199-055 E 0 6 0 1 99-056
E06O199-060 06-0199061
E06-019 9 0 6 5 E06-019 9 0 6 6
E060199070 E06O199071
Sample Description
. n PFOA Concentration
(ng/mU
mPFOS Concentration
f n & rtL )
mPFHS Concentration
(mFmL)
DAL SWS BPP01 0 060413
293 '*> 4 2 3 .
DAL SWS BPP01 DB 060413 Average
307 300
>380 >402 .
%RPD Sampie/Sample Dup
' 4.7
NA
DAL SWS BPP02 0 060413. t DAL SWS BPP02 DB 060413
" 206
J >295
219 " 1 >314
' ` Avenge %RPD SamplwSample Dup.
212 6.1 ,
>304 NA
DAL SWS BPP03 0 060413
DAL SWS BPP03 DB 060413
.
A varsge
%RPD Sampie/Sample Duo
219 214 216 2.3
>272 >256 >264
NA
DAL GWS BPWELL 0 060413 DAL GWS BPWELL DB 060413
>774 >779
>1460 ' >1170
A ve ra g e
>776 MA
>1320 , NA
53 .3. 54,3 53,
1.8 33.2 39.8 39.0 ` 4.1 39.1 40.1 39.6 2.5 ' >145 ` >145 >145 NA
RpFBS Concentration
(ng/mL)
6.98 7.17 7.08
2.7 4.30 4.72 4.66 2.6 4.69 5.05 4.J7 7.4 17.2 17.6 17.4 23
I
I i'
(1) The analytical method uncertainty for PFOA, PFHS, and PFBS was 10O11%, 10Q5.8%, and 1008.8%,
respectively based on m ethod accuracy arid precision. Seri'Section 3.7 fo r additional explanation. The lim it o f
quantitation (LOQ) fo r these samples onlywas 2.50 ng/mL (PFOA) and 1.25 n g /m l (PFHS and PFBS). Results
and average values are rounded to three significant figures according to EPA rounding rules. Percent relative
difference (%RPD) values are rounded to two significant figures. Because o f rounding, values may vary slightly
from those listed in the taw dbta. '
`
'
(2) All PROS sample results presented herd should be considered estimated minimum values as quality
control samples (Held m a trix .spikes and lab matrix spikps) associated with these four samples did not
demonstrate adequate method performance. The accuracy of the PFOS results could be within an order
o fmagnitude. %RPO values not calculated. BPWell results for PFOA and PFHS should also be
considered estimated minimums as held matrix spike recoveries did not meet method acceptance criteria
o f 100*30%. The analytical accuracy o f the PFOA and PFHS estimated values for this sample only could
be within an order o fmagnitude. %RPD values not calculated.
.
2 Methods -
2.1 Sample Collection
Samples were collected in NalgeneTM (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
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3M ENVIRONMENTAL LABORATORY REPORT NO 06-0199
fo jr analytes of interest (PFOA, PFOS, P^HS and PF8S). 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 Collection and Spike information.
3M U M SID #
W eston Sample Description
3M BolSie Number
E06-0199-055 DAL SWS BFP01 0 060413
109
E06-C199-056 EOS-0199-957
DAL SWS BPP01 DB '360413 DALSW SBPFCt LS03C413
110 ' l l
E06-0193-058 E06-0199-059
DAL SWS BPP01 MS 960413 DAL SWS BPP01 HS 060413
'll 2 113
E06-0199-060 DAL SWS BPP02 0 060413
119
E06-0199-061
DAL SWS BPP02 DB 060413
120
E 0 6 -0 1 99 -062 E 06-019 9 -063
DAL SWS BPP02 LS 060413 DAL SWS BPP02 MS 060413
121 122
E06-0199-064 DAL SWS BPP02 HS 060413
123
E06-0199-065 DAL SWS BPP03 0 060413
114
E06-0199-066 DAL SWS BPP03 DB 060413
115
E06-0199-067 DAL SW S BPP03 LS 060413
ms
E06-0199-068 DAL SWS BPP03 MS 060413
E06-0199-069 DAL SWS BPP03 HS 060413
',13
E06-0199-070 DAL GWS BPVUELL 0 060413
72
E 06-0199-071
DAL GWS BPWELL DB 060413
73
E6-0199-072 DAL GWS BPW ELL LS 060413
74
E06-O199-073 DAL GWS BPWELL MS 060413
75
E 06-0199-074
DAL GWS BPWELL KS 060413 ,i ,, l. r . , ,
DAL = Decatur. AL
SWS = Surface W ater Sample
GWS = Ground W ater Sample
0 = Sample
DB = Duplicate
LS = Low Spike
MS = Mid S pite
HS = High Spike
Bottle Dsignation
Sample Sample Dup
FMS Lovi FM SM id FMS High Sample Sample Dup FM3 Low FM SM id FMS High Sample Sample Dup FMS Low FM SM id FMS High Sample Sample Dup FMS Low FMS Mid FMS High
Nominal Spike Level fng/mL)
NA NA 1.0 10 100 NA NA 1.0 10 100 NA NA 1.0 10 100 NA NA 10 100 1000
GPO Location Comment
FSIA Drainage FSIA Drainage FSIA Drainage FSiA Drainage FSIA Drainage FSIA Drainage FSIA Drainage FSIA Drainage FSiA Drainage FSiA Drainage FSIA Drainage FSIA Drainage FSIA Drainage FSIA Drainage FSIA Drainage
BP Property BP Property BP Property BP Property BPFroperty
2.2 Extraction
All samples, calibration standards, and associated quality control samples were extracted using a modified procedure o f ETS-&-154.1 "Determination of Perfluorinated Adds, Aicohols, 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.
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3M ENVIRONMENTAL LABORATORY REPORT NO. 06-0199
The samples and sample duplicates for BPP01, BPP02, and BPP03 were initially extracted undiluted
on April 19,2006. Initial analysis of the undiluted samples exceeded the upper limit o f quantiation {25
ng/m l 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 upper lim it of quantitation. .A ll 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 duplicate,,low spike arid mid spike were diluted 1 50 while the hiah
spike was diluted 1:500.
>- -
- , ' . .... a
2.3 Analysis
i,
All sample and quality control extracts were analyzed for PFOA, PFOS, PFHS, and PFBS using high
performance liquid chromatography/ tandem mass spectrometry (HPLC/MS/MS). Pertinent instrument
parameters, the liquid chromatography gradient program, and the specific mass transitions analyzed
are described in the tables below. ,
y
Table 3. Instrum ent Parameters.
In stru m e n t Name L iq u id C hrom atograph G uard colum n A n a ly tic a l colum n In je ctio n Volum e M ass S pectrom eter Ion S ource E lectrode P o la rity S oftw are
ETSStan
.
. A pient 1100
Betasil C18 (21 mm.X100 mm). 5 urn
Betas C18 (2.1 mm X 100 mm). 5 ,.m
5uL
Applied Biosystems API 4000
' '
Turbo Spray 2-soray
-
N ega tive Analyst 1.4.1
Table 4. Liquid Chrom atography Gradient Program.
Step Humber
0 1 2 3 4 5
Total Time . (min)
0 1.0 14.5 15.5 16.5 20.0
Flow Rate (fJL/mm)
300 300 300 300 300 300
Percent A (2m M ammonium acetate)
80.0 80.0 10.0 10.0 80.0 80.0
Percent B
200 200 900 900 20 0 20.0
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3M ENVIRONMENTAL LABORATORY REPORT NO. 06-0199
Table 5. Mass Transitions.
, Amatyta f'lpF B S |,!p f h s <1,P FO S
mP FO A
Mass Transition Q1/Q3 299/80 299/99 399/80
, 399/99 499/130 499/99 499,SO 413/369 413/219 413/169
Dwell Tints (msec)
125 125 125 125 >25 125 - 125 ; 125 125 125
(1) The individual U aitefjons were summed to produce a ` total io.'i chromatogram" (TIC). T tie TICs were used fo r quantitation.
3 Data Analysis
, /V 'r '/'
t :.' '
3.1 Calibration
Calibration standards were prepared by spiking known amounts of stock solutions containing the target analytes into 40 mL of ASTM type I water, Each spiked water standard was then extracted in the same manner as the. collected samples. A total of twelve spiked standards ranging from 0.025 ng/mL to 25 ng/mL.(nominal) were prepared. A quadratic, 1/x weighted, calibration curve was used to fit the data for each analyte. The date were not forced th-cugh zero during the fitting process. Calculating the standard concentration using the peak area counts and the resultant calibration curve confirmed accuracy o f each curve point. Each extracted calibration standard used to generate the final calibration curve met the method calibration accuracy requirement of 10025%. The correlation coefficients (r)
were greater than 0.999 for all analytes.
3.2 Limit of Quantitation (LOQ)
The LOQ for this analysis, as defined in ETS-8-154.1, is the 'owes! non-zero calibration standard in the
curve in which the area cotints are at least twice those of the method and solvent blank(s). The LOQs
for PFOA. PFOS, PFHS, and PFBS were 0.050C ng/mL,, Q.C999 ng/mL, 0.0250 ng/mL, and 0.0250
ng/mL, respectively. Note: these LOQ values 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 System Suitability
.
Replicate injections of the 1 ng/mL extracted-calibration 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% relative- standard deviation (RSD) for peak area and less than 2%
RSD for retention time for both opening and closing system suitability injections.
3.4 Continuing Calibration
During the course o f the analytical sequence, several continuing calibration verification samples (CCVs) were analyzed to confirm that the instrument response and the initiai calibration curve were still in control. One PFOS CCV (139%) arid one PFHS CCV (153%) exceeded method acceptance criteria o f 10025% for accuracy. Both of these non-ccmpliant CCVs followed a contaminated solvent blank and the high recovery is most likely carryover from the previous injection. A method deviation has been
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3M ENVIRONMENTAL LABORATORY REPORT NO. E06-0199
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 o f 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 m l 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 foe LOQ standard are provided in foe Attachments section at the end ofthis 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 ariaysis, three separate viais of methanol solvent blanks were
contaminated and produced area counts of the target analytes greater than one-half those of foe LOQ
standard. A method deviation has been issued. The solvent blank area count comparison for the April
21,2006 is provided in foe Attachments section at foe end of this report. For the lab matrix spikes
analyzed on April 24,2006, only the initial solvent blanks injected before foe opening system
suitabilities ana the solvent blanks analyzed after foe highest calibration standard exhibited area counts
greater than one-half foe LOG standard.
:
3.5.3 Field/Trip Blanks
..
Prior to sample collection, seven sets of trip/field blanks were prepared. A trip blank consists of a
sample container filled with 450 mL of ASTM Type I water, sealed, and shipped to the sample
collection site along with foe empty containers. The trip blank serves as an additional method blank
that accounts for any storage conditions and/or holding time issues that foe samples may experience.
Results of foe trip blank analyses will be provided in foe final comprehensive report.
.
3.6 Lab Control Spikes (LCSs)
Lab control spikes at nominal concentrations of 0.050 ng/mL, 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/mL LCSs were prepared by spiking known amounts of the analytes into 40 mL of ASTM Type I water to produce foe desired concentration. The spiked water samples were then extracted and analyzed in the same manner as foe samples, For foe 100 ng/mL and 1000 ng/mL LCSs, target analytes were added to 450 mL o f 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 foe various levels cxoss-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 foe LCS recovery results.
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3 M ENVIRONMENTAL LABORATORY REPORT NO. 06-0199
C alculated C oncentration
LC S P ercent R ecovery =
100%
Spike C oncentration
standard deviation LCS replicates LCS% RSD =
100%
average LCS recovery
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3MENVIRONMENTAL LABORATORY REPORT NO 06-0f 99
Table 6. *1fLab`Control Spike Results.
Simple Description
Lab ID
O.OSppbLCS LCS-060410-1
0.05 ppb LCS LCS-060410-2
0.05 ppb LCS LCS-060410-3
5.0 ppb LCS
LCS-060410-4
5.0 ppb LCS
LCS-060410-5
5.0 ppb LCS
LCS-060410-6
0.05 ppb LCS LCS-060421-1
0.05 ppb LCS LCS-060421-2
0 .05 ppb LCS LCS-060421-3
5.0 ppb LCS
LCS-060421-4
5.0 ppb LCS
LCS-060421-5
5.0 ppb LCS
LCS-060421-6
100 ppb LCS
LCS-060421-7
100 ppb LCS
LCS-060421-8
100 ppb LCS
LCS-060421-9
1000 ppb LCS LCS-060421-10
1000 ppb LCS LCS-060421-11
1000 ppb LCS LCS-060421-12
O.OSppbLCS LCS-060425-1
0.05 ppb LCS LCS-060425-2
5.0 ppb LCS
LCS-060425-3
5.0 ppb LCS
LCS-060425-4
100 ppb LCS
LCS-060425-5
100 ppb LCS
LCS-060425-6
1000 ppb LCS LCS-060425-7
1000 ppb LCS LCS-060425-8
Average R ecovery i% RSD
PFOA
Spiked Cone. (ng/mL)
Calc. Cone. (ngtnL)
% Recovery
0.0500 0.0500 0.0500
5.00 5.00 500 0.0500 0.0500 0.0500 5.00 5.00 5.00 100.0 100.0 100.0 1000 1000 1000 0.0500 0.0500 5.00 5.00 100.0 100.0 1000 1000
<0.0500 0 .0 5 0 0 0.0517
4.93 4.86 5.30 0 .0 5 0 .0 5 0.0514 5.02 4,81 4.82 95.0 99.7 96.9 928 977 1030 0.0689 0.0600 4.91 4.87 95.3 98.6 977 972 101%9.7%
mNA NA 104 98.6 97.2 106 *N A NA 103 100 96.2 96.4 95.0 99.7 96.9 928 977 103 |4!138 120 982 97.3 95.3 98.6 97.7 97.2
PFOS
Spiked Cone. (ng/mL)
Calc. Cone. (ngfaiL)
% Recovery
0.0500 0.0500 0.0500
5.00 5.00 5.00 0.0500 0.0500 0.0500 5.00 5.00 5.00 99.9 99.9 99.9 999 999 999 0.0500 0.0500 5.00 5.00 99.9 99.9 999 999
<0.0999 <0.0999 <0.0999
4.93 5.01 5.05 <0.0999 <0 0999 <0.0999 4.53 4.34 4.49 87.3 89.2 88.5 855 899 929 0.0631 0.152 4.79 4.94 84.5 89.8 878 849 93.1%10%
'NA NA NA 98.7 100 101 NA NA NA 90.7 86.9 89.9 87.4 89.3 88.6 85.6 90.0 93.0 >*>126 304 95.9 98.9 84.6 89.9 879 85.0
PFHS
Spiked Cone. (ng/mL)
Cafe. Cone. (ng/mL)
Recovery
0.0500 0.0500 0.0500
5.00 5.00 5.00 Q.OSOO 0.0500 0.0500 5.00 5.00 5.00 100 100 100 1000 1000 1000 0.0500 0.0500 5.00 5.00 100 100 1000 1000
0.0504 0.0480 0.0483
4.98 4.94 4.98 0.0501 0.0485 0.145 4.88 479 490 98.1 100.0 99.4 940 988 1020 0.0578 0.0592 4.98 5.08 95.9 96.8 978 966 99.8%S.6%
101 96.0 96.6 99.6 98.8 99.6 100 97.0 i3I289 97.6 95.8 98.0 98.1 100.0 99.4 94.0 98.8 102 116 118 99.6 102 95.9 96.8 97.8 96.6
PFBS
Spiked Cone. (ngmiL)
Calc.
Cone. (nghiL)
y. Recovery
0.0499
0.0505
0.0499
0.0456
0.0499
0.0480
4.99
4.94
4.99
4.86
4.99
4.94
0.0499
0.0426
0.0499
00427.
0.0499 0.0441
4.99
4.80
4.99 .' 4.71
4.99
4.76 .
99.9
98.5
9 9 9 100.0
99.9
98.0
999 909
999 973
999 1040
0.0499
0.0563
0.0499
0.0507
4.99
4.89
4.99
4.86
99.9
95.2
99.9
966
999 988
999 975
96.9%S.t%
101 91.3 96.1 98.9 97.7 98.9 85.3 85.5 88.3 96.1 94.3 95.3 98.6 100 98.1 91.0 97.4 104 113 102 97.9 97.3 95.3 96.7 98.9 97.6
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3M ENVIRONMENTAL LABORATORY REPORT NO. E06-0199
(1) All results and average values listed to three significant figures according to EPA rounding rules. %RSD values given to two significant figures. Due to rounding, values may vary slightly from those in the raw data.
(2) Low end o f the calibration curve disabled for PFOS and PFOA due to solvent blank contamination. Recovered LCS concentrations were below the established LOG and are not reported.
(3) High recovery due to instrum ent carryover from the previous Section o f a contaminated methanol blank. Recovery excluded fi um average and %RSD calculations. (4) Recovery was outside the method acceptance criteria o f 10Q25%; however, the recovery was included in the calculation o f the overall average and %RSD. (5) Recovery was outside the method acceptance criteria o f 10025%; the recovery value was not included in the calculation o f the overall average and %RSD as it w asdearty a statistical
outlier. The 5 ppb, 100 ppb, and 1000 ppb LCSs are more representative o f the sa m p * concentrations for the results reported in this subreport. Impact to data quality objectives is m inim al.
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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 .8 4 = 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.
m.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 10011% (two significant
figures) for these results. For PFOS, PFHS, and PFBS, the analytical method uncertainty is 10016%
10Q5.8%, and 1008.8%, respectively. It should be emphasized that the analytical method
uncertainty descnbed above only applies to the method and the procedures performed within
Additional quality control samples specific to the sample matrix, in the form of field matrix spikes and
lab matnx spikes, demonstrate that the individual sam ple results are accurate to within 100+30% the
targeted data quality objectives.
'
3.8 Field Matrix Spikes (FMS)
FMS Recovery = (Sam ple C oncentration o f FMS - Average C oncentration: Field Sample & Field Sample Dup )
SSDpiikkea CCoonnccftennttrraattnonri
^00%
3.9 Lab Matrix Spikes (LMS)
The data tables below summarize the sample results, field matrix snik* r ^ n sample duplicate.
_____ 4nfy
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3M ENVIRONMENTAL LABORA TORY REPORT NO E06-0199
BPP01 The endogenous concentration for BPP01 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 for the 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 10030% 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 least twice tne 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 10030% 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 100+30% 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 analytes, 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 10030% 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 o f 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
3M ENVIRONMENTAL LABORATORY REPORT NO. E06-0199
Table 7. ,1,BPP01 Results.
PFOA
PFOS
PFHS
PFBS
3M UM SID
Description
E06-0199-055 DAL SWS BPP01 0 060413 E06-0199-056 DAL SWS BPP01 DB 060413 E06-0199-057 DAL SWS BPP01 LS 060413 E06-0199-058 DAL SWS BPP01 MS 060413 E06-0199-059 DAL SWS BPP01 HS 060413 ... LMS-060425-1 DAL SW S BPP01 0 060413 500ppb LMS Average C oncentration (ngtmL) V*RPD
Cone. (ngtnL)
% Recovery
293 NA 307 NA 292 ,J'NR 328 ,2lNR. 361 i` iNR. 698 79.6
300X4.7%
Cone.
% Recovery
423 NA 380 NA 330 NR 484 mNR 365 NR 704 '" 60.6 `
'">402
Cone. (ngtnL)
% Recovery
53.3 NA
54.3 NA
53.4 niNR
66.6
NR
136 82.2
485 86.2
53.81.r/,
Cone. (ngfmL)
% Recovery
6.98 NA
7.17
NA
7.44 NR
18.8 117
93.8
86.8
444 87.5
7.00x2.7%
NA= Not Applicable.
(1) Table displays rounded values for a ll concentrations and percent recovery values (3 significant figures), %RPD values (2 significant figures). Recovery and RPD values may vary
sNghtty from the values in the raw data. A l samples and associated FMSs were diluted 1:50 in A5TM Type I w ater prior to extraction.' LMS was diluted 1:100 prior to extraction.
(2) NR=Not reportable. FMS level not appropriate for the given matrix. The endogenous sample concentration w as at least hwce spike level.
~
(3) LMS recovery outside of method acceptance criteria of 10030%.
..
(4) PFOS sample results should be considered estim ated minimums onty Sample'matrix specific QC did not meet method criteria. The analytical sample accuracy is arbitrarily
estim ated to w ithin an order of magnitude. %RPD values not reported.
p. 13
PAGE 13 OF 21
p. 14
</)
00
3M ENVIRONMENTAL LABORATORY REPORTNO. 06-0} 99
Table 8. ,1|BPP02 Results.
M U M S ID
Description
E06-0199-060 DAL SWS BPP02 0 060413 E06-0199-061 DAL SW S BPP02 DB 060413 E06-0199-062 DAL SW S BPP02 LS 060413 E06-0199-063 DAL SW S BPP02 MS 060413 E06-0199-064 DAL SWS BPP02 HS 060413 LMS-060425-2 DAL SW S BPP02 0 060413 250ppb Average Concentration (ng/mL) %RPD
PFOA
Cone. (ngfolL)
%
Recovery
206 NA 219 NA 234 |2,NR 220 NR 314 102 400 75.0
212tS.1%
PFOS
Cone. (n & n L )
% Recovery
295 NA 314 NA 388 niNR 346 NR 437 *N R 454 m59.8
m>304
PFHS
Cone. (ngAnL)
% Recovery
382 NA 39.8 NA 4 2 3 WNR 48.0 niNR 134 95.0 256 86.8
39.04.1%
PF
Cone. (ngfaiL)
% Recovery
4.6 NA
4 72
NA
5.9 NR
144 97.5
102 97.5
223 87.4
4.66*2.6%
NA=Not Applicable. (1) Table displays rounded values *br a# conoentratinns and percent recovery values (3 significant figures), %RPD values (2 significant figures). Recovery and RPD values may
vary slightly from the values in the raw data. A l samples and associated QC were diluted 1:50 in ASTM Tyjxs I water prior to extraction. (2) NR=Not reportable. FMS level not appropriate fo r the given matrix. Endogenous concentration was at least twice spike level. (3) LMS recovery outside o f me*hod acceptance criteria o f 100*30% (4) PFOS sam ple results should be considered estim ated mirwnums onk/. Sample m atrix specific QC dirt not meet method criteria. The analytical sample accuracy is arbitrarily
estim ated to w ithin an order o f magnitude. %RPD values not reported
PAGE 14 OF 21
3M ENVIRONMENTAL LABORATORY REPORT NO. E06-0199
Table 9. BPP03 Results.
PFOA
PFOS
PFHS
PFBS
3M UM SID
Description .
Cone. (ngfaiL)
%
Recovery
Cone. (ngAnL)
% Recovery
Cone. (ngAnL)
% Recovery
Cone. (ngAnL)
% Recovery
E06-0199-065 DAL SWS BPP03 0 060413
219 NA 272 NA 39.1 NA 4.69 NA
E06-0199-066 DAL SWS BPP03 DB 060413
214 NA 256 NA 40.1 NA 5.05 NA
E06-0199-067 DAL SWS BPP03 LS 060413
211
CINR
258
' ''NR
40.2
niNR
5.76
" NR
E06-0199-068 DAL SWS BPP03 MS 060413
226 NR 255 NR 50.0 " Vjr 15.0
101
E06-0199-069 DAL SWS BPP03 HS 060413
324 106 315 NR 143 103 139 i3|134
LMS-060425-3 DAL SWS BPP03 0 060413 250ppb LMS
401
73.8
416 ,4|60.8 262
89.0
230
90.2
Average Concentration (noAnU %RPO
216 z r /,
*>264
39.6*2.5%
4.8717.4%
NA=Not Applicable. (1) Table displays rounded values for all concentrations and percent recovery values (3 significant figures), %RPD values (2 significant figures). Recovery and RPD values may vary slightly from the values in the raw data. A l sam ples and associated QC were diluted 1:50 in ASTM Type I w ater prior to extraction. (2) N R -N ot reportable. FMS level not appropriate for the given matrix. Endogenous concentration was at least twice spike level.
(3) FMS recoveries outside method acceptance criteria o f 10Qt30%.
(4) IM S recovery outside o f method acceptance criteria o f 10030%.
r^
.
(5) PFOS sample results should be considered estim ated mmimums only. Sample m atrix specific QC did not meet method criteria. The analytical sam ple accuracy is arbitrarily
estim ated to w ithin an order o f magnitude. %RPD values not reported.
p. 15
PAGE 15 OF 21
3M ENVIRONMENTAL LABORATORY REPORT NO. 06-0199
Table 10. (1,BPWell results.
M U M S ID
Description
PFOA
Cone. (ngtoL)
% Recovery
PFOS
Cone. (ng/mL)
% Recovery
PFHS
1
Cone. |
%
Ing/mL) : R ecovery
PFBS
Cone. (nofaL)
% Recovery
E06-0199-070
DAL GWS BPWELL 0 060413
774 NA 1460 NA 145 NA 17.2 NA
E06-0199-071
DAL GWS BPWELL DB 060413
779 NA 1170 NA 145 NA |7.6 NA
E06-0199-072
DAL GWS BPWELL LS 060413
723 mNR 960 ,2)n r
152 WNR 26.9 95.1
E06-0199-073
DAL GWS BPWELL MS 060413
821
b,NR
1020
*N R
244 NR
122
105
|3|E06-0199-074 DAL GWS BPWELL HS 060413
1020
IS24.4
1200
|6|n m r
375
IS|23.0
286
IS)26.9
|4|E06-0199-074 DAL GWS BPWELL HS 060413
987
|5|21.0
1320
ff|NMR
348
<S120.3
254
IS23.7
LMS-060425-4
DAL GWS BPWELL 0 060413 1000ppb LMS
1630
85.4
1450
|7,13.5
1080
G3 5
988
97.2
Average Concentration (ngAnU %RPD auic.
">776
"> f.1 2 u
">145
1--7--.-4-t-2--.-3--%-------------
(1) ^b ie d te p lB ys rounded values for all concentrations and percent recovery values (3 significant figures), %RPD values (2 significant fiqures). Recovery and RPD values may
^ r y sgh% from the values m he raw data. The sam ple, sam ple duplicate, low FMS, and mid FMS were diluted 1.50 in ASTM Type I w ater prior to extrectten. The high
FMS and 1000 ppb LMS were diluted 1:500 prior to extraction.
(2) NR=Nt reportable. FMS level not appropriate far the given matrix. Endogenous concentration was at toast twice spike level
v
(3) FMS extracted on 4-21-2006 w ith the samples.
(4) FMS re-extracted on 4-25-0006.
(5) FMS recovery outside o f method acceptance criteria o f 10030%. (6) NMR = No measurable recovery.
(7) LMS recovery outside method acceptance criteria o f 10030%. (8)
Pj -? A .'.|PFOlS' a^ F?FH .Sampie^ SUt? shoutd * * " nadered estimated minimums only. Field m atrix spikes did not meet method criteria. The analytical sample accuracy is arbftranty estim ated to within an order o f magnitude. %RPD values not reported.
p. 16
PAGE 16 OF 21
p. 17
3M ENVIRONMENTAL LABORATORY REPORT NO E06-0199
5 Conclusion
, .
ts ' - '-
' - K ; ' ; * ~- t
Sample matrix QC samples for the four samples reported herein did not meet method acceptance
criteria of 10030% for PFOS. Therefore, the values listed in Table 1 and Tables 7-10 for PFOS
should be considered estimated minim urns. The sample analytical accuracy is arbitrarily
estimated to be within an order of magnitude. Furthermethod development is needed for this
matrix as the QC results demonstrated that unknown matrix components preclude accurate analysis
with the method as performed here. Field matrix spikes yielding recoveries within 10030%
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 for these analytes was
presented in T a b le l. PFOA and PFHS results for BPWeH should also be considered estimated
minimums with a sample analytical accuracy within an order o f magnitude as no acceptable
field matrix spikes recoveries were produced. - ,
'
6 Data / Sample Retention
` V :_
"
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
7 Signatures
3M ENVIRONMENTAL LABORATORY REPORT NO. E06-0199
L s Michelle D. Malinsky, Ph D .^M TechnicaMjeao
'1 /
Kent R. Lindstrom,'3M Technical Reviewer
Date
William K. Reagen, Ph.D., Environmental Laboratory Management
Date
The 3M project.
Environmental
Laboratory's
Quality
Assurance
Unit
has
audited
the
data
and
report
for
this
Date
3M CONFIDENT!.
p. 19
3M ENVIRONMENTAL LABORATORY REPORT NO. 06-0199
8 Attachments
8.1 Method Blank/LOQ Area Count Comparison.
Table 11. Method Blank/LOQ Area Count Comparison: April 21, 2006.
Analytical Run: AofU 21.2006
Datafile
Sanale Description Sample Name
PFOA
Area Counts
PFOS
PFHS
PFBS
Method Blanks Prepared with the Extracted Curve
s060421a025 $060421a026
Method Blank-1 Method Blank-2
MB-060410-1 MB-060410-2
s060421a027
Method Blank-3
M B -060410-3
s060421a028
Method Blank-4
M B -060410-4
$060421a029
Method Blank-5
MB-060410-5
S060421a030
Method Blank-6
MB-060410-6
s060421a031
Method Blank-7
M B -060410-7
s 0 6 0 4 2 la 0 3 2
Method Blank-6
M B -060410-8
Method Blanks Prepared with die Extracted Samples
s060421a045
Method Blank-1
MB-060421-1
s060421a046
Method Blank-2
M B -060421-2
S060421a047
Method Blank-3
MB-060421-3
s060421a048
Method Blank-4
MB-060421-4
s060421a049
Method Blank-5
MB-060421-5
s060421a050
Method Blank-6
MB-060421-6
s060421a051
Method Blank-7
MB-060421-7
S060421a052
Method Blank-8
M B -060421-8
55982 18376 16127 22714 21587 25928 21060 16383
12933 12809 13875 22242 19675 17774 13843 14073
3413 1082 1718 1116 792 4338 2143 1776
1591 668 1970 639 1686 2077 2436 1660
1437 1446 2228 2053 1762 1568 1084 1492
PI121128 '"128379 '"66834 '"42902 '"33923 '"13105
6059 5570
2760 2001 2336 1305 2109 5711 3561 4235
277 715 595 1052 826 2071 *19419 450
Area Counts of the LOQ standard
163373
14600
13176
25766
Area Counts of the LOQ standard*0.5
81686.5
7300
6588
12883
Concentration of LOQ standard (ng/mL)
0.0500
0.0999
0.025
0.025
(1) Method blanks injected im m ediately after a highly contaminated solvent blank. Carryover present. Values excluded
when establishing the LOQ fo r PFHS.
(2) Method blank determ ined to be a statistical outlier at the 99% confidence level using Dixon's Q-test. Value excluded when establishing the LOQ fo r PFBS.
PAGE 19 OF 21
p. 20
3MENVIRONMENTAL LABORATORY REPORT NO E06-0199
Table 12. Method Blank/LOQ Area Count Comparison:? April 24, 2006.
Analytical Run: April 24, 2006 '
Datafile
Sample Description Sample Name
PFOA
Method Blanks Pnmeted with the Extracted Curve
s060424a025
M ethod Blank-1
MB-060410-1
">36625
s060424a026
M ethod B)ank-2
MB-060410-2
">42239
s060424a027
Method Blank-3
M B -060410-3
25302
S060424a028
Method Blank-4
M B -060410-4
22151
s060424a029
Method Blank-5
M B -060410-5
30401
s060424a030
Method Biank-6
MB-060410-6
17458
s060424aU31
M ethod Biank-7
M B -060410-7
23 0/4
$060424a032
M ethod Blank-3
M B -060410-8
22049
Method Blanks Prepared with (he Extracted Laboratory Matrix Spikes
S060424a090
Method Biank-1
MB-3S0425-1 | 30448 '
s060424a091 S060424a092
Method Blank-2 Method Blank-3
M B -060425-2 MB-060425-3
15006 11262
s060424at)93
Method Blank-4
MB-060425-4 ' 11867
s060424a094
Method Btank-5
MB-060425-5 ; 16236
s060424a09fi
Method Blank-6
M B -060425-6
15924
s060424a096
Method Blank-7
MB-OS04.75-7
22750
s060424a097
M ethod Blank-6
A rea C oun ts o f th e LO Q standard
A rea C oun ts o f th e LOQ standardD .8
C o nce ntra tion o f LOQ stan dard Ino/m U
M B-06W 25-6
1 1
j ________________ L
192-: 36060 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 13516 0,025
! I !
d ) Value excluded for the LOQ determ ination for the given set. Area counts are very dose to orte-haif the LOO value Prior
w d l a to w L O Q ^ demonstrated area
betaw
25 ppt standard. LMSs analyzed on this day are
PAGE 20 OF 21
3M ENVIRONMENTAL LABORATORY REPORT NO. E06-0199
8.2 Solvent Blank/LOQ Comparison.
Table 13. Area Counts o f Solvent Blank.
! A n a Counts
Fila
Vial Position ' PFOA ; PROS
PFHS
s060421a001 s060421a002 s060421a003 S060421a009 s060421a010 s060421a023 s060421a024 s060421a035 s060421aQ37 S060421a042 $060421a044 s060421a055 S060421a057 s060421a068 s060421a070 s060421a081 s060421a083 s060421a094 s060421a096 s060421a107
91 70233
91 16249
91 18222
91 48287
92 (1|84762
92 48308 ..
92 *" 84666
93 ">162166
93 .
23806 .
93 15939
94 49169 .
4 1268JS
94 47071.
95 53698
95 74125
95 62139
95 68329
96 76799
96 .
77269.
97 14824
3067 2196 .1642 4524 . 5006 . ,4192 . . -.5317. ">283547 . .">8904 2135
. 1141 3382 2525
. 5907 2124 3139 4192 3358 1166
. .
,
,
1853 18511 . 567 1505 2424 4524 4738 '" 52950 2706 1693 '" 274^54 '"3 2 8 8 4 1 "'2 5 7 9 4 6 5237 6588 3945 3951 3512 3905
852
, ,
s060421a109 s060421a120 s060421a122 s060421a127
97
19120 ,
1763
1499
,
97
9918
1028
, .1024
98 24599
1589
2321
98 37573 1305
6127
s060421a129 s060421a135
99
18673
' 110
99 31743 1944
1909 1472
LOQ Standard
163373
14600
13176
Vj'LO Q Standard
81687
7300
6588
(1) Area counts of the solvent blank were greater than V4*the LOQ standard area counts.
PFBS
192 563 471 , 447 889 6609 7007 "> f1 5 8 2 2 3 5 7 ... 1823 1 1 1 8 ,. 547 946 1137 975 1225 1149 10 54'1173 335 . 1289 698 3275 2190 937 632 25766 12883
, .
.
PAGE 21 OF21
