Document OEL0Qx1ZDNq9Kd9mVgdmYGxve
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-frk& S - 368 !
- 3M ENVIRONMENTAL LABORA TORY 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. 06-019 9
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
PO Box 3331 Saint Paul, MN 55133-3331
Phone: (651) 778-5150 Fax: (651) 778-7203
The testing reported herein meet the requirements of ISO/IEC 17025-1999 "General Requirements fo r the Competence of Testing and Calibration Laboratories", In accordance with the A2LA Certificate #2052-01. Testing that complies with this International Standard also operate in accordance with ISO 9001/ISO 9002 (1994).
Certificate #2052-01
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3M ENVIRONMENTAL LABORATORY REPORT NO. E06-0199
3M En viro n m en tal Laboratory 3M Environmental Laboratory Manager: William K. Reageri, Ph.D. 3M Technical Lead: Michelle Malinsky, Ph D. Report Author: M ichelle Malinsky, Ph D.
Analytical Subreport E06-0199
Surface Water Samples BPP01, BPP02, and BPP03; Ground Water Sample BPWell
Decatur Offerte Sampling Event Report Date: M ay 1, 2006
1 Introductiort/Summary
The 3M Environmental Laboratory extracted and analyzed ground water and surface w ater samples collected by W eston Solutions personnel on April 12 and 13: 2006 Tear the 3M Decatur facility. Sam ples were returned to the 3M Environments! laboratory for analysis of perfluorooctanoate (PFO A), perfluorooctane sulfonate (P F O S ), perfluorohexane sulfonate (P F H S ) and perfluorobutane sulfonate (P F B S ) under laboratory project number E06-0199 using modified 3M Environmental Laboratory Method E T S 8-154.1 "Determination of Perfiuorinated Adds, Alcohols, Amides, and Sulfonates in W ater by Solid Ph ase Extraction and High Performance Liquid Chromatography/Mass Spectrom etry.
P e r the dient's request, an initial subreport is being issued for the following four sample locations only: DAl S W S BPP01 . DAL S W S BPP02 DAL SW S BPP03 . DAL. G W S B P W E L L
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 sam ples collected under E06-0199.
T he 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, s third mid-level field sp,ke w as prepared. Each empty container w as marked with a "fill to here" line which corresponded to a final volume of 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 wili 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 with the A2LA Certificate #2052-01. Testing that complies with this International Standard aiso operate in accordance with ISO
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3MENVIRONMENTAL LABORATORY REPORT NO. E06-0199
Sam ples w ere initially extracted and analyzed on April 19, 2006. Sam ples w ere 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 sam ples prepared and ' analyzed with the samples will be reported and discussed elsewhere in this report. All samples were diluted 1:50 in A ST M Type I w ater prior to extraction.
Table 1. Sam p le Results Sum m ary. -
,
.
3M U M SIO E06-0199-055 E06-0199-056
E06-Q199-060 E06-0199-061
E06-0199-065 E06-O199-066
E06-0199470 E06-O199-071
Sample Oescription
n PFOA Concentration
(ng/m L)
<*PFOS Concentration
(ng/m L)
O AL S W S BPP0 1 0 060413 D A L S W S BPP0 1 D B 060413
Avprge
293 307 300
>423 >380 >402
%RPD Sample/Sample Dup DAL S W S BPP0 2 0 060413 . , D A L S W S BPP0 2 D B 060413
" Average %RPO Sample/Sample D trp, DAL S W S BPP0 3 0060413 D AL S W S B PP0 3 D B 060413
A ve rag e %RPD SamplelSample Dup D AL G W S B P W E L L 0 060413 D AL G W S B P W E L L D B 060413
A vw age %RPD Sampte/Sampie Dup \
' 4-7 '
206 . 219
212
6-1 , 219 214 -
216 2.3
>774 >779
" >776 NA
,
NA >295 >314 >304
NA >272 >256 >264
NA >1460 ' >1170 >1320
NA
n PFHS Concentration
(ng/m L)
53.3, 54.3 53,8
1.8 38.2 39.8 39.0 ' 4.1 39.1 40.1 39. . 2.5 >145 ' >145 >145 NA
PFBS C on cen tratio n
(ng/m L)
6.98 717 7.08
2.7 4.30 4.72 4.66 26 4.69 5.05 4.87 7.4 172 17.6 17.4 23
(1) The analytical method uncertainty for PFO A , P F H S , and P F B S was 10O11%, 10Q5.8%, and 1008.8%,
respectively based on method accuracy arid precision. Se^ Sectio n 3 7 for additional explanation. The limit of
quantitation (LO Q ) for these samples only w as 2.50 ng/mL (PFO A ) and 1.25 ng/mL (P F H S and P F B S ). Results
and average values are rounded to three significant figures according to E P A rounding rules. Percent relative
difference (% R P D ) values are rounded to two significant figures. Because of rounding, values may vary slightly
from those listed'in the raw dhta. '
`_
-
(2) A ll PFOS sample results presented here should be considered estim ated minimum values as quality
control samples (field m atrix spikes and lab m atrix spikes) associated with these fo ur samples did not
dem onstrate adequate m ethod performance The accuracy o f the PFOS results could be within an order
o f m agnitude. %RPD values not calculated. BPWeU results fo r PFOA and PFHS should also be
considered estim ated mmimums as field m atrix spike recoveries did not m eet m ethod acceptance criteria
o f 10030%. The an alytical accuracy o f die PFOA and PFHS estim ated values fo r this sample only could
be within an order o f magnitude. %RPD values not calculated.
.
2 Methods - A nalytical`and Preparatory ' ^ f
:
2.1 Sample Collection
Samples were collected in N algeneTM (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. EOS-0199
four analytes of interest (PFO A , P F O S , P r H S and P F S S ). Collected sample bottles w ere received at the laboratory at ambient conditions on April 19, 2006. Table ?. below details the sam ples collected and spikes added to each bottle
Table 2. Sam ple C ollection and Spike information.
3M U M S ID *
W eston Sample Description
3M So ftie Number
E06-0199055 E06-C199-056 E0S-0199-057 E06-193-058 E06-0199-059
D AL S W S BFP01 0 060413 D.AL S W S BPP01 D B '360413 D AL S W S B P P ?1 L S C412 DAL S W S B P P 0 1 M S 060-113 D AL S W S BPP01 H S 060413
109 110 444
!'2 113
E06-0199-060 E06-0199-061 E06-0199-062 E06-0199-063 E06-0199-064
D AL S W S BPP0 2 0 060413 D A L S W S B PP 0 2 D B 060413 D AL S W S B PP 0 2 L S 060413 D A L S W S BPP0 2 M S 060413 DAL S W S B PP 0 2 H S 060413
V9 120 121 122 123
E06-0199-065 E06-0199-066 E06-0199-067 E06-0199-068 E06-0199-069
DAL S W S BPP0 3 0 C60413 D AL S W S BPP0 3 D B 060413 D A L S W S BPP 0 3 L S 060413 D A L S W S BPP 0 3 M S 060413 D AL S W S BPP0 3 H S 060413
114 115 M6 117 113
E06-0199-070
D AL G W S B P W E L L 0 060412
72
E06-0199-071
DAL G W S BPV LL D B 060413
73
E06-0199-072
D AL G W S B P W E L L L S 060413
74
E06-0199-073
D AL G W S B P W E L L M S 060413
75
E06-0199-074
D AL G W S B P W E L L K S 050413
DAL = Decatur. A L
S W S = Surface W ater Sam ple
G W S = Ground W ater Sam ple
0 = Sam ple
O B = Duplicate
L S = Low Spike
M S = Mid Spike
H S = High Spike
*-
B o a r Designation
Sam ple Sample Dup
FM S Low FM SM id FM S High Sam ple Sample Dup FM 3 Low FM SM id FM S High Sam ple Sample Dup FM S Low FM SM id FM S High Sam ple Sample Dup FM S Low FM S Mid FM S High
Nom inal Spike Level Ingim L)
NA NA 1.0 10 100 NA NA 1.0 10 100 NA NA 1.0 10 100 NA NA 10 100 1000
G PO Location Comment
FS IA Drainage FS IA Drainage F S IA Drainage F S IA Drainage FS IA Drainage FS IA Drainage FS IA Drainage FS IA Drainage FS IA Drainage FS iA Drainage FS IA Drainage FS IA Drainage FSIA Drainage FS IA Drainage FS IA Drainage
B P Property B P Property B P Property B P Property B P Fruperty
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, Aicohols, Amides, and Sulfonates in W ater by Solid Ph ase Extraction and High Performance Liquid Chromatography/Mass Spectrometry". Briefly, 40 m L of sam ple were loaded onto a pre-conditioned W aters C18 solid phase extraction (S P E ) cartridge (Sep-Pak, 1.0 g, 6 cc) using a vacuum manifold. The loaded S P E 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 m anner cross-validate all the method modifications/deviations from ETS-8-154.1. S e e Section 3.6 for additional information.
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3M ENVIRONMENTAL LABORATORY REPORT NO E06-0199
The samples and sam ple duplicates for BPP0 1 , BPP0 2 , and BPP0 3 w ere initially extracted undiluted
on April 19,2006. Initial analysis of the undiluted sam ples exceeded the upper limit of quantiation (25
ng/mL nominal) for P F O A and P F O S . Likewise, the sam ple and sample duplicate for B P W E L L were
initially extracted on April 19,2006. The final extracts w ere diluted 1:10 prior to analysis. Analysis of
these diluted extracts also exceeded the upper limit o fquantitation. AJI the samples, sam ple duplicates,
and field matrix spikes were reextracted on April 21,2006. For B P P 0 1 , BPP0 2 , and BPP0 3 , the
samples and associated Q C were diluted 1:50 using A ST M Type I water prior to extraction. For
B P W EL L , the sample, sam ple duplicate,,low spike arid mid spike were diluted 1:50, while the high
spike w as diluted 1:500.
-
. n-
2.3 Analysis
All sample and quality control extracts were analyzed for PFO A , P F O S , P F H S , and P F B S using high performance liquid chromatography/ tandem mass spectrometry (HPLC/M S/M S). Pertinent instrument parameters, the liquid chromatography gradient program, and (he specific m ass transitions analyzed are described in the tables below. .
Table 3. Instrum ent Param eters.
Instrum ent Name Liquid Chromatograph Guard column Analytical column Injection Volume Mass Spectrometer Ion Source Electrode Polarity Software
ETSStan
1
Agilent 1100
. Betasil C18 (2.1 mrn.XI 00 mm), 5 um
Belasi C18 (2.1 mm X 100 mm). 5 um
5 ul
Applied Biosystems API 4000
' Turbo Spray
' Z-sptay
Negative Analyst 1.4.1
Table 4. Liquid Chrom atography G radient Program .
s te p Num ber
0 1 2 3 4 5
Total Time (m in )
0 1.0 14.5 15.5 16.5 20.0
F lo w R a te (jJ J m in )
300 300 300 300 300 300
P ercen t A (2 mM a m m o n iu m acetate)
80.0 80.0 10.0 10.0 80.0 80.0
P e rc e n tB (M e th a n o l)
20.0 20.0 90.0 90.0 20.0 20.0
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3M ENVIRONMENTAL LABORATORY REPORT NO. E06-0199
T a b le s . M ass Transitions.
. Analyte |,|P F B S " 'P F H S ("P F O S
"'P F O A
M ass Transition 01/Q 3
Owe// Tar, (msec)
299/80
125
299/99
125
399/80
125
, 399/99
125
499/130
125
499/99
125
49980
- 125
413/369
; 125
413/219
125
413/169
125
(1) The iiidiwidoal transitions were sunimed to produce a Total ra.'i chrom alograirf (T 1C). T lie TIC s were used for quantitation.
3 Data Analysis
3.1 Calibration
Calibration standards were prepared by spiking known amounts of stock solutions containing the target analytes into 40 rrtL of ASTlifi type I water. Each spiked water standard w as then extracted in the same manner a s the, collected samples. A total of twelve spiked standards ranging from 0.025 ng/mL to 25
ng/mL. (nominal) were prepared. A quadratic, 1lx weighted, calibration curve w as used to fit the data for each analyts. The data 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) w ere greater than 0.999 for all analytes.
3.2 Limit of Quantitation. (LOQ)
The LO Q for this analysis, as defined >n ETS-8-154.1, is the 'owest 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 LO Qs
for PFO A , P F Q S , P F H S , and P F S S were 0.050C ng/mL, 0.0999 ng/mL, 0.0250 ng/mL, and 0.0250
ng/mL, respectively. Note: these LO Q values have not been corrected for sample specific dilution
factors. A rea count comparison for the method blanks and the lowest calibration standard will be
provided in Section 3.5.1.
.
3.3 System Suitability
Replicate injectk>ns 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 % relativ; standard deviation (R SD ) for peak area and less than 2 % R S D for retention time for both opening and closing system suitability injections.
3.4 Continuing Calibration
.
During the course of the analytical sequence, several continuing calibration verification samples
(C C V s) w ere analyzed to confirm that the instrument response and the initial calibration curve were still
in control. O ne P F O S C C V (139%) arid one P F H S C C V (153%) exceeded method acceptance criteria
of 10025% for accuracy. Both of these non-ccmpliant C C Vs 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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3MENVIRONMENTAL 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 sam ple related Q C 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/tnp blanks. Each blank type is described below.
'
35.1 Method Blanks
Several method blanks were prepared by loading 40 mL of A ST M Type f water onto a C18 S P E cartridge and eluting with 5 m L 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, S P E cartridges, etc.) The calibration curve was
sParate day as t o samples. (Calibration standards: April 10, 2006; diluted samplesApril 21,2006). The method blanks prepared with the calibration standards as well as with the samDles were both analyzed during the April 21,2006 analysis. Additional lab matrix spikes were prepared and
l7 aJ f parate 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
ofth!sreportUnt C mpariSOns t0 the L0 Q standard are P ^ d e d in t o Attachments section at the end
3.5.2 Solvent Blanks
Several methanol solvent blanks w ere analyzed to assess system contamination and/or instrument
" 7 ver^ or Apdi21' 2006 analysis, three separate vials of methanol solvent blanks were
aVld Pr ducd araa counts of t o target anaiytes greater than one-half those of the LO Q ! f rS S - . A met^ fd deviation has been issued. The solvent blank area count comparison for the April 21, ,S pr vided ,n t o Attachments section at the end of this report. For the lab matrix s p i t e d
on A P ^ 24' ':006' on|y the initial solvent blames injected before the opening system ^
" " e*b" Kd
3.5.3 Fietd/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 m L of A ST M Type I water, sealed and s h ip ^ t ^ i m i
2 2 2 2 J n9 * * em piy containers ^ t o Wank serves as anadditional mettod blank
1 7 S! 0ra9f conditions and/or holding time issues that the sam ples m ay experience
Results of the tnp blank analyses will te provided in the 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 no/mL
an aiy2 ! ^
da* - t o h . were extraded and a n a ly S S e o S S m L
and 5 0 ng/mL L C S s were prepared by spik.ng known amounts of the analytes into 40 mL of A ST M
^ concentration. Tbe spiked water s a rn ie s i^ r e t ^ S e ib id ^ a n d anslj^ed in the sam e manner a s the samples. For the 100 ng/mL and 1000 ng/mL L C S s taraet
2 * 5 * Type 1 ^ to ^
t o final d ^ c S S f i S . An
aliquot o fth e L C S w as then diluted 1:50 or 1:500 with A S TM T yp e I w a te r prior to extraction in th e
= ^ ^ ' IUted f ' t o '65 This technique was done to demonstrate that the dilution .
procedure used for the sam ples w as able to produce accurate results. Analysis of radicate LCSs at
Section
3.77.' 1-T a^bJle
6
L C S results wiH * *
summarizes the LC S recovery
to determine results.
overall
method
uncertainty ^
in In
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3M ENVIRONMENTAL LABORATORY REPORT NO. E06-0199
L C S Percen t R eco very , Calculated Concentration . 1Q ()% Spike Concentration
L C S % R S D = sl andarci.-de tfiatio n L C Sre P 'icales . , o o % average L C S recovery
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3M ENVIRONMENTAL LABORATORY REPORT NO E06-0199
Table 6. *1*Lab`Control Spike Results.
Sample Description
Lab ID
0.05 ppb LC S
LCS-060410-1
0.05 ppb LC S
LCS-060410-2
0.05 ppb LC S
LCS-060410-3
5.0 ppb LC S
LCS-060410-4
5.0 ppb LC S
LCS-060410-5
5.0 ppb LC S
LCS-060410-6
0.05 ppb LC S
LCS-060421 -1
0.05 ppb LC S
LCS-060421-2
0.05 ppb LC S
LCS-060421-3
5.0 ppb LC S
LCS-060421-4
5.0 ppb LC S
LCS-060421-S
5.0 ppb LC S
LCS-060421-6
100 ppb LC S
LCS-060421-7
100 ppb LC S
LCS-060421-8
100 ppb LC S
LCS-060421-9
1000 ppb LC S LCS-060421-10
1000 ppb LC S LCS-060421-11
1000 ppb LC S LCS-060421-12
0.05 ppb LC S
LCS-060425-1
0.05 ppb LC S
LCS-060425-2
5.0 ppb LC S
LCS-060425-3
5.0 ppb LC S
LCS-060425-4
100 ppb LC S
LCS-060425-5
100 ppb LC S
LCS-060425-6
1000 ppb LC S LCS-060425-7
1000 ppb LC S LCS-060425-8
Average `/Recovery j% R SD
PFOA
Spiked Cone. (ngfatL)
Calc. Cone. (n g *n y
/. Recovery
0.0500 0.0500 0.0500
5.00 5.00 5.00 0.0500 0.0500 00500 5.00 5.00 5.00 100.0 1000 100.0 1000 1000 1000 0.0500 0.0500 5.00 5.00 100.0 100.0 1000 1000
<0.0500 <0.0500 0.0517
4.93 4.86 5.30 <0.05 <0.05 0.0514 5.02 4.81 4.82 95.0 99.7 96.9 928 977 1030 0.0689 0.0600 4.91 4.87 953 96.6 977 972 io v /.ia .7 %
|2,NA eiNA 104 986 97.2 106 NA PINA 103 100 96.2 96.4 95.0 99.7 96.9 92.8 97.7 103 t4|138 120 982 97.3 95.3 98.6 97.7 97,2
PFOS
Spiked Cone. (ngltnL)
Calc. Cone. fngfoiL)
% Recovery
0.0500 <0.0999
0.0500- <0.0999
0.0500 <0.0999
5.00
493
5.00
5.01
5.00
5.05
0.0500 <0 0999
0.0500 <0.0999
0.0500 <0.0999
5.00
4.53
5.00
4.34
5.00
4.49
99.9
87.3
99.9
69.2
99.9
88.5
999 855
999 899
999 929
0.0500
0.0631
0.0500
0.152
500
4.79
5.00
4.94
99.9
845
99.9
89.8
999 878
999 849
93.1%10%
PIN A e 'N A |2iNA 98.7 100 101 C1N A raNA i2In a 90.7 869 899 87.4 89.3 886 85.6 90.0 93.0 w 126 15*304 95.9 98.9 84.6 89.9 879 85.0
PFHS
Spiked Cone. (ngtm U
Calc. Cone. fngAnU
% Recovery
0.0500 0.0500 0.0500
5.00 5.00 5.00 0.0500 0.0500 0.0500 5.00 5.00 5.00 100 100 100 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 4.79 490 98.1 100.0 99.4 940 988 1020 00578 0.0592 4.98 5.08 95.9 96.8 978 966 99.S%5.6%
101 96.0 96.6 99.6 98.8 99.6 100 97.0 ,3|289 97.6 95.8 98.0 98.1 1000 99.4 94.0 98.8 102 116 118 99.6 102 95.9 96.8 97.8 96.6
PFBS
Spiked Cone. {ngknU
Calc.
Cone. (n&m Li
% Recovery
0.0499 0.0499 0.0499
4.99 4.99 499 0.0499 0.0499 0.0499 4.99 4.99 4.99 99.9 99.9 99.9 999 999 999 0.0499 0.0499 499 4.99 99.9 99.9 999 999
0.0505 0 0456 0.0480
4.94 4.88 4.94 0.0426 0.0427. 0.0441 4.80 4.71 4.76 98.5 100.0 98.0 909 973 1040 0.0563 0.0507 4.89 4.86 952 96.6 988 975 96.8%5.S%
101 91.3 961 98.9 97.7 98.9 85.3 85.5 68.3 96.1 94.3 95.3 986 100 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 Hsted to three significant figures according to E P A rounding rules. % R S D values given to two significant figures. Due to rounding, values may vary slightly from those in the raw data.
(2) Low end of the calibration curve disabled for P F O S and PFO A due to solvent blank contamination. Recovered LC S concentrations were below the established LOQ and are not reported.
(3) High recovery due to instrument carryover from the previous injection of a contaminated methanol blank. Recovery excluded fiom average and % R S D calculations. (4) Recovery w as outside the method acceptance criteria of 10025%; however, the recovery was included in the calculation of the overall average and % R S D . (5) Recovery was outside the method acceptance criteria of 10025%; the recovery value w as not included in the calculation of the overall average and % R S D as it was dearly a statistical
outlier. The 5 ppb, 100 ppb, and 1000 ppb LC Ss are more representative of the sample concentrations for the results reported in this subreport Impact to data quality objedives is minimal.
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3M ENVIRONMENTAL LABORATORY REPORT NO E06-0199
3.7 Analytical Method Uncertainty
Both the accuracy (percent recovefy) and precision (% R S D ) of the lab control spikes were used to estim ate the overall method's analytical uncertainty for a given analyte. For example, the overall
predSion * * P FO A based " L C S resutts" a s 101%9.7%. The measured precision (% R S D ) 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, LC S 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 .i% -ioo = ii.i% 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 P FO A is given as 10011 % (two significant
i n ^ f L ^ rth^ t ^ ! U0,t! 0/For P F 0 S ' P F H S ' and P F B S ' * * ana|ytical method uncertainty is 10016% 10Qf_ 8 % ' and 1008-8 /o' respectively. It should be emphasized that the analytical method
" S * - * descnbed above only applies to the method and the procedures performed within
Addfoona! quality control samples specific to the sample matrix, in the form of field matrix spikes and
f J T ^ keS' dm nstrate I*13* individual sam ple results are accurate to within 100+30% 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
M l? e S S rRrtrtd lsappl'^ b,e t0 ^ coHeded matrix. For some locations, a mid-level spike w as also collected. Field matrix spike recovenes within method acceptance criteria of 10030% confirm that unknown ^ p o n e n tsin the sample matrix do not interfere with the extraction and analysis of the
" t* e * F !,d " iatnx spikes wi" b Presented in the next section with the sample data The appropriate spike level for the g6ivaeSnt 5sa0m% p lfethmeaternixd.o9er u * sample concentration to be considered an
F M S Recovery = (Sam ple Concentration of FM S - Average Concentration Field Sam ple & Field Sam ple D up) ..........
Spike Concentrator!
~
*1
3.9 Lab Matrix Spikes (LMS)
s o liS s ^ ffa t
concentrations where nn e of the associated field matrix
E S J T f c * * * * f * * i endogenous co n cen trate, then laboratory matrix spikes (LM S) were
frf !!ere repard by spikin9 a known amount of target analytes into a measured aliquot of the sample matrix. The spiked matrix w as then diluted, if necessary, and extracted in the s a r r ^
m anner as the samples. LM S recoveries within 10030% demonstrated that the analytical method w as appropriate for the given sample matrix only in the absence of an appropriate field matrix S e .
4 Data Summary
^mantndx^ sp?ikeTMrecobveelnWes for the four`Il1ocaStaiomnpsle(BrPePsu0l1ts,' BPP0m2a, tBriPxPs0p3ik,earnedcoBvPeWrieesl,l)anEdaclahbtoarbalteor7y S t e d S S S T 88 COnCentrati n and * * relative P ^ n t difference (R P D ) of the sample and
PAGE 11 OF 21
p. 12
3M ENVIRONMENTAL LABORA TORY REPORT NO. E06-0199
BPP01
The endogenous concentration for BPP01 w as 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 PFO A and P F O S A laboratory matnx spike at 500 ng/mL w as prepared and analyzed. The LM S recovery met method acceptance aiterra of 10030% for P FO A (79.6%), but not for P F O S (60.6%). Therefore, the sam ple results for
P_ r S !LhOU" 08 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 sam ple matrix. F M S and/or LM S recoveries within 10030% for PFO A , P F H S , and P F B S demonstrate that the analytical method is appropriate for the given sample matrix for these analytes.
BPP02
The endogenous concentration for BPP02 w as at least twice the spike concentration for the low spike
y
and mid spike <10
for both P F O A and P F O S as well as the high spike (100 nq/mL)
for P F O S only. A laboratory matrix spike at 250 ng/mL w as prepared and analyzed. The LM S
recovery met method acceptance criteria of 10030% for PFO A (75.0%), but not P F O S (59.8%).
Therefore, the sample results for PFO S should be considered estimated minimums with a
VUith!H an!order ** magnitude as the analytical method has not been * * suitable for the given sam ple matrix. F M S and/or LM S recoveries within
10030 /ofor P FO A , P F H S , and P F B S demonstrate that the analytical method is appropriate for the given sam ple matrix for these analytes.
BPP03
? ^ m <! C^ ? USHCOn<enM ^On/CT B P P 3 W3S at !esst twice * * spike concentration for the low spike
K and mid sp.ke (10 ng/mL) for both P F O A and P F O S as well as the high spike (100 ng/mL) for P F O S only. A laboratory matrix spike at 250 ng/mL w as prepared and analyzed The LM S
recovery met method acceptance criteria of 10Qt30% for P FO A (73.8%), but not P F O S (60.8%)
sa.mple resuttsfor P F 0 S Should be considered estimated minimums with a
^t
accu rac y within an order of magnitude as the analytical method has not been
^ ^ 401,8 suitab,e for the 9lven sam ple matrix. The high level P F B S FM S exceeded
method acceptance criteria of 10030% (134%). However, the P F B S results for this sample are still
10030% because the criteria exceedence was minimal (within 4 % ) and
m'd level F M S and LM S recoveries were excellent. 101% and 90.2%, respectively. High level FM S
* * * 10030% for P F O A and P F H S also demonstrate that the analytical method
is appropnate for the given sample matrix for these two analytes as well.
*
BPW ell
f0r B P W e " w as a{ least
the spike concentration for the low spike
A lth n ^ ih m ^ h T ? ^ P F 0 B ' P H F S ' and P F B S as ^ as be mid spike for PFO A , P F O S , and P F H S Atthough the high level spike (1000 ng/mL) w as an appropriate level for all four analytes the recoveries
3 0 % f0Cal1 analytes' ^ P F 0 S showing no measuring recovery. The high
F ^ ^ aS,, ^ ? XtraCted t0 m e out a P o te ra i preparatory error during the extraction process The
second
P ^ u f e d similar recoveries as the first. A laboratory matrix spike at 1000 ng/mL was
d I u o /qo3^ ' 1116 LM S recovefy met method acceptance criteria of 10030% for PFO A (85 4 % ) " 1 to P F O S (13.5%). T W c , m e
P F 0 S 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 sam ple matrix. Although the LM S produces acceptable recoveries for PFO A and PFH S
S .n ^ l S eJ r SU^ | hOUld h considered estimated minimums as no appropriate
'
S^
T , t Valable- L W 3nd mid l6Vel FM S and LM S recoveries within P F B ,S n 2 . Strate tha the ana|ytical method is appropriate for the given sample matrix
Ss>eee^ittimp^ro\ve^aCrRr U^ AA ,UP^FOO S ,nanndd P F H RSer*OecPornveern^e*s can*be aWcheie"ved. matrixw" 1* * P * TM * t o
PAGE 12 OF 21
3M ENVIRONMENTAL LABORATORY REPORT NO 06-0199
Table 7. ,1,BPP01 Results.
PFOA
PFOS
PFHS
PFBS
3 M U M S ID
D e s c rip tio n
E06-0199-055 DAL S W S BPP01 0 060413
E06-0199-056 E06-0199-057 E06-0199-058 E06-0199-059
DAL S W S BPP01 D B 060413 DAL S W S BPP01 L S 060413 DAL S W S BPP01 M S 060413 DAL S W S BPP01 H S 060413
LMS-060425-1 DAL S W S BPP01 0 060413 SOOppb LM S
A v e n g e C o n c e n tn tio n (n g /m L ) % R P D
C one. (ng A n Q
% R ecovery
293 NA 307 MA 292 ,2,NR 328 |2iNR. 361 '"M R 698 79.6
30C 4. TV.
C one. (n g /m l)
% R ecovery
423 NA 380 NA 330 i2iN R 484 mNR 365 |2|n r 704 |3i60.6
" >402
C one. (n g /m L )
% R ecovery
53.3
NA
54.3
NA
53.4
I2IN R
66.6
(2|n r
136 82.2
485 86.2
53 .fttf.9 S
C one. (n g fin l)
% R ecovery
6.98 7.17 7.44 188 93.6 444
NA NA |2|n r 117 86.8 87.5
7 .0 0 2 .7 %
NA= Not Applicable.
'-
(1) Table displays rounded values for all concentrations and percent recovery values (3 significant figures), % R P D values (2 significant figures). Recovery and R PD values may vary
slightly from the values In the raw data. All samples and associated FM Ssw ere diluted 1 50 in A ST M Type I water prior to extraction: LM S was diluted 1:100 prior to extraction.
(2) NR=Not reportable FM S level not appropriate for the given matrix. The endogenous sample concentration w as at least tvwce spice level.
~
(3) LM S recovery outside of method acceptance criteria of 100+30%.
..
(4) P F O S sample results should be considered estimated minimums only. Sam ple matrix specific Q C did not meet method criteria. The analytical sample accuracy Is arbitrarily estimated to within an order of magnitude. % R P O values not reported.
p. 13
PAGE 13 OF 21
3M ENVIRONMENTAL LABORATORY REPORT NO. E06-0199
Table 8. ,1,BPP02 Results.
PFOA
PFOS
PFHS
PFBS
3 M U M S ID
D e s c rip tio n
E06-0199060 DAL S W S BPP02 0 060413
E06-0199-061 DAL S W S BPP0 2 D B 060413
E06-0199-062 E06-0199063 E06-0199-064
DAL S W S BPP0 2 L S 060413 DAL S W S BPP02 M S 060413 DAL S W S BPP0 2 H S 060413
LMS-060425-2 DAL S W S BPP0 2 0 060413 250ppb
Average C o n c e n tra tio n (n o fm U R P D
C one. (n o tn L )
% R ecovery
206 219 234 220 314 400
NA NA PIN R biN R 102 75.0
2 1 2 t6 .1 %
Cone. (n g to iL )
R e co ve ry
295 NA 314 NA 388 mNR 346 N R 437 " 'NR 454 |3,59.8
'*> 3 0 4
C one. (n o h n U
R ecovery
38.2
NA
39.8
NA
42.3
|2iNR
48.0
NR
134 95.0
256 86.8
3 9 . 4.1 %
Cone. (n g to iL )
R ecovery
4.6 NA
4.72
NA
5.9 N R
14.4
97.5
102 97.5
223 874
4.se2 .6
NA=No1 Applicable.
d i L abte,d^ laf rr,LZ led.Va"Je S 2 >ra# TM lcenl" rtin" s
values (3 significant figures). % R P D values (2 significant figures). Recovery and R PD values may
\ry shghtly trem the values m the raw data. A l cam pier and associated Q C were diluted 1 50 in A STM Ty,ie I water prior to extraction.
(2) NR=Not reportable FM S level not appropriate for the given matrix. Endogenous concentration w as at least twice spike level
(3) LM S recovery outside of method acceptance criteria of lO O t30%
(4)
PFk0 S ^ plC^ SU,tS
^ ixinslriered estimatef) thinimums onk/. Sam ple matrix specific QC did not meet method criteria. The analytical sample accuracy is arbitrarily
estimated to wittwi an order of magnitude. % R P D values not reported.
p. 14
PAGE 14 OF 21
3MENVIRONMENTAL LABORATORY REPORT NO. E06-0199
Table 9. BPP03 Results.
PFOA
PFOS
PFHS
PFBS
3 M U M S ID
D e s c rip tio n
Cone. (n g fo L )
% R ecovery
Cone. (n fm L i
% R ecovery
Cone.
% Cone. % (n a 'm L I
E06-0199-065 DAL S W S BPP0 3 0 060413
E06-0199-066 E06-0199-067 E06-0199-068
DAL S W S BPP0 3 D B 060413 DAL S W S BPP0 3 L S 060413 DAL S W S BPP0 3 M S 060413
E06-0199-069 DAL S W S BPP0 3 H S 060413
LM S-060425-3 DAL S W S BPP0 3 0 060413 250ppb LM S
A verage C o n c e n tratio n ( n o t n U `/.R P D NA=Not Applicahle.
219 NA 214 NA 211 ,aN R 228 " N R 324 108 401 73.8
2 i 6t z r / .
272 NA
256 NA
258 " NR
255
" nr
315 " N R
416 " 60.8
ra>264
39.1
NA
40.1
NA
40.2
" NR
50.0
" NR
143 103
262 69.0
39-ftt2.5%
4.69
NA
5.05
NA
5.76
" NR
15.0 139 230
101 " 134 on?
4.877.4%
( 1)
P! ? 8nl reC0^ ,rl ^ hJes (3
figures), %RPD values (2 significant figures), Recovery and RPD values may
(2)
d l A".6amptes and aEsoaated 0 0 e TM d`M ed 1 5 in ASTM Type I water prior to extraction NR No. reportable. FMS level not appropriate for the given matrix Endogenous concentration was at least twioe spike level
(3) FMS recoveries outside method acceptance criteria of 10O30%
(4) LM S recovery outside of method acceptance criteria of 100i30%
(5)
p. 15
PAGE 15 OF 21
3M ENVIRONMENTAL LABORATORY REPORT NO E06-0199
Table 10. (1,BPWell results.
PFOA
PFOS
PFHS
PFBS
M U M S ID
D e s c rip tio n
Cone. (n g /m L )
% R ecovery
C one. (n g fo tL )
% R ecovery
Cone. (ngA nL)
% R e co v e ry
Cone. (n g /m L )
y. R ecovery
E06-0199-070 E06-0199-071
D AL G W S B P W E L L 0 060413 DAL G W S B P W E L L D B 060413
774
NA 1460 NA
145
NA
17.2
NA
779 NA 1170 NA 145 NA 17.6 NA
E06-0199-072
D AL G W S B P W E L L L S 060413
723 " NR 960 " N R 152 " NR 26.9 95.1
E0 6 O 1 99-073
DAL G W S B P W E L L M S 060413
821
" NR
1020
" nr
244 " NR
122
105
" E06-0199-074 DAL G W S B P W E L L H S 060413
1020
|5124.4
1200
|6iN M R
375
|5|23.0
286
l5|26.9
H,E06-O199074 DAL G W S B P W E L L H S 060413
987
|S|21.0
1320
'''N M R
348
,5)20.3
254
|S|23.7
LMS-060425-4
D AL G W S B P W E L L 0 060413 lOOOppb LM S
1630
85.4
1450
" 13.5
1080
D3.5
m
97.2
Average C o n c e n tra tio n (n o tn U % R P D NA=Not Applicable.
">776
">1320
"> 1 *5
1 7 .4 iZ rA
(1) Table displays rounded values for all concentrations and percent recovery values (3 significant figures), % R P D values (2 significant Squres). Recovery and R PD values may vary slightly from the values in the raw data. The sample, sample duplicate, low CMS, and mid FM S were diluted 1:50 in A S7M Type I water prior to extraction. The high FM S and 1000 ppb LM S were diluted 1:500 prior to extraction.
(2) NR=Not reportable. FM S level not appropriate for the given matrix. Endogenous concentration was at least twice spike level. (3) FM S extracted on 4-21-2006 with the samples. (4) FM S re-extracted on 4-25-0006.
(5) FM S recovery outside of method acceptance criteria of 1DO3G%. (6) NMR = No measurable recovery.
(7) LM S recovery outside method acceptance criteria of 1UQ30%.
(8) PFO A , P F O S , and P F H S sample results shoiid be considered estimated minimums only. Field matrix spikes did not meet m r.thcJ criteria. The analytical sample accuracy is arbitrarily estimated to within an order of magnitude. % R P D values not reported.
p. 16
PAGE 16 OF 21
3M ENVIRONMENTAL LABORATORY REPORT NO. E06-0199
5 Conclusion
Sam ple matrix Q C samples for the four sam ples reported herein did not meet method acceptance
criteria of 10030% for P F O S . Therefore, the values listed in Table 1 and Tables 7-10 fo r PFOS
should be considered estim ated minimums. The sam ple analytical accuracy is arbitrarily
estim ated to b e within an order o f m agnitude. Further method development is needed for this
matnx a s the Q C 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 w as suitable for the given sample matrices for P FO A PFH S
and P F B S for B P P 0 1 , BPP0 2 , and BPP0 3 . 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
m inimums with a sam ple analytical accuracy within an order o f m agnitude as no acceptable
field m atnx spikes recoveries were produced. - .
^
$ Data / Sample Retention
..
Al! remaining sample and associated project data (hardcopy and electronic) will be archived according
to 3M Environmental Laboratory standard operating procedures.
y
7 Signatures
3M ENVIRONMENTAL LABORATORY REPORT NO. 06-0)99
William K. Reagen, Ph.O., Environmental Laboratory Management
Date
The 3M Environmental Laboratory's Qual'tv Assurance Unit has audited the data and report for this project.
Quality Assurance Representative
Date
3M CONFIDENTIAL
PAGE 1BOF21
p. 19
3M ENVIRONMENTAL LABORATORY REPORT NO 06-0)99
8 Attachments
8.1 Method Blank/LOQ Area Count Comparison.
Table 11. Method Blank/LOQ A rea Count Com parison: A pril 21, 2006.
Analytical Run: April 21, 2006
Oataffie
Semple Description Sample Name
i
I ! !
M ethod Blanks Pn
s060421a025
Method Blank-1
MB-060410-1
S060421a026
Method Blank-2
MB-060410-2
s060421a027 S060421a028
Method Blank-3 Method Blank-4
MB-060410-3 MB-060410-4
s060421a029 s060421a030 S060421a031 s060421a032
Method Blank-5 Method Blank-6 Method Blank-7 Method Blank-8
MB-060410-5 MB-060410-6 MB-060410-7 MB-060410-8
M ethod Blanks P nip an d with the Extracted Samples
s060421a04S s060421a046 s060421a047 s060421a048 s060421a049 S060421a050 S060421a051 s060421a052
Method Blank-1 Method Blank-2 Method Blank-3 Method Blank-4 Method Blank-5 Method Blank-6 Method Blank-7 Method Blank-6
MB-060421-1 MB-060421-2 MB-060421-3 MB-060421-4 MB-060421-5 MB-060421-6 MB-060421-7 MB-060421-8
Area Counts of the LOQ standard
Area Counts of the LOQ standard*0.5
Concentration of LOQ standard Ino/m U
when establishing the LOQ lor PF H S .
PFOA
Area Counts
PROS
PFHS
PFBS
55982 18376 16127 22714 21587 25928 21060 16383
3413 1082 1718 1116 792 4338 2143 1776
1591 668 1970 639 1686 2077 2436 1660
2760 2001 2336 1305 2109 5711 3561 4235
12933 12809 13875 22242 19675 17774 13843 14073 163373 81686.5 0.0500
1437
'"121128
277
1446
'" 129379
715
2228
'"66834
595
2053
'"42902
1052
1762
'"33923
826
1568
|1>13106
2071
1084
6059
`"19419
1492
5570
450
14600
13176
25766
7300
6588
12883
0.0999
0.025
0.025
blank. Carryover present. Values excluded
(2) Method blank determined to be a statistical outlier at the 99% confidence level using Dixon's Q-test Value exduded when establishing the LOQ for P F B S .
PAGE 19 OF 21
p. 20
3M ENVIRONMENTAL LABORATORY REPORT NO E06-0199
Table 12. Method Blank/LOQ Area Count Com parison:? April 24, 2006.
I
1 3 I I
A nalytical Run: A p r* 24, 2006
D aune
Sam ple Description Sample Name
PFOA
M ethod Blanks Pre
s060424a25
Method Blank-1
MB-060410-1
(l>36625
s060424a026
Method Blank-2
MB-060410-2
m42239
S060424a027
Method Blank-3
MB-060410-3
25302
s060424a028
Method Blank-4
MB-060410-4
22151
s060424a029
Method Blank-5
MB-060410-5
3041 .
s060424a030
Method Blank-6
MB-060410-6
17458
s060424a031
Method Siank-7
MB-060410-7
23074
s060424a32
Method Blank-8
M B-0604'0-8
22049
M ethod Blanks PreOared with the Extracted Laboratory Matrix Spikes
s060424a090
Method Biank-1
MB-0EC425-1
30448
$060424a091 s060424a092
Method Blank-2 Method Blank-3
MB-060425-2 MB-0O425-3
15006 11262
S060424a093
Method Blank-4
MB-060425-4
11867
S060424a094
Method Blank-5
MB-060425-5
16236
s060424a095
Method Blank-6
MB-0804256
15924
s060424a02C
Method Blank-7
MB-0304.75-7
22750
s060424a097
Method Blank-8
A rea C o un ts of the LO Q standard
A rea C o un ts of the LO Q standard*0.5
C oncentration of LO Q standard Ino/mU
MB-06CK25-8
1923-i 36060 18020 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 3616 4294
1906 2990 1703 6142 2723 5446 4359 1677 27032 13516 0.025
(1) Value excluded tor the LOQ determination tor the given set. Area counts are very dose to one-half the LO G value. Prior
analysis of this extract demonstrated area counts below one-half the 25 ppt standard. LM Ss analyzed on this day are
well above the LOQ.
'
PAGE 20 OF 21
p. 21
3M ENVIRONMENTAL LABORATORY REPORT NO E0&4199
8.2 Solvent Blank/LOQ Comparison.
Table 13. A rea Counts of Solvent Blank.
Area Counts
Fife
Vial Position
PFOA
PROS
PFHS
s060421a001
91 70233 3067
1853
.
s060421a002
91 16249 2196
1851
s060421a003
91
18222
.1642
567
s060421a009
91 . 48287
4524 .
1505
s060421a010
92 '" 84762 5006
2424
s060421a023 s060421a024
92
, 48308.
. .4192
92
H MlBOiaOeOe
; -.5317
4524 4738
s060421a035
93
'" 162166
`" 283647 .
'" 52950
S060421a037
93
23806 .
nl8 9 0 4
2706
S060421a042
93 15939 2135
1693
S060421a044
94 49169 .
'" 274^54
s060421a05S
94
1268p
,1141 .
'" 328841
s060421a057
94
47071.
338? .
`" 257946
s060421a068
95
53698
2525 ,
5237
s060421a070
95
74125
. 5907
6588
s060421a081
95 62139 2124
3945
s060421a063
95 68329 3139
3951
s060421a094
96 76799 4192
3512
s060421a096
96
77269,
3358
3905
s060421a107
97 14824 1166
852
s060421a109
97 19120 1763
1499
s060421a120
97
9918
1028
, 1024
S060421a122
98 24599
1589
2321
S060421a127
98 '
37573
t305
6127
s060421a129
99
18673
' ' 1100
1909
s060421a135
99 31743 1944
1472
LOQ Standard
163373
14600
13176
W L O Q Standard
81687
7300
6588
(1) Area counts ofthe solvent blank w ere greater than '/"the LO Q standard area counts.
PFBS
192 563 471 . 447 889 6609 7007 '" 4 1 5 8 2 2357 , 1823 1118, 547 946 1137 975 1225 1149 1054 v1173 335 . 1289 698 3275 2190 937 632 25766 12883
.
PAGE 21 OF21
