Document 8R4K92bqY4vrZeaZ3a6OJqzdk
3M ENVIRONMENTAL LABORATORY REPORT NO. E08-0363
Final Report
Analysis of PFBA, PFOA, PFBS, PFOS, FBSA, and FOSA in Aqueous Samples from 3M Decatur, Alabama
3M Decatur NPDES Permit Number AL0000205: Quarterly FC Monitoring of Outfall DSN001; 3rd Quarter 2008 Sampling
Laboratory Request Number: E08-0363
Method Requirement: 3M Method ETS-8-154.3
Report Date - July 28,2008
Testing Laboratory
3M EHS Operations 3M Environmental Laboratory
Building 260-5N-17 Maplewood, MN 55144-1000
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
1
I A C C R E D IT E D
Certificate #2052-01
The testing reported herein meet the requirements of ISO/IEC 17025-2005 "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 also operate in accordance with ISO 9001/ISO 9002 (2000).
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3M ENVIRONMENTAL LABORATORY REPORT NO. E08-0363
3M Environmental Laboratory
3M Environmental Laboratory Technical Manager: William K. Reagen, Ph.D. 3M Principal Analytical Investigator and Report Author: Susan Wolf
Analytical Report E08-0363
3M Decatur NPDES Permit Number AL0000205: Quarterly FC Monitoring of Outfall DSN001 ; 3rdQuarter 2008 Sampling
Report Date: July 28,2008
1 Introduction/Summary
The 3M Environmental Laboratory prepared and analyzed outfall samples collected by Enersolv Corporation personnel on July 1, 2008, from 3M Decatur location DSN001. Samples were returned to the 3M Environmental Laboratory for analysis of Perfluorobutanoic acid (PFBA), Perfluorooctanoic acid (PFOA), Perfluorobutane sulfonate (PFBS), Perfluorooctane sulfonate (PFOS), Perfluorobutanesulfonylamide (FBSA) and Perfluorooctanesulfonylamide (FOSA) under laboratory project number E08-0363.
The 3M Environmental Laboratory prepared sample containers for one sampling location. The sample set consisted of a field sample, field sample duplicate, low field spike, mid field spike, and high field spike. Each empty container was marked with a "fill to here" line that corresponded to a final volume of 200 mL. Containers reserved for field matrix spikes were fortified with an appropriate matrix spike solution containing all analytes prior to being sent to the field for sample collection.
Samples were prepared using ETS-8-154.3 "Determination of Perfluorinated Acids, Alcohols, Amides, and Sulfonates in Water by Solid Phase Extraction and High Performance Liquid Chromatography/Mass Spectrometry" on July 7, 008 and analyzed on July 8 and 15, 2008.
Table 1 summarizes the sample results using the analytical method identified above. All results for quality control samples prepared and analyzed with the samples will be reported and discussed elsewhere in this report.
illL
&C C R E D ITED I
The testing reported herein meet the requirements of ISO/IEC 17025-2005 "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 also operate in accordance with ISO 9001/ISO 9002 (2000).
Certificate #2052-01
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3M ENVIRONMENTAL LABORATORY REPORT NO. E08-0363
Table 1. Sample Results Summary.
3M LIMS ID E08-0363-001 E08-0363-002
Sample Description
PFBA"1 Concentration
(n g /m L )
PFOA"' Concentration
(n g /m L )
PFBS"' Concentration
(n g /m L )
DSN001, Sample DSN001 Sample Duplicate
Average %RPD Sample/Sample Dup
9.67 9.67 9.67 0.0
11.5 10.9 11.2 5.4
90.8 90.2 90.5 0.66
3M LIMS ID
Sample Description
PFOS"' Concentration
(n g /m L )
FBSA"' C o n c e n tra tio n
(n g /m L )
FO SA (2) C o n c e n tra tio n
(n g /m L )
E08-0363-001 DSN001, Sample
37.4
92.6
9.51
E08-0363-002 DSN001 Sample Duplicate
37.9
91.9
10.2
Average
37.7
92.3
9 .8 6 (3)
%RPD Sample/Sample Dup
1.3
0.76
7.0
(1) Samples were extracted by solid-phase extraction using method ETS-8-154.3 on July 7, 2008 and analyzed on July 8,2008.
The analytical method uncertainties associated with the reported results are as follows: PFBA 100% 15%, PFOA100%
10%, PFBS 100% 6.6%, PFOS 100% 6.3%, and FBSA 100% 12%.
(2) Samples were extracted by solid-phase extraction using method ETS-8-154.3 on July 7, 2008 and analyzed on July 15, 2008.
The analytical method uncertainty associated with the reported results for FOSA is 100% 26%.
(3) The analytical uncertainty for FOSA has been adjusted for matrix spike recoveries to 100% 32%. See section 4 of the
report for additional information.
2 Methods - Analytical and Preparatory
2.1 Methods
Analysis was completed following 3M Environmental Laboratory method ETS-8-154.3 "Determination of Perfluorinated Acids, Alcohols, Amides, and Sulfonates in Water by Solid Phase Extraction and High Performance Liquid Chromatography/Mass Spectrometry".
2.2 Sample Collection
Samples were collected in NalgeneTM (high-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 analytes of interest. Collected sample bottles were returned to the laboratory at ambient conditions on July 2, 2008.
2.3 Sample Preparation
All samples, calibration standards, and associated quality control samples were extracted using ETS-8154.3. Briefly, 40 mL of sample were loaded onto a pre-conditioned 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).
2.4 Analysis
All samples and quality control samples were analyzed for six target analytes using high performance liquid chromatography/ tandem mass spectrometry (HPLC/MS/MS). Pertinent instrument parameters,
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3M ENVIRONMENTAL LABORATORY REPORT NO. E08-0363
the liquid chromatography gradient program, and the specific mass transitions analyzed are described in the tables below.
Table 2. Instrument Parameters.
Instrument Name Analytical Method followed Liquid Chromatograph Guard column Analytical column Injection Volume Mass Spectrometer Ion Source Electrode Polarity Software
ETS Ginger ETS-8-154.3 Agilent 1100 Betasil C 18 (2.1 mm X 100 mm), 5u Betasil C 18 (2.1 mm X 100 mm), 5p
5gL Applied Biosystems API 5000
Turbo Spray Turbo ion electrode
Negative Analyst 1.4.2
Table 3. Liquid Chromatography Gradient Program.
Step N um ber
0 1 2 3 4 5
Total Time (m in )
0 2.0 14.5 15.5 16.5 20.0
Table 4. Mass Transitions
Flow Rate (fJJm in )
300 300 300 300 300 300
Percent A (2 m M am m onium acetate)
90.0 90.0 10.0 10.0 90.0 90.0
P e rc e n tB (Methanol)
10.0 10.0 90.0 90.0 10.0 10.0
A n a ly te
M ass Transition Q 1 /Q 3
PFBA
213/169
413/369
PFOA
413/219
413/169
PFBS
299/80 299/99
499/99
PFOS
499/80
499/130
FBSA
298/78
FOSA
498/78
The individual transitions were summed to produce a "total ion chromatogram" (TIC),
which was used for quantitation.
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3M ENVIRONMENTAL LABORATORY REPORT NO. E08-0363
3 Data Analysis
3.1 Calibration
Calibration standards were prepared by spiking known amounts of stock solutions containing the analytes of interest into 40 ml. of laboratory reagent 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 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 curve point was quantitated using the overall calibration curve and reviewed for accuracy. Method calibration accuracy requirements of 10025% (10030% for the lowest curve point) were met. The correlation coefficient (r) was greater than 0.995 for all analytes.
3.2 Limit of Quantitation (LOQ)
The LOQ as defined in method ETS-8-154.3 is the lowest non-zero calibration standard in the curve that meets linearity and accuracy requirements and for which the area counts are at least twice those of the appropriate blanks. The analytical LOQs are listed below.
Table 5. Limit of Quantitation (LOQ).
A nalyte PFBA PFOA PFBS PFOS FBSA FOSA
LOQ, ng/m L 0.0995 0.100 0.0246 0.0251 0.100 0.0256
3.3 Continuing Calibration
During the course of the analytical sequence, several continuing calibration verification samples (CCVs) were analyzed to confirm that the instrument response and the initial calibration curve were still in control. Method acceptance criteria are 100% 25%. All CCVs met method criteria.
3.4 Blanks
Four types of blanks were prepared and analyzed with the samples: method blanks, solvent blanks, field/trip blanks, and equipment blanks. Each blank result is reviewed and used to evaluate method performance to determine the LOQ for each analyte.
3.5 Lab Control Spikes (LCSs)
Low and high lab control spikes were prepared and analyzed in triplicate for all analyte. LCSs were prepared by spiking known amounts of the analytes into 40 mL of laboratory reagent water to produce the desired concentration. The spiked water samples were then extracted and analyzed in the same manner as the samples. Analysis of triplicate LCSs at the two specified levels cross-validates the analytical method as used here for any modifications/deviations from ETS 8-154.3. The method acceptance criteria states that the average recovery of all LCS be between 80%-120% with a RSD <20%. All LCS samples met method acceptance criteria and were used in the determination of analytical uncertainty where applicable. The following calculations were used to generate data in Table 6.
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Calculated Concentration
0
LCS Percent Recovery --. ----------
lUU/o
Spike Concentration
LCS% RSD = stg!ldar ^ ev jg tio n jX s replicaJes . 100% average LCS recovery
3M ENVIRONMENTAL LABORATORY REPORT NO. E08-0363
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3M ENVIRONMENTAL LABORATORY REPORT NO. E08-0363
Table 6. Lab Control Spike Results.
Lab ID
PFBAm
S p ik e d
C a lc u la te d
Concentration Concentration
(ng /m L )
(ng /m L )
VoRecovery
LCS-080707-01 LCS-080707-02 LCS-080707-03 LCS-080707-04 LCS-080707-05 LCS-080707-06 Average + %RSD
0.199 0.199 0.199 4.98 4.98 4.98
0.186 0.193 0.188 5.09 4.74 4.61 95.9% 3.5%
93.7 97.2 94.6 102 95.3 92.6
PFOAm
P F B S f1>
Spiked
Calculated
Concentration Concentration
(ng /m L )
(ng /m L )
% R eco very
Spiked
Calculated
Concentration Concentration
(ng /m L )
(ng /m L )
% R eco very
0.201 0.201 0.201 5.02 5.02 5.02
0.192 0.195 0.185 5.07 4.99 5.00 97.5% 3.3%
95.8 97.1 92.1 101 99.4 99.6
0.197 0.197 0.197 4.93 4.93 4.93
0.194 0.195 0.197 4.78 4.74 4.67 97.5% 2.0%
98.6 99.0 99.8 96.9 96.2 94.7
Lab ID
p ro s m
S p ik e d
C a lc u la te d
Concentration Concentration
(ng /m L )
(ng /m L )
LCS-080707-01
0.201
0.201
LCS-080707-02
0.201
0.198
LCS-080707-03
0.201
0.195
LCS-080707-04
5.02
4.95
LCS-080707-05
5.02
4.80
LCS-080707-06
5.02
4.79
Average %RSD
97.6% 1.9%
(1) Samples analyzed July 8, 2008.
(2) Samples analyzed July 15,2008.
VoRecovery
100 98.5 97.1 98.7 95.5 95.5
FBSAW
FOSA
Spiked
C a lc u la te d
Concentration Concentration
(ng /m L )
(ng /m L )
% R eco very
S p ik e d
Calculated
Concentration Concentration
(ng /m L )
(n g /m L )
VoRecovery
0.200 0.200 0.200 5.00 5.00 5.00
0.188 0.182 0.184 4.95 4.79 4.82 94.8% 3.1%
94.1 91.2 92.0 98.9 95.8 96.5
0.205 0.205 0.205 5.12 5.12 5.12
0.226 0.236 0.216 5.15 5.59 6.17 110% 6.2%
110 115 105 101 109 120
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3M ENVIRONMENTAL LABORATORY REPORT NO. E08-0363
3.6 Analytical Method Uncertainty
Analytical uncertainty is based on historical QC data that is control charted and used to evaluate method accuracy and precision. The method uncertainty is calculated following ETS-12-012.2. The standard deviation is calculated for the set of accuracy results (in %) obtained for the QC samples. The expanded uncertainty is calculated by multiplying the standard deviation by factor of 2, which correspond with a confidence level of 95%. A minimum of twenty data points is needed to determine method uncertainty by this method.
Table 7. Analytical Uncertainty.
Analyte PFBA PFOA PFBS PFOS FBSA FOSA
Number of data points used for determining uncertainty 50 50 50 50 47 50
Standard Deviation
7.32 5.01 3.32 3.16 6.21 12.8
Method Uncertainty 100%15% 100%10% 100%6.6% 100%6.3% 100%12% 100%26%
3.7 Field Matrix Spikes (FMS)
Low, mid, and high field matrix spikes were collected at each sampling point to verify that the analytical method is applicable to the collected matrix. Field matrix spikes are generated by adding a measured volume of field sample to a container spiked by the laboratory with the target analytes prior to shipping sample containers for sample collection. Field matrix spike recoveries within method acceptance criteria of 10030% confirm that "unknown" components in the sample matrix do not significantly interfere with the extraction and analysis of the analytes of interest. Field matrix spikes are presented in the section 4 of this report.
FMS Recovery - (Sample Concentration of FMS - Average Concentration: Field Sample & Field Sample Dup.) ,, 1 Spike Concentraton
Table 8. Field Matrix Spike Concentrations
Location
Description
DSN001
Low Field Matrix Spike Mid Field Matrix Spike
High Field Matrix Spike
Low Field Matrix Spike
Trip Blank Mid Field Matrix Spike
High Field Matrix Spike
Final Concentration (ng/mL)
PFBA PFOA PFBS PFOS FBSA FOSA
0.249 0.251 0.246 0.251 0.250 0.256
4.98
5.02
4.93
5.02
5.00
5.12
99.5 100 98.6 100 100 102
0.249 0.251 0.246 0.251 0.250 0.256
4.98 5.02 4.93 5.02 5.00 5.12
99.5 100 98.6 100 100 102
4 Data Summary and Discussion
The tables below summarize the sample results and field matrix spike recoveries for sample location DSN001 as well as the Trip Blank. An equipment blank sample was also collected in the field. The
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3M ENVIRONMENTAL LABORATORY REPORT NO. E08-0363
table provides the average concentration and the relative percent difference (RPD) of the sample and sample duplicate. Results and average values are rounded to three significant figures according to EPA rounding rules. Relative percent difference values are rounded to two significant figures. Because of rounding, values may vary slightly from those listed in the raw data. Field matrix spikes meeting the method acceptance criteria of 30%, demonstrate that the method is appropriate for the given matrix. DNS001 - The recovery of the mid and high FMS for FOSA was 132% and 151 %. Since the mid level FMS is the most appropriate spike level as compared to the sample concentration, the analytical uncertainty for FOSA has been adjusted to 100% 32%.
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3M ENVIRONMENTAL LABORATORY REPORT NO. E08-0363
Table 9. DSN001 Results
3 M U M S ID
Description
E08-0363-001 E08-0363-002 E08-0363-003 E08-0363-004 E08-0363-005
DSN001, Sample DSN001, Sample Duplicate DSN001, Field Matrix Spike Low DSN001, Field Matrix Spike Mid DSN001, Field Matrix Spike High
Average Concentration (ng/mL) %RPD
PFBAm
PFOAm
P F B S f1>
Concentration
(n g /m L )
% R eco very
9.67 9.67
NA NA
10.9 13.8 88.8
NC 83.0 79.5
9.67 ng/m L 0.0%
Concentration
(ng /m L )
% R eco very
11.5
NA
10.9
NA
11.9
NC
14.7
NC
95.9
84.4
11.2 ng/mL 5 .4 %
C o n c e n tra tio n (ng /m L )
% R eco very
90.8
NA
90.2
NA
93.4 94.2
NC NC
183 93.9
90.5 ng/mL 0.66%
PFOSm
F B S A <1>
f o s a <2>
3 M U M S ID
Description
E08-0363-001 E08-0363-002 E08-0363-003 E08-0363-004 E08-0363-005
DSN001, Sample DSN001, Sample Duplicate DSN001, Field Matrix Spike Low DSN001, Field Matrix Spike Mid DSN001, Field Matrix Spike High
Average Concentration (ng/mL) % RPD
C o n c e n tra tio n
(n g /m L )
% R eco very
37.4
NA
37.9
NA
38.6
NC
41.7
NC
127 89.0
3 7 .7 ng/m L 1 .3%
C o n c e n tra tio n
(ng /m L )
% R eco very
92.6
NA
91.9
NA
97.3
NC
94.2
NC
181 88.8
92.3 ng/mL 0.76%
C o n c e n tra tio n (n g /m L )
% R eco very
9.51
NA
10.2
NA
12.7
NC
16.6
132
164 151
9.86 ng/m L 7 .0% m
NA = Not Applicable NC = Not Calculated; Endogenous sample concentration greater than 2x spike level. (1) Samples extracted July 7, 2008 and analyzed July 8, 2008. (2) Samples extracted July 7, 2008 and analyzed July 15,2008. (3) Field matrix spike did not meet method acceptance criteria of 100% 30%. (4) The analytical uncertainty for FOSA has been adjusted for recovery of the most appropriate matrix spike to 100% 32%.
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3M ENVIRONMENTAL LABORATORY REPORT NO. E08-0363
Table 10. Trip Blank Results
3 M U M S ID E08-0363-006 E08-0363-007 E08-0363-008 E08-0363-009 E08-0363-010
Description Trip Blank Sample Trip Blank FMS Low Trip Blank FMS Mid Trip Blank FMS High Equipment Blank
PFBAm
PFOAm
PFBSfv
Concentration
Concentration
(ng /m L )
VoRecovery
(n g /m L )
VoRecovery
<0.0995 0.206 4.47 79.6
<0.0995
NA 82.8 89.9 80.0 NA
<0.100 0.219 4.54 89.5 <0.100
NA 87.3 90.5 89.2 NA
Concentration (n g /m L )
<0.0246 0.224 4.32 81.0
<0.0246
VoRecovery
NA 90.9 87.7 82.2 NA
3M LIM S ID E08-0363-006 E08-0363-007 E08-0363-008 E08-0363-009 E08-0363-010
Description Trip Blank Sample Trip Blank FMS Low Trip Blank FMS Mid Trip Blank FMS High Equipment Blank
PFO S1>
FBSAm
F O S A 121
C o n c e n tra tio n (ng /m L )
<0.0251 0.209 4.15 80.4
<0.0251
C o n c e n tra tio n
VoRecovery
(ng /m L )
NA 83.3 82.7 80.1 NA
<0.100 0.225 4.45 86.1 <0.100
VoRecovery
NA 90.0 89.0 86.1 NA
Concentration (n g /m L )
<0.0256 0.256 5.05 69.7
<0.0256
VoRecovery
NA 100 98.7 6 8 . 1 (3) NA
N/A = Not Applicable (1) Samples extracted July 7,2008 and analyzed July 8, 2008. (2) Samples extracted July 7,2008 and analyzed July 15, 2008. (3) Field matrix spike did not meet method acceptance criteria of 100% 30%.
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3M ENVIRONMENTAL LABORATORY REPORT NO. E08-0363
5 Conclusion
Laboratory control spikes were used to determine the analytical method accuracy and precision for all analytes. The accuracy and precision were then used to estimate the method uncertainty for the results. Field matrix spike recoveries demonstrated that the analytical method was appropriate for the given sample matrix with the exception of FOSA, for which results have been footnoted with an expanded uncertainty. Analysis was completed following 3M Environmental Laboratory method ETS8-154.3 "Determination of Perfluorinated Acids, Alcohols, Amides, and Sulfonates in Water by Solid Phase Extraction and High Performance Liquid Chromatography/Mass Spectrometry". Analytical results are reported in Table 1 of this report.
q Data / Sample Retention
All remaining sample and associated project data (hardcopy and electronic) will be archived according to 3M Environmental Laboratory standard operating procedures.
7 Signatures
The 3M Environmental Laboratory's Quality Assurance Unit has audited the data and report for this project.
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