3M Environmental Laboratory Report No. ISO12

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# Final Report

Analysis of Water Sample s from the Tennessee River

– April 2012

Laboratory Request Number: ISO 12

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Method Requirement: 3M Method ETS

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- 044. 1

Report Date

– April 26

, 2012



## Testing Laboratory

3M Environmental Health and Safety Operations Environmental Laboratory 3M Center, Bldg 260

- 05

- N

- 17 St. Paul, MN 55144

Requester

Gary Hohenstein 3M EHS Operations 3M Building 224

- 5W

- 03 Saint Paul, MN 55144

- 1000 Phone: ( 651 ) 737

- 3570

Testing Cert #2052.01 The testing reported herein meet the requirements of ANSI/ ISO/IEC 17025:2005 “General Requirements for the Competence of Testing and Calibration Laboratories”, in accordance with the A2LA Testing Certificate # 2052.01. Testing that complies with this International Standard also meets principles of ISO 9001:2000.3M Environmental Laboratory Report No. ISO12

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### 3M Environmental Laboratory

3M Environmental Laboratory Manager: William K. Reagen, Ph.D. 3M Principal Analytical Investigator and R eport Author : Susan Wolf


## Analytical Report **ISO12**

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Analysis of Water Samples from the Tennessee River

– April 2012

Report Date: April 2 6 , 2012



## 1 **Summary /Introduction** 

The 3M Environmental Laboratory prepared and analyzed samples collected by Weston personnel from the Tennessee River , conducted per the study work plan titled "Work Plan for Fish Sampling and Analysis for PFOS in Largemouth Bass from the Tenn essee River in the Vicinity of the 3M Decatur Facility "

. Samples were collect ed April 5 and 6 , 2012 . Samples were returned to the 3M Environmental Laboratory on April 13 , 2012 at ambient conditions and analyzed for p erfluorooctane sulfonate (PFOS) under 3M Environmental Laboratory project number ISO12

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.

T he 3M Environmental Laboratory prepared sample containers for nine sampling locations, however only three sampling locations were collected. Each empty container was marked with a “fill to here” line that corresponded to a final volume of 200 mL. Each sample set consisted of a field sample, field sample duplicate, and a field matrix spike

. All samples bottles included the addition of i nternal stan dard [ 13 

### C 8 

### ]

- PFOS and surrogate recovery standard [ 13 

### C 4 

### ]

- PFOS , which were added to the sample containers prior to being sent to the field for sample collection. Sample bottles reserved for field matrix spikes were fortified with appropriate matrix spike so lution s containing PFOS , internal standard [ 13 

### C 8 

### ]

- PFOS and surrogate recovery standard [ 13 

### C 4 

### ]

- PFOS prior to being sent to the field for sample collection.

S ample s were prepared and analyzed using either direct injection or solvent dilution according to 3M Environme ntal Laboratory method ETS

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- 044. 1 “ Method of Analysis for the Determination of Perfluorinated Compounds in Water by LC/MS/M S; Direct Injection Analysis”. The internal standard [ 13 

### C 8 

### ]

- PFOS w as used to aid in the quantitation of the samples.

Table 1 summarize s 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.3M Environmental Laboratory Report No. ISO12

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### Table 1

. Sample Results Summary

.

3M LIMS ID Sample Description PFOS Concentration (ng/mL)

ISO12

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- 001 Location 1

- Sample 0.516
ISO12

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- 002 Location 1

– Sample Duplicate 0.450 **Average** 0.483 **%RPD Sample/Sample Dup** 14
ISO12

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- 004 Location 2

- Sample 0.720
ISO12

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- 005 Location 2

– Sample Duplicate 0.661 **Average** 0.691 **%RPD Sample/Sample Dup** 8.5
ISO12

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- 007 Location 3

- Sample 0.0210
ISO12

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- 008 Location 3

– Sample Duplicate 0.0263 **Average** 0.0237
**%RPD Sample/Sample Dup**  22 (2)

ISO12

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- 010 Equipment Blank 1 <0.00928
ISO12

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- 011 Equipment Blank 2 <0.00928
ISO12

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- 012 Equipment Blank 3 <0.00928
ISO12

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- 013 Trip Blank <0.00928

NA = Not Applicable (1) The analytical meth od uncertainty for the reported results using method ETS

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- 044.1 by direct inject for PFOS is ± 18 %. (2) The sample / sample duplicate RPD value did not meet method acceptance criteria of ≤20%.



## 2 **Method Summary**

2.1 Methods Analysis for PFOS was completed following 3M Environmental Laboratory method ETS

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- 044. 1

“ Method of Analysis for the Determination of Perfluorinated Compounds in Water by LC/MS/MS ”.

Table 2

. Target Analytes.

**Target Analytes Acronym**  **Reference Material Structure**  Perfluorooctanesulfonate (C8 Sulfonate) PFOS Linear + Branched



## 2.2 Sample Collection Water s amples were collected in 25 0 mL Nalgene TM 

### ( high

- density polyethylene) bottles prepared at the 3M Environmental Laboratory. A laboratory prepared Trip Blank an d Trip Blank field matrix spike were sent with the set of collection bottles. Sample bottles were received by the laboratory at ambient conditions on April 13 , 2012 . Samples were stored refrigerated at th e laboratory a fter receipt.



## 2.3 Sample Preparation An aliquot of sample was removed for analysis and placed in an autovial.

During the preparation of the laboratory control samples, an aliquot of a separate internal standard spiking solution and surrogate recovery stan dard solution was added to the laboratory control samples (nominal concentration of 0. 1 ng/mL). The sample bottles were spiked with an internal standard at a3M Environmental Laboratory Report No. ISO12

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PAGE 4 OF 11 

### nominal concentration of 0.1 ng/mL and a surrogate recovery standard at a nominal concentration o f 0.025 ng/ml prior to being sent to the field for sample collection.



## 2.4 Analysis All samples and quality control samples were analyzed for PFOS and the surrogate recovery standard [ 13 

### C 4 

### ]

- PFOS using high performance liquid chromatography/ tandem mass spectrometry (HPLC/MS/MS). Detailed instrument parameters, the liquid chromatography gradient program, and the specific mass transitions analyzed are described in the raw data hard copies placed in the final data packet, and are briefly described below.

Table 3 . Instrument Parameters

.

Instrument Name ETS Kirk Analysis Date s 4/24/12 Analytical Method ETS

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- 044.1 Liquid Chromatograph Agilent 12 90
Guard column Betasil C18 (4.6 mm X 100 mm), 5 μ Analytical column Betasil C18 (4.6 mm X 100 mm), 5 μ Injection Volume 50 μ L Mass Spectrometer Applied Biosystems API 5500
Ion Source Turbo Spray
Electrode Turbo ion electrode Polarity Negative
Software Analyst 1.5.2



### Table 4

. Liquid Chromatography Conditions

.

**Step Number**  **Total Time (min)**  **Flow Rate (**  μ

**L/min) Percent A**  **(5mM ammonium acetate:0.1% acetic acid)**  **Percent B (Methanol)** 

0 0.00 750 90.0 10.0

1 0.50 750 90.0 10.0

2 4.00 750 70.0 30.0

3 6.00 750 70.0 30.0

4 11.0 750 20.0 80.0

5 13.0 750 20.0 80.0

6 13.5 750 10.0 90.0

7 16.0 750 10.0 90.0

8 16.5 750 90.0 10.0

9 19.0 750 90.0 10.03M Environmental Laboratory Report No. ISO12

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### Table 5

. Mass Transitions.

**Analyte Mass Transition**  **Q1/Q3 Internal Standard**  **Mass Transition Q1/Q3** 

**PFOS 499/99**  **[ 13**  **C 8**  **]**

**- PFOS**  **507/80 499/80** 
**499/130 [**  **13 C**  **4 ]** 

**- PFOS**  **503/80 [**  **13 C**  **8 ]** 

**- PFOS**  **507/80**
Dwell time was 3 0 msec for each transition. The individual transitions were summed to produce a “total ion chromatogram” (TIC), which was used for quantitation.



## 3 **Analytical Results**

3.1 Calibration

Samples were analyzed for PFOS and [ 13 

### C 4 

### ]

- PFOS against a stable isotope internal standard calibration curve. Calibration standards were prepared by spiking known amounts of the stock solution containing the target analyte and surrogate recovery standard into a laboratory

- prepared synthetic groundwater containing calcium and magnesium. A separate internal standard spiking solution was prepared and an aliquot was added at the same level to all calibration standards a nd laboratory control samples at a nominal concentration of 1 ng/mL. A calibration curve ranging from approximately 0.00 5 ng/mL to 1 5 ng/ mL was analyzed (0.005 ng/mL to 5 ng/mL for [ 13 

### C 4 

### ]

- PFOS )

. The low and high curve points were disabled for PFOS to me et accuracy or method blank criteria. A quadratic, 1/x weighted, calibration curve of the standard peak area ratios was used to fit the data for each analyte. The data were not forced through zero during the fitting process. Calculating the standard con centrations using the peak area ratios and the resultant calibration curve confirme d accuracy of each curve po int.

Each curve point was quantitated using the overall calibration curve and reviewed for accuracy. Method calibration accuracy requirements of 100±25% (100±30% for the lowest curve point) were met for all analytes. The correlation coefficient (r) was greater than 0.995 for PFOS and [ 13 

### C 4 

### ]

- PFOS

.

It should be noted that the calibration curve that was used to analyze the samples on 4/24/12, expired on 4/17/12. The expiration date assigned to the curve was based on the expiration date of the solutions containing the surrogate recovery standard [ 13 

### C 4 

### ]

- PFOS, which were used to prepared the calibration standar ds. The solutions containing PFOS that were used to prepare the calibation curve were not expired. The solutions containing [ 13 

### C 4 

### ]

- PFOS that were used to prepared the high set of LCS samples and the sample collection bottles, were not expired. The high set of LCSs for [ 13 

### C 4 

### ]

- PFOS surrogate met method acceptance criteria, as did the [ 13 

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- PF OS surrogate in the Tennessee River samples. A method deviation is included in the raw data.



## 3.2 System Suitability A calibration standard was analyzed four times at the beginning of the analytical sequence to demonstrate overall system suitability. T he acceptance criteria of less than or equal to 5% relative standard deviation (RSD) for peak area ratio and retention time criteria of less than or equal to 2% RSD

wer e met for PFOS and [ 13 

### C 4 

### ]

- PFOS

.


## 3.3 Limit of Quantitation (LOQ) The LOQ for this analysis 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 th ose of the appropriate blanks. The LOQ for PFOS was 0.00928 ng/mL

.3M Environmental Laboratory Report No. ISO12

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## 3.4 Continuing Calibration During the course of each analytical sequence, continuing calibration verification samples (CCVs) were analyzed to confirm that the instrument response and the init ial calibration curve were still in control. All reported sample results were bracketed by CCVs that met method criteria of 100% ± 25 %

.


## 3.5 Blanks T hree types of blanks were prepared and a nalyzed with the samples: solvent blanks (procedural blanks), field/t r ip blanks , and equipment rinseate blank s for the groundwater samples . Each blank result

wa s reviewed and used to evaluate method performance

. Procedural blank results were reviewed according to the method and used to evaluate method performance to determ ine the LOQ for each analyte.



## 3.6 Lab Control Spikes (LCSs) Low , mid, and high lab control spikes were prepared and analyzed in triplicate for PFOS , while only low and high lab control spikes were prepared for the [ 13 

### C 4 

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- PFOS surrogate . The LCS samples were prepared by spiking known amounts of the analyte into 1 0 mL of synthetic groundwater to produce the desired concentration. The spiked water samples (LCSs) were then analyzed in the same manner as the samples.

The method acceptance criteria states that the average recovery of LCSs be 100% ± 20% with a RSD ≤20%, when evaluated independently at each concentration level. All LCSs met these criteria. The LCS results were used to determine overall method uncertainty in Section 3 .7

. The following calcula tions were used to generate data in Table 6 for laboratory control spikes

.

100% * ion Concentrat Spike ion Concentrat Calculated Recovery Percent LCS =

100% * recovery LCS average replicates LCS deviation standard RSD LCS% =3M Environmental Laboratory Report No. ISO12

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### Table 6

. Laboratory Control Spike Recovery

.

ETS

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- 044.1 Analyzed 4/24/12 PFOS (Linear + Branched)

Lab ID Spiked Concentration (ng/mL) Calculated Concentration (ng/mL) %Recovery

LCS

- 120424

- 1 0.0231 0.0273 118
LCS

- 120424

- 2 0.0231 0.0257 111

LCS

- 120424

- 3 0.0231 0.0253 110 Average ± %RSD 113 % ± 3.9 %

LCS

- 120424

- 4 0.185 0.174 93.8

LCS

- 120424

- 5 0.185 0.186 100
LCS

- 120424

- 6 0.185 0.175 94.4 Average ± %RSD 96.1 % ± 3 .6%

LCS

- 120424

- 7 4.64 3.75 80.7
LCS

- 120424

- 8 4.64 4.01 86.4

LCS

- 120424

- 9 4.64 4.19 90.4 Average ± %RSD 85.8 % ± 5.7 %

ETS

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- 044.1 Analyzed 4/24/12 [ 13 C 4 ]

- PFOS

Lab ID Spiked Concentration (ng/mL) Calculated Concentration (ng/mL) %Recovery

LCS

- 120424

- 1 (1) 0.0238 0.0246 103

LCS

- 120424

- 2 (1) 0.0238 0.0249 105
LCS

- 120424

- 3 (1) 0.0238 0.0240 101 Average ± %RSD 103 % ± 1.9 %

LCS

- 120424

- 4 0.190 0.204 107
LCS

- 120424

- 5 0.190 0.200 105

LCS

- 120424

- 6 0.190 0.202 106 Average ± %RSD 106 % ± 0.94 %

(1) The solution used to prepare this set of LCS samples expired 4/17/12.3M Environmental Laboratory Report No. ISO12

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## 3.7 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

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- 012.2. The standard deviation is calculated for the set of accuracy results (in %) obtained for the QC samples. For method ETS

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- 04 4.1 , the most recent fifty QC s amples were used. The analytical method uncertainty is calculated by multiplying the standard deviation by a factor of 2, which corresponds to a confidence level of 95%.

Table 7

. Analytical Method Uncertainty



## 3.8 Field Matrix Spikes (FMS) A f ield matrix spike was c ollected at each sampling location 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 100±30% confirm that “unknown” components in the sample matrix do not significantly interfere with the extraction and analysis of the analytes of interest. The refe rence standards for PFOS in the field matrix spiking solution consisted of linear and branched isomers.

In addition, f ield matrix spikes for this project also included the use of stable isotope surrogate spikes of [ 13 

### C 4 

### ]

- PFOS

, which was added at a nomina l concentration of 0.025 ng/mL to all sample bottles prior to sample collection. Surrogate matrix spike recoveries within method acceptance criteria of 100±30% confirm that “unknown” components in the sample matrix do not significantly interfere with the preparation and analys is of the analytes of interest.

Table 8 . Field Matrix Spike Level

.

Sampling location PFOS ng/mL All locations and Trip Blank 0.0232

100% * ion Concentrat Spike Dup.) Sample Field & Sample Field : ion Concentrat Average FMS of ion Concentrat (Sample Recovery FMS −

=



## 4 Data Summary and Discussion

The tables below summarize the sample results and field matrix spike and surrogate recoveries for the sampling locations as well as the Trip Blanks. Results and average values are rounded to three significant figures according to EPA rounding rules. Becau se of rounding, values may vary slightly from thos e listed in the raw data. Field matrix spike and surrogate recoveries meeting the method acceptance criteria of ± 30%, demo nstrate that the method (s) were appropriate for the given matrix and their respective quantitative ranges

. Analyte Standard Deviation Method Uncertainty (%)

PFOS 8.75 ± 18 [ 13 C 4 ]

- PFOS 6.74 ± 133M Environmental Laboratory Report No. ISO12

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### Table 9

. Tennessee River; Location 1

**PFOS [**  **13 C**  **4 ]** 

**- PF**  **OS**

**3M LIMS ID Description**  **Concentration (ng/mL)**  **%Recovery %Recovery** 

ISO12

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- 001 Location 1 0.516 NA 108

ISO12

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- 002 Location 1 Sample Duplicate 0.450 NA 105
ISO12

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- 003 Location 1 FMS 0.537 NC 106

**Average Concentration (ng/mL) ±**  **%RPD / %RSD**  **0.483 ng/mL**  **± 14**  **% 106%**  **± 0.99**  **%**

NA = Not Applicable NC = Not Calculated; Endogenous sample concentration is greater than 2x spiking level

.



### Table 10 . Tennessee River; Location 2

**PFOS [**  **13 C**  **4 ]** 

**- PF**  **OS**

**3M LIMS ID Description**  **Concentration (ng/mL)**  **%Recovery %Recovery** 

ISO12

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- 004 Location 2 0.720 NA 108

ISO12

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- 005 Location 2 Sample Duplicate 0.661 NA 106
ISO12

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- 006 Location 2 FMS 0.654 NC 109

**Average Concentration (ng/mL) ±**  **%RPD / %RSD**  **0.691 ng/mL ±**  **8.5 %**  **108% ±**  **1.5 %** 

NA = Not Applicable NC = Not Calculated; Endogenous sample concentration is greater than 2x spiking level

.



### Table 11 . Tennessee River; Location 3

**PFOS [**  **13 C**  **4 ]** 

**- PF**  **OS**

**3M LIMS ID Description**  **Concentration (ng/mL)**  **%Recovery %Recovery** 

ISO12

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- 007 Location 3 0.0210 NA 105
ISO12

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- 008 Location 3 Sample Duplicate 0.0263 NA 108

ISO12

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- 009 Location 3 FMS 0.0430 83.4 106

**Average Concentration (ng/mL) ±**  **%RPD / %RSD**  **0.0237 ng/mL ±**  **22 %**  **(1) 106%**  **± 1.6**  **%**

NA = Not Applicable (1) The sample / sample duplicate RPD did not meet method acceptance criteria of ≤ 20%.3M Environmental Laboratory Report No. ISO12

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### Table 12

. Rinseate Blanks

**PFOS [**  **13 C**  **4 ]** 

**- PF**  **OS**

**3M LIMS ID Description**  **Concentration (ng/mL)**  **%Recovery**

ISO12

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- 010 Equipment Blank 1 < 0.00928 108

ISO12

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- 011 Equipment Blank 2 <0.00928 105
ISO12

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- 012 Equipment Blank 3 <0.00928 108



### Table 13 . Trip Blanks

**PFOS [**  **13 C**  **4 ]** 

**- PF**  **OS**

**3M LIMS ID Description**  **Concentration (ng/mL)**  **%Recovery %Recovery** 

ISO12

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- 013 Trip Blank <0.00928 NA 105
ISO12

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- 014 Trip Blank FMS 0.0209 90.1 1033M Envimnmental

Laboratory Report No. ISO12-01-01-02



## 5 Conclusion

Laborator y contro l spike s wer e use d t o determin e th e analytica l metho d accurac y an d precisio n fo r PFOS

. Th e accurac

y an d precisio n wer e the n use d t o estimat e th e metho d uncertaint y fo r th e results

. Fiel d matri x spik e recoverie s demonstrate d tha t th e analytica l metho d wa s appropriat e fo r th e give n sampl e matrix

. Analysi s wa s complete d usin g 3 M Environmenta l Laborator y metho d ETS-8-044. 1 "Metho d o f Analysi s fo r th e Determinatio n o f Perfluorinate d Compound s i n Wate r b y LC/MS/MS ; Direc

t Injectio n Analysis"

. Analytica l result s ar e reporte d i n Table s 1 an d 9-1 3 o f thi s report

.


## 6 Data/Sample

Retention

Al l remainin g sample s an d associate d projec t dat a (hardcop y an d electronic ) wil l b e archive d accordin g t o 3 M Environmenta l Laborator y standar d operatin g procedures

.



## 7 Signatures

Susa n Wolf

, 3 M Princi^Analytica l Investigato r Dat e

Willia m K

. Reagen

, Ph.D.

, 3 M Environmenta l Laborator y Manage r Dat e

Th e 3 M Environmenta l Laboratory' s Quality Assuranc e Uni t ha s audite d th e dat a an d repor t fo r thi s project

.

Quality Assuranc e Representativ e Dat e

PAG E 1 1 O F 1 1