# 

U 

## GLP10

- 01

- 01

, Interim Report 28: Analysis of PFOA in Groundw ater Samples

Collected at Decatur, AL for 1 st 

## Quarter 2012

Study Title

Analysis of Perfluorooctanoic Acid (PFOA) in Groundwater, Soil and Sediment for the 3M Decatur

Phase 3 Site

- Related Monitorin g Program



### Data Requirement EPA TSCA Good Laboratory Practice Standards 40 CFR Part 792



### Study Director

Jaisimha Kesari P.E., DEE

Weston Solutions, Inc.

1400 Weston Way

West Chester, PA 19380

Phone: 610

- 701

- 3761



### Author

Susan Wolf

3M Environmental Laborat ory



### Interim Report Completion Date

Date of signing



### Performing Laboratory

3M Environmental Health and Safety Operations

Environmental Laboratory 3M Center, Bldg 260

- 05 -N- 17

Maplewood, MN 55144



### Project Identification

GLP10

- 01

- 01

- 28



### Total Number of Pages

66

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.

### This page has been reserved for specific country requirements.GLP10-01-01 ; Interi m Repor t 2 8 Analysi s o f PFO A i n Groundwate r Decatur

, A L - 1s t Quarte r 201 2 Samplin g



### GL P COMPLIANC E STATEMEN T

Repor t Title : GLP10-01-01

, Interi m Repor t 28

. Analysi s o f PFO

A i n Groundwate r Sample s Colle<::te d

a t Decatur

, A L fo r 1 " Quarte r 201 2

Study : Analysi s o

f Perfluorooctanoi c Aci d (PFOA ) i n Groundwater

, Soi l an d Sedimen t fo r th e 3 M
Decatu r Phas e 3 Site-Relate d Monitorin g Program

.

Thi s analytica l phas e wa s conducte d i n complianc e wit h Toxi c Substance s Contro l Ac t (TSCA ) Goo d
Laborator y Practic e (GLP ) Standards

, 4 0 CF R 792

, wit h th e exception s liste d below :

• Thes e ar e environmenta l sample s wher e ther e i s n o specifi c tes t substance

, n o specifi c tes t syste m an d n o dosin g o f a tes t system

.

• Th e referenc e substance s hav e no t bee n characterize d unde r th e GLP s an d th e stabilit y unde r storag e condition s a

t th e tes t sit e hav

e no t bee n determine d unde r GLPs

.

Gai y Hohenstein

, Sponso r Representativ e Dat e

Jaisimha^Ke^ri

, P.E.

, DEE

, Stud y Directo r ' Dat e 

# 72 ^

Pag e 3 o f 6 6GLP10-01-01 ; Interi m Repor t 2 8 Analysi s o f PFO A I n Groundwate r Decatur

, A L - 1s t Quarte r 201 2 Samplin g



### QUALIT Y ASSURANC E STATEMEN T

Repor t Title : GLP10-01-01

, Interi m Repor t 28

. Analysi s o f PFO

A i n Groundwate r Sample s Collecte d

a t Decatur

, A L fo r 1 " Quarte r 201 2

Study : Analysi s o

f Perfluorooctanoi c Aci d (PFOA ) i n Groundwater

, Soi l an d Sedimen t fo r th e 3 M

Decatu r Phas e 3 Site-Relate d Monitorin g Program

.

Thi s repor

t an d th e accompanyin g dat a wer e audite d b y th e 3 M Environmenta l Laborator y Qualit y Assuranc e Uni t (QAU)

, a s indicate d below

. Th e finding s wer e reporte d t o th e principa l investigato r (P.I.)

, laborator

y managemen t an d stud y director

.

Inspectio n Date s Phas e Dat e Re i jorte d t o Inspectio n Date s Phas e Testin g Facilit y lUanagemen t Stud y Directo r

4/16/1 2 Interi m Repor t 2 8

Dat a an d Repor

t 4/26/1 2 4/26/1 2



### QA U Represe/lfetiv e Dat e

Pag e 4 o f 6 6

# T ABLE OF 

# C ONTENTS

U 

### GLP Compliance Statement

U 

### ...................................................................................................................... 3

U 

### Quality Assurance Statement

U 

### .................................................................................................................... 4

U 

### Table of Contents

U 

### ................................................................................................ ....................................... 5

U 

### List of Tables

U 

### ................................................................................................ .............................................. 6

U 

### 1

U U 

### Study Information

U 

### ................................................................................................ ................................ 8

U 

### 2

U U 

### Summary

U 

### ................................................................................................ ............................................. 9

U 

### 3

U U 

### Introduction

U 

### ................................................................................................ ........................................ 10

U 

### 4

U U 

### Test & Control Substances

U 

### .............................................................................................................. 10

U 

### 5

U U 

### Reference Substances

U 

### ..................................................................................................................... 11

U 

### 6

U U 

### Test System

U 

### ................................................................................................ ...................................... 11

U 

### 7

U U 

### Method Summary

U 

### ............................................................................................................................. 12

U 

### 7.1

U U 

### Methods

U 

### ............................................................................................................................ 12

U 

### 7.2

U U 

### Sample Collection

U 

### ............................................................................................................. 12

U 

### 7.3

U U 

### Sample Preparati on

U 

### .......................................................................................................... 12

U 

### 7.4

U U 

### Analysis

U 

### ............................................................................................................................. 12

U 

### 8

U U 

### Analytical Results

U 

### .............................................................................................................................. 13

U 

### 8.1

U U 

### Ca libration

U 

### ......................................................................................................................... 13

U 

### 8.2

U U 

### System Suitability

U 

### ............................................................................................................. 13

U 

### 8.3

U U 

### Limit of Quantitation (LOQ)

U 

### .............................................................................................. 13

U 

### 8.4

U U 

### Continuing Calibration

U 

### ...................................................................................................... 14

U 

### 8.5

U U 

### Blanks

U 

### ................................................................................................ ................................ 14

U 

### 8.6

U U 

### Lab Control Spikes (LCSs)

U 

### .............................................................................................. 14

U 

### 8.7

U U 

### Analytical Method Uncertainty

U 

### ......................................................................................... 15

U 

### 8.8

U U 

### Field Matrix Spikes (FMS)

U 

### ................................................................................................ 15U 

### 9

U U 

### D ata Summary and Discussion

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### ....................................................................................................... 16

U 

### 10

U U 

### Conclusion

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### ................................................................................................ ......................................... 23

U 

### 11

U U 

### Data/Sample Retention

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### .................................................................................................................... 23

U 

### 12

U U 

### Attachments

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### ................................................................................................ ...................................... 23

U 

### 13

U U 

### Signatures

U 

### ................................................................................................ ......................................... 24



# L IST OF 

# T ABLES

Table 1. Summarized PFOA Results (Decatur Groundwater, 1 st 

### Quarter 2012)

................................... 9

Table 2. Sample Description Key Code.

............................................................................................... 11

Table 3. Instrument Paramet ers.

............................................................................................................ 12

Table 4. Liquid Chromatography Conditions.

........................................................................................ 13

Table 5. Mass Transitions.

...................................................................................................................... 13

Table 6. Limit of Quantitation (LOQ).

...................................................................................................... 14

Table 7. Laboratory Control Spike Recovery.

........................................................................................ 15

Table 8. Analytical Method Uncertainty

................................................................................................... 15

Table 9. Field Matrix Spike Concentrations

........................................................................................... 16

Table 10. DAL GW 203L 120327

........................................................................................................... 17

Table 11. DAL GW 220R 120323

.......................................................................................................... 17

Table 12. DAL GW 220L 120323

........................................................................................................... 17

Table 13. DAL GW 222R 120327

.......................................................................................................... 18

Table 14. DAL GW 227R 120316

.......................................................................................................... 18

Table 15. DAL GW 227L 120316

........................................................................................................... 18

Table 16. DAL GW 310R 120320

.......................................................................................................... 19

Table 17. DAL GW RW312R 120328

.................................................................................................... 19

Table 18. DAL GW 317L 120320

........................................................................................................... 19

Table 19. DAL GW 324L 120314

........................................................................................................... 20

Table 20. DAL GW RW327R 120323

.................................................................................................... 20

### Table 21. DAL GW 328R 120314

.......................................................................................................... 20

Table 22. DAL GW 328L 120314

........................................................................................................... 21

Table 23. DAL GW 330R 120314

.......................................................................................................... 21

Table 24. DAL GW 330L 120314

........................................................................................................... 21

Table 25. DAL GW RW331S 120328

.................................................................................................... 22

Table 26. DAL GW 335R 120322

.......................................................................................................... 22

Table 27. DAL GW GRS04 120328

....................................................................................................... 22

Table 28. Trip Blank 1

............................................................................................................................. 23

Tab le 29. Rinseate Blank

........................................................................................................................ 23

## 1

0B 

## Study Information

Sponsor

3M Company

Sponsor Representative

Gary Hohenstein 3M EHS Operations 3M Building 224

- 5W

- 03 Saint Paul, MN 55144

- 1000 Phone: (651) 737

- 3570

Study Director

Jaisimha Kesa ri, P.E., DEE Weston Solutions, Inc. West Chester, PA 19380 Phone: (610) 701

- 3761 Fax: (610) 701

- 7401 j.kesari@westonsolutions.com

Study Location

Testing Facility

3M EHS Operations 3M Environmental Laboratory Building 260

- 5N

- 17 Maplewood, MN 55106

Study P ersonnel

William K. Reagen, Ph.D., 3M Laboratory Manager Cleston Lange

, Ph.D., Principal Analytical Investigator. (

H U 

### clange@mmm.com

U H 

### ); phone (651)

- 733

- 9860
Susan Wolf

, 3M Analyst

Chelsie Grochow ; A nalyst Kelly Ukes; A nalyst

Study Dates

Study Initiation: March 8 , 2010

Interim 28 Experimental Termination Date : April 10, 2012 Interim Report Completion: Date of Interim Report Signing

Location of Archives

All original raw data and the analytical report have been archived at the 3M Environmental Laboratory according to 40 CFR Part 792. The test substance and analytical reference standard reserve samples are archived at the 3M Environmental Laboratory according to 40 CFR Part 792

## 2

1B 

## Summary

The 3M Environmental Laboratory received groundwater samples from w ells located in Decatur, AL,

r epresent ing eighteen (18) different sampling locations collected March 14

- 28, 2012

. A total of seventy

- seven sample bottles were received at the 3M Environmental Laboratory for perfluorooctanoat e ( PFOA ) analysis, and included du plicate groundwater samples from each sampling

location . Samples also included field matrix spike (FMS) samples for each location

, one trip blank containing Milli

- QTM water and appropriate trip blank spikes, and one equipm ent rinseate blank

. The equipment rinseat e blank did not have a FMS sample prepared for the determination of PFOA

recovery . All of the samples were prepared and analyzed for PFOA following 3 M Environmental Laboratory Method ETS -8- 044. 1 and conducted under 3M project GLP10

- 01

- 01

- 28

.

The g roundwater samples, trip blanks and equ ipment rinseate blank s for GLP10

- 01

- 01

- 28 were received f rom Weston personnel on April 4, 2012

. All of the samples were prepared and analyzed for

PFOA following 3 M Environmental L aboratory Method ETS -8- 044. 1. Many of the groundwater samples required dilution to attain PFOA concentrations w ithin the range of the curve, in some

instances up to 100

- fol d dilution were required

. The average measured PFOA concentrations are

summarized in Table 1. The equipment rinseate and the trip blank s associated with GLP10

- 01

- 01

- 28

w ere below the lower limit of quantitation (LLOQ) of 0.0 24 0 ng/mL . C oncentration results for all groundwater samples ranged from 0.262 ng/mL to 3 890 ng/mL

. The analytical uncertainty for PFOA is

+

U 

### 23 %.

Table 1. Summarized PFOA Results (Decatur Groundwater, 1 st 

### Quarter 2012 )

Sample ID Avg. PFOA Concentration (ng/ mL ) Relative Percent

Difference (RPD)

DAL GW 203L 120327 179 0.56 %

DAL GW 220R 12 0323 37.3 7.0 %

DAL GW 220L 120323 48.1 0.21 %

DAL GW 222R 1 20327 330 1.5 %

DAL GW 227R 120316 339 0.30%

DAL GW 227L 1 20316 82.1 1.7 %

DAL GW 310R 1 20320 929 8.1 %

DAL GW RW 312R 1 20328 934 1.6 %

DAL GW 317L 1 20320 0.262 0.76 %

DAL GW 324L 1 20314 270 0.37 %

DAL GW RW 327R 1 20323 700 0.43 %

DAL GW 328R 1 20314 334 0.60 %

DAL GW 328L 1 20314 96.3 2.6 %

DAL GW 330R 120314 335 2.4 %

DAL GW 330L 1 20314 297 0.34 %

DAL GW RW 331S 1 20328 940 (1) 4.7 %

DAL GW 335R 1 20322 3890 2.3 %

DAL GW GRS04 1 20328 3860 3.9 %
Trip Bl ank (Milli

- QTM Water) < 0. 0240 N/A
Equipment Blank < 0.0240 N/A N/A; not applicable The analytical method uncertainty for PFOA is +

U 23 %. (1) The method uncertainty for sample location RW331S has been adjusted to +

U 32 % due to FMS recovery. See section 9 of the report for additional information.

## 3

2B 

## Introduction

This analytical study was conducted as part of the Phase 3 En vironmental M onitoring and A ssessment

P rogram for the 3M facility located in Decatur, Alabama. The objective of the overall program is to gai n information regarding concentrations of perfluorooctanoate (PFOA) in various environmental media such as groundwater, soils and sediments that are associated with and near the Decatur facility. This analytical study was conducted to analyze ground water samples collected from various well s located

in Decatur, AL for PFOA in an effort to characterize on

- site groundwater conditions.

The 3M Environmental Laboratory prepared sample bottles ( 25 0 mL high

- densi ty polyethylene ) which

were shipped to Decatur, AL Weston personnel prior to field sampling. Sample bottle sets for each groundwater sampling location included a field sample, field sample duplicate, and field spike samples

. Each empty container for groundwater samplings was marked with a “fill to here” line to produce a final sample volume of 200 mL. Containers designated for field matrix samples were fortified with an appropriate matrix spike solution containing PFOA prior to being sent to the field for sample collection.

See section 8.8 of the report for field matrix spike levels

. The aqueous equipment rinseate sample was

collected in a plain bottle without fortification

.

S ample s were prepared and analyzed according to the procedure defined in 3M Environme ntal Laboratory method ETS -8- 044. 1 “ Metho d of Analysis for the Determination of Perfluorinated Compounds in Water by LC/MS/MS; Direct Injection Analysis ”.

Table 1 summarize s the average PFOA concentrations for the duplicate ground water samples

collected

, and for the trip blank and aqueous r inseate sample s

. Tables 10

- 29 summarize the individual sample results and the associated FMS recoveries

. All results for the quality control samples prepared and analyzed with the samples are reported and discussed elsewhere in this report.



## 4

3B 

## Test **& C ontrol Substance**  **s**

Th ere was not a test substance or control substances in the classic sense of a GLP study. This study was purely analytical in nature.

## 5

4B 

## Reference Substances

The analytical reference substances used for this study are l isted below.

Reference Substance PFOA (Linear + Branched) PFOA (Linear + Branched)

Chemical Name Perfluorooctanoate Perfluorooctanoate

Chemical Formula 

### C 7 

### F 15 

### COO - 

### C 7 

### F 15 

### COO Identifier CAS # 335

- 67 -1 CAS # 95328

- 99 -7

Use FMS Reference Standard Target An alyte and LCS

Reference Standard

Source Sigma Aldrich Wellington

Expiration Date 07/27/2016 03/17/2014

Storage Conditions Ambient Frozen

Chemical Lot Number MKBD4574V TPFOA0311

TCR Number TCR 11

- 0029 TCR11

- 0009 , TCR11

- 0042

Physical Description Powder Liquid

Purity 96.8 % 98.3 %



## 6

5B 

## Test System

There was not a test system for this study in the classic sense of a GLP study. This study was conducted for analysis of ground water samples collected from wells located in Decatur, AL by Weston Solutions, Inc. personnel. Samples for this study are “real world” environmental samples.

Table 2

. Sample Description Key Code.

**Example DAL**  **GW 203L**  **DB 1**  **20327**

String Number String Descriptor Example

**1 Sampling Location**  **DAL = Decatur, Alab ama** 

**2 Sample Type**  **GW= Ground w**  **ater**

**3 Well Identifier**  **Example: 203**  **L**

**4 Well Level**  **R = Residu u**  **m shallow water**

**- bearing zone** 

**L = Bedrock water**

**- bearing zo**  **ne**

**S = Epikarst**  **middle water**

**- bearing zone** 

**5 Sample Type**  **0=primary sample**

**DB =duplicate sample** 

**LS = low spike** 

**HS = high spike**

**6 Sampling Date**  **120327 = March 27, 2012**

## 7

6B 

## Method Summary

7.1

12B 

## Methods
Analysis for all analytes was completed following 3M Environmental Laboratory method ETS -8- 044.1

“ Method of Analysis for the Determination of Perfluorinated Compo unds in Water by LC/MS/MS; Direct Injection Analysis ”.



## 7.2

13B 

## Sample Collection
Samples were collected in 25 0 mL Nalgene TM 

### ( high

- density polyethylene) bottles prepared at the 3M Environmental Laboratory. Sample bottles were returned to the laboratory at ambient conditions on April
4, 2012. Samples were stored refrigerated at the laboratory after receipt. One set of laboratory prepared Trip Blank and Trip Blank field matrix spikes were sent with the sample collection bottles.



## 7.3

14B 

## Sample Preparation
Sample s were prepared by removing an aliquot of the well mixed sample and placing it in an autovial for analysis.

Samples that required dilution were prepared as follows: 1:10 dilutions were prepared by diluting 1mL sample with 9 mL of Milli Q water, and

1:1 00 dilutions were prepared by diluting 0.1mL sample with 9.9 mL of Milli Q water.



## 7.4

15B 

## Analysis

All study samples and quality control samples were analyzed for PFOA 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 in Table 3

, Table 4

and Table 5

.

Ta ble 3 . Instrument Parameters

.

Instrument Name ETS Buster

Analytical Method Followed ETS

- 8

- 044. 1

Analysis Dates 4/5/2012

Project GLP10

- 01

- 01

- 28

Liquid Chromatograph Agilent 1100

Guard column Betasil C18 (4.6 mm X 100 mm), 5 μ

A nalytical column Betasil C18 (4.6 mm X 100 mm), 5 μ
Injection Volume 2 or 10 μ L

Mass Spectrometer Applied Biosystems API 4 000

Ion Source Turbo Spray

Electrode Turbo ion electrode

Polarity Negative

Software Analyst 1.4.2

### Table 4. Liquid Chromatography Conditions

.

**Step**

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

**L/min) Percent A** 

**(2 mM ammonium acetate) Percent B** 

**(Methanol)**

ETS

- 8

- 044. 1

0 0 750 97.0 3.0

1 2.0 750 9 7.0 3 .0

2 14

. 5 750 5.0 9 5 .0

3 15. 5 750 5. 0 95 .0

4 1 6.5 750 97 .0 3 .0

5 20.0 750 97 .0 3 .0



### Table 5. Mass Transitions.

**Analyte Mass Transition** 

**Q1/Q3 Reference Material** 

**Structure**

**PFOA 413/369** 

**Linear +**  **Branched 413/219** 

**413/169**

Dwell time was 10 0 msec for each transition. The individual tran sitions were summed to produce a “total ion chromatogram” (TIC), which was used for quantitation.



## 8

7B 

## Analytical Results

8.1

16B 

## Calibration
Samples were analyzed against a n external standard calibration curve. Calibration standards were prepared by spiking known amounts of the stock solution containing PFOA (reference standard containing both linear and branched isomers) into Milli Q water

. Standards ranging from 0.02 50 ng/mL to 100 ng/mL (nominal) were analyzed

. A quadratic, 1/x weighted, calibration curve of the peak area counts was used to fit the data for each analyte. The data were not forced through zero during the fitting process. Calculating the standard concentrations using the peak area 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 100±25% (100±30% for the lowest curve point) were met for all analytes. The correlation coefficient (r) was greater than 0.995 for PFO A.



## 8.2

17B 

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

2% RSD for PFOA

.



## 8.3

18B 

## 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 those of the appropriate
blanks. The nominal LOQ for all analytes can be found in Table 6

.

### Table 6 . Limit of Quantitation (LOQ)

.

**Analysis Date PFOA** 

**LOQ, ng/mL (1)** 



### 4/5/12 0.024 0

(1) Analytical LOQ without sample dilution factor s applied.



## 8.4

19B 

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

.



## 8.5

20B 

## Blanks

Three types of blanks were prepared and analyzed with the samples: method procedural blanks

, a trip blank, and an equipm ent rinseate blank

. Method procedural blank result s were reviewed and used to evaluate method performance and to determine the LOQ for PFOA

. The trip blank reflect s the shipping and sample collection condit i ons the sample bottles and samples experie nce. The equipment rinseate

blank is an aqueous sample that reflect the efficiency of equipment cleaning in the field between different sample collections and are proof of no cross contamination of samples from the equipment.



## 8.6

21B 

## Lab Control Spikes (LCSs)

La b control spikes were prepared and analyzed in triplicate with each preparation set. LCSs were prepared by spiking known amounts of the analyte into laboratory reagent water

, to produce the desired concentration. The spiked water samples were then analyzed in the same manner as the samples. The method acceptance criteria, average of LCS at each level should be within 100% ± 20% with an RSD

≤20% , was met for all LCSs

.

The following calculations were used to generate data in Table 7 for laboratory control spikes :

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

=

100% * recovery LCS average replicates LCS deviation standard RSD LCS%

=

### Table 7. Laboratory Cont rol Spike Recovery

.

ETS -8- 044.1

Analyzed 4/5/12 **PFOA (Linear + Branched)** 

**Lab ID Spiked** 

**Concentration (ng/mL)**  **Calculated**

**Concentration (ng/mL)**  **%Recovery**

LCS

- 120405

- 1 0.477 0.433 90.7

LCS

- 120405

- 2 0.477 0.428 89.7

LCS

- 120405

- 3 0.477 0.431 90.3

Ave rage ± %RSD 90.2 % ± 0.56 %

LCS

- 120405

- 4 4.77 4.53 94.9

LCS

- 120405

- 5 4.77 4.60 96.4

LCS

- 120405

- 6 4.77 4.58 96.0

Average ± %RSD 95.8 % ± 0.81 %

LCS

- 120405

- 7 28.7 25.0 87.1

LCS

- 120405

- 8 28.7 24.6 85.8

LCS

- 120405

- 9 28.7 25.1 87.5

Average ± %RSD 86.8 % ± 1.0 %



## 8.7

2B 

## 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 most recent fifty QC samples. The expanded uncertainty is calculated by multiplying the standard deviation by a factor of 2, which corresponds to a confidence level of 95%.

Table 8 . Analytical Method Uncertainty

Analyte Method Standard

Deviation Method Uncertainty

PFOA ETS

- 8

- 044.1 11.7 ± 23 %



## 8.8

23B 

## Field Matrix Spikes (FMS)

F ield matrix spikes were collected at each sampling point to verify that the analytical method is applicable to the collected matrix

. Field matrix spikes were generated by adding a measured volume of field sample to a container spiked by the laboratory with PFOA (reference standard containing both linear and branched isomers) 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.

Fie ld matrix spike concentrations must be 50% of the sample concentration to be considered an appropriate field spike. Field matrix spikes are presented in section 9 of this report.

### Table 9 . Field Matrix Spike Concentrations

Locat ion (Well ID) Spike Level PFOA Spike

Concentration (ng/mL)

317L L ow Spike 1

H igh Spike 10

220R, 220L, and 328L Low Spike 10
High Spike 100

203L, 222R, 227L, 227R, 324L, 330L, RW327R Low Spike 100

H igh Spike 500

310R, 330R, RW331S Low Spike 500 High Spike 1 000

GRS04, RW312R, 335R Low Spike 1000 High Spike 5000
Trip Blank 1 Low Spike 10 Mid Spike 100
High Spike 1000

100%*

on Concentrat Spike Dup.) Sample Field & Sample Field:ion Concentrat Average FMS ofion Concentrat (Sample Recovery FMS −

=



## 9 **Data Summary and Discussion**

The tables below summarize the sample results and field matrix spike recoveries for the sampling locations as well as the Trip Blanks and rinseate blank

. Results and average values are rounded to three significant figures according to EPA rounding rules. Because of rounding, values may vary slightly

from those listed in th e raw data. Field matrix spike recoveries meeting the method acceptance criteria

of ± 30%, demonstrate that the method was appropriate for the given matrix and their respective quantitative ranges

.

DAL GW RW 331S ( Table 25 ) – The h igh field matrix spike had a recovery of 68.0 % , while the low field matrix spike met method acceptance criteria

. Since both spike levels were appropriate as compared to the sample location, the method uncertainty has been adjusted to ± 32%.

### Table 10

. DAL GW 203 L 120327

**PFOA**

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

GLP10

- 01

- 01

- 28

- 001 DAL

- GW

- 203L

- 0

- 120327 178 NA

GLP10

- 01

- 01

- 28

- 002 DAL

- GW

- 203L

- DB

- 120327 179 NA

GLP10

- 01

- 01

- 28

- 003 DAL

- GW

- 203L

- LS

- 120327 269 90.5

GLP10

- 01

- 01

- 28

- 004 DAL

- G W

- 203L

- HS

- 120327 597 83.7

**Average Concentration (ng/mL) ±**  **%RPD 179**  **ng/mL ±**  **0.56 %** 

NA = Not Applicable Samples analyzed using a 1:10 0 dilution factor.



### Table 11

. DAL GW 220R 120323

**PFOA**

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

GLP10

- 01

- 01

- 28

- 005 DAL

- GW

- 220R

- 0

- 120323 38.6 NA

GLP10

- 01

- 01

- 28

- 006 DAL

- GW

- 220R

- DB

- 120323 36.0 NA

GLP10

- 01

- 01

- 28

- 007 DAL

- GW

- 220R

- LS

- 120323 48.3 NC

GLP10

- 01

- 01

- 28

- 008 DAL

- GW

- 220R

- HS

- 120323 123 85.7

**Average Concentration (ng/mL) ±**  **%RPD 37.**  **3 ng/mL**  **± 7.0**  **%**

NA = Not Applicable
NC = Not Calculated; t he sample concentration is greater than 2x the spike level. Samples analyzed using a 1:10 dilution factor.



### Table 12

. DAL GW 220L 1 20323

**PFOA**

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

GLP10

- 01

- 01

- 28

- 009 DAL

- GW

- 220L

- 0

- 120323 48.1 NA

GLP10

- 01

- 01

- 28

- 010 DAL

- GW

- 220L

- DB

- 120323 48.0 NA

GLP10

- 01

- 01

- 28

- 011 DAL

- GW

- 220L

- LS

- 120323 57.8 NC

GLP10

- 01

- 01

- 28

- 012 DAL

- GW

- 220L

- HS

- 120323 134 86.0

**Average Concentration (n g/mL)**  **± %RPD**  **48.1 ng/mL**  **± 0.21**  **%**

NA = Not Applicable

NC = Not Calculat ed; t he sample concentration is greater than 2x the spike level. Samples analyzed using a 1:10 dilution factor.

### Table 13

. DAL GW 222R 1 20327

**PFOA**

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

GLP10

- 01

- 01

- 28

- 013 DAL

- GW

- 222R

- 0

- 120327 332 NA

GLP10

- 01

- 01

- 28

- 014 DAL

- GW

- 222R

- DB

- 120327 327 NA

GLP10

- 01

- 01

- 28

- 015 DAL

- GW

- 222R

- LS

- 120327 427 NC

GLP10

- 01

- 01

- 28

- 016 DAL

- GW

- 222R

- HS

- 120327 763 86.7

**Average Con centration (ng/mL)**  **± %RPD**  **330 ng/mL**  **± 1.5**  **%**

NA = Not Applicable
NC = Not Calculated; t he sample concentration is greater than 2x the spike level. Samples analyzed using a 1:100 dilution factor.



### Table 14

. DAL GW 227R 120316

**PFOA**

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

GLP10

- 01

- 01

- 28

- 017 DAL

- GW

- 227R

- 0

- 120316 339 NA

GLP10

- 01

- 01

- 28

- 018 DAL

- GW

- 227R

- DB

- 120316 338 NA

GLP10

- 01

- 01

- 28

- 019 DAL

- GW

- 227R

- LS

- 120316 417 NC

GLP10

- 01

- 01

- 28

- 020 DAL

- GW

- 227R

- HS

- 120316 764 85.1

**Average Concentration (ng/mL) ±**  **%RPD 339**  **ng/m L**  **± 0.30**  **%**

NA = Not Applicable
NC = Not Calculated; t he sample concentration is greater than 2x the spike level. Samples analyzed using a 1:10 0 dilution factor.



### Table 15

. DAL GW 227L 1 20316

**PFOA**

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

GLP10

- 01

- 01

- 28

- 021 DAL

- GW

- 227L

- 0

- 120316 82.8 NA

GLP10

- 01

- 01

- 28

- 022 DAL

- GW

- 227L

- DB

- 120316 81.4 NA

GLP10

- 01

- 01

- 28

- 023 DAL

- GW

- 227L

- LS

- 120316 175 92.9

GLP10

- 01

- 01

- 28

- 024 DAL

- GW

- 227L

- HS

- 1 20316 535 90.6

**Average Concentration (ng/mL) ±**  **%RPD 82.1**  **ng/m L**  **± 1.7**  **%**

NA = Not Applicable Samples analyzed using a 1:10 0 dilution factor.

### Table 16

. DAL GW 310R 1 20320

**PFOA**

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

GLP10

- 01

- 01

- 28

- 025 DAL

- GW

- 310R

- 0

- 120320 966 NA

GLP10

- 01

- 01

- 28

- 026 DAL

- GW

- 310R

- DB

- 120320 891 NA

GLP10

- 01

- 01

- 28

- 027 DAL

- GW

- 310R

- LS

- 120320 1290 72.3

GLP10

- 01

- 01

- 28

- 028 DAL

- GW

- 310R

- HS

- 120320 1660 73.2

**Average Concentration (ng/mL) ±**  **%RPD 929**  **ng/m L**  **± 8.1**  **%**

NA = Not Applicable
NC = Not Calculated; t he sample concentration is greater than 2x the spike level. Samples analyzed using a 1:100 dilution factor.



### Table 17

. DAL GW RW 312R 1 20328

**PFOA**

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

GLP10

- 01

- 01

- 28

- 029 DAL

- GW

- RW312R

- 0

- 120328 941 NA

GLP10

- 01

- 01

- 28

- 030 DAL

- GW

- RW312R

- DB

- 120328 926 NA

GLP10

- 01

- 01

- 28

- 031 DAL

- GW

- RW312R

- LS

- 120328 1670 73.7

GLP10

- 01

- 01

- 28

- 032 DAL

- GW

- RW312R

- HS

- 120328 5040 82.1

**Average Concentration (ng/mL)**  **± %RPD**  **934 ng/m**  **L ±**  **1.6 %** 

NA = Not Applicable Sample, sample duplicate, and LS were analyzed using a 1:100 dilution factor. The HS was analyzed using a 1:500 dilution fac tor.



### Table 18

. DAL GW 317L 1 20320

**PFOA**

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

GLP10

- 01

- 01

- 28

- 033 DAL

- GW

- 317L

- 0

- 120320 0.261 NA

GLP10

- 01

- 01

- 28

- 034 DAL

- GW

- 317L

- DB

- 120320 0.263 NA

GLP10

- 01

- 01

- 28

- 035 DAL

- GW

- 317L

- LS

- 120320 1.15 88.8

GLP10

- 01

- 01

- 28

- 036 DAL

- GW

- 317L

- HS

- 120320 8.25 79.9

**Ave rage Concentration (ng/mL)**  **± %RPD**  **0.262 ng/m**  **L ±**  **0.76 %** 

NA = Not Applicable

### Table 19

. DAL GW 324L 1 20314

**PFOA**

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

GLP10

- 01

- 01

- 28

- 037 DAL

- GW

- 324L

- 0

- 120314 270 NA

GLP10

- 01

- 01

- 28

- 038 DAL

- GW

- 324L

- DB

- 120314 269 NA

GLP10

- 01

- 01

- 28

- 039 DAL

- GW

- 324L

- LS

- 120314 364 NC

GLP10

- 01

- 01

- 28

- 040 DAL

- GW

- 324L

- HS

- 120314 682 82.5

**Average Concentration (ng/mL) ±**  **%RPD 270**  **ng/m L**  **± 0.37**  **%**

NA = Not Applicable NC = Not Calculated; the sample concen tration is greater than 2x the spike level. Samples analyzed using a 1:10 0 dilution factor.



### Table 20

. DAL GW RW 327R 1 20323

**PFOA**

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

GLP10

- 01

- 01

- 28

- 041 DAL

- GW

- RW327R

- 0

- 120323 698 NA

GLP10

- 01

- 01

- 28

- 042 DAL

- GW

- RW327R

- DB

- 120323 701 NA

GLP10

- 01

- 01

- 28

- 043 DAL

- GW

- RW327R

- LS

- 120323 779 NC

GLP10

- 01

- 01

- 28

- 044 DAL

- GW

- RW327R

- HS

- 120323 1130 86.1

**Average Concentration (ng/mL) ±**  **%RPD 700**  **ng/m L**  **± 0.43**  **%**

NA = Not Applicable

NC = Not Calcu lated; t he sample concentration is greater than 2x the spike level. Samples analyzed using a 1:10 0 dilution factor.



### Table 21

. DAL GW 328R 1 20314

**PFOA**

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

GLP10

- 01

- 01

- 28

- 045 DAL

- GW

- 328R

- 0

- 120314 335 NA

GLP10

- 01

- 01

- 28

- 046 DAL

- GW

- 328R

- DB

- 120314 333 NA

GLP10

- 01

- 01

- 28

- 047 DAL

- GW

- 328R

- LS

- 120314 424 NC

GLP10

- 01

- 01

- 28

- 048 DAL

- GW

- 328R

- HS

- 120314 772 87.6

**Average Concentration (ng/mL) ±**  **%RPD 334**  **ng/m L**  **± 0.60**  **%**

NA = Not Applicable
NC = Not Calculated; t he sample concentration is greater than 2x the spike level. Samples analyzed using a 1:10 0 dilution factor.

### Table 22

. DAL GW 328L 1 20314

**PFOA**

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

GLP 10

- 01

- 01

- 28

- 049 DAL

- GW

- 328L

- 0

- 120314 95.0 NA

GLP10

- 01

- 01

- 28

- 050 DAL

- GW

- 328L

- DB

- 120314 97.5 NA

GLP10

- 01

- 01

- 28

- 051 DAL

- GW

- 328L

- LS

- 120314 103 NC

GLP10

- 01

- 01

- 28

- 052 DAL

- GW

- 328L

- HS

- 120314 172 75.8

**Average Concentration (ng/mL) ±**  **%RPD 96.3**  **ng/m L**  **± 2.6**  **%**

NA = Not Applicable

NC = Not Calculated ; t he sample concentration is greater than 2x the spike level. Samples analyzed using a 1:10 dilution factor.



### Table 23

. DAL GW 330R 120314

**PFOA**

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

GLP10

- 01

- 01

- 28

- 053 DAL

- GW

- 330R

- 0

- 120314 331 NA

GLP10

- 01

- 01

- 28

- 054 DAL

- GW

- 330R

- DB

- 120314 339 NA

GLP10

- 01

- 01

- 28

- 055 DAL

- GW

- 330R

- LS

- 120314 763 85.6

GLP10

- 01

- 01

- 28

- 056 DAL

- GW

- 330R

- HS

- 120314 1200 86.5

**Average Concentration (ng/mL) ±**  **%RPD 335**  **ng/m L**  **± 2.4**  **%**

NA = Not Applicable NC = Not Calculated; the sample concentration is greater than 2x the spike level. Samples analyzed using a 1:100 dilution factor.



### Table 24

. DAL GW 330L 120314

**PFOA**

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

GLP10

- 01

- 01

- 28

- 057 DAL

- GW

- 330L

- 0

- 120314 296 NA

GLP10

- 01

- 01

- 28

- 058 DAL

- GW

- 330L

- DB

- 120314 297 NA

GLP10

- 01

- 01

- 28

- 059 DAL

- GW

- 330L

- LS

- 120314 378 NC

GLP10

- 01

- 01

- 28

- 060 DAL

- GW

- 330L

- HS

- 120314 707 82.1

**Average Concentration (ng/mL) ±**  **%RPD 297**  **ng/m L**  **± 0.34**  **%**

NA = Not Applicable NC = Not Calculated; the sample concentration is greater than 2x the spike level. Samples analyzed using a 1:10 0 dilution factor.

### Table 25

. DAL GW RW 331S 1 20328

**PFOA**

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

GLP10

- 01

- 01

- 28

- 061 DAL

- GW

- RW331S

- 0

- 120328 962 NA

GLP10

- 01

- 01

- 28

- 062 DAL

- GW

- RW331S

- DB

- 120328 918 NA

GLP10

- 01

- 01

- 28

- 063 DAL

- GW

- RW331S

- LS

- 120328 1300 72.0

GLP10

- 01

- 01

- 28

- 064 DAL

- GW

- RW331S

- HS

- 120328 1620 68.0 (1)

**Average Concentration (ng/mL) ±**  **%RPD 940**  **ng/m L**  **± 4.7**  **% (2)** 

NA = Not Applicable NC = Not Calculated; the sample concentration is greater than 2x the spike level. Samples analyzed using a 1:10 0 dilution factor. (1) FMS d id not meet acceptance criteria. (2) The method uncertainty has been adjusted to ± 32 %.



### Table 26

. DAL GW 335R 1 20322

**PFOA**

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

GLP10

- 01

- 01

- 28

- 065 DAL

- GW

- 335R

- 0

- 120322 3840 NA

GLP10

- 01

- 01

- 28

- 066 DAL

- GW

- 335R

- DB

- 120322 3930 NA

GLP10

- 01

- 01

- 28

- 067 DAL

- GW

- 335R

- LS

- 120322 NR (1) NC

GLP10

- 01

- 01

- 28

- 068 DAL

- GW

- 335R

- HS

- 120322 7760 77.5

**Average Concentration (ng/mL) ±**  **%RPD 3890**  **ng/m L**  **± 2.3**  **%**

NA = Not Applicable NC = Not Calculated; the sample concentration is greater than 2x the spike level. Sample, sample duplicate, and LS were analyzed using a 1:100 dilution factor. The HS was analyzed using a 1:500 dilution factor. (1 ) NR = not reportable; Sample concentration exceeded the calibration range.



### Table 27

. DAL GW GRS04 1 20328

**PFOA**

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

GLP10

- 01

- 01

- 28

- 069 DAL

- GW

- GRS04

- 0

- 120328 3930 NA

GLP10

- 01

- 01

- 28

- 070 DAL

- GW

- GRS04

- DB

- 120328 3780 NA

GLP10

- 01

- 01

- 28

- 071 DAL

- GW

- GRS04

- LS

- 120328 4460 NC

GLP10

- 01

- 01

- 28

- 072 DAL

- GW

- GRS04

- HS

- 120328 7380 70.5

**Average Conce ntration (ng/mL)**  **± %RPD**  **3860 ng/m**  **L ±**  **3.9 %** 

NA = Not Applicable NC = Not Calculated; the sample concentration is greater than 2x the spike level. Sample, sample duplicate, and LS were analyzed using a 1:100 dilution factor. The HS was analyzed using a 1:500 dilution fac tor.

### Table 28 . Trip Blank 1

**PFOA**

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

GLP10

- 01

- 01

- 28

- 074 DAL

- GW

- TRIP01

- 0

- <0.0240 NA

GLP10

- 01

- 01

- 28

- 075 DAL

- GW

- TRIP01

- LS

- 9.40 94.0

GLP10

- 01

- 01

- 28

- 076 DAL

- GW

- TRIP01

- MS

- 91.5 91.5

GLP10

- 01

- 01

- 28

- 077 DAL

- GW

- TRIP01

- HS

- 952 95.2

NA = Not Applicable The MS was analyzed using a 1:10 dilution factor. The HS was analyzed using a 1:100 dilution factor.



### Table 29 . Rinseate Blank

**PFOA**

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

GLP10

- 01

- 01

- 28

- 073 DAL

- GW

- 203L

- RB

- 120327 <0.0 24 0



## 10

8B 

## Conclusion

Laboratory control spikes and field m a trix spikes were used to determine the analytical method accuracy and precision for PFOA

. A nalysis was successfully completed following 3M Environme ntal Laboratory method ETS -8- 044. 1 described herein.



## 11

9B 

## Data/Sample Retention

All remaining sample s and associated project data (hardcopy and electronic) will be archived according to 3M Environmental Laboratory standard operating procedures.



## 12

10B 

## Attachments

Attachment A: Protocol Amendment 28 (General Project Outline) Attachment B: Representative Chromatograms and Calibration Curves

Attachment C : Analytical Method ETS -8- 044.1

Attachment D: Method DeviationGLP I 0-01-01 ; Interi m Repor t 2 8 Analysi s o f PFO A i n Groundwate r Decatur

, A L - 1s t Quarte r 201 2 Samplin g



## 13 Signatures



# S'j2 

# /zo/:

Clesto n Lange

, Ph.D.

, 3 M Principa l Analytica l Investigato r Dat e



## 4" y^y^ VQ-o7^

Willia m K

. Reagen

, Ph.D.

, 3 M Environmenta l Laborator y Departmen t Manage r Dat e

Gar y Hohensfei n ,^ponso r Representativ e Dat e

Jaisimh a Kesari

, Stud y Directo r Dat e

Pag e 2 4 o f 6 6

# A TTACHMENT 

# A: P ROTOCOL 

# A MENDMENT

# A TTACHMENT 

# B: R EPRESENTATIVE 

# S AMPLE 

# C HROMATOGRAMS AND


# C ALIBRATION 

# C URVE 

# ( S 

# )b120405a.rdb (PFOA): "Quadratic" Regression ("1 / x" weighting): y = -9.27e+003 x^2 + 1.24e+006 x + 1.74e+004 (r = 0.9989)0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80 85 90 95Concentration, ng/mL0.05.0e61.0e71.5e72.0e72.5e73.0e73.5e74.0e74.5e75.0e75.5e76.0e76.5e7

Area, countsWorkstation: ETSGINGERBatch Name: b120405a.dab*Data worked up by KJUPage 1 of 1Printing Time: 2:26:16 PMPrinting Date: Tuesday, April 10, 2012Sample Name: "b120405a018" Sample ID: "11012-10-9" File: "b120405a.wiff"Peak Name: "PFOA" Mass(es): "413.0/369.0 amu,413.0/219.0 amu,413.0/169.0 amu"Comment: "2.5 ng/mL FC std in Milli Q Water" Annotation: ""Sample Index: 18Sample Type: StandardConcentration: 2.40 ng/mLCalculated Conc: 2.62 ng/mLAcq. Date: 4/5/2012Acq. Time: 10:13:24 PMModified: YesRT Window: 30.0 secExpected RT: 15.7 minUse Relative RT: NoInt. Type: ManualRetention Time: 15.7 minArea: 3211528 countsHeight: 8.32e+005 cpsStart Time: 15.3 minEnd Time: 15.8 min13.5 14.0 14.5 15.0 15.5 16.0 16.5 17.0 17.5 18.0Time, min0.05.0e41.0e51.5e52.0e52.5e53.0e53.5e54.0e54.5e55.0e55.5e56.0e56.5e57.0e57.5e58.0e5

Intensity, cps15.6616.1515.5216.64Sample Name: "b120405a028" Sample ID: "Solvent Blank" File: "b120405a.wiff"Peak Name: "PFOA" Mass(es): "413.0/369.0 amu,413.0/219.0 amu,413.0/169.0 amu"Comment: "Milli Q Water TN12-0125" Annotation: ""Sample Index: 28Sample Type: UnknownConcentration: N/ACalculated Conc: < 0Acq. Date: 4/6/2012Acq. Time: 1:43:47 AMModified: NoProc. Algorithm: IntelliQuan - MQIINoise Percentage: 50Base. Sub. Window: 1.00 minPeak-Split. Factor: 4Report Largest Peak: NoMin. Peak Height: 0.00 cpsMin. Peak Width: 0.00 secSmoothing Width: 3 pointsRT Window: 30.0 secExpected RT: 15.7 minUse Relative RT: NoInt. Type: Base To BaseRetention Time: 15.6 minArea: 2180 countsHeight: 9.04e+002 cpsStart Time: 15.6 minEnd Time: 15.7 min13.5 14.0 14.5 15.0 15.5 16.0 16.5 17.0 17.5 18.0Time, min0.01.0e42.0e43.0e44.0e45.0e46.0e47.0e48.0e49.0e41.0e51.1e51.2e51.3e51.4e51.5e51.6e51.7e51.8e51.9e52.0e52.1e52.2e52.3e5

Intensity, cps16.13Sample Name: "b120405a029" Sample ID: "LCS-120405-1" File: "b120405a.wiff"Peak Name: "PFOA" Mass(es): "413.0/369.0 amu,413.0/219.0 amu,413.0/169.0 amu"Comment: "0.5ppb LCS" Annotation: ""Sample Index: 29Sample Type: QCConcentration: 0.477 ng/mLCalculated Conc: 0.433 ng/mLAcq. Date: 4/6/2012Acq. Time: 2:04:48 AMModified: YesRT Window: 30.0 secExpected RT: 15.7 minUse Relative RT: NoInt. Type: ManualRetention Time: 15.7 minArea: 553522 countsHeight: 1.52e+005 cpsStart Time: 15.4 minEnd Time: 15.7 min13.5 14.0 14.5 15.0 15.5 16.0 16.5 17.0 17.5 18.0Time, min0.01.0e42.0e43.0e44.0e45.0e46.0e47.0e48.0e49.0e41.0e51.1e51.2e51.3e51.4e51.5e51.6e51.7e51.8e51.9e52.0e52.1e52.2e52.3e5

Intensity, cps16.1315.6615.51Sample Name: "b120405a032" Sample ID: "LCS-120405-4" File: "b120405a.wiff"Peak Name: "PFOA" Mass(es): "413.0/369.0 amu,413.0/219.0 amu,413.0/169.0 amu"Comment: "5ppb LCS" Annotation: ""Sample Index: 32Sample Type: QCConcentration: 4.77 ng/mLCalculated Conc: 4.53 ng/mLAcq. Date: 4/6/2012Acq. Time: 3:08:03 AMModified: YesRT Window: 30.0 secExpected RT: 15.7 minUse Relative RT: NoInt. Type: ManualRetention Time: 15.7 minArea: 5455248 countsHeight: 1.38e+006 cpsStart Time: 15.3 minEnd Time: 15.8 min13.5 14.0 14.5 15.0 15.5 16.0 16.5 17.0 17.5 18.0Time, min0.05.0e41.0e51.5e52.0e52.5e53.0e53.5e54.0e54.5e55.0e55.5e56.0e56.5e57.0e57.5e58.0e58.5e59.0e59.5e51.0e61.1e61.1e61.2e61.2e61.3e61.3e61.4e6

Intensity, cps15.6515.5116.14*** Buster J2930203Batch Name: b120405a.dabData printed by STWPrinting Time: 1:53:31 PMPrinting Date: Tuesday, May 01, 2012Page 1 of 8Sample Name: "b120405a035" Sample ID: "LCS-120405-7" File: "b120405a.wiff"Peak Name: "PFOA" Mass(es): "413.0/369.0 amu,413.0/219.0 amu,413.0/169.0 amu"Comment: "30ppb LCS" Annotation: ""Sample Index: 35Sample Type: QCConcentration: 28.7 ng/mLCalculated Conc: 25.0 ng/mLAcq. Date: 4/6/2012Acq. Time: 4:11:14 AMModified: YesRT Window: 30.0 secExpected RT: 15.7 minUse Relative RT: NoInt. Type: ManualRetention Time: 15.7 minArea: 25307984 countsHeight: 5.53e+006 cpsStart Time: 15.3 minEnd Time: 15.9 min13.5 14.0 14.5 15.0 15.5 16.0 16.5 17.0 17.5 18.0Time, min0.02.0e54.0e56.0e58.0e51.0e61.2e61.4e61.6e61.8e62.0e62.2e62.4e62.6e62.8e63.0e63.2e63.4e63.6e63.8e64.0e64.2e64.4e64.6e64.8e65.0e65.2e65.4e6

Intensity, cps15.6515.5116.13Sample Name: "b120405a044" Sample ID: "GLP10-01-01-28-073" File: "b120405a.wiff"Peak Name: "PFOA" Mass(es): "413.0/369.0 amu,413.0/219.0 amu,413.0/169.0 amu"Comment: "DAL-GW-203L-RB-" Annotation: ""Sample Index: 44Sample Type: UnknownConcentration: N/ACalculated Conc: < 0Acq. Date: 4/6/2012Acq. Time: 7:20:58 AMModified: NoProc. Algorithm: IntelliQuan - MQIINoise Percentage: 50Base. Sub. Window: 1.00 minPeak-Split. Factor: 4Report Largest Peak: NoMin. Peak Height: 0.00 cpsMin. Peak Width: 0.00 secSmoothing Width: 3 pointsRT Window: 30.0 secExpected RT: 15.7 minUse Relative RT: NoInt. Type: Base To BaseRetention Time: 15.7 minArea: 4736 countsHeight: 1.35e+003 cpsStart Time: 15.6 minEnd Time: 15.7 min13.5 14.0 14.5 15.0 15.5 16.0 16.5 17.0 17.5 18.0Time, min0.05000.01.0e41.5e42.0e42.5e43.0e43.5e44.0e44.5e45.0e45.5e46.0e46.5e47.0e47.5e48.0e48.5e4

Intensity, cpsSample Name: "b120405a053" Sample ID: "GLP10-01-01-28-074" File: "b120405a.wiff"Peak Name: "PFOA" Mass(es): "413.0/369.0 amu,413.0/219.0 amu,413.0/169.0 amu"Comment: "DAL-GW-TRIP01-0-" Annotation: ""Sample Index: 53Sample Type: UnknownConcentration: N/ACalculated Conc: < 0Acq. Date: 4/6/2012Acq. Time: 10:30:37 AMModified: NoProc. Algorithm: IntelliQuan - MQIINoise Percentage: 50Base. Sub. Window: 1.00 minPeak-Split. Factor: 4Report Largest Peak: NoMin. Peak Height: 0.00 cpsMin. Peak Width: 0.00 secSmoothing Width: 3 pointsRT Window: 30.0 secExpected RT: 15.7 minUse Relative RT: NoInt. Type: Base To BaseRetention Time: 15.7 minArea: 3210 countsHeight: 1.27e+003 cpsStart Time: 15.6 minEnd Time: 15.7 min13.5 14.0 14.5 15.0 15.5 16.0 16.5 17.0 17.5 18.0Time, min0.05000.01.0e41.5e42.0e42.5e43.0e43.5e44.0e44.5e45.0e45.5e46.0e46.5e47.0e47.5e48.0e4

Intensity, cps16.1318.0917.8517.3216.6517.0815.97Sample Name: "b120405a055" Sample ID: "GLP10-01-01-28-076" File: "b120405a.wiff"Peak Name: "PFOA" Mass(es): "413.0/369.0 amu,413.0/219.0 amu,413.0/169.0 amu"Comment: "DAL-GW-TRIP01-MS-" Annotation: ""Sample Index: 55Sample Type: UnknownConcentration: N/ACalculated Conc: 91.5 ng/mLAcq. Date: 4/6/2012Acq. Time: 11:12:48 AMModified: YesRT Window: 30.0 secExpected RT: 15.7 minUse Relative RT: NoInt. Type: ManualRetention Time: 15.7 minArea: 10615474 countsHeight: 3.09e+006 cpsStart Time: 15.4 minEnd Time: 15.8 min13.5 14.0 14.5 15.0 15.5 16.0 16.5 17.0 17.5 18.0Time, min0.02.0e54.0e56.0e58.0e51.0e61.2e61.4e61.6e61.8e62.0e62.2e62.4e62.6e62.8e63.0e6

Intensity, cps15.6616.1315.51*** Buster J2930203Batch Name: b120405a.dabData printed by STWPrinting Time: 1:53:31 PMPrinting Date: Tuesday, May 01, 2012Page 2 of 8Sample Name: "b120405a138" Sample ID: "GLP10-01-01-28-001" File: "b120405a.wiff"Peak Name: "PFOA" Mass(es): "413.0/369.0 amu,413.0/219.0 amu,413.0/169.0 amu"Comment: "DAL-GW-203L-0-" Annotation: ""Sample Index: 138Sample Type: UnknownConcentration: N/ACalculated Conc: 178. ng/mLAcq. Date: 4/7/2012Acq. Time: 4:22:47 PMModified: YesRT Window: 30.0 secExpected RT: 15.7 minUse Relative RT: NoInt. Type: ManualRetention Time: 15.6 minArea: 2203766 countsHeight: 5.34e+005 cpsStart Time: 15.3 minEnd Time: 15.7 min13.5 14.0 14.5 15.0 15.5 16.0 16.5 17.0 17.5 18.0Time, min0.02.0e44.0e46.0e48.0e41.0e51.2e51.4e51.6e51.8e52.0e52.2e52.4e52.6e52.8e53.0e53.2e53.4e53.6e53.8e54.0e54.2e54.4e54.6e54.8e55.0e55.2e5

Intensity, cps15.61Sample Name: "b120405a142" Sample ID: "GLP10-01-01-28-005" File: "b120405a.wiff"Peak Name: "PFOA" Mass(es): "413.0/369.0 amu,413.0/219.0 amu,413.0/169.0 amu"Comment: "DAL-GW-220R-0-" Annotation: ""Sample Index: 142Sample Type: UnknownConcentration: N/ACalculated Conc: 38.6 ng/mLAcq. Date: 4/7/2012Acq. Time: 5:47:04 PMModified: YesRT Window: 30.0 secExpected RT: 15.7 minUse Relative RT: NoInt. Type: ManualRetention Time: 15.6 minArea: 4675118 countsHeight: 1.11e+006 cpsStart Time: 15.2 minEnd Time: 15.8 min13.5 14.0 14.5 15.0 15.5 16.0 16.5 17.0 17.5 18.0Time, min0.005.00e41.00e51.50e52.00e52.50e53.00e53.50e54.00e54.50e55.00e55.50e56.00e56.50e57.00e57.50e58.00e58.50e59.00e59.50e51.00e61.05e61.10e6

Intensity, cps15.6115.4716.08Sample Name: "b120405a149" Sample ID: "GLP10-01-01-28-009" File: "b120405a.wiff"Peak Name: "PFOA" Mass(es): "413.0/369.0 amu,413.0/219.0 amu,413.0/169.0 amu"Comment: "DAL-GW-220L-0-" Annotation: ""Sample Index: 149Sample Type: UnknownConcentration: N/ACalculated Conc: 48.1 ng/mLAcq. Date: 4/7/2012Acq. Time: 8:14:43 PMModified: YesRT Window: 30.0 secExpected RT: 15.7 minUse Relative RT: NoInt. Type: ManualRetention Time: 15.6 minArea: 5787691 countsHeight: 1.35e+006 cpsStart Time: 15.3 minEnd Time: 15.8 min13.5 14.0 14.5 15.0 15.5 16.0 16.5 17.0 17.5 18.0Time, min0.05.0e41.0e51.5e52.0e52.5e53.0e53.5e54.0e54.5e55.0e55.5e56.0e56.5e57.0e57.5e58.0e58.5e59.0e59.5e51.0e61.1e61.1e61.2e61.2e61.3e61.3e61.4e6

Intensity, cps15.6115.4616.07Sample Name: "b120405a153" Sample ID: "GLP10-01-01-28-013" File: "b120405a.wiff"Peak Name: "PFOA" Mass(es): "413.0/369.0 amu,413.0/219.0 amu,413.0/169.0 amu"Comment: "DAL-GW-222R-0-" Annotation: ""Sample Index: 153Sample Type: UnknownConcentration: N/ACalculated Conc: 332. ng/mLAcq. Date: 4/7/2012Acq. Time: 9:39:11 PMModified: YesRT Window: 30.0 secExpected RT: 15.7 minUse Relative RT: NoInt. Type: ManualRetention Time: 15.6 minArea: 4046752 countsHeight: 9.11e+005 cpsStart Time: 15.2 minEnd Time: 15.8 min13.5 14.0 14.5 15.0 15.5 16.0 16.5 17.0 17.5 18.0Time, min0.05.0e41.0e51.5e52.0e52.5e53.0e53.5e54.0e54.5e55.0e55.5e56.0e56.5e57.0e57.5e58.0e58.5e59.0e5

Intensity, cps15.6115.46*** Buster J2930203Batch Name: b120405a.dabData printed by STWPrinting Time: 1:53:31 PMPrinting Date: Tuesday, May 01, 2012Page 3 of 8Sample Name: "b120405a160" Sample ID: "GLP10-01-01-28-017" File: "b120405a.wiff"Peak Name: "PFOA" Mass(es): "413.0/369.0 amu,413.0/219.0 amu,413.0/169.0 amu"Comment: "DAL-GW-227R-0-" Annotation: ""Sample Index: 160Sample Type: UnknownConcentration: N/ACalculated Conc: 339. ng/mLAcq. Date: 4/8/2012Acq. Time: 12:06:55 AMModified: YesRT Window: 30.0 secExpected RT: 15.7 minUse Relative RT: NoInt. Type: ManualRetention Time: 15.6 minArea: 4125014 countsHeight: 1.04e+006 cpsStart Time: 15.2 minEnd Time: 15.8 min13.5 14.0 14.5 15.0 15.5 16.0 16.5 17.0 17.5 18.0Time, min0.005.00e41.00e51.50e52.00e52.50e53.00e53.50e54.00e54.50e55.00e55.50e56.00e56.50e57.00e57.50e58.00e58.50e59.00e59.50e51.00e6

Intensity, cps15.6115.4616.06Sample Name: "b120405a163" Sample ID: "GLP10-01-01-28-020" File: "b120405a.wiff"Peak Name: "PFOA" Mass(es): "413.0/369.0 amu,413.0/219.0 amu,413.0/169.0 amu"Comment: "DAL-GW-227R-HS-" Annotation: ""Sample Index: 163Sample Type: UnknownConcentration: N/ACalculated Conc: 764. ng/mLAcq. Date: 4/8/2012Acq. Time: 1:10:21 AMModified: YesRT Window: 30.0 secExpected RT: 15.7 minUse Relative RT: NoInt. Type: ManualRetention Time: 15.6 minArea: 8978196 countsHeight: 2.43e+006 cpsStart Time: 15.3 minEnd Time: 15.9 min13.5 14.0 14.5 15.0 15.5 16.0 16.5 17.0 17.5 18.0Time, min0.01.0e52.0e53.0e54.0e55.0e56.0e57.0e58.0e59.0e51.0e61.1e61.2e61.3e61.4e61.5e61.6e61.7e61.8e61.9e62.0e62.1e62.2e62.3e62.4e6

Intensity, cps15.6115.47Sample Name: "b120405a164" Sample ID: "GLP10-01-01-28-021" File: "b120405a.wiff"Peak Name: "PFOA" Mass(es): "413.0/369.0 amu,413.0/219.0 amu,413.0/169.0 amu"Comment: "DAL-GW-227L-0-" Annotation: ""Sample Index: 164Sample Type: UnknownConcentration: N/ACalculated Conc: 82.8 ng/mLAcq. Date: 4/8/2012Acq. Time: 1:31:26 AMModified: YesRT Window: 30.0 secExpected RT: 15.7 minUse Relative RT: NoInt. Type: ManualRetention Time: 15.6 minArea: 1040156 countsHeight: 2.42e+005 cpsStart Time: 15.2 minEnd Time: 15.7 min13.5 14.0 14.5 15.0 15.5 16.0 16.5 17.0 17.5 18.0Time, min0.01.0e42.0e43.0e44.0e45.0e46.0e47.0e48.0e49.0e41.0e51.1e51.2e51.3e51.4e51.5e51.6e51.7e51.8e51.9e52.0e52.1e52.2e52.3e52.4e5

Intensity, cps15.61Sample Name: "b120405b171" Sample ID: "GLP10-01-01-28-025" File: "b120405a.wiff"Peak Name: "PFOA" Mass(es): "413.0/369.0 amu,413.0/219.0 amu,413.0/169.0 amu"Comment: "DAL-GW-310R-0-" Annotation: ""Sample Index: 184Sample Type: UnknownConcentration: N/ACalculated Conc: 966. ng/mLAcq. Date: 4/9/2012Acq. Time: 12:37:43 PMModified: YesRT Window: 30.0 secExpected RT: 15.7 minUse Relative RT: NoInt. Type: ManualRetention Time: 15.6 minArea: 11162173 countsHeight: 2.73e+006 cpsStart Time: 15.3 minEnd Time: 15.9 min13.5 14.0 14.5 15.0 15.5 16.0 16.5 17.0 17.5 18.0Time, min0.01.0e52.0e53.0e54.0e55.0e56.0e57.0e58.0e59.0e51.0e61.1e61.2e61.3e61.4e61.5e61.6e61.7e61.8e61.9e62.0e62.1e62.2e62.3e62.4e62.5e62.6e62.7e6

Intensity, cps15.6515.5016.1115.34*** Buster J2930203Batch Name: b120405a.dabData printed by STWPrinting Time: 1:53:31 PMPrinting Date: Tuesday, May 01, 2012Page 4 of 8Sample Name: "b120405b175" Sample ID: "GLP10-01-01-28-029" File: "b120405a.wiff"Peak Name: "PFOA" Mass(es): "413.0/369.0 amu,413.0/219.0 amu,413.0/169.0 amu"Comment: "DAL-GW-RW312R-0-" Annotation: ""Sample Index: 188Sample Type: UnknownConcentration: N/ACalculated Conc: 941. ng/mLAcq. Date: 4/9/2012Acq. Time: 2:02:08 PMModified: YesRT Window: 30.0 secExpected RT: 15.7 minUse Relative RT: NoInt. Type: ManualRetention Time: 15.6 minArea: 10902692 countsHeight: 2.61e+006 cpsStart Time: 15.2 minEnd Time: 15.9 min13.5 14.0 14.5 15.0 15.5 16.0 16.5 17.0 17.5 18.0Time, min0.01.0e52.0e53.0e54.0e55.0e56.0e57.0e58.0e59.0e51.0e61.1e61.2e61.3e61.4e61.5e61.6e61.7e61.8e61.9e62.0e62.1e62.2e62.3e62.4e62.5e62.6e6

Intensity, cps15.6315.49Sample Name: "b120405b177" Sample ID: "GLP10-01-01-28-031" File: "b120405a.wiff"Peak Name: "PFOA" Mass(es): "413.0/369.0 amu,413.0/219.0 amu,413.0/169.0 amu"Comment: "DAL-GW-RW312R-LS-" Annotation: ""Sample Index: 190Sample Type: UnknownConcentration: N/ACalculated Conc: 1670. ng/mLAcq. Date: 4/9/2012Acq. Time: 2:44:22 PMModified: YesRT Window: 30.0 secExpected RT: 15.7 minUse Relative RT: NoInt. Type: ManualRetention Time: 15.6 minArea: 18236621 countsHeight: 4.49e+006 cpsStart Time: 15.3 minEnd Time: 15.9 min13.5 14.0 14.5 15.0 15.5 16.0 16.5 17.0 17.5 18.0Time, min0.02.0e54.0e56.0e58.0e51.0e61.2e61.4e61.6e61.8e62.0e62.2e62.4e62.6e62.8e63.0e63.2e63.4e63.6e63.8e64.0e64.2e64.4e6

Intensity, cps15.6315.4916.09Sample Name: "b120405b182" Sample ID: "GLP10-01-01-28-033" File: "b120405a.wiff"Peak Name: "PFOA" Mass(es): "413.0/369.0 amu,413.0/219.0 amu,413.0/169.0 amu"Comment: "DAL-GW-317L-0-" Annotation: ""Sample Index: 195Sample Type: UnknownConcentration: N/ACalculated Conc: 0.261 ng/mLAcq. Date: 4/9/2012Acq. Time: 4:29:56 PMModified: YesRT Window: 30.0 secExpected RT: 15.7 minUse Relative RT: NoInt. Type: ManualRetention Time: 15.6 minArea: 341532 countsHeight: 9.56e+004 cpsStart Time: 15.4 minEnd Time: 15.7 min13.5 14.0 14.5 15.0 15.5 16.0 16.5 17.0 17.5 18.0Time, min0.01.0e42.0e43.0e44.0e45.0e46.0e47.0e48.0e49.0e41.0e51.1e51.2e51.3e51.4e51.5e51.6e51.7e51.8e51.9e52.0e5

Intensity, cpsSample Name: "b120405b186" Sample ID: "GLP10-01-01-28-037" File: "b120405a.wiff"Peak Name: "PFOA" Mass(es): "413.0/369.0 amu,413.0/219.0 amu,413.0/169.0 amu"Comment: "DAL-GW-324L-0-" Annotation: ""Sample Index: 199Sample Type: UnknownConcentration: N/ACalculated Conc: 270. ng/mLAcq. Date: 4/9/2012Acq. Time: 5:54:23 PMModified: YesRT Window: 30.0 secExpected RT: 15.7 minUse Relative RT: NoInt. Type: ManualRetention Time: 15.6 minArea: 3311225 countsHeight: 8.27e+005 cpsStart Time: 15.3 minEnd Time: 15.8 min13.5 14.0 14.5 15.0 15.5 16.0 16.5 17.0 17.5 18.0Time, min0.05.0e41.0e51.5e52.0e52.5e53.0e53.5e54.0e54.5e55.0e55.5e56.0e56.5e57.0e57.5e58.0e5

Intensity, cps15.6216.0715.48*** Buster J2930203Batch Name: b120405a.dabData printed by STWPrinting Time: 1:53:31 PMPrinting Date: Tuesday, May 01, 2012Page 5 of 8Sample Name: "b120405b193" Sample ID: "GLP10-01-01-28-041" File: "b120405a.wiff"Peak Name: "PFOA" Mass(es): "413.0/369.0 amu,413.0/219.0 amu,413.0/169.0 amu"Comment: "DAL-GW-RW327R-0-" Annotation: ""Sample Index: 206Sample Type: UnknownConcentration: N/ACalculated Conc: 698. ng/mLAcq. Date: 4/9/2012Acq. Time: 8:22:15 PMModified: YesRT Window: 30.0 secExpected RT: 15.7 minUse Relative RT: NoInt. Type: ManualRetention Time: 15.6 minArea: 8244882 countsHeight: 1.92e+006 cpsStart Time: 15.2 minEnd Time: 15.8 min13.5 14.0 14.5 15.0 15.5 16.0 16.5 17.0 17.5 18.0Time, min0.01.0e52.0e53.0e54.0e55.0e56.0e57.0e58.0e59.0e51.0e61.1e61.2e61.3e61.4e61.5e61.6e61.7e61.8e61.9e6

Intensity, cps15.6015.4616.06Sample Name: "b120405b197" Sample ID: "GLP10-01-01-28-045" File: "b120405a.wiff"Peak Name: "PFOA" Mass(es): "413.0/369.0 amu,413.0/219.0 amu,413.0/169.0 amu"Comment: "DAL-GW-328R-0-" Annotation: ""Sample Index: 210Sample Type: UnknownConcentration: N/ACalculated Conc: 335. ng/mLAcq. Date: 4/9/2012Acq. Time: 9:46:45 PMModified: YesRT Window: 30.0 secExpected RT: 15.7 minUse Relative RT: NoInt. Type: ManualRetention Time: 15.6 minArea: 4075406 countsHeight: 1.05e+006 cpsStart Time: 15.3 minEnd Time: 15.7 min13.5 14.0 14.5 15.0 15.5 16.0 16.5 17.0 17.5 18.0Time, min0.005.00e41.00e51.50e52.00e52.50e53.00e53.50e54.00e54.50e55.00e55.50e56.00e56.50e57.00e57.50e58.00e58.50e59.00e59.50e51.00e61.05e6

Intensity, cps15.6115.4716.06Sample Name: "b120405b204" Sample ID: "GLP10-01-01-28-049" File: "b120405a.wiff"Peak Name: "PFOA" Mass(es): "413.0/369.0 amu,413.0/219.0 amu,413.0/169.0 amu"Comment: "DAL-GW-328L-0-" Annotation: ""Sample Index: 217Sample Type: UnknownConcentration: N/ACalculated Conc: 95.0 ng/mLAcq. Date: 4/10/2012Acq. Time: 12:14:29 AMModified: YesRT Window: 30.0 secExpected RT: 15.7 minUse Relative RT: NoInt. Type: ManualRetention Time: 15.6 minArea: 10998487 countsHeight: 2.29e+006 cpsStart Time: 15.2 minEnd Time: 15.9 min13.5 14.0 14.5 15.0 15.5 16.0 16.5 17.0 17.5 18.0Time, min0.01.0e52.0e53.0e54.0e55.0e56.0e57.0e58.0e59.0e51.0e61.1e61.2e61.3e61.4e61.5e61.6e61.7e61.8e61.9e62.0e62.1e62.2e6

Intensity, cps15.6115.4616.06Sample Name: "b120405b207" Sample ID: "GLP10-01-01-28-052" File: "b120405a.wiff"Peak Name: "PFOA" Mass(es): "413.0/369.0 amu,413.0/219.0 amu,413.0/169.0 amu"Comment: "DAL-GW-328L-HS-" Annotation: ""Sample Index: 220Sample Type: UnknownConcentration: N/ACalculated Conc: 172. ng/mLAcq. Date: 4/10/2012Acq. Time: 1:17:55 AMModified: YesRT Window: 30.0 secExpected RT: 15.7 minUse Relative RT: NoInt. Type: ManualRetention Time: 15.6 minArea: 18646982 countsHeight: 4.42e+006 cpsStart Time: 15.2 minEnd Time: 15.9 min13.5 14.0 14.5 15.0 15.5 16.0 16.5 17.0 17.5 18.0Time, min0.02.0e54.0e56.0e58.0e51.0e61.2e61.4e61.6e61.8e62.0e62.2e62.4e62.6e62.8e63.0e63.2e63.4e63.6e63.8e64.0e64.2e64.4e6

Intensity, cps15.6115.4616.06*** Buster J2930203Batch Name: b120405a.dabData printed by STWPrinting Time: 1:53:31 PMPrinting Date: Tuesday, May 01, 2012Page 6 of 8Sample Name: "b120405b208" Sample ID: "GLP10-01-01-28-053" File: "b120405a.wiff"Peak Name: "PFOA" Mass(es): "413.0/369.0 amu,413.0/219.0 amu,413.0/169.0 amu"Comment: "DAL-GW-330R-0-" Annotation: ""Sample Index: 221Sample Type: UnknownConcentration: N/ACalculated Conc: 331. ng/mLAcq. Date: 4/10/2012Acq. Time: 1:39:01 AMModified: YesRT Window: 30.0 secExpected RT: 15.7 minUse Relative RT: NoInt. Type: ManualRetention Time: 15.6 minArea: 4035184 countsHeight: 1.03e+006 cpsStart Time: 15.2 minEnd Time: 15.8 min13.5 14.0 14.5 15.0 15.5 16.0 16.5 17.0 17.5 18.0Time, min0.005.00e41.00e51.50e52.00e52.50e53.00e53.50e54.00e54.50e55.00e55.50e56.00e56.50e57.00e57.50e58.00e58.50e59.00e59.50e51.00e6

Intensity, cps15.61Sample Name: "b120405b215" Sample ID: "GLP10-01-01-28-057" File: "b120405a.wiff"Peak Name: "PFOA" Mass(es): "413.0/369.0 amu,413.0/219.0 amu,413.0/169.0 amu"Comment: "DAL-GW-330L-0-" Annotation: ""Sample Index: 228Sample Type: UnknownConcentration: N/ACalculated Conc: 296. ng/mLAcq. Date: 4/10/2012Acq. Time: 4:07:07 AMModified: YesRT Window: 30.0 secExpected RT: 15.7 minUse Relative RT: NoInt. Type: ManualRetention Time: 15.6 minArea: 3622901 countsHeight: 9.25e+005 cpsStart Time: 15.2 minEnd Time: 15.8 min13.5 14.0 14.5 15.0 15.5 16.0 16.5 17.0 17.5 18.0Time, min0.05.0e41.0e51.5e52.0e52.5e53.0e53.5e54.0e54.5e55.0e55.5e56.0e56.5e57.0e57.5e58.0e58.5e59.0e5

Intensity, cps15.6015.4616.05Sample Name: "b120405b219" Sample ID: "GLP10-01-01-28-061" File: "b120405a.wiff"Peak Name: "PFOA" Mass(es): "413.0/369.0 amu,413.0/219.0 amu,413.0/169.0 amu"Comment: "DAL-GW-RW331S-0-" Annotation: ""Sample Index: 232Sample Type: UnknownConcentration: N/ACalculated Conc: 962. ng/mLAcq. Date: 4/10/2012Acq. Time: 5:31:32 AMModified: YesRT Window: 30.0 secExpected RT: 15.7 minUse Relative RT: NoInt. Type: ManualRetention Time: 15.6 minArea: 11127866 countsHeight: 2.63e+006 cpsStart Time: 15.2 minEnd Time: 15.9 min13.5 14.0 14.5 15.0 15.5 16.0 16.5 17.0 17.5 18.0Time, min0.01.0e52.0e53.0e54.0e55.0e56.0e57.0e58.0e59.0e51.0e61.1e61.2e61.3e61.4e61.5e61.6e61.7e61.8e61.9e62.0e62.1e62.2e62.3e62.4e62.5e62.6e6

Intensity, cps15.6115.4616.05Sample Name: "b120405b226" Sample ID: "GLP10-01-01-28-065" File: "b120405a.wiff"Peak Name: "PFOA" Mass(es): "413.0/369.0 amu,413.0/219.0 amu,413.0/169.0 amu"Comment: "DAL-GW-335R-0-" Annotation: ""Sample Index: 239Sample Type: UnknownConcentration: N/ACalculated Conc: 3840. ng/mLAcq. Date: 4/10/2012Acq. Time: 7:59:20 AMModified: YesRT Window: 30.0 secExpected RT: 15.7 minUse Relative RT: NoInt. Type: ManualRetention Time: 15.6 minArea: 34116185 countsHeight: 6.67e+006 cpsStart Time: 15.2 minEnd Time: 15.8 min13.5 14.0 14.5 15.0 15.5 16.0 16.5 17.0 17.5 18.0Time, min0.05.0e51.0e61.5e62.0e62.5e63.0e63.5e64.0e64.5e65.0e65.5e66.0e66.5e6

Intensity, cps15.5815.43*** Buster J2930203Batch Name: b120405a.dabData printed by STWPrinting Time: 1:53:31 PMPrinting Date: Tuesday, May 01, 2012Page 7 of 8Sample Name: "b120405b230" Sample ID: "GLP10-01-01-28-069" File: "b120405a.wiff"Peak Name: "PFOA" Mass(es): "413.0/369.0 amu,413.0/219.0 amu,413.0/169.0 amu"Comment: "DAL-GW-GRS04-0-" Annotation: ""Sample Index: 243Sample Type: UnknownConcentration: N/ACalculated Conc: 3930. ng/mLAcq. Date: 4/10/2012Acq. Time: 9:23:46 AMModified: YesRT Window: 30.0 secExpected RT: 15.7 minUse Relative RT: NoInt. Type: ManualRetention Time: 15.6 minArea: 34595866 countsHeight: 6.16e+006 cpsStart Time: 15.2 minEnd Time: 15.8 min13.5 14.0 14.5 15.0 15.5 16.0 16.5 17.0 17.5 18.0Time, min0.05.0e51.0e61.5e62.0e62.5e63.0e63.5e64.0e64.5e65.0e65.5e66.0e6

Intensity, cps15.5815.44*** Buster J2930203Batch Name: b120405a.dabData printed by STWPrinting Time: 1:53:31 PMPrinting Date: Tuesday, May 01, 2012Page 8 of 8

# A TTACHMENT 

# C: A NALYTICAL 

# M ETHOD 

# ( S 

# )

### ETS -8- 044. 1 Page 2 of 22 Method of Analysis for the Determination of Perfluorinated Compounds in Wate r by LC/MS/MS; Direct Injection Analysis 

## 1 Scope and Application

This method describes the direct injection analysis of perfluorinated compounds (PFCs) from water matrices using high

- performance liquid chromatography tandem mass spectrometry (HPLC/MS/MS). The method is generally applicable but not limited to the measurement of perfluoroalkyl sulfonamides and perfluorinated alkyl acids (PFAAs) such as perfluorosulfonic acids (PFSAs) and perfluorocarboxylic acids (PFCAs) (Table 1). Water samples containing heavy particulate may require preparation by an alternate method such as ETS -8- 154

“ Determination of Perfluorinated Acids, Alcohols, Amides, and Sulfonates In Water By Solid Phase Extraction and High Performance Liquid Chromatography/Mass Spectrometry ”. The method is applicable to both external standard and internal standard calibration 1



### .

Table 1. Representative Tar get Analytes

**Acronym Analyte**  **Chemical Abstract Services Registry Number (CASRN)** 

PFBA (C4 Acid) Perfluorobutanoic acid 375

- 22

- 4

PFPeA (C5 Acid) Perfluoropentanoic acid 2706

- 90

- 3

PFHxA (C6 Acid) Perfluorohexanoic acid 307

- 24

- 4

PFHpA (C7 Acid) Perfluoroheptanoic acid 375

- 85

- 9

PFOA (C8 Acid) Perfluorooctanoic acid 335

- 67

- 1

PFNA (C9 Acid) Perfluorononanoic acid 375

- 95

- 1

PFDA (C10 Acid) Perfluorodecanoic acid 335

- 76

- 2

PFUnA (C11 Acid) Perfluoroundecanoic acid 2058

- 94

- 8

PFDoA (C12 Acid) Perfluorododecanoic acid 307

- 55

- 1

PF TrD A (C1 3 Acid) Perfluorotridecanoic acid 72629

- 94

- 8

PFBS (C4 Sulfonate) Perfluorobutanesulfonic acid 375

- 73

- 5

PFHS (C6 Sulfonate) Perfluorohexanesulfonic acid 355

- 46

- 4

PFOS (C8 Sulfonate) Perfluorooctanesulfonic acid 1763

- 23

- 1

FBSA (C4 Sulfonamide Perfluorobutanesulfonamide 30334

- 69

- 1

FOSA (C8 Sulfonamide) Pefluorooctanesulfonamide 754

- 91

- 6



### The Minimum Reporting Level (MRL) is the Limit of Quantitation (LOQ) that meets Data Quality Objectives (DQOs) that are developed based on the intended use of this method.

Method Flexibility – This is a performance

- based method and may be generally applied to the determination of perfluorinated compounds in water matrices when analysis batch quality

c ontrol ( QC ) criteria are met 2



### . Each set of samples are prepared in an analysis batch with calibration standards, LCS s, blanks, and continuing calibration check standards analyzed on the same instrument during a time period that begins and ends with the analysis of the appropriate continuing calibration check standards. The laboratory is permitted to modify the LC column, mobile phase composition, LC conditions, and MS/MS conditions. Method modifications should be considered to improve method performance or to meet data quality objectives for the study. In all cases where method modifications are implemented, the batch

1 The method is supported by validation with internal standard calibration for C4

- C13 PFCAs, C4, C6, and C8 PFSAs, and C8 perfluoroalkane sulfonamide in laboratory control samples under 3M method validation E11

- 0667.

2 Guidance for establishing method QC Criteria based on a.) FDA May 2001, “Guidance for Industry, Bioanalytical

Method Vali dation”, b.) EPA Method 537, and c.) European Commission: Guidance for Generating and Reporting Methods of Analysis in Support of Pre

- registration Data Requirements for Annex II (Part A, section 4) and Annex III (Part A,section 5) of Directive 91/414, SANCO/3029/99 rev. 4 (11/07/00).

### ETS -8- 044. 1 Page 3 of 22 Method of Analysis for the Determination of Perfluorinated Compounds in Wate r by LC/MS/MS; Direct Injection Analysis analytical QCs ( section 9) must be completed and pass QC acceptance criteria ( section 13 ) if the data from the analytical batch are to be reported

.



## 2 Method Summary

Water samples are analyzed as neat aqueous sample or as solvent diluted aqueous samples by direct injection using LC/ MS/MS. Samples containing heavy particulate may not be suitable for analysis by this method. Samples containing suspended particulate should be centrifuge d or filtered prior to removing a sample aliquot or diluting with solvent

. The water sample is mixe d well prior to removing an aliquot or diluting, if necessary, with ASTM Type I water, HPLC water, other suitable water, or solvent (methanol).

Quantitation is by stable isotope internal standard calibration in laboratory reagent water. All perfluorinat ed compounds ( PFC s) target analyte concentrations of perfluorosulfonic acids (PFSAs) and perfluorocarboxylic acids (PFCAs) are reported as anions and corrected for

their salt or free acid forms. Alternatively, quantitation may be performed by external

st andard calibration.

This is a performance

- based method. Method uncertainty for each target analyte is determined for each analytical batch using multiple laboratory control spikes at multiple concentrations. This method also requires that the precision and accuracy for each sample be determined using field matrix spikes to verify that the method is applicable to each sample

matrix.

Calibration standards for PFUnA, PFDoA, PFTrDA, and FOSA have been found to be

un stable for more than 2 days in 100% water. Samples requiring analysis for these compounds by this method should be diluted 1:1 with methanol and analyzed against a calibration curve prepared in 1:1 synthetic groundwater:MeOH.



## 3 Definitions

3.1 Analysis Batch

A set of study samples that are prepared with calibration standards, laboratory control samples, and procedural blanks , and analyzed on the same instrument during a time period that begins and ends with the analysis of the appropriate continuing calibration check

standards.



## 3.2 Analytical Sample

A portion of a laboratory sample prepared for analysis.



## 3.3 Calibration Standard

A solution prepared by spiking a known volume of the Working Standard (WS) into a predete rmined amount of ASTM Type I, HPLC grade water, or other suitable water (i.e. matrix water), and analyzed according to this method. Calibration standards are used to calibrate the instrument response with respect to analyte concentration.



## 3.4 Laboratory Duplicate Sample (LDS, or Lab Dup)

A laboratory duplicate sample is a separate aliquot of a sample taken in the analytical laboratory that is analyzed separately with identical procedures. Analysis of LDSs compared to that of the first aliquot give a measure of the precision associated with laboratory procedures, but not with sample collection, preservation, or storage procedures.

### ETS -8- 044. 1 Page 4 of 22 Method of Analysis for the Determination of Perfluorinated Compounds in Wate r by LC/MS/MS; Direct Injection Analysis 

## 3.5 Field Blank (FB)/Trip Blank (TB)

ASTM Type I, HPLC grade water, or other suitable water, placed in a sample container in the laboratory and treated as a sample in all respects, including exposure to samp ling site conditions, storage, preservation and all analytical procedures. The purpose of the TB is to determine if test substances or other interferences are present in the field environment. This sample is also referred to as a Trip Blank.



## 3.6 Field Duplicate Sample (FDS, Field Dup)

A sample collected in duplicate at the same time from the same location as the sample. The

FDS is handled under identical circumstances and treated exactly the same throughout field and laboratory procedures. Analysis of the FDS compared to that of the first sample gives a measure of the precision associated with sample collection, preservation and storage, as well as with laboratory procedures.



## 3.7 Field Matrix Spike (FMS)

A sample to which known quantities of the target analyte s , ISs and SRSs are added to the sample bottle in the laboratory before the bottles are sent to the field for collection of aqueous samples. A known, specific volume of sample must be added to the sample container without rinsing. This may be accomplished by making a “fill to this level” line on the outside of the sample container. The FMS is analyzed to ascertain if any matrix effects, interferences, or stability issues may complicate the interpretation of the sample analysis.



## 3.8 Trip Blank Matrix Spike ( T BMS )

An aliquot of ASTM Type I, HPLC grade water, or other suitable water, to which known quantities of the target analytes , ISs and SRSs are added in the laboratory prior to the shipment of the collection bottles. The TBMS is analyzed exactly like a study sample to help determine if the method is in control and whether a loss of analyte or analytical bias could be

attributed to sample holding time, sample storage and/or shipment issues. A low and high

TBMS are appropriate when expected sample concentrations are not known or may vary.



## 3.9 Internal Standard (IS)

A compound added to each study sample, calibration standard, laboratory control samples, and procedural blanks at a consistent level (typically around 1 ng/mL). T he internal

standard (s) are stable isotope labeled versions of the target analyte s . The area count ratio of the target analyte to the internal standard is used for calibration. Surrogate ISs are applied when stable isotope ISs of target analytes are unavailable. A surrogate IS is not necessar ily

a stable isotope labeled version of the target analyte, but is treated as an internal standard for quantitation.



## 3.10 Laboratory Control Sample (LCS)

An aliquot of control matrix to which known quantities of the target analytes , ISs and SRSs (when applicabl e) are added in the laboratory at the time when samples are aliquotted . At

least three levels (two levels for SRSs) in triplicate are included, one generally at the low end of the calibration curve and one near the mid range and the upper end of the curve. The LCSs are analyzed exactly like a laboratory sample to determine whether the stability of the

standards . LCSs should be prepared each day samples are aliquoted

. 

## 3.11 Laboratory Matrix Spike (LMS)

A laboratory matrix spike is an aliquot of a sample to which known quantities of target analytes , ISs and SRSs (when applicable) are added in the laboratory. The LMS is analyzed exactly like a laboratory sample to determine whether the sample matrix contributes bias to the analytical results. The endogenous concentrations of the analytes in the sample matrix must be determined in a separate aliquot and the measured values in the LMS corrected for these concentrations. LMSs are optional for analysis of aqueous samples.

### ETS -8- 044. 1 Page 5 of 22 Method of Analysis for the Determination of Perfluorinated Compounds in Wate r by LC/MS/MS; Direct Injection Analysis 

## 3.12 Laboratory Sample

A portion or aliquot of a sample received from the field for testing.



## 3.13 Limit of Quantitation (LOQ)

The lower limit of quantitation (LLOQ) for an analytical batch is the lowest concentration that can be reliably quantitated within the specified limits of precision and accuracy. The LLOQ is generally selected as the lowest non

- zero standard in the calibration curve that meets method acceptance criteria. The LLOQ for each target analyte is established for each analysis batch

as the lowest calibration standard with area counts at least twice that of the average area counts of the procedural blanks.

The upper limit of quantitation (ULOQ) for an analytical batch is the highest concentration that can be reliably quantitated within the specified limits of precision and accuracy. The highest standard in the calibration curve that meets method acceptance criteria is defined as the
ULOQ.



## 3.14 Method /Procedural Blank

An aliquot of control matrix that is treated exactly like a laboratory sample including exposure to all glassware, equipment, solvents, and reagents that are used with other laboratory samples. The method blank is used to determine if test substances or other interferences are present in the laboratory environment, the reagents, or the apparatus.



## 3.15 Sample

A sample is an aliquot removed from a larger quantity of material intended to represent the original source material.



## 3.16 Stock Standard Solution (SSS)

A concentrated solution of a single

- analyte prepared in the laboratory with an assayed reference compound.



## 3.17 Surrogate Internal Standard

An IS that is not necessarily a stable isotopically labeled target analyte, but is treated as an internal standard for quantitation. Surrogate ISs are used when isotopically labeled

counter parts of the target analyte are not commercially or re adily available.



## 3.18 Surrogate Recovery Standard (SRS)

An isotopically labeled standard , not used as an internal standard, that is added to each sample and appropriate QC sample as a means to evaluate the method performance for a chemical class of compounds (e .g., PFSAs, PFCAs)

. 

## 3.19 Working Standard (WS)

A solution of several analytes prepared in the laboratory from SSSs and diluted as needed to prepare calibration standards and other required analyte solutions.



## 4 Warnings and Cautions

4.1 Health and Safety

The acute and chronic toxicity of the standards for this method have not been precisely determined; however, each should be treated as a potential health hazard. The analyst should wear gloves, a lab coat, and safety glasses to prevent exposure to chemicals that might be present.

### ETS -8- 044. 1 Page 6 of 22 Method of Analysis for the Determination of Perfluorinated Compounds in Wate r by LC/MS/MS; Direct Injection Analysis The laboratory is responsible for maintaining a safe work environment and a current awareness of local regulations regarding the handling of the chemicals used in this method. A reference file of material safety data sheets (MSDS) should be available to all personnel involved in these analyses.



## 4.2 Cautions

The analyst must be familiar with the laboratory equipment and potential hazards including, but not limited to, the use of solvents, pressurized gas and solvent lines, high voltage, and

vacuum systems. Refer to the appropriate equipment procedure or operator manual for

additional information and cautions.



## 5 Interferences

During sample preparation and analysis, major potential contaminant sources are reagents and glassware. All materials used in the analyses shall be demonstrated to be free from interferences under conditions of analysis by running method blanks.

Parts and supplies that contain Teflon® should be avoided or minimized due to the possibility of interference and/or contamination. These may include, but are not limited to: wash bottles,

Teflon ® 

### lined caps, autovial caps, HPLC parts, etc.

The use of disposable micropipettes or pipettes to aliquot standard solutions is recommended to make calibration standards and matrix spikes.



## 6 Instrumen tation, Supplies, and Materials

6.1 Instrumentation

Analytical balance capable of reading to 0.0001g

HPLC/MS/MS or HPLC/MS system, as described in Section 10

. 

## 6.2 Supplies and Materials

Sample collection bottles

— HDPE (e.g., NalgeneTM) wide

- mouth bottles with screw cap.

Note: Do not use fluorinated or Teflon® bottles or lined caps.

Coolers or boxes for sample shipment.

15

- mL and 50

- mL disposable polypropylene centrifuge tubes.

Class A pipettes and volumetric flasks, various.

2 mL HPLC auto vial s

Disposable pipettes, polypropylene or glass as appropriate

Centrifuge capable of spinning 15

- mL and 50

- mL polypropylene tubes at 3000 rpm.



## 7 Reagents and Standards

Note: Suppliers and catalog numbers are for illustrative purposes only. Equivalent performance may be ach ieved using chemicals obtained from other suppliers. Do not use a lesser grade of chemical than those listed.



## 7.1 Chemicals

Water – Milli

- Q, HPLC grade, or other suitably appropriate sources

Calcium Acetate - A.C.S. Reagent Grade

### ETS -8- 044. 1 Page 7 of 22 Method of Analysis for the Determination of Perfluorinated Compounds in Wate r by LC/MS/MS; Direct Injection Analysis Magnesium Acetate - A.C.S. Re agent Grade

Methanol – HPLC grade

Ammonium Acetate – A.C.S. Reagent Grade



## 7.2 Representative Target Analytes, ISs, and SRSs

PFBA, Heptafluorobutyric Acid, (C 4 

### Perfluorinated Acid)

PFPeA , Nonafluoropentanoic Acid (C 5 

### Perfluorinated Acid)

PFHxA, Perfluorohexanoi c Acid (C 6 

### Perfluorinated Acid)

PFHpA, Tridecafluoroheptanoic Acid, (C 7 

### Perfluorinated Acid)

PFOA, Ammonium perfluorooctanoate, (C 8 

### Perfluorinated Acid)

PFNA, Heptadecafluorononanoic Acid, (C 9 

### Perfluorinated Acid)

PFDA, Nonadecafluorodecanoic Acid (C 10 

### Per fluorinated Acid)

PFUnA, Perfluoroundecanoic Acid, (C 11 

### Perfluorinated Acid)

PFDoA, Perfluorododecanoic Acid, (C 12 

### Perfluorinated Acid)

PFTrDA, Perfluorotridecanoic Acid, (C 13 

### Perfluorinated Acid)

FBSA, Perfluorobutanesulfonamide

FOSA, Perfluorooctanesulfo nylamide

PFBS, Potassium Perfluorobutane sulfonate

PFHS, Perfluorohexanesulfonate

PFOS, Potassium perfluorooctanesulfonate

PFOA [1,2, 3, 4

- 13 

### C], 13 

### C 4 

### - isotopically labeled perfluorooctanoic acid (SRS)

PFOS [1,2, 3, 4

- 13 

### C], 13 

### C 4 

### - isotopically labeled Perfluorooctanesulfonate (SRS)

PFUnA [1,2

- 13 

### C], 13 

### C 2 

### - isotopically labeled Perfluoroundecanoic acid (SRS)

A custom mix of ISs in a methanolic solution containing ([1,2,3,4

- 13 

### C 4 

### ]PFBA, [1,2

- 13 

### C 2 

### ]PFHxA, [1,2,3,4 ,5,6,7,8

- 13 

### C 8 

### ]PFOA, [1,2,3,4,5 ,6,7,8,9

- 13 

### C 9 

### ]PFN A, [1,2

- 13 

### C 2 

### ]PFDA, [1,2 ,3,4,5,6,7 - 13 

### C 7 

### ]PFUnA, [1,2

- 13 

### C 2 

### ]PFDoA, [1,2 ,3 - 13 

### C 3 

### ]PFHS, [1,2,3,4 ,5,6,7,8

- 13 

### C 8 

### ]PFOS

, and [1,2,3,4,5,6,7,8

- 13 

### C 8 

### ]PFOSA (Wellington Laboratories, Guelph, ON) in combination with added ([1,2,3,4 ,5

- 13 

### C 5 

### ]PFPe A

, ([1,2,3,4

- 13 

### C 4 

### ]PFHpA, and [ 18 

### O 2 

### ]PFBS can be used to prepare a stock IS solution. Alternatively, individual stable isotope ISs can be used to prepare a stock

IS mixture.

Other ISs can be applied.



## 7.3 Reagent Preparation

2 mM A mmonium acetate solution (Analysis)

— Weigh 0.3 g of A mmonium acetate and dissolve in 2.0 L of reagent water.

Synthetic Groundwater (containing 25 ppm Ca and Mg) – Weigh 0.61 g of Calcium Acetate and 0.92 g of Magnesium Acetate and dissolve in 6.0 L of reagent water.

Note: Alternative volumes may be prepared as long as the ratios of the solvent to solute ratios

are maintained.

### ETS -8- 044. 1 Page 8 of 22 Method of Analysis for the Determination of Perfluorinated Compounds in Wate r by LC/MS/MS; Direct Injection Analysis 

## 7.4 Stock Standard Solution (SSS) and Working Standard Solution Preparation

The following standard preparation procedure serves as an example. Weighed amounts and final volumes may be changed to suit the needs of a particular study. For example, μL volumes may be spiked into volumetric flasks when diluting stock solutions to appropriate

levels.

100 μg/mL target analyte SSSs

— Weigh out 10 mg of analytical standard **(corrected for**

**percen t salt**  **, acid [ETS -4-**  **031] and purity**  ) and dilute to 100 mL with methanol or other suitable solvent, in a 100 mL volumetric flask. Transfer to a 125 mL LDPE bottle or other suitable container. Prepare a separate solution for each analyte. Expiration dates and storage conditions of stock solutions should be assigned in accordance with laboratory standard operating procedure. An example of purity and salt correction is given below for

PFOS.



### salt of weight moclecular anion of weight molecular factor correction salt

=

9275.0 538 499 factor correction )salt (K PFOS

== +



### 10 mg C 8 

### F 17 

### S0 3 - 

### K + 

### with purity 90% = 8.35 mg C 8 

### F 17 

### S0 3 – 

### (10 mg*0.90*0.9275=8.35 mg)

10 μg/mL (10,000 ng/mL) mixed working standard

— Add 5.0 mL each of the 100 μg/mL SSSs to a 50 mL volumetric flask and bring up to volume with solvent.

1 μg/mL (1,000 ng/mL) mixed working stan dard

— Add 0.5 mL of the 100 μg/mL SSSs to a 50 mL volumetric flask and bring up to volume with solvent.

0.1 μg/mL (100 ng/mL) mixed standard

— Add 0.05 mL of the 100 μg/mL SSSs to a 50 mL volumetric flask and bring up to volume with solvent.

Storage Conditi ons

— Store all SSSs and working standards in accordance with laboratory standard operating procedure or in a refrigerator at 4°±2°C for a maximum period of 6 months from the date of preparation.



## 7.5 Calibration Standards

Calibration can be performed by IS or external calibration. Using the working standards described above, prepare calibration solutions in ASTM Type I water, HPLC water, other suitable water, or a mixture of solvent and water using the information in Table 2 as a guideline. Note: Volumes of wa ter or water/solvent mixtures and working standards may be adjusted to meet the data quality objectives addressed in the general project outline. Calibration levels other than those listed below can be prepared as needed.

For the quantitation of PFOA and PFOS, reference materials of certified mixed linear and branched isomer are preferred. Alternately, reference materials of primarily linear isomers of PFOA and/or PFOS may be used, however, when quantitating with predominantly linear reference standards, additional LCS samples containing both linear and branched isomers of PFOA and PFOS are required 3



### .

7.5.1 Internal Standard (IS) and Surrogate Recovery Standard (SRS)

For IS calibration, stable isotope internal standards of each target analyte or appropriate surrogate ISs should be spiked at the same level in all calibration standards. Once the calibration standards have been prepared as stated above in Section 7.5, all calibration standards are spiked with a separate internal standard spiking solution. Typically the

3 A report summarizing an assessment of the use of reference standards containing certified linear and branched isomers of
PFOA/PFOS can be found in 3M report E11

- 0560.

### ETS -8- 044. 1 Page 9 of 22 Method of Analysis for the Determination of Perfluorinated Compounds in Wate r by LC/MS/MS; Direct Injection Analysis concentration of the internal standard is consistent with the internal standard concentration expected in the samples being prepared, usually 1 ng/mL. The concentration of the internal standard spiking solution is typically 2 μg/ mL. A separate zero point or method blank is typically prepared at the same time as the calibration standards, using the same solution used to prepare the standards (ASTM Type I water, HPLC water, other suitable water, or a solvent/water mixture), and is spiked with the internal standard at the same concentration as the calibration curve, typically at 1 ng/mL.

If the sample s being analzyed w ere pre

- spiked with SRSs , the calibration curve prepared in

Section 7.5 is spiked with a separate SRS spiking solution. Typically, the sample bottles are spiked with a SRS at 0.1 ng/mL. The final calibration curve must consist of at least six calibration points after analysis. The following table provides an example of spike

concentrations and volumes used to achieve a multi

- point extracted calibration curve with internal standard and surrogate standard.

Table 1 lists recommended stable isotope internal standards for several PFSA and PFCA target compounds. A custom mix of isotopically labeled target analytes in a methanolic solution containing ([1,2,3,4

- 13 

### C 4 

### ]PFBA, [1,2

- 13 

### C 2 

### ]PFHxA, [1,2,3,4,5,6,7,8

- 13 

### C 8 

### ]PFOA, [1,2,3,4,5,6,7,8,9

- 13 

### C 9 

### ]PFNA, [1,2,3,4,5,6

- 13 

### C 6 

### ]PFDA, [1,2,3,4,5,6,7

- 13 

### C 7 

### ]PFUnA, [1,2

- 13 

### C 2 

### ]PFDoA, [ 1,2,3

- 13 

### C 3 

### ]PFHS, [1,2,3,4,5,6,7,8

- 13 

### C 8 

### ]PFOS, and [1,2,3,4,5,6,7,8

- 13 

### C 8 

### ]FOSA (Wellington Laboratories, Guelph, ON) in combination with added ([1,2,3,4 ,5

- 13 

### C 5 

### ]PFPe A

, ([1,2,3,4

- 13 

### C 4 

### ]PFHp A , and [ 18 

### O 2 

### ]PFBS can be used to prepare a stock IS solution. Alternative sources of certified stable isotope labeled target analytes are applicable. Alternatively, individual stable isotope ISs can be used to prepare a stock IS mixture. The table below lists the recommended stable isotope ISs and SRSs applied in the method. Other stable isotope ISs and SRSs of target analytes not listed in the table may be used if supported by validation and/or analysis batch QCs meeting method acceptance criteria (e.g., [ 13 

### C 2 

### ]- PFOA) . The same internal standard should be used for a given analyte throughout the entire project/study. Note: some of the compounds listed below are appropriate to use as surrogate ISs when a stable isotope IS of a target analyte is not available. Generally,
surrogate isotopically labeled PFCAs are used for PFCAs, and surrogate i sotopically labeled

PFSA s are used for PFSAs.

Table 2 provides examples of spike concentrations and volumes used to achieve a multi

- point

calibration curve with ISs and SRSs

.

### ETS -8- 044. 1 Page 10 of 22 Method of Analysis for the Determination of Perfluorinated Compounds in Wate r by LC/MS/MS; Direct Injection Analysis Table 1 . Stable Isotope PFCAs and PFSAs used for ISs and SRSs

Compound Name Synonym or Acronym Analytical Purpose Reference Standard

Source

13 C 4 - Perfluorobutanoic acid [1,2,3,4

- 13 C 4 ]PFBA IS for PFBA Wellington Labs

(Mix or Individual)

13 C 4 - Perfluoro pentanoic acid [1,2,3,4 ,5

- 13 C 5 ]PFPe A IS for PFPeA Wellington Labs

(Mix or Individual)

13 C 2 - Perfluorohexanoic acid [1,2

- 13 C 2 ]PFHxA IS for PFHxA Wellington Labs

(Mix or Individual)

13 C 4 - Perfluoro hept anoic acid [1,2,3,4

- 13 C 4 ]PFHp A IS for PF HpA Wellington Labs

(Mix or Individual)

13 C 8 - Perfluorooctanoic acid [1,2,3,4,5,6,7,8

- 13 C 8 ]PFOA IS for PFOA and [1,2,3,4

13 C 4 ]PFOA Wellington Labs

(Mix or Individual)

13 C 9 - Perfluorononanoic acid [1,2,3,4,5,6,7,8,9

- 13 C 9 ]PFNA IS for PFNA Wellington Labs

(Mix or Individual)

13 C 6 - Perfluorodecanoic acid [1,2,3,4,5,6

- 13 C 6 ]PFDA IS for PFDA Wellington Labs

(Mix or Individual)

13 C 7 - Perfluoroundecanoic acid [1,2,3,4,5,6,7

- 13 C 7 ]PFUnA IS for PFUnA Wellington Labs

(Mix or Individual)

13 C 2 - Perfluorododecanoic acid [1,2

- 13 C 2 ]PFDoA IS for PFDoA, *PFTA Wellington Labs

(Mix or Individual)

18 O 2 - Ammonium Perfluorobutane sulfonate [ 18 O 2 ]PFBS IS for PFBS RTI International (Individual)

13 C 3 - Ammonium Perfluorohexane sulfonate [ 1,2,3

- 13 C 3 ]PFHS IS for PFHS Wellington Labs

(Mix or Individual)

13 C 8 - Sodium Perfluorooctane sulfonate [1,2,3,4,5,6,7,8

- 13 C 8 ]PFOS IS for PFOS and
PFOS[1,2,3,4 13 C 4 ], Wellington Labs

(Mix or Individual)

13 C 8 - Perfluorooctanesulfonamide [1,2,3,4,5,6,7,8

- 13 C 8 ]FOSA IS for FOSA Wellington Labs (mix)

RTI International (Individual)

13 C 4 - Perfluorooctanoic acid [1,2,3,4

- 13 C 4 ]PFOA SRS for all PFCAs : C4

- C8 Wellington

13 C 2 - Perfluoroundecanoic acid [1,2

- 13 C 2 ]PFUnA SRS for all PFCAs C9

- C13 Wellington

13 C 8 - Perfluorooctane sulfonate [1,2,3,4

- 13 C 4 ]PFOS SRS for all PFSA s: C4,
C6, and C8 Wellington

### ETS -8- 044. 1 Page 11 of 22 Method of Analysis for the Determination of Perfluorinated Compounds in Water by LC/MS/MS; Direct Injection Analysis Table 2 . Example Preparation of Calibration Curve with ISs and SRSs

**Sample Description Concentration**  **of WS, μ**  **g/mL Volume of**  **WS,** μ **L Volume of IS**  **(2 μ**  **g/mL),** μ **L Concentration of**  **Surrogate, μ**  **g/mL Volume of**  **Surrogate,** μ **L Volume of ASTM Type I**  **Water, or**

**other suitable solvent**  **(1) , mL** 

0.025 ng/mL curve point 0.10 25 50 0.20 12.5 100

0.030 ng/mL curve point 0.10 30 50 0.20 15 100

0.04 ng/mL curve point 0.10 40 50 0.20 20 100

0.05 ng/mL curve point 0.10 50 50 0.20 25 100

0.1 ng/mL curve point 0.10 100 50 0.20 50 100

0.25 ng/mL curve point 0.10 250 50 0.20 125 100

0.5 ng/mL curve point 1.0 50 50 0.20 250 100

1 ng/mL curve point 1.0 100 50 0.20 500 100

2.5 ng/mL curve point 10.0 25 50 10.0 25 100

5.0 ng/mL curve point 10.0 50 50 10.0 50 100

10.0 ng/mL curve point 10.0 100 50 10.0 100 100

25.0 ng/mL curve point 10.0 250 50 10.0 NA 100

50.0 ng/mL curve point 10.0 500 50 10.0 NA 100

75.0 ng/mL curve point 10.0 750 50 10.0 NA 100

100 ng/mL curve point 10.0 1000 50 10.0 NA 100

N/A - Not Applicable (1) Samples requiring analysis for PFUnA, PFDoA, PFTrDA, and FOSA should be analyzed against a calibration curve prepared in 1:1 synthetic groundwa ter:MeOH.

### ETS -8- 044. 1 Page 12 of 22 Method of Analysis for the Determination of Perfluorinated Compounds in Wate r by LC/MS/MS; Direct Injection Analysis 

## 8 Sample Collection and Bottle Preparation

Sample collection bottles are prepared by 3M Environmental Laboratory (or subcontract supplier) personnel for shipment at ambient temperature to the collection site. Typically, four separate collection bottles are associated with a single collection site: sample, field duplicate sample, low field matrix spike, and high field matrix spike. Alternatively, the sample and field duplicate sample may contain SRSs in lieu of additional target analyte low field matrix spike and target analyte high field matrix spike samples. Depending on the scope of the project, additional replicates of the field sample and field matrix spikes may be added. Also, it is not

uncommon for additional mid

- level field matrix spikes to be collected if the expected sample concentrations are truly unknown or could span a large concentration range.

High

- density polyethylene (HDPE) wide

- mouth Nalgene bottles are used for the sample collection containers. (Volumes of the bottles may vary depending on how much sample is required to meet data quality objectives.) Sample collection volumes are project specific and based on data quality objectives. The Nalgene bottles do not require any pretreatment prior to use. Typically, placement of a sample bottle volumetric “fill to here” line is done by using a sample bottle marker template. Alternatively, bottles may be weighed prior to bottle preparation and weighed again after samples have been collected.

All bottles should be clearly labeled to indicate its intended use as a sample, field sample duplicate, low field matrix spike, high field matrix spike, sample/SRS field matrix spike, field duplicate sample/SRS field matrix spike, trip blank, or trip blank matrix spike. If each location has different designated spike levels, the label should also clearly indicate the sample location designation. Generally, a set of bottles for a given collection site are prepared then grouped together in plastic bags for organizational purposes. For each sample collection event, at least one set of trip blank and trip blank matrix spikes are prepared.

Bottle preparation should be documented in a Note to File or on a sample preparation worksheet and should include the following information: date prepared, total number of bottles prepared, number of sample sites, the standard identification numbers and spike volumes used to prepare spiked bottles, the “fill to here” volume, and any other pertinent information needed for reconstructibility of the data. The Note to File will be included in the final data package for the project.

Samples are collected in the field and shipped to the laboratory at ambient temperature.



## 8.1 Field Matrix Spike Sample (FMS)

Field matrix spike samples are a requirement of the method. A FMS sample is defined as a QC sample to which known quantities of appropriate target analytes are added to the sample bottle in the field or in the laboratory before the bottles are sent to the field. The sample and field duplicate sample may contain appropriate SRSs in lieu of target analyte FMS samples. Sample quantities are determined vol umetrically or gravimetrically. A known, specific volume or weight of sample is added to the sample container without rinsing. Volumetric sample measurements may be acquired by a laboratory applied “fill to this level” line on the outside of the sample container. Target analyte FMS samples should be spiked at approximately 0.5

- 10 times the expected analyte concentration in the sample. If the expected range of analyte concentrations is unknown, multiple spikes at varying levels may be prepared to increase the likelihood that a spike at an appropriate level is made. Typically a low and a high target analyte spike are prepared for each sampling location. In those instances where SRSs are to be used in lieu of target analyte FMS samples, the sample and field duplicate sample are spiked at approximately 2

- 5 times the target LOQ. The FMS is analyzed to ascertain if matrix effects or sample holding time contributes bias to the analytical results. For the sample bottles designated for matrix spikes, an appropriate volume of matrix spiking solution is added to the empty bottle prior to sampling. The volume of spike solution added should produce the desired final concentration of target analytes once the bottle is filled with sample to the “fill to here line”. The matrix spiking solution(s) should be prepared in a suitable solvent and contain all of the appropriate target analytes, ISs, and SRSs. The target analyte matrix spiking solution is often the same as the working standards used to create the calibration standards. An example of a bottle spike is given below.

“Fill to here” volume = 200 mL (A 250 mL Nalgene bottle is used)

Desired Field Spike Concentration = 0.25 ng/mL

### ETS -8- 044. 1 Page 13 of 22 Method of Analysis for the Determination of Perfluorinated Compounds in Wate r by LC/MS/MS; Direct Injection Analysis 500 μ L of a 0.1 μ g/mL spiking solution (containing the target analytes) is added to the bottle and the bottle cap promptly sealed.



## 8.2 Internal Standard and Surrogate Recovery Standard

If analysis of a surrogate recovery standard (SRS) is included in the project objectives, an appropriate volume of a surrogate standard solution is added to all the bottles prior to sampling and SPE. Typically sample bottles are spiked with surrogate recovery standards at a final desired spike concentration of 0.1 ng/mL.

If quantitation by internal standard (IS) is included in the project objective, an appropriate volume of internal standard solution is added to all the bottles prior to sampling and SPE . Typically sample bottles are spiked with internal standard at a final desired spike concentration of 1 ng/mL.

For the trip blank, the SRS spike and IS spike i s added to the bottle and then ASTM Type I water (HPLC grade reagent water or other suitable water may used) is added to the “fill to here” line. The bottle is capped and sealing tape may be placed around the outer edge of the cap. Trip blank matrix spikes are prepared by adding the appropriate volume of target analyte spiking solution, IS, and SRS spiking solutions and filling the bottle to the desired volume with the appropriate water and capping and sealing the cap.



## 9 Quality Control and Data Quality Objectives

9.1 Data Quality Objectives

This method and required quality control samples is designed to generate data accurate to ±30% with a targeted LOQ of 0.025 ng/mL. Any deviations from the quality control measures spelled out below will be documented in the raw data and footnoted in the final report.



## 9.2 Method/Procedural Blanks

The method/procedural blank is zero point calibration standard (which includes ISs) analyzed in a regular basis with each analysis batch. At a minimum, method blanks are analyzed prior to instrument calibration, prior to the analysis of CCV samples, after every 10 sample injections, and at the end of the analytical run.

The mean area count or area ratios when using internal standard calibration, for each analyte in the method

blanks m ust be less than 50% of the area count counts or area ratios when using internal standard calibration, of the LOQ standard. The standard deviation of the area counts, or area ratios when using internal standard calibration, of these method blanks should be calculated. A specific %RSD acceptance criteria is not specified but is assessed on an analytical batch basis. If the mean area counts or area ratios when using internal standard calibration, of the method blanks exceed 50% of the LOQ standard, then the LOQ must be raised to

the first standard level in the curve that meets criteria. Method blanks may be eliminated if technical justification can be provided (e.g. the procedural blank was analyzed after an unexpectedly high level sample). If any procedural blanks are removed from the LOQ determination, document in the raw data and report as appropriate. Laboratory Sample Replicates / Field Duplicate Sample

Typically, samples are collected in duplicates in the field. The relative percent difference (RPD) of duplicate samples should be ≤20% for the precision of sample preparation and analysis to be considered in control. Replicate samples not meeting the ≤20% RPD criteria are flagged and reported as outside of QC acceptance

criteria.



## 9.3 Laboratory Matrix S pikes (LMSs)

LMSs may be performed in lieu of FMSs if FMSs have previously been performed for the sample matrix. Additionally, LMSs may be performed in lieu of FMSs for a sample matrix if the FMS levels were not appropriate for determining spike recoveries relative to endogenous levels of target analytes and appropriate SRSs. Generally, each sample location represents a different sample and sample matrix. LMSs are prepared for each sample and analyzed to determine the matrix effect on spike recovery efficiency of each target analyte and appropriate SRSs. LMSs should be prepared at a minimum of one level and in duplicate. LMS concentrations should be prepared at approximately 0.5

- 10 times the endogenous concentration or approximately 4

- 10 times the LOQ concentration of each target analyte.

### ETS -8- 044. 1 Page 14 of 22 Method of Analysis for the Determination of Perfluorinated Compounds in Wate r by LC/MS/MS; Direct Injection Analysis Lab matrix spike recoveries should fall within ± 30% of expected values. Sample data with LMS recovery outside of ±30% but within ±50% of the expected value are flagged and reported as outside of QC acceptance

criter ia. Data with LMS recovery outside of ±50% of the expected value are reported as NR, where NR is defined as “Not Reportable” data outside of QC acceptance criteria.



## 9.4 Lab Control Sample

Lab control spikes are prepared for each analysis batch to determine method accuracy and precision. LCSs should be prepared at three levels in triplicate for each target analyte and at a minimum of two levels in triplicate for appropriate SRSs. Low lab control spikes should be prepared at a concentration in the range of

a pproximately four to ten times higher than the targeted lower LOQ, the mid lab control spikes should be prepared at a concentration near the mid

- point of the calibration curve and the high lab control spikes at approximately 80% of the upper LOQ. For each target analyte and SRSs, the percent relative standard deviation (method precision) for each control spike level must be less than or equal to 20% and the average recovery (method accuracy) for each control spike level must be 80

- 120%. Sample data for target analytes outside of the laboratory control spike acceptance criteria will be handled as follows:

If the average recovery of a spiking level falls outside method acceptance, but at least 67% (6 out of 9 ) o f LCS samples are within 20 % of their respective nominal value (33% of the QC samples, not all replicates at the

same concentration, may be outside 20% of nominal value), the average recovery will be flagged as outside method acceptance criteria. All LCS samples will be control charted as per ETS -4- 02 6. If the average recovery of one of the spiking levels exceeded the analytical method uncertainty as determined by ETS

- 12

- 012, that analytical batch uncertainty will be expanded for that particular study.

If more than 67% of the LCS samples fail to meet method acceptance criteria, the data will not be reported.

Calibration standards consisting of mixed branched and linear isomer PFOS/PFOA are preferred. However, for PFOS/PFOA target analytes, if the calibration standards are comprised of predominantly linear isomers only, at least one level of triplicate LCSs should be prepared using PFOS/PFOA which contains a mix of linear and branched isomers. These LCSs will be used to demonstrate quantitative equivalency (or quantitative bias) of the isomeric mix when using a predominantly linear standard for calibration. The mixed linear and branched

isomer PFOS/PFOA LCSs recoveries should fall within ± 30% of expected values. Alternatively, in lieu of mixed branched and linear isomer PFOS/PFOA LCSs, mixed branched and linear isomer PFOS/PFOA TBMSs may be applied to demonstrate method accuracy and precision.



## 9.5 Field Matrix Spikes (FMSs) / Surrogate Recovery Standards (SRSs)

FMSs are prepared for each sampling location and analyzed to determine the matrix effect and sample holding time on the spike recovery of each target analyte and/or appropriate SRS. Generally, each sample location represents a different sample and sample matrix.

FMSs are QC samples to which known quantities of appropriate target analytes are added to the sample bottle in the laboratory before the bottles are sent to the field. Typically a low and a high target analyte FMS are prepared for each sampling location. The sample and field duplicate sample may contain appropriate SRSs in lieu of target analyte low field matrix spike and target analyte high field matrix spike samples.

Field matrix spike method acceptance criteria are recoveries within ±30% of the expected value. If FMS recovery (target analyte or SRS spike) is outside of ±30% of the expected value or could not be assessed because the FMS (target analyte) was spiked at an inappropriate level, the sample result is reported as follows:

1.) If target analyte FMS recovery could not be assessed because the FMS's were at an inappropriate level, then Laboratory Matrix Spikes (LMS) may be substituted. If LMS recoveries are within ±30% the data are reportable and flagged to indicate that the FMS spikes levels were inappropriate.

2.) If multiple target analyte FMS's were prepared on a sample and the closest FMS level to the reported sample meets the ±30% acceptance criteria but additional FMS's are outside the ±30% acceptance range, the data are reportable and flagged to indicate that while there were failing FMS’s, the uncertainty will not be expanded since the most appropriate spike level passed.

### ETS -8- 044. 1 Page 15 of 22 Method of Analysis for the Determination of Perfluorinated Compounds in Wate r by LC/MS/MS; Direct Injection Analysis 3.) If the target analyte FMS recoveries are outside of the ±30% acceptance range but at least 30 acceptable historical reportable FMS sample results are available, the data may be reported but flagged with an expanded uncertainty and as not meeting FMS criteria.

4.) Sample data with FMS recovery outside of ±30% but within ±50% of the expected value are flagged and reported as outside of QC acceptance criteria with an expanded uncertainty.

5.) If FMS recovery is outside of ±50%, the sample result is reported as NR, where NR is defined as “Not Reportable” due to noncompliant QC results.

The targeted fortification levels should be at least 50% of the endogenous level and less than 10 times the

e ndogenous level to be used without justification to determine the statement of accuracy for analytical results.

Note: It is possible for bottles utilized for Field Matrix Spike samples to be under

- filled or over

- filled during sample collection. Since this scenario will effect the actual concentration of the FMS sample (surrogate and internal standard concentrations will also be effected, if used), it is important that any obvious under

- filling or

over

- filling of sample bottles be documented in the data package and taken into account in the FMS , ISs, or

SRSs recovery calculations. Samples over

- filled or under

- filled by more than 10% will be require recalculation of the FMS, ISs, and SRS true values.

The average of the sample and the field duplicate should be used to calculate the recovery.



## 10 Procedures

10.1 Water Sample Preparation

This method is applicable to water samples. Samples containing heavy particulate may not be suitable for analysis by this method. Samples containing suspended particulate should be centrifuge prior to removing a sample aliquot, or filtered.

• Thoroughly mix sample before removing a n aliquot and placing in a labeled autovial.

• Dilute sample, if necessary, with ASTM Type I water , HPLC water, other suitable water , or solvent (methanol)

.

• L ab control spikes are prepared for each analysis batch to determine method accuracy and precision. LCSs should be prepared at three levels in triplicate for each target analyte and at a minimum of two levels in triplicate for appropriate SRSs. Low lab control spikes should be prepared at a concentration in the range of approximately four to ten times higher than the targeted lower LOQ, the mid lab control spikes should be prepared at a concentration near the mid

- point of the calibration curve and the high lab control spikes at approximately 80% of the upper LOQ. For IS quantitation, stable isotope internal standards of each target analyte or appropriate surrogate ISs should be spiked at the same level as the samples being analyzed, in all LCSs

.

• If LCSs are being prepared us ing synthetic groundwater, allow the LCSs samples to equilibrate for a

minimum of 4 hours before aliquoting for analysis or diluting with solvent (methanol).



## 11 Sample Analysis - LC/MS/MS

11.1 Instrument Setup

Note: In this example, an Applied Biosystems Sciex API 4000 (API 5000 or API 5500) Tandem Mass Spectrometer (LC/MS/MS) is used. Other brands/models of LC/MS/MS instruments as well as single quadrupole mass spectrometers (LC/MS) may be used as long as the method acceptance criteria are met. Brand names, suppliers, part numbers, and models are for illustrative purposes only. Equivalent performance may be achieved using apparatus and materials other than those specified here, but demonstration of equivalent performance that meets the requirements of this method is the responsibility of the laboratory. The operator must optimize and document the equipment and settings used.

### ETS -8- 044. 1 Page 16 of 22 Method of Analysis for the Determination of Perfluorinated Compounds in Wate r by LC/MS/MS; Direct Injection Analysis Establish the LC/MS/MS system and operating conditions equivalent to the following:

Mass Spec: Applied Biosystems API 4000, API 5000, or API 5500

Ion Source: Turbo Ion Spray (ABS)

Mode: Electrospray Negative

Scan Type: MRM (Multiple Reaction Monitoring)

Computer: Dell DHM

Software: Windows 2000 or Windows XP, Analyst 1.4.2 or higher versi ons

HPLC: Agilent Series 1100,1200, or 1290

Agilent Quaternary Pump

Agilent Vacuum Degasser

Agilent Autosampler

Agilent Column Oven

Note: One or more C18 HPLC analytical columns (2.1 mm x 100 mm, 5 μ m or 2.1 mm x 50 mm, 5 μ m) may be

attached on

- line after the purge valve and before the sample injection port to retard and separate any residue contaminants that may be in the mobile phase and/or HPLC system.

HPLC Column: Betasil C18, 4.6mm x 100mm, 5 μ m (ThermoElectron Corporation)

Column Temperature: 35 ° C

Inje ction Volume: 5μL

Mobile Phase (A): 2mM Ammonium Acetate in ASTM Type I water (See 7.3)

Mobile Phase (B): Methanol

Table 3

. Liquid Chromatography Gradient Program

.

**Step**

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

**L/min) Percent A** 

**(2 mM ammonium**  **acetate) Percent B** 

**(Methanol)**

0 0 750 97.0 3.0

1 2.0 750 97.0 3.0

2 14.5 750 5.0 95.0

3 15.5 750 5.0 95.0

4 16.5 750 97.0 3.0

5 20.0 750 97.0 3.0



### Note: Other HPLC gradients may be used as long as the method criteria and project data quality objectives are

met.

It may be necessary to adjust the HPLC gradient in order to optimize instrument performance. Columns with different dimensions (e.g. 2.1mm x 30mm) and columns from different manufacturers (Keystone Betasil C18 etc.) may be used.

### ETS -8- 044. 1 Page 17 of 22 Method of Analysis for the Determination of Perfluorinated Compounds in Wate r by LC/MS/MS; Direct Injection Analysis Table 4 Suggested MRM Transitions for Target Analytes, Surrogates, and Internal Standards

Analyte Analyte Description Mass Transition

Q1 (amu) Mass Transition

Q3 (amu)

PFBA (C4 Acid) Target 213 169

PFPeA (C5 Acid) Target 263 219

PFHxA (C6 Acid) Target 313 269, 119

PFHpA (C7 Acid) Target 363 319, 169

PFOA (C8 Acid) Target 413 369, 219, 169

PFNA (C9 Acid) Target 463 419, 169, 219

PFDA (C10 Acid) Target 513 469, 269, 219

PFUnA (C11 Acid) Target 563 519, 269, 219

PFDoA (C12 Acid) Target 613 569, 169, 319

PFTA (C13 Acid) Target 663 619, 369, 319

FBSA (C4 Sulfonamide) Target 298 78

FOSA (C8 Sulfonamide) Target 498 78

PFBS (C4 Sulfonate) Target 299 99, 80

PFHS (C6 Sulfonate) Target 399 99, 80

PFOS (C8 Sulfonate) Target 499 80, 99, 130

[1,2,3,4

- 13 C 4 ]PFBA IS for PFBA 217 172

[1,2 ,3,4,5

- 13 C 5 ]PFPe A IS for PFPeA 268 223

[1,2

- 13 C 2 ]PFHxA IS for PFHxA 315 270

[1,2,3,4

- 13 C 4 ]PFHpA IS for PFHpA 367 322

[1,2,3,4,5,6,7,8

- 13 C 8 ]PFOA IS for PFOA 421 376

[1,2,3,4,5,6,7,8,9

- 13 C 9 ]PFNA IS for PFNA 472 427

[1,2,3,4,5,6

- 13 C 6 ]PFDA IS for PFDA 519 474

[1,2,3,4,5,6,7

- 13 C 7 ]PFUnA IS for PFUnA 570 525

[1,2

- 13 C 2 ]PFDoA IS for PFDoA and PFTA 615 570

[ 18 O 2 ]PFBS IS for PFBS 303 84

[ 1,2,3

- 13 C 3 ]PFHS IS for PFHS 402 80

[1,2,3,4

- 13 C 4 ]PFOS IS for PFOS 503 80

[1,2,3,4,5,6,7,8

- 13 C 8 ]FOSA IS for FOSA 507 80

[1,2,3,4

- 13 C 4 ]PFOA Surrogate (C4

- C8 Acids) 417 372

[1,2,3,4

- 13 C 4 ]PFOS Surrogate(Sulfonates, FOSA) 503 80

[1,2

- 13 C 2 ]PFUnA Surrogate (C9

- C13 Acids) 565 520



### Multiple transitions for monitoring the analytes is an option. The use of one daughter ion is acceptable if data sensitivity and selectivity is achieved and provided that retention time criteria are met to assure adequate specificity. While the daughter ions may be chosen at the discretion of the analyst, mass transition 99 is suggested for PFOS. Quantitation may be performed using the total ion chromatogram (TIC, or summed MRMs) for a given analyte. For example, the PFOA TIC would sum all three of the monitored transitions. Use of the suggested primary ion is recommended. Retention times may vary slightly, on a day

- to

- day basis, depending on the batch of mobile phase and the gradient, column, guard column(s) used etc. Drift in retention

times is acce ptable within an analytical run, as long as the drift continues through the entire analysis and the standards are interspersed throughout the analytical run.



## 11.2 Calibration Curve

Quantitation is by internal standard or external standard calibration. Calibration standards may be prepared in ASTM Type I, HPLC water, other suitable water, or a solvent/water mixture. If internal standard calibration does not meet calibration acceptance criteria, external calibration can be applied. See Table 1 for

### ETS -8- 044. 1 Page 18 of 22 Method of Analysis for the Determination of Perfluorinated Compounds in Wate r by LC/MS/MS; Direct Injection Analysis recom mended application of available internal standards. Quantitation of PFOA and PFOS is by summed analyte

- specific mass transitions.

Analyze the standard curve prior to each set of samples. If internal standards were added to the calibration standards area ratios are used to generate the calibration curve. The standard curve may be plotted using a

linear regression (y = mx + b), weighted 1/x or unweighted, or by quadratic fi t (y = ax 2 

### + bx + c), weighted 1/x or unweighted

, using suitable software

. The mathematical method used to calculate the calibration curve should be applied consistently throughout a study. Any change should be thoroughly documented in the raw data.

High and/or low points may be excluded from the calibration curves to provide a better fit over the range appropriate to the data or because they did not meet the pre

- determined acceptance criteria. Low

- level curve points should also be excluded if their area counts (or area ratio if quantitating by IS) are not at least twice that

of the ave rage area counts (or area ratio if quantitating by IS) of method and/or solvent blanks. The coefficient of determination (r 2 

### ) value for the calibration curve must be greater than or equal to 0.990 (or a correlation coefficient (r) of 0.995). Each point in the curve must be within ± 25% of the theoretical concentration with the exception of the LLOQ, which may be within ± 30%. Justification for exclusion of calibration curve points will be noted in the raw data. A minimum of 6 points will be used to construct the calibration curve.

If the calibration curve does not meet acceptance criteria, perform routine maintenance or prepare a new standard curve (if necessary) and reanalyze.



## 11.3 Continuing Calibration Verification (CCV)

Continuing calibration verifications (CCV) are analyzed to verify the accuracy of the calibration curve. Analyze

a mid

- range calibration standard, one of the same standards used to construct the calibration curve, at a minimum after every tenth sample, not including solvent blanks, with a minimum of one per sample set. Calibration verification injections must be within ± 25% to be considered acceptable. The calibration curve and the last passing CCV will then bracket acceptable samples. Multiple CCV levels may be used. Samples must be bracketed by passing CCVs or the calibration curve and a passing CCV to be reportable.



## 11.4 System Suitability

A minimum of three system suitability samples should be injected at the beginning of each analytical run, prior

to th e analysis of the calibration curve. Typically these samples are at a concentration near the mid

- level of the calibration curve and are repeated injections from one autosampler vial. It is suggested that the system suitability injections have area counts or area ratios when using internal standard calibration, with a target RSD of ≤5% and a target retention time RSD of ≤2%. There is no defined acceptability limit on these results as the

%RSD value is dependent on the number of MRM transitions being monitored in the LC/MS/MS run or time period. Ultimately, any effects on these parameters for the System Suitability samples will also be evident on all standards and QC samples analyzed as part of the analysis batch. Any effect of system suitability is incorp orated within QC acceptance criteria. 4



## 11.5 Sample Analysis and QCs

For each analysis batch, the instrument analysis run sequence should include an initial calibration curve, samples, FDSs, interspersed blanks, interspersed CCVs, appropriate QCs (i.e., LCSs, LMSs, FMSs, TBMSs, and TBs), and a final CCV or calibration curve bracketing samples and appropriate QCs

Inject the same volume (between 5 - 100μL) of each standard, analytical sample and blank into the instrument (unless an on

- instrument sample dilution is desired).

Samples containing analytes that are quantitated above the concentration of the highest standard in the curve should be further diluted and reanalyzed.

4 3M Environmental Laboratory study E08

- 0096 evaluated the effect on these results as a function of the number of MRMs being monitored.

### ETS -8- 044. 1 Page 19 of 22 Method of Analysis for the Determination of Perfluorinated Compounds in Wate r by LC/MS/MS; Direct Injection Analysis 

## 12 Data Analysis and Calculations

The chromatography analysis software will typically calculate the amount of target analyte in the sample extracts using the established calibration curve.

Calculate the percent recovery of the LCS using the following equation:



### 100%*

) mL ng (ion Concentrat Spike ) mL ng (ion Concentrat LCS

recovery LCS% =

Calculate the percent recovery of the LMS using the following equation:

100%*
) mL ng ( ion Concentrat Spike ) mL ng ( Sample of ion Concentrat -) mL ng ( ion Concentrat LMS
recovery % LMS

=



### For samples fortified with known amounts of analyte prior to extraction, use the following equation to calculate the percent recovery.



### 100 (ng/mL) added Analyte (ng/mL) sample in found analyte Average- (ng/mL) found analyte Total Recovery × =



## 13 Analysis Batch Method Performance Criteria

Any method performance parameters that are not achieved must be considered in the evaluation of the data. Nonconformance to any specified parameters must be described and discussed in the final report if the Technical Manager (non

- GLP study) or Study Director (GLP study) chooses to report the data.

If criteria listed in this method performance section are not met, maintenance may be performed on the system and samples reanalyzed, or other actions taken as appropriate. Document all actions in the raw data.

If data are to be reported when performance criteria have not been met, the data must be footnoted on tables and discussed in the text of the report.



## 13.1 System Suitability – Analysis Batch

A minimum of three system suitability samples should be injected at the beginning of each analytical run. These samples are run prior to the calibration curve. It is suggested that the system suitability injections have area counts with a target RSD of ≤5% and a target retention time RSD of ≤2%. There is no defined acceptability limit on these results as the %RSDs are dependent on the number of MRM transitions being monitored in the LC/MS/MS run or time period. Any effect of system suitability is incorporated in the QC acceptance criteria.



## 13.2 Calibration and Limit of Quantitation (LOQ) – Analysis Batch

Calibration Curve: The coefficient of determination (r 2 

### ) value for the calibration curve must be greater than or equal to 0 .990 corresponding to a correlation coefficient (r) = 0.995. Each point in the curve must be within

± 25% of the theoretical concentration with the exception of the LLOQ, which may be within ± 30%.

CCV Performance: The calibration standards that are interspersed throughout the analytical sequence are evaluated as continuing calibration verifications in addition to being part of the calibration curve. The accuracy

### ETS -8- 044. 1 Page 20 of 22 Method of Analysis for the Determination of Perfluorinated Compounds in Wate r by LC/MS/MS; Direct Injection Analysis of each curve point must be within 25% of the theoretical value ( within 30% for lowest curve point ) . Samples that are bracketed by CCVs not meeting these criteria must be reanalyzed.

Limits of Quantitation (LOQ): The lower LOQ (LLOQ) is the lowest non

- zero active standard in the calibration curve; the peak area of the LLOQ must be at least 2X that of the average area counts for all prepared procedural blank(s). By definition, the measured value of the LLOQ must be within 30% of the

theoretical value.

Demonstration of Specificity: Specificity is demonstrated by chromatographic retention time (within 4% of standard) and the mass spectral response of unique ions.



## 13.3 Blanks – Method/Procedural Blanks and Trip

Method/ Procedural Blanks: Multiple procedural blanks should be interspersed throughout the analysis batch and the analytical sequence. At a minimum, method blanks are analyzed prior to instrument calibration, prior to the analysis of CCV samples, after every 10 sample injections, and at the end of the analytical run.

The mean area counts (or area ratios when using IS calibration) for each analyte must be less than 50% of the area count of the LOQ standard. If the area counts of the procedural blanks exceed 50% of the LOQ standard,
then the LOQ must be raised to the first standard level that meets criteria.

Trip Blank: A t rip blank of ASTM Type I water (or lab equivalent) is prepared in a sample container in the laboratory and treated as a sample, including exposure to shipping, sampling site conditions, storage, preservation and all analytical procedures. The trip blanks results for each analyte are included with the

repo rted sample results.



## 13.4 Data Accuracy and Precision – Analysis Batch

Lab Control Spikes: The average recovery at each LCS level for each target analyte and appropriate SRS

should be within 80

- 120% and the percent relative standard deviation of the recoveries must be less than or equal to 20%. If the average recovery of a spiking level falls outside method acceptance, but at least 67% (6

out of 9 ) o f LCS samples are within 20 % of their respective nominal value (33% of the QC samples, not all replicates at the same concentration, may be outside 20% of nominal value), the average recovery will be flagged as outside method acceptance criteria. All LCS samples will be control charted as per ETS

- 12

- 012. If the average recovery of one of the spiking levels exceeded the analytical method uncertainty as determined by

ETS

- 12

- 012, that analytical batch uncertainty will be expanded for that particular study. The average recovery

at each LCS level for mixed branched/linear isomer PFOA and PFOS should be within 70

- 130% and the percent relative standard deviation of the recoveries must be less than or equal to 20%.

Field Duplicates: The relative percent difference (RPD) of duplicate samples should be less than 20% for the precision of sample preparation and analysis to be considered in control. Replicate samples not meeting the 20% RPD criteria are flagged and reported as outside of QC acceptance criteria.

Field Matrix Spikes: FMS acceptance criteria are recoveries within ±30% of the expected value for each target analyte and appropriate SRS. Sample data with FMS recovery outside of ±30% but within ±50% of the expected value are flagged and reported as outside of QC acceptance criteria. Data with FMS recovery outside of ±50% of the expected value are reported as NR, where NR is defined as “Not Reportable” data outside of QC acceptance criteria. If FMS recovery could not be assessed because FMSs were at an inappropriate level, then Laboratory Matrix Spikes (LMSs) may be substituted. If LMS recoveries are within

±30% for each target analyte and SRSs the data are reportable but flagged as not meeting the FMS method acceptance criteria.



## 13.5 Analytical Method Uncertainty

Analytical method uncertainty for each target analyte and SRS is determined with control charted historica l analysis batch LCS data for the method and reported with each analysis batch. 5 

### Uncertainty determinations

5 Method uncertainty based on INTERNATIONAL ANS/ISO/IED STANDARD 17025 reference (GUM, Guide to the Expression of

Uncert ainty in Measurement). Method application demonstrated in ETS

- 12

- 012, citing references: a.) EURACHEM/CITAC Guide, “Quantifying Uncertainty in Analytical Measurement,” Second Edition; Editors: S.L.R. Ellison, M. Rosslein, and A. Williams

. b.)Georgian, Thomas, “Estimation of Laboratory Analytical Uncertainty Using Laboratory Control Samples,” Environmental Testing &

### ETS -8- 044. 1 Page 21 of 22 Method of Analysis for the Determination of Perfluorinated Compounds in Wate r by LC/MS/MS; Direct Injection Analysis are based on INTERNATIONAL ANS/ISO/IED STANDARD 17025 reference (GUM, Guide to the Expression of Uncertainty in Measurement) and described in ETS -12- 012 . At least thirty data points are required for determining analytical method uncertainty. The method uncertainty is defined as 2x the standard deviation of the percent recoveries of the pooled lab control spikes. While all LCS data points are control charted, only the most recent fifty data points are used for determining the method uncertainty.

When less than thirty LCS data points have been generated for a given analyte, the analysis batch LCSs are used to determine the data uncertainty. If FMSs meet the ±30% recovery criteria at a level appropriate to the endogenous level, and the LCS meet the ±20% recovery criteria, then the uncertainty of the data is determined

as within 100±20%.

Analysis batch sample data with FMS recovery outside of ±30% but within ±50% of the expected value are flagged and reported as outside of QC acceptance criteria with expanded uncertainties. Data with FMS recovery outside of ±50% of the expected value are reported as NR, where NR is defined as “Not Reportable” data outside of QC acceptance criteria. If FMS recovery could not be assessed because FMSs were at an inappropriate level, then Laboratory Matrix Spikes (LMSs) may be substituted. If LMS recoveries are within ±30% for each target analyte and appropriate SRSs the data are reportable but flagged as not meeting the FMS method acceptance criteria with uncertainties of ±30%. If FMS do not meet the ±30% recovery criteria, and historical FMS data does not exist, the analytical uncertainty is evaluated on a sample

- by -s ample basis, the data may be reported with expanded uncertainty and are flagged.



## 13.6 Quantitation of PFOA/PFOS – Analysis Batch

Calibration standards consisting of mixed branched and linear isomer PFOS/PFOA are preferred. Quantitation is performed by integrating the linear and branched isomers together. Alternately, the linear and branched isomers can be integrated separately, applying the appropriate true value to each calibration curve

po int for each isomer. The LCS and samples are then quantitated by integrating the linear and branched isomers separately (requires separate analytical results files) and quantitating the resulting peak against the

linear or branched calibration curve

. The results from both integrations are then summed to produce the final result. Integrating the linear and branched isomers separately may be helpful for those samples where the linear/branched ratios do not closely match those of the reference standards.

Ho wever, for PFOS/PFOA target analytes, if the calibration standards are comprised of predominantly linear isomers only t he method requires the addition of LCS s of mixed branched/linear isomer PFOS/PFOA. The purpose of including these LCSs is to demonstrate quantitative equivalency (or quantitative bias) of the isomeric mix when using a predominantly linear PFOS or PFOA standard for calibration. Alternatively, in lieu of mixed branched and linear isomer PFOS/PFOA LCSs, mixed branched and linear isomer PFOS/ PFOA TBMSs may be applied to demonstrate method accuracy and precision.

An alternate method of quantitation can be performed whereby only the linear isomer of PFOS/PFOA is integrated and used for generating the calibration curve. The LCS and samples are then quantitated by integrating the linear and branched isomers separately (requires separate analytical results files) and quantitating the resulting peak against the linear calibration curve. The results from both integrations are then summed to produce the final result. Integrating the linear and branched isomers separately reduces the on

column concentration for those samples that contain both linear and branched isomers of PFOA/PFOS. This ensures that the concentration detected is within the a range of the calibration curve that is comparable regardless of whether the calibration curve was generated using predominantly linear isomers of PFOS/PFOA or linear plus branched isomers of PFOS/PFOA.



## 14 Pollution Prevention and Waste Management

Waste generated when performing this method will be disposed of appropriately. The original samples will be archived at the 3M Environmental Laboratory in accordance with internal procedures.

Analysis, November/December 2000. c.)Taylor, B.N. and CE. Kuyatt, NIST Technical Note 1297, 1994 Edition: “Guidelines for Evaluating and Expressing the Uncertainty of NIST Measurement Results.”d.)Adams, T.M., “A2LA Guide for the Estimation of Measurement Uncertainty in Testing”, July 2002.

### ETS -8- 044. 1 Page 22 of 22 Method of Analysis for the Determination of Perfluorinated Compounds in Wate r by LC/MS/MS; Direct Injection Analysis 

## 15 Records

Each data package generated for a study must include all supporting information for reconstruction of the data. Information for the data package must include, but is not limited to the following items: study or project number, sample and standard prep sheets/records, instrument run log (instrument batch records, instrument

ac quisition method, summary pages), instrument results files, chromatograms, calibration curves, and data

calculations.



## 16 Affected Documents

None.



## 17 Revisions

Revision

Number Summary of Changes

1 Section 1

. Included the use of internal standard calibration by this method.

Section 2. Included the use of internal standard calibration by this method. Included the use of a solvent/water mixture when analyzing for PFUnA, PFDoA, PFTrDA, and FOSA.

Section 3

. Added definitions for internal standard, surrogate internal standard, and
surrogate recovery standard. Section 6.Removed the details regarding the instrument parameters to section 10 of the

method

. Section 7. Updated reference standards to include internal standards and surrogates. Changed concentration levels for working standards and included the use of internal
standards and surrogates. Section 8. Inserted a new section on sample bottle preparation.

Se ction 9 Quality Control. This section was previously section 10 in ETS -8- 044.0. Updated

QC criteria to be consistent with method ETS -8- 154.4.

Section 10 Procedures . This section was previously section 8 (Sample Handling) in E TS -8- 044.0. Added detail regarding the preparation of LCSs. Included the use of methanol as a

dilution solvent.

Section 11 Samp le Analysis

. This section was previously section 10 in ETS -8- 044.0.
Included the details regarding the instrument parameters. Section 12 Data Analysis and Calculations. This section was previously section 11 in ETS

8- 044.0. Removed the equation for calculating the analytes concentration, indicating that
this is done by the instrument software.
Section 13 Method Performance. This section was previously section 12 in ETS -8- 044.0. Updated QC criteria to be consistent with ETS -8- 154.4. Added information on the determination of analytical method uncertainty and quantitation of PFOA/PFOS.
Section 14 Pollution Prevention. This section was previously section 13 in ETS -8- 044.0. Section 15 Records. This section was previously section 14 in ETS -8- 044.0.

Section 16 Affected Documents. This section was previously section 15 in ETS -8- 044.0. Section 17 Revisions. This section was previously section 16 in ETS

- 8

- 044.0.

# A TTACHMENT 

# D: D EVIATION 

# ( S 

# )

# R ECORD OF 

# D EVIATION 

# /N ONCONFORMANCE

ETS -4- 008.7 Documentation of Deviations and Control of Nonconforming Testing Page 1 of 1 

## I. Identification
Study / Project No.

GLP10

- 01

- 01

- 28 

### Date(s) of Occurrence: Sequence b120405a 

### Document Number:

ETS -8- 044. 1


### Deviation type  SOP  Equipment Procedure  Method (Check one)  Protocol  GPO  Other: 

## II. Description (attach extra pages a s needed) 

## Method Requirements:

1. FM S (ETS

- 8

- 044. 1 section 13.4 ): re coveries within 100% ± 3 0 %.



## Actual procedure/process:

1. The high FMS for sample location RW331S had a recovery of 68.0 % for PFOA

.



## III. **Actions Taken** (such as amendment issued, SOP revis ion, etc.)



## Corrective Action (  Yes 

##  No 

## ) Reference :

Acceptability of the nonconforming work:

1. The non

- compliant FM S will be flagged in the final report. Since both spike levels were appropriate as compared to the sample location, the method uncertainty for sample location RW331S will be adjusted accordingly to ± 32%.



### Actions:  Halting of Work  Client Notification  Work Recall  Withholding of Report

 Other: Deviations will be noted in final report.



### Project Lead /PAI Approval: 

## Susan Wol f Date:

S tudy Director (if GLP): Date:

Sponsor Approval (for GLP protocol deviations): 

## NA Date: 

## NA

T echnical Reviewer (optional): NA Date: NA

Laboratory Department Manager Approval: Date:



## IV. Authorization to Resume Work

Where halting of work occurred, resum ption of work must first be approved by Laboratory Management 

### Laboratory Department Manager Approval: 

## NA Date: 

## NA

**Deviation No. ______________**

(assigned by Study Director or Team Leader at the end of study or project)