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RESEARCH 

TSCA-HQ-2004-016, RCRA-HQ-2004-0016, TSCA-HQ-2005-5001 

SEP A Fluorotelomer-Based Product Characterization 

Subject: MPI Research Technical Progress Report 

March 31,2010 to April 23, 2010 

1 Introduction 

This document presents the progress of the technical work for characterization of fluoroteiomerbased products and corresponding synthesized or purified polymers in support of the 

Biodegradation Testing Supplemental Environmental Project ("Biodegradation SEP"). This 

progress report is prepared pursuant to Characterization Laboratory Exhibit A: Scope of Wori<, 

Section 4f. This report describes the technical wori< peri'ormed up to the week ending April 23, 

2010. The following components of the Work Plan have been completed: Components 1, 2, 3, 5 

and 6. 

2 Progress Summary 

The initiation of technical work began on March 31, 2010, after acceptance of the MPI Research 

work plan by both EPA and DuPont. 

The fluorotelomer products were received from DuPont and the commercially available standards 

were ordered and received at MPI Research. The invoices are included in Appendix D. 

MPI Research has obtained a quotation from Wellington Laboratories for synthesis of the three 

compounds (Wori< Plan Component 4). MPI Research is waiting for approval to purchase these 

standards. The quotation is included in Appendix E. The estimated time of synthesis is six weeks. 

The synthesis will begin upon the receipt ofthe MPI Research order by Wellington Laboratories. 

The technical wori< consisted of method development outlined in Component 7 of the Work Plan. 

LC/MS/MS methods are being developed for the following analytes: 7-3 Fluorotelomer Acid, 8-2 

Fluorotelomer saturated Acid, 8-2 Fluorotelomer unsaturated Acid, Perfluorooctanoic Acid, 

Perfluorononanoic Acid, Perfluorodecanoic Acid and Perfluoroundecanoic Acid. 

GC/MS methods are being developed for the following analytes: 6-2 Fluorotelomer Alcohol, 8-2 

Fluorotelomer Alcohol, 10-2 Fluorotelomer Alcohol, 8-2 Fluorotelomer Ethene, 8-2 Fluorotelomer 

Iodide, 10-2 Fluorotelomer Iodide, Perfluorooctyl Iodide, Perfluorodecyl Iodide, 8-2 Fluorotelomer 

Acrylate, 7-2 Fluorotelomer iso-ethanol and PFOA telomer 8-2 ester. 

MPI Research 04/29/2010 Technical Progress Report ^^^ ^ ^ °'^ ^ 
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The total method development time incurred for the period of time covered by this report was 22 

hours. The associated cost for this method development work is $5,500 as identified in 

Component 7 of the Wori< Plan. The cost is based upon the daily rate of $2,000. The cost 

associated with commercially available standards that were purchased during the time period 

covered by this report was $2,417.80. This cost is identified in Component 3 of the Wori< Plan. 

The total costs associated with the components initiated with respect to this Progress Report are 

$7,917.80 The associated invoices are presented in Appendix D. 

3 Analysis by LC/MS/MS 

An HP1100 system interfaced to an Applied Biosystems API 4000 LC/MS/MS was used for the 

method development work. A gradient elution using a Zorbax® SB-C18,2.1 X 50 mm, 1.8|jm 

column was used for separation ofthe following analytes: 

Analytes 

8-2 Fluorotelomer saturated Acid 

8-2 Fluorotelomer unsaturated Acid 

7-3 Fluorotelomer Acid 

Perfluorooctanoic Acid 

Perfluorononanoic Acid 

Perfluorodecanoic Acid 

Perfluoroundecanoic Acid 

lUPAC name 

Decanoic acid, 

3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-

heptadecafluoro2-decenoic acid, 

3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-

hexadecafluoroDecanoic acid, 

4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-

pentadecafluoroPentadecafluorooctanoic acid 

Perfluorononanoic acid 

Perfluorodecanoic acid 

Perfluoroundecanoic acid 

CAS# 

27854-31-5 

70887-84-2 

812-70-4 

335-67-1 

375-95-1 

335-76-2 

2058-94-8 

The transitions for Perfluorooctanoic Acid, Perfluorononanoic Acid, Perfluorodecanoic 

Acid, and Perfluoroundecanoic Acid were based on previous work. The transitions for 8-2 

Fluorotelomer saturated Acid, 8-2 Fluorotelomer unsaturated Acid, and 7-3 Fluorotelomer 

Acid were determined using flow injection. A 1 ng/mL methanol standard containing all 

seven analytes was evaluated for chromatographic separation. 

The 8-2 Fluorotelomer saturated Acid was not detected because it was determined to be 

unstable in methanol. The 8-2 Fluorotelomer saturated Acid degrades to the 8-2 

Fluorotelomer unsaturated Acid. Stability conditions will be further investigated and will 

include solvent, temperature, and the effect of light. 

4 Analysis by GC/MS 

The analyses were perfomned on a Hewlett-Packard GC/MS system with positive chemical 

ionization using helium can'ier gas and methane reagent gas. A HP-IMS column was used for 

the development work for the following analytes: 

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Analytes 

6-2 Fluorotelomer Alcohol 

8-2 Fluorotelomer Alcohol 

10-2 Fluorotelomer Alcohol 

8-2 Fluorotelomer Ethene 

8-2 Fluorotelomer Iodide 

10-2 Fluorotelomer Iodide 

Perfluorooctyl Iodide 

Perfluorodecyl Iodide 

8-2 Fluorotelomer Acrylate 

7-2 Fluorotelomer iso-ethanol 

PFOA telomer 8-2 ester 

lUPAC name 

1H,1H,2H,2H-perfluorooctan-1-ol 

1H,1H,2H,2H-perfluorodecan-1-ol 

1H,1H,2H,2H-perfluorododecan-1-ol 

1H, 1 H,2H-perfluoro-1 -decene 

1H,1H,2H,2H-perfluorodecyl iodide 

1H,1H,2H,2H-perfluorododecyl iodide 

Perfluorooctyl Iodide 

Perfluorodecyl Iodide 

2-propenoic acid, 

3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-

heptadecafluorodecyl ester 

2-nonanol, 

3,3,4,4,5,5,6,6,7,7,8,8,9,9,9-

pentadecafluoroOctanoic acid, pentadecafluoro3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-

heptadecafluorodecyl ester 

CAS# 

647-42-7 

678-39-7 

865-86-1 

21652-58^ 

2043-53-0 

2043-54-1 

507-63-1 

423-62-1 

27905^5-9 

24015-83-6 

Not 

Available 

All analytes, with the exception of 6-2 Fluorotelomer alcohol and 7-2 Fluorotelomer iso-ethanol, 

were prepared in methyl tert-butyl ether (MTBE) at concentrations ranging from approximately 

100 pg/mL to 2000 |jg/mL from neat standards. 6-2 Fluorotelomer alcohol and 7-2 Fluorotelomer 

iso-ethanol were purchased as 50 ^ig/mL solutions in methanol. These standard solutions were 

analyzed by PCI/GC/MS in the scan mode to detemnine the appropriate ions to be monitored for 

each analyte. Not all analytes produced dominant molecular ions. Alternate instnjment 

conditions will be investigated. 

For each analyte, a 1 |jg/mL solution was investigated using single ion monitoring. 

An interference signal was detected in the solvent, methyl tert-butylether (MTBE) for the 8-2 

fluorotelomer ethene. Higher purity solvent will be investigated. 

The molecular ion for PFOA telomer 8-2 ester (MW = 860) could not be observed because the 

upper mass range for the instmment is 800. MPI Research is investigating whether a firmware 

solution exists for the instmment limitation. Otherwise, a lower molecular weight fragment must 

be used. 

5 Attachment s 

5.1 Appendix A: 

5.2 Appendix B: 

5.3 Appendix C: 

5.4 Appendix D: 

5.5 Appendix E: 

Raw Data (LC/MS/MS) 

Raw Data (GC/MS) 

Certificates of Analysis 

Invoices 

Quotations 

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•VH;^ -

I certify under penalty of law that I have examined and am familiar with the infonnation submitted 

in this document and all attachments and that this document and its attachments were prepared 

either by me personally or under my direction for supervision in a manner designed to ensure that 

qualified and knowledgeable personnel property gather and present the information contained 

therein. I further certify, based on my personal knowledge or on my inquiry of those individuals 

immediately responsible for obtaining the infonnation, that the information is tme, accurate and 

complete. I am aware that there are significant penalties for submitting false infonnation, including 

the possibility of fines and imprisonment for knowingly and willfully submitting a materially false 

statement. 

'/Af/^^/^ 

Xiang (Robert) Zhu, Study Director Date 

MPI Research 04/29/2010 Technical Progress Report '^'^^^ '^''"^'^