Revision No.: 3
Date: March 18, 2013
Page 1 of 80
Studies of the Degradation of Fluorotelomer Polymers, and
Formation of Fluorotelomer & Perfluorinated Monomers
And
The Analysis of Fluorotelomer & Perfluorinated
Compoundsin SoilsEnvironmental Media
Subtask ERD08102
Level II
Quality Assurance Project Plan (QAPP)
Process Modeling Branch
Ecosystems Research Division
National Exposure Research Laboratory
Office of Research and Development
U. S. Environmental Protection Agency
960 College Station Road
Athens, GA30605
Principal Investigator: John Wm. Washington, Ph.D.
Co-Investigator: Jonathan E. Naile, Ph.D.
Approvals:
______Date______
John W. Washington, Ph.D., Principal Investigator
______Date______
Jonathan E. Naile, Ph.D., Co-Investigator
______Date______
W. Jack Jones, Ph.D., Branch Chief, PMB, ERD
______Date______
Roy C. Sidle, Ph.D., Director, ERD
______Date______
James L. Kitchens, Quality Assurance Manager, ERD
TABLE OF CONTENTS
1.0Project Management
1.1Title and Approval Sheet1
1.2Table of Contents3
1.3Distribution List4
1.4Project/Task Organization4
1.5Problem Definition/Background5
1.6Project/Task Description7
1.7Quality Objectives and Criteria for Measurement Data7
1.8Special Training Needs/Certification9
1.9Documents and Records9
2.0Data Generation and Acquisition
2.1Experimental Schedule & Design10
2.2Sampling Methods10
2.3Sample Handling and Custody11
2.4Analytical Methods11
2.5Quality Control11
2.6Instrument/Equipment Testing, Inspection, and Maintenance15
2.7Instrument/Equipment Calibration and Frequency16
2.8Inspection/Acceptance of Supplies and Consumables17
2.9Non-direct Measurements17
2.10Data Management17
3.0Assessment and Oversight
3.1Assessment and Response Actions18
3.2Reports and Management18
4.0Data Validation and Usability
4.1Data Review, Verification, and Validation19
4.2Verification and Validation Methods19
4.3Reconciliation with User Requirements19
5.0General Perfluorinated Chemicals References.19
Appendix A: State of Knowledge for Perfluorinated Compounds Research...... 24
Appendix B: SOPs Pertaining to this QAPP...... 25
Appendix C: QAR Form...... 54
1.3 Distribution List:
John Washington– PMB, ERD, NERL Principal Investigator
Jonathan Naile– PMB, ERD, NERL Co-Principal Investigator
Thomas Jenkins– SEE Laboratory Technician
Jack Jones– PMB, ERD, NERL Branch Chief
Jim Kitchens– ERD, NERL Quality Assurance Officer
1.4 Project/Task Organization:
Coordinated independent research will be conducted by scientific staff in the National Exposure Research Laboratory, Ecosystems Research Division, Processes and Modeling Branch. This independent research will be conducted by PMB research staff including Drs. John Washington andJonathan Naile. Dr. Washington will guide and oversee work performed by Dr. Tom Jenkins.
Mr. James L. Kitchens is the QA manager for ERD-Athens.
The purpose of this work is to fulfill a request of ORD fromthe EPA Office of Pollution Prevention and Toxics (OPPT) to provide fundamental environmental-fate data on fluorotelomer polymers (FTPs) and fluorotelomer (FTCs) and perfluoro compounds (PFCs) that OPPT and other EPA offices will use to characterize sources and pathways of perfluorooctanoic acid (PFOA)and other PFCs in the environment. These data will ensure that regulations are based on sound science. In OPPT, users of this ORD product include David Widawsky, Director EETD, Cathy Fehrenbacher, EAB Branch Chief, and the staff of EAB (Figure 1).
This work will entail collecting soil samples and other environmental samples as opportunity allows or requests are submitted, characterizing PFCs in these samples, performing laboratory experiments to assess degradation of perfluoroalkyl monomers/polymers, and analysis of soil extracts to monitor disappearance of perfluorinated telomers or ingrowth of degradation products. Responsibilities of the researchers include sampling, recording and validating analytical and experimental results in detail, adjusting and calibrating laboratory equipment, evaluating SOPs and modifying them as need is identified, computing kinetic and, perhaps, thermodynamic parameters, and providing statistical treatment of the experimental data.
The organizational relationship among researchers and OPPT product users is given in Figure 1.
1.5 Problem Definition/Background:
1.5.1 Problem Definition:
Perfluoroalkyl monomers are used to synthesize a variety of fluorotelomer-based polymer products (FTPs). These FTPs are used to impart soil- and liquid-repellent properties to a wide range of modern products including paper, textiles, leather and carpeting. Because of their remarkable stain- and wetting-resistance, FTPs are highly valued by industry and consumer alike, and, consequently, represent a huge commercial market world-wide.
Several species of perfluoroalkyl monomers are volatile, and, when released into the environment potentially can be dispersed through atmospheric transport although the extent to which this occurs remains uncertain. When perfluoroalkyl monomers are subjected to common environmental conditions, oftentimes they can be oxidized to highly persistent acids. One of the chief perfluoroalkyl monomers in commercial production today is the volatile 8-2 telomer alcohol. Under oxidizing conditions, the 8-2 telomer alcohol canbe oxidized to the highly persistent perfluorinated octanoic acid (PFOA). Given the volatility of the telomer alcohols and the inertness of the perfluoroalkyl acids, perfluoroalkyl compounds have the potential for widespread dispersal although the extent to which this occurs remains uncertain. Recognition of the world-wide dispersal of PFOA is relatively recent and numerous toxicity studies on the molecule are underway.
There are several recognized sources to the environment of the 8-2 perfluorinated telomer alcohol and PFOA; however, significant questions remain regarding what role, if any, commercial FTPs might play as potential sources of fluorotelomer precursors of perfluorocarboxylic acids such as PFOA: are residual impurities in FTPs able to leach to the environment?; and, are the FTPs themselves subject to degradation to alcohols or acids under environmental conditions? While we have shown that non-commercial test FTPs do degrade in soils, this remains to be determined with more certainty for commercial FTPs. Resolution of these questions is essential for delineating the source term for PFOA to the environment. If commercial FTPs are a source for PFOA precursors or PFOA, the current source term for PFOA that is based on presently confirmed sources might be underestimated by orders of magnitude.
In order to resolve the above general problem, the concentrations of PFCs in numerous environmental compartments will need characterization, both in the general-ecosystem sense and in the site-specific sense. To address these needs, numerous extraction and analytical methods are required for soils, polymers and other complex matrices. This QAPP addresses quality issues associated with these procedures and their development.
1.5.2 Background:
To address uncertainties regarding sources and pathways of PFOA in the environment, the Office of Pollution Prevention and Toxics (OPPT) plans to prepare an assessment. However, required data elements for such an assessment are incomplete. In an effort to fill these gaps, OPPT is negotiating with a consortium of industries that work with perfluoroalkyl monomers, the Telomer Research Program (TRP). One of OPPT’s objectives in these negotiations is to formulate an Enforceable Consent Agreement (ECA) that calls for TRP to conduct tests on fluorotelomer-based polymers (FTPs) to determine the potential for FTP degradation. FTPs are the purified starting materials that are used in the production of commercial FTPs. The objectives of this testing are to evaluate the stability of FTPs currently in the environment and to determine whether environmental degradation of these FTPs might be a major source of PFOA in the environment. Degradation tests have been developed by the Organization of Economic Co-operation and Development (OECD), and include:
1) Modified SCAS Test - an aggressive test calling for daily replenishment of microbes and organic carbon. The specific protocol is the OPPTS 835.5045, a modification of OECD 302A;
2) OECD 303A - an aerobic sewage-treatment simulation test;
3) OECD 307 - an aerobic and anaerobic test for chemical transformation in soil;
4) OECD 308 - an aerobic and anaerobic test for transformation in aquatic sediment systems; and
5) OECD 311 - an anaerobic test for biodegradability in digested sludge.
OPPT requestedthat the Office of Research and Development (ORD) undertake a research program to adapt these tests, as needed, for testing the degradability of FTPs. Two ORD national labs have been asked to develop research programs to address OPPT’s needs:
1) the Ecosystems Research Division of the National Exposure Research Laboratory (ERD/NERL) has been asked to develop a program to evaluate the biodegradability of FTPs in soils, and analyze selected environmental samples for PFCs; and
2) the Land Remediation and Pollution Control Division of the National Risk Management Research Laboratory (LRPCD/NRMRL) has been asked to develop a program to evaluate the biodegradability of FTPs in sewage and sludge.
This QAPP describes ERD/NERL’s handling, analytical and extraction procedures that will be needed to address the research needs of EPA offices regarding PFCs.
1.6 Project/Task Description:
Questions surrounding the fate of commercialFTPs in the environment include: 1) Can some of the residual monomers leach from the FTP under environmental conditions?; and 2) Does the intended FTP itself (i.e., the polymer and oligomer fractions) degrade under environmental conditions at a significant rate or is the FTP stable? These points are crucial because: 1) if residual monomers can leach from FTPs, they might well be major contributors to PFOA and related compounds in the environment; and 2) if the intended FTP product (polymer + oligomer fractions) breaks down, the potential source term for PFOA, and related compounds, to the environment increases orders of magnitude compared to a scenario where only the residuals degrade to PFOA
We plan to develop methods for the testing of FTPs in soils and anticipate that the resulting protocol can be used directly by others to reproduce our results and/or test additional soils and FTPs.
In this QAPP, we describe:
1) methodsdevelopment testing - an initial phase in which methods are refined and detailed procedures aredeveloped for handling, analysis and extraction of PFCs from environmental matrices such as soil materials; and
2) exploratory testing of compound properties –an early phase in which molecular properties such as ion-pairing propensity, sorption and volatilization under anticipated testing conditions are explored.
Whereas the efforts described above are aimed at addressing uncertainty in sources of PFCs, there are numerous outstanding questions regarding distribution of PFCs in the environment as well. Many of these questions regard distribution of PFCs in generic environmental compartments, but still other questions are expected to arise on a site-specific basis. Armed with the methods we develop to address the FTP-degradation question, we will analyze additional samples, and/or develop methods, as the opportunities or programmatic requests present themselves.
1.7 Quality Objectives and Criteria:
1.7.1 The Problem:
EPA/OPPT has developed a “Road Map” (USEPA, 2003c) which presents its understanding of the potential sources and pathways of PFOA in the environment resulting from the manufacture and use of fluorinated telomers. The Road Map presents an overall summary of the potential sources and pathways so that EPA/OPPT can understand the sources of PFOA and its precursors entering the environment and pathways leading to human exposures. It also states that one of the primary questions facing EPA is to understand whether FTPs can undergo transformation to PFOA in the environment, as well as the mechanisms and rates for such transformation. Plausible source terms for the release of PFOA into the environment include the thermal breakdown of perfluorinated polymers in cookware and internal combustion engines (Stock et al., 2004), and losses from production and application facilities. Some scientists suggest that these source terms seem unlikely to account for the global distribution and levels of PFOA currently being reported. An alternative hypothesis is that perfluoroalkyl telomers, used in a variety of FTPs and which possess high volatility, are released, transported atmospherically and subsequently transformed into PFOA. Of particular interest among the perfluoroalkyl telomers, are the perfluorinated telomer alcohols which are used in the synthesis of dyes, paints, adhesives, polymers and waxes. Telomer alcohols have the common structure CF3(CF2)nCH2CH2OH, where n is an odd number; generally 1 thru 9; the nomenclature refers to the number of fluorine-saturated carbons atoms and fluorine-absent methylene groups (i.e. 8-2 telomer alcohol: CF3(CF2)7CH2CH2OH). The 8-2 telomer alcohol is particularly important as a primary intermediate used in the preparation of FTPs (Lei, 2004). The telomer alcohols have been shown to be present in the troposphere at concentrations ranging from 11-165 pg/m3 and it is estimated that the global production in 2002 exceeded 6.5 million kg/yr (Stock et al., 2004).
Recent studies have shown that PFOA is an end product resulting from the microbially mediated oxidation of the 8-2 telomer alcohol in a mixed-microbial system and activated sludge (Dinglasan, et al., 2004). The proposed reaction pathway for this transformation is illustrated in Figure 2. The oxidation pathway is initiated by oxidation of the 8:2 fluorotelomer alcohol (8:2 FTOH) to the 8:2 fluorotelomer aldehyde (8:2 FTAL), which is considered a transitory intermediate in the mixed microbial system. The 8:2 FTAL is further oxidized to give the 8:2 fluorotelomer acid (8:2 FTCA), which can either undergo elimination of HF to give the 8:2 fluorotelomer 8:2-unsaturated acid (8:2 FTUCA), or alpha-oxidation to give the perfluorinated nonanoic acid (PFNA), which like PFOA is an end metabolite. The 8:2 FTUCA is the major metabolite formed in the mixed-microbial system (Dinglasan, et.al., 2004). The 8:2 FTUCA is then oxidized through the beta-oxidation pathway to give the end metabolite, PFOA. Each of these metabolites has been identified by LC/MS/MS analysis and comparison to authentic standards (Dinglasan et al., 2004). Notably, no evidence has been found for the metabolic or environmental degradation of the end metabolite, PFOA (3M, 2003; Kudo and Kawashima, 2003). To explore these issues, we studied related research efforts (Appendix A) as a starting point to develop fundamental analytical procedures for characterization of PFCs in a variety of matrices (Appendix B). As we receive additional samples, analytical procedures will be developed and applied on an as-needed basis.
Figure 2: Synthesis of FTPs and conceptual degradation scheme.
1.7.2 The Study Questions:
Ultimately, we seek to answer, for OPPT three specific questions regarding the behavior of FTPs in soils:
1) Can the residual monomers leach from the FTPs in environmental settings?;
2) Does the FTP product (polymer + oligomer fractions) degrade?;
3)To what degree, and quantitatively how fast, are products formed from degradation of the FTPs,i.e, whether the source of the PFOA is the FTP product (polymer + oligomer fractions), the residual monomers that remain in the product, or both?and
On a more general basis, we seek to elucidate the concentrations of a variety of PFCs in a variety of environmental samples, and characterize controls on transport and transformations in the environment.
1.8 Special Training Needs/Certification:
Training of researchers on new activities, and of new researchers, will be performed by: 1) remote short courses; 2) on-site short courses; or 3) experienced research team members by demonstration followed by close supervision until the activity is mastered. Mastery of an activity will be determined by direct observation and scrutiny of the learner’s analytical results for known standards.
1.9 Documents and Records:
Researchers are required to document adequately in research notebooks all aspects of research as outlined in Athens LOP No. 5400-3, Laboratory Notebookand ORD-QA-02-0 Standard Operating Procedure Research Notebook Documentation will supercede LOP 5400-3. Researchers will follow the guidance outlined in Athens LOP No. 5400-8 Scientific Recordkeeping: Use of Electronic Media to manage and archive electronic files. When possible, instrument data will be exported to spreadsheets that will be designed to collate and manage data such as PFOA data in degradation studies. One of the spreadsheet cells will contain the unique file numbering information as described below that will link spreadsheet data back to the original instrument file. In some instances data, will be transferred by hand to personal computer where chemical data reduction or conversion will be carried out. Data transfer will be verified by visual and statistical review of the data. Notebooks are reviewed and signed by the principal investigator routinely, and as a regular part of data reduction and entry. All information associated with an experiment (e.g., chromatograms, spreadsheets, analytical spectra) are stored in lab notebooks and/or network drives that are backed-up periodically. Instrument PCs are fitted with either CD-ROM or DVD writers and electronic data files will also be copied to CD or DVD. The label on the CD will reference laboratory notebooks and instruments by EPA property number. Any standard, solution, or sample made during these investigations will be marked with a reference number/name, traceable to a specific entry in the lab notebook, so any member of the staff can verify how a given material has been prepared. The reference number will consist of the date it was received or made recorded as six digits in the order year, month, day so that, for example, November 1, 2005 would appear as 051101; the name will consist of the highest concentration solute and its concentration on a convenient division so that, for example, a 100pg/g PFOA standard made on November 1, 2005 would have a full name similar to “051101-100pg-g.” Results of investigations will be published in refereed journals.
2. Data Generation and Acquisition:
This QAPP covers a wide range of experimental and theoretical research activities with challenging chemicals in complex matrices. And these research activities are oriented toward addressing a wide range of objectives and research pitfalls. As such, not all QA parameters described herein are applicable to all of our planned research activities. Instead, these QA parameters will be applied at the discretion of the PI and co-PI based on their careful expert judgment.
2.1 Experimental Schedule & Design:
Because this QAPP describes procedures for fundamental, exploratory work, which can lead in innumerable directions at any stage, design will follow a course determined by the PI based on data and factors as they accumulate.
Much of this FTPwork will take place in 2012and continue through much of 2014. Coincident with the FTP research and continuing through 2014, additional PFC research will take place. Examples of these efforts might include: 1) analysis of water, soil and/or sediment from specific sites suspected of being contaminated; 2) development of methods for branch chained PFOA; 3) analysis of ‘pristine’ soils from sites around United States and the World; 4) 19F NMR studies of polymer-soil microcosms to allow interpretation of whether the nature of F bonds change with time; and 5) study of whether PFCs occur in petroleum products.