Document ypkYBo1YVDdOnLmdYzO7Rrke4

UNITED STATES ENVIRONMENTAL PROTECTION AGENCY WASHINGTON, D.C. 20460 To: Pauline Wagner, Chief Inert Ingredient Assessment Branch Office of Pesticide Programs OFFICE OF PREVENTION, PESTICIDES AND TOXIC SUBSTANCES From: E. Laurence Libelo, Ph.D., Environmental Engineer David G. Lynch, Environmental Scientist Andrew Manamtov, Ph.D. Chemist Robert Boethling, Ph.D. Microbiologist Exposure Assessment Branch Economic, Exposure and Technology Division Office of Pollution Prevention and Toxics Through M. Catherine Fehrenbacher, Chief Exposure Assessment Branch Date: March 8, 2006 Re: Meeting with Registrant on perfluorinated chemical (Masurf-FS-780, Fluowet PL 80-B and Fluowet PL-80) use as inerts Pauline, As discussed at the meeting on March 5th, 2006 we have serious concerns about the use of perfluorinated surfactant product as inerts in pesticide formulations. We have very little information on the specific chemicals discussed, but based on what we do have and our understanding of these chemicals from other, analogous chemicals, we do not believe that it is possible to say that they will not cause harm to the environment and human health. There were a number of issues discussed regarding the potential for these products to contain or form perfluorinated acids (PFAs), including perfluorinated octanoic acid (PFOA). Based on the process and raw materials used in producing these products OPPT believes that they contain PFOA and other PFAs and, if released to the environment as part of pesticide formulations, will be a source of widespread PFOA and other PFA contamination. OPPT also believes that these compounds themselves will be degraded in the environment to form PFOA and other PFAs. OPPT believes that testing is needed to determine the level of PFOA and PFA precursors present as impurities and minor constituents in perfluorinated products used in pesticide formulations. Internet Address (URL) http://www.epa.gov Recycled/Recyclable Printed with Vegetable Oil Based Inks on 100% Postconsumer, Process Chlorine Free Recycled Paper We also believe that extensive testing is needed to determine the potential for degradation of the parent chemicals, the environmental behavior of the parents and impurities, toxicity of the parent and degradates and their of uptake by plants and animals. Please feel free to contact us to discuss these issues further. Specific Comments: ' 1. As discussed at the meeting on March 2ndbetween OPP, OPPT and the Registrant, OPPT agrees that the NMR data presented indicate that the compounds tested (Masurf FS-780, Fluowet PL-80-B and Fluowet PL-80) show that they contain phosphonic or phoshinic acids and not phosphoric acid above the limit of detection of about 2 ppm. The presence of phosphoric acids below 2ppm cannot be ruled out. The NMR techniques used do not allow the detection and quantification of perfluorocarboxlyates, including PFOA, so it is not possible to determine their presence or concentration without additional analysis. 2. Based on the synthesis pathway using RfI reaction with P, we believe that there will be residual unreacted iodide and other products. Typically these reactions are not 100% complete, and we have seen that other products produced from perfluoroiodides or perfluoro telomer alcohols contain PFAs (including PFOA) and PFA precursors at several hundred ppm up to several percent as residuals and impurities1. An analysis of residuals and impurities, including iodide, alcohols, acids, anhydrides and other perfluorinated chemicals, is needed to determine the amount present. This should be conducted to allow detection and quantification at parts per trillion levels. 3. OPPT believes that the phosphinic and phosphonic acids will be degraded in the environment by abiotic and biologically mediated processes to form perfluorinated acids including PFOA. Phosphonates can be rapidly degraded by cleavage of the C-P bond abiotically in the presence of multivalent cations such as Mn (II) and Fe (III)2. Hydrolysis by oxidation catalyzed by metal ions is rapid and catalysis by soil oxihydrides can be expected once they are released to soils. These compounds are also readily degrade by photolysis when associated with metal ions3 C-P lyase and similar enzymes, common in nature, have been shown to cleave the C-P bond in phosphonic and phoshinic acids4. While these reactions are fairly slow the extreme persistence of the perfluorinated acids in the environment suggest that over time the phosphonic and phosphinic acids will be degraded. Recent data on biodegradation of perfluorinated telomer alcohol has indicated that the C F bond can be cleaved producing shorter perfluoro chains. This suggests that microbially mediated reactions can produce perfluorocarboxylates through removal of the terminal C F fluorines5. Humans and non-human organisms exposed to these products will absorb perfluorinated chemicals. For perfluorinated acids bioaccumulation factors vary with chain length. Longer chain length PFAs have very high bioconcentration factors (BCF), equal to or greater than those of PCBs6, and it is expected that the phosphonic and phoshinic acids will show similar behavior. Bioconcentrtaion tests are required to determine the BCF of all the perfluorinated major and minor constituents and degradation products. Recent data have shown that perfluorinated compounds are readily taken up by plants growing in contaminated soil7. OPPT believes that the phosphonic and phoshinic acids as well as perfluorinated acids including PFOA and other trace constituents and impurities will be taken up by plants grown in soil treated with pesticide formulations containing these products. Plant uptake and rotational crop uptake studies are needed to determine if PFOA and other perfluorinated compounds will be present in crops grown using these products and if so, at what levels. Data on the environmental behavior and fate of all perfluorinated chemicals present in the formulation are needed. These must include basic chemical properties such as Kow, vapor pressure, water solubility etc., as well as lab and field studies to allow evaluation of the release, movement and fate of these compounds. Most of the basic studies can be should be conducted on individual chemicals rather then the bulk formulation. For example, each individual perfluoro chain length acid (C4-C24) present in the product should be studied individually. The field studies can be conducted using formulated products as long as the levels of the chemicals applied are high enough to allow analysis and quantification of each perfluorinated constituent and degradation product. A partial list of studies required to provide necessary information is attached. While there was not an OPPT toxicologist present at the meeting we have spoken with toxicologists in the OPPT Risk Assessment Division (RAD) about the potential toxicity of the phosphonic and phoshinic acids. OPPT/RAD believes that they will exhibit acute and chronic toxicity similar to other perfluorinated acids (for example PFOS and PFOA) based on their structure. Discussion with RAD is needed to determine the toxicity testing needed to understand the effects of these compounds. Partial list of data required to allow evaluation of environmental fate and transport. Chem Properties Testing Study Dissociation constants in water Water solubility Octanol/Water Partitioning Vapor Pressure UV/visible absorption Hydrolysis as a function of pH Environmental Fate Testing Soi dsorption/desorption Modified SCAS Test Recommended OPPTS or OECD Guidelines OECD 112 OECD 105 OECD 107 or 117 OECD 104 OPPTS 830.7050 OECD 111 OPP 163-1 OECD 302b , Aerobic and Anaerobic Transformations in Soil Aerobic and Anaerobic Transformations in Aquatic Sediment systems Direct Photolysis in Water Indirect Photolysis Screening Test Phototransformation of Chemicals on Soil Surfaces Simulation test-Aerobic Sewage Treatment (Activated Sludge Units) Anaerobic biodegradability of organic compounds in digested sludge: measurement of gas production Field Dissipation Prospective Groundwater OECD 307 OECD 308 OPPTS 835.2210 OPPTS 835.5270 OECD Jan. 2002 Draft OECD 303A OECD 311 164-1 (Revised guideline) Draft guideline References Cited: 1. Dinglasan-Panlilo, M.J.A, and S. Mabury, 2006. Significant residual fluorinated alcohols present in various fluorinated materials, Environ. Sci. Technol., 40:1447 2. Nowak, B., and A. T. Stone, 2003. Manganese-catalyzed degradation of phosphonic acids, Environ. Chem. Lett., 1:24-31 3. Steber, J., and P. Wierich, 1986. Properties of hydroxyethane diphosphonare affection its environmental fate: degradability, sludge adsorption, mobility in soils, and bioconcentration, Chemsphere, 15:929-945 4. Raschke H, Rast H-G, Kleinst.uck R, Sicius H, Wischer, D., 1994, Utilization of 2phosphonobutane-l,2,3-tricarboxylic acid as source of phosphorous by environmental bacterial isolates, Chemosphere, 29:81-8 Schowanek D, Verstraete W., 1990. Phosphonate utilization by bactaria in the presence of alternative phosphorous sources, Biodegradation, 1:45-53 Nowack, B., 2003. Review, Environmental chemistry of phosphonates, Water Res, 37: 2533-2546 , 5. Wang, N., Szostek, B., Buck, R. C., Folsom, P. W., Sulecki, L. M., Capka, V., Berti, W. R., Gannon, J. T., 2005. Fluorotelomer alcohol biodegradation-direct evidence that perfluorinated carbon chains breakdown. Environ. Sci. Technol., 39:7516-7528 6. Martin, J.W., S.A.Mabury, K.R. Solomon, and D.C. Muir, 2003. Bioconcentration and tissue distribution of perfluorinated acids in rainbow trout (Oncorhynchus mykiss), Environ. Toxicol. Chem., 22:196-204 7. 3M, 2005. Perfluorooctanoic Acid (PFOA) Site Related Environmental Assessment Program Quarterly Report, U.S. EPA Docket EPA-HQ-OPPT-2004-0112