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Provisional Peer-Reviewed Toxicity Values for Methyl Phosphonic Acid (Casrn 993-13-5)

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Provisional Peer-Reviewed Toxicity Values for Methyl Phosphonic Acid (Casrn 993-13-5) EPA/690/R-09/029F l Final 9-10-2009 Provisional Peer-Reviewed Toxicity Values for Methyl phosphonic acid (CASRN 993-13-5) Superfund Health Risk Technical Support Center National Center for Environmental Assessment Office of Research and Development U.S. Environmental Protection Agency Cincinnati, OH 45268 COMMONLY USED ABBREVIATIONS BMD Benchmark Dose IRIS Integrated Risk Information System IUR inhalation unit risk LOAEL lowest-observed-adverse-effect level LOAELADJ LOAEL adjusted to continuous exposure duration LOAELHEC LOAEL adjusted for dosimetric differences across species to a human NOAEL no-observed-adverse-effect level NOAELADJ NOAEL adjusted to continuous exposure duration NOAELHEC NOAEL adjusted for dosimetric differences across species to a human NOEL no-observed-effect level OSF oral slope factor p-IUR provisional inhalation unit risk p-OSF provisional oral slope factor p-RfC provisional inhalation reference concentration p-RfD provisional oral reference dose RfC inhalation reference concentration RfD oral reference dose UF uncertainty factor UFA animal to human uncertainty factor UFC composite uncertainty factor UFD incomplete to complete database uncertainty factor UFH interhuman uncertainty factor UFL LOAEL to NOAEL uncertainty factor UFS subchronic to chronic uncertainty factor i FINAL 9-10-2009 PROVISIONAL PEER-REVIEWED TOXICITY VALUES FOR METHYL PHOSPHONIC ACID (CASRN 993-13-5) Background On December 5, 2003, the U.S. Environmental Protection Agency’s (U.S. EPA) Office of Superfund Remediation and Technology Innovation (OSRTI) revised its hierarchy of human health toxicity values for Superfund risk assessments, establishing the following three tiers as the new hierarchy: 1) U.S. EPA’s Integrated Risk Information System (IRIS). 2) Provisional Peer-Reviewed Toxicity Values (PPRTVs) used in U.S. EPA’s Superfund Program. 3) Other (peer-reviewed) toxicity values, including Minimal Risk Levels produced by the Agency for Toxic Substances and Disease Registry (ATSDR), California Environmental Protection Agency (CalEPA) values, and EPA Health Effects Assessment Summary Table (HEAST) values. A PPRTV is defined as a toxicity value derived for use in the Superfund Program when such a value is not available in U.S. EPA’s IRIS. PPRTVs are developed according to a Standard Operating Procedure (SOP) and are derived after a review of the relevant scientific literature using the same methods, sources of data, and Agency guidance for value derivation generally used by the U.S. EPA IRIS Program. All provisional toxicity values receive internal review by two U.S. EPA scientists and external peer review by three independently selected scientific experts. PPRTVs differ from IRIS values in that PPRTVs do not receive the multiprogram consensus review provided for IRIS values. This is because IRIS values are generally intended to be used in all U.S. EPA programs, while PPRTVs are developed specifically for the Superfund Program. Because new information becomes available and scientific methods improve over time, PPRTVs are reviewed on a 5-year basis and updated into the active database. Once an IRIS value for a specific chemical becomes available for Agency review, the analogous PPRTV for that same chemical is retired. It should also be noted that some PPRTV documents conclude that a PPRTV cannot be derived based on inadequate data. Disclaimers Users of this document should first check to see if any IRIS values exist for the chemical of concern before proceeding to use a PPRTV. If no IRIS value is available, staff in the regional Superfund and Resource Conservation and Recovery Act (RCRA) program offices are advised to carefully review the information provided in this document to ensure that the PPRTVs used are appropriate for the types of exposures and circumstances at the Superfund site or RCRA facility in question. PPRTVs are periodically updated; therefore, users should ensure that the values contained in the PPRTV are current at the time of use. It is important to remember that a provisional value alone tells very little about the adverse effects of a chemical or the quality of evidence on which the value is based. Therefore, users are strongly encouraged to read the entire PPRTV document and understand the strengths 1 FINAL 9-10-2009 and limitations of the derived provisional values. PPRTVs are developed by the U.S. EPA Office of Research and Development’s National Center for Environmental Assessment, Superfund Health Risk Technical Support Center for OSRTI. Other U.S. EPA programs or external parties who may choose of their own initiative to use these PPRTVs are advised that Superfund resources will not generally be used to respond to challenges of PPRTVs used in a context outside of the Superfund Program. Questions Regarding PPRTVs Questions regarding the contents of the PPRTVs and their appropriate use (e.g., on chemicals not covered, or whether chemicals have pending IRIS toxicity values) may be directed to the U.S. EPA Office of Research and Development’s National Center for Environmental Assessment, Superfund Health Risk Technical Support Center (513-569-7300), or OSRTI. INTRODUCTION Methyl phosphonic acid (MPA) is an environmental hydrolysis product of the chemical warfare nerve agents VX, GB (sarin), and GD (soman) (Munro et al., 1999). MPA has been detected in VX-contaminated soil, presumably as a hydrolysis product of ethyl methyl phosphonic acid, which is, itself, a hydrolysis product of VX at low (<6) or high (>10) pH (Munro et al., 1999). MPA is also formed very slowly in the environment from the hydrolysis of isopropyl methyl phosphonic acid (IMPA), which is a hydrolysis product of GB (Munro et al., 1999). In addition, a small number of bacteria species are capable of metabolizing IMPA to MPA (Zhang et al., 1999; Schowanek and Verstraete, 1990). The chemically related compound, diisopropyl methyl phosphonate (DIMP) is a by-product of the manufacture of GB (ATSDR, 1999; Munro et al., 1999). Sega et al. (1998) reported that the abiotic degradation of DIMP in groundwater resulted in IMPA and MPA, providing another source of MPA in the environment. The slow hydrolysis of pinacolyl methyl phosphonic acid (the primary product of GD hydrolysis) results in MPA formation from the environmental release of GD (Munro et al., 1999). MPA may also be found in the environment as a breakdown product of methyl phosphonate-containing pesticides and flame retardants (Munro et al., 1999). In the environment, MPA is fairly stable because it is resistant to hydrolysis, photolysis, and thermal decomposition (Munro et al., 1999). Its high solubility, low vapor pressure, low Koc, and low Henry’s law constant indicate that MPA will be highly mobile in soils and will exist primarily in aqueous compartments (Munro et al., 1999). Figure 1 shows the chemical structure of MPA. O H3C P OH OH Figure 1. Structure of Methyl Phosphonic Acid 2 FINAL 9-10-2009 No chronic RfD, RfC, oral slope factor, or inhalation unit risk for MPA is available on the U.S. Environmental Protection Agency’s Integrated Risk Information System (IRIS) (U.S. EPA, 2009), Drinking Water Standards and Health Advisories list (U.S. EPA, 2006a), or Health Effects Assessment Summary Tables (HEAST) (U.S. EPA, 1997). No documents for MPA are included on the Chemical Assessment and Related Activities (CARA) list (U.S. EPA, 1991, 1994). The U.S. Army (1999) derived an estimated RfD of 5.7 × 10-2 mg/kg-day for MPA based on a quantitative structure-activity relationship (QSAR) estimate of the chronic rat LOAEL of 566 mg/kg-day from TOPKAT® (Accelrys, Inc.), a commercial software program. Munro et al. (1999) mentioned the U.S. Army (1999) QSAR-based RfD but preferred a different RfD value of 2 × 10-2 mg/kg-day for MPA based on the subchronic rat NOAEL of 279 mg/kg-day for the closely related compound IMPA (Bausum et al., 1999). ATSDR (2007), NTP (2007), IARC (2007), and the WHO (2007) have not reviewed the toxicity of MPA. MPA is not included in the National Toxicology Program’s (NTP’s) 11th Report on Carcinogens (NTP, 2005). The American Conference of Governmental Industrial Hygienist (ACGIH, 2007), Occupational Safety and Health Administration (OSHA, 2007), and National Institute for Occupational Safety and Health (NIOSH, 2007) have not established occupational health standards for MPA. A U.S. Army (1975) review later summarized by Williams et al. (1987) and a review of chemical warfare agent degradation products (Munro et al., 1999) were consulted for relevant information. To identify toxicological information pertinent to the derivation of provisional toxicity values for MPA, literature searches were initially conducted in January 2007 using the following databases: MEDLINE, TOXLINE Special, TSCATS/TSCATS 2, CCRIS, DART/ETIC, GENETOX, HSDB, RTECS (these were not date limited); BIOSIS (from August 2000 to January 2007); and Current Contents (previous 6 months only). A final search for published studies was conducted for the period from July 2008 through March 2009. REVIEW OF PERTINENT DATA Human Studies No data regarding human toxicity resulting from oral or inhalation exposure to MPA were identified in the available reviews or the literature searches. Animal Studies Oral Exposure No chronic, subchronic, developmental, or reproductive toxicity studies conducted by the oral route of exposure were located for MPA. Inhalation Exposure No chronic, subchronic, developmental, or reproductive toxicity studies conducted by the inhalation route of exposure were located for MPA. 3 FINAL 9-10-2009 DERIVATION OF PROVISIONAL SUBCHRONIC AND CHRONIC TOXICITY VALUES FOR METHYLPHOSPHONIC ACID (RfDs, RfCs) Due to a lack of data, no chronic or subchronic RfDs or RfCs are developed. However, the Appendix of this document contains a Screening Value for oral toxicity (RfD) based on an analog approach, which may be useful in certain instances. Please see the attached Appendix for details. PROVISIONAL CARCINOGENICITY ASSESSMENT FOR METHYL PHOSPHONIC ACID Weight-of-Evidence Descriptor Under the 2005 Guidelines for Carcinogen Risk Assessment (U.S.
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