Overview of Antimony Trioxide (ATO) Workplan Risk Assessment Antimony Trioxide (ATO) Metal CASRN 1309-64-4 Sharon Oxendine Office of Pollution Prevention and Toxics Oxide November 13, 2013 Presentation Overview This presentation will provide: Background on ATO Key science issues Please comment on the clarity, strengths and weaknesses of the assessment and how it specifically may be improved. Office of Pollution Prevention and Toxics 2 Basis for Selection * Exposure - 23,000 metric tons imported in 2012 - widespread use in consumer products * Human Health Effects - inhalation toxicity - possible carcinogen * Environmental Releases - persistence - bioaccumulation Office of Pollution Prevention and Toxics 3 Scope of the Assessment × Human health risks were not the focus of this assessment Evaluated ecological risks associated with ATO use in halogenated flame retardants Office of Pollution Prevention and Toxics 4 ATO Antimony Compounds Conceptual Model for ATO Risk Assessment focuses on ecological risks resulting from industrial releases to water Chemistry, Fate and Transport Please comment on the use of chemistry, fate and transport information to evaluate bioavailability in environmental media. Office of Pollution Prevention and Toxics 6 Hazard Characterization Please comment on the use of toxicity data for antimony trichloride to characterize aquatic toxicity. Office of Pollution Prevention and Toxics 7 Criteria for Selection of TRI Facilities NAICS codes Reported water releases Availability of “7Q10” streamflow data Office of Pollution Prevention and Toxics 8 Monitoring: USGS-NWIS & EPA STORET 9 Monitoring Data: Office of Pollution Prevention and Toxics 11 Can we generalize from this data to other regions? Please comment on the use of these data sets to characterize ecological exposures. Do they adequately reflect conditions at other locations in the US? Are there other major sources of environmental monitoring data (or other pertinent information) that EPA should consider in the exposure assessment? If so, please provide the necessary citations and/or data for inclusion in the revised document. Are there concerns or limitations in these data sets that may impact their utility for risk assessment? Office of Pollution Prevention and Toxics 11 Use of the category ‘antimony compounds’ as a surrogate to estimate ATO releases Are there other data sources and/or approaches that EPA should consider for estimating environmental releases? If so, please provide citations or data for consideration in further revision of the draft assessment. Office of Pollution Prevention and Toxics 12 Exposure and Fate Assessment Screening Tool (Version 2) model estimates of surface water concentrations Two release scenarios (assuming total yearly TRI releases occurred over a period of 24- or 250 days/year) were used to provide a range of predicted water concentrations for comparison with hazard benchmarks (concentrations of concern). Please comment on the EFAST2 modeling approach used to assess aquatic risks. Office of Pollution Prevention and Toxics 13 Risk Quotient Approach RQ = Environmental Concentration COC Environmental concentrations reflect measured or estimated values COCs were calculated from the most sensitive effect levels Risks indicated when the environmental concentration exceeds COC (i.e., RQ > 1) Office of Pollution Prevention and Toxics 14 Validity of Assumptions Please comment on the implicit assumption that antimony levels measured in environmental media reflect inputs from various types of antimony compounds and end use applications and how this could impact risk estimates. Findings reported in this assessment are thought to represent conservative estimates of risk. Please comment on the validity of this statement and the likelihood that actual risks have been over (or under) estimated. Office of Pollution Prevention and Toxics 15 Risk Summary Media Type Organism Endpoint COC Monitoring Data Modeled Data C. viridissima 96-hour LC50 = 1.77 mg/L 354 ppb (acute) No exceedance One exceedance P. Promelas 30-day GMATC = 1.62 mg/L 162 ppb (chronic) ~ 0.2% above chronic COC No exceedances 112 mg Sb/kg dw (acute) No exceedances - 11.2 mg Sb/kg dw (chronic) ~ 0.7% above chronic COC - Water Sediment L. variegatus 28-d NOEC = 112 mg Sb/kg dw or C. riparius Office of Pollution Prevention and Toxics 16 Monitoring Results Selected TRI facilities ( ) are shown as a point of reference Office of Pollution Prevention and Toxics 20 Conclusion Minimal risks are expected for ecological organisms: The available environmental monitoring data reflect input from various sources and types of antimony compounds. Use of ‘antimony compounds’ as a surrogate for ATO and model estimates based on the assumption of yearly TRI releases occurring over a 24-day period provide conservative estimates of exposure potential. Use of highly sensitive ecological species showed few instances where measured or predicted concentrations in environmental media exceeded the COC for water-, or sediment-dwelling organisms. Office of Pollution Prevention and Toxics 18 Uncertainty and Data Limitations Risk findings are constrained by a number of uncertainties regarding data quality (e.g., adequacy of TRI reporting, model assumptions, and environmental monitoring data). Environmental fate and transport are influenced by site-specific conditions that can impact bioavailability. Since these parameters vary, it is difficult to extrapolate to other geographic regions within the US. There is little or no overlap between the geographic locations of selected TRI facilities and the available monitoring data, therefore a direct linkage to ATO use as a flame retardant synergist is not possible. Office of Pollution Prevention and Toxics 19 Key Technical Issues Raised in Public Comments • Exposure - Use of conservative assumptions in exposure assessment - Rationale for selection of end-use scenario • Hazard - Lack of transparency in hazard characterization - Unclear criteria for study selection • Risk - Risk quotient versus margin of exposure - Use of phrases such as “minimal concern” Office of Pollution Prevention and Toxics 20 Acknowledgements Kay Austin Jay Jon Stanley Barone Sharon Oxendine Cathy Fehrenbacher Wen-Hsiung Lee Nhan Nguyen Tim Lehman Louis Scarano Sara Pollack Christina Cinalli Emma Lavoie Rick Fehir Kirsten Hesla Contract Support Portions of this document were developed with support from SRC, Eastern Research Group and Versar. Office of Chemical Safety and Pollution Prevention Office of Pollution Prevention and Toxics 21 Thank you! Aquatic Toxicity Data Test Organism Species Endpoint Antimony Compound SbCl3 SbCl3 Fish Aquatic invertebrate Pagrus major Chlorohydra viridissima 96-hour LC50 96-hour LC50 Aquatic plant Pseudokirchneriella subcapitata 72-hour LC50 (growth rate) SbCl3 Aquatic plant P. subcapitata 72-hour LC50 (growth rate) Sb2O3 Fish Pimephales promelas 30-day (growth) SbCl3 Fish P. promelas 30-day (growth) Sb2O3 Aquatic invertebrate Daphnia magna 21-day (reproduction) SbCl3 Value Reference 6.9 mg Sb/L 1.77 mg Sb/L Takayanagi (2001) TAI (1990) EC50 > 36.6 mg/L NOEC = 2.11 mg Sb/L LOEC of 4.00 mg Sb/L GMATC = 2.91 mg Sb/L NOEC = 0.396 mg Sb/L LOEC = 1.32 mg Sb/L GMATC = 0.723 mg Sb/L NOEC = 1.13 mg Sb/L LOEC = 2.31 mg Sb/L GMATC = 1.62 mg Sb/L NOEC >0.0075mg /L Heijerick and Vangheluwe (2004) LISEC (2001) Kimball (1978) LeBlanc and Dean (1984) NOEC = 1.74 mg Sb/L Heijerick and LOEC = 3.13 mg Sb/L Vangheluwe GMATC = 2.33 mg Sb/L (2003b)a) Office of Pollution Prevention and Toxics 23 Sediment Toxicity Data Test Organism Species Antimony Compound Endpoint Value Reference Amphipod Hyalella azteca Survival/growth/ reproduction SbCl3 NOEC = 87 mg Sb/kg ww Heijerick and (124 mg Sb/kg dw) Vangheluwe (2003a) Oligochaete Lumbriculus variegatus Survival/growth/ reproduction SbCl3 NOEC = 78 mg Sb/kg ww Heijerick and (112 mg Sb/kg dw) Vangheluwe (2005a) Midge larvae Chironomus riparius Survival/growth/ reproduction SbCl3 NOEC = 78 mg Sb/kg ww Heijerick and (112 mg Sb/kg dw) Vangheluwe (2005b) Office of Pollution Prevention and Toxics 24 Soil Toxicity Data Test Organism Species Endpoint Antimony Compound Springtail Folsomia candida Reproduction Sb2O3 Earthworm Eisenia fetida Adult survival/ Sb2(SO4)3 juvenile production Enchytraeid Enchytraeus crypticus Adult survival/ Sb2(SO4)3 juvenile production Springtail F. candida Adult survival/ Sb2(SO4)3 juvenile production Value NOECreproduction = 999 mg Sb/kg dw LOECreproduction= 2,930 mg Sb/kg dw NOEC/LOEC adult survival = 617/697 mg Sb/kg NOEC/LOEC juvenile production = 60/86 mg Sb/kg NOEC/LOEC adult survival = 384/538 mg Sb/kg NOEC/LOEC juvenile production = 100/140 mg Sb/kg NOEC/LOEC adult survival = 100/126 mg Sb/kg NOEC/LOEC juvenile production = 100 /126 mg/kg Reference Moser (2007) Simini et al. (2002) Kuperman et al. (2002) Phillips et al. (2002) Office of Pollution Prevention and Toxics 25 U.S. Geological Survey Open-File Report http://mrdata.usgs.gov/geochem/doc/home.htm USGS National Stream Quality Accounting Network (1996-2000) http://pubs.usgs.gov/wri/wri014255/results/detect/pd01095.png 27 ANTIMONY STATISTICS1 (Metric tons of antimony content) United States: Mine production Smelter production: Primary Secondary Exports: Metal, alloys, waste and scrap (gross weight) 2 Antimony oxide Imports for consumption Reported industrial consumption, primary antimony Price, average3 (cents per pound) Global mine production 2008 -- 2009 -- 2010 -- 2011 -- 2012 -- W 3,180 W 3,020 W 3,520 W 3,230 W 3,730 366 1,830 29,000 8,140 279.5 185,000r 385 1,710 20,200 6,770 235.6 154,000 427 2,120 26,200 8,860 401.2 178,000r 581 3,590 23,500 10,200 650.3 183,000r 847 3,870 22,600 10200 564.5 174,000e e Estimated. r Revised. W Withheld to avoid disclosing company proprietary data, -- Zero. are rounded to no more than three significant digits, except prices. 2Antimony content data were calculated by the U.S. Geological Survey. 3New York dealer price for 99.5% to 99.6% metal, cost, insurance, freight U.S. ports. (USGS, 2012) 1Data Office of Pollution Prevention and Toxics 28