August 2017 Office of Chemical Safety and Pollution Prevention U.S. EPA Preliminary Information on Manufacturing, Processing, Distribution, Use, and Disposal: Pentachlorothiophenol CASRN: 133-49-3 August 2017 Support document for Docket EPA-HQ-OPPT-2016-0739 Page 1 of 12 ------- This document provides a preliminary public summary of available information collected by EPA's Office of Pollution Prevention and Toxics (OPPT) in the Office of Chemical Safety and Pollution Prevention (OCSPP) on the manufacturing (including importing), processing, distribution in commerce, use, and disposal of this chemical. This is based on existing data available to EPA, including information collected under the Chemical Data Reporting rule, information from other Agency databases, other U.S. Government agencies, publicly available information from states, and a review of published literature. In addition, the document includes information reported to EPA by producers and users of the chemical in the United States and in other countries. This preliminary use information and any additional use information received in the docket by December 9, 2017, will inform efforts to identify, under section 6(h)(1)(B) of the Toxic Substances Control Act (TSCA), whether exposure to this chemical is likely, under the conditions of use, either to the environment, the general population, or to a potentially exposed or susceptible subpopulation identified by EPA. The information will also inform any risk management efforts following the exposure and use assessment under TSCA section 6(h)(1)(B). Mention of trade names in this document does not constitute endorsement by EPA. To verify products or articles containing this chemical currently in commerce, EPA has identified several examples. Any lists are provided for informational purposes only. EPA and its employees do not endorse any of the products or companies. This document does not contain confidential business information (CBI). Page 2 of 12 ------- TABLE OF CONTENTS TABLE OF CONTENTS 3 CONTACT 3 MANUFACTURING, PROCESSING, DISTRIBUTION, USE, AND DISPOSAL 4 1. Manufacturing (Including Importing) 4 2. Processing 5 3. Products and Articles 5 4. Distribution (Includes Retailers) 6 5. Uses 8 6. Disposal of Waste and Recycling/Recovery 9 USEFUL TYPES OF INFORMATION 9 APPENDIX: ADDITIONAL SOURCES CONSULTED 9 CONTACT Marc Edmonds, OPPT, National Program Chemicals Division (NPCD), (202) 566-0758, edmonds.marc@epa.gov. Docket: EPA-HQ-OPPT-2016-0739 Page 3 of 12 ------- MANUFACTURING, PROCESSING, DISTRIBUTION, USE, AND DISPOSAL 1. Manufacturing (Including Importing) No company has reported manufacture and/or import of pentachlorothiophenol (PCTP) in the U.S. above the reporting threshold of the Chemical Data Reporting (CDR) Rule for 20161. Only one company reported manufacture and/or import of PCTP in the U.S. in 20122. The production volume of PCTP was claimed as confidential business information (CBI). There is no Toxics Release Inventory (TRI) data available for this chemical as it is not required to be reported under TRI3. Manufacturing Process PCTP is created from hexachlorobenzene (a fungicide not used in the U.S. since 19844) by treatment with sodium sulfide and sulfur in methanol, or with sodium hydrogensulfide5. Additionally, PCTP may be created with a "reaction of hydrogen sulfide with pentachlorophenol in the presence of an acidic catalyst, eg, aluminum chloride or boron trifluoride6." 1 Manufacturers (including importers) are required to report under CDR if they meet certain production volume thresholds, generally 25,000 lb or more of a chemical substance at any single site. Reporting is triggered if the annual reporting threshold is met during any of the calendar years since the last principal reporting year. In general, the reporting threshold remains 25,000 lb per site. However, a reduced reporting threshold (2,500 lb) now applies to chemical substances subject to certain TSCA actions, https://www.epa.gov/chemical-data-reporting/how-report- under-chemical-data-reporting. 2 https://iava.epa.gov/oppt chemical search/; Manufacture in the context of CDR means to manufacture, produce, or import for commercial purposes. Manufacture includes the extraction, for commercial purposes, of a component chemical substance from a previously existing chemical substance or complex combination of chemical substances. (40 CFR 711.3) EPA, TSCA Chemical Data Reporting, Fact Sheet: Importers, (Washington DC: Office of Pollution Prevention and Toxics, 2016). https://www.epa.gov/sites/production/files/2015- 12/documents/cdr fact sheet importers final dec2015 O.pdf. 3 https://www.epa.gov/toxics-release-inventorv-tri-program/tri-listed-chemicals 4 Agency for Toxic Substances and Disease Registry, Public Health Statement: Hexachlorobenzene (Atlanta, Georgia: Division of Toxicology and Human Health Sciences, 2015). https://www.atsdr.cdc.gov/phs/phs.asp?id=625&tid=115. 5 Roy K-M; Thiols and Organic Sulfides. Ullmann's Encyclopedia of Industrial Chemistry 7th ed. (1999-2014). NY, NY: John Wiley & Sons. (Online: 2000). http://onlinelibrarv.wilev.com/doi/10.1002/143560Q7.a26 767/full?a26 767-eo- 2093#a26 767-bib-0172. 6 https://pubchem.ncbi.nlm.nih.gov/compound/8620 Page 4 of 12 ------- 2. Processing PCTP is used as a mercaptan (sulfur) cross-linking agent to make rubber more pliable in industrial uses, also called a peptizer7. "Natural rubber must be reduced in viscosity in order to obtain workable compounds. Many different chemical peptizers have been employed over the years for this purpose, including ... [PCTP] or its zinc salt, and dithiobisbenzanilide [135-57-9] or its zinc salt. Dithiobisbenzanilide with an activator and clay diluent is the preferred peptizing agent for natural and synthetic rubbers. The viscosity of natural rubber and synthetic polyisoprene can be reduced by mechanical shear alone, but using a peptizer makes the viscosity reduction during mixing less sensitive to variations in time and temperature, providing uniformity in viscosity from batch to batch8." 3. Products and Articles EPA identified the following types of products and articles based on a search of available sources for products containing PCTP. According to the "Rubber Handbook" available on the website of Struktol Co of America, "STRUKTOL A95 is a 45% pentachlorothiophenol with activator on an inert filler. A95 is used for effective viscosity reduction through chemical peptization of natural rubber and synthetic rubber9." Since Struktol did not submit manufacturing information to CDR in 2016, it is unclear whether this product has been discontinued, or if the manufacture/import amount has dropped below the reporting threshold. PCTP is mentioned over 2,100 patents10 including patents held by the the following companies for the manufacture of golf balls that may include PCTP: • Callaway Golf Co.11 • Acushnet Co.12 • Taylor Made Golf Co.13 • Bridgestone Sports Co. Ltd.14 7 EPA, TSCA Work Plan for Chemical Assessments: 2014 Update, (Washington DC: Office of Pollution Prevention and Toxics, 2014). https://www.epa.gov/assessing-and-managing-chemicals-under-tsca/tsca-work-plan-chemical- assessments-2014-update 8 Ohm, R. F., Rubber Chemicals (Online: Kirk-Othmer Encyclopedia of Chemical Technology, 2000). http://onlinelibrarv.wilev.com/doi/10.1002/0471238961.1821020215Q813.a01/abstract. 9 Struktol, Rubber Handbook (Stow, Ohio: 2004). http://www.struktol.com/pdfs/RubberHB.pdf. 10 https://pubchem.ncbi.nlm.nih.gov/compound/8620 11 http://www.google.com.ar/patents/US71991927chen 12 https://www.google.com/patents/US200901818017chen: http://www.google.tt/patents/US20110237352 13 https://patents.google.com/patent/US20060172823Al/en 14 https://patents.google.com/patent/US6679791B2/en Page 5 of 12 ------- 4. Distribution (Includes Retailers) General internet searches for distributors of PCTP yielded many vendors selling various quantities at different purities. Note that these are defined as distributors due to their marketing of PCTP for sale and distribution. Results of a search of distributors of PCTP are in Table 1 below. This list is provided for informational purposes only. EPA and its employees do not endorse any of the products or companies. Table 1. Distributors of PCTP Name Available Quantity Purity (%) Reference PCTP 100 mg Not specified http://www. sigmaaldrich.com/catalog/Droduct/suDelco/ metl2159b?lang=en®ion=US&cm SD=lnsite- - prodRecCold xviews- -prodRecColdlO-1 PCTP 25g >95.0%(T) http://www.tcichemicals.com/eshop/en/us/commoditv/ P0312/ PCTP lg 98% http://www.ikchemical.com/EN/products/A01371068.ht ml PCTP 5g 98% http://www.ikchemical.com/EN/products/A01371068.ht ml PCTP lOOmg Not specified http://en. merver.com/en/products/detail.aspx?ProlD=ll 7134 PCTP 25g 95% http://en. merver.com/en/products/detail.aspx?ProlD=ll 7133 PCTP 25g >95.0%(T) http://www.tcichemicals.eom/eshop/en/hk/catalog/list/s earch?searchWord=133-49- 3&client=default frontend&output=xml no dtd&proxvst vlesheet=default frontend&sort=date%3AD%3AL%3Adl &oe=UTF-8&ie=UTF- 8&ud=l&exclude apps=l&site=en hk&mode=0 PCTP Up to kgs 98%(Min,HPL C) http://www.capotchem.com/133-49-3.html PCTP 25g 95% https://www.abcr.de/shop/en/AB140076 PCTP Quote provided upon request Not specified http://www.tractuschem.com/productshow/TRA0021029 .html PCTP Backordered; Price not available 96% http://www.aurumpharmatech.com/Product/ProductDet ails/K 4195 PCTP Quote provided upon request Not specified http://www.vitasmlab.com/index.php?option=com searc h stk<emid=22&stk=BBL028077&?utm source=pubche m&utm medium=p search link&utm campaign=pubche m search&utm content=pubchem slink PCTP Quote provided upon request Not specified http://www.apichemistrv.com PCTP Quote provided upon request Not specified http://www.1717chem.com/ Page 6 of 12 ------- Name Available Quantity Purity (%) Reference PCTP Quote provided upon request Not specified http://www.akosgmbh.de/AKosSamples/index.html PCTP Quote provided upon request Not specified http://www.debvesci.com/ PCTP Quote provided upon request Not specified http://www.anpharma.net PCTP Quote provided upon request Not specified http://www.ichemical.com/chemicals/cas-133-49-3 PCTP Quote provided upon request Not specified https://www.biosvnth.com/en/products/chemical- intermediates/advanced-intermediates/products/Q- 201540.html PCTP lOmg 92% https://mcule.com/MCULE-6962967512/ PCTP Up to 25g minimum order value required >95% http://online.aurorafinechemicals.com/info?ID=A13.141. 039 PCTP Quote provided upon request Not specified https://aksci.com/item detail.php?cat=M803 PCTP Quote provided upon request Not specified http://www.anward.com/pro result/28277/ PCTP 50g 95% http://www. labseeker.com/goods. php?id=24282 PCTP Quote provided upon request Not specified http://www.achemica.com PCTP Quote provided upon request Not specified http://www.chemtik.com PCTP Quote provided upon request 97% http://www.rennotech.com/product show.asp?id=28872 PCTP Quote provided upon request (research only but not for commercial purposes) Not specified http://www.chembopharma.com PCTP 500g 98% http://www.ahhchemical.com/product/MT-20665.html PCTP lOOmg Not specified https://www.scbt.com/scbt/product/pentachlorothiophe nol-133-49-3 Page 7 of 12 ------- 5. Uses Industrial Uses Chemical peptizers are used to reduce viscosity during the production of rubber materials. "For many years the preferred peptizer was PCTP or its zinc salt. Meanwhile PCTP is banned in most parts of the world because it forms several teratogenic decomposition products. PCTP is replaced by 2,2'-dibenzamidodiphenyldisulfide (DBD) which is less toxic and reacts similarly15." Uniroyal, Inc., now owned by Michelin, owned a patent for producing pentachloronitrobenzene, a soil fungicide, by the reaction of PCTP with nitric acid in the presence of sulfuric acid or oleum16. Naphthalene can be extracted from aqueous samples with PCTP -gold colloid on magnetic microparticles17. The Swedish Chemicals Agency KEMI Commodity Guide suggests that PCTP may be found in butadiene rubber, isoprene rubber, natural rubber, and other rubber materials18. So it is possible that imported products containing these materials could contain PCTP. However, a letter to EPA from the Rubber Manufacturers Association, dated Feb. 22, 2017, indicates that its members "do not currently use ... PCTP to manufacture tires produced in the U.S. or imported into the U.S19." Commercial Uses Commercially available PCTP is used in laboratories for research purposes. See Section 4 above. Consumer Uses EPA is not aware of consumer uses for PCTP. 15 Engels H-W et al; Rubber, 9. Chemicals and Additives. Ullmann's Encyclopedia of Industrial Chemistry 7th ed. (1999- 2014) (New York, New York: John Wiley & Sons, 2014). http://onlinelibrarv.wilev.com/doi/10.1002/143560Q7.a23 365.pub3/pdf. 16 https://www.google.com/patents/US4454362 17 Mosier-Boss PA, Lieberman SH, Surface-enhanced Raman spectroscopy substrate composed of chemically modified gold colloid particles immobilized on magnetic microparticles, (Anal. Chem., 2005). https://www.ncbi.nlm.nih.gov/pubmed/15858982. 18 http://www.kemi.se/en/directlv-to/statistics/the-commoditv-guide 19 Amick, Hexachlorobutadiene (HCBD) and Pentachlorothio-phenol (PCTP) not currently used to make RMA member company tires manufactured in the U.S. or imported into the U.S., Ltr to Doug Parsons, from Rubber Manufacturers Association, Feb. 22, 2017. EPA-HQ-OPPT-2016-0739-0002 Page 8 of 12 ------- 6. Disposal of Waste and Recycling/Recovery PCTP is not regulated as hazardous waste. EPA is not aware of information regarding the recycling and recovery of PCTP, nor the disposal of PCTP as waste. USEFUL TYPES OF INFORMATION This document presents a summary of information currently available to EPA on this chemical. EPA is interested in obtaining information to more fully characterize the manufacturing, processing, distribution, disposal, and use of this chemical, to inform the development of the exposure and use assessment for this chemical, and to inform any subsequent risk management efforts. For example, EPA is interested in obtaining information on: • the functional uses for this chemical; • what types of products contain this chemical; • which industry sectors use this chemical; • what volume of the chemical is used; • which uses have been discontinued or phased out; • exposure scenarios for this chemical; and • in which articles this chemical is found. APPENDIX: ADDITIONAL SOURCES CONSULTED • U.S. EPA Chemical Inventory https://www.epa.gov/tsca-inventory • U.S. National Library of Medicine ChemlDplus https://chem.sis.nlm.nih.gov/chemidplus/ • U.S. EPASffS https://iaspub.epa.gov/sor internet/registry/substreg/searchandretrieve/substancese arch/search.do • U.S. EPA HPV HC (access through Chemical Data Access Tool - CDAT) https://java.epa.gov/oppt chemical search/ • U.S. National Library of Medicine Hazardous Substance Data Bank (HSBD) https://toxnet.nlm.nih.gov/newtoxnet/hsdb.htm • U.S. EPA HPVIS and HPV HC (access through Chemical Data Access Tool - CDAT) https://java.epa.gov/oppt chemical search/ • SRC FatePointers Search Module PHYSPROP http://esc.syrres.com/fatepointer/search.asp Page 9 of 12 ------- • U.S. EPA Superfund chemical data matrix https://www.epa.gov/superfund/superfund- chemical-data-matrix-scdm-query • U.S. EPA ChemView https://iava. epa. gov/chem view • U.S. EPA InertFinder https://iaspub.epa .gov/apex/pesticides/f?p=101:l: • U.S. EPA Pesticide Chemical Search https://iaspub.epa .gov/apex/pesticides/f?p=CH EM ICALSEARCH: 1:0:: NO:!:: • U.S. EPA Endocrine Disruptor Screening Program https://www.epa.gov/ingredients-used-pesticide-products/endocrine-disruptor- screening-program-tier-l-assessments • U.S. EPA Hazardous Air Pollutants https://www.epa.gov/haps/initial-list-hazardous-air- pollutants-modifications • U.S. EPA Significant New Alternatives Policy (SNAP) https://www.epa.gov/snap • U.S. EPA Volatile Organic Compounds https://www.epa.gov/indoor-air-qualitv-iaq/technical-overview-volatile-organic- compounds#definition • U.S. EPA Toxic and priority pollutants under the Clean Water Act https://www.epa.gOv/eg/toxic-and-priority-pollutants-under-clean-water-act#toxic • U.S. EPA Contaminant Candidate list under the Safe Drinking Water Act https://www.epa.gOv/ccl/contaminant-candidate-list-3-ccl-3#chemical-list • U.S. EPA IRIS Assessment https://cfpub.epa.gov/ncea/iris2/atoz.cfm • OSHA Chemical Hazards and Toxic Substances https://www.osha.gov/SLTC/hazardoustoxicsubstances/index.html • NIOSH Workplace Safety and Health Topics Chemicals http://www.cdc.gov/niosh/topics/chemical.html • NIOSH Pocket Guide to Chemical Hazards http://www.cdc.gov/niosh/npg/npgdcas.html • CPSC Chemicals http://www.cpsc.gov/en/Research--Statistics/Chemicals/ • CPSC FHSA https://www.cpsc.gov/Business--Manufacturing/Business-Education/Business- Guidance/FHSA-Requirements/ • Food and Drug Administration List of Databases http://www.fda.gov/Forlndustrv/FDABasicsforlndustry/ucm234631.htm • NTP (National Toxicology Program) Substances studied by NTP http://ntpsearch.niehs.nih.gov/?e=True&ContentType=Testing+Status • Department of Energy Protective Action Criteria Database http://energy.gov/ehss/protective-action-criteria-pac-aegls-erpgs-teels-rev-29- chemicals-concern-may-2016 Page 10 of 12 ------- • California DTSC Toxics in Products http://www.dtsc.ca.gov/PollutionPrevention/ToxicslnProducts/index.cfm http://www.dtsc.ca.gov/SCP/CandidateChemicalsList.cfm http://www.dtsc.ca.gov/SCP/WhatlsAPriorityProduct.cfm • California OEHHA Biomonitoring http://biomonitoring.ca.gov/chemicals • California Permissible exposure limits for chemical contaminants https://www.dir.ca.gov/title8/5155table acl.html • California Hazardous substance list https://www.dir.ca.gov/title8/339.html • California Safe Cosmetics Program - list of chemical agents known or suspected to cause cancer or developmental or other reproductive harm. http://www.cdph.ca.gov/programs/cosmetics/Pages/default.aspx • Maine Chemicals of high concern http://www.maine.gov/dep/safechem/highconcern/ • Michigan Environmental Health Topics http://www.michigan.gov/mdhhs/0,5885,7- 339-71548 54783 54784 74881-13050~.00.html • New Hampshire Regulated Toxic Air Pollutants http://des.nh.gov/organization/commissioner/legal/rules/documents/env-al400.pdf • New Jersey Right to Know Hazardous Substances http://web.doh.state.ni.us/rtkhsfs/rtkhsl.aspx • Oregon Priority Persistent Pollutants (in water) http://www.deq.state.or.us/wq/SB737/ • Oregon Pollutant Profiles http://www.deq.state.or.us/wq/SB737/docs/LegRpAtt420100601.pdf • Oregon Reducing Toxics in Oregon http://www.oregon.gov/deq/Pages/ToxicsReduction.aspx • Oregon Chemicals of Concern for Children's Health http://public.health.oregon.gov/HealthvEnvironments/HealthvNeighborhoods/ToxicS ubstances/Pages/childrens-chemicals-of-concern.aspx • Pennsylvania Department of Labor and Industry Hazardous Substance List http://www.pacode.com/secure/data/034/chapter323/chap323toc.html • Rhode Island Air Resources - Air Toxics http://www.dem.ri.gov/pubs/regs/regs/air/air22 08.pdf • Vermont Chemical Disclosure Program for Children's Products http://www.healthvermont.gov/enviro/chemical/cdp.aspx • Washington Chemicals of High Concern to Children http://www.ecy.wa.gov/programs/hwtr/rtt/cspa/chcc.html • Washington Children's Safe Products Act http://apps.leg.wa.gov/RCW/default.aspx?cite=70.240 • Washington Department of Labor & Industries SHARP Publications http://www.lni.wa.gov/Safety/Research/Pubs/default.asp • Lowell Center for Sustainable Production Chemical, Policy and Science Initiative http://www.chemicalspolicv.org/chemicalspolicy.us.state.database.php Page 11 of 12 ------- • National Conference of State Legislatures http://www.ncsl.org/research/environment- and-natural-resources/state-chemical-statutes.aspx • OECD eChemPortal http://www.echemportal.org/echemportal/index?pagelD=0&request locale=en • Stockholm Convention on Persistent Organic Pollutants http://chm.pops.int/TheConvention/ThePOPs/ListingofPOPs/tabid/25Q9/Default.aspx http://chm.pops.int/TheConvention/ThePOPs/ChemicalsProposedforListing/tabid/251 O/Default.aspx • WHO IPCS (UN) http://www.who.int/ipcs/en/ • Other - worker protection information http://www.dguv.de/ifa/gestis/gestis-internationale-grenzwerte-fuer-chemische- substanzen-limit-values-for-chemical-agents/index-2.jsp • U.S. EPA Chemical and Product Categories (CPCat) Database https://actor.epa.gov/cpcat/faces/home.xhtml • U.S. National Library of Medicine Hazardous Substance Data Bank (HSBD) https://toxnet.nlm.nih.gov/newtoxnet/hsdb.htm • CPSC Chemicals http://www.cpsc.gov/en/Research--Statistics/Chemicals/ • U.S. Department of Health & Human Services Household Products Database https://hpd.nlm.nih.gov/index.htm • DeLima Associates Consumer Product Information Database (CPID) https://www.whatsinproducts.eom/chemicals/index/l • Product and company websites https://safecosmetics.cdph.ca.gov/search/Default.aspx • U.S. EPA Hazardous Waste https://www.epa.gOv/hw/learn-basics-hazardous-waste#regulations • Pollution Prevention information, includingTRI https://www.epa.gov/p2/pollution-prevention-tools-and-calculators • DfE Alternatives Assessments https://www.epa.gov/saferchoice/design-environment-alternatives-assessments • Safer Chemical Ingredients List https://www.epa.gov/saferchoice/safer-ingredients • Green Chemistry awards - information regarding possible alternatives https://www.epa.gov/greenchemistrv/presidential-green-chemistry-challenge- winners • Pollution Prevention - information regarding possible alternatives https://www.epa.gov/p2/pollution-prevention-case-studies https://www.epa.gOv/p2/grant-programs-pollution-prevention#sra • Greener products and services (e.g. some of the electronic standards include alternative assessments) https://www.epa.gov/greenerproducts/identify-greener-products-and-services Page 12 of 12 ------- |