Fluorosilicic Acid Supply Chain - Executive Summary Fluorosilicic Acid Direct Use Chemical H2SiF6 (liquid) Inputs to Manufacturing Process: Phosphate Rock Sulfuric Acid J* Derivative Water Treatment Chemicals: * None % of Total Domestic Consumption Attributed to Water Sector: Approximately 63% Understanding Chemical Supply Chains Map of Suppliers & Manufacturers A. Product Family: „u Phosphate CAS No.: 16961-83-4 2 Shelf Life: 1 Month — RISK OF SUPPLY DISRUPTION (Assessed in 2022) RISK RATING: Moderate-Low J*** V«e .-Low Modern Rar>e>n s/> f I RISK DRIVERS Production of fluorosilicic acid depends on the production of phosphate rock and manufactur- ing of sulfuric acid. Planned fa- cility downtime at the limited number of domestic manufac- turing facilities has resulted in recurring volatility in the supply of fluorosilicic acid. RISK PARAMETERS Criticality: Low. Used widely but in discretionary application. Likelihood: High. Previous widespread disruptions in supply that impacted the water sector. Vulnerability: Moderate-High. Lim- ited domestic manufacturing con- centrated in select geographic areas and strong reliance on imports. MANUFACTURING PROCESS Water Treatment Applications Phosphate Rock Sulfuric Acid Fluorosilicic Acid Input End Use Fluoridation of drinking water Other Applications • Production of metal fluorosilicates • Masonry and ceramic hardening • Solar panel and chip production DOMESTIC PRODUCTION AND CONSUMPTION, AND INTERNATIONAL TRADE Domestic Manufacturing Locations (2017): 5, in Florida, North Carolina, Louisiana, and Wyoming (S* International Trade (2019) Primary Trading Partner (Imports): China Primary Trading Partner (Exports): China Domestic Consumption (2019): 58 M kg ¦ Domestic Production (29 M kg) ¦ Imports for Consumption (39 M kg) ¦ Export of Domestic Production (10 M kg) &EPA ------- Fluorosilicic Acid Supply Chain - Full Profile Product Description Fluorosilicic acid (FSA) (H2SiF6), a halogenated inorganic acid, is the water fluoridation compound most widely used in community water systems in the U.S. as it yields free fluoride rapidly when mixed with water. The majority of FSA produced is used for municipal water fluoridation, and the remainder is mostly consumed by the aluminum industry to produce aluminum fluoride. Use in Water Treatment FSA is used in water treatment for drinking water fluoridation (AWWA, 2011). Use as a Precursor to Other Water Treatment Chemicals None. Other Applications FSA is used in aluminum fluoride and other metal fluorosilicate manufacturing, hardening masonry and ceramics, metal surface treatment, and solar panel and silicon chip production. It is also used in hydrofluoric acid production (ATSDR, 2003; USGS, 2020a). Primary Industrial Consumers Water fluoridation is the primary use of FSA. In 2001, it is estimated that approximately 63% of FSA was consumed for water fluoridation (ATSDR, 2003). Manufacturing, Transport, & Storage Manufacturing Process Production of FSA for water fluoridation takes place as a byproduct of the reaction to produce wet-process phosphoric acid. The majority of phosphate rock, represented in Figure 1 as fluorapatite (Ca5(P04)3F), contains approximately 3-4% fluoride. The primary reaction, which involves digestion of phosphate rock with sulfuric acid to produce phosphoric acid, is shown in Figure 1. During this reaction, sulfuric acid reacts with other elements in phosphate rock and through these reactions fluoride and silicon are mobilized to form silicon tetrafluoride and hydrogen fluoride, as shown in the secondary reaction in Figure 1. The hydrogen fluoride and silicon tetrafluoride vapors can be recovered through filtration and evaporation. When the gases are scrubbed with water, FSA is formed as a waste stream (Solvay, 2013). FSA is not a discrete compound, but rather an aqueous mixture of fluorosilicated compounds (AWWA, 2011). Primary Reaction Phosphate Rock + Sulfuric Acid —> Phosphoric Acid + Gypsum + Hydrogen Fluoride Cas(P04)3F + 5H2SO4 —> 3H3PO4 + 5CaS04 + HF Secondary Reaction (Gas Capture) Silicon Tetrafluoride + Hydrogen Fluoride —> Fluorosilicic Acid Si F4 + 2HF —> H2SiFs Figure 1. Chemical Equation for the Reaction to Manufacture Fluorosilicic Acid EPA 817-F-22-028 | December 2022 f/EPA ------- Fluorosilicic Acid Supply Chain - Full Profile Product Transport FSA is considered a strong, corrosive acid, but is commonly transported by rail and tanker truck (OxyChem, 2018). Given the limited number of domestic production facilities which are concentrated in Florida, Louisiana, North Carolina and Wyoming, long-distance transport may be required to deliver FSA throughout the U.S. Storage and Shelf Life FSA should be stored in cool, well-ventilated areas and under these conditions has a shelf life of one month. It is highly corrosive, and exposure to strong oxidizers or elevated temperatures can lead to the release of hydrogen fluoride and hydrogen gas through decomposition (Simplot, 2021; Solvay, 2013). Domestic Production & Consumption Domestic Production Production data was collected from the U.S. Geological Survey (USGS), while trade data was collected from the U.S. International Trade Commission (USITC) Dataweb, as shown in Table 1. While production data is specific to fluorosilicic acid, trade data represents import and export of inorganic acids, 'not elsewhere specified' (NES). Table 1. FSA Production and Trade Data Sources Production and Trade Data Category Data Source Identifier Description Domestic Production U.S. Geological Survey 2019 Fluorspar Data Sheet1 CAS No.: 16961-83-4 Fluorosilicic Acid Imports and Exports International Trade Statistics U.S. International Trade Commission HS Code: 2811.19 HTS Code: 2811.19.60 Inorganic Acids Other than Hydrogen Fluoride Inorganic acids, NES Total U.S. domestic production of FSA from phosphate rock was approximately 29 million kilograms (M kg) in 2019 (USGS, 2021). The vast majority of domestic commercial manufacture of FSA is integrated with manufacturing of phosphoric acid from phosphate rock (USGS, 2020a). Domestic commercial manufacturing of FSA as a co-product of phosphoric acid production has historically taken place in Florida, Louisiana, North Carolina, and Wyoming by J.R. Simplot, Mosaic Company, and PCS Phosphate Company (USGS, 2020a). The number of domestic manufacturing locations has fluctuated between 2010 and 2019, varying between four and six facilities. The number of domestic manufacturing locations shown in Figure 2 represents operating facilities as of 2017 (USGS, 2020a). Supply of NSF/ANSI Standard 60 certified fluorosilicic acid for use in drinking water treatment is widely distributed throughout the U.S. (NSF International, 2021). For a more current listing of manufacturing locations and supplier locations, visit the U.S. Environmental Protection Agency's (EPA's) Chemical Locator Tool (EPA. 2022a). 1FSA production, as sourced from phosphate rock, is included in the USGS profile for fluorspar (U.S. Geological Survey. 2020. 2017 Minerals Yearbook: Fluorspar, https://www.usgs.gov/centers/national-minerals-information-center/fluorspar-statistics-and- information) 2 f/EPA ------- Fluorosilicic Acid Supply Chain - Full Profile O O o © o ,Q.. Bw... o 00 f O Q> © Off*. ^ o CL ° O o o d? oS GO" o T C»S^ Co Domestic Supply and Manufacturing of Fluorosilicic Acid O 103 NSF-60 Certified Suppliers (NSF International, 2021) £ 5 Domestic Manufacturing Locations (USGS, 2017) OiKfri Figure 2. Domestic Supply and Manufacturing of Fluorosilicic Acid Domestic Consumption U.S. consumption of FSA in 2019 is estimated at 58 M kg. This estimate includes production of 29 M kg, import of 39 M kg, minus export of 10 M kg (USGS, 2021; USITC, 2021), as shown in Figure 3. Imports and exports represent trade of inorganic acids, NES (HTS Code 2811.19.61), while production data is specific to FSA. Domestic Consumption (2019): 58 M kg ¦ Domestic Production (29 M kg) ¦ Imports for Consumption (39 M kg) ~ Export of Domestic Production (10 M kg) Figure 3. Domestic Production and Consumption of Fluorosilicic Acid in 2019 Trade & Tariffs Worldwide Trade Worldwide import and export data for FSA is reported through the World Bank's World Integrated Trade Solutions (WITS) software, as a category representing a class of inorganic acids other than hydrogen fluoride. In 3 oEPA ------- Fluorosilicic Acid Supply Chain - Full Profile 2021, the U.S. ranked ninth worldwide in total exports and fourth in total imports of inorganic acids other than hydrogen fluoride. In 2021, China ranked first worldwide in total exports and total imports (WITS, 2022), as shown in Table 2. Import and export data specific to FSA is unavailable from the referenced sources. Table 2. WITS Worldwide Export and Import of Inorganic Acids Other than Hydrogen Fluoride, including Fluorosilicic Acid, in 2021 2021 Worldwide Trade Inorganic Acids Other than Hydrogen Fluoride (HS Code 2811.19) Top 5 Worldwide Exporters Top 5 Worldwide Importers China 92 M kg China 71 M kg Israel 40 M kg Sweden 67 M kg Poland 27 M kg Germany 33 M kg Germany 15 M kg United States 31 M kg Malaysia 14 M kg Brazil 17 M kg Domestic Imports and Exports Domestic imports and export data are reported by USITC in categories for inorganic acids, NES. Figure 4 summarizes imports for consumption2 and domestic exports3 between 2015 and 2020. During this period, the overall quantity of exports and imports remained relatively steady, with imports for consumption exceeding domestic exports. Over this five-year period, China was the primary recipient of domestic exports and the primary source of imports (USITC, 2021). Domestic Trade of Other Inorganic Acids, NES cn . ~ . .. ^ cn HI b Lode 2bii.iy.bi /in 30 _ 5 ?n . ¦ £-\J 1 n ¦ ¦ ¦ ±u n _ - u Imports CO O Q. X LU Imports (/) O a. X LU Imports Exports Imports to O Q. X LU Imports l/l o Q. X LU Imports to O Q. X LU 2015 2016 2017 2018 2019 2020 ¦ Imports from China ¦ Imports from Taiwan Imports from Other Countries ¦ Exports to China ¦ Exports to Canada Exports to Other Countries Figure 4. USITC Domestic Import and Export of Inorganic Acids, NES, including Fluorosilicic Acid, between 2015 and 2020 2 Imports for consumption are a subset of general imports, representing the total amount cleared through customs and entering consumption channels, not anticipated to be reshipped to foreign points, but may include some reexports. 3 Domestic exports are a subset of total exports, representing export of domestic merchandise which are produced or manufactured in the U.S. and commodities of foreign origin which have been changed in the U.S. 4 f/EPA ------- Fluorosilicic Acid Supply Chain - Full Profile Tariffs There is a 4.2% general duty for import of FSA, and an additional 25% duty on imports from China (USITC, 2022), as summarized in Table 3. Table 3. 2020 Domestic Tariff Schedule for Inorganic Acids, NES, including Fluorosilicic Acid HS Code General Duty Additional Duty-China (Section 301 Tariff List) Special Duty 2811.19.61 4.2% 25% Free (A, AU, BH, CA, CL, CO, D, E, IL, JO, KR, MA, MX, OM, P, PA, PE, SG)4 Market History & Risk Evaluation History of Shortages As noted, FSA is most commonly produced by capturing and processing the offgas from the wet method of phosphoric acid production. Flowever, the infrastructure necessary to capture and process the offgas is not present at all phosphoric acid manufacturing locations, both domestic and worldwide. Disruptions in the supply chains for phosphate rock and phosphoric acid at the facilities that can capture and process the offgas can therefore have a significant impact on availability of FSA. Phosphate rock is mined in large quantity in a limited number of countries worldwide. In 2017, Morocco, China, and the United States were the leading producers of phosphate rock (USGS, 2020b). The Hubei Province of China, which experienced a prolonged lockdown in 2020 due to the COVID-19 pandemic, is the location of 30% of the country's phosphate production. Similar supply chain disruptions, impacting shipping and transport activities have occurred elsewhere. Though the supply shocks resulting from COVID-19 lockdowns appear to have been temporary, other supply challenges to the phosphate rock market were ongoing in 2022. In 2020, Mosaic, a leading domestic manufacturer of phosphate-based products, petitioned the US Department of Commerce to investigate alleged unfair government subsidies of phosphate fertilizers produced by Russia and Morocco. Mosaic alleged the unfair subsidies increased prices for phosphate in the US, which affected the prices of phosphate-based products such as phosphoric acid. Initial action in 2020 by the Department of Commerce led to a shift in trade flow and an increase in the domestic price for phosphate, a trend that continued through 2021 (INN, 2021). The American Water Works Association (AWWA) released a memo in 2012 remarking on ongoing shortages of FSA supplied to water utilities. AWWA noted that FSA shortages were cyclical and typically seen after June, and recommended utilities ensure full storage by June each year and prepare for increased lead times during warmer months (AWWA, 2012). 4 Symbols used to designate the various preference programs and trade agreements. A full list of special trade agreements and associated acronyms can be found at https://help.cbp.eov/s/article/Article-310?laneuaee=en US and the General Notes Section of the Harmonized Tariff Schedule https://hts.usitc.eov/current 5 f/EPA ------- Fluorosilicic Acid Supply Chain - Full Profile Risk Evaluation The complete risk evaluation methodology is described in Understanding Water Treatment Chemical Supply Chains and the Risk of Disruptions (EPA, 2022b). The risk rating is calculated as the product of the following three risk parameters: Risk = Criticality x Likelihood x Vulnerability Criticality Measure of the importance of a chemical to the water sector Likelihood Measure of the probability that the chemical will experience a supply disruption in the future, which is estimated based on past occurrence of supply disruptions Vulnerability Measure of the market dynamics that make a chemical market more or less resilient to supply disruptions The individual parameter rating is based on evaluation of one or more attributes of the chemical or its supply chain. The ratings and drivers for these three risk parameters are shown below in Table 4. Table 4. Supply Chain Risk Evaluation for Fluorosilicic Acid Risk Parameter Ratings and Drivers 1 1 1 Criticality Low 1 Likelihood High 1 [Vulnerability Moderate-High 1 FSA has widespread but discretionary application for fluoridation and is not used as a precursor to manufacture other water treatment chemicals. The water sector has experienced widespread FSA supply disruptions in the past. FSA is produced at a small number of facilities concentrated in Florida and Louisiana. The facilities that produce FSA as a byproduct of phosphoric acid production routinely experience periods of planned downtime, which results in recurring volatility in the supply of FSA. Limited domestic manufacturing concentrated in select geographic areas, strong reliance on imports with high tariffs, and limited shelf life lead to an elevated vulnerability. The lack of considerable competing uses for FSA slightly reduces the vulnerability. Risk Rating: Moderate-Low ,e.L°w Moderaf Rar>ge 'e/> /\\ fe. t o OQ 6 f/EPA ------- Fluorosilicic Acid Supply Chain - Full Profile References Agency for Toxic Substances and Disease Registry (ATSDR), 2003. Toxicological Profile for Fluorides, Hydrogen Fluoride, and Fluorine, retrieved from https://www.atsdr.cdc.gov/toxprofiles/tpll.pdf American Water Works Association (AWWA), 2011. B703 Fluorosilicic Acid. Denver, CO: American Water Works Association. American Waterworks Association (AWWA), 2012. Fluoridation Chemicals (memo). Denver, CO: American Water Works Association. EPA, 2022a. Chemical Suppliers and Manufacturers Locator Tool, retrieved from https://www.epa.gov/waterutilitvresponse/chemical-suppliers-and-manufacturers-locator-tool EPA, 2022b. Understanding Water Treatment Chemical Supply Chains and the Risk of Disruptions, retrieved from https://www.epa.gov/waterutilitvresponse/risk-disruptions-supplv-water-treatment-chemicals Investing New Network (INN), 2021. 'Phosphate Outlook 2021: Price Rally Expected to Continue', retrieved from https://investingnews.com/dailv/resource-investing/agriculture-investing/phosphate- investing/phosphate-outlook/ NSF International, 2021. Search for NSF Certified Drinking Water Treatment Chemicals, retrieved from https://info.nsf.org/Certified/PwsChemicals/ Potash Corporation of Saskatchewan, Inc. (PotashCorp), 2015. Form 10-K2014, retrieved from https://www.sec.gov/Archives/edgar/data/855931/000119312515062Q91/d863198dl0k.htm Simplot. 2021. Fluorosilicic Acid Safety Data Sheet, retrieved from http://sds.simplot.com/datasheets/17200.pdf Solvay, 2013. Product Safety Summary: Fluorosilicic Acid, retrieved from https://www.solvav.eom/sites/g/files/srpend221/files/2021-01/PSS-Fluorosilicic-Acid.pdf U.S. Geological Survey (USGS), 2020a. 2017 Minerals Yearbook: Fluorspar, retrieved from https://www.usgs.gov/centers/national-minerals-information-center/fluorspar-statistics-and- information U.S. Geological Survey (USGS), 2020b. 2017 Minerals Yearbook: Phosphate Rock, retrieved from https://www.usgs.gov/centers/national-minerals-information-center/phosphate-rock-statistics-and- information U.S. Geological Survey (USGS), 2021. Mineral commodity Summaries for Fluorspar, retrieved from https://www.usgs.gov/centers/national-minerals-information-center/fluorspar-statistics-and- information U.S. International Trade Commission (USITC), 2021. USITC DataWeb, retrieved from https://dataweb.usitc.gov/ U.S. International Trade Commission (USITC), 2022. Harmonized Tariff Schedule (HTS) Search, retrieved from https://hts.usitc.gov/current World Integrated Trade Solutions (WITS), 2022. Trade Statistics by Product (HS 6-digit), retrieved from https://wits.worldbank.org/trade/countrv-bvhs6product.aspx?lang=en#void 7 f/EPA ------- |