1,2-Dichloropropane: Technical Report on Conditions of Use

Table of Contents: A. Identifications B. Manufacturing C. Importation D. Processing E. Distribution F. Disposal G. Releases

About this Technical Report

On August 23, 2019, the U.S. Environmental Protection Agency (EPA) released what it describes as “reasonably available information” about 1,2-dichloropropane (1,2, DCP) and requested comments about the chemical’s conditions of use. 1,2, DCP is one of twenty proposed high-priority substances for evaluation under the Toxic Substances and Control Act.

In response to EPA’s call for further information, this Technical Report provides an overview of the manufacturing, processing, importation, distribution into commerce, and disposal of this chemical. It also provides an accounting of 1,2, DCP waste transfers and releases from these conditions of use.

The majority of the information in the following report is not in EPA’s Supporting Information document.

Specifically, the EPA does not:

. Name the manufacturers, importers, processors, distributors, or disposers of 1,2- dichloropropane. . Identify industries in which 1,2-dichloropropane is processed, including those that manufacture paper sizing agents, flame retardants, isocyanates and epichlorohydrin. . Identify articles in which 1,2-dichloropropane is distributed into commerce as an ingredient, including polyurethane and epoxy plastics. . Consider the distribution of 1,2-dichloropropane into commerce through imported articles, including paints that contain this chemical as a solvent, or, potentially, foods that may contain biocide residues used overseas. . Consider releases from disposal practices that disperse this chemical into the air, water, and land. Prepared for Earthjustice by Material Research L3C 1 November 2019

In short, the EPA document fails to identify many conditions of use of 1,2-dichloropropane where it is released into the environment, even though this information is publicly available from EPA and other government agency data.

This report is based on public information, including company literature and filings, state and federal agency data especially from the EPA, Centers for Disease Control and Prevention, and U.S. Customs and Border Protection Agency, and overseas government reports.

A. Identifications

Chemical Name: 1,2-Dichloropropane CAS RN : 78-87-5 (primary); also registered as 26198-63-0. UN Code: 12791 USEPA/OPP Pesticide Code: 029002 EPA Docket: https://www.regulations.gov/docket?D=EPA-HQ-OPPT-2018-0428 EPA Supporting Information Document: https://www.epa.gov/sites/production/files/2019- 08/documents/12-dichloropropane_78-87-5_high-priority_proposal_designation_082219.pdf

Synonyms2: Most commonly: Propylene dichloride; Also: • .alpha.,.beta.-Dichloropropane • .alpha.,.beta.-Propylene dichloride • 1,2-D • 1,2-DCP • 1,2-dichloro-propane • 1,2-dichlorpropan • 2,3-dichloropropane • alpha,beta-Dichloropropane • alpha,beta-Propylene dichloride • Bichlorure de propylene • Chlorinated C3 hydrocarbons • component of D-D Mixture (Salt/Mix) • Dichloro-1,2 propane • Dichloropropane, 1,2- • Dichloropropanes • Dwuchloropropan • Propane, 1,2-dichloro- • Propane, 2-dichloro- • Propylene chloride • PDC

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Trade Names: • CSF / Crude Soil Fumigant (mixture; reaction mass of 1,2-dichloropropane and 1,3- dichloropropene) • DD (in mixture with 1,3-dichloropropene)

B. Manufacturing

1,2-dichloropropane is a by-product of the reaction of propene and chlorine in epichlorohydrin manufacturing.3 (Epichlorohydrin is a key ingredient of epoxy resins). 1,2-dichloropropane also can be manufactured from propylene chloride and antimony pentachloride.4

In 2013, Dow estimated that worldwide, between 400 and 510 million pounds of 1,2- dichloropropane were made annually.5

1. U.S. Manufacturing

Chlor-alkali chemical complexes run by Dow, in Freeport, Texas, and Plaquemine, Louisiana, are the only places in the U.S. where 1,2-dichloropropane manufacturing has been reported since at least 1992.6 Two small, and now closed, chemical plants were producing 1,2-dichloropropane in the 1980s.7

In 1972, about 41 million pounds of 1,2-dichloropropane were sold in the U.S. from domestic and overseas manufacturing facilities. From 1986 to 2002, domestic manufacturing and imports of 1,2-dichloropropane exceeded 100 million pounds (except for 1990, when EPA reported that between 50 and 100 million pounds were made or imported). EPA and Dow do not disclose how much the company itself manufactures in the U.S., and to protect what Dow claims to be confidential information, EPA has not provided national estimates since 2002.

The lack of data about this industry is longstanding. Thirty years ago, an EPA/ATSDR toxicological profile for 1,2-dichloropropane noted:

Current information concerning production volume and use is lacking. This type of information is absolutely necessary for estimating the potential for environmental releases from various industries, as well as potential concentrations in the environmental. Knowledge of what consumer products contain 1,2-dichloropropane is essential for estimating general population exposure. Unfortunately, this type of information is difficult to obtain in detail since companies consider it to be confidential business information.”8

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a. Dow Chemical (Freeport, Texas, and Plaquemine, Louisiana)

Dow’s Freeport, Texas, and Plaquemine, Louisiana, plants have been the only known U.S. manufacturers of 1,2-dichloropropane since at least 1992.9 While Dow lists manufacturing capacities for this chemical worldwide, it does not provide this information on an individual plant basis. EPA’s public versions of Dow’s 2012 and 2016 Chemical Data Reporting do not quantify the amount of 1,2- dichloropropane it makes or imports.

b. Olin (Freeport, Texas)

Olin produces 1,2-dichloropropane in Freeport, according to its 2016 chemical data reporting. EPA’s public version of Olin’s 2016 Chemical Data Reporting provides no further details on the sources or quantities of the chemicals it used. It said the chemical is used as an intermediate in basic organic chemical manufacturing.10

2. Overseas Manufacturers

1,2-dichloropropane is a major product of Dow’s chlor-alkali plants in Aratu, Bahia, Brazil. Dow exports most of its output from Aratu to its isocyanate plant in Freeport, Texas.11 In addition to Dow in Brazil and Stade, Germany, other companies are manufacturers of 1,2-dichloropropane in Europe and Asia.

In Europe, a Hexion plant in Rotterdam-Pernis, Netherlands, has been producing 1,2-dichloropropane since at least 1994, when Shell owned it.12 According to recent European Environment Bureau research, three other European companies produce more than 2 million pounds of 1,2-dichloropropane, combined: Olchim (Ramnicu Valcea, Romania); PCC Rokia (Brzeg, Poland), and PPG Central (Stowmarket, U.K.).13 The PCC Group markets the use of this chemical as a biocide (see below).

In Asia, Asahi has produced 1,2-dichloropropane at its plant in Kashima, Japan (it was the leading air pollutant there in 2003). However, this chemical plant was heavily damaged by the Fukushima earthquake of 2011.14 China is also producing 1,2- dichloropropane. The annual manufacturing output of 1,2-dichloropropane in China was estimated at between 100 and 150 million pounds in 2008.15

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C. Importation

Figure 1. Graph based on U.S. International Trade Commission Dataweb records for Harmonized Tariff Schedule 2903.19.05, 1,2-Dichloropropane (Propylene dichloride) and dichlorobutanes.

U.S. companies import 1,2-dichloropropane and related dichlorobutanes mainly from Dow plants in Brazil and Germany. Since 2009, these imports have averaged 31.4 million pounds per year, according to official U.S. International Trade Commission (ITC) statistics.

An examination of individual (rather than aggregated) U.S. Customs shipping records suggests that figures provided by the U.S. ITC are low: in 2016 alone, for example, Dow imported over 64 million pounds and in 2018, 71 million pounds, from ports in the Netherlands and Brazil.16

1. Dow Chemical / Dow Agrosciences

U.S. Customs records reveal that Dow is responsible for most of the 1,2- dichloropropane that is shipped to the United States. Dow ships most of its 1,2- dichloropropane output from Aratu, Brazil, to Freeport, Texas, for processing in its isocyanates plant.17

Dow Agrosciences imported six million pounds of 1,2-dichloropropane from Taiwan and China in 2016.

2. Others

A Laredo, Texas company called Feria & Associates, a small brokerage,18 imports 1,2-dichloropropane from China. The first shipment, in 2016, weighed 10,540 Prepared for Earthjustice by Material Research L3C 5 November 2019

kilograms, or 23,236 pounds. This is just under the CDR reporting threshold of 25,000 pounds. The second shipment, of 17,654 kg (38,920 pounds), occurred in 2018. The supplier from China, Hangzhou Dayangchem of Shanghai, contracts with other chemical factories in China to produce certain chemicals.19

D. Processing

1. Dow (Freeport, Texas and Plaquemine, Louisiana)

According to Dow’s CDR reporting, it uses the chemical as an intermediate in formulations, mixtures, or reaction products. In 1983, according to Dow, “over 95% of the isolated product manufactured by Dow Chemical [was] used on-site as a captive intermediate in the production of perchloroethylene and other chlorinated products by their 'per-tet' process.”20

In a 2014 company publication, Dow says it processes 1,2-dichloropropane internally to make products, “such as chlorinated solvents, toluene diisocyanate (a chemical used in polyurethane manufacture), photographic film, and ion-exchange resins.”21

2. Olin (Freeport, Texas)

In the 2016 CDR, Olin said it processes 1,2-dichloropropane at its Freeport, Texas, plant as an intermediate for “Basic Organic Chemical Manufacturing.” Olin obtained two of the world’s largest epoxy manufacturing units – located within Dow’s chemical complexes in Freeport, Texas, and Plaquemine, Louisiana – from Dow in 2015. Olin describes its Freeport plant as “the lowest cost producer of epoxies globally.”22

3. Solenis (Courtland, Virginia)

The main unit at the Solenis LLC plant in Courtland, Virginia, is called the Aquapel® process. It is “a batch process that converts fatty acids to an alkyl ketene dimer, a sizing agent for the fine paper industry,” according to the State of Virginia.23

Paper sizing agents are applied to paper for water resistance and printability.

The plant, formerly owned by Hercules Chemical, was acquired by Ashland Chemical in 2008, which in turn became Solenis in 2014.24 Hercules held a patent, which expired in 2018, in which 1,2-dichloropropane is used as a solvent in the production of alkaline paper surface sizing agents. At the end of doing its part in the production, the chemical is “evaporated.” 25 Solenis is the country’s leading source of reported 1,2-dichloropropane air releases (see G. Releases, below).

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Solenis is not identified in public CDR data about this chemical.

E. Distribution into Commerce

1,2-dichloropropane is distributed into commerce in biocides and flame retardants. It also is an unintentional residual of polyvinyl chloride plastics.

Current use information is sparse. According to an EPA/ATSDR toxicological profile of 1,2- dichloropropane:

Outside of its use as a chemical intermediate, Dow Chemical Company's use pattern for 1,2-dichloropropane in 1982 was 41% in ion exchange manufacturing, 34% in toluene diisocyanate (TDI) production, 19% in photographic film production, 4% in paper coating, and 2% in petroleum catalyst regeneration.26

1. Biocides

Until 1976, Dow marketed a soil fumigant called DD, or D-D, which it registered for use in a wide array of croplands.27 A 1977 Shell memorandum said 1,2- dichloropropane was present in D-D at levels of between 19% and 28% by weight.28 1,2-dichloropropane has been a component of other soil fumigants including Dow- 421, Dowfume EB-5, Nematox, Telone II, and Vidden D.29

In 1976, Dow stopped making 1,2-dichloropropane available for pesticidal mixtures in the U.S.30 However, in 2018, Dow Agrosciences imported 2,000 metric tons of “dichloropropane” from Taiwan. This indicates continued distribution of this chemical by Dow’s agricultural chemical division.

D-D is no longer registered for use in the U.S.31; however, it is still registered in Europe. Dow’s plant in Stade, Germany, and Hexion‘s plant in the Netherlands are registered in the European Union as suppliers of “a reaction mass of 1,3- dichloropropene and 1,2-dichloropropane," a “multi-constituent substance" sold as a “Crude Soil Fumigant” or CSF.32

Biocide mixtures containing 1,2-dichloropropane continue to be used outside the U.S. For example, a 2016 Oxfam study said, "DD dicloropropano” Biocide is used to kill nematodes on pineapples.33

“Soil fumigants based on 1,2-Dichloropropane are still used in some Asian countries,” stated the PCC Group of Poland in a 2018 blog post.

In the agrochemical industry, dichloropropane is also used as an insecticide ingredient. Such preparations are used to protect fruit trees against feeding insects. In addition, DCP also helps in the elimination of mold and other

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pathogenic fungi in crops of cereals, rapeseed, vegetables and fruits, root crops, legumes and many other agricultural crops (e.g. against fusariosis, powdery mildew, snow mold, rust and spots).”34

2. Food

1,2-dichloropropane has been identified as a trade impurity (no higher than 100 parts per million by weight) in 1,3-dichloropropene, a more widely used fumigant.35

There are no testing requirements for residues of 1,2-dichloropropane in imported foods. However, “significant residues are unlikely to occur in edible crops, because these are not normally planted until most of the fumigant has dissipated,” according to a 1992 World Health Organization report. “1,2-Dichloropropane can be taken up by edible crops, but residues detected have been low (< 0.01 mg/kg) and are unlikely to be biologically significant.”36

3. Flame Retardant Plasticizers

ICL-IP Americas produces flame retardant plasticizers at a plant in Gallipolis Ferry, West Virginia. One of these, Phosflex 314, contains up to 0.02% 1,2- dichloropropane.37 The company describes it as

a proprietary low color plasticizer blend containing triaryl phosphate esters. This mixture is useful in a number of PVC applications including vinyl wall covering, sheet goods, and laminates requiring a high degree of flame resistance.38

ICL-IP Americas is not identified in public CDR data with regard to this chemical.

4. Paints

In 2012, Intochem S.A., a chemical distributor, shipped 21 tons of 1,2- dichloropropane from Haifa, Israel, to Sur Quimica of Costa Rica. Sur Quimica sells a paint called Polysur Fondo Acabado Satinado. According to its safety data sheet, this paint contains 15-20% 1,2-dichloropropane by weight.39

Sur Quimica, in turn, ships paints, varnishes and other articles from Costa Rica to Pinturas Sur de Puerto Rico Corp., near Bayamon, Puerto Rico.40

5. PVC

1,2-dichloropropane is a constituent of “heavy ends,” a mixture of by-products from the reaction of chlorine and ethylene to make ethylene dichloride (EDC). These heavy ends, including 1,2-dichloropropane, can contaminate vinyl chloride monomer

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(VCM) made from EDC and subsequently, polyvinyl chloride plastic made from VCM.41

A 1977 internal Shell memo said 1,2-dichloropropane is present at a “fraction of a %” in VCM heavy ends and crude epichlorohydrin.42

A study of PVC drinking water pipes in 2019 detected 1,2-dichloropropane contaminants in the water. It found the chemical in the drinking water of “all pipes used” in the migration experiment, with a mean value of 13.437 µg/L, and a maximum concentration of 19.93 µg/L. “The levels of 1,2-dichloropropane in (the) leaching process are below the allowable limits of WHO (30 µg/L),” noted the study’s authors.43

6. Historical Uses

In addition to being used as a solvent in processing paper sizing agents, 1,2- dichloropropane has been used as an industrial solvent in the of fats, oils, resins, waxes, and rubbers.44

It was also “widely used” for degreasing and in dry cleaning fluids in 1977, according to NIOSH.45

Other historical uses include: cellulose plastics manufacturing; furniture finishes, gums, paint stripper, scouring compounds, and stain removers.46

F. Disposal

Most 1,2-dichloropropane waste is burned, mainly in hazardous waste incinerators but also in a spent carbon thermal treatment and a cement kiln.

1. Incineration

The great majority of 1,2-dichloropropane waste is incinerated by Dow Chemical in Freeport, Texas. More than 99.98% of waste transfers reported to EPA between 2012 and 2018 were burned, 88% of which was incinerated by Dow in Freeport (Table 1). The waste burned by Dow came from its and Olin’s operations in Freeport and Plaquemine. Overall, incinerators received 9,252,746 pounds of 1,2- dichloropropane waste between 2012 and 2018. Incinerator operators (including cement kilns) reported releasing 1,292 pounds of 1,2-dichloropropane into the air during this period.

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2. Landfills

A leading recipient of 1,2-dichloropropane waste from 2012 to 2018 was Waste Management’s Woodside Landfill in Walker, Louisiana. This dumpsite received 388 pounds of waste from Dow’s Plaquemine complex and 41 pounds from Hexion’s epichlorohydrin plant in Norco, Louisiana. The Louisiana Environmental Action Network, with assistance from the Tulane Environmental Law Clinic, has long sought to close the Woodside Landfill due to air and water quality concerns.47 Other landfills receiving 1,2-dichloropropane are located in Ohio, Indiana, Michigan, and Louisiana.

Further details are found in the G. Releases, below.

Table 1. 1,2-Dichloropropane Waste Transfers

To Facility Type Pounds (2012-2018) Dow Chemical (Freeport, TX) Incinerator 8,148,977 Dow Chemical (Midland, MI) Incinerator 932,309 Clean Harbors Deer Park (La Porte, TX) Incinerator 99,125 Clean Harbors - El Dorado AR (El Dorado, AR) Incinerator 53,971 Veolia Es Technical Solutions (Port Arthur, TX) Incinerator 15,235

Ross Incineration Services Inc (Grafton, OH) Incinerator 1,399

Clean Harbors El Dorado, LLC (El Dorado, AR) Incinerator 1,026 Shell Norco Chemical Plant West Site (Norco, LA) Wastewater Treatment 679 Waste Management Woodside Landfill (Walker, LA) Landfill 421 Beech Hollow Landfill (Wellston, OH) Landfill 168 Tradebe Treatment & Recycling LLC (East Chicago, IN) Recycling: 135 Solvents/Organics Recovery

Veolia Es Technical Solutions LLC (West Carrollton, OH) Other Waste Treatment 60 Rineco Chemical (Benton, AR) Incinerator 41 Heritage-WTI Inc (East Liverpool, OH) Incinerator 26 Michigan Disposal (Belleville, MI) Landfill 24 Heritage Environmental Services LLC (Indianapolis, IN) Landfill 15 Calgon Carbon Corporation (Pittsburgh, PA) Recycling: Transfer to 11 Waste Broker Chemical Waste Management - Sulphur LA (Sulphur, LA) Landfill 8 Wayne Disposal Inc (Belleville, MI) Landfill 7.9 Clean Harbors Environmental Services (La Porte, TX) Incinerator 5 Waste Management - Sulphur LA (Sulphur, LA) Incinerator 3 TOTAL 9,253,647

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G. Releases

1. Releases from Manufacturing and Processing

a. Solenis (Courtland, Virginia)

According to Toxic Release Inventory reports, the leading reported source of 1,2-dichloropropane from 2012 to 2018 was the Solenis specialty chemical plant in Courtland, Virginia. This plant accounted for 76% of all reported releases of 1,2-dichloropropane in the U.S. from 2012 to 2014. On average, in those three years, it reported releasing 70,000 pounds per year, out of a nationwide average of 92,000 pounds per year. During the processing of 1,2-dichloropropane in this plant, the chemical is “evaporated.” 48

In 2012, the Courtland plant released 55,197 pounds of 1,2-dichloropropane. In 2013 and 2014, the Courtland plant released a reported 85,503 pounds and 66,039 pounds. Since then, releases have declined by over 90%, according to its new owner, Solenis. It reported nearly identical figures each year from 2015 to 2018. It is unclear why the reported releases dropped so dramatically.49

In addition, from 2012 to 2018, the Hercules/Ashland/Solenis plant in Courtland, Virginia, sent a reported 1,024 pounds of 1,2-dichloropropane waste to the Clean Harbors incinerator in El Dorado, Arkansas.50

Solenis is not identified in public CDR data about this chemical. It is the leading source of reported 1,2-dichloropropane releases in the US.

Chemical plants release 1,2-dichloropropane mainly into the air, although some is also released into adjacent waterways, including the Ohio and Mississippi Rivers.

The processing of 1,2-dichloropropane can also contaminate groundwater. 1,2- dichloropropane is the primary contaminant in groundwater around the Solenis chemical plant in Virginia. Due to this pollution, the site is undergoing corrective action enforced by EPA under the Solid Waste Disposal Act.51

b. Olin (Freeport and Plaquemine)

Toxic Release Inventory data submitted by Olin also shows significant, on-going releases of 1,2-dichloropropane in its part of the Plaquemine plant.

Olin also produces epichlorohydrin at its Plaquemine, Louisiana, plant, where it reports releasing 1,2-dichloropropane into the air (see Releases below). Olin’s Prepared for Earthjustice by Material Research L3C 11 November 2019

operations in Plaquemine are not identified in public CDR data for 1,2- dichloropropane. Receiving toxic substances from domestic sources is not subject to CDR reporting.

From 2015 to 2018, Olin reported releasing, on average, 586 pounds per year of 1,2-dichloropropane into the air and 1 pound into the Brazos River next to its Freeport plant.

c. Dow (multiple locations)

Dow’s manufacturing, importation, and disposal practices lead to releases of 1,2- dichloropropane on-site and offsite. Dow reported releasing 1,2-dichloropropane into the environment at four facilities. Between 2012 and 2018, Dow’s operations reported releasing 53,650 pounds, including 41,024 pounds into the air, 3,191 pounds into water (mainly the Mississippi and Brazos Rivers), and 9,435 pounds into an on-site landfill. In 2018, Dow reported transferring 380 pounds of 1,2- dichloropropane waste from its Plaquemine plant to the Waste Management Woodside Landfill in Walker, Louisiana.

Most of Dow’s releases were reported from its Freeport and Plaquemine operations. Smaller, ongoing releases (less than 100 pounds) per year were reported from Dow’s Midland, Michigan, and Paincourtville, Louisiana, facilities. Paincourtville, in Assumption Parish, is the site of Dow’s Grand Bayou brine production operations.52 Brine – a mixture of water and salt mined from the area - is the essential feedstock for chlor-alkali plants in Louisiana, including the Olin/Dow operation in Plaquemine.

d. ICL-IP America (Gallipolis Ferry, West Virginia)

ICL-IP America's flame-retardant plasticizers plant in Gallipolis Ferry, West Virginia, is the second leading source of 1,2-dichloropropane releases to air in the U.S. According to TRI data, between 2012 and 2018, ICL released over 3 tons of this chemical into the air and water (Ohio River) each year. Since 1992, this chemical plant, has released over 372,000 pounds of 1,2-dichloropropane.53

e. Hexion (Norco, Louisiana)

Hexion was the fifth highest source of 1,2-dichloropropane releases into air between 2012 and 2018. It also reported transferring 1,2-dichloropropane waste to a water- treatment system, owned by Shell, in Norco, Louisiana from 2012 to 2016. Hexion is closing this plant, which produced epichlorohydrin.54

Hexion is not identified in public CDR data about this chemical.

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Table 2. 1,2-Dichloropropane Releases by Manufacturers & Processors, pounds, total, 2012 – 2018

Facility Name Related Air Water Land Off-Site Sum Products Transfer Olin Blue Cube EDC/PVC, 2,343 2 7,888,720a 7,891,065 (Freeport, TX) Epoxies Dow Chemical 1,2-DCP, 31,278 1,082 4,974 1,333,897b 1,371,231 (Freeport, TX) isocyanates, Incinerator Solenis LLC Paper sizing 221,878 215 1,024c 223,118 (Courtland, VA) agents ICL-IP America Inc Flame retardant 44,807 28 182d 45,018.4 (Gallipolis Ferry, plasticizers WV) Dow Chemical Isocyanates 9,675 1,969 4,461 14,636e 30,741.0 (Plaquemine, LA) Texas Barge & Boat Unknown 126 12,384f 12,510 Inc (Freeport, TX) Hexion Inc (Norco, Epichlorohydrin 5,555 720g 6,275 LA) Blue Cube (Olin) Epoxies 1,327 377h 1,704 (Plaquemine, LA) Calgon Corp Waste treatment 1,091 1,091 (Catlettsburg, KY) Occidental Chemical EDC/PVC 610 610 (Geismar, LA) Westlake Vinyls EDC/PVC 80 80 (Geismar, LA) The Dow Chemical Brine 21 21 Grand Bayou Operations (Paincourtville, LA) Southwest Shipyard Unknown 19 19 LP (Channelview, TX) TOTAL (2012 to 318,811 3297 9435 9,251,941 9,583,484 2018) Blank = No information reported in TRI or Chemical Data Exchange. a Destinations: Dow Chemical – Freeport TX (7,830,398 lbs), Clean Harbors – El Dorado AR (53,971 lbs), Veolia Es Technical Solutions LLC – Port Arthur TX (2,849 lbs), Clean Harbors Deer Park, L.P. – La Porte TX (1,494 lbs), Clean Harbors Environmental Services – La Porte TX (5 lbs), Waste Management – Sulphur LA (3 lbs) b Destinations: The Dow Chemical Company Midland – Midland MI (932,309 lbs), The Dow Chemical Company Freeport – Freeport TX (304,674 lbs), Clean Harbors Deer Part L.P – La Porte TX (9,614 lbs) c Destination: Clean Harbors El Dorado LLC – El Dorado AR (1024.4 lbs) d Destinations: Beech Hollow Landfill – Wellston OH (168.46 lbs), Calgon Carbon Corporation – Pittsburgh PA (11.42 lbs), Ross Incineration Services (2.9 lbs) e Destinations: The Dow Chemical Company Freeport – Freeport TX (13751 lbs), Clean Harbors Deer Park, L.P. – La Porte TX (495 lbs), Waste Management Woodside Landfill – Walker LA (380 lbs), Chemical Waste Management – Sulphur LA (8 lbs), Veolia Es Technical Solutions LLC – Port Arthur TX (2 lbs) f Destination: Veolia Es Technical Solutions LLC Port Arthur Facility – Port Arthur TX (12383.8)

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g Destinations: Shell Norco Chemical Plant West Site – Norco LA (697 lbs), Waste Management Woodside Landfill – Walker LA (41 lbs) h Destinations: Clean Harbors Deer Park, L.P. – La Porte TX (222 lbs), Dow Chemical Texas Operations Freeport – Freeport TX (154), Clean Harbors El Dorado LLC – El Dorado AR (1 lb)

2. Releases from Product Use

a. Agriculture

The historical use of the biocide D-D in the U.S. has contaminated groundwater with 1,2-dichloropropane. A 1989 study found it in groundwater samples in 7 states.55 A routine well test in 2008 found 1,2-dichloropropane contamination in North Carolina, decades after it was used on the soil, 100 feet above.56

A World Health Organization study notes:

Leaching of 1,2-dichloropropane occurs from soil and can contaminate upper and deeper ground water in areas where ‘Mix D/D’ has been used as a soil fumigant. In well water and groundwater in the USA, concentrations of up to 440 µg/litre and 51 µg/litre, respectively, have been found. In the Netherlands, concentrations of up to 160 µg/litre have been measured in well water and 1,2-dichloropropane has been found to a depth of 13m.”57

A webpage updated last in 2015, the Centers for Disease Control states:

1,2- Dichloropropane is found in a few drinking-water supplies, and most of those are from groundwater sources. A nationwide survey of groundwater supplies showed that 1.4% of these supplies contained 1,2- dichloropropane levels at around 1 part per billion (ppb). The highest amount of 1,2-dichloropropane in the survey was 21 ppb. Private wells in farming areas where 1,2-dichloropropane was once used as a soil fumigant have the greatest risk for contamination.”58

b. Spray Foam Insulation

1,2-dichloropropane is a degradation product from a flame retardant, tris (1- chloro-2-propyl) phosphate (TCPP). TCPP is widely used in spray polyurethane foam (SPF) insulation for buildings. Air chamber tests from newly-reacted SPF insulation found high concentrations of 1,2-dichloropropane. The highest concentrations occurred soonest after installation. In at least three separate studies, air concentrations approached the occupational safety threshold of 350 ug/m3. A test by Bayer found 276 ug 1,2-dichloroprane/m3 at zero hour. Two

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tests by the National Institute for Standards and Technology found over 300 ug 1,2-dichloroprane/m3 in the first few hours.59 Air concentrations remained above 50 ug/m3 through 50 hours, which exceeds safety limits in at least five countries.60

Air Chamber Tests of Emissions from Spray Polyurethane Foam

Figure 2. Reproduced from Poppendieck, D., M. Schlegel, A. Connor, and A. Blickley. “Flame Retardant Emissions from Spray Polyurethane Foam Insulation.” ASTM Standard Selected Technical Papers. National Institute of Standards and Technology, 2017. https://www.astm.org/DIGITAL_LIBRARY/STP/PAGES/STP158920150044.htm.

3. Releases from Waste Disposal and Treatment Operations

Overall, six incinerators reported releasing at least 1,292 pounds of 1,2- dichloropropane into air during the period 2012 to 2018.

By far, the leading destination for 1,2-dichloropropane waste transfers is Dow Chemical’s incinerator in Freeport, Texas, which received 8.1 million pounds between 2012 and 2018. It is not possible to determine the proportions of Dow’s overall air emissions in Freeport attributable to this incinerator. Dow also receives, burns and releases 1,2-dichloropropane in Midland, Michigan, where it reported releasing relatively small quantities into the air and water (see Table 3).

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The leading source of reported 1,2-dichloropropane releases into air is a spent carbon treatment plant, owned by Calgon Carbon, in Catlettsburg, Kentucky. Calgon Carbon told EPA this treatment facility released 1,091 pounds of 1,2- dichloropropane into air between 2012 and 2018.

At least 624 pounds of 1,2-dichloropropane was released into land through transfers and disposal of waste in landfills.

Table 3. 1,2-Dichloropropane Releases by Waste Disposal Sites, pounds, total 2012 - 2018

Facility Name, Waste Origins Air Wat Land Off-Site Sum Location, Type er Transfer Heritage - WTI Thermal Norlite 33.8 0.07 1,409a 1,443 Services (East Liverpool, OH) incinerator Calgon Corp ICL-IP 1,091 1,091 (Catlettsburg, KY) spent carbon treatment Waste Management Dow (Plaquemine); 421 421e Woodside Landfill Hexion (Walker, LA) Norlite LLC (Cohoes, NY) Unknown 119 296b 415 cement kiln Beech Hollow Landfill ICL-IP 168 168 e (Wellston, OH) Dow Chemical (Midland, Dow (Freeport) 7 20 27 MI) incinerator Veolia Es Technical Olin (Freeport); Dow 26.6 26.6 Solutions (Port Arthur, (Plaquemine); Texas TX) incinerator Barge Michigan Disposal Heritage – WTI 24 24e (Belleville, MI) landfill incinerator (East Liverpool) Heritage Environmental Heritage – WTI 15 15e Services LLC incinerator (East (Indianapolis, IN) landfill Liverpool) Clean Harbors Deer Park Dow (Freeport and 12.4 1c 13.4 LLC (La Porte, TX) Plaquemine); Olin incinerator (Freeport and Plaquemine) Chemical Waste Olin (Freeport); Dow 8 8e Management - Sulphur (Plaquemine) LA (Sulphur, LA) landfill Wayne Disposal Inc Heritage – WTI 7.9 7.9e (Belleville, MI) landfill incinerator (East Liverpool) Clean Harbors El Dorado Olin (Freeport and 1.8 1.8 LLC (El Dorado, AR) Plaquemine); incinerator Solenis; Clean Harbors (Deer Park)

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Dow Chemicals Dow (Freeport and See Table 2d (Freeport, TX) incinerator Plaquemine); Olin (Freeport and Plaquemine) TOTAL (2012 to 2018) 1,292 d 20 d 644 d 1,706 d 3,662 d Blank = No information reported in TRI or Chemical Data Exchange. a Destinations: Ross Incineration Services Inc – Grafton OH (1,261.55 lbs), Veolia Es Technical Solutions LLC – West Carrollton OH (60 lbs), Rineco Chemical – Benton AR (40.94 lbs), Michigan Disposal – Belleville MI (24.1 lbs), Heritage Environmental Services LLC – Indianapolis IN (15.16 lbs), Wayne Disposal Inc – Belleville MI (7.9 lbs) b Destinations: Tradebe Treatment Recycling LLC – East Chicago IN (135.15 lbs), Ross Incineration Services – Grafton OH (134.4 lbs), Heritage-WTI Inc – East Liverpool OH (26.14 lbs) c Destination: Clean Harbors El Dorado LLC – El Dorado AR (1 lb) d Dow’s Freeport plant is a manufacturer, processor, and disposer of 1,2-dichloropropane. TRI reporting (see Releases by Manufacturers table) does not provide a breakdown of releases by phase of use. Unknown portions of the site’s reported releases come from an onsite incinerator, to which 8.1 million pounds of 1,2-dichloropropane were transferred between 2012 and 2018 (see Table 1,Transfers).

e This facility did not report 1,2-dichloropropane releases to EPA’s Toxics Release Inventory. This figure is based upon reported transfers of 1,2-dichloropropane waste to this facility and assumes this waste is landfilled.

ENDNOTES

1 National Oceanic and Atmospheric Administration. “Chemical Data Sheet 1,2-Dichloropropane.” Cameo Chemicals, n.d. https://cameochemicals.noaa.gov/chemical/4358. 2 Healthy Building Network. “1,2-Dichloropropane.” Data Commons, n.d. https://commons.healthymaterials.net/chemicals/2004481. 3 TNO Centre for Technology and Policy Studies. “A Chlorine Balance for The Netherlands,” November 16, 1996. https://openaccess.leidenuniv.nl/bitstream/1887/8010/1/11_502_007.pdf. 4 International Agency for Research on Cancer. “1,2-Dichloropropane.” IARC Monographs, n.d. https://monographs.iarc.fr/wp-content/uploads/2018/06/mono110-03.pdf and U.S. National Library of Medicine. “1,2-Dichloropropane.” Hazardous Substance Data Base, n.d. https://toxnet.nlm.nih.gov/cgi- bin/sis/htmlgen?HSDB. 5 Dow. “Product Safety Assessment of Propylene Dichloride.” Dow Materials Safety Data Sheets, October 14, 2014. http://msdssearch.dow.com/PublishedLiteratureDOWCOM/dh_091a/0901b8038091ae34.pdf?filepath=pro ductsafety/pdfs/noreg/233-00427.pdf&fromPage=GetDoc. (Dow 2014) 6 SRI. “1992 Director of Chemical Producers: United States of America.” SRI International, 1992. U.S. Environmental Protection Agency. “ChemView,” 2019. https://chemview.epa.gov/chemview (output selected: Chemical Data Reporting: 2012 and 2016 Reporting Years). 7 In 1988, Columbia Organics in Cassatt, SC, was still operating. Another, Mannsville Chemical Products (New York), stopped producing in 1984 (ATSDR Toxicological Profiles). 8 Agency for Toxic Substances and Disease Registry. “Toxicological Profile 1,2-Dichloropropane.” ATSDR Toxicological profiles, 1989. https://www.atsdr.cdc.gov/toxprofiles/tp134-c4.pdf.

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9 SRI. “1992 Directory of Chemical Producers: United States of America.” SRI International, 1992. U.S. Environmental Protection Agency. “ChemView,” 2019. https://chemview.epa.gov/chemview (output selected: Chemical Data Reporting: 2012 and 2016 Reporting Years). 10 U.S. Environmental Protection Agency. “ChemView,” 2019. https://chemview.epa.gov/chemview (output selected: Chemical Data Reporting: 2012 and 2016 Reporting Years). 11 Vallette, Jim, and Connie Murtagh. “Chlorine and Building Materials: A Global Inventory of Production Technologies and Markets - Phase 2: Asia • Including Worldwide Findings.” Chlorine and Building Materials. Healthy Building Network, March 2019. https://healthybuilding.net/reports/20-chlorine-building- materials-project-phase-2-asia-including-worldwide-findings. 12 SRI. “1994 Directory of Chemical Producers: Western Europe.” SRI International, 1994. 13 Santos, Tatiana. “Companies Behind Incomplete Dossiers“ European Environmental Bureau, 2018. 14 SRI International, 1994/95 Directory of Chemical Producers East Asia, 1994. Also: “Asahi Glass Sustainability Report 2004.” 2004. AGC: Asahi Glass Company. https://www.agc.com/en/csr/pdf/2004.pdf. 15 International Agency for Research on Cancer. “1,2-Dichloropropane.” IARC Monographs, n.d. https://monographs.iarc.fr/wp-content/uploads/2018/06/mono110-03.pdf. (IARC) 16 U.S. Customs and Border Patrol records as obtained through the Panjiva trade database. 17 Vallette, Jim, and Connie Murtagh. “Chlorine and Building Materials: A Global Inventory of Production Technologies and Markets - Phase 2: Asia • Including Worldwide Findings.” Chlorine and Building Materials. Healthy Building Network, March 2019. https://healthybuilding.net/reports/20-chlorine-building- materials-project-phase-2-asia-including-worldwide-findings. 18 LinkedIn. “Victor Feria,” n.d. Accessed September 13, 2019. 19 “About Us.” Hangzhoudayang Chem Co. Ltd, 2006. http://www.chinadayangchem.com/about/42- en.html. 20 ATSDR 1989. 21 Dow. “Product Safety Assessment of Propylene Dichloride.” Dow Materials Safety Data Sheets, n.d. http://msdssearch.dow.com/PublishedLiteratureDOWCOM/dh_091a/0901b8038091ae34.pdf?filepath=pro ductsafety/pdfs/noreg/233-00427.pdf&fromPage=GetDoc. 22 Olin Corporation. “KeyBanc Capital Markets.” presented at the Basic Materials & Packaging Conference, September 3, 2015. https://www.sec.gov/Archives/edgar/data/74303/000095015715001063/ex99-1.htm 23 Commonwealth of Virginia. “Statement of Legal and Factual Basis.” Department of Environmental Quality, April 2015. https://www.deq.virginia.gov/Portals/0/DEQ/Air/Permitting/TitleVPermits/60188_statement.pdf. 24 Solenis. “The Diversity of Our Past Makes Us Strong.” Our History, Solenis, n.d. https://solenis.com/en/about-us/history/. 25 Brungardt, Clement, Richard Riehle, and Jian Jian Zhang. Alkaline paper surface sizing agents. USPTO US6048392A, filed December 23, 1997, and issued April 11, 2000. 26 ATSDR 1989. 27 “Synthetic Organic Chemicals. United States Production and Sales, 1972.” United States Tariff Commission, 1973. “Synthetic Organic Chemicals. United States Production and Sales, 1963.” United States Tariff Commission, 1964. 28 Superintendent - Environmental Conservation - Deer Park Mfg. Complex, Shell Oil Company. “Subject: Toxic Substances Control Act (TOSCA) Inventory List.” Shell Chemical Company, November 11, 1977. https://cdn.toxicdocs.org/XR/XRq0yVo9ZKKejbar61wXy9Gjx/XRq0yVo9ZKKejbar61wXy9Gjx.pdf. 29 California Environmental Protection Agency. “Public Health Goal for 1,2-Dichloropropane In Drinking Water.” Office of Environmental Health Hazard Assessment, February 1999. https://oehha.ca.gov/media/downloads/water/chemicals/phg/12dcpf.pdf. 30 U.S. Geological Survey. “Agricultural Pesticides Found in Ground Water on the Quincy and Pasco Basins.” USGS, July 1996. https://pubs.usgs.gov/fs/1995/0240/report.pdf and (ATSDR Toxicological Profiles). Prepared for Earthjustice by Material Research L3C 18 November 2019

31 National Pesticide Information Retrieval System. “D-D, Active Ingredient Information.” NPIRS Public, n.d. http://npirspublic.ceris.purdue.edu/ppis/chemical.aspx. 32 European Chemicals Agency. “Reaction Mass of 1,2-Dichloropropane and 1,3-Dichloropropene.” Registration Dossier - ECHA, n.d. https://echa.europa.eu/registration-dossier/-/registered-dossier/13157. 33 Asociación Regional Centroamericana para el Agua y el Ambiente. “Condiciones de Producción, Impactos Humanos y Ambientales En El Sector Piña En Costa Rica.” Oxfam Deutschland, April 2016. https://www.oxfam.de/system/files/condiciones_laborales_y_ambientales_de_la_pina_en_costa_rica_- _mayo_2016.pdf. 34 PCC Group. “Dichloropropane and Its Properties. Where Can It Be Used?” PCC Group Products Portal, July 2018. https://www.products.pcc.eu/en/blog/dichloropropane-and-its-properties-where-can-it-be- used/. 35 OEHHA; and, Dow AgroSciences LLC. “1,3-Dichloropropane, a Profile.” Dow Materials Safety Data Sheets, February 1996. http://msdssearch.dow.com/PublishedLiteratureDAS/dh_0932/0901b80380932f25.pdf?filepath=usag/pdfs /noreg/010-32489.pdf&fromPage=GetDoc. 36 IPCS International Programme on Chemical Safety. “1,3-Dichloropropene, 1,2-Dichloropropane, and Mixtures: Health and Safety Guide.” World Health Organization, 1992. http://apps.who.int/iris/bitstream/10665/40039/1/9241510765_eng.pdf. 37 ICL Industrial Products. “Phosflex 314 Materials Safety Data Sheet.” ICL IP, n.d. http://icl-ip.com/wp- content/uploads/2012/03/7055_usPhosflex314.pdf. 38 ICL Industrial Products. “Phosflex 314.” Accessed September 25, 2019. https://web.archive.org/web/20190310175404/http://icl-ip.com:80/products/phosflex-314/. 39 Surquímica S.A. “Hoja de Datos de Seguridad Del Material, Polysur Fondo Acabado Satinado.” Grupo Sur, n.d. http://www.gruposur.com/download/hojas_de_seguridad/msds-508-11007-900.pdf. 40 Grupo Sur. “Pinturas Sur de Puerto Rico Corp.” Grupo Sur, n.d. https://www.gruposur.com/web/location/pinturas-sur-de-puerto-rico-corp-2/. 41 Shell Chemical Company, and Occidental Chemical Corporation. “Vinyl Chloride Monomer. Confidential Supply Agreement. Dated December 14, 1984. Control No. 18036-85.,” December 14, 1984. https://www.toxicdocs.org/d/5oQmMv9oaKZKwgDRpqjevnEJ. 42 Shell 1977. 43 Shaikh, Muhammad Mansoor, Awadh AlSuhaimi, and Marlia Mohd Hanfiah. “Release of Organic Contaminants Migrating from Polyvinyl Chloride Polymeric into Drinking Water under Three Successive Stagnant Periods of Time.” Desalination and Water Treatment 149 (May 2019): 105–16. https://doi.org/10.5004/dwt.2019.23840. 44 California Office of Environmental Health Hazard Assessment. “Chemicals.” OEHHA, n.d. https://oehha.ca.gov/chemicals. 45 U.S. National Library of Medicine. “1,2-Dichloropropane.” PubChem, n.d. https://pubchem.ncbi.nlm.nih.gov/compound/1%2C2-DICHLOROPROPANE. 46 “Occupational Diseases: A Guide to Their Recognition. Revised Edition.” National Institute for Occupational Safety and Health, June 1977. International Agency for Research on Cancer. “IARC Monographs.” 1,2-dichloropropane, n.d. https://monographs.iarc.fr/wp- content/uploads/2018/06/mono110-03.pdf and Environmental Protection Agency. “Envirofacts Report ICL-IP AMERICA INC.” TRI Search, n.d. https://enviro.epa.gov/enviro/tris_control_v2.tris_print?pPrev=1&tris_id=25515KZCHMSTATE. 47 Anderson, Bob. “Waste Firm Loses Ruling.” Baton Rouge Advocate, July 21, 2008. https://leanweb.org/uncategorized/waste-firm-loses-ruling-2/. 48 Brungardt, Clement, Richard Riehle, and Jian Jian Zhang. Alkaline paper surface sizing agents. USPTO US6048392A, filed December 23, 1997, and issued April 11, 2000. 49 Environmental Protection Agency. “Envirofacts Report Solenis LLC.” TRI Search, n.d. https://enviro.epa.gov/enviro/tris_control_v2.tris_print?pPrev=1&tris_id=23851HRCLSROUTE. Prepared for Earthjustice by Material Research L3C 19 November 2019

50 Ibid. 51 Environmental Protection Agency. “Statement of Basis, Former Hercules Facility Courtland, VA.” EPA, September 2016. https://www.epa.gov/sites/production/files/2016-09/documents/ashlandherclues_sb.pdf. 52 Dow. “Locations - Grand Bayou Operations.” Dow, 2019. https://corporate.dow.com/en- us/about/locations/louisiana/locations/grand-bayou. 53 Environmental Protection Agency. “Envirofacts Report ICL-IP AMERICA INC.” TRI Search, n.d. https://enviro.epa.gov/enviro/tris_control_v2.tris_print?pPrev=1&tris_id=25515KZCHMSTATE. 54 Stefan Baumgarten. “Hexion Confirms June Closure of US ECH Plant.” ICIS Explore, May 13, 2016. https://www.icis.com/explore/resources/news/2016/05/13/9998176/hexion-confirms-june-closure-of-us- ech-plant/. And Larino, Jennifer. “Hexion to Close Norco Plant, Lay off 97 Workers.” The Times-Picayune, May 12, 2016. https://www.nola.com/news/business/article_623ba1da-d187-5453-996c- cbc00fb8434a.html. 55 National Research Council (US) Committee on Pesticides in the Diets of Infants and Children. “Pesticides in the Diets of Infants and Children.” NCBI Bookshelf, 1993. https://www.ncbi.nlm.nih.gov/books/NBK236264/. 56 Bruce Henderson. “Many Wells Contaminated by Pesticide.” Panna, September 2008. http://www.panna.org/sites/default/files/imported/files/CharlotteObserverWellsContaminated20080922.pdf 57 International Programme on Chemical Safety. “1,3-Dichloropropene, 1,2-Dichloropropane and Mixtures, Health and Safety Guide.” WHO, 1992. https://apps.who.int/iris/bitstream/handle/10665/40039/9241510765_eng.pdf?sequence=1. 58 Agency for Toxics Substances and Disease Registry. “Public Health Statement for 1,2- Dichloropropane.” ATSDR Public Health Statement, n.d. https://www.atsdr.cdc.gov/phs/phs.asp?id=829&tid=162#bookmark02. 59 Poppendieck, D., M. Schlegel, A. Connor, and A. Blickley. “Flame Retardant Emissions from Spray Polyurethane Foam Insulation.” ASTM Standard Selected Technical Papers. National Institute of Standards and Technology, 2017. https://www.astm.org/DIGITAL_LIBRARY/STP/PAGES/STP158920150044.htm. Also: Karlovich, Brian, Carl Thompson, and Jim Lambach. “A Proposed Methodology for Development of Building Re- Occupancy Guidelines Following Installation of Spray Polyurethane Foam Insulation.” Bayer MaterialScience, February 2011; and Poppendieck, Dustin G., Mengyan Gong, and Lauren E. Lawson. “Lessons Learned from Spray Polyurethane Foam Emission Testing Using Micro-Chambers.” In The 59th Annual Polyurethanes Technical Conference. Baltimore, MD, 2016. http://ws680.nist.gov/publication/get_pdf.cfm?pub_id=921259. 60 Five countries limit occupational exposures to 1,2-dichloropropane to less than 50ug/m3 over 8 hours: Belgium, Hungary, Ireland, Poland and Spain. https://monographs.iarc.fr/wp- content/uploads/2018/06/mono110-03.pdf

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