FINAL (October 14, 2014)



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# Significant New Alternatives Policy Program

Refrigeration and Air Conditioning Sector

Risk Screen on Substitutes in Heat Transfer

Substitute: trans -1-Chloro-3,3,3-trifluoroprop-1-ene

This risk screen does not contain Clean Air Act (CAA) Confidential Business Information (CBI) and, therefore, may be disclosed to the public.



### 1. INTRODUCTION

Ozone-depleting substances (ODS) are being phased out of production in response to a series of diplomatic and legislative efforts that have taken place over the past two decades, including the Montreal Protocol and the Clean Air Act Amendments of 1990 (CAAA). The U.S. Environmental Protection Agency (EPA), as authorized by Section 612 of the CAAA, admini sters the Significant New Alternatives Policy (SNAP) Program, which identifies acceptable and unacceptable s ubstitutes for ODS in specific end-uses based on assessment of their health and environmental impacts.

EPA’s decision on the acceptability of a substitute is based on the findings of a screening assessment of potential human health and environmental risks posed by the substitute in specific applications. EPA has already screened a large number of substitutes in many end-uses within all of the major ODS-using sectors, including refrigeration and air conditioning, solvent cl eaning, foam blowing, aerosols, fire suppression, adhesives, coatings and inks, and sterilization. The r esults of these risk screens are presented in a series of Background Documents that are available in EPA's docket.

The purpose of this risk screen is to supplement EPA’s Background Document on the refrigeration and air conditioning sector (EPA 1994) (hereinafter referred to as the Background Document). This risk screen evaluates the potential use of trans -1-chloro-3,3,3-trifluoropro-1-ene (hereinafter referred to as SolsticeTM 1233zd(E)) as a substitute in the heat transfer end-use. As indicated by the submitter, SolsticeTM 1233zd(E) is intended for use in organic rankine cycle (ORC) and sensible (i.e., non-mechanical) heat transfer end-uses. SolsticeTM 1233zd(E) has previously been listed by EP A’s SNAP as acceptable for use in centrifugal chillers. Table 1 presents information on the proposed substitute.

Table 1. Composition of SolsticeTM 1233zd(E)

Constituent Chemical Formula CAS Number Percent of Total (by weight)

trans -1-Chloro-3,3,3-trif luoroprop-1-ene C 3 H 2

ClF 3 102687-65-0 >99%

Potential Impurities (maximum concentration)FINAL (October 14, 2014)



### 2 The potential risks associated with use of substitutes in heat transfer have been examined at length in the Background Document. The reader is referred to this reference for a detailed discussion of the methodologies

used to conduct this risk screen. This risk screen addresses flammabilit y risk and assesses the impact of potential releases of SolsticeTM 1233zd(E) on the atmos phere and climate. Additionally, occupational exposure modeling was performed to ensure that manuf acture and application of the proposed substitute in the proposed heat transfer end- uses do not pose unacceptable risk to workers. Lastly, general population exposure was assessed to ensure that the proposed s ubstitute would not pose an unacceptable risk to the population at large.

Section 2 of this report summarizes the results of the risk screen for the proposed substitute. The remainder of the report is organized into the following sections:

 Section 3: Atmospheric Assessment

 Section 4: Volatile Orga nic Compound Assessment

 Section 5: Discussion of End-Use Scenarios

 Section 6: Potential Health Effects

 Section 7: Flammability Assessment

 Section 8: Occupationa l Exposure Assessment

 Section 9: General Population Assessment

 Section 10: References



### 2. SUMMARY OF RESULTS

SolsticeTM 1233zd(E) is recommended for SNAP appr oval as a heat transfer fluid for ORC and nonmechanical heat transfer uses. EPA’s risk screen indicates that the use of the proposed substitute will be less harmful to the atmosphere than the continued u se of CFC-113, HCFC-123, and other commonly used refrigerant, as it is less harmful to the ozone layer, has lower climate impact, and a shorter atmospheric lifetime. In addition, SolsticeTM 1233zd(E) contributi ons to volatile organic compound (VOC) emissions are not a concern as SolsticeTM 1233zd(E) is exempt unde r CAA regulations (40 CFR § 51.100(s)). Given that appropriate personal protective equipm ent (PPE) and engineering controls (e.g., exhaust ventilation, vaporin-air detection systems) will be used during installa tion, maintenance, and disposal activities, no significant toxicity risks to workers or the general population are expected. In addition, based on the characteristics ofFINAL (October 14, 2014)



### 3 the proposed substitute and the proper precautions listed in the MSDS for SolsticeTM 1233zd(E), the proposed substitute is not expected to present a signi ficant flammability concern during manufacture or enduse (see Section 7).



### 3. ATMOSPHERIC ASSESSMENT

This section presents an assessment of the potential ri sks to atmospheric integrity posed by the use of SolsticeTM 1233zd(E) as a heat transfer fluid. The ozon e depletion potential (ODP), global warming potential (GWP), and atmospheric lifetime (ALT) of the pr oposed substitute are presented in Table 2.

The proposed substitute is substantially less harmful to the ozone layer, has lower climate impact, and a shorter atmospheric lifetime when compared to refrigera nts currently used in heat transfer, such as CFC-113, HCFC-22, HCFC 141b, and HCFC-123. In addition, Sols ticeTM 1233zd(E) also has lower climate impact and a shorter atmospheric lifetime than those predicte d for other substitutes examined in the Background Document, as well as commonly utilized substitutes HFC-245fa, HFC-236fa, and HFC-134a. SolsticeTM 1233zd(E) has a non-zero ODP, but at 0.00024, this value is very small when considering continued use of CFC-113, HCFC-22, HCFC-141b, and HCFC-123. A recen t report by Wang et al. (2011) modeled the potential of SolsticeTM 1233zd(E) to affect the amount of ozone in the global atmosphere (tropospheric and stratospheric). This report found that the release of all SolsticeTM 1233zd(E), assu ming it were substituted for all compounds it might replace and that the entire amount used would be released, there would be a statistical impact of zero on global atmospheric ozone (l ess than 0.01% change in total column ozone). Thus, EPA believes that use of SolsticeTM 1233zd(E) would r esult in substantially less harm to the climate and ozone layer than the continued use of OD S and other commonly used refrigerants.

Table 2. Atmospheric Impacts of SolsticeTM 1233zd(E) Compared to Other Heat Transfer Refrigerants

Chemical ODP c GWP (100-year) d ALT d SolsticeTM 1233zd(E) 0.00024 a 4.6 b 30.5 days b

CFC-113 0.85 c 6,130 85 years

HCFC-123 0.01 c 77 1.3 years

HCFC-22 0.05 c 1,810 12 years

HCFC-141b 0.12 c 725 9.3 years HFC-245fa 0 1,030 7.6 years HFC-236fa 0 9,810 240 years HFC-134a 0 1,430 14 years

a Assuming SolsticeTM 1233zd(E) emissions occur with the same geographic distribution as the blowing agents it might replace (Wang et al. 2011).

b Wuebbles et al. (2013)

c WMO (2011)

d IPCC 4 th Assessment Report (Forster et al. 2007).



### 4. VOLATILE ORGANI C COMPOUND ASSESSMENT

SolsticeTM 1233zd(E) is exempt from the definiti on of volatile organic compound (VOC) under CAA regulations (40 CFR 51.100(s)). Therefore, environm ental impacts from the release of SolsticeTM 1233zd(E)

as a VOC are not a concern.



### 5. DISCUSSION OF END-USE SCENARIOS

SolsticeTM 1233zd(E) has been proposed for the non-mech anical heat transfer end-use, including ORC and sensible (non-mechanical) heat transfer applications. As indicated by the submitter, the applications for ORC include geothermal and waste heat recovery systems generating from less than 1 megawatt (MW) to approximately 5 MW of power. Such systems can be installed in both small power plants and supplementalFINAL (October 14, 2014)



### 4 systems in larger steel, cement, or refining industrial plants. In addition, end-users may also develop custom systems in which several smaller systems are coupled together to generate a higher output (i.e., serially connect eight-125 kW systems to generate a 1 MW out put system). Although geothermal applications utilize the largest charge size of this proposed substitute (i.e ., up to 75 metric tons [MT]), these applications are typically located outdoors in a remote area. (Anonymous Submitter 2013b)

Non-mechanical heat transfer applications include solar water heating, immersion cooling/heating, recirculating coolers, and thermosiphons. These applica tions, which are typically located indoors and used commercially, operate using a smaller charge size than ORC applications (i.e., less than 10 kg). Despite the differences in size and application between ORC and non-mechanical heat transfer systems, these applications are anticipated to have similar release patterns. Specifically, charging and recovery of the proposed substitute from both system types occur us ing a refrigerant recovery unit or vacuum pump following similar procedures. Furthermore, the submitte r estimates that the annual leak rate from ORC systems using HFC-245fa can reach up to approximately 2 percent; however such leak rates are expected to be much smaller for systems using SolsticeTM 1233zd(E) because of its lower operating pressure and also for larger ORC systems, which are expected to have annu al leak rates similar to chillers (i.e., 0.5 percent) (Anonymous Submitter 2011). Because non-mechanical heat tr ansfer systems typically operate at relatively lower pressures (e.g., vacuum, atmospheric) than ORC, annual leak rates from these systems are expected to be even smaller. Therefore, any potential exposure to the proposed substitute is expected to occur in the same manner and at low amounts for both types of heat transfer applications.



### 6. POTENTIAL HEALTH EFFECTS

To assess potential health risks from exposure to this proposed substitute, the submitter provided a workplace environmental exposure limit (WEEL) of 8 00 ppm for SolsticeTM 1233zd(E) (OARS 2013). The WEEL represents the maximum 8-hour time weighted average (TWA) at which a worker can be exposed regularly without adverse effects.

According to the MSDS, exposure to SolsticeTM 1233zd(E) through ocular or dermal absorption, inhalation, or ingestion may be harmful. Ocular exposures to So lsticeTM 1233zd(E) will cause serious eye irritation and may cause frostbite through dermal exposure. In case of ocular exposure, the MSDS for SolsticeTM 1233zd(E) recommends that person(s) should immediately flush the eyes, including under the eyelids, with water for 15 minutes; should frostbite occur, affected areas should be rinsed with lukewarm water. Medical attention should be sought if i rritation develops or persists.

In the case of dermal exposure to SolsticeTM 1233zd( E), the MSDS for SolsticeTM 1233zd(E) recommends that person(s) should immediately wash the affected area with water and remove all contaminated clothing to avoid irritation; should frostbite occur, bathe (do not r ub) the affected area with lukewarm, not hot, water. If water is not available, cover the affected area with a cl ean, soft cloth. Medical attention should be sought if irritation develops or persists. So lsticeTM 1233zd(E) vapors are heavier than air and cause suffocation by reducing oxygen available for breathing, causing asphyxi ation in high concentrations. If person(s) are exposed to high concentrations, the person(s) will likel y not realize that he/she is suffocating, but may experience central nervous system effects, such as drowsiness and dizziness. If SolsticeTM 1233zd(E) is inhaled, person(s) should be immedi ately removed and exposed to fresh air. The MSDS recommends that if breathing is difficult, person(s) should be given oxygen, provided a qualified operator is present, and medical attention be sought.

SolsticeTM 1233zd(E) is not likely to be hazardous by i ngestion; however, in case of ingestion, the MSDS recommends the person(s) drink a cup of water, if fully conscious, and consult a physician immediately. DoFINAL (October 14, 2014)


### 5 not induce vomiting without medical advice. EPA’s revi ew of the human health impacts of this proposed substitute is contained in the pub lic docket for this decision.

The potential health effects of SolsticeTM 1233zd(E) are unlikely to occur when following good industrial hygiene practices and the PPE and engineering control (e.g., ventilation) recommendations outlined in the MSDS for SolsticeTM 1233zd(E) and Secti ons 7 and 8 of this risk screen.



### 7. FLAMMABILITY ASSESSMENT

SolsticeTM 1233zd(E) is not considered to be flammable at ambient temperatures and atmospheric pressure, but can ignite when mixed with air under pressure and e xposed to strong ignition sources; also, containers of SolsticeTM 1233zd(E) may rupture when exposed to he at or temperatures above the proposed substitute’s auto-ignition temperature of 380°C (Anonymous Submitter 2011). By keeping Solstice TM 1233zd(E) away from all sources of ignition and high heat and adheri ng to the other precautions listed in the proposed substitute’s MSDS, Solstice TM 1233zd(E) does not pose a significant flammability risk.



### 8. OCCUPATIONAL EXPOSURE ASSESSMENT

This section assesses potential exposures to workers during manufacture, installation, servicing and disposal of SolsticeTM 1233zd(E) in heat transfer systems, including ORC and non-mechanical heat transfer applications. As indicated by the submitter, the ma nufacture of the proposed substitute for use in heat transfer is similar to manufacture at refrigerant f acilities and is conducted in a closed system (Anonymous Submitter 2012); as a result, exposure during manufactu ring operations is not anticipated. However, exposure to the proposed substitute can occur dur ing charging and de-commissioning activities during installation, servicing, and disposal.

The potential occupational exposure to SolsticeTM 1233zd(E) during installa tion, servicing, and disposal of heat transfer systems was analyzed. Potential exposures to the proposed substitute are anticipated to occur during charging and de-commissioning activities of the heat transfer system. The submitter provided exposure monitoring data for the heat transfer end- use, specifically ORC. Monitoring was conducted in two scenarios, i.e., charging and de-commissioning of the heat transfer system, to determine the concentration of SolsticeTM 1233zd(E) during installation, service, and di sposal operations. The total quantity of refrigerant used in this monitoring data was 9.1 – 11.3 kg (20 – 25 lbs.). 1 The first scenario, which modeled the charging of the proposed substitute into a previously evacuated system, demonstrated a peak concentration of 86 ppm. The second scenario, which modeled the de-c ommissioning of the system, demonstrated a peak concentration of 114 ppm. (Anonym ous Submitter 2013a) These maximum measured vapor-in-air values, as shown in Table 3, are well below the pr oposed substitute’s WEEL of 800 ppm.

Table 3. Exposure Monitoring Da ta for the Heat Transfer Applic ation of SolsticeTM 1233zd(E) a

Scenario Peak Concentration (ppm) Average Concentration (ppm) b WEEL (ppm)
Charging 86 1.4 800 De-commissioning 114 0.61

a The concentrations were measured by a room sniffer that was located nearby where a technician would be servicing the equipment

. b Concentrations were recorded in one second intervals for a 24-hour period.

To further minimize potential exposures when systems ar e located indoors, engineering controls should be in place during installation and servicing of SolsticeTM 1233zd( E) heat transfer systems, such as vapor-in-air detection systems. Adequate ventilati on should always be established during any use, handling, or storage of

Anonymous SubmitterFINAL (October 14, 2014)



### 6 SolsticeTM 1233zd(E). In addition, an eye wash and safe ty shower should be near the manufacturing facility and ready for use. In general, use of PPE is r ecommended, such as respiratory protection (a NIOSHapproved positive-pressure supplied-air respirator is recommended where there is insufficient ventilation; self-contained breathing apparatus should be used fo r rescue and maintenance work in storage tanks), chemical splash goggles or face shield, impervious gloves, and chemical-resistant boots and clothing (Anonymous Submitter 2011, OSHA 1994). Contaminated clothing is not to leave the workplace and must be cleaned before reuse (Anonymous Submitter 2011).

During handling of liquid SolsticeTM 1233zd(E), there is also a risk of generation of toxic decomposition products such as hydrochloric acid, hydrofluoric acid, and carbonyl halides if liquid SolsticeTM 1233zd(E) is exposed to fires or temperatures greater than 250°C. Containers of SolsticeTM 1233zd(E) should not be allowed to contact open flames, glowing metal surfaces, or electrical heating elements.

EPA believes that if proper handling guidelines are fo llowed in accordance with good industrial hygiene and manufacturing practices and the MSDS for SolsticeTM 1233zd(E), as described above, manufacture, installation, and disposal of SolsticeTM 1233zd(E) wh en used as a heat transfer fluid does not present a significant risk to workers. In addition, all technicians should possess EPA section 608 technician certification and be properly trained in working with h eat transfer systems and related refrigerant recovery equipment.



### 9. GENERAL POPULATION EXPOSURE ASSESSMENT

SolsticeTM 1233zd(E) is not expected to cause a signifi cant impact on human health in the general population

when manufactured or used as a heat transfer fluid. The proposed substitute will be manufactured in a closed process and any transfer of fluids during installation, servicing, or disposal is also conducted in a closed process. Should air releases during manufacturing operati ons occur, engineering controls should be used (e.g., carbon absorption scrubbers) to collect and preven t the release of the proposed substitute to the atmosphere. In addition, all service technicians shoul d be properly trained in working with SolsticeTM 1233zd(E) in heat transfer systems and related r ecovery equipment and possess EPA section 608 technician certification. In heat transfer applications, SolsticeTM 1233zd(E) is proposed for use in closed systems that are operated near atmospheric pressure (and would therefor e release slowly into the outside air) and at room temperature, SolsticeTM 1233zd(E) is a gas. Theref ore, releases to ground or surface water are not anticipated, as SolsticeTM 1233zd(E) is anticipated to dissipate into the atmosphere upon release to outside air (i.e., because natural ventilation rates would be high er and there is no enclosed space to keep SolsticeTM 1233zd(E) concentrated).

Due to the low toxicity of SolsticeTM 1233zd(E) and minimal expected release, EPA believes that such exposures do not pose a significant toxicity risk, and thus, SolsticeTM 1233zd(E) is not expected to cause a significant impact on human health in the general popula tion when used as a heat transfer fluid in ORC and

non-mechanical heat transfer.FINAL (October 14, 2014)



### 7 10. REFERENCES

Anonymous Submitter 2011. SNAP Submission to EPA for SolsticeTM 1233zd(E). May 13, 2011.

Anonymous Submitter 2012. Conference Call with Submitter on June 6, 2012 on SolsticeTM 1233zd(E) in the Heat Transfer End-Use. June 6, 2012.

Anonymous Submitter 2013a. Exposure Monitoring Data for the Heat Transfer (ORC) Application of SolsticeTM1233zd(E). June 27, 2013.

Anonymous Submitter 2013b. Response to 1233zd – Refrigeration Sector Letter sent on July 31, 2013. September 17, 2013.

Forster, P., V. Ramaswamy, P. Artaxo, T. Berntsen , R. Betts, D.W. Fahey, J. Haywood, J. Lean, D.C. Lowe, G. Myhre, J. Nganga, R. Prinn, G. Raga, M. Schulz and R. Van Dorland. 2007. Changes in Atmospheric Constituents and in Radiative Forcing. In: Climate Change 2007: The Physical Science Basis. Contribution of Working Group I to the Fourth Assessment Report of the Intergovernmental Panel on Climate Change [Solomon, S., D. Qin, M. Manning, Z. Chen, M. Marquis, K.B. Averyt, M.Tignor and H.L. Miller (eds.)]. Cambridge University Press, Cambridge, United Kingdom and New York, NY, USA.

ICF International. 2012. Determination of an Acceptable Exposure Limit (AEL) for SolsticeTM 1233zd(E). Prepared for U.S. Environmental Protection Agency. January 23, 2012.

Occupational Alliance for Risk Science (OARS) . 2013. Workplace Environmental Exposure Level (WEEL): trans-1-Chloro-3,3,3-Trifluoropropene (1233 zd(E)). Conducted for Ho neywell International,

2013.

OSHA. 1994. General description and discussion of the levels of protection and protective gear. 1910.120 App B. Last updated August 22, 1994. Available at: http://www.osha.gov/pls/oshaweb/owadisp. show_document?p_table =STANDARDS&p_id=9767

U.S. EPA. 1994. Significant New Alternatives Polic y Technical Background Document: Risk Screen on the Use of Substitutes for Class I Ozone-depleting S ubstances: Refrigeration and Air Conditioning. U.S. Environmental Protection Agency, March 1994.

Wang D., Olsen S., Wuebbles D. 2011. “Preliminary Report: Analyses of tCFP’s Potential Impact on Atmospheric Ozone.” Department of Atmospheric Scien ces. University of Illinois, Urbana, IL. September 26, 2011.

WMO (World Meteorological Organization). 2011. Sc ientific Assessment of Ozone Depletion: 2010, Global Ozone Research and Monitoring Project—Rep ort No. 52, 516 pp., Geneva, Switzerland, 2011.

Wuebbles, D.J., Wang, D., Patten, K.O., et al. 2013. Analyses of new short-lived replacements for HFCs with large GWPs. Geophysical Research Letters. Vol. 40, Issue 17. pp. 4767-4771. September 16, 2013.