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MANDATE The Ad hoc Working Group on Further Commitments from Annex I Parties under the Kyoto Protocol (AWG-KP), at its sixth session, requested the secretariat to prepare a compilation of technical information on the following gases included in the Fourth Assessment Report (AR4) of the Intergovernmental Panel on Climate Change (IPCC):
as well as on existing stocks and potential emissions of chlorofluorocarbon (CFCs) and
hydrochloro-fluorocarbons (HCFCs), and to make it available on the UNFCCC website for consideration by the
AWG-KP at its resumed sixth session. The list of gases included in the AWG-KP report from its sixth session covers substances referred in table 2.14 (addendum1) of the IPCC AR4 - including the new HFCs and PFCs - that were not listed in the Second Assessment Report (SAR) of the IPCC, and that are not included in the reporting and accounting obligations under the current commitments of the Kyoto Protocol. According to the IPCC (section 2.10.2 of volume 3 of the AR4) table 2.14 covers all gases for which either significant concentrations or large trends in concentrations have been observed, or a clear potential for future emissions have been identified. 1 The addendum of the IPCC AR4 was released on 5 August 2008 and it is available at http://www.ipcc.ch/publications_and_data/ar4/wg1/en/errataserrata-errata.html APPROACH The secretariat invited Parties and experts to provide relevant information on the new gases mentioned above, which they could share with other Parties and the secretariat. The secretariat also contacted experts from the Montreal Protocol secretariat, the Technology and Economic Assessment Panel (TEAP) of the Montreal Protocol, and the Intergovernmental Panel on Climate Change (IPCC). The secretariat also reviewed other relevant information. SOURCES OF INFORMATION Information collected by Parties and experts is mostly found on the internet. Important sources of information are:
All values of Global Warming Potential (GWP), radiative efficiency and lifetime for gases included in this compilation are from table 2.14 of the AR4. Information on methodologies to estimate GHG emissions is found in the Revised 1996 IPCC Guidelines for national greenhouse gas inventories (hereinafter referred to as the Revised 1996 IPCC Guidelines ), and associated Good practice guidance and uncertainty management in national greenhouse gas inventories (hereinafter referred to as the good practice guidance). Another source of information is the 2006 IPCC Guidelines for national greenhouse gas inventories (hereinafter referred to as the 2006 IPCC Guidelines ) that was prepared upon invitation of the UNFCCC. The 2006 IPCC Guidelines comprise the most recent scientific information on methods to assess emissions by source and removals by sinks. Parties to the UNFCCC are using the 2006 IPCC Guidelines on a voluntary basis. When considering information on methodologies due consideration is to be given to dependency of the occurrence of emissions to the atmosphere on the conditions under which the chemical substance is manufactured, transported, used and disposed. Also relevant are the conditions under which equipments containing the substance are operated, serviced and decommissioned. In some situations, such as high temperatures, compounds may be emitted even if they have low volatility and are inert substances at normal temperatures and pressures. OVERVIEW OF THE INFORMATION AVAILABLE The compilation by the secretariat includes information on a gas-by-gas basis, on GWP, application (where the gas is actually or potentially used), production, substitutes and alternative technologies, and the existence of methodologies to estimate greenhouse gas (GHG) emissions. Links to web sites on which more information on these gases can be found are also included.
Also included is a summary on available information on existing stocks (banks) and potential emissions of
CFCs and HCFCs. UPDATES This compilation reflects the information available to the secretariat as at 27 July 2010, updated after request from some Parties. This most recent update comprises, in addition to the information previously compiled by the secretariat, further information on HFCs, NF3 and HFEs.
List of substances: The AR4 includes a number of HFC compounds proposed for inclusion in the accounting of GHGs in addition to the HFCs that were already covered by previous IPCC reports2 and the IPCC good practice guidance.
Main applications: possible ozone depleting substitutes (ODS) foam blowing agents. Generally, substances listed as HFCs and PFCs are primarily used to replace ODS controlled under the Montreal Protocol, and their use has became more prevalent in developed countries. Also generally, HFCs include substances that can be used for refrigeration and air conditioning, foam blowing, aerosols and fire extinguishing. HFC-245fa and HFC-365mfc were originally used in developed countries as a substitute for the HCFC-141b in foam blowing applications, and following the phase-out of this substance. Their use is decreasing however, since other options are available for foam blowing which do not include HFCs or that use co-blowing with HFCs and water. In developing countries, the replacement of HCFC-141b, will be to some degree done by HFC-245fa, but also in these countries activities are underway to develop and apply low-GWP alternatives such as methyl formate and other blowing agents. The other gases on the list, HFC-152, HFC-161 and the isomers HFC-236cb and HFC-236ea have not seen significant application. These substances are not in commercial use yet and there are no indications for any significant production on a commercial scale in the future. Given the current trend to replace HCFCs and HFCs with hydrocarbons, mixes of hydrocarbons, HFCs of lower GWP value or recent unsaturated HFCs such as HFC-1234ze, it is very likely that the use of HCFC-161 and HFC-152 will never be globally significant.
Emissions reduction options Several non-fluorocarbon blowing agents technologies (applying other products such as hydrocarbons, carbon dioxide, water and supercritical carbon dioxide gas) and new lower GWP blowing agent gases have already been developed and are being used. The TEAP has published an assessment of alternatives to HCFCs and HFCs and updated the data in the 2009 and 2010 TEAP reports. The TEAP reports contain a detailed analysis of the current status of use of fluorinated gases for each sector (refrigeration and air conditioning in domestic, commercial and industrial uses, transportation, foam blowing, fire protection, solvents and inhaled therapy). The TEAP reports show potential opportunities to replace HFCs with substances that have low global warming effect, as follows:
Production The main producers of HFC-245fa are in the United States of America and Japan, while those of HFC-365mfc are in Europe. Global annual production of these gases is estimated around 20,000 tonnes per year each. Methodologies to estimate emissions Methodologies to estimate “emissions of fluorinated substitutes for ODS”, available in the 2006 IPCC Guidelines, or “emissions of substitutes for ODS” from the good practice guidance, are usually not specific of individual gases, and may be used to estimate emissions for the extended list of HFCs. Specific emission factors to estimate emissions of some new HFCs (HFC-245fa and HFC-365mfc) from the production and use of foams are available in the 2006 IPCC Guidelines. References EU. 2006. Directive 2006/40/EC of the European Parliament and of the Council of 17 May 2006 relating to emissions from air-conditioning systems in motor vehicles and amending Council Directive 70/156/EEC. Available at http://eur-lex.europa.eu/LexUriServ/LexUriServ.do?uri=OJ:L:2006:161:0012:0018:EN:PDF
UNEP/TEAP. 2009. Assessment of Alternatives to HCFCs and HFCs and Update of the TEAP 2005 Supplement Report
Data. Task Force Decision XX/8 Report. UNEP Technology and Economical Assessment Panel. Available at
UNEP/TEAP. 2010. Assessment of HCFCs and environmentally sound alternatives;
Scoping study on alternatives to HCFC refrigerants under high ambient temperature conditions. Task Force
Decision XXI/9 Report. UNEP Technology and Economical Assessment Panel. Available at
2For the Kyoto Protocol in its first commitment period the GWP used to calculate the
CO2 eq of anthropogenic emissions by sources and removals by sinks of greenhouse gases listed in
Annex A shall be those accepted by the IPCC and agreed upon by the Conference of the Parties at its third
session. Any revision to a global warming potential shall apply only to commitments under Article 3 in
respect of any commitment period adopted subsequent to that revision. (paragraph 3 of Article 5 of Decision
1/CP.3). Paragraph 3 of Decision 2/CP.3 reaffirms that GWP used by Parties should be those provided by the
IPCC in its Second Assessment Report (1995 IPCC GWP values). .
List of substances: PFC-9-1-18 is also referred to as Perfluorodecalin
Main applications: medical applications Perfluorodecalin is used in several cosmetic and medical applications as a first-generation PFC-based blood substitutes, exploiting its ability to carry oxygen to living tissues. It is also used in retinal surgery (to repair retinal tears), for treating lung disorders (pneumonectomy), wound healing, as an ultrasonic contrast agent in MRI and ultrasonic examinations, treatment of diseases of the middle ear, and in organ storage for transplants (e.g. pancreatic tissue). In all these uses, this PFC is vented to the atmosphere, although current global production is small (of order 10 tonnes per year). All but pancreatic storage and eye surgery involve only small quantities and are at the research stage. Recently, perfluorodecalin has been proposed as a carrier of glassified microspheres that contain vaccines, reducing the need for refrigeration. This potential use would increase emissions substantially, to the same order of magnitude of current day emissions of SF6. Emissions Perfluorodecalin is a heavy cyclic molecule, with high boiling point (142 C), and emissions or atmospheric abundance depend on the conditions under which this chemical is managed (e.g. high temperature conditions). The amount of this substance that is being used today combined with the low emissions occurring under most use circumstances indicate that emissions have small significance so far. Methodologies to estimate emissions Methodology guidance to estimate emissions of Perfluorodecalin is included in chapter “Use of SF6 and PFCs in other products” of the 2006 IPCC Guidelines (chapter 8.3, volume 3). References IPCC. 2006. 2006 IPCC Guidelines for National Greenhouse Gas Inventories. Prepared by the National Greenhouse Gas Inventories Programme, Eggleston H.S., Buendia L., Miwa K., Ngara T. and Tanabe K. (eds). Published: IGES, Japan. Available at http://www.ipcc-nggip.iges.or.jp/public/2006gl/index.html. Shine K.P et al. 2005. Perfluorodecalin: global warming potential and first detection in the atmosphere, Atmospheric Environment 39 (2005) 1759–1763. Other names Nitrogen fluoride, Trifluoramine and Trifluorammonia
Main applications: manufacture of semiconductors, LCD and photovoltaic cells Nitrogen trifluoride is used as a replacement for PFCs (mostly C2F6) and SF6 in the electronic industry (plasma etching and chamber cleaning), manufacture of semi-conductors and LCD panels (Liquid Crystal Display). NF3 is broken down into nitrogen and fluorine gases in situ, and the resulting fluorine radicals are the active cleaning agents that attack the poly-silicon. Nitrogen trifluoride is also used in the photovoltaic industry (thin-film solar cells) for "texturing, phosphorus silicate glass (PSG) removal, edge isolation and reactor cleaning after deposition of silicon nitrate or film silicon". Nitrogen trifluoride is further used in hydrogen fluoride and deuterium fluoride lasers, which are types of chemical lasers. Emissions One key reason for increasing interest in nitrogen trifluoride by the semiconductor industry is that it has a higher percentage of conversion to fluorine, which is the active agent in the industrial process, than PFCs and SF6 for the same amount of electronics production. Depending on the cleaning technology (i.e., remote or in-situ), the fraction released ranges usually from 2 to 5 per cent, but may reach up to 16 percent of the quantities of gas used. Recent atmospheric measurements imply that the average release rate may be closer to the upper end of this range. Emissions reduction options
Some emission reduction goals have already been established in the semiconductor and LCD industries.
Mitigation efforts in the semiconductor industry focus on process improvements/source reduction, alternative
chemicals, capture and beneficial reuse, and destruction technologies. Some companies are reducing emissions
by adopting alternatives to NF3. Linde, Toshiba Matsushita Display, Samsung and LG have installed
systems that generate fluorine (F2) on-site at some of their LCD and semiconductor facilities,
replacing the use of NF3 and SF6. The on-site systems could eliminate NF3 consumption.
However, the implementation of these systems requires upfront costs that smaller LCD manufacturers find it
difficult to support due to safety issues related to handling fluorine, a reactive and toxic material.
In Japan and Taiwan, hexafluorobutadiene (C4F6 or CF2=CF-CF=CF2)
has already been tested in industry as a possible replacement as etching agent. The use of remote plasma cleaning is an alternative technology that, by breaking NF3 in a remote container and injecting only the active ingredient, fluorine, together with nitrogen, in the vacuum chamber, can reduce the fraction of gas released from 16 per cent to 2 per cent. Production A 2005 report by the global semiconductor industry states that C2F6 (a PFC already included in the Kyoto basket of gases) continues to be the primary chamber cleaning gas and currently makes up the majority of semiconductor PFC emissions. However, NF3 is fast catching up with the use of C2F6 to both growth in total semiconductor manufacture (with estimated production increases of 15-17 per cent per annum) as well as displacement of older PFC technology for new production lines that use NF3. Since 1992, when less than 100 tonnes of nitrogen trifluoride were produced, production grew to an estimated 4,000 tonnes in 2007 and is projected to increase significantly, reaching 8,000 tonnes per year by 2010 and this is expected to grow further Nitrogen trifluoride is mostly produced in Japan, the Republic of Korea, Taiwan and the United States of America. Methodologies to estimate emissions Methodologies to estimate NF3 emissions in the electronics industry are available in the good practice guidance and the 2006 IPCC Guidelines. References
Paper no 1.B: Australia. Views on the coverage of greenhouse gases. Submission to the AWG-LCA and
AWG-KP. Available at Prachi Patel-Predd. 2008. Electronics Industry Changes the Climate with New Greenhouse Gas. Available at http://www.sciam.com/article.cfm?id=electronics-industry-contributes-new-greenhouse-gas Prather, M J, and J. Hsu. 2008. NF3, the Greenhouse Gas Missing From Kyoto. Geophys. Res. Lett., 35. L12810, doi:10.1029/2008GL034542, p. 1 Reichardt, H, Frenzel, A and K. Schober. 2001. Environmentally friendly wafer production: NF3 remote microwave plasma for chamber cleaning. Microelectronic Engineering 56. doi:10.1016/S0167-9317(00)00505-0. Robson, J I; Gohar, L K, Hurley, M D, Shine, K P and Wallington.2006. Revised IR spectrum, radiative efficiency and global warming potential of nitrogen trifluoride. Geophys. Res. Lett., 33, L10817, doi:10.1029/2006GL026210. Weiss, R F, Muhle, J, Salameh, P, and C. Harth. 2008. Nitrogen trifluoride in the global atmosphere. Geophys. Res. Lett., in press, October 1, 2008. http://www.airproducts.com/markets/electronics/newsletter/solutionsupdatevol1.htm 4. Trifluoromethyl sulphur pentafluoride (SF5CF3)
Main applications: unknown The concentration of trifluoromethyl sulphur pentafluoride in the atmosphere has been increasing, and some studies indicate that this is coupled with the increase of concentration of sulphur hexafluoride (SF6). There are assumptions that, because it is closely chemically related to SF6, it could originate as a breakdown product of (SF6) in high voltage equipment, via the spark discharge reactions of (SF6) with a few fluorocarbons. Methodologies to estimate emissions Emissions of Trifluoromethyl sulphur pentafluoride, when generated as by products from production of fluorinated compounds, could be estimated using high tier methodologies from the 2006 IPCC Guidelines. (chapter 3.10.2, volume 3) References IPCC. 2006. 2006 IPCC Guidelines for National Greenhouse Gas Inventories. Prepared by the National Greenhouse Gas Inventories Programme, Eggleston H.S., Buendia L., Miwa K., Ngara T. and Tanabe K. (eds). Published: IGES, Japan. Available at http://www.ipcc-nggip.iges.or.jp/public/2006gl/index.html Li Huang, Lili Zhu, Xunxi Pan, Jianliang Zhang, Bin Ouyang and Huiqi Hou. 2005. One potential source of the potent greenhouse gas SF5CF3: the reaction of SF6 with fluorocarbon under discharge. In Atmospheric Environment.Volume 39, Issue 9, March 2005, Pages 1641-1653. Available at http://www.sciencedirect.com Sturges, W T, Wallington, M D, Hurley, K P, Shine, K, Sihra, A, Engel, D E Oram, S A, Penkett, R, Mulvaney and C. A. M. Brenninkmeijer. 2000. Trifluoromethyl Sulfur Pentafluoride (SF5CF3) and Sulfur Hexafluoride (SF6) from Dome Concordia. In Trends: A Compendium of Data on Global Change. Carbon Dioxide Information Analysis Center, Oak Ridge National Laboratory, U.S. Department of Energy, Oak Ridge, Tenn., U.S.A. Available at http://cdiac.esd.ornl.gov/trends/otheratg/sturges/sturges.html Sturges, W T, Wallington, T J, Hurley, M D, Shine, K, Sihra K P, Engel, A, Oram, D E, Penkett, S A, Mulvaney, R. and M. Brenninkmeijer. A Potent Greenhouse Gas Identified in the Atmosphere: SF5CF3. Available at http://www.sciencemag.org/cgi/content/abstract/289/5479/611 Tucket, R. 2006. Trifluoromethyl sulphur pentafluoride(SF5CF3): Atmospheric Chemistry and its environmental importance via the Green-house effect in Fluorine and the Environment By Alain Tressaud. Available at http://books.google.co.uk/books?id=-xYG7Fchbl4C WMO. 2006. Scientific Assessment of Ozone Depletion: 2006 – Report no. 50. World Meteorological Organization. Global Ozone Research and Monitoring Project. Available at http://www.wmo.int/pages/prog/arep/gaw/ozone_2006/ozone_asst_report.html Other names Hydrofluorinated ethers, Hydrofluoro ethers.
Main applications: solvents and cleaning Potential applications: refrigerants, heat transfer fluids in refrigeration, foam blowing, plasma etching; industrial heat transfer fluids, fire suppressant and solvents. The main sector in which fluorinated ethers have been used is in the electronics, metal, and precision cleaning industry, replacing solvents such as CFC-113, methyl chloroform, HCFC-141b, n-propyl bromide and, and to a lesser extent, HFC-43-10mee. The pure HFEs are limited in utility in cleaning applications due to their mild solvent strength. However, HFEs are also used in azeotropic blends with other solvents (such as alcohols and trans 1,2 dichloroethylene) and in co-solvent cleaning processes, giving them broader cleaning efficacy. Currently, the HFEs most widely used in industry as cleaning solvents are HFE-7200 (HFE-569sf2), HFE-7100 (HFE-449s1), HFE-7500 (3-ethoxy-1,1,1,2,3,4,4,5,5,6,6,6-dodecafluoro-2,2,2-trifluoromethyl-hexane) and HFE-7000 (HFE-347mcc3). Currently the amount of the use of these HFEs is estimated around thousand tones per year. Also, HFE-236fa can have a potential role as a solvent. The 2009 TEAP report listed HFEs as possible alternatives for replacement of HCFC and HFC solvents in specialized niche applications, but it is expected that their use will be limited due to high cost. Another use of the fluorinated ethers is as a substitute for CFC-113 and HCFC-141b solvent in technical aerosols (group of pressurized products used to clean, maintain, fix, test, manufacture, disinfect, or apply lubricant and mould release agents to various types of equipment) in a number of industrial and commercial processes. Also for this application, the relatively higher costs of HFE in comparison to HCFC-141b may cause replacement difficult Fluorinated ethers such as HFE 125, HFE-134, HFE-143a, HFE-227me, HFE-245mf and HFE-245mc have been identified as potential refrigerants based on properties such as thermal stability, cycle performance, flammability, toxicity and tropospheric lifetime. However, the role of HFEs as replacement of refrigerants such as HFCs will depend on the accommodation of their higher price (generally ten times higher than HFCs), and the competition from other alternatives such asthe unsaturated HFCs(also named HFOs). HFE-43-10pccc124 ((H-Galden 1040x), HFE-236ca12 ((HG-10) and HFE-338pcc13 ((HG-01) are used as heat transfer fluids in refrigeration systems. An emerging application in which HFEs have the potential to replace HFCs is as a secondary refrigerant in refrigeration systems. Since the 1950-60s, α-fluorinated ethers were used as fast-acting inhalation anaesthetics and anti-inflammatory agents (e.g. HFE-235da2–isoflurane and HFE-236ea2–desflurane). Some fluorinated ethers have been identified, on the basis of thermal conductivity properties, as potential alternatives to HCFC-22 and HCFC-141b as foam blowing agents. Typical examples are HFE-347mcc3, HFE-347mmy, HFE-245mc, HFE-227me, and HFE-254cb2. HFE-245mf, HFE-245mc, HFE-254pc and HFE-356mec are particularly promising. However, it is not expected the use of HFEs in this application considering the availability of less expensive alternatives.
Also, HFEs including HFE-227me and CF(CF3)CF2OCHFCF3 have been proposed for
use as clean etching agents in semiconductor manufacture and some fluorinated ethers have been proposed for
use as fire suppressants, such as H Galden 1040x and possibly The IPCC/TEAP suggests that as a result of the relatively low GWPs of some HFEs, their use as a replacement for other gases would “significantly reduce” greenhouse gas emissions. However, they are currently more expensive to produce than HFCs that can be used for the same purposes, so far use is minimal, and future developments are difficult to forecast. Emissions reduction options There is little information available regarding the costs of HFE mitigation. Currently, HFEs use is concentrated in specialised high value sectors (such as precision cleaning) where the main alternatives are higher GWP fluorocarbons. There is therefore limited scope for mitigation. Producers Main producers of HFEs are in located in the United States of America and to some degree in the European Union, but not in Japan. Methodologies to estimate emissions HFE are potential substitutes of ODS and emissions may be estimated using methodologies comparable to those used for ODS substitutes. Methods are available in the 2006 IPCC Guidelines for specific uses of these substances such as heat fluids. References
IPCC/TEAP. 2005. Special Report on Safeguarding the Ozone and the Global Climate System: Issues relating
to hydrofluorocarbons and perfluorocarbons p. 391. Available at Frederic R L , Baptiste M, Jean- Pierre V and S Pazenok. 2008. Trifluoromethyl ethers - synthesis and properties of an unusual substituent. J. Org. Chem. 2008, 4, No. 13. doi:10.3762/bjoc.4.13
Paper no 1.B: Australia. Views on the coverage of greenhouse gases. Submission to the AWG-LCA and
AWG-KP. Available at UNEP/TEAP. 2009. Assessment of Alternatives to HCFCs and HFCs and Update of the TEAP 2005 Supplement Report Data. Task Force Decision XX/8 Report. UNEP Technology and Economical Assessment Panel. Available at http://ozone.unep.org/Assessment_Panels/TEAP/Reports/TEAP_Reports/teap-may-2009-decisionXX-8-task-force-report.pdf UNEP/TEAP. 2010. Assessment of HCFCs and environmentally sound alternatives; Scoping study on alternatives to HCFC refrigerants under high ambient temperature conditions. Task Force Decision XXI/9 Report. UNEP Technology and Economical Assessment Panel. Available at http://www.unep.ch/ozone/Assessment_Panels/TEAP/Reports/TEAP_Reports/teap-2010-progress-report-volume1-May2010.pdf The Significant New Alternatives Policy (SNAP) Program of the US EPA. Available at http://www.epa.gov/ozone/snap/ http://www.wipo.int/pctdb/en/wo.jsp?IA=US1994006439&WO=1995001320&DISPLAY=DESC http://www.wipo.int/pctdb/en/wo.jsp?IA=US2001044256&DISPLAY=CLAIMS 6. Perfluoropolyethers (PFPEs) Other names perfluoropolymethylisopropyl ethers (PFPMIE) are also named polyperfluoromethylisopropyl ethers, Fomblin HC or Galden.
* for PFPMIE (CF3OCF(CF3)CF2OCF2OCF3) Main applications: heat transfer fluids, cleaning and dermatologicalcosmetics Potential application: fire extinguisher Only one per-fluorpolyether is listed in the IPCC AR4: perfluoropolymethylisopropyl ether (PFPMIE). Reported uses for perfluoropolyethers as a chemical group include industrial heat transfer fluids, electronic reliability testing, metal and electronics cleaning, and lubricant applications. However, the majority of the cleaning industry have moved away from high-Ozone Depletion Potential (ODP) and/or high-GWP gases (e.g. CFC-113, methyl-chloroform, PFCs and PFPEs). Largely, this industry has adopted alternative technologies such as no-clean, aqueous and semi-aqueous cleaning; and solvents such as HFCs, HFEs, hydrocarbons and alcohols. Notwithstanding, certain specialty solvent applications (mainly precision cleaning) still require PFPEs as solvents owing to reliability, compatibility, stability and low toxicity. There is little information available regarding how large the PFPE share of this market is. Another application for which PFPEs have been identified as chemically suitable is as a fire extinguisher. However, there is little evidence available that PFPEs are used for this purpose at present. PFPMIE has been used as a dermatological and a cosmetic product, and as a heat transfer fluid and dielectric applications. Methodologies to estimate emissions Emissions for PFPEs used as transfer fluids and solvents may be estimated using the methodologies presented in the 2006 IPCC Guidelines. References Cora J. Young, Michael D. Hurley, Timothy J. Wallington, and Scott A. Mabury (2006) “Atmospheric Lifetime and Global Warming Potential of a Perfluoropolyether.” Environ. Sci. Technol., 2006, 40 (7), pp 2242–224
IPCC/TEAP. 2005. Special Report on Safeguarding the Ozone and the Global Climate System: Issues relating
to hydrofluorocarbons and perfluorocarbons. p. 391. Available at Paper no 1.B: Australia. Views on the coverage of greenhouse gases. Submission to the AWG-LCA and AWG-KP. Available at http://unfccc.int/resource/docs/2008/awglca3/eng/misc02a01.pdf 7. Dimethylether (DME) (CH3OCH3) Other names Methoxymethane, DME, Wood ether, Dimethyl oxide, Demeon, Dymel A
Main applications: aerosol propellant and synthetic fuel Dimethylether has been used as an aerosol propellant since the 1970s. In developed countries, 98 per cent of non-medical aerosols now use non-ozone-depleting, very low GWP propellants (hydrocarbons, dimethylether, CO2 or nitrogen). It is also used as a synthetic fuel that can be a substitute for liquefied petroleum gas (LPG), as a blended fuel in diesel or petrol engines, or reformed into hydrogen for fuel cells. Potential uses, in the development stage are power generation and petrochemical stocks. Several thousand tonnes are consumed annually for the production of dimethyl sulphate. Production Mostly from natural gas or coal as a synthetic fuel. May also be derived from many sources, including renewable materials (biomass, waste and agricultural products). Asia has the largest potential market for dimethylether as a domestic fuel. Most factories are in China. There are plans to construct new plants of dimethylether in Japan, Iran and New Guinea. Production capacity has grown exponentially from 20,000 million tonnes in 1993 to 545,000 million tonnes in 2006, and is forecasted to reach 11,317,000 million tonnes by 2012. Methodologies to estimate emissions No specific methodologies are available in the IPCC guidelines. References
The Catalyst Group, 2007, Global Dimethyl Ether Emerging Markets Available at http://sci-toys.com/ingredients/dimethyl_ether.html http://www.aboutdme.org/index.asp?bid=275 8. Methyl chloroform (CH3CCl3) Other names 1,1,1-Trichloroethane, TCA, Chlorothene
Main applications: solvent, cleaning, lubricant and chemical processing
Together with CFC-113, methyl chloroform was one of the most used solvents and degreaser in industry (metal
cleaning, electronics cleaning, and precision cleaning.). It was also used as: · as a component of aerosols formulations, particurlarly for brake cleaning; · as a coolant and lubricant in metal cutting oils; · component of adhesives; · in the manufacture of vinylidene chloride;
· the standard cleaner for photographic film (movie/slide/negatives, etc). It was registered as a pesticide and used in adhesives, aerosols, coatings, chemical process intermediates and in laboratory and analytical applications (Petroleum analyses). This compound is included as a controlled substance in the Montreal Protocol annexes. Reporting to this Protocol have shown that production of methyl chloroform has gone to a minimum level, and analyses made by the Science Panel under the MP have shown that concentrations of this chemical in the atmosphere are rapidly declining to virtually zero emissions. Methodologies to estimate emissions No specific methodologies are available in the IPCC guidelines, although general methodologies may be used when the substance is used as a solvent. References
IPCC/TEAP. 2005. Special Report on Safeguarding the Ozone and the Global Climate System. p. 391.
Available at Available at
UNEP. 2008. May 2008 Report of the Technology and Economic Assessment Panel. Volume 1. Progress Report,
2008. United Nations Environment Program (UNEP). Technology and Economic Assessment Panel. Available at
WMO. 2006. Scientific Assessment of Ozone Depletion: 2006 – Report no. 50. World Meteorological Organization. Global Ozone Research and Monitoring Project. Available at http://www.wmo.int/pages/prog/arep/gaw/ozone_2006/ozone_asst_report.html http://www.scorecard.org/chemical-profiles/html/methyl_chloroform.html http://www.hsia.org/white_papers/111tri wp.html 9. Methylene chloride (CH2Cl2) Other names Dichloromethane, R-30, Freon 30, Methylene dichloride, Solmethine, Narkotil, Solaesthin, Di-clo, DCM, UN 1593, MDC
Main applications: blowing agent polyurethane foams, solvent and extraction of oils. Methylene chloride was used, together with HCFCs (transitionally), HFC and CO2, as a blowing agent of foams. Has substituted CFC-11 for flexible low density polyurethane (PU) foams in developing countries. Together with trichloroethylene and perchloroethylene methylene chloride has been used as a primary in-kind substitute for 1,1,1-trichloroethane and carbon tetrachloride.
Other reported uses of methylene chloride are:
It is believed that the quantities used and emitted are relatively small, considering that methylene chloride is toxic to a certain degree. Methodologies to estimate emissions No specific methodologies are available in the IPCC guidelines, although general methodologies may be used when the substance is used as a solvent. References IPCC/TEAP. 2005. Special Report on Safeguarding the Ozone and the Global Climate System: Issues relating to hydrofluorocarbons and perfluorocarbons. p. 391. Available at http://www.ipcc.ch/pdf/presentations/briefing-bonn-2005-05/safeguarding-ozone-layer.pdf The Significant New Alternatives Policy (SNAP) Program of the US-EPA. Available at http://www.epa.gov/ozone/snap/ The US-EPAs Technology Transfer Network Air Toxics Web Site. Available at http://www.epa.gov/ttn/atw/hlthef/methylen.html The US Department of Health and Human Services - Agency for Toxic Substances and Disease Registry. Available at http://www.atsdr.cdc.gov/substances/methylene_chloride/index.html The Australian National Pollutant Inventory (NPI). Dichloromethane fact sheet. Available at http://www.npi.gov.au/database/substance-info/profiles/34.html Other names Chloromethane, R-40, Freon 40, Artic, UN 1063
Main applications: chemical processing, solvent, aerosol propellant and natural processes Chloromethane is used almost entirely as a chemical intermediate to make other chloromethanes, silicone intermediates, butyl rubber, pesticides, quaternary amines and surfactants and as a methylation reactant for various other processes. It is also used as industrial solvent and cleaner; heat transfer medium in fire extinguishing, aerosol propellant, extractant for greases, oils and resins, catalyst carrier in low-temperature polymerization, as a propellant and blowing agent in polystyrene foam production and as a as a fluid for thermometric and thermostatic equipment. Uses such as an anaesthetic and refrigerant were discontinued due to its toxicity and flammability. Together with methyl bromide (CH3 Br), it is one of the naturally occurring ozone-depleting substances (ODS). The large majority of emissions (90-99 per cent) are produced naturally in the oceans, from biomass burning in grasslands and forested areas, vegetation in tropical forests, and degradation of vegetal materials. The oceanic source estimate, once understood as the major source, has been revised downward. Methodologies to estimate emissions No specific methodologies are available in the IPCC guidelines, although general methodologies may be used when the substance is used as a solvent. References IPCC/TEAP. 2005. Special Report on Safeguarding the Ozone and the Global Climate System: Issues relating to hydrofluorocarbons and perfluorocarbons. p. 391. Available at http://www.ipcc.ch/pdf/presentations/briefing-bonn-2005-05/safeguarding-ozone-layer.pdf
WMO. 2006. Scientific Assessment of Ozone Depletion: 2006 – Report no. 50. World Meteorological Organization. Global Ozone Research and Monitoring Project. Available at http://www.wmo.int/pages/prog/arep/gaw/ozone_2006/ozone_asst_report.html http://www.epa.gov/ttn/atw/hlthef/methylch.html Other names Methylene bromide, Methylene dibromide, Methyl dibromide, DBM, MDB, Refrigerant-30B2, UN 2664
Main applications:solvent, gage fluid, plasma etching, pesticide, fire retardant and natural sources Naturally, dibromomethane is a primary emission product of macroalgae, in particular brown and green (e.g. Fucales sargassum, Laminariales lamanaria), occurring along beaches. Dibromomethane finds limited use in chemical synthesis, as a solvent, and as a gage fluid. It is also used with SiCl4+Cl2 for plasma etching, replacing HBr. It is also a pesticide intermediate, and an ingredient (limited use) in fire extinguishing fluid (fire retardant when added into the polymers). It can be released to the atmosphere as a by-product of tap water disinfection. Production Natural emission sources are estimated between 90 to 99 per cent of total global emissions and anthropogenic production represents a minor contributor. Methodologies to estimate emissions No specific methodologies are available in the IPCC guidelines, although general methodologies may be used when the substance is used as a solvent. References Philip H H, 1989, Handbook of environmental fate and exposure data for organic chemicals CRF Press. Available at http://books.google.co.uk/books?id=HdhohbQrg8IC http://www.ewg.org/tapwater/contaminants/contaminant.php?contamcode=2408 http://www.speclab.com/compound/c74953.htm http://www.made-in-china.com/showroom/cnzoutong/offer-detailMqbxmXyvAEYO/Sell-Dibromomethane.html http://www.wipo.int/pctdb/en/wo.jsp?wo=2005017961 12. Bromodifluoromethane (CHBrF2) Other names Difluorobromomethane, Halon 1201, HBFC-22B1, FC-22B1, R-22B1, FM-100
Main applications: Bromodifluoromethane is used as a fire extinguisher-suppressant, particularly in hand-held fire extinguishers. Bromodifluoromethane is included as a controlled substance in the Montreal Protocol annexes, and analyses made by the Science Panel under the MP have shown that concentrations of this chemical in the atmosphere have so far not reached significant levels. There is also no evidence that this chemical is being produced as a replacement for any conventional use. Methodologies to estimate emissions No specific methodologies are available in the IPCC guidelines, although general methodologies may be used when the substance is used as a solvent. References http://en.wikipedia.org/wiki/Bromodifluoromethane http://www.wipo.int/pctdb/en/wo.jsp?wo=1991005585 http://www.freepatentsonline.com/EP0383443.html 13. Trifluoroiodomethane (CF3I) Other names Trifluoromethyl iodide, Iodotrifluoromethane, Monoiodotrifluoromethane, Trifluoromethyl iodide, Perfluoromethyl iodide, Freon 13T1
Main application: reagent Potential applications: plasma etching, fire suppressant and medical sterilizer Trifluoroiodomethane is referred for plasma etching in the patent literature, and its composition makes potential use as refrigerants. It is used as a reagent in the rhodium-catalyzed a-trifluoromethylation of a,b-unsaturated ketones. It has being considered as a fire suppressant as a replacement for halon-1301 in unoccupied spaces, and as a flooding agent for in-flight aircraft and electronic equipment fires. It also has been proposed for use in blends with CO2 and ethylene oxide as a medical sterilizer, as a substitute for CFCs and HCFCs. Information from the Montreal Protocol Technology Panel is that no significant use is foreseen so far. This substance might in the future be controlled under the Montreal Protocol due to a small ODP value (from 0.011 to 0.018 dependent on where emissions take place) in spite of being a short lived substance. Methodologies to estimate emissions No specific methodologies are available in the IPCC guidelines, although general methodologies may be used when the substance is used as a solvent. References Clewell, H. and G. Lawrence. 1999. Position Paper for Trifluoroiodomethane (CF3I). U.S. Environmental Protection Agency, Office of Air and Radiation, Stratospheric Protection Division. Available at http://www.concentric.net/~cf3i/pospaper/posp.htm Dodd, D E ; Vinegar A. 1978. Cardiac sensitization testing of the halon replacement candidates trifluoroiodomethane (CF3I) and 1,1,2,2,3,3,3-heptafluoro-1-iodopropane (C3F7I), Drug and chemical toxicology ISSN 0148-0545. Available at http://cat.inist.fr/?aModele=afficheN&cpsidt=2251203 Dodd, DE, Leahy, H F; Feldmann, M L; Vinegar, . and J. H. English. 1998. Reproductive Toxicity Screen of Trifluoroiodomethane (CF31) in Sprague- Dawley Rats. Available at http://www.stormingmedia.us/03/0347/A034763.html The Significant New Alternatives Policy (SNAP) Program of the US EPA. Available at http://www.epa.gov/ozone/snap/ http://www.freepatentsonline.com/6270689.html http://www.sigmaaldrich.com/catalog/search/ProductDetail/ALDRICH/171441
EXISTING STOCKS AND POTENTIAL EMISSIONS OF CFCs AND HCFCs The estimate of the quantities of existing banks - banked chemicals in equipment and products - of CFCs and HCFCs is well documented in the following reports:
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http://ozone.unep.org/Assessment_Panels/TEAP/Reports/TEAP_Reports/teap-may-2009-decisionXX-8-task-force-report.pdf