UP20 D A0 1 TE UNEP Protecting the Ozone Layer V o l u m e 5 Aerosols, sterilants, carbon tetrachloride and miscellaneous uses This booklet is one of a series of reports prepared by the OzonAction Programme of the United Nations Environment Programme Division of Technology, Industry and Economics (UNEP DTIE). UNEP DTIE would like to give special thanks to the following organizations and individuals for their work in contributing to this project: United Nations Environment Programme (UNEP) Ms. Jacqueline Aloisi de Larderel, Director, UNEP DTIE Mr. Rajendra M. Shende, Chief, UNEP DTIE Energy and OzonAction Unit Ms. Cecilia Mercado, Information Officer, UNEP DTIE OzonAction Programme Mr. Andrew Robinson, Programme Assistant, UNEP DTIE OzonAction Programme Editor: Geoffrey Bird Design and layout: ampersand graphic design, inc. © 2001 UNEP This publication may be reproduced in whole or in part and in any form for educational and non-profit purposes without special permission from the copyright holder, provided acknowledgement of the source is made. UNEP would appreciate receiving a copy of any publication that uses this publication as a source. No use of this publication may be made for resale or for any other commercial purpose whatsoever without prior permission in writing from UNEP. The technical papers in this publication have not been peer-reviewed and are the sole opinion of the authors. The designations employed and the presentation of the material in this publication therefore do not imply the expression of any opinion whatsoever on the part of the United Nations Environment Programme concerning the legal status of any country, territory, city or area or of its authorities, or concerning delimitation of its frontiers or boundaries. Moreover, the views expressed do not necessarily represent the decision or the stated policy of the United Nations Environment Programme, nor does citing of trade names or commercial processes constitute endorsement. ISBN: 92-807-2162-3 UP20 D A0 1 TE UNEP Protecting the Ozone Layer V o l u m e 5 Aerosols, sterilants, carbon tetrachloride and miscellaneous uses Contents Foreword 3 Acknowledgements 4 Executive summary 5 Ozone depletion: an overview 6 Requirements of the Montreal Protocol 8 CFC use in aerosol products 12 CFC use in sterilants 15 Carbon tetrachloride 16 Miscellaneous uses 18 Prospects for action: 20 • • Aerosol products 20 Sterilants 26 Resources: 29 • • • • the implementing agencies 29 contact points 30 further reading 32 glossary 33 About the UNEP DTIE OzonAction Programme 34 About the UNEP Division of Technology, Industry and Economics 36 PROTECTING THE OZONE LAYER • TECHNICAL BROCHURE UPDATES • AEROSOLS AND STERILANTS Foreword When the Montreal Protocol on Substances that Deplete the Ozone Layer came into force, in 1989, it had been ratified by 29 countries and the EEC, and set limits on the production of eight man-made chemicals identified as ozone depleting substances (ODS). By July 2001 there were more than 170 Parties (i.e. signatories) to the Protocol, both developed and developing countries, and production and consumption of over 90 substances were controlled. Linking these two sets of figures, which attest to the success of the Montreal Protocol, is a process of elimination of ODS in which ratification of the Protocol was only a first step. It was recognized from the start that the Protocol must be a flexible instrument and that it should be revised and extended to keep pace with scientific progress. It was also recognized that developing countries would face special problems with phase out and would need assistance if their development was not to be hindered. To level the playing field, the developing countries were given extra time to adjust economically and to equip. A Multilateral Fund (MLF) was also set up early in the process to provide financial and technical support for their phase out efforts. Exchanges of information and mutual support among the Parties to the Montreal Protocol – via the mechanisms of the MLF – have been crucial to the Protocol’s success so far. They will continue to be so in the future. Even though many industries and manufacturers have successfully replaced ODS with substances that are less damaging to the ozone layer or with ODS-free technology, lack of upto-date, accurate information on issues surrounding ODS substitutes continues to be a major obstacle for many Parties, especially developing country Parties. To help stimulate and support the process of ODS phase out, UNEP DTIE’s OzonAction Programme provides information exchange and training, and acts as a clearinghouse for ozone related information. One of the most important jobs of the OzonAction programme is to ensure that all those who need to understand the issues surrounding replacement of ODS can obtain the information and assistance they require. Hence this series of plain language reports – based on the reports of UNEP’s Technical Options Committees (TOC) – summarizing the major ODS replacement issues for decision makers in government and industry. The reports, first published in 1992, have now been updated to keep abreast of technological progress and to better reflect the present situation in the sectors they cover: refrigerants; solvents, coatings and adhesives; fire extinguishing substances; foams; aerosols, sterilants, carbon tetrachloride and miscellaneous uses; and methyl bromide. Updating is based on the 1998 reports from the TOCs and includes further information from the TOCs until 2000. Updating of the reports at this point is particularly timely. The ‘grace period’ granted to developing countries under the Montreal Protocol before their introduction of a freeze on CFCs came to an end in July 1999. As developing countries now move to meet their Protocol commitments, accurate and upto-date information on available and appropriate technologies will be more important than ever if the final goal of effective global protection of the ozone layer is to be achieved. The publications in this series summarize the current uses of ODS in each sector, the availability of substitutes and the technological and economic implications of converting to ODS-free technology. Readers requiring more detailed information should refer to the original reports of the UNEP Technical Options Committees (see Further Reading) on which the series is based. 3 PROTECTING THE OZONE LAYER • TECHNICAL BROCHURE UPDATES • AEROSOLS AND STERILANTS Acknowledgements This report was written by Dr. Helen Tope (EPA Victoria, Australia) and Dr. Stephen O. Andersen (US EPA), based on the work of TEAP and its ATOC. The report was peer reviewed by Mr. Jose Pons, Prof. Ashley Woodcock, and members of the ATOC. Thanks are due to those members of the ATOC who gave freely of their time to ensure that this publication, while written in plain language, reflects the more detailed information available in the original report as accurately as possible. MEMBERS OF THE 2001 UNEP AEROSOL PRODUCTS, STERILANTS, MISCELLANEOUS USES AND CARBON TETRACHLORIDE TECHNICAL OPTIONS COMMITTEE 4 Co-chairs Affiliation Country Jose Pons Spray Quimica Venezuela Helen Tope Environment Protection Authority, Victoria Australia Ashley Woodcock University Hospital of South Manchester UK Members Affiliation Country D. D. Arora Tata Energy Research Institute India Paul Atkins Glaxo Wellcome USA Olga Blinova Russian Scientific Centre "Applied Chemistry" Russia Nick Campbell Elf-Atochem SA France Hisbello Campos Ministry of Health Brazil Christer Carling Astra Zeneca Sweden Francis M. Cuss Schering Plough Research Institute USA Chandra Effendy p.t. Candi Swadaya Sentosa Indonesia Charles Hancock Charles O. Hancock Associates USA Eamonn Hoxey Johnson & Johnson UK Javaid Khan The Aga Khan University Pakistan P. Kumarasamy Aerosol Manufacturing Sdn Bhd Malaysia Robert Layet Ensign Laboratories Australia Robert Meyer Food and Drug Administration USA Hideo Mori Otsuka Pharmaceutical Company Japan Robert F. Morrissey Johnson & Johnson USA Geno Nardini Instituto Internacional del Aerosol Mexico Dick Nusbaum Penna Engineering USA Tunde Otulana Aradigm Corporation USA Martyn Partridge Whipps Cross Hospital UK Fernando Peregrin AMSCO/FINN-AQUA Spain Jacek Rozmiarek Glaxo Wellcome SA Poland Abe Rubinfeld Royal Melbourne Hospital Australia Albert L. Sheffer Brigham and Women’s Hospital USA Greg Simpson CSIRO, Molecular Science Australia Roland Stechert Boehringer Ingelheim Pharma KG Germany Robert Suber RJR-Nabisco USA Ian Tansey Expert UK Adam Wanner University of Miami USA You Yizhong Journal of Aerosol Communication China PROTECTING THE OZONE LAYER • TECHNICAL BROCHURE UPDATES • AEROSOLS AND STERILANTS Executive summary The use of ozone-depleting substances in industry increased significantly until about 1990. The result has been serious depletion of the ozone layer. The hole in the Antarctic ozone layer is now larger than ever before and similar depletion frequently occurs over the Arctic. The Montreal Protocol, drafted under the auspices of the United Nations Environment Programme (UNEP), will phase out the production and consumption of the man-made substances that deplete stratospheric ozone. This action will prevent further damage to the ozone layer, and should eventually allow the ozone layer to repair itself. This report considers CFC uses in aerosol products, as sterilants, and in a range of miscellaneous applications including food freezing, tobacco expansion, fumigation and cancer therapy. It also covers the use of carbon tetrachloride. Aerosol products were, at one time, the source of 60 per cent of global CFC uses and emissions, as much as 300,000 tonnes in 1986. Substitutes for CFC aerosol products are readily available except for a few specialized medical and industrial applications. CFC use in aerosol products will be reduced to insignificant amounts by 2005. Currently about 1500 tonnes of CFCs are used in the sterilization of equipment. The most widely used sterilant is ethylene oxide, a substance that is toxic, mutagenic, a suspected carcinogen, flammable and explosive. To reduce these risks, ethylene oxide can be used in a mixture that contains 88 per cent CFC-12 by weight. The alternatives to CFCs include the use of undiluted ethylene oxide, steam, formaldehyde, a mixture of ethylene oxide and carbon dioxide, and mixtures of ethylene oxide with HCFCs. These techniques enabled CFC phase out in developed countries by 1995. Carbon tetrachloride is used as a feedstock in the production of CFC-11 and CFC-12, in the production of key pharmaceuticals and agricultural chemicals, and as a catalyst promoter. Its use in the CFC industry will be progressively reduced as CFCs themselves are phased out. The Montreal Protocol allows the use of carbon tetrachloride as a feedstock wherever carbon tetrachloride is destroyed in the production process, or where it is used as a process agent. (for more information see TEAP, 2001 at http://www.teap.org). The miscellaneous uses of CFCs cover a wide variety of fields but use only small amounts of CFCs. They are therefore not covered in detail in this publication. 5 PROTECTING THE OZONE LAYER • TECHNICAL BROCHURE UPDATES • AEROSOLS AND STERILANTS Ozone depletion: an overview Most of the oxygen in the Earth’s atmosphere is in the form of molecules containing two oxygen atoms, known by the familiar chemical symbol O2. In certain circumstances, three atoms of oxygen can bond together to form ozone, a gas with the chemical symbol O3. Ozone occurs naturally in the Earth’s atmosphere where its concentration varies with altitude. Concentration peaks in the stratosphere at around 25–30 kilometres from the Earth’s surface and this region of concentration of the gas is known as the ozone layer. The ozone layer is important because it absorbs certain wavelengths of ultraviolet (UV) radiation from the Sun, reducing their intensity at the Earth’s surface. High doses of UV radiation at these wavelengths can damage eyes and cause skin cancer, reduce the efficiency of the body’s immune system, reduce plant growth rates, upset the balance of terrestrial and marine ecosystems, and accelerate degradation of some plastics and other materials. A number of man-made chemicals are known to be harmful to the ozone layer. They all have two common properties: they are stable in the lower atmosphere and they contain chlorine or bromine. Their stability allows them to diffuse gradually up to the stratosphere where they can be broken down Effects of CFCs on stratoshperic ozone UV radiation series of reactions CFCl3 chlorine monoxide free chlorine radical When gases containing chlorine, such as CFCs, are broken down in the atmosphere, each chlorine + chlorine radical atom sets off a reaction that may destroy hundreds of thousands ozone (O3) CFCl2 of ozone molecules. oxygen molecule (O2) by solar radiation. This releases chlorine and bromine radicals that can set off destructive chain reactions breaking down other gases, including ozone, and thus reducing the atmospheric concentration of ozone. This is what is meant by ozone depletion. The chlorine or bromine radical is left intact after this reaction and may take part in as many as 100,000 similar reactions before eventually being washed out of the stratosphere into the troposphere. 6 PROTECTING THE OZONE LAYER • TECHNICAL BROCHURE UPDATES • AEROSOLS AND STERILANTS How CFC Nomenclature Works F F CFC numbers provide the information needed to deduce the chemical structure of the compound. The digit far right Cl C C CFC 114 Cl provides information on the number of fluorine atoms, the digit second from the right provides information on hydrogen atoms, and the digit on the left provides F F number of carbon atoms minus one (omitted if 0) number of hydrogen atoms, plus one number of flourine atoms in one molecule information on carbon atoms. Vacant valencies are filled with chlorine atoms. Adding 90 to the number reveals the numbers of C, H and F atoms more Note: 1. All spare valencies filled by chlorine atoms 2. Different isomers are indicated by a suffic of lower case letters 3. Bromine atoms are indicated by a suffic B plus number of atoms 4. Hundreds number = 4 or 5 for blends (e.g. R-502) directly. Another important environmental impact of a gas is its contribution to global warming. Global Warming Potential (GWP) is an estimate of the warming of the atmosphere resulting from release of a unit mass of gas in relation to the warming that would be caused by release of the same amount of carbon dioxide. Some ODS and some of the chemicals being developed to replace them are known to have significant GWPs. For example, CFCs have high GWPs and the non-ozone-depleting hydrofluorocarbons (HFCs) developed to replace CFCs also contribute to global warming. GWP is an increasingly important parameter when considering substances as candidates to replace ODS. During past decades, sufficient quantities of ODS have been released into the atmosphere to damage the ozone layer significantly. The largest losses of stratospheric ozone occur regularly over the Antarctic every spring, resulting in substantial increases in UV levels over Antarctica. A similar though weaker effect has been observed over the Arctic. At present, scientists predict that, provided the Montreal Protocol is implemented in full, ozone depletion will reach its peak during the next few years and will then gradually decline until the ozone layer returns to normal around 2050. 7 PROTECTING THE OZONE LAYER • TECHNICAL BROCHURE UPDATES • AEROSOLS AND STERILANTS The Montreal Protocol The Montreal Protocol, developed under the management of the United Nations Environment Programme in 1987, came into force on 1 January 1989. The Protocol defines measures that Parties must introduce to limit production and consumption of substances that deplete the ozone layer. The Montreal Protocol and the Vienna Convention – the framework agreement from which the Protocol was born – were the first global agreements to protect the Earth’s atmosphere. The Protocol originally introduced phase out schedules for five CFCs and three halons. However, it was designed so that it could be revised on the basis of periodic scientific and technical assessments. The first revisions were made at a meeting of the Parties in London, in 1990, when controls were extended to additional CFCs and halons as well as to carbon tetrachloride and methyl chloroform. At the Copenhagen meeting, in 1992, the Protocol was amended to include methyl bromide and to control HBFCs and HCFCs. A schedule for phase out of methyl bromide was adopted at the Vienna meeting in 1995, and this was later revised in 1997, in Montreal. In 1999, the Parties met in Beijing, where they extended control to bromochloromethane (CBM). By July 2001, there were 177 Parties to the Montreal Protocol and more than 90 chemicals are now controlled. Ozone-depleting substances (ODS) covered by the Montreal Protocol and their ozone-depletion potential (ODP)* Ozone-depleting substance (ODS) Major uses Ozone-depletion potential (ODP) Chlorofluorocarbons Refrigerants; propellants for spray cans, inhalers, etc.; 0.6–1 (CFC) solvents, blowing agents for foam manufacture Halons Used in fire extinguishers 3–10 Carbon tetrachloride Feedstock for CFCs, pharmaceutical and agricultural 1.1 chemicals, solvent 1,1,1-trichlorethane Solvent 0.1 Developed as ‘transitional’ replacement for CFCs. 0.01–0.52 (HCFCs) Developed as ‘transitional’ replacement for CFCs. 0.02–7.5 Methyl bromide Fumigant, widely used for pest control 0.6 Bromochloromethane (CBM) Solvent 0.12 (methyl chloroform) Hydrobromofluorocarbons (HBFCs) Hydrochlorofluorocarbons * Where ranges of ODP are given, readers requiring the exact ODP for a given CFC, halon, HBFC or HCFC should refer to the Handbook for the International Treaties for the Protection of the Ozone Layer, published by the UNEP Ozone Secretariat, or other accredited sources. 8 PROTECTING THE OZONE LAYER • TECHNICAL BROCHURE UPDATES • AEROSOLS AND STERILANTS How regulation works All ODS do not inflict equal amounts of damage on the ozone layer. Substances that contain only carbon, fluorine, chlorine, and/or bromine – referred to as fully halogenated – have the highest potential for damage. They include CFCs and halons. Other substances, including the hydrochlorofluorocarbons (HCFCs), developed as replacements for CFCs, also contain hydrogen. This reduces their persistence in the atmosphere and makes them less damaging for the ozone layer. For the purposes of control under the Montreal Protocol, ODS are assigned an ozone-depletion potential (ODP). Each controlled chemical is assigned an ODP in relation to CFC-11 which is given an ODP of 1. These values are used to calculate an indicator of the damage being inflicted on the ozone layer by each country’s production and consumption of controlled substances. Consumption is defined as total production plus imports less exports, and therefore excludes recycled substances. The relative ozone-depleting effect of production of a controlled ODS is calculated by multiplying its annual production by its ODP, results are given in ODP tonnes, a unit used in this series of publications and elsewhere. The ODS currently covered by the Montreal Protocol are shown, with their ODPs, in the table opposite. Developing countries and the Montreal Protocol From the outset, the Parties to the Montreal Protocol recognized that developing countries could face special difficulties with phase out and that additional time and financial and technical support would be needed by what came to be known as ‘Article 5’ countries. Article 5 countries are developing countries that consume less than 0.3 kg per capita per year of controlled substances in a certain base year. They are so called because their status is defined in Article 5 of the Protocol1. Financial and technical assistance was provided under the 1990 London Amendment which set up the Multilateral Fund (MLF). Activities and projects under the MLF are implemented by four implementing agencies: UNDP, UNEP, UNIDO and the World Bank. Article 5 countries were also granted a ‘grace period’ of 10 years to prepare for phase out. 1999 marked the end of that period for production and consumption of CFCs. Article 5 countries have, since 1999, entered the ‘compliance’ period in which they will have to achieve specific reduction targets. The requirements of the Montreal Protocol as of December 2000 for both developed and Article 5 countries are shown in the table on page 10. 1 This is often written Article 5(1), indicating that status is defined in paragraph 1 of Article 5 of the Protocol. ‘Article 5 Parties’ is also used. 9 PROTECTING THE OZONE LAYER • TECHNICAL BROCHURE UPDATES • AEROSOLS AND STERILANTS Requirements of the Montreal Protocol including amendments and adjustments to the end of 1999** Controlled Substance Reduction in consumption and production for developed countries Reduction in consumption and production for developing (Article 5) countries CFC-11, CFC-12, CFC- 113, Base level: 1986 Base level: Average of 1995–1997 CFC-114, CFC-115 1989: Freeze 1999: Freeze 1994: 75 per cent 2005: 50 per cent 1996: 100 per cent 2007: 85 per cent 2010: 100 per cent Halon 1211, halon 1301, halon Base level: 1986 Base level: Average of 1995–1997 2402 1992: 20 per cent 2002: Freeze 1994: 100 per cent 2005: 50 per cent 2010: 100 per cent Base level: 1989 Base level: Average of 1998–2000 1993: 20 per cent 2003: 20 per cent 1994: 75 per cent 2007: 85 per cent 1996: 100 per cent 2010: 100 per cent Base level: 1989 Base level: Average of 1998–2000 1995: 85 per cent 2005: 85 per cent 1996: 100 per cent 2010: 100 per cent 1,1,1-trichloroethane Base level: 1989 Base level: Average of 1998–2000 (methyl chloroform) 1993: Freeze 2003: Freeze 1994: 50 per cent 2005: 30 per cent 1996: 100 per cent 2010: 70 per cent Other fully halogenated CFCs Carbon tetrachloride 2015: 100 per cent HCFCs Consumption Consumption Base level: 1989 HCFC consumption + Base level: 2015 2.8 per cent of 1989 CFC consumption 2016: Freeze 1996: Freeze 2040: 100 per cent 2004: 35 per cent Production 2010: 65 per cent Base level: 2015 2015: 90 per cent 2001: Freeze 2020: 99.5 per cent 2030: 100 per cent Production Base level: 1989 HCFC consumption + 2.8 per cent of 1989 CFC consumption 2004: Freeze 10 PROTECTING THE OZONE LAYER • TECHNICAL BROCHURE UPDATES • AEROSOLS AND STERILANTS Requirements of the Montreal Protocol including amendments and adjustments to the end of 1999** Controlled Substance Reduction in consumption and production for developed countries Reduction in consumption and production for developing (Article 5) countries HBFCs 1996: 100 per cent 1996: 100 per cent Bromochloromethane 2002: 100 per cent 2002: 100 per cent Methyl bromide Base level: 1991 Base level: Average of 1995-1998 1995: Freeze 2002: Freeze 1999: 25 per cent 2005: 20 per cent 2001: 50 per cent 2003: review of reduction schedule 2003: 70 per cent 2015: 100 per cent 2005: 100 per cent ** The Protocol allows some exemptions, e.g. for "essential uses." Readers requiring full details of phase out for a given substance should refer to the Handbook for the International Treaties for the Protection of the Ozone Layer, published by the UNEP Ozone Secretariat, or other accredited sources. Progress in the ratification of the Montreal Protocol and its amendments 200 150 No. of Countries Ratifying 100 50 0 Vienna Convention Montreal Protocol London Copenhagen Amendment Amendment Montreal Beijing Amendment Amendment Agreement Source: Caleb Management Services, UK 11 PROTECTING THE OZONE LAYER • TECHNICAL BROCHURE UPDATES • AEROSOLS AND STERILANTS CFC use in aerosol products Compressed gas propellants were first used in 1923 as a foams means of dispersing Aerosol product uses others 7% insecticides. An aerosol propellant must evaporate quickly and disperse the active currently account for about 27 percent of all CFC usage but reductions are aerosols 27% solvents 16% being rapidly introduced in most countries. ingredient effectively. Compressed gas is of limited use as a propellant since the refrigeration 25% gas pressure in the container falls as the container empties. CFC-12 was introduced, during World War II, because it maintains constant pressure until all of the product is dispensed. CFCs are also not explosive, flammable or toxic, can be produced in very pure form and are good solvents. These properties made them the preferred propellant in an industry that expanded rapidly after World War II. By 1987, more than 8000 million aerosol cans were being produced annually – the equivalent of 15,000 per minute. CFCs have been used to dispense a wide variety of sprays, including lacquers and paints, deodorants, shaving foam, perfume, insecticides, window cleaners, oven cleaners, pharmaceutical and veterinary products, glues and lubricating oils. CFC-12 was the most widely used propellant but CFC-114 was also used to disperse products containing alcohol. CFC-11 is not a propellant, but was added to some formulations as a solvent and carrier. The fact that CFCs were both good propellants and good solvents accounted for many of their uses in aerosol products. In some formulations, CFCs had the added advantage of suppressing the flammability of other ingredients. CFCs are also used in aerosol products designed to produce a chilling effect that occurs when compressed gases are sprayed. Aerosol chilling products include local anaesthetic and sprain treatment, freezing of liquids in leaking pipes to cut off flow while repairs are made, freezing of chewing gum so that it can be removed from fabrics, and identification of electronic circuit faults by cooling solder joints so that the electrical circuit is interrupted. CFCs can also be used to remove dust from photographs, disks and tapes because they evaporate quickly and leave no residues. And, finally, the sudden escape of CFCs from a small orifice is used to create noise in fog and sports horns, and alarm equipment. In the mid-1970s, aerosol products accounted for 60 per cent of all the CFC-11 and CFC-12 used worldwide. By the end of the decade, however, countries were beginning to ban or restrict the use of 12 PROTECTING THE OZONE LAYER • TECHNICAL BROCHURE UPDATES • AEROSOLS AND STERILANTS CFCs in aerosol products and, after the introduction of the Montreal Protocol in 1987, CFC use in aerosol products began to decline rapidly. Overall consumption was about 300,000 tonnes in 1986 but was reduced to some 180,000 tonnes in 1989. Progress since then has been rapid. There are now no technical barriers to global transition to alternatives. In 1991 about 115,000 tonnes of CFCs were used in aerosol products. By 1999 this had fallen to about 9000 tonnes (excluding MDIs – metered-dose inhalers). The table below summarizes regional consumption in 1999. Regional use of CFCs in aerosol products (excluding MDIs) CFC Used (tonnes) 1999 ASEAN countries 900 China 2300 Indian subcontinent countries* 1000 Latin America 500 Middle East and Africa 400 Russian Federation 3500 Ukraine 500 Other CEIT, including CIS** 100 Total 9200 * India, Pakistan, Sri Lanka, Bangladesh, Nepal and Bhutan ** Other countries with economies in transition, including the Commonwealth of Independent States How countries reduced CFC use in aerosol products There have been four distinct stages in phasing out CFCs from convenience and cosmetic aerosol products: Stage 1: Stage 2: Stage 3: Stage 4: Before 1987 1987 to 1990 1990 to 1992 1992 to 2001 Canada, Sweden, Australia, Austria, Brazil, Egypt, Finland, All countries except and the United States Denmark, Germany, Hungary, Norway, some developing Mexico, New Zealand, Switzerland, and countries and some United Kingdom, and Trinidad and Tobago CEITs Venezuela 13 PROTECTING THE OZONE LAYER • TECHNICAL BROCHURE UPDATES • AEROSOLS AND STERILANTS CFC use in metered dose inhalers CFC-containing metered dose inhalers (MDIs) provide reliable and effective therapy for respiratory diseases such as asthma and chronic obstructive pulmonary disease (COPD). MDIs generally use CFC-12 as a propellant. To suspend or dissolve medication, most use CFC-11 and CFC-114, either alone or in a mixture. Approximately 500 million MDIs were used annually worldwide in 1998, using approximately 10,000 tonnes of CFCs. The prevalence of asthma and COPD is increasing worldwide. In 1998 there were estimated to be 300 million patients with asthma and COPD throughout the world. Evidence confirms that asthma prevalence is increasing as urbanization of developing countries continues. There is international consensus that primary treatment of these diseases should be by the inhaled route. Inhalation permits fast and efficient delivery of treatment to the airways with minimal risk of adverse reactions. Therapy requires regular treatment, often with more than one drug. MDIs remain the dominant inhaled delivery system in most countries and for all categories of drugs. Overall, use of inhaled medication is increasing because of increased prevalence of disease. World Health Organization/US National Heart, Lung and Blood Institute (WHO/NHLBI-GINA) guidelines on asthma management also encourage the inhaled route as the preferred method of administering medicine. Therapy administered by the inhaled route is likely to remain the mainstay of therapy for asthma/COPD. An MDI is a complex system designed to provide a fine mist of medicament for inhalation directly to the lungs to treat respiratory diseases such as asthma and COPD. The active ingredient may be dissolved in the propellant but is more often present as a suspension of particles, the majority of which are less than 5 micrometers in diameter. A surface-active agent may be included to ensure that the drug is well suspended and to help lubricate the metering valve. When a patient uses an MDI, the drug/propellant mixture in the metering chamber of the valve is expelled by the vapour pressure of the propellant through the exit orifice in the actuator. As droplets of drug in propellant leave the spray nozzle the propellant gases expand, with very rapid evaporation, resulting in a fine aerosol cloud of drug particles. Alternatives to CFC-based MDIs are primarily hydrofluorocarbon (HFC) based MDIs, dry powder inhalers (DPIs) (single or multi-dose), nebulizers (hand held or stationary), orally administered drugs (tablets, capsules or oral liquids) and injectable drugs. It is likely that a wide range of reformulated products will be available in many developed countries and transition to these products away from CFCs will be making good progress by the year 2005. 14 PROTECTING THE OZONE LAYER • TECHNICAL BROCHURE UPDATES • AEROSOLS AND STERILANTS CFC use in sterilants A mixture of ethylene oxide and CFC-12 is used to sterilize medical equipment. The CFC is used to KEY FACTS reduce the flammability and explosive risk of ethylene oxide. The most common mixture contains 88 per cent CFC-12 by weight, and is commonly known as 12/88. Use of CFC-12 in sterilization has been successfully phased out in most developed countries and in some countries with economies in transition; it is still used in developing countries. Worldwide, use of CFC-12 for this purpose was estimated to be less than 1500 tonnes in 1998 (compared with approximately 25,000 tonnes in 1989). Ethylene oxide penetrates packaging materials, destroys microorganisms and diffuses away from the package leaving almost no residues. It is used to sterilize medical and surgical equipment and devices such as catheters and fibre optic medical equipment that are sensitive to heat and moisture. Since ethylene oxide is toxic, mutagenic, a suspected carcinogen, flammable and explosive, its use requires stringent safety precautions and is strictly regulated in some countries. This has led to widely differing sterilization practices in different countries. Great efforts have been made to replace ethylene oxide as a sterilant, particularly in hospitals, owing to concerns about exposure of personnel. The fact that ethylene oxide is still widely used as a sterilant is evidence that, in numerous applications, the benefits of its use outweigh these disadvantages. Consumption patterns vary globally so that while no use of 12/88 is reported for China, its use has been reported in more than 40 other developing countries. There are also indications of increasing use of CFC-12 in sterilization in some developing countries. Some manufacturers of surgical equipment may even be shipping products from developed to developing countries for sterilization with 12/88. A range of sterilization methods is available. Some use ethylene oxide, others do not. Ethylene oxide can be used as a sterilant either alone or diluted with other gases such as CFC-12, HCFCs or carbon Ethylene oxide can be used to sterilize medical equipment, either alone or diluted with other gases such as CFC-12, HCFCs or carbon dioxide (CO2). Mixtures of CFC-12 and ethylene oxide are used in some developing countries. Mixtures of HCFCs and ethylene oxide are used in some developed countries. Methods that do not rely on ethylene oxide include steam sterilization, dry heat, formaldehyde, radiation and ionized gas plasma. Health and safety regulations on ethylene oxide in some countries have led to the use of processes such as steam, formaldehyde and radiation. dioxide (CO2). Methods that do not rely on ethylene oxide include steam sterilization, dry heat, formaldehyde, radiation and ionized gas plasma. HCFC replacement mixtures for 12/88 are used mostly in the United States and in some European countries. The European Union has legislation restricting the use of HCFCs in emissive applications such as sterilization. Mixtures of HCFCs and ethylene oxide are virtual drop-in replacements for 12/88. HCFCs have been found to be important as transitional products in sterilization in those countries that previously employed 12/88 extensively. The use of HCFC replacement mixtures was estimated to be less than 3000 metric tonnes in 1998 (some 90 ODP tonnes). 15 PROTECTING THE OZONE LAYER • TECHNICAL BROCHURE UPDATES • AEROSOLS AND STERILANTS Carbon tetrachloride Carbon tetrachloride (CCl4) – a controlled substance under the Montreal Protocol – is used as a KEY FACTS Carbon tetrachloride is a controlled substance under the Montreal Protocol. feedstock for the production of other chemicals, as a process agent, and for other uses. As a feedstock, carbon tetrachloride is the basic chemical building block in the production of other CFCs, notably CFC-11 and CFC-12. The carbon tetrachloride undergoes transformation in the process and is converted from its original composition. Only insignificant trace emissions, allowed Its main use is as a feedstock for the production of CFCs – a use that will disappear along with CFCs. under the Montreal Protocol, remain. Other uses are as a process agent in the chemical industry, as a solvent and for grain insecticide fumigation. The Montreal Protocol allows the use of carbon tetrachloride as a feedstock and specific uses as a process agent. of ibuprofen (a basic drug used for analgesic formulations in painkillers). Some products can be When used as a process agent, carbon tetrachloride’s unique chemical or physical properties facilitate an intended chemical reaction and/or inhibit an unintended one. Carbon tetrachloride is used as a process agent in a variety of applications including the chlorination of rubber and the production produced without the use of carbon tetrachloride, for others, carbon tetrachloride cannot be replaced for reasons of health, safety, environment, quality, yield, cost effectiveness, technical and economic feasibility. The Montreal Protocol allows specific uses of carbon tetrachloride as a process agent (for elaboration see TEAP, 2001 at http://www.teap.org). The use of carbon tetrachloride as a solvent includes simple solvent extraction, such as caffeine extraction and palm oil extraction, and cleaning applications such as metal degreasing and textile spotting. Substitutes are commercially available and economic. These uses should therefore be discontinued to protect the ozone layer and safeguard the health and safety of people using carbon tetrachloride. Carbon tetrachloride can also be used in miscellaneous applications such as fire extinguishers, grain insecticide fumigation, and as an anti-helminthic agent (especially for the treatment of liver fluke in sheep). In 1996, estimated atmospheric emissions of carbon tetrachloride were 41,000 tonnes. The primary source of atmospheric emissions of carbon tetrachloride is its use as a feedstock in the production of CFCs. Emissions have been estimated at around 28,000 tonnes for 1996, about 70 per cent of total emissions. The majority of feedstock use emissions originate from CFC production in developing countries and countries with economies in transition. As production of CFCs is phased out under the Montreal Protocol, carbon tetrachloride emissions will continue to decline. Atmospheric levels of carbon tetrachloride have already reduced as a result of the phasing out of CFC consumption in developed countries. 16 PROTECTING THE OZONE LAYER • TECHNICAL BROCHURE UPDATES • AEROSOLS AND STERILANTS There are a number of measures that can lead to reductions in carbon tetrachloride emissions to the environment: • closure of CFC manufacturing facilities; • conversion of facilities using carbon tetrachloride as process agents to alternatives; • further use of improved emission control technology in carbon tetrachloride and CFC manufacturing facilities; • further use of improved containment and emission control technology in manufacturing facilities using carbon tetrachloride as process agents. As the bulk of carbon tetrachloride production is for use as a feedstock for CFC production this use will be eliminated along with CFCs. Carbon tetrachloride is not dealt with further in this publication (for more information see TEAP, 2001 at http://www.teap.org). 17 PROTECTING THE OZONE LAYER • TECHNICAL BROCHURE UPDATES • AEROSOLS AND STERILANTS Miscellaneous uses CFCs have been used in small amounts in many different ways in many different industries. The minor KEY FACTS There are many miscellaneous uses of CFCs in industry but none use substantial amounts. The two remaining consumers are the expansion of cured tobacco to provide low tar cigarettes, and laboratory and analytical uses. uses described below now consume insignificant amounts of CFC. In 1998, tobacco expansion was thought to be the largest of these small uses. Laboratory and analytical uses of CFCs are perhaps the most widespread of these uses globally. • CFC-11 has been used to expand dried tobacco to its original size to provide low tar cigarettes. Worldwide use is difficult to estimate. About 4050 tonnes was used in China in 1996. Carbon dioxide is an alternative expansion agent used in many countries. Others used less commonly are nitrogen, propane, and iso-pentane. The principal difficulty for developing countries is the high capital cost of conversion to alternative technologies. Most are converting to carbon dioxide expansion technologies. • Laboratory and analytical uses of ozone depleting substances such as CFC-113 and carbon tetrachloride include: equipment calibration; extraction solvents, diluents, or carriers for specific chemical analyses; inducing chemical-specific health effects for biochemical research; as a carrier Substitute chemicals and processes are available for all miscellaneous uses. for laboratory chemicals; and other critical purposes in research and development where With the phase out of CFCs in developing countries, these substitutes will be used or the processes abandoned. conditions (see Decisions VI/9)2. International and national organizations are working to eliminate substitutes are not readily available or where standards set by national and international agencies require specific use of the controlled substances. The Montreal Protocol allows a global exemption for laboratory and analytical uses for developed countries until the end of 1995 under strict the use of ozone depleting substances in many laboratory and analytical uses. Decision XI/193 eliminates three major uses from the global exemption from 1 January 2002: testing of oil, grease and total petroleum hydrocarbons in water; testing of tar in road paving materials; and forensic finger-printing. • Food can be frozen through contact with liquid CFC-12, which boils at -30 °C at normal pressure. CFC consumption has been totally eliminated from this application using available alternative freezing methods. 2 Decision VI/9 adopted by the 6th Meeting of the Parties to the Montreal Protocol. For details, see the Handbook for the International Treaties for the Protection of the Ozone Layer (UNEP Ozone Secretariat). 3 Decision XI/19 adopted by the 11th Meeting of the Parties to the Montreal Protocol. For details, see the Handbook for the International Treaties for the Protection of the Ozone Layer (UNEP Ozone Secretariat). Food freezing Tobacco expansion Fumigation 123005700150004 IER GLAC FROZE N SHR IMPS alternatives: liquid nitrogen and air blast freezing Metal purification alternatives: HCFC-123, propane, steam, liquid N2 and CO2 Thermostats/thermometers 20 70 80 0 25 -10 fah -20 -5 160 10 70 30° 145 10° 40 100 130 25° 5° 30 85 60 40 10 55 Radiation therapy 5 11 20° Double glazing 50 15° alternatives: conventional fumigation l ce siu s little used: abandon technique? 18 re nh eit new formulations being developed temporary exception PROTECTING THE OZONE LAYER • TECHNICAL BROCHURE UPDATES • AEROSOLS AND STERILANTS • Fumigation with CFC/ethylene oxide mixtures can be used to treat an assortment of objects, including spices, rare books and manuscripts, and beehives. Consumption of CFCs for this application in developed countries has been eliminated. Consumption would be minimal, if any, in developing countries. • CFC-12 and a halide detector can be used to detect leaks in pressure vessels. A combination of HCFC-22 and nitrogen is one alternative, another is the use of helium with helium detectors. • Wind tunnels are sometimes filled with CFCs because the velocity of sound is much lower in CFC than in the air. This means that supersonic conditions can be reached with much lower circulation rates. Possible alternatives are sulphur hexafluoride and HFC-134a. • In the United Kingdom, graphite rods for nuclear reactors used to be purified by heating them in a furnace filled with CFC-12. The process is no longer used. A similar process has been used in the Middle East to refine aluminium. • Refrigerator and central heating thermostats and thermometers have made use of the rate at which CFCs expand as temperature rises to operate on/off switches and turn dials on rotary thermometers. Other fluorinated chemicals are alternatives for this application. • Double glazing sometimes uses a gas mixture that includes CFC-12 to lower thermal conductivity and increase transparency. Other insulating gases such as argon are used as alternatives. European insulating window manufacturers sometimes use sulphur hexafluoride – one of the most potent greenhouse gases known – but this use may be environmentally counterproductive and could be banned under new regulations to protect the climate. • Linear accelerators used for radiation therapy have used CFC-12 as a dielectric medium in the transmission of energy at radio frequencies. Sulphur hexafluoride is used as an alternative. • Solar tracking systems have made use of CFC expansion to tilt solar panels towards the sun. HCFC22 is a substitute and mechanically driven systems are also available. The latter, however, are more prone to wind damage and are less energy efficient since they use tracking motors. Other minor uses of CFCs may exist. However, with phase out of CFCs, most have either been abandoned or replaced by alternative substances and processes. A few very minor uses, such as laboratory and analytical uses have required temporary exemption in developed countries since 1996. As these minor uses of CFCs are relatively insignificant, they are not considered further in this publication. Laboratory analysis Leak testing Wind tunnels 6 19.2 temporary exeption Ice plugs in piping alternatives: HCFC-22 and HCFC-152 temporary exemption Drug manufacturing substitutes by the year 2000 little used: abandon technique? Solar tracking systems HCFC-22 and mechanical systems 19 PROTECTING THE OZONE LAYER • TECHNICAL BROCHURE UPDATES • AEROSOLS AND STERILANTS Aerosol products CFCs are used in aerosol products as propellants, as solvents, as a means of reducing the KEY FACTS The aerosol products industry can eliminate CFC usage by converting to alternative propellants, including: flammability of the active ingredient and as the active ingredient itself in aerosol products designed to chill and to produce noise. Substitutes for CFCs are chosen with these properties in mind. Many different substitutes have been adopted and proposed to replace CFCs. One approach involves finding a substitute for the aerosol concept itself – such as the use of solid sticks for deodorants. The range of possibilities is shown in the table below. • hydrocarbons; • dimethyl ether; Substitutes for propellants • compressed air, CO2 or nitrous oxide; and Hydrocarbons and dimethyl ether • HFCs and HCFCs. propellants. They are cheap and efficient, but highly flammable. Operators can minimize risks by HFC-134a, which is non-flammable and has an ODP of zero, also has a high GWP. Its use will therefore be limited. installing fire detection and extinguishing systems, reinforcing buildings to reduce explosion damage, Some products can be redesigned to eliminate the use of propellant aerosols. The hydrocarbons, propane, normal butane and isobutane are the most common substitutes for CFC and providing safety training. The average cost of converting a filling plant to hydrocarbons varies according to the location and size of the facility. Hydrocarbons generally cost between one-third and one-fifth as much as CFCs, and the savings obtained soon pay back the conversion costs. However, if the hydrocarbons need to be purified, operating costs may increase considerably. Dimethyl ether is used extensively as a propellant, particularly in Europe. It has excellent solvency and compatibility with water. Although it is flammable it can be used in aerosol filling plants if the usual safety procedures for flammable propellants are followed. Hydrocarbons and dimethyl ether share the same disadvantage: they are volatile organic compounds (VOCs) that take part in chemical reactions in the atmosphere in the presence of sunlight resulting in the production of toxic ground-level ozone. However, dimethyl ether has been used to produce low VOC formulations with a high water content, which replaces organic solvents. Aerosol products: currently available alternatives alternative propellants alternative solvents alternative delivery systems • hydrocarbons (propane, butane) • water • finger and trigger pumps • dimethyl ether • alcohols (ethanol, iso- • mechanical pressure dispensers • compressed gases (CO2, N2, N2O, air) • HFC-152a • HFC-134a • HFC-227ea • HCFC-22 and n-propanol) • chlorinated solvents perspirants, insect repellents) (methylene chloride, • rollers, brushes and cloths trichloroethylene, • bag-in-can and piston-in-can perchloroethylene) • pentane, hexane, white spirits, acetone, methyl ethyl ketone • HCFC-141b, HFC-43-10mee, volatile silicones 20 • sticks (for deodorants, anti- systems PROTECTING THE OZONE LAYER • TECHNICAL BROCHURE UPDATES • AEROSOLS AND STERILANTS Compressed gas If a coarse spray is acceptable, air, nitrogen, carbon dioxide and nitrous oxide can be used instead of CFC propellants. The main limitation with these compressed gases is that the pressure inside the container falls as it empties reducing the delivery rate, spray quality and even the quantity of spray dispensed. Careful quality control is needed to avoid propellant leaks. Carbon dioxide can produce corrosion in the can if the formula and can specifications are not carefully chosen. The percentage of aerosol products using compressed gases is currently 7–9 per cent of all products. HFCs and HCFCs HFC-134a and HFC-227ea are new replacements for CFCs. Both of these are non-flammable and both have an ODP of zero. HFC-134a is the principal replacement of CFC-12 in pharmaceutical inhalants, HCFC-22 for certain industrial products. HFC-227ea is also being used for pharmaceutical inhalants. These substances have a high global warming potential. Their use will be limited. Use of HCFC-22 is not permitted in either the United States or the European Union. HCFC-22 has been used in place of CFCs for some industrial and technical uses where non-flammable propellants are essential. HCFC-22 has also been used in some personal products, such as hair sprays and aerosol fragrances, although use in this category is minimal. HCFC-22 has a higher pressure than CFC-12. Substitutes for solvents Methyl chloroform, CFC-113 and carbon tetrachloride have all been used as solvents in aerosol formulations and they are still used in some developing countries and countries with economies in transition. These substances are all non-flammable, have large evaporation rates, high density, low viscosity and surface tension, and are reasonably low cost where they are still available. Their solvency power varies from very high (carbon tetrachloride and methyl chloroform) to very low (CFC113). CFC-113 has generally been considered safe for most uses. However methyl chloroform has much lower exposure levels and should be used only in well-ventilated places. Carbon tetrachloride is a well-known carcinogen; for that reason alone it should not be used in aerosols. It is possible to replace these solvents with non-ODS alternatives. However, in developed countries, particularly in some parts of the United States, VOC regulations have made replacement more difficult by limiting the amount of VOCs that could be used in each product category. The two properties that are most difficult to duplicate simultaneously are high evaporation rate and non-flammability. Where VOC regulations do not limit available options, formulators can usually use mixtures of chlorinated solvents, such as non-ozone-depleting methylene chloride and perchloroethylene, with alcohols, ketones, and aliphatic and/or aromatic hydrocarbons. In other cases it may be possible to replace the ozone-depleting solvent with a mixture of dimethyl ether and water. The multiplicity of aerosol products requires that each formulation has to be carefully analysed in each case to determine which characteristics are more desirable. 21 PROTECTING THE OZONE LAYER • TECHNICAL BROCHURE UPDATES • AEROSOLS AND STERILANTS Alternative non-aerosol methods Improvements in the design of finger pumps and trigger pumps have allowed these mechanical dispensing devices to increase their market share. Modern pumps are capable of dispensing fine mists of low viscosity products at any angle of operation. The disadvantages of pump sprays are that they produce larger droplets, and the spray penetrates less than that produced by aerosol products. Aerosol products still offer some unique advantages over these mechanical devices, such as total enclosure that prevents tampering with the product or oxidation due to air intake (in pumps, air is admitted to replace the liquid that is dispensed). Total investment will be lower than for an aerosol facility with similar throughput. The cost of the package for pumps is highly dependent on the style of the bottle and pump, degree of construction, order quantity, local supply and economics. However, in most cases pumps will be at least as expensive as aerosol products or even more so. On the other hand, pump dispensers can be refilled many times, thus saving cost and reducing waste. The solid stick dispenser is a non-spray dispenser for deodorant or antiperspirant. Pack costs for solid sticks vary with the degree of package sophistication and will, in some cases, exceed the price of an aerosol can and valve. However, the finished product will last longer than an aerosol product, with substantial savings to the customer. Capital costs for filling and assembling of roll-on dispensers are lower than those for an aerosol line of similar capacity (typically half the investment cost). Alternatives to propellant aerosol products. suction created by trigger action product drawn up dip tube product in bag product product piston propellant propellant in bag propellant In two compartment aerosol (or “pressurized”) products the concentrate and propellant inside the aerosol package are separated, either by use of a piston, an inner bag containing the product, or an expanding bag containing propellant. A number of systems are available, some of which have been commercialized for a long time. Designed originally for dispensing of viscous products (gels, pastes, cheese spreads, etc.) they can be used with liquids to provide a propellant free spray. A two compartment pressurized can costs about twice as much as a normal aerosol product. Special filling machines that are more expensive than normal aerosol fillers are needed for these systems. 22 PROTECTING THE OZONE LAYER • TECHNICAL BROCHURE UPDATES • AEROSOLS AND STERILANTS Potential problems Specialized aerosol product uses CFCs are difficult to replace for some specialized uses of aerosol products. Propellants in medical aerosol products must be neither toxic nor flammable. Propellants and solvents in aerosol products used for many industrial purposes must be non-flammable and inert. CFCs are still being used as propellants in some developing countries, for medical aerosol products containing substances such as anaesthetics and antiseptics. Medical aerosol products that are not inhaled can be converted to alternative propellants, dispensed by mechanical pump sprays, or produced as powders. The CFC-free products will need to be approved by local health authorities. This can be a lengthy process. CFCs are also used as propellants and solvents in aerosol products for lubricating, cleaning and faultchecking of electrical equipment. Most of these products have been converted to use HFC-134a as propellant. HCFC-141b can be used in developing countries as a partial replacement for CFC-113, but its use for this purpose is not allowed in developed countries. Developing countries’ perspective Use of CFC in aerosols in developing countries is declining slowly. A faster decline will not occur unless the specific problems of reformulation of medical aerosols and industrial and technical aerosols are solved. Where lack of availability of hydrocarbons is stopping conversion of non-metered dose inhaler medical aerosols, availability problems need to be solved. Final phase out of the use of CFCs will also require conversion of small users, overcoming any potential public safety issues for small aerosol fillers operating in congested areas. Final phase out As most aerosol products have been converted to non-ODS propellants and solvents, an accelerated phase out of CFCs would be relatively simple. In 2000, it was estimated that less than 10,000 tonnes of ozone-depleting substances were used worldwide in the manufacture of aerosols (excluding MDIs). Most of this amount was used for the manufacture of non-MDI medical aerosols in developing countries and countries with economies in transition. 23 PROTECTING THE OZONE LAYER • TECHNICAL BROCHURE UPDATES • AEROSOLS AND STERILANTS Metered dose inhalers Currently available alternatives to CFC-based metered dose inhalers (MDIs) are, primarily: • CFC-free MDIs; • dry powder inhalers (DPIs) (single or multi-dose); • nebulizers (hand held or stationary); • orally administered drugs (tablets, capsules or oral liquids); • and injectable drugs. All the CFC-free MDIs under development contain the same components as the CFC products, but the very different physical properties of the HFC propellants have meant that significant changes have had to be made. CFC-free MDIs will contain the new propellants HFC-134a or HFC-227ea, and some products may contain both. The HFCs have very different properties to the CFCs. This has resulted in new formulations being developed. The CFC-free MDI may superficially look the same as the CFC MDI, but it will have a different taste and mouth feel that will be obvious to the user. In the future, alternatives are likely to include non-CFC MDIs, new DPIs, new nebulizers, novel noninhaled treatments, and new propellant-free inhalation devices. Some of these are already on the market, and many others are in the late stage of development or under regulatory evaluation. They will reach the market place in the next few years. DPIs can now be used successfully for most anti-asthma drugs. These inhalers are an immediately available alternative for a large proportion of patients, although they may not represent a satisfactory alternative to the pressurized MDIs for all patients or for all drugs. Currently available DPIs are lightweight and portable like MDIs; they require less coordination to use than most MDIs; they have the potential to use pure drugs without additives; they are difficult for patients with very low inspiratory flow, e.g. small children and the elderly; they may require special packaging for use in humid climates; some require special handling during use; the cost compared with MDIs varies between products and countries; patient acceptability is not uniform. In some countries, over 85 per cent of inhalers used are DPIs. There is an increasing use of the multi-dose dry powder inhaler and this is likely to accelerate as new multiple dose devices are produced, particularly as they may be more suitable for young children, provided their inspiratory flow is sufficient. DPI usage globally, as a percentage of all inhaled medication, is estimated to be around 17 per cent. This figure varies considerably from country to country. For example, it is currently 85 per cent in Sweden, less than 2 per cent in the USA, and no DPIs are available yet in Japan. It seems unlikely that uptake of DPIs in most countries will be at the levels seen in Scandinavian countries. Nebulizers are devices that are filled with a drug that is dissolved or suspended in aqueous solution and that is converted to inhalable droplets using compressed air or ultrasonic waves. Nebulizers are generally not considered to be alternatives to MDIs. They are mainly restricted to the treatment of infants and severely ill patients where patient cooperation is minimal, or to situations when larger doses of drug and/or prolonged administration times are desired. Oral medications include tablets, capsules, and oral liquids and have been the standard form of therapy for most diseases for many years. For existing products such as steroids and 24 PROTECTING THE OZONE LAYER • TECHNICAL BROCHURE UPDATES • AEROSOLS AND STERILANTS bronchodilators, tablet therapies involve higher doses and greater risk of side effects. Regulatory authorities in some countries have approved novel oral compounds (e.g. leukotriene modifiers) for the treatment of asthma. These may be of value to certain asthma sufferers, but it is unlikely that they will be a full substitute for the current inhaled preventive therapy. Some drugs used for the treatment of asthma and COPD are also available in injection form. However, injection is not practical for general use in ambulatory patients. It is therefore reserved for the treatment of hospitalized patients. Continued provision of MDIs in developing countries will depend either on import of products or local production. Local production of CFC MDIs is likely to continue for some time after cessation of their use in developed countries and will overlap with the importation and local production of CFC-free MDIs by multinational and national companies. Local production of CFC-free MDIs by a local producer, a multinational company, or by a local producer in collaboration with a multinational company will require the transfer of new technologies and may require new licensing arrangements and transfer of intellectual property. The costs of local production of CFC-free inhalers will include capital costs and licensing arrangements. Multinational companies operating in Article 5 countries should be encouraged to make the technology transfer as soon as possible. One company is already committing resources to set up manufacturing capacity for HFC MDIs in Latin America (Brazil) and Eastern Europe (Poland). The manufacturing plants will be operational in the next couple of years and will serve local and regional market needs. 25 PROTECTING THE OZONE LAYER • TECHNICAL BROCHURE UPDATES • AEROSOLS AND STERILANTS Sterilants Ethylene oxide mixed with CFC-12 (a mixture known as 12/88) is used to sterilize medical equipment. KEY FACTS Hospitals, medical equipment manufacturers and commercial sterilizing facilities also use a range of Commercial sterilization plants can reduce CFC12 use by converting from 12/88 to techniques based on 100 per cent ethylene oxide, HCFC and ethylene oxide mixtures, 10/90 and radiation. other sterilizing substances and processes for particular products. For smaller units, such as those used in hospitals, 12/88 use can be reduced or eliminated by a combination of steam, formaldehyde, ethylene oxide or HCFC/ethylene oxide mixtures. deficiencies in the level of sterility. Not every process or sterilant will be compatible with all products. Methods for sterilization of medical and surgical equipment and devices have developed differently in each country, influenced by country-specific codes and regulations for fire protection, occupational safety, validation of results, liability considerations, availability of sterilization equipment and materials, and medical practices. Quality health care is dependent on ensuring the sterility of medical devices. Validation of processes for an intended application is important to avoid problems of incompatibility with certain materials or However, once a technology is validated for a specific application it becomes a viable alternative for that application. Alternative sterilization processes The alternative processes listed below can be used to reduce or replace the use of ozone-depleting substances in sterilization. Techniques for reducing or eliminating 12/88 use in hospitals Steam sterilization • sterilizing heatresistant equipment with steam; used for equipment that can withstand high humidity and temperatures of at least 113 °C. Steam Steam sterilization is the least expensive of all sterilization methods and is widely used by medical equipment manufacturers and hospitals. This process is non-toxic, economical and safe. It can be sterilization cannot be used to sterilize certain heat and moisture-sensitive medical equipment, e.g. the equipment used for operations such as organ transplants. • sterilizing heatsensitive equipment with formaldehyde; Hospital practice can minimize the use of mixtures of ozone-depleting substances with ethylene oxide by separating the majority of equipment that can be sterilized with steam (and/or formaldehyde) • using 100 per cent ethylene oxide sterilizers in units where this is safe and practical; from the heat- and moisture-sensitive equipment sterilized with the ethylene oxide mixture. Formaldehyde Formaldehyde has been used as a sterilant for many years. However, as it is toxic and a suspected carcinogen, its use is restricted in some countries. The most common formaldehyde sterilization process can be used on equipment that can withstand temperatures of 80–85 °C, with some • using HCFC/ethylene oxide mixtures; operating temperatures as low as 60–65 °C. • recovering and recycling 12/88. It is cheaper to sterilize with steam than formaldehyde. However, the formaldehyde process is cheaper than 12/88 and, where regulations allow, it is a viable alternative for the sterilization of equipment that can withstand the required operating temperatures. Ethylene oxide Medical equipment manufacturers and hospitals use undiluted ethylene oxide to sterilize heatsensitive materials and equipment. This flammable gas can be used where safety requirements can be met. Sterilization is usually carried out at atmospheric pressure, or below, to reduce the risk of fire and explosion. Equipment varies from large industrial units to small hospital units that use canisters 26 PROTECTING THE OZONE LAYER • TECHNICAL BROCHURE UPDATES • AEROSOLS AND STERILANTS containing less than 200 g of ethylene oxide. Safety precautions are necessary for the storage and handling of ethylene oxide. In hospitals, steam and formaldehyde are used to sterilize most equipment. Ethylene oxide is used only for heat-sensitive equipment that cannot withstand sterilization by other methods. Ethylene oxide, used in conjunction with other sterilization processes, is a possible alternative to use of 12/88 in hospitals. Blends of ethylene oxide and CO2 Non-flammable mixtures of ethylene oxide and carbon dioxide (CO2) are sometimes suitable alternatives to ODS mixtures with ethylene oxide. Common mixtures are 10 percent ethylene oxide and 90 percent CO2 (known as 10/90), and 8.5 percent ethylene oxide and 91.5 percent CO2. These mixtures are non-flammable, not explosive or environmentally damaging, and are also currently available. However, operating pressures are about ten times higher than for 12/88, requiring more expensive equipment. They also have other disadvantages, such as composition changes during the progressive use of a single tank or cylinder, increased polymerization problems, and compatibility and corrosion problems caused by the acidity of CO2. Flammable mixtures of ethylene oxide and CO2 are also used in some countries, with safety precautions necessary to reduce operating risks. Blends of ethylene oxide and HCFC-124 Blends of ethylene oxide and HCFC-124 are virtual drop-in replacements for 12/88. HCFCs are good flame-retardants; have low ODP, GWP and toxicity; are compatible with medical equipment; and blend with ethylene oxide. With minor control adjustments, these mixtures allow continued use of expensive 12/88 sterilizing equipment. The gas mixture requires validation for the particular application before use. Product and packaging compatibility needs to be established. Radiation Two radiation processes are used, one based on gamma radiation the other on electron beam irradiation. Both processes are well established and used in large facilities. Globally, a large proportion of all single-use medical products is sterilized by irradiation. Product manufacturers usually have their own on-site equipment for irradiation, whereas hospitals usually send equipment to specialized facilities for irradiation. Hospitals do not have their own facilities because of construction costs and the complexities of irradiation. For example, processes using gamma radiation need to dispose of spent isotopes and are therefore generally not acceptable for hospitals. Sterilization techniques: alternatives to 12/88 cheaper than 12/88 steam • formaldehyde • ethylene oxide suitable for heat-sensitive equipment nontoxic nonflammable • • cheapest sterilization method • use restricted in some countries some • • comments conversion costs; safety procedures essential ethylene oxide/ • • • operating problems • • • safety procedures essential • • sterilized equipment must be • virtual drop-in replacement carbon dioxide radiation dry heat • used immediately ethylene oxide/ HCFC 124 • for 12/88 27 PROTECTING THE OZONE LAYER • TECHNICAL BROCHURE UPDATES • AEROSOLS AND STERILANTS Radiation is a very reliable sterilization technique. Irradiated equipment can be released as sterile without holding it under quarantine to conduct sterility tests. However, radiation is not compatible with all materials. Some products and packaging are irreversibly damaged by radiation. Dry heat Metal and other items that can withstand temperatures up to about 190° C can be sterilized by exposure to dry heat. A wide selection of dry heat equipment is available worldwide, and is cheap to buy, operate and maintain. Items sterilized by this technique must be used immediately as they are not protected by a sterilized package. Dry heat sterilization would therefore, for instance, be a suitable technique for a small dental surgery, but not for a large hospital where equipment is unlikely to be used immediately after it is sterilized. Ionized Gas Plasma Several ionized gas plasma processes have been commercialized. In one process the plasma is generated in a hydrogen peroxide atmosphere, while in another it is generated in a peracetic acid environment. Many ionized gas plasma units have been sold worldwide, mostly to hospitals. One of these processes (using peracetic acid plasma)–and which had not received FDA approval for this application–was recently associated with patient injuries when ophthalmic surgical instruments sterilized with this system were used. A global recall of equipment using this particular ionized gas process was issued. Developing countries In 1998, total global use of blends of ethylene oxide and CFC-12 was estimated to be 1500 tonnes, consumed almost exclusively in developing countries. Most developing countries have some hospitals using advanced medical techniques and equipment. A few developing countries have at least one commercial sterilization facility, and many have one or more hospital sterilization units. To reduce CFC use, commercial sterilization facilities are phasing out 12/88 and converting to other sterilization methods. However, in some developing countries there have been indications of increased use of CFC-12, with the possibility that some surgical equipment manufacturers are shipping products from developed to developing countries for sterilization. Developing countries can take steps to minimize CFC use. Hospital practice can minimize the use of mixtures of ethylene oxide with CFC-12 by separating the majority of equipment that can be sterilized with steam (and/or formaldehyde) from the heat- and moisture-sensitive equipment sterilized with the ethylene oxide mixture. Units using 12/88 should be identified, and assistance provided to convert to 100 per cent ethylene oxide or HCFC/ethylene oxide mixtures. Developing countries can convert 12/88 equipment to the virtual drop-in replacement HCFC/ethylene oxide mixtures with no changes to operating procedures and at reasonable cost. Developing countries can also: ensure that no new commercial facilities using 12/88 are built in the country; provide commercial sterilization facilities and hospitals with technical information and financial assistance to help them convert from 12/88; train personnel in commercial facilities and hospitals in alternative techniques; and encourage hospitals to choose non-CFC technology when purchasing new sterilizers. Forecast of usage By 1998, CFC use in sterilization had been successfully eliminated in most developed countries. In 1998, use in developing counries and in some countries with economies in transition was estimated to be less than 1500 tonnes. In these countries, 12/88 can be eliminated from commercial and hospital units if financial and technical assistance is available. 28 PROTECTING THE OZONE LAYER • TECHNICAL BROCHURE UPDATES • AEROSOLS AND STERILANTS Resources Secretariats and Implementing Agencies UNDP Dr. Suely Carvalho, Deputy Chief Montreal Protocol Unit, EAP/SEED Multilateral Fund Secretariat United Nations Development Programme Dr. Omar El Arini (UNDP) Chief Officer 304 East 45th Street Secretariat of the Multilateral Fund for Room FF-9116,New York, NY 10017 the Montreal Protocol United States of America 27th Floor, Montreal Trust Building Tel: 1 212 906 6687 1800 McGill College Avenue Fax: 1 212 906 6947 Montreal, Quebec H3A 6J6 Canada Email: [email protected] Web site: www.undp.org/seed/eap/montreal Tel: 1 514 282 1122 Fax: 1 514 282 0068 E-mail: [email protected] Web site: www.unmfs.org UNIDO Mrs. H. Seniz Yalcindag, Chief Industrial Sectors and Environment Division United Nations Industrial Development UNEP Ozone Secretariat Mr. Michael Graber Acting Executive Secretary UNEP Ozone Secretariat PO Box 30552 Gigiri, Nairobi Kenya Tel: 2542 623-855 Fax: 2542 623-913 Organization (UNIDO) Vienna International Centre P.O. Box 300 A-1400 Vienna Austria Tel: (43) 1 26026 3782 Fax: (43) 1 26026 6804 E-mail: [email protected] Web site: www.unido.org Email: [email protected] Web site: www.unep.org/ozone World Bank Mr. Steve Gorman, Unit Chief UNEP Mr. Rajendra M. Shende, Chief Energy and OzonAction Unit United Nations Environment Programme Division of Technology, Industry and Economics (UNEP DTIE) 39-43 quai Andre Citroen 75739 Paris Cedex 15 Montreal Protocol Operations Unit World Bank, 1818 H Street NW Washington DC 20433 United States of America Tel: 1 202 473 5865 Fax: 1 202 522 3258 Email: [email protected] Web site: www.esd.worldbank.org/mp/home.cfm France Tel: 33 1 44 3714 50 Fax: 33 1 44 3714 74 Email: [email protected] Web site: www.uneptie.org/ozonaction 29 PROTECTING THE OZONE LAYER • TECHNICAL BROCHURE UPDATES • AEROSOLS AND STERILANTS Contact points American Hospital Association American Chemistry Council 840 North Lakeshore Drive (Formerly the Chemical Manufacturers Association) Chicago, IL 60675 703-741-5000 phone United States 703-741-6000 fax Tel: 1 312 280 6360 1300 Wilson Blvd. Fax: 1 312 280 5923 Arlington, VA 22209 http://www.aha.org http://www.cmahq.com/ Comité Français des Aérosols Asociación Española de Aerosoles 32 rue de Paradis Loreta 2-Entresuelo 4°, 08029 F-75484 Paris Cedex 10 Barcelona, Spain France Tel: +34 93 410 60 65 Tel: 1 47 70 26 42 Fax: +34 93 419 37 56 Fax: 1 47 70 34 84 [email protected] http://www.aerosols-info.org/index.html Associação Portuguesa de Aerossois European Council of Chemical Manufacturers Avenida Antonio José d’Almeida Nº 7-2º Federations 1000 Lisbon, Portugal Avenue E. Van Nieuwenhuyse, 4 Tel: +351 1 799 1550 B-1160 Brussels Fax: +351 1 799 1551 Belgium [email protected] Tel: 322 676 7211 Fax: 322 676 7300 Association for the Advancement of Medical http://www.cefic.org/ Instrumentation 3330 Washington Boulevard Federation of European Aerosol Associations Suite 400 Square Marie-Louise, 49 Arlington, VA 22201-4598 B-1040 Brussels United States Belgium Tel: 1 703 525 4890 Tel: 322 238 9711 Fax: 1 703 276 0793 Fax: 322 231 1301 http://www.aami.org/ http://www.aerosol.org/ British Aerosol Manufacturers Association Health Industry Manufacturers Association King’s Buildings 1200 G Street, NW 16 Smith Square Washington, DC 20005 London SW1P 3JJ United States United Kingdom Tel: 1 202 783 8700 Tel: 71 828 5111 Fax: 1 202 783 8750 Fax: 71 834 8436 http://www.bama.co.uk/ Hellenic Aerosol Association (includes directory of global aerosol associations and Eleftherias & Melpomenis str government departments) 15th Klm Nat.Rd Athens-Lamia, 14564 Kifissia-Athens, Greece Suomen Aerosoliyh Tel: +30 1 80 77 403 (Finnish Aerosol Association) Fax: +30 1 80 76 084 PO Box 073 E-mail: [email protected] SF-00131 Helsinki Finland International Aerosol Association Tel/Fax: 358 01 3451400 Waisenhausstrasse, 2 E-mail: [email protected] CH-8001 Zurich Switzerland Tel: 01 211 5255 Fax: 01 221 2940 30 PROTECTING THE OZONE LAYER • TECHNICAL BROCHURE UPDATES • AEROSOLS AND STERILANTS Further reading Brandberg et al. Sterilisering med etylenoxid (EO). På 4:e året i Göteborgs sjukvård, Sjukhuset, nr 2/1985, årgång 62. ‘CFC Replacement, Are we Ready?’ Deposition, Clearance and Effects in the Lung, Consensus Seminars on Issues of Aerosol Therapy. Davos, Switzerland, April 1991. Journal of Aerosol Medicine, Vol 4 No 3 1991. Chest, The Environmental Impact of Chlorofluorocarbon Use in Metered Dose Inhalers. 100, No. 4 October 1991. CMA reporting companies. Grant Thornton Report 1991. Chlorofluorocarbons (CFCs) 11 and 12 – Cumulative Production through 1979 and Annual Production and Sales for the years 1980–l989. CMA, Washington D.C., United States. Figurama, Metal Box Aerosols, l987. Independent Committee on Smoking and Health. Developments in Tobacco Products and the Possibility of ‘Lower Risk’ Cigarettes. Second Report, page 7, 1979. Midwest Research Institute. Addenda to EPA Regulatory Impact Analysis Document, Miscellaneous Uses, vol III, part 5. October 1987. Midwest Research Institute. Addenda to EPA Draft Regulatory Impact Analysis, vol III, part 6, Sterilants. October 1987. National Swedish Environmental Protection Board. CFCs/Freons – Proposals to Protect the Ozone Layer. Report 3410. Radian, Essential Aerosols Update. EPA Contract No. 68-02-4288, January 1989. UNEP. Report of the Aerosol Products, Sterilants, Miscellaneous Uses and Carbon Tetrachloride Technical Options Committee, 1992. UNEP. Report of the Aerosol Products, Sterilants, Miscellaneous Uses and Carbon Tetrachloride Technical Options Committee, 1994. UNEP. Report of the Aerosol Products, Sterilants, Miscellaneous Uses and Carbon Tetrachloride Technical Options Committee, 1998. UNEP. Report of the Technology and Economic Assessment Panel, 2001. USEPA. Future Concentrations of Stratospheric Chlorine and Bromine. USEPA, 1989. 31 PROTECTING THE OZONE LAYER • TECHNICAL BROCHURE UPDATES • AEROSOLS AND STERILANTS Glossary CFC 32 chlorofluorocarbon carcinogen causing cancer in animals and humans compressed gas a high pressure propellant that behaves like a gas inside the aerosol DPI dry powder inhaler DME dimethyl ether GWP global warming potential HCFC hydrochlorofluorocarbon HFC hydrofluorocarbon hydrocarbon organic substance made of hydrogen and carbon MDI metered dose inhaler mutagenic causes mutation ODP ozone-depletion potential OAIC OzonAction Information Clearinghouse ozone gas formed from three oxygen atoms propellant a liquid or gas inside an aerosol product that provides pressure to expel the contents VOC volatile organic compound – constituents will evaporate at temperature of use, and may react photochemically with atmospheric oxygen to produce toxic and smog-producing tropospheric ozone 12/88 a mixture of ethylene oxide and CFC-12 in the proportion 12:88 per cent 10/90 mixture of ethylene oxide and CO2 in the proportion 10:90 PROTECTING THE OZONE LAYER • TECHNICAL BROCHURE UPDATES • AEROSOLS AND STERILANTS About the UNEP DTIE OzonAction Programme Nations around the world are taking concrete actions to reduce and eliminate production and consumption of CFCs, halons, carbon tetrachloride, methyl chloroform, methyl bromide and HCFCs. When released into the atmosphere these substances damage the stratospheric ozone layer – a shield that protects life on Earth from the dangerous effects of solar ultraviolet radiation. Nearly every country in the world has committed itself under the Montreal Protocol to phase out the use and production of ODS. Recognizing that developing countries require special technical and financial assistance in order to meet their commitments under the Montreal Protocol, the Parties established the Multilateral Fund and requested UNEP, along with UNDP, UNIDO and the World Bank, to provide the necessary support. In addition, UNEP supports ozone protection activities in Countries with Economies in Transition (CEITs) as an implementing agency of the Global Environment Facility (GEF). Since 1991, the UNEP DTIE OzonAction Programme has strengthened the capacity of governments (particularly National Ozone Units or “NOUs”) and industry in developing countries to make informed decisions about technology choices and to develop the policies required to implement the Montreal Protocol. By delivering the following services to developing countries, tailored to their individual needs, the OzonAction Programme has helped promote cost-effective phase out activities at the national and regional levels: Information Exchange Provides information tools and services to encourage and enable decision makers to make informed decisions on policies and investments required to phase out ODS. Since 1991, the Programme has developed and disseminated to NOUs over 100 individual publications, videos, and databases that include public awareness materials, a quarterly newsletter, a web site, sector-specific technical publications for identifying and selecting alternative technologies and guidelines to help governments establish policies and regulations. Training Builds the capacity of policy makers, customs officials and local industry to implement national ODS phase out activities. The Programme promotes the involvement of local experts from industry and academia in training workshops and brings together local stakeholders with experts from the global ozone protection community. UNEP conducts training at the regional level and also supports national training activities (including providing training manuals and other materials). Networking Provides a regular forum for officers in NOUs to meet to exchange experiences, develop skills, and share knowledge and ideas with counterparts from both developing and developed countries. Networking helps ensure that NOUs have the information, skills and contacts required for managing national ODS phase out activities successfully. UNEP currently operates 8 regional/sub-regional Networks involving 109 developing and 8 developed countries, which have resulted in member countries taking early steps to implement the Montreal Protocol. Refrigerant Management Plans (RMPs) Provide countries with an integrated, cost-effective strategy for ODS phase out in the refrigeration and air conditioning sectors. RMPs have to assist developing countries (especially those that consume 33 PROTECTING THE OZONE LAYER • TECHNICAL BROCHURE UPDATES • AEROSOLS AND STERILANTS low volumes of ODS) to overcome the numerous obstacles to phase out ODS in the critical refrigeration sector. UNEP DTIE is currently providing specific expertise, information and guidance to support the development of RMPs in 60 countries. Country Programmes and Institutional Strengthening Support the development and implementation of national ODS phase out strategies especially for low-volume ODS-consuming countries. The Programme is currently assisting 90 countries to develop their Country Programmes and 76 countries to implement their Institutional-Strengthening projects. For more information about these services please contact: Mr. Rajendra Shende, Chief, Energy and OzonAction Unit UNEP Division of Technology, Industry and Economics OzonAction Programme 39-43, quai André Citroën 75739 Paris Cedex 15 France E-mail: [email protected] Tel: +33 1 44 37 14 50 Fax: +33 1 44 37 14 74 www.uneptie.org/ozonaction.html 34 UNEP PROTECTING THE OZONE LAYER • TECHNICAL BROCHURE UPDATES • AEROSOLS AND STERILANTS About the UNEP Division of Technology, Industry and Economics The mission of the UNEP Division of Technology, Industry and Economics is to help decision-makers in government, local authorities, and industry develop and adopt policies and practices that: • are cleaner and safer; • make efficient use of natural resources; • ensure adequate management of chemicals; • incorporate environmental costs; • reduce pollution and risks for humans and the environment. The UNEP Division of Technology, Industry and Economics (UNEP DTIE), with its head office in Paris, is composed of one centre and four units: • The International Environmental Technology Centre (Osaka), which promotes the adoption and use of environmentally sound technologies with a focus on the environmental management of cities and freshwater basins, in developing countries and countries in transition. • Production and Consumption (Paris), which fosters the development of cleaner and safer production and consumption patterns that lead to increased efficiency in the use of natural resources and reductions in pollution. • Chemicals (Geneva), which promotes sustainable development by catalysing global actions and building national capacities for the sound management of chemicals and the improvement of chemical safety world-wide, with a priority on Persistent Organic Pollutants (POPs) and Prior Informed Consent (PIC, jointly with FAO). • Energy and OzonAction (Paris), which supports the phase out of ozone depleting substances in developing countries and countries with economies in transition, and promotes good management practices and use of energy, with a focus on atmospheric impacts. The UNEP/RISØ Collaborating Centre on Energy and Environment supports the work of the Unit. • Economics and Trade (Geneva), which promotes the use and application of assessment and incentive tools for environmental policy and helps improve the understanding of linkages between trade and environment and the role of financial institutions in promoting sustainable development. UNEP DTIE activities focus on raising awareness, improving the transfer of information, building capacity, fostering technology cooperation, partnerships and transfer, improving understanding of environmental impacts of trade issues, promoting integration of environmental considerations into economic policies, and catalysing global chemical safety. 35 www.unep.org United Nations Environment Programme P.O. Box 30552 Nairobi, Kenya Tel: (254 2) 621234 Fax: (254 2) 623927 E-mail: [email protected] web: www.unep.org
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