[] TL: CLEAN OPPORTUNITIES Without Chlorinated Solvents (GP) SO: Greenpeace Sweden DT: May 1989 Keywords: toxics pulp ozone chlorine alternatives greenpeace groups sweden reports gp effluent / [part 1 of 4] CONTENTS 1. Prevent environmental problems at the source! 2. Chlorinated solvents 2.1 occurrence in the environment 3. Effects on health and the environment 3.1 health effects 3.2 effects on the ozone layer 3.3 climate effects 3.4 other environmental effects 4. Chlorinated solvents in Sweden 4.1 production 4.2 import/export 4.3 transport 4.4 uses 4.5 waste treatment 5. Alternatives 6. Regulatory measures 7. Summary 8. Greenpeace demands 9. Appendix 1: Alternatives to halogenated solvents 10. References Biological life is an extremely delicate phenomenon. It thrives only under very particular and delicately balanced conditions. We call these conditions our environment. 1. PREVENT ENVIRONMENTAL PROBLEMS AT THE SOURCE! Today there are about 8 million registered chemicals in the world. Most of them exist only in laboratories, but 60,000 to 70,000 of them are used daily by industries and individuals in our society. Industrialism has created such a multiplicity of chemicals for so many purposes that we have almost completely lost control over the effects. Every one of these substances affects its environment. A few of them are necessary for life, while others have negative effects on our health, on animal and plant life, or on the climate. Most chemicals are produced by man, and do not occur naturally. Unlike natural substances, which have a cycle in nature, these synthetic substances flow along a one-way street. We use raw materials and "refine" them into products which, after they are used, become persistent and toxic waste. Many new substances are stable; i.e. they are virtually immune to biological breakdown, and therefore they will be in our environment for a long time. One example is freon, which will lead to damage of the ozone layer for at least the next 100 years. DDT and PCB are other "old" environmental toxins that will continue to cause damage for decades. If the use of synthetic chemicals is allowed to keep increasing, we risk a steady increase in environmental crises. The flood of chemicals has to be reduced - but how? Is it possible to break the trend? Traditionally, environmental efforts in Sweden have focused on reducing the environmental load caused by emissions of various kinds. Purification plants are built to take care of harmful substances in industrial and household wastes. We use incinerators to try to destroy the toxins we have produced. The problem is that most of the synthetic (un-natural) substances that we have produced can't be destroyed, only redistributed. Purification plants transfer the chemicals from the water to the sludge. Incineration creates gases containing new and often even more toxic substances. We must ask ourselves where all these poisonous substances come from. We must stop the creation of waste and toxic emissions. We can't afford to make any more mistakes. Adopting a preventive strategy will open a wide range of new opportunities to avoid negative environmental consequences in the future. Such an attitude may make today's environmental problems unnecessary, perhaps even unprofitable. Greenpeace would like to demonstrate that this is possible. In this report we describe a major environmental problem. It is only one of the problems we face today. But by showing how a preventive strategy can be applied here, we indicate a better approach for present and future use of chemicals. 2. CHLORINATED SOLVENTS. A solvent, as the name implies, is something that dissolves something else. The most common solvent is ordinary water. Most substances are soluble in water. Many substances foreign to nature, however, are not soluble in water. Their chemical characteristics are wrong. To dissolve them, you have to use substances not found in the natural environment. Various petroleum-based organic solvents are therefore produced, with qualities that make them suitable for this purpose. Table 1 lists a few of the most common of these organic solvents. Table 1. A few common organic solvents. Hexane Phenol Styrene Toluene Benzene Xylene Naphthalene Acetone Acetonitrile Formaldehyde Chlorinated solvents are organic solvents that contain the element chlorine. This gives them certain special characteristics. The most common chlorinated solvents are listed in Table 2. Table 2. The most common chlorinated solvents. Name Systematic name Example of use Methyl chloroform 1,1,1-trichloroethane cleaner Methylene chloride 1,2-dichloroethene paint remover Trichloroethylene (tri) trichloroethene degreaser Perchloroethylene (per) tetrachloroethene drycleaning Carbon tetrachloride tetrachloromethane metal cleaning Methyl chloride chloromethane coolant, paint remover Chloroform trichloromethane metal cleaning Ethylene dichloride (EDC) 1,2-dichloroethane PVC manufacture Vinyl chloride vinyl chloride PVC manufacture The element chlorine is classified as a halogen. The other halogens are bromine, iodine and fluorine. Organic substances that contain halogens are called halogenated hydrocarbons. In addition to chlorinated solvents, this group contains many other environmental toxins such as the pesticides DDT and lindane, and also dioxins and PCBs (polychlorinated biphenyls). It is important to remember that all organic solvents cause environmental problems. We have decided to limit this report to the chlorinated solvents, since many of these have particularly serious effects on the environment and on human health. Our ultimate goal, however, must be to phase out the use of all stable and toxic organic solvents. 2.1 Occurrence in the environment. The most common chlorinated solvents are today spread around the world. Since the substances are volatile, they evaporate very easily. They are found at all levels in the atmosphere and in areas remote from human activities. They are in the oceans, in the groundwater and in our food. A few chlorinated solvents can be formed by natural processes. One of these is methyl chloride, which can be produced by bacteria in the oceans (2, 3). The substance is also formed by forest fires and by human activities such as garbage incineration (4). Other chlorinated solvents originate entirely within our industrialized society. For these, no natural source has been found. Of the total atmospheric content of halogenated hydrocarbons, less than 1 percent comes from natural sources (5). Chlorinated solvents also occur as a result of industrial use of chlorine. Chloroform can be formed in drinking water as a result of chlorination, and also in water used for cooling in industry. It is also formed in large amounts with chlorine bleaching of paper pulp (6, 7). The amount of a chlorinated solvent in the atmosphere is determined by the lifetime of the substance in question and the rate at which it is added by emissions. Carbon tetrachloride, which is an extremely stable substance in the atmosphere, remains in the air for over half a century. Since the substance has been used in large amounts during the past decades, high concentrations have already been accumulated. Table 3. Global emissions and lifetimes of some chlorinated substances. Substance Emission Lifetime in Reference (1000 ton/year) atmosphere Methyl chloride 2500-5000 1-2 years (2) Methylene chloride 240-270 77 days (8) Chloroform 210 100 days (9, 10) Carbon tetrachloride 66 67 years (11) 1,2-dichloroethane 1200 56 days (9) 1,1,1-trichloroethane 474 8 years (11) Lifetime in the atmosphere: The literature reflects considerable variation in this value. Calculations include emission data, mixing in the atmosphere, transformation processes etc. These data are uncertain for several reasons. The values in the table should therefore be regarded as representative approximations. 3. EFFECTS ON HEALTH AND THE ENVIRONMENT. 3.1 Health effects. Chlorinated solvents have been used in industry for several decades. Their health effects in the working environment are therefore quite well known. Our understanding of the health risks of chlorinated solvents has changed dramatically during the 50 years they have been in use. They were initially regarded as relatively harmless substances with low toxicity. The danger of skin damage or poisoning from long-term inhalation was of course known, but not considered a hindrance to their use. Even into the 70s vinyl chloride was thought generally harmless, and even used as a propellant in spray cans! Many chlorinated solvents are fat-soluble, and thus accumulate in the fatty tissues of animals and man. This enrichment enhances the harm they do. Many of them are classified as carcinogens. Table 4 gives a brief survey of the health effects of some common chlorinated solvents. When these solvents break down, they form new substances that are often as toxic as the original substance - sometimes even more so. "Tri" and "per" break down into vinyl chloride (12). Many commercially sold solvents also contain toxic additives or contaminants. One such is 1,4-dioxane, which can occur as a stabilizer in methylene chloride, trichloroethane etc. (13): 1,4- dioxane is a carcinogen (14). 3.2 Effects on the ozone layer. Chlorinated solvents are stable substances with long lives in the atmosphere. They either gradually break down in the troposphere or are further transported up to the stratosphere. The use of freons (CFC) contributes to the thinning of the earth's ozone layer. This fact has resulted in a prohibition on the use of freons in Sweden as of 1994. The environmental problem arises when the stable freons reach the stratosphere where they are broken down by solar radiation, releasing free chlorine atoms. This chlorine is extremely reactive, and quickly breaks down the surrounding ozone. A single chlorine atom breaks down several hundred ozone molecules. The chlorinated solvents that reach the stratosphere are broken down in the same way as freons, and have the same dire effect on the ozone layer. Only a very small part of emissions of the most stable solvents reaches the stratosphere (10), but since the global emission is so large solvent use nevertheless has a considerable effect on the ozone layer. Other factors also play a role. There are indications that perchloroethylene in the atmosphere breaks down to the considerably more stable carbon tetrachloride (16). The use of "per" therefore may contribute considerably more to the ozone problem than earlier believed: possibly up to 4% of chlorine in the stratosphere. Emissions of carbon tetrachloride are estimated to cause about 10% of ozone breakdown in the stratosphere (17). Table 4. Summary of the health effects of some common chlorinated solvents found in the working environment. Substance Health effect Metbylene chloride Suspected carcinogen. Bacterial mutagen. Irritates respiratory passages, eyes and skin; easily penetrates skin. When heated creates phosgene, an extremely toxic gas that can severely damage lungs, etc. Transformed in the body to carbon monoxide, which reduces the blood's ability to carry oxygen and can cause brain damage. Trichloroethylene Suspected carcinogen. Carcinogenic in animal experiments. Bacterial mutagen. Forms phosgene when heated (see above). Perchloroethylene Suspected carcinogen. Can damage nervous system, liver, kidneys, brain. Forms phosgene when heated (see above). Chloroform Carcinogenic. Absorbed via lungs and skin. Accumulates in fatty tissue. Can damage nervous system, liver, kidneys, brain. Breaks down into carbon monoxide (see above). Carbon tetrachloride Carcinogenic. Easily absorbed by skin contact. Forms phosgene when heated (see above). Can damage nervous system, brain, etc. 1,2-Dichloroethane Carcinogenic. Easily absorbed by lungs and skin. Can damage liver and kidneys. Vinyl chloride Carcinogenic. Easily absorbed by lungs and skin. Suspected to affect fetuses. 1,1,1-Trichloroethane Suspected carcinogen. Irritates eyes and respiratory passages. Methyl chloride Damage to brain and nervous system. Can also damage liver, lungs, kidneys. Substances listed as carcinogenic are so classified by the National Swedish Institute of Occupational Health (14). A brief summary of health risks is given for each substance in References 13 and 15. 3.3 Climate effects. Chlorinated solvents also contribute to the rise in global temperature that is now occurring: the "greenhouse effect." This warming is caused by substances in the atmosphere that absorb the heat radiated by the earth. Carbon dioxide is the most important "greenhouse gas" but chlorinated hydrocarbons are also important. They absorb a somewhat different type of heat radiation and thus don't "drown" in the large amounts of CO2. Chlorinated hydrocarbons are therefore considered to have as much or nearly as much importance as carbon dioxide for the greenhouse effect (1). 3.4 Other environmental effects. When chlorinated solvents break down they form hydrochloric acid, which contributes to the acidification of rainwater and soil. Hydrochloric acid is ranked the third most important cause of acidification, after oxides of sulfur and nitrogen (18). It has been calculated that the present global emission of chlorinated hydrocarbons yields at least 2 million tons of hydrochloric acid per year. The OECD countries alone emit 600,000 tons of chlorine annually as chlorinated solvents (19). In addition to contributing to acidification of the environment and corrosion of metal, hydrochloric acid has the ability to form microscopic drops in the air (aerosols). Particularly trichloroethylene, because of its relatively short lifetime (3 to 7 days), contributes to the formation of aerosols known as smog. Many states in the U.S. recommended earlier that 1,1,1- trichlorethane be used as a replacement for "tri" in order to reduce the smog problem (20). [] TL: CLEAN OPPORTUNITIES Without Chlorinated Solvents (GP) SO: Greenpeace Sweden DT: May 1989 Keywords: toxics pulp ozone chlorine alternatives greenpeace groups sweden reports gp effluent / [part 2 of 4] 4. CHLORINATED SOLVENTS IN SWEDEN. The effects of chlorinated solvents on health and the environment are thus well documented. Sooner or later, 100% of the amount used enters the environment. There - in pure form, as breakdown products or after reacting with other substances -they affect plants, animals and humans. Material flow analysis - a way to understand the problem In order to prevent environmental problems, an understanding of how toxins are spread is of critical importance. This makes it easier to find the sources and to take measures to prevent emissions of toxic substances into the environment. A material flow analysis makes it possible to follow the paths a substance can take from the time it is imported or produced until it is finally used and becomes waste, or is exported from the country. It is important to study not only pure chemicals, but also goods and products that contain these chemicals. The number of pathways studied depends on the amount of detail needed in the analysis. Some of the most important are the following: production Import/export Transportation Use Waste handling 4.1 Production. Chlorinated solvents are no longer produced industrially in Sweden. From 1933 to 1986, however, trichloroethylene and perchloroethylene were produced at Skoghall Kemi in Karlstad (21). Norsk Hydro Plast AB in Stenungsund produces 1,2-dichloroethane (EDC), but only for use in the company's PVC production. Most of the amount used in Sweden is imported from the Common Market countries, where trans-national chemical companies dominate the market. A large proportion is imported from ICI plants in West Germany and Great Britain. ICI is one of Europe's chemical giants, with a total annual turnover of about 120 billion SEK (USD 20 billion). ICI produces large amounts of freons and other chemicals. The company's factory in Runcan, Merseyside, England, produces some of the chlorinated solvents exported to Sweden. The Runcan factory lies in one of England's most polluted areas. ICI's emissions into the nearby Mersey river contain high amounts of chlorinated toxins. Limit values for emissions of chlorinated solvents have often been exceeded. The company was taken to court several times during the 80s, but was never convicted (22). 4.2 Import/export. The law on chemical products places the environmental responsibility for a chemical on the importer/manufacturer (see section 6). It is thus the responsibility of the company itself to research the health and environmental effects of the chemical's use. One Swedish importer of solvents is Malmsten and Bergvall in Gothenburg. They sell and distribute chemicals, raw plastics and other raw materials. The company is importer, wholesaler and sales agent for several chlorinated solvents, including trichloroethylene, perchloroethylene, 1,1,1-trichloroethane and chloroform. M&B also imports around 4,000 other chemicals. Skoghall Kemi - a spider in the chemical net Skoghall's shipments of solvents and chlorine provide a good illustration of how chemicals travel in and out across Sweden's borders. Skoghall Kemi (formerly Billerud Kemi) manufactures chlorine that is exported to the chemical company ICI in West Germany. ICI uses the chlorine to produce solvents and sends these products back to Skoghall, which in turn sells them to Swedish industry as degreasers, etc. Skoghall sells about 10,000 tons of solvents per year to various users. About 1,500 tons of the degreasers used by industry are recovered by Skoghall and sent to England for purification. This then goes to ICI, where it is mixed with newly produced solvents. But of the 10,000 tons initially distributed, only a few hundred kilos can be re-used (23, 24). Norsk Hydro Plast AB annually generates over 1,000 tons of chlorine waste from vinyl chloride manufacture (25). This waste is also sent to ICI in England, where it is used to make tri-and perchloroethylene, which is subsequently imported by Skoghall Kemi and sold on the Swedish market. Skoghall is involved several ways in solvent handling. The company phased out manufacture, considering it too difficult to meet Sweden's increasingly stringent environmental regulations, and decided instead to buy solvents from other countries. What responsibility does the company take today for the environmental effects of these solvents? Government control The customs office keeps some statistics on import an export. The statistics contain information only on substances occurring in pure form, not those in imported products. Sometimes statistics for several substances are added together under a single heading, and some information is confidential. How reliable are the customs statistics? According to information from the Customs Office (26), in 1987 Sweden imported about 200 tons of chloroform. That same year, we exported about 60,000 tons. Sweden has no domestic production of chloroform. The Swedish National Chemicals Inspectorate (Kemikalieinspektionen) is the authority that supervises use of chemicals in Sweden. All importers and manufacturers are required to report all handling of solvents, and this information is assembled in the Inspectorate's product register. The product register, however, has several major shortcomings. Some of the information is classified as confidential to protect company secrets, for example, making it difficult to use the register's information for surveys of chemical use. Companies are required to register import and manufacture, but the statistics in the product register usually don't show these figures separately. Volumes and contents of substances are reported within such wide ranges that the statistics are in general worthless. For trichloroethylene, for example, the product register indicates a use between 3,500 and 21,000 tons (in 1987). Importers and manufactures make their own assessments of how dangerous their products are and whether alternative raw materials or less dangerous production methods can be used. Products that constitute a threat to the environment but are not acutely dangerous to human health are not registered. Inconsistencies are also apparent when the information from the customs office is compared with that from the Chemicals Inspectorate. Today there is no way to survey Sweden's chemical use. 4.3 Transportation For transport, most chlorinated solvents are classified as hazardous goods. In Sweden about 15 million tons of hazardous goods are transported annually by truck or tank truck. This is a estimate made by the Central Bureau of Statistics, since the customs office keeps no such records. SJ, the state railroad, has only an estimate of the amount of hazardous goods transported by rail: about 2.5 to 3 million tons annually. The National Civil Aviation Administration keeps no statistics whatever on amounts of hazardous goods carried by air, for which they are responsible. The statistics kept by the police are limited to a few spot checks. These samples indicate that about half of all hazardous goods being transported have some deficiency in security, marking, handling, etc. (37). One source of emissions is cleaning/airing of tank trucks that have transported chlorinated solvents (28). One way to get rid of the solvent residues is to let them evaporate by leaving the truck hatches open during the return journey. What can happen in an accident? In Sweden, there are each year 250 to 300 reported accidents involving transport of hazardous goods, and many that are not reported. Five to ten of these have extended effects, causing fires or deaths or necessitating major cleanup jobs (27). Hazardous goods are often transported through cities, where accidents can have particularly serious consequences. A basic ingredient in the manufacture of chlorinated solvents is chlorine gas. At the central railway station in Karlstad, a row of tank cars filled with chlorine gas is a common sight. If a serious accident such as an explosion should occur there while the wind is blowing from the north, all the people outdoors in the central part of town would be dead within five minutes (29). There was an incident at the Karlstad station in April, 1989. Chlorine began leaking from a tank car (which later proved to be empty). The central station had to be evacuated and the car sent back to Skoghall Kemi. In other countries there have been many accidents with multiple fatalities and damage sometimes amounting to millions. In addition, chemical emissions during these accidents often have long-term effects on the environment. 4.4 Uses. Both industries and households use solvents, in pure form or as components in products ranging from industrial degreasers to home spot removers. Major users include the automotive and electronics industries. Solvents are very volatile, and evaporate rapidly during use. The largest source of emissions is products that consist mainly of trichloroethylene. Industrial emissions of solvents used in degreasing account for 3,400 tons of chlorine per year (30). Perchloroethylene is used for commercial drycleaning. With a typical drycleaning run, 1% goes into solid waste (distillation sludge), less than 1% leaves in sewage, and up to 20% evaporates. In some shops evaporation can be as high as 40%. This means that more than 95% of the cleaning fluid eventually evaporates during use (31). Since the government authorities have no comprehensive overview of the problem, one way to obtain information on solvent use and environmentally harmful emissions would be for the companies and their organizations to report how much they handle. The trade organizations, however, either say they have no statistics or refuse to divulge them. The companies also have information, of course, but this is usually kept confidential. Smaller wholesalers release no information whatever on users or customers. Processing Chlorinated solvents are used as ingredients in a large number of chemical products and goods that are distributed throughout the world. Usually with no control whatever. In 1987 Norsk Hydro Plast AB in Stenungsund produced 70,000 tons of 1,2-dichloroethane for manufacture of PVC plastic, but for that year the Chemical Inspectorate's product register shows only 11,000 tons reported for all of Sweden. The company released 16 tons of 1,2-dichloroethane to the air during 1987, not counting "diffuse leakage" (32). 4.5 Waste treatment. Solvent wastes and other chemical wastes are a major environmental problem. Questionnaires have been used to discover how companies and households dispose of these wastes. In drycleaning shops, for example, some goes into ordinary garbage disposal, some goes to SAKAB (Svensk AvfallsKonvertering AB in Kumla), some is poured into the sewage system; and some people bury the hazardous waste in the garden (33). Environmentally hazardous wastes containing chlorinated solvents are received by SAKAB for incineration. A high chlorine content in the waste creates new toxins in the stack gases and in the ash (34). Dioxins and PCBs are only a few of the hundreds of chlorinated toxins in emissions from SAKAB. Most of them are unidentified. To dilute the problem, the chlorine-loaded waste is mixed with other waste before incineration. Chlorinated solvents are today the dominant source of chlorine at SAKAB. Export of environmentally hazardous wastes SAKAB receives about 38,000 tons of waste per year. Of this, 30,000 tons is incinerated and the rest is stored in outdoor depots. But we produce so much toxic waste in Sweden that SAKAB can handle only a small part of it. The rest of our waste is therefore exported to various Western European countries and then re-shipped to the Third World, where the industrialized countries have their chemical waste dumps (9). The National Swedish Environment Protection Board (Naturvhrdsverket) has the overall responsibility for supervision and monitoring of emissions, and also for issuing permits for export of toxic wastes. In 1987 permits were issued for export of 45,000 tons of toxic wastes. One exporter of toxic waste is Ciba-Geigy in Gothenburg, which exports 250 tons of solvent waste annually to Switzerland (23). 5. ALTERNATIVES. For most uses of chlorinated solvents in Sweden, there are alternative processes and products that are more acceptable from an ecological point of view. Appendix 1 presents a review of alternatives (with references). Here we will take up a few illustrative examples. Alternatives can be divided into three groups: chemical alternatives, process alternatives and system alternatives. Chemical alternatives The principle here is to find chemicals that will do the same job without having the disadvantages of the chemicals currently used. The chlorinated solvents that are foreign to nature are replaced with a natural substance such as water, our most common solvent. The largest industrial use of chlorinated solvents is for degreasing. Here there are replacements based on natural substances such as terpenes or alcohols. For better effect these can sometimes be combined with an ultrasonic bath, and then water-soluble detergents can also be used. Among consumer products, "Tipp-ex" is a good example of a product for which there is already an alternative. The solvent 1,1,1-trichloroethane is replaced by water. Water-based alkaline detergents are used for car washing at many gas stations, but are not marketed as consumer products since there is considered to be no demand for them. It's obvious that consumers won't request products if they don't even know they exist! Process alternatives Replacing a chemical with a safer one generally requires that the process be adapted. The purpose of the process remains the same, e.g. to obtain a certain product. Choosing the right process alternative sometimes makes it possible to completely eliminate the use of solvents. To avoid degreasing, for example, laser techniques can replace metalworking processes such as die stamping and machining. For paint removal, alternative processes can be based on freezing or burning, or on mechanical methods such as grinding or blasting. Another major user of chlorinated solvents is the drycleaning industry. It may be necessary to re-design the machines to use other cleaners where water-soluble cleaners don't do the job. System alternatives In these cases, the purpose of the process or product is questioned, and the solution to the environmental problem is to see that demand ceases. Many of our cleaners are unnecessarily strong and can contain chlorinated solvents. This implies that using them is a risk to health, and also a source of environmental problems once they enter the sewage system. Here there is reason to consider whether perhaps a milder cleaner might work just as well, or whether things really need to be all that clean! [] TL: CLEAN OPPORTUNITIES Without Chlorinated Solvents (GP) SO: Greenpeace Sweden DT: May 1989 Keywords: toxics pulp ozone chlorine alternatives greenpeace groups sweden reports gp effluent / [part 3 of 4] 6. REGULATORY MEASURES. There is presently a debate on whether Sweden should introduce a law on advance registration of new chemicals, something that the Common Market countries and the U.S. already require. It is important to get more information on new substances, but we already know enough to tackle the problems caused by today's chemical use. Our government has passed laws to impede the spread of environmental toxins. Sweden's use of chemicals is regulated by the Law on Chemical Products (LKP), which went into force in 1986. The intent of the law is to prevent damage to human health and the environment that can be caused by chemical substances. Chlorinated solvents have begun to attract the attention they deserve. In November 1988, the government stated its goal to "completely eliminate emissions and use of chlorinated solvents" (35). So far, however, no concrete plan for reaching this goal has been presented. Begin by following the law! The law proposal explains how these effects can be prevented (36): - "all substances and other products that are handled shall be well researched with regard to their effects on health and the environment." - "hazardous chemical products shall be replaced by products that can be handled more safely ." The text also states that "a suspicion of risk based on good scientific grounds is sufficient basis for intervention." The Law on Chemical Products (37) contains the statement that: "It is the particular responsibility of the manufacturer or importer of a chemical product, by his own research or in some other way, to see to it that there is sufficient basis for assessing the risk to health or the environment that the product can cause." In other words, the producer/importer is responsible for showing whether the chemical is dangerous or not. Does the law work? Our authorities are responsible for seeing to it that the law is followed. A number of different bodies are responsible for making environmental work as effective as possible. The Swedish National Chemicals Inspectorate is responsible for government control of the use of chemicals. Today the only substances that have to be controlled before they are used are insecticides and pesticides. For example, it is not permitted to import pesticides that have not been approved by the Inspectorate. For all other substances, there are no such rules. In principle, anyone can import, manufacture or sell an environmentally toxic product without requesting a permit or even reporting it. The only requirement today is that there must be a warning text on the product sold. The law paragraph outlining the importer/producer's responsibility for a product is today only empty words. Nobody follows the law. The proposal on replacing harmful chemicals with safer ones has had no real effect, either. The information that companies are required to give to the authorities is extremely sketchy. Most information can be kept secret for reasons of company security. The National Environment Protection Board has the overall responsibility for control of emissions to air and water. Major users of solvents are usually required to have permits for their operations, stating limits for emissions to air or water. Society thus has some control over the chlorinated solvents that are entering the environment via smokestacks and sewage pipes. The amounts that pass out through the factory gates in the form of products, on the other hand, is completely uncontrolled. A common sewage treatment method uses aeration tanks where simple compounds are broken down by oxidation. Stable substances, however, evaporate to the surrounding air. The water is cleaned of its solvent content, but it winds up in the surrounding atmosphere. This kind of short-term thinking leads only to a relocation of the environmental problem. The problem also has an organizational side. Today the Institute of Occupational Health supervises solvent uses in industry, the National Environment Protection Board is responsible for emissions from factories, and the National Chemicals Inspectorate is responsible for control of products leaving the companies. How can this work be better coordinated? The way the authorities are operating today, usually by requiring external purification, only perpetuates the present system. Purification plants improve the local situation but solve no long-term problems. 7. SUMMARY. Most of the 60,000 to 70,000 chemicals used daily in our society are harmful to the environment, and many of them are resistant to breakdown. Traditional waste treatment methods are therefore not enough. Stack filters and purification plants neutralize only a small portion of these substances, while the rest is only transferred from water to sludge, or leaves the incinerators as new and often still more toxic compounds. However, toxic emissions and wastes can be virtually eliminated by reduced use of these "unnatural" chemicals. All organic solvents cause environmental problems. This report, for example, discusses only chlorinated solvents, since many of these are proven to be particularly dangerous to the environment and human health. Besides, there are already alternatives for use in industrial processes and consumer products. Many organic compounds are so stable that they remain in our environment unaltered for decades or centuries, whether they enter the environment as emissions from factories or as discarded consumer products thrown on a garbage dump. Chlorinated solvents break down the ozone layer and contribute to the greenhouse effect and to acidification. Several of them are carcinogenic. They are easily absorbed by skin and respiratory passages, and can damage the central nervous system, brain, lungs and kidneys. To obtain a comprehensive view of solvent use and its environmental effects, a map is needed - a MATERIAL FLOW ANALYSIS. The National Chemicals Inspectorate, the responsible government body, has today no way to control the movement of e.g. chlorinated solvents. This lack of control makes the laws on production, use, transport and disposal of hazardous chemicals virtually unenforceable. The excuse that there are no economically feasible and technically effective alternative solutions is not acceptable. Better alternatives are there to be discovered at several levels.: - chemical alternatives - process alternatives - system alternatives. Alternatives to chemicals are in most cases available today. When chemicals are not directly replaceable, it is usually possible to change the process so that more environmentally sound solutions can be used. In those cases where neither chemical nor process alternatives exist, we have to find other systems. We must ask ourselves whether certain phenomena have a right to exist in our environment and in our society. 8. GREENPEACE DEMANDS. Chlorinated solvents have got to go! Chlorinated solvents are just one in a long list of examples of short-sighted environmental efforts. Instead of attacking the problem at the source, we concentrate on the symptoms. Present "purification" of emissions only moves the environmental problems, it doesn't solve them. The rapidly increasing flood of chemicals must be slowed. We can never obtain control over a constantly increasing use of substances foreign to the environment. The risks of introducing new substances suspected to be harmful to the environment are altogether too great to be taken. The only way to lick the problem is to concentrate on prevention. Greenpeace demands: Open the companies! Comprehensive reports of substances used and included in products must be presented. Use of chlorinated solvents in consumer products must be immediately prohibited. All chlorinated solvents must be phased,out within two years. Invest in clean technology to reduce the number of hazardous chemicals. APPENDIX 1: ALTERNATIVES TO HALOGENATED SOLVENTS some examples from Sweden a) Production and process alternatives for halogenated hydrocarbons as "pure" chemicals. - degreasing - drycleaning - paint removal - printed circuit manufacture - extraction - foaming of plastics - cooling b) Uses of and alternatives for halogenated hydrocarbons as solvents in products. Industrial: - pill coating - glues, paints and lacquer - lubricants In consumer products Other products a) Production and process alternatives for halogenated hydrocarbons as "pure" chemicals. This section covers degreasing, drycleaning, paint removal, printed circuit manufacture, extraction, plastic foaming and uses as a coolant. We have used the term "halogenated solvents" because some applications involve halogens other than chlorine. DEGREASING Process Degreasing with halogenated solvents is presently done both manually and mechanically, usually to clean items before a surface coating is applied. The dominant mechanical method, steam degreasing, is used mainly for metal products. The items are placed in a basket that is lowered into the vapor zone over a bath of boiling solvent. The vapor condenses on the items, and the condensate dissolves and carries away impurities. Various kinds of equipment, cooling pipes, carbon filter systems etc. are used to reduce loss of solvents to the surrounding air. "Tri" (trichlorethylene) is the most common solvent, particularly in the metalworking industry. Other substances can also be used, and the choice made depends largely on the type of product to be cleaned (38). Manual degreasing can be done by spraying the items or by wiping them with a rag dipped in solvent. 1,1,1-trichlorethane is widely used because it has occupational exposure limits higher than those for "tri" and "per" (perchlorethylene). Measures A company in Landskrona that makes lighting fixtures degreases items from machine processing in trichlorethylene. Efforts to replace this resulted in the discovery of more environmentally sound degreasers, made by Petroferm Inc. in Florida. The products are called Bioact and are based on terpene extracted from citrus peels. Three different kinds were tested: Bioact DG-1 and DG-3, both of which are meant to replace trichlorethyl-ene, and Bioact EC-7, intended to replace CFC-113 in the electronics industry. Bioact EC-7 has been used successfully for a couple of years by AT&T in the U.S. Experiments in Landskrona showed that Bioact DG-1 was at least as good as "tri" for degreasing (39). Bioact products are also being tested at Ericsson RE in Molndal, and the tests have shown that DG-1 and DG-3 give a better degreasing result for machine parts than "tri" and CFC 113 (40). Here the cleaning fluid is used in an ultrasonic bath. SKF has developed a cleaning method, the "SKF Washing Principle," in which the parts pass through various rinses and an ultrasonic bath. The cleaning fluid consists of water and a water-soluble detergent. Halogenated solvents are also used for cleaning in the electronics industry. Integrated circuit boards, which are cleaned from oxides with flux before being soldered into place, no longer need to be washed before soldering since there is now a "low-molecular" flux that does not require washing. Ericsson RE and ABB Automation have begun using this type of flux. Other ways of removing flux are used for surface-mounted circuit boards. Very good results have been achieved with ethanol or isopropanol as a cleaning fluid in combination with ultrasound. Both alcohols and terpenes increase the risk of fire. Alcohols belong to class 1, the highest; while terpenes are in class 2. Machines and equipment must be constructed with this in mind. There is such equipment that conforms to German safety standards. Moreover, when ultrasound is used together with alcohol or terpene, it usually works better to use an aqueous solution (for alcohol) or an emulsion (terpene), and this largely eliminates the risk of fire. Ultrasound is unsuitable for certain applications. Terpene degreasers (including Bioact EC-7) are therefore being tested for degreasing of surface-mounted circuit boards (40). Spray application of Bioact EC-7 is simple and effective, but requires investment in new equipment. Spraying with terpene as a degreaser requires use of the pure substance, i.e. not a water emulsion. Cleaning equipment can be made sealed or semi-sealed and the process can be carried out in a nitrogen gas atmosphere. This is also a trend for other operations in the electronics industry, since it eliminates oxidation problems. For high-tension electronics, both grease and salts (e.g. from fingerprints) must be removed. Berol Kemi in Stenungsund has developed a water-based washing system, Meqqem 8624, that works well for this purpose and can replace halogenated solvents. New metalworking methods that completely eliminate the need for degreasing can also avoid the use of halogenated solvents. Laser processing and electrochemical processing are two methods that are being used. Laserstans AB cuts plate with lasers. The technique is particularly well suited for geometrically complicated "holes." Milling operations are also now done with lasers. But for simple jobs, laser technique is still too expensive compared with traditional stamping (41). DRYCLEANING Process Drycleaning machines operate in the same way as conventional washing machines, except that an organic solvent, now usually perchlorethylene or CFC 113, is used as cleaning fluid. Swedes dryclean their clothes more seldom than other Europeans. However, many clothes are drycleaned that really don't need it (42). The reason for drycleaning is that some textile fibers are less affected by drycleaning than by washing in water. Measures The drycleaning business has started a project, Tvatt 113, that is intended to reduce consumption of CFC 113 (43). It is hoped that this will lead to an exemption after 1994, which is the presently projected cutoff date for CFC use in Sweden. Current international research will reportedly lead to replacements for today's cleaning fluids within the next 3 or 4 years (44). An alternative cleaning method is emulsion washing, which is well suited for cleaning work clothes (45). Two Swedish companies, Leitex AB and TT-Tvatt in Karlstad, now use this method. The Swedish Institute for Water and Air Pollution Research (IVL), which is investigating the environmental effects of emulsion washing, believes that in the future it can be an alternative to perchlorethylene cleaning (46). Emulsion washing is suitable only for textiles that can tolerate water. Before halogenated solvents appeared, various kinds of naphthalene were used for drycleaning. Many drycleaning establishments caught fire because of the explosive vapors. Modern drycleaning machines are sealed in a different manner, but they are not constructed for use with flammable fluids. One development possibility is design of sealed machines that work in an inert gas such as nitrogen. PAINT REMOVAL Process Most shops that do painting also do some kind of paint removal, primarily to clean their painting equipment: hooks, racks, etc. A common method of paint removal is to dip the object into a room-temperature solvent bath, containing for example a mixture of methylene chloride and acetic acid. Alternatives Several different methods are used and have been used for removing paint and lacquer. The most common involve dissolving or loosening the paint with a hot alkaline solution. The paint can also be burned off, either with flame or in a fluid bed with aluminum oxide powder; acid or salt baths can be used for oxidative breakdown; or mechanical methods such as sandblasting or grinding can be used (47). One method developed in recent years is paint removal by freezing in liquid nitrogen. The method has many advantages from an environmental point of view, and is suitable for several different kinds of paint. ACA Innovation and the Institute of Production Engineering Research (IVF) have collaborated to develop equipment adapted to production (48). A combination of freezing/blasting was tried, for example. SAAB PB in Trollhitten has been using such equipment for a couple of years, and it has functioned with no major problems. One problem solved was that the wax used to protect the enamel finish formed sticky balls. AGA has further refined the method. Svenska Hoechat AB markets a process developed by Messer Criesheim GmbH in Dusseldorf. It combines dipping in liquid nitrogen with subsequent vibration treatment in a separate machine (49). PRINTED CIRCUITS Process A card with a thin layer of copper covered by a light-sensitive "photoresist" layer that becomes hard on exposure to light is the starting point for a printed circuit. The pattern for the circuit is photographed onto the card from a "blueprint" and the unexposed photoresist is then washed away, exposing the underlying copper. The plate is then etched so that the copper has the same pattern as the exposed area. After etching, the hardened photoresist must be removed. This is often done with a bath of methylene chloride. Alternatives There are several newly developed methods for removing the photoresist. A potassium hydroxide solution is used instead of methylene chloride. Several large chemical companies, including Hoechst, Du Pont and PC Trading, sell photoresist that can be removed with a potassium hydroxide solution (50). EXTRACTION Process Extraction is using a liquid to draw out a desired substance from solid materials, powders etc. A common example is brewing tea or coffee. There are many industrial extraction processes, using both water and organic solvents. Sugar is made from sugar beets by extraction with water, and oil is extracted from oil plants (e.g. at EXAB in Karlshamn) with industrial hexane. Two of the most important extraction processes internationally are decaffeination of coffee and the production of hops extract. Neither of these processes exist in Sweden (51, 52), but decaffeination is a common process in the U.S. and is also done in several places in Europe. Methylene chloride is the most common extractant. Methylene chloride is also used as an extractant in the Swedish pharmaceutical industry. Alternatives General Foods in Germany has an extraction method for decaffeination of coffee beans, the "Kaffe-Haag" process, which uses as extractant carbon dioxide at very high (supercritical) pressure. Possible applications for this kind of extraction method are now being studied at the institute for food technology at Lund University. FOAMERS FOR PLASTICS Background In Sweden, before the regulation on use of CFC and halones (law SFS 1988: 716), plastic foaming was the process that used the most CFC: CFC 11 and CFC 12. The product register kept by the Swedish National Chemicals Inspectorate indicates that 140 tons of methyl chloride were used for plastic foaming in 1987 (30). It has not been possible to determine the context for this use. Polyurethane plastic Process Polyurethane plastic foam (PUR) is the most common foam plastic product in Sweden. Soft foam (mattresses, upholstery), hard foam (construction panels, pipe insulation) and integral foam (molded PUR with a foam core and a skin-like surface) are the primary groups of polyurethane foam products that have long been made with CFC 11. Methylene chloride is also used in other countries, primarily in the U.S. Alternatives When polyurethane is made, two components are mixed and react with each other in a way that forms a three-dimensional network. The physical characteristics of the foam, such as its hardness or softness, are governed largely by the choice of components. A foaming agent is added to create the foam. The reaction between the components makes the agent boil, thus causing the foaming. When water is used instead of a foamer such as CFC, it reacts with one of the components and releases carbon dioxide gas. Polyurethane foam can thus be made without CFC. This is the method that several polyurethane foam manufacturers will be using. AB Svenska Shell has been experimenting with making hard foam with water and new components, which are necessary for the physical properties of the foam. Powerpipe AB in Hisings Kirra is starting production of CFC-free foam for culvert pipes in 1989. Dow Chemicals can also offer a recipe for CFC-free PUR production on the same principle. There is also a vacuum technique for insulating pipes (53). Between the carrier pipe and the mantle pipe there is a non- conducting filler that retards heat radiation. It is manufactured in Germany by Mannesmann Seiffert. Extruded plastic foams Polystyrene and polythene, extruded together with a suitable gas, form foam. CFC 12 is presently the most common gas. Dow and Rockwool Eccoprim, the two manufacturers of panels of extruded polystyrene (XPS) in Sweden, have both announced plans to replace CFC 12 by unsaturated halogenated gases. Scandplast, the only Swedish manufacturer of food packaging in XPS, replaced CFC 12 with pentane two years ago. Extruded polythene is also made with butane gas instead of CFC 12. Since these processes cause emissions of pentane and butane respectively, they are not entirely satisfactory. [] TL: CLEAN OPPORTUNITIES Without Chlorinated Solvents (GP) SO: Greenpeace Sweden DT: May 1989 Keywords: toxics pulp ozone chlorine alternatives greenpeace groups sweden reports gp effluent / [part 4 of 4] COOLANTS Halogenated compounds used as coolants in compressor-driven systems are usually CFCs. As a result of the decision to phase out CFCs, the affected industries are seeking substitutes. The primary candidates are unsaturated halogenated and chlorine-free fluorocarbons. Ammonia can be used in compressor-driven cooling systems, particularly large systems in stores, where a water-glycol mix can be used to distribute the cooling medium from a compressor. This system is already in use for ice rinks. Heat pumps can be constructed on the absorption principle. An aqueous solution of lithium bromide salt is the usual medium. The Sivenis municipal waste incineration plant in Gothenburg uses four such heat pumps, which have been running with very few problems (54). b) Uses of and alternatives for halogenated hydrocarbons as solvents in products. INDUSTRIAL Background Industrial products containing halogenated solvents are usually for covering surfaces. The function of the solvent is to help spread a substance, such as paint or lacquer, evenly over the surface. In general, there are two approaches: either to replace the product with one dissolved in water or to use a product containing another non-halogenated solvent. Pill coating, glues and lacquers, and casting lubricants are discussed below. PILL COATING In the pharmaceutical industry, many medicines are made in the form of pastilles or coated pills. The active substance is encased in a coating of some substance that allows the medicine to dissolve at a suitable speed. In manufacture, a solution containing this binder is sprayed on the pastilles and the solvent then evaporates. There are several different kinds of pastilles. The most common have been covered with a binder dissolved in methylene chloride. At Astra, this method has now been 90% replaced by a water-based system (55). Another kind of pill, as big as a pinhead, is fast replacing the traditional tablet. A capsule of these, with coatings of different thicknesses, provides better dose delivery. So far, the pinhead pills have been covered by a binder containing a solvent. Water-based systems are being developed, primarily in the U.S. and in collaboration between Swedish and American companies such as that between Astra in Sweden and Merck in the U.S. Riker Laboratories in Northridge, California has also begun using water-based binders (56). GLUES AND LACQUERS Uses in this area are technically very similar to those in the pharmaceutical industry, since in both cases a binder is dissolved in a solvent that evaporates when the substance has been spread over a surface. One use for halogenated solvents in the rubber industry is in glues to fasten rubber to metal. Another is methylene chloride in glue for soft polyurethane foam. In general, the trend is to try to replace these products with waterbased products, powdered paints and melted glues. A good example is the use of water-based printing ink as a replacement for alcohol-based inks for flexograph printing on polythene (57). CASTING LUBRICANTS Process In casting of heat-hardened plastics such as epoxy (EP), polyester (AP) or polyurethane (PUR), and also in some casting of thermoplastics such as polypropene, it is necessary to get the material out of the casting mold. Some type of lubricant is therefore used, either mixed with the plastic to be cast or coated onto the mold. External lubricants are generally some form of wax dissolved in a halogenated solvent such as 1,1,1-trichlorethane, methylene chloride, CFC 11 or CFC 113. Alternatives Several good water-based external lubricants have been developed for use with PUR (58). These can contain small amounts of solvents, 1 to 10% ethanol, for example. Developments in this area are rapid. For over a year now Nobel Plast has made components with water- based lubricants, and lubricants based on halogenated solvents are being completely phased out (59). The possibility of using water-based lubricants instead of solvent-based lubricants in casting epoxy plastic is now being explored in a doctoral study in collaboration between Ericsson RE in Molndal and Kemisk Miljovetenskap at Chalmers Institute of Technology. The final report is expected in May, 1989. Preliminary results are promising. Several different kinds of lubricants are being tested. A relatively new kind of permanent surface coating, dispersion coating, is being tested at IVF, primarily for use in casting forms for epoxy plastic (60). The surface is a dispersion of PTFE (Teflon) in nickel, precipitated from an electrolytic bath. IN CONSUMER PRODUCTS This area is almost impossible to survey. A recently published doctoral thesis presents studies of 70 consumer products in six product groups (61). - Degreasers - Rust preventives - Rust removers - Automobile maintenance products (vinyl polish etc.) - Furniture polishes - Spot removers About a quarter of the examined products contained chlorinated hydrocarbons. Many of these are completely unnecessary. One product, a lubricant for rubber moldings, contained 1,1,1-trichlorethane to dilute glycerol, which was the actual lubricant. In some other products the solvent may do more harm than good; in polishes for vinyl surfaces such as instrument panels, for example. These vinyl leathers contain softeners that can probably be dissolved by strong solvents such as 1,1,1-trichlorethane. If this happens the vinyl will age faster, and will weaken and probably crack faster. Correction fluids (Tippex and other brands) that are found in virtually every office account for about 20 tons of 1,1,1-trichlorethane emission in Sweden alone. Total emissions from consumer products may amount to hundreds or even thousands of tons, but unfortunately it is difficult to get reliable information, since a product's content of halogenated solvents is often stated very approximately (e.g. 30 to 100%), and suppliers and retailers are reluctant to report sales volumes (61). The National Chemicals Inspectorate nevertheless concludes that the use of organochlorines here is at most a couple of percent of industrial use (62). Their product register contains information on a total of 4,500 substances connected to products, 288 of them containing organochlorines. Consumer products contained 1,100 substances; 44 contained organochlorines (62). Compounds that are dangerous to health but not a threat to the environment are not taken up in the product register, and neither are substances that occur in such low concentrations that they are not measurable. These unknowns are hard to quantify. Alternatives A strong driving force for alternatives in this area is the market, i.e. the consumer. Correction fluid is one example. A sales agent handling correction fluid reports that sales of water-based fluid have increased rapidly since people found out about its existence. Many consumer products have parallels in industrial use. Often, however, industry is under strong pressure to phase out substances dangerous to health (and the environment). These improved products should be placed on the consumer market faster. Municipal regulations have caused many gas stations to use water-based alkaline detergents to wash vehicles. The detergent is not marketed as a consumer product. The company that sells it doesn't believe there's a market for it among "private" consumers. Of course there's no demand, when the consumer doesn't even know the product exists! Many substances are unnecessarily strong. It may be unhealthy to use them indoors or in a small garage. A much milder cleaner can often be quite adequate. Other products A report such as this is not intended to be comprehensive, and there are no doubt a number of applications with larger or smaller emissions of halogenated solvents which have not been identified and for which no alternative is presented. One example is vulcanization. The only use found, in spite of contacts with the Plastic and Rubber Institute, is as solvent in glue in bicycle repair kits. This use can not quite account for the entire use of halogenated solvents in vulcanization, which according to the product register amounts to about 120 tons annually.