Document n9OzzmqEBmQX6qxLpzKnkX33m

CHLMICAL MANUFACTLJRf.RS ASSOCIAl ION August 6, 1991 A! 16 9 To: Vinylidene Chloride Panel Members Re: Greenpeace Report For a Chlorine Phase-out Attached for your review is a copy of "The Product Is the Poison", a Greenpeace initiative to phase out all chlorine products. Also attached is a memorandum from the Chlorine Institute requesting industries with an interest in chlorine chemistry to analyze and comment on the Greenpeace report. If you have any comments on the Greenpeace report or believe that the Panel should provide an official response to the initiative, please let me know by August 16, 1991. If you have any questions regarding the Panel's activities, please call me at 202-887-1146. Thank you. Regards, Kathleen M. Roberts Manager Vinylidene Chloride Panel SL 062247 250' M Street NW. Washington. DC 20037 202-887-1100 Panafax 202-887-1237 Telex 89617 (CMA WSH) The Product Is the Poison The Case for a Chlorine Phase-out A GREENPEACE Report By Joe Thornton The author gratefully acknowledges Pal Costner, Jack Weinberg. Paul Johnston, Robert Glnsburg, and Jeff Howard, whose research and counsel were Indispensable to the preparation of this report. SL 62248 Copyright 1991 by Greenpeace U.S-A1436 U Street. N.W. Washington, DC 20009 primed in Canada Greenpeace Great Lakes Project 1017 W. Jackson Boulevard Chicago, IL 60607 (312)666-3303 183 Spadina Avenue, *600 Toronto, Ontario M5T2C6 (416) 345-8408 Greenpeace is an international environmental organization dedicated to preserving the earth and all dte life it supports. ^ This publication is made possible by more than four million supporters around the world. SL 062249 TH{ PRODUCT ____ IIT M IP 0 I I o N CONTENTS Summary and Recommendations 1 Chlorine and Organochlorines in the Global Ecosystem Chlorine and Organochlorines in Nature Chlorine and Organochlorines in Industry Behavior of Organochlorines in the Environment Persistence in air Persistence in water Resistance to biodegradation B ioac cumulation Toxicity Global Accumulation of Organochlorines Government Responses to Organochlorine Pollution Shifting the Focus: From Individual Organochlorines to Chlorine 2 Organochlorines in the Great Lakes Ecosystem Assessing Chemical Mixtures Occurrence of Organochlorines in the Great Lakes Effects on Fish and Wildlife Lake trout Bald eagles Gulls, terns and cormorants Ecosystem and interspecies effects Effects on Humans TimeTrtnds in Great Lakes Contamination 3 Chlorine and Organochlorines in Industry: Releases and By-Products Releases of Organochlorine Products By-Product Formation Chlorine Manufacture Chlorine Use Pulp and paper Water treatment Metallurgical process Combustion of Organochlorines Manufacture of Organochlorines Use of Organochlorines 4 Economics of the Chlorine Phase-Out Implications for Industries That Use OUorine Reaction of Chlor-Alkali Corporations Protecting Workers References SL 062250 1 7 19 33 49 53 THE P *0 0 U CT I$ THE *___ o iiod SUMMARY AND RECOMMENDATIONS The purpose of this report is to show that the Indus* trial production of chlorine poses a severe threat to the ecosystem and must be phased out t CHLORINE, ORGANOCHLORINES, AND THE CHLOR-ALKALI INDUSTRY The chlor-alkali industry starts with ordinary salt -- in abundant, natural compound. The chemical name for ordinary salt is sodium chloride. Each molecule contains one atom of sodium bound to one atom of chlorine. Through a process called electrolysis, the chlor-alkali industry uses large amounts of electricity to break the bond between the sodium and chlorine atoms, split ting the salt molecule. The sodium reacts with water to form sodium hydroxide, sold commercially as <uh!a, Chlorine is released in the form of chlorine gas, also called "elemental chlorine.** Chlorine gas is a human invention. It does not exist in nature, and there is no known natural process that creaies it. Chlorine gas is extremely unstable and reactive: when it comes into contact with organic (carbon-containing) molecules, the chlorine binds tightly to the carbon atoms, creating new substances called organochlorincs. These organochlorines may be produced on purpose or by accident For instance, the chemical industry combines chlorine with petrochemicals to create thousands of organochlorine pesticides, plastics, solvents, refrigerants, and other chemicals. 11,000 organochlorines are now in commerce. The combination of chlorine with organic molecules takes place very quickly, and it produces a wide variety of organochlorines. When chlorine is used as bleach in pulp mills or as a disinfectant in sewage or water treatment hundreds of organochlorine by products are formed. Similarly, when chlorine is used to manufacture specific organochlorine products, many unwanted by-products form, as well. These are collected as wastes or remain in the product as impu rities. Whenever organochlorines are burned thou sands more by-products are created. When organo chlorines are used, by-products are frequently formed especially in high-temperature or chemically unstable environments. These by-products include some of the most toxic and persistent organochlorines. such as the dioxins, furans, PCBs. and hexachlorobenzene. Even the least toxic organochlorine products produce the most dangerous organochlorines at some point in their industrial life-cycle. When organochlorines enter the environment, still more organochlorincs are produced in reactions with sunlight, other chemicals, or biological agents already present in the ecosystem. SL 062251 rnc PRODUCT IS TNI p 0 I SON PROPERTIES OF ORGANOCHLORINES Orgaiwuiloiines an almost completely foreign to nature. In contrast id tbe thousands of organochlorines produced by the industrial use of chlorine, only one organochlorine compound -- chloromethane -- is produced in nature in significant quantities. The simplest of the organochlorines. chloremethane evidently plays a role in the natural regulation of the ozone layer. Many organochlorines are very stable. Once they enter the environment, they resist natural breakdown processes and persist for long periods of time. Some organochlorines can be broken down slowly in the environment, but the breakdown produces -- usually other organochlorines -- are often more toxic and persistent than the original substance. mune suppression, and damage to the liver, kidneys, and other organs. For some organochlorines, these effects are known to occur at unimaginably low doses (as low as a few pans per trillion or even less); others require doses in the pans per million to cause measur able effects. ORGANCHLORINES IN THE GLOBAL ECOSYSTEM Most of the 40 million tons of chlorine produced each year is convened to organochlorines, either purpose fully or as accidental by-products. This production rate far outstrips the slow me at which organo chlorines can be convened back into salts and other forms of inorganic chlorine. The total burden of organochlorines in the environment thus grows each year. Breakdown is not complete until the chlorine atom has once again been incorporated into salt (or some other inorganic molecule, such as hydrochloric acid). Complete breakdown of organochlorines takes place extremely slowly, requiring hundreds of yean or more in some cases. This slow process stands in stark contrast to the chlor-alkali industry's rapid conversion of salt to chlorine, now occurring at the rate of 40 million ions per year worldwide. Many organochlorines are more soluble in fats than in water, once in the environment, they tend to migrate into living tissues -- a process called bioaccumulanon. Contaminant levels are multiplied as they move from one level of the food chain to the next Often, the concentrations of organochlorines found in the tissues of fish, wildlife and humans are thousands of times greater than the levels found in the ambient environment. As a result, organochlorines can now be detected absolutely everywhere on Earth. They are present in the stratosphere, where they have caused depletion of the earth's protective ozone layer. They migrated into the air and water of the entire planet, even at the North and South poles. And they have accumulated in the tissues of living things, even in the deep oceans and polar regions. Species near the top of the food web bear the greatest burdens. Marine mammals and fish-eating birds and wildlife across the planet have the highest concentra tions of organochlorines in their tissues. At least 177 organochlorines have been found in the tissues and fluids of humans in the U.S. and Canada, including adipose tissue (fat), mother's milk, blood, semen, and breath. Organochlorines are passed from one genera tion to the next through the placenta and breast milk. Because virtually all organochlorines are foreign to nature, most living things have not evolved methods to detoxify and excrete them. Organochlorines are known to cause reproductive, developmental, and r.curr'.cgical impairment, cancer, birth defects, im SL 062252 THI PRODUCT IS T HI l___ # t t 0 N EFFECTS OF ORGANOCHLORINES IN THE GREAT LAKES Ai it*st 168 organochlorines art "unequivocally presenT in the water, sediments, and living tissues of the Great Lakes ecosystem, according International Joint Commission Science Advisory Board. These include an array of pesticides, industrial chemicals, and by-products from chlorine and organochlorines in paper mills, incinerators, and other industries. Thou sands more are presumably present but have not yet been detected, due to limitations in the design and technology of monitoring programs. Organochlorines have been linked to epidemic health effects among 13 species of fish and wildlife near the top of the Great Lakes food web. In every case, the effects involved the ability of the exposed organisms to produce health offspring that developed properly. These effects, which show a remarkably consistent pattern, include infertility, birth defects, embryonic mortality, developmental impairment, and behavioral abnormalities. Great Lakes contamination has caused similar devel opmental effects in humans. A group of hundreds of infants bom to mothers who ate Great Lakes fish were bom sooner, weighed less, and had smaller heads than infants from the same community whose mothers did not eat Great Lakes fish. The infants behaved abnor mally and, in tests ax 7 months and 4 years of age, had difficulty learning because of impairments in short term memory and other mental functions. The effects were annbuted to infant organochlorine exposure trcr^fcmd from the tissues of mothers who had consumed Great Lakes fish. Each of the.* epidemics has been associated with exposure to one or more organochlorines. In no case have healLh effects been attributable to individual chemicals. The documented epidemics have clearly been caused by mixtures of numerous organo chlorines. Effects in the Great Lakes are an early warning of effects that may occur across the rest of the planet Many industrial dischargers release organochlorines directly into the Great Lakes. When facilities near the Lakes discharge organochlorines into the air or put them in landfills, a major portion ends up in the water. The Great Lakes also serve as a sink for organochlorines transported by air fiom as &ras Latin America. Once in the Great Lakes basin, or ganochlorines are very slow to leave it Less than one percott of the water in the Great Lakes flows out of the Lakes into die ocean each year. The effeets of organochlorine contamination thus show up more quickly in the Great Lakes than in other aquatic ecosystems. But as organochlorines art slowly dis tributed across the planet similar effects are likely to occur worldwide. Not only does this problem show up more quickly in the Great Lakes, but even after world society finally stops producing and using organochlorines, the Great Lakes will take a very long time to recover--several generations or more. Faster flushing inland water systems can recover more quickly by transferring their pollution to the ocean, where it is more easily ignored. If action is not taken quickly enough, the Great Lakes ecosystem could be destroyed for genera tions. Organochlorine pollution is thus of special urgency to the people of the Great Lakes ecosystem. GOVERNMENT RESPONSES TO ORGANOCHLORINE POLLUTION Some of the most infamous organochlorines have already been banned or severely restricted: DOT, PCBs, chlordane, mirex, dieldrin. heptachlor, chlorofiuorocarbons, etc. Governments have taken these actions after receiving evidence that contamination and effects had already occurred. These banned chemicals have been the focus of virtually all assessments of trends in contamination levels. Despite reduced inputs of these chemicals following government action, levels of banned or- SL 062253 3 ganochiorines in the Great Lakes ecosystem have declined more slowly than expected. In some cases, their great persistence and continuing input from external sources have resulted in stable or even increasing levels in the Great Lakes food web. produce organochlorines. all uses of chlorine must be phased out as well For virtually all known uses of chlorine and organochlorines, effective alternatives are readily available. Meanwhile, the thousands of organochlorines that have not been restricted continue to be released in the Great Lakes and elsewhere. Many banned substances have merely been replaced with other organo* chlorines. Total chlorine production has slowly increased, leading to increased organochlorine pro* duction and release, as welL As persistent organochlorines continue to enter the environment, total contamination undoubtedly increases. Continuing epidemics among Great Lakes species offer further evidence that meaningful decreases in total contami nation have not occurred. No monitoring programs, however, have attempted to determine trends among the thousands of uncontrolled organochlorines or trends in overall measures of contamination (such as total organically-bound chlorine). Most of the organo chlorine compounds present in the environment has not even been identified, much less assessed for historical trends. Enough is known about the persistence and toxicity of organochlorines as a class to justify an outright ban. Only a tiny portion of the many organochlonies in commerce have been subjected to even preliminary hazanj assessments, and many more organochlorine by-products and breakdown products remain unidenti fied and thus unassessedL Regulating organochlorines one*by-one is doomed to failure. A shift of regulatory focus from individual chemicals to the class Of organochlorines is necessary. The banning of individual organochlorines over the last two decades has resulted in drastic reductions in inputs of these chemicals to the environment. Now, that strategy must be applied to the entire class of organochlorines. To prevent further continually increasing levels of organochlorine contamination, the manufacture and use of all organochlorines must be phased oul Because all uses of chlorine also RECOMMENDATIONS U.S. and Canadian governments should implement the following policies to phase-out the production (purposeful or unintended) and use of organo chlorine*: 1 Acknowledge the severe damage to human and ecosystem health caused by the class of orgarochlorines. 2 . Establish a plan to phase-out the use, export, and import of all organochlorines, elemental chlorine, and chlorinated oxidising agents (e.g., chlorine dioxide, sodium hypochlorite)/ 3 Implement an immediate ban on the introduction of chlorinated organic compounds to any combustion device, including trash incinerators, hazardous waste incinerators, boilers, kilns, smelters, and vehicles. 4 Require major users (industries, armed forces, municipal sanitary districts, etc.) of organochlorines, elemental chlorine, and chlorinated oxidizing agents to submit rapid timetables for the phase-out of these substances. Priority should be given to the following sectors which cause severe organochlorine pollution: A) Pulp and paper -- a rapid and complete phase-out of chlorine and chlorine com pounds in bleaching and delignification. B) Solvent users -- a rapid phase-out of chlo rinated solvent use in manufacturing indus tries including automobile manufacture, metal working, electronics and electroplat ing. Alternatives include water-based paints, unproved housekeeping, replacement of toxic materials requiring solvent washes, and substitution of aqueous, biogenic, or mechanical cleaning methods. -- Si, 06225* THt PRODUCT IS T N f 0 ISOM Q Chlorinated biocides -- a rapid phase-out of chlorinated pesticides, herbicides, fungicides, and slimicides excluding those that contain chlorine as a non-biocidal element, such as auazine and alachlor) in agriculture, wood treatment, forestry, and other uses. Govern ment programs should encourage the transi tion to pesdeide-free farming techniques, such as improved crop rotation and diversity, use of natural pesticides, and preservation and introduction of predators that prey on pests. D) Chlorinated plastics. A rapid phase-out of chlorinated plastics, especially for disposable purposes 0>e.. plastic packaging). 5 Protea workers and communities now involved in the manufacture of chlorine and organochlorines. Funds and programs should be established immedi ately tc provide compensation, retraining, and place- merit of workers displaced from such industries and to provide similar assistance to communities now dependent on such industries. The funds for such programs should be derived from the chlorine industry itself. For example, a $100 per ton surcharge on chlorine production would generate approximately $1.2 billion per year in the United States and $110 million per year in Canada at current production rates. The actual design of the program should be established through consultation with representatives of the workers and communities involved. 6 Prohibit the substitution of other halogens and organohalogens (e.g, bromine or fluorine compounds) for chlorine and organochlorines since these classes of compounds also tend to be foreign to nature, toxic, persistent, and bioaccumulative. t That may be certain minor but "essential" usee of chlorine for which alternatives have not beet developed (Santibiotics). Temporary exception* to the phase-out will be permitted if it can be provat beyond any reasonable doubt that for a specific use of an or|inochJorine. all of the following conditions can be met: (s) the use serves a compelling noed: (b) no alternative* can be foimd: Bid (e) intensive research has beat initiated to develop alternatives and eliminate the use in question. SL 062255 T. N ( 9 R0 DUCT IS THE 9 0 I f 0 ft CHLORINE AND ORGANOCHLORINES IN THE GLOBAL ECOSYSTEM CHLORINE AND ORGANOCHLORINES IN NATURE Chlorine gas (Cy -- the elemental form of chlorine -- is a human invention; it does not occur naturally. In the form of chloride ions (G-). however, chlorine is plentiful in nature. Chloride ions occur predominaltly as sodium chloride (NaG) -- sea salt and table sal: -- end in other metallic chlorides in the earth's crust. Chloride ions do not bond with the carbon atoms that are the basic building blocks of "organic" matter-- the substances that comprise or are derived from the tissues of living organisms. Chloride ions circulate constantly through the Eanh's oceans and through the blood and other body fluids of almost all living organisms. The chemical behavior of artificially-created chlorine gas is entirely different from that of chloride ions. Is highly reactive. It combines readily with carbon-based material to form a whole new class of chemicals -- organochlorines -- in which at least one carbon atom is directly bonded to one or more chlorine atoms. Organochlorines are not known to occur nawrally in the tissues of humans, vertebrates, [Vallentyne 19891, or any "terrestrial animals." [Ncidleman 1986] A number of organochlorines can be produced by other organisms but only in very small quantities. [Neidle- man 1986} These organochlorines appear to play important antibiotic and messenger roles and to be ddicately regulated by metabolic and ecological balances. [Neidleman 1986] The only organochlorine that occurs naturally in significant quantities is chloromethane, which is produced by marine microorganisms and fungi at the nue of about 4 million tons per year. [SRC 1989a] The simplest of the organochlorines, this substance evidently plays a role in the natural regulation of the ozone layer. [Lovelock 1975] The quantity of chlo romethane in the environment at any one time was strictly regulated by its relatively slow production rate and nature's limited capacity to convert it back into chloride ions (through reaction with light and other chemicals in the atmosphere). [Lovelock 1975] CHLORINE AND ORGANOCHLORINES IN INDUSTRY By passing large amounts of electricity through brine -- a salt-water solution -- the "chlor-alkali" industry converts sodium chloride into chlorine gas and alkali, also called sodium hydroxide (NaOH). This process, known as brine electrolysis, is one of the most en ergy-intensive industrial processes known. [Schmitlinger 1986] First undertaken on an industrial scale in 1893. chloralkali manufacture grew slowly until World War II. SL 062256 7 TME product is t ht * o i ten after which pnwA rates averaged as much 8 percent annually. [Verbanic 1990] By 1989.55 U.S. chloralkali plants wert producing 11.6 million tons of chlorine annually. [Cl 1989] 13 Canadian plants have the capacity to produce about 1.7 million tons per year. [CIS 1989] World production of chlorine now totals about 40 million tons per year. [Rossberg 1986] Either intentionally or unintentionally, most of this elemental chlorine is eventually incorprated into organochlorines. In the U.S., about 70 percent of all chlorine produced [Cl 1989] is combined with petrochemicals to produce some 11,000 organochlorine products (pesticides, solvents, refrigerants, chemical intermediates for the production of inorganic chemicals, etc.). [Braungan 1987] The remaining 30 percent of chlorine is used in its elemental form -- for bleaching in the pulp and paper industry, for the disinfection of wastewater and drinking water, or to produce purified metals or metal oxides. [C! 1989, Vonkeman 19911 In these cases, chlorine'combines with organic matter (wood pulp, sewage, etc.) to form hundreds or organochlorine by-products. BEHAVIOR OF ORGANOCHLORINES IN THE ENVIRONMENT The properties of organochlorines make them very long-lived in the environment: c orriTiOChlorines arc very stable. The chlorine-carbon bond at the heart of these conipounds is, in general, a strong bond requiring large amounts of energy to break. Many organochlorines thus persist in the environment, resisting degradation by physical and chemical processes. Organochlorines, with few exceptions, do not occur in narure. Living organisms thus have developed few methods to metabolize them. Organochlorines thus resist breakdown by biological processes. Many organochlorines are more soluble in fat than in water. As a result, they tend to bio accumulate (migrate from the environment into the tissues of living organisms). The breakdown of an organochlorine is not complete until the chlorine atom has once again been convened into sodium chloride or hydrogen chloride. Because organochlorines are chemically stable and resistant to biodegradation. Namre's ability to conven them back into chloride ions is extremely limited and takes place -- with few exceptions -- very slowly. i "In general, the environmental degradability of heavily chlorinated organic compounds, whether by biotic or abiotic mechanisms, is low," according to one industrial reference. [Rossberg 1986] A report by the Federation of European Chemical Industries echoed this view: The vast majority of these [orginochlorine] compounds do not occur naturally, are rather persistent and can harm the environment more or less severely. An important pan of the organo-halogen compounds produced may remain in use for a shorter or longer period, but will finally appear in the environment. After sometimes 100 yean, the compounds will decompose, releasing their chlorine in some form and producing (directly or indirectly) carbon dioxide from the hydrocarbon part. [CEF1C 1989] Persistence In air Organochlorines released into the air resist degrada tion by sunlight or other chemicals in the atmosphere. For example, carbon tetrachloride, uichloroethsne, and chlorofiuoroarbons have atmospheric lifetimes ranging from 25 to 150 yean [Howard 1990]. Nanirally-occuring chloromethane has an atmospheric half- life of 1.5 yean [SRC 1989a]. The pesticide alachlor -- specifically designed to break down more easily than other organochlorine pesticides--can be 062257 SL THE PRODUCT IS T H *o|s0N found in rainwater throughout the Midwestern U.S. in concentrations as high as 4 pans per billion. [Goolsby 1991] Trichloroethylene, which has a half-life of only sever?! months, merely breaks down into other organochlorines, including phosgene, dichloioacetyl chloride, and formyl chloride. [HSDB 1991] When organochlorines do break down in the air, the by-products are often more persistent and more toxic than the original compound. For instance, the pesti cide mirex can be broken down by light within weeks; however, the breakdown product -- photomirex -- is even more persistent and at least as toxic as mirex itself. [HSDB 1991] The case of trichlorophenol is similar. When exposed to light. It can be transformed into 2.3,7,8-TCDD (a very stable chlorinated dioxin), which is far more persistent and far more toxic than trichlorophenoL [Catabeni 1985] Once released into the environment. 2,3.7,8- TCDD can persist fbr years or decades. [USEFA 1988] Persistence In water Organochlorines also resist chemical breakdown in water. In pure water, for instance, chloroform and trichlomethane remain intact for 1,850 and l million years, respectively. [Jeffers 1989] Chlorinated diox ins. too, are resistant to aquatic breakdown processes, remaining intact for decades. "PCDDs are expected to be very persistent in aquatic media," according to USEPA. [USEPA 1985a] Some organochlorines can degrade slowly in water thraejh hydrolysis or other reactions. Many of these compounds art not soluble in waicr, however, and they escape from surface waters before such reactions can take place. For instance, a large number of or ganochlorines are very volatile (i.c.. most chlorinated ethanes, methanes, and lower-chlorinated benzenes), evaporating from water resources within minutes or hours of their discharge. Chloromcthane, for instance, will evaporate quickly from water, decreasing to 50 percent of its original concentration within 1 day. [SRC 1989a] In addition, volatile organochlorines can attach themselves to suspended panicles and sedi ments, remaining intact in aquatic ecosystems for many years. Many of the less volatile organochlorines are not soluble in water, either. Many non-volatile organo chlorines are mote soluble in organic matter than in waten these migrate into living tissues or adsorb onto sediments, where they can persist for decades. Hexachlorobutadieae, for instance, reacts with water with a half-life of only a few weeks [HSDB 1991]; neverthe less, it has been found to accumulate in fish tissues in concentrations thousand of times times greater than the concentrations found in ambient water. [HSDB 1991] Fbr all these reasons, breakdown in water does not result in significant overall degradation of organo chlorines in the environment According to one study of grounewaierpollution in Milan, Italy, organochlorine contaminants are likely to remain at signifi cant levels for "very many yean" despite stringent reclamation efforts. [Cavellaro 1986] At least 19 organochlorines have been identified as common water contaminants throughout the U.S. [Bminister 1982]; however, the actual total is probably fir greater, since only 10 percent of the chemicals in groundwater have been identified. [Connor 1984] For the few organochlorines that do degrade in water, the breakdown products may be more hazardous than the original pollutants. Fbr instance, high molecular weight organochlorines (e.g.. chlorolignins) make up a large portion of the organically- bound chlorine in pulp mill effluents. They are generally considered relatively non-toxic and non-persistent. However, they are slowly degraded into lower-weight organo chlorines (e.g., chlorinated phenols, guaiacols, cat echols) which are quite toxic. [Bonsor 1988] These compounds may then degrade slowly to produce chloroverauoles which may be of even greater long term toxicity. [Bonsor 1988] Similarly, teuachloroethylene in groundwater may be slowly degraded (over a period of months) into vinyl chloride, which is itself more persistent and far more carcinogenic than the original compound. [HSDB 1991] SL 062258 9 THI PRODUCT IS TNI >011 0 N Kcsisuiice to biodegradation Organochlorines also resist biological breakdown by living organisms. Over thousands of yean, living have evolved methods to metabolize or excrete naturally-occurring chemicals. Because organochlorines are almost completely foreign to nature, however, few organisms have developed processes to break them down. ISAB 19891 Consequently, the biological transformation of organochlorines into chloride takes place very slowly, if at all. "Halogenated aliphatic hydrocarbons are generally thought to be resistant to biodegradation.'* according to one reference. (Howard 19901 Similarly, aromatic organochlorines -- especially the more highly chlo rinated molecules -- also resist biological breakdown. [Webster 1990] Those compounds listed by the U.S. Environmental Protection Agency (EPA) as most resisunt to biodegradation in sewage treatment plants are all chlorinated or brominated compounds. The extent of halogenadon also influences the relative biodegradability of the compounds (i-e., the more halogens in a chemical compound by weight, the less biodegradation will be in evidence)," EPA writes. [USEPA 1986] migrate from the environment into the fatty of living things. For instance. TCDD (the most toxic form of dioxin, also known as Z3.7.8- tetrachlorodibenzo-p-dioxin). has been shown to accumulate in fish tissues at concentrations up to 159,000 times greater than the concentration in the water in which the fish swam. [USEPA 1988] (This figure is known as a bioconcentration factor.) Highly chlorinated aromatic organochlorines are generally regarded as the most bioaccumulalive organochlorines. Bioaccumulation factors for PCBs, bexachlorobenzene. octachlorostyrene, chlorinated dibenzofurans, and tetrachloroazoxybenzene are all estimated at 10,000 or more, according to EPA. [USEPA 1985b] Many chlorinated pesticides -- such as DDT. chlordane. mirex. and others -- have simi larly high bioconcrentradon factors. [HSDB 1991] Many aliphatic and cyclic organochlorines. because they are so volatile, are regarded as less bioaccumulative. Some aliphaxics, however, bioaccumulue sub stantially. Hexachlorobutadiene. for instance, has been found to bioaccumulate by factors as great as 17,000. [HSDB 1991] Similariy. bioconcentration factors for hexachlorocydoperaadiene have been estimated at up to 1600. [HSDB 1991] Most examples of organochlorinc biodegradation involve in- idual microorganisms that transform specific o lochlorine compounds into other organochlorines. 1 nese breakdown products may be more toxic than the original pollutant. DDT, widely re garded as extremely persistent, is actually broken cc-n '-.thin weeks into DDE, which then persists for decades, bioaccumulates, and is actively toxic in mammals. [HSDB 1991] As noted above, chlorophenols are metabolized into the more toxic chlorovera* troles. [Bonsor 1988] Bioaccumulation Many organochlorines build up in Utc tissues of living organisms. Because most organochlorines are more soluble in oils and fats than in water, they tend to Humans occupy a position near the top of the food chain, and their exposures to bioaccumulalive organo chlorines are thus among the highest of any species. At least 177 organochlorines have been detected in the tissues, mother's mQk, semen, breath and blood of the U.S. and Canadian population, (see tables 1.1 through 1.5.) These include the most bioaccumulnive organochlorines, such as the dioxins. PCBs. DDT. and other pesticides. However, volatile organo chlorines generally not regarded as bioaccumuladve also appear to be ubiquitous in human tissues and fluids, including chloroform, trichloroethane, tetrachlorocthyicnc, and chlorobenzene. Though many organochlorines resist biochemical alteration and excretion, they can be eliminated from the body through mother's milk, blood, and semen. to SL 062259 THI f *0 0UCT II T Nt >0lt0 Bioaccumulated organochlorines are thus transferred from one generation to its ofTspring through these fluids. Infants in utero receive significant doses via cross-placental transfer. Following their birth, they receive even greater doses when raining. These doses can be many times greater than the original environmental exposures to which their mothers were subject. [Swain 19881 Toxicity The Science Advisory Board to the International Joint Commission on the Great Lakes (UC) has summa rized the nature of organochlorincs as follows: There is something inherently nonbiological about halogenated organics (excluding iodinated compounds)-.. They have been intro duced in the last one hundred yean into a planetary ecological system that has bocn in operation for several million yean. One does not have to be a biologist to know that random changes introduced into integrated systems have a high probability of being harmful. This statement should be equally obvious to a politician, medical practitioner, or car mechanic-- Most synthetic industrial chemicals for which there are toxicological data are known to cause advene effects-- Chemicals [that) do not occur naturally -- are often persistent, since there are often no natural biological process id metabolize or deactivate them. In contrast, there are natural biological processes to metabolize or deactivate naturally occuring chemicals. [SAB 1989] Cl chlorines are widely recognized as a highly toxic chemical class, causing a wide range of health effects in a broad array of species. Because organochlorines are largely foreign to nature, few living organisms have developed methods to detoxify them. [Webster 1990] Many organochlorincs thus lead to reproductive failure and infertility; many cause birth defects; some are known to cause embryonic mortal ity or impair the development of children; some are known to disrupt the immune system; many cause cancer, virtually all damage the liver, kidneys, nerv ous system, and other organs or systems. According to one industrial reference, "Many, if not most, chlorinated substances can be made to produce an increase of tumors in certain laboratory animals." [Rossberg 1986] Organisms have evolved natural methods to alter and excrete external compounds that occur in nature id avoid the build-up of "foreign" chemicals within the organism. But organochlorines are almost completely alien to nature, and few natural breakdown mediods have been developed. Organisms with longer life times (such as mammals) have had few generations in which to alter, detoxify, and excrete organochlorines. Thus the presence of more than 100 organochlorines in in the fatty tissues, mother's milk, semen, and blood of humans is not surprising. For instance, humans have no process by which to alter and excrete 23,7,8-TCDD. The major enzyme system induced in response to its presence has little or no ability to metabolize it. [Webster 1990] TCDD thus has a half-life in the human body of as much as 29 yean. The major pathways by which it is excreted include mother's milk and semen. [USEPA 1988] Many polychlorinated aromatics, including hexachlorobenzene, chlorinated dibenzofurans, and PCBs, are also resistant to mammalian metabolism. [Webster 1990] Some organochlorines mimic naturally occuring hormones or enzymes. For instance, DDT has an estrogenic effea that can lead to feminization, infer tility, and developmental impairment. Further, chlo rinated aromatics induce an enzyme system involved in the metabolism of hormones that aTect growth, sexual development and the detoxification of other chemicals. These hormones and enzyme systems function in a naturally self-regulating equilibrium: naturally* circulating hormones induce enzymes which lead to breakdown of the hormones, resulting in relatively stable levels within the body. Because many organo chlorines cannot be broken down, however, they can lead to runaway biochemical reactions and a cascade SL 62260 11 T W I> W 0 0 U C TI T H E * 0 I SON of health effects. [Webster 1990] These effects include birth defects, embryonic mortality, infertility, immune suppresion, and the conversion of cancercausing chemicals into more carcinogenic forms. [Webster 1990. SUbergeld 1987, Silbcrgcld 1989] GLOBAL ACCUMULATION OF ORGANOCHLORINES For millions of years, natural processes have limited the amount of carbon-bound chlorine in the global ecosystem to only trace quantities. Now, the industrial production of 40 million tons of chlorine per year has severely disrupted this delicate balance. The gzneraden and dispersal of persistent synthetic organochlorines has far outstripped nature's ability to break them down. Meanwhile, the continuing release of persistent organochlorines further dirupts this equilibrium. As a result, organochlorines have built up throughout the biosphere. They can be detected in the air, water, and food web of the global ecosystem. Throughout the United States and Europe, an array of organo chlorines can be found in the air, surface waters, and groundwater. Persistent organochlorines -- even those not regarded as air contaminants, like PCBs -- are also transported long distances on air currents, leading to r. .advely uniform global distribution. [Travis 1991] Even in the planet's most remote regions -- such as uic mww wubic or the Pacific ocean -- chlorinated pesticides, PCBs, dioxins, and chlorinated solvents can be found in air, water, snow, and living tissues. [Travis 1991, deLorey 1988, Gregor 1989. Rossberg 1986] Recently, Inuits living in Arctic Quebec -- remote from industrialization -- were found to have extremely high levels of organochlorines in their tissues and mother's milk, due to their position at the apex of a short and direct aquatic food chain containing large amounts of marine mammal blubber. [DewaiUy 19891 Organochlorines are also ubiquitous in the upper atmosphere. Oilorofluorcarbons, trichloroethane, and carbon tetrachloride are now globally distributed in the stratosphere, where their tendency to react with ozone has resulted in the depletion of 2 to 6 percent of the earth's ozone shield in temperate and near-absolute depletion of the ozone layer over Antarctica. [UNEP 1989] Because of its persistence, global organochlorine pollution will not be easily reversed. Any further releases of CFCs, for instance, are expected to result in continually increasing levels of stratospheric chlorine. Even if releases were stopped immediately, it would still take sixty years for chlorine concentra tions to return to the 1985 level (at which significant ozone depletion occurred over Antarctica). [Hoffman 1988] Similarly, If all PCB exposures could be stopped immediately, it would require approximately 6 gen erations for the PCBs in die human population to drop below detectable levels, due to the passing of these contaminants from one generation to the next. [Swain 1988! GOVERNMENT RESPONSES TO ORGANOCHLORINE POLLUTION In the 1960$ and 1970s, scientists discovered ex tremely toxic organochlorine compounds building up throughout the worldwide ecosystem. In many eases, these chemicals were linked to health problems among humans and wildlife, including birth defects and reproductive failure, cancer, and neurological impairment. The emergence of this information led governments to ban or severely restrict uses of such organochlorines as DDT, PCBs, dieldrin. endrin. pentachlorophenol, heptachlor, chlordane. lindane, and toxaphene. In the 1980s, the focus began to shift from individual organochlorines to groups of organochlorines and industrial sectors using chlorine or organochlorines. n ------------ ------------------------------------ --------1-- gL 062261 THE ft ft 0 0 U C T IS THE *___ o lien The discovery of worldwide depletion of the strato spheric ozone led to international agreements that will eventually eliminate the production of chlorofiuorocarbons. carbon tetrachloride, and 1.1,1-trichloroethane; however, it allows the substitution of other ozone-depleting organochlorines in their place. Some limits have also been placed on the discharge of individual organochlorines compounds in effluents from paper mills and water treatment plants using chlorine for bleaching or disinfection in the U.S., Canada, and Europe. Analyses of regulatory strategics in the U.S. have shown that total discharges and levels of contamina tion in the environment and human tissues have been reduced only in those cases when the production and use of chemicals have been banned. Fbr instance, tissue levels of the banned organochlorine pesticides 2,4,5-T and DDT in human tissues have declined significantly since their phaseout [Stanley 1986a], In contrast, strategics that have allowed air or water discharges of chemicals within specified concentra tions have merely shifted releases from one environ mental medium to another without significant im* . provement in total contamination of the environment or of human tissues. [Commoner 1990J SHIFTING THE FOCUS: FROM INDIVIDUAL ORGANOCHLORINES TO CHLORINE Tc* dr-, * number of organochlorines and small groups of organochlorines have been the target of phase-out regulations. But there are approximately 11,000 organochlorine products in commerce. [Braungart 1987] An unknown but possibly greater number of organochlorines arc formed as by-products in the manufacture, use or combustion of all organo chlorines and in all uses of elemental chlorine. The majority of these organochlorines are discharged into the environment without assessment or approval. Of the many industrial chemicals in circulation. information for preliminary hazard assessments are available for less than 2 percent, and new chemicals are bang brought on the market faster than testing programs can catch up. [NRC1984] Not only are most of the organochlorines discharged without hazard assessments, most have not even been identified. Organochlorines are almost always dis charged into the environment as diverse mixtures, the chemical character of which is unknown. As dis cussed in chapter 3. only a fraction (ranging from 1 to 30 percent) of the organochlorines discharged from paper mills, incinerators, and water treatment plants have been identified. Similarly, most of the organo chlorine pollutants that have accumulated in the fat. semen, and eggs of humans, fish, and wildlife remain of unknown identities, as detailed in chapter 2. As a result, adequate information will never be available to regulate pollutants -- organochlorines in particular -- on a chemical-by-chemical basis. Scien tists, environmentalists, and government officials have argued for a pro-active phase-out of the entire organochlorine class rather than reacting after the fact to scientific proof that contamination and environ mental effects have occurred. For instance, the chair man of the Science Advisory Board has argued: The general rule is that governments ban chemi cals on a one- by-one basis and only when "proof" of adverse effects is found. In the opinion of the Science Advisory Board, this reactive behavior is unwise, unscientific, and immoral-- The time is ripe (in fact, overdue) to end the laissez-faire policy for persistent toxic chemicals, organohalogens in particular. It is neither intelligent nor economically feasible to attempt to control them reactively, one-by-one. An anticipate and prevent policy makes far more sense. [Vallentyne 1989] A report by the Federation of European Chemical Industries came to the similar conclusion that organo chlorines will be addressed as a class rather than in isolation: To judge the role of halogenated organic susbtanccs. or rather organic chi rine com pounds as industrial chemicals, we cannot see SL 062262 13 TNI p *oouer Is T *E 0 SOD them isolated from the role of chlorine at a whole-- One may argue that the only funda mental solution for the environmental problems caused by organohalogonaied products and their r,*erts ir ts dnsricaUy reduce their production and restrict their use to closed systems. [CEFIC 1989] Hie Science Advisory Board has recommended a phase-out of all organohalogens, with exceptions only "in individual cases in which the weight of evidence supports the view that the chemicals in the approved dose do not jeopardize the health and integrity of natural ecosystems." (SAB 1989J The Board's chair man explained that the recommendation for a chlorine phase-out was not only necessary but feasible -- even inevitable: Given that organohalogens are inherently harmful to most forms of life, including humans, the GLSAB believes that a systematic phasing out of organohalogens is not only desirable but, with improving kn ledge, inevitable. Health concerns, the velopment of biospherically friendly technologies, and aging infrastructures wiB act as agents of change-- Based on health defects in the progeny of adults exposed to organohalogens, and recog nition of the need for global consols, there may be a general move in Europe and North America toward the phasing out ofindustrial processes leading. (Erectly or indirectly, to the produyetion oforganohalogens. If that proves to be the case, industries using chlorine tech nologies will be subject to chlorine phase-out policies and regulations in the not-too-disunt future--(VaQeatyne 1989] To eliminate orginochlorine pollution, chlorine production itself must be phased out. As long as chloride is convened to chlorine, contamination of the ecosystem with persistent organochlorines will con tinue. Organochlorine pollution can be stopped only by going to the root of the problem--eliminating industrial chlorine production. 0622&3 Si te TH P ft 0 D U C T IS THE ft 0 1 5 0 a TAIlf 1.1 OR&ANQCHLQRIMES Dl Ul. *h4 CANADIAN HUMAN POPULATIONS -- ADIPOSE TISSUE -- COMPOUNO Pmldlaa ftwtan* haueMoridC btnzMW hoKMnoc ftchbrtanc* tftbfdincyD0E.SJDOT: oj'* DOT: DJM0MI hwuenter wesdft lineaM rfim nerxMor-tll nentCiMr atnemcMor. tnnt-nonsNor diycnbrOiM tnisnana POi l*2nomw*) Chldrinstad dinim HpCDD 1 13 4.1,71 HeCDO 113.4.71* IfctCSD (taut) HiCLIO i 13,4.71 *CDD 113171 (Rff) 11 1 34 34 1 34 1 33 33 11 1 3S 34 33 34 1 1. a. 25.2134 a i i a a COMPOUND KriSO 11171ftOCDO (tool) PaCOO 11171 TCD02171 CMartoatad dlharadw HpCOf 1114171 MDFOBOO KxCDf 113.4,71 IteCDF 113171 rttOf 214171 0C0F(totd) PCDf 214.71 TCDF2171 Othar Chlorinate Aramtis cftbratenana dbftbmtenani dieibmtenanc 13dicftbrnteflanc 11 dfehbmtensna: 1.4tricftbmdaana ill trictibrotenana 114tncabmtenana 115tttnEnbmtenant 113.4linehlereBanani 1131 haadibrMaiBMW (REP) a i i i i i a a a i i i i i i ii i 34 1 34 34 34 a I a I COMPOUND acacMoraatyiana dhld2-(phtiylnadiyl)-dhnBt 4chleift 4 (mahytiuitonyi)- Imwic 1* table ftmrtryl-teiaBidtolca(4-chtomoh*ny0eh>ny< 4wmwaad dmcaioradiehtnyl aiMr htpuchtorediBteny mar hcacMoradiphany iomt nomettemdphmK mar ocacMoradieMnyl mar Aflphaic a^snedhlsrinad ciuaivlami kreffleeMereMuotomiiw toiftonochtoridetabb pad. Imathytmpr dieftbm-1-emnc 1.1diotbmftiranc 1,4haachbrl.3-buadbiM laracnbrnminp 1.112tmcabmaBiybra thehbroanan* 1.1.1tnchbreatnylana OiXSOUeroatihPlpAMShda vuiyUdana chbnda (REP) 34 34 11 11 11 1 Z7 V V V 1 11 11 11 11 11 1 1 1 1$ 1 TAIlfTI ORSANOCHLONIKES IN U.S. in* CANADIAN HUMAN POPULATIONS -- MOTHER'S MU -- compound (Rm Pmiddaa b*nan fttucnbndt btenant hweniond# (total) tenant hme.tend* * enbfliMcabman# y- DDD PiDDE BJ* DOTolDDT BJ* <4 . <>.< nwtienor tec.jcnior tgoxid* iincin* mtm ttanvnonacNor axycabreint 14 4 14 a a a 14 14 14 a s a 14 14 14 a POi (ES nomtet) 3.21.24. K.21X Chlorinat'd Dioiiw HeCCD 1.2.3.4,*.7.5HpCDD H3 4.7,5.5HO0 (tout) HCDO 1.13 4 7 5HiCOO 1i3.17.5- 30 a a a a COMPOUND KxCDO 111741 OCDO (tot*) OCDO 113.AI.71ftPiCO011171 TCD0U71 Chlorinate Dfcweohiraia HpCDf 1114171 HpCOF 1114.71ftHtCDF(tota) HcCDF 1114JJKiCDf 113171 HrCOf 113.741 ttrCDF 114.4.71 0CDF111A41.il OCOFdeaO PfCDF(MM) PfCDF 11171 P^DF 114.71 TCDF 13.71 Othar Chlsrinitid AramitiB chbmtemm dtcMoreMAtim dieftbmtenani ildichlorpMnana 1> dantomtenana i> (REP) a 31 a a a a 31 a a a a a a a a a a a i 1 a 2S a COMPOUND hcochbrotenanp ptmxNomtanana trichbrotenana tnehbrotentote 113triehbrotefmna 114chbmanyi-banana Atlfthatil Orpinechlorina* tafton UtncManda dhbredaiw chbremud eftbmiorm dhbrehcana shbieirwiwb chbfbpana dihrornocMoromahinp dibronMicNomrnatAana didibromytona dfeMoreofeeana FiaanllS FraealS FraaalS iwnyiiM chbnai tBtrxhbrMthybni tnehbreainybiM thchbroatanp 1.1.1Inehbrpfluommtthinp SL 062264 (REF) IS a 5 a a 5 i i i i i t i i i 5 1 5 t 5 1 i 1 V . IS T H IP COMPOUND Patlddee tenant heoebondeb* DDE M** DOT pjdtednn hecaettefeeodde eenacmer tnniHienaeMor wyciilordvie Chlerineted Dioxin HeCOD 12.3,4,17,0* feCDO mat) taCDD U3.4.7JHiOO 1222.72- 0 D U C TII T H CP 0 I SON TAIL! 12 ORGANOCHLORINES IN U.S. AND CANADUN HUMAN POPULATIONS -- HOOD -- (REF) 2 2 2 2 2 2 2 22 32 22 22 COMPOUND HriOO 1247J> OCODdsol) PeCOO 12i.7JTCD022JJChlerineted DAenaMim HpCDF 12.14.12J* terCDF (lets) MeCDF 12.3,4,7JFfcCDF 12JJ.7JHeCOF22.4J.7Jnote) PeCOF 22.4.72TCOF 22.7.1- (REF) 22 22 22 22 22 22 22 i 22 22 COMPOUND Other Aramaic Ofiinothlerinn didiiofOMnane heociuoretenene AHehetit OrienoeWerinee cvtoflUnuMndi cnonMi 1.1. methylene chloride tancMolMBtyMM (REF) 13 2 13 13 13 13 13 TAIL! 14 ORGANCHLORIHES IN U.S. AND CANADIAN HUMAN POPULATIONS COMPOUND PCS* (35 iiornerD Other Qriinediiorinee DDEdJhBocMorotenzane tmcMerMetenyl ether (REF) 12 12 S COMPOUND haacMoronapmMene pefiacitorepheM lenanoieehenel tncieofeoMM tnMlKMeiprePyllPMWW (REF) I C I 10 Table 1J ORGANOCHLORINES IN U.S. AND CANADUN HUMAN POPULATIONS -- IREATN -- COMPOUND (REF) Aram*tit Ortanediiorirae chiore tenant dfciiloro tenant dicftloretenane 1.2dichloroMnane 1> dicftloreunsne 1,4PCS* (teal) t Chlorofluoroarfcon* tnehtorofljoremethane dromochiorotnlluoroethane 1i-dit!Hofo-i.1.1J-i*fhuortethine Freeh 113 Freon 114 Freon 12 Fron2l 7 10 7 14 17 7 10 7 7 7 7 10 COMPOUND Other Aliphatic triairadUorinai diddeieeoiane 12lendiieroetnene 1,1,12leneMeroetnane 1.122* tMncMoroethyMie trtchbretenane trichbreethane 1,1.1tridibreethane 1,12tnefttorofttyene earten Utrshiende chbrodeone etibreterm cfitarehaone 1* ehbremetnine dientoroaetytene dieuorofitromethane methylene cnionde (REF) 7 14 14 7 II 7 7 7 7 II 7 17 It 17 17 7 062265 Si* TNE 6 0 0 U C TI ITHE f 0 ISON REFER)iCS FM TABUS 1.4,1.S, 1.1, AMD 1.7 1 J. Stanley. Breed lea* analytis of the Ft 1912 National Hus Adipose Tata* Surrey ipearoau. Vd 1; onm summary. Waahmg- too DC VS. Euvimuiiaul Prcaeeriat Agnney, Offis of Tcnic Sob- mw (EPA-56Q/5-16-03JX 1916. 2 2. and C Harvey. *Keaidn*i ad mwthnlhw et alowad peiisum halogcnseed hydtmartens is bleed ipcuuimi from gneil pumlirinr aarvey." Eirvutammiel Health Parapesiv** 60b 115*130.1915. 3 F. Kna. m *L "Survey ef selected otgmochlormc prrriirirlei to the gmcnl populism ef the United States: fissl yon 1970-197J." Amali ef the New York Academy at Sdnca 320:60-61.1979. 4 A. Jbmb. *Otereieel ccewiivuiii in tune milk.' Parirha Review* 19: M26. 1913. 5 E.P. Savage, w *L "Narional mdy of dtlorinatert bydrosrbm ietedofU rchduea in human milk, USA: geographic diatribnrim ef dieldna. heptachJor. hcptachlor ^oxide, chlorrianc, oxychlorta, md mirex" Amerioei Journal ef Epidemiology 113(4): <13-422.1911. 6 K Doughery at ai"Spem desrity md taxie aubftanos: a pomtial key te mvirortroettal health hazards.* Environmmtal Haalth Osuirrty The Qeniray ef Envirmmoul Agmta al Petenual Htznae Hazards. Jame D. McKinney, ad. Aon Arbor, ML Aim Arbor Same*. 1911. p- 363-371. 7 L Wallas aL 'Personal apmure te volatile organic earn- pound*: dima measursznent in breathing-ionc air, drinking wets, feed, and shalod breath." Emriranmatial Re*enn 35:293- 319,1914. I E. Palliari e aL *Purgeable organic compounds in ntothar'l milk.* Bullesn ef Envirmmcnul Goreaimnaam and Toxicology 21:333- 32S. 1911 9 A. Jetas. *PoJyehlc*xpheTyli (PCBsX polydUetwdiUiun p dioxina (PCDDa) and pelyddotedibauoAinM (VCDFi) in hizitm milk. Meed and adipeac uiua.* Seims ef the Toul Environment 64(3): 259- 393.19r. IQl T. Hudac, m al *Tris(didtloroptopyi)phof^iaie. a mtaagwnc flame retarder*; fraquou occurretcc te human roninal pLaxma.* Some 211: 931-951 1911. II J. OnatA. at al CharaoeiiuBen ef HRCOMS imidwuificd pcaka from tba analyiii of himan adipeac tissue. volume 1; tadtnisl approach. Wathingtai DC: U.S. EPA. Offis ef Toxic Subatanes (EPA-560/547- 002AX May 19r. 12 B. Bush e al "Polychlombiphmyi emgmcn, p.p'-DDE. and apmu funoiai in humane." Archive* of Enviranmonal Contaminatim and Tsieology 15 334-341,1916. 13 J. Laaeier and B. Dowry. *AaaocUtiai of biorefiacuris m drinking waio md body burdoi in people,* Aimal* ef the New York Academy ef Science* 291:547-556,1977. 14 1 Wallas, al "The California TEAM mdy: breath ememirw- 6BJ and pensial exposures to 26 volatile competed! in air sd drMxng wars ef 1 It rertdenu ef Lot Angela. Antioch. and Phlebagh, CA-* Atmoaphcnc Environs*)* 23(10)2141-2163,1916. 15 J. Ocutw and J. Stanley. Idmofistion ef SAXA eempomda in adipeac eitua. Washington DC: UJ. EPA OCRs ef Toxic Subnansa (EPA*560/J-I9-OD3), 1919. 16 C. Taka, a al.*Analyte* ef htsnan milk lampla wfletid in Hawaii for fviiduc* ef organochlornw pettiddea and polyehlottbiphm* yla.* Bulletin of Environmental Comwnination and Toxicology 30:606- 613.1913. 17 B. Kroterzynib. a al'Meaturmeii ef chemical inhaladen exposure in urban population in the pretence of endogenoul eflluatta." Journal ef Analytical Toxicology 3: 225-334.1979. II J. Mej, a iL "Polychjonnaicd biphety) and other chlorinated hydrocarbon reiiduea in adipotc tiatua of Canadiaru." Bulletin ef Environmental Contamination and Toxicology 21:97-104,19C. 19 B. Krotoarytitto and K. 0*NeilL*lBvolstary btoaccteitulwien ef svironmwxal poOixanta in nainnoiani hwcrogeuoua htonatt pr^iuli Os' Journal of Eavironnmtal Seats A Hslth A17(6V 655-463.1912. 30 K Srhcrtrr and T. Gaiiraria "Health hazard iiiiiimn of dblorinatnd **"** and dibeixofurmj ------f ia i--- --nv * Cbesoephew 16(1-9): 3147-2154.1967. 21 A. Scheos, m aL *Lervla of polydtlormaied dibaisefaMa, diltniMaEoxaa. PCBa, DDT and DDE, hiiarMnrrdsnaia. dicldiin, hsachloreeydoriexaaea and oxychlotdse in hums bnmet milk from Ac United Stats. Thailmd, Vicaas, and Gomany." Qmaeplina 16(14): 445-454.1969. 22 * **-'----- * *fv'-~~- --~* "------ *------ r "--' irf rfigmin dteua ef Agst Otmgt- spoaed ViautaiB reurm md matched eemmli.* Jesnal ef the Amoiean Madcal Aaiedatien 259(11): 1661-1667,1966. 23 A. Scheos m aL "Poiyddorinaiad biphenyl (POX DDT, DDE std Srr rhlorobenxaac (HCB) and PCDD/F iroewer Irwla at varies organa md nsopey sane from North Amsiem padettta.* Otantoaphew 1K1-6X 611416.1969. 24 J. Ms md L Marehand. *Conpariaon ef tone specific polychlori nated biphenyl iasnen at taman and monkey milk.* Bulletin ef Ea*uoamrraa] Contammaciee md Toxicology 39:736- 742,1967. 25 D. Devis and J. Mae, "Campariaoo of maids Icvala of ass orgwioehloriM compounds m breaat milk ef the gmcml and mdigswm Canadian population.* BuOam ef Environmental Coraaminaaon and Toxicology 39:743-749,1967. 36 S. Sevn, at aL "Polyehlorktaied biphmyta: eongms-^iadfie analyiii rf a eonmcreial mixan std a human milk nuns* Journal of Agrioilniml md Feed Qsniauy 33:24-29,1965. 27 J. Stanley, aL*Dmcsnhiaricn ef ihc prevalence ef pdychlarinated 4phmyl a^si (PCTPEa) m htenan adipeac ritas aarnpis." Qianoephac 20(7-9): 911-965.1990. 26 J. Ms and D. WcbB.*Nmrtheehlorint lubaooned coplanar pelychlorstwed txphsiyl eenganen in Cmadiaa adipeac tilsue. bread milk aedfwiy fooda.* Qsneephcrc 19(6-9X 1357-1365,1969. 29 D. Williams and G. LtBcL "Polydtlorinated biphmyl eengswr meiduea m hmss adipos naas samples from fivt Ontario mutudpeli6s* Qsnetpham 20(1-2): 33-42.199a 30 A Srhmrr a aL "Polydtlorinaied dioxin and dibenxofiirm levels from livenan milk from several locations ii the United Stain. Goman md VitmaA* Qtcmoephcm 19(14): 979- 964.1969. 31 A. Sdtaos. W aL 'Chlorinaiad 4axin and boniefunn levels m human milk fron Africa, Pakistan. Southern Visum, the Southern US. md England." Chencephoc 20(7-9): 919-925,199a 32 A. Sdmaa. a iL `Paroe'awg of 2J.7J-dtlorinated dibm p dioxina and dibmiefurani between adipoac tissue and plasms lipid ef 70 Maraarhnrmt VJcmam varrwu.' Omuus^han 20(7- 9): 951-951,199a 33 F. Kua "Orginochlorine peancida and polydtlorinaied biphmyl* in btstm adipse tissue.* Rcvfc** of Environmental Caitanunariai and Toxicology 120:142,1991. 34 J. Ms at al "Organodtlorine residues in adipose 6ssue of Canadians." Bulletin of Enviiceunmtal Ccraaminadorn and Toxicology 45: 661461.199a 35 M. Dearth and R_ Kitet. `Highly chlormatnd dimWhancfluromna in technical ehlordanc and in human adipotu tissue.* Journal of Ihc American Soocry ter Mast Spectrometry 1:92-91,199a 36 J. Mci aL "Spea/ic polydtlorinated biphmyl eengena diatribuooo in adipoee tissue of Canadians." Esrvirenmeital Technology 11:747-756.199tt Note: Data from the forthcoming J. Howard and J. Thornton. Body Surds: Toxic Contamination of Human Tissues and Fluids. Washington DC Greanpcas USA, in prcperiuav. SL 62266 17 THE PRODUCT II THE P0 II0 ORGANOCHLORINES IN THE GREAT LAKES "Seven recent reports have concluded that toxic chemicals, in large pan organochlorines, have im paired and are impairing the health of natural popula tions of fish, reptiles, birds and mammals in the Great Lakes basin. The concentrations of organochlorines in the wild populations are in the same general range as those in human populations. Because of their short generation times, populations of fish and wildlife may be showing effects that will appear later in human populations." (Vallentyne 1989) ASSESSING CHEMICAL MIXTURES The total impact of the hundreds of organochlorines in the Great Lakes ecosystem has never been fully assessed. The information and tools available to scientists preclude such a complete evaluation: r Mor.y crganochlorine contaminants presumably present in the Great Lakes ecosystem remain unidentified, due to limitations in analytical methods. Data on toxicology and environmental behavior is available for only a fraction of the chemicals that have been identified. Of necessity, epidemiological srudies of Great Lakes humans and wildlife have been limited to the few pollutants that have been thoroughly studied. Data on historical trends in contamination have generally been limited to pollutants that have been thoroughly studied and regulated, as well Epidemiology is not well-poised to detect subtle . or slowly manifested health effects, those that effect the offspring of exposed organisms, those that disrupt relationships among species, or those caused by pollutants for which there is no uncontammated control group. Despite these limitations, organochlorines have been linked to epidemics of reproductive failure, birth defects, and developmental impairment among at least 14 fish-eating species (including humans). In some cases, levels of specific organochlorine compounds in the tissues of the affected organism have been correlated with the severity of the effect (see table 2.1.) These associations, however, do not prove that the chemical correlated is the sole (or even primary) cause of the effect In no case have individual chemi cals been established as the cause of health effects. Instead, these associations point to certain chemicals as contributing to the effects and -- since high levels of one persistent organochlorine are usually accompa nied by others -- imply that groups of chemicals may be to blame. Great Lakes species are exposed to hundreds of chemicals that cause a diverse partem of health SL 062267 19 T H tP R 0 0 U C T . IIT M E 0 I SON TAILS 2.1 EftOEMICS IN SREAT LAKES SPKJE3 ATTRIBUTED TO ORSANOCHLOMNES ifMMt ERMt Ids Taut Pociiaben Mura Embryonic mommy bochorraot eftangos Huneit infants Dacmoad iwad dreundamn* OoemaMd arm wdgld Irnoerm oayehomsr domiopfflM InpdrO eogruova dMiopmant laidUQie Popiiation aachna Failure to east Aflurt earthy Enaryome and hateming mommy EggsMl thinning Wacng tyndroma Mnk FoeiAaddfl dMdna Raomdurtvo fHurs Waasng syndrom in othenng omr FoeidadondsclM Doubia-crscad fOfflBIMt Poeiiahon daSna Egg-shad thinning Raoreduelva afMs Voeharnof ehangas aim dorms fcactermnad sgnt-ftaron FoeJabon dochno Eggshdl tfannng Birth dafms Socharmed ehangM Hsnng-guS Common am Embryonic mommy Wassng syndrom linn oofs Fwniujnon of mala chads Livor aniargomaM fcoefarmed ehangaa tMiMidcisgs EggVsd thinning Emeryoroc rrertaiity Birth onfaes B>otrsmcd ehangM Rodroduesm ofScs PSathoCam' ram*. DOT. PCGa DOE. RCSs, dasea PCBa-toa PCfe DOE. Pdl (toot DOE.PCUdisda ton, Hd.PCB* PC8i.HCB.DOE SpasiM EDM Hng-bOM gul rthdafMS OtnafS Fomda famss tdMdg Caapiansm RaoroductvsfaBsn Birth drtacs Altamasonsia scnMnsm SnaogingtBma iithddMS Fdiurt Shaath PortsrtTant Embryonic rnmmy BrSdofaes Warn wasSng tyndram Noehtmaf ahanoonmoni of aggs iochmal ehangM Bduga Whda bmwnoMBpisiiod Tm RwtodueWoMam Pbttthrs Caaaa1 D0E.diddrtn. PCBc dmn PCla. ton PCBc, dienn PCBs,dosn RAHam. KBt Ssniok Allan 1091; Coibon 1000; Vdar 1M4; Fry 1U7; GEborson Ittft UC 1900. ChamcafshypothacadShivseaisadaffacstasadoncDrTaMonsith timii Imii and/or tmilarlty to affcs ind jcao by ateotura ia tha laborsdry. Titan chariots should not ba winad to raomamina srciwsvs ausa. snea organism In tha Gnat Likat neoMd s ana organocniormt at coewti to deans at otrar organoentorvsc tnat may causa tha sam. raiatM. at Other syrrptons. " PetyhaieganataO aromde bydrocarbona (Induing Mn, furana, FCBv and numson ethar organochlonrsa) HI eaun an Sanded swS at fyrtetofm through an idanteH Hochamcat rrsenanism. In some mat, intfvtdud ctudiec ttava eorraatad diaaw mm with tlaua to* ottpaeftcconvounds. m Mynudaar aromatte hydrocarbons. Ugh loads at unehtortnitad PAHs hava baan arwwatad wrth Bduga wtola haafth atfaes. effect; ;r. any can aa additfvely or synergistically to produce a single effect or suite of effects. In realworld ecosystems, actual impairment is almost al*.vays caused by groups or classes of chemicals. Indeed, the panem of epidemic impairment in the Great Lakes, in fact, is consistent with the known effects of hundreds of individual organochlorine compounds. According to the Science Advisory Board, chemicalspecific causality is nearly impossible to determine. btrause individual chemicals do not cause health efleas that are unique. Also, in many instances, the health effects caused by contami nants may be similar or identical to those caused by other agents. This phenomenon means that many different chemicals can result in similar health effects. (SAB 1989] 168 organochlorines are "unequivocally" present in the Great Lakes ecosystem, according to the Interni' tional Joint Commission on the Great Lakes (HQ* 20 -- SL 062268 THE 9 n e 0 U C T______ I $ T HI f0IS0N [GLWQB 1989] These organochlorines are those listed in the UC's comprehensive track of 362 pollut ants "about whose environmental and human health hazard little or nothing is known." [GLWQB 1989] (see table 22) In addition, at least 177 organochlorines have been detected in the tissues and fluids of the U.S. and Canadian human populations. Pesticides, PCBs. industrial chemicals, and by- products of the manu facture. use, or incineration of other organochlorines are ubiquitous in the fat. mother's milk, semen, blood, and breath of the general human population, (see tables 1.1 through 1.5) The National Research Council has noted that toxicity information is available to support hazard assess ments for less than 2 percent of the chemicals in commerce. [NRC 1984] Data on accidental by products and breakdown products are presumably even less ample. Because of these many unknowns, policymakers and scientists have focused on chemicals whose effects have been clearly demonstrated. In 1985. the DC identified 11 pollutants "known to be persistent and highly toxic, and known to be present in the Great ' Lakes ecosystem at levels of concern." [GLWQB 1989] This list was given priority for regulatory actions to reduce contaminant levels. Of these 11 "Primary Track" pollutants, eight are organo chlorines: PCBs 2.:.".! TCDD (dioxin) 2.3.7,8-TCDF Hexachlorobenzene DDT and metabolites Dieldrin Toxaphene Mirex All but two of these (TCDD and TCDF) were already subject to federal bans or restrictions in the U.S. and Canada. t These policies were implemented in the 1970s or eariy 1980s based on clear evidence of their toxicity, persistence, bioaccumulation, and widespread occurrence. The focus on contaminants whose threat is wellestablished has diverted attention from other pollut ants. Because of their "recognized threat to human health and the aquatic ecosystem," [GLWQB 1987] the Primary Track chemicals have been the subject of virtually all the field research and subsequent regula tory action. According to one reviewer, "Most atten tion has focused on the 11 critical pollutants' major sources, trends in concentration levels, and additional control strategies." [Colbom 1990] Most of the chemicals present in the Great Lakes have thus been neglected in field investigations. The contribution of the 362 chemicals on the DCs "Com prehensive Track List" to health effects among Great Lakes species has seldom been investigated. Virtually no information is available concerning historical trends in the contamination level of these pollutants. According to a Science Advisory Board review of all available literature on the effects of persistent toxic substances on Great Lakes species: An immediate and somewhat surprising observation after scanning the list of studies is that only a small number of specific persistent toxic substances (alone or in combination), including those listed in the Great Lakes Water Quality Agreement, have been assessed by in situ or laboratory studies for their effects on Great Lakes species. Most of the diverse Great Lakes aquatic populations have not been studied. These types of studies are indispen sable to understand and corroborate the observed functional responses to the ambient Great Lakes environment and to identify the major causal agents). [Fitchko 1986] Of course, results are available only for those chemi cals and effects that have been Investigated. The limited scope of available information concerning organochlorines In the Great Lakes is an inifact of the state of scientific knowledge and government priorities. The available information does not reflect the actual extent of contamination, impacts, and trends. SL 062269 21 THE PRODUCT IS T NI P 0 I ION TABLE 2.2 0RCAN0CHL0RINE3 ON THE UC `COMPREHENSIVE TRACT UST OF POLLUTANTS UNEQUIVOCALLY PRESENT IN THE SHUT LUES CHLORINATED BENZENES CftWBbWM* 1>dicMoroMam l.d-dieMGfpPanWI* HaocMorabbfiaM PwiUBMoteMiam 1,13.4mtneMeiMnM 1 ZSXat'icNerebwan* lAXneWorabpnWb 12.4-wchiorabBbn O.SKMreMnaM CHLORINATED PHENOLS dicMOWtiMM pmier*ofMrtPOb pmx!o/opMMl UHnouaraeiwnai 4>tncittmoMMl 2,4,S-ineMc>`spiwtM CHLORINATED TOLUENES 2<!tbrffd!MM KMorptbupn* 2.4- dicJtbfPtpiMM ;.t4!c!)ttrSUIUM haeniereteium 13.S.8*t*tre!*oretaluni 2J,*-tne!*oTMtdHanp 2,4XneNomoiiMm tncAtomitfluereteiiMM nKNereiaumtrtfluonM 2<StoraCM u*nnftuenM POLYCHLORINATED BIPHENYLS PCB-12S PCB-lSC pcn:a PCS-12S4 PCB-128) PCI-126 22`.L4,S.S',S-hwachtor>1.V-l(phn)f HmeMpoI.r-fcpfldnyl 2S'.13*i4.4,-Ktaeiiief>1.V-btB(wiiyt 2jrjk4.4.S.5'-*wucMere>U,-biiiiyl 22\3,4,4`,SV>oeftio^1.r^ip*iflii1 2J2\4.4\S,5'H'oenipi>1,1'-dtphPfll4 .1.-l.l'-biptwflyl . 7.3,4.4'.(.r-h*>acmof>1.r**<0M< 25`J.3,.4.4'S,S-ocae(owt.r-bi9Nn< ptnxnsroaontryi 22J.*S-wac-`,ioe>1.y-btph*rf 2.?,lS',S*B*flaehiofM.r-bipn*flH ir.4.S.r-g*n3cii<er-l.r4<pn<iyl L2\T.S*-t#irachioro-l,1'*&ph*nyl 22\4.5'-lftfpeNor-1,11*biBhMyt 2J\6.6MScNoo1 .V-hpibiryl 2.3.4,4*-l*r*(#oW-1,1 'hpharyl 2.3.4X<faef<on>1.1`-fcphnyt 2.3'.4'.S-ir.->c woro* i.1-bo hpnyi 2'J.Lifithe rp-1.1 ' hp hnyl OTHER CHLORINATED POLYNUCLEAR AROMATIC HYDROCARBONS 1<lUpfWMpWhNPM 2<hbrenipMhtlM 0exMofoorrwa DieftbronaoMMana 1 S-OkMoiorapmattna 1.7-dicnbrewioMBbPW 13-die!Upwaon)a* noMCfborpytpnp IftradtloreuDMMMM 1Z44ncNeiMRtMaMM utefitomipmAaMM trichbrppi*M}ibM pwiocneisarpiMnyi fimMoraafbtsfurM 13.7J-tatncNon0it*nB-P-<npa **) OTHER AROMATIC OR&ANOCHLOROIES pMitacMonsprtn* Hteacttonayrti* epcancuMct>orsoirp*<frnrrpdidini ptfycftioriniiad Mask (Nl pptycMorinaiPd Mnzyl ngoMM ctibrebMBtnfiuoriM J-ehboiTiydrp*yibiphai<oi T<>Mr*ffatnyLl>bn (pnAymtiiy()bMaM 2>dicMeratnfluprprwtypflatia 14-0ienierWtfluB((TtnylPanani 3,4-Oc.ilprBinfluofonWyiPonanp 2<W0fo(tnl1ourom*tfry()P*nw>p 3,4*4ici\tpr4'-(t(Tfleu>etTUiy<) bwopphpnoni 4<Mpra(mtwreRitnyi)bMaM 4'<S`T-t>'vWOf>3*-mMiy(-lXN*-PM<^ ylrauiyi) baron* 3S.4'-tncMe(QUiolMnyt(WMM 4\S\4*-UKl*ow,3*-wn4-t> bi*(pri(yim<OTy()Pisnt tncMorp<nDiylpiM<T)4)plipnylmMMMB r.^jT^'-pbnwtowJ'mMiiyi* t> M4phny<fTwnyi)baww 4-cAbre-4*-nMiy)apnflyirnRiiaM CHLORINATED METHANES, ETHANES. AHDETHYUNES kiompePoreratWw ftfpfflBdcMofWMMnp bramppieMerarathiM W* WrtBlNondb cnbipdiMenwwm cMprplorffl cftteremMMb 1.14ibrens-2<fMrotnM 1.1-dicNow-2-bfTtWno I i-Aeftbro- 1-brtnwtlbn* dicftiorelvo'PfflpBitM 1.1-dtcnioroMRsiM 15-oieAbfpotfiwo dicMOfOMNSP* dMorO(T(lttN hnocnio'OrtMn* II pj-iuehiorodHuni ifPKMo'PdtlrytMP 1,1,1 HneMprodiMnd 1,i.2-wworoinn* ttcWorotiiytono tncAbraflupreRbtMM tnctibrotnflooorediMM OTHER ALIPHATIC ANO AUCYCUC ORQANOCMLfiMNES U-UicAbWWWt iMMiaiiiM 1.1A3.4.4 b--Maw 13-bntttfww brociuortcydopwafliob XAbro-l-ertoynyfeyoofiroM CHLORINATED PESDCOU OJtycnbW* pj^doo M-COO U-OtE l*00 M'-OOMU W-OOT j'-OOT b-anoowflo MpWIUttMP hoptacMor mbd* HCH B^mdOM^cMer ea-MnapMot tnm-flonicMof ocaeniarppaDd* taOONMM Chhnehwxy tmtooOm 2.4-0 Off* dbMortrtO MCPA 4*T 10-nvnoH-<nro pibtontro Othtn tlrant cyimsM nun* MCMOf nwobeMar SL 062270 22 TMI PRODUCT IS THE POISON OCCURRENCE OF ORGAKOCHLORINES IN THE GREAT LAKES Table 22 lists the 168 otganochlorines on the UCs "comprehensive track" of pollutants detected in the Great Lakes ecosystem. These organochlorines include an array of pesticides, industrial solvents and intermediates, by-products of the manufacture, combustion, and use of chlorine and organochlorines, and unusual compounds that may be the result of environmental transformations of other organochlorines. Unquestionably, even this list contains only a fraction of the organochlorines present in the Great Lakes. In a given sample, current analytical technology can identify only those compounds present above a detection limit (usually in the low pans per trillion). Chemicals present in quantities less than this limit remain unidentified. When hundreds or thousands of chemicals are present in quantities less than detection limits, the total amount of unidentifed "trace" con taminants may make up the bulk of the total chemical burden. For instance, thousands of combustion by products are present in trace quantities in emissions from hazardous waste incinerators, but fewer than 100 have been identified. These unidentified chemi cals account for 40 to 99 percent of the total mass of unbumed chemicals emitted, according to the U.S. Environmental Protection Agency (JEPA). [USEPA 1990a] Moreover, exotic or novel compounds (Le., by products. breakdown products, or metabolites of better known organochlorines) are often difficult or impossible to identify in laboratory analysis. In most cases, the only pollutants that can be identified are those that can be matched to an existing database of chemicals and their behavior within laboratory analytical equipment As a result, chemicals that are not pan of the analytical database usually go uncharacterized. For example, the pesticide chlordane is a mixture of at least 50 individual compounds, many of which have not been identified: as a result these compounds have not been sought in human tissue analyses [Dearth 1990], and they are presumably not included in the chromatographic libraries used tot most identifications. Similarly, the pesticide toxaphene is a mixture of up to 670 individual com pounds, few of which have been identified or sought in human tissue samples. [Stanley 1986b] As a result, unknown compounds in biological samples usually outnumber the chemicals that are identified. For instance, Swedish analysts were able to identify less than 5 percent of the total mass of organ!ally-bound chlorine in fish tissues from the North Sea. [Sodergren 1989] A small but unquanti fied portion of the total pollutant burden in the fatty tissues and seminal fluid of the US. human popula tion has been identified [Stanley 1986a: Dougherty 1980]. At least 700 of the compounds in human adipose tissue "remain unchancterized. [Onstot 1987] Chemical analysis of organochlorines in Lake Ontario herring gull eggs was able to identify only 25 to 75 percent of the total organically-bound chlorine present. [Norstrom 1981] Of course, the toxicity of unknown compounds cannot be evaluated. Unidentified organochlorines thus pose an unknown but potentially serious threat to ecosystem integrity. The class of organochlorines shows a clear pattern of toxicity, often at very low doses; there is every reason to suspect that the un known compounds may be having significant effects on the health of Great Lakes populations. In a report on chlorine use in the paper industry. Environment Ontario has argued that trace unidentified contami nants could pose a threat as great or greater than known pollutants: One further thing is. however, most important. Ninety-seven percent of the total amount of organochlorine from a kraft bleach plant has not been identified as specific substances. Certain subtle toxicants such as chlorinated dioxins have recently been identified in some mill effluents. Although they form an infinitessimally small proportion of total organchlorines... they could be creating some real ----- SL 062271 23 TME PRODUCT IS THE 9 o I SO* The obvious question ic tow many ether subtle toxicants in bleach plant waste await discovery? (Bonsor 1988. Emphasis in original] cw.<Wc National Environmental Protection Board came to a similar conclusion concerning their failure to identify the hulk of the organically-bound chlorine in fish from the Korsunndet area of the Baltic Sea: U was found that only a minor pan of the persistent amount of EOC1 [extractable organi cally-bound chlorine] in the sediments could be explained by known susbtances. Is addition, there was a larger proportion of unknown, pasistem, lipophilic material in the fish populations at Norrsundet than in fish boat nonpotluted areas. There is a risk that among this material there are further substances which sre dresdy or will become distributed over wide geographical areas. Despite the fact that no biological effects could be associated to this persistent material, its actual occurence gives cause for concern, particularly with regard to what is earlier mown of substances with similar prepenicsJn addition, it is unacceptable that there is a risk that such material attains large-scale dispersal since, in such cases it is impossible to introduce counter-measures to reduce the damage. It is therefore of extreme urgency that methods are developed to reveal whether this large-scale dispersal of persistent substances also causes biological effects. [Sodergren 1989] EFFECTS OK GREAT LAKES FISH AKD WILDLIFE Organochlorines have been associated with epidemic hcahh cfTccis in 13 Great Lakes species of fish and wildlife, (see Table 2.1.) "All of these animals derive their sustenance from animals in the Great Lakes food web. especially fish," according to one review of health effects among Great Lakes species. [Colbom 1990] Typically, concentrations of highly bioaccumulative organochlorines in the tissues of these species are thousands of times greater than concentrations in the lakes themselves. The effects are truly epidemic. They have not frwn limited to the immediate areas in which pollution sources are located, although in some cases the most severe effects have occurred in such areas (Le, alterations in fish community structure near a paper mQl discharge on Nipigon Bay [Fitchko 1986]). For the most part, effects among fish-eating species have occurred across large areas of lakes (le., Green Bay. southern Lake Michigan) and may ever have been basin-wide or lake-wide. Bald eagle reproduction, for instance, appears consistently impaired along the entire perimeter of the Great Lakes, although the most severe population declines persist on the shores of Lake Ontario. The universality of organochlorine contamination and effects in the Great Lakes reflects the dispersion of pollutants throughout the food chain of the entire ecosystem. A recent scientific conference investigated whether these effects could be definitively linked to toxic pollution. The conference, which focused on primary track organochlorines, discussed epidemics of repro ductive and developmental failure or impairment among Great Lakes humans, terns, bald eagles, mink, trout, and turtles. The conference came to the follow ing conclusion: There are strong indications of a variety of in some Great Lakes fish and wildlife populations that are causally linked to the presence of persistent toxic substances -- specifically to DDT and metabolites, dieldrin, PCBs, and polychlorinated dibenzo-p-dioxins. [DC 1989a] Another review surveyed epidemics of reproductive failure from the eariy 1970s to the mid-1980s in Great Lakes mink, herring gulls, double-crested cormorants, Forster's terns, common terns, Caspian terns, and black-crowned night-herons. It concluded is follows: These case histories concerning reproductive dysfunction in populations of fish-feeding mammals and birds formally demonstrate the causal interrelationship between the observed epidemics and contamination of Great Lakes fish with organochlorine chemicals. This formal demonstration is based on a consistency of the 24 SL 062272 V THEPRODUCTI THEP 0 ISON i. .'iii.-icc relating the characteristics of the observed reproductive pathology to the pro* ence of specific chemicals in the fish and adults and in their progeny and to the experimentally determined toxicological properties of the Chemicals. [Gilbertson 1988] In some cases, research has attempted to link specific health effects to exposure to individual pollutants. Often, levels of specific organochlorines (Le.. PCBs. DDE) in an organism's tissues have been associated with the severity of the effect But Great Lakes species are exposed to hundreds of organochlorine chemicals, many of which cause identical, parallel, or synergistic effects. Only in the case of DDT*related thinning of eggshells have documented health effects been related to individual compounds. [Colbom 1990] New evidence, however, indicates that even this situation may be more complex. Although DDT and metabolites appears to have caused the eggshell thinning, the thinning does not appear to be the primary cause of the loss of eagle reproduction. According to one reviewer. The mechanism of the effect of DDE oo productivity of bald eagles was not by eggshell thinning but by some other mechanism. Egg shell thinning was a parallel symptom. Probably this whole field of ecological effects of toxic ctemicals- is full of parallel symptoms and we don't know what the full causal chain is for any species in the wild. [Ntsbet 1989) The partem of effects among Great Lakes species reflects exposure to a great number of organochlorines, rather than to specific compounds. For instance, the reproductive and developmental effects that have occurred among a number of species appear to hie uken place through metabolic and endocrine disruption caused by induction of enzymes associated with the aryl hydrocarbon (Ah) receptor. (Allan 1991) This enzyme system, which -- with minor variations -- is common to many fish, birds, mammals, and humans, can be induced by hundreds of different organochlorines. (see table 2.3) For example, the entire class of aromatic organochlorines are inducers of the Ah system; the most toxic forms (i.e., certain dioxins, furans, and PCBs) are the most potent ir^-rrv. [GLWQB 1989] Induction of this enzyme system is associated with developmental birth defects, wasting syndrome and embryonic mortality, genetic mutations and congeni tal birth defects, and cancer promotion. In some cases, the enzymes convert other chemicals (for instance, benzo-a-pyrene) into more toxic and carcinogenic forms). (Webster 1990] In addition, induction of the Ah enzyme system may lead to disruptions in the metabolism of sex hormones leading to infertility, impaired sexual development and behavior, immune suppression, and behavioral changes. [Nebert 1981. Silbergeld 1987. SUbergeld 1989) TAMILS CHEMCALS THAT INDUCE Ah EXZTMES (PARTIAL UST) AROMATIC ORGANOCHLORINES CMorOMUNMi OUonnM phmfe pcii PetjfcNeriniM na 9 dome PotycftoriMue tfbMnfunis CMonnud napMNmi QitoniiMd tmiwnyle M sow treratk orswioeiUortwe ORGANOCHLORINE K5T1CDIS DOT HeucMoiwydohcofl* (LineiM) OTHER ORGANOCHLORINES CMoicytti* OUoreiem*M OTHER CDWOUNDS S^rwfiyicMamMM Soufoc N*bt 1M1. Wrtmr 1ML Induction of the Ah enzyme system has been docu mented in numerous Great Lakes species among which epidemic health effects have occurred: Lake Michigan trout gametes [Binder 1984], Lake Ontario and Saginaw Bay herring gull embryos [EUenion 1983], embryonic Forster's terns, common terns, and black-crowned night herons from Green Bay [Hoffinan 1987], and newborn cormorants from Green Bay. [Allan 1991] In addition, enzyme induc tion has been hypothesized as a cause of near-total reproductive failure among mink living along the shores of Lake Ontario. (Allan 1991] Induction of enzyme systems is clearly a response to a large group of compounds rather than a single or ganochlorine. According to Environment Canada: (Researchers] ire finding an extremely high degree of correlation between the EROD induction capacility of egg extracts and certain SL 62273 sf developmental toxicity ind retrod success in colonial birds. However the correla tions betwen these measurements and levels of any single chemical measured in conventional residue analyses is very poor. [Allan 1991] Similar biological disruptions caused by multiple chemicals and leading to multiple effeas include alterations of thyroid function and interference with vitamin A/retinol levels. In each case, again, the effects are not unique to single chemicals but may be caused by chemical mixtures. Diverse groups of organochlorines are known to effect both systems. For instance. DDT, dieldrin, PCBs, dioxins, mirex, and octachlorostyrene are all known to disrupt thryoid function. Both thyroid and retinol disruptions have been documented among numerous Great Lakes species in which epidemic effects have occurred. [Allan 1991] A detailed dismission of all the major epidemic health effects associated with organochlorine exposure in the Great Lakes is beyond the scope of this document. Nevertheless, a few examples may illustrate the extent of the problem. Lake trout From 1965 to 1979, an average of two million lake trout were planted in Lake Michigan each year. Nevertheless, a viable self* reproducing population has failed to establish itself, apparently due to wide* spread mortality during embryonic and swim-up (new*bom) stages. [Fitchko 1986] Researchers found 167 organic chemicals -- many of them organo* chlorines -- present in adult trout tissues from south* em Lake Michigan. (Mac 1988] PCBs, dioxins, furans and other contmainants were also found in trout eggs from the same area. [Binder 1984] A subsequent study found that fry exposed in the labora tory to PCBs and DDT at the levels found in Lake Michigan had mortality twice that of unexposed fry. [Berlin 1981] Ah system enzymes in Lake Michigan trout gametes were 3.5 to 8.6 times higher than in control groups, and induction was associated with organochlorine contaminant levels, especially PCBs [Binder 1984]. When eggs from Lake Michigan trout were incubated in water from Lakes Huron and Superior (and vice versa), mortality was highest among the t v Michi gan eggs regardless of the water in which they were incubated: the cause of mortality was thus associated with the source of the eggs and sperm, and the re searchers pointed to "parentally transferred contami nants." [Mac 1985] PCBs and DDT were elevated in the trout from Lake Michigan and were considered contributing factors but could not hilly account for the elevated mortality. [Mac 1985] Subsequent reviewers wrote: The likelihood of separating out the effects of individual chemicals from mixtures is small since the number of permutations and combina tions is overwhelming... Although the evidence strongly suggests a chemical etiology, the responsible chemicals may neva be identified. [Allan 1991] The trout's reproductive failure was attributed to exposure to a number of organochlorines. As noted above, the Ah enzyme system had been disrupted in trout gametes, an effect that can be caused by hun dreds of organochlorines. [Binder 1984] One investi gator summed up: In spite of the planting of a total of 50 million lake trout in Lake Michigan in 1965-1985 and the development of a large papulation of marure adults, natural reproduction of lake trout was almost nonexistent. Laboratory studies and field verification studies have suggested that chlorin ated hydrocarbons, such as DDE and PCBs, along with other chemical contaminants may be contributing factors in the reproductive failure of lake trout, especially in industrialized regions on southeastern Lake Michigan. [Passino 1987] Bald eagles Bald eagles suffered severe population declines throughout North America in the 1950s and 1960s due to DDT-tnduced eggshell thinning. Since the ban on DDT, populations across most of the continent recovered. "Unfortunately, this was not so in the Greai Lakes," according to one review. "In 1986, there were reported to be only 25 nests on the Lake SL 062274 TNIPRODUCTI 8T H If Q ISOM Superior shoreline, 4 on Lake Michiagan. 4 on Lake Huron and 12 at the western end of Lake Erie. There were no nests on Lake Ontario." [Colbom 1990] A disproportionate number of bald eagles along Lake ivudugia shores are still unable to produce viable young compared to inland populations from the same states. [Colbom 1990] The cause is no longer thought to be a single chemical. One reviewer wrote: A case can be made that PCBs and possibly dioxins and furans contributed to embryonic mortality of bald eagles in the Great Lakes basin. The loss of bald eagle productivity is associated with a suite of clinical symptoms in addition to eggshell thinning, including embry* ooic and hatchling morality, failure of eggs to hatch, failure of established mature pain to nest adult sterility and excessive loss ofyoung birds__Levels of organodtlorine chemicals in the Great Lakes remain too high for successful re-establishment of bald eagle populations. [Coiborn 1989] Organochlorine are also known to have caused "feminization" among bald eagles and herring gulls. Exposure of male birds to DDT and methoxydilor in the laboratory has caused malformed testicles and the development of ovaries. [Fry 1987] Surveys of gulls in areas with significant organochlorine pollution in the Great Lakes. Puget Sound, and Southern Califor nia discovered widespread decreases in actively breeding males, unusual female-female pairing, and supernormal clutches of eggs attended by groups of females. [Fry 1987] "Stable breeding colonies of gulls in less polluted areas have not exhibited SNC [super normal clutches] or female-female pairing," the authors wrote. [Fry 1987] Gulls, terns, and cormorants A pattern of "chronic impairment of reproduction," [Gilbenson 1989] consisting of embryonic and chick mortality, growth retardation, wasting syndrome, and developmental abnormalities has occurred among numerous Great Lakes colonial bird species: Herring gulls in the lower Great Lakes during the early 1970s; Forster's terns in Green Bay in 1983; Double-crested cormorants and Caspian terns in various locations in the upper Great Lakes from 1986 onwards. [Gilbenson 1989] The partem of effects is consistent with "chick edema disease," which is caused by PCBs, TCDD. and other aromatic organochlorines. [Gilbertson 1989] One group of reviewers summarized the widespread nature of the disease:' 7he disease has been found in a variety of species in a variety of locations by different observers using different sudy designs. Out breaks of the disease have occurred at different times and seem only to be related to exposures of developing embryos to high levels of chickedema active compounds. [GHbouon 1989] Although researchers have estimated that several PCB congeners are responsible for the majority of the "chick-edema" toxicity, no direct relationship has been demonstrated between tissue levels of PCBs and the frequency and severity of effects. Instead, the effects appear to be caused by a mixture of PCBs. dioxins, furans. and other contaminants. [Allan 1991] It Is notable that dioxins, hexachlorobenzene. other aromatic organochlorines, and the pesticides DDT. heptachlor, chlordane, and toxaphene are also known to result in lowered testosterone levels; mice fed hexachlorobenzene in the laboratory had lowered serum testosterone and developed shrunken seminal vesicles and prostate glands [Haakc 1987. Elissade 1979] ` Ecosystem and Interspecies effects Virtually no informnion has been gathered concern ing the effects of organochlorine pollution on the integrity and structure of the Great Lakes food web. Effects on microorganisms at the base of the food web can have broad and serious consequences for the many species that depend on that food web for survivaL SL 062275 27 A number of organochlorines are known to be toxic to plankton, zooplankton, and other microorganisms. Tests of bacteria and phytoplankton in dilute solutions of organochlorine pesticides. PCBs, and dichlorophenol. for instance, have resulted in decreases in some organisms and increases in others. Such "selective" toxicity can have serious effects on biological diver* sity. According to the Science Advisory Board. These changes in phytoplankton species composition, although they may not reduce algal biomass, may have important implications for food chain dynamics through selective grazing preferences by zooplankton-- This may result in alterations to the species composition of the zooplankton community and perhaps the fish community. [Fitchko 1986] A few srcdies have documented such localized effects in the Great lakes. "The data show PC5 contamina* tion in the Great Lakes tends to cause growth reduc tion in nannoplankton species, including mostly small diatoms and phytoflageDates. Since nannoplankton has been shown to be a major food sources for many zooplankton species, the communities forming higher trophic levels would be affected," according to the Science Advisory Board. [Fitchko 19861 Pulp mill discharges in Lake Superior were found to have "decimated the benthic community of the extreme inner pan of Moberiy Bay of Jackfish Bay in Lake superior." [Fitchko 1986] PCBs and their metabolites are thought to have affected the Saginaw Bay nannoplankton and zooplankton communities, as welL [Fitchko 1986] Resulting changes in species balance at this level the Science Advisory Board wrote, "may not be desirable in an ecologically balanced ecosystem and may destabilize food-chain dynamics." [Fitchko 1986] "Few studies have assesssed the direct impact of toxic chemicals on fish community structure," according to the Science Advisory Board. [Fitchko 1986] No studies are known that have investigated the impacts of altered species-balance at the base of the food web on fish and wildlife in the Great Lakes or elsewhere. EFFECTS ON HUMANS In 1989, the DC issued the following warning con cerning the threat to human health posed by Great Lakes contamination: We have concluded from wildlife and labora tory animal information that persistent tpxk substances in the Great Lakes Basin ecosystem pose serious health risks to living organism. Sixteen Great Lakes wildlife species near the top of the food web have had reproductive problems or declines in population at one time or another since 1950. In each ease, high concentrations of contaminants have been found in animal tissue. Together with available human data, the information leads us to con clude that persistent toxic substances in the Great Lakes environment also threaten human, health. (UC 1990b] The contaminants to which humans in the Great Lakes are exposed are no different from those to which other species are exposed. A total of 177 organochlorines have been detected in the following tissues and fluids of the U.S. and Canadian human populations (see tables M through 1.5): 108 organochlorines have been detected in human adipose (fatty) tissues; 134 in mother's milk; 29 in blood: 43 in semen; 30 in breath. For the most part, these organochlorines in human tissues are the same ones present in the Great Lakes ecosystem (and in other ecosystems across North America). Again, these may represent only a partial picture of the total organochlorine burden '-hat has accumulated in human tissues and fluids. Despite certain variations, humans are essentially similar in genetic code and metabolic systems to the species in which epidemic health effects have been documented (Muir 1987]. According to a report for Environment Canada, similar effects can be expecti 2S SL 062276 TM ( PRODUCT IS T Nt R 0 I > 0 ft to occur in both humans and wildlife, but the larger size and slower reproductive cycles of humans "re quire more time to observe patterns of effects on the most sensitive life-stage -- the unborn and future [Muir 1987] Unking individual chemicals to human health effects is at least as difficult as linking them to wildlife effects, for the following reasons: There is no uncontaminated control group against which to make comparisons, leading to a failure to detea population-wide effects; Some effects -- Le., cancer and tnuldgene rational reproductive effects--may take up to 30 yean to appear, Humans are exposed to thousands of chemicals with identical, additive, inhibitive, or synergistic effects; Subtle changes in development, fertility, behavior, cognition, and immune response are difficult to measure; a Suspected effects cannot be confirmed in the laboratory for ethical reasons. As a consequence, little conclusive research is avail able on the effects of Great Lakes organochlorines on humans. The only major study undertaken to date -- published between 1984 and 1990 -- compared the development of children bom to mothers eating Lake Michigan fish to infants in a control group whose mothers did not eat Great Lakes Ash. Mothers who * fish per month gave birth about a week early to babies that weighed less (by about one-half pound) and had smaller head circumferences. The infants showed significant behavioral problems, including jerky, unbalanced movement and increased startle reflexes, decreased interest in novel stimuli, and a greaier number of abnormally weak reflexes. , [Jacobson 1988] The infants bom to fish-eating mothers had an im paired ability to learn. After 5 and 7 months, these infants performed poorly on visual recognition tasks. After four years, the children bom to fish-eating mothers the infants showed impaired short-term memory in both verbal and quantitative tests. [Jacob son 1988] One reviewer summed up the effects as follows: The tendency [of infants bom B mothers eating Great Lakes fish] to respond to a new nimalis decreased in direct proportion to the level of maternal exposure to contaminants is flsh consumption, suggesting a more than ten percent decline in visual recognition memory, this observation suggests an effect ofcoactminuts upon the centers of higher integration in infants secondarily exposed via maternal circulation. [Swain 1988] The authors investigated a correlation of the effects with in utero PCB exposures. Fish-eating mothers had higher concentrations of PCBs in their blood and umbilical cord serum. Further, these levels were correlated with the severity of the cognitive and physical effects in the infants. The data demonstrate' the continuation of a toxic impact received in utero and observed initially during infancy on a dimension of cognitive functioning fundamental to learning." the authors wrote. [Jacobson 1990] Undoubtedly, PCB exposure was associated with the infants' impairment. However, this association did not mle out other chemicals as additional, or even primary causes. Children bom to mothers eating Great Lakes fish are almost certain to have elevated levels of the many other organochlorines in those fish. The authors did measure serum levels of DDT. hexachlorobenzene, oxycHondane, heptachlor epox ide, trans-nonachlor. Mirex, and polybrominated biphyenyls; they found no association with the effects they examined. However, no other organochlorines were investigated, including the dioxins, furans. or any other chlorinated aromatics. "Environmental exposures include a mix of highly toxic organic chemical contaminants, such as the dibenzoforans and dioxins, which are present only at trace levels, and therefore could not be evaluated." the authors explained. [Jacobson 1990] 29 SL 062277 Nouuljr. i study of newborn rhesus monkeys exposed to TCDD in the laboratory -- but not to PCBs -- had strikingly similar results. The offspring of mother monkeys fed extremely low levels of dioxin (from 5 to 25 puti per trillion in their diet) showed subtle cognitive and behavioral impairment. Although there were no obvious physical effects, the infants bom to exposed mothers were unusually dependent and, in turn, their mothers treated them as if they were ill or injured. Months later, the exposed young performed poorly in memory and other learning tasks. In peer groups, the dioxin-exposed young were unusually aggressive, initiating violent behavior more often than unexposed monkeys. [Bowman 1989a, Bowman 1989b. Scharnz 19861 Several recent reports on the Great Lakes have pointed to large-scale deterioration of health parame ters that can be affected by exposure to persistent toxic chemicals, including organochlorines. [Muir 1987. Colbom 1990] While no causality could be demonstrated, the authors noted similarities between human health trends and the effects in wildlife attrib uted to synthetic chemicals. For example, one report for Environment Canada pointed to increasing rates of infertility, many types of birth defects and chronic neurological conditions, and total cancer incidence footh including and excluding lung and skin cancers) -- all since the 1950s. [Muir 1987] In addition, one review found that mean sperm density had fallen by 30 to 50 percent since 1930; about one-fourth of the decline was statistically conel3md with the presence of PCBs and other individual organochlorines detected in human sperm. The remainder of the decline could not be associated with specific chemicals. [Dougherty 1980] Despite the paucity of information directly document ing human health effects, there is good reason to be concerned by human exposures to the same c-emicals that are causing epidemics among Great Lake wild life. The Science Advisory Board summarized: There is..abundant evidence of health effects, paniculary in early developmental stages in wildlife populations. Although the human data are limited, it is likely that exposed human populations behave in a similar way to exposed wildlife populations. This phenomenon exists because we share similar ancestries and evolu tionary histories. We are exposed to the toxic chemicals; we accumulate the chemicals in our bodies, and toxic chemicals often have similar mechanisms of action in humans and wildlife. On this basis, it is reason able to presume that toxic chemical exposures may have a significant effect on the health of our children at the community and population levels. Because of their shorter generation times, fish and wildlife may truly be what many have suggested: environmental equivalents of miners' canaries. If such should prove to be the case, then we will have doubly jeopardized the lives of our children trough the shameful legacies of prenatally impaired health and toxic ecosystems. [SAB 1989] The Board's chairman continued: The concentrations of organochlorines in these wild populations [in which epidemic health effects have occurred] are in the same general range as those found in human populations. Because of their short generation times, popula tions of fish and wildlife may be showing effects that will appear later in human popula tions. [Vallentyne 1989] Given the biological similarity between humans and other affected species, this conclusion is hardly surprising. Humans, after all, occupy a position on the food chain that is as high or higher than pisciverous birds and mammals. Human infants, who receive bioaccumulated contaminants eross-placenially or via mothers* milk, occupy an even higher level. Environ ment Canada summed the situation up as follows: Since both human and wildlife populations are exposed to similar types of contaminants and have many biological similarities (physiologi cal, biochemical, cellular orgination) it is not unreasonable to anticipate that at equivalent levels of exposure there could be some similar effects in both groups.. The similarity of the effects across species is striking--While there 30 SL 062278 THE P * 0 0 U C TI 1T H E POISON Ore oaly limited dan on human health effects available, there is more information on effecs in wildlife. Both data sets suggest that develop mental effects occur in the offspring of exposed parents rather than in the parents themselves. [Allan 1991] TIME TRENDS IN GREAT LAKES 0RGAN0CHL0R1NE CONTAMINATION Claims that toxic pollution in the Great Lakes -- organochlorines in particular--has improved signifi cantly cannot be defended by available information. While there have been clear improvements in conven tional pollution (oil, grease, fecal coliform), there are insufficient data to support conclusions about con taminant trends for virtually all the organochlorines in the Great Lakes. For many of those organochorines the: hove been assessed, levels in the Great Lakes food web are stable or increasing. Determinations of contaminant trends have been almost completely confined to the primary track chemicals. Concentrations in Great Lakes water and sediments of most of the organochlorines that were banned in the 1970s decreased in the decade follow ing their phase-out. [Allan 1991] There is a similar pattern -- but with important exceptions -- for concentrations of banned organochlorines in the food web; levels of rairex. heptachlor, chlortiane, and some congeners of PCBs decreased in the tissues of most tiuiii ihe mid-1970s through the 1980s. [Allan 1991] However, the decreases of these chemicals have equilibrated -- or "flattened out** -- in the last five years. The now-stable concentrations continue to threaten the integrity of the ecosystem. "Early de creases in certain persistent toxic chemicals have leveled out above presently acceptable targets, and no clear strategy has been established to achieve further reductions," according to the UC. [UC 1989b] Some of the severely restricted organochloriraa, however, did not decrease in living tissues. DDT levels in Lake Superior trout, for instance, doubled between 1985 and 1988 [Allan 1991]. Dieldrin in Lake Ontario fish decreased from the 1970s to the early 1980s. but then increased before equilibrating again. [Allan 1991] The most toxic PCB congeners, however, have shown no decrease whatsoever. (Allan 1991] The lack of overall improvement in organochlorine contamination has been attributed to the great persistence of these chemicals in the environ ment and their transfer from one generation to its progreny, as well as to "inputs from remaining point sources, cycling of contaminants within the aquatic ecosystem, remobilization of sediments, as well as continued inputs to the Great Lakes from atmospheric deposition and leaking hazardous waste rites." [Allan 1991] The chemicals that have been tracked are, with few exceptions, the primary track chemicals -- those already identified as serious problems and subject to regulatory restrictions. Data are available for virtually none of the hundreds or thousands of compounds that have not been restricted. As a result, the available information allows an evaluation of the effectiveness of the phase-outs applied to a number of primary track organochlorines. It provides no basis for evalu ation of time trends for the entire class of organo chlorines. Of the many organochlorines that have not been restricted, there are historical data for only a few. Of these, concentrations in the food web do not appear to have decreased. For instance, "dioxins and furans are widely distributed through! the ecosystem; based on limited data, concentrations in fish from Lake Ontario have remained relatively constant," according to Environment Canada. [Allan 1991] In human tissues, beta-hexachlorocyclohexane and hcxachlorobenzene may be inceasing, and sufficient data are not available to assess human tissue trends for other organo chlorines, including the dioxins. [Coibom 1990] SL 062279. ________________ 3' T tt I PRODUCT IS T nI * o t SOM For iauM ui*inochlorines, however, there are no data whatsoever to support conclusions about contaminant trends. Ho information is available concerning trends in food web levels of chlorinated phenols, benzenes, styran, toluenes and other contaminants. Even in the present, according to Environment Canada, "wildlife data are available on levels of only about twenty wellknown organochlorine contaminants." [Allan 1991] Further, changes in analytical methods over the last 20 years make those data sets incomparable. As discussed above, many chemicals have not been identified at all. and there is thus no current concen tration data, not to mention historical dam Of course, chemicals that have not been identified cannot be assessed for chemical trends. Since the bulk of organochlorines in the Great Lakes have not been chemically characterized, a comprehensive evaluation of contaminant trends cannot be performed. Without chemical-by-chemical analyses, the only way to assess trends in organochlorine contamination would be to compare measurements of total organi cally-bound chlorine. Methods to measure this pa rameter, however, have only been developed in the last five yean. There are no comprehensive examina tions of this parameter in Great Lakes water, sedi ments, or tissues at current levels, not to mention historical levels. An historical assessment, then, cannot be performed. Given the fact that paper mills, incinerators, and other sources are known to be continuing the discharge of persistent organochlorine contaminants into the Great Lakes, it is unlikely that total organochlorine contamination is improving. The continued occurrence of organochlorine-associtied epidemic health effects is further evidence of the lack of meaningful improvement in total organo chlorine contamination. Effects on terns, bald eagles, turtles, mink, and trout have all been documented within the last five years. [Allan 1991] Thus the VC refers to "the continued and growing dangers posed to living organisms, including humans, by the presence of persistent toxic chemicals in the Great Lakes environment." [UC 1989b] 32 SL 062280 TKf P H 0 0 U C T________ 18 T W I________ P Q ISON CHLORINE AND ORGANOCHLORINES IN INDUSTRY: RELEASES AND BY-PRODUCTS About 70 percent of chlorine is used to produce the 11.000 organochlorine chemicals that are used as solvents, pesticides, plastics, refrigerants, degreasers, chemical imcnnediates for the production of inor ganic chemicals, and for other purposes. The remain* ing 30 percent is used as elemental chlorine (or derivative chlorinated oxidizing agents, such as chlorine dioxide and hypochlorite) in bleaching, disinfection, or metallurgical processes, (see table 3.1.) TAIL! 3.1 U.S. USES OF CXIQMNE III IMS userggyrof mm. BmmataMm Pulp and paw Inoifuae eWracat' Wrv trasram Titanium dioxoa IS 0) I (1) S HI 3 (1) OrymclUomm FNCVC.tl.Y*'* dtcrtond* Oilerinxad mMiim" CnienncadaoivNrtKaittMBandtuiylifla) cKmoienyonN 004 organKrtomW* tor prooyWw d* Oirw wrrpounda 24 (1) 7 (2) 7 (2) S (1) (2) S (1) 12 (1J) t IndudM im of Nomonta eiibnno to producad pun irvtoI cfllondaa, .nd mat* dUoratoX " QitoHuid mothanM am uwd cctoniWy in ttio pmdudtai of ethor orjanocMonm, tucft a cNomfluomearbom and p+ocoat. m Indudo* cMonnilad pfppan**. propantt. butanaa, PuuSn, and oift* OfganocftlonnM wiUi 3 of 4 uroon OPfls. Sourcax 1mm (1) Vonkanan 1991: (2] Cbnitaon 1990. Bacauoa ftguw fmm tNo aoumo* WgM W4Wtt, tool Poo ret aqua! 100 Mrcwt. AH uses of organochlorines and chlorine contribute to the global accumulation of organically-bound chlo rine. In many uses, organochlorine products are released directly and immediately into the environ ment. In others, organochlorines are transformed by use, treatment or degradation processes. In some cases, their release is delayed by storage or other waste "disposal" methods, such as landfilling. The full impact of a single organochlorine product (i.e., the use trichloroethylene as a degreasing agent) includes releases of both products and wastes during the manufacture, use and disposal of that product. Such releases involve numerous chemicals and take place at different times at diverse locations. Assessing the full impacts of even a single use of a single organochlorine is thus extremely complex. Moreover, numerous organochlorine by-products are formed in virtually all process involving chlorine and organochlorines: all uses of chlorine and chlorinated oxidizing agents, a the manufacture of all organochlorines, the combustion of all organochlorines, and some industrial uses of organochlorine products. In every case, these by-products include the most stable, persistent, ubiquitous, and toxic organo chlorines (e.g,, dioxins, fiirans. hexachlorobenzene. etc.). Even organochlorine products of lesser persis SL 062281 33 TNI PRODUCT I* THE * 0 SON tence and toxicity are associated with these extremely hazardous by-products. Because these by-products are common to virtually all processes involving chlorine/ organochlorines, linking individual products or processes to chemical contamination is virtually impossible. RELEASES OF ORGANOCHLORINE PRODUCTS In many uses, the release of organochlorines to the environment takes place directly. For example, pesticides have been described as "purposeful envi ronmental contaminants'* that are deliberately dis persed into the ecosystem. [Metcalf 1987) Only a tiny fraction reaches the target pest, while "the remainder, greater than 99.9 percent, is essentially wasted and enters the environment through air drift and soil runoff, by leaching into groundwater, by entrapment into dust and air currents, and by deposition in rain." [Metcalf 19871 Similarly, the bulk of chlorinated solvents produced are released directly into the air (via evaporation , during product use, fugitive emissions, or wastewater discharges). From 60 percent (for tetrachloroethylene) to 85 percent (for dichloromethane) of total amounts of solvents used in industry evaporate into the air at their place of use. [Lawrence and Foster 1987] According to the Federation of European Chemical Industries. 7:volatile organo-halogen compounds, like the halogenaied solvents, the vast majority of the production will ultimately evaporate into the atmosphere.* [CEFIC1989] In some uses, organochlorines are released to the environment after a delay or in the form of other organochlorine compounds. For example, polyvinyl chloride used in plastic packaging enters the munici pal waste stream, which is often burned. A broad range of organochlorine by-products have been identified in the emissions from incinerators burning chlorinated plastics. [Yasuhara 1986] Some of these by-products will also be captured in incinerator ashes, which are then landfilled, contributing to groundwater contamination. Even the so-called "recycling" of organochlorine products or wastes merely delays or alters the form of their release to the environment According to the Federation of European Chemical Industries: Successful recycling of such products means the' i an amount of chlorine becomes in , for which industry will try to find an st, probably in anotho- organohaloge scycfing might only result in an inci. i volume of orpnohalogens present at any momeu. [CEFIC 1989] Because of the number of industries using chlorine and organochlorines and the complexity with which releases into the environment take place, the risks of individual uses of chlorine and organochlorines cannot-be separately assessed. Because organo chlorines are globally distributed following their release, linking industrial sources of organochlorines to local contamination, exposure, and health problems is even more difficult. Nevertheless, some Individual uses of chlorine and organochlorines have been linked to elevated levels of contamination and health problems among communi ties and workers receiving the most immediate expo sures. Examples include the following: Contamination of rainwater and groundwater by the organochlorine pesticides alachlor and atrazine is especially severe in the Midwestern U.S. where use is highest [Goolsby 1991. NCAMP 1990] Applicators of certain organochlorine pesticides have been found to have high rates of certain types of rare cancers, including soft tissue sarcoma and lymphatic cancers. [Erikkson 1990. Wiklund 1989] 3.5 million U.S. workers experience direct exposures to trichloroethylene; 500,000 to tetra chloroethylene; and 1.5 million to 1,1,1-trichlo-fl roethane, according to The National Institute for 34 SL 062282 TNI PRODUCT II T Nt *__ 0 ISON Occupational Safety and Health. [SRC 1989b. SRC 1989c, SRC 1989d] For each chemical BY-PRODUCT FORMATION workers are listed as "populations at high risk.'* Chlorine is an extremely reactive substance that tends Occupational exposure to organic solvents in to combine almost immediately with organic or other general has been linked to neurological disor material with which It comes in contact It acts as a ders, but only very limited epidemiological data powerful oxidizing agent bonding with available are available concerning individual chlorinated electrons in organic maner or other materials. solvents. [OTA 1990] Chlorine's reactivity accounts for its uses. As s Pulp mill discharges have been linked to malfor bleach, it reacts with and destroys the natural organic mations and population declines among fish molecules that cause stains or unwanted color. As a populations in the Baltic Sea. [Sodergren 1989] disinfectant it destroys living organic molecules. In Dioxin and furan accumulation in fish caught chemical manufacture, chlorine replaces one or more downstream from U.S. paper mills poses calcu hydrogen atoms bonded to carton in petroleum-based lated cancer risks up to 1 in SO, according to chemicals. EPA. tUSEPA 1990b] Workers in chlorine-bleaching pulp mills have Chlorine-carton bonds tend to be stronger than shown elevated rates of cancer. According to the chlorine-hydrogen bonds, leading to organochlorine International Agency for Research on Cancer, products that ait often more stable, more persistent "Several studies of pulp and paper workers have less flammable, and more toxic than their unchlori demonstrated increased risks for certain cancer nated relatives. As a result organochlorines are used sites, e.g.. rumors of the lymphatic and hemato extensively as coolants, solvents, plastics, and bi poietic system as well as stomach cancer. An ocides. Some organochlorine products are less stable; impressive lung cancer excess was found among these tend to be used as chemical Intermediates and in paper and board mill workers in Finland, but not other reactive uses. in studies elsewhere... It is impossible to link any of the excesses to specific single compounds or mixtures, of which there are a multitude in Due to elemental chlorine's great reactivity, its reactions with organic muter cannot be easily or pulp and paper industries." [Hogstedt 1990] At least 18 studies [Doull 1977, Doull 1980a, Doull 1980b. Cantor. 1987] have linked human cancer to drinking chlorinated drinking water. A 1?S8 study found that non-smokers drinking chlorinated water for 60 years had bladder cancer rates 4 times greater than a control group fully controlled. In all uses of elemental chlorine -- bleaching, disinfection, metallurgical processes, and the manufacture of organochlorine products -- unwanted organochlorine by-products are formed. In addition, the incineration of organochlorines and some uses of organochlorines also generate a large number of organochlorine by-products. that drank unchlorinated water, [Cantor 1987] "Analytical case control studies have shown a modest increase in risk of bladder cancer and colon cancers with relatively long-term exposure to chlorinated drinking water," according to one review. [Murphy 1990] These by-products include the organochlorines of greatest persistent and toxicity -- the chlorinated dioxins, furans, FCBs, and hexachlorobenzene. Even the least toxic organochlorines appear to give rise to the most ecocidal by-products at some p int in their lifetimes. Processes in which these by-products have Chemical workers exposed to vinyl chloride been identified are listed in table 3.2. have exhibited elevated levels of brain cancer and other cancers. [HSDB 1991] Vinyl chloride is considered a known human carcinogen. SL 062283 __ 35 TAILSM processes THAT form extremely fersitent orcanochlorixe it-pmqucts CModaapndudMi Pulp Md paper Maadftig MamAdtun of ndinad nwafo ito cMoriaa Wm iMoiinatoa 08 ndbaag taftt otganocMprino eaafyof Um of eMorfniftd dagtoaftng oofcanft Ino'noafion of onanocfdoitna MaftAon of onanoeNortna panda MaruAeturo of $3 Inducttft orpnecttednai Um orsanoeMortno itmnrwMM ft immAcftit 17 ogn-tittorinaud OMmotS MuitaowoefFSto ManiAeturo of cMoropnenott Mamdaeura of eMorotenanoa Manufacluro of wieHorptiyenn, hsacftoroMiaiM, 1J-oiemoro*thflo Manufaeuro of tatneMorootnytoM Manufacture of tneMorefthyMM Manufacture of carton totnoHondo Manufacture of hcaeMoreeyftoeonftftono and ponatMorenRreoamaa Manufaeuro of vinyl cftoddo Manufacture of cMoroftiianap Manufaeuro of DoHdittratanM IT^ROOUCIS taacMeradaiatna. oeacMoreotyrenai ftofta doom, funis, DfttaeMorgbofBM ftoBM. funis. hMacMoretwsant oeachlorealyiMa tin* ftoont. fonts dfednt. hint* octacMoreityreis, hatacNoredatam dtodnc, funis, hsacdleredaiaAo, hotacNoreduaftana dftatita. dtacMoredatafta dfenni. funis, ttsuchlorabanftno dtantfwaia, hoacMoredamna dMflftfwaift dmdis. funis, hcucMorobanano. hcacMoiedutaSana hcactuorePomm hnehtorodamna. taacNoredutarfana dcocMorotoRiana hcscMoredanrei* isxacMoreduaftiM ficocMorotaiaaa dtaus. turns* diesis--pofycltlonnatad dibensdiegns funis -- potycHohnatoJ fiidonsdunis. t InrecSgatore found thaw oiganocittoiinaa a amamnams m eommweiS hnacNorobamna dot could not dotormno fha method of forrmoon m _ tha precwedon procaaa. (Espoott 1980) Sourcaa; (1) SNEPB 1990- (2) HSOB1991: (3) Vorechuoron 1983: (8) tonot 198ft (5) Sunilo 1988; (8) Oadma 1990: (7) Rao 1989: (8) Thonpoon 1990; (9) Hondl 1987; (10) USiPA 1989. USEPA 1987a; (11) Ewooito 1980; (12) La 1987; (13) Rousarg 1988. (14) EPA 1985b (IS) FTCN 1988. 38 SL 062284 THE PRODUCT I> THE9 Q ISON CHLuRiNE MANUFACTURE The electrolytic production of chlorine requires careful purification of raw materials and equipment surfaces. (Schmiainger 1986] Little or no organic material is present, except as trace contaminants, is relatively stable plastic materials, or as graphite electrodes in some electrolytic cells. [Schmitringer 1986] Nevertheless, organochlorine by-products are pro duced in this carefully controlled process. Ocuchlo* rostyrene. hexachlorobenzene. and hexachloroethane have all been identified as wastes from electrolytic chlorine production. [HSDB 1991. Verschueren 1983] Polychlorinated dioxins have also been identified in graphite sludges from Swedish chlor-alkali plants. [SNEPB 1990] ELEMENTAL CHLORINE USE The reaction of chlorine with organic maser produces an extremely broad spectrum of organochlorines. In pulp mill bleaching, water treatment, and metallurgi cal processes, these by-products include the most persistent, toxic organochlorines. Pulp and paper Hundreds of organochlorine by-products have been identified in the effluents from mills that use elemen ts rMorinr to bleach and deligmfy pulp, (see table 3.3). These by-products include a range of mutagenic and carcinogenic compounds as well as reproductive and developmental toxicants [Bonsor 1988]. Only a small fraction of the total organically-bound chlorine in pulp mill effluents have been accounted for by chemical-specific analyses. An estimated 80 percent of the total consists of high molecular-weight organochlorines that are not amenable to chromato graphic analysis. Unidentified low- and mediumweight organochlorines account for another 10 to 17 percent, leaving only 3 percent composed of identified compounds. (Bonsor 1988] The many organochlorines found in the bleaching process are distributed to wastewater discharges, warer treatment sludges, air emissions, and the paper products themselves. Pulp mill sludges have been found to contain a broad range of organochlorine compounds, including the chlorinated dioxins. [Mantykoski 19891 Organically-bound chlorine typieally composes as much as 4 percent of the sludge. (Mantykoski 1989]. The sludges are usually disposed of directly on land or through incineration. By-products identified in emissions from pulp mill sludge incinerators include the chlorinated phenols, catechols, guaiacols, benzenes, biphenyls (PCBs). dioxins, and funns. [Mantykoski 1989] Bleached paper products contain organochlorines as well. PCDDs and PCDFs have been identified in the low parts per trillion in diapers, cigarette paper, tampons, coffee filters, cosmetic tissues, and bleached milk cartons. [Rappe 1990b] Environment Ontario estimates that approximately 2 percent of the organo chlorines formed in a bleaching plant remain in the pulp product, leading to total organochlorine concen trations of as much as 1 percent in bleached pulp. (Bonsor 1988] "However, date on organochlorine content of pulps is very sketchy and unpublished, since there was no interest in it until recently, and there are as yet no accepted testing protocols." the report noted. [Bonsor 1988] In addition, detergents, liquid soap, and tall oil pre pared from bleached pulp contain dioxins and funns in concentrations up to 447 pans per trillion, meas ured as toxic equivalency factors relative to the toxicity of 2.3,7,8-TCDD. [Rappe 1989b] No other organochlorines have been investigated in these products. The use of chlorine dioxide and other chlorinated oxidizing agents produces a similar range of by products. Chlorine dioxide substitution allows lower total chlorine input and a consequent lowering of SL 062285 37 TUI > A00UCT IS T H* *9I0A discharges of total organically-bound chlorine; however, the chlorine in chlorine dioxide appears to bind to organic mailer as readily as elemental chlo rine, The replacement of 70 percent of free chlorine with chlorine dioxide in a pulp mill reduces dis charges of TOX (total organically-bound halogens) . by about 50 percent [Bonsor 1988]. including pulp mill effluents. The authors wrote; The paseni identified in this report_could be called the chlorine panem. For the tetxaCDFs it consists of the same isomers as the pulp bleaching pattern. However, the chlorine pattern also contains higher chlorinated PCDFj, but no PCDDs. (Rappe 1989] Water treatment A diverse array of otganochlorine by-products has also been detected in drinking water and wastewaters treated with chlorine, chlorine dioxide, or other chlorinated oxidizing agents. According to one review: Almost everyone drinls chlorinated water every day because drinking water needs disinfection and chlorine is both inexpensive and effective. Unfortunately, the organic compounds found in natural waters, particularly surface water, react with chlorine. Hundreds of chlorination by products are then produced, some of which are toxic and apparently carcinogenic [Johnson 1990] A similar array of by-products is formed when drink ing water, sewage treatment plant effluents, and power plant effluents are chlorinated. [Stevens 1990]As with pulp mill effluents, only a fraction (approximately 25 to 50 percent) of the total organi cally-bound chlorine in chlorine-treated water has been identified. [Amy 1990, Veruresque 1990] Significant amounts of the unchancterized portion are non-volatile compounds, which are often regarded as more oersistent and toxic than volatile orginochlonnes. [Jolley 1986, Amy 1990] The compounds detected include a wide range of chlorinated methanes, ketones, acids, phenols, dibenzofurans. phenoxyphenols (also called pre-dioxins), and other complex compounds, (see table 3.4.) Notably, one study detected the extremely toxic chlorinated dibenzofurans in chlorinated drinking water. [Rappe 1989) The congener partem resembled that found in other waters treated with chlorine. Metallurgical processes Dioxins, ftixans. hexachlorobenzene, and octadilorostyrene have been identified as by-products in the emissions ftom nickel and magnesium production processes that use elemental chlorine as a catalyst, intermediate, or precipitating material. [Oehme 1989] The emission rate of hexachlorobenzene ftom a magnesium factory in Norway has been estimated at 7 kilograms per week. (Oehme 1989] High concentra tions of PCDFs were found in fish tissues caught near a nickel refinery in Norway. [Oehme 1989] Because temperatures in the metallurgical processes were as low as 150 degrees C, the authors hypothesized that the metals had a catalytic effect, speeding the forma tion of dibenzofurans with chlorine in the i2J,7 and 8 positions. They also noted however, that "direct chlorination'* may have played a significant role in by-product formation. [Oehme 1989] COMBUSTION OF ORGANOCHLORINES When organochlorines are burned, a full spectrum of by-products are produced. In theory, a properly designed and operated incinerator is interned to convert organochlorines to hydrochloric acid, carbon dioxide, and water. However, real-world combustion systems never take this reaction to completion. According to CPA: The complete combustion ofall hydrocarbons to produce only water and carbon dioxide is theoretical and could occur only under ideal conditionsTM Real-world combustion systems -- virtually always produce PICs [products of 31 SL 062286 T H t9 W 0 0 U C TI TNI9 Q | o incomplete combustion], some of which hive been determined to be highly toxic. [USEPA 1990i] EPA estimates that these PICs -- new chemicals acwauy formed in the incineration process -- number in the thousands, though only about 100 hive been identified to date. [USEPA 1990a] The most compre hensive research bums have identified no more than 60 percent of the total mass of unbumed hydrocar bons in incinerator stack gases. [USEPA 1990a] Most field tests have had far less success in identifying PICs emitted. The bulk of the compounds thus remain of unknown character. [USEPA 1990a] In laboratory incineration tests, more than 100 organochlorine PICs have been identified as by-prod ucts of the combustion of methane with a chlorine source. The author hypothesized that the chlorinated alkanes, alkenes, and aromatics -- including the dioxins, furans. and PCBs -- were involved in a single set of equilibrium reactions common to all incineration processes with chlorine present. [Eklund 1988] PICs identified in emissions from incinerators burn ing organochlorine wastes include chloromethanes, chloroethanes, chlorobutanes, chlorohexanes, chlorononanes, chlorodecanes, chloroethers, chloroben zenes, chlorophenols. PCBs, dioxins, furans, hexachlorobenzene, and hexachlorobutadiene, according to six reports written by or for EPA. (see table 3.5.) Emissions from garbage incinerators burning chlorin ated wastes produce similar by-products. According to one review. The major obstacle to construction of new MSWI [municipal solid waste incinerators] is that incineration produces seven' hundred stable and toxic compounds, including poly chlorinated dibenzodioxins. These compounds art always present at pans per million concen trations in all MSWI units, both in the fly ash formed during combustion and in the stack emissions. [Hutzinger 1986] A British review offered the following summary: Comprehensive tests have established that aD waste incinerators, independent of type of incinerator or waste composition, are likely to produce all of the possible 75 PCDD and 135 PCDF isomers and congeners as well as about 400 other organic compounds. [UKDOE 1989] These organochlorine PICs form as products of diverse and unpredictable reactions that take place both in the furnace and the cooler zones of an incin erator (the smokestack, pollution control devices, etc.). In the real world, localized and short-term variations from ideal combustion occur constantly. These transient departures from ideal conditions may decrease the destruction efficiency, increasing re leases of both unbumed wasms and PICs. According to one analysis, deviations from intended combustion conditions usually are a consequence of a rapid perturba tion in the incinerator operation resulting from a rapid transient in feed rate or composition, failure to adequately atomize a liquid fuel, excursions in operating temperature, instances where the combustible mixture fraction is outside the range of good operating practice, or inadequate mixing between the combustibles and the oxidant-- The amount and composition of PICs wOI depend in a complex and unpre dictable way on the nature of the perturbation. [USEPA 1989] Such transient variations cannot be prevented in realworld incinerators. Changes occur constantly in the rate and type of waste fed, temperature, pressure, mixing, and meteorological conditions. Higher chlorinated PICs are also thought to form in the "cooler downstream regions of the incinerator'* due to "relatively slow recombination reactions" of radicals escaping the combustion zone. [Dellinger 1988] Despite high temperatures, then, incinerators serve to manufacture organochlorines as well as destroy them, due to the formation of PICs during constant transient upsets and during the cooling of combustion gases in smokestacks and pollution control devices. SL 062287 __________________39 TUI p noouer Is T NE * c ts0N MANUFACTURE OF ORGANOCHLORINES SimQaiiy unpredictable and unproventable reactions also take place when chlorine is combined with hydrocarbon feedstocks to manufacture organo chlorine products. Despite a high degree of control over production conditions including material purity, temperature, and pressure, transient variations occur during chemical manufacture just as they do during incineration. As a result of such transient ``upsets." the production of organochlorines always results in the formation of by-products. According to one EPA report. The manufacture of halogenated organic chemicals results in the formation of snail amounts of undesirable side reaction by products. These contaminants may be contained in the product chemical, separated into a processing sup residue, or lost to the air or wastewater as a pollutant. [Lee 1987] The production of specific organochlorine products requires a very narrow range of operating parameters. Deviations from these parameters results in the unintended reaction products. For example, the production of methallyl chloride requires near-perfect conditions: Proper mixing of the components by the inlet jet is a prerequisite to obtaining a high yield of methallyl chloride; reaction is so rapid that high local concentrations of chlorine cannot be dissipated. leading instead to (he prohduction of more highly chlorinated products. [Rossberg 1986] The chlorination of methane -- one of the simplest of all organochlorine manufacturing processes -- also requires a narrow range of conditions; In the [temperature] region of commercial interest -- 350 to 550 degrees C -- the reaction proceeds very rapidly. If a certain criticial temperature is exceeded in the reaction mixture (ca. 550-700 C, dependent on both the resi dence time in the hot zone and on the materials malcin up the reactor), decomposition of the meiastable methane chlorination products 40 occurs. In that event, the chlorination lewis id formation of undesirably byproducts, including highly chlorinated or high molecular mass compounds (tetrachlorothylene, hexachlo. roethane. etc.). [Rossberg 1986] While production units can generally be maintained within these parameters, local and transient variations do occur. As a result, by-products are formed in the real-world production of all organochlorines. No attempt has been made to assess fully the quanti ties or identies'' by-products in products and wastes from organoch ie manufacture. No attempt has been made to t .ate the quantity of unidentified pollutants, eith: As noted above, only t fraction of the organocriorines formed in bleat ;, water treatment and combustion has been idu led. " Presumably, it Is no less difficult to ideu-Jy trace amounts of the many by-products that occur in chemical manufacturing wastes and products. Only a portion of chemical manufacturing processes have been subject to any by-product assessment whatsoever. According to a comprehensive EPA review on the formation of dioxins in manufacturing process, "Much of what is known about the formation of PCDDs and PCDFs has been derived from investi gating manufacturing processes for chlorinated phenols-- Identification of sources of these com pounds will aid strategies to protect die public from exposure to these chemicals." [Lee 1987] A recent study noted that "the present knowledge about annual emission rates and sources [of PCDDs/PCDFs] is not sufficient to explain transport mechanisms and levels found in the environment, which indicates that PCDD/PCDF are produced by additional processes not known at the moment." [Oehme 1989] By-products from some processes have been identi fied, however. Although the quantities of individual by-products varies from process to process, certain by-products have been detected in the manufacture of seemingly diverse organochlorines-- from the simplest chlorinated aliphatics to the more complex chlorinated phenolic and aromatic chemicals. These by-products include the most stable, persistent, and SL 062288 TNC * X 0 0 U C TI T H I X 0 ISON toxic organochlorines: dioxins, fttrans, PCBs, hexachlorobenzene, and octachlorostyrene. These are the same by-products that have also been detected in all processes that use elemental chlorine. According to EPA's review of the formation of dioxins as by-products in the manufacture of other chemicals, PCDDs and PCDFs are formed from a wide variety of chemicals, involving complex reaction pathways-- 13S PCDF and 75 PCDD isomers are theoredaOy possible__The large number of isomers is one of the reasons for the complexity and difficulty in the analysis and determination of dioxins and furans [as impuri ties in other organochlorines]. [Lee 1987] Chlorinated dioxins are known or suspected by products in the production of 104 pesticides, includ ing many organochlorine pesticides and a number of organophosphate pesticides (e.g,, panihion) that are manufactured with organochlorine intermediates. [Esposito 1980, PTCN 1985] In addition. EPA has identified 53 commercial industrial chemicals "known or suspected" to be contaminated with polychlori nated dioxins. This list includes the chlorinated phenols, chlorobenzenes, chloroanilines. chloronitrobenzenes, and a number of non-chlorinated chemicals made from organochlorine intermediates. [Esposito 1980] (see tables 3.6 and 3.7.) These stable aromatic by-products have also been found where they were least expected, such as the in simple shon-chain organochlorine solvents. Dioxins and fiirans have been detected in commercial ehlo* roethancs and chloroethylenes [Heindl 1987], which are used widely as solvents and in the production of polyvinyl chloride. Those products with detectable levels included trichloroethylene. 1.2- dichloroethane. epichlorohydrin, and hexachlorobutadiene. [Heindl 1987] Individual dioxin and furan congeners were present in concentrations ranging from 13 to 425 pans per trillion. The authors offered this conclusion: These results suggest that the synthesis of shonchain chlorinated hydrocarbons can lead to PCDD/PCDF formation. [Heindl 1987] Hexachlorobenzene (HCB) has also been identified as a consistent contaminant in processes that involve organochlorines or elemental chlorine. HCB occurs as a by-product in the manufacture of all chloroben zenes, pentachlorophenoL, hexachlorocyclopentadiene, pentachloronitrobenzene, vinyl chloride, and tetrachloroethylene [Rossberg 1986, USEPA 1985a]. It is also formed in the electrolytic production of chlorine [HSDB 1991] and in the incineration of chlorinated wastes. [USEPA 1989] HCB is also a known or suspected by-product in the manufacture of 20 pesticides, including the widely-used pesticides auazine and simazine. [Veischueren 1983] (see tables 3.8 and 3.9.) Quantities of hexachlorobenene produced may be large. In the manufacture of tetrachloroethylene, for instance, from 1 to 7 percent of the total output is composed of hexachlorobenzene, hexachlorobutadi ene, and hexachloroethane. [Rossberg 1986] Com mercial grade pesticides have been found to contain as much as 5000 pans per million HCB. [PTCN 1985] Hexachlorobenzene itself has been found to contain dioxins and furans at concentrations greater than 200 ppm. [Esposito 1980] Given the similarity of the dioxins and HCB and the occurrence of dioxin as a by-product in HCB itself, the presence'of hexachlo robenzene in any product or process points to the likely presence of dioxins, as well. According to one review: Hexachlorobenzene, octachlorostyrene, aad other highly chlorinated compounds are formed under similar conditions as FCDD/PCDF, and their presence in the emissions of a technical process shoud therefore be a good indicator for reaction mechansims which may also create PCDD/PCDF. tOehroe 1989] This group of highly chlorinated, stable, persistent, and toxic by-products appear to form in the manufac ture of all organochlorines, all uses of elemental chlorine, all combustion sources of organochlorines, and some uses of organochlorines. Even the simplest aliphatic organochlorines produce these complex by products. SL 622S9 TH I f noouer it r mi *9o USE OF ORGANOCHLORINES Many organochlorines are used in industrial environ ments cuuducive to chemical transformations. For instance, pentachlorophenol is used to treat wood at elevated pressures and temperatures. Under such circumstances, organochlorines can decompose and recombine to form an array of new organochlorines. Chlorinated dioxins and furans have been identified as by-products when pemachlorophenate wood preservatives are heated slightly, to temperatures similar to those used in pressure treatment. [Rappe 1978] Dioxins and furans have also been identified in stack emissions and wastewater effluents from oil refineries that use organochlorine compounds to regenerate spent catalysts. Dioxins and furans con taining four, five, six, seven, and eight chlorine atoms were detected in effluents at concentrations ranging into the high pans per quadrillion [Thompson 1990] Chlorinated dioxins and dibenzofiuans have also been detected in emissions from eombustive uses of or ganochlorine solvents. For instance, dioxins were detected in tailpipe emissions from automobiles burning fuel with organochlorine additives. [Marklund 1990] Significant dioxin releases have also been identified from secondary copper smelters reclaiming FVC-coaied wire. [USEPA 1987a, USEPA 1987b] By-products have also bees found in more surprising processes. For example, the most hazardous organo chlorine by-products may be formed when solvents are used as degreasers. According to one study, even the simplest aliphatic organochlorine solvents are convened in alkaline environments into aromatic organochlorines. By-products detected when trichlo roethylene was combined with sodium hydroxide included hexachlorobenzene, octachloros" rene, octachloronaphthaJene, dioxins, and furar. [Heindl 1987] The authors noted, "It should be pointed out that trichloroethylene in. alkaline medium is used occasionally in an industrial process: for the de- grasing of metals, a combination of trichloroethylene, alkaline cleaners, and emulsifiers is used at elevated temperatures." [Heindl 1987] Limited information is available concerning by products formed when organochlorines are used in the production of non-organochlorine chemicals. How ever, organochlorine by-products are known to be formed in these processes, as welL USEPA's list of commercial chemicals with known or suspected dioxin contamination includes 17 nonchlorinated products made from chlorinated intermediates, (see table 3.5). The list of pesticides with known or sus pected dixin contamination also includes s number of nonchlorinated pesticides (Le., parathion). (see table 3.7.) A report for the European Commission pointed to the formation of organochlorine by-products in all uses of organochlorine intermediates: Indusnisi representatives often state these types of processes have little relevance to the chlorine problem__Losses and byproducts always occur and chlorine-containing emissions and wastes cannot be ivoidedL Even minor percentages can be meaningful given the large volume of production and the nature of the substances [Vonkeman 1991) In summary, a large number of processes involving chlorine and organochlorines have been assessed: they have been found consistently to result in the formation of a variety of by-products, including the most toxic and persistent organochlorines. A large number of processes remain unassessed, but the formation of by-products in all uses of chlorine, the manufacture and combustion of all organochlorines, and some organochlorine uses appears to occur. Dioxins, furans and hexachlorobenzene appear to be universal contaminants when chlorine is manufac tured and used and when organochlorines are manu factured and burned (as well as in many cases when organochlorines are used). Any strategy to stop emissions of the most toxic and persistent organochlorines, then, must address the n SL 062290 TKi PRODUCT I* TUI *0Itoa entire class of industrial processes that use chlorine or subsequently produced organochlorines. A ban on processes that produce such extremely hazardous by* products would, of necessity, involve a probidon on the use of elemental chlorine in industrial processes, a prohibition on the manufacture of all organochlorras, and a ban on the introduction of chlorine and organo chlorines to combustion units, including incinerators. TAILESJ. ORGANOCHLORINES M EFFLUENT FROM KRAFT MILLS USING CHLORINE I Acidic tampeanda QNoresf&c add DdRbroacaac add Tricnoreacaec add Dientoropreoanob add Tnedoreoropandc add Tncworebutanac Kid TancMeiobutawie add feniorocaar* add Ctidrefgrmra aad CVNererraiaK aid Ddfltoronndc add Midremueontc add 0dfW3,4-etliyorypanie add DcR<er*3.4-diftydnxybaab add (3 item**) Tne**or>3>di!iydn*yeanjne add Oenbro-fritydrwyoenwe aad CMonuamiiic aad OcmerwiAdic aed TntitonMiiilic add OdMeratynngie add CuefemMMxypratOdRKhiK nd CUoot-tiMenanK add 0dMo>2-mdei*ae add Otdroeaftydroabiatc d IJ-Otoreetffydrwdat* add . laoreractrrydfeiSdtic add Ddneraeanydraadatic add llia-OichiorooaflydraaBiaae acid TncNoiv-2'<i-^Mfflano)C add donor 1 Tncer>2->3-oaffitnotc aod dome 2 51.5- TneWore-2<xo-3-oamno* add 3,4.Si-Titraei>loro-2'e-3*artened add Trrac`l>ore-2-cx>3-p*<i'^noe acd denar 1 Tacr*nioo-2-oxe-3-otntanoe aod denar 2 3.4.Si.S-Pnaendfe-2-o-3-panienea aad Ottorethioenancbarbcayle add I nranefla cempean* 2- Pitoreonand 3- Qtlerepftenol 4- ChdrepnaneM.SI ij-Lncwropnand 2,4^)id!ttnph#nol 2*-OieMoroofttno( 1.5- CrtMoropnanoi 2J.S-Tneworopnand 2.4.5- TneWoepnend 2.4.5- Tncwofopnend 2J.4>TffrxniorDdhMd Z.3.4.S*Tt<nenioropfnol 2i^fi-TuxdanoIanei PtntxMcrocnanol D'CMorma.'iol (2 donais) 3.4-Ooiorea!aeno< Tnentorecranoi (3 iterran) 3.4.5- Tncnio'ocaachd 3.4.frTneNorouen TatacMorocsiaenol 3.4 ,S.S-TatrxMorecadend CMofocusni DxMoroguaiacd 4S-0>cntoroecsaeer S.a.t-TricMerogudKd S.4,s-TncWoreguKd 4j,f>TrieAdngiaacd TtDxMeregusMl 3.4jj>TncMeigtaiKM KWewadia 5.5- OieMenuidKd DicMomaalBa TneNorovariNa S-Mbweie-Mrydrorybanaldeliyde OiiorepreioaucdiPMeHydP DithioroeroacaiacAuMaflydt CMerefynneaddeliyda DbbieroiynnfaaldeHydP Dilor>1 Z3-uiiiydm*yPana< D*nior>iA3-Wtyefeiybaflaai TneWerM AS-tnhydreiybarnant Chloiwl 2,4-Uiltydraxybanaia D>cner>1,2,4-Wiydwaytenaae Triedor>l2,4-tnrryerexybanana 3.4.5- Tncfloieynngd Dicnbroacateayniigoae Oicfiiere-1 .2^ihydfM^3-itatlioybnana Ctoore-3.4-diiyro*ypfopboiaidaa Dteftbrfrl4-diNyfoxyprooopiitnont (2 itenatt) Otle<eonodgvaaena (didnprpodviiullona) OididroGentaiyi aueftd TrtcNorofltNydfoeonldryt dcehd 3.4.5- Tr\c,lor>2.P-dmtttoxypftanol 3S-0duow-ZWnathflypiaed III Natural tompoaoda Oiieoi*(2Wiydtexy)itaerepiM'natli)il banaM 0icfttor>1-{2-Nydre(r)tteprepyMwnnyl banana (5 aomin) 1J-Otemore^-ereeMd 1.1 .3-TrK*ore-2-preeand CMemautaldaliyda OinroaeaaMaii)dP Tnehtoroacawflatiyde 2-CWoreoraoand QilorobUtanN DtcMorpeutand CUdrebdtaWiiiyde BcmerebtaaMaflydl Otlereadera ObbtoroacelBM 1.1- 0<cMereaeaie IJ-Oididnaedeae TneWoreacatena 1.1.1- TncWereaeawie l.t>TncdenaeaBM Tatrachdroaftone 1,1,1>TatracMereacalpnt l.i.SJ'TatneMefeacaiPM Pan-jchio readout Htxa.Voroadoia Tnenioreeyelooropanont Tneruorocyefobuianena Ownareerdoeamana-124na Tftcdowcydoeamanp-lZdiona (2 uomarai Ti:;aenioroeydootntan*-1,2-dena 0icnro-l2-banunona TL-*nk>re-12*banauinona 3-Ptdre 4 OicWororraCTyi-S- hyeray2(5HMnnoi* Oicfitoreacfbe add mdnyi mm Otioroaauc add adiyi mm * Oentoroaeatt add auy adtar TheWoreaeabe add adiyi taw tNeMerenatlune - OHoretortn Carbon lauacdortda IromodteMorerraUida DibrerocMoienatnana li-Odftdrodiane 1.1.1-TncworeaOana 1.12-TracfforeaDtane TncMerMOaea Tacxntoreaftara TatracNoreoreoMa (3 domm) PtnubMoroeraewa DbMereerooKdna Tncdoreeropaddm TKaitdrooreotaana Tnedorobutitnara (2 denart) Pamxndrebudddne <2 denan) Mattiyt cftdroedant (S denan) TancMerecydoeanaddne HaaaeMennaatnaM (S denan) HteacftdroftauguM (2 aenan) Quorebanana !3t<OicMenbMam 1.4-0rnlorebanana lAS-TricNonbanane li4-TrKworebanana 1J>Tne Wore banana 12.3.4-TatneMerabtnaM 12.3J-TatneNerebanana lZ.4>TatncWerebaM PantacMerebanane hnacmorebanana Odre-p<ynane(1) pnoie-p-cynanog) OicMere-yRane OdJidre-e-cyiraMd) OdMere-ddynane (2) Tncwore p eyrrane Oidreeaiarranane Iremeedananam DdredlrraiftytprepyWhydrenapAtMdM OdMeronaOryipnepyidinydrenjoUaiaM DdMeredifTatrypieortnapMiadM CWoremnatnotjbanana TricNeietniratbexybanaM 1.1-OdMorednatnyduireM 1.1.3-TxdoredirartrtyiaUlona TricNerethieprane TavahleretbioeRane 0<cniore-2>d'm/tMoelidd TncMeo2*torrnynnteerana 2-4eaty'deMoroth<ooNna (2 taorrar*) 2-*#VtrKdoreinioBnana 0nd'^2-p'oo<e(Tynniepnant (2 rieman) Source Sunbe 19M. SL 062291 Tn t fA00UCT tI T H| * c I SON TAILS J.4 iy-products in chlorinated drinking water and wastewater REFERENCE ALIPHATIC OR(UNOCHLORINES Sramcefltoroiccwnitnic IremoaiddoreffliiMn* SrwMtdnn Cvwn MneMoNd* Quor* (TncfloreauaMl) CMomiirem OcmUoorreedmiLPmtNmdetnnyRdni aM Ksiern-t-t^KorerflKftyO- S-fr,w/*2{iH)*<urMow Chtoreform ' CNorebcnn (mtroeWoreform) C*d iMtflyi rear (CMC #27) Cyinogon cMonda OicAtoroacratecnydc Dieittorwccairedc tsomor (#513) OKnarexMonreut 3J-O*f>torm2-Manara 1.1- OOtore-2-tuunono 1.1- QtcfltoreoraotnoM Hcaciwremono SJ>Txf<ore<omqrerooM l,l.3J-T*ref4orwc*Dnd ToneworeMfrytono TrtcraoreaciiMoAyd* 1.1.1- TnutoreKf0M TxNorexnnitnlo TncNereotnyfOM 1.i,1*TKMoreereMMM 1, U<TxMore>2-4uBneno 1, 1, 1, 1 t, S I S 1 S 1 S S 1 12 i S S CHLORINATED DIIEKZQRJRANS lZ7>TCDf 2J.7*TC3f 12.J.9-TCDF 12.3,7,l*PCDF 2J.4.7.S-PCDF 12.3.4,7.40f 12.34,7>K*CDf 12.3.7,S.9+MCDF 12.1.4. C.7>HoCDF 12.3.4.7.S,94taCDF OCDF a a .3 a 3 3 3 3 3 3 3 Cmoptwtrsn PHFNOLS/PHENOXrFHENOlS 13 4<Moro*2*mtto*Yph*n0( 1 4<fti;ro>>,-ni,^i>oltnof 3 S-cMs2-niAexypA*not 3 C-cfitor>noioxypftnol 3 CWorefyraana < i4H3<tftoresNonof 2, W*-itor4*m*ttwypl*nel 1J 4,5-0* ?re-2-m*thYpf*nd 3 Dieiitoi stream | Pontx^oregAtoof 1 2J,4.$-TtraeNefOBhoncl 2.4 S-Tx!Koreoxfot 2.4. c-TxMoreoMnd 1J COMPOUND REFERENCE CHLORINATED AOO COMPOUNDS *c*c tat, cMoro*. nwsiyf mtt Acjoc X>c tnciioro-, rraciyt tfar Aobc abd, tfeidore-, nauryi mm | S I SromocMoraaeaDC aed. motfiyt mm (Ml #7) S SutiMOae cod (Mine acid) 1 Oitoreacooc aed (CMorecttenaic add) 1 et-Oitoreduunodioc add (ditorerralae add) 1 Chtorobt!tanadio add. Smcuiyl mm team* S OUoreoutanodoM add (cAJorecuccutic add) 1 CNore>mdire*y-dfcrty'i* add. dimMMaaur S Cd matliyt *r (GAC /IS) S OicMoreHMieadd 22-Oteiorebutanoie add. metnyi tar 12 S ct-Oichtorebmncdtoeaeid (dieNoreralaie aid) 1 inire-OicMoreauunidieie add (dwMoretufldrie add) 1 PicWoreowcMadoit add (dicderemdodc add) Z2-OicMoreprapandc add 3>0idiloreorepanoic add i 1 1 3>0icHoreoree*Aoie add. mdtiyf adar S 22H)teiloreaicdiic add 1 QititiorT*Otp'baft* add. ratnyf add imar S MonedMorwcadc add Ptocmoc adl 22-dt4or>. mathyf mm I S Precanoie adl 2-eNore>, matnyf aaar S Tricdoreaeadc add 22>TheMoreereoandc add 12 1 UNKNOWN COMPOUNDS C(i)es*?(GAC#31) 0 W? (LM #71) CUD s*?(LM#210) 7 9Cf7(IC/10) > i tad? (LM #200 Jt) SM? (LM #53) id) cad? (ML #13) O(i) cad (HM) 0(a) cad (#512) Q(x) Od? (PIH) 0<*) cad? (LM P31S) Q(x) sad? (Pitt) C(*) cad? (PISS) 0(a) cad? (ML #11) Q(i) cad? (LM HS) Q(x) cad (PSC7) 0(x) cad? (PiM) Q(x) cad7 (11 PIS) Cd) cad? (LM #143) Q(i)cad?(#1S4) 0(i) ead? (IM #314) 0(z) cod? (PiSS) 0(i) cad? (#1Sl) 0(i) cad? (LM #307) 0(i)eod?(#i?3) 6 cm? (LM #77) COMPOUND REFERENCE 0(z) cad? (#114) 0(x)cad?(LM#SS) 0(1) cad (#517) 0(D cad (#51*) 0(i) cad (SAC #42) 0(Dcad(#4iS) C(i) cad (#335) 0(x) cad (#430 0<r) ead? (#412) O(i)cad?(#1S0) 0<i) ead? (#i13) 0(x) ead (#510 Q(z)cad?(#lf9) 0(i) ead (#330 0(x) ead? (#150) 0(i) cad (LM #212) 0(x) cad (hi #10 0(i) cad (#532) 0-(C10 Hi OhCOOCHS tunar (II #20) Q(i) cad? (LM #127) 0(x} cad (LM #130 REFEREXC8 (1) National Runic* CnredL *DriakiBC Vim ad Hnlih: Diiretauau and Difinfaaiat By-fcodueu,' VoL 7, Natiaul Academy Pro*: Wadmfwn, D.G, 1917. ffJ5. 37.163.144.134.157,169 0) Riff* 1919 (3) OiwdOT 1919 (4) Mky 19S6 0)Sunch199O SL 062292 THI P ROD U C TI T H IP Q I $ 0M TAI1134 QR8AN0CML0RIXE IT-PRODUCTS FROM HAZARDOUS WASH INOHERATWN Cirton totrtrtortd# (144.44) OilenbtnsM (1,3,4) KtierebuHn* (4) CNotMydohtuMd (1) 1- Chicredraft* (4) OHoretfbiomonUWM (3) 2- OHoreoCiyl vinyl hor (3) CMomtorm (14.3,4,5) KJUOrotmn# (4) Oitoromntno (34) 1-Oikjrenew* (4) l^tloropenano (4) DicMoroaeotiflono (3) OieniorediomoiTeUiino (3) 13^)ie<tombonano (4j) 1,4-Oiefttorobonano (44) 1,14iUor04UiM(S) U-OtttofMUuM (3.44) 1.14)iM0(0cny<m (34) OiciUoradifuonftaUttM (S) DWi)0f0WJn (14.44) 2.4- OidlioioplMflgJ (3) HmeNorobviano (15) Hnachtorobutsdim (3) PotycHorinatd bipheiyi* (Kit) (3) PotycMorintad dborap p diora (P0) (24.D PotycNorlntad tfbMofuiM (PCDFt) (24.1) 1,144-TMefltofOfaitM (44) ToncMorocnyant (144.44) 14.4- TrieMonb4naM (44) 1.1,1-TrteMommno (144) 1.14-TricNofMtlaM (S) TneNoiMUiylono (14.44) Triddorofluoromtdaao (3) TricNorstriflupfOKMM (4) 2J4-Tnetdmpnonoi(S) Vinyl tforido (34) itfftnm 0) TitUn 19H (th W nit KmjAm *uu bciamMn) (Z) DtSiat 1911 Qwtaln Dmm--------- ) 0) TmAda 1917 (MI nk rwy kOa (4) Qn 190 taVtafliM mw) (3) USE7A TIC daw* it USEPA1919 (review at vlhi da* a varied tin) (O USEPA 19T* a>419S7N (two hO-mk TAILE34 COMMERCIAL CHEMICALS KNOWN OR SUSPECTED TO K ACCOMPAKIB IT DIOXIN FORMATION 0URIN8 THEIR MANUFACTURE HICK PROIAStUTT OF DIOnN FORMATION 4-brQfT9-24^cMoroohMOl 2<Moro^lluofcoh*nol 2.4-aibwrnoWiwol 24-dicftloroehonol 2,4^ientorhenol 24-dienaroontMl 24*diento(ooonol 3.4-Oiefttorse nonet i44-tneorephend 2-cntor>t.4-ei(A<ar-$>fltoobMSno 5-enioro-l*-dirTWi>My*<ii0 ehtofolrydrodwnono 2<Morf4-pftonytehtMl 4<hto'Weo(oel 34-dithioro*aticy*e m# P0SSI1IUTT OF DIOXIN FORMATION ecMorofluorebensnt J-cnbro-r-Sjofo-n/trobenane Xniofo-Llluwoenonet XWof>2-ittopnonod ehtofopeinjllvoro benzene 3.4^icntof04ndino o^icmorsbonsno 3.4-dicnioroOonatfohyeo ].4^icMofOMnaincnier4o 3,4-akn torosenzotnfl uoneo 144nbrs~t-nitrobonno 3,4-didibroononyiitoeyiiaio 14^ihydrary5nan*-34-omil1ore Ntodiumai 24^ttiydrwybnnmfonie Kid 34-dUiydnBy^nanowtlonicad. potassoman 44-dlnitoohonot 2,44in>OoenioiytMnol 34-dtnttntAieyliCBd tunariead tratoe intiydrtdi 0-mtotmie 2-rtte-p-crwM iHubdptanot penOCMoreatfne e-ptaobdino ptanol (Hem cMerobwiant) 1-p(and-2-tJfoiC tad. lormildthydi phenyl phthdie tnhyortdo odumpicm 144i-tft'Ktdo)ebnsno tftrxhtorepMhalic innyonop 14.4-(ncntonben9M 2.4.6-tflnitomronei Source Eteottie. 1M0 Note ongiiut M indudK cenaoundt Uy 10 product any Mogeniud Nbensdiesm, Muding brotibniud, fluorinUd, tnd iedintud eorooundt. The* compound! favo boon orvned from W* GtL Homer, MA-halogonCM products rrmd* from chlorinated imanadiwt have n ftarmaMd. SL 062293 45 THE r o ouet ls the f 0 ION TABLE 1.7 PEST1CJCEJ KNOWN OR SUSPECTED TO IE ACCOMPANIES IT DlOXflt FORMATION DURIN8 THEIR MANUFACTURE 5!CX!K CONTAWPATICN KNOWN lilara It CMewtl 0 2AS,S-ac*hiora-2,S"eyeiohad*l ,44wm Oiierapntndt, Nmouo* 2.4-0 and asert and trftl ff (2.4-deMoraoAanffly) aeafc sd 2.4-CS vttxxtt 2.4-ditt*orcphon<aybiflyTW aed 2.4-OP B2-{2.4-dieAioreonanoxyipraeo tot DicwrM. dmanyumn* alt B 3,frdienfoo2-m<Cic*yboHie aed. Qicum*// lS-oedora-2-m*hybae tot. DiostAM B Pbownoretluorc aed <2hloi*4-nitraohanyH t.o-dfratftyi mo Dicnelamnion U PAoerioratnioie tot. *JL4-dicNofeft*fl>< o.a-daikyl mm DitJ uaum (mem) If 2.4-ditdorooneftoaywnyi WHia. Mium an OMPA Eibgn 3 22-dbboraoraeanoie aed 2-&4,5-tneMorapftene*y) atnyt mm Haaeraonent//2J`-mtnytani bW3,4,F-triefiioehind) bow 20II ZT-Wrfo* bs (3.4.6-tncMorooiwnel), monotedium ait tbtradn U 2.44icbomenony4-niffoohnyl ana PwracMomonona (PCP) and sam Nonna II pnotenaetniee aed, o.<iratnyv4-[14>trisMorepMnyl) moo ftiand n and abb // 2-{2,4.S-6'iehJoraoAano*y)oraDionie add 2.4.S-T and mo\ art tats 0 (2,4,S-trieMoraen>o*y) acne aed 2.4XneMerepMna 2J.4.C WAigroonona Jmnmam BIBXIN CONTAMINATION `POSSIBLE* AKsn!! 0 S-Ciioro-l-ilS^eniaednonylHinyl) 0,0-diatfyt photphdrathiona Any, amoey i>-fliO>oro:ny amrartum etarido liltnat II nwatf J-(2.4-dieftloraDnono*yh2-itrebanad CvaonpntnoiiMn it Photonoraotniorc aed -([{4*duorapAaflyt)8iioJ maoy<] o.o-c*uy mm CNoiai CMemronwM S<ftiora-2*42.4-dienioreononory)pheflol 1^4<Juomonawy)-lWimnTi-1-41H-1i4.triaaN-1ifi)-2-buttnoia CNorcm B1,4-dicNom-2.4mameytenant CMorcmadni Dtoreaireo B l-(4-(4-cflorepriefiy) phonyM.I-dnetnyiurai Cntonboohot Crufonwa 8 4-tal-euty*-2hiorociaryl rratnyf nwnyipnotolwaibdad OCPAi/LI5KndtUo(^1.4-b*nanadiearooiylie aed SmdUiyl ntar DOT DacaeNorcbrt (2.4<ydopaffladan#.l-y0 DiemoMni II 2.4-sehiofobeisodtnd OtcAbtantMon h 3-(14-dicftiomenaiyi) 0.0-diahyipnoe>mtNoali Dwiuona u 2.3-dNora-1,4-AaoWiadnodiona (bet Drcioioo-manyi p>mtropMry< alar (TON) w-r\wi;>`<wrMni-nohd*nbaiM 2.frdbAbm-4. ntmanbno 0>fluoaeufon B M((<^toraonony1>*nino)6a/&ory)-2.P-afluorc&e-/T*da] 0-mr.ry laU'ac.Mere'.araonttiaiaie Oinmooutyipnona. ammonium tan 4>$"difutrc^*o**cywfli ciurcn II 3-(3,4-d*if roenonyiH .l^menyluraa Endotuitaa Elba* ftnvdertta B cyino(3<ibnqypi*ny0mdIiyM<hlorc done- 0 -many^anytV-Hnantacaat fluvaiinaa // N-2<num-4-tnfluomwiiyl}^nnyKX.'naaia(*>yana (3-phencxyphaflyDmaoiyi taa FunQiflor It 1-{2-(2.4-(ieMomonaRyl)-2'K2-moam4oir)anyl}-tH4i)tdwu Simon//2-cnioc1-<2.4J-tneAiernnoiyynyidm*nyi pnevftata HeacMoraaonaM letyi* Kamana t l,l-pit(MQraoneny<)-2J-vicNoraaeiaNl Lindane // g-1 .2.3.4,S.S-haucNorccydoMuM. UCPA//(4-yvora<-ttiary<) acme aed MCFS It 4-(2-fflanyM-cNorophifta(y) butyric add Maceorap B 2-(<<nioo2-(T*tfT/iBhno*y) prapmde add 2X-matfry<*-di<3,4.MneWofO"0hend) 2T*m*Bryien*bia(A<AioraonenoO Monuren tricNoreacetite// 3^p-chtemelanytV1.HbradiytMW triouoraaeaaa Naburpn t l-tuy-J-da-dieniornonaiWl-naPTyitm tttadaan B 2-bvbutyU-(2.4-diauorp S iaepiepeypiawyt)ddtd1. * 3,4-ojadajetin-j-ono) o^anzyHXiuoreoiwad OK4-bren^23-dkNoropiany(>4.0Hfiradiyi phttphoranbap Pamdion // pnotenorcOiioic aed, a.o-daciyt-o-(4-nmophenyi) mm PtnaeMombaftsmMo PtntaaMomnRrebtniMw Ppntacftioreenanyt lama Rpedincpropyv3.4-dicNoraba<aDaa npomrtun It 3-C2-manyieoondino)pmpyl-144icMoibMi9aa nanawn // 4-(matnyltidteiT|flh2^4initre-N.N-diprodylanriint Praanoiot// 0-(4-bienv2<MorwnanylH>nyt Sbrepyl pnotenorp-modd) Preeani // lA-diciUoreprootonaniida p-OUompnanyt.2.4S^neWo>opnanybd#do p-0temofO6*inn* Raben 8 EOboolKld.^icNompMflyt) vinyl danyi phoonat Rodlan 13-<3>dcnioroplMny(>5atnonyl-^maiiyi-2.4aBiidnodiona SttOAP Sodium pontaeMoiopianad 124i-tairtcitoro-3-nitiPbonia TameWommeeiniaatrilo TancMompnanau TatncMompianett 2jr*Oiiobit(4<ftioro4'mitnyipiaMi) 2J.S4ricftcrot>*nie aid TiicNorabMsyi chiorida 13,l-tricMorepiany(acatic add and tedium aR Source*: Etootrte 19ML PTCN lift No* original Ea ineudad comooundt fury te predueaany haloganatad dibanaadiOBnt. indueng bmntnaad. PuonnaiaaL and iodinaiad eoneoundL Ttuta compound* navt boan ontnad tram Art fti. Howe, nen^iaioganatad preduca nda Iram emonnead imarrmsiaiat lava bwn imnamad. AS SL 062294 TH I P H0 0 U CT I IT H IP 0 I ( o N TAIIXU Chemical* *Wha*a Uinufactarc It Knari* la Haxachle/cbamaa (1) Carton tatncttorida Qiienuud banana* CMortna HcadUorecydopantadana PantKAJofoictrebanana PunacAlorodhandi Tadaeftlowatfiyiane TricNoroaUiylan* Source EPA IMSk TAILESJ. PESTiODES KNOWN OR SUSPECTED TO IE CONTAMINATED WITH HEXACHLOROIENZENE. 1111 (S) DCPA(D#Ul) ' Chtorcstalonil (D*omi J7I7, Ircvo. Tamil) Ptnachiororitrobadan* (PCNS, Tarracftalor) S.S.7>Tr*."WroflurwtiJrni (lued. CMorgiimx) PartacAloiooAaflOl (Ouorchan) PtmacMomonmi arc an PwiacAierooftwot adium tan (Oowioda 6) PwitzMoreoArai sotatsum an DaftydroabtaryUrtina paraeAiorophana* 1A4J-T*caenk>ro-3-fMro6*nan* (fokwafl, TONS) 2^4nC!*ort-W-<panOcAlorofi*nyl) acacmdoytctlorid* Matty 115,S-lncftlofo-N-rTaAo*y-N-m*tl)yt iOTricicorophanayiedCe add [2.4J-T) 2J>Tnelborcbi< aed (2J>TU) Indite Ally) eMondaWehtofoeropana lAS-Tnefloroprocane 17 ?.Triofliafa-W-ranao'teropAnyl) icximidty ehlendi DaftydmibaatytafliA* pa/iacntoropftanai* Rdodnni ' Manutetirm hsa adwowtadgad s>* prtwnea d haaadNorobanane a an Inpurrty in thnaa prodira. Source PCTN1M5. SL 062295 A' ECONOMICS OF THE CHLORINE PHASE-OUT IMPLICATIONS FOR WORKERS AND CORPORATIONS As noted in Chapter 1. the UC's Science Advisory Board has recommended a phase-out of organocWorines and other organohalogens. Despite repeated claims by some industries that toxic substances are necessary to economic productivity and health, the DC has argued that the environmental and health effects of persistent toxic substances are far more costly than the expense of implementing alternatives: The technology either exists--or can, with vey few exceptions, be developed at some cost -- to replace (or control in the interim) the use of persistent toxic substances. Sufficient information is now known for society 10 take a very restrictive approach to allowing persistent toxic substances in the ecosystem and to declare such materials too risky to the bioshpere and humans to permit their release in any quantity. They result in implications far beyond conven tional measures of long-term net economic costsTM." [DC 19S9b]. IMPLICATIONS FOR INDUSTRIES THAT USE CHLORINE In many cares, changes in industry to comply with the chlorine phase-out will cause little economic disloca tion. For instance, in the pulp and paper industry, chlorine-free alternatives are readily available. Pro duction of unbleached paper, prolonged pre-blcaching, improved preparation and choice of woods, and use of oxygen, ozone, hydrogen peroxide, and other chlorine-free bleaching methods can produce quality products without chlorine. [Dillner 1990, Bonsor 1988, Sixta 1990] Such changes will, of course, require some capital investment, but they can also produce long term savings through reduced chemical costs and other efficiencies. In North America, if the U.S. and Canadian governments establish a rational coordinated time-table for a phase-out of chlorine based bleaching, neither counoy's pulp and paper industry need suffer a net loss of markets or jobs. In feet, facilities that produce a portion of their product for the world market would likely see a net gain. Alternatives to organochlorine solvents are already being introduced in the automobile, electronics, and aerospace industries. Water-based alternatives have replaced chlorosolvent paints and dyes. Better house keeping, process changes, mechanical cleaning methods, and use of aqueous or biogenic solvents have made chlorinated solvents unnecessary. Accord ing to the Office of Technology Assessment, such changes result in reduced costs and unproved produc tivity. [OTA 1986] Similarly, chlorinated pesticides can be eliminated in agriculture without diminished productivity. Accord ing to a 1989 study by the National Research Council, reduced use of synthetic pesticides can actually increase yields and lower costs for fanners. (NRC 1989] Alternatives include better crop rotation and mixing, introduction and preservation of natural predators that prey on pests, and use of natural pesticidal chemicals. [NRC 1989] Government programs ____________49 SL 062296 that now apply financial pressure to farmers to use pesticides and maximize short-term yields should be reformed to provide incentives for farmers to forego use of pesticides -- organochlorine pesticides in particular. Alternatives are also available for chlorinated plastics, chemical intermediates, and blowing agents and for elemental chlorine in water treatment. For instance, glass, paper, metals, and non-chlorinated polymers can replace all uses of polyvinyl chloride. Ozone treatment is considered a more effective disinfectant for drinking water supplies and for waste water than chlorine, chlorine dioxide, or chloramine. [Moser 1990] (In some cases, drinking water delivery systems would need redesign.) Other alternatives to chlorination include, in many eases, no treatment whatsoever and reduction and prevention of wastewa ter discharges through water conservation measures, such as closed-loop systems. The most effective alternative, of course, is to prevent contamination of water supplies in the fust place through various measures, such as dry sewage systems. [Costner 19S6] Alternatives to the chemical intermediates in the manufacture of other chemicals also exist. For stance, phosgene in the manufacture of resins be replaced by dimethyl sulfate and dimethyl carbonate; chlorohydrins in propylene and ethylene oxide can be replaced by metallic catalysts; and epichlorohydrin in the production of epoxy resins and olefins can be replaced by electrochemical oxidation with metal catalysis. [Costner 1989] In some cases, the shift to chlorine-free alternatives will add to the costs of production. In many others, it will yield a substantial, long term savings. In all cases, however, this shift wQl not jeopardize the survival of the industries that use chlorine and organochlorines. REACTION OF CHL0R-ALKAL1 CORPORATIONS In those industries that manufacture chlorine and organochlorines, the chlorine phase-out will be of far greater economic significance, causing major eco nomic dislocations. The U.S. chlor-alkali sector is described as a "S3 billion per year'' industry, p/er* banic 1990] U.S. and Canadian producers are listed in tables 4.1 and 4.2. Environmental pressure has already led to downturns in the chlor-alkali industry. Reductions in certain uses of chlorine (i.e., CFCs, pulp and paper, banned pesticides) have resulted in lost markets, declining growth, and lost jobs. Qilorine demand grew by only 0 to 1 percent through 1990, and analysts predict stagnant demand and prices through the next decade. [Hoffinan 1990b],Chlorine contract prices tumbled at least 35 percent between 1986 and 1990. [Gilges 1990] Numerous plant closures and consolidations have resulted, and mote can be expected in the future. According to one market report, "as many as eight chlor-alkali plants in the U.S. are expected to close in the next five yean as a result of high operating costs and the loss of chlorine end-use outlets." [PPW1990] The chlor-alkali industry dearly recognizes the trend away from uses of chlorine, but it is striving to protect its markets and capital by increasing public relations, fighting further regulation, and expanding markets where environmental regulations are less stringent. The Chairman of Occidental Chemical, for instance, recently argued that the "survival of the chlorine industry is directly linked to the survival of Us key markets in what is becoming an increasingly hostile environment for chlorine-based processes." [Hill 1990] He urged the industry to become "more adept at communicating chlorine health, safety and environ mental information...or be swept away with the consequences." The president of the Chlorine Institute is preparing to "overcome negative images and concerns-- even though some are unfounded, out dated. and ill-conceived." [Verbanic 1990] JO SL 062297 TH I f i0 0UCT 1S T H IP 0 I I o Li wiuluuti. the industry has begun to expand its markets by exporting more organochlorines -- especially ethylene dichloride and vinyl chloride, the precursors for polyvinyl chloride -- to nations with iuLigeiit regulations. Prime targets for new FVC factories include Brazil. Mexico, Venezuela. Nigeria, the Pacific Rim, and the Middle East [Endo 1990] Organochlorine pesticides banned or unregistered in the U.S.. Canada, and Europe (Le.. chlordane, lindane, haloxyfop, etc.) continue to be manufactured and exported to developing nations, as well At the same time, some alkali producers are investing in new ways to produce alkali without producing chlorine. Because most alkali markets are increasing while chlorine growth has stagnated [Christaens 1950], alkali producers are looking for alternative production processes. Several have invested in tech* oologies that produce alkali from trona ore without chlorine. From 1987 to 1990,300,000 tons of U.S. caustic production was convened from chlor-alkali eiecirolysis to trona ore purification. Four companies -- Tenneco, FMC, Atoehem. and Texasgulf -- have made major investments in trona facilities. [Hoffinan 1990a] PROTECTING WORKERS The large corporations that manufacture chlorine and organochlorines are taking steps to diversify and protea their capital in the face of a likley decline in this industry. No large-scale programs, however, have oeen established to protea the workers and communi ties that are dependent on this industry for their livelihoods. Greenpeace believes that the phase-out of chlorine production must include such programs. Workers displaced from this industry need compen sation, retraining and new opportunities for higher education. They should be given the time and re sources to learn new skills and secure quality jobs without being forced to accept major cuts in income. Communities that depend on these indtmries also need help to anxaa new businesses and diversify their economic base. The cost of such programs should be financed by the chlor-alkali industry itself. Labor groups have advocated such an approach, which they call the "Superfund for Workers." It is based on the principle that workers should not be forced to bear the economic burden of the transition to a non-toxic economy: Polluters (should] be held responsible for the entire cost of their negligence, not only of the environment but also of the millions of woriong people who devote the better pan of their lives to making the toxic industries profitable. Modeled on the GI Bill of Rights enacted at the end of World War Q. which provided income and tuition support to mil lions of returning veterans, the Superfund for Workers is pro posed as a way of jxoviding similar support to the millions of people who currently are dependent upon the toxic economy for their livelihood. As such, b is more than amply a retraining program for another group of work ers who unfortunately find themselves unem ployed. (Merrill 1991] For example, a government imposed S100 per ton surcharge on chlorine production would generate about SO billion per year in the U.S. and SI 10 mil lion per year in Canada, based on current production rates. If chlorine were phased out over a ten year period, for example, this surcharge would generate a fund of S6 billion in the U.S. and S550 million in Canada. Greenpeace supports the Superfiind for Workers approach. The phase-out of the chlorine industry offers a prime and necessary opportunity for imple mentation of a meaningful, industry-financed worker protection program. SL 062298 si LOCATION ALBurMBo ALLaMoyna ALMeintoati AL Mobil ALMusde Shoals CA Pittsburgh DE Delaware Qty GA Augusta GA Brunswick GA Brunswick IN ML Vernon KSWIehSa KYCahrertOty LA Baton Rouge LA Convert LAGaismar LAGramsrey LALakaOtanas LAPIaouamina lAPIaquamine TABU 4.1. U.S. CHLORINE MANUFACTURERS IN DU COMPANT Canard BecMc Ateo Chemical OUn Corporation Ocddantd Chanded Ocddantd Cherried Oow Cherried Oeddantal Chanded Ota Corporation LCPOwnded Georgia Pseffle Ganard Baetrie Vutcan Cherried IF Goodrich Formoa Ptaafle* Oeddantal Charrded VdeanChended LaRocho Chonded PPG Dow Chanded Georgia Gutt LOCATION COMPANY LASLGabrid UTaft Pioneer Odor-Alkal Ocddwital Qtarried MEQrrington LCPOsartded MSVtcktavrg Cedar Chandal NVHandareon NVHandarxon Pioneer CNondkdl Titanium Metals NYWagareFdts NY Niagara Fafla NY Niagara Fans NY Niagara Falls DuPont MaeMor Oeddantal Chanded OOn NC Aetna OHAshtatuda OH Ashtabula LCP Chandeais . Undwffl RM OK Muskogee ran wvvu OR Albany OR Portland Oregon Mataflurgial AlochenYPennwalt TNChsrtadon Ota LOCATION TXBeyton IX Corpus OuMS TX Dear Part TX Freeport TXLaPorta TX Snyder COMPANY Mobiy Gherrial Ocdderrtd Oeddantal DowChanded Oeddantal Americai Magnesium ITT Rowdy mva 1no-ptwBrei AnvMagnadum Hercules. Inc. WA Baffingham WA Longview wa Tacoma ya Tacoma Georgia Padttc Weyarhsusar Oeddantal Chanded Atoeham/PannwiA WVMoundsvfle LCP Chandcils WA Naw MardnsvQt PPG Industrie* WI Green Bay Wl Port Edwards Fort Howard Vulcan Chemicals Source 01Ml TAIL! 4.2 CANADIAN CHLORINE MANUFACTURERS IN IMS LOCATION COMPANY AB ft. Saskatchewan Dow Cherried Canada BC Vancouver BC Souanish BC Nanaimo Canadian Orycfttm Canadian Oxychem Canadian teyehem ON Cornwall ON Sarnia ON Drydan IC1 Canada/C-K Dow Cherried Canada Great Lata Forest LOCATION COMPANY NSDalhoudo NBNafitawie IQ Cwada/C+l St Anna Chanded NS Abercrombie PoLit Canto Chemicals QUBuuhamoia QUBacaneour PPG Canada ICI Canada/C+-L SK Saskatoon Saskatoon Chemicals Soufta:CMM9.C8iaa 52 SL 062299 THE PKOBUCTI TNI POISON REFERENCES Allan, A., A. Ball, V. Cairns, 6. Fox, A. Gilman, 0. PeakaJL 0. Pieiarz, J. van Oostdam, 0. Vlllanauva, and D. Williams (1991). Toxic Chemicals in tht Great Lakes and Associated Effects. 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Mackay (1988). *A review of the nature and properties of chemicals present in pulp mill effluents.' Chemosphere, 17 (7): 1249-1290. Swain, W. (1988). 'Human health consequences of con sumption of fish contaminated with orgenochlorins compounds.' Aquatic Toxicology 11 (3.4);357*377,1988. Thompson, T,, R. Clement, N. Thornton, end J. Luyt (1990). *Formation and emission of PCODs/PCOFs in the petroleum refining industry.' Chemosphera 20 (10):1525-1532. Travis, C^andS. Hester (1991). "Global chemical pollution.* Environmental Science end Technoloy25(5):814-819. Trenholm, A. and C.C. Lee (1986). 'Analysis of PIC and total mass emissions from an incinerator.* Land Disposal, Remedial Action, Incineration and Traatment of Hmrdous Waste, Proceedings of the Twelfth Annual Research Sympo sium, Cincinnati: U.S. Environmental Protection Agency Hazardous Waste Engineering Research Laboratory, EPA 600/9-86/022, August 1986. Trenholm, A., and R. Thumau (1987). 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"Wfty dioxins and other halogenated hydrocarbons are bad news." Journal of Pesticide Reform 9 (4)32-35, Winter 1990. Yasuhara, A^ and M. Morita (1988). *Formation of chlorinated aromatic hydrocarbons by thermal decomposi tion of vinyfidene chloride polymer.* Environmental Science and Technology22 (6): 646-650. SL 062306 59 THE CHLORINE INSTITUTE, INC., 2001 L STREET NW WASHINGTON. D C 20 202-775-2 Fa* 202-223-7^ Teie* 276636 ChlOA w. n s TO: Board of Directors Board Task Group on Outreach Communications Committee Health and Environment Committee Government Relations Committee Federation Arseen Seys, Euro Chlor Contact Neville Ginn, ECDC Contact FROM: DATE: July 29, 1991 SUBJECT: Greenpeace Report on Chlorine and Related Matters Last week many of you received a copy of the press materials issued by Greenpeace in Buffalo, New York on July 25, 1991 on its call for a phaseout of chlorine use. The material contained what turned out to be a long summary of a very extensive report. Enclosed is the full 59 page report with well over 100 references. On the face of it, 1 consider this document to be a thorough piece of work that must be taken very seriously by everyone connected with chlorine chemistry. Also enclosed is the schedule for the entire antichlorine Greenpeace campaign. Therefore, I am requesting that the Institute and the other trade associations with an interest in chlorine chemistry make an all-out effort to analyze the report and to develop responses to any assertions, claims or `facts" it presents. This work should begin immediately given that the Institute is conducting its first-ever public outreach effort starting August 11, 1991 at the National Conference of State Legislators in Orlando, Florida. The Institute must be prepared to deal with the possibility of getting ques tions from attendees who have been exposed to the Greenpeace initiative. Furthermore, Greenpeace could be successful in persuading the Congress to begin to look into zero discharges of organochlorines. The Senate version of amendments to the Clean Water Act already contains zero dis charge limitations for some chemicals. Finally, since the national media did not pick up this story immediately, they either decided to ignore it or to do something more than same-day coverage. We must be prepared for the worst case. By this memorandum, I am requesting that the following Cl units immediately begin to take action on this Greenpeace document in keeping with their overall missions: Board Task Group on Outreach Communications Committee Government Relations Committee Environment and Health Committee ST. 062307 It is my intention that the Environment and Health Committee take up the matter of developing the scientific basis for any response that might be made by Cl. The Communications and Government Relations Committees will determine the nature and timing of our responses to the media and government bodies. The BTGO will assume responsibility for coordinating any Cl initiatives on the Greenpeace documents with our outreach program. It is my understanding that the Communications Committee will address this matter at its meeting on August 31, 1991; and the Environment and Health Committee will teleconference on Monday, August 5, 1991 to begin the process of developing the scientific basis from which responses can be made. Also, by this memorandum, I am requesting that members of the Federation and our colleagues in Euro Chlor and the ECDC provide us with information they believe can help us address the Greenpeace report. I consider this to be a very hi - priority item that is going to require a lot of effort. Clearly Greenpeace h . expended considerable resources in developing this document. We cannot afford to expend any less. It is particularly important that our front-end analysis of the document identifies clearly what information is already in hand at Cl and within its members, and what new information needs to be developed to support our positions. This effort will be a major test of Cl's and the industry's ability to move quickly and smartly. If you have any questions, please give me a call. I will be coordinat ing the overall effort by the Institute at the outset. RGS/tk misc/GrnPcRpt.Mem SL 062308 ZERO ui^hmRGc CAMPAIGN (Stops planne Greenpeace GREAT LAKES PROJECT ERO tuSCHARGE TOUR i^^j^Ferrapin or both vehicles) Tentative Schedule July 14-15 July 15 July 17 July 18 July 19-21 July 21 July 22 July 23 July 24 July 24-26 July 26 July 27 July 28 July 30 July 31 - August 2 August 3--11 August 14 August 17 August 20 August 21-23 August 25 August 26 August 27-29 August 27 August 28 August 31 S ptember 1 September 2 September 3 S>^2eCpytewmn\ibe^rr 4e/ September 8 September 9 S ptember 10 September 10-12 September 14-15 S ptember 17-19 S ptember 19-22 September 24 September 26 September 27 S ptember 28 - October 1 Mohawk Community of Akvasasne Cornwall, Ontario Ottawa, Ontario Brighton, Ontario Toronto, Ontario Orillia, Ontario Hamilton, Ontario London, Ontario St. Catharines, Ontario Niagara Palls/Buffalo, New York Clarence, New York Lewiston, New York Erie, Pennsylvania Ashtabula, Ohio Cleveland, Ohio Detroit, Michigan area Sarnia, Ontario Bay City, Michigan Alpena, Michigan Sault Ste. Marie, Michigan/Ontario Thunder Bay, Ontario Marathon, Ontario Duluth, Minnesota Terrace Bay, Ontario Red Rock, Ontario Bayfield, Wisconsin Ontonagon, Michigan Houghton, Michigan Cloquet, Minnesota Superior, Wisconsin Marquette, Michigan Quinnesec, Michigan Escanaba, Michigan Menominee, Michigan Green Bay, Wisconsin Milwaukee, Wisconsin Northwest Indiana Chicago, Illinois Muskegon, Michigan Lansing, Michigan Petoskey, Michigan Travers City, Michigan GREENPEACE GREAT LAKES 1017 W. Jackson Blvtl. Chicago, II 60007 (312) 666-3305 GREENPEACE TORONTO 185 Spadina Ava../600 Toronto. Ontario M5T 2C5 (416)345-8408 Printed on non-chbrine bleached wper, which does not contribute chlorinated tones to the environment SL 062309 SL 062310 SL 062311