Document Gm906G2g2bdOnLVykDQbQprYq

. ( * vivif: DIOXIN REPO RT B A C&EN SPECIAL ISSUE G03718 ti In the annals of environmental con widely varying toxicity. Although no practical applications, no benefits tamination, few if any chemicals many health effects studies are under to weigh on the scale against the have achieved the widespread noto way, scientists have yet to find that risks, even if the most dire of the riety of 2,3,7,8-tetrachlorodibenzo- any human death has resulted from potential human risks have as yet p-dioxin. Under its simple if scien exposure to dioxin. only circumstantial support. tifically imprecise sobriquet - of Nevertheless, such exposure is the Dioxin is an intriguing substance, dioxin, it has acquired a mystique subject of numerous lawsuits. It has from its completely symmetrical that has moved it into the forefront moved the U.S. government to buy structure to its widely variable tox of hazardous substances. out an entire town. It has under icity. And there isn't very much of Much in the news of late, it is sel mined company reputations. It the chemical around. The concen dom mentioned or written about practically has made household trations that drive people and gov Without the additional notation that names of such geographically diverse ernments to action are cited in parts it is the most toxic chemical made by designations as Seveso, Times Beach, per million, parts per billion, even - man. Less often isit'm entioned that and Tittabawassee.-------- "" parts per quadrillion. such a statement is based on test re Yet dioxin lacks redeeming Because of the compound's con sults on a certain species of what is a virtues. Although it is a contaminant troversial reputation, and because species-specific substance with of useful products, dioxin itself has current events have brought dioxin 20 Junes. 1983 CEN prominently into the public con aftermath of that accident has been a nent, short-term effects is obvious. sciousness, C&EN is devoting this saga of missing waste and lawsuits in Evidence for long-term effects, such ` issue of the magazine to an exami Europe that are now in the courts. as cancer, although suggestive, is far nation of the topic. A scientific and Last fall, attention focused on from conclusive. environmental concern, the dioxin Times Beach, Mo., when the gov There also are unanswered, and problem impinges as w ell on the ernment found what it perceived as perhaps for now unanswerable, political, judicial, philosophical, and health-threatening levels of dioxin in questions about cleanup of dioxin- psychological spheres. In the fol the environment there resulting contaminated wastes. The relatively i lowing articles, C&EN examines such from previous waste disposal activi concentrated wastes likely w ill not ! topics as the current environmental ties. Concern intensified in suc prove to be too much of a problem. ! concerns, the status of toxicological ceeding months with fears that Technology for treating them is and epidemiological studies, where flooding, then taking place, would available and new methods are on dioxin comes from and how its gen: spread the dioxin contamination to the way. But the logistics that would eration can be controlled, available other communities. The climax came be involved in treating acres of con technology for disposing of existing in March, when the government taminated soil are mind-boggling, to contamination, the legal ramifica announced it would buy out the say the least. tions of dioxin exposure, and the town. The book on the Times Beach Another dimension to the dioxin current level of concern and status of affair is far from closed. issue is being added by the court regulations in Europe. Now another episode has opened cases now shuffling their way along I The object of current scrutiny, in Midland, Mich. The concentra the litigation route, as well as those 2,3,7,8-tetrachlorodibenzo-p-dioxin, tions involved are much lower than that may yet be instituted. The po is a colorless, crystalline solid at room those found in Times Beach and most tential outcomes raise major concerns temperature. It was first synthesized of the attention is focused on dioxin among the companies involved and in 1957 by catalytic chlorination of contamination of fish. Unlike the their insurance underwriters over I the unsubstituted dibenzo-p-dioxin. Missouri episode, no one is sure the-matter of liability. That synthesis and the recognition of where the dioxin is coming from-- Despite the ad hoc nature of the the compound as a contaminant in although theories have been put reactions to the dioxin incidents-- the herbicide 2,4,5-trichlorophen- forth. In this case, the government's not to mention the comic-opera as oxyacetic acid (2,4,5-T) came nearly reaction has not been a buyout but a pect of the Seveso aftermath--the a decade after the herbicide was study. dioxin situation is potentially serious. registered for use. Legal, regulatory, and other ac Despite uncertainties, action must be 2,4,5-T is made from 2,4,5-trichlo- tions regarding these incidents, and taken. But as so often seems to be the rophenol (TCP). The production of others, continue. Meanwhile, scien case with exposures to what may be, TCP is a major route for the forma tists are continuing studies to deter but are yet to be proved, hazardous tion of dioxin and the source of the mine the health effects of dioxin in substances, for now there are still lI contaminant in 2,4,5-T. humans. That there are nonperma more questions than answers. Early exposures of people to dioxin came about primarily through pro duction or use of dioxin-contami nated herbicides. Such herbicides became widely distributed in the environment because they were ef fective against broadleaf weeds and undergrowth plants and less toxic to grasses, canes, and established trees. Indeed, 2,4,5-T was one of the com ponents of the defoliants, the best known of which is agent orange, which the U.S. military began using in 1962 in Vietnam. Use of agent or ange in Vietnam was halted in 1970. But the repercussions of its use still are being felt in lawsuits, brought by veterans exposed to the defoliant, which currently are being litigated. Then came Seveso. In 1976, a re actor at a chemical plant near Seveso, Italy, making TCP for use in hexa- chloro ph ene7fcWefir15Urtif^Contrcrlr spewing its contents, including an estimated several pounds of dioxin, over a densely populated area. The June 6. 1983 C&EN 21 Dioxin Issue Focuses on Three Major Controversies in U .S. Furor developing around the question of dioxin exposure has reached a head in three historic cases-- agent orange, Times Beach, and Tittabaw assee River Janice R. Long, David J. Hanson, C&EN Washington When the history of human problems with exposure to toxic chemicals is discussed in the years to come, one of the principal topics of de bate will be the effects of the compound called diox in. And, in that debate, if it focuses on the U.S., three names will be recalled -- agent orange, Times Beach, and the Tittabawassee River. More than any other incidents, these three widely differing exam ples of dioxin exposure point out the problems our scientific, regulatory, and legal systems have in handling the undefined hazards of potentially very dangerous substances. Central to the entire problem is the herbicide 2,4,5-trichlorophenoxyacetic acid (2,4,5-T). Developed d u r ing World War II, it was first regis tered in the U.S. as a pesticide March 2, 1948, and it has been the subject of considerable study ever since. There were some health problems associated with 2,4,5-T almost from the beginning. In 1949, an industrial accident at a Monsanto plant in Nitro, W.Va., exposed 250 workers to the compound, with a n u m b ef 6'f re sulting illnesses. But it wasn't until about 1955 that the cause of the ill nesses, mostly the severe skin rash called chloracne, was found. West German physician Karl Schulz, treating workers from a Boehringer Ingelheim pesticide plant in that year, identified 2,3,7,8-tetrachlorodibenzo-p-dioxin as the cause of the chloracne. Schulz's work was pub lished in West G erm any in 1957, and appeared in Chemical Abstracts in Decem ber 1958. Still, despite this problem, 2,4,5-T was considered a good herbicide and its use spread. It was used extensively on rangeland and pastures to kill unw anted weeds, and also on rice and nursery crops. Because 2,4,5-T is quite biodegradable and works so well, it, as well as other herbicides (particularly 2,4-dichlorophenoxyacetic acid) was considered by the military in the early 1960s as the best means of defoliating large sections of forest in Vietnam to take away cover from the enemy. Spraying began in Viet nam in January 1962, using a variety of herbicide con coctions. Only small amounts were used at first, but the am ounts jum ped at the end of 1965 and heavy use continued until 1969, when mounting concerns about damage to Vietnam's ecology led to a tapering off and finally a halt to the spraying of 2,4,5-T in 1970. Of the seven or so herbi cide formulations used, the most significant was called agent orange, an oily liquid that was a 50-50 mixture of the ?i-butyl esters of 2,4,5-T and 2,4-D. However, because the 2,4,5-T was contaminated with dioxin, and be cause during this time it was discov ered that dioxin is frighteningly toxic in some animals, and because an un k n o w n num b er of U.S. personnel were exposed to the herbicide while in Vietnam, an exceedingly complex problem has arisen. Vietnam veterans, learning from press accounts du rin g the 1970s that dioxin was hazardous and that they might have been exposed, began to ask the Veterans Administration some tough questions. The Chicago VA office really started things mov ing when a case worker there asked veterans about their possible expo sure to agent orange and any subse quent illnesses. She compiled a list of apparently affected veterans that June 6. 1983 C&EN 23 Dioxin Report found its way into the hands of a local news pro ducer who made a docu mentary pointing out the possible connection. As a result of the fears raised by this and other ac counts, VA reports that as of May 1 of this year, 17,068 veterans have put in claims for disability payments be cause of agent orange ex posure, and VA hospitals have treated 369,000 out patients and hospitalized 9600 veterans who claim their medical problems are related to dioxin exposure. (These numbers also in cluded a relatively small number of veterans seeking help because of radiation exposure during early atomic bomb tests.) The problem, according to VA, is that it has essentially no evidence that the variety of complaints being described by the veterans had any thing to do with exposure to agent orange or its dioxin contaminant. Consequently, VA has balked at of fering compensation. Part of VA's reason for rejecting the agent orange connection is a large amount of data compiled by the Air Force in the early 1970s on the use and fate of the herbicide and its contaminant, dioxin. This work finds, in general, that the herbicide, when sprayed on the top of a forest, quickly was destroyed by sunlight; that very little penetrated through the forest canopy to the ground; and that if it did get into the soil, the dioxin stayed there. But the growing cries from veter ans groups that their problems were caused by agent orange prompted Others to act. Seeking some hard in formation on the potential problems from agent orange exposure, Con gress passed a law at the end of 1979 that required VA to do an epidemi ology study of Vietnam veterans and to compile a complete bibliography of 2,4,5-T and dioxin health studies. VA also began an agent orange reg istry, an effort to identify all veterans ^concerned about exposurejo agent orange and find out what health problems they are experiencing. Veterans' records are computerized for future work. The biggest problem VA has had is getting the epidemiology study under way. Plans to contract out de sign of the study to the University of California, Los Angeles, School of Public Health were countered by a lawsuit from the National Veterans Law Center. Lewis Milford of the center says veterans did not believe VA would do an objective job in an alyzing the data, because of a preju dice against blaming agent orange. Subsequently, bowing to pressure from the House Veterans Committee Subcommittee on Oversight & In vestigations, as w ell as other Con gressmen, VA transferred the whole epidemiology study to the Center for Disease Control. Still, this did nothing for the growing number of veterans who wanted medical attention for prob lems they assumed were caused by the herbicide. In 1981, Congress passed the Veterans' Health Care, Training & Small Business Loan Act, which, in part, changed the rules for treatment at VA hospitals so that medical treatment for agent orange claims could be provided. Although this means most veterans who want it can get some medical attention, the question of disability compensation has not been resolved. For veterans groups, the disability compensation issue is a top priority. According to Milford, there is enough.medical eyidence of a link between dioxin and cancer to allow VA to make payments. But VA claims the only confirmed medical problem is chloracne and VA has yet to grant the first disability claim for agent orange exposure. Not that veterans haven't tried. As of May 1, 17,068 claims had been filed by persons who say they have been exposed to agent or ange. Some 8400 were found to have a valid med ical complaint and 1328 ciaims have been honored, but for reasons other than agent orange exposures. According to VA, 8617 of the claimants, when exam ined, had no diagnosable illness. In fact, 4102 did not even have a medical complaint, diagnosable or not. To break this impasse, Rep. Thomas A. Daschle (D.-S.D.) has in troduced legislation that would make any veterans suffering from chlor- acne, soft-tissue sarcoma, or the liver condition called porphyria cutanea otarda automatically eligible for compensation, whether or not any link to agent orange exposure could be made. It is hoped that the large number of research programs now under way or starting soon w ill help answer all the various questions. There are at least 65 federally supported pro grams, expected to cost more than $100 million, in the works to study dioxin. The largest of these is the epidemiology study being done for VA by CDC. This will involve 30,000 people divided into five cohorts and will be looking for any health prob lems that could be associated with military service in Southeast Asia. The study is not expected to be com pleted until late in 1987, but other work will be finished earlier. One of the first is the Ranch Hand study by the Air Force of about 1200 military personnel who worked spraying agent orange on South Vi etnamese forests. A mortality study of these individuals has shown no evidence of a problem one way or the other, but the sample size is far too small to mean anything. More sig nificant will be the morbidity anal- ysi of thesepeople that isexpected this fail. ! Another VA mortality study will gather data on all veterans who served in Vietnam from 1964 to 1975 24 June 6, 1983 C&EN ^-< 0 and compare their cause of death with that of veterans who were not stationed there. A twins study is also part of the VA program. About 500 pairs of twins have been found, one of which served in Vietnam and the other did not. They will be given psychological, physiological, and biochemical tests to see if any health differences can be found. VA also is utilizing the Environ mental Protection Agency's National Human Adipose Tissue Study, which has been examining human fat tissue since 1972 for the presence of about 20 chemicals, but not for dioxin. VA plans to backcheck 550 samples available from men born between 1937 and 1952 who could have served in Vietnam. VA does not ex pect to finish this analysis until 1985. However, under the direction of Alvin R. Young, an Air Force scientist w ho has been involved with agent orange studies since 1969, a small pilot study of fat tissue from exposed veterans already has been done. It casts some doubt on the ability of this kind of analysis to detect any con nections between illnesses and dioxin exposure. Then there is the chloracne task force, a major effort by VA to find veterans who have the one health problem that has been confirmed as dioxin related. But to date, about 4300 claims of skin disease have been made, and only 13 could be consid ered service related by VA and only one of those appeared to be truly chloracne. Another large project that has just begun at VA is a case-controlled ep idemiology study for possible oc currence of soft-tissue sarcomas. These cancers, usually veiy rare, have been linked to dioxin exposure by two Swedish studies and some U.S. industrial experiences. About 1000 soft-tissue sarcomas recorded at the Armed Forces Institute of Pathology involve men aged 25 to 40 who might have been in Vietnam when the spraying was done. Although the protocol still is being developed, final results are expected by the end of 1985. These federal programs are only part of the work under way. Most were started only in the past couple of years when it was realized that huge potential problems related to 1 Dioxin history at a glance 1872 Chlorinated dioxins first synthe sized by German chemists. 1948 2,4 ,5-T registered as a pesticide with U.S. Department of Agricul ture. 1949 First industrial accident involving dioxin at Nitro, W .V a ., 2,4,5-T plant. 1957 Dioxin identified as an unavoid able contaminant in 2,4,5-T. 1 9 6 2 -7 0 2,4 ,5 -T used in defoliants in Vietnam. - 1966 U.S. Department of Agriculture and Food & Drug Administration established residue tolerances for 2,4,5-T on food products. 1970 Dioxin's teratogenicity, fetotox- icity first reported in animals. U.S. Department of Agriculture suspends uses of 2,4,5-T that might lead to greatest human exposure. 1971 Environmental Protection Agency cancels 2,4,5-T use on most food crops. Stables in eastern Missouri sprayed with dioxin-contaminated oil. 1972 FDA bans use of hexachloro- phene in nonprescription soaps and deodorants. 1973 Vietnam ese study links higher incidences of liver cancer, abor tions, and birth defects to agent orange spraying in that country. 1976 Explosion at ICMESA chem ical plant in Seveso, Italy, releases several pounds of dioxin in a densely populated area. 1978 EPA issues rebuttable presump tion against registration for re- maining uses of 2,4,5-T based on evidence, that 2,4 ,5 -T and dioxin cause cancer, birth defects, and fetal deaths. 1979 Environmental Protection Agency issues emergency suspension order to ban remaining 2,4,5-T uses except on rangeland and rice fields. Class action suit filed on behalf of Vietnam veterans against five U.S. chemical companies that made agent orange. Companies, in turn, file a third-party action against the U.S. government passing responsibility for alleged harm to the government for its negligent misuse of the chemi cals. 1980 EPA requires advance notice of disposal of dioxin-contaminated waste. 1981 Class action suit on behalf of Vietnam veterans filed against Veterans Administration and Department of Defense. FDA advises people not to eat fish containing 5 0 ppt or more of dioxin. 1982 Extensive dioxin contamination found in eastern Missouri. 1983 EPA offers to buy the town of Times Beach, Mo. EPA issues proposed rule allow ing disposal of dioxin-contami nated wastes only in approved landfills. dioxin exposure existed. Several states have set up their own task forces to help veterans, and there are many international investigations that are trying to find a link between the phenoxy herbicides and a variety of health problems. Veterans with disabilities they believe were caused by exposure to dioxin in Vietnam quickly learn that unless they get compensation from VA, no other government aid w ill be forthcoming. There is a strong feel ing among many of these veterans that the government has a responsi bility not to expose its people to hazardous substances, and that, if it does so, it should be liable. But there is a long history of the courts refus ing to allow veterans to sue the gov ernment for this type of injury. So, attention has been turned to the companies that manufactured the herbicides that became agent or ange. In 1979, Victor J. Yannacone Jr., representing the survivors of a heli copter pilot who served in Vietnam, sued 11 companies for their part in exposing veterans to toxic chemicals. The number of plaintiffs has since climbed to about 9000, including 5000 veterans and 4000 survivors and children of veterans. The suit insists that the companies knew of the tox icity of agent orange's components June 6. 1983 C&EN 25 i * < 9 ____________ Dioxin Report and failed to inform the government against the companies stems from a eroded by the actions of other federal and that, therefore, the companies meeting in 1965 between Dow and agencies in response to dioxin con should be liable for injuries caused other agent orange makers in which tamination, and the difference has by the herbicide and the dioxin con the toxicity of dioxin was discussed. not been lost on veterans. Although taminant. The suit has become Dow is supposed to have told the most regulatory action against 2,4,5-T lengthy, complex, and costly. manufacturers they would have to do and its contaminant dioxin was not The original companies named something about the levels of dioxin begun until after 1970--after most were Dow Chemical, Monsanto, in agent orange, or the government troop exposure in Vietnam was Hercules, Thompson-Hayward, Uni- would take regulatory action against past--concerns about health effects . royal, Diamond Shamrock, Thomp the use of 2,4,5-T. Shortly after that, of dioxin from agencies such as EPA son Chemical, Aggrasit, Hoffman- Dow bought a license to use a process . and CDC appear to be far greater Taft, Riverside Chemical, and developed by West Germany's than those voiced by officials at VA. Hooker Chemical (which made the Boehringer Ingelheim that reduced Nothing makes this clearer than the 2,4,5-T precursor 2,4,5-trichloro- levels of dioxin in 2,4,5-T to less than dramatic actions taken to remedy the phenol). 1 ppm and urged the other makers to dioxin .contamination problem in Most of the companies asked U.S. do the same. According to Dow, some Times Beach, Mo. Federal District Court judge George did and some did not. Whether the .Times Beach has a most unenviable Pratt for a summary dismissal of the 1-ppm level is a safe one for dioxin is reputation as the town too poisoned claims that they are responsible for one of the questions that has not to live in. Just a few miles west of St. any injuries, under the government been answered, though that is just Louis, its fate has been sealed as the contractor defense. This means that what the jury may be asked to decide result of some poor waste disposal the government, as the user of the at this trial. practices, insufficient environmental herbicides, knew as much as or more If the companies are found liable laws in the early 1970s, and political than did chemical companies about for the injuries allegedly resulting pressures for action. Because of the the hazards and should have used from dioxin exposure, they can be contamination and the federal gov this knowledge to warn those who sued in state courts by veterans or ernment's decision to buy the town, might be exposed. They also contend, their survivors for damages. In most Times Beach is expected to disa'p- and have proved to the judge's satis states, the statute of limitations w ill ' pear. faction, that the Department of De have expired for taking action The story traces back to the 1960s fense had set standards for agent or against the companies and special and begins w ith agent orange. ange which were met by all the legislation will have to be passed, as Hoffman-Taft, one of the original companies. Two companies that have it has been in New York for instance, defendants in the agent orange trial, not asked for a summary judgment if the veterans are still going to be made 2,4,5-T for the Department of are Monsanto and Diamond Sham able to sue over agent orange expo Defense for a w hile, but ceased pro rock. sures. duction in 1969, about the time eco For a variety of reasons, some of Just how many vets actually were logical concerns led the military to the companies have been released exposed is a question impossible to halt spraying. In November of 1969, from the suit. Those remaining are answer. The military records are not the plant in Verona, Mo., was leased Monsanto, Diamond Shamrock, Uni accurate enough to tell exactly where to North Eastern Pharmaceutical & royal, Thompson-Hayward, and the every soldier was when spraying was Chemical Co., and then later sold to IS largest producer, Dow. The trial had done in an area. And wind drift or Syntex Agribusiness, which let the been scheduled to begin June 27, but, elapsed time before troops entered a pharmaceutical company stay to in a procedural move, Pratt post sprayed area also would determine produce hexachlorophene. poned the opening until completion exposure. DOD had said early in the According to EPA's records, wastes of the discovery process, an infor agent orange controversy that it kept from the plant were being disposed mation gathering period that attor troops out of sprayed areas for up to of properly by shipping them to a neys say could take another year or six weeks, but many reports show waste facility owned by what is now two. that gound troops entered some Rollins Environmental Service near The judge's decision to go ahead sprayed areas as early as the next day. Baton Rouge. But in early 1971, al with the trial means that the com Veterans groups say they have an legedly to save money, North Eastern panies must prove they withheld no ecdotal evidence that planes sprayed contracted with a firm called Inde health data from the government some troops directly, or that troops pendent Petrochemical to haul away that would have made a difference in had loads of agent orange dumped its sludge bottoms. Independent, in the spraying of the herbicide. Al on them when a plane was damaged turn, subcontracted the job to Russell though there are some data in the by enemy fire and had to return Bliss, a waste oil hauler in Missouri. early work on 2,4,5-T on the prob quickly to its base. The records show that Bliss hauled lems from dioxin, they are scanty. Despite the controversy over ex away 18,500 gal of waste bottoms Dow, which made more than 30% of posure and possible health problems, containing dioxin from the Verona " the total agent orange used in Viet VA still holds that no long-standing plant, which he apparently stored in nam, is sure the government had all health problems exist from agent waste oil tanks near Frontenac, Mo., the safety data it needed. orange exposure. It appears, how between February and October One of the allegations raised ever, that this position is being 1971. 26 June 6. 1983 C&EN But Bliss used some of this con taminated waste oil to spray horse arenas in May of 1971. Three stables apparently were sprayed, and the consequences were severe. Over the next few days and weeks, hundreds of animals got sick and died, includ ing at least 65 horses. One six-yearold child, the daughter of one of the stable owners, developed an in flamed and bleeding bladder after playing in the soil of the arena, and three other children and one adult complained of skin lesions after ex posure to the stable's. All the symp toms disappeared after exposure was halted and have not recurred. State of Missouri investigators, reasoning that something must have been in the oil that was sprayed, sent samples to CDC for analysis. The arena owner asked Bliss if anything dangerous had been in the oil and Bliss reportedly said there was not. In the meantime, the state had the are na's dirt hauled away and placed in a distant landfill. Some of it, how ever, was used as fill dirt for resi dential construction, in what has now become known as the Minker/ Stout site. CDC, with few clues to go on, took until 1974 to identify dioxin as the toxic compound in the oil. Scientists there, led by pathologist Renate Kimbrough, eventually determined that the oil was contaminated at about 33 ppm, a level far higher than any that occurred in Vietnam from agent orange. Crystals of trichlorophenol found during the soil analysis extraction led the investigators to the Then, in 1979, EPA's office in Hoffman-Taft plant in Verona, and Kansas City received an anonymous the thinking was that 2,4,5-T pro telephone call that toxic wastes were duction was the culprit. But it was buried on the James Denney farm, then discovered that the hexachlo- near Verona. The tip checked out, rophene wastes made by North and a number of drums of dioxin- Eastern had been disposed of im contaminated waste eventually were properly. removed from the site. This got EPA By this time, Bliss had sprayed,oil investigators thinking. v: - over many sites in eastern Missouri. It had been believed in the early EPA has reconstructed as much of the 1970s that the half-life for degrada Bliss operation as possible and be t io n ^ dioxin in soil was less than a lieves there were more than 150 sites year, based on tests by the Air Force sprayed with the waste oil, but how, and U.S. Department of Agriculture. many are contaminated with dioxin That was wrong. EPA found that won't be known until testing, can be waste leakage from the drums still completed. had high concentrations of dioxin, The search for contaminated areas when almost-all of it should have did not begin immediately, however, decomposed after being buried for as might have been expected. A large six or seven years. This prompted storage tank of wastes was found at them, after much record searching, to the Verona site, heavily contami go back to the stables that originally nated with dioxin. Levels of extracts were sprayed and to the sites where were measured at 356 ppm by the the contaminated earth was dumped CDC researchers. This became the to measure present dioxin levels. The primary concern because its potential levels found were essentially as high for human health injury was seen as as they had been in 1971. At the site high. Syntex, which now owned the where the soil had been used as a plant, had the wastes detoxified by landfill, levels ranged from 10 ppb to ultraviolet treatment at its expense. 300 ppb. At the Shenandoah Stables, It should be remembered that at that concentrations were still as high as time there were no federal laws 1750 ppb. governing waste cleanup or proper These tests began in spring of 1982, disposal. The Resources Conserva and the first data were released in tion & Recovery Act was not passed August. The findings prompted a until 1976, and the abandoned waste more exhaustive sampling of all the cleanup law, superfund, didn't go areas known to have been sprayed. into effect until 1981. By December, more than 300 samples With no further reports of serious had-been analyzed and the results illnesses, the issue faded away after released. EPA had found dioxin lev about 1975. els of up to 300 ppb in the Times Beach area and contamination in about 14 other sites. The news of extensive dioxin contamination in Missouri came at a critical time for the agency. EPA Administrator Anne Gorsuch Bur- ford was under intense pressure from Congress for information relating to actions the agency had or had not taken under the superfund law, and that body was moving in early De cember towards finding Burford in contempt of Congress. The situation was complicated w hen the Meramec River, which flows by Times Beach, flooded just before Christmas 1982, and officials worried about the dioxin spreading to other com munities. (Followup tests Showed that the dioxin had not moved with the flood waters.) June 6, 1983 C&EN 27 ! ______________ l Dioxin Report CAEN*taft photo I The situation now began to get moved because they do not want to tense. Residents of the community be expected to provide services, such demanded that the government buy as water, to the areas. There were, last i their homes so they could move to a month, about 50 families that were safe place. Some people began com not moving, but a second flooding of paring the contamination problem at the Meramec seems to have con Times Beach to the situation at Love vinced them it was time to leave. Canal in New York. Then, in early Spokesmen for the Federal Emer February, the EPA assistant admin gency Management Administration, istrator in charge of waste cleanup which has been on the site since the and superfund, Rita Lavelle, was first flood in December and is re fired by President Reagan, amid al sponsible for dealing with the resi legations she had used the superfund dents on the buyout, say it appears for political leverage in favor of Re that all the former residents are publican candidates. leaving. In addition, an unofficial Possibly pushed a little faster than and unapproved agreement may she would have been otherwise, EPA have been reached that would permit Administrator Burford announced the property to first be assigned to Feb. 22 that the federal government the city of St. Louis, so the cleanup would buy up all the contaminated could get started, then transferred to property in Times Beach, paying the Missouri when that state's conditions residents a price reflecting property are met. In the meantime, the resi values before the dioxin contamina dents are living elsewhere and have tion was found and before the yet to receive the promised com flooding. Superfund would supply pensation. $33 million and the state of Missouri As of this writing, there are 31 would supply $3.3 million more. confirmed sites of dioxin contami Young: doubt cast on ability to link Subsequently, on April 5, EPA of nation in eastern Missouri, all trace -illness with exposure to dioxin fered to buy a number of homes in able to the spraying by Russell Bliss. the contaminated M inker/Stoutsite Officials believe the final list could objections to the draft report centered that had been built on dirt from the contain more than 100 sites. How on a statement that EPA concludes stables originally sprayed by Bliss. A many more people might have to be that Dow's Midland facility is a third area, the Quail Run mobile moved and how much it will cost is major, if not the only source, of home park, was found to be contam pure speculation, but the expenses dioxin contamination in the Titta- inated with up to 1100 ppb of dioxin can be expected to rise. bawassee and Saginaw Rivers and in a sample dug out from beneath a Midland, Mich., is another city Saginaw Bay in Michigan. That six- paved road, with levels of 2 ppm in that has become associated in the line draft conclusion did not appear side two of the mobile homes. EPA public mind with dioxin contami in the final report. has also offered to buy the trailer nation. Ronald O. Kagel, director of envi park. At this time, no other areas are The Midland connection first sur ronmental quality for Dow Chemical being bought out. faced in the national news media last USA, who reviewed the report for r; The decision to move residents, March when Rep. James H. Scheuer EPA, says, emphatically, that he did either temporarily or permanently, (D.-N.Y.) charged that he had evi not ask EPA to delete that six-line i is made by CDC and the Missouri dence showing that then EPA acting paragraph from the report. He says Department of Public Health, on the administrator John Hernandez had he did point out that "the whole gi basis of results from samples sub intervened personally to allow Dow paragraph was lifted out of a 1978 mitted by EPA. The belief that a level Chemical Co. to alter a draft EPA re report and it appeared again almost of 1 ppb is probably safe comes from port on the sources and effect of word-for-word in a report written in 1 a CDC estimate using a number of dioxin in the Great Lakes region, 1979. At that time we could not dis studies, and is discussed on page suppressing all references to Dow's pute that and we didn't. But in 1981 48. responsibility for dioxin contami there had already been an interna When EPA told the residents of nation in and around its plant. tional dioxin conference. There had Times Beach the government was In fact Scheuer charged that owing been many papers published sup going to buy their homes, the process to Hernandez's intervention, and by porting our theory that dioxin can be was expected to take 60 to 90 days. implication Dow's, all references to created by combustion. I said, 'Gee Now, after three months, there is still studies showing the adverse health guys, that's a 1978 statement in a 1981 a hangup. The federal government effects of dioxin were removed from report and I really think you should cannot take title to the property be the report. change the word 'concludes' to c a u s e the law forbids spending-su -- Testifying before Scheuer's natural 'speculates' because of the data that perfund money to clean up federally resources subcommittee on March 23, support our theory.'" owned property. Missouri w ill not Valdas Adamkus, EPA's Region V Kagel says that in making his take title until all the residents have administrator, said that Dow's comments he was "strictly trying to 28 June 6. 1983 C&EN speak to the validity and technical accuracy of the report and specifi cally those portions that were taken out of Dow's work." Further, he says that many;of the portions of the draft report released by Scheuer that were marked "cut" already had been de leted from the copy of the report he received. Others had markings indi cating that somebody already had decided they should be cut. At just about the time the charges of undue influence were being aired two Michigan environmental groups--the Foresight Society, headquartered in Lansing, and the Environmental Congress of MidMichigan, headquartered in Mid la n d -filed a citizens petition with EPA asking for a full field investiga tion of central Michigan. They said an investigation was needed to de termine the effect of the pollution caused by disposal and emissions into the air, land, and water of chemical substances that threatened the health of the residents and the integrity of the environment. At a press conference in Washington, D.C., Andrea K. Wilson, director of ECOMM, explained that "given the fact that soft- and connective-tissue cancers among white females in Midland County are four times the national average, the birth defect rate is now being re-evaluated, and Dow's own data indicate that soil samples taken at their Midland plant contain a range of TCDD (dioxin) from 0.3 ppb to 100 ppb, w e feel that a full field investigation, including an ep idemiological study, is warranted." Hard on the heels of the petition came an announcement by EPA's Region V office (which covers the upper midwest) that a preliminary investigation had found more than 40 toxic chemicals, mostly in the low parts-per-billion range, in the ef fluent from Dow's Midland facility. Dioxin was found at levels of 50 parts per quadrillion in the effluent and at levels of 100 ppt in caged whole fish that were exposed to the effluent. The search for dioxins in Midland may very well have been initiated by a false-positive test result. Dow pe riodically monitors its discharges for TCDD and on April 13,1977, the lab reported a positive number--8 ppt with a detection limit of 3 ppt. "That got us concerned," Kagel explains, "because we had never seen dioxin before . . . but it triggered a number of things." The first thing that was done was an analysis of some fish that had been caught in the Tittabawassee River the year before during Dow's biennial river survey and placed in the freezer. Analysis of the fish showed dioxin levels ranging from nondetectable to 0.19 ppb, with a detection limit of 0.02 ppb. In May of 1977 the company collected more fish--mostly bottom feeders--from the river, analyzed them, and again found positives. Kagel points out that the state-of-art analytical method at that time allowed only the detection of 2,3,7,8-TCDD, plus 16 other tetra isomers. After the second batch of fish was analyzed, Dow devised some exper iments using caged fish to determine where the dioxin was coming from. The first shipment of fish ordered died before it got to Dow. The second batch of fish all had a fatal fish dis ease, commonly known as the "Ick." The third shipment from the East was A n o n if A r a n n a f a r l a c c r iir w t n f h f l r i b a r l i o r O A 'K'JT l a Assumed level from one known and four probable samples of purple. Nofe: Pink'and green levels are twice that " p of pwpie because they were fult-strength 2.4,5-T. Sources: Proceedings from 2nd Continuing Education Conference ^ ij on Herbicide Orange. May 1980; and Air Force OEHL technical report on toxicology,' fate, and risk from agent orange /ji and dioxin, October 1978 t .ui:'.f found to be loaded with PCBs, which would have interfered at the time with the TCDD analysis. Finally, towards the end of 1977 Dow got a batch of usable trout and put them in cages where its effluent mixed with the river water under flowing con ditions. Bioanalysis of the caged fish was completed in May 1978. Positives were found for most fish in the mix ing zone. At the same time, Kagel says the fish research lab, which had been doing studies on the biomag nification of TCDD by trout, reported a biomagnification factor of 6600. Dow reported all of its findings to the State Department of Natural Re sources in June of 1978. In July, the company met with state representa tives and made a commitment to find the source of the dioxins. The first thing Dow did, Kagel says, was to look at its own internal waste streams, where it might expect to find dioxins, and didn't find any thing that could be considered sig nificant. Then, he says, "Quite by accident two of the chemists in the lab went up to the second floor to get a control sample of dust off a book shelf. They analyzed that dust and found it contained all the dioxins-- the tetras, the heptas, the hexas, the octas. We said, 'My God, we've been looking for a waterborne source and we know that. . . the second floor has never been under water. So it's got to be from somewhere else that's air borne." That, he explains, is when "we started looking around the division at dirt samples and seemed to find more dioxins as we got closer to our incinerator and power plants." Thus was Dow's combustion theory born. The company dispatched scientists to several cities to collect soil samples around municipal incinerators and powerhouses. In almost every case they found dioxin, although not necessarily 2,3,7,8-TCDD. They ana lyzed the carbon soot inside mufflers collected in Detroit and found diox ins. They also found 100 ppt of 2,3,7,8-TCDD in the soot from a fire place, which happened to belong to Kagel. According to Kagel, the formation of dioxins is maximized and its de struction minimized when the tem perature is low, below 750 C. At June 6, 1983 C&EN 29 Dioxin Report Road going through Times Beach, Mo., is blocked b y sign warning o f dioxin temperatures above 1000 C just the opposite occurs--formation is mini mized and destruction maximized. Thus, municipal incinerators could be expected to produce more dioxins than industrial incinerators, which burn at 1000 C, because the munic ipal facilities operate at generally lower temperatures. Dow Chemical researchers sample Tittabawassee River for dioxin near the company's Midland, Mich., plant While it was doing this work Dow also was perfecting its analytical techniques, Kagel says, using a mix ture of three different methods dur ing the course of study. The first separated out 2,3,7,8-TCDD plus 16 other tetra isomers; the second, 2,3,7,8-TCDD plus 11 others; and the third 2,3,7,8-TCDD plus two other isomers. Then in late 1978 a tech nique was developed that isolated all 22 tetra isomers. Since 1979 Dow has done several other studies. Having, as Kagel says, "made the comment that we thought that dioxin had been around since the advent of fire" and figuring that wood was one of the earliest fuels, a study was done of residential woodburning stoves in Minnesota, New Hampshire, Oregon, and Michigan's upper peninsula. The source of the wood for each stove was carefully documented to make sure it had never been sprayed, never treated with pentachlorophenol, Kagel says. But in each case some dioxins were found in the soot from the stoves. As Kagel points out, one of the components of wood is lignin, a phenolic material. There is also a natural chlorine content in wood which will vary from 14 to 84 ppm. "Remember," he says, "we're talking about reactions that occur with a yield of 10-10%. These are trace re actions, and 14 ppm, when you're looking., at a m illionth of a m il lionth--a ppt--is a lot of stuff. It's the same with coal, which actually has a much higher chlorine content than wood, and is nothing more than a whole mess of ring compounds of one sort or another. So the basic building blocks are there." "This is as close as we can come," he says, "to confirming the de novo principle, that dioxin is made from carbon, hydrogen, oxygen, and chlorine. Nobody has done a defini tive experiment on that that I know of. But the preponderance of evidence right now would support the fact that you can get dioxins formed at very low levels in the combustion processes from common fuels." If that is true it would go some way towards explaining the results of a recent study which shows dioxin contamination in fish in many rivers in Michigan. The fish were collected from 19 Michigan rivers, plus Sag inaw Bay and Lake Erie by DNR. Their skinless fillets were analyzed by Swiastolov Kadzmar, a graduate student working under Matthew J. Zabic, professor of entomology and assistant director of Michigan State ,,University's pesticide research cen ter. Thirty-four of the 62 fish ana lyzed had no detectable levels of dioxin. Levels of 2,3,7,8-TCDD in the other fish samples ranged from a low of 17 ppt, with a detection limit of 12 ppt, to a high of 586 ppt, with a de tection limit of 81 ppt. Many of the positive samples came from fish taken from waters that had no con nection with the Tittabawassee rivershed and therefore they could not have been contaminated by Dow's effluent, though the samples did come from rivers in industrialized areas. Typically, Kagel says, dioxin is very tightly bound to fly ash, as it is to soil. To remove dioxin from fly ash one has to do exhaustive benzene or toluene soxhlet extractions for 24 hours. "It's very tightly held," he says, "so the question is how does it get off the fly ash and into the fish?" D ow has been involved with EPA's Duluth, Minn., lab in a joint study designed to answer that question. Duluth supplied some carp fingerlings, Kagel explains, "which we put into a fish tank with some municipal fly ash of which the 2,3,7,8-TCDD content was about 160 ppt. That rep resented about 0.48% of the total tetra isomers, all of which were present. After 30 days in the tank the fish I j | 30 June 6,1983 C&EN ' . Dioxin Report ';|2,4,5-T containing lo w levs oTdio xin //^/tam i natd 'w a ste,,under tho Resource a ( n'^ A m n ^ A r l f i t s ' l l C / r i k n n U m A M i a I J r . T V i r i e o n i Q t n n f A ' J D / ' r t i i n r ' A /%f ' T K i r ///th e compour^^'permitting use/:only/^oni|^cbn^mihatec!' waste; onlyrat/facilities *} //forests/1righ ts/o f/w ^ ^ th a t-'a re ;fully licensed by- EPA .'The"; ,.|an d rice fields^njadd itfpn, a' voluntary .^agency says potential problerns might J/ ------ - j !_ aiiowed'at unper-v' In'lncinerators' th at;/ rinq/ properiyJlTiis r l I supersede Ih e l'/ . Environmental ProtectlonVAgeh^ rule. -, / / ' / / ' / / - ; / / yf!u ^ ! r 'h " i 'n n t [ n i i o 7 i ' [ te ' in w o c 4 in a t)n n tt an H '/.is.1:tT h A ? n th P r f l f p a ' Iri lA /hiph P P A " Iq j \ Dioxin Monitoring ' Program^ to" m o n ito r^ to r|rig effluents; from . chemical plants / residues of dioxin In hu'rnan 'and e n v iO ^ to determine.tf clioxin is present a n d /if !//ronm ental/sam ples/PA attempted tq ^ n s /a t wht'concentratiorirThese data ^ /,, c a n c e l all uses.f herbicides that w e r e ^ c ld be/usetJ inp reparati n'o f a w a- } derived from '2,4,5-trichldrophenol in' f^ t r quality criteria dcxjument. th is would j { /t h a t year'but eventually had to .cancel give manufacturers an idea "of what . t h e proceedings because the an alytK // EPA thinks is a s a f 'ie v e ljo r dioxin in ' | i/" c a l methods' necessary /to determine ///water and probably/would p'r e s a g e fu r -// (-\lpw:.levels pf'^pxinlw ere not available, 4 h e i; regulation-of dioxin/urider either/?! pi/The agency/began/a/rebuttable p re -/^ th e Clean/Water Act or TSCA. (Because/. [ .sumption against registration process^/dioxin is a priority water pollutant, som e/;/ Lion 2, 4, 5- TJn`i _ J//.fstates/have reigulatlons tha(require no^/^ ` . // / T h e n in May~ 1979, 'on th basis of /^detectbl/levels in plant effluents.)* `f ' : ' ' .heavily criticiz_ed\studies/' linking the //^//The'only other significant action tak/v ; ip/spraying f,,fprestrres/jyith '2,4,5-T ^/ri on;dioxin/is 'by. the Food *& Drug"/ jp.Tto Tn umbr.-of:miscarriages^among / / Administrattari. seristaf recomrnem:` f j^women in.Oregon, EPA issued an emer- ^datlons ^(not /regu!ations)/ by FDA In-.! ! r gency suspension that allowed the h er-/ ' 4 9 8 1 advised people not to t fish ; ['^bicide to b e/used just on rangeland. with dioxin1levels greater than 5 0 p p t;./; and rice fields because Ep saw little ^ but that /fish with .less than 25 ppt t Trisk/of human exposure there'. `/ di oxi n wereAokay to eat! Because these : / } T h eJ hearings o n /ca n c ellatio n of are not regulations, an FDA spokes--.-j i ;/2,4,5-T have dragged on. They currently .. 'man points out that if the levels do// | p i;are su sp en d ed ,w h ile E P A /and th e 1 'ris e above'50 ppt, the agency cannot 'J 'chem ical manufacturers try to reach take any action to remove the product. j ,j som e kind of agreement, possibly on J, Thus, aside from the restrictions on * permitting some use of the herbicide the use of 2,4,5/T (because of its dioxin ` '4 if dioxin levels in it can be kept very contamination) and the current 60-day "1 low. *f ; " . -1' /; notification rule for waste disposal, But other tools have passed Into -dioxin is-not specifically'regulated by "T EPA's hands for regulating dioxin. On the federal government. 'I 32 June 6, 1983 C&EN were taken out an4 analyzed and 84% of what was found in the fish was 2.3.7.8- TCDD." Kagel theorizes: "There's some weird mechanism in the fish--that was phase two of our study, to try and find out what that mechanism is--that makes them selectively ac cumulate 2,3,7,8-TCDD, or, the other way around, there is some mecha nism whereby they break- down or metabolize the other isomers. That was a preliminary experiment and w e were going on to controlled ex periments w hen all of this started and we never got back to it.. . . I sure would like to get an answer." So would everybody else. Dow says that it has no manufacturing operation anywhere in the U.S., in cluding Midland, that has any 2.3.7.8- TCDD associated with it. But EPA's Region V office in Chicago isn't so sure. On April 11 it asked Dow for any and all process- and waste-related information the com pany m ight have pertaining to dioxins. Dow delivered the first set of data--2000 pages worth--on May 12. The company said it took 26 em ployees, 13 of them working full time, to compile that information and it is still collecting data. Among the data submitted were the results of a new soil analysis conducted by Dow, repeating the analysis done in 1978, except this time the analytical technique was isomer specific. Five soil samples collected inside the plant site showed levels of 2,3,7,8-TCDD of 0.08, 0.38, 2.04, 0.018, and 0.02 ppb. The levels in two samples from Midland were 0.0016 and 0.0072 ppb; Chicago, 0.0010 and Q.0042 ppb; Lansing, Mich., 0.0030 ppb and not detected; and Detroit, 0.0036 and 0.0021 ppb. "There is no health hazard in Mich igan because of dioxin in the dirt or in Chicago. Not at the levels we find it," Kagel says. Midland's mayor Joseph Mann agrees. "So what if we've got 7 ppt in the soil here. Being bound the way it is how do you get to it? How do you come in contact with it? How do you assimilate it?" He points out that if the exposure were causing harm it would manifest itself somehow. But he says studies by the State Depart ment of Public Health have shown that "the overall cancer rate in Mid- I A# _ J ___________ Dioxin Report land is low --below the national av erage, below the state average, and below the average for the surround ing region." He says there was a soft-tissue sarcoma in women that was higher than normal. 'There was one case in the 1950s, five cases in the 1960s, and eight cases in the 1970s. This was a matter of concern to the county health department, the state health department, and certainly to us," Mann says. The State Health Department conducted a study and released its results on May 4. And according to Mann "could not ascribe any particular causes to the rate of increase. There was no commonality between the cases that could be found; although the department felt there must have been a commonality, they certainly couldn't say that it was dioxin." The department did recommend development of a registry of persons most likely to be exposed to dioxins as evidenced by their occupations, fish consumption patterns, or loca tion of residence. Such a cohort of people, it said, could serve as a framework for possible future epi demiologic studies. Meanwhile, Midland's attitude to the dioxin issue is expressed in a va riety of ways. Mann says that "the perception within the community is that there's nothing out of the ordi nary, nothing dangerous." But he adds, "That's not the perception if you get more than 100 miles away from here and have gotten most of your information from the news media." Then there are the retirees from and employees of Dow who come into Rep. Donald J. Albosta's (D Mich.) local office and who, says of fice manager Pat Casey, feel as if the criticism is being directed at them. "Their feelings, and I think their beliefs, are that they worked for a high-class company that spent a lot of bucks on environmental concerns and research. Dow has always had a very aggressive in-plant safety pro^ gram. So the employees don't feel there is any justification for the in sinuation they pick up that Dow has done something wrong." City manager Clifford Miles thinks that one of the reasons for the very low level of concern in the city, and one he personally subscribes to, "is Kagel: dioxin dust on a bookshelf that the people who have done the testing, the measuring, the toxicolo gy and epidemiology studies are all Midland people. They all live here with their families. It isn't some outsiders coming in and saying ei ther it's safe or unsafe. It is Midland people that are doing these things and they have significant reputations not only in Midland but worldwide." Certainly no one is going to stay here if they know their family is in jeop ardy, he says. Miles explains that over the years, because of Dow's en vironment and safety record, "people have built up a wealth of confidence in that corporation that could not be Mann: nothing out of the ordinary bought." And he says, 'They [Dow] have done everything they can and should have done to alert the public, the media, the state and federal gov ernment." Some people aren't so confident. As Dianne Herbert, one of the lead ers of ECOMM, sees it, "Dioxin is a sexy issue that has gotten the atten tion of the media, but it certainly isn't the only environmental or health problem in Michigan." She also thinks it's good that the attention of EPA is focused on Midland. How ever, she notes the city itself is fighting any investigation. 'They naturally want to get the focus off," she says. "Their strategy is let's spread it out and say, 'Oh yes, dioxin needs to be looked at, but all over the country.' There are problems--peo ple don't want to move to Midland; people have called and asked, 'What kind of place is it?' Maybe the prob lems should have been taken care of earlier on. They accumulated until they all blew up and that's too bad. I'm from Michigan and I like living here. I don't want to give up my house. I don't want to move." Herbert says she understands the reluctance of any community to believe that there is something wrong or that the company that many of them work for has done something that is illegal or bad for their health. "The average person you talk to," she says, "will say that Dow has been good to us and I would never disagree with that. For a com munity this size to have its own symphony, a beautiful center for the arts--that is very unusual. But I don't think that gives them the right to do what they want with the air, and the water, and the land. The bottom line is that in this community Dow de cides what is safe and what is dan gerous. They make those decisions for people and I think that people should be allowed to make their own decisions." Others are seeking further infor mation. That was the purpose of a late May forum on dioxins organized by the Midland sections of the American Chemical Society, Ameri can Institute of Chemical Engineers, and Sigma Xi. At the forum, which about 500 people attended, a panel of five technical experts on dioxin issues 34 June 6. 1983 C&EN Dioxin Report answered questions from five local ment? Is that a problem? And, finally, planned. As Mann puts it, "First you citizens--none of whom worked for are national standards needed to deal say there's a ticking time bomb, a K D ow --and the audience. with the problem? life-threatening situation, and then According to Susan Butts, a senior The study as now planned would you do these studies--the results of research chemist at Dow and an or be run by the Region V office. A which won't be out for two or three ganizer of the forum, its impetus prototype study costing $2 million to years, What we need is a reasonable came from the fact that "we were $3 million would first be done in amount of analysis in a reasonable aware that a lot of studies had been Michigan. That study then would be amount of time, primarily to reassure done on various aspects of the dioxin expanded to a national level at a total people outside this community that problem, but w e hadn't really heard cost of about $12 million. According it isn't as bad as had been pic very much about the results of those to Richard Powers of DNR's toxic tured." studies. Our concern was really in chemical evaluation section, the Along the same lines, the Midland trying to hear a more detailed expla Michigan part of the study, as tenta City Council, three of whose five nation of the sitution, in terms that tively planned, would consist of a members, as well as Mann, work for would be understandable not only to study in the vicinity of Midland to Dow, passed a resolution expressing scientists but to the general public." determine the extent of contamina its support of scientific studies on In putting the panel together, she tion in that area. This would mean exposure levels and effects of dioxin says, "We tried to be sure that we sampling soil, air emissions, and on the environment and the public fairly represented all points of view. water effluents from the plant site, health as long as they weren't limited We did rather heavily weight it and river sediments. The second to Michigan, but also expressing the towards people with a biomedical component of the study would be council's feeling that $12 million was background, because we thought monitoring fish, including game fish just too much. most of the questions from the audi and bottom-feeding carp, in 15 Further study is quite probably the ence would concern human health Michigan rivers for dioxin contami proper response to the levels of problems. And most of them did. nation. dioxin contamination that have been There were a lot of questions about As part of the national study, air found in Michigan. And, although the toxicity of dioxins, about the and soil sampling and possibly fish EPA appeared to rush into Missouri meaning of toxicity, and about how monitoring would be done at other in an attempt to improve'its public dioxins would be rated relative to sites, perhaps in Michigan, perhaps image when everything the agency i other health hazards." in Region V, or perhaps somewhere did was being looked at with cynical For her part, Butts says she never else in the country. Powers says, "It eyes, hindsight may show the deci had a personal concern about her doesn't make any difference to us sion to be justifiable and prudent. own health, but she did want to where they're done, as long as they Other human exposures to dioxin, know where Midland stood in rela are done. We feel it is necessary to such as those of soldiers in Vietnam tion to other places in the U.S. that have comparability studies in other or the people in Seveso, Italy, in 1976, have problems with dioxin contam areas of the country, both areas that involved considerably less dioxin ination. "I felt quite reassured," she would be expected to be contami than those of the Times Beach resi says, "by what we were told by the nated and others which should be dents. panel members. There were some relatively clean." In Vietnam, for instance, the Air minor disagreements about inter Protocols for the study are being Force's Young calculates that the pretation of data. But, if I were going developed, but actual work is pretty level of dioxin in the soil would have to try to summarize what the panel much on hold because everything is been 0.017 ppb, 20,000 times less than said, it would be that they didn't feel contingent on getting federal fund the 300 ppb found in Missouri. That that there was any significant health ing. The House Appropriations assumes that agent orange, with an problem in Midland. But until we Committee has included $5 million average dioxin concentration of 2 know more about the situation they in EPA's fiscal 1984 funding bill for ppb, is sprayed at a rate of 3 gal per would like to continue monitoring nationwide dioxin studies--$1 mil acre and that all the dioxin falls right health in Midland to make sure." lion for R&D and $4 million for to the forest floor (although studies In fact just about everybody seems monitoring studies in Michigan and found that only about 7%of the agent to agree that what is needed is con Missouri as well as other places. The orange penetrated the forest tinued monitoring and more study, Senate Appropriations Committee canopy). preferably not just in Midland, nor has not yet made a decision. EPA's Similar types of exposure com even just Michigan, but nationwide. new administrator, William D. parisons can be made for the resi Rep. Albosta is seeking funding for Ruckelshaus, is expected to ask dents of Seveso, leading to the con just such a study. He feels that a Congress for more money for the clusion that the Missouri experience number of questions need to be an agency both in this and the next fis may represent the largest, long-term swered. Questions such as: How cal year and reportedly has expressed exposure to dioxins that humans pervasive is dioxin? At what con his support for a national dioxin have endured. If dioxin is the hazard * centration is it present in the envi study. that some believe, then the costs of ronment? Where is it coming from? Although everybody, including moving entire towns probably are What are safe levels? Are dioxins Dow, supports a study, not every not greater than the risks of letting bioaccumulating in the environ body is happy about what is being people continue to live there. 36 June 6, 1983 C&EN 4* Dioxin's Human Toxicity Is M ost D ifficult Problem Dioxin is extrem ely toxic to certain animals, but scientists are only beginning to understand the nature of its toxicity and exactly w hat it does to humans Rebecca L. Rawls, C&EN Washington animal yet tested. Rabbits, mice, and monkeys cluster somewhere in the Of all the questions that surround m iddle--roughly 200 times less dioxin, probably the most important sensitive than guinea pigs and 50 one, and one of the most difficult to times more sensitive than hamsters. answer, is: What is its effect on Dioxins are not the only com human health? Although its pres pounds that show this range of ence in the environment still would sensitivities from one animal species cause problems if it were harmful to another. Such a pattern is charac only to horses or guinea pigs or some teristic of several halogenated aro other animals, it is the possibility that matic compounds, including chlori dioxin may be very hazardous to nated dibenzofurans and chlorinated people that is behind most efforts to and brominated biphenyls. The fact understand how the compound be that all of these compounds have haves in the environment and to closely related chemical structures learn how to deal with it. leads some toxicologists to study That dioxin is extremely toxic to them as a class and has led to prom certain animals, causes many differ ising work that is beginning to un ent toxic effects in a wide range of ravel how these compounds cause animal species, and is harmful to their toxic effects. humans when they are exposed to Dioxins and these other halogen relatively large amounts of it are facts ated aromatic hydrocarbons cause that are well established. But even many different effects simulta after more than a decade of intensive neously in treated animals, and the study, scientists are only beginning relative importance of these effects iT to understand how dioxin causes its varies from species to species. Thus, toxic effects, and the key question of this makes dioxin some 2000 times dioxin appears to kill rats by causing J whether it causes any long-term, ir more toxic than strychnine, for ex severe liver damage, but in the reversible health effects in humans ample, in the mouse. Only a hand guinea pig the liver lesions seem less remains unanswered. ful of substances are known to be more serious and the animal appears to die The widely made claim that dioxin toxic than dioxin is in guinea pigs. from a starvationlike wasting away of 1 is one of the deadliest substances But dioxin is much less toxic to the entire animal. Both the liver le known, or that it is the deadliest mice than it is to guinea pigs. In fact, sions and the wasting away occur to man-made substance, is based on its one of the striking features of diox some degree in all of the animals that extreme toxicity in guinea pigs. As in's toxicity in animals is that the le have been studied; only the relative little as 0.6 /rg per kg of body weight thal dose varies so much from one importance of these effects varies. given orally will kill half of the male species to another. The guinea pig, Similarly, all species studied lose guinea pigs that receive the'dose. the most sensitive animal yet tested, lymphoid tissue, particularly from Illness occurs immediately and death is 5000 to 10,000 times more sensitive the thymus, and become more sen within about a week. Mole for mole, than the hamster, the least sensitive sitive to infections. However, it Junes, 1983 C&EN 37 Dioxin Report usually is not the infection that kills them, and putting treated animals in a germ-free environment w ill not save them. Not all effects are found in all an imals. Chloracne, a skin lesion that is the most characteristic and fre quently observed effect of chlori nated aromatic hydrocarbons on humans, does not occur in guinea pigs, hamsters, or some mice. Hair less mice, however, do develop a chloracnelike skin condition when exposed to dioxin, and so do rhesus monkeys and rabbits. Cattle develop skin lesions, too, but they are quite different from the kind that are seen in humans, monkeys, and rabbits. In addition to these acute, or im mediate, effects, dioxin produces at least two types of serious long-term effects in some laboratory ani mals--reproductive effects and can cer. As is true for nearly all long-term health effects studies, most of the work on dioxin effects has been done on rats and mice. Because dioxin is so acutely toxic to many adult laboratory animals it is difficult to examine its teratogenic and reproductive effects. However, several studies in mice have found cleft palates and kidney abnormali ties in offspring of animals fed 1 to 3 ng of dioxin per kg of body weight per day. Rat studies do not show birth defects. Instead, dioxin kills the developing fetus or embryo at levels similar to those that cause birth de fects in mice. Small-scale studies on monkeys show that dioxin is fetotoxic to these animals as well. Pathologist James P. Allen of the University of Wisconsin medical school has found that breeding female monkeys fed 1.7 ng of dioxin per kg of body weight per day for two years aborted four of seven pregnancies. In a study by Wilber P. McNulty of the Oregon Regional Primate Research Center, pregnant monkeys were given doses ranging from 9.5 to 240 ng per kg of body weight per day for three weeks during their gestation period. The two animals in the highest dose group died from their dioxin expo sure. They also aborted. At the level of 48 ng per kg per day, the mothers were only slightly sick, but three of the four animals in the study aborted. At the lowest level, the mothers ap- 38 June 6.1983 C&EN Researchers seek to explain dioxin's effects on cellular biology O LIVING CELL EUj1T-Krt--`Pmx t v'-? S ' i^sog^TSMsaasisEsnBEc N u cleu s C F3 Unknown site In nucleus Innocuous products excreted Message now received" Response is synthesis of specific messenger RNAs ^"mRNAs direct ^ s y n th e s is of M \ specific p ro teins^ >v*(cytochrome jg a * Reactive Intermediate Unknown critical target d rl m If the exquisite sensitivity of some, but not all, animals to dioxin is a frustration to many researchers, it is a source of delight to one group: the molecular pharmacologists. It is not an accident that some cells are incredibly sensitive to dioxin, and by exploiting the differ ences between dioxin response in dif ferent types of cells, these scientists have a probe for examining some of the very intricate inner workings of cells. " if morphine addiction w eren't a problem, morphine would still be an in teresting drug for what it can tell us about enkephalins. That's the way we feel about dioxin," explains one re searcher in the field. A consistent picture of some of dioxin's interactions with animal cells is emerging from work going on in several laboratories including those of Alan Poland and Joyce C. Knutson at the University of Wisconsin; Robert A. Neal and William Greenlee at the Chemical Industry Institute of Toxicology, Re search Triangle Park, N.C.; and Daniel W . Nebert at the National Institutes of Health, Bethesda, Md. Though this work does not explain all of dioxin's toxic ef fects, it does begin to make some sense out of one of the more puzzling aspects of dioxin's toxicity-- the great range in acute toxicities found in different animal species. According to this picture, dioxin is only one exam ple of a larger class of halogenated aromatic hydrocarbons. All of these materials bind to the same re ceptor, a soluble protein within the cytoplasm of susceptible cells. The binding site of this receptor has been quite well mapped out. Substrates need to be generally planar and pretty well fill a rectangle 10 A long and 3 A wide. Highly polarized groups, like chlorine atoms, need to be in at least three of the four corners and nowhere else in the molecule. These requirements fit dioxin exactly, but other molecules like chlorinated dibenzofurans or brominated biphenyls also can be accommodated in this at tachment site and induce dioxinlike toxicity in animals. The site's geometry goes a long way toward explaining why the 2,3,7,8-tetrachioro isomer of dioxin is the most toxic, since this is the one that has all four corner positions of the 1 .9 peared to be healthy, and their abor tion rate, one in four, was about the same as that of the nontreated group, molecule and no others occupied by gists considers dioxin to be a foreign where three abortions occurred in 11 chlorine atoms. molecule that Just happens to fit into a pregnancies. O nce bound, the dloxin-proteln receptor and turn on a cell system Clearly, dioxin is fetotoxic to some complex moves Into the nucleus where originally designed to respond to an animals and causes birth defects in it turns on the activity of a specific set of endogenous molecule and that once had genes called the Ah (for aromatic hy some useful purpose. Such a model others. However, its high toxicity to the mother means that the range in drocarbon) locus. These genes, In turn, makes dioxin analogous to morphine, w hich it causes toxic effects on the produce messenger RNAs that direct the which stimulates a natural pain-killing fetus but not on the mother is very I1 synthesis of a family of proteins called system in place of the body's own narrow. Thus, some toxicologists I cytochrome P-450s within the cell. Cy trigger molecule-- enkephalin. But to classify dioxin as a weak teratogen. tochrome P-450s are enzymes whose have dioxin fit a similar pattern, there Ironically, the fact that humans ap function is to react with foreign mole- would need to be a structurally related pear to be less sensitive to the acute culesTike dioxin so they can be metab compound naturally present, at least on effects of dioxin means that it could olized and eventually excreted from the occasion, in the body. There also would be a more potent teratogen for them body. need to be some advantage in certain than it seems to be for laboratory To this point, the system seems to be circumstances to triggering the ordi animals. a beneficial one for the cell. Unfortu narily toxic responses that the body Several independent tests in rats or nately, among the metabolites of dioxin makes to dioxin. mice show that dioxin is an ex as it Is processed by the cytochrome The body's response to dioxin, theo tremely potent carcinogen in these P-450 system there seems to. be a sub retically, at least, might sometimes be animals. Richard J. Kociba of Dow stance that is toxic. Inadvertently, a useful. Properly controlled, the ability to Chemical's Toxicology Research system that was intended to rid the body stimulate cell proliferation, for example, Laboratory found that female rats fed of foreign chemicals by making them could lead to useful growth or repair of 10 or 100 ng of dioxin per kg of body easier to excrete has converted a fairly tissues instead of cancer. So far, how weight developed a greatly increased innocuous substance into a toxic one. ever, a natural dioxinlike m olecule has number of liver tumors. At the It now seems apparent that this whole not been found in animal tissue. higher dose level, both male and fe process is controlled genetically at two Useful as this picture of dioxin's role male rats developed increased num points, at least. One of these is the Ah in cellular biology is, it does not explain bers of tumors in the mouth, nose, locus, which controls the amount and all the chemical's toxic effects. Indeed, and lungs, as well as in the liver. structure of the receptor protein within the model purposely focuses on those Nearly half the female rats in the the cell and turns on production of the effects of dioxin that vary most widely higher exposure group developed cytochrome P-450s, Experiments in from species to species. But dioxin has tumors. When the data on female rats mice have shown that genetically inbred other effects, like the wasting away of are used to calculate the potency of strains that do not have the Ah locus are tissue, that appear to be common to all dioxin as a carcinogen, dioxin comes not susceptible to some of dioxin's toxic animal species exam ined. Tissue out to be about three times as potent effects. But the Ah locus alone is not wastage is not a trivial effect of dioxin; a carcinogen as aflatoxin Bi, which is enough to produce toxicity, as is shown it is probably the cause of death in the one of the most potent carcinogens by experiments in which cytochrome very sensitive guinea pig. known. Equally significant, how activity is turned on by the presence of British studies in the m id-1970s ever, according to Kociba, is the dioxin though there is no toxic response. showed that animals recovering from finding that at doses below 10 ng Poland and Knutson have found that dioxin exposure had unexpectedly high even the female rats showed no in chloracne can be produced by dioxin in numbers of cells with m ore than one creased incidence of tumors in this a certain strain of hairless mice even nucleus, suggesting that perhaps cell study. He considers this evidence though mice generally do not show this membrane proliferation had been im that there is a no-effect level for reaction to dioxin. It is not the lack of paired by dioxin exposure. This work dioxin-induced cancers in the rat. hair itself that is responsible for chlor might provide a clue to the wasting ef A similar study conducted for the acne in these mice, they find. Instead, fect dioxin has on animals. National Cancer Institute by re some part of the genetic locus that is Certain experiments Indicate that searchers at Illinois Institute of responsible for the hairless trait in mice some of dioxin's effects are brought Technology found statistically sig ) is also necessary to produce the chlor about by such incredibly small doses of nificant increases in thyroid tumors acne response. the compound that the number of mol in male rats at all doses studied and It is interesting to speculate on why ecules in the dose is too small to ac an increase in subcutaneous tissue animals have evolved an elaborate count for the observed effect-- at least fibronomas in male rats at the high system for dealing with foreign chemi In terms of a receptor binding model, in est dose level (0.5 mg per kg of body cals and why it sometimes goes awry these cases, at least, there seems to be weight per week). In female rats, the. " with molecules like dioxin, making them some sort of chain reaction that mag study found an increase in tumors'of more, rather than less, toxic to cells. nifies the effect of a small dose of the liver, subcutaneous tissue, and One model that satisfies pharmacolo dioxin. the brain at this same dose level. Besides these two studies there June 6, 1983 C&EN 39 Dioxin Report 2,3,7,8-Tctrachlorodibenzo-p-dioxin is a crystalline solid at room temperature have been about a half-dozen others that provide some evidence that dioxin is a carcinogen in rats and mice. Although some of these other studies have methodological flaws that make them less definitive than either the Kociba or the NCI study, a panel evaluating the carcinogenic potential of dioxin for the Environ mental Protection Agency in 1981 concluded that collectively these studies support the conclusions of the Kociba and NCI studies and pro vide strong evidence that dioxin is a potent carcinogen in animals. Most chemical carcinogens tend to attack specific organs and produce large increases in one particular type of tumor. Dioxin produces many different tumor types in different organs, which has led some re searchers to speculate that it may be a promoter, rather than an initiator, of carcinogenicity. In other words, dioxin might not actually be re sponsible for tumor formation, but might instead work in some way that makes the cells more receptive to tumor formation if some other acti vating agent is present to begin the process. Several studies have been de signed to consider this possibility. One, by Henry C. Pitot and cowork ers at the University of Wisconsin, examined the effect of dioxin on rats that already had been exposed to another carcinogen, diethylnitrosamine. Animals receiving both substances had a greatly increased incidence of liver tumors compared to those that received dioxin alone, suggesting that dioxin can be a pro moter of carcinogenicity. However, in a series of studies by D. L. Berry of Oak Ridge National Laboratory's bi ological division, dioxin neither in itiated nor promoted carcinogenicity when administered along with polycyclic aromatic hydrocarbon carcinogens. Instead, it appeared to block the effect of these carcinogens in mice. Dioxin's chemical structure suggests that it could intercalate into DNA as several carcinogen initiators are believed to do. However, exper iments designed to show such inter action have, so far, given only nega tive results, possibly because the molecule is so highly reactive with cellular proteins that it is not actually available to react with DNA. The highest estimate of the degree of co valent bonding of dioxin to rat liver DNA in vivo is less than 1 molecule of dioxin per 1011 nucleotides, or four to six orders of magnitude less than what is found for most chemical car cinogens. As is almost always the case in dioxin research, the interpretation given to these and other animal test findings depends very much on who is making the interpretation. To Dow Chemical's director of biomedical research, James H. Saunders, the an imal data show that dioxin is a pro moter, but not an initiator, of carci nogenicity in animals. The EPA car cinogen assessment group, on the other hand, says that since promoters generally do not produce the large increases in tumor formation when given alone that dioxin produces, dioxin should be regarded as both an initiator and a promoter of carcino genicity. The differences in interpretation given to the animal data on dioxin toxicity, however, pale almost to insignificance when compared with the differences that arise from ex amining the human data. All of the data on humans come from people w ho somehow have been inadver tently exposed to dioxin, always in combination with many other halogenated aromatic chemicals, and often in situations where the expo sure occurred years or even decades before anyone realized that it might have important health consequences. As a result, such basic information as exactly who was exposed to dioxin at what concentration and for how long often can only be estimated. As with animal studies, the acute effects of dioxin exposure are the easiest to establish. Most of these data come from industrial accidents in which a fairly small number of workers received a single exposure to dioxin. There have been more than 800 reported cases of this type of ex p osu re. In addition, some 37,000 people may have been exposed to measurable amounts of dioxin when a 2,4,5-trichIorophenol-manufacturing reaction went out of control at the ICMESA chemical plant near Seveso in northern Italy. More than 500 residents of nearby towns were treated for what were presumed to be toxic effects follow ing the accident. Thus, Seveso stands out as the single most important industrial accident in terms of the information it can pro vide about the human health effects of dioxin. By far the most significant finding from the Seveso data and those of the other industrial accidents is that hu mans are much less sensitive to the immediate toxic effects of dioxin than are guinea pigs. So far, there has been no clear case of a human death caused by dioxin exposure, dis counting voluntary abortions that were performed following the Sev eso accident. There are, however, many well-documented toxic ef fects. The bellwether of these acute ef fects is thought by many epidemiol ogists to be chloracne, a skin condi tion in which circular patches of blackheads and pale yellow cysts develop on the face and, in more se vere cases, on other parts of the body. 40 June 6, 1983 C&EN Dioxin Report More than 800 workers have been exposed to dioxin in industrial accidents D ate 1949 1953 1956 1963 1964 1965-69 1966 1968 1976 Worfcors exposed Location of accident 250 Monsanto's 2,4,5-trlchlorophenol plant at Nitro, W.Va. 75 BASF's 2,4,5-trichIoropheno! plant at Ludwlgshafen, West Germany 7 Rhdne-Poulenc's 2,4,5trichlorophenol plant In Grenoble, France R em arks 122 cases of chloracne being studied; so far, 32 deaths vs. 46.4 expected; no excess deaths from malignant neoplasms or circulatory disease; studies continue 55 cases of chloracne, 42 severe; 17 deaths so far vs. 11 to 25 expected (4 gastrointestinal cancers and 2 oat-cell lung cancers); most common injuries were impaired senses and liver damage; studies continue 17 cases of chloracne, also elevated lipid and cholesterol levels In blood 106 NV Philips' 2,4,5-T ptant in Amsterdam, the Netherlands 61 Dow Chemical's 2,4,5trlchlorophenol plant at Midland, Mich. 44 chloracne cases (42 severe), of whom 21 also had internal damage or central nervous system disturbances; 8 deaths so far (6 possible myocardial Infarctions); some symptoms of fatigue; full report planned 49 cases of chloracne; deaths so far 4 vs. 7.8 expected, 3 cancer deaths vs. 1.5 expected, one a soft-tissue sarcoma; studies continue 78 Continuing leaks In 2,4,5trlchlorophenol processing area of Spolana's 2,4,5-T plant near Prague, Czechoslovakia 78 cases of chloracne; so far 5 daths; many of the 50 workers studied for more than 10 years have hypertension, elevated blood levels of lipid and cholesterol, prediabetes; significant amounts of severe liver and neurologic damage; studies continue ? Rhone-Poulenc's 2,4,5- 21 chloracne cases trichlorophenol plant in Grenoble, France 90 Coalite & Chemical's 2,4,5trichlorophenol plant in Derbyshire, U.K. 79 chloracne cases; so far 1 death from coronary thrombosis; cohort study planned; company refuses to divulge any more information 156a ICMESA's 2,4,5-trichIorophenol plant at Seveso, Italy Workers are being studied along with exposed townspeople; more than 500 residents treated for presumed toxic symptoms; 134 confirmed chloracne cases; overall mortality rate normal so far; studies continue a In addition to these (CMESA workers, some 37.000 residents ot nearby towns also were exposed to dioxin in this incident. Source: American Medical Association study, 1981 By itself, chloracne is not considered Of more concern at Seveso and dioxin have been proved. Stated just a serious condition, although it can elsewhere are the possible chronic that way, probably few epidemiolo be disfiguring while it persists. After effects, especially those that might be gists would disagree. But there are I mild exposure it usually clears up in caused by lower-level exposures like studies that suggest long-term health a few months, but for more severe those experienced by soldiers serving problems and literally thousands of cases it can last for as long as 15 years. in Vietnam during the 1960s when anecdotal incidents that link dioxin Hundreds of cases of chloracne have dioxin-contaminated herbicides were exposure to health problems. been seen after industrial accidents, used there, by workers in plants Probably the most highly respect including 134 confirmed cases at making dioxin-contaminated prod ed studies suggesting a link between Seveso. Most of the Seveso cases were ucts and by their families, by citizens dioxin exposure and long-term elementary school children. living in communities like Times health effects are those of Swedish In addition to chloracne, other Beach, Mo., with its unexpectedly epidemiologist Lennart Hardell at symptoms develop with increasing high levels of dioxin in the soil, or University Hospital, Umea. HardeH's dioxin exposure. These include a even by the population of areas work links use of dioxin-contami general sense of fatigue or malaise, where 2,4,5-T or other dioxin-con nated phenoxy herbicides with an disturbances in the responses of the taminated herbicides may have been increased incidence of soft-tissue peripheral nervous system such as a used during the long period when sarcomas, a rare form of cancer that measurable slowing down of the such use was allowed in the U.S. Po affects muscle, nerve, and fat tissue. speed at which nerve impulses travel tentially exposed people in these In two studies he finds a five- to six through the limbs, and liver toxicity categories easily number in the fold increase in the incidence of this including changes in many enzyme hundreds of thousands. type of tumor in people who have levels and in some cases enlargement Fortunately, the evidence for used phenoxy herbicides compared of the liver. Industrial exposure data chronic health effects in humans is with his control group. seem to indicate that these conditions much less substantial than for acute Dow scientists, and others, have generally disappear after a few years effects. There are, in fact, distin criticized the Hardell studies on and the experience at Seveso seems guished researchers who argue that several counts. For one thing, the largely to confirm these findings. no chronic human health effects of determination of whether or not 44 June 6, 1983 C&EN ,0 subjects were exposed to phenoxy vated incidence of soft- and connec- herbicides was made by asking them ,tive-tissue cancers among women in Dioxin's lethality compared to or their relatives whether they could remember any exposure. This is not a very accurate method, and, ac cording to Dow's Saunders, people in the exposed group more frequently were asked if they could recall her bicide use than were people in the control group. Another point that concerns epidemiologists is that the the period from 1960 to 1978. Exactly what this finding means is unclear, according to a report from the Michigan Department of Public Health released last month. "It is not my judgment at this point that there is a clear link [between dioxin exposure and incidence of soft-tissue sarcomas in humans]," other poisons Substance Botulinum toxin A Tetanus toxin Diphtheria loxln 2,3,7,8-TCDD Bufotoxln Curare Strychnine Animal Mouse Mouse Mouse Guinea pig Cat Mouse Mouse Minimum lethal dosa (molea per kg body weight) 3.3 x ic r 17 1.0 X 10" 15 4.2 X 1 < r12 3.1 X 1CT9 5.2 X 1CT7 7.2 X 10~7 1.5 X 10- people in one study apparently were Saunders says. "It is a question that Muscarln Cat 5.2 X KT exposed to products that contained merits further study. We do not see DJlsopropylfluoro- Mouse 1.6 X 10" 5 much lower levels of dioxin than sarcomas in animals [exposed to phosphate those in the other study, but both dioxin]," he points out. "What w e see Sodium cyanide Mouse 2.0 X 10" 4 groups showed the same degree of are carcinomas, [which are] epider- Source: EPA increased risk. Such data suggest that mally derived tissue tumors, partic some factor other than dioxin might ularly liver cancer, as in the rat. Fur be responsible for the elevated cancer thermore, when one sees cancer in have an increased incidence of soft- \ risk. Finally, there is a problem with rats, one sees it at a level 10 times that tissue sarcomas. The study, being \ the identification of the tumors as which produces obvious toxicity in directed by epidemiologist Han K. j soft-tissue sarcomas. Because this is a the animal. In other words, when Kang, w ill use data from the Armed rare cancer type, most pathologists one produces liver cancer with Forces Institute of Pathology, which have very little experience in iden dioxin in the rat, one has a very sick is, in effect, the U.S. center for the tifying it. It is, to some degree, a rat who is very sick for a long time evaluation of soft-tissue sarcomas. ^ classification that is used for tumors and then develops cancer." This is The institute has on file some 8500 ij j that don't fit into other, more clearly very different from the humans who cases of soft-tissue sarcoma, or ;j definable categories. Hardell relied develop soft-tissue sarcomas, he roughly one quarter to one third of ; on medical records to identify the maintains. all the cases ever reported in the U.S. 1i sarcomas; he did not examine the Other studies do not show an as The study will examine tumors re- 'i ~ tissues himself. sociation between phenoxy herbicide ported to the institute between 1975 Nevertheless, the Hardell studies use and increased incidence of soft- and 1980 to see if Vietnam veterans cause concern, and that concern is tissue sarcoma. One study that ex are overrepresented in this group. A increased by early results from amined the relationship among final report of the study .is expected studies of Monsanto and Dow people in various occupations in the in 1985. Chemical workers who were exposed state of Washington and incidence of One potential problem with this j- to dioxin in separate industrial acci soft-tissue sarcoma found that the study is that the latency period for [ dents in 1949 and 1964. Altogether, occupations with the greatest num soft-tissue sarcomas is thought to be 1 182 workers from these two incidents ber of soft-tissue sarcomas, as deter about 15 years. Since dioxin con- are being monitored. By 1979, 36 of mined by data on death certificates, tamination of Vietnam occurred in these workers had died, fewer than were marine engineers and bankers, the 1960s, the time period may be too the 54 that would have been expect groups that would not be expected to short to evaluate properly what effect 1 ed based on national mortality sta have had particularly high exposure dioxin use in Vietnam had on de tistics. However, three of the people to dioxins. Allan H. Smith and asso velopment of this type of tumor. who died had soft-tissue sarcomas, ciates at the school of medicine at However, by 1980, reports of Har- j; and a fourth, who has died since Wellington Hospital, New Zealand, dell's findings were causing pathol- j: 1979, also had soft-tissue sarcoma. For are in the midst of a study of the in ogists to look more closely for soft- j. a form of cancer with a predicted in cidence of soft-tissue sarcomas tissue sarcomas, and the researchers !j cidence of less than 1%among cancer among herbicide applicators in New chose a 1980 cutoff to remove this },j victims, finding four in such a small Zealand. Because New Zealand re bias from their study. =I sample is unexpected. "It certainly quires herbicide applicators to be In addition to cancer, animal .j raises the question as to whether registered, records of exposure to studies raise concern about the pos there is something there," says Dow's phenoxy herbicides are particularly sibility of fetotoxicity in humans ex Saunders, "but, [although] it is sta good in that country. In a prelimi posed to dioxin. Several studies and tistically significant, there is always nary report presented in 1982, Smith many anecdotal reports of such ef that uncertainty of what would have had not found any instances of soft- fects in humans have appeared. By I been the luck of the draw in a sample tissue sarcomas in this group. and large, however, these studies his small." The Veterans Administration is have methodological flaws that bring Examination of death certificates putting together a study designed to their findings into question. and hospital records for Midland see if Vietnam veterans, who may One of the most important of these County, Michigan, where Dow's have been exposed to dioxin through studies, at least politically, involved plant is located, also shows an ele the use of agent orange in Vietnam, a group of nine women in the Alsea June 6, 1983 C&EN 45 jI Dioxin Report i i Basin in Oregon who lived near for the ICMESA accident. However, ests that were sprayed seasonally there is so much uncertainty about w ith dioxin-contaminated herbi what levels should be considered cides. The women were concerned that 13 miscarriages in their group in normal for this population that it is unlikely that the question of whether the mid-1970s seemed to be linked the Seveso incident caused increases chronologically with the spraying of in these conditions w ill ever be re the forests. The Environmental Pro solved. Epidemiologists who think tection Agency conducted two stud there may be an association between ies, one examining just these nine dioxin exposure and these effects call women and a larger one looking at the Seveso data "suggestive" of an miscarriage rates in that part of Ore .effect; those who think that these gon. Although the first study did not effects probably don't occur in hu find a statistical relationship between mans point out that the levels were the women's miscarriages and the w ell within the normal range fjor spraying, the second study did. This western countries. study played a major role in EPA's There exist, in addition, several decision in 1979 to issue an emer studies that do not show any increase gency suspension against many uses find out if dioxin causes human re in miscarriages or birth defects of the dioxin-contaminated herbicide productive effects. At least two Vi among populations that might be 2,4,5-T. etnamese studies, one from the early considered at risk because of their .However, the study did not stand 1970s and one announced earlier this dioxin exposure. Studies of Dow up to critical evaluation. A team of year, claim to show a substantial in Chemical and Monsanto chemical University of Oregon researchers in crease in these conditions as w ell as workers and their wives show no 1979 panned the study on practically cancer following the spraying of increase in either of these factors. So all counts. Among other things, they agent orange in that country. How does a study released last month by found that the study did not have a ever, western epidemiologists are the Michigan Department of Public proper control, its data both on mis uncomfortable with the lack of data Health that examined the rate of carriages and on 2,4,5-T spraying on normal rates for miscarriage and birth defects in Midland County, were inaccurate, there were many birth defects in the Vietnamese where Dow made 2,4,5-trichloro- other factors besides 2,4,5-T spraying population. They also question the phenol until 1979. that varied among the three groups way in which the Vietnamese data A recently released study of the examined, and the variations in the were collected. reproductive effects of dioxins on the levels of miscarriages reported by the Similarly, data from Seveso seem families of Australian soldiers who study were w ell within expected to show an increase in both the fought in Vietnam during the period ranges. number of spontaneous abortions when agent orange was being Poorly designed or conducted and in the number of birth defects in sprayed there shows no increase in studies seem to plague the effort to the period immediately following miscarriages or birth defects among these families. The study is highly praised scientifically, but there is Dioxin has different effects in different animals uncertainty as to whether these Symptom Mon Guinea Rab Chick Ham k ey Plfl Cow Ral M ouse bit en s ter Australian soldiers received very much exposure to dioxin while they Abnormal cell proliferations were in Vietnam. Consequently, this or organ enlargement Gastric mucosa ++ 0 + 0 0 negative finding does little to allay 0 the fears of those who think dioxin Intestinal mucosa Urinary tract Bile duct/gall bladder Lung Skin Atrophy or decreased cell proliferation Thymus Bone marrow Testicle Other effects + ++ ++ ++ 0 0 ++ + ++ ++ ++ a 0 0 ++ + ++ ++ ++ + ++ ++ + + + ++ + may cause human reproductive problems. So the overall picture that has emerged so far shows dioxin as ex tremely toxic and carcinogenic based on animal studies, but the picture is much less clear about human health effects. Human studies are continu in g--the U.S,government is spend ing more than $100 million on sev Liver lesions Edema +0 +0 ++ + ++ + + 0+ ++ + eral epidemiologic studies of the health consequences of possible Hole: 0 Indicates lesion not observed; + indicates lesion observed (number of pluses notes severity), a Skin lesions are observed In cattle, but they are different from the lesions seen In other species. Source: Poland and Knutson, Annual Review o f Pharmacology & Toxicology, 1982 dioxin exposure to veterans who served in Vietnam, and major studies also are under way in Australia, New Zealand, Finland, Sweden, the U.K., 46 Junes, 1983 C&EN Dioxin Report and many other countries. Most of the U.S. studies are scheduled to be completed by 1987, but already epi demiologists wonder whether uncertainties about exposure levels and questions about what other fac tors may have accompanied dioxin exposure will weaken the value of the studies' findings. Not surprisingly, current assess ments of the risk dioxin poses to human health vary greatly depend ing on which of the available data seem most important to the assessor. A reasoned argument can be made that the animal data show, in addi tion to severe toxic effects in certain species, that great variability can be expected from one animal species to another and that the available human data suggest that humans are among the least sensitive of animals to dioxin's effects. That interpretation is not incompatible with any of the human epidemiologic data published so far, and it may turn out to be the true picture of dioxin's hazard. Most toxicologists, however, are much more conservative in their risk assessment. This means that, in the absence of stronger evidence to the contrary than has been seen so far for dioxin, a proven risk in animals is considered to be a potential risk in humans, and a substance that causes acute effects in humans is viewed with suspicion as a possible cause of chronic effects. It is in this spirit of prudence that EPA views the cancer risk of dioxins in humans. "Carcinogenic responses have been induced in mice and rats at very low levels of [dioxin]," EPA's carcinogen assessment group con cluded in 1981. "In addition, dioxin has been shown to be a potent cancer promoter. These results, together with the strongly suggestive evi dence in epidemiologic studies, constitute substantial evidence that dioxin is likely to be a human car cinogen." Such assumptions are only the first step in coming up with an estimate of human risk in any particular situa tion, however. At a site like Times Beach, Mo., explains Renate D. Kim brough, medical officer for the center for environmental health at the Center for Disease Control, assessors also need to know how much dioxin people exposed to contaminated soil Saunders: experimental uncertainty are likely to absorb. That's not w ell established, she says, although one study at the University of California has shown that when dioxin is on the skin, 1 to 10% w ill be absorbed. Dioxin binds to soil, so probably less is absorbed from there than if the dioxin were applied directly to the skin. One Seveso study found that about 1%of soil dioxin was absorbed, but the sample size was small and the results are inconclusive. Besides, Kimbrough points out, absorption may not be the only route of exposure. Some contaminated dust may float in the air and enter the lungs, and some may be eaten, espe cially by children. Given all these uncertainties, CDC still came up with a level of soil con tamination that it believed was low enough to pose no threat to the health of Times Beach residents. "We decided to take one increased inci dence in a million as a reasonable risk," Kimbrough says, and to base their hazard assessment on studies of birth defects caused by dioxin in rhesus monkeys. Toxicologists usu ally allow a factor of 100 below the no-effect level in an animal study as a margin of safety when extrapolat ing to humans, she explains. How ever, in the case of the monkey study, the animals had limited, not lifetime, exposure to dioxin, so the standard safety factor was increased to 1000. The resultant calculations come up with 1 ppb as a level likely to be safe. A similar calculation based on the 48 June 6. 1983 C&EN carcinogenicity of dioxin in rats gives about the same level, Kimbrough says. Such values ought not to be taken as a national standard for dioxin in the soil, she cautions. CDC will be reviewing its assessment procedure with outside consultants to see if it is possible to come up with national standards for soil contamination. Even if such standards can be drawn up, there is not likely to be a single level that w ill be appropriate for all sites, she points out. For example, in desert areas, where very few people live, soil probably could contain higher levels of dioxin before the total health risk became equivalent to the one at Times Beach. On the other hand, data from the U.S. Department of Agriculture indicate that grazing livestock easily pick up dioxin from the soil, probably because they eat so much soil as they graze. People who eat the meat from these animals or drink their milk have an additional route of exposure to dioxin. Thus, soil levels in areas where animals graze must be lower to obtain an equiva lent risk. Is it really appropriate to base human health risk estimates on the experience of laboratory animals w hen limited data suggest that hu mans may be a good deal less sus ceptible to dioxin than some labora tory animals are? Kimbrough thinks it is. There is very little information on what chronic exposure levels have been in workplaces, she points out, so it is difficult to know how much weight to place on long-term studies of workers' health that seem to find no ill effects. Also, except for Seveso, there is very little information on the effects of dioxin on women or chil dren. And even at Seveso, soil dioxin levels in areas where people were allowed to return to their homes were generally in the parts-per-bil- lion range or lower. Animal studies show that dioxin's effects vary greatly from one species to another. In some cases the effects have even been pinned down to the presence of a particular genetic locus within a species. But the human population is genetically very diverse, so that even if many people are not susceptible to the hazards of dioxin, there may be subpopulations who face a substan tial risk. ^ Dibxin Report Both Incidence, Control o f D ioxin Are Highly Complex A by-product of many industrial processes, dioxin presents big problem in w aste disposal; the technology is : on hand, but econom ic, political barriers persist j Ward Worthy C&EN Chicago C&EN's dioxin coverage now turns to the practical world of industry. How and where, exactly, do dioxins turn up? And how can they be controlled? It's a complicated situa tion, in part because of the myriad of dioxin structures and reactions. So a short review of chemistry is in order before a look at com mercial reactions and dis posal methods. On the dioxin molecular frame work--consisting of two benzene rings connected by two oxygen bridges--there are eight positions where substitutions can take place. In any or all of these eight substituent positions, hydrogen atoms can be replaced by other atoms or by organic or inorganic radicals. The number of possible combinations is almost limitless. These days, of course, when people speak of dioxins, they likely are re ferring to the black-sheep branch of the family, the chlorinated dioxins (CDDs), in which one to eight of the substituent positions are occupied by chlorine atoms. The arrangement allows for a total of 75 different CDDs; most but not all of them have either been synthesized or identified as by-products or contaminants in other materials. There are 22 isomers of tetrachlorodibenzo-p-dioxin (TCDD) alone, all of which have been synthesized. However, the bulk of attention has gone to what is apparently the most toxic member of the group, 2,3^7,8TCDD. This isomer is symmetrical across both horizontal and vertical axes. At room temperature, it is a colorless crystalline solid. It melts at 305 C. Chemically, it is quite stable; for example, its thermal destruction requires temperatures of more than 700 C. It is lipophilic, and it binds strongly to soils and other particulate matter. It is only sparingly soluble in water and most organic liquids. Although 2,3,7,8-TCDD is the most notorious of the dioxins, it usually occurs mixed with other chlorinated dioxins. Some of these also are quite toxic. How, then, do these compounds arise? To oversimplify the situation, a dioxin comes from a dioxin precursor. This compound must contain an ortho-substituted benzene ring, and one of the sub stituents must include an oxygen atom attached di rectly to the ring. In addi tion, two substituents (but not the oxygen atom itself) must be able to react with each other to form another compound. The reaction is favored by basic conditions and by temperatures in the range 180 to 40 C. The presence of a catalyst; such as copper powder, promotes the reaction. Although there exist a multitude of organic chemicals that qualify as dioxin precursors, perhaps th most notable of these is 2,4,5-trichlorophenol (TCP). It's notable--if for no other reason--because its geometry is such that when two TCP molecules condense, the likely result is 2,3,7,8-TCDD. According to several studies, the reaction takes place in two steps, with a diphenyl ether serving as the intermediate. That's one way dioxins can be formed. However, it's not the only way. Actual findings don't always conform to what would be expected from that straightforward conden sation reaction. Other, more complex mechanisms for forming CDDs have been discovered and still others proposed. In fact, a case can be made--and June 6, 1983 C&EN 51 Dioxin Report has been made--that many reactions can occur whenever, organic and chlorine-containing materials are burned together, and that one of the things that happens is the formation of trace amounts of CDDs. There is evidence to suggest that the hy pothesis is true, at least in principle, at least some of the time. Whether it's relevant to current problems of dioxin contamination is a matter of controversy, with the dispute stemming in good part from differ ing opinions as to what level of dioxins, if any, is acceptable in the environment. In the great majority of everyday combustion processes, the amount of dioxins produced is likely to be very small--and not much can be done about it anyway. In certain cases, however, the combustion hypothesis should be (and is being) looked at from a practical standpoint: for ex ample, in the incineration of munic ipal wastes that may contain signifi cant amounts of polyvinyl chloride or chlorophenol-preserved wood products. Regardless of how many odd ways trace amounts of dioxins may enter the environment, and regardless of what they may mean, the fact re mains that those dioxin-related in cidents that have become public scandals--Seveso, agent orange, Love Canal, Times Beach--can fairly be traced tjack to the chemical in dustry. Specifically, they can be traced to producers of halogenated phenols and their derivatives. Among these chlorinated organics, o-chlorophenols deserve particular attention. One of these, TCP, practi cally demands especially close scru tiny. TCP is made in large quantities. It's an intermediate in the manufac ture of several other widely used products, including 2,4,5-trichlorophenoxyacetic acid (2,4,5-T) and re lated herbicides. As noted, its struc ture is such that 2,3,7,8-TCDD is a likely by-product of its manufacture. TCP's the one that, directly or indi rectly, has caused most of the trouble with dioxins. Although it's not the only possible way to do it, commercial production of TCP in the U.S. was carried out by hydrolyzing 1,2,4,5-tetrachlorobenzene, which is one of the isomers obtained by rechlorinating o-di- chlorobenzene. Reaction of 1,2,4,5tetrachlorobenzene with sodium hydroxide yields, mostly, the sodium salt of TCP. That salt can be used as is to make derivatives, or it can be neutralized with a mineral acid to give TCP. Process details vary. For instance, one of several solvents (including methanol and water) can be used for the hydrolysis. Proper attention to temperature and pH control can minimize the formation of dioxins during the hydrolysis. However, trace amounts of dioxins usually are formed, along with other impuri ties. As one step in the purification process, the crude salt is washed with toluene, which removes some of the high-boiling impurities, including dioxins. The organic and aqueous phases are allowed to separate and the toluene layer is sent to a still for recycling. The product can be further purified--for example, by vacuum distillation. Current production of chlorinated phenols and related products is monitored very carefully for dioxin content. However, purity is a relative term--in the chemical industry, at least--and, in general, higher purity is reflected in higher cost for the product. So, before the nature of the dioxin problem became evident, producers weren't always so careful. Consequently, there have been many confirmed instances in which com mercial products--some quite widely used--have been found to contain trace levels of dioxin. Many millions of pounds of chlo rinated phenols and related com pounds are made and used each year. N ot surprisingly, they turn up ev erywhere. Pentachlorophenol (PCP), for example, is used in large tonnages to preserve wood. PCP, TCP, and re lated products are used as biocides for process and cooling waters in many industries and in a host of small-volume applications. Given that any of these products may contain some level of dioxin contamination, there are several sources from which dioxins can enter the environment. Obviously, the 52 June 6.1983 C&EN . -- -r < I t. III. i products themselves are one source, and this can be a matter of concern to those who work routinely with those products. But they probably aren't the most important source, from the standpoint of imminent danger to the public. Many dilution effects are at work, so just traces of dioxins are what finally get into the environ ment. Many combustion processes afford some possibility of release--or even creation--of dioxins, with the degree of hazard depending on what is being burned and the conditions under which combustion takes place. Again, concentrations typically are very low. Accidents or mistakes in manu facturing chlorinated organics are another potential source of dioxins. They can be an extremely dangerous source of heavy local contamination, as demonstrated by the release from the TCP reactor at Seveso. In addi tion, there have been numerous other smaller, less-publicized--but not necessarily insignificant--acci dents involving the making of TCP. Aside from Seveso, the most fa mous cases of dioxin contamination of the environment have resulted from improper disposal, by certain manufacturers or by their agents, of products and process wastes con taining relatively high concentra tions of dioxins. To return to the aforementioned production example, crude TCP can be purified by washing it with tolu ene (which is distilled and recycled, so that the impurities accumulate in the still bottoms). It can be further purified by vacuum distillation (again, the impurities collect in the bottoms). The dioxins and other im purities aren't destroyed in these operations. They're just moved somewhere else and, in the process, concentrated to even more danger ous levels. These highly contaminated wastes can be rendered essentially harmless by a number of methods, including incineration. That isn't what always happened, however. Incineration is a comparatively expensive disposal option. In all too many instances, it was cheaper--or so it seemed at the time--just to put the stuff in drums and bury it where it couldn't hurt anybody. That would have been fine, except that the drums inevitably leaked and the dioxins (and other nasty compounds) started showing up in the water and soil around the storage site, such as at Love Canal. Or, as happened at Times Beach, the producer simply turned his wastes over to some guy with a truck, who hauled them away, mixed the dioxins with oil, and sprayed them over the countryside. Once at large, dioxins spread at varying rates and to varying degrees through soil, water, and air, and through living things. The ultimate fate of dioxins depends on circum stances. Although the details vary, a number of studies have shown that dioxins are degraded rather quickly by sunlight or artificial ultraviolet light. For this to happen, however, the photolytic rays must be able to reach the dioxin molecules, and hy drogen for the reaction must be available from some organic donor. In the real world, such a hydrogen donor usually is nearby--either some other component of the waste of which the dioxins are a part, for example, or even the vegetation on which the dioxins have been depos ited. Thus,, dioxins spread thinly in the sun will, within a few days, usu ally disappear or at least diminish to undetectable levels. However, once dioxins penetrate the soil, they are there to stay for quite a long time, according to a number of studies. Some studies in dicate that no significant degradation of dioxins occurs in the soil. Other studies suggest that some degrada tion does take place, but it's usually too slow to be of any comfort. In any event, places like Seveso and Times Beach demonstrate that dioxins, un disturbed, can persist in soils for many years, unless they are washed, blowm or otherwise carried away. Since dioxins have spread rather extensively throughout the envi ronment, what can be done about them? More to the point, perhaps, what should be done about them? Answers to the first question are fairly clear. Answers to the second question are much less clear, and subject to honest differences of opinion. In the case of extremely low dioxin levels--a few parts per trillion or lower--the answer to both questions Making 2,4,5-trichlorophenol can lead to dioxin contamination 1,2,4,5-Tetrachlorobenzene ^ ^ ^ ^ ^ S o d i u m hydroxide Air emissions8 Water Alcohol recycle Toluene plus Impurities Na-TCP in water Hydrochloric I acid-- i I Toluene * Wastes8 (still bottoms) Conversion* ` (optional) Wastewater8 Air emissions8 TCP Wastes8 (still bottoms) a Potential sources of environmental dioxin contamination. Source: Adapted from EPA, "Dioxins" is probably nothing, except to stem the high-level sources, to prevent any more of the leaks, emissions, and improper disposal operations that were the original source of most of the low-level contamination. In the case of the more highly contaminated dioxin dumps, there are a number of things that could be done, all of them quite a bit of trou ble. Although something should be done to clean up these worst cases, there is much disagreement as to what. In the "in-between" cases, the cost-benefit analyses get even blurrier, and there is even less agree- ment. June 6, 1983 C&EN 53 , f Dioxin Report GC, MS useful techniques in the analysis of dioxin How does one determine whether and to what extent something is contaminated by dioxins? The easy tnswer is that it's usually done with gas chromatography and mass spectrometry. But there's a lot more to it than that. Normally, dioxins are present, if at all, at levels rangingfrom parts per million down to the van ishing point. They coexist with many other compounds, and many of these are present in much larger amounts and capable of interfering with the anal ysis. Since it's impossible to run a sack of dirt or a Coho salmon through even the most user-friendly GC/MS setup, sample preparation is an extremely important part of the process. The first step is to transfer the dioxins (and other chlori nated organics) from the sample matrix to an organic liquid, by a series of ex tractions. An isotopically labeled internal standard is added to help determine how much sample is lost in later steps, and to assist in quantitation. The organic extract Is cleaned up with another series of washings with aqueous base and acid solutions and distilled w ater. Then the organic extract under goes a sequence of preliminary liquid chromatographic separations, using a variety of columns and eluents. All the fractions from these separations are recombined and concentrated for GC/M S analysis. Usually, the sample first goes through a GC/low-resolution MS system for preliminary screening. This can show that TCDDs, for example, are present, but it isn't sensitive enough to distinguish among the various isomers. If TCDD or other dioxins of interest are revealed by this preliminary analysis, the^sample then goes to a second GC/high-reso!u- tion MS analysis. The presence and amount of specific isomers like 2,3,7,8-TCDD then can be determined from the ratios of certain key mass fragments. With such techniques, and depending on the nature of the sample, it's possible to detect and quantify dioxins down to low parts-per-trillion levels with rea sonable confidence. In the case of a "simple" sample like water, one can go even lower, down to the parts-per-quadrillion level, by taking a very large sample and concentrating the dioxins into a much smaller volume by solvent extraction. In the case of more complex samples, like soils, this approach is probably beyond the capabilities of to day's analytical laboratories. All this is terribly tedious, time-con suming, and expensive. A lot of work is going on to find simpler alternatives, especially for the preliminary screening steps. UV light degrades dioxins The basic disposal options for Perhaps the largest dioxin de- j dioxins are the same as for other struction operation to date involved to less toxic products hazardous wastes: to contain them or the incineration of more than 2 mil- ! to destroy them. Some argue that lion gal of agent orange left over : containment in a secure landfill from defoliation activities in South { (with all that that implies, including east Asia. That operation took place. "impervious" liners and eternal in 1977, in mid-Pacific Ocean, aboard monitoring of leachate and sur the seagoing incinerator M / T Vul- rounding groundwaters) is a satis canus, which at that time was owned factory means of dealing with dioxin .by a Dutch company. Chemical wastes. Waste Management, the current But security, like purity, is a rela owner of the ship, notes that more tive term. Dioxins, at least some of trial burns of dioxin wastes are set to them, aren't considered just hazard take place soon in the Gulf of ous wastes. They're considered ex Mexico. tremely hazardous wastes. Thus, Mere "burning," however, isn't a there's growing sentiment not to satisfactory method for disposing of settle for containment of dioxins, no dioxins. If temperatures aren't high matter how good the containment enough, there's a good possibility not system, but to demand their outright only of failing to destroy all the destruction. Meanwhile, of course, dioxins already present, but also of I much of the world's dioxin wastes is actually forming new dioxins from resting in dumps, some many years precursor compounds contained in old, that bear little resemblance to a the wastes. modern, secure landfill. Although test data are scanty, it's The barriers to destruction of these reasonable to assume that some of the dioxin caches are mainly economic "advanced" incineration processes and political, rather than techno now under development, including logical. Although dioxins are chem molten salt combustion and micro- ically stable, they certainly can be wave plasma destruction, might be destroyed, with high efficiency, by suitable for destruction of dioxin- the same high-temperature (1000 to containing wastes. 1500 C) incineration systems used to Several chemical means of dioxin destroy other hazardous organic destruction also have been proposed wastes. and, to some extent, tested. These 54 June 6, 1983 C&EN Dioxin Report Successful dioxin cleanup operation is complex, costly One of the better-documented dioxin cleanup operations demonstrates that dioxin hazards can be dealt with re sponsibly and effectively. It also points up the tremendous complexity and ex pense of such an undertaking. In 1969, Syntex Agribusiness bought a chemical plant at Verona, Mo., for the manufacture of animal feed additives. The previous owner had leased part of the plant and property to another firm for the manufacture of trichlorophenol and further conversion to hexachlorophene. After hexachlorophene essentially was banned in 1972, that firm went out of business and abandoned the Verona plant. In 1974, the Syntex plant manager discovered that a steel tank on the property-- never used by Syntex and presumed to be empty-- actually con tained about 4 6 0 0 gal of dark sludge. Analysis showed the sludge to contain 3 5 6 ppm of dioxins, about 7 kg. Although Syntex perhaps could have denied legal responsibility for the sit uation, the company felt that it was in its own best interests, as well as the pub lic's, to dispose of the dioxins in a safe and acceptable manner. The first step was to protect the tank. A concrete dike, big enough to hold all the tank's contents, was built under the tank. A building was erected over it and a fence was put around it. That was only the beginning of what would turn out to be a six-year project. The easiest way to get rid of the dioxins would have been to incinerate them. However, there were no suitable incinerators in Missouri. Efforts to in Syntex photolysis process unit cinerate the wastes elsewhere were thwarted because Syntex was prohibited from shipping them across state lines. So Syntex started exploring the possi bilities of on-site destruction. In 1978 Syntex engaged IT Enviroscience to undertake a three-phase program: technology review to deter mine the best method, laboratory de velopment and refinement of the chosen process, and finally the actual detoxifi cation. A committee of experts was formed to provide independent evalua tion and guidance. The Environmental Protection Agency also was intimately involved, along with other agencies. Building a suitable incinerator on-site for a one-time operation would have been prohibitively expensive. IT Enviroscience cam e up with three other candidate processes: catalytic w et ox idation, photochemical reduction, and chemical treatment. After extensive evaluation, the photolytic method was chosen, mainly for reasons of safety, since it operated at ambient pressures. This approach required that the dioxins first be separated from the wastes by hexane extraction. A period of refinement and scaleup followed, leading eventually to a full-size extraction and photolysis unit that in cluded a bank of 10-kW industrial ultra violet lamps. All this time, of course, much analytical chemistry was being conducted, along with contingency planning, industrial hygiene,legal ac tivities, and liaison. | Finally, in May 1980, EPA approved the plan. Photolytic destruction was carried out batchwise, over a period of several weeks, with a destruction effi ciency of 9 9 .9 4 % . Neither Syntex nor IT Enviroscience will reveal what the total operation cost. According to a 1980 article in Waste Age, the installed equipment cost Syn tex about $ 5 00 ,0 00 . But with all of Syntex's other expenses, that was probably just the tip of the iceberg. include ozonolysis, chlorinolysis, .ins was extracted from 4600 gal of catalytic wet oxidation, and various TCP wastes and then degraded to catalytic dechlorination processes. relatively nontoxic compounds by However, none have been applied exposure to ultraviolet light. full-scale. Biological methods may That case brings up the question of prove useful, especially for eco whether it's better to treat dioxin- nomical treatment of large amounts contaminated materials in bulk, or to of very lightly contaminated mate extract and concentrate the dioxins rials. So far, however, test results before they're destroyed. As with have been equivocal. many other dioxin questions, the In fact, aside from incineration, the answer isn't obvious. Both ap only dioxin destruction method to be proaches have been used. employed on a large (by dioxin Dioxins can be efficiently and standards) scale has been photolysis. fairly selectively removed from, for In that operation, some 7 kg of diox- example, contaminated soils by re peated extractions with various or ganic solvents, including hexane. Supercritical fluid extraction of the dioxins also has been proposed, and it might work. Where millions of tons of materials are contaminated by a few kilograms of dioxins, as at Seveso, it might prove easier and more economical to extract the dioxins and destroy them separately rather than to incinerate the whole mess. Either way, the lo gistics strain the imagination. Even tually, experience likely will provide the best solutions. 56 June 6, 1983 C&EN *I g0 ____________________________________________________________________ ________________ i Dioxin Liability Is Huge Problem for Companies, Courts Lawsuits for personal injury are mounting with massive potential compensation; com panies scram ble for insurance, look to asbestos cases for precedents David Webber, C&EN New York Earlier this year, a major chemical company settled a lawsuit out of court. A farmer whose land is bi sected by a utility right-of-way claimed that 2,4,5-trichlorophenoxyacetic acid (2,4,5-T), sprayed by the utility to control vegetation under its power lines, fell onto his land as well, despite elaborate precautions by the sprayers. His family's health, he charged, had been undermined by the dioxin often found as a contami nant in the herbicide. There was, however, no visual evidence on his fields of the sort of defoliation 2,4,5-T causes. Testing detected minimal amounts of the chemical. It could have been residue from earlier sprayings. Examination of the farm er's family revealed no health prob lems unusual for either their age or location. On the evidence, it had all the earmarks of a case the chemical company involved would have won in court. Still, the firm elected to settle. The chemical company in the suit is not known for its reluctance to defend itself. But cases involving dioxin elicit a different response from it and other companies associ ated in any way with the notorious by-product contaminant. The po tential stakes are too high to worry about the relatively petty sum in volved in satisfying one aggrieved farmer. Any trial involving dioxin may establish legal precedents about the compound's hazardousness to human beings. A precedent unfa vorable to business could have grave financial consequences, companies believe, and their strategy has been to settle whenever possible. But time may be running out for this policy. The lawsuits filed by Vietnam war veterans against the producers of agent orange, begin ning in 1979, brought dioxin, the agent orange contaminant the vet erans blame for their variety of ail ments, to national attention. The discovery of large quantities of dioxin in Times Beach, Mo., last De cember made the chemical into a menace that might be anywhere. With public sentiment against dioxin blooming, litigation is almost sure to increase to the point where--if that point has not already been reached--the companies being sued no longer will be able to afford not to defend themselves. For claims man agers advising their companies which suits to fight and which to settle on the basis of economics, it is a fretful and dangerous time. Up to now, the dioxin issue has centered on the question of estab lishing the compound's hazardous ness to humans. As far as most sci entists are concerned, the jury is still out on that. But if research eventually proves, or if the courts, .without waiting for conclusive scientific ev idence, establish a presumption that the levels of dioxin to which people have been exposed are harmful, then the focus of attention is sure to shift rapidly. It will shift to compensation, and, unless Congress legislates a program to compensate victims on an exclusive basis, lawsuits--of possibly mammoth proportions--will be in evitable. The bulk of the litigation would be made up of product liability suits by individuals or groups seeking com pensation for personal injury. There also would be other types of suits. People in situations like that of the June 6, 1983 C&EN 57 Dioxin Report five years ago, when the insurance market was tight, to take risks. But there are major problems. The biggest is the tremendous difficulty involved in predicting the potential losses dioxin suits could entail. In surance carriers customarily set their premiums according to actuarial ta bles based on the rate of accidents and the size of awards in the past. In the case of dioxin, however, there is no past to refer to. The agent orange suit, a decision in which would de fine the nature of dioxin liability somewhat, is undoubtedly months if not years away. And even given that, the primary issue in the case at this point is whether or not--regardless of the ultimate establishment of the compound's hazardousness--the producers of the herbicide are liable at all for spraying controlled by the government. So the giant trial pre Kloman: producers will bear bulk sumably could run its course without ever establishing precedents on residents of Times Beach, for in dioxin liability. stance, could sue for, among other Dioxin-associated firms and in things, payment for the loss of the surers, however, are not planning use of their property. For companies insurance strategies wholly in a associated with dioxin--either as vacuum. There are lessons to be producers of chemicals contaminated gleaned, unpalatable as they might with it, as users of such products, or be to industry, from the ongoing as as transporters--the possibility of bestos litigation. The thousands of such suits already has been the im criss-crossing suits among asbestos petus for the review and bolstering victims, producers, users, and insur of existing insurance coverage. For ance carriers touch on a welter of the liability insurance industry, issues that include most of the lia which feels comfortable only when bility problems concerning hazard it knows today precisely what its ous materials. Despite the major dif compensation costs w ill be a decade ference that asbestos' long-term or more hence, the possibility con health hazard to humans has been notes so many unpredictables that proved and dioxin's has not, analysts the current mood among insurers is cannot avoid detecting potential an somewhere between bewilderment alogies between asbestos litigation and horror. today and dioxin litigation to Chemical companies have to pro morrow. tect themselves now, if they have not "What ultimately happens in re already done so, against the chance solving the asbestos claims will be of massive compensation losses. To a come a precedent of sorts in resolv great extent, they have taken on that ing suits in all sorts of toxic task themselves. But whether they problems," comments Rita Epstein, retain self-insurance or establish a director of communications at the captive insurance firm, they ulti Risk Studies Foundation in New mately must go into the traditional York City. insurance market to seek reinsu And companies can go to school on rance. And though wary, insurance more than an implied analogy. The firms are not entirely unwilling to farmer's 2,4,5-T suit is one of more write policies where dioxin might be than a score of lawsuits filed in the involved. The insurance industry U.S. in which dioxin is the prime happens to be, in its own way, in a issue. Of those cases, only one major - state of overcapacity. They are far one has passed through the entire more willing now than they were trial process to a decision. For Frayer, avoid legal precedents dioxin-associated companies and insurers, it is a disheartening exam ple of what dioxin-related litigation of the future might hold in store. In the case Lowe vs. Norfolk & Western Railway, 47 employees of the Norfolk & Western sued the railroad, Monsanto, and two other firms for injuries attributed to a Jan. 10, 1979, rail accident in which car bolic acid and other chemicals were spilled along the tracks outside Sturgeon, Mo. The plaintiffs, most of whom helped in the cleanup, claimed to have suffered a variety of disorders including fatigue, bald ness, liver damage, brain disease, and high blood pressure as a consequence of their exposure to dioxin, which Monsanto conceded could have been formed in small quantities by the chemicals involved in the spill. Just before the trial began in March 1982, Monsanto, which owned the chemicals spilled, and the two other companies, which had built the car whose coupler yoke had ruptured, settled with the plaintiffs for a reported total of $7 million. The railroad pursued the case and lost. The jury awarded the workers more than $58 million. An appeal is under way. The verdict was reached despite the fact that the Environmental Pro tection Agency detected no dioxin at the spill site, physicians found no 58 June 6.1983 C&EN i'ijXj&r.'J. dioxin in the plaintiffs, and the re port of health disorders made by the - ^plaintiffs' physician was refuted by a team of St. Louis University physi cians. To industry, an award of this size made without proof of dioxin's haz ardousness or even proof of any exposure tp the compound raises the specter of a terrifyingly resilient legal precedent. Business' hopes that the appeal will discredit the case's con clusions, however, are likely to be fulfilled, according to legal experts, because of a number of apparently [ questionable aspects of the trial. J American Lawyer, for instance, in a biting article about the handling of the case by the judge and the plain tiffs' attorney, Paul Pratt, paints the entire trial as one-sided. It calls the site of the trial, Madison County in Illinois, a "plaintiff's paradise." And in his appeal brief, Norfolk & West ern counsel Albert Schoenbeck wrote: "The verdicts in the case are so out rageous in light of the evidence that they display, more effectively than words can describe, the total unfair ness of the trial and the complete bias and prejudice of the jury.'" It is the risk of verdicts such as this, however, that has kept dioxin-asso ciated chemical companies doing much as Monsanto did in the case: settling out of court. Dow Chemical, for instance, is or has been the subject of nearly 20 suits in which dioxincontaminated 2,4,5-T is blamed for health disorders. Donald R. Frayer, claims manager in Dow's legal de partment, says the company tries to settle when the cost can be kept within a limit deemed reasonable by the company. "Frankly," he says, "we would intend to handle these things in such a way that they would not set any legal precedents." The proliferation of dioxin-related lawsuits, however, w ill make that difficult. Besides the agent orange trial, there are two other major cases now in litigation that worry the chemical industry. In one, Monsanto is defending itself against former employees of its Nitro, W.Va., plant, which produced 2,4,5-T up to 1969. / The plaintiffs are asking $700 million in damages for their exposure to several chemicals including dioxin. The trial could begin early next year. LABTECH70 It's Second To None In R&D M icrocom puter Perform ance Today's microcomputers can free you from dependence upon shared computer systems, giving you back the control. * your research and development demand. But there's a catch. . . ' finding a system that's not only affordable, but one that provides* a complet&solution to your real-time, high-speed data a c q u it , sition, monitoring and control, and sophisticated.number" . crunching needs.. 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If you're . ,, ' involved in serious analytical research or real-time process; ; . monitoring:you can't'affordnotto:* . . Call us at (617) 497-1010 for details or to schedule a Labtech 70 : ` demonstration; Laboratory^ > ^Technologies C orporation^ * r 328,BroadwayfC am bridge,^ ' M assachusetts02139% iW ^ - - . > ' ` b - LABORATORY^ t e c h n o l o g ie s ? C O R P O R A T IO N : -?f CIRCLE 43 ON READER SERVICE CARD Junes, 1983 C&EN 59 ORG ANIC Dioxin Report IN TER M ED IA TES FR O M SW ITZERLAND In the other, Monsanto and Dow on a combination of factors, incluc are being sued by a group of Union ing the size and type of risk and th I dyestuffs perfumes^ I pharmaceuticals' flavours 3` ' * I agrochemicals - photo chemicals^ Electric Co. employees who claim to have been harmed as a result of ex posure to dioxin while climbing utility poles. To the displeasure of the state of the insurance market. Typ; cally, most polides fall somewhere i between. For chemical companies lookin, I P two companies, the case was filed in for protection from future dioxii the same court that handled the suits, there is little chance of findinj 34iydroxy^n^thoxyanilr>e^^H^:4^ minbguiacol^ Lowe vs. Norfolk & Western case by an independent insurance carrie the same attorney, the now-notorious w illing to underwrite an "occur Pratt. For this reason, notes Dow rence" policy providing coveragt lawyer Frayer, "It is the most dis from the first dollar of a claim on. Bui turbing case we now have." because the insurance market is soft, The first major dioxin cases came at carriers eager for business might take the time of an epoch in the insurance on the dioxin risk on that basis but at ,1^ h Iro^ 3,4^ in itrob en zen C ^ i industry. Insurers are being com a higher dollar level, or "layer." This pelled, as a result of the asbestos suits, means that chemical companies to deal with the problem of covering cover themselves, either through "rionsudden" accidents--accidents self-insurance or via a captive insur that manifest their injuries, in the ance company, up to a .certain manner of asbestos, long after the amount. Once that deductible is occurrence of the exposure--in ad passed, the insurance carrier's cov dition to their traditional coverage of erage would begin. "sudden" accidents, like car crashes, Again, the asbestos problem in which the occurrence and the suggests a precedent. Users of as manifestation of injuries more or less bestos-associated products, like 5-N ifr<risopIm coincide. manufacturers of brake linings, for Since many asbestos producers and example, still can buy liability in users had several different liability surance. The reason is that under insurers over the 30- to 40-year span writers know that the average as between the exposure of workers to bestos award is under $10,000. A the substance and manifestation of policy therefore can be written with health disorders, it has not been dear a deductible of about that size that who should be liable for the victims' mitigates the risk of the carrier and 5-C hi o ro -2^n it ro b e n z o ic^aci d ;; compensation. Three court rulings covers the insured against cata and 6 th fC i^ iV i r e ^ ^ ^ ' i ^ v^ ^ rt - on the issue have not resolved it. strophic losses. Once precedents are Liability insurers would like to set for dioxin awards, the insurance avoid problems like this in future industry presumably could respond cases involving "nonsudden" acci in a similar way. At this point, how dents by adhering to what they call ever, underwriting such policies is a. a, - T ritIu o ro -m -to lu idi n e ;/Pv: 3^ijiiipben^rifiuoride '-. y M - W . S r x '\;i'r, *>'-*11'- "claims-made" policies. In this type considered risky. of liability insurance, the important "Since there are no figures, no date is not so much that of occurrence losses to project on, it is up to each or manifestation, but when a claim is underwriter to decide," says John filed. If the claim is made during the Gross, a senior vice president of C u s t o m m a d e in te r m e d ia te s period of insurance, the insurer pays. Marsh & McLennan. "He might be m To a certain extent, this form makes willing to write it at a price--that the jOur traditional p ro c e s s e a n .^ % a \a v w it stuVv |-,N U ra o n * -`* 5 '. insurers liable for events of the past market would bear--or, through lack that have not shown up yet, but in of knowledge, he might end up giv '-C a ta ly tic hydrogenation a n d o th e r re a ctio n s? ' S~ For catalog, samples, surance firms prefer it. ing it away." technical data please contact: US-A gents: Riches-N elson, Inc. But insurance buyers are no fans of "It's a shot in the dark," remarks 254 Mill Street, Greenwich. Conn, 06830 claims-made policies. What they Risk Studies Foundation's Epstein. Phone: 203-869-3088 Telex: 68 19 177ricnetinc grc Samples (or commercial trade only want is a "tail," insurance industry "The industry is in a state of flux, and Agents in other countries: Please inquire parlance for coverage that, being on everybody's scared. Still the market an occurrence basis, would indem is soft. People will write just about nify them for future losses stemming anything." from current accidents. Since most "I suspect the insurance market policies for large firms actually are will respond in part," says H. Felix written on a customized, "manu Kloman, president of the Risk Plan script" basis, whether a particular ning Group in Darien, Conn. "The policy tends more towards claims- bulk of it, however, will be borne by CIRCLE 38 ON READER SERVICE CARD made or shows signs of a tail depends the producers." 60 June 6, 1983C&EN Europe Provides Test Case o f Human Exposure to Dioxin Severe disaster of 1 976 has had profound im pact internationally on w aste disposal standards, production of chem icals, liability law s, labor relations Patricia L. Layman C&EN London If it had not been for the seriousness of the subject it would have read like an operetta by Gilbert and Sullivan/ based on Homer. In the course of what orig inally started out to be le gitimate disposal/ 41 drums of toxic wastes generated by the notorious accident at the Seveso, Italy, 2,4,5-trichlorophenol plant in 4976 went astray somewhere on an odyssey that started in Seveso, moved across Italian borders to stor age in St. Quentin in France (per haps), to disposal in exhausted salt mines at Herfa-Neurode in West Germany (perhaps), to who-knowswhere. There was talk that the material, contaminated with dioxin, had been dumped into the sea; that the Italian government has had it all along and was waiting until the furor died down to, send it to the U.K. for in cineration; that it has been inciner ated already, at some unknown fa cility in Europe; that it was buried in East Germany; that it was tucked away, an inconspicuous 41 drums, in obscurity somewhere on the conti nent; that it was being trucked around Europe as its holders sought somewhere to dispose of it. The wastes finally were found on May 19, in a French village between St. Quentin and Laon, about halfway between Paris and the Belgian bor der. They had been stored in an abandoned abattoir in Anguilcourtle-Sart. Military personnel and police have moved the wastes to a nearby military base. The president of the French waste company involved, Spelidec, had refused to divulge the drums' whereabouts, but following seven weeks of imprisonment by the French authorities, he presumably changed his mind. The next question is: What hap pens now to the 41 drums? No one wants them, but no one knows quite what to do with them. The Italian authorities refuse to permit their re turn. At the same time that this tale of wandering and looking-for-a-home was being played out, a related saga was working its way into the Italian courts. The Seveso incident oc curred in July 1976. A plant operated near that town by Industrie Chemiche Meda Societa, Anonima (ICME- SA), an Italian company owned by Givaudan, a Swiss subsidiary of the Swiss pharmaceutical manufacturer Hoff- mann-La Roche, was mak ing 2,4,5-trichlorophenol (TCP) for use in production of hexachlorophene. Cool ing water to the reactor apparently had been turned off inadvertently at the end of the day, and the resulting rise in temperature and buildup of pressure caused a safety disk to rupture and a safety valve to open. As a result, the reactor contents were released di rectly to the atmosphere, contami nating a widespread area. Now, nearly seven years after that accident, the Italian government has begun its trial of some of the people involved. Five defendants--down from an original 12--have been charged with causing, without pre meditation, the dissemination of TCP and dioxin over a vast expanse of land, resulting in death of animals, destruction of vegetation, evacuation of certain inhabitants of the land, and appearance of dermatological lesions, among other charges. The trial opened April 18 in Monza, just north of Milan, in the absence of all five defendants, and June 6, 1983 C&EIM 61 o Dioxin Report was adjourned until May 11. On May 11, a strike by lawyers forced a sec-' ond postponement until June 17. The lawyers called the strike to press the government to provide more court staff to speed up proceedings. That court action is being joined by several others. In Switzerland, for example, Hoffmann-La Roche is fil ing suit against the West German industrial firm Mannesmann A.G., with whom it had contracted to dis pose of the dioxin waste, an estimat ed 2.5 tons of contaminated soil. Mannesmann, in turn, subcontracted the disposal to the French firm Spelidec--and the waste then dis appeared. The Green political party in West Germany already has pressed charges against Mannesmann and the West German representative of H off mann-La Roche, in an attempt to force disclosure of what happened to the wastes. And, in part prompted by a European Bureau of Consumer Unions boycott of all products made by Hoffmann-La Roche, physicians in West Germany reportedly have stopped prescribing the Swiss phar maceutical company's drugs. The consumer union decided on its action to pressure Hoffmann-La Roche into, in turn, pressuring Mannesmann into disclosing the whereabouts of the wastes. The consumer group was thwarted in a boycott of Mannes mann because, as an industrial firm, none of its products reach the con sumer directly. Meanwhile, the French authorities had arrested and jailed the president of Spelidec for failing to declare the contents and destination of the dioxin wastes, which his firm trans ported to St. Quentin--and for fail ing to divulge their whereabouts after that. And during the height of the furor over the missing wastes, the archac tivist environmental group Green peace blocked border crossings that might be used to ship the wastes, in cluding one into a potential disposal site in East Germany. West German protests, in fact, in directly have caused Boehringer In- gelheim , which produces 1000 tons per year of the herbicide 2,4,5-tri- chlorophenoxyacetic acid (2,4,5-T) at Hamburg, to get out of the business. Last month, it stated that it had stopped producing the herbicide, primarily because of the controversy over dioxin and dioxin disposal. For Europe, Seveso has the same umbrella connotation of pollution as Love Canal in the U.S. There have been other industrial exposures in Europe besides the accident at the ICMESA plant. And many environ have an impact on the regulatory mental groups and labor unions scene across Europe. charge that 2,4,5-T herbicide spray In 1978 the European Economic and its dioxin contaminent have af Community set up a waste-control fected many times more people-- program for monitoring hazardous industrial workers, agricultural and chemical wastes in its member forestry workers, workers' families, countries. Implementation was set and residents of areas that have been for March 1980. But there was a major sprayed--than the accident at loophole: The monitoring did not Seveso. apply to wastes moving across na But Seveso has been the main tional borders. That encouraged horror story, and it is beginning to transfrontier shipping--such as was done with the Seveso wastes. Stung by the outcry over the Sev eso wastes, member states are tight ening their own internal regulations, and EEC has begun to move to tight en the loophole in its waste-control program. For example, France last month adopted measures that make a pro ducer of toxic waste entirely re sponsible for all operations until its final disposal, even if subcontractors are involved. Dumping sites must report every three months any dis posal of toxic waste. Subcontractors must inform the producer of the wastes about the conditions of transport, stocking, and disposal of the waste. And shippers across the French borders will have to specify the type of waste, the identity of the I  transporters, and the wasted final destination. Similarly, West Germany's interior ministry has proposed to amend the country's 1972 laws on toxic-waste transport. The legislation would re quire each federal state within West Germany through which the toxic waste passes to grant a special permit "only under the most restrictive conditions," with crossings only at a few predetermined border crossing points. A new EEC proposal, adopted Jan. 17, would enable monitoring of toxic wastes down the line from producer to eventual disposal in another member state. It basically proposes that notification of transfrontier shipment must be made; that con tractual commitments between the producer of the waste and the re ceiver in the recipient country are subject to the appropriate authorities and that they must be notified in advance; and that the shipment must be accompanied by a standard docu ment all along its route, as well as a label indicating its nature, composi tion, quantity, place of origin, and security instructions. The pace of proposals moving through EEC is usually glacially slow. But many observers believe that the Seveso controversy may speed up the timetable considerably. Some form of action obviously is needed. As one EEC official notes, the Italian authorities kept insisting, about the temporarily missing Seveso wastes, that all pertinent points of the 1978 directive had been adhered to. "There are now doubts as to that, but no proof," the EEC official says. "For us, that is one more argument for the new directive to make illegal all aspects of this famous story. If the Jan. 17 directive had been law, unless a member state was in manifest in fraction of the law, this [episode] would have been impossible." He thinks the Seveso controversy will help push through the proposed directive in a time period shorter than the one and a half to two years normally needed for environmental issues, with further, quick imple mentation by the member states. "Our member states are all embar rassed by this issue," he says, "so we hope it will go through quickly." THE WORLD'S STANDARDS TOR -mm B.E.T. SURFACE AREA ANALYZERS ,, .......... ...... ...... 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CIRCLE 48 ON READER SERVICE CARD June 6. 1983 C&EN 63 Giulio Natta Present significance of his scientific contribution 1 GIUUONATO Sergio Carra, Federico Paris, italo Pasquon, andPiero Pino, Editors A fascinating and highly readable account of the career of Giulio Natta, 1963 Nobel laureate for studies in stereospecific polymerization and macromolecular stereochemistry. Describes his scientific activities and the developments made in each area since he interrupted his work. Shows his research themes as still in the vanguard of scientific and industrial significance. Written by experts in each specific area who recall the principle lines of Natta's research. Confirms Natta as one of the most significant figures in 20th century chemistry, CONTENTS The Human Personality of Giulio Natta (A. Ouilico) Natta's Work until 1949 (R. Rigamonti) The Scientific Activity of Giulio Natta from 1949 to 1973 (P. Pino) Chemicals and Fuels from Synthesis Gas (/. Wendei) Recent Advances in Heterogeneous Catalysis (G.A. Somorjai, P.R.Watson) Synthetic Hydrocarbon Rubbers (M. Bruzzone) The Role of the Discovery and Investigation of Stereoregular Polymers in Macromolecular Chemistry (P. Corradinl) Some Aspects of the Mechanism of Slereospecific Polymerization of a*Olefins (A. Zambeih) Stereospecific Polymer ization of Dienes: Achievements and Perspectives [L. Porrfy Asymmetric Polymerization {M. Farina) Conforma tions and Dynamics of Macromolecules (G. Allegra) Olefin Metathesis ( Y. Chauvin) This volume is published under the auspices of the Italian Chemical Society and the Italian National Council for Research Published by the Editrice di Chimica Sri 232 p ages (1982) Paperbound ISBN 88-85034-02-0 US & C anada S19.95 Export S23.95 O rder trom : A m erican C hem ical Society D istribution O ffice D ept. 14 1155 S ix teen th S t., N.W. W ashington, DC 20036 or CALL TOLL FREE 800-424-6747 a n d u s e y o u r VISA o r M asterC ard . 64 June 6, 1983 C&EN Dioxin Report In countries on the Continent, That is welcome news to many of most of the concern over dioxin has the U.K. labor unions. Most of the centered on Seveso and the possi pressure against dioxin, or rather bilities that the formerly missing against the products that contain it, waste might be found in one's own has come from labor unions. Chief country. There already is dioxin- among them are the Agricultural & contaminated waste in various Allied Workers section of the Trans dumps throughout the Continent. port & General Workers' Union; the Rhone-Poulenc, for example, has General, Municipal & Boilermaker disposed of its 2,4,5-T wastes in Workers' Union (most chemical plant landfill dumps in France. workers); and the Association of In the U.K., attention also is fo Scientific, Technical & Managerial cused on the Seveso wastes, but from Staffs (which includes laboratory a different perspective: the possibil personnel). ity that after the wastes were found, The Agricultural & Allied Workers they would be sent to the U.K. for union, for example, passed a resolu incineration. The controversy there tion in mid-May, says safety research centers on Rechem International, a officer Chris Kaufman, urging the chemical-waste disposal firm located government to bar dioxin wastes in Southampton. from Seveso from being imported "If one assumes it would be a solid into the U.K. "If it sneaks in, we are material, Rechem is the only com asking our TGU colleagues--the pany with the appropriate disposal lorry drivers, port workers, and oth facilities in the U.K./' agrees Arthur ers--to not handle, to block it," Coleman, managing director of Re Kaufman says. chem. That's a hypothetical assump Wouldn't it be better, in the long tion, he emphasizes. Coleman echoes run, to incinerate the dioxin, ending Giles Shaw, an official in the U.K. the saga once and for all? "From our Department of the Environm ent,- viewpoint, there are no guarantees who said earlier this year in a state that the incineration process is safe," j ment to the House of Commons that says Kaufman. "Within the furnaces ; "in principle" the dioxin would be a there are eddies and currents--it \ most unwelcome import were it sent doesn't ensure that the whole con- j to the U.K. "We are not interested in signment w ill go up and be safe." | doing the work," says Coleman, be Besides, he adds, "Our workers are in 1 cause of the tremendous emotion that plant. We don't want them to be generated about that possibility. exposed to the material. We can "I personally think it is sad that we sympathize with the Italians, but we have to adopt a political stance like don't want it here." this, but we are living in a real Dioxin also has become one key world/' Coleman says about Re- weapon in the unions' battle for chem's position. "We have demon representation on the advisory com strated disposal of dioxin, with in mittees that recommend licensing or i dependent checking of emissions. not licensing pesticides to the gov Technically, we have the capability. ernment. The present advisory It comes down to individuals, emo committees "contain no representa tions, and so on, in spite of anything tives from workers, who are directly we could say to the community. involved," chafes David Gee, safety That's the real issue." officer of the General, Municipal & Rechem already has learned one Boilermaker Workers' Union. "The bitter lesson about that. A number of Nature Conservancy is on it--the years ago, it was ready to accept committee can protect bees, but not Kepone wastes from Virginia for in people." cineration. Public outcry forced the The unions also want assessment company to abandon the plan. "It of pesticide safety taken from the took us many years to overcome the Ministry of Agriculture, Fisheries & stigma and aggravation that left us," Foods and given to the Health & says Coleman. "Forty-one barrels is Safety Executive, a sort of British a very insignificant commercial op version of the U.S.'s Occupational portunity--it would not be worth the Safety & Health Administration, aggravation it would cause us. We're with statutory requirements for li just not interested in the business." censing.