Document omBj65j5zQzDEd8nYr43NbxXo

DIOXIN REPORT A C&EN SPECIAL ISSUE 003718 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. v * 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 pf 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-mentioned'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 Jane 6, 1983 C&EN v*v 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 lowing articles, C&EN examines such from previous waste disposal activi concentrated wastes likely will not topics as the current environmental ties. Concern intensified in sue- 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 how shuffling their way along 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 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 a s - . oxyacetic acid (2,4,5-T) came nearly reaction has hot 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 contaminant in 2,4,5-T. humans. That there are nonperma- more questions than answers. P Early exposures of people to dioxin came about primarily through pro duction or use of dioxin-contami nated herbicides. Such herbicides ;:,"r Dioxin is a shortened^ -and misleading-- n a m e .^ ^ v ; ' ' ' i . n s? became widely distributed in the environment because they were ef fective against broadleaf weeds and undergrowth plants and less toxic to subject of this special -issue; of v C&EN, ts^he"compound 2,3,7,8-tetra- ^Ipfodibenzo^p-dioxin (shown right), . . referred to by most nohscientists simply ' Cl Cl j 3'-' grasses, canes, and established trees. T a s d i o x f e ' v ,.' \ _ L, Indeed, 2,4,5-T was one of the com ponents of the defoliants, the best known of which is agent orange, 'chemic:aal c< nomenclature ' because, The -abbreviation ^TCDD ^also is ^ which the U.S. military began using ;properiyspeaking, dioxin isanother sgmettmes seen:forith i s^compound,f|| in 1962 in Vietnam. Use of agent or ^com pound. th e .stxrmembeVed ring'^ s tan d in g 'fo rj^ ange in Vietnam was halted in 1970. 'C4H4O2 is dioxin; when the two oxygen, However, wittveight ring positions that'Vp But the repercussions of its use still j.atoms occupy positipnsoppqsitaeach:Imight possibly be*ocajpjed ttythe four^jj are being felt in lawsuits, brought by j.'iofenrin thering (as inthe centralring of: "'chlorineatorins;^a tetrachiorbisonfe veterans exposed to the defoliant, : .thejcompound shown), it^is p-dioxin.,. ^there work out to be'22'possibIeletra-c| which currently are being litigated. ' ^TRus, the'compound shown is a substi- - chloro isomers,ofwhich 2p3,7,^tetra-^ Then came Seveso. In 1976, a re ^'tut^p^ioxin inwhich the-four hydrogenr:-,. chlorodibenzo-prdioxin is bniyone. A i-^ actor at a chemical plant near Seveso, ^/atoms of. the'original compound:have^^ogether,,there are 75 ^en^pbioxinsli^ Italy, making TCP for use in hexa- [v-beerij replaced' by ;.tw6 dichlonhatecl =containing.chlorine a to i^ .'^ ^ v f chlorophe"ne,*'w eriPotit Uf"C<3ntro1;-- Hbehzenetring'srThe r^uitant molecule^'* Because u sb r^ .te--r-m--jm s-be-cm spewing its contents, including an j'~'hasTourchIorine:atoms.andthey;oo-'-.- iso widespreabrc&EN also will refer to.. estimated several pounds ofdioxin; Tcpy .the 2r3i&7rarid :8 ring positions;- It ^ *the cpm pbuntfasrdibxlh^ over a densely populated area. The L i X S t T J ii T ~ f- .r. .- TM- r- f --Ls r i ahj June 6,1983 C&EN 21 4t Dioxin Issue Focuses on Three /itrq-j M ajor Controversies in U .S. / .`.Mji < : Furor developing around the question of dioxin ; f ;.q exposure has reached a head in three historic cases-- agent orange, . Times Beach, and Tittabawassee 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 w ill be recalled-- agent orange, Times Beach, and the Tittabawassae 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 dur 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'compouridrwith a'numbeFdffe-' suiting illnesses. But it wasn't until about 1955 that the cause of the ill nesses, mostly the severe skin rash Spraying began in Viet nam in January 1962, using a variety of herbicide con coctions. Only small amounts were used at first, but the amounts jumped 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 called chloracne, was found. West agent orange, an oily liquid that was German physician Karl Schulz, a 50-50 mixture of the n-butyl esters treating workers from a Boehringer of 2,4,5-T and 2,4-D. Ingelheim pesticide plant in that However, because the 2,4,5-T was year, identified 2,3,7,8-tetrachloro- contaminated with dioxin, and be dibenzo-p-dioxin as the cause of the cause during this time it was discov chloracne. Schulz's work was pub ered that dioxin is frighteningly toxic lished,in West Germany in 1957, and in some animals, and because an un appeared in Chemical Abstracts in known number of U.S. personnel December 1958. were exposed to the herbicide while Still, despite this problem, 2,4,5-T in Vietnam, an exceedingly complex was considered a good herbicide and problem has arisen. , its use spread. It was used extensively Vietnam veterans, learning from on rangeland and pastures to kill press accounts during the 1970s that unwanted weeds, and also on rice dioxin was hazardous and that they and nursery crops. Because 2,4,5-T is might have been exposed, began to quite biodegradable and works so ask the Veterans Administration well, it, as well as other herbicides some tough questions. The Chicago (particularly 2,4-dichlorophenoxya- VA office really started things mov cetic acid) was considered by the ing when a case worker there asked "military inthe'early 1960s as'thebest- " veterans about their possible expo means of defoliating large sections of sure to agent orange and any subse forest in Vietnam to take away cover quent illnesses. She compiled a list of from the enemy. 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 th in g 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.aboutexposure to 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 well 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 24 June 6, 1983 C&EN 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 claims 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 tarda automatically eligible for compensation, whether or not any link to agent orange exposure could be made. 1 *- * 1<' ^ 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 w ill 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- this fall. Another VA mortality study will gather data on all veterans who served in Vietnam from 1964 to 1975 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 who 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 very 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 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.Va., 2,4,5-T plant. 1957 Dioxin identified as an unavoid able contaminant in 2,4,5-T. 1962-70 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, fetotoxicity 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 hexachlorophene in nonprescription soaps and deodorants. 1973 Vietnamese study links higher incidences of liver cancer, abor tions, and birth defects to agent orange spraying in that country. 1976 Explosion at ICMESA chemical 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 u ses 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 50 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 w astes 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 will 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 H 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 Dioxin Report and failed to inform the government against the companies stems from a and that, therefore, the companies meeting in 1965 between Dow and should be liable for injuries caused other agent orange makers in which by the herbicide and the dioxin con the toxicity of dioxin was discussed. taminant. The suit has become Dow is supposed to have told the lengthy, complex, and costly. manufacturers they would have to do The original companies named something about the levels of dioxin were Dow Chemical, Monsanto, in agent orange, or the government Hercules, Thompson-Hayward, Uni- would take regulatory action against . royal, Diamond Shamrock, Thomp the use of 2,4,5-T. Shortly after that, son Chemical, Aggrasit, Hoffman- Dow bought a license to use a process Taft, Riverside Chemical, and developed by West Germany's Hooker Chemical (which made the Boehringer Ingelheim that reduced 2,4,5-T precursor 2,4,5-trichloro- levels of dioxin in 2,4,5-T to less than phenol). - - - *'-fi ' 1 ppm and urged the other makers to Most of the companies asked U.S. do the same. According to Dow, some Federal District Court judge George did and some did not. Whether the Pratt for a summary dismissal of the 1-ppm level is a safe one for dioxin is claims that they are responsible for one of the questions that has not any injuries, under the government been answered, though that is just contractor defense. This means that what the jury may be asked to decide the government, as the user of the at this trial. herbicides, knew as much as or more If the companies are found liable than did chemical companies about for the injuries allegedly resulting the hazards and should have used from dioxin exposure, they can be this knowledge to warn those who sued in state courts by veterans or might be exposed. They also contend, their survivors for damages. In most and have proved to the judge's satis states, the statute of limitations will faction, that the Department of De have expired for taking action fense had set standards for agent or against the companies and special ange which were met by all the legislation will have to be passed, as companies. Two companies that have it has been in New York for instance, not asked for a summary judgment if the veterans are still going to be are Monsanto and Diamond Sham able to sue over agent orange expo rock. sures. For a variety of reasons, some of Just how many vets actually were the companies have been released exposed is a question impossible to from the suit. Those remaining are answer. The military records are not Monsanto, Diamond Shamrock, Uni accurate enough to tell exactly where royal, Thompson-Hayward, and the eveiy soldier was when spraying was largest producer, Dow. The trial had done in an area. And wind drift or been scheduled to begin June 27, but, elapsed time before troops entered a in a procedural move, Pratt post sprayed area also would determine poned the opening until completion exposure. DOD had said early in the of the discovery process, an infor agent orange controversy that it kept mation gathering period that attor troops out of sprayed areas for up to neys say could take another year or six weeks, but many reports show two. that gound troops entered some The judge's decision to go ahead sprayed areas as early as the next day. with the trial means that the com Veterans groups say they have an panies must prove they withheld no ecdotal evidence that planes sprayed health data from the government some troops directly, or that troops . that would have made a difference in had loads of agent orange dumped the spraying of the herbicide. Al on them when a plane was damaged though there are some data in the by enemy fire and had to return early work on 2,4,5-T on the prob quickly to its base. lems from dioxin, they are scanty. Despite the controversy over ex Dow, which made more than 30% of posure and possible health problems, ---^-the total agent orange used in Viet _ VA still holds that no long-standing nam, is sure the government had all health problems exist from agent the safety data it needed. orange exposure. It appears, how One of the allegations raised ever, that this position is being eroded by the actions of other federal agencies in response to dioxin con tamination, and the difference has not been lost on veterans. Although most regulatory action against 2,4,5-T and its contaminant dioxin was not begun until after 1970--after most troop exposure in Vietnam was past--concerns about health effects of dioxin from agencies such as EPA and CDC appear to be far greater than those voiced by officials at VA. Nothing makes this clearer than the dramatic actions taken to remedy the dioxin .contamination problem in Times Beach, Mo. .Times Beach has a most unenviable reputation as the town too poisoned to live in. Just a few miles west of St. Louis, its fate has been sealed as the result of some poor waste disposal practices, insufficient environmental laws in the early 1970s, and political pressures for action. Because of the contamination and the federal gov ernment's decision to buy the town, Times Beach is expected to disap pear. The story traces back to the 1960s and begins with agent orange. Hoffman-Taft, one of the original defendants in the agent orange trial, made 2,4,5-T for the Department of Defense for a while, but ceased pro duction in 1969, about the time eco logical concerns led the military to halt spraying. In November of 1969, the plant in Verona, Mo., was leased to North Eastern Pharmaceutical & Chemical Co., and then later sold to Syntex Agribusiness, which let the pharmaceutical company stay to produce hexachlorophene. . _. According to EPA's records, wastes from the plant were being disposed of properly by shipping them to a waste facility owned by what is now Rollins Environmental Service near Baton Rouge. But in early 1971, al legedly to save money, North Eastern contracted with a firm called Inde pendent Petrochemical to haul away its sludge bottoms. Independent, in turn, subcontracted the job to Russell Bliss, a waste oil hauler in Missouri. The records show that Bliss hauled away 18,500 gal of waste bottoms containing dioxin from the Verona plant, which he apparently stored in waste oil tanks near Frontenac, Mo., between February and October 1971. ,, ___ 26 June 6. 7983 C&EN ft ft 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 extraction led the investigators to the Hoffman-Taft plant in Verona, and the thinking was that 2,4,5-T pro duction was the culprit. But it was then discovered that the hexachlo- rophene wastes made by North Eastern had been disposed of im properly. .- By this time, Bliss had sprayed oil Then, in 1979, EPA's office in Kansas City received an anonymous telephone call that toxic wastes were buried on the James Denney farm, near Verona. The tip checked out, and a number of drums of dioxincontaminated waste eventually were removed from the site. This got EPA investigators thinking. ' -rr stable owners, developed an in over many sites in eastern Missouri. It had been believed in the early flamed and bleeding bladder after EPA has reconstructed as much of the 1970s that the half-life for degrada playing in the soil of the arena, and Bliss operation as possible and be tion of dioxin in soil was less than a three other children and one adult lieves there were more than 150 sites year, based on tests by the Air Force complained of skin lesions after ex sprayed with the waste oil, but how and U.S. Department of Agriculture. posure to the stables. All the symp many are contaminated with dioxin That was wrong. EPA found that toms disappeared after exposure was won't be known until testing can be waste leakage from the drums still halted and have not recurred. completed. had high concentrations of dioxin, State of Missouri investigators, The search for contaminated areas when almost* all of it should have reasoning that something must have did not begin immediately, however, decomposed after being buried for been in the oil that was sprayed, sent as might have been expected. A large six or seven years. This prompted samples to CDC for analysis. The storage tank of wastes was found at them, after much record searching, to arena owner asked Bliss if anything the Verona site, heavily contami go back to the stables that originally dangerous had been in the oil and nated with dioxin. Levels of extracts were sprayed and to the sites where Bliss reportedly said there was not. In were measured at 356 ppm by the the contaminated earth was dumped the meantime, the state had the are CDC researchers. This became the to measure present dioxin levels. The na's dirt hauled away and placed in primary concern because its potential levels found were essentially as high a distant landfill. Some of it, how for human health injury was seen as as they had been in 1971. At the site ever, was used as fill dirt for resi high. Syntex, which now owned the where the soil had been used as a dential construction, in what has plant, had the wastes detoxified by landfill, levels ranged from 10 ppb to now become known as the Minker/ ultraviolet treatment at its expense. 300 ppb. At the Shenandoah Stables, Stout site. It should be remembered that at that concentrations were still as high as CDC, with few clues to go on, took time there were no federal laws 1750 ppb. until 1974 to identify dioxin as the governing waste cleanup or proper These tests began in spring of 1982, toxic compound in the oil. Scientists disposal. The Resources Conserva and the first data were released in there, led by pathologist Renate tion & Recovery Act was not passed August. The findings prompted a Kimbrough, eventually determined until 1976, and the abandoned waste more exhaustive sampling of all the that the oil was contaminated at cleanup law, superfund, didn't go areas known to have been sprayed. about 33 ppm, a level far higher than into effect until 1981. By December, more than 300 samples any that occurred in Vietnam from With no further reports of serious had been analyzed and the results agent orange. Crystals of trichloro- illnesses, the issue faded away after released. EPA had found dioxin lev phenol found during the soil analysis 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 j 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 when the Meramec River, which fiows 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 Trees (upper left) in this part of Vietnam were defoliated with 2,4,5-T the flood waters.) June 6,1983 C&EN 27 Dioxin Report C&EN Stef! photo The situation now began to get tense. Residents of the community demanded that the government buy their homes so they could move to a safe place. Some people began com paring the contamination problem at Times Beach to the situation at Love Canal in New York. Then, in early February, the EPA assistant admin istrator in charge of waste cleanup and superfund, Rita Lavelle, was fired by President Reagan, amid al legations she had used the superfund for political leverage in favor of Re publican candidates. . 1 Possibly pushed a little faster than she would have been otherwise, EPA Administrator Burford announced Feb. 22 that the federal government would buy up all the contaminated property in Times Beach, paying the residents a price reflecting property values before the dioxin contamina tion was found and before the flooding. Superfund would supply .$33 million and the state of Missouri would supply $3.3 million more. Subsequently, on April 5, EPA of fered to buy a number of homes in the contaminated Minker/Stout site that had been built on dirt from the stables originally sprayed by Bliss. A third area, the Quail Run mobile home park, was found to be contam inated with up to 1100 ppb of dioxin in a sample dug out from beneath a paved road, with levels of 2 ppm in side two of the mobile homes. EPA has also offered to buy the trailer park. At this time, no other areas are being bought out. The decision to move residents, either temporarily or permanently, is made by CDC and the Missouri Department of Public Health, on the basis of results from samples sub mitted by EPA. The belief that a level of 1 ppb is probably safe comes from a CDC estimate using a number of studies, and is discussed on page 48. - When EPA told the residents of Times Beach the government was going to buy their homes, the process was expected to take 60 to 90 days. Now, after three months, there is still a hangup. The federal government cannot take title to the property be---'cause -the law-forbids spending-su' perfund money to clean up federally owned property. Missouri will not take title until all the residents have moved because they do not want to be expected to provide services, such as water, to the areas. There were, last month, about 50 families that were not moving, but a second flooding of the Meramec seems to have con vinced them it was time to leave. Spokesmen for the Federal Emer gency Management Administration, which has been on the site since the first flood in December and is re sponsible for dealing with the resi dents on the buyout, say it appears that all the former residents are leaving. In addition, an unofficial and unapproved agreement may have been reached that would permit the property to first be assigned to the city of St. Louis, so the cleanup could get started, then transferred to Missouri when that state's conditions are met. In the meantime, the resi dents are living elsewhere and have yet to receive the promised com pensation. As of this writing, there are 31 confirmed sites of dioxin contami nation in eastern Missouri, all trace able to the spraying by Russell Bliss. Officials believe the final list could contain more than 100 sites. How many more people might have to be moved and how much it will cost is pure speculation, but the expenses can be expected to rise. Midland, Mich., is another city that has become associated in the public mind with dioxin contami nation. The Midland connection first sur faced in the national news media last March when Rep. James H. Scheuer (D.-N.Y.) charged that he had evi dence showing that then EPA acting administrator John Hernandez had intervened personally to allow Dow Chemical Co. to alter a draft EPA re port on the sources and effect of dioxin in the Great Lakes region, suppressing all references to Dow's responsibility for dioxin contami nation in and around its plant. In fact Scheuer charged that owing to Hernandez's intervention, and by implication Dow's, all references to studies showing the adverse health effects of dioxin were removed from the report. -- Testifying before Scheuer's natural resources subcommittee on March 23, Valdas Adamkus, EPA's Region V administrator, said that Dow's Young: doubt cast on ability to link illness with exposure to dioxin objections to the draft report centered on a statement that EPA concludes that Dow's Midland facility is a major, if not the only source, of dioxin contamination in the Tittabawassee and Saginaw Rivers and Saginaw Bay in Michigan. That sixline draft conclusion did not appear in the final report. Ronald O. Kagel, director of envi ronmental quality for Dow Chemical USA, who reviewed the report for EPA, says, emphatically, that he did not ask EPA to delete that six-line paragraph from the report. He says he did point out that "the whole paragraph was lifted out of a 1978 report and it appeared again almost word-for-word in a report written in 1979. At that time we could not dis pute that and we didn't. But in 1981 there had already been an interna tional dioxin conference. There had been many papers published sup porting our theory that dioxin can be created by combustion. I said, 'Gee guys, that's a 1978 statement in a 1981 report and I really think you should change the word 'concludes' to -'speculates' because of the data that support our theory.'" Kagel says that in making his comments he was "strictly trying to 26 June 6, 1983 C&EN 9 speak to the validity and technical upper midwest) that a preliminary found to be loaded with PCBs, which accuracy of the report and specifi investigation had found more than would have interfered at the time cally those portions that were taken 40 toxic chemicals, mostly in the low with the TCDD analysis. Finally, out of Dow's work." Further, he says parts-per-billion range, in the ef towards the end of 1977 Dow got a that many of the portions of the draft fluent from Dow's Midland facility. batch of usable trout and put them in report released by Scheuer that were Dioxin was found at levels of 50 parts cages where its effluent mixed with marked "cut" already had been de per quadrillion in the effluent and at the river water under flowing con leted from the copy of the report he levels of 100 ppt in caged whole fish ditions. Bioanalysis of the caged fish received. Others had markings indi that were exposed to the effluent. 'V was completed in May 1978. Positives cating that somebody already had The search for dioxins in Midland were found for most fish in the mix decided they should be cut. may very well have been initiated by ing zone. At the same time, Kagel At just about the time the charges a false-positive test result. Dow pe says the fish research lab, which had of undue influence were being aired riodically monitors its discharges for been doing studies on the biomag two Michigan environmental, TCDD and on April 13,1977, the lab nification of TCDD by trout, reported groups--the Foresight Society, reported a positive number--8 ppt a biomagnification factor of 6600. headquartered in Lansing, and the with a detection limit of 3 ppt. "That Dow reported all of its findings to the Environmental Congress of Mid- got us concerned," Kagel explains, State Department of Natural Re Michigan, headquartered in Mid "because we had never seen dioxin sources in June of 1978. In July, the land--filed a citizens petition with before . . . but it triggered a number company met with state representa EPA asking for a full field investiga of things." The first thing that was tives and made a commitment to find tion of central Michigan. They said done was an analysis of some fish the source of the dioxins. an investigation was needed to de that had been caught in the Tittaba- The first thing Dow did, Kagel termine the effect of the pollution wassee River the year before during says, was to look at its own internal caused by disposal and emissions Dow's biennial river survey and waste streams, where it might expect into the air, land, and w ater. of placed in the freezer. Analysis of the to find dioxins, and didn't find any chemical substances that threatened fish showed dioxin levels ranging thing that could be considered sig the health of the residents and the from nondetectable to 0.19 ppb, with nificant. Then, he says, "Quite by integrity of the environment. At a a detection limit of 0.02 ppb. In May accident two of the chemists in the press conference in Washington, of 1977 the company collected more lab went up to the'second floor to get D.C., Andrea K. Wilson, director of fish--mostly bottom feeders--from a control sample of dust off a book ECOMM, explained that "given the the river, analyzed them, and again shelf. They analyzed that dust and fact that soft- and connective-tissue found positives. Kagel points out that found it contained all the dioxins-- cancers among white females in the state-of-art analytical method at the tetras, the heptas, the hexas, the Midland County are four times the that time allowed only the detection octas. We said, 'My God, we've been national average, the birth defect rate of 2,3,7,8-TCDD, plus 16 other tetra looking for a waterborne source and is now being re-evaluated, and Dow's isomers. we know that. . . the second floor has own data indicate that soil samples After the second batch of fish was never been under water. So it's got to taken at their Midland plant contain analyzed, Dow devised some exper be from somewhere else that's air a range of TCDD (dioxin) from 0.3 iments using caged fish to determine borne." ppb to 100 ppb, we feel that a full where the dioxin was coming from. That, he explains, is w hen "we field investigation, including an ep The first shipment of fish ordered started looking around the division idemiological study, is warranted." died before it got to Dow. The second at dirt samples and seemed to find Hard on the heels of the petition batch of fish all had a fatal fish dis more dioxins as we got closer to our came an announcement by EPA's ease, commonly known as the "Ick." incinerator and power plants." Thus Region V office (which covers the The third shipment from the East was was Dow's combustion theory Tft i Agent orange had far less dioxin than earlier 2 ,4 ,5-T born. The company dispatched scientists to several cities to collect soil samples Co~de namwe i ,4'j. Herbicide'*' , . ; ' Quantity, gal - Period of us around municipal incinerators and 2,3,7,8-TCDD,. t powerhouses. In almost every case r ; ppm `; they found dioxin, although not Orange' '* ^ 2.4-D; 2,4,5-T* 10,646,000 ' '1965-70 *1.98 necessarily 2,3,7,8-TCDD. They ana T White ' v -L' -2,4-D; picloram 5,633,000 1965-71 1 -- - ;- '' Blue' Cacodyiic acid * 1,150,000' '> ` 1962-71 ' ' - "i lyzed the carbon soot inside mufflers collected in Detroit and found diox Purple . 2,4-D; 2,4,5-T '< ' . - -145,000 1962-65 Pink . j * 2,4,5-T ; . - ' 123,000 . , 1962-65 Green . V .TOTAL ,f. 2, t*, 4 , 5 - T V -rvK ^ - 8,200' ,/ ti 1962-65 V 17,705,200^ 'V ' . 32.8a ' 65.6 - ' 65.6 v < k -,- 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. a Assumed level from one known and four probable samples ol purple. Note: Pink and y e e n levels are twice that of purple because they were full-strength 2,4,5-T, Sources: Proceedings from 2nd Continuing Education Conference on Herbicide Orange. May 1980; and Air Force OEHL technical report on toxicology, fate, and risk from agent orange and dioxin, October 1978 > ^ * -/ 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 i Dioxin Report 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 evi dence right now would support the fact that you can get dioxins formed at very low levels in the combustion processes from common fuels." r;* If that is true it would go some way towards explaining the results of a recent study which shows dioxin ,Road going through Times Beach Mo., is blocked by sign warning of dioxin contamination in fish in many rivers in Michigan. The fish were collected from 19 Michigan rivers, plus Sag temperatures above 1000 C just the While it was doing this work Dow inaw Bay and Lake Erie by DNR. opposite occurs--formation is mini also was perfecting its analytical Their skinless fillets were analyzed mized and destruction maximized. techniques, Kagel says, using a mix by Swiastolov Kadzmar, a graduate Thus, municipal incinerators could ture of three different methods dur student working under Matthew J. be expected to produce more dioxins ing the course of study. The first Zabic, professor of entomology and than industrial incinerators, which separated out 2,3,7,8-TCDD plus 16 assistant director of Michigan State burn at 1000 C, because the munic other tetra isomers; the second, University's pesticide research cen ipal facilities operate at generally 2,3,7,8-TCDD plus 11 others; and the ter. Thirty-four of the 62 fish ana lower temperatures. third 2,3,7,8-TCDD plus two other lyzed had no detectable levels of isomers. Then in late 1978 a tech dioxin. Levels of 2,3,7,8-TCDD in the nique was developed that isolated all other fish samples ranged from a low 22 tetra isomers. of 17 ppt, with a detection limit of 12. % Since 1979 Dow has done several ppt, to a high of 586 ppt, with a de other studies. Having, as Kagel says, tection limit of 81 ppt. Many of the "made the comment that we thought positive samples came from fish that dioxin had been around since taken from waters that had no con the advent of fire" and figuring that nection with the Tittabawassee riv- wood was one of the earliest fuels, a ershed and therefore they could not study was done of residential wood- have been contaminated by Dow's burning stoves in Minnesota, New effluent, though the samples did Hampshire, Oregon, and Michigan's come from rivers in industrialized upper peninsula. The source of the areas. wood for each stove was carefully Typically, Kagel says, dioxin is documented to make sure it had very tightly bound to fly ash, as it is never been sprayed, never treated to soil. To remove dioxin from fly ash with pentachlorophenol, Kagel says. one has to do exhaustive benzene or 3: But in each case some dioxins were toluene soxhlet extractions for 24 found in the soot from the stoves. hours. "It's very tightly held," he As Kagel points out, one of the says, "so the question is how does it components of wood is lignin, a get off the fly ash and into the fish?" phenolic material. There is also a Dow has been involved with EPA's natural chlorine content in wood Duluth, Minn., lab in a joint study which will vary from 14 to 84 ppm. designed to answer that question. "Remember," he says, "we're talking Duluth supplied some carp finger- about reactions that occur with a lings, Kagel explains, "which we put yield of 10~10%. These are trace re into a fish tank with some municipal actions, and 14 ppm, when you're fly ash of which the 2,3,7,8-TCDD .lookin g, at. a millionth of .a mil content was about 160 ppt. That rep Dow Chemical researchers sample Tit- lionth--a ppt--is a lot of stuff. It's the resented about 0.48% of the total tetra tabawassee River for dioxin near the same with coal, which actually has a isomers, all of which were present. il company's Midland, Mich., plant much higher chlorine content than After 30 days in the tank the fish 30 June 6 , 1983C&EN Dioxin Report Few regulations aim specifically at dioxin Despite all the problems-- medical, May 19, 1980, EPA published a rule political, and social-- associated with' under the Toxic Substances Control dioxin, it remains a remarkably unreg 'Act that requires any person intending ulated compound. Early concerns fo to dispose of wastes that contain dioxin, cused on exposure to the dioxin- or even of substances produced on contaminated herbicide 2,4,5-T; only equipment that previously was used to recently has dioxin itself been regu-. make 2,4,5-trichlorophenol, to notify lated. EPA 60 days in advance of such in 1970 a Congressional hearing disposal. That notification must include took place and the National Institute of details on the amount being disposed Environmental Health S cien ces an of and the method to be used. nounced a study that showed birth de-, .> Just recently, the agency proposed fects in animals that were exposed to' a regulation for treating dioxin-con 2,4,5-T containing low levels of dioxin. taminated waste under the Resource This prompted the U.S. Department of j Conservation & Recovery Act. This Agriculture to disallow most u ses of would perm it d isp o sa l of dioxin- the compound, permitting use only on contaminated waste only at facilities forests, rights-of-way, open rangeland, that are fully licensed by EPA. The and rice fields. In addition, a voluntary agency says potential problems might "agreement by 2,4,5-T makers limited arise if disposal is allowed at unper dioxin concentrations to less than 0.1 mitted landfills or in incinerators that ppm. \ might not be working properly. This The ball w as passed to the new rule, if adopted, would supersede the Environmental Protection A gency, 60-day notification rule. which'continued its investigations and The other area in which EPA is soon moved to further limit the herbi moving forward Is dioxin contamina- cide's use. In 1973, EPA set up the 'tion of water. EPA presently is moni j Dioxin Monitoring Program to monitor toring effluents from chemical plants residues of dioxin in human and envi to determine if dioxin is present and, if ronmental sam ples. EPA attempted to so, at what concentration. These data cancel all uses of herbicides that were could be used in preparation of a wa derived from 2,4,5-trlchiorophenol in ter quality criteria document. This would | that year but eventually had to cancel give manufacturers an Idea of what | the proceedings because the analyti- EPA thinks is a safe level for dioxin in | cal methods necessary to determine water and probably would presage fur- . ) low levels of dioxin were not available. ther regulation of dioxin, under either I ~The agency began a rebuttable pre- the Clean Water Act or TSCA. (Because ! sumption against registration process dioxin is a priority water pollutant, some I on 2,4,5-T in 1978. states have regulations that require no | Then in May 1979, on the basis of detectable levels in plant effluents.) j heavily criticized studies linking the ` The only other significant action tak spraying of forest areas with 2,4,5-T en on dioxin is by the Food & Drug to a number o f miscarriages among Administration. A series of recommen | women in Oregon, EPA issued an emer- . dations (not regulations) by FDA in . * gency suspension that allowed the her- 1981 advised people not to eat fish j blcide to be used just on rangeland with dioxin levels greater than 50 ppt, | and rice fields because EPA saw little . but that fish with less than 25 ppt of I risk of human exposure there. ' ' dioxin were okay to eat. Because these j The hearings on cancellation of are not regulations, an FDA sp ok es-- . 2,4,5-T have dragged on. They currently man points out that if the levels do ! are suspended while EPA and the rise above 50 ppt, the agency cannot : chemical manufacturers try to reach take any action to remove the product. , som e kind of agreement, possibly on Thus, aside from the restrictions on i permitting som e use of the herbicide - the use of 2,4,5-T (because of its dioxin if dioxin levels In it can be kept very contamination) and the current 60-day l o w . _______ _____ ___ notification rule for waste disposal, " ''But other tools have passed'into --dioxin is not specifically'regulated by EPA's hands for regulating dioxin. On the federal government. ' ' " r were taken out ancj 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 we were going on to controlled ex periments when 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 might 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 Dioxin Report land is low --below the national av erage, below the state average, and below the average for the surround bought." And he says, 'They [Dow] have done everything they can and should have done to alert the public, ing region/'' He says there was a the media, the state and federal gov soft-tissue sarcoma in women that ernment." was higher than normal. `"There was Some people aren't so confident. one case in the 1950s, five cases in the As Dianne Herbert, one of the lead 1960s, and eight cases in the 1970s. ers of ECOMM, sees it, "Dioxin is a This was a matter of concern to the sexy issue that has gotten the atten county health department, the state health department, and certainly to us," Mann says. The State Health tion of the media, but it certainly isn't the only environmental or health problem in Michigan." She also Department conducted a study and thinks it's good that the attention of released its results on May 4. And EPA is focused on Midland. How according to Mann "could not ascribe ever, she notes the city itself is any particular causes to the rate of fighting any investigation. 'They increase. There was no commonality naturally want to get the focus off," between the cases that could be she says. 'Their strategy is let's found; although the department felt spread it out and say, 'Oh yes, dioxin there must have been a commonality, needs to be looked at, but all over the they certainly couldn't say that it was country.' There are problems--peo dioxin." Kagel: dioxin dust on a bookshelf ple don't want to move to Midland; The department did recommend people have called and asked, 'What development of a registry of persons that the people who have done the kind of place is it?' Maybe the prob most likely to be exposed to dioxins testing, the measuring, the toxicolo lems should have been taken care of as evidenced by their occupations, gy and epidemiology studies are all earlier on. They accumulated until fish consumption patterns, or loca Midland people. They all live here they all blew up and that's too bad. tion of residence. Such a cohort of with their families. It isn't some I'm from Michigan and I like living people, it said, could serve as a outsiders coming in and saying ei here. I don't want to give up my framework for possible future epi ther it's safe or unsafe. It is Midland house. I don't want to move." demiologic studies. people that are doing these things Herbert says she understands the Meanwhile, Midland's attitude to and they have significant reputations reluctance of any community to the dioxin issue is expressed in a va not only in Midland but worldwide." believe that there is something riety of ways. Mann says that "the Certainly no one is going to stay here wrong or that the company that perception within the community is if they know their family is in jeop many of them work for has done that there's nothing out of the ordi ardy, he says. Miles explains that something that is illegal or bad for nary, nothing dangerous." But he over the years, because of Dow's en their health. 'T he average person adds, "That's not the perception if vironment and safety record, "people you talk to," she says, "will say that you get more than 100 miles away have built up a wealth of confidence Dow has been good to us and I would from here and have gotten most of in that corporation that could not be never disagree with that. For a com your information from the news munity this size to have its own media." symphony, a beautiful center for the Then there are the retirees from arts--that is very unusual. But I don't and employees of Dow who come think that gives them the right to do into Rep. Donald J. Albosta's (D.- what they want with the air, and the Mich.) local office and who, says of water, and the land. The bottom line fice manager Pat Casey, feel as if the is that in this community Dow de criticism is being directed at them. cides what is safe and what is dan "Their feelings, and X think their gerous. They make those decisions beliefs, are that they worked for a for people and I think that people high-class company that spent a lot of should be allowed to make their own bucks on environmental concerns decisions." and research. Dow has always had a Others are seeking further infor very aggressive in-plant safety pro mation. That was the purpose of a gram. So the employees don't feel late May forum on dioxins organized there is any justification for the in by the Midland sections of the sinuation they pick up that Dow has American Chemical Society, Ameri done something wrong." can Institute of Chemical Engineers, City manager Clifford Miles thinks and Sigma Xi. that one of the reasons for the very' -- At the forum, which about 500 low level of concern in the city, and people attended, a panel of five one he personally subscribes to, "is technical experts on dioxin issues 34 Jane 6, 1983 C&EN  ------------Dioxin Report answered questions from five local ment? Is that a problem? And, finally, citizens--none of whom worked for are national standards needed to deal D ow--and the audience. with the problem? According to Susan Butts, a senior The study as now planned would research chemist at Dow and an or be run by the Region V office. A ganizer of the forum, its impetus prototype study costing $2 million to came from the fact that "we were $3 million would first be done in aware that a lot of studies had been Michigan. That study then would be done on various aspects of the dioxin expanded to a national level at a total problem, but we hadn't really heard cost of about $12 million. According very much about the results of those to Richard Powers of DNR's toxic studies. Our concern was really in chemical evaluation section, the trying to hear a more detailed expla Michigan part of the study, as tenta nation of the sitution, in terms that tively planned, would consist of a would be understandable not only to -study in the vicinity of Midland to scientists but to the general public." determine the extent of contamina In putting the panel together, she tion in that area. This would mean says, "We tried to be sure that we sampling soil, air emissions, and fairly represented all points of view. water effluents from the plant site, We did rather heavily weight it and river sediments. The second towards people with a biomedical component of the study would be background, because we thought monitoring fish, including game fish most of the questions from the audi and bottom-feeding carp, in 15 ence would concern human health Michigan rivers for dioxin contami problems. And most of them did. nation. There were a lot of questions about As part of the national study, air the toxicity of dioxins, about the and soil sampling and possibly fish meaning of toxicity, and about how monitoring would be done at other dioxins would be rated relative to sites, perhaps in Michigan, perhaps other health hazards." in Region V, or perhaps somewhere For her part, Butts says she never else in the country. Powers says, "It had a personal concern about her doesn't make any difference to us own health, but she did want to where they're done, as long as they know where Midland stood in rela are done. We feel it is necessary to tion to other places in the U.S. that have comparability studies in other have problems with dioxin contam areas of the country, both areas that ination. "I felt quite reassured," she would be expected to be contami says, "by what we were told by the nated and others which should be panel members. There were some relatively clean." minor disagreements about inter Protocols for the study are being pretation of data. But, if I were going developed, but actual work is pretty to try to summarize what the panel much on hold because everything is said, it would be that they didn't feel contingent on getting federal fund that there was any significant health ing. The House Appropriations problem in Midland. But until we Committee has included $5 million know more about the situation they in EPA's fiscal 1984 funding bill for would like to continue monitoring nationwide dioxin studies--$1 mil health in Midland to make sure." lion for R&D and $4 million for In fact just about everybody seems monitoring studies in Michigan and to agree that what is needed is con Missouri as well as other places. The tinued monitoring and more study, Senate Appropriations Committee preferably not just in Midland, nor has not yet made a decision. EPA's even just Michigan, but nationwide. new administrator, William D. Rep. Albosta is seeking funding for Ruckelshaus, is expected to ask just such a study. He feels that a Congress for more money for the number of questions need to be an agency both in this and the next fis swered. Questions such as: How cal year and reportedly has expressed pervasive is dioxin? At what con his support for a national dioxin centration is it present in the envi study. ronm ent? Where is it comingTrom? -Although everybody, including What are safe levels? Are dioxins Dow, supports a study, not every bioaccumulating in the environ body is happy about what is being planned. As Mann puts it, "First you say there's a ticking time bomb, a life-threatening situation, and then you do these studies--the results of which won't be out for two or three years. What we need is a reasonable amount of analysis in a reasonable amount of time, primarily to reassure people outside this community that it isn't as bad as had been pic tured." Along the same lines, the Midland City Council, three of whose five members, as w ell as Mann, work for Dow, passed a resolution expressing its support of scientific studies on exposure levels and effects of dioxin on the environment and the public health as long as they weren't limited to Michigan, but also expressing the council's feeling that $12 million was just too much. Further study is quite probably the proper response to the levels of dioxin contamination that have been found in Michigan. And, although EPA appeared to rush into Missouri in an attempt to improve its public image when everything the agency did was being looked at with cynical eyes, hindsight may show the deci sion to be justifiable and prudent. Other human exposures to dioxin, such as those of soldiers in Vietnam or the people in Seveso, Italy, in 1976, involved considerably less dioxin than those of the Times Beach resi dents. In Vietnam, for instance, the Air Force's Young calculates that the level of dioxin in the soil would have been 0.017 ppb, 20,000 times less than the 300 ppb found in Missouri. That assumes that agent orange, with an average dioxin concentration of 2 ppb, is sprayed at a rate of 3 gal per acre and that all the dioxin falls right to the forest floor (although studies found that only about 7%of the agent orange penetrated the forest canopy). Similar types of exposure com parisons can be made for the resi dents of Seveso, leading to the con clusion that the Missouri experience may represent the largest, long-term exposure to dioxins that humans have endured. If dioxin is the hazard that some believe, then the costs of moving entire'towns probably'are not greater than the risks of letting people continue to live there. Dioxin's Human Toxicity Is -xC>i ' . t mu . L i r ` 1 (j .-! -'isti 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 what it does to humans R ebecca 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 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 1 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 i 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 fig 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 June 6, 1983 C&EN 37 : . Dioxin Report usually is not the infection that kills them, and putting treated animals in a germ-free environment will 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 Junes, 1983 C&EN Researchers seek to explain dioxin's effects on cellular biology s r f i*s f. LIVING CELL i - V I;fi? --IB- W Nucleus r E* S p Dioxin Inducer-receptoM IReceptor .-.complex moves ^ ,, r -_ J ^ c e l l ' ^ T Into nucleus goes membrane, reacts ' with dioxin - Erxl Unknown site in nucleus ih Message now received' Dioxin Innocuous products excreted ji-j ' - J> i ?... .O' 11 L"V-h2'.*j RRfecsoppounusoeciIs syiniLthiiecasios oufi }^ h 7 specific messenger RNAs mRNAs direct, -^ ^'"synthesisof - specific proteins"'^ - (cytochrome JV IUInnlkr_no_w_n critical target Reactive intermediate _ ( ^ 1^0 rW'--rrTM-- ^ ' ^ `1- I i. . . . . ' iV m r* " _r 1 0^1 Reactive ' ^ ` Iintermediate R7 binds critical target '< * J , ,'Lf-- 3j If the exquisite sensitivity of som e, 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 som e cells are incredibly sensitive to dioxin, and by exploiting the differ en ces between dioxin response in dif ferent types of cells, these scientists have a probe for examining som e of the very intricate inner workings of cells. "If morphine addiction weren'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 som e 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 som e 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 example of a larger class of halogenated aromatic hydrocarbons. All of these materials bind to the sam e 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, tike chlorine atoms, need to be in at least three of the four corners and nowhere else in the molecule. "v^` These requirements fit dioxin exactly, but other m olecules like chlorinated di- benzofurans or brominated biphenyls also can be accommodated in this at tachment site and induce dioxinlike toxicity in animals. The site's geometry g o es a long way toward explaining why the 2,3,7,8-tetrachloro isomer of dioxin is the most toxic, since this is the one that has all four corner positions of the i < t molecule and no others occupied by chlorine atoms. Once bound, the dioxin-protein complex moves into the nucleus where it turns on the activity of a specific set of gen es called the Ah {for aromatic hy drocarbon) locus. These genes, in turn, produce messenger RNAs that direct the synthesis of a family of proteins called cytochrome P-450s within the cell. Cy tochrome P-450s are enzymes whose function is to react with foreign mole cules like dioxin so they can be metab olized and eventually excreted from the body. ' Li' - To this point, the system seem s to be a beneficial one for the cell. Unfortu nately, among the metabolites of dioxin as it is processed by the cytochrome P-450 system there seem s to. be a sub stance that is toxic. Inadvertently, a system that was intended to rid the body of foreign chemicals by making them easier to excrete has converted a fairly innocuous substance into a toxic one. It now seem s apparent that this whole process is controlled genetically at two points, at least. One of these is the Ah locus, which controls the amount and structure of the receptor protein within the cell and turns on production of the cytochrome P-450s. Experiments in mice have shown that genetically inbred strains that do not have the Ah locus are not susceptible to som e of dioxin's toxic effects. But the Ah locus alone is not enough to produce toxicity, as is shown by experiments in which cytochrome activity is turned on by the presence of dioxin though there is no toxic response. Poland and Knutson have found that chloracne can be produced by dioxin in a certain strain of hairless mice even though mice generally do not show this reaction to dioxin, it is not the lack of hair itself that is responsible for chlor acne in these mice, they find. Instead, som e part of the genetic locus that is responsible for the hairless trait in mice is also necessary to produce the chlor acne response. It is interesting to speculate on why animals have evolved an elaborate system for dealing with foreign chemi cals and why it som etim es goes awry ~with molecules like dioxin, making them more, rather than less, toxic to cells. One model that satisfies pharmacolo gists considers dioxin to be a foreign molecule that just happens to fit Into a receptor and turn on a cell system originally designed to respond to an endogenous molecule and that once had som e useful purpose. Such a model makes dioxin analogous to morphine, which stimulates a natural pain-killing system in place of the body's own trigger m olecule-- enkephalin. But to have dioxin fit a similar pattern, there would need to be a structurally related compound naturally present, at least on occasion, in the body. There also would need to be som e advantage in certain circumstances to triggering the ordi narily toxic responses that the body makes to dioxin. The body's response to dioxin, theo retically, at least, might som etim es be useful. Properly controlled, the ability to stimulate cell proliferation, for example, could lead to useful growth or repair of tissues instead of cancer. So far, how ever, a natural dioxinlike molecule has not been found in animal tissue. Useful as this picture of dioxin's role in cellular biology is, it does not explain all the chemical's toxic effects. Indeed, the model purposely focuses on those effects of dioxin that vary most widely from species to species. But dioxin has other effects, like the wasting away of tissue, that appear to be common to all animal sp ecies examined. Tissue wastage is not a trivial effect of dioxin; it Is probably the cause of death in the very sensitive guinea pig. British studies in the mid-1970s showed that animals recovering from dioxin exposure had unexpectedly high numbers of cells with more than one nucleus, suggesting that perhaps cell membrane proliferation had been im paired by dioxin exposure. This work might provide a clue to the wasting ef fect dioxin has on animals. Certain experiments indicate that som e of dioxin's effects are brought about by such incredibly small doses of the compound that the number of mol ecules in the dose is too small to ac count for the observed effect-- at least in terms of a receptor binding model. In these cases, at least, there seem s to be som e sort of chain reaction that mag nifies the effect of a small dose of dioxin. peared to be healthy, and their abor tion rate, one in four, was about the same as that of the nontreated group, where three abortions occurred in 11 pregnancies. . .. Clearly, dioxin is fetotoxic to some animals and causes birth defects in others. However, its high toxicity to the mother means that the range in which it causes toxic effects on the fetus but not on the mother is very narrow. Thus, some toxicologists classify dioxin as a weak teratogen. Ironically, the fact that humans ap pear to be less sensitive to the acute effects of dioxin means that it could be a more potent teratogen for them than'it seems to be for laboratory animals. ^ 1 Several independent tests in rats or mice show that dioxin is an ex tremely potent carcinogen in these animals. Richard J. Kociba of Dow Chemical's Toxicology Research Laboratory found that female rats fed 10 or 100 ng of dioxin per kg of body weight developed a greatly increased number of liver tumors. At the higher dose level, both male and fe male rats developed increased num bers of tumors in the mouth, nose, and lungs, as well as in the liver. Nearly half the female rats in the higher exposure group developed tumors. When the data on female rats are used to calculate the potency of dioxin as a carcinogen, dioxin comes out to be about three times as potent a carcinogen as aflatoxin Bj, which is one of the most potent carcinogens known. Equally significant, how ever, according to Kociba, is the finding that at doses below 10 ng even the female rats showed no in creased incidence of tumors in this study. He considers this evidence that there is a no-effect level for dioxin-induced cancers in the rat. A similar study conducted for the National Cancer Institute by re searchers at Illinois Institute of Technology found statistically sig nificant increases in thyroid tumors in male rats at all doses studied and an increase in subcutaneous tissue fibronomas in male rats at the high est dose level (0.5 mg per kg of body weight per week). In female rats, the. study found an increase in tumors'of the liver, subcutaneous tissue, and the brain at this same dose level. Besides these two studies there June 6, 1963 C&EN 39 Dioxin Report 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 who somehow have been inadver tently exposed to dioxin, always in combination with many other halo- genated 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 2,3,7,8-TetrachIorodibenzo-p-dioxin is a crystalline solid at room temperature exactly who was exposed to dioxin at what concentration and for how long have been about a half-dozen others in a series of studies by D. L. Berry of often can only be estimated. that provide some evidence that Oak Ridge National Laboratory's bi As with animal studies, the acute dioxin is a carcinogen in rats and ological division, dioxin neither in effects of dioxin exposure are the mice. Although some of these other itiated nor promoted carcinogenicity easiest to establish. Most of these data studies have methodological flaws when administered along with come from industrial accidents in that make them less definitive than polycyclic aromatic hydrocarbon which a fairly small number of either the Kociba or the NCI study/ a carcinogens. Instead, it appeared to workers received a single exposure to panel evaluating the carcinogenic block the effect of these carcinogens dioxin. There have been more than potential of dioxin for the Environ in mice. 800 reported cases of this type of ex mental Protection Agency in 1981 Dioxin's chemical structure posure. In addition, some 37,000 concluded that collectively these suggests that it could intercalate into people may have been exposed to studies support the conclusions of DNA as several carcinogen initiators measurable amounts of dioxin when the Kociba and NCI studies and pro are believed to do. However, exper a 2,4,5-trichlorophenol-manufac- vide strong evidence that dioxin is a iments designed to show such inter turing reaction went out of control at potent carcinogen in animals. action have, so far, given only nega the ICMESA chemical plant near Most chemical carcinogens tend to tive results, possibly because the Seveso in northern Italy. More than attack specific organs and produce molecule is so highly reactive with 500 residents of nearby towns were large increases in one particular type cellular proteins that it is not actually treated for what were presumed to be of tumor. Dioxin produces many available to react with DNA. The toxic effects following the accident. different tumor types in different highest estimate of the degree of co Thus, Seveso stands out as the single organs, which has led some re valent bonding of dioxin to rat liver most important industrial accident in searchers to speculate that it may be DNA in vivo is less than 1 molecule terms of the information it can pro a promoter/ rather than an initiator, of of dioxin per 1011nucleotides, or four vide about the human health effects carcinogenicity. In other words, to six orders of magnitude less than of dioxin. dioxin might not actually be re what is found for most chemical car By far the most significant finding sponsible for tumor formation, but cinogens. from the Seveso data and those of the might instead work in some way that As is almost always the case in other industrial accidents is that hu makes the cells more receptive to dioxin research, the interpretation mans are much less sensitive to the tumor formation if some other acti given to these and other animal test immediate toxic effects of dioxin vating agent is present to begin the findings depends very much on who than are guinea pigs. So far, there has process. is making the interpretation. To Dow been no clear case of a human death Several studies have been de Chemical's director of biomedical caused by dioxin exposure, dis signed to consider this possibility. research, James H. Saunders, the an counting voluntary abortions that One, by Henry C. Pitot and cowork imal data show that dioxin is a pro were performed following the Sev ers at the University of Wisconsin, moter, but not an initiator, of carci eso accident. There are, however, examined the effect of dioxin on rats nogenicity in animals. The EPA car many well-documented toxic ef that already had been exposed to cinogen assessment group, on the fects. another carcinogen, diethylnitro- other hand, says that since promoters The bellwether of these acute ef samine. Animals receiving both generally do not produce the large fects is thought by many epidemiol substances had a greatly increased increases in tumor formation when ogists to be chloracne, a skin condi incidence of-liver tumors compared given alone that dioxin-produces, t i o n in' which circular patches of to those that received dioxin alone, dioxin should be regarded as both an blackheads and pale yellow cysts suggesting that dioxin can be a pro initiator and a promoter of carcino develop on the face and, in more se moter of carcinogenicity. However, genicity. 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 1 ~ D ate 1949 1953 1956 W orkers exposed Location of accident 250 Monsanto's 2,4,5-trichlorophenol plant at Nitro, W.Va. 75 BASF's 2,4,5-trichlorophenol plant at Ludwlgshafen, West Germany ? Rhone-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 1963 1964 106 NV Philips' 2,4,5-T plant In Amsterdam, the Netherlands 61 Dow Chemical's 2,4,5trichlorophenol plant at Midland, Mich. 44 chloracne cases (42 severe), of whom 21 also had internal damage or central nervous system disturbances; 6 deaths so far (6 possible myocardial infarctions); some symptoms of fatigue; full report planned . . 49 cases of chloracne; deaths so far 4 vs. 7.6 expected, 3 cancer deaths vs. 1.5 expected, one a soft-tissue sarcoma; studies continue a:-.:. - -1 x'm 1965-69 1966 ;78 ? Continuing leaks in 2,4,5- -1- trichlorophenol processing area of Spolana's 2,4,5-T plant near Prague, Czechoslovakia - Rhone-Poulenc's 2,4,5trichlorophenol plant in Grenoble, France 78 cases of chloracne; so far 5 deaths; 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 21 chloracne cases * < ; - - .<3 .r:C 1968 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 1976 156a ICMESA's 2,4,5-trichlorophenol 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 I a In addition to these ICMESA workers, some 37,000 residents of 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 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-Sevescfseems '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 subjects were exposed to phenoxy herbicides was made by asking them 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 people in one study apparently were exposed to products that contained much lower levels of dioxin than those in the other study, but both groups showed the same degree of increased risk. Such data suggest that some factor other than dioxin might be responsible for the elevated cancer risk. Finally, there is a problem with the identification of the tumors as soft-tissue sarcomas. Because this is a rare cancer type, most pathologists have very little experience in iden tifying it. It is, to some degree, a classification that is used for tumors that don't fit into other, more clearly definable categories. Hardell relied on medical records to identify the sarcomas; he did not examine the tissues himself. Nevertheless, the Hardell studies cause concern, and that concern is increased by early results from studies of Monsanto and Dow Chemical workers who were exposed to dioxin in separate industrial acci dents in 1949 and 1964. Altogether, 182 workers from these two incidents are being monitored. By 1979, 36 of these workers had died, fewer than the 54 that would have been expect ed based on national mortality sta tistics. However, three of the people who died had soft-tissue sarcomas, and a fourth, who has died since 1979, also had soft-tissue sarcoma. For a form of cancer with a predicted in cidence of less than 1%among cancer victims, finding four in such a small sample is unexpected. "It certainly raises the question as to whether there is something there," says Dow's Saunders, "but, [although] it is sta tistically significant, there is always that uncertainty of what would have been the luck of the draw in a sample this small." Examination of death certificates and hospital records for Midland County, Michigan, where Dow's plant is located, also shows an ele vated incidence of soft- and connec tive-tissue cancers among women in 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 j'udgment at this point that there is a clear link [between dioxin exposure and incidence of soft-tissue sarcomas in humans]," Saunders says. "It is a question that merits further study. We do not see sarcomas in animals [exposed to dioxin]," he points out. "What we see are carcinomas, [which are] epidermally derived tissue tumors, partic ularly liver cancer, as in the rat. Fur thermore, when one sees cancer in rats, one sees it at a level 10 times that which produces obvious toxicity in the animal. In other words, when one produces liver cancer with dioxin in the rat, one has a very sick rat who is very sick for a long time and then develops cancer." This is very different from the humans who develop soft-tissue sarcomas, he maintains. Other studies do not show an as sociation between phenoxy herbicide use and increased incidence of softtissue sarcoma. One study that ex amined the relationship among people in various occupations in the state of Washington and incidence of soft-tissue sarcoma found that the occupations with the greatest num ber of soft-tissue sarcomas, as deter mined by data on death certificates, were marine engineers and bankers, groups that would not be expected to have had particularly high exposure to dioxins. Allan H. Smith and asso ciates at the school of medicine at Wellington Hospital, New Zealand, are in the midst of a study of the in cidence of soft-tissue sarcomas among herbicide applicators in New Zealand. Because New Zealand re quires herbicide applicators to be registered, records of exposure to phenoxy herbicides are particularly good in that country. In a prelimi nary report presented in 1982, Smith had not found any instances of softtissue sarcomas in this group. The Veterans Administration is putting together a study designed to see if Vietnam veterans, who may have been exposed to dioxin through the use of agent orange in Vietnam, Dioxin's lethality compared to other poisons Substance Botulinum toxin A Tetanus toxin Diphtheria toxin 2,3,7,8-TCDD Bufotoxln Curare Strychnine Muscarln Dllsopropylfluoro- phosphate Sodium cyanide Animal Minimum lethal dose (moles per kg body weight) Mouse 3.3 X 10"17 Mouse , ,, .1.0 X 10-15 Mouse ,4.2 X 10"12 Guinea pig 3.1 X 10"9 Cat 5.2 X 10"7 Mouse 7.2 X 10~7 Mouse J :: 1.5 X 10"6 Cat 5.2 X 10"6 Mouse 1.6 X 10"5 Mouse ; 2.0 X 10-* Source: EPA * *1>f i1< have an increased incidence of softtissue sarcomas. The study, being directed by epidemiologist Han K. Kang, will use data from the Armed Forces Institute of Pathology, which is, in effect, the U.S. center for the evaluation of soft-tissue sarcomas. The institute has on file some 8500 cases of soft-tissue sarcoma, or roughly one quarter to one third of all the cases ever reported in the U.S. The study will examine tumors re ported to the institute between 1975 and 1980 to see if Vietnam veterans are overrepresented in this group. A final report of the study .is expected in 1985. One potential problem with this study is that the latency period for soft-tissue sarcomas is thought to be about 15 years. Since dioxin con tamination of Vietnam occurred in the 1960s, the time period may be too short to evaluate properly what effect dioxin use in Vietnam had on de velopment of this type of tumor. However, by 1980, reports of Hardell's findings were causing pathol ogists to look more closely for softtissue sarcomas, and the researchers chose a 1980 cutoff to remove this bias from their study. In addition to cancer, animal studies raise concern about the pos sibility of fetotoxicity in humans ex posed to dioxin. Several studies and many anecdotal reports of such ef fects in humans have appeared. By and large, however, these studies have methodological flaws that bring their findings into question. One of the most important of these studies, at least politically, involved a group of nine women in the Alsea Dioxin Report Basin in Oregon who lived near for ests that were sprayed seasonally with dioxin-contaminated herbi cides. The women were concerned that 13 miscarriages in their group in the mid-1970s seemed to be linked chronologically with the spraying of the forests. The Environmental Pro tection Agency conducted two stud i e s , one examining just these nine women and a larger one looking at miscarriage rates in that part of Ore gon. Although the first study did not find a statistical relationship between the women's miscarriages and the spraying, the second study did. This ' study played a major role in EPA's decision in 1979 to issue an emer gency suspension against many uses of the dioxin-contaminated herbicide 2,4,5-T. .However, the study did not stand up to critical evaluation. A team of University of Oregon researchers in 1979 panned the study on practically all counts. Among other things, they found that the study did not have a proper control, its data both on mis carriages and on 2,4,5-T spraying were inaccurate, there were many other factors besides 2,4,5-T spraying that varied among the three groups examined, and the variations in the levels of miscarriages reported by the study were well within expected ranges. Poorly designed or conducted studies seem to plague the effort to Dioxin's lethal dose varies in different species0 * Animal ' r' ^ LD50 (*<0 per ,' V. - -k g body weight) - "Guineapig' Ra (male)' . "* 1 *>- ^ -2 2 :' . i Monkey V R a b b lt^ r ; i,; ^ Mouses - 'v* Ooqi/ ^ Z :;p 1>. A >X; >300:;if.. * i; : Bullfrog j Y <i'? '- 7 ; Y>500; --'-/'.Li; ri Hamster - t .Y"50OO,:, J Source: Poland and Knutson* Annual Review of Phar- Vmacohgy& Toxicology: I3B2' : ** ' <'J' Y- s ' find out if dioxin causes human re productive effects. At least two Vi etnamese studies, one from the early 1970s and one announced earlier this year, claim to show a substantial in crease in these conditions as w ell as cancer following the spraying of agent orange in that country. How ever, western epidemiologists are uncomfortable with the lack of data on normal rates for miscarriage and birth defects in the Vietnamese population. They also question the way in which the Vietnamese data were collected. Similarly, data from Seveso seem to show an .increase in both the number of spontaneous abortions and in the number of birth defects in the period immediately following Dioxin has different effects in different animals Symptom Mon- G uinea key pig Cow R at Abnormal cell proliferations or organ enlargement Gastric mucosa Intestinal mucosa ++ 0 + 0 + Urinary tract Bile duct/gall bladder Lung Skin ++ ++ ++ 0 . ++ + ++ ++ a 0 Atrophy or decreased cell proliferation Thymus Bone marrow Testicle + + + ++ + + + + Other effects Liver lesions Edema +0 +0 ++ 0 Rab Chick Ham Mouse bit en ster 0 0 ++ o 1 ++ 0 ++ + + .+ ++ ++ + ++ + + ++ + + Note: 0 Indicates lesion not observed; + Indicates lesion observed (number o( pluses notes severity), a Skin lesions are observed In cattle, but they ere different from the lesions seen In other species. Source: Poland and Knutson, Annual Review of Pharmacology & Toxicology, 1982 46 June 6,1983 C&EN the ICMESA accident. However, there is so much uncertainty about what levels should be considered normal for this population that it is unlikely that the question of whether the Seveso incident caused increases in these conditions will ever be re solved. Epidemiologists who think there may be an association between dioxin exposure and these effects call the Seveso data "suggestive" of an effect; those who think that these effects probably don't occur in hu mans point out that the levels were well within the normal range or western countries. There exist, in addition, several studies that do not show any increase in miscarriages or birth defects among populations that might be considered at risk because of their dioxin exposure. Studies of Dow Chemical and Monsanto chemical workers and their wives show no increase in either of these factors. So does a study released last month by the Michigan Department of Public Health that examined the rate of birth defects in Midland County, where Dow made 2,4,5-trichloro- phenol until 1979. A recently released study of the reproductive effects of dioxins on the families of Australian soldiers who fought in Vietnam during the period when agent orange was being sprayed there shows no increase in miscarriages or birth defects among these families. The study is highly praised scientifically, but there is uncertainty as to whether these Australian soldiers received very much exposure to dioxin w hile they were in Vietnam. Consequently, this negative finding does little to allay the fears of those who think dioxin 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 ing--the U.S. government is spend ing more than $100 million on sev eral epidemiologic studies of the health consequences of possible dioxin exposure to veterans who served in Vietnam, and major studies also are under way in Australia, New Zealand, Finland, Sweden, the U.K., ! , ,,i fc 1 Dioxin Report i;! 's u .y 4 i f -j >) and many other countries. Most of the U.S. studies are scheduled to he 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 well 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 w ill 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 will 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 when 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. ^ Dioxin Report Both Incidence, Control of Dioxin Are Highly Complex A by-product of many industrial processes, dioxin presents big problem in w aste disposal; the technology is on hand, but economic, political barriers persist 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 400 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 the 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 back 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. Not 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 ni 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, blown, 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-trichIorophenoI can lead to dioxin contamination 1,2,4,5-Tetrachlorobenzen e Sodium hydroxide Air em issions8 Water Alcohol recycle Toluene plus ^Mixing and impurities ^phase.^lj Distillation' Toluene I$ Wastes8 (still bottoms) Na-TCP in water Conversion8 1(optional) Hydrochloric a c id ^ ^ IS IS Ij i i M ^ ~ ii[l1W i iliT iM [ f i Centrifugation ,, Wastewater8 Air emissions8 Wastes8 (still bottoms) TCP a Potential sources o! environmental dioxin contamination. Source: Adapted from EPA, `'Dioxins1' 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 9 Dioxin Report GO, MS useful techniques in the analysis of dioxin tion MS analysis. The presence and amount of sp ecific isom ers like How does one determine whether and to standard is added to help determine how 2,3,7,8-TCDD then can be determined what extent something is contaminated much sample is lost in later steps, and from the ratios of certain key mass by dioxins? The easy answer is that it's to assist in quantitation. fragments. usually done with gas chromatography The organic extract is cleaned up with With such techniques, and depending and mass spectrometry. But there's a lot another series of washings with aqueous on the nature of the sample, it's possible more to it than that. Normally, dioxins base and acid solutions and distilled to detect and quantify dioxins down to are present, if at all, at levels ranging- water. Then the organic extract under low parts-per-trillion levels with rea from parts per million down to the van goes a sequence of preliminary liquid sonable confidence. In the ca se of a ishing point. They coexist with many chromatographic separations, using a "simple" sample like water, one can go other compounds, and many of these variety of columns and eluents. All the even lower, down to the parts-per-qua- / are present in much larger amounts and fractions from these separations are drillion level, by taking a very large capable of interfering with the anal recombined and concentrated for sample and concentrating the dioxins ysis. GC/MS analysis. into a much smaller volume by solvent Since it's impossible to run a sack of Usually, the sample first goes through extraction. In the case of more complex dirt or a Coho salmon through even the a GC/low-resolution MS system for sam ples, like soils, this approach is most user-friendly GC/MS setup, sample preliminary screening. This can show probably beyond the capabilities of to preparation is an extremely important that TCDDs, for example, are present, day's analytical laboratories. part of the process. The first step is to but it isn't sensitive enough to distinguish All this is terribly tedious, time-con transfer the dioxins (and other chlori among the various isomers. If TCDD or suming, and expensive. A lot of work is nated organics) from the sample matrix other dioxins of interest are revealed by going on to find simpler alternatives, to an organic liquid, by a series of ex this preliminary analysis, the^sample especially for the preliminary screening tractions. An isotopically. labeled internal then g o es to a second GC/high-resolu- steps. - UV light degrades dioxins to less toxic products The basic disposal options for Perhaps the largest dioxin de dioxins are the same as for other struction operation to date involved 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 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 Repori 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 trichiorophenol 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 4600 gal of dark sludge. Analysis showed the sludge to contain 356 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. S o Syntex started exploring the possi bilities of on-site destruction. In 1978 Syntex engaged IT Enviroscien ce 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 wet ox idation, photochemical reduction, and chemical treatment. After extensive evaluation, the photolytic method was chosen, mainly for reasons of safety, sin ce it operated at ambient pressures. This approach required that the dioxins first be separated from the w astes 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 w eeks, with a destruction effi ciency of 99.94% . 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 $500,000. 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 1I I* \ - . Dioxin Liability Is Huge Problem i for Companies, Courts Lawsuits for personal injury are mounting with massive potential compensation; companies 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--w ill 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 i r i Dioxin Report Kloman: producers will bear bulk residents of Times Beach, for in stance, could sue for, among other things, payment for the loss of the use of their property. For companies associated with dioxin--either as producers of chemicals contaminated with it, as users of such products, or as transporters--the possibility of such suits already has been the im petus for the review and bolstering of existing insurance coverage. For the liability insurance industry, which feels comfortable only when it knows today precisely what its compensation costs will be a decade or more hence, the possibility con notes so many unpredictables that the current mood among insurers is somewhere between bewilderment and horror. Chemical companies have to pro tect themselves now, if they have not already done so, against the chance of massive compensation losses. To a great extent, they have taken on that task themselves. But whether they retain self-insurance or establish a captive insurance firm, they ulti mately must go into the traditional insurance market to seek reinsu rance. And though wary, insurance firms are not entirely unwilling to write policies where dioxin might be involved. The insurance industry happens to be, in its own way, in a ..state of overcapacity. They are far more willing now than they were 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 sumably could run its course without ever establishing precedents on dioxin liability. Dioxin-associated firms and in surers, however, are not planning insurance strategies wholly in a vacuum. There are lessons to be gleaned, unpalatable as they might be to industry, from the ongoing as bestos litigation. The thousands of criss-crossing suits among asbestos victims, producers, users, and insur ance carriers touch on a welter of issues that include most of the lia bility problems concerning hazard ous materials. Despite the major dif ference that asbestos' long-term health hazard to humans has been proved and dioxin's has not, analysts cannot avoid detecting potential an alogies between asbestos litigation today and dioxin litigation to morrow. "What ultimately happens in re solving the asbestos claims will be come a precedent of sorts in resolv ing suits in all sorts of toxic problems," comments Rita Epstein, director of communications at the Risk Studies Foundation in New York City. And companies can go to school on more than an implied analogy. The farmer's 2,4,5-T suit is one of more than a score of lawsuits filed in the U.S. in which dioxin is the prime issue. Of those cases, only one major one has passed through the entire 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 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 LABTECH" 70 It's Second To None cians. To industry, an award of this size In R&D M icrocom putermade without proof of dioxin's haz ardousness or even proof of any exposure to the compound raises the specter of a terrifyingly resilient legal Perform ance 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. 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 Today's microcomputers carvfree 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 complete:solution to your real-time, high-speed data acqui* sition, monitoring and control, and sophisticated, number' crunching needs.. We've taken the most advanced VLSI technology and combined it with firsthand experience in chemistry, physics; engineering and other analytical sciences. The result? Compare * foryourselfu 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.*" Analog Data Acquisition Speed Real-Time Multitasking Standard . System Languages LABTECH 70 650 kHz 64 K Tasks FORTRAN77 IBMINSTRUMENTS 9000 30 Hz 7 Tasks BASIC DEC MINC--23 (RSX-11M) 16 kHz 64K Tasks BASIC, 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 Floating Point Hardware Multi-User Menu-Driven Software Included in Basic System CP/M-86 Compatibility Yes (80 bit) IEEE Standard Yes Curve fitting, Graphics, Data acquisition, Networking Yes No No None No Yes (64 bit) Yes None No health disorders. Donald R. Frayer, claims manager in Dow's legal de Slave Processing Yes No No partment, says the company tries to ' settle when the cost can be kept Standard Winchester Yes No No - . 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, will 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, We didn't stop with making LABTECH 70 a powerhouse of performance: We also made it accessible, -adaptable and upgradable,-with hardware and software you can get into, V understand and modify. Take a look at LABTECH 70., If you're involved-in serious analytical research or real-time process monitoring^ you can't afford not to. , Call us at (617) 497-1010 for details or to schedule a Labtech 70" demonstration: Laboratory Technologies Corporation, 328 Broadway,Cambridge,Massachusetts 02139!*: 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 LABORATORY: t e c h n o l o g ie s ; CORPORATION year. CIRCLE 43 ON READER SERVICE CARD June 6, 1983 C&EN 59 t O R G A N IC Dioxin Report IN TER M ED IA TES FROM SW ITZER LAND for* " ,, ; - . ( 'dyestuffs'- perfumes^* ^ pharmaceuticals? flavours*-" ' *v ' -NHj, ,, agrochemicals?- photocherhicalsC 3-Hydroxy-4-methxyaniline ocna 5-Aminoguaiacol.* ' -''F*'-j `j*v''r. . * 1"Chloro~3,4"dinitrobenzene ' NHa :-A ^-'CHjOk^CHa V ;? W : 2,4,6-Trimethylahiline ', ch3 Mpsidine- 4-^ 5-Nitroiso'phthalic acid cooh and derivatives jv- . -* . COOH COOH. 5:hlor-2-nitrbbenzdic cid and other isomrs Tt< ^ , v ` .;v- NHj LOJ cf3 a,a,a-Trifloro-rn-toluidihe 3-Aminobenzotrifluoride ' V s ; 'f Tp . v i , '^ Custom made intermediates against secrecy ag reem ent., .Ourtraditlonalprocesscs:* r r ' - ,N itratio n ^ -. , ... - *. * 1--C ataly tich y d ro g en atlo n a n d o th e r react loner For catalog, samples, technical data please contact: US-Agents: Riches-Nelson, Inc. 254 Mill Street. Greenwich, Conn. 06830 Phone: 203-869*3088 Telex; 6 8 1 9 1 7 ? ricnelinc grc Sam ples for commercial trade only Agents in other countries: Please inquire CIRCLE 38 ON READER SERVICE CARD In the other, Monsanto and Dow on a combination of factors, indue are-being sued by a group of Union ing the size and type of risk and th Electric Co. employees who claim to state of the insurance market. Typi have been harmed as a result of ex cally, most policies fall somewhere i: posure to dioxin while climbing between. utility poles. To the displeasure of the For chemical companies lookinj two companies, the case was filed in for protection from future dioxii the same court that handled the suits, there is little chance of finding Lowe vs. Norfolk & Western case by an independent insurance carrie: the same attorney, the now-notorious willing to underwrite an "occur Pratt. For this reason, notes Dow rence" policy providing coverage 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 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 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 clear a deductible of about that size that who should be liable for the victims' mitigates the risk of the carrier and compensation. Three court rulings covers the insured against cata 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 "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 period of insurance, the insurer pays. Marsh & McLennan. "He might be To a certain extent, this form makes willing to write it at a price--that the 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 surance firms prefer it. ing it away." But insurance buyers are no fans of "It's a shot in the dark," remarks claims-made policies. What they Risk Studies Foundation's Epstein. want is a "tail," insurance industry 'The industry is in a state of flux, and 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 w ill 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 made or shows signs of a tail depends the producers." 60 June 6, 1983 CSEN Europe Provides Test Case o f Human Exposure to Dioxin Severe disaster of 1976 has had profound impact internationally on waste disposal standards, production of chem icals, liability laws, 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 1976 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 Societ, 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&EN 61 Dioxin Report was adjourned until May 11. On May had arrested and jailed the president 11, a strike by lawyers forced a sec-' of Spelidec for failing to declare the ond postponement until June 17. The contents and destination of the lawyers called the strike to press the dioxin wastes, which his firm trans government to provide more court ported to St. Quentin--and for fail staff to speed up proceedings. ing to divulge their whereabouts That court action is being joined by after that. several others. In Switzerland, for And during the height of the furor example, Hoffmann-La Roche is fil over the missing wastes, the archac ing suit against the West German tivist environmental group Green industrial firm Mannesmann A.G., peace blocked border crossings that with whom it had contracted to dis might be used to ship the wastes, in pose of the dioxin waste, an estimat cluding one into a potential disposal ed 2.5 tons of contaminated soil. site in East Germany. Mannesmann, in turn, subcontracted West German protests, in fact, in the disposal to the French firm directly have caused Boehringer In- Spelidec--and the waste then dis gelheim, which produces 1000 tons appeared. per year of the herbicide 2,4,5-tri- The Green political party in West chlorophenoxyacetic acid (2,4,5-T) at Germany already has pressed charges Hamburg, to get out of the business. against Mannesmann and the West Last month, it stated that it had German representative of Hoff stopped producing the herbicide, mann-La Roche, in an attempt to primarily because of the controversy force disclosure of what happened to over dioxin and dioxin disposal. the wastes. And, in part prompted by For Europe, Seveso has the same a European Bureau of Consumer umbrella connotation of pollution as Unions boycott of all products made Love Canal in the U.S. There have ICMESA's Seveso plant during toxic by Hoffmann-La Roche, physicians been other industrial exposures in material cleanup after 1976 accident in West Germany reportedly have Europe besides the accident at the 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 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 Italian police guard one entrance to Seveso following evacuation of area the type of waste, the identity of the 62 June 6.1983 C&EN < 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 FOR B.E.T/ s u r f a c e a r e a a n a l y z e r s :arsae**-'----- R Ki V Vi ' i <"i i W ..MORE LABORATORIES ' PURCHASE THESE * INSTRUMENTS.TH A N ^ -c & M - ....S..a..f.t.'.....5- r' fl ?W N YvTHER^:',--' vok1 r lW L t'C MODERN, RELIABLE DYNAMIC FLOW used by both instruments with any non-corrosive adsorbate. No ideal gas corrections or void volume *-' measurements required. Extreme sensitivity for a r, V Q UANTASO RB - ! wide range A very fast,.accurate * of applications. and versatile " 4 _instfumeht for surface ^ " `. area/pore size ---------, -v . , ByTar the world's fastest and most . ` distributions;, adsorption and; versatile single point B.E.T. surface1 ^ ^desorption isotherms!, r ; .area analyzer/Direct digital *7 /' ' .,i! * ' / _ > ideal for measuring, * readout of surface area w itlr 7 . / / ) chemisorption uptake.; . extreme simplicity and accuracy/ \ , *. 1 h - monitoring and other ".quality control " * L' ; / - applications! J ^ Q U A IU T A C H R O M E 77-7=1 c o r p o r a t i o n , powder instrumentation - :\A Six Aerial Way, Syosset, NY 11791 /%/ ! ,TWX: 510 22T2239 TEL: 516 935-2240 *K CIRCLE 33 ON READER SERVICE CARD # H IT A C H I SCIENTIFIC1NSTRUMENTS HITACHISCIENTIFICINSTRUMENTS Nissei Sangyo America, Ltd. SPRINGCLEANINGSALE 460 E. Middlefield Road Mountain View, CA 94043 We are cleaning out our closets of demonstrator equipment at incredibly low prices! For example: SINGLE BEAM UV-VIS SPECTROPHOTOMETERS LIST p RiCS SALE PRICE Model 100-20 Digital R eadout Model 100-40 Digital R eadout $2850 4120 $2300 2500 DOUBLE BEAM SPECTROPHOTOMETERS Model 100-60 (Manual) Model 100-80 (Computerized) Model 110A Variable slit com puterized Model 2 2 0 High R esolution ZEEMAN AA Model 180-80 Flame Furnace Model 170-70 Furnace $ 6240 10200 11950 14950 35000 19600 $ 3200 7000 9950 11960 27000 13000 HPLC Isocratic HPLC S ystem UV D etectors (variable w avelength) 9000 5000 7200 3975 And m ore! Call any of th e following c o m p a n ies In your a re a for m ore details. ANALYTICAL SOURCES Covington, KY (606) 431-3954 BAY STATE ANALYTICAL PRODUCTS Franklin, MA (617) 528-8739 DANA SCIENTIFIC Dana Point. CA (714) 495-0492 GK INSTRUMENTS Montevallo, AL (205) 655-7128 HILTECH Albuquerque, NM (505) 268-1733 LEE SCIENTIFIC Houston, TX (713) 460-3337 MOORE ASSOCIATES Richardson, TX (214) 690-4929 PETERSON ASSOCIATES. INC. Nutley, NJ (201) 235-0241 SOUTHEASTERN ANALYTICAL Roswell, GA (404) 998-7870 SPECTRA-CHROM INSTRUMENTS Gaithersburg, MD (301) 428-9072 THOMSON INSTRUMENT COMPANY Newark, DE (302) 368-8616 VARITECH COMPANY Santa Clara, CA (408) 248-2946 WESTLUND TECHNICAL SERVICES W est Jordan, UT (801) 968-6861 NISSEI SANGYO AMERICA, LTD. Mountain View, CA (415) 969-1100 New York, NY (212) 755-2900 Gaithersburg, MD (301) 840-1650 Rolling Meadows, IL (312) 981-8750 Torrance, CA (213) 328-9700 All p ric e s FOB shipping polm ta x e s a nd freight e x tra , all Instrum ents c arry a 6 m onth w arranty a nd a re su b jec t to prior sa le , (T he quantity Is lim ited). CIRCLE 48 ON READER SERVICE CARD June 6, 1983C&EN 63 Giulio Natta Dioxin Report Present significance In countries on the Continent, That is welcome news to many of of his scientific contribution 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 Rhne-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 Sergio Carra, Federico Parisi, Italo P asq uon , and Piero Pino, Editors 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 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. material, Rechem is the only com pany with the appropriate disposal facilities in the U.K.," agrees Arthur Coleman, managing director of Re chem, That's a hypothetical assump tion, he emphasizes. Coleman echoes Giles Shaw, an official in the U.K. Department of the Environment, who said earlier this year in a state ment to the House of Commons that "in principle" the dioxin would be a most unwelcome import were it sent asking our TGU colleagues--the lorry drivers, port workers, and oth ers--to not handle, to block it," Kaufman says. Wouldn't it be better, in the long run, to incinerate the dioxin, ending the saga once and for all? "From our viewpoint, there are no guarantees that the incineration process is safe," says Kaufman. "Within the furnaces there are eddies and currents--it doesn't ensure that the whole con CONTENTS to the U.K. "We are not interested in signment will go up and be safe." The Human Personality of Giulio Natta {A. Quilico) Natta's Work until 1949 (R. Rigamontl) The Scientific Activity doing the work," says Coleman, be Besides, he adds, "Our workers are in cause of the tremendous emotion that plant. We don't want them to be of Giulio Natta from 1949 to 1973 (P. generated about that possibility. exposed to the material. We can Pino) Chemicals and Fuels from Synthesis Gas (/. Wendei) Recent Advances in Heterogeneous Catalysis "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." (G.A, Somorjai, P.R. Watson) Synthetic Hydrocarbon Rubbers {M. Bruzzone) The Role of the Discovery 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 and Investigation of Stereoregular chem's position. "We have demon representation on the advisory com -? Polymers in Macromolecular Chemistry (P. Corradinlj Some Aspects of the Mechanism of Stereospecific strated disposal of dioxin, with in mittees that recommend licensing or dependent checking of emissions. not licensing pesticides to the gov Polymerization of -Olefins [A. Technically, we have the capability. ernment. The present advisory Zambeth) Stereospecific Polymer ization of Dienes: Achievements and Perspectives (L. Porr^ Asymmetric It comes down to individuals, emo committees "contain no representa tions, and so on, in spite of anything tives from workers, who are directly Polymerization (M. Farina) Conforma tions and Dynamics of Macromolecules ( G.Allegra) Olefin Metathesis (V. Chauvin) w e 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 This volume is published under the auspices o f the Italian Chemical Society and the Italian National Council for Research Published by the Editrice di Chimica Sri 232 pag es (1982) Paperbound ISBN 88-85034-02-0 US & C anada S19.9 5 Export S23.95 bitter lesson about that. A number of years ago, it was ready to accept Kepone wastes from Virginia for in cineration. Public outcry forced the company to abandon the plan. "It took us many years to overcome the Nature Conservancy is on it--the committee can protect bees, but not people." The unions also want assessment of pesticide safety taken from the Ministry of Agriculture, Fisheries & O rder from: A m erican C hem ical Society D istribution O ftice 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. stigma and aggravation that left us," says Coleman. "Forty-one barrels is a very insignificant commercial op portunity--it would not be worth the aggravation it would cause us. We're Foods and given to the Health & Safety Executive, a sort of British version of the U.S.'s Occupational Safety & Health Administration, with statutory requirements for li just not interested in the business." censing. 64 June 6. 1983 C&EN