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7: * URL 04726 -fc. I *jkm*iQn,+tem Vwyhpvripsrtedtoti liaueatoflndtadMdual toner* *Mh IGuft eggs exposed to the pesticide'DOT.UJavete tT Bftfe found In tie environment In 4mnsfty ttWa'indeed to mete gulls with abnormal development - -ovarian tissue end ovtouctt.^aeyD. Tdichasl fry end C. ** -KueWer Toone of the University of Celifomla, Davis [Science, 213, 622 0991)1- Such femlntaation of male bird embryos affects reproductive behavior of these birds when they mature, the researchers say.' tissue to*T**es at * #art+er. apa tat contalnedtbe compounds tewefof spout 3-ppb and tea seal fatatab Paofeapa .ohps jp *\e two species were ^ idea) *nd suggest to the researchers that xtetxrceof the compounds Is probably direct contaml-' L---- \ . - *;,y ^oation by polychlorinated biphenyls (PCB's). They suggest fiat male gulls exposed to DOT os em bryos may be less likely to migrate to bleeding colo nies--explaining the markedly skewed sex ratio of adult birds that is observed on Santa Barbara island Education ChM named to anglnooiinB faculty project Insects may team to respond to pheromones An insect's response to pheromones may be teamed to some extent, say researchers Bernard D Roitberg . end Ronald J. Prokopy of the University of Aivtoerst -[Nature, 292, 540 (1981)]. They have studted female, -epple maggot files. These fHes deposit a pheromone an ihe surface of fruit in which they have tekf eggs to . A manager for ihe engineering faculty shortage .project of Ihe American Association of Engineering _ ' Societies has been named by the American Society . *sef Engineering Education, which is performing the ^two-year project for AAES. He is electrical engineer - .-~4ohn W. Sells, currently director of the network de sign division at American Telephone & Telegraph. Pella wtii become a staff executive of ASEE Sept. t. -vfThemajoremphasis of the project is to develop a fcm .'? I? -*feeep other flies from depositing eggs In the same data base upon which solutions to the crisis In ehgi- iutt. However, the researchers And that female* lhat ertucaflonoan be.deveioped, with special em- : have never been exposed to pheromone-treated fruit ^are not Inhibited by tt; tt Is edy after antettta! encoun- ... sterthat they avoid pheromone marked frolt. 'Thb - ^^ '`-YT*.' o-j n rotaintog-do* ctoral degree engineers in iap' , -/rJjs'.ar.-v^i.fj,', . \r .r ... / : ^^mechanism may provide flies with a means of redu> - :r" Jng the ooet of continually mairttaintng an imuaed kv formation processing system," ^ toe iracnnology j&v *. * AC ivv* .. , ,. 1: . iV.. ? f rftaturaMy occurring toxins found In parsnip t\' ?'. ^hacanipe, and perhaps othar rotated vaoatahNp nrh! Paltry endparetey, mntjiln apprecaabte tevate ef f-v v :V -./t#ree phototoxic, mutagenic,-endghmpcwflrtepwnic F- - '^-chemicals that are not dertmyed by nongal cooking. wpronedureB, according to Qagpyna tetg agd rtnwnrk-tfe C^rp.'ajtosphotusiohemlcate divisionhas beep ' <U^S.4^32,260) foruse sodbt iteeenj thalt dhteary sodium compoutos. iskturnstaoces, I'm t^AwdimMMasaTteas been mcot^Btuncii - > iir niriw~ URL 04727 276 On the basis of the data obtained, the agency concluded that PCBs do not pose an imminent threat to homes using natural gas. The letter to transmission companies directed the firms to take steps to assure proper disposal of any contaminants found and to prevent further contamination from entering their systems or other systems they connect with. Transmission Company Reports EPA said it first wanted reports from the companies on the amounts found, where they were located, how workers would be protected from them, and how the companies would handle, mark, store, and dispose of them. Next, the agency asked firms to report "all possible alternatives'' for preventing the movement of PCBs into other pipe systems: estimates of the cost, effectiveness, and time needed for each alternative; an assessment of the feasibility of each method: and a discussion of the exposure potential from each method. With that data. EPA said it would discuss with each firm the best method to put into effect. Once a method was agreed upon, the agency said transmission companies should report the time the plan would take to be put into operation, and other data such as worker safety procedures, disposal procedures, and procedures to monitor the effectiveness of the method. The agency additionally asked companies to report data on sources of the contamination and how it could be eliminated and monitored. If companies did not remove all contaminants from their systems, the agency directed them to submit yet another report on the length of pipe still contaminated, an estimate of the concentration of PCBs in the pipeline condensate, and a description of all possible methods for removing it. EPA asked that companies report within two weeks of receiving the letter when they would be able to submit all the required information. Contacting Distribution Companies The agency also asked regional offices to contact local gas distribution companies about developing procedures to locate any PCB contamination, determine its health hazard, prevent its movement or remove it. and possibly monitor the ambient air in customers' homes for indications of contamination. EPA headquarters said the regions should "use their best efforts" to bring all gas distributors into the monitoring and cleanup program. The kinds of distribution companies EPA said should participate in the program were those that had compressors or any other equipment that "could be the source of PCBs.'' those that fogged their systems in the past, those that were supplied by a transmission company that had detected contaminants in its feed lines, and those that served a "substantial population." "Substantial populations" were defined as portions of large cities, medium-sized cities, and "several rural counties " Although the letter to regional offices set forth recommen dations for having distribution companies report different kinds of data, the cover letter said the guidelines "are meant to be flexible." In some cases, headquarters said, no cleanup would be necessary It added, however, that if "any PCB exposure is found to be occurring above background levels.' EPA could "require immediate action to remove the hazard, including extensive measures, if necessary." CHEMICAL REGULATION REPORTER Raaaarch NI08H BEGINS REPRODUCTIVE STUDY ATGHEMtCAL MAMUFAr turint; pi amt----- " The National Insti ute for uc 'al Safety and Health is conducting a heah. hazard evalu of workers at a West Virginia plant whi manufactures :oluene diamine and dinitrotoluene, two c - emicals produced at a Kentucky facility where reduced sperm counts among workers were found earlier this year. Richard Ublar, an industrial hygienist with the Internation al Chemical Workers Union, told BNA that his union requested the new study at the Allied Chemical Co. plant in Moundsville. W. Va., after learning of the results of the earlier investigation. In that study, workers at an Olin Chemical Corp. facility in Brandenburg, Ky., were found to have significantly reduced sperm counts as compared with workers not exposed to toluene diamine and dinitrotoluene. The earlier study said the findings could not be considered '`conclusive'' in showing a reproductive effect from the two substances without further information, but at the same time it said the data should not be dismissed as insignificant (Current Report, March 20, p. 1601). Steven Ahrenholz, the NIOSH project officer for the study, reported that the institute hopes to complete data collection by mid-July. After that, it will decide what further action to take, he added. The Allied plant is "fairly similar" to the Olin facility in Kentucky, although the Allied plant, in addition to producing toluene diamine, also uses it on-site to manufacture toluene diisocyanate, the researcher said In requesting the study, the union "wanted to see if there were any particular problems" among the Allied workers in view of the Olin investigation results. Uhlar told BNA. The union also requested health hazard evaluations at two other toluene diamine facilities -- an AmericanjCyanamid Co. plant in Bound Brook. N.J., and a Mobay Co. facility in New Martinsville. W. Va. Lead COST/BENEFIT TERMED INAPPROPRIATE FOR EVALUATION OF CURRENT STANDARD The concept of cost/benefit analysis "is inappropriate for an agency designed to save lives" and is an "infeasible technique" for the Occupational Safety and Health Adminis tration's decisionmaking purposes, according to the United Steelworkers of America. Further, the International Association of Machir hs argued that such an analysis is neither implied in the Occupational Safety and Health Act nor suggested by legislative history and "constitutes a transgression of congressional prerogative." These comments were submitted to OSHA in response to its April 21 announcement that it was reopening the rulemaking record to conduct a cost/benefit analysis and was requesting comments on the economic and technological feasibility of provisions of the lead standard (Current Report. April 24. p. 93>. However, if OSHA decides to go ahead with the analysts, the Steelworkers want the agency to follow rulemaking procedures, making sure to publish its initial determination on the protocol it plans to use OSHA should conduct its cost benefit study from the view of the affected workers rather than the employer, should use its subpoena power to get the cost data it needs from industry, and in the event the 6-19-81 Copyright C 196i by Tht BufMu Of National Affairs Inc <m8-7S73/1/SOO so Books URL 04728 Coping ineffectively with an environmental disaster "All the relevant institutions of de mocracy failed. Rather than working for the public good they operated, Events following the individually ana collectively, against it--not out of malice, but simply be tragic contamination of cause this was an event outside their experience and beyond their bud Michigan farms with PBB getary means to resolve." With these succinct--yet sympa are spelled out in a thetic--statements, Joyce Egginton introduces her account of the acci clear and balanced account dental contamination of livestock and people in Michigan by polybrominated biphenyls (PBB). In "The Poisoning of Michigan," she has crafted a concise and sensitive report "The Poisoning of Michigan** by Joyce Egginton, W. W. Norton & Co., New York, 1960,351 pages, 113.95 of the actions taken by individuals and organizations to identify the na ture of the problem and assess its scope, to control the spread of the pollutant, to evaluate damage to life and property, and to counteract the economic and health effects of this episode. For the student of environ mental health, this book can serve as the best available chronicle of Mich igan's PBB affair. It provides a clear perception of the etiology and pro Reviewed by laadore A. Bernstein, pro fessor of biological chemistry at tke University of Michigan's medical school, professor of environmental and indus trial health in its school ofpublic health, and associate director for research for its Institute of Environmental & Industrial Health. Bernstein headed a scientific panel that advised the governor of Michigan following the 1973 PBB con tamination there gression of the contamination and the steps which must be taken to mini mize chances of repetition. The first part of the book covers cations of the incident in the farm the story from late spring in 1973, areas of the state. By the time the when Michigan Chemical Corp. re contaminant had been identified, it sponded to an order for magnesium had permeated through most of oxide by erroneously shipping PBB (a Michigan. The contamination was far commercial fire-retardant mixture) wider than anyone imagined. to the Farm Bureau Services' feed mill Each party dealt with the situation near Battle Creek, to April 1974, according to its own perceptions of when PBB was identified as a con the problem and in its own best in taminant in feed on a dairy farm terests. The Michigan Department of whose milk production had decreased Agriculture (MDA) attempted to be precipitously. It chronicles the per the quiet eye at the center of a hurri sistent efforts of one farmer to obtain cane which kept increasing in inten the assistance of various state and sity as the broad geographic scope of federal institutions in explaining the the contamination became apparent. "plague" which had enveloped his Other state agencies kept a low pro livestock. Milk production had file. The federal Food & Dmg Ad dropped 60%. Cows were ill. Some ministration saw the issue as pri died. Although dedication and per marily a state problem. It did set what sistence ultimately triumphed, the it considered a safe "action level" for story emphasizes the nearly insur PBB above which contaminated farm mountable obstacles an individual products could not be sold. This level faces in confronting the various in was based upon estimates of the tox stitutions of our complex society. icity of PBB. Insufficient information The second part concerns actions was available to be certain. MDA en taken by the various government forced this ruling. agencies and the companies involved It was to everyone's advantage to to define the extent of the contami play down the entire affair. Farmers nation, to limit its spread, and to deal whose herds were affected preferred with the economic and health impli- not to broadcast their plights, fearing that their economic positions and their reputations would suffer. Companies found it expedient to deal quietly with insurance claimants one by one. Government agencies hid behind their duties as regulators, professing not to have the resources to obtain new pertinent information. Universities claimed to have no money to do the necessary research. The possible effect of the contam ination on the urban population of the state was generally ignored. At tention was concentrated initially on farm families. The episode was con sidered to be a simple agricultural problem that would be resqlved by routine action. The legislative, and executive branches of the state gov ernment appeared to subscribe to this view. Although not ignoring the sit uation, neither responded en thusiastically to requests for addi tional funds or new initiatives. The right of farmers to be reim bursed for damages resulting from contamination of their livestock at concentrations of PBB above the "action level" set by FDA was never disputed. Both Michigan Chemical and Farm Bureau Services had in surance to protect themselves against liability in such incidents, and ex tensive payments were made to owners of quarantined livestock. The episode became controversial onlyover what to do with livestock that had detectable levels of PBB below the "action level." Some of these herds also were quarantined by MDA. The third part of the book deals with the controversy over disposition of animals contaminated at low levels and with the question of possible ef fects of PBB on human health. Should the "action level" be lowered by the state government? What risk to the consumer's health would result from ingestion of food products con taining low levels of PBB? Unlike most other facets of the episode, this aspect gained widespread public in terest in the state and became known beyond the borders of Michigan. Various influences heightened the public interest in this issue. For farmers who were considering the sale of animals that were contaminated at low levels, moral and economic questions had to be faced. Studies of "low-level" animals carried out at the 12 C&EN Fab. 16, 1981 state's agricultural university and outside the state failed to show ab normalities related to low body bur dens of PBB, but charges surfaced that the studies were not impartial. For the nonfarm consumer, the possible effects of long-term retention of PBB in body fat was a consider ation in deciding whether to buy Michigan farm products. For new mothers who were breast-feeding, there was a concern over the possible effects on their babies of transferring PBB in the milk. Of mothers in the lower peninsula of Michigan, 90% had detectable levels of PBB in their milk. Aware that they would be subject to further liability if Michigan offi cially lowered the "action level" for PBB and thereby legally devaluated animals with levels of PBB below the national "action level," both com panies lobbied against its doing so. An upcoming election made politics a factor as attempts were made to blame the state administration for "covering up what two corporations were doing to the people of Michigan" and for "telling farmers to sell sick cows to the public" so that their farms would be saved. The final chapters describe the manner in which the "disposition" question was resolved and the social, economic, and political forces that influenced this resolution. The "ac tion level" was lowered by legislative action. The issue of whether a body burden of PBB is detrimental to human health is also discussed Iron ically, this latter question received a "definitive" answer only in the courts, where a judge stated that "in small amounts, PBB is not toxic." From a scientific point of view, this question is still unanswered. Some of the farm families who owned "high-level" animals and who themselves had high body burdens of PBB in their fat depots were not visibly ill, whereas some individuals with relatively low body burdens of the chemical mixture claimed health problems that could be caused by residues of halogenated hydrocar bons. It has not been possible to de fine a dose-response relationship be tween the level of PBB in the body and the state of health--a basic re quirement for relating an environ mental chemical and a toxic response. This state of knowledge, of course, does not support the conclusion that PBB impairs health or that small amounts of PBB have no toxic effect. It is entirely possible that the wrong parameters have been compared. Joyce Egginton, New York corre spondent of the Observer of London, obviously spent a great deal of time and effort in researching the subject and in formulating the text. Charac ters who played key roles in the drama are realistically and dis passionately described. The clay feet of the heroes are occasionally ex posed, but no one is painted as all bad. The author tries to present each event within the perspective of its time, place, and relevance. This is in sharp contrast with the more emotional presentation of the story in "PBB: An American Trage dy" by Edwin Chen (C&EN, April 21, 1980, page 54). Chen's book concen trates on quotations from the various protagonists to highlight the charged atmosphere in which individuals and institutions tried to cope with the problem. He provides little perspec tive from which to judge indepen dently the propriety or effectiveness of these attempts. In Egginton's book, scientific ma terial is presented at the level of the layman but with the objectivity ex pected by the professional. The in advertent misspelling of one chemical name does not detract from the aura of reliability that the scientific in formation exudes. Items of human interest are dis persed throughout the book, but only occasionally do they appear to cloud the author's generally critical evalu ation of the matter being described. One such lapse involves the un equivocal statement that "one Michigan general practitioner came up with a correct diagnosis" of human toxicosis from PBB. Although the physician believed that his diagnosis was correct, he never provided data to support his contention. Even today, no such data are available. These vignettes of human activity do serve to remind the reader that the story is about individual men and women, as well as about corporations and institutions. Actions taken bv particular people in accord with their personalities, prejudices, interests, and education influenced the course of events. It was a farmer with a master's de gree in chemical engineering and in dustrial chemical experience who led the effort to identify the contami nant, which had been fed in largt quantities to his dairy herd, but who did not support the later efforts to keep "low-level" animals from the market. He concluded that consum ing the meat of such animals posed no risk to the consumer. Some scientist* and physicians allowed their concern for the public welfare or for the in stitutions they represented to affet-. their professional wigments. As a consequence, their renouncements lost credibility, Most important. people with in adequate educatior and with little understanding of tt* importance of their jobs were invo'-ed in the erro neous shipment fron the chemical company to the fe*v suU and in the introduction of the #rroneous mate rial into the feed miwf Interestingly, the chemical worke>' union is re ported to have disci*-med responsi bility for the erroneous shipment since its members w** on strike be tween Oct. 5 and 1973, during which time the a<on considers the shipment to ht'* been made. Shipping records, tv*ever, indicate that PBB went to F*~-n Bureau Ser vices in May of that \*ar. In any case, farm problems weir clearly evident by September. In the final analysis, people both influenced all the events and bore the brunt ct the effects. Governmental and educational institutions of Michigan provided.- little effective help in the efforts to deal with the problems generated by the presence of PBB in the environ ment. Egginton blames the "power lines" that linked state governmental agencies and the universities for this. Personal and professional relation ships among the personnel of the various organizations were close. MDA had a laboratory on the campus of Michigan State with which uni versity scientists were involved. Egginton charges that the univer sity's "dependence upon the legisla ture for appropriations made it al most impossible to keep politics out of research, particularly agricultural research." Admittedly, the state's educational institut ions are depen dent on the legislature for funds, and individual staff members may have had problems with divided loyalties but, in the opinion of this reviewer, to imply that the university was a party to purposefully obfuscating the issue is clearly beyond the evidence that is presented. The presence of an MDA laboratory at Michigan State is not prima facie evidence for such collu sion between the two organizations. Egginton appreciat*** the difficulty in establishing that an environmental chemical causes an efiect on human health and closes h**r book with a quotation from a Mi' higan legislator who said that "as tim*' ges on Mich igan people may suff*'r from a lot of different diseases, probably due to PBB ... and there n*-v*r will be a way ... to prove that tL* poisoning of Michigan was the cause. This statement has the of truth. O URL 04729 Feb *$ 1981 C*EN 53 TECHNOLOGY URL 04730 Researchers Providing Some Details About Hazards of Fire Computer model to predict spread of fire and combustion gases is devised; studies of lethal gases, combinations yield surprising results It seems like an easy question: What is it about fires that makes them hazardous to people? But detailed answers are proving extraordinari ly difficult to establish. Like snow flakes, no two fires are exactly alike, and these differences greatly com plicate the task of determining where their hazards come from. Progress is being made, however. Some of that progress, from indus trial, university, and government laboratories all over the U.S., was described in a day-long symposium sponsored by the Division of Chem ical Health & Safety. An initial version of a computer model that can predict the spread of fire, smoke, and toxic gases throughout a building has been de veloped by researchers at the Na tional Bureau of Standards' Center for Fire Research. Though the mod el will be updated as better fire tox icity data come in, in its present form it is already useful to fire fight ers, architects, and others concerned with the fire safety of buildings, says Richard W. Bukowski, head of the smoke hazard group at the Cen ter for Fire Research. Smoke and toxic gases are of particular con cern, because 80 to 90% of the peo ple who die in fires succumb to smoke and gas rather than to flames or heat. The version of the program that is now available models the build up of a fire in one compartment, such as a room in a house, and then tracks the movement of smoke, gases, and the fire itself from that com partment throughout a one-story structure. The program presents data in graphic form--"so that you can essentially watch a picture of what is happening during the fire instead of having to pour through stacks of computer printout, tables, and graphs," Bukowski says. The cur rent program can make predictions for essentially any number of com partments on a single floor. Devel opment work under way will ex tend its capability to multiple-story buildings. The computer program is based on data collected during 10 years of test bums--in which a piece of fur niture or a room or sometimes a whole building is constructed and *>- BuJrowsJri; model is already useful then deliberately burned to collect data on how fires develop and spread under different circum stances. These burns were conduct ed at NBS and elsewhere and cost, on average, $10,000 apiece, Bukow ski says. The computer program can simulate such a burn in a few min utes at a cost of about $100. Thus, with the program it is feasible to "run" several burns under slightly varying circumstances to see what conditions make a building safej. "Using the computer, you can run multiple fires in a building before the building is even built, looking for sources of hazard, and then make design changes" to make the build ing safer, Bukowski explains. Or fires can be modeled in existing buildings to see what kinds of retrofitting might be needed. Fire departments in Phoenix and Los An geles have expressed interest in us ing the system for fire fighter training. Eventually, NBS hopes to devel op a computer program that models real fires well enough to be used for setting performance-based fire codes. Most fire codes today describe the way a building must be built or retrofitted to provide adequate safe ty, Bukowski explains. But if accu rate and comprehensive computer models can be developed, codes could be written instead to specify how a building has to perform in a fire--how long escape routes must be clear of incapacitating gases, for example--and builders could choose their own methods for providing that performance. Such a change could reduce the cost of complying with fire codes very substantially, especially in older buildings, Bu kowski says. In other work at NBS, Barbara C. Levin, head of fire toxicity research in the Center for Fire Research, and * tih URL 04731 Technology coworkers from NBS, the American Iron & Steel Institute, and the Uni versity of Pittsburgh are develop ing some of the data to be incorpo rated into future computer programs to predict fire hazard. In particular, this group is studying the toxicity of single and multiple gases pro duced in fires to determine just how many of the thousands of combus tion products present in fires actu ally contribute to fire deaths. "We want to know if you can explain the toxicity of fires based on (just] the primary toxic combus tion products or if you need to take into account some more minor or obscure combustion products that are also generated in a fire/' Levin explains. Their method is to expose male rats in groups of six to various con centrations of the major gaseous by products of fires for different peri ods of time. The animals are ex posed to both single gases and to combinations of gases that would be expected to be present in an ac tual fire. In some cases, all of the animal deaths can be accounted for by only considering a few of the primary combustion products, the researchers find. For example, hydrogen cya nide and carbon monoxide appear to act in an additive manner so that in the presence of just those two gases, all of the exposed animals may die, even though the concen tration of each gas alone is not high enough to account for the deaths. More striking is the effect of car bon dioxide in gas mixtures. The gas is essentially harmless by itself-- levels of up to 40% (400,000 ppm) can be tolerated before any of the exposed rats die. Such concentra tions are never found in real fires. Levin says, where the maximum at tainable level is about 21%, How ever, in the presence of 5% carbon dioxide, carbon monoxide becomes twice as toxic as it is alone. The carbon dioxide appears to work by increasing the rat's uptake of car bon monoxide and by increasing and prolonging the effect of the carbon monoxide on blood acidity. "Five per cent carbon dioxide is not an uncommon concentration in a real fire," Levin says. "So what people have thought about as a le thal amount of carbon monoxide should probably be cut in half if it is in the presence of 5% carbon dioxide." But even if the assumed lethal dose of carbon monoxide is cut in half and the effect of the concentra tion of hydrogen cyanide found in certain real fires is considered, many of the deaths that occur in these fires still are not explained, accord ing to William T. Lowry, assistant professor of pathology at the Uni versity of Texas Health Science Cen ter at Dallas. Lowry has studied gas samples from about 100 fires in the Dallas area and finds many cases where the concentrations of none of the gases he measured--carbon monoxide, hydrogen cyanide, hy drogen chloride, and aldehydes-- can account for the fire deaths. Lowry's own candidate for the agent responsible for at least some of these deaths is a relatively stable free radical, as yet unidentified, which he has produced in controlled bum conditions. Under these con ditions, the free radical was trapped at concentrations up to 1200 ppm, reaching this level within four min utes and maintaining it until the fire was extinguished. Such a con centration is capable of causing im mediate incapacitation, Lowry says. Studies of the lungs of rats ex posed to fire gases in three test bums of houses found changes in a sur face-active material located in the lining of the lung, Lowry says. This material--a surfactant made up of phospholipids, neutral lipids, and proteins--was found to undergo lip id peroxidation caused by exposure to free radicals in the fire gases. The effect was to increase pulmo nary surface tension, which reduc es the lung's ability to take up oxy gen. Autopsies of 30 human fire victims showed similar changes "consistent with rapid incapacita tion due to rapid rise in lung sur face tension," Lowry says. Preliminary studies of burn vic tims and fire fighters exposed to sublethal levels of combustion gases show changes in blood chemistTy that suggest the presence of free radicals in the blood, Lowry says. Malondialdehyde, one product of lipid peroxidation, was also detected in the blood. Although these-stud ies were performed on a very small number of patients, they do sup port the hypothesis that fires gen erate a free radical that has biologi cal consequences, Lowry says. The relationship between toxici ty results obtained in test situations and what happens in real fires was examined in several laboratories. For instance, estimates of the amount of potentially lethal hydrogen chlo ride produced when polyvinyl chlo ride is involved in a fire may be 1/ much too high, says Chris A. Berteio, a senior polymer chemist for Tenneco Polymers. In work supported by the Vinyl Institute, Berteio mea sured the production of hydrogen chloride when polyvinyl chloridecoated electrical wiring was caused to bum by a power overload on the wiring. The wire was located in a 4-foot-high chamber above an 8-foot by 12-foot by 8-foot room. These conditions were intended to simu late real building conditions in which wiring is usually enclosed in walls or plenums. Berteio finds that even in condi tions that lead to extensive decom position of the polyvinyl chloride, as much as 30% of the hydrogen chloride formed is never released into the atmosphere. An additional 20 to 40% remains within a few inch es of the site of decomposition. Less than half the hydrogen chloride pro duced is released into the general atmosphere. Deposition of the ma- ss May 20. 1985 C&EN Technology URL 04732 terial was so great near the wire, Bertelo says, that without extra cir culation, the concentration in the adjacent room never exceeded 10 ppm. Separate studies by the Food Sl Drug Administration on baboons show tolerance levels for hydrogen chloride as high as 12,000 ppm, he adds. "It cannot be assumed that all the chlorine in polyvinyl chloride will be released as hydrogen chlo ride," Bertelo says. "In addition, pro vision must be made for the rapid decay of the product. .,. The haz ard of polyvinyl chloride decompo sition in fire situations is much less than originally thought." For both wood and polyvinyl chloride, the shape of the object being burned affects the amount of smoke and toxic gases it will pro- duce, says George V. Alexeeff, a tox icologist for Weyerhaeuser Co., Longview, Wash. A cubic piece of Douglas fir produced smoke and car bon monoxide much more slowly than did the same weight of wood in the form of shavings or a thin flat piece, Alexeeff says. Even after half an hour, when smoke produc tion had reached its maximum for all three shapes of wood, the cube produced only about 4500 ppm of carbon monoxide, compared with 7000 to 8000 ppm for the flat piece and shavings. Similarly, in the Weyerhaeuser tests, a flat piece of polyvinyl chloride takes about 15 minutes to reach its maximum pro duction of hydrogen chloride, com pared with about 25 minutes for a cubic piece of the same weight. Progress reported in coupling LC and MS The efficient coupling of liquid chromatography and mass spectrom etry 'LC-MS) has been a subject of continuing interest to practitioners of both arts (C&EN, Sept. 26, 1983, page 19). Evidence of recent prog ress in the field was presented at an LC-MS symposium sponsored by the Division of Analytical Chemistry. There are at least two basic ap proaches to getting analytes out of the liquid chromatograph and into the mass spectrometer. In one, ex emplified by moving belt interfaces, the solvent is evaporated from the LC eluate before the analyte passes into the mass spectrometer system. There it is ionized by conventional means. In another approach, the el uate, or a portion of it, is injected directly into an interface, where the analyte is ionized by one of several desorption techniques. The various techniques are competitive to a de gree, but also complementary, be cause each has advantages and drawbacks, depending on the appli cation. At the symposium, several of the presentations focused on the mech- anisms underlying the different LCMS methods. For example, mass spectrometrist Robert J. Cotter of Johns Hopkins University noted that the thermospray technique (pioneered by Marvin Vestal at the University of Houston) is actually a desorption technique and therefore related to techniques such as fast atom bom bardment (FAB), secondary ion mass spectrometry (SIMS), and electrohydrodynamic ionization (EH). The thermospray technique is a desorption technique. Cotter ex plains, because the ions are formed within the buffered solvent matrix. The LC eluate enters the interface as droplets, from which the solvent evaporates until an imbalance of charges causes ejection of analyte ions. That happens. Cotter says, be cause the statistical imbalance of charges actually creates a high local field in the droplet. A few years back. Cotter, work ing with Catherine Fenselau and other associates at Johns Hopkins, compared the relative abundances of doubly charged ions obtained with two desorption techniques: field desorption (FD) and FAB. In the absence of a field, doubly charged ions aren't easily observed, Cotter says, because they are more strongly attracted to the matrix than the singly charged ions. But in the presence of a high electric field. they should be favored. Indeed, ex periments with bis-pyridinium salts showed that doubly charged ions were more abundant with FD than with FAB. More recently, the idea was ex tended to comparisons of FAB and thermospray. Experiments involved tubocurarine hydrochloride, which has a divalent cation. In general, thermospray produced more modes of fragmentation, more fragment ions, and fewer molecular ions, com pared with FAB. In addition, dou bly charged ions were relatively abundant with thermospray, but al most completely absent with FAB. According to Cotter, the findings suggest that the ion formation mech anisms of the two processes are ba sically different. In another mechanism-related presentation, Kelsey D. Cook of the University of Tennessee rioted^ that many LC/MS interface systems ex ploit the LC eluate as a vehicle for solution chemical ionization, rather than expend effort to remove the solvent matrix before MS analysis, as is the case with the older movingbelt interfaces. In fact. Cook says, some of the newer moving-belt sys tems also rely on matrix assistance, by replacing the chromatographic solvent with a second solvent (on the belt) that facilitates FAB analysis. With such systems. Cook says, one should consider the factors that af fect how efficiently the process re moves ions from a liquid matrix. They're important for quantitation of LC-MS, and also for determining the sensitivity and efficacy of other liquid desorption ionization pro cesses, especially FAB and liquid SIMS. In most of the LC-MS experiments to date, however, it is hard to dis tinguish the energetics of ion re moval from the energetics of other processes taking place in the exper iment, Cook says. As examples, he cites the heating that results from collisions with the hot probe used for thermospray and the ion-mole cule reactions associated with chem ical ionization in direct liquid in troduction systems. These factors tend to complicate studies of basic mechanisms. Electrohydrodynamic ionization, in contrast, depends on field evap- 38 May 20. 1985 CAEN 32L S. fc. CARR02a g-l-ff -a/a/W ^ -jrrr CHEMICAL REGULATION REPORTER^ A weekly review of acilvtfy'dltoiSng chemical users and manufacturers Volume 7, Number 40 ".*1 i .A ' S* THE BUREAUOF NATIONAL AFFAIRS. INC - :l4anuaiye,1M4 :v HIGHLIGHTS ".car:rii* . ' *.r*r \S'i -0 '='. -'t ."s- vv: t'r-}-Lt PotychtortnMfd Bipb+nyb ' -*?.:*: - -- j.'-t" j-.i TRANSFORMER FIRES C0N8TTTUTE HEALTH RISK. . r - PRODUCE DIOXINS. FURANS, EPA SCIENTIST SAYS .-rr ... Fires associated with PCBelectrical equipment constitute a "previously unrecognised health heard by exposing par sons In hooindustrial environments' to toxic chemicals such u polychlorinated biphenyls, chlorinated dioxins, chlorinat ed furaasT end other chlorineted organic compounds "~*- to an Environmental Protection ' bl oeuumen: W EFAfr Office of foal teat PUB l^i produce sic HBu of deadly polychlorinated dtbenso-fMUoxiiis and -farans found in the.United States. . According to ^runnerrecently submitWl to toe Btoctric fwwrJhMiyj|>iB|BL .Nonrafter studying data train Jemal Area Inrolriag PGB transformers and capadtori. .-.A-ri; - -Jvh vtii-- The information comas a EPA is attempting to deter mine what risks are associated with PCB transformer flres rand whether federal regulations are needed to limit toeae risks. :r;i rr.n>~i:j2w '* srq ^ Under a settlement reached with environmentalists chal lenging:the 1982 PCB electrical equipment rule,EPA la required to tent an advance notice of proposed rulemaking ia March to solicit information on transformer Ares (Oct 28, .IMS, p.1114). That tafoettatton wllf torn be used to deter- mine whether regulations are neeemary. . Dioxkts and PCBa'Ctoaiaiad 'V- V-aj. -- EPA'sresearch ofico Is now. to thaprocem of securing aoot samples from PCB elecnlce! Area that occurred to Chicago, San .Francisco, Sjrscme^N.Yi, aad Btnghamten, JlA* detRosiers said. .-v afty*5 f .ceJ.-i., The agency's analytical laboratoey to.Ctaichmsti, Otto, ..will conduct a chlorobename tamer screen ontbe ir-T1** for toe purpose of attempting to correlate toe and farad content in aoot and wipe escapist with ddorobenaeoe rend PCB content in the transformer BnkLTh^ work Mould help EPA predict toe amount of-dibetni end faranathat would be generated from tot rnmfaittknof-various PCB : dielectric Anlds, deaRoNers explained... a. ^: In his paper, dtoRostors noted that a 1M1 Stedy of aoot -fran a PCB transformer Are to Binghamton, N,Yn demon strated that dioxins and farans to ton aoot werebMoflcally .Actfve.i*lhe soot, toerefore can bo considered toxir ; -r-lhis^if 'in contrast to datg on Ay ash. frdm^imaanpal tectoerators. Altooogb meb Ay ate .to laiown^toj^nouin ''dioxins andforaat,'the cbenrinals are toaottve fotUcfixin. rmfioordUg to desRoNecs' paper, toceh^ve TCdtoxin7bo. smers and' 1JS faran toomors. A^ete tp^etty. among toe i- isomers can my by .ip to 100^WO_tbbe^ he.said. -&y comparison, the moat acutely toxic J*C8 isomer is only about one-fourth as toxic as toe most toxic dioxin Lacauea -- -rv^T }i' r ' / ,7 uawirno Bensenea.-.- J PCBs cootaln a complex nrittnieef farans, with up to 40 Isoaners bring presml/deiRtefqt ssld. fle explained that although jBwdna are'not'found'to PCB transformers under eorinal coaadittoiia, toey do occur when a transformer con taining a mixture of PCBt and chlorinated bwnenes under- *goei combustiocortocnhalstrem.lbefannattouofdioxins is believed to be due to intennotocular ruactiOQS of chlorin ated bensenea and oxygen onder thermal eoodltloaa, toe SPA sricotist added. Thu, dtadntf areproduced only when chlorobename ffihNnts are preeent in PCB mlxtara, be jdded. ; - Furaiis, 00 toe other hand,' are found at yarious^ levels in ahnoet all PCB transformers and capacttori^ be said. Bowoyer, the amount of tome sabotanctu appears to* Increase -wHh the age of too equipment and is giuei stiid at substanfol Into whan toe eqriprueirt b under tbenhal gu ess. *Tn ireVtewing `data from a PCB fransfonner Are in a 22story ottco huOdlng In Btoghamton, N.Y^ deiRoriers arid anafysis of aoQt Ttmplrr food In toe bullring Mowed-Ann isomers -as Ugh as 2,1*8 ndefocrams per gram of aoot, Afawriii isomen as Ugh as l8-2* ag/g. and PCBs as hl^ ns l*D,OOh -tp 2M,000 pgfg. DesRoeiers said the most toxic gloxin and faranlsbmen were toe major components within toe aoot, including 2A7.8-TCDD; 24,7A-tatrachlorodlbeaxh jy^tamn; i4A7**psMstolarodtoimich2>dtoxin; TA2<7,8-peDtachlorodibenm-p-farnic and 2^,4,7A-PCDF. -^Atnee the tri- and tetracfalorinatad hensenes comprise 28 percent of toe dielectric Arid, it is not imreasooable to assaroe this ffluent mixture repreocyts toe preenmor to toe FCDDs [dioxins]produced as a result of the Are," desRoaters concluded from .toe data.- 1: DesRosiersalso said Oat even after parts of tor Ringham- ton office were decontaminated using steam and detergents, trade amounts (nanograms per square meter) of farans and ffioxina were stQl present 1- K.