Observations and Notes on the Effect of Methanol Antifreeze on Health

Nov 4, 2010 - In view of the rather sudden increase in the use of methanol as an antifreeze for automobile radiators and the consequent anxiety as to ...
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NEWS

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EDITION

Vol. 8, No. 23

Observations and N o t e s on the Effect of Methanol Antifreeze on Health R . R. S A Y E R S A N D W. P. Y A N T 1

I n view of the rather sudden increase in the use of methanol as an antifreeze for automobile radiators and the consequent anxiety as to the possible health hazard i n dispensing and using the product, the chemical industry interested in. the manufacture and marketing of methanol requested t h e Bureau of Mines t o make an impartial and extensive investigation of the hazard involved. This is now in progress and will extend throughout the winter. The development of a synthetic process for the manufacture of methanol and its marked reduction in c o s t during the past two years have placed it in competition with denatured alcohol for use as an antifreeze. It is estimated that i n the winter of 1930— 31 from 10 t o 15 per cent of the low-boiling antifreeze materials used will be methanol. The product is a t present dispensed t o the consumer as a mixture of 76.5 per c e n t methanol and 23.5 per cent water. I t has been found that 1 gallon of this mixture has an antifreeze value equivalent t o that of 1 gallon of antifreeze ethyl alcohol. TOXICITY OF M E T H A N O L

The observations and discussions of t h e poisonous effect of methanol which have been recorded in the literature are in many cases conflicting and confusing. Some h a v e explained the differences in results on the basis of individual susceptibility. While this explanation is no doubt valid in part, it is also just as possible that many of the differences arise through the difficulty in obtaining accurate quantitative details, particularly if it involves the possible use of methanol for beverage purposes. I n surveying past experience, however, there are certain consistent observations. I t has been shown beyond doubt that methanol is a poison and will produce serious poisoning when sufficient amounts are taken into the body. Also there is no practical difference between the toxicity of crude and refined methanol, or between methanol made by the wood distillation process and that made by the recent synthetic process. Further, i t cannot b e made nonpoisonous by any known method or process. T h e s e facts need emphasis because some persons have held the erroneous opinion that the poisonous action of methanol is d u e mainly t o impurities and that the purified product is relatively less toxic. The quantity of methanol required to produce poisoning when the product is taken into the stomach i s pretty well known. Small amounts have been taken without apparent harm, but o n the average 1 to 2 ounces (the contents of 1 to 2 ordinary whiskey glasses) will cause serious poisoning with possibly blindness and death, and twice that amount will frequently cause death. The effects of inhaling air containing various amounts of methanol vapor are not so well known. Records of cases of severe poisoning b y inhaling methanol vapor, however, show the large majority of serious cases to have occurred in the use of methanol, principally as a solvent for paints and varnishes, in relatively small confined and unventilated places. The potential health hazards from air containing methanol vapor thus depend on the degree of exposure; accordingly t h e safety of methanol for antifreeze purposes depends o n whether or n o t the exposure involved in a particular usage will exceed the range of tolerable exposure. Less is known of the dangers t o health from absorption of methanol through the skin. In reviewing the literature n o conclusive information could be found that serious poisoning has been acquired in this manner. A few cases are described a s possibly being due to skin absorption. In these instances exposure was either so slight that it is rather hard to believe that the trouble was due to absorption of methanol through the skin, or the situation was complicated by the possibility of high concentrations of vapor in the air breathed. When one considers the large amounts of methanol that have b e e n used and t h e frequency with which it has undoubtedly c o m e in contact with the skin, in many instances even having been used for treatment of wounds and for "rubbing" purposes, it is apparent t h a t n o appreciable hazard exists from this manner of exposure t o methanol as an antifreeze. SCOPE OF INVESTIGATION

The primary objective of the investigation now being conducted is to ascertain whether or not t h e use of methanol for antifreeze purposes will constitute a health hazard t o persons involved in its distribution and use. In more detail, the investi1 Abstracted from U. S. Bureau of Mines Information Circular 6415. The report represents work done under a cooperative agreement between the U. S. Bureau of Mines and the Carbide & Carbon Chemicals Corp., D u Pont Ammonia Co., and the Commercial Solvents Corp.

gation entails a laboratory study of the toxicity of methanol when acquired b y inhaling air containing its vapor and when acquired b y skin absorption. Simultaneously with the laboratory study, a practical field investigation is being made of the amount of methanol vapor to which persons are exposed in closed cars and in private and public garages b y escape of the vapor from the radiator, or spillage and drip from leaky radiators. The exposure of the garage or filling station attendant while dispensing methanol is also considered. The conditions under which the tests are being made range from the normal operating conditions t o overheated engines and boiling radiators. An investigation is also being made of the exposure and the health experience in the manufacture of methanol. This phase of the investigation affords opportunity for obtaining information based on long experience with methanol under many conditions of exposure which simulate those encountered in its use as a n antifreeze, and thereby gives earlier information on continued exposure than is possible t o obtain from a study of antifreeze usage. The s t u d y made by the Bureau of Mines will not include work o n the toxicity of methanol when taken into the stomach. It is not only a well-known fact that i t will produce serious poisoning, b u t the quantities required to produce poisoning have been established. Further, the ingestion of enough methanol to cause poisoning is not an apparent hazard in its use as a n antifreeze. R E S U L T S OF INVESTIGATION

Although the investigation will not be completed for several months, a survey of the conditions of exposure prevailing in four plants engaged in the manufacture of methanol, and physical examination of 3 6 men who have worked in these plants for periods of a few months to 10 to 15 years, have been completed. This survey consisted of making general observations of duties and exposure of t h e workmen, and quantitative chemical determinations of the amount of methanol t o which the workmen were exposed, and a physical examination of the workmen. The physical examination included a n occupational history, a health history, and a complete physical examination with special attention t o vision, pupil reflex, and eye pathology as revealed b y ophthalmoscopic examination. Urine specimens were examined for albumin, sugar, specific gravity, reaction to litmus, and methanol content; and blood specimens for methanol, hemoglobin content, number of red and white cells, and differential cell counts. These persons were engaged i n all the operations of manufacturing methanol wherein there was exposure t o air containing t h e vapor and exposure by contact with the skin. In nearly all cases both types of exposure were present. The manner of exposure to vapor ranged from working over drums being filled with methanol, inserting bungs in filled drums the exterior of which was usually w e t with drippings, working over an open drain pan continuously wet with methanol, taking samples of methanol from drums and still-house look-boxes, making hydrometer tests, and general exposure resulting from leaks and spillage in t h e working places. Contact with t h e skin was a common finding, occurring many times daily with some persons. I n one operation a man wet the palm and fingers of one hand t w o hundred to three hundred times daily and in addition was continuously working over drums being filled with antifreeze methanol. I n a similar operation another person wore gloves, the palms and fingers of which were w e t practically all of the time. Other operations required almost constant contact of the fingers with methanol. It is a rather common practice among still-house operators at wood distillation plants to w e t their hands with methanol and smell the product a s d guide in still operation. Likewise it is a common practice a t these plants t o use methanol for washing wood tar from the hands and tools and for cleaning parts of machinery. The above are usual and observed exposures. Under unusual conditions i t was learned b y interview of workmen that some frequently get their trouser legs wet, and others on a number of occasions have been practically drenched with methanol. They stated that the usual procedure i n these cases is merely to allow t h e methanol to evaporate, as they suffer no discomfort other than the cooling effect produced by the rapid evaporation. A number of persons stated that they had used methanol on wounds, a n d as a liniment for "rubbing" purposes, and a considerable number had used it in automobile radiators for antifreeze. None of the m e n expressed fear of exposure t o the vapors or b y skin contact because they had never experienced ill-health from it, nor did t h e y know of serious effects having occurred t o

December 10, 1930

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workers in t h e industry from this manner of exposure. There is, on the other hand, universal knowledge that methanol is poisonous and cannot be taken into the stomach. The results of the physical examination of these men revealed no acute or chronic illness, and no defective vision or eye pathology attributable to methanol. There was also no indication of deleterious action revealed by blood and urine analysis. I n a considerable number of cases of comparatively severe exposure, methanol was found in both the blood and urine when the specimens were taken after several hours' work. This confirms actual exposure and acquiring methanol but, on the other hand, substantiates experience that certain amounts of methanol can be acquired without apparent harm. Specimens taken the following morning from several of these persons showed methanol to be practically absent in most cases and markedly reduced in t h e others. In all cases the amounts in the blood and urine were far below those which have been found in the laboratory part of t h e study to be harmful to dogs. SUMMARY

The information which t h e Bureau of Mines has obtained to date indicates that there is no hazard to health from t h e reasonable use of methanol for antifreeze purposes. Many of the conditions of exposure to vapor and b y contact with the skin, which were observed in the manufacture of methanol and for which no health hazard was found, are very comparable to the degree of exposure observed in usage as an antifreeze. Also the exposure in both cases is below those which laboratory experiments with animals have indicated to be harmful. JfcThe investigation i s being continued for the completion of information on the toxicity of methanol, particularly from the viewpoint of obtaining more comprehensive data regarding allowable concentrations for industrial uses and for investigating further the mechanism of methanol poisoning. Also, while there are no reasons t o believe danger to health will occur in the use of the product as an antifreeze, the Bureau of Mines will observe its use throughout the present winter, as this procedure is always desirable where new uses of products involve the question of hazard to health. CONCLUSIONS AND RECOMMENDATIONS

The following conclusions and recommendations are based on studies and observations to date : Observations made by the Bureau of Mines have indicated that there is no danger of poisoning from t h e reasonable use of methanol a s an antifreeze for automobile radiators. The evidence that methanol poisoning has been caused by absorption through t h e skin is rare and inconclusive. Practically continuous exposure to low concentrations and short intermittent exposure to high concentrations of methanol cause no apparent harm; but, on the other hand, continued exposure to high concentrations will cause serious poisoning. All methanol, whether made b y wood distillation methods or synthetic methods, or whether it is crude, refined, or highly purified, is poisonous when taken internally. It will cause serious poisoning, blindness, and possibly death when as little as 2 ounces is taken into the stomach. To avoid misuse it is recommended that, in the future, all antifreeze methanol b e brightly colored to enable garage attendants and the public to identify it as methanol; and to warn against misuse, particularly for beverage purposes. The largest producers of methanol antifreeze label their containers so as t o call attention t o the hazards of misuse of methanol and also issue information and instructions to garage attendants and the consuming public warning against its misuse. I t is recommended t h a t these precautionary measures be adopted b y all producers.

Third International Bituminous Coal Conference Announced A third international conference on bituminous coal will be held a t the Carnegie Institute of Technology in November, 1931, according t o a recent announcement by Thomas S. Baker, president of t h e Institute of Technology and organizer of the first two international congresses. A n invitation will be extended to scientists of all countries t o take part in the meeting, which i s the only one of its kind of international scope. Prominent m e n of affairs in America will assist Doctor Baker in organizing the meeting. T h e purpose of t h e congress, President Baker announced, will b e similar t o t h a t of t h e meetings held in 1926 and 1928—to present for discussion t h e results of recent studies of coal. Particular attention will b e paid to t h e economics of the new methods and processes that are being evolved. The program will include papers o n carbonization, liquefaction, and gasification of coal; by-products of coal; the mechanism of combustion; cleaning of coal and i t s preparation for the market; pulverized fuels; power

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plants, and domestic heating. The discussions will be confined to coal above ground. Beginning at t h e mouth of the mine, however, practically every phase of distribution a n d consumption will be treated b y outstanding authorities i n the several fields. Announcement of this third world meeting comes in logical sequence to t h e previous congresses. The first conference w a s organized by President Baker in 1926 for the purpose of finding new uses for bituminous coal a n d especially to discuss the problem of liquefying c o a l to supplement the petroleum oil supply of the world. This meeting, although it w a s the first of its kind t o be held, attracted 1700 scientists from thirteen different countries. T w o years later followed t h e second congress which w a s broader in its scope, including discussions o n pulverized fuel, low-temperature carbonization of coal, rubber from coal, the hydrogénation of coal, a n d by-product nitrogen.

Engineering Index Service T h e Engineering Index Service offers a comprehensive and complete a n n o t a t e d index of t h e current engineering literature of the world, made possible through t h e cooperation of the Engineering Societies Library in New York. The 180O engineering, scientific, technical, a n d trade publications received b y the library are regularly and promptly indexed by the Engineering Index Service. These publications cover all branches of engineering and industry, over half of them coming from 3 7 countries outside the United S t a t e s . Regular periodicals are indexed, as well a s society transactions, government bulletins, engineering experiment station reports, research reports, etc. Approximately 50,000 annotated i n d e x items are produced each year b} r a staff of engineers who translate from the 17 foreign languages in which the publications are written. T h e index i s available on cards and in annual volumes. The card service i s arranged i n 223 divisions, a n y one or more of which may be subscribed t o separately. Items are printed on standard library filing cards, mailed daily to subscribers of the entire service and weekly t o subscribers of part of the service. Each year the cards produced are published in a volume of over 200Ô pages, with an author index of about 20,000 names. A. valuable feature of the service is t h e provision of annotations, which enable the user to appraise t h e articles and select those of particular interest. T h e subject heading classification, alphabetically arranged, is another outstanding feature. Since its inception in 1884 the service has been steadily expanded to keep pace w i t h the rapid developments in engineering, and t o give the engineer a n essential tool for h i s work.

Special Water-Power Publication Under t h e title, "National Aspects of "Water Power Development—A Review of the Facts," b y the National Water Power Policies Committee, consisting of twelve members active in the fields of finance, engineering, education, journalism, business, and agriculture, t h e Chamber of Commerce of the United States, Washington, D . C-, has issued a 179-page, 8 X 10 inch, paperbound book. I t is a compact, non-technical presentation o f a study of waterpower development, particularly those features of a political nature involving the federal and state governments. While the textual m a t t e r is of chief interest t o the layman, i t a t the same time correlates the many sides of water-power development in a manner valuable t o experts, executives, and officials having t o do with w a t e r power. Beginning with a discussion of the uses o f water and their interrelation, attention i s given to the basic data available and the various governmental agencies engaged i n its compilation. Following this, considerable space is given t o the legal aspects of the water question in a somewhat historical manner, pointing out the growing conflict between federal and state supervision. Before entering upon a summary of the important questions of rates for electric service and regulation o f electric power utilities, facts are presented which show the trends i n the hydroelectric and steam-electric power fields. Rate structures and regulation are treated mainly as state problems. Then, follows a chapter on the federal government's interest in water-power development, which includes a discussion of the Federal Power Commission. Another feature of the report of general interest is a summary of conditions under which federal and municipal power plants have been constructed, and the extent and significance of such development. The final chapter is a full presentation of the Muscle Shoals problem as i t relates to agriculture, national defense, and power policies. The report is followed by numerous appendixes, containing tabulations of statistical matter, charts and maps, and excerpts from reports and law, references t o which are made throughout the report proper. Copies m a y b e procured from the Chamber of Commerce of the United States for $1.00 each.

NEWS

Patent Office Spelling Cadmus is a n overrated man. H e did not discover cadmium and he did invent spelling; t h e which i s a perennial nuisance. The curse of Cadmus is o n the whole English language, the worst spelled in the world; a n d particularly o n the chemical sections thereof. Take "phthalein." N o reasonable m a n can spell that word unassisted and get i t right in five tries. Proverbially, it is a weak-minded man who can spell a word o n l y one w a y ; and chemists are mostly strong minded and impartial. T h e standardized orthography and nomenclature of t h e publications of t h e AMERICAN CHEMICAL SOCIETY, or their "style" a s a printer would call it, stand between us and verbal anarchy. But it must b e hard on the proof-readers. What they would d o to a m a n w h o used "quinolin" and "chinolin" in adjacent sentences is an interesting query. Something drastic likely. Spelling is o n e of the things that variegate t h e chore of being a chemical patent attorney. T h e Patent Office has n o particular "style," orthographical o r otherwise. I t did once, a long time ago; but not now. In 1930 i t considers permissible for chemical terms any spelling of any word in a n y dictionary- This does n o t mean much, a s very m a n y chemical terms are n o t in the dictionary; and some that occur are non-naturalized aliens, like "kali" and "azote." Nor are the dictionaries so h o t as regards chemistry. All dictionaries give as the secondary meaning of "oxygen," either chlorine or bleaching powder. However, while t h e Patent Office as a n organization h a s n o orthographical opinions, there are six-hundred-odd examiners who do have. Their ideas, which a r e many a n d valions, generally go. For instance, t h e y mostly have a prejudice against ending words with "ise" instead of "ize," and I have spent weary hours i n changing British-written specifications t o " i z e " t h e "ises." " Diazotising" things with an e s s is a favorite indoor sport i n some foreign circles. In zeeing the esses I get i n D u t c h (which is n o t so good) with t b e English chemists; but t h e y a r e abroad a n d t h e Patent Office h a s me on t h e spot with a big stick which fits certain wales on m y personal contours. Officially, before the Patent Office the standardized orthography

EDITION

Vol. 8, No. 23

subjects: advanced inorganic chemistry; analytical chemistry; organic chemistry; and physical chemistry. Applicants must show that they have been graduated w i t h a bachelor's degree from a college or university of recognized standing, such degree requiring t h e completion of a t least 118 credit hours, 30 credit hours of which must have been in chemistryFull information may be obtained from t h e United States Civil Service Commission, Washington, D . C , or from t h e secretary of the United States Civil Service Board of Examiners a t the post office or customhouse in any city.

Fellowships in Foreign Countries

A limited number of foreign study fellowships is offered under the international student exchanges of t h e Institute of International Education to American students. Tbese fellowships have been established as an international exchange i n appreciation of fellowships offered by American colleges to foreign students. A candidate must be an American citizen; a graduate of a college, university, or professional school of recognized standing, or a senior who will have met this requirement before entering upon the fellowship; of good character a n d ability; in good health; able to d o independent study and research ; and must have a practical reading, writing, and speaking knowledge of the language of instruction in the particular country. Preference is given t o candidates under thirty years of age. Several fellowships covering board, lodging, and tuition (a few providing free tuition only) are available i n Austria. T h e Czechoslovak Ministry of Education offers several fellowships of 15,000 Czechoslovak crowns (equivalent t o about $500, which approximately covers room, board, and tuition) i n Charles University, the University of Technological Sciences, t h e Arts Academy and Commercial College in Prague, the Masaryk University and the Institute of Technology in Brno, and t i e Komensky University in Bratislava. In· France fellowships are available a t the Universities of Grenoble, Lyon, Strasburg, and Toulouse; a t Bordeaux and a t the Ecole Supérieure de la Métalof the AMERICAN CHEMICAL SOCIETY is n o w j u s t as good a s a n y other; a n d no better. Some of the examiners l i k e i t and some lurgie e t de l'Industrie des Mines a t Nancy for men; and a t t i e Ecole Normale Supérieure de Sèvres and t h e University of Paris do not; and local option prevails. The Government Printing Office is even less addicted t o t h e for women. Some include board, lodging, and tuition, and some free tuition only. SOCIETY'S spelling; nowadays, that is. I n 1930, i t prints patents following the copy sent i t , whatever the eccentricities of orthogGerman universities have established a number of fellowships raphy, b u t it does n o t enjoy s o doing—it yearns for uniformity covering board, lodging, and tuition at the Universities of Berlin, and a style; i t s own style of course. For its o w n purposes, i t Bonn, Breslau, Frankfurt, Freiburg, Gottingen, Halle, Hamburg, likes Webster's International Dictionary, which calls for "sulphur" Heidelberg, Kiel, Kôln, Leipzig, Marburg, Munich, Munster, and for "oxide" with a neat little decorative "e" o n the latter end. Tubingen, and "Wurzburg, and at the technological institutes a t Like any other bunch of printers, it dislikes "simplified spelling," Danzig and Munich. Fellowships in Hungary are available a t and I have no doubt bobtailing "chloride" t o "chlorid" looks the University of Budapest, t h e Technical University of Budagruesome t o it. The advantage of differentiating "chlorid" from pest, t h e University Faculty of Economic Sciences, t h e Veteri"chlorite" by sight and sound does not appeal t o a printer. nary College, and t h e Music Academy, all in Budapest. The. Italian Government offers five fellowships, including board, However, all this is the 1930 picture. I n 1896 there was publodging, and tuition, for study a t the institutions of higher learnlished a style book, "Rules Governing the Printing of Specifications" of patents, governing both the Patent Office a n d t h e ing in Italy. T h e Spanish Government offers several graduate fellowships covering fees, board, and lodging at the University Printing Office and carrying the SOCIETY'S chemical spelling. of Madrid or t h e Centro d e Estudios Historicos. These fellowAnd for 15 or 2 0 years thor»e rules went; t h e examiners enforced ships are o n a direct exchange basis, and the candidate should them with a vigor t h e i \ i les and Persians h a d not much o n . ascertain whether t h e institution from which he was graduated T h a t was their job of course; b u t most of them approved anyway. has entered into the exchange agreement. The universities of Among these examiners was Doctor Seaman, "who handled all Switzerland offer a number of tuition scholarships, in some cases inventions in organic chemistry and heavy chemicals. Doctor supplemented b y stipends covering board and lodging or their Seaman w a s t h e chemist who took t h e p H out o f "sulphur" and induced t h e SOCIETY to like it that way. The SOCIETY spelling equivalent. These are available a t t h e Universities of Basle, Berne, Fribourg, Geneva, Lausanne, Neuchâtel, and Zurich, and was popular w i t h him. at the Eidgenôssische Technische Hochschule in Zurich, a n d t h e But new people came i n t o both offices, and the 1896 style book Handelshochschule i n St. Gallen. faded into "innocuous desuetude." And i t is there now thickly encrusted with oblivion. Its rules have never b e e n formally abroApplications for German fellowships must b e submitted on gated, so far a s I can learn; just forgotten. I n the old *'Little or before January 1 5 , a n d for other fellowships on or before Tycoon" was a topical song running in part something like "All February 1. Detailed information concerning these and certain serene as a canned sardine. Canned for the siege of Troy." Someother fellowships m a y b e obtained direct from t h e Student how the old s t y l e book reminds me of t h a t sardine. Bureau, Institute of International Education, 2 West Forty-fifth St.. N e w York, Ν . Y . All of which i s to say t h a t in this year of grace 1930. a man with an application i n t h e Patent Office is entirely free t o u s e a n y spelling h e pleases unless some examiner objects; in which e v e n t it is sanitary for the man t o change his mind. I n 1930, t h e w a y t h e AMERICAN CHEMICAL SOCIETY prefers t o spell i s of no impor-

tance to t h e Patent Office or t o the Government Printing Office. K . P. M C E L R O Y

C. S. Examination, for Junior Chemist T h e United States Civil Service Commission announces an open competitive examination for junior chemist, applications for which must be on file witb the V. S . Civil Service Commission, Washington, D . C , not later than January 27, 1931. T h e entrance salary i s $2000 a year. This examination is to fill v a cancies in the departmental service or in t h e field. Competitors will b e rated on general chemistry and elementary physics, and o n one or more of t h e following-riamed optional

Association of Consulting Chemists Elects New Officers

The Association of Consulting Chemists and Chemical Engi­ neers, a t t h e recent annual meeting, elected the following new officers : president, Allen Rogers; vice president, Robert Schwarz; treasurer, Alvin C. Purdy; secretary, Paul Mabler; and chair­ man, advertising and publicity, Irving Hochstadter. This association has grown substantially since i t s organization over three years ago, a n d n o w includes a great many of t h e leading national consultants i n t h e chemical field. M u c h h a s been accomplished b y t h e cooperative work of the association t o provide highly specialized a n d competent consulting service for the chemical and related industries. T h e secretary's office is maintained a t T h e Chemists' Club. 52 East Forty-first St., New York. Ν . Υ .