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NORMAN V. STEERE Intelligent handling of chemicals requires recognition of the hazard8 of the chemicals ns a prerequisite for understanding and contt.olling the hasards. Recognition is complicated by the great, variation in hheling systems used (or not used) in the U.S. and other countries, by the general reluctance to report chemical accidents in reaenrch papers or other puhlioations, and by the expenses of tesling chemienln and preparing articles for the scientific litemtore. There are other reasons of course, h u t these three seem central. Variation- in labeling or marking nystems used in the U.S. ranee from thp SYSsingle-hazard, single-degree-of-11-d tem which uses three different types of labels or placards, to the s y t e m adopted and advocated fnl. other sitnations which employs detailed precautionary wording plus a symbol which shows degrees of three kinds of hazard. Understanding the different systems is difficnlt hecause the definitions and ranges of terms vary from system tosystem. Before comparing definitions of terms and chemical labeling systems in use nr development, let os look hriefly a t some of the organisations that make recommendntions or regulalions for identifying hazardnus mnterinls, not including drugs, economic poisons or radioactive mnterinls. The National Fire Protection Association and the Mmofacturing Chemists Assoriation have recnmmended nystems for labeling and marking hwaardolls mat,erisls. Legal regulations are astahlishrd and enforced hy the Department of Transport.xtion, the Food and Drug Administrat,ion, the Ikpnrtment of Defense, and the Depart,ment.of Lahor.
Associations Recommending Hazard Identification The National Fire Protection Asnoriat,ion (NFPA) obtains and circulates information on fire protertion m d provew tion, and tht.ough it.s open membership and meetings and committee procedures develops standard whirh me nst,ionallyrecognized as consensus standards. Some NFPA pnhlicatians are Hazardnus Chemicals Data (NFPA No. 40), Mxnonl of Hasnrdous Chemical Renctions (NFPA No. 4'913\1), Fire I3nan1.d Pvope~?ies of Flxmmahle Liquids, Gases, and Volatile Solids (NFPA No. 325M), and Rerommended System for t,he Identification of the Fire Hazard of Matwials (NFPA No. 704M). The NFPA hazard identification system provides n simple method of rommrmirat-
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The DOT system is actually made up of four systems which are almost totally nnrelated except for definitions of hazardous material8 and specifications of containers. The markings for containers are diamond-shaped hhelr with wording ing a t a distance t,he relat,ije severit,y of for surface shipment,, and with warding. the hazards of a mnt,erial in terms of and pictographs for air shipment,. The emergencv health hazard, flammahiliby, markings for brucks me placards with one and instshilit,y or reactivity. The system or two words, such as Corrosives or Flamis in use in tank farms, indust,rial plants mahle Gas. The marking of railroad cars may he a diamond-shaped placard for and Iahoratories, hospitals, and universiby some dangerons commodities or a rectanlaboratories on all sises of containers. gular plaoard for others. Precautionary The NFPA h ~ a e r didentification system wording is limited and may not even inprovides for rating the spill and fire hasdicate the specific nature of the hazardnrds of ehemirnls on a scale from "0" for on up to no hazard or no 1mus11~1 e.g., t,he label required for drums of flam,,4,, for extreme hazards.hhaeard, When the ~ y s - mable liquids does not contain the word tem is used on a container, t,he degrees of "flammable." haaard appear in quadrants of a, lnrger One of the most serious criticisms of the "danger shape"-a diamond. (The apsystems inherited by DOT is that only one plication of t,he hazard identification kind of hazard is indicated and that there system is described in more detail in is no way of indicating m y degree of hazard. Many chemicrtls shipped in bulk "Fire Safety Standard for Hospital Labhave severd very serious hazards, but oratories," which appeared in THIS JounNAI. in September, 1971.) only one is indicated hy the lahel or plrtcard. Several hazardous chemicals can be The Manufacturing Chemists Associashipped without any required identification (MCA) formed R. Labels and Pretion of the hazard becnnse of arbitrary calttionary Informntion (LAPI) Commitdefinitions. A detailed study of the tee in 1044 which developed the "Gnide to Precautionary Laheling of H a ~ ~ r d o r l s deficiencies of the existing DOT system wit,h recommendntions for improvements Chemicals." This Onide, often referred was prepared in 1960. "A Study of to as t,he LAP1 hlamtnl, has heen used by Transportation of Hasxrdous Materials" the chemical industry and has served as a. was made under contract hy the Highway model for regulations. The 7th Edition Researoh Board and the Committee on was published in 1070. Hasnrdous Mat,erinls, National Academy The "Gnide to Preca~rtionaryLabeling of Sciences-National Research Council. of Haanrdona Chemicals" outlines some The Depart,ment of Defense (DO1)) has principles of labeling that sho~ildbe tanght adopted a standard pat,terned after the and used in the laboratory-from grade NFPA hazard identifimt,ion system plus school on. For example, "The use of the MCA gnide for prerantionnry Inheling. precautionary labels for relatively harmAdopt,ed in August,, 1070, the document less products, or the use of unnecessary is ent,itled "Symhols for Parkages and words, may develop a disregard for preContainers for Hazardous Industrial cautionary texts and defeat their purpose Chemicals and Ma.t,erinls," and referred t o as sorely as will failr~reto give adequate a*MIIATD-134IA.. notice of hazards." Renders are invited The DOD standnrd r ~ l l for s symhols to t o see whether they e m find m y hazardous he applied to rontainel.~of any mrtterid chemicals in s laboratory that have any listed as hazardolrs in NFPA pnhlirntinns precautionary lnhel, except, those from a or having similar charncteristirs, or as major marn~fact,~~rer or snpplier. defined in the MIT,-STD-I34lA. The The Mannfnct~wing chemist,^ Associaforeword states "The purpose of this. t,ion is located a t 1825 Cnnneot,icnt, Avestandnrd is t,o establish x tiniform symbol m e N.W., Washington, D. C. 20009. t,o warn personnel of t,he potential dangers They piihlish Chemical Safety Data Sheets involved wit,h handling and storing mateon many chemicals, and other safety rial in containers." information. The DOD standard excludes explosives, Organizations Regulating Hazard hulk fuels, and rhemiealn or drugs "procured dirertly hy medical department Identification pharmacies or clinicill or chemical IahoraOne of the moat widely used systems tories." The exception of laboratory of identifying hazardous materials is chemicals is difficnlt to mderstand in view administered by the Department of Transof the hasards of large glass hottles of portation (DOT). The system has been flammable solvent,^ nnd other hazardous in legal force for over fi0 years and is based chemicals which are often stored or handled on trmsportstinn industry reg~dations in lahorntories. established emlirlier h v t,he Bweao of Explosives of the Assoriat,ion of American Rnilroads.
Identification of Hazardous Materials-Part
Volume 48, Number 10, October 1971
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The Food and Drug Administration has the responsibility of enforcing the reguls, tions of the Federal Hazardous Substances Act (FHSA), adopted in 1960 and amended in 1966. Although the Act and regulations adopted under the act are not likely to affect laboratory operations or the identification of chemicals entering the laborstory, the system is worth noting as the best currently in use for providing precautionary information on all containers of hazardous materials regulated. The Act applies to any hazmdous substance whieh moves in interstate commerce and is intended for use in the household or by children, or whieh is packaged in a form suitable for such use. Regulations adopted under the Act define such hszardous suhstanees as those which might he brought into or around any dwelling, carport, barn, storage shed, or similar building. "The test is whether it is reasonably foreseeable that the container would be found in or around a dwelling and thereby expose persons to the particular hazards of the substance," aceording toFDA publication number 35, March, 1968. Excluded from the regulations and the Act are industrial materials not intended for home use, materiale brought into a home by a repair man, and the materials regulated by Federal laws on drugs and economic poisons. The Department of Labor (DOL) has had a growing role in regulating hazardous
m&terids in the workplace, and two examples will be mentioned. One area. of activity in which the DOL has taken recent steps to control hsaardons materials is ship repairing, shipbuilding, and shipbreaking. DOL adopted regulations in 1968, under the Longshoremen's and Harbor Worker's Cornpensstion Act, that required employers to obtain specific information on certain defined hazardous materials. The Material Safety Data Sheet required under this set is known as LSB-OOS-4, the same form also being required for hazardous materials regulated by the DOD military standard. The Department of Lnhor has been given broad new responsibility for adoption and enforcement of safety standards for every employer engaged in intirstate commerce. The 1970 Occupational Safety and Health Act gives the Secretary of Labor the authority to adopt existing consensus standards which have been developed by t,he American National Standards Institute and the National Fire Protection Association. The Secretary of Health, Edncat,ion, and Welfare has been given eertain responsibilities under the 1970 Occupationa.1 Safety and Health Act, including the preparation and publiention of a list of d l known toxic substances, gathering of statistics on work injuries and illnesses, and the acquisition of information regarding potentially toxic and harmful materials. The Act also established a National Institute for Oeeupational Safety and Health which is authorized to develop and establish recommended standards.
Our examinntion of hazardous nmterials identification systems will include illustrations of labels and discussion of labeling problems, after we look a t the confusing matter of definitions and terminology. The first subject for consideration will be flammable materials, beginning wrlh flemmableliquids.
FLAMMABLE MATERIALS Flammable Liquids and Combustible Liquids As one example of a hazard term having different meanings, consider flammable liquids. Flammable means "capable of being easily ignited and of burning with extreme rapidity" according to Webster's Third New International Dictionary, 1961. The technical definition used in regulations 'by the Department of Transportation limits flammable liquids to those whieh give off flammable vapors a t or below a temperature of UOPF (26.67"C), as determined by Tagliabue's Open Cup Test. Flammahle liquids are defined by the National Fire Protection Association in NFPA No. 321-1965 as any liquids having a flash point below 140°F (60°C), and having s. vapor pressure not exceeding 40 psia (2068.6 mm) a t 1 0 0 T (37.U°C). Not only is there s 60°F or 37'C range of flash points in whether a. liquid called flammable in NFPA gtandards is called flammable by DOT regulat,ions, there is great variation in whether the term will be used on the chemical container. NFPA stmdards have not usually had the force of law for making containers or vessels, although the standards may he applied under the 1970 Occupational Safety and Health Act. Under DOT regulations, flammable liquids with flash points a t or below 80°F are not identified as "flammable" on the container unless they are in a tank truck. Flammable liquids regulated by DOT in containers other than tank trucks or tank cars, are required to be marked with a red label except if the containers arenot over 1 pint or 16 ounces or are metal containers not over 1 quart in capacity. Red labels for flammable liquids must be of diamond shape, bright red in color, and with each side 4 in. long. The precautionary wording on the red label is limited to "Keep away from fire, heat, and open-flame Iights-CAUTION-Leaking packages must be removed to a.sde place." Flammable liquids regulated by DOT are identified, ss are most other dangerous materials in rdilroad cars, by a. 108/, in. square diamond placard whieh must contain the following precautionary information: "Keep lights and fires away!DANGEROUS-(Name of cont,ents)Handle carefully-This ear must not he next to a ear placarded ExplosivesAvoid contact with leaking acid or eorrosive liquid-Beware of fumes or vspors-When lading is removed this plaeard must be removed or reversed." I n certain new regulations the Department of Labor and the Department of
(Continued on page A6BO)
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Defense prefer use of the NFPA definition of flammable liquids by defining hazardous material to include any with a flash point below 140°F, closed cop. The two Departments also refer in the same part of their definitions to materials subject to
M I L - S T T ~ - ~ ~ ~ which IA calls for- all flsmmahle and combustible materials to be in containers marked with the hasard identification signal described in NFPA SeptemNo. 704M (see also Tnrs JOURNAL, her, 1971, "Safety in the Chemical Laboratory"). The diamond-shaped hasard signal would show a. hasard devee of 2 for combustible and flammable liquids with flash points ranging fram 200°F down to just ahove 10O0F, a hazard rating of 3 for flammable liquids with flash points below 100°F and boiling point a t or ahove 100°F a. hazard ratine of 4 for 1R7.U°C). and ~ ~ .- , z ~ . flammable liquids with flash p&ts below 73OF (22.R°C) and boiling point,s below 100°F (37.R°C). The hazard rating of 4 is the hiehest degree of hazard assigned t o any material i n the categories of emergency health hasard, flammability hazard, and instability or reactivity hnsard. The flammabilit,y hazard of 4 also includes flammable gases, flammable cryogenic materials, and other materials which will rapidly or completely vaporize or disperse and h i m readily. The Department of Defense has also adopted MIL-STD-129 which requires labeling in accordance with the Manufacturing Chemists' Associat,ion "Guide to Precautionary Labeling of Haaardous Chemicals." The eomhinst,ion of this system with the NFPA hazard signal system wonld provide a chemical container label with several very desirable features: a "headlinen-visible from n. distnneesignaling t,he relative degree of hnsard in case of a spill or fire for emergency health hasard, flammability hasard and instability hazard; a "suhhead" consisting of the name of the chemical and x signal word designating degree of hazardDanger!, Warning!, or Caution!; and a brief text on hazards, precaotionary messores and other pertinent information. Labeling requirements under the 1970 Occupational Saiety and Health Act have not yet been fully spelled out. However, the Boreau of Labor Standards of the Department of Labor provided technical assistance in the development of MILSTD-1341A and has expressed strong interest in having the same combination of systems used as broadly as possible in workplaces in theU.S. The Federal Hasardous Suhstances Act defines two different berms for flammable liquids. Extremely flammable applies to any substance which hes a flash point a t or below 20aF, as determined by the Tagliabue Open Cup Tester, and flemmable applies to any substance with a. flash point fram 20°F to and indnding 80°F.
(Continued on page A66.7)
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The Manufacturing Chemists Association (MCA) have definit,ions for +,hi-ee classifications of liquids that produce flammable vapors. The definitions are cont,ainedin their "Guide to Precautionary Labeling of Hazardous Chemicals," Manual L-1, 7th Edition, 1070. The definitions for extremely flammable liquid and flammable liquid are identical to the definitions given in the Federal 11Iazardons Substances Act, which undoubtedly d e rived the definitions from one of the editions of the Guide. The MCA Guide or Manual defines liquids that have x flash point above 80°F t o and including 150°F as comhustibleliquids. Table 1 shows a tahulation of the flash pnint ranges in the definitions used by several organizations for flammable and combustible liquids.
Table 1. Definitions of Flammable Liquids and Combustible Liquids
Extremely flammable Flammable N Combustible Volume 48, Number 10, October 1971
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