in the Chemical f aboratory Edited by NORMAN V. STEERE, 140 Melbourne Ave., S.E. Minneapolis, Minn. 55414
XC. Identification of Hazardous Materials-Part
VI
Stringent New Pmckmghg Req~irementrfor Niolosic Agsntr to be Set
NORMAN V. STEERE FEDERAL STANDARD FOR CHEMICAL HAZARD SYMBOLS The U S . Federal Gov'ernment has established a new standard for symbols for hasardous material shipped to and by Government activities, and has taken initial steps to implement the requirements of the standard. The Federal Standard, No. 313, is entitled "Symbols far Packages and Containers for Hazardous Industrial Chemicals and Materials." The standard was adapted under provisions of the Federal and Administrative Service Act of I949 and coordinated with all Government departments for publication on July 23, 1971. First action to ~ u the t standard into effect was a notice in the Federal Register an November 17, 1971, that after November 1 the Department of the Navy of the Department of Defense will incorporate the st.andard into invitations for hid and requests far quotation. The Federal Register notice states that the standard requires application of new symbols depicting haaardous characteristics and submission of Mat,erial Safety Data Sheets, tells where copies of the standard can be obtained, and explains that the standard incorporates two industry standards by reference, the NFPA Fire Pmtection Guide on Hazardous Materials and the MCA Guide to Precautionary Labeling of Hazardous Materials. Single copies of the Federal Standard No. 313 are available without charge from Business Service Centers a t General Services Administration Begiond Offices in Atlanta, Boston, Chicago;Eort Worth, Kansas City (Mo.), Los Angeles, New York, San Francisco, Seattle, and Washington, D. C. Additional copies can he obtained for 25 cents each fmm General Services Administration, Specification Sales, Self Service St,ores and Fuels Division, Building 197, Washington Navy Yard, Washington, D. C. 20407. Government contracbors can obtain the standard from the Navd Publication and Farms Center, 5801 Tabor Avenue, Philadelphia, Pa. 19120. Further information on Federal Standard No. 313 may he obtained from the Commander, Naval Supply Systems Command (Attention: SUP 056), Washington, D. C. 20390.
Review and Comment on the Stondord Application of the Federal Standard No. 313 in laboratories will provide safety benefits but will also create problems which may be difficult and expensive to deal with. Precautionary information on
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labels of hazardous materials and in Material Safety Data. Sheets will be available to guide chemical users and their upervisors, and the hazard symhols will help direct attention to the more important precautions and to preparation for handling and controlling emergencies from spills and exposures. However, there are going to he the problems of training people to read the labels, understand the data sheets, and recognize the meaning and limitations of the hazard symbols, and the additional problem of maintaining a reasonable continuity of labeling when chemicals are repackaged, dispensed or transferred to smaller cantainers for temporary storage. Federal laboratory personnel have procedures and channels prescribed by the standard for citing difficulties and inadequacies of the standard. Federal agency laboratories which consider that the new Federal standard does not provide far their essential needs should cite inadequacies and conflicts with any referenced specifications to the General Services Administration, Federal Supply Service, Standardization Division, Washington, D. C. 20406. Military laboratories are to submit comments via, appropriate de~artmental custodians (Air Force-43. A r k y - ~ b ,Navy-SA) to 'the preparing activity (NavySA). Since Federal Stmdard No. 313 will probably farm the basis of regulations for all laboratories under the Occupational Safety and Health Act of 1970, nonFederal laboratories should review the standard to see how i t may affect operations and whether any changes appear necessary or desirable to make the standard more workable without any loss of effective protection. Comments may he directed to the Hazardous Material Program Coordinator, John Neubauer, Naval Supply Systems Command, Attention: SUP 056B, Washington, D. C. 20390.
Purpose and Scope of the Standard The purpose of Federal Standard No. 313 is to require uniform symhols and labels for packages and containers of hasardous materials shipped to and by Federal agencies, and to require suhmission of Material Safety Data Sheets by contractors and manufacturers selling hasardous material to the Federal government. Requirements established in the standard provide for application of hazard symbols and labels to shipping containers and interior packages down to a certain size, when the hazards are greater than a prescribed minimum level. The standard
The Hazardous Materials Regulations Board of the U.S. Department of Transportation is proposing to establish stringent new packaging snd labeling requirements for shipment of viable micro-orgitnismr and toxins which cause or are sospected of causing human disease. Interested persons may submit comments before April 4, 1972 for consideration before final action is taken. The Proposed Reqnirements for Shipment of Etiologic Agents were published in the Federal Register on Wednesday, Decemher29,1971.
This proposal is made under the authority of sections 831-835 of title 18, United States Code, section 9 of t,he Department of Transportation Act (49 U.S.C. 1657), and title V I and section 902(h) of the Federal Aviation Act of 1958 (49 U.S.C. 1421-1430 and 1472(h)). is to be referenced in Federal comrnodit,y specifications, purchase descriptions, purchase orders, contracts and other purchase documents.
Deflnitions The standard defines some packaging terms, same specific hazards, and the degrees of emergency health hazard, fire hazard, and reactivity (instability) hazards. Degrees of hazard were reprinted with permission from NFPA No. 704M.
Packaging Terms The following packsging terms are used in the standard: Unit Load-a. shipping unit comprising two or mare shipping containers on runnee, platform, skid or pallet. Shipping Container-a container in which material may he shipped wit,hout addiaional protection. Inteiior Container-a eont,ainer that ia not a. shipping container. (Continued on page A140)
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Interrnediote P a c k a g e a n interior container that holds two or more unit packages of the same item of supply. Unit P a c k a g e t h e first container that holds an item identified by a single stock number as the identifiable stock unit. Sub-unit Package-the first container that holds an item identified as a component of astock unit.
Speciflc Hazards Five different specific hazards may be identified by abbreviation or symbol in the bottom quadrant of the hasard symbol: oxidizers, acids, alkalies, corrosives, and water reactive materials. The abbreviations or symbols corresponding to the characteristics listed are: OXY, ACID, ALK, COR, a n d W . The definitions given in the standard are as follows: Ozidizing Material-a substance such as chlorate, permanganate, peroxide, or a. nitrate that yields oxygen to support combustion or which reacts readily to oxidize fuels or other combustible materid. Corrosive Material-acids, alkali or other material that will cause severe damage to living tissue or to other materialit contacts. Water Reactivity Hazard (Use No WaterFsny material that because of specific reactivity with water may be a hazard. (The explanation of the symbol 'LW" in NFPA NO. 704M is that it is the recommended signal to indicate "unusual reactivity with and to alert the fire fighting personnel to the possible hazard of using water." Figures in the standard show the meaning of 'W." as "Use NO WATER" which is enerally incorrect information for fire fghting, fire protection, and first aid.)
Degrees of Emergency Health, Fire and Instability (Reactivity) Hazards Federal Standard No. 313 incorporates a, hazard symbol system that is designed to signal relative degrees of hazard for three kinds of hazard. The system, which is established in NFPA No. 704M, provides for five rankings of hazard from concentrated, short-term exposure of personnel, from fire, and from reaction of chemicals. Rankine range from "0" (zero) for ordinary materials with no unusual hazards, such as water and nitrogen, to "4" for extreme hazards such as the emergency health hnzard of phosgene, the flammability of hydrogen, and the instability of aeetyl peroxide. Limitations of the hazard signal system and the needs for further definitions to guide the assignment of hasard rankings will be discussed rtt the conclusion of this article. Since the hazard signal system is to be applied widely, i t is no longer possible for all hazard degrees to be selected by one committee or a few individuals, so that more detailed definitions must be developed to provide the basis for uniform selection by all the people who will now have such responsibility. (Continued on page A1481
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Federal Standard No. 313 includes the following definitions of degrees of healt,h hazard, flammability hazard, and r e activity (instability) hazard reprinted from NFPA No. 704M with permission of the National Fire Protection Association. Certain explanatory material from PTFPA No. 70431 was omitted, so that anyone who becomes responsible for implementing the hazard signal system should he certain to obtain NFPA No. 704M separately or as part of the NFPA Fire Protection Guide on Hazardous Materials. (The Guide is avsilahle for $5.30 from the NFPA a t 60 Batterymarch St., Boston, Mass. 02110.)
Degrees of health hazard are ranked according to the probable severity af hamrd to personnel, as follows: 4 Materials whieh on very short exposure conld cause death or major residual injury even though prompt medical treatment, were given, including t.hose which are too dangerou to be approached without specialized protective equipment. This degree should include: Materials which can penetrate ordinary rubber protective clothing; Materials which under normal conditions or under fire conditions give offgases which are extremely hasardous (i.e., toxic or corrosive) through inhalation or through contact wibh or ahsorption through theskin. 3 Materials which on short exposure could cause serious temporary or residual injury even though prompt medical treatment were given, including those requiring protection from all bodily contact. This degree should include: Materials giving off highly toxic combustion products; Xsteridls corrosive to living tissue or toxic by skin absorption. 2 Materials whieh an intense or continued exposure could cause temporary incapacitation or possible residual injury unless prompt medical treatment is given, including t,hose requiring use of respiratory protective equipment with independent air supply. This degree should include: Materials giving off toxic comhustion pro duet^; Materials giving off highly irritating comhustion products; Materials which either under normal conditions or under fire conditions give off toxic vapors lacking warning properlies. 1 Materials which on exposure would cause irritation hut only minor residnal injury even if no treatment is given, including those which require use of an approved canister type gas mask. This degree should include: llaterids which under fire conditions would give off irritating combustion products; (Continued on page A144)
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Materials which a n the skin could cause irritation without destruction of tissue. 0 Materials which on exposure under fire, conditions would offerno hazard beyond that of ordinary combustible material.
materials to burning ss follows: 4 Materials which will rapidly or completely vaporize a t atmosphe~icpressure and normal ambient temperature or which are readily dispersed in air, and whieh will hurn readily. This degree should include: Gases; Cryogenic materials; Any liquid or gaseous material which i8 a liquid while under pressure and having a flash point below 73°F (22.8'C) and having a boiling point below l O O 0 F (37.8'C). (Class IA flammable liquids) Materials which on account of their physical farm or environmental conditions can fonn explosive mixtures with air and whieh are readily dis-
3 Liquids and solids that can he ignited under almost all ambient temperature conditions. Materials in this degree produce hazardous atmospheres with air under almost all ambient temperatures or, though unaffected by ambient temperatures, are readily ignited under almost all conditions. This degree shouldinclude: Liquids having s flash point below 73'F (22.8%) and having a boiling paint a t or above 100°F (37.8'C) and those liquids having a flash point a t or above 73°F (22.8'C) and below 100°F (37.8"C). (Class IR and Class IC flammable liquids); Solid Materials in the farm of coarse dusts which may hurn rapidly but which generally do not form explosive atmospheres with air; Solid materials in a fibrous or shredded form which may burn rapidly and create flesh fire hazards, such as cotton, sisal and hemp; Materials which burn with extreme rapidity, usually by reason of selfcontained oxygen (e.g., dry nitrocellulose and many organic peroxides); Materials which ignite spontaneously when exposed to air. 2 Materials that must be moderately heated or exposed to relatively high ambient temperatures before ignition can occur. Materials in this degree would not under normal conditions form hazardous atmospheres with air, but under high ambient temperatures or under moderate heating may release vapor in sufficient quantities to produce hazardous atmospheres with air. This degree should include:
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Liquids having a flash point ahove 10O0F, but not exceeding 200°F; Solids and semi-solids which readily give off flammable vapors. 1 Materials that must he preheated before ignition can occur. Materials in this degree require considerable preheating, under all ambient temperature condibians, before ignition and combustion e m occur. This degree should include: Materials which will burn in air when exposed to a temperature of 1500°F' for a period of 5 minutes or Igs; Liquids, solids and semi-solids having aflsshpoint ahove 200°F; This degree includes most ordinary combustiblematerials. 0 Materials that will not hum. This degree should include any material which will not bum in air when exposed to a temperature of 1500'F for a period of 5 minutes.
The degrees of reactivity hazard are ranked according to ease, rate and quantity of energy release as follows: 4 hlaterials which in themselves tlre readily capable of detonation or of explosive decomposition or explosive react,ion a t normal temperatures and pressures. This degree should include materials which are sensitive to mechanical or localised thermal shock s t normal temperatures and pressures. 3 Materials which in themselves are capable of detonation or of explosive
decomposition or explosive reaction hut which require a strong initiating source or which must be heated under confinement before initiation. This degree should inclnde materials which are sensitive to thermal or mechanical shock a t elevated temperatures and pressures or which react explosively with water without requiring heat or confinement. ? Materials which in themselves are normally unstable and readily undergo violent chemical change but do not detonate. This degree should include materials which can undergo chemical change with rapid release ifenergy a t normal temperatures and pressures or which can undergo violent change a t elevated temperatures and pressures. I t should also include those materials which may react violently with water or which may form potentially explosive mixtures with water. Materials whieh in themselves are normally stable, hut whieh can become unstable a t elevated temperatures and pressures or which may react v i t h water with some release of energy hut not violentlv. 0 Materials which in themselves are normally stable, even under fire exposure conditions, and which are not reactive with water.
Hazard Identification on Material Safety D d a Sheets Federal Standard No. 313 specifies that the hazard identification signal and any
specific hazard abbreviation or symbol be shown on the Material Safety Data Sheet. On Form LSB-OOS-4 the hazard identification is to be entered immediately to the right of the heading Material Safety Data Sheet, in the sequence beginning with the emergency health hazard a t the left center of the diamond signal and proceeding clockwise through the flammability hazard to the instability (reactivity) hazard, if any. This format is consistent with the method used in NFPA tables, with the format used in the Consolidated Hazardous Item List issued by the Navy, and with computer tabulations used in industry. One method of showing the data, given as an example in the standard, for a material hazardous to health (2), flash point ahove 200°F ( I ) , ~mstahle if heated (I), and a corrosive acid, would be: H2, F1, R1, S. ACID The method used in the Consolidated Hazardous ltem List would show the data in columns: 2 1 1 under the headings: H F R. One method used in industry tilbdates the numbers as 2-1-1. For uniformity and to avoid error in transfer of data, the author believes the same sequence of data should he entered next to the heading Material Safety Data Sheet on Form DL) 1813 if that form is used. Farm 1)U 1813 provides blanks in Section I to enter hazard signal numhem, hut, the sequence lists flammability hazard before rather than after health hazard. (To be continued)
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