Hazardous Materials

he events that initiated the war against al-Qaida and other Islamic terrorist groups in ~hich the United States and its allies are now engaged.

During the aftermath of 9-11, emergency responders widely acknowledged the evolu- tion of a new component of their workload: the necessity to conduct rescue and recovery work at incidents where hazardous materials were intentionally released to the environ- ment, Although emergency responders continue to serve the nation by saving lives, prop- erty, and the environment, they now also must help secure the homeland and preserve our way of life.

The 9-11 incidents changed the course of world events and drew attention to the presen~e of a religious ideolo~y th~t promotes terrorism internationally. Islamic extremists have now expanded mto virtually every civilized country, where they spon- sor suicide attacks against the local population. The more notorious incidents spear- headed by radical Islamic terrorists occurred in 2004 when bombings of Madrid's commuter trains_ killed 191 people; in 2005, when bombings in London's. underground transit system killed 52 people; in 2008, when bombings in Mumbai's financial dis- trict killed 166 people; in 2010, when synchronized twin bombings in Kampala (Uganda) killed 76 people; and in 2011, when a suicide bomb at Moscow's Domode- dovo Airport killed 37 people. In each instance, the extremists chose to produce injury and death by detonating explosives.

Americans have also been attacked by terrorists within our domestic borders. In 2013, for example, two terrorists, ethnic Chechens, detonated two shrapnel-packed pressure- cooker bombs within seconds of each other near the finish line of the Boston Marathon. Now considered the worst terrorist attack on American soil since the events of 9-11, the lawless deed killed three people and injured over 260.

The nature of hazardous materials did not change since the 9-11 incidents, nor did the manner in which we respond at hazardous materials scenes; but the 9-11 terrorist events did spawn a heightened awareness of the unorthodox ways in which hazardous materials may be used as weapons of mass destruction to intentionally kill and injure vast numbers of people, cause substantial property damage, and affect economic stability. They also alerted emergency responders to perform their jobs with an intensified sense of vigilance by anticipating that the acts may be executed within their communities, espe- cially during large crowd gatherings.

We begin our study in this first chapter by broadly examining the general features of all hazardous materials. We also observe how federal statutes aim to eliminate or reduce the risks associated with the usage, storage, and transportation of hazardous materials, and how they may assist emergency responders at disaster scenes. Finally, we learn that allied professionals stand ready to help responders when hazardous materials are involved in emergencies.

1.1 WHY MUST EMERGENCY RESPONDERS STUDY CHEMISTRY?

Odds are you have never considered what life would be like without chemistry. If you had, it would soon be apparent that chemistry affects everything we do. There is not a single instant during which we are not affected by a chemical substance or a chemical process. . Chemistry is regarded as a natural science; that is, it is a subject concerned with study- mg natural phenomena. Specifically, the science of chemistry is the st udy of substances, their composition, properties, and the changes they undergo. Chemistry concerns itself not only with substances that occur naturally but also with synthetic substances.

. By understanding the interplay of various substances, chemists have successfully con- tributed to combating the scourges of hunger, disease, and human deprivation throug hout the world. By using established methods, chemists aspire to further improve the quality of

chemistry The natural science concerned with the properties, composition, and reactions of substances

Chapter 1 Introduction 3

o rgan ic chem istry The study of the prop- erties of substances that contain carbon in their chemical composition

inorgan ic chemistry The study of the prop- erties of substances that do not contain carbon in their chemical composition

our lives in the future . For instance, during the twenty~first century, ~e anticipate th chemistry will radically alter the methods used to ~reat sicknesses and ~1sease. a

Chemistry is broadly divided int~ two mam branches: _organic chemistry a inorganic chemistry. At one time, chemists presumed that certam substances couJd ~c in the world only if they had originated in living things-plants and animals . These elQsi stances included sugars alcohols, waxes, fats, and oils, all of which were called or su?.

' · · h · 1 f f 1·c · gan1c substances because their origin was believed to require t e vita orce o 11e itself. In 1828, this hypothesis was disproved when Friedrich Wohler prepared a substa

called urea, a known constituent of urine. Wohler succ~ssfully pr~pare~ urea frorn s:~~ stances having no apparent connection to plants or ammals. This achievement cau

· d f h d · sed chemists to abandon the idea that a vital force was reqmre or t e pro uct1on of cen . substances. Despite abandonment of the hypothesis, however, the name of this branch chemistry has been historically retained.

Organic chemistry is now recognized as the study of substances that contain carbo in their chemical composition. Although some organic substances are actually found i: living systems, many others have been synthesized that have no known natural counter. part. The study of organic substances that affect the life process is now regarded as a subdivision of organic chemistry called biochemistry. By contrast, the study of those sub. stances that do not contain carbon in their composition is known as inorganic chemistry. Inorganic substances include aluminum, iron, sulfur, oxygen, table salt, and many others.

To be an effective emergency responder, is it necessary to study organic and inorganic chemistry? It would be misleading to give the impression that the academic pursuit of chemistry is essential for achievement of successful careers as firefighters, police officers and other emergency responders. Nonetheless, the study of hazardous materials by emer'. gency responders achieves the major objective of enriching their sense of inquiry while investigating accident scenes at which hazardous materials are implicated. Without the knowledge acquired from the study of hazardous materials, emergency responders are severely limited when they must select a course of action during the performance of duty.

1.2 FEDERAL HAZARDOUS SUBSTANCES ACT The Federal Hazardous Substances Act, or FHSA, was first enacted by Congress in 1960. Thereafter, it was amended to focus on the protection of users against unsuspecting expo· sure to hazardous substances contained within consumer products. The statute is adrnin· istered by the Consumer Product Safety Commission (CPSC) .

One way by which CPSC fulfills its congressional mandate is to require manufacturers to affix appropriate labeling on the containers of consumer products that contain hazard· ous substances. This labeling information is directed primarily at consumers, bur it is potentially helpful to emergency responders and others. At 16 C.F.R. § 1500.121, 1 CPSC requires the following information to be clearly and conspicuously provided on the labels affixed to containers of consumer products having hazardous substances as components:

Federal Hazardous Subst a nces Act The federal statute that empowers the CPSC to protect the public against unsuspecting exposure to hazardous substances contained within household products

The name and place of business of the manufacturer, packer, distributor, or seller The common or usual name or the chemical name of each hazardous ingredient The signal word DANGER for products that are corrosive extremely flammable, or highly toxic ' The signal word CAUTION or WARNING for all other hazardous products . The word POISON in addition to the signal word DANGER for the highly roxic products listed at 16 C.F.R. §1500.129

1R l . . ' d l I · -oo 121 e evam citations to 1e era regu at10ns are noted throughout this text. The reference to 16 C.f.R. §l_J · ub· means T1~le 16 of the Code_ of Federal Regulations, Part 1500, Section 121. The parts are a lso di vid ed inro :

0 05 p_arts,_ which are denoted with capital letters A, B, C, and so on. Readers ma y electronically access all regul arI cited m this text on the Internet.

4 Chapter 1 Introduction

1 Railroad accidents involving passenger trains or any train accident that results in at least one fatality or major property damage

1 Major marine accidents and marine accidents involving watercraft 1 Pipeline accidents involving a fatality or substantial property damage 1 Releases of hazardous materials in all forms of transportation 1 Selected transportation accidents involving problems of a recurring nature

The NTSB has investigated numerous accidents and developed factual records and safety recommendations. Its findings are made public on the Internet and elsewhere.

1.8 INTEGRATED CONTINGENCY PLANS Although the owners and operators of a facility may be subject to preparing and imple- menting one or more separate, stand-alone emergency response plans, they may also elect to consolidate them into a single contingency plan called an integrated contingency plan, ICP, or one plan.

4 This document sets forth the following goals:

To provide a single integrated plan that consolidates the requirements of multiple facility emergency response plans To improve coordination of planning and response activities within a facility and with public and commercial emergency responders To minimize duplication

If a facility's owners or operators elect to prepare an ICP, the document must comply with the individual requirements of the plans concerned with emergency response activi- ties mandated by several federal statutes and administered by multiple participating agen- cies. The following five plans noted in this chapter may be incorporated into an ICP, as they are needed:

Risk management plan mandated by Clean Air Act regulations (40 C.F.R. Part 68) Facility response plan mandated by Clean Water Act regulations (40 C.F.R. §§112.20 and 112.21) Contingency plan mandated by RCRA regulations (40 C.F.R. §§264.52 and 265.52) Emergency action plan mandated by OSHA regulations (29 C.F.R. §§1910.38)

I Vessel or facility response plan mandated by DOT regulations (49 C.F.R. Part 194 and 33 C.F.R. Part 154, Subpart F)

integrated conti ngency plan (ICP, one plan) A single emergency response plan that incorporates into one document the regula- tory requirements of the emergency and contingency plans man- dated by multiple fed- eral statutes

Standard formats for the preparation of ICPs have been developed by EPA. This for- mat may be adopted by facility owners and operators as they integrate multiple plans into a single plan.

1.9 GLOBAL HARMONIZATION CONCERNING THE CLASSIFICATION AND LABELING OF HAZARDOUS CHEMICALS

Over the years, most civilized countries have implemented methods for identifying haz- ards and classifying and labeling chemical products. In many instances, these methods vary significantly from country to country. Even within the United States, four federal authorities-OSHA, CPSC, EPA, and DOT-have the responsibility to warn consumers that certain products are potentially harmful. Although similarities exist, the agencies'

:j":--_ 61 Fed. Reg. 28642 (June 5, 1966 ).

,., I ; ~ii United Nations

Chapter 1 Introduction 17

r . . d of classification and labeling have created unneces. inconsistent and confhcnng metho s sary confusion for the public. . I for defining and classifying hazards and To circumvent this use of mwnp ehsy~e~sd Nations designed the GHS, known fo ,_

communicating hazard informauon,St e ni ; Classification and Labeling of Chemical mally as the Globally Harmonized _Ystem O f rules with a common format and content Substances.5 The basis of the ~ystem ths ahset O d f chemical products on warning label

I GHS The United Nations system for defining and classifying hazards and communi- cating hazard informa- tion on labels and safety data sheets by means of a common international format

for worldwide use when classifying t e azar s O s and Safety Data Sheets. nd OSHA revised their regulations to align with the GH.s,

In the United States, DOT~ . . Ch • I manufacturers are now in th and EPA and CPSC are studying 1ts adoption. emica c Process of complying with these regulations. . I 'f' · d I b . 'd b . f greater consistency in the c ass1 icatton an a eltno The GHS prov1 es a aSlS or a . · h k 0 of hazardous chemicals, thus enhancing their safe handh~g and st0.rage m t e wor place

· GHS b dly uses the term to include unique substances, prod-or a consumer-use setting. roa ff d d h · that could potentially cause harm. It a or s emergency

ucts, adn ot _ethr prepharattons of rapidly identifying the hazard(s) associated with expo- respon ers wt anot er means bl' h I h sure to substances that could cause an unreasonable risk of injury to pu 1~ ea_ t . or the environment. Its worldwide utilization also provides a means for r~pidly identify~g ~ e nature of a hazardous material that was manufactured abroad but imported and distrib- uted in the United States.

GHS communicates hazard information in the three major hazard groups listed in Table 1.2: physical hazards, health hazards, and environmental ~az~rds. _Most hazard classes are further subdivided into multiple categories, each of which 1s derived from cri- teria that are based on the results of prescribed testing procedures. These individual cate- gories are not of interest here. . .

Inherent in the GHS is information that manufacturers and d1stnbutors of products affix on the labels to product containers. This information consists of the following:

The product identifier (product name, UN/NA identification number, and DO'f proper shipping name) 6 Either of the signal words WARNING or DANGER to denote the more and less severe hazard categories of the product, respectively One or more hazard statements One or more pictograms, of which there are two types: GHS pictograms that are dis- played on the labels of chemical products, and transport pictograms that are dis- played when the products are transported in commerce One or more precautionary statements including first-aid instructions Supplier identification (i.e., the name, address, and telephone number of the manu- facturer or distributor)

The GHS pictograms associated with the hazards exhibited by chemical products are displayed in Table 1.2. They are black-and-white, red-bordered, diamond-shaped warn· ing signs. Multiple pictograms may be displayed on the same container label to warn the observer of the potential hazards posed by the container's contents.

The ~rans~ort pictograms are displayed in Table 1.3. They have background colors and symbols identical to those used on the DOT labels and placards noted later in Figures 6.5 and 6.12, respectively. When a transport pictogram is displayed on a label, the red-bordered pictogram for the same hazard is not shown.

5 Globally Harm?nized System of Classification and Labeling of Chemical Substances (GHS ), (New York , N'i

and Geneva, Switzerland, 2011), ISBN-13: 978-92-1-117006-l. 6 The nature of the UN/NA identification number and DOT proper shipping name is discussed in Section 6.1.

18 Chapter 1 Introduction

N ,

E:

TABLE 1.2 GHS Pictograms for Labeling the Containers of Hazardous Chemicals

TYPES OF HAZARDOUS MATERIALS REPRESENTED BY NATURE OF GHS PICTOGRAM GHS PICTOGRAM GHS PICTOGRAM Exploding grenade Explosives; certain self-reactive substances and mixtures; certain

organic peroxides

- Flammable gases; flammable aerosols; flammable liquids; flammable Flame solids; certain self-reactive substances and mixtures; pyrophoric liq- uids and solids; self-heating substances and mixtures; substances and mixtures, that, in contact with water, emit flammable gases; certain organic peroxides

Flame over the letter "O" Oxidizing gases, liquids, and solids

Gas cylinder Gases under pressure

0 Corrosion Substances that corrode skin and serious eye damage; substances

that corrode metals

Skull and crossbones Certain acute toxicants

Health hazard Carcinogens (substances that cause cancer or are suspected of caus- ing cancer); respiratory sensitizers; reproductive toxicants; specific target organ toxicants (single exposure); certain specific target organ toxicants (single exposure) and target organ toxicants (repeated exposure); germ-cell mutagens;• aspirants

Exclamation point Certain acute toxicants, skin irritants, eye irritants, skin sensitizers,

¢ and specific target organ toxicants (single exposure) Environment (aquatic toxicity) Aquatic toxicants

aGerm.cell mutagens are substances that cause a permanent change in the amount or structure of a cell's genetic material.

Chapter 1 Introduction 19

I TABLE 1 .3 GHS Pictograms for Transporting Hazardous Chemicals TRANSPORT PICTOGRAM

NAME OF TRANSPORT PICTOGRAM

TRANSPORT PICTOGRAM

NAME OF TRANSPORT PICTOGRAM

TRANSPORT PICTOGRAM

NAME OF TRANSPORT PICTOGRAM

TRANSPORT PICTOGRAM

NAME OF TRANSPORT PICTOGRAM

Explosive 1.1

Explosive 1.6

Flammable Solid

Poison Inhala- tion Hazard

Explosive 1.2 Explosive 1.3

Flammable Gas Non-

Spontaneously Combustible

Material

,,•~:--. / ~" ;-, ·, ,,

~ -- Corrosive Material

Flammable Gas

Dangerous When Wet Material

Explosive 1.4

Poison Gas

Oxid izer

Explosive 1.S

Flammable Liquid

Organic Peroxide

The hazard and preca utionary statements are respectively coded with numbers pre- ceded by an Hor P, as relevant, Some representative examples are provided in Table 1.4. Aside from their use on the labels of chemical products, these statements are also compo- nents of the "Hazards Information" section of an SDS for a given chemical product,

OSHA's adoption of the GHS requires each chemical manufacturer, distributor, and importer to select the appropriate pictograms that describe their produces, The use of the environmental pictogram is optional because environmental hazards are regulated by EPA , not OSHA, Emergency responders may rapidly identify the hazards associated with the chemical products by looking at their labels and acknowledging the significance of rhe pictograms ,

When we study the properties of individual hazardous materials beginning in Chapter 7, GHS pictograms will be displayed with their hazard diamonds (Section 1.1 I) in the page margin near the point at which a discussion of each haz ar dous material fir5t begins ,

20 Chapter 1 Introduction

TABLE 1.4

HAZARD CLASS

PHYSICAL HAZARD GROUP Explosives (Division 1 .1)

Flammable gases

Flammable aerosols

Oxidizing gases

Gases under pressure

Flammable liquids

Flammable solids

Self-reactive substances and mixtures Pyrophoric liquids

Pyrophoric solids

Self-heating substances and mixtures

Substances and mixtures which, in contact with Water, emit flammable gases

Oxidizing liquids -

Some Representative Hazard and Precautionary Statements for the GHS Hazard Classes

HAZARD STATEMENTS

CODE EXAMPLE CODE H201 Explosive; mass explosion hazard . P201

P210

P202

H220 Extremely flammable gas. P210

P377

H222 Extremely flammable aerosol. P251

P211

H270 May cause or intensify fire; oxidizer. P244

H280 Contains gas under pressure; may explode if heated.

P410

P403 H224 Extremely flammable liquid and P240

vapor.

P241

P242 P243

H228 Flammable solid. P210

H240 Heating may cause an explosion. P220

H250 Catches fire spontaneously if P222 exposed to air.

H250 Catches fire spontaneously if P335 exposed to air.

P334 H252 Self-heating in large quantities; may P407

catch fire. P403

H260 In contact with water releases P223 flammable gases that may ignite spontaneously.

P234

H271 May cause fire or explosion; strong P283 oxidizer.

PRECAUTIONARY STATEMENTS

EXAMPLE Obtain special instructions before use. Keep away from heat/sparks/open flames/hot surfaces. No smoking. Do not fight fire when fire reaches explo- sives. Keep away from heat/sparks/open flames/hot surfaces. No smoking. Leaking gas fire : Do not extinguish, unless leak can be stopped safely. Pressurized container: Do not pierce or burn, even after use. Do not spray on an open flame or other ignition source. Keep reduction valves free from grease and oil. Protect from sun I ight.

Store in a well-ventilated place. Ground/bond container and receiving equipment. Use explosion-proof electrical/ventilating/ lighting/ .. ./equipment. Use only non-sparking tools. Take precautionary measures against static electricity.

Keep away from heat/sparks/open flames/hot surfaces. No smoking . Keep away from clothing/ .. ./combustible materials.

Do not allow contact with air.

Brush off loose particles from skin.

Immerse in cool water/wrap with wet bandages. Maintain air gap between stacks/pallets.

Store in a well-ventilated place. Keep away from possible contact with water, because of violent reaction and possible flash fire .

Keep only in original container. Wear fire/flame resistant/retardant clothing.

(Continued)

Chapter 1 Introduction 21

TABLE 1.4 f ary Statements for the Some Representative Hazard and Precau ion

GHS Hazard Classes (Continued)

HAZARD CLASS HAZARD STATEMENTS PRECAUTIONAR Y STATEMENTS PHYSICAL HAZARD GROUP CODE EXAMPLE CODE EXAMPLE

P220 Keep/Store away from clothing/combustible

I materials.

P280 Wear protective gloves/protective clothingt eye protection/face protection.

Oxidizing solids H272 May intensify fire; oxidizer. P378 Use for fire extinction. Organic peroxides H240 Heating may cause an explosion. P411 Store at temperatures not exceeding_ 'F

L'C). P410 Protect from sunlight.

Substances corrosive H290 May be corrosive to metals. P390 Absorb spillage to prevent material damage. to metals

P406 Store in corrosion-resistant/ ... container with a resistant inner liner.

Health Hazard Group Acute toxicity, oral H301 Toxic if swallowed. P310 Immediately call a POISON CENTER or doctor/

physician. Acute toxicity, H331 Toxic if inhaled. P271 Use only outdoors or in a well-ventilated inhalation area.

P340 Remove victim to fresh air and keep at rest in a position comfortable for breathing .

Acute toxicity, dermal H311 Toxic in contact with skin. P361 Remove/Take off immediately all contami- nated clothing .

Skin corrosion/irritation H314 Causes severe skin burns and eye P350 Gently wash with plenty of soap and water. damage. Serious eye damage/eye H320 Causes serious eye damage. P305 Rinse cautiously with water for several irritation

minutes P351 Remove contact lenses, if present and if easy

to do. P338 Continue rinsing.

Skin sensitization H317 May cause an allergic skin reaction. P350 Wash with plenty of soap and water. Germ cell mutagenicity H340 May cause genetic defects (Included P281 Use personal protective equipment as in the statement is the route of required.

exposure, if it is conclusively proven that no other routes of exposure cause the hazard.)

Carcinogenicity (cancer- H350 May cause cancer (Included in the P313 Get medical advice/attention . causing hazard) statement is the route of exposure, if known, when it has been conclu-

Reproductive toxicity H360

sively proven that no other routes of exposure cause the hazard.) May damage fertility or the unborn child (Included in the statement are the specific effect, if known, and the

P405 Store locked up.

route of exposure, when it has been conclusively proven that no other routes of exposure cause the hazard.)

22 Chapter 1 Introduction (Co ntinuedi

TABLE 1.4

HAZARD CLASS

PHYSICAL HAZARD GROUP specific target organ toxicity, single exposure

Specific target organ toxicity, repeated exposures

Aspiration hazard

Environmental Hazard Group Hazardous to the aquatic environment (acute hazard) Hazardous to the aquatic environment (chronic hazard) Hazardous to the ozone layer

Some Representative Hazard and Precautionary Statements for the GHS Hazard Classes (Continued)

HAZARD STATEMENTS PRECAUTIONARY STATEMENTS

CODE EXAMPLE CODE EXAMPLE H372 Causes damage to organ (Included P264 Wash thoroughly after handling

in the statement are the organ affected, if known, and the route of exposure, when it has been conclu- sively proven that no other routes of exposure cause the hazard.)

H373 May cause damage to organs P260 Do not breathe dust/fume/gas/mist/-vapor/ through prolonged or repeated spray. exposure. (Included in the state- ment are the organ affected, if known, and the route of exposure, when it has been conclusively proven that no other routes of exposure cause the hazard.)

H304 May be fatal if swallowed and P331 Do not induce vomiting. enters airways.

H400 Very toxic to aquatic life. P273 Avoid release to the environment.

H401 Toxic to aquatic life. P391 Collect spillage.

H420 Harms public health and the envi- P502 Refer to manufacturer/supplier for ronment by destroying ozone in the upper atmosphere.

information on recovery/recycling.

1.10 CANADA' S WORKPLACE HAZARDOUS MATERIALS INFORMATION SYSTEM

Chemical products are regularly transported across the common borders shared by the United States with Canada and Mexico. Although Mexico has adopted the GHS for vol- untary use, Canada was still considering the potential implementation in its workplace regulations during 2013 . Hence, it is relevant to note here how Canada communicates information concerning the hazards of chemical products to workers.

In Canada, when a hazardous material is encountered in the workplace, it is referred to as a controlled product. The Canadian Centre for Occupational Health and Safety, or CCOHS, regulates certain aspects of the controlled products used by employees through its Workplace Hazardous Materials Information System, or WHMIS. These regulations require suppliers to use the symbols for six hazard classes (denoted A through F) when labeling the containers of controlled products. They also require employers to ensure that their workers understand the meaning of these symbols and their use on MSDSs and labels. . The hazard classes of controlled products are depicted by the eight hazard symbols shown in Table 1.5. The symbols consist of black encircled pictograms on a white background.

Chapter 1 Introduction 23

TABLE 1.5

CLASS OF CONTROLLED PRODUCT

Class A: Compressed Gas

Class B: Flammable and Combustible Material

Class C: Oxidizing Material

Class O: Poisonous and Infectious Material

Division 1: Materials causing immediate and serious toxic effects

Class D: Poisonous and Infectious Material Division 2: Materials causing other toxic effects

Class D: Poisonous and Infectious Material Division 3: Biohazardous Infectious Material

Class E: Corrosive Material

Class F: Dangerously Reactive Material

24 Chapter 1 Introduction

NATURE OF CONTROLLED PRODUCTS . . d d ases hquef1e

Compressed gases, dis'.olved _gases, an g by compression or refrigeration

ble of catching fire in the Solids, liquids, and gases cap:iame under normal work- presence of a spark or open ing conditions

f f 'f they contact Materials that increase the risk o. ,re , flammable or combustible materials

Materials that cause death or immediate injury when a person is exposed to small amounts

Materials that can cause life-threatening and serious long-term health problems as well as less severe but immediate reactions in a person who ,s repeatedly exposed to small amounts

Materials containing an organism that has been shown to cause disease or to be a probable cause of disease in persons or animals

Includes caustic and acidic materials that can destroy the skin or "eat" through metals

Materials that self-react dangerously (e.g., they may explode} upon standing or when exposed to physical shock or increased pressure or temperature; materials that decompose or polymerize vigorously; and materi- als that react with water to release a toxic gas.

HAZARD SYMBOL

0 @

'<::::)

@

Al hough they are intended primarily to c · h d · · · h t ornmurucate azar mformat1on to employees mt e

workplace, th

e haza rd

symbols are also useful to emergency responders who encounter con- trolled products durmg a tra~sportation mishap or elsewhere.

Given th.e dose proxim_ity between the United States and Canada, GHS and WHMIS information is likely to be cited on th~ labels on chemical products imported from Canada into the U~ited S

t ates and exported mto Canada from the United States. The label illus-

trated in Figure. 1.3 pro~ides an e~ample of the manner by which the GHS and WHMIS convey _hazard mformatton associated with a 35% solution of hydrogen peroxide. The GHS pictograms a

nd WHMIS symbols inform the observer that the solution is an oxi-

dizer and corrosive m_aterial. that. damages the skin and eyes upon exposure. GHS also includes the product identifier, signal word, and hazard and precautionary statements including f1rst-a1d mstructions.

1.11 NFPA SYSTEM OF IDENTIFYING POTENTIAL HAZARDS

At the scene of an emergency, how is it possible to identify the potential hazards associ - ated with the presence of a given hazardous material? The answer to this question is based on recognizing certain markings that are posted on stationary tanks, exterior building walls, pipelines, and other fixed facilities at which hazardous materials are stored or used.

The National Fire Protection Association, or NFPA7 uses a procedure that provides a means for rapidly identifying the relative degree of three chemical properties associated with a given hazardous material: its health, flammability, and instability hazards. 8 NFPA implements this procedure by assigning one of five numbers, 0 through 4, to each prop- erty for a given hazardous material. The numbers in Table 1.6 identify the relative degree of hazard that corresponds to a relevant property. The number O signifies that the hazard- ous material at issue does not possess the relevant hazard, whereas the number 4 denotes that it possesses the highest degree of that hazard.

National Fire Protection Association (NFPA) The professional organ- ization that promotes and improves fire pro- tection and prevention and establishes safe- guards against loss of life and property by fire

SOLVED EXERCISE 1.2

Wh en fi refi ghters respond to a fire in a tan k farm , what informati on is im me diately needed to help them effec- tively fight the fire ?

Solution: When they respond to a fire within a tank fa rm, fire fighters require re~dily accessible and accurate in - formati on concern ing the hazards of the tank contents. Accordingly,. t he inform~t,on marked on the tanks should be easily vi sible and legible and should incl ud e th e.nam es of the l1qu 1ds stored w1th1n them, the ir general hazards, and speci al fi refig hting precautions of which th e f1ref1ghters should be aware . . .

To conve hazard information, NFPA recommends the use of n.umbe'. codes that are marked w1 th1n the top th d y f d' d haped symbol pa inted on or otherwise affixed to, the exterior surfaces of storage ree qua rants o a 1amon -s ' . d h 1 • tanks. Be in nin with the left-hand quadrant and proceeding cloc kwise, the number codes enote t . e re at,ve d gf h lg h fl blt and inst abi lity hazards of the su bstances stored w1th1n each ta.nk . Firefighters c~~e:;e

0 eac~an~~ b=~::\~ ;~:·a propriate information listed in Table 1 :6. Spedal codes are provided 1n the bot-

t P d Th ' b' t' pf ·nformation helps fi refi ghters determ ine wh,ch actions to take an d not to tak e om qua rant. ,s com ,na ,on o , when they fi rst encounter a fire within a storage tank.

'N · · · 1 B h Park Quincy MA 022 69- 9101. attonal Fire Protection Assoc1at1on, atterymarc ' , C . h © JQl 1 8NFPA 704-2012 , System for the Identification of the Hazards for Emergency Response, opyng t -

(Quincy, MA: National Fire Protection Assoc1at1on) .

Chapter 1 Introduction 25

I TABLE 16 M&idifl-. !ITU:151' . F INSTABILITYb IDENTIFICATION 0

IDENTIFICATION OF FLAMMABILITY" IDENTIFICATION OF HEALTH HAZARD COLOR CODE: YELLOW

HAZARD COLOR CODE: RED HAZARD COLOR CODE : BLUE SUSCEPTIBILITY TO

SUSCEPTIBILITY OF RELEASE OF ENERGY SIGNAL TYPE OF POSSIBLE INJURY SIGNAL

MATERIALS TO BURNING Materials that in themselves SIGNAL Materials that will rapidly or 4 are readily capable of detona- Materials that on very short 4 4 completely vaporize at nor· tion or of explosive decompo- exposure could cause death mal pressure and tempera· sition or reaction at normal or serious residual injury ture, or is readily dispers~d temperature and pressures even though prompt medi- in air, and will burn readily Materials that in themselves cal treatment was given 3 Materials that on short 3

Liquids and solids that can are capable of detonation or 3 be ignited under almost all explosive reaction but require exposure could cause serious ambient conditions a strong initiating source or temporary or res idual injury

that must be heated under even though prompt medi - confinement before initiation, cal treatment was given or that react explosively with water

Materials that must be mod- 2 Materials that in themselves

Materials that on intense or 2 are normally unstable and 2 continued exposure could erately heated or exposed to readily undergo violent cause temporary incapacita- relatively high temperature decomposition but do not tion or possible residual before ignition can occur detonate; also, materials that injury unless prompt medical may react violently with treatment is given water or may form potentially

explosive mixtures with water

Materials that must be pre- 1 Materials that in themselves Materials that on exposure 1 are normally stable but which 1 heated before ignition can would cause irritation but can become unstable at ele- only minor residual injury occur vated temperatures and pres- even if no treatment is give n sures or which may react with

water with some release of energy but not violently

0 Materials that will not burn 0 Materials that in themselves 0 Materials that on exposure are normally stable, even under fire conditions would under fire exposure condi- offer no hazard beyond that tions, and which are not reac- of ordinary combustible tive with water materials

asee also Section 3.1-C. bsefore 1966, NFPA referred to this property as "chemical reactivity."

Each number is then displayed in the appropriate top three quadrants of the diamond-shaped diagram in Figure 1.4, called the hazard diamond. Each quadrant of the diamond is color-coded, beginning with the left-hand quadrant and proceeding clockwise: blue for the health hazard, red for the fire hazard, and yellow for the instability hazard. When warranted, the following symbols are displayed in the bottom white-colored quad- rant of the diamond:

hazard diamond A diamond-shaped figure divided into four quad- rants, each of which is color-coded for each of a substance's three hazards-health, fire, and instability-and The letter W with a line drawn through its center (W) to caution firefighters against marked with a number the application of water designating the relative The letters CRY to indicate the storage of a cryogen (Section 2.13) degree of th e hazard The letters OX or OXY to indicate the storage of an oxidizer (Section 11.1 ) 26 Chapter 1 Introduction

BLUE Health

FIGURE 1 .4 four potential hazards of a substance may be rapidly and simultaneously identified by the use of a color-coded numeral system on this hazard diamond . Beginning with the left-hand quadrant and advancing clockwise, the quadrants are rnlor-coded as follows : blue for the health hazard; red for the fire hazard ; and yellow for the instability hazard . A number from O to 4 is entered in each of the top three quadrants con- sistent wi.th the information compiled in Table 1.6 to identify the seventy of the health, fire, and chemical reactivity hazards . Each of several symbols, such as W and/or OXY, may also be entered. 1n the b?ttom white quadrant to provide additional hazard 1nformat1on . (Reprinted with permission from NFPA 704-2012, System for the Identification of the Hazards of Materials for Emergency Response, Copyright <e 2012, National Fire Protection Association . This reprinted maten'af is not the complete and official position of the NFPA on the referenced subject, wh ich is represented solely by the standard in ~ts entirety. The classification of any particular material with in th is system 15 the sole responsibility of the user and not the NFPA. NFPA bears no responsibility for any determinations of any values for any particular material classified or represented using this system.)

I The letters AS to i_ndi~ate ~he storage of nitrogen, helium, neon, argon, krypton, or xenon, e_ac~ of which 1s a simple asphyxiant (Section 10.3-A) The radiation ha~ar~ symbol, which resembles a three-bladed propeller, or trefoil (Section 16.3), to md1cate the storage of a radioactive material The ~ord AC!D or the letters ALK or CORR to indicate the storage of an acid, alkalme matenal, or corrosive material, respectively.

Only Wand OX are cited by NFPA, but the other symbols have such widespread use that they are included here.

As noted earlier, beginning in Chapter 7, appropriate GHS pictograms and hazard diamonds will be displayed in the page margin near the point at which a discussion of each hazardous material first begins.

1.12 CHEMTREC The Chemical Transportation Emergency Center (CHEMTREC) serves as a state-of-the-art communications center that deals with transportation mishaps by reinforcing the effec- tiveness of specialized emergency response groups and enhancing hazardous materials transportation security. Within the United States, CHEMTREC may be contacted by telephoning the following number, which is often posted on cargo tanks, rail tankcars, and other bulk packaging used to transport hazardous materials:9

CHEMTREC (800) 424-9300

Companies that list CHEMTREC's emergency number on their packaging must be regis- tered with CHEMTREC, and pay an annual fee.

CHEMTREC Formally known as the Chemical Transportation Emer- gency Center, a public- service hotline for firefighters, law enforcement, and other emergency responders for obtaining informa- tion and assistance for incidents involving haz- ardous materials

9 For calls originating outside the United States, telephone collect (703) 527-3887. Within Canada, telephone Le

Centre canadien d'urgence transport du Ministere des transports (the Canadian Transport Emergency Centre of the Department of Transport), or CANUTEC, at (613) 996-6666 . Within Mexico, telephone the Secretar(a de Comunicaciones y Transportes (Secretariat of Communications and Transportation of Mexico), or SCT, at 52-5-684-1275. These numbers have been widely circulated in the professional literature distributed to emer- gency service personnel, shippers and carriers, and members of the chemical industry, and they have been further circulated in bulletins of governmental agencies, trade associations, and similar groups.

Chapter 1 Introduction 27