Hazardous Materials
Help with Board Question and PowerPoint
Board Question
We come in contact with toxic substances every day. After reviewing the material in this unit, share with the class what you think are the two or three potentially most toxic substances that can enter our everyday lives. Do you think that the Occupational Safety and Health Administration (OSHA), the Environmental Protection Agency (EPA), the Consumer Product Safety Commission (CPSC), and/or businesses are doing enough to limit these potential exposures? Why, or why not?
Unit PowerPoint Presentation
For this assignment, you have been tasked with presenting information to your company’s board regarding a hazardous materials incident involving the transport of toxic substances that falls under the hazard classifications that we have studied so far (water/air reactive, corrosive, or toxic) identified on the following Web page(s):
http://www.csb.gov/investigations
Your presentation must include the following information:
summary of the incident;
identification of the information (hazard class, description, labels, markings, and placards) that the DOT requires when transporting toxic substances and information about workplace exposure concentrations of the substance involved in the incident;
description of the elements of the emergency response to the incident including a discussion on its environmental and human health impacts (be sure to address how the toxic substance’s chemical properties, uses, and ill effects may affect the tasks and safety of an EHS and FS professional working the incident);
Discussion of your opinion on the response to the incident
For this assignment, you will create a PowerPoint presentation consisting of at least 5 slides (not including your title slide and reference slide) containing the information described above. All sources used, including the textbook, must be referenced. You must include at least two sources. Paraphrased and/or quoted materials must have accompanying citations in APA format.
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Course Learning Outcomes for Unit
Upon completion of this unit, students should be able to:
5. Classify hazardous materials according to Department of Transportation (DOT) classification and
warning systems.
5.1 Identify the hazard class, descriptions, labels, markings, and placards that DOT requires when
transporting toxic substances.
5.2 Identify the response actions that are applicable to incidents involving toxic substances.
6. Determine strategies for dealing with chemical properties of specific types of hazardous substances.
6.1 Identify the chemical properties, uses, and ill effects associated with common toxic substances
as related to the tasks and safety of an EHS & FS professional.
6.2 Identify workplace exposure concentrations associated with common toxic substances.
Course/Unit
Learning Outcomes
Learning Activity
5.1
Unit IV Lesson
Chapter 10 Reading
Unit IV PowerPoint Presentation
5.2
Unit IV Lesson
Chapter 10 Reading
Unit IV PowerPoint Presentation
6.1
Unit IV Lesson
Chapter 10 Reading
Unit IV PowerPoint Presentation
6.2
Unit IV Lesson
Chapter 10 Reading
Unit IV PowerPoint Presentation
Reading Assignment
Chapter 10:
Chemistry of Some Toxic Substances, pp. 345-416
Unit Lesson
For this unit, we will study the chemistry of some toxic substances, which are covered in Chapter 10 of our
textbook. You may notice that some of the hazardous materials that we just covered under the corrosive and
water/air-reactive classification can also be classified as toxic since these substances can possess multiple
hazardous characteristics. When these hazardous materials are transported, the Department of
Transportation (DOT) description indicates which hazard is primary.
Toxic substances (also known as toxicants or poisons) can cause injury, illness, or possibly death when
exposed to the body, even in small quantities. As such, these substances require special attention when they
are encountered during their manufacture, storage, transport, use, or in an emergency response incident.
Other toxic substances are produced due to the interaction of hazardous/non-hazardous materials. An
example of a toxic substance encountered at fire incidents is carbon monoxide (CO). CO is the result of
incomplete combustion (not enough oxygen/air to completely burn an organic material that is not necessarily
hazardous).
UNIT STUDY GUIDE
Chemistry of Toxic Substances
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UNIT x STUDY GUIDE
Title
Chapter 10 focuses on the following toxic substances that could be present as environmental health and
safety (EHS) and (FS) professionals perform their duties: carbon monoxide (CO), hydrogen sulfide (H2S),
sulfur dioxide (SO2), hydrogen cyanide (HCN), nitrogen dioxide (NO2), ammonia (NH3), asbestos, and
pesticides. Warfare agents such as ricin are also briefly discussed. Just like in the previous units, workplace
regulations, transport requirements, and recommended incident response actions are also covered.
The study of toxic substances is toxicology. Specifically, toxicology studies the symptoms, mechanisms,
treatments, and detection of poisoning, especially the poisoning of people (News Medical, n.d.). Toxicology,
which is a field on its own, investigates the manner by which toxic substances adversely affect a living
organism, the diseases they may cause, the concentrations at which the onset of the adverse effects are
noted, and ways to prevent or minimize them.
Epidemiology is the study of the adverse effects of these substances and diseases, specifically the how,
when, and where they occur. In this course, we cover only the very basic toxicology and epidemiology terms
and concepts that are applicable to our study of hazardous materials interactions.
You should know that we can get exposed to toxic substances by inhalation, ingestion, and skin absorption.
These exposure pathways are discussed with illustrations on pages 350-351 in your textbook.
We will also review the following common ways that toxic substances can adversely impact health. According
to Meyer (2014),
Exposure may cause immediate dysfunction, impairment or death.
Exposure may affect only the site of contact.
Exposure may affect the whole body so the ailment is not localized; this is called systemic effect.
Exposure may target specific organs. There are specific terms used to describe these substances,
such as the following:
o Hemotoxicant, a substance that decreases the function of the blood’s hemoglobin and deprives
the tissues of oxygen
o Hepatotoxicant, a substance that causes liver damage
o Nephrotoxicant, a substance that causes kidney damage
o Neurotoxicant, a substance that adversely affects the central nervous system (the brain and
spinal cord)
o Respiratory toxicant, a substance that adversely affects the nasal passages, pharynx, trachea,
bronchi, and lungs
o Reproductive toxicant, a substance that adversely affects sexual function and fertility in adults, as
well as development in their offspring. (Meyer, 2014, p. 352)
Toxic substances can also be classified as:
Asphyxiant: “any gas or vapor that dilutes or displaces air and, when inhaled, causes
unconsciousness or death” (Meyer, 2014, p. 352). An asphyxiant interferes with oxygenation of the
tissues and the affected individual may literally suffocate. According to Plog (1988), these are
generally divided into:
o Simple asphyxiant: physiologically inert gases that dilute or displace atmospheric oxygen below
that required to maintain blood levels sufficient for normal respiration. Examples: carbon dioxide,
helium, hydrogen, methane, and nitrogen
o Chemical asphyxiant: This prevents or interferes with the uptake or transport of oxygen through
their chemical action. Examples: Carbon monoxide prevents oxygen transport by preferentially
combining with hemoglobin. Hydrogen sulfide paralyzes the respiratory center of the brain and
the olfactory nerve.
Irritants: Any substance that on immediate, prolonged, or repeated contact with living tissue, induces
a local inflammatory reaction (Meyer, 2014).
The harmful effects of toxic substances can be classified as chronic, acute, short term, and latent health
effects (Meyer, 2014).
There are several factors that affect the degree of toxicity. Since everybody is different, the effects of the toxic
substances also vary to a certain degree based on several factors:
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UNIT x STUDY GUIDE
Title amount of toxic substance that is inhaled, ingested, or absorbed;
length of time of exposure;
rate at which the toxic substance is absorbed in the bloodstream;
age, sex, ethnicity, and general health of individuals (e.g., the elderly could be more sensitive);
individual sensitivities—could be genetic; and
adverse health impacts on a developing fetus. One example observed involved a pregnant woman
ingesting a material with very high levels of lead, which impacted her baby. The baby had very high
levels of lead when she was tested (only a few days old).
Measures of toxicity are classified as follows:
Lethal dose, 50% kill, or LD50: dose when 50% of a test group die
Lethal concentration, 50% kill or LC50: concentration of the substance that kills 50% of a test group
Threshold limit value (TLV): This is a time-weighted average concentration under which most people
can work consistently for eight hours a day, day after day, without harmful effects (Plog, 1988). A
table of these values is published by the American Conference of Governmental Industrial Hygienists
(ACGIH).
References
Meyer, E. (2014). Chemistry of hazardous materials (6th ed.). Upper Saddle River, NJ: Pearson.
News Medical. (n.d.). What is toxicology? Retrieved from http://www.news-medical.net/health/Toxicology-
What-is-Toxicology.aspx
Plog, B. (1988) Fundamentals of industrial hygiene (3rd ed.). Chicago, IL: National Safety Council.
Suggested Reading
This is a general informative article describing the field of toxicology and the scientific study of the effect of
chemicals on living organisms. The article describes mechanisms, treatments, dose, and poisoning.
News Medical. (n.d.). What is toxicology? Retrieved from http://www.news-medical.net/health/Toxicology-
What-is-Toxicology.aspx
http://www.news-medical.net/health/Toxicology-What-is-Toxicology.aspx
http://www.news-medical.net/health/Toxicology-What-is-Toxicology.aspx
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FORM OF AQUEOUS AMMONIA SOLUTION SHIPPING DESCRIPTION
Aqueous ammonia solut,on, 10-35% a~monia, relat ive UN2672, Ammonia solution, 8, PG IU
density between O 880 and 0.957 at 15 . UN2073, Ammonia solut ion, 2.2
Aqueous ammonia solution .• 35-50% ammonia, relative
density less than 0.880 at 15 C .
Aqueous ammonia solution, >50% ammonia, relative
density lessthan0.880at 1s•c
Aqueous ammonia solution, >50′- ammonia, relative
density less than 0.880 at 1s•c
•0omert/c transportation.
l>i nterm1lor,altr1osponulon.
UN3318, Ammonia solution, 2.2
(Inhalation Hazard)~ ‘
UN3318, Ammonia soluti~
(Poison · Inhalation Hazard, zo~e o)b
10.16 RESPONSE ACTIONS AT SCENES INVOLVING
A RELEASE OF TOXIC SUBSTANCES
At the scenes involving transportation mishaps, emergency responders may establish that
a roxic subs tance has been released ro the environment by observing any of the
following:
The hazard class numbers 2.3 or 6.1 are included in the shipping description of a
toxic substance on a shipping pape
r
Either POISON or INHA LATION HAZARD is marked on irs packaging
Whire POISON GAS, POISON INHALATION HAZARD, or POISON labrls ar,
affoced to che packaging
A white POISON GAS placard is displayed on each side and each end of the bulk
packaging or transport vehicle containing any amount of a poisonous gas.
A whire POISON 11\’HALATION HAZARD placard is displayed on each side and each
end of the bulk packaging or transport vehicle containing any amount of a toxic sub
–
stance rhar poses a health hazard by inhalation and is classed in hazard Zone A or Zone B.
initial isolation distance A white POISON placard is displayed on each side and each end of the bulk packag•
ing or transport vehicle used to transport 1001 pounds (454 kg) or more of a toxic
substance in hazard class 6. l orher than those rhat pose a health hazard by inhalation
in hazard Zone A or Zone B.
• For purposes of DOT
regulations, the dis-
tance from a transpor-
tation mishap involving
the release of a hazard-
ous material to which
everyone should be
quickly moved in a
crosswind direction
initial isolation zone
• For purposes of DOT
regulations, the area
surrounding a transpor-
tation mishap involving
the re/ease of a hazard-
ous material in which
persons maybe
exposed to dangerous,
life-threateningcon-
centratiomofa gas or
vapor that poses an
inhalation hazard
~en a toxic substance has spilJed or leaked during a transportation mishap, DOT
prov1d:5 ~me:rgency responders with a table of initial isolation and protective-action dis•
r~nces .m its Emergency Response Guidebook (Section 6. 7). Excerpts of this table are pro-
vided. m T~ble 10.23 for the toxic substances nored in this chapter. To use this table
ef~ecri vely, firsr-on-rhe-scene responders must first determine whether a “small” or a “large~
spill ~f the_ toxic ~ubsrance has occurred. This determination can ordinarily be made b)’
speakmg ~uh the: mdividual most immediately responsible for rransporration of the hazard·
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~ ~ateml. A “small”. spill is one that involves a single package such as a 55-gallon
(2 f LJ drum, a small cylmder; or a small leak from a large package A “large” spill im•olres
a re ~se fro; bulk_pac_kaging or multiple releases from several sm;II packages.
b k .nee ad etermmat~on rega rding the size of the release has been established, the guide·
oo is use to determine each of the following:
The initial isolation distan · h d. h · h
everyone should be uick/ m ~e JS t e 1_stan~e fr?m an emergency ~c7~e ~o w _I’
zone shown in Fig~re 16 11~;ed ma ~r~~swr~td d1recr1on ro establish rhe in1t1a/ 1s~lati~~ . · ). The mn1al isolation zone is the area surrounding 392 Chapter 10 Chemistry of Some Toxic Substances I
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FROM MANY SMALL PACKAGES) THEN PERSONS DOWNWIND DURING ISOLATE THEN 10 NO. GUIDE NAME OF MATERIAL m – PROTECT IN ALL DIRECTIONS – “””‘ -~ ””‘ PERSONS DOWNWIND DURING – ‘.;;; lm,I~ m..=’ ft km ml km Tm1 ft 1067 124 Nitrogen dio1dde WJG 12S Phosgene 100
300
0 .6 … 2 .7 1.7 500 1500 3.1 1.9 10.8 6.7
l079b 125 Sulfu r dlo,cide 100
·- — -300 0.1 0.4 2 .8 1.1 1000 3000 s .6 _3.s 11 .0 , • ~ 1.0, 100 0. 1 0 .1 0.3 0 .2 I 60 I 200 I 0.8 I o.s 2.S 1.6 (when spilled In t—1250 1 55 Methyltr lchlo ro •silane 30 0:. 0 . I 0 .3 0.2 I I 00 300 0 .9 I 0 .6 I 2.6 I 200 \ o1 \ •4 22 r• spilled In water) 60 200 0.2 0 .1 0.2 0.1 150
~ 500 I OS I 0 3 13 °8 a queous solution, with not more than 20% hydrogen cyanide – 1613 I 154 I Hydrogen cyanide, 100 300 0.3 02 1 2 08
Potassium cyanide 30 100 0. 1 0.1 0.2 0.1
1680 157
(when spilled in konrfn~
Mfli!il•f!F ln1t1al Isolation and Protectlvll!’ -A ct1o n Dh ,tances (cont,nu IDNO. GUIDE
1680 157 1689 157
1689 157 1717 155
1749 124
1829 137
1829 137 1831 137 19S3 I 119
1953 I 11 9
(FROM A SMAU PACKAGE OR FIRST THEN IN AU DIRECTIONS PERSONS DOWNWIND DURING
DAY NIGHT ! ;~;~mi;;::~,cwhen I 30 I 100 I 0 .1 I 0.1 I 0.2 I 01 Acetyl chloride(when 30 100 0. 1 0 .1 0.3 02 Chlorine t ri fluoride 60 200 0 .3 0.2 1.2 0.8 Sulfur tr ioxide, Sulfuric acid, fuming 100 300 0.4 02 0.9 0.5
Sulfuric acid, fuming, I Compressed gas, I 100 I 300 I •. , I 0 3 I 22 I 1., I Compressed gas, 30 100 0.1 0 .1 0 .3 0 .2 FIRST lARGESPILLS FROM MANY SMALL PACKAGES)
THEN IN ALL DIRECTIONS PERSONS DOWNWIND DURING m ft km mi km m; –
I 100 I 300 I o.4 I 02 I 1.4 / 0.9
100 300 1.0 0.6 2.8 1.7
300 1000 LS 0.9 4.6 2.9 400 1250 2.9 1.8 5.7 3.5
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300 I 1000 l u I a.a I 3.s 1 2.2
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FI GLI RE 10, 11 The. initial isolation zone and the p1otect1ve-act1on zone shown m (al and {bl, respectively, con- emergency scene in which persons may be exposed to dangerous, life- threatening concemra- The protective-action distance is the distance downwind from the scene that protectiv,e..actlon of DDT regulations, the protective-action zone regulations, the area in SOLVED EXERCISE 10.7
S.,ow how an emergency responder uses TabIe 10 23 to 1dent1fy the 1n111al isolation and protectIve-actIon d1s- Solution: It Is first necessary for the responder to 1dent1fywhether this incident mvotves a “small” or a ” large· When emergency responders are required to encounter a_ t~~c subst~nce, 1hey mu~1 Chapter 10 Chemistry of Some Toxic Substances 397 I 111 I’
I’ stanceoragentthat 1, b , inhal:ition but also by skin absorption, the use of 3 fully e emer. the body “~1 on :im!zes or elim inates the risk of ~xposure_ to t?e_ substanct’ b ~~fl- h is usually crmcad ;: !:~ s:bstances, even if they do ~ot ex_hibit a Caution alwa}’S needs robe exercised when em_ergency responders a~e calld 10 a Use impermeable coveralls or simi lar fully-encapsulated body suit and self-comained
~::~~n;;;~:;:s~;e to rhe smoke or fumes that evolve from these fires by attacking 10.17 CARCINOGENESIS In some instances, the onset of cancer may be traced co exposures to cenain agtms 1 1
Thc_Americ:in.Association of Poison _Cont rol Centers can be ,messed by telephone at (800) 221- 1222. h is
~~-e~tull~· a libmy mffed by nonmcdu:.:il personnel. Be prepJted to give the name of the poisonous prodc.t ‘ P mng ean dilofasc. O1w 12 million new cas.cs .1re di.1gno,cd ann1.1.1 ll y.
398 Ch apter 10 Chemistry of Some Toxic Substances
nc predispOSit(on to”.”ar_d~ con,tracting cancer from their ancestors In this text our con- ,es cancer are den ,-:iu :a:::t?i~;~~:i: 1.0 varyi_ng’ d~scs ?fa substance to determine \\ hmoncal exposures of humans to
I 1 expose popu auons. corrupt them. They acl wi~h . vastly different potencies, differing in their abilities to Although the mec~an~sm of carcinogenesis-the production of cancer-is not com- 1 During the initiation stage, the_ genetic . ma1erial within a healthy cell or group of thway by which cancer can occur ts established during the initiation stage. Overall Cancer may also be initiated without exposure 10 any agent whatsoever. This hap- During the subsequent promotion stage, the damaged cell divides into new but I During the fina l progression stage, the damaged cells invade nearby tissues and Tobacco smokers represent a unique group of individuals for whom. 1he i_n_cidence of cancer during which promotion• The sec- suethatpersists and prog ression third t ion of a malignant Chapter 10 Chemistry of Some Toxic Substances 399
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ill I II :/ syne-rgism • The ph~ . ,· h h m. By so doing, heavy smokers assume a liferime risk of ac The emt’rgencC” 0 ru f the organs to carcmogens that are 1101 c lllal 0 of rwo or more caran;;no/may be evident b}’ the onset of an adverse health effec-t than cancer. For e~p . ‘than are nonsmokers. Asbestos-exposed smokers are about ~lllg like/~ to de,·elop testicular cancer, muluple myeloma (a cancer of the bon.e marrow), non. 10.17-A CLASSIFICATION OF CHEMICAL CARCINOGENS The various procedures employed for the study of carcinogenic potentiality have pr0o ifriii/.itl IARC’s Class1f1cat1on of Carcinogens 1•Grace le,\fa~rers er al “Cancer r’ k . . • Chapter 10 Chemistry of Some Toxic Substances iher ;1 subStan.ce causes cancer in th~ human organism. Research studies in carcino- ‘ n rcinogen is known to be a co~slltu~n~ of a commercial product, some st:ue laws require O 17.9 WORKPLACE REGULATIONS INVOLVING CARCINOGENS !1b~n 1he use of ca rci.nogens is ~equired !n the workplace, OSHA requires employers to ires employers to post m this area a sign rhat 1dent1fies the carcinogen and its physical r——–, EXTREMELY CANCER-SUSPECT \rinyl chloride is a human ca rcinogen (Section 14.6). had this warning when they enter buildings in which carcinogens are stored or used. In chis and future chapters, we recognize the carcinogens of immediate concern to 10.18 COMPOUNDS OF TOXIC METALS Essential elements. Trace amounrs of 14 metals and metalloids are essential in the diet Toxic metals. Certain other metals and metalloids are nor known to offer any IJUnkss otherwise indicated the designations in th is m.:t arc those JcnotC’d by the U.S. Department of Health essential ellement human diet that Is toxic metal Any met- Chapter 10 Chemistry of Some Toxic Substances 401 1, ii I
I 402
Lud lead-ba~p.iint • For /· and rnecalloids may be either roxic or beneficial, dependin rhtir concrnrr.1non aud . h exrrt a roxic effect or perform an essrntia! bi ! ~lr. LEAD AND ITS COMPOUNDS fires in old scrucru.r;-formerly were used as pigments in surface coatings to provide co! and pre~·ent corros1′:::~e~oatf’ngs are ca lled lead-based _paints . EPA banned the u~a~d 1 conrainin some lead-based pa int. When these srrucrures c?llapse during ongoing build. L~ad poisoning is the collecti~n of ~dverse health p~oblems caused by lead exPosutt. Lead exposure in children also 1mpa1rs the1~ ab1ht) to lea rn and execute ~enral lNd poisoning• The larly ro their IQ measurements obtained as ad ults. This fi~dmg suggests that the ill are disproportionately affected compared to children who live elsewhere. The lead-b.1Std Adults may also bt adversely affected by lead exposure. They experience reproductfre 1 one of che most severe consequences of chronic lead poisoning. Exposure to certain lead ; Chapter 10 Chemistry of Some Toxic Substances S CONSUMER PRODUCT REGULATIONS INVOLVING LEAD 8 CJ’S; ~~ R- S iJOJ.4, it ba ns lead in pa!nt and ocher similar surface-coa ting materials; toys I ,kS rha cent above 0.06% by dry weight {other than artist’s paint) in the United States. peciall)’ those manufactured outside the United States. Furthermore, the lead content en who play with them. To minimize or eliminate the potential for lead ro •sand ocher produc_cs designed or intended pri~aril)’ for use by children 12 years or ,oun~e; :issura nce that they do nor contain more than 90 mg.lkg of lead. CPSC also requires k on children’s products and their packaging to ascertain 1he sources of the products. ;:r s ma rks include the production loca1ion, date of production, name of manufacmrer, Manufacturer Toddler’s Toys Production Location. Port-au-Prince, Ha1t1 10.18-C WORKPLACE REGULATIONS INVOLVING LEAD OSHA also requires at 29 C.F.R. S 1926.62 that emplo~e rs indu_de the fol lo~ving infor- CAUTION
CLOTHING CONTAMINATED WITH LEAD IN ACCORDANCE WITH FEDERAL REGULATIONS I’ I I I I 404
Asbestos
REGULATIONS INVOLVING LEAD D ENVIRONMENTAL housing and proV1dc avai\ad po provide an EPA-approved lead-hazard inform . pamphlet to potenna O h b ers 3 10-day period in which to conduct a lead-b p:un~ 1~:t:~.o\:s::rs, and real estate agents share responsibility for ensuring comp\iaflet Wlt a app \ . . . ed for all firms who intend to conduct renovation repa· Other environmental statutes, including the following, impact EPA’s regulations concem. Using the legal authority of the Clean Air Act, EPA regulates th~ concentration of Using the legal authority of RCRA, EPA regulates th~ t~eatmem_, ~torage, and di~ Using the legal authority of TSCA, EPA regulates th_c manner by whtch_ c_omraaors 10.18-E TRANSPORTING LEAD We note the DOT requirements for transporting oxidizing lead compounds in Chapter 11.
10.19 ASBESTOS When mixed with magnesium oxide, asbestos was formerly used for a variety of fire· 0 en mto Srrong, flcx1ble threads that could be converted into fireproof
l i An example is the EPA document • . . . S Chapter 10 Chemistry of Some To:,dc Substances
·cs. Although th~se asbeSt0S products once were _prized for their desirable feamres, their ,, 9 A ILL EFFECTS CAUSED BY EXPOSURE TO ASBESTOS 1 i\{tcnt;:n six minera_l types: the serpemi~e mineral chrysoti/e (commonly called white asbes- 1 1re1_ d Siaies. There 1s substantial sc1enufic evidence supporting the observation that cxpo- en ~~aks apart into tiny fibers, ~u~h smalle~ and more buoyant than ordina’:)’ dust. 0 !t ~a~: or swallow its fibers. . ~gand have a diameter of only 30 nanometers. They float almost indefinitely in the g Exposure to friable asbestos potentially causes the onset of the followmg diseases, 1 Lung cancer, the growth of malignant tumors in the lungs. Microscopic asbestos friable • Brittle or lung Cancer asbestosis A scarring mesothelioma The 1 Mesothelloma, cancer of the mesothelium, the protective membrane or sac sur- mesothelium • The pro- pleural mesothelioma protective linings Fog
Bacteria
Asbestos(lengthl
Finesend – 0:;;0<-.....~~,~.,~~=.L.~=w,t;,~~~,oo~ - 101000 ::::~~~~~u:;;A~Ol1rn;8~7::a~r:8~o-
Size range, microns hi.ml
Chapter 10 Chemistry of Some Toxic Substances 405 i !1
countabl i! elongate evidence associ.:uing mesorheliom:1 in human_s. wi th :1sbestos exposure is 0\ h The flkeiihood rhar individuals wil! c~n.trncr lung cancer, ~sbestos1s, or mesotheho Smokers exposed to :isbesros fibers are about 50% more likely than nonsmokers
to d~v~:~}:r:!_;:;,::d smokers are about 90% more likely than nonsmokers to con. These examples suggest that tob:icco smoking ~eakens the lu_ngs and prov ides 3 \·u]. 10.19-B CONSUMER PRODUCT REGULATIONS The CPSC has promulgated regulations to eliminate or reduce asbestos in consumer 10.19-C WORKPLACE REGULATIONS INVOLVING When rhe use of asbestos is needed in the workplace, N IOSH requires employers IO limit When asbestos is present in the workplace, OSHA requires employers ro post 1hesign t- ·MMfl#i• AVOID BREATHING DUST t•·tVMii• AVOID CREATING DUST 406 Chapter 10 Chemistry of Some Toxic Substances
19.D ENVIRONMENTAL REGULATIONS INVOLVING ASBESTOS 10 ~ 1\~~ard, commerc ial paper, specialty pap~r, and flooring felt. ‘ !o safeguard the _hea lth of school children and others who work in schools, EPA ~:~:~red 10 accomplish the following within their jurisdictions:
Inspect for the presen~e of friable asbestos in its school buildings EPA also regulates at 4? C.F.R. S61.145 how the asbestos is to be stripped fro~ wa\ls, , Sealing a work site befor~ the asbestos-containing material is removed 1 Placing the asbestos debris in leak-right containers that subsequently are sealed 10.19-E TRANSPORTING ASBESTOS DOT also requires shippers to identify asbestos on an accompanying shipping paper NA2212, Asbestos, 9, PG Ill
When bulk quantities of asbestos are transported, this shipping description is preceded by DOT requires carriers who transport bulk quantities of asbestos by highway or :ail to Although DOT generalli· requi res carriers to post placards when using thfe shquared-on- pomt diamonds and orange panels to display t e I .ent.J ica ton CLASS 9 placa rds on the ,·chicles used to transp?rt asbestos . no tes rh ar these ttansporration req uirements do not a pply to asbestos that a~ e h I esins or mineral o re, or con- Chapter 10 Chemistry of Some Toxic Substances. 407 I 408
10 19-F RESPONDING TO INCIDENTS INVOLVING D ice efforts to eliminate asbestos in buildings, emerg~ncy. respond:rs_are most like] . 3 route ~f exposure route is inhalation of the ~ust generated_ when wa lls, ce1l1ngs, and rooi Firefighters also put their families an~ col!eagu~s at nsk of contracting an asbcstcs. 10.20 PESTICIDES There are rwo cbemical rypes of pesticides: inorga nic pesticides and organic pesti- Although organic pesticides may be classified in several ways, we divide them inrothr 0 Carbamate pesticides, deri va tives of carbamic acid, HiN- \ Organochlorine pesticides, ch lorinated deri va ti ves of ce rtain complex hydroca rbons 0 Organophosphorus pesticides, deriva tives of phosphoric acid , Ho- 1;-oH Thiocarbamate pesticides, derivatives of thiocarbamic acid H1N-J , . I Thi~ c.hemica l classification scheme is employed by DOT for generica lly describing organic 10.20-A ENVIRONMENTAL REGULATIONS PERTAINING To advise consumers of the hazards posed by exp “f • ‘des EPA uses the Chapter 10 Chemistry of Some Toxic Substances o-B TRANSPORTING PESTICIDES OT requires shippers an car~iers co 1d~nt1 fy the shi pping description of a pesticide on h names of the principal const ituents that cause the pesticide to meet the definition of also requires s~ippers and carriers to comply with all applicable labeling, marking, 10.zo-C PESTICIDES AND FIREFIGHTING :~~uld use self-contained breathing_ appara~us and _””.ear fully encapsulating suits. . . h dache, vomiting, sa livation, and lack of coordination. These symptoms may be mis- Pesticide fires should always be fought from the upwind d1recuon or at nght angles. raise coxic dusts. To protect the environment, the runoff water generated during the Mil\iii¥1 Organochlorine Organophosphorus Pesticides, solid, toxic
Thiocarbamate Representative Generic Shipping Descnpt1ons of Some Sohd Pesticides
SHIPPING DESCRIPTION ~N27S7, carbamate pesticides, solid, toxic, {ethyl carbamate), 6.1, PG 111 {Poison) ~~2761 , Organochlorine pesticides, solid, toxic, (Endosulfan), 6.1, PG II (Poiso~) ~rN2783, Organophosphorus pesticides, solid, toxic (Chlorpyrifos), 6.1, PG’ ‘. (Poison)
UN2588, Pesticides, solid, toxic, n.o.s. (ammonium sulfamate), 6. 1, PG I (Poison)
:~2588, Pest icides, solid, toxic, n.o.s. (ammonium sulfamate), 6.1, PG II (Poison)
or Pesticides sol id toxic, n.o.s. (ammonium sulfamate), 6.1, PG Ill (Poison) . or . . lid toxic (ethylenebisdithiocarbamic acid), 6.1, PG I {Poison) or . . I’d t ic (ethylenebisdithiocarbamic acid), 6.1, PG I (Poison) Chapter 10 Chemistry of Some Toxic Substances 409 biological warfare infKtious pathogen or fungus that may 10.2 1 BIOLOGICAL WARFARE AGENTS An infectious pathogen consists of living bacteria, viruses, fungi, rickettsiae . ~though ~he dissemination ~f inf~crious patho~ens or toxins could cause large-scale a living organism or practice has been condemned by civilized countries as unethical a nd inhumane. re 1925. Despite irs ratification by 130 nations, the mistrust and fear among nations han ifrjijj,f}j Some Infectious Pathogens and Toxins &cillus anthracis, a spore-form ing &cillus cereus Bacillus subtilis
Bruce/la abortus (multiple biotypes)
/ ADVERSE HEALTH EFFECTS CAUSED BY INFECTION
Anthrax, usually fatal in the inhaled form (The symptoms of exposure are provided in Food-poisoning-like symptoms
Produces a protease enzyme that interferes with protein metabolism Unknown
Unknown ~:~~:~:ts, an infectious disease that may cause an infected pregnant woman to abort
Bruce/la melitensis
Burkholderia ma/lei ~:af:~:~.s,~u~~~:a;:hzt~:J:: acquired ~y humans from infected animals; ch~racterized
Burkholderia pseudomallei
Clostridium botulinum (seven seizure· light ·r . ‘ rs, cheSt pain, muscle tenderness, weakness, weight loss; Meli~dosis, a d isease similar to glanders and characterized by the same symptoms (continued!
410 Chapter 10 Chemistry of Some Tox ic Substances
j!Hii.ft• Some Infectious Pathogens and Toxins (continued) oosrrid/um perfringens
(lostridium tetani
~ rynebacreriu~ diphtheriae
coxiel/aburnetu
Ebola virus (four types)
francise/la tularensis
Listeria monocytogenes
Marburg virus
Plasmodium malaria
Pneumocystiscarinii
Poxvirusvariola
Ricin
Rickettsia prowazekii
Salmonella enteritidis
Salmonella typhimurium•
Staphylococcus aureus (multiple Streptococcus pneumoniae
Vibrio cholerae
ADVERSE HEALTH EFFECTS CAUSED BY INFECTION :~~e;it_ir the inflammation of the small intestine; gas gangrene, respiratory distress, Tetanus(lockjaw)
Diphtheria, anoftenfatal respiratorydisease Ebola hemorrhagic fever, a highly contagious disease that has ended in death for 90% ~ever; m~scle ache, nausea, and diarrhea; can lead to meningitis, encephalitis, and Marburg hemorrhagic fever, a disease similar to but distinct from Ebola hemorrhagic Malaria, a mmquito-borne infectious disease characterized in the most severe Smallpo1t, a hlghly infectious, often fatal disease characterized by high fever, head• Acts as a hemotoxin (The symptoms of ex.posure are provided in Section 10.21-F.)
Typhus, a disease caused by louse-borne bacteria, characterized by severe Salmonellosis, characterized in the same manner as exposure to Salmonella enteritidis; Staphylococcus food poisoning, characterized by sudden severe nausea, vomiting, Pneumonia Yetlinia pestisb,c Bubonic plague, a disease associated with the production of ugly black. welts and ‘The flr1t known act of bioterror\sm on American soil was carried out In 1984 by members of the Rajneeshees, an Indian rellglous ~ult . The bloter- ~:~;~:n~iol~gfcal Weapons and Americ~’s S~cre the lo c P ague has ohen been assoc at~ b f Is that the loss of llfe was caused by deadly bacUI\ that were tra nsmitted from fleas carfled
0 <~~:~e;\~;dh:~;nt;
0
~~~~~~j~~ an anth;ax.-like bacll lus. \Norman F. Cantor, In the Wake of 1he Plague (New York:
:~ee Press, 2001).) di d when they consumed rice and wheat that had been \ntentlonally contaminated chapter 10 Chemistry of Some Toxic Substanc.es 4 i 1 Bicterrorism Acts • The select agent •For pur- 10.21-A SELECT AGENTS here as the Sioterrorism Acts. Using the authorities of the Bioterrorism Acts, the _U.S . Department of Health and Those th.it potentially pose a threat to public health and safety. HHS publishes this Those that potentially pose a threat to animal health and animal products, D Those that potentially pose a threat to plant health and plant products. DA ub- t at possess, use,. or transf~r select agents to register with the appropriate federal agenC)’ 10.21 -B DISSEMINATION OF INFECTIOUS PATHOGENS AND TOXINS Containerization in canisters I b b h . d missile heads or artillery shellsor c USter om s t at are then inserted into mod1fie
Aerosolized dispersal from ai f . robotic craft ) ·n I d rcra t \e.g., crop dusters, helicopters, or low-fl)’1ng Aerosolized d1spersa\ using enera . y or over a city g tors ea rned on trucks or boats in an enclosed spacr
Direct introduction into food o d . . pass_ aher _it ~as been disseminat~d. The me;tposure to a pathogen, a period of time 1niu 412
Du~mg 1h1s tune the pathogen enters the tod~d ma~ be_ h~urs, days, weeks, or even )~ar until the symptoms and ai lments of a dis ies of its v1ct11ns and multiplies cxponenu:111\ apter 10 Chemistry of Some Toxic Substances ·od or gap between the exposure and the appearance f \” . . pe rt . ‘ nticroorganism is insufficient in number t O c mical sym_ptoms, the disease- Jr~ ~\edical authorities ~ategori~ally recommend the isolation of infected individuals The _isolanon of persons mfc~ted wit~ a cont_agious disease serves to prevent the spread 10.21 -C RESPONDING TO INCIDENTS INVOLVING A RELEASE Hazardo~s material tea1:1s are now trained to identify infectious pathogens or toxins even When a bioterronsm act has been committed, emergency responders need to cordon Areas contaminated with an infectious pathogen or toxin may be decontaminated by 10.21 -D TRANSPORTING INFECTIOUS SUBSTANCES
infectio us substance Although the general public fears exposure to biological warfare agents, microbiologists DOT refers to infectious pathogens and toxins as infectious substances, and regu- World Health Organiza- that we note here. Provided in Table 10.27. Chapter 10 Chemistry of Some Toxic Substances 413
\\ diagnostic sprcimen ifriijj,Q Risk Groups for Pathogens A pathogen that usually causes serious human. or :;~:~~i~~l:h:~ ~:”a ‘:e~~~uhth:~~r~: :~~ma~!:!si;~e A microorganism that is unlikely to cause human or ‘NotsubitcttoDOT reguJatlons.
RISK TO High
High Moderate
None or very RISK TO Low
Low DOT regulates the transponation of hazardous materials in division 6.2 having ihe When sh.ippers prepare the applicable shippi ng paper, they are obligated to include UNITS
l glass tube HM
SHIPPING DESCRIPTION UN2~14, Infectious substances, affecting humans WEIGHT Al~hough an infectious substance is not assigned a packing group it is packaged 10 Shipper or carrier’s full name address and tel h b 414 Chapter 10 Chemistry of Some Toxic Substances
Cross section Name, address, and FIGURE 10,13 When shippers offer an 1nlect1ous substance for transportation, DOT 1eq1,.mes them to use tnple packaging 1 Precautionary statement The net quantity of infectious substance
In addition, DOT requires shippers to display the orange-and-black DOT also requires INFECTIO US SUBSTANCE labels to be BIO HAZARD
£ Carriers are obligated to notify the consignee and either the .National Response Cen· llous substance.
10,21 -E ANTHRAX chapter 10 Chemistry of Some Toxic Substances 415 r eo le and made 17 others sick. In 2008 , an Army scien_tist, the fede:al government’s The anthrax pathogen is not new to b1oterronsm. ~~nng . ‘ . oth Gern1an The bacterium Bacillus anthracis causes anthrax. The spores of the bacterium can be The initial symptoms of exposure to the anthrax bacillus. are s1m1lar. to those experi- 10.21-F RICIN The chemical analysis of ricin reveals that it is a solid polymer (Chapter 14). In war- The following incidents involving the use of ricin toxin as a biological warfare agent In 1978, Georgi Markov, a Bulgarian exiled journalist living in London, was jabbed When ricin is assimilated into the body, its victims experience fever, cough, shortness 416 Chapter 10 Chemistry of Some Toxic Substances CHAPTER 10
Chemistry of Some Toxic 5’5< w 72 q: & Courtesy of The Fertilizer Institute, Washington, DC.
acid rain, p. 378 3
asbestosis, p. 405 epidemiology, p. 346 1
friable, p. 405 lethal concentration, 50% kill 350
metastasis, p. 399 80
oxyhemoglobin, p. 365 345 1/ I
I
protective–actlon distance-. p. 397 risk group, p. 413 sensitizer, p. 356 synergism, p. 400 359 I Ii
,I: I toxin, p. 410 ‘P. 345 smoke, p. 361 tumor, p. 399
toxi c su bsta nce The study epidem iolog y • The i +M,Mill health. · · I · f ;=:~:he mechanisms by which carbon monoxide and hydrogen cyanide interfere Certain substances cause death, illness, injury, or incapacitation when rhe body is exposed to them in relatively small quantities. They are called toxic substances, toxicants, or poisons. Throughout the remainder of this text, these terms are used The study of roxic substances is called toxicology. In particular, it investigates the Toxic substances are routinely encountered by firefighters and other emergency r
burn, and asbestos and lead are encounrered in the dust that is generated as o ld buildings a need ~xists for emergency responders ro stud y the commonly encountered roxic sub· 346 Chapter 10 Chemistry of Some Toxic Substances
T hough ihe l:lypers~~ genera ll y understands the . . fl)’ review how toxicity affects workpla . d m government regulations We O 1.A WORKPLACE REGULATIONS INVOLVI 1 . g its responsibilities, OSHA requires em I NG TOXIC SUBSTANCES 0
0 pl 3~~ cJuse their death or serious physical harn iesht at:re ~ecognized as hazardous and ‘i~: ha za rds. Beyond this general duty ob li gat;~:, :~;/re 1~ a feasible method to abare 3 OSHA also r~qu1res employers to tag, label, or otherwise .d .fy As we first_ noted in Section 1.9, O~HA also requires chemical manufacturers dis- 10.1-B RCRA TOXICITY CHARACTERISTIC
RCRA toxic ity gas poison ous-by- EP~ ~ses RC~ to regul~tc. the treatment, storage, and disposal of hazardous waste that a pressure of 14.7 psi. poisonous material regulations, a material In ~hapter 6, we first noted that DOT regulates the transportation of severa l types of ;:~~~nde~r:t;e~:~l. \~hen toxic substances are transported, DOT requires shippers and earners t? com- extreme irritation, espe- Chapter 10 Chemistry of Some Toxic Substances 347
10.1-C TRANSPORTING TOXIC SUBSTANCES rn I
l ifrii¥11 0 004 0 7
0025 28
0029 D009 0039 Id Co ncentra ti o ns of Some Representa tive Wa t HAZARDOUS WASTE Arsenic
Ba rium
Ben zene Ch rom ium
p -Cresol Lead Selen ium I Tr ich loroethylen e
I;:~c,HOLD LE\/El 100.0
0 .5
1.0
0.5
5 .0
200.0
0 .5 0 .2
1.0 0 .7
0 .5 ..,,,
s hipping descrip tio n of a roxic substance, DOT req uires shippe r_s co includ ~ th e expres- DOT requires ca rriers to disp lay th e PO ISO N GAS o r PO ISON IN HAL ATIO N DOT requires ca rrie rs ro displa y the a pplica ble PO ISON GAS o r POI SO N L~- DOT req ui res ca rriers to dis play POISON GAS placards w hen tra nsportin g any DOT requires carrie rs to display POISO N IN H ALATION H AZARD placards A s noted in Section 6.6-D, when carrie rs tra nspo rt a haza rd o u s ma terial whose When ca rri ers transport multiple toxic substan ces w hose haza rd cl a sses :u e dtsig· When the subsidiary ha zard class o f a haza rd o us ma teria l is 6. 1, D OT requires . When a ma ter ia l th a1 poses a hea lth haza rd by in ha la ti o n is ship pe d in bulk pack ~g· Cha pter 10 Chemistry of So me Toxic Substa nces
Shipping Descnpt1ons of Some ox1c1ty Charactern,t,c
11DousWASTE . haz ardou s waste th at exhi bits the 1 1 SH IPP ING DESCRIPTION
~.’°;;ci~,~,(~l~~~~~~~aste, liqui d, n.o.s. (arsenic), 1 NA3077, Haz ar dous waste, soli d, n.o.s. (mercury), ~.A:i:1: ,(~~~;;dou s waste, so li d, n.o.s. (m ercury),
the words INH ALAT ION H AZ~ RD . E~en when a haza rdous materia l in di vision 6.1 When ca rri ers tra nspo rt mo re tha n 1.06 q ua rt (1 L) per pac kage of a material th at A materia l th a t poses an inhalatio n health hazard and meets the crit eri a fo r Zone A in Table 6.2 no tes th a t DOT requ ires sh ippers to identify a ny hazard o us w aste th a t in gestio n • The rece ipt skin absorption • The 10.2 HOW TOXIC SUBSTANCES ENTER THE BODY : r::~a~:~;~t A toxic substa nce ma y enter the bod y by vario us rout es including dir ect injectio n into the ::;c:a;ot~~~~ : i! t Chapte r 10 Chemistry of Some Toxic Substances 349 FIG URE 10 , 1 The ma,« metabolism • The sum S•li”‘Y glaod
) Pharyn x
T .. lh ~ ?-: Tongue Epiglottis Salivary glands
Laryn ~ J. 4—
Stomach
Du ode num .–+-+- +— Pancreas Small intestine
10.2-A ORAL INGESTION 10.2-B SKIN ABSORPTION The skin, a cross sed ion of which is illustrated in Figure 10.2, constitutes the largest si~e 350 Ah.hough the skin aCIS as an organ of defe nse, it also can act as a permeable membra ne. Chapter 10 Chemistry of Some Toxic Substances ….,.
URE 10,2 Th e cro,ss sect ron of human skm showing some of its pllncipal comP011ents The outer layer of and ent er the unde~l ying dermis or subcutaneous tissue, from which th ey may be funher 10_2-C IN HALATION Diaphragm Alveol i
Pharynx
Laryn x Bronchiole
Terminal FI GURE 10.3 The maJor components of the human respiratory system Inhaled gases, fumes, and vapors- Chapter 10 Chemistry of Some Toxic Substances 351 I loaltffect • Arty.t il- systemlc etftct • Arty hemotoJF:iant • Arty htpatotollicant • Arty n,phrotollic.Jn t • Art y neuroto)lk.ant • Any respir.1110rytoJF:ican t rtproductivt taJF:iuint orvapor thatd il utesor d , rJ pid lv into the bloo dstr e.1m .i nd th en OMMON WAYS TOXIC SUBSTANCES eral war s: . d”are dysfu ncci on, impairment , or death . 1 h_ m~ y c: ;efin’:~~ n: ineha l:;ion of hyd rogen fl uoride. . Pulrno . Hemotoxicant., a substa nce that decreases the funcu on of th e b loo d’s hemoglobin Its met::ibolic by -prod ucts may ca use the host vic tim to ex pen ence 111 effects. For 1O.3-A ASPH YXIANTS The re are 1hree commo n mea ns by wh ic h an :isph yxiant ca us es u nco nsciousness Simple asphyxiants. As first noted in Sec tion 2 .5- 8, a gas having a vapo r densit}’ The reduced OX}’gen concentra tion, not the asp hyxi ant concent ratio n, is usua llJ’ 352 Chapter 10 Che mistry of Some Tox ic Substa nces
SOLVED EXERCISE 10.1 ~:~:~dn airr,osp here con tamin g 42 % methane and 9% oxygen by an emergency responder who
saw1ion~ 1 1 1 ~ ss, an ashen face, fan tmg, andmenta lfa 11ure ytoeaper1tncenauseavom1.ng,uncon-
1 Action as a h~moto~ican_t. Asphy xiati on ca n a lso be c:i used by chemical ae1 io n 11 11 os) gen in rhe -~ 7 dSlr e~mil ;\ltho~g~ co_nsc iousness ca n be regai ned when fr es h ai r o r
0X}~:~c;: t~~~; 0 Jnabili~ to 11 ti!ize ~ellt1lar OX)•~en, -~ no th er way that an as ph yxia m causes un • 10,3-B IRRITANTS Not all irrita nt s are gases o r va po rs. Skin ex pos ure to a solution o f a wea k aci d , for CPSC reg ulates ex pos ure co irritants in consu mer produ c1s. For it s purposes, a n ir ri – The CHS excl am ati o n-po int pie1 ogr;1m is affi xe d o n th e contain er labels of chemica l 10.4 TYPES OF TOXICOLOGICAL EFFECTS a ntldot, An agent capable of caus ing a Chapter 10 Chem istry of Some Tox ic Substa nces 353 r I I I’ ; I
.nitthNlth dlronlchNltheffKt coroNryheartdisuse short -tenn hu lth
d iSNseofrelative ly laten thu ftheffect
thatmariiffitliiUe tf 10 4-A A CUTE HEALTH EFFECT . An acute hea~ ~I· mes to a cnsis fo ll o\\11ig exposure 10 a subs tance for less than , hollI\ 10.4 -B CHRONIC HEALTH EFFECT 10.4-C SH ORT-TERM HEALTH EFFECT 10.4-0 LATENT HEALTH EFFECT 15 rega rded as a latent health effect, because these dmases usually eme rge 20 co 40 )’ean 10.5 FACTORS AFFECTING THE DEGREE OF TOXICITY Fortunately, the body ha s natural mechanisms for protecting i1sdf aga ins1 the imp.ia Aside from these natural protective mechanisms, the body is sometimes incapable of 10.S-A QUAN TITY OF SUBSTANCE 354 Chapter 10 Che m istry of Some Tox ic Substances
of the subs rnnce admin is1c red or ab so b d 1 :1 t,J 1. fo rtu na tel y, th ere arc rclaci vd y ft’w s b of mort than 100,000 md 1• 11d~:/~f tox ic11y. . u stanc es ihat exhibit thi s pronounct>d r ihe consumption o f alcoholic bcvuagcs affects t~: o~~s ose. For e~a~~l c, cons_1dcr 0 rno g subdued, relaxed, perhaps ei·en cl t>vated . . . mg.ldl , he or she may feel ,o.S-8 DURATION OF EXPOSURE The answe~ to this qucs_n_on ~s connected to che fact that che initiation, promotion, Alro, indi1·idua_ls do not respond in an identical fashion when exposed 10 a gi\len con- 1 Althoug h so me individuals experience ill effects from exposure to a toxic substa nce, I Alrhough some individ ual s ex perience adverse hea lth effects from exposure co a gi”en 1 Some individua ls who do not experience ill effects from a short-term exposure co one 10.5-C RATE AT WHICH A SU BSTANCE ABSORBS l.'(1hrn a toxic substance is inha led, the adverse effec1 cau sed by its presence m:i y not be a substance per body inwhichthealveoll in d isease in which the Chapter 10 Chemistry of Some Toxic Substances 355 I _ /
runcetha t c.iu~a bt,ylliumsensitiz.atlon
. m ested or ab sorbed through the sk111, suffici(nt tune !Tl thrn r]Jpse for rh r subst:1~:c:-fr~m ,he scom.1ch into 1he sma ll mtc- stme, when: ir 15 ;~ It 1s fort u_iwus that 11f~; :~ sm·.1m. The ume- needed . nnd can .1dm1ms1er an antidote, in duce vomitin 1• 10.S-D AGE, SEX, ETHNICITY, AND THE GENERAL HEALTH which toxic subst:1nces affect Ln d1 v1duals often depends o r~ thC’ ir age, st~, 1 _Ch1ldre~ ~re pa~~’t:r:~;~;e sull dtvcloping. A ~ ea~ immun e sym·m lea ves everyo= The sex and echniciry of 3 person also affrct the susc~pt1b1hty to comr~crmg crruin Likrn’lse, tho~ persons already weaken ed from disease are more _li kely than healthy A well-acknowledged group of unhealt hy indi,,iduals are- tobacco smok ers. As a gen• ::~~r?~~;=:~s;, 10.5-E INDIVIDUA L SEN SITIVITIES 10 experience an allergic reaction. An exposu re to a sensitizer can also influ ence the de,·d· niJ)’ play a role 1_n. exp lain ing why some individuals tole rat e ex posu re 10 a gi1·en 1 tc0 nip0ncnts of consu mer products. . fi h wheat, and any food wh ose treatm ent produces a sulfite (S01 – ) concentration 1 3 eQ • OSHA regu late_s e~posure to se_nsmzers that are stored and used in , he workp lace. T~;;ab}’ oSH~ to affi~ hea lth haza rd and ex clamation point CHS pic1ograms on rh ei r 10 When a pregnan t woman ha s been exposed _10 a toxic substance, her placenta ma y shiel d :s : provide the f~ tus with oxygen and ~utr~ents, but ii can also function as a b:’.lfrier by p Notwithsta nd mg this stateme nt , the placenta does not always block the passage of 1 :ncing growth and development or contributing to an illness or disab iliry. n.ini woman is exposed to illega l drugs. A prrgnant woman who uses cocaine or heroin, A developi ng fetus is also affe-cte d when a woman smokes tobacco products d uring We shall not e lat er that a developing fetus may also be negati vely impacted when its mothe r 10.6 MEASUR ING TOXICITY unique concentration of a substa nce, a nimals and humans do not always respond in the Chapter 10 Chemistry of Some Toxic Substances 357 r In the wo rkpl:ice, OSHA and J’\ IOS H require emp loyers to reduce o r dinti nai ltkchhood thac employtts w,11 exper1~nce advc-rse hea lth effec ts fro_m ex posure to e tht hstc~~ ~:l~~”;o~~f}:;:~ea;~:1;;~v::!t!~:ev:~e:rss~mnc n1s noted in th is section ar,
MtlJlj(,iM Tox1c1ty Measurem~nts of Some Comm o n Gases a nd Va pors LC~ SHORT-TER M DAN GE ROU S- TO-LIFE- Ammorua ,ooo 25 ppm (1 8 mg.lm 1) (NI OS H) SO ppm (35 mg /m 1) 300 Carbon mono,ude 3760 SO ppm (55 mg.lm 1J {OSHA) 1200 0,1onne 293 Cedm g 1 pp m (3 mg/m 3) (OSHA) 10 Flu orme 185 01 ppmj0.2mgtm 3J 25 Hydrogen chloride 2810 Ce 1hng Sppm(7mglm1J so Hydrogen cyan.de lOppm (11 mgtm 1),sk in 4.7ppm(5 mgtml), so (NlOS H) —- (OSHA) 10 ppm (15 mgtm 1), N1uico:.;1de 115 2Sppm(30mgtm 3J I 100 I (OS HA/NI OSH) l (OS HA) (N IOS H) 0.1 ppm (0.4 mglm 1) Phosph 1M 20 0.3 ppm(0.4mg/ml) 1 ppm(l mg!m 3J so (OSHA/N IOSH) (N IOS H) 2 ppm {5 mgtml) (NI OS H) (NI OS H)
358 Chapt er 10 Ch e m i stry of Som e Toxic Subst an ces
,o.6·A LETHAL DOSE, 50% KILL 1113 :a,ured b)’ co nsidering th e ma ss o f th at organ . ects a spec ifi c o rgan , th e LD 50 ma y be obr.iuied fro m a nima l stud ies. Fo r a n ave rage perso n ha vin a g e 50 ~eas uremem leth al dose, SO o/. klll Leth al dose :: LDso x w
SOLVED EXERCISE 10.2
: ::h~l~~~ •~1~:e~:7~~;sa Solution : Thel etha\ doseofphenolfora200-poundpe f!.Onby !.k.,nton1aetiscalculatedasfolk:,•,•.-s
200),:i X 2 ~ X 630 X~)( l ~ g~ = 57g
::n 10.6-8 LETHAL CONCENTRATION, 50% KILL The le thal co nc e nt ra ti o n o f a sub stance to human s is ca lc ulat ed using the LC50 mea- Le thal dose = LD so X w
10.6-C THRESHOLD LIMIT VALUE 1 l etha l co n cent rat ion, th~sho\d l imi t val ue
st an dard estab lished by 1TI.V~ arc published by rhe American Conference oi Governmental lndumia l Hyg,enists in Donm>t”,,t,mo” of Chapter 10 Chemi stry of Some Toxic Su bstances 359 11:
pem,iuiblev:pos urt ma•1mum perm iu,ble centru10nof asub- bomtconctntrationof “”””” r«o mfflfndtdDposurt 10 6 -D PERMISSIBLE A ND CEI LING EXPOSU RE LIM ITS The pe rm lss1ble expo,:~ ch workers can be exposc-d connnuously for either an to The ceiling hmlt, · he maximum concentrauon co which workers ma 1–l to 10.6-E SH ORT-TERM EXPOSURE LIMIT . . 10.6-F IMMEDI ATELV-DANG EROUS-TO•LIFE-AND· HEALTH LIM IT 10.6-G RECOMMENDED EXPOSURE LIMIT NIOSH develops and publishes RELs that are based on a time-weighted average con- 10.7 CPSC CRITERIA OF A TOXIC SUBSTANCE ~:::n!/1~N~~~ 1STEL.s, PEW, Jnd IDLHs He pubh~hrd by rhr Nmona l lnsmu1r of O.:, upauon3J SJfrty and Hal!h in !\JOSH :ro;h~:t’;’/~;-~ ‘”‘;ry work er~ publ,;hrd JI 29 C.F.R. Sl91 0. IOOQ, Table Z-1: for conmuc11on mJ,1:n” 360 Chapter 10 Chem istry of Some Toxic Substances
,\t 16 C.f. R. S I S00}~\{2 )( i), CPS C defines a consumer product as highl y toxic 1f it It produces de~l h wi th111 14 da ys _111 half or more th an half of a group of 10 or more 1 111111 p(r millio~ by vo lume or less 0 ~ gas_ or_ vapor or 2 mg/L by volume or less of mlSI or 1 10,8 TH E HAZARD ZONE 1 When the LCso is eq ual to or less than 200 parts per million, DOT assigns Zone A to 1 When 1hc LC 50 is grea ter than 200 parts per million but equ:il to or less than 1000 Emergency responders use the hazard zone designation to determine the dcg.rtt of tox.ic- 10.9 TOXICITY OF THE FIRE SCENE smoke • Thfairdisper- Puc simply, smoke is the gra y-to-blac k plume of matter consisting of an airborne dis· Chapter 10 Chemistry of Some Tox ic Substances 361
II r I I I
I
sub- cili• • Fmehai rhkepro- l re m:mtr inro rwo classC’S, P~vl-2.5 and PM-JO. PM 2 5 ‘° ultra~nC’ parr;culatc . ·culate m:mcr ha\·ing parudc diamerc-rs ranging fro~ 2~crolll- , d~ I tn the lungs and arc not cleared by c~ug~mg. Trapped_ by ihe su rround<>q 1 ulmonary ill n~~ and premature death. . incompleie combusiion of matter. When produced at a fi_rc scene, the smoke and combus. Fires are not the sol e source of soot particles, al though th ey generally arc the indi 10.9-A TH E IMPACT OF SMOKE ON VISION 10.9·8 ILL EFFECTS CAUSED BY INHALING SMOKE Another serious problem caused by smoke inhalation is deposition of carbon parrica- Breaching particulate matter also inc reases th e likelihood of contracti ng lung 0111cn, 2 362 Chap ter 10 Chem istry of Some Toxic Substances
Smoke
Heat
10.9-C THE ADSORPTION OF GASES ON TH E SURFACES Smo ke
The ca rbon paniculac cs in smoke act as adsorbents for gases. This implies that when we FIGU RE 10.4 Smoke, Which gases adsorb to the particulates? To answer this ques tion, ii is nc_ccssa ry 1_0 Chapter 1D Chemistry of Some Tox ic Substances 363 r _111
C..rbonmonoxidt
FIGURE 10.s The ,ncomp,ete comov1t,o-i of :;:~!~~a~s ~~1-rrch Smoke H;O
co co , H,O co t ! )co,I
“”‘ Incomplete combust ion is tht burning_ ph enom enon occms when the supply of air By contrast, complete combus tion is the bu rn1~g process .that occurs when plenty Although carbon monoxide and carbon dioxide arc the pr inc ipal gases present at I’ll’· 10.9-D ENVIRONMENTAL REGULATIONS INVOLVING Using t.he authority of th e Clean Air Act, EPA regu lates the conce ntra tion of particulate ITlJ t· 10.10 CARBON MONOXIDE 364 Ch apte r 10 Chem istry of Some Toxic Substance~
jbl•ii¥1 Physical Properties of Carbon Monoxide 125% by volume
742 % byvolume
In the “1l’ tallurg1cal indu stry, carbon monoxide is used 10 reduce metallic oxides 10 CuO(s) – CO(_i:-J —. Cu(J) – CO2(.~) 10.10·A PROD UCTION OF CARBON MONOXIDE 10.1 0·B Ill EFFECTS CAUSEO BY INHALING CARBON MONOXIDE When ai r is inhal ed into the lungs , a supply of atmospheric oxygen is assimilated into When hemoglob in unites with oxygen, the compoun d called oxy hemoglo bin is pro- ll b(aq) + 0 1(11q) – 02 Hb(oq) As oxy hemoglobin molecules move about the circulamry sys tem, th ey arri\’e at the When ca rbon monoxide is inhaled into the lungs, it imerrupts normal respirati on by Hh(aqJ + CO(K) – CO Hb(aq) ponentof red b lood compound that forms c;Hbo xy h, m oglob ln forms when carbon Cha pter 10 Chem istry of Some Toxic Substances 365
II r devi ce that maybe iiH¥11 111 Effects AssociatMI with Varto~s Carboxyhemoglobrll Concentritttons in Human Bl ood 10-Z0 , Tighmessacron fo re ht>ad: po~ e huda~he —- ~ udache, wHkne11,d1 zz mess; dimv1s ion,na ~ 40-50
50-60
60- 70
, …. Same as immed iately abov~ wrth greater possi b ility of collapse ;;;– l convu ls1ons funct 1on, poss1bteduth I Outh When hemoglobin is bound to carbon monoxide as CO Hb, it is u~~ble to perform its The ill effects caused by inhaling carbon monoxide a rc not solely associated with the Individuals who inhale carbon monoxide expe rience the symptoms li stt”d in Tab le IOJ, When the srmptoms art’ expericnct>d by individuals who have in haled ca rbon monox· o1tyhemoglob in, car• 10. 10·C CARBON MONOXIDE AT FIRE SCENES AND OTHER LOCATIONS J lb co nce nt rn tion m th e blood of th e use JC 1 I, however, survivors may mil ex pen <' ncc lo ng- term ca rdia c, neuroco •n11 ive and
:~ropsych1acnc ~amage (s uch as r~e onset of demenua ). g •
ExPo5~tc~~~;;~~~ :,T1~0 ~~~: .1~~~=: ~<' ~ith th e ma jor it}'. of th e illnes ses and death s chJ r art ><' . • carbon mon oxide 1s not associated so lel y
111th ch<' burnm g of buildings and ot he r str uctures. As ill ustrat ed in Figure 10.6, the
–.0-Chimoov fl,e FIGURE 10.6 The comb1m1on productspro-ducedw,th nanoperaton9!,re~actmayenter thenono ewhen ach,mney flu ebecofl’es b’ocked Underth,scircumstance, tilefire~ace serve1asapo1en11alsource olcarbonmonox- 1A.i J!\J.logo us &vice ,~ the bl ood-oxygen-s~ rurat io n meter calle d in o:C)gtt1 p11/u o.tm1eter. h meJ;um blood• :~;~~ ~~ :: &r1c,st1 (Quincy, MHsJchuset1s: Nmonal Fire Prorcc non Agency, 2008 ). d dunns the use o.f fau lty furnaces, sto\’es, sp~ct hcJWS, b]oeked ch1~1; ~:.· an . lly wary of exposuri:- to carbon monoxide \\;’omen w 0s ~:pable of crossing th e Pi3”::\.)’gen it is subj«-te d to an increased n.l: Airhough th ~ primary/:~~ ;:ss pose th e nsk of fi re and explos ion. When ignuro,
wx1c1ty, bulk qu;inun; s o to carbon dioxide. (a,t,.,nd1owk’
SOLVED EXERCISE 10.3 Thr ~rwn ~de c011Crn:rat on n 1ne ;iha~\1:;;!:,~;;;:~u~a ~~:~Y;~’e ‘:;r:rt~~~ ~;P~°:i’~:,~: SOLVED EXERCISE 10.4 10.10-D WORKPLACE REGULATIONS INVOLVING CARBON MONOXIDE 10 .10-E ENVIRONMENTAL RE GULATIONS INVOLVING ~;l~~~·~it~ow c~nc~ntrat~ns of carbon monoxide are natura l compo nents of pol!utd 4 3 368 Chapter 10 Chemistry of Some Toxic Substances mg/m ) as :t I-hour a1·er;1ge.
A DANGER NEVER use Inside a home On ly use OUTSIDE and Avo idothergeneratorhuards. 10 7 =—- CARBON MONOXID E As note:d e:t rlier i n Section 7.6-G, CPSC req u ires cha rcoal manufacturers to affix 1ofa1alitic s,
10.1 0-G TRANSPORTIN G CARBON MONOXIDE iilhll·IM C.ubonmonoxide, Sh1ppmg Descriptions of Carbo n Monoxide
SHIPPING DE SCRIPTION Chapter 10 Chemistry of Some Toxic Substances 369 r G TO INCIDENTS ASSOCIATED W ITH EXPosu~ TO CA RBO N M ness from inhaling carbon monox1d,.., thq• sh 1 mo1ed swiftl y to ;rn opt rfun IOO¾ oxygen fo r on~ hou_r _reduces the conct>ntrai( &eti When rm ergency respon f:c1li1 where arr noxidc, 5 ber of the type h (202 6 kra ) for ½ to I hour can be hfe-savmg bt’caust’ 1l i an tO aid divers suffering from wo rk -relat ed disorders. When divers movl’ dl’l’per and d~Ptt
FIGU RE 10.B Hyl)frt:anc oxygen therapy ,nvolves adm,n ,ste ring 100% O)()’gen at a pre\1ure up to three t rrt! 370 Chapte r 10 Chem istry of Some Toxic Substances
Jcrii :itt’f, th<' 1'.1'~~ 3 s~d pre ss ure/{ ihc surroundings cau st's more rntrogt' n and oxygen
;; Jis sohe 111
th 1 ,hr d11’rrs retu~st ream and tissues. Tfus )’ th e-e gases form bubbl es th Jt relea se rapidl y ~nJ l)n1phaw: v~::1~’. ~:~;~n~ t~:c~~ti~ng pam,. esprc1all y m the joint s. This pa inful ndit1on is com ) 5• To avo id it, divers must return 10 tht’ surface Hyperb.:mc chambers ha ve ?et’~ ~St’d not only 10 tn.””at divers and mdi\’iduals exposed 1 The use of a h)•perbari c chamber incrt’ases the amou nt of oxygen that the blood 1 Bre:11hi ng oxy~en undt’ r inc~eased pressure allows th e blood to carry oxygen Although the use of hyperba ric OX}’gen therap y ha s bttn successfu l for 1rt’at ing indi- 10.11 HYDROGEN CYANIDE Hyd rogen cya nide g:is possesses the di stinccivt’ odor of bitter almond s, which nor- iilhil·il Physical Properties of Hydrogen Cyamde ———t-‘:.c”:::(-::”;;”’;J:;;;;;:;——- Hydrogen Chapter 10 Chem istry of Some Toxic Substances 371 r cyi nosi s • ni,comb1- As shoirn m the follo win g dlusira 11on, there :irr l\10 thcorrf1cal Lt’.’wi~ StrlJ II N ~ C
Th unds repreS( [l[ed by rhese di stinctly differc-nt ~trucrur(.”s are inse p,ir,1b l , h1s10nc rea sons, t e su ‘ c ern1Cill 10. 11-A PRODUCTIO N OF HY DROGEN CYANID E :!NH1(~l -+- 30:(ef – 2CH_ifgl – :2 HCN(g) ._ 6H10(g)
0 ,.~ .. n \k1lunc HJ The hydrogen cy:im de molrcults produced by the reaction !~nd to ~eac1 at an explos ii·e 1 0 .11-B ILL EFFECTS CAUSED BY I NHA LI NG HYD ROGEN CYANIDE Expos ure to hydrogen cya nide generally 1s associated with _the onset of cyanos l 5 and tongu e. CyJnosis 1s caused when th e la ck ~f oxygen m 1he blood (hypo:i:,a ) is ~v:: Mflhilil:M Ill EffKts Caused by lnhahng Hydrogen Cyanide .. 02-50
10 SIGNS AND SYMPTO MS
Odor thresho ld
Thruholdl imitvalue
10-36 ______ ~::..D”=’ ;:::°’c::”•c:h•:::•d:::•::: 120-150
‘” Toleratedfor20mintolhourw ithoutd ifl iculty
~ fatalafter30·m lnexposure
____ L_ike-‘ly-“-tobefatalafter 10-minexposure
372 Chapter 10 Chem istry of Some Toxic Substances
The rncch :rn1s m by 11h1ch h)drogen C)anidc kills m energy produ cnon Cya d c oxidase, an en:i;)me csscm 1 1] fo r 0 r cell bod) St1 ssues mJ y be plcn ufu l, th e roccss forms cytotoxic byp rod uct s v.ho bod) is mcapJble of using OX)ge n :~~t ro c1Jrnde to x1c1 ty ‘ sc accumulation m th e bloodstream con
10.11-C USE OF HYDROG EN CYA NID E FOR LEGAL EXECUTIONS ~~!Jrcd by certain judicial coum. Toda y, only six :~a::;:mg Olli lh c death penalties Jc is thr lerhal ga s, It IS gene~atcd by dropping mmll .d I Y g ) · :; .1cid wirhin an rnclosrd, ai mght gas chamber. ic cyam c pc lets mto a container
N:iCN (1l -f- HCl(aq) –. N:1C haq) + HCN!gl In contcmporar)’ mnes, most stat es have condemned the use of 3 lethal gas for con – 1 frired mea ns o execution.
10.11-D HYDROGEN CYAN I DE AS A CHEM ICAL WARFARE A GENT Zyklon B was us ed b)’ the Nazis_ as a weapon of ma ss destruction to systematical\ )’ The most infamous Nazi death camp was loca ted in Auschwitz, Poland. Hmonans In modern times, therr have been allegations that domestic terrorists attempted to use Given rhe unorthodox ways by which tt rrorim may potentially use hazardous mat e- 3R.on Su1\c.,nd, T/J, 011, Prruut Doctrmt (New Yo rk, NY: S,mon Schu~m, l 007), pp. 194- 196. I I .:a JU nsd1cuonJ I accou nnng of the cya nide produc ts that tt’ rro nscs ma y obt ain for clJn d<'\,
une purposrs.
10 11 -E HYDROGEN CYANIDE AT FIRE SCENES Hydrogr n cya nidr 15 gdc-~; products m,a~fa ==t~rt Thc-sr produc ts includc- fabri cs, carpeu ng. a~d m:Htrt’ssc-s ma nu(~· … 502(.g) – 4CO(g) + … th dro ~nc)Jn,dc
–1/I CN(g) + 90 211.’) –IC0 2(g) _.. –I N0:(1.’J + The c-as e of combustion implies rhal hydrogen cyanidt” is lik~ly to be ~resent at its hightti Nonvithsrnndmg its ease of combumo n, .h)’drogrn cyamdr 1113~ survive m the atm01· Firefighte rs who hav e survived acute exposurt’ to hydrogen cyanid e are treated by 10.11 -F WORKPLACE REGULATIONS INVOLVING =~:i:h::;~o~-~:: ~~:~:~;~:n~d:oi~c~~:~~~~ ~t 1\~o;:~tlsa;:r~~i~~t~e(jL;ir~:J:Yil:::: 10.11 -G TRANSPORTING HYDROGEN CYANIDE 6 acute cyanide po1sonmg by IMge)flon or ,nh~l mon, • A m;r, j. Emng. ,\!rd., vol. l S (l 007), PP· 55 1- 558 . Shipping D@Scr,pttons of Hydrog@ n Cy,m,de
t1¥D~OGEN CYANID_E___ , -+ SHIPPING DE SCRI PTION ~ cyan ide, stablhled(conta lnsltssthan UN1614.Hydrogencyan ,de,sub ilized, 61 . 1r:a1er i1 1l’ 1 l0,11 -H HYDROCYANIC ACID d. Soluuons containing more than 20 ¼ hydrogen cyamdc are so vo]311 le that they have 10,11· 1 TRANSPORTI NG HYDRDCYANIC A CI D 10.11 -J M ETALLIC CYANIDES One of the m3jor commercia l uses of sodium cyanide is connee1ed with the leaching illi!ll·ll·I Shipping Descr1pt1ons of Hydrocyamc Acid Hydrocyanicacid,aqueousso\utions SHIPPING DESCRIPTION
UN1613, Hydrocyan ic add aqueous solutions, Sodium Chapter 10 Chem istry of Some Toxic Substances 375 I Sulfur li+iiiHll&iiM ptro n s of Some R@presentativ ., Potass ium cy•n ide, sol,d
Sod,um cy;m ide, solld
Zone cyan ide
SHI PPING D ESCRIPTIO N
UN1680, Potamum cyanide , SO ii d, 6 1 PG 1 (M • — Sod ,um cyan ide, solid, 6 1, PG l (Mar,ne
– UN1713 , Z1nc~a~ 1. PGi(Mar ~ ePof~
CPSC b3nned rhe sale of products co ntaining warcr-so/uhle me rallk cy .d 1 0.1 1 – K TRANSPORTI NG METALLIC CYANIDES When th e name of a metallic cya nide or its so lut io n is not lis ted in th e H d 10. 12 SULFUR DIOXIDE Toda>•, s ulfur dioxide is used mainly as a bleaching agent by the pu lp and paperindu s• Sul fur d ioxide is also used to fum iga te sto rage co mpartm en ts o nb oard ships, wheren Ai+l!IIIIN Phys tcal Properties of Sulf ur 01ox1de Boiling point
Specific grav ity at 68 • F (2o• q
-10S “F(-76 °C)
14″F(-10 “C)
Vapor density (a ir= l) 2 .22
376 Chapter 10 Chemistry of Some Tox ic Substances
su lfU l’I DIOXIDE (PPM ) SIGNS A.No S’f’MPTOMs
d)l
;,O 1 ~ oco~~ ct lon in se’.1_111,ve. e1tercis,ng a1;;;;:.a1,c, !_::. lung~ ct 1onchange1lnh~ lth — 1 20-50
20 minute exposur e produce ;erman ent pulmonary impairment eyes an~ de,..ctopment of chroni~ S0-100 Ma1timumtolerab!eexpo1urehm ,tfor)()..(;Om in – ::~\:~;~:ym1~1~:’.e \Ource1 Incl uding CHEM/NfO. s.,11~, Oiox ldt, Ci n..dlin Ctnt,t for Occupitloni l Hulth
10.12-A ILL EFFECTS CAUSED BY INHALING SULFUR DIOXIDE Ast hmati cs ar e especia ll y susce pt ible 10 ex perienci ng ill effec1s from inha ling sulfur 10.12-8 ENVIRONMENTAL EV ENTS ASSOCIATED WITH THE ln December 1952, coa l was virt uall y. th e so le. fuel use~ in \ond;~~~r ~:~:~.:t::s1~;.1i:~ 10 rlepen ds on the q ual ity o f th e ai r we breathe.
Leth al Londo n Smog occurred when London Chapter 10 Chemistry of Some Toxic Substances 377 r acid r,1 in • PrK1 prt at1on umes sulfur dioxide 1s sull a ma jor air compo nen t. Almost 1~’0- by the use of’ scri~~~/:~:d ~~hJ~i~~~\•ays other than th ~_bu ro ing of coal . It is udt~fu~t~~i:~ reacts with atmosph(‘ric moisrnre to form sulfuric acid.
250 1(g) + O~(g ) – 2S0j(g) S~lfurmo\l.k Sulfu ncac,d
The presence of sulfu ric acid in the atmosphere produces a type of acid rain, that is, prt• The relea~ of su lfur dioxide to the atmosphere produces the environmental probltm 10.12-C SULFUR DIOXIDE AT FIRE SCENES Coal, natural gas, and crude oil encounte r it wh en the y respond to fi res invol ving their combustion or the bur ning of 10.12-D WORKPLACE REGU LATI ONS INV OLVING SULFUR DIOXID E ~:it !~~~::~;,’·•1;~;~:•;;~~n.1 fo r nupri ve pr oces1e.1 as ind ,cJt ed by sulfur d10.~ idc em1.11 1om irom K,butJ ‘ ‘ J. Volcano/, Grorl,rrm. Rn ,Vo l. 108 12001) pp. 283-302. 12.E ENVIRON MENTAL REGU LATIONS INVOLVING 10, SULFUR DIOXIDE
Osing 1he ;i uth o r_ir r of th~ Cl_ean _Air Act, EPA regulates rhe sul fur dioxide concentration ~l ;d for su lfur dio~ide at O. t 4 pans per milli on (365 µi;,’m 3) and 0.03 parts pe r million 10_12.F TRANSPORTING SULFUR DIOXIDE ~~n~pOrt sulfur dioxide, DOT requires 1hem to identify it on an accompanying shipping UN 1079, Sul fu r dioxide, 2.3, (8), (Poison – Inhalation Hazard, Zone C)
oOT also requires shippe rs and carriers to comply with all applicabl e labeling, mark- When fi rst-on -t he scene emergency re sponders are called to a transpor1arion mishap 10.13 HYDROGEN SULFIDE ihhiiMI Physical Properties of Hydrogen Sulfide -Boiling ~ ———-l..- ~ ordensity(a!r::1) Autoign il ionpo int
Lower flammabl e limit
Upperflammable hm,t
1.54
1.18 500″F(260′ C)
4.3¾ byvolume
46¾byvolume
‘r~blc 3, Emtrgmcy Rl’spot1u Gwdebook (W~ihington, DC : U.S. Deprnmrnt of Tr msportati on, 2012 ), p. 35 5.
Chapter 10 Chemistry of Some To xic Substances 379 r Althou h h droge n sul fide is avJtlable as 3 liqu efii:-d com,r r~sse~ g.1s , ll is 1101 a etro kum rdineries and n:uural g;1s wdls. In th~ ch emical mdus~r y. hydrog metallic ~ul fid~ such as nickd sulfide and molrbd enunt sulfid e, and co
pho~ u~ed in tcl~~i~io_~ ~~~s~ced n:iturally by the decay of organi sm s m swamps late ~::li~;d~:~~~ sulfide ha s a highly repulsi l’e odor, mo st people become aw 10.13-A ILL EFFECTS CAUSED BY INHALING HYDROGEN SULFIDE The mech:inism by which hydrogen sulfide causes adverse ailments is similar to diai id=l!il•lti 0.011
2.8 7or14 28 >140
>560
.- 100
Ill Effects Cause d by lnhahng Hydro gen Sulfide’
SIGNS ANO SYMPTOMS
Odorthrl!shold F~t1~ue, loss of appetite, headache, irritability, poor memory, I Respfrato~d ;,tce,, ~~:::1 ;1~::~~~;~::tt;;(~ Chou, “H~d,ogtn sulfide : Hum an he alth aspem • c~ 380 Chapter 10 Chem istry of So me Toxic Substances
10 Ji)d rose n sulfid e is a fbmmahle gas. Wh en ignitt’d in air, it readil y bu ms as foll ows:
21-1!5(.11) + 30 2(g) –. 2H ~Otg J .., ~O,(~) At fi re scen es, the presence of hy~rogen sulfide-although possible-is gen eral] ‘ im rob – 10.13 -C :~::i~~Es~i~i~’:TIONS INVO LVING
When .the use of hydrogen sulfide is n~e ded in th e workplace, OSHA requi res employers HYDROGEN SULFIDE MAY BE PRESENT
10.13-D TRANSPORTING HYDROG EN SULFIDE UN IO H, Hydrogen sulfide, 2.3, (2 .1 ), (Poison- lnhala1ion Haurd, Zone A)
DOT also requires shippers and carriers to comply with all applicable labeli ng, mark – 10.13-E RESPONDING TO INCIDENTS INVOLVI NG A RELEASE ,\lost fata lit ies associated wit h hydrogen sulfide exposure have occur red wh en employ- Special attention must be given to enclosures in which hydrogen sulfide may be gen• Chaptl!r 10 Chemistry of Some Toxic Substances 381 Nitricollid•
totheab1 htyof asub- • breathmg air from self-contained sources. Work sh 10.14 NITROGEN OXIDES 1 0 3 formulas are ‘.’\O and :-;o , respecti\’ely. Tht molecules of mtnc oxide an d n1trogcn diox.
idearcst:ible frer radicals.
Ikea use th ey often are produced m combination, ni u ic ~xid e and ni~rog:n dioxide com- 3 ing a pungent, acrid odor. They arc ~oisonous, nonflammable, an~ corrosive substancrs_ Desp ite its poisonous nature, mmc ox_1d_e often is_ enco untered m modern hospi- Kirrogen dioxide is used by the aerospace industry to oxidize rocket fuels. Fo r mm- CH , H CH3 H A mix ture of ni~rogen dioxide and unsym- dimeth ylh ydr.izine is se lf- reactive, or illlill1iti Physical Properties of N1tnc Oxide and Nitrogen D10,nde Bo iling po int
Spec ificgravitya t6B ‘ F(20’ Q
Vapordensity(air:: 1)
I NITRIC OXIOE – 243’F(-153 ‘ C)
1.34
1.04
NITROGEN DIOXIDE
12°F(-11 “C)
6B ‘ F(20’C)
1.49
1.59
382 Chapter 10 Chemistry of Some Toxic Substances
SOLVED EXERCISE 10.5
i•:i r1,0 n,irogen d ox de molecu ‘es comb, ne to proa uce a s,ng e mo’ecue of d 11,u-ogen tetrox,de1
~1~tio\!:s\e~~~~;~::sn’.i~~~~ ~’.~~~:~/=rt~;ga~”f: 11:: are ·’- · and O, respe<1Ntly Us1rig them, the
1o; ,,,.,pg
-~:N:: O: or 0-\,_Q
. ,ieth, 5wucturehasanunpairede lectron,1tae1ua’ ly 1epresentsafree-rad,calmo’ecule (Stct,onSl1) To d• n trogen 1e11ox de mo’oo.J’e
10.14·A PRODUCTION OF NO,
0-N=O
I
0-N=O l\itric oxide rand ni1roge n dioxide are produced for comme rcial use by the catalytic oxida• -INl-\i(g) + 501 (8) –o -INO(g) + 6H~O(g) 2NO(g) + Ozlg) -,. 2NO~(gl When confi ned in a cylinder at room temperature, 1he nitrogen dioxide com bines with 2N0 1lg) -, N104(/) Although di ni troge n letroxide exists at room conditions, iris commo nl y sti ll refe rred to as 10.14-B ENVIRONMENTAL ISSUES ASSOCIATED !n the lower atmosphe re, nitrogen and oxyge n combine ve ry slowly to produce nit ric N2(g) + 02(&) 2NO(g) 2NO(g) + Oig) –, 2NO~(g) Ai fo~sil-fue l-fi red powe r plan ts and in the combustion cha mbers of motor vehicles, nitro· is regarded as a ma jor air pollu tant. It is the principal culprit responsib le for t he Nitrogen Chapter 10 Ch e mistry of Some Toxic Substances 383 r R GURE 10.9 NN!fy.ill W”-‘O,ll’lthe,lJTll;rtflt.:l,r e~~ dunngtrans• ~~’Wlg(‘Cl’I.DC)
Nonchem 1cal Ch emicel 1%
Fuel 46%
The presence of ~ Ox in the lower. atm?spher_e is dircc.tly .lin~ed wi~h _the prod ut- N0 1{g) – NO(g) + ·Q ·(g) 01(g) • -ii•(gl – OJ(g) Nitrog en dioxide is also re sponsible for th e formation in the lowe r atmosphmof 0 R- C Pr ru~);ic)! nllmlt These constituents of polluted air are especially powe rful respira tory and eye irritants. Concerned about the advers e impact on public hea lth posed by NO.n es peciallJ· in 384
. Alt~ough t~e nitrogen oxides can migrate to the ozone laye r, t hei r presence dOt”s I\Of Chapt er 10 Chem istry of Some Toxic Substances
1, 0 gen dioxide a ll : rcfon n n11rous ox1 e, w ic t en proceeds agai n to rea ct wi th ozo ne.
NO(g) + 01(g) -.. N02(g) -t- 02(gl N02(~l + ·9 ·(1:) – NO($) 10_14.C ILL EFFECTS CAUSED BY INHALING NO, lmon ary edema. Hb(aq) + NO~(g) –. (N02)Hb(llq) Mcthemoglobin is an oxidized form of hemoglobin. The iron in its molecul es occurs Hyper baric oxygen therapy is ineffective whe n used to treat individuals afflicted with iili!IWI Ill Effects Caused by lnhahng Nitrogen D1ox1dei) 10-20
25-<0
S-0
80 >200
25-0
Thresholdl imitfor detectio nbysme ll
Mild irr ita tion to the eyes, nose, and upper respiratory tract
No adverse effects to workers exposed over a period of ye ars
Distinct irritationtotheeyes, nose,andupperresp!ratorytract
Tightnessinthechestafter3-to 5-minexposure
Lung injury; bronchopneumon ia:threattolifeafter20-to60-min ‘Ad.ipt,d from mu ltiple sources lnclud,ng Center5 for D15e;i~ Control arocl Prevent ion, 1988 Permissible hposuie met hemoglo bln produced whennitro• methemogl obin emla resultingfromanindi· Cha pt er 10 Chemistry of Some Toxic Substances 385 . d s exacerba1ed by the ability of th e gas to \\ -;Her. A nuxture of mtrous ac, an m \ itr0~nd10\1.li: 0 W.hen 1t 1s inhale~, n~tr e:tl within the respirator~ sys~em. Because nnric acid is a mixture of chese acids ir [ h I s and conneco,•e msues, and even at low c tr0rig acid. it damages the hmng o tul~ ~~!rr edema, oncentr1. 10 14-D NITROGEN OXIDES AT FIRE SCENES . l’\iinc oxide and miror~ IOXln–containing mamials. Examples of nit rogenous Ille COQl. 1 puls~~r?a-i~~:::~rcial explosives also p~o.duce nitr ogen di~ xide when they detona it. 10.1 4-E WORKPLACE REGULATIONS INVOLVING When the use of ni tr ic oxide and nitrogen dioxide is ~eede d in the w~rkplace, OSHA 10.14-F ENVIRONM ENTAL REGULATIONS INVOLVING EPA regula tes the concent ration of NOx in the ambient air.as a cri teria air pollutant. EPA 3 0.053 pa ns per million (100 µg/m ) as an annu al amhmeuc mean.
10.14-G TRANSPORTING TH E NITROG EN OXIDES iilhll·if:i Dinitrogentetrolide
Nitricol ide
Sh1ppmg Oescr1pt1ons of the NO.– Components
SHIPPING DESCRIPTION UN1067, Dinitr ogentetrolide,2 .3, (5 .1), (8), (Poison Inhalation 386 Chapter 10 Chem istry of Som e To~ ic Substances
Physica l Properti es of Amm onia
i,4tlt•fl!lpoint -10~ o ____ _ 1 ~ d~ —__,1,.:’c:”::’_ – • I –+ 16%by volume Wh~n these nitroi:;en oxides, are transported by rai l in bulk packaging, DOT requires 1o.15 AMMON IA Om 80 % of th e ammoma produced m the United Stales is applied to farm lands as a Lm than 2 % of th e ammon ia produced in the United States is used as a refrigerant in When ammonia is used as a refrigerant or fe rtilizer, it is enco unte red as th e liquefied Anhydrous ammonia is also used in shuttl ec raft, wh ere it se rves as the coolant in the 10.1 S-A PRODUCTI ON OF AMMONIA 2NH3(g)
Anhydrou s nu rse Forp ur- Chapter 10 Chemist ry of Some Toxic Substances 387 388
FIGU RE 10. 10 DOT requ.res a nur;e tanl: used for the appl1 c.1 t1on of anhyd rous ammoni a to agncult ur;ij ~ h ~hemica/ manufacturers generally produce ammonia at a pressure and tempe rature rang• 10.15-B AMMONIA AT FIRE SCENES . . ,_ammonia dissipates with the wind, and a flammable m1xrure m air1s 4NHJ(g) + 30 2(8) — 2N2(g) + 6H, 0 ( ) This heat of combusrion is low com d . Chapter 10 Chemistry of Some Toxic Substances •. ,, .• :::;;—- …. Detectable hm it by ~ or Ill Effects Cause d by lnho1hng Ammonia•
5tl -,. Odor detected, but no chronic effects
150-200 J Verys-trongodor;.genera l discomfortand irr itationofnose throat.–;-;;– —-f exposedmo1stsk,n, eye-tear,ng ‘ ::::s~vr~se eye irr itation that may lea d to (oss of ;1ght f~llow ing —20IJ0-300o Barely tol~rable for more than a few moments, convulsive coughing accompanied by severe ~e Irritat ion and blistering of the skin· danger s000-10,000 Resp iratoryspasms;rap!dasphyxia; deathbysuffocationwith inm lnutes Ammonia ma y be generated at a fire scene in at leas1 two ways:
, ,\\ac eria ls manufactured from anima l produc1s- like leather items and wool • Frrtilizers containing ammonium compounds decompose on exposu re to heat. For Ammo niurn,ul fa tc Ainn10ma Nmub’tn Su lfu1d10,;1dc Wa1cr
10.1 5-C ILL EFFECTS CAUSED BY INHALING AMMONIA 10.15-0 WORKPLACE REGULATIONS INVOLVING ‘X’hen t~e _use of anhydrous ammonia is needed in the wor kplace, OSH~ ~eq uires emp\of 10.15-E TRANSPORTING ANHYDROUS AMMONIA Chapter 10 Chemirtry of Some Toxic Substances 389 m nnW-iif.l:54¥iMl::l::1·1:li iflt:er~- —-… Ol EMJCAL COMMOOJTY ,I UN1005, Arnmon ia anrlydrous, 2.2 (l nhal atio ~
Anhydrous Am moru il UNlOOS, Ammo~ia, anhydrous, 2 J, {8) (Pois~ ‘Oomestkrr• tt$pOl’U!IOll. also requ ire-s shiprxrs a nd carriers ro compl y wi1h all applicabl e labeling, marking, i~ 10. 15-f RESPONDING TO INCIDENTS INVOLVING A RELEAS E Ammonia injures rhe human organism rhrough two differenr mechanisms:
As cold liquid ar _28″F (-JJ°C), anhydrous ammonia freezes skin and orh e, tlss ties
at th e ~inrsl o/ccodat:~~,viduals who brearhe :immonia experience the adverse hea /.1 As previous y no e , 111 ronr.1ined breaching appararus is essenti:tl when_ emergency re~po_nde rs arrrve at _a SCCII(‘ The v:ipor den siry /isred in Table JO. l ~ 1s :in md1~ar10~ that ~mmom~ 1s l1ghrer 1hJn such conditions, these droplets behave as a dense gas, traveling along th e surfa ce of 1he Warer absorbs 3 very large volume of am monia: Ar room condi tions, one volume of “” e~posure to ammonia bums !he eyes and na~I PIS\.39fWays ilnd the mhalatl()(l of elevated 1tsflammo1ble 1 hdve ,nhaled ammonia The treatmMt may be l;m,ttd to itdm,n.stering oxygen unt,1 thty can When first-o n-the scene eme~gency responders are called to a 1ran spor1ation mi shap 1 hr 53 fery of 1he tea m, transportation personnel, and th e gene ral public is ar risk. The spills of an hrdrous ammoma occur from multiple sma ll cylinders, single ton cyhn- , iling wind condmon s. ;~~oni::a resulted i~ the d~ath ?fa lo~%! residenr. More th an 1400 others expe rienced 10,15· G AMMONIA SOLUTIONS :queous solution of ammon ia as ammonium l,ydroxide, aqtfeous ammo,_,ia, or ammo11′.a Commercia l ammon ia solution s co ntain disso lved ammonia that ranges in concenc~a- 10.15· H TRANSPORTING AMMONIA SOLUTIONS
SOLVED EXERCISE 10.6
DOT reg ulates the tra nspo rtat ion o( am monia soluti~ns acc~rding to their am n~on ia co n• 390
To p,otte1 public health, safety, and the envrronment what imm ediate action sh ould be tak en by f,rst-on•:1-l- Chapter 10 Chem istry of Some Toxic Substances 1 8 Rdme of Anhydrous AmmoniJ Near Minor, North DJkOtl, January , – -, ‘ chapter 10 Chemist ry of Some Toxic Substances 391
SMALL LEAi( FROM A LARGE PACKAGE) —
FIRST l ISOLATE PROTECT IN ALL DIRECTIONS
-t– r-
-i–
1242 139 M ethyldichlorosilane 30
water)
100
(when spilled In
w;ater) – 139
Trichlorosilane {when 30 100 0 .1 0.1 0 .3 I • 2 60
1295
16 13 154 Hydrocyanic acid,
–,_ , –
aqueous solution, with
not more than 20%
hydrogen cyanide ~l t—- 150 500 o .s 04 1 7 I Hydrogen cyanide, 60 200 0 .2 0 .1 0 .7 0.4 1614 152 stabilized (absorbed) 300 0.6 04 2 J I 5 30 100 0. 1 0 .1 0 .6 0.4 100 1660 Nitric oxide 1660 124 Nitric oxide, com-pressed
water)
SMALLSPIUS
1831 137
SMALL LEAK FROM A LARGE PACKAGE)
ISOLATE PROTECT
NAME OF MATERIAL m ft km mi km mi
Potassium cyanide,
solid (when spilled in
water)
Sodium cyanide, solid
(when spilled in
water)
spilled in water)
Sulfur trioxide, 100 300 0.4 0 .2 0 .9 0.S
inhibited
stabilized
with not less than
30% free sulfur
trioxide
flammable, poisonous,
n .o.s. (Inhalat ion
Haza rd Zone A)
flammable. poisonous,
n.o .s. (Inhalation
Hazard Zone B)
{FROM A lARGE PACKAGE OR
ISOLATE PROTECT
DAY NIGHT
400 1250 2.9 1.8 5.7 35
396
~I I
0 0
Protective-
actionzone
zone /
Spj ll
isolation
distance
).,wte regions 1n which md1v1duals risk. exoosure to a hazardous ma~enal mat poses a health hazard by ,nhala-
. From a practu:al vitwpoint. the initial isolation zone 1s tlie area of a orcle whose radius equals the 1n1t1al
: atond,stance, andtheproiect1Ve-ac.t1on_zone1s theareaofasquareeachofwhosesid~equalsthe
p-o·.rct ~,-action (downwind) diSlance The initial isolation d1stan” and protective-act1on distance are pubk,hed
11 L’lt gr~n se
cionsof a toxic gas or vapor that poses an inhalation hazard. Emergency responders should
fll’SI direct persons to areas outside the initial isolation zone.
rsiablishcs the protective-action zone shown in Figure 10.1 l (b). The protecti”e-action
zone is the area in which persons may become incapacitated and unable to take protective
action and/or incur serio us, irreversible health effects. After they direct persons outside
th~ initial isolation zone, emergency responders then should direct others outside the
protective-action zone, beginning with those individuals nearest the right-hand semicir-
cular component of the ini1ial isolation zone.
For purposes
minimum distance
downwind from a
transportat ion mishap
involvlngthe release of
a hazardous material at
which emergency
responders and the
publ ic can reasonably
anticipate that their
health, safety,andwel-
farewillbepreseNed
For purposes of DOT
which persons may
become incapacitated,
unable to take protec-
t ive action, and/or incur
serious, Irreversible
health effects
ta~m recommended by DOT for protection of public health at an I 1 00 , 1.1 domestic transportation mishap
111,olvng a leaking 75-pound (34-kg) cylinder of hydrogen sulfide.
!pill o! hydrogen sulfide It Is prudent to acknowledge that 75 pounds (34 kg) constitutes a ~large” sp1\I of a toll.IC
IUbstance Furthermore, In most pal’U of the United States. 11 1sdark: at 11 oo, M Hence, we examine Table 10 23
~nder the heading ., night ” for the 1n1tial I~olat1on and prote
6m don appropriate protective clothing to prevent the poss1b1hry of skin_ contact. T~is
protective clothing includes impermeable coveralls or similar cncapsulat1~g body suit ,
glo1·es, head coverings, :md self-contained breathing apparatus. Because toxic substances
cancu • A. large group
ofdisease1character-
ized by the uncon-
trolled growth and
5preadofabnormal
cell5
cancontributetocaus-
ingtheformation ofa
tumor in a living
organ ism
sulanng body_ suit ~ • ubstance h;1s come in conrn: t w_1th clothing, n 1s essential 1; uoth routes. Once a toxic : . with water before removing It , . thor.
oughlr wash the cl~~ 1? . kl provide professional medical :m ention · .
who have betn e_xl:’°se Whenever a team responds to any accident . or
sym~~oms of an ~nJ~~f~rmation concerning the unique properties ~f the poison !Tl~ , of
a toxi~ s~bs:~~,s~ccessful protection of Jives, property, and 1he env1ronn~ent. ht
esSt’~;~~/:n accident occurs within an enclos~d area, the use of a confined-space en ,
monitor (Fi ure J. l ) can quickly provide an esumare of the vapor concentration to wh~
the workerf or other individuals are exposed: _CHEY1!REC a~d the Amerii~n AssOCia.
tion of Poison Control Centers may also be uuhzed as mformau.onal sources, and When
an injury has occurred in connecrion with the use of a c~rmerc1al product, the U.S. Con.
sumer Product Safety Commission should be contacted.
transportation mishap involving the release of a toxic ~ubstance. As a ?as1s for tnaking
technical decisions, firefighters may compa re the readmg. from a confmed~spacc entry
monitor with the STEL, PEL, and IDLH values _for the wxic substance. If the decision to
fight 3 fire involving a toxic substance is m:ide, firefighters should also observe the follow-
ing basic principles;
them from an upwind location.
Use fog instead of direct streams of water to limit the generari_on of poisonous duR
Keep runoff water to a minimum, and channel runoff water into a temporary r™r•
voir to prevent its entrance into local sewers or waterways.
Notify rhe operators of the relevant storm and sanitary sewer system and water treat-
mem plant of the ongoing fire.
Cancer is the name given to a relatively large group of diseases cha racte ri zed by rhe
uncontrolled growth and spread of abnormal cel ls. Ir is the most fearsome disease among
populations living in developed countries. Despite decades of research work and billions
of dollars spent to combat cancer, millions o( individuals are still diagnosed with it annu-
ally. 13 Nor only docs cancer often cause 1heir deaths directly, but the current cancer ma1•
ment processes-chemotherapy and radiation-compromise the immune systems of
cancer patients so severel y that individuals who survive treatment may ultimately sue·
cumb from pneumonia or other diseases.
c_alled carci~ogens. Chemical ca rcinogens, physical carcinogens (like ultraviolet rad1a·
non), and viru ses cause cancer in living tissues. In addition, many individuals inheri1 a
:~;11\ ·: ~ ;~;~~;:~~1~~1C:d provided on the label. The poison ho tl ine may also be conmi(I]
:~;i;;o~·i· ~~o:I~ ;;:a~uct Commission mny be comacted ar (800) 638-CPSC.
wide eve~ su r J . h th _Organuation reported tha t cJ ncer had become th t· leading c.iusc of death world-
S’tl< is prini:1rily Wllh an mdivtdual s poiential exposure to chemical and physical c:i~ino ens.
('(I'll t he two moSt co~nmon method~ for determining whether exposure to a subsfance
1
v:d from stud_ies conducted by toxicologists and epidemiologists.
. P g.tsts rev1e
ncedto dete
rn:ime whether the rate of development of cancer, if any, has
1 Cancer may star1 as a disease of ~ells that malfunction because of an exposure 10
J ors externa l to rbe body. Th~se carcmo~ens enter or penetrate the cells (e.g. , radiation)
: use cancer b)’ as much a~ a nulhon-~old.
pktel)’ understood, sct~nnSts.now know tha_t !t_c~nsists of a muhistepped cellu lar phc•
nomenon that can be viewed m three stages; mmatton, promotion, and progression.
health)’ cells beco~es altered. Somcumes, this cellula r alteration results from a single
exposure to a carcino~e~,. whereas on other occasions it results from repe::i ted exposures.
Carcinogens tha.t are m1t1ators transf~rm or mutate cellular DNA. Thus, ihe molecular
~J we\·er, these initially d:imaged cells rarely cause cancer, because there are many cellula;
moechanisms for repairing the damaged ON~. h is when the cells are unable rn repair the
damage that they are more prone 10 becommg cancerous.
pens when _genetic errors occur natural!y during the replication phase of cellular behavior.
stnUlarly damaged cells, each of which subsequently divides without restraint into new,
similarly damaged cells. Ln most instances, cell division is accelerated when the damaged
cells are exposed to carcinogens; chat is, these carcinogens act as promoters rather than
ini tiators. When cell division occurs over an extended period, the aggregates of damaged
cells often create a mass of tissue called a tumor. (Leukemia is a cancer of the blood-
forming parts of the body, particularly bone marrow and spleen, in which cancerous
white blood cells form a diffuse liquid tumor throughout the circulatory system. ) It is
mind-boggling to realize that each tumor has descended from a single ancestral cell or
group of cells that went awry. Some carcinogens are so powerful that they cause can-
cer without the need for promotion. Exposure to ionizing radiation (Section 16.2), for
m mple, directly initiates a variety of cancers.
migrate to other tissues and organs in the body, where they may provoke the emergence
of tumors. Although tumors may be either benign or malignant, it is generally during the
progression stage that malignant growths first develop … Malignant” is a term applied to
growths that penetrate the 1issues in which they originated, spread further (metastasize)
1oother locations in the body, or cause death. Cancer is viewed, in pan, as the transfo~-
mation of previously heahhy tissue cells into malignant tumors. The phenomenon assoc1-
a1ed with the formation of a malignant growth at one site in the body from cells derived
fro m a malignancy located elsewhere is ca lled metastasis. A tumor t.h~t is lo_ca lizcd and
noninvasive is benign, whereas a tumor that is invasive and metastatic 1s mal1gnan1.
cancer is especially high. More than 60 chemical carcino~ens have been 1denuf1ed amo_ng
ihe approximately 4000 substances known ro be consntuents of tobacco smoke. W1t.h
rach puff, ciga rette smokers inhale these ca rcinogens and bathe the surfaces of their
one or more h@althy
cells are triggered to
subsequently respond
to the actions of a
promoter
ond 5tage of cancer,
during which the for-
mation of malfunction-
ing cells is accelerated
to produce tumors
grows independently of
its surrounding 1truc-
tures and ha5 no
known physiological
function
stage of cancer, during
which tumors evolve
into malignant growth5
in the body
growth at one site in
the body from cells
derived from a malig-
nancy located else-
where in the body
I
I
400
nomeoon in which two
ormorrsubn•nces
int!’factinsuchaway
that their combined
effects are more severe
th.nthesumoftheir
individual effects
resp1r.Ho(}’ tracts\\ •~ ~;re than ZO-fold higher than that of nonsmokers. %r.
ing lung cancer th:u 1; mors within the lungs and ot~er org:rns of tobacco smoker~
t’\’Cll be acctler.1tc-d by ~x~s~:~ros, ethanol, and radon are nontobacco car
~oOOccosmoke. For:~~c{ct~cer de\•dops in smokers compare~ to the m_te t
increase the r.:He at . h enon is an example of synergrsm; that 1s, the inc
ment in nonsmoktrs: Thi:
~ er~:ces more profound effects 1han either carcinoge;:ct1on
O separa tt’ly. Tht’ pht’nO It’ smokt’rs exposrd to asbestos are more vulnerable to contra t’.icr
(noncancerous) as rostsbcs is than are nonsmokers with an equal exposure, %
mor;i:;~;;;~:;::: an;:er group ~hat is more prone than. th~.pe.neral population to
de,•elo cancer. &ised on inform:nion der.1ved from research studies, firefighters are twK:t
35
Hod kin ·s I homa, and prostate cancer compared ro t.h~ ~eneral population. Ir is prudcm
co aS:ume J::~r least in some instances, the firefighters 1~111ally contracted these cancers ii}·
exposure to carcinogens like certain 3sbesros fibe~s (Section IO. l 9);. soot, polynudear aro.
matic hydrocarbons, and other diesel fuel combu~aon prod~crs. (Sccno1~ 12. l 2-C); and poll’·
chlorinatrd dibenzofurans and po!ychlorin:md d1benzo-p-d1oxms (Secnon l 3.4-B).
At least five organizations study whether exposur~ to a substance adversely impacts the
human organism or experimental animals as a carcmogen: E.PA, OSHA, NIOSH, the U.S.
Departmenr of Health and Human Servi~es’ National Toxicology Program (NTP), and
the World Health Organization ‘s lnternauonal Agency for Research on Cancer (IARC).
The 1’1TP publishes biennially reports on carcinogens. The rwelfrh report, published in
10 11 listed 240 substances as carcinogens.
– £lch of these agencies classifies the carcinogenic potential of a substance similarly,
but yet, differently. For example, IARC pro,·ides the procedure of classification for gii·en
substances as shown in Table J0.24.
duced a scientific literature peppered with such terms as “known human carcinogen,•
“suspect ca rcinogen,” “probable carcinogen,” “potential occupational carcinogen,” and
“reasonably anticipated robe a human carcinogen. ” This classification sometimes isn«•
essary, because the existing data do not always enable toxicologists to clearly ascertain
GROUP SHIPPING DESCRIPTION
Group 1 carcinogenic to humans
Group1A Probably carcinogenic to humans
Group2B Possibly carcinogenic to humans
Group) Not classifiable as to its carcinogenicity to humans
Group4 Probably not carcinogenic to humans
Enwo11, Mrd., \’ol. 48 iioo6), pp. ~\sa:~;g/refighrm: A review and mcta-.-ina/ysis of 31 s1ud1es, /. Ot,:uP.
11 h:sis are cornphcated by th e observation that certain substances appear incapable of
gerl “ii)’ causing canc~r, b.ut the.y can affect the rate of tumor formation when ex osure to
J1r~ occurs in combmauon with exposure ~o orher substances. p
chc individuals are exposed to cancer-causing substances in a variety of wars. Because
crrain carcin~gens. occur natur.ally, exposur~ to th~m often is unavoidable. Carcinogens
13
r be conta ined JI\ commercial . product s, mcludmg gasoline and diesd fuel. When a
.J,ising rhe con_sumer. Co.nveymg ~his mformation is the responsibi lity of the seller, who
~sobhga ted to display the information at the locations where the product is sold.
proi·ide employ~es w~th protecuve ~lothmg; self-contained breathing apparatus, and a
segregated area 111 which t~e w~rk with c.amnog~ns be safely conducted. OSHA also
~:rds. For example, OSHA requires the area of a workpl ace where vinyl chloride is
used to be posted as follows!
VINYL CHLORIDE
FLAMMABLE GAS
UNDER PRESSURE
AGENT
To reduce or elimina te their exposure to carcinogens, emergency responders should
The)’ also should heed the health hazard pictogram 1hat OSHA requires the manufactur-
m, distributors, and importers of carcinogens to display on container labels.
emergency responders as they are first encoumered. 15
From a nutritional viewpoint, metallic compounds may be classified as follows:
for the proper functioning and survival of the human organism. For this reason, nurritionim
refer to them as the essential elements. They are calcium, phosphorus, potassium, sulfur,
sodium, chlori ne, magnesium, iron, zinc, copper:, molybdenum, cobalt, iodine, and selenium.
Their proper balance and availabili ty are essentia l for proper biological function. This is
nor meant to imply that the essential elements are beneficial in all doses. The ingestion of
de\’ated concentrations may cause illness or death, often by damaging cellular components.
dietary benefit to the human organism. These toxic metals include arsenic, ~arium, beryl-
lium, lt’ad, and thallium. The consumption of even minute amounts of thear compounds
can cause illness or death.
1nd Hum,1n Services and the \x,orld Health Org.-inizarion’s lnternanona l Agency for ResC’arch on Cancer (!ARC).
Any element in the
needed for the proper
functioning and sur-
vival of the human
organism
als or metalloids whose
consumption, even in
minute amounts, can
cause illness or death
I
dlloridt
the purposes of the
TSCA regulations. paint
andotherrurfacecoat-
ingsthatcont.-iin l!ad
in concentrations equal
to or greater than
1.0 mgtcm2, or 0.5% by
weight
Certain oth~r mera ~orher factors. The}’ include th e compounds of manganes,, & Ofi
nium, and tungsten. The}’ can eH er o ogi~!
function in che human body.
10.18-A . I he compounds of lead arc most likely tO be regularly encounte
Of all che toxic mera s, r F pie firefighters may bt exposed to them as the b trd
by emergency responders. or exam ‘ y attk
Lead compoun_ s am Jes of these pigments are lea~ acetate, lead chrornaie ot
lead oxide. T_he “/d ‘ s intended for residential use m 1978. of
le:id:::r1 :c:~::~n
~~ited States an estimated 38 million homes_ built before 1978
in fires l!ad-Jaden dust is dispersed into rhe armosp~ere. Frrcfight~rs are t?en put at risk
of~nhaling lead particufates, a10ough the use of respiratory protectJon equipment signjfi.
c::rntl reduces or eliminates their exposure.
This affliction is most prominent m children. Lea_d may dam_agc the nervo~s S}’S!rms of
children expostd to lead by causing them to expenence behav1_oral and learning probltm.
such as hyperactivity and reduced anenrion span, or to physically de,,eJop more slowly
than nonexposed children. . . . . . ,
processes effectively. Further?1ore, rese~rch stud1~s dem_onstrate that IQ {Inrellig:nce
Quotient) measurements obtamed for children dun~~ the~r s~ho_ol-age yea rs relate simi-
combinationofheafth effects caused by lead exposure in children do not terminate, bur continue imo
ailments caused by adulthood. :~c;:::~evers of lead Children who !i,,e in older dwellings in economically disadvantaged communirirs
paint in these substandard dwellings is considered the greates t remaining source ?f
childhood lead exposure. Formerly, experts concluded that the children forced to lfre m
rhese dwellings were at risk of e3ting flaking paint or plaster containing lead. Today,
howevei; they belie,·e rhat the ingestion of household dust containing lead from deterio-
rating or abraded lead-based paint is the most likely cause of lead poisoning in
children.
problems, high blood pressure, nervous system disorders, and memory problems. Whrn
ingested or inhaled, lead primarily affects the human blood-forming, nervous, and kidnq
systems, bur to a lesser extent, it also harms the reproductive, endocrine, hepatic, cardio-
vascular, immunologic, and gastrointestinal processes. Lead interferes with the body’s
mechanism for absorbing the essential elements calcium and iron. Elevated lead concen-
rr~rions can cause severe hea lth problems, including brain disease, colic, palsy, and ant-
m1a. Damage to rhe central nervous system in genera /
and to the brain in parcicula~ ii
compounds ma y also cause latent health effects. In particular, lead acetate and lead phos·
phare are regarded as probable human carcinogens.
6;t MazumddJ~ er at., “Low-beJ en\·ironmenial lead exposure in children and :idulr intcllectuJl funcuoo: 1 0 ow•upstu Y, Enwo11mt11ta!Health, \’ol. lO(ZOll ),pp. 24-JO.
10· 1
~ published regulations 10 reduce or eliminate rhe risk of consumer exposure to lead.
/,.f !orher articles intended ~or use by children that bear lead-based paint; and furniture arti-
;itd
t,ear lead-based paint. Ar 16 C.F.R. §1500.17, CPSC bans 1hesaleof paint having a
Jc3d~~rwithstanding CPSC’s efforts, lea~-based ~ int has ~n used as a surface coating on
10J”S, es • products is sufficiently eleva1ed chat the lead may cause adverse health
en, CPSC set standards for both the lead in paint and the tota l lead content
) r cPSC now requi res the manufacturers and importers of children’s produces to test
th,m h~ total lead content of any children’s produce be limited to less than 100 mg/kg.
chat ~pSC also requires manufacturers and imponers to affix permanent, disringuishing
~n;%r or batch nu mber. The following is an example of 1he required marking:
Date of Production: 9/10
Lot/Batch Number 12345678
When rhe use of lead compounds is needed in the workplace, OSHA requires employers
ro limit employee exposu re to a concentration of 0.050 mg/m3, a\’eraged over an 8-hour
workday. OSHA also req uires the posting of the following warni ng sign in work :i reas
where airborne lead is generated:
mation on bags or conta iners of lead-contaminated protecm·e c/01hmg and eq uipment:
DO NOT REMOVE DUST BY BLOWING OR SHAKING
DISPOSE OF LEAD-CONTAMINATED WASHWATER
APPLICABLE LOCAL, STATE, OR
Chapter 10 Chemistry of Some Toxic Substances 403
I
II
I
10.18- fl d-b d paint hazards pursuant to the Residenti l l(
EPA regulates certain asptc:t~ 0 ea f ~~92 enacted using the legal authority of T~c ad.
B:m
Sellers and landlor s mu5t 17 a11on . I h mebuyers and renters.
. Sellers_ must ~~:;~ss::~e~ of the target home. 3!.td
. h u rcable aspects of the act
EPA _ce~u 1cat1~n is rhe~u~;sturb lead-based paints in homes constructed befo;e l97i and repamnng proJects t a ,
inglead:
lead in the ambient air as a criteria air pollutant. In 2008, EPA se~ the primary and second-
ary national ambient air-quality standards for lead at 0.15 µWm as a quarterly average.
posal of lead-laden wastes that exhibit the RCRA characteristic of toxtcir~.
become certified for removing lead-laden dust from housing ?s well as requmng cenain
procedures to be implemented during the actual removal actions. These regulations are
published ar 40 C.F.R. \\745.226 – 745.227.
When shippers offer a nonoxidizing lead compound for transportation, DOT requim
them to identify it in the shipping description on an accompanying shipping paper. Thrrt
examples of these descriptions are “UN l616, Lead acetate, 6.1, PG III (Poison),”
~uN1620, Lead cyanide, 6.1, PG II (Poison),” and “UN2291, Lead compounds, soluble,
n.o.s., 6.1, PG Ill (Poison).” DOT also requires shippers and ca rriers to comply with a!I
applicable labeling, marking, and placarding requirements.
Asbestos is the generic name of a complex namrally occurring mineral composed of se1••
era\ compounds that conta in silicate (SiO!- ) groups linked into chains. Several types of
asbestos have been used to produce commercial produe1s all of which arc nonflammable
and excellent insulators. ‘
proo~ng, insulating, soundproofing, and decorative purposes. It was a component of prod·
ucts hke_ asbcst?s pipe ~o~er~ngs, flooring- and ceiling-tile products, paper products, ther~l
::~:~a;~s~ilr:t\::• ant1fnct1on materials (e.g., ?rake linings ~nd clutch facings ), _roofHl~
could als~ be w o~ doors, and sur~ace-coatmg and patchrng compounds. Their fibm
En1•ironmema\ Prot«rion Agency, !o~;~:c~;;;4\~~-::~~};_From Lead in Your Home~ (\Vashing1on, DC. U.
fJbrt .1. in roday s market has been sharply curtatlcd or entirely eliminated. a1\:l b1 ity
10-
.• to the adverse health effects caused by exposure to asbestos fibers cypically has
focust’ l,ite serpentme), and the amphtbolc minerals, cummingtonite-grunerite asbestos
10s or.”\ riebeckite asbestos (crocidofite), actinolite asbestos, anthophy/lite asbestos, and
\a fll
~;;~:e ‘asbestos . C~rysotile w_as th~ m?~t co~mon form of asbestos formerly used in the
LJ[llle hesc fibers cause serious health problems, including at least C’No types of cancer.
sure ~o; ss asbestos has been completely scaled into a product, as in asbestos floor tiles, it
oft _ curs when the asbestos-contammg matenal is damaged or disintegrates with age .
T~is
~d to be friable. It is friable asbestos that poses severe health hazards to those who
111 f’ ure t0.12 illustrates that asbestos fibers may range from 0.1 to 10 micrometers m
le.ngi d may be readily inhaled or swallowed. When they are inhaled, asbestos fibers
::;imes arc removed by the cilia lining the respiratory tract. Then, they move into the
throat, where they usually arc swallo~cd. ~nee swallowed, they pose the threat of caus-
in cancer of the esophagus, stomach, m~cstmes, and rectum. . .
typically after a substantial latency period ranging from approximately 20 to 40 years:
fibers have been observed in pieces of tumors surgically removed from the lungs. Such
biopsies dearly link the onset of lung cancer to asbestos exposure. .
Asbestosis, a progressive, irreversible, and noncancerous scarring of lung ns~ue that
occurs when sharp asbestos fibers deposit deep in the respiratory tract followmg pro•
longed exposure. There is no known cure or treatment for asbestosis.
capable of readily
being crumbled, as in
friable asbestos
characterized by the
emergence of malig-
nant tumors on the
lungs
of lung tissue by asbes-
tos fibers
cancer of the mem·
branes lining the chest
and abdominal cavities
resulting from exposure
to asbestos fibers
rounding the lungs, abdomen, heart, and other internal organs. The most common
asbestoMelatcd form of this disease is pleural mesothelioma, cancer of the prorec•
tive linings surrounding the lungs and chest. Mesothclioma is uniquely di~tin_ct_ive to
asbestos exposure, because the disease essentially is never contracted by md1v1dua ls
who were not exposed to asbestos. It weakens the lungs so that th~y become ~ore
vulnerable to attack by other diseases. it is characterized by pers1ste~t coughmg,
weight loss, fever, rasping, and coughing up blood. Although mesothehoma may be
treated by chemotherapy, radiation, and surgery, it is virtually always fatal.
tective linings and sacs
surrounding certain of
the body’s internal
organs and cavities
The cancer of the
surrounding the lungs
and chest
FIGURE 10 .12 The typical size of an asbestos fiber var-
ies from 0.1 to 1 O m1c1ons. shown here relatwe to the
size of some other mate11a\s. These sizes are too small to
be v1s1ble to the human eye. {Courresyof1/le U.5 Eno1roo-
mema! Prorection A(JE’fl()’. ·Asbesros-Conta1mng Materials 1n
I
mineral particle • Any
mineral having the ele-
mental composition
and crystal structure of
the forms of asbestos
that cause cancer
w Because of this association, asbestos is class1f1ed as a huma_n carcinogen. tr.
from ex osure ro friab le asbestos is s1gnif1canrly elevated ~’ hen 1hcy art’ smokers.~
im act. c’:used by rhe simultaneous ex posure to .asbestos fibers and the c~rcinogens I
ro~cco smoke is greater than rhe impa~t _rh~t asbestos or the to~acco ca rcinogens caui:
separately. Two examples of this synerg1suc impact are the fo\lowmg:
tract asbestosis.
nerabi lity to contracting asbestos- rel ated di seases that 1s not experienced bi·
nonsmokers. ‘
INVOLVING ASBESTOS
products sold for use in the United States .. F_or ex~mple, at 16 C._F.R. §1304.4, the use
of consumer p:irching compounds comammg friable asbes tos 1s banned; and at \6
C.F.R. SS I 305.4 and 1500.1 7, the use of general-use garments, tape joint com.
pounds, a nd artificial firep lace ash and embers conrain ing friabl e asbestos is ba nned.
The manufacturers of handheld hair dryers voluntarily ceased using asbestos in hair
dryers.
ASBESTOS
employee exposure to an airborne concentration of asbestos fibers denoted as “0.1 count-
able elongate minera l panicles from one o r more covered minera ls per cubic centimeter
averaged over 100 minutes.” A countable elongate mineral particle is any mineral ha1·-
ing the elemental composition and crystal structure of chrysocile, crocidoli re, amosire,
anrhophyllire, tremolire, acrinolite, or other fo rms of asbestos.
on r~e lefr below ro identify rhc potential harm caused by asbestos exposure. OSHA also
requires employers ro post the sign on the right on the outside surfaces of bags or ocher
~~~;:r~se~~b~:/roreccive clorhing and equipment, scrap, waste, and debri s cont.tining
ASBESTOS
CANCER & LUNG
DISEASE HAZARD
CONTAINS ASBESTOS FIBERS
CANCER AND LUNG DISEASE HAZARD
.” rhe authority of the Clean Air Act, EPA banned the use of asbestos in pipe and ~:re~ coverings ~s well as 3 11 uses of asbestos materials that are applied by spraying.
. the au1horny of TSCA, EPA :ilso banned the use of asbestos in corrugated paper
hed a program cited at 40 C.F. R. §763.91 in which each loca l educational agency is
• Determine whether frrnble asbestos fibers are being released into the air
: Remove and repa ir all damaged :isbestos-cont:iining material
ceilings, and other locat\Ons. The proper abatement procedures include the following:
Preventing the asbestos fibers from becoming airborne by keeping them wet
Removing, encapsulating, repairing, enclosing, or encasing the asbestos-containing
material
Posting warning signs that contain relevant information noted earlier.
When shippers offer asbestos or asbestos waste for transportation, DOT requires them to
fi rst comply with certain packaging requirements published at 49 C.F.R. S 173.216. Th~se
regulations cite the use of ri~id, leak-proof dr.ums and p?rtable tanks, an~ bags _for ship-
ment in closed freight comamers, motor vehicles, or ra1lcars. DOT requires shippers to
affix CLASS 9 labels on rwo opposing sides of the chosen nonbulk packaging and to mark
it with the notation” Asbestos, NA2212.”
as follows:
“RQ,” because the reportable quantity of white asbestos is only l pound~ (0.454 kg) . .
display rhe identification number 2212 on each side and each end of the transp~:>rt v~hide on
orange panels or across the center of CLASS 9 placards or white square-on-point diamonds.
. · h ·d “f t” number o a azar ous
material transported in bulk , it does not reqmre earners to poSt
72 101 156
~he DOT regulauon at 49 C.F.R. §l h. b ·en immersed or fixed in a natural o r
synthetic binder material, such as cement, p\::tStJC’ asp a t, r ‘
rained in manufactured producrs.
I
. A RELEASE OF ASBESTOS
be~~ osed to airborne asbestos fibers as they combat fires mold bmldm~~- The pri~
1~
collapse. To reduce or eliminate chis porenual _exposure, f~refighters should combat thest
fi res from upwind loca tions and u~e-self-contamed breath1~g apparat us . .
reb.t ed disease. After firefighters combat fires m which asb~stos exposure was probable
the fibers may lodge on their hair, skin, shoes, and clothm~. ~ater, the f ibers can~
brought from the fire scene and into the home. To rcduc~ or eh~mn.ate the likelihood that
rheir family members will become exposed _to asbestos fibers, firefighters should shower,
change their cloches, and launder their umforms separately fro m other clothing befor,
leaving rhe fi rebouse.
As first noted in Section 1.4-B, EPA defines a pesticide in part at 40 C.F.R. §152.3 as am•
substance or mixture of substances intended for preventing, destroying, repelling, or miti.
gating any pest, or intended for use as a plant regulator, defoli~nt, or desiccant. In more
general terms, a pesticide generally is regarded as a com~emal prod~ct that has been
inrenriona lly designed co destroy or control the spread of insects, fungi, rodents, weeds,
mold, mildew, algae, and other pests.
cides. Inorganic pesticides generally are identified either by the name of their active com-
ponent or rhe use of a generic term like arsenica/ pesticide. Because their application
leaves a hazardous substance in the environment to pose long-term damage, few inorganic
pesticides are encountered in today’s commercial markers.
foUowing four groups based on their chemical st ructures:
//
OH
(Section 12. I I
II
OH
s
OH
pescmdes.
TO PESTICIDES
authori ty of FlFRA (Sectio I 4 B osu re to spcc1 ic pest1c1 .’ ‘. forrna·
tion on pesticide product l;beis.· ) to compel manufacturers to provide advisor} in
10,Z . d . . .
D shipping pap~r accon~~anymg_the shipment. The Haza rdous Materials Table at 40
~~.R. § J 72. l 01 ~1st~ specif1e ~h~imc_al ~ames as w_ell as ge neric descriptions of pesticides.
· \Xlhen the sh1ppm~ ~escnpuo~ is listed generica lly, DOT requires its technical name
:r~iv~sion 6.1, Packing Group l or l~ , to ~e ~mered in parentheses in the shipping descrip·
. Some examples of these genenc sh1ppmg descriptions are provided in Table 10.25.
and placa rding requi rements.
E p0sure to the airborne smoke and combustion products produced during pesticide fires
x id be fatal. Consequenrly, emergency responders who attempt to ext ingu ish these fires
The common symptoms associated wnh pest1c1de exposure include blurred v1s10n,
rae:en by responders as those associated with hear exhausc_ion. . . .
The use of fog is preferable to the use of direct streams of water because fog is less likely
rosponse action should be stored in a te mporary resen·oir, neutralized with soda ash, and
:~sorbed into sawdust or clay following extinguishment of the fire. Thereafter, the residue
may be disposed of in accordance with applicable environmental laws.
PESTICIDE
Carbamate pestic ides,
solid, toxic
pesticides, solid, toxic
pest icides, sol id, toxic
Pesticides, solid, toxic
UN2757, Carbamate pesticides. solid, toxic (ethyl carbamate), 6. 1, PG I (Poison)
o,
UN2757, Carbamate pesticides, solid, toxic (ethyl carbamate), 6.1, PG II (Poison)
UN2761, Organochlorine pesticides, solid, toxic {Endosulfan), 6.1, PG I (Poison)
UN2783, Organophosphorus pesticides, solid, toxic (Chlorpyri fos), 6. 1, PG I (Poison)
UN2588, ‘ ‘ . “d I’d toxic (ethylenebisdithiocarbamic acid), 6.1, PG I (Poison)
UN2771, Thiocarbamate pest1c1 es, soi ,
UN2772, Thiocarbamate pest1C1des, so ,
UN2772, Thiocarbamate pest1c1des. soi , ox
• ~nt (germ warlat’e
olgf’Ot} • Any b iocide
that ca~ death or
injury to humans,
pJ•nn. o r animals when
intentionally d issemi-
n.rted throughout a
population during
warfare
Any bacterium. virus,
cause a deadly d isease
to exposed individuals
Ce.rra in microorganis ms and roxins are so highly poi~onous_ t? hm~1an s, plants, and a
mals rhat d uring wartime, their disseminatio~ coul~ sicken, m1ure, incapacitate, or or Ill•
wi~ ca use m.:i ss casualties. They are call~d b1olog1cal warfare ag~nts, or germ Warf:,r-
agents. Their common forms are infecnous pathogens and roxms, some examples~~
which are listed in Table 10.26.
rozoa, exposure ro which causes such deadly diseases as anthrax, botulism, •6~~~:
plague, cholera, and smallpox.
A toxin is a poisonous substance biologicall_y p~oduced by ce~tain plants and animals
Examples of organisms that produce roxms . include ce rtain m.ushrooms, spide ·
frogs, toads, jellyfish, and snakes. On ~ntry mto the body, coxms typically acr
either the cenmil nervous system or rhe. circulatory sy~rem, or both; that is, they act as
neurotoxins and/or cyrotoxins, respectively. They typically cause death by produci
paralysis and respiratory failure. ng
1mpa1rmenr, disease, death, or b1olog1cal m a lfonct1on s amo ng the enemy, this warfa tcu.in • A poisonous substance produced by
bacterium
As nored in Section 7.3-A, rhe League of Nations introduced the Geneva Protocol i
resulted in the production and stockpiling of biological warfare agents for defensiv;
purposes.
INFECTIOUS PATHOGEN OR TOXIN
bacterium
&cillus licheniformis
Bacillus megaterium, a spore-
forming bacterium
Section 10.21-E.)
Fatigue, loss of appetite, and other symptoms
biotypes)
‘ senSi Mty, pus-forming skin infections, diarrhea, and headache
Botulism, characterized by vo • • . .
headache, fever, dizziness do m~~ing, paralysis~~ the muscles, constipation, thirst,
d ilation of the pupils ‘ u e or blurred v1s1on, deadening of the nerves, and
\NfECf lOUS PATHOGEN OR TOXIN
biotypes)
ai ure of the body’s internal organs
Q feve_r, characterized by chills, fever, coughing, headache, fatigue, hallucination, and
sometimes chest pain
of the those ex.posed to the virus; characterized by bleeding from the eyes, ears, nose,
mouth, and rectum, eye inflammation, seizures, coma, and delirium
Tul~remia, a disease often contacted by rodents and transmitted to humans; charac-
tenzed ~y sudden chills, fever, coughing, severe weakness, and the development of
large skm lesions; can lead to fata l pneumonia
intrauterine and cervical infections in infected women
fever but characterized with the same symptoms
instances by hot-and-cold sweats, hemorrhaging, convulsions, coma, and death
Pneumonia
ache, body ache, vomiting, and the appearance of a rash on the tongue and in the
mouth that turns to blisters
headache, sustained high fever, severe muscle pain, rash, sensitivity to light, and
delirium
Salmonellosis, or “food poisoning, • characterized by nausea, vomiting, abdominal
cramps, diarrhea, intestinal inflammation, and ulceration
in severe cases, accompanied by typhoid fever and hemorrhaging in the intestines .
abdominal cramps, muscle pain, severe diarrhea, headache, fever, and chills
Cholera, an acute intestinal d isease characterized by a profuse watery diarrhea and
vomiting
bulges called buboes in the groin or near the armpits
ror tsm act Involved contam lnatin the foods displayed on salad bars In several Oregonian re~aurants with Salmonella typh/mur1um. More than
7SO people who consumed food gfrom the salad bars were Infected wlth salmonellosls. [Judith MIi ier, Stephen Engelberg, and WIH\am Broad,
1
~::~e(~~:a~~~:B~~~~no:a;~h~~:~\~~:i~~~-,:~~t!·~ with k1H1ng 20 mlll1on Europeans during
urteenth century. The convent\ona e ie however scientists are seriously cons\derlng whether the Black Death was actually
l’< i~~l~I::~~~::~ : l~~o::~~n~: ~e~~t~~e/ro:a;~~:::~~pe~ by the Japanese from a\rcrah on Chlnese and Manchurian towns and cities.
federa l rtaMesthat
address the prevention,
preparedness. and
response to acts of bio-
terrorism and other
public health emergen-
cies from human, ani-
mal. or plant exposure
to~lectagents
poses of Bioterrorism
Acts regulations, any
infectious pathogen or
toxin listed at42C.F.R.
§733, 7 C.F.R. 3313, or
9(.F.R.1213
Toda y, infectious pathogens and toxins are as_sociared wi~h the likelih~d that bioter
ists will coverdy obtain and deploy 1hem to sicken and kill or create disruption a d to1.
among segments of ,h, American population. Two federal statutes seek
0
Human Services (HHS) and the. U.S. Department of Agriculture (DA) ha ve prepared li)ts
of infectious pathogens and toXJns. Both departments refer to them as select agent Th
app,op,ia« depa,rmen< lists the fo llowing chm types of select agents, s, '
list of selecr agents at 42 C.F.R. S73.3.
publishes this list of select agen1s at 7 C.F.R. S33 l.3. A
lishes this list of select agents at 9 C.F.R. St2t.3. p
All examples of the infectious pathogens and toxins li sted in Table 10.26 are select age
. HHS’s method fo, choosing a select agent is based on the following cdte,ia, ;~;
1m~act on huma? health from an exposur~, 1~s degre_e o~ comagi~usness, the methods b)·
which the agent 1s transferred to humans, ns 1mmumzauon effecti veness, its pmemia\ for
use as a weapon, and the threat posed by its use to vulnerable portions of the population
such as children and the elderly. The USDA’s criteria for choosing select agents are basro
largely on their adverse impact on animals and plants: the relative ease with which th
agent may be disseminated o, o-ansmitted from animal
with regulauons published at 7 C.F.R. Part 33 1, 9 C.F.R. Part 121, and 42
Infectious pathogens and taxi , b I . . include ,he following: ns ma} e covert Y disseminated by several means tha1
• _1 an enc ose space or over a cit
Inoculation of fabric dr ~m_km~ water supplies ‘ paper~ an smular Items
To maximize the adverse im act fro
5
I
5
-.
Ch . • case”‘ clearly evident. Dming chis incubano<
cJllS~ng ,a , be transmitted to others. An e ide ? cause sy~ptoms or mfect other people,
ju<;' 1:~ lware tha< the disease has sprea/ mcc could exist befme medical authorities
fro lll the gene_ral ~opul~uon until a bacterium is identified as conta ious or nonconta-
gious, Conrngcous tfecu~ns may~: ttansmitted from pmon to pmo~ by inhaling bacte-
ria spewed into _r e air. y coug mg or sneezing, contacting body fluids, and simply
tooching som~thing the mfec_ted perso~ previously touched.
of the disease to olhers. Fol\O\\ mg a bioterronst event involving numerous individuals
srate and local governments would moSr likely use their legal authorities co quarantin;
infeered persons so they can be treated medically to prevent further spread of the disease.
OF INFECTIOUS PATHOGENS AND TOXINS
mote rapidly than. medical_ personnel. They use detection equipment that first became
Jvailable ~ommercially. du~mg the late 2000s. Doctors and nurses stand ready to confirm
their findmgs. In com?mat~on, the emergency response and medical personne\ are the first
individ_ua.ls to clearly 1de~~1fy th~t an ~ct of bioterrorism has occurred. Once the pathogen
or toxin has been specifically 1dent1fied, an appropriate antibiotic or vaccine can be
administered t_o curb i_ts impact and protect the exposed victims against death.
off the ar:as pot~ntia\ly c.om~minated with an infectious pathogen or toxin from the gen-
eral pub_hc. While workmg 1~ these areas, personnel need to wear fully encapsulating
body ~ull~ and use self-~o_ntamed breathing apparatus. They also should advise people
who live m th~ comrn~mues surrounding the contaminated areas not only of the impor-
tance of seeking medical treatment but that failure to do so could well be fatal and
adversely affect those with whom they live and work.
knowledgeable professionals, typically through use of a microbiocide such as chlorine
dioxide (Section l 1.8). For individual protection, these workers also need to wear fully
encapsulating body suits and use self-contained breathing apparatus.
• For purposes of DOT
regulations, a material
known to contain or
suspected o-f containing
an infectious pathogen
or toxin
risk group • For pur-
poses of DOT regula-
tions, a ranking of a
microorganism’s ability
to cau~ injury through
development of a dis-
ease as defined by crite-
ria developed by the
often study the nature of microorganisms as a routine component of their profession.
Consequently, it is necessary to transport bacteria and viruses for legitimate purposes
from their point of production to clinical laboratories and elsewhere.
lates their transportation as division 6.2 hazardous materials. Certain special rules apply
tion (WHO) based on
the severity of the dis-
ease caused by the
organism, the mode and
relative ease of trans-
mission, the degree of
r\\k to both an individ-
ual and a community,
and the reversibility of
the disease through the
availability of known
and effective preventive
agents and treatment
. When shippers and carriers intend to transport an infectious substance, they must
hr~t_become aware of its risk group. A risk group is a ranking of a microorganism’s
abilny to cause injury through disease as defined by criteria develo~ed by the :<'orld
H~alth Organization tWHO). These criteria are based on the seventy of the disease
c~used by the microorganism, the mode and relative ease o~ t.r~nsmission'. the degree of
risk to both an individual and a community, and the revers1b1hty of the dlsease through
thc availability of known and effective preventative agents a~d .treatment. The risk
grou~s are identified by the numbers \ through 4, and the crnena for each rank are
• For purposes of DOT
regulations, a human
or animal material,
including excreta,
blood and its compo-
nents, tissue, and tissue
fluids being trans-
ported for diagnostic or
investigational purpose
(but excluding live
infected humans or an i-
mals), when the source
human or animal has or
may have a serious
human or animal dis-
ease from a Risk Group
4 pathogen
RISK
GROUP PATHOGEN
an imal d isease and that can be readily tran.sm,.tted
from one individua l to another, directly or tndir~ctly,
andforwhicheffectivetreatmentsandprevent1ve
measuresusuallyarenotavailable
A pathogen that usually causes serious human or
animal disease but ordinarily does not spread f_rom
one infected individual to another, and for which
effroive treatments and preventive measures are
available
capable of causing serious infection on exposure, 1s
one for which there are effective treatments and
preventive measures ava ilable and the risk of spread
of infection is limited
animal disease’
INDIVIDUALS
low
COMMUNIT’t
High
Low
propersh.ipping names, “infectious substances, affecting humans,” “infectious substances,
affecting animals,” and “diagnostic specimen. ” A diagnostic specimen is any human or
animal m:Jterial, including excreta, blood and its components, tissue, and tissue fluids
being transported for diagnostic or investigational purposes {but excluding live infemd
humans or animals), when the sou rce human or animal has or may have a serious human
or animal disease from a Risk Group 4 pathogen.
the technica l name of the infectious substance in its shipping description. For example,
when shippers transpon 1 gram of Bacillus anthracis, they enter the fo llowing shipping
description on the accompanying shipping paper:
(UN6PJ
{IDENTIFICATION NUMBER, PROPER SHIPPING NAME,
PRIMARY HAZARD CLASS OR DIVISION, SUBSIDIARY
HAZARD CLASS OR DIVISION, ANO PACKING GROUP)
(Baollus anthracis), 6 2
(g)
meet r;go~ous DOT performance tests. Figure 10.13 illustrates the tri;le packaging that
genera ly is encountered_ when an infectious substance is transported. It consists of 3 pri·
marb~~ptacl~, wat~r-tight secondary packaging, and rigid outer packaging.
informatior~:qu1res shippers and carriers to mark the outer packaging wich the following
Proper shipping name includ’i h ‘ ep one num er
UN number ‘ ng t e name of the infectious substance
of proper packing
telephone number
of shipper
,ompnsing a primary receptacle, water-tight secondary packaging, and rigid outer packaging
1 24-hour emergency response telephone number
BIOHAZARD marking shown to the right on two opposing sides or
two ends other than the bottom of its packaging when it has a capacity
!rss than lO00 ga llons (3785 L) or on each side and each end when the
packaging has a capacity equal to or greater than 1000 gallons (3785 L).
affixed to packaging containing an infectious substance. The INFEC-
TIOUS SUBSTANCE label was previously illustrated in Figure 6.5.
DOT also requires shippers to afftx the applicable NON-FLA.i\.1MA-
BLE GAS or CLASS 9 labels to the packaging i11 addition to the INFECTIOUS SUBSTANCE
labels when the infectious substance is preserved in dry ice or nitrogen, respectively. When
50 milliliters or 50 grams of the infectious substance is to be transported by cargo_aircraft,
DOT requires them also to affix CARGO AIRCRAFT ONLY labels 10 the packagmg.
ter (Section 6, 10) or the Centers for Disease Control and Prevenn~n at (800) 232-0124 ~f
an incident involving the release of an infectious substance. This telephone number IS
printed on the INFECTIOUS SUBSTANCE label. . .
. DOT does not require carriers to placard the transport vehicle used to ship an mfec-
Special concern about potential exposure to anthrax was first rnised int~ Unite~_Stat~s
in 2001 just after the 9-1 l attacks, following the appearance of anthra:,· a en ;~ u~gs m
l>Ostal areas and throughout the Hart Sena re Office Building i.n Was mg~hn, . . . ;ven
~nthrax-tainted letters were mailed to U.S. senators an~ media outlets. ese mc1 ents
constituted the first major acts of biocerrorism in our nauon and caused the deaths of five
I
11
p . p ‘d ‘f d ti sole individual most likely responSible for them .1 pnme suspect, was I enu ie as 1e he committed suicide, a1 .
ings. As he was about to be arrested by the FBI, . . World War II b
and Allied scientists developed varieties of anthrax bacilh, alrhough neither side ever actu-
ally employed them as biological weapons. .
absorbed by the skin, ingested, and inhaled, giving rise to th ree forms of ant~rax infec-
tion: skin anthrax, intestinal anthrax, and inhalation anthrax. The mo5r potenually lethal
form of the disease is inhalation anthrax. . . .
enced by individuals having the common cold: high f~ve_rs, fangue, coughing, hard breath-
ing, and chest discomfort. As time progresses, the v1cnms of anth~ax poisonmg develop
severe respiratory distress, hemorrhage of the lungs, heavy convulsions., a.nd p~rspiration,
followed by the onset of shock. Anthrax victims may b’:’ treated by anttmtcrobtal therapy.
Untreated victims usually die 24 to 36 hours aher the first onset of symptoms.
Ricin is a toxin produced by the common castor plant, Ricin~s cot~~u.nis, the beans of
which also serve as a source of castor oil, the well-known laxauve. R1cm IS produced from
the waste generated when castor beans are processed.
fare jargon, it is known as Agent W. Its LD50 is estimated to be approximately 3 mg/kg.
Ricin can be inhaled as a mist or powder, swallowed as a pellet or dissolved in a liquid, or
injected into muscle. Its use is banned by chemical and biological weapons treaties.
have been documented:
in the thigh with an umbrella by an individual suspected of being a KGB agent. Two
days later, he died from cardiac arrest. An autopsy revealed the presence of a small 1
metal ball with four holes in his thigh.
In Paris, a similar platinum-iridium ball was removed from the back of a friend of the
journalist. The wax used to seal the holes in the ball had not yet melted. Chemical
analysis of the residue in the ball revealed the presence of ricin. The friend recalled
being jabbed with an umbrella on the Paris Metro.
In 1980, a Soviet citizen visiting Tyson Corners, Virginia, also was jabbed. He died en
route to the local hospital. A similar platinum-iridium ball was removed from the
deceased.
In 2003, London antiterrorism police and security service agents arrested seven ter-
rorists who were plotting to use ricin to kill and terrify the local population. The
details of their methods were never made public.
On several occasions in 2013, ricin was identified in envelopes addressed to certain
public officials, including the President, a U.S. Senator, the New York Mayor, and
judges in Mississippi and Washington.
of breath, chest tightness, and low blood pressure within 8 hours. When inhaled, ricin can
cause respiratory failure, and when ingested, it can cause organ dysfunction leading to
death. Inhalation of ricin can cause death 36 to 72 hours after the initial exposure. There
is no specific treatment for ricin exposure.
Substances
acute health effect, p. 354
antidote, p. 35
asphyxiant, p. 352
beryllium sensitization, p. 356
beryllosis (chronic beryllium
disease), p. 356
biological warfare agent
(germ warfare agent), p. 410
Bioterrorism Acts, p. 412
cancer, p. 398
carboxyhemoglobin, p. 365
carcinogen, p. 398
ceiling limit (C), p. 360
chronic bronchitis, p. 355
chronic health effect, p. 354
cilia, p. 362
coronary heart disease, p. 354
countable elongate mineral
Particle, p. 406
cyanosis, p. 372
diagnostic specimen, p. 414
dose, p. 355
emphysema, p. 355
essential element, p. 40
gas poisonous-by-inhalation
(poison gas), p. 347
hemoglobin, p. 365
hemotoxicant, p. 352
hepatotoxicant, p. 352
hyperbaric oxygen
therapy, p. 370
hypergolic, p. 382
immediately-dangerous-to-life-
and-health limit (IDLH), p. 360
infectious pathogen, p. 410
infectious substance, p. 413
ingestion, p. 349
inhalation, p. 349
initial isolation distance, p. 392
initial isolation zone, p. 392
initiation, p. 399
irritant, p. 353
lacrimator, p. 362
latent health effect, p. 354
lead-based paint, p. 402
lead poisoning, p. 402
(LCsol, p. 359
lethal dose, 50% kill (LD50), p. 359
Lethal London Smog Episode
(Great Smog), p. 377
local effect, p. 352
lung cancer, p. 405
mesothelioma, p. 405
mesothelium, p. 405
metabolism, p.
methemoglobin, p. 385
methemoglobinemia, p. 385
nephrotoxicant, p. 352
neurotoxicant, p. 352
nurse tank, p. 387
olfactory fatigue, p. 3
particulate matter, p . 361
permissible exposure limit
(PEL), p. 360
pleural mesothelioma, p. 405
poisonous material, p. 347
progression, p. 399
promotion, p . 399
protective–action zone, p. 397
pulse CO-Oxlmeter, p . 366
RCRA toxicity characteristic. p. 347
recommended exposure limit
(RELj, p. 360
select agent. P- 412
short-tenn exposure limit (STEL}, p. 360
short-tenn health effect. p. 354
skin absorption, P· 349
systemic effect, p . 352
threshold limit value (TLV), p .
toxic metal, p. 401
toxicology, p. 346
toxic substance (toxlcant; Poison)
I
reproductive toxicant. p . 351
respiratory toxicant. p . 352
soot p. 361
(toxicant po ison) • Any
subnance that neg a-
tively im pacts an ind i-
vidu al exposed to
relat ive ly sma ll concen-
trations, resulting in
death, incapacitation.
or the onset of d isease
or other forms of harm
of toxic substances that
adversely imp act the
health of humans and
other organ isms, as
well as the ways the
impact may be
counteracted
study of the adverse
effects that tox ic sub-
stances and d iseases
pose to human
populations
Associa te rhe physical and health hazard~ of rhe tox.ic substances nored i_n this cha .
rer with the informacion provided by rhe1~ hazard diamonds and GHS pictogram/
Idenrify rhe common means by which toxic substances may enter the body and
adversd}’ impact human health. .
Describe generally the ways in which a toxic substance may adversely affect one’s
Identify the factors that affect the degree of rox1c1ty resu tmg rom chemical
with the proper transfer of oxygen to the cell~ of the body.
Identify how on-dury firefighters may determ1~e whether they have been overex-
posed ro carbon monoxide and hydrogen cyamde.
Identify the chemical features of commercial products that produce su lfur dioxide,
hydrogen sulfide, and nitrogen oxides w_hen the products smolder or b~rn.
Identify the primary industries rhat are likely rouse anhyd~ous ammonta.
Identify the labels, markings, and placards that DOT requires on the packaging of
roxic substances and the transpo rt vehicles used for their shipment.
Identify the response actions to be executed w hen toxic substances are released from
their packaging into the environment.
Describe how emergency responders use DOT’s Emergency Response Guidebook to
establish the initial isolation and prorecti ve•action zones associated with large and
sma ll spills of a toxic substance .
intercbangeably.
manner in which how roxic substances adversely affect a living organism, the diseases
they may cause, the concentrations at which the onset of the adverse effects is noted, and
ways IO prevent or minimize them. The study of the adverse effects that toxic s ubstances
and d iseases have on human populations is called epidemiology.
responders. For example, carbon monoxide gas is produced by the assorted materials rha
burn or are otherwise wracked by rhe forces associated with fires. It is for this reason th31
stances m some detai l.
1 TOXIC SUBSTANCES AN 10, REGULATIONS D GOVERNMENT
t~~flo”‘\edge the spcc1f1c :v?y the term is defined a:e:~:ng. of a poiso n, it is important to
bne,[3tions. ce, env ironm enta l, and transporta.tion
rc&l
At110
f employment free of conditions or acti;t?yer~ to provide their employees with a
1
t din rhe workplace, OSHA a lso requires empl toxic substances are stored or
use xic substa nces is limited to no more t han certo~ers to .ensure that emp loyee exposure
:::~
ged over the 8-h.our workday. am maximum allowable concentrations
toxic substances m th.e workplace by the use of accident- rev I e_ntt the presence of
signs. These ra~s ~nd signs_ warn employees that they should~xer:7t1on rags and wor~ed
co reduce or e!tm1~ate _their exposure to toxic substances. Most b;e atequate precaution
·n 3ddition to the ,mpnnt of a skull and crossbones which h l art e word P?ISON
:ionJlly acknowledged symbol for poison. ‘ as ong served as the mterna•
tributors, an_d importers to mark co.ntamer labels with signa l words, GHS icto ;ams
and app~opnate haza~d and preca_ut1onary statements. The health hazards afe ide~tified
by markm? rhe. container labels w ith the skull-and-crossbones, health hazard, and excla•
mation pomt p1ctograms.
characteri stic• For
purposes of RCRA
regulations, the charac-
teristic of a waste that
contains one or more
of listed constituents at
concentrations equal to
or greater than the
threshold levels desig•
nated at 40 C.F.R.
§261 .24
inhalation (poiso n gas)
• For purposes of DOT
regulations, a gas at
68″F (20″0 or less and
exh1b.1ts certain charact~nsncs, one of which is toxicity. As noted at 40 C.F.R. §261.24, a
che?1_1cal analyst d_et~rmmes wheth.er a representative sample of a waste exhibits the RCRA
tox1c1ty characteristic by perform.mg a laboratory test designed to simulate the environ-
me nt wit~in a landfill. In practice, the a nalyst conducts certain specified test procedures
to determme whether one or more of the waste constituents listed at 40 C.F.R. S261.24
leaches from the sample at concentrations equa l to or greater than their relevant threshold
levels. Some representative waste constituents and their threshold levels are listed in
Table 10.1. Each listed substance adversely affects public health and the environment.
When the analyst determines that at least one constituent leaches from the sample at a
conce ntration equal to or exceeding the threshold le vel, the waste is said to exhibit the
RCRA toxicity characteristic.
(101.3 kPa) that is
known to be so toxic to
humans as to pose a
health hazard during
transportation; or in
the absence of ade-
quate data on human
toxicity, is presumed to
be toxic to humans
because when tested
on laboratory animals,
it has an LC50 of less
than 5000 mUm3
For purposes of DOT
other than a gas that is
known to be so toxic to
humans as to afford a
hazard to health during
transportation, or that
in the absence of ade-
quate data on human
toxicity, is presumed to
be toxic to humans
because of data
roxi~ substances: gases poisonous-by-inhalation (poison gases), poisonous materials, and inhalation toxicity
~nd mfectious substances. These toxic substances are designated as hazardous materials tests performed on ani-
m hazard classes 2.3, 6.1, and 6.2, respectively. All hazardous materials in hazard classes mals; or is an irritating
2 3 d 6 h I f h H d M · l material with proper-! an . I t at are designated by a 1, 2, 3, or 4 in co umn 7 o t e aza r ous l atena s tiessimilar to those of
ab le pose a health threat by inhalation . . . tear gas that causes
p]y With applicable labeling, marking, and placarding requirements. \Vhen preparmg the dally in confined spaces
348
EPA HAZARD OUS
WASTE NU MBER
0005
0018
0006
0019
00
00
0 008
0010
D0 11
0040
1 40C.F.R. §261.14.
Thresho ts Sub1ect to the RCRA Toxicity Character, st•
Contam1nan s 1(‘1
CONTAMINANT
I Cadm ium
1 Carbo n tetrachlor i de
l ,2-0 ichloroethane
l , 1-Dich loroethyl ene
M ercury
Silver
Tetrachloro e thylene
5.0
0 7
5 .0
5 .0
sion ” Poiso n _ Inhalation Hazard” a nd the releva nt haza rd zone m t he desc riptio n. DOT
also requires shippers ro affix the app licable POISON GAS o r PO ISO N IN HALATION
HAZARD la bels co the rele vant packaging.
HAZARD placards shown in Figure 6. 13 as fo llows:
HALATION HAZARD placa rds o n both sides an d both en ds of the transport vehicl e,
freight container, porta ble tank , uni t load device, or ra il ta nk ~a r use d fo r shipment of a
haza rdous material ha ving the haz.a rd code 2.3 o r 6. 1, respecti ve ly.
quantity of a substance that has bee n ass igned a haza rd cl ass numbe r 2 .3 .
when transporting any quant ity of a su bstance tha t has been ass igned a haza rd cl ass
nwnber 6. 1 and a haza rd zo ne classifica tio n as Zo ne A o r Zone B.
ha za rd class is 2.3 or 6. 1 by rail, DOT requ ires them to post PO ISON GAS or POI SO:-.l
IN HA LATIO N HAZA RD placards on white squ a res w ith bl ac k borde rs w hen the haza rd
zone fo r the haza rdo us ma teria l is Zone A.
nated 2.3 and 6. l in no nbulk packages in the same tra nspo rt vehicle, DOT a ll ows them
to pose POISO N GAS placa rds only o n the ve hicle.
carrie rs co display PO ISO N IN HALATIO N HAZ ARD placa rds on its packagi ng.
mg, DOT a lso requires th e shipper to mark the packagi ng on rwo o pposin g sides \\’lth
Wastes Exhibiting the EPA li ~epresentat,ve Haza rdous
tt,lZA ardous waste that exhibits the
;~~~~~;:~a racteristic fo r arsenic
~~
~
tY ch aracte ristic for me rcury
o,
~.’°;,3ci~
~,( ~~~:;dous waste, liquid, n.o.s. (arseni c),
9, PG Il l (E PA to J1.icity)
o,
does not pose a hea lt.h haza rd by mhalauo n, DOT may o bligate shippers and ca rri ers to
d’ close th at iri s po iso no us. T hey do so by entering ” Poiso n” o r ” Toxic”‘ in the ship-
p:~g desc ription, a ffi xin g_ POIS?N la bels to the pac ka ging, ma rkin g POISO N orTOXl C
00 the pac kag ing, a nd d1 splay mg POISO N placa rds on the tr ansport ve hicle when the
agg regate gross mass equ a ls or exceeds 1001 po unds (454 kg).
poses a hea lth ha za rd b y inhalati o n a nd meets the crit eri a fo r Z one A, DOT a lso
requires them to pr epa re a nd implement a secu rity p lan whose co mp o nents comp ly
with the requirements o f 4 9 C .F.R. S 172. 802, Motor carr ie rs a re a lso requi red to
obtai n a haza rd o us ma te ri a ls sa fety permit (Secti o n 6. 10 ) befo re tr a nspo rt ing an y o f
the foll owing:
an amount more th a n 1.08 po unds { 1 L) per pac kage
A material that poses a n inha lat io n he alth haza rd and mee ts the c riteri a fo r Z o ne B in
bulk packaging [ca paci ty grea ter than 11 9 gallons {4 60 L)l
A materi a l tha t poses an inhalatio n health haza rd and meets the criteria for Zone C
or Zo ne D in packagin g hav ing a ca pac ity equal to or greate r tha n 35 00 gallons
113,248 L)
exhibits the to xicity ch a rac terist ic in its shipping descriptio n b y using the term ” EPA
toxici ty” or the rel eva nt EPA hazardo us waste numbe r listed in Ta ble 10 .1. For ex am-
pl e, when shippe rs offe r for do mes ti c tr a nspo rt a ti o n a haza rd o us wast e that ex hibits
the tox icity charac te risti c ow ing to its a rsenic or mercury co nce ntratio n , DOT requires
1he was te ch aracte ri st ic to b e pa renthetically noted o n the acco mpa nying w aste mani-
fest by use of eithe r “EPA t oxicity” o r the EPA haza rdo us waste number o f the haza rd –
ous co nsti tue nt. So me re prese ntat ive exa mples a re cited in Ta ble 10.2 .
of a substance through
the mouth and into the
digestive sy stem
passage through the
epidermis into the
derm is or subcutaneous
tissue
1
:~ub –
bloodst rea m, bur we a re concern ed here w ith the three mea ns o f most conce rn to e mer- or dust into the
ge ncy responders: o ra l ingestion , skin a bsorption, a nd in hal ation . respir ato ry system
com~tS of tht
humand~~tm
Asubstancttakt11 oro1!ty
passes1hrou9h tht
mouth,into!N!tSOoha-
gus, and then 11to tht
stomachPartialdtgrada-
!IOn or comp’e1e chtn’l1cal
a1t,n1nonofthesub-
S”…an(‘!~ ll’ltnt
mouth and nomach. Mol-
ecuJes of the sut::s-.ance
tht-nmaypas.sttv’ough
thestomach walldiJ’Ktly
inrothebloodstrNo’n
Mcn~ly,~.
ab:sorpncn intotheblood·
st1Nmoccur;afterthe
m~ of thesub-
S”..J!’IC’!Ofitsdegradanon
produopas:s ll”ltothe
small ll”ltestu’le
totalofthe thE! m ita l
pr0Cf!S!eS tha t occu r in
th e body’s ce lls to
break down absorbed
Esophagus
Large intestine
As shown in f igure IO.I , oral ingestion refers to the swallowing of a substance through
the mo uth into the stomach and its subsequent movement throug h th e gastrointesti nal
tract. Once it is inges ted, components of the substance may pass through the intestinal
walls and into the circulatory system, where their molecules are further disseminated to
the organs and ti ss ues of th e body. The substance may undergo chemica l changes in the
cells of th ese organs and tissues. The combination of these chemical reactions is called
metabolism. Although th e indi vidual organs of th e digestive system metabolize ma n)’
substances, metabolic processes also occur within th e li ve r.
foods and ingested
i ubrunces
organ of the hwnan bod y. The skin of an average adult has an area of 21 square feet (2 m· ),
weighs 9 pounds (4 kg), and contains more than 11 mil es ( 18 km ) of blood vessels. The skin
he lps the body maintain a normal temperature. It also protec ts the internal o rgan s and pre-
vents direct contad berween them and foreign substances.
This is es pecia ll y tru e when rox ic substances directly contact the mu cous membran es and
th e eyes. Some foreign substanc es also pene1ra1e the epidermi s, the outermo st skin la re~
f!G tn is tt,e ,piderm1s, a thin surface membrane of dead cell s Before a substance may be absorbed into the
~ trean’I, it must first penetrate paSt the epidermis an.d t nter the derm is, a collection of ce lls that collectively ! as .i p0rous me dium From the derm1s, the substance is abso rbed Into th e bloodstream
al,sorbed into th e circu latory system and spread throughout th e bod y.
Inhalation is the rout e respo~sible for th e movement of gases, vapors, and fumes through
ihe compone~ts of the re spiratory sys~em. Eme rgency respond ers are most commonly
injured by this route of exposure. As illustrated in Figure 10.3, th e respiratory system
cons ists of the nasal pa ssageways, pharynx, larynx, trachea, bronchi, and lungs. When an
inhaled substa nce enter~ the lungs, it is exposed to blood vessels that cover an average
su rface area of approx imately 90 square yards (75 m2). Given this ma ssive area of
Trachea
bronchiole
11’1Clud.ng air-first pass through e1ther the mouth or nose, throu gh the pharynx, and into the trach ea (com-
rr.on~ called the w in dpipe) at the larynx. These inhaled substances then ent er either of two bronch i, each of
¼hich leads to a lung The ind 1Vl dual d1Vl sIons of each bronc hus are ca ll ed bronchioles.
me-ntocturrinqatth e
site o r •~ thatat~c
s.u bstanct in1t,a lly
cnntacttd
.tilme-nt occurTing
omywh~ in the body,
indud inq throughout
the e ntire body.
substance th at
decreasesth,functron
of the blood ‘s hemo-
globm and deprives the
tis.sl.Jes of oxygen
su bstance that causes
liver dama ge
su bstance that causes
kid~ dama ge
su bstanct tha t
adve ~ ly affecuth,
centtal nervous~em
• Any su bruinceca pa-
blto f infl am ing the
auw ays orotherwise
decreas ing lung
fu nct io n
• Anysubsu nce that
adv,rst lya ffectssuu al
fun ctio n and fe rtJlity in
adu lts, aswe ll asnor-
ma l development in
th eirothpr in g
displacesa ira nd,wh t n
inhaled,cau~uncon •
sciousness or dea th
exposure-, the subs r:ince is .1bsor~· /t~; bod )’, . c1 rcul arrd
to all che o cher org:lll5 .1nd nssue) o
10.3 !~~:R~ELY AFFECT HEALTH
Once a wxic s ubs1.1ncr h:is be<"n abso rbed in to th e bo dy, it ac ts in t he following &e~ .
It ma y C-J Ust’ ,mme
1 ff ct the si te or area o f contact , s uch as th e onset of
~:i;a e.d:ffect the body as a whole , an d thereby, cause an ail ment that is not lacalii
to on! s c or area. Thi s 15 3 systemic effect. H uman expos~re to ce rta in poisons, f~
e..’
and depri\•es rhe ti ssues of oxygen .
Hepatotoxicant., a substance th:it causes h:e r da ma ge
Nephrotoxicant, a subsc:ince that causes kidn ey damage
Neurotoxicant., 3 substance th at adve rsel y affects th e ce ntr al ne rvo us system (the
brain an d spina l co rd)
Respiratory toxicant, a subs tance tha t adve rsely affecrs th e nasa l passages, phar-
ynx, trachea, bronchi, and lungs
Reproductive toxicant, a substance tha c a.dve rsdy a ff ec~s sexual fu nction and
ferrilit}’ in ::idulrs, as well as develo pment in th71r _o ffsprmg . .
instance when an indivi du al ingests metha nol and eth ylen e glycol, neith er su bstance
causes iii effects direc dy; nonetheless, cheir metabo lites a re toxic substa nces and ma)”
cause che indi vid ual to expe rience ill effects, inclu d ing dea th.
One wa y that a gas or vapor adversely affects health is by indu cing unc o nsciousness when
inha led. T he gas or vapo r ch:1 1 affects th e hum a n bod y in this ma nn er is ca ll ed an
asphyxfant. Th e most common asphyxia nts a re carbon mo noxi de, ca rbon di ox ide, ni tro-
gen, metha ne, and the noble gases. Asphyx.iants may be toxi c o r nontoxic.
in hum ans:
greater 1han l disp laces the air within the lowe r reg ions o f a n enclos ure. An example of
such a gas is ca r bon dioxi de. A person who in ha les ca rbon dioxid e ca n lose con sc ious·
ness, because the body is denied sufficient oxygen. Wh en prov id ed fresh ai r or oxygen in
a timely fashion , conscious ness c:i n be rega ined, bu t if una ne nd ed , th e in di\·idu:il mu all1·
d ies from as ph yxia tion or experi ences long- term neur o logica l d amage .
used t_o establish 1he nega til’e impact that is likely 10 res ult fr o m in h a ling an :isphpiJnf.
T he _signs and sympcoms associate d wi1h brea thin g a reduce d -oxygen a tm o sphere \IW
previousl y noted in Sect ion 7. l.
, 7 210 ,dent1fy theadve1sehealtheHect§mostt,~ely tobeex
0
~;e
: ; / ~~~
;a~~.~;
:~~e 9:~0\:~ga;n ~~1~;1, ~t:,~:! on the mfo,mat,on 1n Table 7 2. any ind.
5u tis 1:i nces tha t chcrmca l_ly impa ir th e body’.s use o f oxygen ar e chemica l asph yxi ants. Fo;
e,:a rnp le, ca rbo_n monoxi de_ ca use~ unco n_scmusness as a chemica l asphyx.ia nt by reacting
h thf blood s hemog lob m . T hi s chemica l actio n preve nt s th e no rma l tra nsmissio n o f
1
f ~on~ ;~:nis ;:~~~-n JO . IO that a sho rt-t erm exposu re 10 certai n
,onsc 1ousn~ss is by hmd erm g th ~ ce ll s :ibili ty to utili ze oxyge n. T his occ ur s w hen an
indil’ idua l inhales hydrog~n cya md e. In Section IO. I ! -A, we s hall lea rn tha t the inhal a-
uon expasu~e rend ers a~ impo rtant enzy me inacti ve . Indi vidu als wh o have inha led hy –
drogen cya nid e ma y ha\c ::in ad equ:i~e oxyg.e~ _lev~ I in thei r bl ood, but th e inacti vity of
rhe enzy me prevent s.th em from effecnv_ely unlm ng It. Su bse qu ent ex pos ure 10 fres h air o r
oxygen ma )’ not re vive t_hem, a~d surn val may be possib le o nl y w hen t hey are pro mptl y
crot td wit h a n appro prrn1 c antidote.
The in h:i lation of a ga s or va po r ma y al so affect th e bod y as an irritant by injurin g th e
115,;ues that it contacts . W hen a low co ncentra tion of an irritant is inhal ed, th e res ult
is ofte n minor inflamn~a tion of the ti ss ues that line the respira1or y passa geways . T hi s
hap pen s wh en a rela tivel y sm a ll a mount o f ammonia vap o r is inhal ed . How ever,
inhal at io n o f an ele va1 ed con centra tion of th e same sub stance may cau se res piratory
fa il ure . Wheth er a s u bstan ce cau ses res pi rator y irritat ion or fai lur e is ofte n associated
wit h the degr ee to which it corr o des th e no se , pharyn x, la ryn x, trac hea , br o nc hi ,
and lungs .
exam pl e, may cau se 1he deve lopment o f a ra sh or other skin diso rder at th e s i1 e of co nt ac t
1n susceptibl e indi viduals, especi ally after pro lo nged or re peated contact.
tJn t is defin ed as any no nco rr os ive s ubstance, which , on imm edi a te , prolon ge d , or
repea ted co mac c wi1h li vin g ti ss ue, ind uces a local inflammator y react ion.
products holdin g skin a nd ey e irrita nt s un less the corrosio n o r hea lth hazard pictogram
also is affi xe d.
Th e ha rmful hea lth effec ls asso ci ated with ex pos ure to sub stan c<"S a re o ft en cl assi fied
as ac ut r, c hroni c , shon-lerm , o r latent. Wh en th ese s ub s rnnc es are consti t uent s of
commercial chemi ca l produ cts, th ese effects a re note d b y th e ma n u fac ture r o n la bels
~nd SDSs.
t hat counteracts the
ab llityofasubst ance t o
act as a poison
reve rsible inf lammato ry
effectatasiteupon
immed iate, prolonged,
or repeated co ntact
with 11 vingt issue
I
f’ffK1 • AAyd1$easeor
1mp1 1rmtnt whose
oruet and progrwion
occur rap idly after
,q,osureto•to:uc
ffldtN>al atilSU bt, th al
concentra tion
• Arrycf!Setieor 1mpalf•
ment whose onset and
progt’t’Ss.ionoccurslowly
overant.n~~
peood(monthsto
yN r\) afterexposureto
ato.ocmatNVl ata
~l conttntrat1on
• Any di~ disorder,
ordebilita tionassoci•
at~withthenormal
operation of the heart,
such as a myocardia l
infarct1 on (” heart
.nack ” J, congenita l
heart disease, ilndcon-
ge:sti-..! heartfa il ure
short duration caused
byexposure to a sub-
staince and fromwh1 ch
tKOVet)’OCCVl”S tap id ly
on ly after considerable
ti me has paned fo llow-
ing one or more initi al
uposurestoa
su bnanc e
• Hect is an lllJ UJ’}’, diS(‘J.St’. or death tha t de \’elo ps rapid[ )’ (in nun ui e-s
2
orda rs ) and qt’k? _co health effect is te-J ring of the eyes upo n exposu re to anini o/ ho~tt
~:n:~\~ju~ ~ers \linu:ill )’ immtdJat d y from 3 short -term expos ure. ia 1allt\
A chronic health effect is an in1uf)’: di sease, or deat h that de \·el: ps slowl y o1·er a
da ·s week s., yea rs. or deca des fo Uowmg an exposure or repea_ted exp os ure to a substa ft-t.,
,\l ~s~ types of coronary heart disease are cx:t mples of chrome heahh effects. Oct,
A short•term health effect 1s m:tnifested wh~n a~ injury or di sea se of rc-lati\’t[). sh
dur.ic io n and from which reco\’er)’ occurs rapidl y 1s ca~sed by exposure to a su bs t,1 flfl
Fo r example, wben an indi vidual is _temporarily asph yx1at: d from car~n _dioxide extlct.
sure but reco\lcrs when pro\lided with :imple oxygen or air, th e asphyxiation is call e~
short· termhealtheffect.
A latent health effect is man ifested_ wh~n an i~jury or disease caused by exposure to a
substance occu rs only after an cxtcnsJ1’e time period ha.s passed. For example, the Onstt of
certain cancerous and noncancerous di seases foll_owmg exposu re to asbestos fibers
aher an indi \lidual’s initial expo sure to the fibe rs.
The human bod y is a \/Cry complex and delicately balanced system. Its cells .:1ssirnilau
nutrients from foods, resi st biological .:1rtack, reproduce, and gen erate the substances tlut
Ul e body needs for ics survi”al. Ccllubr reactions arc responsible for li fe itself; but wh m
toxic substances .:1rc absorbed across cellula r membranes, _ they can upse_t 1_hese del icate!r
controlled biochemical processes. When the cells malfunction, the hose v1cum exprricncrs
impaired health, disea se, or death.
of foreign substances. One such mechanism in\lo!ves the specific actio ns of its organs. for
instance, che liver is particularly effective at conve rt ing many harmful substances into
harmless on es or into substances that can be rapid ly excre ted . As a result of these meta•
bolic changes, wxic substances may be modified in chemical structure, temporarilr stottd
in specific organs, and/or dirmly eliminated from the bodr.
protecting itself from invasion br toxic substances. Whether exposure to a tox ic substa nct
actuall y causes death, disease, or injury depend s on several factors, the most important of
which arc th e foll owing: th e quant ity of substance, the duration of exposure; the rate~r
which a substance is abso rbed into th e bloodstream; the age, sex, ethnicity, and heahhof
the affl icted person; and indi \li dual sensiti \li ties. A parent’s exposure to toxic substanctS
ma y al so affect the hea hh of hi s or her children, including unborn children. We examir.r
each fact or ind ependentl y.
Although all sub stances have the potential to be toxic, we are concerned with those sub-
stances that cause an ad verse impact on an organism in relatively small amounts. Th
J~11.:, unt t,srnnces are so toxic tha t exposur t’ to ;h e . ~ r bod y weight 1s ca ll ed the dose.
5onir d051r1d111m bo t11 /m 11m, th e ca usa tive a ge ne :~•~tt ~ose is le1_hal. For instance, the
10′
~trriulll w patent that just I gram can cau se th e d~~i:;• JS a smgle cell that rel~a s~s
Jc£ A sprcific subscance impacts 1he body as a funcii o f . d .
hO’ u h alco hol to ach ie”e a blood alcohol concentration of ~-
Whcn an mdmdual dnnk s
J1s~:l~ed IO ac hic”e _blood alcohol concemraci~~ ~1;1l~ b;c when sufficient _alcohol is
~::xicaced. (One deciliter (dl ) is 100 milliliters, or one- tenth ~1~1i’i~;.rrson JS patentl y
i\S ll genera l palicy, ~rcquenc expos~res to a toxic substance cause ind ividuals ro cxpe ri-
rnce 1!1 effects. Consider ihe approximatel y 4000 substances that ha\lc been id entifi ed as
eonsiituents of tobacco smoke, about 200 of which are wxic . Exposure co 1hem causes
mon)’ tob;icco smokers _to develop emphysema , chronic bronchitis, and/or cancers of th e
lung>, mouth, la rynx, ki dney, or bladder; )’e c_, the exposu re appears to impact ocher smok-
rrs a; if they were nonsmokers. If 200 toxic substances in tobacco smoke cause health
probkins, why do son_1c smok.crs ~ppea r to be shielded from contracting these diseases?
Jnd manifcscanon of a specific d1sc~sc occur stepwise. Alt hough manr random facto rs
can accele rate or delay the_ progress ion ~f these steps, the possibi li ty cha, ill effects will
r~ult from exposure to toxic substances increases when individuals are exposed mori:- and
more frequentlr to them.
centration of a cox1c substance over tht’ same lengt h of time. Some individuals arc more
capable th an ot_hers of tolcraci~g_toxic substances in their environment. Some even appear
10 adapt to 1hc1r presence. lnd1v1dua ls respond co toxic subs1anccs 01·er a given length of
time in rhe following ways:
others experience the same effcc1s only aftt> r they ha”c been repeatedlr exposed to the
substance in the aggregate for a longer period of time.
concentration of a substa nce, they may not experience chc same effects on subsequent
exposure co the same concentration of the same substance.
concentration of a substance may be unable to colcrati:- a long-term exposu re to a
smaller co ncentration of the same substance. These individuals require chis longer
prriod of exposu re to reac h th eir body burden, chat is, the concentration that causes
them co expe rience ill effects.
INTO THE BLOODSTR EAM
ti id ent immediate!)’. Inhaling a lethal concent rat ion of chlorine or carbon monoxide, for
mmple, causes dcJth within seconds or minut es, whereas inha ling a lethal concentration
of hrdrogen chloride or nitrogen dioxid e may result in death hours or da1·s later. These
observations demonstrat e ch at the manifestation of an effec t caused by exposure to :i
toxic substance depends not only on the conccnu aci on to which an individual is exposed
but on the race of ch c mechanism chat causes th e impairment or death.
we1ghtadm inls-tered
directly to and
absorbed by an
organism
thelungsbecome irre-
versibtyd is-tended,
decreasingtheeHi•
dencyofrespiration
and causing breathless•
nessandwhee zy
cough ing
bronch i ofthelungs
become permanently
inflamed.causing
breathlessness and
chronic cough ing
subsuntial proportion
oftxpowd peop/e or
anim.i lJtodevelopan
all erg icrHctionafter
repeatM uposures
Whc-n a toxic subsra~cc 15 /rt: absorbrd into the blood stream. When ingested Us1
subsr-Jncr must usu~~ rC’am. When exposC’d to skin, 1he subs1ance muse first Nss inro
::abrorbN mro the ~I . bsorbtd t1110 ihe bl oodsiream.
the dernus. where Lt 1s th C’n a d fo r thr absorption of :1 subs1.:ince into the bl
1
:C’;::~s to occur _provides a w~ndow _of opponunil)•: ·
ing which emergencr-mrd1ct lfipt;:d measures. g, o,
implrmC”nl other appropru te irs
OF INDIVIDUALS . . .
ThC’ d~rtt to al st.m of health. Young children and th e elderl y typJCall y are lllor,
C’thmc1r:r, or ge ner ‘ddk-a C’d indi ,·iduals to the effects of exposure _to t~xic substances.
suscC’pnb!e th30 i:1″1
l g I erable because their average bod y weight rs rela1ively lo
aocl th~1r =~e ro !onir:ict ing diseases and ~x~ nencmg othe r hea lrh-relatC’d compl 1C;1.
;:; : ‘~~wborn infu nrs :are at th e highes t nsk, becau_se ~h ey mu sr rel y heavil y on the
imm~nC’ factors acquired from cheir mothers before ,heir bm_h. _ . .
diseases For uamp!e, ei•rn th ough the physiology of th e c1rculat~ry system 1s the sa me in
bO!h m~n and womrn, wome n are more prone co contract certain typrs o f hrart disrase
tha t arr fundamrnrally different from the types contra.cted by men. Ano ther example is
rvident whrn exa mining the diseasrs con rracrrd by whit e and bl ac k peop_le. E1·r n though
thr composition of chr blood 1s the same i_n all races, bl~ck people of Af~1can descrm are
mo rr prone to devrloping sickle-cr ll anemia than ~re ~vh1te ~eople. Wh y IS o ne sex or one
ethnic group more prone to be stric ken_ with cert_ain diseases. ~ h ~~ugh the answer to tlus
question has nor been identified, genetics most likely p_lays a significant. ro le.
people to be susceptible to the effects resulting from _exposure to toxic subst~nces. This
~ nsitil’ity is pamcularly evident in indiv idual s suffering from hea rt a~d respi rator}’ ail•
ments. Indi viduals suffering from heart ailments , fo r example, ma y be incapable of roler•
acing exposure to low concenuation s of ground-le1•el ozon e, but _healthy peop le ma)
experience no srmp1oms at all when exposed to th e sa me concentration.
eral rule, nonsmo kers can tolerat e an exposure 10 toxic substanc es better than smohrs
because che immune srsrems of smokers ha l’e been compromised. Smoking inc reases the-
potential that particulate matter will adhere to lung ti ss ue and delay th e rate of remo1eal
of hai.ard ous sub stances. Th is may expla in why smoke rs are more like ly to suffer from
asbestos – or radon-induced cancers than nonsmokers for the same expo sure.
~~!um duru and Sensitizers are a unique group of substan ces that cause on ly cer1ai11 expos<.'d indi viduals
beryllosis {thronic opmenr of a more se rious disease. For instance, exposure to 1he dust s and metal fum es of
be,yllium disene) • Th, beryllium can promote th e allergic reaction ca lled beryllium sensitization, whose S)’mP-
::::!7z9~i;at:a,. toms !nclude coughing, short ness of breath , fatigue, fever, and night sweats. Con rracring
ring of tht lung tissu, ~ rrll 1~m Rnsiri~ uon is the fi m m p towa rd s de\·eloping bery/losis, or chron ic beryl·
following th, inhal•- li um disease, a painful sca rring of lung ti ssue for whic h there is no cure.
t1on of t>,ryHi um dusts To explain why only cen::iin people adversely respo nd ro sensitizers is nm str.iighc for·
and fumes ward. The explana tion may ha Ye som<.'th ing to do with one's inherired trait s; ih:11 is, our
356 Chapter 10 Chem istry of So me Tox ic Substances
6,nes n1r:1non of .1 scns1 11 zer where::is _ot her ind1v1duals experience ill effects from expo-
conc:0 the s:unc or a lcs_ser concentration.
,,;rtlltrtc fr,J aa l agencies regul::itc exposure to sensi tize rs:
CPSC regulates exposure ro th e sensitizers li strd ac 16 C.F. R. §1500.13 when 1hey
Jr I FDA regubr es expos ure to foods contaming peanuts, uee nuts, eggs, milk , shrll-
fis ~;1
; 0 ~r greater than IO pamper mi~li_on,
nufacturers, d1 s1r1burors, an d importers of res piratory and skin se nsitize rs are re –
~pectivc contamer labcls.
_5.F ADVERSE HEALTH IMPACTS ON A DEVELOPING FETUS
h dei·eloping fetus from exposure to a toxic substance. The placenta’s primary func rion
0
reienting the tox!c sub~tance from passmg into the mother’s womb.
·ic substances into the wo mb. Some substances appear to move unhindered through the
~:cenca an d enter the fetu s’s blood, after which they may cause harm by negativel y influ •
The adverse hea lth effects face d by a develo ping fetus are Yividly ev ident when a preg-
for example, puts her unborn child ::i t ris k because the mother is likely to expe rience pre-
rnarurc labor, miscarriage, and stillbirth. Babies who survive their mother’s exposure a re
nol on l)’ born unde1·elope d, bu t they m::iy be addicted and requi re treatment for with•
drawal from the drug . A woma n’s use of ill ega l dru gs during her pregnancy may al so
wl.’3kcn th e placenta and allow ot her toxic substance-s to cross mo re readily into her womb.
h:r pregnancy, Inha ling t he toxic substa nces in tobacco smoke nearl y dou bles her risk of
gi~ing birth to a n undevelo ped baby and increases he r risk of a prererm de li\’ery. Th e risk
10 ~ bab)”s hea lth is ex tended beyo nd the nine mo nt hs during whic h the fetus is carried in
1cs mother’s womb. When a woman smokes du ring he r pregnancy, her newborn chi ld is
likely 10 experie nce more illnesses and disa bilities compared 10 a child that is born to a
nonsmo king mother. Beca use i1s lun gs are often unde1•e loped, the newborn chi ld may
exwience difficulty in breathi ng. Later in life, the child is likely 10 experience disabilities
such as mental re tardation and learning problems.
kl rxposed during her pregnancy to ethanol (Section 13.2-E), Bisphe nol-A (Section 13.2-0),
rthylene glrco l alkyl ethers (Section 13.3-E), and die rhylh exyl phthalare (Section 13.7-8).
Toxico logi sts ha\’C dev ise d procedures for measuring the concentratio n of a su~stance
1h.i1 causes an o rganis m to experie nce inj ury, disease, or dea th. These procedures invol ve
exposi ng groups of laborato ry anima ls 10 concentra tions of a substance, obse rving the
dfec ti caused by 1he exposure, and extrapolating the resul1s to humans. Whe n ex po~rd to
SJme way. hen different anima ls res pond differently to an exposure. Consequently, these
PJranmers ma y have o nl r limited releva nce.
subst:i.nces. To do so. c-mplo ye rs consider thr:e releva nt 7xposu~e hm1ts: t he short to~ ,c
exposure lml\t, chc permi ss ible ex pos ure hm1t, a nd the 11nmed 1ate ly•d ~ngc rous-t~terrn
and-hcahh level. f irefighters ma y also use these lumt s to evalua te the impac t Posc~i ft.
mhalmg a known conccntr.rn on of an airborne wxic s ubs t:m cc. ~-
IMMED IATELY-
TOXIC SU8STANCE (PP M) EXPOSUR E UM1T EX POS URE LI MI T ‘ AN D-H EA LTH LIMIT (PPM)
(OSHA)
JS ppm (27 mg.lm 1)
(NI OSH )
35ppm(40mg/m1)
Ceil in g 200 ppm (229 mg/m 1)
(N1 0S H)
Ceiling 0.S ppm(14Smg/ml),
15m in (Nl OSH)
{05 HAJNIO SH J
{OSHAJNIOS H)
I absorption {O SHA} sk i n absor pt ,on
Hydrogen sulf ide 712 Ceilin g 20 ppm (2 8.4 mg/ml) 100 ! SO ppm/1 O•m in maximum peak
lO•min maumum peak (NIOSH )
Nitrogen d ioxide 115 Ceil in g 5ppm(9mgtm 3) 1 ppm(l .8 mgJm 3) 20
Phosgene 0. 1 ppm {0.2 mgtm 3) (OS HA)
CeJh ng O 2 ppm (0 8 mgtml),
lS·minexposure(N IOS H)
Su lfurd~
2520 5 ppm (13 mgtm 3)( 0S HA) S pp m(13mglm1) 100
Th letha l d ose, 50% kill , o r LD so , is the a moum f b f; bo rato r )’ anima ls co whic h th r s ub sta nc . 0 J s~ _5(a ncr th a t kill s half of a group
0 nt:. The LD;o 1s ex presse d in milli grams o f a:~ :n~s t:~~lSCe~ed during a p reestabli shcd
11
1111 kilogra ms (mg/kg ). When a substan ce aff su ~t.a nce per bo dy mass o f the
The leth al do~e o f a su_bstance to humans is calcula ted usi n h l.D
I
kchal dose is th e prod uc t o f the LD so a nd the mass: g mass of w kil ograms, th e
(LD sol • The doseof a
su bn ancethat hletha l
to SO¾ of a group of
l abora tory ani mals
tested dur in g a
spe ci f iedt, me
6ig,~;d~~~•~~~:~::1~ ~:~~l!m~ as a technical bas,s to estJmate
1
1
:~~~-pound emergency res ponder absorbs 57 g 01 more of phenol through the ~n. the exposure is likely
The leth al co nce ntratio n , SO % kill , or LC so, is th e conc emrat io n of a substa nce tha t kills
ha lf of a _gro up _of labo ra1orr anii:n::i.ls 10 w hich the s ub stanc e is admin istered during a
precstabh shed tim e. A LCso IS t ypica ll y ex pressed in pa rt s per milli o n (ppm ) by vo lume .
These measu rem e m s are use d in d iffe rem di sc ip lines for a va riety of purposes. DOT u ses
LCso v:ilues to ch a racteri ze ma te rials in ha zard classes 2. 3 and 6. 1 10 esta b li sh th e ha z-
ard zo ne fo r a s ubsta nce t ha t poses a hea lt h haza rd by inha la ti on. \Y/e rev iew this proce ss
inS<:c tion 10.8.
sureme nt obtained from anim al stud ies. For a n a,·erage perso n ha vin g a mass of w kil o-
grams, the leth al con centrat ion is th e pro duct of th e LC50 and th e mass :
The t hres h o ld li m it va lu e , o r TLV, is the uppe r li mi t of a co ncentra tion co wh ic h an a vera ge
healt hy person ca n be repea tedl y expose d on a n all-d ay, eve ryda y basis wit hout s uffe rin g
adi·erse health effec ts. Th e TLV fo r a irborn e gaseous sub stances is us ua ll y expressed in pa rts
prr millio n. The TLV fo r ai rborne fumes, mists , and particulates is e xpressed in m illi gr a ms
prr cubic me1 c r (m g! m 3). The TLV is 1he level o f ex posure a t w hich th e pro bability of the
occu rrence of adv e rse health effects is deemed negl igible. Th ese values ar e es ta bl ished by 1he
America n Co nferen ce of Government al Jndusuial Hygie nists {AC GIH ), w hich rec ommends
them to OSH A for it s con side ration of th e ad,•erse impact o n a worker’s long- term hea lth.
50% kill (LCsol • The
concentration ofa sub-
stan ce t hatis let halto
so •;. ofa groupoflab-
oratoryani mal s t ested
during a specif ied t ime
ACG l H for exposure t o
ana irbomeconce ntra •
ti onof a substa nceto
w hich an ave rage
w orkerm ayb erepeat-
ed \y e)(posed , dayaher
day,without exp erienc-
ingadver se h ealt h
effects
lb, Tlnnhold Lmrrt \’,;1/r1t$ 111,,/ B,ologi(,1 / £-.:posure Indu~s, C,ncmn,u i, Ohio (20 12).
limit(PE U• Forp ur-
po5flof OSHA
rt91.1 l.1t,on1.thtt,mt-
wt,gh1i!d,1vtrage
thmho ldhm itvalutof
1ubst.1nctstowhlch
wor!o:.tnc1,n betxpo1td
continuously during an
8-hourwor!o:.sh1ftw,th-
outsufftrmg i!l tfftcts
concentr,1tionofa
subrulnct lnaworklng
environment that
shouldn-rbt
,xcffdi!dfor any
dur,111on
short-tfrmex posu,.
n,ll(f to which worke11
C.illnbfe:o:pos.-dcontinu•
ous/yfor,15hortper10d
oft1m,withoutsuffer-
ing initat10n.chron1C.
or irr-niblttiUUf
dam,19e,ornarcosj1of
sufficifntdt9rttto
inat.1se the likelihood
of,1ccid.-nt.1l injury,
1mp,1ir self-rtK1Jt,or
n,,1teri,1llyri!duct work
,fficiel’ICY, and provided
th.ithedailythrfihold
!im1tvalue.nmt-
we1ghtedavuageisnot
v:cttdtd
lmmtdiatt ly-d angu-
ous-to-li f…and-h u lth
a.nysubnancethat
po5ean immediate
thrf,1 tto l,ff,G1U lfiiln
1rrtvfflibltordflayi!d
advernohea!thefftct.or
,nterler~wrthan !nd l•
vidual”sabnitytoesc.ape
during,13(}.m inute
limit(IIE U • ThtO
· . e lim it, or PEL 1s 1he rime-we1ght~d average level of c-xpos
a cox1c sub stancc- tor workweek in conformance wit h relevant OSHA regu lations tu
workday or_~ 40-~ou or C for some substances is al~o recommended by Nlo·s
~S~- :~s” ~~~~:;e:;;;:r~c:ng 111 effects. When ~orkers ~re c-xp_osed to a co:c:;;~Y
tion o7: substance that exceeds its ceiling lima. their safe ty is considered to be 11111111111:
nem danger.
The short-term exposure limit, or STEL. is the max~mum c~ncentrat10~ of a substanct 10
which workers may be exposc-d continuo~sly for a time pwod of 5 mm_u~es without suf.
fering irritation, chronic or irre\·ersibl e msue damage, or _narcos1s suff1c1em ro incre,1~
the risk of accidental Jn]Uf}’. impair self-rescue, or mate~1ally reduce work-related tffi.
ciency. The STEL should not be exceeded more than four nm~~ throughout a working~)’
with at least 60 minutes bern·een ex posures. STELs for spec1f1c subs1ances are published
when toxicological effects from relati\·ely elev,ued short-term ex~sures to ei ther huma ns
or animals have been reponed. They are established by NIOSH.·
The immediately-dangerous-to-life-and -health limit, or IDLH , 1s the airborne concem~-
tion of any substance that poses an in_1mcdi~te ~h_reat t.o !if~•-causes irreversi~lc or delayed
adverse health effects, or interferes with an md1 \’idual s ability to escape durmg a 15-rnm-
ute period from a dangerou s atmosphere. These values arc estab lis hed by NIOSH.
f\lOS H also recommends to OSHA the concentrations of certain subs1:1nccs that a focd –
ity may use as guidelines for protecting its workers against an injurious outcome. Each
concentration is called a recommended ex posure limit, or REL They account for th:
safety of an employee during his or ha tenure at a facility when the y are used in combi-
nation wi th recommended protecm·e equipment such as gogg les and masks, posted signs
that warn of potenual dangers from e)(posurc, monitoring of exposure lc\’els, and ocher
prudent safety measures.
cent ration for a JO-hour workday.
At 16 C.F.R. S1500.3(c)(I) , CPSC defin es a consumer product as wx1c if it can product
pe rsona l injury or illness 10 humans when it is inhaled, swall owed, or absorbed throuj;h
the skin . Certain tests are conducted on anima ls 10 det ermin e wh ether a product can
cause immediate injury. CPSC also regards a product as wxic if it ca n cause long-1enn
chronic effects like cancer, birth defects, or neurotoxicity.
for adoption as a per- ~ itt 7wdt 10 a,,,,uc.i/ H~::.mls. U.S. DrpJrtn1rnt of HrJlrh and Hum.rn Serv1c ts Public 1-kJlth k n·'”‘
m1n1ble ex.posure li m,t d t7’ or Disuw- Control Jnd Pm rrmon. \l:’Jshmg1on, DC 12010) PELI Hr c~mponrnr:s oi 1hr mr.J
· S 926.H, Ap~nd,x A: Jnd for mmumr wor h ri JI 29 C. F.R. §1915.10 00, Ta~lr Z
‘°~iplics with an}’ of the ow mg co~d111ons:
IJborator)’ whne rals, each weighi_ng between 200 an d 300 gram s, at a single dose of
-o mg/ks or less when orally adm1mstered; or
tt produces de:ith wi th1 n 14 d~ys _in half or more than half of a group of 10 or more
\.lbor,itof}’ white r~ts, eac h weighing between 200 and 300 grams, when inhal ed con•
ously for a penod of 1 hour or less at an a1mos pheric concent ration of 100 parts
dust, prO\’ided su~h conce ntration IS likely to be encountered by humans wh en th e
,ubsta nc e is used m _an~· reasonabl)’ foreseeable manner; or
It produces death w1thm 14 da ys in half or more than half of a grou p of JO or more
rabhitS rested m a_ dosage of 20~ mg/kg of body weight, when administered by con·
t1nuous contact with the bare skm for 24 hours or less
In Chapter 6, it was n?te~ that DOT assigns one of four hazard zones to gases and one of
t\\’O hJza rd zones lo liquids that pose a _health hazard by inhala tion of their vapors. DOT
dmrniin es the ha zard zones fo r all tox ic gases and liqui ds by reference to their LC_’iQS as
follo ws:
th e gas or liquid.
parts per million, DOT assigns Zone B to the gas or liquid.
When the LCso is greater tha n 1000 parts per milli on but equal to or less than 3000
pamper mi ll ion, DOT assigns Zone C to the gas.
When th e LCso is greater than 3000 parts pe r million but equal to or less th an 5000
pJrts per million, DOT :issign s Zone D co the gas.
1l)’ Of a gi\·en gas or liquid. Although exposure to a gas with a Zone A des ignation is likely ro
lie immediately dangerou s to life, exposu re to a gas with a Zone D designation could be
momentarily tolerable for some indi\· iduals. This disrincrio n notv:iths1anding, the warning to
emergency responders at tr.:ansportarion mishaps involving the spill or leak of a gas or liquid
to which any of the four haz.1rd zones has bttn assigned is to don fully-encapsulating protec-
rnedothing and use se lf-contained breathing apparatus before executing a response action.
The fire scene is usually an extremely dangerous environment. Even if all its physica l hazards
coul d be elim inated, 1hc atmosp here would s1ill be filled with smoke, dust, toxic gases, and
other hazardous substances. The potential for illness and death at a fire scene most often
results when individuals arc exposed to the smoke and mxic ga ses produced during 1he fi re.
donofpart iclesof
carbon and other solids
andl iquidsofincom-
p!etecombust ion
partku la! t matter
• Sol idandl iquidpar-
ticle1suspendedlnthe
atmosphere
pmion of finely divided particulate matter co mposed of carbon par1ides whose diamc-
1m range from 0.0 I to 10 micrometers. During most fires, carbon is initially produced as
a product of incomp lete combustion as microscopic par1icl es, which rapidly agglomerat e ::~t ;,r;:rt~~ii’:t;era –
mco blac k particulates coll ectively referred to as soot. When they are inhaled, 1he larger matter generated
particula tes in smoke arc usually filtered in the nasal passageways, but the smaller o~es dur ing the incomplete
can be drawn into the bronchi and lungs. When soot is produced during the combusuon combustion of carbona –
of petroleum products, ii is primarily carbon black (Sectio n 7.6-F). ceous materials
st.nctthatause, the
eyes to involuntarily
tur,ndclose
JKtionssuchu tho5e
alongtMe.rteriorof
the resp iratory tract
thatmove inunisonto
htlppreventthepas-
s.ageofftu id5andfine
partirulate matter into
thtlung5
EPA di\idrs partic~ner havmg paroclc diamrtcrs equal to or ltss than 2; · teb1
~heers/~1~r~1 paruclts pose rhc greater ri_sk co one’s heal1h, brca~sc’;h~O
~=~e of
t[ lungs, they obstruct their proper funcuon mg and conmbutc to the 0 ftsct1~
p The long-rum inhalation of parcic~latC’ rnan~ r h~s ~c~n lmked wn~ an increaSt I
cardio\·ascubr and pulmonary diseases m susccpablc 1~d1v1duals. In particular, the in~o
lation of p3rncul:ite marcer hastens the deaths of th e sick and eldc.rly b~ contributing~
the premature onset of heart attacks, strokes, and _emp hysema. le ts logical 10 infer l/ut
soot parricul.ues can also comributc 10 the mcept!on of adverse healt h effects in t~
fi fi hrers who inhale soot regularl y while combati ng fi res. .
ire lgure J0.4 demonstrates chac the produccion of smoke 1~ directly linked with th(
rion products like ca rbon monoxide and hydrogen c~am?e often represe nt a greater Jui.
ard to life and a more serio us hindrance co firefighting ef~orts 1han the fire it~lf
individuals who are unable to escape from a fi re sce ne often di e from smo ke inhalario~
e\·cn beforethefire reaches th em.
source. Ocher sources include the flyash in stack emis~io_ns fro~ ~ossi l-fucl-fired po::
plants and industrial manufacturing plants an d 1he ra1lp1pc emiss ions from hea vy-duty
\·ehiclesand m.achiner}’-
When che eyes are exposed 10 che irritant compo?e~cs _of sm~ ke, they sting and in volun-
tarily tear and close due to the presence of certain 1rntants m smoke ca lled la crlmators
(Section 13.12). Their \’apors act on the sensi ti\·e nerve end ings of the muco us membranr
of the eyes and cause an excessive, involuntary unleashing of :a flood of tears . Two exam-
ples of lacrima1ors found in wood smo ke arc fo rmald ehyde and ac rol ci n. In the most
severe instances, exposure to 1hcm causes u ro \’is ibiliry, especially when smo ke canllOI
readily esca pe from a burning structure.
The most immediate ill effect caused by inhaling smok e is hear dam age to the ti ssues of
che respiratory tract. This damage is usually limited to [he tiss ues of 1he mouth and upptt
ch roat, bur in the most egregious instances, it can cause pulmonary edema of the lungs
{Section 7.3- B).
laces on the surfaces of the respiratory pass:agcs. The trac hea and bronchi arc lined with
[iny hairl ike projections called cifla th at act in a wavelik e manner to force deposi ted p~r-
ticlcs upward towards chc esophagus, where they generally are swa ll owed or deposited in
phlegm. lnhal cd smo ke, however, greatly impai rs the abi lity of th e cil ia to cffccti\·dt·
remove ca rbon particulates from the respiratory passages. Ci lia that ha ve been dam agtd
br hear cause an indi vid ual co choke, gag, and experience labored brea th ing. Th en, OX)’•
gen levels in the blood drop to serio usly low le\·el s, and fatalities arc more lik ely.
t~c form of cancer characterized by the emergence of ma lignant tumors on the lungs. lndi-
\·1duals who regularly inhale particulate matter :arc 8% more likely to develop lung canctr
r~an noncxposcd ind ividuals. The onset of lung cance r is typica ll y cx:accr bated by tht
simultaneous exposu re to certain compounds 1hat arc adsorbed on smoke particulates.
: .:c:~i:~;~~~:~ ;~~lt
~c the ca ncer-causi ng polynuclear aromatic hyd roca rbons, which
OF CARBON PARTICULATES
inha le smoke, i1 isn’t just chc carbon paniculatcs that are drawn into our bronchi and lungs.
cafbonmono;,ude.and
wattrvapora re typ,ull1
produ
rnisit two processes int roduced earlier: incom pl ete and complete combus tion. The ir
natu re is schema tica ll y shown in Figure 10.5. When carbon-ric h materials igni te and
fOSSil fuels snowr on tN’ ltit. proJucts ca rbon
e
burn, th e carbon unite s with oxygen co form car~n monoxide or carbon dioxide, both of
wh ic h are colorless, odorless gases. Th ei r formauon occurs as follo ws:
or oxygen, or access to cithrr air or oxygen. ts lnmted; th at 1s, mcompletc- combumon
m fuel-rich firi=-s . When fo ssil fuels bum, incomplete combusuon p~occsses produce C-Jrbon
monoxide and soot. Jn ordin:i ry c1rcumitancts, the_ carbon m~n?x1de produced.dunng 111.
complete combuscion ent ers the atmosphere, where 1t slowly ox1d1zes to carbon dioxi de.
of air or oxygen is a\’ailable. The compl ete combusnon of fossil fuels produces car bon
diox ide. Complete combustio n occurs when the flow o f fuel and air can be regulated, .s
m a normal heatmg sys1em.
rnally all fi re sce nes, se\’era l other gaswus co~b~stion _produc1s_ “‘? also be present. They
include hydrogen cyanide, ammonia, sulfu r.dmx1de, nitroge n d1ox1~e, hydrogen chlonde,
and acrolein. Wheth(‘r one or more of them IS actually prese nt at a g1\’C’ n fire sce ne deprnds
on the chem ical n.:uure of the material that burns, smolde rs, or undergoes thrrmal d«om-
pos ition. We sh,1 11 derermine how they are produced in lat er sections of thi s chapt er.
PARTICULATE MATTER
cer (other than windblown dust or soils ) in th e ambient air as :1 criteria air pollutant (X’C·
tion 1.3-A). For pamcles having a diameter of 2.5 micrometers or less (PM- 2.5 ), EPA set tlit
primary and secondary daily sta nd ards at 35 µg.lm1 of air, averaged over 3 yea rs. It al soS(l
t.he prinury and secondary national ambi ent air-quality annual sta ndard s at 15 µ!ifm 1 anJ
12 µg.lm 3 of air, each averaged ove r 3 yea rs, respect i\·e ly. For particles ha \’i ng a diJ~ltr
ranging b<.-tween 2.5 and 10 micrometers (PM-IO ), EPA set the primary and seconda r)'
national air-qua lity daily and annua l standards at 150 µg.!m 3 of ai r, averaged ove r J yea ri.
Ca rbon monoxide is an odorl ess, colorle ss, taste less, and nonirritat ing gas at ordinl!’}’
room conditions. It is also th e major poison most likely co be enco un te red by emergtng’
responders. Some othrr importan t ph}•sica! properties are provi ded in Table I0.4.
. As a commercial chemical product, ca rbon monox ide is l.irgely used by th e chemical
mdu stry for th e production and manufacture o f other subst ances like methan ol (Ste·
tion 13.2-~ ). Because it is a component of water gas {Section 7. 2-C), carbon monox:idt~
produced m large vo lumes b)’ the chemical mdustry during the manufactu re of h>·drogen
– 341 . F{-20 7′ O – —–3 14″FH 92 ‘ CJ – ——-081
11 28 ‘ f {609’ Q
iheir corrrsponding metals. F?r example, the fo llowing equation shows tha t metalli c cop-
rer is produced by the redurnon of copper(II ) oxide:
Copp,.:r,ll \0,1 ,J,c C.11bonn1000\IJ., CoPf'(r Cirb,.,nd,o , ,J<
The isolation of carbon monoxide from water gas serves as the primaf)’ means by which
mbon mono xi de is produced for commercial use.
lnh.tla tion toxiciry is 1he primaf}’ risk associated with expos ure to carbon monoxide. To
undmtand why this gas is poisonous, we must first ex amin e the ch emistf}’ that occurs
du1ing respira1ion.
the bloods tream. The oxygen is carried throughout the body by a complex component of
1he blood called hemoglob in. Each red blood ce ll comains about 300 million hemoglob in
molecules, each of which contains iron in the fo rm of the ferrous ion (Fe!’) , The molecu-
br struct ure of each hemoglobin molecul e is ve ry complex; hence, we represent it her e by
the srmbo l 1-lb.
duced. Because its moleculrs are also co mplex, we rep resent them as O! l-l b. The impor-
tance of its formation during respiration is represented as follows:
O,)hrmog!ob,n
mious tissues and orga ns of 1he body, where the oxygen is rel eased at 1hc cellular level
and they again become hr moglobin molecules. The hemogl obin then returns th~ough the
CJrculato ry sys tem to th e lungs, where they secure a new suppl y of oxygen. This process
occur. O\’ t r and over with every breath we take. . .
bonding to th e blood’s hemoglobin molecules. This union produ ces the substance called
ca rboxyhe mogl o bin, represent ed as CO Hb.
lfonoglobm C.uboo mono”M Carbo•)h.:nl(‘lglobm
cells that transports
oxygentothetissuesof
the body
when oxygen comb in es
with the blood ‘s
hemoglob in
compound that
monoxide reacts with
hemoglob in
u1edtomeasurethe
~~~;YHfMOGLOBIN INHALATION AN~PTOMS
0- l O Nosymptoms __ _
ZO-JO Headache, thr~ g in thetempl es; slow1ngofn! l le~
vom1t1ng, collapse
80-90
fa mt,ng, 1ncrused res:..pir_” -‘°-” -“‘- ‘-‘ ‘-” —-
Fainting, incru~d resp1rat1on and pulse, coma wit h i nt er;;;;;;;;–
I Comaw,th interm1ttentco nvulsions; depressedresp iraUon~
weak pulse and slowe d resp irat ion ; resp iratory fa ilure and duth
90-100 Death
•A(l.lpud In part from Liurtnct Brunton, Bruce o,, t,ne r, and Bjorn Kr,ollman. Goodm4n and G/lm,n) n,,
F’NmYcologiCII B•liJ o f rt,r,, peu !KS, !1th eclnkln (Ntw Yori(, NY· McGr, w-H UI Bo o~ (omp1n y, 1001), p, l&8I ,
normal bodily funct ion. This is particularly gra~·e because. hemog!obm s chemical affinity
for carbon monoxid e is roughl y 210 times greater Lhan its affimty for oxygen. Bet.iUSt
COHb forms so readily when elevated conc(‘ntra1ions of carbon monoxide arc inhaled,
th e situation may be immediate!)· deadly.
production of CO Hb. Carbon monoxide inhaled into the lungs does 1101 always bond to
th e blood’s hemoglobin; instead, it assimila tes into the cells of the body’s tissues, whm it
may interfere with enzymatic processes. For this reason, long•tcrm exposure to a low con•
ce mration of carbon monoxide may cause ill effects that are not otherwise experienced by
a shorr-term exposure to the same concentration.
but there arc multiple ways m acqui re lower-than-normal blood oxygen levels. Firefightm,
for example, are rarely exposed at fire scenes to ca rbon mo noxide alone. h usually is pro-
duced with otht>r combustion products like hydrogen cyanide and nitrogen oxides, Const·
quemlr, when firefighters inhale these mixtures of noxious gases, they may t’Xpericnce 111
effects that are dissimilar from those listed in Table 10.5 for carbon monoxide alone.
idc, the y are link ed v.ith the conversion of hemoglobin into the biologically useless m·
boxyhemoglobin. It is the presence of CO Hb in the bloodstream that hindt>rs the transpon
of oxy.gcn and causes th e headaches, fainting, throbb ing in the temples, and other symp,
roms listed in Table 10.5.
~::::mJ~~~~n, arici Carbon mon?xi~e becomes a component of the atmosphe re at virtually every fire scent. To
concen1rationi in a assure that firefigh1crs do no t inhal e a letha l concent ration of carbon monoxidt , cxJ)frtl
per1on’s blood r«:omm end their use of a pulse CO-oximeter. This device has been constructed to t’stimate
366 Chapter 10 Chem istry of Some Toxic Substances
tti< CO ·it ion of CO i lh, but also chcconcentraci o~s f urre nt models measu re no t onl y th e
c,Jfl(<'n cr.10. 14-B). These me:1sumnents are ('SS<'nual oty~cmoglobm and m('th emoglobm
1Sr-1'1on Monitonng fo r poisoni ng by p I CO or ac1 natmg the on-seen(' f ('COV('ry of
fi r<'figh1;~\ ,;, NFPr\ 4 fo r Mall )' fi refight er e~i:sed ,; ximmy or mher avai labl e m~thod s is
~1JodJt use;1 shortn ess of brea th or g . .carbo n monox ide or pr<'Se nt mg w11h hrlJ~;:;~ ,;a ixrs~ n·s CO Hb concentr~u ona;~;;:~; 1~ ~ S)'~lptom s. M
JI<' ITl<'dica l actenti~n for the md.1vidual. fae n when th; •s~i,!'! ~c~: ~: ;;; :c:;:t1s
::: ~;:
1depo,son,ng Topreventthedevelopmen1ola
poisonousatmosphere,nthetiome,occup,;JnU
\h0ul(la!waysconf,rmtha! ch ,mneyfluesare
unblocl::ed , so1henox1ouscom~t,onproducts
prope•ly vent up tilellueand 1ntotheouu,de
atmo1phere
Oiyg(n saru, at, on, i.e. , the r:i tio of 1hr mtal o.xyhr moglobin conctntrm oo ro th e wu l hrmoglobin rnnctntrJ•
IJO:l l!l the blood. Normal read ings u nge fro m 95% to !00% at SCJ le·, d. Va luC”S brio ~ 90 % u e com1dcr~
~. £xperc\ recommend th at pilon u\.C i n o~-ygr n pulse oximctet when flyi ng unprt”S1unl~ planC’S :i t 1h1~des
t.::ween 8000 fe.: t 1243 8 m) ~rid 12,000 fn:t t3658 m) m determine whether they rcq u1rr supplemcnul 0~1gcn
0;,:-,::::;d0 :~;~;· Rrh.1bJ/ itarion rroasJ fo r Me,rrbt rs D11rmg Emergt11C)’ Optral/Om a11d TrJ mmg
Chapter 10 Chemistry of Some To.x ic Substances 367
inh;ifauou of c:irbon nio~ox1d; N::;~:t;onsidered rh e !(;1ding causi:- of acc1di:- ntal P01SOrJ.
1ng 111 the Ame~ic:in pregnant must bi:- espra ral barrier 3 nd dissolving in the blOOd J
becauS<' rhe f;d1 Jkc"Juse rhe fe tus recewes esshe moth~rs have inh.aled sufficient c.1rbo
ihe. un~~~' ~irth defects, parocularl~ : ·:::sst. . . . c
~o~:~idc t~ cause chem to ]oSc ':;;;;d with exposure IO carbon mon.ox1de lS mhalatio~
3150
c:irbon monoxide ox1 izes JC(Xg) … O~(g ) __. !CO;(g)
by volume whtn t/’le c.tr s di /I~. b
occurs and carbotl moMl!de 11 Pd n ,di,ng than when the car 1s mo~mg Th, s ca 1Jses a cor rt’Spond ng’, iar:jfl’ :o~:s;~,t~:i=~ ,:’pr!IJCed wt,en the car 1s 1dl: ng comoared 10 when ,t 1s movmg
usmg a pu~ (C)-0.Qrreter, a paramed< establ,shes mat the b'ood of an on-duty f1ref19h 1er cont a ns carbe')flt-
rnog'OOln a1 a concentrabon ol 62'Ml by volum e lsth,sconc entraboncons,deredhle-threatenmg ?
Solution: T;ib'e 105 ,nd.ca:estha1acarbol)'hernog'ob1nconcen trat1on 1n1he rangeof60% to70%cou'dt:t
fa-.al BaSld on tt\js mform~bOl'I, 11 ,s prudent to conclude that a u rboryhemog!obm concentrat1on of 62~ 5
ife-tllfeaten,ng
Wh en t~c ~se of carbon monoxide is necessary In the workplace, OS HA requires emplo)’·
ers ro hmn employee exposure to 3 maximum concentration of 50 pans per million
(55 mglm \ averaged ove r an 8-hou r workday.
CARBON MONOXIDE
1~;tion in th; :~tbi:~~t~i; a: ae ,;iir:ar~a Act, EPA regulat.es the c;1r.bon mon~xlde conctn·
a1r-qualit)’ s1and3rd for c3 rbon mon ·lollutant by settm? ,.he p ri ma ry nat1011:tl ambirm aver3gc and J5 pans per million (
0oxi e jt 9 pamper million (10 mg/m
) as :in 8-hour
Us in g II generator Indoors. CAN KI LL YOU IN MINUTES,
Ge nerator e)( haust contains carbon mono)(•d e. Th is Is
a po ison you cannot see or sme ll .
or garage, EVEN IF doors far awav from win dows ,
and windows are open . doors,andven1s.
REA D MANUA L BE FORE USE .
To m1n .m,ze or ehm1na 1e exoosure to carbon monoJUde from the use of portable 9enera101s. ~~~:q .i r;s ai 16 c FR 1407 3 to affix this label to portab1e generators and the,r pa<:k.a9 1ng
10. 10-F CONSUMER PRODUCT REG ULATIONS INVOLVING
The death toll from i.nh.aling c:trbon monoxide In the home is considi:-rable. T h is fact has
caused th e CPSC to mform the public that exposu re to the gas is potenti:i ll y letha l. The
CPSC uses lab eling to warn peop le abou t two relatively common ways of generating car-
bon monoxide: the burning of cha rcoa l in doors in gr ill s, hibac h is, and similar items; and
che operation indoo rs of portable gene rators. The production of ca r bon monoxide in
bo1h inst:tnces m.ay kill a home’s occupants in minu tes.
the label shown In Figure 7. 17 on charco;1I packaging. CPSC a nd FEMA also requi re
pomblc generator ma n ufacturers to affix the label shown in Figure 10.7 on po rtable
generators to warn the unsuspecting pub lic that using these device s indoors co ul d lead
Ca rbon monoxide is comme rcia ll y av:tilable as a nonliquefied compressed gas and cryo-
genic liquid. When shippe rs offe r ei the r commodity fo r transportation, DOT requires
chem 10 provide the re levant shipping descriptio n shown in Table 10.6 o n the accompany•
mg shi pping paper. DOT a lso requires shippers and carriers to comply wi th a ll app licab le
IJbdmg, marking, and placa rding requirements.
CAR BON MONO XIDE
compressed gas
Carbon monoxide
cryogenicliqu id ‘
UN1016, Carbon monox ide, compressed, 2.3, (2 .1).
(Poison – Inhalation Hazard, Zone DJ
NA9202, Carbon monoxide, refr igerated liq uid, 2.3, (2 .1),
(Polson – Inhalation Hazard, Zone D )
hypetb•rit oxygt n
thtr• py • The1nhala-
uonofoxygenunder
incru~pres~re
w1th1nar.ea!Mstttl
ch amber
10.1 0-H RESPONDIN ONOXIDE E
Wh en md1\ 1du;1.l s lose ‘
~:s:~:u:·here 3 mrans of amfic1al rc:sp irauon an d fre~h :ul~ bi:
c;i n be :idmmist ned. ~;e~loolro approximately half its 1m11al con ce ntration. on or
carbon monoxide mt de s hav<' b('en excessively exposed to carbon rn o
th(}’ :ire o.ften mmspo~;r~ to aunde r : physic1a
hyperbanc oxygen thi ,h!~rhan -normal-oxygen ~unos~hue 1~s1de a pr
subiecong them
~::.n Figure IO.S. The intermittent mhala.tl on o~ 10 0 oxygen at
pressure of 2 a~:;:~o~r:f ca rboxyhemoglobm to oxyhemoglobm co mpared wnh /h~~t1
~nf ;hoeo~::: ~oen at I atmos ph ere (10 1.J kPa ) for the same period . . \’<' hen hypcrbaric OX)~
gen ther.ip/i~ ust"d to trea t indi viduals exposed to ca rbon monoxide, the ox}gen acts ~
3~~~:t:~ of a hyperbaric cham ber was fi rst introduced ~uring the nineteenth cent llrj•
the normal atmo1ohenc pressu re for 30 to 60 minutes to patents wh,le they l, e ,ns,de enc losed ct,arr bers TN
u1eolhyperba11c oryg enth erapyat2atmmpheres (2026k Pa)acceleratesthe removalof carbonmonoxid!
from the blocdstrearn fo r this reason. 11 can potent,ally save the lives of emerge ncy responder; who ha·ie t:,et,
o~ere;po1ed to carbon mono)(Jde (Co,,rresyo/Perrys,,romro,c.i1coroor,1 r,on, R,wy,1Be-ac.n. noroa)
~
;0 1: ;~ ~mounr dissolYt’d a11he water’s surface. When
ntO their bloo 1 . omprt’sses nen·es and obstructs arteries, vem s,
~r} slowl y or rakr advanta g~ of th t’ use of a hypt’rbanc chamber. The hypt” rbanc cham-
~ r 3u0 ws the di~·ers 10 ~~pmence th e same pressure that they experienced at undtrwater
~rrihs. Undt’r 1h1 s cond1oon, the gases t’SCapt” naturall y.
ro ,.,rbon monox ide, but also individuals subj ected wit h certam o1her ailments. Ph ysi-
o~ns h:1. 1·c successfull y treated d1ab_t”t1c foot ukt’rs, bone infecti ons, ,humal burn s, and
rJdiauon bur~s 10 _ bone and soft tissue: The success of hyperhanc o xygen th erapy fo r
crtJllllS th ese m1unes occu rs fo r two ma,or reaso ns:
Jr~irrs ro a patient’s organs and tissues.
drtP”r m!O the body s org:ins ~nd m sue s. ~ nd er th is increased pressure, th e capillarit’s
diffuse the blood f_:irtht’r, allowmg oxygen-rich blood to be carried to areas that may oth-
trwisc be maccess1ble.
iiduals exposed to c:1rbon mono xide, the same degree of success has not been achieved
~·hen i1 is use d for the trea tm en t of indi vi duals exposed to other poi so nou s gases like
hid rogen cyanide (Section 10. 1 l l and hydrogen sulfide (Section 10. 13).
At te mpera tures above 79°F (26°C), hyd rogen cya nide is a colo rless, toxic gas. Some of its
ph)’>ical properti es are prov ided in Table 10.7. ln the chemical industry, it is used prima r-
J), to produce methac rylates (Section 14.6-E ). In the pa st, hydrogen cyanide w:is used as
i fum igant to kill rodents and in sect s, especially onboard ships, but given 1he accompan y•
ing huma n dange r, thi s practice is no longer popular.
mJlly is pt’rceived at a concent ration of 0.2-5.0 parts per million. Due to a unique geneuc
pred1spos1 tion, how eve r, some peop le cannot perceive th e odor of bitter almonds.
“1elt1ngpoint 1•F(-14•Q
Boiling point 79″F(26•CJ
Spe< 1fic gravi tyat68°F (20 ' C) 0.69
~ ens ity{air : I) 0.938
Auto ign ition point – 1ooo•F(-538′ Cl
Lower flammab le limit 6% by volume
lipper flam ma ble limit 41 % by volume
cy1n ld1
n11.Jonofphysical
iymptomsis~itl!d
with.ir ed uced o.:ygen
concentrat10n jnth@
blood
for .i subscJncr whose molecules contJin onlr one ca rhon , hydrogt’.’n, and n11::t~
1
econ po h b;fJnce called hydrogrn cyanide is rrpresemcd hy the h e. f0r
fo rmu!J HC , .
Hrdr ogen cyanide 15 produced as :1 commw:ial chrm1cal product by the ca ral nic reaqlOn
bemeen :i.mmonia and air w11h na rur:il gas.
r:He wnh other hydrogen qanide molecuks. To preveor thi s reac11on, the cornrn
grades of h)drogen cya nid e arc srab1lizc-d wirh wartr and 0.05% phosphoric acid . trciil
Exposure to hyd rogen cyanide occurs primarily when th e gas is inhalrd, as a resu l
which rhc bod y ex periences 1hc ill effects hst~d in ‘.able 10.8. Th e initial sy mpt;~;
include dizziness, headache, diarrhc.1, and anemia, w~1ch arc also characte ri stic of expo.
sure to most poisons. Exposure to hydrogen cyanide can a lso occur by absorpt ion
throu gh rhe skm. . . .
bluish colorauon m the finge rnail btds, lips, ca r lobes, conjuncuvc, mucous membra
‘
The general public 1s most famili:ir wnh cyanos1s as th~ ca use of the bfo e- baby S)’ndromt.
C)·anosis is not so!cl r symptomanc of h)•drogcn cyanide exposure. It also results v. hrn
ccrta m ot herharmfulgasesarcmhaled.
HYDROGEN CYANIDE (PPM)
JOO
1 b1olog1cal acnvity of C)tochromc dnidual s is lmkcd v.1th 11 s ab1l11 y
‘ ce lls
~\:e expos,u re renders th e enzyme m3 c
v.h csnt~h~sc rhe ox)gen effcctnel)
5
Jrogcn cyanide formerly was used as a means f
\Jnd, ~!ississi ~p1, i\’11 ssoun, and Wyoming-srill authorize ttnzona, California, .\ilary –
crf!Jl tl cOJ1d111ons for c?nductmg 1udicially mandJt ed cxccut~o~: ~ ~hac!c~h~ r!a:::~:r
So,hum,);m l..k, ll )dro..hlol’l(C a.: 1J ‘,o,,humchlonJ.c lt )Jrogcns)llH,k
ducting death sentences. In bet, there exists toda y a nationwid e inclination towards abol-
1slung the d_cath sentrncr altogether-by any mean s. In states where capi tal punishment is
sull authonzc
, the us~ of 3 lethal gas has been rtplaced by lethal inJcction as the pre –
During the HolocauSr in Wo~ld War II, Nazi Germany used hydrogen cyanide as a chcmi-
cil wa~fare agent for th e ~akmg of h’.1man lifo. Th e Germans had dc\·t loped a method for
adso rbing hydrogen C)’_a~ 1de on calcium sulfate pcllm, and sca ling chem in steel cans for
po1rn1ial use as~ pc:t 1c1dc callc~ Zyklon B, wh ere th e “BR refers to the German word
Blau;ii11re, meaning hydrocyarnc. Hyd rogen cyanid e was gene rated wh en the pellets
were exposed to the atmosphere.
mermmatc European Jews, non -Jewish Pol es, political opponents, gypsits, homosexuals,
dtSJbl ed, _and other people d~emcd to be “undesirablc.R At the Nazi death camp s, pellets
of the poison were _dropped mto the _\’ents of locked rooms that served as ga s chambers.
The hydrogen cyanide tha t evolved kill ed the occupants within 20 minute s.
mimatt that exposure to hydrogen cyanide at this single camp alone caused the deaths of I
10 2 million people. lbcir murders sc n·e as one of the wo~t instances of genocide in the
t’olentie1h century. In all, it has bee n estimated that 6 million people died in the death camp s.
h)”drogcn cyanide as a weapon of ma ss de struction. In 2003, the U.S. Dcpar1m ent of
Home!Jnd Security issued a warning to la w enforcement personnel tha t al-Qaida opera-
mes planned to use hydrogen cyanide within the confines of the New York City subway
$)Stem. Although this incident was never confirmed, it highlights the fact that cya nid e
could be used as a chemical weapon against Americans.5
rials to kill massive numbers of people, law enforcement agencies should be pro1·idtd wi1h
Chapter 10 Chem istry of Some Tox ic Substances 373
I
! 374
• d t fi rt’ scc-nes by fht’ th c- rmJl dt”CO mpos111011 of c
0
::~amc compounds wh osr mol.c-culc-s have one or 11~0~:u~
mdc- group~ ( C-, J I nd pol )•urt’ th:inc. Hydrogc-n cya mdc- 1s rc-lc-a sc-d i a,.
turc-d fro.m pol y:icr;m:~11t~//produc[ of thrir dt’Co~posit.ion.. nto the
su rr~;h::::~v-~;~gen cy:i mde ma r forni dur ing a fire, sc1e1_1t1 ~1s. generally bc- lic-\’t’ th,u
does not ultim: rel y sun·1\’C’ bc-ca use HS lower flammabl t’ lin1tt LS onl y ~% hr \’Olulll(~
Hydrogen cya nide readil y ignit es by mcomplet c- and complc-tc- combustion, as dernon:
srr.u ed by tht’ fo l!owmg equatwns:
(a.,t,.,ii ,uono”clc ,,mco<1dc
C:ffl’Ond1
concentration durmg the early srage s of 3 fire, whrn sufficient ht-at 15 prt-scm to initiatr
rhtrma l decomposition bur before the ga ~ ox,d1 zes. . . .
ph ere of a fire scene when cext iles smolder m confined·Sp3Ct’ env1ronme n_ts having low
levds of ox rgen. On-scene firefighters must be wary because th t”y may mhale the ~ 1
before it oxidizes. Because of thi s possibility, they a r~ often trratt”d 3S a precautioruiy
me:isure even when 1t is unclear whether they actu3Jly mhaled th t” gas.
admini stration of an 3ntidote. Tod3y, manr physicians choost’ 10 3dminister hrdroxoco-
balamine.6 Whc-n injected intra 11enously, prefernbly by paramedics a t the fire scene, this
substance binds the cyan ide to form cyanocobalamin e, whic h subsequently is excrmd
from th e body in urin e.
HYDROGEN CYANIDE
3ged O\’er an 8-hour workday.
When shippers offer hydrogen cyanidr for transportation, DOT requires thrm to pro1·idt
th e relevant shipping description shown in T3ble 10.9 on the accompan ying sh ipp ing
pa per. DOT also requi res shippers and ca rriers to comply wi th all applicable l3bth ng,
ma rking, 3nd placarding requirements. As noted in Sectio n 6.6-D, when h>·drogc-n C)’J ·
nide is transported by rail in bulk pacbging, DOT requires th e car ri ers 10 displa )’ tht
PO ISO N INHALATION HAZARD plac3 rds on whi te squa res with b[3ck borders.
Stephm W. Borron, f ridfoc J. 8Ju d, Bru no Mi-g.i rbJ nr ~nd ChJnt~I Bismuth ·HydroxocobJ!Jmin lo1 i!” C/1′
Chap ter 10 Chem istry of Some Toxic Subnances
;;;drogen ?’a nide, sta bili zed (c onta ins len than UN1051 Hydrog en cya nide nab ih zed 6 1(3)
J’!o wattd :~~a(~.a~;~::;•utant) (Polson lnhal,1t1on
water; abrorbed into a porous Inert PG 1 (M,r ine Pollutant)
:::~:: :~:.;~n~r~ : :: ~t~~i’1,
: 1~0′:f~°’.1o~f ,:~~bltar>Ce to hydrogen cya nide 10 lnh,bit its aut opolyrntr•
H ·drogen cyanide dissolves .in W3te.r to . form a colo rl ess solution known as hydroC)’anic
a/id, or p~uss1c acid_. ‘.he 3Ctd solution ~s so weak it is in_capable of tur~ing litmus paper
:en used 35 fumigants 3nd rodenticid es in ships, warehouses, and green houses.
Thret” hydroqanic acid solutions are avai lable in commerce. When shippt- rs intend to
transport a hydr ocyanic acid solution in bulk, DOT requires 1hem to identify the appro-
priate sol uc_ion 35 shown i~ Table 10.10 o~ 3n accom~anying shi_pping p3 ~r. DOT also
requires sh ippers and ca rriers to comply with 3]\ applicable labdmg, markmg, and plac•
~rdmg requi reme nt s.
,\ let:il!ic cya nides 3re ionic compounds composed of me1allic and cyanide ions. Sodium
cyanide3n d p01assium cyanidt” arc 3vailable commercially as so lids and 3queou5 so luti ons,
whmas copper(ll) cyanide and zinc cya nide are 3vaibblt’ sold y as solids. The 3queous
sol utions of the se la ue r two substances are used to elect rop late copper 3nd zi nc,
rrs pcctively.
of precious mt’tals from th eir ores. As the price of gold a nd si lver began to inc rease
throughou t the 2000s, mining for precious mern ls became profitable. Accordingly, th e
commc-rci3 1 demand fo r sodium cyanide has grown.
FORM OF HYDROCYANIC ACID
contain ing not mo re than 20% hydrogen
cyanide
Hyd1ocyanicacid, aqueo us solut ions
conta ininglessthanS ‘”- hydrogen cyan ide
Hydrogen cyanide, solution in alcohol
conta ining notmore than45% hydrogen
cya ni de
6.1,PGl(MarinePollutant)(Poison – lnhalation
Hazard,ZoneB)
NA1613, Hydrocyanlc ac id aqueous solutions,
6.1, P’G II
UN3294, Hydrogen cyan ide solution in alcohol,
6.1, (3), PG l(Mar ineP’ollutant)(Po lsonlnhalation
Hazard,ZoneB)
cy1nld1
I
diox ide
METALLIC CYANIDE
(Poison) _ ‘ arine Po llut~
stuuent s of consumer produc ts intended for use in the Urured Stares. This r:n~i”s as con.
is published at 16 C.F. R. 5 1500. 17. g 3 toryb~ n
When sh ippt” rs trnnspon a me1altic cyanide in bu lk , DOT requires them to id .
approp riate su bsrnnce on an acco mpanying ship ping paper. Table J 0. 11 prov·~ntify tlk
represemari ve examples. DOT a lso requires sh ip pers and carriers to comp! 1 ts. s:~
applicable labeling, marking , and p lacards rcquiremcnrs. y wu all
Materials Ta bl e at 49 C. F.R. § 172. 101 , DOT requires s hi ppers to provid e rh/;3( 0ui
shipping .de script ion gene rically a nd ro prov ide the name of th e speci fi c com~:::~ paremhct1cally.
Sulfu r d ioxide is a co lo rl ess, nonflammable, toxic gas havi ng th e s h arp, pungent odor
associated wit h burning matches or ti res. Some ot her p h ysical propert ies of th is gas are
note d in Table 10.12 . These d a ta indicate ch a t su lfur dioxide m a y a lso be encountered
comme rcia ll y as a liquefied gas. W hen used as a comme rci al c hem ica l product, sulfur
dioxide is primarily produced by burning sulfur.
try. It is a lso use d by the agri cu ltura l indu stry to w hit en refi ned sugar a nd 10 lengthen the
shelf li fe of dried fruits. When g rapes arc dri ed a nd processed in a n annosphere of sulfur
di oxid e, raisins wit h a go lden color are p ro duced. When th ey are nor exposed to sulfur
dioxide, rh e ra isins arc dark brown. Foods th at have been lreated w ith sulfur dioxide do
not ferment or support rh e growth of fungus a nd mold .
functio ns as an in secticid e a nd rodenricide. In rh e chemica l industr}’, it is use d prima ril)·
for the production and manufacture of sulfuric acid (Sectio n 8.7) a nd metallic su!fit~
Meltin g po int
1.436
~allydetcc1ab le ~1ane and1m;i1 –
,S ___ Rtpeated ~
e Ynona ~ at ,cln d ,,..,d ual\
— ~ ddeningofthethroatandm,!d
of breath, and connr,ct,on of ~h: 0:,~•;i· (hen pa,n1, 1honne11
;,100 lmmed1a te lydangeroustoh, ft;,———
Inhalation toxicity is the pr imary hazard associa ted wi th exposure 10 su lfu r dioxide. As
$hown in Table 10. 13, coug hing, ches1 pa ins, shortness of brea1h, and co nstr iction of the
ai rways sy mptoms a ssoc iated wit h an exposu re 10 thi s gas. These toxic effec1s are derived
…. holly from rh e abilitr o f sulfu r dioxide 10 directly irritate the mois1 mucou s membranes
o( the uppe r res piratory tra ct an d rh e lun gs. Although many indiv idu als are ab le 10 tol er-
ate \’Cr}’ low concentrations of sul fur dioxide-such as those routi nely fou nd in po llut ed
ai r-for sho rt periods of time, an ex posure to a concenrrat ion of 100 part s per million in
air is usually fatal. The specific cause of respira1ory fai lure from exposure to su lfur di ox-
ide 1s mos , likel y assoc iat ed with rap id lowering of 1he blood’s pH.
dioxide. Typically, whe n exe rci si ng, they a re unable to tole rate a short ex posure to a co n-
centra tion as low as 0. 1 part per mill ion wit ho ut exper iencing constriction of the bronchi-
olr tubes.
GENERATION OF SULFUR DIDXIDE
dwellings and operating local factoncs. Durmg th~•~::d~’ !n~ articulate ma iler were
lo~don~rs burned coa l for thes.e pu~poses, sul fu~ n~ became d:adl)’, The situation was
emitted mto th e at mosph ere unol .ihe ir conce~:~:~ the llut ants from di ssipa ring, forc-
~xacc rbated by the absence of a wmd th at p~c\oo Lond:ers died during the initia l da ys
mg Londoners to inhal e th em. Subsequ cntl), d , ti c event is recalled as thr Lethal
and ano thrr 8000 died in the next rwo mo~ :~. a~te~~;ioi~
the fact that our well -being London Smog Episode, or Great Smog. It re
Eplsod t (G,.at Smog)
re~ idents inhaled sulfur
d ioxide that could not
d in iP3te due 10 mete•
orolog icalcond1t 1on1
I I
having an approximate
pHofS.6orlessand
caused by disso lved
nitrogen oxides and
sul fur diOlllde
In contemporary _cl .’ h air 15 gent’r:Hed by the c~a l-fi red powe r plants th
thi rds of the sulfu r dioxide mt ; PA regulations that req111re If s curbing in stac k e a~ 0.Ptr-
ate in cheUnitedSrntes, espne n11 ss1oni,
duceSdu~~;u~~f1; dunng thterupoon of vok:rnoes. In Haw311, fo~ e~ample, the kil:;:·
volcano has contin uo usl y spewed massive amounts of sulfur d1ox1?e a_nd panicuta,:
mamr into the a~morhere since at least January 3, 1983, when SC1Cnt1 s 1s first ~ n
st
1
t r:i eased into th e ai r slowly ~xidi_zes to sulfur trioxide, wh ich in turn
Sul for(!iO., Jc 0,)gcn Su\fo, 1n o\1 d~
cipitation having a pH of 5.6 or Im. Aci? rain has severely_ dam aged building maitria ls
made of co ncrete marble mortar, and limeston e. A startlmg example of the ntgai ii·t
im pact that acid :ain ha s had on stone structures is evident fro _m ~bserving Cleopatr;i’s
Need.le an obelisk that was moved from Egypt to Ne w York City m the late nin eteenth
cent~. Its surface has dereriorated more in 100 years from exposure to acid rain than it
did during the 3000 years it stood in Egypt. .
referred to as atmospheric cooling. Wh en sulfur dioxide is_ ejee1ed into the atmosphere by
an erupting volcano, it oxid izes to sulfuric acid, which m turn seeds aerosol part icles.
These particles reflec t th e incoming sun’s rays away from our planet bac k into spm,
thereb y reducing 1he amount of radiation that reach es Earth’s surface. This ph enomenon
can cause a seve re drop in temperature that pers ists for eons. For exa mple, scientists ha1t
proposed that th e sulfuric acid aeroso ls produced during volcanic eruptions in lndontSia
caused the Lud e Ice Age, the approxima1e period from 1550 to 1850 du ring which ba·
terly cold winters were experienced in many parts of th e world.
Sulfur-containing co mpounds are consriruen ts of many producrs including th e followin g:
Complex protei ns present in woo l, hair, and animal hides (S mion 14.5-B)
Se\·eral natural and sy nthetic polymers, including vulcanized rubber (Section 14.1 I-Ci
When th ese products bum, the sulfur is converted into sulfur dioxide. Firefighters
other products ro which sulfur was added.
‘.Vh_en the us e of sulfur dioxidt is ~eeded in the workplace, OS HA req uires employers j0
limn empl oyee ex posure to a maximum concentration of 5 parts per mi ll ion ( 13 mglm I,
averaged ol’e r an 8-hour workday.
378
Chapter 10 Chem istry of Some Toxic Substances
ht’ arnb1ent air as a cmcria air pollutant. EPA set th e daily and annual primary Slan-
SO µg./111 3), respccovely. EPA3 also set the secondary sta ndard for sulfur dioxide at 0.50 ~ ris per mill ion ( 1300 µg/m ) as a 3-hour average.
1f r dioxide is available commercially as a liquefied comp ressed gas, When shippers
paper as follows:
ing, and placarding requirements.
101-olving the release of a bulk shi~ment of sulfur dioxide, they must acknowledge 1ha1
ihe 53 fcry of the team, transportation personnel, and the general public is at ri sk. The
Emergency Response Guidebook recommends isolation and evacuation distances when
la rge spills of s~ lfur dio~ide occur from ~ultiplc small cylinders, single ton cylinders,
multiple ton c~l~nder:, rail tankcars, and highway tank trucks and trailers under prev ail –
ing wind condmons.
Hi·drogt n sulfide is a colorless, flammable, and toxic gas having the physical properties
nottd in Table 10.14. Perhaps its mos! immediately apparent featu re is the disagree able
siench of rott en eggs. Humans detect this smell at just 2 pam pe r billion. The stench is
truly offensive at co ncentrations as low as 3 to 5 parts per million. Sometimes individu-
als describe the odor of a material by saying that it smells lik e sulfur. Because elemental
sulfur is an odorless so lid, what they actuall y mean to say is that the mat erial smells like
hydroge n sulfide.
Me lti ngpo in l i -11 rF(-86 ‘ Q
~ cgravltyat68•F(20″Q
Fl ashpo in t
-116′ F(-82’O
oH.ct oryfa-ligu e • The
temporary in.tb ilityto
1dentifythe odorofan
a1rbomesubstance
after prol011ged
expoiure
1..ir comme~c1a/ product. For its hmm:d use m commerce, ~t rs primarily dcrivedPoP\I.
m roduce de mcntal sulfur :md sulfuric :acid, to pr~ ess mmeral ores,
under \;~;~”s:~r~ ~;,uns, and oth er an.ae robic (~o_noxrnen ) envir~nments fro~s:11·er1,
the ga~ seeps mm the armospht’re. The dccom posJUon_ of sewage gives rise 10 th e t~:ch
sewer gas, 3 term usrd by sanitary enginerrs who wo rk m sewers a nd at se wage treat Ill
fu cili ues. Th e odor of hyd rogen sulfide is also c-nco untered at petroleum refineries, “‘~!
ihe gas is reco\·ered by the desulfu rizatton of sour crude (Section 12 . 13 -F), and as 3 ~,
sntuent of mammalian flatulence. The bod y generates trlce amounts that it uses to r:::
irs presc-nce immediatel y upon expo.sure. Noneth eles~, when the.y ,experience long~;:r~
exposure to low concentratmns, their sens.e of smell 1s temporanh deadened. This pht.
nomenon is called olfactory fatigue . Connnued exposu re causes them ro become ob!
ous ro th e pre se nce of hrdrogen su.lfide, increasi ng the possib iliry that th ey
unknowingl y inhale a lethal concenrrauon.
Table 10. 15 indicaies that inhalation toxicity is ih e primary hazard associa ted with expo.
sure to h}’drogen sulfide. Exposure initially givrs rise to di zzi ness and the on se t of a h~aJ .
achr, but unconsciousness and respiratory paral ysis can follow immrdiately. Inhalation of
air having a hydrogen sulfide concentration ~f 1000 plrts per mi!lion is rega rded as fac al.
previously noted for hydrogen cyanide poisoning: Hydrogen sulfide reacts with cyro-
chrome c oxidase, th ereby prrventing cellular respi rati on. The treatment of indi\·iduali
exposed to d evated concemrations of hydrogen sulfidr with hyperb:i ric oxygen has bttn
only minimally successful. There is no known antidote.
HYDROGEN SULFIDE (PPM)
5.0
5-29
Bronchialconstriction inasthmaticindividuals ___ _
Increased eye compla ints
Decreasedoxygl!nuptake
Eye irritat ion
d1uiness
Olfactory paralys is
Death
n tnt~,;i. Sw,tlerland, World Health Organ izat ion, 2003), p. 14.
_13.e HY_DR_OGEN SULFIDE AT FIRE SCENES
ll )dro~c n ,ullijc O, )ftn \l, JICI Sulfu, d~u\lJC
~bl,, Althou ~h small con ce mran ons m~y evolve dur ing the th ermal decomp~si ti~n o f
certJlll niarenals n~anuf~ctured from animal products (i nclud ing leather items and wool
cirptung), 1he gas 1s easily co nsumt”d by combust ion.
10 ]tm it emplo~ ee expos~re to a maximum concemr:mon of 50 pans per million in a
10-min~ce maximum permd. :vhen an area may contain an atmosph ere of hyd rogen sul-
fi de, 3 sign such as the followmg should be posted:
GAS
H)·drogen sulfide is transpo rted in steel cy linde rs an d bulk tran sport vehicles. When ship-
pm offe r hydrogen sulfide fo r transportation, DOT r(‘quires th(‘ m to provide its shipping
descri ption on an accompanying shipping paper as follow s:
ing, and placa rd ing requirements. When hydrogen sulfide is transported by rail, DOT
requires carriers to post th e POISON GAS placards on white sq uares with black borde rs
on the bulk packaging used for shipment.
OF HYDROGEN SULFIDE
m ignored safety practices at petroleum refin eries and chemical manufacturing facili-
ti es, in sewer sys tems, and at other locations where hydrogen sulfi de was stored or
generact’d.
n,ned unknowi ngly. For example, chambers are used for storing se wage onboard mod-
ern sh ips, umil i1 can be treat ed on shore. Hydrogen sulfide can accumu late in th ese
chambers at a lethal concentration. When it is necessary to repair fractures in the wa ll s
or their connecting pipes, worke rs mus t avoid exposure to this deadl y gas by wraring
stanceto ignitesponta-
neouslyoncontactwith
anothers1.1bstance
fully-enca psula1ed sui ts ari
known but we are concerned here \~ith only two n ~:i
~~ (:~s:1ti~~:;
:~ nitrog;n monoxide ) and nitr~g~n dioxide. T~eir ~h:~;
1
monly are repr esr nt ed jointly as NO.r and ar~ called c~e _nnr_ogen oxides. Nitric oxi& IS
colorless gas with an irritaung odor, and nitrogen d1ox1de 1s a dark red-brown gas hai·-
Thei r phy si ca l propert ies are listed in Table 10. 16. Both are avai lable comme rcially as
HazardClass 2.3gases. . . . . _
tals and clinics, where low doses are administered with oxygen to treat emp h}·uma
and other pulmonary diseases. Nitric oxide caus~s the blo~d vessels to dilate; conse-
quently, respiratory pati en ts experience reduced mflammauon and lower blood pres•
sure. Nitric oxide has sa1•ed the lives of premature babies, because i1 red uces the mk
of fatalitie s from such diseases as bronchopulmonary dys plasil. It has also helptd
firefighters avoi d labored breathing, especially whe n their lungs were coa ted with soot
while combating fires .
pie, the Apollo astronauts used it with unsymmetrical dimerhylhydrazine to leave the
moon’s surface.
\ I
N- N
I \
w1151m- D1 11l(th} lh~d1:11mc
~ypergolic; that 1_s, the substances react immediatd}· on contact. The ni 1rogen diox-
ide an~ uns)’m-dim ethylhydrazine act as an oxidizi ng age nt a nd a reducing agem,
resp ect 11·e!y.
Melti ng po int
– 263 ‘ F(-164″C)
00
it<~e·t the unf,l'ed octet and ach eve e'ectron c stability, two n,trogt:ri d ox.de molerules comb,ne to produce a
110n of ammonia as fo ll ows:
,\’itncoudt
N1tnC O\ldt N11rogcnd1oudc
11sd f, mole fo r mole, ro become dini1rogen tet roxide.
/l.’nrogcnd10x11k D,n11rogtnteuo”Je
nuroge n dioxide.
WITH THE NITROGEN OXIDES
oxide and nitrogen dioxide at ambie nt 1emperatures. However, the combination occurs
rapidly at elevated temperatures.
Nitrogen
N1tnc u~1dc N11rogcndn>l1dc
gen dioxide is produced at (he concentrations shown in Fi gure 10.9. For this reason, the
rown atmosphe ric haz e 1hac hangs O\’er many ci1ies.
dioxide
ocr.attonandfuel-
ccrnounionactrYltlts
1Ca.n!’5Yol t.nrfd5~res
industria l
lndustri•I
processes
combusti on
tio n of ground-level ozone. Sunlight d1ssoc1ates ~mog_cn d1ox1de mt_o mtnc oxide and
oxygen atoms. The oxygen atoms rapidl y combine wnh atmospheric oxygen to form
\ iirogen d1oud,: , nn, 0~1dc o~> scn 01001
0\)gt”n O~}S~n:11001 OtQ nt:
a group of unstable compounds called peroxyacyl nitrates, or PANs. These compounds
have the following gene ral ch emical formu la, where R is an alkyl or aryl group (XC –
tions 12.2-C and 12.11, respecti\•ely ).
//
\
O – O -N0 2
(PAN )
The presence of ozone and PA Ns is characteristic of photochemica l smog.
urban atmospheres, EPA required automobile ma nufac turers to bui ld cars that reduced
the a~ount of_ NOx emincd in vehicular ex haus t. In response, cata lyt ic convrners
were installed m new automobiles. One chemical reac tio n that occurs on the surface
of th e convener is the reduction of nit ric oxide into environmenta ll y friendly nitrogen
and ox ygen. The use of conveners during the ope ration of modern-day moto r veh icles
has red uced th e amount of N Ox t hat otherwise wo ul d be ejec ted into the
atmosphere.
impact us quality. In th e ozone layer, the nitrogen oxides react with ozone 10 produce
d. ~orni~! ~X);en. The nitrogen dio xi de th en reacts w11h oxy ge n atom s
t-..,1rou,o,.,.k Olooc- ,\urog~n d10\1Je
J\ 1!rofc nd1o”dl’ O,) gcnaiom J\itl’O\l\o,iJ.o
tn hJl ltion toxi~ity_ is th e _p~ imary hazard associated wirh ex posure to both nitric oxide
,1 nd nitrogen dioxide. lmtial exposure produces irritation of the mucous membran es
of th e e)’CS, ~hroat, “?sc ‘. a nd lun~s._ ~s Tab le 10.1 7 shows, when an individual 1s
,~posed 10 mt rogen d1ox1de, t~esc 1m11al sy mpt oms arc followed by coug hin g, chok-
ing, he:idac ~e, ~a_usca, and fattgue. Wh ~n _the exposure is grea ter than 200 parts per
millio n, th e individual suffer s from lung tnJur y, bronchopneumonia, :ind possible fatal
pu Both nitric oxide and nitrogen dioxide arc readil y absorbed into the bloodstream,
i\here the y com bine _wir_h h~~oglobin to fo rm met hemogl obin !( NO z)HbJ. For exam-
ple, when nitrogen dmx1de 1s inha led, methemoglobin is produced as follows:
lk nioglobm NUro£C11d10Auk Mc1hen10globin
as the ferric ion (Fe3*), not the fe rrous io n (Fe2*). Li ke carboxyhemoglobin. methemoglo-
bin cannot effectivel y transport oxygen to the body’s tissues, so the host suffers from the
:ul ment called methemoglobinemia . Individuals who inhale nitric oxide or nitrogen
dioxide ex hibit the in itial sy mptoms of poisoning (dizzine ss, headac he, diarrhea , and anc·
mia ), but thei r blood also becomes chocolate brow n in color. It is this color that initially
sign als the severity of i\”O., poisoning.
mtt hemoglobinemia. In stea d, blood exchange transfus ions are usuall y needed to dec rease
the methemoglobin concentration in the bloodstream. Latent effects ma y also be experi-
enced, and dea th can occ ur da ys afte r the initial exposure.
NITRO GE N DIO XIDE (PPM) SIGN S AND SYMPTOMS
exposure from pulmonary edema
Immediate danger of death follow in g short-term exposure
llmltiPro)ectOocumentatlon,CDC24/7.
hemoglob!n,
gen dioxide reacts with
the blood’s hemoglobin
health ailment
vidual’sexposureto
nitrogen dioxi de,
metallicnitrites,m etal •
lic nitrates,andsimil ar
substances
The toX !Clt)’ of nitrogen d~rl l !;IC acid IS produced as follows: reaq …. ,th
,~0,(“‘) … l-i!Ol’-‘l __. I-INO~(aqJ + lli\O, (lltl)
– · • • “11 rou , .1<.1J '\ 11n~ .11.1J
•
en dioxide reacts with atmospheric moi ~tu re to Prod
5
Ucc i
11 0 ns, its presencecanc;1use P
· d’ ‘de art’ the produm of tht’ inco mplete an d co mpl et
bustti~~~~::~; ::~~;:~mxide 1~c l~de the polyur~thane pro ducts use~ in b::~~:~
~ha :ddin and furniture cush1om ng. ~though its r~d-brown color is essentii
msullno n, b ~• “ble 10 decect the color ma predommantly black, smoky pl Y
~i~:h ti;r~::a/d
;:~:~e wheiher they have bee n overl y exposed to NO x by use u~
Exa mples of these explos ives include mmtrotol_uene (Sectron 15.9), cyclonite (Sec.
tion 15.10), terry! (Section 15. 11),and H.t\i!X (Section 15.13 ).
THE NITROGEN OXIDES
requi res em ployers to limit emp loyee ex~osure to maximum conce ntrations of 25 p;lrri
per millio n (30 mglm 3) and 5 pans per million {9 mg/m 3), res pecti\’ely.
THE NITROGEN OXIDES
has se1 both the primary and secon
da rr national am?ient a~r-qua li ry stand ard s for N0, 31
When shippe rs transpo rt nitrogen dioxi de (dinitrogen tetroxide ) or nitr ic oxide, DOT
requires them to provide the shipping description of the gas as shown in Table l0.18 o~
an accompanying shi pp ing paper. DOT also requires shippers and ca rri ers to compl y with
all applicabl e labeling, mark ing, and placarding requirements.
NITROGEN OXID E
Haza rd, Zo neA)
UN1660. N1tr icoxide,comp re1sed, 2.3. (5 .1). (8), (Po i~on – In ha lation
Hazard. Zone A)
,11119Po1nl _ …..,28′ F(-33′ C) :~ ty (li quid) at 68 ‘ F (20″() o 77
;ific!lr~ 8′ F{ 20 ‘ Cl __ _
:;,:.—t52′ F’11 “C)
_A11to•gn1t ionP01nt –+- 1204′ F(651 ‘ 0 ~
~ m•t 2S %byvo lum e
the earners to post th e POISON GAS placa rd s on whi te squares wi th bl ac k borders.
Animonia is a colorless gas_ that is easilr det ected and recognized by its familiar pungent
odor. It ha s been kn own smce the dars of alchemy, when it wa s produced by hea ting
either coal or an imal hoofs and horn s. Some of its impo rtant ph ysica l prope rties are noted
1nTable 10. 19 . . .
ferti lizer, Because the nitrogen coment of ammonia is 82% by mass, it is an idt”a l agricul-
tutJ I fer tilize r. Wh en form ers apply i1 10 farmland, they di spense the gas di rectly to the
soil or into irri gatio n waters throug h a di str ibution pod fr om a rra ctor sadd le tank or
nurse tank like th at shown in Figure 10.10. A nurse tank is a spec ific type of portable
!Jnk with :i capacity of 3000 gallons (1 1 m3) or less, is pa inted white or aluminum, and is
nem filled completely. It is mounted behind the tillage too!.
[Jrge refrige rat io n srstems. It is th e most economical coola nt of choice for meatpacking
p!Jnrs, da iries, an d similar faci lities.
com pr essed gas called a11hydro11s ammonia. This product is transported by hi ghwa y, rail –
war, and watercraft and transferred by pipeline. In Alaska, anhydro us ammonia is rhe
mos t prev alent hazardous sub sta nce throughout the sta te, where it is used as a refrigerant
31 sea food-p rocess ing plants and in radiators associated wit h th e Trans-Alaska Pipeline
System. In th e latter, th e ammo nia disperses the hea t th at evolves from the hot crude oil as
it travels through elevated pans of the 799-mile (1242-km) pipeline. The heat must be
dispmed to preve nt th e melting of the underly ing permafrost, the permanently froz en
rnbsoil in which th e sup ports for the elevated portions of 1he pipeline are embedded.
3ir-conditioning syste m. Ir is al so being used to cool the Internationa l Space Starion.
For commercial use, ammonia is produced from atmospheric nitrogen and hydrogen at
clm1ed tempe r:nure and pressu re. The production reaction is represented as follows:
1mmonl1
posesofDOTregu la-
tions,acargotank
having a capac ity of
3000gallons(11 m1) or
less, pa inted wh ite or
a!uminum,neverfil le d
to capacity. and used
solely forthetrarispor-
tat ionof anhydrous
ammon ia
to be mark ed AN HYDROUS AM MONIA on all four sides and INHAtATION HAZA RD on two op~ rng si d~ Th@
DO T 1dEm,fication numbe< 1005 must also be displayed aaoss the center of green 1'.QN.f tA MMABLE GAS
p/acardspos:1ed onallfour1,desoftlieta nh 1Counesyo/Thefert//!lf' /rnr,ru1e,Wash,ngton, DC J
rng from 3000 pounds per square inch (20,300 kPa) ro 8900 pounds per square inch
/10,800 kPa ) and 842°F (450°C) to 1 I l2°F (600°C), respectively.
~;;i~uitd~~:mmable ~s .wi_chin the_ range o~ 16% to 25% by vo lu~e. W~en !t
nor ordrn,m/y arramed. ~nder th ese circumstances, an ammonia fire cannot occur.
. None rhe_less, ammo~ia concentrations within the flammable range are a1tained due·
mf amdenr ~e naraos like rhe indoor release of ammonia into a confined area from
~:ei~s ~ig~J~~~::~:i’3~~t escape. I~ this circumstance, the occurrence of an ammoni.i
122 5 kJ/g) and de. _en ammonia burns in air, the combustion evol\’es 9650 Brullb · pro uces nitrogen and water vapor.
Ammonia O\y~n Nurosr n \\;:Ue rg
subsrances. fr is for rhis reason rhat ~:e w.irh _rhe \’alucs listed in Table 5.2 for och er
exposed roan addiriona/ hea t sou rce. mama fires are noc susta inable unless rh ey are
Af,!r.40NIA(PPM) _1 SIGNS~ –
.::!- – ‘
400-700 ~rd inari ly, no ser ious results following short exposures; pronounced 1rr.1tation, d1Komfort to the ears, nose, throat. bronch i lungs and mo ist
I
~i:~’:::~eedema, asphyxia, and death by suffocation even· after a
•,l,d, pttll In p~rt from OSHA Regu lat ions Applltiblf’ to Ammonia (2007)
GJ.rpeting-thermall y decompose when they are exposed ro intense heat. When chese
ni;1terials a_re present al ~re sce nes, the odor of ammonia often is perceptible, but the
concentration generally 1s coo low to cause harm.
rxamplc, when ammonium s_ulfate fertilizer is heated t0 high temperatures, it th er-
mal!)’ decomposes to ammonia, sulfu r dioxide, ni1rogen, and water as foUows:
When individuals are exposed to ammonia vapor, they expe rience the ill effects listed in
Table 10.20. The eyes, skin, mouth, trachea, bronchi, and lungs are particularly suscepti-
blr ro se\·ere irritation from the exposure. The inha lation of ammonia at concentrations
exceeding approximacelr 2000 pans per million causes death by suffocation.
ANH YDROUS AMMONIA
ers ro limit employee exposure to a concentration of 50 parts per m1 lhon (35 mg/m ),
ave raged over an 8-hour workdar. OSHA also regu lates how anhydrous ammonia is
Sro red and hand led in all workplaces other than ammonia manufactu ring facilitie s and
refrige ration plants using anhydrous ammonia solely as a refrigerant.
Wh en shippers offer anh yd rous ammonia for uansponation, DOT requires them ro pro-
vide the relevant shipping description shown in Table I 0.21 on a shipping paper. DOT
SHIPPING DESCRIPTION
Anhydrous Ammon ,a H.1nrd. zone DJ
“111ttm.111oNI 11,nsportat,on.
pbc:Jrding requirements.
Of ANHYDROUS AMMONIA
3
effecrs nored in T:ib/e 10.20.
Gi,·en rhe nature of the iJ1 effects resufring from exposure to ammonia, ,_he use of stlf.
im,o/ ving a release of ammon ia. When rel eased dire’:”rly from a /1.qu_1d storage tank mtothc
atmosphe re, ammonia gc-ncra J/y is visible as a white fog co~s•~ rm ~ ~f-~ro~lcts of con.
densed atmospheric moisrure. Alrho~gh its presence severely l1m1 ts v1S1b 1l1ty m the irnmt-
&are em•ironmenr, the initial fo rmation of rhe fog hel~s workers loca te rhe spot at which
rhe ammonia is /caking from ifs sror:ige ran~ or c?nr~me_r. . . .
air. When it is rele:ised outdoors into dry :ur, ammoma qu1 cklf d~spe rses m~o ~he armos.
here especially under windy conditions. When anhydrou s l1qwd ammonia 1s releasrd fnw dioist :iir, however, sm:i/1 liquid droplets of :immonia in _ water are produced. Un~,
ground instead of rising into the air and dispersing.
wa ter absorbs l l i6 volumes of ammonia gas. This physical property is used to advanr3gc
when responding ro incidents involving a release of ammonia. The recommended prncrice is
to est.1blish a warer currain downwind from rhe poinr 3t which the ammonia is being relm n!.
The wa ter &sso/ves rhe ammonia 3nd reduces rhe concentra tion rhar ca n rravel farther.
,mm e-d ate asohy.i<1flon, tht lmp!ementat.Ol'I of any em'ergfncy response act,on ,nvoh,,ng
nl, ~eiy ,f the ammor-1,1 sub~equen tly 1gr11tes Rtscue workers m~ be unable to successfully
:movtd to a med,ca lfac1l11y
ni·olrins the release of 3 bulk sh1pme~u of anhydrous .1mmonia, the )’ mu st acknow ledge
: ~;gene)’ Response Guidebook. recommends isola_ri on and ev3~uacio n ~isr:mces wh_en
multiple ton cy_li.nder;, r.1il tankcars, and highw.1y rank trucks .1nd 1railers under
P~’;he largest rran spo rrat io n spill of ammoni.1 in the United Stat es occur red in 2002,
when J I rail t~n kcars ~era.il_ed near Minot, No rth D.1kora, ~uring the wreck of_a Can a-
d Pacific Radway mun. Five of th e 3 1 tank c3 rs catastrophica ll y ruptured and instantly 1
::sed 146,700 ga ll ons (555 m3) of 3mmonia into the atmosp here. Exposure to rhe
some degree of respir:1.tory 1mpa1rmenr.
Almost everro ne has encou ntered ammoni.1 as the gas that esopes from the commerci~ I
deaning product ca ll ed household ammo11ia. This is ~n aqueous soluri?n of ammonia
rim.1 ril y used for deaning glass, marble, and porcel:iin su rfa ces. Chen11 srs refer to an_y
solution. Its chemical formula is NH3(aq ), or NH. OH. The concentrauon of ammonia
dissoh·ed in household ammonia ranges from 2% to 5% by vo lum e. The vapo r is percep-
uble at concentrati ons as low as approximately 5 parts per mi llion. Most individuals do
not find this concentration irritating. .
rio n fro m 10% to more rhan 50 %. These aqueous solu ti ons are hazardous primanl y
owing w the ammonia that rapidly escapes from them .
cemrarions. When shippe rs offer an aqueo us .1 mmoma soluuon for .rran sportauon, DOT
rrquires rh em to provide the relevant shi pping ~escription _shown m ~a bl e I0.2_2. DOT
also requi res shippers 3nd ca rri ers ro comply wuh all apphcable label ing, markmg, and
plm rd ing requirement s.
.scene responders when they encounter a s-trong odor of ammonia 1n an enclosed room ar an ice -cre.im piano
Solution: Ammonia cannot ignite 1t1 air unless a concentration within ,ts fl am mable range 1s exposed to an 19 “‘
tion source The flammable range of ammon,a is 16% to 25% by vofume A concemrat1on within this r.ai,qt~
read1fy ach,eved when ammonia eS(..3pes from large refngeratJon units into an enclosed room When emer9erq
responders frn detect an espec1a1fy strong odor of ammonia, th eir pnmary concern should be aimed at eJ.m not·
Ing the nsk of its ign,tJon. They can do th,s by o~nrng doors and windows to ven t the ammonia from the encJi>-
sure while s,muhaneovsly taking precautJons to avoid generatJng a spark
7Jb/e I, Eme~t•tcy Rt spo115e Guid_rbook (WJshingt.on, DC; U.~a~t.::rcr;r:~1 :ti;::i;a9~~:iz:n~o ~: ~~::~;
R,11/roJd Acci dent Re-port, ·oerarlmen ~ of Ca nJdian Pacific ;
., ~.,. NTSRIRAR -04/0 1 PB2 004 –
91610 1 (Wn hingron, DC: Nation;1I TrJnspormion Safery BoJrd, 2004).