Hazardous Materials
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Ch.10pg392-416.pdf
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eo=,:11·r:L · Ill 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 paper 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· 0
~ ~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
15 l'J5 § 0
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•n:;;;.,. SMALL SPILLS
LAR<H! s,ius <FROM A SMALL PACKAGE OR
(FROM A LARGE PACKAGE OR SMALL LEAi( FROM A LARGE PACKAGE) --FIRST
FROM MANY SMALL PACKAGES) THEN FIRST l ISOLATE PROTECT IN ALL DIRECTIONS
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 -t-- r-
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, -i--
100
0. 1 0 .1 0.3 0 .2 I 60 I 200 I 0.8 I o.s 2.S 1.6 1242 139 M ethyldichlorosilane 30
(when spilled In water)
t---1250 1 55 Methyltr lchlo ro •silane 30 100
0:. 0 . I 0 .3 0.2 I I 00 300 0 .9 I 0 .6 I 2.6 (when spilled In w;ater) - 139 Trichlorosilane {when 30 100 0 .1 0.1 0 .3 I • 2 60
I 200 \ o1 \ •4 22 r• 1295
spilled In water) 16 13 154 Hydrocyanic acid,
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, 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
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 water)
konrfn~
Mfli!il•f!F ln1t1al Isolation and Protectlvll!' -A ct1o n Dh ,tances (cont,nu SMALLSPIUS
IDNO. GUIDE
1680 157
1689 157
1689 157
1717 155
1749 124
1829 137
1829 137
1831 137 1831 137
19S3 I 119
1953 I 11 9
(FROM A SMAU PACKAGE OR SMALL LEAK FROM A LARGE PACKAGE)
FIRST THEN ISOLATE PROTECT
IN AU DIRECTIONS PERSONS DOWNWIND DURING
DAY NIGHT NAME OF MATERIAL m ft km mi km mi Potassium cyanide, solid (when spilled in water)
! ;~;~mi;;::~,cwhen I 30 I 100 I 0 .1 I 0.1 I 0.2 I 01 Sodium cyanide, solid (when spilled in water)
Acetyl chloride(when 30 100 0. 1 0 .1 0.3 02 spilled in water)
Chlorine t ri fluoride 60 200 0 .3 0.2 1.2 0.8 Sulfur trioxide, 100 300 0.4 0 .2 0 .9 0.S inhibited
Sulfur tr ioxide, stabilized
Sulfuric acid, fuming 100 300 0.4 02 0.9 0.5
Sulfuric acid, fuming, with not less than 30% free sulfur trioxide
I Compressed gas, I 100 I 300 I •. , I 0 3 I 22 I 1., flammable, poisonous, n .o.s. (Inhalat ion Haza rd Zone A)
I Compressed gas, 30 100 0.1 0 .1 0 .3 0 .2 flammable. poisonous, n.o .s. (Inhalation Hazard Zone B)
FIRST
lARGESPILLS {FROM A lARGE PACKAGE OR
FROM MANY SMALL PACKAGES)
THEN ISOLATE PROTECT
IN ALL DIRECTIONS PERSONS DOWNWIND DURING DAY NIGHT
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 35
400 1250 2.9 1.8 5.7 3.5
I ... I 2000 1 2.6 l u T 8~ \ 5.4
300 I 1000 l u I a.a I 3.s 1 2.2
(continued)
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1n1t1a1 isolation Protective- actionzone
Wind di rect ion
---- zone /
d "'''"'"''" v dlst,oce 1/2 downwind d istance Spj ll
Init ial isolation
zone 1/2downwind distance
Spill
lbl
FI GLI RE 10, 11 The. initial isolation zone and the p1otect1ve-act1on zone shown m (al and {bl, respectively, con- ).,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<tion of the f~ Re5pO(lle Gwdebook (1Na!>h1ngton, DC U.5 Departm!flt of Transportauon, zOll)(Stct'on 6 7) for small and large spills of matenab that pose a health hazard by !nhalauon
emergency scene in which persons may be exposed to dangerous, life- threatening concemra- 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.
The protective-action distance is the distance downwind from the scene that 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.
protectiv,e..actlon For purposes
of DDT regulations, the 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
protective-action zone For purposes of DOT
regulations, the area in which persons may become incapacitated, unable to take protec- t ive action, and/or incur serious, Irreversible health effects
SOLVED EXERCISE 10.7
S.,ow how an emergency responder uses TabIe 10 23 to 1dent1fy the 1n111al isolation and protectIve-actIon d1s- 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.
Solution: It Is first necessary for the responder to 1dent1fywhether this incident mvotves a "small" or a " large· !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<tIve•action distances in relauon to potential exposure to hydrogen sul fi de. These distances are listed m TabIe 10 23 as 1000 feet (300 m) and 3 5 mites (5 6 km), I~ 11<ely
When emergency responders are required to encounter a_ t~~c subst~nce, 1hey mu~1 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
Chapter 10 Chemistry of Some Toxic Substances 397
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I' cancu • A. large group ofdisease1character- ized by the uncon- trolled growth and 5preadofabnormal cell5
stanceoragentthat cancontributetocaus- ingtheformation ofa tumor in a living organ ism
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- 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 · .
h is usually crmcad ;: !:~ s:bstances, even if they do ~ot ex_hibit a 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.
Caution alwa}'S needs robe exercised when em_ergency responders a~e calld 10 a 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;
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 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.
10.17 CARCINOGENESIS 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.
In some instances, the onset of cancer may be traced co exposures to cenain agtms 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 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 :~;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-
' P mng ean dilofasc. O1w 12 million new cas.cs .1re di.1gno,cd ann1.1.1 ll y.
398 Chapter 10 Chemistry of Some Toxic Substances
nc predispOSit(on to"."ar_d~ con,tracting cancer from their ancestors In this text our con- 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
,es cancer are den 1 v:d from stud_ies conducted by toxicologists and epidemiologists.
,-:iu :a:::t?i~;~~:i: 1.0 varyi_ng' d~scs ?fa substance to determine . P g.tsts rev1e\\ hmoncal exposures of humans to
I ncedto dete
1 rn:ime whether the rate of development of cancer, if any, has
expose popu auons. 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)
corrupt them. They acl wi~h . vastly different potencies, differing in their abilities to : use cancer b)' as much a~ a nulhon-~old.
Although the mec~an~sm of carcinogenesis-the production of cancer-is not com- 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.
1 During the initiation stage, the_ genetic . ma1erial within a healthy cell or group of 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
thway by which cancer can occur ts established during the initiation stage. Overall ~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.
Cancer may also be initiated without exposure 10 any agent whatsoever. This hap- pens when _genetic errors occur natural!y during the replication phase of cellular behavior.
During the subsequent promotion stage, the damaged cell divides into new but 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.
I During the fina l progression stage, the damaged cells invade nearby tissues and 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.
Tobacco smokers represent a unique group of individuals for whom. 1he i_n_cidence of 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
cancer during which one or more h@althy cells are triggered to subsequently respond to the actions of a promoter
promotion• The sec- ond 5tage of cancer, during which the for- mation of malfunction- ing cells is accelerated to produce tumors
suethatpersists and grows independently of its surrounding 1truc- tures and ha5 no known physiological function
prog ression third stage of cancer, during which tumors evolve into malignant growth5 in the body
t ion of a malignant growth at one site in the body from cells derived from a malig- nancy located else- where in the body
Chapter 10 Chemistry of Some Toxic Substances 399
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syne-rgism • The ph~ nomeoon in which two ormorrsubn•nces int!'factinsuchaway that their combined effects are more severe th.nthesumoftheir individual effects
. ,· h h m. By so doing, heavy smokers assume a liferime risk of ac 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~
The emt'rgencC" 0 ru f the organs to carcmogens that are 1101 c lllal 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:
0 ~ er~:ces more profound effects 1han either carcinoge;:ct1on
of rwo or more caran;;no/may be evident b}' the onset of an adverse health effec-t O separa tt'ly. Tht' pht'nO It' smokt'rs exposrd to asbestos are more vulnerable to contra t'.icr
than cancer. For e~p . 'than are nonsmokers. Asbestos-exposed smokers are about ~lllg (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
like/~ to de,·elop testicular cancer, muluple myeloma (a cancer of the bon.e marrow), non. 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).
10.17-A CLASSIFICATION OF CHEMICAL CARCINOGENS 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.
The various procedures employed for the study of carcinogenic potentiality have pr0o 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
ifriii/.itl IARC's Class1f1cat1on of Carcinogens 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
1•Grace le,\fa~rers er al "Cancer r' k . . • Enwo11, Mrd., \'ol. 48 iioo6), pp. ~\sa:~;g/refighrm: A review and mcta-.-ina/ysis of 31 s1ud1es, /. Ot,:uP.
Chapter 10 Chemistry of Some Toxic Substances
iher ;1 subStan.ce causes cancer in th~ human organism. Research studies in carcino- 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
n rcinogen is known to be a co~slltu~n~ of a commercial product, some st:ue laws require .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.
O 17.9 WORKPLACE REGULATIONS INVOLVING CARCINOGENS !1b~n 1he use of ca rci.nogens is ~equired !n the workplace, OSHA requires employers to 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
ires employers to post m this area a sign rhat 1dent1fies the carcinogen and its physical ~:rds. For example, OSHA requires the area of a workpl ace where vinyl chloride is used to be posted as follows!
r--------, VINYL CHLORIDE
EXTREMELY FLAMMABLE GAS UNDER PRESSURE
CANCER-SUSPECT AGENT
\rinyl chloride is a human ca rcinogen (Section 14.6). To reduce or elimina te their exposure to carcinogens, emergency responders should
had this warning when they enter buildings in which carcinogens are stored or used. The)' also should heed the health hazard pictogram 1hat OSHA requires the manufactur- m, distributors, and importers of carcinogens to display on container labels.
In chis and future chapters, we recognize the carcinogens of immediate concern to emergency responders as they are first encoumered. 15
10.18 COMPOUNDS OF TOXIC METALS From a nutritional viewpoint, metallic compounds may be classified as follows:
Essential elements. Trace amounrs of 14 metals and metalloids are essential in the diet 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.
Toxic metals. Certain other metals and metalloids are nor known to offer any 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.
IJUnkss otherwise indicated the designations in th is m.:t arc those JcnotC'd by the U.S. Department of Health 1nd Hum,1n Services and the \x,orld Health Org.-inizarion's lnternanona l Agency for ResC'arch on Cancer (!ARC).
essential ellement Any element in the
human diet that Is needed for the proper functioning and sur- vival of the human organism
toxic metal Any met- als or metalloids whose consumption, even in minute amounts, can cause illness or death
Chapter 10 Chemistry of Some Toxic Substances 401
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lead-ba~p.iint • For 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
/· and rnecalloids may be either roxic or beneficial, dependin Certain oth~r mera ~orher factors. The}' include th e compounds of manganes,, & Ofi
rhtir concrnrr.1non aud . h exrrt a roxic effect or perform an essrntia! bi ! ~lr. nium, and tungsten. The}' can eH er o ogi~! function in che human body.
LEAD AND ITS COMPOUNDS 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
fires in old scrucru.r;-formerly were used as pigments in surface coatings to provide co! Lead compoun_ s am Jes of these pigments are lea~ acetate, lead chrornaie ot
and pre~·ent corros1':::~e~oatf'ngs are ca lled lead-based _paints . EPA banned the u~a~d lead oxide. T_he "/d ' s intended for residential use m 1978. of le:id:::r1 :c:~::~n
1 ~~ited States an estimated 38 million homes_ built before 1978
conrainin some lead-based pa int. When these srrucrures c?llapse during ongoing build. 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.
L~ad poisoning is the collecti~n of ~dverse health p~oblems caused by lead exPosutt. 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. . . . . . ,
Lead exposure in children also 1mpa1rs the1~ ab1ht) to lea rn and execute ~enral 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-
lNd poisoning• The larly ro their IQ measurements obtained as ad ults. This fi~dmg suggests that the ill 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
are disproportionately affected compared to children who live elsewhere. The lead-b.1Std 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.
Adults may also bt adversely affected by lead exposure. They experience reproductfre 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 /
1 and to the brain in parcicula~ ii
one of che most severe consequences of chronic lead poisoning. Exposure to certain lead 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.
Chapter 10 Chemistry of Some Toxic Substances
S CONSUMER PRODUCT REGULATIONS INVOLVING LEAD 10· 1
8 ~ published regulations 10 reduce or eliminate rhe risk of consumer exposure to lead.
CJ'S; ~~ R- S iJOJ.4, it ba ns lead in pa!nt and ocher similar surface-coa ting materials; toys /,.f !orher articles intended ~or use by children that bear lead-based paint; and furniture arti- ;itd
I t,ear lead-based paint. Ar 16 C.F.R. §1500.17, CPSC bans 1hesaleof paint having a
,kS rha cent above 0.06% by dry weight {other than artist's paint) in the United States. Jc3d~~rwithstanding CPSC's efforts, lea~-based ~ int has ~n used as a surface coating on
peciall)' those manufactured outside the United States. Furthermore, the lead content 10J"S, es • products is sufficiently eleva1ed chat the lead may cause adverse health
en who play with them. To minimize or eliminate the potential for lead en, CPSC set standards for both the lead in paint and the tota l lead content
ro •sand ocher produc_cs designed or intended pri~aril)' for use by children 12 years or ) r cPSC now requi res the manufacturers and importers of children's produces to test
,oun~e; :issura nce that they do nor contain more than 90 mg.lkg of lead. CPSC also requires 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
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, ~n;%r or batch nu mber. The following is an example of 1he required marking:
Manufacturer Toddler's Toys Date of Production: 9/10
Production Location. Port-au-Prince, Ha1t1 Lot/Batch Number 12345678
10.18-C WORKPLACE REGULATIONS INVOLVING LEAD 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:
OSHA also requires at 29 C.F.R. S 1926.62 that emplo~e rs indu_de the fol lo~ving infor- mation on bags or conta iners of lead-contaminated protecm·e c/01hmg and eq uipment:
CAUTION
CLOTHING CONTAMINATED WITH LEAD DO NOT REMOVE DUST BY BLOWING OR SHAKING DISPOSE OF LEAD-CONTAMINATED WASHWATER
IN ACCORDANCE WITH APPLICABLE LOCAL, STATE, OR
FEDERAL REGULATIONS Chapter 10 Chemistry of Some Toxic Substances 403
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Asbestos
REGULATIONS INVOLVING LEAD D ENVIRONMENTAL 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<l Paint Haza~d Re.ducno~-~::d Paint' Hazard Reduction _Act influences the ma~• In p;uticular, the res1dennal Lea h d Id. Some requirements include the followin . ner b . which housing is now boug tan so . g, } d d"sclose known lead-based pamt hazards in the 1 Sellers and _landlo~ sbr:~:t ~ts to buyers and renters. arg~
housing and proV1dc avai\ad po provide an EPA-approved lead-hazard inform . Sellers and landlor s mu5t 17 a11on . I h mebuyers and renters.
pamphlet to potenna O h b ers 3 10-day period in which to conduct a lead-b . Sellers_ must ~~:;~ss::~e~ of the target home. 3!.td
p:un~ 1~:t:~.o\:s::rs, and real estate agents share responsibility for ensuring comp\iaflet . h u rcable aspects of the act
Wlt a app \ . . . ed for all firms who intend to conduct renovation repa· EPA _ce~u 1cat1~n is rhe~u~;sturb lead-based paints in homes constructed befo;e l97i and repamnng proJects t a ,
Other environmental statutes, including the following, impact EPA's regulations concem. inglead:
Using the legal authority of the Clean Air Act, EPA regulates th~ concentration of 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.
Using the legal authority of RCRA, EPA regulates th~ t~eatmem_, ~torage, and di~ posal of lead-laden wastes that exhibit the RCRA characteristic of toxtcir~.
Using the legal authority of TSCA, EPA regulates th_c manner by whtch_ c_omraaors 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.
10.18-E TRANSPORTING LEAD 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.
We note the DOT requirements for transporting oxidizing lead compounds in Chapter 11.
10.19 ASBESTOS 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. '
When mixed with magnesium oxide, asbestos was formerly used for a variety of fire· 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
0 en mto Srrong, flcx1ble threads that could be converted into fireproof
l i An example is the EPA document • . . . S En1•ironmema\ Prot«rion Agency, !o~;~:c~;;;4\~~-::~~};_From Lead in Your Home~ (\Vashing1on, DC. U.
Chapter 10 Chemistry of Some To:,dc Substances
·cs. Although th~se asbeSt0S products once were _prized for their desirable feamres, their fJbrt .1. in roday s market has been sharply curtatlcd or entirely eliminated. a1\:l b1 ity
,, 9 A ILL EFFECTS CAUSED BY EXPOSURE TO ASBESTOS 10-
1 .• to the adverse health effects caused by exposure to asbestos fibers cypically has
i\{tcnt;:n six minera_l types: the serpemi~e mineral chrysoti/e (commonly called white asbes- focust' l,ite serpentme), and the amphtbolc minerals, cummingtonite-grunerite asbestos 10s or."\ riebeckite asbestos (crocidofite), actinolite asbestos, anthophy/lite asbestos, and \a fll
1 ~;;~:e 'asbestos . C~rysotile w_as th~ m?~t co~mon form of asbestos formerly used in the
1re1_ d Siaies. There 1s substantial sc1enufic evidence supporting the observation that cxpo- 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
en ~~aks apart into tiny fibers, ~u~h smalle~ and more buoyant than ordina':)' dust. oft _ curs when the asbestos-contammg matenal is damaged or disintegrates with age . T~is
0 ~d to be friable. It is friable asbestos that poses severe health hazards to those who
!t ~a~: or swallow its fibers. . 111 f' ure t0.12 illustrates that asbestos fibers may range from 0.1 to 10 micrometers m
~gand have a diameter of only 30 nanometers. They float almost indefinitely in the 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. . .
g Exposure to friable asbestos potentially causes the onset of the followmg diseases, typically after a substantial latency period ranging from approximately 20 to 40 years:
1 Lung cancer, the growth of malignant tumors in the lungs. Microscopic asbestos 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.
friable • Brittle or capable of readily being crumbled, as in friable asbestos
lung Cancer characterized by the emergence of malig- nant tumors on the lungs
asbestosis A scarring of lung tissue by asbes- tos fibers
mesothelioma The cancer of the mem· branes lining the chest and abdominal cavities resulting from exposure to asbestos fibers
1 Mesothelloma, cancer of the mesothelium, the protective membrane or sac sur- 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.
mesothelium • The pro- tective linings and sacs surrounding certain of the body's internal organs and cavities
pleural mesothelioma The cancer of the
protective linings surrounding the lungs and chest
Fog
Bacteria
Asbestos(lengthl
Finesend - 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
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
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countabl i! elongate mineral particle • Any mineral having the ele- mental composition and crystal structure of the forms of asbestos that cause cancer
evidence associ.:uing mesorheliom:1 in human_s. wi th :1sbestos exposure is 0\ w Because of this association, asbestos is class1f1ed as a huma_n carcinogen. tr.
h The flkeiihood rhar individuals wil! c~n.trncr lung cancer, ~sbestos1s, or mesotheho 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:
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. tract asbestosis.
These examples suggest that tob:icco smoking ~eakens the lu_ngs and prov ides 3 \·u]. nerabi lity to contracting asbestos- rel ated di seases that 1s not experienced bi· nonsmokers. '
10.19-B CONSUMER PRODUCT REGULATIONS INVOLVING ASBESTOS
The CPSC has promulgated regulations to eliminate or reduce asbestos in consumer 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.
10.19-C WORKPLACE REGULATIONS INVOLVING ASBESTOS
When rhe use of asbestos is needed in the workplace, N IOSH requires employers IO limit 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.
When asbestos is present in the workplace, OSHA requires employers ro post 1hesign 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
t- ·MMfl#i• ASBESTOS
AVOID BREATHING DUST CANCER & LUNG DISEASE HAZARD
t•·tVMii• CONTAINS ASBESTOS FIBERS
AVOID CREATING DUST CANCER AND LUNG DISEASE HAZARD
406 Chapter 10 Chemistry of Some Toxic Substances
19.D ENVIRONMENTAL REGULATIONS INVOLVING ASBESTOS 10 ." 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
~ 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 hed a program cited at 40 C.F. R. §763.91 in which each loca l educational agency is
~:~:~red 10 accomplish the following within their jurisdictions:
Inspect for the presen~e of friable asbestos in its school buildings • Determine whether frrnble asbestos fibers are being released into the air : Remove and repa ir all damaged :isbestos-cont:iining material
EPA also regulates at 4? C.F.R. S61.145 how the asbestos is to be stripped fro~ wa\ls, ceilings, and other locat\Ons. The proper abatement procedures include the following:
, Sealing a work site befor~ the asbestos-containing material is removed Preventing the asbestos fibers from becoming airborne by keeping them wet Removing, encapsulating, repairing, enclosing, or encasing the asbestos-containing material
1 Placing the asbestos debris in leak-right containers that subsequently are sealed Posting warning signs that contain relevant information noted earlier.
10.19-E TRANSPORTING ASBESTOS 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."
DOT also requires shippers to identify asbestos on an accompanying shipping paper as follows:
NA2212, Asbestos, 9, PG Ill
When bulk quantities of asbestos are transported, this shipping description is preceded by "RQ," because the reportable quantity of white asbestos is only l pound~ (0.454 kg) . .
DOT requires carriers who transport bulk quantities of asbestos by highway or :ail to 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.
Although DOT generalli· requi res carriers to post placards when using thfe shquared-on- . · h ·d "f t" number o a azar ous
pomt diamonds and orange panels to display t e I .ent.J ica ton CLASS 9 placa rds on the material transported in bulk , it does not reqmre earners to poSt
,·chicles used to transp?rt asbestos . 72 101 156
no tes rh ar these ttansporration ~he DOT regulauon at 49 C.F.R. §l h. b ·en immersed or fixed in a natural o r
req uirements do not a pply to asbestos that a~ e h I esins or mineral o re, or con- synthetic binder material, such as cement, p\::tStJC' asp a t, r ' rained in manufactured producrs.
Chapter 10 Chemistry of Some Toxic Substances. 407
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10 19-F RESPONDING TO INCIDENTS INVOLVING . A RELEASE OF ASBESTOS
D ice efforts to eliminate asbestos in buildings, emerg~ncy. respond:rs_are most like] . be~~ osed to airborne asbestos fibers as they combat fires mold bmldm~~- The pri~
3 1~
route ~f exposure route is inhalation of the ~ust generated_ when wa lls, ce1l1ngs, and rooi 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 . .
Firefighters also put their families an~ col!eagu~s at nsk of contracting an asbcstcs. 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.
10.20 PESTICIDES 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.
There are rwo cbemical rypes of pesticides: inorga nic pesticides and organic pesti- 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.
Although organic pesticides may be classified in several ways, we divide them inrothr foUowing four groups based on their chemical st ructures:
0 //
Carbamate pesticides, deri va tives of carbamic acid, HiN- \ OH
Organochlorine pesticides, ch lorinated deri va ti ves of ce rtain complex hydroca rbons (Section 12. I I
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Organophosphorus pesticides, deriva tives of phosphoric acid , Ho- 1;-oH OH s
Thiocarbamate pesticides, derivatives of thiocarbamic acid H1N-J , . I OH
Thi~ c.hemica l classification scheme is employed by DOT for generica lly describing organic pescmdes.
10.20-A ENVIRONMENTAL REGULATIONS PERTAINING TO PESTICIDES
To advise consumers of the hazards posed by exp "f • 'des EPA uses the 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
Chapter 10 Chemistry of Some Toxic Substances
o-B TRANSPORTING PESTICIDES 10,Z . d . . .
OT requires shippers an car~iers co 1d~nt1 fy the shi pping description of a pesticide on 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
h names of the principal const ituents that cause the pesticide to meet the definition of :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.
also requires s~ippers and carriers to comply with all applicable labeling, marking, and placa rding requi rements.
10.zo-C PESTICIDES AND FIREFIGHTING 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
:~~uld use self-contained breathing_ appara~us and _"".ear fully encapsulating suits. . . The common symptoms associated wnh pest1c1de exposure include blurred v1s10n,
h dache, vomiting, sa livation, and lack of coordination. These symptoms may be mis- rae:en by responders as those associated with hear exhausc_ion. . . .
Pesticide fires should always be fought from the upwind d1recuon or at nght angles. The use of fog is preferable to the use of direct streams of water because fog is less likely
raise coxic dusts. To protect the environment, the runoff water generated during the 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.
Mil\iii¥1 PESTICIDE Carbamate pestic ides, solid, toxic
Organochlorine pesticides, solid, toxic
Organophosphorus pest icides, sol id, toxic
Pesticides, solid, toxic
Thiocarbamate Pesticides, solid, toxic
Representative Generic Shipping Descnpt1ons of Some Sohd Pesticides
SHIPPING DESCRIPTION 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)
~N27S7, carbamate pesticides, solid, toxic, {ethyl carbamate), 6.1, PG 111 {Poison) UN2761, Organochlorine pesticides, solid, toxic {Endosulfan), 6.1, PG I (Poison)
~~2761 , Organochlorine pesticides, solid, toxic, (Endosulfan), 6.1, PG II (Poiso~) UN2783, Organophosphorus pesticides, solid, toxic (Chlorpyri fos), 6. 1, PG I (Poison)
~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) . UN2588, ' ' . "d I'd toxic (ethylenebisdithiocarbamic acid), 6.1, PG I (Poison) UN2771, Thiocarbamate pest1c1 es, soi ,
or . . lid toxic (ethylenebisdithiocarbamic acid), 6.1, PG I {Poison) UN2772, Thiocarbamate pest1C1des, so ,
or . . I'd t ic (ethylenebisdithiocarbamic acid), 6.1, PG I (Poison) UN2772, Thiocarbamate pest1c1des. soi , ox
Chapter 10 Chemistry of Some Toxic Substances 409
biological warfare • ~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
infKtious pathogen Any bacterium. virus,
or fungus that may cause a deadly d isease to exposed individuals
10.2 1 BIOLOGICAL WARFARE AGENTS 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.
An infectious pathogen consists of living bacteria, viruses, fungi, rickettsiae 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
. ~though ~he dissemination ~f inf~crious patho~ens or toxins could cause large-scale 1mpa1rmenr, disease, death, or b1olog1cal m a lfonct1on s amo ng the enemy, this warfa tcu.in • A poisonous substance produced by
a living organism or bacterium
practice has been condemned by civilized countries as unethical a nd inhumane. re As nored in Section 7.3-A, rhe League of Nations introduced the Geneva Protocol i
1925. Despite irs ratification by 130 nations, the mistrust and fear among nations han resulted in the production and stockpiling of biological warfare agents for defensiv; purposes.
ifrjijj,f}j Some Infectious Pathogens and Toxins INFECTIOUS PATHOGEN OR TOXIN
&cillus anthracis, a spore-form ing bacterium
&cillus cereus &cillus licheniformis Bacillus megaterium, a spore- forming bacterium
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 Section 10.21-E.)
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 Fatigue, loss of appetite, and other symptoms
~:af:~:~.s,~u~~~:a;:hzt~:J:: acquired ~y humans from infected animals; ch~racterized
Burkholderia pseudomallei
Clostridium botulinum (seven biotypes)
seizure· light ·r . ' rs, cheSt pain, muscle tenderness, weakness, weight loss; ' senSi Mty, pus-forming skin infections, diarrhea, and headache
Meli~dosis, a d isease similar to glanders and characterized by the same symptoms 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
(continued!
410 Chapter 10 Chemistry of Some Tox ic Substances
j!Hii.ft• Some Infectious Pathogens and Toxins (continued) \NfECf lOUS PATHOGEN OR TOXIN
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 biotypes)
Streptococcus pneumoniae
Vibrio cholerae
ADVERSE HEALTH EFFECTS CAUSED BY INFECTION
:~~e;it_ir the inflammation of the small intestine; gas gangrene, respiratory distress, ai ure of the body's internal organs
Tetanus(lockjaw)
Diphtheria, anoftenfatal respiratorydisease Q feve_r, characterized by chills, fever, coughing, headache, fatigue, hallucination, and sometimes chest pain
Ebola hemorrhagic fever, a highly contagious disease that has ended in death for 90% 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
~ever; m~scle ache, nausea, and diarrhea; can lead to meningitis, encephalitis, and intrauterine and cervical infections in infected women
Marburg hemorrhagic fever, a disease similar to but distinct from Ebola hemorrhagic fever but characterized with the same symptoms
Malaria, a mmquito-borne infectious disease characterized in the most severe instances by hot-and-cold sweats, hemorrhaging, convulsions, coma, and death Pneumonia
Smallpo1t, a hlghly infectious, often fatal disease characterized by high fever, head• ache, body ache, vomiting, and the appearance of a rash on the tongue and in the mouth that turns to blisters
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 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
Salmonellosis, characterized in the same manner as exposure to Salmonella enteritidis; in severe cases, accompanied by typhoid fever and hemorrhaging in the intestines .
Staphylococcus food poisoning, characterized by sudden severe nausea, vomiting, abdominal cramps, muscle pain, severe diarrhea, headache, fever, and chills
Pneumonia Cholera, an acute intestinal d isease characterized by a profuse watery diarrhea and vomiting
Yetlinia pestisb,c Bubonic plague, a disease associated with the production of ugly black. welts and bulges called buboes in the groin or near the armpits
'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- 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,
~:~;~:n~iol~gfcal Weapons and Americ~'s S~cre 1 ~::~e(~~:a~~~:B~~~~no:a;~h~~:~\~~:i~~~-,:~~t!·~ with k1H1ng 20 mlll1on Europeans during
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 urteenth century. The convent\ona e ie however scientists are seriously cons\derlng whether the Black Death was actually
<~~:~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 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.
chapter 10 Chemistry of Some Toxic Substanc.es 4 i 1
Bicterrorism Acts • The 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
select agent •For pur- 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
10.21-A SELECT AGENTS 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 <o imp,:/:• ability to prevent, prepare for, and respond rn ~cts of b_1oterronsm and other public he ut emergencies: The Public Health Security and B1oterronsm Preparedness and Respo a!th of 2002 and the Agricultural Bioterrorism Protection Act of 2002. They are refe~~dA~
here as the Sioterrorism Acts. 0
Using the authorities of the Bioterrorism Acts, the _U.S . Department of Health and 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, '
Those th.it potentially pose a threat to public health and safety. HHS publishes this list of selecr agents at 42 C.F.R. S73.3.
Those that potentially pose a threat to animal health and animal products, D publishes this list of select agen1s at 7 C.F.R. S33 l.3. A
Those that potentially pose a threat to plant health and plant products. DA ub- 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 <O animal o, into ,he envirnnm<n: ~vhere 1t cou_ld pr~duce a deleterious e_ffect upon animal or plant hea lth, the potential impact for high ~mmal or plant mortality rates, the potential impact for a major animal or plant hea_lth impact, and the likelihood for misuse resulting in mass panic or Olher forms of socia l or economic disruption. h The Bioterrorism Act regulations require r~searc~ labora tories and other facilities
t at possess, use,. or transf~r select agents to register with the appropriate federal agenC)' with regulauons published at 7 C.F.R. Part 33 1, 9 C.F.R. Part 121, and 42
10.21 -B DISSEMINATION OF INFECTIOUS PATHOGENS AND TOXINS Infectious pathogens and taxi , b I . . include ,he following: ns ma} e covert Y disseminated by several means tha1
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 • _1 an enc ose space or over a cit
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 . . Inoculation of fabric dr ~m_km~ water supplies ' paper~ an smular Items To maximize the adverse im act fro
pass_ aher _it ~as been disseminat~d. The me;tposure to a pathogen, a period of time 1niu 5 I
412
Du~mg 1h1s tune the pathogen enters the tod~d ma~ be_ h~urs, days, weeks, or even )~ar 5 -.
until the symptoms and ai lments of a dis ies of its v1ct11ns and multiplies cxponenu:111\ Ch . • case"' clearly evident. Dming chis incubano<
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- 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
Jr~ ~\edical authorities ~ategori~ally recommend the isolation of infected individuals 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.
The _isolanon of persons mfc~ted wit~ a cont_agious disease serves to prevent the spread 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.
10.21 -C RESPONDING TO INCIDENTS INVOLVING A RELEASE OF INFECTIOUS PATHOGENS AND TOXINS
Hazardo~s material tea1:1s are now trained to identify infectious pathogens or toxins even 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.
When a bioterronsm act has been committed, emergency responders need to cordon 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.
Areas contaminated with an infectious pathogen or toxin may be decontaminated by 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.
10.21 -D TRANSPORTING INFECTIOUS SUBSTANCES
infectio us substance • 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
Although the general public fears exposure to biological warfare agents, microbiologists 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.
DOT refers to infectious pathogens and toxins as infectious substances, and regu- lates their transportation as division 6.2 hazardous materials. Certain special rules apply
World Health Organiza- 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
that we note here. . 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
Provided in Table 10.27. Chapter 10 Chemistry of Some Toxic Substances 413
\\
diagnostic sprcimen • 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
ifriijj,Q Risk Groups for Pathogens RISK GROUP PATHOGEN
A pathogen that usually causes serious human. or 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
:;~:~~i~~l:h:~ ~:"a ':e~~~uhth:~~r~: :~~ma~!:!si;~e 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
A microorganism that is unlikely to cause human or animal disease'
'NotsubitcttoDOT reguJatlons.
RISK TO INDIVIDUALS
High
High
Moderate
None or very low
RISK TO COMMUNIT't High
Low
Low
Low
DOT regulates the transponation of hazardous materials in division 6.2 having ihe 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.
When sh.ippers prepare the applicable shippi ng paper, they are obligated to include 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:
UNITS
l glass tube (UN6PJ
HM
SHIPPING DESCRIPTION {IDENTIFICATION NUMBER, PROPER SHIPPING NAME, PRIMARY HAZARD CLASS OR DIVISION, SUBSIDIARY HAZARD CLASS OR DIVISION, ANO PACKING GROUP)
UN2~14, Infectious substances, affecting humans (Baollus anthracis), 6 2
WEIGHT (g)
Al~hough an infectious substance is not assigned a packing group it is packaged 10 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
Shipper or carrier's full name address and tel h b Proper shipping name includ'i h ' ep one num er UN number ' ng t e name of the infectious substance
414 Chapter 10 Chemistry of Some Toxic Substances
Cross section of proper packing
Name, address, and telephone number of shipper
FIGURE 10,13 When shippers offer an 1nlect1ous substance for transportation, DOT 1eq1,.mes them to use tnple packaging ,ompnsing a primary receptacle, water-tight secondary packaging, and rigid outer packaging
1 Precautionary statement 1 24-hour emergency response telephone number
The net quantity of infectious substance
In addition, DOT requires shippers to display the orange-and-black 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).
DOT also requires INFECTIO US SUBSTANCE labels to be 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-
BIO HAZARD
£ 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.
Carriers are obligated to notify the consignee and either the .National Response Cen· 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-
llous substance.
10,21 -E ANTHRAX 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
chapter 10 Chemistry of Some Toxic Substances 415
r
I
11
eo le and made 17 others sick. In 2008 , an Army scien_tist, the fede:al government's 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
The anthrax pathogen is not new to b1oterronsm. ~~nng . ' . oth Gern1an and Allied scientists developed varieties of anthrax bacilh, alrhough neither side ever actu- ally employed them as biological weapons. .
The bacterium Bacillus anthracis causes anthrax. The spores of the bacterium can be 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. . . .
The initial symptoms of exposure to the anthrax bacillus. are s1m1lar. to those experi- 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.
10.21-F RICIN 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.
The chemical analysis of ricin reveals that it is a solid polymer (Chapter 14). In war- 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.
The following incidents involving the use of ricin toxin as a biological warfare agent have been documented:
In 1978, Georgi Markov, a Bulgarian exiled journalist living in London, was jabbed 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.
When ricin is assimilated into the body, its victims experience fever, cough, shortness 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.
416 Chapter 10 Chemistry of Some Toxic Substances
