Hazardous Materials

f

518

Fi-Hii&@M·llli',I ~:~:: : ~: Chloroflu orocarbons II CFC OR HCFC OESIGN.::A:CTl.::CON::.._,__:C;__H<:-:M_IC:-::CAL N_A_M::-< :::-:-:-:-----,M_ OlECULAR FOR,_, CFC-11 Tnch lorofluoromethane I ~

I CFC-12 Dic hlorod1fluoromethan e

CFC-13 Chlorotr1f luorom ethane

CFC-21 I Dichlorofluoromethane I

CFC-113 / 1, 1,2-Trichloro- 1,2,2-trifluoroethane

I CFC-tt4

1

1.2-Dk hlo co-1, 1,2,2-l etca fl uo,oelhaoe

HCFC-22 ! ChlorodifJuo ro methane

I HCFC-123

1 2, 2-D,chloco -1, 1, 1-Jciflu o,oethao e

HCFC-124 2-Chtoro-1, 1, 1,2-tetraflu oroethane

HCFC-1 23a 1,2-Dichloro-1, 1,2-trifluoroethane

HCFC-134a 1,1 ,1,2-Tetrafluoroethane

Chapter 12 Chemistry of Some Haz ardous Organic Compounds: Part I

I Cl - ~ - CI I f

f I

ci- c- 0 I f

f I

CI - C-F I f

H I

CI - C- Cl I f

f I

CI - C- H I f

f f I I

CI - C- C- F I I Cl Cl

f f I I

CI - C- C- CI I I f f

Cl f I I

CI- C-C- F I I H f

f H I I

F- C-C-F I I f Cl

f f I I

CI -C - C- CI I I f H

f H I I

F- C- C-F I I f H

,\!though the CFCs served well fo r thi s b' . J(SirJb le featu res: They are among th e mostco~e !nation of pu rP? ses, they also have less

greenho use ga se s. The global warm ing po ~t ozone-depleung subs1ances, an d th ey ;;;01 5310 to 11 ,000 over a 20-year ti me ~:::n~ia~::

3 1he comme rcialized CFCs ~anges

arrnosphe re se.riuu ~ly exace rbates st rat ospheric ~zon u;e the. presence of CFCs m .our tn1·1ronmemal1Sts view positively th e restriction in thei; w:~i1:~~.~;e ::n~~~~t~r:a rm1n g,

12,15-A HOW THE CFCs DESTROY STRATOSPH ERIC OZONE The CFCs are extre mely stable compounds - h . . -long enough to be transported h Wit atmo_spheri c lifetime s of hundreds of ;~~: the ozone la yer, hig h levels of u:~r~i·~o~:~::~fa~:nc ozone l~yer. W~en their va~ors simpl~ r subs rnnces.

14 The ~FC mol ec ul:s absorb cer: ~: c1:~:l:n~~h:oof :~:":if1~::i1; ,~~ r.idiauon fr<:>m th e su n, .which ca uses their ca rbon-<:hl orine bonds to rupture res ultin in

the produ_cu?n of chlonne atoms, When a chlorofluoromethane molec ul e absorbs ul~ra - i·iol et rad1at1on, for exa mple, chl orine atoms are produ ced.

CF,,Cl, - n(g) -- CF~C1, -n- r (g) + :i:"J ·(g) A chlorofluomcaroon A chlorofluonx:artxin r.ld1cal Ch l;nnc ~tom

When these c~lo rine atoms are exposed 10 ozone molec ul es in th e ozone la ye r, the y react by the following three-step process:

0 3(g) + :c'l· (g) - CIQ·(g) + o2Jg) 0 1.onc Chlonnc atom Chl onnc n10no.1.1de O,)gc n

md1cal

Ch!onnc1r10110,1de 010111: nidic:il

CIO !(g) ----1- :¢) ·(g) + 02(8) Chl onncd10 , 1de Chlonncatom O.1. }'gcn

The first two steps of t hi s process result in the destruction of ozone. The actual ozone- destroying agent s are the chlorine atom and chlorine monoxide radical. The cumulative impact of th ese reactions in the upper atmosphere caused ozone holes to form, through which ultraviolet radiation could penetrate and travel into the lower atmosphere.

To protec t the integ rity of the ozone layer, the member cou ntri es of the Unit ed Nations have banned the production of CFCs through implementation of the Montrfol Protocol (Section 7.1-N ). In the Uni ted States, EPA has used the authori ty of th e Clean Air Act to ind ependently ban rhe use of chlorofluorocarbons as refrigerants, foam-bl owing agents, an d aeroso l propellants. Furthermore, the CPSC has used th e authority of the Federal Hazardous Substances Act ro ban the use of consumer products containing a CFC propel- lant. The impact of the combination of the se actio ns has led to the reduction or di sa ppear- ance of virt ually all CFCs from the commercial ma rketpl ace.

12,15-B HYDROFLUOROCARBON S AND HYDROCHLOROFLUOROCARBONS

When the use of chlorofluorocarbons was banned, chemical manufacturers sought 10 fi.nd envi ronment all y friendly replacements for use as refr igeram s, coolants, and foa~,-blo~\'. mg agents, Two groups of such transitional CFC replacements substances were 1dennf1ed:

J. Molina and F. S. Rowland , ~siratospheric sink for chloron uorome1hu1es: Chlorine atom-ca1al yied des tru ction of omn e," Nature, Vol. 249 (1974 ), pp. 810-812.

Chapter 12 Chemistry of Some Hazardous Organic Compounds: Part I 519

r

/1 I/'

I I I

/I

hyJro/lll orocarbons, or H FCs , and hydrochlo ro{lu orocarbo11s, or H CFC.s . HF cu/es hai·t onl y C- 11 and C- F bonds. bu1 H CFC molrcu/es have C- H , C- 1-. :inJ llloJ,. bonds. Examples of subs tances 111 th ese two gro ups arc datluoromc rh ane and chloro2 '('J romC' than e, respt,crn•cl y. n~o.

F I

H-C- H I F

(Hf'C. l~ J

F I

F- C-H I

Cl Chlon.xl 11l uon ,mc1hJnc

(l tCrf' 221

Jnirial scientific research s uggesred ch a~ mos t HFCs a nd H C FCs were desrro, d . a rmosphere ar low a/rirudes and did not s1gnificanrly diffuse upward to the oz~~e t '.ht Wh en rh is initial information could no r m:-_corrobo r:it ed, however, 190 counrrieso:~: United Nations agr~d through rhe Montreal Protocol to phase o ur rhe product use of aH HCFCs ocher than rho se used as refrig erants by 20 15. T he protocol ter:~;

1 ~

che production of all HCFCs by 2030. Sever:il HCFCs have a/read~ been specifica lly banned by EPA for use as refrigerant

gases, coo/anrs, and foam-blowing age nt s. Fo r examp le, HCFC - 14 J b (1, l -dichlor0- i. fluoroethane ) was banned in 2003, and H CFC- ~42b ( l -ch loro- 1, 1-difl uoroethane) and HCFC-22 (chlo rodifluoromet hanej were banned m 20!0 although EPA pe rm its rhtir uS(' in tq uipmenr manufacrured before 2010. Sevtral HCFCs ?1a y be used as EPA -approi·(l! halon subsriru res (Section 12. 15-C) for now. The production and use of rhe HFCs h,n t nor ye r been resrricred.

The HFCs and HCFCs are nor only ozone-depleting subs tances; they are also gretfi • house gases. The global w:i rming potential of th e co mm on H FCs and HCFCs rangts from 43 ro 12,000 and 273 ro 5490, respectively, over a 20-yea r rime period (Sec tion 5.8).

Several HCFC replacements have betn sugges ted by chemica l manufacrurtrs, indudmg J, J, I ,3,3-penufluoropropane and the hydrofJuoroolefins (HFO), 2,3,3,3-reuafluoroproprne trans-1,3,3,3-tetr:afluoropropene, and Jrans- l -chloro--3,3,3-tritluoropropene. EPA apprm·td the use; of I, J, 1,J,3-penrafluoropropane as a refrigerant, coola nr, and foam-blowing agenc and 2,3,3,3-rerraalluoroproptne as an auromoti\'e air-conditioni ng refrigera nt.

F H F I I I

F- C- C-C- H I I / F H F

J.J . J_l.J PcniJ nuorop rop.:mc (llfC.2.i5J)

F H \ I C= C I \

I-I CF1 1ran.r·I.JJ.J. TctrJnuorop rofl("nr

(lff0-123~,~,

F F I I

Cl l2= C -C- F I F

2.3.3.J-Tcu,, nuorop,o~nc WFQ . 123.i)f)

C/ H I / C= C I \

H CF3 1ranJ-I-Cl!roro-J.J.l. tnfluoroprop,.•nr

(Hl'0- 1233 ,d)

In 2011, auromake rs first bega n to consider replacing HFC-1J 4a wit h HF0-123 4yf as rh e air-condiri?ning fl~id in new-model ca rs. Although HFO - l 234yf has a GWP of 4 over a JOO-yea r nm e homon, .rh e autom.:1kers used ir ro replace HFC-l34a , which ha~ ~

?f 1_430 o~e~ rhe same rime horizon. Howe ve r, rh e use of HFO-l234yf as an~ir· c

nd u,omng fluid 1~ not p roblem-free: Ir is a flammable gas, causing au tomak ers ro b(

cinc ern ed th

ar l~ak mg HFO- J2 34yf may ca use a fir e during a head-on collision, f ur· t ermo re, when mh aled at elevated concentrations, HFO - l 234yf causes as ph rx iarion and central nervous sysrem disorders.

520 Chapter 12 Chem istry of Some Hazardous Organic Compounds: Part J

12,15-C SUBSTITUTE~ FOR THE HALON FIRE-EXTINGUISHING AGENTS A firs t noted 1n Sec11on ) . 14, H:i lon l 30 J (b bs 0111oc h!orod iflu orometh :i ne) once W~re ro

1 mot~ifl uoromc tha nc ) and Hal on 1211

( r r11pk s of brom of111 orocarbo"s or BFCs popdu ; r fi re extmguis hm g age nt s. The y arc ~:pect1vel y. As pre,·io usly noted, 'clean Atr' ~:t r/~'[~od,lorofli. oroca r~o11s, o~ BC FCs , ducuon and manu fa cture in Janua ry 1994 . g lions banned the,r Ame ncan pro-

Et\::: r~itc:~";~r t~,\~i~ ~i !n umber of co~mercia! fire C'Xtinguishing agC' ms that :~e s~bs1iruu agenrs are subj « r 10 n::r:;_r::e~;~~

1 ;s~: fo: .nonres1dent ial uses onl r,

ozone .nor contribute as,s~s n'.ficant [y to global warmm~ as (ol!owmg: HCFC- l~ J f-,--di chloro-l ,1,1 -trifl uoroethane ), HCFC- 124 (2-chro ro -1 I I l . lt'tr.1fluoroethan~), I lalotron I, HFC- 227ea, HFC-236fa , and Nov« l2 J0. ' ' ·-

F F F FF F F F F I I I l I I 1 1 I F-y-y -y-F F-r-r- ~ -?-?-F F -C-Cl-1 ,-C- F F 1-1 F F F O C F1 F } - }

U,! .: .J~ ;~J~~~~~e~•opropan~ I , J. l,].2.-l.5,S.5-Non:~~~~tn 1 ~~~-thi 1._ 3 ~ntano~c 1.1.1.2-3 :i:;g;~:~:tirrorane

Ha lotron I co~sim of a th ree -component propne1ary blend based on HCF C- 123. It is most commonly d1schargC'd as a Streamin g agent. Following use, it do es not lea,·C' a resi• du e. Halo tron I ha s hecn approved by the U.S. Coast Guard as a halon substi rut e fo r maritime application onbo3rd w:itercraf1.

The Federa l Avia tion Adminis trat ion has :ipproved HFC-22 7ea and HFC-236fa 35 fire-e xtinguis hing age nts to replace Halon 1211 . The agent s may be used not onl y onboard

Jircra ft , but 3lso on re sc ue and firefighting \'e hicles. Ai rbus uses onl y HFC-236fa, but Boeing uses both J-IFC-227ea and HF C-236fa.

12.15·0 STORING OZONE-DEPLETING SUBSTANCES Owoc-depleting sub stances, including the CFCs, HFCs, and HCFCs, are s1ill likely to be encountered toda y wit hin storage conta iners and tanks, especia ll y at facilities 1hat rece1 vtd an exemption from EPA or those th3t nt3i ntain, repair, or dispo se of refr ige rat ion and air- co nd itioning equipment. When an ozo nt-depleti ng substance is stored, EPA regulations requ ire it s ow ners 10 mark their comaincrs and tan ks wi th 3 warning statement that reads as fo llows: "WAR NING: Contains !or manufactured with, if app licable] [insert name of substance /, a subs tance which harms public health and en vironment by destroying ozone in the uppe r atm osphere." For exa mpl e, at 40 C.E R. S82. 106, EPA requires ow ners of HCFC-22 to mark their co nt aine rs and tanks of chlorodifluoromethane as fo ll ows:

CONTAINS CHLORODIFLUOROMETHANE (HCFC-22), A SUBSTANCE WHICH HARMS PUBLIC HEALTH AND THE ENVIRONMENT BY DESTROYING OZONE IN THE

UPPER ATMOSPHERE

Thrs statement serves 10 assist first-on-the-scene responders who encounter .ozon e- de~leting imb scances in storage. To pro tect r.he environment, they n~t~ s~era;;e ~:~:a~::t,~e:'~~~ht: pre \•~n.t th e rupture of these con~ame rs and t~nks; fo\~

1 ~:n 'tur; doe~ occur, eme rgency

prodigious volume of water durmg an. ongomg fire. confinepthe contaminated water fo r res ponders should implement appropriate measu res to su bsequent co ll ection.

Chapter 12 Chemistry of Some Hazardous Or ganic Compounds: Part I 521

I I 11

522

ii·+l&ilfflih' t1ons of Some ReprMen tatt\le CFCs, CFC. HFC. OR HCFC ---- - Bromotr,fl uorom,thane

I-ChJoro-l,l<Q1fluoroethane

----- l-Chforo-1,2,2, 2-tetraffuoroethane

Chlorotriffuoroethane

1, 1,1,2-Tetraf!uoroethane

1,1,1-Triffuoroethane

SHIPPING OESCRIPTJON

UN1009, Bromotrifluoromethane, 2 2

---.._

" UN1009, Refrigeran1gasR-1Js1, 2.2 UN2~ 1, 1-ch/~ifluoro~ne~, M • . J

---i UN2517,Refn~as ~ J~ ~ 1 NT021, 1-Chloro-1,2,2,2-tetraffuoree~

UN1021, Refrigerant gas R-124, 22

l UN1022, Ch lorotr ifluorom ethan~ Jo,

UN1 022, RefrigerantgasR -1 3,2.2

UN3l5 9, 1,1,1,2-TetrafJuoroethane, 22

UN3l 59, RefrigerantgasR-134a,22

/ UN2035, 1,1,1-Trifluoroethane,comp~ ( M '

/ UN2035, Refrigeran1gasR-143a, 2.1

12.15•E TRANSPORTING CFCs, HFCs, AND HCFCs When shippers offer a CFC, HFC, or HCFC for transportation, DOT requires rhem ro idenrify th e appropriare commodity on an accompanying shipping paper rit hf'r by usmg irs IUPAC name or .. Rcfrigeram gas R-Ut.\")'Z, .. where rhe meaning of the suffix WX)'l wa

5 nored ea rlier. Some examples of the shipping names for several represe nrarive CFCs, HFCs, and HCFs are provided in Table 12.18.

Wh en carriers transport CFCs, HFCs, or HCFCs by highway or rai l, DOT requirf'! them to display the wo rds "Dispersant Gas" or " Refrigerated Gas" on two opposing si des of th e rransporr ,,chid e.

12. 16 POLYCHLORINATED BIPHENYLS I Th e polychlorinated biphenyls, or PCBs, are th e chlorinated derivat ives of rh e complex hydrocarbon biphenyl, which ha s rh e fol lowing molecular sr ru cture:

00 There are 209 strucruraJ isomers of th e PCBs, each of which ha s t~e chemical ~ormu~ C11 l·lxCI; , where x ranges from Oro 9, and y equals JO - x . Approximately 130 ,some d we re components of rh e PCB products manufactured and marketed throughout the worl from the J 930s through most of rh e l9 70s

Ar ordinary ambient conditions, produ~ts containing PCBs usuall y are viscous, sricky liquids. faen ar ele va ted temperatures, rheir individual componenrs are nonflam~J ble, inc redibly stable compounds that can be heated ro th eir res pective boiling poin ts with~ur undergoi ng decomposirion or bu rsting into flame. This combin:irion of prop erries

Chapter 12 Chem istry of Some Hazardous Organic Compounds: Part I

fo rmerly was considered ideal fo r implcmentin cen . . high 1en1pcrarurcsand fi re resistance. g ain mdustnal practices that required

In ihe 1960s, however, 1hc PCBs first be c0n<luct t'd on ammal s. T~ese studies pointed ;:~~~h\focus of seve ral sc1enrifi~ ~rud 1es subs1:1 nce s th,ll do nor biodegrade in the environ

1 t t _e PCB.s are extraordinarily ~tabl e

udies also showed tha t PCB exposu re co !d n ent, th:1t 1~, they arc pe rS/5tent. The s~Jor:1cne (J disfiguring skin condition that u ca~lse cancer, bmh defects, liver damage, ; m these stu dies, we also learned that rese~ es severe acne ), 1mpotenc~, and death. r~oepror tissues o~ th e thymus, lungs, sp];;:,e ~;::;;1:\i~he PCB_s mig rate into \'anous ll'here they are primarily re ta ine d or bioaccumufate~ 'in t~r, brain; muscle, ~nd t~sc es, rdease from th e fatty ti ss ues has been linked with a . ef body~ fat. ,!heir ~wod1c and bin h ~bnormal~ties. For example, children who :::;::x~:;~r: ~~~ 1

1 ~:\sd~sr°; t~:

during _their mo th

er 5 pregnancy often are born with reduced motor ski ll s and sbort• term memories.

Tod;\ w~ ~o~\' kno\~ that PCBs ca use ph ysiologica l d1s~ rdm by mimick ing the action° t e O Y s own orm_one! or by inttrfering with their norma l functions. Hor- mones ar e subs tance_s ~~creted m minute quamities by th e endocrine glands, the organs rha r com r~l such 3Ctn·it,es as growth , development, metabolism, and reproduc tion. When Jbsorbed 1~to the bod)'., th e PCBs like th ese hormones, sending false signals that interfe re _with th~ bo?y s normal aCt1vn1es. Th ey are exampl es of endocrine disrupters. Gi\·en tlus ~o mbmatron of ad\'e rse properties, PCBs are rnnked by epidemiologists as huma ncarcm oge ns.

12.16-A USE OF Pees IN ELECTRICAL EQUIPMENT

I

from approximarely 1930 10 1977, product s conta ini ng PCBs were ma rketed for com- mercial utilization within crrtJin types of electrical equ ipment such as tran sformers, vol t- age regubtors, circui t brrakrrs, capaCl tors, motors, electroma gn ets, reclosers, cables, and fluo rescent light ballasts. They were also mJnufactured as hea t-tran sfe r, hydraulic, lubri- cating, and cutt ing fluid s. PCBs were al so used to manufacture carbonl ess copy paper, and ,hey were incorporated as constituents in certain plastic, paint, wax, and rubbe r prod ucts. ln all th ese instances, the purpose of the PCBs was primarily to provide these commercial products wit h a greater degree of fire resistance.

Beca use PCBs pose an unreaso nable risk to public health and the enviro nment, EPA ba nn ed th ei r rnanufo cr ure, sal e, impo rt , and distribution in 1978 by using the legal amho nt)' of TSCA. The rele vant rrgulations are published at 40 C.F.R. S76l et st_q. Al though th eir producrion and manufacture is ba nned. in the United States, _EPA pe rm its 1he in definite use of PCBs in systems that werr opera11ng before 1978, albe11 under spe•

hormont • Ach emlcal subst;mceproduced ln minute amounts by an endocrine gland and carried through the bloodstream to target organsoragroupof cellsofthebody,where it regulates growth, reproduct ion, and other biological funct iom

duct lessgland,sucha1 theadrenal,lhyro id. and pituitary glands, that secretes fluids directly Into the gen• eralcirculatorysystem t nd ocr ln e dls rupttr

compound that mim ic.saho1moneor Interferes with hormonal actionwhenlngested into the body

cific regularory conditions. Even today, PCBs can be lega lly used in a "toiallr enclosed dlt !t ct ric fl uid • The man ner," th at is, within equipm ent that ha s bee n designed Jnd consti:ucted.so as t~ ens_ure fluid used in cenain rhat no human or environmental ex posu re to rhem occurs, When th1 s eqUt_Pme!it is wi th_ types of electrical drawn from service or repaired, EPA requires rep lacement of the PCB flmd wuh a non- ;~~r:~~t~~~tt~ease PCB-co nt ain ing alternati ve producr. II I d One type can arcing and serve as a

An e!ecrri ca l transfo rmer is an example of a tota Y e~c osc . S}'S tem. · · heat-transfer med ium ohen be observed near the tops of electric po!~:ft is a sr:ir dev:::tc~v~~:~s~~~~::nh~s t~ PCB transform er . For transfe ~ elec trica l energy _ betwee n ci rcuits ~f winli~enst ovroc:~r~f a metal suc h as copper. purpom of TSCA regu- magnet1c core around which there are s:vera .

1 • h g ·mmersed in a flu id within a tank. lations. a transformer

This assembly of co re ~nd cur rcnt- c~ r~m;;,c~l~~~s :s :: :ncrease che resistance of the unit :~~:~n~i:~ 1 ~;~~~:~id

The pu~pose of _th e fluid, ca ll ~d a d1t e~-rransfe; medi um. Large numbers of sue~ trans- nated bipheny(s at a to susramcd arcing and to se n e as a e? d by municipal uti lity companies. concentration equa l to fo rme~s a_re loca ted at elccrricJI sub:atr~~fa~:~:,r~PA defines 3 PC~ transformer a1 40 or meed in g 500 parts

Wuhm rh e contex t o( rh ee;;~t : :~rain s PCBs at a concentrnnon of 50 0 pamper per million C.F. R. S761.3 as a rr.rnsform . H dous Organ ic Compou nd s: Part I 523

Chapter 12 Chemistry of Some azar

II

524

min e r a l o il transform e r •AA@'lectrie.tl trani- former conta in ing m ineral oil as ,ts

million o r g reater. A 1ypical PC B tra nsfor me r co nta ins approxuna td , ( 1500 LJ of fluid with a PCB concen tra tion of approximately 50 % to 60; -io ga l] 0n bu r a forge PCB tran sform er may hold .as much as .1000 ga llo _ns (7500 L) ~f ; ~\:lurr.r'. The remaining 40 ro 50 % cons ists of d1J ue nt s, a m ixture of tn c hlo ro bcn ze ne a nd tl 111d, chlor obe nu ne iso mers. rt r;i.

die le-ctr,c fl u ,d

PCB-<on~minated ttarufo~r • Fo r pur- po~ of TSCA regula- t ions, a transformer whose d ieJKtric flu id conta ins polyct,lor, - n.tted b iphenyls at a concentra tion greater than SO parts per m il- lio n but l~s than S00 parts per million

The vasr majoriry of t~nsfo~mer~ m se_n •ice r~~y were m.:mufactured with the int using mineral oil as thetr d,electrJc flwd. Mm eral 0 1] 1s a pe troleu~-based o il, and th etii ot an- called mineral oil transformers. Alt.hough PCBs we re ne ve r intentionally add/se lln1tl minera l oil used in these transformers, the oil ohen became conraminared with PC d to ~ workers conducted routine equipme nt mai ntenance .on both tran sformer ty pes ll~tn"/itn sa me hoses and pumping e~u.ipn_1ent. EPA ~efine~ a unn a_s a PCB-<on ta minated tran sfo~ thr when sampling and analysis indicates t.h:r its flu id conta'.n~ PC Bs at a concentration &rei~' than 50 pa~ per million but less th_an .>00 pares pe r m1Jl1o n. A non -PCB transtorrn,r t unit contairung PCBs at a concentration equal fO or less than 50 ppm.

no n-PCB transform er • For purposes of TSCA regu lations, a trans- former who~ d ielectric fluid cont,1ins polychlo- rin ated biphenyb at a concentr•tion equal to or less than SO parts

1 2. 16-B PCBs AND FIREFIGHTING AJrho ugh PCB fluids do no r rea dily burn, rh ~y may ignite ~i th'.n. an ene rgized lransformrr whe n high-energy arcing, elt"CTrica l o~e rl oadmg, o r s~ort-c1rcumng occu rs. These fires arr characterized by la rge amounts ~f 01/y, blac~ s':>o t rn r?e _accompanying smoke plumr Wh en the energized transformer 1s loca ted wnh m a buildrng, t he soo t and PCB va · travel w'irh the smoke p lu me throug h ve nti lat ion sha fts, building ductwork , and

0 :,~

per m illion

open-constr uctio n areas. Today's fi refighters respond ra rely fO PCB tra nsfo rmer fires, but beca use rh r scn·ict

lifetime of a transforme r is 40 to 85 years, such an action is not ou tside the real m of possj. bi /i ry. Firefighters are faced with an unwa r ra nted heal th risk when they are exposed to Ulf smoke from these class C fi res. To red uce the ma gnitude of the ri sk, EPA req uires the O\\n• 1 ers of the PCB transfonners to prominent ly affix the ML ma rk ing shown in figure 12. IOso that it is easily read by firefighting person nel who respo nd to an electrical-eg uipmem fur. EPA requires the Ms marking shown in Figu re 12. 10 to be affixed ro PCB eq uipmcm 1hJr can not accommo date rh e larger ML ma rking. EPA a lso imposes mandatory reponing requiremenrs ar 40 C. F. R. S76 1.30 to ens ure that the Na tiona l Respo nse Cemer (S«tion l . 13) is contacted immedia tely on the occ urrence of an accid enra l fire in vo lvi ng PCBs.

EPA also imposes reporting req uiremenrs on the owners of facili ties tha r still use dee· trical eg uipmenr conta in ing PCBs. Fo r exa mpl e, EPA req uires the registration of PCB transform ers, incl uding o ur-of-service transforme rs held in sro rage fo r reuse. Fir e depart· ment pe rso nne l should identify the location of th ese tra n sfo r mers with in thc- ir area of jurisdiction an d p lan a response actio n in case of an accide nta l PCB release.

When PCBs unde rgo incomp le te com bustion during t ransfo rm er a nd o th er electrical· equipme nt fi res, they p rod uce the highl y toxic compo un ds ca lled polychl orina ted dibenzo, fura~s and !'°lychlorinated dibenzo-p-diox.ins (Section 13.4-B). D uring electrica l-equipm ent fires mvoJvmg PCBs, these subs tances a lso may be re leased into th e enviro nment. Firefight· ers should b_e especia lly wa ry when co mbat ing elec trica l equi p m ent fires, beca use exposurt co rhese toXJ~ substa nces could ca use long-term ill effec ts. Rega rdl ess o f the magnitude of the fi r e, fU"ef1g hrers shou ld always wea r self-conra in ed brea thing a p pa ra t us to elimin:lfeor red uce th e potenrial for expos ure to these s ubstan ces. Pub lic h ea lth ca n also be effec ri\·dr p rotected by constru cting suitable d iki ng, d ive rsion cu r bi ng, or g ra di ng to confint th e sp read ?f ~ese conra rn ina nrs and prevenr th ei r d ra inage into sco rm sewe rs.

1 ~ fi re im•? lvi ng elec trica l equi pme nt is no c th e o nl y type d urin g whi ch PCBs, polr·

c hl orm ated d1 benzofura ns, a nd polyc hl o rina red d ibe n zo-p- d iox ins m ay be rde.ase~- Before 197 7, PCBs we re components of some p rotecrive and decorative pain rs, \'armshes, lacg u~rs, sealanrs, ad hesi\•es, ca ulk ing, and s im il a r co nstru ction p rod ucts. Some of th ,m co nramed 5 % to 30% PCBs. Altho ugh th ese products were used severa l decades ago, ,he

Chapter '2 Che mist ry of So me Hazardo us Organic Co mpou nds: Part r

CONTAINS

IPolvchl ~ ,S~B~ph,oy1, 1 ~ ;s:\.~ Atox,cenv1ronmentelconte special hendl,ng and disposa7l~ent r~qulrlng

'' ;;~~~t~o;~~ 1 CtRm7~n1t~l:~~~1~g~~r:

'' Jnf?rmetroncontact the nearest US E p Off,ce. . . ·.,A, ~

~ U lo 5case of ecc,den1 or sp,11, cell toll free the · · Coast Guard National Response Cente r: ~, 800--424-8802 '-.

Also ~,

~~(""

f lGURE 12

- 1

0 The~e two EPA markin gs are calle d the M t and M, markings, respective ly Th ey differ on ly by the,r wording and s,ze The le tters and strip ing on both mark,ngs are b

1 acl:. on a yellow backg round and ,nclude the warn ing CAUTION CONTA> NS PC Bs and instruct,ons

to be 1mpiemented m t he event of a PCB re'ease The M, mark ing also ,nd udes the telephone number of the Nat,ona! Response Center Th e TSCA regu lat ,on at

4 0 C FR § 76 1 4 5 requires a mar king to be affixed to PCB transformers and PCB capaotors 1n seMce and PC B ,terns

con:a ,n1ng or contam inated w ,th PCBs •n storage for disposal when t ~ PCB concentrat,on 1s eq ual to or greater than so parts pe r m,llton The regulation a lso requires t he marl:.1ng to be aff,xed to all doors or accesses leading from the outermost door 10 the door 1mmed 1ately ,K(USin gthePC8umt

PCBs st ill remain in surface coa tings, joint sealams around wi ndows, caulk ing between maso nry pane ls, and elsew here. As fir es occ ur in the buildings in whic h these PCB- conia in ing prod ucts we re once app li ed or used, the PCBs and the ir incomplete comb us- tion products a re re leased into th e environment.

12 .1 6-C THE AD VERSE IMPACT ON THE ENVIRONMENT CAUSED BY PCBs

Why are PCBs regarded as ult ra- haza rd ous substa nces? The answe r to th is qu estion is linked wi th th e ho rrifi c impac t they could have not only on pub lic hea lth but also on a wide segme nt of 1he en vi ronm ent. The wo rst PCB-conta mina ted site in the United Stales 1s a 200· mile stretc h o f the H udso n River in New Yor k nort h of Alba ny. An estimated 1.3 mi ll io n po un ds (-0.6 million kg ) of PCBs was all eged ly dwnped inro th e rive r by an el«rrica l•transfo rmer man ufactu rer from 1947 to 1977.

The adve rse envi ro nm ent al impact fro m expos ure to PCBs is li nked wilh its passage from anima l co ani ma l. W hen PCBs are co nsu med by a n ani mal th at is then e~ten by anot her anima l, th e PCBs pass progressively through the food chain: worms to. f.' sh and birds; fis h to birds; and birds and fis h to mamma ls. T his process is ca lled biomagnif1catlon, or bioamplification, beca use the PCBs increasi ngly concentrate .3~ t hey pas~ up_ th e f~od chain, T he PCBs may th ereby affec t the we ll -bei ng of many ind1 v1dual ~pec1es, md ~dmg humans who co ns ume fi sh or mea t co ntami nated with ~CB~. 1n th e Unned States a ~ne, EPA has id ent ified 703 bod ies of water where hea lt h adviso ri es have been posted to \\arn

peo ple against consumi ng PCB• ridhde ~ ~i_s~. d fis h ? The answer to th is questio n ce nte rs H?\\'. do PCBs affect tl1~ hea lt \':rc;::~med PCBs become sexuall y dysfunct ional.

on rhe1 r immu ne syste ms. Fis h who 3 • • the m to experience a reduced The fe ma le fis h a re born wi th immature ova ri es causing

blomag n ifi catlon (bloampliflca tio n) • The retention of a sub· stance in human and animatt lssuesat Increas ingly higher con• centratlonsasthesub· stance passes through success ive leve ls of the food cha in

Chapter 12 Ch emistry of Some Haza rd ous Org anic Compounds: Part I 525

I r l r I I

526

PCBs

. , Boch fish and birds who ha\'e con.sumed PCBs experience &row ab1l1cy to s;aw~. amnent. In birds, these pr~ble_ms m~lude _cggs_hell thinning, lowtb iJld r:~~:i:~:('d::eased egg hatching, deformi'.1cs m the JU\'emle birds that doernerg:;rtgg

s and reduction in their growth and surv1\•a l rates. . . . °Ill gg i-he em·ironmentol impacr from exposure to PC~s 1s especia ll y ev ident in

3 u

an ·sms Within the ocean hierarchy, for example; killer whal~s are :ontarninareJ it!( ~lBs :c c~ncenrr.uions higher than chose obse~\'Cd m other marine anunals ~a use ~th arc at the top of the food chain. Although herrmg may ca rry PCBs_ ac an average conceey trarion of onl)' 1 part pe r million, the seals _rhat eat chem may conta in 20 parts per miUi n. and the killer whales that ear cheseconcam1nated seals may have PCB level~ a~ highasi~ am r million. The male killer whales carry r_he P~Bs throug?our th eir li ves, but tbt

imal::periodicaJ/y rid these pollutants from their bodies by passing them to thc-ir call-~ This couJd explain why the mal es live_ on_ly half as long as the females, and wh>• ITld~~ calves die within Se\'eral months of their birth.

12.16-0 FDA REGULATIONS INVOLVING PCBs Because PCBs have become an unavoidable co~rami~ant in the environment, FDA pu ~ lishes the following tolerance limits for PCB residues m foods , at 21 C.F. R. Sl09JO:

1.5 ppm in milk (fa t basis) . I.5 ppm in manufactured dairy produm (fa r basis) 3 ppm in poultry /fa t basis )

: g:J :~ ll:J:hed animal feed for food -producing an imals {ot her than feed concrn- trares, feed supplements, and feed premixes) . . . . 2 ppm in animal feed components of anima l ongm, mcl ud mg fis hmet1 l and orher by. products of marine origin and in anim_al fe e~ concentrates, feed suppl emc-ms, and feed premixes intended for food-prod ucing an_1mals 2 ppm in th e edibl e portio ns of fis h and she llfrsh 0.2 ppm in in fant and junior foods

12. 16-E TRANSPORTING PCBs Whe n shippers offer polychlori na ted biphenyls for transportation , DOT re~uires them 10 identify th e PCBs on an accompany ing shipping paper as one of the follow mg:

UN2315, Polychlorinatcd biphcnyls, liquid, 9, PG II (Marine Pollutant ) UN2315, Polychlorinated biphen yls, solid, 9, PG 11 (Ma rine Pollutant)

DOT also requires them to affix CLASS 9 labels on its packagi ng. When bulk quantit ies of PCBs a re transport ed, DOT requires th e ide nti fication

number 2315 to be on displayed on orange panels or white squa re-on- point diamonds on th e packaging. DOT do es not require CLASS 9 placards to be displayc-d on rhr transpon vehicle.

When shippe rs offer a PCB-conraining electrica l unit including a PCB-co nt amina_tcd transformer fo r tra nspo rtatio n, EPA requires th em to affix the app rop ri ate marking shown in Figure 12.1 0 on the unit when it is transpo rt ed. EPA requires this mark in~io~ affixed on an elec trica l unit e\•en when the fluid has been drained from it, as the umr 1YP1• cally contains residual PCB fluid.

12. 17 ORGANOCHLORINE PESTICIDES The organocl~lorine pesticides arc chlorina ted organic compo und s rhat fo rmers form:rl! used as insecticides. Mose are chlorina ted hydrocarbons like the PCBs. Also lik e rhe PCB,, rhey are exrremelr sta ble subs rances that do not biodegrade in the environment. fnSrcad,

Chapter 12 Che mis try of Some Hazardo us Orga nic Compounds: Pa rt 1

formrr use has resulted in their bioaccum ! • h ,neir 1 5 e<:ics, ultimately causing their dem u ation 1 ~ough the food web in diff~rcnr 3

" 1 "

13 a~oc hl orine pcsueides to osc- 3 su m.· or_ drc_lme in numbers. EPA now considers

ihe o~ health and the environm!t Cons bstant1al ~1sk of causing a negative impact on num

3 1 4_8 ) to their potential · f equemly, it does not issue FIFRA registrations

~~~~

1

~ 1~ 1erda ll y, o_r their u_se is~~nug ~~~::~\~te~;:h:h~:i::CJt~:~~:.are either unavail- Jn 200hl,1

th .e Um te~ -~atiobns_ also took action on banning or severely limiting 1he use

of orga noc orme p~mc, es Y _implementation of 1he international treaty known 3s the Stockholm Convention on Pe~istent Organic Pollutants, or the POPs Treaty. The POPs are a group _of

th e

13 moSt persi 5t ~nt, toxic substancc-s tht1t pose a threat to human health

and rhe environment, The grou~ is i~f"posed of aldrin, chlordane, dieldrin, endrin, hep- r.1chlor, hexachlorob~nzene, Mi_rex_ ' , To xapbeneTM, DDT, PCBs, the polychlorinated dibentofura ns and dibenzo-p-~io_xms, and hexabromocyclododecane (Section 14.2-A ). The first nin e membe rs of this listing are organochlorine pesticides. Ahhough it is doubt - ful that eme rgency responders would ever encoumer them, this brief introduction is pro- rided here to emp ha size that some toxic subsiances are considered so ultra-haza.rdous tha t rhei r production, ma nufac1ure, and use must be regulated.

Stock holm Con vention on Pers istent Organic Polluta nts (POPs

Nillt ionstrHtythat bans or lim its the worldwideu~of nineorganochlorine pest icides, P<Bs, thepolythlorinned d1benzofuransand dibenzo-p-Oio.1dns,illnd he.11i11bromocyclo• dodecane

Chapter 12 Chem istry of Some Hazardous Organic Compounds: Part I 527