22
for E .., ... tonl R"l; ofCh<=<>.IIOj"'Y' K...... ODd N"...b""",. Iloou. &04 EcMy>l<1D> Edi'od V9 V""t. G C 9",h D. G Hod ODd D 9 !'unO C 19lllSCOPl; 2 Methods for Estimating Exposure to Chemicals· 2.1 ll'oTRODUCTION is. basic In 10xicololY. Without exposu,.. tUUl it is virtually impossible '0 a rdoabk es,imale of potential damallC to buman health and non·human bIota attributable to p..... nce of chemab in For ",gulalory purposes, i. usually defined as tM ccncenlration of a al ,utfaet of orpnism. Thi. definition ba5 advantallC ccntael bet"· .. na and o<pntsm..... hich the effect$, i5 far ccmplcx than thi. might5U&llCSt, As al ..... y. in,olv.. time, tither e.p1icitly or implicitly. follo.. -;nli defini'ion oeerM app,op,iale (UNEP WHO. 1977; oee also WHO, 1982: Miller, Ibe to a pollutant is a of the oontact hel"'een Ihe pollutanl and IN: OUler or in.... ' (e.a. al_eolar surface or liut) surface of human body, It is u.ually cxpr"""" in lerms of ooncenlration5 of tN: pollutanl in tN: medium (e.l- and food) interfacing "'itb body sutfacn. Once absorbed through body .utface>, pollutant JIves nO<! 10 dOKS in , .. rious orpn5 or ti ..116 no.... are mea.ured in of conccntratioM In Ihe ",.Ut<. Rorords of .. and dosc should include an indicauon and at whICh an Indll'ldualls suhJeeted to tbem.' for man and mammalJ, the imponan, in'erfaces het.. orpni"", and a", $kin and linings of t<'$piratory and tract.: for fi.h. the dili .. tract and &ill$, for plant$, 51omata. leafsurfaceand ,heroo': fo' aquat;,;, plant$, and the lea"", ( ..... llte.. ealled rout .. of .. posu,... Since ;t may be difficult to 'he conttn'ralionl at all ,nterfaces, in'erfaoc concentrations usually .. timate<! from the I'rcpo.,Nl bj' G. C. I"le, (a.... --.), I0 D.•. Po!;!l<,. J K. """,,,,,,,,,.od <\, SorJ. ,

2 Methods for Estimating Exposure Chemicals· '0 · 2 Methods for Estimating Exposure to Chemicals· 2.1 ll'oTRODUCTION Exposu

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Page 1: 2 Methods for Estimating Exposure Chemicals· '0 · 2 Methods for Estimating Exposure to Chemicals· 2.1 ll'oTRODUCTION Exposu

~",t""l> for E..,...tonl R"l; ofCh<=<>.IIOj"'Y' K...... ODd N"...b""",. Iloou. &04 EcMy>l<1D>Edi'od I» V 9 V""t. G C 9",h D. G Hod ODd D 9 !'unOC 19lllSCOPl;

2 Methods for Estimating Exposure toChemicals·

2.1 ll'oTRODUCTION

Exposu<~ is. basic ~QnI;:(:P' In 10xicololY. Without adequat~ exposu,.. tUUl it isvirtually impossible '0 mak~ a rdoabk es,imale of potential damallC to bumanhealth and non· human bIota attributable to ,h~ p.....nce of chemab in lb~

~n",ronm~nl.

For ",gulalory purposes, cxpo.ur~ i. usually defined as tM ccncenlration ofach~mK:a1 al Ih~ ~.t~mal ,utfaet of tb~ targ~t orpnism. Thi. definition ba5 ,b~

advantallC ohimplicit~. Ho"'~'~r. th~ ccntael bet"·..n a ch~mK:al and lb~ ta'g~t

o<pntsm.....hich dn~rmlnes the effect$, i5 far mor~ ccmplcx than thi. d~finitionmight5U&llCSt, As ~xposur~ al.....y. in,olv.. time, tither e.p1icitly or implicitly. th~follo..-;nli defini'ion oeerM mo<~ app,op,iale (UNEP WHO. 1977; oee alsoWHO, 1982: Miller, 1983~

Ibe ~.po.ur~ to a &i,'~n pollutant is a mea.ur~ of the oontact hel"'een Ihepollutanl and IN: OUler or in....' (e.a. al_eolar surface or liut) surface oflh~ human body, It is u.ually cxpr"""" in lerms of ooncenlration5 of tN:pollutanl in tN: medium (e.l- amb~n,.ir and food) interfacing "'itb th~ bodysutfacn. Once absorbed through body .utface>, th~ pollutant JIves nO<! 10dOKS in ,..rious orpn5 or ti..116 no.... are mea.ured in t~nn5 ofconccntratioM In Ihe ",.Ut<. Rorords of ..posur~ and dosc should includean indicauon ofth~ tim~ and frequ~flCJI at whICh an Indll'ldualls suhJeeted totbem.'

for man and t~rrestrial mammalJ, the imponan, in'erfaces het ..'~ lh~

orpni"", and tb~ ~nvironm~nt a", Ih~ $kin and th~ ~pl1b~lial linings of tb~

t<'$piratory and digeStiv~ tract.: for fi.h. the dili..ti"~ tract and th~ &ill$, fort~rrestrial plant$, th~ 51omata. th~ leafsurfaceand ,heroo': fo' aquat;,;, plant$, lh~st~ln$ and the lea"", (..... Butl~r. 1918~ llte.. int~rfacesar~ oft~n ealled rout.. of..posu,... Since ;t may be difficult to mc:asu,~ 'he conttn'ralionl at all lb~

pertin~nl ,nterfaces, in'erfaoc concentrations ar~ usually ..timate<! from the

• I'rcpo.,Nl bj' G. C. I"le, (a....--.), I 0 _"~ D.•. Po!;!l<,. J K. """,,,,,,,,,.od <\, SorJ.,

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a"erage mass concentration of the chemical in the rele>'anl rompartmenlS ofthe environment such as ai" ""Ier and food,

When eXpo$Uf< oa:urs at an inlernal 'nterfa« such as the epilheliallining of therespiratory or dig..ti,'e lract, il hal to be estimated from Ihe mtake (or rate ofintah~ i,e, the amount of a ,ubslaTlOl: inhaled and or ingested. Intake dependsboth on e'''ironmental and physiological nriables

B,ological df<ct. of chemical. are better correb.ted ",tb 'dose' than tbcy are,,'i,b exposuf< 0' intake, '~. has been defined as the amount or concentrat,onofa substance at the s"e ofeffect, that is. ,"'''''re ils presence causes a ai'en effect(,"'hOle o,ganism, organ or tissue) (oe<: for example, Nordberg, 1976. or Butlcr,1978~ The level of exposure (or dose) determines the effCC1 but the way in whicbe.posure 0' dosc is diStnbuted may also determine the 'ype and magnitude ofIbeeffCC'l. Ther. is a whole spectrum of ronccn..ation-tim.....,ffCC1 f<b.tionships.,wbicb depend on tbe pbysical and chemical propenie. and toxicity of 'hechemICal invoived ($C<:, for example:. Piotrowski and Buchanan, 1982~ For somecbemical" 'be instantaneou. or peak concentra'ion in 'he target orpn de·termin", Ihe likelihood and the type of effect .... hich may be Immed,ate and of.hon duralion; immediate bu' of long duration (chronic~deb.yed and of sbortduration; or delayed and chronic. For other chemical. some effCC1. may resultfrom rep.eated '" ronunucd dehvery of the agenllO the \.arget orpn or lissue,These effCC'ls may apin b<: either o{shOrt Or lonl! dural ion. occurrinl! after shortor lonl! delay and rC\'ersible or irreversible.

In some ca.... 'he mapllude of the effCC'l is related '0 the I",'el ofexposure ordose (graded dfects~ Some effCC'l' do not sho.... gradation; they either do oa:ur ordo not occur (quantal effects) and their incidence (called 'respon",' by someaUlhors. lee Nordberg. 1976; WHO, 1978) and not their mll!ni'ude is. fUllC1.ionof the exposUf< or dosc.

When a.....inl! tbe effects of releasinl! chemicals in'o the environment. thepossibih,y of thelt cont,nued pr=nce in the en'"ironment and potential risk f",fumre a.....'.n a. present gen......tions have to be con.idercd, Modelling (..., Miller,(978) and e>.POSUf< commilment analy<;, (..., Barry, 1979; O'Brien, 1919,Bennett, 1981) are useful app<o.<:he!i to ..timlling future e.pooures and theirconSC<lllCn<:es. Exposur. comm,tment is defined as the int.gral ofconcentration,n a compartment o,'er ,n6nlte time:

(2.1)

"'hef< r, i. the ...erage malSconcentr.,ion in compartment j at Ume I. Esposurecomml1ment is measurW in units of malS concentration multiplied b) time, forexample, ml!' m-·')'cars.

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2.2 IDENTIFICATION AND ASSESS.\IENT Of SOURCES OfENVIRONMEI'oTAL CHE.\UCALS

Expo,ure """ssment begin< with the ....m;nat,on orthe total input ofa .hemil;:a]into the en,ironment, and th;, involves idemification and qualitat;'·. andquantitati"e description of sources of chemicals. For local problems, the a<:Iualamoun, IOvohed in a gi"en ""ti"ity i' impot1.l.nt. If pollution ;, more widespread,th. anal)'>is requires consideration of the chemical and physical form of tbesubl\.ance, tot.1 amoun's. palterns ofdIstribution, use and disposal (including thepossib~ity of spills, dissipative uses.. and recyclinsl and routes of enlTy intoth. environment (lluller, 1978~

The total attKIunt of. substance produced, eith.r in a particular geographicregion Or globally, i, in many eaSel oot ealy to obtain. In addi'ion. some hIghlytosic organic ,ynthetic compounds are not produced d.liberat.ly but OCCur asImpurities In more Or less innocuous prodl>l;lI (.... Holdgate, 1919). Naturalsources may dominlte for certain substances. especially metals, Some environ·mental pollutants may also orisinate in natural sources from which they may bereleas.ed ,,'hen sl>l;h sources are ..p1o;ted. For ""ample, th. main source ofenvirontlt<';ntal pollution by mercury relllled to human acti'ity i' now thecombu'tion of fo..il fueb ,,'hich generally rontain m.rcury ... an impurity inconcentrations of less than one part per mIllion (WHO, 19(6). The same i' truefor SOme oth.r elements, for esampl•• vanadium (NAS NRC, 1974~

Global release rates are notortou.ly hard to estimate IMiller .nd IIl>1;hanan,19'79~ Thu.. for many subst.nce:s ",'en the tot.l amounll ....iIable for possibleen"ironmental dischari" ..e not lCCuratt!y ho"". SIl'll;t; ",\"(:Tl1 thousandlubstanttS esill in amOunl> adequate to produce "'id..pread .nvironmentalpollution (Korte. 19(7). it i' ,urprillns that .uch a le,-el or uncertalnty ."111 inregard 10 th" basic information_ Some of it is now being lCC\Imulated (IRPTC,1978, 1979; Ott ~t al., 1978~ ho,,'e"cr, additional data are ,ull required for a lali.number of narural .nd manufu,ured substance:s.

Another probl.m is '0 predict th. physical and ch.mical form in which a,ubstance "'ould he releas.ed and "-hether it "-ould be r.leased at all. tf the rei.....is. ,...pour or a rompound bound to ' ..ry fine particl....n'·ironmenLlltran.portover looS di<tanttS i' likely to occur (Whelpdale, 1978) tfth. release il an organiccompound or.n .Iement ch.lated to organic subslancel. bioaccumulation andfood-chain magnification ..eto be expected (l."orski. 1919).

2.3 APPROACHES TO EXPOSURE ESTI\lATION

Ellposure estImation i, hl-sed On a variety of techniques ,,'hich, in order to be.trec",'e, mult be "-ell coordinated. Mod.llinll and monitoring are tWI> of 'hemain technique, used; in addltion, luch techniques ... laboratory and field t..ting.""amina'ion of human activity pall.rns and methods based on cbclltlCalcharacteristics may be jnvol--ed.

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Two dilTerenl approaches to e~posure estimation are in gencralusc, For maJOrenvirol1tl1OntaJ pollutants of concern, such ... metals (for eumplc:. Pb. Cd. Hil~

COmmOn atmosph.ric pollutants such ... SO,. CO. NO.~ pesticides and somepemst.nt organic compound. (for in'ta~ polychlorinated biph.nylsj.,posur.estimations ha.'. largely been carried out through a combination of .n,·iron_mental and biological monitorinil and mod.lling. h.n for these ",id.ly studiedpollution problems. expo,ur. estimates are usually fa' from reliable. Foreumple, for lead Ih.... i. srill con"derabk .onlrov.rs.y about the relati""contribution of emission. from molor v.hicles. The .nvironmental fat. of ...·en",.n·studied pollutants i. often poorly unders.tood. Vet 'his is vital for theestabhshment of em,ss,on oonrrols '0 achie"e acceptable exposure I...·.ls.

A. far ... tile actual measur.ment or estimation of .'poIar. is concerned. thesituation is uneven. Fo!Substances such as PI>. Cd. Hg and some orgamlChlorin.compounds. analy.i. of biological lamples (bioanalysis) may proVld. a goodmeasure of ••posure, Ho......'er. bioanalysis cannol be used to estimat•••posure10 pollUWlIl .""h a. SO, or NO., 11 is also r<eogniud 'hat for Ih"", ""born.substances ambient moniloring provides a poor m....ur. of individual exposure.s...'.ral pilot pro,teet. are no'" und.r way to mea.me actual individual.'poIure'oair pollutants and itS d.pend.nce On human acti.'ity pall.rns. and to corr.lal.th.results of these measur.m.nll wilh Ih. resulls of ambient monitorina (WHO,1982~

Numerous .h.mical notification sch.mes now in operation are anoth.r morereunt approach to e'poIure estimation. A'lhese schemes deal ma,nly ...,th n....·.h.."icals. tbe approach is of n<ee:ssity predicli.-e. Sueh ••poIur. esllmalions r.lymainly on laboratory d.t.rmination of ph}·oicoeh.mical propertie. and degra.dation and _umulation p,"""".... and on knowledge of the USC, ..",ssion anddisposal pan.rns and eharaeleristieo of populations likely to be exJlO$"d.

In practice. the actual estimation procedure "ill d.pend on a large number off""'tors. and Ih.re can be no de...i!ed prescribed procedures: ....h esumalion mustbe geared to the spe<:1fic s"oallon. ThUs. the estimation is either carned Out at thepremarkelinll 'tall. or after th. cllemical hal been r.leased or used, Fo'pr.mIlrketing decisions. predictive estimations are required. These ar. largelybased on laboratory and microcosm tests. on basic physicocllemical propertiesand on the study of similar .hernK:a!s-

Th. r""luired precision ofexposure estimates d.pends on th. amounl prodoccdand released, th. lil:e1~ .itt of the ••posed popula,ion and Ihe type of biological.ffecl' that may OO;:ur, A major faclor in d<eiding On the r""luired pr<eision of.'poIur. estimation i. th. 'pot.ntial for .'poIur.' "bich increases in th.following ord.r.

--<:!I.mical, used only a> process inl.rmediales---ch.mical. used in closed syst.=---ch.micals in .onsum.r products--<:!I.mical. di.persed on Ih••nvironment

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U:po$uTe estunahon for cheltlJCllls mainly usod in consumer producrs r<bespnmanly on the knowledae of u.. pauems and consum.r habits. Estimation fordispersed substances requIres ",..Iuation of .nvironm.ntal path ....Y' aod tran..fen between environmental companm.nt.. In many cues. Ih. chemical ofinter..t may fit into mor< than On. ofth... cat.goTies (for eumpk lead is bothused ,n wnmmer products and emitted inlo Ih••n.'ironm.nt~

Th. charact.ri,tics of th. popullotion •• posed ha.. a major in8 ...nce on tb.type of exposure ..,ima,. reqUIred. As r.ga.rds buman target.. "'. arc g.nrn.lIyconcerned with on'OT morc of Ihe followinglypcs of popullotJons,

--oa:upallo....lly ..posod groups-<;Onsurne,..-the mOSI biibly ..posed groups in the g'n<:ral population-groups of susceptibl. indi'iduals-~n.ral population.

Whil. in many cases the problem of ..timatinll or m....uring population"po«urc i$ "milar for the ..."ou< groups. the difficulti.. In ..tabli,binllthe....ntial links hetween all sou",", and ..pasu.... becomes prolVcuiv.ly mOr<difficult as on<: goes down Ihe list.

Th. oth., main wnsid.rallon is wbether on. tries to ..timat. Individual OTpopulation ••pasure. PredlCll'" ..pasur< estimates deal primanly with av.rallCpopulation "po$ur._ Environmental monito"ng .nd modelling ,r. u«<l forestimating population ..posures. ,,·h.reas diff.rent forms of biolollical monitor·ing deal with IndIviduals Or groups of individual..

On. Imponant Wik in th.d",·.lopmcnt of..pasur< ..t,mal" will be to hnk thepopulallon 10 be US6<Cd with individual ..pasur. estimates. In many casespopulation ••'.raged ..timat.. may pmpoint groups from "-h,,,h indi.>dualscanbe ",lected for th. mOre ••pensi,-. biolopeal monitorinll prograrnn>cs.

U:posur. estimations ofl.n requir. consider.ble 6....1IC1l1 .nd manpo..·.rresour=. II is, Ih....fo....ital to specify dearly lhe purposc: for whoch the..tnnation is 10 be "",d._ Wilhm th. risk estimalion proceu it..lf•••pasur.estimation, may be required in support of on. or mor. of tilt: followtngobjccti.es:

-hazard' Id.nlificalion-haatd ranking-hazard estimation,

Ho..·",'" •••posu....timat.. arc .Iso required for otllt:r purposes wbicb include:

-d.monstration of oompliance with regulations

• 1b<tt .. "" ...,.raUy ...-. cle6loi""" of 'Ilant<l· IWO<Ill<d ~1I~ • cbt;1DICI!, Tho Im1I iI"""umco used 10 lrxI..... tloo ~ulil>ood w.t • ,_.ad ..ill co... 1»... _ th< _,""", ,n"_11 n prod""';. _ '"dl~ t_ WHO, 1m),

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12 Mrrlwds fcr E.fIl",aring Risk t>/ Chrmicalilljury

-..;upport of research programmes, in particular .pid.miological inl'estigalions-..;upporl of modelling aw,'i,ies.

2.4 [r\VIRO~'lE~TAl TRANSPORT A'\"D D1STRIBliTIO.'

2.4.1 b.';rOl'mencII'Iodellinl\

The basI( lIOl>I;<;ptS Ind prO<:>;SSe$ of cydmg of Crace .ubstances in lhe.n.ironmem are rea>onabl)' ,,·.n und.mood. and r.I......nl mod.ls ha,.., be<:ndeveloped 10 describe th." .n,ironm.ntal behli,·iour. Many mod.ls ha,. be<:nformulated to describe the mo".menl of radionuclid.. r.1ea>cd from nuclearinstallations Or from atmosph.ric nuclear lests, These m.lhod, are g.n.rall)'applit:abl.to airborne ,ubstances present in pan~lat .. or as p"",,us pollutants,Th.r. are atmospheric di,persion mod.ls. aql>ltic tran'porl mod.ls. and food·chain and <cosy".m model' (see Mill.r, 1978~

Mort ,han on. mod.1 may be reqUited m condUC1ing an a:posur• .,Iimalionfor a chemit:a!. For example. alf d..pel'SJon or aquall'; 'Tlnsporl mod.ls may beapplied to the initial mo,'.ment of the ,;hemical from Ih. sources to the point ofmterest. Food-<:hain and o'her mort local transport models may then be used tod.t.rmlne fUrlher transf.r of the chemical to the receptor.

Modelling beglns with the .pecification of th. compattmental a'Tlngementwhich reft..,ts the syst.m components, emly a. much d.lail as may be ....nlial i'Introduced. StmpliJied model' ha,·. ad"antages, and incroaSJng the «rmplexity i'justified only for substantialtmpro'-ements in reliabilily of result..

Models can be broadly dassiJie>d either as hme-dependcnt or lime·independent, Time-d.pend.nt mod.ls outline Ihe shott·t.rm ~ineticbeha,iour ofa cllemica1 substance in the environment. First-order ~inetics i. 1""'.",1Iyassumed. and a .ystem of differential equatIon. d...,ri\>es the changes Inromparlm.nt eontent•. Many paramet.r '·alu., are required for thIS type ofmOOel. but the outpUt e,'aIUllion i. most romplet. "'ilh amounts and lransf.,rates Jiven for all poin" arid al aU tim.. (Dra~. arid BarflFr, 1979~

Atune.independ.nt de!iCription of the behaviour of. ,;hemical can be based onmo,. limite>d data. In Ihis ca5O, the obp:ri'....re 10 determine the panitioning ofthe ,;hemica1 in path"...y rompartmenll and 10 estimate the total amounts ,,'hichultimat.ly reach Ih. receptor, Th. relalien,htps bet"'een compartm.ntalamounts .r. o.pr.osed as the ralios al stead)' state, called concentration factors,The time-independent app,oach is oft.n ref.rre>d 10 as the COl>l;<;ntration faero'method.

An ",pression ,,'hich il useful In describmg the en,'ironmental belu."our ofch.mit:al$ is the tim. tnt.gral ofconcentratiOn, FOJ' lransf.rs of trace SUMtancesbet,....n environment.1 reservoirs "'h"'h can be described by linear fust'orderkinetri. lhe mtegrale>d concentrations in Iu<:ccss"e compartment.. and alsointegrated nux.. (cumulative inta~.. to rompartmen"~ maintain constant

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M~tlw<h for utimating £xpollir~ to C/tmtirol. IJ

r.lalion.hlps. n.e ra,ios of ;nt.graled concen,ratlons per unn r.least: of ach.mQI .ubs'ance define ,he 'ransfer factors for mo".menl be' .....n sllCOOSSi,"companments. Th. in'.gra'ed concen'ra'ion. refle.:t 'h. ae.:"mulat;on in ,h.compar,men, or 'ransfer ofth. ,ubstano: ,hrouih a oompanmcnl. n.e im.gralan"ring ,he .n,ir. period of Ih. presence of ,h••ubs'ance In 'h. finalcompartm.nt i. 'ermed expo,ur. commi,men, (Barry. 1979; see equalion :U~

for a g,,·.n rdease. th;s isa wef,,1 meaS"r. of the p<l<Slble long_,erm ,ran.fer ofachemical through an .n"ironmental r.gion.

In applYing general models '0 .pecific chemQIs, appropna'e ",lues mu.1 beasslgned '0 ,h. ''''''''u' paramt:,.... and 'his is 'he major difficulty. Th. physical.ch.mical. biological and interaetion fae,or. mUSt be $elected from a wid. rang. ofpo<slbl~ ,·a.!ues. Due to inherenl '':I.J'iabili,ies and incomplete dna bases.particularly for new chemQIs, uncerta,ntl« In ••posur......Iualion. eanno, bea"olded

2.1.1./ Air DisfHrsWn Models

In 'he loeal r.gion of relea... dispersIon models based on Ih. Gaussian di[lISionequa'ion are most commonly uled. Dispersion .'Iimal" ean be made for a",ri'ly of me,eorological oondilions such as wind,peed, (Puquill. 1974~ Aparticular ....ult d.pends on constanl wind and stabilily oonditions and.th.refor•. Ih.r. are lim;" on ,;me and distance ,...Iidi'y, G.n.rally. prediction. areoonsid.red reliable only wi'hin a f.w I.ns of kilometres from ,he ",ura:.

Trajeaory mod.ls may be used '0 estimat. ,h. di,persion of subs,ances '0grea,er di'tances (Nordo t1 01.. 1974~ These models may be qui" rompl...requiring large compul.r <:apacity and mu" be backed by detailed "..ind <!ala.How..'er. accounl eao be taken of a ...ide variety ofchanging conditions and of~ompl•• I.rrain.

It is also n~ry to accounl rDr ,... riDUS remo,...l pr<>eeSSe5 from the plumesand fDr ch.micallransfDrmalion, "..hleh may OCC1Ir during lransport. Thi' may bedDne by ""imating .[eoi,'e soura: .lr.ngIlIS or by estima,ing depletiDn a,variOIlS stages Df Ih. 'ran'porl. Kno... ledgc of chemical klne,ic< is required forreacti"e gases and aerosol,. Deposition of par'i<:ulales occurs by precip;,atiDnand by impaction On the und.rlying surfaces.

2.1,/,2 Aqutll'" TrDnJpDrl Models

Aqua,ic ,ran,port Df ch.mical subs,ances is go,'eme<! by ,en<:ral wa,er mO''''m.nlS and by sedImentation prOCt<leS, Mod.ls are ea'.gDrized according 10 ,he'ype of ......'.r bodIes into ...·hich chemicals are r.l....sed lri"..... lakes. ""uaries Orcoas,al areas) (..... for eample, UNSCEAR, 1982~ It may be assumed tbal"la,i"ely npld mi.ing DecU'" in lhe r=i~ing """er "olume or 'hal equilibrium is

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14 Mellwds If>' EstimaliltfJ Rut ~IClwmlc"llnjIDy

achlC'-ed. Other...-i5e. fto,.. characteri.lic$ can be modelled if hydrologicalinformation i......ailablo {see Imboden and Gichtor. 1979~

An important inpul of chemicals '0 aqualic sy.Mms is pro>'ided by th. surfacerun-otf from soils t~ lak.. and stream!; and the d~...-n"...rd penelration throughsoil. to ground"...ter (free,e and Cherry. 1979~ Down"...rd migration ofchemicals in soils i. due to leacrung wl\h ramfall Or trription " ...tor, Factonaffecting the m",.."",nl compri.. solubi~ly. so,) proper"... including potenlialfor adsorp,ion to roil nuneral. Or orpnic malerial. and "'aler influx (.... forexample. Le>ter n 01.• 1975; Cameron and Klule. 1971~ Chcnllcals soluble in"''''Ier and poorly adrorbed bl roil oomponent. are the 10051 mobile, Down•.-ardmo,..ment occun in preference 10 .urface run-off unt,) 'he surface layer is...,......,td.

Modelling of migralion ofchemicab in ground•.-ater (Mihl'l.lIl. 1971: Duguidand R.., ... 1976) depend. on acquiflng h)'drographic infotIDation for lhespecific localion, It may be particularly important to determine migration umos.dilu!Jon effoelS and amoun" returntd to drinkmg " ...t.. rourcos

2.4,13 FooJ~ItJJi>, ruuJ EeosrJltm M<><kls

Transfers along le"..trial and aqualic food chain' are represenltd as compart.mental SC<lucnces wl\h transfer factor, or concentration ratios ""pressing there!ation:;hiput stead)' .tate. So'-m,l stages in Ihe modelling may be identified. forexample. lIOil pasture grass-row~milk-man,An o'erall transfer in a .inglo stepmay also be evaluattd. such as in aq ....lic models in which Ihe concentrationfaclor from waler to aquatic orpnisms is used, Linear models mal' also beformulated to describe food-chain tran.fers, The interhnking tran,rer raleconstant, musl be .....Iuattd; Ihe so(ullon then ~,... concc:ntration ,...riations as afunction of time (set Miller. 1971l~

Ecosystem tbeory. tm'olving e.amination of aspoc1S such as "r.... 'tabllity.energy flu.... nutrient cycl... carbon ""'tabo~sm and trophic structure. is beingapp~td in models to descnbe chemlCll pollUtant bella'iour in .pe.oific en,'iron·menU. A"ailab~it)' of infotIDation ;s the major limiting factor in directapplicationS of largo·scale ""oslSlem model..

2.4,1.4 Cltemk,,1 Tr"nslor"",'iQII and Spuimion

Models for tbe beha"iou' ofchemICals m the .nv"onm.nl may not he .ullie..nt ,fonly one set of rat. con"ants and transfer proce.... i. included. More often thannot. clu:mlcal tran.format,ons take place In the en>';'ooment. and tbe modelsIoU>! deal simultaneou.ly ,.,th mOre than on. chemICal .I"<'i the parametersg",'eming their bella,'iour betng often quite different. In sucb ca the danger i.ofha"inglO sel up a mood ofO\'crpo",enngcomplexitl. Tbe number ofp"'.ible<hem"'al form. ofany element is endle... and the attempt to deal w"h aU p"'Stbk

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M~,Mds Ib' EslimlJ'ing £XPtJ"'r~ 'b CMmkfll. IS

In'ercon.'",,,ons will demoy any h"pe "f inc",poralini the details in'" amanageable pic'ure "f ,,"erall dynamICS.

Thus a ',rade-(lff' be,wttn Slmpliclly and role"ance has to be made, If a smallnumber of chemical speei... "f the element In quos'ion ,,'hi.h arc of paniculartn' "onm.nt~l"initiea".., can be ldenulied, then a mana~.abl. m<><lel "f"'-eralldynamtcs rna}' be achi,,'ed

The diff.rences in en,-imnmen'al bebavt"ur "f. f", • .ample. ",pnic 'pee... "fmetals as "pposed 10 the" Inorpnic f"rms are profound. In Ih. now well-StudIedea~ of mercury. ,he co"".,..ion ofa qUlie small fractIon ofth. Inorgan'" form 10

11>0 lipophilic meth}'lated form re.ull5 in ,1>0 accumulalion in a food chaIn of lheorpnlc f"rm. and a .iiruticant heallb hazard rna)' re,ull (sec Wood, 1974, J.n~nand JemelOY. 1%9). ThIS hazard could nO"er ha"e been predicled (and ",IS notfor....n) on the baSI' of chem'cal proper"... of Ihe parent substan«, Howe"".no'" lhat the transformation is understood, the ,ilualion can be described wilhmOre aoeuracy by simpl. partlllOn c""llki.,,,, (MIller. 1978), The case ofmercury i' rela'ively simple. for lhere are only two chemical .peo:i.. a<counlmifor the bulk of Ibe materIal and also the bulk oflox",it)' In other "''''''. Vo-e mayneed '0 'hmk of. larier number of parallel m<><lds, Each of them desc"bes theen,'ironmental behas-ioilr of"ne species and a coupling of the models has to bemade in each compartmenl Vo here chemicallramformatl"n take' place, There i'a. ;et IIltle ..perie".., wi'h .""h muhiple models; th" is a part of lhe m<><leBiniart whICh IS In need of furth.r de,..lopmtnt

2,4.1,S V"lidOlwn wuI C'eJ,bi!iIJ tJ/ Modeb

For )'ears. computer applicatIons have been open to ~rilicisms in aU area, andenvironmental m<><leillng is no exceptIon. Th.,. C""Clsms refer to uncwicalaccepta"'" of computet-generated data on the one hand and to unreasonablerejecli"n on the other. as " ..11 as '0 the possiblllt)' Ihat m<><lel' are "rele"ant In IheIi"" pIa..

The a<:<:ep,a".., by some d....,on·makers of c"nclu'lons based on en',ron­men,al mooelling ha' been Ie.. lhan enthu'iastic. This may '0 a great ex'tnt beblamed on the modell." ,hemselves whQ SOmetimeS make unsupported claimsbased Qn po<>rl;' f"'mulated mooel' and expeo:t autho"'i.. '0 ac' upon ,uchstatem.nl> in .xcluSlon of o'her conSIderation' (Frankiel and Goodall. 1979).E.-en loda;'. i' is quite t}'pical tQ sec conclusion' of m<><l.llIng Stud,.. presen'ed,,'itboul an ...."mpan)'lng ,tatement Q(error bound' or uncertainty Ie.'els in Ihere'ul" Qb'ained (Miller ~I a!.. 1976). Th" need no, haH happened..."..,IeChn"llleS for m<X!e1 validation ha"e been "'ailable a, Ion. a, modellin,'lself(Naj'lor., al.. 19(6), Wbile Ibi. i. not the place to pr.sen, a ,u""C}' of m<><ld."lidali"n I..hniqu... " m,ghl be POln'ed QU' 'ha' .alidaliQn need n<>1 be....1l1Cled 10 a companson of m<><lel OUtpUt with field o\l$cl""uttons (Mlhram,1973).

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16 Mrrlwds fot BIlmtllitr(j Risk of Clt£mi(1l1 I")~r)'

Other appr<>a.ches (0 valida lion and OTTOr ~(imallOn al1' al'ailable. such a, (Ilta..ig"'n<nt ofa ~a""nable .rror range for each parameler and runmng a Mont.·Carlo "mulalion 10 find Ih. errOr distrlbulion of lh. resull, Such lechnlqu«h,a'-e been a"ailable for SOme lime (Miller. 1974, Bum.. 1975) and are bemglncorporal«l inlO rettnt modelhng stud,« (O'/'o.;",U and Rust. 1979), Ne'er_th.less. in man)' mod.lIing sludies such technIques a~ often omllted,

A rectnl publicalion (Frank..l and Goodall. 1978) report«l that man,problems of modd USC and a«<plance "'.re ll<It due 10 lbe lechnocal aspocls ofmodel <truc1ure and performance. but "-er. shortc"mlng< resulling from tbe ladof In,ol,-emenl ,n lhe "o,klng d«lgn and mlllal con<trucl;on (HolcombResear<:h Immul•. 1976), Models and rondu,i"n' from mooelhng "ud,(s ,,-ereunlIkely '0 be g;"en much ...-.ij.ht by Ihosc respon,ible for .n,·ironmenlaldec..ions unle.. ,h... models had been d",do~ ...-ilh spocific need, of lhedecISIon-maker m mmd, In fael. lh. model spocialill "-a. rarely able to fo=these need, On his O"'n (Holromb Research Inslitute, 1976) and lhe.ucc«sn"rmally dcpcnd«l on lhe aClual ;n~ol"Cmenl of lhe USCr Or hi, ~rresenlali"e

early in lh. proce,..Anolher a,peeI of uscr acceptance of mod.l, mlj.hl be term«l access.bllil). or

"'hal In .....nl computer parlan« 's ,.rmed ·fn.ndhn...'_ ·Fnendltn...· i' tbeea.. "'-llh ...-h"h a n"n-specialist in .omputer procedur~ and modellinglechniques can under'land mood performance and imeract "'i'h it. An.mp" b)mod.lling ,pociali5l' 10 ,ncrea.. lbe ""phi'licalion of 'heir mod.I, ma, be ..If.d.feallng. f"r lhe model. b«ome les< accesSIble 10 lh. user (Holhng. 1973),Those responsibl. for d..i,;on, in tbe public sector are ad,'e,... to accepllnginformalion Ih. d",clopmenl of "'hich lhey do nOl undersland (HolcombR.....ar<:h In5litu'e. 1976). In thi' ronn..tion. ...-. nole 'hat u..r-on.nted model.wllh VIdeO graphICS and "mple provamming are galnmg w>dcr acceplan« lh,anmore ""phi'ticated models thaI only a spoc,ahSl 'an unders'and (Holhng. 1973),

The conllnued d...·.lopmcot of en"ironmental model. in Ih. direction ofImpro,'«1 'ahdalion. error .pecificalion and uSCr onenlallon may be secnas ....nllal if s""h models arc 10 be useful in Ih.... r.tj ......lualion of chemi·~,.

1.4.1 [n.'iron"",alal Monitorinl

Exposures of ammal and planl organisms and man 10 chem...,als In lheen''ironment can be e..lual«l wllh most certa,nl)' by direct mea.urement ofConc.nlrallon, and ftUXC5. PCO\lded Ihallhe sampling and analyt"al proceduresare adequalC, Exlen,,'e and comprehen.,,'. m.asurements are de"rabl. bUlhmll«l r«ou..-o« USUall)' requIre lha' sclcc""e measuremenlS be If\lIdc 10 pc"vldeessential Informalion Moniloring and mod.lIinl programme< a~ mu'uaU)'supporl"'e In IMI modeillng stud,« ,uggcsllhe most imponant m.asuremenlS

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and c~tcnd 'M relevance of 'M results ofmea,urement. Moni'oring programm..pro'"id. basic dala for ;npu' '0 and ""lidaHon of modelling .ffons.

Bsen'ial f.a'ur.. of mon;toring proaramm.. Includ. sile sel"",ion. samplingmelhods. mcasuremCnl$ '0 be undenak"". frequency of measul'C1l\enl$ andprocedure, for reporting and inl<rprcta'ion of result>. M.a.urements includw Inmoniloring programme' must be appropnal< 10 'M purpose of ,he programme.rellcc' ,pa'ial and I.mporal '·arialion•. pro"id. d.'all. of physical and chemIcalf011lls and be report«l "11h relevan' dala On en""onmenlal cond"ions, Anin'.graled approach 10 moni'orins. i.. mulli-m.dia and mulli-$ubstancralUlly... at specific Icca'ions, IS required 10 .valoal< ,h. hehaviour ofch.micalsand their inlerac,ion. in tM .n,'ironmen,.

Moni'or;ng sMs arc gcnnally chosen because they are considned ..represen'al"". bu' in some ca....il.. mal' be sel""lw randomly. This OCCUfl

usuall}' In mOre Iiml1t:d proaramm('S for ,pecific purpo..., for .""mple. '0del.mUn. ,h••xlent ofg.round contaminalion follo"';ng an ao::id.ntal rekasc. Ar.pr....n'ali'·. si,c fOT amb,cnl mCasuremCnts should be related to ,he uposure.stimal< For .xampk. OUtdoof mea,urem'nts may be "'ailab1< but thepopula'ion in q....'ion 1'CS1<ks primarily indoo... RclaHon,hlp> between outdoorand Indoor coo«nlra1l0ns of pollutants In air mUSI 'h"" be found. and moremea.uremen" must be mad. in th. rel.vanl Iccations, More an.nlion is nO'"bemll paid '0 the dis'nbu';on of moniloring si,es and to mdoor exposur.. (seeWHO, 1982),

MOnttoringdata should indicate changes with tim. ofchemical cooccntra,ionsand media propenies to ••tablisb wbetber equilibrium conditions ha,.. beenreacbed Or to reflcct trends In ao::umulation Or d,m",u'ion of the amounts ofchemical. Of degradalion products. Analysis of s,ored specimen., so-calledh;stoneal monitorinli. is und.nak.n to d.termin. retrospecli"., long-term "endsin background 1.,,·.1•. It is important 'hal no, only prescnl and past .xposu.... bedelCrmlne<!, bu' tbe build-Up of chemical substances;n soil. «durn;nts Or Olhn.inko be monitored, alld the long·term potentialtran.fer 10 differen' organi,msand man be ""alea,e<!

Wh.n tb. obje<li". i. the .Sl;mation of buman .xposure, ambi.nt monitoringbas '0 be closely linked '0 indi"dual activity pallern,. Alternal,,'ely. personalmoni'ors may he worn '0 oblaln a mOre direct ""male of uposure fromatrbom. cbemicals (see WHO. 1982). P.rsonal mon"o" are u,ually passi".filt.nng de>'i<:e-s ..·bicb haw demonstrated uscfulncl-> for SOme chemleals bu,ba'" limila'ions ror oth... ,

Mon,tonng programm.. mal' be condUCted '0 "udj' ,h. mecbanism. of"ansfn of chemical •. Th. result. of mea.uremenlS may se",.-e a, da,a ba... forthe formula'ion of models tbat descnbe .nVlronm.nlal behaviour

Monitoflng for .xposu.... of elfeclS to ec<>$j·Slcm. rna)' oflen be conductedbj sampltng and aJall'''s of rcpresenta'iv. ,xposed sp«ics (!iCC, fOI example.Cairnl, 1981). In some case<. this may be a ~n>cularll' avaIlable Specl" or onewhteb bas a<cumula,ed billh I."..ls of a ch.mical. Monlloflng in remole ar.as,

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,uch a, m b,ospheK resef\'e.. may be conducled 10 study Klennl changes In lheglobal backg.ound of pollu'ant kvel.,

B BEHAVIOUR or CHBIICAI..'> IN THE ORCANIS...I

2.5.1 Metlbolk Models

Melabolic model. aK u!or<! '0 describe lhe "'lalions bel"'..n ,nlake ofchenllcalsu!ls'.n«< and 'hei' absnrpllon (uplake). d'llnbUllon, ",tenllon. transform­ation and e..""ion b}' 'he o.ganism, The.. mod.l, may be useful in ",Ia',ng,nlake.to m.asured le".ls ,n body f1u,d,. 'uch a, blood and Unne. On Ihe Olh.,hand. lhe)' may be U!or<!IO calculal' doses Ind integraled doses 10 la'gel organ'

A' in .n,·"onmenlll mod.lIing.•ilher urne-in&penden' or limNkpcnd.nlmetabolic modd' may be app'Oprial., A's,eady "ate. 'he concentralion fa<1o ..Ii'" a ,imple e~pressioo of lhe 6nal di'poiilion ofch.mical, 'aken in al con,lantra'., II maj' be difficuh'o assume lhallhe... "a ,'ead)' Slate. panlCularl}' if lhe..a.. long-term transfe.. or ...-id. varialion', The "alue. of concenlratlon fa<1orsapply to panieula••n"lronmen,al condilion,. bUl ""der applic<lbility ,an u,uall)be assumed for rea>onabl} ,omparable cir<:umstan<eS.

Compa.tmenl model. of more or I"", &'aillnd complexily ""'j' be U!or<!IOdescribe metabolic beha"iour of chemicals, Companmenl5 rna}' r.pr.sent aphysicll .tru<1U'" of lhe orll"n"m, .uch as malO organ. and lissu.., or lhe) ma)'...present , ..riou.components of ..ten' ion, R.tention .qua'ion. con,iiling ofa,urn of exponecnliall.rm, are often U!or<!I0 r.flect o"erall me'abolism (Butler.1978)

Model. have been d....lope<! "'hich reflecl phy'.'ological pr...:nses follo"',nl\inlake on human. and animals, These include a lung mod.l (ICRP. 1966b) and amodel for Ihe gamoin,..';nal tracl (E,... 1%6). Summari•• ofabsorpllon ,..lu..and olh« metabolic dala for chemicalel.menl5 an: gi".n by ICRP (1979).

Muhicompartm.nt models hi,.. been formulated 10 r.pre>enllhe m.taboli.mof ,pec,6c chemical ,u!lstance<. for .umple. an eigh'<omparlmen, metabolicmodel for cadmium (Kjellmom and Nordberg. 1978) or a he-eompanmentmodd for lead (Bernard, 1977). R.viev." of lhi. and olher a,peclS of lhemodelling procedures are iI,.n by Gehnng <I 01. (1976). BUlkr (1978), WHO(1978) and Camn« tr or (l979),

In &.iJOing a model for an}' partICular chemlCal. one has 10 cons,&. ",,'.rala.peelS ofmetabolic beha"iou" each ofv.-hich call' for a .peci!k lrealment. Suchaspeeli mal" be lhal

(I) chemical•. and organic compound. 10 particular. may underso a bin­lransformanon as a ...,uh of wbich ""'.... I new chemical ent,li...merse.each Wilh differenl k,oelic propcm.. and loxici".., Combining lhe o".,allprocess inlo one model may be a Ian of••ee..,,'o complex,'Y. and ,her.ron:.r<a>onabi. ,implificatlon, of lhe 'j"5lem rna)' be >oughl;

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M"ItOods fer Emmaling ExpoSJJ." 10 CMmicai. 19

(2) .ubstance. rna}' be<:orn~ ~h<m>CI.lly or phy'lCally bound a' .p«ifi~ 1,lt.,'''Ulllng in somi·irrt--er'lblc d~po<il' Ih~ bella'iour of ,,'hich cannol bedtsenbtd by tht killttle> offim·ord~r pr~. A sp«ific tumplt i. leadand ot btr osleilph,llC ~I<m"" lS. whort Ibe pa nial kinelic coeffiCltn IU-rt UJl\t·deptndent. One ofthe ..,IUlion.to .ucb .ituatlon. rna}' be lhe uSO ofa PO"«'fU"",,,on modt!. Olhor ..,IUlions may be ..,ught by IIm,"nll tbe >eopt ofmod<llInlllO a purely empmcal de$Cripli"n oflhe holla"iour in a given organor II"U., in isolation from the o''Crall fal. ,n Ib~ orllani>m:

(3) tb. assumption. und~r1)ma, in aeneral. lho kin.lic modelling "f 'hobella"our of cb.mical. by' u.ing fim-ord.. pr""",so., may DOl he "alid forhigh dose> of cbernical•. Thi•. ho..'.v.r. rarel} rep.....nt. a problem m~n,ironmenlal 10xicoiollY "'he,e I"w e<>ncenu'ations of chomicals arenormally ~ounl<red m biological media,

2.3.2 Biologinl Mooiloriog

The term 'biological monilonnll' has bttn used tn t"O dJlr.",nl way"

(I) Ch.mical analy". ofb,ol"&ical .pteim~ns, luch a, blood 0' .XCrtU ...mples.t<> det.rmin. ,h. concen'''''ion of polluUln1$ (0' ,h." m<taboht..) (hil>­anal)'sis).

(2) B'ological rcsponso, meUUreJl\tn, ofb,oloa,cal.I"",uon.,n.n oraani"",popUlalion. communi')' or ecosys'.m ....ullin' from ••posur•.

In SOJl\t ,n<lances ,he '.rm biolollical monnoring i' al... applied 10 lh.p'ocedurt "f ~'JIO'mll solected tts' 'pee,ts 10 a polluled Jl\td,um of unkno..'ne<>mJlO'ilion and recordin, ,hon·'.rm effects. Only one Uptel of biolopealm"nnonn, (chomical analy". of biological .pee,Jl\tn.) will be di$Cu,sed in 'hisstC"O"

Th. multi of cbemical analy.il of b'olollical 'peelmen, (bioa....ly,i,) rnay beused with Jl\tlabolic mod.l...boch describe ,b. prO«$llnl of lubslances by lheor,ani,m, luch a.lh••hsorphon r<"Sulling from spteific intake mode' and forms,and lho di5tribulion and rtl.nlion Oflh~ cbtmical, ,n ,be body Bo'h dynamo::and I,ead)'...al~ m<><l<:l. a", a,·ailable.

A. II well known.•p«ial precautions must be laken ,n ",mpl,n, and anal)"$1$of biologic.I specimens. The 1",.1, ofch"""cals may be quite low. and cart mustbe taken '0 avo,d con'aminauon from ...mphn, equipment. Th~ d,fficult,.. ofoblaininllaccural< anal)'!ical ....ults ,n b,oloaical 'pteim.n, have stimulaled aninl.....l in .011aborati,'. >ludie< lnl.rlaboralory e<>mpari..,n. IIave bttn unde,·lak"". but lb. r••ull. of lbest Sludi<"S art ofl.n di..ppoinlinl.•ho..'ing widedifferences ~v~n fo' qu,,~ common mea,ur~men". The n<ed fo' Ilnct anal)'11Cl1qualilyConuol ha' bttn frequentlypomlo:t!oUI (d. WHO UNEP. 197\1: Fribtrgand Vable" 1983),

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20 M~'1wd< fo' £<tima'ing RiM of CMmkaJ Injun

2.$.2.1 H~oltlr-rtlat~d BioiO/Jirol Mon,l(),ing

ChemICal analy.i. of b'ologlCal 'p«'m"", (b'oanaly,i,) " .... developed linl In,ndu"rial tolicoloay as a method for estim.ll,na exl'O"u", of ntd,vo<lual$.Ho"-e-..,r. ahl>ough human blOloJlcal 'p«'men, are uK<!, the data cannot beal"...ys ,n'erpl1:1c<! ,n 'enns of ,od,"idu.al eXI'O"Ule be<cause lllt: ......ults obHUned,,'nh diff."'n' ind"iduab may be ''''ry d,ll.r.n' for the >am. ,xl'O"ur. For thi."'a50n. b,oanaly,i, i' 5Ometime> uK<! only for e5tlmalina collecu,-. or aroup(Xl'O'ure (T."ina.r. 196I!)

B,oanaly,i, has al50 been uK<! .. a method of mea,urinilolal eXp"'Ul1: 10.ub$'anttS "hi<:h a,e ea.,ly abs-orbed throuah ,k,o and lunp. such as anllone.ni1fobenz.en•. benzidine. para'hioo, dimelhylfonnamide and olhers (Piotro".-.ki,1977; Lau",.,.y. n 01.. 1980)

An inl.malional proS',mm. of biolO£ic.aI monitorioi (bioanaly.i,) ha' been,nlllated b) WHO and LNEP 10 ..,ima" human exposure, '0 sel..,to<lpollu,.,n,s. In ,his p,oject. the leve!> ofkad 'od clldm,am In blood, cadm'um inkidney con.x and ""nain orpnochlorin. compound, in bre"t milk are beinidc'enn,nod io selecled popula,ion seamen" in 1O~12 coaoln.. m differ.n, part<of the "orld (WHO, 1980: Friberi and Vahl.r, 1983). Infonnation on methodsfor bio.o.naly.i, 'Xi'l' for about SO-fiO organi<: .ub$lances. Thi. numher ha'i""rnKd l""ally o,-er th. pa" 15 years due '0 me'hodolOa>cal dn.lopm<nu,panicululy in g.. ~h,oma'og'aphy.

It .hould be pointed oallhal it does nol .ufti<:e to be able 10 delecland quantifya cherntc.al subolance. For a ""'aningl"ul b'oanaly"$ programme, il i. ne<:ess.ary 10have 'tandardized or agreed-upon >amplini procedur., and adequal' inl.r·laboratory compari50n prog....mme$. The number of sub$'an«s for" hlCh 'lIt:secondition. are >alisJied i' ralher .mall

Wh.re.. th. oldc' pr""edurtS were ma,nly based on lhe analy'" of me,ab­ali'.. in unitt;. lhe more recenl method. anen recommend the analy.i. of blood(or .xpired air fa' .."la"l. compounds) and 'he onilna1 .ub$lance i' u,uallydetermined, For se'.."al orpni<: chemical. alt.maliv. p'ocedu'.. are nowa,...ilahk, baKd on 'he detrnn,nalion af e'ther lhe ori£inal .ubotanee or il>metabolites in dlffer.nl 'p«imen. (urine. blood.•'Plfed ai,). For lipophilICcompound$ "'hlCh have a lona half·time m 'he orpn"m. 'uch as DDT and otherchlo'inated hydrocarbon•. f.l tinuc i' oft"" used as ,he monnonna medium(WHO, 1979),

Th.d.gree '0 ",h,ch relul" of ,uch mon'tonni can be m'erpreled in ,.la,ion 10"l'O"u,( d,ffel'$ con,;derably fo' , ..riou, chemical•. A f.w .ub$lanccs, such asbenune, toluene, trichloroethy'kn. and $')"en•. hav. consumed mo<, of 1M.ffort ,,'herea5 for mao)' other chemical. me{aboli<: Sludie> in man ba,.., n....,rbeen performed. The appllCabilily of many of lh. a,'a,lab\<: procedur.. to lowkvd. non-«cupat,onal e'po,ures is doubtful.

Much effort has been dO\'oted '0 1M bioanal)',,, of .k"",n{> such a, lead.

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Mrthodsf<tr EsIIltWIi"l1 UjHJSIJU 10 Ch~",i~als 21

mercury. cadmium. arsenic and othe'rs. Th<; bioanaly"" of metal. and metal-likedemtllts ha, been performed in a "ariely of .pectmen. using many proe<edu,".The earl) data refer mo.tl)' to urine. but blood anal)'", hal recently replacedmuch of the' routiM anal}"" of un,.,. .Th<; analy.i, of hair ha' ptned recognitiononly ,n a f.... ca.... "'here the' detemllnation i' ,uffic,endy rehable andblololl,cally meaningful

Ti"ues not routinel)' a,-a,lable fOf a""lysi' mal be ""meltmes obtainedfrom autopsy An example from lhe WHO UNEP international programme(WHO UNEP, 1979) tHad'llm, for wh~h the most rehabl. "timat< oflife·lonlle,~ure may be obtamed f,om ,t< l.v.1 to th. kldne).. (Fnber. and Vahter.1983),

Ifapplicable, bioanalysi. may pro"ide a dose rale-time function \l.-hich rnay beused for more ""phtsticated approaches of "'k es"mallon. 1$ is lhe case ,"'l1hmethylmercury (PiOtto... ,kl and In,k,p. 1981: P:tOlfO'" ,ki and Buchanan. 1982).

2.5.2.2 l·,. of BioiOflieal MoniIO,Ul{j (8i(){lJlQIJsu; for £$limarlltfJ£xposu,~

Althou.h b,olnaly.i. yltld' the 'oncentrat,on of a .h.m....1in 'issues 0' bodyflUId' (8). th. r.al object may be Ih. est;mation of e.polure (El "'hleh i, theindependent "anable In the <quallon:

B _ f(El (2.2)

Dependmg on th. use of monito"n, dotta, e.posure rna)' be es"mate<! in a"an~ty ofways. for single rout•••posu," the .oncentration in the rele"ant typeof en'ironmental .pecimen may be u>ed as a m••sure of ~'posure. Fo,mull"ou" uposurts. ho"e>'<T. "posure should be consid.re<! in t.rm. of thetotal tntake or uptake rate. I,e. as the tOlal amount 'aken ln'o 'he body orabsorbed in a unIt of tIme

Wh.n bloanalysis is used for ..posure estlmat;on, three .tages should bedutl}, distinguished;

(I) elabo'ation of a procedure "hereby the function f(El in equation (2,2) isestablished (.alibration).

(2) lampl. analysis and(3) eakulat;on of ..posure from equation (2.2)

Cahb'a'ion of exposure function rnay be ach...'ed "'ther by conltolled.••posure studies "'ith volunt..". OT by usinil propedy seleete<! dlua from fi.ldstudies. Controlled exposure studies ha,.. been performed in SC'o'o,..llabora,onesw,th ofpnic chemtcals of .ho't b,olo,'tll half_timo. especially for use inindustnaltoxicology. Simllar studies ,,-jtb chemicals .. hich ha.·. a long biologg\half-lime are much more difficult, Long-term studit~ w.'" performed In th. past

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22 M~tlood.f for U'imDllFlfJ Risk of Clrmli~aJ ".j~,y

for lead. DDT, and aklnn (for a re'o'iew~ Piotro",~ki. 1977). Of nect$\;IY, suchlong,term studies in"ohe ..,veral problems, bolh .Ihical and t(>Chn>ea1. Thesedifficullies juslify att.mpts to establish the form ofthe function f(E) in C<juation(2.2) compuuotionally by using data from single..xposurc studies. It has to beemphaSIzed. h",,'.>,Cf, tha' such mod.lhnlt""hniq.... arc slill under d.>,clop­men"

Although 'I has not been explic,lIy Slated. estimat,oo from hlO<inal}'s" daUl ofthe total ,xlX'sure contnbuted to b}' various routes i' "'"oed on Ih. assumedadditivity of aboorbed dose' .xpressed as funchon, of exposure:

(2,3)

where the biolop:alle".1 B ,nt'grates ab$o,hcd dose< f,I£,) via routes i .. a. b.c To ",I,••quatton (2.3), a..,t of C<juation, sh061d be con"ructed u>in,additional dala. The procedure may rai......-eral problem, both computationaland t""hnical.

S,mpl,fied 'ituation' ex"t ,n which .xpooures. expr."ed .. ootake ratts. areC<ju.al to uptllke ""OS (aboorp,"on ratts). and the fUDCtions are tinear andaddi",e, as may be the ca.. "mh SOme orpn", compound, ab$orbcd through th.lungs and 'kin ,imultan.ously. H",,-e>'•• , .ven in 'uch simple 'ystems theestima"on of total do.. inwl>'os ..'-eral a.sumpllons ,,'hich ha,.. been rar.l)>·.nlied .xpenmentally. The.. procedures. ",hen used for muh,med,a pollu\llnts.clearly require further expenm.ntal and Ihcor.ttcal support and de,'elopmenl,

].5.]..1 Usc of Bi<>I~kaJ .1!lHfiloring (B~I'Ju) fel Pm!;'tingH~aJlh £jJ«1J

Th. lev.ls ofa chemical ,n organs or ti rcllcc1 the .xpo,u.. of th. indl"idual(or population) and in 'urn de'erm,,,,, ad ~ .If,,,,,, wh,ch may be ma",fested ,ntl>< sam. individual (or populatton). Therefor., if d~ff<C1 or .xposu....lf«1r.lation,h,p> ar. a"ailable. biO<inal)'ii. daUl can be used fot pre<het,n, h""lth.ff«ts directly. i", nol in>'ol>'in, es,ima'es of .xposure as di5CU..ed abo>'.,DependOOI on ,he ,ntended U.. of monitoring data, the melhodology ofbiO<inal)'si, should be d.,.·.lopc<! along different hn..,

As poInted out e1.... he.. (NordbctJ, 1976). ad"ersc .If<<ts show fi...t in som<ti".... or orpns ,,'hich a.. Ih. crilical orpns, In this cont.Xllhe 'cmical orpn'is d.fined as tha' pamcular orpn "hich fi ...t allain~ tl>< critical concentration ofacherni",,1 und•••pecified cin:um51ar.ces of .xposu•• and for a Ii'·.n population,entical orpn conccntrat,on i' ddined a. lhe m.an co"""ntration in the orpn a'tl>< tim. Ih. cooc<n"a,ion in any of itt cell. r.ach.. a Critical concentration. Thecntical cooc<nttauon for a ",11 i. the """""ntrat,on at which undesirabl.fuoctional chan,.s. ..,.·...ible or irrey...ible. o«ur in ,he cell. (TGMA. 1973).n"s d.nmt,on of Ihe cntical orptt d'ff.... from the definition &i>-en by til<

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Inl.malional Commi"ion on Radiologial Prot<C1ion (ICRP. I%N). Tho "'oro'crilical' ""a, u5<d by 1M CommIsSIon 10 d.sctlbo Ih. o.pn of Ih. body ....hose:",ad,auon ",'as likely 10 bo of veat.,t importallCC .ith.. b<cau~of 1M dose: IIrecei"". it< ..n,il;..ily. or the importallCC 10 heallh of any damage Ihal may..sull, The Commlso,on no.... con51<le" lhal it i' necc....ry to spcclf) ""'eralorpns and lissues Ihal ha'.. 10 bo con.idered b<c.u~ of 1I,." ,usc.phblilly todamage. the ..riousn." of such damage and Ih. eu.nl 10 "'hich il could bo".alable (ICRP. 1977). Th. definllion ofcrilical o'llan Ii'..n in Ihe report of theSubcommmtt on the TO'IColoIlY of M..als ohh. Perman.nl Comm..,ion and[nt.rnallonal Associahon on Oa:up.illlonal Health (Nordbor,. 1976) imph.. tha'no effCClud'..r.. '0 'M '" hoi. orpni,m ",II occur if ctlllCaleffects in lhe crilicalo'pn. are ldenlified and can bo p",,'emed. Thus. the bost .....yof .."malln, lhelikehhood of effect< ....ould bo to oblaln Ihe le..el of Ihe chemical in Ihe crilicalorpn' directly (for example. in bram. her or kldne}'.). This is usually nOtpo5stble and. therefore. a subsmul' biologICal medium is ..lccled "hlOh IS eaSIlyanilable (such as blood 0' hair) under the assumptlon that lh..e i. a hIghcomlauon bo:t....ttn lilt CO""cnU'allOn, In ,he 1"'0 media. In Ihis ca... lhemonilorinll by biOlnal)".. ;. ba5<d on an assumed function:

B _ 4'(DmJ (2.4)

"'here D<m 1$ theCOroccntrallon ,n lhe crltl(2l orpn and ~ 1$ some fuocllon. Ifalinea' relal;"n,hlp applies. 4> is limply a coefficient of proportionalilY, In comrast'0 the .stimalion of ..posure by hioanalys;" the ."lidil}' of function (2.4) canonl) rarel}' be proved on human subject< dirccll) and the .xacl form of Ih.fuoclion is n",'", kno....n ....ilh ce'tamly. Instead, anImal e.perlmenu are u5<d 10asCerta,n If (I) a high correlalion .aim and (2) some charact..istic, of lhefunclion (such as llnearily and range of partilion cocffictento) Can be establi.hedThe m"'l rel",'anl factor Sttm, 10 be the correlation cnefficltnl; 11 d.termm.. lhed.ll.... ofas"""alion bet""ttn the l.,d of the chemical in 1M biolollical medium..lccted and lhe COllCCn"alion in th. crilical orpn(.),

SillCC blood transports cMmical. 1o lISO"". 11 is nflen assumed that il;S lhemOlt ,uilabl. hiolollical medium for monilorlnll if Ih. a,m of mOnllOrlng is 10pro,,;de support dala for ri.k a.....menl. Ho"'....·... any otM' medIUm Can alsobo u5<d (.uch as exp"ed a" fo' ""Ialil. compound,. hair or nail. for el.ment>...,umulaunll in Ihese lissue,). pro.'ided Ihe relalion (2.4) IS ,..bd.

U CONCLUSIONS

(l) E.po,ure .....,ments require. in addil;on to the ..Iimat,on of concen·tralion. allarUlS. information of .n,·"onmental sources .nd ~Ih,,-a)'•. Thesedata art oflen u~ in Ihe rcaul,uory pr<JoCCSS. A.....m.nt of human .~posure,

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24 M~'1wd4 lor £mma,~ RiM< olChnnkll1 {,,1",)'

alw mjui,," much detaIled mformauon aboUl the life-Sl}'les of lhe exposedpeeple

0) M.thods for eshmaung "l'<>5u", of non-human tarll"ls 10 en""onmentalchemical. are nol ,ufficienlly developed,

(3) Methodology for relaling environmental beha",our of ch.m",als 10,xp05u", is in a >late of dC\'e\opmenl. SC\-eral differem t«hniqlle5 a", in u'" andthey mu.t be adequately COOrd'llaled, Environm.ntal tran.port model. areu..ful for ",Ia"nl <xl'O'u,,", to Utes of ",lea", but lhey requi", ,mpro"emenl asregard, ground"'al" modening. identifK:alion ofchemIcal .pecies in>-ol>'ed and>'alidalion.

(4) Much eO\;ronmenlal monltonn, bas been carried oul. It has beeninc",a.in,ly recognized that ,t 'hould be mo'" closely "'Iated to expasureeslimalion. In addnion to th. contln"ing need 10 ImprO>'e samphn, procedu,,",and anal)'ticalt«hniques. spectal auenl,on sbould be dJl'«'w 10 <baractenungchemical 'pec1es in"ol...d, Mult,-med,a and mulu-,ubslan<:e mea,u",ments a",lmportan, for undemanding lbe tran,fe.. and ",aclions of en,',ronmenlalchemical',

(S) En>-ironm.nlal monnonng is needed to >..lidate exposure prediclion. forne'" chemicals based on laboratory le'lin,.

(6) Metabolic model' are requlfed 10 <!eslgn the most informat",. blok>pcalmonllonng melhods and to a\.$OS' the ,,",ull., The.. model. mu.1 be ",Ialed 10the roules of ,make and 10 the loxicological properties of lhe chemIcal. They.",also need.d for esumoIllng,h. tOtal,nlak. ,,",ulllng from uposu,,", by mulupkroule.

(7) For ,o",oolol,oal ,n<O'Pr<la"on. blologioal monl1oring should pro"ide,nformation from "'hich the do.. 10 tbe lareet can be eslimated,

1.7 RECOMMENDAT10l"S

(I) Procedure. 'hould be d.'-eloped for obtaIning beuer informallon about,b. ",ka.. of na,ural and man-made chemICal' '0 tbe en>.,ronmen1.

(2) For a....';ng human 'Xl'O'UIff. esJle(:LiIllly ,n the home er""ronmcnt, moremformatlon is needed about tbe we of consumer products and about humanaOll'lty pall..n•.

(3) Beuer met bods 'hould be developed for e"unalin, expasu", of non­human targets and ecOI)'.<oms

(4) Ground"'a,er tran'port and dISpersion models 'hould be further d~­

,,,loped and Impro>ed(5) The e.ilung mode" for environm.n'al,unsport should be modIfied 10

lake Into account ch.micaltransformalions lhallake place durin,'he mo>'ementof chemICals through lhe en"lronment.

(6) Env,ronmental tran.port modelhng procedures sbould be Impro>'ed

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panicularly a' regard, 'alidallon. ~,ro, ,pKlfica,ion and u..., o,ien'a,ion ofmodel'.

(7) Where pos,ible. en.ironmemal monll,mng should be orien'ed 10 e~posure

",I;ma';on, To im~,o'" e~posu",esllmal... les,ing and t>-aluallon ofchemical'should mclude me,abolic "ud,." follow,ng "nlie. repea'ed and long.,ermexposures and in,ak." by all roules 'hould be con$ldered.

(8) En'1Tonmenlal mOnilOnn. 'bould include ,denllficallon and analy.is ofall chemical form' of a pollu,an'

(9) [n'"onmenllll momlonng 'bould co"", as many m..lla and con·,ammaled malerials al ,h~ ~m~ $ll~ as possible

(10) The le"el5 of.bmllcal, mOS' closely relaled to lh~ ad'-e.... efT..:' should bemea,ured 10 define ~fT",,"Ye npo'u,~

z.8 llEfERENCES

Barr." P J (1979). An Inl.<>dIIctioflto IIw~t C""""a""," C"""" .·iIA hit"""'a &<i._.,111 Mt""'Y- MARC R.port Number 12. Moni'orinl a:>:l A'se<'rn<n,R<iUreh Ceo're. Cbc:1... CoI~, Uo;',,"", of Lol'ldon. London: 9l1'&....

IIcnne't 8. G. (1981), ul'J"'" C""""i,......, A.......... rs 01 htfircNYonl',,) IoIh"""IS,VoL I. No. I MARC Rtport Numbe, n. p. J. Monllonnland A.........n' R<iUrebCen're. Cbc:1... Colk,.. Uni,.."", of Lcl'ldon. Lcndon

IIcrNrd, S R. (l<nn. 00'''''«'''' da'a and melOboh" mo<lcl fo' kad, /fI,A Ph)'I.. n.~-Bum•. J C, (197~1, Error analy". of """hl>Cal "mull<oons: appllCa'ion, 10 wn<1ddj"nam"".IEE£ r."",. S)'". M<u:. CJ'bmt.• SMC·'. ))1- 340.

Bu,k,. G. C (1<n8), E.lIrnallOn of dooes.:>:I iot<l...ted dooes. In Butk,. G. C. (Ed.)PriMipk. 01 frotoxiro!ogy, SCOPE: J], pp, 91-112. John Wilry & Son., Chicltn'<f,N.... York. Bn.boa..... Toron,o

Ca"n•. J Jr. (l981~ 8",lop;a1 moMonng. Part Vl-Fu,ure needs: Wa'. IMs, I~.941-912

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Fnonk"l. F N.. and Goodall. O. w. (Ed•.)(lm). S""""',,"" MO<klling 01&<i."""".,a1hobJmv, SCOPE:9. John Wik, & Son•. Chl<bn«r. Nrw York. Brioboa"". To,on,o'12!pog«.

ffC<2C, R. A .. and Ch<ny, J A (1979). GroIlnIl>o'au,. Prrn,n-H.Il, Irw;. EngltwoodOilJi. N.L 1""6Ol pqeo.

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26 ,l{tl!w<h fo' EJ'imtlW'fI Risk of Cilmflcollnju,>,

Fnbr'l;, L, iUHl '1.1".,. M. (l9S]). A.......... , <>I <Xposure 10 l<td and Cldm,um lhroupbo.oiop;al """"I<mnl, R..ull. of a UNEP WHO &lobal ,'udy. L!<". 1M... 30. 95-1<8.

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M'hram. G. A. (1973). Some p<*:'ia.1 urea' of ,he "."fIca"on and vallda"on of"mula"on model.. 0"" ilu :13, 17-29.

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UNEP WHO (1911). iI.po" 01 1M M"'~ of" G....""...'" Exptrr Gwup ... H.oJ,h·"/;:,,d M"';lo<iIIg eEl' 77.fJ. World Heal'h 0.,,0"'''00. Geneva: Ui pas'"

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WHO (1980~ Jo;", £.f0 WHO food _ Atrimm furl C...'''''''''''';"" MMi'","'ip,Ofj"'_' PlOirtn R~pD<II, M"'cI< /980. HCS fCM MJ.l. World HealthOrpn",,'ion. Gell<\'a' 6 ~J"

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