Document Erk9d132rRrdDrmGE29N3gkg

PCB Confsronoo II Stookholn 1972 KBIMOG KB D WAXES ABB WTLDIJTU A.T. Holdon (freshwater fisheries Laboratory, fitloahry, Scotland) IBTMODCTICi Althou(h polyohlorinated biphsnyla (KB) hay* bsan Muufaoturod fox Tarlom purpossa fox do paat forty years, It wo not until 1966 that Janaan than in a variety of anvlronnantal oarplea, usInf tho ga0 ohroantogiistiio nployad also# 19^2 for tha dataotlon and. aaaauxaaant of tha porolotent crgmoohlerlm paatloldaa ouoh a BOX (and Ita natcbolltaa) ami dlallrln. Couflasatioa of the identity of tha KB-residues -was nada by kjo apootroaotry, which at tho ease tics inlloated tha pnaanoa of a larger manbar of po'-rpiUotlnated blphonyla thm was mggoated by Hm nunbar of rat ohrouatographio paaka* In tha analyala of alldllfa aanplaa for organochlorlao paatloldaa ilnaa 1968, aavaral workers had raoordad tha preasnoe of a nunbar of unldentlflabia OLD paaka* Jsnaon's dlaoovazy of tha praaanoo of KB residues, while assisting la tha datazmlaat&an of a furtbav group of dataetabla contaminants, aads It evident that aana of tha arllir analytical rasulta raportad la tha literature, particularly for pp'-IBV and pp>a8H, war* probably arxooaoua* Subsequently teolmiquea ham boon developed to anahla a raaaoaabla degroe of aaparatlca of KB froa nany orgaaoohlorlaa paatloldaa to bo achieved bafoxo OLD analyala, but tha KB roalduaa mat still bo aatlaatad aa a mom at proaont* Bslyohlerlaatod blphonjlo oan bo uood for a wide Tarlaty of puapeseo, and tha ixturoa of laonara produoad by tha varloua naaafaetuxrra my ruaga fro* thaao amtain lag about 800 by weight of ehlorlaa, averaging about one ehlorlna atm par nolaoulif to om omtalnlng about 700 ef ohlorlno, averaging almost nine ohlorlno atom par --lamia. A total of 809 ohlorlnatod blpbanyla, oentalnlng frm ana to tm ehlorlna atma, 1|. theoretically possible, and It baa baan shown (Blaaona and Walti, 1971) that m pmt&aolar 940 ohlorlnatod ulxturo omtalnn at laaat fifty dlffaraat laornro* Boa of thorn have boon pxoparsd individually, md oonaequently fox routlna analyala of witi--U1 HONS 043876 2, naaplea the comnerelally-avoilable mixture* mist be used as refereno* itttlarta, Som degradation of the leesar-chlorlnatmd member* of the eerloe probably ocean in tlw L-nvi roruoent, uvl in consequence the pattern of GU3 peeks obtained froa wildlife o^vlae d Iffera froa that of the corawreial mixture*. T^e estimation of total BOB eoatoat toxicity of the wildlife residues da therefore only approximate at the present tin. In view of the peraiitenoe of the hitter polychlorinated biphenyls, t^ir prosenoe at all envlronaental level*, their potential interference in the analysis for orgaoochlorine pesticides, and their possible toxioity to vorloua foas of lift, oeoslderabl* attention haa baan given in reoont year* to the problea of their vorld-wid# dletrlbutlon. lioet etndlea have involved fish and birds, but in view of the possibility that global monitoring program** for pollutant* tuoh as organoohloriss* nay b* astab* llehad in the near futur* eons consideration must be givon to the types of unlrnwiilal samples snot suitable for the jwrpoe* of monitoring. The Organisation for Eoonomlo Co-operation and heveloptont(CB9CD) has for several years sponsored voluntary international studies of the problea of ssapling and aaalyeiag wildlife wpeolmena for organochlorine residues, and this paper wumuurisas the results of the first eix years of investigation, and indlo&tee the diirioultie* Involved both in the analysis of the aaotplee and in the seleotlon and acquisition of tbs aeotssmry ooaple material. It has been poeelbla to compare the efficiency of analysis la different oountriee, and to aaseas the inportano* of analytical error* a* aapar*d with the variations between individuals la populations of oertala speolse. The oa*ugx*ns* of FOB conoentratlons in envlronmsntal Bella as opposed to living orgaaiaa* la also discussed, nedia ample* sometime! being euggeeted In profereno* to vlldlife sample* for aonltoriag purpose*. ANALYTICAL HDTHOBB BOB* are extracted and analyead by the ease teUinlquss as ar* esployod for orgeat chlorine peetioldee, and appear to b# r*ccr*B*d froa water and tlaeu* aenplee with tbs samerfflclenoy, but mat be separated fron the majority of pesticide* bafor* SIC analysis to avoid interferenos Separation is usually mad* using sillea colum chromatography. MONS 043877 2 3. O'l PCB compound* bIng eluted with p,p1-IHJK (Bolden and Kandta, 19<>9), Armour and Burk* (1970) achieved a degree of 3*paratian of th* Rh fro* m itb a tore active type of allies, Several method* have boon propoo-d for tha determination of the total FOB content froe th* gaa chromatographio trace, hut a raaaot QBCB atwly (Holden, In preparation) haa shown that a considerable measure of agreeoent can bt obtained among analyst* using different method* of estimation. Peak height ia usually measured althoiyrh peak Area, meaeured by electronic inten tion or mechanical device*, la aometiaee used; 4 to 6 CLC peaks are oommonly involved* The eatioation of PCB concentration la influanoad to acne extant by tb* choice of a suitable reference standard, which la usually arbitrary la view of th* dlffarano* In proportions of tha various FCB peaks, as between errrirnnuital caaplee and eomerolal produota* Heverthaleea, in the reoant OECD atudy, eight analyst* using different methode of estimation but similar chlorinated reference mixtures obtained result* on a cormorant aaaple which showed a ooeffloient of variation of -14jC, a value no greater than was obtained for bob* Individual peatioidea la another exchange aaaple used in the e%ma COCD etudy. in alternative method of aaaeeaaent, not yot widoly used, ie the coBplet* chlorination of all PCB realdue* found to tha daeat-hloro compound, giving a ingle QIC peak which la coaparod with th* in* peak produced froa any PCB foraulatlon, or a daoa-chloro-M phenyl standard* Where low-level concentrations are being doterained, as In water or plankton eaaplsa, great car* la naeeaeary to avoid contamination froa laboratory or othar aourcae which may give GXC paaka in position* ainllar to thoa* froa the aaaplea* look oontaalnation, inolgnifleant In th* analysis of aaaplea containing high concentration* of FCBa, can be derived froa plaatioa (particularly PTC), oil used la air compressors, human skin (if not adequately washed beforehand), Internal seals of aetal containers, and in th* eelventa or adeerbenta used in analysis. Ml aolventa must b* purified by diatlllatlOD, and all adsorbents or drying media (e.g. alumina, ellloa, sodium sulphate) must be calolned or solvent-washed before us*. Blank runs through tha oonplet# analytical procedure auet be mad* frequently to oheok for poaeibl* contaainatien. 3 0^38^8 KONS 4. pcs LrVKu; m the isvibonmekt (a) Vr tr$ Pflfo No reference hu been found In the literature to concentrations of <Cit In gatcous form in :ilr, and It Is quite poeelble that atnocpherlc PCB lo associated wilh articulate matter (duet) or water droplet*. In the campling of air, cuch forw vruld be removed by filter* and analysed as particulate natter. Riaebrough 1 aIL (196S)* found 1 to 64 ppb of organoehlorlnee In duet from air over Barbados, but did not por.ltively idei.tify PCB. Analyela of airborne duet off the California coast did not reveal the presence of PCB, and the deduction was node that PCB do not adsorb to ^articulate matter. In the sampling and analyses of atmospheric precipitation for organoehlorlnaa, only the common pesticides <- and f--SBC, dieldrln, pp* EOT and its metabolites pp'^m and pp'-UDK have been reported In detail. Wheatley and TT-Mmaw (196$) and Torrent ad Tattoo (l9^8) found thee# reelduee In rain In the United Kingdom, but the latter also noted the presence of other reelduee believed to be PCB, without quantifying them. Th*-lr '-x.lutenc* we confirmed In further rain camples collected in London (Annual Report 1970), cf the Laboratory of the Government Chemist/ with oa approximate (TIC) estimate of their concentration a* 50-100ng/l. Rain complee have been colleeted and analysed from and analyced in the author's laboratory, four different sites In Sootland during 1972,/and preliminary results Indicate that PCB levels are la the range 20-40ng/l, with total EOT levels of 5~20ng/l* These samples are taken in all-glass equipment, protected from birds, the serial debris (duet, pollen, ete.) being retained separately an pre-washed glees wool filters which arc also analysed. Several hundred millilitres of rain met be oolleoted, the auepllmg period* being Irregular according to the prevailing weather conditions. The oenoentr^ tione of orgtnochlorlnee found In the samples are nevertheless much higher than In river and stream waters In Scotland, furthermore, there 14 so far no evidence that the residues are transported from Industrial areas of Scotland by prevailing winds mod It oeeae likely that the contamination is of more distant origin, or perhaps reflects a general level of atmoepherlo oontsolnation. In this form of sampling, however, it is Impossible to exclude the possibility of transient local contamination, whether from 4 HONS 043879 5. th>' excreta of Hying Mrde, from inaeota, or passing transport* and such .'ould tot be ignored. 'r.y.h \<-\Wra K fee rti'erencoe to FCB concentrations in rivora have appeared in the- Uterature although thee* generally refer to local contamination* Is the ; ilwmScee River, U.S.A., 20-260ppt of Aroclor 1260 end 8Q-2Q70ppb of drooler 1242 uere detected (Veith and Lea 1971). In lake Hlwa, Japes, 100-1000ppt of FCB were round (Ieono, 1971)* Ahling & Jensen (1970) round 0*33 and O.^Oppt In natural eaten In Sv. .'den, but particulate material contained 1350ppt. The sediments In Ontario (Cmada) rivers have been found to contain up to 0.6p.p.a. (Bara efr ^t*i071. nd In several l).S. rivers up to 3*2pi (Tatee &.&, 1972). The latter also Towd 0.1<4pph In unflltered river waters from the Dnlted States* The Michigan Water Reeouioee aiecion ha* reported 10-2900ppt In 30 tributary atreaae to the Qreat Lakee O-.on, 1972). Analyser; of Scottish etrewsr- and rlvere for organochlorlnee in 1971 axii 1972 ) ,.vc ehown ihnt, even in streams with no evldenoe of industrial or gross eewage ''ution, the FCB concentrations are in the range 2-20ppt in unfiltered emiplee* concentrations of organochlorine pestloldea found were d.1-5.1ppt dleldrln, c.3>%3ppt BBS, 0.3-6*4ppt TDK and 0.2-5*7ppt BUT, oxoluding badly-polluted rlvere* i'lcoe reelduee, with the possible exception of dleldrln (used for about ten yeare In licep dips throughout Scotland until 1966), are believed to result from atmospheric, rather than terrestrial contamination. The PCB estimations ears made on the basis or fewer reeks then U ouxtooary for tissue templet, and further examination is likely to reduoe the values quoted abofe. (c) Be* Wateff Anolyels of sea-water sample from tho Firth of Clyde, last Scotland, an aria whleh reocives about one million tpna of sewage sludge per rh'-.ed a concentration of 6ppt* Previous investigations (Bolden, 197(4 bad shown that >cut one ;on of FCBe were probably contained In the annual ditcherge of sludge but it,i-ing 1972 the ocurce from which the FCB entered the sewer was removed* Se-*itir t :::ii'lco from toe Firth of Tay, fast Scotland, contained 5-20ppt, the higher values 5 MONS 043880 6, (d) Pavahwatew Tith The levels of JCD la freshwater fish have been reported ftm only a few areas, partly due to the foot that pesticide concentrations la riven ad streams in agricultural arses ere often greatly la excess of PCB levels, bat alee, m in Scotland, because terrestrial to ureas of direct contamination are often aon-axLetent. The PCB problem hea eo frequently been related to the marine environment that their presence la fresh waters stay have been overlooked, yet dischargee of industrial wastes or crude sewage to rivers would be expected to result la elgolfioant PCB eeausnlatlea in the bioaase. Possibly the feet that euoh rivers, if heavily polluted, asy eeatala no fish has produced this situation, ee fish are oeanonly used as the annllunlm species for such pollutants. Yet fish, like many other aquatic epaciea, can conoentrate PCB by at lasat three orders of magnitude, and it would be surprising if PCB residues were not deteotable la the fish of the aore polluted riven end lakes. Zitko and Choi (1971) reported a con centration of 14*6 ppm in a coho salaon ftaoorhvnnhua kfautahl from take Uiohlgmu Other fleh from Lake Michigan analysed by Veith and Lee (1970) contained 15-25p^ Tiuh from the Great Kiwi Hlver (Kroner, 1971) had up to 150ppm, the PCB being discharged by paper mills. Zitko (1971) found 0.36-1.01ppm in Anericaa eel (inmilla wtrata) from Hew Brunswick (Canada) rivers end, as there wee no endseoe of Industrial m of thee# sewage pollution In eoWrivers, Zitko considered atmospheric fallout to be a feasible souroe. () freshwater Invartabrataa Invertsbaatse ere lose often studied than fleh, but SBdergren $& (1972) used the enphipod both DOT and PCB in streams in southern Sweden. ee m iadioetor organism for mere was evidenee of a eeaeoaal variation, with higher residue levels in August than in April, the POB eemaentratiam being 0*002-0,011 ppm. A number of other invertebrates were also examined, but |QB concentrations never exceeded 0.020ppm, total DOT being up to 0.04dppm. 6 MONS CW3S81 (D r<ah and Bhillflffh. Zltko and auanriiad ths analytical ']:,<* ctiiortnd for marine fish, the concentratlone/io the presumably unpolluted areas `r i-it' :ras t' an O.lppm* In areas known to be polluted,such as the Callflanla eoaat* im Baltic and the Bay of Fundy, values up to 1 Oppo have been fotuttl. In a heavily i.ollMted area euoh as Ifccanbla Bay* Florida- conoentratione from 4*5 to ZOpga ewe detected* Tissues containing a high proportion of lipids ware aore heavily contaminated* In a surrey of the orgsnochlorine content of comroial twine flab epeolee from ^atert around the United Kingdom, (Portoarm end Holden* unpublished)* PCS concentre tlone in musele tieeue ranged from leee than O.lppm in fish such ss eod JMttMft) up to 1.5pp In pleioe (Pleuroneetes olatessa) and mackerel (Soonbsr soonhrua) la thm polluted waters of the Firth of Clyde* Fish liver reflected contamination of tbs environment even sore aarkodly, with ooooentrations in cod liver ranging from 0*4 to 43ppm. Bbepreeoed In tone of extractable lipid* FCB levels nay range ftom Ippm la unpolluted to over 300ppa in polluted areas* The shellfish most commonly used for pollution studies have been noUueoe such ae oysters end mussels. However* thee# epeolee seen to be able to rid thenaelvee of eontsninente such rs pesticides relatively quickly, and ths ooaoentratlona found aay not always reflect the external conditions at ths tiaa of ssapllag* nevertheless, pcrslotent r-ollution In estuaries will give flee to abnormally high reelduo levels la flier,olo at found in surveys aade In Scotland* using Mvtllua edulla. Speolaans la the Firth of Clyde contained up to }.Oppm* while In olean waters tfie oonoentratlons of 0.1-C.2ppn were nore usual* As overall range* however, la not very large* (g) g|ElALBlafifc&8B Marina sseplankton, with a alpiifloant lipid eontaat, mi^t bn oxyeeted to reflect PCS levels In ths surrounding aqueous esdium, but two major llffloultist arias in their use for nonltorlng. Booplenkton samples usually vary Ln opeciee cobposition* and this aay result in s between-eample variation in PCI ;ontent by virtue of the different lipid contents of the various speolts. Analysts based on lipid content night* however, rsduoe ths influence of apeolee opposition. K store serious problen arises from ths possibility of collecting in the plankton net HONS 043882 7 refuse i.uyjj extraneous material as/froa ship*, and tar or oil, whioh an found alaoot .-verywhere on the ocean surface. Hats used for plankton should be elosad when sntarlag or leaving the satar surface. As oil la an excellent solvent for PCI, rm a snail amount uay produce a significant enhancement of PCB concentrations In plankton sMplee. Feint, hydraulic fluid or lubricating oil fkos ehlpa could alao ba sources of PCI. Despite these potential errors, analyses of nixed aosplankton easels# in the eastern Atlantic and Firth of Clyde have shown a consistent pattern, the latter oentainlng higher concentrations, as ezpeoted frea thd local PCS oontaalnatlos. The nasplco fron the north-east Atlantic contained 0.01-O.llpja wet weight (0*1 - 4.2pj* in lipid), whilo eanplrs froa the Firth of Clyde, Including soae unpolluted aceaa, contained 0.04 - 2.20ppa wet weight (1.1 - 20.0ppo In llpld). Sxtreasly hl^ PCI concentration* oxpresned In taraa of extractable lipid, ware obtained froa plankton (store correctly seaton) samples In the Bristol Charnel, 8.V. Btogland, where tbs aadlo.ent is continually disturbed by tidal aovemente. The area receives a eozaldarabla amount of Industrial v.aste, and FCB values of up to 7000pjn in llpld were calculated seaton. Such a cltuation would be unlikely In the open ocean. Reoent analyses af ^^..xton from the Clyde suggest that r-eoiee ooapoeltlon nay have little Influenee on the Pi-3 levels in aooplankton saaplee. (h) Beth terrestrial and aquatic spools# of bird# aay aeeianlate hl^i PCI concentration*, but the placivoroua species, particularly in the sarins snvlrosasnt, fTncrally contain results of nost. Blssbrough ^ ^ (l?68) rtoorded tbs/analysss of beth DDT group and PCI residues froa a wide range of avian speolea in forth America. Beam tpecles contained lees than 0*01 ppm in ousels tissue, but values between 0*1 snA1ppi were notion, and 1a ejseise feeding on fish in polluted areas oaooentratlone be Noon 10 and lOOpgm ware oension. Zitko end Choi (1971) summarised the analyses of bdzda fTesi a master of literature rsfsrsnoes, and in a few instances, such as In the Stockholm PCB Arohipelage, valuta between 100 and I0,000ppm/oere found. 8uoh oooosntratlons would sees to be potentially, if not actually, toxlo to the birds. The eggs of several epeelas In contaalnatad areas have also boon found te oontaln high levols of PCB, sosstisag 10 - lOOpps. MANS 043883 I 9. Tli* range of FCB residues in birds from various locations is thus extremely aids, 'roa 0.01 to 10,000ppm, arid ouch lerger than Is found in fish, for example* Xn ** birds would appear to he noct appropriate organism for monitoring the distrlla lion of ICS in ths environment, although other considerations must qualify *Mr tient, as dicoussed later. (1) Uar^j Mnsnals Holdon, (1972, and 1973 In preuo) has deaerlbed tbs analysis of :'cal and porpoise fat (blubber) for organochlorins rosiduss, and the variation la KS concentrations found In seals froa different parte of the world. Cenoentretlona in extractable lipid range froa Ippn In the Arctic to 250pjo on the weet ooast of the tolled Kingdoa, bub In starving apeclasns, which have metabolised aoat of their fat rroorvss, up to 2&00ppa has been found* The increase in concentrations la lipid* m (hr rosult of starvation stress and reduction of body fat reserves, Is a oenplioetlag factor in the ^ee of reeidue concentration! in organlsaa for assessing ths extent ef }-'>:al environmental contamination. )tc::7T0Rdc icb w the ErmcaiHEiT Thr above summary has indicated the r^nge of eoneentret) one of ICB to be found In the environment, but before ary selection of epeolee appropriate for monitoring la male rfvrral aepeote of the problem of environmental contamination ant be ooneIdsred. Thr oontomlnant in question may entor cn organiea froa the external a*Alia, such aa i ir or water, or iron rediments in the oase of an aquatio filter-feeder, and ttaua the media might be appropriate for sampling end analyale. However, oontmainatiom ef water or air night fluctuate appreciably with time, end organisms. Is whloh the finetan* tlone would be reduoed, oould reflect the general situation more effectively, while at '.io c-atRfi time providing higher oonoentrationa for eaeler Aeteraisatiom. Ae uptake from food ir an alternative, end often the only* source of contamination la meet apeelee, the concentration in ths external medium may not be dlreetly relevant* Speeieo of whloh the individuals move over oonelderable distenoee, either for fcdlnr or on migration, nay give residue information whloh la difficult to interprat, ar 'he residues nay not have been lngeated In the area in which the spas Inane were HONS 043664 9 10. obtained. Thus adult migratory bird* arc riot appropriate nonltorlng organlaam. for chc same reason, trine flat* which may nov* from catuarlna to oosmoIo wat*z% eeuld alno be unsuitable. freshwater fish which remain in a lake over a oonplete lifo-pai9 or invertebrate^ which nova ever relatively abort dlatanoee* can on tha other hMg provide information relevant only to their local environment. A further Important consideration In the choloe of epeelea for monitoring le that ruffle lent indlvlduale mat be available for eenpllnc ** the required time* without ).uving a significant influent* on the total population* Aa residue levels often Increase with age. and nay also dlffar between the aexee, the apeolnene may have to be ealeoted both for age and asx, tMa lnoreamlng tha problem of templing. PurtharmBra, thre Ik always a natural and sometimes considerable variation among indlvlduala withla a j>opulation, even when of one eex and age* In oonaequance, to obtain a re--nmsblj Hccuxate estimate of tha man level of contamination la any cm population* a largs number of indlvlduale may be required* creating problems both in sampling mi mmlyslm* At thia point, it le worth considering the jurpoee for which a monitoring pnfnm may be dsclgned. Initially it Le intended that the level of oontemlmatloa im several ort-ae *iH be determined* ao that the more heavily oontesdnat'>d areas oan ba Identified, and the roureee of pollution controlled* Yet* unless these are already known or sum* pocted, end aampling areas ohoeen accordingly, n gmnsrml monitorixig jrogrease im unlikely to reveal euoh "bot-epot*" * On the other hand* oontamlnatlcm over large was, or due to aerial fallout from distant aouroas* may ba dsteotsd im a general survey. The Information obtained most, however* be euffloiently aoourats to eetablimh statistically that levels of oontamlnatlcm appearing to be hl^ are im fast highs try comparison with those Im other areas* IlmUsrly^ It ebowld be possible far changes in the contamination level Area year to year to be dsteotsd Sltb approgrists statistical sigrdflosnoe. 9umh information is of vain* im assessing tha oaaaaqusaaaa of government or induetrial action whioh has been taken to reduce pollmtiom* The aocureey of the eetiaatee of contamination levels depends In part on the ftvaialm if the enalywee* whioh In turn is dependant on the experience and effleleney of ttaw analysts* MQNS 043885 10 11. In lurge-ecal* ronltoring program** many analyst* *111 bo involved, but aft adequate acceoumnt of their egr**nt can be obtained by tha use of aThrmgr saaplaa. Finally, tha acquisition of analytical data la not tha ultimate porpoaa of ronltoring, Th* underlying faar la that contaalnation 1st*la nay ba aufflclaat to !>tve adverts biological affacta at ona or sore point# in an soo-eyetaa, bat m y*t adequate svidancs of such affaota has baan aatabllahad In vary fa* instore**. It i ej*e: tial that tha concentrations In various apaciaa which ar* capabl# of oouslng advsras offsets should ba daterftlnad, whether tha affaota ay* Co* exaftpls, reduced photosyrthetic activity in alias, tha fallurs to r*produos In Invert*tratso, i behaviour- in vsrtabratss, or rortality In any apeoies. OECD STDDUB OF UtflTORIlfG Tha Organisation for Boonomlc Co-operation and Davelopoant (QE9CD), In a oarlaa of International collaboratlva studies on tha aonltorlng of organoehlorln* rasldua* in the sm'lronftont, has attempted to examine sons of the problems rafsrrad to in th* '`receding paragraphs In tha second programs (Holden, 1<npb)*tha ability of analyst* in several countries to obtain tha naaa raoults, both qualitatively and quantitatively, la tha analyal* of exchange sanplos wa neaotirad* At that tine (1966-69)1 tha variation botwaon analyst* increased with tha difficulty of processing tha samples, ini for tha only railduaa la -hioh there was general egresnont on identity (dlsldrln, VOt, T1 and Wt\ tha oo offloiont of variation aa t*5 to ttQfL, In tha third program* (Holden, la preparation) a substantial inproveaent was noted far tha period 1969*71, tha ooofClolaat of vnrlatlOft for si* peetloldo residues and VCls In samples requiring full processing being &10 t* "**16H sftong 17 laboratories. Tb* question of tha maber of individuals of a population required to provide a moan value of avfflolant precision for detecting differences bate*an populations or changes froft year to year, vaa also axaslnad In the aaoond yrngr--a. In both etaerllag ird pika population* (with no selection for age or aox), fifty Individual* would have bean required tc detect a 2% difference between aaana, but ten would have boon 11 MONS 043886 sufficient to detect a 73^ diffsrenos. The naln nmor for auoh low precision *m tlurt the residues In the Individuals were usually akewly distributed, bat this my has* baa* due to the verlatlon in age within snsples. The third study programme Included the analysis of PCI reelduee in addition to orgsnochlorins pesticide residues In selected wildlife species* and ssnples were taken fron uooontanlnatsd sad oontoalnated areas* The results of this program* have provided information on the extent of PCI contamination, and alee on the difficulty of identifying the contaminated areas* It aiat be bolno In nlnd that. In cannon with all other FOB analyses at the present tine, the taluee obtained are estlnstee of the total PCI ooaoentratlon exproseod in tejime of a oosnerolal mixture of spoelflod chlorine content. Tbs pro portions of the various isonere and honologues poreient In tbs *angles usually differ fron those In the cosx.srclsl mixtures, and no information on the eonoentratlone of Individual compounds Is afforded by the analysis. The eeesaeneat of the potential toxicity of the reslduet dstootsd is thus rsodered difficult, any suoh aetlnmta oust be regarded with eautlcm* Ten countries tanpled sad --lysed the Missel (Mvtllua coastal oaten, both In areas considered to bo uncontsnlnatsd and in other areas known to bo polluted* The aeoesenent of pollution rarloo considerably, boms polluted areas giving fOI oow eentratlon in nuesels as low as 002mg/kg, and one unpolluted area giving 0* Areas with varying degrees of pollution govs values of 0*0t - 1*7ngfa* A eiallan situation arose with the ssnples of herring iUSIBflH) chalyied by sl^t ssa* tries* Those fron ereso olsased as unpolluted had 101 o--eatsmtlana la --sis tleeue --els renting fron 0*10 to 0,54a^((t hut the rang* In flsh/fM polluted areae was 0*19 9s j.jhA*. Freshwater flah show lees evldanoe of FOI aomt--nation. The pike (kfl illlM) sampled in six oountrles usually contained little IC1 even in polluted waters, Ifen values generally being lees then 0.1^/k* let where serious pollution by JOB exists the eonoontrstlona oan be --h hltfwr, ss is the saaplss malyeed by the lethsrl --in, with FOB levels of 0,47 - 099ug/fcff* 18 HONS O<*30d7 13. Tho eggs of fish-eating birds can demonstrate the accuailatlcm of organoehlarl## rnjlduso from tholr food Tory affectively* Fggs of the heron &fltt M :.Mlyor,d by the United Kingdom and the Netherlands* In samples froa roast# gew of i.r. united linedon concentrations beloe a.5mg/1cg were found la the tap, with up to 7.3e/kg is a very polluted area* Id the Netherlands the ooneeatratloae la pollute* areas were up to ten tines greater, 33 - 74&gAff> This ability to ooaoaeferate roaddaoa la ages wss also shown by ths samples fToa two oeoaoa ton lends# la Canada* The relatively uncontaminated colony gave.2 - 4agAff PCS but that la a polluted area contained a aten of Mtag/fcg la eggs* fiisctrssiCM third 03CD * - The/programs ha# indicated tho difficulties of identifying areas polluted te <, rcanoehloriaee, and la particular FC5, by erldenoe other then ehenloal analysis. Consequently the identification of local sources of PCS pollution by the eaalywi# of - niiicator or monitoring opcodes would entail a very large end detailed ampllag d j^lytJcol prcgracM involving maarous sites* Ob the other hand, the detention of v.ore general pollution over large area#, if suoh pollution exists, should be disclosed i> h puttem of fewer sampling sltse at which an appropriate *.peclee could bs used for "cnltorlng on a regular basis. Ideally, this speolee should accumulate the oontainants to such an extent that there is a considerable difference between FCJ content of uncontaninated and polluted specimen#* The tpeoiea should therefor* bs relatively resistant to the offsets of tho pollutant* Referring to the information provided by tho head GKD etudy, oumsentretione of FOB in mnsools ohowed an overall range of about ItlOO, with only a 1iJ0 range tm burring* The egga of herons showed at least a range of 1i190, and m even greater rt.ge eight bo revealed by further aanplea* A heron in the Stockholm irohipelego we# j mod by Jenson p (1p6$) to oontaln 9,400a^tg ln'Msole, ehioh auggosta that tm fi-tm suoh birds could also oontaln exceptionally high levels* fhlls eggo nay bs particularly useful In revealing areas of pollution, ths enbwi ,,/.liable for aialysia could bo limited* Oka the other hand epeolts such ee nseesln or HONS 043888 13 ,^rjrip$ oau usually b* collated In quantity. Tho greater pmlalm of th* ectinatlon of th* Man lav*l of oontanlnatlon of % population of nasals, herring or *IwlTadVabundant apaolaa oould tharofora ba aa lnportant In tha chains ad monitoring apaolaa aa tha wldar rang* of contaninatlon lovals Uksly to oaoog In th* of pteolvorous birds. 1 furthar raatrloticn In plaoad on stapling bjr tea habitat of tte spsakss. oollaotad Idiessls can only W f*h ooaatal waters. for auaplo* and awala, In which aatoawa in oontanlnatlon larol haeva also boon 4anoo*$rwted' (Holdon, 1J7J) * Unitod In KMt distribution. Aa nany ooal oolonlaa aro protested. It haqr bo diffloalt to main nor* than a faw sp*olntas for analywla* Tha aajor problos vhloh aslaoo In 1hs salofrtion of an appropriate aanltorlng apaolaa for global survwUlanoa, howoaat, in that vary fov ooour in all aroaa of tha world, although an soologloally oqalwalnrt apaalaa ean often artand tha rang*. fpaolaa whloh asm ldaal from nogr points at wJaw (adoquate nonbara. oaaa of sax and aga dotoxnlaatlon. cnad ff aaagflf$nqr to Unfttni to tha northtm hsalophsrw. or to ono oootinont. Marina apoaloa ara sonatina* news wid**prad. but olsarly oaonot rafloot oontanlnatlon in terraatrlal on fiusbaslts i.vireanoota. whar* pollution nay originate. Tha (SOB atudloo havo onablod aana aaaoaanant to ba nada of malytloal aasnamaj. of tha ability to obtain aanplsa of ehooan apaolba in tha rofulrod aariterw (on af tea attondant difflenltlaa), and of tha rangst of various xoalftuaa whloh onlnt In palIntoA and unpolluted aroaa Tboy havo alao shown tho difficulty of poaltivwly Idtetlfylag suob aroaa prior to parfowning tha analyaoa. fia paartlnular. tha oholoo of apoalon whloh would ta appropriate for flobal wenitaring has boaa wndac awatmt dlaonalan. d no opoolow haa ywt boon pvopoaod whloh aoota all tho ngulraraotu fod on* a pwvpooo. It la llkoly that a wldo variety of apoolaa mat avwntually ta propoood. tea asnooawant of tho extent of pollution boing bosadon tha rwowltoy fron savsral apaolaa In aaoh anwa. ratbor than on mf partlaulor apaolaa. HONS 043889 14 U, nartatEKciB AIUHG, B. nd JWSBI, g. Anil. Chan. /Q, 1483 (1970) r Al'OH. FCB Baaalattar Bo. 4, p.16, Maroh 1972 ASlOTt, J.A. and BDBKZ, J.A. J. Aaaoc. Offlc. Inal. Chaa., 761 (1970) IPIBG, O.W., DIOEABT, ?.L. and KEBB, O.A.V. Papar to 164th Etj. of Anorlcui Cbaalcal goclaty, 28-31 Auguat 1972 HOIDD:, A.T. Batura, jgg, 1220 (1970a) - O' - Paat. Monlt. J., 4, 117 (1970b) In Karina Pollution and 8aa Ufa (Plahlag Baaa (State) Ltd.) 1972, 266;. D" - In Synpoaiun on tha Biology of tha Baal, Oaalph, Auguat 1972, to bo publiahod by IC3* (1973) ' [I?CBO, II. and KABSBK, X. J. Chronatog., 44, 4B1 (1969) Critical Baaa Mo. 1 (1971) I JliMSK, 3. Boa Scl.nti.t4 34, 12 (1966) - , JOKBIIE. A.G., OISMJ, M. and arMUDIB, 0. Batura, 2ii> 247 (1969) EIGHTH, It.C. PCB Baaolattar Bo. 3, p,7, July 1971 L.BGHA10HY OP THE OOVEBBUOIT CrODST, London, Ann. Bap., 1970 HIJEHIOCGH, B.W., HOGCSFT, BJ., GBHTOI, J_J. and GOimOC, EJ). (olanaa 1W. L - 1233 (1968a) , SEICHE, ?., KAHILI, B.B., HEEKAB, 8. and ISEVte, H. Batura, 220. 1098 (1968b) D" SISGOKS, B.. and BIUTI, 0. J. Chronatog., &, 19 (1971) fl" SOIOOHBI, A., STOSSCH, I). and OUBTBABB, S. krlron. Poll., i, 25 (1972) TAETUMT, X.B. and TATTOB, J.O'G., Batura, ill, 725 (1968) I YK1TH, C.B. and IEZ, G.P. Bator Baa., 4, 26; (1970) B BMSATUr, C.A. and HABniAK, J.A. Batura, 207. 486 (1969) YITBSp M.La Papor to lC4th Mooting of Amvlean Chaaleal loelciy, 28-31 Auguat 1972. zmo, 7. Ball BurIron. Contaa. and Toxicol.* ^ 484 (1971) - * and CIBI T.B.I. Fish. Rat. Bd Canada Todi*!bp., Bo* 272 (1971) L MONS 043890 I