Document 9JRpKmbxj3X8zRq0377dKkpqe

/KA^juUmJ, JCryn-t-ui-a ^ 7/ MV i*r\t(iimiuf. del ]Ulcl:>liinJ.i irlii. Dir Ndminj V), 57 In fimilili'ff* In "'< HjSMlvll III!'ll' J Sc`l. I'OOll , (ImiHWigi'lilc linn)' K-nci'lit . IMirinl AST. ClinnlMi is, ,i .i- vlun klmiieillcldcr edi I mu'll (inmlrl Inn 1901iliitlnri ikiiIIiIiIn ml nrionlo Ili martict In 1001-1007. Act* "ptrd 0 Krlmmy 1070. l '* ' i r v . . ' `` .' r ** ' . rosticiilc residue nnnlysis in the presence of Polychlorobiplicnyls (X'CB'j) By L. M. llumoms* Contents 1. Introduction.................................................................................................. 27 II, Presence of TCUr In tho environment................................................. 31 Ilf. J>Cn inlcrfcrcncc will) pesticide residue analysis.............................. 32 IV. Uses and properties of PC)>'s.................................................................. 3J V, 1'osslbto modes of entry of PCHs Into tho ecosystem........................ 31 VI. Toxicity of Ten's...........................................................................................30 VII. Analysis of pesticide residues In the presence of FCITs............................. 37 VIII. Confirmation of pcsilcido identity .................................................................. 39 IX. Identification of PCB's in samples........................ ..........................40 X. Estimation of PCD**......................................................................................44 XI. Separation rf PCB's from organophosphorus compounds by the Fiorisft tochnkjuo. ...................................................................................... 45 XII. Residue* of organocblorino pesticides and PCB's In Canadian wildlife 45 Summary...............................................................................................................52 H6sumd........................................................................................ Zuianuncnfcssttng.............................................................................................. 54 References.............................................................................................................. 54 I. Introduction Although there has been so much discussion on the pros and cons of pesticide use, it would be unthinkable to start this review without a few comments on the controversy. The recent banning of DDT by some countries and the widespread aud increasing animosity towards the use of the orgunochlorinc pesticides in general are due to a number of factors including: a) The largo annual additions of the pesticides to the environ* ment coupled with their apparent persistence. b) Their known acute toxicitics. c) Their widespread distribution in biological materials and their reported buildup in tho food chains. * Ontario Research Foundation, Sheridan Park, Ontario, Canada. *7 n'rfm 63 MONS 083208 IS L. M. Rkynomm d) TboJr rooro recent implication In the derangement of calcium metabolism (IV.akau, 1007, Simkis 1007, Wr.t.cu cf <d. 1000) possibly causing tbo decrease In eggshell thickness ami the population decline of certain raptorial aperies of birds (JIatcmkpik 1067, Hickey And Andemson 1008, Stickhi, 1009). a) Their Adverse effects on flsli reproduction (Bunmetc cl nl 1001) and high vcsklno lovols found In Colvo salmon in l.nkc Michi* gnn in 1000. ^ ertain "fears" involving chronic toxicltlcs and snblcthnl doses with possiblo deleterious effects on man and wildlife and the ultimate survival of mnn., Tito above factors aro very compelling nml certainly warrant man's concern about Iho threat to his environment and his very existence. Nevertheless, one cannot deny that these pesticides have been impor tant hi ensuring the supply of man's rapidly increasing food require ment and in the protection of his health, ns well ns the saving of millions of lives. Surely, this Is a case whero the benefit-risk* equation as well as tho Alternatives to the organochlorine pesticides should bo carefully studied and evaluated to avoid the possibility of getting into a worse predicament. It was quite ironic when recently a large city publicised thnt, because of an imponding ban on DDT, the garbage collector would pick up separately all home garden sprays and oilier materials which contained even traces of DDT. The material that had been used more than generously and cherished for almost 30 years had suddenly become monstrous even in trace quantities. Wasn't there much greater danger posed to the collectors, children, and animals by such collec tion than if the home supplies had been allowed to run out gradually with no chance of replenishment? In fact, the announced bans on DDT so far are generally not total, and hence servo the same purpose as merely tightening the control on tho uses of such pesticides. In other words, when it is necessary. And until suitable and satisfactory replacements are avail able, limited and judicious use will be made of these pesticides. With regard to the use of substitutes, caution is essentia) to avoid premature use of any compounds. It is now known that potentiation (or antagonism) of toxicity is possible with certain combinations of pesticides and with combinations of pesticide and drugs or environ mental chemicals (Dunozs 1908). A compound might be fairly safe by itself ycl harmful In the presence of others. It is a foct that even if suitable substitutes were found and tho use of the organochlorine pesticides was banned completely, a need would still exist for at least a number of years to have reliable analyti cal methods for the determination of their residues. The present re view discusses tho status of organochlorine pesticide residue analysis HONS 083209 i derangement of calcium 067, wkijcii et l. 19C9) gOtrll thickness nml (ho Mortal species of birds ,on 1068, SncKr.L 1909). I(oh (Kvkimcx of of. 1901) io aalmoii In Lake Mlchl- rllk and aublclhnl doses nan And wildlife And (ho d certainly warrant mnn's it And his very existence, nitrides hove been Imporf Increasing food requireai well as the saving of the benefit-risks equation lilorlne pesticides fhould the possibility of getting irgc city publicised that, yarlmgc collector would iwt other materials which Tint tlmt had been used ost 90 yean had suddenly Wasn't (hero much greAter d animals by such collccitwcd to run out gradually ao far are generally not as merely tightening the other words, wlicn it is iy replacements Are availade of these pesticides, mlion is essential to avoid v known that potentiation ih ccilain combinations of hie and drugs or environound might be fairly safe r*. itntrs were found and the \innrd completely, a need .in In have relinblo annlyttr residues. The present to<* pesticide residue Analysts I'olycliloruhiplit-nyls so with particular reference to serious inaccuracies caused by the pres ence of polychlorobiplicnyls (PCH's) in some samples. As would be expected, hi order to cope with the numerous new pesticides that have been put into use;, pesticide residue methodology has changed diastically over the years. Zwi.ic (1903) point'd out that until about 1040, the life of oil analytical chemist working hi tho pesticide held was' a relatively serene one In which the chemist had to bo familiar only with analytical methods for arsenic, lead, fluoride, pyretInins, rotenone, ami a few others. Just about ti n years book, DDT and other organochlorine compounds wero estimator! by colorimetric methods (SciiRcncn et al 1945) which obviously did not givo precise Infoimation on the amounts and identities of tho individual compounds present. Today's residue methodology Is much more complex, and in order to cope with the new pesticides being introduced, the techniques arc constantly being modified and improved. The wide variations In toxicity and persistence of pesticides, new or old, dictate refine ments in methods in order to differentiate and determine individual residues. . Bearing In mind the complexities mentioned above and the fact that the spray history of most samples (excluding controlled spraying experiments) is unknown to the analyst, the availability of chromato graphic techniques which afTord separation of a number of compounds in a mixture has made the multi-residue screening approach1 (If. S. Food and Drug Administration 1969 revision) the method of choice. Tho gas liquid chromatographic (CLC) separation with electron capture (EC) detection is presently the most popular analytical com bination for organochlovino pesticide residues. Multi-residue analysis involving CLC generally Involves five prin cipal steps: . ' a) Sampling to procure a representative aliquot of the sample. b) Extraction of the residue with a solvent (usually organic since most of the organochlorincs (OC's) end many of the organo phosphates (OP's) arc fat soluble). c) Cleanup of tire extract to remove Interfering materials such as ` fats, waxes, pigments, etc. d) Analysis of the clcancd-up extract, generally by CLC-EC technique. e) Confirmation of the pesticide identity. Certainly there arc A great number of variations in carrying out theso steps, depending on the nature of the pesticide and its substrate. 1 Editor's note: See Buwus, I. A.: Development of the Food and Drug Ad ministration's method of analysis for multiple residues of organochlorine pesti cides fa) foods and feeds. Residue Reviews, this volume. MQNS 083210 30 L. M. ni'YNOl.KS tho limit of dclcctnbillty required, and (lie In1>orntoiy si nil nnd equip ment available. H is beyond tbc scope of Ibis review lo discuss any of these methods in detail. Furthermore, Guntiikm (1962) nnd Samuki. and lionets (1907) have reviewed this topic adequately. Accordingly, this review will deal mainly with problems involving PCB's nnd re lated compounds. No attempt will no made to review gas chromatog raphy for pesticide residue analysis, burner-: (1005) has discussed some practical aspects of litis topic, while Thompson cl al. (1909 and 1000 a) nave evaluated different gas chromatographic columns for chlorinated pesticides. Before) discussing the PCI3$ and their interference with pesticide residue analysis, some' key references in the English language on residue methodology aro appropriate. Theso arc listed alphabetically as follows: 1. Advances in pest control research, vols. 1-4. New York: Inter science (1957 et sen.) 2. A guide to the analysis of pesticides by gas chomalography, 2nd cd. S. T. Treston, Jr. Evanston, III.: Polyscience (1968). 3. Analysis of insecticides and acaricidcs, Gunther and Blinn. New York-IiOndon: Interscience (1955). 4. Analytical methods for pesticides, plant growth regulators and food additives, vols. 1-V, Zweig. New York: Academic Press (1963). 5. Guide to the analysis of pesticide residues, vols. 1 and 2, Burch field and Johnson. U. 5. Public Health Service, Office of Pesticides, Washington, D. C. (1965). 6. Manual of methods for the determination of residues of Shell pesticides, Shell Chemical Company, Agricultural Chemicals Divi sion, Now York (1969). 7. Official methods of analysis, Association of Official Analytical Chemists, 10th cd. Washington, D. C. (1905). 8. Pesticide analytical manual, vols. I and 11, If. S. Detriment of Health, Education, and Welfare, Food and Drug Administration, Washington, D. C. (1908). 9. Pesticide residue analysis handbook, Bonclli. Wilkins Instrument end Research, Inc., Walnut Crook, Calif. (1965). 10. Besiduo Reviews, vols. 1-34. Gunther. New York: Springcr-Vcrlag (1902 el scq.) It should be empWfeod that theso references were all written prior lo tho knowledge that there was a possibility of PCH interference with 1 Editor's note: There sre now more then 05 books concerned wHli pesticide residue* Including 00 that discuss analytics) methodology In some rntpedi: eight oountries are represented by the authors. Cvktiwh, F. A.: Pesticide residues in the total envIfonmcot-Aetlablo detection and determination, mitigation, and legis lative control and surveillance programs. Pure and Applied Chem. ft, 355 (1970). ' MQNS 083211 tAmMory staff mid equipiUit tc\ icw to discuss any yiitui(1062) and Samuel W, arf'-quatoly. Accordingly, ,, Involving I'CU's owl re to review giis clnomntog(1005) hni discussed some ,;s rtfti (I960 awl 19G9a) lie columns for chlorinated ntrrfprcnco with pesticide tle English lnnguago on ti oro listed alphabetically hu 1-8. New York: Inter- I* gas chomalocraphy, 2nd (science (1068). Cttnlher and Blinn. Now growth regulators and food ; Academic Press (1063). ucx, wab. 1 and % Burchrrvlcr, Office of Pesticides, tiov\ of residues of Shell pindiural Chemicals Divi- imt of Official Analytical 1003). III, (A 5. Deportment of and Drug AdminlHraUon, enclli. Withlm Instrument T. (100$). few York: Sprlnger-Vcrlag ts were all written prior to of PCD interference with fata ronrrmrd with pesticide 'dfllcpy In some respects] eicht ' P. A.: Pesticide residues tn minetlen, mftlgstton, end fecitnd Applied Oictn. tl, 355 rolycMoroMplienyl.i 31 certain pcsticido residue analyses. In general, (ho methods described in these references can bo modified to cope with PCM interference. II. Presence of PCD's in the environment Following the development of the EC detectors and their use with CLC, most residue chemists have observed unidentified peaks i on their gas chromatograms- Generally, there was no specific pattern . to these peaks, but analysts concerned with poslicldo residues hi wildlifo, especially In Europe (Rouuhn 1065, IIahmson 1066, Hoiufn and Maiisden I960), sometimes observed a particular series (with as many : as ten or more peaks) of the unidentified peaks in thdr sample cx i tracts. The materials giving rise to these unidentified responses . occurred most frequently and in the largest proportions in extracts from aquatic raptorial species of birds and fishes. The general siipjwsilion was that theso responses were from condensation products of the metabolites of the organochlorinc pesticides, since they were gen erally observed when large amounts of pesticides were also present. RobunN (1065) reported them to be organochlorinc compounds with fairly high chlorine contents, which no doubt accounts for thdr high sensitivities to the KC detector. However, Jensen (1066) wan the first to state that these unidentified peaks corresponded to I'd) com pounds, based on the analysis of a number of pike samples, an carle, and human hair. Initially, the CLC and thin-layer chromatographic (TLC) patterns and chemical inertness were used to identify tho unidentified peaks as PCBs (Jensen and Widmatik J9C7). v Other workers in Crent Britain (Holmes ct al. 1067, IIoi.mi n and Mausden 1907) and the Netherlands (Koeman ct al. 1007) also made early reports on tho presence of PCBs in their fish and wildlifo Samples. At tho Organisation for Economic Co-operation and Development (OECD) Conference on "The Unintended Occurrence of Pesticides in the Environment," held in Scotland in September, 1967, tho Euro pean chemists in particular showed much concern regarding the pres ence of PClVs In their wildlife samples and the possibility of inter'fcrcnco with their organochlorinc pesticide residue analysis. Up to that time, there had been no report on the occurrence of these mate rials in North American samples. However, in a December, 19G7, /report on organochlorinc pesticides in seals and porpoises, Holden .and Mausden included a comparison of tho amounts of PCB type . materials found in Scottish and Canadian samples. They reported that the levels of these non-hydrolysnblu materials were generally '''much lower in lho Canadian specimens.'Since that time Risitnnouctt al (1968) have reported that the PCB's arc widely dispersed in _^the global ecosystem, while Reynolds (1968, 1909, and 1969 a) has found them in somo Canadian wildlife samples. MONS 063211 L. M. HEwni ns Positive confirmation of tho PCBs by gas chromnlogrnpby*mj*ss spectrometry (GC-MS) has now been reported In Sweden (Wiumaiuc 1067), the Netherlands (Koeman el at. 1060), and In the United States (Rkicju-.l 1089). m- PCD Intcrfercnco with pesticide residue analysis The polychlorobiphcnyls (X Indicates tho possible chlorine posi tions) and related compoundss (polychlorinated triphcnyls, naph- thalenes, tcrpcncs, etc.) have nu merous important industrial uses but arc not used as pesticides. Because of their similarities in structure and properties to tho DDT pcsticido group, tho l*CBs--If present in a substrate--ore carried through the usual pesticide extraction and screening procedures, and since they possess electron absorbing properties, will interfere with G1..C-EC analysts of orcanochlorinc as well as a number of the organophosphorus pesticides (Reynolds I960 b). Tho reported CLC patterns indicating TCB interferences havo shown marked resemblances with `Aroc)or )254 and 12GQ (Jensen and Wiomahk 1907, Holmes cl al. 1967, Reynolds 10C8 and J0G9, and JCoeman et al 1069). This typo of interference with pesticide residue analysis is demonstrated with a standard mixture of oignnochlorine pesticides and a commercial RGB mixture (Aroclor )Vi) Jn tho chromatograms of Figuro 1. lire results confirm that the pres ence of PCB's in the sample extracts will cause interference with pcsticido rcsiduo analysis under these or similar operating condition*. It should bo emphasized that throughout this review when the term "PCll" is used, this includes the polychlorobiphcnyls ami also tho other closely related compounds mentioned above. Jlowrvpr, the polychlorobiphcnyls are the most important from the point of view of interference with pesticide residue analysis. Under the GI.C opernting conditions, the chlorinated polyphenyls and other related com pounds with molecular weights greater than the chlorinated biphenyls will generally not be separated and observed on the gns chromato grams. Modification of the operating parameters such as higher col umn temperatures or changes in the liquid stationary phases are usu ally necessary to dotcct the presence of such compounds. It must be borne in mind that when high molecular weight com pounds arc present, their peaks can appear on subsequent chromato grams and cause "secondary interference." This occurrence can be recognised easily by the early emergence of unusually broad interfer ing peaks on the chromatograms. Secondary interference" is a term used by the author to imply that the interfering peak does not have MONS 0832X3 fi1 chromatography-mas* jrt| (n Sweden (Wiiimaiuc !l(lll). *ntl in tho United p redduc imlysls he possible cWorlnc posllinnted biphenyls, ii.ipliiprtips, etc.) hnvo mi* mtnnl Induitrinl uses but d ns pesticides. Bccnuso lilntitics in slructurc and to tbc DOT peslleldo .arc curried through tho orethnrs, and since tliey inierfere with CI.OKC niilirr of tho orgnnoplfqs- l*CB Inlcrforcnocs liavo ' )25i and 1200 (Ihnsism IIkikouis 1008 mill 1909, lU'itercnco with pesticide imlnrd mixture of orgnnol mixture (Aroclor 1251) nils conlinn thnt the pros it r,ime Interference with milar operating conditions, nut Ibis review when tlie lyrlilnrohiphcnyls and also muni above. However, tho tit 'from tho point of view us.' Under tho G1.C opornth and other related comn the ehlorinatcd biphenyls ived on the gas chromato'nirters sueh at higher col1 stationary phases aro usu'eh compounds. ilgli molecular weight comu on subsequent chromalo- Till* occurrence can bo uf immunity broad interferluy Ininferenee" is a term firing peak docs not have I'olychloroblphenyls 33 tho saino retention time as thnt of the compound of interest under tho same operating conditions. The interfering peak often originates from a previous injection and cannot be simply repeated. Of course, if tho elution timo Is very long, tho peak might be broad enough to oscapc detection and ip such a case would not Interfere. In contrast FI*. 1. rCB Interference with orgnnoclilorinc ncsticldo residue analysis on four percent SE-30/six percent QIr-l on 60/80 mesh Chromosorb W, %' x 6' boioslltcate column. Chromatogram A: standard mixture of orgnnochlorlne ' . pesticides; peak numbers: 1 * 0 08 ng. of lindane, 2 0.10 ng. of ficptachlor, 3 0.10 ng. of aldrin, 4 TM 0.14 ng. of heptachlor epoxide, 5 TM 0.20 ng. of DDE, 6 " 0.20 ng. of dicldrin, 7 0.30 ng. of DDD, and 8 - 0.50 ng. of DDT. Chromatogram 0; 5 ng. of Arodor 1254 (the 14 major peaks arc numbered I to XIV). Chromatogram C: combina tion of above oreanochlorino standard postlclde mixture and Aroclor 1254. Injector 250*C., oolumn 200*C. detector baso 250*C., Ni it 20 90 cc/minute to this type of interference, materials which have identical retention times will cause "'primary interference** which is easily repeated by reinjection of the extract. With this form of interference a single, sharp peak Is obtained, and in the absence of confirmatory and other precautionary measures, misinterpretation can occur easily. PCB-type Interference falls mainly in this group. i hqns 0832b4 34 L. M. Rkynolus IV. Uses nml properties on FCB's In order lo undcrstitml how it is possible for I'CJi's to be present In wildlife nnd cause interference witli pesticide residue analysis, it is necessary lo give a brief description of some of their propci lies nnd uses. The PCfl's are produced nnd marketed under a number of com* mcrcinl trade names, c.g., 'Aroclor,* 'Clophcn,' and 'Phcnocblor.' KokMan ct nl. (3969) rcpoilcd marked resemblance between Aroclur 1260, Clophcn ACO, and Phcnochlor DPO. The 'Aroclor' nlnstici/.crs, a series of chlorinated biphenyls and chlorinated polypbcnyl.i, arc typical of these compounds. As stated by the manufacturers (Mommt/o Co. 1007), the 'Aroclor' compounds arc among the most versatile chemically produced materials available. They vary from mobile, oily liquids to white crystals and hard transparent resins. They arc non-oxi dizing, inert, permanently thermoplastic, of low volatility, non corrosive to metals, insoluble in water, and resistant to alkalies, acids, and corrosive chemicals. The viscous, more highly chlorinated liquid and resin members do not support combustion mul they Impmt fire rcturduncc to other materials. The crystalline 'Aroclor compounds are relatively insoluble but the liquid nnd resinous compounds arc soluble in most of the common organic solvents, thinnrrs, nml oils. These compounds are used in protective coatings, ns placlidzns and extenders, as sealers in water-proofing compounds nnd putty, in asphaltic materials, printing inks, waxes, nnd synthetic ndhrsives. Liquid PCH's arc used as dielectrics, as hydraulic fluids, in thermo stats, In cutting oils, as extreme pressure lubricants, ns grinding fluids, and as heal transfer media. Solid PCB's arc used to impregnate carbon resistors nnd ns sealers in impregnating agents for electrical apparatus. The properties of many products can be vmied and improved by tho use of these compounds either as primary or secondary plasticizers. Further details concerning tho different 'Aroclor' scries, the grada tion of their properties, and the numerous possible applications can be found in tho manufacturer's technical bulletin (Momanto Co. 1967). In the system of designation for tiro 'Aroclors,' the first two digits indicate the type of material, while the lost two digits givo tho approximate weight percentage of chlorine in the product. For example, 'Aroclor* 1254 indicates a chlorinated biphenyl with approxi mately 54 percent chlorine, while 'Aroclor' 5460 indicates a chlorinated trlphcnyl containing about 60 percent chlorine. ' V. Possible modes of entry of PCB's Into tho ecosystem The means by which PCB's enter the ecosystem to contaminate fish and wildlife are still not dearly understood. There arc however, MCNS 063215 , ,, rc' ,,|P to, I'ClI't to lie present ...tiriile residue analysis, it Unr of tMf properties ml I ,.,l under n number of com'ii end Thenocldor. Koi-i-,iitit:inec between Aroclor Tin' 'Aroclor' nlnstlclzni, * led polyphony's, ere typical nwnufneturcrs (Monsanto oniong tbo most versntilo I'licy very from mobile, oily , lit rrsins. They ore non-oxip, of low volatility, non,| ri'iislant to olkolics, nclds, re highly ehlorinnlcd liquid milfoil and thoy Impafi flro lalline 'Aroclor' ccmqwtimls ml resinous conqioimds arc i-viits, Ihinncrs, and oils, live coatings, as plaetiri/.ers Hug compounds and putty, p, and synthetic adhesives, hyihaulic fluids, In thcrinoliifiricnnis, ns grinding fluids, c mill to impregnate carbon [cuts for electrlcal apparatus. ie varied and improved by iry or secondary plasticizers, it 'Aroclor' series, the grndn>ns possible applications con al bulletin (Monsanto Co. the 'Aroclors,' the first two isle the last two digits giva himInc in the product. For Hated biphenyl with approxl' 5 ICO Indleatcs a chlorinated Mine. It's Into the ecosystem lie rcosyslcm to contaminate drislooa. There arc however, Polyclilorubijilicnyls 35 four most likely pathways by which PCB's enter fish and wildlife: a) Because of their inertness and versatility and consequent numerous applications, it Is quilo conceivable that PCII's . could be flushed ns wastes into rivets, lakes, etc. to pollute? fish nnd other wildlife. b) There Is ft possibility that some contamination could proceed via the atmosphere when wastes containing these compounds are burnt c) Although it Is unlikely, some typo of Uflmnn reaction with condensation of aromatic halides with the aid of metallic agents such as copper to give rise to the formation of biaryls, cannot be completely ruled out. - d) Lastly, but not nccossarily the least likely, there Is the possi bility that some companies arc using PCJVs In some Insecticide formulations to increase the kill-life. lire Idea of increasing the residual persistence of insecticides has been investigated for somo time and a brief r6sum6 on tire moro Important background work is in order. The early investigations by Lindquist el ok (1945) and Broca (1948) indicated that the residual effectiveness of DOT was pro longed when the DDT was applied in resins and paints, van Tikl (1952) continued along these lines when he increased both the effeetivo period and the toxicity of a DDT deposit on a glass sin face by the Addition of n small amount of coumnronc resin to n DDT solution hi kerosene. Subsequently, cmphnsls was placed on work involving the more volatile insecticides like lindane -n very rfTretivo pcsticido but one which soon loses its activity because of volatilization. Suixivan and IIomnstkin (1953) in their experiments with tlio American cockroach, Perlplanela amcricana, found that lindane resi due remained toxic longer when it was compounded with Aroclor 5460. They suggested that the chlorinated polypheny] prevents crystal lization ot the lindane and lowers the vapor pressure of the lindane in the mixture, thereby preventing unsightly residues on surfaces ns well as extending the effective kill-life of the insecticide. Tsao el al. (1953) obtained similar results against house flics, Aftuca domesUca L. Continuing this work, Hohnstfin and Sui.mvan (1953) con firmed these findings and described a general method for prolonging the residual effectiveness of volatile insecticides, lire method consisted of preparing concentrated solutions of the pesticides in the film-form ing polychlorinated polyphcnyls. A Monsanto Co, Technical Bul letin (1965) states that because " `Aroclors' in formulations `trap' and hold more volatile ingredients, they make volatile insecticides and repellents last longer' in residual Activity." Attempts to determine whether this IdcAhad been put into practice bavo so far been unsuccessful. However, if the PCB's arc being used MONS 083216 30 L. M. RtiVNOUM In pesticide formulation, then tins coupled with t!c numerous other uses suggested In a later Afonwiuto Co. Bulletin (1907), might cer tainly explain their presence In wildlife tissues ami other fjtmnlrs. Thcro is an obvious need for clarification of the sources of I*CB's in fish and wildlife, apd this could probably be accomplished using tracer techniques. VI. Toxicity of PCD'* The PCB's were studied as early os 1881 (Schmidt and Sciim.T/.) and were in wide use by 1930 (Penning 1930). Later Jonj;s and Ai.nr.N (1936) reported that tho compounds wero toxic. CwxNninc cf nf. (1939) reported that PClVs and polychlorinated naphthalenes caused tho deaths of three workers. Men employed in the production and uso of PCBs developed acnc-lypc skin eruptions (ScmvAur/. and llAiti/JW 1942, Sciiwaiviv. and Puck 19d3, Schwartz 1943). Mn.ucu (194*1) reported ihnl POB's caused pathological changes m in laboratory animals. Brown (1947) warned aliout the toxicity dan gers of the `Aroclors' when there was a suggestion that one of tho VVroclors' be used as the melting point bath liquid in preference to the customary sulfuric acid. Later, McI.auciii.in cl rtf. (1963) found that Aroclor 1242, besides being toxic, produced teratogenic effects 1 in chick embryos at lower dosage levels. llisnimoucn cf at, (1908) r.'' reiterated that PCB's along with other chlorinated biocides, such as 1 DDT, could account for a large part of the aberration in calcium : metabolism that has been observer! in many species since the second } world war. With high dosage of PCB s, hydroperienrds have been observed in quails ( Kokman ct al. 1909). ' It has been stated (Monsanto Co. 1967) that at ordinary tern\ pcrnturcs tho 'Aroclor* chlorinated polyphcnyls do not present Indus* ; trial toxicological problems. However, caution was advised in handling l*` these materials. Tho hazard of potential toxic exposure varies with t_.`thc volatility of the compounds: the lower chlorinated, more volatile ones present more of * potential problem from the standpoint of c botli inhalation and skin contact. Al elevated temperatures, the use *of PCB's requires very effective and efficient exhaust ventilation systems. ... It has also been stated by the m/miifnctmcrs that "tests on animals Indicate that tho maximum safe concentration of vapor is in the range ; . of from 0.5 to 1.0 milligram of the lower chlorinated `Aroclor* plastil-_.ci7.crs per cubic meter of air. The threshold limits (maximum alkiw` able concentration for an 8-hour working day) set by the American 1 Conference of Government Hygienists arc 1.0 milligram of the lower . chlorinated 'Aroclor* compounds per cubic meter ofair and 0.5 mfftlgram of the more highly chlorinated compounds, such as 'Aroclor* 1254, per cubic meter of air." HGNS QQ3217 /* . >ii. thr innucious other ..... . ** thcrr$z, ,,, ,,| On- wk** of 1CB1 ;;;.;* *h 11 | (Schmidt ami Schui.t/.) 1030). Lntcr lows and b were toxic. ir))ii in.ited naphthalenes imloycd in tho production iiuptionx (Schwahtk and nwAnr/. 19-13). used pathological changes ml about tho toxicitt dani]*|rsiioii that one cl the [h liquid in preference to situs ci id. (1903) found nhicrd teratogenic effects ItiMiMHOwn cl al (1968) urinated biocides, such as (Vm* alienation In calcium v specie* since the socond fqumpcric.irds have hem >7) that at ordinary 1cmuyl* do not present Indushi was advised in handling nxie exposure varies with chlorinated, more volatile it (tout the standpoint of tint temperatures, tho use leient exhaust ventilation wro thnt "tests on animals on of vapor is tn the range chlorinated `Arcelor* plastlId limits (maximum allow* d.w) set by the American l.w milligram of the lower meter ofair and 0.5 milli'poundi, such tt `Aroclor* rolycliloi ubtplicnyh 37 However, as Risi.nnoucn ct al (1968) pointed out, only relatively small Amounts of chlorinated hydrocarbons arc required to cause cnzymc-lnduccd breakdown of steroids, thus making Irrelevant much of the p.p.m. approach to pollutant ecology based on toxicity data alone. There is no doubt thnt further research In this area is urgently needed. VII. Analysis of pesticide residues In the presence of PCBs PCBs aro of interest to analysts for throe main reasons: a) Tho compounds arc toxic. . b) Thoy arc widely distributed ami their uses arc increasing. c) They interfere with GI.C determinations of orgnnocliforino ml orgnnophosphorus pesticide residues. The first two reasons have been dealt with earlier and therefore need no further elaboration. Accordingly most of tho rctnaindri of tills review will be concerned with tire analysis of pesticide residues in tho presence of PGB't. Also the present methods of estimating tho amounts of PCBs will be discussed. As mentioned earlier, it was emphasized at the 1907 OECD confer ence that PCB's were in fact being detected in fish and wildlife, especially in Europe. 'Hie conference among other things served to alert other chemists ami scientists to the problems of PGU* and their Interference with pesticide residue analysis. Since the discovery thnt PCB's arc contaminating fish and wildlife and that they intnfrro with organochlorinc pesticide analysis, very little has hern published on how to copo with these interferences and how to differentiate the PCB's from pesticides. Based on preliminary work, Jknsi-n ami WiuMAmc (1967) suggested a nitration technique based on the incli nes* of the PCB's compared to the relatively easier nitration of the pesticides. Riswmoven cl al (1968) reported the use of this method, out Reynolds (1969 b) pointed out tliat nitration h not a suitable approach since some pesticides (lindane, toxapene, Strobnne, etc.) apparently will not nitrate, while some of the PCBs appeared to be nitrated under the suggested conditions. In addition, there Is tlic problem of further complication from the interference of the nil roderivatives formed, especially when the DDT-group pesticides are present in large amounts. To avoid the above complications and at the same time facilitate the chromatographic interpretations and afford a means of estimating tho PCB's and pesticides independently, Reynolds (1969 b) Intro duced a FJorisil separation scheme. Kokman el ol (1969) have also reported a similar Florisfl column technique to separate tho PCBs from the pesticides. rtONS 08321* 38 L. M. RkYNOI.I* In Rkykolos' method, the partially elenned-up sample extract con taining the pesticides and PCUs is placed on a Florisil eohmm and tho Ten's arc eluted first with n-hcxnnc, followed by elution of the pesticides with an ether-hexane mixture. Originally, tins technique was intended to serve ns the final cleanup step, as well as effecting separation of tho PCB's from the pesticides. As will be explained, tho method has since been slightly modified (miniaturized) to serve mainly as n separation technique. Of tho many pesticides investigated, only hcptnchlor, aldrln, nnd Inc DDT metabolite p,p'*DDE me eluted with tho I*CJVs. With the exception of p.p'-DDl'., those do not present difficult problems since chemical reactions (cpoxidatlon, hydrohioinination, etc.) can be used to differentiate hcptnchlor and aldrln from the rCBV Furthermore, these two pesticides arc more frequently found as tho more stable epoxy products which arc separable fiom the FCB's by this scheme. p,p'-DDE on the other hand presents a more difficult problem on account of its chemical inertness. Its greater stability resembles that of the PCB's, and the compound is not amenable to any simple and convenient method of structure modification to give a product which is readily detected within the usual GLC-EC operating param eters. Of course the ideal situation would be a convenient addition of one mole of hydrochloric add to tho p,p'*DDE to form p.p'-DDT while tho rCB's arc not affected. Tills would afford confirmation and quantitative estimation of p.p'-DDE in the presence of Kill's. Gen erally under such circumstances it would not be necessary to do an additional Florisil separation. The amount of p.p'-DDE present could bo estimated Indirectly from the n.p'DDT produced since, ns will bo discussed Inter, the p,p'-DDT (and p,p'-DDD) can be separated from the POB's by the use of highly polar liquid phases. It sliould bo emphasised that although p.p'-DDD and p,p'-DDT aro mostly separated by the polar phase columns, without introducing a Florisil separation tho earlier emerging pesticides are superimposed on the POB's and lienee a separation 1$ necessary to identify and to quantify these latter pesticides. After tho Florisil separations of POBs and pesticides are made, the two duates arc chromatographed separately on the SK-30/QP-1 column and compared with appropriate standards for quantitation. This is normally followed by confirmation of the identities of the pestioidcs. Vm. Confirmation of pesticide Identity Despite the separation of the PCB's and their elimination as sources of Interference, the non-specific nature of the EC detector HONS 063219 ,| nil sample cxlrnct con| n a Ilw|*ll CT,lumn "Ht* MIoutiI l>y chillon of llio , (iiifjn.illy, till* (cclmlrjuo it slip. *s will "s clfccllnp ili-j. As "III be explained, (mlrilalmlzc(l) to servo i,(ny pesticides tnvcslignlcrl, lioiilr p,p'-13DIC ro eluted |l)OB, tlieso do not present (r|KKlilntion, hydrobroml[rrptnrhliw end eldrln from [Ules ere more frequently which ero separable from H moro difficult problem greater stebility resembles nl emrnnblc to eny Viniplo (lealion to give e product CIX-EC operating parem- r a convenient addition of /DUE to form p.p'-DDT aid afford eonlinnatlon end ic presence of rCH's. Gcn- iml lie necessary to do an of p.p'-DOE present could |>T inoduced sinco, es will p'-lJIJD) cen bo separated jitptid phases. Illi pp.,tjrr'*iD: DD and p.p'-DDT I'lnmns, without Introducing jpcstiridci are superimposed i necessary to locntify And t nnd pesticides are mode, mrntrly on the SE-30/QF-1 standards lor quantitation, on of tire Identities of the Wdc Identity ' a and their elimination at nature of tlio EC detector rolyclilyioblpliciiyU 39 makes It necessary to confirm tho Identity of tlio pesticides by addi tional techniques. Tlio sequence usually followed by our laboratory Is: Fig. t. Separation of PCB's and orgunoclitorlnc ncsllcidcx on polar phase column , . (five percent DECS/two peroent llePOs). Chromnlogrnm A: standard . . mixture of organocWorJne pesticides wilh saino amounts as in Figure 1; peak mimboN: 1 - hcptacnlor and aldrln, 2 - Undone, 3 hcplachlor ' qioililo, A - DDE, 5 < dlcldrin, 8 DDT, 7 " DDD. Chromatogram . S: 6 ng. of Aroefor 1254 (the 14 major peob arc numbered I to XIV . ' ' aa In clmwiAtocrani B of Figure 1, assuming that tho order of elution ... Is unchanged). Chromatogram C: combination of organochlorine standard , ... pcsticido mlxturo and Aroclor 1284. Other GLC parameters as in ; ' Figure 1 I; , *v separations of pesticides, PCB's, and a mixture of the two .- .... --v' i - group wo shown in Figure 2. The reversal of p,;/-DDD and ' V.v ' p,p'*DDT and their separation from most of the PCB's is note* ~*. J>.; v., worthy and quite useful. One drawback Is that peak No. 13 ` ` > of Aroclor 1260 Interferes partially with p,o'-DDT. Other use* \ ful Information can be obtained by study of the retention times vV.\v\ 'r. *; fv * V*\sO,,y . ' VCO' MOWS 083^20 . L. M. ItnvNOuwi of individual pesticides, For example, this approach afford* separation of Inc three main BJJC isomers. Inc technique is especially useful for ruling out the presence of pesticides in dicated as possildy present by the S15-30/QF-I column. How ever, the retention times on two or more stationary phases cannot bo regarded as independent parameters of identity (Roiiinson 1907). b> Dcrivatixntion and use of characteristic CLC retention times 5 of the derivatives. As reported corlier (Reynolds 1909 a), our laboratory bas increasingly utilised chemical reactions for conUrinations of pesticide residues because the samples to bo analysed aro generally small and the amount of residue Is in- 1 sufficient to allow effective application of infrared, mass, and , other spectroscopic methods. t ' The dcrivnllzatfon technique has been used by a number of work ers (CuNninn 1062, Klein et at 1904, Hammence ct at 1965, Sans i 1967, Duffy and Wong 1967, Osapciwx and Wanusss 1968, Cochrane > | and Chau 19G8, Chau 1969, Chau and CocimANE 19G9, Wiknckb and ] | Buiike 1969) and is gaining in popularity. Success of the technique usually depends on the specific derivative remaining lipophilic and therefore extractable with the organic solvent (usually hexane) for direct analysis by the usual GLC-EC method. '' -. A number of chemical reactions is available, but two of the moro broad-spectrum types that are quite useful for the pesticides generally 1; > ii \ !I found in wildlife ru e: (I) Reaction with etlinnolic potassium hydroxide (mainly dehy * : drochlorlnntion) to give; products with shorter retention - , times, lids Is effective for DDT, DDD, and their isomers, as : ' ' well as fr- and y-BIIC; the /J-isomcr is not affected. , \\ f ; '(11) Reaction with hydrogen bromidc/nectic anhydride reagent \ ] to givo biomohyarin or bromoaccloxy derivatives with longer I __ ___^________ retention times. This reaction has been found useful for hep1 !, , tacldor, aldrin, hcplachlor epoxide, dieklrin, and endrin. . | , c) .Thin-layer chromatography. In spito of certain drawbacks with TLC for confirmation of small amounts of pesticide residues (Reynolds 1969 a) the technique Is still valuable for the con firmation of DDE. TLC can do quite useful also for some group separation, as an ancillary cleanup technique, and for semiquantitatlve estimation of some pesticide residues. \ IX. Identification of FCU's in samples ; . Data obtained by our laboratory in the course of work conducted for The Canadian Wildlife Service have demonstrated that PCB's ; are present in some but not all species of Canadian wildlife. Undoubt- t j ;` 'f HONS 083221 il)i5 approach Affords 'iJmns. The lrflmic]llc is , ot pcslicidet InSlvW/yiM column. Howor more stationary phases nt p.uamctcrs of identity Mir CI.JC retention times r (Hkynoliw I960 a), our jirmicnl reactions for contame the samples to be K amount of residue is in* inn of infrared, mass, nnd urd by ft number of workmnu.no: cl al. 1965, Sans I Wani.uss 1008, CorntiANK :imANi: 1009, Wwnukr nnd Success of the technique remaining lipophilic and rent (usually hexane) for \, l.thlc, but two of lire more for the pesticides gcnernlly hydroxide (mainly dchyl\ with shorter retention 101), nnd their isomers, as r is not nffcctcd. fwvtic nnhydridc reagent \y derivatives with longer I men found useful for hep* , (lieldrin, and endrin. of (Titain drawbacks with mots of pesticide residues still valuable for the con|iiilc useful also for some -Icamip technique, and for pesticide residues. in snmplci course of work conducted demonstrated that PCIVs anudian wildlife. Undoubt rolycIt!orol)Jpl-nyls 41 edly the presenee of PCIVs has complicated llic pesticide ri-.ulni; methodology, but this complication cannot be avoided if meaningful results we to he obtained. Since not all samples contain VC,t\ it would bo unwise to do n Florisil separation on all extracts- brfmr having some indication whether or not the separation is neecssary. Accordingly our laboratory uses the approach described below. The sample to be analysed is extracted, clcam-d-up, nnd assayed using the SF-30/QF-J column. Depending on the KC lesnlts, n deci sion is made whether or not to make a Florisil separation and rhrek further for the presence of PCIVs. This decision is based on (lie as sumption that if there arc no apparent p,p'-DDD and p.p'-DDT peaks, then the presence of l'CB's would not be expected. The DDD-DDT combination is chosen ns the criterion because peaks eight nnd ten, two of the larger peaks in Aroclor 125-1 and 1260 have identical reten tion times with p.p'-DDD and p.p'-DDT, respectively. Also, the PGB components giving riso to peaks eight nnd ten arc less likely to be metabolized than the earlier emerging compounds. Hence, if PCIVs (123-1 or 1260 pattern) arc present, peaks should show up giving apparent p.p'-DDD and p,p'-DDT values with the EC detection system. Ollier useful information regarding the presence of PCIVs can be obtained from the initial gas chromatography. If the GhC pattern (prior to PCB separation on Florisil) shows high `'apparent** p,p'-DDE with little or no p.p'-PDD and p,p'-DDT present, then all or most of the `'apparent" DDE is probably "true" DDK. This Is because peak five (the peak which interferes with p.p' DDK) in the common l'CB commercial mixtures (Aroclor 125-1 nnd 1200) is relatively small compared to the DDD- and DDT-inlrrfermg freaks (eight mid ten) ns shown in Memo 1. This rule lias been Ironic out by TEC confirmation of DDK in n number of such eases. As mentioned above, the two most commonly found PCB types In wildlife samples resemble Aroclov 1254 and 1260. Although these two Aroclors are, quite similar in many respects, certain difTerrners in their GLC patterns, as shown in Figure 3, can be used to identify one from the other. With a higher chlorine content, Aroclor 1200 shows about 17 major peaks (SE-30/QF-1 column) compared to 14 with Aroclor 1.25*1. Besides this, one other obvious major difference Is the peak-height ratio of peaks len and 13. This ratio has rough values of 0.3 nnd 1.0 for Aroclors 1254 nnd 1260, respectively. Additional information regarding the PCB mixture present in a sample can be obtained by comparisons of other peak-height ratios of the PCB standards and the PCB's in the sample. However, it must be borne in mind that in practice one might be faced with complex mixtures of PCB's rather than a single, specific mixture. In such cases an average value seems to be the best compromise. 1110 method of estimating PCB's described below attempts to take this into account. * X v- ^ MUNS 083222 I' ii 42 M. 11i:ynoi.s Although most of the early reports on tho presence of PC Ms in samples indicated the Aroclor 1254 CLC pattern, more recent woik by Kokman cl al (I960) and tire author's laboratory has indicated that a proportion of the specimens docs contain the Avoclor 1200 "J CLC pattern. Tltis apparent predominance of the Aroclor 1251 type might have been duo to its availability as a standard and lack of the Aroclor 1260 type in the early developmental stages of PCI) methodology. The CLC profiles of a number of commercially available PCI) mixtures were determined using the SE*30/QF*1 column. These re shown in Figure 4 and Indicate that tiro more highly chlorinated 1 l i Fig. 3. Comparison of Amclors )254 and 1200. Chromatoguun A: 5 PR- of Aroclor 1254; the 14 major peaks arc numbered 1 to XIV as lu chroma togram n of Figure 1. Chromatogram D: 5 ng. of Aroelor 12G0; the 17 major peaks arc numbered I to XVII (the early peaks correspond to thoso In Aroclor 1254). GLC parameters ns in Figure 1 r biphenyls (Aroclors 1254 and 1260) nrc easily detected with the usual operating parameters. On the other hand, the compounds of the lower chlorinated mixtures (Aroclors 1221, 3232, and 1242) and the higher molecular weight mixtures (o.g., Aroclor 5460) nrc less responsive and nrc, therefore, more likely to go undetected under normal operat ing conditions. Apparently, the lowered sensitivity is due to low chlo rine content in the first group and to high molecular weight with resultant long retention times in the second group. In both eases, therefore, higher concentration would be a prerequisite to ensure detection under normal conditions. This, as well as the possibility of metabolism of the less highly chlorinated biphenyls (Kokman ct 1 MOMS 0032*3 l,. piesciicc of J'CIts hi ,11,111. more remit work t.ilioi.ilory Inn Imlicolal Miil.iiii till' Avoik.r 1200 ,,f the Arocloi ]2j-l typo n iliimliml ' 1'irk of iiiinrnliil Mnrej of 1'CB >f rmmmrclally nvnllnl.lc ;.J0/Qlr-J column. These more highly chlorlnntod A / I ItllltllllMiiliiUltli. I IS 90 99 (liitwniUogrAni A: 5 ng. of Ht<d I (o XIV m to diruina ng. of Aroclor 1200; Uio 17 * rally peaks correspond lo in Figure ) ly detected with the usual c compounds of the lower md 12-12) mid the higher *100) are less responsive ( led under normal opera!* dimly is due to low chlo* ,h molecular weight with nd group. In both cases, a prerequisite to ensure it well as the possibility d Mphcnylt (Kokman ci Polychlorohfphcnyli 43 at 1909), might explain the general absence or rarity of these coin* pounds in wildlife samples. It must not be overlooked, therefore, that in the presence of large amounts of the lower chlorinated biphenyls (c.g., Aroelors 1221, 1232, rig. 4. GLC profiles of tlic more popular Aroclor mtaturrs itndcr nonnnl analy tical conditions. Noto: All peak numbers correspond to tlrose of Aroclor 1254. ChomntogrnniSi A -- 5 ng. of Aroclor 1221, B - 5 ng. of Aroclor 1232, C " 5 ng. of Aroclor 1242, D > 5 ng. of Aroclor 1254, E 5 ng. of Aroclor 1200, and F 5 ng. of Aroclor 5400. GI.C parameters as In Figuro 1 and 1242) and negligible quantities of the higher chlorinated bi phenyls (c.g., Aroelors 1254 end 12G0), different criteria would be necessary to detect PCB interference. To date, this condition has not been encountered in Canadian wildlife samples. *ONS 44 I.. M. ltKVN'Of.US As might be expected from tbe complex nature of iho IX*H mix tures and tho chemical inertness of tbe individual compound", the confirmation of identities of these materials is much junre dillhnlt than with tho oiganochloiine pesticides. 'Jims, in the; nb'.onec of o mass speclromclcr, confirmation of the PCW's is mainly by their Cl.C retention times and patterns on the mixed and polar phase columns In conjunction with their non-reactivities with the two general reagents used for the organocblorine pesticides. The prior separation of the PCB's from the oignnocblorinc pestb cldcs by the Florlsil tcclmhptc also aids In the Wentificalion of the PCW's. X. Estimation of TCH's Since the PCB's are themselves toxic, attempts have been made to estimate Iho amounts present in samples. It should, however, be recognized that only rough estimates can be made since pure stan dards of the individual compounds in the mixtures aro to dale unavail able. The situation resembles that of toxaphene estimation, but is of greater complexity. Koeman cl at. (1969) based their IXUl estimation on the peak of phcnoclor DPG having r, (relative retention lime with dicldrin - 1 under his operating conditions) ccjunl to 1.45. Wisr.imown ct at. (1969) estimated the PCW's on the assumption that they have similar EC responses to p,p'-DDF and applied a factor to fit the assumed 54 percent chlorine content of the PCW's. Jknsen ct at. (1009) ieported estimates as the sum of all the PCB components. The authors laboratory uses a method very similar to Koi man's with the exception that an average based on two peaks is usually employed. Should the two values before averaging vary to any extent, additional estimations arc made using oilier peaks, and all the results arc averaged. In the ease of a few samples, the PCTJ level was ob tained by averaging results from all the major peaks in the mixture; however, the use of peaks eight and ten only has been found to pattern. Peaks eight and ten were chosen because of their stability (sec section on identification)- In a hater section the above points arc Illustrated by analysis of resin powder taken from a fish hatchery trough. The total PCB results obtained by the method described may bo slightly higher than the actual values because the early emerging PCB peaks (mainly one, two, and three) arc usually absent from the chromatograms of sample extracts. However, this should not affect tho overall results greatly since these peaks represent minor compo nents In tho mixtures. Furthermore, there might be compensation, since no attempt has been made to apply recovery correction factors. MQNS 0632^5 v ,nhur of llc PCH mix* ulividti.il compounds, the Is is much more cliflU-oll Ims, in the absence of a , is mainly by their GLC niu) polar phase columns li |)ir two general reagents tlic organochlorlno pest!* i the iurnUflcalion of tho *s illempts have been made ]| .should, however, be |>c made since pure stanixtims arc to date tylavnfl* iphene estimation, but is 1) estimation on tl^o peak ion time with dickhin " 1 i 1.45. ItiNKimoucii ct a!. lion that they have similar fiidur to fit the assumed ct aJ. (I960) rc- timjxmrnts. vciy similar to Xorman's 1 on two peaks is usually vraglng vary to any extent, t peaks, and all the results s, the PCH level was oh* ajnr peaks in the mixture; only has been found to it results arc reported as mling on the overall GLC i hiTansc of their stability set lion the aliovc points taken horn a fish hatchery he method described may because the early em'/rging ) are usually absent from 'ever, this should not ofTcct da repiescnt minor compo* t might be compensation, rrover)* correction factors. rolyc1i!orol>|*lic'yli 45 The method of estimation described above appears to give a rea sonable estimate of PCH contamination based on commeieial PCI! mixtures. For absolute measurement of PCII content it would hr necessary to prepare standards for the individual PCH component*, and, even if these were available, tho dcteiminalions would he complex and cosily. Considering our present limited knowledge of total PCD toxicity and our even greater ignorance about the toxicity of the Individual components of the mixtures, It is doubtful whether such accurate determinations would be meaningful at this time. As stressed earlier, the most urgent need is for toxicological investigation In this area to indicate whether some of the PCJI compounds arc more toxic or have greater sublcliud effect than others, as observed with tho HI1C isomers. At that point it would becomo essential to Identify and estimate accurately specific individual compounds in the mixtures. XL Separation of FCH's from orgnnophosphm us compounds by the Florisil technique A limited amount of work has been carried out In our laboratory to determine whether the Florisil column technique is applicable to the separation of the PCIPs from the organophosphorus compounds. Preliminary results on those tested (phoratc, dinzinon, round, mala* thion, parnthion, methyl Trithion, cthion) indicate that they arc not eluted with the PCU's by hexane, and can therefore be separated. In comparison to the organochlorinc pesticides, the organophosphorus compounds generally require larger volumes of the ether-hexane mix* turo for elution from the FlorJsil column, most likely because of their more polar nature. As with the organochloi ino pesticides, the presence of PCH's in a sample extract will interfere with some of the more common organophosphates when the EC detection system is used. However, with the use of a dual detector (EC *f- phosphate or thermionic) connected to a dual-pen recorder, the effluent from a single injection containing PCB's and organophosnhntcs enn be split and differentiation made as shown In Figure 5. Like the organochlorinc pesticides, the PCH's arc not detected on the phosphate detector. Nevertheless, in the ab sence of a detector which is specific for phosphorus, the Florisil col umn technique can bo used to separate the PCRs from the organophosphates to facilitate the analyses. XII. Residues of organochlorinc pesticides and l'CBs in Canadian wildlife Following the approaches outlined, the authors laboratory has analysed a number of Canadian wildlifo specimens for residues of MONS 083226 40 L. M. Rxynoi.os rig. s. Differentiation of Aroclor 1251 and organophosphoru* pesticides uung dual detectors aim) effluent split. Chromatogram A: organophrwpliftru* ' standard pesticldo mixture; peak numbers 1 M 1.75 ng. of photak*, 2 2.0 nc. oi diar.inon, 3 ** 3.0 ng. of Iloimcl, 4 - 13.0 ng. of nwlathb.n, 5 5.0 ng. of naralhion, 0 15.0 ng. of methyl Trllhlon, and 7 * 10.0 ng. of ctliion. Chromatogram B: combination of organophosphonts inix: ture (chromatogram A) and 10 ng. of Aroclor 1254 numbered I to XIV as In chromatogram Jl of Klguio I (a compromise of the K.C. response is necessary to obtain maximum response on the phosphorus detector). P * phosplionis detector and FC - electron capture detector. Column four percent OV-100/six percent OV-210 on GO/80 mesh Chrommoib \V (AW); other GLC parameters as in Figure 1 orgnnochlorlne pesticides and PClVs. Some of the data on aquatic birds from Western Canada arc given in Table I. The inclusion of these tabulated results, which represent only a minor pm lion of the total number of samples analysed, is intendrd to illustrate the types of analytical problems created by the presettee of PClVs, and to indi cate potential errors due to high levels of PClVs in samples. Referring to Tablo 1, some general remarks arc in order: 1. The greater portion of the apparent DDK in samples is In fact DDK. Hits is predictable from the comparatively smaller amounts of apparent DDD and DDT, and has been verified by TLC. 2. A largo proportion of the apparent DDD in the samples is due i to PCB's. However, DDD is present in some samples. HONS 083227 r i i t iiliUiiiiiiLiiijijiili. ,13 90 95 mplimphonw pciHcKlrs using A: ornimoplinsplionn I 1.75 up. ol J'liornlc, ?. 11, 4 13.0 ng. of mnlnlhion, tm'lhyl Trillilon, mil 7 " 10.0 lion of orgnmipluMpltmut; mixi*rlro 1K-1 numbnicil 1 to XIV tijtiomhr of llto K.C, response on tin- phosnlioms detector). ion rapture ortcetor. Column m G0/b0 mesh Chromosorb W r] o of (he data on aquatic Table I. The inclusion of ily n minor portion of the ilvtl to illustrate (he types net* of PCB's, nml to intlif IXIll's in samples, limit* ore In order: >1)1' In samples is in fact parativrly smaller amounts .`t n verified by TIjC. >D in tho samples is due me samples. | ; | \ j [ I 1'olyclilornhlplu.nyh 47 Tito cfTcc-t of Kill contamination on DDT values is less mailed than in the ease of DDD, but it is still substantial. 4. The apparent JI);I values arc in most cases due entirely to Ihr pesticide. This is somewhat incongruous with the rest of the data since peak four of tho commercial PCB mixtures docs intoifeic with IllC. However, this anomaly may be explained on (ho basis that the l'CJl component giving rise to peak four Is degrad' d ex tensively In the bird's metabolic processes. 5. Based on all of the PCM estimates in wildlife samples noted to date, including those in Table I, the following general trends ore evident: (a) Afiualic rnplorfals generally contain higher residue levels of pesticides and PCB's than other wildlife species. (l>) High levels of PCB's arc found only in the presence of high levels of orgmroehlorine pesticides (tho resin powder mentioned below is an obvious exception) but high levels of organoclilorinc pesticides arc not necessarily accompanied by high levels of l'CH's. (c) The most abundant l'CB types delected arc those which show Aroclor 1254 and 1200 patterns and, therefore, fit well with the Jiroposcd method of quantitation. However, it should not be over- ooked llmt with the present residue methodology some other PCBtype compounds might go undetected. 6. It is important to measure moistmc and fat content of samples in conjunction with residue levels. This allows for reporting on a wet-, dry-, or fat-weight basis. However, enution should he used when reporting residues in wildlife samples, for example, on a fat basis when the fat content is very low. Such figures can be inaccurate ns well as highly misleading. Tho gns chromatogram of a typical sample showing the presence of PCB's is given in Figure 0. It indicates the Aroclor 1260 pattern and was obtained from ft duckling found dead in tbc Toronto nrra in the summer of 10G9. A good example of FCB's showing up in unexpected places oc curred recently. A wildlife biologist was faced with the problem of fish dying in a hatchery for no apparent reason. He scraped some of the resin powder from the hatchery trough and found, surprisingly, that experimental fish were susccplmlc to even a dilute solution of the powder. Ho submitted a sample of the resin powder to the author's laboratory, and upon analysis a typical GLC pattern of PCB's (Aroclor 1254 type) was obtained. Tills is shown in Figure 7. Using the meth odology described earlier in tin's review, the sample was found to contain PCB's but no pesticides. Based on calculations from 11 indi vidual peaks of Aroclor 1254, tho PCB concentration was estimated at 35 p.p.m (range 25 to 40). Using the avcr8go results based on peaks eight and ten only, tho PCB estimnto was 29 p.p.m. This is i { HONS 083226 T vu'iONAMii q | f Table L Orfmocfdorlnt residues (p.p.m, on a vet-weight bcsis) In Canadian aquatic birds as measured before and after FCB FtarisU separation . Description of specimen* P.P" DietDDE* drin4 p.p'-DDD Before (apparent) After %* p.p'-DDT Before (apparent) After a* HE Before (apparent) After PC3' % California Gnlls Abd. fat bird 1 Abd. fat bird 2 Abd. fat bird 3 Abd. fat bird 4 Abd. fat bird 5 Abd. fat bird 6 Brain bird 7 Liver bird 7 Ovary bird 7 Abd. fat bird 7 Egg ares 1 Egg area 2 D C. Cormorant Egg* Sample 1 area 3 Sample 2 area 3 10 pooled area 4 Mallard Duck Eggs 10 pooled area 4 (.Wwwi 'i tm tggs Sample 1 area 5 Sample 2 area 3 Great Blue Heron Egg* Sample 1 area 3 241 133 240 246 169 296 3.6 15.7 22.9 416 21.8 2.9 3.3 3.3 3.5 0.2 33.3 5.1 78.0 1.36 1.02 1.23 1.91 1.73 1.51 0.04 0.07 0.12 1.93 0.19 0.09 0.11 0.10 0.21 0.08 0.15 0.02 0.05 3.16 1.02 2.63 1.59 1.71 3.09 0.04 0.11 0.17 4.64 0.20 0.11 0.11 0.12 0.03 0.01 ... 0.06 0.27 ND' SO so SD SO ND N-D 0.02 0.04 0.34 SD ND 0 0 0 0 0 0 0 14 24 7 0 0 SD ND SD 0 0 0 0.01 89 0.02 SD 13 0 0.27 1C9 3.17 1.04 3.47 2.41 2.05 3.33 0.04 0.11 0.23 4.43 0.25 0.11 0.12 0.12 0.07 0.15 0.26 0.16 0.41 SD 0.14 0.25 1.27 0.35 1.09 SD 0.01 0.02 0.62 0.03 0.02 0 7 7 53 17 33 0 2 3 14 33 18 0.03 0.02 0.03 22 13 41 0.15 100 0.15 0.15 51 90 0.42 102 SD 0.23 0.19 ND 0.33 0.42 ND 0.03 0.05 1.19 0.07 0.01 0.01 0.03 0.03 0.01 SD SD 0.02 SD 0.22 0.21 SD 0.19 0.36 SD 0.03 0.04 0.73 0.05 0.01 0.01 0.03 0.04 0.01 SD SD 0.02 50.3 96 25.3 10? 62.6 -- 36.7 53 23.2 S7 23.0 - 0.S1 n 1.69 S3 2.52 65 3S.4 65 1.74 93 1.57 100 110 2.21 106 0.67 100 0.09 _ 1.57 0.94 94 Trace* MONS 0 8 3 2 2 9 OE?fBO SNOW tlXunijdiqonijtp/jo^ -1 , ii ;; 1 t ;1 jj 1 t I' i: Ahd/fat bin! 7 ; 410 1.93 21.8 0.19 2.9 0.99 D.C. Cwmrcit Eft* , Sample 1 area 3 : 3 3 ! 0.11 3.3 < 0.10 10 pooled area 4 j 3.5 0.21 ifafford thuk Efg* | 10 pooled area 4 1 0.3 | 0.03 Common Tern Effft | j 33.3 0.15 Sample 2 area 5 ! 5.1 0.02 Great Blue Herm Eff*'- , Sample l area 5 78.0 j 0.05 4.64 0.20 o.u o.u 0.12 0.03 0.01 0.17 0.09 0.27 9.31 HD >- 7 0 0 HD 0 HD 0 HD 0 9.01 80 0.02 13 HD 0 0.27 100 0.25 0.11 0.42 H ! 9.9S 33 ` 0.02 IS 0.12 0.12 0.07 0.03 0.02 0.03 22 13 41 0.15 0.15 100 0.28- /3.15 51 0.18 r0.15 90 0.41 0.42 102 t.13 0.V7 0.01 0.01 0.03 0.03 0.01 HD HD 0.02 : 9.7v * 0.95 0.01 r-j ;.74 V. 1.57 0.01 j ICO 0.93 110 0.04 105 1.94 2.21 0.G7 0.01 HD HD 1 100 1 !-- 0.99 1.57 0.94 __ 0.02 | 94 Traced N* Description of specimen* Sample 1 area 8 Sample 2 area 8 Sample 3 area 8 Sample 1 area 7 Sample 2 area 7 Sample 1 area 3 Sample 2 area 9 Table L (continued) PP- Die!DDE* drin* 24.0 11.3 13.7 13.5 3.7 6.3 0, 0.42 0.19 0.74 0.07 0.C8 0.63 0.07 Pjp'-DDD Before (apparent) After 0.33 0.07 1.83 0.07 0.12 0.09 0.06 0.27 HD 1.70 0.05 HD 0.05 0.03 81 0 104 64 0 49 p^'-DDT l 1 HE Before (apparent) After! 1 1 %* ! 1 Before (apparent) After PCB* 0.18 0.30 0.08 0.05 0.14 0.04 0.07 1 0.10 0.23 j 0.06 | 0.02 0.03 | 0.01 0.05 | ~| 77 ! 69 | 33 1 IS ; 22 ! "1 0.15 0.10 0.05 0.02 0.02 0.02 0.03 0.12 Trace* 0.03 Trace* Trace* 0.01 0.01 S3 ICO -- 52 44 3.41 1.93 1.09 0.57 1.3S 0.53 0.33 These specimens are from western Canids (Vermeer and Reynolds 1979). * These are '`Before PCB-Florisil separation" rallies and are likely to include ?C3 contributions. The "After" values (which do not change significantly from the "Before" values) are not given because the ?CB peak five (the DDE-interfering peak) of Aroclor 1254 or 1280 is not separated from DDE by this method, but, as discussed earlier, the PCS contributions to the DDE values are expected to be relatively snail compared to the contributions to DDD or DDT. * These are "Before" v&iues. The "After" values (not given) ire not sigcifcantly different from the "Before" values since there is no direct PCB interference. However, in the presence of high levels of D DE, lew levels o? dieldria will be masked. In such cases a separation (e g., PCB-Florisil technique) is necessary1 and the "After" value would be reported as the dleldra level. *% After value Before value 100 and indicates the percentage of the total apparent pesticide level that was actually due to the pesticide. * Values (p.p.m.) based on peaks eight and ten of Aroclor 1254. 1 HD -- none detected - <C.CC3l p.p.m. Trace -- <0.001 p.p.m. o | j . ji ii l! 50 L. M. rir.yNOi.ni Fig. 0. Typical sample indicating the ptcscnco of PClVs of the Aroclor 12H0 typo In a duckling from the Toronto area. Chromatogram A: 5 ng. of Aroclor 1200 numbered I to XVII w in chromatogram B of Figure 3. Chromatogram B: the cqulvolcnt of 0.35 mg. of duck sample (hexane portion of Florlsll spill). Nolo tho DDL contribution to I*CR peak V. CLC parameters as In Figure 1 i: 1 ! I; 1; "V-T_ Klt.T. ftrsin powder extract Indicating the presence of PCfl's of tire Arorlor 1254 type. Chromatogram A: 5 nc. of Aroclor 1254 ountbered I to XIV at in chromnlogram B of Figure 1. Chromatogram fl: The equivalent of 0.02 mg. of resin powder extract (hexane portion of Flmlsil split), numbered I to XIV as (n Aroclor 1254. CLC parameters as in Figure 1 MONS 083231 rolychlorobiphcnyls 51 A ft ttii.liUi liJj.l'iiiilu *> 5S '^ %tnn- of K:H'i of tlie Aioclnr *trn. Chromatogram Ar 5 ng <! |l as In chtomatogtain B of Hr.mc .1. f,i* tti|;, of duck sample (hcxvi- > ))I)K cnntiibutioii to I11B peal: V. A aii interesting rxnmplc of l'CJTs causing contamination as n dual ,t.N,,U of fmluj trial application. With regard to the Klorisil technique for the separation of Toil's from pesticides, one impoitanl modification to the oiigiiuil mr-lhod (Hr.YNOLns J9(jfJ) is now used routinely in the wildlife studies. Oiigiivilly the scheme was designed to accommodate simultaneously belli tlio cleanup of the sample extract and the sepmation of PGH's. How ever, ns poinlcd out earlier in tin's review, not all samples contain PCH's. Consorpicnlly, for general samples, to avoid unnecessary split ting of nil snmplo extracts (each split doubles the number of dilates to he ehromntogrnphed), n normal cleanup including a Mnri.xil col* unm, hut no differential elution, is conducted. The KloiisibTdll sepa ration is then carried out on the clenned-up extinct, if it Is rcqniicd. Under these conditions smaller columns hnvc been found to he as efficient ns the larger columns used in the original method, nnd there (j a substantial saving in the amount of reagents required. Details of (he modified procedure arc ns follows: A glass column (44 cm. X 1 cm. Id. having a 50-m!. reseivoir on top) Ji pricked with 30 cm. (--10.7 g.) of Florisil (00/100 mesh. Mondin Co., pesticide grade, stored at 130*C. until rendy for use) am) topped with a 2-cm. tnycr of anhydiotis NoiSO,. The snmplo extract of shout 5 ml. (n-hrxnnc) fa added to the colunm. The first elution which remover pCIVs, lreplnehlor, nlrirfn, ind 13DIi, is cflwtnl with 00 ml. of n-lmmw; (Nnnogrodc, Mallinckrodl). The remaining pesticides sre thru rlnled with 40 ml. of 50 percent ethyl clhor in hexano. Note that in filling (ho columns, the Morisil is packed down hy gentle i tapping, and the sample extract b added to diy colunm, i.r., no prc. wetting. After tlio first elution tlto receiver is changed as soon as the InU of tho hexano meets tlio Na>SO<. It should he noted also that with our hatch of pesticide grade Florisil, some PCH peaks (two, six, nine, 11) j showed partial elution hi the second clnatc. These, however, are com /> paratively minor peaks and do rot interfere with any of lire common organochlorino pesticides. As thoro are differences in batches of Florisil, lire procedure has to be checked out fully prior to application to actual samples. Modifications of volumes, etc., may be necessary to cfTcet the desired separation. It fs likely that adsorbents other than Klorisil, eg., silica gel or alumina, will givu ritnllnr separation of PCB's from pesticides but theso have not been investigated to date. >0 win , 90. M tl.t rwcM-lwr of rCB'l of fho A'"1;'' or. oi Atoclor 1254 numbered 1 to M I. Chromatogram B: The equivalent " tact (hrsano portion of Flprtoll spmh ir 1254. CtC parameters as In Flgm * l 1 j | ; j J Acknowledgments Work in connection with this review was supported by funds from the Pesticide Section, Canadian Wildlife Service, OtUwa, and from llio Province of Ontario through the Department of Trnde and Devel opment. The writer gratefully acknowledges helpful suggestions of Dr. S. C. Reid, Director of Organic Chemistry Department, Ontario ) M0NS 08323 62 L. M. Hkynoids Research Foundation in preparing this review for publication. Tho technical assistance of Terry Cooper anti Sandra Tatacs is gratefully acknowledged. Table II. Chemical dctlgnntlons of pesticides mentioned fn (erf Fcelioldo ' Chemical name* 1 idrin p,pM)1>D (TDE) p.p'-DDE p,pM)DT dintinon dicldrin ethion hepiaehlor facpUchlor epoxide lindane (t-BJIC) mMaUiion methyl Trithion paralhion phorftto (Thlraol) Konnei 1,2,3,-f, I 0, JO-hcxiicliloro-1,4,1n,!>,R,ftn-)>ctnhydTO- exa-5,8-dimctlinnonnphthalcne 2l2-bi5(p'Clloroj>itonyI)-l,l*dichlurcthne 1, l-dohlcro-2,2*bw(p' chlf/ropbanyljcthyienc l(l,l-trichlora-2,2-bis(j>-clilorophctiyl)clhne 0,O-<liHhyl-0-(2-UopropyM-inethyl*(l-pyrirmdyl)*pluw- phorolhirmto l,2,3l't,]0,10ht!xnchtoro-0,7-Qpoxy-l,4,4A*6lr,7,fl,ftA'Ofla> hydro-j,4fndo,txo-5,ft-dimcUmfiona|*lilhalcnc 0.0.0',0-tcli nctliyl-5,i5'-methylene b/ftphosf>tior<"IftliifMlA I,4,5,f,7f8l8-ht!|*tael>loTCk3ft,4l7,7n-tclrniy<lro-1,7-fn<h>- molltiihni*uJciio 1,'l|/,r>,7,a,8 ltcj>(rJifoto-2,3-eiiovy 3rt,4,7,7A-tclrnhydr<M, 7-mcthonom<lnnc Y-l,2,3,4,5,0-hcxAchlorncyclohcx urm S-(I,2-tm(ethoxy enrl>nny))cthyi|f/,0-(lmi<'thyi phoftfihorodi- thionlo 0,0-dimathyl 5-(j>-chloropbct>yUho) methyl plionphorodi- thionlo 0,0-dicthyl O-p-nitroplicnyl phosphorolhiontr 0,0-diclhyl A-(clhyllhio) methyl phoapharodilliioate dimethyl 2,4,6-lrichforop/icnyl phosphorothinnnta - Summary Since 1966, PCB's have been detected in Osh and wildlife, espe. cially In Europe and North America. Contamination from industrial wastes via the water ways appears to he the main source of J'CH's In aquatic species. The PCB's have many important industrial uses but arc not utilized as pesticides. Due to their similarities in structure and properties to the organochlorine pesticides, the PCB's tend to interfere with accurate GIAM'.C determination of orgnnochlorine and many organophosphorus pesti cides. In addition to their interference with pesticide residue analysis the PCB's arc themselves toxic so that their quantitation is desirable. A method for recognising tho presence of PCB's in samples, sep arating them from pesticides, ana determining the pesticide levels accurately is described. Simultaneously an estimate of total PCD con tent is afforded. MONS 083233 I I, view lor piililirtillon. Tho I S.iilm Tnknrs is gratefully tMthi irnwirrf < oniral nama 1, t, h,\R,K*licxili),ilro-l,4-rrfi tllinivitf .|.liih1mwthMHi lilmnplifnyOtiHnne v|.ljiwt1tyl*0*|*yrin>Myl)*lho- r.(;.rpi\)M,M-'V0,7.Mn-oclaliiiM thannnaphthnlwic ' mMliyVnp WM>h**|*hwfrtUhio^ .`.Itimxy.to^.T.Tti-totrRhydro-l, mImIm-xmio > lj*ll.)l|W/#-dimrUyl |>hoapborodi- lilirttvllliio) methyl phaaphorodl- njl |ihimpliorolliionio mMiivI pbnejWiororfiUiioate Itniyl piivMphvrulliioimlo d in fish awl wildlife, ospemnl.tminnlion from industrial im the main source of PCBs my important industrial uses ami properties to the orgnnotiifrrc with mnirflto GDC-KC >.my orgnnophosphorus pcstiivillt pesticide residue analysis dr quantitation is desirable, nee of PCB's In samples, sepennining tho pesticide levels an estimate of total FOB con- l'oIyehioJoMplicttyk The residue data of some Canadian aquatic birds indicate that high levels of PCB's arc found only in the presence of correspondingly high levels of the DDT pesticide group. On the other hand, high orgnnocMorme pesticide levels arc not necessarily accompanied ly high PCB content. Further research on toxicity and sublclhnl effects of PCB mixtures and their individual components is required. If particular components are shown to be more toxic than others, refining of the TCB quantita tion methods will be necessary Rdsrnnd* Analyso do rdsidus do pesticides cn presence do diphdnyls polycldords Dennis 19CG dcs diphenyls polychlorcs (PCBs) ont 6to ddtcctcs dam fes poissons et !e gilder, portieuMrcincnt cn Europe ct cn Amdrlquc du Nord. 11 apparnit quo In presence dc PCIIs dam la faunc nquntique suit due pi muipalemenl ft la contamination dcs cours dean par dcs dcchcts iwhislricJs. Dcs PCBs soul utilises pour un grand nomine dc precedes induslriets impoitanls, mais lls no soul pas appliques commo pesticides. Klanl donne quo la slruclnrc ct les propridlrs drs PCBs soot scmblahlos ft cellos drs pesticides organochlores, ils ont tendance ft fausscr la determination cxactc dcs snbstnnees ovganochlorvn rt organophosphorccs lors d'annlyscs par chromatographic cn phase ga/eusc via capture detections. Kn plus dc leur Inleifeuuee lors dc Tanalyse dcs resides des pesticides, les PCBs sonl cuxmrmcs des composes toxiques donl la determination quantitative rst souhnitablc. Dc present article contienl unc mthhodc qui permcl dc rucnnnaltic la presence dcs PCBs dans des <5chnntillons ct, cn mdme temps, dc les stfpnrcr dcs pesticides dont lc taux dc rdsidus pent (lire exaetcmcnt determine. La mlthodc permcl dgalcmcnt tine estimation du coulenii total en TCBs. Dcs r&nltnts d'analyscs portnnt sur dcs oisenux aquntiques cimadiens indiquent qu'un taux dlevd clc PCBs c$t li6 ft un taux clrvc dc rfcidus dc pesticides du grotipc DDT. D'autre part, dcs taux dlcves dc rfoidus dc substances orgnnochlorccs nc sonl pas ndecssairement ccompagnds d'un taux dlcvd dc PCBs. Dcs rcchcrcbcs supplemcntaircs sur la toxicit 6 ct les clTcts sub16taux dcs melanges dc PCBs ct dc lours composes individuols seront ndcdssnircs. Si on peut ddmontrer quo dcs substances paiticuli&rcs sont plus toxiques que d'nutros, on aura besoin d'unc mlthodc plus spdcifiquc permettant l'annlyso Individucllc dcs PCBs. * Traduit par H. CemathiLea. HONS 083234 54 J,. M. JUvkou>s ZiismiimcnfnsMing* Die Analyse von rflnnz.cnschulAinfUcJ-Ruch.stiimlcn in Ccgcnwnrl von Palyeldordiphcnylcn Scit 3966 werden PolycMordiphcnyle (PCB S(offr) in Fischcn und Wildlicrcn, bcsondeis Jn Kuropa und Nord.uncrlka, nachgcwicscn. Die Vcrschmut/.niig dcr Wnsserwege durch Industiicabfiillc sclieint dnbei dio JlaupUusncho von PCB-Riicksliindcn in dcr nquatischcn Fauna 7.\1 scin. Die PGB-Slofic werden fur cine AnzaM wichligur Induslricptozcssc gcbrnucht, als Sclmdlingxbckiiinpfungsmittcl wcrcion tio jedoch nielli ringrsel/t. bn die PCB SlofTe in Hirer Slruktur und in Jlircn Kigrnseltnflrn den chloiinlcn Koblcmvasscisioff-Ihsokti/idcn sehr Khnlich sind, konnrn sic die gtisclironiiilogirtpliiselic Brsiimmung mil Klcklronencinfnng-Dcleklor von cliloriorlun Kohlemvnssei steffen und mnnrlurr Pho.sphorsiUirccstcr verfiilsolirn. Die PGB-Stoffo kiimun lilolil nnr Riickstnndsnnnlysrn bcrinlriiclitigcn, sentient sic sind selbst toxischc Subslanzen, deren Nncbweis sicb nufdriingt. Im vorlicgnnden Arlikcl wird cine Mclliode bcsrhriebrn, 1<* <s crlmibt, das Vorhnrulcmotn von PCB-Sloffon in Proben nmhymvr'is'n. sio von den SclifidlingsbekitinpfuiigsmiUeln nlv.ulrrnnrn und die Riickslsiiido dcr lel/.lern genau zu bestinunen. Dmiiber liinaus gcslaltct die Methodo, den Tolalgchalt an PCB-StofTcn nbznschiit/ni. . Hiickstmidsdaten cinigrr kanndiseber Wasseivogcl wciwn daratif bin, dass hohe PCB-Konzcntrationcn nur in Gogenwart holier , Rilcksliindc von Substanzen dcr DUT-Gruppe anflrctcn. Andrrsrils . sind hohe TUicksliindc von cliloricrten Kohlcnwnsscrslofl-InsoUizidcn riicht unbedingt von liohcn PCB Konzcnlrnlioncn bcglrilrt. Wcitcrc IJnicrsuchungcn iiber die Toxiziliit und die sublctliatc Wlrkung von PCB-Miscbungcn und ihrer individucllcn Koni|>oiicnlcn Sind angezeigt. Solllc cs sich dabci ergeben, dass gewisse Kinzelstoffr toxischcr sind als anderc, wird cine Verfeinenmg dcr Nachwris- und Bestimmungsmclhodcn fiir PCB-StoiTc notwendig. References Bnoex, S. S.: Insecticidal surface coatings. Soap ft Sand. Clicm. 24 (2),138 ' (1018). . Bnoww, l\. M.: On (ho toxicity of the "Aroclors", Chemist Analyst 30, 33 (1917). Bmuxer, C. K., K. J. IIatiim, Jl. 1. Dran, T. M. Waj.kfh, J. Skza, and D. ____ Coi.nv:,The accmmilnlion of pf)T in lake trout and the effect on reproduc tion. Trans. Amcr. Fisheries Soc. 93 (ft),127 (1964). Burner., J. A.: Cas chromatography for pesticide residue analysis; some practical aspects. J. Assoc. OOicinl Anal. Chemists 48, 1037 (1905). CHAU, A. S. Y.: Derivative formation for the confirmation of endosulfan by gas chromatography. J. Assoc. Official Anal. Chemists 52, 1240 (1009;. * Obersetzt von H. CwasoOtiLKn. MQNS 083*35 / / , i-i.inilcn In Ccgrmvnrl ,l.n (.ll.Slollr) hi rijchcn uml H|,niinll:n, nnrliginvimn. I, iwlnilrlenbllillo scliclnt mili'ii In *lnr nqimllsdicn nr rlnc AiwnM wlchlir.cr K'l;:iiii|ifiingsinilli-I wcitlcn III In Ihrcn Higi iisdinflnl lilni K'lir Klmlirli ilml, liinimiiiR mil Khiklroncnuurrslonm mid inniiclicr Slollo kliiinui niclit nur in tin Hind ndUUJoxisclic llmdn I'r.iclu irln'n, die on n in l'rolion narhniwciicn, 111 nlw.nlrriiiinii mill die liiiniioii. Dmiilicr lilnmis l'ClI Slollcii nlw.mdiiil7.on. V.moi \ (i|;il wolsoi dnrnuf nir in CJcgonwnrl holier iippo millrclon. Andcrsolts ilonwnMorsli>lf-lidili7.idrn liniu n lwglollol. vl/illll mid die sublolhnlc ndivldiirllen Koinponcnlcn i, dnu gowhtc Kliwclstoffe liming dor Nndnvols- und rondig. *|* h Sunil. Chrm. 84 (8),138 ClwmM Analyrt 98, 33 (1017). M. Waiiik,], Skta, iml D. "nit and the tlfrtl On rrproduc* 1 terttlur anilytlij some practical mi (1003). rmifttmallnn of rndnsulfan hy iL CSrtnlm 81, 1140 (1000). Poiychloiohiphcnyls 55 ------, and W. I*. CoumANr.: Cyctodicnc chemistry, HI. Derivative fonnntirm fur tin; lilcntific.ilinn of huplachlor epos Mr, cIseMoiclnnr, lionviM'>diuK*, dlcldrin, am) endrin pe.'iHcldc residues by gas chiomaloginphy. J. Asvoc. Official Anal. Chemists 53, 1820 (1000). CoCiiuank, W. I'., and A. S. Y. Ciiau: Note on gas clnomntogtnphlc idn>tific:'ti'ii* of hratAclilor pesticide residues by derivative formation. Assoc. Oflirinl Ana). Chemists SI, J207 (1008). Dunois, K. P.: Combined efTrets of pesticides. In: Current views on pesticides, p. 33. Symposium sponsored by Food and Drug Directorate, Deportment of Noliowtf Health and Welfare, Ottawa, 10G8; reprinted from Can. Mi d, Assoc. I. 100 (No. 4) ()nn. 25, 1000). Dur'iT, ). it., and N. Wonc: Residues of organoeldorino Inseclickles and their metabolites in soils In the Atlantic: provinces of Canada. J. Agr. Food Chem. IS, 457 (1007). Ciwi'niiuim?, L., M. R. Matchs, A. II. Smith: Tho systemic effects resulting from exposure to certain clilorln.iteel hydrocarbons. J. Ind. Ilyg. Toxicol! 31, 80 (1030). Cuntj!i:h, F. A.: Instrumentation In pesticide residue determinations. Adv. Test Control nescareh 5, 191 (1002). IIammknck, J. II., P. S. llAt.r, and D. J. Caveiu-y: Tho Identification and deter mination of chlorinated pesticides residues. Analyst 00, 040 (1005). Haimuson, It. I).: Residues In wlldllfo with special rcfercnco to endiln. J. Sci. Food Agr. 17, 10 (1000). Hickry, J. j., and D. W. Amhuson: Chlorinated hydrocRtlons and eggshell changes In rantorla) and fish-eating bitds. Science 102, 271 (IMS). lloi.tn.N, A. V., anu K. Mausukn; The examination of smfnrc wains and scwngi' effluents for organochlorlno pesticides. J. I'roc. Inst. Sewage 1'iirif. p. 295 (1000). ------- ------------- Organochlorlno pesticides In seals and porpoises. Nature 810, 1274 (1007). Uolmks, D. C., 1. II. Simmons, ami J. O'C. Tati ON: Chlorinated hydrocarbons in British wildlife. Nature 210, 237 (1007). IIonNSTKm, I., and W. N. Sullivan: Tho role or chlorinated polyphenyls In improving lindane residues. J. F.eon. JSnlomol, 40, 037 (1053). . Jensen, S.: Re|wrt of a new chemical hnanid. New Scientist 32, 012 (1000). --------- , A. G. John-.u, M. Oi.sson, and G. OntcHLiNii: DDT and )*CR In marine animals from Swedish waters. Nature 824, 847 (1000). --------- f and G. Wjumahk : Swedish report at the OECD pesticide conference on "Unintended residues in the environment** (1007). Jones, J. W., and II. S. Aldrn: An acneform dcnnalcrgosls. Arch. Dermatol. Syphilol. 33, 1022 (1030). Klein, A. K., and J. O. Watts: Separation and mcasuiemcnt of perthanc, DDD (TDE), and DDT in leafy vegetables by electron enpturo gas chroma tography, J. Assoc. Official Anal. Chemists 47, 311 (1004). Koeman, J. I!., A. A. G. Oskamp, J. Veen, E. Brouweii, J. Rootii, P. 7.wart, E. v. . Broek, and H. van Cknuehen: Meded. Hijk$-foeullcit Isintlbouw- wctcti*c]uippcn Cent. 32, 841 (1007). Koeman, J. H., M. C. ten NoEven dr Riiav, and R. IT. he Vos: Chlorinated biphenyls In ffsh, mussels and birds from the River Rhino and the Nether* lands coastal area. Nature 821, 1180 (1909). - Lindquist, A. W., A. H. Madden, H. C. Wilson, and E. F. Kkii'mnc: DDT as a residual.type treatment for control of house flics. ). Econ. Entomol. 38, 857 (1015). McLauchun, J., Jr., J. P. Marliac, M. J. VEnmrrr, M. K. Kfvroii.Rn, and O. C. Fn'Aiiucii: The Injection of chemicals Into the yolk sac of fertile eus prior to Incubation as a toxicity test. Toxicol. Applied Pharmacol. VT00 (1903). HONS 083236 / ' : 1 1 so I.. M. UcvNor.ns Mltl.vn, J. W.: Pathologic changes in animals exposed to a rommrrcM rlil'iriuatrd diphenyl. U. S. Public llriilth Rrpnrts fi|>, 1083 (1044). Monuinto Co.: 'Ilto Aroelor compounds, p. 17 (J9U5). --Aroelor plasticizers. Tech. Boll. 0/1*1 .-300 {1007). Osaitciiuck, M., and IS. B. Wani,i*s; Identification aihI rpiantitallve estimation of aldiln rcsldncs In (he presence of Interfering materials In samples of plant and animal origin. J. Assoc Official Anal. Chemists 51, 1204 (JOOfl). Pkakam., I). FI.: Pesticide-lnauccil enzyme breakdown of steroids In birds. Nature 810, 505 (1007). Fknninc, C. II.: Physical characteristics and commercial possibilities of chlori nated biphenyl. 1ml. ling. Chem. 22, 1180 0030). Ratci.ii'FK, IX A.f Decrease In eggshell weight In certain birds of prey. Naturo 215,208 (1007). Rrjemu., W.; Personal communication (1060). yteiwor.n*, L. M.: Canadian wildlife service reports (Unpublished dale) (1908, 1900). ---- Pesticide residue analysis in the presence of PCB's. 4lh Annual W. Can. Seminar on Pesticide Residue Analysis. Winnipeg, June 2-4 (1009 a).* -------- Polychlnrobiphcnyls (PCB's) and tlrcir inlcrfcrcnco with pesticide residue analysis. Bull. Environ. Contamination Toxicol. 4, 123 (1000 b). RtSKimouuti, It. W., P. Rttcuu, S. C. Hkhman, D. B. Pi:akam., and M. N. Krnvr.N; Polychlorinated hiphcnyls In the global eco-system. Nature 220, 1008 (1068). ----------, P. Rn.cn>:, and 11. S. Ou:Ott: Current progress In the determination of the polychlorinated biphenyls. Bull. Environ. Contamination Toxicol. 4, 102 (I9G0). KoniNSOM, Residues of oignnochlminu Insecticides in dead birds In the United Kingdom. J. Chem. Iml., p. 1074 (1967). Roihmin, ).: A simple concentration-cell technique for determining small amount* of halide Ions and its use In the. determination of residues of oigannrlifoiinr pesticides. Analyst 00, 407 (1005). Samwl, B. L., and If. K. IfoncKS: Inscctidde screening methods for oiganoelilo- rlno and organophosphotc Insecticides In foods and feeds. Residue Reviews 17, 35 (1067). Sans, W. W.: Multiple Insecticide residue determination using column chromatog raphy, chemical conversion, and gas liquid chromatography. J. Agr. Komi Chem. 15, 102 (1007). ScilMtUT, If., and C. Scmn.TV.: Patent for manufacture of pcntnchlorohiphenyl. Ann. 207, 338 (1881). ^ Schwautz, L.: An outbreak of halnwax acne ("cable rash") among electricians. J. Amcr. Med. Assoc. 122, 158 (1943). -------and K. A. Bahi-ow; ChlorAcno from cutting oils. Public Health Rrpt. 57, 1747 (1942). ----------, and S. M. Prex! Oecnpatlnnal acne. N. Y. State Med. }. 43, 1711 (1943). SciiKCtmm, M. S., S. B. Soi.oway. R. A. IIayks, and H. 1,. Havlkii; Colorimetric determination of DDT. Ind. King. Clicrn., Anal. ed. 17, 701 (1915). Simkiss, K.: Calcium In reproductive physiology. New York: Rclnhnld (1967). Sticxki*, L: Wisconsin hearings. Science 103,551 (1909). Svu.ivan, W. N., and I. Hohnstkin: Chlorinated poJyphcnyls to improve lindane residues. J. Kron. Entomol. 40, 158 (1953). Thompson, J. F., A. C. WAi.rcr.n, and It. F. Mosfman: Study of the performance of gas chromatographic columns under severe Injection loading, j. Assoc. Official Ana). Chemists 52, 1251 (1909 a). . ....... - . -- --...... - Evaluation of eight chromatographic columns for chlori nated pesticides. J. Assoc. Official Anal. Chemists 52,1263 (1009 b). MONS 083237 L,,r,l to I cwwnerelal chlorinated V. (IWM). i imi) ,,|,m nn() quantitative estimation .ifritnr material* In samples of ,,1 CkmMs5l.l?.m (IfNUl). |v,|,.wn of steroids In bird*. Nature ,lMnt)H'iHnl pnssIbiHllcs of clilorl(l!M0). I in Vcrlaln birds of prey. Nnluro polls (Unpublished daia) (1008, .flier of PCIVs. 4lh Annua! W. is. Winnipeg, Juno 2-4 (1000 ). Intulmmec with |rcstlcklo residue oskol. 4, 128 (1000 b). IAN, 1). n. IVakai.i., and Kf. N. global reo-system. 'Nature 220, rut progress In the determination nviinn. Contamination Toxicol. 4, tk-klrs in dead birds In (be Untied pir fru determining small amounts itiim of residue* of orgnnnrlilorino set,erring method* for orgnnochlohinds and feeds, Residue Review* iiniiislton using eotmmi chrom*tog> ltd chromatography. J. Agr. Food inrtfitclute of pentacliloroMphcnyl. ("table rasliM) among electricians. rutting oils. Public Health Kept. e. N. Y. Slate Med. j. 4.1, ITU S and I). 1., llAt.t.Kn: Colorimetric n.. Ana), rd. 17, 701 (1045). New Ycnlcs ftelnhold (1007). y>\ (loco). itt d pnlyphrnyls to Improve lindane l*n 'tav: Study of tire pciformante eric Injection loading. J. Assoc. Iifwinatopiapliie columns for ehlort* IrcmUts 62, 1203 (1200 b). I'olychhmdiipWoyls i>7 TlAO, C. li., W. N. Sui.uvan, and 1. IlonN'mN: A comparison of cvniMratlmr rates and toxicity to house flics of lindane ami lindane-chlorinated polyphenyl dcnoxils. J. )inm. Kntoinul. 40, 882 (1053). V, S. Food Olid Dntn AdminhlioHoii: IY.Nlit.ide Analytical Manual, Vnl. ] ami II, revised annually. Washington, D.CI. (lOfiO). Vam N.J improvement of the residual toxicity of DDT solution' |y ihc addition of coutnntone resin. Hull. Knlnmoi. ltesemeh 4.1, 411 (|U'2). VniMKicn, K., and I.. M. Rmnoips: Orgnnocldorinc residues In aquatic hitdj in tire Canadian Prairie Provinces. (In preparation, 1970). Wei-cii, n. M., M. LrviNK, and A. II. Conncv: Effect of chlorinated Insert Iridrs on steroid metulwHxm. In: Chemical fallout. Proc. 1st Rochester Conf. on Environmental Toxicity, Uriiv. of Rochester (1069), WioafAHK, C.; IUPAC commission on methods of pesticide rcsidito analysis. J. Assoc. Official Anal. Chemists 50, 1009 (1907). WfENCKK, W. W., and 1. A. But\kk: Dcrivatlzatlon of dicidrin and endrb) for eonRrmalion of residue identity. I. Assoe. Official Anal. Chemists 52. 1277 (1909). Zweio, C. (ed.)r Analytical methods for pesticides, plant growth regulators and food additives, vol. J, p. 1. New Yorx; Academic Press (1983). Manuscript received 20 January 1970; accepted 17 Fobmary 1970. MONS 083233