Document qdy98p0EzaKmr566Ka32QbmMG

( SOCIAL ..1C?0ni at 70V:Z'10?JxVi7ZD 3ZT.1aV:iz (r-C3s) ?olychlorinatad biphenyls are chemical mixtures of chlorinated biphenyl Isomers and find wide industrial application requiring heat stable*, non- fa fleviable liquids* ?23s in the UCA are marketed as the Aroclor -1200 series* Residues of ?G3s occur globally In fish and wildlife* In fish, residues of rOBs are principally the result of exposure to low levels of four Aroclor formulations: Aroclor^ 1242 (used as a hydraulic fluid), Aroclor 1240 (used In electronic and Industrial electrolytic capacitors), Arocloi^l254 (used in heat exchangers and dielectrics in large electrical transformers) end Aroclor^ 125C (a plasticizer)* The routes by which these materials enter acuatic ecosystems are not well known* Research problems receiving our immediate attention are: 1) ?CB Intovforrenc* in analytical determinations for pesticide residues; 2) unkr.cnm biological effects of 2C3 exposure* to Aquntic organisms as well as significance of ?CB residues in fish, and 3) the as yet undefined potential for ?CC-pecticide interactions in fleh and invertebrates* , Chemical Studies on ?CBc Analysis: The composition of the various Aroclor'n' formulations is boot illustrated in Figures ? and 10* The number above the chromatographic peak designates the number of chlorine atoms substituted on the biphenyl ring* The chromatograms were obtained by separating the Aroclor' form ulations with a oupport-eoated, open tubular capillary column in our L'erklnSlmor 270 gas chromatograph-mass spectrometer* Techniques for the separation and analysis of TCB and pesticide rosldues were ovaluated* The most satisfactory approach at present is to -68- MGNS 048398 ""I 1 150150152 156 160 1&4 158 172 178 180 TEMPERATURE,*C Figure 9. - GC-MS of Aroclor^ PCBs. SCOT GC-MS separation of Aroclor materials. The underlined numbers designate the Aroclor formulation and numbers above the peaks designate the number of chlorine atoms in the compound(s) determined from the mass spectrum. Temperature program rate 2 C/min, He 9 pslg, 50* x 0.020" SE-30 SCOT column, PE-270 GC-MS. 69 MGNS 048399 Figure 10. GC-MS of Aroelor' PCBa. SCOT GC-MS separation of Aroelor materials. The underlined numbers designate the Aroelor formulation and numbers above the peaks designate the number of chlorine atoms In tho compound (s) determined from the mass spectrum. Temperature program rate 2 C/mln, He 9 pslg, 50* x 0.020*' SE-30 SCOT column, PE-270 CC-MS. 70 HQNS 048400 separate pesticides and Aroclor^ formulations by silicic add chromatography* I.Te carefully evaluated tho procedure developed by Armour and Burke (J*A.O*A*c* il lie* 4, 751-763, 1370) and are satisfied that separation of PCBs and pesticides Is adequate* The response of two chlorine specific GC detectors, the electrolytic conductivity or microcoulometrlc, can be calibrated In ug or 03 of compounds when the molecular weight of the component is Thus, the concentration of an Aroclor" component can be calculated when no standards are availeble using the following equation: )1Z -C3 component - 137 . Ho. of Cl ur* Cl 35*5 Determination of the amounts of AroclorS 1243, 1254, end 1250 In residue extracts is poaolblo because each Arocior^ formulation contains two major components which are not precant In tho next higher eluting Aroclor formu lation* This technique requires cleaned-up extracts* reaticides should not be present in these extracts unless mass spectrometry Is employed to confirm GC peal: Identity* Standardization of various laboratory methodc remains undefined for analysis and reporting residues of Arcelor*** formulations in samples which contain more than one formulation or for samples in which the Isomer can- position is radically altered* Proportion of 3S::i-radiol*balod :''3c:--rudiolabalad 35C1 vara developed and utilized la developing analytical methodology and In studies of biological uptake and metabolism. Cne-gram quantities of 33Cl-radioactive * lalolad Aroclor^ 1243 and 1254 vero prepared by neutron irradiation In a nuclear reactor* These irradietod materials were cloaned-up using silicic -71- MONS 048401 add chromatography. The radio-labeled materials vere identical to the starting materials Javid L. Stalling Jamoo IT, huchine Blolorleaj. studies on 222a Acuta tonicity of ?C3s to fish:--1The toxicity of the Aroclor** series vaa determined using the standard rS-hr static bioasoay and cutthroat trout. Additional taste wore also made with bluagills and channel catfish 'Cable 14), The solubilities of the .'.roclor formulations in water aro reported In the range of 0,1-0.3 pg/I The results of theoe toots indicate a decrease In acute toxicity for Aroclor^ 1254 and higher. The COB tonicity Indicated by these tests o mis leading In that most fish mortalitias occurred in the last 24 hours of the test and the concentrations of the tast solutions were considerably above the true solubilities. The toxicitios of thaoo compounds became more apparent In lon^ taro, intermittent-flow bioaosays. Donald 7. Cvedborg Tarry D. T.ennady Clie oral toxicity of Arocloi 1242 and 1252 to rainbow trout was greater than 15C0 ng/T:g ("Ivon ner os for 5 days at 330 rag/hg/day). ?ostor L. ` jqrer, Jr. -72- HONS I Table 14. Acuta tcxtclty^/ of sovaral Arocloro to (elected flahea Aroclor mi 1232 1242 1248 1254 1260 1262 126C 4465 5442 5460 1240 1254 1243 1254 Specie* Cutthroat trout II ft * If II It l> II II II II 11 n 11 ii II n II ii II 3>annel catflah II II Bluesillt Temperature W) o.s2/ 8.5 8.5 8.5 8.5 0.5 0.5 0.5 8.5 8.5 8.5 18.32/ 18.3 13.32/ 10.3 ^ Static bloeclsy ^ Alkalinity, IS? pea; pH 7,6 ^Alkalinity, 35 ppm; pT. 7.1 5S-Hr TL^q Oig/1) 1,170 2,500 5,430 5,750 42,500 60,500 >50,000 >50,000 > 50,000 > 50,000 > 50,000 6,000 12,000 270 2,740 HONS 048403 73- Chronic toxicity of PCBs to fish71ftccn intermittent-flow bloassayc vara conducted with rainbow trout, channel catfish, and bluegllls* The chainleal> were Arocloi^ 1242, 1240* 1254* 1260 and DDT* The trials vara oonductod at 20 C I-Iowcvor, ArocloiS 124Q was also tested at 27 C against channel catfish and bluegills (Table 15)* Ilainbow trout wore the most susceptible to the Aroclor*- compounds, followed by bluegills and channel catfish* Aroclo^ 1240 was more toxic to all species tosted than Arocloi 1254* These teats served in setting guideline concentrations for chronic uptake studies* Further studies are required to establish the time-independent TL50- Foster L iiayor, Jr* 3iyglologlcal effects of ?CBs on fishT/e began studying chronic* sublethal offsets of ?C3o on fishes only recently and consequently wo have l l i limited observations* But* several inferences can be made at present* ?3a la fish food at concentrations known to occur in food organisms may well constitute a hasard to natural populations* For example, growth of lake trout was retarded by Aroclor" 1245 in the diet for 3 months Concentrations of 1*2, 3*5, and 12 ppm decreased weight gain by 6, 10, and 23Z, respectively, below that of controls* Growth of the high-expooure group was only about half that of the controls after 6 months* Conversely, thyroid activity, as i Indicated by 72-hr radioiodine uptake, was stimulated by ?C3 exposure (Figure 11)* Serum cortisol concentrations ranged from 33 to 46Z below that of the controls (see endocrine effects)* Depressed growth rates and elevated thyroid activity imply metabolic inefficiency producing a "loading" tress that can adversely effect viability and reproductive success* i -74- Blaka F* Grant Donald Swedberg HONS 048404 UPTAKE PERCENTAGE . Figure 11. Thyroid stimulation by 6 month dietary exposure to Aroclor 1248. t : 75 \ t 1 > HONS 048405 Tabla 15. Interoittaat-fflow bioaasays of Aroclora against throo fiahaa'V^ Arooloi 124227 Sooclos Itainbcv trout TL5o (jig/1) aftor-- , 5 days 10 days 15 days 20 days 25 days 30 days IOC 39 - - - - 1248^ 12S4 1250 DOC 1242 1243 1254 1250 1242 Rainbow trout aiuo^iiiD channel catfish 51 156 8 - 240 2.26 0.87 154 72 307 ISO - 443 - - - 174 54 0.26 54 75 204 - 107 21 10 135 245 - 54 212 - -' - 151 . 1248 1254 12S0 12432/ 124fl2/ Blua^llla Channel catfish 137 - 255 - 76 54 127 741 -- 57 300 256 - - 113 166 - - 137 - - l/lanparaturtf', 20C; alkalinity, 250; p:;, 7.4 ?7 Trallailnary bloasaaya ^Tamyaratura, 273 76- HONS 048406 Toxicity of >C3a to InvertebratesTests vara conducted to determine tUo tonicity of TCBo to selected Invertebrates* Static and continuous-flow tests with Invertebrates did not differ as much as with fish assays* In general, insects are much more resistant to the Aroclors than are crustacea (Table 13)* Herman 0* Sanders Bloconcentratlon of TCBs by aquatic microorganismsAroclors, ll!:e some of the organochlorine Insecticides, appear to be rapidly and greatly eoncoutratod by various organisms* For example, preliminary exparlmoncs hawed that Daohnla uarma concentrated ^C1- ArocloxP 1254 by 45,000 times aftor only 43 hours of exposure to a concentration of 300 ng/l. These data closely parallel that obtained in DDT and aldrln investigations with Daohnla mama* B* TItomas Johnson Bloconcentratlon of PCBs by aquatic Invertebrates?--The potential of 1254 to accumulate In fish-food organisms was investigated by exposing several species of aquatic Invertebratas to a ^01-labeled formulation of thle chemical in a continuous-flow oystea* All invertebrates exposed to 1254 shoved an initial period of rapid uptahe and residua magnification any times greater than the concentrations In water* For example, late Inetar mosquito larvae, Sulex tarsalis. which were exposed to 1.5 pg/1 of 1254 accumulated a residue of IT mg/Ug within 24 houro* This represents a 12,600-fold Increase over the reolduos in water* The tissue residues con tained to accumulate until the oevcnth day of exposure when the mosquito larvae were transforming Into pupae* -77- HGNS 046407 Tub la 16. Arocloi and DDT toxicity to lnvartabratas. Compound Arocloif 1242 Organism^ Crayfish Arocloi 1254 Crayfish Arodoi 1254 Crayfish DDT Crayfish Arocloi? 1242 Scud Arodoi 1242 Scud Aroclo^l248 Scud Aroclor 1254 Scud DDT Seed. DDT Scud Arocloi 1254 Glass shrimp DDT Glass shrimp DDT Glaaa shrimp Aroclor--^1242 Dragonfly Aroclor^1254 Dragonfly Aroclor 1242 Damoalfly Aroelor 1254 Damselfly DDT Damaalfly Bloassay typa=/ Zxpoauro (days) static 7 static 7 continuous-flox/ 7 tatlc 4 continuous-flow 4 continuous-flow 10 static 4 tatlc 4 atatle 4 contlnuoua-flow 5 contlnuoua-flow 7 static 5 contlnuoua-flow 5 static 7 atatle 7 contlnuoua-flow 4 continuous-flow 4 static 4 -so Cus/i) 30 100 80 100 10 5.0 52 2,400 3.2 0.6 3.0 1.0 1.3 800 1,000 400 200 56 ^Crayflah CSrconactes nala). Scud (Samnarua fasclatua), Glaaa shrimp Oalnacicnotaa Itr.dlahanala) , Dragonfly Caterer.!a bp.), Daaaalfly (I.chnura vortlcalla). ^Tamparatura, 15.6C{ al'.-.alinity, 35 ppm} pK, 7.1 -78- HONS 048408 In sobs expartaunts, wc were oblo to continue the bioessays until an apparent plateau, or equilibrium concentration was reached within the organism. For example, tho scud, Gamarus psau iGllraaeus, was exposed continuously to 1*6 /i'j/1 of 12S4 in water until residues reached an apparent equilibrium concentration at 14 days; total body residues at this tine wora 38 mg/kg* a concentration 27*000 tinea that In water. Ones this equilibrium v/ia reached within the organism, no further residue ratification was recorded after an additional 21 days of exposure (Figure 12) In similar experiments, oarly instar crayfish, Orconcctes nala. exposed to 1.2 pg/1 of 1234 accumulated residues at a slower rate than other invertebrates Investigated. The crayfish were accumulating 1254 at a linear rate when the _x>eriner.t wc.s terminated after a 23-day exposure (Figure 13). " Homan 0. SanJers ResiduesScud exposed to 1254 wore analyze! by gas-liquid chrcna- Cogreeny to investigate potential shifts in tho residue compos!tien which swy hava occurred as a rasult of oatibollsn. llewever, we found no significant altontlons in the chenical, but soma isoner9 were accumulated sore than othors. Tho most notable shift of residue components was a two-fold Increase in concentrations of the lower chlorine isenurs (tri- and tatrachlaroblphunyl isoasrs). The relative concentration of higher chlorinated isonars (pent?.- and hexachloro biphenyls) wore h-.craascl by on* half. . David. L. Stalling James L. Johnson -79- HONS 048409  Analysis of bluegill and channel catfish oxpoaud to Azaclet'0ft 1249 an.I 1254 ravelled tha fallowing high concentrations of PC3 residues. Expj.urc ('lays) water PC3 F.oSiduuS (u~A vh;lo fish or u~/l wr.tar) Aruclji*3 1248 Arr'clcr5'1 1254 chuan-l channel catfish water bluugills vaeur catfish water bluerills 23 13.3 500 4.9 177 4.1 177 6.3 44 60 13.3 958 4.9 312 4.1 312 6.8 87 Raslduas In bluucills vera lower then fur channel catfish. Araclor1*' 1248 was concentrate! to a neater extant than Aroclox 1254, but no sign ificant chances were obsurvud in isonar carvesitlan. dosiluc concentrations In tha fish wore 6,300 to 71,400 tlaua the uxy.'sure levels nfcar 60 'ays. Foa ling studies './ita PCBs are being conducts! to detenaine the significance of dietary uptake an! to deterslne adverse effects on growth and other physiological functions. PC3 residua analyses fren fish in these studies have yet to ba conploted. Janes U. .'iuckins David L. Stalling PCB-Paoticide Interactions:--;fo perspective interactions in fish has as yet bean penetrate:!, but analyses of fish fron natural ecosystem show that they contain PCb residues which are 2-5 Clues greater than tha residues of the DDT cncplex. V*esocrch will bo conducted to dwteruinu whether exposures of fish end invertebrate to Pda intensifiuS the effects of PCDs ou the chenical kenetico of. pestlcl !e uptake and atcragc, Inforsation on tha effects of PC3 exposures on fish reproduction and the pwtential for inter action with curtain organochlorinc pesticides will he useful in cstinating tho onvironuental lupact cf these Materials. M0NS 048410 WATER CONCENTRATION (116/1) EXPOSURE II MO DATS Flgur* 12. Biological magnification by acud, Gammarua pseudo!Imnaqua of 36Cl-Aroclor 1254 from water during 35 days axpoaura. SI mons 04(1411 MAGNIFICATION WATER CONCENTRATION(U G /l) Figure 13. Biological magnification by crayfish Orconectes nals of 36Cl-Aroclor 1254 from water during 21 days of exposure. 82 HONS 048412