Document rp1EXkjDnawDrg6OE4qqJpqwG

, 11 Decenocr 1970 FC3 NZWSLZTTZP. ANALYTICAL METHODS ANT) CHEMICAL CHADACTEDASTICS _ ' Jerry Burke Residue Chemistry Branch, De. lartment cf Health, Educaticr., ar.d Welfare, Feed and Drug Administration. Washington, D. C. A paper, by Judith Armour and Jerry Burke of this laboratory, v/as presented at the 1970 meeting of the AOAC and v/ill le published in the January, 1971 . issue cf nhe JAOAC. - Behavior of Chlorinated Naphthalenes in Analytical Methods for Crganochlorine Pesticides and Polychlorinated Biphenyls Abstract Chlcrinared naphthalenes, industrial che.v, cals with properties similar zc polychlorinated biphenyls (PCB), are recovered by the Food and Drug Administration's.methods for multiple pesticide residues. These materials cculd interfere with the gas chi onatographic determination cf several crganochlorine pesticides. A sil:cic acid column chromatographic procedure previously developed to separate PCB from pesticide residues, : r-articularlv DDT and its analogs (Armour, J. and Burke, J., JAOAC ` 761-765 (1970), has been found to also separate chlorinated naphthalenes from the common crganochlorine pesticides. i ' Bernard K. Mulhern, Eugene Crcmartie, William L. Heichel, and Andre A. Belisle, Bureau of Sport Fisheries and Wildlife, Patuxent Wildlife : Pesearch Center, Laurel, Maryland 20310 Semi-cuantitative Determination cf Polychlorinated Biphenyls in Tissue Samples by Thin Layer Chromatography i (.Accepted for publication in JAOAC, Spring, 1971) Abstract : A method is described for the analysis of polychlorinated biphenyl ' (PCB) compounds in tissue samples. Cleanup by hexane-acetenitrile i partitioning and Florisil column chromatography are performed on samples \ prior to oxidative treatment to convert DDE to DC3P. PCB's are then j - determined se.mi-cuantitatively by TLC. No prior separation of PCB's \ from chlorinated pesticides is required. The lower limit of sensitivity ] is 0.2 micrcgrams. DSW 282612 STLCOPCB4063941 4 PCS Newsletter 2 H. G. V.'&bb, F.vDA, Southeast l.'ater Laboratory, Athens, Goor-ja Solubilities of PC3's The solubilities of the identified components of Aroclor 1221 in water at roc.r. temperature (24+ 1C) were determined. Excess of the pure component was equilibrated with one liter of distilled water for at least 15 hours, with occasional shaking. The mixture was filtered through a sintered glass filter of Fine porosity' and 500 ml of the filtrate was extracted with hexane. The concentrated hexane extracts were analyzed by gas chromatography. Biphenyl, 4-chlorobiphenyl, and 4,4 -dichiorcbiphenyl could also be determined by uv fluorescence. The latter technique was applicable to the saturated aqueous solution as well as to the hexane extract and provided a check on the extraction efficiency. At least four determinations were made for each compound, using a statistical design. 2n:h block of four simultaneous runs included a pair made with the same solute but using hot and cold w; ter for the initial equilibration. Analysis of the data is not complete but the final values are expected to be withi:il5w* of the following values: Biphenyl 3.0 mg/1' 2-chloro- 1.6 mg/1 4-chloro- 1.0 mg/1 2,2 -Dichloro- 1.0 mg/1 i 2,4'-Diehloro- 0.5 mg/1 -" ` i 4, 41 -Dichlcro- 0.C5 mg/1 i Composition of Arochlor 1221 and 1254 . The composition of Aroclor 1221 was estimated by gas chromatography on SZ-30. The detector sensitivity to the individual components was checked with standard solutions of the pure compounds so far as these have bee:: identified. The Coulson conductivity detector gave the most consistent response but did not detect biphenyl. The flame ionization detector picked up biphenyl but gave variable response to the chlorinated compounds. i In the following table, the percentage^of biphenyl was determined from, the ratio of biphenyl to 2-chiorobiphenyl and the remaining weight i percentages were derived from the Coulson results: i Biphenyl 18% it 2-Chloro- 31% \ 4-Chloro- 19* 2,2'-Diehloro- r% ij 2,4 -Dichloro- 20 % V 4,4 -Dichloro- 5cr/3,t id i An unidentified dichiorcbiphenyl elutes between 2,2'- and 2,4'- which comprises perhaps 5'% hut a standard is not available for calibration of the demector. The peak ascribed to 4,4 - also includes a contribution l prom some trichlorc'piphenyl material. l1 Gas chromatography of Aroclor 1254 on 6' x 1/4" of 6% SE-30 using a ;-i Coulson detector gives nine measurable peaks. From the area of each j j i S ] t)S\N 282613 iI STLCOPCB4063942 : PCB Newsletter peak and the number of chlorines in each peak (determined independently by mass spectrometry), the weight percen.tage of each material can be calculated: _Pea,k /Cl wt.ss 1T 9 2 5 12 , 3 5 18 4 3 23 O5S' 6 6 14 12 7 8 6Or . 9 2 9' 6 1 Detector response for Components of Aroclor 1221 . The Ccuisor conductivity de tector appear,; to respond linearly with the amount of chlorine in each PCB. Fluore scence results are highly variabie with some components giving no response at all. Cur data also indicates that the relative resporj se of the flame ionization detector (based on biphenyl =100) and eleciron capture detectors (2,4'response = 100) varies considerably from compound to compound: Compound FID ECD ` Biphenyl 2-C13P 4-C13? 2,2'-DCS 2,4'-DC3 4,4'-DCB ICO 7./ 60 36. 24 13 0 20 7 19 100 17 For additional information on solubilities, percentage composition, or detector response, please contact Dr. Tom Hoover, 404-546-3185- Chemical Identification of Individual PCB Isomers ; Ir. the last newsletter we reported the identity of several components i cf Aroclcr 1221. We also assigned these materials a relative retention i index based on their retention times on 6' x 1/4" of 8p SE-30 at 200. For example, the index for 4,4'-dichlorobiphenyl is 0.4i under these conditions. We postulated that the peak at 0.32 was 2,4'-. This has been confirmed. We have also shown by comparison of the 12 spectra of knowns and the Aroclcr fraction that in 1242 the peal-: at 0.41 contains at least three components: 4,4'-; 2,5,2'-; and 2,4,2'-. The peak at 0.46 contains 2,3,2'- and probably another component as well. There is reasonably good GC and 13 data to suggest that 0.54 contains 2,5,^'- and 2,4,4'-. Capillary GC-MS shows that the peak I at 0.58 contains at least three separate materials, two zeirz-chlcro isomers and a trichloro isomer. This latter material has been positively 1 identified as 3,4,2'-. The GC retention times also indicate that i 2,3'-; 3,4'-; 2,4,2',4'-; and 2,4,5,2',5'- may be present in peaks 0.32, 0.4l, 0.69, and 1.19 but no 13 data is available to confirm this 1 1 yet. I oS\N 2826<'4 STLCOPCB4063943 FC5 Newsletter R. G. V/ebb (Continued) Capillary GO of the Aroclors mixed with synthetic PCB's shews that 2,3i4'-; 3,4,4'-; ar.d 2,4,6,2* ,4' ,6'- are not in Arocior 1248. A Work is in progress to identify some of ;he tetra and pentachlcro- iscmers. A feu of these materials have been purified and are available in cne milligram or larger quantities. If lack of pure PCB iscmers is the major obstacle in anyone's program, please contact Dr. Ren V/ebb at 4o4-546-3lS3. EXVIRCM'ENT.AL CCCURE2KC2 AND FA7I G. Fred Lee and Gilman D. Veith, V/ater Chemistry Laboratory, University of .vescensir., Kacison. V.isco..sir. Gilman D. Vc-ith completed his Ph.D. thesis cn "!The Environmental Chemi: try of the Chiorcbiphenyis in the Milwaukee River" in .August, 1970. Copies of Dr. Veith :s thesis may be obtained for short term loan by writing ., to G. 7red Lee. Microfilm copies may be obtained from the.Ann Arbor Microfilming Service. This thesis provides data cn the amounts of PCD ! compounds found in the Milwaukee River yater, plankton, and fish. Also, 1 limited data is provided on concentration of PCB in municipal and industrial waste water effluents. > Current studies on PCB include work of Dr. Veith cn the major sources of PCB's in the Green Bay region of Lake Michigan and compositional char.ges of the commercially prepared mixtures of the PCB's in the environment. In particular, the chemical and biological degradation of the PCB's will be evaluated in an effort to predict the fate cf the compounds in tne environment. Additional studies have been initiated in the development of chemical confirmation methods for the PCB's. INTERACTIONS ADD UPTAKE STUDIES Dr. Daniel V. .Anderson, Bureau cf Sport Fisheries and Wildlife, Davis, California__________________________________________ ________________ I am planning some PCB research with Bob Risebrcugh this spring and will ce involved in brown pelican research. V/e are interested in PC3-DDE interactions, re: eggshell thinning, etc. i I DSW 282615 STLCOPCB4063944 PCB Newsletter 5 David L. Stalling, bureau of Sport Fisheries and Wildlife, Fish-Pesticide Research Laboratory, Columbia, Missouri_________ ____________________________ We have been successful in preparing radioactive ^ Cl-Aroclor 12^8 and 125^ by neutron irradiation. Using these materials to evaluate the cleanup procedure reported by Armour and Eurke (JACAC, 53i No. 4, pp. 7oi-?6S, 1970) less than 2 percent of the PCB's were present in the pesticide fraction. Fish PCB uptake studies are currently underway using the radioactive materials. Whole body residues of 2-k ^g/g resulted from 3-day exposures of channel catfish to k--10 )xg/l of each PC3. These data are from a six week PC3 exposure of bluegill and channel catfish to determine residue changes upon uptake and to examine the possibility of metabolism by fish. Data from PCB feeding studies is not yet available. TOXICITY R. G- Heath, J. V/. Spann, J. F. Kreitzer, and C. Vance, Bureau of Sport Fisheries and Wildlife, Patuxent Wildlife Research Center, Laurel, Maryland "effects of Polychlorinated Biphenyls on Birds" Presented at the Ipth International Ornithological Congress, The Hague, Netherlands,-Sept. 1970. Abstract - Toxicities of six technical polychlorinated biphenyl (PCB) compounds (Monsanto Company's Aroclors 1232, 12^27.12^8, 125^, 1260, and 1262) were studied on penned mallards (Anas platyrhynchos), pheasants (Phasianas colchicus), bobwhite (Colir.us vnrginianus), and Japanese quail (Ccturnix coturnix) at the Patuxent 'Wildlife Research Center, Laurel, Maryland. LC^q's expressed as ppm of PCB in dry feed, were determined for 2-week-old birds fed treated diets for 5 days. Arcelor toxicity, generally less than that of DDT, was found to be positively correlated with chlorine percentage (last two digits of Aroclor number). The joint toxicity of Aroclor 125^ and SOB on Japanese quail was additive, not synergistic. Low dietary levels (25 and 50 ppm) of .Aroclor 125^ produced no measurable reproductive effects on mallards and bobwhite. . David L. Stalling, Bureau of Sport Fisheries and Wildlife, Fish-Pesticide Laboratory, Columbia, Missouri 'We have made progress in the PC3 toxicity testing and are including three tables which summarize -cur findings for both acute and chronic bicassays with fish and invertebrates. (See following 4 pages.) DSW 282616 STLCOPCB4063945 J o Bureau of Sport Fisheries and Wildlife rish-?escicido Research Laboratory Route 1, Columbia, Missouri 65201 November 12, 1970 Aroclcr0- and DDT tonicity to invertebrates Compound Organism3 Bioassay type0 ' Aroclori 1242 Crayfish static Aroclor^ 1254 Aroclo/ .1254 Crayfish Crayfish static continuous-flow Exposure (days) 7 7 7 TL50 (DS/x) 30 ICO 80 DDT Aroclov 1242 Arocloj^ 1242 Aroclor(r^) ..248 Aroclor^1254 DDT Aroclot^ 1254 Crayfish static Scud con t inuo us - flev/ Scud continuous-flow Scud static Scud . static Scud Scud static . r* con tinu6us-flow Glass-shrimp con t ir.uous-flow 4. 4 10 . 4 4 4 5 7 100 10 5.0 52 2,400 . 3.2 0.6 3.0 DDT Glass-snrimp static 5 1.0 i * DDT Glass-shrimp continuous-flow 5 1.3 i \ Aroclor^ 1242 Dragonfly static- 7 . 800 . /*t\ Aroclor^1254 Dragonfly static 7 1,000 AroclcrS* 1242 Damselfly continuous-flow 4 400 11 Aroclor1254 Damselfly continuous-flow 4 200 DDT Danselfly static 4 55 " Cravfish (Orconer.tes nai.s). Scud (Gsaa'.r.rus fas ciatus), Glass-shrimo (la laar.-.onatas <Cd-- c?-iCCin.S is ) 9 Dragonfly (Macror.i ci s? ) f Duu.o alfiy ;i;i IiI (xschnura vertlealis). D Temperature, 15.6C; alkalinity, 35 ppm; pH, 7.1 DSW 282617 tI i STLCOPCB4063946 i Fish-?csticide Research Laboratory .newsletter Acute tonicity of several Aroclcrs"'to selected fishes. Aroclot 1221 ' Species Cutthroat Ter.oerature ' (C) Ob' 3.9 S6hr TL50 0*s/D 1,170 1232 Trout 8.9 2,500 * 1242 1248 1254 1260 1262 1268 4465 5442 5460 . . 3.9 3.9 3.9 3.9 3.9 3.9 3.9 8.9 3.9 5,430 5,750 42,500 60,900 50,000 50,000 50,000 50,000 50,000 , i 1248 Channel catfish A5*3 6,CC0 1254 # IS. 3 12,000 13.3^ 1248 Bluegills 278 ij 1254 13.3 2,740 Alkalinity, 159 ppa; pH, 7.6 c-'Lr Alkalinity, 35 ppt:; pH, 7.1 1 j 1 Dsw 282618 STLCOPCB4063947  Fish-Pesticide Research Laboratory ?C3 Newsletter n G ; Chronic toxicity of Aroclors"^ to three fishes3. ; /^N TLsn (u?/l ) Aroclor^1 Species 5 day 10 clay 15 day 20 day 25 day 30 day 12421 Rainbow . 109 39 - - - - 1 1248 trout 51 -- ---- 1254 156 8 - - - - 1260 - 240 94 21 . - - o 1242 Eluegills 154 72 54 - - - 124 S 307 160 76 10 - - 1254 - 443 204 135 54 - 1260 - - - 245 212 1 51 1242 1248 Channel catfish " 174 107 255 127 - - .- 1254 - - 741 300 1-13 i 1260 1 -f - 296 166 137 124 S Eluegills 137 76 - - - - 124Sb Channel catfish - 94 57 - - - DDT Rainbow 2.26 0.87 0.26 - - - trout a Ter-paratere, 20C; alkalinity, 260; pH, 7.4 i Temperature, 27C 1 i Preliminary bioassays j ij jii i4 i 1 Jj/CCl'Soh-Vj/ i DSW 282619 i \ STLCOPCB4063948 Fish-Pesticide Research Labo tory - ..CWoiC t. .0, 9 -< Estimated cine for DDT and Aroclori" 1242, 1243, 1254, and 1250 to .'i 50 percent of selected fishes. Chemical /fT\ Aroclor^ 1242 Concentration (pg/1) 50 Aroclor^ 1243 50 Estimated tire for 5CM r.ortalitv Rai o\: trout: 20C Dlucnills 20i'C 27C Char r. 2 1 tat:ish iO'C i~r c 7.21 5.21 11.7 13.0 12.9 15.8 22.7 16.S .1 Aroclor-'' 50 1254 8.3 27.5 - 27.6 lI Aroclor^ 50 I is 1260 DDT 2 16.8 5.0 36.4 - 59.3 - - '- - I * i 1 Prelim: Ccrn?i-tir rb nary bioassays A. i r- - ! ( O.rcr.ic e fleets cf Arcelor^ 12l-i S or. '2. :e- Ti*out. v'-'-'or-.' unit y} ! he exposure of immature lake trout to Aroclcr'^ 1248 will continue fc: c* n hree tore- it oaths. C Growth continues to be better in. the control lots than in the Aroclor-";-treated lots. During the first 7 months, lake treut receiving control food grew 1.6 tirr.es more the; . these receiving 1 i relatively high amounts of FOB in. their diets. ^Mortality was also higher in the PC3-treated lots, The iodine uptake, by lake trout, after 6 months of exposure , suggests that Aroclcr^ stimulated their metabolic rates. Serum, cor tisol concentrations in all treatmen groups were depressed 33 to 46,'i. These results imply that dietary doses cf 1.2 to 12 m.g/kg of Arocl or-' 1248 in natural or synthetic die nay well influence osmoregulation in fish, and their ability to tcler; e 3 ur ss t i DSW 282620 STLCOPCB4063949 1- .1 f ' ; i .j PCB Newsletter Alan V. Neb e her, F.-/QA, National Water Quality Laboratory, Duluth, kirne-sota Testing the effects of ?C3's cn survival and re^oducticn cf feehr. fa re~rz is essentially completed. Sight Arcclcr^", 1221-I26S, v:ere uscc. in static nesting. The Danhnia v;ere tested from nev.'ly-bcrn young (I 12 hours old) through no reproduction "id growth of their young * (3 weeks) with new solutions changed once a week. Safe levels for survival and reproduction were determined: 125^ was the most toxic wi;h a safe level near 20 ppb. The toxicity decreased for 12o0 with a safe level near 35 ppb. Aroclor 1262 had a safe level near *rC ppb,and 12co was safe at 250 ?pb. Toxicity also decreased below 125^. Arcelor 12-.-3 was safe near 30 ppb with 12':2 being safe at 50 ppb. Arcelor 1232 was safe at approximately 75 ppb. Aroclor 1221 was the least tc:-:!c w; th a safe; level near 300 ppb. Continuc-us -flev/ testing with Arcclors 12 ?. end 125'* with Oaphnia m--r indicate that 30 ppb 12;.-2 ; ' 15 ppb 125^ arc safe levels. I: runs rus "seudcliun;eus have survived and reproduced at 12^2 levels cf up to ca. 15 ppb. The fathead minnow survived IOC ppb for one month but was obviously stressed. (The concentrations given above are apprexinctiers since we have not yet developed analytical methods to measure these levels.) . .. ; i } 1 ! I J!:: DSW 282621 STLCOPCB4063950