Nationwide Residues of Organochlorine Pesticides in Wings of Mallards and Black Ducks

Transcription

1 Uiversity of Nebraska Licol of Nebraska Licol US Fish & Wildlife Publicatios US Fish & Wildlife Service Natiowide Residues of Orgaochlorie Pesticides i Wigs of Mallards ad Black Ducks Robert G. Heath Patuxet Wildlife Research Ceter Follow this ad additioal works at: Heath, Robert G., "Natiowide Residues of Orgaochlorie Pesticides i Wigs of Mallards ad Black Ducks" (1969). US Fish & Wildlife Publicatios his Article is brought to you for free ad ope access by the US Fish & Wildlife Service at DigitalCommos@Uiversity of Nebraska Licol. It has bee accepted for iclusio i US Fish & Wildlife Publicatios by a authorized admiistrator of DigitalCommos@Uiversity of Nebraska Licol.

2 Reprited by the U. S. Departmet of the Iterior Bureau of Sport Fisheries ad Wildlife Patuxet Wildlife Research Ceter Laurel, Marylad Natiowide Residues of Orgaochlorie Pesticides i Wigs of Mallards ad Black Ducks Robert G. Heath' ABSRAC Natiowide moitorig of orgaochlorie pesticides i wigs of more tha 24,000 mallards ad black ducks bagged durig the 1965 ad 1966 hutig seasos showed DDE to be the predomiat residue, followed i order by DD, DDD, dieldri, ad heptachlor epoxide. Residues were geerally highest i wigs from the Atlatic ad Pacific Flyways, ad lowest i the Cetral Flyway. DDE was reported for every State ad was otably high i wigs from New Jersey, Mas.~achusetts, Coecticut, Rhode Islad, New York, Pesylvaia, Alabama, Califoria, ad Utah. Dieldri residues were prevalet i wigs from Arkasas, exas, Utah, Califoria, ad several States i the Atlatic Flyway. Itroductio Natiowide moitorig of orgaochlorie pesticides i wigs of wild mallards ad black ducks was iitiated by the Bureau of Sport Fisheries ad Wildlife i late 1965 as a segmet of the Natioal Pesticide Moitorig Program. Fidigs reported here are based o chemical aalyses of wigs from more tha 24,000 ducks bagged durig the 1965 ad 1966 hutig seasos. he data provide base readigs from which future treds i residue levels ca be measured, ad they permit geographic comparisos of residues. Wig moitorig is scheduled hereafter at 2 to 3year itervals. A full descriptio of the Bureau's moitorig commitmets has bee give by Johso, Carver, ad Dustma (5). he decisio to moitor mallard ad black duck wigs was based o several factors: (a) he combied rage of the two species covers the cotietal' Uited States, the mallard beig relatively abudat i all but the Easter States where the black duck predomiates; (b) Wigs were readily available as a byproduct of a established I PatuxeN Wildlife Research Ceter, Bureau of Sport Fisheries ad Wildlife, U.S. Departmet of the Iterior, Laurel, Md atiowide survey of waterfowl productivity wherei each fall cooperatig huters mail the Bureau tes of thousads of duck wigs for biological examiatio; ad (c) Didal ad Peterle (3), usig DD, riglabeled with chlorie36, to study DD dispersio' i a marsh ecosystem, foud highly sigificat correlatios i 104 captive mallards ad scaup ducks betwee DD residues i wigs ad those i breast ski, kidey, breast muscle, uropygial glad, adreal glad, pacreas, brai, goads, liver, ad thyroid. he average level i the wigs was essetially equal to the media level i the above body parts; it was approximately twice that : breast muscle ad about oeeighth that i the urotgial ~~. A he moitorig methodology was successfully tested i early 1965 with wigs from mallards ad black ducks take i New York ad Pesylvaia durig the fall of 1964, as reported by Heath ad Prouty (4). Fidigs based o aalyses of 36 "'pools" of wigs, each pool composed of 25 defeathered wigs chopped ad bleded ito a homogeate, idicated that orgaochlorie residues were preset i all pools ad that levels of DDE teded to be higher i wigs of adults tha i those of immature birds. Wigs were aalyzed i pools rather tha idividually to icrease the precisio of estimates of average residue levels from a fixed umber of aalyses. Variability of residue levels amog replicated pools idicated that pool size should ot be reduced from 25 wigs. Methods Wigs from the 1965 ad 1966 hutig seasos were mailed by selected huters throughout the Uited States to oe of four regioal collectig poits ad held i froze storage for examiatio i early 1966 ad Durig examiatio mallard wigs from most States ad VOL. 3, No.2, SEPEMBER 1969 Pesticides Moitorig Joural 115

3 black duck wigs from Easter States were first segregated ito State groups of immature ad adult wigs, ad each group was the systematically sorted ito pools of 25 wigs each. A radom sample of these pools, roughly proportioal i umber to a State's mallard or black duck harvest, was selected for pesticidal aalysis. Pools ot selected were discarded. Each selected pool was eclosed with a idividually umbered tag i a plastic bag, packaged i dry ice, ad shipped to the aalytical laboratory. Records associatig pool umber with pool descriptio (State ad age) were retaied by the ivestigators; thus, pools were idetified oly by umber durig chemical aalysis. Wigs were aalyzed i 1966 by the Hazleto Laboratories, Falls Church, Va., ad i 1967 by the Wiscosi Alumi Research Foudatio, Madiso, Wis. Laboratory selectio was by bid. Prior to selectio both laboratories satisfactorily aalyzed material treated with kow amouts of the pesticides expected i moitorig; recovery rates geerally exceeded 84 %. Preparatory to aalysis, wigs were trimmed of flight feathers with a bad saw ad chopped ad bleded ito 25wig homogeates with a Hobart food cutter. Residues ~ere measured to a limit of sesitivity of 0.05 ppm (wet weight). Aalytical procedures (l) were as follows: Hazleto Laboratories. A 20g aliquot of the homogeate was dried by gridig with ahydrous sodium sulfate; extracted by shakig ad cetrifugig three times with petroleum ether (oe lo<hml portio ad two 50ml portios); cleaed by acetoitrilepetroleum 'ether partitioig ad elutio through a FIorisil colum i two fractios, the first cotaiig 6% ethyl ether ad 94% petroleum ether, ad the secod cotaiig 15% ethyl ether ad 85% petroleum ether. he two fractios were aalyzed separately by electro capture gas chromatography usig a Chromalab Model AltO gas chromatograph with a radium226 detector (Gtowall Corporatio). he operatig parameters were: Colum: Carrier Gas: Glass, 6' x ~" 00, packed with 10% DC200 o 100/120 mesh Gaschrom Q N2 at 120 ml/mi emperatures: Ilet 225 C Colum 205 C Detector '250 C WARF Istitute. A 40g aliquot of the homogeate was airdried hours at 40 C; extracted i Soxhlet for 8 hours with 70 ml ethyl ether ad 170 ml petroleum ether; cleaed ad separated by elutio through a FIorisil colum i two fractios, the first cotaiig 5% ethyl ether ad 95% petroleum ether, ad the secod cotaiig 15% ethyl ether ad 85% petroleum'ether. he 116 two fractios were aalyzed separately by electro capture gas chromatography usig a BarberColma Pesticide Aalyzer Model 5360 with a strotium90 detector. he operatig parameters were: Colum: Carrier Gas: Glass, 4' x 4 mm 00, packed with 5% DC200 o 70/90 mesh Chromport XXX N2 at 7090 mi/mi emperatures: Ilet 230 C Colum 200 C Detector 240 C able 1 lists, by State of collectio, the average residue levels of DOE, DD, DOD, ad dieldri i the wigs of adult ad immature birds i late 1965 ad he 2year rage i levels ad the umber of pools i each set are also preseted. able 2 lists the 2year average levels ad stadard errors of these chemicals, derived by combiig both years' data. he 2year averages are iteded as referece poits for detectio of treds i future levels. Other chemicals were detected i o more tha trace amouts ad are discussed i text oly. States are listed i both tables i orthtosouth order withi each of the four cotietal waterfowl flyways: Atlatic, Mississippi, Cetral, ad Pacific. Geographic rather tha alphabetical listig was used to facilitate geographic comparisos. States were stratified (2) by flyways sice a majority of mallards ad black ducks remai withi a give f1ywav durig migratio. Essetially, the, we are moitorig flyway as well as State populatios, the wigs from each State beig a sample of that part of a flyway populatio frequetig the State durig its hutig seaso. able 3 gives the 2year flyway meas ad stadard errors for the subject pesticipes, derived by weightig (2) each State statistic by the estimated total bag i that State of the respective species ad age group. Results DOE proved to be the predomiat residue throughout the survey. Me'asurable amouts of this stable metabolite of DD ~ere reported i early all pools of adult wigs ad i most pools of immature wigs. Residues of DOE were geerally from two to five times higher tha those of DD which, i tur, teded to be higher tha those of DOD. Dieldri was foud i wigs from more tha 30 States, although aldri, which coverts to dieldri, was ot detected. Heptachlor epoxide was reported at trace levels from oethird of the States; heptachlor was ot detected. Lidae was foud i wigs from oly two States, ad edri was ot detected. Proouced State ad regioal differeces i average levels of DOE were apparet. Some of the highest levels were ecoutered i adult black ducks from a cotigu PESICIDES MONIORING JOURNAL

4 ous group of Atlatic Flyway States that icluded New Hampshire, Massachusetts, Rhode Islad, Coecticut, New York, Pesylvaia, New Jersey, ad Delaware. DOE averages raged from 0.88 ppm i New Hampshire to 2.10 ppm i New Jersey. Mallards from the three States sampled i this groupnew York, Pesylvaia. ad New Jerseyexhibited similarly high residues. Elsewhere, oly Alabama. Califoria, ad Utah showed comparable levels of DOE. Adult mallards from Alabama had the highest average level i the survey (2.17 ppm), adult black ducks from New Jersey the secod highest level (2.10 ppm), ad adult mallards from Califoria the secod highest level amog mallards (1.45 ppm). I cotrast, DOE averaged below 0.14 ppm i both adult ad immature mallards from Illiois ad Missouri i the Mississippi Flyway ad from North Dakota, South Dakota, easter,motaa, Nebraska, Kasas, ad Oklahoma i the Cetral Flyway. DD ad DOD residues i a give set of pools teded to parallel those of DOE, but at lower levels. Natiowide. DD exceeded 0.50 ppm i oly five sets of pools (immature black ducks from New Jersey were high at ppm DD), ad DOD averages failed to exceed 0.50 ppm. Compariso of average DOE residues i flyway populatios Cfable 3) shows that levels i black ducks, i the Atlatic Flyway, were the highest i the survey. Amog mallards. averages were similarly high i the Atlatic ad Pacific Flyways, ad about oethird as high i the Mississippi ad oriefourth as high i the Cetral as i either coastal flyway. Average levels of DD ad DOD were highest i the Atlatic Flyway ad were usually too low to be quatified i the Mississippi ad Cetral Flyways. Dieldri was detected most frequetly i the Atlatic Flyway i both mallards ad black ducks: wigs from oly Maie ad the combied States of Georgia ad Florida failed to show residues. Dieldri also was prevalet i wigs from Arkasas, exas, Utah, ad Califoria; otherwise it was either udetected or preset i little more tha trace amouts. State averages rarely exceeded 0.25 ppm. Residue levels of DOE teded to be higher i wigs of adults tha i those of immature birds, a differece ot apparet with DD. DOD, or dieldri. his pheomeo. first observed i trial moitorig (4), suggests that equilibrium betwee chemical storage ad elimiatio, i at least the wig, is less readily attaied with DOE tha with the other chemicals. Heptachlor epoxide was reported i at least oe pool from each of 16 States, ie of them i the Atlatic VOL. 3, No.2, SEPEMBER 1969 Flyway. Residues were most prevalet i both mallard ad black duck wigs from New York ad Coecticut where levels averaged about 0.06 ppm. races of heptachlor epoxide were also recorded for New Hampshire, Massachusetts, Rhode Islad, Pesylvaia, Marylad, Virgiia, ad North Carolia i the Atlata Flyway; Ohio, Wiscosi, ad Iowa i the Mississippi Flyway; Nebraska i the Cetral. Flyway; ad Washigto, Orego, ad wester Motaa i the Pacific Flyway. Lidae at trace levels was recorded i wigs from Washigto ad Michiga; otherwise, it was ot reported. Lidae is recommeded by the U. S. Departmet of Agriculture primarily to cotrol aphids i apple ad pear orchards (7), which could explai the residues associated with these two orchard States. Aalysis of the groud wig material showed that the homogeates cotaied approximately 11 % lipid material ad 36% moisture. (Precise percetages of moisturead lipid cotet for specific sets of pools are available upo request.) Discussio While agricultural uses 'of pesticides probably accouted for much of the residue material detected i wig moitorig, other sources of cotamiatio should be cosidered. Sewage from populatio ceters may cotribute sigificat amouts of pesticides to some aquatic; eviromets. Similarly, idustrial effluets from pesticide maufacturig piats have bee kow to cotai substatial residues of pesticides lost i chemical processig. It is well kow that i some States, vast quatities of DD have bee applied to coastal marshes over the past 2 decades i mosquito cotrol programs. he practice has bee especially otable i those States extedig from Massachusetts to Delaware. Because of persistece ad a tedecy to accumulate i may orgaisms, substatial residues of DD, ad especially the metabolite DOE, are ow preset i marsh soils ad faua. Wood well, Wurster, ad Isaacso (6) report that residues of DD ad its metabolites averaged more tha 13 Ibl acre i the soil of a extesive salt marsh o the south shore of Log Islad, ad that withi the marsh, residues icreased with trophic levels from 0.04 ppm i plakto to 75 ppm i a rigbilled gull. DOE residues were exceptioally high i wigs of both mallards ad black ducks from New Jersey, where for may years coastal marshes have bee treated with repeated aerial applicatios of DD. A umber of States are ow usig chemicals less persistet tha DD i mosquito cotrol work. Summary ad Coclusios he fidigs from 2 years of moitorig idicate that duck wigs ca fuctio as sesitive detectors of eviro 117

5 metal DD ad the metabolites DOE ad DOD, as well as dieldri ad udoubtedly other orgaochlorie compouds. Despite some variatio due to samplig ad aalytical processes, residue statistics were sufficietly precise to show differeces i levels betwee flyways, various groups of States, ad frequetly betwee idividual States. I some istaces adjacet States, udoubtedly frequeted by may of the same ducks, showed clear differeces i residue levels, suggestig rapid assimilatio of pesticides ito the wig, probably through the diet. he precisio with which moitorig will detect treds i wig residue levels will vary from State to State depedig upo umbers of wigs sampled ad the variability i residue cocetratio withi a State's waterfowl habitat. Ackowledgmets Wig moitorig is a cooperative effort of the Divisio of Wildlife Research ad the Divisio of Wildlife Services. I am especially idebted to Dr. J. B. Elder of the latter Divisio ad to Messrs. J. M. Valetie ad L. O. Walker of the Divisio of Wildlife Refuges, who devised, sampled, ad packaged the wigpools ad maitaied pool idetity records. Wigs were provided by the Migratory Bird Populatios Statio: my thaks to Messrs. S. M. Carey ad M. G. Smart of that Statio for their cooperatio. Dr. E. H. Dustma, Dr. L. F. Stickel, ad Mr. W. H. Stickel participated i developig the moitorig protocol. Mrs. H. M. Nelso performed the may statistical computatios. See Appedix for chemical ames of compouods metiooed i this paper. LIERAURE CIED (1) Barry, H. C., J. G. Hudley, ad L. Y. Johso (Revised 1964, 1965, 1968.) Pesticide aalytical maual, Vol. I ad II, Food ad Drug Admi., U. S. Dep. Health, Educ., ad Welfare, Washigto, D.C (2) Cochra,W. G Samplig echiques. Joh Wiley & Sos, Ic., Lodo. 330 p. (3) Didal, Daiel L. ad. J. Peterle Wig ad body tissue relatioships of DD ad metabolite residues i mallard ad lesser scaup ducks. Bull. Eviro. Cotamiatio oxicol. 3(1):3748. (4) Heath, Robert G. ad Richart:' M. Prouty rial moitorig of pesticides i wigs of mallards ad black ducks. Bull. Eviro. Cotamiatio oxicol. 2(2): (5) Johso, R. E.,. C. CarvPr. ad E. H. Du<t... a. /967. Idicator species ear top of foo'! chai chose for assessmet of pesticide base levels i fish ad wildlifec1ams, oysters, ad sedimet i estuarie eviromet. Residues i fish, wildlife, ad estuaries. Pesticides Moit. J. 1(1):713. (6) Woodwell, George M., Charles F. Wurster, Jr., ad Peter A. Isaacso DD residues i a east coast estuary: A case of biological cocetratio of a persistet isecticide. Sciece. 156(3776): (7) U. S. Departmet of Agriculture Suggested guide for the use of isecticides to cotrol isects affectig crops, livestock, ad households. Agriculture Hadbook No ABLE I.Natiowide residue levels of DDE, DD, DDD, ad dieldri i pools of 25 wigs of mallards or black ducks: fall, 1965 ad 1966 REsmUES IN PPM (WE WEIGII) DDE DD DDD DIELDRIN NUMBER OF POOLS POOL MEANS 1 POOL MEANS I POOL MEANS/ POOL MEANS 1 2YEAR 2YEAR 2YEAR 2YEAR SAE AGE RANGE RANGE RANGE RANGE BLACK DUCKS, ALANIC FLYWAY Maioe o o " o 0.41 o Vt co o o o o 1.30 N.H o o 0.10 Mass o o o o o Coo o o o o 2.97 R. I O.OS o o o 0.23 N.Y U o o UO o o 0.17 Pa o o o O.sS ~.OS o o 0.13 N.J o o U Del o o o o o PESICIDES MONIORING JOURNAL

6 ABLE I.Natiowide residue lel'els of DDE, DD, DDD. alld dicldrill ill pools of 25 willgs of mallards or black ducks: fall, 1965 allll 1966Cotiued SAE AGE NUMBER OF POOLS RESIDUES IN PPM (WE WEIGH) DDE DD DDD DIELDRIN POOL MEANS I POOL MEA"S I POOL MEANS r POOL MEANS 1 2YEAR 2YEAR 2YEAR 2YEAR 1965 I ~66 I RAN,GE RANGE I RANGE RANGE BLACK DUCKS, ALANIC FL YW A Y Cotiued Md. Va. N.C. Ad, Imm, S. C , , O.O~ MALLARDS, ALANIC FLYWAY N.Y. Pa, N.J. Md. Va. S.C, Ga. ad Fla. Imm, , , , M~LLARDS, MISSISSIPPI FL YW A Y Mi. Wis. Mich. Iowa imm Id. Ohio Mo. Ky. Ark. e. La , S S , O.O~ 0.16 S I :; , , ;j S S S 6 0, VOL. 3, No.2, SEPEMBER

7 ABLE I.Natiowide residue levels of DDE, DD, DDD, ad dieldri i pools of 25 wigs of mallards or black ducks: fall, 1965 ad 1966Cotiued RESIDUES IN PPM (WE WEIGH) DDE DD DDD DIELDRIN NUMBER OF POOLS POOL MEANS 1 POOL MEANS 1 POOL MEANS 1 POOL MEANS 1 2YEAR 2YEAR 2YEAR 2YEAR SAE AGE 1!l !l RANGE RANGE RANGE RANGE MALLARDS, MISSISSIPPI FL YW A Y Cootiued Miss o o Ala o MALLARDS, CENRAL FL YW A Y Mot (easter) N.Dak S.Dak Wyo (easter) U.I0 0 0 Nebr Colo (easterr s Kas N.Mex (easter) Okla ex > ~ MALLARDS, PACIFIC FLYWAY Wash. Art Oreg Idaho ~ Moot (wester) Wyo (wester) o Calif Nev Utah : o Colo (wester) Ariz. aod N.Mex (wester) NOE: Meaos were computed by assigmg the trace value 0.02 pp.m to pool residues below the limit of sesitivity (0.05 ppm). = Residues reported, but mea level probably a trace (below 0.05 ppm). = Residues ot detectable at 0.05 ppm limit of seositivity. 120 PESICIDES MONIORING JOURNAL

8 ABLE 2.Natiollwide residue levels of DDE. DD, DDD, ad dieldri ill willgs of mallards or black ducks: [Estimates are 2year meas ad stadard errors for pools of 25 wigs each] RESIDUES IN PPM (WE WEIGH) DDE DD DDD DIELDIIIN SAE AGE I SANDARD 2YEAR I SANDARD 2YEAR I SANDARD OAL POOLS 2YEAR MEAN ERROR MEAN ERROR MEAN ERROR BLACK DUCKS, ALANIC FLYWAY 2YEAR MEAN I SANDARD ERROIl Maie (0.04).015 1(0.02) 1(.006) (0.02) (.006) Vt (0.04) (.018) (0.03).017 (0.02) (.008) N.H (0.02) (.008) (0.04) (.017) Mass Co R. I N.Y Pa (0.03) (.016) (0.04) (.021) N.J (0.03) (.010) (0.03) (.012) Del (0.02) (.008) Md (0.02) (.008) (0.03) (.010) Va (0.03) (.012) (0.03 ) (.015) 0.11, N.C (0.02) (.017) S.C (0.02) (.013 ) (0.04) (.022) (0.03) (.017) MALLARDS, ALANIC FLYWAY N.Y Pa N.J Md Va (0.04) (.016) (0.04) (.026) s. C. Ga. ad Fla (0.02) (.008 ) (0.02) (.008) (0.02) (.010) VOL. 3, No.2, SEPEMBER

9 ABLE 2.Natiowide residue le\"els of DDE, DD, DDD, ad dieldri i wigs of mallards or black ducks: Cotiued [Estimates are 2year meas ad stadard errors for pools of 25 wigs each 1 RESIDUES IN PPM (WE WEIGH) DOE DD DOD DIELDRIN SAE AGE I SANDARD 2YEAR I SANDARD 2YEAR I SANDARD OAL POOLS 2YEAR MEAN ERROR MEAN ERROR MEAN ERROR MALLARDS, MISSISSIPPI FL YW A Y 2YEAR MEAN SANDARD ERROR Mi. Wis. Mich. Iowa III. Id. Ohio Mo. Ky. Ark. e. La. Miss. Ala (0.03) (.053 ) (0.02) (.004) (0.03) (.011 ) 10 (0.04) (0.04) (.014) MALLARDS, CENRAL FL YW A Y Mot. (easter) N.Dak. S.Dk. Wyo. (easter) Nebr. Colo. (easter) Kas. N.Mex. (easter) Okla. ex l' (0.03) (.003) (0.04) (.009) PESICIDES MONIORING JOURNAL

10 ABLE 2.Natiollwide residue it'l"els of DDE. DD, DDD. alld dieldri ill wigs of mallards or black ducks: Cotiued [Estimates are 2year meas ad stadard errors for pools of 25 wigs each 1 RESIDUES IN PPM (WE WEIGH) DDE DD DDD DIELDRIN SAE AGE OAL POOLS 2YEAR 1% MEAN ERROR MEAN ERROR MEAN ERROR I SANDARD 2YEAR I SANDARD 2YEAR I SANDARD MALLARDS, PACIFIC FLYWAY 2YEAR MEAN I SANDARD EoR Wash. Oreg. Idaho Mot. (wester) Wyo. (wester) Calif. Nev. Utah Colo. (wester) Q (0.03) (.009) (0.02) (.010) (0.02) (.008) (0.03) (.020) (0.04) (.015) (0.02) (.008) Ariz. ad N.Mex Parethesized trace values were estimated umerically to compute average flyway levels; correspodig stadard errors are maximized estimates. NOE: Meas were computed by assigig the trace value 0.02 ppm to pool residues below the limit of sesitivity (0.05 ppm). = Residues reported but mea level probably a trace (below 0.05 ppm). =: Residues ot detectable at 0.05 ppm limit of sesitivity. ABLE 3.Residues of DDE, DD. DDD, ad dieldri, by waterfowl flyways, i pools of 25 wigs of mallards or black ducks: [Estimates are 2year meas ad stadard errors weighted by each State's total bag of the give species ad age group.] RESIDUES IN PPM (WE WEIGII) DDE DD DDD DIELDRIN NUMBER OF 2YEAR SANDARD 2YEAR SANDARD 2YEAR SANDARD 2YEAR SANDARD SPECIES FLYWAY AGE POOLS MEAN ERROR MEAN ERROR MEAN ERROR MEAN ERROR Blackduck Atlatic Mallard Atlatic Mallard Mississippi Oll Oll Mallard Cetral ll Maard Pacific ll O.ll NOE: Meas were computed by assigig the trace value 0.02 ppm to pool residues below the limit of sesitivity (0.05 ppm). =: Residues reported, but mea level probably a trace (below 0.05 ppm). VOL. 3, No.2, SEPEMBER