Document Evd5QmOvG7Lr2OMgKRGr5rJnR
Insecticides, Polychlorinated Biphenyls and Mereury In Wild Cormorants, Pelicans, their Eggs, Food and Environment1
bjr Yvonne A. Gbeicnue, A. Citicwt*. tod R. J. Emcbjck Ciftrimmt SliriM Biocftmiitty and Enlemdogy-ZooUty Ptpmrtm
South PAOta &( ViUvoruiy, Brookings S. D. $790o
The blologloal concentration of orgaaochlorlne Insecticides
is the food shale of flth and fifth-eating birds Sob been frequently roportod (NICXXT tt U., 1966j BASSOS U f., 19T0| ORSICKUS tf ., 19691 VOODVXLL U of., 1967| COLS U of., 196?). Both or|>-
chlorlne insecticides and polychlorinated biphenyls (TCl't) are torad &b the ft of birds sad oro difficult to eliminate from tbs
body (LUO U af,, 19701 SAXLORBt U ., 1971). Therefore, It could bo expected tbot PCS'a -would also bo concentrated In tho food
obnln of carnivorous birds.
Thoro la llttlo data avallablo rslating lovola of aoreury with its McvaalkUwi la animals la tho top of tho food chain. FlMtBXTS It at., (1971) bars roportod a positive correlation between aoreury concentration la blrda and tbo preparation of animal food In the *
diet. Predominately flab-eating birdn bad aoreury levels approx* lmately 10-fold greater thaa lovola la fleh.
The pmrpoto of this study van tot (1) exsainn the levels of
orgaaeohlorlBo Insecticides, PCS'* tad mercury la water, bottom
sediments, fish aad birds la tho Lake Poinsett, South Dakota
ecosystem, (2) determine whether or act biological concentratloa
oat occurring aad, (3) import tba distribution of these compounds
la various tissues,
..
Methods aad Materials
Itmxale Collection
Staples of water aad bottom sediments were collected from six
ltos oa Lake Poinsett aad Dry Lake, South Dakota, ftrenty fish from eaeb of four epeeiee including carp (Cgptfmtf caAplo), crapple {femiU anmifss.il), black bullhead (IdfdfuAui mcfju), and blgmouth buffalo (letiofcu cgptfitcffitt) were collected from diverse areas of
tho lake. Only fleh under 30 am were Included since larger fish are not nnmmnnly used ee food by pelicans end cormorants. These
^Approved for publication by the Director of the South Dakota Agricultural Experiment Station as paper So. 1120 of the Journal series. Supported la part by latiooal Science Foundation Orent Re. CD*19121.
Mbit, tt Kv.lra.aMt* Cl.tfli lib, ft V*. ft. lb.. O l*n b ftnb, i.Vabj Mm Tok te. (
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flak eonatltuto Ut ujor portion of tha diet of theae bird. In ull
w* (ndUSMM, 19511 pereonnl observation), The double-created corasraat (PkdfddAdMtot awUtui), vhlta pal loan (Pcftenmu vuithte-
*8*ahed) aid their an> vara eellaetad frea rookarlaa on Dry Lake
ad South Vaubay Laka, South Dakota, All aaaplaa vara placed la
tlaat eootelnera vbleh had baaa thoroughly alaanad and haatad la an
ovum at 5*0 C.
.
UMti49 srt rg
------------------------
Inter aaaplaa vara r11 tarad aad analytad ualnc tha proaadura
f M1DSMAC1 gf ili, (lf6h), lottea aadlaaati vara air drlad aad 100 ( aaaplaa vara extrutad vlth bexane/propexol-2 (Shall Davalap. aaat Coapaay, 19<I). Uto tha lataatlaal Sraat vaa ruaovad, tao
flab ef tha aaaa apaolaa vara rlnely greuad togathar aad a 15 s
hlluat vaa entreated vtah ethyl-petrolevn athar la a forrall kovodaelavr. Jka athar sstraat from tha flak aad aaa | aaaplaa of brmla, llvar, fat aad kldaay and flva s aaaplaa af auaola, body
aad ags* af blrda vara extracted and purlflad by tha Plorlell coltan aathod (ST1MP tf af,, 196h| OMIChUS ef af., 1968), Tha body
aaaplaa conalatad ef tka flaaly around body vhleh ravalaad after
tha raaovel ef tha abort aaaplaa tad Included the head) faat, faathara and aapty lntaatlaal tract. Its* vara hevocedited vlthoat tha akalla.
She PCS'a vara aaparatad free the lneectleldea by thin-layer ehreoatography after tha aaaplaa vara aaponlflad vlth alcoholic KOI (U.S, Pood and Drop Adnlnlatratlon, 1971) and oxldltad vltb
CrOj (NULSSM df af,, 1971). Tha aaaplaa vara apotted on 0,25 aa allfaa gal platan and tha hexane aolrant vaa advanced 1} ca rroo tha apettlag lisa. Thla proaadura aaparatad PCS'a frca Boat organoahlorlaa inaactlcldaa but not frea aldrln, p.p'-DDL or p,p'-DOT.
Aldrla data net ccaaonly occur In anlanl tlaauaa and In otkar aar.plaa It" vpa datarvlaad by ualnp aultlpla coluana on tha paa ohrooatopreph. Tha larala of p,p'-DDI In noat bird tlaauaa vara auch that vhen the aaapla vaa diluted auffleleatly to produce a peak eiallar to that of tha DCS ataadard, tha PCS peak* could no longer ha aaan on tha ehroaatograa. PCS'a Interfere vlth p,p'-DDT on noat paa chrcaatograpby aoliaaaa, ao DDT vaa converted to p.p'-DDL by aaponlfleatloo and tha daeraaaa In tha alaa of tha interfering PCS peak vaa aaaaumd. Oxidation oonvartnd p,p'-DDS to h,b'*dlehlorobenaophonooe vhlah vaa oaaily aaparatad froa PCS'a hy thln-loyar ahronatopraphy.
Tha inatrunanto uaad for paa ehroatttoprephy analyala lnoludad
tvo Vartan Aerograph SY-PI aodala 600D equipped vlth nodal 8-1 1 av organ! rveordara ud an electron capture dteter cell vltb either 4 t^OHilUlettrlt trltlw or- 4 3-iUUerl 11*3 aourea. Injector and aelrm tMp*ntwi vara 210 and 160 C, raapaetlvalyp and tha totfotor imptraturaa vara 210 C for the trltlw and 260 C for tha >1*3 aourea. Throe 1/8-lneh outside dleaeter by 5 faat boroellleate
>1444 eeluuM vara used vltb packings eonaiatlac oft (a) 21 Qf-1
1114044 (fluore)g (b) 51 Oov 11 Silicone and (c) 111 nixturv of 15$ QF-1 nod 10> DC-200 Silicone. All packings vara on 60/100 ash
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7
ehroaoeorb V (H/P A,V, DMC8), Tb nitrogen carrier gee m operated vith a flow rate of bO al par alnute.
All solvents used lo this study were nanogrede (Malllnckrodt Cbealcal Works). Boas batches of Plorlsil (Fisher Scientific
Coapeny) and silica gal vara found to ba contaminated with PCB's so th7 were washed repeatedly vith hexane until no PCB's could
ba detactad In tha bexane rinse,- -
Mass epectroaetrlc analysis of PCB's ip coraorant and nellean aaaplas wee done by Flanigan lnstruaents Corporation, Sunnyvale, California eaployibg tbs coupling of gas chromatography with siass peotroaetry (BORBLL1, mi).
Average percent racovarlas, standard deviations and alnlaus : confidence levels of orgsnochlorlne insecticides and PCB's free fortified saaplas are given la Table 1.
TABU 1
Average Recoveries of Insecticides and Polychlorinated Biphenyls
Material
Organochlorlas
losactlcldss
f Recovery
Minima
S 6D
Confidence
Polychlorinated
Biphenyls
% Recovery Minimal
S SD
Confidence
n>*> VP*
Bottom sedlaentftl Fish Bird tliitt*.
85 < 9 71 S 10
T* * T 89 < 9
lii!-----------,,--^
0,0$ 0.1 1.0 *0 10
8* 5 88 * 11
99 * 7 95 * 9 69 t 10
0.5 5.0 90 100100
Mercury Analysis
The flaseless atonic absorption aetbod for nercury analysis (HATCB tt ad., 1965) was used on substantially all flab tissues, coreorent nusels tissues and lake-bottoa sedlaents. All the pelican tissues, tbs remaining oomoraat tissues, and pelican and coraorant eggs were analysed by the A.O.A.C. aetbod (1970). These saaples were stored frosen until analysed, Veter eaaplee preserved with 10 al concentrated nitric ncld per liter were analysed for aereuvy using tbs provisional P.V.Q.A. asthod (1970) ns follows a 100 al water staple was acidified with 9 al concentrated sulfuric acid and *.9 al oooeeotreted nitric acid. One al of a 5* (w/v) poteaelim pansaaganata solution vas added end allowed to stand for at leant 19 aln, 2 al of a $$ (w/v) potasslua persulfate solution was added
m
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&M ths oanplo m allovsd to stood for at least m additional 30 lii Tbs flaaelves otsnlc absorption procedure used to datanlM Mroury eoatant of tha oxidised saaplo vaa essentially that of HATCH and OTT (1966).
All tissue and bottoa aadlaaota analysed by fleualees steals
absorption vara subjected to prior exhaustive sold digestion (Personal Connuolcatloa, PDA, 19T0), Body tissue sanplas vslgbed fna 2 to T f (vot basis) and bottoa ssdlaent ssaplss vslphad 1 g (vat basis). A solution consisting of 25 al of i 3kt9 (v/v) mixture of ooaesntratod sulfuric acid, concentrated nitric add and vatsr and 1 al of H (w/v) sodltai nolybdats solution vas addod to tha staple la a 8b/b0 V 830 al round bottom flask. Ssroral boiling ships vsrs addod and tbs flask wi conntctsd to a boo m s 13 m 1.4. vatsr ooadsnssr modified to bold 6 an Kasohl* rings. Tbs aoadoaasr vaa paekad to a balgbt of 100 an vith Puchig rings
plus an additional 80 an vith * an glass bsada. Tbs dlgsstlon mixture vas rafluxsd for 1 br Tbs flask vaa allovas to cool, vatsr vas dlpeonasctsd fron ths eondonssr and 10 nl of a lil (/) alxtura of soaoaatratsd aitrls and psrablorla adds vas addsd through tha top of tbs eondsnasr. Tbs dlgsst vas bolltd 10 nln. bsyoad tbs tins that vblts fuui appssrsd In tbs flask, Aftar
bting allovod to cool | tbs condenser vas vashsd down with approx* Uataly 1$ al vatsr. Tha dlgsat vaa ogala ballad for 3 ala,
allovad ta pool, and tbs eondsnssr va-unshod dovn vith an edditteesi 10 al sf vstor. Aftar cooling to rooa tanpsrsturs ths
dlgsst vag trsssforrod to s 30 al voluaetrle flask snd asds to voluas. Mercury vas dstemlaed on s B$ nl aliquot.
Xa a coapsrlsos of tbs flsnslsss stoeie sbsorptlsa sad A.0.A.C. aatbods of aaslyols for 9 ssaplss of cornorsat llrtr, svqysgs aorcury vslaos vsrs b6 ppn (rsngs. 0.16 to lk.O ppn) far stools sbserptloe sad b.3 ppn (rsngs, 0.16 to 13*0 ppm) for tbo A.0.A.C, aotbed vith s oorrslstton oosfflclsnt of 0.9T1 a 0,016.
Hoeoaorlos of 69 to 1031 (swags, 99.08) vsrs obtslnsd relieving tbs addition of asreurls chlorlds to brsast snd liver snplot st levels equivalent to O.b ppn Rg in ths ssaplss. Vitb tbs sddltloa of asrourle ohlorido to lsko vstsrs st s lml equlv-
slant to 10 ppb Ig, recoveries of 96 to 1038 (average, 101,78) vora obtalaod.
- fsults snd PHousslon
, ."sf-
Tbo eoaceatratieo of orgsnosblorlno Insocticlda rsslduss in
bottca sodlasnto vss about T-foii grsstor than In tbs vstor vhsrsss
tbo oonesntrotlon of rsslduss la flab orsr botton ssdinsnts vas free lO* to 60fold (Tsbls 8), PCI's vsrs eonesntrstsd in fish an
arcrags of 12*fold orsr bottom ssdlasats. lbs levels of PCI'a la
both bottom godlaoato sad flab vsrs bighsr than those of Insect!oidss. Mercury rsslduss vsrs not dstactsd In vatsr, bottom
ssdlasats or flab sxespt ssrp vhleh also bad ths hlghsst lsrsls of
M .
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insecticides and KB residues. Concentrations of total mercury So lake trout ware round by BACH tt at*, (1971) to increase with the age of the fish and ranged from 0.19 to 0.66 n.
Bodies of adult cormorants had 250-fold greater levels of Insecticides than fish and .adult pelleaas vers 260 tines greater (Tables 2 and 6). KB's were concentrated in bodies of oormoraats 60-fold over fish but only 30-fold la pelicans. This could repre sent a difference la the amount of KB's In food at their wintering grounds* Levels of laseotloldes and KB's la nestling cormorants appeared to reflect tbs levels la local fish at both the fish sad young birds had more KB residues than Insecticides whereas the opposite was true with adult birds (Tablt 3).
TABL| t
Average Levels of Insecticides, Polychlorinated Blpbelylt and
Material Sampled
Ro* of Samples
Average Total Insecticides
w
Average
PCB's vm
Average Mercury
PI*
Water
c
0.00023
< a 0005
* 0.0003
Bottom aedlmants
c
0.0016*
0*00613
Pish*
Onrp
8 0*092 0*11 o.u
Crnppio
.8
0.01
* 0.03
M 0.03
Buffalo
8
0.038
0.06
* 0.03
8
0.031
___ SUil_-aPj.Q2,,
*Dry weight oasis.
*Sncb staple Is a composite of 10 fish (wet weight basis)
Insecticide and PCB levels la cormorant aggs appeared to
reflect body levels but la pelican ogge they did not* However,
because the number of pelican body temples was aaall, i.e. 3, It
le difficult to draw conclusions from the date* BXBBBKOUOH it of.,
(1966) reported average total anounte of DPT and Its metabolites la
California brown pelican eggs to be 33 ug end amount of PCI's te be
10k mg* Brandt's cormorant aggs had an average of 326 ug of total
1ST and 113 ug of PCB's* The ratio of BBT and Its metabolites to
PCB was 9il for pelioan and 3il for cormorant aggs, while la the
present study the ratio waa 2il far both cormorant end pelloen
eggs (Table
.
.
Presence of PCB's in bodies of pelicans* cormorants and
,
oormorant eggs was demonstrated by compering the mats spectra ef
10 PCI packs (Aroelor 125k) with peaks in the samples having the
earns relative gea chromatographic retention times* ,
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TAILS 3
Anrtfl Levels of Xostctleldss, Polychlorinated Biphenyls end
, Mercury 1b Cormorant end Pelican Tissues.
Material Barreled
Bo. of Awrcgc Total Average
Sennits In*ctleides
PCB'a
Average Mercury
Adult Cormorant
(ppn wet weight basisJ
toty Muscle
10 20.7 7
k.6 0.6b 2,3 0.78
Liver .
20
s.t
2.0 7.98
Kidney
6 ^1 --
1.91
**
5 10,1
3.7 0.29
Beetling Cormorant!
*oty
3
0.8k
0.39
0.06
Liver
3
0.39
0.60
0.20
Adult Pelican
Body
3 IS.3
2.3 0.29
Muscle
S 11,3
Um Utoar
.
3 8
<.
<. a
--tell------- -----------__ 2___ ______M_____
..
3.1 k.3
3.1 2.T
0.25 0.99
0.37 0.22
?Ubole egg minus shell. Vim Li vnki*
Mereury u highest la the 11m of eoraorante and pelicans.
PU8TH1B t1 ,, (1970) found aarcury higher la the liver of Mrdt
tthan la tba breast mmole, kidnap or carcass. Coneaatratlon factors
* of lit and ^feld over fish vara found In bodlas of eoraorante and
pelicans respectively. This any reflect grantor aereury eontaalna-
tloa la tba food of aoraoranta la tha wintering areas as the
concentration in nestling cornorante vas only 1.3-tlaes that of
flab* Cormorant eggs bad blgbar levels of Insecticides, PCB'a and
aarcury than pelican eggs.
.
Qrganoeblofina Insecticides and PCB'a vare acre concentrated
in tba fat of aonsoranta and palicana than In any other tlasuc with p,p'*DDS eeostltutlng tha greatest single contaminant (Tabic fc). Bodies, liver, fat nod aggs bad greater amounts of total insectlaldaa than FCB*a but brain tissue had acre FCB's. This van true la 20 of 23 brain samples.
Studies completed in tble letoratory on the effects of DDT, ODD and DPS on panned eomorents Indicated that 20 ug/g of ODD in
tha brain van diagnostic of approaching toxleeela (HAlffiOIT, 1972) As birds approached death* there occurred a depletion of lipid
tores in the body while the amount of brain lipids remained the erne* Body iMactlelde residue levels decreased vhlla brain realduee iseraasad* This vas also true of cormorants that vare stressed by a decrease la food (UAMBOK, 2972).
Adult censorante In tha present study avsragad 2,200 g in valght and had 2*00 ppn of GOD la thslr bodlss (Table M or i total of 2,200 ug* Stress conditions such as migration, reproduction or
Ob*?39 HONS
dlseasa My cause a derftftft In body lipid stores. It appear* that the accumulation of 20 ug of DDD per g of brain could possibly occur. Also, there are many typee of toxic chamiealt la theae bird* and the effect* of the combination of these chemicals la difficult to ascertain.
There vaa an unknown peak on the chromatoerams of cormorant brain which was later Identified by mss spectroaetry as possibly being a phthalate eater. This peak vat also observed in numerous cormorant tissue* but less frequently In pelican samplti. This type of ceapound was recently reported as a toxic envlronaental oootaalnant found la aquatic oeosysteas and may ba ooncentratad in food Ohalae (BOWER U *., 19T0t 8HEA, lpTlt Presa Ralesse, U.6. Bureau or Sport Fiahorl.s ad Vlldllf*, 1971).
TABLE k
Average levels of SndlTidual Xneeetleldes and Polyehlorlnntod
Blphsnarla la Cormorant and Pelican Tlaauea.
Hepta.
Tissue Bo, Eaoxlde Lindane Dleldrla DDE ODD DDT Total PCB tppu - vet weight basis)
Coronal Bodies 10 + 0,03 *0.05
0.09
9.12 1.00 0.51 10.6 1.6
Brain Liver Pat m*1
10 10 6
17
+ 0,03 +0,03
0.25 0.05
<0.05 *0.05
0.26
0,05
0.12 0.13 1.38 0.13
0.56 2.70 107.8k 10.36
0.09 o.u 2.U O.kT
0.06
0.31 2,it
0.67
0.9 3.6
Uk.O
11.7
1.3 2.0 22.1
5.9
Pelican
Bodies 3 *0.05 *0.05 0.12 11.56 0.53 0.05 12.3 2.3
Brain 3 *0.05 *0.05
Livar 3 *0.05 *0*05 fat . 3 1.33 0.25 fcn1 ? 0.05 0.05
AVhole agg minus shell.
0.10
0.2T 1.T8 oao
0.67
5.37 15k.50
2.07
0.05 0.56
7.32 0.16
0.05 0.60
2.91 0.05
1.1 6.0 166.1
?
1.3
4.5 31.k
reacae
Aiwljtiool M*tbod> -k3/6k, 15 n (196k) null knl, Co. .
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HONS 064740
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.
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'
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12S
MQNS 0 b's?'*1