Document 3QLe49r8JjqaeLJoMg1Nj35kD
InwcliriilcN Polychlorinated Biphenyl* and Mercury
in Wild Cormor.-mls, Pelican*, their Egg*,
Food anil F.iivironinenl1
by Y\ov> A. Cbmciii i. A. CtiMUii.w4 R. J. Emcssck
EMptrimrnt 5i**
*ai Jfeelcfy Dtpmtmfull
SluNlk tlalrM* Six# I'aii MNt), Bi*4w|i, & 0.17M
The bloloulcil eoaentrttlM of oriinocLloriM luwCfeHN
In tha food eloli or fish ood flsh-eetlng bird* boo boon frequently rporl*4 (KXCK3.Y U at., 1966; UAIROO U ., 19T0; CRZ1CKUS of *,, 1969; W03WHJ* ef a*.. 1967; COLE U e/., 1967). Beth
ehloriae lnoeetieldce ood polychlorinated bipfceapla (VCB'o) oro
iorod In tha fot of birds nod oro dlfflcolt to elftolaate froo tho body (1AKB U of.. 1970; DAM1CRE3 U of.. 19T1). Therefore, It oould bo espected tint K>* would oloo bo ooncontrotod la tbo food
chain of carnivorous birds.
Thors Is little dots available relntleg levels of mercury with Its oeeMmloUon la miImIi la Uvs top of the fOod ohola. flRItni of of.. (1971) hare reported a realties eorrelation between norcoiy concentration la birds and the oroporatloa of aalaal food la the * diet. Predominately flob-eatinc birds had mercury locals appras laately 10-fold greater than levels la fish.
The purpose of this study wee tot (1) exatlaa the levels of organoehlnrlee lneeetleldes. PCB's and oersnry la eater, bottoo eedlocets, fish and birds la the Labe Poinsett, Booth Dakota ecosystem. (2) dctcrelac whether er not biological ooneoatratloa eat occurring and. (3) report the distribution of those nnopwoods fa various tissues.
Methods and Materials
triple Collection
Ssoples of enter and bottora icllainti were collected freei els
sites on Lake f'olnsctt and Dry Inks. South Dakota. TVenty flah
fro* rach of four i^eiee including carp (CtfpaouU UMp/s), erapplc
irri'CMS
black bullhead (JcJa/nAtii ne&u). and blguouth
buffalo {Ictioku* cifpfUJtt.tZiU) were collected fren diverse areas of
the lake. Only rich under 30 as were included since larger flah
are not coDonly weed as food by pelicans and cormorants. These
*Arfrofd for publication by the Director of the South Dakota
Agricultural Lspcrlneat Station as paper Bo. 1120 of the jwrnsl aeries. Supported la part by Rational Science Foundation Omnt Bo. CB-191?!.
;
r i > '
**... .4 [...wi.11 --...mm 1 TMw.
V*. I, K*. *. o MSI
V.iU* Cm Turk he.
MONS 085690
fish constitute the major portion nf the diet of these MrH In thin
area (TKAU7VJ*. 19511 yoreowe I observation). the Imkls-cmtii eor-
aorsat
mtUiU), vMts pelican (Fr/ieffma mhAm*
xAtfneJtss) oim! their agge wrt eelleoted free rootarise no Ary Lnhe
Md Sooth Uaabey Lnhe, Sooth DtkeU* All saaplee were placed la
glees containers vhiah had Wen ilnrimMy elesaad md heated An no
ona at 580 C.
Insecticide wd fCB toslnia
Veter senrplce vsre filtered ud tMlyted osli% the procedure
of hRLlDUrBACM < n/., (196*). Fottam scdlsuta were nlr dried nod
100 | soa^leo vere extracted with hexeae/propeael-? (Shell Develop
ment CMpany, 1961). After the iatentlaal tract wee rtsertd, ten
fish of the sene species wore finely crewid tofether tad i 2> g
aliquot was astractedi with (thyl-yctaeleei ether la n Sorrell
geaiter. The ether extract from the fish and too $ Samples of
Praia, liver, fat and kidney and fire g enables af bmc1, My
aad ecya of birds were extracted eaA purified by the Flerisll toltas
method (STDfT tX ml,, 196*1 ORUChUS U. ml., 1968). The body
samples consisted of the finely gngii body whleh ronlatd after
the rewral of the above seaples and taoluded tho Md, feet,
feathers sod empty lntestlaal tract. 4vi
iMcnlnad *ith>
cat tho sheila.
The rci's wars separated froi the laseetleldes If tbln-loyer chromatography after the samples ware saponified with sicohollo
ton (U.S. rood and Drug Ahslnlstretloo. 1971) and axldlsad with
CrOj (W/lHDti if (., 1971). Tho scopies wore spotted on 0.25 an silica gel plates nod the hexene solvent wee advanced IS am from the spotting 11ns. This procedure separated PCI's fron east organa* ehlorlaa iaseetielden hat not fren aldrln, p,p*-MC or p,p*-BGY. Aldrln does not cnroaly occur In nnlnal tlosuen and In other ssmples It* was determined by using multiple colons on tbs gas chranntagraph.
The levels of p.p'-DOE in coot bird tlonuos vere such that whan the sample wan diluted sufficiently to produce a peak similar to that or the DDK standard, the FCb peats could no longer ho soon on tho chromatogram. PCI's interfere with p,p*-Dl/r on moot gas ebroatttogreply column, so DDT was converted to p,p*-DDK by saponifica tion and tho decrease in the alta af the Interfering PCI peak was measured. Oxidation converted p,p*-DDB to *,**-41chlorobennpbanone which was easily separated fren PCI'a by thin-layer chromatography.
The instruments used for gas chromatography analysis Included two Variao Aerograph HI-FI models 6000 equipped with model 6-R 1 mv Sargent recorders and an electron capture detector cell with either a PVO-Dlllicuric tritium or a 8-nllllcurle Ml3 source. Injector
and column temperatures were 210 and 100 C, respectively, sad the detector tei.pemtures vere 210 C for the trltlua and 200 C for the Pi"* source. Three 1/tt-lnch outside diameter by 5 feet borosillcate
glass columns were used with rachlng3 eoaelnting ofi (a) 7% 0F-1 Slllronc (rjuorp), (to) >S Dow ll Silicone and (c) 1:1 mixture of
155 QV-J and 10* HC-200 nilconc. All packings were on 00/100 mesh
M0NS 085691
hroMwrk V (If/P A.w. RCS), lit *Hra|ta ctrrltr im OptrtlN with flow ml* of bO ml ptr alsuit.
All aoltentfi used in tbit study er* mMrrtAt (Ktlllaekndt CkMletl Vorfca). Sn batches of PlartiU (Pltlwr Scientific Ctapwqr) and silica ptl wra found to bo tteUalutti with KB*i o they vtr* washed repeatedly with btunt until no Kb's could bo Iriteiti in the btsasa rlsao.
Mom uncclitattrlc analysts of KB's is conaorant and nellCan sooplcs was dons by Klnniaan Iastruosnts Corporation, Sunnyvale, Callforala esploytsc the coupling of fas chranategraphy with boos spectronetry (BOKIUI, 1911).
Average percent recoverlas, standard deviatiana and niaiaua aonf&donce levels of orpaaaehlorlne Insecticides and KB's free fortified stop!** arc slven in Table 1.
Average Recoveries of Isseeticldes sod Polychlorinated Biphaayls
Material
Organoehlorlno
Tnseetleidea
% Recovery
HIsIm
a SB
Confldaaea
Polychlorinated
Blrtwavls
% Rcooeory
Minlaua
am
Contldanea
Pk
Water
W* 9
0,0$
Botton eedlneats* T1 a 10
run
7 7
0,1 1,0
Bird tl.maa
89 * 9
JO
SB!--------- ---------------82_i--2--____is___________ Qry weight baal7
* * J 88 U
93 7 * 9 w
0.1 J.O 50 100
...ISP--..
Mercury Analysis
The flamleta static absorption ncthod for stresry saalyslo (HATCB tX of., 1906) was used oa substantially all flah tissues, eornorsftt ousele tissues and lake-bottea sedisents. All ths rellcan tissues, the retaining consoraot tissues, and pelican and cormorant fgi were analysed by the A.O.A.C. wethod (1V70). These atopies were stored froxen until analysed. Water save)as prettrved with 10 nl concentrated nitric acid per liter were analysed for --iciuj bsint the protlnian^l F.V.Q.A. nsthod (1910) as follows? a 100 al water staple wns acidified with 9 nl concentrated sulfuric acid and 2.5 stl concentrated nitric aeld. One nl of a 51 (*/) potsatins pemangaaate solution was added and allowed to stand for ot least 15 nln, 2 nl of a 5? (w/t) petasaiun persulfate aolutlon was added
MQN
and the Maplv VM Uom4 to stand for ftl X*Mt m additional 30 li, The flaaiXtM atomie kMrpllM procedure need to determine *rct7 coairat of tK oxidised tiipla m tiHaililli tlwt of MTCM u4 OR (19U).
All tluw an* but* H41KHI Hl]nrt br rlMlm ,toat
tlMorptlon wit MbJectH to prior tikooilv* eU lUtatim
(^r*n*) CuMHaleatioa, FDA, 1970). Mjr tlntr
weighed
froo 2 to 7 f (i Pool*) Mi botion dineat males wlubei 1 g
(vet banish A solution consisting of 25 ml of 0 5b9 (?/t)
mixture of concentrated cuifurlc ocitf, metatmti nitric odd
aci outer Mi 1 ml of 2% (v/v) oil molybdate solution added to the sample to u tk/ko V 250 ml room# batten flask, gctaral
toiling chips vorc liitd end the flul u eamtetai to a bOO
am x 13 cm 1,1, water eltMr milflai to kali 6 mo ftasehl* rlaga,
lit condenser was packed to e freight of 100 m with Itnachig rings
plus an additional 20 on with k am gloss hoods. The digestion
mixture wee refluxed for 1 hr* The flush ai allowed to cool,
voter woo disconnected from the condenser sod 10 nl of s ltl (e/e)
mixture of eemcestrsted nitric end perehlorlc odds cat odded through the top of the condenser* The digest von hulled 10 mto.
beyond the time that white fumes sppesred in the flesh* After
being allowed to cool, vtm condenser vaa washed down with arcret-
imataly 15 ml wutor. The digest won a|sia boiled for 5 min,
allowed to cool, sod the coodeaser u unshed down with so addi
tional 10 ml of water. After cooling to room temperature the
digest was transferred to a 50 ml roliaaotrlc flask and had* to
mlkae. Hareurjr was determloed 01 a 25 d allgoot.
la a comparlaoo of the flameless atomic abaorptiom omd A*0*A*C. methods of analysis for 9 samples of cormorant liver,
average mercury values ware 1,0 ppm (range, 0,16 to U0 ppm) for
atoaaic absorptism sod 1,5 pfm (range, 0.16 to 15*0 pym) for tho
A.0.A.C, method with a correlation coefficient of O.pTl i 0,010*
Recoveries of 09 to 1051 (average, 99*05) were obtained
following the addition of oereurle chloride to breoat sod liver ssaplcs at levels equivalent to O.b ppm Ng In the eamplee. With the addition of oereurle chloride to lake voters at a level ecvlv* slant to SO ppb tig* recoveries of 9 to 1051 (average, 101,71) were obtained.
Itoaulti and Mscusslon
The concentration of organochlorlne insecticide residues is bottom sediments was about 7wfold greater than In the water whereas the concentration of residues in fish over bottom sediments was from 10- to bO-fold (Table 2). rcb*s were concentrated In fish an average of 12-fold over bottom ceUinesta, The level* of l*Cfr*s In
both bottom sediments and fish vere higher than those of insecti cides. Mercury residues vere not detected in voter, bottom
sediments or fish except carp which also had the highest levels of
4
HONS 035693
Insecticides ul PO mUWfl. OMccnirttlMi ef total nrevr 1a late inmt were found ly MCH it it., (1971) U lMNU< vitk tka ape af ite flik ate |a4 tna 0.19 to O.di p*a.
Mlti of adult ewwMti had tSO-foll gnattr lvla of imeUc!4et tltna flak M adult pelicans van 28D tires creator (Table* ? and 3). PCI's ware naMRtrnttd la kodlx or eorooraata (0foU over fik but aaljr 30-fold la pelicans. Hit erwld rtpre* ftit a difference la tte iroist of rci*a la food at their viatarlnc grounds. UmU of laecctlcideo wd PCB's la nestling eonouti appcartd to reflect the lavale la local flak a* both the flak ao4 jom| kirdi k*l aoro VCI mlkm thaa laaaotl*14ao vhereaa tka opooalta vaa true oitk oftolt MrM (Table 1),
---Altmc Levels of XaneetlclAos, MjallirlMtid Blpkelyla and
K.t.rl.1 --.1--
e. or ftwvloe
Average Total
W
Average
BOa
Average
pmWereury
Water Battov aodiaevte riok*
CCanr*p4.
Buffalo
< 0.00003 t 0.0U6X
e 00003 P.00661
< 0.000$ < 0.1
9 o.u0.090
0.11
tB2
0.016 0.030
< o0..0o9o
* 0.0$ *0.0*
__Sifiu_____eai___ . it!ta_
ttacb lUfl* la
ilto of 10 flak (vet uelvbt koala).
Insecticide and KB 1avals la corvoraat eggs appeared to rofleet body levels bat la poUese acre they 414 not. lowever kaeauae the maker of pelican body aaoplaa vaa avail, l.a. 3. It la difficult to 4raw eoaclualene free tka 4ata. MSEBPOUBtt it /.. (1900) reported average total nooeata of BB? aa4 lie oataboiltea la California lrt*vn **UM. s*a to be $3 us ad aoount of KB'e to ko 10.k us Brandt*8 eemrut esse had as averase of 326 us of total BUT aad 1J3 us of PCB's, The ratio ef EOT and Ita aetabolltee to KB woo 5*1 for pelican aad 3il for corvoraat eggs, wklla la tka present study tka ratio vaa 2*1 for both cevnrant and pelican eyre (Table k).
Presence ef KB*a la bodies of pelicans, coraoraata oad servo* eat eggs vaa dcraastreted by ccantering the eaea apeetra of 10 KB peaka (Areclor 125k) vlth pooka la the samples having the nave relative gas chromatesrupklc rvtaatloa tlvoe.
M0NS 005694
TAMS 1
AmK Levels of lucetleHN, Polychlorinated Biphenyls m
bO. Cf ATT* :i 'iT: .1 Avc:,..s
Average
f-.al--
i ret***
tfrreenr
(FP> - w*t
u.i.r
Adult Coraorcat
BoAr
10 10.7
4.0 0.04
IVecle
Liver Kidney
Eras*
T c.i
2.3 0.71
10 t
.*
_1
2.0
T.M l.M
3 10.1
9.7 0.29
Bsstllag Goraoraatl
Body
9
0.24
0.39
o.ot
Liver
>
o.
0.(0
0.28
Adult Pelican
Nnsele
Liver
i U.) 3 11.3 i t.s 2 (.8
i.) 0.29 3.1 0.23
k.5 #. 3.1 0.3T
_______________________i_________ill___________
*Bet analysed.
_________o.
SVlwli egg iImb riwU.
3a*s fU Hki.
Mrnqr blfhMt la the liver af cormorants al pelicans. BUCTMAB AC t, (1970) foaaA aertwy higher la tla Hear of blrii than la Ua breast Midi, bidasgr or eareaas. Caaseatrstlan factors af it* aa4 6*raid over flih vara feaad la bodlos of eoraaraata aai pelicans respectively. this aagr rsfleet |mur wrivy r^milns tloa la lit food of somersets la tb islrtia areas as tbs concentration in oastllng eoraaraata vae only 1,1*tines tint of
flab, Cormorant sgf bad higher levels of Insecticides, Kl'a and mercury than pellcaa sms.
nrfsaoeblorlns lasectlcltfea and PCS'a vara nora concentrated
la the fat of cornoraata and pelleama than la any other tissue with p,p*-PDE constituting the greatest single contaminant (Tabls 4). Bodies, liver, fat and eggs bad greater snouats nf total Insecti cides than FCb'a but hrala tlasaa bad nare PCB'a. This vaa true In 10 of 13 brain staples.
Studies completed In this laboratory on the effects of SOT, BOD and DDK on pruned eorrorantn Indicated that 20 ujr/g of OBO In the brain vas dlarnostlc of approschlnr toxicosis (KACbON, 1972). As birds approached tfastb, thcic occurred a deflation of lipid stores In the body while the errouat of brain ltplda renslned the sane. Body ftaacctlclde rcslaue levels decreased while brain residues increased. Ibis wit3 also true of cornoraats that were stressed by a dccrcsis la food (hAACOK. 1972).
Adult eornoiants la the present study averaged 9,200 g in weight and bad 1.00 pfo of B00 In their bodies (Table 4) nr a total of 2,200 ug. Stress conditions such aa nlgratloa, ripeninslion sr
Ilitua My cause a Acertua In body Hrid stores. It appears that the accumulation of 20 u* af CCO rr r of brain could poeelMjr occur. Also* there ere tafijr tjryM of totic ctcaicol* In these bird* end the effect* of the cenb&entioa of these ebcaicnls to Oiffteult to ascertela.
There ves an unknown peak on the chrenatocraoi of cormorant brain which vr.s later Identified by r.-.u aractresttry as foeslMr beiad a pbtbhti ester. This pesc vas also observed In nunerous conarut tissues but less frequently In rellcea eeaples. This type of cospotrl v;it recently reported as a toxic cnvlrorsientol cootnrlnant found In aquotlc ecosystems end wy be coaeentreted In food ebeios (KWEff et /. 1970( Shin, 19711 Press Beleese, U.S. baareeu of 6port fisheries and Wildlife, 1971).
Avarats Levels of Individual Insecticides and Pelychlorlnetsd
Tissue
Montane in con
-- TMS!b-
Keptn.
Re. Leoxldo Lindens
ODE m 0DT
(ppa - vet weight basis)
_E*
Cormorant
Bodies 10 <0.03 e0.0$
Brain 10 *0.0$ .0.09
Liver 10 *0.0$ *0.0$
Pat
a 0.29
0.(6
17 0.0$ 0.0$
Psllcaa
Bodies 3 *0.0$ *0.0$
Brain 3 *0.0$ *0.0$
Liver 3 *0.0$ *0.0$
Pet
3 1.13 0.29
ffttL 0.09 D.0*>
am alnus shell
0.0$ 0.12 .11 1.18 0.13
9.12 0.96 2.70 107.8b 10.38
1.00 0.89 0 .11
t.u 0.17
0.$1
o.oe o.n
2.16
0.67
10.8
0.9 3.0 Ub.O 11.7
1.6 1.3 2.0 22.1 9.9
0.12 0.10
0.27 1.70 0.10
11.96 0.87
9.17 19b.90
2.07
8.91 0.0$ 0.0$ 0.0$ 0.96 0.60 T.V t.91
. o.pt
12.3 1.1 0.6
168.1
2.3 1.3 b,9 31.1 1.2
Heftrecces
Analytical *atbo4* we~b3/6b, 19 rr (19b) 8k.11 Daaal. Ca.
MCU.C.A., V.H. CUTWKARi, and 0.2. UB, 8cIn*. 172. 991 (1971).
808ELLI, E.J., Mr. Lab., fab. Isaua (1971).
OH), 8.1.. 8. HAHER'A., >M T.D. K1KT08, 2. Unura. Rnptl. Tbarap. 171, Jib (1970).
meibhimcr ,a.w,, j.j. uamnm, o.r. urn. j.j. smith, j.w. QCIUIUHU, Jr., an. 8. STUMl, Ra*. Ed. U.8. bant. Haa 1th. Education and Walfar*, Fublla 8**1lb Bar*. 9ubl. I2bl, <3 (1971).
COU., I., 9. MHIIY. nd D.E.R. EltEAB, Bull, tnalna. CottM. and
iniiMi. r, is? (19C7).
m
WNLCMS, B.B., 7.A. ntlcm, an* 9.1. UK>UI, J. Midi. Ks*l. ii, 6Z1 (1*71).
bustkab,
L.r. ancm, and j.a. nan, hunati. iw. an
knliu, Ksrcury Canine., Ann Arbor, Mcklm (1919).
riwmr, v.t. aouvewn. j.a. man. *.a. ruicc, and i.n.
CTOChr, Canadian Nald Natural<>l gj, 211 (19T1).
cnncHus, t.a.. m.*. k/kioh, a.c. m, and b.i. appuoati, m.
.D. Acad. let. *8, 157 (1969).
0M3CMJB, T.A.. D. un, and C. unm, Analyst j)J, Ml (1*M).
unoa,
ni.B. MaaartMlon, S.D. Rials Bala. 53 yp. (1973).
MAIMOU, M.M., T.A. OWCMIR, R.L. AfniCATX, and A.C. m, Trana. Anar. 71ak. Baa. 2J, k9< (1970).
HCB, V.B. and V.L. OTT, Anal. Cto. *, BOB* (1*CA).
wscm, j.j., a. nm, m r.n. mm, j. Ami. Csai. *, in (1966).
IAMB. S.V.. T.A. BRBCaUE, and 9.1. UXEBM. Aar. tod Own. 18,
lit (1970).
MILBBOI. B.N.. B. CMBim, K.t. MQCBKL, and A .A. BUIU, J. Assoc. Ottla. Anal. Ckaa. , 5K (1971).
Official Matbada of Analysis (utk ad), (1970), Aaaaa. Offla. Ar. dm* v VMblB|tw, P.C.
CamnUfttlM,
Quillti Clrl UtifiUij,
Fadtril Vtr Quality AUnlalatratlan, Cincinnati, Ohio (1970).
Feotleldi Analytical Kanual Val. I, Beetle* 211.1)4 (1971), 0.8. foot and Ont| Adniaiatratloe.
fmi RtlNM, U.8. Bureau of Sport Pickeries and wildlife, Columbia, Nlaeourl, June 29, 1971.
RJ8E8MUBB, R.V.v D.B. PEAKALL, 8.C. MIWIAI, and N.l. KJKfEB, Batura 220, 1096 (i960).
8KKA, K.P., Enalroa. J, 2 (1971).
STWr, A.R*, B.Ja UCLA, B.E. LAKOL018, and W.J. STAHUIAB, Poultry Sc1. ii, 273 (196b).
TRAUlMAJt, C.O., 9.0. Conacre. Discat 1ft, 3 (19)1).
W0QWUX, G.M., C.K. WWTU, Jr., and FJk. XBAACBQ8, Belcnea 156,
921 (1967).
"
MONS 085697