Evaluation of toxicity and sex-related variation of PCB levels in Mediterranean striped dolphins...

11
Pe911111~11 Chem05phere, V01. 32, N0. 12, pp. 2359-2369, 1996 C0pyr19ht 0 1996 E15ev1¢r 5c1mac¢Ltd Pr1nted 1n Cre5t 8r1ta1n. A11r~h~ m~rved PH: 50045-6535(96)00143.9 0045-6535/96 $15.00+0.00 EVALUA710N 0F 70X1C17Y AND 5EX-RELA7ED VAR1A710N 0F PC8 LEVEL51N MED17ERRANEAN 57R1PED D0LPH1N5 AFFEC7ED 8Y AN EP120071C ~ * , A9u11ar, A.*, C0r5011n1 5.** and F0card1 5.** *Department 0f An1ma1 810109y (Verte6rate5), Facu1ty0f 810109Y,Un1ver51ty 0f 8arce10na, 08071 8arce10na, 5pa1n. **Department 0f Env1r0nmenta1810109y,Un1ver51ty 0f 51ena, v. de11e Cerch1a 3, 53100 - 51ena, 1ta1y (Rece1ved 1n 6er•many 5 0ct06er 1995; accepted 12 Match 1996) 5UMMARY 1nd1v1dua1PC8 c0n9ener c0ncentrat10n5, 1nc1ud1n9n0n-0rth0 ch10r0 5u65t1tuted, were determ1ned 1n 30 5tr1ped d01ph1n5 (5tene11a c0eru1e0a16a) affected 6y the 1990-92 Med1terranean ep1200t1c t0 1nve5t19ate the1r t0x1c p0tent1a1. PC8 c0n9ener c0ncentrat10n5 1n the5e d01ph1n5 were am0n9 the h19he5t ever f0und 1n c0mpara61e 5tud1e5 0n mar1ne mamma15. C0ncentrat10n5 1n ma1e5 and fema1e5 were 519n1f1cant1y d1fferent 6ecau5e 0f p011utant tran5fer t0 0ff5pr1n9 6y fema1e5. 7hu5, PC8 c0ncentrat10n5 and 2,3,7,8- tetrach10r0d16en20-p-d10x1n (7CDD) t0x1c e4u1va1ent5(7EQ) 1n ma1e5 were appr0x1mate1y d0u61e th05e 1n fema1e5. N0n-0rth0, m0n0-0rth0 and d1-0rth0 c0p1anar c0n9ener5 acc0unted f0r appr0x1mate1y0ne th1rd 0f the 0vera11 t0x1c1tya55e55ed thr0u9h t0x1c e4u1va1ent fact0r5 (7EF5), a5 def1ned 6y Ah160r9 et a1. (1994). D1- 0rth0 c0n9ener 170 and n0n- 0rth0 c0n9ener 126 were the maj0r c0ntr16ut0r5 t0 7EQ (33% and 30% re5pect1ve1y). C0pyr19ht • 1996 E15ev1er 5c1ence Ltd 1N7R0DUC710N P01ych10r1nated 61pheny15(PC8), a fam11y 0f 209 c0n9ener5 that c0n5t1tute a 9r0up 0f 1mp0rtant 1ndu5tr1a1 chem1Ca15u5ed a5 n0n-f1amma61e0115 1nmany c0mmerc1a1 pr0duct5, are extreme1y per515tent and d1ff1cu1t t0 de9rade. 7he 11p0ph111c nature and per515tence 0f PC85 c0ntr16ute t0 the1r h19h 610accumu1at10n p0tent1a1 and capac1ty t0 610ma9n1fy a10n9 the tr0ph1c we6. 1nd1v1dua1 PC8 c0n9ener5 d1ffer 9reat1y 1n the1r t0x1c 2359

Transcript of Evaluation of toxicity and sex-related variation of PCB levels in Mediterranean striped dolphins...

Pe911111~11 Chem05phere, V01. 32, N0. 12, pp. 2359-2369, 1996

C0pyr19ht 0 1996 E15ev1¢r 5c1mac¢ Ltd Pr1nted 1n Cre5t 8r1ta1n. A11 r~h~ m~rved

PH: 50045-6535(96)00143.9 0045-6535/96 $15.00+0.00

EVALUA710N 0F 70X1C17Y AND 5EX-RELA7ED VAR1A710N 0F PC8 LEVEL51N MED17ERRANEAN

57R1PED D0LPH1N5 AFFEC7ED 8Y AN EP120071C

~ * , A9u11ar, A.*, C0r5011n1 5.** and F0card1 5.**

*Department 0f An1ma1 810109y (Verte6rate5), Facu1ty 0f 810109Y, Un1ver51ty 0f 8arce10na, 08071 8arce10na,

5pa1n.

**Department 0f Env1r0nmenta1 810109y, Un1ver51ty 0f 51ena, v. de11e Cerch1a 3, 53100 - 51ena, 1ta1y

(Rece1ved 1n 6er•many 5 0ct06er 1995; accepted 12 Match 1996)

5UMMARY

1nd1v1dua1 PC8 c0n9ener c0ncentrat10n5, 1nc1ud1n9 n0n-0rth0 ch10r0 5u65t1tuted, were determ1ned 1n 30

5tr1ped d01ph1n5 (5tene11a c0eru1e0a16a) affected 6y the 1990-92 Med1terranean ep1200t1c t0 1nve5t19ate the1r

t0x1c p0tent1a1. PC8 c0n9ener c0ncentrat10n5 1n the5e d01ph1n5 were am0n9 the h19he5t ever f0und 1n

c0mpara61e 5tud1e5 0n mar1ne mamma15. C0ncentrat10n5 1n ma1e5 and fema1e5 were 519n1f1cant1y d1fferent

6ecau5e 0f p011utant tran5fer t0 0ff5pr1n9 6y fema1e5. 7hu5, PC8 c0ncentrat10n5 and 2,3,7,8-

tetrach10r0d16en20-p-d10x1n (7CDD) t0x1c e4u1va1ent5 (7EQ) 1n ma1e5 were appr0x1mate1y d0u61e th05e 1n

fema1e5. N0n-0rth0, m0n0-0rth0 and d1-0rth0 c0p1anar c0n9ener5 acc0unted f0r appr0x1mate1y 0ne th1rd 0f

the 0vera11 t0x1c1ty a55e55ed thr0u9h t0x1c e4u1va1ent fact0r5 (7EF5), a5 def1ned 6y Ah160r9 et a1. (1994). D1-

0rth0 c0n9ener 170 and n0n- 0rth0 c0n9ener 126 were the maj0r c0ntr16ut0r5 t0 7EQ (33% and 30%

re5pect1ve1y). C0pyr19ht • 1996 E15ev1er 5c1ence Ltd

1N7R0DUC710N

P01ych10r1nated 61pheny15 (PC8), a fam11y 0f 209 c0n9ener5 that c0n5t1tute a 9r0up 0f 1mp0rtant 1ndu5tr1a1

chem1Ca15 u5ed a5 n0n-f1amma61e 0115 1n many c0mmerc1a1 pr0duct5, are extreme1y per515tent and d1ff1cu1t t0

de9rade. 7he 11p0ph111c nature and per515tence 0f PC85 c0ntr16ute t0 the1r h19h 610accumu1at10n p0tent1a1

and capac1ty t0 610ma9n1fy a10n9 the tr0ph1c we6. 1nd1v1dua1 PC8 c0n9ener5 d1ffer 9reat1y 1n the1r t0x1c

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p0tency. N0n-0rth0 ch10r1nated PC8 c0n9ener5, and m0n0-0rth0 and d1-0rth0 c0n9ener5 (t0 a 1e55er extent)

have 51m11ar pr0pert1e5 t0 7CDD and are the m05t t0x1c 0f th15 type 0f ha109enated ar0mat1c5.

Prev10u5 5tud1e5 1n mamma15 have 5h0wn that the5e c0mp0und5 cau5e we19ht 1055, repr0duct1ve

1mpa1rment, thymu5 atr0phy, 1mmune d150rder5, terat09ene515 and Ah recept0r 61nd1n9 (5afe, 1990). 8a5ed

0n the5e re5u1t5, 1n the 1a5t year5 a num6er 0f t0x1c e4u1va1ent fact0r5 (7EF5)-5cheme5 have 6een

deve10ped f0r d10x1n-11ke PC85 (5afe, 1990; Ah160r9 et a1. 1992). 7he 7EF 15 a mea5ure 0f the re1at1ve

t0x1c1ty 0f d1fferent c0mp0und5 w1th re5pect t0 2,3,7,8-7CDD, the m05t p0tent mem6er 0f th15 fam11y 0f

chem1ca15. Rec09n151n9 the nece551ty f0r a m0re c0n515tent appr0ach t0ward5 5ett1n9 1nternat10na11y a9reed

7EF5, 7he W0r1d Hea1th 0r9an15at10n-Eur0pean Centre f0r Env1r0nment and Hea1th (WH0-ECEH) and the

1ntemat10na1 Pr09ramme 0n Chem1ca1 5afety (1PC5) rec0mmended a 5et 0f 7EF5 (Ah160r9 et a1., 1994). D1-

0rth0 138 and 153 5u65t1tuted c0n9ener5 were n0t 1nc1uded 1n th15 1a5t 5cheme 6ecau5e 0f the1r weaker

act1v1ty a5 Ah-recept0r a901n5t5 and the1r 1ack 0f 6101091ca1 519n1f1cance 1n the c0ntext 0f 7EF5 f0r d10x1n-11ke

chem1ca15.

A1th0u9h the h19h t0x1c1ty 0f c0p1anar PC8 c0n9ener5 ha5 6een c1ear1y dem0n5trated, 11tt1e 1nf0rmat10n 15

ava11a61e 0n the 10n9 term effect5 0f env1r0nmenta1 c0ntam1nat10n. C0p1anar PC8 c0n9ener5 0ccur 1n

techn1ca1 m1xture5 (Kannan et aL, 1987, H0n9 et a1., 1993) and theref0re d15per5e 1n the env1r0nment

t09ether w1th the 0ther PC85. H0wever, the c0mp051t10n 0f PC8 m1xture5 chan9e5 dramat1ca11y 1n the f00d

cha1n; 1n 9enera1 the h19h1y ch10r1nated c0n9ener5 tend t0 1ncrea5e the1r re1at1ve a6undance, wh11e th05e

10w1y ch10r1nated 6ec0me 5carce 0r d15appear fr0m 6101091ca1 c0mpartment5. 7he preferent1a1 meta60115m

and 5u65e4uent excret10n 0f 10wer ch10r1nated PC85 and the p00r a650rpt10n 0f h19her ch10r1nated PC85

pr06a61y acc0unt5 f0r the5e chan9e5. 7h15 pr0ce55 re5u1t5 1n an enr1chment 0f the m0n0- and d1-0rth0

5u65t1tuted PC85, env1r0nmenta1 PC8 m1xture5 wh1ch are t0x1c01091ca11y m0re act1ve than m05t 1ndu5tr1a1

PC85 (Park1n50n and 5afe, 1987). 7heref0re, the1r 610accumu1at10n 1n the f00d we65 and the c0n5e40ent

re51due5 1n the t155ue5 0f the 0r9an15m may have a 9reat 1mp0rtance 1n the t0x1c r15k a55e55ment 0f the

m05t harmfu1 c0ntam1nant5.

8ecau5e d01ph1n5 have a h19h meta6011c rate and feed at h19h tr0ph1c 1eve15, and the1r 60d1e5 c0nta1n a 1ar9e

pr0p0rt10n 0f fat (up t0 40%), they accrue 1ar9e 10ad5 0f 0r9an0ch10r1ne c0mp0und5 1n the1r 60dy (80rre11,

1993). M0re0ver, 7ana6e eta/. (1988) and N0r5tr0m et aL (1992) have 5h0wn that m05t 0d0nt0cete5 are

1ncapa61e 0f meta601151n9 certa1n PC8 c0n9ener5, f0r wh1ch rea50n the1r p0tent1a1 f0r accumu1at10n 15

5u65tant1a11y 1ar9er than that 0f 0ther mamma15. 7he5e tw0 fact0r5 c0m61ne t0 make d01ph1n5 part1cu1ar1y

5u5cept161e t0 the 1mpact 0f PC85.

1n the pre5ent 5tudy, the c0ncentrat10n 0f c0p1anar p01ych10r1nated 61pheny1 and 0ther PC8 c0n9ener5 wa5

determ1ned 1n the 61u66er 0f 30 5tr1ped d01ph1n5 k111ed 6y a m0r61111v1ru5 ep1200t1c that affected the 5pec1e5 1n

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the Med1terranean 5ea dur1n9 1990-92 (A9u11ar and Ra9e, 1993) t0 eva1uate t0x1c1ty and d1fference5

6etween 5exe5. 8ecau5e 0f the h19h 1eve15 0f PC85 detected 1n the t155ue5 0f the 5tr1ped d01ph1n5 exam1ned

and the 1mmun05uppre551ve capac1ty 0f the5e c0mp0und5, 1t wa5 5u99e5ted that PC85 may have tr199ered

the 1n1t1at10n and 5u65e4uent deve10pment 0f the ep1200t1c (A9u11ar and 80rre11, 1994).

MA7ER1AL AND ME7H0D5

81u66er fr0m the re910n p05ter10r t0 the d0r5a1 f1n wa5 exc15ed fr0m 30 5tr1ped d01ph1n5 (5tene/1a

c0eru1e0a/6a - 17 fema1e5 and 13 ma1e5), c011ected dur1n9 the m0r61111v1ru5 ep1200t1c 1n the Med1terranean

5ea. 5emp1e5 were wrapped 1n a1um1n1um f011, and kept 1n deep free2e (-20°C) unt11 ana1y515.

81u66er 5amp1e5 were 9r0und w1th anhydr0u5 50d1um 5u1phate 1n a m0rtar. 7he m1xture wa5 extracted w1th

n-hexane f0r 4 h0ur5 1n a 50xh1et apparatu5. 7he extract wa5 evap0rated and dr1ed t0 determ1ne t155ue fat

c0ntent 9rav1metr1ca11y.

PC85 were extracted and c1eaned up fr0m 61u66er 5amp1e5 6y the meth0d 0f a1ka11ne-a1c0h01 d19e5t10n

(Wak1m0t0 et a1., 1971). 5amp1e wa5 d19e5ted 1n a 1N K0H-ethan01 501ut10n f0r 1 h and the extract5 were

tran5ferred t0 hexane. 7he c0ncentrated hexane 1ayer wa5 c1eened 0n 1.5 9 0f 5111ca 9e1 (wak0 9e~ 5-f)

packed 1n a 91a55 c01umn (10 mm 1.d. x 20 cm 1en9th). 7he e1uate wa5 c0ncentrated t0 6 m11n a r0tarvap0r.

A 5 m1 a114u0t 0f th15 extract wa5 run 0n a 5 mm 1.d. c01umn packed w1th 125 m9 0f act1vated car60n t0

5eparate n0n-0rth0 c0p1anar PC8 c0n9ener5 fr0m 0ther PC8 150mer5. 7he 1n1t1a1 fract10n e1uted w1th 100 m1

0f 20% d1ch10r0methane 1n hexane c0nta1ned PC85 w1th 0rth0 ch10r1ne5, 0ther xen0610t1c5 and 6109en1c

5u65tance5. 7he 5ec0nd fract10n e1uted w1th 100 m1 0f 6en2ene/ethy1 acetate (50150) c0nta1n1n9 n0n-0rth0

ch10r1ne-5u65t1tuted c0p1anar PC85 wa5 m1cr0c0ncentrated wh11e re51due5 ware tran5ferred t0 5 m1 0f

hexane. 7h15 hexane extract wa5 5ucce551ve1y c1eaned w1th 5 m1 0f 100 fum1n9 5u1phur1c ac1d and r1n5ed 1n

d15t111ed water. Ana1y515 0f a11 c0n9ener5 0f PC85 wa5 perf0rmed w1th a Perk1n-E1mer aut05y5tem 9a5

chr0mat09raph e4u1pped w1th = N1 e1ectr0n capture detect0r. A 5P8-5 60nded pha5e (0.25 ~m f11m

th1ckne55) fu5ed 5111ca cap111ary c01umn (30 m 10n9, 0.2 mm 1.d.) fr0m 5upe1c0 wa5 u5ed. 7he carr1er 9a5

wa5 he11um at 110kPa (5p11t rat10 2511). the detect0r 5caven9er wa5 ar90n/methane (9515) at a f10w 0f 30

m1/m1n. 0ven temperature wa5 5et at 100 °C f0r 10 m and wa5 then 1ncrea5ed 6y 5°C1m1n t0 280°C,

wherea5 1nject0r temperature and detect0r temperature ware 5et at 200°C and 380°C re5pect1ve1y. 7he

ana1y515 0f n0n-0rth0 PC8 c0n9ener5 (1UPAC N5. 77, 126 and 169) and 0ther PC8 c0n9ener5 (1UPAC N5.

60, 105, 118 and 149) wa5 carr1ed 0ut w1th a F1nn19an MA7 6C-M5 Ma9num 17D 5y5tem. 7he f0110w1n9

ma55e5 ware u5ed f0r 1dent1f1cat10n and 4uant1f1cat10n: 292, 326 and 360 f0r tetra-C8, penta-C8 and hexa-

C8 re5pect1ve1y.

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A m1xture 0f 5pec1f1c PC8 150mer5 wa5 u5ed f0r ca116rat10n, rec0very eva1uat10n and c0nf1rmat10n. 51x

5amp1e5 were f0rt1f1ed w1th a m1xture 0f d1-0rth0 (1UPAC N5. 137, 138, 153, 170 and 194), m0n0-0rth0

(1UPAC N5.. 60, 105, 118 and 156) 0f n0n-0rth0 (1UPAC N5. 77, 126 and 169) PC8 c0n9ener5, at 1eve1 0f

1 n9/9 ad1p05e t155ue. Rec0very rate5 f0r n0n-0rth0 PC8 c0n9ener5 were: PC877; 97+12%, PC8126;

93-j:18% and PC8169; 86-j:19%.

51nce PC85 are h19h1y ap01ar c0mp0und5, c0ncentrat10n5 are expre55ed 1n part5 per m11110n (m9/K9)

ca1cu1ated 0n the 6a515 0f the we19ht 0f the Up1d5 extracted(11p1d 6a515).

5ex and repr0duct1ve c0nd1t10n wa5 determ1ned 6y exam1nat10n 0f d01ph1n 90nad5.

5tat15t1ca1 ana1y515. D1fference5 6etween 5exe5 and 5exua1 c0nd1t10n were exam1ned u51n9 0ne-way ana1y515

0f var1ance f0110wed 6y the 7ukey mu1t1p1e c0mpar150n te5t at p<0.05. A11 5tat15t1ca1 ca1cu1at10n5 were carr1ed

0ut u51n9 the 5P55-X 5tat15t1ca1 packa9e,

RE5UL75 AND D15CU5510N

0vem11PC8 c0ncentrat10n5

Prev10u5 5tud1e5 0n the 5tr1ped d01ph1n5 affected 6y the m0r61111v1ru5 ep1200t1c 0f the Med1terranean 5ea

dur1n9 1990-1992 (A9u11ar and Ra9a, 1993) 5h0wed that PC8 1eve15 1n the t155ue5 0f 1nd1v1dua15 that

5uccum6ed t0 the pr0ce55 were much h19her than 1n 0ther cetacean5, and am0n9 the h19he5t ever f0und 1n

w11d an1ma15 (Kannan et a1., 1993, A9u11ar and 80rre11, 1994). Re5u1t5 fr0m the pre5ent 5urvey c0rr060rate

the5e c0nc1u510n5. 7hu5, a5 5h0wn 1n ta61e 1, mean PC8 c0ncentrat10n5 1n the d01ph1n5 ana1y5ed were

855.9 ppm (=~69), an 0ut5tand1n91y h19h 1eve1 1n re1at10n t0 th05e prev10u51y rep0rted f0r 0ther mar1ne

mamma15.

1n term5 0f 150mer c0mp051t10n, the5e PC85 1nc1ude 3.98% pentach10r061pheny15, 51.05%

hexach10r061pheny15, 36.42% heptach10r061pheny15, and 8.55% 0ctach10r061pheny15. 7h15 c0mp051t10n

ref1ect5 the preva1ence 0f h19h1y ch10r1nated PC8 c0n9ener5 1n the m1xture. 7he re1at1ve r1chne55 0f a PC8

150mer 1n a 91ven 0r9an15m 15 the re5u1t 0f the c0mp051t10n 0f PC85 pre5ent 1n the env1r0nment m0du1ated

6y the dec0mp051t10n pr0ce55e5 that 0ccur fr0m the1r entrance 1nt0 the env1r0nment t0 the accumu1at10n 1n

the 0r9an15m. PC85 w1th h19her ch10r1ne c0ntent are u5ua11y m0re d1ff1cu1t t0 meta60115e (5awhney, 1986),

and theref0re the1r 610ma9n1f1cat10n p0tant1a115 h19her. 5tr1ped d01ph1n5 are 51tuated at the end 0f 10n9 f00d

we65, f0r wh1ch rea50n PC85 have under90ne 5u65tant1a1 meta60112at10n 6ef0re they are 1n9e5ted 6y

d01ph1n. 7h15 c0ntr16ute5 t0 exp1a1n the preva1ence 0f h19h1y ch10r1nated c0n9ener5 1n the1r 61u66er.

2363

F19ure 1 5h0w5 the mean c0ncentrat10n 0f PC8 c0n9ener5 1n the d01ph1n5 6y 5exe5. C0ncentrat10n5 0f a11

c0n9ener5 1n ma1e5 were d0u61e th05e 1n fema1e5. 1n the 11terature ava11a61e, ma1e5 a1m05t a1way5 pre5ented

h19her c0ncentrat10n5 than fema1e5, the d1fference 6etween 5exe5 ran91n9 fr0m a60ut a tw0f01d t0 0ver a

51xf01d var1at10n (A9u11ar et a1., 1n pre55). M0re0ver, 1n the Med1terranean 5tr1ped d01ph1n5 ana1y5ed,

c0n¢e,~;~at10n5 tended t0 1ncrea5e w1th a9e 1n ma1e5 and decrea5e 1n fema1e5, a1th0u9h 1he re1at10n5h1p

065erved wa5 n0t 519n1f1cant, pr06a61y 6ecau5e 0f 1n5uff1c1ent 5amp1e 512e. H0wever, when the 5amp1e wa5

ana1y5ed tak1n9 1nt0 acc0unt the 9r0wth 5tate, AN0VA and 7ukey te5t5 revea1ed a 519n1f1cant d1fference 1n

c0ncentrat10n5 0f a11 c0n9ener5 6etween mature ma1e5 and mature fema1e5 (p<0.05), 6ut n0 d1fference

6etween 1mmature ma1e5 and fema1e5..

7he rea50n 0f the5e d1fference5 15 the d1551m11ar1ty 1n 0r9an0ch10r1ne accumu1at10n pattem5. 1n mar1ne

marnma15, 0r9an0ch10r1ne 10ad5 tend t0 1ncrea5e w1th a9e dur1n9 the juven11e 5ta9e, 60th 1n ma1e5 and

fema1e$, 6ecau5e the uptake 0f c0ntam1nant u5ua11y exc~=d5 meta60112at10n and excret10n. 1n adu1t ma1e5,

th15 pattem c0nt1nue5 thr0u9h0ut the1r 11fe5pan and the1r c0ntam1nant 1eve15 1ncrea5e w1th a9e. 1n adu1t

fema1e5, h0wever, tran5fer 0f c0ntam1nant5 t0 0ff5pr1n9 dur1n9 9e5tat10n and 1actat10n cau5e p011utant

c0ncentrat10n5 t0 dec11ne Pr09re551ve1y w1th a9e. 7he5e d1ver91n9 trend5 1n adu1t ma1e5 and fema1e5 exp1a1n

the d1fference5 065erved 6etween 5exe5 1n the 5amp1e 0f Med1terranean 5tr1ped d01ph1n5 ana1y5ed.

200

150

50

8 0

,,x ~x -,.x

PC8 c0n9ener (1UPAC nr)

F19ure 1. C0ncen6~a~n 0f PC8 c0n9ener5 (m9/k9 11p1d we19ht) 1n ma1e5 and fema1e5.

2364

N0n 0rth0 5u1~t1tuted PC8 c0n9ener5

1n 60th c0mmerc1a1 preparat10n5 and 6101091ca1 5amp1e5, n0n-0rth0 5u65t1tuted PC8 c0n9ener5 are u5ua11y

1n extreme1y 10w c0ncentrat10n5 (Kannan eta/., 1987, H0n9 eta/., 1993). F0r th15 rea50n, the1r ana1y515 15

d1ff1cu1t and they are theref0re n0t r0ut1ne1y 4uant1f1ed w1th the 0ther PC8 c0n9ener5. 1ndeac1, 0n1y 1n t0p

predat0r 5pec1e5 d0 n0n-0rth0 5u65t1tuted c0n9ener5 610accumu1ate and reach 5uff1c1ent c0ncentrat10n5 t0

6e w1th1n the detect10n 11m1t5 0f the u5ua1 ana1yt1Ca1 pr0Cedure5. 1nf0rmat10n ava11a61e 0n the5e c0mp0und5

1n mar1ne mamma15 15 thu5 extreme1y 11m1ted.

7a61e 1 deta115 C0ncentrat10n5 0f n0n-0rth0 5U65t1tUted PC8 C0n9ener5 pre5ent 1n the 61U66er 0f the 5tr1ped

d01ph1n5 ana1y5ed 1n th15 5tudy and c0mpare5 them t0 th05e prev10u51y detected 1n 0ther mar1ne mamma15.

M05t p0pu1at10n5 0f mar1ne mamma15 5tud1ed t0 date pre5ent c0ncentrat10n5 0f t0ta1 n0n-0rth0 5u65t1tuted

PC8 0f the 0rder 0f few pp6 (ca1cu1ated 0n a 11p1d we19ht 6a515), C0ncentrat10n5 1n k111er wha1e5 fr0m the

Pac1f1c c0a5t 0f Japan (Kannan eta/., 1989) reached 50me d02en5, wh11e a11 Med1terranean d01ph1n5

(R1550•5, 60tt1en05e, and 5tr1ped d01ph1n5) ana1y5ed t0 date, 1nc1ud1n9 th05e ana1y5ed 1n the pre5ent 5urvey,

5h0wed 61u66er t155ue 1eve15 ran91n9 fr0m 50me ten5 t0 0ver 0ne hundred pp6 (Kannan eta/., 1993;

C0r5011n1 eta/., 1n pre55). Am0n9 the Med1terranean d01ph1n5, 5tr1ped d01ph1n5 affected 6y the m0r61111v1ru5

ep1200t1c are the m05t p011uted (Kannan et a/., 1993 and pre5ent 5urvey). 7he5e data 5u65tant1ate the h19h

preva1ence 0f c0-p1anar PC85 1n the Med1terranean 5ea.

F19Ure 2 5h0w5 5tr1ped d01ph1n PC8 c0mp051t10n 1n term5 0f 0rth0 5u65t1tut10n5. N0n-0rth0 PC8 c0n9ener5

repre5ented 0n1y 0.02% 0f the t0ta1 PC8 m1xture, fr0m wh1Ch the C0ntr16ut10n 0f c0n9ener 77 wa5 0.014%,

that 0f C0n9ener 126 wa5 0.005%, and that 0f c0n9ener 169 wa5 0.002%.

- n0n-0rth0

0ther

F19ure 2. Percenta9e 0f c0ncentrat10n 0f m0n0- d1- and n0n-0rth0 PC85 re5pect t0 the t0ta] PC8.

7a61

e 1 :

C0n

cent

rat1

0n 0

f n0n

-0rth

0 5u

65t1

tute

d P

C8

c0n9

ener

5 (n

9/9

11p1

d we1

9ht)

and

tPC

8 (m

9/K

9 11

p1d w

e19h

t) 1n

the

61u6

6er 1

f mar

1ne

mam

ma1

5. (

* w

et w

e19h

t 6a5

15).

$PE

C1E

5 A

RE

A

N

77

126

169

tC0

P.

tPC

8 R

EFE

RE

NC

E

pp6

ppm

P1

NN

1PED

1A

H. 9

rYpu

5 8a

1t1c

5ea

7

2,91

0 1,

810

1,13

0 5,

85

K01

5t1n

en, 1

990

H. 9

rYP

u5

8a1t

1c 5

ea

1 2,

960

1,84

0 1,

090

5,89

22

7 P

aa51

v1rta

and

Ran

t10,

199

1 P

. h15

p1da

8a

1t1c

5ea

7

7,17

0 2,

210

0,20

0 9,

58

K01

5t1n

en, 1

990

P. h

15p1

da

8a1t

1c 5

ea

1 8,

070

2,23

0 0,

110

10

,41

40

,9

Paa

51v1

rta an

d R

ant1

0, 1

991

P. h

15p1

da

Can

ad1a

n A

rct1

c 8

0,10

3 0,

112

0,01

8 0,

23

0,7

F0rd

et a

1., 1

993

P.

v1tu

/1na

* D

enm

ark

21

0,02

5 0,

324

0,03

3 0,

38

11

,3

5t0r

r-H

an5e

n an

d 5p

111d

, 199

3 P

. v1

tu11

na

N0r

th 5

ea

5 0,

140

0,14

8e

ck e

t a1.

, 199

0 P

. v1

tu11

na*

Ca1

1f0r

n1a

3 7,

300

3,00

0 n.

d.

10,3

0 H

0n9

et a

1., 1

993

P.

v1tu

11na

5c

0tt1

and

1 0,

259

1,88

2 1,

882

4,02

1

4,0

W

e115

and

Ech

arr1

, 199

2 P

. v1

tu11

na*

U5A

At1

ant1

c 6

0,31

6 1,

450

0,01

9 1,

79

12

Lake

et a

1., 1

995

P.

v1tu

11na

* U

5A A

t1an

t1c

4 0,

073

0,53

3 0,

013

0,62

6,

66

Lake

et a

1., 1

995

P. 9

r0en

1and

1ca*

6r

een1

and

5ea

10

0,17

9 0,

215

0,19

0 0,

58

2,85

0e

hme

et a

1., 1

995

P.

ca5p

1ca*

C

a5p1

an 5

ea

1 0,

069

0,18

5 0,

029

0,28

1,

36

Vet

ter e

t a1.

, 199

5

CE

7AC

EA

P

. maC

r0ce

pha1

u5

5c0t

t1an

d 1

3,23

3,

15

0,92

3 7,

31

5,5

We1

15 an

d E

char

r1, 1

992

0. 0

rca*

Ja

pan

3 48

,00

3,70

7,

70

59,4

0 37

0 K

anna

n et

a1.

, 198

9 8.

6a1

rd11

* Ja

pan

3 1,

300

0,35

0 0,

240

1,89

2,

3 K

anna

n et

a1.

, 198

9 M

. m0n

0cer

05

Ca

na

d1

an

Arc

t1c

17

0,20

6 0

,18

1

0,05

6 0,

44

5,2

F0rd

et a

1., 1

993

D./

euca

5 C

anad

1an

Arc

t1c

6 0,

233

0,11

5 0,

015

0,36

5,

6 F0

rd e

t a1.

, 199

3 7.

tru

ncat

u5

U5A

At1

ant1

c 5

0,67

8 0,

606

0,26

8 1,

55

102

Kue

h1, 1

991

7. t

runc

atu5

5c

0tU

and

1 2,

73

1,36

0,

614

4,70

1

6,5

W

e115

and

Ech

arr1

, 199

2 7.

tru

ncat

u5

Med

1t. 5

ea

8 59

,57

7,02

14

,47

81,0

6 13

30

C0r

5011

n1 et

a1.

, 199

5 6.

9d5

eu5

Med

1t. 5

ea

2 29

,63

7,96

10

,74

48,3

3 52

0 C

0r50

11n1

et a

1., 1

995

5. c

0eru

1e0a

16a

Med

1t. 5

ea

10

104,

9 16

,59

19,0

2 14

0,49

95

9 K

anna

n et

aL,

199

3 5.

c0e

ru1e

0a16

a M

ed1t

. 5ea

30

12

2,0

43,0

0 21

,00

186,

00

855

Pre

5ent

5ur

vey

D01

ph1n

• W

e5t 1

re1a

nd

1 4,

53

3,02

6,

63

14,1

9 80

er e

t a1.

,199

2 P

. ph0

c0en

a N

0rth

5ea

1

0,58

0 0,

58

K01

5t1n

en, 1

990

P. p

h0c0

ena

5c0

tt1

an

d

1 1,

65

0,44

3 0,

215

2,30

33

,2

We1

15 an

d E

Cha

rr1, 1

992

P.

da11

1*

Japa

n 5

2,30

0,

160

0,11

0 2,

57

8,6

Kan

nan

et a

1., 1

989

N. p

h0ca

en01

de5*

N

.N. P

ac1f

1c

1 14

,00

0,89

0 0,

640

15,5

3 32

0 K

anna

n et

a1.

, 198

9 tJ

L

~

2 3 6 6

7h15 1nd1cate5 that the 0rder 0f PC8 c0p1anar c0ncentrat10n5 f0und 1n the 5tr1ped d01ph1n5 wa5

7,C8>P5C8>H5C8, a pr0p0rt10n 51mUar t0 that f0und 1n m05t 0ther mar1ne mamma15 5urveyed (7ana6e et

aL, 19876), a1th0u9h 1t apparent1y c0ntrad1ct5 f1nd1n95 6y Kannan et a1. (1993), wh0 5u99e5ted a rever5ed

trend a5 a c0n5e4uence 0f act1vat10n 0f m1xed funct10n 0x1da5e en2yme5 6y h19h t155ue PC8 c0ncentrat10n5

1n the 5ame 5pec1e5. 1t 15 unc1ear why the5e 0pp051te re5u1t5 were f0und 1n para11e1 5tud1e5 carr1ed 0ut 0n the

5ame p0pu1at10n 0f d01ph1n5, a1th0u9h 1nter1a60rat0ry d1fference5 1n ana1yt1ca1 techn14ue5 0r the effect 0f

rand0mne55 0n reduced 5amp1e 512e5 may acc0unt f0r them.

70x1c1ty

F19ure 3 5h0w5 the mean c0ncentrat10n 0f c0p1anar PC8 c0n9ener5 and c0rre5p0nd1n9 7EQ5 f0r each

c0mp0und, ca1cu1ated a5 pr0p05ed 6y Ah160r9 eta/. (1994), 1n the 5tr1ped d01ph1n5 5tud1ed f0r the pre5ent

5urvey. 7he u5e 0f th15 meth0d 0f ca1cu1at1n9 7EQ5 rendered 5u65tant1a11y d1fferent re5u1t5 fr0m prev10u5

e5t1mate5 carr1ed 0ut u51n9 5afe•5 (1990) fact0r5, a5 app11ed 6y Kannan et a/. (1993). Part1cu1ar1y, the

519n1f1cance 0f n0n-0rth0 5u65t1tuted PC85 1n the t0x1c1ty 0f the m1xture 15 e5t1mated t0 6e much h19her u51n9

Ah160r9 eta/. (1994) 7EF5 than than th05e 0f 5afe (1990).

7EF5

77

126 c

~ 105

118 03

C 156 0 0

n4 170 (9 Q•

180

).0001

70 60 50 40 30 20 10 0 1 2 3 4 5 6 7

C0ncentrat10£ (ppm 11p.6a515) 7EQ (pp6 11p.6a515)

F19ure 3: C0ncentrat10n 0f c0p1anar PC8 c0n9ener5 and 7CDD-E4u1va1ent5.

Acc0rd1n9 t0 0ur ca1cu1at10n5, t0x1c1ty due t0 c0p1anar c0n9ener5 d15tr16ute5 51m11ar1y 6etween n0n-, m0n0-

and d1-0rth0 5u65t1tuted c0n9ener5, each 9r0up acc0unt1n9 f0r m0re 0r 1e55 0ne th1rd 0f the 0vera11 t0x1c1ty.

2367

F19ure 4 5h0w5 the t0x1c1ty c0ntr16ut10n 0f the c0p1anar c0mp0und5 1n deta11. N0n-0rth0 c0n9ener5

acc0unted f0r 32.3% 0f the 0vera11 t0x1c1ty, wherea5 m0n0-0rth0 and d1-0rth0 c0ntr16uted 30.4% and 37.3%

re5pect1ve1y. D1-0rth0 c0n9ener 170 and n0n- 0rth0 c0n9ener 126 were the maj0r c0ntr16ut0r5 t0 7EQ (33%

and 30% re5pect1ve1•)•).

1t 15 n0tew0rthy that, de5p1te tha fact that n0n-0rth0 5u65t1tuted PC8 c0n9ener5 repre5ent 0n1y 0.02% 0f the

t0ta1 PC8 1cad 1n 5tdped d01ph1n5, the1r t0x1c1ty c0ntr16ut10n 15 0ne th1rd 0f the 0vera11 t0x1c1ty. 7h15 15 a re5u1t

0f the extreme1y h19h t0x1c1ty 0f the5e c0mp0und5.

1n terre5tr1a1 mamma15 and 61rd5, t0ta1 PC8 c0ncentrat10n5 are a1m05t a1way5 10wer than 1n mar1ne

mamma15. 7h15 15 a150 true f0r the c0p1anar f0rm5. 0n the 0ther hand, 1n terre5tr1a1 mamma15 and 61rd5, n0n-

0rth0 c0n9ener5 are re5p0n5161e f0r a h19her pr0p0rt10n 0f the 7EQ than 1n the ca5e 0f mar1ne mamma15, a

d1fference that ha5 6een a550c1ated w1th a h19her capac1ty 0f mar1ne mamma15 t0 meta60115e n0n-0rth0

c0n9ener5 (Kannan eta1., 1993).

m0n0-0rth0 30.4% n0n-0rth0

118 169 32.3%

126 105 ) F19ure 4. Percenta9e t0:~c1ty c0n~16ut10n 0f m0n0- d1- and n0n- 0rth0 PC85 re5pect t01he t0ta17EQ.

ACKN0WLED6EMEN75

Rec0very 0f carca55e5 and t155ue 5amp1e c011ect10n were funded 6y 5pec1f1c 9rant5 fr0m 1C0NA, and the

Aut0n0m0u5 60vemment5 0f Cata10n1a and Va1enc1a. Many 1nd1v1dua15 c0ntr16uted per50na11y t0 the 5trand1n95

netw0rk w1th the1r eff0rt5 and c00perat10n, and we w0u1d 11ke t0 expre55 0ur 51ncere 9rat1tude t0 a11 0f them. 7h15

re5earch wa5 made p055161e thr0u9h part1a1 fund1n9 9ranted 6y 5pa1n•5 C0m1510n 1ntrm1n15ter1a1 de C1enc1a y

7ecn01091a (AM894-0399 Pr0ject) and 1C0NA. Dur1n9 th15 5urvey, A. 80ne11 wa5 5upp0rted 6y a p05t d0ct0ra1

fe110w5h1p fr0m the C1R17.

2368

818U06RAPHY

A9u11ar, A. and 80rre11, A. 1988. A9e- and 5ex-m1ated chan9e5 1n 0r9an0ch10r1ne c0mp0und 1eve15 1n f1n wha1e5 (8a/aen0ptera phy5a1u5) fr0m the ea5tem N0rth At1ant1c. Mar.En¢4r0n. Re5., 25:195-211.

A9u11ar, A. and Ra9a, J. A. 1993.7he 5tr1ped d01ph1n ep1200t1c 1n the Med1terranean 5ea. Am610, 22(8): 524-528. A9u11ar, A. and 80rre11, A. 1994. A6n0rma11y h19h p01ych10r1nated 61pheny1 1eve15 1n 5tr1ped d01ph1n5 (5tene//a

c0eru/e0a16a) affected 6y the 1990-1992 Med1terranean ep1200t1c. 5c1. 70ta1 Env1r0n., 154(2-3): 237-247. A9u11ar, A., 80rre11, A and Pa5t0r, 7. (1n pre55): Fact0r5 affect1n9 var1a6111ty 0f per515tent p011utant 1eve15 1n cetacean5.

Rep. 1nt. Wha1. C0mmn. (5pec1a1155ue ), Ah160r9, U.6., Han6er9, A. and Kenne, K. (1992). R15k a55e55ment 0f p01ych10r1nated 61pheny15. N0rd1c C0unc11 0f

M1n15ter5, C0penha9en, N0n:1 1992:26. Ah160r9 U.6., 8eck1n9, 6.C., 81m6aum, L.5., 8r0wer, A., Derk5, H.J.6.M., Fee1ey, M., 6010r,6., Han6er9, A., Lar5en,

J.C., L1em, A.K.D., 5afe, 5.H., 5ch1atter, C. Waem, F. Y0une5, M. and Yrj8nhe1kk1, E. 1994. 70x1c e4u1va1ency fact0r5 f0r d10x1n-11ke PC85. Chem05phere 28 (6):1049-1067.

8eck, H.; 8reuer, E.M.; Dr06,A. and Mathar, W. 1990. Re51due5 0f PCDD5, PCDF5, PC85 and 0ther 0r9an0ch10r1ne c0mp0und51n har60ur 5eaL5 and hart)0ur p0rp015e. Chem05phere 20:1027-1034.

80er, J. de; 5tmnck, C. J. N.; Va1k, F. van den; We5ter, P. 6. and Daudt, M. J. M. 1992. Meth0d f0r the ana1y515 0f n0n-0rth0 5u65t1tuted ch10r061pheny151n f15h and mar1ne mammaL5. Chem05phere, 25 (7-10): 1277-1283.

80rre11, A. 1993. D1n•m1ca de15 c0mp05t05 0r9an0d0rat5 en 1a 6a1ena d•a1eta, e1 cap d•011a d•a1eta 11ar9a 1 e1 d0ff 1115tat d•a190e5 at1~nt14ue51 med1terr~n1e5. PhD. 7he515. Un1ver51ty 0f 8arce10na.

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Kannan, N.; 7ana6e, 5., Wak1m0t0, 7. and 7at5ukawa, R. 1987. C0p1anar PC85 1n Ar0c10r5 and Kanmh10r5, J. A550c 0ff Ana1 Chem 70:451-454.

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Paa51v1rta,J. and RanU0,7. 1991 Ch10r0terpene5 and 0ther 0r9an0ch10r1ne5 1n 8a1t1c, F1nn15h and Arct1c w11d11fe. Chern05phere, 22(1-2): 47-55.

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