Organochlorine compounds in Baltic salmon and trout. I. Chlorinated hydrocarbons and chlorophenols 1982

Chemosphere, Vol.14, No.ll/12, Printed in Great Britain

pp 1729-1740,

1985

0045-6535/85 $3.00 + .OO @1985 Pergamon Press Ltd.

ORSANOCHLORINE COMPOUNDS IN BALTIC SALMON AND TROUT. I . CHLORINATED HYDROCARBONS AND CHLOROPHENOLS 1982 Pekka J. Vuorinen F i n n i s h Same and F i s h e r i e s Research I n s t i t u t e , F i s h e r i e s D i v i s i o n U n i o n i n k a t u 45 B 42, SF 00170 H e l s i n k i 17, F i n l a n d Jaakko P a a s i v i r t a , Teuvo P i i l o l a , Kari Surma-Aho and Juhani Tarhanen Department of Chemistry, U n i v e r s i t y of J y v i s k y l ~ K y l l i k i n k a t u 1-3, SF 40100 J y v ~ s k y l ~ 10, F i n l a n d

ABSTRACT

P o l y c h l o r i n a t e d hydrocarbons and c h l o r o p h e n o l compounds were analyzed i n three populations of Baltic salmon (Salmo s a l a r ) and one p o p u l a t i o n of Bothnian Bay t r o u t (Salmo t r u t t a ) . Muscles, l i v e r s and u n f e r t i l i z e d eggs were s t u d i e d and t h e a n a l y s i s r e s u l t s t r e a t e d by standard s t a t i s t i c a l methods. PCB, DDT r e s i d u e s , HCB and l i n d a n were d e t e c t e d i n most, 2,3, b - t richlorocymene in s o m e samples a t l e v e l s which a r e near t o t h e g l o b a l b a s e l i n e . Ten chlorophenol compounds were d e t e c t e d , 34DCC a t 0-1000 ug/kg t h e o t h e r s 0-100 ug/kg ( f r e s h w e i g h t ) l e v e l s . Chlorohydrocarbons showed some s i g n i f i c a n t p o s i t i v e c o r r e l a t i o n s w i t h w e i g h t , a n d f a t c o n t e n t s of t h e f i s h . S i g n i f i c a n c e s o f t h e d i f f e r e n c e s between p o p u l a t i o n s and t i s s u e s were low or n e g l i b l e except t h a t t h e c h l o r o p h e n o l s i n l i v e r were a t c l e a r l y h i g h e r l e v e l than i n muscle or eggs.

INTRODUCTION

P e r s i s t e n t and t o x i c o r g a n o c h l o r i n e compounds form a t h r e a t t o man and environment which has been i n t e n s i v e l y s t u d i e d w h i l e t h e s e substances can be monitored by e x t r e m e l y s e n s i t i v e a n a l y s i s methods. B a l t i c salmon (Salmo s a l a r ) and t r o u t (Salmo t r u t t a ) have a g r e a t importance as food and, w h i l e l o c a t i n g a t high t r o p h i c l e v e l of t h e a q u a t i c ecosystem, appeared t o be a v e r y s u i t a b l e sample m a t e r i a l t o s t u d y t h e appearance o f t h e p o t e n t i a l l y harmful x e n o b i o t i c s . The accumulation of these substances i n t i s s u e s of p a r e n t f i s h might a l s o d i s t u r b t h e development of t h e i r gametes, and even t h e i r of÷springs. In t h e p r e s e n t s t u d y t h e w e l l known b i o c i d i c o r g a n o c h l o r i n e hydrocarbans were s e l e c t e d t o be a n a l y z e d . In a d d i t i o n , c h l o r o p h e n o l i c compounds, among which some might be p e r s i s t e n t and harmful i n b i o s p h e r e , were taken %o be s t u d i e d , because we i n J y v i s k y l i posess a complete r e f e r e n c e standard c o l l e c t i o n of p o l y c h l o r o p h e n o l s (PCP), c a t e c h o l s (PCC) and g u a i a c o l s (PCS) and have developed t h e i r a n a l y s i s methods a t l oN l e v e l i n b i o l o g i c a l samples.

1729

1730

. .,..,.,. ) '~'~.,.,'~. -a'i "~

SAMPLES

Catching areas o f the s t u d i e d p o p u l a t i o n s are i n d i c a t e d as numbers i n t h e map (Fig. 1). The ~ l~ sampled p o l u l a t i o n s were s e l e c t e d on t h e b a s i s ~ ') of d i f f e r e n t m i g r a t i n g b e h a v i o u r . Salmons of I ./ p o p u l a t i o n 1 (Kemi River) m i g r a t e t o t h e B a l t i c I'. ~.~ p r o p e r , and those o f p o p u l a t i o n 3 (Kymi R i v e r ) ~ ~) .) mainly m i g r a t e i n the Gulf o~ F i n l a n d 111. Trout ~ . /-.9~ ~. ~weoen ) USSR ( p o p u l a t i o n 2, Kemi r i v e r ) are q u i t e l o c a l , y ~ # , j, r "~ P o p u l a t i o n s (1-:3) were catched by p r o f e s s i o n a l /.yr "x fishermen d u r i n g spawning m i g r a t i o n on the Sea ~__ ? r|nland ") near t h e corresponding r i v e r m o u t h . P o p u l a t i o n s ~ Gulf ) .,," 1 (salmon) and 2 ( t r o u t ) were kept a l i v e i n ~ B0~hni,~ // freshwater f l o w o f Kemi r i v e r and p o p u l a t i o n 3 ~. [ / / ~ (salmon) i n Kymi r i v e r , r e s p e c t i v e l y , from 3une ¢ ~ ' ~'~v.''~'~r~ .,--'--~ r , J ~ - ' " ~ "~.._ '~ \/~ ) a t the Central Fish C u l t u r e S t a t i o n of Northern ~//_ ~...L"~ -• 8'1ttc .~T T F i n l a n d o f t h e F i n n i s h Game and F i s h e r i e s Research ~a (--"\,~ I n s t i t u t e . In October eggs were s t r i p p e d and f i s h ~ F ~ -I were s a c r i f i e d . They were measured, weighed, and Y / ~J t h e muscle, l i v e r and u n f e r t i l i z e d egg samples were taken and stored f r o z e n . FIGURE 1. Sampling areas. COMPOUNDS ANALYZED S t r u c t u r e s and names of t h e compounds sought from a l l samples are given below, chlorohydrocarbons i n F i g . 2, c h l o r o p h e n o l s i n F i g . 3. In a d d i t i o n , p o l y c h l o r i n a t e d dibenzofurans (PCDF), p o l y c h l o r i n a t e d d i b e n z o - p - d i o x i n s (PCDD) were s t u d i e d from t h r e e muscle samples of each f o u r p o p u l a t i o n s ( r e s u l t s are not included h e r e ) . CCl2

CHCI z

CCl]

Cl

c, DOE

Cl ~ C I

c,

ODD

/

c, o, Q ,e Cl

DOT

Clp

HCB

PCB

Hexachloro- Polychlori nated

P e r s i s t e n t residues o f the i n s e c t i c i d e DDT

benzene

CH 3

CI

Cl

Cl

Cl

C

I

o

C! .cl

Cl

a

cl

Lindan

H3C CH3 GYM

Cl

¢1 0 '~ ~1

LIND

Cl

..o

OXY

0

bi phenyls

C!

o

CI

¢1

"¢~1

C!

CI

c, GAMMA

ALPHA

TRANS

2,3,6-Trichlo- Oxychlordane y"-Chlordane o~-Chlordane Trans-nonachlor rocymene FIGURE 2. S t r u c t u r e s and names o f t h e chlorohydrocarbons analyzed.

1731

23DCP

Cl

26DCP

2LIDCP

I

el" v

345TCP ~ C H

2346TECP 3

4SDCG H3CO

DMP

"CI

2356TECP

3LI5TCG

CL~H3

q56TCG

I

"'CI

PECP

TECG

H

CI

245TCP

Clf ~ ,

L ~ I cLH3 C 1 ~ H 3

H3

Cl" "~,~ ~1

246TCP

Ci

CI

34DCC

CI

L

345TCC

H

Cl" ~1 "el TECC

FIGURE 3. Structures and name abbreviations of the chlorophenol analyzed in the present study.

compounds

Seventeen chlorophenol compounds which have been found in aquatic w i l d l i f e /2-5/ were chosen to the analytical reference standard (Fig. 3). The authentic reference compounds were p u r i f i e d (PCPs) or synthesized (PCCs and PCGs) and t h e i r analytical properties exposed in Jyviskyl& /6-10/.

ANALYSIS PROCEDURES Chlorohvdrocarbons and chloroohenols Weighed part of the homogenized muscle, l i v e r or egg sample was mixed with 3 times higher amount of dry sodium suphate and measured amounts of the internal standards (2,4,6-trichlorobiphenyl for chlorohydrocarbons and 2,3,6-trichlorophenol f o r chlorophenol compounds). Soxhlet extraction with a solvent mixture hexane-acetone--diethyl e t h e r - l i g h t petroleum b.p. 40-60 (2.5:5.5:1:9 v/v) was performed f o r 6 hours and the extract evaporated by nitrogen gas stream. The residue was weighed %o obtain f a t contents and then dissolved in 5 ml of hexane.

1732

P a r t o f t h e hexane s o l u t i o n (2 ml) was shaken w i t h conc. sulphuric acid and a n a l y s e d by SC/ECD f o r chlorohydrocarbons as d e s c r i b e d p r e v i o u s l y / 5 / .

C h l o r o p h e n o l d e t e r m i n a t i o n p r o c e d u r e was somewhat m o d i f i e d from

the

pre-

v i o u s one / 5 / . A n o t h e r 2 ml o f t h e hexane s o l u t i o n was mixed w i t h 2 ml o f e t h e r s 3 ml o f 0 . 2 N NaOH and 3 ml o f wet a n i o n exchange r e s i n Sephadex QAE-25 and shaken f o r 5 m i n u t e s . The s o l v e n t s were d e c a n t e d away, 2 ml e t h e r and 2 ml o f w a t e r s o l u t i o n o f KC1 ( 0 . 0 5 N) and HC1 ( 0 . 2 N) added and shaken f o r 2 min. The e t h e r l a y e r was added t o 50 ml of water solution which contains 1 ml o f 70 % p o t a s s i u m c a r b o n a t e and 1 ml o f a c e t i c a c i d a n h y d r i d e and shaken f o r 5 min. w i t h 5 ml o f hexane. The hexane l a y e r was e v a p o r a t e d t o 1 ml volume and sample o f i t i n j e c t e d t o a gas chromatograph O r i o n A n a l y t i c a MICROMAT HRGC 412 w i t h d u a l column o p e r a t i o n . The columns were o f ~used s i l i c a c o a t e d w i t h SE 54 and OV 1701. N i - 6 3 EC d e t e c t o r s were used i n t e m p e r a t u r e - p r o g r a m m e d r u n n i t r o g e n as c a r r i e r gas. Chlorophenol a c e t a t e s were i d e n t i f i e d comparing t o t h e a u t h e n t i c r e f e r e n c e s t a n dard m i x t u r e and q u a n t i f i e d u s i n g r e s p o n s e f a c t o r s against the internal standard. L i m i t o f d e t e r m i n a t i o n was ( i n f r e s h w e i g h t ) 0 . 5 n g / g (ppb) ~or chloroh y d r o c a r b o n s and c h l o r o p h e n o l s c o n t a i n i n g t h r e e o r more c h l o r i n e s , 4 ppb for chlorophenols containing 2 chlorines. The a n a l y s i s r e s u l t s

were s t o r e d i n computer memory and h a n d l e d

dard s t a t i s t i c a l methods p r e v i o u s l y employed food chain x e n o b i o t i c s s t u d i e s / 5 , 1 1 , 1 2 / .

in

our f i s h

by

stan-

and a q u a t i c

RESULTS AND DISCUSSION

Basic s t a t i s t i c s o f t h e samples and t h e i r o r g a n o c h l o r i n e compound c o n t e n t s were c a l c u l a t e d f o r each p o p u l a t i o n ( 1 - 4 ) and f o r each t i s s u e (muscle, livers eggs) and a r e p r e s e n t e d on f r e s h w e i g h t b a s i s i n T a b l e s 1-7. Q u i t e a l a r g e v a r i a t i o n o c c u r e d i n w e i g h t and l e n g h t o f t h e f i s h e s and i n fat c o n t e n t s o f t h e t h r e e t i s s u e s as seen i n T a b l e 1. Chlorohydrocarbons ( F i g . 2 . ) were d e t e c t e d i n a l l p o p u l a t i o n s and t i s s u e s e x c e p t 2 , 3 , 6 - t r i c h l o r o c y mene (SYM) which was n o n - d e t e c t a b l e i n a l l t r o u t t i s s u e s and i n muscles o f t h e Kymi r i v e r salmons ( p o p u l a t i o n 3; see T a b l e s 2 - 4 ) . The l e v e l o f PCB o f t h e w i l d salmons ( p o p u l a t i o n s 1 and 3) was a l i t t l e lower than t h a t o b s e r ed i n Sda~sk Bay salmon / 1 3 / , b u t t h e l e v e l o f SDDT (= DDE + DDD + DDT) o f salmon p o p u l a t i o n s 1 and 3 was a b o u t s i x t i m e s h i g h e r . Ten o f t h e s e v e n t e e n s t u d i e d c h l o r o p h e n o l compounds ( F i g . 3) were d e t e c t e d b u t o n l y i n p a r t o f t h e samples, most f r e q u e n t l y i n l i v e r s where t h e i r l e v e l was h i g h e r t h a n i n o t h e r t i s s u e s . S t a t i s t i c s which i n c l u d e s t h e zero values are presented in Tables 5-7.

1733

TABLE 1. S t a t i s t i c s of the Baltic salmon and trout samples c o l l e c t e d 1983 f o r t h e p r e s e n t a n a l y s e s i n c l u d i n g r e s u l t s o f t h e f a t d e t e r m i n a t i o n s . N o t a t i o n s : x = a v e r a g e , s = s t a n d a r d d e v i a t i o n , N = number o~ s a m p l e s , MIN = s m a l l e s t v a l u e and MAX = l a r g e s t v a l u e . Expl.

Weight kg

x s N MIN MAX

5.00 2.67 15 2.30 10.00

Population 1. Kemi r i v e r Salmon

Lenght cm

Muscle Fat %

Liver Fat %

Egg Fat %

82.0 12.3 15 67.5 101.5

5.43 2.26 15 2.11 9.35

2.37 0.69 15 1.39 3.56

5.68 1.13 15 2.70 7.42

2. Kemi river Trout

x s N MIN MAX

3.15 .619 11 2.30 4.40

66.9 3.38 11 62.5 73.0

3.15 1.21 11 1.62 5.53

2.72 0.70 11 1.86 3.85

5.94 1.33 11 4.31 8.35

3. Kymi r i v e r Salmon

x s N MIN MAX

4.63 .737 3 3.80 5.20

77.3 4.62 3 72.0 80.0

4.45 3 . Za3 3 1.50 8.01

2.06 0.31 3 1.85 2.42

5.54 0.13 3 5.40 5.64

4. H a t c h e r y Salmon

x s N MIN MAX

3.22 .536 10 2.44 4.02

65.1 3.90 10 59.0 71.5

4.02 1.34 10 1.93 5.92

2.30 0.20 10 2.09 2.69

5.13 2.43 10 3.58 11.9

TABLE 2. C h l o r i n a t e d h y d r o c a r b o n s n g / g (ppb) i n f r e s h muscles of Baltic salmon and t r o u t . SDDT = DDE + DDD + DDT. F o r n o t a t i o n s s e e T a b l e 1. HCB

PCB

DDE

DDD

DDT

S D D T OXY GAMMA ALPHA TRANS

LIND

1. K e m i r i v e r , x 19.3 333 s 6.34 115 N 14 14 MIN 10 146 MAX 32 491

Salmon 202 141 4 8 . 0 85.7 74.1 2 3 . 5 14 14 14 83 11 15 373 267 93

390.5 168.0 14 116 713

13.6 10.7 14 4 40

13.3 11.3 14 0 32

15.1 8.31 14 0 30

14.2 6.41 14 0 24

5.00 5.75 14 0 20

2. K e m i r i v e r , x 4.91 425 s 2.26 173 N 11 11 MIN 1 147 MAX 9 733

Trout 145 1 6 . 6 3 0 . 5 59.7 19.6 13.6 11 11 11 41 1 5 241 71 48

191.6 75.1 11 47 282

10.5 6.56 11 0 19

0.91 2.07 11 0 6

1.73 1.68 11 0 5

7.18 4.51 11 0 13

1.36 1.29 11 0 3

3. Kymi r i v e r 5 Salmon X 9.67 350 109 112 5 5 . 7 s 8.96 136 5 4 . 5 60.6 27.6 N 3 3 3 3 3 MIN 4 199 55 53 27 MAX 20 464 164 174 82

276.0 142.5 3 135 420

28.7 7.77 3 20 35

10.7 5.51 3 5 16

3.00 5.20 3 0 9

12.3 6.03 3 6 18

5.67 2.31 3 3 7

4. Hatchery, Salmon X 5.10 240 76o8 29.6 20.6 s 2.13 116 4 4 . 8 2 6 . 1 1 1 . 0 N 10 10 10 10 10 MIN 3 120 40 3 8 MAX 10 469 192 64 41

127.0 64.6 10 51 234

10.0 7.80 10 3 21

5.20 3.58 10 0 12

5.80 10.7 5.09 6.86 10 10 0 0 19 20

2.10 1.66 10 0 4

SYM 18.8 35.7 11 0 115

5.40 6.99 5 0 17

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1735

TABLE 5. A v e r a g e c o n t e n t s ( x ) o f c h l o r o p h e n o l s ppb i n f r e s h m u s c l e s o f Baltic salmon and t r o u t , s t a n d a r d d e v i a t i o n s (s) and numbers o f samples (N) included. 246TCP 245TCP

TeCP

1. K e m i r i v e r , x 1.9 0.2 s 4.5 0.6 N 13 13

Salmon 5.0 13.6 13

1.8 6.1 13

19.2 50.6 13

5.2 10.0 13

9.3 26.4 13

9.7 17.0 13

9.2 17.7 13

17.2 40.5 13

68.2 85.2 15

2. K e m i r i v e r , x 5.9 2.5 s 8.4 7.2 N 11 11

Trout 29.3 26.9 11

4.2 4.4 11

89.9 185.0 11

2.2 5.8 11

2.9 5.6 11

3.6 6.5 11

2.5 8.4 11

17.8 59.1 11

160.9 269.5 11

3. Kymi r i v e r , x 1.0 0.0 s 1.7 0.0 N 3 3

Salmon 17.3 23.4 3

3.0 3.0 3

0.0 0.0 3

0.0 0.0 3

1.3 2.3 3

0.0 0.0 3

0.0 0.0 3

7.0 6.2 3

29.7 21.4 3

2.0 2.3 10

332.0 330.9 10

4.0 9.9 10

2.6 4.5 10

0.0 0.0 10

0.0 0.0 10

2.0 3.3 10

350.1 336.0 10

4. H a t c h e r y , Salmon x 1.7 3.5 2.3 s 3.5 5.3 2.8 N 10 10 10

P e C P 34DCC 345TCC

DMP

T E C C 456TCB

TEC8

SUM

TABLE b. A v e r a g e c o n t e n t s ( x ) o f c h l o r o p h e n o l s ppb i n f r e s h l i v e r s a m p l e s o f B a l t i c salmon and t r o u t , s t a n d a r d d e v i a t i o n s ( s ) and numbers o f samples (N) included. 246TCP 245TCP

TeCP

1. K e m i r i v e r , x 5.9 18.5 s 10.3 39.3 N 15 15

Salmon 2.2 3.4 15

2. Kemi r i v e r , x 15.0 25.6 s 16.2 54.8 N 11 11 3. x s N

Kymi r i v e r , 2.3 74.3 4.0 128.7 3 3

P e C P 34DCC 345TCC

DMP

TeCC

456TC8

TeC8

SUM

3.1 5.4 15

247.7 202.2 15

4.7 6.8 15

14.9 35.8 15

3.4 9.5 15

8.4 24.4 15

17.0 29.1 15

325.9 227.6 15

Trout 28.9 22.4 11

12.8 9.9 11

319.5 377.4 11

15.1 33.9 11

8.6 15.4 11

6.4 13.3 11

5.1 13.2 11

6.5 17.2 11

443. & 457.7 11

Salmon 196.7 278.4 3

68.7 50.3 3

118.7 121.6 3

0.0 0.0 3

4.3 7.5 3

0.0 0.0 3

30.0 39.7 3

2.0 3.5 3

497.0 497.0 3

1.4 3.1 10

210.9 128.8 10

5.& 4.7 10

3.8 4.0 10

18.5 57.5 10

5.4 6.9 10

1.6 3.1 10

260.8 139.9 10

4. H a t c h e r y , Salmon x 10.3 3.3 0.0 s 31.5 5.1 0.0 N 10 10 10

1736

TABLE 7 . A v e r a g e c o n t e n t s (×) o f c h l o r o p h e n o l s ppb i n f r e s h egg s a m p l e s o f Baltic salmon and t r o u t , s t a n d a r d d e v i a t i o n s ( s ) and numbers o f samples (N) included. 246TCP 245TCP

TeCP

P e C P 34DCC 345TCC

DMP

TeCC

1. K e m i r i v e r , x 5.4 1.2 s 9.2 2.5 N 15 15

Salmon 13.1 35.0 15

1.4 2.6 15

26.8 47.7 15

1.0 2.4 15

2.0 4.1 15

4.7 12.2 15

2. K e m i r i v e r , x 10.7 6.7 s 10.1 22.3 N 11 11

Trout 37.2 26.8 11

9.9 9.1 11

32.9 108.8 11

0.0 0.0 11

0.1 0.3 11

3. x s N

Kymi r i v e r , 2.3 0.0 3.2 0.0 3 3

Salmon 22.7 26.4 3

1.7 2.1 3

0.0 0.0 3

0.0 0.0 3

4. × s N

H a t c h e r y , Salmon 1.1 0.5 0.3 1.5 1.6 0.7 10 10 10

1.2 2.6 10

17.6 25.5 10

2.9 4.0 10

456TC8

TeC8

SUM

1.7 4.4 15

7.9 16.7 15

65.1 72.7 15

2.2 4.4 11

0.0 0.0 11

1.4 2.2 11

101.1 172.2 11

1.0 1.7 3

0.0 0.0 3

4.0 6.9 3

3.0 2.6 3

34.7 28.0 3

1.3 2.4 10

6.0 12.1 10

1.8 5.7 10

0.1 0.3 10

32.8 32.4 10

TABLE 8 . P e a r s o n c o r r e l a t i o n c o e f f i c i e n t s i n f r e s h muscles o f t h e w i l d salmons ( p o p u l a t i o n s 1 and 3 ) . S i g n i f i c a n c e s : * * p =< 0 . 0 1 and * * * p =< 0 . 0 0 1 . Fat Weight Lenght DDE DDD DDT LIND HCB PCB OXY ALPHA GAMMA TRANS TeCP PeCP TECG 246TCP DMP

.4257 .4813 .9768 .9958 .9387 -.4040 .7079 .9456 .7965 .9256 .1190 .9211 -.6960 -.2470 .2578 -.1044 -.7170

** ** *

* * *

Weight

Lenght

1.0000 .9801 * * .2948 .4250 .4859 .3474 -.2663 .5055 .4806 .4054 .8919 * .5346 .5876 .9834 * * -.0378 -.4119 -.3014

.9801 * * 1.0000 .7298 .7990 .8260 .0313 .1848 .8811 .8434 .6045 .6979 .8334 .4364 .9750 -.1521 -.4268 -.4808

1737

Pearson c o r r e l a t i o n s ( T a b l e 8) oT t h e measured r e s i d u e c o n t e n t s w i t h Tat w e r e p o s i t i v e and many a l s o s i g n i T i c a n % T o t c h l o r o h y d r o c a r b o n s e x c e p t T o t l i n d a n ( L I N D } . I n c o n t r a r y , c h l o r o p h e n o l s showed no s i g n i n i T i c a n c e i n the corresponding correlations. T h e r e T o r e , i n c o m p a r i s o n s between p o p u l a t i o n s and t i s s u e s T a t b a s i s i s t a k e n T o t c h l o r o h y d r o c a v b o n s and Tresh w e i g h t basis Tor c h l o r o p h e n o l s . Due t o t h e common s o u r c e sum oT t h e DDT r e s i d u e s (SDDT = DDE+DDD+DDT) and sum oT t h e c h l o r d a n e r e s i d u e s (SCHL = OXY+GAMMA+ ALPHA+TRANS) on T a t b a s i s i s compared. I n c o m p a r i s o n oT t h e c h l o r o p h e n o l s o n l y t h e i r sum i s t a k e n i n t o a c c o u n t w h i l e i t showed l o w e r v a r i a t i o n than the individual compounds ( T a b l e s 5 - 7 ) . These s u m m a r i s i n g c o m p a r i s o n s a r e p r e s e n t e d i n F i g . 4.

.T~O;ppb

HCB in f a t liver

muscle

ppm

m.

eggs

PCB in f a t liver

muscle

eggs

20~

o

1 2

ppm 1o.

~i

q

1 2

3

~

I

2

3

o

q

ppm 2.

Sum of DDT residue~ in f a t muscle liver eggs

NNn 1

2 3

q

1 2

ppm LIND [:3 z~ muscle

)

q

i,-,

12

and liver

SYM r~

z 3

3

1

in f a t eggs

q

12

I-1FlnF1 1

3 q

2 ,3 q

Sum of chlordanes in f a t muscl e I i ver eggs

I

3 q

2 )

2

3

q

1 2

3 4

1

2 ]$

q

ppb Sum of chlorophenols in fresh eggs i .muscle l i v e r

°"

o

I

r~

F-1

2 I q I

;,

Ix

q I

qlz

....

z 3

q 1 ~

il ,t-t 1 2'3

q

I Fdt. q

12

~ q

FIGURE 4. A v e r a g e c o n t e n t s i n d i f f e r e n t t i s s u e s o f t h e four populations: 1. Kemi r i v e r s a l m o n . 2 . Kemi r i v e r t r o u t . 3. Kymi r i v e r s a l m o n . 4. H a t c h e r y salmon.

1738

Weight and l e n g t h showed no s i g n i f i c a n t Pearson c o r r e l a t i o n s i n fish muscles e x c e p t weight t o PeCP and GAMMA| T a b l e 8. More i n f o r m a t i o n on p o s s i b l e i n t e r f e r e n c e s was o b t a i n e d by s t e p w i s e m u l t i p l e l i n e a r regression analyses / 1 1 / where F a t , Weight, Lenght and P o p u l a t i o n were taken t o be e x p l a n a t o r y v a r i a b l e s . The l a t t e r were f r e q u e n t l y s i g n i f i c a n t f o r chlorohydrocarbons e x c e p t never f o r OXY, LIND and SYM, n o n s i g n i f i c a n t f o r c h l o rophenols. Covariance ANOVA t e s t which e l i m i n a t e s t h e i n t e r f e r e n c e of Weight, Lenght and Fat showed t h a t t h e d i f f e r e n c e s between t h e chlorohydrocarbon c o n t e n t s of p o p u l a t i o n s were s i g n i f i c a n t e x c e p t f o r LIND and SYM. In c o n t r a r y , o n l y few s i g n i f i c a n t d i f f e r e n c e s o f t h e p o p u l a t i o n s were o b t a i n e d f o r chlorophenols. The l a t t e r were those of PeCP i n a l l t i s s u e s and those o f TeCP i n muscles and l i v e r s . For

chlorohydrocarbons5

t h e d i f f e r e n c e s between t i s s u e s

were

nonsignifi-

cant. However, contents in l i v e r f a t i n most cases were s l i g h t l y lower than i n muscle o r egg f a t ( F i g . 4 ) . More v i s i b l y , c h l o r o p h e n o l l e v e l s o f liver were h i g h e r than t h o s e of muscle o r eggs ( f r e s h weight b a s i s ; F i g . 4). A general food chain enrichment power o f o r g a n o c h l o r i n e s c o u l d be

estima-

ted by comparing average c o n t e n t s measured i n s p e c i e s r e p r e s e n t i n g d i f f e r e n t t r o p h i c l e v e l s . With t h e p r e s e n t salmon r e s u l t s such comparisons might be done as presented i n Tables 9 and 10.

TABLE 9.

Average c o n t e n t s ppm i n muscle f a t

Species/ Population

HCB

PCB

Starling/ F i n l a n d 1983

.043

1.44

Pike/Vatia f r e s h w a t e r 83

.020

Herring/ B a l t i c 1982

Sum of DDT

tissues. Sum of Chlord.

LIND

Refefence

.523

.076

.334

14

2.68

.061

.000

.020

15

7.00

2.14

.563

16

Salmon/ 1. Kemi r i v e r 82

.401

6.68

7.70

1.03

.000

T h i s work

Sea g u l l / B a l t i c 83

.460

86.3

31.6

1.35

.006

17

Osprey/ F i n l a n d 70-82

.21&

29.1

16.7

.847

.201

17

White-tailed eagle/Baltic 1980-83

13.0

12182

3603

148.3

7.08

17

1739

Table 10. Average c h l o r o p h e n o l c o n t e n t s ppb i n f r e s h muscles. Species/ Population

34DCC

246TCP

TeCP

PeCP

.083

1.21

14 15

Starling/ F i n l a n d 1983

.000

Burbot/Vatia # f r e s h w a t e r 83

37.3

9.20

12.1

2.6

Salmon/ 1. Kemi r i v e r 82

19.2

1.9

5.0

1.8

White-tailed eagle/Baltic 1980-83

0.00

63.8

89.0

2152 ##

Refefence

T h i s work 17

# F i v e km downstreams from a pulp b l e a c h i n g p l a n t ## Very l a r g e v a r i a t i o n from 14 t o 8571 ppb

Comparison o f t h e c h l o r o h y d r o c a r b o n l e v e l s p o i n t s o u t c h l o r d a n e s as possible e n v i r o n m e t a l p o i s o n s which a r e s i m i l a r t o PCB and DDT r e s i d u e s . T h e i r l e v e l i n t h e p r e s e n t salmon samples i s however low, ~hich i s unders t a n d a b l e because c h l o r d a n e s never have been used i n S c a n d i n a v i a . They form an i m p o r t a n t group o f g l o b a l p o l l u t a n t s which come t o our environment by athmospheric t r a n s f e r and are d e t e c t a b l e a l l around i n biosphere /1420/. P e s t i c i d e LIND and g l o b a l p o l l u t a n t HCB which i s a f u n g i c i d e b u t comes i n major amounts from combustions / 2 1 , 2 2 / were w i d e l y d e t e c t e d i n salmons, t o o , b u t showed n o t v e r y h i g h food chain enrichment p o t e n t i a l . 34DCC i s one of t h e main c h l o r o p h e n o l s formed i n pulp bleaching ( l i g n i n c h l o r i n a t i o n ) process. T h e r e f o r e i t s appearance i n salmons c o u l d i n d i c a t e a wide i n f l u e n c e range of c h l o r i n a t i o n s . The o t h e r c h l o r o p h e n o l s g e n e r a l l y found 246TCP, TeCP and PeCP a r e formed i n c h l o r i n a t i o n o f phenol t o make wood p r e s e r v a t i v e s and i n waste combustions / 2 3 , 2 4 / . These f o u r components do n o t show v e r y high enrichment poNer a l t h o u g h PeCP was once anomalously found a t h i g h l e v e l i n r o t t e n w h i t e - t a i l e d e a g l e muscle / 1 7 / . In c o n t r a r y , some o t h e r PCPs and PCGs had shown b i o a c c u m u l a t i o n and enrichment p r o p e r ties i n a q u a t i c food c h a i n / 4 , 5 , 1 2 , 1 5 / which was seen i n t h e p r e s e n t s a l mon and t r o u t samples o n l y as an o c c a s i o n a l appearance o f t h e s a m e compounds (Tables 5 - 7 ) . To a c h i e v e more p r e c i s e i n f o r m a t i o n o f p o s s i b l e environmental impact of o r g a n o c h l o r i n e compounds d e t e c t e d i n f i s h , b i r d s p e c i e s , t h e i r eggs and j u v e n i l e s which have f i s h as food should be s t u d i e d by manner d e s c r i b e d by i n one o f our r e p o r t s i n 1981 / 2 5 / . There are o t h e r p e r s i s t e n t o r g a n o c h l o r i n e s , p o t e n t i a l b i o c i d e s , which are not y e t w e l l s t u d i e d . We suspect t h a t c h l o r o p h e n o l s might form p e r s i s t e n t m e t a b o l i t e s . Consequently, p o s s i b l e appearance of b i o m e t h y l a t e d c h l o r o p h e n o l i c ( a l s o d i m e r i c ) compounds and n e u t r a l c h l o r o p h e n o l dimers (PCDPE, PCDF and PCDD), c a l l e d t o g e t h e r a r o m a t i c c h l o r o e t h e r s (ACEs) / 2 6 / , i n s a l mon and t r o u t i s under s t u d y i n our l a b o r a t o r i e s .

A~knowledoements. We would l i k e to extend our thanks t o Kemijoki Oy f o r t h e salmons and t r o u t o f t h e K e m i j o k i p o p u l a t i o n . The s t u d y was f i n a n c i a l l y supported by t h e M i n i s t r y o f A c r i c u l t u r e and F o r e s t r y of Finland (LYSTI workgroup).

1740

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(Received in Germany 24 June 1985; accepted

ii October

1985)