- Email: [email protected]
Chlorinated dioxin and dibenzofuran levels in food and wildlife samples in the North and South of Vietnam
C h e m o s p h e r e , Vol.19, Nos.l-6, P r i n t e d in Great B r i t a i n
CHLORINATED
pp 493-496,
1989
0 0 4 5 - 6 5 3 5 / 8 9 $3.00 + .00 P e r g a m o n Press plc
D I O X I N A N D D I B E N Z O F U R A N LEVELS IN FOOD A N D W I L D L I F E S A M P L E S IN THE N O R T H A N D S O U T H OF V I E T N A M
K. Olie l, A. S c h e c t e r 2, J. C o n s t a b l e 3, R.M.M. K o o k e I, P. S e r n e I, P.C. Slot I and P. de V r i e s I
I. L a b o r a t o r y of E n v i r o n m e n t a l and T o x i c o l o g i c a l C h e m i s t r y U n i v e r s i t y of A m s t e r d a m N i e u w e A c h t e r g r a c h t 166, 1018 W V Amsterdam, The N e t h e r l a n d s 2. D e p a r t m e n t of P r e v e n t i v e M e d i c i n e C l i n i c a l C a m p u s of Binghampton, S t a t e U n i v e r s i t y Health Science Centre / Syracuse 88 A l d r i c h Avenue, Binghampton, NY 13903, U.S.A. 3. D e p a r t m e n t of S u r g e r y H a r v a r d M e d i c a l School M a s s a c h u s e t t s G e n e r a l Hospital,
Boston,
MA 02119,
of N e w Y o r k
U.S.A.
ABSTRACT More than 35 food and w i l d l i f e s a m p l e s from N o r t h and S o u t h V i e t n a m were a n a l y z e d in o r d e r to s t u d y the l o n g - t e r m effects of "Agent O r a n g e " spraying. The a n a l y t i c a l r e s u l t s are presented. The results i n d i c a t e that the levels in the S o u t h V i e t n a m e s e s a m p l e s are h i g h e r than in the N o r t h V i e t n a m e s e samples. It is s u g g e s t e d that p a r t of this d i f f e r e n c e may be due to the s p r a y i n g of "Agent Orange".
Keywords:
PCDD,
PCDF,
food,
wildlife,
Vietnam
INTRODUCTION During the S e c o n d I n d o c h i n a W a r of 1961 - 1975, 10% of the land area of the south of V i e t n a m is b e l i e v e d to h a v e been c o n t a m i n a t e d w i t h about 170 kg of 2,3,7,8 - TCDD. The estimated amount per unit area, assuming uniform d i s t r i b u t i o n , is 2 6 3 m g / h a (Westing et ai.,1984). Some areas are s p r a y e d more than once, 19x103 ha even five or m o r e times. In those areas an amount of more than 500 m g / h a can be expected. The action of w a t e r and w i n d is likely to have d e c r e a s e d the c o n c e n t r a t i o n s in these areas. A good p i c t u r e of c o n c e n t r a t i o n s in soil is not available. One of the aims of this study is to find out w h e t h e r or not there is p e r s i s t e n c y of the 2,3,7,8 - T C D D c o n t a m i n a n t in w i l d l i f e and food in the south of Vietnam. 2,4,5-T, one of the active s u b s t a n c e s in "Agent Orange", has 2 , 3 , 7 , 8 - T C D D as the only p e r s i s t e n t d i o x i n as a contaminant. In other sources (municipal waste and industrial incineration, paper and pulp b l e a c h i n g etc.) 2 , 3 , 7 , 8 - T C D D is found t o g e t h e r with o t h e r c h l o r i n a t e d dioxins and d i b e n z o f u r a n s . To see w h e t h e r or not t h e r e is still the p e r s i s t e n c e of T C D D from the h e r b i c i d e spraying, it is n e c e s s a r y to c o m p a r e the r e s u l t s w i t h a n o t h e r area /
493
494
w h i c h is k n o w n not to be c o n t a m i n a t e d w i t h 2,3,7,8 - T C D D from h e r b i c i d e use. We u s e d the n o r t h e r n p a r t of V i e t n a m for this purpose. Previous studies (Schecter et ai.,1986) showed e l e v a t e d 2,3,7,8 -TCDD in human a d i p o s e t i s s u e and milk, p a r t i a l l y from "Agent Orange", and other p e n t a - o c t a PCDD/FS from industrial sources in the South but not in the North. M A T E R I A L S AND M E T H O D S Food and w i l d l i f e s p e c i m e n s w e r e c o l l e c t e d by two of us (AS & JC) from m a r k e t s in the n o r t h and s o u t h of Vietnam, from f i s h e r m e n and w o m e n and in fields, b e t w e e n 1985-1987. S p e c i m e n s were frozen and sent to Europe for chemical analysis at the L a b o r a t o r y of E n v i r o n m e n t a l and T o x i c o l o g i c a l C h e m i s t r y of the U n i v e r s i t y of Amsterdam. T h e y are a n o n - r a n d o m sample and, therefore, not n e c e s s a r i l y r e p r e s e n t a t i v e of the c o u n t r y as a whole. The treatment, c l e a n - u p and a n a l y s i s of the samples has b e e n d e s c r i b e d e a r l i e r (Schecter et al., 1989). All results are b a s e d on wet weights. The last column in t a b l e II shows the total burden, expressed in Toxic Equivalents. RESULTS More than 35 s a m p l e s w e r e analysed. The a n a l y s i s was s p e c i f i c for the 2,3,7,8 s u b s t i t u t e d d i o x i n s and d i b e n z o f u r a n s . Several samples from the S o u t h as well as from the N o r t h did not c o n t a i n c h l o r i n a t e d d i o x i n s or c h l o r i n a t e d d i b e n z o f u r a n s a b o v e the d e t e c t i o n limit of our method. Listed in t a b l e I are the a n a l y z e d isomers, the c o r r e s p o n d i n g p e a k numbers and the T o x i c E q u i v a l e n c e Factors (Zorge et al., 1988) as d e f i n e d by the Dutch State D e p a r t m e n t of E n v i r o n m e n t a l Health. In table II our analytical results are presented.
TABLE I. Congeners,
p e a k n u m b e r s and T o x i c E q u i v a l e n c y Factors
compound 2 1,2 1,2,3 1,2,3 1,2,3 1,2,3,4
3,7,8-T4CDD 3,7,8-P5CDD 4,7,8-H6CDD 6,7,8-H6CDD 7,8,9-H6CDD 6,7,8-H7CDD OCDD
2 3,7,8-T4CDF 1,2 3 , 7 , 8 - P s C D F (+1,2 3 , 4 , 8 - P 5 C D F ) 2,3 4 , 7 , 8 - P s C D F 1,2,3 4 , 7 , 8 - H 6 C D F (+1,2,3 4 , 7 , 9 - H 6 C D F ) 1,2,3 6 , 7 , 8 - H 6 C D F 1,2,3,7,8,9-H6CDF 2,3,4,6,7,8-H6CDF 1,2,3,4,6,7,8-H7CDF 1,2,3,4,7,8,9-H7CDF OCDF
peaknr, 7 48 79 80 82 98 103
tox.eq.factor (TEF) 1 0.5 0.i 0.i 0.i 0.01 0.001
37 64
0.i 0.05
74 88
0.5 0.i
89 94 96 99 102 104
0.I 0.i 0.i 0.01 0.01 0.001
Isomers w i t h i n p a r e n t h e s e s are not s e p a r a b l e from the p r e v i o u s one.
495
TABLE I I - A : PCDDCONCENTRATIONS(pPT/WET WEIGHT) IN VIETNAMESESAMPLES; CONGENERS ARE IDENTIFIED BY PEAKNUMBERAS EXPLAINEDIN TABLE I;
peaknr. tox.eq.
40 0.5
79 0.1
60 0.1
02 0.1
90 0.01
103 0.001
< 0.32 < 0.61
< 0.57 2.24
< 2.00 < 0.36
< 2.96 1.27
< 0.74 < 0.60
< 4.55 3.40
< 22.63 25.53
S. S. S.
60,16 11.50
< 0.06 < 0.07 < 0.10 M.D. 1.26 0.67 7.97 1,82 1.35 21.53 1.10 < 0.15 < 1.24 < 0,13 0.02 < 0.92 0.21 M.D. M.D. H.D. N.D. N.D. N.D. 1.50 N.D. < 0,19 N.D. 0.43 0,51 N.D. 3.43 5.74 < 0.91
0.14 0.14 0.15 N,D. 0.94 N.D. 6,57 1.22 0.26 4.14 1.16 0.16 0.43 < 0.07 0.02 3.58 0.11 0.26 N.O. H.D. N.D. 0.66 H.D. 0.56 N.D. 0.14 M.D. 0.72 2.23 1.02 1.60 5.45 1.28
< 0.05 0.13 0.15 0.40 1.12 0.92 2.97 0.60 0.66 3.65 1.28 0.16
S.
0.37 0.13 0.23 M.D. 0.05 0.77 3.14 0.77 0.47 3.13 0.16 0.33 0.46 0.07 0.11 2.45 0.06 N.D. M.D. H.D. M.D. M.D. H.D. O.30 < 1.20 < 0.02 N.D. 1.01 1.35 19,04
0.76 1.15 1.39 7.70 IO,01 8.77 25.99 6.86 26,69 134.09 10.65 1.49 1.44 0.31 0.38 10.45 0.88 5.70 0.69 2.10 1.40 5.80 1.20 4.80 2.10 2.72 N.D. < 1.03 N,D. N.D. N.D. N.D. 5.54
PORK PORK
HANOI HANOI
H.
PORK FAT CAT FISH CARp EEL COW FAT CHICKEN FAT PORK FAT PORK FAT PORK PAT CHICKEN FAT CHICKEN EGG FISH PISH CNAHNA FISH MUSCLE CHANNA FISH MUSCLE CHANNA FISH LIVER CLARIUS FISH MUSCLE CAT FISH EEL EEL SEA FISH SONG BIEN CNIVANG FISH SONG LAM FISH CRAB CRAB MEAT CHICKEN EGGS DUCK EGGS TURTLE PAT TURTLE MUSCLE TURTLE LIVER TURTLE GALL- BLADDER TURTLE OVARIES SNAKE
HANOI KA~OI HANOI HANOI HA~OI HA/401
H. N. H. N. N. N. S. S.
S O N G BE S O N G BE TA/4UY EN TANUYEN TA~ IHAN
S,
H.
S. S. S. S. S. S. S. S. B I N H T H I T H I E N S. HOCMCITY S. HOCMCITY S . HOCMCITY S. HDCMCITY S. HOCMCITY S. HO ~MCITY S. HOCMCITY S. HOCMCITY S. qOCMCITY S. S, S.
TANHANH
7 1
2.20
0.27 0.24 0.41 0.42 3.27 1.13 6.13 2.42 1.51 29,92 2.15 0.42 0.62 0.14 0.04 4.20 0.15 1.20 0.12 M.D. N.D. 0.75 0.82 i.i0 0.26 0.67 N.D. 1.00 4,73 3.55 3,95 28.26 2.50
0,20
< 0.04 0.05 < 1.30 0.06 0.66 H.D. N,D. N.D. N.D, N.D. 0.92 0.17 0.23 N.D. 1.05 N.D. 2.86 N.D. 23.24 1.01
2.53 3.99 6.90 58.00 14.57 21.50 90,28 23.60 91,09 96.86 69.00 6,47 6.02
< 0.55 0.54 16.70 2.33 N.D. 12.00 20.00 18.00 N,D. 11.00 12.60 9.10 17.77 N.D. ND N.O. N.D. N.D. N.D. 55.58
N.=North Vietnam; S.:South Vietnam
TABLE II-B : PCDFCONCENTRATIONS(PPT/WET WEIGHT) IN VIETNAMESESAMPLES; CONGENERSARE IDENTIFIED 8Y PEAK NUMBERAS EXPLAINEDIN TABLE I. LAST COLUMNPRESENTSTOTAL (PCDD+PCDF) BURDENIN TOXIC EQUIVALENTS;
peaknr. tox. aq.
37 0.1
PORK
}t~OI
H.
2.47
PORK PORK FAT CAT F I S H CARP EEL COW FAT CHICKEN PAT
HANOI HANOI HANOI HANOI HANOI HANOI HAHOI
H. H. N. N. N.
0.|1 0.06 0.3S 0.77 H.D. 1.00 4.10
PORK FAT PORK FAT PORK FAT CHICKEN FAT CHICKEN EGG FISH FISH CHANRA FISH MUSCLE
S O N G 80 S O N G BE TA~rUYEH TANUYEN TANIHAM
CNAHNA F I S H MUSCLE
N. H.
S. S. S. SS~ S. S. S.
4.95 2.12 2.11 8.44 < 0.20 0.58 0.12 0.19
64 0.05
74 0.5
3.61
2.63
1.58 0.1| 0.41 < 0.32 M.D. 2,62 4.51
1.22 0,20 < 0.16 0.40 N.D. 1.92 1.95
4.19 0.14 1.71 14.08 0.66 < 0.40 O.68 0.21
1.12 2.10 2.08 15.54 0,18 < 0,16 0.16 0.11
1.29 0.75 0.06 0.07 0.22 0.32 0.92 0.99
1.53 1.69 1.42 I0.24 0.69 0.07 0.32 < 0.03
89 0.1
94 0.1
0.61
96 0.1
< 0.92
< 1,02
0,63 < 0.04 0.00 0.12 0.12 0.81 0.53
< 0.12 0.26 < 0.11 < 0.06 H.D. M.D. N.D.
< < < <
0.69 0.87 0.95 3.73 0.27 0.00 0,56 < O.O9
O.61 < O.49 H.D, 15.16 < 0.16 0.30 < 0.05 < 0.06
1.61 < 0.54 0.66 0.57 0.44 < 0,44 < 0.I0 < 0.03
0.39 0.16 0.12 0.07 N.D. N.D. N.D.
99 0.01
102 0.01
104 0.001
< 1.20
TOTAL
< 5.79
<40.66
1.99
0.99 1,16 0.45 0.64 6.40 N.D. 1.34
< 0.82 < 0,17 N.D. 0.23 N.D. N.D. N.D.
< 6.90 < 1.31 N.D. < 1.72 N.D. M.D. N.D.
2.24 0.59 0.26 0.64 0.35 3.51 3.30
4.33 6.16 5.50 13.06 1.06 0.26 0,35 0.10
< 1.20 < 2.11 N.D. N.D. < 0.15 0.13 < 0,34 0.15
< 4.91 < 5.79 N,D, N,D. 0.$2 0.64 < 2.92 < 0.99
10,99 4.07 3.46 31.54 1,62 0.53 0.92 0.17
S. S.
0.15 2.67
0,14 3.77
0,05 1.70
0.04 1.49
< 0.02 < 1.24
< 0.03 < 1.36
0.09 3.19
0.09 < 2.88
< 0.49 < 7.15
0.26 4.16
BINH TRI THIEN HOCMCITY HOCMCITY HOCMCITY HOCMCITY HOCMCITY
S. S. S. S. S. S. S.
0.26 M.D. H.D. M.D. H.D. M.D. M.D.
0.29 M.D. M.D. M.D. M.D. M.D. M.D.
0.15 I0.60 N.D. N.D. M.D. M.D. 0.03
0.12 0.66 0.07 H.D. M.D. 2.50 N.D.
0.09 M.D. H.D. H.D. M.D. H.D. N.D.
0.04 M.D. M.D. N,D. H.D. H.D. M.D.
0.10 M.D. N.D. M.D. N,D. N.D. H.O.
0.37 4.00 0.49 2.70 1.50 45.00 0.65
< 0.II H.D. N.D. N.D, N.D. M.D. N.D.
< 0.36 N.D. N.D. M.D. N.D. M.D. H.D.
0.36 ~.65 0.04 O.O7 0.05 0.90 0.28
CRAB CRAB MEAT
HOC~CITY HOCMCITY
S. S.
7.50 M.D.
1.10 N.D.
079 0.85
0.33 N.D,
N.D. M.D.
H.D. N.O.
N.D. N.D.
1.20 2.10
N.D. N.D.
N.D. N.D.
2.64 0.52
CHICKEN EGGS DUCK EGGS
HOCMCITY HOCMCITY
S, S.
0.47 R. D.
0.47 H. D.
0.37 M.D.
0.94 N.D.
0.15 M.D.
0.29 M.D.
< 0.27 N.D.
1.42 M.D.
< 0.35 M.D.
< 3.48 N.D.
0.36 M.D.
0.39 N.D.
0.19 N.D,
< 0.00 N.D.
< 0.17 M.D.
< 0.19 N.D.
0.53 N,D.
< 1,11 H.D.
M.D. N.D.
1.76 2.56
S.
2.95 0.06
4.27 2.80
2.13 2.96
2.03 2.12
1.23 N.D,
M.D. M.D.
N.D. N.D,
i.ii 10.31
N.D, H.D.
N.D, N.D.
39.95 1.29
22,40 1.59
9.28 0.91
4.64 0.39
N.D. < 0.38
M.D. < 0.42
N.D. 0.61
N.D. < 0.64
N.D. < 2.73
21.70 6.54 85,71
CHANHA FISH LIVER CLARIUS FISH MUSCLE CAT FISH EEL EEL SEA FISH SONG BIEN CHIVARG FISH SONG LAM FISH
TURTLE TURTLE
FAT MUSCLE
TURTLE LIVER TURTLE GALL-BLADDER TURTLE OVARIES SNAKE
S, S.
sS~ TANHANH
S.
0.22 2.57
23.91 < 0.65
0.1| < 1.21
88 0.1
0.55 0.00
13,17
496
CONCLUSIONS AND DISCUSSION We can confirm and extend our previous conclusions (Schecter et al., 1989). It is evident that the Vietnamese samples show a wide spread of PCDD and PCDF levels. This suggests that localized sources play an important role. In order to compare the PCDD and PCDF burden in North and South Vietnam, the mean concentration per isomer was calculated. Samples with concentrations below the detection limit were omitted from the mean value calculation. Therefore, the figures cannot be easily used to assess the 2,3,7,8 -TCDD uptake by food. In addition, the South Vietnamese turtle samples were omitted from this calculation, because these samples were all derived from the same animal. The mean total (PCDDs + PCDFs) concentration in the samples from the South (78 ppt) is higher than in samples from the North (36 ppt). This can well reflect the difference in industrialisation between the North and South of Vietnam. In the samples from the South, 2,3,7,8-TCDD accounts for 2.5% of the total of the PCDD-PCDF burden. In the Northern samples the relative amount is 1.3%. The higher relative abundance of 2,3,7,8-TCDD in the South suggests that 2,3,7,8-TCDD from "Agent Orange" spraying has entered the ecological system. The results for fresh water fish from the North and South of Vietnam show low contaminations of the fish and resemble more or less samples from other industrialized areas in the world, although the Vietnamese concentrations are less contaminated (Stalling et al., 1983; Rappe et al., 1987). Unfortunately a comparison for our crab sample and the Swedish results is not possible because there only the hepatopancreas is measured (Rappe et al.,
1983). It seems that for sea fish the contamination lower than in fish from industrialized areas.
with
chlorinated
dioxins
is
REFERENCES Rappe, C., Andersson, R., Bergqvist, P., Brohede, C., Hansson, M., Kjeller, L., Lindstr6m, G., Marklund, S., Nygren, M., Swanson, S.E., Tysklind, M., Wiberg, K., Chemosphere 16, 1603-1618, 1987. Schecter,
A., Ryan, J., Constable,
J., Chemosphere
15, 1613-1620,
Schecter, A., Kooke, R., Sern~, P., Olie, K., Constable, D6 Quang Huy, Chemosphere, 18, 621-628, 1989. Schecter, A., F~rst, Chemosphere, in press.
P.,
KrUger,
C.,
Meemken,
H.A.,
1986.
J., Nguye~ Duc Hu~, and
Groebel,
W.,
Stalling, D.L., Smith, L.M., Petty, J.D., Hogan, J.W., Johnson, J.L.,Rappe, C., Buser, H.R., "Residues of polychlorinated dibenzo-p-dioxins and dibenzofurans in Laurentian Great Lakes fish.", from "Human and Environmental risks of chlorinated dioxins and related compounds.", Eds. Tucker, R.E., Young, A.L., Gray, A.P., Plenum Publ. Corp., New York, 1983. "Herbicides in war. The long term ecological human consequences." Westing, A.H., Taylor and Francis, London and Philadelphia, 1984. Zorge, J.A.v., Theelen, R.M.C., Wijnen, J.H.v., Olie, K., Berg, Report: "Werkgroep toxiciteitsequivalentiefactoren", maart 1988.
Ed.
M.v.d.,
CHLORINATED
pp 493-496,
1989
0 0 4 5 - 6 5 3 5 / 8 9 $3.00 + .00 P e r g a m o n Press plc
D I O X I N A N D D I B E N Z O F U R A N LEVELS IN FOOD A N D W I L D L I F E S A M P L E S IN THE N O R T H A N D S O U T H OF V I E T N A M
K. Olie l, A. S c h e c t e r 2, J. C o n s t a b l e 3, R.M.M. K o o k e I, P. S e r n e I, P.C. Slot I and P. de V r i e s I
I. L a b o r a t o r y of E n v i r o n m e n t a l and T o x i c o l o g i c a l C h e m i s t r y U n i v e r s i t y of A m s t e r d a m N i e u w e A c h t e r g r a c h t 166, 1018 W V Amsterdam, The N e t h e r l a n d s 2. D e p a r t m e n t of P r e v e n t i v e M e d i c i n e C l i n i c a l C a m p u s of Binghampton, S t a t e U n i v e r s i t y Health Science Centre / Syracuse 88 A l d r i c h Avenue, Binghampton, NY 13903, U.S.A. 3. D e p a r t m e n t of S u r g e r y H a r v a r d M e d i c a l School M a s s a c h u s e t t s G e n e r a l Hospital,
Boston,
MA 02119,
of N e w Y o r k
U.S.A.
ABSTRACT More than 35 food and w i l d l i f e s a m p l e s from N o r t h and S o u t h V i e t n a m were a n a l y z e d in o r d e r to s t u d y the l o n g - t e r m effects of "Agent O r a n g e " spraying. The a n a l y t i c a l r e s u l t s are presented. The results i n d i c a t e that the levels in the S o u t h V i e t n a m e s e s a m p l e s are h i g h e r than in the N o r t h V i e t n a m e s e samples. It is s u g g e s t e d that p a r t of this d i f f e r e n c e may be due to the s p r a y i n g of "Agent Orange".
Keywords:
PCDD,
PCDF,
food,
wildlife,
Vietnam
INTRODUCTION During the S e c o n d I n d o c h i n a W a r of 1961 - 1975, 10% of the land area of the south of V i e t n a m is b e l i e v e d to h a v e been c o n t a m i n a t e d w i t h about 170 kg of 2,3,7,8 - TCDD. The estimated amount per unit area, assuming uniform d i s t r i b u t i o n , is 2 6 3 m g / h a (Westing et ai.,1984). Some areas are s p r a y e d more than once, 19x103 ha even five or m o r e times. In those areas an amount of more than 500 m g / h a can be expected. The action of w a t e r and w i n d is likely to have d e c r e a s e d the c o n c e n t r a t i o n s in these areas. A good p i c t u r e of c o n c e n t r a t i o n s in soil is not available. One of the aims of this study is to find out w h e t h e r or not there is p e r s i s t e n c y of the 2,3,7,8 - T C D D c o n t a m i n a n t in w i l d l i f e and food in the south of Vietnam. 2,4,5-T, one of the active s u b s t a n c e s in "Agent Orange", has 2 , 3 , 7 , 8 - T C D D as the only p e r s i s t e n t d i o x i n as a contaminant. In other sources (municipal waste and industrial incineration, paper and pulp b l e a c h i n g etc.) 2 , 3 , 7 , 8 - T C D D is found t o g e t h e r with o t h e r c h l o r i n a t e d dioxins and d i b e n z o f u r a n s . To see w h e t h e r or not t h e r e is still the p e r s i s t e n c e of T C D D from the h e r b i c i d e spraying, it is n e c e s s a r y to c o m p a r e the r e s u l t s w i t h a n o t h e r area /
493
494
w h i c h is k n o w n not to be c o n t a m i n a t e d w i t h 2,3,7,8 - T C D D from h e r b i c i d e use. We u s e d the n o r t h e r n p a r t of V i e t n a m for this purpose. Previous studies (Schecter et ai.,1986) showed e l e v a t e d 2,3,7,8 -TCDD in human a d i p o s e t i s s u e and milk, p a r t i a l l y from "Agent Orange", and other p e n t a - o c t a PCDD/FS from industrial sources in the South but not in the North. M A T E R I A L S AND M E T H O D S Food and w i l d l i f e s p e c i m e n s w e r e c o l l e c t e d by two of us (AS & JC) from m a r k e t s in the n o r t h and s o u t h of Vietnam, from f i s h e r m e n and w o m e n and in fields, b e t w e e n 1985-1987. S p e c i m e n s were frozen and sent to Europe for chemical analysis at the L a b o r a t o r y of E n v i r o n m e n t a l and T o x i c o l o g i c a l C h e m i s t r y of the U n i v e r s i t y of Amsterdam. T h e y are a n o n - r a n d o m sample and, therefore, not n e c e s s a r i l y r e p r e s e n t a t i v e of the c o u n t r y as a whole. The treatment, c l e a n - u p and a n a l y s i s of the samples has b e e n d e s c r i b e d e a r l i e r (Schecter et al., 1989). All results are b a s e d on wet weights. The last column in t a b l e II shows the total burden, expressed in Toxic Equivalents. RESULTS More than 35 s a m p l e s w e r e analysed. The a n a l y s i s was s p e c i f i c for the 2,3,7,8 s u b s t i t u t e d d i o x i n s and d i b e n z o f u r a n s . Several samples from the S o u t h as well as from the N o r t h did not c o n t a i n c h l o r i n a t e d d i o x i n s or c h l o r i n a t e d d i b e n z o f u r a n s a b o v e the d e t e c t i o n limit of our method. Listed in t a b l e I are the a n a l y z e d isomers, the c o r r e s p o n d i n g p e a k numbers and the T o x i c E q u i v a l e n c e Factors (Zorge et al., 1988) as d e f i n e d by the Dutch State D e p a r t m e n t of E n v i r o n m e n t a l Health. In table II our analytical results are presented.
TABLE I. Congeners,
p e a k n u m b e r s and T o x i c E q u i v a l e n c y Factors
compound 2 1,2 1,2,3 1,2,3 1,2,3 1,2,3,4
3,7,8-T4CDD 3,7,8-P5CDD 4,7,8-H6CDD 6,7,8-H6CDD 7,8,9-H6CDD 6,7,8-H7CDD OCDD
2 3,7,8-T4CDF 1,2 3 , 7 , 8 - P s C D F (+1,2 3 , 4 , 8 - P 5 C D F ) 2,3 4 , 7 , 8 - P s C D F 1,2,3 4 , 7 , 8 - H 6 C D F (+1,2,3 4 , 7 , 9 - H 6 C D F ) 1,2,3 6 , 7 , 8 - H 6 C D F 1,2,3,7,8,9-H6CDF 2,3,4,6,7,8-H6CDF 1,2,3,4,6,7,8-H7CDF 1,2,3,4,7,8,9-H7CDF OCDF
peaknr, 7 48 79 80 82 98 103
tox.eq.factor (TEF) 1 0.5 0.i 0.i 0.i 0.01 0.001
37 64
0.i 0.05
74 88
0.5 0.i
89 94 96 99 102 104
0.I 0.i 0.i 0.01 0.01 0.001
Isomers w i t h i n p a r e n t h e s e s are not s e p a r a b l e from the p r e v i o u s one.
495
TABLE I I - A : PCDDCONCENTRATIONS(pPT/WET WEIGHT) IN VIETNAMESESAMPLES; CONGENERS ARE IDENTIFIED BY PEAKNUMBERAS EXPLAINEDIN TABLE I;
peaknr. tox.eq.
40 0.5
79 0.1
60 0.1
02 0.1
90 0.01
103 0.001
< 0.32 < 0.61
< 0.57 2.24
< 2.00 < 0.36
< 2.96 1.27
< 0.74 < 0.60
< 4.55 3.40
< 22.63 25.53
S. S. S.
60,16 11.50
< 0.06 < 0.07 < 0.10 M.D. 1.26 0.67 7.97 1,82 1.35 21.53 1.10 < 0.15 < 1.24 < 0,13 0.02 < 0.92 0.21 M.D. M.D. H.D. N.D. N.D. N.D. 1.50 N.D. < 0,19 N.D. 0.43 0,51 N.D. 3.43 5.74 < 0.91
0.14 0.14 0.15 N,D. 0.94 N.D. 6,57 1.22 0.26 4.14 1.16 0.16 0.43 < 0.07 0.02 3.58 0.11 0.26 N.O. H.D. N.D. 0.66 H.D. 0.56 N.D. 0.14 M.D. 0.72 2.23 1.02 1.60 5.45 1.28
< 0.05 0.13 0.15 0.40 1.12 0.92 2.97 0.60 0.66 3.65 1.28 0.16
S.
0.37 0.13 0.23 M.D. 0.05 0.77 3.14 0.77 0.47 3.13 0.16 0.33 0.46 0.07 0.11 2.45 0.06 N.D. M.D. H.D. M.D. M.D. H.D. O.30 < 1.20 < 0.02 N.D. 1.01 1.35 19,04
0.76 1.15 1.39 7.70 IO,01 8.77 25.99 6.86 26,69 134.09 10.65 1.49 1.44 0.31 0.38 10.45 0.88 5.70 0.69 2.10 1.40 5.80 1.20 4.80 2.10 2.72 N.D. < 1.03 N,D. N.D. N.D. N.D. 5.54
PORK PORK
HANOI HANOI
H.
PORK FAT CAT FISH CARp EEL COW FAT CHICKEN FAT PORK FAT PORK FAT PORK PAT CHICKEN FAT CHICKEN EGG FISH PISH CNAHNA FISH MUSCLE CHANNA FISH MUSCLE CHANNA FISH LIVER CLARIUS FISH MUSCLE CAT FISH EEL EEL SEA FISH SONG BIEN CNIVANG FISH SONG LAM FISH CRAB CRAB MEAT CHICKEN EGGS DUCK EGGS TURTLE PAT TURTLE MUSCLE TURTLE LIVER TURTLE GALL- BLADDER TURTLE OVARIES SNAKE
HANOI KA~OI HANOI HANOI HA~OI HA/401
H. N. H. N. N. N. S. S.
S O N G BE S O N G BE TA/4UY EN TANUYEN TA~ IHAN
S,
H.
S. S. S. S. S. S. S. S. B I N H T H I T H I E N S. HOCMCITY S. HOCMCITY S . HOCMCITY S. HDCMCITY S. HOCMCITY S. HO ~MCITY S. HOCMCITY S. HOCMCITY S. qOCMCITY S. S, S.
TANHANH
7 1
2.20
0.27 0.24 0.41 0.42 3.27 1.13 6.13 2.42 1.51 29,92 2.15 0.42 0.62 0.14 0.04 4.20 0.15 1.20 0.12 M.D. N.D. 0.75 0.82 i.i0 0.26 0.67 N.D. 1.00 4,73 3.55 3,95 28.26 2.50
0,20
< 0.04 0.05 < 1.30 0.06 0.66 H.D. N,D. N.D. N.D, N.D. 0.92 0.17 0.23 N.D. 1.05 N.D. 2.86 N.D. 23.24 1.01
2.53 3.99 6.90 58.00 14.57 21.50 90,28 23.60 91,09 96.86 69.00 6,47 6.02
< 0.55 0.54 16.70 2.33 N.D. 12.00 20.00 18.00 N,D. 11.00 12.60 9.10 17.77 N.D. ND N.O. N.D. N.D. N.D. 55.58
N.=North Vietnam; S.:South Vietnam
TABLE II-B : PCDFCONCENTRATIONS(PPT/WET WEIGHT) IN VIETNAMESESAMPLES; CONGENERSARE IDENTIFIED 8Y PEAK NUMBERAS EXPLAINEDIN TABLE I. LAST COLUMNPRESENTSTOTAL (PCDD+PCDF) BURDENIN TOXIC EQUIVALENTS;
peaknr. tox. aq.
37 0.1
PORK
}t~OI
H.
2.47
PORK PORK FAT CAT F I S H CARP EEL COW FAT CHICKEN PAT
HANOI HANOI HANOI HANOI HANOI HANOI HAHOI
H. H. N. N. N.
0.|1 0.06 0.3S 0.77 H.D. 1.00 4.10
PORK FAT PORK FAT PORK FAT CHICKEN FAT CHICKEN EGG FISH FISH CHANRA FISH MUSCLE
S O N G 80 S O N G BE TA~rUYEH TANUYEN TANIHAM
CNAHNA F I S H MUSCLE
N. H.
S. S. S. SS~ S. S. S.
4.95 2.12 2.11 8.44 < 0.20 0.58 0.12 0.19
64 0.05
74 0.5
3.61
2.63
1.58 0.1| 0.41 < 0.32 M.D. 2,62 4.51
1.22 0,20 < 0.16 0.40 N.D. 1.92 1.95
4.19 0.14 1.71 14.08 0.66 < 0.40 O.68 0.21
1.12 2.10 2.08 15.54 0,18 < 0,16 0.16 0.11
1.29 0.75 0.06 0.07 0.22 0.32 0.92 0.99
1.53 1.69 1.42 I0.24 0.69 0.07 0.32 < 0.03
89 0.1
94 0.1
0.61
96 0.1
< 0.92
< 1,02
0,63 < 0.04 0.00 0.12 0.12 0.81 0.53
< 0.12 0.26 < 0.11 < 0.06 H.D. M.D. N.D.
< < < <
0.69 0.87 0.95 3.73 0.27 0.00 0,56 < O.O9
O.61 < O.49 H.D, 15.16 < 0.16 0.30 < 0.05 < 0.06
1.61 < 0.54 0.66 0.57 0.44 < 0,44 < 0.I0 < 0.03
0.39 0.16 0.12 0.07 N.D. N.D. N.D.
99 0.01
102 0.01
104 0.001
< 1.20
TOTAL
< 5.79
<40.66
1.99
0.99 1,16 0.45 0.64 6.40 N.D. 1.34
< 0.82 < 0,17 N.D. 0.23 N.D. N.D. N.D.
< 6.90 < 1.31 N.D. < 1.72 N.D. M.D. N.D.
2.24 0.59 0.26 0.64 0.35 3.51 3.30
4.33 6.16 5.50 13.06 1.06 0.26 0,35 0.10
< 1.20 < 2.11 N.D. N.D. < 0.15 0.13 < 0,34 0.15
< 4.91 < 5.79 N,D, N,D. 0.$2 0.64 < 2.92 < 0.99
10,99 4.07 3.46 31.54 1,62 0.53 0.92 0.17
S. S.
0.15 2.67
0,14 3.77
0,05 1.70
0.04 1.49
< 0.02 < 1.24
< 0.03 < 1.36
0.09 3.19
0.09 < 2.88
< 0.49 < 7.15
0.26 4.16
BINH TRI THIEN HOCMCITY HOCMCITY HOCMCITY HOCMCITY HOCMCITY
S. S. S. S. S. S. S.
0.26 M.D. H.D. M.D. H.D. M.D. M.D.
0.29 M.D. M.D. M.D. M.D. M.D. M.D.
0.15 I0.60 N.D. N.D. M.D. M.D. 0.03
0.12 0.66 0.07 H.D. M.D. 2.50 N.D.
0.09 M.D. H.D. H.D. M.D. H.D. N.D.
0.04 M.D. M.D. N,D. H.D. H.D. M.D.
0.10 M.D. N.D. M.D. N,D. N.D. H.O.
0.37 4.00 0.49 2.70 1.50 45.00 0.65
< 0.II H.D. N.D. N.D, N.D. M.D. N.D.
< 0.36 N.D. N.D. M.D. N.D. M.D. H.D.
0.36 ~.65 0.04 O.O7 0.05 0.90 0.28
CRAB CRAB MEAT
HOC~CITY HOCMCITY
S. S.
7.50 M.D.
1.10 N.D.
079 0.85
0.33 N.D,
N.D. M.D.
H.D. N.O.
N.D. N.D.
1.20 2.10
N.D. N.D.
N.D. N.D.
2.64 0.52
CHICKEN EGGS DUCK EGGS
HOCMCITY HOCMCITY
S, S.
0.47 R. D.
0.47 H. D.
0.37 M.D.
0.94 N.D.
0.15 M.D.
0.29 M.D.
< 0.27 N.D.
1.42 M.D.
< 0.35 M.D.
< 3.48 N.D.
0.36 M.D.
0.39 N.D.
0.19 N.D,
< 0.00 N.D.
< 0.17 M.D.
< 0.19 N.D.
0.53 N,D.
< 1,11 H.D.
M.D. N.D.
1.76 2.56
S.
2.95 0.06
4.27 2.80
2.13 2.96
2.03 2.12
1.23 N.D,
M.D. M.D.
N.D. N.D,
i.ii 10.31
N.D, H.D.
N.D, N.D.
39.95 1.29
22,40 1.59
9.28 0.91
4.64 0.39
N.D. < 0.38
M.D. < 0.42
N.D. 0.61
N.D. < 0.64
N.D. < 2.73
21.70 6.54 85,71
CHANHA FISH LIVER CLARIUS FISH MUSCLE CAT FISH EEL EEL SEA FISH SONG BIEN CHIVARG FISH SONG LAM FISH
TURTLE TURTLE
FAT MUSCLE
TURTLE LIVER TURTLE GALL-BLADDER TURTLE OVARIES SNAKE
S, S.
sS~ TANHANH
S.
0.22 2.57
23.91 < 0.65
0.1| < 1.21
88 0.1
0.55 0.00
13,17
496
CONCLUSIONS AND DISCUSSION We can confirm and extend our previous conclusions (Schecter et al., 1989). It is evident that the Vietnamese samples show a wide spread of PCDD and PCDF levels. This suggests that localized sources play an important role. In order to compare the PCDD and PCDF burden in North and South Vietnam, the mean concentration per isomer was calculated. Samples with concentrations below the detection limit were omitted from the mean value calculation. Therefore, the figures cannot be easily used to assess the 2,3,7,8 -TCDD uptake by food. In addition, the South Vietnamese turtle samples were omitted from this calculation, because these samples were all derived from the same animal. The mean total (PCDDs + PCDFs) concentration in the samples from the South (78 ppt) is higher than in samples from the North (36 ppt). This can well reflect the difference in industrialisation between the North and South of Vietnam. In the samples from the South, 2,3,7,8-TCDD accounts for 2.5% of the total of the PCDD-PCDF burden. In the Northern samples the relative amount is 1.3%. The higher relative abundance of 2,3,7,8-TCDD in the South suggests that 2,3,7,8-TCDD from "Agent Orange" spraying has entered the ecological system. The results for fresh water fish from the North and South of Vietnam show low contaminations of the fish and resemble more or less samples from other industrialized areas in the world, although the Vietnamese concentrations are less contaminated (Stalling et al., 1983; Rappe et al., 1987). Unfortunately a comparison for our crab sample and the Swedish results is not possible because there only the hepatopancreas is measured (Rappe et al.,
1983). It seems that for sea fish the contamination lower than in fish from industrialized areas.
with
chlorinated
dioxins
is
REFERENCES Rappe, C., Andersson, R., Bergqvist, P., Brohede, C., Hansson, M., Kjeller, L., Lindstr6m, G., Marklund, S., Nygren, M., Swanson, S.E., Tysklind, M., Wiberg, K., Chemosphere 16, 1603-1618, 1987. Schecter,
A., Ryan, J., Constable,
J., Chemosphere
15, 1613-1620,
Schecter, A., Kooke, R., Sern~, P., Olie, K., Constable, D6 Quang Huy, Chemosphere, 18, 621-628, 1989. Schecter, A., F~rst, Chemosphere, in press.
P.,
KrUger,
C.,
Meemken,
H.A.,
1986.
J., Nguye~ Duc Hu~, and
Groebel,
W.,
Stalling, D.L., Smith, L.M., Petty, J.D., Hogan, J.W., Johnson, J.L.,Rappe, C., Buser, H.R., "Residues of polychlorinated dibenzo-p-dioxins and dibenzofurans in Laurentian Great Lakes fish.", from "Human and Environmental risks of chlorinated dioxins and related compounds.", Eds. Tucker, R.E., Young, A.L., Gray, A.P., Plenum Publ. Corp., New York, 1983. "Herbicides in war. The long term ecological human consequences." Westing, A.H., Taylor and Francis, London and Philadelphia, 1984. Zorge, J.A.v., Theelen, R.M.C., Wijnen, J.H.v., Olie, K., Berg, Report: "Werkgroep toxiciteitsequivalentiefactoren", maart 1988.
Ed.
M.v.d.,