Chlorinated dioxin and dibenzofuran levels in sediments collected from rivers in Vietnam, 1984-6

Chlorinated dioxin and dibenzofuran levels in sediments collected from rivers in Vietnam, 1984-6

Chemosphere, Vol.18, Nos.l-6, Printed in Great Britain pp 831-834, 1989 0045-6535/89 $3.00 + .00 Peraamon Press plc C H L O R I N A T E D DIOXIN A...

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Chemosphere, Vol.18, Nos.l-6, Printed in Great Britain

pp 831-834,

1989

0045-6535/89 $3.00 + .00 Peraamon Press plc

C H L O R I N A T E D DIOXIN AND D I B E N Z O F U R A N LEVELS IN SEDIMENTS COLLECTED FROM RIVERS IN VIETNAM, 1984-6

A r n o l d Schecter 1, Brian D. Eitzer, and Ronaid A. Hites 2" IDept. of Preventive Medicine, Clinical Campus, State U n i v e r s i t y of New York, 88 Aldrich Ave., Binghamton, NY

13903

2School of Public and E n v i r o n m e n t a l A f f a i r s and D e p a r t m e n t of Chemistry, I n d i a n a University, Bloomington, IN 47405 A b s t r a c t . G r a b s e d i m e n t s a m p l e s w e r e t a k e n f r o m t h r e e r i v e r s in V i e t n a m ; t h e s e s a m p l e s r e p r e s e n t e d t h e i n d u s t r i a l s o u t h ( S a i g o n R i v e r ) , t h e A g e n t O r a n g e s p r a y e d a r e a ( D u n g Nai River) and the n o n - i n d u s t r i a l north (Red River). Samples were analyzed for the tetra- through octa- chloro-homologs of polychlorinated dibenzo-p-dioxins and furans (PCDD/F). The homologs were present in p a t t e r n s a n d amounts previously seen for e n v i r o n m e n t a l samples. Introduction. A n u m b e r of recent studies have focused on the presence of P C D D / F in human a d i p o s e t i s s u e (]-6). T h e s e s t u d i e s h a v e r e s u l t e d in m u c h s p e c u l a t i o n a b o u t t h e s o u r c e of t h e s e c o m p o u n d s to h u m a n s . Possible sources include direct contamination of the environment by i n d u s t r i a l d i s c h a r g e s or s p r a y i n g of P C D D / F c o n t a i n i n g m a t e r i a l s s u c h as A g e n t O r a n g e or i n d i r e c t c o n t a m i n a t i o n by t h e p r o d u c t i o n a n d e m i s s i o n of t h e s e c o m p o u n d s d u r i n g c o m b u s t i o n followed by a t m o s p h e r i c t r a n s p o r t and deposition. Of

the recent studies on adipose tissue, one focused on V i e t n a m .

This

study

compared

P C D D / F l e v e l s in b o t h t h e n o r t h a n d s o u t h of V i e t n a m w i t h the l e v e l s r e p o r t e d f r o m o t h e r industrialized countries (4). It was f o u n d that the industrialized south had levels c o m p a r a b l e to or h i g h e r t h a n o t h e r i n d u s t r i a l i z e d c o u n t r i e s , a n d t h e more r u r a l N o r t h had levels which were an order of magnitude less. Thus, studies which compare the North and South of Vietnam might shed some light onto the source of these compounds to the e n v i r o n m e n t and, ultimately, the h u m a n population. It h a s b e e n s h o w n t h a t s e d i m e n t s c a n p r o v i d e a r c h i v e s o f e n v i r o n m e n t a l p o l l u t i o n t r e n d s P C D D / F have been f o u n d in sediment at remote sites at low concentrations (8), indicating that sediment can be used to study the atmospheric transport of these compounds. Thus, in an a t t e m p t to u n d e r s t a n d d i f f e r e n c e s in P C D D / F c o n t a m i n a t i o n in V i e t n a m , it was of i n t e r e s t to compare sediment from various areas in Vietnam.

(7).

ExPerimental. S e d i m e n t was o b t a i n e d f r o m t h r e e r i v e r s in V i e t n a m w h i c h are s h o w n in F i g u r e 1. T h e s a m p l i n g l o c a t i o n s a r e the S a i g o n R i v e r in the Ho Chi Mirth C i t y a r e a ( p o p u l a t i o n 2,700,800), f o r m e r l y S a i g o n , f o l l o w e d by f i v e s i t e s a l o n g t h e D o n g Nai r i v e r in the heavily c o n t a m i n a t e d (by Agent Orange) area a r o u n d Tan Uyen village, and two sites in the Red River, in the Hanoi area (population 880,000), where Agent Orange was never used. At each location, grab samples were taken from the bottom of the river by a diver. T h e e x p e r i m e n t a l p r o c e d u r e has been r e p o r t e d e l s e w h e r e (9). It c o n s i s t s of s p i k i n g the sediment with carbon-13 labeled OCDD, soxhlet extraction, chromatographic clean-up, and GC/MS in the e l e c t r o n c a p t u r e , n e g a t i v e i o n i z a t i o n mode u s i n g s e l e c t e d ion m o n i t o r i n g . It s h o u l d be n o t e d t h a t t h i s i o n i z a t i o n m o d e g i v e s a p o o r r e s p o n s e f o r 2 , 3 , 7 , 8 - T C D D , b u t it r e s p o n d s well for all the other congeners (including other tetras).

831

832


Figure I. Map of Vietnam showing the Dong Nai River, Saigon River, and Red R i v e r about 1140 km from Hanoi to Ho Chi Minh City.

l!

is

833

Results and Discussion. The results of the study are shown in Table 1. An e x a m i n a t i o n of t h i s t a b l e s h o w s t h a t t h e c o n c e n t r a t i o n l e v e l s in a g i v e n s a m p l e d i f f e r d r a m a t i c a l l y f r o m one another but that the relative amounts of the various chloro-homologs w i t h i n a given sample are quite similar to one another. For example, all samples have OCDD as highest homolog but its concentration ranges from 210-4530 pg/g. T h e s e d a t a show t h e h i g h e s t c o n c e n t r a t i o n s in the Saigon R i v e r , m e d i u m c o n c e n t r a t i o n s in t h e D o n g N a i R i v e r , a n d t h e l o w e s t c o n c e n t r a t i o n s in the Red River. The overall p a t t e r n of P C D D / F chloro-homoiogs is one which might be related to c o m b u s t i o n p r o c e s s e s f o l l o w e d by a t m o s p h e r i c d e p o s i t i o n . T h e p a t t e r n of c h i o r o - h o m o l o g s is also similar to what was seen in the h u m a n f a t tissue from Vietnam previously reported (4).

TABLE 1 VIETNAM SEDIMENT CONCENTRATIONS IN PG/G DRY VEIGHT OF PCDD/F FROM RIVERS IN THE NORTH AND SOUTH OF VIETNAM, 1984/5

SAMPLE

TCDD PnCDD HxCDD HpCDD OCDD

Saigon R i v e r

--

87

220

Dang Nai R i v e r 1

-*

6.8

33

120

1200

Dang Nai R i v e r 2

--

4.2

11

68

750

11

Pang Rat R i v e r 3

--

6.7

17

140

1200

18

Dong Nai R i v e r 4

--

t.2

Dang Nai R i v e r 5

*-

0.9

Red R i v e r #1 Red R i v e r ~2

. . . . . . . .

8.2 13 0.5 0.9

940

TCDF

4530

PnCDF H x C D F

55 .

.

160 .

.

240 .

3.2 14

320

4.1 8.4

63

950

16

4.1

1120

11

4.0

25

0.4 0.4

---

240 210

2.6 1.8

230

.

160 10 5.1

NpCDF OCDF

2.8

2.2

3.1

2.9

21

2.1

3.3 48 1.0 0.4

12 4.1 51 0.9 0.8

TOTAL

6782 1365 858 1437 1052 1433 255 219

A BLANK INDICATES THAT THE ROMOLOG GROUP WAS NOT DETECTED AT A LIMIT OF DETECTION OF ABOUT 0.1 PG/G

TABLE 2 AVERAGE TOTAL CONCENTRATIONS OF PCDD/F |N PG/G FOR UPPERMOST LARE SEDIMENTSa AND VIETNAM RIVER SEDIMENTSb ~ietnem R i v e r s Sediments

Lake SedimenTs Site

Cone.

Site

Conc.

Lake Nuron

1240

Ssigo~

6800

Lake Michigan

1600

Dons Uai

1200

Lake E r i e

2150

Red R i v e r

Lake O n t a r i o S t s k t w l t Lake Lake Z u r i c h Lake | a L d e r s Lake L w s n o

11000 7"50 1500 1500 2000

a)

From J. M. Czuczve, Ph.D. Thesis (Reference I 1 0 )

b)

This s t u d y

240

834

In Table 2, the total average concentrations of P C D D / F are compared to the concentrations f r o m t h e u p p e r m o s t l a y e r of l a k e s e d i m e n t s p r e v i o u s l y r e p o r t e d (10). T h i s c o m p a r i s o n is not exact because river sediments reflect conditions upstream and lake sediments reflect conditions over most of the lake's watershed. E v e n so, it c a n be s e e n t h a t the S a i g o n R i v e r has c o n c e n t r a t i o n s o n l y e x c e e d e d b y L a k e O n t a r i o w h i c h is t h o u g h t to h a v e some direct c o n t a m i n a t i o n by P C D D / F f r o m p e n t a c h l o r o p h e n o l w a s t e s (10). T h u s , t h e S a i g o n R i v e r , in a h e a v i l y i n d u s t r i a l i z e d a r e a in w h i c h b o t h d i r e c t a n d i n d i r e c t c o n t a m i n a t i o n m i g h t be e x p e c t e d , has t h e h i g h e s t c o n c e n t r a t i o n a m o n g t h e V i e t n a m r i v e r s s t u d i e d . T h e n e x t h i g h e s t level of c o n c e n t r a t i o n is t h a t o f t h e D o n g N a i R i v e r . H e r e , the c o n c e n t r a t i o n s a r e s i m i l a r to lakes which are near industrial areas and receive considerable atmospheric input. As can be seen in Figure 1, the entire Dong Nai River is within 200 km of the industrialized area of Ho Chi Mirth C i t y , a n d t h u s , m i g h t be e x p e c t e d to r e c e i v e a t m o s p h e r i c d e p o s i t i o n o f P C D D / F . T h e lowest level o f c o n c e n t r a t i o n is t h a t seen in the Red R i v e r . T h i s level is e v e n less t h a n t h a t seen in the v e r y r e m o t e S i s k i w i t L a k e . A l t h o u g h t h i s is s o m e w h a t s u r p r i s i n g c o n s i d e r i n g the a r e a ' s p o p u l a t i o n (880,000), t h e s e low P C D D / F c o n c e n t r a t i o n s m i g h t be i n d i c a t i v e of conditions upstream. It s h o u l d be p o i n t e d o u t t h a t the H a n o i a r e a is not heavily industrialized and that the Hanoi area is where the lowest h u m a n adipose tissue levels of P C D D / F were seen. That TCDD was not f o u n d at any site, including Agent Orange sprayed areas, could have several explanations. F i r s t , s a m p l i n g s i t e s were g r a b s a m p l e s of the u p p e r m o s t s e d i m e n t , a n d TCDD c o n t a m i n a t e d material could have been buried by fresh sediment. It is also possible that the poor i n s t r u m e n t a l r e s p o n s e f o r 2 , 3 , 7 , 8 - T C D D in the n e g a t i v e i o n i z a t i o n m o d e p r e v e n t s its detection. To s u m m a r i z e , it h a s b e e n s h o w n t h a t r i v e r s e d i m e n t s in V i e t n a m a r e c o n t a m i n a t e d w i t h PCDD/F. T h e l e v e l s o f c o n t a m i n a t i o n f r o m the d i f f e r e n t a r e a s c o r r e l a t e w i t h the l e v e l s seen in h u m a n adipose tissue from the d i f f e r e n t areas. The levels are in the range previously seen f o r lake s e d i m e n t s a n d c a n p o s s i b l y be r e l a t e d to the a t m o s p h e r i c d e p o s i t i o n of P C D D / F produced by combustion sources. REFERENCES I. M. Nygren, C. Rappe, G. Lindstrom, M. Hanson, P. A. Berqvist, S. Marklund, L. Domellof, L. H a r d e l l a n d M. O i s s o n in Chlorinated Dioxins and Dibenzo/urans in Perspective (Eds. C. Rappe, G. C h o u d h a r y and L. Keith), Lewis Publishers, pp. 17-34 (1986). 2. A. J. S c h e c t e r , J. J. R y a n , M. Gross, N. C. A. W e e r a s i n g h e , a n d J. D. C o n s t a b l e Chlorinated Dioxins and Dibenzo/urans in Perspective (Eds. C. R a p p e , G. C h o u d h a r y a n d Keith), Lewis Publishers, pp. 35-50 (1986).

in L.

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in

4.

A.J. Schccter, J. J. Ryan and J. D. Constable, Chemosphere 15, l113-1670 (1986).

5.

M. Ono, T. Wakimoto, R. T a t s u k a w a and Y. Masuda, Chemosphere 15, 1629-1684 (1986).

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C. Rappc, M. Nygren, G. Lindstrom, and M. Hanson, Chemosphere 15, 1635-1639 (1986).

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Pollutants

(Eds.

R.

A. Hires

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