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Organic chlorine compounds in lake sediments. IV. Dioxins, furans and related chloroaromatic compounds
Chemosphere, Vol.21, No.12,pp Printed in Great Britain
1371-1379,
1990
0 0 4 5 - 6 5 3 5 / 9 0 $3.00 + .00 Pergamon Press plc
O R G A N I C C H L O R I N E C O M P O U N D S IN LAKE SEDIMENTS. IV. DIOXINS, FURANS AND R E L A T E D C H L O R O A R O M A T I C COMPOUNDS. J a a n a Koistinen-,
J a a k k o P a a s i v i r t a - and J u k k a S H r k k ~ b
" D e p a r t m e n t of Chemistry, U n i v e r s i t y of J y v ~ s k y l ~ K y l l i k i n k a t u I-3, SF-40100 Jyv~skyl~, F i n l a n d b D e p a r t m e n t of Biology, U n i v e r s i t y of J y v ~ s k y l ~ Y l i o p i s t o n k a t u 9, SF-40100 Jyv~skyl~, F i n l a n d
ABSTRACT P o l y c h l o r o d l b e n z o - p - d i o x i n s (PCDDs), p o l y c h l o r o d i b e n z o f u r a n s (PCDFs), polyc h l o r o n a p h t h a l e n e s (PCNs) and c o p l a n a r PCBs w e r e m e a s u r e d in s u r f a c e sediments from 18 lake areas in C e n t r a l Finland. T o x i c 2 , 3 , 7 , 8 - s u b s t i t u t e d PCDD and PCDF c o n g e n e r s o c c u r r e d at low levels (<20 - 230 p g / g dw). PCNs a p p e a r e d at few ng/g (total PCNs) levels. Pulp mills or any o t h e r local sources could not be a s s o c i a t e d w i t h the s e d i m e n t e d PCDDS, PCDFs and PCNs. C o p l a n a r PCB c o n g e n e r s 77 and 105 (IUPAC Nr) w e r e g e n e r a l l y found at 20-550 p g / g levels. The most toxic c o n g e n e r 126 was m e a s u r e d (110 pg/g) only at one a r e a near a local PCB leakage. Pulp mill o r i g i n a t e d a r o m a t i c c h l o r o c o m p o u n d s w h i c h coelute with PCDDs and PCDFs in c l e a n up, p r o b a b l y alkyl p o l y c h l o r o b l b e n z y l s (R-PCBBs) a p p e a r e d at n g / g levels and showed a clear g r a d i e n t d o w s t r e a m s from p u l p mill effluent points. INTRODUCTION Sediment s t u d i e s are f r e q u e n t l y u s e d to follow the e n v i r o n m e n t a l fate of p e r s i s t e n t o r g a n i c c h l o r o c o m p o u n d s . I-7 The n o t o r i o u s PCDDs and PCDFs w e r e included in these studies in 1980s. e-~' B e c a u s e toxic PCDDS and PCDFs were d e t e c t e d at very low levels in p u l p mill e f f l u e n t s and products, they were studied in p u l p m i l l r e c i p i e n t sediments, as well. ~2 In the p r e s e n t study, we include PCDDs and PCDFs to our r e s e a r c h on o r g a n o c h l o r i n e s ' ' 6 " 7 " I m ' ~ + in C e n t r a l F i n l a n d lake sediments. A l s o o t h e r a r o m a t i c p o l y c h l o r o c o m p o u n d s which are s t u c t u r a l l y s i m i l a r to and c o e l u t e in c l e a n u p w i t h PCDDs and PCDFs are analyzed. T h e s e PLACs (Planar A r o m a t i c C h l o r o c o m p o u n d s ) include c o p l a n a r PCBs ~5-~6 and U P A C s (Unknown P l a n a r A r o m a t i c C h l o r o c o m p o u n d s ) ~7. Some d i c h l o r o - U P A C s are e l u t e d in GC at the same r e t e n t i o n w i n d o w g i v i n g low r e s o l u t i o n SIM ions by the same m/e 320, 322 and 324 as TeCDDs. ~7"~" SAMPLES, A N A L Y S E S AND R E S U L T S Sampling areas Study area and s a m p l i n g sites are shown in Fig. I. D e t a i l s of the s a m p l i n g places and m e t h o d s have b e e n d e s c r i b e d in the s e c o n d p a p e r of the p r e s e n t series. 13 O n l y s u r f a c e s e d i m e n t s w e r e a n a l y z e d in the p r e s e n t study.
1371
1372
Norway ,-. ,.,'.
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Adnekoskt
,'
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Sweden ~
Jyvaskyla~ ~
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S
~4
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J~ms "
/Finland : /
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o~.;op,., I
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i
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v
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I
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1~" Fig. I. The sampling sites.
,o ~
S
' ' 2~° ~ 4~
Compounds studied The compounds analyzed are shown in Fig. 2.
PCDD
PCB 77
PCDF
PCN
PCB 105
clClc l ~ PCB 126 Fig.
PCB 169
2. Structure type formula of polychlorodibenzo-pdioxins (PCDD), polychlorodibenzofurans (PCDF) and polychloronaphthalenes (PCN). Formula and name abbreviations of four coplanar PCBs analyzed: PCB 77 = 3,3',4,4'-tetrachlorobiphenyl, PCB 105 = 2,3,3',4,4'-pentachlorobiphenyl, PCB 126 = 3,3',4,4'5-pentachlorobiphenyl and PCB 169 = 3,3',4,4'5,5'-hexachlorobiphenyl.
Analysis prodecure The surface sediment sample was freeze-dried and the residue (2-16 g) was weighed. Samples taken in 1988 (areas 1-8) were extracted in Soxhlet with toluene-for 48 hours after s p i k i n g with 13Ci~-labelled internal standards, 2378-TeCDF and 2378-TeCDD (2.5 ng each). The samples taken in 1989 (areas 9-18) were treated with a modified method using duplicates: a mixture containing IsC12-1abelle d 2378-TeCDF, 12378-PeCDF, 12378-PeCDD and 1232478-HxCDD (5 ng each) was added. ~sC-2378-TCDD was not used, because it interferes with HxCN in SIM. Then, one sample was extracted in Soxhlet with toluene for 48 hours and the duplicate sample with methanol-dichloromethane 1:2 (v/v) for 24 hours.
1373
Each e x t r a c t was e v a p o r a t e d in R o t a v a p o r to 5 ml and then g e n t l y to dryness w i t h n i t r o g e n gas flow. The r e s i d u e was d i s s o l v e d in 4 ml of h e x a n e and shaken two times w i t h 4 ml of conc. s u l f u r i c acid. Then, sulfur was r e m o v e d by adding about I g of Cu p o w d e r (activated w i t h conc. HCl) and s h a k i n g for 2 min. The h e x a n e was c o n c e n t r a t e d w i t h n i t r o g e n gas flow to 0.5 ml and t r a n s f e r r e d to an a c t i v a t e d c a r b o n c o l u m n c o n t a i n i n g 50 mg of SK-4 A l l t e c h b a r b o n (80/100 mesh) in 10 cm long, 6 mm o.d. and 4 m m i.d. g l a s s tube (plugs of h e x a n e w a s h e d cotton). The total length of the c a r b o n part was 10 mm. N o n p l a n a r c o m p o u n d s w e r e e l u t e d out from the c o l u m n w i t h 10 ml of h e x a n e d i c h l o r o m e t h a n e 1:1 (v/v). T h e n the c o l u m n was i n v e r t e d and the d i o x i n f r a c t i o n e l u t e d (reverse elution) w i t h 10 ml of toluene. T e t r a d e c a n e (20 ~i) was added and t o l u e n e e v a p o r a t e d g e n t l y w i t h n i t r o g e n gas flow. The r e s i d u e was r e d i s s o l v e d in 0.5 ml of h e x a n e and i n t r o d u c e d to a c o l u m n of 2 g of b a s i c a l u m i n a (Alumina B, A c t i v i t y I, ICN B i o m e d i c a l s ) in a P a s t e u r pipette. A f t e r e l u t i o n w i t h 10 ml of h e x a n e - d i c h l o r o m e t h a n e 98:2 (v/v) the d i o x i n f r a c t i o n was c o l l e c t e d by e l u t i n g w i t h 10 ml of h e x a n e : d i c h l o r o m e t h a n e 1:1 (v/v). A f t e r a d d i n g t e t r a d e c a n e (20 ~i) the d i o x i n f r a c t i o n was c o n c e n t r a ted in n i t r o g e n gas flow for the GC/MS analysis. One or two ~i of s o l u t i o n was i n j e c t e d s p l i t l e s s l y to a gas c h r o m a t o g r a p h / m a s s s e l e c t i v e d e t e c t o r s y s t e m m o d e l HP 5970 e q u i p p e d w i t h a SE-54 fused silica c a p i l l a r y c o l u m n (25 m, 0.21 mm i.d., film t h i c k n e s s 0.11 ~m). I n j e c t o r t e m p e r a t u r e was 250°C. O v e n t e m p e r a t u r e p r o g r a m e m p l o y e d was: 100 ° isothermal for 1 min, then + 20°/min to 180 ° , and finally + 5°/min to 290 ° . H e l i u m was u s e d as c a r r i e r gas (30 cm/s). CG/MS t r a n s f e r line was kept at 300°C. Low r e s o l u t i o n SIM mode was used at s t a n d a r d EI c o n d i t i o n s m o n i t o r i n g three s e l e c t e d m/e values (M ÷, M÷+2, M÷+4) for e a c h c o n g e n e r group. I d e n t i f i c a t i o n was b a s e d on the r e t e n t i o n times c o m p a r e d to those of the a u t h e n t i c s t a n d a r d c o m p o u n d s and on the i n t e n s i t y ratios of the peaks. While d i c h l o r o - U P A C m o l e c u l a r ions give peaks to the same w i n d o w as TeCDDs, Iv identity of the l a t t e r was c h e c k e d by high r e s o l u t i o n GC/MS ( V G 7 0 - 2 5 0 S E in the U n i v e r s i t y of Kuopio): w h e n ion m/e 319.8965 was m o n i t o r e d U P A C peaks were absent but "other TeCDD" peaks w e r e still present. Q u a n t i t a t i o n of PCDDs, PCDFs and c o p l a n a r PCBs was b a s e d on the r e s p o n s e factors o b t a i n e d from the G C / S I M of s t a n d a r d m i x t u r e s and internal standards. For PCNs and UPACs, the r e s p o n s e factor one r e l a t e d to ~ s c ~ 2 - 2 3 7 8 - T e C D F was a s s u m e d and used, because single m o d e l c o m p o u n d s w e r e not available. Results
No s i g n i f i c a n t d i f f e r e n c e s b e t w e e n the two e x t r a c t i o n m e t h o d s w e r e obtained. C o n s e q u e n t l y only results from m e t h a n o l - d i c h l o r o m e t h a n e e x t r a c t s are p r e s e n t e d here. C o n t e n t s of PCDDs are shown in T a b l e I, PCDFs in T a b l e 2, PCNs and c o p l a n a r PCBs in T a b l e 3 and UPACs in T a b l e 4. For e s t i m a t i o n of the dioxin type of toxic load in the samples, the c o n c e n t r a t i o n s of o b s e r v e d 2,3,7,8- s u b s t i t u t e d c o n g e n e r s were m u l t i p l i e d by N o r d i c TEF factors 19 and summarized. The levels of m e a s u r e d c o p l a n a r PCBs w e r e m u l t i p l i e d by TEF factors r e c e n t l y s u g g e s t e d in D i o x i n ' 9 0 s y m p o s i u m and summarized, as well. The o b t a i n e d T E Q - v a l u e s (2378-TeCDD equivalents) are p r e s e n t e d in T a b l e 5.
DISCUSSION The m o s t toxic 2 3 7 8 - T e C D D was not d e t e c t e d in any samples, but its two noni d e n t i f i e d isomers w e r e c o m m o n and a b u n d a n t in pulp mill r e c i p i e n t s and showed a clear g r a d i e n t d o w n s t r e a m s (Table I and Fig. 3). W h i l e s e d i m e n t a t i o n rates of dry m a t t e r b e l o w mill, e s p e c i a l l y at area 4 (Kuh 4) are v e r y high, 7,13 the amounts of a n n u a l l y p r e c i p i t a t e d T e C D D s m u s t m a k e a still m o r e steep gradient. Therefore, one can c o n c l u d e that these less toxic T e C D D s in s e d i m e n t s o r i g i n a t e from the c h l o r o b l e a c h i n g of pulp.
1374
In c o n t r a r y to the o b s e r v e d TeCDDs, the toxic hexa-, h e p t a - and o c t a c h l o r o dioxins found (Table 1 and Fig. 4) are c e r t a i n l y not p u l p mill originated. The same is the case for 1 2 3 4 6 7 8 - H p C D F and OCDF (Table 2) w h i c h m i g h t come from c o m b u s t i o n s at the m o r e d e n s e l y p o p u l a t e d and i n d u s t r i a l i z e d areas in South Finland. TABLE 1 . 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 p g / g in dry s u r f a c e sediments. L i m i t of d e t e r m i n a t i o n for areas 1-8 was 50 and for areas 9-18 20 pg/g. Sample
2378TeCDD
I. Kei 2. Kii 3. Kuh 3a 4. Kuh 4 5. Vat 6. Lep 7. Pot 8. Ris 9. Van 1 0 . Sou 11. Olk 12. Tii 13. Leh 14. Jud 15. Teh 16. Vir 17. Asi 18. V~
Other TeCDDs
0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
12378PnCDD
0 0 930 1010 1400 590 280 420 110 100 40 80 70 90 50 40 0 0
123478- 123678- 123789HxCDD HxCDD HxCDD
0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 20 0 0
0 0 0 0 0 0 61 0 82 78 0 0 79 77 0 40 0 0
0 0 0 0 0 0 0 0 39 0 0 0 34 0 0 0 0 0
1234678HpCDD
OCDD
0 0 0 0 0 0 0 0 34 0 0 0 0 25 49 36 0 0
0 0 0 0 0 0 0 0 34 0 0 0 0 34 0 42 0 0
TABLE 2. P o l y c h l o r i n a t e d d i b e n z o f u r a n s pg/g in dry s u r f a c e sediments. L i m i t of d e t e r m i n a t i o n for areas I-8 was 50 and for areas 9-18 20 pg/g. Sample
2378- 12378- 23478- 123478 123678 123789 234678 1234678 1234789 T e C D F PnCDF PnCDF -HxCDF -HxCDF -HxCDF -HxCDF -HpCDF -HpCDF
1. Kei 2. Kii 3. Kuh 3a 4. Kuh 4 5. Vat 6. Lep 7. Por 8. Ris 9. Van 10. Sou 11. Olk 12. Tii 13. Leh 14. Jud 15. Teh 16. Vir 17. Asi 18. Vaa
0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
0 0 0 0 0 0 64 0 79 63 42 0 32 39 39 44 230 150
0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
OCDF 0 0 0 0 0 0 0 0 22 0 0 0 0 0 0 0 160 75
1375
1600
pg/g
dw
1
3
1400 1200 1000
800600400200 0 A r e a
Fig.
2
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
3. C o n c e n t r a t i o n s of TeCDDs ( 2 , 3 , 7 , 8 - i s o m e r not detected) in dry s e d i m e n t samples.
200 Octa-CDD
Pg/g
1234678-HpCDD
dw 150
....
123678-HxCDD
................................................m i
............
123478-HxCDD 100
0
Area
.....................................................................................................................
I
I
I
I
I
t
I
I
I
I
2
3
4
5
6
7
8
9
Fig.
4.
10
11
12
13
14
15
16
17
18
Concentrations of toxic PCDD c o n g e n e r s in dry s e d i m e n t samples.
2 3 7 8 - T e C D F and 2 3 4 7 8 - P n C D F w h i c h were found to be in m a n y cases the most a b u n d a n t toxic P C D D / F c o n g e n e r s in a q u a t i c animals 12,2°,21 and also in pulp c h l o r o b l e a c h i n g w a s t e s 22-23 w e r e n o n d e t e c t a b l e in the p r e s e n t s e d i m e n t samples. The P C D D / F c o n g e n e r ratios show m o r e "backround" than "bleaching" pattern w h e n c o m p a r e d to the results of R a p p e et al. ~4-2s This i n d i c a t e s that d i o x i n p o l l u t i o n from C e n t r a l - F i n n i s h p u l p mills, at least in recent years, has b e e n very low. E.g. c o n t e n t s of toxic P C D D / F s in s u r f a c e sediments near p u l p m i l l s at S w e d i s h West Coast w e r e c o n s i d e r a b l y higher. 12-zs
1376
TABLE
3. P o l y c h l o r o n a p h t h a l e n e s and c o p l a n a r PCBs p g / g in dry s u r f a c e sediments. L i m i t of d e t e r m i n a t i o n for a r e a s I-8 was 50 pg/g and for areas 9-18 20 pg/g. N o t anal y s e d = -I.
Sample
Pol¥chloronaphthalenes TeCN PnCN HxCN HpCN OCN
1. Kei 2. Kii 3. Kuh 3a 4. Kuh 4 5. Vat 6. Lep 7. Por 8. Ris 9. V a n 10. Sou 11. Olk 12. Tii 13. Leh 14. Jud 15. Teh 16. V i r 17. Asi 18. V ~
TABLE
UPAC
Kei Kii Kuh 3a Kuh 4 Vat Lep Por Ris Van
TABLE
1
0 0 0.21 2.70 1.00 1.70 0.26 0.11 0.06
0 0 250 170 0 0 0 0 30 30 0 0 30 40 70 50 130 50
0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
98 61 0 0 0 160 89 130 120 250 0 0 550 270 230 200 210 110
-1 -1 -I -1 -I -1 -I -I 98 100 52 90 120 110 120 100 120 54
PCBs 126
169
0 0 110 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
UPAC
2
UPAC
0 0 0.06 0.91 0.32 0.37 0.08 0 0.02
3
!
Sample
0 0 0.31 4.50 1.30 1.70 0.45 0 0.12
! ! ! ! ! ! ! ! !
10 11 12 13 14 15 16 17 18
UPAC
SOU 01k Tii Leh Jud Teh Vir Asi V~
1
UPAC
0.07 0.06 0.19 0.10 0.04 0.02 0 0 0
2
UPAC
0.02 0.03 0.10 0.09 0.02 0 0 0 0
Kei Kii Kuh 3a Kuh 4 Vat Lep Por Ris Van
PCDD+PCDF 0 0 0 0 0 0 6.7 0 13.0
Copl.
PCB
1.0 0.6 11.0 0 0 1.6 0.9 1.3 1.7
!
Sample
! ! ! ! ! ! ! ! !
10. 11. 12. 13. 14. 15. 16. 17. 18.
Sou Olk Tii Leh Jud Teh Vir Asi V~
PCDD+PCDF
Copl.
8.4 0.4 0 12.0 8.4 0.9 6.8 2.5 1.6
* S u g g e s t i o n of S . S a f e in D I O X I N ' 9 0 s y m p o s i u m in B a y r e u t h FGR, S e p t e m b e r 10th 1990: TEF factors for PCBs 77, 105 and 126 s h o u l d be 0.01, 0.001 and 0.1, r e s p e c t i v e l y .
3
0.13 0.08 0.18 0.17 0.08 0.05 0.02 0 0
5. S u m m a r i z e d c o n c e n t r a t i o n s of o b s e r v e d toxic P C D D s + P C D F s (NORDIC 19) and c o p l a n a r PCBs (77+105+126; Safe *) pg/g as 2 3 7 8 - T e C D D e q u i v a l e n t s (TEQs) in dry s u r f a c e sediments.
Sample 1. 2 3 4 5 6 7 8 9
140 140 0 150 370 460 240 370 110 320 0 0 120 120 240 130 490 170
Coplanar 105
4. D i c h l o r o - U P A C s (names in Ref 17) n g / g in dry s u r f a c e sediments. Limit of d e t e r m i n a t i o n for areas 1-8 was 0.05 and for areas 9-18 0.02 ng/g.
Sample I. 2. 3. 4. 5. 6. 7. 8. 9.
790 1400 3200 3000 1300 1000 540 1400 600 2500 490 610 400 450 1600 370 2200 680
77
PCB
2.6 0.1 0.1 5.6 2.8 2.4 2.1 2.2 1.2
1377
Low levels of d i o x i n s in the r e c i p i e n t s e d i m e n t s s t u d i e d in this w o r k are p a r a l l e l w i t h o b s e r v a t i o n s on local mill effluent. T o x i c PCDDs and PCDFs were n o n d e t e c t a b l e (< 50 pg/l) in the e f f l u e n t w a t e r I" and in m u s s e l s (< 50 p g / g dw) i n c u b a t e d n e a r to the e f f l u e n t pipe 26 of the a c t i v a t e d sludge t r e a t m e n t plant of a k r a f t p u l p mill. In contrary, five t o x i c c o n g e n e r s w e r e m e a s u r e d (total 600 p g / g dw) in m u s s e l s incubated b e l o w k r a f t m i l l s w i t h o u t b i o l o g i c a l purification. 27 PCNs have b e e n o b s e r v e d as g e n e r a l l y occurring, p e r s i s t e n t and b i o a c c u m u l a t i n g traces in B a l t i c e n v i r o n m e n t . 16-2°-21,28 A c c o r d i n g l y , p r e s e n t s e d i m e n t s c o n t a i n e d d e t e c t a b l e levels of t e t r a - h e x a C N s (Table 3). No g r a d i e n t s from pulp m i l l s w e r e o b s e r v e d . One could c o n c l u d e that P C N s here are a i r b o r n e pollutants. C o p l a n a r PCBs (Table 3) a p p e a r e d at low b a c k r o u n d levels. The m o s t toxic c o n g e n e r PCB 126 was found only in one area (Kuh 3a) w h i c h is l o c a t e d nearest to a PCB l e a k a g e point. 26 D i c h l o r o - U P A C s w h i c h are a r t i f a c t s of TeCDDs in low r e s o l u t i o n G C / S I M (Table 4 and Fig. 5) s h o w e d c l e a r g r a d i e n t s d o w n s t r e a m s from p u l p mills. T h e i r o r i g i n from p u l p b l e a c h e r y had b e e n p r e v i o u s l y seen by a n a l y s e s of c o f f e e filter paper and effluent. ~7-Is Code names UPAC 1, 2 and 3 w e r e g i v e n to the isomers in the p r e v i o u s p u b l i c a t i o n . ~7 There they w e r e s u g g e s t e d to be C 6 - a l k y l d i c h l o r o - d i b e n z o f u r a n s . However, model s u b s t a n c e s t u d i e s t h e r e a f t e r indicated that these U P A C s w e r e not R-PCDFs but a l k y l a t e d d i c h l o r o b i b e n z y l s (R-PCBBs), instead.~9. 3o
ng/g
dw UPAC 3
.~.....~.PA.C...2
. . . . . . . . . . . . . . . . .
UPAC 1
4
0 -u--l
Area
1
2 Fig.
l
I
I
I
I
I
I
I
I
I
I
I
I
J
3
4
5
6
7
8
9
10
11
12
13
14
15
16
5. A p p r o x i m a t e contents of d i c h l o r o - U P A C s named in R e f . 1 7 (probably R-2CBBs) in dry s e d i m e n t samples.
17
18
1378
The contents measured for dioxins, furans and coplanar PCBs expressed as TEQs (equivalents of 2378-TeCDD; Table 5) are very low for these groups of toxins. Therefore, no significant direct environmental threat of this depot can be expected. Instead, other more clearly pulp mill originated organochlorines in these sediments must be more significant as potential environmental harm in the future while they appear in many orders of magnitude higher amounts. ACKNOWLEDGEMENTS We are grateful to MSc Juhani Tarhanen, University of Kuopio, for high resolution MS operations. National Science Council of the Academy of Finland, Helsinki Metropolitan Area Water Co and Water and Environment District of Central Finland are acknowledged for financial support. REFERENCES
1. J.Paasivirta, J.S~rkk~, T.Leskij~rvi and A.Roos. Transportation and enrichment of chlorinated phenolic compounds in different aquatic food chains. Chemosphere 9 (1980) 441-456. 2. S.J.Eisenreich and T.C.Johnson. PCBs in the Great Lakes: Sources, Sinks, Burdens. Chapter 4 in: PCBs: Human and Environmental hazards. Ed. by F.M.D'tri and M.Kamrin. Butterworth, Boston (1983) 49-75. 3. W.M.J.Strachan and C.J.Edwards. Organic pollutants in Lake Ontario. Chapter 11 in: Toxic Contaminants in the Great Lakes. Ed. by J.O.Nriagu and M.S.Simmons. Wiley, New York (1983) 239-264. 4. M.E.Pariso, J.R.St.Amant and T.B.Sheffy. Microcontaminants in Wisconsin's Coastal Zone. Chapter 12 in: Toxic Contaminants in the Great Lakes. Ed. by J.O.Nriagu and M.S.Simmons. Wiley, New York (1983) 265-285. 5. M.S.Simmons. PCB contamination in the Great lakes. Chapter 13 in: Toxic Contaminants in the Great Lakes. Ed. by J.O.Nriagu and M.S.Simmons. Wiley, New York (1983) 288-309. 6. J.Paasivirta, K.M~ntykoski, R.Paukku, T.Piilola, H.Vihonen, J.S~rkk~ and K.Granberg. PCB in the sediments of the Lake Jyv~sj~rvi. Aqua Fennica 16,1 (1986) 17-23. 7. First part of the series: J.Paasivirta, J.Knuutinen, P.Maatela, R.Paukku, J.Soikkeli and J.S~rkk~. Organic chlorine compounds in lake sediments and the role of the chlorobleaching effluents. Chemosphere 17 (1988) 137-146. 8. J.M.Czuczwa and R.A.Hites. Environmental fate of combustion-generated polychlorinated dioxins and furans. Environ. Sci.Technol. 18 (1984) 444-450. 9. J.M.Czuczwa, B.R.McVeety and R.A.Hites. Polychlorinated dibenzodioxins and dibenzofurans in sediments from Siskiwit Lake, Isle Royale. Chemosphere 14 (1985) 623-626. 10. J.M.Czuczwa, F.Niessen and R.A.Hites. Historical record of polychlorinated dibenzo-p-dioxins and dibenzofurans in Swiss lake sediments. Chemosphere 14 (1985) 1175-1179. 11. J.M.Czuczwa and R.A.Hites. Sources and fate of PCDD and PCDF. Chemosphere 15 (1986) 1417-1420. 12. C.Rappe, R.Andersson, P-A.Bergqvist, C.Brohede, Marianne Hansson, L-O.Kjeller, G.Lindstr~m, S.Marklund, M.Nygren, S.E.Swansson, M.Tysklind and K.Wiberg. Overview on environmental fate of chlorinated dioxins and dibenzofurans. Sources, levels and isomeric pattern in various matrices. Chemosphere 16 (1987) 1603-1618. 13. Second part of the series: P.Maatela, J.Paasivirta, J.S~rkk~ and R.Paukku. Organic chlorine in lake sediments. II. Organically bound chlorine. Chemosphere, submitted. 14. Third part of the series: J.Paasivirta, H.Hakala, J.Knuutinen, T.Otollinen, J.S~rkk~, L.Welling, R.Paukku and R.Lammi. Organic chlorine in lake sediments. III. Chlorohydrocarbons, free and chemically bound chlorophenols. Chemosphere, submitted. 15. S.Tanabe, N.Kannan, An. Subramanian, S.Watanabe and R.Tatsukawa. Highly toxic coplanar PCBs: occurence, source, persistency and toxic implications to wildlife and humans. Environ. Pollution 47 (1987) 147-163.
1379
16. J.Tarhanen, J.Koistinen, J.Paasivirta, P.J.Vuorinen, J.Koivusaari, I.Nuuja, N.Kannan and R.Tatsukawa. Toxic significance of planar aromatic compounds in Baltic ecosystem - new studies on extremely toxic coplanar PCBs. Chemosphere 18 (1989) 1067-1077. 17. J.Paasivirta, K.M~ntykoski, J.Koistinen, T.Kuokkanen, E.Mannila and K.Rissanen. Structure analyses of planar polychloroaromatic compounds in environment. Chemosphere 19 (1989) 149-154. 18. T.Kuokkanen and J.Koistinen. Contents of aromatic chlorohydrocarbons, toxaphene, PCDDs and PCDFs in spent bleach liquors after biological purification. Chemosphere 19 (1989) 727-730. 19. Nordic Expert Group. Nordisk Dioxinrisk BedSmning. NORD 1988:49 Nordisk Ministerr~d, Kobenhavn (1988). 20. J.Koistinen, J.Paasivirta and P.J.Vuorinen. Dioxins and other planar polychloroaromatic compounds in Baltic, Finnish and Arctic fish samples. Chemosphere 19 (1989) 527-530. 21. J.Koistinen. Residues of planar polychloroaromatic compounds in Baltic fish and seal. Chemosphere 20 (1990) 1043-1048. 22. G.Amendola, D.Barna, R.Blosser, L.LaFleur, A.McBride, F.Thomas, T.Tiernan and R.Whittemore. The occurence and fate of PCDDs and PCDFs in five bleached kraft pulp and paper mills. Chemosphere 18 (1989) 1181-1188. 23. D.W.Kuehl, B.C.Butterworth, W.M.DeVita and C.P.Sauer. Environmental contamination by polychlorinated dibenzo-p-dioxins and dibenzofurans associated with pulp and paper discharge. Biomed. Environm. Mass Spectr. 14 (1987) 443-447. 24. S.E.Swanson, C.Rappe, J.MalmstrSm and K.P.Kringstad. Emissions of PCDDs and PCDFs from the pulp industry. Chemosphere 17 (1988) 681-691. 25. C.Rappe, P-A.Bergqvist and L-O.Kjeller. Levels, trends and patterns of PCDDs and PCDFs in Scandinavian environmental samples. Chemosphere 18 (1989) 651-658. 26. S.Herve, P.Heinonen, R.Paukku, M.Knuutila, J.Koistinen and J.Paasivirta. Mussel incubation method for monitoring organochlorine pollutants in watercourses. Four-year application in Finland. Chemosphere 17 (1988) 1945-1961. 27. S.Herve, P.Heinonen, J.Paasivirta and T.Rantio. Monitoring of organochlorine compounds in the recipients of pulp and paper industry by mussels. Kemia-Kemi 16,10B (1989) 1104, and paper to be published. 28. B.Jansson, L.Asplund and M.Olsson. Analysis of polychlorinated naphthalenes in environmental samples. Chemosphere 13 (1984) 33-41. 29. T.Nevalainen and J.Koistinen. Model compounds synthesis for the structure determination of new unknown planar aromatic compounds originating from pulp mill. DIOXIN'90, 10th International Meeting, Bayreuth, F.R.G. 1014.9.1990. Short Papers 4 (1990) in print. 30. J.Koistinen, R.Herzschuh and J.Stach. PCDDs, PCDFs and some unknown chlorinated planar compounds in pulp mill products, effluents, sediments and exposed biota. DI0XIN'90, 10th International Meeting, Bayreuth, F.R.G. 10-14.9.1990. Short Papers 3 (1990) 259-262. (Received
in Germany
17 October
1990;
accepted
5 November
1990)
1371-1379,
1990
0 0 4 5 - 6 5 3 5 / 9 0 $3.00 + .00 Pergamon Press plc
O R G A N I C C H L O R I N E C O M P O U N D S IN LAKE SEDIMENTS. IV. DIOXINS, FURANS AND R E L A T E D C H L O R O A R O M A T I C COMPOUNDS. J a a n a Koistinen-,
J a a k k o P a a s i v i r t a - and J u k k a S H r k k ~ b
" D e p a r t m e n t of Chemistry, U n i v e r s i t y of J y v ~ s k y l ~ K y l l i k i n k a t u I-3, SF-40100 Jyv~skyl~, F i n l a n d b D e p a r t m e n t of Biology, U n i v e r s i t y of J y v ~ s k y l ~ Y l i o p i s t o n k a t u 9, SF-40100 Jyv~skyl~, F i n l a n d
ABSTRACT P o l y c h l o r o d l b e n z o - p - d i o x i n s (PCDDs), p o l y c h l o r o d i b e n z o f u r a n s (PCDFs), polyc h l o r o n a p h t h a l e n e s (PCNs) and c o p l a n a r PCBs w e r e m e a s u r e d in s u r f a c e sediments from 18 lake areas in C e n t r a l Finland. T o x i c 2 , 3 , 7 , 8 - s u b s t i t u t e d PCDD and PCDF c o n g e n e r s o c c u r r e d at low levels (<20 - 230 p g / g dw). PCNs a p p e a r e d at few ng/g (total PCNs) levels. Pulp mills or any o t h e r local sources could not be a s s o c i a t e d w i t h the s e d i m e n t e d PCDDS, PCDFs and PCNs. C o p l a n a r PCB c o n g e n e r s 77 and 105 (IUPAC Nr) w e r e g e n e r a l l y found at 20-550 p g / g levels. The most toxic c o n g e n e r 126 was m e a s u r e d (110 pg/g) only at one a r e a near a local PCB leakage. Pulp mill o r i g i n a t e d a r o m a t i c c h l o r o c o m p o u n d s w h i c h coelute with PCDDs and PCDFs in c l e a n up, p r o b a b l y alkyl p o l y c h l o r o b l b e n z y l s (R-PCBBs) a p p e a r e d at n g / g levels and showed a clear g r a d i e n t d o w s t r e a m s from p u l p mill effluent points. INTRODUCTION Sediment s t u d i e s are f r e q u e n t l y u s e d to follow the e n v i r o n m e n t a l fate of p e r s i s t e n t o r g a n i c c h l o r o c o m p o u n d s . I-7 The n o t o r i o u s PCDDs and PCDFs w e r e included in these studies in 1980s. e-~' B e c a u s e toxic PCDDS and PCDFs were d e t e c t e d at very low levels in p u l p mill e f f l u e n t s and products, they were studied in p u l p m i l l r e c i p i e n t sediments, as well. ~2 In the p r e s e n t study, we include PCDDs and PCDFs to our r e s e a r c h on o r g a n o c h l o r i n e s ' ' 6 " 7 " I m ' ~ + in C e n t r a l F i n l a n d lake sediments. A l s o o t h e r a r o m a t i c p o l y c h l o r o c o m p o u n d s which are s t u c t u r a l l y s i m i l a r to and c o e l u t e in c l e a n u p w i t h PCDDs and PCDFs are analyzed. T h e s e PLACs (Planar A r o m a t i c C h l o r o c o m p o u n d s ) include c o p l a n a r PCBs ~5-~6 and U P A C s (Unknown P l a n a r A r o m a t i c C h l o r o c o m p o u n d s ) ~7. Some d i c h l o r o - U P A C s are e l u t e d in GC at the same r e t e n t i o n w i n d o w g i v i n g low r e s o l u t i o n SIM ions by the same m/e 320, 322 and 324 as TeCDDs. ~7"~" SAMPLES, A N A L Y S E S AND R E S U L T S Sampling areas Study area and s a m p l i n g sites are shown in Fig. I. D e t a i l s of the s a m p l i n g places and m e t h o d s have b e e n d e s c r i b e d in the s e c o n d p a p e r of the p r e s e n t series. 13 O n l y s u r f a c e s e d i m e n t s w e r e a n a l y z e d in the p r e s e n t study.
1371
1372
Norway ,-. ,.,'.
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,'
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Sweden ~
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1~" Fig. I. The sampling sites.
,o ~
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' ' 2~° ~ 4~
Compounds studied The compounds analyzed are shown in Fig. 2.
PCDD
PCB 77
PCDF
PCN
PCB 105
clClc l ~ PCB 126 Fig.
PCB 169
2. Structure type formula of polychlorodibenzo-pdioxins (PCDD), polychlorodibenzofurans (PCDF) and polychloronaphthalenes (PCN). Formula and name abbreviations of four coplanar PCBs analyzed: PCB 77 = 3,3',4,4'-tetrachlorobiphenyl, PCB 105 = 2,3,3',4,4'-pentachlorobiphenyl, PCB 126 = 3,3',4,4'5-pentachlorobiphenyl and PCB 169 = 3,3',4,4'5,5'-hexachlorobiphenyl.
Analysis prodecure The surface sediment sample was freeze-dried and the residue (2-16 g) was weighed. Samples taken in 1988 (areas 1-8) were extracted in Soxhlet with toluene-for 48 hours after s p i k i n g with 13Ci~-labelled internal standards, 2378-TeCDF and 2378-TeCDD (2.5 ng each). The samples taken in 1989 (areas 9-18) were treated with a modified method using duplicates: a mixture containing IsC12-1abelle d 2378-TeCDF, 12378-PeCDF, 12378-PeCDD and 1232478-HxCDD (5 ng each) was added. ~sC-2378-TCDD was not used, because it interferes with HxCN in SIM. Then, one sample was extracted in Soxhlet with toluene for 48 hours and the duplicate sample with methanol-dichloromethane 1:2 (v/v) for 24 hours.
1373
Each e x t r a c t was e v a p o r a t e d in R o t a v a p o r to 5 ml and then g e n t l y to dryness w i t h n i t r o g e n gas flow. The r e s i d u e was d i s s o l v e d in 4 ml of h e x a n e and shaken two times w i t h 4 ml of conc. s u l f u r i c acid. Then, sulfur was r e m o v e d by adding about I g of Cu p o w d e r (activated w i t h conc. HCl) and s h a k i n g for 2 min. The h e x a n e was c o n c e n t r a t e d w i t h n i t r o g e n gas flow to 0.5 ml and t r a n s f e r r e d to an a c t i v a t e d c a r b o n c o l u m n c o n t a i n i n g 50 mg of SK-4 A l l t e c h b a r b o n (80/100 mesh) in 10 cm long, 6 mm o.d. and 4 m m i.d. g l a s s tube (plugs of h e x a n e w a s h e d cotton). The total length of the c a r b o n part was 10 mm. N o n p l a n a r c o m p o u n d s w e r e e l u t e d out from the c o l u m n w i t h 10 ml of h e x a n e d i c h l o r o m e t h a n e 1:1 (v/v). T h e n the c o l u m n was i n v e r t e d and the d i o x i n f r a c t i o n e l u t e d (reverse elution) w i t h 10 ml of toluene. T e t r a d e c a n e (20 ~i) was added and t o l u e n e e v a p o r a t e d g e n t l y w i t h n i t r o g e n gas flow. The r e s i d u e was r e d i s s o l v e d in 0.5 ml of h e x a n e and i n t r o d u c e d to a c o l u m n of 2 g of b a s i c a l u m i n a (Alumina B, A c t i v i t y I, ICN B i o m e d i c a l s ) in a P a s t e u r pipette. A f t e r e l u t i o n w i t h 10 ml of h e x a n e - d i c h l o r o m e t h a n e 98:2 (v/v) the d i o x i n f r a c t i o n was c o l l e c t e d by e l u t i n g w i t h 10 ml of h e x a n e : d i c h l o r o m e t h a n e 1:1 (v/v). A f t e r a d d i n g t e t r a d e c a n e (20 ~i) the d i o x i n f r a c t i o n was c o n c e n t r a ted in n i t r o g e n gas flow for the GC/MS analysis. One or two ~i of s o l u t i o n was i n j e c t e d s p l i t l e s s l y to a gas c h r o m a t o g r a p h / m a s s s e l e c t i v e d e t e c t o r s y s t e m m o d e l HP 5970 e q u i p p e d w i t h a SE-54 fused silica c a p i l l a r y c o l u m n (25 m, 0.21 mm i.d., film t h i c k n e s s 0.11 ~m). I n j e c t o r t e m p e r a t u r e was 250°C. O v e n t e m p e r a t u r e p r o g r a m e m p l o y e d was: 100 ° isothermal for 1 min, then + 20°/min to 180 ° , and finally + 5°/min to 290 ° . H e l i u m was u s e d as c a r r i e r gas (30 cm/s). CG/MS t r a n s f e r line was kept at 300°C. Low r e s o l u t i o n SIM mode was used at s t a n d a r d EI c o n d i t i o n s m o n i t o r i n g three s e l e c t e d m/e values (M ÷, M÷+2, M÷+4) for e a c h c o n g e n e r group. I d e n t i f i c a t i o n was b a s e d on the r e t e n t i o n times c o m p a r e d to those of the a u t h e n t i c s t a n d a r d c o m p o u n d s and on the i n t e n s i t y ratios of the peaks. While d i c h l o r o - U P A C m o l e c u l a r ions give peaks to the same w i n d o w as TeCDDs, Iv identity of the l a t t e r was c h e c k e d by high r e s o l u t i o n GC/MS ( V G 7 0 - 2 5 0 S E in the U n i v e r s i t y of Kuopio): w h e n ion m/e 319.8965 was m o n i t o r e d U P A C peaks were absent but "other TeCDD" peaks w e r e still present. Q u a n t i t a t i o n of PCDDs, PCDFs and c o p l a n a r PCBs was b a s e d on the r e s p o n s e factors o b t a i n e d from the G C / S I M of s t a n d a r d m i x t u r e s and internal standards. For PCNs and UPACs, the r e s p o n s e factor one r e l a t e d to ~ s c ~ 2 - 2 3 7 8 - T e C D F was a s s u m e d and used, because single m o d e l c o m p o u n d s w e r e not available. Results
No s i g n i f i c a n t d i f f e r e n c e s b e t w e e n the two e x t r a c t i o n m e t h o d s w e r e obtained. C o n s e q u e n t l y only results from m e t h a n o l - d i c h l o r o m e t h a n e e x t r a c t s are p r e s e n t e d here. C o n t e n t s of PCDDs are shown in T a b l e I, PCDFs in T a b l e 2, PCNs and c o p l a n a r PCBs in T a b l e 3 and UPACs in T a b l e 4. For e s t i m a t i o n of the dioxin type of toxic load in the samples, the c o n c e n t r a t i o n s of o b s e r v e d 2,3,7,8- s u b s t i t u t e d c o n g e n e r s were m u l t i p l i e d by N o r d i c TEF factors 19 and summarized. The levels of m e a s u r e d c o p l a n a r PCBs w e r e m u l t i p l i e d by TEF factors r e c e n t l y s u g g e s t e d in D i o x i n ' 9 0 s y m p o s i u m and summarized, as well. The o b t a i n e d T E Q - v a l u e s (2378-TeCDD equivalents) are p r e s e n t e d in T a b l e 5.
DISCUSSION The m o s t toxic 2 3 7 8 - T e C D D was not d e t e c t e d in any samples, but its two noni d e n t i f i e d isomers w e r e c o m m o n and a b u n d a n t in pulp mill r e c i p i e n t s and showed a clear g r a d i e n t d o w n s t r e a m s (Table I and Fig. 3). W h i l e s e d i m e n t a t i o n rates of dry m a t t e r b e l o w mill, e s p e c i a l l y at area 4 (Kuh 4) are v e r y high, 7,13 the amounts of a n n u a l l y p r e c i p i t a t e d T e C D D s m u s t m a k e a still m o r e steep gradient. Therefore, one can c o n c l u d e that these less toxic T e C D D s in s e d i m e n t s o r i g i n a t e from the c h l o r o b l e a c h i n g of pulp.
1374
In c o n t r a r y to the o b s e r v e d TeCDDs, the toxic hexa-, h e p t a - and o c t a c h l o r o dioxins found (Table 1 and Fig. 4) are c e r t a i n l y not p u l p mill originated. The same is the case for 1 2 3 4 6 7 8 - H p C D F and OCDF (Table 2) w h i c h m i g h t come from c o m b u s t i o n s at the m o r e d e n s e l y p o p u l a t e d and i n d u s t r i a l i z e d areas in South Finland. TABLE 1 . 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 p g / g in dry s u r f a c e sediments. L i m i t of d e t e r m i n a t i o n for areas 1-8 was 50 and for areas 9-18 20 pg/g. Sample
2378TeCDD
I. Kei 2. Kii 3. Kuh 3a 4. Kuh 4 5. Vat 6. Lep 7. Pot 8. Ris 9. Van 1 0 . Sou 11. Olk 12. Tii 13. Leh 14. Jud 15. Teh 16. Vir 17. Asi 18. V~
Other TeCDDs
0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
12378PnCDD
0 0 930 1010 1400 590 280 420 110 100 40 80 70 90 50 40 0 0
123478- 123678- 123789HxCDD HxCDD HxCDD
0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 20 0 0
0 0 0 0 0 0 61 0 82 78 0 0 79 77 0 40 0 0
0 0 0 0 0 0 0 0 39 0 0 0 34 0 0 0 0 0
1234678HpCDD
OCDD
0 0 0 0 0 0 0 0 34 0 0 0 0 25 49 36 0 0
0 0 0 0 0 0 0 0 34 0 0 0 0 34 0 42 0 0
TABLE 2. P o l y c h l o r i n a t e d d i b e n z o f u r a n s pg/g in dry s u r f a c e sediments. L i m i t of d e t e r m i n a t i o n for areas I-8 was 50 and for areas 9-18 20 pg/g. Sample
2378- 12378- 23478- 123478 123678 123789 234678 1234678 1234789 T e C D F PnCDF PnCDF -HxCDF -HxCDF -HxCDF -HxCDF -HpCDF -HpCDF
1. Kei 2. Kii 3. Kuh 3a 4. Kuh 4 5. Vat 6. Lep 7. Por 8. Ris 9. Van 10. Sou 11. Olk 12. Tii 13. Leh 14. Jud 15. Teh 16. Vir 17. Asi 18. Vaa
0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
0 0 0 0 0 0 64 0 79 63 42 0 32 39 39 44 230 150
0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
OCDF 0 0 0 0 0 0 0 0 22 0 0 0 0 0 0 0 160 75
1375
1600
pg/g
dw
1
3
1400 1200 1000
800600400200 0 A r e a
Fig.
2
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
3. C o n c e n t r a t i o n s of TeCDDs ( 2 , 3 , 7 , 8 - i s o m e r not detected) in dry s e d i m e n t samples.
200 Octa-CDD
Pg/g
1234678-HpCDD
dw 150
....
123678-HxCDD
................................................m i
............
123478-HxCDD 100
0
Area
.....................................................................................................................
I
I
I
I
I
t
I
I
I
I
2
3
4
5
6
7
8
9
Fig.
4.
10
11
12
13
14
15
16
17
18
Concentrations of toxic PCDD c o n g e n e r s in dry s e d i m e n t samples.
2 3 7 8 - T e C D F and 2 3 4 7 8 - P n C D F w h i c h were found to be in m a n y cases the most a b u n d a n t toxic P C D D / F c o n g e n e r s in a q u a t i c animals 12,2°,21 and also in pulp c h l o r o b l e a c h i n g w a s t e s 22-23 w e r e n o n d e t e c t a b l e in the p r e s e n t s e d i m e n t samples. The P C D D / F c o n g e n e r ratios show m o r e "backround" than "bleaching" pattern w h e n c o m p a r e d to the results of R a p p e et al. ~4-2s This i n d i c a t e s that d i o x i n p o l l u t i o n from C e n t r a l - F i n n i s h p u l p mills, at least in recent years, has b e e n very low. E.g. c o n t e n t s of toxic P C D D / F s in s u r f a c e sediments near p u l p m i l l s at S w e d i s h West Coast w e r e c o n s i d e r a b l y higher. 12-zs
1376
TABLE
3. P o l y c h l o r o n a p h t h a l e n e s and c o p l a n a r PCBs p g / g in dry s u r f a c e sediments. L i m i t of d e t e r m i n a t i o n for a r e a s I-8 was 50 pg/g and for areas 9-18 20 pg/g. N o t anal y s e d = -I.
Sample
Pol¥chloronaphthalenes TeCN PnCN HxCN HpCN OCN
1. Kei 2. Kii 3. Kuh 3a 4. Kuh 4 5. Vat 6. Lep 7. Por 8. Ris 9. V a n 10. Sou 11. Olk 12. Tii 13. Leh 14. Jud 15. Teh 16. V i r 17. Asi 18. V ~
TABLE
UPAC
Kei Kii Kuh 3a Kuh 4 Vat Lep Por Ris Van
TABLE
1
0 0 0.21 2.70 1.00 1.70 0.26 0.11 0.06
0 0 250 170 0 0 0 0 30 30 0 0 30 40 70 50 130 50
0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
98 61 0 0 0 160 89 130 120 250 0 0 550 270 230 200 210 110
-1 -1 -I -1 -I -1 -I -I 98 100 52 90 120 110 120 100 120 54
PCBs 126
169
0 0 110 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
UPAC
2
UPAC
0 0 0.06 0.91 0.32 0.37 0.08 0 0.02
3
!
Sample
0 0 0.31 4.50 1.30 1.70 0.45 0 0.12
! ! ! ! ! ! ! ! !
10 11 12 13 14 15 16 17 18
UPAC
SOU 01k Tii Leh Jud Teh Vir Asi V~
1
UPAC
0.07 0.06 0.19 0.10 0.04 0.02 0 0 0
2
UPAC
0.02 0.03 0.10 0.09 0.02 0 0 0 0
Kei Kii Kuh 3a Kuh 4 Vat Lep Por Ris Van
PCDD+PCDF 0 0 0 0 0 0 6.7 0 13.0
Copl.
PCB
1.0 0.6 11.0 0 0 1.6 0.9 1.3 1.7
!
Sample
! ! ! ! ! ! ! ! !
10. 11. 12. 13. 14. 15. 16. 17. 18.
Sou Olk Tii Leh Jud Teh Vir Asi V~
PCDD+PCDF
Copl.
8.4 0.4 0 12.0 8.4 0.9 6.8 2.5 1.6
* S u g g e s t i o n of S . S a f e in D I O X I N ' 9 0 s y m p o s i u m in B a y r e u t h FGR, S e p t e m b e r 10th 1990: TEF factors for PCBs 77, 105 and 126 s h o u l d be 0.01, 0.001 and 0.1, r e s p e c t i v e l y .
3
0.13 0.08 0.18 0.17 0.08 0.05 0.02 0 0
5. S u m m a r i z e d c o n c e n t r a t i o n s of o b s e r v e d toxic P C D D s + P C D F s (NORDIC 19) and c o p l a n a r PCBs (77+105+126; Safe *) pg/g as 2 3 7 8 - T e C D D e q u i v a l e n t s (TEQs) in dry s u r f a c e sediments.
Sample 1. 2 3 4 5 6 7 8 9
140 140 0 150 370 460 240 370 110 320 0 0 120 120 240 130 490 170
Coplanar 105
4. D i c h l o r o - U P A C s (names in Ref 17) n g / g in dry s u r f a c e sediments. Limit of d e t e r m i n a t i o n for areas 1-8 was 0.05 and for areas 9-18 0.02 ng/g.
Sample I. 2. 3. 4. 5. 6. 7. 8. 9.
790 1400 3200 3000 1300 1000 540 1400 600 2500 490 610 400 450 1600 370 2200 680
77
PCB
2.6 0.1 0.1 5.6 2.8 2.4 2.1 2.2 1.2
1377
Low levels of d i o x i n s in the r e c i p i e n t s e d i m e n t s s t u d i e d in this w o r k are p a r a l l e l w i t h o b s e r v a t i o n s on local mill effluent. T o x i c PCDDs and PCDFs were n o n d e t e c t a b l e (< 50 pg/l) in the e f f l u e n t w a t e r I" and in m u s s e l s (< 50 p g / g dw) i n c u b a t e d n e a r to the e f f l u e n t pipe 26 of the a c t i v a t e d sludge t r e a t m e n t plant of a k r a f t p u l p mill. In contrary, five t o x i c c o n g e n e r s w e r e m e a s u r e d (total 600 p g / g dw) in m u s s e l s incubated b e l o w k r a f t m i l l s w i t h o u t b i o l o g i c a l purification. 27 PCNs have b e e n o b s e r v e d as g e n e r a l l y occurring, p e r s i s t e n t and b i o a c c u m u l a t i n g traces in B a l t i c e n v i r o n m e n t . 16-2°-21,28 A c c o r d i n g l y , p r e s e n t s e d i m e n t s c o n t a i n e d d e t e c t a b l e levels of t e t r a - h e x a C N s (Table 3). No g r a d i e n t s from pulp m i l l s w e r e o b s e r v e d . One could c o n c l u d e that P C N s here are a i r b o r n e pollutants. C o p l a n a r PCBs (Table 3) a p p e a r e d at low b a c k r o u n d levels. The m o s t toxic c o n g e n e r PCB 126 was found only in one area (Kuh 3a) w h i c h is l o c a t e d nearest to a PCB l e a k a g e point. 26 D i c h l o r o - U P A C s w h i c h are a r t i f a c t s of TeCDDs in low r e s o l u t i o n G C / S I M (Table 4 and Fig. 5) s h o w e d c l e a r g r a d i e n t s d o w n s t r e a m s from p u l p mills. T h e i r o r i g i n from p u l p b l e a c h e r y had b e e n p r e v i o u s l y seen by a n a l y s e s of c o f f e e filter paper and effluent. ~7-Is Code names UPAC 1, 2 and 3 w e r e g i v e n to the isomers in the p r e v i o u s p u b l i c a t i o n . ~7 There they w e r e s u g g e s t e d to be C 6 - a l k y l d i c h l o r o - d i b e n z o f u r a n s . However, model s u b s t a n c e s t u d i e s t h e r e a f t e r indicated that these U P A C s w e r e not R-PCDFs but a l k y l a t e d d i c h l o r o b i b e n z y l s (R-PCBBs), instead.~9. 3o
ng/g
dw UPAC 3
.~.....~.PA.C...2
. . . . . . . . . . . . . . . . .
UPAC 1
4
0 -u--l
Area
1
2 Fig.
l
I
I
I
I
I
I
I
I
I
I
I
I
J
3
4
5
6
7
8
9
10
11
12
13
14
15
16
5. A p p r o x i m a t e contents of d i c h l o r o - U P A C s named in R e f . 1 7 (probably R-2CBBs) in dry s e d i m e n t samples.
17
18
1378
The contents measured for dioxins, furans and coplanar PCBs expressed as TEQs (equivalents of 2378-TeCDD; Table 5) are very low for these groups of toxins. Therefore, no significant direct environmental threat of this depot can be expected. Instead, other more clearly pulp mill originated organochlorines in these sediments must be more significant as potential environmental harm in the future while they appear in many orders of magnitude higher amounts. ACKNOWLEDGEMENTS We are grateful to MSc Juhani Tarhanen, University of Kuopio, for high resolution MS operations. National Science Council of the Academy of Finland, Helsinki Metropolitan Area Water Co and Water and Environment District of Central Finland are acknowledged for financial support. REFERENCES
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in Germany
17 October
1990;
accepted
5 November
1990)