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A graphical presentation of the composition and properties of chlorinated dibenzodioxins and dibenzofurans
The Science of the Total Environment, 83 (1989) 191 194 Elsevier Science Publishers B.V., Amsterdam -- Printed in The Netherlands
191
Short Communication A GRAPHICAL P R E S E N T A T I O N OF THE COMPOSITION A N D P R O P E R T I E S OF CHLORINATED D I B E N Z O D I O X I N S A N D DIBENZOFURANS
V. ZITKO Marine Chemistry Division, Physical and Chemical Sciences Branch, Department of Fisheries and Oceans, St. Andrews, N.B. EOG 2XO (Canada)
(Received September 6th, 1988; accepted February 17th, 1989)
ABSTRACT A graphical display of chlorinated dibenzodioxins (CDD) and dibenzofurans (CDF) is described. Coordinates of the congeners are calculated by assigning powers of 2 to the substitution sites. Values of substituted sites are added. The system also results in a compact congener designation.
INTRODUCTION
As a c o n s e q u e n c e of efficient s e p a r a t i o n techniques, a n a l y s t s are able to d e t e c t a n d q u a n t i t a t e large n u m b e r s of closely r e l a t e d c o m p o u n d s such as i n d i v i d u a l c h l o r o b i p h e n y l s (PCB), c h l o r i n a t e d dibenzodioxins (CDD), and dib e n z o f u r a n s (CDF). It is difficult to see p a t t e r n s in the r e s u l t i n g long tables of d a t a d e a l i n g with l a r g e n u m b e r s of c o n g e n e r s . A g r a p h i c a l display of P C B was described r e c e n t l y [1]. E a c h PCB c o n g e n e r was assigned a pair of c o o r d i n a t e s by g i v i n g v a l u e s t h a t are powers of 2 to the sites on the two benzene rings of the b i p h e n y l molecule, respectively. The values of the s u b s t i t u t e d sites were t h e n added. A c o n c e n t r a t i o n or a p r o p e r t y was used as the 3rd c o o r d i n a t e . The r e s u l t i n g t h r e e - d i m e n s i o n a l p r e s e n t a t i o n helped in visual p a t t e r n r e c o g n i t i o n . RESULTS AND DISCUSSION This S h o r t C o m m u n i c a t i o n extends the a b o v e principle to CDD and CDF. To c l u s t e r the h i g h l y toxic '~2,3,7,8"-substituted c o n g e n e r s , h i g h values are assigned to these sites: Site
1
2
3
4
Value
1
4
8
2
Site
6
7
8
9
W i t h t h e s e a s s i g n m e n t s , the h i g h l y toxic isomers h a v e c o o r d i n a t e s 12 (2,3-;
0048-9697/89/$03.50
© 1989 Elsevier Science Publishers B.V.
192
DIOXINS
/o~
/
/
/
/
/oHo-4o °-oO°yo
/--,-
-oo
,s
.
olo
.~o ~ / ° / o ° - ~ o ° . / o / /oO__/__ o o /o .o o // /o ~oOoO___~oOo~_oO__~-oO' /oO o=oO_O__~o oo 0
4
8
12
16
Fig. 1. Positions of all 75 chlorinated dibenzodioxins (CDD). The toxic "2,3,7,8"-type congeners are indicated by bars.
DIBENZOFURANS
/
/
'
/ )0 o
/ 0
/
/--,--
_
,s
o ,~-~0 u 7
/ o °-~o°o-/o -o~ o ~ Z : o ~ : o ° ~ ° o°~ //_ _ . / o % -~o%/-o-~o°--~oe-/-o
o OVOo°--~o ooO° oF
.Ao_~oO_/_.o o / 0
o /-o
o ° o'- o - o ° o ° o~°o ° o ~ . . . . . . . 4
8
12
16
Fig. 2. Positions of all 135 chlorinated dibenzofurans (CDF). The toxic "2,3,7,8"-type congeners are indicated by bars.
7,8-), 13 (1,2,3-; 6,7,8-), and 14 (2,3,4-; 7,8,9-); see Figs 1 and 2 for CDD and CDF, respectively. Figure 3 depicts the mixture of CDF detected by Ono et al. [2] in killer whales. Unresolved congeners are indicated by numbers at the top of the bars and are assigned equal concentrations. Concentrations of minor components may be highlighted by plotting square root of concentration on the Z-axis. One can see that the very toxic 2,3,7,8-tetrachlorodibenzofuran (coordinates 12,12) and 2,3,4,8-tetrachlorodibenzofuran (coordinates 14,8) are not resolved and that relative concentration of their mixture is very low. Similarly, another very toxic congener, 1,2,3,7,8-pentachlorodibenzofuran (coordinates 13,12), is not resolved from 1,2,3,4,8-pentachlorodibenzofuran (coordinates 15,8). The pattern of CDF in killer whales is easily distinguishable from the pattern of CDF in the fly ash of a municipal incinerator (Fig. 4, [3]). The assignment of coordinates to CDD and CDF is similar to the proposed
193
7/12 F/
0
2
4
6
8
10
12
14
16
Fig. 3. Chlorinated dibenzofurans (CDF) in killer whales [2]. Numbers indicate unresolved congeners.
YASU
1
SQR Scale
4
3 /----
~3~
6
l--
'-- s •
0
2
4
6
8
10
'
16
d" I±
,~2
7,,0
12
14
16
Fig. 4. Chlorinated dibenzofurans (CDF) in fly ash of a municipal-waste incinerator [3]. Numbers indicate unresolved congeners. " s h o r t h a n d " n u m b e r i n g [4]. In the s h o r t h a n d n u m b e r i n g , the s u b s t i t u t i o n p a t t e r n is r e d u c e d to two symbols by u s i n g letters for n u m b e r s l a r g e r t h a n 9 (10 = A, 11 = B . . . . 15 = F; h e x a d e c i m a l notation). T h u s the s h o r t h a n d desi g n a t i o n of a 2,3,7,8-tetrachloro c o m p o u n d s is CC. One m u s t i n d i c a t e w h e t h e r it is a dibenzodioxin or dibenzofuran, unless clear from the context. A p r o g r a m for c a l c u l a t i n g a n d p l o t t i n g the c o o r d i n a t e s is available from the author. ACKNOWLEDGEMENTS I t h a n k Messrs W.G. M c M u l l o n and F.B. C u n n i n g h a m for p r e p a r i n g the figures.
194 REFERENCES 1 2 3 4
V. Zitko, Anal. Chem., 60 (1988) 1998. M. Ono, N. Kannan, T. Wakimoto and R. Tatsukawa, Mar. Pollut. Bull., 18 (1987) 640. A. Yasuhara, H. Ito and M. Morita, Environ. Sci. Technol., 21 (1987) 971. V. Zitko, Chemosphere, 14 (1985) 165.
191
Short Communication A GRAPHICAL P R E S E N T A T I O N OF THE COMPOSITION A N D P R O P E R T I E S OF CHLORINATED D I B E N Z O D I O X I N S A N D DIBENZOFURANS
V. ZITKO Marine Chemistry Division, Physical and Chemical Sciences Branch, Department of Fisheries and Oceans, St. Andrews, N.B. EOG 2XO (Canada)
(Received September 6th, 1988; accepted February 17th, 1989)
ABSTRACT A graphical display of chlorinated dibenzodioxins (CDD) and dibenzofurans (CDF) is described. Coordinates of the congeners are calculated by assigning powers of 2 to the substitution sites. Values of substituted sites are added. The system also results in a compact congener designation.
INTRODUCTION
As a c o n s e q u e n c e of efficient s e p a r a t i o n techniques, a n a l y s t s are able to d e t e c t a n d q u a n t i t a t e large n u m b e r s of closely r e l a t e d c o m p o u n d s such as i n d i v i d u a l c h l o r o b i p h e n y l s (PCB), c h l o r i n a t e d dibenzodioxins (CDD), and dib e n z o f u r a n s (CDF). It is difficult to see p a t t e r n s in the r e s u l t i n g long tables of d a t a d e a l i n g with l a r g e n u m b e r s of c o n g e n e r s . A g r a p h i c a l display of P C B was described r e c e n t l y [1]. E a c h PCB c o n g e n e r was assigned a pair of c o o r d i n a t e s by g i v i n g v a l u e s t h a t are powers of 2 to the sites on the two benzene rings of the b i p h e n y l molecule, respectively. The values of the s u b s t i t u t e d sites were t h e n added. A c o n c e n t r a t i o n or a p r o p e r t y was used as the 3rd c o o r d i n a t e . The r e s u l t i n g t h r e e - d i m e n s i o n a l p r e s e n t a t i o n helped in visual p a t t e r n r e c o g n i t i o n . RESULTS AND DISCUSSION This S h o r t C o m m u n i c a t i o n extends the a b o v e principle to CDD and CDF. To c l u s t e r the h i g h l y toxic '~2,3,7,8"-substituted c o n g e n e r s , h i g h values are assigned to these sites: Site
1
2
3
4
Value
1
4
8
2
Site
6
7
8
9
W i t h t h e s e a s s i g n m e n t s , the h i g h l y toxic isomers h a v e c o o r d i n a t e s 12 (2,3-;
0048-9697/89/$03.50
© 1989 Elsevier Science Publishers B.V.
192
DIOXINS
/o~
/
/
/
/
/oHo-4o °-oO°yo
/--,-
-oo
,s
.
olo
.~o ~ / ° / o ° - ~ o ° . / o / /oO__/__ o o /o .o o // /o ~oOoO___~oOo~_oO__~-oO' /oO o=oO_O__~o oo 0
4
8
12
16
Fig. 1. Positions of all 75 chlorinated dibenzodioxins (CDD). The toxic "2,3,7,8"-type congeners are indicated by bars.
DIBENZOFURANS
/
/
'
/ )0 o
/ 0
/
/--,--
_
,s
o ,~-~0 u 7
/ o °-~o°o-/o -o~ o ~ Z : o ~ : o ° ~ ° o°~ //_ _ . / o % -~o%/-o-~o°--~oe-/-o
o OVOo°--~o ooO° oF
.Ao_~oO_/_.o o / 0
o /-o
o ° o'- o - o ° o ° o~°o ° o ~ . . . . . . . 4
8
12
16
Fig. 2. Positions of all 135 chlorinated dibenzofurans (CDF). The toxic "2,3,7,8"-type congeners are indicated by bars.
7,8-), 13 (1,2,3-; 6,7,8-), and 14 (2,3,4-; 7,8,9-); see Figs 1 and 2 for CDD and CDF, respectively. Figure 3 depicts the mixture of CDF detected by Ono et al. [2] in killer whales. Unresolved congeners are indicated by numbers at the top of the bars and are assigned equal concentrations. Concentrations of minor components may be highlighted by plotting square root of concentration on the Z-axis. One can see that the very toxic 2,3,7,8-tetrachlorodibenzofuran (coordinates 12,12) and 2,3,4,8-tetrachlorodibenzofuran (coordinates 14,8) are not resolved and that relative concentration of their mixture is very low. Similarly, another very toxic congener, 1,2,3,7,8-pentachlorodibenzofuran (coordinates 13,12), is not resolved from 1,2,3,4,8-pentachlorodibenzofuran (coordinates 15,8). The pattern of CDF in killer whales is easily distinguishable from the pattern of CDF in the fly ash of a municipal incinerator (Fig. 4, [3]). The assignment of coordinates to CDD and CDF is similar to the proposed
193
7/12 F/
0
2
4
6
8
10
12
14
16
Fig. 3. Chlorinated dibenzofurans (CDF) in killer whales [2]. Numbers indicate unresolved congeners.
YASU
1
SQR Scale
4
3 /----
~3~
6
l--
'-- s •
0
2
4
6
8
10
'
16
d" I±
,~2
7,,0
12
14
16
Fig. 4. Chlorinated dibenzofurans (CDF) in fly ash of a municipal-waste incinerator [3]. Numbers indicate unresolved congeners. " s h o r t h a n d " n u m b e r i n g [4]. In the s h o r t h a n d n u m b e r i n g , the s u b s t i t u t i o n p a t t e r n is r e d u c e d to two symbols by u s i n g letters for n u m b e r s l a r g e r t h a n 9 (10 = A, 11 = B . . . . 15 = F; h e x a d e c i m a l notation). T h u s the s h o r t h a n d desi g n a t i o n of a 2,3,7,8-tetrachloro c o m p o u n d s is CC. One m u s t i n d i c a t e w h e t h e r it is a dibenzodioxin or dibenzofuran, unless clear from the context. A p r o g r a m for c a l c u l a t i n g a n d p l o t t i n g the c o o r d i n a t e s is available from the author. ACKNOWLEDGEMENTS I t h a n k Messrs W.G. M c M u l l o n and F.B. C u n n i n g h a m for p r e p a r i n g the figures.
194 REFERENCES 1 2 3 4
V. Zitko, Anal. Chem., 60 (1988) 1998. M. Ono, N. Kannan, T. Wakimoto and R. Tatsukawa, Mar. Pollut. Bull., 18 (1987) 640. A. Yasuhara, H. Ito and M. Morita, Environ. Sci. Technol., 21 (1987) 971. V. Zitko, Chemosphere, 14 (1985) 165.