Solving Hazardous Waste Problems - American Chemical Society

Chapter 31

Chemical Degradation of Selected Polychlorinated Compounds by Means of Polyethers, a Base, and an Oxidant 1

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Downloaded by UNIV OF MASSACHUSETTS AMHERST on June 2, 2018 | https://pubs.acs.org Publication Date: April 24, 1987 | doi: 10.1021/bk-1987-0338.ch031

G. Nobile , W. Tumiatti , and P. Tundo

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Sea Marconi Technologies, Strada Antica di Collegno, 196-10146 Torino, Italy Istituto di Chimica Organica dell'Università di Torino, Via G. Bidone, 36-10125 Torino, Italy 2

Mixtures of polyethyleneglycols (and ethylene oxide-propylene oxide copolymers), a base and a peroxide (or other radical initiators) allow the preparation of several reagents which, suitably formulated according to their different use, are able to degrade the chemically stable chlorinated aromatics. Such a method, called CDP-Process, is active on TCDD and can be applied in different ways; as an example, the reagent, when immobilized on a solid bed, allows the continuous-flow decontamination of mineral oils containing PCB; this is useful for the decontamination of an electrical transformer during operation. Another reported example is the decontamination of surfaces contaminated by PCB or PCB fires (where PCDF and PCDD are also present). Since the ecological and environmental hazard related to stable polyhalogenated aromatic compounds has been recognized, many efforts have been done by chemists both for limiting their spreading in the environment and for their elimination. In order to reach this aim the contaminated material is put in landfills or incinerated, or the organic pollutants are chemically decomposed. Each method has its peculiarity and applicability. The advantages of chemical methods of decontamination are in the ultimate elimination of the problem, in the possibility of operating in situ, and in the use of inexpensive equipment. For these reasons new chemical methods able to destroy the stable molecules of chlorinated aromatics are being examined. For polychorinated biphenyls (PCB), many methods have been reported. For example: the reaction of polyethyleneglycols (PEG) of low molecular weight (MW) in the presence of strong bases (i.e. KOH) and stirring (1, 2); the use of sodium polyethyleneglycolates (3); the utilization of alkali metal hydroxide/glycol mixture in the presence of dimethylsulfoxide (4) and u.v. irradiation (5). Several methods have also been described for the more toxic of such compounds, that is the 2,3,7,8tetrachlorodibenzo-p-dioxin (TCDD); among them, remarkable are the u.v. irradiation (6), the 0097-6156/87/0338-0376$06.00/0 © 1987 American Chemical Society

Exner; Solving Hazardous Waste Problems ACS Symposium Series; American Chemical Society: Washington, DC, 1987.

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e x h a u s t i v e c h l o r i n a t i o n ( 7 ) , t h e r e a c t i o n w i t h sodium g l y c o l a t e s (8). A new method o f d e g r a d a t i o n , c a l l e d CDP-Process (Chemical D e g r a d a t i o n o f P o l y h a l o g e n a t e d compounds), i s d e s c r i b e d t o g e t h e r w i t h i t s a p p l i c a t i o n i n t h e f i e l d ( 9 ) . A c c o r d i n g t o t h e CDPP r o c e s s p o l y c h l o r i n a t e d compounds a r e e a s i l y degraded i f t h e r e a c t i o n i s c a r r i e d o u t i n t h e presence o f PEG o f h i g h MW, a base (even K CO3 o r NaHC0 c a n be u s e d ) , a p e r o x i d e o r a r a d i c a l i n i t i a t o r ; moreover, t h e r e a g e n t s m i x t u r e c a n be s u i t a b l y f o r m u l a ted i n o r d e r t o o b t a i n d i f f e r e n t a p p l i c a t i o n s . 2


Chemical Degradation of Polychlorinated Compounds

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CDP-Process A p p l i c a t i o n o f t h i s method t o TCDD, has been p r e v i o u s l y r e p o r t e d (10) . The r e l a t e d experiments were performed a t t h e E s t a b l i s h m e n t o f t h e European Community ( I s p r a ) and a t t h e ICMESA p l a n t ( S e v e s o ) ; t h e s e r e a c t i o n s , c a r r i e d o u t on pure d i o x i n and on s e v e r a l contaminated m a t e r i a l s o f t h e r e a c t o r , gave good r e s u l t s (11) . In F i g u r e 1 i s shown t h e e l i m i n a t i o n o f pure TCDD from a ndecane s o l u t i o n . In both cases t h e two i m m i s c i b l e phases were stirred magnetically. A n a l y s e s were c a r r i e d o u t on t h e hydrocarbon s o l u t i o n . The s o l e i d e n t i f i a b l e p r o d u c t s i n t h e r e a c t i o n m i x t u r e were d i b e n z o d i o x i n s p r o g r e s s i v e l y d e c h l o r i n a t e d (no c i n e s u b s t i t u t i o n was o b s e r v e d ) ; moreover, no t r a c e o f compounds c o n t a i n i n g - OH i n p l a c e o f - CI was d e t e c t e d (GC/MS). A t t e n t i o n was n o t addressed i n d e t e c t i o n o f e v e n t u a l compounds h a v i n g a p o l y e t h y l e n e g l y c o l group bonded t o t h e a r o m a t i c , s i n c e t h e i r c h e m i c a l p r o p e r t i e s , v e r y c l o s e t o those o f t h e r e a g e n t , make t h e i r s e p a r a t i o n v e r y d i f f i c u l t . So, no q u a n t i t a t i v e r e s u l t s are a t t h e moment a v a i l a b l e . I t was a l s o r e p o r t e d t h a t t h e r e a c t i o n m i x t u r e was n o t t o x i c on t h e g u i n e a p i g s ( 1 0 ) . Such r e s u l t s i n d i c a t e t h a t , from a m e c h a n i s t i c p o i n t o f view, i t i s not a matter o f a simple aromatic n u c l e o p h i l i c s u b s t i t u t i o n ( i n any case v e r y d i f f i c u l t i f n o t v i a benzyne), b u t more p r o b a b l y o f a r a d i c a l s u b s t i t u t i o n on an a c t i v a t e d complex o f t h e TCDD (SRN1 mechanism) ( 1 2 ) ; t h i s mechanism i s f a v o u r e d by t h e f a c t t h a t t h e r a d i c a l a n i o n o f TCDD i s p a r t i c u l a r l y s t a b i l i z e d ( 1 3 ) . How t h i s r a d i c a l a n i o n i s g e n e r a t e d from t h e i n i t i a t o r p e r o x i d e and how i t r e a c t s w i t h t h e hydrogen donor (PEG o r t h e s o l v e n t ) i s n o t at t h i s moment c l e a r ; however, i n t e r e s t i n g t o n o t e , d e g r a d a t i o n o f TCDD by u.v. i r r a d i a t i o n l e a d s t o t h e same i n t e r m e d i a t e compounds. The d i f f e r e n c e o c c u r r i n g i n r e a c t i o n s c a r r i e d o u t i n t h e presence o f p e r o x i d e o r o f s t r o n g bases (1-4) i s e x p l a i n e d by t h e f o l l o w i n g example which moreover i l l u s t r a t e s a d e c o n t a m i n a t i o n from PCB o f m i n e r a l o i l s : 5.0 mL o f m i n e r a l o i l contaminated w i t h 1300 ppm o f PCB ( A r o c h l o r 1260) were m a g n e t i c a l l y s t i r r e d a t 80 °C w i t h 2.5 g o f two d i f f e r e n t m i x t u r e s (A and B; % a r e i n w e i g h t ) . A: 8 6 % PEG 6000 (PEG o f MW = 6000), 12% K0CO3, 2% N a 0 . B: 77.5% PEG 6000, 10% K0CO3, 12.5% ^ O N a . Gas c h r o m a t o g r a p h i c a n a l y s e s on t h e o i l showed t h e f o l l o w i n g r e s i d u a l c o n t a m i n a t i o n s (ppm o f PCB a f t e r O.5, 1.0 and 1.5 h, r e s p e c t i v e l y ) ; A: 9 0 , 26 and 13; B: 350, 211 and 142. From the r e s p e c t i v e concentration r a t i o s i t r e s u l t s t h a t the r e a c t i o n c a r r i e d o u t w i t h sodium p e r o x i d e i s a t l e a s t 15 times f a s t e r than 2

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t h e r e a c t i o n c a r r i e d out w i t h methoxide, i n s p i t e o f the s t r o n g e r base c h a r a c t e r o f t h e l a t t e r ; a c c o r d i n g l y , t h e r e a c t i o n i s not r e l a t e d t o t h e s t r e n g t h o f t h e base a l t h o u g h i t s presence i s needed (sodium b i c a r b o n a t e i s a l s o e f f e c t i v e i f a p e r o x i d e i s p r e s e n t ) . Other d a t a i n d i c a t e t h a t t h e r e a c t i o n does not depend on s t i r r i n g ; i t i s p o s s i b l e t o o p e r a t e w i t h o t h e r p e r o x i d e s ( B a 0 as an example) and even i n t h e presence o f water ( t i l l 30% i s allowed). A l t h o u g h t h e r e a c t i o n mechanism i s not a t t h e moment f u l l y c l a r i f i e d , some p o i n t s seem t o be w e l l e s t a b l i s h e d : the r a d i c a l c h a r a c t e r o f t h e r e a c t i o n and the contemporary need o f an a n i o n a c t i v a t o r as PEG i s (maybe t h e f u n c t i o n o f the a n i o n a c t i v a t o r i s t o i n c r e a s e the s t r e n g t h of t h e base as they do i n P h a s e - T r a n s f e r C a t a l y s i s ) ( 1 4 ) . In p l a c e o f PEG o t h e r a n i o n a c t i v a t o r s may be used, a s the c o n d e n s a t i o n compounds between e t h y l e n e o x i d e and p r o p y l e n e o x i d e ; such l a t t e r p o l y m e r s , b e i n g v i s c o u s l i q u i d s , o f f e r some advantage i n p a r t i c u l a r a p p l i c a t i o n s such a s the decontamination of s u r f a c e s .


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Applications The CDP-Process works w e l l on s e v e r a l s t a b l e , h a l o g e n a t e d a r o m a t i c d e r i v a t i v e s ; mainly studied, also i n connection with i t s indust r i a l a p p l i c a t i o n has been the PCB and t h e d e g r a d a t i o n p r o d u c t s t h a t PCB forms as a consequence o f f i r e ; t h a t i s 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 and d i o x i n s (PCDF and PCDD, r e s p e c t i v e l y ) . By s u i t a b l y changing the t y p e o f p o l y e t h e r , the base and the p e r o x i d e , and i n case by adding a s o l v e n t , d i f f e r e n t " r e a g e n t s " can be p r e p a r e d which are a b l e t o a t t a c k and decompose such s u p e r t o x i c m o l e c u l e s even i f they are p r e s e n t i n d i f f e r e n t materials (mineral o i l s , surfaces, s o i l , e t c . ) ; i n f a c t d i f f e r e n t p r o c e d u r e s must be f o l l o w e d , i n c o n n e c t i o n w i t h the t y p e o f p o l l u t a n t , the e n v i r o n m e n t a l r e q u i r e m e n t s , and the i n v o l v e d materials. A f e w a p p l i c a t i o n s o f the method t h a t i l l u s t r a t e i t s p e c u l i a r i t i e s are shown.

D e c o n t a m i n a t i o n o f M i n e r a l O i l C o n t a i n i n g PCB i n a B a t c h P r o c e s s . T a b l e I r e p o r t s some r e s u l t s o f C D P - P r o c e s s i n d e s t r o y i n g PCB f r o m i t s hydrocarbon solutions ( f o r a n a l y t i c a l convenience an n-decane solution was u s e d ) . The r e a c t i o n i s e f f e c t i v e even i n t h e presence o f a c t u a l l y c a t a l y t i c q u a n t i t i e s o f peroxide; without p e r o x i d e , no r e a c t i o n o c c u r s a t a l l .

At t h e end o f the r e a c t i o n s no t r a c e o f PEG was d e t e c t e d i n ndecane ( e x p e r i m e n t s o f T a b l e 1) o r i n m i n e r a l o i l s t r e a t e d i n the same way (IR and NMR a n a l y s i s ) . In the r e a c t i o n s o f T a b l e 1 as i n t h e f o l l o w i n g ones here r e p o r t e d , t h e r e s i d u a l PCB were u s u a l l y t h e l o w - c h l o r i n a t e d p o l y c h l o r o b i p h e n y l s ; t h e s e ones have been r e p o r t e d t o be the l e s s t o x i c . The e l e c t r i c a l p r o p e r t i e s o f m i n e r a l o i l s a f t e r the CDP-Process r e n d e r such d i e l e c t r i c f l u i d s s u i t a b l e f o r t h e i r use i n e l e c t r i c a l transformer without f u r t h e r treatment ( u s u a l l y the d i e l e c t r i c a l c h a r a c t e r i s t i c s of the o i l are improved).


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T a b l e I . Chemical D e g r a d a t i o n o f PCB by CDP-Process. Influence o f % N a 0 2

% Nao0

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i n the reagent mixture

8 2 O.78 O.21 O.00

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Initial Contamination

Final Contamination (ppm) (ppm)

16,000 16,000 16,000 16,000 16,000

23 32 190 5000

no reaction

C o n d i t i o n s : 3.0 mL o f n-decane, 2.0 g o f r e a g e n t m i x t u r e : 12% (by w e i g h t ) K0CO3 and t h e d i f f e r e n c e a t 100 o f PEG 6000; T = 85°C.; magnetic s t i r r i n g f o r 3 h o u r s . D e c o n t a m i n a t i o n o f M i n e r a l O i l s C o n t a i n i n g PCB, i n an Open and a C l o s e d C o n t i n u o u s - F l o w P r o c e s s . The r e a g e n t s i n t h e CDP-Process can be i m m o b i l i z e d by a d s o r p t i o n onto a s o i l d bed; i n such a way a s o l i d r e a g e n t can be produced which can be used t o decontaminate PCB m i n e r a l o i l s p a s s i n g t h r o u g h i t (15). T h i s i s made p o s s i b l e , from a c h e m i c a l p o i n t o f v i e w , by two f a c t s : i . t h e r e a g e n t i s n o t s o l u b l e i n t h e o i l . i i . t h e PCB's d e c o m p o s i t i o n p r o d u c t s a r e c o m p l e t e l y r e t a i n e d on t h e s o l i d bed ( t h e PCB a r e n o t ; i t i s n o t a matter of adsorbtion). Figure 2 i l l u s t r a t e s the r e s u l t s obtained w o r k i n g w i t h an i m m o b i l i z e d r e a g e n t and by f l o w i n g through t h e c o n t a m i n a t e d o i l ; t h e o i l c o n t a i n i n g 900 ppm PCB f l o w e d c o n t i n o u s l y i n t o t h e column c o n t a i n i n g a bed o f 30 g s o l i d r e a g e n t (2.6 g PEG 6000, O.7 g p o t a s s i u m t - b u t o x i d e , O.7 g N a 0 , 26 g K C 0 ) and was c o l l e c t e d a t i t s o u t l e t . As shown i n F i g u r e 2, t h e column i s p r o g r e s s i v e l y exhausted; o p e r a t i n g i n a p p r o p r i a t e c o n d i t i o n s and changing t h e r e a c t i v e bed when i t becomes exhausted o r o p e r a t i n g i n s e r i e s w i t h more t h a n one column, one c a n o b t a i n a decontaminated o i l w i t h o u t t h e t r o u b l e s o f b a t c h o p e r a t i o n ( s t i r r i n g , charge o f t h e r e a c t o r , d r a i n , i n c i d e n t a l f i l t r a t i o n o r centrifugation of the o i l , e t c . ) . A n o t h e r v e r s i o n o f t h e CDP-Process u t i l i z i n g i m m o b i l i z e d r e a g e n t s i s a c o n t i n u o u s and c l o s e d p r o c e s s ; a c c o r d i n g l y , t h e same c o n t a m i n a t e d o i l i s c o n t i n u o u s l y r e c y c l e d i n t h e same column u n t i l t h e d e c o n t a m i n a t i o n l i m i t s imposed by law a r e r e a c h e d . The commercial v e r s i o n o f such c o n t i n u o u s p r o c e s s e s i n v o l v e s t h e p r e s e n c e o f t h e i m m o b i l i z e d r e a g e n t i n c a r t r i d g e s , easy t o h a n d l e and t o t r a n s p o r t ; such c a r t r i d g e s o f s t a n d a r d d i m e n s i o n s a r e t h e c o r e o f a p l a n t which c o n t i n u o u s l y pumps t h e c o n t a m i n a t e d o i l from a t a n k , heats i t t o t h e d e s i r e d t e m p e r a t u r e , sends i t t o t h e c a r t r i d g e and g i v e s i t back t o t h e t a n k . In t h i s way t h e volume of t h e o i l t o be t r e a t e d i s independent from t h e volume o f t h e plant: i t i s enough t o change t h e c a r t r i d g e when i t becomes exhuasted. 2

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2

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380


Oil

Time ( h )

Fig.

1. D e g r a d a t i o n o f TCDD.

• T = 50°C.; 1500, O.15 g Na 0 . • T = 85°C.; 6000, O.53 g 2

2.0 mL o f n-decane c o n t a i n i n g 5 g o f TCDD, O.9 g PEG KoCOo, O.10 g d i e t h y l e n e g l y c o l m o n o b u t h y l e t h e r , O.10 g

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2.0 mL o f n-decane c o n t a i n i n g 5 g o f TCDD, 2.06 g PEG K C0 and O.37 g N a 0 . 2

3

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100

200

300

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hOO

500

600

700

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F i g . 2 . D e c o n t a m i n a t i o n from PCB o f M i n e r a l O i l i n a C o n t i n u o u s and Open P r o c e s s . • T = 90°C.; f l o w 60 mL/h ( t h e f i r s t 120 mL c o n t a i n e d 38 ppm o f PCB). • T = 60°C.; PCB).

f l o w 120 mL/h ( t h e f i r s t 100 mL c o n t a i n e d 550 ppm o f



31.

NOBILEETAL.


F i g u r e 3 shows how the PCB c o n t a m i n a t i o n o f a l a r g e q u a n t i t y of o i l i s p r o g r e s s i v e l y decreased t o 42 ppm by changing f i v e c a r t r i d g e s c o n t a i n i n g 16 Kg each o f s o l i d b e d . I n t h i s e x p e r i m e n t , 440 kg o f o i l c o n t a i n i n g 4,000 ppm PCB was r e c y c l e d c o n t i n u o u s l y a t 100 L/h a t 80° C. Some advantages o f such a v e r s i o n o f the method are t h a t the p l a n t , which c a n be c l o s e d i n a c o n t a i n e r , works w i t h o u t t h e s t e a d y presence o f manpower and t h a t i t can be d i r e c t l y connected to the a p p a r a t u s c o n t a i n i n g the o i l t o be decontaminated. Such c h a r a c t e r i s t i c s a l l o w t h i s c o n t i n u o u s - f l o w method, i t s r e a g e n t s and c o n d i t i o n s t o be employed i n the d e c o n t a m i n a t i o n o f e l e c t r i c a l transformers. D e c o n t a m i n a t i o n o f S u r f a c e s Contaminated by PCB, PCDF and PCDD. T h i s v e r s i o n o f CDP-Process uses reagent m i x t u r e s i n l i q u i d phase and a t room t e m p e r a t u r e ; the r e a g e n t i s spread on the s u r f a c e t o be decontaminated. U s u a l l y t h e r e a g e n t i s f o r m u l a t e d by u s i n g copolymers between e t h y l e n e o x i d e and p r o p y l e n e o x i d e ( t h e s e c o n d e n s a t i o n p o l y m e r s , manufactured by M o n t e d i s o n , a r e c a l l e d 'Nixolen'). The e f f i c a c y o f the r e a c t i o n was p e v i o u s l y r e p o r t e d on TCDD (10). Here i s d e s c r i b e d an a p p l i c a t i o n i n t h e f i e l d , f o r t h e c l e a n - u p o f s u r f a c e s c o n t a m i n a t e d by PCDF and PCDD coming from a PCB a c c i d e n t . In an e l e c t r i c a l s u b - s t a t i o n i n I t a l y , because o f a s h o r t c i r c u i t , a r e c t i f i e r w i t h about 300 l i t t l e c a p a c i t o r s c o n t a i n i n g PCB burned (50 g each c a p a c i t o r and a t o t a l amount o f PCB o f about 10 Kg). The f i r e l a s t e d f o r about one hour b e f o r e i t was extinguished. The thermal o x i d a t i o n o f PCB produced a l a r g e q u a n t i t y o f s o o t c o n t a i n i n g PCDF and PCDD. The, s o o t was spread i n s i d e t h e s u b - s t a t i o n c o n t a m i n a t i n g about 1500 n r o f s u r f a c e s and items. D u r i n g t h e s a m p l i n g o p e r a t i o n s f o r t h e mapping o f t h e c o n t a m i n a t i o n and the d a t a a c q u i s i t i o n n e c e s s a r y f o r t h e d e s i g n o f t h e d e c o n t a m i n a t i o n , a few t e s t s were performed t o c h a r a c t e r i z e t h e b e s t method o f a p p l i c a t i o n o f CDP-Process i n o r d e r t o r e a c h t h e complete i n s i t u d e s t r u c t i o n o f PCDF and PCDD. D i f f e r e n t s u r f a c e s ( f l o o r , r o o f , w a l l s ) were s e l e c t e d t o p e r f o r m the a s s a y s . On t h o s e s u r f a c e s the r e a g e n t , l i q u i d a t room temperature ( 9 5 % of N i x o l e n and 5% o f sodium a l k o x i d e ) , was spread at room temperature t o produce a l i q u i d f i l m ; such a f i l m a t t h e same time a v o i d e d the t r a n s f e r o f the contaminant t o the e n v i r o n ment. A f t e r about 90 hours o f a c t i o n a t room t e m p e r a t u r e , t h e l i q u i d f i l m was then removed. Samples were t a k e n e i t h e r on the s u r f a c e s (wipe t e s t s , b e f o r e and a f t e r the t r e a t m e n t were made) and on the removed r e a g e n t . T a b l e 2 shows the v a l u e s o f c o n t a m i n a t i o n on t h e s e r e p r e s e n t a t i v e s u r f a c e s b e f o r e and the r e s u l t s a f t e r d e c o n t a m i n a t i o n . No contaminant was d e t e c t e d i n the removed r e a g e n t . A l l t h e s e d a t a demonstrate t h e e f f e c t i v e d e g r a d a t i o n o f PCDF and PCDD by CDPP r o c e s s , e i t h e r on the s u r f a c e s and i n the r e a g e n t .


381


382


Uooo

1

3

2 n°

5

h

o f Cartridges

F i g . 3. D e c o n t a m i n a t i o n from PCB o f M i n e r a l O i l i n a Continuous and C l o s e d P r o c e s s . T a b l e I I . In S i t u D e c o n t a m i n a t i o n o f S u r f a c e s C o n t a i n i n g PCDF and PCDD, Coming from a PCB F i r e

Contaminant (PCDF + PCDD)

Sample Taken on F l o o r Before After (ng/m ) (ng/m )

Sample Taken on Roof Before After (ng/m (ng/nr)

2,3,7,8-TCDF TCDF PeCDF HxCDF HpCDF OCDF

256 1169 678 426 336 284

ND 27 13 ND 11 20

1060 4841 2809 1762 1391 1029

174 362 92 22 ND ND

2,3,7,8-TCDD TCDD PeCDD HxCDD HpCDD OCDD

ND 24 36 45 42 35

ND ND ND ND ND 114

33 100 148 187 174 143

ND ND ND ND ND ND

z

z

ND = Not D e t e c t a b l e ( d e t e c t i o n v a r y i n g from 2 t o 8 n g / n r ) .

z

l i m i t depends from t h e sample,


31.

NOBILE ET

AL.


383

Acknowledgments T h i s work was p a r t l y a r e s e a r c h program o f t h e C o n s i g l i o N a z i o n a l e d e l l e R i c e r c h e , P r o g e t t o F i n a l i z z a t o 'Chimica F i n e e S e c o n d a r i a ' .


Literature 1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13. 14. 15.

Cited

Brunelle, D. J.; Singleton, D.A. Chemosphere 1983, 12, 183. Brunelle, D. J. U.S. Patent Appl. n° 314,163 (1981) (General Electric Company). Pytlewsky, L. L.; Krevitz, K.; Smith, A. B. U.S. Patent Appl. n° 142,865 and 158,359 (1980) (Franklin Institute). Peterson, R. L. U.S. Patent Appl. n° 501,620 (1983) (Galson Research Corporation). Draper, W. M. Chemosphere, 1985, 14, 1195. Kitchens, J. A. F. U.S. Patent Appl. n° 890,871 (Atlantic Research Corporation). Shannahan, C. E. et al. Report EPA-600/-78-146 (1978). Howard, K. J.; Sidwell, A. E. Eur. Patent n° 0 021 294 A1 (Vertac Chem. Corporation). Tundo, P. U.S. Patent Appl. n° 771,404 (1985) (Sea Marconi Technologies). Tundo, P.; Facchetti, S.; Tumiatti W.; Fortunati, U. Chemosphere, 1985, 14, 403. Tundo, P.; Facchetti, S.; Tumiatti, W.; Fortunati, U. Report to the President of the Lombardia Region (1983). March, J. "Advanced Organic Chemistry"; Wiley: New York, 1985; 3rd Ed.; p. 582. Miller, G.; Sontum, S.; Crosby, G. Bull, Environ. Contam. Toxicol. 1977, 18, 611. Starks, C. M.; Liotta, C. "Phase Transfer Catalysis"; Academic Press: New York, 1978. Tundo, P. U.S. Patent Appl. n° 632,718 (1984) (Sea Marconi Technologies).

R E C E I V E D December 5,

1986


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