Document 5D05yOMzwkX18x9Bzk65mqMV

Analy tic al Cne mis S p ec i al Study "0 -4 J o b No. 163034c 1 * i STUDY OF AROCLOR C H E M I C A L C L E A N - U ? P R O C E D U R E S FOR USE INTRODUCTION * The e ff e c t s of t h r e e c h e m i c a l c l e a n - u p p r o c e d u r e s on the A r o c l o r 1200 s eries have been investigated. The chemical p ro c e d u re s in question: nitration, saponification, and treatment with sulfuric acid - were originally proposed by pesticide analysts for the clean-up and identification of p e s ti c id e s in re s id u e e x t r a c t s . L a t e r when p o ly c h lo rin at ed biphenyls (PCB's) were identified as environmental contaminants these procedures w e r e e x t e n d e d tc the c l e a n - u p anc i d en t i f i c a t i o n of P C E ' s in r e s i d u e extracts. SUM VARY 1. T h e q u r r . t i t a t i v e r e c o v e r y and EC r e s p o n s e of A r o c l o r m a t e r i a l s are not affected by saponification or treatment with sulfuric acid. 2. N it r a t io n can have a significant del eter io us effect on the q u a n t i tative r e c o v e r y and EC res p o n s e of A r o c lo r 1242. 3. The excer.t of the effect of the n i t r a t i o n t r e a t m e n t is d e p e n d e n t on the te m p e r attire and exposure time employed as well as the specific Aroclor treated. 4. Analysts employing nitration procedures p rio r to EC analysis m a y or na> not , d e p e n d i n g on the c o n d i t i o n s u s e d , s e e an Z Z r e s p o n s e for A r o c l o r 1242 if presen t. DISCUSSION W*e h a v e f ound t h a t s a p o n i f i c a t i o n a n d t r e a t m e n t w i t h s u l f u r i c a c i d does not affect the quantitative recovery nor the electron capture (EC) resp o n se of the A roclor m a te r ia ls . However, the nitration procedures have significant deleterious effects cn both the quar.tita tive r e c o v e r y and EC re s p o n s e of the lower ch lorinate d biphenyls such as A r o c l o r 1242, The effect of this t r e a tm e n t on the A r c e l o r se rie s is shown g r a p h ic a ll y in F igures 1-7. The fact that the lower chlorinated biphenyls are nitrated under these conditions has been verified by C C / M a s s identification of the PLAINTIFF'S EXHIBIT 003332 S p e c i a l Study 70 -4 Pase 2 products as nitrochlorobiphenyls. The nitration procedure employed was referenced by Risebrough* [Erro, F . , B e v e n u e , A . , and B e c k m a n , H. , Bull . E n v i r o n . Cont . T o x i c o l . , 372 (1967)] in his Nature a r t i c l e on P C B r e s i d u e s in the en v iro n m en t. Additionally, we have i n v e st ig at ed a s i m i l a r nit rat io n p r o c e d u r e used by W idm ark and c o - w o r k e r s (private com munication via R. E. Keller). This tre a tm e n t differs from R isebrough's in that a sh o rter exposure time and a lower te m p eratu re are employed. The Widmark method greatly dimishes the effects observed with Risebrough's referenced me thod. RESULTS V e r i f i c a t i o n of the c on cl u s i o n drawm a r e shown in F i g u r e s 1-7. E x t r a c tion and m e a s u r e m e n t were p erfo rm e d as described in Analycical Method No. 69-13. * A quote f r o m R i s e b r o u g h ' s a r t i c l e N a tu r e , 2 2 0 , 1098 ( 1968) , "The DDT compounds are destroyed by nitration and p ,p '-D D T , DDD, and toxapnene a r e d e h y d r o c h l o r i n a t e d by s a p o n i f i c a t i o n wdth a l cohol ic KOK. PCB is not degraded by either procedure. " MONSANTO COMPANY Organic Chemicals Division Applied Sciences Section St. Louis, M i s s o u r i 3- 70 E. S. T u c k e r , W. J. L i t s c h g i , R. E . K e l l e r am 0 J b 8 3 3 *1- FIGURE 1 . *.. Electron capture cas chror.atoerapntc wtrace of (A} bipher.yl treated * 1:1 mixture of nitric and sulfu ric acids and extracted into hexane t (B) biphenyl treated with distilled vfater and extrac ted ,into hexane and (C) untreated biohe n y * standard in hexane. ADM 00563A \ ^ ^ AROCLCR 12 t 2 'v FIGURE 2 . Electron capture cas chromatographic t;race of (A) Aroclor 1242 and trears with 1:1 mixture cf nitric and sulfu acids and extracted into hexane, (3) *Aroclor 1242 treated with disrilled water and extracted into hexane, and (C) untreated Aroclor 1242 standard i hexane. / AO M 005)835 MJ ll A M * 05'3a FTCURK 5 . Kloctron capture gas chromatographic trace of (A) Aroclor 1260 and treated with 1:1 mixture of nitric and sulfuric acids and extracted into hexane, (n) Aroclor 1260 treated with distilled water and extracted into hexane, and (C) untreated ' Aroclor 1260 standard in hexane. AM G0583