Pesticides Identification at the Residue Level - ACS Publications

'he newly formed Division of Pesticide Chemistry of the American. Chemical Society has as one of its central objectives ... effects of these chemicals...
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PREFACE

'he n e w l y f o r m e d D i v i s i o n of P e s t i c i d e C h e m i s t r y of the A m e r i c a n C h e m i c a l S o c i e t y has as one o f its c e n t r a l objectives

the task o f

i n c r e a s i n g a n d d i f f u s i n g k n o w l e d g e r e l a t i n g to the c h e m i c a l , p h y s i c a l , a n d b i o l o g i c a l p r o p e r t i e s of t h e c h e m i c a l s u s e d to c o n t r o l pests of p l a n t s , Downloaded by 118.139.178.67 on April 19, 2018 | https://pubs.acs.org Publication Date: June 1, 1971 | doi: 10.1021/ba-1971-0104.pr001

a n i m a l s , a n d m a n . I n this r e g a r d , the D i v i s i o n promotes r e s e a r c h i n a n u m b e r of i m p o r t a n t areas of p e s t i c i d e c h e m i s t r y r a n g i n g f r o m t h e s y n thesis of n e w e r , m o r e effective pest c o n t r o l m a t e r i a l s a n d t e c h n i q u e s to scientific a p p r a i s a l s of the fate a n d persistence of these c o m p o u n d s

in

the e n v i r o n m e n t . D i r e c t l y p e r t i n e n t to v i r t u a l l y e v e r y area of s t u d y is the d e v e l o p m e n t a n d u t i l i z a t i o n of m e t h o d s f o r o r g a n i c a n d i n o r g a n i c p e s t i c i d e analysis. T h e t r e m e n d o u s achievements w h i c h h a v e b e e n a c c o m p l i s h e d

by

the j u d i c i o u s use of pesticides i n i n c r e a s e d w o r l d - w i d e f o o d p r o d u c t i o n a n d t h e c o n t r o l of v e c t o r - b o r n e diseases are v e r y e v i d e n t . p e s t i c i d a l m a t e r i a l s c o n t r i b u t e to the effective

c o n t r o l of

In addition, undesirable

species of pests i n c l u d i n g insects, p l a n t s , b a c t e r i a , f u n g i , etc., a n d assist i n the n u t r i t i o n , g r o w t h , a n d r e p r o d u c t i o n of c e r t a i n d e s i r a b l e species. H o w e v e r , b e c a u s e o f w i d e s p r e a d use i n these a p p l i c a t i o n s , pesticides h a v e p r o l i f e r a t e d intensely i n the b i o s p h e r e a n d thus h a v e s i g n i f i c a n t l y c o n t r i b u t e d to p r o b l e m s of e n v i r o n m e n t a l p o l l u t i o n . F o r e x a m p l e , the effects of these c h e m i c a l s o n p u b l i c h e a l t h a n d t h e s u r v i v a l of species of fish a n d w i l d l i f e are t w o specific areas of c r i t i c a l c o n c e r n . T h e a t t e n t i o n w h i c h has b e e n f o c u s e d i n recent years o n the o c c u r r e n c e o f residues o f pesticides a n d t h e i r m e t a b o l i t e s , as w e l l as other i n d u s t r i a l l y significant c h e m i c a l s i n the e n v i r o n m e n t , is d e m o n s t r a t e d b y the n u m e r o u s reports of v a r i o u s official a n d u n o f f i c i a l c o m m i t t e e s o f i n q u i r y w h i c h h a v e c o n s i d e r e d this p r o b l e m a n d h a v e r e p o r t e d the results of l a r g e n u m b e r s of assays of p e s t i c i d e residues i n s u c h d i v e r s e substrates as h u m a n a n d a n i m a l tissues, f o o d , p l a n t s , w a t e r , s o i l , a n d a i r . A m a j o r i t y of these r e s i d u e d e t e r m i n a t i o n s are m a d e at the parts p e r m i l l i o n a n d parts p e r b i l l i o n levels w h i c h r e q u i r e o n the o n e h a n d t h e a v a i l a b i l i t y of a n a l y t i c a l t e c h n i q u e s of r e m a r k a b l e s e n s i t i v i t y , a c c u r a c y , a n d i n t e g r i t y i n r e c o r d i n g p r o p e r a n d r e l i a b l e d a t a a n d o n the other, s k i l l e d i n t e r p r e t a t i o n , experience a n d k n o w l e d g e of the c a p a b i l i t i e s a n d l i m i t a t i o n s of these t e c h n i q u e s , a n d t h e a p p l i c a t i o n of s u i t a b l e c o n f i r m a vii

Biros; Pesticides Identification Advances in Chemistry; American Chemical Society: Washington, DC, 1971.

t o r y m e t h o d s of i d e n t i f i c a t i o n . I n a d d i t i o n to these p r o b l e m s of d e t e c t i o n a n d i d e n t i f i c a t i o n of infinitely s m a l l amounts of these m a t e r i a l s , t h e c o m p l e x i t y of the analysis of p e s t i c i d e residues is f u r t h e r c o m p o u n d e d b y the p r o l i f i c d e v e l o p m e n t

of efficient n e w classes of pesticides

which

u n d e r g o e n v i r o n m e n t a l d e c o m p o s i t i o n to a series of b r e a k d o w n p r o d u c t s b y a n u m b e r of m e c h a n i s m s i n c l u d i n g m e t a b o l i s m , p h o t o d e c o m p o s i t i o n , h y d r o l y s i s , a n d / o r o x i d a t i o n . E a c h of these t r a n s f o r m a t i o n p r o d u c t s m u s t b e m o n i t o r e d to a n extent e q u a l to that of the p a r e n t m a t e r i a l , p a r t i c u l a r l y i n those cases w h e r e the t o x i c o l o g i c a l characteristics h a v e n o t

been

ascertained. T h e c o n t i n u e d u t i l i z a t i o n of m a n y " c l a s s i c a l " p e s t i c i d a l m a t e r i a l s o f

Downloaded by 118.139.178.67 on April 19, 2018 | https://pubs.acs.org Publication Date: June 1, 1971 | doi: 10.1021/ba-1971-0104.pr001

d e m o n s t r a t e d u b i q u i t o u s n e s s a n d persistence a n d the presence of u n k n o w n or u n s u s p e c t e d i n d u s t r i a l c h e m i c a l p o l l u t a n t s other t h a n pesticides i n the e n v i r o n m e n t are other areas of c o n c e r n c o n f r o n t i n g p u b l i c h e a l t h officials a n d r e s i d u e chemists a l i k e . T h u s , the a n a l y t i c a l c h e m i s t is f a c e d w i t h a c o n t i n u i n g r e s p o n s i b i l i t y to d e v e l o p , evaluate, a n d i m p r o v e t h e confidence of the t e c h n i q u e s w h i c h are u s e d to i d e n t i f y a n d q u a n t i t a t i v e l y m o n i t o r these c h e m i c a l s i n h u m a n , a n i m a l , a n d e n v i r o n m e n t a l samples. W i t h i n the f r a m e w o r k of this p h i l o s o p h y , this s y m p o s i u m is c o n c e r n e d w i t h s e v e r a l t o p i c areas p e r t i n e n t to the p r o b l e m s associated w i t h the i d e n t i f i c a t i o n a n d c o n f i r m a t i o n of p e s t i c i d e residues at s u b m i c r o g r a m levels. T h e p u r p o s e of this s y m p o s i u m is to s u r v e y the present status of the c l a s s i c a l p h y s i c a l , c h e m i c a l , a n d b i o c h e m i c a l t e c h n i q u e s e m p l o y e d for r e s i d u e a n a l y s i s ; to e v a l u a t e c r i t i c a l l y the m o r e r e c e n t l y a p p l i e d , r e l a t i v e l y u n e x p l o i t e d t e c h n i q u e s w h i c h h a v e b e c o m e a v a i l a b l e for the d e t e c t i o n , q u a n t i t a t i o n , a n d c h a r a c t e r i z a t i o n of p e s t i c i d e residues; a n d

finally,

to

e x a m i n e a n d discuss the c u r r e n t needs a n d p r o b l e m s , s t i m u l a t e a n d e n c o u r a g e greater r e s e a r c h a c t i v i t y , a n d p o i n t the w a y to f u t u r e d e v e l o p ments i n the analysis of p e s t i c i d e residues. T h e f o u r g e n e r a l t o p i c areas to b e d i s c u s s e d i n the papers of t h e s y m p o s i u m i n c l u d e : p h i l o s o p h i c a l aspects of u l t r a m i c r o a n a l y s i s , i n s t r u m e n t a l t e c h n i q u e s , m i c r o c h e m i c a l m e t h o d s , a n d b i o l o g i c a l assay m e t h o d s . T h e aspects c o n s i d e r e d i n most d e t a i l o b v i o u s l y w i l l i n v o l v e those e n compassing instrumental techniques. I n d i v i d u a l emphasis w i l l be p l a c e d o n g a s - l i q u i d c h r o m a t o g r a p h i c detectors, i n f r a r e d a n d u l t r a v i o l e t s p e c t r o p h o t o m e t r y , p a p e r a n d t h i n - l a y e r c h r o m a t o g r a p h y , mass

spectrometry,

a n d n e u t r o n a c t i v a t i o n analysis. O t h e r papers w i l l discuss r e c e n t l y d e v e l oped techniques employing chemical a n d photochemical conversion

of

pesticides i n t o derivatives u s e f u l for the c o n f i r m a t i o n of the p a r e n t r e s i d u e at p i c o g r a m a n d n a n o g r a m c o n c e n t r a t i o n levels. T h e u t i l i t y of b i o l o g i c a l assay m e t h o d s for the i d e n t i f i c a t i o n of residues w i l l also b e

explored

p a r t i c u l a r l y f r o m the p o i n t of v i e w of e n z y m a t i c a n d i m m u n o l o g i c a l t e c h n i q u e s . T h e s e m e t h o d s h a v e b e e n s h o w n to possess h i g h sensitivity viii

Biros; Pesticides Identification Advances in Chemistry; American Chemical Society: Washington, DC, 1971.

a n d t h e i r usefulness i n c e r t a i n a p p l i c a t i o n s is w e l l e s t a b l i s h e d .

Finally,

the p h i l o s o p h i c a l aspects of u l t r a m i c r o a n a l y s i s w i l l b e d i s c u s s e d

with

e m p h a s i s o n a s u r v e y of the specific p r o b l e m s associated w i t h i d e n t i f i c a t i o n at s u b m i c r o g r a m levels. F.

J.

Perrine Primate Research B r a n c h Division

of P e s t i c i d e C h e m i s t r y a n d T o x i c o l o g y

F o o d a n d Drug A d m i n i s t r a t i o n D e p a r t m e n t of H e a l t h , E d u c a t i o n a n d W e l f a r e P e r r i n e , Florida 33157

Downloaded by 118.139.178.67 on April 19, 2018 | https://pubs.acs.org Publication Date: June 1, 1971 | doi: 10.1021/ba-1971-0104.pr001

A u g u s t 1970

IX

Biros; Pesticides Identification Advances in Chemistry; American Chemical Society: Washington, DC, 1971.

BIROS