B A S I C   F L U O R O E L A S T O M E R   ( C O P O L Y M E R ,   T E R P O L Y M E R   a n d   P E R F L U O R O E L A S T O M E R )   D A T A   A u g u s t   2 0 0 3     F l u o r o p o l y m e r s   M a n u f a c t u r e r s   G r o u p   ( F M G )   S o c i e t y   o f   t h e   P l a s t i c   I n d u s t r y ,   I n c .   ( S P I )   1 8 0 1   K   S t r e e t   N W   W a s h i n g t o n ,   D C   2 0 0 0 6       T a b l e   o f   C o n t e n t s     I t e m   1 .   I n t r o d u c t i o n   I t e m   2 .   P - c h e m   p r o p e r t i e s   t o   i n f o r m   f a t e   t e s t i n g     I t e m   2 . 1   C o p o l y m e r   a n d   T e r p o l y m e r       I t e m   2 . 1 . 1   P o l y m e r i z a t i o n       I t e m   2 . 1 . 2   P r o p e r t i e s         I t e m   2 . 1 . 2 . 1   M o l e c u l a r   S t r u c t u r e         I t e m   2 . 1 . 2 . 2   C r o s s - l i n k i n g   C h e m i s t r y         I t e m   2 . 1 . 2 . 3   C h e m i c a l   R e s i s t a n c e         I t e m   2 . 1 . 2 . 4   T h e r m a l   S t a b i l i t y         I t e m   2 . 2   P e r f l u o r o e l a s t o m e r       I t e m   2 . 1 . 1   P o l y m e r i z a t i o n       I t e m   2 . 1 . 2   P r o p e r t i e s         I t e m   2 . 1 . 2 . 1   M o l e c u l a r   S t r u c t u r e         I t e m   2 . 1 . 2 . 2   C r o s s - l i n k i n g   C h e m i s t r y         I t e m   2 . 1 . 2 . 3   C h e m i c a l   R e s i s t a n c e                                   RECEIVED OPPT NCIC 2003 August 12 8: 12AM OPPT 2003 0012 0165 B a s i c   F l u o r o p o l y m e r   D a t a   ( A u g u s t   2 0 0 3 )   I t e m   1 .   I n t r o d u c t i o n     C o m m e r c i a l   f l u o r o e l a s t o m e r s   a r e   m a i n l y   c a t e g o r i z e d   i n t o   t w o   c l a s s e s .   O n e   i s   b a s e d   o n   v i n y l i d e n e   f l u o r i d e   ( V D F ;   C A S   n u m b e r   7 5 - 3 8 - 7 )   a s   t h e   m a i n   m o n o m e r ,   t h e   o t h e r   i s   b a s e d   o n   t e t r a f l u o r o e t h y l e n e   ( T F E ;   C A S   n u m b e r 1 1 6 - 1 4 - 3 ) .       I n   t h i s   p a p e r ,   t h e   f o l l o w i n g   f l u o r o e l a s t o m e r s   a r e   r e p o r t e d ;   1 )   C o p o l y m e r   ( C A S   n u m b e r   9 0 1 1 - 1 7 - 0 )   o f   V D F   a n d   h e x a f l u o r o p r o p e n e   ( H F P ;   C A S   n u m b e r   1 1 6 - 1 5 - 4 )     2 )   T e r p o l y m e r   ( C A S   n u m b e r   2 5 1 9 0 - 8 9 - 0 )   o f   V D F ,   H F P   a n d   T F E       3 )   P e r f l u o r o e l a s t o m e r   ( C A S   n u m b e r   2 6 4 2 5 - 7 9 - 6 ) ,   c o p o l y m e r   o f   T F E   a n d   p e r f l u o r o m e t h y l   v i n y l   e t h e r   ( P M V E   C A S   n u m b e r   1 1 8 7 - 9 3 - 5 )       A l t h o u g h   t h e r e   a r e   s o m e   o t h e r   f l u o r o e l a s t o m e r s   c o m m e r c i a l l y   a v a i l a b l e ,   t h e s e   e l a s t o m e r s   p l a y   a   m a j o r   p a r t   i n   t h e   f l u o r o e l a s t o m e r   i n d u s t r y .     C o p o l y m e r   1 )   a n d   t e r p o l y m e r   2 )   a b o v e   a r e   V D F - b a s e d   f l u o r o e l a s t o m e r s   a n d   3 )   i s   a   T F E - b a s e d   f l u o r o e l a s t o m e r .     H o m o p o l y m e r s   o f   V D F   a n d   T F E   a r e   h i g h l y   c r y s t a l l i n e   p o l y m e r s .   C o p o l y m e r i z a t i o n   o f   t h e s e   m o n o m e r s   w i t h   s u i t a b l e   c o m o n o m e r s ,   s u c h   a s   H E P   a n d   P M V E ,   c a n   d e c r e a s e   c r y s t a l l i n i t y   t o   g i v e   e l a s t o m e r i c   p r o p e r t i e s 1 ) .           I t e m   2 .   P - c h e m   p r o p e r t i e s   t o   i n f o r m   f a t e   t e s t i n g     “ P - c h e m   p r o p e r t i e s ”   i s   t h e   a b b r e v i a t i o n   f o r   p h y s i c o - c h e m i c a l   p r o p e r t i e s   o f   f l u o r o e l a s t o m e r s .   T h e   i n t e n t   o f   t h i s   I t e m   i s   t o   e x p l o r e   p h y s i c a l - c h e m i c a l   p r o p e r t i e s   t h a t   p r o v i d e   i n f o r m a t i o n   ( “ i n f o r m ” )   a b o u t   t h e   d e s t i n y   ( “ f a t e ” )   o f   f l u o r o e l a s t o m e r s   a f t e r   t h e y   h a v e   b e e n   p r o d u c e d ,   b e   i t   i n   a p p l i c a t i o n   o r   o t h e r   m a n n e r s   o f   p r e s e n c e .       I t e m   2 . 1   C o p o l y m e r   a n d   T e r p o l y m e r ,   V D F - H F P   [ C A S   n u m b e r   9 0 1 1 - 1 7 - 0 ]   a n d   V D F - H F P - T F E   [ C A S   n u m b e r   2 5 1 9 0 - 8 9 - 0 ]     I t e m   2 . 1 . 1   P o l y m e r i z a t i o n     V D F - b a s e d   f l u o r o e l a s t o m e r s   c a n   b e   p r o d u c e d   b y   b u l k - ,   s o l u t i o n - ,   s u s p e n s i o n -   a n d   e m u l s i o n - p o l y m e r i z a t i o n .   I n d u s t r y   g e n e r a l l y   u s e s   f r e e - r a d i c a l   p o l y m e r i z a t i o n   t e c h n o l o g y   i n   a q u e o u s   m e d i a .   T h e   i n i t i a t o r   f o r   t h e   p o l y m e r i z a t i o n   i s   u s u a l l y   a   w a t e r – s o l u b l e   p e r o x i d e   s u c h   a s   a m m o n i u m   p e r s u l f a t e   o r   p o t a s s i u m   p e r s u l f a t e .   A   r e d o x   c a t a l y s t   s u c h   a s   s o d i u m   s u l f i t e   c a n   a l s o   b e   c o m b i n e d   w i t h   t h e   p e r o x i d e   a s   a n   i n i t i a t o r .   A m m o n i u m   p e r f l u o r o o c t a n o a t e   ( A P F O ;   C 7 F 1 5 C O O N H 4 )   i s   g e n e r a l l y   u s e d   a s   a   p e r f l u o r i n a t e d   e m u l s i f i e r   t o   s t a b i l i z e   e m u l s i o n   t h a t   i s   p r o d u c e d   d u r i n g   p o l y m e r i z a t i o n .   T h e   p o l y m e r   e m u l s i o n   o b t a i n e d   i s   m o s t   f r e q u e n t l y   c o a g u l a t e d   b y   i n o r g a n i c   s a l t s   s u c h   a s   m a n g a n e s e   s u l f a t e   o r   a l u m i n u m   p o t a s s i u m   s u l f a t e ,   t h e n   w a s h e d   w i t h   w a t e r   a n d   d r i e d .   T h e   f i n i s h e d   B a s i c   F l u o r o p o l y m e r   D a t a   ( A u g u s t   2 0 0 3 )   p r o d u c t s   a r e   s u p p l i e d   a s   p e l l e t s ,   l u m p s   o f   m i l l e d   s h e e t s .   S o m e   f l u o r o e l a s t o m e r s   a r e   a l s o   a v a i l a b l e   i n   l a t e x   f o r m 2 ) .       I t e m   2 . 1 . 2   P r o p e r t i e s     B o t h   c o p o l y m e r   a n d   t e r p o l y m e r   a r e   d e s i g n a t e d   a s   F K M   b y   t h e   A m e r i c a n   S o c i e t y   f o r   T e s t i n g   a n d   M a t e r i a l s   ( A S T M )   D - 1 4 1 8 .     I n   I S O - R 1 6 2 9   i t s   d e s i g n a t i o n   i s   F P M .     F K M   h a s   n o   m e l t i n g   p o i n t   d u e   t o   i t s   a m o r p h o u s n e s s .     F K M   i s   c r o s s - l i n k e d   b y   i o n i c   c u r i n g   a n d   r a d i c a l   c u r i n g   d u r i n g   p r o c e s s i n g   t o   m a k e   e n d   p r o d u c t s .         I t e m   2 . 1 . 2 . 1   M o l e c u l a r   S t r u c t u r e     F i g u r e   1   s h o w s   t h e   c h e m i c a l   s t r u c t u r e s   o f   c o p o l y m e r   a n d   t e r p o l y m e r .                                                   C o p o l y m e r                   T e r p o l y m e r           H           F                       F           F                                                           H           F                     F             F                   F             F         ( C           C ) x           ( C         C ) y                                                   ( C           C ) x           ( C           C ) y         ( C           C ) z                                                                                H           F                       F         C F 3                                                     H           F                     F           C F 3                 F             F                       F i g u r e   1   C h e m i c a l   s t r u c t u r e s   o f   F K M     C o p o l y m e r   i s   r a n d o m l y   s e q u e n c e d   b y   V D F   a n d   H F P .     T h e   m o l a r   r a t i o   o f   V D F   ( x )   r e q u i r e d   t o   o b t a i n   a   r u b b e r - l i k e   p o l y m e r   i s   5 0   –   8 0   m o l e   % .   F i g u r e   2   r o u g h l y   s h o w s   t h e   c o m p o s i t i o n s   a t   w h i c h   t h e   t e r p o l y m e r   ( V D F - H F P - T F E )   e x h i b i t s   a n   e l a s t o m e r i c   r e g i o n 1 ) .                                 F i g u r e   2   C o m p o s i t i o n   o f   V D F - H F P - T F E   3 )     B a s i c   F l u o r o p o l y m e r   D a t a   ( A u g u s t   2 0 0 3 )     F K M   a s   p o l y m e r i z e d   i s   t r a n s p a r e n t   t o   t r a n s l u c e n t .   T h e   m o l e c u l a r   w e i g h t   o f   F K M   a s   p o l y m e r i z e d   c a n   b e   m e a s u r e d   w i t h   g e l   p e r m e a t i o n   c h r o m a t o g r a p h y ,   s i n c e   F K M   i s   g e n e r a l l y   s o l u b l e   i n   c e r t a i n   o r g a n i c   s o l v e n t s   s u c h   a s   k e t o n e s ,   e s t e r s   a n d   e t h e r s .     T h e   m o s t   c o m m o n   r a n g e   o f   m o l e c u l a r   w e i g h t s   f o r   c o m m e r c i a l   p r o d u c t s   i s   1 0 0 , 0 0 0   t o   2 0 0 , 0 0 0 3 ) .       I t e m   2 . 1 . 2 . 2   C r o s s - l i n k i n g   C h e m i s t r y     A s   m e n t i o n e d   a b o v e ,   F K M   i s   c r o s s - l i n k e d   d u r i n g   p r o c e s s i n g .   T h e r e   a r e   t w o   c r o s s - l i n k i n g   m e t h o d s ,   i o n i c   c r o s s - l i n k i n g   a n d   f r e e   r a d i c a l   ( p e r o x i d e )   c r o s s - l i n k i n g .   I n   i o n i c   c r o s s - l i n k i n g ,   t h e   c u r i n g   a g e n t   u s e d   n e e d s   t o   b e a r   t w o   f u n c t i o n a l   g r o u p s ,   o r   s o - c a l l e d   b i s - n u c l e o p h i l e s ,   s u c h   a s   b i s p h e n o l s   a n d   d i a m i n e s .       F r e e   r a d i c a l   c r o s s - l i n k i n g   i s   u s e d   w h e n   F K M   i s   p o l y m e r i z e d   w i t h   a n o t h e r   m o n o m e r   b e a r i n g   a   f u n c t i o n a l   g r o u p   t h a t   c a n   b e   a t t a c k e d   b y   a   r a d i c a l 1 ) .       T a b l e   1   s h o w s   t y p i c a l   c r o s s - l i n k i n g   c o n d i t i o n s   f o r   F K M .       T a b l e   1   T y p i c a l   C r o s s - l i n k i n g   C o n d i t i o n s   4 )     C u r e   s y s t e m   B i s p h e n o l   D i a m i n e   P e r o x i d e   M e c h a n i s m   I o n i c   I o n i c   F r e e   r a d i c a l   P o l y m e r   C o -   a n d   T e r -   T e r -   C o -   a n d   T e r   F o r m u l a t i o n   P o l y m e r                                       1 0 0 M T   c a r b o n   b l a c k               2 0 C a ( O H ) 2                                           6   M g O                                                         3   P o l y m e r                                       1 0 0   M T   c a r b o n   b l a c k               2 0   M g O                                                     1 5   C u r i n g   a g e n t   a )                       3   P o l y m e r                                           1 0 0   M T   c a r b o n   b l a c k                   2 0   T A I C   b )                                                   4   P e r o x i d e   c )                                         1 . 5 P r e s s   1 0   -   4 5   m i n     a t   1 6 0   -   1 7 0 o C   2 0   m i n     a t   1 6 0 o C   1 0   –   1 5   m i n   a t   1 6 0 o C   O v e n   2 4   h o u r s   a t   2 3 0 o C   2 4   h o u r s   a t   2 0 0 o C   0   -   4   h o u r s   a t   1 8 0 o C   a )   F o r   i n s t a n c e ,   N , N ’ - d i c i n n a a m y l i d e n e - 1 , 6 - h e x a n e d i a m i n e   b )   F o r   i n s t a n c e ,   2 , 5 - d i m e t h y l - 2 , 5 - d i - ( t - b u t y p e r o x y ) h e x a n e   c )   T r i a l l y l i s o c y a n u r a t e       O n c e   F K M   i s   c r o s s - l i n k e d ,   t h e   m o l e c u l a r   w e i g h t   c a n   b e   n o   l o n g e r   m e a s u r e d ,   s i n c e   c r o s s - l i n k e d   F K M   i s   n o t   s o l u b l e   i n   o r g a n i c   s o l v e n t s   a n d   d o e s   n o t   m e l t   a t   h i g h   t e m p e r a t u r e .   I t   s h o u l d   b e   n o t e d   h e r e   t h a t   c r o s s - l i n k i n g   i s   p a r t   o f   t h e   F K M   m o l d i n g   p r o c e s s .   T h e   p r o c e s s   i n c l u d e s   m i x i n g ,   k n e a d i n g ,   e x t r u s i o n   o r   c a l e n d a r i n g   a n d   c r o s s - l i n k i n g .   P r e - c u r i n g   a n d   p o s t - c u r i n g   a r e   g e n e r a l l y   n e c e s s a r y   t o   c o m p l e t e   t h e   c r o s s - l i n k i n g   r e a c t i o n .       I t e m   2 . 1 . 2 . 3   C h e m i c a l   R e s i s t a n c e     T h e   s u b s t i t u t i o n   o f   h y d r o g e n   b y   f l u o r i n e   i n   p o l y m e r s   i n c r e a s e s   1 )   r e t e n t i o n   o f   p r o p e r t i e s   a t   h i g h   t e m p e r a t u r e ,   2 )   f l e x i b i l i t y   a t   l o w   t e m p e r a t u r e ,   a n d   3 )   r e s i s t a n c e   t o   B a s i c   F l u o r o p o l y m e r   D a t a   ( A u g u s t   2 0 0 3 )   s o l v e n t s 2 ) .   T h e r m a l   s t a b i l i t y   a n d   c h e m i c a l   s t a b i l i t y   o f   F K M   a r i s e s   f r o m   i t s   h i g h   f l u o r i n e   c o n t e n t s   ( 6 5   –   7 0 % ) .   G e n e r a l   c h e m i c a l   r e s i s t a n c e   o f   F K M   i s   s h o w n   i n   T a b l e   2 .         T a b l e   2   G e n e r a l   C h e m i c a l   R e s i s t a n c e s   o f   F l u o r o e l a s t o m e r s   ( F K M )   5 )     O u t s t a n d i n g   R e s i s t a n c e   G o o d   t o   E x c e l l e n t   R e s i s t a n c e   P o o r   R e s i s t a n c e   H y d r o c a r b o n   S o l v e n t s   A u t o m o t i v e   f u e l s   a )   E n g i n e   o i l s   b )   A p o l a r   c h l o r i n a t e d   s o l v e n t s   H y d r a u l i c   f u e l s   A i r c r a f t   f u e l s   a n d   o i l s     L o w - p o l a r i t y   s o l v e n t s   O x i d a t i v e   e n v i r o n m e n t s   D i l u t e   a l k a l i n e   s o l u t i o n s   A q u e o u s   a c i d s   H i g h l y   a r o m a t i c   s o l v e n t s   W a t e r   a n d   s a l t   s o l u t i o n s   S t r o n g   c a u s t i c   ( N a O H ,   K O H )   A m m o n i a   a n d   a m i n e s   P o l a r   s o l v e n t s   ( K e t o n e s )   ( M e t h y l   a l c o h o l )   a )   U n l e a d e d   f u e l s   c o u l d   a f f e c t   p e r f o r m a n c e   o f   t h e   f l u o r o e l a s t o m e r s   d u e   t o   t h e   p r e s e n c e   o f   m e t h y l   a l c o h o l .   b )   C e r t a i n   a m i n e   a d d i t i v e s   i n   e n g i n e   o i l s   c a n   b e   d e t r i m e n t a l .       T a b l e   3   c o n t a i n s   t h e   c h e m i c a l   r e s i s t a n c e   o f   F K M   a n d   o t h e r   e l a s t o m e r s .   F K M   s h o w s   e x c e l l e n t   c h e m i c a l   r e s i s t a n c e   c o m p a r e d   w i t h   o t h e r   e l a s t o m e r s   6 ) .                                                 B a s i c   F l u o r o p o l y m e r   D a t a   ( A u g u s t   2 0 0 3 )     T a b l e   3   C o m p a r i s o n   o f   c h e m i c a l   r e s i s t a n c e   o f   s e l e c t e d   e l a s t o m e r s   6 )             F l u o r o e l a s t o m e r ( V D F - H F P )     P o l y s u l f i d e   S i l i c o n e   E P D M   A m m o n i u m   c h l o r i d e     E   E   F   E   A m m o n i u m   n i t r a t e     E   E   F   E   A r o m a t i c   h y d r o c a r b o n s     E   N D   F   N R   A S T M   f u e l   B     E   E   N R   G   A S T M   N o . 3   o i l     E   G   N R   G   A u t o m a t i c   t r a n s .   f l u i d     E   N D   N R   N R   A u t o m o t i v e   g a s o l i n e     E   N D   N R   N R   A v i a t i o n   g a s o l i n e     E   N D   N R   N R   B e e r     E   N R   E   E   B r o m i c   g a s     E   G   N R   N R   B u t a n e     E   E   N R   N R   B u t y l   a l c o h o l     E   G   G   G   C h l o r i n a t e d   s o l v e n t s     E   N R   N R   N R   C h r o m i c   a c i d   ( 7 0   % )     E   N R   F   N R   C r u d e   o i l     E   G   N R   N R   C y c l o h e x a n e     E   E   N R   N R   D i e s e l   o i l     E   E   N R   N R   F a t t y   a c i d s     E   N R   F   F   F l u o r o b e n z e n e     E   N D   N R   N R   F u e l   o i l     E   E   N R   N R   H e x a n e     E   E   N R   N R   H y d r o c h l o r i c   a c i d     E   N R   G   G   H y d r o g e n   g a s   ( 6 0   o C )     E   N R   F   E   H y d r o f l u o r i c   a c i d   ( 6 0   % )     E   N R   N R   G   J e t   f u e l   ( J P I )     E   G   N R   N R   K e r o s e n e     E   G   N R   N R   M i n e r a l   o i l     E   G   G   N R   N a p h t h a     E   G   N R   N R   N i t r i c   a c i d   ( 9 0   % )     E   N R   N R   N R   P h o s p h o r i c   a c i d   ( 8 5   % )     E   N R   N R   E   S u l f u r i c   a c i d   ( 9 5   % )     E   N R   N R   N R   T o l u e n e     E   N R   N R   N R   T r i c h l o r o m e t h a n e     E   N R   N R   N R   T r i f l u o r o e t h a n e       E     N R   N R   N R     E   –   e x c e l l e n t   G   –   g o o d   F   –   f a i r   N R   –   n o t   r e c o m m e n d e d   N D   –   n o   d a t a   a v a i l a b l e       B a s i c   F l u o r o p o l y m e r   D a t a   ( A u g u s t   2 0 0 3 )     I t e m   2 . 1 . 2 . 4   T h e r m a l   S t a b i l i t y     F i g u r e   3   s h o w s   t h e   u s e f u l   s e r v i c e   t e m p e r a t u r e   r a n g e   o f   c o m m e r c i a l l y   a v a i l a b l e   f l u o r o e l a s t o m e r s .           F i g u r e   3   U s e f u l   s e r v i c e   t e m p e r a t u r e   r a n g e s   f o r   c o m m e r c i a l   f l u o r o e l a s t o m e r s   7 )               I t e m   2 . 2   P e r f l u o r o e l a s t o m e r   [ C A S   n u m b e r   2 6 4 2 5 - 7 9 - 6 ]     I t e m   2 . 2 . 1   P o l y m e r i z a t i o n   P e r f l u o r o e l a s t o m e r   c a n   b e   p r o d u c e d   b y   e m u l s i o n - p o l y m e r i z a t i o n .   I n d u s t r y   g e n e r a l l y   u s e s   f r e e - r a d i c a l   p o l y m e r i z a t i o n   t e c h n o l o g y   i n   a q u e o u s   m e d i a .   T h e   i n i t i a t o r   f o r   t h e   p o l y m e r i z a t i o n   i s   u s u a l l y   a   w a t e r – s o l u b l e   p e r o x i d e   s u c h   a s   a m m o n i u m   p e r s u l f a t e   o r   p o t a s s i u m   p e r s u l f a t e .   A m m o n i u m   p e r f l u o r o o c t a n o a t e   ( A P F O ;   C 7 F 1 5 C O O N H 4 )   i s   g e n e r a l l y   u s e d   a s   a   p e r f l u o r i n a t e d   e m u l s i f i e r   t o   s t a b i l i z e   e m u l s i o n   t h a t   i s   p r o d u c e d   d u r i n g   p o l y m e r i z a t i o n .   T h e   p o l y m e r   e m u l s i o n   o b t a i n e d   i s   m o s t   f r e q u e n t l y   c o a g u l a t e d   b y   i n o r g a n i c   s a l t s   s u c h   a s   m a n g a n e s e   s u l f a t e   o r   a l u m i n u m   p o t a s s i u m   s u l f a t e ,   t h e n   w a s h e d   w i t h   w a t e r   a n d   d r i e d .   T h e   f i n i s h e d   p r o d u c t s   a r e   s u p p l i e d   a s   p e l l e t s ,   l u m p s   o f   m i l l e d   s h e e t s   2 ) .       I t e m   2 . 2 . 2   P r o p e r t i e s     P e r f l u o r o e l a s t o m e r   i s   d e s i g n a t e d   a s   F F K M   b y   t h e   A m e r i c a n   S o c i e t y   f o r   T e s t i n g   a n d   M a t e r i a l s   ( A S T M ) .   P e r f l u o r o e l a s t o m e r   h a s   n o   m e l t i n g   p o i n t   d u e   t o   i t s   a m o r p h o u s n e s s .     P e r f l u o r o e l a s t o m e r   i s   c r o s s - l i n k e d   b y   i o n i c   c r o s s - l i n k i n g ,   r a d i c a l   c r o s s - l i n k i n g ,   n i t i r i l e   c r o s s - l i n k i n g   a n d   i r r a d i a t i o n   c r o s s - l i n k i n g   d u r i n g   p r o c e s s i n g   t o   m a k e   e n d   p r o d u c t s .       B a s i c   F l u o r o p o l y m e r   D a t a   ( A u g u s t   2 0 0 3 )     I t e m   2 . 2 . 2 . 1   M o l e c u l a r   S t r u c t u r e     F i g u r e   4   s h o w s   t y p i c a l   c h e m i c a l   s t r u c t u r e s   o f   p e r f l u o r o e l a s t o m e r s .                                                                                F           F                       F           F                                                                                ( C           C ) x           ( C         C ) y                                                                                F           F                       F         O   -   R f                                               R f ;   C F 3 -   ( m a j o r   p r o d u c t s )   a n d   o t h e r   C n F 2 n + 1 -                                                             F i g u r e   4   C h e m i c a l   s t r u c t u r e s   o f   p e r f l u o r o e l a s t o m e r       C o m m e r c i a l l y   a v a i l a b l e   p e r f l u o r o e l a s t o m e r s   a r e   b a s e d   o n   a   c o p o l y m e r   o f   t e t r a f l u o r o e t h y l e n e   a n d   p e r f l u o r o   ( a l k y l   v i n y l   e t h e r ) .   P e r f l u o r o m e t h y l   v i n y l   e t h e r   ( P M V E ;   C A S   n u m b e r   1 1 8 7 - 9 3 - 5 ) .   i s   m o s t   c o m m o n l y   u s e d .   E v e n   u n c u r e d   p e r f l u o r o e l a s t o m e r   i s   n o t   s o l u b l e   i n   o r g a n i c   s o l v e n t s   d u e   t o   i t s   h i g h e r   f l u o r i n e   c o n t e n t ,   a n d   t h e r e f o r e   i t s   m o l e c u l a r   w e i g h t   c a n n o t   b e   m e a s u r e d .       I t e m   2 . 2 . 2 . 2   C r o s s - l i n k i n g   C h e m i s t r y     A s   m e n t i o n e d   a b o v e ,   p e r f l u o r o e l a s t o m e r   i s   c r o s s - l i n k e d   d u r i n g   p r o c e s s i n g .   T h e r e   a r e   f o u r   c r o s s - l i n k i n g   m e t h o d s :   i o n i c   c r o s s - l i n k i n g ,   f r e e   r a d i c a l   ( p e r o x i d e )   c r o s s - l i n k i n g ,   n i t i r i l e   c r o s s - l i n k i n g   a n d   i r r a d i a t i o n   c r o s s - l i n k i n g 1 ) .   I n   i o n i c   c r o s s - l i n k i n g ,   t h e   c u r i n g   a g e n t   u s e d   n e e d s   t o   b e a r   t w o   f u n c t i o n a l   g r o u p s ,   o r   s o - c a l l e d   b i s - n u c l e o p h i l e s ,   s u c h   a s   b i s p h e n o l s .     F r e e   r a d i c a l   c r o s s - l i n k i n g   i s   u s e d   w h e n   p e r f l u o r o e l a s t o m e r   i s   p o l y m e r i z e d   w i t h   a n o t h e r   m o n o m e r   b e a r i n g   a   f u n c t i o n a l   g r o u p   t h a t   c a n   b e   a t t a c k e d   b y   a   r a d i c a l .       N i t r i l e   c r o s s - l i n k i n g   i s   u s e d   w h e n   p e r f l u o r o e l a s t o m e r   i s   p o l y m e r i z e d   w i t h   a   m o n o m e r   c o n t a i n i n g   n i t r i l e   g r o u p 1 ) .   T h e   c r o s s – l i n k i n g   i s   i n i t i a t e d   b y   a   c a t a l y t i c   i n t e r a c t i o n   o f   a l k y l   t i n   c o m p o u n d s   w i t h   n i t r i l e   g r o u p s ,   f o l l o w e d   b y   a   t r i a z i n e   c r o s s - l i n k e d   s t r u c t u r e .     P e r f l u o r o e l a s t o m e r   c a n   b e   c r o s s - l i n k e d   w i t h o u t   a   c r o s s - l i n k i n g   a g e n t   t h r o u g h   t h e   u s e   o f   h i g h - e n e r g y   r a d i a t i o n 1 ) .     C r o s s - l i n k e d   p e r f l u o r o e l a s t o m e r   i s   n o t   s o l u b l e   i n   o r g a n i c   s o l v e n t s .   I t   s h o u l d   b e   n o t e d   h e r e   t h a t   c r o s s - l i n k i n g   i s   p a r t   o f   t h e   p e r f l u o r o e l a s t o m e r   m o l d i n g   p r o c e s s .   T h e   p r o c e s s   i n c l u d e s   m i x i n g ,   k n e a d i n g ,   e x t r u s i o n   o r   c a l e n d a r i n g   a n d   c r o s s - l i n k i n g .   P r e - c u r i n g   a n d   p o s t - c u r i n g   a r e   g e n e r a l l y   n e c e s s a r y   t o   c o m p l e t e   t h e   c r o s s - l i n k i n g   r e a c t i o n .       I t e m   2 . 2 . 2 . 3   C h e m i c a l   r e s i s t a n c e     P e r f l u o r o e l a s t o m e r   e x h i b i t s   m o r e   e x c e l l e n t   c h e m i c a l   r e s i s t a n c e   t h a n   f l u o r o e l a s t o m e r s   ( F K M )   d u e   t o   t h e   h i g h e r   f l u o r i n e   c o n t e n t   o n   t h e   p o l y m e r   b a c k   b o n e .     T a b l e   4   s h o w s   a   l i s t   o f   c h e m i c a l   r e s i s t a n c e   a n d   i t s   c o m p a r i s o n   w i t h   V D F - b a s e d   f l u o r o e l a s t o m e r s   ( F K M )   8 ) .     B a s i c   F l u o r o p o l y m e r   D a t a   ( A u g u s t   2 0 0 3 )       T a b l e   4   C o m p a r a t i v e   c h e m i c a l   r e s i s t a n c e s   o f   f l u o r o e l a s t o m e r s   8 )     F l u i d   T y p e       T y p i c a l     e x a m p l e     P e r f l u o r o e l a s t o m e r       F l u o r o e l a s t o m e r s   ( F K M )   A l i p h a t i c   h y d r o c a r b o n s       P r o p a n e     E x c e l l e n t       E x c e l l e n t   A r o m a t i c     h y d r o c a r b o n s       B e n z e n e     E x c e l l e n t       E x c e l l e n t   O r g a n i c   a c i d s       A c e t i c   a c i d     E x c e l l e n t       F a i r   –   G o o d   I n o r g a n i c   a c i d s       S u l f u r i c   a c i d   E x c e l l e n t       E x c e l l e n t   A l c o h o l s       M e t h a n o l     E x c e l l e n t       F a i r   -   E x c e l l e n t   I n o r g a n i c   b a s e       S o d i u m     h y d r o x i d e     E x c e l l e n t       P o o r   –   F a i r   O r g a n i c   b a s e       A n i l i n e     E x c e l l e n t       F a i r     E t h e r s       M e t h y l   t -     b u t y l   e t h e r     E x c e l l e n t       F a i r   –   G o o d   K e t o n e s       A c e t o n e     E x c e l l e n t       P o o r     N i t r o u s   o x i d i z e r s       A m m o n i u m     n i t r a t e     E x c e l l e n t       G o o d   H a l o g e n   o x i d i z e r s       C h l o r i n e     E x c e l l e n t       E x c e l l e n t   H e a t   t r a n s f e r   f l u i d s       E t h y l e n e     g l y c o l     E x c e l l e n t       E x c e l l e n t   O i l s   &   g r e a s e s       M i n e r a l   o i l     E x c e l l e n t       E x c e l l e n t   H a l o g e n a t e d   r e f r i g e r a n t s       H F C - 1 3 4 a     F a i r   -   G o o d       P o o r   –   F a i r   P o l a r   s o l v e n t s       W a t e r     E x c e l l e n t       E x c e l l e n t                   B a s i c   F l u o r o p o l y m e r   D a t a   ( A u g u s t   2 0 0 3 )     R e f e r e n c e s     1 .   S c h e i r s ,   J . ,   M o d e r n   F l u o r o p o l y m e r s ,   E d . ,   W i l e y   S e r i e s   i n   P o l y m e r   S c i e n c e ,   J o h n   W i l e y   &   S o n s ,   N e w   Y o r k ,   1 9 9 7 .     2 .   D r o b n y ,   J .   G . ,   T e c h n o l o g y   o f   F l u o r o p o l y m e r s ,   C R C   P r e s s .     3 .   F i g u r e   2 . 1 ,   S c h e i r s ,   J . ,   M o d e r n   F l u o r o p o l y m e r s ,   E d . ,   W i l e y   S e r i e s   i n   P o l y m e r   S c i e n c e ,   J o h n   W i l e y   &   S o n s ,   N e w   Y o r k ,   1 9 9 7 .     4 .   D a i k i n   A m e r i c a ,   I n c .   D A I - E L   H i g h   P e r f o r m a n c e   F l u o r o e l a s t o m e r s   P r o d u c t   I n f o r m a t i o n   ( E R C - 1 a ) .     5 .   T a b l e   2 . 5 ,   S c h e i r s ,   J . ,   M o d e r n   F l u o r o p o l y m e r s ,   E d . ,   W i l e y   S e r i e s   i n   P o l y m e r   S c i e n c e ,   J o h n   W i l e y   &   S o n s ,   N e w   Y o r k ,   1 9 9 7 .     6 .   T a b l e   2 3 . 2 ,   S c h e i r s ,   J . ,   M o d e r n   F l u o r o p o l y m e r s ,   E d . ,   W i l e y   S e r i e s   i n   P o l y m e r   S c i e n c e ,   J o h n   W i l e y   &   S o n s ,   N e w   Y o r k ,   1 9 9 7 .     7 .   F i g u r e   1 . 2 3 ,   S c h e i r s ,   J . ,   M o d e r n   F l u o r o p o l y m e r s ,   E d . ,   W i l e y   S e r i e s   i n   P o l y m e r   S c i e n c e ,   J o h n   W i l e y   &   S o n s ,   N e w   Y o r k ,   1 9 9 7 .     8 .   T a b l e   1 9 . 2 ,   S c h e i r s ,   J . ,   M o d e r n   F l u o r o p o l y m e r s ,   E d . ,   W i l e y   S e r i e s   i n   P o l y m e r   S c i e n c e ,   J o h n   W i l e y   &   S o n s ,   N e w   Y o r k ,   1 9 9 7 .


submitted under DACO 4.5.9.  This review is a joint effort of the PMRA
and the EPA.

	870.7600	Dermal Absorption - Rat

		Prothioconazole

			This study (MRID 46246423) was submitted in support of the proposed
registration of a new end use product, Proline 480 SC Foliar Fungicide,
containing the active ingredient prothioconazole.  This is a preliminary
study performed to obtain basic information on absorption of the use
product (JAU 6476 250 EC) and a 373 fold aqueous dilution (field
dilution) thereof.  Three other dermal absorption studies conducted in
monkeys were also submitted, one on the parent compound and two on the
prothioconazole desthio metabolite.

Two groups of five male Wistar rats were administered nominal doses of
2.5 or 0.0067 mg/cm2 of prothioconazole in 100 ·L of the respective
solutions to a 10 cm2 area of the back, and monitored up to 24 hr
post-dosing.  The skin wash was conducted after 24-hours and all animals
were sacrificed immediately after.  Dermal absorption was calculated by
adding residues measured in the excreta (urine + cage wash + feces),
carcass (blood + GI tract + carcass) and skin bound residues (skin test
site + residual skin).  Skin bound residues were included in the
calculation of dermal absorption, as the monitoring period (24- hours)
was not long enough to characterize skin bound residues.  As the high
dose exceeds the recommended guideline dose, it is not considered to be
useful to determine dermal absorption, as saturation of the treated site
may have occurred.  Mean dermal absorption at the low dose was 49.4%
(n=5).  This value is considered to be conservative because: (1) a
portion of the active ingredient was retained at the skin site (35.3%)
and it is unlikely that all of the skin bound residues will become
systemically available, and (2) the skin wash was not performed until 24
hours after exposure and 10 hours is considered most applicable to the
typical worker exposure time.

In addition, the formation of the potential metabolite, prothioconazole
desthio was investigated in the rinsing solutions of the application
site and in the applied skin on 1 animal at each dose level.  The
rinsing solutions of the application site and the applied skin at the
end of the 24 hour exposure period were analyzed by HPLC and TLC.  At
the high dose, the degradation product amounted to 0.5% on the skin at
the application site.  The metabolite was not found in the skin extracts
(extraction efficiency = 84%).  At the low dose, 6.3% of the applied
dose was due to prothioconazole desthio in the skin rinse and 3.3% of
the applied dose was detected as the metabolite in the skin extracts
(extraction efficiency = 64%).

________

			This study (MRID 46246424) was submitted in support of the proposed
registration of a new end use product, Proline 480 SC Foliar Fungicide,
containing the active ingredient prothioconazole.  The purpose of this
study was to determine the rate and route of elimination of
radiolabelled prothioconazole following a single intravenous or dermal
administration to male rhesus monkeys.  This exploratory study was to
aid in the design of a definitive dermal absorption and mass balance
study.  Three other dermal absorption studies conducted in rats and
monkeys were also submitted, one on the parent compound and two on the
desthio metabolite.

The purpose of this study was to determine the rate and route of
elimination of prothioconazole derived radioactivity following a single
intravenous or dermal administration to male rhesus monkeys.  A single
male rhesus monkey received either an intravenous dose of 240 g
prothioconazole-phenyl-UL-14C or a dermal dose of 240 g (10 g/cm2)
prothioconazole SC 480 containing 14C prothioconazole.

Dermal administration of prothioconazole SC 480, containing 14C
prothioconazole, for 8 hours to a male rhesus monkey resulted in
recovery of 3.30% of the dose in excreta (1.91% in urine, 0.90% in
feces, and 0.33% in cage debris/rinse samples) over 192 hours.  The
majority of the administered dermal dose was recovered from the skin was
of the application site (87.25 %).  The overall recovery of
radioactivity from the dermally dosed animal was 92.51% indicating that
7.49% of the administered dose was unaccounted for.  Total recovery of
the intravenous dosed animal through 192 hours post-dose was 35.68% in
urine, 13.91% in feces and 31.13% in cage debris/rinse samples
(attributed primarily to urinary excretion).  The overall recovery of
radioactivity for the intravenously dosed animal was 81.25%, indicating
that 18.75% may have remained in the body.

		Prothioconazole-desthio

			This (MRID 46246425) study was submitted in support of the proposed
registration of a new end use product, Proline 480 SC Foliar Fungicide,
containing the active ingredient prothioconazole.  The purposed of this
study was to determine the rate and route of elimination of
radiolabelled prothioconazole following a single intravenous or dermal
administration to male rhesus monkeys.  This exploratory study was to
aid in the design of a definitive dermal absorption and mass balance
study.  Three other dermal absorption studies conducted in rats and
monkeys were also submitted, two on the parent compound and one on the
prothioconazole desthio metabolite.

The purpose of this study was to determine the rate and route of
elimination of prothioconazole-desthio, a metabolite of prothioconazole,
derived radioactivity following a single intravenous or dermal
administration to male rhesus monkeys.  A single male rhesus monkey
received either an intravenous dose of 240 ug prothioconazole
desthio-phenyl-UL-14C or a dermal dose of 240 ug (10 g/cm2)
prothioconazole desthio SC 480 containing 14C prothioconazole desthio
for 8 hours.

Dermal administration of prothioconazole desthio SC 480, containing 14C
prothioconazole desthio, to a male rhesus monkey resulted in a dermally
absorbed dose of 7.11% (3.74% in urine, 2.19% in feces, 0.60% in cage
debris/rinse samples, 0.57% in the pan wash/wipe and chair wipe, and
0.01% in tape strips) through 192 hours.  However, 10.47% of the applied
dose was recovered from the non-occlusive cover and therefore not
available for absorption.  The majority of the administered dermal dose
was recovered from the application site (83.28 %) with 0.01% of the
applied dose recovered in the tape strips.  The overall recovery of
radioactivity from the dermally dosed animal was 100.92%.  The overall
recovery of radioactivity for the intravenously dosed animal was 97.54%,
indicating that 2.46% may have remained in the body.

Based on the results of this exploratory study, it was decided that only
dermal administration of prothioconazole desthio would be performed in
the definitive dermal absorption and mass balance study in monkeys.

________

			The purpose of this study (MRID 46246426) was to determine the rate
and route of elimination of prothioconazole-desthio, a metabolite of
prothioconazole, derived radioactivity following dermal administration
to male rhesus monkeys.  Five male rhesus monkeys received a dermal dose
of 144 ·g (6 ·g/cm2) prothioconazole-desthio SC 480 containing 14C
prothioconazole-desthio for 8 hours.

Dermal administration of prothioconazole-desthio SC 480, containing 14C
prothioconazole-desthio, to male rhesus monkeys resulted in a mean
recovery of 18.61% of the dose in excreta (10.25 % in urine, 5.79 % in
feces, 1.50 % in cage debris/rinse samples, and 1.07 % in the pan
wash/wipe and chair wipe) through 144 hours.  The majority of the
administered dermal dose was recovered from the application site (mean =
73.54 %).  The overall mean recovery of radioactivity from the dermally
dosed animals was 92.15 %.  In a previously conducted pilot study, the
overall recovery of radioactivity in a monkey dosed intravenously with
prothioconazole-desthio and followed for 192 hours was high (97.54 %).

In an exploratory study, dermal administration of
prothioconazole-desthio SC 480, containing 14C prothioconazole-desthio,
to a male rhesus monkey resulted in a dermally absorbed dose of 7.11%
(3.74% in urine, 2.19% in feces, 0.60% in cage debris/rinse samples, and
0.57% in the pan wash/wipe, chair wipe, and 0.01% in tape strips)
through 192 hours.  However, 10.47% of the applied dose was recovered
from the non-occlusive cover and therefore was not available for
absorption.  The majority of the administered dermal dose was recovered
from the application site (83.28 %) with 0.01% of the applied dose
recovered in the tape strips.  The overall recovery of radioactivity
from the dermally dosed animal was 100.92%.  The overall recovery of
radioactivity for the intravenously dosed animal was 97.54%, indicating
that 2.46% may have remained in the body.

A.3.9	Special Studies

In a Liver Foci study (MRID 46246437), SXX 0665 (95.4 % a.i.; Batch
No.1717008/90) was administered to 6 groups of Wistar Bor:WISW
(5/sex/group) in the diet with 1% peanut oil at a dose level of 980 ppm.
 An initiator, N-nitrosomorpholine (NNM), and a regenerative cellular
proliferation inducer, D-galactosamine (DGA), were administered to some
of the treatment groups.

The incidences of foci of altered hepatocytes (FAH) were slightly
increased in males and females administered the test substance (980 ppm)
for 6 weeks (groups 1 and 7) compared to their controls (groups 2 and
8).  The incidence of FAH was slightly decreased in males and females
administered the test substance (980 ppm) for 12 weeks (groups 3 and 9)
compared to their controls (groups 6 and 12).  The incidences of FAH
were higher in the control males compared to the females.
Administration of the test substance to animals previously treated with
an initiator (NNM) and a regenerative proliferation inducer (DGA)
(groups 4 and 10) produced only slightly elevated (no statistical
significance) incidences of FAH relative to those in the corresponding
control groups (groups 5 and 11).  Severe cytoplasmic vacuolation,
particularly following the 12-week treatment, was found in the Zone II
hepatocytes of nearly all males that had been exposed to the test
substance and exhibited this increased activity (this correlation was
absent in animal no. 19).  These vacuoles appeared void to the eye in
sections that had been treated with solvents. In native sections, these
vacuoles were highly refractive. Isolated cellular destruction and
mitosis of parenchyma1 cells were also observed in these animals.”  In
males administered the test substance, there was an increase in the
glucose-6 phosphate dehydrogenase activity in 3/5 animals compared to
0/5 controls after 6 weeks, and in 5/5 animals compared to 1/5 controls
after 12 weeks.  “This rise in activity was limited to the Rappaport
Zone I hepatocytes.”  The enzyme induction in the periportal
hepatocytes was stronger at 13 weeks in the males administered test
substance without NNM and DGA than with.  There were no clear patterns
with the incidence or severity of enzyme induction findings in the
females.  “No evident hepatocytic vacuolation was observed in the
females of any group.  However, in animals that had been treated with
the test substance, it was noted that the stored glycogen in perivenular
cells was distributed very uniformly throughout the cytoplasm, whereas
structures having the appearance of densely packed glycogen pools -
often concentrated at the cellular periphery - were observed in the
pertinent controls.”

This study reaffirms that there were no liver tumors in the long-term
studies and supports the findings that there are other effects in the
liver (vacuolation and enzyme induction).  A NOAEL or LOAEL will not be
established on this study since it is non-guideline and supplementary.

This study is non-guideline and is classified as supplemental.  This
review is a joint effort of the PMRA and the EPA.

________

In an acute intraperitoneal toxicity study (MRID 46246434), groups of
unfasted, 8- to 11-week-old SPF-bred Wistar Bor:WISW (SPF-Cpb)rats
(5/sex/dose, with some exceptions) were given a single intraperitoneal
dose of SXX 0665 (94.0% a.i.) in 1% v/v Cremophor EL at doses of 10,
100, 355, 400, 450, 500, 800, or 1000 mg/kg bw and observed for 14 days.

Both male and female animals at the 100 mg/kg bw dose level showed signs
of apathy and labored breathing.  The males in this dose group also
showed decreased motility, staggering gait, and atony.  Females showed
these signs at higher dose levels.  Both sexes also displayed at doses
higher than 100 mg/kg bw piloerection, poor or no reflexes, lying on the
side, spasmodic state, transient convulsions, stretched legs, and
lacrimation.  Clinical signs were not observed in either sex at 10 mg/kg
bw.  Male animals dosed with 10 and 100 mg/kg bw gained body weight
throughout the study.  Above these doses, a number of surviving males
showed initial decreases in body weight before body weight gains were
observed.  Four of five females dosed with 10 mg/kg bw gained weight
during the study period.  The majority of surviving females in the other
dose groups showed a decrease in body weight at some point during the
observation period.  A number of male animals dosed with 355 to 450
mg/kg bw or higher showed whitish liver surface in places.  Males dosed
at 500 mg/kg bw or greater showed pale organs and patchy and/or
distended lungs.  Males dosed with 800 mg/kg bw were found with mucid
contents in the small intestine.

Estimated Intraperitoneal LD50:	Males: between 450 and 500 mg/kg bw

										Females: 632 mg/kg bw

This acute intraperitoneal study is acceptable as a supplementary study
only because there is no guideline requirement for acute intraperitoneal
toxicity.  This review is a joint effort of the PMRA and the EPA.

________

In this study (MRID 46246436), JAU 6476 (purity not provided) was
studied in vitro using solubilized hog thyroid microsomes as an enzyme
source in order to determine if there is an interaction with thyroid
peroxidase (TPO).  As a source of reference, ethylenethiourea (ETU),
propylthiouracil (PTU), 3-mercapto-1,2,4-triazole (a basic thiourea
moiety of JAU 6476), and JAU 6953 (a related thiourea derivative) were
investigated under similar conditions.

Thyroid peroxidase (TPO)-catalyzed guaiacol oxidation was inhibited by
compounds tested. 3-mercapto- 1,2,4-triazole had the lowest IC50 value
(i.e.: lowest concentration required to inhibit the reaction by 50%),
followed by PTU then JAU 6476 and JAU 6953.  This provided initial
indication that TPO may be irreversibly inhibited.

PTU, ETU, JAU 6476, JAU 6953 and 3-mercapto-1,2,4-triazole
dose-dependently suppressed TPO- catalyzed iodine formation temporarily.
 Following suppression, iodine reappeared.  The rate was then similar to
controls.  3-mercapto-1,2,4-triazole suppressed the rate of the
reappearing iodine formation longer than the other compounds.

This study showed inhibition of guaiacol and iodine oxidation with the
compounds tested.

This study is classified as supplementary.  This study is non-guideline.
 This review is a joint effort of the PMRA and the EPA.

________

In an immunotoxicity study (MRID 46246438) JAU 6476 (Purity: 98.4%) was
administered to 8 CRL:CDI(ICR) mice/sex/dose by gavage at dose levels of
0, 25, 100 and 400 mg/kg bw/day. Clinical observations and body weight
measurements were performed daily.  Animals were exposed to the test
substance or positive control for 28 days, then injected intravenously
with sheep erythrocytes on day 24.  On day 28 (males) or 29 (females)
(peak day of IgM response), the animals were sacrificed, spleens were
removed and weighed, then spleen cells were prepared on day 30.  The
primary response to sheep erythrocytes was measured using a plaque assay

Piloerection was noted in the high-dose males from days 13-21.There were
no significant effects on body weight, food consumption or spleen
weights.  Under the conditions of this study, JAU 6476 did not suppress
the humoral immune response in a dose-dependent manner in that it did
not significantly decrease the IgM antibody-forming cell response to the
T-dependent antigen (sheep erythrocytes).  An increase in plaque-forming
cells was noted in the high-dose males ((125%).

This immunotoxicity study is classified as supplemental and does not
satisfy the guideline requirement for an immunotoxicity study (OPPTS
870.7800) in the mouse. Thymus weights, spleen cell viability and IgM
PFC activity per spleen were not measured/reported.  The range of
historical control data for spleen cell counts was not reported and the
positive control validation study was not provided.  This review is a
joint effort of the PMRA and the EPA.

________

A review was performed of ovarian toxicity in rats and mice following
varying lengths of exposure to SXX 0665 (MRID 46246441).  These studies
were: 4-weeks, 14-weeks with 5-weeks recovery, combined chronic toxicity
and carcinogenicity, and two-generation reproduction in rats as well as
13-weeks (range-finding) and carcinogenicity in mice.

Appendix B:  Metabolism Assessment  TC \l1 "Appendix B:  Metabolism
Assessment

B.1	Metabolism Guidance and Considerations TC \l2 "B.1	Metabolism
Guidance and Considerations

Figure B.1. Proposed metabolic pathway for [phenyl and
triazole-14C]-prothioconazole (JAU6476) in/on sugar beet, wheat and
peanut:

Figure B.2.  Proposed metabolic pathway for
[triazole-3,5-14C]-desthio-prothioconazole (SXX 0665) in/on summer
wheat:

Figure B.3.  Proposed metabolic pathway for Prothioconazole (JAU6476)
in livestock.

P = poultry   G = goat

Figure B.4. Proposed metabolic pathway in laying hens for [triazole- or
phenyl-14C]-prothioconazole (JAU6476):

Figure B.5. Proposed metabolic pathway in lactating goat for [triazole-
or phenyl-14C]-prothioconazole (JAU6476):

Figure B.6.  Proposed metabolic pathway for
[phenyl-14C]-desthio-prothioconazole (JAU6476-desthio or SXX0665) in
lactating goat:

Figure B.7. Proposed metabolic pathway for prothioconazole (JAU6476) in
rats following oral administration (extracted from page 18 of the
registrant’s study report).

Table B.1.	Chemical Names and Structures of Prothioconazole and its
Transformation Products.

Common Name/Code

Matrix	Chemical Name	Structure

Prothioconazole; JAU6476

[Parent]

Wheat forage, hay, straw, and grain

Peanut hay

Sugar beet tops

Rotated Swiss chard, turnip tops and root, and wheat straw

Goat milk, liver, kidney, muscle, and fat

Hen egg, liver, muscle, and fat
2-[2-(1-chlorocyclopropyl)-3-(2-chlorophenyl)-2-hydroxypropyl]-1,2-dihyd
ro-3H-1,2,4-triazole-3-thione

Prothioconazole-desthio; JAU6476-desthio

[included in tolerance expression for plant and animal commodities]

Wheat forage, hay, straw, and grain

Peanut hay and nutmeat

Sugar beet tops and root

Rotated Swiss chard, turnip tops and root, and wheat forage, hay, straw,
and grain

Goat milk, liver, kidney, muscle, and fat

Hen egg, liver, muscle, and fat
α-(1-chlorocyclopropyl)-α-[(2-chlorophenyl)methyl]-1H-1,2,4-triazole-1
-ethanol

Prothioconazole-4-hydroxy; JAU6476-4-hydroxy

[included in tolerance expression for animal commodities]

Goat milk, liver, kidney, muscle, and fat

Hen liver and muscle
2-[2-(1-chlorocyclopropyl)-3-(2-chloro-4-hydroxyphenyl)-2-hydroxypropyl]
-1,2-dihydro-3H-1,2,4-triazole-3-thione

JAU6476-α-OH-desthio

Wheat forage, hay, straw, and grain

Sugar beet tops

Rotated Swiss chard, turnip tops and root, and wheat forage, hay, straw,
and grain
2-(1-chlorocyclopropyl)-1-(2-chlorophenyl)-3-(1H-1,2,4-triazol-1-yl)-1,2
-propanediol

JAU6476-3-OH-desthio

Wheat forage, hay, and straw

Peanut hay

Rotated Swiss chard, turnip tops and root, and wheat forage, hay, straw,
and grain

Goat milk, liver, kidney, muscle, and fat

α-(1-chlorocyclopropyl)-α-[(2-chloro-3-hydroxyphenyl)-methyl]-1H-1,2,4
-triazole-1-ethanol

JAU6476-4-OH-desthio

Wheat forage, hay, and straw

Peanut hay

Rotated Swiss chard, turnip tops and root, and wheat forage, hay, straw,
and grain

Goat liver

Hen egg and liver
α-(1-chlorocyclopropyl)-α-[(2-chloro-4-hydroxyphenyl)-methyl]-1H-1,2,4
-triazole-1-ethanol

JAU6476-6-OH-desthio

Wheat forage, hay, and straw

Rotated turnip tops and root and wheat forage and straw
α-(1-chlorocyclopropyl)-α-[(2-chloro-6-hydroxyphenyl)-methyl]-1H-1,2,4
-triazole-1-ethanol

JAU6476-OH-desthio isomers

Wheat forage and straw

Sugar beet tops

JAU6476-triazolinone

Wheat forage, hay, straw, and grain

Peanut hay

Sugar beet tops and root

Rotated Swiss chard, turnip tops and root, and wheat forage, hay, and
straw
2-[2-(1-chlorocyclopropyl)-3-(2-chlorophenyl)-2-hydroxypropyl]-2,4-dihyd
ro-3H-1,2,4-triazole-3-one

JAU6476 sulfonic acid

Wheat forage, hay, and straw

Peanut hay and nutmeat

Sugar beet tops

Rotated Swiss chard, turnip tops, and wheat forage, hay, and straw
1-[2-(1-chlorocyclopropyl)-3-(2-chlorophenyl)-2-hydroxypropyl]-1H-1,2,4-
triazole-5-sulfonic acid

JAU6476-α-acetoxy-desthio

Wheat forage, hay, straw, and grain

Rotated wheat forage, hay, and straw
2-(1-chlorocyclopropyl)-1-(2-chlorophenyl)-2-hydroxy-3-(1H-1,2,4-triazol
-1-yl)propyl acetate

JAU6476-disulfide

Wheat forage, hay, straw, and grain

Peanut hay

Rotated Swiss chard, turnip tops and root, and wheat forage, hay, and
straw

JAU6476-benzylpropyldiol

Wheat straw

Rotated Swiss chard, turnip tops and root, and wheat straw
2-(1-chlorocyclopropyl)-3-(2-chlorophenyl)propane-1,2-diol

Triazolyl-ethanol

Wheat straw

Peanut hay

Sugar beet tops

Rotated Swiss chard, turnip tops and root, and wheat forage, hay, and
straw

Hen egg, liver, muscle, and fat
1-(1-chlorocyclopropyl)-2-(1H-1,2,4-triazol-1-yl)ethanol

JAU6476-desthio-phenyl-cysteine

Wheat forage

Peanut hay

JAU6476-dihydroxy-diene sulfonic acid

Peanut hay

JAU6476-dihydroxyolefin sulfonic acid

Peanut hay

JAU6476-desthio-hydroxy-dienyl-cysteine

Peanut hay and nutmeat

Sugar beet tops and root

JAU6476-S-methyl

Goat liver

α-(1-chlorocyclopropyl)-α-[(2-chlorophenyl)methyl]-3-(methylthio)-1H-1
,2,4-triazole-1-ethanol

JAU6476-lactoside

Goat milk

JAU6476-dihydroxy-diene

Goat milk

Hen liver and muscle
2-[2-(1-chlorocyclopropyl)-3-(2-chloro-3,4-dihydroxycyclohexa-1,5-dien-1
-yl)-2-hydroxypropyl]-2,4-dihydro-3H-1,2,4-triazole-3-thione 1

JAU6476-desthio-dihydroxy-diene

Goat milk and liver
3-chloro-4-[2-(1-chlorocyclopropyl)-2-hydroxy-3-(1H-1,2,4-triazol-1-yl)p
ropyl]cyclohexa-3,5-diene-1,2-diol 1

Triazole metabolites

1,2,4-Triazole

Hen egg, liver, muscle, and fat	1,2,4-triazole

Triazolylalanine (TA)

Wheat forage, hay, straw, and grain

Peanut hay and nutmeat

Sugar beet tops and root

α-amino-1H-1,2,4-triazole-1-propanoic acid

Triazolylacetic acid (TAA)

Wheat forage, hay, straw, and grain

Peanut hay and nutmeat

Rotated Swiss chard, turnip tops and root, and wheat forage, hay, straw,
and grain	1H-1,2,4-triazole-1-acetic acid

Triazolylhydroxypropionic acid (THPA)

Wheat forage, hay, straw, and grain

Peanut hay and nutmeat

Sugar beet tops

Rotated Swiss chard, turnip tops and root, and wheat forage, hay, straw,
and grain	α-hydroxy-1H-1,2,4-triazole-1-propanoic acid

Thiocyanate

Goat milk, liver, kidney, muscle, and fat

Hen egg, liver, muscle, and fat	thiocyanate ion

Glucosides

JAU6476-desthio-glucoside

Wheat hay and straw

JAU6476-OH-desthio glucoside isomers 2

Wheat forage, hay, straw, and grain

Peanut nutmeat and hay

Rotated Swiss chard, turnip tops and root, and wheat forage, hay, and
straw

JAU6476-OH-desthio glucoside isomers

Sugar beet tops

or

JAU6476-desthio-malonyl-glucoside

Wheat forage and hay

JAU6476-OH-desthio-malonyl-glucoside

Wheat forage, hay, and straw

Peanut hay

JAU6476-dihydroxy-desthio-malonyl-glucoside

Wheat forage

JAU6476-benzylpropyldiol glucoside

Wheat hay, straw, and grain

Rotated turnip tops and root and wheat forage and straw
2-(1-chlorocyclopropyl)-3-(2-chlorophenyl)propane-1,2-diol glucoside

Triazolyl-ethanol-glucoside

Wheat forage, hay, and straw

Peanut hay

Sugar beet tops

Rotated turnip tops and root and wheat forage, hay, and straw

Triazolyl-sulfonic acid-ethanol-glucoside

Sugar beet tops

JAU6476-OH-sulfonic acid-glucoside isomers

Wheat forage and hay

Sugar beet tops

JAU6476-hydroxy-di-sulfonic acid glucoside

Sugar beet tops

JAU6476-desthio-dihydroxy-olefin glucosides

Peanut hay and nutmeat

Rotated Swiss chard, turnip tops and root, and wheat forage, hay, and
straw

Glucuronides

JAU6476-hydroxy-glucuronide 2

Goat milk, liver, kidney, muscle, and fat

Hen liver

JAU6476-S-glucuronide

Goat milk, liver, kidney, muscle, and fat

Hen egg, liver, muscle, and fat

JAU6476-O- or S-glucuronide

Goat milk, liver, kidney, muscle, and fat

Hen egg, liver, muscle, and fat

JAU6476-N-glucuronide

Goat milk, liver, kidney, muscle, and fat

Hen liver and muscle

JAU6476-desthio-3,4-dihydroxy-dienyl-glucuronide

Goat liver

Hen liver and muscle

JAU6476-4-hydroxy-desthio-glucuronide

Goat milk

JAU6476-dihydroxy-desthio-glucuronide

Goat milk

JAU6476-hydroxy-methoxy-desthio-glucuronide

Goat milk

JAU6476-desthio-glucuronide

Goat milk

Sulfate conjugates

Sulfate conjugate of JAU6476-hydroxy

Goat liver

Sulfate conjugate of JAU6476-hydroxy-desthio

Hen liver and fat

Sulfate conjugate of JAU6476-dihydroxy-desthio

Hen liver, muscle, and fat

Sulfate conjugate of JAU6476-hydroxy-methoxy-desthio

Hen liver, muscle, and fat

1  When chemical names were not provided by the petitioner, the chemical
naming feature of ISIS/Draw was used to generate the name.

2  Including 3-hydroxy and/or 4-hydroxy isomers.

Table B.2.  Tabular Summary of Metabolites & Degradates of
Prothioconazole.

Chemical Name

Matrix

Percent TRR

Structure

Major Residue (>10%TRR)

Minor Residue (<10%TRR)

Prothioconazole

2-[2-(1-chlorocyclopropyl)-3-(2-chlorophenyl)-2-hydroxypropyl]-1,2-dihyd
ro-3H-1,2,4-triazole-3-thione

Wheat , grain

Yes

Wheat ,forage

Yes

Wheat, hay

Yes

Wheat, straw

Yes

Sugar beet, root

NF

Sugar beet, tops

Yes

Peanut, nut meat

NF

Peanut, hay

Yes

Goat, milk

Yes

Goat, liver

Yes

Goat, kidney

Yes

Goat, muscle

Yes

Goat, fat

Yes

Hen, egg

Yes

Hen, liver

Yes

Hen, fat

Yes

Hen, muscle

Yes

Hen, egg

Yes

Rat

Yes 22% adm dose (feces)

Water

JAU6476-O- or S-glucuronide

Wheat

NF

Sugar beet

NF

Peanut

NF

Goat, milk

Yes

Goat, liver

Yes

Goat, kidney

Yes

Goat, muscle

Yes

Goat, fat

Yes

Hen, egg

Yes

Hen, liver

Yes

Hen, fat

Yes

Hen, muscle

Yes

Hen, egg

Yes

Rat

Yes 46% adm dose (bile)

Yes 8% adm dose (urine)

Water

Prothioconazole-Desthio

Wheat , grain

15.9% (0.0139 ppm)

Wheat ,forage

35.3% (3.7 ppm)

Wheat, hay

18.5% (1.64 ppm)

Wheat, straw

22.3% (5.95 ppm)

Sugar beet, root

41% (0.048 ppm)

Sugar beet, tops

26% (1.14 ppm)

Peanut, nut meat

NF

Peanut, hay

26.7% (1.14 ppm)

Goat, milk

Yes

Goat, liver

Yes

Goat, kidney

Yes (Glucuronide)

Goat, muscle

Yes

Goat, fat

Yes (free & Glucuronide)

Hen, egg

Yes

Hen, liver

Yes

Hen, fat

Yes

Hen, muscle

Yes

Hen, egg

Yes

Rat

Yes 18% adm dose (feces)

Water

Yes

1,2,4-triazole

Wheat

NF

Sugar beet

NF

Peanut

NF

Goat

NF

Hen

Yes (egg and muscle)

Yes (liver)

Rat

Water

Yes

Triazolyalanine (TA)

Wheat

Yes (all except straw)

Yes (straw)

Not available

Sugar beet

Yes (roots)

Yes (tops)

Peanut

Yes (nutmeat)

Yes (hay)

Goat

NF

Hen

NF

Rat

Water

Triazolylacetic acid (TAA)

Wheat

Yes (grain)

Yes (forage, hay, & straw)

Sugar beet

NF

Peanut

Yes (nutmeat & hay)

Goat

NF

Hen

NF

Rat

Water

Thiocyanate

thiocyanate ion

Wheat

NF

Sugar beet

NF

Peanut

NF

Goat

Yes (milk, fat, muscle)

Yes (liver, kidney)

Hen

Yes (all tissues)

Rat

Water

JAU6476-4-hydroxy

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ro-3H-1,2,4-triazole-3-thione

Wheat

NF

Sugar beet

NF

Peanut

NF

Goat

Yes (liver)

Yes (milk, muscle, kidney, & fat)

Hen

Yes (liver)

Rat

Water

JAU6476-4-hydroxy-glucuronide

Wheat

NF

Structure not available

Sugar beet

NF

Peanut

NF

Goat

Yes (muscle)

Yes (kidney)

Hen

NF

Rat

Water

Wheat:

MRID:  46246141;  Haas, M.; Bornatsch, W. (2000) Metabolism of JAU 6476
in Spring Wheat (after foliar application).  Project Number:
M/1730851/5, 110880, MR/198/99.  Unpublished study prepared by Bayer Ag
Institut fuer Ruckstands-Analytik.  149 p.

MRID:  46246142;  Haas, M. (2001) Metabolism of JAU 6476 in Spring Wheat
after Seed Dressing.  Project Number: M/1730885/2, 110881, MR/467/99.
Unpublished study prepared by Bayer Ag Institut fuer
Ruckstands-Analytik.  84 p.

MRID:  46246143;  Duah, F.; Lopez, R. (2004) The Metabolism of
[Triazole-3, 5-(Carbon 14)] JAU6476 in Wheat.  Project Number: J6041601,
200733.  Unpublished study prepared by Bayer Corp.  197 p.

MRID:  46246144;  Vogeler, K.; Sakamoto, H.; Brauner, A. (1993)
Metabolism of SXX 0665 in Summer Wheat.  Project Number: M/1730365/5,
MR/PF3906, PF/3906.  Unpublished study prepared by Bayer Ag Institut
fuer Ruckstands-Analytik.  114 p.

Peanut:

MRID:  46246145;  Haas, M. (2001) Metabolism of [Phenyl-UL-(Carbon
14)]JAU6476 in Peanuts.  Project Number: M/1730984/2, MR/193/01.
Unpublished study prepared by Bayer Ag Institut fuer
Ruckstands-Analytik.  130 p.

MRID:  46246146;  Haas, M. (2003) Metabolism of [triazole-UL-(Carbon
14)]JAU6476 in Peanuts.  Project Number: M1731145/2, MR/194/02.
Unpublished study prepared by Bayer Ag, Institute of Product Info.  145
p.

Sugar Beet:

MRID:  46246147;  Beedle, E.; Ying, S. (2004) The Metabolism of
[Triazole-UL-(Carbon 14)]JAU6476 in Sugar Beets.  Project Number:
J6041603, 200467.  Unpublished study prepared by Bayer Corp.  91 p.

MRID:  46246148;  Beedle, E.; Ying, S. (2004) The Metabolism of
[Phenyl-UL-(Carbon 14)]JAU6476 in Sugar Beets.  Project Number:
J6041602, 200466.  Unpublished study prepared by Bayer Corp.  86 p.

Livestock (Goat):

MRID:  46246149;  Weber, E.; Weber, H.; Spiegel, K. (2003)
[Triazole-UL-(Carbon 14)]JAU6476: Absorption, Distribution, Excretion,
and Metabolism in the Lactating Goat.  Project Number: M51819114,
MR/448/02.  Unpublished study prepared by Bayer Ag, Institute of Product
Info.  308 p.

MRID:  46246150;  Weber, H.; Spiegel, K. (2001) [Phenyl-UL-(Carbon
14)]JAU6476: Absorption, Distribution, Excretion, and Metabolism in the
Lactating Goat.  Project Number: M/91819082, MR/092/01.  Unpublished
study prepared by Bayer Ag Institut fuer Ruckstands-Analytik.  205 p.

MRID:  46246201; Weber, H.; Weber, E.; Spiegel, K. (2002)
((Phenyl-UL-(Carbon 14))JAU6476-desthio: Absorption, Distribution,
Excretion, and Metabolism in the Lactating Goat Including the Validation
of the Residue Analytical Method for the Determination of
JAU6476-desthio, JAU6476-3-hydroxy-desthio.  Project Number: M91819091,
SXX1, SXX2.  Unpublished study prepared by Bayer Ag Institut fuer
Ruckstands-Analytik.  399

Livestock (Hens):

MRID:  46246202;  Weber, H.; Spiegel, K. (2001) ((Phenyl-UL-(Carbon
14))JAU6476: Absorption, Distribution, Excretion, and Metabolism in
Laying Hens.  Project Number: M/81819090, MR/309/01.  Unpublished study
prepared by Bayer Ag Institut fuer Ruckstands-Analytik.  142 p.

MRID:  46246203; Weber, H.; Justus, K. (2003) ((Triazole-UL-(Carbon
14))JAU6476: Absorption, Distribution, Excretion, and Metabolism in
Laying Hens.  Project Number: M/91819118, MEF005/03.  Unpublished study
prepared by Bayer Ag, Institute of Product Info.  157 p.

Minor metabolites (<10% TRR) that were found in only one study or
matrices were not included in this table.

NF = not found.

Table B.3.  Summary of physical/chemical and environmental fate and
transport properties of prothioconazole combined residues of concern.

PARAMETER	VALUE(S) (units)	SOURCE MRID	COMMENT

  Chemical Name	Prothioconazole:

  SEQ CHAPTER \h \r 1
2-[2-(1-Chlorocyclopropyl)-3-(2-chloropheny1)-2-hydroxypropyl]-1,2-dihyd
ro-3H-1,2,4-triazole-3-thione;

Prothioconazole-desthio:

2-[2-(1-Chlorocyclopropyl)-3-(2-chlorophenyl)-2-hydroxy-propyl]-1,2-dihy
dro-3H-1,2,4-triazole

Prothioconazole-S-methyl:

alpha-1(1-chlorocyclopropyl)-alpha-[(2-chlorophenyl)methyl]-3-(methylthi
o)-1H-1,2,4-triazole-1-ethanol	46246003   SEQ CHAPTER \h \r 1 46477401
–

  Molecular Weight	Prothioconazole:   SEQ CHAPTER \h \r 1 344.264

Prothioconazole-desthio: 312.2

Prothioconazole-S-methyl: 358.3	46246003 46477401	–

  Solubility

                   (pH 4 (20 oC))

                   (pH 8 (20 oC))

                   (pH 9 (20 oC))	Prothioconazole:

5 mg/L or ppm

300 mg/L or ppm

2000 mg/L or ppm	46246003	  SEQ CHAPTER \h \r 1 Moderately solubility at
acidic pH, highly soluble at alkaline pHs.

  Vapor Pressure (20 oC and          25 oC)	Prothioconazole:   SEQ
CHAPTER \h \r 1 <<4 x 10-7 Pa	46246003	  SEQ CHAPTER \h \r 1 Relatively
non-volatile under field conditions.

  Henry’s Law constant (20 oC)	Prothioconazole: <2.96 x 10-10
atm-m3/mol	46246003	Estimated from vapor pressure and water solubility.

  pKa (20 oC)	Prothioconazole: 6.9	46246003	  SEQ CHAPTER \h \r 1 Weak
acid, anion at neutral and alkaline pHs.

 Octanol-Water Partition

 Coefficient (log KOW,  at 20 oC)

                 Unbuffered

                  pH 4

                  pH7

                  pH9	Prothioconazole:

4.05

4.16

3.82

2.00	46246003	  SEQ CHAPTER \h \r 1 Potential for bioaccumulation at
neutral and acidic pH.

  Hydrolysis Half-life

  (pH 4, 7, 9; (25 oC))

	Prothioconazole and Prothioconazole-desthio:

stable

(Prothioconazole-S-methyl is not formed from prothioconazole
hydrolysis.)	  SEQ CHAPTER \h \r 1 46246505

  SEQ CHAPTER \h \r 1 46246506	Study (46246505) conducted on
prothioconazole at 50 oC; results extrapolated to 25 oC.  Phenyl label
only.  Stable at all three pHs.

Study (46246506) conducted on prothioconazole-desthio as “parent” at
25 oC.  Degradation slopes not significantly different from zero; phenyl
label only.

  Aqueous Photolysis Half-life

  (pH 7, at 25 oC)	Prothioconazole:

t1/2  = 9.7 days

Prothioconazole-desthio:

Increasing at study termination

Prothioconazole and Prothioconazole-desthio:

t1/2  = 101.9 days

(Prothioconazole-S-methyl is not formed from prothioconazole aqueous
photolysis.)	46246507	Value corrected to represent natural sunlight at
40°N latitude; uncorrected laboratory half-life of 19.9 days for both
phenyl and triazole labels (continuous irradiation; xenon lamp).
Concentration of prothioconazole-desthio was still increasing at
prothioconazole aqueous photolysis study termination.

  Soil Photolysis Half-life	Prothioconazole and Prothioconazole-desthio:

stable

(Prothioconazole-S-methyl is not formed from prothioconazole soil
photolysis.)	46246510	Half-life could not be calculated as parent
degraded faster in dark samples than in irradiated samples.  Phenyl
label only.  Concentration of prothioconazole-desthio was still
increasing at study termination.

  Aerobic Soil Metabolism

  Half-life	Prothioconazole combined residues of concern:

t1/2 =  533.2 days (silt; phenyl),                         866.4 days
(silt; triazole).                                   990.2 days (loamy
sand; phenyl),                   1386.3 days (loamy sand; triazole),
               866.4 days (sandy loam; phenyl) ,
462.1 days (silty clay loam; phenyl).

                                                  	46246511 46246512
Half-lives are calculated via linear regression on log-transformed data,
combining amounts of prothioconazole, prothioconazole-desthio, and
prothioconazole-S-methyl per sampling interval.   Phenyl and triazole
labels treated separately, labeled accordingly.  Non-extractable
residues added in as parent.

  Anaerobic Aquatic Metabolism

  Half-life	Prothioconazole combined residues of concern:

t1/2  = stable (total system);

56.8 days (water layer).

	46246516	  SEQ CHAPTER \h \r 1 Fuquay, GA pond sediment/water system.
Sandy clay loam/water, phenyl label only.  Half-lives are calculated via
linear regression on log-transformed data, combining amounts of
prothioconazole, prothioconazole-desthio, and prothioconazole-S-methyl
per sampling interval.  Non-extractable residues added in as parent.

  Aerobic Aquatic Metabolism

  Half-life	Prothioconazole combined residues of concern:

t1/2 = 433.2 days (H, total system, p),                346.6 days (H,
total system, t),                            106.6 days (A, total
system, p),                           67.3 days (A, total system, t).

t1/2  = 17.2 days (H, water layer, p),                    16.2 days (H,
water layer, t),                               23.3 days (A, water
layer, p),                              21.7 days (A, water layer, t).

	  SEQ CHAPTER \h \r 1 46246515	Two systems tested: (H) Honniger Weiher
pond (loam/water) and (A)   SEQ CHAPTER \h \r 1 Anglerweiher lake (loamy
sand/water). Both phenyl (p) and triazole (t) labels in each system.
Half-lives are calculated via linear regression on log-transformed data,
combining amounts of prothioconazole, prothioconazole-desthio, and
prothioconazole-S-methyl per sampling interval.  Non-extractable
residues added in as parent.

Organic Carbon Partition

  Coefficient (KOC)	(mL/gOC)	LS	SCL	SL	S

Prothioconazole	--

	--	--	--	  SEQ CHAPTER \h \r 1 46246539   SEQ CHAPTER \h \r 1 46246504

	Parent mobility cannot be determined due to instability and low column
resolution; very high sorption estimated, lower mobility than
transformation products

	Prothioconazole-desthio	523	536	617	625	  SEQ CHAPTER \h \r 1 46246450

	Conducted on prothioconazole-desthio as “parent.”  Used four soils:
loamy sand (LS) at 0.79%OC, silty clay loam (SCL) at 1.66%OC, sandy loam
(SL) at 2.02%OC, silt (S) at 2.14%OC.

	Prothioconazole-S-methyl	1973	2484	2772	2995	  SEQ CHAPTER \h \r 1
46246501	Conducted on prothioconazole-S-methyl as “parent.”  Used
same soils as MRID: 46246450.

  Soil Partition Coefficient (Kd)	(mL/g)	LS	SCL	SL	S

Prothioconazole	--	--	--	--	  SEQ CHAPTER \h \r 1 46246539   SEQ CHAPTER
\h \r 1 46246504	Same as for KOC.

	Prothioconazole-desthio	4.13	8.90	12.46	13.38	  SEQ CHAPTER \h \r 1
46246450	Same as for KOC.

	Prothioconazole-S-methyl	15.6	41.2	56.0	64.1	  SEQ CHAPTER \h \r 1
46246501	Same as for KOC.

  Terrestrial Field Dissipation

  Half-life1	California (sandy loam/loam):        Prothioconazole:
                                                t1/2 (in surface soil)=
2.2 days;

Not detected above LOD below a depth of 15 cm nor after 7DAT.
                           Prothioconazole-desthio:
                      t1/2 (in surface soil)= 84.5 days;

Detected above LOD to a depth of 45 cm and through 307DAT.

Georgia (sand/sandy loam):

Prothioconazole:
                            t1/2 (in surface soil)= 4.7 days;

Not detected above LOD below a depth of 15 cm nor after 14DAT.

Prothioconazole-desthio:

t1/2 (in surface soil)= 96.3 days;

Detected above LOD to a depth of 30 cm through 7DAT.

New York (loamy sand):

Prothioconazole:

t1/2 (in surface soil)= 96.3 days;

Not detected above LOD below a depth of 15 cm nor after 211DAT.

Prothioconazole-desthio:                                       t1/2 (in
surface soil)= 315.1 days;

Not detected above LOD below a depth of 15 cm (except for one sampling
interval  (211DAT) where detected above LOD to 30 cm); detected above
LOD through study completion (567DAT).	46246517

46246518

46246519	Studies conducted on prothioconazole as parent.  For   SEQ
CHAPTER \h \r 1 half-lives calculated for degradates from parent
dissipation studies, day of max concentration of degradate is used as
day zero in regression.

  Aquatic Field Dissipation

  Half-life1	California (clay):
Prothioconazole:                                                    t1/2
(in sediment)= 203.9 days;                               t1/2 (in paddy
water)= 1.7 days.                Prothioconazole-desthio:
                       t1/2 (in sediment)= 122 days.

Arkansas (loam):                                 Prothioconazole:
                                            t1/2 (in sediment)= too few
detections;                   t1/2 (in paddy water)= 0.9 days.

Prothioconazole-desthio:                                       t1/2 (in
sediment)= 121.6 days.

Arkansas-cropped (loam):               Prothioconazole:
                                  t1/2 (in sediment)= too few
detections;                   t1/2 (in paddy water)= 0.6 days.

Prothioconazole-desthio:                                       t1/2 (in
sediment)= 90.0 days.	46246522

46246523

46246524	Studies conducted on prothioconazole as parent.  For   SEQ
CHAPTER \h \r 1 half-lives calculated for degradates from parent
dissipation studies, day of max concentration of degradate is used as
day zero in regression.

Bioconcentration Factor (BCF) 	Prothioconazole and
prothioconazole-desthio do not appear to bioaccumulate. 	  SEQ CHAPTER
\h \r 1 46246034   SEQ CHAPTER \h \r 1 46246035	BCF cannot be calculated
due to   SEQ CHAPTER \h \r 1 lack of a clear accumulation plateau.

1DAT= days after treatment.

Appendix C:  Tolerance Reassessment Summary and Table TC \l1 "Appendix
C:  Tolerance Reassessment Summary and Table

Appendix C.	Tolerance Summary for Prothioconazole.

Commodity	Proposed Tolerance (ppm)	Recommended Tolerance (ppm)	Comments/

Correct commodity definition

Tolerances for residues of prothioconazole and the desthio metabolite

Barley, grain	0.2	0.35	The proposed tolerance is too low.

Barley, hay	7.0	7.0

	Barley, straw	2.0	4.0	The proposed tolerance is too low.

Barley, pearled barley	0.2	Delete, not needed	A separate tolerance is
not needed for pearled barley.

Barley, bran	0.4	Delete, not needed	A separate tolerance is not need for
barley, bran.

Black mustard, seed	0.1	Delete, not allowed at this time	Additional crop
field trial data are needed to support this tolerance.

Borage, seed	0.1	Delete, not allowed at this time	Additional crop field
trial data are needed to support this tolerance.

Canola, seed	0.1	Delete, not needed	As specified under 40 CFR
§180.1(h), a tolerance for rapeseed applies to canola seed and crambe
seed.

Crambe, seed	0.1	Delete, not needed

	Field mustard, seed	0.1	Delete, not needed	Covered under the tolerance
for rapeseed.

Flax, seed	0.1	Delete, not allowed at this time	Additional crop field
trial data are needed to support this tolerance.

Grain, aspirated fractions	13.0	11	The proposed tolerance is too high;

Grain, aspirated grain fractions

Indian mustard, seed	0.1	Delete, not allowed at this time	Additional
crop field trial data are needed to support this tolerance.

Indian rapeseed	0.1	Delete, not needed	Covered under the tolerance for
rapeseed.

Pea and bean, dried, shelled, except soybean, subgroup	0.8	0.90	The
proposed tolerance is too low.

Pea and bean, dried shelled, except soybean, subgroup 6C

Peanut, nutmeat	0.02	0.02	Peanut

Peanut, hay	5.0	6.0	The proposed tolerance is too low.

Peanut, meal	0.3	Delete, not needed	A separate tolerance is not needed
for peanut meal.

Rapeseed, seed	0.1	0.15	The proposed tolerance is too low.

Rice, grain	0.25	Delete, not needed	Petitioner intends to remove rice
from their tolerance petition.

Rice, straw	1.5	Delete, not needed	Petitioner intends to remove rice
from their tolerance petition.

Rice, hulls	1.0	Delete, not needed	Petitioner intends to remove rice
from their tolerance petition.

Wheat, grain	0.06	0.07	The proposed tolerance is too low.

Wheat, forage	7.0	6.0	The proposed tolerance is too high.

Wheat, hay	4.0	4.5	The proposed tolerance is too low.

Wheat, straw	2.3	5.0	The proposed tolerance is too low.

Wheat, bran	1.5	Delete, not needed. 	Covered under the tolerance for
wheat, grain

Wheat, germ	0.15	Delete, not needed.	Covered under the tolerance for
wheat, grain.

Tolerances for the combined residue of prothioconazole, the desthio
metabolite, and conjugates convertible to these two compounds by acid
hydrolysis, calculated as prothioconazole

Milk	0.006	0.02	The proposed tolerance is too low.

Cattle, fat	0.1	0.1

	Cattle, meat	0.01	0.02	The proposed tolerance is too low.

Cattle, meat byproducts	1.2	0.2	The proposed tolerance is too high.

Goat, fat	None	0.1	Extrapolated from cattle.

Goat, meat	None	0.02	Extrapolated from cattle.

Goat, meat byproducts	None	0.2	Extrapolated from cattle.

Hog, meat byproducts	None	0.05	Extrapolated from cattle.

Horse, fat	None	0.1	Extrapolated from cattle.

Horse, meat	None	0.02	Extrapolated from cattle.

Horse, meat byproducts	None	0.2	Extrapolated from cattle.

Sheep, fat	None	0.1	Extrapolated from cattle.

Sheep, meat	None	0.02	Extrapolated from cattle.

Sheep, meat byproducts	None	0.2	Extrapolated from cattle.

Poultry, liver	None	0.02	A tolerance is needed.

Page   PAGE  1  of   NUMPAGES  220

Page   PAGE  103  of   NUMPAGES  220


[Federal Register Volume 84, Number 140 (Monday, July 22, 2019)]
[Notices]
[Pages 35177-35178]
[FR Doc No: 2019-15527]

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DEPARTMENT OF TRANSPORTATION

Federal Aviation Administration

Noise Exposure Map Notice; Westfield-Barnes Regional Airport,
Westfield, Massachusetts

AGENCY: Federal Aviation Administration, DOT.

ACTION: Notice.

-----------------------------------------------------------------------

SUMMARY: The Federal Aviation Administration (FAA) announces its
determination that the noise exposure maps for Westfield-Barnes
Regional Airport, as submitted by the City of Westfield, Massachusetts,
under the provisions of Title I of the Aviation Safety and Noise
Abatement Act of 1979, are in compliance with applicable requirements.

DATES: The effective date of the FAA's determination on the noise
exposure maps is June 13, 2019.

FOR FURTHER INFORMATION CONTACT: Richard Doucette,<PHONE_NUMBER>,
Federal Aviation Administration, New England Region, Airports Division,
1200 District Avenue, Burlington, Massachusetts 01803.

SUPPLEMENTARY INFORMATION: This notice announces that the FAA finds
that the noise exposure maps submitted for Westfield-Barnes Regional
Airport are in compliance with applicable requirements of Part 150,
effective June 13, 2019.
    Under Section 103 of Title I of the Aviation Safety and Noise
Abatement Act of 1979 (hereinafter referred to as ``the Act''), an
airport operator may submit to the FAA noise exposure maps that meet
applicable regulations and that depict non-compatible land uses as of
the date of submission of such maps, a description of projected
aircraft operations, and the ways in which such operations will affect
such maps. The Act requires such maps to be developed in consultation
with interested and affected parties in the local community, government
agencies, and persons using the airport.
    An airport operator who has submitted such noise exposure maps that
are found by FAA to be in compliance with the requirements of 14 CFR
part 150, promulgated pursuant to Title I of the Act, may submit a
noise compatibility program for FAA approval that sets forth the
measures the operator has taken, or proposes, for the introduction of
additional non-compatible uses.
    The FAA has completed its review of the noise exposure map and
related descriptions submitted by Westfield, Massachusetts. The
specific maps under consideration were ``Figure 3-9. DNL Contours for
Average Daily Aircraft Operations for CY2019'' (page 41) and ``Figure
4-1. DNL Contours for Average Daily Aircraft Operations for CY2024
NEM'' (page 53) in the submission. The FAA has determined that these
maps for Westfield-Barnes Regional Airport are in compliance with
applicable requirements. This determination is effective on June 13,
2019.
    FAA's determination on an airport operator's noise exposure maps is
limited to a finding that the maps were developed in accordance with
the procedures contained in Appendix A of 14 CFR part 150. Such
determination does not constitute approval of the applicant's data,
information or plans, or a commitment to approve a noise compatibility
program or to fund the implementation of that program.
    If questions arise concerning the precise relationship of specific
properties to noise exposure contours depicted on a noise exposure map
submitted under Section 103 of the Act, it should be noted that the FAA
is not involved in any way in determining the relative locations of
specific properties with regard to the depicted noise contours, or in
interpreting the noise exposure maps to resolve questions concerning,
for example, which properties should be covered by the provisions of
Section 107 of the Act. These functions are inseparable from the
ultimate land use control and planning responsibilities of local
government. These local responsibilities are not changed in any way
under Part 150 or through FAA's review of a noise exposure map.
Therefore, the responsibility for the detailed overlaying of noise
exposure contours onto the map depicting properties on the surface
rests exclusively with the airport operator that submitted the map or
with those public agencies and planning agencies with which
consultation is required under Section 103 of the Act. The FAA has
relied on the certification by the airport operator, under Section
150.21 of 14 CFR part

150, that the statutorily required consultation has been accomplished.
    Copies of the noise exposure maps and of the FAA's evaluation of
the maps are available for examination at the following locations:

Westfield-Barnes Regional Airport, 110 Airport Drive, Westfield, MA
01085.
Federal Aviation Administration, New England Region, Airports Division,
1200 District Avenue, Burlington, Massachusetts 01803.

    Questions may be directed to the individual named above under the
heading: FOR FURTHER INFORMATION CONTACT.

    Issued in Burlington, Massachusetts on June 13, 2019.
Richard P. Doucette,
Environmental Program Manager, FAA New England Region, Airports
Division.
[FR Doc. 2019-15527 Filed 7-19-19; 8:45 am]
BILLING CODE 4910-13-P


[Federal Register Volume 83, Number 112 (Monday, June 11, 2018)]
[Notices]
[Pages 27076-27077]
[FR Doc No: 2018-12455]

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DEPARTMENT OF TRANSPORTATION

Pipeline and Hazardous Materials Safety Administration

Hazardous Materials: Notice of Applications for Special Permits

AGENCY: Pipeline and Hazardous Materials Safety Administration (PHMSA),
DOT.

ACTION: List of applications for modification of special permits.

-----------------------------------------------------------------------

SUMMARY: In accordance with the procedures governing the application
for, and the processing of, special permits from the Department of
Transportation's Hazardous Material Regulations, notice is hereby given
that the Office of Hazardous Materials Safety has received the
application described herein.

DATES: Comments must be received on or before June 26, 2018.

ADDRESSES: Record Center, Pipeline and Hazardous Materials Safety
Administration, U.S. Department of Transportation, Washington, DC
20590.
    Comments should refer to the application number and be submitted in
triplicate. If confirmation of receipt of comments is desired, include
a self-addressed stamped postcard showing the special permit number.

FOR FURTHER INFORMATION CONTACT: Ryan Paquet, Director, Office of
Hazardous Materials Approvals and Permits Division, Pipeline and
Hazardous Materials Safety Administration, U.S. Department of
Transportation, East Building, PHH-30, 1200 New Jersey Avenue
Southeast, Washington, DC 20590-0001,<PHONE_NUMBER>.

SUPPLEMENTARY INFORMATION: Copies of the applications are available for
inspection in the Records Center, East Building, PHH-30, 1200 New
Jersey Avenue Southeast, Washington, DC or at http://regulations.gov.
Each mode of transportation for which a particular special permit is
requested is indicated by a number in the ``Nature of Application''
portion of the table below as follows: 1--Motor vehicle, 2--Rail
freight, 3--Cargo vessel, 4--Cargo aircraft only, 5--Passenger-carrying
aircraft.
    This notice of receipt of applications for special permit is
published in accordance with part 107 of the Federal hazardous
materials transportation law (49 U.S.C. 5117(b); 49 CFR 1.53(b)).

    Issued in Washington, DC, on June 4, 2018.
Donald P. Burger,
Chief, General Approvals and Permits Branch.

                          Special Permits Data
------------------------------------------------------------------------
                                                        Nature of the
 Application No.     Applicant      Regulation(s)      special permits
                                       affected            thereof
------------------------------------------------------------------------
11447-M.........  SAES PURE GAS,   ...............  To modify the
                   INC.                              special permit to
                                                     authorize an
                                                     increase in the
                                                     amount of nickel
                                                     content from 5,200
                                                     pounds to 12,500
                                                     pounds. (modes 1,
                                                     3, 4)
12412-M.........  CLEAR VIEW       ...............  To modify the
                   ENTERPRISES                       special permit to
                   LLC.                              authorize
                                                     transporting hazmat
                                                     in manifolded IBCs
                                                     on a flatbed
                                                     trailer. (mode 1)
14154-M.........  CARLETON         ...............  To modify the
                   TECHNOLOGIES,                     special permit to
                   INC.                              authorize
                                                     additional Division
                                                     2.2 gases. (modes
                                                     1, 2, 3, 4, 5)
14603-M.........  YIWU HAUNQIU     173.304(d).....  To modify the
                   CANS                              special permit to
                   MANUFACTURING                     update technical
                   CO., LTD.                         drawings and to
                   (FORMER                           authorize higher
                   GRANTEE: YI WU                    distortion and
                   HAUN QIU CAN                      minimum burst
                   MANFACTURE).                      pressures. (modes
                                                     1, 2, 3, 4)
15507-M.........  YIWU JINYU       173.304(d).....  To modify the
                   MACHINERY                         special permit to
                   FACTORY.                          authorize a new can
                                                     design and increase
                                                     the burst and
                                                     equilibrium
                                                     pressures. (modes
                                                     1, 2, 3, 4)
20323-M.........  JOHNSON          ...............  To modify the
                   CONTROLS                          special permit to
                   ADVANCED POWER                    authorize
                   SOLUTIONS, LLC.                   additional
                                                     packaging. (mode 4)
20546-M.........  DEPARTMENT OF    173.159(d).....  To modify the
                   DEFENSE                           special permit to
                   (MILITARY                         authorize the
                   SURFACE                           transportation in
                   DEPLOYMENT &                      commerce of
                   DISTRIBUTION                      batteries in boxes
                   COMMAND).                         as strong outer
                                                     packagings. (modes
                                                     1, 2, 3, 4)
20597-M.........  DEPARTMENT OF    173.220........  To modify the
                   DEFENSE                           special permit
                   (MILITARY                         initially granted
                   SURFACE                           on an emergency
                   DEPLOYMENT &                      basis to permanent
                   DISTRIBUTION                      and to authorize an
                   COMMAND).                         increase in the
                                                     amount of fuel to
                                                     be transported in
                                                     the remotely
                                                     piloted vehicles
                                                     which are fueled
                                                     while in
                                                     transportation.
                                                     (modes 1, 2, 3, 4)
------------------------------------------------------------------------

[FR Doc. 2018-12455 Filed 6-8-18; 8:45 am]
 BILLING CODE 4909-60-P


[Federal Register Volume 82, Number 124 (Thursday, June 29, 2017)]
[Rules and Regulations]
[Pages 29400-29401]
[FR Doc No: 2017-13576]

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DEPARTMENT OF HOMELAND SECURITY

Coast Guard

33 CFR Part 165

[Docket No. USCG-2017-0560]

Safety Zones; Ashland 4th of July Fireworks Display, Chequamegon
Bay, Ashland, WI

AGENCY: Coast Guard, DHS.

ACTION: Notice of enforcement of regulation.

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SUMMARY: The Coast Guard will enforce the safety zone for the Ashland
4th of July Fireworks Display in Ashland, WI from 9:30 p.m. through
11:30 p.m. on July 4, 2017. This action is necessary to protect
participants and spectators during the Ashland 4th of July Fireworks
Display. During the enforcement period, entry into, transiting, or
anchoring within the safety zone is prohibited unless authorized by the
Captain of the Port Duluth or her designated on-scene representative.

DATES: The regulations in 33 CFR 165.943(b) will be enforced from 9:30
p.m. through 11:30 p.m. on July 4, 2017, for the Ashland 4th of July
Fireworks Display safety zone, Sec.  165.943(a)(6).

FOR FURTHER INFORMATION CONTACT: If you have questions on this
document, call or email LT John Mack, Chief of Waterways Management,
Coast Guard; telephone<PHONE_NUMBER>, email<EMAIL_ADDRESS>
SUPPLEMENTARY INFORMATION:
    The Coast Guard will enforce the safety zone for the annual Ashland
4th of July Fireworks Display in 33 CFR 165.943(a)(6) from 9:30 p.m.
through 11:30 p.m. on July 4, 2017 on all waters of Chequamegon Bay
bounded by the arc of a circle with a 560-foot radius from the
fireworks launch site with its center in position 46[deg]35'50'' N.,
090[deg]52'59'' W.
    Entry into, transiting, or anchoring within the safety zone is
prohibited unless authorized by the Captain of the Port Duluth or her
designated on-scene representative. The Captain of the Port's
designated on-scene representative may be contacted via VHF Channel 16
or telephone at<PHONE_NUMBER>.
    This document is issued under authority of 33 CFR 165.943 and 5
U.S.C. 552(a). In addition to this publication in the Federal Register,
the Coast Guard will provide the maritime community with advance
notification of the enforcement of this safety zone via Broadcast
Notice to Mariners. The

Captain of the Port Duluth or her on-scene representative may be
contacted via VHF Channel 16 or telephone at<PHONE_NUMBER>.

    Dated: June 22, 2017.
E.E. Williams,
Commander, U.S. Coast Guard, Captain of the Port.
[FR Doc. 2017-13576 Filed 6-28-17; 8:45 am]
BILLING CODE 9110-04-P