Global Slag Utilisation Nick Jones Slag Business Development Manager.
Arsine Poisoning in Slag Plant
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7/28/2019 Arsine Poisoning in Slag Plant http://slidepdf.com/reader/full/arsine-poisoning-in-slag-plant 1/4 Brit. J. industr. Med., 1964, 21, 74. ARSINE POISONING IN A SLAG-WASHING PLANT BY M. D. KIPLING and R. FOTHERGILL From H.M. Medical Inspector of Factories and Little Bromwich Hospital, Birmingham (RECEIVED FO R PUBLICATION MAY 21, 1963) An investigation was carried out in an aluminium recovery works after the simultaneous occurrence of haemolytic anaemia in two workers in the slag disposal plant. The first worker was admitted to hospital suffering from nausea, backache, and haematuria. Jaundice developed on the next day. His urine contained protein, urobilin, haemoglobin, and methaemoglobin but no red cells. During the course of his illness the haemoglobin was reduced to 6-8 g./100 ml. There was no abnormality of the blood film and red cell fragility was normal. A fellow worker was affected at the same time and was treated at home for the same symptoms. Examination five days later showed a haemoglobin level similar to that of the first worker. He had suffered the same symptoms eight years previously, and at this time another worker had suffered from jaundice at home and a third had been investigated for neurological symptoms. Te n years previously another worker had been admitted to hospital with anaemia, jaundice, and haemoglobinuria. At this works scrap aluminium is melted with sodium chloride and fluorspar as a flux. The slag from the furnace is later broken up and dissolved in a rotating drum by a stream of water. The soluble portion is carried into a lagoon, whilst the 3 % aluminium is retained in the drum and dis- charged weekly. Tw o men are employed at a time and another six have been employed in the past 10 years. Five parts per million of arsine were found to be present in the atmosphere during slag washing, but higher levels would have occurred on the occasions when slag from the making of an aluminium copper alloy from copper with an arsenic content was similarly treated. The mechanism of arsenic production is discussed and the literature on the role of aluminium reviewed. The process consists essentially of washing slag containing aluminium to dissolve out the soluble constituents. At this factory high-grade aluminium scrap is melted in a furnace to which sodium chloride and fluorspar are added as a flux to remove impurities. The salt and fluorspar slag, which contains 3 % aluminium, is removed as a hard cake and taken to the slag-washing plant. In this plant the cake of slag is broken by sledge hammers and placed in an iron drum revolving on a horizontal axis. Water from a brook is directed through the drum and dis- solves the slag, which is carried through a gully to a lagoon. The slurry contains nitrides which decom- pose in solution to give an ammoniacal liquor of about 0- 1 % ammonia content. Aluminium is retained in the drum to be discharged into a pit at the end of the week to be used in subsequent melts. The process is carried out in an open shed with three walls in an outlying part of the works and is operated by two men at a time, an average of 100 tons of slag a week being treated in this way and three tons of aluminium recovered. Approximately one-third of the man's working day is spent in the shed to charge the drum and one half-day a week is spent recovering aluminium. The aluminium scrap was routinely tested for impurities, including possible arsenic contamination to a limit of 10 parts per million, with consistently negative results. Case Reports Case 1.-A 54-year-old worker in the slag-washing plant was admitted to the Infectious Diseases Unit on January 21, 1961, with the notified diagnosis of infectious hepatitis. 74
Transcript of Arsine Poisoning in Slag Plant
7/28/2019 Arsine Poisoning in Slag Plant
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B r i t . J . i n d u s t r . M e d . , 1 9 6 4 , 2 1 , 7 4 .
ARSINE POISONING IN A SLAG-WASHING PLANTBY
M. D . KIPLING a n d R . FOTHERGILL
From H.M. M e d i c a l I n s p e c t o r o f F a c t o r i e s a n d L i t t l e B r o m w i c h H o s p i t a l , B i r m i n g h a m
( R E C E I V E D FO R PUBLICATION MAY 2 1 , 1 9 6 3 )
An i n v e s t i g a t i o n w a s c a r r i e d o u t i n a n a l u m i n i u m r e c o v e r y w o r k s a f t e r t h e s i m u l t a n e o u so c c u r r e n c e o f h a e m o l y t i c a n a e m i a i n t w o w o r k e r s i n t h e s l a g d i s p o s a l p l a n t .
T h e f i r s t w o r k e r w a s a d m i t t e d t o h o s p i t a l s u f f e r i n g f r o m n a u s e a , b a c k a c h e , a n d h a e m a t u r i a .
J a u n d i c e d e v e l o p e d on t h e n e x t d a y . H i s u r i n e c o n t a i n e d p r o t e i n , u r o b i l i n , h a e m o g l o b i n , a n dm e t h a e m o g l o b i n b u t no r e d c e l l s . D u r i n g t h e c o u r s e o f h i s i l l n e s s t h e h a e m o g l o b i n w a s r e d u c e dt o 6 - 8 g . / 1 0 0 m l . T h e r e w a s no a b n o r m a l i t y o f t h e b l o o d f i l m a n d r e d c e l l f r a g i l i t y w a s n o r m a l .
A f e l l o w w o r k e r w a s a f f e c t e d a t t h e s a m e t i m e a n d w as t r e a t e d a t home f o r t h e s a m e s y m p t o m s .E x a m i n a t i o n f i v e d a y s l a t e r s h o w e d a h a e m o g l o b i n l e v e l s i m i l a r t o t h a t o f t h e f i r s t w o r k e r .
He h a d s u f f e r e d t h e s a m e s y m p t o m s e i g h t y e a r s p r e v i o u s l y , a n d a t t h i s t i m e a n o t h e r w o r k e rh a d s u f f e r e d f r o m j a u n d i c e a t home a n d a t h i r d h a d b e e n i n v e s t i g a t e d f o r n e u r o l o g i c a l s y m p t o m s .
Ten y e a r s p r e v i o u s l y a n o t h e r w o r k e r h a d b e e n a d m i t t e d t o h o s p i t a l w i t h a n a e m i a , j a u n d i c e ,a n d h a e m o g l o b i n u r i a .
At t h i s w o r k s s c r a p a l u m i n i u m i s m e l t e d w i t h s o d i u m c h l o r i d e a n d f l u o r s p a r a s a f l u x . T h e s l a gf r o m t h e f u r n a c e i s l a t e r b r o k e n u p a n d d i s s o l v e d i n a r o t a t i n g d r u m b y a s t r e a m o f w a t e r . T h es o l u b l e p o r t i o n i s c a r r i e d i n t o a l a g o o n , w h i l s t t h e 3 % a l u m i n i u m i s r e t a i n e d i n t h e d r u m a n d d i s -c h a r g e d w e e k l y . Tw o m e n a r e e m p l o y e d a t a t i m e a n d a n o t h e r s i x h a v e b e e n e m p l o y e d i n t h e p a s t
1 0 y e a r s .F i v e p a r t s p e r m i l l i o n o f a r s i n e w e r e f o u n d t o b e p r e s e n t i n t h e a t m o s p h e r e d u r i n g s l a g w a s h i n g ,
b u t h i g h e r l e v e l s w o u l d h a v e o c c u r r e d on t h e o c c a s i o n s w h e n s l a g f r o m t h e m a k i n g o f a n a l u m i n i u mc o p p e r a l l o y f r o m c o p p e r w i t h a n a r s e n i c c o n t e n t w a s s i m i l a r l y t r e a t e d .
T h e m e c h a n i s m o f a r s e n i c p r o d u c t i o n i s d i s c u s s e d a n d t h e l i t e r a t u r e on t h e r o l e o f a l u m i n i u mr e v i e w e d .
T h e p r o c e s s c o n s i s t s e s s e n t i a l l y o f w a s h i n g s l a gc o n t a i n i n g a l u m i n i u m t o d i s s o l v e o u t t h e s o l u b l ec o n s t i t u e n t s .
At t h i s f a c t o r y h i g h - g r a d e a l u m i n i u m s c r a p i s
m e l t e d i n a f u r n a c e t o w h i c h s o d i u m c h l o r i d e a n df l u o r s p a r a r e a d d e d a s a f l u x t o r e m o v e i m p u r i t i e s .T h e s a l t a n d f l u o r s p a r s l a g , w h i c h c o n t a i n s 3 %a l u m i n i u m , i s r e m o v e d a s a h a r d c a k e a n d t a k e n
t o t h e s l a g - w a s h i n g p l a n t . I n t h i s p l a n t t h e c a k e o f
s l a gi s b r o k e n
b y s l e d g eh a m m e r s a n d
p l a c e di n a n
i r o n drum r e v o l v i n g o n a h o r i z o n t a l a x i s . W a t e rf r o m a b r o o k i s d i r e c t e d t h r o u g h t h e drum a n d d i s -s o l v e s t h e s l a g , w h i c h i s c a r r i e d t h r o u g h a g u l l y t o a
l a g o o n . T h e s l u r r y c o n t a i n s n i t r i d e s w h i c h d e c o m -p o s e i n s o l u t i o n t o g i v e a n a m m o n i a c a l l i q u o r o f
a b o u t 0 - 1 % ammonia c o n t e n t . A l u m i n i u m i sr e t a i n e d i n t h e drum t o b e d i s c h a r g e d i n t o a p i t a tt h e e n d o f t h e w e e k t o b e u s e d i n s u b s e q u e n t m e l t s .
T h e p r o c e s s i s c a r r i e d o u t i n a n o p e n s h e d w i t h
t h r e e w a l l s i n a n o u t l y i n g p a r t o f t h e w o r k s a n d i so p e r a t e d b y t w o m e n a t a t i m e , a n a v e r a g e o f
1 0 0 t o n s o f s l a g a w e e k b e i n g t r e a t e d i n t h i s way a n dt h r e e t o n s o f a l u m i n i u m r e c o v e r e d . A p p r o x i m a t e l yo n e - t h i r d o f t h e m a n ' s w o r k i n g d a y i s s p e n t i n t h es h e d t o c h a r g e t h e drum a n d o n e h a l f - d a y a w e e k i ss p e n t r e c o v e r i n g a l u m i n i u m .
T h e a l u m i n i u m s c r a p w a s r o u t i n e l y t e s t e d f o r
i m p u r i t i e s ,i n c l u d i n g
p o s s i b l e a r s e n i cc o n t a m i n a t i o n
t o a l i m i t o f 1 0 p a r t s p e r m i l l i o n , w i t h c o n s i s t e n t l yn e g a t i v e r e s u l t s .
C a s e R e p o r t sC a s e 1.-A 5 4 - y e a r - o l d w o r k e r i n t h e s l a g - w a s h i n g
p l a n t w a s a d m i t t e d t o t h e I n f e c t i o u s D i s e a s e s U n i t o nJ a n u a r y 2 1 , 1 9 6 1 , w i t h t h e n o t i f i e d d i a g n o s i s o f i n f e c t i o u sh e p a t i t i s .
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ARSINE POISONING IN A SLAG-WASHING PLANT
TABLE 1
CASE 1 : SUMMARY OF INVESTIGATIONS
D a t e 2 1 . 1 . 6 2 2 2 . 1 . 6 2 2 3 . 1 . 6 2 2 4 . 1 . 6 2 2 5 . 1 . 6 2 2 6 . 1 . 6 2 2 7 . 1 . 6 2 2 8 . 1 . 6 2
AdmittedIB l o o d u r e a ( m g . / 1 0 0 m l . ) 1 4 9H a e m o g l o b i n ( g ./ 1 00 m l . ) 1 0 - 4 7 - 9 7 - 2 7 - 3 6 - 8 1 1 1
Serum b i l i r u b i n ( m g . / 1 0 0 m l . ) 5 - 3 6 - 0 1
U r i n a r y o u t p u t ( o z . ) 2 6 6 6 5 7 5 1 4 2 ? 2 8 3 6
H a e m o g l o b i n u r i a ++ +++± ++ ++ -He h a d b e e n w e l l u n t i l t h e d a y b e f o r e , w h e n h e f e l t
s h i v e r y a n d n a u s e a t e d a n d s h o r t l y a f t e r w a r d s d e v e l o p e d
h e a d a c h e a n d b a c k a c h e . A t 2 . 0 p . m . h e f i n i s h e d w o r k a n d
w e n t h o m e t o b e d , a n d a t 3 . 3 0 p . m . h e p a s s e d r e d u r i n e .T h a t n i g h t h e h a d n o s l e e p , b e c a u s e o f f r e q u e n t v o m i t i n g ,
a b d o m i n a l p a i n , a n d b a c k a c h e . T h e f o l l o w i n g m o r n i n g
h e w a s s l i g h t l y j a u n d i c e d .On e x a m i n a t i o n i n h o s p i t a l l a t e r i n t h e d a y h e l o o k e d
i l l , b e i n g b e m u s e d a n d s h a k e n . H i s t e m p e r a t u r e w a s
1 0 0 ° F . , p u l s e 1 0 0 , r e s p i r a t i o n s 2 0 , a n d b l o o d p r e s s u r e1 1 0 / 7 5 m m . H g . T h e r e w a s p a l l o r o f t h e m u c o u s m e m-
b r a n e s , a w e a t h e r - b e a t e n o r b r o n z e d s k i n , r e d n e s s o f t h ee y e s , a i n d i c t e r u s o f t h e s c l e r a e . I n t h e a b d o m e n t h e r e w a s
s o m e t e n d e r n e s s o v e r t h e l i v e r , w h i c h w a s n o t e n l a r g e d ;t h e s p l e e n w a s n o t p a l p a b l e , b u t t h e r e w a s m a r k e d
t e n d e r n e s s i n t h e r e n a l a n g l e s . T h e u r i n e w a s p o r t w i n e
c o l o u r e d .
I n v e s t i g a t i o n s ( T a b l e 1 ) . - T h e u r i n e s h o w e d g r o s sp r o t e i n u r i a . On m i c r o s c o p y o f t h e d a p o s i t s c a n t y l e u c o c y t e sw e r e s e e n a n d n o r e d c e l l s o r c a s t s . L a r g e c o n c e n t r a t i o n s
o f u r o b i l i n , h a e m o g l o b i n , a n d m e t h a e m o g l o b i n w e r e
d e t e c t e d .T h e s u p e r n a t a n t p l a s m a f r o m a c l o t t e d s p e c i m e n o f
b l o o d w a s r e d f r o m t h e p r e s e n c e o f h a e m o g l o b i n . T h e
h a e m o g l o b i n l e v e l w a s 1 0 4 g . / 1 0 0 m l . No a b n o r m a l i t y
w a s s e e n o n a b l o o d f i l m , a n d r e d c e l l f r a g i l i t y w a s
n o r m a l . T h e w h i t e b l o o d c o u n t w a s 1 4 , 0 0 0 / c . m m . w i t h
82% p o l y m o r p h s . T h e s e r u m b i l i r u b i n w a s 5 - 3 m g . / 1 0 0
m l . ( w i t h a d i r e c t / i n d i r e c t q u o t i e n t o f 1 5 ) . B l o o d u r e a
w a s 1 4 9 m g . / 1 0 0 m l . C o o m b s , H a i n e s , D o n a t h -
L a n d s t e i n e r , W a s s e r m a n n , a n d Kahn t e s t s w e r e n e g a t i v e .T h e i n t e r p r e t a t i o n p u t o n t h e s e r e s u l t s w a s t h a t t h e
p a t i e n t w a s s u f f e r i n g f r o m a n a c u t e i n t r a v a s c u l a r h a e m o -
l y s i s , w it h c o n s e q u e n t a n a e m i a , h a e m o g l o b i n u r i a , a n d
j a u n d i c e .F o r t h e f i r s t 7 2 h o u r s a f t e r a d m i s s i o n t h e u r i n e was
d e e p r e d a n d t h e n i t g r a d u a l l y c l e a r e d o v e r a f u r t h e r4 8 h o u r s . T h e r e w a s a h i g h o u t p u t a t f i r s t , f a l l i n g s l i g h t l ye a c h d a y f o r a w e e k , b u t a n u r i a d i d n o t s u p e r v e n e .
H a e m o l y s i s l a s t e d f o r t h e f i r s t f e w d a y s , b y w h i c h t i m e
a b o u t h a l f h i s b l o o d h a d b e e n d e s t r o y e d . T h e h a e m o -
g l o b i n w a s 6 - 8 g . / 1 0 0 m l . T h i s was a l s o t h e p e r i o d t h a th e r e m a i n e d d i s t r e s s e d a n d i l l ; a b d o m i n a l p a i n w as
f r e q u e n t . C l i n i c a l i m p r o v e m e n t c a m e a s t h e u r i n e
c l e a r e d .On J a n u a r y 2 8 , 1 9 6 1 , s e v e n d a y s a f t e r a d m i s s i o n , h e
w a s g i v e n f o u r p i n t s o f p a c k e d c e l l s w h i c h r a i s e d h i sh a e m o g l o b i n t o 1 1 1 g . / 1 0 0 m l . P r o g r e s s b e i n g s a t i s -f a c t o r y , h e was d i s c h a r g e d h o m e 1 0 d a y s l a t e r , h i s o n l yc o m p l a i n t t h e n b e i n g o f s l i g h t w e a k n e s s . He r e t u r n e d
t o w o r k t h r e e w e e k s l a t e r a n d w h e n s e e n a f t e r s i x m o n t h s
w a s f i t a n d w e l l .
T h e p a t i e n t w o r k e d i n t h e s a m e p l a n t a s h i sb r o t h e r - i n - l a w , w h o w a s t a k e n i l l o n t h e s a m e d a y .On r e c e i p t o f t h i s i n f o r m a t i o n a r r a n g e m e n t s w e r e
m a d e f o r h i s a d m i s s i o n .
C a s e 2 . - T h i s m an w a s 4 7 y e a r s o l d a n d w o r k e d i n t h es l a g p r o c e s s . H i s s y m p t o m s b e g a n a t 3 p . m . o n J a n ua r y
2 0 , 1 9 6 1 , w h e n h e h a d n a u s e a f o l l o w e d b y a b d o m i n a l
c o l i c , v o m i t i n g , b a c k a c h e , a n d s h o r t n e s s o f b r e a t h . T h en e x t m o r n i n g e a r l y h e p a s s e d r e d u r i n e a n d w a s s l i g h t l yj a u n d i c e d . F o r t h r e e d a y s h e s u f f e r e d f r o m l e f t - s i d e dl o i n p a i n , a b d o m i n a l p a i n s , a n d v o m i t i n g . On t h e f o u r t h
d a y h e w a s f e e l i n g b e t t e r a n d t h e u r i n e w a s n o r m a l i nc o l o u r .
A t t h e t i m e o f a d m i s s i o n o n J a n u a r y 2 5 , 1 9 6 1 , t h e o n l y
p h y s i c a l s i g n w a s p a l l o r o f t h e m u c o u s m e m b r a n e s . A
h a e m o g l o b i n l e v e l o f 8 5 g . / 1 0 0 m l . , w i t h 6 - 5 % r e t i c u l o -c y t e s a n d p o l y c h r o m a s i a , i n d i c a t e d a r e c e n t a c u t e b l o o d
l o s s .T h e t e s t s o n t h e u r i n e f o r b i l e p i g m e n t s a n d h a e m o -
g l o b i n w e r e n e g a t i v e , a n d t h e s e r u m b i l i r u b i n w a s
n o r m a l ; t h e f i n d i n g s w e r e c o m p a r a b l e w i t h t h o s e o f
c a s e 1 a t t h i s l a t e s t a g e o f t h e i l l n e s s ( T a b l e 2 ) .
T A B L E 2
A C T I V A T I O N ANALYSIS OF ARSENIC CONTENTOF HAIR AND N A I L S
N a i l s H a i r
C a s e 1 2 - 5 0 0 - 4 0 p . p . m .C a s e 2 1 - 6 6 0 - 2 3 p . p . m .
Normal 0 - 8 2 - 3 - 5 0 - 5 - 2 - 1 p . p . m .S m a l e s a n d P a t e ( 1 9 5 2 )
P a s t i l l n e s s e s . - On A p r i l 2 , 1 9 5 4 , c a s e 2 h a d h a d a
s i m i l a r a t t a c k , t h e m a i n f e a t u r e s o f w h i c h w e r e j a u n d i c e
a n d r e d u r i n e f o r a f e w d a y s . A f t e r t h e a c u t e p h a s e h e
h a d b e e n r e f e r r e d t o a s u r g i c a l o u t - p a t i e n t c l i n i c f o r t h ei n v e s t i g a t i o n o f ' h a e m a t u r i a ' . T h e r e w a s a n o t e o f
' p a l l o r s u g g e s t i n g t h e l o s s o f a f a i r a m o u n t o f b l o o d ' a n d
r e f e r e n c e t o a s e v e r e h e a d a c h e . C y s t o s c o p y f a i l e d t or e v e a l a c a u s e f o r t h e ' h a e m a t u r i a ' .
C a s e 1 a n d c a s e 2 h a d w o r k e d on w a s h i n g a l u m i n i u ms l a g f o r 1 7 y e a r s a n d s e v e n y e a r s r e s p e c t i v e l y . O n l ys i x o t h e r m e n h a d h e l p e d o n t h i s j o b d u r i n g t h a t t i m e ,a n d i n v e s t i g a t i o n s b r o u g h t t o l i g h t t ha t t h r e e w o r k e r s
h a d b e e n t r e a t e d e l s e w h e r e f o r c o n d i t i o n s c o n s i s t e n tw i t h a r s i n e p o i s o n i n g .
C a s e 3.-A 2 0 - y e a r - o l d m a n was a d m i t t e d t o h o s p i t a li n J u l y 1 9 5 2 . w i t h s e v e r e b a c k a c h e , h e a d a c h e , a b d o m i n a l
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BRITISH JOURNAL OF INDUSTRIAL MEDICINE
c o l i c , a n d j a un d i c e o f t h r e e d a y s ' d u r a t i o n . On a d m i s s i o nh e w a s s l i g h t l y j a u n d i c e d , w i t h a p e c u l i a r b l u e - g r e yp i g m e n t a t i o n o f t h e m u c o s a o f t h e m o u t h a n d o f t h e
f i n g e r s a n d t o e s . B l o o d e x a m i n a t i o n s h o w e d a h a e m o -g l o b i n o f 5 2 g . / 1 0 0 m l . , a m a r k e d r e t i c u l o c y t o s i s , a n d t h ep r e s e n c e o f m e t h a e m o g l o b i n a e m i a . H a e m o g l o b i n u r i aw a s a l s o p r e s e n t . I n r e t r o s p e c t t h e c l i n i c a l a n d h a e m a t o -l o g i c a l p i c t u r e a n d t h e p r e s e n c e o f a m a r k e d h a e m o -
g l o b i n u r i a l e a v e n o d o u b t t h a t t h i s m a n w a s s u f f e r i n gf r o m a n a c u t e s e v e r e h a e m o l y s i s d u e t o a r s i n e .
C a s e 4.-A f o u r t h m a n h a d b e e n t r e a t e d a t h o m e i n1 9 5 4 f o r j a u nd i c e o f a n o r a n g e c o l o u r w i t h d a r k u r i n e .He h a d b e e n a f f e c t e d o n t h e s a m e d a y a s c a s e 2 s u f f e r e dh i s f i r s t a t t a c k .
C a s e 5 . - A n o t h e r s l a g w o r k e r h a d b e e n a d m i t t e d t oh o s p i t a l o n A p r i l 9 , 1 9 5 4 , f o r i n v e s t i g a t i o n o f a p p a r e n t
p o l y n e u r i t i s . He h a d n u m b n e s s i n h i s h a n d s , i n a b i l i t yt o t e l l w h e t h e r h e w a s h o l d i n g a n y t h i n g p r o p e r l y , a n d a
l i a b i l i t y t o d r o p t h i n g s . T h e r e w a s l o s s o f f i n e m o v e m e n ti n t h e h a n d s , u n s t e a d i n e s s i n t h e f e e t w i t h d i f f i c u l t y i nj u d g i n g w h e r e o n e t o o t w o u l d b e i n r e l a t i o n t o t h e o t h e r ,
i n v o l u n t a r y t w i t c h i n g i n t h e r i g h t f o o t w h e n s i t t i n g d o w n ,a n d h y p e r a e s t h e s i a i n t h e f i n g e r s . C l i n i c a l e x a m i n a t i o nr e v e a l e d s o m e l o s s o f v i b r a t i o n s e n s e i n t h e r i g h t a rma n d l o s s o f j o i n t s e n s e i n t h e r i g h t f o o t . O t h e r s e n s a t i o n sw e r e n o r m a l , a n d t h e r e w a s n o g r o s s a b n o r m a l i t y o f
p o w e r o r r e f l e x e s . T h e c e r e b r o s p i n a l f l u i d w a s n o r m a l .
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f i v e w e e k s a f t e r t h e o n s e t o f s y m p t o m s . He made a
c o m p l e t e r e c o v e r y .
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I n v e s t i g a t i o n s a t t h e p l a n t s h o w e d t h a t d u r i n g t h ep r o c e s s o f d i s s o l v i n g t h e s l a g i n t h e r o t a t i n g d r u ma n a c e t y l e n e - l i k e o d o u r w a s c o n s t a n t l y p r o d u c e d
a n d t h a t a c o n c e n t r a t i o n o f 5 p . p . m . o f a r s i n e w a sp r e s e n t . A n a l y s i s o f t h e s l a g s h o w e d a t o t a l a r s e n i cc o n t e n t o f 1 0 t o 1 5 p a r t s p e r m i l l i o n .
D i s c u s s i o n
T h e l i t e r a t u r e a n d t o x i c o l o g y o f a r s i n e h a v e b e e n
r e v i e w e d b y B u c h a n a n ( 1 9 6 2 ) .I n 1 8 1 5 t h e f i r s t r e c o r d e d f a t a l i t y d u e t o a r s i n e
o c c u r r e d i n a German c h e m i s t , a n d t h i s w as f o l l o w e d
i n 1 8 7 3 b y t h e f i r s t r e c o r d e d i n d u s t r i a l p o i s o n i n g i nG e r m a n y i n t h e d e - s i l v e r i n g o f l e a d a n d z i n c o r e s
( L e g g e , 1 9 0 2 ) .T h e f i r s t c a s e s i n G r e a t B r i t a i n o c c u r r e d i n 1 8 8 9
i n t h e r e c o v e r y o f ammonium c h l o r i d e f r o m t h e f l u xu s e d i n g a l v a n i z i n g b a t h s . G l a i s t e r ( 1 9 0 8 ) c o l l e c t e d1 2 0 r e c o r d e d c a s e s i n a v a r i e t y o f t r a d e s a n d o c c u p a -
t i o n s . B e t w e e n 1 9 0 0 a n d 1 9 5 9 , 1 2 0 s u s p e c t e d c a s e s
o f a r s i n e p o i s o n i n g , o f w h i c h 2 7 w e r e f a t a l , w e r e
i n v e s t i g a t e d i n G r e a t B r i t a i n b y H.M. F a c t o r y
I n s p e c t o r a t e ( B u c h a n a n , 1 9 6 2 ) .B u c h a n a n ( 1 9 6 2 ) h a s d e s c r i b e d t h e n a t u r e o f t h e
r e a c t i o n s , w h i c h i n s u i t a b l e c i r c u m s t a n c e s g i v e r i s e
t o t h e p r o d u c t i o n o f a r s i n e , a n d h a s d r a w n a t t e n t i o nt o t h e r o l e o f a l u m i n i u m . A r s i n e m a y b e p r o d u c e db y t h e r e d u c t i o n o f a r s e n i c a l c o m p o u n d s b y n a s c e n t
h y d r o g e n g e n e r a t e d b y t h e a c t i o n o f a c i d o n t h em e t a l when a r s e n i c i s p r e s e n t i n e i t h e r t h e a c i d o r
m e t a l o r b o t h , o r b y n a s c e n t h y d r o g e n g e n e r a t e d b yt h e a c t i o n o f a l k a l i s on l i g h t m e t a l s .
T h e l a t t e r m e c h a n i s m w a s e x e m p l i f i e d w h e n c o n -t a i n e r s w h i c h h a d b e e n u s e d f o r a l u m i n i u m p a i n tw e r e p a s s e d f o r c l e a n i n g t h r o u g h a 1 0 % c a u s t i c s o d ab a t h w h i c h h a d p r e v i o u s l y b e e n c o n t a m i n a t e d w i t h
s o d i u m a r s e n i t e ( B u c h a n a n , 1 9 6 2 ) .T h e h y d r o l y s i s o f m e t a l l i c a r s e n i d e i s a r e a c t i o n
t h a t h a s b e e n f o u n d t o c a u s e t h e p r o d u c t i o n o f
a r s i n e i n i n d u s t r y . L e g g e ( 1 9 2 3 ) r e p o r t e d a f a t a l c a s e
w h e n p r i n t e r ' s d r o s s w a s f l o o d e d i n a t h u n d e r s t o r m .T h e d r o s s c o n t a i n e d l e a d , a n t i m o n y , t i n , c o p p e r , a n da l u m i n i u m w i t h a n a r s e n i c c o n t e n t o f 1 6 % , a n da t t e n t i o n w a s d r a w n t o t h e f a c t t h a t e x p e r i m e n t a l l ya n a l u m i n i u m a r s e n i c c o m p o u n d r e a d i l y e v o l v e s
a r s i n e w h e n w e t t e d .F a t a l a r s i n e p o i s o n i n g h a s o c c u r r e d f r o m t h ew e t t i n g o f d r o s s i n t i n r e f i n i n g , w h e n a l u m i n i u m h a s
b e e n a d d e d t o t h e m o l t e n m e t a l t o i m p r o v e d r o s sf o r m a t i o n . I t w a s c on s i d e r e d t h a t t h e a l u m i n i u m
s e l e c t i v e l y c o m b i n e s w i t h t h e i m p u r i t i e s p r e s e n t i nt h e m e t a l a n d f o r m s a l u m i n i u m a r s e n i d e w i t h a n ya r s e n i c p r e s e n t ( B o m f o r d a n d H u n t c r , 1 9 3 2 ;M a c a u l a y a n d S t a n l e y , 1 9 5 6 ) .A s i m i l a r p o i s o n i n g o c c u r r e d i n t h e U n i t e d S t a t e s ,
a f f e c t i n g 1 3 m e n , w i t h f o u r f a t a l c a s e s ( S p o l y a r a n dH a r g e r , 1 9 5 0 ) . T h i s w as a l s o a t t r i b u t e d t o t h eh y d r o l y s i s o f a l u m i n i u m a r s e n i d e , b u t M o r s e a n d
S e t t e r l i n d ( 1 9 5 0 ) , a f t e r a f u l l i n v e s t i g a t i o n o f t w o
f a t a l c a s e s o f a r s i n e p o i s o n i n g w h e r e a l u m i n i u m w a ss i m i l a r l y u s e d t o remove a r s e n i c , s u g g e s t t h e p r o -
d u c t i o n o f n a s c e n t h y d r o g e n b y a n e l e c t r o l y t i cr e a c t i o n b e t w e e n t h e l e a d a n d a l u m i n i u m . B u c h a n a n( 1 9 6 2 ) d e s c r i b e d a r s i n e p o i s o n i n g i n t h r e e w o r k e r sf r o m s l a g p r o d u c e d i n t h e m a n u f a c t u r e o f s i l i c o ns t e e l , i n w h i c h a l u m i n i u m i n t r o d u c e d i n t o t h e m o l t e nm e t a l s u c c e s s i v e l y a b s t r a c t e d a r s e n i c a l i m p u r i t i e st h r o u g h s u c c e s s i v e p o u r i n g s a n d t h e s l a g f r o m t h el i n i n g o f t h e l a d l e e v o l v e d a r s i n e o n e x p o s u r e t om o i s t u r e .
T u r n i n g no w t o c o n s i d e r o u r o w n i n c i d e n t , t h es o u r c e o f a r s e n i c a n d t h e m e c h a n i s m o f p r o d u c t i o no f a r s i n e i n t h i s s l a g - w a s h i n g p l a n t h a v e n o t b e e n
d e f i n i t e l y p r o v e d .T h e a l u m i n i u m s c r a p was known t o c o n t a i n l e s s
t h a n 1 0 p . p . m . o f a r s e n i c , a n d t h e r e w as no e v i d e n c e
t h a t t h e b r o o k h a d b e e n c o n t a m i n a t e d b y a r s e n i ci n t h e f o r m o f s h e e p d i p o r w e e d k i l l e r , b u t t h ei n t e r m i t t e n t m e l t i n g o f c o p p e r s c r a p , w h i c h a t t i m e si n c l u d e d c o p p e r t u b e s c o n t a i n i n g u p t o 0 - 3 6 %a r s e n i c t o make a c o p p e r a l u m i n i u m a l l o y , c o u l d
7 6
7/28/2019 Arsine Poisoning in Slag Plant
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ARSINE POISONING IN A SLAG-WASHING PLANT
h a v e p r o d u c e d a n a r s e n i c - c o n t a m i n a t e d s l a g . Fromt h i s s l a g a r s i n e m a y h a v e b e e n p r o d u c e d e i t h e r b yh y d r o l y s i s o f a l u m i n i u m a r s e n i d e , t h e p r o d u c t i o n
o f n a s c e n t h y d r o g e n b y f i n e l y - d i v i d e d a l u m i n i u m i na n a l k a l i n e m e d i u m , o r b y a n e l e c t r o l y t i c a c t i o nb e t w e e n t h e r e v o l v i n g i r o n d r u m a n d t h e a l u m i n i u m .
T h e f i n d i n g o f a n o r m a l o r s l i g h t l y r a i s e d a r s e n i cc o n t e n t o f t h e h a i r a n d n a i l s s u p p o r t s t h e t h e o r y o fh i g h i n t e r m i t t e n t e x p o s u r e , w h i c h i s c o n s i s t e n t w i t h
t h e p o s s i b i l i t y o f o c c a s i o n a l c o n t a m i n a t i o n o f t h es l a g b y a r s e n i c f r o m t h e c o p p e r t u b e s r a t h e r t h a nf r o m r e g u l a r c o n t a m i n a t i o n f r o m t h e v e r y s m a l l
q u a n t i t i e s o f a r s e n i c p r e s e n t i n t h e a l u m i n i u m s c r a p .T h e f i n d i n g t h a t t h e r e h a d b e e n p r e v i o u s o u t b r e a k s
o f h a e m a t u r i a a n d j a u n d i c e i s i n a c c o r d a n c e w i t h
w h a t i s o f t e n f o u n d i n t h e i n v e s t i g a t i o n o f a r s i n ep o i s o n i n g .
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p a r t i c u l a r i n t e r e s t a n d m i g h t b e c o n s i d e r e d r e l e v a n tt o e x p o s u r e t o a r s i n e i n t h e l i g h t o f p r e v i o u s r e p o r t s .
D u d l e y ( 1 9 1 9 ) d e s c r i b e d 3 0 c a s e s o f h a e m o l y t i ca n a e m i a d u e t o a r s i n e i n t h e c r e w s o f s u b m a r i n e s ,o f w h o m 2 6 c o m p l a i n e d o f n e u r i t i c s y m p t o m s , v a g u et i n g l i n g a n d n u m b n e s s , p i n s a n d n e e d l e s i n t h e
h a n d s a n d f e e t , l e g s p r o n e t o g o t o s l e e p e a s i l y ,c r a m p s , a n d v a g u e s h o o t i n g p a i n s . A l l h a d n o r m a lr e f l e x e s a n d no c u t a n e o u s a n a e s t h e s i a . I n s o m e t h ea n a e m i a w a s o f m i l d d e g r e e o n l y .
G u e l m a n ( 1 9 2 5 ) r e p o r t e d an o u t b r e a k o f p o i s o n -i n g a f f e c t i n g 1 2 w o r k e r s i n a g a l v a n i z i n g a n d e t c h i n gd e p a r t m e n t o f a z i n c p l a n t , s e v e r a l o f w h o m com-
p l a i n e d o f p a i n i n t h e n e r v e t r u n k s a n d o f i m p a i r e d
s e n s a t i o n w i t h o u t m o t o r i n v o l v e m e n t .H a w l i c k a n d L e y ( 1 9 4 6 ) a t t r i b u t e d t h e r a d i a t i n g
p a i n s i n a c a s e d e s c r i b e d b y t h e m t o a p e r i p h e r a l
n e u r i t i s .Ou r c a s e 5 r e s e m b l e s t h o s e d e s c r i b e d i n s u f f e r i n g
f r o m n u m b n e s s a n d p a r a e s t h e s i a e a n d a t a x i a . Th ei l l n e s s a r o s e a t t h e s a m e t i m e a s c a s e 4 a n d c a s e 2
s u f f e r e d t h e i r f i r s t i l l n e s s e s . H o w e v e r , i n t h e a b s e n c e
o f r e c o r d s o f b l o o d a n d u r i n e t e s t s , i t i s i m p o s s i b l et o c o r r e l a t e t h e s e s y m p t o m s d e f i n i t e l y w i t h e x p o s u r et o a r s i n e .
We a r e i n d e b t e d t o D r . W. D . B u c h a n a n f o r a d v i c e ,t o M r . S . G . L u x o n f o r a n a l y s i s o f t h e a t m o s p h e r e a n ds l a g , t o D r . J . M. A . L e n i h a n f o r a c t i v a t i o n a n a l y s i s o fh a i r a n d n a i l s a m p l e s , a n d t o D r . J . S h a r k e y f o r i n f o r -m a t i o n o n c a s e 3 .
R E F E R E N C E S
B o m f o r d , R . R . , a n d H u n t e r , D . ( 1 9 3 2 ) . L a n c e t , 2 , 1 4 4 6 .B u c h a n a n , W. D . ( 1 9 6 2 ) . T o x i c i t y o f A r s e n i c C o m p o u n d s . E l s e v i e r
P u b l i s h i n g C o . , A m s t e r d a m .D u d l e y , S . F . ( 1 9 1 9 ) . J . i n d u s t r . H y g . , 1 , 2 1 5 .G l a i s t e r , J . ( 1 9 0 8 ) . P o i s o n i n g b y A r s e n i u r e t t e d H y d r o g e n o r H y d r o g e n
A r s e n i d e . L i v i n g s t o n e , E d i n b u r g h .G u e l m a n , 1 . ( 1 9 2 5 ) . J . i n d u s t r . H y g . , 7 , 6 .H a w l i c k , G . F . , a n d L e y , E . B . ( 1 9 4 6 ) . O c c u p . M e d . , 1 , 3 8 8 .L e g g e , T . M . ( 1 9 0 2 ; 1 9 2 3 ) . A n n u a l R e p o r t s C h i e f I n s p e c t o r o f
F a c t o r i e s a n d W o r k s h o p s . H . M . S . O . , L o n d o n .M a c a u l a y , D . B . , and S t a n l e y , D. A . ( 1 9 5 6 ) . B r i t . J . i n d u s t r . M e d . , 1 3 ,
2 1 7 .M o r s e , K . M . , a n d S e t t e r l i n d , A . N . ( 1 9 5 0 ) . A r c h . i n d u s t r . H y g . , 2 ,
1 4 8 .S m a l e s , A . A . , a n d P a t e , B . D . ( 1 9 5 2 ) . A n a l y s t , 7 7 , 1 9 6 .S p o l y a r , L . W . , a n d H a r g e r , R . N . ( 1 9 5 0 ) . A r c h . i n i d u s t r . H y g . , 1 , 4 1 9
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