forensic article.pdf
Post on 26-Feb-2018
233 Views
Preview:
TRANSCRIPT
-
7/25/2019 Forensic article.pdf
1/10
Z . R e e h t s m e d i z i n 6 9, 5 2 - 6 1 1 97 1)
b y S p r i n g e r - V e r l a g 1 97 1
Gas Chromatography M ass Spectrom etry
in F orensic C hem istry for Identification
of Substances Isolated from Tissue
M . B L O ~ q m S T , R . B O ~N IC H SV ,N , C . - G . F ~ I , Y . M X ~ D v . , a n d R . R Y ~ A G ~
G o v e r n m e n t L a b o r a t o r y f o r F o r e n si c C h e m i s tr y , S t o c k h o l m a n d
L a b o r a t o r y fo r M a s s S p e c t r o m e t r y , K a r o l in s k a In s t i t u t e r , S t o c k h o l m S w e d en )
l~eee ived M arch 17, 1971
Summary.
T h e u s e o f c o m b i n e d g a s c h r o m a t o g r a p h y - m a s s s p e c t r o m e t r y i n f o r e n s i c
c h e m i s t r y i s d e m o n s t r a t e d i n 1 3 c a s es w h e r e v a r i o u s s u b s t a n c e s h a d t o b e i s o l a t e d a n d i d e n t i -
f i e d , t h e s u b s t a n c e w a s p r e s e n t i n s m a l l a m o u n t s i n s o m e s a m p l e s w h i le in o t h e r s t h e s a m p l e
a v a i l a b l e w a s v e r y s m a l l . I n o t h e r i n s t a n c e s a r a p i d a n d c e r t a i n i d e n t if i c a t io n w a s i m p o r t a n t .
T h e r e s u l t s a r e c o m p a r e d w i t h d a t a o b t a i n e d b y c o n v e n t i o n a l p r o c e d u re s . T h e a d v a n t a g e o f
t h i s m e t h o d i s d i s c u s s e d a n d i t i s e m p h a s i z e d t h a t a c o l le c t io n o f m a s s s p e c t r a o f a l l c o m m o n
subs tance s sea r ched in fo r ens ic chem is t ry s impl i f ie s t he inden t i f i ca t ion . Refe rence ma ss spec t r a
o f s o m e d r u g s a r e g i v e n .
Zusammen[assung.
D i e A n w e n d u n g e i n e r k o m b i n i e r t e n g a s c h r o m a t o g r a p h i s c h e n u n d
m a s s e n s p e k t r o p h o t o m e t r i s c h e n M e t h o d e i n d e r g e r ie h t l i e h e n C h e m i c w u r d e u n h a n d y o n 1 3
u n t e r s u e h t e n F i i l l e n d i s k u t i e r t . V e r s c h ie d e n e S u b s t a n z e n , z . T . i n k l e i n s t e n M e n g e n , w u r d e n
i s o l ie r t u n d i d e n t i f iz i e r t . D i e e r h a l t e n e n E r g e b n i s s e w a r d e n m i t d e n g e s u l t a t e n d e r k o n v e n t i o -
n e l l e n M e t h o d e n v e r g l i c h e n , z u d e m w i r d a u f d i e V o r t e il e d e r G C - M S - K o p p l u n g h in g e w i e se n .
G l e i c h z e it i g w a r d e n e i n i g e M a s s e n s p e k t r e n w i e d e r ge g e b e n .
N i n e M a s s e n s p e k t r e n s a m m l u n g y o n d e n i n d e r g e r i e h t l ic h e n C h em i c h ~ u fi g a n z u t r e f fe n d e n
Subs tanzen i s t f i i r e ine r asche und e in f ache Iden t i f i z i e rung e r fo rder l i ch .
Key Words:
F o r e n s ic c h e m i s t r y - - G a s C h r o m a t o g r a ph y - M a s s S p e c t r o m e t r y - -
M e t h a q u a t o n - - I )e t h id i n e - - O r p h e n a d ri n e .
A s d r u g s b e c o m e m o r e p o w e r f u l a n d t h u s d e c r e a s e t h e a m o u n t o f s u b s t a n c e
n e c e s s a r y f o r s e r io u s o r f a t a l i n t o x i c a t i o n s , t h e m e t h o d s u s e d b y t h e f o r e n s ic
c h e m i s t m u s t f a c i l i t a t e t h e d e t e c t i o n a n d i d e n t i f i c a t i o n o f s m a l l e r a n d s m a l l e r
a m o u n t s o f s u b s t a n c e . T h e n u m b e r o f d r u g s a r e a ls o s t e a d i l y i n c r ea s i n g a n d
t h e r e fo r e m e t h o d s f o r sc r e en i n g a n d i d e n t i f y i n g m u s t b e s im p l e r , a n d a l s o m o r e
s p e c if ic . S e v e r a l w o r k s d e a l i n g w i t h t h i s s u b j e c t h a v e b e e n p u b l i s h e d [ 1 -4 ] . F r o m
t h e s e p a p e r s i t i s e v i d e n t t h a t m a s s s p e c t r o m e t r y g i ve s u n d o u b t e d l y t h e m o s t
s p e ci f i c i n f o r m a t i o n i n c o m p a r i s o n t o o t h e r a n a l y z i n g m e t h o d s . F o r t h i s r e a s o n
t h e i d e n t i f i c a t i o n o f t h e a n a l y z e d s a m p l e c a n b e r a t h e r s i m p l e i n a s m u c h a s t h e
m a s s s p e c t r u m h a s b e e n c o l l e c te d i n th e r e f e r e n c e l i b r a r y . T h e m e t h o d o f s e a r c h i n g
n d c o m p a r i n g a n u n k n o w n m a s s s p e c t r u m w i t h r ef e re n c e s p e c t r a c a n b e a c c o m -
p l i s h e d u s in g a c o m p u t e r w i t h t h e k n o w n s p e c t r a o n m a g n e t i c t a p e o r f r o m b o o k s
h a v i n g a n i n d e x o f m a s s s p e c t r a l d a t a [ 5] .
H i t h e r t o , g a s c h r o m a t o g r a p h y - m a s s s p e c t r o m e t r y h a s f u n d a m e n t a l l y b e e n
u s e d i n f o r en s i c c h e m i s t r y t o i d e n t i f y a n d t o d e t e r m i n e t h e s t r u c t u r e o f s p e c i a l
c o m p o u n d s a n d m e t a b o l i t e s a n d n o t i n r o u t i n e w o r k . I n t h i s p a p e r w e d e s c r i b e
-
7/25/2019 Forensic article.pdf
2/10
G a s C h r o m a t o g r a p h y -M a s s S p e c t r o m e t r y i n F o r e n s ic C h e m i s t r y
53
s o m e c a s es , s e le c t e d a t r a n d o m , w h e r e t h e s a m p l e s e n t to t h e l a b o r a t o r y w a s
s m a l l o r t h e c o n c e n t r a t i o n o f t h e s u b s t a n c e t o b e a n a l y z e d v e r y l o w . T h u s i t
w o u l d h a v e t a k e n a l o n g t i m e a n d a l o t o f w o r k t o e x a m i n e t h e c a s e s w i t h o u t
u s i n g t h e G C - M S m e t h o d , i f p o s s i b l e a t al l. I n s o m e c a s e s t h e r e w a s s p e c i a l
n e e d f o r a n a c c u r a t e a n d r a p i d i d e n t i f i c a t i o n . T h e r e s u l t s a r e s u m m a r i z e d i n t h e
T a b l e .
Methods
In ad d i t i o n t o t h e co n v en t io n a l me th o d s (y i e ld o f w h ich i s g iv en i n t h e re fe ren ces o r i n
p rev io u s ly p u b l i sh e d w o rk s re fe r red t o i n t ex t ) t h e s u b s t an ces w ere an a ly zed b y LK B 9 0 0 0
g a s c h r o m a t o g r a p h - m a s s s p e c t r o m e t e r . W h e n s u f f i c i e n t a m o u n t s o f s a m p l e w e r e a v a i l a b l e ,
c o m p l e t e m a s s s p e c t r a w e r e t a k e n a t t h e G C - p e a k s . F o r s a m p l e a m o u n t s i n t h e n a n o g r a m
ran g e o n ly se l ec t ed mass n u mb ers w ere s t u d i ed u s in g t h e A V A (A cce l e ra t i n g V o l t ag e A l t e r -
n a t o r ) u n i t , c o n n e c t e d t o t h e m a s s s p e c t r o m e t e r [ 6 ] . I f t h e d e s i r e d m a s s n u m b e r s d i f f e r e d
i n m a s s m o r e t h a n 1 0 o f t h e h i g h e s t m a s s n u m b e r , s e p a r a t e r e g i s t r a ti o n s w e r e m a d e .
Th e m ass sp ec t ra w ere o b t a in ed a t a co n s t an t acce l e ra t i n g v o l t ag e o f 3 5 0 0 V . Th e e l ec t ro n
en e rg y w as n o rma l ly 7 0 eV , b u t i n so me cases l ow ered t o 1 5 eV . Th e t em p era tu re o f t h e i o n
so u rce w as 27 0 C . Th e co lu mn s u sed w ere 1 SE-3 0 o n Ch ro mo so rb W (8 0 -1 0 0 mesh )
1 .5 m 2 m m i . d. an d 5 Ca rb o w ax - t-5 K O H o n Ch ro mo so rb G (8 0 -1 0 0 mesh ) 2 m 2 m m
i . d. T h e t e m p e r a t u r e o f t h e i n j e c t i o n p o r t a n d t h e m o l e cu l e s e p a r a t o r w a s a b o u t 3 0 h i g h e r
t h a n t h e t e m p e r a t u r e o f t h e c o l u m n .
History Analysin g Methods and Results of Thirteen Cases of Poison ing
1 . Tw o w o men w ere fo u n d i n a ca r . Th e y o u n g e r o n e w as d ead an d t h e o ld e r o n e u n co n -
sc io u s . A ru b b e r t u b e w as l ed i n to t h e ca r f ro m th e g as o u t l e t . Mu rd e r w as su sp ec t ed . Th e
d ead w o m an su f fe red f ro m ep i l ep sy w i th sev e re p sy ch ica l d i s t u rb an ces . Sh e h ad b een p re sc r i b ed
ma n y d i f fe ren t d ru g s b y v a r io u s d o c to rs . Th e l i v e r w as g ro u n d a n d ex t r ac t ed w i th a l co h o l [7] .
A f t e r cen t r i fu g a t i o n , a p a r t o f t h e a l co h o l ex t rac t w as ev ap o ra t ed t o d ry n ess o n a w a t e r -b a th .
Th e re s id u e w as d i s so lv ed i n h o t d i l u t ed h y d ro ch lo r i c ac id an d t h e fa t r emo v ed b y co o l i n g
a n d f i l t r a t i o n [ 8 ] . T h e a c i d w a t e r s o l u t i o n w a s t h e n e x t r a c t e d w i t h c h l o r o f o r m . P a r t o f t h e
c h l o ro f o r m e x t r a c t w a s s h a k e n w i t h 0 .5 N N H ~ O H a n d t h e U V - s p e c t r a o f t h e a m m o n i a
s o l u t i o n w a s r e c o rd e d . A n o t h e r p a r t o f t h e c h l or o f o rm e x t r a c t w a s u s e d f o r p a p e r c h r o m a t o -
g r a p h y . P a r t o f t h e c h l o r o f o r m e x t r a c t w a s e v a p o r a t e d t o a s m a l l v o l u m e a n d u s e d f o r
GC-MS.
T h e s u b s e q u e n t c h e m i c a l a n a l y s i s r e v e a l e d t h a t t h e b l o o d f r o m t h e y o u n g e r w o m a n
co n ta in ed 3 2 ca rb o n mo n o x id e . N o a l co ho l w as d e t ec t ed . In t h e l i v e r ab o u t 1 2 rag b a r -
b i t u r a t e a c c o r d i n g to u l t r a - v i o l et s p e c t r u m w a s f o u n d , a n d i n t h e b l o o d a b o u t 4 r a g . S i n ce
t h e g i r l h a d b e e n p r e s c ri b e d p h e n o - b a r b i t o n e i t w a s o f g r e a t i m p o r t a n c e t o m a k e a n a c c u r a t e
i d e n t if i c a t i o n o f t h e b a r b i t u r a t e . N o c e r t a i n c o nc l u si o n co u l d b e d r a w n , f r o m p a p e r c h r o m a t o -
g r a m s , p r o b a b l y b e c a u s e s o m a n y m e t a b o l i t e s of b a r b i t u r a t e s a n d o f o t h e r d r u g s w e r e p r e s e n t.
T h e f i r s t r e p o r t g i v e n t o t h e p o l ic e w a s t h a t t h e d r u g w a s D i m i n a l D u p l ex @ ( a p r o b a r b it o n e
a n d v i n b a r b i t o n e ) a c c o r d i n g t o p a p e r c h r o m a t o g r a p h y . A c c o r d i n g t o g a s c h r o m a t o g r a p h y -
m a s s s p e c t r o m e t r y t h e m a i n p a r t o f t h e b a r b i t u r a t e w a s p h e n o b a r b i t o n e , r u n a t a t e m p e r a t u r e
of 155C on a SE -30 co lumn. P eak s of h igh in ten si ty are m /e 77 , 117 , 146 , 161 , 174 , 189 , 204
an d 2 3 2 . Base p eak i s 2 0 4 an d mo lecu l a r p eak i s 2 3 2 [4 ] .
2 . A d r iv e r , 5 8 y ea rs o ld , d ro v e h i s car o n t h e w ro n g s id e of t h e ro ad . H e w as ap p r eh en d ed
b y t h e p o l i ce , l q o a l co h o l co u ld b e d e t ec t ed i n t h e b lo o d . U r in e w as n o t av a i l ab l e . Th e b lo o d
w a s e x t r a c t e d w i t h c h l o ro f o r m o f a b o u t p H 3 . T h e c h l o r o f o rm w a s e v a p o r a t e d a n d t h e r e s id u e
f reed f ro m fa t a s d esc r ib ed ab o v e . Th e ch lo ro fo rm w as ex t rac t e d w i th 0 .5 N N H 4 0 H to g e t
r i d o f ac id s an d t h e n a p a r t o f t h e ch lo ro fo rm w as ev ap o ra t ed a n d t h e re s id u e d i s so lv ed in 7 0
a l k a li n e e t h an o l . U l t r a - v i o l e t s p e c t r u m o f b lo o d e x t r a c t s u g g e s te d s m a l l a m o u n t s o f m e t h a -
q u a l on e , a b o u t 0 .3 m g . T h e p r e s e n c e o f m e t h a q u a l o n e i n t h e e x t r a c t w a s p r o v e n b y g a s
c h r o m a t o g r a p h y a n d m a s s s p e c t r o m e t r y . A n S E - 3 0 c o l u m n w a s u s e d a t a t e m p e r a t u r e o f
1 9 5 C a n d a c o m p l e t e s p e c t r u m w a s r e c o r d e d . F r o m t h e r e f e r e n c e m a s s s p e c t r u m o f m e t h a -
q u a lo n e (F ig. 1 a ) i t c an b e seen t h a t t h e an a ly zed s amp le (F ig . 1 b ) h a s t h e same c rack in g
-
7/25/2019 Forensic article.pdf
3/10
5 4 M . B l o m q u i s t , R . B o n n i e h s e n , C . -G . F r i , Y . M ~ r d e , a n d R . R y h a g e :
p a t t e r n i n t h e h i g h m a s s r e g i o n w i t h t h e s a m e c h a r a c t e r is t i c p e a k s a n d s i m i l a r r e t e n t i o n t i m e
o n t h e g a s c h r o m a t o g r a m . C o n s e q u e n t l y t h e c o m p o u n d w a s i d e n ti f i ed a s m e t h a q u a l o n e .
3 . A f o u r - m o n t h o l d c h i l d w a s f o u n d d e a d i n b e d . U p o n a u t o p s y o l d c ra c k s in t h e s k u l l
w e r e f o u n d . A l c o h o l e x t r a c t i o n w a s p e r f o r m e d a s d e s c r i b e d i n c a se 1 . P a r t o f t h e a l c o h o l
e x t r a c t w a s e v a p o r a t e d a n d t h e re s i d u e d i s s o lv e d i n 5 0 K O H a n d h y d r o l y s e d o n a b o i li n g
w a t e r - b a t h . T h e s o l u ti o n w a s c o ol ed a n d e x t r a c t e d w i t h d i e t h y l e t h e r a n d r e e x t r a c te d i n t o
s u l p h u r i e a ci d . T h e a c i d w a s m a d e a l k a li n e a n d e x t r a c t e d w i t h c h l o r o fo r m . A p a r t o f t h e
c h l o r o fo r m w a s e v a p o r a t e d a n d t h e r e s i d ue w a s d i ss o l v ed i n 7 0 a l k a l in e e t h a n o l .
A p a r t o f t h e c h l o ro f o r m w a s u s e d f o r t h e U V - s p e e t r u m , a n o t h e r p a r t w a s c h r o m a t o g r a p h e d
o n a t h i n - l a y e r p l a t e ( m e t h a n o l : 2 5 a m m o n i a , 1 0 0 : 1. 5 , s p r a y i n g r e a g e n t D r a g e n d o r f f) .
T h e r e s t o f th e c h l o ro f o r m e x t r a c t w a s u s e d f or G C - M S , S E - 3 0 c o l u m n a t 1 8 0 C . T h e c h e m i c a l
a n a l y s i s o f t h e l i v e r r e v e a l e d a b o u t 1 m g o f a m i t r i p t y l i n e . B y t h e m a s s s p e c t r u m t h e
c o m p o u n d w a s i d e n t i f i ed a s a m i t r i p t y l i n e . F i g . 2 a s h o w s t h e r e f e r en c e m a s s s p e c t r u m o f
a m i t r i p t y l i n e r u n o n t h e G C - M S u n d e r n o r m a l c o n d i t i o n s ( i on s ou r c e 27 0 C , e l e c t ro n e n e r g y
7 0 e V ) . T h i s m a s s s p e c t r u m w a s d i f f i c u lt t o u s e f o r t h e i d e n t i f i c a t i o n o f a m i t r i p t y l i n e , d u e
t o t h e d - c l e a v a g e of t h e a m i n e g r o u p , w h i c h g a v e c a u s e t o a n e n o r m o u s p e a k a t m / e 5 8 , a n d
t h a t a l l o t h e r p e a k s w e re le ss t h a n 3 r e l a ti v e in t e n s i t y . T h e m o l e c u l a r io n a t ) / [ ~ 2 77 w a s
o f v e r y l o w i n t e n s i t y b u t t h e p e a k a t m / e 27 5 ( M -2 ) w a s s e v e r a l ti m e s h i g h e r . F ig . 2 b s h o w s
a r e fe r e n ce m a s s s p e c t r u m o f a m i t r i p t y l i n e w h e r e t h e s a m p l e w a s d i r e c t ly i n t r o d u c e d i n t o
t h e i o n s o u r ce w h i c h w a s k e p t a t 1 0 0 C a n d t h e p r o b e w a s h e l d a t a b o u t 3 0 C . I n t h i s c a s e
t h e m o l e c u l a r i o n M ~ --2 77 w a s o b t a i n e d b u t s t i ll r a t h e r l o w i n c o m p a r i s o n t o m / e 5 8 . T h e
p e a k s f r o m
m e
6 1 w e r e e n l a r g e d t e n t i m e s i n t h e d r a w i n g .
4 . A 4 7 y e a r - o l d f e m a l e w a s f o u n d d e a d . D u e t o c e r t a i n c i rc u m s t a n c e s m u r d e r w a s
s u s p e c t e d a n d i t w a s o f g r e a t i m p o r t a n c e t o m a k e a n a c c u r a t e i d e n t i f i c a t io n of t h e t y p e o f
d r u g i n t h e li v er . B y c h e m i c a l a n a l y s i s 0 . 1 4 a l co h o l w a s f o u n d i n t h e b l o o d a n d 0 .3 2
i n t h e u r i n e , a n d t r a c e s o f c h l o r d ia z e p o x i d e ( < 0 . 02 m g ) i n t h e u r i n e . T h e s a m e e x t r a c t i o n
m e t h o d f o r t h e l i v e r w a s u s e d a s f o r c a s e 3 . B y u l t r a - v i o l e t s p e c t r o m e t r y a b o u t 7 m g o f a
t r ic y c l ie a m i n e o f a m i t r i p t y l i n e t y p e w a s d e t e c t e d i n t h e l i v er . A c c o r d i n g t o t h i n - l a y e r a n d
g a s c h r o m a t o g r a p h y i t w a s n o r t r i p t y l i n e , w h i c h w a s c o n f i r m e d b y m a s s s p e c t r o m e t r y . A n
S E - 3 0 c o l u m n w a s u s e d a t a t e m p e r a t u r e o f 1 80 C . F ig . 3 a s h o w s t h e r e fe r e n ce m a s s s p e c t r u m
o f n o r t r i p t y l i n e r u n o n t h e G C - M S i n s t r u m e n t u n d e r n o r m a l c o n d i ti o n s . T h i s s p e c t r u m w a s
e n l a r g e d t e n t i m e s f r o m m / e 4 7 . A s d i s t i n g u i s h e d f ro m a m i t r i p t y l i n e t h e s p e c t r u m s h o w e d
t h e m o l e c u l a r i o n M ~ 2 6 3 u n d e r t h e s e c i r c u m s t an c e s . W h e n t h i s s u b s t a n c e w a s r u n w i t h a n
e l e c tr o n e n e r g y o f 1 5 e V o n l y t h e m o l e c u l a r i o n a n d a f e w f r a g m e n t s c o u l d b e d e t e c t e d a s
s h o w n i n F i g . 3 b .
5 . A 2 9 - y e a r- o l d m a l e w a s f o u n d d e a d . U l t r a - v i o l e t a b s o r p t i o n o f t h e l i v e r e x t r a c t c o u l d
b e d u e t o o r p h e n a d r i n e . E x t r a c t i o n w a s c a r r i e d o u t a s d e s c r ib e d f o r c as e 3 . T h e G C - M S
c o n f i r m e d t h e p r e s e n c e o f o r p h e n a d r i n e a n d a c c o r d i n g t o u l t r a - v i o l e t s p e c t r o m e t r y a n d g a s
c h r o m a t o g r a p h y t h e c o n c e n t r a t i o n w a s c a lc u l at e d t o a b o u t 2 0 m g . ( T h e s t o m a c h c o n t a i n e d
a b o u t 0 . 6 5 g o r p h e n a d r i n e ) . T h e c o l u m n u s e d w a s S E - 3 0 a t 1 8 0 C . F ig . 4 a s h o w s t h e r e fe r e n ce
m a s s s p e c t r u m o f o r p h e n a d r i n e , w h i c h g a v e o n l y a f e w p e a k s o f h i g h i n t e n s i t y . T h e b a s e p e a k
m / e 5 8 w a s t h e s a m e f r a g m e n t a s i n a m i t r i p t y li n e , a n d o t h e r c h a r a c t e ri s t i c p e a k s u s e d f o r
i d e n t i fi c a t io n w o r k , w e r e f o u n d b e t w e e n m / e 16 0 a n d m / e 1 85 . T h e m o l e c u l a r i o n w a s n o n -
d e t e c t a b l e a n d e v e n f o r a l o w e r e l e c t ro n v o l t a g e o f 1 2 e V t h e i o n i n t e n s i t y d i d n o t i n c r e as e .
I n l~ ig . 4 b t h e m a s s s p e c t r u m o f t h e l i v e r e x t r a c t g i v e s e v i d e n c e fo r t h e a s s u m p t i o n o f
o r p h e n a d r i n e c o n t e n t .
6 . A n a u t o m o b i l e w a s d r i v e n b y a 3 9 y e a r - o ld m a l e i n a v e r y q u e e r m a n n e r . T h i s w a s
r e p o r t e d t o t h e p o l i c e . A b l o o d s a m p l e w a s d e s t i l l e d a n d t h e v o l a t i l e w a s t r a p p e d i n c o l d
e t h a n o l a n d q u a n t i t a t i v e d e t e r m i n a t i o n w a s d o n e b y a m o d i fi e d F u j i w a r a m e t h o d [9 ]. T h e
s u b s e q u e n t a n a l y s i s o f t h e d e s t il l a te o f t h e b l o o d b y g a s c h r o m a t o g r a p h y s h o w e d a p e a k
o n t h e r e c o r d er w h i c h a c c o r d in g t o s t a n d a r d s w a s e q u a l t o a b o u t 0. 5 r a g t r i c h l o r o e t h y l e n e
i n t h e b l o o d . T h i s m e t h o d h a s a l o w s p e c i f ic i t y a n d c o n f i r m a t i v e i d e n t i f i c a t i o n w a s c a r r i e d
o u t b y t h e G C - M S m e t h o d o n t h e e t h a n o l s o l u ti o n . S i n c e o n l y a s m a l l a m o u n t o f s a m p l e
w a s a v a i l a b l e t h e t w o m o s t c h a r a c t e r i s t i c p e a k s m / e 9 5 ( M -C 1 ) a n d m / e 1 3 0 ( M ) w e r e s t u d i e d
b y t h e A V A u n i t . T h e C a r b o w a x c o l u m n w a s u s e d a t a t e m p e r a t u r e o f 4 0 C . T h e i n t e n s i t y
r a t i o s a g r e e w i t h t h e r e f e r e n c e m a s s s p e c t r u m o f t r i c h l o r o e t h y l e n e [5 ] . ( T h e b l o o d a ls o
c o n t a i n e d 4 . 4 r a g t r i e h l o r o a e e t i e a c i d . T h e u r i n e c o n t a i n e d 7 6 r a g t r i e h l o r o a c e t i c a c i d ).
-
7/25/2019 Forensic article.pdf
4/10
G as Ch ro ma to g rap h y -Mass Sp ec t ro m e t ry i n Fo ren s i c Ch em is t ry 5 5
7 . A 1 4 y ea r -o ld b o y w as accu s to med to s t ay in g aw ay f ro m sch o o l p e r io d i ca l l y . Wh i l e
v i s i t i n g a b ak e rs sh o p , h e su d d en ly d i ed . U p o n au to p sy a sp i ra t i o n o f s t o mach co n t en t w as
fo u n d . B lo o d an d b ra in w ere d es t i l l ed an d t h e d es t i l l a t e w as ex t rac t ed w i th n -h ex an e .
Fu j iw ara ' s t e s t g av e a co lo u r i n d i ca t i n g t h e p re sen ce o f mo re t h an o n e c lo r i n a t ed ca rb o n .
T h e n - h e x a n e x t r a c t w a s u s e d f o r G C - M S. T w o G C - p e ak s w e re o b t a i n e d a n d b y m a s s s p e c tr o -
me t ry t h e se p eak s w ere i d en t i f i ed a s t r i ch lo ro e th y l en e an d ch lo ro fo rm (ab o u t 2 rag ch loro -
fo rm a n d l e s s t h a n 0 .4 mg t r i ch lo ro e th y l en e i n t h e b lo o d . Th e b ra i n co n t a in ed ab o u t 1.3 rag /0
ch lo r in a t ed h y d ro ca rb o n s ca l cu l a t ed a s ch lo rofo rm) . Th e Ca rb o w ax co lu mn w as u sed a t a
t e m p e r a t u r e o f 5 5 C a n d c o m p l e t e m a s s s p e c t r a w e r e t a k e n . T h e b o y m u s t t h u s s o m e h o w
h av e h ad access t o ch lo ro fo rm.
8 . So me ch i l d ren fo u n d a n u mb er o f g l a ss amp u l s co n t a in in g a co lo u red so lu t i o n in a
san d b o x . So o n a f t e rw ard s o th e r am p u l s w ere a l so fo u n d i n d if fe ren t p laces i n t h e s u r ro u n d in g .
T h e p o li c e w a n t e d t o k n o w i f t h e c o n t e n t w a s d a n g e r o u s a n d i f t h e i n h a b i t a n t s i n t h e a r e a
s h o u l d b e a l a r m e d a s s o m a n y c h i ld r e n w e r e f o u n d p l ay i n g w i t h t h e a m p u l s .
A rap id an a ly s i s w as t o b e p e r fo rmed . Th e so lu t i o n w as v o l a t i l e , an d u sed d i rec t l y fo r
G C-MS. Becau se t h e SE-3 0 co lu m n w as a l read y i n t h e g as ch ro ma t o g ra p h o f t h e m ass sp ec t ro -
m e t e r i t w a s us e d, a t r o o m t e m p e r a t u r e . I n a f ew m i n u t e s t h e s o l u t i o n w a s s h o w n t o c o n t a i n
d i ch lo ro me th an e . Th e mass sp ec t ru m w as i d en t i ca l t o t h e re fe ren ce sp ec t ru m [5 ] . La t e r
o n t h e co lo u r i n t h e so lu t i o n w as fo u n d t o b e a me th y l o ran g e i n d i ca to r .
I n t h e f o l l o w in g f iv e c as e s t h e e x t r a c t i o n m e t h o d s w e r e a s fo l lo w s :
T h e b l o o d o r u r i n e w a s e x t r a c t e d a t a b o u t p H 8 . 5 w i t h c h l o r o f o r m ; b i c a r b o n a t e b u f f e r
w as u sed t o co r rec t t h e p H . Th e ch lo ro fo rm w as reex t ra c t ed i n to 0 .1 N H 2 SO 4 . Th i s ex t rac t
w as u sed fo r u l t ra -v io l e t sp ec t ro me t ry . Th e su lp h u r i c ac id w as a lk a l i zed an d ex t rac t ed
w i t h d i e t h y l e t h e r . G a s e h r o m a t e g r a p h y , a n d i f t h e r e w a s e n o u g h m a t e r i a l , a ls o t h i n - l a y e r
ch ro ma to g rap h y w ere ca r r i ed o u t . Th e e th e r ex t rac t w as u sed fo r G C-MS. A l fe s an d C la s in g
h a v e d e s c r i b e d a m e t h o d u s i n g t h i n - l a y e r c h r o m a t o g r a p h y a n d m a s s s p e c t r o m e t r y , f o r d e te r -
m i n a t i o n o f d a n s y l a t e d m e t h a m p h e t a m i n e ( d a n s y l = 1 - d i e m e t hy l a m i n o - na p h t a le n e - 5 - s ul f o n y l)
[ I0 ] .
9 . A 2 2 y ea r -o ld s t u d en t , w h o h a d b e h av ed s t ran g e ly , w as k i l l ed b y a t ru ck . H e w as
s u s p e c t e d t o h a v e t h r o w n h i m s e l f i n f r o n t o f t h e t r u c k . I n t h e b l o o d w a s f o u n d , b y g a s
c h r o m a t o g r a p h y , a p e a k w i t h t h e s a m e r e t e n t i o n t i m e a s a m p h e t a m i n e , t h e a m o u n t c o rr e -
sp o n d in g t o ab o u t 1 7 ~g p e r 1 0 0 ml o f b lo o d . Th e co n cen t ra t i o n i n t h e samp le w as f~o sma l l
t o b e i d e n t i f i e d b y o u r u s u a l m e t h o d ( c o l o u r r e a c t i o n o n t h i n - l a y e r e h r o m a t o g r a m ) . B y
G C - M S t h e b l o o d e x t r a c t w a s p r o v e n t o c o n t a i n a m p h e t a m i n e . T h e s m a l l a m o u n t p r e s e n t
ma d e i t n ecessa ry t o u se t h e A V A u n i t , a n d t h re e ch a rac t e r i s t i c p eak s a t m /e 4 4 , 9 1 an d 1 2 0
w ere reco rd ed . Th e i n t en s i t y ra t i o o f t h e se p eak s w ere i d en t i ca l t o t h e same p eak s i n t h e
r e f er e n ce m a s s s p e c t r u m o f a m p h e t a m i n e .
1 0. A 1 7 y ea r -o ld g i r l h a d p rev io u s ly u sed n a rco t i c s . I t w as su sp ec t ed t h a t sh e h ad b eg u n
to u se n a rco t i c s ag a in . A v e ry sma l l samp le w as sen t t o u s . Th e b lo o d ex t rac t g av e a t t h e g as
c h r o m a t o g r a m a p e a k w i t h e x a c t l y t h e s a m e r e t e n t i o n t i m e a s a m p h e t a m i n e , c o r r e s po n d i n g
t o a b o u t 0 .3 r a g . A c c o r d i n g t o m a s s s p e c t r o m e t r y t h e p e a k w a s n o t a m p h e t a m i n e . T h e
Carb o w ax co lu mn w as u sed a t a t emp era tu re o f 1 4 0 C . Tw o p eak s w ere fo u n d , b u t t h ey
h a v e n o t y e t b e e n i d e n t i f i e d . T h e y b o t h h a v e t h e b a s e p e a k a t m / e 7 5 a n d p r o b a b l y c o n t a i n
ch lo r in e . Th e r e t en t i o n t imes w ere 0 .4 an d 0 .5 re l a t i v e t o n i co t i n e .
Pea ks of h ig h in tens i ty were for GC- peak one m/e 47, 75 , 103 , 185 and 187, for GC-pe ak
tw o m/e 4 7 , 75 , 1 0 3, 1 4 5, 1 4 7, 2 19 an d 2 2 1. Ju d g in g f ro m th e i n t en s i t y ra t i o s o f t h e a s su m ed
mo lecu l a r p eak s (18 5 an d 1 87 , 2 1 9 an d 2 2 1) t h ey co u ld co n t a in tw o a n d t h ree ch lo r in e a to m s
respect ive ly .
1 1. A 2 6 y ea r -o ld ma le sh o t h imse lf . H e w as a k n o w n n a rco t i c u se r t o t h e p o l ice . A s a
w o man w as p re sen t i n t h e ap a r tmen t d u r in g t h e su i c id e a ch emica l an a ly s i s w as p e r fo rmed .
A c c o r d i n g t o t h e s t o r y t h e m a n s h o u l d h a v e i n j e c t e d a m p h e t a m i n e i m m e d i a t e l y d e a t h . T h e
a m p u l s f o u n d i n t h e a p a r t m e n t c o n t a i n e d a m p h e t a m i n e . I n t h e b lo o d 0 . 04 a l co h ol w a s
f o u n d . A c c o r d in g t o ga s c h r o m a t o g r a p h y a n d t h i n - l a y e r c h r o m a t o g r a p h y 5 r a g p h e n -
m e t r a z i n e w a s f o u n d i n t h e
urine
0 .8 rag i n t h e b lo o d an d 0 .7 rag i n t h e l i v er . O n t h e g as
e h r o m a t o g r a m o f t h e b l o o d e x t r a c t w a s o b t a i n e d a n a d d i t i o n a l p e a k w i t h p r a c t i c a l l y t h e
-
7/25/2019 Forensic article.pdf
5/10
56 M. B lomq u i s t , R . Bonn ichsen , C . -G . Fr i , Y . M rde , and R . Ryhag e :
100 100
METHAQUALONE M-15 235
235
.__>,.75 ~ .N., 75 ; 50
M
~
2 250 c
c E
~ 50 -~ 50
> 91 M.w. = 250 >
- - k , ~
~ ~ 25
~ 25
. . , .,, ,...~,I..,If,.I,.,,,. ,...... .I ....................... [
0 50 100 150 200 250 250
M/E M/E
b
Fig . 1. a Re fe rence mass spec t rum o f me th aqua lo ne , b T he h igh mass reg ion o f a mass spec t rum
from b lood ex t rac t i n ca se 2 . Bo th spe c t ra w ere run u s ing an SE-30 co lumn a t 195C
100
~:
75
O
c
>_ 50
a: 25
a 0
100
75
5O
25
0
h
. . , ,
AMITRIPTYLINE
58
CH CH2tCHz N< CH3
L,..58 CH3
M.w. = 277 M
277
, . ' J, , ' , ' ' , ' , , , ,,,, ', , ,, , L ' '; , ; , , ; , , , ,
AMITRIPTYUNE
58
i / 2 o 3
111
. , L,.,,t ..,......, . , .11 . . .
50 I00 t50 200 250
N/E
Fig . 2a an d b . Re fe r ence mass sp ec t ra o f ami t r i py l i ne . See ca se 3 . a A n S E-30 co lum n a t
180C w as u sed . The i on sou rce w as ke p t a t 270C . b T he d i rec t i n l e t w as u sed a t 30C .
The i on sou rce w as kep t a t 100C . A l l peaks f rom m/e 61 w ere en l a rged t en t imes
s a m e r e t e n t i o n t i m e a s a m p h e t a m i n e . B y ( ] C - M S u s i n g t h e C a r b o w a x c o l u m n a t 1 5 0 C t h i s
peak w as show n to be 2 -pheny l e thy l amine , w i th t he cha rac t e r i s t i c peaks a t m/e 30 , 91 (M-30 )
and 121 (M) . F ig . 5 show s a re fe rence mass spec t rum o f 2 -pheny l e thy l a mine . To t he s t o ry
m u s t b e a d d e d t h a t t h e s u i c i d e w a s n o t r e p o r t e d t o t h e p o l i c e u n t i l t w o d a y s l a t e r , s o s o m e
p u t r e f a c t i o n o f t h e b l o o d h a d p r o b a b l y t a k e n p l a c e .
12. Th ree ca ses o f quee r ca r d r i v ing . O n ly b lood w as ava i l ab l e . N o a l coho l w as found a nd
s y m p a t h o m i m e t i c a m i n e s w e r e su s p e ct e d . S m a l l a m o u n t s o f b l o o d w er e s e n t t o t h e l a b ,
e x t r a c t e d a n d a n a l y z e d b y g a s c h r o m a t o g r a p h y . V e r y s m a l l p e a k s , w h i c h c o u l d c o r r e s p o n d
-
7/25/2019 Forensic article.pdf
6/10
Gas Chromatography-Mass Spectr ometry in Forensic Chemistry 57
I00
~ 75
-~
-~
} 5o
r~
a:: 25
a 0 ;I
100
~>. 75
._
m
-~ 5O
.~
Q
-~
Y 25
NORTRIPTYLINE
44
CH-CH2TCH2-NH-CH~
L-,-44
M.w. = 263
,~,.-xl0 /203
~
,, , , ~?1, . .~
44
NORTRIPTYLINE
M-70 M-43 M
193 220 263
0 50 100 150 200 250
b M/E
Fig. 3a and b. Reference mass spectra of nortrip tylin e run on an SE-30 column at 180C.
See case 4. a The ionization potenti al was 70 eV All pesks from m/e 47 were enlarged ten
times b The ionization potential was 15 eV
100
>, 75
2
~> 5O
-~
r,- 25
0
100
58
73
.] ] . ..;
ORPHENADRINE
181,~.. ..~-58
(~ /-- CH-IrO- C H 2~CH2- N.75
5
_c 50
a~ ~5
58
166
~ 8~
. . . . h L h _ ~ ~
. . . . . . . . . . . . . . . . . . . . . . ~
0 50 100 150 200 250
5 M/E
Fig. 4. a Reference mass spectr um of orphenadrine b Mass spect rum from liver ext ract in
case 5. Both spectra were run using an SE-30 column at 180C
-
7/25/2019 Forensic article.pdf
7/10
5 8
M . B l o m q u i s t , R . B o n n i c h s e n , C .- G . F r i , Y . M r de , a n d R . R y h a g e :
100
?5
c 50
~: 25
3 0 2 PHENYL ETHVLAMINE
~ o
M.w. = 121
M 3 0
91
0 50 100
M/ E
F i g . 5. R e fe r e n c e m a s s s p e c t r u m o f 2 - p h e n y l e t h y l a m i n e r u n o n a C a r b o w a x c o l u m n a t 1 5 0 0 .
S e e c a se 11
100
75
~ 50
- 6
Or
25
57
. f l . I . : L .
5O
PETHIDINE
71 CH3
COOC2Hs 247
100 150 200 250
M / E
100
f 7 5
s o
~: 25
0
b
71
57
5O
2Z,7
I 2 1 8
I J f .: h
] , . ,
I l ~ ~ . I l
, . , , . . , J , , : . , , . ,
IL ~ 1 7 4
, . ,. . ,. . ,, , . , , . , . , , ,
100 150 200 250
M / E
F i g . 6 . a R e f e r e n c e m a s s s p e c t r u m o f p e t h i d i n e , b M a s s s p e c t r u m o f u r i n e e x t r a c t i n c a s e 1 3.
B o t h s p e c t r a w e re r u n u s i n g a C a r b o w a x c o l u m n a t 1 8 5 C
t o p h e n m e t r a z i n e w e r e o b t a i n e d . B y G C - M S t h e p e a k s w e r e s h o w n t o d o so . T h e s a m p l e s
w e r e i n j e c t e d o n t h e C a r b o w a x c o l u m n a t 1 9 0 C , a n d t h e m o l e c u l a r i o n in t h e p h c n m e t r a z i n e
s p e c t r u m m/e 1 7 7 ) w a s r e g i s t e r e d u s i n g t h e A V A [ 3 ] .
1 3. A u r i n e s a m p l e w a s s e n t t o t h e l a b t o b e t e s t e d f o r c e n t r a l - s t i m u l a t i n g a m i n es . A
p e a k i n t h e g a s c h r o m a t o g r a m i n d i c a t e d t h e p r e s e n ce o f p h e n m e t r a z i n e . M u c h f u r t h e r o n t h e
r e c o r d i n g t h e r e w a s a n o t h e r p e a k . A s t h e r e s u l t s w e r e o f s o m e i m p o r t a n c e m a s s s p e c t r a o f
t h e t w o p e a k s w e r e t a k e n . T h e o n e c o r r e s p o n d i n g t o p h e n m e t r a z i n e w a s a n o t h e r s u b s t a n c e
-
7/25/2019 Forensic article.pdf
8/10
G a s C h r o m a t o g r a p h y - M a s s S p e c t r o m e t r y i n F o r e n s ic C h e m i s t r y
T a b l e . sum m ary o ] t he r e su l t s ] rom the t h i r t e e n c ase s a s de sc r ibe d in t he t e x t
5 9
N o . M a t e r i a l C o n - C o n - G C - M S r e s u l t s C o l u m n A d d i t i o n a l r e s u l t s
v e n t i o n a l c e n t r a t i o n t e m p e r a t u r e C
m e t h o d s
1 . l i v e r U V , P C 1 2 r a g - p h e n o b a r b i t e n e S E - 3 0 , 1 5 5 3 2 C O
b l o o d U V , P C 4 m g - p h e n o b a r b i t o n e - -
2 . b l o o d U V , G L C 0 ,3 m g - m e t h a q u a l o n e S E - 3 0, 1 9 5 - -
3 . l i v e r U V , T L C , 1 m g - a m i t r i p t y l i n e S E - 3 0 , 1 8 0 - -
G L C
4 . b l o o d . . . . 0 ,1 4 a l c o h o l
u r i n e . . . . 0 ,3 2 a lc o h o l , e h lo r -
d i a z e p o x i d < 0 , 0 2 r a g -
l i v e r U V , T L C 7 m g - n o r t r i p t y l i n e S E - 3 0 , 1 8 0 - -
5 . l i v e r U V , G L C 2 0 r a g - o r p h e n a d r i n e S E - 3 0 , 1 8 0
s t o m a c h U V t o t a l a m o u n t o r p h e n a d r i n e - -
0 , 65 g
6 . b l o o d F u j i w a r a , 0 ,5 m g - t r i c h l o ro e t h y l e n e C a r b o w a x , 4 0 c h l o r i n a t e d h y d r o c a r b o n s
G L C c a l e u l a t e d a s t r i c h l o ro -
a c e t i c a c i d 4 , 4 m g -
u r i n e . . . . d : o 76 ra g -
7 . b l o o d F u j i w a r a 2 r a g - c h l o r o f o r m C a r b o w a x , 5 5
< 0 , 4 m g - t r i e h l o r o e t h y l e n e
b r a i n F u j i w a r a e 1 ,3 m g - c h l o r o fo r m a n d - -
t r i c h l o r o e t h y l e n e
8 . a m p u l - - - - d i e h l o r o m e t h a n e S E - 3 0 , 3 0 i n d i c a t o r m e t h y l o r a n g e
9 . b l o o d G L C 1 7 ~ g / 10 0 m l a m p h e t a m i n e C a r b o w a x , 1 5 0 - -
1 0. b l o o d G L C - - u n i d e n t i f i e d C a r b o w a x , 1 40 ( t h e u n i d e n t i f i e d p e a k ,
( e x p e c t e d c o r r e s p o n d s t o 0 . 3 m g -
a m p h e t a m i n e ) a m p h e t a m i n e )
1 1. b l o o d G L C - - 2 - p h e n y l - C a r b o w a x , 1 5 0 0 ,8 m g - p h e n m e t r a z i n e
e t h y l a m i n e 0 , 04 e t h a n o l
u r i n e . . . . 5 m g - p h e n m e t r a z i n e
l i v e r . . . . 0 ,7 m g - p h e n m e t r a z i n e
1 2 a ) b l o o d G L C t r a c e s p h e n m e t r a z i n e C a r b o w a x , 1 9 0 - -
b ) b l o o d G L C t r a c e s p h e n m e t r a z i n e C a r b o w a x , 1 9 0 - -
c ) b l o o d G L C ~ r ac e s p h e n m e t r a z i n e C a r b o w a x , 1 9 0 - -
1 3 . b l o o d G L C 0 , 8 m g - p e t h i d i n e a C a r b o w a x , 1 8 5 - -
a A n o t h e r p e a k w i t h a p p r o x i m a t e r e t e n t i o n t i m e l ik e p h e n m e t r a z i n e w a s i n v e s t i g a t e d a n d
f o u n d n o t t o b e p h e n m e t r a z i n e , b u t c o u l d n o t b e i d e n t i fi e d .
-
7/25/2019 Forensic article.pdf
9/10
60 M. Blomquist, R. Bonnichsen, C.-G. Fri, Y. Mrde, and R. Ryhage:
not yet identified. The other peak was identified as being pethidine (0.8 mg ). At 185C on
the Carbowax column, the unknown peak had a retention time of 1.8, and pethidine a retentio
time of 4.0 relative to nicotine.
Fig. 6 a shows that the base peak in the reference spectrum of pethidine arises from cleavage
of the methyl-piperidyl part of the molecule. The peak at m/e 57 comes from loss of a methylene
group from the base peak at m/e 71. The peak at m/e 174 corresponds to the loss of the ester
group from the molecule. The loss of the ethyl group gives rise to a peak at m e 218. The
molecular ion at m/e 247 is about 40 as compared to the base peak. Fig. 6b shows the mass
spectrum of the urine extract.
i s cuss ion
Fro m the described cases of intoxicat ion it is shown that the combined GC-MS
method can be used for identification of quite different analytical problems.
Almost all types of drugs or other similar compounds can usually be run by the
GC-MS instrument. Compounds impossible to run on the gas chromatograph
can in some cases be analyzed using the direct inlet of the mass spectrometer.
If suitable derivatives are made, the y can be run on the GC-MS. The mass spectro-
metric studies of several types of drugs have shown that the cracking patterns
of molecules are, in general, characteristic for each one. There are however
exceptions to this rule. Fr om the reference mass spectra available it is for instance
indicated that when a side chain contains an amine group, a very high peak is
obtained for a fl-cleavage. Mass spectra of such compounds normally exhibit a
small or non-detectable molecular ion.
Fig. 2 shows mass spec tra where the intensity of m/e 58 is extremely high
as compared to the other peaks in the spectrum. Fig. 3 shows a similar cracking
pattern with a very intense peak at m/e 44. There are however, groups of small
peaks which are very characteristic for each compound. Even if it is difficult to
show the structure of all these fragments they can be used for identification of
drugs. I f the electron energy is decreased from 70 eV to ab out 12 to 15 eV the
relative intensity of the fragments change in such a way that most of the peaks
decrease except the molecule ion. An example of this meth od is shown in Fig. 3 b.
To obtain a high intensity of the molecular ion these and similar compounds
should be run on a gas chromatograph combined with a mass spectrometer with
chemical ionization [11 ]. In the case of amitriptyline and nortrip tyline small peaks
of M-2 and M-1 are observed along with the molecular ion M. It seems evident
tha t M-2 is a thermal degradation product, which is dependent upon the operating
temperature of the ion source and introduction line and M-1 fragments are often
seen in mass spectra from amino compounds. Methaqualone and six metabolite
isomers have been studied by other scientists [12,13]. There are however several
metabolites which show different molecular weights and a separate study of this
subject is under examination.
In case 10 it was suspected tha t ampheta mine should be indicated, but
instead, two mass spectra of unk nown compounds were recorded. These compounds
must be studied further before an exact structure determination can be made.
This and other identification problems show that it is of importance to develop
a library of reference mass spectra of all available drugs and toxi-compounds,
which will reduce the time required for identification. Whe n only small amo unts of
sample are available, great de mands are made upon the accurac y of the analyzing
method. On the other hand, when methods become so sensitive that a few nano-
-
7/25/2019 Forensic article.pdf
10/10
G a s C h r o m a t o g r a p h y -M a s s S p e c t r o m e t r y i n F o r e n s i c C h e m i s t ry 6 1
g r a m s c a n b e d e t e c t e d a n d i d e n ti f ie d , i t i s o f u t m o s t i m p o r t a n c e t o b e e x t r e m e l y
c a re fu l . T h e s a m p l e s a r e e a s i l y c o n t a m i n a t e d w h e n w o r k i n g w i t h s u c h s m a l l
a m o u n t s . M a n y s u b s t a n c e s a r e e x c r e t e d t h r o u g h t h e s k i n a n d t h u s , s i m p l y h a n d l i n g
o f t h e s a m p l e c o u l d ca u s e c o n t a m i n a t i o n . R e a g e n t s u s e d f o r a n a l y s i s c o u l d a l s o
c o n t a i n t i n y a m o u n t s o f t h e p a r t i c u l a r s u b s t a n c e . P e o p l e a r r i v in g f r o m c o u n t r ie s
w h e r e t h e u s e o f c e r t a i n n a r c o t i c s i s l e g al , c o u l d s t il l h a v e n g o f t h e d r u g i n t h e i r
u r i n e m a n y d a y s a f t e r h a v i n g l e f t t h e c o u n t r y .
Acknowledgement T h i s w o r k h a s b e e n s u p p o r t e d p a r t l y b y t h e S w e d i s h M e d i c a l R e s e a r c h
Coun ci l pro ject No. B71-13X-171-07C) .
e l e r e n c e s
1 . C u r r y , A . S . : M o d e r n t e c h n i q u e s f o r t h e d e t e c t i o n a n d e s t i m a t i o n o f d r u g s o f a d d i c t i o n .
M ed. Sci . La w. 8 , 257-260 1968).
2 . A l t h a u s , J . R . , B i e m a n n , K . , B i l le r , J . , D o n a g h u e , P . F . , E v a n s , D . A . , F o e r s t e r , H . J . ,
He r t z , H . S . , H ign i t e , C . E . , M urphy , R . C . , P r e t i , G . , Re inho ld , V . : I den t i f i ca t io n o f t he
d r u g D a r v o n a n d i t s m e t a b o l i t e s i n th e u r i n e o f a c o m a t o s e p a t i e n t u s i n g a g a s c h ro m a -
t o g r a p h - m a s s s p e c t r o m e t e r - c o m p u t e r s y s t e m . E x p e r i e n t i a B a s e l) 2 6, 71 4 1 97 0).
3 . B o n n i e h s e n , R . , M a e h l y , A . C ., M r d e , Y . , R y h a g e , R . , S c h u b e r t , B . : D e t e r m i n a t i o n a n d
i d e n t i f i c a t io n o f s y m p a t h o m i m e t i e a m i n e s i n b l o o d s a m p l e s f r o m d r i v e r s b y a c o m b i n a t i o n
o f g a s c h r o m a t o g r a p h y a n d m a s s s p e c t r o m e t r y . Z . R e c h t s m e d i z i n 6 7, 1 9 - 2 6 1 97 0).
4 . I d e n t i f i c a t i o n o f s m a l l a m o u n t s o f b a r b i t u r a t e s e d a t i v e s i n b i o l o g ic a l
s a m p l e s b y a c o m b i n a t i o n o f g a s c h r o m a t o g r a p h y a n d m a s s s p e c t r o m e t r y . Z a c c h i a 6 , 1
1970).
5 . M a s s s p e c t r a ~ ro m A S T M E l 4 , D o w , A P I a n d M C A c o l l e ct io n s o n m a g n e t i c t a p e . M a s s
S p e c t r o m e t r y D a t a C e n t re , A W t ~ E , A l d e r m a s t o n .
6 . S w e e l e y , C . C ., E l l i o t t , W . H , F r i e s , I . , R y h a g e , R . : M a s s s p e c t r o m e t r i c d e t e r m i n a t i o n
of un reso lved componen t s i n gas ch romatograph ic e f f luen t s . Ana ly t . Chem. 38 , 1549
1966).
7 . Bonn iehsen , R . : To b e pub l i shed .
8 . - - M a e h l y , A . C ., F r a n k , A . : B a r b i t u r a t e a n a l y s is : M e t h o d a n d s t a t is t i c a l s u r v ey . J .
foren s. Sci. 6, 411 1961).
9 . - - - - P o i s o n i n g b y v o l a t i l e c o m p o u n d s . I I . C h l o r i n a t e d a l i p h a t i c h y d r o c a r b o n s . J . f o re n s .
Sei. 11, 414 1966).
1 0. A l f es , H . , C l a si n g, D . : I d e n t i fi z i e r u n g g e r i n g e r M e n g e n M e t h a m p h e t a m i n s n a c h K 5 r p e r p a s -
s a g e d u r e h K o p p l u n g y o n D i i n n s c h i c h t c h r o m a t o g r a p h i e u n d M a s s e n s p e k t r o m e t r i e . I V .
M it t . Dtsc h. Z. ges. ger ic ht l . M ed. 64, 235 1969).
1 1. F a l e s , t t . M . , M i l ne , G . W . , A x e n r o d , T . : C h e m i c a l i o n i z a t i o n m a s s s p e c t r o m e t r y o f
c o m p l e x m o l e cu l e s. I d e n t i f i c a t i o n o f b a r b i t u r a t e s b y c h e m i c a l i o n i z a t i o n m a s s s p e c t r o m e -
t ry . Ana ly t . Chem. 42 , 1432 1970).
1 2. N o w a k , I t . , S c h o r re , G . , S t r u l le r , R . : U n t e r s u e h u n g e n z u m M e t a b o l i s m u s y o n M e t h a -
qua lon . Arzn e im i t t e l -For sch . 16 , 407-411 1966).
1 3. P r e u s s , F . R . , H o f f m a n n - P i n t e r , I t . , A c h e n b a c h , H . , F r i e b o l i n , I t . : Z u r B i o t r a n s f o r m a t i o n
des 2 -M ethy l -3 -odo ly l -4 - 3H) -eh inazo l inon Methaqua lon) , Pharm az ie 25 , 752 1970).
D o z e n t R . R y h a g e
L a b o r a t o r y f o r M a ss S p e c t r o m e t r y
K a r o l i n s k a I n s t i t u t
S-10401 Stockholm 60
P r o f e ss o r D r . R . B o n n i c h s e n
G o v e r n m e n t L a b o r a t o r y f o r F o r e n s i c C h e m i s tr y
S-10401 S tockh o lm 60
top related