forensic article.pdf

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


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


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 ).


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


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


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


7/10

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


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 .


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-


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

forensic article.pdf

Documents