A Comparison of Heroin Samples - ACS Symposium Series (ACS

18 A Comparison of Heroin Samples S.

P.

SOBOL

and

A.

R.

SPERLING

Downloaded by MONASH UNIV on February 23, 2016 | http://pubs.acs.org Publication Date: June 1, 1975 | doi: 10.1021/bk-1975-0013.ch018

U. S. D e p a r t m e n t of Justice, Drug E n f o r c e m e n t A d m i n i s t r a t i o n , S p e c i a l T e s t i n g a n d Research L a b o r a t o r y , M c L e a n , V a . 22101

The comparison o f evidence i s a w e l l - e s t a b l i s h e d f u n c t i o n o f the f o r e n s i c l a b o r a t o r y . F i e l d s o f e x p e r t i s e such as document examination, f i n g e r p r i n t a n a l y s i s , firearms examination, as w e l l as a myriad o f other types of examination, all rely on the com- p a r i s o n of an e x h i b i t with e i t h e r a reference c o l l e c t i o n or another s p e c i f i c e x h i b i t . Little a t t e n t i o n , however, has been given t o the comparison o f drug e x h i b i t s . The p o t e n t i a l value o f such types o f analyses is e q u a l l y as great as i n other fields. I f c o r r e l a t i o n s among drug e x h i b i t s can be made, then d i s t r i b u t i o n systems may be identified and conspiracy cases developed. A l s o , comparisons o f e x h i b i t s can provide more s p e c i f i c information t o the i n v e s t i g a - t o r or i n t e l l i g e n c e a n a l y s t . One means o f comparing drug e x h i b i t s i s t o i d e n t i f y the i m p u r i t i e s which are present i n the m a t e r i a l and t o determine t h e i r r e l a t i v e c o n c e n t r a t i o n s . Although some previous work has been reported regarding i m p u r i t i e s a s s o c i a t e d with c l a n d e s t i n e l y produced methamphetamine ( 1 , 2 ) most o f the comparison analyses have d e a l t with h e r o i n . As a r e s u l t o f the c l a n d e s t i n e processes used i n the production of h e r o i n , the final product may contain not only h e r o i n but a l s o monoacetylmorphine, a c e t y l c o d e i n e , opium a l k a -loids, and other t r a c e i m p u r i t i e s . At the s t r e e t level, h e r o i n e x h i b i t s a l s o contain a d u l t e r a n t s such as q u i n i n e , p r o c a i n e , methapyrilene, and various sugars. The determination of all these substances provides a good b a s i s on which t o compare heroin e x h i b i t s . S c h l e s i n g e r et al (3) r e p o r t e d t h a t non-destructive neutron a c t i v a t i o n a n a l y s i s (NAA) can be employed t o compare drugs s o l d in illicit channels through the determination o f t h e i r elemental compositions. This e a r l y work was a m p l i f i e d by Pro and B r u n e l l e (4), combining atomic absorption a n a l y s i s with NAA. Although the determination of elemental composition can be u s e f u l , t h i s approach s u f f e r s from the f a c t that i t may not be used when h e r o i n has been packaged d i f f e r e n t l y or a d u l t e r a t e d with another

170

In Forensic Science; Davies, Geoffrey; ACS Symposium Series; American Chemical Society: Washington, DC, 1975.


18.

SOBOL

A N D SPERLING

Heroin

Samples

171

material. L e r n e r a n d M i l l s (5) r e p o r t e d t h e p r e s e n c e o f 0 ^ - m o n o a c e t y l m o r p h i n e as a common c o n s t i t u e n t i n h e r o i n a n d s u g g e s t e d t h a t t h e r a t i o o f h e r o i n t o m o n o a c e t y l m o r p h i n e w o u l d n o t change d u r i n g a d u l t e r a t i o n . O t h e r s have d e a l t p r i m a r i l y w i t h t h e i d e n t i f i c a t i o n o f the adulterants present, e i t h e r other drug substances o r sugars (6,7). Grooms ( 8 ) and M i l l e r (9) h a v e attempted t o i n c l u d e t h e a n a l y s i s o f adulterants w i t h the presence o f monoacetylmorphine. I n each o f these c a s e s , t h e r e s o l u t i o n o f t h e v a r i o u s components was i n s u f f i c i e n t t o p r o v i d e good q u a n t i t a t i v e d a t a . We h a v e d e v e l o p e d method f o r t h e 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 o f h e r o i n , 0 -monoacetylmorphine, a c e t y l c o d e i n e , morphine, and c o d e i n e w h i c h i s a p p l i c a b l e t o a w i d e v a r i e t y o f h e r o i n samples. Since t h e r e l a t i v e p r o p o r t i o n o f these substances s h o u l d r e m a i n u n c h a n g e d d u r i n g any a d d i t i o n a l h a n d l i n g o f t h e m a t e r i a l , t h i s method e n a b l e s one t o compare s e e m i n g l y u n l i k e h e r o i n samples. This i n f o r m a t i o n , coupled w i t h other a n a l y t i c a l i n f o r m a t i o n s u c h as t h e p h y s i c a l a p p e a r a n c e o f t h e e x h i b i t and t h e p r e s e n c e o r a b s e n c e o f a d u l t e r a n t s , p r o v i d e s a good b a s i s on w h i c h t o compare e x h i b i t s . Two p r o c e d u r e s a r e p r e s e n t e d f o r t h e a n a l y s i s o f t h e s e h e r o i n i m p u r i t i e s , one i n v o l v i n g d e r i v a t i z a t i o n o f t h e m a t e r i a l f o l l o w e d b y gas c h r o m a t o g r a p h i c a n a l y s i s , and t h e o t h e r a d i r e c t gas ch romat o g r a p h i c a n a l y s i s . The d e r i v a t i z a t i o n method i s t h e p r e f e r r e d p r o c e d u r e i n t h a t a l l components a r e w e l l r e s o l v e d on t h e chromâtogram w h e r e a s 0 ^ - m o n o a c e t y l m o r p h i n e and a c e t y l c o d e i n e a r e n o t t o t a l l y s e p a r a t e d i n t h e d i r e c t method. A l s o , t h e r e p r o d u c i b i l i t y o f t h e f o r m e r has been f o u n d t o be superior. A l t h o u g h t h e d e r i v a t i z a t i o n method i s p r e f e r r e d , i t i s n o t a p p l i c a b l e t o many h e r o i n e x h i b i t s , due t o t h e a d u l t e r a n t s present. Sugars, i n p a r t i c u l a r , w i l l react with s i l y l a t i n g reagents, thus causing incomplete r e a c t i o n o f the reagent w i t h t h e i m p u r i t i e s o f i n t e r e s t o r i n t e r f e r i n g w i t h t h e peaks o f i n t e r e s t i n t h e chromâtogram. T h e r e f o r e , p r e l i m i n a r y s c r e e n i n g c o n s i s t i n g o f m i c r o s c o p i c e x a m i n a t i o n , c o l o r and c r y s t a l t e s t s , and t h i n - l a y e r chromat οgraphy must be p e r f o r m e d t o t e n t a t i v e l y i d e n t i f y t h e a d u l t e r a n t s p r e s e n t , i f any. 6

Derivatization

Procedure.

Transfer a p o r t i o n o f t h e e x h i b i t equivalent t o approximate l y 25 mg o f h e r o i n t o a 1 m l g l a s s - s t o p p e r e d t e s t t u b e . Add 0.2 m l o f c h l o r o f o r m a n d 0.3 m l o f Ν, 0 - B i s - ( t r i m e t h y I s i l y l ) t r i f l u o r o a c e t ami de ( B S T F A ) . M i x a n d h e a t a t 75°C f o r n i n e t y m i n u t e s g i v i n g t h e t u b e an o c c a s i o n a l s h a k e . Use 2-5 m i c r o l i t e r s o f t h e s o l u t i o n f o r gas c h r o m a t o g r a p h i c a n a l y s i s . Due t o t h e w i d e d i f f e r e n c e s i n c o n c e n t r a t i o n s o f t h e s e s u b s t a n c e s u s u a l l y f o u n d i n h e r o i n e x h i b i t s , t h e peak a r e a s must



172

FORENSIC

SCIENCE

be determined on an e l e c t r o n i c i n t e g r a t o r . To obtain a r e l a t i v e concentration o f these components, the area normalizat i o n technique i s u t i l i z e d . The peak area o f each component o f i n t e r e s t i s d i v i d e d by the sum t o t a l peak area obtained i n the chromâtοgram and m u l t i p l i e d by 100. For example, the percentage o f morphine would be determined by the f o l l o w i n g formula : Area o f morphine-TMS peak χ 100 T o t a l peak area i n chromâtοgram Equipment : Gas Chromâtograph: Perkin-Elmer Model 900 E l e c t r o n i c I n t e g r a t o r : I n f o t r o n i c s CRS-101 Gas Chromatographic Conditions : Detector: flame i o n i z a t i o n C a r r i e r gas : n i t r o g e n Flow rate : 60 ml/min. Column : g l a s s column, 6 f t . χ 1/4 i n . packed with 3% OV-25 on Gas Chrom Q*, 100/120 mesh Injector Temperature : 26 5° C Column Temperature :

approximately 240°C

Detector Temperature : 265°C The column temperature should be adjusted t o give the f o l l o w i n g r e t e n t i o n times : APPROXIMATE RETENTION COMPOUND TIME IN MINUTES Morphine-T MS Codeine-TMS 0 -monoacetylmorphine -TMS Acetylcodeine Heroin 6

5.6 6.7 9. 8 12. 4 19.0

A t y p i c a l chromâtogram i s shown i n F i g u r e 1. Morphine and codeine u s u a l l y occur i n the samples at very low concentrations. Under the conditions used the p r a c t i c a l lower l i m i t of d e t e c t i o n i s approximately 15 t o 25 nanograms. L i n e a r i t y s t u d i e s were run and the compounds were found t o be l i n e a r i n at l e a s t the ranges i n d i c a t e d .

Applied Science L a b o r a t o r i e s , Inc., State College , Pa.



18.

SOBOL

AND

SPERLING

Heroin

Samples

COMPOUND

RANGE

Codeine-TMS Morphine-TMS 0 ^ - m o n o a c e t y l m o r p h i n e -TMS Acetylcodeine

25 25 1 1

nanograms nanograms microgram microgram

173

to to to to

2 4 7 9

micrograms micrograms mi c r ο grams micrograms

To c h e c k on t h e r e p r o d u c i b i l i t y o f i n j e c t i o n s , f o u r s a m p l e s were s t u d i e d . They were i n j e c t e d t e n t i m e s e a c h a t a c o n c e n t r a t i o n o f 60 mg/ml and t e n t i m e s e a c h a t a c o n c e n t r a t i o n o f 10 mg/ml. The r a n g e and c o e f f i c i e n t s o f v a r i a t i o n were c a l c u l a t e d and a r e g i v e n i n T a b l e I . D i r e c t Gas C h r o m a t o g r a p h i c A n a l y s i s . As m e n t i o n e d a b o v e , c o m p l e t e s e p a r a t i o n o f components u s i n g t h i s p r o c e d u r e c a n n o t be a c h i e v e d , ( F i g u r e 2 ) . Acetylcodeine i s n o t c o m p l e t e l y r e s o l v e d f r o m 0 " - m o n o a c e t y l m o r p h i n e and t h u s t h e peak a r e a s r e p r e s e n t o n l y a good e s t i m a t e o f t h e r a t i o s . A l s o , because o f t h e a d d i t i o n a l substances present i n a d u l t e r a t e d s a m p l e s , t h e peak a r e a n o r m a l i z a t i o n method i s a p p l i e d o n l y t o t h o s e p e a k s due t o h e r o i n p r o c e s s i n g , i n c l u d i n g opium a l k a l o i d s , i f present. To a p p r o x i m a t e l y 30 mg o f sample , add 0.5 m l o f m e t h a n o l . Use 2-5 m i c r o l i t e r s f o r gas c h r o m a t o g r a p h i c a n a l y s i s . Equipment : Chromâtograph: P e r k i n - E l m e r M o d e l 900 Electronic Integrator: I n f o t r o n i c s CRS-101 Gas C h r o m a t o g r a p h i c C o n d i t i o n s : Detector: flame i o n i z a t i o n C a r r i e r Gas : n i t r o g e n F l o w r a t e : a p p r o x i m a t e l y 60 m l / m i n . Column : g l a s s column 6 f t . χ 1/4 i n . p a c k e d w i t h 3% 0V-25 on Gas Chrom Q*, 100/120 mesh Injector Temperature :

275°C

Column T e m p e r a t u r e : Detector Temperature:

265°C 275°C

* A p p l i e d Science L a b o r a t o r i e s , I n c . , S t a t e C o l l e g e , Pa. U s i n g t h e s e c o n d i t i o n s , t h e r e t e n t i o n t i m e s a r e as f o l l o w s .


FORENSIC

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SCIENCE


6

Sample 4B Morphine .151 Codeine .034 0^-monoacetyl morphine 2.45 Acetylcodeine 5.46 Heroin 91.7

Sample 4A Morphine .143 Codeine .029 0 -monoacetyl morphine 2.50 Acetylcodeine 5.41 Heroin 91.7

4% 6%

0.7% 0.1%

- 2.52 - 5.59 - 91.9

3.3% 6.2% 0.1%

3.7% 7.9%

C o e f - V a r i a t i on

- .158 - .036

- 2.81 -6.18 - 91.9

- .160 - .037

60 mg/ml Range P e r c e n t

TABLE I ( C o n t i n u e d )

2.26 5.16

.135 .020 - 2.40 - 5.68

.166 .028

10 mg/ml Range P e r c e n t


4.2% 3.3%

6.2% 2.9%

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CO

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FORENSIC

H Ac ACETYLCODEINE


O

6

O-MONOACETYLMORPHINE-TMS

Figure 1.

Derivatized

heroin

Ac ACETYLCODEINE O

6

0 MONOACETYL: e

MORPHINE C

CODEINE

H

HEROIN

M

MORPHINE

Figure 2.

Ac.

Underivatized

heroin


SCIENCE

18.

SOBOL A N D SPERLING


COMPOUND Methapyrilene Procaine Acetylprocaine Codeine Morphine Acetylcode i n e 0^-monoacetylmorphine Thebaine Heroin Papaverine Noscapine*

Heroin

177

Samples

APPROXIMATE RETENTION TIME IN MINUTES 1.0 1.1 2.5 3.4 3.9 4.5 4.7 5.7 6.6 13.5 32.2

* Noscapine has been found to occur i n such low concentra t i o n s that i t i s not u s u a l l y detected under the above c o n d i t i o n s . The above techniques have been used i n t h i s l a b o r a t o r y on over 100 d i f f e r e n t h e r o i n e x h i b i t s i n the past two y e a r s . For the most p a r t , the analyses have been l i m i t e d t o s p e c i f i c e x h i b i t s where i n t e l l i g e n c e had i n d i c a t e d a probable connection between two or more cases. The l a b o r a t o r y examination was requested t o prove or disprove t h i s connection. The f o l l o w i n g s t u d i e s demonstrate how the a n a l y t i c a l information can be used. Table I I shows the percent o f heroin-HCl i n e i g h t e x h i b i t s . The f i r s t s i x e x h i b i t s are a s s o c i a t e d with a case o r i g i n a t i n g i n Texas ; the l a s t two e x h i b i t s are a s s o c i a t e d with a case o r i g i n a t i n g i n Michigan. The microscopie appearance o f the three uncut h e r o i n e x h i b i t s was i d e n t i c a l (T 1775, Τ 1776 , M 1832). The microscopie appearance o f the f i v e samples cut with l a c t o s e r e v e a l e d the presence o f p o o r l y c r y s t a l l i z e d l a c t o s e monohydrate. The X-ray d i f f r a c t i o n patterns of a l l the cut samples were s i m i l a r . Table I I I shows the r a t i o s o f the impuri t i e s present i n each o f the e x h i b i t s . Even though many o f the e x h i b i t s had been c u t , a constant r e l a t i o n s h i p o f the r e l a t i v e con cent rat i ons o f the by-products was found, except with the l a s t sample (M 1833). From these r e s u l t s , we concluded that the h e r o i n i n one o f the e x h i b i t s (M 1832) i n the Michigan case d i d correspond with those found i n Texas. We a l s o concluded that a l l e x h i b i t s o f the Texas case came from a common source, a n d , f i n a l l y , that two sources o f h e r o i n e x i s t e d i n the Michigan case. The comparison o f h e r o i n e x h i b i t s has a l s o been used s u c c e s s f u l l y i n court i n h e l p i n g t o e s t a b l i s h a conspiracy. Comparative analyses were conducted on f i v e e x h i b i t s from two d i f f e r e n t cases. The p r e l i m i n a r y examination r e v e a l e d t h a t the e x c i p i e n t s and d i l u e n t s i n each case were: sucrose, quinine h y d r o c h l o r i d e , mannitol, corn s t a r c h , and l a c t o s e monohydrate.


FORENSIC

TABLE I I


H e r o i n Comparison Percent L a b , No.

Heroin-HCl

Lactose

Τ 1771

30.2

+

Τ 1772

32.6

+

Τ 177^

31Λ

+

Τ 1775

9^.9

Τ 1776

93-0

Τ 1777

36.0

Μ 1832

95.1

Μ 1833

19-3

+

+


SCIENCE


-

-

-

0.03

-

-

0.03

0.03

Τ 1772

Τ 1774

Τ 1775

Τ 1776

Τ 1777

Μ 1832

Μ 1833

Morphine

T 1771

Lab. No.

6

2.40

1.92

1.80

1.95

1.90

1.89

1.81

1.70

0 -MonoacetylMorphine

Ratio o f By-Products

TABLE I I I

0.30

0.10

-

0.12

0.06

-

0.09

0.13

Codeine


3.35

3.13

3.01

3.25

2.97

2.88

2.85

2.69

AcetylCodeine

93.2

94.8

95.2

94.7

95.0

94.7

95.2

95.5

HeroinHC1


1 2

Exh.

1

Exh. 2

17.9

14.0 18.7 17.0 18.1 17.7 17.8 17.3 17.7 18.5 17.1 17.1

19.2

5

1 2 3 4 5 6 7 8 9 10 11

17.1 16.5 16.5

1

Heroin>HCl

1 2 3

Exh.

Packet #

Assay,%

4.32

4.49 4.88 3.24 3.93 4.18 4.39 4.33 3.90 3.94 3.69 4.32

4.49

4.62 5.43 4.64

Quinine- HC1

TABLE IV

0

6

2.57 3.77

4.19 3.98 2.53 4.05 3.59 2.14 2.66 2.66 4.00 2.86

1.76 2.09 3.98 3.27 3.27

Monoacetylmorphine

0.90 0.85

0.82 1.18 0.73 0.71 0.68 1.02 1.14 1.14 0.79 0.85

0.82 0.80 0.69 0.80 0.80

Acetylcode i n e

Profilej%


96.5 95.4

95.0 94.8 96.7 95.2 95.7 96.8 96.2 96.2 95.2 96.3

97.4 97.1 95.3 95.9 95.9

Heroin


1 2

Exh

3

Exh. 2

16.6

17.7 18.4 18.1 18.2 17.7 17.2 18.1 17.0 15.9

Heroin*HC1

4.56

4.24 3.97 4.35 4.02 3.76 4.57 4.09 4.26 5.37

Quinine»HC1

1

2.05 1.72

6.07 1.78 5.57 3.50 2.73 6.64 3.43 4.76 2.50 1.86

0.93 0.90

0.86 1.11 0.68 0.79 0.76 0.85 0.92

0.77 0.80

Profile^ 0^ Monoacetylmorphine Acetylcodeine

(Continued)

Heroin

97.0 97.4

93.2 97.5 94.4 95.6 96.2 92.7 95.8 94.5 96.7 97.2

These percentages are determined by d i v i d i n g the area obtained f o r each a l k a l o i d by the t o t a l area f o r a l l three a l k a l o i d s .

1 2 3 4 5 6 7 8 9 10

Packet §

Assay,%

TABLE



182

FORENSIC SCIENCE

Q u a n t i t a t i v e a n a l y s i s showed that t h e concentrations o f h e r o i n and quinine i n a l l e x h i b i t s were approximately equal. The determination o f the r e l a t i v e concentrations o f h e r o i n impuri t i e s are given i n Table IV, and were a l l s i m i l a r . Expert testimony was given that a l l f i v e e x h i b i t s o r i g i n a t e d from a common source and t h i s testimony was an i n t e g r a l part o f the prosecution*s case e s t a b l i s h i n g a conspiracy. Work i s continuing on the a n a l y s i s o f h e r o i n e x h i b i t s t o develop a l a r g e r data base. Work i s also continuing on more q u a n t i t a t i v e methods f o r a d u l t e r a t e d h e r o i n samples. In c o n c l u s i o n , methods have been presented f o r the comparison o f h e r o i n samples. These a n a l y t i c a l procedures have been s u c c e s s f u l l y used f o r both i n t e l l i g e n c e purposes and court testimony. Literature Cited 1. L e B e l l e , Μ., Sileika, Μ., and Romack, Μ., (1973) J . PHARM. SCI., 62, 862. 2. Barron, R., Kruegel, A., Moore, J. and Kram, T., J. ASSOC. OFFICIAL ANAL. CHEM. ( i n p r e s s ) . 3. S c h l e s i n g e r , Η., P r o , Μ., Hoffman, D., and Cohan, Μ., (1965), J. ASSOC. OFFICIAL ANAL. CHEM., 48, 1139-1147. 4. P r o , M. and B r u n e l l e , R., (1970), J. ASSOC. OFFICIAL ANAL. CHEM., 53, 1137-1139. 5. L e m e r , M. and Mills, A., (1963), U.N. BULL. NARCOTICS, 15, 37. 6. F u l t o n , C., (1965), INTERN. MICROFILM J. LEGAL MED., 1, Card 2, G-1. 7. B r o i c h , J., DeMayo, Μ., and D a l C o r t i v o , L., (1968) J . CHROM., 33, 526-529. 8. Grooms, J., (1968), J. ASSOC. OFFICIAL ANAL. CHEM., 51, 1010-1013. 9. M i l l e r , Μ., (1972), J. FORENSIC SCIENCES 16 , 150-163.


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