Methods for impurity profiling of heroin and cocaine

72

Methods for impurity profiling of heroin and cocaine

Figure VI. GC-ECD chromatogram of the determination of truxillines 

in a cocaine comparison case

(Truxillines indicated by square bracket)

Source: J. M. Moore and J. F. Casale, “Cocaine profiling methodology: recent advances”, Forensic

Science Review, vol. 10, 1998, pp. 13-46. Copyright Forensic Science Review. Reprinted with per-

mission.

---

Annex III

73

Figure VII. Expanded “window” of the chromatogram in figure VI, 

showing chromatography and identification of the individual truxillines

Source:  J. M. Moore and J. F. Casale, “Cocaine profiling methodology: recent advances”, Forensic

Science Review, vol. 10, 1998, pp. 13-46. Copyright Forensic Science Review. Reprinted with per-

mission.

Truxilline isomers:

---

---

BIBLIOGRAPHY

A.

General

Cartier, J., O. Guéniat and M. D. Cole. Headspace analysis of solvents in cocaine and

heroin samples. Science and justice (Harrogate, United Kingdom) 37:3:175-181, 1997.

Morello, D. R., and R. P. Meyers. Qualitative and quantitative determination of residual

solvents in illicit cocaine HCl and heroin HCl. Journal of forensic sciences (West

Conshohocken, Pennsylvania) 40:6:957-963, 1995.

United Nations. The feasibility of using chemical characteristics for identifying sources of

heroin and for tracking its movement in the illicit traffic; report of an expert group, Hong

Kong, 17-21 October 1977. 24 p. (MNAR/8/1977) Mimeographed.

__________. Drug characterization/impurity profiling; background and concepts; manual

for use by national law enforcement authorities and drug testing laboratories. 2001. 14 p.

(ST/NAR/32/Rev.1) Sales No. E.01.XI.10.

__________. Economic and Social Council. Commission on Narcotic Drugs. Report of the

expert group to coordinate research on the physical and chemical characteristics of heroin

to trace its origin and movement in the illicit traffic. 15 November 1982.

(E/CN.7/1983/2/Add.4)

__________. Report of the consultative meeting on chemical characterization/profiling of

drug seizures, Vienna, 30 November-2 December 1992. 18 p.

B.

Heroin

Ahond, A., and others. Modification de la réaction de Polonovski; préparation d’un nou-

veau réactif de Mannich. Bulletin de la société chimique de France 7:2707-2710, 1970. 

Allen, A. C., and others. 

ͬ-

16,17

-Dehydroheroinium chloride; synthesis and characterization

of a novel impurity detected in illicit heroin. Journal of organic chemistry (Washington,

D.C.) 48:22:3951-3954, 1983.

__________, and others. Thebaine rearrangements; nonclassical D ring migrations. Journal

of organic chemistry (Washington, D.C.) 49:19:3462-3465, 1984.

75

---

76

Methods for impurity profiling of heroin and cocaine

__________,  and others. Illicit heroin manufacturing byproducts; capillary gas chromato-

graphic determination and structural elucidation of narcotine- and norlaudanosine-related

compounds.  Analytical chemistry (Washington, D.C.) 56:14:2940-2947, 1984.

Barnfield, C., and others. The routine profiling of forensic heroin samples. Forensic sci-

ence international (Shannon, Ireland) 39:2:107-117, 1988.

Bedford, K. R., and others. The illicit preparation of morphine and heroin from pharma-

ceutical products containing codeine; “homebake” laboratories in New Zealand. Forensic

science international (Shannon, Ireland) 34:3:197-204, 1987.

Bernhauer, D., E. F. Fuchs and H. Neumann. Nachweis von 3-O-Acetylmorphin als

Zersetzungsprodukt des Diacetylmorphins (Heroin) mit HPLC und Capillar-GC. Fresenius’

Zeitschrift für analytische Chemie (Berlin) 316:501-504, 1983.

__________,  and others. Zum Auftreten von O

3

-Monoacetylmorphin in Heroinproben.

Archiv für Kriminologie 168:139-148, 1981.

Besacier, F., and H. Chaudron-Thozet. Chemical profiling of illicit heroin samples. Forensic

science  review (Taipei, Taiwan Province of China) 11:2:105-119, 1999.

__________, and others. Isotopic analysis of 

13

C as a tool for comparison and origin assign-

ment of seized heroin samples. Journal of forensic sciences (West Conshohocken,

Pennsylvania) 42:3:429-434, 1997.

Bora, T., M. Merdivan and C. Hamamci. Levels of trace and major elements in illicit heroin.

Journal of forensic sciences (West Conshohocken, Pennsylvania) 47:5:959-963, 2002.

Cooper, D. C., A. C. Allen and J. M. Moore. Mass spectral identification of neutral impu-

rities found in heroin samples. In  Proceedings of 31st Annual Conference on Mass

Spectrometry and Allied Topics, Boston, Massachusetts, 8-13 May 1983.

Dams, R., and others. Heroin impurity profiling; trends throughout a decade of experi-

menting.  Forensic science international (Shannon, Ireland) 123:1-2:81-88, 2001.

__________,  and others. Sonic spray ionization technology; performance study and appli-

cation to a LC/MS analysis on a monolithic silica column for heroin impurity profiling.

Analytical chemistry (Washington, D.C.) 74:13:3206-3212, 2002.

Dautraix, S., and others.

13

C Isotopic analysis of an acetaminophen and diacetylmorphine

mixture.  Journal of chromatography A (Amsterdam) 756:1-2:203-210, 1996.

Desage, M., and others. Gas chromatography with mass spectrometry or isotope-ratio mass

spectrometry in studying the geographical origin of heroin. Analytica chimica acta

(Amsterdam) 247:2:249-254, 1991.

Dujourdy, L., and others. Evaluation of links in heroin seizures. Forensic science interna-

tional  (Shannon, Ireland) 131:2-3:171-183, 2003.

---

Bibliography

77

Ehleringer, J. R., and others. Geo-location of heroin and cocaine by stable isotope ratios.

Forensic science international (Shannon, Ireland) 106:1:27-35, 1999.

Esseiva, P., and others. A methodology for illicit heroin seizures comparison in a drug

intelligence perspective using large databases. Forensic science international (Shannon,

Ireland) 132:2:139-152, 2003.

Gloger, M., and H. Neumann. Analysis of heroin samples by capillary gas chromatogra-

phy; comparison of glass capillary column and packed column. Forensic science interna-

tional  (Shannon, Ireland) 22:1:63-74, 1983.

Gol’dfarb, Y. L., and L. I. Belen’kii. Comment; concurring the paper of R. P. Mariella

and K. H. Brown “A novel SN1 displacement: the reaction of tertiary amines with acetic

anhydride”.  Canadian journal of chemistry (Ottawa) 51:2174, 1973. 

Gonzalez, J., and others. Authentication of lemon juices and concentrates by a combined

multi-isotope approach using SNIF-NMR and IRMS. Journal of agricultural and food

chemistry  (Washington, D.C.) 46:6:2200-2205, 1998.

Hayashi, Y., and others. Trapping an intermediate of the Polonovski reaction. Tetrahedron

letters (Oxford, United Kingdom) 15:14:1299-1302, 1974.

Huizer, H. Analytical studies on illicit heroin; I. The occurrence of O

3

-monoacetylmor-

phine.  Journal of forensic sciences (West Conshohocken, Pennsylvania) 28:1:32-39, 1983.

Ihle, E., and H. L. Schmidt. Multielement isotope analysis on drugs of abuse; possibility

for their origin assignment. Isotopes in environmental and health studies (Abingdon, United

Kingdom) 32:226-228, 1996.

Infante, F., and others. Metal contamination in illicit samples of heroin. Journal of foren-

sic sciences (West Conshohocken, Pennsylvania) 44:1:110-113, 1999.

Jamin, E., and others. Improved detection of sugar addition to apple juices and 

concentrates using internal standard 

13

C IRMS. Analytica chimica acta (Amsterdam)

347:3:359-368, 1997.

__________, N. Naulet and G. J. Martin. Multi-element and multi-site isotopic analysis of

nicotine from tobacco leaves. Plant, cell and environment (Oxford, United Kingdom)

20:5:589-599, 1997.

Janhunen, K., and M. D. Cole. Development of a predictive model for batch membership of

street samples of heroin. Forensic science international (Shannon, Ireland) 102:1:1-11, 1999.

Johnston, A.,  and L. A. King. Heroin profiling; predicting the country of origin of seized

heroin.  Forensic science international (Shannon, Ireland)  95:1:47-55, 1998.

Klein, M. Analysis of impurities in illicit heroin by mass spectrometry. In Mass spectrom-

etry in drug metabolism. A. Frigerio and E. Ghisalberti, eds. New York, Plenum Publishing,

1977. p. 449-463.

---

78

Methods for impurity profiling of heroin and cocaine

Klemenc, S. In common batch searching of illicit heroin samples; evaluation of data by chemo-

metrics methods. Forensic science international (Shannon, Ireland) 115:1-2:43-52, 2001.

__________. Noscapine as an adulterant in illicit heroin samples. Forensic science inter-

national  (Shannon, Ireland) 108:1:45-49, 2000.

Lurie, I. S., and S. M. Carr. The quantitation of heroin and selected basic impurities via

reversed phase HPLC; I. The analysis of unadulterated heroin samples. Journal of liquid

chromatography and related technologies (New York) 9:11:2485-2509, 1986.

__________, and A. C. Allen. Isolation, separation and detection via high-performance liq-

uid chromatography of acidic and neutral acetylated rearrangement products of opium alka-

loids.  Journal of chromatography A (Amsterdam) 317:427442, 1984.

__________,  and others. Use of dynamically coated capillaries for the determination of

heroin, basic impurities and adulterants with capillary electrophoresis. Journal of chro-

matography A (Amsterdam) 1034:1-2: 227-235, 2004. 

Mariella, R. P., and K. K. Brown. A novel SN1 displacement: the reaction of tertiary

amines with acetic anhydride. Canadian journal of chemistry (Ottawa) 49:3348, 1971. 

__________, and K. K. Brown. Comment; concurring the cleavage of tertiary amines with

acetic anhydride. Canadian journal of chemistry (Ottawa) 51:2177, 1973.

Myors, R. B., and others. Investigation of heroin profiling using trace organic impurities.

Analyst (Cambridge, United Kingdom) 126:5:679-689, 2001.

Neumann, H. Comments on the routine profiling of illicit heroin samples. Forensic sci-

ence international (Shannon, Ireland) 44:1:85-87, 1990.

__________. Comparison of heroin by capillary gas chromatography in Germany. Forensic

science international (Shannon, Ireland) 69:1:7-16, 1994.

__________. Vergleichende Heroinanalyse mit der Kapillar-GC; Bestimmung charakteris-

tischer Größen.  Toxichem+Krimtech  (Berlin) 59:3-4:121-124, 1992.

__________,  and G. Vordermaier. Anwendung der NMR-Spektrometrie zur schnellen

Identifizierung von O

3

- und O

6

-Monoacetylmorphin in Heroinproben.  Archiv für

Kriminologie 167:1-2:33-42, 1981. 

__________,  and M. Gloger. Profiling of illicit heroin samples by high-resolution capil-

lary gas chromatography for forensic application. Chromatographia (Wiesbaden, Germany)

16:261264, 1982.

Polonovski, M., and M. Polonovski. Sur les aminoxydes des alcaloïdes (II). Bulletin de la

société chimique de France 41:116:1186-1190, 1927. 

__________,  and M. Polonovski. Sur les aminoxydes des alcaloïdes; III. Action des an-

hydrides et chlorures d’acides organiques; préparation des bases Nor.  Bulletin de la société

chimique de France 41:117:1190-1208, 1927.

---

Bibliography

79

Pupin, A. M., and others. Use of isotopic analyses to determine the authenticity of Brazilian

orange juice (Citrus sinensis).  Journal of agricultural and food chemistry (Washington,

D.C.) 46:4:1369-1373, 1998.

Roßmann, A., and H.-L. Schmidt. Assignment of ethanol origin and proof of sugar addi-

tion to wine through positional 

2

H and 

13

C isotope ratio measurement. Zeitschrift für

Lebensmitteluntersuchung und -Forschung (Heidelberg) 188:434-438, 1989.

Strömberg, L., and others. Heroin impurity profiling; a harmonization study for retrospec-

tive comparisons. Forensic science international (Shannon, Ireland) 114:2:67-88, 2000.

Tamminen, T., and others. Indoloquinolizidine iminium species formed under the modi-

fied Polonovski reaction conditions. Tetrahedron (Oxford, United Kingdom) 45:9:2683-

2692, 1989.

United Nations. Recommended methods for testing opium, morphine and heroin; manual

for use by national drug testing laboratories. 1998. 71 p. (ST/NAR/29/Rev.1).

Wells, R. J., and others. Trace element analysis of heroin by ICP-MS. Chemistry in

Australia (Melbourne) 62:7:14, 1995.

Zhang, B.-L., and others. Characterization of glycerol from different origins by 

2

H- and

13

C-NMRE studies of site-specific natural isotope fractionation. Journal of agricultural and

food chemistry (Washington, D.C.) 46:4:1374-1380, 1998.

Zhang, D., and others. Component analysis of illicit heroin samples with GC/MS and its

application in source identification. Journal of forensic sciences (West Conshohocken,

Pennsylvania) 49:1:81-86, 2004.

C.

Cocaine

Casale, J. F. A practical total synthesis of cocaine’s enantiomers. Forensic science inter-

national  (Shannon, Ireland) 33:4:275-298, 1987.

__________. Detection of pseudoecgonine and differentiation from ecgonine in illicit

cocaine. Forensic science international (Shannon, Ireland) 47:3:277-287, 1990. Article con-

tains synthesis details for p-fluorococaine. 

__________. Methyl esters of ecgonine: injection-port produced artifacts from cocaine base

(crack) exhibits. Journal of forensic sciences (West Conshohocken, Pennsylvania)

37:5:1295-1310, 1992.

__________, and J. M. Moore. Detection and determination of pseudococaine in coca leaves

and illicit cocaine samples. Journal of forensic sciences (West Conshohocken,

Pennsylvania)  39:6:1537-1543, 1994.

---

80

Methods for impurity profiling of heroin and cocaine

__________,  and J. M. Moore. Lesser alkaloids of cocaine-bearing plants II. 3-Oxo-sub-

stituted tropane esters; detection and mass spectral characterization of minor alkaloids found

in South American Erythroxylum coca var. coca.  Journal of chromatography A

(Amsterdam) 749:1-2:173-180, 1996.

__________,  and J. M. Moore. Lesser alkaloids of cocaine-bearing plants III. 2-

Carbomethoxy-3-oxo substituted tropane esters; detection and gas-chromatographic-mass

spectrometric characterization of new minor alkaloids found in South American

Erythroxylum coca var. coca. Journal of chromatography A (Amsterdam) 756:1-2:185-192,

1996.

__________,  and J. M. Moore. 3’,4’,5’-Trimethoxy-substituted analogs of cocaine, cis-

/trans-cinnamoylcocaine and tropacocaine; characterization and quantitation of new alka-

loids in coca leaf, coca paste and refined illicit cocaine. Journal of forensic sciences (West

Conshohocken, Pennsylvania) 39:2:462-472, 1994.

__________, J. M. Moore and N. G. Odeneal. Comparative determination of 2-car-

bomethoxy-3-alkyloxy- and heteroaroyloxy-substituted tropanes in illicit South American

cocaine using capillary gas chromatography-single ion monitoring.  Journal of forensic sci-

ences (West Conshohocken, Pennsylvania) 43:1:125-132, 1998.

__________, and R. W. Waggoner, Jr. A chromatographic impurity signature profile analy-

sis for cocaine using capillary gas chromatography. Journal of forensic sciences (West

Conshohocken, Pennsylvania) 36:5:1312-1330, 1991.

Clark, C. C. Cocaine comparison parameters. Microgram 11:184-187, 1978.

Ehleringer, J. R., and others. Tracing the geographical origin of cocaine. Nature (London)

408:311-312, 2000.

Janzen, K. E. Cross-matching of cocaine samples; a case study. Canadian Society of

Forensic Science journal (Ottawa) 20:77-81, 1987.

__________, A. R. Fernando and L. Walter. A database for comparison analysis of illicit

cocaine samples. Forensic science international (Shannon, Ireland) 69:1:23-29, 1994.

__________, L. Walter and A. R. Fernando. Comparison analysis of illicit cocaine sam-

ples. Journal of forensic sciences (West Conshohocken, Pennsylvania) 37:2:436-445, 1992.

LeBelle, M., and others. Comparison of illicit cocaine by determination of minor components.

Journal of forensic sciences (West Conshohocken, Pennsylvania) 36:4:1102-1120, 1991.

Lurie, I. S., and others. Isolation, identification and separation of isomeric truxillines in

illicit cocaine. Journal of chromatography A (Amsterdam) 504:391-401, 1990.

__________, and others. Analysis of manufacturing by-products and impurities in illicit

cocaine via high-performance liquid chromatography and photodiode array detection

Journal of chromatography A (Amsterdam) 405:273-281, 1987.

---

Bibliography

81

Moore, J. M. Identification of cis- and trans-cinnamoylcocaine in illicit cocaine seizures.

Journal of the Association of Official Analytical Chemists (Gaithersburg, Maryland)

56:5:1199-1205, 1973.

__________,  and J. F. Casale. Cocaine profiling methodology; recent advances. Forensic

science  review (Taipei, Taiwan Province of China), vol. 10, 1998, pp. 13-46.

__________,  and J. F. Casale. Lesser alkaloids of cocaine-bearing plants; part I.

Nicotinoyl-2’-pyrroloyl, and 2’- and 3’-furanoylecgonine methyl ester—isolation and mass

spectral characterization of four new alkaloids of South American Erythroxylum coca.

Journal of forensic sciences (West Conshohocken, Pennsylvania) 42:2:246-255, 1997.

__________, J. F. Casale and D. A. Cooper. Comparative determination of total isomeric

truxillines in illicit, refined, South American cocaine hydrochloride using capillary gas chro-

matography-electron capture detection. Journal of chromatography A (Amsterdam) 756:1-

2:193-201, 1996.

__________,  and D. A. Cooper. The application of capillary gas chromatography-electron

capture detection in the comparative analyses of illicit cocaine samples.  Journal of foren-

sic sciences (West Conshohocken, Pennsylvania) 38:6:1286-1304, 1993.

__________, R. P. Meyers and M. D. Jimenez. The anatomy of a cocaine comparison case;

a prosecutorial and chemistry perspective. Journal of forensic sciences

(West

Conshohocken, Pennsylvania) 38:6:1305-1325, 1993.

__________, and others.  Capillary gas chromatographic-electron capture detection of coca-

leaf-related impurities in illicit cocaine; 2,4-diphenylcyclobutane-1,3-dicarboxylic acids,

1,4-diphenylcyclobutane-2,3-dicarboxylic acids and their alkaloidal precursors, the trux-

illines.  Journal of chromatography A (Amsterdam) 410:297-318, 1987. 

Morello, D. R., and others. The effects of microwave irradiation on occluded solvents in

illicitly produced cocaine hydrochloride. Journal of forensic sciences (West Conshohocken,

Pennsylvania) 45:5:1126-1132, 2000.

Neumann, H., and T. Holdermann. Comparison of cocaine samples by isotope ratio mass

spectrometry (1998-2001). Unpublished manuscript.

United Nations. Recommended methods for testing cocaine; manual for use by national

narcotics laboratories. 1986. 32 p. (ST/NAR/7)

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Sales No. E.05.XI.14

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Document Outline

• Contents
• I. INTRODUCTION
• II. ASPECTS OF DRUG CHARACTERIZATION AND IMPURITY PROFILING
• III. METHODS FOR IMPURITY PROFILING
• IV. DATA HANDLING, INTERPRETATION OF RESULTS AND APPROACH TO SETTING UP PROFILING DATA COLLECTIONS
• ANNEX I SUPPLEMENTARY INFORMATION (FOR BOTH HEROIN AND COCAINE)
• ANNEX II IMPURITIES IN HEROIN AND COCAINE AND THEIR “SOURCES”
• ANNEX III REFERENCE CHROMATOGRAMS AND PEAK IDENTIFICATION TABLES
• BIBLIOGRAPHY