Solid phase microextraction and gas chromatography–mass spectrometry methods for residual solvent assessment in seized cocaine and heroin

Abstract

A simple sample pre-treatment method based on solid phase microextraction (SPME) and gas chromatography–mass spectrometry (GC-MS) has been optimized and validated for the assessment of 15 residual solvents (2-propanol, 2-methylpentane, 3-methylpentane, acetone, ethyl acetate, benzene, hexane, methylcyclohexane, methylcyclopentane, m-xylene, propyl acetate, toluene, 1,2,4-trimethylbenzene, dichloromethane, and ethylbenzene) in seized illicit cocaine and heroin. DMSO and DMF as sample diluents were found to offer the best residual solvent transference to the head space for further adsorption onto the SPME fiber, and the developed method therefore showed high sensitivity and analytical recovery. Variables affecting SPME were fully evaluated by applying an experimental design approach. Best conditions were found when using an equilibration time of 5 min at 70 °C and headspace sampling of residual solvents at the same temperature for 15 min. Method validation, performed within the requirements of international guidelines, showed excellent sensitivity, as well as intra- and inter-day precision and accuracy. The proposed methodology was applied to 96 cocaine samples and 14 heroin samples seized in Galicia (northwestern Spain) within 2013 and 2014.

This is a preview of subscription content, access via your institution.

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5

References

  1. 1.

    ICH Topic Q3C (R4) Impurities: guideline for residual solvents. European Medicines Agency, 2010. www.ema.europa.eu

  2. 2.

    Mulligan K, Brueggemeyer TW, Crockett D, Schepman J. Analysis of organic volatile impurities as a forensic tool for the examination of bulk pharmaceuticals. J Chromatogr B. 1996;686:85–95.

    CAS  Article  Google Scholar 

  3. 3.

    Chiarotti M, Marsili R, Moreda-Piñeiro A. Gas chromatographic-mass spectrometric analysis of residual solvent trapped into illicit cocaine exhibits using head-space solid-phase microextraction. J Chromatogr B. 2002;772:249–56.

    CAS  Article  Google Scholar 

  4. 4.

    Sköld KS. Validation of a generic analytical procedure for determination of residual solvents in drug substances. J Pharm Biomed. 2004;36:401–9.

    Article  Google Scholar 

  5. 5.

    Cheng C, Liu S, Mueller B, Yan Z. A generic static headspace gas chromatography method for determination of residual solvents in drug substance. J Chromatogr A. 2010;1217:6413–21.

    CAS  Article  Google Scholar 

  6. 6.

    Otero R, Carrera G, Dulsat JF, Fábregas JL, Claramunt J. Static headspace gas chromatography method for quantitative determination of residual solvents in pharmaceutical drug substances according to European Pharmacopoeia requirements. J Chromatogr A. 2004;1057:193–201.

    CAS  Article  Google Scholar 

  7. 7.

    El-Haj BM, Al-Amri AM, Ali HS. Heroin profiling: mannitol hexaacetate as an unusual ingredient of some illicit drug seizures. Forensic Sci Int. 2004;145:41–6.

    CAS  Article  Google Scholar 

  8. 8.

    Collins M, Casale E, Hibbert B, Panicker S, Robertson J, Vujic S. Chemical profiling of heroin recovered from the north Korean Merchant Vessel Pong Su. J Forensic Sci. 2006;51(3):597–602.

    CAS  Article  Google Scholar 

  9. 9.

    Casale J, Boudreau D, Jones L. Tropane ethyl esters in illicit cocaine: isolation, detection and determination of new manufacturing by-products from the clandestine purification of crude cocaine base with ethanol. J Forensic Sci. 2008;53(3):661–7.

    CAS  Article  Google Scholar 

  10. 10.

    Esseiva P, Gaste L, Alvarez D, Anglada F. Illicit drug profiling, reflection on statistical comparisons. Forensic Sci Int. 2011;207:27–34.

    CAS  Article  Google Scholar 

  11. 11.

    Debrus B, Broséus J, Guillarme D, Lebrun P, Hubert P, Veuthey JL, et al. Innovative methodology to transfer conventional GC-MS heroin profiling to UHPLC-MS/MS. Anal Bioanal Chem. 2011;399:2719–30.

    CAS  Article  Google Scholar 

  12. 12.

    B’Hymer C. Residual solvent testing: a review of gas chromatographic and alternative techniques. Pharm Res-Dordr. 2003;20(3):337–44.

    Article  Google Scholar 

  13. 13.

    Urakami K, Higashi A, Umemoto K, Godo M. Matrix media selection for the determination of residual solvents in pharmaceuticals by static headspace gas chromatography. J Chromatogr A. 2004;1057:203–10.

    CAS  Article  Google Scholar 

  14. 14.

    Guidance for industry. Bioanalytical method validation. U.S. Department of Health and Human Services. Food and Drug Administration (FDA). 2013

  15. 15.

    Dujourdy L, Besacier F. Headspace profiling of cocaine samples for intelligence purposes. Forensic Sci Int. 2008;179:111–22.

    CAS  Article  Google Scholar 

Download references

Acknowledgments

The authors wish to thank the European Commission Directorate-General Justice (JUST/2011/ISEC/DRUGS/AG/3670) for support in this investigation.

Author information

Affiliations

Authors

Corresponding author

Correspondence to Ana María Bermejo.

Ethics declarations

Conflict of interest

The authors declare that they have no conflict of interest.

Electronic supplementary material

Below is the link to the electronic supplementary material.

ESM 1

(PDF 173 kb)

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

Cabarcos, P., Herbello-Hermelo, P., Álvarez-Freire, I. et al. Solid phase microextraction and gas chromatography–mass spectrometry methods for residual solvent assessment in seized cocaine and heroin. Anal Bioanal Chem 408, 6393–6402 (2016). https://doi.org/10.1007/s00216-016-9754-y

Download citation

Keywords

  • Residual solvents
  • Seized cocaine
  • Seized heroin
  • GC-MS
  • SPME