title: THCVA-A - a new additional marker for illegal cannabis consumption.
abstract: The aim of the present investigations was to find markers for differentiating between the consumption of illegal cannabis products and legal medication containing fully synthetic Δ9-tetrahydrocannabinol (Δ9-THC), e.g., Marinol capsules. Δ9-Tetrahydrocannabinolic acid A (Δ9-THCA-A) and Δ9-tetrahydrocannabivarinic acid A (Δ9-THCVA-A) were taken into consideration for analysis, because these substances are the precursors of Δ9-THC and Δ9-tetrahydrocannabivarin (Δ9-THCV) in plant material of Cannabis sativa and are not contained in medical THC formulations. Whereas Δ9-THCA-A is an already well investigated substance, there is little analytical data on Δ9-THCVA-A. The reason for the presented investigations was a case in which a man was tested positive for Δ9-THC during a routine traffic control claiming that the positive serum sample resulted from the intake of a THC medication (Marinol) and not from consuming illegal cannabis products. Sample preparation consisted of a protein precipitation with acetonitrile. Analysis was carried out on a Thermo Fisher LCQ Deca ion trap LC-MS-MS-system using electron spray ionization (ESI) in negative mode. MS(2)- and MS(3)-full scan spectra were recorded for Δ9-THCA-A and Δ9-THCVA-A starting from [M-H](-). Reference spectra were obtained by measuring a Δ9-THCA-A reference solution and an ethanolic cannabis extract for Δ9-THCVA-A as there is no reference material for this cannabinoid available on the market yet. Main transitions for Δ9-THCA-A were m/z 357→313 and 339 in the MS(2)-spectrum and m/z 313→245 and 191 in the MS(3)-spectrum. Fragmentation pattern of Δ9-THCVA-A was identical with a difference of 28 amu less for the precursor ion as well as the fragments due to a shorter alkyl side chain in the molecule (MS(2): m/z 329→285 and 311; MS(3): m/z 285→217 and 163). The two plant cannabinoids Δ9-THCA-A and Δ9-THCVA-A could be detected in the serum sample by LC-MS-MS which proved the intake of illegal cannabis products derived from plant material of C. sativa in the described case.
authors: Institute of Legal Medicine, University Hospital Schleswig-Holstein, Campus Kiel, Arnold-Heller-Str. 12, 24105 Kiel, Germany. lars.raduenz@freenet.de
authors: Lars
authors: L
authors: Radünz
authors: Folker
authors: F
authors: Westphal
authors: Edmund
authors: E
authors: Maser
authors: Gertrud
authors: G
authors: Rochholz