Proof of active cannabis use comparing 11-hydroxy-∆9-tetrahydrocannabinol with 11-nor-9-carboxy-tetrahydrocannabinol concentrations.

Testing hair for cannabis use has increasingly been scrutinised due to exposure to second-hand smoke or environmental contamination. Confirmation of drug use involving detection of metabolites such as 11-nor-9-carboxy-delta-9-tetrahydrocannabinol (THC-COOH) and 11-hydroxy-delta-9-tetrahydrocannabinol (THC-OH) having very rarely been considered. We developed a new, simplified procedure with regard to expenditure of time and material to determine delta-9-tetrahydrocannabinol (THC, qualitatively), as well as THC-OH and THC-COOH (quantitatively) from 587 hair samples by liquid chromatography-tandem mass spectrometry (LC-MS/MS) which was compared to hitherto established methods (n = 3). Compared to conventional methanolic extraction alkaline dissolution resulted in higher concentrations for THC-OH. Concentrations determined from specimens ranged from 0.01 to 18.7 ng THC/mg hair, 0.05-37.6 pg THC-OH/mg hair, and from 0.1 to 54.3 pg THC-COOH/mg hair. THC was detectable in 70.4% samples along with both metabolites from more than half of these samples. In 12.9% of THC-positive cases, neither THC-OH nor THC-COOH were present. In 8.9% of THC-negative cases, it was possible to detect metabolites either alone or in combination. THC-OH could more frequently be detected than THC-COOH and appeared to be less susceptible to cosmetic treatment. In summary, THC-OH turned out to be a further suitable marker to prove cannabis use. Determination of both metabolites is recommended to unequivocally differentiate consumption from external exposure or contamination.

Determination of hydroxy metabolites of cocaine in hair samples for proof of consumption.

Although hair is widely used to identify drug use, there is a risk of false positives due to environmental contamination. This especially applies to cocaine (COC). Several strategies such as detection of norcocaine (NCOC) or cocaethylene, metabolite concentration ratios or intricate washing procedures have been proposed to differentiate actual use from contamination. The aim of the present study was to identify hydroxy metabolites of COC in hair specimens, thus enabling unambiguous prove of ingestion. A suspect screening of 41 COC-positive samples for these compounds was performed by liquid chromatography-quadrupole time of flight-mass spectrometry (LC-QTOF-MS). Once identified, mass transitions for o-, p- and m-isomers of hydroxy COC as well as p- and m-isomers of hydroxy benzoylecgonine (BE) and hydroxy NCOC were introduced into a routine procedure for testing drugs of abuse in hair by liquid chromatography-tandem mass spectrometry (LC-MS/MS) which was applied to 576 hair samples. Hydroxy metabolites were present in 92.2% of COC-positive hair samples; their detection rate exceeded that of cocaethylene and NCOC. Moreover, p-OH-BE, m-OH-BE as well as p-OH-NCOC and m-OH-NCOC have been identified for the first time in COC-positive hair specimens. Hydroxy cocainics could be detected in samples having a negative conclusion on drug use applying hitherto established criteria. We suggest a more conclusive interpretation outcome including detection of hydroxy metabolites into the evaluation of COC-positive hair samples.

Determination of hydroxy metabolites of cocaine from hair samples and comparison with street cocaine samples.

Drugs which are commonly smoked or sniffed (e.g. cocaine), can contaminate hair through smoke or dust; therefore testing for metabolites, especially hydroxy metabolites, is highly recommended. The presence of hydroxy metabolites in street-cocaine (COC) has been discussed. To check if detection of hydroxy metabolites definitely proves ingestion, the presence of these metabolites in street COC samples has to be checked. It is expected that the more hydrophilic hydroxy metabolites of COC are incorporated into the hair-matrix to a lesser extent. For this study 576 COC positive hair samples (≥0.1ng COC/mg hair) were analysed by LC-MS/MS for benzoylecgonine (BE), norcocaine (NC), cocaethylene (CE), ortho-, meta- and para-hydroxy COC (o-, m-, p-OH-COC), meta- and para-hydroxy BE (m-, p-OH-BE), and meta- and para-hydroxy NC (m-, p-OH-NC). The results were compared with the respective metabolite/COC concentration ratios in 146 street COC samples, confiscated by the Bavarian police. Peak areas were used to estimate BE/COC, NC/COC, CE/COC and hydroxy metabolites/COC. Similar metabolic ratios were found for o-OH-COC in 88% of the samples, but for p-OH-COC and m-OH-COC only in 5.1% and 6.8%, respectively. Notably, p- and m-OH-BE as well as p- and m-OH-NC could not be identified from seized samples. We propose that area ratios exceeding the ratios of street COC more than twice or identification of OH-BE and OH-NC enable to differentiate COC consumption from contamination. Using these criteria, consumption of the drug could be proven in 92% of COC positive samples. As detection of meta- and para-hydroxy metabolites using the above mentioned criteria is a reliable tool to distinguish between ingestion and external contamination, it is recommended to implement their measurement into daily routine work.