Adsorption of Therapeutic and Recreational Drugs During Prolonged Storage of Plasma Samples in Gel Separator Tubes.

Hospital samples collected in gel separator tubes are often submitted to forensic toxicology laboratories for analysis in impaired driving and death investigations. Drug adsorption to the gel separator material may lead to underestimation of the drug concentration present at the time of sample collection, potentially affecting the interpretation of analytical results. Using liquid chromatography--tandem mass spectrometry (LC--MS-MS), decreases in plasma concentration of 53 drugs and metabolites relevant to forensic toxicology casework were investigated in samples stored in BD Vacutainer® PSTTM tubes for up to 3 months. After storage for only 1 day, approximately 50% of the drugs and metabolites had significantly lower concentrations in plasma separation tubes (PSTs) compared to non-gel tubes (up to 27% lower). After storage for 3 months, approximately 75% of the drugs and metabolites had significantly lower concentrations in PSTs compared to non-gel tubes (up to 69% lower). Fentanyl, carfentanil, ketamine, diphenhydramine and several antidepressants were among the drugs most susceptible to adsorption. Central nervous system stimulants (e.g., methamphetamine and amphetamine) as well as naturally-occurring and semi-synthetic opioids (e.g., morphine, hydromorphone and oxycodone) were among the drugs least susceptible to adsorption and displayed only minimal relative decreases in concentration (if any) over the 3-month sample storage period. The potential for decreases in drug concentration due to adsorption of drugs to the gel material should be considered for toxicological interpretation based on the analysis of a sample collected in a gel separator tube.

Analysis of DOM phototransformation using a looped NMR system integrated with a sunlight simulator.

Photochemical transformation plays an important role in functionalizing and degrading dissolved organic matter (DOM), producing one of the most complex mixtures known. In this study, using a flow-based design, nuclear magnetic resonance (NMR) spectroscopy is directly interfaced with a sunlight simulator enabling the study of DOM photodegradation in situ with high temporal resolution over 5 days. Samples from Suwannee River (Florida), Nordic Reservoir (Norway), and Pony Lake (Antarctic) are studied. Phototransformation of DOM is dominated by the degradation of aromatics and unsaturated structures (many arising from lignin) into carboxylated and hydroxylated products. To assess longer term changes, the samples were continuously irradiated for 17.5 days, followed by the identification a wide range of compounds and assessment of their fate using off-line 2D-NMR. This study demonstrates the applicability of the looped system to follow degradation in a non-targeted fashion (the mixture as a whole) and target analysis (tracing specific metabolites), which holds great potential to study the fate and transformation of contaminants and nutrients in the presence of DOM. It also demonstrates that components that remain unresolved in 1D NMR can be identified using 2D methods.

Development of an in Situ NMR Photoreactor To Study Environmental Photochemistry.

Photochemistry is a key environmental process directly linked to the fate, source, and toxicity of pollutants in the environment. This study explores two approaches for integrating light sources with nuclear magnetic resonance (NMR) spectroscopy: sample irradiation using a "sunlight simulator" outside the magnet versus direct irradiation of the sample inside the magnet. To assess their applicability, the in situ NMR photoreactors were applied to a series of environmental systems: an atmospheric pollutant (p-nitrophenol), crude oil extracts, and groundwater. The study successfully illustrates that environmentally relevant aqueous photochemical processes can be monitored in situ and in real time using NMR spectroscopy. A range of intermediates and degradation products were identified and matched to the literature. Preliminary measurements of half-lives were also obtained from kinetic curves. The sunlight simulator was shown to be the most suitable model to explore environmental photolytic processes in situ. Other light sources with more intense UV output hold potential for evaluating UV as a remediation alternative in areas such as wastewater treatment plants or oil spills. Finally, the ability to analyze the photolytic fate of trace chemicals at natural abundance in groundwater, using a cryogenic probe, demonstrates the viability of NMR spectroscopy as a powerful and complementary technique for environmental applications in general.