Screening for illicit drugs in pooled human urine and urinated soil samples and studies on the stability of urinary excretion products of cocaine, MDMA, and MDEA in wastewater by hyphenated mass spectrometry techniques

Abstract

Monitoring population drug use through wastewater-based epidemiology (WBE) is a useful method to quantitatively follow trends and estimate total drug consumption in communities. Concentrations of drug biomarkers might be low in wastewater due to dilution; and therefore analysis of pooled urine (PU) is useful to detect consumed drugs and identify targets of illicit drugs use. The aims of the study were (1) to screen PU and urinated soil (US) samples collected at festivals for illicit drug excretion products using hyphenated techniques; (2) to develop and validate a hydrophilic interaction liquid chromatography - mass spectrometry / mass spectrometry (HILIC-MS/MS) method of quantifying urinary targets of identified drugs in wastewater; and (3) to conduct a 24 h stability study, using PU and US to better reflect the chemical environment for targets in wastewater. Cocaine (COC) and ecstasy-like compounds were the most frequently detected illicit drugs; an analytical method was developed to quantify their excretion products. Hydroxymethoxymethamphetamine (HMMA), 3,4-methylenedioxymethamphetamine (MDMA), 3,4-methylenedioxyamphetamine (MDA), HMMA sulfate (HMMA-S), benzoylecgonine (BE), and cocaethylene (CE) had 85-102% of initial concentration after 8 h of incubation, whereas COC and ecgonine methyl ester (EME) had 74 and 67% after 8 h, respectively. HMMA showed a net increase during 24 h of incubation (107% ± 27, n = 8), possibly due to the cleavage of HMMA conjugates, and biotransformation of MDMA. The results suggest HMMA as analytical target for MDMA consumption in WBE, due to its stability in wastewater and its excretion as the main phase I metabolite of MDMA. Copyright © 2016 John Wiley & Sons, Ltd.

3-Fluorophenmetrazine, a fluorinated analogue of phenmetrazine: Studies on in vivo metabolism in rat and human, in vitro metabolism in human CYP isoenzymes and microbial biotransformation in Pseudomonas Putida and wastewater using GC and LC coupled to (HR)-MS techniques

“…Wastewater microbial biotransformation of 3-FPM was tested using a setup previously described [8,9], briefly: 3-FPM (1 mg/L) was incubated in grab sample, influent wastewater from a WTP in Homburg (Saarland, Germany) serving about 35,000 inhabitants, and in deionized water to correct for non-enzymatic oxidation and hydrolysis transformations. Incubations were performed in duplicate in closed, constantly, gentle moving amber glass reactors with a free flow of air through 0.20 µm sterile air filters, in a thermostated room at 22 °C.…”

“…Microbial biotransformation of 3-FPM in wastewater after 7 d of incubation was N-oxidation (1) and biotransformation on the alpha-methyl position, first through hydroxylation (6), then oxidation to the aldehyde (7) and finally, eluting in the neutral fraction, the carboxylic acid (8). Oxidation of tolyl-groups to carboxylic acids is observed in wastewater for the tolyl-methyl in the pyrrolidine phenone-type NPS 4'-Methyl-α-pyrrolidinohexiophenone (MPHP) and 4'-Methyl-α-Pyrrolidinobutiophenone (MPBP), and Noxidations for methylenedioxy-pyrovalerone, MPHP and MPBP [11].…”

“…Before analysis by WBE, drugs and NPSs go through two biotransforming systems: first, the human metabolic system where extensive metabolism could cause very low amounts to be excreted [7], and then the wastewater microbiome in the transit from toilet to the wastewater treatment plant (WTP), where further biotransformation of unchanged excreted drug and drug metabolites can occur [8][9][10][11].…”

Wastewater-Based Epidemiology of Cocaine in the Brazilian Federal District: Spatial Distribution, Weekly Variation and Sample Preservation Strategies

“…Also for this reason, analytical data concerning benzoylecgonine in wastewater samples has been used as a near real-time tool to estimate cocaine consumption for a given population. 8,9 Several works have explored different aspects of the WBE approach including other cocaine metabolites, 10 estimation of other consumed drugs, [10][11][12] influence of recreational events, [13][14][15][16] consumption dynamics in restricted facilities, [17][18][19] temporal and spatial variability, [20][21][22] stability of target chemicals, 23,24 refinement on estimates calculation, [25][26][27] innovations in sample preparation and analysis, [28][29][30] among others. In Brazil, the first work to put the WBE approach into practice was designed to assess cocaine consumption on regions served by six wastewater treatment plants (WWTP) installed in the Brazilian Federal District (FD).…”

Analytical Profiling of Airplane Wastewater - a New Matrix for Mapping Worldwide Patterns of Drug Use and Abuse

“…Conventional methods include analysis of seized materials and biological samples such as urine, saliva, hair, and blood. Newer methods include wastewater-based epidemiology (WBE) [2], screening of pooled urine [3][4][5], urinated soil [4], and exhaled breath samples [6]. Low concentrations of analytical targets in pooled and diluted samples call for sophisticated sample work-up and/or highly sensitive and selective analytical equipment such as tandem mass spectrometry (MS/ MS) or high resolution MS in target screening mode [2;5;7].…”