LC-MS-MS Method Development and Analysis of Stimulants, Opiates, Synthetic Opiates, PCP, and Benzodiazepines in Wastewater. Preponderance of these Drugs During Football Games

Abstract

A method was developed for the analysis of stimulant drugs, opiates, synthetic opiates, PCP, and benzodiazepines in wastewater samples using liquid chromatography coupled with tandem mass spectrometry (LC-MS-MS). A total of 33 compounds (stimulant-type drugs and metabolites of opiates, synthetic opiates, PCP, and benzodiazepines) were analyzed. These drugs included amphetamine (Amp) (1), methamphetamine (Meth) (2), methylenedioxyamphetamine (MDA) (3), methylenedioxymethamphetamine (MDMA) (4), methylenedioxyethylamphetamine (MDEA) (5), benzoylecgonine (BE, the major metabolite of Coc) (6), cocaine (Coc) (7), 6-monoacetylmorphine (6-MAM, the primary urinary metabolite of heroin) (8), codeine (9), hydrocodone (10), hydromorphone (11), morphine (12), norhydrocodone (the primary urinary metabolite of hydrocodone) (13), oxycodone (14), oxymorphone (15), 2-ethylidine-1,5-dimethyl-3,3-diphenylpyrolidine (EDDP, the primary urinary metabolite of methadone) (16), fentanyl (17), meperidine (18), methadone (19), norfentanyl (the primary urinary metabolite of fentanyl) (20), normeperidine (the primary urinary metabolite of meperidine) (21), phencyclidine (PCP) (22), tramadol (23), alprazolam (24), temazepam (25), nordiazepam (26), chlordiazepoxide (27), flurazepam (28), oxazepam (29), α-OH-alprazolam (the primary urinary metabolite of alprazolam) (30), α-OH-triazolam (the primary urinary metabolite of triazolam) (31), 2-OH-ethylflurazepam (the primary urinary metabolite of flurazepam) (32), and 7-NH-flunitrazepam (the primary urinary metabolite of flunitrazepam) (33). These drugs were chosen because of their widespread abuse. Wastewater samples were collected at both the Oxford Wastewater Treatment Plant in Oxford, Mississippi (MS), and the University Wastewater Treatment Plant in University, MS. Samples were collected on weekends on which the Ole Miss Rebel football team held home games (Vaught-Hemingway Stadium, University, MS 38677). The collected samples were analyzed using a validated method and found to contain Amp, Meth, MDMA, MDA, Coc, BE, codeine, hydrocodone, hydromorphone, morphine, norhydrocodone, oxycodone, oxymorphone, tramadol, EDDP, meperidine, normeperidine, methadone, alprazolam, α-OH-alprazolam, nordiazepam, oxazepam, and temazepam. None of the samples contained MDEA, 6-MAM, fentanyl, norfentanyl, PCP, chlordiazepoxide, flurazepam, 2-OH-ethylflurazepam, 7-NH-flunitrazepam, and α-OH-triazolam.

Site- and event-specific wastewater-based epidemiology: Current status and future perspectives

“…hourly samples to study time-dependent use patterns [26], and samples collected over an extended period (72-h composite samples) at sites with limited access [22,27,28]. For estimating drug consumption during special events, 24-h composite samples are commonly collected (Table 2) while grab sampling, which is not recommended because of its inability to J o u r n a l P r e -p r o o f capture high intraday variability of drug excretion, has rarely been applied [29][30][31]. Tables 1 and 2, list the three most common autosampling modes: flow-, volume-and time-proportional, which were used to obtain composite wastewater samples in specific catchments and during special events.…”

“…J o u r n a l P r e -p r o o f J o u r n a l P r e -p r o o f The primary source of uncertainty in sampling, which can exceed 100%, depends on catchment characteristics, mode of sampling, and sampling frequency [10,29]. Burgard et al [22] are the only group so far to determine sampling uncertainty connected with at source sampling (e.g.…”

“…[29] AMPamphetamine, BUPbuprenorphine, COCcocaine, CODcodeine, GHBgamma-hydroxybutyrate, HERheroin, KETketamine, LSDlysergic acid diethylamide, MAMPmethamphetamine, MBDB -3,4-methylenedioxy-N-methyl-butanphenamine, MDA -3,4-methylenedioxyamphetamine, MDEA -3,4-methylenedioxy-N-ethylamphetamine, MDMA -3,4 methylendioximethamphetamine, MEPHmephedrone, MORmorphine, MTHDmethadone, PCPphencyclidine, PEPHpseudoephedrine J o u r n a l P r e -p r o o f…”

Current and future perspectives for wastewater-based epidemiology as a monitoring tool for pharmaceutical use

“…An under-explored area is the use of WBE within sub-catchments such as hospitals or university campuses, suburbs, or aged care facilities. Limited studies show the potential for WBE to monitor the consumption of pharmaceuticals in subsets of the population and during specific events (Burgard et al, 2019;Gomez-Canela et al, 2019;Gul, Gul, Stamper, Godfrey, & ElSohly, 2018;Gushgari et al, 2018;Kosma, Nannou, Boti, & Albanis, 2019;Mackulak et al, 2016;Ort, Lawrence, Reungoat, Eaglesham, et al, 2010;van Dyken et al, 2016). In this light, three WBE studies focused on the consumption of opioids and benzodiazepines during football games at the Mississippi University campus (Gul et al, 2018(Gul et al, , 2016Stamper et al, 2016) and found substantial increases in tramadol and hydrocodone while concentrations in the municipal IWW samples were unchanged.…”

Rapid Assessment of Opioid Exposure and Treatment in Cities Through Robotic Collection and Chemical Analysis of Wastewater

“…SPE cartridges were eluted with 100% methanol, dried down using a Vacufuge, and analyzed by high performance liquid chromatography tandem-mass spectrometry (HPLC-MS/MS) [13]. We used a library of human metabolites of heroin, fentanyl, codeine, morphine, hydrocodone, hydromorphone, oxycodone, oxymorphone, tramadol, methadone, buprenorphine, and naloxone, as well as substances that serve as positive controls, such as nicotine, acetaminophen, and caffeine (Table 2).…”