Simultaneous analysis of opioid analgesics and their metabolites in municipal wastewaters and river water by liquid chromatography–tandem mass spectrometry

Abstract

Although published literature provides a clear demonstration of widespread occurrence of opioid analgesics (OAs) in the aquatic environment, analytical methods suitable for a systematic study of this pharmaceutical class, which would include a broad spectrum of opioid analgesics and their metabolites, are still missing. In this work, a comprehensive multiresidue method for quantitative analysis of 27 opioid analgesics and their metabolites, including 2 morphine glucuronide conjugates, was developed and validated for three matrices: raw wastewater (RW), secondary effluent (SE) and river water. The method comprised different classes of opioid analgesics, including natural opiates (morphine and codeine), their semi-synthetic derivatives (hydrocodone, hydromorphone, oxycodone, oxymorphone and buprenorphine) as well as fully synthetic opioids such as methadone, fentanyl, sufentanil, propoxyphene and tramadol. The optimized enrichment procedure involved mixed-mode, strong cation-exchange sorbent in combination with a sequential elution procedure. The extracts were analyzed by reversed-phase liquid chromatography using a Synergy Polar column coupled to electrospray ionization tandem mass spectrometry (LC-MS/MS). Accurate quantification of target OAs was achieved using 19 deuterated analogues as surrogate standards. Method accuracies for RW, SE and river water varied in the range from 91 to 126%, 74 to 120% and 75 to 116%, respectively. Careful optimization of the procedure allowed reliable determination of OAs with method quantification limits in the low ng/L range (RW: 0.3-3.5 ng/L; SE: 0.2-1.9 ng/L, river water: 0.1-0.8 ng/L. The developed method was applied for analysis of RW, SE and river water samples from Croatia. The concentrations of individual OAs in municipal wastewater varied in a wide range (from < QL to 859 ng/L) and the most prevalent representatives were tramadol, codeine, morphine and methadone and their derivatives. Elevated concentrations of morphine glucuronides (up to 370 ng/L) found in raw municipal wastewater indicated their importance in the overall morphine mass balance.

Sample Preparation to Determine Pharmaceutical and Personal Care Products in an All-Water Matrix: Solid Phase Extraction

“…For this reason, some studies chose different volumes of water (depending on its characteristics) with the same method. For example, influent wastewater samples were generally analyzed with smaller volumes compared to effluent samples [46,48]. Figure 2 compares the various volumes that were selected in the different studies.…”

Perspectives and challenges associated with the determination of new psychoactive substances in urine and wastewater – A tutorial

“…A non-selective and versatile sample preparation protocol for the enrichment and clean-up of samples capable of retaining a wide range of NPS with broad physicochemical properties is preferred and applied by the vast majority of reported studies. Pooled urine samples are usually treated by performing a hydrolysis step to cleave drug-glucuronide conjugates with β-glucuronidase and arylsulfatase prior to solid-phase extraction (SPE), liquid-liquid extraction and/or dilute and shoot techniques [21,44,45], while wastewater samples do generally not require this hydrolysis step due to in-sewer deconjugation [46][47][48][49][50] and are normally filtered and solid-phase extracted [17], although a less labor-intensive and quicker preparation procedure following the QuECHeRS principle has also been applied [51]. In order to cover the broadest range of substances possible, multiple SPE cartridges or cartridges consisting of several layers with different stationary phase chemistries can be used [27,52].…”

Sub-Part-Per-Billion Level Sensing of Fentanyl Residues from Wastewater Using Portable Surface-Enhanced Raman Scattering Sensing

“…For instance, municipal wastewater testing methods are readily scalable and anonymous and can eliminate self-reporting surveys, map drug consumption, and can provide an early warning in the constantly changing landscape of substance abuse for proactive responses. High-performance liquid chromatography in tandem with mass spectrometry (HPLC-MS) [7][8][9][10][11] is the most widely used wastewater sensing technique, which can detect various drugs including opioids in the wastewater stream and can differentiate between drugs that were discarded and drugs that were metabolized. Such extraordinary analytical techniques can be adopted to address practical questions and dynamic monitoring of illicit drug use.…”