Validation of LC-MS/MS method for opioid monitoring in Valencia City wastewater: Assessment of synthetic wastewater as potential aid.

In this study, a comprehensive and sensitive method for the simultaneous detection of 17 opioids (OPs) and their human metabolites in wastewater using high-performance liquid chromatography coupled to tandem mass spectrometry was validated. The chromatographic separations of opioids were carried out on a Kinetex® Biphenyl column (1.7 µm, 100 Å, 50 × 2.1 mm). A synthetic wastewater approach was used for recovery studies to mimic a contaminant-free matrix. Two solid-phase extraction (SPE) sorbents (hydrophilic-lipophilic balance and mixed mode with the previous phase and a weak cationic exchange) were studied to optimize sample treatment and obtain higher recoveries. The mixed mode was chosen because the recoveries of 17 target analytes at three spiked concentrations (25, 50, and 100 ng mL-1) were > 80 % for 75 % of the analytes in a simulated wastewater. The intra- and inter-day relative standard deviations (RSDs) were between ±1 % and ±20 %. The method limits of quantification ranged from 5 to 25 ng L-1, the only exceptions being heroin (275 ng L-1) and morphine-3ß-glucuronide (250 ng L-1). Suppression/enhancement is comparable between the synthetic and the influent wastewater. The analytical method was applied to the OPs analysis in twenty-one influent samples collected from the treatment plants treating the wastewater of Valencia City (Spain). Twelve OPs were detected with total daily concentrations ranging from 1 ng L-1 to 2135 ng L-1. The widespread presence of these compounds in water suggests potential widespread exposure, highlighting the need for increased environmental awareness. Furthermore, the estimated daily intake results raise concerns about opioid use as a potential future health and social issue.

Pharmaceuticals and personal care products in a Mediterranean coastal wetland: Impact of anthropogenic and spatial factors and environmental risk assessment.

The present study focused on the occurrence, distribution and risk assessment of 32 pharmaceuticals and personal care products (PPCPs) in water and sediment, as well as the surrounding soil of the irrigation channels and lake of a Mediterranean coastal wetland, the Albufera Natural Park (Valencia, Spain). Moreover, the influent and effluent of ten wastewater treatment plants (WWTPs) that treat wastewater from Valencia and the surrounding areas were also studied. BPA, caffeine, diclofenac, ethyl paraben, methyl paraben, metformin, tramadol and salicylic acid were the predominant PPCPs detected in the channels and the lake, and are in good agreement with those detected in the effluent. Furthermore, 22 PPCPs were detected in >47% of the sediment samples. Of them, BPA, ethyl paraben, furosemide, ibuprofen and salicylic acid were at higher concentrations. In contrast, only seven PPCPs were detected in >44% of the soil samples. Spatial variation showed that the concentration of many PPCPs was higher in the northern area of the park, whereas the ibuprofen concentrations were higher in the south. Differences were also observed according to the type of water used for irrigation and the land uses of the area. A risk assessment based on the hazardous quotient (HQ) indicated that caffeine is a compound of concern, and tramadol at the highest concentration showed a moderate risk for the organisms assessed. Considering the mixture of the PPCPs found at each sampling point, the green algae are at risk, particularly in those points located near the city of Valencia (the most important nearby human settlement). These results indicate the need for further studies.

Systematic assessment of extraction of pharmaceuticals and personal care products in water and sediment followed by liquid chromatography-tandem mass spectrometry.

Two solid-phase extraction methods were systematically studied to determine 32 pharmaceuticals and personal care products in water and sediments by ultrahigh-performance liquid chromatography-tandem mass spectrometry. One involves HLB cartridges activated with sodium dodecyl sulfate before the passage of the sample to form an ion pair with cationic analytes, and the other uses mixed HLB-cation exchange cartridges. The accuracy of the sodium dodecyl sulfate method was good for most compounds (recoveries of 61-120% with relative standard deviation less than 23%). However, the recoveries for atorvastatin, codeine, paracetamol, flufenamic acid, and salicylic acid were approximately 50% and for omeprazole and triclocarban were even lower (from 0 to 12%). The detection limits were 1.65-25 ng L-1 in water and 0.33-4.00 ng g-1 (dry weight) in sediment. The recoveries for the mixed-mode cartridge (Strata-X-CW) method ranged from 57% to 120% with relative standard deviation less than 21%, with the exception of codeine [25% (water)], metformin [11% (sediment)], paracetamol [48% (sediment)], and salicylic acid [32% (sediment)]. The detection limits were 1.65-38.35 ng L-1 in water and 0.33-10 ng g-1 (dry weight) in sediment. Both methods followed the same pattern when applied to water. For sediments, the recoveries, which offer good performance, were not very high, although 60% of the compounds had recoveries greater 80%. The methods were applied to the analysis of surface water and sediments from the Albufera Natural Park (Spain). Twenty-seven of 32 analytes were detected in the samples analyzed.