Development of a new multi-residue laser diode thermal desorption atmospheric pressure chemical ionization tandem mass spectrometry method for the detection and quantification of pesticides and pharmaceuticals in wastewater samples

A new solid phase extraction (SPE) method coupled to a high throughput sample analysis technique was developed for the simultaneous determination of nine selected emerging contaminants in wastewater (atrazine, desethylatrazine, 17β-estradiol, ethynylestradiol, norethindrone, caffeine, carbamazepine, diclofenac and sulfamethoxazole). We specifically included pharmaceutical compounds from multiple therapeutic classes, as well as pesticides. Sample pre-concentration and clean-up was performed using a mixed-mode SPE cartridge (Strata ABW) having both cation and anion exchange properties, followed by analysis by laser diode thermal desorption atmospheric pressure chemical ionization coupled to tandem mass spectrometry (LDTD-APCI-MS/MS). The LDTD interface is a new high-throughput sample introduction method, which reduces total analysis time to less than 15 s per sample as compared to minutes with traditional liquid-chromatography coupled to tandem mass spectrometry (LC–MS/MS). Several SPE parameters were evaluated in order to optimize recovery efficiencies when extracting analytes from wastewater, such as the nature of the stationary phase, the loading flow rate, the extraction pH, the volume and composition of the washing solution and the initial sample volume. The method was successfully applied to real wastewater samples from the primary sedimentation tank of a municipal wastewater treatment plant. Recoveries of target compounds from wastewater ranged from 78% to 106%, the limit of detection ranged from 30 to 122 ng L−1 while the limit of quantification ranged from 90 to 370 ng L−1. Calibration curves in the wastewater matrix showed good linearity (R2 ≥ 0.991) for all target analytes and the intraday and interday coefficient of variation was below 15%, reflecting a good precision.

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► We analyzed emerging contaminants of varied origins.
► We used a single mixed-mode solid phase extraction protocol for all analytes.
► We analyzed the samples in <15 s using an ultrafast LDTD-APCI-MS/MS method.
► Recoveries of target compounds were from 76% to 106%.
► Limits of detection were from 30 to 122 ng L−1.