Rapid direct injection LC-MS/MS method for analysis of prioritized indicator compounds in wastewater effluent
04 Sep 2015-Vol. 1, Iss: 5, pp 632-643
TL;DR: In this paper, the authors used a detailed literature review and scoring system to establish a list of twenty priority indicator trace organic compounds (TOrCs) in US wastewaters.
Abstract: Trace organic compounds (TOrCs) have been detected in drinking water sources for several years, raising concerns due to their potential risks to public health. The main contributor of TOrCs to drinking water is through wastewater discharges. However, there are several hundred TOrCs currently known with numerous new organic chemicals being released daily, making it unfeasible to monitor each one in water. This study used a detailed literature review and scoring system to establish a list of twenty priority indicator TOrCs in US wastewaters. Next, a rapid direct injection LC-MS/MS method for analysis of these compounds was developed without the need for an extraction step and only 80 μL sample volume while providing method reporting limits of 3–39 ng L−1 for all but one TOrC (sucralose: 302 ng L−1). The elimination of an extraction step reduced matrix effects considerably making the method suitable for wastewater analysis. Method validation including matrix spike recoveries, linearity of calibration curve and inter- and intra-day variability was successfully performed. Finally, the twenty indicator TOrCs were evaluated in four different wastewater treatment plant (WWTP) effluents through four sample campaigns spread across a year. The occurrence data indicated that all indicator TOrCs were detected in at least three out of the four WWTP effluents. Sucralose, iohexol, TCPP, acesulfame and gemfibrozil were detected in all samples at the four WWTPs indicating they could be used as indicators of wastewater influence in receiving waters. DEET, caffeine, triclosan, iopromide and others are effective indicators at showing seasonal variations, treatment process efficacy, and consumption patterns. Overall, the impact of this study will help develop more effective monitoring programs for TOrCs in water reuse schemes.
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TL;DR: Data comparisons indicate that pharmaceutical exposures in river systems are highly variable regionally, in part due to variability in prescribing practices, hydrology, wastewater management, and urbanisation and that select annual median pharmaceutical concentrations observed in this study were higher than those previously observed in the European Union and Asia thus far.
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TL;DR: The effluent composition of the 22 TOrCs were similar within the three WWTPs but quite different to those seen in the US, indicating the importance of region-specific monitoring.
89 citations
TL;DR: The results highlight the importance of analyzing water samples using multiple separation techniques and in multiple ionization modes to obtain a comprehensive chemical contaminant profile.
Abstract: Efficient strategies are required to implement comprehensive suspect screening methods using high-resolution mass spectrometry within environmental monitoring campaigns. In this study, both liquid and gas chromatography time-of-flight mass spectrometry (LC-QTOF-MS and GC-QTOF-MS) were used to screen for >5000 target and suspect compounds in the Sacramento–San Joaquin River Delta in Northern California. LC-QTOF-MS data were acquired in All-Ions fragmentation mode in both positive and negative electrospray ionization (ESI). LC suspects were identified using two accurate mass LC-QTOF-MS/MS libraries containing pesticides, pharmaceuticals, and other environmental contaminants and a custom exact mass database with predicted transformation products (TPs). The additional fragment information from the All-Ions acquisition improved the confirmation of the compound identity, with a low false positive rate (9%). Overall, 25 targets, 73 suspects, and 5 TPs were detected. GC-QTOF-MS extracts were run in negative chemi...
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...Absolute recoveries withmore complexmatrices such aswastewater can be significantly lower, and accurate chemical quantification often requires the use of deuterated standards (Anumol et al., 2013; Anumol et al., 2015)....
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References
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TL;DR: In this article, a benchtop continuous-flow reactor was developed for the purpose of studying the activity, inhibition, and deactivation of immobilized TiO 2 photocatalysts during water treatment applications.
Abstract: Titanium dioxide (TiO 2 ) photocatalysts have been shown to be effective at degrading a wide range of organic micropollutants during short-term batch experiments conducted under ideal laboratory solution conditions (e.g., deionized water). However, little research has been performed regarding longer-term photocatalyst performance in more complex matrices representative of contaminated water sources (e.g., wastewater effluent, groundwater). Here, a benchtop continuous-flow reactor was developed for the purpose of studying the activity, inhibition, and deactivation of immobilized TiO 2 photocatalysts during water treatment applications. As a demonstration, degradation of four pharmaceutical micropollutants (iopromide, acetaminophen, sulfamethoxazole, and carbamazepine) was monitored in both a pH-buffered electrolyte solution and a biologically treated wastewater effluent (WWE) to study the effects of non-target constituents enriched in the latter matrix. Reactor performance was shown to be stable over 7 d when treating micropollutants in buffered electrolyte, with 7-d averaged k obs values (acetaminophen = 0.97 ± 0.10 h −1 ; carbamazepine = 0.50 ± 0.04 h −1 ; iopromide = 0.49 ± 0.03 h −1 ; sulfamethoxazole = 0.79 ± 0.06 h −1 ) agreeing closely with measurements from short-term circulating batch reactions. When reactor influent was switched to WWE, treatment efficiencies decreased to varying degrees (acetaminophen = 40% decrease; carbamazepine = 60%; iopromide = 78%; sulfamethoxazole = 54%). A large fraction of the catalyst activity was recovered upon switching back to the buffered electrolyte influent after 4 d, suggesting that much of the observed decrease resulted from reversible inhibition by non-target constituents (e.g., scavenging of photocatalyst-generated OH). However, there was also a portion of the decrease in activity that was not recovered, indicating WWE constituents also contributed to photocatalyst deactivation (acetaminophen = 6% deactivation; carbamazepine = 24%; iopromide = 16%; sulfamethoxazole = 25%). Experiments conducted using pretreated WWE and synthetic WWE mimic solutions indicated that both effluent organic matter and inorganic constituents in WWE contributed to the observed photocatalyst inhibition/deactivation. Analysis of immobilized TiO 2 thin films after 4 d of continuous treatment of the WWE matrix indicated minor deterioration of the porous film and formation of surface precipitates enriched in Al and Ca. Results demonstrated the marked influence of non-target constituents present in complex matrices on long-term photocatalyst activity and highlighted the need for further study of this important issue to advance the development of practical photocatalytic water treatment technologies.
121 citations
TL;DR: Surrogate predictions using UV254 and TF provide valuable tools for rapid or on-line monitoring of GAC performance and can result in cost savings by extended GAC run times as compared to using DOC breakthrough to trigger regeneration or replacement.
116 citations
TL;DR: The analysis of several wastewater, surface water and groundwater samples from the US showed that sucralose can be found in the aquatic environment at concentrations up to 2.4microg/L, thus providing a good indication of wastewater input from beverage sources.
108 citations
TL;DR: An analytical method allowing for simultaneous detection and identification of 20 pharmaceutical compounds from various therapeutic classes using solid phase extraction (SPE) followed by liquid chromatography-electrospray ionisation mass spectrometry (LC-MS/MS).
107 citations
TL;DR: Household HPVs were consistently detected in raw sewage entering three full-scale wastewater treatment plants and compounds such as vanillin, DEET, benzophenone, 3-indolebutyric acid, bisphenol A, triclosan and triclocarban were detected in all wastewater influent and effluent samples.
96 citations