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Journal ArticleDOI

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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Citations
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Journal ArticleDOI
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.

127 citations

Journal ArticleDOI
TL;DR: The present study shows the development and validation of a DI-based method by ultra-high-performance liquid chromatography quadrupole-linear ion trap analyser (UHPLC-QqLIT-MS/MS) applied to the monitoring of 115 organic microcontaminants at the ngL-1/μg L-1 level in wastewater effluents from urban WWTPs.

91 citations

Journal ArticleDOI
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

Journal ArticleDOI
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...

81 citations

Journal ArticleDOI
TL;DR: Assessing whether current in vitro bioassays are suitable to detect endocrine activity in a range of water types can help provide guidance on in vitroBioassay selection and required sample enrichment for optimised detection of endocrineactivity in environmental waters.

71 citations


Cites background from "Rapid direct injection LC-MS/MS met..."

  • ...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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Journal ArticleDOI
TL;DR: Acidic pharmaceuticals, caffeine, and the antibacterial triclosan were quantified at four different steps of wastewater treatment from three urban wastewater treatment plants, yielding expected surface water concentrations of 13 to 56 ng/L.
Abstract: Pharmaceuticals are a class of emerging contaminants whose fate in the wastewater treatment process has received increasing attention in past years. Acidic pharmaceuticals (ibuprofen, naproxen, mefenamic acid, ketoprofen, and diclofenac), caffeine, and the antibacterial triclosan were quantified at four different steps of wastewater treatment from three urban wastewater treatment plants. The compounds were extracted from wastewater samples on Waters Oasis hydrophilic-lipophilic balance solid-phase extraction columns, silylated, and analyzed by gas chromatography-mass spectrometry. For the chemicals studied, it was found that the majority of the influent load was removed during secondary treatment (51-99%), yielding expected surface water concentrations of 13 to 56 ng/L.

193 citations

Journal ArticleDOI
TL;DR: Across the treatment systems examined, the majority of pharmaceuticals observed in on-site and municipal effluent discharges were predicted to potentially present therapeutic hazards to fish, and removal by these wastewater treatment systems was generally not influenced by season.

193 citations

Journal ArticleDOI
TL;DR: In the current study, empirical correlations for ΔUV(254) and ΔTF were developed for the oxidation of 18 trace organic contaminants and a predictive model for OH exposure based on ΔUV (254) or ΔTF was also proposed.

178 citations

Journal ArticleDOI
TL;DR: The results of this study confirm that sucralose will function well as an indicator compound for anthropogenic influence on source, finished drinking and distribution system water, as well as a indicator compounds for the presence of other recalcitrant compounds in finished drinking water in the U.S.
Abstract: The artificial sweetener sucralose has recently been shown to be a widespread of contaminant of wastewater, surface water, and groundwater In order to understand its occurrence in drinking water systems, water samples from 19 United States (US) drinking water treatment plants (DWTPs) serving more than 28 million people were analyzed for sucralose using liquid chromatography tandem mass spectrometry (LC-MS/MS) Sucralose was found to be present in source water of 15 out of 19 DWTPs (47–2900 ng/L), finished water of 13 out of 17 DWTPs (49–2400 ng/L) and distribution system water of 8 out of the 12 DWTPs (48–2400 ng/L) tested Sucralose was only found to be present in source waters with known wastewater influence and/or recreational usage, and displayed low removal (12% average) in the DWTPs where finished water was sampled Further, in the subset of DWTPs with distribution system water sampled, the compound was found to persist regardless of the presence of residual chlorine or chloramines In order to u

176 citations

Journal ArticleDOI
TL;DR: Results of this study indicate that natural attenuation can result in significant decreases in concentrations of wastewater-derived contaminants in large rivers.
Abstract: Although wastewater-derived chemical contaminants undergo transformation through a variety of mechanisms, the relative importance of processes such as biotransformation and photolysis is poorly understood under conditions representative of large rivers. To assess attenuation rates under conditions encountered in such systems, samples from the Trinity River were analyzed for a suite of wastewater-derived contaminants during a period when wastewater effluent accounted for nearly the entire flow of the river over a travel time of approximately 2 weeks. While the concentration of total adsorbable organic iodide, a surrogate for recalcitrant X-ray phase contrast media in wastewater, was approximately constant throughout the river, concentrations of ethylenediamine tetraacetate, gemfibrozil, ibuprofen, metoprolol, and naproxen all decreased between 60% and 90% as the water flowed downstream. Comparison of attenuation rates estimated in the river with rates measured in laboratory-scale microcosms suggests that b...

174 citations