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.
127 citations
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
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...
81 citations
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
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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: Liquid chromatography-tandem mass spectrometry coupled with the calibration technique of isotope dilution were able to accurately quantify most compounds with an average bias of <10% for both matrixes, suggesting that this method of analysis is suitable at environmentally relevant levels for most of the compounds studied.
Abstract: An evaluation of existing analytical methods used to measure contaminants of emerging concern (CECs) was performed through an interlaboratory comparison involving 25 research and commercial laboratories. In total, 52 methods were used in the single-blind study to determine method accuracy and comparability for 22 target compounds, including pharmaceuticals, personal care products, and steroid hormones, all at ng/L levels in surface and drinking water. Method biases ranged from 15...
26 citations
TL;DR: The stability of selected markers (sucralose, carbamazepine, gadolinium anomaly, iohexol, and atenolol) was evaluated through bench-scale studies designed to simulate environmental conditions associated with biodegradation, adsorption, and photolysis.
25 citations
TL;DR: This monograph contains papers presented at the Prague workshop and follows the session structure of the meeting, focusing on four main topics: “Indicators of Human and Wildlife Exposure to EDCs” reports on new findings relating human exposure to endocrine disruptors in Europe to reproductive disorders, including cryptorchidism, hypospadias, and semen quality.
Abstract: With the aim of discussing new research findings about chemicals able to interfere with the endocrine system, so-called endocrine disruptors, an international workshop was held in Prague, Czech Republic, 10–12 May 2005. The workshop was organized jointly by the EDEN project (Endocrine Disrupters: Exploring Novel Endpoints, Exposure, Low-Dose and Mixture-Effects in Humans, Aquatic Wildlife and Laboratory Animals; http://www.edenresearch.info) and the FIRE project (Risk Assessment of Brominated Flame Retardants as Suspected Endocrine Disrupters for Human and Wildlife Health; http://www.rivm.nl/fire), both large-scale consortia funded by the European Union (EU). The meeting was attended by more than 170 scientists from academia, industry, government agencies, and other organizations.
EDEN and FIRE were part of the CREDO cluster (Cluster for Research on Endocrine Disruption), an umbrella organization of more than 60 EU-funded laboratories working on endocrine disruptors. Together with the COMPRENDO (Comparative Research on Endocrine Disruption) and the EURISKED projects (Multi-organic Risk Assessment of Selected Endocrine Disruptors; http://www.eurisked.org), EDEN and FIRE formed the core of the cluster. CREDO served as a platform for cooperation and exchange between its constituent projects. With the completion of almost all its member projects, CREDO has recently ceased to exist, but information about the cluster is still available on online (http://www.credocluster.info).
The Prague workshop was the last in a series of meetings organized under the auspices of the CREDO cluster. The themes of previous workshops were risk assessment and the ecologic relevance of chemically induced endocrine disruption in wildlife (Jobling and Tyler 2006).
This monograph contains papers presented at the Prague workshop and follows the session structure of the meeting, focusing on four main topics:
“Indicators of Human and Wildlife Exposure to EDCs ” reports on new findings relating human exposure to endocrine disruptors in Europe to reproductive disorders, including cryptorchidism, hypospadias, and semen quality. New information about exposure trends for brominated flame retardants in freshwater and marine ecosystems is also given.
“Novel models, end points, and biomarkers” summarizes research on the effects of endocrine disruptors on steroid-metabolizing enzymes and gives new data on alkylphenols as endocrine disruptors. Additional articles focus on the consequences of prolonged phytoestrogen exposure for reproductive organs and the outcomes of in utero exposure to endocrine disruptors for testicular dysgenesis, prostate development, and the thyroid hormone axis.
“Low-dose effects of endocrine disruptors” gives a synthesis of recent observations in in vitro systems and highlights the importance of statistical power considerations in resolving the low-dose issue.
“Mixture effects of endocrine disruptors and their assessment” contains reviews of combination effects, assesses the implications of low-level exposure to multiple chemicals and describes the joint effect of endocrine disruptors in fish and in a developmental toxicity rat model.
Taken together, the articles presented in this monograph capture a great deal of the lively debates that took place during the Prague workshop and within the CREDO cluster as a whole. The workshop made considerable progress toward answering key questions that were unresolved a few years ago. It has also stimulated a consensus statement among scientists actively engaged in research in this field, the “Prague Declaration on Endocrine Disruption.” The Prague Declaration, also published as part of this monograph (available as Supplemental Material online at http://www.ehponline.org/docs/2007/10517/suppl.pdf), summarizes issues upon which the majority of scientists can agree, outlines research priorities for the next decade, and highlights steps that can be taken today to prevent health risks to humans and wildlife. It has been signed by more than 200 scientists from all over the world.
All contributors to the workshop are thanked cordially. Without their enthusiasm and hard work the meeting and this monograph would not have happened.
17 citations
TL;DR: The mobile exposure laboratory proved capable of maintaining U.S. Environmental Protection Agency- recommended exposure conditions while providing flexibility for rapid deployment at multiple sites with minimal operational disruption and further studies using this platform hold promise to resolve the convoluted interactions between complex effluents and inherent biological complexity.
Abstract: This study tested the hypotheses that (1) exposure to treated Water Reclamation Plant (WRP) effluent will induce biological effects in exposed fish that are consistent with environmental estrogen (EE) exposure; and (2) seasonal differences in effluent composition will moderate biological effects. We conducted seven on-site exposures using a mobile laboratory. Total estrogenicity of effluents was 10- to 20-fold higher during spring than in fall. Common EEs including steroid estrogens, alkylphenols, and bisphenol-A were ubiquitous. An unusual spike in total estrogenicity identified a combined sewer overflow event. Fathead minnows (Pimephales promelas) responded to exposure with subtle changes in vitellogenin concentrations and secondary sex characteristics. An opportunity to assess a common carp (Cyprinus carpio) population permanently sustained inside the Stickney WRP revealed pronounced exposure effects, but also the resilience of biological organisms even under long-term exposure. In contrast to other studies, no histopathological changes were found. The mobile exposure laboratory proved capable of maintaining U.S. Environmental Protection Agency-recommended exposure conditions while providing flexibility for rapid deployment at multiple sites with minimal operational disruption. Further studies using this platform hold promise to resolve the convoluted interactions between complex effluents and inherent biological complexity.
16 citations
TL;DR: Most target analytes suffered signal suppression in the presence of both fractionated and un-fractionated SROM, however greater interferences were measured with fractionated relative to bulkSROM, consistent with the view of organic matter as a supramolecular association of low molecular mass components having separate charged and structural features revealed only after dissociation.
15 citations