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: In this paper, the authors analyzed for the first time a group of 46 emerging contaminants (ECs) in the secondary effluent of the wastewater treatment plants (WWTP) of Prague.
Abstract: Emerging contaminants (ECs) are not monitored nor regulated consistently, but may have negative effects on human health and ecosystem balance. Although pharmaceuticals and personal care products are among the main ECs found in surface and wastewater, their toxicity and fate are currently not sufficiently studied. In this study, we analyzed for the first time a group of 46 ECs in the secondary effluent of the wastewater treatment plants (WWTP) of Prague. Thirty-seven compounds were identified in the discharge to surface water. Three compounds had no toxicology information on Artemia salina: furosemide, hydrochlorothiazide, and tramadol. We performed acute toxicity (LC50) tests and enzyme assays after 24 and 48 h at room temperature and 28 °C for these three compounds. LC50 ranged from 225.01 mg/L for furosemide, the most toxic, up to above 14,000 mg/L for tramadol. Changes in enzymatic activity for GST, GPx, AChE, and LDH when A. salina were exposed to LC25 for each contaminant were conspicuous and significant in a contaminant-, exposure time-, and temperature-dependent manner. These biochemical markers complement the toxicity profile of these contaminants in aquatic ecosystems and highlight the need for further research on other ECs and their implications, and the regulations required to protect human and ecological health.
23 citations
TL;DR: Evaluated a sludge pretreatment for simultaneously TOrCs attenuation and methane accumulation, laying foundation for promotion of sludge resource recycling.
19 citations
TL;DR: An overview of extraction methods for environmental water samples containing trace levels of pharmaceuticals and how current applications will mold how they are analyzed in the future is provided.
Abstract: Pharmaceuticals play a vital role in the prosperity of human and veterinarian health by diagnosing, treating, or preventing diseases. Produced in large quantities for various applications, pharmace...
15 citations
TL;DR: Artificial sweeteners and iodinated X-ray contrast media as tracers detected in surface water samples indicated that inputs to the aquatic environment via WWTP effluents are widespread and ACE was detected in every surface water sample indicating that it is chemically stable.
14 citations
TL;DR: In this article, a rapid and simple method was optimized and validated for the separation and quantification of anthracene and benzo(a)pyrene, two of the most toxic polycyclic aromatic hydrocarbons, at ultratrace levels in aqueous samples by direct injection.
Abstract: A rapid and simple method was optimized and validated for the separation and quantification of anthracene and benzo(a)pyrene, two of the most toxic polycyclic aromatic hydrocarbons, at ultratrace levels in aqueous samples by direct injection. The determination of anthracene and benzo(a)pyrene was carried out by reverse-phase high-performance liquid chromatography (HPLC) with fluorescence detection. A fractional factorial matrix and a Box-Behnken design were chosen for screening and optimization purposes, respectively. The optimized parameters that significantly influenced the system were the flow rate (1 mL min−1), the mobile phase strength (90% acetonitrile:10% deionized water), the column temperature (35°C), and the excitation wavelength (254 and 267 nm for anthracene and benzo(a)pyrene, respectively). The injection volume and the emission wavelength were fixed at 100 µL and 416 nm, respectively. The quantification limits were 75 ng L−1 for anthracene and 30 ng L−1 for benzo(a)pyrene. The relati...
13 citations
Cites methods from "Rapid direct injection LC-MS/MS met..."
...advantages of this technique are high reproducibility and accuracy, rapid analysis times, and reduced sample manipulation, subsequently minimizing sample contamination and compound loss (Buczyńska et al. 2014; Anumol et al. 2015; Boix et al. 2015)....
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...The advantages of this technique are high reproducibility and accuracy, rapid analysis times, and reduced sample manipulation, subsequently minimizing sample contamination and compound loss (Buczyńska et al. 2014; Anumol et al. 2015; Boix et al. 2015)....
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References
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TL;DR: The U.S. Geological Survey used five newly developed analytical methods to measure concentrations of 95 organic wastewater contaminants (OWCs) in water samples from a network of 139 streams across 30 states during 1999 and 2000 as mentioned in this paper.
Abstract: To provide the first nationwide reconnaissance of the occurrence of pharmaceuticals, hormones, and other organic wastewater contaminants (OWCs) in water resources, the U.S. Geological Survey used five newly developed analytical methods to measure concentrations of 95 OWCs in water samples from a network of 139 streams across 30 states during 1999 and 2000. The selection of sampling sites was biased toward streams susceptible to contamination (i.e. downstream of intense urbanization and livestock production). OWCs were prevalent during this study, being found in 80% of the streams sampled. The compounds detected represent a wide range of residential, industrial, and agricultural origins and uses with 82 of the 95 OWCs being found during this study. The most frequently detected compounds were coprostanol (fecal steroid), cholesterol (plant and animal steroid), N,N-diethyltoluamide (insect repellant), caffeine (stimulant), triclosan (antimicrobial disinfectant), tri(2-chloroethyl)phosphate (fire retardant), and 4-nonylphenol (nonionic detergent metabolite). Measured concentrations for this study were generally low and rarely exceeded drinking-water guidelines, drinking-water health advisories, or aquatic-life criteria. Many compounds, however, do not have such guidelines established. The detection of multiple OWCs was common for this study, with a median of seven and as many as 38 OWCs being found in a given water sample. Little is known about the potential interactive effects (such as synergistic or antagonistic toxicity) that may occur from complex mixtures of OWCs in the environment. In addition, results of this study demonstrate the importance of obtaining data on metabolites to fully understand not only the fate and transport of OWCs in the hydrologic system but also their ultimate overall effect on human health and the environment.
7,036 citations
TL;DR: This review attempts to synthesize the literature on environmental origin, distribution/occurrence, and effects and to catalyze a more focused discussion in the environmental science community.
Abstract: During the last three decades, the impact of chemical pollution has focused almost exclusively on the conventional "priority" pollutants, especially those acutely toxic/carcinogenic pesticides and industrial intermediates displaying persistence in the environment. This spectrum of chemicals, however, is only one piece of the larger puzzle in "holistic" risk assessment. Another diverse group of bioactive chemicals receiving comparatively little attention as potential environmental pollutants includes the pharmaceuticals and active ingredients in personal care products (in this review collectively termed PPCPs), both human and veterinary, including not just prescription drugs and biologics, but also diagnostic agents, "nutraceuticals," fragrances, sun-screen agents, and numerous others. These compounds and their bioactive metabolites can be continually introduced to the aquatic environment as complex mixtures via a number of routes but primarily by both untreated and treated sewage. Aquatic pollution is particularly troublesome because aquatic organisms are captive to continual life-cycle, multigenerational exposure. The possibility for continual but undetectable or unnoticed effects on aquatic organisms is particularly worrisome because effects could accumulate so slowly that major change goes undetected until the cumulative level of these effects finally cascades to irreversible change--change that would otherwise be attributed to natural adaptation or ecologic succession. As opposed to the conventional, persistent priority pollutants, PPCPs need not be persistent if they are continually introduced to surface waters, even at low parts-per-trillion/parts-per-billion concentrations (ng-microg/L). Even though some PPCPs are extremely persistent and introduced to the environment in very high quantities and perhaps have already gained ubiquity worldwide, others could act as if they were persistent, simply because their continual infusion into the aquatic environment serves to sustain perpetual life-cycle exposures for aquatic organisms. This review attempts to synthesize the literature on environmental origin, distribution/occurrence, and effects and to catalyze a more focused discussion in the environmental science community.
4,347 citations
TL;DR: In this article, the occurrence of 32 drug residues belonging to different medicinal classes like antiphlogistics, lipid regulators, psychiatric drugs, antiepileptic drugs, betablockers and β 2 -sympathomimetics as well as five metabolites has been investigated in German municipal sewage treatment plant (STP) discharges, river and stream waters.
3,015 citations
TL;DR: Atenolol, atrazine, DEET, estrone, meprobamate, and trimethoprim can serve as indicator compounds representing potential contamination from other pharmaceuticals and EDCs and can gauge the efficacy of treatment processes.
Abstract: The drinking water for more than 28 million people was screened for a diverse group of pharmaceuticals, potential endocrine disrupting compounds (EDCs), and other unregulated organic contaminants. Source water, finished drinking water, and distribution system (tap) water from 19 U.S. water utilities was analyzed for 51 compounds between 2006 and 2007. The 11 most frequently detected compounds were atenolol, atrazine, carbamazepine, estrone, gemfibrozil, meprobamate, naproxen, phenytoin, sulfamethoxazole, TCEP, and trimethoprim. Median concentrations of these compounds were less than 10 ng/L, except for sulfamethoxazole in source water (12 ng/L), TCEP in source water (120 ng/L), and atrazine in source, finished, and distribution system water (32, 49, and 49 ng/L). Atrazine was detected in source waters far removed from agricultural application where wastewater was the only known source of organic contaminants. The occurrence of compounds in finished drinking water was controlled by the type of chemical oxi...
1,481 citations
TL;DR: Conventional treatment would have low removal of many EDC/PPCPs, while addition of PAC and/or ozone could substantially improve their removals, and existing strategies that predict relative removal of herbicides, pesticides, and other organic pollutants can be directly applied.
Abstract: The potential occurrence of endocrine-disrupting compounds (EDCs) as well as pharmaceuticals and personal care products (PPCPs) in drinking water supplies raises concern over the removal of these compounds by common drinking water treatment processes. Three drinking water supplies were spiked with 10 to 250 ng/L of 62 different EDC/PPCPs; one model water containing an NOM isolate was spiked with 49 different EDC/PPCPs. Compounds were detected by LC/MS/MS or GC/MS/MS. These test waters were subjected to bench-scale experimentation to simulate individual treatment processes in a water treatment plant (WTP). Aluminum sulfate and ferric chloride coagulants or chemical lime softening removed some polyaromatic hydrocarbons (PAHs) but removed 98% of GC/MS/MS compounds (more volatile) and 10% to >95% of LC/MS/MS compounds (more polar); higher PAC dosages improved EDC/PPCP removal. EDC/PPCP per...
1,433 citations