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: 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.
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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: This study examined the occurrence in wastewater of 11 aromatic biocides, pesticides and degradates, and their fate during passage through US treatment plants, as well as the chemical mass contained in sewage sludge (biosolids) destined for land application to address some of the data gaps identified by the National Research Council.
Abstract: This study examined the occurrence in wastewater of 11 aromatic biocides, pesticides and degradates, and their fate during passage through US treatment plants, as well as the chemical mass contained in sewage sludge (biosolids) destined for land application. Analyte concentrations in wastewater influent, effluent and sludge from 25 facilities in 18 US states were determined by liquid chromatography electrospray (tandem) mass spectrometry. Dichlorocarbanilide, fipronil, triclocarban, and triclosan were found consistently in all sample types. Dichlorophene, hexachlorophene, and tetrachlorocarbanilide were detected infrequently only, and concentrations of the phenyl urea pesticides diflubenzuron, hexaflumuron, and linuron were below the limit of detection in all matrixes. Median concentrations (±95% confidence interval) of quantifiable compounds in influent ranged from 4.2 ± 0.8 μg L−1 for triclocarban to 0.03 ± 0.01 μg L−1 for fipronil. Median concentrations in effluent were highest for triclocarban and triclosan (0.23 ± 0.08 and 0.07 ± 0.04 μg L−1, respectively). Median aqueous-phase removal efficiencies (±95% CI) of activated sludge treatment plants decreased in the order of: triclosan (96 ± 2%) > triclocarban (87 ± 7%) > dichlorocarbanilide (55 ± 20%) > fipronil (18 ± 22%). Median concentrations of organohalogens were typically higher in anaerobically than in aerobically digested sludges, and peaked at 27 600 ± 9600 and 15 800 ± 8200 μg kg−1 for triclocarban and triclosan, respectively. Mass balances obtained for three primary pesticides in six activated sludge treatment plants employing anaerobic digestion suggested a decreasing overall persistence from fipronil (97 ± 70%) to triclocarban (87 ± 29%) to triclosan (28 ± 30%). Nationwide release of the investigated organohalogens to agricultural land via municipal sludge recycling and into surface waters is estimated to total 258 000 ± 110 00 kg year−1 (mean ± 95% confidence interval), with most of this mass derived from antimicrobial consumer products of daily use. This study addresses some of the data gaps identified by the National Research Council in its 2002 study on standards and practices of biosolids application on land.
80 citations
TL;DR: Results suggest that conservative mass transport is an important boundary condition for assessment of the input, fate, and effects of CECs in estuaries at the bottom of these watersheds.
Abstract: ySouthern California Coastal Water Research Project Authority, Costa Mesa, California, USAzCalifornia Regional Water Quality Control Board, Los Angeles Region, Los Angeles, California, USAxAdvanced Water Technology Center, Department of Civil and Environmental Engineering, Colorado School of Mines, Golden, Colorado, USAkChemical and Environmental Engineering, University of Arizona, Tucson, Arizona, USA#Los Angeles County Sanitation Districts, Whittier, California, USA(Submitted 2 July 2013; Returned for Revision 15 August 2013; Accepted 2 November 2013)Abstract: To inform future monitoring and assessment of chemicals of emerging concern (CECs) in coastal urban watersheds, theoccurrence and fate of more than 60 pharmaceuticals and personal care products (PPCPs), commercial/household chemicals, current-usepesticides, and hormones were characterized in 2 effluent-dominated rivers in southern California (USA). Water samples were collectedduring 2 low-flow events at locations above and below the discharge points of water reclamation plants (WRPs) and analyzed using gaschromatography–massspectrometryandliquidchromatography–tandemmassspectrometry.Approximately50%oftargetedCECsweredetectableatstationsdownstreamfromWRPs,comparedwith<31%and<10%atthereferencestationsabovetheWRPs.Concentrationsof chlorinated phosphate flame retardants were highest among the CECs tested, with mean total aggregate concentrations of tris(2-chloroethyl) phosphate (TCEP), tris(1-chloro-2-propyl) phosphate (TCPP), and tris(1,3-dichloro-2-propyl) phosphate (TDCPP) of3400ng/Land2400ng/L forthe 2rivers. Maximum in-stream concentrationsof pyrethroids (bifenthrin andpermethrin), diclofenac, andgalaxolide exceeded risk-based thresholds established for monitoring of CECs in effluent-dominated receiving waters. In contrast,maximumconcentrationsofPPCPscommonlydetectedintreatedwastewater(e.g.,acetaminophen,N,N,diethyl-meta-toluamide[DEET],and gemfibrozil) were less than 10% of established thresholds. Attenuation of target CECs was not observed downstream of WRPdischarge until dilution by seawater occurred in the tidal zone, partly because of the short hydraulic residence times in these highlychannelizedsystems(<3d).InadditiontoconfirmingCECsforfuturein-streammonitoring,theseresultssuggestthatconservativemasstransport is an important boundary condition for assessment of the input, fate, and effects of CECs in estuaries at the bottom of thesewatersheds. Environ Toxicol Chem 2014;33:350–358. # 2013 SETACKeywords: Chemicals of emerging concern (CECs) Pharmaceuticals and personal care products (PPCPs) Occurrence FateUrbanized coastal watersheds Water reclamation plantsINTRODUCTION
78 citations
TL;DR: Results from this study provide a good foundation in deciding whether advanced treatment is necessary to attenuate TOrC deemed to be of concern in effluents, or if natural treatment such as managed aquifer recharge provides sufficient protection to public health.
76 citations
TL;DR: The proposed analytical method is sensitive, rapid and robust; hence it can be used to analyze a large variety of trace organic compounds in different water matrixes.
Abstract: The widespread utilization of organic compounds in modern society and their dispersion through wastewater have resulted in extensive contamination of source and drinking waters. The vast majority of these compounds are not regulated in wastewater outfalls or in drinking water while trace amounts of certain compounds can impact aquatic wildlife. Hence it is prudent to monitor these contaminants in water sources until sufficient toxicological data relevant to humans becomes available. A method was developed for the analysis of 36 trace organic contaminants (TOrCs) including pharmaceuticals, pesticides, steroid hormones (androgens, progestins, and glucocorticoids), personal care products and polyfluorinated compounds (PFCs) using a single solid phase extraction (SPE) technique with ultra-high performance liquid chromatography coupled to tandem mass spectrometry (UHPLC-MS/MS). The method was applied to a variety of water matrices to demonstrate method performance and reliability. UHPLC-MS/MS in both positive and negative electrospray ionization (ESI) modes was employed to achieve optimum sensitivity while reducing sample analysis time (<20 min) compared with previously published methods. The detection limits for most compounds was lower than 1.0 picogram on the column while reporting limits in water ranged from 0.1 to 15 ng/L based on the extraction of a 1 L sample and concentration to 1 mL. Recoveries in ultrapure water for most compounds were between 90-110%, while recoveries in surface water and wastewater were in the range of 39-121% and 38-141% respectively. The analytical method was successfully applied to analyze samples across several different water matrices including wastewater, groundwater, surface water and drinking water at different stages of the treatment. Among several compounds detected in wastewater, sucralose and TCPP showed the highest concentrations. The proposed method is sensitive, rapid and robust; hence it can be used to analyze a large variety of trace organic compounds in different water matrixes.
70 citations
TL;DR: No difference was observed in the ozone dose required for the concentration of SMX to fall below the limit of detection in pure water and wastewater, and four peaks obtained during experiments at low concentration were observed at the same retention times as four of the peaks obtained in higher concentration samples.
68 citations