Occurrence and distribution of benzothiazole in the Schwarzbach watershed (Germany)
Institute of Environmental Systems Research, University of Osnabrueck, Barbarastrasse 12, D-49090, Osnabrueck, Germany.Journal of Environmental Monitoring (Impact Factor: 2.18). 08/2011; 13(10):2838-43. DOI: 10.1039/c1em10474h
This study quantifies the regional distribution of the micropollutant benzothiazole (BT) in river water by sampling 15 river sites in the Schwarzbach watershed (about 400 km(2)) from November 2008 to February 2010. Additionally, wastewater samples from three municipal wastewater treatment plants (WWTPs) in Germany were analyzed. BT was detected in all wastewater influent and effluent samples as well as in all river water samples collected downstream of wastewater discharge. This corroborates the ubiquitous occurrence of BT in the aqueous environment. Concentrations were between 58 and 856 ng L(-1) in the river water. The observed mean concentration at the outlet of the investigated catchment was 109 ng L(-1). With only a few exceptions, temporal and spatial variations of BT concentrations in river water were low. Rather similar BT concentrations over a wide range of river discharge indicate that dilution along the mainstream is negligible and, thus, supports the hypothesis that paved surface runoff during rain events is an important BT source not only for wastewater influent but also for river water. This was supported by detecting the highest BT concentrations at sampling locations close to the dense highway network around the city of Frankfurt. Since BT was also detected in river water collected from locations that were clearly unaffected by wastewater effluent discharge, surface runoff must be considered as a diffuse source of BT in river water.
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ABSTRACT: Challenging tasks, increasing demands, and new generations of powerful analytical instruments initiated considerable progress in aquatic environmental analysis and led to a considerable improvement of analytical performance during the last few years. The ever growing number of emerging pollutants is tackled by specific and highly sensitive analytical methods with detection limits of a few nanogram per liter and even lower. Wide-scope monitoring techniques and multiclass and multiresidue analysis allow for the simultaneous determination of hundreds of compounds. The high mass resolution capability and mass accuracy of advanced mass spectrometric instruments, i.e., time-of-flight (TOF) MS or Fourier transform (FT)-Orbitrap MS, enable combined target and non-target analysis, including the identification of metabolites and abiotic degradation products. This minireview highlights some of the most recent developments in the trace analysis of important organic water pollutants and focuses on some specific groups of emerging contaminants, i.e., pharmaceuticals, flame retardants, disinfection by-products, surfactants, per- and polyfluorinated compounds, benzotriazoles, and benzothiazoles, as well as on the identification of transformation products and on non-target analysis. References were selected according to their exemplary and innovative character and to their practical relevance.
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ABSTRACT: ABSTRACT In recent years, emerging pollutants (xenobiotics) have become a highly relevant topic in science due to their constant release into the environment and their potential adverse effects on human health. The main objectives of this thesis were to develop sensitive and selective analytical methods for the determination of benzotriazoles, benzothiazoles, bisphenol A diglycidyl ethers, p-hydroxybenzoic acid esters (parabens), benzophenonetype UV filters, triclosan, and triclocarban in human biological media (urine) by LCMS/ MS, as well as to determine concentrations in individuals from different countries, establish correlations among the target chemicals, and estimate the potential human exposure doses. The thesis presents the aforementioned chemicals and their methods of analysis. Herein, an elaborate review of the existing bioanalytical methodologies is undertaken for all assessed xenobiotics. The experimental section of the thesis is constituted of four parts: (1) Determination of benzotriazoles and benzothiazoles in human urine by liquid chromatography-tandem mass spectrometry (Chapter 3) (2) Benzotriazoles and benzothiazoles in human urine from several countries: A perspective on occurrence, biotransformation, and human exposure determination (Chapter 4) (3) A multi-class bioanalytical methodology for the determination of bisphenol A diglycidyl ethers, phydroxybenzoic acid esters, benzophenone-type UV filters, triclosan, and triclocarban in human urine by liquid chromatography-tandem mass spectrometry (Chapter 5) (4) Widespread occurrence of bisphenol A diglycidyl ethers, p-hydroxybenzoic acid esters (parabens), benzophenone type-UV filters, triclosan, and triclocarban in human urine from Athens, Greece (Chapter 6). It is hoped that these studies will provide a major step forward in better understanding methods of determination, occurrence and human exposure, metabolism, and biotransformation pathways of these xenobiotics in humans. SUBJECT AREA: Bioanalytical Chemistry KEYWORDS: Xenobiotics, LC-MS/MS, urine, exposure, metabolism
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ABSTRACT: Benzotriazoles (BTs) and benzothiazoles (BTHs) are extensively used chemicals found in a wide range of household and industrial products. They are chemically stable and are therefore ubiquitous in the aquatic environment. The present study focuses on the potential of ultraviolet (UV) irradiation, alone or in combination with hydrogen peroxide (H2O2), to remove BTs and BTHs from contaminated waters. Six compounds, three out of each chemical class, were investigated using a low-pressure mercury lamp (main emission at 254 nm) as the radiation source. Initially, the direct phototransformation kinetics and quantum yield in dilute aqueous solution was studied over the pH range of 4-12. All BTs and BTHs, except for benzothiazole, exhibited pH-dependent direct phototransformation rate constants and quantum yields in accordance to their acid-base speciation (7.1 < pKa < 8.9). The direct phototransformation quantum yields (9.0 × 10(-4)-3.0 × 10(-2) mol einstein(-1)), as well as the photon fluence-based rate constants (1.2-48 m(2) einstein(-1)) were quite low. This suggests that UV irradiation alone is not an efficient method to remove BTs and BTHs from impacted waters. The second-order rate constants for the reaction of selected BTs and BTHs with the hydroxyl radical were also determined, and found to fall in the range of 5.1-10.8 × 10(9) M(-1) s(-1), which is typical for aromatic contaminants. Finally, the removal of BTs and BTHs was measured in wastewater and river water during application of UV irradiation or the advanced oxidation process UV/H2O2. The latter process provided an efficient removal, mostly due to the effect of the hydroxyl radical, that was comparable to other aromatic aquatic contaminants, in terms of energy requirement or treatment costs. Copyright © 2015 Elsevier Ltd. All rights reserved.
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