Photochemical degradation of the antidepressant sertraline in aqueous solutions by UVC, UVC/H2O2, and UVC/S2O82.

Antidepressants are released into the aquatic environment because of their incomplete removal from wastewater treatment plants. In the present work, we investigated the photochemical degradation of a commonly prescribed antidepressant, namely sertraline, in aqueous matrices. The molar absorption coefficient of sertraline at 254 nm and at various pH values in the range from 4.0 to 9.0 was 444±65 L•mol-1•cm-1, while the quantum yield of its direct photolysis under UVC radiation (λ = 254 nm) was (1.7±0.1) × 10-2 mol∙einstein-1 (i.e., both values were relatively low). Next, we investigated the photochemical degradation of sertraline under UVC radiation in the presence of hydrogen peroxide, H2O2 (i.e., UVC/H2O2) or persulfate ions, S2O82- (i.e., UVC/PS). Several parameters were studied, such as the initial concentrations of the oxidants, solution pH, and the composition of the aqueous matrix (experiments were carried out in aqueous phosphate buffers, in synthetic wastewater, as well as in synthetic fresh and hydrolyzed human urine). It was found that, in all aqueous matrices, the photochemical degradation of sertraline followed pseudo first-order kinetics. The values of the observed pseudo first-order rate constants in the UVC/H2O2 and UVC/PS processes were from one to three orders of magnitude higher than the corresponding value in the UVC process. The UVC/PS process was more efficient than the UVC/H2O2 process, either in aqueous phosphate buffer solutions or in synthetic wastewaters, despite the comparable reactivity of sertraline towards hydroxyl and sulfate radicals. However, both processes resulted in partial mineralization of the compound after prolonged irradiation. In the UVC/H2O2 process, there was an optimum H2O2 concentration which depended on the aqueous matrix, while in the UVC/PS process, there was an almost linear increase in treatment efficiency as a function of PS concentration, at least in the range of concentrations studied in the present work. Solution pH in the range from 6.0 to 9.0 had a relatively negligible effect on treatment performance for both processes. In synthetic urine matrices, despite the reduction in reaction rate (the observed pseudo first-order rate constants were reduced by approximately one to two orders of magnitude), the photochemical degradation of sertraline proceeded to a relatively satisfactory degree. Finally, the calculations of the electrical energy per order and the associated cost showed that the UVC/H2O2 and UVC/PS processes are cost-efficient and suitable for full-scale applications.

Assessment of tetrabromobisphenol-A (TBBPA) content in plastic waste recovered from WEEE.

Due to the variability of additives and polymer types used in electrical and electronic equipment (EEE), and in accordance with the European Directive 2012/19/EU, an implementation of sound management practices is necessary. This work focuses on assessing the content of tetrabromobisphenol-A (TBBPA) in acrylonitrile-butadiene-styrene (ABS), polypropylene (PP), polycarbonate (PC) and their polymer blends (i.e. PC/ABS). A total of 36 plastic housing samples originating from microwave ovens, electric irons, vacuum cleaners and DVD/CD players were subjected to microwave-assisted-extraction (MAE) and/or ultrasound-assisted-extraction (UAE). Maximum mean concentration values of TBBPA measured in DVD/CD players and vacuum cleaners ranged between 754-1146 µg/kg, and varied per polymer type, as follows: 510-2515 µg/kg in ABS and 55-3109 µg/kg in PP. The results indicated that MAE was more sufficient than UAE in the extraction of TBBPA from ABS. To optimize the UAE procedure, various solvents were tested. Higher amounts of TBBPA were obtained from ABS and PP using a binary mixture of a polar-non-polar solvent, isopropanol:n-hexane (1:1), whereas the sole use of isopropanol exhibited incomplete extraction.

Rapid determination of octanol-water partition coefficient using vortex-assisted liquid-liquid microextraction.

Vortex-assisted liquid-liquid microextraction (VALLME) coupled with high-performance liquid chromatography (HPLC) is proposed here for the rapid determination of octanol-water partitioning coefficients (Kow). VALLME uses vortex agitation, a mild emulsification procedure, to disperse microvolumes of octanol in the aqueous phase thus increasing the interfacial contact area and ensuring faster partitioning rates. With VALLME, 2min were enough to achieve equilibrium conditions between the octanolic and aqueous phases. Upon equilibration, separation was achieved using centrifugation and the octanolic microdrop was collected and analyzed in a HPLC system. Six model compounds with logKow values ranging between ∼0.5 and 3.5 were used during the present investigations. The proposed method produced logKow values that were consistent with previously published values and the recorded uncertainty was well within the acceptable log unit range. Overall, the key features of the proposed Kow determination procedure comprised speed, reliability, simplicity, low cost and minimal solvent consumption.

Validity and reliability of the Greek version of Brown's locus of control scale (BLOCS).

Studies in different research fields have shown that locus of control is a meaningful concept. A translated measurement of locus of control in Greece is the Brown locus of control scale (BLOCS), but the translation has not been yet validated. Construct validity and reliability of the BLOCS Greek version was investigated in a sample of employees in five public institutions. Three dimensions identified in the original study were observed. A reduced scale of 20 items showed better psychometric properties: Cronbach's alphas were for the total scale .76 (McDonald's omega = .72), and internal .76, external social .73, and external other .73, comparable to the original and improved if 5 items are removed.

Fast screening of perfluorooctane sulfonate in water using vortex-assisted liquid-liquid microextraction coupled to liquid chromatography-mass spectrometry.

Fast screening of trace amounts of the perfluorooctane sulfonate anion (PFOS) in water samples was performed following a simple, fast and efficient sample preparation procedure based on vortex-assisted liquid-liquid microextraction (VALLME) prior to liquid chromatography-mass spectrometry. VALLME initially uses vortex agitation, a mild emulsification procedure to disperse microvolumes of octanol, a low density extractant solvent, in the aqueous sample. Microextraction under equilibrium conditions is thus achieved within few minutes. Subsequently, centrifugation separates the two phases and restores the initial microdrop shape of the octanol acceptor phase, which can be collected and used for liquid chromatography-single quadrupole mass spectrometry analysis. Several experimental parameters were controlled and the optimum conditions found were: 50 µL of octanol as the extractant phase; 20 mL aqueous donor samples (pH=2); a 2 min vortex extraction time with the vortex agitator set at a 2500 rpm rotational speed; no ionic strength adjustment. Centrifugation for 2 min at 3500 rpm yielded separation of the two phases throughout this study. Enhanced extraction efficiencies were observed at low pH which was likely due to enhanced electrostatic interaction between the negatively PFOS molecules and the positively charged octanol/water interface. The effect of pH was reduced in the presence of sodium chloride, likely due to electrical double layer compression. The linear response range for PFOS was from 5 to 500 ng L(-1) (coefficient of determination, r(2), 0.997) and the relative standard deviation for aqueous solutions containing 10 and 500 ng L(-1) PFOS were 7.4% and 6.5%, respectively. The limit of detection was 1.6 ng L(-1) with an enrichment factor of approximately 250. Analysis of spiked tap, river and well water samples revealed that matrix did not affect extraction.

Vortex-assisted liquid-liquid microextraction of octylphenol, nonylphenol and bisphenol-A.

A new and fast equilibrium-based solvent microextraction technique termed vortex-assisted liquid-liquid microextraction (VALLME) has been developed and used for the trace analysis of octylphenol, nonylphenol and bisphenol-A in water and wastewater samples. According to VALLME, dispersion of microvolumes of a low density extractant organic solvent into the aqueous sample is achieved by using for the first time vortex mixing, a mild emulsification procedure. The fine droplets formed could extract target analytes towards equilibrium faster because of the shorter diffusion distance and larger specific surface area. Upon centrifugation the floating extractant acceptor phase restored its initial single microdrop shape and was used for high-performance liquid chromatographic analysis. Different experimental parameters were controlled and the optimum conditions found were: 50 microl of octanol as the extractant phase; 20 ml aqueous donor samples; a 2 min vortex extraction time with the vortex agitator set at a 2500 rpm rotational speed; centrifugation for 2 min at 3500 rpm; no ionic strength or pH adjustment. The calculated calibration curves gave high levels of linearity yielding correlation coefficients (r(2)) greater than 0.9935. The repeatability and reproducibility of the proposed method were found to be good and the limits of the detection were calculated in the low microg l(-1) level ranging between 0.01 and 0.07 microg l(-1). Matrix effects were determined by applying the proposed method to spiked tap, river water and treated municipal wastewater samples. The proposed method was finally applied to the determination of target pollutants in real wastewater effluent samples using the standard addition method.

Simultaneous photocatalytic oxidation of As(III) and humic acid in aqueous TiO2 suspensions.

The simultaneous photocatalytic oxidation of As(III) and humic acid (HA) in aqueous Degussa P25 TiO(2) suspensions was investigated. Preliminary photocatalytic studies of the binary As(III)/TiO(2) and HA/TiO(2) systems showed that As(III) was oxidized more rapidly than HA and the extent of photocatalytic oxidation of each individual component (i.e. As(III) or HA) increased with decreasing its initial concentration and/or increasing catalyst loading. The simultaneous photocatalytic oxidation of As(III) and HA in the ternary As(III)/HA/TiO(2) system showed that both As(III) and HA oxidation was reduced in the ternary system compared to the corresponding binary systems. The effect of operating conditions in the ternary system, such as initial As(III), HA and TiO(2) concentrations (in the range 3-20mg/L, 10-100mg/L and 50-250 mg/L respectively), initial solution pH (3.6-6.7) and reaction time (10-30 min), on photocatalytic As(III) and HA oxidation was assessed implementing a two-level factorial experimental design methodology. Seven and ten factors were found statistically important in the case of photocatalytic As(III) and HA oxidation respectively. Based on these statistically significant factors, a first order polynomial model describing As(III) and HA photocatalytic oxidation was constructed and a very good agreement was obtained between the experimental values and those predicted by the model, while the observed differences may be readily explained as random noise.

Arsenic mobility and stabilization in topsoils.

Agricultural topsoil can be polluted with arsenic due to irrigation with contaminated water from geothermal sources. This work evaluates the mobility of arsenic in topsoils and stabilization of arsenic with zero valent iron (ZVI), in short term experiments. The objective of this study was the development of a simplified empirical model that can predict the concentration of iron released from ZVI and the concentration of arsenic remaining in the solution during short term stabilization experiments. The empirical model correlates the release of arsenic from soil with dissolved iron concentration during stabilization experiments, in different pH and ZVI/solution ratios. Reaction time and the ratio of ZVI/soil affect the efficiency of arsenic stabilization in topsoils with ZVI. In addition, the release/desorption experiments and adsorption experiments, under different conditions, showed that the concentration of arsenate desorbed from soil depends on the temperature. Higher concentrations of arsenate were reported, as the temperature increased.