Comparison of benzotriazole ultraviolet stabilizers (BUVs) removal from wastewater after subsequent stages of sequencing batch reactor (SBR) treatment process.

The research focused on benzotriazole ultraviolet stabilizers (BUVs) which are commonly used compounds despite being found dangerous, e.g. promoting breast cancer cell proliferation, damaging vital organs such as hearts, brains livers and kidneys. The aim of the study was to analyse the efficiency and removal rate of BUVs from wastewater depending on the quantity of tested compounds and SBR anaerobic-aerobic conditions. The study was conducted in sequencing batch reactors (SBRs - 17 L) with real flocculent activated sludge (8 L) and model wastewater (5 L) containing UV-326, UV-327, UV-328, UV-329 and UV-P from 50 to 600 µg∙L-1. The SBR were operated in 390 cycles of 7 h and 10 min over 130 days. The similarity of the technological parameters of the treatment process to those used in a real wastewater treatment plant was maintained. Efficiency removal of individual BUVs was strictly dependent on the dose of compounds introduced into wastewater and ranged from 68.2 to 97 %. Removal of UV-329 occurred with lowest efficiency (from 68.2 to 85.2 %) while UV-326 was most efficiently removed from the wastewater (from 94.1 to 97 %). UV-329 was removed from wastewater with the lowest (0.0968-0.9524 µg∙L-1∙min-1) average removal rate while UV-327 with the highest (0.16-1.3357 µg∙L-1∙min-1), irrespective of BUVs dose in the influent. Secondary release of BUVs into the wastewater occurred in SBR during the settling phase and was dependent on the type and concentration of the BUVs in the raw wastewater. This occurrence was noted for UV-326 ≥ 100; UV-327 = 600; UV-328 ≥ 200; UV-329 ≥ 50 and UV-P ≥ 100 µg∙L-1. The settling phase needs to be shortened to the required minimum. This is an important conclusion for WWTPs in regards to SBR cycle duration and technological parameters of the treatment process.

Degradation of UV-P mediated by hydroxyl radical, sulfate radical and singlet oxygen in aquatic solution: DFT and experimental studies.

2-(2'-hydroxy-5'-methylphenyl) benzotriazole (UV-P) is a type of emerging persistent organic pollutant that is reported harmful to organisms. However, its degradation mechanisms and transformation behaviors in aquatic environments are not yet clear, which are significant for better understanding its environmental fate and potential toxicological impacts. In present work, the degradation mechanisms, kinetics, half-life times and eco-toxicity assessment of UV-P initiated by hydroxyl radical (•OH), sulfate radical (SO4•‾), and singlet oxygen (1O2) are systematically studied using density functional theory (DFT) and experimental methods. The initiated reaction results show that benzene ring of UV-P is vulnerable to attack by •OH, while benzotriazole is easily attacked by SO4•‾. The kinetic calculations indicate that •OH-addition reaction R15 is dominant initial pathway. And the half-life (t1/2) of UV-P is calculated according to rate constants, t1/2 decreases rapidly with [ROS] increasing. UV-P exhibits environmental persistence when [•OH] ≤ 10-17 M. The subsequent degradation mechanisms of hydroxylated UV-P react with •OH and O2 are also calculated. A novel ring-opening reaction channel is proposed that O2-addition intermediate combines with hydroperoxyl radical (HO2•) to cleave aromatic ring. The rate-determining step is intramolecular dehydration reaction with the energy barrier of 32.98 kcal mol-1 and 41.13 kcal mol-1 to cleave benzene ring and benzotriazole ring, respectively. The degradation experiments of UV-P are conducted in Co3O4 activated potassium peroxymonosulfate (PMS) system, and liquid chromatograph-mass spectrometer (LC-MS) results identified that dihydroxylated species are main intermediates, which is consistent with theoretical calculation results. Furthermore, the eco-toxicity assessment shows that the acute and chronic toxicities of most degradation products are reduced compared with UV-P, however, their toxicity levels still keep at toxic and harmful. The environmental risk of UV-P deserves more attention.

Benzotriazole UV-stabilizers and benzotriazole: Antiandrogenic activity in vitro and activation of aryl hydrocarbon receptor pathway in zebrafish eleuthero-embryos.

Benzotriazole UV-stabilizers (BUVs) are applied in materials for protection against UV-irradiation. They are widely used, bioaccumulate and share structural similarities to benzotriazole. Benzotriazole (1HBT) finds application as corrosion inhibitor in dishwashing detergents, antifreeze (vehicles) and aircraft de-icing agent. BUVs and 1HBT are persistent and ubiquitous in the aquatic environment, but there is little understanding of the ecotoxicological implications. Here, we comparatively analyze the hormonal activity in vitro and effects in zebrafish eleuthero-embryos in vivo. 2-(2-Hydroxy-5-methylphenyl)benzotriazole (UV-P), 2-(3-t-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotriazole (UV-326), UV-327, UV-328, UV-329 and UV-320 showed no estrogenicity (YES assay) and androgenicity (YAS assay). However, UV-P and 1HBT showed significant antiandrogenic activity. We assessed the transcription profiles of up to 26 genes associated with different toxicological pathways in zebrafish eleuthero-embryos to elucidate potential modes of action of UV-P, UV-326 and 1HBT. Embryos were experimentally exposed for 144hpf to three measured concentrations of 15.8, 70.8, and 690µg/L UV-P, 7.5, 31.7, and 84.3µg/L UV-326 and 7.9, 97.3 and 1197.3µg/L 1HBT. Among the 26 transcripts, the induction of the aryl hydrocarbon receptor (AHR) pathway by UV-P and UV-326 was the most significant finding. UV-P led to dose-related induction of AHR1, ARNT2 and cyp1a1, as well as of phase II enzymes glutathione-S-transferase (gstp1) and ugt1a. UV-326 led to a significant induction of cyp1a1 and AHR2, but down-regulation of gstp1 at 84µg/L. Only little transcriptional alterations occurred in genes related to apoptosis, oxidative stress, hormone receptors, and steroidogenesis including aromatase. 1HBT led to only a few expressional changes at 1197µg/L. Our data lead to the conclusion that UV-P and UV-326 activate the AHR-pathway, whereas 1HBT shows only little transcriptional alterations. It should be noted, however, that effects have been observed at concentration much higher than those occurring in the environment. Forthcoming studies should show whether the observed antiandrogenic activities and transcriptional changes translate into physiological effects .