Transformation and toxicity studies of UV filter diethylamino hydroxybenzoyl hexyl benzoate in the swimming pools.

Diethylamino hydroxybenzoyl hexyl benzoate (DHHB), an ultraviolet (UV) filter, can be found in sunscreens and other personal care products and thus can be introduced into swimming pools through the swimmers. In outdoor pools, DHHB will inevitably interact with free chlorine and sunlight. Therefore, the mechanism of solar­chlorine chemical transformation of DHHB, as well as the environmental risk, were investigated in this work. In chlorinated with solar (Cl + solar) process, free chlorine was the dominant contributor to 85% of the DHHB degradation, while hydroxyl radicals and reactive chlorine species contributed only 15% because of low free radical generation and fast DHHB and free chlorine reaction rates. Scavenging matrices, such as Cl-, NH4+, and dissolved organic matter (DOM), inhibited the degradation of DHHB in the Cl + solar process, while Br-, HCO3-, NO3-, and urea promoted DHHB degradation. DHHB degradation was inhibited in tap water swimming pool samples, while it was enhanced in seawater pool samples by the Cl + solar process. Seven transformation by-products (TBPs) including mono-, dichlorinated, dealkylate, and monochloro-hydroxylated TBPs were identified. Three degradation pathways, chlorine substitution, chlorine and hydroxyl substitution, and dealkylation were proposed for DHHB transformation in the Cl + solar process. Both Quantitative structure-activity relationship and Aliivibrio fischeri toxicity tests demonstrated increased toxicity for the chlorinated TBPs. A risk assessment of the DHHB and its TBPs suggested that both DHHB and its chlorinated TBPs pose a significant health risk.

Stable isotope labeling for detection of ozonation byproducts in effluent organic matter with FT-ICR-MS.

Despite effluent organic matter (EfOM) being a major consumer of ozone during wastewater treatment, little is known about ozonation byproducts (OBPs) produced from EfOM. To unambiguously identify OBPs, heavy ozone was used to ozonate EfOM, resulting in 18O labeled and unlabeled OBPs. Labeled OBPs mostly represent a single 18O transfer and were classified as either direct or indirect OBPs based on the 18O/16O intensity ratios of the isotopologues. Of the 929 labeled OBPs, 84 were unequivocally classified as direct OBPs. The remainder suggest a major contribution by indirect, hydroxyl radical induced formation of OBPs in EfOM. Overall, labelled OBPs possess a low degree of unsaturation and contributed most to OBP peak intensity - marking them as potential end products. A few direct and indirect OBPs with high peak intensity containing 18O and heteroatoms (N, S) were fragmented with CID FT-ICR-MS/MS and screened for indicative neutral losses carrying heavy oxygen. The neutral loss screening was used to detect the 18O location on the OBP and indicate the original functional group in EfOM based on known reaction mechanisms. We identified sulfoxide and sulfonic acid functional groups in selected OBPs - implying the presence of reduced sulfur in EfOM molecules - while no evidence for nitrogen containing functional groups reacting with ozone was found.

Visible-Light Activation of Persulfate or H2O2 by Fe2O3/TiO2 Immobilized on Glass Support for Photocatalytic Removal of Amoxicillin: Mechanism, Transformation Products, and Toxicity Assessment.

Fe2O3/TiO2 nanocomposites were fabricated via a facile impregnation/calcination technique employing different amounts iron (III) nitrate onto commercial TiO2 (P25 Aeroxide). The as-prepared Fe2O3/TiO2 nanocomposites were characterized by X-ray diffraction (XRD), Raman spectroscopy (RS), scanning electron microscopy/energy-dispersive spectroscopy (SEM/EDXS), X-ray photoelectron spectroscopy (XPS), Brunauer-Emmett-Teller analysis (BET), electron impedance spectroscopy (EIS), photoluminescence spectroscopy (PL), and diffuse reflectance spectroscopy (DRS). As a result, 5% (w/w) Fe2O3/TiO2 achieved the highest photocatalytic activity in the slurry system and was successfully immobilized on glass support. Photocatalytic activity under visible-light irradiation was assessed by treating pharmaceutical amoxicillin (AMX) in the presence and absence of additional oxidants: hydrogen peroxide (H2O2) and persulfate salts (PS). The influence of pH and PS concentration on AMX conversion rate was established by means of statistical planning and response surface modeling. Results revealed optimum conditions of [S2O82-] = 1.873 mM and pH = 4.808; these were also utilized in presence of H2O2 instead of PS in long-term tests. The fastest AMX conversion possessing a zero-order rate constant of 1.51 × 10-7 M·min-1 was achieved with the photocatalysis + PS system. The AMX conversion pathway was established, and the evolution/conversion of formed intermediates was correlated with the changes in toxicity toward Vibrio fischeri. Reactive oxygen species (ROS) scavenging was also utilized to investigate the AMX conversion mechanism, revealing the major contribution of photogenerated h+ in all processes.

Phase transformation-driven persulfate activation by coupled Fe/N-biochar for bisphenol a degradation: Pyrolysis temperature-dependent catalytic mechanisms and effect of water matrix components.

Fe-N co-doped biochar is recently an emerging carbocatalyst for persulfate activation in situ chemical oxidation (ISCO). However, the involved catalytic mechanisms remain controversial and distinct effects of coexisting water components are still not very clear. Herein, we reported a novel N-doped biochar-coupled crystallized Fe phases composite (Fe@N-BC800) as efficient and low-cost peroxydisulfate (PDS) activators to degrade bisphenol A (BPA), and the underlying influencing mechanism of coexisting inorganic anions (IA) and humic constituent. Due to the formation of graphitized nanosheets with high defects (AI index>0.5, ID/IG = 1.02), Fe@N-BC800 exhibited 2.039, 5.536, 8.646, and 23.154-fold higher PDS catalytic activity than that of Fe@N-BC600, Fe@N-BC400, N-BC, BC. Unlike radical pathway driven by carbonyl group and pyrrolic N of low/mid-temperature Fe@N-BCs. The defective graphitized nanosheets and Fe-Nx acted separately as electron transfer and radical pathway active sites of Fe@N-BC800, where π-π sorption assisted with pyrrolic N and pore-filling facilitated BPA degradation. The strong inhibitory effects of PO43- and NO2- were ascribed to competitive adsorption of phosphate (61.11 mg g-1) and nitrate (23.99 mg g-1) on Fe@N-BC800 via electrostatic attraction and hydrogen bonding. In contrast, HA competed for the pyrrolic-N site and hindered electron delivery. Moreover, BPA oxidation pathways initiated by secondary free radicals were proposed. The study facilitates a thorough understanding of the intrinsic properties of designed biochar and contributes new insights into the fate of degradation byproducts formed from ISCO treatment of micropollutants.

Metformin Contamination in Global Waters: Biotic and Abiotic Transformation, Byproduct Generation and Toxicity, and Evaluation as a Pharmaceutical Indicator.

Metformin is the first-line antidiabetic drug and one of the most prescribed medications worldwide. Because of its ubiquitous occurrence in global waters and demonstrated ecotoxicity, metformin, as with other pharmaceuticals, has become a concerning emerging contaminant. Metformin is subject to transformation, producing numerous problematic transformation byproducts (TPs). The occurrence, removal, and toxicity of metformin have been continually reviewed; yet, a comprehensive analysis of its transformation pathways, byproduct generation, and the associated change in adverse effects is lacking. In this review, we provide a critical overview of the transformation fate of metformin during water treatments and natural processes and compile the 32 organic TPs generated from biotic and abiotic pathways. These TPs occur in aquatic systems worldwide along with metformin. Enhanced toxicity of several TPs compared to metformin has been demonstrated through organism tests and necessitates the development of complete mineralization techniques for metformin and more attention on TP monitoring. We also assess the potential of metformin to indicate overall contamination of pharmaceuticals in aquatic environments, and compared to the previously acknowledged ones, metformin is found to be a more robust or comparable indicator of such overall pharmaceutical contamination. In addition, we provide insightful avenues for future research on metformin.

Solar-light driven photodegradation of antimicrobials, their transformation by-products and antibiotic resistance determinants in treated wastewater.

This study aimed to assess the possibility of using solar light-driven photolysis and TiO2-based photocatalysis to remove (1) antibiotic residues, (2) their transformation products (TPs), (3) antibiotic resistance determinants, and (4) genes identifying the indicator bacteria in a treated wastewater (secondary effluent). 16 antimicrobials belonging to the different classes and 45 their transformation by-products were selected for the study. The most susceptible to photochemical decomposition was tetracycline, which was completely removed in the photocatalysis process and in more than 80% in the solar light-driven photolysis. 83.8% removal (on average) was observed using photolysis and 89.9% using photocatalysis in the case of the tested genes, among which the genes sul1, uidA, and intI1 showed the highest degree of removal by both methods. The study revealed that applied methods promisingly remove the tested antibiotics, their TPs and genes even in such a complex matrix including treated wastewater and photocatalysis process had a higher removal efficiency of antibiotics, TPs and genes tested. Moreover, the high percentage removal of the intI1 gene (>93%) indicates the possibilities of use of the solar light-driven photolysis and TiO2-based photocatalysis in minimizing the antibiotic resistance genes transfer by mobile genetic elements.

Insight into BDD electrochemical oxidation of florfenicol in water: Kinetics, reaction mechanism, and toxicity.

Antibiotics in the environment provoke serious consequences on living beings and can be effectively remediated by prominent advanced oxidation process. In this study, electrochemical advanced oxidation treatment in a lab-scale reactor for the degradation of florfenicol (FLO) was studied with the aid of boron-doped diamond anode (BDD). The results exhibited that the FLO degradation follows pseudo-first-order kinetics. As the current intensity rose from 60 mA to 250 mA, the FLO removal efficiency increased and the corresponding reaction rate constant increased from 0.0213 to 0.0343 min-1, which was likely due to the more efficient participation of free hydroxyl radical (•OH) generated at the BDD anode. Faster degradation and higher mineralization of electrolyzed FLO solution were achieved at higher current intensity as well as in higher SO42- concentration medium, as a consequence of catalytic participation of oxidants (free •OH as well as sulfate radical (SO4•-) and persulfate (S2O82-)). The increase in FLO concentration from 30 to 50 mg L-1 resulted in a reaction rate constant decrease (from 0.0235 to 0.0178 min-1). Eight transformation by-products (m/z = 372.99, 359.8, 338.0, 324.04, 199.00, 185.02, 168.99 and 78.989) and three inorganic ions (NO3-, Cl- and F-) were analyzed by UPLC‒Q‒TOF‒MS/MS and Ion‒chromatography, respectively. The Vibrio fischeri bioluminescence inhibition revealed an increase of toxicity during the electrochemical oxidation that could be attributed mostly to the generated organic chlorinated by-products (m/z = 372.99, 359.8) and inorganic species (ClO2- and ClO3-).

Oxidative degradation and mineralization of the endocrine disrupting chemical bisphenol-A by an eco-friendly system based on UV-solar/H2O2 with reduction of genotoxicity and cytotoxicity levels.

A solar-driven advanced oxidation process at a lab scale was studied for the degradation and mineralization of the known endocrine disrupting chemical (EDC), bisphenol A (BPA). Preliminary tests were performed varying the irradiation source, BPA/H2O2 ratio, temperature, initial H2O2 concentration, initial solution pH, and initial BPA concentration, then, the operational conditions of the UV-solar/H2O2 were optimized by a response surface methodology (RSM), providing the following responses: UV-solar/H2O2 process at pH 3.0, [BPA]0 = 25 mg L-1, [H2O2] = 350 mg L-1, T = 50 °C, achieving BPA degradation of 77.4% and BPA mineralization of 38.2%, H2O2 consumption of 230 mg L-1. From the optimized condition, different pH ranges were tested (3.0; 5.0; 7.0; 9.0; and 11.0), where, at solution pH 5.0 the best removal rates were achieved (89.2% BPA degradation and 49.0% BPA mineralization). The BPA amount in solution was monitored by High Performance Liquid Chromatography (HPLC) and a study of the intermediate reaction by-products was performed by Gas Chromatography-Mass Spectrometry (GC-MS) analyses, highlighting the lower amount of by-products identified when the solution pH 5.0 was employed, rather than the solution pH 3.0. Genotoxicity tests with Zebrafish (Danio rerio) and cytotoxicity tests with Allium cepa were performed aiming to evaluate errors in the cells and nuclear abnormalities of the tested organisms induced by BPA raw samples, as well as by the BPA samples treated by the UV-solar/H2O2 process. Therefore, the bio-toxicity levels for an animal and a vegetal bio-indicator were reduced by applying a renewable source of energy as the irradiation source for the UV/H2O2 process, representing an efficient and eco-friendly alternative for BPA treatment in aqueous solutions.

Potential toxic effects of chlorination and UV/chlorination in the treatment of hydrochlorothiazide in the water.

Chlorination is a common disinfection method in water treatment. This method can be converted into an advanced oxidation process by incorporating UV irradiation during water treatment. This study investigated the degradation of hydrochlorothiazide (HCTZ) by chlorination and UV/chlorination in water. HCTZ is a diuretic medication that has been frequently detected in wastewater. For chlorination, the second-order rate constant for the reaction between HCTZ with free available chlorine was found to increase with increasing pH from 5 to 8 due to the increase of the anionic HCTZ fraction. UV/chlorination was found to be more efficient in removing HCTZ as compared with chlorination due to the presence of reactive radical species such as hydroxyl radicals. For transformation by-products, chlorination was found to produce two by-products via chlorination and hydroxylation reactions that occurred at the aromatic ring of HCTZ. For UV/chlorination, an additional by-product formed through a radical reaction at the heterocyclic moiety of HCTZ was detected. Based on the Escherichia coli inhibition study, chlorination and UV/chlorination were found to increase the toxicity of the HCTZ solution. This result indicated that even UV/chlorination showed higher effectiveness in removing HCTZ; however, it also has the potential to generate toxic by-products and effluent.

Fungal biodegradation of the N-nitrosodimethylamine precursors venlafaxine and O-desmethylvenlafaxine in water.

Antidepressant drugs such as Venlafaxine (VFX) and O-desmethylvenlafaxine (ODMVFX) are emerging contaminants that are commonly detected in aquatic environments, since conventional wastewater treatment plants are unable to completely remove them. They can be precursors of hazardous by-products, such as the carcinogenic N-nitrosodimethylamine (NDMA), generated upon water chlorination, as they contain the dimethylamino moiety, necessary for the formation of NDMA. In this study, the capability of three white rot fungi (Trametes versicolor, Ganoderma lucidum and Pleurotus ostreatus) to remove both antidepressants from water and to decrease NDMA formation potential was investigated. Furthermore, transformation by-products (TPs) generated along the treatment process were elucidated and also correlated with their NDMA formation potential. Very promising results were obtained for T. versicolor and G. lucidum, both being able to remove up to 100% of ODMVFX. In the case of VFX, which is very recalcitrant to conventional wastewater treatment, a 70% of removal was achieved by T. versicolor, along with a reduction in NDMA formation potential, thus decreasing the associated problems for human health and the environment. However, the NDMA formation potential remained practically constant during treatment with G. lucidum despite of the equally high VFX removal (70%). This difference was attributed to the generation of different TPs during both fungal treatments. For example, G. lucidum generated more ODMVFX, which actually has a higher NDMA formation potential than the parent compound itself.

The fate of sotalol in aqueous chlorination: Kinetics, mechanisms and ecotoxicity assessment.

Unmetabolized pharmaceuticals often enter the water treatment plants and exposed to various treatment processes. Among these water treatment processes, disinfection is a process which involves the application of chemical oxidation to remove pathogen. Untreated pharmaceuticals from primary and secondary treatment have the potential to be exposed to the chemical oxidation process during disinfection. This study investigated the kinetics and mechanism of the degradation of sotalol during chlorination process. Chlorination with hypochlorous acid (HOCl) as main reactive oxidant has been known as one of the most commonly used disinfection methods. The second order rate constant for the reaction between sotalol and free available chlorine (FAC) was found to decrease from 60.1 to 39.1M-1min-1 when the pH was increased from 6 to 8. This result was mainly attributed by the decreased of HOCl concentration with increasing pH. In the real water samples, the presence of the higher amount of organic content was found to reduce the efficiency of chlorination in the removal of sotalol. This result showed that sotalol competes with natural organic matter to react with HOCl during chlorination. After 24h of FAC exposure, sotalol was found to produce three stable transformation by-products. These by-products are mainly chlorinated compounds. According to the acute and chronic toxicity calculated using ECOSAR computer program, the transformation by-products are more harmful than sotalol.

Advanced oxidation of preservative agents in H2O2/UVC system - Kinetics study, transformation products and toxicity assessment.

Phenylphenol isomers (hydroxylated derivatives of biphenyl) are widely used as a preservative agents and disinfectants in many branches of industry. This work focuses on removal of phenylphenol isomers from aqueous solution using H2O2/UVC process. The influence of different operating variables such as pH, initial concentration of hydrogen peroxide, initial concentration of target compounds, fluence rate and presence of radical scavengers on degradation rate was investigated. Moreover, transformation products and toxicity of the reaction solutions were studied. The reaction rate constants of hydroxyl radicals with phenylphenol isomers were determined by using classical and competition kinetics. The value of reaction rate constant depends on the position of the hydroxyl group in the aromatic ring and follows the order: ortho- phenylphenol

Chlorination of bisphenol F and the estrogenic and peroxisome proliferator-activated receptor gamma effects of its disinfection byproducts.

The reaction kinetics and transformation pathways between bisphenol F (BPF) and sodium hypochlorite were investigated at pH values ranging from 6.5 to 8.5 and with different initial concentration ratios. The reaction rate was pH- and free available chlorine (FAC)-dependent: the reaction rate at pH 8.5 was almost 10 times than that at pH 6.5. A total of 40 compounds were tentatively identified as chloro-substituted BPF and polyphenolic compounds by liquid chromatography quadrupole time-of-flight mass spectrometry operating in electrospray ionization mode (LC-ESI-Q-ToF), and 4 main byproducts were confirmed by 1H and 13C nuclear magnetic resonance (NMR). Toxicity tests indicated that the estrogenic effects of chloro-substituted BPF decrease as the chlorine substitution increase. On the contrary, increasing numbers of chlorines on the phenolic rings of BPF enhanced the nuclear receptor peroxisome proliferator-activated receptor gamma (PPARγ) activity. Tetra-chlorinated BPF had an approximately 6.9-fold higher activity than BPF.

Degradation kinetics and pathways of three calcium channel blockers under UV irradiation.

Calcium channel blockers (CCBs) are a group of pharmaceuticals widely prescribed to lower blood pressure and treat heart diseases. They have been frequently detected in wastewater treatment plant (WWTP) effluents and downstream river waters, thus inducing a potential risk to aquatic ecosystems. However, little is known about the behavior and fate of CCBs under UV irradiation, which has been adopted as a primary disinfection method for WWTP effluents. This study investigated the degradation kinetics and pathways of three commonly-used CCBs, including amlodipine (AML), diltiazem (DIL), and verapamil (VER), under UV (254 nm) irradiation. The chemical structures of transformation byproducts (TBPs) were first identified to assess the potential ecological hazards. On that basis, a generic solid-phase extraction method, which simultaneously used four different cartridges, was adopted to extract and enrich the TBPs. Thereafter, the photo-degradation of target CCBs was performed under UV fluences typical for WWTP effluent disinfection. The degradation of all three CCBs conformed to the pseudo-first-order kinetics, with rate constants of 0.031, 0.044 and 0.011 min(-1) for AML, DIL and VER, respectively. By comparing the MS(2) fragments and the evolution (i.e., formation or decay) trends of identified TBPs, the degradation pathways were proposed. In the WWTP effluent, although the target CCBs could be degraded, several TBPs still contained the functional pharmacophores and reached peak concentrations under UV fluences of 40-100 mJ cm(-2).

Photochemical transformation of ibuprofen into harmful 4-isobutylacetophenone: pathways, kinetics, and significance for surface waters.

The harmful compound 4-isobutylacetophenone (IBAP) can be formed photochemically from the anti-inflammatory drug ibuprofen (IBP), upon direct photolysis (yield 25 ± 7%, µ ± σ), reaction with ·OH (yield 2.3 ± 0.1%) and reaction with triplet states of chromophoric dissolved organic matter, (3)CDOM* (yield 31 ± 4%). In the latter case, anthraquinone-2-sulphonate was used as CDOM proxy. The three processes would account for most of the photochemical transformation of IBP and IBAP in surface waters. IBAP formation from IBP involves the propanoic acid chain, which is more reactive than the aromatic ring as shown by quantum mechanical calculations. IBAP is expected to undergo slightly faster photochemical transformation than IBP in surface waters, with a modelled pseudo-first order rate constant that is higher by 1.5-1.9 times compared to IBP. Due to fairly high formation yields and depending on IBP emission scenarios, photochemical modelling suggests that IBAP could reach concentration values up to ~15% of IBP in surface waters, thus being a potentially important transformation intermediate. This issue prompts for the need of field studies that provide information on IBAP environmental occurrence, which is virtually unknown at the present moment.