Novel insight into dissolved organic nitrogen (DON) transformation along wastewater treatment processes with special emphasis on endogenous-source DON.

Knowledge of endogenous-source dissolved organic nitrogen (esDON) produced in wastewater treatment processes is critical for evaluating its potential impacts on receiving waters because esDON is a recognized concern, as it causes eutrophication. However, differentiating esDON from influent residual DON in real wastewater is always a challenge. Here, we deciphered esDON information in DON transformation processes along a full-scale wastewater treatment train by combining multiple chemometric tools with ion-mobility separation quadrupole time-of-flight mass spectrometry (IMS-QTOF MS) analyses. In total, DON became more refractory and compact with shorter carbon chains and fewer nitrogen atoms, and esDON composed a nonnegligible fraction that dominated DON transformation and characteristics. New esDON produced in treatment processes constituted a crucial part (>35.5%) of wastewater DON, and its contributions to wastewater DON are augmented along the train. Evidence of molecular conformations further confirmed dominant roles of esDON in DON characteristics. Moreover, esDON participated in 46.7% of core biochemical reaction networks, explaining the importance of esDON in DON transformation. Our study offers a tool to gain esDON characteristics and transformation mechanisms, and highlights the importance to control esDON for alleviating adverse influences from DON in receiving waters.

Indirect Photodegradation of Sulfamethoxazole and Trimethoprim by Hydroxyl Radicals in Aquatic Environment: Mechanisms, Transformation Products and Eco-Toxicity Evaluation.

The bacteriostatic antibiotics, sulfamethoxazole (SMX) and trimethoprim (TMP), have frequently been found in wastewater and surface water, which raises the concerns about their ecotoxicological effects. The indirect photochemical transformation has been proven to be an efficient way to degrade SMX and TMP. In this study, the reaction mechanisms of the degradation by SMX and TMF by OH radicals were investigated by theoretical calculations. Corresponding rate constants were determined and the eco-toxicity of SMX and TMP and its degradations products were predicted using theoretical models. The results indicate that the most favorable pathways for the transformation of SMX and TMP are both •OH-addition reaction of benzene ring site with lowest Gibbs free energy barriers (6.86 and 6.21 kcal mol-1). It was found that the overall reaction rate constants of •OH-initial reaction of SMX and TMP are 1.28 × 108 M-1 s-1 and 6.21 × 108 M-1 s-1 at 298 K, respectively. When comparing the eco-toxicity of transformation products with parent SMX and TMP, it can be concluded that the acute and chronic toxicities of the degraded products are reduced, but some products remain harmful for organisms, especially for daphnid (toxic or very toxic level). This study can give greater insight into the degradation of SMX and TMP by •OH through theoretical calculations in aquatic environment.

Chlorination of antiviral drug ribavirin: Kinetics, nontargeted identification, and concomitant toxicity evolution.

Residual antiviral drugs in wastewater may increase the risk of generating transformation products (TPs) during wastewater treatment. Therefore, chlorination behavior and toxicity evolution are essential to understand the secondary ecological risk associated with their TPs. Herein, chlorination kinetics, transformation pathways, and secondary risks of ribavirin (RBV), one of the most commonly used broad-spectrum antivirals, were investigated. The pH-dependent second-order rate constants k increased from 0.18 M-1·s-1 (pH 5.8) to 1.53 M-1·s-1 (pH 8.0) due to neutral RBV and ClO- as dominant species. 12 TPs were identified using high-resolution mass spectrometry in a nontargeted approach, of which 6 TPs were reported for the first time, and their chlorination pathways were elucidated. The luminescence inhibition rate of Vibrio fischeri exposed to chlorinated RBV solution was positively correlated with initial free active chlorine, probably due to the accumulation of toxic TPs. Quantitative structure-activity relationship prediction identified 7 TPs with elevated toxicity, concentrating on developmental toxicity and bioconcentration factors, which explained the increased toxicity of chlorinated RBV. Overall, this study highlights the urgent need to minimize the discharge of toxic chlorinated TPs into aquatic environments and contributes to environmental risk control in future pandemics and regions with high consumption of antivirals.

Insights into the photocatalytic degradation of hydrophobic organic contaminants on the surface of nitrogen doped silica: New findings of the formation of silicon-based substitution products.

In this work, nitrogen-doped SiO2 (N-SiO2) was successfully synthesized to develop an "adsorption-photocatalytic degradation" water purification technology to remove hydrophobic organic contaminants (HOCs). As a representative of HOCs, decabromodiphenylethane (DBDPE) could be efficiently degraded under simulated sunlight after adsorption on the surface of N-SiO2. Due to the generation of reactive oxygen species (ROS) and silicon-based radicals, the photodegradation rate of DBDPE on water-SiO2 interface was 1.5-fold higher than that in water. Furthermore, the transformation pathways of DBDPE on N-SiO2 surface were compared with that in water. Bond breaking and debromination reactions were the common pathways, while hydroxylation and silicon-based substitution reactions were the specific transformation pathways for DBDPE on the surface of N-SiO2. Density functional theory (DFT) calculation was used to reveal the generation mechanism of silicon-based radicals and determine the rationality of the involvement of silicon-based radicals in DBDPE transformation. The energy barriers of silicon-based substitution reaction were comparable to that of hydroxylation and debromination reactions, which confirmed the plausibility of the generation of silicon-based substitution products. This study provides an efficient method for the disposal of HOCs, which also gives some new insights into the conversion mechanism of organic pollutants mediated by silicon-based radicals.

Expression and function of NF-Y subunits in cancer.

NF-Y is a Transcription Factor (TF) targeting the CCAAT box regulatory element. It consists of the NF-YB/NF-YC heterodimer, each containing an Histone Fold Domain (HFD), and the sequence-specific subunit NF-YA. NF-YA expression is associated with cell proliferation and absent in some post-mitotic cells. The review summarizes recent findings impacting on cancer development. The logic of the NF-Y regulome points to pro-growth, oncogenic genes in the cell-cycle, metabolism and transcriptional regulation routes. NF-YA is involved in growth/differentiation decisions upon cell-cycle re-entry after mitosis and it is widely overexpressed in tumors, the HFD subunits in some tumor types or subtypes. Overexpression of NF-Y -mostly NF-YA- is oncogenic and decreases sensitivity to anti-neoplastic drugs. The specific roles of NF-YA and NF-YC isoforms generated by alternative splicing -AS- are discussed, including the prognostic value of their levels, although the specific molecular mechanisms of activity are still to be deciphered.

Selenium-Mediated (-)-Epigallocatechin-3-Gallate Dynamics via Flavanone-3-Hydroxylase Regulation of Flavonoid Biosynthesis in Fu Tea (Camellia sinensis (L.) O. Kuntze).

Tea (Camellia sinensis (L.) O. Kuntze) is a highly selenium enrichment capacity plant; high selenium concentration contributes to the occurrence of oxidative stress and protein misfolding in tea plants, whereas flavonoids can chelate heavy metals to protect plants from oxidative stress caused by metal exposure. Nevertheless, the role of catechins in flavonoid synthesis and nutrient metabolism under selenium stress remains unidentified. Combining Word2vec and HNSW utilizing UHPLC-Q-Orbitrap HRMS-MS/MS to implement rapid matching annotation of the structural information on metabolites in Fu tea, we found that selenium-mediated changes in catechins in Fu tea were mainly associated with flavonoid biosynthesis pathways. The results demonstrated that selenium treatment increased benign selenol analogues (glutathioselenol) in tea and identified the novel selenopeptide PRSeMW (m/z 636.22571, Pro-Arg-SeMet-Trp) in selenium-enriched Fu tea samples to enhance the health benefits of tea. The selenium levels were negatively correlated with N5-ethyl-l-glutamine (11.63 to 4.26 mg kg-1) and (-)-epigallocatechin (13.26 to 11.19 mg kg-1), increasing the accumulation of tea polyphenols ((-)-catechin gallate, (-)-epigallocatechin 3-gallate, and (+)-gallocatechin), and decreasing the level of caffeine. These discoveries provide new insights into the mechanism of tea polyphenol-mediated transformation of selenium in Fu tea and theoretical support for the quality assessment of selenium-enriched tea.

Coherent Phase Change in Interstitial Solutions: A Hierarchy of Instabilities.

Metal hydrides or lithium ion battery electrodes can take the form of interstitial solid solutions with a miscibility gap. This work discusses theory approaches for locating, in temperature-composition space, coherent phase transformations during the charging/discharging of such systems and for identifying the associated transformation mechanisms. The focus is on the simplest scenario, where instabilities derive from the thermodynamics of the bulk phase alone, considering strain energy as the foremost consequence of coherency and admitting for stress relaxation at free surfaces. The extension of the approach to include capillarity is demonstrated by an example. The analysis rests on constrained equilibrium phase diagrams that are informed by geometry- and dimensionality-specific mechanical boundary conditions and on elastic instabilities-again geometry-specific-as implied by the theory of open-system elasticity. It is demonstrated that some scenarios afford the analysis of chemical stability to be based entirely on a linear stability analysis of the mechanical equilibrium, which provides closed-form solutions in a straightforward manner. Attention is on the impact of the system geometry (infinitely extended or of finite size) and on the chemical (closed or open system) and mechanical (incoherent or coherent) boundary conditions. Transformation mechanism maps are suggested for documenting the findings. The maps reveal a hierarchy of instabilities, which depend strongly on each of the above characteristics. Specifically, realistic, finite-sized systems differ qualitatively from idealized systems of infinite extension. Among the transformation mechanisms exposed by the analysis are a uniform switchover to the other phase when the open system reaches its chemical spinodal, practical coherent nucleation, as well as chemo-elastically coupled spontaneous buckling modes, which may take the form of either, single-phase or dual-phase states.

Formation of ibrutinib solvates: so similar, yet so different.

The transformation processes of non-solvated ibrutinib into a series of halogenated benzene solvates are explored in detail here. The transformation was studied in real time by X-ray powder diffraction in a glass capillary. Crystal structures of chlorobenzene, bromobenzene and iodobenzene solvates are isostructural, whereas the structure of fluorobenzene solvate is different. Four different mechanisms for transformation were discovered despite the similarity in the chemical nature of the solvents and crystal structures of the solvates formed. These mechanisms include direct transformations and transformations with either a crystalline or an amorphous intermediate phase. The binding preference of each solvate in the crystal structure of the solvates was examined in competitive slurry experiments and further confirmed by interaction strength calculations. Overall, the presented system and online X-ray powder diffraction measurement provide unique insights into the formation of solvates.

Chlorination of methotrexate in water revisited: Deciphering the kinetics, novel reaction mechanisms, and unexpected microbial risks.

Chlorination of a typical anticancer drug with annually ascending use and global prevalence (methotrexate, MTX) in water has been studied. In addition to the analysis of kinetics in different water/wastewater matrices, high-resolution product identification and in-depth secondary risk evaluation, which were eagerly urged in the literature, were performed. It was found that the oxidation of MTX by free available chlorine (FAC) followed first-order kinetics with respect to FAC and first-order kinetics with respect to MTX. The pH-dependent rate constants (kapp) ranged from 170.00 M-1 s-1 (pH 5.0) to 2.68 M-1 s-1 (pH 9.0). The moiety-specific kinetic analysis suggested that 6 model substructures of MTX exhibited similar reactivity to the parent compound at pH 7.0. The presence of Br- greatly promoted MTX chlorination at pH 5.0-9.0, which may be ascribed to the formation of bromine with higher reactivity than FAC. Comparatively, coexisting I- or humic acid inhibited the degradation of MTX by FAC. Notably, chlorination effectively abated MTX in different real water matrices. The liquid chromatography-high resolution mass spectrometry analysis of multiple matrix-mediated chlorinated samples indicated the generation of nine transformation products (TPs) of MTX, among which seven were identified during FAC oxidation for the first time. In addition to the reported electrophilic chlorination of MTX (the major and dominant reaction pathway), the initial attacks on the amide and tertiary amine moieties with C-N bond cleavage constitute novel reaction mechanisms. No genotoxicity was observed for MTX or chlorinated solutions thereof, whereas some TPs were estimated to show multi-endpoint aquatic toxicity and higher biodegradation recalcitrance than MTX. The chlorinated mixtures of MTX with or without Br- showed a significant ability to increase the conjugative transfer frequency of plasmid-carried antibiotic resistance genes within bacteria. Overall, this work thoroughly examines the reaction kinetics together with the matrix effects, transformation mechanisms, and secondary environmental risks of MTX chlorination.

Overlooked environmental risks deriving from aqueous transformation of bisphenol alternatives: Integration of chemical and toxicological insights.

Owing to the widespread prevalence and ecotoxicity of bisphenol alternatives such as bisphenol S, bisphenol F, and bisphenol AF, the past decade has witnessed the publication of a remarkable number of studies related to their transformation and remediation in natural waters. However, the reactivity, removal efficiency, transformation products (TPs), and mechanisms of such emerging pollutants by different treatment processes have not been well elucidated. Particularly, the transformation-driven environmental risks have been mostly overlooked. Therefore, we present a review to address these issues from chemical and toxicological viewpoints. Four degradation systems can be largely classified as catalytic persulfate (PS) oxidation, non-catalytic oxidation, photolysis and photocatalysis, and biodegradation. It was found that bisphenol alternatives possess distinct reactivities with different oxidizing species, with the highest performance for hydroxyl radicals. All systems exhibit superior elimination efficiency for these compounds. The inadequate mineralization suggests the formation of recalcitrant TPs, from which the overall reaction pathways are proposed. The combined experimental and in silico analysis indicates that many TPs have developmental toxicity, endocrine-disrupting effects, and genotoxicity. Notably, catalytic PS systems and non-catalytic oxidation result in the formation of coupling products as well as halogenated TPs with higher acute and chronic toxicity and lower biodegradability than the parent compounds. In contrast, photolysis and photocatalysis generate hydroxylated and bond-cleavage TPs with less toxicity. Overall, this review highlights the secondary environmental risks from the transformation of bisphenol alternatives by conventional and emerging treatment processes. Finally, future perspectives are recommended to address the knowledge gaps of these contaminants in aquatic ecosystems.

Iodide promotes bisphenol A (BPA) halogenation during chlorination: Evidence from 30 X-BPAs (X = Cl, Br, and I).

As a well known endocrine-disrupting and model chemical, bisphenol A (BPA) may pose a serious threat to human health, since it and its disinfection by-products (DBPs) have been detected in drinking water, urine, human colostrum, adipose tissue, and placenta samples. Although chlorinated BPAs (Cl-BPAs) and iodinated BPAs (I-BPAs) have been well studied, brominated BPAs (Br-BPAs), and mixed halogenated DBPs like bromo-iodo-BPAs (Br-I-BPAs), and bromo-chloro-iodo-BPAs (Cl-Br-I-BPAs) are less well understood. Notably, the role of iodide (I-) during chlorination is not well understood, since the studies of the I-DBPs mainly focus on their genotoxicity and cytotoxicity. To understand the formation mechanisms of halogenated bisphenol A (HBPs) during chlorination with bromide (Br-) and/or I-, and the role of I- during chlorination, three set of reactions were performed in the laboratory ("BPA + chlorine + Br-", "BPA + chlorine + I-" and "BPA + chlorine + Br- +I-" assigned as group A, B and C respectively). Thirty HBPs were identified and 18 of them were never reported before. I- increases the transformation rate of BPA into HBPs as I-BPAs act as intermediate HBPs during chlorination that easily react with HClO/ClO- and HBrO/BrO- to form Cl-BPAs and Br-BPAs. HIO/IO- showed higher reactivity towards BPA and HBPs than that of HBrO/BrO- and HClO/ClO-. The recycling of I- was observed in the reactions of "BPA + chlorine + I-" and "BPA + chlorine + Br- +I-", which may explain why I- can induce BPA to transform into HBPs and suggests that I- may act as a catalyst during the BPA chlorination reactions. The reaction pathways are proposed which present the reactions of BPA and HBPs with HClO/ClO-, HBrO/BrO-, and HIO/IO-, as well as the recycling of I-. This study describes the potential DBP formation and transformation mechanisms of BPA and its 16 alternatives, as well as the role of I- on the transformation of phenol compounds during chlorination.

Mechanisms, kinetics and eco-toxicity assessment of singlet oxygen, sulfate and hydroxyl radicals-initiated degradation of fenpiclonil in aquatic environments.

Fenpiclonil is an agricultural phenylpyrrole fungicide, which raise the concern about its ecotoxicological effects. In this paper, we investigate the indirect photochemical transformation mechanisms, environmental persistence and eco-toxicity of fenpiclonil initiated by various active oxidants (1O2, •OH and SO4•‾) in aquatic environments. The results shown that 1O2 can react with pyrrole ring by cycloaddition pathways to form the endo-peroxides. In addition, •OH and SO4•‾ initial mechanisms are calculated, suggesting that •OH-initiated mechanisms play a dominant role in the degradation process of fenpiclonil at high rate constants (2.26 ×109 M-1 s-1, at 298 K). The kinetic calculation results indicate that high temperature is more favorable for the degradation of fenpiclonil. To better understand the adverse effects of the transformation products formed during the subsequent reaction of •OH-adduct IM10, the computational toxicology has been used for the toxicity estimation. The results show that aquatic toxicity of these products decrease with degradation process, especially the decomposition products (TP3 and TP4). However, TP1 and TP2 are still toxic and developmental toxicant. The study provides guidance for further experimental research and industrial application of fungicide degradation from the perspective of theoretical calculation.

A New Concept for Modeling Phase Transformations in Ti6Al4V Alloy Manufactured by Directed Energy Deposition.

The microstructure directly influences the subsequent mechanical properties of materials. In the manufactured parts, the elaboration processes set the microstructure features such as phase types or the characteristics of defects and grains. In this light, this article aims to understand the evolution of the microstructure during the directed energy deposition (DED) manufacturing process of Ti6Al4V alloy. It sets out a new concept of time-phase transformation-block (TTB). This innovative segmentation of the temperature history in different blocks allows us to correlate the thermal histories computed by a 3D finite element (FE) thermal model and the final microstructure of a multilayered Ti6Al4V alloy obtained from the DED process. As a first step, a review of the state of the art on mechanisms that trigger solid-phase transformations of Ti6Al4V alloy is carried out. This shows the inadequacy of the current kinetic models to predict microstructure evolution during DED as multiple values are reported for transformation start temperatures. Secondly, a 3D finite element (FE) thermal simulation is developed and its results are validated against a Ti6Al4V part representative of repair technique using a DED process. The building strategy promotes the heat accumulation and the part exhibits heterogeneity of hardness and of the nature and the number of phases. Within the generated thermal field history, three points of interest (POI) representative of different microstructures are selected. An in-depth analysis of the thermal curves enables distinguishing solid-phase transformations according to their diffusive or displacive mechanisms. Coupled with the state of the art, this analysis highlights both the variable character of the critical points of transformations, and the different phase transformation mechanisms activated depending on the temperature value and on the heating or cooling rate. The validation of this approach is achieved by means of a thorough qualitative description of the evolution of the microstructure at each of the POI during DED process. The new TTB concept is thus shown to provide a flowchart basis to predict the final microstructure based on FE temperature fields.

Water-soluble fluorine detoxification mechanisms of spent potlining incineration in response to calcium compounds.

In this study, the detoxification mechanisms of water-soluble fluorine in the bottom ash and the distribution of fluorine during the spent potlining (SPL) incineration were characterized in response to four calcium compounds using an experimental tube furnace. CaSiO3, CaO, Ca(OH)2, and CaCO3-assisted SPL incineration converted NaF to low toxicity compounds in the bottom ash yielding a conversion range of 54.24-99.45% relative to the individual SPL incineration. The two main mechanisms of the fluorine transformation were the formations of CaF2 and Ca4Si2O7F2. The fluorine transformation efficiency was greater with CaSiO3 than CaO, Ca(OH)2, and CaCO3. Our simulations demonstrated that SiO2 enhanced the conversion of NaF. The fluorine leaching content of the bottom ash was estimated at 13.71 mg⋅L-1 after the SPL co-incineration with CaSiO3 (Ca:F = 1.2:1). The acid-alkali solutions had no significant effect on the fluorine leaching content of the bottom ash when 3 ≤ pH ≤ 12. Fluorine during the SPL co-incineration with CaSiO3 (Ca:F = 1.2:1) at 850 °C for 60 min was partitioned into 83.37, 13.90, and 2.72% in the bottom ash, fly ash, and flue gas, respectively. The transformation and detoxification mechanisms of water-soluble fluorine provide new insights into controls on fluorine emission from the SPL incineration.

MnO2 nanozyme-driven polymerization and decomposition mechanisms of 17ß-estradiol: Influence of humic acid.

Nanozymes, which display the bifunctional properties of nanomaterials and natural enzymes, are useful tools for environmental remediation. In this research, nano-MnO2 was selected for its intrinsic enzyme-like activity to remove 17ß-estradiol (E2). Results indicated that nano-MnO2 exhibited laccase-like activity (7.22 U·mg-1) and removed 97.3 % of E2 at pH 6. Humic acid (HA) impeded E2 removal (only 72.4 %) by competing with E2 for the catalytic sites of the MnO2 nanozyme surface, and there was a good linear correlation between the kinetic constants and HA concentrations (R2 = 0.9489). Notably, the phenolic -OH of E2 interacted with HA to yield various polymeric products via radical-driven covalent coupling, resulting in ablation of phenolic -OH but increase of ether groups in the polymeric structure. Intermediate products, including estrone, E2 homo-/hetero-oligomers, E2 hydroxylated and quinone-like products, as well as aromatic ring-opening species, were identified. Interestingly, HA hindered the extent of E2 oxidation, homo-coupling, and decomposition but accelerated E2 and HA hetero-coupling. A reasonable catalytic pathway of E2 and HA involving MnO2 nanozyme was proposed. These findings provide novel insights into the influence of HA on MnO2 nanozyme-driven E2 radical polymerization and decomposition, consequently favoring the ecological water restoration and the global carbon cycle.

New insights on mercury abatement and modeling in a full-scale municipal solid waste incineration flue gas treatment unit.

Modeling approaches are generally used to describe mercury transformations in a single step of flue gas treatment processes. However, less attention has been given to the interactions between the different process stages. Accordingly, the mercury removal performance of a full-scale solid waste incineration plant, equipped with a dry flue gas treatment line was investigated using two complementary modeling strategies: a thermochemical equilibrium approach to study the mercury transformation mechanisms and speciation in the flue gas, and a kinetic approach to describe the mercury adsorption process. The modeling observations were then compared to real-operation full-scale data. Considering the typical flue gas composition of waste incineration facilities (high concentrations of HCl compared to Hg), it was found that a process temperature decrease results in better mercury removal efficiencies, associated with a higher oxidation extent of Hg in HgCl2, and the enhancement of the sorbent capacity. Improvements can also be attained by increasing the sorbent injection rate to the process, or the solid/gas separation cycles. An empirical correlation to predict the mercury removal efficiency from the main operating parameters of dry flue gas treatment units was proposed, representing a useful tool for waste incineration facilities. The presented modeling approach proved to be suitable to evaluate the behavior of full-scale gas treatment units, and properly select the most adequate adjustments in operating parameters, in order to respect the increasingly constraining mercury emissions regulations.

Chemical transformation of silver nanoparticles in aquatic environments: Mechanism, morphology and toxicity.

Silver nanoparticles (Ag NPs) have been inevitably introduced into ecological environment during their extensive applications in daily human life. Thermodynamically, Ag NPs are unstable and transform into other species under various aqueous conditions. Ag NPs and their transformation products pose potential threats to environment and humans. However, the complex environmental conditions and transformations of Ag NPs complicate their human health and environmental risk assessment. To bridge the knowledge gap, four essential environmental transformations, oxidative dissolution, sulfidation, chlorination and photoreduction, of Ag NPs are reviewed herein. The mechanism, morphology and size change, as well as the toxicity of Ag NPs during these transformations under certain aqueous conditions are detailed. In particular, these environmental transformations have shown strong correlations that are discussed. The transformation, fate, bioavailability, morphology and toxicity of Ag NPs are critical factors and should be considered in a complete human health and environmental risk assessment of Ag NPs. The fluctuation of these factors in the realistic environment is also vital and should be considered.

An automated on-line turbulent flow liquid-chromatography technology coupled to a high resolution mass spectrometer LTQ-Orbitrap for suspect screening of antibiotic transformation products during microalgae wastewater treatment.

The evaluation of wastewater treatment capabilities in terms of removal of water pollutants is crucial when assessing water mitigation issues. Not only the monitoring of target pollutants becomes a critical point, but also the transformation products (TPs) generated. Since these TPs are very often unknown compounds, their study in both wastewater and natural environment is currently recognized as a tedious task and challenging research field. In this study, a novel automated suspect screening methodology was developed for a comprehensive assessment of the TPs generated from nine antibiotics during microalgae water treatment. Three macrolides (azithromycin, erythromycin, clarithromycin), three fluoroquinolones (ofloxacin, ciprofloxacin, norfloxacin) and three additional antibiotics (trimethoprim, pipemidic acid, sulfapyridine) were selected as target pollutants. The analysis of samples was carried out by direct injection in an on-line turbulent flow liquid chromatography-high resolution mass spectrometry (TFC-LC-LTQ-Orbitrap-MS/MS) system, followed by automatic data processing for compound identification. The screening methodology allowed the identification of 40 tentative TPs from a list of software predicted intermediates created automatically. Once known and unknown TPs were identified, degradation pathways were suggested considering the different mechanisms involved on their formation (biotic and abiotic). Results reveal microalgae ability for macrolide biotransformation, but not for other antibiotics such as for fluoroquinolones. Finally, the intermediates detected were included into an in-house library and applied to the identification of tentative TPs in real toilet wastewater treated in a microalgae based photobioreactor (PBR). The overall approach allowed a comprehensive overview of the performance of microalgae water treatment in a fast and reliable manner: it represents a useful tool for the rapid screening of wide range of compounds, reducing time invested in data analysis and providing reliable structural identification.

Degradation of ketoprofen by sulfate radical-based advanced oxidation processes: Kinetics, mechanisms, and effects of natural water matrices.

Ketoprofen (KET) is a mostly used nonsteroidal anti-inflammatory drug that has been frequently detected in wastewater effluents and surface waters. In this study, we investigated the degradation of KET by sulfate radical (SO4-) based advanced oxidation processes (SR-AOPs) in aqueous solution. The degradation kinetics, mechanisms, and effects of natural water matrices on thermally activated persulfate (TAP) oxidation of KET were systematically investigated. Increasing the temperature and persulfate (PS) concentrations greatly enhanced the degradation of KET. KET degradation is pH-dependent with an optimum pH of 5.0. Reactions in the presence of radical quenchers revealed the dominant role of SO4- in oxidizing KET. Water matrix significantly influenced the degradation of KET. The common inorganic anions present in natural waters exhibited inhibitory effect on KET degradation, and the inhibition followed the order of Cl- > CO32- > HCO3- > NO3-; however, no significant inhibition of KET degradation was observed in the presence of Ca2+ and Mg2+ cations. The presence of natural organic matter (NOM) suppressed KET degradation, and the suppression increased as NOM concentration increase. Products identification and mineralization experiments revealed that KET and its degradation intermediates were finally transformed into CO2 and H2O. The results of this study indicated that applying SR-AOPs for the remediation of KET contaminated water matrix is technically possible.

Elucidation of microbial nitrogen-transformation mechanisms in activated sludge by comprehensive evaluation of nitrogen-transformation activity.

Using prepared nitrifying sludge, anaerobic ammonia oxidization (anammox) sludge and two heterotrophic ammonia oxidization bacterial (AOB) species as inocula, this study elucidated the effect of oxygen conditions, assay media, and selective metabolic inhibitors on various microbial nitrogen (N)-transformation activities including aerobic chemolithotrophic ammonia and nitrite oxidization, aerobic heterotrophic ammonia oxidization, anammox, and aerobic and anoxic denitrification. The oxygen conditions and assay media effectively differentiated among almost all ammonia removal pathways except for separating aerobic chemolithotrophic ammonia oxidization from aerobic heterotrophic ammonia oxidization. A final allylthiourea concentration of 10mg·L-1 was optimal for accurate determination of aerobic heterotrophic ammonia oxidization activity in the presence of aerobic chemolithotrophic AOB. Finally, this study developed a simple and reliable method to individually determine and compare the comprehensive N-transformation activity characteristics of several activated sludge samples from different origins, and to elucidate the major microbial N-transformation mechanisms for ammonia removal and N2 production.