Zeolite Imidazolate Frameworks-8@SiO2-ZrO2 Crystal-Amorphous Hybrid Core-Shell Structure as a Building Block for Water Purification Membranes.

Metal-organic frameworks (MOFs) are emerging as promising materials for water purification membranes, owing to their uniform microporous structures and chemical functionalities. Here, we report a simple procedure for depositing MOF-based nanofiltration membranes on commercial TiO2 ceramic tubular supports, completely avoiding the use of dispersants or binders. Zeolite imidazolate frameworks-8 (ZIF-8) nanocrystals were synthesized in methanol at room temperature and subsequently coated with an amorphous SiO2-ZrO2 gel to generate a dispersion of ZIF-8@SiO2-ZrO2 core-shell nanoparticles. The amorphous SiO2-ZrO2 gel served as a binding agent for the ZIF-8 nanocrystals, thus forming a defect-free continuous membrane layer. After repeating the coating twice, the active layer had a thickness of 0.96 µm, presenting a rejection rate >90% for the total organic carbon in an aquaculture effluent and in a wastewater treatment plant, while reducing the concentration of trimethoprim, here used as a target pollutant. Moreover, the oxide gel provided the MOF-based active layer with good adhesion to the support and enhanced its hydrophilicity, resulting in a membrane with excellent mechanical stability and resistance to fouling during the crossflow filtration of the real wastewater samples. These results implied the high potential of the MOF-based nanocomposite membrane for effective treatment of actual wastewater streams.

Mercury and Organic Pollutants Removal from Aqueous Solutions by Heterogeneous Photocatalysis with ZnO-Based Materials.

The removal of four Contaminants of Emerging Concern, namely bisphenol A, sulfamethoxazole, diclofenac and benzotriazole; two odorous compounds, geosmin and 2-methylisoborneol, frequently detected in recirculating aquaculture systems; and Hg(II) was investigated using ZnO-based materials doped or co-doped with Ce and Cu under simulated solar radiation. Photocatalysts were synthetized via a hydrothermal route and their efficiency was assessed by changing some operational parameters in different water matrices of increasing complexity. The mixture of contaminants was successfully degraded in just 1 h, while the complete mineralization was achieved in a few hours; experiments performed in an actual aquaculture water confirmed the efficiency and broad versatility of the synthesized materials.

Natural solar activation of modified zinc oxides with rare earth elements (Ce, Yb) and Fe for the simultaneous disinfection and decontamination of urban wastewater.

This study investigates the capability of modified zinc oxides (ZnO) with Ce, Yb and Fe towards the simultaneous inactivation of pathogenic bacteria (Escherichia coli, Enterococcus faecalis and Pseudomonas aeruginosa) and Contaminants of Emerging Concern (CECs, Diclofenac, Sulfamethoxazole and Trimethoprim) under natural sunlight. Several catalyst loads (from 0 to 500 mg/L) were assessed as proof-of principle in isotonic solution followed by the evaluation of organic matter effect in simulated and actual urban wastewater (UWW), using bare TiO2-P25 as reference. The order of photocatalysts efficiency for both bacterial and CECs removal was: ZnO-Ce â‰… TiO2-P25 > ZnO-Yb > ZnO-Fe > photolysis > darkness in all water matrices. The best photocatalytic performance for water disinfection and decontamination was obtained with 500 mg/L of ZnO-Ce: 80% of ∑CECs removal after 45 min (4.4 kJ/L of accumulated solar UV-A energy (QUV)) and the total inactivation of bacteria (Detection Limit of 2 CFU/mL) after 120 min (14 kJ/L of QUV) in UWW. The microbial and CECs abatement mechanism was described based on the generation of hydroxyl radicals, which was experimentally demonstrated for ZnO-Ce. Additionally, no significant release of Zn2+ and Ce was detected after the solar exposure. These results point out for the first time the capability of ZnO-Ce for the simultaneous UWW disinfection and decontamination under natural sunlight.

Biomimetic photooxidation of noscapine sensitized by a riboflavin derivative in water: The combined role of natural dyes and solar light in environmental remediation.

Noscapine (NSC) is a benzyl-isoquinoline alkaloid discovered in 1930 as an antitussive agent. Recently, NSC has also been reported to exhibit antitumor activity and, according to computational studies, it is able to attack the protease enzyme of Coronavirus (COVID-19) and thus could be used as antiviral for COVID-19 pandemic. Therefore, an increasing use of this drug could be envisaged in the coming years. NSC is readily metabolized with a half-life of 4.5 h giving rise to cotarnine, hydrocotarnine, and meconine, arising from the oxidative breaking of the CC bond between isoquinoline and phthalide moieties. Because of its potentially increasing use, high concentrations of NSC but also its metabolites will be delivered in the environment and potentially affect natural ecosystems. Thus, the aim of this work is to investigate the degradation of NSC in the presence of naturally occurring photocatalysts. As a matter of fact, the present contribution has demonstrated that NSC can be efficiently degraded in the presence of a derivative of the natural organic dye Riboflavin (RFTA) upon exposure to visible light. Indeed, a detailed study of the mechanism involved in the photodegradation revealed the similarities between the biomimetic and the photocatalyzed processes. In fact, the main photoproducts of NSC were identified as cotarnine and opianic acid based on a careful UPLC-MS2 analysis compared to the independently synthesized standards. The former is coincident with one of the main metabolites obtained in humans, whereas the latter is related to meconine, a second major metabolite of NSC. Photophysical experiments demonstrated that the observed oxidative cleavage is mediated mainly by singlet oxygen in a medium in which the lifetime of 1O2 is long enough, or by electron transfer to the triplet excited state of RFTA if the photodegradation occurs in aqueous media, where the 1O2 lifetime is very short.

UV-Cured Chitosan and Gelatin Hydrogels for the Removal of As(V) and Pb(II) from Water.

In this study, new photocurable biobased hydrogels deriving from chitosan and gelatin are designed and tested as sorbents for As(V) and Pb(II) removal from water. Those renewable materials were modified by a simple methacrylation reaction in order to make them light processable. The success of the reaction was evaluated by both 1H-NMR and FTIR spectroscopy. The reactivity of those formulations was subsequently investigated by a real-time photorheology test. The obtained hydrogels showed high swelling capability reaching up to 1200% in the case of methacrylated gelatin (GelMA). Subsequently, the Z-potential of the methacrylated chitosan (MCH) and GelMA was measured to correlate their electrostatic surface characteristics with their adsorption properties for As(V) and Pb(II). The pH of the solutions proved to have a huge influence on the As(V) and Pb(II) adsorption capacity of the obtained hydrogels. Furthermore, the effect of As(V) and Pb(II) initial concentration and contact time on the adsorption capability of MCH and GelMA were investigated and discussed. The MCH and GelMA hydrogels demonstrated to be promising sorbents for the removal of heavy metals from polluted waters.

Development and application of high resolution mass spectrometry analytical method to study and identify the photoinduced transformation products of environmental pollutants.

Terpenes are among the major causes of pleasant or unpleasant odors close to active or inactive landfills. We studied R-limonene and p-cymene environmental degradation products using the heterogeneous photocatalysis mediated by titanium dioxide to explore the odor pollution. The aim of the study was the development of mass spectrometry based methods both hyphenated with GC and HPLC to identify and characterize transformation products (TPs) derived from photodegradation of R-limonene and p-cymene. With the GC-MS method we identified three TPs for R-limonene and two for p-cymene comparing the obtained mass spectra with those in the NIST library. While with HPLC-MS method, thanks to the use of the high resolution of MS tool, we recognized four and five TPs for R-limonene and p-cymene respectively. No p-cymene was detected as R-limonene transformation product. The methods developed were then applied to real environmental samples coming from landfills active (Lan1) or inactive (Lan2 and Lan3) located in northern Italy. R-limonene was detected in the active landfill (Lan1 at the concentration of 2.35 µg/mL) together with one of its TPs and one TP derived from p-cymene. p-Cymene was detected in the other two inactive landfills (Lan2 and Lan3 concentrations 0.025 and 0.15 µg/mL, respectively) together with one of its TP and two TPs coming from R-limonene photodegradation. The finding of TPs together with R-limonene and p-cymene both in active and inactive landfills point out the attention on the reduction of these molecules in the environment to reduce pollution and human risks.

Integrated approach for the analysis of neonicotinoids in fruits and food matrices.

We searched for five neonicotenoids (namely acetamiprid, clothianidin, imidacloprid, thiacloprid and thiamethoxam) in 67 samples of fruits, leaves, pollen and honey via HPLC-MS by employing QueChERs for extraction and purification. Clothianidin was never detected, while imidacloprid was identified in apple (9.2 µg/kg) and pollen (18-28 µg/Kg), thiacloprid in peaches (21-35 µg/kg) and acetamiprid was identified in the hazel leaves (1266 µg/kg), honey (13-26 µg /Kg) and pollen (11-24 µg/kg). Since the levels found of acetamiprid in hazel, honey and pollen were concerning, we accomplished a study to identify and characterize the possible transformation products via a laboratory simulation. The methodology exploited the analysis by HPLC-HRMS and its application in all matrices. We identify twelve transformation products, whose formation involved dimerization, hydroxylation, oxidation, demethylation and cleavage of the molecule. Three of them were also detected in hazel leaves.

Investigation of the Aquatic Photolytic and Photocatalytic Degradation of Citalopram.

This study investigated the direct and indirect photochemical degradation of citalopram (CIT), a selective serotonin reuptake inhibitor (SSRI), under natural and artificial solar radiation. Experiments were conducted in a variety of different operating conditions including Milli-Q (MQ) water and natural waters (lake water and municipal WWT effluent), as well as in the presence of natural water constituents (organic matter, nitrate and bicarbonate). Results showed that indirect photolysis can be an important degradation process in the aquatic environment since citalopram photo-transformation in the natural waters was accelerated in comparison to MQ water both under natural and simulated solar irradiation. In addition, to investigate the decontamination of water from citalopram, TiO2-mediated photocatalytic degradation was carried out and the attention was given to mineralization and toxicity evaluation together with the identification of by-products. The photocatalytic process gave rise to the formation of transformation products, and 11 of them were identified by HPLC-HRMS, whereas the complete mineralization was almost achieved after 5 h of irradiation. The assessment of toxicity of the treated solutions was performed by Microtox bioassay (Vibrio fischeri) and in silico tests showing that citalopram photo-transformation involved the formation of harmful compounds.

Elucidation of the photoinduced transformations of Aliskiren in river water using liquid chromatography high-resolution mass spectrometry.

Aliskiren was selected as a compound of potential concern among a suspect screening list of more than 40,000 substances on a basis of high occurrence, potential risk and the absence of information about its environmental fate. This study investigated the photoinduced degradation of aliskiren in river water samples spiked at trace levels exposed to simulated sunlight. A half-life time of 24 h was observed with both direct and indirect photolysis playing a role on pollutant degradation. Its photo-induced transformation involved the formation of six transformation products (TPs), elucidated by LC-HRMS - resulted from the drug hydroxylation, oxidation and moieties loss with subsequent cyclization structurally. The retrospective suspected analysis performed on a total of 754 environmental matrices evidenced the environmental occurrence of aliskiren and two TPs in surface waters (river and seawater), fresh water, sediments and biota. In silico bioassays suggested that aliskiren degradation undergoes thought the formation of TPs with distinct toxicity comparing with the parent compound.

Photocatalytic degradation of drugs in water mediated by acetylated riboflavin and visible light: A mechanistic study.

There is a current concern, among the scientific community, on the pollutants classified as "persistent organic pollutants (POPs)". Pharmaceuticals and personal care products (PPCPs) belong to this family of contaminants; therefore, it is necessary to find more efficient techniques able to achieve their removal from the environment. This study focuses on two different pharmaceuticals: carbamazepine and atenolol, chosen for their widespread use and their different chemical and medical properties. In this work, an organic dye, acetylated riboflavin, has been used in combination with visible light to achieve the photodegradation of these two POPs in <2 h. Moreover, photophysical experiments demonstrated the involvement of the singlet and triplet excited states of acetylated riboflavin and the generated singlet oxygen in the removal of these drugs. Besides, a detailed UFLC-MS-MS analysis of the photoproducts confirmed the oxidation of the drugs. Finally, a plausible mechanism has been postulated.

The "Lab4treat" Outreach Experience: Preparation of Sustainable Magnetic Nanomaterials for Remediation of Model Wastewater.

The Lab4treat experience has been developed to demonstrate the use of magnetic materials in environmental applications. It was projected in the frame of the European project Mat4Treat, and it was tested several times in front of different audiences ranging from school students to the general public in training and/or divulgation events. The experience lends itself to discuss several aspects of actuality, physics and chemistry, which can be explained by modulating the discussion depth level, in order to meet the interests of younger or more experienced people and expand their knowledge. The topic is relevant, dealing with the recycling of urban waste and water depollution. The paper is placed within the field of water treatment for contaminant removal; therefore, a rich collection of recent (and less recent) papers dealing with magnetic materials and environmental issues is described in the Introduction section. In addition, the paper contains a detailed description of the experiment and a list of the possible topics which can be developed during the activity. The experimental approach makes the comprehension of scientific phenomena effective, and, from this perspective, the paper can be considered to be an example of interactive teaching.

Occurrence and Human Health Risk Assessment of Pharmaceuticals and Hormones in Drinking Water Sources in the Metropolitan Area of Turin in Italy.

Pharmaceuticals and hormones (PhACs) enter the aquatic environment in multiple ways, posing potential adverse effects on non-target organisms. They have been widely detected in drinking water sources, challenging water companies to reassure good quality drinking water. The aim of this study was to evaluate the concentration of sixteen PhACs in both raw and treated drinking water sources in the Metropolitan Area of Turin-where Società Metropolitana Acque Torino (SMAT) is the company in charge of the water cycle management-and evaluate the potential human health risks associated to these compounds. Multivariate spatial statistical analysis techniques were used in order to characterize the areas at higher risk of pollution, taking into account the already existing SMAT sampling points' network. Health risks were assessed considering average detected concentrations and provisional guideline values for individual compounds as well as their combined mixture. As reported in the just-issued Drinking Water Directive 2020/2184/UE, in order to establish priority substances, a risk assessment of contaminants present in raw drinking water sources is required for monitoring, identifying potential health risks and, if necessary, managing their removal. The results showed negligibly low human health risks in both raw water sources and treated water.

Structural elucidation of bisphenol E and bisphenol S photoinduced by-products by high-resolution electrospray ionisation mass spectrometry and tandem mass spectrometry.

RATIONALE: Bisphenol E (BPE) and bisphenol S (BPS) have recently replaced bisphenol A as monomers for producing polycarbonates. However, BPE and BPS can pose hazards as they are known to be endocrine disruptors. Despite the huge increase in their use, there is a lack of data regarding the toxicity and effects of BPE and BPS. METHODS: We investigated the photoinduced transformation of BPE and BPS when subjected to sun-simulated radiation and using TiO2 as a photocatalyst. Analyses of BPE, BPS and their by-products were performed by high-performance liquid chromatography/high-resolution mass spectrometry (HPLC/HRMS) using an orbitrap mass analyzer in negative electrospray ionisation (ESI) mode. The chromatographic separations were achieved by employing a C18 reversed-phase column, and the transformation products (TPs) were elucidated structurally using HRMS and multistage MS experiments performed in collision-induced dissociation (CID) mode. RESULTS: The transformation of bisphenol S involved the formation of twelve by-products, while ten TPs were detected following BPE degradation. For bisphenol S, the cleavage of the molecule is a very important transformation route, together with the hydroxylation of the substrate to provide mono- and poly-hydroxylated TPs. For bisphenol E, the two main routes were hydroxylation and ring opening. Acute toxicity for BPS, BPE and their TPs was assessed using the Vibrio fischeri assay, highlighting that their initial transformation involved the formation of TPs that were more toxic than the parent compound. CONCLUSIONS: The HPLC/HRMS method developed was useful for characterising and identifying newly formed TPs from bisphenol E and bisphenol S. This study aimed to examine the structure of twenty by-products identified during TiO2 -mediated photolysis and to evaluate acute toxicity over time.

Non-purified commercial multiwalled carbon nanotubes supported on electrospun polyacrylonitrile@polypyrrole nanofibers as photocatalysts for water decontamination.

We present a photoactive composite material for water decontamination consisting of non-purified commercial multiwalled carbon nanotubes (CNT(NP)s) supported on an electrospun polymeric mat made of core-sheath polyacrylonitrile-polypyrrole nanofibers. This is the first system that specifically exploits the superior photocatalytic activity of CNT(NP)s compared with the purified carbon nanotubes usually employed. A CNT(NP) still contains the catalytic metal oxide nanoparticles (NPs) used for its synthesis, embedded in the nanotube structure. Under UV-visible irradiation, these NPs generate highly reactive ˙OH radicals capable of degrading the organic molecules adsorbed on the nanotube. Photocatalytic tests on the composite material show that CNT(NP)s act mostly as a source of photogenerated charge carriers. The adsorption of target substrates occurs preferentially onto the polypyrrole sheath, which shuttles the reactive carriers from CNT(NP)s to the substrates. In addition, UV-visible irradiation of semiconducting polypyrrole generates radical species that directly react with the adsorbed substrates. All synthetic procedures reported are scalable and sustainable. This mechanically resistant and flexible composite overcomes one of the weakest aspects of water treatments that employ suspended nanocatalysts, namely the expensive and poorly scalable recovery of the catalyst through nanofiltration. All these features are required for large-scale photocatalytic treatments of polluted water.

Study of the photoinduced transformations of sertraline in aqueous media.

In the present study, the photoinduced degradation of the antidepressant drug sertraline under artificial solar radiation was examined. Photolysis was studied under different experimental conditions to explore its photolytic fate in the aqueous environment. Photolytic degradation kinetics were carried out in ultrapure water, wastewater effluent, as well as in the presence of dissolved organic matter (humic acids), bicarbonate and nitrate ions which enabled their assessment on sertraline photo-transformation. The reaction of sertraline with photoactive compounds accelerated sertraline transformation in comparison with direct photolysis. Moreover, TiO2-mediated photocatalytic degradation of sertraline was investigated, and focus was placed on the identification of by-products. As expected, photocatalysis was extremely effective for sertraline degradation. Photocatalytic degradation proceeded through the formation of forty-four transformation products identified by HPLC-HRMS and after 240 min of irradiation total mineralization was achieved. Microtox bioassay (Vibrio fischeri) was employed to assess the ecotoxicity of the photocatalysis-treated solutions and results have indicated that sertraline photo-transformation proceeds through the formation of toxic compounds.

Study of the photoinduced transformations of maprotiline in river water using liquid chromatography high-resolution mass spectrometry.

Maprotiline was identified as a compound of potential interest further to a suspect screening test carried out for a list of more than 40,000 substances based on specific occurrence, hazard and risk indicators. Despite the high frequency of appearance of this drug in wastewater treatment stations, his environmental fate is still unknown. Herein, we investigated for the first time the maprotiline degradation pathways in river water spiked with the drug at a concentration close to those detected in natural waters. Preliminary photocatalytic experiments in ultrapure water produced 32 transformation products (TPs) resulted mainly from the multiple hydroxylation/oxidation in different positions of the drug molecule. From the river water experiments, 12 TPs were formed by photolysis matching with those observed in ultrapure water experiments, and 2 were also formed resulted from biotic degradation. Employing HPLC-HRMS, we were able to elucidate the chemical structures of TPs and assess the overall degradation mechanism. Preliminary bioassays suggested lower toxicity of TPs relatively to the parent compound.

Effect of UV-A, UV-B and UV-C irradiation of glyphosate on photolysis and mitigation of aquatic toxicity.

The active herbicide ingredient glyphosate [N-(phosphonomethyl)glycine] is frequently detected as a contaminant in groundwater and surface waters. This study investigated effects of UV-A (365 nm), UV-B (302 nm) and UV-C (254 nm) irradiation of glyphosate in water on photolysis and toxicity to aquatic organisms from different trophic levels. A test battery with bacteria (Bacillus subtilis, Aliivibrio fischeri), a green microalga (Raphidocelis subcapitata), and a crustacean (Daphnia magna) was used to assess biological effect of glyphosate and bioactive transformation products before and after UV irradiation (4.7-70 J/cm2). UV-C irradiation at 20 J/cm2 resulted in a 2-23-fold decrease in toxicity of glyphosate to aquatic test organisms. UV-B irradiation at 70 J/cm2 caused a twofold decrease whereas UV-A did not affect glyphosate toxicity at doses ≤ 70 J/cm2. UV-C irradiation of glyphosate in drinking water and groundwater with naturally occurring organic and inorganic constituents showed comparable or greater reduction in toxicity compared to irradiation in deionized water. High-resolution mass spectrometry analyses of samples after UV-C irradiation showed > 90% decreases in glyphosate concentrations and the presence of multiple transformation products. The study suggests that UV mediated indirect photolysis can decrease concentrations of glyphosate and generate less toxic products with decreased overall toxicity to aquatic organisms.

Liquid chromatography/mass spectrometry analytical determination of gabapentin transformation products by heterogeneous photocatalysis and environmental evaluation.

RATIONALE: Gabapentin is a drug used to treat epilepsy and peripheral neuropathic pain. It is an analog of gamma-aminobutyric acid, and it is a selective blocker of voltage-gated calcium channels. The drug is excreted unmetabolized; it is stable in the environment and is classified as a persistent mobile organic contaminant. Because wastewater treatment plants (WWTPs) are not completely efficient, some bioactive molecules may be released unaltered into the environment. The aim of this study was to provide information about degradation pathways of gabapentin in water by studying its photoinduced transformation products (TPs) through laboratory simulation experiments. Gabapentin and its TPs were monitored in influent and effluent water samples from WWTPs in Germany and Italy. METHODS: The laboratory simulation used heterogeneous photodegradation mediated by titanium dioxide (TiO2 ). Chromatographic separation was achieved using a C18 reverse-phase column, and the structural identification of TPs was performed using high-resolution electrospray ionization high-resolution mass spectrometry (ESI-HRMS) and multistage MSn experiments. RESULTS: Several TPs were observed during TiO2 photodegradation. Nine new compounds were detected, and potential structures were assigned by studying the fragmentation pathways of the [M + H]+ ions of these TPs and gabapentin. Gabapentin and some of the newly identified TPs were found in environmental samples from WWTPs. CONCLUSIONS: The developed high-performance liquid chromatography/high-resolution mass spectrometry method was used to identify TPs from gabapentin. It was then successfully applied to real environmental samples to monitor the TPs as potential environmental pollutants.

Use of Low-Cost Magnetic Materials Containing Waste Derivatives for the (Photo)-Fenton Removal of Organic Pollutants.

Hybrid magnetite/maghemite nanoparticles (MNP) coated with waste-sourced bio-based substances (BBS) were synthesized and studied for the degradation of phenol, chosen as a model pollutant, in water. A systematic study was undertaken in order to rationalize MNP-BBS behavior and optimize their performance. The effect of experimental parameters, such as light irradiation, addition of hydrogen peroxide, and the ratio between hydrogen peroxide and MNP-BBS concentrations, was studied. The generation of hydroxyl radicals was assessed, and the recovery and re-cycle of the material was investigated. Our results indicate that phenol degradation could be attained by both Fenton and photo-Fenton processes, with higher efficiency in dark condition and in the presence of a suitable amount of hydrogen peroxide. Evidence was obtained for the roles of iron ions leached from the materials as well as of organic matter released in the solution upon partial photodegradation of the organic coating. The reusability tests indicated a lower but still valid performance of the material. Optimization of the experimental conditions was performed to achieve the highest efficiency in substrate degradation, and fundamental insights into the mechanism of the MNP-BBS Fenton-like reaction were obtained.

Surfactant-Assisted Fabrication of Alumina-Doped Amorphous Silica Nanofiltration Membranes with Enhanced Water Purification Performances.

Surfactant-templated 5 mol% Al2O3-doped silica membranes nanofiltration membranes were synthesized via the sol-gel method, and afterward, were optimized, and tested with respect to the permeability and rejection rate. The disordered silica network was stabilized by doping 5 mol% alumina. Tetraethyl orthosilicate and aluminum isopropoxide were used as the silica and alumina precursors, respectively. Cetyltrimethylammonium bromide (CTAB) was used not only as a pore-forming agent, but also to control the reaction rate of the aluminum isopropoxide, thus obtaining highly homogeneous materials. The results about filtration of model solutions showed that the optimized membranes are featured by both a relatively high water permeability (1.1-2.3 L·m-2·h-1 ·bar-1) and a high rejection for salts (74% for NaCl, and >95% for MgSO4 and Na2SO4) and organic pollutants (e.g., about 98% for caffeine). High rejection of divalent ions and organic molecules was also observed when a real wastewater effluent was filtered. The influence of the synthesis conditions on the membrane performance is discussed.