Chemical characterization and speciation of the soluble fraction of Arctic PM.

The chemical composition of the soluble fraction of atmospheric particulate matter (PM) and how these components can combine with each other to form different species affect the chemistry of the aqueous phase dispersed in the atmosphere: raindrops, clouds, fog, and ice particles. The study was focused on the analysis of the soluble fraction of Arctic PM samples collected at Ny-Ålesund (Svalbard Islands, Norwegian Arctic) during the year 2012. The concentration values of Na, K, NH, Ca, Mg, Mn, Cu, Zn, Fe, Al, Cl, NO, NO, SO, PO, formate, acetate, malonate, and oxalate in the water-soluble fraction of PM were determined by atomic spectroscopy and ion chromatography.

Phototransformation of Vanillin in Artificial Snow by Direct Photolysis and Mediated by Nitrite.

The photodegradation of vanillin, as a proxy of methoxyphenols emitted by biomass burning, was investigated in artificial snow at 243 K and in liquid water at room temperature. Nitrite (NO) was used as a photosensitizer of reactive oxygen and nitrogen species under UVA light, because of its key photochemical role in snowpacks and atmospheric ice/waters. In snow and in the absence of NO, slow direct photolysis of vanillin was observed due to back-reactions taking place in the quasi-liquid layer at the ice-grain surface.

Assessing the photodegradation potential of compounds derived from the photoinduced weathering of polystyrene in water.

Benzoate (Bz) and acetophenone (AcPh) are aromatic compounds known to be produced by sunlight irradiation of polystyrene aqueous suspensions. Here we show that these molecules could react with OH (Bz) and OH + CO (AcPh) in sunlit natural waters, while other photochemical processes (direct photolysis and reaction with singlet oxygen, or with the excited triplet states of chromophoric dissolved organic matter) are unlikely to be important. Steady-state irradiation experiments were carried out using lamps, and the time evolution of the two substrates was monitored by liquid chromatography.

Solar photodegradation of irinotecan in water: optimization and robustness studies by experimental design.

Irinotecan, a widely prescribed anticancer drug, is an emerging contaminant of concern that has been detected in various aquatic environments due to ineffective removal by traditional wastewater treatment systems. Solar photodegradation is a viable approach that can effectively eradicate the drug from aqueous systems. In this study, we used the design of experiment (DOE) approach to explore the robustness of irinotecan photodegradation under simulated solar irradiation.

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.

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.

Evaluation of Fenton and modified Fenton oxidation coupled with membrane distillation for produced water treatment: Benefits, challenges, and effluent toxicity.

Membrane distillation is a promising technology to desalinate hypersaline produced waters. However, the organic content can foul and wet the membrane, while some fractions may pass into the distillate and impair its quality. In this study, the applicability of the traditional Fenton process was investigated and preliminarily optimized as a pre-treatment of a synthetic hypersaline produced water for the following step of membrane distillation.

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.

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.

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.

The role of direct photolysis in the photodegradation of the herbicide bentazone in natural surface waters.

The photochemical fate of the herbicide bentazone was assessed by lab experiments and modeling tools. Experimental and modeling results showed that bentazone is mainly photodegraded by direct photolysis in natural water samples, even in the presence of dissolved organic matter (DOM) that can act as light-screening agent, photosensitizer and scavenger of reactive species. Even when it was dissolved in natural water samples containing different DOM amounts, the phototransformation kinetics of bentazone was unchanged compared to irradiation runs in ultrapure water.

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

Surfactant-templated 5 mol% AlO-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.

Evaluation of transformation products from chemical oxidation of micropollutants in wastewater by photoassisted generation of sulfate radicals.

In this research, the degradation of seven different micropollutants (MPs) and the formation of their transformation products (TPs) have been assessed during the application of different advanced oxidation processes: photolytic and photocatalytic activation of peroxymonosulfate (PMS) and persulfate (PS). The results were compared with those obtained from the photolytic experiments using hydrogen peroxide (HO) as oxidant. A significant abatement of almost all MPs was achieved, even with very low UV-C contact time (9 and 28 s).

Photocatalytic abatement of emerging pollutants in pure water and wastewater effluent by TiO and Ce-ZnO: degradation kinetics and assessment of transformation products.

Here, the performances of two different catalysts, Ce-ZnO and TiO2 synthetized in our laboratories, were compared with the commercial TiO2-P25 for degradation of a mixture of seven emerging pollutants under UV irradiation. The investigation included monitoring pollutants abatement in Milli-Q water and in wastewater effluent and identifying their transformation products by HPLC-HRMS. Structural characterization of intermediates supported by data available from literature allowed elucidation of the transformation pathways occurring in the presence of all investigated catalysts in the wastewater effluent.

New Insights on the Photodegradation of Caffeine in the Presence of Bio-Based Substances-Magnetic Iron Oxide Hybrid Nanomaterials.

The exploitation of organic waste as a source of bio-based substances to be used in environmental applications is gaining increasing interest. In the present research, compost-derived bio-based substances (BBS-Cs) were used to prepare hybrid magnetic nanoparticles (HMNPs) to be tested as an auxiliary in advanced oxidation processes. Hybrid magnetic nanoparticles can be indeed recovered at the end of the treatment and re-used in further water purification cycles.

A model assessment of the potential of river water to induce the photochemical attenuation of pharmaceuticals downstream of a wastewater treatment plant (Guadiana River, Badajoz, Spain).

We predicted the possible direct and indirect phototransformation kinetics of carbamazepine (CBZ), ibuprofen (IBU) and diclofenac (DIC) in river water, based on data of water chemistry obtained for the Guadiana River near Badajoz (Southwestern Spain) during a year-round sampling campaign. The three compounds were chosen, (i) because they occurred at the outlet of the wastewater treatment plant (WWTP) in Badajoz, as well as in river water sampled 1 km downstream of the WWTP, and (ii) because their photochemical fate in surface waters is known well enough to be modelled. The predicted phototransformation kinetics would be negligible in winter and fastest in April-August, with comparable rate constants in April through August despite differences in sunlight irradiance.

Effects of the antioxidant moieties of dissolved organic matter on triplet-sensitized phototransformation processes: Implications for the photochemical modeling of sulfadiazine.

Previous studies have shown that the photodegradation of some pollutants, induced by the excited triplet states of chromophoric dissolved organic matter (CDOM*), can be inhibited by back-reduction processes carried out by phenolic antioxidants occurring in dissolved organic matter (DOM). Here, for the first time to our knowledge, we included such an inhibition effect into a photochemical model and applied the model predictions to sulfadiazine (SDZ), a sulfonamide antibiotic that occurs in surface waters in two forms, neutral HSDZ and anionic SDZ (pK = 6.5).

High-performance liquid chromatography/high-resolution mass spectrometry for the characterization of transformation products of ionic liquids.

Rationale: Ionic liquids (ILs) are a subject of active research in the field of alternative solvents. We studied the behaviour of a piperidine IL, 1-butyl-1-methylpiperidinium tetrafluoroborate (BMPA), through the elucidation of its transformation products (TPs) in water.

Methods: The transformation pathways of BMPA were investigated using high-performance liquid chromatography (HPLC) combined with a hybrid LTQ-Orbitrap instrument on the basis of mass defect filtering.

Assessment of the photocatalytic transformation of pyridinium-based ionic liquids in water.

We studied some ionic liquids (ILs) belonging to the pyridinium class under photocatalytic treatment. In particularly, we analysed how the length of the alkyl chain, the kind of inorganic ion and the type of substituents could influence the disappearance rate, the mineralization extent, the acute toxicity and the transformation mechanism. For such, we selected some pyridinium derivatives with different alkyl chain but the same anion, namely tetrafluoroborate (1-ethylpyridinium, 1-butylpyridinium, 1-hexylpyridinium), with two alkyl substituents (4-methyl-1-butylpyridinium) and with a different substituent (1-cyanopropylpyridinium).

Photoinduced transformation of pyridinium-based ionic liquids, and implications for their photochemical behavior in surface waters.

The photochemical reactivity of three ionic liquids (1-ethylpyridinium tetrafluoroborate, 1-butyl-4-methylpyridinium tetrafluoroborate, and 1-(3-cyanopropyl)pyridinium chloride) was studied by combining laboratory experiments and photochemical modeling, to get insight into the possible behavior in surface-water environments. Among the studied compounds, phototransformation in sunlit surface waters could be an important attenuation pathway for 1-butyl-4-methylpyridinium tetrafluoroborate (BMPOTFB). In this case the reaction with the carbonate radicals (CO) would prevail at low values of the dissolved organic carbon (DOC), while the direct photolysis would be important at intermediate to high DOC values.

Degradation of Methyl 2-Aminobenzoate (Methyl Anthranilate) by H₂O₂/UV: Effect of Inorganic Anions and Derived Radicals.

This study shows that methyl 2-aminobenzoate (also known as methyl anthranilate, hereafter MA) undergoes direct photolysis under UVC and UVB irradiation and that its photodegradation is further accelerated in the presence of H₂O₂. Hydrogen peroxide acts as a source of hydroxyl radicals (·OH) under photochemical conditions and yields MA hydroxyderivatives. The trend of MA photodegradation rate vs.

Modelling the photochemical attenuation pathways of the fibrate drug gemfibrozil in surface waters.

Gemfibrozil (GFZ) is a relatively persistent pollutant in surface-water environments and it is rather recalcitrant to biological degradation. The GFZ photochemical lifetimes are relatively short in shallow waters with low levels of dissolved organic carbon (DOC), but they can reach the month-year range in deep and high-DOC waters. The main reason is that GFZ undergoes negligible reaction with singlet oxygen or degradation sensitised by the triplet states of chromophoric dissolved organic matter, which are the usually prevalent photochemical pathways in deep and high-DOC sunlit waters.

Assessing the phototransformation of diclofenac, clofibric acid and naproxen in surface waters: Model predictions and comparison with field data.

Phototransformation is important for the fate in surface waters of the pharmaceuticals diclofenac (DIC) and naproxen (NAP) and for clofibric acid (CLO), a metabolite of the drug clofibrate. The goal of this paper is to provide an overview of the prevailing photochemical processes, which these compounds undergo in the different conditions found in freshwater environments. The modelled photochemical half-life times of NAP and DIC range from a few days to some months, depending on water conditions (chemistry and depth) and on the season.