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At the European level (CEN/TC386), some efforts are currently devoted to new standards for comparing the efficiency of commercial photocatalytic material/devices in various application fields. Concerning prototype or commercial indoor photocatalytic air purifiers designed for volatile organic compounds (VOC) abatement, the methodology is based on a laboratory airtight chamber. The photocatalytic function is demonstrated by the mineralization of a mixture of five VOCs. Experimental data were obtained for four selected commercial devices and three commercial materials: drop of VOC concentration, but also identification of secondary species (with special attention to formaldehyde), mineralization rates, and Clean Air Delivery Rate (CADR). With two efficient air purifiers, these laboratory experiments were compared to the results in two experimental rooms (35-40 m) where air pollution was introduced through wooden floor and furniture. The systems' ageing was also studied. The safety of the commercial products was also assessed by the determination of nanoparticle release. Standardized tests are useful to rank photocatalytic air purifiers and passive materials and to discard inefficient ones. A good correlation between the standard experiments and the experimental room experiments was found, even if in the latter case, the concentration of lower weight VOCs drops less quickly than that of heavier VOCs. [ABSTRACT FROM AUTHOR]

Highlights: [•] Preparation of mesoporous Pt-doped titania thin film by EISA process. [•] Characterization of the Pt oxidation state at the surface of the films. [•] Comparison of the UV and visible photocatalytic activity of doped/undoped films. [•] Quantification of hydroxyl radicals production at the films surface. [ABSTRACT FROM AUTHOR]

Abstract: The photooxidation of dimethylsulfide (DMS) in the gas phase was studied with two different materials, under identical conditions. The first material (TiO2-QZ) is based on titanium dioxide (TiO2) deposited on quartz bars by the sol–gel method. The second one (DCA-SG) is based on the well known photosensitizer, 9,10-dicyanoanthracene (DCA) encapsulated in a sol–gel silica network. In spite of non-optimized conditions, both materials allow the oxidation of DMS in air under irradiation. However, the oxidation products are strikingly different: dimethyldisulfide is the main product detected in the gas phase with TiO2-QZ due to a too short residence time to achieve complete mineralization. With DCA-SG no gaseous product is detected in the treated gaseous flow for more than 100h, due to the exclusive formation of polar dimethylsulfoxide and dimethylsulfone which are totally adsorbed on the highly polar silica gel. The efficiency of this latter reaction depends on the DMS concentration, gas flow and light intensity, but is not affected by the presence of small amounts of water. Singlet oxygen appears to be formed efficiently under these conditions. The saturation of DCA-SG by the oxidation products was demonstrated by several complementary methods, and some possible solutions to regenerate the material are proposed. The complementarities of both TiO2-QZ and DCA-SG could be used to achieve the oxidation of different classes of pollutants. [Copyright &y& Elsevier]

Abstract: This study describes a method derived from ISO/TC 206/SC specifications to assess the bactericidal activity against a bacterial strain, Pseudomonas fluorescens, of various photocatalytic fabrics, under UVA and filtered visible light. The experimental method allowed the accurate quantification of bacteria survival on photoactive surfaces and films under UVA and UV-free visible irradiation. Cotton fabrics coated with TiO2, anthraquinone or anthraquinone-sensitized TiO2 display a significant bactericidal efficiency. TiO2-coated fabrics are very efficient against P. fluorescens after 4h UVA irradiation (bacteria survival below the detection limit). Under UVA-free visible light, anthraquinone-sensitized TiO2 coated fabrics induced a significant bactericidal activity after 2h irradiation, while anthraquinone alone-coated fabrics were not as efficient and TiO2 coated fabrics were almost inefficient. These results show that although exhibiting a weak n–π* band in the 350–420nm range, anthraquinone is a good candidate as an efficient visible light photosensitizer. A synergy effect between anthraquinone and TiO2 was demonstrated. A possible reaction mechanism, involving a synergy effect for singlet oxygen formation with anthraquinone-sensitized TiO2 is proposed to account for these results. [Copyright &y& Elsevier]

In the past few years, there has been an increasing interest in mycosporines-UV-absorbing molecules-bringing important insights into their intrinsic properties as natural sunscreens. Herein, mycosporine-serinol and gadusol (enolate form)/gadusolate were exposed to UV radiation via a solar simulator and the photostability was assessed in pure water and different natural matrices like river, estuary and ocean water. In general, this study revealed that the photodegradation of gadusolate and mycosporine-serinol was higher in natural matrices than in pure water due to the generation of singlet oxygen on UV irradiation. In pure water, in terms of photostability, both gadusolate and mycosporine-serinol were found to offer good protection and high performance in terms of photodegradation quantum yield ((0.8 ± 0.2) × 10 -4 and (1.1 ± 0.6) × 10 -4 , respectively). Nonetheless, the photostability of mycosporine-serinol was found to be superior to that of gadusolate in natural water, namely, ocean, estuary and river. The present work highlights how mycosporine-serinol and gadusolate resist photodegradation, and supports their role as effective and stable UV-B sunscreens.

Galaxolide (HHCB) is the most common synthetic musk compound detected in numerous daily products. Despite its persistence in the aquatic environment, the photodegradation of HHCB remains poorly understood. In this study, we investigated the direct and indirect photolysis kinetics of HHCB under simulated sunlight and UVC light. Our aim was to determine the role of reactive oxygen species (ROS) responsible for HHCB degradation in the aquatic environment and to identify its transformation products. The influence of environmental factors on indirect photolysis was investigated by testing both synthetic waters (containing humic acid, carbonate (CO 3 2- ), and nitrate (NO 3 - )) and real waters (riverine and effluent). Hydrogen peroxide (H 2 O 2 /UVC) was tested to simulate the wastewater treatment process. Quencher experiments were conducted to identify the role of ROS in HHCB photodegradation, including hydroxyl radicals (˙OH), carbonate radicals (CO 3 ˙ - ), triplet states of dissolved organic matter ( 3 DOM*), and singlet oxygen ( 1 O 2 ). The results clearly indicated that HHCB was efficiently degraded by direct photolysis under both light conditions. The presence of H 2 O 2 led to the most efficient HHCB degradation due to the high production of ˙OH induced under UVC. Indirect photolysis contribution was observed, induced by ˙OH, CO 3 ˙ - , 3 DOM*, and 1 O 2 to different extents depending on the light and matrix composition. The experiments led to the detection of transformation products: HHCB lactone, a well-known transformation product, and two other substances with proposed structures. This study provides a comprehensive identification of the processes involved in the direct and indirect photodegradation of HHCB, which could serve as the basis for evaluating and modeling the fate of HHCB in aquatic environments.

Background: High dietary carbohydrates can spare protein in rainbow trout (Oncorhynchus mykiss) but may affect growth and health. Inulin, a prebiotic, could have nutritional and metabolic effects, along with anti-inflammatory properties in teleosts, improving growth and welfare. We tested this hypothesis in rainbow trout by feeding them a 100% plant-based diet, which is a viable alternative to fishmeal and fish oil in aquaculture feeds. In a two-factor design, we examined the impact of inulin (2%) as well as the variation in the carbohydrates (CHO)/plant protein ratio on rainbow trout. We assessed the influence of these factors on zootechnical parameters, plasma metabolites, gut microbiota, production of short-chain fatty acids and lactic acid, as well as the expression of free-fatty acid receptor genes in the mid-intestine, intermediary liver metabolism, and immune markers in a 12-week feeding trial., Results: The use of 2% inulin did not significantly change the fish intestinal microbiota, but interestingly, the high CHO/protein ratio group showed a change in intestinal microbiota and in particular the beta diversity, with 21 bacterial genera affected, including Ralstonia, Bacillus, and 11 lactic-acid producing bacteria. There were higher levels of butyric, and valeric acid in groups fed with high CHO/protein diet but not with inulin. The high CHO/protein group showed a decrease in the expression of pro-inflammatory cytokines (il1b, il8, and tnfa) in liver and a lower expression of the genes coding for tight-junction proteins in mid-intestine (tjp1a and tjp3). However, the 2% inulin did not modify the expression of plasma immune markers. Finally, inulin induced a negative effect on rainbow trout growth performance irrespective of the dietary carbohydrates., Conclusions: With a 100% plant-based diet, inclusion of high levels of carbohydrates could be a promising way for fish nutrition in aquaculture through a protein sparing effect whereas the supplementation of 2% inulin does not appear to improve the use of CHO when combined with a 100% plant-based diet., (© 2024. The Author(s).)

High value food products are subject to adulterations and frauds. This study aimed to combine, in our knowledge for the first time, inorganic chemical tracers (multi-elements and Sr isotopy) with volatile organic compound (VOCs) to discriminate the geographic origin, the varieties and transformation processes to authenticate 26 tea samples. By measuring Sr isotope ratio using the multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS), 6 out of 11 regions were successfully discriminated. The combination with the ICP-MS inorganic pattern allowed to discriminate 4 more regions with a significance level of 0.05. VOCs fingerprints, obtained with selected ion flow tube mass spectrometer (SIFT-MS), were not correlated with origin but with the cultivar and transformation processes. Green, oolong, and dark teas were clearly differentiated, with hexanal and hexanol contributing to the discrimination of oxidation levels. With this multi-instrumental approach, it is possible to certify the geographical origin and the tea conformity., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023. Published by Elsevier Ltd.)

Inulin affects nutrition and metabolism in many animals. Although inulin is widely used in the diet of teleosts, its mechanism of action is unknown. Here, we investigated the effect of inulin (2 %) on the intestinal microbiome and metabolism in rainbow trout ( Oncorhynchus mykiss ) selected for growth and survival when fed a 100 % plant-based diet ( suave ) and a control line ( temoin ). Metabolic responses to the two factors (line and inulin) in liver, intestine, muscle and adipose were tissue-specific, with line and interaction between the two factors influencing overall expression in liver. In the intestine, inulin and line and in muscle, line influenced the expression of metabolic genes. Microbiota between the mucus and digestive contents was significantly different, with genera from Proteobacteria being more abundant in the mucus, whereas genera from the Firmicutes and Planctomycetes being more abundant in contents. Effect of inulin and interaction between factors on the microbiome was evident in contents. The significant taxa of control and inulin-fed groups differed greatly with Streptococcus and Weissella being significantly abundant in the inulin-fed group. There was a general trend showing higher levels of all SCFA in temoin group with propionic acid levels being significantly higher. An operational taxonomic unit (OTU) belonging to the Ruminococcaceae was significantly abundant in suave . The tissue-specific correlations between OTU and gene expression may indicate the link between microbiome and metabolism. Together, these results suggest that line and inulin impact the gene expression in a tissue-specific manner, possibly driven by specific OTUs enriched in inulin-fed groups and suave .

The key factors which affect the abiotic photodemethylation process of monomethylmercury (MMHg) in the freshwaters has remained unclear. Hence, this work aimed to better elucidate the abiotic photodemethylation pathway in a model freshwater. Anoxic and oxic conditions were implemented to investigate the simultaneous photodemethylation to Hg(II) and photoreduction to Hg(0). MMHg freshwater solution was irradiated through exposure to three wavelength ranges of full light (280-800 nm), without short UVB (305-800 nm), and visible light (400-800 nm). The kinetic experiments were performed following dissolved and gaseous Hg species concentrations (i.e., MMHg, iHg(II), Hg(0)). A comparison between two methods of post-irradiation purging and continuous-irradiation purging confirmed MMHg photodecomposition to Hg(0) is mainly induced by a first photodemethylation step to iHg(II) followed by a photoreduction step to Hg(0). Photodemethylation under full light extent normalized to absorbed radiation energy showed a higher rate constant in anoxic conditions at 18.0 ± 2.2 kJ -1 compared to oxic conditions at 4.5 ± 0.4 kJ -1 . Moreover, photoreduction also increased up to four-fold under anoxic conditions. Normalized and wavelength-specific photodemethylation (K pd ) and photoreduction (K pr ) rate constants were also calculated for natural sunlight conditions to evaluate the role of each wavelength range. The relative ratio in wavelength-specific K PAR : K long UVB+ UVA : K short UVB showed higher dependence on UV light for photoreduction at least ten-fold compared to photodemethylation, regardless of redox conditions. Both results using Reactive Oxygen Species (ROS) scavenging methods and Volatile Organic Compounds (VOC) measurements revealed the occurrence and production of low molecular weight (LMW) organic compounds that are as photoreactive intermediates responsible for MMHg photodemethylation and iHg(II) photoreduction in the dominant pathway. This study also supports the role of dissolved oxygen as an inhibitor for the photodemethylation pathways driven by LMW photosensitizers., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

Three-dimensional photoactive self-standing porous materials have been synthesized through the integration of soft chemistry and colloids (emulsions, lyotrope mesophases, and P25 titania nanoparticles). Final multiscale porous ceramics bear 700-1000 m 2 g -1 of micromesoporosity depending on the P25 nanoparticle contents. The applied thermal treatment does not affect the P25 anatase/rutile allotropic phase ratio. Photonic investigations correlated with the foams' morphologies suggest that the larger amount of TiO 2 that is introduced, the larger the walls' density and the smaller the mean size of the void macroscopic diameters, with both effects inducing a reduction of the photon transport mean free path ( l t ) with the P25 content increase. A light penetration depth in the range of 6 mm is reached, thus depicting real 3D photonic scavenger behavior. The 3D photocatalytic properties of the MUB-200(x) series, studied in a dynamic "flow-through" configuration, show that the highest photoactivity (concentration of acetone ablated and concentration of CO 2 formed) is obtained with the highest monolith height (volume) while providing an average of 75% mineralization. These experimental results validate the fact that these materials, bearing 3D photoactivity, are paving the path for air purification operating with self-standing porous monolith-type materials, which are much easier to handle than powders. As such, the photocatalytic systems can now be advantageously miniaturized, thereby offering indoor air treatment within vehicles/homes while drastically limiting the associated encumbrance. This volumetric counterintuitive acting mode for light-induced reactions may find other relevant advanced applications for photoinduced water splitting, solar fuel, and dye-sensitized solar cells while both optimizing photon scavenging and opening the path for the miniaturization of the processes where encumbrance or a foot-print penalty would be advantageously circumvented.

Organophosphate esters are an emerging environmental concern since they spread persistently across all environmental compartments (air, soil, water, etc.). Measurements of semivolatile organic compounds are important but not without challenges due to their physicochemical properties. Selected ion flow tube-mass spectrometry (SIFT-MS) can be relevant for their analysis in air because it is a direct analytical method without separation that requires little preparation and no external calibration. SIFT-MS is based on the chemical reactivity of analytes with reactant ions. For volatile and semivolatile organic compound analysis in the gas phase, knowledge of ion-molecule reactions and kinetic parameters is essential for the utilization of this technology. In the present work, we focused on organophosphate esters, semivolatile compounds that are now ubiquitous in the environment. The ion-molecule reactions of eight precursor ions that are available in SIFT-MS (H 3 O + , NO + , O 2 •+ , OH - , O •- , O 2 •- , NO 2 - , and NO 3 - ) with six organophosphate esters were investigated. The modeling of ion-molecule reaction pathways by calculations supported and complemented the experimental work. Organophosphate esters reacted with six of the eight precursor ions with characteristic reaction mechanisms, such as protonation with hydronium precursor ions and association with NO + ions, while nucleophilic substitution occurred with OH - , O •- , and O 2 •- . No reaction was observed with NO 2 - and NO 3 - ions. This work shows that the direct analysis of semivolatile organic compounds is feasible using SIFT-MS with both positive and negative ionization modes.

Volatile organic compounds (VOCs) emitted by food products are decisive for the perception of aroma and taste. The analysis of gaseous matrices is traditionally done by detection and quantification of few dozens of characteristic markers. Emerging direct injection mass spectrometry technologies offer rapid analysis based on a soft ionisation of VOCs without previous separation. The recent increase of selectivity offered by the use of several precursor ions coupled with untargeted analysis increases the potential power of these instruments. However, the analysis of complex gaseous matrix results in a large number of ion conflicts, making the quantification of markers difficult, and in a large volume of data. In this work, we present the exploitation of untargeted SIFT-MS volatile fingerprints of ewe PDO cheeses in a real farm model, using mixOmics methods allowing us to illustrate the typicality, the manufacturing processes reproducibility and the impact of the animals' diet on the final product., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

In situ chemical oxidations are known to remediate PAH contaminations in groundwater and soils. In this study, batch-scale oxidations aim to compare the PAC (polycyclic aromatic compound) degradation of three oxidation processes traditionally applied for soil treatment: permanganate, heat-activated persulfate (60 °C) and Fenton-like activated by magnetite, to results obtained with ferrates (Fe VI ). Widely studied for water treatments, ferrates are efficient on a wide range of pollutants with the advantage of producing nontoxic ferric sludge after reaction. However, fewer works focus on their action on soil, especially on semi-industrial grade ferrates (compatible with field application). Oxidations were carried out on sand spiked with dense non-aqueous phase liquid (DNAPL) sampled in the groundwater of a former coking plant. Conventional 16 US-EPA PAHs and polar PACs were monitored, especially potential oxygenated by-products that can be more harmful than parent-PAHs. After seven reaction days, only the Fenton-like showed limited degradation. Highest efficiencies were obtained for heat-activated persulfate with no O-PAC ketones formed. Permanganate gave important degradation, but ketones were generated in large amount. The tested ferrates not only gave slightly lower yields due to their auto-decomposition but also induced O-PAC ketone production, suggesting a reactional pathway dominated by oxidoreductive electron transfer, rather than a radical one.

Rationale: The concentrations of aldehydes and volatile fatty acids have to be controlled because of their potential harmfulness in indoor air or relationship with the organoleptic properties of agri-food products. Although several specific analytical methods are currently used, the simultaneous analysis of these compounds in a complex matrix remains a challenge. The combination of positive and negative ionization selected ion flow tube mass spectrometry (SIFT-MS) allows the accurate, sensitive and high-frequency analysis of complex gas mixtures of these compounds., Methods: The ion-molecule reactions of negative precursor ions (OH - , O •- , O 2 •- , NO 2 - and NO 3 - ) with five aldehydes and four carboxylic acids were investigated in order to provide product ions and rate constants for the quantification of these compounds by negative ion SIFT-MS. The results were compared with those obtained by conventional analysis methods and/or with already implemented SIFT-MS positive ionization methods. The modelling of hydroxide ion (OH - )/molecule reaction paths by ab-initio calculation allowed a better understanding of these gas-phase reactions., Results: Deprotonation systematically occurs by reaction between negative ions and aldehydes or acids, leading to the formation of [M - H] - primary ions. Ab-initio calculations demonstrated the α-CH deprotonation of aldehydes and the acidic proton abstraction for fatty acids. For aldehydes, the presence of water in the flow tube leads to the formation of hydrated ions, [M - H] - .H 2 O. With the NO 2 - precursor ion, a second reaction channel results in ion-molecule association with the formation of M.NO 2 - ions., Conclusions: Except for formaldehyde, all the studied compounds can be quantified by negative ion SIFT-MS with significant rate constants. In addition to positive ion SIFT-MS with H 3 O + , O 2 + and NO + precursor ions, negative ionization with O •- , O 2 •- , OH - , NO 2 - and NO 3 - extends the range of analysis of aldehydes and carboxylic acids in air without a preparation or separation step. This methodology was illustrated by the simultaneous quantification in single-scan experiments of seven aldehydes and six carboxylic acids released by building materials., (© 2019 John Wiley & Sons, Ltd.)

The oxidative action of a solid and stable potassium sulfatoferrate(VI) material on phenol was studied in aqueous solution under different stoichiometries. The performance towards phenol and the total organic carbon is compared to that of potassium permanganate and calcium hypochlorite. The total mineralization of phenol is not completely achieved by the studied chemical oxidants, and some oxidation products have been identified by gas chromatography-mass spectrometry and gas chromatography-flame ionization detector analysis. A radical reaction pathway, involving the formation of oxidation intermediates or by-products such as benzoquinone, phenoxyphenol and ring opening products, is proposed for the decomposition of phenol by ferrate(VI). Phenoxyphenol is also involved in the oxidation mechanism for permanganate whereas chlorinated phenols are produced by hypochlorite. The role of the chloride anion impurity of the potassium sulfatoferrate(VI) material has been highlighted in this study; no negative impact on the removal of phenol and its mineralization is observed compared to the use of a pure commercial ferrate(VI). The efficiency of sulfatoferrate(VI) for the oxidative removal of phenol from industrial wastewater is also confirmed., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

Various photosensitizers were grafted by conventional peptide coupling methods to functionalized silica with several macroscopic shapes (powders, films) or embedded in highly transparent and microporous silica xerogel monoliths. Owing to the transparency and free-standing shape of the monoliths, the transient species arising from irradiation of the PSs could be analyzed and were not strikingly different from those observed in solutions. The observed reactivity for either liquid-solid (α-terpinene oxygenation vs dehydrogenation) or gas-solid (dimethylsulfide, DMS, solvent-free oxidation) reactions was consistent with the properties of the excited states of the PSs under consideration. Immobilized anthraquinone-derived materials preferentially react in both cases by electron transfer from the substrate to the triplet state of the sensitizer, in spite of an efficient singlet oxygen production. The recently developed 9,14-dicyanobenzo[b]triphenylene-3-carboxylic acid, DBTP-COOH, efficiently reacts via energy transfer to yield singlet oxygen from its triplet state. It was shown to perform better than 9,10-dicyanoanthracene and rose bengal for DMS oxidation and α-terpinene photooxygenation to ascaridole, respectively. Thus, by a proper choice of the organic immobilized photocatalyst, it is possible to develop efficient and reusable materials, activated under visible light, for various applications and to tune the reaction pathway, opening the way to green oxidation processes., (© 2013 The American Society of Photobiology.)