After particulate matter (PM) collection in Cotonou (Benin), a complete physicochemical characterization of PM2.5 and PM>2.5 was led. Then, their adverse health effects were evaluated by using in vitro culture of human lung cells. BEAS-2B (bronchial epithelial cells) were intoxicated during short-term exposure at increasing PM concentrations (1.5–96 μg/cm2) to determine global cytotoxicity. Hence, cells were exposed to 3 and 12 μg/cm2 to investigate the potential biological imbalance generated by PM toxicity. Our findings showed the ability of both PM to induce oxidative stress and to cause inflammatory cytokines/chemokines gene expression and secretion. Furthermore, PM were able to induce gene expression of enzymes involved in the xenobiotic metabolism pathway. Strong correlations between gene expression of metabolizing enzymes, proinflammatory responses and cell cycle alteration were found, as well as between proinflammatory responses and cell viability. Stress oxidant parameters were highly correlated with expression and protein secretion of inflammatory mediators.

The chemical composition of Beijing aerosol was measured during summer and winter. Two distinct episodes were identified. Water-soluble potassium (K+) increased significantly during the firework episode in winter with an episode to non-episode ratio of 4.97, whereas the biomass burning (BB) episode in summer was characterized by high episode to non-episode ratios of levoglucosan (6.38) and K+ (6.90). The BB and firework episodes had only a minor influence on the water-soluble OC (organic carbon) to OC ratio. Based on separate investigations of episode and non-episode periods, it was found that: (i) sulfate correlated strongly with both relative humidity and nitrate during the typical winter period presumably indicating the importance of the aqueous-phase oxidation of sulfur dioxide by nitrogen dioxide, (ii) oxalate and WSOC during both winter and summer in Beijing were mainly due to secondary formation, and (iii) high humidity can significantly enhance the formation potential of WSOC in winter.

So far only a few publications have explored the development of extraction methods of cyanotoxin extracted from complex matrices. With regard to cyanobacterial microcystins (MCs), the data on the contamination of the flesh of aquatic organisms is hard to compare and very limited due to the lack of validated methods. In recent years, evidence that both free and bound fractions of toxin are found in these tissues has highlighted the need to develop effective methods of quantification. Several techniques do exist, but only the Lemieux oxidation has so far been used to investigate complex tissue matrices. In this study, protocols based on the Lemieux approach were adapted for the quantitative chemical analysis of free MC-LR and MMPB derived from bound toxin in the tissues of juvenile trout gavaged with MC-LR. Afterwards, the NF V03 110 guideline was used to characterize the protocols elaborated and evaluate their effectiveness.

Even though antimony (Sb) and arsenic (As) are chemical analogs, differences exist on how they are taken up and translocated in plants. We investigated 1) Sb uptake, efflux and speciation in arsenic hyperaccumulator Pteris vittata after 1 d exposure to 1.6 or 8 mg/L antimonite (SbIII) or antimonate (SbV), 2) Sb uptake by PV accessions from Florida, China, and Brazil after 7 d exposure to 8 mg/L SbIII, and 3) Sb uptake and oxidation by excised PV fronds after 1 d exposure to 8 mg/L SbIII or SbV. After 1 d exposure, P. vittata took 23–32 times more SbIII than SbV, with all Sb being accumulated in the roots with the highest at 4,192 mg/kg. When exposed to 8 mg/L SbV, 98% of Sb existed as SbV in the roots. In comparison, when exposed to 8 mg/L SbIII, 81% of the total Sb remained as SbIII and 26% of the total Sb was effluxed out into the media. The three PV accessions had a similar ability to accumulate Sb at 12,000 mg/kg in the roots, with >99% of total Sb in the roots. Excised PV fronds translocated SbV more efficiently from the petioles to pinnae than SbIII and were unable to oxidize SbIII. Overall, P. vittata displayed efficient root uptake and efflux of SbIII with limited ability to translocate and transform in the roots.

A laboratory study was performed to investigate the composition of products formed from OH–initiated oxidation of aromatic hydrocarbon 1,3,5–trimethylbenzene. The experiments were conducted by irradiating 1,3,5–trimethylbenzene/CH3ONO/NO/air mixtures in smog chamber. The chemical composition of gas and particle–phase products have been investigated with gas chromatography/mass spectrometry (GC/MS) and the aerosol laser time–of–flight mass spectrometer (ALTOFMS), respectively. Experimental results showed that 3,5–dimethyl benzaldehyde, 2,4,6–trimethylphenol, 2–methyl–4–oxo–2–pentenal and 3,5–dimethyl–2–furanone were the predominant products in both the gas and particle–phases. However, there were some differences between detected gas–phase products and those of particle–phase, for example, oxalic acid, 2–methyl–2–hydroxy–3,4–dioxo–pentanal, and 2,3,5–trimethyl–3–nitro–phenol were only existing in the particle–phase. The possible reaction mechanisms leading to these products are also proposed. Compared to offline methods such as GC–MS measurement, the ALTOFMS detection can analyze real–time the secondary organic aerosol (SOA) successfully and provide more information on the products. Thus, ALTOFMS is a useful tool to reveal the formation and transformation processes of SOA particles in smog chambers.

The degree of iron pyritization (DOP) and degree of trace metal pyritization (DTMP) were evaluated in mangrove soil profiles from an estuarine area located in Rio de Janeiro (SE Brazil). The soil pH was negatively correlated with redox potential (Eh) and positively correlated with DOP and DTMP of some elements (Mn, Cu and Pb), suggesting that pyrite oxidation generated acidity and can affect the importance of pyrite as a trace metal-binding phase, mainly in response to spatial variability in tidal flooding. Besides these aerobic oxidation effects, results from a sequential extraction analyses of reactive phases evidenced that Mn oxidized phase consumption in reaction with pyrite can be also important to determine the pyritization of trace elements. Cumulative effects of these aerobic and anaerobic oxidation processes were evidenced as factors affecting the capacity of mangrove soils to act as a sink for trace metals through pyritization processes.

Activated natural siderite (ANS) was used to investigate its characteristics and mechanisms of As(V) adsorption from aqueous solution. Batch tests were carried out to determine effects of contact time, initial As(V) concentration, temperature, pH, background electrolyte, and coexisting anions on As(V) adsorption. Arsenic(V) adsorption on ANS well-fitted pseudo-second-order kinetics. ANS showed a high-adsorption capacity of 2.19 mg/g estimated from Langmuir isotherm at 25 °C. Thermodynamic studies indicated that As(V) adsorption on ANS was spontaneous, favorable, and endothermic. ANS adsorbed As(V) efficiently in a relatively wide pH range between 2.0 and 10.0, although the removal efficiency was slightly higher in acidic conditions than that in basic conditions. Effects of background electrolyte and coexisting anions were not significant within the concentration ranges observed in high As groundwater. Results of XRD and Fe K-edge XANES analysis suggested ANS acted as an Fe(II)/(III) hybrid system, which was quite effective in adsorbing As from aqueous solution. There was no As redox transformation during adsorption, although Fe(II) oxidation occurred in the system. Two infrared bands at 787 and 872 cm⁻¹after As(V) adsorption suggested that As(V) should be predominantly adsorbed on ANS via inner-sphere bidendate binuclear surface complexes.

The coffee agro-industry generates a large volume of wastewater that is notable for its high organic strength as well as its color content. Due to the seasonal nature of the harvest (3–4 months per year), this particular industrial waste needs a treatment method that is both reliable and fast (in terms of start-up time). As part of investigating a system capable of treating a coffee wastewater, this research evaluated four electrochemical advanced oxidation processes (EAOPs) using boron-doped diamond (BDD) electrodes. The processes were anodic oxidation (AO), anodic oxidation with electrogenerated H₂O₂(AO-H₂O₂), electro-Fenton (EF), and photoelectro-Fenton (PEF). Experimental conditions were as follows: 40 mA cm⁻²current density (all EAOPs), 0.3 mmol Fe²⁺L⁻¹(Fenton systems), 300 mL air min⁻¹(AO-H₂O₂, EF, PEF), and 500 μW cm⁻²UV irradiation (photo-Fenton systems). The performance of the four EAOP treatment methods (in terms of color and organic carbon removal) was compared against two conventional chemical oxidation methods, namely, Fenton and photo-Fenton. The research indicated that the four EAOPs were better at removing color (89–93 %) and total organic carbon (TOC) (73–84 %) than the respective chemical Fenton (58 and 4.8 %) and photo-Fenton (61 and 7 %) methods. The trend in performance was as follows: AO-H₂O₂ > AO > PEF ≈ EF. It appeared that the ferrous iron reagent formed a dark-colored complex with some coffee components, diminishing the effect of Fenton reactions. In addition, the dark color of the wastewater limited the effect of light in the UV-Fenton processes. Analysis showed that acceptable levels of Fe²⁺(0.3 mmol L⁻¹) and energy (0.082–0.098 kWh g⁻¹TOC) were required by the EAOPs after 4-h treatment time. In conclusion, the use of electrochemical methods (equipped with BDD electrodes) seems a promising method for the effective treatment of coffee wastewaters.

This contribution is concerned with the comparison of the efficiency of the removal of four pure neonicotinoid active ingredients (AIs) and their commercial formulations (CFs) from aqueous solutions by using different advanced oxidation processes at the pH 2.8. The AIs of thiamethoxam and imidacloprid, and their CFs (Actara and Confidor), having a nitroguanidine functional group, exhibited low persistence to photolysis. In contrast to them, thiacloprid and acetamiprid and their CFs (Calypso and Mospilan), containing a cyanoimine functional group, were stable during the UV irradiation period. As expected, the degradation rate of the studied neonicotinoids increased significantly in the combined action of UV radiation and H₂O₂. In the case of thiacloprid and acetamiprid and their CFs, the reaction of the OH radicals formed and molecules of these insecticides was the major destruction pathway. The increased photodegradation efficiency of the UV/7.2Fe/TiO₂/H₂O₂ and vis/7.2Fe/TiO₂/H₂O₂ processes was attributed to the surface photoreduction of Fe³⁺ to Fe²⁺, which produces new OH radicals in the reaction with H₂O₂. In the presence of visible light, the efficiency may be partly due to the formation of the H₂O₂–TiO₂ complexes. For the 7.2Fe/TiO₂/H₂O₂ process in the presence of UV or visible radiation, no significant influence on the efficiency of photodegradation was observed in dependence of the structural differences of selected neonicotinoids. These results strongly suggest that highly reactive hydroxyl radicals, generated on the catalyst’s surface in the reaction involving H₂O₂, are responsible for this oxidation. In order to investigate degree of mineralization for all insecticides, TOC measurements were also conducted. Also, it was observed that the removal of pure AIs and their CFs by dark adsorption was almost negligible.

The transformation of less toxic Cr(III) species to harmful Cr(VI) is worth concerning. Compared with free Cr(III), however, the photo-oxidation of Cr(III)–organic acid complexes is seldom reported. In this study, Cr(III)–malate complex was synthesized and purified, and its photo-oxidation was investigated to reveal the potential conversion pathway of Cr(III) to Cr(VI). The results indicated that Cr(III)–malate complex could be gradually photo-oxidized to Cr(VI) through a ligand–metal charge transfer path. Higher pH and stronger light intensity promoted the conversion process. A 50-μM Cr(III)–malate complex was almost completely oxidized to Cr(VI) within 420-min irradiation of 500 W medium-pressure mercury lamp at pH 12. The introduction of H₂O₂, considered as a direct source of hydroxyl radicals (·OH) in the presence of Cr(II), markedly enhanced the yield of Cr(VI), and a complete oxidation of Cr(III)–malate complex (50 μM ) was realized within 20 min. Under a weak acidic condition, the production of Cr(VI) was coupled with the reduction of Cr(VI) by malic acid and its free radical generated from Cr(III)–malate complex, leading a gradual decrease in Cr(VI) concentration with the reaction.