Effects of typical algae species (Aphanizomenon flosaquae and Microcystis aeruginosa) on photoreduction of Hg2+ in water body

Photoreduction characteristics of divalent inorganic mercury(Hg~(2+)) in the presence of specific algae species are still not well known. Laboratory experiments were conducted in the present study to identify the effects of different concentrations of living/dead algae species, including Aphanizomenon flosaquae(AF) and Microcystis aeruginosa(MA), on the photoreduction rate of Hg~(2+)under various light conditions. The experimental results showed that percentage reduction of Hg~(2+)was significantly influenced by radiation wavelengths, and dramatically decreased with the presence of algae. The highest percentage reduction of Hg~(2+)was induced by UV-A, followed by UV-B, visible light and dark for both living and dead AF, and the order was dark UV-A UV-B visible light for both living and dead MA. There were two aspects, i.e., energy and attenuation rate of light radiation and excrementitious generated from algae metabolisms, were involved in the processes of Hg~(2+)photoreduction with the presence of algae under different light conditions. The percentage reduction of Hg~(2+)decreased from 15% to 11% when living and dead AF concentrations increased by 10 times(from 106 to 105 cells/mL), and decreased from 11% to ～ 9% in the case of living and dead MA increased. Algae can adsorb Hg~(2+)and decrease the concentration of free Hg~(2+), thus inhibiting Hg~(2+)photoreduction, especially under the conditions with high concentrations of algae. No significant differences were found in percentage reduction of Hg~(2+)between living and dead treatments of algae species.The results are of great importance for understanding the role of algae in Hg~(2+)photoreduction.     

Increasing chloride concentration causes retention of mercury in melted Arctic snow due to changes in photoreduction kinetics

Mercury(Hg) in the Arctic is a significant concern due to its bioaccumulative and neurotoxic properties, and the sensitivity of Arctic environments. Previous research has found high levels of Hg in snowpacks with high chloride(Cl~-) concentrations. We hypothesised that Cl~- would increase Hg retention by decreasing Hg photoreduction to Hg(0) in melted Arctic snow. To test this, changes in Hg photoreduction kinetics in melted Alert, NU snow were quantified with changing Cl~- concentration and UV intensity. Snow was collected and melted in Teflon bottles in May 2014, spiked with 0–10 μg/g Cl~-, and irradiated with 3.52–5.78 W·m~(-2) UV(280–400 nm)radiation in a Luz Chem photoreactor. Photoreduction rate constants(k)(0.14–0.59 hr~(-1)) had positive linear relationships with [Cl~-], while photoreduced Hg amounts(Hg(Ⅱ)_(red)) had negative linear relationships with [Cl~-](1287–64 pg in 200 g melted snow). Varying UV and[Cl~-] both altered Hg(Ⅱ)_(red) amounts, with more efficient Hg stabilisation by Cl~- at higher UV intensity, while k can be predicted by Cl- concentration and/or UV intensity, depending on experimental parameters. Overall, with future projections for greater snowpack Cl~- loading,our experimental results suggest that more Hg could be delivered to Arctic aquatic ecosystems by melted snow(smaller Hg(Ⅱ)_(red) expected), but the Hg in the melted snow that is photoreduced may do so more quickly(larger k expected).     

Detoxification of hexavalent chromium in wastewater containing organic substances using simonkolleite-TiO2 photocatalyst

Innovative simple method for the preparation of simonkolleite-TiO₂ photocatalyst with different Zn contents was achieved. The prepared photocatalysts were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), FT-IR, Raman and diffuse reflectance spectroscopy techniques. The photocatalytic activities of the materials were evaluated for the simultaneous detoxification of hexavalent chromium (Cr(VI)) and oxidation of organic compounds commonly present in wastewater under simulated solar light. The best photoreduction efficiency of Cr(VI) has been achieved at 1000 ppm simonkolleite-TiO₂ photocatalyst of 5% Zn/TiO₂ weight ratio, and pH value of 2.5 to enhance the adsorption onto catalyst surface. Photoreduction was significantly improved by using formic acid as holes scavenger owing to its chemical adsorption on the catalyst surface. Finally, 100% photoreduction of Cr(VI) could be achieved using formic/simonkolleite-TiO₂ systems under sunlight.     

Triethylamine induced photolysis of endosulphan

Photolysis of pure isomers of endosulphan in the presence of triethylamine gives products arising by the loss of a chlorine atom from the geminal bridge. The structures of these products have been established. The α‐isomer of endosulphan isomerised to ß‐isomer on a leaf surface.     

Novel functional fiber loaded with carbon dots for the deep removal of Cr(VI) by adsorption and photocatalytic reduction

A novel functional fiber (PAN-CDs) loaded with carbon dots (CDs) with excellent photoreduction and adsorption properties for Cr(VI) was prepared via an amidization reaction between the CDs' carboxyl groups and amine groups on polyacrylonitrile (PAN)-based ion exchange fibers, which could completely preserve the fluorescence properties of the CDs. The photoluminescence (PL), photocatalysis and adsorption properties of PAN-CDs were characterized and analyzed. The PAN-CDs possess high adsorption capacity (297.6?mg/g) and excellent kinetic behavior (attaining adsorption equilibrium in 30?min) for Cr(VI) adsorption. Furthermore, the residual Cr(VI) (approximately 3?mg/L) after adsorption could be removed completely by subsequent photoreduction by the PAN-CDs. The Cr-saturated PAN-CDs could be easily separated by filtering and regenerated, with no observable decay of removal efficiency after five regeneration cycles. In addition, due to the PL quenching action of Cr(VI), the PAN-CDs can also be used as sensor for quantitative detection of trace Cr(VI) in aqueous solution.     

Aqueous photoreduction of oxidized mercury species in presence of selected alkanethiols

Mercury is a global environmental contaminant with severe toxicity impact. The chemical processes resulting in the transformation of oxidized mercury species (Hg²⁺) to elemental mercury (Hg⁰), greatly affects the fate and transport of mercury in the natural environment. We hereby provide the first study on the photochemistry of Hg²⁺ with selected alkanethiols (R-SH) as model compounds to represent thiols and thiol-type binding sites on humic substances in natural waters because of the common sulfhydryl functional group (-SH). Kinetic studies were performed using cold vapor atomic fluorescence spectroscopy (CVAFS), the formation of Hg²⁺-thiol complexes (Hg(SR)₂) were confirmed by UV-visible spectrometry and Atmospheric Pressure Chemical Ionization-Mass Spectrometry (APCI-MS), and the reaction products were analyzed using Electron Impact-Mass Spectrometry (EI-MS) and Solid Phase Microextraction coupled with Gas Chromatography-Mass Spectrometry (SPME/GC-MS). Our results indicated that the photoreduction of Hg²⁺ by selected alkanethiols may be mediated by Hg²⁺-thiol complexes to produce Hg⁰. Under our experimental conditions, the apparent first order rate constants obtained for 1-propanethiol, 1-butanethiol, and 1-pentanethiol were (2.0 ± 0.2) × 10⁻⁷ s⁻¹, (1.4 ± 0.1) × 10⁻⁷ s⁻¹, (8.3 ± 0.5) × 10⁻⁸ s⁻¹, respectively. The effects of ionic strength, dissolved oxygen or chloride ion on reaction rates were found to be minimal under our experimental conditions. The identified products of the reaction between oxidized mercury species with selected alkanethiols (C₃-C₅) were Hg⁰ and disulfides (RS-SR). The potential environmental implications are herein discussed.     

Mercury photoreduction and photooxidation in lakes: Effects of filtration and dissolved organic carbon concentration

Mercury is a globally distributed, environmental contaminant. Quantifying the retention and loss of mercury is integral for predicting mercury-sensitive ecosystems. There is little information on how dissolved organic carbon(DOC) concentrations and particulates affect mercury photoreaction kinetics in freshwater lakes. To address this knowledge gap,samples were collected from ten lakes in Kejimkujik National Park, Nova Scotia(DOC: 2.6–15.4 mg/L). Filtered(0.2 μm) and unfiltered samples were analysed for gross photoreduction, gross photooxidation, and net reduction rates of mercury using pseudo first-order curves. Unfiltered samples had higher concentrations(p = 0.04) of photoreducible divalent mercury(Hg(II)RED)(mean of 754 ± 253 pg/L) than filtered samples(mean of 482 ± 206 pg/L);however, gross photoreduction and photooxidation rate constants were not significantly different in filtered or unfiltered samples in early summer. DOC was not significantly related to gross photoreduction rate constants in filtered(R~2= 0.43; p = 0.08) and unfiltered(R~2= 0.02; p = 0.71) samples; DOC was also not significantly related to gross photooxidation rate constants in filtered or unfiltered samples. However, DOC was significantly negatively related with Hg(Ⅱ)_(RED) in unfiltered(R2= 0.53; p = 0.04), but not in filtered samples(R~2= 0.04;p = 0.60). These trends indicate that DOC is a factor in determining dissolved mercury photoreduction rates and particles partially control available Hg(Ⅱ)_(RED) in lake water. This research also demonstrates that within these lakes gross photoreduction and photooxidation processes are close to being in balance. Changes to catchment inputs of particulate matter and DOC may alter mercury retention in these lakes and could partially explain observed increases of mercury accumulation in biota.