Photochemical degradation of environmentally persistent perfluorooctanoic acid (PFOA) in the presence of Fe(Ⅲ)

Environmentally persistent and bioaccumulative perfluorooctanic acid （PFOA） was difficult to be decomposed under the irradiation of 254 nm UV light. However, in the presence of 80μmol/L Fe（Ⅲ）, 80% of PFOA with initial concentration of 48μmol/L （20 mg/L） was effectively degraded and 47.8% of fluorine atoms in PFOA molecule were transformed into inorganic fluoride ion after 4 h reaction. Shorter chain perfluorocarboxylic acids bearing C3-C7 and fluoride ion were detected and identified by LC/MS and IC as the degradation products in the aqueous solution. It was proposed that complexes of PFOA with Fe（Ⅲ） initiated degradation of PFOA irradiated with 254 nm UV light.

Photochemical Degradation of Triadimefon in Seawater

The photochemical degradation of triadimefon in seawater was investigated under different reaction conditions in this study. The results showed that triadimefon could be effectively degraded by the irradiation of a high-pressure mercury lamp and the photodegradation rates were influenced by aquatic media, heavy metal ions and photosensitizers. The photochemical degradation of triadimefon followed the first-order reaction kinetic behavior, with the rate constants ranging from 0.0027 to 0.0128 min-1 under the studied conditions. The photolysis of triadimefon was slower in natural seawater than in distilled water or synthetic seawater. All the heavy metal ions studied in this paper had inhibition effects on the photolysis of triadimefon. Acetone, as a common photosensitizer, could accelerate the photolysis of triadimefon. Three photoproducts were identified by GC-MS analysis. Our study confirmed that photochemical degradation is an effective pathway to remove triadimefon in seawater.

Photochemical Degradation Study of Polyurethanes as Relic Protection Materials by FTIR-ATR

Polyurethanes are one kind of relic protection materials commonly used. During artificial photo-ageing, three polyurethanes, HDI-based polyurethane, MDI-based polyurethane and TDI-based polyurethane, have been considered to undergo UV radiation. Photochemical degradation of the polyurethanes has been monitored by means of Fourier transform infrared spectroscopy with attenuated total reflection accessory （FTIR-ATR）. It was proved that the mechanism of the photochemical degradation of polyurethanes might be the scissions of carbamate （urethane） groups and the re-reactions of radical groups formed in the scission reactions. From the experiment results HDI-based polyurethane, an aliphatic diisocyanate, could be considered to be more suitably used as relic protection materials among these three polyurethanes for its ageing products with less color.

Effects of acid mine drainage on photochemical and biological degradation of dissolved organic matter in karst river water

Dissolved organic matter(DOM)can be removed or transformed by photochemical and biological processes,producing the negative effect of transforming organic carbon into inorganic carbon,which plays a vital role in the karst carbon cycle.However,acid mine drainage(AMD)will affect this process,so the degradation of DOM in karst river water(KRW)needs to be studied in this context.In this study,to reveal the evolution processes of DOM under photochemical and biological conditions in AMD-impacted KRW,AMD and KRW were mixed in different ratios under conditions of visible light irradiation(VL),biodegradation(BD),ultraviolet irradiation(UV)and ultraviolet irradiation+biodegradation(UV+BD).The average DOC concentrations in samples after mixing AMD and KRW in different proportions decreased significantly(by 23%)in UV+BD,which was 1.2–1.4 times higher than under the other conditions and would lead to a significant release of inorganic carbon.Further analysis of the fluorescence parameters via parallel factor analysis(PARAFAC)revealed that the DOM fluorescence components in AMD comprised mainly protein-like substances derived from autochthonous components,while the DOM fluorescence components in KRW were mainly humic-like substances with both autochthonous and allochthonous sources.Therefore,AMD could promote both the photochemical and biological degradation of DOM in karst receiving streams,resulting in the conversion of DOC to inorganic carbon.The results showed that the synergistic effects of UV+BD and AMD accelerated the degradation of DOM and the release of inorganic carbon in KRW,thus affecting the stability of the karst carbon cycle.

Prediction of the Photofading of Selected Derivatives of 5-(4-X-Phenylazo)-3-Cyano-1-(H or Ethyl)-6-Hydroxy-4-Methyl-2-Pyridone: Theoretical Studies, Comparison of AM1 and PM3 Methods

We analysed the photooxidation reaction in the electro-(1O2) and nucleophilic (O2•−) reaction of 2-pyridone azo derivatives. First, we calculated the energy (enthalpies) of tautomers formation, which is a measure of durability and the probability of their formation. We performed the light fastness calculations of the monoazopyridone dyes. Using the semi-empirical methods of quantum chemistry AM1 and PM3, the reactivity indicators of superdelocalisability (SrE(N)) and the electron density distribution in ground state on the highest occupied HOMO orbital and the lowest unoccupied excited state LUMO in 2-pyridone phenylazo derivatives were calculated. Superdelocalisability coefficients enable the stability to oxidising agents of various chemical molecules depending on the tautomeric forms in which they may occur. The results of the electron density calculations at the HOMO and LUMO boundary orbitals allow to determine the tendency to electrophilic attack with singlet oxygen 1O2 or nucleophilic attack of the superoxide anion O2•−on a specific atom in the molecule. The structure of the dyes was optimised with MM+, MD and AM1 or PM3 until a constant energy value was achieved with a convergence criterion of 0.01 kcal/mol.

UV-Catalytic Treatment of Municipal Solid-Waste Landfill Leachate with Hydrogen Peroxide and Ozone Oxidation

The performance of UV/H_2O_2, UV/O_3, and UV/H_2O_2/O_3 oxidationsystems for the treatment of municipal solid-waste landfill leachatewas investigated. Main objective of the experiment was to removetotal organic carbon (TOC), non-biodegradable organic compounds(NBDOC) and color. In UV/H_2O_2 oxidation experiment, with theincrease of H_2O_2 dosage, removal efficiencies of TOC and coloralong with the ratio of biochemical oxygen demand (BOD) to chemicaloxygen demand (COD) of the effluent were increased and a betterperformance was obtained than the system H_2O_2 alone.

A New Method for the Synthesis of C/D Ring Synthon of Vitamin D

A C/D ring synthon of vitamin D is readily obtained from cholesteryl acetate via oxidation, elimination of acetoxy group and Norrish type II photochemical reaction.

Experimental and model comparisons of H_2O_2 assisted UV photodegradation of Microcystin-LR in simulated drinking water

The degradation of Microcystin-LR (MC-LR) in water by hydrogen peroxide assisted ultraviolet (UV/H2O2) process was investigated in this paper. The UV/H2O2 process appeared to be effective in removal of the MC-LR. MC-LR decomposition was primarily ascribed to production of strong and nonselective oxidant-hydroxyl radicals within the system. The intensity of UV radiation, initial concentration of MC-LR, MC-LR purity, dosages of H2O2, the initial solution pH, and anions present in water, to some extent, influenced the degradation rate of MC-LR. A modified pseudo-first-order kinetic model was developed to predict the removal efficiency under different experimental conditions.

Characteristics of ozone and ozone precursors(VOCs and NOx) around a petroleum refinery in Beijing, China

A field measurement campaign for ozone and ozone precursors （VOCs and NOx） was conducted in summer 2011 around a petroleum refinery in the Beijing rural region. Three observation sites were arranged, one at southwest of the refinery as the background, and two at northeast of the refinery as the downwind receptors. Monitoring data revealed the presence of serious surface 03 pollution with the characteristics of high average daily mean and maximum concentrations （64.0 and 145.4 ppbV in no-rain days, respectively） and multi-peak diurnal variation. For NOx, the average hourly concentrations of NO2 and NO were in the range of 20.546.1 and 1.8-6.4 ppbV, respectively. For VOC measurement, a total of 51 compounds were detected. Normally, TVOCs at the background site was only dozens of ppbC, while TVOCs at the downwind sites reached several hundreds of ppbC. By subtracting the VOC concentrations at background, chemical profiles of VOC emission from the refinery were obtained, mainly including alkanes （60.0% ± 4.3%）, alkenes （21.1% ± 5.5%） and aromatics （18.9% ±3.9%）. Moreover, some differences in chemical profiles for the same measurement hours were observed between the downwind sites; the volume ratios of alkanes with low reactivity and those of alkenes with high reactivity respectively showed an increasing trend and a decreasing trend. Finally, based on temporal and spatial variations of VOC mixing ratios, their photochemical degradations and dispersion degradations were estimated to be 0.15-0.27 and 0.42-0.62, respectively, by the photochemical age calculation method, indicating stronger photochemical reactions around the refinery.