Organic matter(OM) is an important component of sediment. Bioturbation/bioirrigation can remobilize OM and heavy metals that were previously buried in the sediment. The remobilization of buried organic matter, thallium(Tl), cadmium(Cd), copper(Cu) and zinc(Zn) from sediment was studied in a laboratory experiment with three organisms: tubificid,chironomid larvae and loach. Results showed that bioturbation/bioirrigation promoted the release of dissolved organic matter(DOM) and dissolved Tl, Cd, Cu and Zn, but only dissolved Zn concentrations decreased with exposure time in overlying water. The presence of organisms altered the compositions of DOM released from sediment,considerably increasing the percentage of fulvic acid-like materials(FA) and humic acidlike materials(HA). In addition, bioturbation/bioirrigation accelerated the growth and reproduction of bacteria to enhance the proportion of soluble microbial byproduct-like materials(SMP). The DOM was divided into five regions in the three-dimensional excitation emission matrix(3 D-EEM), and each part had different correlation with the dissolved heavy metal concentrations. Dissolved Cu had the best correlation with each of the DOM compositions, indicating that Cu in the sediment was in the organic-bound form.Furthermore, the organism type and heavy metal characteristics both played a role in influencing the remobilization of heavy metal.
Yi HeBin MenXiaofang YangYaxuan LiHui XuDongsheng Wang
Pre-oxidation is widely used to reduce ultrafiltration membrane fouling. However, the variation in the composition of microbial communities and extracellular polymeric substances （EPSs） accompanying pre-oxidation in drinking water treatment has received little attention. In this study, hydrogen peroxide （H2O2） was used in a coagulation- ultrafiltration process with Al2（SO4）3.18H2O. A long-term reactor experiment （60 d） showed that pre-oxidation alleviated membrane fouling, mainly due to its inhibition of microbial growth, as observed by flow cytometry measurements of the membrane tank water. Further analysis of the formed cake layer demonstrated that the corresponding levels of EPS released from the microbes were lower with than without H202 treatment. In comparison to polysaccharides, proteins dominated the EPS. 2D-electrophoresis showed little difference （p 〉 0.05, Student＇s t-test） in the composition of proteins in the cake layer between the treatments with and without H2O2. The molecular weights of proteins ranged from approximately 30-50 kDa and the majority of isoelectric points ranged from 6 to 8. Highthroughput sequencing showed that the predominant bacteria were Proteobacteria, Bacteroidetes, and Verrucomicrobia in both cake layers. However, the relative abundance of Planctomycetes was higher in the cake layer with H2O2 pre-oxidation, which was likely probably due to the strong oxidative resistance of its cell wall. Overall, our findings clarify the fundamental molecular mechanism in H2O2 pre-oxidation for ultrafiltration membrane bio-fouling alleviation in drinking water treatment.
The effect of phosphate on adsorption and oxidation of catechol, 1,2-dihydroxybenzene,in a heterogeneous Fenton system was investigated. In situ attenuated total reflectance infrared spectroscopy（ATR-FTIR） was used to monitor the surface speciation at the nano-Fe_3O_4 catalyst surface. The presence of phosphate decreased the removal rate of catechol and the abatement of dissolved organic compounds, as well as the decomposition of H2O2. This effect of phosphate was mainly due to its strong reaction with surface sites on the iron oxide catalyst. At neutral and acid pH, phosphate could displace the adsorbed catechol from the surface of catalyst and also could compete for surface sites with H2O2. In situ IR spectra indicated the formation of iron phosphate precipitation at the catalyst surface. The iron phosphate surface species may affect the amount of iron atoms taking part in the catalytic decomposition of H2O2 and formation of hydroxyl radicals,and inhibit the catalytic ability of Fe3O4 catalyst. Therefore, phosphate ions worked as stabilizer and inhibitor in a heterogeneous Fenton reaction at the same time, in effect leading to an increase in oxidation efficiency in this study. However, before use of phosphate as pH buffer or H2O2 stabilizer in a heterogeneous Fenton system, the possible inhibitory effect of phosphate on the actual removal of organic pollutants should be fully considered.
Xiaofang YangJie HeZhongxi SunAllan HolmgrenDongsheng Wang
The heterogeneous Fenton reaction can generate highly reactive hydroxyl radicals（·OH）from reactions between recyclable solid catalysts and H2O2 at acidic or even circumneutral pH.Hence,it can effectively oxidize refractory organics in water or soils and has become a promising environmentally friendly treatment technology.Due to the complex reaction system,the mechanism behind heterogeneous Fenton reactions remains unresolved but fascinating,and is crucial for understanding Fenton chemistry and the development and application of efficient heterogeneous Fenton technologies.Iron-based materials usually possess high catalytic activity,low cost,negligible toxicity and easy recovery,and are a superior type of heterogeneous Fenton catalysts.Therefore,this article reviews the fundamental but important interfacial mechanisms of heterogeneous Fenton reactions catalyzed by iron-based materials..OH,hydroperoxyl radicals/superoxide anions（HO2./O2^-.）and high-valent iron are the three main types of reactive oxygen species（ROS）,with different oxidation reactivity and selectivity.Based on the mechanisms of ROS generation,the interfacial mechanisms of heterogeneous Fenton systems can be classified as the homogeneous Fenton mechanism induced by surface-leached iron,the heterogeneous catalysis mechanism,and the heterogeneous reaction-induced homogeneous mechanism.Different heterogeneous Fenton systems catalyzed by characteristic iron-based materials are comprehensively reviewed.Finally,related future research directions are also suggested.
De veloping transition metal oxides/carbon substrate hybrids as highly promising non-precious metal oxygen reduction reaction(ORR) electrocatalysts is crucial to replace the scarce platinum and solve the world-wide energy predicament. In this work, γ-Fe2O3/N-carbon nanotubes(N-CNTs) and α-Fe2O3/N-CNTs nanocatalysts were successfully synthesized by simultaneous formation of crystal configuration of Fe2O3 and the doping of nitrogen on CNTs. α-Fe2O3/N-CNTs catalysts exhibited superior ORR electrocatalytic activity with lower onset and peak potential of-0.21 and-0.27 V, and possessed a more efficient four-electron-dominant ORR process compared with γ-Fe2O3/N-CNTs, N-CNTs and CNTs. The crystal distortions on octahedral α-Fe2O3 held great potential for displacement of either iron or other ions, serving as the active sites and contributing to its better ORR catalytic ability than the vacancies integrated in γ-Fe2O3/N-CNTs. Both the two nanocatalysts possessed superior methanol tolerance and long-term stabili ty of ORR compared with Pt/C, indicating great potential for their practical utilization in fuel cells.
Ferrate（Ⅵ ） salt is an oxidant and coagulant for water and wastewater treatment. It is considered as a possible alternative method in greywater treatment. However, challenges have existed in putting ferrate（Ⅵ ） technology into full-scale practice in water and wastewater treatment due to the instability of ferrate solution and high production cost of solid ferrate products. This study demonstrated a new approach of greywater treatment with on-line batch production of Fe（Ⅵ ） to which Fe（Ⅲ ） salt was oxidized at a weak acidity solution. A series of experiments were conducted to investigate the effect of Fe（Ⅵ ） on light greywater（total organic carbon（TOC） = 19.5 mg/L） and dark greywater（TOC = 55 mg/L）treatment under different conditions with varying p H and Fe（Ⅵ ） doses. In addition, the combination use of Fe（Ⅵ ） and Al（Ⅲ ） salts was proved to be more efficient than using the Fe（Ⅵ ） salts alone at greywater recycling. The optimum dosage of Fe（Ⅵ ）/Al（Ⅲ ） salts was 25/25 mg/L for light greywater, 90/60 mg/L for dark greywater, respectively. The TOC values of both light greywater and dark greywater were reduced to less than 3 mg/L with the dosages.The cost for treating greywater was 0.06–0.2 $/ton at ferrate（Ⅵ ） dosage of 25–90 mg/L and0.008–0.024 $/ton at AlCl3 dosage of 25–60 mg/L. The full operating cost needs further assessment before the Fe（Ⅵ ）/Al（Ⅲ ） technology could be implemented in greywater treatment.
