Hydrogen peroxide (H2O2) requirement for the oxidation of crude oil in contaminated soils by a modified Fenton's reagent

The oxidation of soil organic matter (SOM) and total petroleum hydrocarbon were investigated in two soils at eight different hydrogen peroxide (H₂O₂) concentrations to determine the optimal H₂O₂ dosage for the efficient remediation of soils contaminated by crude oil with minimal SOM removal. In our study, H₂O₂ concentrations up to 1100 mM increased the SOM destruction up to 10%–15% in the two soils while no improvement of the crude oil removal efficiencies was observed. The results indicate that the destruction of SOM significantly limits the oxidation of crude oil because SOM might consume H₂O₂ more effectively than crude oil at H₂O₂ concentrations above 1100 mM. In addition, H₂O₂ concentrations higher than 1100 mM were not expected for both soils because of the extremely rapid H₂O₂ decomposition, and low H₂O₂ utilization, of both soils.     

Sonocatalytic degradation of tetracycline antibiotic in aqueous solution by sonocatalysis

Tetracycline (TC), one of the most common antibiotics, is often poorly bio-degraded in conventional wastewater treatment plants. In this study, the sonocatalytic degradation of TC was investigated using TiO₂ nano-particles as catalyst. The effect of pH, initial TC concentrations, reaction times, and H₂O₂ concentrations were evaluated. The efficacy of ultrasonic irradiation alone in the removal of this pollutant was negligible but removal efficiency increased upon addition of TiO₂ up to 250 mg L^?1; increase of pH and initial TC concentration attenuated TC degradation. Addition of H₂O₂ raised the removal efficiency so that complete removal of TC was achieved within 75 min.     

Removal of chromium(VI) by ZnCl2 activated coir pith carbon

The adsorption of chromium(VI) onto ZnCl₂ activated carbon developed from coir pith was investigated to assess the possible use of this adsorbent. The influence of contact time, adsorbent dose, Cr(VI) concentration, pH and temperature were investigated. The two theoretical adsorption isotherms, namely, Langmuir and Freundlich were used to describe the experimental results. The Langmuir adsorption capacity (Q ₀) was found to be 120.5?mg Cr(VI) per g of the adsorbent. The adsorption followed the second-order kinetics and was found to be maximum at pH 2.0. The pH effect and the desorption studies showed that ion exchange mechanism might be involved in the adsorption process. The effects of foreign ions such as chloride, sulphate, phosphate, selenite, molybdate, nitrate and perchlorate on the removal of Cr(VI) have been investigated. The removal of Cr(VI) from synthetic ground water was also tested. The results show that ZnCl₂ activated coir pith carbon is effective for the removal of Cr(VI) from water.     

五氧化二钒类Fenton降解邻苯二甲酸二乙酯的机制研究

发展了基于五氧化二钒(V_2O_5)和过氧化氢(H_2O_2)的新型类Fenton体系,探索了此体系产生羟基(·OH)的机制及降解邻苯二甲酸二乙酯(DEP)的效率;并考察了V_2O_5投加量、H_2O_2浓度,以及草酸对DEP降解的影响。结果表明,当V_2O_5投加量为0.1 g·L-1,H_2O_2浓度为2.0 mmol·L-1,反应24 h后,对DEP(25 mg·L-1)的降解率可达61.1%,增加或降低V_2O_5投加量和H_2O_2浓度均不利于DEP的降解。利用电子顺磁共振技术(Electron Paramagnetic Resonance,EPR)耦合5,5-二甲基-1-吡咯啉氮氧化物(DMPO)为捕获剂对反应体系中的主导自由基进行鉴定,发现·OH是体系降解DEP的主要活性物种,利用苯甲酸作为探针分子实现了·OH的间接定量,并初步推测了V_2O_5活化H_2O_2的过程。     

HO ‐ initiated oxidation of acridine and aminacrine in aqueous media: Kinetic model

The photodecomposition of diluted aqueous solutions of acridine and aminacrine in the presence of hydrogen peroxide was studied. Irradiation was carried out with a low pressure mercury vapour lamp. The kinetic model describes the photodegradation rate of the organic compound with respect to the technological parameters of the reactor and provides the reaction rate constants of hydroxyl radicals towards these two molecules. This model was extented to high hydrogen peroxide concentrations ([H₂O₂] > 200 μmol/l) by considering the reactivity of hydroxyl radicals towards hydrogen peroxide. This assumption allows us to define an optimal hydrogen peroxide concentration.     

Removal of methylene blue by coupling black carbon adsorption with TiO2 photodegradation

In this study, the removal of methylene blue (MB) by the coupling of black carbon (BC) and TiO₂ was investigated. The effects of different parameters such as catalyst dose, sorbent, initial concentrations of dye, pH of the solutions, recycles on discoloration, and chemical oxidation demand (COD) reduction of MB were monitored to optimize the reaction conditions. The discoloration and COD conversation rate of MB obtained by the coupling process were 100% after 90?min irradiation. The synergistic effect of MB-adsorption on BC followed by degradation through TiO₂ photocatalysis was proved by FT–IR spectrophotometer. The BC as by-product of natural materials is a promising adsorbent for waste water treatment.     

Detoxification of 4-chlorophenol in TiO2 sunlight system: effect of raw and treated solution on seed germination and plants growth of various sensitive vegetables

The mineralization and detoxification of 4-chlorophenol (4-CP) were studied using a TiO₂-paper/sunlight system. The possibility of reusing the photocatalyst was examined to determine the cost effectiveness of the method. Experiments were performed to establish optimum conditions for 4-CP removal. Phytotoxicity of photo-treated and raw 4-CP (100 mg L^?1) solutions on seed germination and plant growth were carried out with the aim of water reuse and environment protection. The seeds irrigated with raw 4-CP solution showed lower sprout length while increase in sprout length was observed with the photo-treated solution for tomato (Lycopersicon esculentum), lettuce (Lactuca sativa), onion (Allium cepa), and turnip (Brassica rapa). Plant growth tests with the photo-treated 4-CP solution did not affect the leaf numbers compared to those irrigated with tap water. Photo-treated 4-CP solution can be used for irrigation in agriculture.     

Ag–TiO2 doped photo catalytic degradation of Procion blue H-B dye in textile washwater

The photocatalytic degradation of Procion blue H-B dye in biodegraded textile washwater has been investigated for the complete removal of color and maximum reduction of chemical oxygen demand (COD). Pseudomonas putida was utilized for obtaining biodegraded textile washwater. In this process, silver-doped TiO₂ photocatalyst was prepared and experiments were carried out to study the effects of UV and mercury lamp irradiations on COD reduction and removal of color. The thus prepared silver-doped TiO₂ catalyst was characterized by thermogravimetric and differential thermal analysis, UV-visible spectrometer, X-ray diffraction, scanning electron microscope, energy dispersive X-ray microanalysis, and BET surface area techniques. Adsorption studies were also carried out to evaluate the fitness of isotherm models. The results show that the silver-doped TiO₂ has enhanced the photodegradation of Procion blue H-B dye under UV and mercury lamp irradiations. The enhanced activity of silver-doped TiO₂ is due to the enrichment of electron–hole separation by electron trapping of silver particles.     

Photocatalytic formation of hydrogen peroxide over highly porous illuminated ZnO and TiO2thin film

The photocatalytic formation of hydrogen peroxide over ZnO and TiO₂thin films has been investigated in aqueous phase in the presence of molecular oxygen as an electron acceptor. These films are highly porous and showed enhanced catalytic activity in the photochemical formation of hydrogen peroxide. The amount of H₂O₂formed during 2 hour light illumination is 4–6 μM and the rates of formation of hydrogen peroxide of both the films are almost comparable. The yield of hydrogen peroxide increases with the increase in irradiation time and a trend of steady state concentration of H₂O₂is observed in the case of TiO₂thin film. Photodissolution of ZnO particles is observed in some extent during the process of prolonged UV light illumination.     

Inactivation of bacteria by sun light in a solar reactor with Immobilised TiO2

The photocatalytical inactivation of bacteria (Escherichia coli, Staphylococcus epidermidis,...) in the flow‐through plate solar reactor by sunlight was investigated. The low stability of bacteria in the reactor was attributed to bacteria sensitivity to mixing and/or gas bubbling. Sunlight inactivation proceeds with sufficient rate even under cloudy conditions.     

Effect of silica additive on the thermal stability of catalysts for NOx abatement

The aim of the plesent investigation was to study the effect of SiO₂ addition on the thermal deactivation of V₂O₅/WO₃/TiO₂ catalysts used for NOx pollution abatement. The results suggest that the degradation of the catalytic properties is strongly correlated to the structural ageing which is, in turn, mainly related to the anatase–rutile phase transformation and to the WO₃ phase segregation. The addition of SiO₂ strongly influences the temperature at which these phenomena occur. In fact, it was found that the introduction of this oxide stabilizes the material, retarding the collapse of surface area, and increases the temperature of the anatase to rutile phase transition.     

H_2O_2致大鼠RTE细胞系氧化应激作用及GSH保护作用的体外研究

许多具有氧化作用的空气污染物,均能使细胞产生氧化损伤,使胸腺基质淋巴生成素(thymic stromal lymphopoietin,TSLP)含量上升。而TSLP是一种启动过敏性炎症的重要因子,会导致哮喘等疾病发生率的上升。在本研究中用过氧化氢(H_2O_2)模拟具有氧化作用的空气污染物进行染毒,研究细胞氧化应激水平的变化,并讨论还原型谷胱甘肽(GSH)对细胞受氧化损伤的保护作用。将大鼠支气管上皮细胞(RTE)分组培养,每组设置6个平行实验,分别用低、中、高剂量H_2O_2染毒3 h;高剂量设置1个重复,作为保护组,在染毒前用GSH保护2 h。结果显示,高剂量组H_2O_2(3.2 mmol·L~(~(-1)))染毒的细胞,其细胞活力下降(P0.01),丙二醛(MDA)水平上升(P0.01),TSLP水平上升(P0.05),与之相比,用GSH保护后的同剂量染毒组,上述指标得到全面缓解(P0.01)。这表明高浓度的H_2O_2会损伤细胞活力,并使MDA及TSLP水平上升,而GSH对TSLP及MDA的升高有极显著的抑制作用,即对细胞有一定的保护作用。     

Different proxies for the reactivity of aquatic sediments towards oxygen: A model assessment

Information on benthic carbon mineralization rates is often derived from the analysis of oxygen microprofiles in sediments. To enable a direct comparison of different sediment environments, it is often desirable to characterize sediments by a single proxy that expresses their “reactivity” towards oxygen. For this, there are three commonly used proxies: the oxygen penetration depth (OPD), the oxygen flux at the sediment-water interface (DOU), and the maximum volumetric oxygen consumption rate (R_max). The OPD can be directly determined from the oxygen depth profile, while the DOU is usually obtained by a linear fit to the oxygen gradient either in diffusive boundary layer. The oxygen consumption rate R_max requires the fitting of a reactive-transport model to the data profile. This article shows that the OPD alone is a suboptimal proxy, because it shows a strong dependence on the half-saturation constant K_s, and secondly, because it is sensitive to the particular re-oxidation conditions right above the oxic-anoxic interface. Similarly, the volumetric oxygen consumption rate R_max is rather strongly dependent on the kinetic model formulation employed. To show this we fitted three different (Bouldin, Blackman and Monod) kinetics to the same oxygen data profiles. When fitting these models, the R_max values obtained differed by 20% for exactly the same oxygen profile. Accordingly, if one reports R_max values, it is crucial to specify the kinetic model alongside. Overall, DOU emerges as sediment reactivity proxy which is the least model dependent.     

Photodegradation of an azo dye by silver-doped nano-particulate titanium dioxide

The synthesis of silver doped nano-particulate titanium dioxide (Ag/TiO₂) using a microemulsion method and an investigation of its photocatalytic activity for the degradation of Acid Red 27 in distilled water under UV-irradiation is reported. The prepared Ag/TiO₂ is characterized using transmission electron microscopy, X-ray diffraction, and energy-dispersive X-ray spectroscopy. The size of the Ag nanoparticles is around 5–15?nm, with almost uniform distribution on the TiO₂ particles. The efficiency of the photocatalytic process is evaluated to establish the optimum conditions, found to be at 2?wt% of Ag loading on TiO₂, catalyst dosage of 400?mg?L^?1, and calcination temperature of 300°C. Complete decolorization of the dye solution on Ag/TiO₂ was observed in 20?min of UV irradiation in the optimum conditions.     

Histopathology of cerebro neuronal cells in freshwater snail Bellamya bengalensis: impact on respiratory physiology,by acute poisoning of mercuric and zinc chloride

Mercuric (Hg) and zinc (Zn) chloride toxicity was investigated in cerebroneuronal cells and gills of Bellamya bengalensis using sublethal concentrations under lab conditions. Freshwater snail B. bengalensis was exposed to mean LC₅₀ concentration (1.56 ppm and 12.7 ppm) of Hg and Zn chloride, respectively. Bioaccumulation of Hg and Zn was observed in nervous and gill tissue in proportion to the time of exposure. Respiratory mechanisms and rate of oxygen consumption was depleted by both metals. Histopathological alterations in cerebro neuronal cells (giant, large, medium, and small) and gill filamental epithelia were apparent in Hg and Zn-exposed snails. Histopathology demonstrated increased cytoplasmic basophilia, extreme indentation of plasma membrane, karyolitic and eccentric nuclei, nuclear envelope with irregular size, and shrunken appearance of cerebroneuronal cells. Histologically, gill filamental epithelia showed hypertrophy, enlarged ciliated margins reduced length of cilia, nuclear dilations, thickening of basal lamina, and hemocytic accumulations in induced cells and severe loss of goblet mucus cells at the tip. Histopathology was accompanied by dysfunctioning cilia with decreased rate of respiration. Overall, neuronal impairment with damaged gill filament produced improper gaseous exchange leading to sluggish movement.     

Integrating soil carbon cycling with that of nitrogen and phosphorus in the watershed model SWAT: Theory and model testing

In this paper we describe and test a sub-model that integrates the cycling of carbon (C), nitrogen (N) and phosphorus (P) in the Soil Water Assessment Tool (SWAT) watershed model. The core of the sub-model is a multi-layer, one-pool soil organic carbon (S_C) algorithm, in which the decomposition rate of S_C and input rate to S_C (through decomposition and humification of residues) depend on the current size of S_C. The organic N and P fluxes are coupled to that of C and depend on the available mineral N and P, and the C:N and N:P ratios of the decomposing pools. Tillage explicitly affects the soil organic matter turnover rate through tool-specific coefficients. Unlike most models, the turnover of soil organic matter does not follow first order kinetics. Each soil layer has a specific maximum capacity to accumulate C or C saturation (S_x) that depends on texture and controls the turnover rate. It is shown in an analytical solution that S_x is a parameter with major influence in the model C dynamics. Testing with a 65-yr data set from the dryland wheat growing region in Oregon shows that the model adequately simulates the S_C dynamics in the topsoil (top 0.3 m) for three different treatments. Three key model parameters, the optimal decomposition and humification rates and a factor controlling the effect of soil moisture and temperature on the decomposition rate, showed low uncertainty as determined by generalized likelihood uncertainty estimation. Nonetheless, the parameter set that provided accurate simulations in the topsoil tended to overestimate S_C in the subsoil, suggesting that a mechanism that expresses at depth might not be represented in the current sub-model structure. The explicit integration of C, N, and P fluxes allows for a more cohesive simulation of nutrient cycling in the SWAT model. The sub-model has to be tested in forestland and rangeland in addition to agricultural land, and in diverse soils with extreme properties such high or low pH, an organic horizon, or volcanic soils.     

Spatial variations in the N2O emissions and denitrification potential of riparian buffer strips in a contaminated urban river

Spatial variations in the N₂O emissions and denitrification potential of riparian buffer strips (RBS) in a polluted river were examined. The river received large pollutant inputs from urban runoff and wastewater discharge, resulting in impaired water quality in the river and downstream reservoir. The potential for nitrogen removal by RBS was evaluated by measuring in situ N₂O emission fluxes in static closed chambers and sediment denitrification potentials with acetylene inhibition techniques. The results showed that N₂O emission fluxes decreased from the upstream (16.39 μg/(m²·h)) to downstream (0.30 μg/(m²·h)) sites and from the water body to upland sites. The trend in decreasing N₂O emission fluxes in the downstream direction was mainly associated with sediment/soil textures (clay loam→sandy soil) and sediment/soil water contents and was also related to the vegetation along the RBS and nutrients in the sediments/soils. The correlation coefficient was highest (r=0.769) between the N₂O emission flux and sediment/soil water content. Sediment/soil denitrification potentials under N-amended and ambient conditions were higher (highest 32.86 mg/(kg·h)) for the upstream sites, which were consistent with in situ N₂O flux rates.     

培养基对大型溞(Daphnia magna)生长、繁殖和子代的影响

大型溞(Daphnia magna)急性活动抑制试验和繁殖试验是研究和评价新化学物质对水生生物危害性的重要手段之一。由于经济合作与发展组织(Organization for Economic Co-operation and Development, OECD)测试导则推荐的Elendt M4培养基中含有的乙二胺四乙酸(EDTA)可能会影响金属离子的活性,不适合用于含有金属离子样品的毒理学测试。为选出合适的替代培养基,采用Elendt M4培养基、美国材料与试验协会(American Society for Testing and Materials, ASTM)推荐的ASTM培养基和国际标准化组织(International Organization for Standardization, ISO)推荐的ISO培养基进行大型溞繁殖试验,并收集繁殖试验中亲溞产下的非头胎幼溞进行重铬酸钾的急性活动抑制试验。结果表明,3种培养基对大型溞的生长、存活均无抑制作用,ASTM培养基和ISO培养基中大型溞的繁殖量分别为111±10和70±13,显著低于Elendt M4培养基的132±4 (P 0.05)。3种培养基中大型溞的繁殖量均能满足OECD 211-2012大型溞繁殖试验标准中繁殖量大于60的要求,但在ISO培养基中有死胎出现。重铬酸钾对Elendt M4培养基、ASTM培养基和ISO培养基中繁殖幼溞的24 h半数效应浓度(24 h-EC_(50))值分别为1.29、1.84和0.772 mg·L~(-1),均在OECD 202-2004大型溞急性活动抑制试验标准要求的0.6～2.1 mg·L~(-1)范围内,说明3种培养基中繁殖的大型溞均能用于大型溞急性活动抑制试验的标准测试中。综上所述,进行含有金属离子样品的毒理测试时,ASTM培养基和ISO培养基均可用于大型溞的短期驯养和急性活动抑制试验,ASTM培养基还可以用于长期驯养和繁殖试验。以上结果为大型溞毒性试验中试验培养基的选择提供理论依据。     

Plant acclimation to elevated CO2—From simple regularities to biogeographic chaos

Upon exposure to altered levels of CO₂, plants express a variety of acclimations to CO₂ directly, over and above acclimations to indirect changes in temperature and water regimes. These acclimations commonly include increased photosynthetic CO₂ assimilation and increased water-use efficiency with reduced N content and reduced stomatal conductance. The robust generic acclimations are explicable by combining simple models of carboxylation, stomatal control, energy balance, and functional balance. Species- or genotype-specific acclimations are overlaid on these generic acclimations. Several such specific acclimations that are often seen are readily incorporated in an extended model. These specific acclimations generate a great spread of values in key performance measures of photosynthesis, water- and N-use efficiencies, and rates of water and N use, even among C₃ species that are the focus of this work. These performance measures contribute strongly to relative fitness and thus to evolving biogeographic distributions. The spread in fitness values is so large as to impend “chaotic” shifts in biogeography (and, ultimately, evolution) that are not understandable with models specific to species or functional groups; rather, a systematic study of key physiological and developmental parameters is merited. Also merited is a coherent extension of the model used here, or similar models, to include other phenomena, including mycorrhizal associations, transience in resource availability, etc. The composition of useful approximate fitness functions from physiological and allocational responses is a major challenge, with some leads originating from the model. In the search to extract patterns of responses, arguments based on the responses being close to optimal or adaptive will be misleading, in view of the absence of selection pressure to perform adaptively at high CO₂ for over 20 million years. I offer suggestions for more useful research designs.