Synthesis of α-Fe2O3 nanofibers for applications in removal and recovery of Cr(VI) from wastewater

Purpose

Nanomaterials such as iron oxides and ferrites have been intensively investigated for water treatment and environmental remediation applications. The purpose of this work is to synthesize α-Fe₂O₃ nanofibers for potential applications in removal and recovery of noxious Cr(VI) from wastewater.

Methods

α-Fe₂O₃ nanofibers were synthesized via a simple hydrothermal route followed by calcination. The crystallographic structure and the morphology of the as-prepared α-Fe₂O₃ nanofibers were characterized by X-ray diffraction, scanning electron microscope, and transmission electron microscope. Batch adsorption experiments were conducted, and Fourier transform infrared spectra were recorded before and after adsorption to investigate the Cr(VI) removal performance and adsorption mechanism. Langmuir and Freundlich modes were employed to analyze the adsorption behavior of Cr(VI) on the α-Fe₂O₃ nanofibers.

Results

Very thin and porous α-Fe₂O₃ nanofibers have been successfully synthesized for investigation of Cr(VI) removal capability from synthetic wastewater. Batch experiments revealed that the as-prepared α-Fe₂O₃ nanofibers exhibited excellent Cr(VI) removal performance with a maximum adsorption capacity of 16.17 mg g^?1. Furthermore, the adsorption capacity almost kept unchanged after recycling and reusing. The Cr(VI) adsorption process was found to follow the pseudo-second-order kinetics model, and the corresponding thermodynamic parameters ΔG°, ΔH°, and ΔS° at 298 K were calculated to be ?26.60 kJ?mol^?1, ?3.32 kJ?mol^?1, and 78.12 J?mol^?1 K^?1, respectively.

Conclusions

The as-prepared α-Fe₂O₃ nanofibers can be utilized as efficient low-cost nano-absorbents for removal and recovery of Cr(VI) from wastewater.     

Effects of hydromorphology and riparian vegetation on the sediment quality of agricultural low-order streams: consequences for stream restoration

Intensive agricultural land use imposes multiple pressures on streams. More specifically, the loading of streams with nutrient-enriched soil from surrounding crop fields may deteriorate the sediment quality. The current study aimed to find out whether stream restoration may be an effective tool to improve the sediment quality of agricultural headwater streams. We compared nine stream reaches representing different morphological types (forested meandering reaches vs. deforested channelized reaches) regarding sediment structure, sedimentary nutrient and organic matter concentrations, and benthic microbial respiration. Main differences among reach types were found in grain sizes. Meandering reaches featured larger mean grain sizes (50–70 μm) and a thicker oxygenated surface layer (8 cm) than channelized reaches (40 μm, 5 cm). Total phosphorous amounted for up to 1,500 μg?g^?1 DW at retentive channelized reaches and 850–1,050 μg?g^?1 DW at the others. While N-NH₄ accumulated in the sediments (60–180 μg?g^?1 DW), N-NO₃ concentrations were generally low (2–5 μg?g^?1 DW). Benthic respiration was high at all sites (10–20 g O₂ m^?2?day^?1). Our study shows that both hydromorphology and bank vegetation may influence the sediment quality of agricultural streams, though effects are often small and spatially restricted. To increase the efficiency of stream restoration in agricultural landscapes, nutrient and sediment delivery to stream channels need to be minimized by mitigating soil erosion in the catchment.     

In vitro Cr(VI) reduction by cell-free extracts of chromate-reducing bacteria isolated from tannery effluent irrigated soil

Four efficient Cr(VI)-reducing bacterial strains were isolated from rhizospheric soil of plants irrigated with tannery effluent and investigated for in vitro Cr(VI) reduction. Based on 16S rRNA gene sequencing, the isolated strains SUCR44, SUCR140, SUCR186, and SUCR188 were identified as Bacillus sp. (JN674188), Microbacterium sp. (JN674183), Bacillus thuringiensis (JN674184), and Bacillus subtilis (JN674195), respectively. All four isolates could completely reduce Cr(VI) in culture media at 0.2 mM concentration within a period of 24–120 h; SUCR140 completely reduced Cr(VI) within 24 h. Assay with the permeabilized cells (treated with Triton X-100 and Tween 80) and cell-free assay demonstrated that the Cr(VI) reduction activity was mainly associated with the soluble fraction of cells. Considering the major amount of chromium being reduced within 24–48 h, these fractions could have been released extracellularly also during their growth. At the temperature optima of 28 °C and pH?7.0, the specific activity of Cr(VI) reduction was determined to be 0.32, 0.42, 0.34, and 0.28 μmol Cr(VI)?min^?1?mg^?1 protein for isolates SUCR44, SUCR140, SUCR186, and SUCR188, respectively. Addition of 0.1 mM NADH enhanced the Cr(VI) reduction in the cell-free extracts of all four strains. The Cr(VI) reduction activity in cell-free extracts of all the isolates was stable in presence of different metal ions tested except Hg²⁺. Beside this, urea and thiourea also reduced the activity of chromate reduction to significant levels.     

Kinetics of phenol biodegradation at high concentration by a metabolically versatile isolated yeast Candida tropicalis PHB5

A highly tolerant phenol-degrading yeast strain PHB5 was isolated from wastewater effluent of a coke oven plant and identified as Candida tropicalis based on phylogenetic analysis. Biodegradation experiments with C. tropicalis PHB5 showed that the strain was able to utilize 99.4 % of 2,400 mg l^?1 phenol as sole source of carbon and energy within 48 h. Strain PHB5 was also observed to grow on 18 various aromatic hydrocarbons. Haldane model was used to fit the exponential growth data and the following kinetic parameters were obtained: μ _max?=?0.3407 h^?1, K _S?=?15.81 mg l^?1, K _i?=?169.0 mg l^?1 (R ²?=?0.9886). The true specific growth rate, calculated from μ _max, was 0.2113. A volumetric phenol degradation rate (V _max) was calculated by fitting the phenol consumption data with Gompertz model and specific degradation rate (q) was calculated from V _max. The q values were fitted with Haldane model, yielding following parameters: q _max?=?0.2766 g g^?1 h^?1, K _S ′?=?2.819 mg l^?1, K _i ′?=?2,093 (R ²?=?0.8176). The yield factor (Y _X/S ) varied between 0.185 to 0.96 g g^?1 for different initial phenol concentrations. Phenol degradation by the strain proceeded through a pathway involving production of intermediates such as catechol and cis,cis-muconic acid which were identified by enzymatic assays and HPLC analysis.     

Characterization of carbonaceous aerosols over Delhi in Ganga basin: seasonal variability and possible sources

The mass concentration of carbonaceous species, organic carbon (OC), and elemental carbon (EC) using a semicontinuous thermo-optical EC-OC analyzer, and black carbon (BC) using an Aethalometer were measured simultaneously at an urban mega city Delhi in Ganga basin from January 2011 to May 2012. The concentrations of OC, EC, and BC exhibit seasonal variability, and their concentrations were ～2 times higher during winter (OC 38.1?±?17.9 μg m^?3, EC 15.8?±?7.3 μg m^?3, and BC 10.1?±?5.3 μg m^?3) compared to those in summer (OC 14.1?±?4.3 μg m^?3, EC 7.5?±?1.5 μg m^?3, and BC 4.9?±?1.5 μg m^?3). A significant correlation between OC and EC (R?=?0.95, n?=?232) indicate their common emission sources with relatively lower OC/EC ratio (range 1.0–3.6, mean 2.2?±?0.5) suggests fossil fuel emission as a major source of carbonaceous aerosols over the station. On average, mass concentration of EC was found to be ～38 % higher than BC during the study period. The measured absorption coefficient (b_abs) was significantly correlated with EC, suggesting EC as a major absorbing species in ambient aerosols at Delhi. Furthermore, the estimated mass absorption efficiency (σ_abs) values are similar during winter (5.0?±?1.5 m² g^?1) and summer (4.8?±?2.8 m² g^?1). Significantly high aerosol loading of carbonaceous species emphasize an urgent need to focus on air quality management and proper impact assessment on health perspective in these regions.     

Removal of Cr(VI) onto Ficus carica biosorbent from water

The utilization of sustainable and biodegradable lignocellulosic fiber to detoxify the noxious Cr(VI) from wastewater is considered a versatile approach to clean up a contaminated aquatic environment. The aim of the present research is to assess the proficiency and mechanism of biosorption on Ficus carica bast fiber via isotherm models (Langmuir, Freundlich, Temkin, Harkin’s–Jura, and Dubinin–Radushkevich), kinetic models, and thermodynamic parameters. The biomass extracted from fig plant was characterized by scanning electron microscopy and Fourier-transform infrared spectroscopy. To optimize the maximum removal efficiency, different parameters like effect of initial concentration, effect of temperature, pH, and contact time were studied by batch method. The equilibrium data were best represented by the Langmuir isotherm model, and the maximum adsorption capacity of Cr(VI) onto biosorbent was found to be 19.68 mg/g. The pseudo-second-order kinetic model adequately described the kinetic data. The calculated values of thermodynamic parameters such as enthalpy change (?H ⁰), entropy change (?S ⁰), and free energy change (?G ⁰) were 21.55 kJ/mol, 76.24 J/mol?K, and ?1.55 kJ/mol, respectively, at 30 °C which accounted for spontaneous and endothermic processes. The study of adsorbent capacity for Cr(VI) removal in the presence of Na⁺, Mg²⁺, Ca²⁺, SO ₄ ^2? , HCO ₃ ^? and Cl^? illustrated that the removal of Cr(VI) increased in the presence of HCO^3? ions; the presence of Na⁺, SO ₄ ^2? or Cl^? showed no significant influence on Cr(VI) adsorption, while Ca²⁺ and Mg²⁺ ions led to an insignificant decrease in Cr(VI) adsorption. Further, the desorption studies illustrated that 31.10 % of metal ions can be removed from an aqueous system, out of which 26.63 % of metal ions can be recovered by desorption in first cycle and the adsorbent can be reused. The results of the scale-up study show that the ecofriendly detoxification of Cr(VI) from aqueous systems was technologically feasible.     

Assessing the enrichment of heavy metals in surface soil and plant (Digitaria eriantha) around coal-fired power plants in South Africa

Nine metals (Fe, Cu, Mn, Ni, Cd, Pb, Hg, Cr, and Zn) were determined in soil and Digitaria eriantha plants within the vicinity of three coal power plants (Matla, Lethabo, and Rooiwal), using ICP-OES and GFAAS. The total metal concentration in soil ranged from 0.05?±?0.02 to 1836?±?70 μg g^?1, 0.08?±?0.05 to 1744?±?29 μg g^?1, and 0.07?±?0.04 to 1735?±?91 μg g^?1 in Matla, Lethabo, and Rooiwal, respectively. Total metal concentration in the plant (D. eriantha) ranged from 0.005?±?0.003 to 535?±?43 μg g^?1 in Matla, 0.002?±?0.001 to 400?±?269 μg g^?1 in Lethabo, and 0.002?±?0.001 to 4277?±?201 μg g^?1 in Rooiwal. Accumulation factors (A) of less than 1 (i.e., 0.003 to 0.37) at all power plants indicate a low transfer of metal from soil to plant (excluder). Enrichment factor values obtained (2.4–5.0) indicate that the soils are moderately enriched with the exception of Pb that had significant enrichment of 20. Geo-accumulation index (I-geo) values of metals indicate that the soils are moderately polluted (0.005–0.65), except for Pb that showed moderate to strong pollution (1.74–2.53).     

Removal mechanisms and kinetics of trace tetracycline by two types of activated sludge treating freshwater sewage and saline sewage

Understanding the removal mechanisms and kinetics of trace tetracycline by activated sludge is critical to both evaluation of tetracycline elimination in sewage treatment plants and risk assessment/management of tetracycline released to soil environment due to the application of biosolids as fertilizer. Adsorption is found to be the primary removal mechanism while biodegradation, volatilization, and hydrolysis can be ignored in this study. Adsorption kinetics was well described by pseudo-second-order model. Faster adsorption rate (k ₂?=?2.04?×?10^?2?g?min^?1?μg^?1) and greater adsorption capacity (q _e?=?38.8 μg?g^?1) were found in activated sludge treating freshwater sewage. Different adsorption rate and adsorption capacity resulted from chemical properties of sewage matrix rather than activated sludge surface characteristics. The decrease of tetracycline adsorption in saline sewage was mainly due to Mg²⁺ which significantly reduced adsorption distribution coefficient (K _d) from 12,990?±?260 to 4,690?±?180 L?kg^?1. Species-specific adsorption distribution coefficients followed the order of $ K_{\mathrm{d}}^{{ + 00}} \gg K_{\mathrm{d}}^{{ + - 0}} > K_{\mathrm{d}}^{{ + - - }} $ . Contribution of zwitterionic tetracycline to the overall adsorption was >90 % in the actual pH range in aeration tank. Adsorption of tetracycline in a wide range of temperature (10 to 35 °C) followed the Freundlich adsorption isotherm well.     

Single and combined effects of aluminum (Al<Subscript>2</Subscript>O<Subscript>3</Subscript>) and zinc (ZnO) oxide nanoparticles in a freshwater fish, <Emphasis Type="Italic">Carassius auratus</Emphasis>

The increasing use of nanoparticles (NPs) worldwide has raised some concerns about their impact on the environment. The aim of the study was to assess the toxicity of metal oxide nanoparticles, singly or combined, in a freshwater fish (Carassius auratus). The fish were exposed for 7, 14, and 21 days to different concentrations of NPs (10 μg Al₂O₃.L^?1, 10 μg ZnO.L^?1, 10 μg Al₂O₃.L^?1 plus 10 μg ZnO.L^?1, 100 μg Al₂O₃.L^?1, 100 μg ZnO.L^?1, and 100 μg Al₂O₃.L^?1 plus 100 μg ZnO.L^?1). At the end of each exposure period, antioxidant enzyme activity (catalase, glutathione-S-transferase, and superoxide dismutase), lipid peroxidation, and histopathology were assessed in the gills and livers of C. auratus. The results show an increase in catalase (CAT) and superoxide dismutase (SOD) activity in the gills and livers of fish, especially after 14 days of exposure to single and combined NPs, followed by a reduction at 21 days. An increase in glutathione S-transferase (GST) was observed in gills after 7 days for all tested NP concentrations (single and combined); while in livers, a significant increase was determined after 14 days of exposure to 100 μg.L^?1 of both single ZnO and Al₂O₃ NPs. Lipid peroxidation (LPO) significantly increased in gills after 7 days of exposure to 100 μg.L^?1 Al₂O₃ NPs (single or combined). In livers, LPO increased significantly after 7 days of exposure to all tested concentrations of both single ZnO and Al₂O₃ (except for 10 μg Al₂O₃.L^?1), and after 14 days of exposure to ZnO (10 and 100 μg.L^?1) and Al₂O₃ (100 μg.L^?1)_. The results from histological observations suggest that exposure to metal oxide NPs affected both livers and gills, presenting alterations such as gill hyperplasia and liver degeneration. However, the most pronounced effects were found in gills. In general, this study shows that the tested NPs, single or combined, are capable of causing sub-lethal effects on C. auratus, but when combined, NPs seem to be slightly more toxic than when added alone.     

Evaluation of Acinetobacter sp. B9 for Cr (VI) resistance and detoxification with potential application in bioremediation of heavy-metals-rich industrial wastewater

Present work demonstrates Cr (VI) detoxification and resistance mechanism of a newly isolated strain (B9) of Acinetobacter sp. Bioremediation potential of the strain B9 is shown by simultaneous removal of major heavy metals including chromium from heavy-metals-rich metal finishing industrial wastewater. Strain B9 tolerate up to 350 mg L^?1 of Cr (VI) and also shows level of tolerance to Ni (II), Zn (II), Pb (II), and Cd (II). The strain was capable of reducing 67 % of initial 7.0 mg L^?1 of Cr (VI) within 24 h of incubation, while in presence of Cu ions 100 % removal of initial 7.0 and 10 mg L^?1 of Cr (VI) was observed with in 24 h. pH in the range of 6.0–8.0 and inoculum size of 2 % (v/v) were determined to be optimum for dichromate reduction. Fourier transform infrared spectroscopy and transmission electron microscopy studies suggested absorption or intracellular accumulation and that might be one of the major mechanisms behind the chromium resistance by strain B9. Scanning electron microscopy showed morphological changes in the strain due to chromium stress. Relevance of the strain for treatment of heavy-metals-rich industrial wastewater resulted in 93.7, 55.4, and 68.94 % removal of initial 30 mg L^?1 Cr (VI), 246 mg L^?1 total Cr, and 51 mg L^?1 Ni, respectively, after 144 h of treatment in a batch mode.     

Human health risk from organ-specific accumulation of toxic metals and response of antioxidants in edible fish species from Chenab River,Pakistan

In the current study, the bioaccumulation of essential and nonessential metals and related antioxidant activity were analyzed in three organs (muscle, gills, and liver) of herbivorous (HF) and carnivorous (CF) edible fish of Chenab River. The comparative analysis revealed a more heterogeneous accumulation of metals in the muscles of HF fish than that of CF fish [chromium (Cr, 3.4 μg g^?1), cobalt (Co, 1.7 μg g^?1), copper (Cu, 3 μg g^?1), and iron (Fe, 45 μg g^?1) versus Cr (1.3 μg g^?1), Co (0.1 μg g^?1), Cu (1.1 μg g^?1), and Fe (33 μg g^?1), respectively, P?<?0.001]. These results implied an organ-specific accumulation of metals at different trophic levels. According to logistic regression analysis, the bioaccumulation of metals had marked differences in HF and CF. The antioxidant activity was significantly related to the tissue type and the metals to which the organs are exposed to. The liver of CF fish had a higher activity of antioxidant superoxide dismutase (SOD), catalase (CAT), glutathione (GSH), and lipid peroxidase (LPO) than that of HF (P?<?0.05). LPO and guaiacol peroxidase (POD) in both groups were associated with a number of metals, but in HF, cadmium (Cd), Cr, Pb, and Zn were more related with the LPO and SOD activities. Moreover, Cd, Co, Fe, Pb, Ni, Cu, and Zn were above the permissible limits set by various agencies. In numerous cases, our results were even higher than those previously reported in the literature. The results provide an insight into the pollution pattern of Chenab River. These results may be helpful in the future to identify biomarkers of exposure in aquatic organisms.

Cr(VI) and COD removal from landfill leachate by polyculture constructed wetland at a pilot scale

Four subsurface horizontal-flow constructed wetlands (CWs) at a pilot scale planted with a polyculture of the tropical plants Gynerium sagittatum (Gs), Colocasia esculenta (Ce) and Heliconia psittacorum (He) were evaluated for 7 months. The CW cells with an area of 17.94 m² and 0.60 m (h) each and 0.5 m of gravel were operated at continuous gravity flow (Q?=?0.5 m³ day^?1) and a theoretical HRT of 7 days each and treating landfill leachate for the removal of filtered chemical oxygen demand (COD_f), BOD₅, TKN, NH₄ ⁺, NO₃ ^?, PO₄ ^3?–P and Cr(VI). Three CWs were divided into three sections, and each section (5.98 m²) was seeded with 36 cuttings of each species (plant density of six cuttings per square metre). The other unit was planted randomly. The final distributions of plants in the bioreactors were as follows: CW I (He-Ce-Gs), CW II (randomly), CW III (Ce-Gs-He) and CW IV (Gs-He-Ce). The units received effluent from a high-rate anaerobic pond (BLAAT®). The results show a slightly alkaline and anoxic environment in the solid-liquid matrix (pH?=?8.0; 0.5–2 mg L^?1 dissolved oxygen (DO)). COD_f removal was 67 %, BOD₅ 80 %, and TKN and NH₄ ⁺ 50–57 %; NO₃ ^? effluents were slightly higher than the influent, PO₄ ^3?–P (38 %) and Cr(VI) between 50 and 58 %. CW IV gave the best performance, indicating that plant distribution may affect the removal capacity of the bioreactors. He and Gs were the plants exhibiting a translocation factor (TF) of Cr(VI) >1. The evaluated plants demonstrated their suitability for phytoremediation of landfill leachate, and all of them can be categorized as Cr(VI) accumulators. The CWs also showed that they could be a low-cost operation as a secondary system for treatment of intermediated landfill leachate (LL).     

Remediation of acid mine drainage (AMD)-contaminated soil by Phragmites australis and rhizosphere bacteria

Experiments were conducted to assess the impact of citric acid (CA) and rhizosphere bacteria on metal uptake in Phragmites australis cultured in a spiked acid mine drainage (AMD) soil. Rhizosphere iron-oxidizing bacteria (Fe(II)OB) enhanced the formation of Fe plaque on roots, which decreased the uptake of Fe and Mn. CA inhibited the growth of Fe(II)OB, decreased the formation of metal plaque, raised the metal mobility in soil, and increased the accumulation of metals in all tissues of the reeds. The higher the CA dosage, the more metals accumulated into reeds. The total amount of metals in reeds increased from 7.8?±?0.5?×?10^?6 mol plant^?1 (Mn), 1.4?±?0.1?×?10^?3 mol plant^?1 (Fe), and 1.0?±?0.1?×?10^?4 mol plant^?1 (Al) in spiked soil without CA to 22.2?±?0.5?×?10^?6 mol plant^?1 (Mn), 3.5?±?0.06?×?10^?3 mol plant^?1 (Fe), and 5.0?±?0.2?×?10^?4 mol plant^?1 (Al) in soil added with 33.616 g C₆H₈O₇·H₂O for per kilogram soil. CA could be effective at enhancing the phytoremediation of metals from AMD-contaminated soil.     

Elevated water temperature reduces the acute toxicity of the widely used herbicide diuron to a green alga, Pseudokirchneriella subcapitata

In the actual environment, temperatures fluctuate drastically through season or global warming and are thought to affects risk of pollutants for aquatic biota; however, there is no report about the effect of water temperature on toxicity of widely used herbicide diuron to fresh water microalgae. The present research investigated inhibitory effect of diuron on growth and photosynthetic activity of a green alga Pseudokirchneriella subcapitata at five different temperatures (10, 15, 20, 25, and 30 °C) for 144 h of exposure. As a result, effective diuron concentrations at which a 50 % decrease in algal growth occurred was increased with increasing water temperature ranging from 9.2 to 20.1 μg L^–1 for 72 h and 9.4–28.5 μg L^–1 for 144 h. The photochemical efficiency of photosystem II (F _v/F _m ratio) was significantly reduced at all temperatures by diuron exposure at 32 μg L^–1 after 72 h. Inhibition rates was significantly increased with decreased water temperature (P?<?0.01). Intracellular H₂O₂ levels as an indicator of oxidative stress were also decreased with increasing temperature in both control and diuron treatment groups and were about 2.5 times higher in diuron treatment groups than that of controls (P?<?0.01). Our results suggest water temperatures may affect the toxicokinetics of diuron in freshwater and should therefore be considered in environmental risk assessment.     

Decomposition of phenylarsonic acid by AOP processes: degradation rate constants and by-products

The paper presents results of the studies photodegradation, photooxidation, and oxidation of phenylarsonic acid (PAA) in aquatic solution. The water solutions, which consist of 2.7 g dm^?3 phenylarsonic acid, were subjected to advance oxidation process (AOP) in UV, UV/H₂O₂, UV/O₃, H₂O₂, and O₃ systems under two pH conditions. Kinetic rate constants and half-life of phenylarsonic acid decomposition reaction are presented. The results from the study indicate that at pH 2 and 7, PAA degradation processes takes place in accordance with the pseudo first order kinetic reaction. The highest rate constants (10.45?×?10^?3 and 20.12?×?10^?3) and degradation efficiencies at pH 2 and 7 were obtained at UV/O₃ processes. In solution, after processes, benzene, phenol, acetophenone, o-hydroxybiphenyl, p-hydroxybiphenyl, benzoic acid, benzaldehyde, and biphenyl were identified.     

1985 Directory of Governmental Air Pollution Control Agencies

Abstract

Clay that contains kaolinite has been used extensively as a raw material for manufacturing of bricks and china at 900–1100 °C. This study used clay to stabilize the contaminant chromium(VI) [Cr(VI)] through a heating process at 500–1100 °C. X-ray absorption spectroscopic results indicated that the 500–900 °C heating process transformed hazardous Cr(VI) to nontoxic Cr(III); Cr₂O₃ was the species detected as most abundant. The 1100 °C heating process caused the formation of Cr₂SiO₅, which was not detected in the samples heated at 500–900 °C. Fourier transformed extended X-ray absorption fine structure spectra were fitted by use of WinXAS software. Phase shifts and backscatter(ing) amplitudes for specific atom pairs, based on the crystallographic data for CrO₃ and Cr₂O₃, were theoretically calculated with the FEFF software. The processed XAS data show that the first shell coordination numbers were similar to each other as the temperature was increased from 500 to 900 °C and 1100 °C, implying that their Cr(III) crystallite size was relatively similar. The interatomic distance between the target center element and the first shell for the 500– 1100 °C samples was 1.98Å. The Debye-Waller factor for the 1100 °C sample was increased compared with the 500 and 900 °C samples and probably indicates the formation of Cr₂SiO₅.     

Electrooxidation of industrial wastewater containing 1,4-dioxane in the presence of different salts

The treatment of 1,4-dioxane solution by electrochemical oxidation on boron-doped diamond was studied using a central composite design and the response surface methodology to investigate the use of SO₄ ^2? and HCO₃ ^? as supporting electrolytes considering the applied electric current, initial chemical oxygen demand (COD) value, and treatment time. Two industrial effluents containing bicarbonate alkalinity, one just carrying 1,4-dioxane (S1), and another one including 1,4-dioxane and 2-methyl-1,3-dioxolane (S2), were treated under optimized conditions and subsequently subjected to biodegradability assays with a Pseudomonas putida culture. Electrooxidation was compared with ozone oxidation (O₃) and its combination with hydrogen peroxide (O₃/H₂O₂). Regarding the experimental design, the optimal compromise for maximum COD removal at minimum energy consumption was shown at the maximum tested concentrations of SO₄ ^2? and HCO₃ ^? (41.6 and 32.8 mEq L^?1, respectively) and the maximum selected initial COD (750 mg L^?1), applying a current density of 11.9 mA cm^?2 for 3.8 h. Up to 98 % of the COD was removed in the electrooxidation treatment of S1 effluent using 114 kWh per kg of removed COD and about 91 % of the COD from S2 wastewater applying 49 kWh per kg of removed COD. The optimal biodegradability enhancement was achieved after 1 h of electrooxidation treatment. In comparison with O₃ and O₃/H₂O₂ alternatives, electrochemical oxidation achieved the fastest degradation rate per oxidant consumption unit, and it also resulted to be the most economical treatment in terms of energy consumption and price per unit of removed COD.     

Effects of nitrogen application rate and a nitrification inhibitor dicyandiamide on methanotroph abundance and methane uptake in a grazed pasture soil

Methane-oxidizing bacteria (methanotrophs) in the soil are a unique group of methylotrophic bacteria that utilize methane (CH₄) as their sole source of carbon and energy which limit the flux of methane to the atmosphere from soils and consume atmospheric methane. A field experiment was conducted to determine the effect of nitrogen application rates and the nitrification inhibitor dicyandiamide (DCD) on the abundance of methanotrophs and on methane flux in a grazed pasture soil. Nitrogen (N) was applied at four different rates, with urea applied at 50 and 100 kg N ha^?1 and animal urine at 300 and 600 kg N ha^?1. DCD was applied at 10 kg ha^?1. The results showed that both the DNA and selected mRNA copy numbers of the methanotroph pmoA gene were not affected by the application of urea, urine or DCD. The methanotroph DNA and mRNA pmoA gene copy numbers were low in this soil, below 7.13?×?10³ g^?1 soil and 3.75?×?10³ μg^?1 RNA, respectively. Daily CH₄ flux varied slightly among different treatments during the experimental period, ranging from ?12.89 g CH₄ ha^?1 day^?1 to ?0.83 g CH₄ ha^?1 day^?1, but no significant treatment effect was found. This study suggests that the application of urea fertilizer, animal urine returns and the use of the nitrification inhibitor DCD do not significantly affect soil methanotroph abundance or daily CH₄ fluxes in grazed grassland soils.     

Spatial and temporal variations of nitrous oxide flux between coastal marsh and the atmosphere in the Yellow River estuary of China

To investigate the spatial and seasonal variations of nitrous oxide (N₂O) fluxes and understand the key controlling factors, we explored N₂O fluxes and environmental variables in high marsh (HM), middle marsh (MM), low marsh (LM), and mudflat (MF) in the Yellow River estuary throughout a year. Fluxes of N₂O differed significantly between sampling periods as well as between sampling positions. During all times of day and the seasons measured, N₂O fluxes ranged from ?0.0051 to 0.0805 mg N₂O m^?2 h^?1, and high N₂O emissions occurred during spring (0.0278 mg N₂O m^?2 h^?1) and winter (0.0139 mg N₂O m^?2 h^?1) while low fluxes were observed during summer (0.0065 mg N₂O m^?2 h^?1) and autumn (0.0060 mg N₂O m^?2 h^?1). The annual average N₂O flux from the intertidal zone was 0.0117 mg N₂O m^?2 h^?1, and the cumulative N₂O emission throughout a year was 113.03 mg N₂O m^?2, indicating that coastal marsh acted as N₂O source. Over all seasons, N₂O fluxes from the four marshes were significantly different (p?<?0.05), in the order of HM (0.0256?±?0.0040 mg N₂O m^?2 h^?1)?>?MF (0.0107?±?0.0027 mg N₂O m^?2 h^?1)?>?LM (0.0073?±?0.0020 mg N₂O m^?2 h^?1)?>?MM (0.0026?±?0.0011 mg N₂O m^?2 h^?1). Temporal variations of N₂O emissions were related to the vegetations (Suaeda salsa, Phragmites australis, and Tamarix chinensis) and the limited C and mineral N in soils during summer and autumn and the frequent freeze/thaw cycles in soils during spring and winter, while spatial variations were mainly affected by tidal fluctuation and plant composition at spatial scale. This study indicated the importance of seasonal N₂O contributions (particularly during non-growing season) to the estimation of local N₂O inventory, and highlighted both the large spatial variation of N₂O fluxes across the coastal marsh (CV?=?158.31 %) and the potential effect of exogenous nitrogen loading to the Yellow River estuary on N₂O emission should be considered before the annual or local N₂O inventory was evaluated accurately.