Changes in the system of chemical bonds in gibbsite under the impact of NH<Subscript>4</Subscript>H<Subscript>2</Subscript>PO<Subscript>4</Subscript> solutions of different concentrations

The participation of anionic aluminum hydroxo complexes in the binding of phosphate anions on the surface of gibbsite has been shown. The succession of changes in the anionic aluminum phosphate complexes under increasing concentration of phosphate solution has been studied. It has been found that aluminum polyphosphate complexes responsible for the intensive dissolution of gibbsite are formed, along with aluminum orthophosphate complexes, at phosphate solution concentrations of 1 and 2 mol P/L. The decisive role of polyphosphate (P–O–P) groups in the ligand structure of anionic complexes in the transformation of gibbsite to a phosphate mineral (ammonium taranakite) has been revealed. The role of hydrogen bonds with the participation of ligand P(O)OH groups in the formation of ammonium taranakite crystals has been discussed.     

Improved Photodegradation Efficiency of 2,4-DCP Through a Combined Q<Subscript>3</Subscript>Fe(III)-Decorated Porous g-C<Subscript>3</Subscript>N<Subscript>4</Subscript>/H<Subscript>2</Subscript>O<Subscript>2</Subscript> System

Graphitic carbon nitride (g-C₃N₄) is a photocatalyst with wide application in removal of organic pollutants. In this study, we designed a porous g-C₃N₄ (p-g-C₃N₄)/8-quinolinolato iron(III) (Q₃Fe)/H₂O₂ system to enhance the organic pollutant removal efficiency by combining photocatalysis and Fenton interaction under neutral condition. The p-g-C₃N₄ was prepared through a two-step thermal oxidation reaction. Afterwards, Q₃Fe-coupled p-g-C₃N₄ was prepared by an impregnating method. The 2,4-dichlorophenol (2,4-DCP) photodegradation ratio and decomposition rate of the p-g-C₃N₄/Q₃Fe/H₂O₂ system are approximately 5 and 18 times as high as those of individual p-g-C₃N₄ system, respectively. Besides, its degradation rate is 4.3 times as high as that in the p-g-C₃N₄/H₂O₂ system. Meanwhile, Q₃Fe/g-C₃N₄ also exhibits higher activity than individual p-g-C₃N₄ in 2,4-DCP photo-decomposing. On the basis of the results of the radical trapping experiments and the Fe(II) concentration in different systems, the synergistic effect between photocatalysis and Fenton reaction is vital for the efficient pollutant degradation. The coupled system combining p-g-C₃N₄ with Q₃Fe and H₂O₂ shows potential for efficient treatment of recalcitrant organic pollutants. The combined system in this work indicated a new idea for the decomposition of organic pollutants.     

Solar Decolorization of Methylene Blue by Magnetic MgFe<Subscript>2</Subscript>O<Subscript>4</Subscript>-MWCNT/Ag<Subscript>3</Subscript>VO<Subscript>4</Subscript> Visible Active Photocatalyst

MgFe₂O₄-MWCNT/Ag₃VO₄ photocatalyst was prepared for benefiting the visible region of solar spectrum. Prepared catalyst was characterized by using scanning electron microscope (SEM), X-ray diffraction (XRD), and energy-dispersive X-ray spectroscopy (EDX). Photocatalytic activity was measured by methylene blue (MB) decolorization under visible light obtained from a 105-W tungsten light bulb. Dye decolorization and its kinetics were followed up by means of a UV-vis spectrophotometer. Kinetic model of decolorization was found to be compatible with first-order kinetics. The effects of pH and concentration of MB solution on the decolorization efficiency were determined. Low and high pH conditions were found to be more effective in increasing the MB decolorization yield and rate. On the other hand, due to the low transparency of concentrated MB solutions, an increase on decolorization time and a lowering in decolorization yield were encountered. Thanks to the magnetic MgFe₂O₃ nanoparticles, 96% of the catalyst could be recovered by a simple magnetic bar. It was observed that simulated wastewater containing MB was also successfully decolorized showing that visible region-sensitive MgFe₂O₄-MWCNT/Ag₃VO₄ photocatalyst can be benefited as a potential, efficient, and reusable material for the removal organic pollutants in aquatic environment.     

Response of CH<Subscript>4</Subscript> oxidation and methanotrophic diversity to NH<Subscript>4</Subscript><Superscript>+</Superscript> and CH<Subscript>4</Subscript> mixing ratios

Methane oxidising activity and community structure of 11, specifically targeted, methanotrophic species have been examined in an arable soil. Soils were sampled from three different field plots, receiving no fertilisation (C), compost (G) and mineral fertiliser (M), respectively. Incubation experiments were carried out with and without pre-incubation at elevated CH₄ mixing ratios (100 ml CH₄ l⁻¹) and with and without ammonium (100 mg N kg⁻¹) pre-incubation. Four months after fertilisation, plots C, G and M did not show significant differences in physicochemical properties and CH₄ oxidising activity. The total number of methanotrophs (determined as the sum the 11 specifically targeted methanotrophs) in the fresh soils was 17.0×10⁶, 13.7×10⁶ and 15.5×10⁶ cells g⁻¹ for treatment C, G and M, respectively. This corresponded to 0.11 to 0.32% of the total bacterial number. The CH₄ oxidising activity increased 10⁵-fold (20–26 mg CH₄ g⁻¹ h⁻¹), the total number of methanotrophs doubled (28–76×10⁶ cells g⁻¹) and the methanotrophic diversity markedly increased in treatments with a pre-incubation at elevated CH₄ concentrations. In all soils and treatments, type II methanotrophs (62–91%) outnumbered type I methanotrophs (9–38%). Methylocystis and Methylosinus species were always most abundant. After pre-incubation with ammonium, CH₄ oxidation was completely inhibited; however, no change in the methanotrophic community structure could be detected.     

Removal of As(III) from Aqueous Solution Using Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> Nanoparticles: Process Modeling and Optimization Using Statistical Design

In this study, Extran (biodegradable surfactant) was used for the preparation of Fe₃O₄ nanoparticles by microemulsion process to improve removal efficiency of As(III) from aqueous solution. Fe₃O₄ nanoparticles were characterized by XRD, FTIR, FESEM, TEM, HRTEM, and VSM instrumental techniques. The effect of different parameters such as adsorbent dose, initial As(III) concentration, and solution pH were studied by response surface methodology (RSM) based on Box-Behnken design (BBD). The optimized condition for adsorption of As(III) from aqueous solution was obtained as adsorbent dose of 0.70 mg/g, solution pH of 7.7, and initial As(III) concentration of 33.32 mg/L. In this optimum condition, about 90.5% of As(III) was removed from the aqueous solution. Isotherm studies have been done at optimal condition, and it was observed that the Langmuir isotherm models were fitted well with experimental data having a high correlation coefficient of 0.993. From the Langmuir isotherm data, the maximum adsorption capacity of Fe₃O₄ nanoparticles was found to be 7.18 mg/g at pH 7.7 in room temperature. This study revealed that Fe₃O₄ nanoparticles can be used as an efficient, eco-friendly, and effective material for the adsorptive removal of As(III) from aqueous system.     

Preparation of Highly Efficient CoFe<Subscript>2</Subscript>O<Subscript>4</Subscript>/Zn<Subscript>2</Subscript>SnO<Subscript>4</Subscript> Composite Photocatalyst for the Degradation of Rhodamine B Dye from Aqueous Solution

CoFe₂O₄/Zn₂SnO₄ composite was synthesized using a simple two-step process and applied as a novel-efficient photocatalyst for the rhodamine B degradation from aqueous solution. Characterization techniques such as X-ray diffraction (XRD), N₂ adsorption-desorption isotherms, scanning electron microscopy (SEM), EDS analysis, and diffuse reflectance spectroscopy were employed in order to investigate the physical and chemical properties of composite. Higher values of the specific surface area, pore volume and diameter, and a smaller band-gap energy promoted a greater catalytic activity of CoFe₂O₄/Zn₂SnO₄ composite when compared to Zn₂SnO₄. A rapid decolorization of dye solution was observed at 40 min of reaction using the CoFe₂O₄/Zn₂SnO₄ catalyst, being 2.5 times faster than the Zn₂SnO₄ alone. Therefore, the CoFe₂O₄/Zn₂SnO₄ composite shows extraordinarily high photocatalytic activity toward the degradation of rhodamine B dye from aqueous solution.     

Porous Materials Modified with Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> Nanoparticles for Arsenic Removal in Drinking Water

The contamination of drinking water with arsenic has been a problem in a lot of countries around the world because of its toxicological and carcinogenic effects on human health. Porous materials modified with Fe₃O₄ nanoparticles (Fe₃O₄ NPs) represent convenient removers for that contaminant. A co-precipitation method of Fe(III) and Fe(II) in alkaline media was applied to obtain Fe₃O₄ NPs. In a first stage, single nanoparticles were synthesized and stabilized with carboxylic acids. A characterization with attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR), Raman spectroscopy, and X-ray diffraction (XRD) confirms a magnetite-type structure. Moreover, transmission electron microscopy (TEM) and calculations from XRD data using Scherrer’s equation indicate an average particle size of 13 nm and an average crystallite size of 10 nm, both independent of the stabilizer used. Then, the co-precipitation method studied was applied to modify kaolin, bentonite, diatomite, and silica and thus prepare magnetic composites having support-magnetite weight ratios of 2:1. Among them, silica-modified material presented the best hydraulic characteristics, an important aspect for large-scale applications such as removal under gravity. This composite has the capacity to remove up to 80 and 70% for initial concentrations of 25 and 50 μg/L, respectively, representing a convenient remover for processes developed in subsequent stages or in continuous flow.     

Soil nitrogen mineralization and fate of (<Superscript>15</Superscript>NH<Subscript>4</Subscript>)<Subscript>2</Subscript>SO<Subscript>4</Subscript> in field-incubated soil in a hardwood plantation of subtropical Australia: the effect of mulching

Background, aim, and scope  

Mulching is frequently used to overcome the drought problem in hardwood plantations that are increasingly being established in lower rainfall areas of Queensland, Australia because of increasing land values. In addition to soil water content, soil nitrogen (N) availability is another critical determinant of plantation productivity in these areas. The purpose of this study was to understand how soil mineral N dynamics, in situ N mineralization, and the fate of fertilized N would be affected by mulching during the early establishment of hardwood plantations.     

A comparison of soil food webs beneath C<Subscript>3</Subscript>- and C<Subscript>4</Subscript>-dominated grasslands

Soil food webs influence organic matter mineralization and plant nutrient availability, but the potential for plants to capitalize on these processes by altering soil food webs has received little attention. We compared soil food webs beneath C₃- and C₄-grass plantings by measuring bacterial and fungal biomass and protozoan and nematode abundance repeatedly over 2 years. We tested published expectations that C₃ detritus and root chemistry (low lignin/N) favor bacterial-based food webs and root-feeding nematodes, whereas C₄ detritus (high lignin/N) and greater production favor fungal decomposers and predatory nematodes. We also hypothesized that seasonal differences in plant growth between the two grassland types would generate season-specific differences in soil food webs. In contrast to our expectations, bacterial biomass and ciliate abundance were greater beneath C₄ grasses, and we found no differences in fungi, amoebae, flagellates, or nematodes. Soil food webs varied significantly among sample dates, but differences were unrelated to aboveground plant growth. Our findings, in combination with previous work, suggest that preexisting soil properties moderate the effect of plant inputs on soil food webs. We hypothesize that high levels of soil organic matter provide a stable environment and energy source for soil organisms and thus buffer soil food webs from short-term dynamics of plant communities.     

Effect of CO<Subscript>2</Subscript> on nitrification and immobilization of NH<Subscript>4</Subscript><Superscript>+</Superscript>-N

A laboratory incubation experiment was conducted to demonstrate that reduced availability of CO₂ may be an important factor limiting nitrification. Soil samples amended with wheat straw (0%, 0.1% and 0.2%) and (¹⁵NH₄)₂SO₄ (200 mg N kg^–1 soil, 2.213 atom% ¹⁵N excess) were incubated at 30±2°C for 20 days with or without the arrangement for trapping CO₂ resulting from the decomposition of organic matter. Nitrification (as determined by the disappearance of NH₄⁺ and accumulation of NO₃^–) was found to be highly sensitive to available CO₂ decreasing significantly when CO₂ was trapped in alkali solution and increasing substantially when the amount of CO₂ in the soil atmosphere increased due to the decomposition of added wheat straw. The co-efficient of correlation between NH₄⁺-N and NO₃^–-N content of soil was highly significant (r =0.99). During incubation, 0.1–78% of the applied NH₄⁺ was recovered as NO₃^– at different incubation intervals. Amendment of soil with wheat straw significantly increased NH₄⁺ immobilization. From 1.6% to 4.5% of the applied N was unaccounted for and was due to N losses. The results of the study suggest that decreased availability of CO₂ will limit the process of nitrification during soil incubations involving trapping of CO₂ (in closed vessels) or its removal from the stream of air passing over the incubated soil (in open-ended systems).     

Suppression of NH<Subscript>3</Subscript> and N<Subscript>2</Subscript>O emissions by massive urea intercalation in montmorillonite

Purpose  

A large amount of nitrogen (N) fertilizers has been broadcasted over soil surface for reliable crop production. Unfortunately, the broadcasted N vulnerable to volatilization and leaching can lead to serious environmental problems. As a new approach to mitigate N loss of broadcasted fertilizers, massive intercalation of urea into montmorillonite (MMT) was recently proposed to innovatively enhance the urea use efficiency. This study focuses on demonstrating the behaviors of the urea intercalated into MMT in soils.     

Effectiveness of Air,N<Subscript>2</Subscript> (gas), Fe<Superscript>+3</Superscript> and Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> Nanoparticles on the Sonication of Less and More Hydrophobic Polycyclic Aromatic Hydrocarbons (PAHs) and Toxicity

In this study, the effects of 1 h aeration, nitrogen gas N₂(g) sparging (15 and 30 min) and increasing ferric ions (Fe⁺³) as FeSO₄ (10, 20 and 50 mg L⁻¹) and Fe₃O₄ nanoparticles (1, 2 and 4 g L⁻¹) concentrations on three less hydrophobic and three more hydrophobic polycyclic aromatic hydrocarbons (PAHs) and toxicity removals from a petrochemical industry in Izmir (Turkey) were investigated in a sonicator with a power of 650 W and an ultrasound frequency of 35 kHz; 1 h aeration increased the yields in benzo[b]fluoranthene, benzo[k]fluoranthene and benzo[a]pyrene PAHs (less hydrophobic) from 62% to 67% to around 95–97% after 150 min sonication at 60°C. However, 1 h aeration did not contribute to the yields of more hydrophobic PAHs (indeno[1,2,3-cd]pyrene, dibenz[a,h]anthracene, benzo[g,h,i]perylene). The maximum yields were obtained at acidic and alkaline pH for more and less hydrophobic PAHs, respectively, after 60 and 120 min sonication at 30°C; 30 min N₂(g) sparging, 50 mg L⁻¹ Fe⁺³ increased the yields of less hydropobic PAHs after 150 min sonication at 60°C. Two milligrams per liter of Fe₃O₄ nanoparticles increased both less (87–88%) and more (96–98%) hydrophobic PAH yields. The Daphnia magna acute toxicity test showed that the toxicity decreased significantly with an hour aeration, 30 min N₂(g) sparging, 50 mg L⁻¹ Fe⁺³ and 2 g L⁻¹ Fe₃O₄ nanoparticles at 60°C after 120 and 150 min sonications. Vibrio fischeri was found to be more resistant to the sonicated samples than D. magna. Significant correlations were found between the physicochemical properties of sonicated PAHs and acute toxicities both organisms.     

Net and gross mineral N production rates at three levels of forest canopy retention: evidence that NH<Subscript>4</Subscript><Superscript>+</Superscript> and NO<Subscript>3</Subscript><Superscript>−</Superscript> dynamics are uncoupled

Alternative silvicultural systems were introduced in Coastal Western Hemlock forests of British Columbia, Canada, to reduce disturbance incurred by conventional clear-cutting and to maintain the forest influence on soil nutrient cycling. As we hypothesized, in situ pools and net mineralization of NH₄ ⁺ were lower under no and low disturbance (old-growth forest and shelterwood) compared to clear-cuts (high disturbance); in situ pools and net production of NO₃ ⁻ were very low across all treatments. Gross transformation rates of NH₄ ⁺ increased while those of NO₃ ⁻ decreased with increasing disturbance, suggesting that these processes were uncoupled. We conclude that shelterwood harvesting reduces the impact on forest floor NH₄ ⁺ cycling compared to clear-cutting, and that neither low nor high disturbance intensity results in substantial NO₃ ⁻ accumulation, as what occasionally occurs in other ecosystems. We hypothesize that the uncoupling of NH₄ ⁺ and NO₃ ⁻ dynamics may be due to the predominance of heterotrophic nitrification by lignin-degrading fungi that oxidize organic N rather than NH₄ ⁺–N, and whose activities are suppressed at high NH₄ ⁺ concentrations.     

pH-Based Strategies for an Efficient Addition of H<Subscript>2</Subscript>O<Subscript>2</Subscript> During Ozonation to Improve the Mineralisation of Two Contaminants with Different Degradation Resistances

Ozonation is an efficient process for the primary degradation of most substrates but not for their mineralisation. In this work, the ozonation enhanced with the addition of H₂O₂ was studied for two substrates with very different oxidation resistances: the dye rhodamine 6G (R6G) and the surfactant linear alkylbenzene sulfonate (LAS). With O₃ only, the primary degradation of R6G was completed in less than 10 min but its TOC removal only reached 45% in 1 h. By adding H₂O₂, TOC removal was increased to 70% with a molar ratio (mol H₂O₂/mol substrate) of 10. The analysis of pH decrease served to define the specific basicity loss (SBL). The optimum conditions for the R6G mineralisation were found to be associated with a SBL value between 1 and 10 ((min/g)/L)^?1, through an adequate addition of H₂O₂. Moreover, in the case of LAS, the addition of H₂O₂ for a greater efficiency should occur after the foaming period, above all formed at acid pH. LAS degradation was also considerably improved, and the optimum for primary degradation achieved in 10 min with a TOC removal of over 65% with a molar ratio (mol H₂O₂/mol substrate) of 20.

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? Graphical Abstract

     

Influence of Biochar Addition on the Denitrification Process and N<Subscript>2</Subscript>O Emission in Cd-Contaminated Soil

The aim of this study was to investigate the effect of biochar addition on the denitrification process and N₂O emission in Cd-contaminated soil. Four different biochars, i.e., dairy manure and rice straw pyrolyzed at 350 and 550 °C, respectively, were added into a Cd-contaminated soil and incubation experiments were conducted for 8 weeks. Results showed that Cd had an inhibitory effect on denitrifying reductase enzymes and reduced the abundance of functional genes. On the contrary, amendment with the biochars increased denitrifying enzyme activity and gene abundance, and thus, enhanced the denitrification process. Labile carbon (C) in the biochar-amended soil, which was calculated based on the two-pool exponential model, was the key factor to facilitate this process. As a less important factor, elevated soil pH by biochar addition also increased denitrifying activity as well as the nosZ abundance. Decrease of Cd bioavailability by the biochar addition was beneficial to the denitrification process. Addition of the biochars with higher amount of NO₃ ^?-N, especially the rice straw-derived biochars, increased cumulative N₂O emission by more than ten times relative to the Cd-contaminated soil. With the great amount of labile C and NO₃ ^?-N, the treatment of biochars prepared at 350 °C released the larger amount of CO₂ and N₂O than other treatments. The biochar addition could totally release the heavy metal stress and restore the Cd-contaminated soil in terms of bacterial community.     

不同热解温度制备的香菇菌糠生物炭对孔雀石绿的吸附及其机理分析

为探讨菌糠原料及其所制备生物炭的理化性质与其对染料孔雀石绿吸附性能之间的内在关系,以香菇菌糠为原料,在不同热解温度下(350℃和750℃)制备菌糠生物炭(LS350和LS550),研究热解温度对生物炭理化性质与染料吸附性能的影响,并利用扫描电子显微镜(SEM)、X射线衍射仪(XRD)和傅里叶变换红外光谱(FTIR)技术...     

TiO<Subscript>2</Subscript> photocatalytic degradation of 4-chlorobiphenyl as affected by solvents and surfactants

Purpose  

TiO₂ photocatalytic degradation of 4-chlorobiphenyl (PCB3) in aqueous solution under UV irradiation was investigated as affected by different environmental factors, including initial PCB3 concentration, TiO₂ content, UV intensity, H₂O₂ concentration, cosolvents, and surfactants.     

Influence of Sulfonation of Inert Macroporous and Macronet Resins on the SO<Subscript>2</Subscript> Adsorption Capacity

The influence of sulfonation of both macroporous and hyper-cross-linked polystyrenic polymers on their adsorption capacity for SO₂ removal from residual gases was studied through equilibrium experiments and microstructural analysis. The results showed that the insertion of functional sulfonic active groups leads to a decrease of adsorption capacity of macroporous and macronet resins mainly due to decreasing of specific surface area of the resins. The results were compared with those obtained for powdered activated carbon, which has an adsorption capacity higher compared with that of macroporous resins and lower than those of macronet resins. The high adsorption capacity of macronet resins has been attributed to the advanced cross-linking of the polystyrene chains that leads to the formation of a three-dimensional network with a high specific surface area. The fitting of the experimental data on the typical adsorption isotherms (Langmuir and Freundlich) highlighted the surface heterogeneity of macroporous and macronet resins.     

A Stable Fe<Subscript>2</Subscript>O<Subscript>3</Subscript>/Expanded Perlite Composite Catalyst for Degradation of Rhodamine B in Heterogeneous Photo-Fenton System

A stable and efficient Fe₂O₃/expanded perlite (Fe₂O₃-Ep) composite catalyst was synthesized by a simple hydrothermal method for degradation of refractory contaminants in heterogeneous photo-Fenton system. X-ray diffraction and FT-IR analyses confirmed the presence of the Fe₂O₃ in the synthesized catalyst. The catalytic activity of the Fe₂O₃-Ep catalyst was evaluated by the degradation of rhodamine B (RhB, 5 mg/L) and metronidazole (MET, 5 mg/L) in the presence of H₂O₂ under visible light irradiation. The Fe₂O₃-Ep catalyst exhibited high efficiency for degradation of RhB at a wide pH range from 2 to 10 and showed excellent catalytic property for decomposition of MET as well. The degradation ratio of RhB was achieved 99%, and the removal ratio of COD was 62% within 90 min at the best experimental conditions (0.5 g/L of Fe₂O₃-Ep catalyst, 2 mL/L of H₂O₂). Furthermore, iron leaching of the Fe₂O₃-Ep catalyst during the catalytic degradation reaction was negligible and the catalyst still exhibited high catalytic activity and stability after five cycles. These results show that the catalyst can be used as a highly efficient heterogeneous photo-Fenton catalyst for the degradation of non-biodegradable refractory pollutants in water.