Dissolution of Gibbsite and Its Transformation to Taranakite Depending on the Concentration of Phosphate Anions in the Solution

Structural changes of gibbsite at the binding of phosphate anions from NH₄H₂PO₄ solutions of different concentrations (from 10^–6 to 2 mol P/L) have been studied using an X-ray diffractometer and an electron scanning microscope with a spectrometric microanalyzer. It has been shown that, beginning from a concentration of 10^–3 mol P/L, the binding of phosphate anions has been accompanied by the release of anionic aluminum–phosphate complexes into the liquid phase. The content of these complexes has increased with the phosphate solution concentration and the time of its contact with gibbsite. The treatment of gibbsite with a 1 M phosphate solution for two months has resulted in the pronounced dissolution of the gibbsite crystal surface, accompanied by the formation of ammonium taranakite (ammonium salt of complex aluminophosphoric acid). Successive changes in size and form of the initially formed ammonium taranakite crystal has occurred in a 2 M phosphate solution. The degradation of the layered structure of taranakite and the enrichment of degradation products with phosphorus and nitrogen have been revealed. The significant increase of the P/Al ratios in the degradation products compared to the corresponding ratio in the initially formed taranakite indicates the formation of new phosphate phases resulting from the transformation of taranakite under the impact of free phosphate anions in a high-concentration solution.     

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.     

聚磷酸铵在土壤中有效性的变化及其影响因素

  【目的】  明确聚磷酸铵在土壤中有效性的变化及影响因素，为聚磷酸铵的合理高效施用提供参考。  【方法】  选用pH不同的两种供试土壤进行室内恒温培养试验和盆栽试验。培养试验总时长331 h (14天)，设置4个磷肥处理:不施磷肥处理 (CK)，及分别施磷酸二氢铵 (MAP)、聚合度4的聚磷酸铵 (APP-4) 和聚合度6的聚磷酸铵 (APP-6)处理；除CK外，其他3个处理均施用P₂O₅ 83.8 mg/kg，每个处理重复4次。于施肥后第0、3、24、96、144、240和331 h采样测定土壤有效磷含量。盆栽试验以玉米为供试材料，设置5个磷肥处理:不施磷肥处理(CK)，及分别施磷酸二氢铵 (MAP)、过磷酸钙 (SSP)、聚合度4的聚磷酸铵 (APP-4) 和聚合度6的聚磷酸铵 (APP-6)处理；除CK外，其他处理均以每盆 (2 kg土) 施N 0.400 g、P₂O₅ 0.764 g、K₂O 0.386 g，玉米苗移栽后第30天收获植株，测定地上部与地下部干重和全磷含量，同时测定土壤pH和有效磷含量。  【结果】  相比于MAP处理，APP处理能在较长时间内维持土壤中的有效磷含量。在酸性土中，APP-4和APP-6处理的磷肥利用率较SSP处理分别提高了49.5%和84.3%，在碱性土中较SSP处理分别提高了307.3%和316.2%。在酸性土中，APP处理的玉米地上部全磷含量较SSP处理提高了7.9%～12.4%，APP-6处理的玉米地下部全磷含量较SSP处理提高了13.5%；在碱性土中，APP处理的玉米地上部全磷含量较SSP处理提高了175.0%～177.6%，玉米地下部全磷含量提高了111.2%。APP-4和APP-6处理的玉米植株吸磷量在酸性土中较SSP处理提高了43.3%和74.0%，在碱性土中分别提高了244.6%和251.7%。与SSP处理相比，APP处理玉米地上部干重显著提高了17.2%～51.9%，地下部干重显著提高了13.3%～49.5%。  【结论】  聚磷酸铵比普通磷酸二氢铵能在更长的时间范围内维持土壤有效磷的含量，显著增加玉米对磷素的吸收利用效果，从而促进玉米的生长。聚合度和土壤酸碱性对聚磷酸铵的肥效响应显著，聚合度6的聚磷酸铵肥效显著优于聚合度4的聚磷酸铵，聚磷酸铵在碱性土壤中施用的效果好于酸性土壤。     

农用聚磷酸铵在土壤中的有效性研究进展及在农业上的应用

近年来,农用聚磷酸铵作为一种新型肥料逐渐进入我国化肥领域,常用作高浓度液体复合肥料的基础磷肥。聚磷酸铵pH值近中性,结晶温度低,具有螯合性、缓释性,有着很大发展空间。本文综述了聚磷酸铵在土壤中有效性(溶解性与移动性)的影响因素,重点分析水解速率、土壤矿物、土壤质地与水分对聚磷酸铵在土壤中的有效性,并分析聚磷酸铵在农业上的应用与发展前景。     

Aluminum solubility of strongly acidified allophanic Andosols from Kagoshima Prefecture,southern Japan

Abstract

The aluminum solubility of acidified soils both from furrows and under tree canopies of a tea garden was studied using equilibrium experiments in 0.01 mol L^?1 CaCl₂ solution systems. The soils were originally classified as allophanic Andosols. The furrow soils were more severely acidified because of the heavy application of nitrogen fertilizer, especially in the upper soil horizons (pH[H₂O] of 3.6–3.8 in the A1 and 2A2 horizons). These acidified soils were characterized by the dissolution of allophanic materials (allophane, imogolite and allophane-like materials) and by an increase in Al–humus complexes. Ion activity product (IAP) values of the strongly acidified soil horizons were largely undersaturated with respect to imogolite (allophanic clay) or gibbsite. Plots of p(Al³⁺) as a function of pH strongly indicated that Al solubility of the soils was largely controlled by Al–humus complexes, especially in the A1 horizon. In the canopy soils, which were more weakly acidified (pH[H₂O] 4.9–5.0), Al solubility was close to that of gibbsite and allophanic materials, indicating that the solubility is partly controlled by these minerals.     

Activated Biochar Prepared by Pomelo Peel Using H<Subscript>3</Subscript>PO<Subscript>4</Subscript> for the Adsorption of Hexavalent Chromium: Performance and Mechanism

Adsorption of hexavalent chromium (Cr(VI)) using pomelo peel activated biochar (PPAB) as a adsorbent was investigated. The characterization of the adsorbent was studied by Brunauer-Emmett-Teller (BET), thermogravimetric analysis (TGA), X-ray diffraction (XRD), and zeta potentials analysis. The results showed that the PPAB had a high microporous structure and the existence of organic compounds such as hemicellulose, cellulose, and lignin. Various parameters including initial Cr(VI) concentration, pH, and adsorbent dosage were studied. The results indicated that the adsorption process was pH dependent and maximum adsorption capacity of Cr(VI) was 57.637 mg/g at pH 2.0 and 35 °C with PPAB dosage of 0.05 g. The adsorption kinetics fitted well to the pseudo-second-order model and the correlation coefficients were greater than 0.999. The adsorption isotherm data could be better described with the Langmuir model, suggesting the homogeneous and monolayer adsorption. Moreover, the scanning electron microscopy (SEM), energy dispersive spectrometry (EDS), and Fourier transform infrared spectrum (FTIR) results showed that the surface of PPAB had plenty of developed pores after activation and the modification process was deemed to proceed between the O–H groups from pomelo peel and H₃PO₄ molecules. The main adsorption mechanism was attributed electrostatic interaction and ion exchange between the surface of PPAB and Cr(VI).     

Polyphosphate‐fertilizer solution stability with time,temperature, and pH

Ammonium polyphosphate fertilizers are gaining popularity in agricultural industry due to ease of application and yield benefits in calcareous soils. In this study, the effects of temperature, pH, and time on the stability of ammonium polyphosphate–fertilizer solution simulating a range of storage conditions were evaluated. Ion chromatography was used for the speciation of orthophosphate, pyrophosphate, and tripolyphosphate in the polyphosphate‐fertilizer solution over time. Polyphosphate solutions were very stable when the pH was maintained close to neutral (pH 6.4) and the temperature was less than 25°C. In contrast, at the lowest pH (2.3) and highest temperature (50°C) almost all tripolyphosphate and 96% of pyrophosphate was hydrolyzed after 28 d. The hydrolysis rate constant for tripolyphosphate at 50°C was calculated to be 9.2 × 10^–7 s^–1 and the half‐life 20 d. At 25°C, the half‐life of tripolyphosphate was 34 d at pH 2.3 and 174 d at pH 5.4. The activation energy at pH 2.3 was 12.7 kJ mol^–1. The results demonstrate that increasing temperature and decreasing pH have a deleterious effect on the stability of condensed P species in polyphosphate fertilizer. The effect of acidification on polyphosphate‐fertilizer composition requires consideration when formulating mixed ammonium polyphosphate blends with acids and trace elements for application in the field.     

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.     

An investigation of phosphate adsorbed on aluminium oxyhydroxide and oxide phases by nuclear magnetic resonance

The adsorption of phosphate by soil minerals controls availability of P to plants, but the chemical environments of adsorbed phosphate are poorly known. We used ³¹P MAS NMR to study the adsorption of phosphate on to boehmite (γ‐AlOOH) and γ‐Al₂O₃ with large surface areas. The solid phases were reacted in 0.1 m phosphate solutions at pH from 3 to 11 and in solutions with pH 5 at concentrations from 10^?1 m to 10^?4 m . The spectra suggested three different phosphate environments: (i) orthophosphate precipitated from the residual solution after vacuum filtering, (ii) surface‐adsorbed phosphate in inner‐sphere complexes, and (iii) Al‐phosphate precipitates on the surfaces of the minerals. The chemical shifts of both the inner‐sphere complexes and surface precipitates became progressively less shielded with increasing pH and decreasing concentration of phosphate solution. For the inner‐sphere complexes, we interpret these changes to be the result of decreasing phosphate protonation combined with rapid proton exchange among phosphate tetrahedra with different numbers of protons, which causes peak averaging. The chemical shifts of ³¹P of the Al‐phosphate precipitates were more negative than those of the surface phosphates at a given pH and solution concentration, probably because of a larger number of P–O–Al linkages per tetrahedron. The observed trend of decreasing shielding is probably due to the decreasing average number of P–O–Al linkages per tetrahedron combined with decreasing protonation and an increasing number of K⁺ next‐nearest neighbours. Even at small concentrations of phosphate solution, a significant amount of Al‐phosphate precipitate was present.     

Einfluß langjähriger Düngung mit verschiedenen N-Formen auf die Phosphat-Dynamik einer Ackerbraunerde

Influence of long-term application of different nitrogen sources on the dynamics of phosphate in an arable brown earth In a long-term field experiment parameters of the soil phosphate status were determined after 53 years. Soil characteristics of the arable brown earth are: sandy silt loam; pH 5,9–6,6; total carbon 0,9%; CEC 13–15 meq/100 g soil; effective field capacity 160 mm unto 150 cm. The following results were obtained: Total P content was slightly higher in the plots without mineral N and with farm manure (90 and 93 mg P/100 g soil resp.) than in the plots with mineral N supply (Ø 85 mg P/100 g soil). Application of farm yard manure and ammonium sulfate caused higher proportions of ?Fe and Al phosphates”? (56–57% of inorganic phosphate) whereas calcium cyanamide, calcium nitrate and ammonium sulfate with annual liming led to higher a content of Ca-phosphate (52–56% of inorganic phosphate). When pH was brought to 6,5 by liming, P uptake of rye grass and green oats/green rape-seed in a pot experiment depended on the soil content of ?Fe- and Al-phosphates”?. Without liming, P uptake was lower in the plot with ammonium sulfate, however, in the calcium cyanamide plot P uptake was higher than expected from the content of ?Fe- and Al-phosphate”?.     

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.     

The effect of moisture on nitrous oxide emissions from soil and the N<Subscript>2</Subscript>O/(N<Subscript>2</Subscript>O+N<Subscript>2</Subscript>) ratio under laboratory conditions

Nitrous oxide (N₂O) contributes to greenhouse effect; however, little information on the consequences of different moisture levels on N₂O/(N₂O+N₂) ratio is available. The aim of this work was to analyze the influence of different soil moisture values and thus of redox conditions on absolute and relative emissions of N₂O and N₂ at intact soil cores from a Vertic Argiudoll. For this reason, the effect of water-filled porosity space (WFPS) values of soil cores of 40, 80,100, and 120% (the last one with a 2-cm surface water layer) was investigated. The greatest N₂O emission occurred at 80% WFPS treatment where conditions were not reductive enough to allow the complete reduction to N₂. The N₂O/(N₂O+N₂) ratio was lowest (0–0.051) under 120% WFPS and increased with decreasing soil moisture content. N₂O/(N₂O+N₂) ratio values significantly correlated with soil Eh; redox conditions seemed to control the proportion of N gases emitted as N₂O. N₂O emissions did not correlate satisfactorily with N₂O/(N₂O+N₂) ratio values, whereas they were significantly explained by the amount of total N₂O+N₂ emissions.     

Soil N<Subscript>2</Subscript>O emissions and N<Subscript>2</Subscript>O/(N<Subscript>2</Subscript>O+N<Subscript>2</Subscript>) ratio as affected by different fertilization practices and soil moisture

The objective of this work was to evaluate the effect of the chemical nature and application frequency of N fertilizers at different moisture contents on soil N₂O emissions and N₂O/(N₂O+N₂) ratio. The research was based on five fertilization treatments: unfertilized control, a single application of 80 kg ha⁻¹ N-urea, five split applications of 16 kg ha⁻¹ N-urea, a single application of 80 kg ha⁻¹ N–KNO₃, five split applications of 16 kg ha⁻¹ N–KNO₃. Cumulative N₂O emissions for 22 days were unaffected by fertilization treatments at 32% water-filled pore space (WFPS). At 100% and 120% WFPS, cumulative N₂O emissions were highest from soil fertilized with KNO₃. The split application of N fertilizers decreased N₂O emissions compared to a single initial application only when KNO₃ was applied to a saturated soil, at 100% WFPS. Emissions of N₂O were very low after the application of urea, similar to those found at unfertilized soil. Average N₂O/(N₂O+N₂) ratio values were significantly affected by moisture levels (p = 0.015), being the lowest at 120% WFPS. The N₂O/(N₂O+N₂) ratio averaged 0.2 in unfertilized soil and 0.5 in fertilized soil, although these differences were not statistically significant.     

Abundance of transcripts of functional gene reflects the inverse relationship between CH<Subscript>4</Subscript> and N<Subscript>2</Subscript>O emissions during mid-season drainage in acidic paddy soil

Agricultural management significantly affects methane (CH₄) and nitrous oxide (N₂O) emissions from paddy fields. However, little is known about the underlying microbiological mechanism. Field experiment was conducted to investigate the effect of the water regime and straw incorporation on CH₄ and N₂O emissions and soil properties. Quantitative PCR was applied to measure the abundance of soil methanogens, methane-oxidising bacteria, nitrifiers, and denitrifiers according to DNA and mRNA expression levels of microbial genes, including mcrA, pmoA, amoA, and nirK/nirS/nosZ. Field trials showed that the CH₄ and N₂O flux rates were negatively correlated with each other, and N₂O emissions were far lower than CH₄ emissions. Drainage and straw incorporation affected functional gene abundance through altered soil environment. The present (DNA-level) gene abundances of amoA, nosZ, and mcrA were higher with straw incorporation than those without straw incorporation, and they were positively correlated with high concentrations of soil exchangeable NH₄⁺ and dissolved organic carbon. The active (mRNA-level) gene abundance of mcrA was lower in the drainage treatment than in continuous flooding, which was negatively correlated with soil redox potential (Eh). The CH₄ flux rate was significantly and positively correlated with active mcrA abundance but negatively correlated with Eh. The N₂O flux rate was significantly and positively correlated with present and active nirS abundance and positively correlated with soil Eh. Thus, we demonstrated that active gene abundance, such as of mcrA for CH₄ and nirS for N₂O, reflects the contradictory relationship between CH₄ and N₂O emissions regulated by soil Eh in acidic paddy soils.     

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).     

An assessment of factors controlling N<Subscript>2</Subscript>O and CO<Subscript>2</Subscript> emissions from crop residues using different measurement approaches

Management of plant residues plays an important role in maintaining soil quality and nutrient availability for plants and microbes. However, there is considerable uncertainty regarding the factors controlling residue decomposition and their effects on greenhouse gas (GHG) emissions from the soil. This uncertainty is created both by the complexity of the processes involved and limitations in the methodologies commonly used to quantify GHG emissions. We therefore investigated the addition of two soil residues (durum wheat and faba bean) with similar C/N ratios but contrasting fibres, lignin and cellulose contents on nutrient dynamics and GHG emission from two contrasting soils: a low-soil organic carbon (SOC), high pH clay soil (Chromic Haploxerert) and a high-SOC, low pH sandy-loam soil (Eutric Cambisol). In addition, we compared the effectiveness of the use of an infrared gas analyser (IRGA) and a photoacoustic gas analyser (PGA) to measure GHG emissions with more conventional gas chromatography (GC). There was a strong correlation between the different measurement techniques which strengthens the case for the use of continuous measurement approaches involving IRGA and PGA analyses in studies of this type. The unamended Cambisol released 286% more CO₂ and 30% more N₂O than the Haploxerert. Addition of plant residues increased CO₂ emissions more in the Haploxerert than Cambisol and N₂O emission more in the Cambisol than in the Haploxerert. This may have been a consequence of the high N stabilization efficiency of the Haploxerert resulting from its high pH and the effect of the clay on mineralization of native organic matter. These results have implication management of plant residues in different soil types.     

N<Subscript>2</Subscript>O,CO<Subscript>2</Subscript>, Production,and C Sequestration in Vineyards: a Review

Even if it is less polluting than other farm sectors, grape growing management has to adopt measures to mitigate greenhouse gas (GHG) emissions and to preserve the quality of grapevine by-products. In viticulture, by land and crop management, GHG emissions can be reduced through adjusting methods of tillage, fertilizing, harvesting, irrigation, vineyard maintenance, electricity, natural gas, and transport until wine marketing, etc. Besides CO₂, nitrous oxide (N₂O) and methane (CH₄), released from fertilizers and waste/wastewater management are produced in vineyards. As the main GHG in vineyards, N₂O can have the same harmful action like large quantities of CO₂. Carbon can be found in grape leaves, shoots, and even in fruit pulp, roots, canes, trunk, or soil organic matter. C sequestration in soil by using less tillage and tractor passing is one of the efficient methods to reduce GHG in vineyards, with the inconvenience that many years are needed for detectable changes. In the last decades, among other methods, cover crops have been used as one of the most efficient way to reduce GHG emissions and increase fertility in vineyards. Even if we analyze many references, there are still limited information on practical methods in reducing emissions of greenhouse gases in viticulture. The aim of the paper is to review the main GHG emissions produced in vineyards and the approached methods for their reduction, in order to maintain the quality of grapes and other by-products.     

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.     

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.     

ADSORPTION ON HYDROUS OXIDES. III. FULVIC ACID AND HUMIC ACID ON GOETHITE, GIBBSITE AND IMOGOLITE

Adsorption isotherms were obtained for fulvic and humic acids on synthetic gibbsite and goethite and on a natural imogolite. The results were interpreted with the help of spectra of the adsorption complexes, and measurements of hydroxyl displaced. The mechanism of adsorption involved ligand exchange with the surface hydroxyl groups and hydrogen bonding. The hydroxyl groups displaced included singly coordinated species on the (100) face of goethite and on the edge faces of gibbsite. The doubly coordinated hydroxyl groups on the (001) face of gibbsite were not replaced, and this face adsorbed only un-ionized fulvic acid probably by a hydrogen bonding mechanism. Imogolite adsorbed most fulvic acid because of its high porosity. Only isolated places on its surface reacted with fulvic acid to form carboxylate groups.