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Copper Speciation in Soil: Time Evolution and Effect of Clay Amendment
2015
Montenegro, Andrea C. | Ferreyroa, Gisele V. | Parolo, María E. | Tudino, Mabel B. | Lavado, Raúl S. | Molina, Fernando V.
Copper bioavailability, specially to plants, is strongly dependent on its chemical form, as for most metals. Copper-contaminated soil can be treated in situ by the addition of minerals such as Na-bentonite, which mixed with surface soil, can transform this pollutant to non-bioavailable forms. In this work, shelter experiments were conducted to study the time evolution of Cu speciation, in pristine soil as well as in amended one. A selective sequential extraction method was employed to determine the metal speciation in the samples. The results show that the major metal fraction is the organic matter-bound one, whereas the exchangeable fraction is very low, even the first day after Cu addition. The time evolution shows a slow decrease of the organic-bound Cu and a corresponding increase of the most stable mineral fractions. With the addition of Na-bentonite to copper-contaminated soil, the most stable mineral fractions increase whereas the organic-bound one decreases, showing essentially similar time dependence of the several metal fractions. Sodium bentonite could be effectively used for remediation of soils polluted with Cu.
Show more [+] Less [-]Effectiveness and Mode of Action of Calcium Nitrate and Phoslock® in Phosphorus Control in Contaminated Sediment, a Microcosm Study
2015
Lin, Juan | Qiu, Peihuang | Yan, Xiangjun | Xiong, Xiong | Jing, Liandong | Wu, Chenxi
Calcium nitrate and a lanthanum-modified bentonite (Phoslock®) were investigated for their ability to control the release of phosphorus from contaminated sediment. Their effectiveness and mode of action were assessed using microcosm experiments by monitoring the variation of physiochemical parameters and phosphorus and nitrogen species over time following the treatment for 66 days. Phoslock® was more effective reducing phosphorus in overlaying water and controlling its release from sediment. Calcium nitrate improved redox condition at the sediment-water interface and temporally reduce phosphorus in overlaying water but phosphorus level returned back in a long run. Phosphorus fractionation suggested that Phoslock® converted mobile phosphorus to more stable species while calcium nitrate increased the fractions of mobile phosphorus species. Phoslock® generally showed no effect on nitrogen species. Whereas calcium nitrate temporally increased nitrate, nitrite, and ammonium concentrations but their concentrations quickly reduced likely due to the denitrification process. Results suggested that Phoslock® can be more effective in controlling the release of phosphorus from sediment than calcium nitrate. However, calcium nitrate can improve the redox condition at the sediment-water interface, which may provide other benefits such as stimulating biodegradation.
Show more [+] Less [-]Adsorption of Cobalt(II) from Aqueous Solutions by Fe3O 4/Bentonite Nanocomposite
2015
Hashemian, Saeedeh | Ṣaffārī, Ḥusayn | Ragabion, Saeedeh
Fe₃O₄and Fe₃O₄/bentonite were prepared by chemical co-precipitation method. They were characterized by X-ray powder diffraction (XRD), Fourier infrared spectroscopy (FTIR), and transmission electron microscope (TEM). Adsorption of cobalt(II) on the bentonite, Fe₃O₄, and Fe₃O₄/bentonite nanocomposite was studied. The results indicated that the metal oxides mainly occurred in the form of spinel structure of Fe₃O₄and the presence of Fe₃O₄significantly affect the surface area and pore structure of the bentonite. The specific surface area (Brunauer–Emmett–Teller (BET) method) of bentonite, Fe₃O₄, and Fe₃O₄/bentonite were determined to be 34.44, 98.44, and 140.5 m² g⁻¹, respectively. TEM image of Fe₃O₄/bentonite shows the particle diameter at 10 nm. The maximum adsorption capacity of cobalt(II) by Fe₃O₄/bentonite nanocomposite was determined to be 18.76 mg g⁻¹. The adsorption strongly depends on pH, where the removal efficiency increases as the pH turns to alkaline range (pH 9). The results suggest that higher adsorption capacity of composite than bentonite is attributed to the presence of Fe₃O₄. The adsorption process follows pseudo-second-order kinetics. The equilibrium data was analyzed by Langmuir model showing high correlation coefficient. The thermodynamic study of adsorption process showed that the adsorption of Co(II) onto Fe₃O₄/bentonite was carried out spontaneously.
Show more [+] Less [-]Removal of Phosphate from Aqueous Solutions by Chemical- and Thermal-Modified Bentonite Clay
2015
Tanyol, Mehtap | Yonten, Vahap | Demir, Veysel
The study investigated phosphate adsorption from aqueous solutions using chemical- and thermal-modified bentonite in batch system. The adsorbent was characterized by SEM, BET, and FTIR spectroscopy. Contact time, beginning phosphate concentration, pH of the solution, and the effects of the temperature on phosphate adsorption capacity were determined by a series of experimental studies. In a wide pH range (3–10), high phosphate removal yields were obtained (between 94.23 and 92.26 %), and with the increase in temperature (from 25 to 45 °C), phosphate removal increased. Langmuir and Freundlich isotherms were used to determine the sorption equilibrium, and the results demonstrated that equilibrium data displayed better adjustment to Langmuir isotherm than the Freundlich isotherm. Phosphate sorption capacity, calculated using Langmuir equation, is 20.37 mg g⁻¹ at 45 °C temperature and pH 3. Mass transfer and kinetic models were applied to empirical findings to determine the mechanism of adsorption and the potential steps that control the reaction rate. Both external mass transfer and intra-particle diffusion played a significant role on the adsorption mechanism of phosphate, and adsorption kinetics followed the pseudo-second-order-type kinetic. Furthermore, thermodynamic parameters (ΔH°, ΔG°, ΔS°) which reveal that phosphate adsorption occur spontaneously and in endothermic nature were determined. The results of this study support that bentonite, which is found abundant in nature and modified as an inexpensive and effective adsorbent, could be used for phosphate removal from aqueous solutions.
Show more [+] Less [-]Deployment of Microbial Biosensors to Assess the Performance of Ameliorants in Metal-Contaminated Soils
2015
Maletić, Snežana P. | Watson, Malcolm A. | Dehlawi, Saad | Diplock, Elizabeth E. | Mardlin, David | Paton, Graeme I.
The remediation of metal-impacted soils requires either the enhanced mobility (and capture) of the target analytes or their effective complexation/immobilisation. In this study, a range of ameliorants (activated carbon, bonemeal, bentonite and CaSx (calcium polysulphide)) were compared to assess their effectiveness in immobilising metals in soils. In addition to chemical analysis (pH and trace element analysis), microbial biosensors were used to assess changes in the water-soluble biotoxicity of metals as a consequence of ameliorant dosing. Management of soil ameliorants requires an enhancement of K d (solid/solution partition coefficient) if soil leachate is to meet predefined environmental quality standards. Of the ameliorants tested, CaSx was the most effective per unit added for both laboratory-amended and historically contaminated soils, regardless of the metal tested. At the ameliorant concentrations used to effectively immobilise the metals, the biosensor performance was not impaired. Microbial biosensors offered a rapid and relevant screening tool to validate the reduced toxicity associated with the ameliorant dosing and could be calibrated to complement chemical analysis. While laboratory-amended soils were a logical way to evaluate the performance of the ameliorants, they were generally associated with K d values an order of magnitude lower than those of historically contaminated soils.
Show more [+] Less [-]Modification of bentonite with cationic surfactant for the enhanced retention of bisphenol A from landfill leachate
2015
Li, Yi | Jin, Fenglai | Wang, Chao | Chen, Yunxiao | Wang, Qing | Zhang, Wenlong | Wang, Dawei
Bentonite was modified with cationic surfactant hexadecyl trimethyl ammonium bromide (HTAB) as landfill liner to retard the transportation of bisphenol A (BPA) for the first time. The modification was confirmed to form a lateral bi-layer in the interlayer space of bentonite by scanning electron microscope, X-ray diffraction, and Fourier transform infrared spectroscopy. The introduction of HTAB into the internal position of bentonite led to an increased interlayer space of bentonite from 15.0 to 20.9 Å and a higher sorption affinity for BPA (10.449 mg/g of HTAB-bentonite and 3.413 mg/g of raw bentonite). According to the Freundlich model, the maximum adsorption capacity of the HTAB-bentonite was found to be 0.410 mg/g. The sorption capacity of raw bentonite and HTAB-bentonite both decreased at alkaline conditions. Although the hydraulic conductivity of HTAB-bentonite was higher than that of raw bentonite, results of laboratory permeability and column tests indicated that HTAB-bentonite obviously extended the BPA breakthrough time by 43.4 %. The properties of the HTAB-bentonite revealed its notable advantages as components of landfill liners material to retain BPA in leachate.
Show more [+] Less [-]Surfactant-modified bentonite clays: preparation, characterization, and atrazine removal
2015
Dutta, Anirban | Singh, Neera
Bentonite clay was modified using quaternary ammonium cations, viz. phenyltrimethylammonium (PTMA), hexadecyltrimethylammonium (HDTMA), trioctylmethylammonium (TOMA) [100 % of cation exchange capacity of clay], and stearylkonium (SK) [100 % (SK-I) and 250 % (SK-II) of cation exchange capacity of clay]. The organoclays were characterized using X-ray diffraction (XRD), infrared (IR) spectroscopy, and scanning electron microscopy (SEM). Atrazine adsorption on modified clays was studied using a batch method. Bentonite clay was a poor adsorbent of atrazine as 9.4 % adsorption was observed at 1 μg mL⁻¹atrazine concentration. Modification of clay by PTMA cation did not improve atrazine adsorption capacity. However, atrazine adsorption in HDTMA-, TOMA-, and SK-bentonites varied between 49 and 72.4 % and data fitted well to the Freundlich adsorption isotherm (R > 0.96). Adsorption of atrazine in organoclays was nonlinear and slope (1/n) values were <1. The product of Freundlich adsorption constants, Kf(1/n) in HDTMA-, TOMA-, and SK-I-bentonites was 239.2, 302.4, and 256.6, respectively, while increasing the SK cation loading in the clay (SK-II) decreased atrazine adsorption [Kf(1/n) − 196.4]. Desorption of atrazine from organoclays showed hysteresis and TOMA- and SK-I-bentonites were the best organoclays to retain the adsorbed atrazine. Organoclays showed better atrazine removal from wastewater than an aqueous solution. The synthesized organoclays may find application in soil and water decontamination and as a carrier for atrazine-controlled released formulations.
Show more [+] Less [-]Alleviating the toxicity of heavy metals by combined amendments in cultivated bag of Pleurotus cornucopiae
2015
Liu, Hongying | Guo, Shanshan | Jia, Zhilei | Han, Yue | He, Qi | Xu, Heng
The substrate of mushroom can be polluted with heavy metals and subsequently contaminate mushroom, which requires alternative solutions to reduce associated environmental and human health risks. The effects of amendment application on alleviating Cu and Cd toxicities to Pleurotus cornucopiae were investigated in a cultivated bag experiment conducted with the naturally contaminated substrate. Addition of combined amendments (sodium bentonite, silicon fertilizer, activated carbon, and potassium dihydrogen phosphate) increased the P. cornucopiae biomass and substrate pH. Cu and Cd concentration in P. cornucopiae as well as the available Cu and Cd in substrate reduced for the presence of amendments, and the silicon fertilizer had the biggest inhibition on metal uptake. The smallest amount of Cu and Cd in P. cornucopiae was only 30.8 and 5.51 % of control, respectively. Moreover, application of amendments also decreased malondialdehyde (MDA) and hydrogen peroxide (H₂O₂) level in metal-stressed mushroom by 4.38–53.74 and 8.90–58.42 % relative to control, respectively. The decreased oxidative stress could well contribute to the growth of P. cornucopiae, and the elevated substrate pH might lead to the lower metal availability, thus resulting in the reduction of metal accumulation in mushroom. These above results suggest that application of combined amendments in mushroom substrate could be implemented in a general scheme aiming at controlling metal content in P. cornucopiae.
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