Halloysite nanotubes as hydrogen storage materials

The hydrogen adsorption capacities of halloysite nanotubes (HNTs), subjected to different treatments, were investigated at room temperature. The three different treatments included thermal, acid, and palladium modification. The hydrogen adsorption capacity of the HNTs was 0.436 % at 2.63 MPa and 298 K whereas those of the thermally treated HNTs, palladium-modified HNTs (Pd-HNTs), and acid-treated HNTs (A-HNTs), under the same conditions, were 0.263, 1.143, and 1.371 %, respectively. The hydrogen adsorption capacities of both HNTs and treated HNTs are among the highest values reported in the literature so far. Large surface areas were advantageous in promoting hydrogen adsorption via a physisorption mechanism, which was directly related to the aluminosilicate structure of HNTs. It was also possible to enhance the hydrogen adsorption capacity through a chemisorption or spillover mechanism by modifying HNTs with Pd. The HNTs and treated HNTs show potential as physisorption-based mediums for hydrogen storage at room temperature, in particular HNTs and A-HNTs show excellent stability and high hydrogen adsorption capacities.     

Co3O4 nanoparticles on the surface of halloysite nanotubes

Co₃O₄ nanoparticles were successfully deposited on the surface of natural halloysite nanotubes (HNTs) to produce Co₃O₄/HNTs composites. The structure and morphology of the samples were characterized using X-ray diffraction, field-emission scanning electron microscope, transmission electron microscope and Fourier transform infrared. The results indicated that Co₃O₄ nanoparticles were uniformly attached on the surface of HNTs with narrow size distribution. Co₃O₄/HNTs exhibited an excellent photocatalytic efficiency for degradation of methyl blue under UV light, better than Co₃O₄ and HNTs mixture, HNTs and pure Co₃O₄. The mechanism of enhanced photocatalytic activity of Co₃O₄/HNTs was also proposed.     

苏州阳西风化型高岭土矿物的形成与演化

苏州高岭土矿床可划分为两种成因类型^[1,2],即风化型¹⁾和热液蚀变型。高岭土集中分布在阳山东、西、北三个矿区。本文仅就阳西风化型高岭土中产出的不同种类高岭土矿物的形成及其互相演变的关系作初步探讨。     

Significance of co-immobilized activated carbon and Bacillus subtilis on removal of Cr(VI) from aqueous solutions

Batch sorption system using co-immobilized (activated carbon and Bacillus subtilis) beads as adsorbent was investigated to remove Cr(VI) from aqueous solution. Fourier transform infrared spectroscopy analysis showed the functional groups of both bacteria and activated carbon in co-immobilized beads. Experiments were carried out as a function of contact time (5–300 min), initial metal concentration (50–200 mg L^?1), pH (2–8), and adsorbent dose (0.2–1 g L^?1). The maximum percentage of removal was found to be 99 %. Langmuir model showed satisfactory fit to the equilibrium adsorption data of co-immobilized beads. The kinetics of the adsorption followed pseudo-second-order rate expression, which demonstrates that chemisorption plays a significant role in the adsorption mechanism. The significant shift in the Fourier transform infrared spectroscopy peaks and a Cr peak in the scanning electron microscope–energy dispersive spectroscopy spectra further confirmed the adsorption. The results indicate that co-immobilized beads can be used as an effective adsorbent for the removal of Cr(VI) from the aqueous solution.     

Mesoporous material Al-MCM-41 from natural halloysite

Aluminum-containing hexagonally ordered mesoporous silica (Al-MCM-41) with specific surface area of 509.4 m²/g was first synthesized using natural halloysite as source material by hydrothermal treatment, without addition of silica or aluminum regents. The samples were characterized by X-ray diffraction, transmission electron microscopy, N₂ adsorption–desorption measurements, and Fourier transform infrared spectra techniques. The results indicate that process parameters, including calcination temperature, pH value, n(SiO₂)/n(CTAB)/n(H₂O) ratio, and hydrothermal reaction time, show moderate effects on the preparation of Al-MCM-41. SiO₂/Al₂O₃ molar ratio could be effectively modulated by the calcination temperature for halloysite. Furthermore, we first clarified the structural evolution from natural halloysite to mesoporous material Al-MCM-41 at the atomic level.     

Kinetic and equilibrium study of Ni(II) sorption from aqueous solutions onto Peganum harmala-L

In this study, the adsorption behavior of Ni(II) in an aqueous solution system using natural adsorbent Peganum harmala-L was measured via batch mode. The prepared sorbent was characterized by scanning electron microscope, Fourier transform infrared spectroscopy, N₂ adsorption–desorption and pH_zpc. Adsorption experiments were carried out by varying several conditions such as contact time, metal ion concentration and pH to assess kinetic and equilibrium parameters. The equilibrium data were analyzed based on the Langmuir, Freundlich, Temkin and Dubinin–Radushkevich isotherms. Kinetic data were analyzed using the pseudo-first-order, pseudo-second-order and intra-particular diffusion models. Experimental data showed that at contact time 60 min, metal ion concentration 50 mg/L and pH 6, a maximum amount of Ni(II) ions can be removed. The experimental data were best described by the Langmuir isotherm model as is evident from the high R ² value of 0.988. The adsorption capacity (q _m) obtained was 68.02 mg/g at an initial pH of 6 and a temperature of 25 °C. Kinetic studies of the adsorption showed that equilibrium was reached within 60 min of contact and the adsorption process followed the pseudo-first-order model. The obtained results show that P. harmala-L can be used as an effective and a natural low-cost adsorbent for the removal of Ni(II) from aqueous solutions.     

湖南辰溪仙人湾埃洛石型高岭土矿床特征及成因分析

在野外地质矿化特征调查的基础上,通过化学成分分析、光学显微镜、红外吸收光谱、X射线衍射、扫描电镜等手段,对新发现的湖南辰溪仙人湾埃洛石型高岭土矿床特征及成因进行研究发现:此高岭土矿体呈似层状与囊状形态,就位于二叠系/石炭系角度不整合面及二叠统/下二叠统假整合面上,分布在岩溶洞穴体系中。矿石中主要矿物为1nm管状埃洛石,部分为0.7 nm管状埃洛石,原生带矿石中埃洛石的含量达95%以上。该高岭土矿床为次生淋滤胶体溶液沉积-重结晶成因高岭土矿床矿床,系温暖湿润、岩溶发育的环境中,受强淋滤作用,由来自上覆地层砂页岩、煤层、泥灰岩及泥质灰岩中的硅铝物质经过相对富集,形成硅铝溶胶,迁移,在岩溶洞穴中沉淀并再次富集成为凝胶体,脱水老化形成埃洛石。     

The products of the interaction of feldspars with aqueous solutions at 25°C

Chemical analyses of 300 solutions produced by the artificial weathering of eight different feldspars in fourteen experiments of up to 1200hr duration were used to study the evolution of water during weathering. The range of pH was between 4 and 5·5. Within 4 hr of dissolution, the activity of Al was controlled by the pH and the solubility of microcrystalline gibbsite. After 100 hr of dissolution, the pH and microcrystalline halloysite controlled the activities of Al and silicic acid in all of the solutions.Microcrystalline halloysite was the only phase identified in the weathering of plagioclases in distilled water and 1 atm CO₂ partial pressure. Montmorillonites, halloysite and other clay minerals were produced from oligoclase in aqueous solutions containing high initial concentrations of Ca. Mg, K and SiO₂.The experimentally determined log solubility product of microcrystalline gibbsite was ?32·78 ± 0·04 and log $\text{K}$ for the hydrolysis of microcrystalline halloysite was 11.58 ± 0·05. The results suggest that very poorly crystalline metastable phases may control the initial compositions of some waters in contact with rocks containing feldspar minerals.     

NaOH-treated dead leaves of <Emphasis Type="Italic">Ficus racemosa</Emphasis> as an efficient biosorbent for Acid Blue 25 removal

A novel biosorbent synthesized from Ficus racemosa leaves based on the treatment using NaOH was applied for removal of Acid Blue 25 from aqueous solution. The synthesized biosorbent was characterized using scanning electron microscopy, Fourier transform infrared spectroscopy and Brunauer–Emmett–Teller analysis. NaOH treatment was demonstrated to remove lignin content from the biomass and to induce the development of significant pores. Batch experiments were performed to evaluate the effect of important operating parameters such as pH (range of 2–10), biosorbent dose (range of 1–10 g/L), contact time (range of 0–5 h), initial dye concentration (range of 50–400 mg/L) and temperature (range of 293–323 K) on the extent of removal of Acid Blue 25. The established optimum conditions were pH of 2, biosorbent dose of 4 g/L, contact time of 3 h and temperature of 323 K, yielding maximum removal of dye. Pseudo-second-order model was found to best fit the kinetic data. Langmuir and Temkin isotherm models were found to best fit the equilibrium data. The obtained thermodynamic parameters confirmed endothermic and spontaneous nature of adsorption. The study established the utility of novel biosorbent for removal of Acid Blue 25 with higher adsorption capacities (83.33 mg/g) as compared to the more commonly used adsorbents. Desorption-adsorption  studies conducted for seven cycles indicated potential reusability of synthesized biosorbent for the treatment of dye effluents.     

Rheological characteristics of mixed kaolin–sand slurry,impacts of pH,temperature, solid concentration and kaolin–sand mixing ratio

Significant amount of slurry waste is produced from mineral processing plants globally constituting high levels of both kaolin and sand in aqueous suspension. Large quantities of slurry and mine tailings require efficient handling, transportation and storage system. The transportation and treatment of kaolin–sand slurry is dependent on its rheological behaviour which is a function of temperature, total solid concentration and pH. In this study, the effects of total solid concentration, pH and temperature on rheological behaviour of kaolin–sand mixture were investigated. These parameters were varied to analyse the viscosity, yield stress, flow index and shear force requirements of the mixed kaolin–sand suspension as a function of these varying parameters. Experimental rheological investigation conducted on rotational stress-controlled rheometer equipped with Peltier concentric cylinder system showed that the kaolin–sand mixture suspension is shear thickening in nature. The shear stress-rate rheograms for the kaolin–sand suspension can be modelled by the Herschel–Bulkley model with high levels of accuracy for pH range of 4–11, temperature range of 20–50 °C and solid concentration of 5–50 %. Solid concentration of the suspension was found to significantly affect the rheological behaviour of the mixture where higher kaolin–sand slurry concentration resulted in greater viscosity and the trend becoming less predictable for solid concentration greater than 50 % by weight. pH was another factor affecting the rheological behaviour of kaolin–sand slurry. pH of 3 or less resulted in the dramatic increase of viscosity of the suspension possibly due to the isoelectric point of the mixture system found between pH of 3 and 4.     

Novel preparation of sensitized ZnS nanoparticles and its use in photocatalytic degradation of tetracycline

Sensitized ZnS nanoparticles were synthesized by chemical precipitation method using anthocyanin as the capping agent and sensitizer. X-ray diffractometer, field-emission scanning electron microscope, transmission electron microscopy, UV visible spectrophotometer, Fourier transform infrared spectroscopy and photoluminescence spectrometry methods were used for the characterization of nanoparticles. The electron microscopy studies of nanoparticles showed that the size of crystallites is in the range of 35–80 nm and optical studies showed a blue shift in the absorption edge by adding capping agent. The effective band gap energy was increased with decrease in the particle size. Photocatalytic activities of sensitized ZnS and pure ZnS were evaluated by degradation of tetracycline in aqueous solution under visible light irradiation, and progress of the reaction was monitored spectrophotometrically. The different parameters affecting degradation such as the pH of solution, amount of semiconductor and reusability of catalyst for three cycles and the photocatalytic degradation kinetics of tetracycline were studied. More than 80% degradation was achieved within 5 h under visible light.     

Preparation and characterization of biosorbents and copper sequestration from simulated wastewater

This paper reports the potential of chemically treated wood chips to remove copper (II) ions from aqueous solution a function of pH, adsorbent dose, initial copper (II) concentration and contact time by batch technique. The wood chips were treated with (a) boiling, (b) formaldehyde and (c) concentrated sulphuric acid and characterized by Fourier transform infrared spectroscopy, scanning electron microscopy and energy dispersive analysis X-ray. pH 5.0 was optimum with 86.1, 88.5 and 93.9 % copper (II) removal by boiled, formaldehyde-treated and concentrated sulphuric acid-treated wood chips, respectively, for dilute solutions at 20 g L^?1 adsorbent dose. The experimental data were analysed using Freundlich, Langmuir, Dubinin–Radushkevich and Temkin isotherm models. It was found that Freundlich and Langmuir models fitted better the equilibrium adsorption data and the adsorption process followed pseudo-second-order reaction kinetics. The results showed that the copper (II) is considerably adsorbed on wood chips and it could be an economical option for the removal of copper from aqueous systems.     

Removal of anthropogenic lead pollutions by a potent <Emphasis Type="Italic">Bacillus</Emphasis> species AS2 isolated from geogenic contaminated site

A total of 422 bacterial isolates were obtained from the lead (Pb) ore in north-eastern Iran. The Pb tolerances of these strains were studied using microbroth serial dilution approach and 35 strains could grow up to 3250 ppm Pb concentration. Of these strains, 10 of them represented qualitatively high levels of Pb adsorption and were selected for quantitative studies. Strain AS2 which is phylogenetically related to genus Bacillus showed the highest level of Pb remediation. The effects of different factors, including pH, initial Pb concentration, temperature and inoculum size, were studied on the remediation process. Pb remediation capacity was reached at 74.5 mg/g (99.5 % of initial Pb) at pH 4.5, temperature 30 °C, inoculum size 1.0 % (v/v) and an initial Pb concentration of 500 ppm after 24 h. Pb desorption capacity of strain was 66 %. The novel isolate could remove 98 % of Pb from the contaminated industrial wastes after 24 h. Pb uptaking to the cell surface was proven using scanning electron microscopic micrograph and energy-dispersive X-ray spectroscopy analysis. Most Pb removal efficiency was observed in the active cell culture as compared to the inactive cell and extracellular polymeric substances. The novel strain represents a good candidate for removal of environmental anthropogenic Pb pollutions.     

Assessment of Cement Kiln Dust-Treated Expansive Soil for the Construction of Flexible Pavements

An expansive soil (black cotton soil) treated with up to 10 % cement kiln dust (CKD), a waste obtained from the manufacture of cement, was evaluated for use as a flexible pavement construction material. Laboratory tests were carried out on specimens compacted with British Standard light, British Standard light or standard Proctor (relative compaction = 100 %) energy. Results obtained show that the index properties of the soil improved with CKD treatment. Peak unconfined compressive strength of 357.07 kN/m² and California bearing ratio (CBR) of 7 % as well as resistance to loss in strength of 44 % were recorded at 10 % CKD treatment. Reduction in the particle sizes with curing period was observed when samples were viewed through the scanning electron microscope. The study showed that CKD can be beneficially used to improve the subgrade of lightly trafficked roads and as admixture in lime stabilization during construction of flexible pavements over expansive soil.     

Removal of phosphorus from water using scallop shell synthesized ceramic biomaterials

This study describes the development of scallop shell synthesized ceramic biomaterial for phosphorus removal from water. The synthesized biomaterial was characterized by scanning electron microscope, Brunauer–Emmett–Teller and X-ray diffractometer methods. The influences of contact time, initial phosphate concentration, initial solution pH, co-existing ions and temperature for phosphorus removal were investigated by batch experiments. The results indicated that the equilibrium data can be fitted by the Langmuir isotherm model at temperatures ranging from 15 to 55 °C, with the maximum sorption capacity of 13.6 mg/g. Sorption kinetics followed a pseudo-second-order kinetic equation model. The sorption process was optimal at a wide range of solution pH (above 2.4), with a relatively high sorption capacity level. Phosphorus sorption was slightly impeded by the presence of F^?, HCO₃ ^? and NH₄ ⁺ ions, and significantly inhibited by Cl^?, SO₄ ^2? and NO₃ ^? ions. Sorption process appeared to be controlled by a chemical precipitation processes. The mechanism may be attributed to ion complexation during subsequent sorption of phosphorus on scallop shell synthesized ceramic biomaterial.     

Lead and nickel biosorption with a fungal biomass isolated from metal mine drainage: Box–Behnken experimental design

The Pb(II) and Ni(II) biosorption of a fungal biomass isolated from mine drainage of metal-processing industries in Balya (Bal?kesir province, Turkey) was optimized using a response surface methodology by altering parameters such as pH, initial metal concentration, contact time and biosorbent dosage. This strain was shown to be highly similar to Penicillium sp. Furthermore, zeta potential measurements and Fourier transform infrared spectroscopy were performed to understand the adsorption mechanism. A Box–Behnken design with 29 experiments was used to evaluate the interactions between independent variables. The results showed that the fungal biomass isolated from the metal mine drainage could have a significant environmental impact through the biosorption of Pb(II) and Ni(II) in waters polluted with heavy metals, particularly in the drainage from metal mines. The maximum removal values were 76 and 47 % at pH 4.5 for both Pb(II) and Ni(II), with 123 and 33 mg/L initial metal concentrations, 65 and 89 min contact times and 0.2 and 1.6 g/L biosorbent, respectively.     

Direct analysis of microaggregates shrinkage for drying: Application to microaggregates from a Brasilian clayey Ferralsol

Subrounded microaggregates 100 to 500 μm in diameter were collected in a Ferralsol located in the state of Goiàs. Observation of these microaggregates in dry conditions in scanning electron microscopy showed morphological characteristics that are representative of microaggregates described earlier in many Ferralsols. The shrinkage for drying of initially water saturated microaggregates was studied using an environmental scanning electron microscope. Results showed very small shrinkage for the microaggregates usually studied. However, the shrinkage varies since the volume of dried microaggregates was found to be 93 to 99% of their volume when they are saturated. To cite this article: N. Volland-Tuduri et al., C. R. Geoscience 336 (2004).     

Heating–freezing effects on the pore size distribution of a kaolinite clay

This study aims to quantify the effect of heating and freezing temperatures on the pore size distribution of saturated clays. Three kaolinite clay specimens were subjected to different temperatures: 20, 70, and ? 10 °C. Upon achieving the desired temperature for each specimen, the specimens were flash frozen in liquid nitrogen to preserve their microstructure. Each specimen was, then, freeze-dried for 24 h after which consecutive two-dimensional (2-D) SEM images were taken using a dual focused ion beam/scanning electron microscope. The produced 2-D images of each specimen were used to reconstruct three-dimensional tomographies of the specimens, which were analyzed to determine the pore size distribution at each temperature. Compared to the specimen at room temperature, the pores in the specimen subjected to ? 10 °C were larger; this is believed to be due to the formation of ice lenses inside the pores upon freezing and potential merging between initial pores to form larger pores. On the other hand, the heated specimen showed an increase in the volume of the smaller pores and a decrease in the volume of the larger pores compared to the specimen at room temperature. This opposite behavior between the small and large pores in the heated specimen is justified considering (1) the easier flow of water out of the larger pores compared to that in the smaller pores and (2) the anisotropic nature of the thermal expansion of the clay particles.     

Novel sensible thermal storage material from natural minerals

Novel sensible thermal storage materials (TSM) were first synthesized via thermally treating the green compact obtained using clay, kaolin tailings, and hematite as major raw materials. The samples were characterized using differential scanning calorimetry and thermogravimetric, X-ray diffraction, thermal conductivities, petrography analysis, Fourier transformation infrared spectroscopy, and scanning electron microscopy. The thermal conductivity of the green compact reached 1.11–1.64 W m^?1 K^?1 after thermally treated at 200–1,000 °C. The clay component was proven to have a predominant effect on the thermal conductivity of the green compact. Kaolin tailings could act as a “modulator” for adjusting the thermal conductivity from 1.42 to 1.92 W m^?1 K^?1. Affecting mechanism of microstructural change of main components during sintering on thermal conductivity of TSM was prominently investigated. TSM could provide a potential candidate for thermal energy storage systems of concentrated solar power.