Evaluation of natural quartz and zeolitic tuffs for As(V) removal from aqueous solutions: a mechanistic approach

Naturally occurring pyroclastic materials, quartz-rich tuffs (Qz) and stellerite tuffs, were evaluated for their capacities to remove As(V) from aqueous solutions. The mechanism of As(V) uptake was evaluated using sequential extraction of As(V)-loaded adsorbent which entailed that the plausible removal mechanism is sorption to short-range ordered hydrous oxides of iron and aluminum. In addition, buffering effects of adsorbents could form favorable charges upon them through hydrolysis of amphoteric oxides, enhancing the performance of sorption. The influence of anions co-existing with As(V) in water such as carbonate, bicarbonate, nitrate, chloride, phosphate, and sulfate was studied in a batch sorption process. The impact of most anions on As(V) removal was found to be negligible except phosphate. The sorption behavior well fitted to Langmuir and Freundlich models. Estimated maximum sorption capacities of 0.42 and 0.23 mg/L were observed using quartz-rich tuffs and stellerite tuffs, respectively. As(V) concentration of 0.8 mg/L was easily decreased to below the drinking water standard of 0.01 mg/L using Qz adsorbent, whereas 0.1 mg/L As(V) decreased to below this limit upon the use of stellerite tuffs under similar conditions. The buffering capacity of quartz-rich tuffs and stellerite tuffs induced a pH increase to 5.76 and 5.40, respectively, from initial pH of 3.50, which will incur an important asset in real applications.     

季胺盐阳离子插层蒙脱土对铀吸附性能的研究

通过十六烷基三甲基溴化铵（CTMAB）与钠基蒙脱土离子交换制备出季胺盐阳离子插层蒙脱土（CTMA’-M）,采用小角X射线衍射仪、傅里叶变换红外光谱仪和高分辨透射电镜表征微观结构,研究CTMA’的插层量、溶液的初始pH值、初始浓度和其他共存离子对吸附铀性能的影响,考察了CTMA’-M处理铀矿水）台废水的应用性能。结果表明：CTMA’插层后蒙脱土的层间距由1．21nm增加到4．09nm,但仍保持钠基蒙脱土原有的晶体结构。随CTMAB用量的增加,插层到蒙脱土层间的CTMA’量增加,对铀离子的吸附容量逐渐增大,当CTMAB的用量超过阳离子交换容量的1．4倍时,铀吸附容量基本保持不变。溶液pH和接触时间对铀离子吸附性能影响较大．CTMA’-M最佳吸附pH值为6．0,平衡吸附时间为80min,CTMA’插层能够改善蒙脱土对铀离子的选择性吸附。在1L含有15mg／L铀的废水中加入1．5gCTMA’-M时,铀的去除率达到98％以上。     

Evaluating the effectiveness of a hybrid sorbent resin in removing fluoride from water

In some regions of the world, the concentration of fluoride in groundwater is high. To reduce the amount of fluoride to acceptable drinking water standard, it is highly recommended to treat the water. Fluoride adsorption in aqueous solution by a hybrid resin was studied in this research because of its functional groups likeness with goethite. Kinetic data showed that F adsorption was rapid in the beginning and maximum uptake occurred in within 10 min and equilibrium reached within 100 min. The experimental results showed that fluoride adsorption was influenced by pH of solution and optimum operating pH was in the range of 3 to 5.5. Langmuir model was applicable to the present study and F ions were exchanged with hydroxide ions in nano-scaled structure on the surface of sorbent. This adsorbent with 61 % efficiency is suitable for the regions where F concentration is less than 4 mg/L.     

Sorptive removal of ibuprofen from water using selected soil minerals and activated carbon

Pharmaceuticals have gained significant attention in recent years due to the environmental risks posed by their versatile application and occurrence in the natural aquatic environment. The transportation and distribution of pharmaceuticals in the environmental media mainly depends on their sorption behavior in soils, sediment?Cwater systems and waste water treatment plants, which varies widely across pharmaceuticals. Sorption of ibuprofen, a non-steroidal anti-inflammatory drug, onto various soil minerals, viz., kaolinite, montmorillonite, goethite, and activated carbon, as a function of pH (3?C11), ionic strength (NaCl concentration: 0.001?C0.5?M), and the humic acid concentration (0?C1,000?mg/L) was investigated through batch experiments. Experimental results showed that the sorption of ibuprofen onto all sorbents was highest at pH 3, with highest sorption capacity for activated carbon (28.5?mg/g). Among the minerals, montmorillonite sorbed more ibuprofen than kaolinite and goethite, with sorption capacity increasing in the order goethite (2.2?mg/g)?<?kaolinite (3.1?mg/g)?<?montmorillonite (6.1?mg/g). The sorption capacity of the selected minerals increased with increase in ionic strength of the solution in acidic pH condition indicating that the effect of pH was predominant compared to that of ionic strength. An increase in humic acid concentration from low to high values made the sorption phenomena very complex in the soil minerals. Based on the experimental observations, montmorillonite, among the selected soil minerals, could serve as a good candidate to remove high concentrations of ibuprofen from aqueous solution.     

Interactions of copper, organic acids, and sulfate in goethite suspensions

Sorption of copper and sulfate onto goethite (-FeOOH) in aqueous solution is examined in Cu---SO₄ binary-sorbate systems and in Cu-SO₄-organic acid (either phthalic acid or chelidamic acid) ternary-sorbate systems. Compared to single-sorbate systems, sorption of Cu onto goethite was enhanced at low pH values in the presence of sulfate. Sorption data for Cu and SO₄ in Cu---SO₄ binary-sorbate systems were described with the Generalized Two Layer Model by proposing formation of a Cu---SO₄ ternary surface complex. Addition of sulfate to a Cu-phthalic acid binary sorbate system had little effect on Cu sorption. However, addition of sulfate to Cu-chelidamic acid binary-sorbate systems resulted in significant reduction of Cu sorption at low pH values, primarily due to competition for surface sites between sulfate and Cu-chelidamic acid ternary surface complexes. While organic acids such as humic substances can potentially influence sorption of metal ions, results from this study suggest that the extent of such influence may be strongly dependent on the presence of other sorbing anions, such as sulfate. Sorption of Cu and SO₄ in Cu---SO₄-organic acid ternary-sorbate systems was predicted reasonably well, based on surface reactions and equilibrium constants derived from fitting of sorption data from single- and binary-sorbate systems. These modeling results provide a validation of the extrapolation of sorption from simple systems to multicomponent systems through surface complexation modeling.     

Comparison of fast elimination of Cr(VI) by alumina nanofiber and alumina nanoporous

The goal of this study is examination of the mixture between adsorption and permeation process for removing chromium (VI) from the water. Two types of supported membranes are developed: The first one which was made by sol–gel method is called nanoporous and the second one which was made by electrospinning is called nanofiber. The sorption capacity of nanoporous and nanofiber is examined in single batch experiments at various pH values, and it is found that maximum chromium removal is observed for both nanoporous and nanofiber at pH 3.5. Adsorption studies illustrated that the Cr(VI) adsorption onto alumina nanoporous and nanofiber is affected by changes in pH, contact time, dosage of adsorbent, concentration of chromium and solution volume. Langmuir and Freundlich isotherms can be used to explain the adsorption equilibria of Cr(VI) onto alumina nanoporous and nanofiber. It was found that balance adsorption data adequate Langmuir isotherm more than Freundlich model. Adsorption kinetics was found to be fitted to pseudo-second order and Weber and Morris model. The output of multiple linear regressions was run for the second-order response surface model implied that the linear agents of pH, sorbent dosage and Cr(VI) concentration are more significant factors. Manufacturing electrospun alumina nanofiber and sol–gel nanoporous with these cheap materials, renewable and fast methods are so important although the removal percentage is significant.     

Batch and Column Experiments on Fluoride Removal from Waters Using Modified Zeolite

INTRODUCTIONNatural and m odified zeolites have been widely used inboth catalytic conversion processes and adsorption separationprocesses. Recently,because of their unique properties,growing interest has been focused on the zeolites for use in ionexchange separation in water softening,pollution abatem ent,energy production,agriculture,metal processing and biomedi-cal areas. Most of the previous work was concentrated on thecation exchange property of zeolites. Several zeolites werefound to…     

Separation of concentrated acid and salt solutions in nanoporous media as the basis for a new technology of processing of phosphorus-containing raw materials

The physical and mathematical models were used to study the method of acid retardation for separating acids from their salts in concentrated multicomponent solutions using nanoporous sorption materials. A combined mechanism of separation relies on the fact that in the sorption phase having a low dielectric permittivity, smaller-sized acid particles, namely, the molecules or strongly bound and weakly hydrated ion pairs, can penetrate the nanopores and are retained within these pores due to molecular sorption or competitive solvation forces. The dissolved salts presented by highly hydrated ions or weakly bound ion pairs can easily pass through the porous medium with a flow of concentrated solution, which is pumped through the column packed with the granulated bed of gel-type ion exchange resins or hypercrosslinked polymers. In conventional cyclic AR processes, purified acid is desorbed by water according to the mechanism of competitive solvation. However, such processes can be successfully used only when the salts separated from acids are highly soluble, as is the case with chloride and nitrate solutions free of components that may form compounds insoluble in neutral medium. At the separation in real sulfate and phosphate media, which normally contain alkaline earth metals and other components, conventional AR- based technologies proved to be unsuccessful. The new modified version of acid retardation is based on the previously discovered effect of stabilization of colloidal systems and supersaturated solutions in porous ion exchange media. A distinctive feature of the proposed technique is the use of weakly acidic aqueous solutions, instead of water, at the stages of acid displace in the cyclic AR processes. The proposed technique of WPA purification using strong-base gel-type ion exchangers in the phosphate form opens up the possibility of stable and feasible processes of acid separation and purification with simultaneous extraction of valuable components, e.g., REE concentrate.     

黄铁矿净化水中低浓度磷

以产自安徽铜陵新桥矿的黄铁矿为典型样品,研究黄铁矿对磷的吸附作用。静态实验考察黄铁矿粒度、固液比、pH值、离子强度、温度、吸附时间等因素对黄铁矿去除磷效果的影响,XPS和FE-SEM研究吸附磷后黄铁矿颗粒表面形貌和成分特征。结果表明：黄铁矿粒径越小（50～180目）,去除磷效率越高（9.3%～90.7%）;提高固液比（0.2～2 g/L）,磷的去除率增加（6.5%～97.1%）;在pH值3～9.65范围内黄铁矿对磷都有很好的去除效率（95%以上）;NO3-对磷的去除效果表现为微弱的促进作用,Cl-有微弱的抑制作用,溶液中SO42-、HCO3-对黄铁矿吸附磷表现出较强的抑制作用。温度对黄铁矿吸附效率基本没有影响。黄铁矿对磷吸附动态实验表明除磷效率在16 h后接近最大值。除磷作用机理是黄铁矿表面缓慢氧化产生的三价铁对磷的化学吸附。成果表明黄铁矿用于净化污水中低浓度磷具有很大的潜力。     

A zinc oxide-coated nanoporous carbon adsorbent for lead removal from water: Optimization, equilibrium modeling, and kinetics studies

A zinc oxide-coated nanoporous carbon sorbent was prepared by acid modification and ZnO functionalization of mesoporous carbon. The synthesized materials, such as mesoporous carbon, oxidized mesoporous carbon and zinc oxide-coated nanoporous carbon, were characterized by nitrogen adsorption–desorption analysis, Fourier transform infrared spectra, scanning electron microscopy, and transmission electron microscopy. ZnO on oxidized mesoporous carbon gradually increased with increase in the number of cycles. Furthermore, the effects of agitation time, initial metal ions concentration, adsorbent dose, temperature and pH on the efficiency of Pb(II) ion removal were investigated as the controllable factors by Taguchi method. The value of correlation coefficients showed that the equilibrium data fitted well to the Langmuir isotherm. Among the adsorbents, zinc oxide-coated nanoporous carbon showed the largest adsorption capacity of 522.8 mg/g (2.52 mmol/g) which was almost close to that of the zinc oxide-coated (2.38 mmol/g), indicating the monolayer spreading of ZnO onto the oxidized mesoporous carbon. The results of the present study suggest that ZnO-coated nanoporous carbon can be effectively used for Pb(II) adsorption from aqueous solution, whereas a part of acidic functional groups may be contributed to binding the Pb(II) for the oxidized mesoporous carbon and mesoporous carbon. Kinetic studies indicated that the overall adsorption process of Pb(II) followed the pseudo-second-order model. The ZnO-coated nanoporous carbon was regenerated and found to be suitable of reuse of the adsorbent for successive adsorption–desorption cycles without considerable loss of adsorption capacity.     

Experimental study on prevention of acid mine drainage by silica coating of pyrite waste rocks with amorphous silica solution

Acid mine drainage (AMD) is a widespread environmental problem associated with working and abandoned mining operations. It results from the microbial oxidation of pyrite in the presence of water and air, affording an acidic solution that contains toxic metal ions. Pyrite microencapsulation, utilizing silica coating, is a novel approach for controlling AMD that has been shown to be very effective in controlling pyrite oxidation. The roles of the solution pH and silica concentration in the formation mechanism for the AMD-preventing coating were investigated. A silica coating can be formed from silica solution at pH 7, at which the amount of Fe eluted from pyrite into the solution is small. No coating was formed at other pH values, and the amounts of eluted Fe were larger than at pH 7, especially at pH 11. The silica coating forms from 2,500 to 5,000 mg/L silica solutions, but not from 0 or 1,000 mg/L silica solutions. The coating formation rate was slower in the 2,500 mg/L silica solution than in the 5,000 mg/L silica solution. The formation of silica coating on pyrite surfaces depends on three main steps: formation of Fe(OH)₃ on the surface of pyrite, reaction between Fe(OH)₃ and silicate in the solution on the pyrite surface, and growth of the silica layer on the first layer of silica. The best pH condition to enable these steps was around 7, and the silica coating formation rate can be controlled by the concentration of silica.     

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.     

Adsorption of aluminium by a latosol as affected by phosphate and glutamic acid

The effect of phosphate and glutamic acid on adsorption of aluminium onto a latosol was investigated as a function of pH and ligand concentrations through batch equilibrium experiments. The results showed that adsorption of aluminium by the soil was enhanced after addition of phosphate at low pH, and this promotive effect was gradually eliminated with the increase in pH. The positive effect of phosphate on aluminium adsorption onto latosol was attributed to phosphate-induced surface negative charge and formation of ternary surface complexes involving aluminium and phosphate. While using silica as adsorbent, the inactive surfaces for phosphate, promotion of adsorption of aluminium by phosphate was also found. Then it was proposed that additional aluminium might bind to the phosphate adsorbed onto the silica in the form of surface complexes silica–aluminium–phosphate again, and the mechanism might operate in the soil systems as well. Glutamic acid exhibited no influence on the adsorption of aluminium by the soil at low pH. After increasing the pH, adsorption of aluminium was inhibited especially with the highest addition of glutamic acid, probably owing to weak affinity of complexes between glutamic acid and aluminium to the soil.     

Geochemical characteristics of fluoride in groundwater of Gimcheon, Korea: lithogenic and agricultural origins

The occurrence of fluoride in groundwaters can be influenced by many factors. In Korea, the fluoride-rich groundwaters are normally associated with rock types, especially granite and gneiss. In Gimcheon, high-fluoride groundwaters (up to a maximum of 2.15 mg/L) were observed with bimodal distribution of concentrations. The groundwater in this area showed relatively high concentrations of anthropogenic chemicals such as nitrate, chloride, and sulfate. Statistical analysis showed that fluoride is positively correlated with pH, alkalinity, sodium, and lithium, indicating that the interaction with granite is the main cause enriching its concentration. In Gimcheon, δ¹⁸O data of groundwater showed a negative correlation with nitrate and can be used as an indicator of groundwater age. The four samples of fluoride-rich groundwater were plotted in the light δD and δ¹⁸O region, showing that they were the result of long water–rock reaction. However, other groundwater with a low-fluoride concentration was evenly distributed throughout all δD and δ¹⁸O ranges and did not show a statistically significant correlation with nitrate, indicating possible mixing with another source of fluoride. Considering the influence from the surface on the geochemical characteristics of groundwater in this area, anthropogenic sources including phosphate fertilizer containing fluoride and pesticides may also have partly contributed to the concentrations of fluoride in the low-fluoride groundwater. The scattered distribution of fluoride-rich groundwater and the significant correlation with lithium suggest that pegmatite is the main rock type increasing fluoride concentration in this area.     

一种用于铀同位素比值α能谱分析的磷化膜制源新技术

研发了一种用于铀同位素比值α能谱分析的磷化膜制源新技术。试验发现,当镍镀片面积为3.14cm2,盐酸浓度为0.5mol/L,氯化钠浓度为2.5mol/L,磷酸二氢钾浓度为0.08mol/L,抗坏血酸浓度为20g/L,溶液体积为25 mL,恒温90℃,振荡速率为160次/min,振程20 mm时,磷化膜制源70min,200μg以下的铀可在镍箔上定量转化为磷化膜。与传统的电沉积制源技术相比较,应用磷化膜制源技术进行测量源制备时无需电沉积装置,制源过程简单快速,工效高,大量共存的232 Th、230 Th、226 Ra、231Pa等核素均不产生干扰,铀的全程回收率接近100%,α能谱峰分辨率较好。     

Surface complexation effects on phosphate adsorption to ferric iron oxyhydroxides along pH and salinity gradients in estuaries and coastal aquifers

Non-conservative behavior of dissolved inorganic phosphate (DIP) in estuaries is generally ascribed to desorption from iron and aluminum (hydr)oxides with increasing salinity. Here, we assess this hypothesis by simulating the reversible adsorption of phosphate onto a model oxide (goethite) along physico-chemical gradients representative of surface and subsurface estuaries. The simulations are carried out using a surface complexation model (SCM), which represents the main aqueous speciation and adsorption reactions of DIP, plus the ionic strength-dependent coulombic interactions in solution and at the mineral-solution interface. According to the model calculations, variations in pH and salinity alone are unlikely to explain the often reported production of DIP in surface estuaries. In particular, increased aqueous complexation of phosphate by Mg²⁺ and Ca²⁺ ions with increasing salinity is offset by the formation of ternary Mg-phosphate surface complexes and the drop in electrical potential at the mineral-water interface. However, when taking into account the downstream decrease in the abundance of sorption sites, the model correctly simulates the observed release of DIP in the Scheldt estuary. The sharp increase in pH accompanying the admixing of seawater to fresh groundwater should also cause desorption of phosphate from iron oxyhydroxides during seawater intrusion in coastal aquifers. As for surface estuaries, the model calculations indicate that significant DIP release additionally requires a reduction in the phosphate sorption site density. In anoxic aquifers, this can result from the supply of seawater sulfate and the subsequent reductive dissolution of iron oxyhydroxides coupled to microbial sulfate reduction.     

Uranyl and arsenate cosorption on aluminum oxide surface

In this study, we examined the effects of simultaneous adsorption of aqueous arsenate and uranyl onto aluminum oxide over a range of pH and concentration conditions. Arsenate was used as a chemical analog for phosphate, and offers advantages for characterization via X-ray absorption spectroscopy. By combining batch experiments, speciation calculations, X-ray absorption spectroscopy, and X-ray diffraction, we investigated the uptake behavior of uranyl, as well as the local and long-range structure of the final sorption products. In the presence of arsenate, uranyl sorption was greatly enhanced in the acidic pH range, and the amount of enhancement is positively correlated to the initial arsenate and uranyl concentrations. At pH 4-6, U L_III- and As K-edge EXAFS results suggest the formation of surface-sorbed uranyl and arsenate species as well as uranyl arsenate surface precipitate(s) that have a structure similar to trögerite. Uranyl polymeric species or oxyhydroxide precipitate(s) become more important with increasing pH values. Our results provide the basis for predictive models of the uptake of uranyl by aluminum oxide in the presence of arsenate and (by analogy) phosphate, which can be especially important for understanding phosphate-based uranium remediation systems.     

溶液介质条件对重金属离子与石英表面反应的影响

实验研究表明,随着溶液ＰＨ值的升高石芟夺Ｃｕ＾２＋、Ｐｂ＾２＿、Ｃｄ＾２＋等重金属离子的吸附量和表面吸附覆盖率逐渐增大,而表面反应产物的结合开矿相应地出现由单核化合物、多核化合物〖ＳＯＣｕ４（ＯＨ）３＾４＋〗,直至表面沉淀（ＳＯＨ…Ｃｕ（ＯＨ）２（ｓ）〗。随着温度升高,石英对Ｃｕ＾２＋、Ｐｂ＾２＋、Ｃｄ＾２＋等重金属离子的吸附量逐渐减是随着溶液离子强度的增大,石英对Ｃｕ＾２＋离子的吸附量和表面离了     

Wastewater dephosphorization using crude clays

The present work aims to establish the possibility of using local clays to treat wastewater. Thus, three clay samples extracted from two localities in the south of Côte d’Ivoire have been studied in their crude state. The qualitative physicochemical study that consisted in measurement of pH variation and argillaceous particles zeta potential showed that the Nieki-Agneby clay and the Beige Anyama clay presented disposal to uptake phosphate ions in solution at pH 5. For each clay, it is shown that the tension accompanying the sorption of a phosphate ion could be estimated to ?5 mV. Differences in their composition and in the number of hydrating molecules of water were also accessible. The quantitative study performed with the Nieki-Agneby clay thereafter consisted following the sorption kinetic. The adsorption was found to reach the maximum after 5 h. of exchange, and almost 400 μg phosphate ions in per gram of clay were fixed. Future studies will focus on the modification of these materials in order to increase their sorption capacity.     

Aqueous heavy metals removal by adsorption on β-diketone-functionalized styrene–divinylbenzene copolymeric resin

An investigation was undertaken regarding the adsorption of different heavy metal ions from aqueous solutions using ??-diketone-functionalized styrene divinylbenzene resin under different experimental conditions such as initial concentration of metal ions, contact time, pH, and chelating capacity. The functionalization of resin was carried out by the condensation reaction of sodium salt of ??-diketones (pentane-1,3-dione) and chloromethylated styrene?Cdivinylbenzene resin in dichloromethane. Functionalized resin beads were characterized by Fourier transform infrared spectroscopy. The batch method was employed using different metal ions solution from 5 to 15?mg/L at different contact times. The adsorption kinetics was tested for the pseudo-first order, pseudo-second order reaction at different experimental conditions. The rate constant of adsorption kinetic models were also calculated and good correlation coefficient (R ²?>?0.9941) was obtained for pseudo-second order kinetic model. The maximum adsorption value obtain for lead (0.725728?mg/g), chromium (0.9199?mg/g), nickel (0.4974?mg/g), cobalt (0.6196?mg/g) and cadmium (0.6519?mg/g) at equilibrium condition, which shows that ??-diketone-functionalized styrene divinylbenzene resin is an effective adsorbent for toxic metal ions.