Removal of As(V) by Cu(II)-, Ni(II)-, or Co(II)-doped goethite samples

The present study reports removal of As(V) by adsorption onto laboratory-prepared pure and Cu(II)-, Ni(II)-, and Co(II)-doped goethite samples. The X-ray diffraction patterns showed only goethite as the crystalline phase. Doping of ions in the goethite matrix resulted in shift of d-values. Various parameters chosen for adsorption were nature of adsorbent, percentage of doped cations in goethite matrix, contact time, solution pH, and percentage of adsorbate. It was observed that the pH(pzc) of the goethite surface depended on the nature and concentration of metal ions. The surface area as well as the loading capacity increased with the increase of dopant percentage in goethite matrix. A maximum loading capacity of 19.55 mg/g was observed for 2.7% Cu(II)-doped goethite. The adsorption kinetics for Ni(II), Co(II) and for undoped goethite attained a quasi-equilibrium state after 30 min with almost negligible adsorption beyond this time. In case of Cu(II)-doped goethite samples, the quasi-equilibrium state for As(V) adsorption was observed after 60 min. At each studied pH condition, it was observed that the percentage of adsorption of As(V) decreased in the order Cu(II)-doped goethite > or = Ni(II)-doped goethite > Co(II)-doped goethite > pure goethite. The adsorption followed: Langmuir isotherm, indicating monolayer formation.     

Slow adsorption reaction between arsenic species and goethite (alpha-FeOOH): diffusion or heterogeneous surface reaction control

The slow stage of phosphate or arsenate adsorption on hydrous metal oxides frequently follows an Elovich equation. The equation can be derived by assuming kinetic control by either a diffusion process (either interparticle or intraparticle) or a heterogeneous surface reaction. The aim of this study is to determine whether the slow stage of arsenic adsorption on goethite is more consistent with diffusion or heterogeneous surface reaction control. Adsorption kinetics of arsenate and dimethylarsinate (DMA) on goethite (alpha-FeOOH) were investigated at different pH values and inert electrolyte concentrations. Their adsorption kinetics was described and compared using Elovich (Gamma vs ln time) plots. Desorption of arsenate and DMA was studied by increasing the pH of the suspension from pH 4.0 to pH 10.0 or 12.0. The effective particle sizes and zeta-potential of goethite were also determined. Effective particle size increased rapidly as the pH approached pH(IEP), both in the absence and presence of arsenic. Inert electrolyte concentrations and pH had no effect on the slow stage of arsenate adsorption on goethite, while the kinetics of DMA adsorption on goethite was influenced by both parameters. The slow stage of arsenate adsorption on goethite follows an Elovich equation. Since effective particle size changes with both pH and inert electrolyte concentrations, and effective particle size influences interparticle diffusion, the arsenate adsorption kinetics indicate that the slow adsorption step is not due to interparticle diffusion. DMA also has complex adsorption kinetics with a slow adsorption stage. DMA desorbed completely and rapidly when the pH was raised, in contrast to the slow adsorption kinetics, indicating that the slow adsorption step is not due to intraparticle diffusion. The slow adsorption is not the result of diffusion, but rather is due either to the heterogeneity of the surface site bonding energy or to other reactions controlling arsenic removal from solution.     

Copper and arsenate co-sorption at the mineral-water interfaces of goethite and jarosite

The co-sorption reaction products of arsenate (As(V)) and copper (Cu(II)) on goethite (alpha-FeOOH) and natro-jarosite (Na(3)Fe(3)(SO(4))(2)(OH)(6)) were investigated with extended X-ray absorption fine structure (EXAFS) spectroscopy to determine if Cu(II) and As(V) would form precipitates or compete with each other for surface sites. The reaction products were prepared by mixing 250 microM Cu(SO(4)) with 10, 25, or 50 microM Na(2)HAsO(4) at pH 5.65 and allowing the mixture to react in 10 m(2) L(-1) goethite or jarosite suspensions for 12 days. In addition, EXAFS data of Cu(SO(4)) and As(V) sorbed on goethite and jarosite were collected as control species. All reaction conditions were under-saturated with respect to common copper bearing minerals: tenorite (CuO), brochantite (Cu(4)(OH)(6)SO(4)), and hydrated clinoclase (Cu(3)(AsO(4))(2)2H(2)O). The extents of the As(V) and Cu(II) surface adsorption reactions showed a strong competitive effect from Cu(II) on As(V) adsorption for a nominal Cu:As mole-ratio of 25:1. With increasing nominal As(V) concentration, As(V) sorption on goethite and jarosite increased without diminishing the amount of Cu(II) sorption. In the absence of either co-sorbate, As(V) and Cu(II) formed the expected surface adsorption species, i.e., bidentate binuclear and edge-sharing surface complexes, consistent with previously published results. In each other's presence, the local bonding environments of As(V) and Cu(II) showed that the co-sorbates form a precipitate on the goethite and jarosite surface at nominal concentrations of 10:1 and 5:1. At nominal Cu:As mole-ratios of 25:1, Cu(II) did not form significantly different surface complexes on goethite or jarosite from those in the absence of As(V), however, As K-edge EXAFS results distinctly showed Cu(II) atoms in As(V)'s local bonding environment on the goethite surface. The structures of the two precipitates were different and depended on the anion-layer structure and possibly the presence of structural oxyanions in the case of jarosite. On goethite, the copper-arsenate precipitate was similar to hydrated clinoclase, while on jarosite, a euchroite-like precipitate (Cu(2)[AsO(4)](OH)3H(2)O, P 2(1)2(1)2(1)) had formed. Despite under-saturated solution conditions, the formation of these precipitates may have occurred due to a seed-formation effect from densely surface adsorbed Cu(II) and As(V) for which the "new" saturation index was significantly lower than homogeneous values would otherwise suggest. Synergistic reactions between two co-sorbates of fundamentally different surface adsorption behaviour can thus be achieved if the number of available sites for surface adsorption is limited.     

Copper and zinc removal from aqueous solution by mixed mineral systems I. Reactivity and removal kinetics

This study investigates the reactivity and removal kinetics of Cu and Zn onto mixed mineral systems from aqueous solution related to acid mine drainage impacted areas. The sorbents used were kaolinite, Al-montmorillonite, goethite, and their mixtures. The effects of surface charge, proton coefficient, and sorption kinetics were studied at room temperature (23+/-2 degrees C). Using an empirical model, mineral mixing reduced the exchange of protons for sorbing ions and the acidity of the reactive sites, thus impeding Cu and Zn removal by proton exchange. Based on the amount of Cu and Zn sorbed on the mixed mineral suspensions at ionic strength 0.01 to 0.1 M and pH 4, it is suggested that Cu and Zn removal from aqueous solution was by both inner and outer sphere complexation. Mineral mixing reduced the transfer rate of Cu relative to the single mineral suspensions in both slow and fast reaction phases. The behavior of the mixed suspensions in Cu and Zn sorption suggest that different reactive sites were involved at the onset of sorption, becoming similar to those of the single mineral components over time.     

Adsorption of sulfate and copper(II) on goethite in relation to the changes of zeta potentials

The amount of adsorption of sulfate and Cu(II) from single- and binary-adsorbate systems on goethite were measured. All experiments were carried out with and without supporting electrolyte (0.01 M NaNO(3)) as a function of equilibrium pH (2 - 7), adsorbate concentration (0.21 - 1.57 mM), and temperature (15 - 35 degrees C). At a given equilibrium pH, it was shown that the adsorption isotherms of single sulfate, rather than Cu(II), could be well described by the Langmuir equation. The isosteric enthalpy of sulfate adsorption was also evaluated. In contrast to a single-adsorbate system, the adsorption of Cu(II) was enhanced and that of sulfate was inhibited in binary adsorbate systems under the conditions studied. Finally, the changes in zeta potentials of the goethite suspensions with solution pH before and after adsorption were measured, which could be macroscopically related to the amount of sulfate adsorption even in binary-adsorbate systems.     

偕胺肟合铁（III）纤维对还原棕BR染料的吸附

以部分偕胺肟化的聚丙烯腈纤维与铁离子反应,形成偕胺肟合铁（III）吸附纤维,以此为吸附材料,吸附水溶液中的还原棕染料。研究吸附的工艺条件、吸附规律及吸附反应动力学,结果显示：最佳吸附工艺条件：pH值11.5-12.5、温度600 ℃和吸附时间60 min。偕胺肟合铁（III）纤维对还原棕的吸附符合Langmiure方程和Freundlich等温吸附经验式。由不同的初始浓度下吸附时间与溶液的浓度的关系,用微分法确定反应的级数和反应速率常数。由不同温度下的速率常数,结合Arrhenius方程得出反应的活化能。偕胺肟合铁（III）纤维对还原棕的吸附符合一级反应动力学特征;其速率方程c=c₀e^-kt,速率常数k=32.01e^-E_a/RT,活化能E_a=11.55 kJ/mol。     

Kinetics of solute adsorption at solid/aqueous interfaces: searching for the theoretical background of the modified pseudo-first-order kinetic equation

It is shown that the modified pseudo-first-order (MPFO) kinetic equation proposed recently by Yang and Al-Duri simulates well the behavior of the kinetics governed by the rate of surface reaction and described by our general kinetic equation, based on the statistical rate theory. The linear representation with respect to time, offered by the MPFO equation seems to be a convenient tool for distinguishing between the surface reaction and the diffusional kinetics. Also, a method of distinguishing between the surface reaction and the intraparticle diffusion model based on analyzing the initial kinetic isotherms of sorption is proposed. The applicability of these procedures is demonstrated by the analysis of adsorption kinetics of the reactive yellow dye onto an activated carbon.     

Adsorption kinetics of phosphate and arsenate on goethite. A comparative study

The adsorption kinetics of phosphate and arsenate on goethite is studied and compared. Batch adsorption experiments were performed at different adsorbate concentrations, pH, temperatures and stirring rates. For both oxoanions the adsorption rate increases by increasing adsorbate concentration, decreasing pH and increasing temperature. It does not change by changing stirring rate. The adsorption takes place in two processes: a fast one that takes place in less than 5 min and a slow one that takes place in several hours or more. The rate of the slow process does not depend directly on the concentration of phosphate or arsenate in solution, but depends linearly on the amount of phosphate or arsenate that was adsorbed during the fast process. Apparent activation energies and absence of stirring rate effects suggest that the slow process is controlled by diffusion into pores, although the evidence is not conclusive. The similarities in the adsorption kinetics of phosphate and arsenate are quantitatively shown by using a three-parameters equation that takes into account both the fast and the slow processes. These similarities are in line with the similar reactivity that phosphate and arsenate have in general and may be important for theoretical and experimental studies of the fate of these oxoanions in the environment.     

自然水体生物膜吸附Co,Ni和Cu的特征研究

研究了在自然水体中培养的生物膜吸附Co,Ni和Cu等3种重金属的热力学和动力学特征,并对生物膜吸附各重金属的热力学数据进行了非线性拟合.结果表明,3种重金属的吸附过程均符合Langmuir吸附等温曲线.在溶液中重金属浓度<0.5μmol/L时,生物膜对3种重金属元素的吸附能力顺序是Co>Cu>Ni;在重金属浓度>0.5μmol/L时,顺序是Cu>Co>Ni.对动力学数据进行非线性拟合的结果表明,生物膜对Co,Ni和Cu的吸附均在数小时内达到平衡,吸附过程符合Langmuir等动力学曲线.     

Adsorption of tetracycline onto goethite in the presence of metal cations and humic substances

Adsorption of tetracycline, one of the most widely used antibiotics, onto goethite was studied as a function of pH, metal cations, and humic acid (HA) over a pH range 3-10. Five background electrolyte cations (Li(+), Na(+), K(+), Ca(2+), and Mg(2+)) with a concentration of 0.01 M showed little effect on the tetracycline adsorption at the studied pH range. While the divalent heavy metal cation, Cu(2+), could significantly enhance the adsorption and higher concentration of Cu(2+), stronger adsorption was found. The results indicated that different adsorption mechanisms might be involved for the two types of cations. Background electrolyte cations hardly interfere with the interaction between tetracycline and goethite surfaces because they only form weak outer-sphere surface complexes. On the contrary, Cu(2+) could enhance the adsorption via acting as a bridge ion to form goethite-Cu(2+)-tetracycline surface complex because Cu(2+) could form strong and specific inner-sphere surface complexes. HA showed different effect on the tetracycline sorption under different pH condition. The presence of HA increased tetracycline sorption dramatically under acidic condition. Results indicated that heavy metal cations and soil organic matters have great effects on the tetracycline mobility in the soil environment and eventually affect its exposure concentration and toxicity to organisms.     

FT-IR、XPS和DFT研究水杨酸钠在针铁矿或赤铁矿上的吸附机理

采用傅里叶变换红外(FT-IR)光谱、X射线光电子能谱(XPS)以及基于周期平面波的密度泛函理论(DFT)分别研究了水杨酸钠在针铁矿或赤铁矿表面上的吸附结构,并将计算得到的光电子能谱移动(CLS)和电荷转移与实验得到的XPS结果进行对比。FT-IR结果表明,水杨酸钠可能以双齿双核(V)和双齿单核(IV)的形式分别吸附于针铁矿或赤铁矿表面。由DFT计算结果可知,水杨酸钠在针铁矿(101)晶面上形成双齿双核化合物(V)的吸附能为-5.46 eV。而水杨酸钠在针铁矿(101)晶面上形成双齿单核化合物(IV)的吸附能为3.80 eV,因此水杨酸钠在针铁矿上基本不以双齿单核化合物(IV)构型存在。水杨酸钠在赤铁矿(001)晶面上形成双齿单核化合物(IV)时吸附能为-4.07 eV,说明水杨酸钠在赤铁矿(001)晶面上形成了双齿单核化合物(IV)。另外,理论计算的针铁矿(101)晶面上吸附位点铁原子的Fe 2p的CLS值(-0.68 eV)与实验观察到的Fe 2p的CLS值(-0.5 eV)吻合。理论计算的赤铁矿(001)晶面上吸附位点铁原子的Fe 2p的CLS值(-0.80 eV)与实验观察到的Fe 2p的CLS值(-0.8 eV)吻合。因此,水杨酸钠吸附在针铁矿表面时能够通过羧酸基团上一个氧原子和酚羟基上的氧原子与针铁矿(101)表面上的两个铁原子形成双齿双核(V)结构,而在赤铁矿(001)表面上,水杨酸钠中羧酸基团上一个氧原子和酚羟基上的氧原子与赤铁矿(001)表面上的一个铁原子形成了双齿单核(IV)结构。     

羧甲基壳聚糖对亚铁离子的吸附

壳聚糖是由甲壳素经脱乙酰基后得到的一种天然高分子氨基多糖 ,它是金属离子的良好配体 ,其配合物在工业、农业、食品、环保、医药等方面的应用已有许多研究 [1～ 4 ] .脱乙酰基后的壳聚糖溶解性有很大改善 ,但仍只能溶于酸或酸性水溶液 ,限制了它的推广应用 .通过化学改性的羧甲基壳聚糖 ( CMCS)具有良好的水溶性、保湿性、乳化性 ,其分子中含有— OH、— NH2 、—COOH等基团 ,能有效络合金属离子 [5] .人体对壳聚糖 -亚铁络合物的吸收远远大于传统的 Fe SO4 药物 [6 ] ,壳聚糖及其衍生物与 Fe2 的络合物有可能用于治疗缺铁性贫血 …     

Cu单原子修饰对Fe(111)表面CO吸附性能及电子性质调变的第一性原理研究

采用密度泛函理论方法研究了Cu单原子修饰对Fe(111)表面CO吸附性能和电子性质的调变作用,其中,Cu单原子修饰研究了吸附和取代两种方式。结果表明,CO在Cu修饰的Fe(111)面吸附能力都会变弱,一是Cu原子自身提供的位点对CO的吸附较弱;二是Cu会使其附近的Fe对CO的吸附变弱。分析电子性质表明,Cu作用于Fe表面后,会导致Cu附近Fe原子部分电子向Cu原子转移,进而削弱了Fe与吸附分子间电子交互作用而改变Fe原子的吸附能力。故Cu原子改性Fe表面可以很好地调变CO的吸附、解离及后续反应催化活性,这为进一步探究Cu改性Fe表面的合成气催化反应机理提供了基础信息。     

Kinetics and Thermodynamics of the Adsorption of Copper(Ⅱ) onto a New Fe-Si Adsorbent

A new kind of Fe-Si adsorbent was synthesized by iron oxide and diatomite after calcining and hydrothermal process. The influences of the initial Cu2+ concentration, p H and adsorption time on the Cu2+ removal efficiency were discussed. Three adsorption empirical kinetics equations and two thermodynamics equations were used to simulate the adsorption process. The microstructures of newly developed copper removal materials and properties of copper removal are characterized in details by SEM and EDS. Adsorption mechanism of the adsorbent was discussed. The suitable p H value for Cu2+ removal is 5.0 to 6.0 and the adsorption capacity increases with increasing the initial Cu2+ concentration. The adsorption kinetics of the adsorbent could be better described by pseudo second order kinetic model, whereas the adsorption isotherms highly conform to the Freundlich equation. The main crystalline phase of the adsorbent is Fe(Si O3) which can build porous structures conducive to the Cu2+ adsorption.     

Adsorption and desorption of copper and zinc in the surface layer of acid soils

The environmental and health effects of the contamination of soils by heavy metals depend on the ability of the soils to immobilize these contaminants. In this work, the adsorption and desorption of Cu and Zn in the surface layers of 27 acid soils were studied. Adsorption of Cu(II) from 157-3148 mumol L(-1) solutions was much greater than adsorption of Zn(II) from solutions at the same concentration. For both Cu and Zn, the adsorption data were fitted better by the Freundlich equation than by the Langmuir equation. Multiple regression analyses suggest that Cu and Zn adsorption depends to a significant extent on pH and CEC: for both metals these variables accounted for more than 80% of the variance in the Freundlich pre-exponential parameter K(F), and pH also accounted for 57% of the variance in 1/n for Zn and, together with carbon content, for 41% of the variance in 1/n for Cu. The percentage of adsorbed metal susceptible to desorption into 0.01 M NaNO3 was greater for Zn than for Cu, but in both cases depended significantly on pH, decreasing as pH increased. In turn, both pH(H2O) and pH(KCl) are significantly correlated with cation exchange capacity. Desorption of metal adsorbed from solutions at relatively low concentration (787 mumol L(-1)) exhibited power-law dependence on Kd, the quotient expressing distribution between soil and soil solution in the corresponding adsorption experiment, decreasing as increasing Kd reflected increasing affinity of the soil for the metal. The absence of a similarly clear relationship when metal had been adsorbed from solutions at relatively high concentration (2361 mumol L(-1)) is attributed to the scant between-soil variability of Kd at these higher concentrations. In general, adsorption was greater and subsequent desorption less in cultivated soils than in woodland soils.     

Kinetics and thermodynamics studies of copper exchange on Na-montmorillonite clay mineral

The kinetics of Cu ion exchange on Na-montmorillonite clay has been investigated at 20, 30, and 40 degrees C in water, methanol, and ethanol. The reaction is endothermic in nature. Solvent effects on the reaction rate have been discussed. The thermodynamic activation parameters were calculated and discussed in terms of solvation effects. A multiple reaction rate order equation was used to describe the adsorption process. Lower rates and higher activation energies (Ea) were observed in aqueous solution than in either of the alcohols. The Ea values ranged from 20.88 kJmol(-1) in water to 9.20 kJmol(-1) in ethanol, while at 20 degrees C the rate constant (k) varied from 0.111 ppm(-1)s(-1) in water to 0.205 ppm(-1)s(-1) in ethanol. The main factor influencing the rate of the adsorption process is the mobility of the adsorbed Cu cations, which is apparently larger in alcohols than in water, due to the difference in the molar activation energy of the solvent. The determined isokinetic temperature indicates that the reaction is enthalpy-controlled, where the interaction between solvent and clay surface plays an important role. A reaction mechanism that describes the solvent effect on the rate of Cu ion exchange is proposed.     

Surface complexes of monomethyl phosphate stabilized by hydrogen bonding on goethite (α-FeOOH) nanoparticles

Typically, a significant fraction of phosphorus in soils is composed of organic phosphates, and this fraction thus plays an important role in the global phosphorus cycle. Here we have studied adsorption of monomethyl phosphate (MMP) to goethite (α-FeOOH) as a model system in order to better understand the mechanisms behind adsorption of organic phosphates to soil minerals, and how adsorption affects the stability of these molecules. The adsorption reactions and stability of MMP on goethite were studied at room temperature as a function of pH, time and total concentration of MMP by means of quantitative batch experiments, potentiometry and infrared spectroscopy. MMP was found to be stable at the water-goethite interface within the pH region 3-9 and over extended periods of time, as well as in solution. The infrared spectra indicated that MMP formed three predominating pH-dependent surface complexes on goethite, and that these interacted monodentately with surface Fe. The complexes differed in hydrogen bonding interactions via the auxiliary oxygens of the phosphate group. The presented surface complexation model was based on the collective spectroscopic and macroscopic results, using the Basic Stern approach to describe the interfacial region. The model consisted of three monodentate inner sphere surface complexes where the MMP complexes were stabilized by hydrogen bonding to a neighboring surface site. The three complexes, which had equal proton content and thus could be defined as surface isomers, were distinguished by the distribution of charge over the 0-plane and β-plane. In the high pH-range, MMP acted as a hydrogen bond acceptor whereas it was a hydrogen bond donor at low pH.     

Kinetics and equilibrium adsorption of Cu(II), Cd(II), and Ni(II) ions by chitosan functionalized with 2[-bis-(pyridylmethyl)aminomethyl]-4-methyl-6-formylphenol

Chitosan biopolymer chemically modified with the complexation agent 2[-bis-(pyridylmethyl)aminomethyl]-4-methyl-6-formylphenol (BPMAMF) was employed to study the kinetics and the equilibrium adsorption of Cu(II), Cd(II), and Ni(II) metal ions as functions of the pH solution. The maximum adsorption of Cu(II) was found at pH 6.0, while the Cd(II) and Ni(II) maximum adsorption occurred in acidic media, at pH 2.0 and 3.0, respectively. The kinetics was evaluated utilizing the pseudo-first-order and pseudo-second-order equation models and the equilibrium data were analyzed by Langmuir and Freundlich isotherms models. The adsorption kinetics follows the mechanism of the pseudo-second-order equation for all studied systems and this mechanism suggests that the adsorption rate of metal ions by CHS-BPMAMF depends on the number of ions on the adsorbent surface, as well as on their number at equilibrium. The best interpretation for the equilibrium data was given by the Langmuir isotherm and the maximum adsorption capacities were 109 mg g-1 for Cu(II), 38.5 mg g-1 for Cd(II), and 9.6 mg g-1 for Ni(II). The obtained results show that chitosan modified with BPMAMF ligand presented higher adsorption capacity for Cu(II) in all studied pH ranges.     

Diffusion-limited thiol adsorption on the gold(111) surface

An optical second harmonic generation measurement of the kinetics of self-assembly of a monolayer of thiols on the Au(111) surface reveals a marked dependence of the adsorption rate upon the solution flow rate. The nature of this dependence indicates that at low concentration and low flow rate the monolayer growth is limited by the existence of a Nernst diffusion layer, not by surface reaction rate kinetics.