Adsorption efficiency,thermodynamics and kinetics of Schiff base-modified nanoparticles for removal of heavy metals

Nanosilica particles modified by Schiff base ligands 3-methoxy salicylaldimine propyl triethoxysilane (MNS₁), 5-bromo salicylaldimine propyl triethoxysilane (MNS₂) and 3-hydroxy salicylaldimine propyl triethoxysilane (MNS₃) were prepared, and their potential for separation of copper, lead, zinc, cadmium, cobalt and nickel ions from aqueous solutions was examined. The effect of parameters influencing adsorption efficiency including aqueous-phase pH, amount of adsorbent, stirring time and initial concentration of the metal ions was assessed and discussed. Although MNS₁ and MNS₃ removed lead ions efficiently, all adsorbents showed strong selectivity toward copper ions. It was shown that, under some circumstances, MNS₃ decreased the amount of other ions, particularly cobalt, in the aqueous phase. The adsorbents were also applied for removal of copper and lead ions from real samples. Possible quantitative desorption of the metal ions loaded onto the adsorbents suggests their multiple uses in adsorption–desorption process. Investigation of temperature dependency of the process led to determination of the ΔH°, ΔS° and ΔG° values. This investigation indicates that the adsorption of copper ions onto the all studied adsorbents and lead ions onto MNS₁ and MNS₃ is endothermic. The Langmuir, Freundlich, Temkin and Dubinin–Radushkevich isotherms were tested to describe the equilibrium data. Pseudo-first-order, pseudo-second-order, Elovich and intra-particle diffusion equations were applied to study the kinetics of copper and lead adsorption onto the modified nanoparticles. This investigation indicates that the process for all adsorbents follows pseudo-second-order kinetics and suggests a chemisorption mechanism for the adsorption processes by the studied adsorbents.     

Insight into adsorption equilibrium,kinetics and thermodynamics of lead onto alluvial soil

In the present study, adsorption of lead (II) ions from aqueous solution by alluvial soil of Bhagirathi River was investigated under batch mode. The influence of solution pH, sorbent dose, initial lead (II) concentration, contact time, stirring rate and temperature on the removal process were investigated. The lead adsorption was favored with maximum adsorption at pH 6.0. Sorption equilibrium time was observed in 60 min. The equilibrium adsorption data were analyzed by the Freundlich, Langmuir, Dubinin–Radushkevich and Temkin adsorption isotherm models. The kinetics of lead (II) ion was discussed by pseudo first-order, pseudo second-order, intra-particle diffusion, and surface mass transfer models. It was shown that the adsorption of lead ions could be described by the pseudo second-order kinetic model. The activation energy of the adsorption process (E _a) was found to be ?38.33 kJ mol^?1 using the Arrhenius equation, indicating exothermic nature of lead adsorption onto alluvial soil. Thermodynamic parameters, such as Gibbs free energy (?G ⁰), the enthalpy (?H ⁰), and the entropy change of sorption (?S ⁰) have also been evaluated and it has been found that the adsorption process was spontaneous, feasible, and exothermic in nature. The results indicated that alluvial soil of Bhagirathi River can be used as an effective and low cost adsorbent to remove lead ions from aqueous solutions.     

Removal of diazinon pesticide from aqueous solutions using MCM-41 type materials: isotherms,kinetics and thermodynamics

In this research, ordered mesoporous silica, including MCM-41, was synthesized via sol–gel process and a propyl methacrylate-modified ordered mesoporous silica (MPS-MCM-41) was successfully synthesized via a postsynthesis grafting process. Then both MCM-41 and MPS-MCM-41 were characterized using FTIR, XRD, SEM and BET techniques. The synthesized materials were utilized as adsorbent for removal of diazinon pesticide from aqueous solutions. The effects of pH, contact time, adsorbent dose, initial concentration and temperature have been evaluated using removal efficiencies. Also, the kinetic, thermodynamic and isotherm models of diazinon adsorption were studied for the both MCM-41 and MPS-MCM-41. The results showed that the maximum adsorption capacities are 142 and 254 mg g^?1 for the MCM-41 and MPS-MCM-41, respectively, at the initial concentration of 50 mg L^?1, temperature of 298 K and adsorbent dose of 0.1 g L^?1. The highest percentages of diazinon removal are 56.4 and 87.2 (at adsorbent dose of 2 g L^?1 and the temperature of 318 K) for the MCM-41 and MPS-MCM-41, respectively. The Freundlich and Langmuir models are more compatible for describing equilibrium data of the diazinon adsorption capacity on the MCM-41 and MPS-MCM-41, respectively. Thermodynamic study indicated that the adsorption process of diazinon onto MCM-41 and MPS-MCM-41 is exothermic and has a spontaneous nature. The higher adsorption capacity and higher spontaneous nature of MPS-MCM-41 in comparison with MCM-41 might be due to the presence of the both hydrogen bonding and hydrophobic interaction between surface functional groups of MPS-MCM-41 (hydroxyl and propyl methacrylate) and diazinon functional groups.     

Adsorption kinetics of herbicide paraquat in aqueous solution onto a low-cost adsorbent, swine-manure-derived biochar

Biochars have received increasing attention in recent years because of their significant properties such as carbon sequestration, soil fertility, and contaminant immobilization. In this work, the adsorptive removal of paraquat (1,1′-dimethyl-4,4′-dipyridinium chloride, one of the most widely used herbicides) from aqueous solution onto the swine-manure-derived biochar has been studied at 25 °C in a batch adsorption system. The adsorption rate has been investigated under the controlled process parameters including initial pH (i.e., 4.5, 6.0, 7.5, and 9.0), paraquat concentration (i.e., 0.5, 1.0, 2.0, 4.0, and 6.0 mg/L), and biochar dosage (i.e., 0.10, 0.15, 0.20, 0.25, and 0.30 g/L). Based on the adsorption affinity between cationic paraquat and carbon-like adsorbent, a pseudo-second order model has been developed using experimental data to predict the adsorption kinetic constant and equilibrium adsorption capacity. The results showed that the adsorption process could be satisfactorily described with the reaction model and were reasonably explained by assuming an adsorption mechanism in the ion exchange process. Overall, the results from this study demonstrated that the biomass-derived char can be used as a low-cost adsorbent for the removal of environmental cationic organic pollutants from the water environment.     

Adsorption of hexavalent chromium onto activated carbon derived from <Emphasis Type="Italic">Leucaena leucocephala</Emphasis> waste sawdust: kinetics,equilibrium and thermodynamics

The adsorptive removal of Cr(VI) was studied using activated carbon derived from Leucaena leucocephala (ACLL). The physico-chemical properties of ACLL were determined using proximate analysis and N₂ BET surface area analysis. The N₂ BET surface area of ACLL was determined to be 1131 m² g^?1. The point of zero charge (pH_pzc) of 5.42 indicated that ACLL surface was positively charged for pH below the pH_PZC, attracting anions. The effect of experimental operating parameters such as time of contact, ACLL dose, pH, initial concentration and temperature was investigated. The optimum values of parameters such as concentration of 100 mg L^?1, 300 mg of ACLL dose, time of contact of 60 min, pH of 4 indicated the maximum Cr(VI) uptake of 13.85 mg g^?1. The pseudo-second-order kinetic model best fitted with the Cr(VI) adsorption data. Adsorptive removal of Cr(VI) onto ACLL satisfactorily fitted in the order of Redlich–Peterson > Freundlich > Langmuir > Temkin adsorption isotherm model. The thermodynamic parameters showed the adsorption of Cr(VI) onto ACLL was an endothermic and spontaneously occurred process.     

Ni/Fe双金属对PCE脱氯影响因素研究

以四氯乙烯(PCE)为目标污染物, 利用批试验研究Ni/Fe双金属对氯代烃脱氯的影响因素.结果表明: (1)当参加反应的Ni/Fe双金属分别为10 g和20 g时, 反应速率常数k_obs分别为0.047 7 h-1和0.097 0 h-1, 说明增加参加反应的Ni/Fe双金属的质量可提高脱氯速率; (2)当粒度分别为20~ 40目、40~ 65目和80~ 100目时, k_obs分别为0.047 7 h-1, 0.059‥ 8 h-1和0.088 6 h-1, 说明选用Ni/Fe双金属颗粒越小脱氯速率越快; (3)当Ni/Fe质量比分别为0.024%, 0.048%和0.072%时, 所得k_obs分别为0.047 7 h-1, 0.066 2 h-1和0.073 4 h-1, 说明Ni/Fe双金属系统中Ni/Fe质量比越高脱氯效果越好, 但最优Ni/Fe质量比还有待于进一步研究.      

纳米镍／铁对四氯乙烯快速脱氯试验

实验室合成的纳米Ni/Fe(粒径20~60nm,比表面积为52. 61m2 /g),在固液比相对较低条件下(5. 4g/L),对四氯乙烯(PCE)能够快速并完全脱氯,在6h时,脱氯率为99. 70%,反应符合准一级反应动力学方程,标准化反应速率常数kSA为3. 04mL·m-2·h-1。反应过程中水样未检测到其他的氯代中间产物或最终产物,无毒的烃类乙烷(C2H6 )是主要产物,约占加入时PCE总碳质量的94% ~110%。试验结果说明加氢催化剂Ni的存在,通过原电池腐蚀作用提高了脱氯速率并同时增加了良性产     

Oxidation modes and thermodynamics of Fe oxyhydroxycarbonate green rust: Dissolution-precipitation versus in situ deprotonation

Fe^II-III hydroxycarbonate green rust GR(CO₃²⁻), Fe^II₄ Fe^III₂ (OH)₁₂ CO₃·3H₂O, is oxidized in aqueous solutions with varying reaction kinetics. Rapid oxidation with either H₂O₂ or dissolved oxygen under neutral and alkaline conditions leads to the formation of ferric oxyhydroxycarbonate GR(CO₃²⁻)∗, Fe^III₆ O₁₂ H₈ CO₃·3H₂O, via a solid-state reaction. By decreasing the flow of oxygen bubbled in the solution, goethite α-FeOOH forms by dissolution-precipitation mechanism whereas a mixture of non-stoichiometric magnetite Fe_(3−x)O₄ and goethite is observed for lower oxidation rates. The intermediate Fe^II-III oxyhydroxycarbonate of formula Fe^II_6(1−x) Fe^III_6x O₁₂ H_2(7−3x) CO₃·3H₂O, i.e. GR(x)∗ for which x ? [1/3, 1], is the synthetic compound that is homologous to the fougerite mineral present in hydromorphic gleysol; in situ oxidation accounts for the variation of ferric molar fraction x = [Fe^III]/{[Fe^II]+[Fe^III]} observed in the field as a function of depth and season but limited to the range [1/3, 2/3]. The domain of stability for partially oxidized green rust is observed in the E_h-pH Pourbaix diagrams if thermodynamic properties of GR(x)∗ is compared with those of lepidocrocite, γ-FeOOH, and goethite, α-FeOOH. Electrochemical equilibrium between GR(x)∗ and Fe^II in solution corresponds to E_h-pH conditions close to those measured in the field. Therefore, the reductive dissolution of GR(x)∗ can explain the relatively large concentration of Fe^II measured in aqueous medium of hydromorphic soils containing fougerite.     

纳米镍/铁去除氯代烃影响因素的探讨

氯代烃是地下水中最常检出的有机污染物之一,传统的处理方法去除率很低。近年来随着铁还原技术的发展,纳米铁和纳米双金属也成为一个活跃的研究领域。利用批实验的研究方法以四氯乙烯(PCE)和四氯化碳(CT)为目标污染物,研究纳米镍/铁在去除PCE过程中的影响因素。实验结果表明,在碱性条件下,纳米Ni/Fe对PCE脱氯速率比在酸性和中性条件下脱氯速率更快;纳米Ni/Fe对初始浓度为6·51mg/L的PCE溶液脱氯速率是对初始浓度为20·56mg/L的PCE溶液脱氯速率的1·8倍;对于氯代程度相同的CT和PCE,对CT的脱氯速率明显快于对PCE。     

Adsorption isotherms, kinetics and mechanism for the adsorption of cationic and anionic dyes onto carbonaceous particles prepared from Juglans regia shell biomass

In the present study, Juglans regia shells were used to prepare activated carbon by acid treatment method. J. regia shell-based activated carbon was used for the adsorption of two synthetic dyes namely, a basic dye malachite green and an acid dye amido black 10B. The prepared adsorbent was crushed and sieved to three different mesh sizes 100, 600 and 1,000 μm. The adsorbent was characterized by scanning electron microscopy, surface acidity and zero-point charge. Batch experiments were carried out by varying the parameters like initial aqueous phase pH, adsorbent dosage and initial dye concentration. The equilibrium data were tested with Langmuir, Freundlich, Redlich–Peterson and Sips isotherm at three different temperatures 293, 300 and 313 K and it was found that the Freundlich isotherm best fitted the adsorption of both the dyes. Kinetic data were tested with pseudo first-order model and pseudo second-order model. The mechanism for the adsorption of both the dyes onto the adsorbent was studied by fitting the kinetic data with intraparticle diffusion model and Boyd plot. External mass transfer was found to be the rate-determining step. Based on the ionic nature of the adsorbates, the extent of film diffusion and intraparticle diffusion varied; both being system specific. Thermodynamic parameters were also calculated. Finally, the process parameters of each adsorption system were compared to develop the understanding of the best suitable system.     

Redox potential measurements and Mössbauer spectrometry of Fe adsorbed onto Fe (oxyhydr)oxides

The redox properties of Fe^II adsorbed onto a series of Fe^III (oxyhydr)oxides (goethite, lepidocrocite, nano-sized ferric oxide hydrate (nano-FOH), and hydrous ferric oxide (HFO)) have been investigated by rest potential measurements at a platinum electrode, as a function of pH (−log₁₀[H⁺]) and surface coverage. Using the constant capacitance surface complexation model to describe Fe^II adsorption onto these substrates, theoretical values of the suspension redox potential (E_H) have been computed, under the assumption that Fe^II adsorption occurs at crystal growth sites of the substrate surface. Good agreement between calculated and experimental E_H values is observed for nano-FOH and HFO, however the redox potentials measured for lepidocrocite and goethite are significantly more oxidizing than predicted. Mössbauer spectroscopic analysis of ⁵⁷Fe^II adsorbed onto HFO and goethite shows that in both cases the adsorbed ⁵⁷Fe^II is incorporated into the crystal structure of the substrate, in broad agreement with the thermodynamic model, but is almost completely oxidized to ⁵⁷Fe^III. The mechanism by which the adsorbed ⁵⁷Fe^II is oxidized is not resolved in this work, but is thought to be due to electron transfer to the substrate, rather than a net oxidation of the suspension. The disagreement between experimental and calculated rest potential measurements in the goethite and lepidocrocite systems is thought to be due to the poor electrochemical equilibration of these suspensions with the platinum electrode, rather than a failure of the thermodynamic model. The model developed for the redox potential of adsorbed Fe^II allows direct assessment of the reactivity of this species towards oxidized pollutants.     

Stabilization of Fe/Cu nanoparticles by starch and efficiency of arsenic adsorption from aqueous solutions

Due to the severity of arsenic contamination of soil and water resources around the world, finding new adsorbents for arsenic removal from the water is of high importance. The present study investigates the possible use and effectiveness of starch-stabilized Fe/Cu nanoparticles for adsorption of arsenic from aqueous solutions. First, Fe/Cu nanoparticles at various starch concentrations of 0, 0.02, 0.04 and 0.06 wt% were synthesized and characterized by X-ray diffraction, transmission electron microscopy and zeta potential/particle size analyzer. Then 0.04 wt% stabilized Fe/Cu nanoparticles were tested for the sorption of As(III) and As(V) from synthetic arsenic-contaminated water. To have an understanding about the arsenic adsorption mechanism of nanoparticles, X-ray photoelectron spectroscopy (XPS) was performed before and after adsorption. The results showed that starch provides nanoparticles with a neutral surface and stabilization of nanoparticles is possible with 0.04 wt% or higher concentrations of starch. For 0.04 wt% starch-stabilized Fe/Cu nanoparticles, the adsorption isotherms fit well within the Langmuir equation, with maximum sorption capacities of 90.1 mg/g for As(III) and 126.58 mg/g for As(V) at a pH of 7.0 from the aqueous arsenic solutions. Examining the XPS spectra of nanoparticles before and after adsorption showed that arsenic adsorption by this nanoparticle can be due to the formation of inner-sphere arsenic complexes on the particle surface, and the surface oxygen-containing functional groups involved in adsorption. The high sorption capacity suggests the potential for applying starch-stabilized Fe/Cu nanoparticles to the contaminated waters for removal of arsenic.     

Adsorption of copper and zinc onto natural clay in single and binary systems

Calcareous and smectitic clay samples from the Coniacian–Lower Campanian system, Tunisia, were used as adsorbents for the removal of copper and zinc from aqueous solutions in single and binary systems. Calcareous clay sample was treated with acetic acid to obtain carbonate-free sample that was also used for metals removal. The adsorption of metal ions onto natural clay was tested in a batch method by mixing 1 g/L of each sample with a metal ion solution of zinc (300 μmol/L) and/or copper 600 μmol/L under the operating pH of 6, and agitation speed of 200 rpm within the equilibrium time of 60 min at 25 °C for single and binary systems. Our results showed that natural clay samples were mainly composed of silica, alumina, iron, and magnesium oxides. Adsorption data showed that the studied clay samples removed substantial amounts of heavy metals in single and mixed systems. Initial solution pH and carbonates contents enhanced the removal capacities of the studied clay samples, confirming their strong influencing effects. Thermodynamic parameters indicated an endothermic adsorption for metals removal by calcareous clay, but exothermic process for the smectitic sample. These results suggest that the Late Cretaceous clays, Tunisia, can be effectively used as natural adsorbents for the removal of toxic heavy metals in aqueous systems.     

伟晶岩结晶动力学和热力学及稀有金属超常富集成矿机制

本文综述了伟晶岩结晶动力学、热力学和伟晶岩熔体稀有金属元素实现超常富集成矿的机制。结晶动力学涉及成核动力学和晶体生长动力学两个方面。低成核速率和高晶体生长速率是伟晶岩结晶动力学的重要特征,在结晶过程受到水、助溶剂以及过冷条件三个因素共同制约。伟晶岩熔体的相态（超临界态）可能在伟晶岩形成和稀有金属元素超常富集中扮演重要角色。花岗伟晶岩稀有金属超常富集程度受到岩浆源区成分、岩浆结晶分异过程与熔体化学成分等因素的控制。花岗质岩浆高度分异结晶或者变质沉积岩部分熔融直接形成的成矿伟晶岩熔体均需要源岩中稀有金属元素预富集。深熔作用产生的低程度、小体积的伟晶岩熔体具有更高的稀有金属元素成矿潜力。在岩浆分异演化过程中,稀有金属元素的超常富集主要通过超临界熔体/流体、岩浆熔体作用、过冷作用实现。超临界熔体/流体发生熔体- 流体不混溶作用使稀有金属元素在熔体相和流体相间再分配和富集;岩浆熔离作用使稀有金属元素选择性分配到富挥发分的熔体中,导致稀有金属元素再次富集;过冷作用降低稀有金属矿物结晶的饱和浓度,促进稀有金属矿物结晶。熔体的化学成分（如挥发分）直接影响熔体的物理、化学性质。例如,挥发分的富集能够降低熔体黏度,促进岩浆分异结晶过程。挥发分和稀有金属元素的亲和性也控制稀有金属元素在不同相熔体中的分配和富集,显著增加稀有金属元素的溶解度和迁移富集能力,有助于伟晶岩中稀有金属超常富集和成矿。     

Cation distribution in pentlandites (Fe,Ni)9S8: Dependence on pressure and temperature and kinetics of the cation exchange reaction

This paper describes the distribution of Fe and Ni between the octahedral and tetrahedral sites in pentlandite (Fe,Ni)₉S₈. The dependence of the distribution on pressure and temperature and the activation energy of the cation exchange reaction were determined through annealing experiments. Synthetic crystals were annealed at 433–723 K and pressures up to 4 GPa, and natural crystals were annealed at 423, 448 and 473 K in evacuated silica capillary tubes for various durations. The cation distributions in the synthetic crystals were determined with an X-ray powder method employing the anomalous dispersion effect of CuK. and FeK radiations, while those of natural crystals were calculated from the cell dimensions. The values of U, S and V for the Fe/Ni exchange reaction are –6818 J mol^–1, 20.52 J K^–1 mol^–1, and 6.99 × 10^–6 m³ mol^–1, respectively. The dependence of the Fe/Ni distribution on pressure (Pa) and temperature (Kelvin) was determined as lnK = 2.47+8.20 × 10² T ^–1+8.41 x 10^–7 T ^–1 P, where K = (Fe/Ni)_octahedral /(Fe/Ni)_tetrahedral. The activation energy of the cation exchange reaction was 185 kJ mol^–1.     

Adsorption of lead, ethylenediaminetetraacetic acid and lead-ethylenediaminetetraacetic acid complex onto granular activated carbon

This study investigated simultaneous removal of lead and ethylenediaminetetraacetic acid from synthetic wastewater samples using granular activated carbon adsorption. Data from a 1 × 10^?4 M lead-ethylenediaminetetraacetic acid adsorption isotherm study fitted well to Freundlich isotherm. Furthermore, for the pH-dependent 1 × 10?4 M lead-ethylenediaminetetraacetic acid study both lead and ethylenediaminetetraacetic acid adsorptions increased reaching values of 82 % and 93 % respectively at pH 5.8. However, a further increase in pH resulted in decreasing but near equal lead and ethylenediaminetetraacetic acid removals. Results for the 2 × ^10?4 M lead-ethylenediaminetetraacetic acid system showed a behavior that was qualitatively similar to the 1 × ^10?4 M lead-ethylenediaminetetraacetic acid findings. However, the 1×10^?3 M lead-ethylenediaminetetraacetic acid study showed only a decreasing adsorption trend. An increasing-decreasing type lead/ethylenediaminetetraacetic acid adsorption behavior was also noted for the 1× 10^?4 M lead/2 × 10^?4 M ethylenediaminetetraacetic acid system. Nevertheless for the 2×10^?4 M lead/1×10^?4 M ethylenediaminetetraacetic acid system, lead removal at increased pH was comparatively higher. Furthermore, results from a continuous column study completed at 1 × 10^?4 M lead and 0.75 × 10^?4 M ethylenediaminetetraacetic acid showed high saturation times both for lead and ethylenediaminetetraacetic acid. Results from the present work show that a notable removal of aqueous phase lead and ethylenediaminetetraacetic acid could be achieved using activated carbon adsorption. The details related to the effect of pH and pollutants’ concentration on the overall adsorption efficiency, as reported in the present work, would be of much use for an effective carbon adsorption process design for the treatment of respective wastewaters.     

Adsorption of Pentachlorophenol onto Oxide and Clay Minerals： Surface Reaction Model and Environmental Implications

The adsorption of pentachlorophenol （PCP） onto quartz, kaolinite, illite, montmorillonite and iron oxides has been investigated by batch equilibrium techniques. The pH-dependent isotherms are curves with peak values, the position of which is at about pH = 5-6 depending on the mineral species. Based on distribution of both speciation of surface hydroxyls on minerals and PCP in solution a surface reaction model involving surface complexation and surface electrostatic attraction is presented to fit the pH-dependent isotherms, and both reaction constants are calculated. The results show that on quartz and phyllosilicate minerals the predominant adsorption reaction is surface complexation, meanwhile both of surface electrostatic attraction and surface complexation are involved on the iron oxide minerals. The reaction constants of surface electrostatic adsorption are usually one to three orders in magnitude, larger than that of surface complexation. The concentration-dependent isotherms can be well fitted by Langmnir equation with the correlation coefficient R〉0.93 for kaolinite and iron oxides. The maximum adsorption is found in the order： hematite 〉 lepidocrocite 〉 goethite 〉 kaolinite 〉 quartz 〉 montmorillonite ≈ illite, which can be interpreted by consideration of both reaction mechanism and surface hydroxyl density. The significant adsorption of PCP onto mineral surfaces suggests that clay and iron oxide minerals will play an important role as HIOCs are adsorbed in laterite or latertoid soil, which is widespread in South China.     

Adsorption of thorium and protactinium onto different particle types: experimental findings

Here we present the results of experiments investigating the adsorption of Protactinium and Thorium onto different particle types in natural seawater. Particle types studied were smectite as a representative of clay, biogenic opal from a cleaned diatom culture, manganese dioxide precipitate, and calcium carbonate. The particles were added to three different types of natural seawater (0.5 mg/L) which were first 0.2 μm-filtered, and the distribution of Pa and Th between dissolved and particulate phase (>0.2 μm) was monitored for 4 to 5 d at increasing time intervals. The tracers applied were the β-emitters ²³³Pa and ²³⁴Th. The measurement technique via β-counting for both nuclides in the same sample is reported here for the first time.The observed recoveries during the experiment range from 40 to 99 (±5) % for Th and from 51 to 105 (±6) % for Pa. The distribution coefficients (K_d) after establishment of an equilibrium cover a wide range for Th from 0.5 to 107 × 10⁶ ml/g, and from 0.03 to 166 × 10⁶ ml/g for Protactinium, depending on particle type and on the type of seawater used.Thorium revealed a specific affinity for all particle types investigated, with varying degree and adsorption kinetics. The results suggest that all particle types investigated may serve as Th carrier phases in the sediment. Pa was found to be less particle reactive than Th in most cases. Th/Pa fractionation factors (F_Th/Pa) were also obtained. Weakest fractionation was found on MnO₂ (F_Th/Pa=1), followed by the chemically cleaned biogenic opal (2.8) and smectite (5.4). The results for calcium carbonate were highly variable. Our experimental results imply that particle composition is indeed playing a role in the differing marine geochemistry of Th and Pa. We conclude that experiments with filtered natural seawater using particle concentrations on a natural level are a helpful approach when investigating the geochemical behaviour of strongly particle-reactive elements like Th and Pa in the marine environment.     

Removal of 4-chloro-2-nitrophenol occurring in drug and pesticide waste by adsorption onto nano-titanium dioxide

The present study deals with removal of 4-chloro-2-nitrophenol (4C2NP) as a model contaminant from pharmaceutical and pesticide industries using titanium dioxide nanoparticles as an adsorbent. 4C2NP is recalcitrant and persistent toward biodegradation and its generation in aqueous environment during formulation, distribution and field application of pesticides is often unavoidable. Batch experiments were carried out to investigate the effect of contact time, nano-titanium dioxide dosage, initial pH, initial 4C2NP concentration and temperature on adsorption efficiency. The results showed that the adsorption capacity was increased with increasing 4C2NP concentration and temperature. Optimum conditions for 4C2NP adsorption were found to be initial pH????2, nano-titanium dioxide dosage????0.01?g/250?mL and equilibrium time????1?h. Titanium dioxide nanoparticles recorded a maximum capacity of 86.3?mg/g at optimal conditions. The linear correlation coefficients of Langmuir, Freundlich and Temkin isotherms were obtained. The results revealed that the Freundlich isotherm fitted the experimental data better than the other isotherm models.