Hexavalent chromium removal from aqueous solutions by using low-cost biological wastes: equilibrium and kinetic studies

The batch removal of hexavalent chromium from aqueous solutions using almond shell, activated sawdust, and activated carbon, which are low-cost biological wastes under different experimental conditions, was investigated in this study. The influences of initial concentration, adsorbent dose, adsorbent particle size, agitation speed, temperature, contact time, and pH of solution were investigated. The adsorption was solution pH dependent and the maximum adsorption was observed at a solution pH of 2.0. The capacity of chromium adsorption under equilibrium conditions increased with the decrease in particle sizes. The equilibrium was achieved for chromium ion after 30?min. Experimental results showed that low-cost biosorbents are effective for the removal of pollutants from aqueous solution. The pseudo-second-order kinetic model gave a better fit of the experimental data as compared to the pseudo-first-order kinetic model. Experimental data showed a good fit with the Freundlich isotherm model. Changes in the thermodynamic parameters, including Gibbs free energy (??G_o), enthalpy (??H_o), and entropy (??S_o), indicated that the biosorption of hexavalent chromium onto almond shell, activated sawdust, and activated carbon was feasible, spontaneous, and endothermic in the temperature range 28?C50?°C.     

Adsorption of heavy metals in glacial till soil

The charged sites on soil particles are important for the retention/adsorption of metals. Metallic counterions can neutralize the intrinsic charges on the surfaces of soil particles by forming complexes. In this study, efforts have been made to determine the effect of surface potential, pH, and ionic strength on the adsorption of four metal ions, hexavalent chromium Cr(VI), trivalent chromium Cr(III), nickel Ni(II) and cadmium Cd(II), in glacial till soil. Batch tests were performed to determine the effect of pH (2–12) and ionic strength (0.001–0.1 M KCl) on zeta potential of the glacial till soil. The point of zero charge (pH _PZC ) of glacial till was found to be 7.0±2.5. Surface charge experiments revealed the high buffering capacity of the glacial till. Batch adsorption experiments were conducted at natural pH (8.2) using various concentrations of selected metals. The adsorption data was described by the Freundlich adsorption model. Overall glacial till shows lower adsorption affinity to Cr(VI) as compared to cationic metals, Cr(III), Ni(II) and Cd(II).     

Optimization of a PRB structure with modified chitosan restoring Cr(VI)-contaminated groundwater

Hexavalent chromium is a soluble, mobile, and highly toxic metal ion in groundwater. Adsorption by permeable reactive barriers (PRBs) with special sorbent is a common method to remove hexavalent chromium. A series of experiments have been performed to remove hexavalent chromium in groundwater under PRB with modified chitosan. Therefore, in this paper, the authors first estimated adsorption characteristics of the modified chitosan in a column test, and then calibrated the PRB adsorption parameters in a sandbox test, and finally designed an optimal width, length, and depth of the PRB with the same reactive media in a three-dimensional aquifer. The results showed that the modified chitosan might be a potential adsorption medium. The design schemes can meet the water quality standard of 0.1 mg/L Cr(VI). Heterogeneity of dispersion is a crucial factor when designing the PRB. Therefore, the design of the PRB structures can be appropriate and serve as reference for groundwater remediation.     

Ionic solid-impregnated sulphate-crosslinked chitosan for effective adsorption of hexavalent chromium from effluents

Microwave-assisted tetrabutyl ammonium-impregnated sulphate-crosslinked chitosan was synthesized for enhanced adsorption of hexavalent chromium. The adsorbent obtained was extensively characterized using Fourier transform infrared, X-ray diffraction, scanning electron microscopy and energy-dispersive X-ray studies. Various isotherm models such as Langmuir, Freundlich and Dubinin–Radushkevich were studied to comprehend the adsorption mechanism of hexavalent chromium by the adsorbent. Maximum adsorption capacity of 225.9 mg g^?1 was observed at pH 3.0 in accordance with Langmuir isotherm model. The sorption kinetics and thermodynamic studies revealed that adsorption of hexavalent chromium followed pseudo-second-order kinetics with exothermic and spontaneous behaviour. A column packed with 1 g of adsorbent was found to give complete adsorption of Cr(VI) up to 900 mL of 200 mg L^?1 solution which discerns the applicability of the adsorbent material for higher sample volumes in column studies. The effective adsorption results were obtained due to both ion exchange and ion pair interaction of adsorbent with hexavalent chromium. Greener aspect of overall adsorption was regeneration of the adsorbent which was carried out using sodium hydroxide solution. In the present study, the regenerated adsorbent was effectively reused up to ten adsorption–desorption cycles with no loss in adsorption efficiency.     

An experimental study on diffusion characteristics of hardened liner materials to inorganic chemicals

For materials of very low hydraulic conductivity used in the landfill liner systems, e.g., natural clay liners, soil-cement liners, etc., diffusion characteristics should be evaluated, as the transport mechanism of contaminant through them is diffusion controlled. Studies on the diffusion characteristics of the hardened liner materials, such as the soil cement, are relatively few compared with those of clayey soils. In this paper, diffusive characteristics of hardened liner materials (HLMs) applied to the liner system of Sudokwon Metropolitan Landfill in Korea, were studied. Laboratory pure diffusion column tests in the pure- and the advection-diffusion status were performed for the chemicals, NaCl, KCl, and CaCl₂. To evaluate the diffusion coefficient of a HLMs system, a one-dimensional numerical transport program was developed for use in a multi-layered HLMs system. The range of dispersion coefficients of advection diffusion column tests was a little narrower than that of diffusion coefficients of pure diffusion tests, although the two coefficients were quite close. The effective diffusion coefficients of chloride ions of a HLMs were about a half of those in clayey soil due to the high density by compaction and curing. Diffusion coefficients of chloride ions in this study were correlated closely with hydraulic conductivities of the materials tested and were consistent with work in the literature.     

垃圾填埋场斑脱土衬里可行性评价

首先对斑脱土衬里(粘土-斑脱土、砂-斑脱土) 进行变水头实验, 得粘土-斑脱土的渗透系数为6.0×10-9~3.0×10-8cm/s, 砂-斑脱土的渗透系数为1.0×10-9~3.0×10-9cm/s.从防渗角度分析, 2种斑脱土混合物均适合作垃圾填埋场的底层衬里.然后对斑脱土衬里进行持水与水迁移实验, 评价斑脱土衬里水的迁移特性.以水迁移实验为基础, 模拟斑脱土衬里与地基5种不同含水量的条件, 对斑脱土衬里进行直接剪切实验, 测定斑脱土衬里的剪切强度及斑脱土衬里与地基接触面的剪切强度.再对斑脱土衬里进行三轴固结不排水实验, 测定其总剪切强度与有效剪切强度.实验结果表明: 地下水具有很大的潜力从地基流向斑脱土衬里, 从而大大提高斑脱土衬里的含水量; 随着含水量的增加, 粘土-斑脱土、砂-斑脱土衬里的抗剪强度逐渐减小.根据实验所获得的抗剪强度参数, 选择日本山谷型垃圾填埋场典型剖面, 对山谷型垃圾填埋场进行稳定性评价.结果表明: 对于角度小于20°的缓倾角山谷型垃圾填埋场, 使用粘土-斑脱土、砂-斑脱土作为底层衬里是稳定的.因此, 2种斑脱土混合物适合作山谷型垃圾填埋场的底层衬里.      

Efficient removal of hexavalent chromium from aqueous solutions using autohydrolyzed Scots Pine (Pinus Sylvestris) sawdust as adsorbent

In this work, a low-cost lignocellulosic adsorbent with high biosorption capacity is proposed, suitable for the efficient removal of hexavalent chromium from water and wastewater media. The adsorbent was produced by autohydrolyzing Scots Pine (Pinus Sylvestris) sawdust. The effect of the autohydrolysis conditions, i.e., pretreatment time and temperature, on hexavalent chromium biosorption was investigated using energy-dispersive X-ray spectroscopy (EDS) and UV–visible spectrophotometry. The Freundlich, Langmuir, Sips, Radke-Prausnitz, Modified Radke-Prausnitz, Tóth, UNILAN, Temkin and Dubinin-Radushkevich adsorption capacities and the rate constant values for pseudo-first- and pseudo-second-order kinetics indicated that the autohydrolyzed material exhibits significantly enhanced hexavalent chromium adsorption properties comparing with the untreated sawdust. The Freundlich’s adsorption capacity K _F increased from 2.276 to 8.928 (mg g^?1)(L mg^?1)^1/n , and the amount of hexavalent chromium adsorbed at saturation (Langmuir constant q _m) increased from 87.4 to 345.9 mg g^?1, indicating that autohydrolysis treatment at 240 °C for 50 min optimizes the adsorption behavior of the lignocellulosic material.     

Decontamination of hexavalent chromium and tri-ethyl phosphate stimulants through photacatalytic oxidation

In this paper, the photocatalytic decontamination of hexavalent chromium and tri-ethyl phosphate, two important wastewater contaminants, are studied by the ultraviolet / nano-titanium dioxide process. The pH value and synergic effect between the oxidation of tri-ethyl phosphate and the reduction of hexavalent chromium were investigated in different concentrations of tri-ethyl phosphate and hexavalent chromium. Furthermore, the effects of ultraviolet and nano-titanium dioxide were investigated in a solution which contained tri-ethyl phosphate and hexavalent chromium. Results of adsorptions showed that hexavalent chromium was adsorbed better in acidic pH while the better adsorption for tri-ethyl phosphate was occurred in alkalinity pH. The reduction rate of hexavalent chromium was higher in acidic solutions while it was obtained at natural pH for tri-ethyl phosphate. In co-adsorption of hexavalent chromium and triethyl phosphate pollutants, tri-ethyl phosphate slightly increased adsorption of hexavalent chromium, but hexavalent chromium had no influence on the adsorption of tri-ethyl phosphate on nano-titanium dioxide particles. In contrast, triethyl phosphate has an improving effect on the reduction reaction rate of hexavalent chromium which increases with the interaction of the concentration of tri-ethyl phosphate in mixture. The same is true for the oxidation rate of tri-ethyl phosphate.     

Sorption capacity on lead,copper and zinc by clay soils from South Wales,United Kingdom

The sorption capacity of five clay soils from South Wales in the United Kingdom was investigated using two main tests; physico-chemical and batch equilibrium (BET). The physico-chemical property results show that soil weathered mudrocks (MR1), glacial till (GT1), and estuarine alluviums (NEA4, PEA3 and CEA3) are capable of being used as landfill liners and are chosen for further sorption tests. The batch tests (i.e. sorption tests) on soil suspension produce adsorption-pH curves, showing increasing adsorption at higher pH levels. The sorption data are also presented using adsorption isotherm curves and are best fitted using the Langmuir adsorption equation that yields the maximum adsorption capacity of the soils. The sorption capacity of soils are ranked as estuarine alluvium soils>glacial till>weathered mudrocks. Estuarine alluvium soils show a good buffering capacity and high sorption capability compared to glacial till and weathered mudrocks. The study also discovers that the maximum sorption capacities are highly influenced by the chemical properties of the soils.     

Hydraulic conductivity of remolded fine-grained soils versus index properties

Hydraulic conductivity is a dominant parameter in the design of engineered waste disposal facilities such as landfill liners and covers, lagoon liners and slurry walls. It is of interest to a geotechnical or geo-environmental engineer to develop a predictive method of determining the hydraulic conductivity of fine-grained soils, in order to assess its suitability as a liner material. To predict the hydraulic conductivity of soils, researchers and geotechnical engineers have attempted to correlate it with index properties of the soils, such as the liquid limit, void ratio and specific surface. Based on the present study a predictive method has been developed in this paper to predict the hydraulic conductivity in terms of void ratio and shrinkage index (Liquid limit – shrinkage limit) for remoulded fine-grained soils. Though the initial conditions for the soil will affect the hydraulic conductivity behaviour to some extent, both the void ratio and soil characteristics are primary factors in affecting the hydraulic conductivity. Therefore for predictive purpose, the study of hydraulic conductivity behaviour of remoulded fine-grained soils as presented in this paper can be found to be useful for compacted soils also.     

Removal of hexavalent chromium from aqueous solution by barium ion cross-linked alginate beads

Barium ion cross-linked alginate beads have shown great affinity to toxic hexavalent chromium ions in aqueous solution, in contrast to the traditionally used calcium alginate beads. Our adsorption experiments were carried out by the batch contact method. The optimal pH for removal was found to be pH 4. The equilibrium was established in 4 h, and the removal efficiency of chromium(VI) was found to be 95 %. The adsorption data were applied to Langmuir, Freundlich, Dubinin–Redushkevich (D–R), and Temkin isotherm equations. Both Langmuir and Freundlich isotherm constants indicated a favorable adsorption. The value of mean sorption energy calculated from D–R isoterm indicates that the adsorption is essentially physical. The high maximum chromium(VI) adsorption capacity was determined from the Langmuir isotherm as 36.5 mg/g dry alginate beads. The chromium(VI) adsorption data were analyzed using several kinetic models such as the pseudo-first-order, pseudo-second-order, intraparticle diffusion, and Elovich models, and the rate constants were quantified. Our study suggests that barium alginate beads can be used as cost-effective and efficient adsorbents for the removal of chromium(VI) from contaminated waters.     

基于混合物理论的水力-化学-力学污染物输运模型研究

由于废弃物的堆积以及填埋场上覆盖层的重量,衬垫因此承受一定的压力,发生力学固结;由于黏土本身的结构特性,当污染物通过黏土垫层时可能会发生化学固结,而固结作用可直接对污染物的对流输运产生影响,也会引起土层体积和结构的变化,从而改变其固有的输运性质。从混合物理论出发,建立了水力-化学-力学作用下的溶质输运理论框架,统一地描述了水力-化学-力学作用下变形、水的吸附或解吸附、对流和扩散现象。将输运系数考虑为有效孔隙率的函数,由此反映固结对输运参数的影响。对所建立的数学模型进行无量纲化处理,并使用有限元软件COMSOL Multiphysics进行求解,最后进行了参数分析。研究结果表明,垫层土体中吸附水和自由水之间的化学势差异越大,层间吸附水的解吸附量越大;当土体的软硬性质不同时,当层间吸附水解吸附后,土体固结程度不同,从而对污染物输运过程的影响不同。而当垫层上覆荷载增大时,土体宏观孔隙的扩张的限制作用增强,从而对土体产生一种修复作用,抑制污染物在土体中的输运。     

Adsorption studies of 1,2,4-Trichlorobenzene onto shallow aquifer media at the Luhuagang landfill site in Kaifeng,China

The Luhuagang landfill site (LLS) in Kaifeng, China, lacks liner and leachate collection systems. Thus, leachate generated from the waste dump has contaminated the surrounding subsoil and shallow aquifer with various chemicals, including 1,2,4-Trichlorobenzene (1,2,4-TCB). This paper is a part of a series of studies on adsorption, transport and biodegradation and fate of 1,2,4-TCB in the shallow aquifer beneath LLS. Here, adsorption of 1,2,4-TCB onto silt, fine sand and medium sand aquifer deposits collected at LLS was conducted by performing batch experiments involving four common adsorption kinetic models. The results of the analyses showed that the pseudo-second-order adsorption kinetic model provided the best fit for the equilibrium data with a coefficient of determination (R ²) greater than 0.99. Least squares analysis of Henry, Freundlich and Langmuir linearly transformed isotherm models was used to establish the best isotherm for 1,2,4-TCB adsorption onto the three aquifer materials. The Freundlich isotherm provided the best fit for experimental data with R ² > 0.99. The results further suggested that the highest adsorption rate of 1,2,4-TCB (27.55 μg/g) was onto silt deposit, followed by fine sand (21.65 μg/g) and medium sand (14.88 μg/g). This showed that silt layer beneath the LLS was critical for retarding the downward percolation and migration of 1,2,4-TCB into the shallow aquifer systems under the landfill. The findings of the study were adopted as basis for designing the slated transport and biodegradation study of 1,2,4-TCB in aquifer system at LLS.     

Analysis of flow behavior in a landfill with cover soil of low hydraulic conductivity

 This paper presents the results of field tests of hydrologic parameters in a landfill and the results of numerical simulation to find the efficiency of the pumping method to reduce leachate levels in the landfill. The field hydraulic conductivity and storativity of waste and buried cover soils in the landfill are measured by pumping and slug tests. The hydrologic condition inside the landfill is first calibrated using the drawdown-time curve obtained from the pumping test, and the flow behavior of leachate during pumping in the landfill, when various layers of waste and buried cover soil exist, is analyzed through three-dimensional numerical simulation of flow. The results of the field investigation show that the buried cover soil of low hydraulic conductivity forms an impermeable layer preventing the downward flow of leachate and upward flow of landfill gas. The hydraulic conductivities of the pumping test and slug tests were quite close on the same order of magnitude. It was also possible to match the drawdown-time data of the field tests with those of the model using input data close to the hydrologic property obtained from the field tests. The numerical flow analysis showed that pumping was possible up to 120 tons/day for a single well without a drain, while the pumping rate could be increased to 300 tons/day for the same well with the drain. From the vertical section of the flow vector with a horizontal drain, the barrier role of buried cover soil is identified, which was proposed by examining the water contents of the disposed cover soil and waste in the field. Received: 15 May 1998 · Accepted: 4 January 1999     

废旧轮胎胶粉对高岭土变形和渗透性质的影响

废旧轮胎胶粉用于填埋场衬垫材料改性,是提高衬垫系统有效性和扩展废旧轮胎资源化利用途径的一种手段。以高岭土作为黏性土的代表,开展废旧轮胎胶粉-高岭土混合土的力学和水力学性质试验,重点探讨胶粉掺量及尺寸对混合土渗透性、压缩性和收缩性的影响规律。研究表明,废旧轮胎胶粉-高岭土混合土的渗透系数、压缩系数、回弹指数、固结系数和体缩率等均随胶粉掺入比的增加而增大。高岭土及混合土的无侧限抗压强度大于200kPa,50kPa和200kPa压力下渗透系数满足≤1.0×10-7cm·s-1的要求,均属于中压缩性土,且体缩率小于体积应变合格值4%。与30目胶粉相比,12目胶粉-高岭土混合土压缩性和回弹量较小、固结系数较大,胶粉尺寸对无侧限抗压强度、体缩率和渗透系数的影响不显著。在本文试验条件下,为提高黏土衬垫对有机污染物的吸附能力并满足渗透性、强度及变形的要求,12目25%胶粉改性黏土可作为填埋场黏土衬垫材料。     

Adsorption of arsenic(V) on bone char: batch,column and modeling studies

Bone char has been used as a low-cost adsorbent for the removal of As(V) from waste water. The batch experiments show that the Langmuir isotherm describes well the adsorption behavior. The adsorption process follows a pseudo-second-order kinetic model. The column experiments were conducted at pH = 4 and 10 mg/L an initial concentration of As(V). The breakthrough curves were investigated for various conditions, such as different flow rates, column bed heights, adsorption cycles, coexisting cations and anions such as Mn²⁺, Al³⁺, PO₄ ^3?, SO₄ ^2? and SiO₃ ^2?. The convection–diffusion equation was used to model the experimental transport data of As(V) for these conditions. It has been found that the coexisting cations can enhance As(V) immobilization and increase retardation factor (R _f), and coexisting anions significantly decrease the diffusion coefficient (D _L) of As(V). The secondary adsorption phenomena were observed in the breakthrough curves of column studies of As(V) with cations, especially Mn²⁺. The regeneration experiments using distilled water and 0.1 mol/L NaOH solution were done to evaluate the desorption degree. The total desorbed amounts from whole column for three experiments decreased from 8.98 to 7.67 mg and the desorption degrees increased from 0.51 to 0.71 unexpectedly, which indicates that the regeneration operation is feasible. Finally, the chemical analysis of column effluents and infrared spectroscopic analysis of absorbent both revealed that the ligand exchange and electrostatic interaction are the main removal mechanisms.     

Use of sulfur-oxidizing bacteria for assessment of chromium-contaminated soil

In recent years, biological toxicity tests have been conducted for soil assessment of environmental pollutants to evaluate the environmental risk due to heavy metals. In this study, batch tests were conducted with soils contaminated with hexavalent chromium (Cr⁶⁺) using sulfur-oxidizing bacteria (SOB). For control soils (without Cr⁶⁺), the electrical conductivity (EC) increased linearly over time in all samples, indicating that no toxic substances were present in the soil. The initial EC varied between 6 and 7.8 mS/cm, and the final EC varied between 22 and 27 mS/cm after incubation for 65 h. For batch tests performed using Cr⁶⁺-contaminated soil, the EC increased slightly or remained stable in all the test samples after a few hours. Thus, the presence of toxic substance Cr⁶⁺ inhibited the SOB, which leads to no sulfuric acid formation and therefore, no change in EC. These results indicated that SOB can be employed as a test microorganism to assess the quality of heavy metal-contaminated soils.     

Formation of one-dimensional composites of poly(<Emphasis Type="Italic">m</Emphasis>-phenylenediamine)s based on <Emphasis Type="Italic">Streptomyces</Emphasis> for adsorption of hexavalent chromium

Here, a novel one-dimensional composite of poly(m-phenylenediamine)s coating on filamentous Streptomyces was successfully constructed via a controllable polymerization reaction. The synthesized composites were characterized by scanning electron microscopy, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy. Their adsorption isotherm and kinetics for aqueous hexavalent chromium were also systematically examined. The results of scanning electron microscopy analysis indicated that the obtained composites based on Streptomyces were showed a uniform and stable one-dimensional morphology with distinct core–shell configuration. Moreover, the Langmuir isotherm model (R ² > 0.96) and pseudo-second-order equation (R ² = 0.9996) described well the equilibrium adsorption behavior and kinetics of hexavalent chromium adsorption by the composites. In addition, bath adsorption experiments demonstrated the highest adsorption capacity of hexavalent chromium by the composites reached 320.03 mg g^?1 in an acid solution, which was 5.6 times as that of the pure Streptomyces filaments. The results of Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy analyses suggested that the adsorption of hexavalent chromium by the composites possibly involved the protonation, redox, and chelation reactions. Therefore, a promising application of these composites in treating acid hexavalent chromium-contaminated wastewater is expectable.     

Potential biosorbents for treatment of chromium(VI)-contaminated water discharged into Asopos River

The present study reports on the preliminary investigation of three low-cost natural materials with respect to their chromium(VI) removal efficiency from contaminated water. The tested materials were reed, in milled and chopped form, compost, and dewatered sludge from a municipal wastewater treatment plant. The chromium(VI) removal capacity of the aforementioned materials was investigated by simulating the physicochemical conditions prevailing in a stormwater outfall flowing into the Asopos River in Inofyta, Central Greece. Thus, batch and column experiments were carried out using solutions of 3–5 mg/L chromium(VI) and pH value 8.5 ± 0.5. The results showed that the tested materials were capable of removing 3 mg/L chromium(VI), however by allowing different contact times for each material. The chromium(VI) removal kinetics were studied through batch experiments, and reed was found to be the most efficient material. Therefore, at a second series of batch and up-flow column experiments, the effect of the liquid-to-solid ratio, pH, and contact time on chromium(VI) removal using chopped reed was investigated. Chromium(VI) removal took place through both reduction and adsorption mechanisms, while the released soluble organic matter from reed seemed to favor the reduction mechanism. As a result, reed is a potential biosorbent capable of treating heavily chromium(VI)-contaminated water flows, although a high mass of reed is required for a treatment process, such in the case of the stormwater discharged into Asopos River.     

Synthesis of nano-γ-Al<Subscript>2</Subscript>O<Subscript>3</Subscript>/chitosan beads (AlCBs) and continuous heavy metals removal from liquid solution

In this work, synthesis of chitosan beads impregnated with nano-γ-Al₂O₃ (AlCB) was carried out. The characteristics of the synthesized adsorbent were obtained by using Brunauer Emmett and Teller technique and Scanning Electron Microscopy method. The use of AlCB in continuous removal of chromium, lead, nickel and cadmium ions from liquid solution was studied using fixed-bed column system. Bed depths and flow rate effects on breakthrough and uptake capacity of the adsorbent in column were also examined. Dynamic parameters of the adsorption were calculated by using bed depth service time (BDST) and Thomas models. In both models, the data were analyzed by error analyzing and combining the values of determined coefficient (R ²) from regression analysis. The adsorption capacities of AlCB in breakthrough were 158.33, 183.33, 63.33 and 31.67 mg/g for chromium, lead, nickel and cadmium, respectively. In addition, BDST model was found to be an acceptable kinetic model to describe the experimental data.