Adsorption kinetic studies for removal of methylene blue using activated carbon prepared from sugar beet pulp

Sugar beet pulp is an abundant, renewable and low-cost precursor for production of activated carbon. In the present study, sugar beet pulp based activated carbon was prepared by using phosphoric acid as activating agent for adsorption of methylene blue. The conditions of preparation process had a significant influence on the adsorption of methylene blue, and the optimal preparation conditions were obtained as follows: liquid-to-solid ratio of 5, temperature of 450 °C and phosphoric acid concentration of 3 mol/L. The properties of sugar beet pulp based activated carbon were characterized by nitrogen adsorption isotherm. The adsorption increases as the increase of contact time, adsorption temperature and pH, and initial concentration of methylene blue. Batch kinetic studies showed that an equilibrium time of 100 min was needed for the adsorption, and the adsorbance of methylene blue is 244.76 mg/g at equilibration. Kinetic models, Weber’s pore diffusion model and Boyd’s equation were applied to the experimental data to study the mechanism of adsorption and the controlled step. The results showed that the adsorption kinetics followed the pseudo-second-order type kinetic model, intraparticle diffusion was not the rate-limiting mechanism and adsorption process was controlled by film diffusion.     

Evaluation of coal as adsorbent for phosphate removal

This paper reports the adsorption of phosphate ions on coal, charcoal, and coal ash. The influences of factors such as contact time, and initial adsorbate concentration have been studied. Adsorption of phosphate ions on virgin coal was significant compared to charcoal, coal and coal ash evacuated at 200°C. The significant adsorption capability of coal is due to the porosity as well as due to organic carbon and inorganic elements present in coal. The evacuation of coal proved to be ineffective in enhancing its capability for phosphate ions retention. The adsorption behaviors of all the three adsorbent used was conformed using Freundlich’s adsorption model. The results suggest that coal could be used as an efficient adsorbent for removing phosphate ions from wastewater.     

Accelerated aqueous leaching of selenium and arsenic from coal associated rock samples with selenium speciation using ultrasound extraction

Ultrasound extraction was used to compare the accelerated release rates of selenium and arsenic from three rocks (BT700, BT 571 and BT 60) that are associated with mountaintop mining and valley fill coal mining practiced in southern parts of West Virginia, USA. The concentrations of arsenic released from rocks were found to be three orders of magnitude higher than that of selenium. The accelerated leaching rate constants were ten times higher for arsenic compared to selenium. Se (IV) was found to be stable under ultrasound extraction conditions used whereas As (III) was quickly oxidized to As (V). BT700 was found to have more Se (IV) compared to BT571 while BT60 did not have any significant Se (IV) concentrations. Such compositional and kinetic information becomes important when determining suitable mining waste treatment protocols that have to be undertaken to different types of overburden before it is dumped in valleys.     

Phosphate removal using compounds prepared from paper sludge and fly ash

Using waste as a resource to control phosphate pollution is a rising trend. This study describes the use of paper sludge (PS) and fly ash (FA), industrial solid wastes, to prepare materials with high phosphate uptake efficiency. The process consisted of pretreatment (mechanical milling), calcination, acidification (HCl), and post-treatment (aging, drying and grinding). The maximal phosphate uptake (>92 %) was achieved using PS together with FA either at PS/FA = 0.5 g/g or at PS/FA = 2.0 g/g, both calcined at 900 °C for 2 h and stirred with HCl (HCl/FA = 3 mL/g) for 1 h. With increasing calcination temperature and decreasing acid, the crystallinity of samples declined, and phosphate uptake (PU) increased. The PU process could be well described by the pseudo-second order kinetic model, while equilibrium state could be reasonably modeled by Langmuir isotherm. Neutral and weak alkaline pH promoted the PU efficiency, and 0.3 g sample/100 mL was the cost-effective dosage under the experimental conditions. The enhanced phosphate uptake of PS and FA provides alternative materials for phosphate removal from wastewater by the use of solid wastes in paper-making industries.     

Modeling transport of arsenic through modified granular natural siderite filters for arsenic removal

Groundwater arsenic(As)contamination is a hot issue,which is severe health concern worldwide.Recently,many Fe-based adsorbents have been used for As removal from solutions.Modified granular natural siderite(MGNS),a special hybrid Fe(II)/Fe(III)system,had higher adsorption capacity for As(III)than As(V),but the feasibility of its application in treating high-As groundwater is still unclear.In combination with transport modeling,laboratory column studies and field pilot tests were performed to reveal both mechanisms and factors controlling As removal by MGNS-filled filters.Results show that weakly acid pH and discontinuous treatment enhanced As(Ⅲ)removal,with a throughput of 8700 bed volumes(BV)of 1.0 mg/L As(Ⅲ)water at breakthrough of 10 μg/L As at pH 6.Influent HCO_3~-inhibited As removal by the filters.Iron mineral species,SEM and XRD patterns of As-loading MGNS show that the important process contributing to high As(Ⅲ)removal was the mineral transformation from siderite to goethite in the filter.The homogeneous surface diffusion modeling(HSDM)shows that competition between As(III)and HCO_3~-with adsorption sites on MGNS was negligible.The inhibition of HCO_3~-on As(Ⅲ)removal was connected to inhibition of siderite dissolution and mineral transformation.Arsenic loadings were lower in field pilot tests than those in the laboratory experiments,showing that high concentrations of coexisting anions(especially HCO_3~-and SiO_4~(4-)),high pH,low EBCT,and low groundwater temperature decreased As removal.It was suggested that acidification and aeration of highAs groundwater and discontinuous treatment would improve the MGNS filter performance of As removal from real high-As groundwater.     

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.     

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.     

Microbial fuel cell operation using nitrate as terminal electron acceptor for simultaneous organic and nutrient removal

A double-chambered biocathode microbial fuel cell with carbon felt employed as electrodes was developed for wastewater treatment and bioelectricity generation simultaneously. The system was operated in fed-batch mode for over eight batches. The effect of circuit connections on organic and nitrate reduction was investigated. The maximum power density recorded was 21.97 mW/m² at current density of 88.57 mA/m². The Coulombic efficiency and internal resistance of the system were 5% and 100 Ω. Up to 89.9 ± 5.9% of chemical oxygen demand reduction efficiency achieved with an influent of 1123 ± 28 mg/L. There was no significant difference in the chemical oxygen demand reduction when system operated in either open or closed circuit. This study clearly showed that higher nitrate reduction efficiency obtained in closed circuit (74.7 ± 7.0%) due to bio-electrochemical denitrification compared to only 41.7% in the open circuit. The result also successfully demonstrated nitrate as terminal electron acceptor for the cathodic nitrate reduction.     

Identification of potential soil adsorbent for the removal of hazardous metals from aqueous phase

The present study attempted to identify the efficient hazardous metal-removing sorbent from specific types of soil, upper and middle layer shirasu, shell fossil, tuff, akadama and kanuma soils of Japan by physico-chemical and metal (arsenic, cadmium and lead) removal characterizations. The physico-chemical characteristics of soil were evaluated using X-ray diffraction and scanning electron microscopy with energy dispersive spectroscopy techniques, whereas metal removal properties of soil were characterized by analyzing removal capacity and sorption kinetics of potential metal-removing soils. The chemical characteristics revealed that all soils are prevalently constituted of silicon dioxide (21.83–78.58 %), aluminum oxide (4.13–38 %) and ferrous oxide (0.835–7.7 %), whereas calcium oxide showed the highest percentage (65.36 %) followed by silicon dioxide (21.83 %) in tuff soil. The results demonstrated that arsenic removal efficiency was higher in elevated aluminum oxide-containing akadama (0.00452 mg/L/g/h) and kanuma (0.00225 mg/L/g/h) soils, whereas cadmium (0.00634 mg/L/g/h) and lead (0.00693 mg/L/g/h) removal efficiencies were maximum in elevated calcium oxide-containing tuff soil. Physico-chemical sorption and ion exchange processes are the metal removal mechanisms. The critical appraisal of three metal removal data also clearly revealed cadmium > lead > arsenic order of removal efficiency in different soils, except in tuff and akadama soils followed by lead > cadmium > arsenic. It clearly signified that each type of soil had a specific metal adsorption affinity which was regulated by the specific chemical composition. It may be concluded that akadama would be potential arsenic-removing and tuff would be efficient cadmium and lead-removing soil sorbents.     

Nettle ash as a low cost adsorbent for the removal of nickel and cadmium from wastewater

This study was focused on nettle ash as an alternative adsorbent for the removal of nickel (II) and cadmium (II) from wastewater. Batch experiments were conducted to determine the factors affecting adsorption of nickel (II) and cadmium (II). The adsorption process is affected by various parameters such as contact time, solution pH and adsorbent dose. The optimum pH required for maximum adsorption was found to be 6. The experimental data were tested using Langmuir, Freundlich and Tempkin equations. The data were fitted well to the Langmuir isotherm with monolayer adsorption capacity of 192.3 and 142.8 mg/g for nickel and cadmium, respectively. The adsorption kinetics were best described by the pseudo second order model. The cost of removal is expected to be quite low, as the adsorbent is cheap and easily available in large quantities. The present study showed that nettle ash was capable of removing nickel and cadmium ions from aqueous solution.     

Application of zeolitic volcanic rocks for arsenic removal from water

Natural zeolitic rocks consisting mainly of chabazite-phillipsite, clinoptilolite, and volcanic glass have been evaluated by means of batch methods to remove arsenic from waters with different mineralization degree (from deionized water to natural water with a specific conductivity of 1,600 μS cm^− 1). Arsenic was previously spiked in the studied waters at concentrations of about 100 µg l^− 1 to simulate actual cases. The compositional range of natural waters is representative of large hydrogeochemical regions around the world. The experiments were focussed on the application of natural common zeolitic rocks to water treatment for human consumption. The removal efficiency observed rises, in the better cases, 60–80% for chabazite-phillipsite raw materials whereas is 40–60% for clinoptilolite-bearing ones. The arsenic removal tends to increase with water mineralization degree, independently of the zeolitic rock type. A large zeolitic content in the chabazite-phillipsite raw materials increase the removal. Instead, the inverse situation is observed in the clinoptilolite-bearing rocks. The relevance of the quantitative mineralogical analysis, determining also the content of volcanic glass, as well as the use of natural waters in the removal tests has been demonstrated.     

利用体外方法评估不同淋洗剂对土壤中砷的淋洗效果及其健康风险

土壤砷污染已成为我国严重的环境问题,淋洗法是修复土壤砷污染较为有效的手段之一。文中以砷污染土壤为研究对象,运用2种环境友好的淋洗剂KH2PO4和草酸进行振荡淋洗实验,探究两种淋洗剂对不同砷污染土壤的淋洗效果,在此基础上,通过2种不同的体外方法 (physiologically based extraction test,PBET;in vitro gastrointestinal,IVG),探索其生物可给性及对人体的健康风险。结果显示,KH2PO4和草酸对土壤中砷有不同程度的去除,草酸对土壤砷的去除率较高,平均去除率为54.3%。运用PBET方法得到的土壤砷的生物可给性高于IVG方法,KH2PO4淋洗后土壤砷的生物可给性高于草酸。与草酸相比,KH2PO4淋洗会在一定程度上增加土壤砷的健康风险。不同in vitro方法对不同淋洗剂修复后效果有不同的评估结果,应该根据不同的淋洗剂选择较为保守的体外方法来评估淋洗后土壤的生物可给性及健康风险。     

Adsorption isotherm models and error analysis for single and binary adsorption of Cd(II) and Zn(II) using leonardite as adsorbent

Leonardite, a by-product from coal mines, was applied to adsorb Cd(II) and Zn(II) from aqueous solutions. Individual and simultaneous adsorptions of the two metal ions were investigated. In a single-component adsorption system, Langmuir and Freundlich isotherms were fitted to the adsorption data. Linear and nonlinear regression methods were used for the assessment of the optimum adsorption isotherm. Error functions including root-mean-square error, sum of the squares of the errors, mean absolute percentage error, Marquardt’s percent standard deviation (MPSD), and Chi-square were applied in the nonlinear regression. The most suitable model for the adsorption of Cd(II) and Zn(II) in the single system is the Freundlich isotherm. The isotherm parameters calculated by MPSD provided the lowest sum of normalized error (SNE) value. The adsorption capacity was found to be 23.89 mg/g for Cd(II) and 16.86 mg/g for Zn(II). It was observed that the adsorption of Cd(II) on leonardite is greater than that of Zn(II). For binary component adsorption systems, Cd(II) and Zn(II) showed antagonistic behavior. The presence of the other metal ions could decrease the amount of metal adsorbed. Binary adsorption of Cd(II) and Zn(II) was tested with regard to four multi-component isotherms: Extended Langmuir, Modified Langmuir, Sheindorf–Rebuhn–Sheintuch, and Extended Freundlich. The Extended Freundlich isotherm proved to be a good fit for the experimental data.     

Distribution of selenium and arsenic in differentiated multicellular eukaryotic fossils and their significance

We present variation patterns of trace elements within different sequences of the Ediacaran Doushantuo Formation(DST,635-551 million years ago),and inside the cells of the earliest differentiated multicellular eukaryotic fossils of the Weng'an biota in the Weng'an County of Guizhou Province.The results showed that selenium is the most enriched and significantly varied trace element among the 22 trace elements throughout the DST,followed by arsenic.The highest selenium and arsenic content sequences are consistent with the first appeared sequence of the earliest differentiated multicellular eukaryotic fossils Megasphaera at the middle to upper parts of the DST.Nanoman secondary ion mass spectrometry analyses show that selenium and arsenic have an inhomogeneous and punctate distribution in the nucleus and cytoplasm.The nucleus has anomalously enriched levels of selenium and arsenic among the organelles.The selenium and arsenic concentrations exhibit a positive correlation with the diversity of fossilized Megasphaera.These new findings give us a clue that the anomalous enrichment of selenium and arsenic might contributes to the cell differentiation in Ediacaran Doushantuo period.     

Potentiality of open burnt clay as an adsorbent for the removal of Congo red from aqueous solution

Open burnt clay was studied as a potential adsorbent for the adsorption of Congo red (a reactive dye) from aqueous solution. The effect of contact time, pH, adsorbent dosage and temperature were studied. It was observed that the amount of Congo red retained increase with decreasing pH and increasing initial concentration. Removal percentage at pH 2 and 3 are almost same. The adsorption capacity of regenerated burnt clay was showed more than 98 % recovery of the adsorption efficiency of initial virgin adsorbent. The equilibrium data were described well by both Langmuir and Freundlich isotherm model. The adsorption capacity of some natural adsorbents, namely rice husk, wood charcoal, tea waste etc. were also investigated and compared with that of open burnt clay.     

2,3-二羟基萘-6-磺酸钠接枝吸附剂去除水中微量硼的机理

以11B NMR法研究了硼酸与2,3-二羟基萘-6-磺酸钠的配位反应。结果表明,2,3-二羟基萘-6-磺酸钠与水溶液中的硼酸根离子反应生成五元环的1:1和1:2(化学计量比)的配合物,配合物的形成常数分别为logβ1=5.22、logβ2=6.10。利用离子交换法制备了2,3-二羟基萘-6-磺酸钠接枝硼选择性吸附剂,吸附剂上2,3-二羟基萘-6-磺酸钠担载量为1.20mmol/g。以bath法研究了2,3-二羟基萘-6-磺酸钠接枝吸附剂对水中硼的去除作用,考察了溶液p H值、初始硼浓度、温度、吸附时间等因素对硼去除率的影响。在该吸附剂吸附硼的热力学和动力学研究中发现,硼的吸附符合准二级速率方程,是化学吸附和物理吸附共同作用的结果,B(OH)4-以1:1配合物的形式和静电吸引的方式结合在吸附剂上;吸附速率主要为化学吸附控制。     

A preliminary geochemical map for arsenic in surficial materials of Canada and the United States

Over the past 30 a, regional and national solid-phase geochemical surveys have been conducted by the United States Geological Survey and the Geological Survey of Canada. In the present paper the authors have examined the distribution of As in stream-sediment and soil samples of the US and Canada in terms of geologic and anthropogenic components. The results of the compilations indicate that the distribution of As in stream sediments, lake sediments, and soils in Canada and the US shows that most of the variability is controlled by the bed rock characteristics.     

Speciation studies of arsenic in the environment and in human

Arsenic is the 20th most abundant element in the Earth crust. Humans are exposed to naturally occurring and anthropogenic sources of arsenic compounds in the environment. A wide variety of adverse health effects have been attributed to chronic exposure to high levels of arsenic. More than two-dozen arsenic compounds （species） are present in the environment and in biological systems. The various arsenic species have dramatically different behavior and toxicity. This presentation briefly describes arsenic speciation analysis, human exposure to and metabolism of arsenic species. Environmental issues on arsenic in Canada are briefly discussed. These include （1） the arsenic waste left from previous gold mining and smelting activities; （2） the domestic use of wood treated with chromated copper arsenate; and （3） use of well water as the source of drinking water by approximately one third of the Canadian population.     

Adsorption capacity of iron oxide-coated gravel for landfill leachate: simultaneous study

Landfill leachate is a high-strength wastewater. If it is not managed properly, it can pollute surrounding environment. The aim of this study is to determine the simultaneous adsorption capacity of iron oxide-coated gravel for metals such as Cd(II), Cu(II), Fe(II), Ni(II) and Zn(II) in high-strength leachate sample. Different operating conditions such as pH, time, and dosages were investigated to determine the kinetics and mechanism of adsorption process. Coating with iron oxide changed the external surface of gravel. The adsorption capacities increased with increased pH, and the optimum pH was found to be 7. High removal rates were observed in a short period of time. The Freundlich model fitted reasonably well to the experimental data, indicating multilayer adsorption process and the heterogeneity of the surface (R ² ranging 0.57–0.94). The Temkin model fitted well to the experimental data as well (R ² ranging 0.67–0.98), indicating that the adsorption is an exothermic process. The adsorption of ions was found to obey second-order kinetics, indicating one-step, surface-only adsorption process. The degree of metal adsorption on iron oxide-coated gravel at pH 7 was in the order Cu(II) > Cd(II) > Fe(II) > Zn(II) > Ni(II).