Cadmium adsorption and desorption behaviour on goethite at low equilibrium concentrations: effects of pH and index cations

The transport and bioavailability of cadmium is governed mainly by its adsorption-desorption reactions with minerals such as goethite--a common iron oxide mineral in variable charged and highly weathered tropical soils. Soil factors such as pH, temperature, solution Cd concentration, ionic strength and ageing affect Cd adsorption on goethite. The desorption behaviour of Cd from goethite at low concentrations is not fully understood. This study investigates the adsorption-desorption of Cd at low Cd concentrations (Cd adsorbed on goethite from 20 to 300 microM Cd solutions) in Na and Ca nitrate solutions of 0.03 M nominal ionic strengths. Synthetic goethite prepared by ageing a ferric hydroxide gel at high pH and room temperature was used for Cd adsorption and desorption studies. For desorption experiment 10 successive desorptions were made for the whole range of initial Cd concentrations (20-300 microM) in the presence of 0.01 M Ca(NO3)2 or 0.03 M NaNO3 solutions. Cadmium adsorption was found to be higher in Na+ than Ca2+ probably due to the competition of Ca2+ ions with Cd2+ ions for adsorption sites on the surfaces of goethite. The effect of index cation on Cd adsorption diminished with increase in pH from 5.0 to 6.0. Cadmium desorption decreased with increase in pH from 5.0 to 6.0 in both Na and Ca systems. After 10 successive desorptions with 0.03 M NaNO3 at the lowest initially adsorbed Cd approximately 45%, 20% and 7% of the adsorbed Cd was desorbed at pH 5.0, 5.5 and 6.0, respectively. The corresponding desorptions in the presence of 0.01 M Ca(NO3)2 were 49%, 22% and 8%, respectively. The Freundlich parameter, k, based on each progressive step of desorption at different adsorbed concentration increased with increasing desorption step, which may indicates that a fraction of Cd was resistant to desorption. Low Cd desorbability from goethite may be due to its specific adsorption and/or possibly as a result of Cd entrapment in the cracks or defects in goethite structure.     

Adsorption and desorption of cadmium by goethite pretreated with phosphate

The adsorption of Cd by oxides or soils have been extensively studied, however, the desorption has received relatively limited attention, especially in the presence of phosphate. In this study, a batch equilibration method was used to investigate Cd sorption and desorption by goethite pretreated with phosphate. Phosphate not only enhanced Cd adsorption, but also accelerated the adsorption process. Compared with Cd adsorption by goethite alone, phosphate substantially moved the adsorption curves (edges) to lower pH range, indicative of enhancement of Cd sorption. The Cd adsorption by the pretreated goethite reached apparent equilibrium within 24 h at 20 degrees C, while such equilibrium was not observed after 4 weeks in the absence of phosphate. Cadmium was more readily released from phosphate-treated goethite. It is believed that phosphate blocked the pores on goethite surface, which lead to the fast adsorption kinetics and high extraction percentage. These results provided strong support for the diffusion of Cd into goethite particles.     

Mutual effects of cadmium and phosphate on their adsorption and desorption by goethite

Adsorption of cadmium (Cd) and phosphate by oxides or soils has been extensively studied, but the adsorption/desorption kinetics and mutual effects of these two species in co-existing systems has received little attention. In this study, a batch equilibration method was used to investigate the effect of phosphate and its application time on Cd adsorption and desorption on goethite. The influence of Cd and its application time on phosphate sorption and desorption kinetics was also determined. For Cd adsorption, phosphate was introduced into the system by two sequences: pre-treating goethite at 40 (degrees)C for 1 week, and applying with Cd simultaneously. Similarly, for phosphate sorption, Cd was applied by pre-treating goethite at 40 (degrees)C for 1 week or simultaneous addition with phosphate. Results demonstrated that phosphate added to goethite enhanced Cd adsorption, and facilitated Cd release as compared to untreated goethite. Cadmium had slightly higher adsorption, but a significantly faster desorption rate from the goethite simultaneously treated with phosphate and Cd, as compared to phosphate-pretreated goethite. Cadmium and its application time had little impact on phosphate sorption by goethite. However, phosphate desorption kinetics was affected by Cd application time. When the sorption time was short (15 min), phosphate desorption was faster from the goethite that was simultaneously treated with phosphate and Cd, as compared to Cd pretreated or untreated goethite. In contrast, a longer sorption time (4 weeks) resulted in a higher desorption rate of phosphate from Cd pretreated goethite than simultaneously phosphate-Cd treated goethite. This study provided useful information on adsorption/desorption kinetics in complicated Cd-phosphate-goethite systems.     

Inhibition of rainbow trout acetylcholinesterase by aqueous and suspended particle-associated organophosphorous insecticides

Cadmium (Cd) adsorption on 14 non-calcareous New Jersey soils was investigated with a batch method. Both adsorption edge and isotherm experiments were conducted covering a wide range of soil composition, e.g. soil organic carbon (SOC) concentration ranging from 0.18% to 7.15%, and varying Cd concentrations and solution pH. The SOC and solution pH were the most important parameters controlling Cd partition equilibrium between soils and solutions in our experimental conditions. The Windermere humic aqueous model (WHAM) was used to calculate Cd adsorption on soils. The effect of solution chemistry (various pH and Cd concentrations) on Cd adsorption can be well accounted for by WHAM. For different soil compositions, SOC concentration is the most important parameter for Cd binding. Only a fraction of SOC, the so-called active organic carbon (AOC), is responsible for Cd binding. We found a linear relationship between SOC and AOC based on the adsorption edge data. The linear relationship was validated by the independent data sets: adsorption isotherm data, which presumably can be used to predict Cd partition equilibrium across a wide range of soil compositions. The modeling approach presented in this study helps to quantitatively predict Cd behavior in the environment.     

Effect of arsenate on adsorption of Cd(II) by two variable charge soils

The effect of arsenate on Cd(II) adsorption in two variable charge soils and the desorption of Cd(II) pre-adsorbed in the presence of arsenate were studied. The batch type experiments showed, the presence of arsenate led to increase in Cd(II) adsorption and the desorption of pre-adsorbed Cd(II). Further it was observed that the extent of adsorption and desorption of Cd(II) was greatly influenced by the initial concentrations of arsenate and Cd(II), the solution pH, and the nature of the soils. In general the increase in arsenate concentration and pH favored the uptake of Cd(II). Moreover, the arsenate concentration influenced more in Hyper-Rhodic Ferralsol than Rhodic Ferralsol at least for the Cd(II) adsorption/desorption. This may be due to the content of Fe/Al oxides in these soils. The larger the content of Fe/Al oxides, the more the adsorption of arsenate by the soil, hence greater the uptake of Cd(II). It can be assumed that the enhanced Cd(II) adsorption was mainly due to the increase in net negative surface charge of the soil induced by the adsorption of arsenate, because the presence of arsenate led to the decrease in zeta potential of these soil suspensions. The increase of electrostatically adsorbed Cd(II) was responsible for the increase in the desorption of Cd(II) pre-adsorbed in the presence of arsenate.     

改性多壁碳纳米管对水中Cd2+的去除

为了增加多壁碳纳米管(multiwall carbon nanotubers,MWNTs)对水中Cd2+的吸附量,使用混酸对多壁碳纳米管进行氧化处理,采用红外光谱进行结果表征,并探讨了吸附时间、pH值和MWNTs的使用量、Cd2+的浓度及干扰离子对镉离子吸附的影响。结果表明,吸附时间为1.5 h、pH为5.3、吸附效果最佳,随MWNTs量的增加Cd2+去除量增加,共存的阳离子会降低对Cd2+的吸附效果,对Cd2+的吸附符合Longmuir吸附定律。研究同时表明,pH小于2时Cd2+能容易从碳纳米管上解吸。初步探讨了Cd2+吸附机制。     

一株产絮酵母菌废菌体对Cd~（2＋）的吸附特性

将一株产絮酵母菌（编号B-02号）发酵后的废菌体制成生物吸附剂,研究该生物吸附剂对废水中Cd2＋的生物吸附特性。结果表明：（1）pH值对Cd2＋会产生较大的影响,偏酸性（pH=4～6）条件利于吸附;该吸附剂对Cd2＋吸附速率较快,8～10 min就可达到吸附平衡;（2）吸附剂的吸附动力学符合二级动力学模型,吸附Cd2＋的实验数据对Langmuir等温式的拟合情况良好,吸附剂吸附Cd2＋的最大吸附量为70.752 mg/g。用0.5 mol/L HNO3对吸附Cd2＋的酵母菌进行解吸,解吸率可达89.7%。     

改性多壁碳纳米管对水中Cd~（2＋）的去除

为了增加多壁碳纳米管（multiwall carbon nanotubers,MWNTs）对水中Cd2＋的吸附量,使用混酸对多壁碳纳米管进行氧化处理,采用红外光谱进行结果表征,并探讨了吸附时间、pH值和MWNTs的使用量、Cd2＋的浓度及干扰离子对镉离子吸附的影响。结果表明,吸附时间为1.5 h、pH为5.3、吸附效果最佳,随MWNTs量的增加Cd2＋去除量增加,共存的阳离子会降低对Cd2＋的吸附效果,对Cd2＋的吸附符合Longmuir吸附定律。研究同时表明,pH小于2时Cd2＋能容易从碳纳米管上解吸。初步探讨了Cd2＋吸附机制。     

一株产絮酵母菌废菌体对Cd2+的吸附特性

将一株产絮酵母菌(编号B-02号)发酵后的废菌体制成生物吸附剂,研究该生物吸附剂对废水中Cd2+的生物吸附特性。结果表明:(1)pH值对Cd2+会产生较大的影响,偏酸性(pH=4～6)条件利于吸附;该吸附剂对Cd2+吸附速率较快,8～10 min就可达到吸附平衡;(2)吸附剂的吸附动力学符合二级动力学模型,吸附Cd2+的实验数据对Langmuir等温式的拟合情况良好,吸附剂吸附Cd2+的最大吸附量为70.752 mg/g。用0.5 mol/L HNO3对吸附Cd2+的酵母菌进行解吸,解吸率可达89.7%。     

Adsorption-desorption behaviour of zinc(II) at iron(III) hydroxide-aqueous solution interface as influenced by pH and temperature

Batch studies were carried out to investigate the adsorption of zinc(II) from fresh waters on an iron(III) hydroxide surface maintained at the pH of zero point of charge of hydroxide (ZPC, 6.85) and also on both the acidic (5.5) and alkaline (8.2) sides of pH of ZPC, at 15 and 35 degrees C. Zinc(II) adsorption on iron(III) hydroxide increased with an increase in pH. The rise in temperature from 15 to 35 degrees C increased zinc(II) adsorption at pH 5.5 and 6.85, but decreased it at alkaline pH (8.2). In none of the cases did adsorption attain a maximum adsorption density. The results indicate the presence of heterogeneous sites of varying affinity on the adsorbent. Zinc(II) adsorption followed Langmuir behaviour only at small adsorption densities (less than 10(-2.95) M Zn/kg at pH 5.5) and at higher adsorption densities, the availability of strongest binding sites decreased. Nonspecifically adsorbed zinc(II) (reversible to Ba(II)) decreased with the increase in pH and temperature. Sequential desorption experiments also revealed that desorption of adsorbed zinc(II) decreased with an increase in pH.     

Effects of organic acids on adsorption of lead onto montmorillonite,goethite and humic acid

Adsorption isotherms for Pb onto six soil components (quartz, feldspar, kaolinite, montmorillonite, goethite and humic acid) were studied. The influence of pH, EDTA and citric acid on the adsorption of Pb onto montmorillonite, goethite and humic acid were considered. Results indicate that the experimental data fit the Langmuir Adsorption Isotherm. The adsorption capacity for Pb at pH 6 was found to be in the order: humic acid (22.7 mg g(-1)) > goethite (11.04 mg g(-1)) > montmorillonite (10.4 mg g(-1)) > kaolinite (0.91 mg g(-1)) > feldspar (0.503 mg g(-1)) > quartz (0.148 mg g(-1)). Generally, the amount of Pb adsorbed onto montmorillonite, goethite and humic acid decreased with increasing concentrations of EDTA and citric acid and with increases in alkality. However, there were two exceptions: (1) addition of citric acid increased the amount of Pb adsorbed onto humic acid; and (2) the amount of Pb adsorbed onto goethite decreased with increasing pH in the presence of EDTA. Some mechanisms involved in the adsorption reactions are discussed.     

棘孢曲霉(Aspergillus aculeatus)对Pb~(2+)和Cd~(2+)的吸附特征

为了研究棘孢曲霉(Aspergillus aculeatus)对溶液中Pb~(2+)和Cd~(2+)吸附过程的特征,分别从动力学、热力学和吸附等温线三方面进行了实验,同时还研究了pH、温度、时间、重金属离子起始浓度和吸附剂用量对吸附过程的影响。等温吸附过程可以用Langmuir方程来描述。在实验设定条件下,棘孢曲霉对Pb~(2+)和Cd~(2+)最大吸附量分别为71.2 mg/g和59.8 mg/g;动力学实验数据很好的符合二级动力学方程,吸附达到平衡的时间为3 h;热力学实验数据显示该吸附过程为自发的、吸热的过程。     

Removal of Pb(II), Cd(II), Cu(II), and Zn(II) by hematite nanoparticles: effect of sorbent concentration, pH, temperature, and exhaustion

Nanoparticles offer the potential to improve environmental treatment technologies due to their unique properties. Adsorption of metal ions (Pb(II), Cd(II), Cu(II), Zn(II)) to nanohematite was examined as a function of sorbent concentration, pH, temperature, and exhaustion. Adsorption experiments were conducted with 0.05, 0.1, and 0.5 g/L nanoparticles in a pH 8 solution and in spiked San Antonio tap water. The adsorption data showed the ability of nanohematite to remove Pb, Cd, Cu, and Zn species from solution with adsorption increasing as the nanoparticle concentration increased. At 0.5 g/L nanohematite, 100 % Pb species adsorbed, 94 % Cd species adsorbed, 89 % Cu species adsorbed and 100 % Zn species adsorbed. Adsorption kinetics for all metals tested was described by a pseudo second-order rate equation with lead having the fastest rate of adsorption. The effect of temperature on adsorption showed that Pb(II), Cu(II), and Cd(II) underwent an endothermic reaction, while Zn(II) underwent an exothermic reaction. The nanoparticles were able to simultaneously remove multiple metals species (Zn, Cd, Pb, and Cu) from both a pH 8 solution and spiked San Antonio tap water. Exhaustion experiments showed that at pH 8, exhaustion did not occur for the nanoparticles but adsorption does decrease for Cd, Cu, and Zn species but not Pb species. The strong adsorption coupled with the ability to simultaneously remove multiple metal ions offers a potential remediation method for the removal of metals from water.     

棘孢曲霉（Aspergillus aculeatus）对Pb^2＋和Cd^2＋的吸附特征

为了研究棘孢曲霉（Aspergillus aculeatus）对溶液中Pb^2＋和Cd^2＋吸附过程的特征，分别从动力学、热力学和吸附等温线三方面进行了实验，同时还研究了pH、温度、时间、重金属离子起始浓度和吸附剂用量对吸附过程的影响。等温吸附过程可以用Langmuir方程来描述。在实验设定条件下，棘孢曲霉对Pb^2＋和Cd^2＋最大吸附量分别为71．2mg／g和59．8mg／g；动力学实验数据很好的符合二级动力学方程，吸附达到平衡的时间为3h；热力学实验数据显示该吸附过程为自发的、吸热的过程。     

Column- and catchment-scale transport of cadmium: effect of dissolved organic matter

In the Ellen catchment on the Pinjarra Plain, NE of Perth in Western Australia, cadmium from fertilisers is starting to leach from soils. About 70% of surface soils in the Ellen catchment are sandy and often on top of a shallow ephemeral water table. Adsorption of Cd in the sandy soils of the Ellen catchment was studied by batch adsorption and by leaching small columns of soil. Adsorption of Cd increases linearly with increasing soil organic matter content and exponentially with increasing pH. Cadmium is significantly mobilised in the sandy soils by dissolved organic matter.The capacity of most of the sandy soils in the Ellen catchment to adsorb phosphate from fertiliser has been saturated. Resulting concentrations in Ellen Brook average 500 μg L⁻¹ P. Cadmium is adsorbed more strongly in the sandy soils than phosphate and is just starting to leach into Ellen Brook. From a comparison of Cd/P ratios in water, soils and fertiliser, cadmium concentrations in Ellen Brook are estimated to be at 10–30% of their maximum for complete breakthrough from soils. Present concentrations of Cd in Ellen Brook average 0.1 μg L⁻¹ and are estimated to approach the maximum for complete breakthrough in 100 yr. Maximum Cd concentrations in Ellen Brook could range from 0.6 to 2 μg L⁻¹, depending on rates of input with fertiliser and future increases in agricultural land use in the catchment.Breakthrough curves, resulting from leaching Cd through small columns of sandy soil, indicate that adsorption significantly increases the effective hydrodynamic dispersion of Cd. Longitudinal dispersivities, measured at pore-water velocities of 0.7–14 m day⁻¹, were 5 cm for Cd and 0.1–0.2 cm for chloride. The much greater dispersion of Cd in the sandy soils than of chloride is shown not to be caused by non-equilibrium adsorption.     

棘孢曲霉（Aspergillus aculeatus）对Pb2＋和Cd2＋的吸附特征

为了研究棘孢曲霉（Aspergillus aculeatus）对溶液中Pb^2＋和Cd^2＋吸附过程的特征，分别从动力学、热力学和吸附等温线三方面进行了实验，同时还研究了pH、温度、时间、重金属离子起始浓度和吸附剂用量对吸附过程的影响。等温吸附过程可以用Langmuir方程来描述。在实验设定条件下，棘孢曲霉对Pb^2＋和Cd^2＋最大吸附量分别为71.2 mg/g和59.8 mg/g；动力学实验数据很好的符合二级     

Study on fractions of adsorbed Pb and Cd onto natural surface coatings

The speciation and extent of migration of adsorbed Pb and Cd in natural surface coatings (NSCs) were investigated using sequential extraction procedure to provide an understanding of distribution of the adsorbed Pb and Cd. Extractions were conducted on NSCs before and after Pb and Cd adsorption treatment under controlled laboratory conditions with initial Pb and Cd concentrations ranging from 0.2-2.5 mol/l. The Langmuir adsorption isotherms were applied to estimate equilibrium coefficients of Pb and Cd adsorption to NSCs components. The results showed that 58.50% of adsorbed Pb in average existed in tightly adsorbed form, and the remaining Pb was mostly present as solid oxides/hydroxides (34.00%) and exchangeable and soluble form (7.50%) in NSCs, respectively. Large amount of adsorbed Cd (70.51% in average) was present in exchangeable and soluble form, following a decreasing order in tightly adsorbed form (18.61%), solid oxides/hydroxides (9.87%), and easily oxidizable solids/compounds (1.01%), respectively. No Cd was found in strongly held oxides and precipitates. Compared to the distribution of adsorbed Pb in NSCs, Cd distribution showed that less migration of Cd from exchangeable and soluble form to solid oxides/hydroxides after adsorbed to NSCs, indicating fewer sites for Cd to adsorb to NSCs and less affinity of Cd to the NSCs. These percent distributions of metals provided an additional interpretation to that Pb adsorption to the NSCs greater than that of Cd, less retention of Cd than that of Pb and less roles attributed for Pb/Cd adsorption by organic materials in NSCs, which were observed based on the selective extraction techniques in the independent investigations.     

Removal of As(III) and As(V) using iron-rich sludge produced from coal mine drainage treatment plant

To test the feasibility of the reuse of iron-rich sludge (IRS) produced from a coal mine drainage treatment plant for removing As(III) and As(V) from aqueous solutions, we investigated various parameters, such as contact time, pH, initial As concentration, and competing ions, based on the IRS characterization. The IRS consisted of goethite and calcite, and had large surface area and small particles. According to energy dispersive X-ray spectroscopy mapping results, As was mainly removed by adsorption onto iron oxides. The adsorption kinetic studies showed that nearly 70 % adsorption of As was achieved within 1 h, and the pseudo-second-order model well explained As sorption on the IRS. The adsorption isotherm results agreed with the Freundlich isotherm model, and the maximum adsorption capacities for As(III) and As(V) were 66.9 and 21.5 mg/g, respectively, at 293 K. In addition, the adsorption showed the endothermic character. At high pH or in the presence of phosphate, the adsorption of As was decreased. When the desorption experiment was conducted to reuse the IRS, 85 % As was desorbed with 1.0 N NaOH. In the column experiment, adsorbed As in real acid mine drainage was 43 % of the maximum adsorbed amount of As in the batch test. These results suggested that the IRS is an effective adsorbent for As and can be effectively applied for the removal of As in water and wastewater.     

Tetracycline removal enhancement with Fe-saturated nanoporous montmorillonite in a tripartite adsorption/desorption/photo-Fenton degradation process

The adsorption and photo-Fenton degradation of tetracycline (TC) over Fe-saturated nanoporous montmorillonite was analyzed. The synthesized samples were characterized using XRD, FTIR, SEM, and XRF analysis, and the adsorption and desorption of TC onto these samples, as well as the antimicrobial activity of TC during these processes, were analyzed at different pH. Initially, a set of adsorption/desorption experiments was conducted, and surprisingly, up to 50% of TC adsorbed was released from Mt structure. Moreover, the desorbed TC had strong antibacterial activity. Then, an acid treatment (for the creation of nanoporous layers) and Fe saturation of the montmorillonite were applied to improve its adsorption and photocatalytic degradation properties over TC. Surprisingly, the desorption of TC from modified montmorillonite was still high up to 40% of adsorbed TC. However, simultaneous adsorption and photodegradation of TC were detected and almost no antimicrobial activity was detected after 180 min of visible light irradiation, which could be due to the photo-Fenton degradation of TC on the modified montmorillonite surface. In the porous structures of modified montmorillonite high, ˙OH radicals were created in the photo-Fenton reaction and were measured using the Coumarin technique. The ˙OH radicals help the degradation of TC as proposed in an oxidation process. Surprisingly, more than 90% of antimicrobial activity of the TC decreased under visible light (after 180 min) when desorbed from nanoporous Fe-saturated montmorillonite compared to natural montmorillonite. To the best of our knowledge, this is the first time that such a high TC desorption rate from an adsorbent with the least residual antimicrobial activity is reported which makes nanoporous Fe-saturated montmorillonite a perfect separation substance of TC from the environment.

     

土壤颗粒级配对镉吸附-解吸规律的影响

利用甘肃金川某地土壤通过批实验进行等温吸附和动力学解吸实验,研究不同颗粒级配的中砂对镉的吸附、解吸特征,并采用Freundlich和一级动力学方程对其吸附解吸方程进行拟合。结果表明,(1)Freundlich和一级动力学方程对该土壤吸附、解吸镉的实验适用;(2)等温吸附实验中4组不同颗粒级配的中砂对镉的吸附性很强,最大平衡吸附量依次为260.667、286.107、299.362和292.232 mg/kg,吸附性能与颗粒级配中的细粒土相对含量大小成正比;(3)4组土壤对镉的解吸在初期2 h内解吸速率均较快,在3 h左右达到吸附-解吸平衡。平衡后4组土样Ⅰ、Ⅱ、Ⅲ和Ⅳ的最大解吸量依次为0.752、0.561、0.44和0.54 mg/kg,解吸速率和平衡时最大解吸量均与颗粒级配中细颗粒相对含量密切相关。