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.     

Desorption of cadmium from goethite: effects of pH, temperature and aging

Cadmium is perhaps environmentally the most significant heavy metal in soils. Bioavailability, remobilization and fate of Cd entering in soils are usually controlled by adsorption-desorption reactions on Fe oxides. Adsorption of Cd on soil colloids including Fe oxides has been extensively studied but Cd desorption from such soil minerals has received relatively little attention. Some factors that affect Cd adsorption on goethite include pH, temperature, aging, type of index cations, Cd concentrations, solution ionic strength and presence of organic and inorganic ions. This research was conducted to study the influence of pH, temperature and aging on Cd desorption from goethite. Batch experiments were conducted to evaluate Cd desorption from goethite with 0.01 M Ca(NO3)2. In these experiments Cd desorption was observed at 20, 40 and 70 degrees C in combination with aging for 16 h, 30, 90 and 180 d from goethite that adsorbed Cd from solutions containing initial Cd concentrations of 20, 80 and 180 microM. Following the adsorption step Cd desorption was measured by 15 successive desorptions after aging at various temperatures. At the lowest amount of initially adsorbed Cd and equilibrium pH 5.5, cumulative Cd desorption decreased from 71% to 17% with aging from 16 h to 180 d and the corresponding decrease at equilibrium pH 6.0 was from 32% to 3%. There was a substantial decrease in Cd desorption with increasing equilibration temperature. For example, in goethite with the lowest amount of initial adsorption at equilibrium pH 5.5, cumulative Cd desorption decreased from 71% to 31% with increase in temperature from 20 to 70 degrees C, even after 16 h. Dissolution of Cd adsorbed goethite in 1M HCl, after 15 successive desorptions with 0.01 M Ca(NO3)2, indicated that approximately 60% of the Cd was surface adsorbed. Overall, dissolution kinetics data revealed that 23% to 88% Cd could not be desorbed, which could possibly be diffused into the cracks and got entrapped in goethite crystals. At elevated temperature increased equilibrium solution pH favoured the formation of CaCO3 and CdCO3 which reasonably decreased Cd desorption. Cadmium speciation showed the formation of calcite and otavite minerals at 40 and 70 degrees C due to increase in pH (>9.5) during aging. X-ray diffraction analysis (XRD) of these samples also revealed the formation of CaCO3 at elevated temperatures with aging. While mechanisms such as Cd diffusion and/or entrapment into fissures and cracks in goethite structure with increase in temperature and aging are possible.     

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.     

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。     

Adsorption of molybdate and tetrathiomolybdate onto pyrite and goethite: effect of pH and competitive anions

The adsorption of two major molybdenum (Mo) species, molybdate (MoO4(2-)) and tetrathiomolybdate (MoS4(2-)) onto two main iron minerals pyrite (FeS2) and goethite (FeOOH) is addressed to elucidate the possible mechanisms of molybdenum immobilization in anoxic sediments. Suspensions of MoS4(2-) (or MoO4(2-)) and goethite (or pyrite) in 0.1M NaCl solution were equilibrated under anoxic conditions at 25 degrees C in the pH range from 3 to 10. The competitive effects of sulfate, phosphate, and silicate on the adsorption of MoO4(2-) and MoS4(2-) by pyrite and goethite are also addressed. Adsorption of MoO4(2-) and MoS4(2-) on pyrite and goethite is in general well described by a Langmuir model at low pH; the extent of sorption is a function of pH and the surface loading. Maximum sorption is observed in the acidic pH range (pH<5) at low surface loading. The adsorption of molybdenum (micromol g(-1)) depends upon Mo species and on the type of iron mineral following the order: MoS4(2-)-goethite > MoO4(2-)-goethite > MoS4(2-)-pyrite > MoO4(2-)-pyrite. Phosphate appears to compete strongly with MoO4(2-) and MoS4(2-) for the sorption sites of pyrite and goethite. The strength of the phosphate competitive effect follows the sequence of MoO4(2-)-goethite approximately = MoO4(2-)-pyrite > MoS4(2-)-pyrite > MoS4(2-)-goethite. Silicate and sulfate have a negligible effect on the sorption of MoO4(2-) and MoS4(2-). The preferred adsorption by iron mineral of MoS4(2-), as well as its behavior in the presence of competitive anions suggests that tetrathiomolybdate species may be an ultimate reservoir and may control Mo enrichment in the sediments.     

Geochemical modeling of cadmium sorption to soil as a function of soil properties

Cadmium sorption experiments were conducted to infer Cd sorption mechanisms to a reference smectite and three fractions of a Vertisol soil. Untreated Vertisol has a higher adsorption capacity for Cd than that of reference smectite. Surface complex modeling was used to calculate the potential contributions of Cd complexation reactions with permanent charge sites and pH-dependent charge sites over ranges in pH, for soils with given surface areas, and sorption site densities. The Langmuir model produced relatively good predictions of Cd sorption on reference smectite and Vertisol. However, the results of the triple-layer model (TLM) were inadequate to describe Cd adsorption on fixed-charge sites because the model could not account for the ion-exchange reaction on the basal plane. Based upon the two geochemical models of Cd adsorption to the reference smectite and Vertisol, it appears that the basal plane siloxane cavities are the most important sites for Cd complexation at pH < 6.5. For the pH-dependent sites, the edge-site aluminol appears to be the dominant surface functional group responsible for Cd adsorption at pH > 6.5.     

Sequential sorption of lead and cadmium in three tropical soils

It is important to examine mechanisms of Pb and Cd sorption in soils to understand their bioavailability. The ability of three tropical soils to retain Pb, Cd, and Ca was evaluated. The objectives of this study were to (1) determine the extent to which soil sorption sites are metal specific, (2) investigate the nature of reactions between metals and soil surfaces, and (3) identify how metals compete for sorption sites when they are introduced to soils sequentially or concurrently. Lead was shown to be much less exchangeable than Cd and inhibited Cd sorption. Cadmium had little effect on Pb sorption, though both Ca and Cd inhibited the adsorption of Pb at exchange sites. Lead appears to more readily undergo inner-sphere surface complexation with soil surface functional groups than either Cd or Ca. Thus, regardless of when Pb is introduced to a soil, it should be less labile than Cd.     

Adsorption and desorption processes of MCPA in Polish mineral soils

Studies on the adsorption and desorption of MCPA (4-chloro-2-methylophenoxyacetic acid) were performed in soil horizons of three representative Polish agricultural soils. The Hyperdystric Arenosol, the Haplic Luvisol and the Hypereutric Cambisol were investigated in laboratory batch experiments. Initially, both the adsorption and desorption proceeded rapidly, and either the equilibrium was reached after approximately 30 min or the process slowed down and continued at a slow rate. In the latter case, the equilibrium was reached after 8 hours. Data on the adsorption/desorption kinetics fitted well to the two-site kinetic model. The measured sorption and desorption isotherms were of L-type. The sorption distribution coefficients (K(ads) (d)) were in the range of 0.75--0.97 for Ap soil horizons and significantly lower in deeper soil layers. The corresponding desorption coefficients (K(des) (d)) were higher and ranged from 1.02 to 2.01. Both the adsorption and desorption of MCPA in all soil horizons was strongly and negatively related to soil pH. It appears that hydrophobic sorption plays a dominant role in the MCPA retention in topsoils whereas hydrophilic sorption of MCPA anions is the dominant adsorption mechanism in subsoils.     

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。     

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。     

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。     

Sorption of Cr(VI) from dilute solutions and wastewater by live and pretreated biomass of Aspergillus flavus

Sorption of Cr(VI) was carried out from dilute solutions using live and pretreated biomass in a batch mode. Effects of agitation time, adsorbent dosage and pH were examined. The autoclaved biomass that showed maximum adsorption capacity (Q(0)=0.335 mg g(-1)) was used as an adsorbent in column studies. The optimized flow rate of 2.5 ml min(-1) and bed height 10 cm were used to determine the effect of metal ion concentration on removal of Cr(VI). Applying the BDST model to calculate the adsorption capacity (N(0)) of column, which showed 4.56 x 10(-5), 7.28 x 10(-5), 6.89 x 10(-5), 3.07 x 10(-5), 2.80 x 10(-5)mg g(-1) for 4, 8, 12, 16 and 20 mg dm(-3) of Cr(VI), respectively. Batch sorption proved to be more efficient than the column sorption and hence batch sorption was used to remove Cr(VI) from a textile dyeing industry wastewater. The phytotoxic effect of treated and untreated wastewater was studied against Zea mays. Toxicity was reduced by 50% in the treated effluent.     

Effect of phosphate on the adsorption of Cu and Cd on natural hematite

Interactions between anions and cations are important to understand the chemical processes of pollutants in environment. In this study, batch experiments were carried out to investigate the simultaneous adsorption of Cu and Cd on hematite as affected by phosphate. Phosphate pretreatment suppressed the maximum adsorption of Cu and Cd on hematite and moved the adsorption pH edges to a higher pH range. Phosphate application time had a marked impact on Cu and Cd adsorption and longer contact time resulted in more reduction of Cu and Cd adsorption. Results of back-titration, Fourier transform infrared (FTIR) spectroscopy study and ionic strength effect on the adsorption revealed that Cu and Cd were adsorbed on hematite mainly through the inner-sphere complex formation mechanism and phosphate treatment reduced the inner-sphere adsorption sites, thus decreasing Cu and Cd adsorption on hematite.     

Sorption, desorption, and degradation of (4-chloro-2-methylphenoxy)acetic acid in representative soils of the Danubian Lowland, Slovakia

Herbicide leaching through soil into groundwater greatly depends upon sorption-desorption and degradation phenomena. Batch adsorption, desorption and degradation experiments were performed with acidic herbicide MCPA and three soil types collected from their respective soil horizons. MCPA was found to be weakly sorbed by the soils with Freundlich coefficient values ranging from 0.37 to 1.03 mg^1−1/n kg⁻¹ L^1/n. It was shown that MCPA sorption positively correlated with soil organic carbon content, humic and fulvic acid carbon contents, and negatively with soil pH. The importance of soil organic matter in MCPA sorption by soils was also confirmed by performing sorption experiments after soil organic matter removal. MCPA sorption in these treated soils decreased by 37-100% compared to the original soils. A relatively large part of the sorbed MCPA was released from soils into aqueous solution after four successive desorption steps, although some hysteresis occurred during desorption of MCPA from all soils. Both sorption and desorption were depth-dependent, the A soil horizons exhibited higher retention capacity of the herbicide than B or C soil horizons. Generally, MCPA sorption decreased in the presence of phosphate and low molecular weight organic acids. Degradation of MCPA was faster in the A soil horizons than the corresponding B or C soil horizons with half-life values ranging from 4.9 to 9.6 d in topsoils and from 11.6 to 23.4 d in subsoils.     

Sorption of thiamethoxam in three Indian soils

The sorption behavior of the insecticide thiamethoxam [3-(2-chloro-1,3-thiazol-5-ylmethyl)-5-methyl-1,3,5-oxadiazinan-4-ylidene(nitro)amine] on three Indian soils with different physico-chemical properties was investigated. The soils represent the major grapevine growing areas of India, where the vineyards frequently receive thiamethoxam applications as foliar spray, soil drenching and through drip irrigation for the management of various insect pests. The rate constants for adsorption and desorption at two different temperatures were obtained from the Lindstrom model, which simultaneously evaluated adsorption and desorption kinetics. The data for rate constants, activation energies, enthalpy of activation, entropy of activation and free energy indicated physical adsorption of thiamethoxam on soil. The adsorptivity of different soils might be attributed to the organic matter and clay contents. A good fit to the linear and Freundlich isotherms was observed for both adsorption as well as desorption. Thiamethoxam could be categorized as a chemical with medium leaching potential.     

Sorption and desorption of glyphosate,MCPA and tetracycline and their mixtures in soil as influenced by phosphate

Phosphate fertilizers and herbicides such as glyphosate and MCPA are commonly applied to agricultural land, and antibiotics such as tetracycline have been detected in soils following the application of livestock manures and biosolids to agricultural land. Utilizing a range of batch equilibrium experiments, this research examined the competitive sorption interactions of these chemicals in soil. Soil samples (0-15 cm) collected from long-term experimental plots contained Olsen P concentrations in the typical (13 to 20 mg kg^?1) and elevated (81 to 99 mg kg^?1) range of build-up phosphate in agricultural soils. The elevated Olsen P concentrations in field soils significantly reduced glyphosate sorption up to 50%, but had no significant impact on MCPA and tetracycline sorption. Fresh phosphate additions in the laboratory, introduced to soil prior to, or at the same time with the other chemical applications, had a greater impact on reducing glyphosate sorption (up to 45%) than on reducing tetracycline (up to 13%) and MCPA (up to 8%) sorption. The impact of fresh phosphate additions on the desorption of these three chemicals was also statistically significant, but numerically very small namely < 1% for glyphosate and tetracycline and 3% for MCPA. The presence of MCPA significantly reduced sorption and increased desorption of glyphosate, but only when MCPA was present at concentrations much greater than environmentally relevant and there was no phosphate added to the MCPA solution. Tetracycline addition had no significant effect on glyphosate sorption and desorption in soil. For the four chemicals studied, we conclude that when mixtures of phosphate, herbicides and antibiotics are present in soil, the greatest influence of their competitive interactions is phosphate decreasing glyphosate sorption and the presence of phosphate in solution lessens the potential impact of MCPA on glyphosate sorption. The presence of chemical mixtures in soil solution has an overall greater impact on the sorption than desorption of individual organic chemicals in soil.     

Sorption-desorption of cadmium in aqueous palygorskite, sepiolite, and calcite suspensions: isotherm hysteresis

Sorption isotherms have been widely used to assess the heavy metal retention characteristics of soil particles. Desorption behavior of the retained metals, however, usually differ from that of sorption, leading to a lack of coincidence in the experimentally obtained sorption and desorption isotherms. In this study, we examine the nonsingularity of cadmium (Cd) sorption–desorption isotherms, to check the possible hysteresis and reversibility phenomena, in aqueous palygorskite, sepiolite and calcite systems. Sorption of Cd was carried out using a 24-h batch equilibration experiment with eight different Cd solution concentrations, equivalent to 20–100% of maximum sorption capacity of each mineral. Immediately after sorption, desorption took place using successive dilution method with five consecutive desorption steps. Both Cd sorption and desorption data were adequately described by Freundlich equation (0.81 < r² < 0.99). The sorption and desorption reactions, however, did not provide the same isotherms, indicating that hysteresis occurred in Cd sorption–desorption processes. The extent of hysteresis was quantified based on the differences obtained from sorption and desorption isotherms regarding the amount of Cd sorbed, the Freundlich exponent, and the Cd distribution coefficient. The results revealed that, sepiolite possessed the most hysteretic behavior among the minerals studied. Calcite showed much smaller hysteresis compared to the other two silicate clays at low Cd surface load, but its hysteresis indices significantly increased, and exceeded that of palygorskite, as the amount of Cd in the systems increased. The average amount of Cd released after five desorption steps, was 13.8%, 2.2% and 3.6% for the palygorskite, sepiolite and calcite, respectively, indicating that a large portion of Cd was irreversibly retained by the minerals.     

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.     

Influence of extracellular polymeric substances (EPS) on Cd adsorption by bacteria

The role of extracellular polymeric substances (EPS) in Cd adsorption by Bacillus subtilis and Pseudomonas putida was investigated using a combination of batch adsorption experiments, potentiometric titrations, Fourier transform infrared spectroscopy (FTIR). An increased adsorption capacity of Cd was observed for untreated bacteria relative to that for EPS-free bacteria. Surface complexation modeling of titration data showed the similar pK_a values of functional groups (carboxyl, phosphate and hydroxyl) between untreated and EPS-free bacteria. However, site concentrations on the untreated bacteria were found to be higher than those on the EPS-free bacteria. FTIR spectra also showed that no significant difference in peak positions was observed between untreated and EPS-free bacteria and carboxyl and phosphate groups were responsible for Cd adsorption on bacterial cells. The information obtained in this study is of fundamental significance for understanding the interaction mechanisms between heavy metals and biofilms in natural environments.     

针铁矿对Pb~(2+)的吸附特征及影响因素研究

通过恒温振荡平衡法研究了Pb~(2+)在针铁矿上的等温吸附和吸附动力学特征,探讨了吸附的影响因素.结果表明:(1)随Pb~(2+)平衡浓度和pH的增大,针铁矿对Pb~(2+)的吸附量逐渐增大.(2)针铁矿对Pb~(2+)的等温吸附可用Freundlich和Langmuir方程较好地拟合.(3)在相同温度和pH下,随离子强度的提高,针铁矿对Pb~(2+)的吸附量增大.(4)在相同离子强度和pH下,针铁矿对Pb~(2+)的吸附量总体随温度升高而增大.针铁矿对Pb~(2+)的吸附是自发进行的吸热反应.(5)针铁矿吸附Pb~(2+)的过程可分为初始的快吸附和随后的慢吸附2个阶段.pH影响吸附反应快慢,随pH增大吸附速率增大;随着pH的增大,达到平衡吸附的时间缩短.吸附动力学方程用Elovich方程拟合最佳.