Sorption-desorption tests to assess the risk derived from metal contamination in mineral and organic soils

We obtained the sorption isotherms of Cd, Cu, Pb and Zn from seven soils with contrasting properties, including mineral and organic soils. The distribution coefficients (Kd) were determined from batch tests in a solution that simulated the soil solution cationic composition. The Kd values of the target metals varied greatly depending on soil type and initial metal concentration. Sorption isotherms were fitted to Freundlich and Langmuir models, and derived parameters were correlated to soil properties through the construction of a correlation matrix and application of Principal Component Analysis. The batch Kd showed a satisfactory agreement with the Kd obtained from field-contaminated soils. The sorption tests were complemented with the estimation of the reversibility of metal sorption by the application of an extraction test. The extraction yields, which did not relate to the initial metal concentration, depended on the metal-soil combination, and showed no correlation to batch Kd values. The risk derived from a contamination event was estimated through the quantification of a Retention Factor, defined as the ratio of the Kd versus the extraction yield. Results showed that this was an excellent index to highlight which metal and soil represent the most vulnerable scenarios after a contamination event.     

The interaction of heavy metals with urban soils: sorption behaviour of Cd, Cu, Cr, Pb and Zn with a typical mixed brownfield deposit

This study investigated the sorption characteristics and release of selected heavy metals (Cd, Cu, Cr, Pb and Zn) from a typical urban soil material from a derelict brownfield site in Western Scotland, UK. The study aimed to evaluate contaminant interactions with an urban substrate, comprising a mix of mineral soil and residue materials (e.g. brick, concrete, wood). This type of material has received little consideration in the literature to date. Soil samples were subject to a sequence of test involving batch equilibration and dynamic leaching, in single (non-competitive) and multi-element (competitive) solutions. The batch experiments were carried out in unadjusted and close to soil field pH conditions (pH 2 and 7, respectively). The equilibrium adsorption capacity for heavy metals was measured and extrapolated using the Langmuir isotherm. The parameters of the isotherms x(m) (the maximum amount adsorbed per unit mass of adsorbent (mg/g)) and b (adsorption constant (m(3)/g)) were calculated for Cd, Cu, Cr, Pb as single-element and multi-element solutions. The adsorption from the single-element solution was more effective than adsorption under multi-element conditions, due to competitive effects. For example, the adsorption of copper from a single-element solution was over four times greater than for a multi-element solution. In the case of Cr and Zn, migration of metal from soil to solution was observed. Adsorption capacity at pH 2 followed the order Cr>Cu>Pb>Cd and at pH 7 Cd>Zn, with precipitation affecting Cu and Pb behaviour. During the column leaching experiment, most of the heavy metals were irreversibly bound to the soil, but in the case of Cr some movement from soil into solution was observed. The results also showed that Cd, Cu, Pb and Zn were removed from the solution and adsorbed on the soil. No significant difference in the metal removal from single- and multi-element solutions was observed. Overall, the urban residue behaved in a similar manner to mineral soils despite a significant component of anthropogenic solid materials.     

Kinetics of trace element uptake and release by particles in estuarine waters: effects of pH,salinity, and particle loading

The uptake and release of 109Cd, 51Cr, 60Co, 59Fe, 54Mn, and 65Zn were studied using end-member waters and particles from Port Jackson estuary, Australia. The kinetics of adsorption and desorption were studied as a function of suspended particulate matter (SPM) loading and salinity. Batch experiments showed that the position and slope of the pH edges are dependent on the metal and on the salinity of the water (except for Mn). The general effect of salinity was to move the adsorption edge to higher pH values, with the greatest change being found for Cd. Most of the metals showed relatively simple kinetics with an increase in uptake as a function of time and suspended particle concentrations. The time dependence of Cd uptake was more complex, with an initial adsorption phase being followed by strong mobilization from the suspended sediments, explained by chlorocomplexation and competition with seawater major cations. The reversibility of the sorption decreased in the order Co>Mn>Zn>Cd>Fe>Cr. The percentage of adsorbed metal released in desorption experiments was greater in seawater than freshwater for Cd, Zn, and Co. These results are important in understanding the cycling of pollutants in response to pH, salinity, and particle concentrations in estuarine environments. In addition, they give valuable insight into the important mechanisms controlling the partitioning of heavy metals in the Port Jackson estuary.     

Adsorption and desorption of iodine by various Chinese soils: I. Iodate

In order to assess the adsorption of iodate by different soils from China, a series of batch experiments were conducted. It was found that soils rich in iron oxide had high affinity for iodate. Iodate adsorption isotherms could be well fitted with both Langmuir and Freundlich equations. Iodate adsorption by 20 different soils from China revealed that iodate adsorption was significantly correlated with soil organic matter negatively and positively with free iron oxide contents. At initial concentration of 4 mg I L(-1), iodate adsorption ranged between 9 and 34 mg kg(-1) soil. No correlation between iodate adsorption and cation exchange capacity and soil pH was found. For a single soil, there was a significant linear relationship between the amounts of iodate adsorbed and desorbed, but for a group of different soils, the relationship between the amounts of iodate adsorption and desorption followed a nonlinear relationship, the deviation mainly occurred at high adsorption side. The relationship between K(d) and free aluminum oxide and free iron oxide contents showed an exponential relationship for various soils with exception of the soil from Hetian in Xinjiang.     

Adsorption of thorium from aqueous solutions by perlite

The use of expanded perlite for the adsorption of thorium from aqueous solution by batch technique is presented. The effects of particle size, pH of the solution, initial thorium concentration, shaking time, V/m ratio and temperature were determined. It was found that the adsorption capacity increases by the increase in the pH of the suspensions. The rate of thorium adsorption on expanded perlite was observed to be fast in the first hour of the reaction time. Adsorption isotherms were expressed by Langmuir and Freundlich adsorption models and the adsorption experiments conducted at 30 ± 1 °C showed that the adsorption isotherms correlated well with the Langmuir model. From the adsorption data, thermodynamic parameters such as ΔG^o, ΔH^o and ΔS^o were calculated as a function of temperature.     

Investigation of 85Sr adsorption on selected soils of different horizons

Studies on the mechanism of (90)Sr migration in soil require many processes to be considered. One of the most important is sorption on the surface of mineral components of the soil. In this study adsorption of (85)Sr on a variety of soil types from different horizons has been investigated. Adsorption isotherms show various affinities of (85)Sr, depending on soil type and to a lesser extent the horizon. An important effect of pH was found with a maximum in the range 5-7. The influence of calcium ions on the extent of adsorption of (85)Sr isotope on soil samples from surface horizons of four sites is presented. Depending on the soil type differing degrees of competitive adsorption of Sr and Ca were observed. Desorption of (85)Sr by distilled water as well as Ca(NO(3))(2) solution was also examined. Both methods resulted in the removal of a considerable proportion of the adsorbed isotope from the soil. Additionally the kinetics of the desorption process were studied.     

Sorption of metal ions from aqueous solution using bone char

The sorption of cadmium, copper and zinc from aqueous solutions onto bone char has been studied in both single and binary multi-component systems. Equilibrium experimental studies have been performed to determine the sorption capacity of bone char for each metal ion. The isotherm results have been analysed using single and multi-component equilibrium models. The rate of sorption of the metal ions onto bone char has been studied using an agitated batch adsorber. The concentration versus time decay curves have been measured and a number of mass transfer models have been developed and tested based on diffusion controlled sorption. The results of the equilibrium and rate studies are presented and discussed in the paper. The possible mechanisms of metal sorption are also discussed. Finally a series of fixed bed column studies have been performed and analysed using a diffusion mass transport model. The experimental results show a displacement effect for the binary metal ion breakthrough curves.     

Adsorption studies on coir pith for heavy metal removal

Biosorption efficiency of coir pith, a waste product from coir industry, was investigated in this study for the removal of metallic pollutants such as Ni, Cu and Zn from aqueous solutions. The disposal of coir pith is a major problem associated with the coir industries, especially working in the small-scale sector. The present study explores the effectiveness of utilization of coir pith, an accumulating waste, as a biosorbent for heavy metal removal. Batch mode studies were done to evaluate the efficiency of removal of metals under varying adsorption conditions of pH, metal concentration and contact time. Characterization studies of the biosorbent and SEM analysis were done. Kinetic modelling studies were tried using Lagergren pseudo-first-order and second-order models. Equilibrium studies were done using well-known Freundlich, Langmuir and D–R isotherm models. It was found that all isotherms are fitting well indicating the efficiency of coir pith as an adsorbent of heavy metals. The applicability of all the three isotherms to the sorption processes shows that both monolayer adsorption and heterogeneous energetic distribution of active sites on the surface of the adsorbent are possible. Due to the abundance and low cost of these materials, adsorption technologies developed can act as good sustainable options for the future in heavy metal removal from industrial effluents.     

Assessment of hydrothermally modified fly ash for the treatment of methylene blue dye in the textile industry wastewater

Dyes and pigments are one of the major water pollutants and if not discharged properly cause ecological disturbance. Considering this, the current study investigates the application of thermal power plant by-product, i.e., fly ash for the elimination of a hazardous methylene blue dye from its synthetic aqueous solution. Experiments were conducted in batch mode to study the effect of pH, temperature, adsorbent dose and contact time. Highest dye removal (94.3%) was achieved at pH 10 using adsorbent dose of 10 g/L in 90 min of contact time at 40 °C. However, for cost-effective operation at neutral pH and room temperature (30 °C), it yields 89.3% dye removal having similar dose and contact time. Equilibrium isotherms for adsorption were analyzed by Langmuir and Freundlich, Temkin and Dubinin–Radushkevich isotherm equations. The results revealed that the best fit model of adsorption closely followed Langmuir adsorption. Based on adsorption isotherm models, thermodynamics parameters ΔG, ΔH and ΔS were calculated. The negative value of ΔG and ΔH revealed that adsorption process was exothermic, spontaneous and physical. The present work suggests that through simple process hydrothermally modified fly ash has the potential to be used as cost-effective and efficient adsorbent for the treatment of wastewater from textile industries.     

Sorption of volatile organic compounds on typical carpet fibers

Measurements of adsorption isotherms for three volatile organic compounds (VOCs) (toluene, 1,2-dichlorobenzene and 1,1,1-trichloroethane) on polyacrylonitrile carpet fibers over the temperature range 25-45 degrees C were carried out in a thermogravimetric analyzer (TGA). Linear isotherms were observed in all cases with values of the Henry coefficient ranging from 0.063 to 0.941 mm. The results of additional experiments carried out in a simple test chamber containing a single source of VOC showed that the carpet fibers acted as a significant sink causing a prolonged elevation of VOC concentration in the air within the chamber. An unsteady-state model is presented, which adequately described the adsorption and desorption phenomena occurring in the test chamber and yielded realistic values of the adsorption and desorption rate constants. There was good agreement between the equilibrium and kinetic constants obtained in the TGA and test chamber experiments.     

Sorption of metals onto natural organic matter as a function of complexation and adsorbent-adsorbate contact mode

The effect of complexing anion and adsorbate-adsorbent contact mode (static equilibrium or dynamic non-equilibrium) on binding and partition of Cu(2+), Cd(2+) and Zn(2+) onto organic matter (exemplified in a low-moor peat) was studied. The study comprised comparative batch and column flow-through sorption experiments on monometallic solutions of Me-Cl and Me-SO(4) salts, at pH 4.0, and sequential fractionation of sorbed metals with respect to binding strength. Both the presence of an anion having complexing properties (Cl(-)) as well as a contact mode was found to quantitatively and qualitatively affect the sorption capacity and binding strength of organic matter (peat) for metal ions. Complexing effect of Cl(-) on metal ions resulted mostly in reduction of metal ability to form strongly bound metal-organic compounds, in accordance with the order of stability constant of complex ions log K: Cd>Zn>Cu. Flow-through (dynamic) contact mode, which is the most appropriate to simulate environmental conditions, appeared to strongly attenuate the complexing effect of chloride ions on Cd and Zn sorption, and significantly enhance sorption capacity also in the absence of complexing ions. For Cd, it was mainly due to the enrichment in the strongly bound "insoluble organic" fraction, while for Zn the quantitative increase of sorption capacity did not alter significantly its partitioning. Neither a quantitative nor qualitative effect of contact mode on Cu binding was observed. Complex and diverse effects of different environmental parameters on metal sorption capacity and binding strength onto organic matter, which strongly influence metal mobility, leads to the conclusion that the correct simulation of these parameters for ecotoxicological testing is crucial for the reliable predicting of metal bioavailability under actual terrestrial environmental conditions.     

Impact of water quality parameters on the sorption of U(VI) onto hematite

In this study, the sorption of U(VI) from aqueous solution on hematite was studied as a function of various water quality parameters such as contact time, pH, ionic strength, soil humic acid (HA) or fulvic acid (FA), solid content and temperature by using a batch technique. The results demonstrated that the sorption of U(VI) was strongly dependent on ionic strength at pH < 6.0, and outer-sphere surface complexation may be the main sorption mechanism. The sorption was independent of ionic strength at pH > 6.0 and the sorption was mainly dominated by inner-sphere surface complexation. The presence of HA/FA increases U(VI) sorption at low pH, whereas decreases U(VI) sorption at high pH. The thermodynamic parameters (ΔH⁰, ΔS⁰, and ΔG⁰) were calculated from the temperature dependent sorption isotherms, and the results suggested that U(VI) sorption was a spontaneous and endothermic process. The results might be important for the application of hematite in U(VI) pollution management.     

Experimental values for 241Am and 239+240Pu Kd's in French agricultural soils

Experiments resulted in determination of K(d) values for (241)Am and (239+240)Pu in 6 soils whose characteristics are representative of agricultural soils found around French nuclear power plant sites. These experiments were conducted in stirred batch reactors and the sorption isotherms were plotted. For americium, the experimental K(d) values varied from 60 to 4000 Lkg(-1) (d.w.) and correlated well with soil pH, K(d) increased with increasing pH. As regards plutonium, the experimental K(d) values varied between 300 and 9600 Lkg(-1) and decreased with increasing total sand content. The estimation of the total residence time determined by using a particular and experimentally refined value for K(d)-with a model similar to those currently used for impact assessments-illustrates the importance of establishing values that are better suited to specific soils than generic values. Lastly, depending on the type of evaluation envisioned, it might be important to look for a specific value of K(d)-and even modelling-more suited to the specificity of the scenario studied, by performing more complex, or even in situ, experiments.     

Irreversible sorption of pentachlorophenol to sediments: experimental observations

The partitioning behavior of pentachlorophenol (PCP) in five sediments was studied using equilibrium sorption experiments and multiple cycles of sorption and desorption experiments. The results of the equilibrium sorption experiments showed that the isotherms of PCP on five sediments were linear and the partitioning coefficients (Kd) were proportional to the organic carbon content of the sediments. The average organic carbon content normalized partitioning coefficient (logK oc) of five sediments was 2.83 +/- 1.48. In multiple cycles of sorption and desorption experiments, the five sediments were found to exhibit statistically significant sorption-desorption hysteresis, and the hysteresis indices (HI) varied over a wide range (0.72 - 11.82). Correlations between the HI value and the percentage of lipid in the total organic matter in the sediment indicated that lipid was the main fraction to affect the hysteresis phenomenon, i.e., the higher the lipid percentage the greater the HI value. The hysteresis phenomenon was mostly caused by irreversible sorption of PCP on lipids, including entrapment by lipids, which induced the slow desorption rate from the sediment. Because of hysteresis in the sorption and desorption, the PCP ecological toxicity would be lower than expected.     

长江三角洲地区海相沉积物母质土壤对Cu的吸附解吸特性

分别以长江三角洲地区海相沉积物母质土壤的表层土和心层土为例,考察了其对重金属Cu的吸附、解吸及固定特性,目的是了解其在不同土壤结构的存在形态和迁移特性。研究表明：不同表层土和心层土的铜吸附容量可用Langmuir,Freundlich和Temkin吸附等温方程拟合,其中以Langmuir方程吻合度最高,回归计算出的最大吸附容量与实验结果基本一致;而其解吸动力学大部分符合指数方式。研究发现,大多数土壤的心层土的最大吸附容量大于表层土,解吸量小于表层土;表层土中对Cu的固定吸附量最大的是滩涂泥,最小的是滩砂泥;心层土中对Cu的固定吸附量最大的是滩潮土,最小的是滩砂泥。不同土壤对Cu的固定吸附量存在差异性,这与土壤自身的pH、OM等多种因素有关, 一般pH值大、OM值高的土壤对Cu的固定吸附量越大.     

Removal of uranium(VI) from aqueous solutions by manganese oxide coated zeolite: discussion of adsorption isotherms and pH effect

This paper discusses the adsorption properties for uranium(VI) by manganese oxide coated zeolite (MOCZ). The removal of uranium(VI) from aqueous solution by adsorption onto MOCZ in a single-component system with various contact times, pH, competitive ions, temperatures and initial concentrations of uranium(VI) was investigated. The experimental results were fitted to the Langmuir, Freundlich and the three-parameter Redlich-Peterson model isotherms to obtain the characteristic parameters of each model. Both the Langmuir and Redlich-Peterson isotherms were found to best represent the measured adsorption data. According to the evaluation using the Langmuir equation, the maximum adsorption capacity of uranium(VI) ions onto MOCZ was 15.1 mg g(-1) at 293K and pH 4.0. Using the thermodynamic equilibrium constants obtained at different temperatures, various thermodynamic parameters, such as DeltaG(0), DeltaH(0) and DeltaS(0), have been calculated. The thermodynamics of uranium(VI) ion/MOCZ system indicates the spontaneous and endothermic nature of the process. It was noted that an increase in temperature resulted in a higher uranium loading per unit weight of the adsorbent.     

Study of Ni adsorption on NKF-6 zeolite

The adsorption of ⁶³Ni from aqueous solutions using NKF-6 zeolite was investigated by a batch technique under ambient conditions. The adsorption was investigated as a function of contact time, pH, ionic strength, foreign ions, humic substances (FA/HA) and temperature. The kinetic adsorption was well described by the pseudo-second-order rate equation. The adsorption of ⁶³Ni on NKF-6 zeolite was strongly dependent on pH and ionic strength, and the adsorption of ⁶³Ni increased with increasing NKF-6 zeolite content. At low pH values, the presence of FA enhanced the adsorption of ⁶³Ni on NKF-6 zeolite, but the presence of HA had no drastic effect. At high pH values, the presence of FA or HA decreased the adsorption of ⁶³Ni on NKF-6 zeolite. The adsorption isotherms were well represented by the Langmuir model. The thermodynamic parameters (i.e., ΔH⁰, ΔS⁰and ΔG⁰) for the adsorption of ⁶³Ni were determined from the temperature dependent isotherms at 293.15, 313.15 and 333.15 °K, respectively, and the results indicate that the adsorption reaction was favored at high temperature. The results suggest that the adsorption process of ⁶³Ni on NKF-6 zeolite is spontaneous and endothermic.     

Chemisorption and Physical Adsorption Roles in Cadmium Biosorption by Chlamydomonas Reinhardtii

The aim of this study was to investigate the mechanism of cadmium (Cd) adsorbed by microalgae Chlamydomonas reinhardtii (C.reinhardtii). The kinetic and adsorption isotherm of the process could be well described by mathematical models. Chemical modification experiments and Fourier transform infrared spectra indicated that carboxyl and amine groups were the important functional groups for adsorption of Cd. The maximum contribution of physical adsorption in the overall adsorption process was evaluated as 5.5%...     

Sorption behavior of selenium on humic acid under increasing selenium concentration or increasing solid/liquid ratio

The sorption of selenium (Se) on humic acid (HA) was investigated in order to better understand the fate of stable and radioactive Se in soils and sediments. An ultrafiltration technique was used to determine size distributions of HA-sorbed-Se when increasing Se concentration and solid/liquid ratio. The results showed that the Se sorption onto HA followed the Freundlich isotherm. No solid/liquid ratio-dependence was observed especially when <3 kDa molecular size fraction was used from solid/liquid separation. The Freundlich isotherm parameters K(F) and n obtained using the <3 kDa molecular size fraction for solid/liquid separation were 3.7 x 10(2) and 0.82, respectively. In addition, since dissolved HA increased with decreased ionic strength in the HA suspension, ionic strength could promote aggregation of HA. The conformational change of HA could affect the sorption behavior of Se on HA.     

Cadmium biosorption by cells of Spirulina platensis TISTR 8217 immobilized in alginate and silica gel

The biosorption of cadmium by immobilized Spirulina platensis on alginate gel and silica gel was studied. The maximum biosorption capacities for alginate immobilized cells and silica immobilized cells were 70.92 and 36.63 mg Cd/g biomass, respectively. Temperature did not have an influence on metal sorption, whereas an initial pH solution did. Sorption occurred in a wide pH range (pH 3-8). The highest adsorption of alginate immobilized cells was at pH 6, while silica immobilized cell adsorption was not affected at pH between 4 and 7. The immobilized cells were reused in consecutive adsorption-desorption. The results showed that immobilized cells could be repeatedly used in the sorption process up to five times.