水稻土中重金属元素Cd、Pb的竞争吸附 ——以长株潭地区水稻土为例

对中国南方的3个水稻土样品进行了Cd、Pb单一离子和混合离子吸附特点的研究。结果表明,3个水稻土样品中Cd、Pb的吸附特点都相似,Langmuir等温方程可很好地描述Cd、Pb的吸附等温线。3个土壤样品中,有较高pH值和较低有机物、CEC浓度、粘土含量、高岭石含量的2个土壤样品对Cd、Pb有较大的吸附量,且其等温吸附拟合的最大吸附量(B)也较大。在两组分混合溶液中,尽管共存离子的存在影响了土壤对单一离子的吸附,同时土壤对Cd的吸附在一定程度上受影响的程度大,但3个土壤样品都表现出对Pb有强的吸附能力。在3个土壤样品中,Langmuir等温方程中Pb的健合能常数(K)都大于Cd的健合能常数(K),混合溶液中的K值高于单一溶液的K值,表明2种金属离子对吸附位点的竞争提高了特定吸附位点的保持力,使金属离子在土壤中特定位点的吸附更加坚固。     

水稻土中重金属元素Cd、Pb的竞争吸附——以长株潭地区水稻土为例

对中国南方的3个水稻土样品进行了Cd、Pb单一离子和混合离子吸附特点的研究。结果表明,3个水稻土样品中Cd、Pb的吸附特点都相似,Langmuir等温方程可很好地描述Cd、Pb的吸附等温线。3个土壤样品中,有较高pH值和较低有机物、CEC浓度、粘土含量、高岭石含量的2个土壤样品对Cd、Pb有较大的吸附量,且其等温吸附拟合的最大吸附量（B）也较大。在两组分混合溶液中,尽管共存离子的存在影响了土壤对单一离子的吸附,同时土壤对Cd的吸附在一定程度上受影响的程度大,但3个土壤样品都表现出对Pb有强的吸附能力。在3个土壤样品中,Langmuir等温方程中Pb的健合能常数（K）都大于Cd的健合能常数（K）,混合溶液中的K值高于单一溶液的K值,表明2种金属离子对吸附位点的竞争提高了特定吸附位点的保持力,使金属离子在土壤中特定位点的吸附更加坚固。     

A surface complexation and ion exchange model of Pb and Cd competitive sorption on natural soils

The bioavailability and fate of heavy metals in the environment are often controlled by sorption reactions on the reactive surfaces of soil minerals. We have developed a non-electrostatic equilibrium model (NEM) with both surface complexation and ion exchange reactions to describe the sorption of Pb and Cd in single- and binary-metal systems over a range of pH and metal concentration. Mineralogical and exchange properties of three different acidic soils were used to constrain surface reactions in the model and to estimate surface densities for sorption sites, rather than treating them as adjustable parameters. Soil heterogeneity was modeled with >FeOH and >SOH functional groups, representing Fe- and Al-oxyhydroxide minerals and phyllosilicate clay mineral edge sites, and two ion exchange sites (X⁻ and Y⁻), representing clay mineral exchange. An optimization process was carried out using the entire experimental sorption data set to determine the binding constants for Pb and Cd surface complexation and ion exchange reactions.Modeling results showed that the adsorption of Pb and Cd was distributed between ion exchange sites at low pH values and specific adsorption sites at higher pH values, mainly associated with >FeOH sites. Modeling results confirmed the greater tendency of Cd to be retained on exchange sites compared to Pb, which had a higher affinity than Cd for specific adsorption on >FeOH sites. Lead retention on >FeOH occurred at lower pH than for Cd, suggesting that Pb sorbs to surface hydroxyl groups at pH values at which Cd interacts only with exchange sites. The results from the binary system (both Pb and Cd present) showed that Cd retained in >FeOH sites decreased significantly in the presence of Pb, while the occupancy of Pb in these sites did not change in the presence of Cd. As a consequence of this competition, Cd was shifted to ion exchange sites, where it competes with Pb and possibly Ca (from the background electrolyte). Sorption on >SOH functional groups increased with increasing pH but was small compared to >FeOH sites, with little difference between single- and binary-metal systems. Model reactions and conditional sorption constants for Pb and Cd sorption were tested on a fourth soil that was not used for model optimization. The same reactions and constants were used successfully without adjustment by estimating surface site concentrations from soil mineralogy. The model formulation developed in this study is applicable to acidic mineral soils with low organic matter content. Extension of the model to soils of different composition may require selection of surface reactions that account for differences in clay and oxide mineral composition and organic matter content.     

自然水体生物膜、悬浮颗粒物和沉积物吸附铅、镉的热力学参数比较

采用实验室模拟的方法研究了松花江自然水体生物膜、悬浮颗粒物和沉积物吸附铅、镉的热力学规律。根据吸附热力学参数（Γ_max、k和K_d）综合比较3种固相物质的吸附能力,并讨论吸附能力存在差异的原因。结果表明：Langmuir型及Freundlich等温式可以很好地描述3种固相物质吸附热力学规律,三者吸附铅、镉的能力为生物膜>悬浮颗粒物>沉积物,生物膜、悬浮颗粒物和沉积物对铅的吸附能力均明显高于对镉的吸附能力。     

Competitive adsorption of metal cations onto two gram positive bacteria: testing the chemical equilibrium model

In order to test the ability of a surface complexation approach to account for metal-bacteria interactions in near surface fluid-rock systems, we have conducted experiments that measure the extent of adsorption in mixed metal, mixed bacteria systems. This study tests the surface complexation approach by comparing estimated extents of adsorption based on surface complexation modeling to those we observed in the experimental systems. The batch adsorption experiments involved Ca, Cd, Cu, and Pb adsorption onto the surfaces of 2 g positive bacteria: Bacillus subtilis and Bacillus licheniformis. Three types of experiments were performed: 1. Single metal (Ca, Cu, Pb) adsorption onto a mixture of B. licheniformis and B. subtilis; 2. mixed metal (Cd, Cu, and Pb; Ca and Cd) adsorption onto either B. subtilis or B. licheniformis; and 3. mixed or single metal adsorption onto B. subtilis and B. licheniformis. %Independent of the experimental results, and based on the site specific stability constants for Ca, Cd, Cu, and Pb interactions with the carboxyl and phosphate sites on B. licheniformis and B. subtilis determined by Fein et al. (1997), by Daughney et al. (1998) and in this study, we estimate the extent of adsorption that is expected in the above experimental systems.Competitive cation adsorption experiments in both single and double bacteria systems exhibit little adsorption at pH values less than 4. With increasing pH above 4.0, the extent of Ca, Cu, Pb and Cd adsorption also increases due to the increased deprotonation of bacterial surface functional groups. In all cases studied, the estimated adsorption behavior is in excellent agreement with the observations, with only slight differences that were within the uncertainties of the estimation and experimental procedures. Therefore, the results indicate that the use of chemical equilibrium modeling of aqueous metal adsorption onto bacterial surfaces yields accurate predictions of the distribution of metals in complex multicomponent systems.     

The adsorption of Cu,Pb, Zn,and Cd on goethite from major ion seawater

The adsorption of Cu, Pb, Zn, and Cd on goethite (αFeOOH) from NaNO₃ solutions and from major ion seawater was compared to assess the effect of the major ions of seawater (Na, Mg, Ca, K, Cl, and SO₄) on the adsorption behavior of the metals. Magnesium and sulphate are the principal seawater ions which enhance or inhibit adsorption relative to the inert system. Their effect, as determined from the site-binding model of Davis et al. (1978), was a combination of changing the electrostatic conditions at the interface and decreasing the available binding sites.The basic differences between the experimental system of major ion seawater and natural seawater were examined. It was concluded that: 1) although the experimental metal concentrations in major ion seawater were higher than those found in natural seawater, estimates of the binding energy of Cu, Zn, and Cd with αFeOOH for natural seawater concentrations could be made from the data, 2) Cu, Pb, Zn, and Cd showed little or no competition for surface sites on goethite, and 3) the presence of carbonate, phosphate, and silicate had little or no effect on the adsorption of Zn and Cd on goethite.     

Metal binding capacity of northern European surface waters for Cd,Cu, and Pb

Total concentrations of and binding capacities for Cd, Cu, and Pb were measured in selected surface waters from northwestern Europe. Linear multiple regression predictive models explained 97, 93, and 96% of the observed variation in Cd, Cu and Pb binding capacities, respectively. The models constructed used (CO₂^3?) and (SO₂^2?) to predict Cd binding capacity, (OH^?) and (SO₄^2?) to predict Cu binding capacity and (OH^?), (CO₃^2?) and (SO₄^2?) to predict Pb binding capacity. Organic carbon was not significantly correlated with binding capacities for Cd, Cu, and Pb and was unimportant in explaining a significant amount of the variability in binding capacities for the metals of northern European surface waters. Thus, the effects of these organics on trace metal speciation can be ignored and predictive models of trace metal speciation constructed, using inorganic solubility equilibria only. Ratios of total Cd, Cu, and Pb concentrations to their respective binding capacities were much less than unity for all waters studied. Copper exhibited the greatest metal concentrations: binding capacity ratio in all waters investigated.     

A comparison of organic wastes as bioadsorbents of heavy metal cations in aqueous solution and their capacity for desorption and regeneration

The adsorption capacity of seven organic wastes/by-products (slash pine, red gum and western cypress bark, composted green waste, prawn exoskeletons, spent brewery yeast and mill mud from a sugar mill) for transition metals were determined at two metal concentrations (10 and 100 mg L⁻¹) and three equilibrium pH values (4.0, 6.0 and 8.0) in batch adsorption experiments. All tested materials indicate a positive affinity to adsorb metal cations from aqueous solution and spent yeast was the least effective. Adsorption generally increased with increasing pH and the order of selectivity of metals was: Cr³⁺ > Cu²⁺ > Pb²⁺ > Zn²⁺ ≥ Cd²⁺. For pine bark, compost, spent yeast and prawn shell, quantities of previously adsorbed Pb and Cd desorbed in 0.01 M NaNO₃ electrolyte were negligible. However, 0.01 M HNO₃, and more particularly 0.10 and 0.50 M HNO₃ were effective at removing both adsorbed Pb and Cd. Using 0.10 M HNO₃ as the regenerating agent, pine bark and compost maintained their Pb and Cd adsorption capacity over eight successive adsorption/regeneration cycles. For mill mud and prawn shell, there was a pronounced decrease in adsorption capacity after only one regeneration cycle. A subsidiary experiment confirmed that acid pre-treatment of the latter two materials appreciably reduced their Pb and Cd adsorption capacity. This was ascribed to the metal adsorption capacity of prawn shell and mill mud being partially attributable to their significant CaCO₃ content and acid treatment induces dissolution of the CaCO₃. It was shown that in relation to both adsorption capacity and desorption/regeneration capability, composted green waste showed the greatest potential.     

Interactions between Cd,Cu, Pb,and Zn and four different mine soils

The chemical associations of Cd, Cu, Pb, and Zn in four mine soil samples from the Amizour-Bejaia Pb/Zn mine (Algeria) have been investigated by a five-step sequential extraction procedure. Although Cd preferentially binds to carbonates, Cu, Pb, and Zn are mainly associated with the organic and reducible fractions. Batch adsorption experiments with either mono- or multi-metallic solutions are described with the Freundlich isotherm model. Whatever the nature of the soil sample, the sorption behavior for each given metal except Pb is very similar, indicating that the binding sites at the soil surface are progressively occupied by the metal from the solution. On each soil sample, the decreasing order of sorption can be established as Pb >> Cu > Cd > Zn. When the four metals are simultaneously applied to each soil sample, their specific behavior is strongly affected by their interactions and/or competition for the available surface sites: we generally observed isotherm curves with a slight maximum before the plateau at higher solution concentration. Although Cu is only slightly affected by the other metals, in the case of Pb, Cd, and Zn, the sorbed amounts strongly decreased.     

Similar Adsorption Parameters for Trace Metals with Different Aquatic Particles

Conditional surface binding constants and complexation capacities for Zn, Pb, Cd, and Cu were determined from surface titration experiments of heterogeneous natural aquatic particulate matter of different origin and composition. Metals and particles were evaluated in naturally occurring concentration ranges in river water.The adsorption of trace metals can be adequately described with a single conditional binding constant over a wide range of metal : particle ratios. Binding constants for aquatic particles at pH 8.0 are remarkably independent from particle composition and are specific for each metal: log K^ads _Zn = 8.39, log K^ads _Pb = 9.67, log K^ads _Cd = 8.61, log ^ads _Cu = 9.84. From competition experiments with Ca and Pb we extracted a sorption coefficient for Ca of log K^ads _Ca = 2.5 (pH 8.0). Maximum surface binding capacities for all metal ions were found for particles containing high fractions of Mn-oxides which are associated with large specific surface areas. Generally, we found sorption capacities to decrease in the sequence Cu Pb, Zn > Cd.The experiments suggest that the conditional surface binding constants and complexation capacities are applicable to model trace metal adsorption in the concentration ranges of natural waters under conditions similar to the experiments. Results also imply that the chemical nature of particle surface sites is rather uniform in the intermediate concentration range or that the array of binding sites averages out differences in sorption strength over the prevailing concentration range of metal ions, respectively.     

Cd adsorption onto Pseudomonas putida in the presence and absence of extracellular polymeric substances

The role of bacterial extracellular polymeric substances (EPS) in metal adsorption was determined by studying Cd adsorption onto the gram-negative bacterial species Pseudomonas putida with and without enzymatic removal of EPS from the biomass material. A range of experimental approaches were used to characterize the Cd adsorption reactions, including bulk proton and Cd adsorption measurements, FTIR spectroscopy, and fluorescence microscopy. The proton-reactivities of the biomass samples with EPS are not significantly different from those obtained for EPS-free biomass. Similarly, the presence of EPS does not significantly affect the extent of Cd removal from solution by the biomass on a mass-normalized basis, based on bulk Cd adsorption measurements conducted as a function of pH, nor does it appear to strongly affect the Cd-binding groups as observed by FTIR. However, fluorescence microscopy indicates that Cd, although concentrated on cell walls, is also bound to some extent to EPS. Together, the results from this study suggest that the P. putida EPS can bind significant concentrations of Cd from solution, and that the nature and mass-normalized extent of the binding is similar to that of the cell wall. Therefore, the EPS-bearing systems do not exhibit enhanced mass-normalized removal of Cd from solution relative to the EPS-free systems. The presence of the EPS effectively increases the viability of cells exposed to aqueous Cd, likely due to sequestration of the Cd away from the cells due to Cd-EPS binding.     

<Superscript>1</Superscript>H NMR-based serum metabolic profiling of <Emphasis Type="Italic">Carassius auratus gibelio</Emphasis> under the toxicity of Pb<Superscript>2+</Superscript> and Cd<Superscript>2+</Superscript>

Lead and cadmium are the two widely recognized toxic metals, with known ecological risk to freshwater fish in contaminated ecosystems. However, their effect at environmentally realistic level in a mixture has been rarely investigated. In the present study, serum metabolic responses of Crucian carp exposed to Pb (30 µgL^?1), Cd (100 µgL^?1) and Pb+Cd (30 + 100 µgL^?1) for 21 days were investigated by ¹H NMR-based metabolomics. The metabolic responses were compared to control by multivariate techniques (PCA, PLS-DA and OPLS-DA), and metabolites that significantly contributed to the variation were identified. Metal dependent metabolic responses revealed a decline of alanine, lysine and tyrosine in Pb exposed fish, indicating changes in neurotransmitters, and amino acid metabolism, while fish exposed to Cd showed significant decrease in lysine, isoleucine, leucine, alanine and increase in 3-hydroxybutyrate, acetone, lactate, choline, inosine, guanosine and threonine. The coexposure of Pb and Cd had additive effect on metabolic profile with increase in pyruvate, guanosine and inosine. The overall metabolic changes due to Pb and Cd were characterized by disturbed energy metabolism, impaired osmotic regulation and a shift from aerobic to anaerobic respiration. Moreover, ¹H NMR-based metabolomics was proved to be a powerful tool in elucidating the toxic effects of environmental pollutants and underlying mechanism.     

Trace metals in oxic lake sediments: possible adsorption onto iron oxyhydroxides

Apparent overall equilibrium constants for the adsorption of Cd, Cu, Ni, Pb and Zn onto natural iron oxyhydroxides have been calculated from the partitioning of these trace metals in oxic lake sediments and the in situ measurement of trace metal concentrations in the associated pore waters. Such values obtained from lakes of various pH located on the Precambrian Shield, in the area of Sudbury, Ontario, are compared with equilibrium constants obtained for the adsorption of the trace metals onto iron oxyhydroxides in well-defined media.The field data are consistent with laboratory experiments reported in the literature and with theory. Both the influence of pH upon adsorption and the binding strength sequence observed for the field data agree with theory. At high sediment pH values, the partitioning of Cd, Ni and Zn between the pore waters and the natural iron oxyhydroxides is similar to those reported in the literature for the adsorption of these metals at low surface coverage onto amorphous iron oxyhydroxides in a NaNO₃ medium; deviation from this simple model is however observed for Cu and Pb, presumably due to the competitive action of dissolved ligands. At low sediment pH values, the adsorption is much higher than predicted by the simple model and can be explained by the formation of ternary complexes with the iron oxyhydroxide surface.     

利用GCMC分子模拟技术研究页岩气的吸附行为和机理

揭示页岩气的吸附机理是阐明页岩气的吸附规律及转化条件、建立具有普适意义的定量评价模型的基础.采用GCMC（Grand Canonical Monte Carlo）分子模拟方法,对不同温压条件下CH₄和CO₂在不同孔径的伊利石狭缝形孔隙中的吸附行为进行模拟,结果表明,分子模拟与实验所得的吸附量归一化到单位表面积才具有相同的内涵和比较的意义.在此基础上进行的对比表明,分子模拟与实验结果相近,奠定了由分子模拟考察页岩气吸附行为和机理的基础:气体吸附于矿物表面的内因（机理）是气-固分子之间的范德华力和库仑力,伊利石表面对CO₂的吸附能力比其对CH₄的吸附能力强是其结合能更高的反映;CH₄和CO₂在伊利石表面的吸附虽然并非严格的单分子层吸附,但以一个强吸附层为主;孔径减小到微孔后吸附相密度将发生叠加,形成微孔填充,也是其结合能叠加的结果.      

Modeling the adsorption of Cd (II), Cu (II), Ni (II), Pb (II) and Zn (II) onto montmorillonite

The adsorption of five toxic metallic cations, Cd(II), Cu(II), Ni(II), Pb(II) and Zn(II), onto montmorillonite was investigated as a function of pH and ionic strength and a two-site surface complexation model was used to predict the adsorption data. The results showed that in the lower pH range, 3∼6 for Cd, Cu, Ni and Zn, and 3∼4.5 for Pb, the adsorption was greatly affected by ionic strength, while in the higher pH range, the adsorption was not. In the lower pH range, the metallic cations were mainly bound through the formation of outer-sphere surface on the permanently charged basal surface sites (≡X⁻), while in the higher pH range the adsorption occurred mainly on the variably charged edge sites (≡SOH) through the formation of inner-sphere surface complexes. Acid-base surface constants and metal binding constants for the two sites were optimized using FITEQL. The adsorption affinity of the five metallic cations to the permanently charged sites of montmorillonite was Pb > Cu > Ni ≈ Zn ≈ Cd, while that to the variable charged sites was Pb ? Cu > Zn > Cd > Ni.     

Marine scavenging: Trace metal adsorption by interfacial sediment from MANOP Site H

The adsorption of thirteen trace metals from seawater was studied on interfacial sediment from MANOP site H. The adsorption data indicate a long (~20 day) equilibration time for most metals, an increase in adsorption with an increase in pH and particle concentration, a dependence of adsorption on total metal concentration at high adsorption densities, and a lack of correlation between metal binding ability and metal hydrolysis in solution.Apparent equilibrium binding constants normalized to the total number of available sites on the solid were determined for metal binding with the interfacial sediment. The binding constants indicate that the affinity sequence for metal interactions with the interfacial sediment is: Pb > Fe > Sn ? Co≈ Mn > Cu > Be > Sc ? Zn > Ni > Cd ? Ba > Cs at pH 7.82 in seawater.A comparison of the binding constants for suspended particles, interfacial sediment, and surface sediment indicate that the composition of particles influences the binding ability of the particles. Biogenic particles tend to bind most metals more strongly than lithogenic or authigenic particles.Based on limited data, there is a strong positive correlation between the measured binding constants and the observed partitioning of metals between sediment and seawater.     

Molecular modeling of Al and benzene interactions with Suwannee fulvic acid

The effects that Al³⁺ and benzene interactions exhibit on a model fulvic acid were investigated. Energy minimizations of the structures mimicking the interactions of Al³⁺-Suwannee fulvic acid (SFA), benzene-SFA and Al³⁺-benzene-SFA were run with a solvation sphere of 60 H₂O molecules with the semi-empirical methods PM3 and PM5. The semi-empirical method PM3 was run with Gaussian 98 and CAChe Workstation Pro 6.1.1 to compare the results of the energy minimization algorithms in the two programs. PM5 calculations were run with CAChe Workstation Pro 6.1.1. Molecular dynamics (MD) simulations were run in Cerius² (Accelrys Inc., San Diego, CA) using the Universal Force Field (UFF) 1.02 [Rappé A. K., Casewit C., Colwell K., Goddard W., and Skiff W. (1992) UFF, a full periodic-table force-field for molecular mechanics and molecular dynamics simulations. J. Am. Chem. Soc.114(25), 10024-10035] and COMPASS force field [Sun H. (1998) COMPASS: an ab initio force-field optimized for condensed-phase applications—overview with details on alkane and benzene compounds. J. Phys. Chem. B102, 7338-7364]. Single point calculations were run on the minimized structures at the B3LYP/6-31G(d) level to obtain more accurate estimates of the energy on the minimized structures derived from the PM3, PM5, and UFF methods and to normalize energies to the same reference state. This methodology was used as the standard of comparison for all the models to assess whether or not a given configuration was reasonably stable.The PM3/G03 energy minimizations predicted the lowest B3LYP/6-31G(d) potential energies of the methodologies examined in this study. Thus, this method is considered the most reliable of those tested. The PM3/G03 method predicted that there would be aromatic-aromatic interactions between benzene and SFA. The presence of Al³⁺ was predicted not to interfere with aromatic-aromatic interactions between benzene and SFA, but benzene may influence the location of metal complexation to SFA.     

Risk of metal mobility in soils from a Pb/Zn depleted mine (Lugo,Spain)

The risk of Pb, Zn and Cd mobility is evaluated in soils from a depleted mine at Rubiais (Lugo, Spain). This area is under special protection because of its outstanding natural value. Soils from nine different areas were selected: at the mining zone (R1, R2, R3), at minespoils (R4, R5, R6) and soils developed on the settling pond (R7, R8, R9). A control soil (RC) was sampled outside the mine. The objectives are (i) to study the characteristics of soils with high influence on metal retention, (ii) to determine the content of Pb, Zn and Cd comparing it with the generic reference levels, and (iii) to evaluate the distribution and the interactions between the metals and the soil geochemical phases by means of sequential chemical extraction, X-ray diffraction, field emission scanning electron microscopy/energy-dispersive X-ray spectroscopy (FE-SEM/EDS) and time of flight secondary ion mass spectrometry (TOF–SIMS). The concentration of Pb, Zn and Cd ranges 850–6,761, 1,754–32,287 and 1.8–43.7 mg kg^?1, respectively, and the highest proportion is in the residual fraction. The Mn oxides highly influence the retention of Cd while Pb retention is mainly influenced by Fe oxides. Zn is uniformly distributed amongst the residual fraction and the Fe and Mn oxides. TOF–SIMS and SEM/EDS techniques confirm the fractionation results, showing how Pb and Zn are as sulphide and associated with Fe and Mn oxides. Nevertheless, care should be taken since oxides and sulphides could suffer sulphide oxidation processes or alteration of the oxides causing leaching and the contamination of the protected ecosystem.     

Biosorption of heavy metals by organic carbon from spent mushroom substrates and their raw materials

The use of agricultural wastes as biosorbents is gaining importance in bioremediation of heavy metal-polluted water and soils, due to their effectiveness and low cost. This work assesses the Cd, Pb and Cu adsorption capacity of the raw materials used in the production of substrates for mushroom production (Agaricus bisporus and Pleurotus ostreatus) and the spent mushroom composted (SMC), based on the functional groups of their organic carbon. The raw materials studied included agricultural wastes (wheat straw, wheat and rice poultry litter, grape pomace) and inorganic substances (gypsum and calcareous sand). Organic carbon from wastes and their composting products were characterized by CP-MAS ¹³C NMR. Langmuir adsorption isotherms of metals were plotted for each raw material, composting step, spent A. bisporus and P. ostreatus substrates and the final SMC. The maximum adsorption capacities of SMC were 40.43, 15.16 and 36.2 mg g^?1 for Cd, Pb and Cu, respectively. The composting process modified the adsorption properties of raw materials because of the enhanced adsorption of Cd and Cu and decreased adsorption capacity of Pb. CP-MAS ¹³C NMR and potentiometric titration were used to identify the functional groups of the organic carbon responsible for the metal adsorption. The content of cellulose was correlated with Pb adsorption (p < 0.001), alkyl and carboxyl carbon with Cd adsorption (p < 0.001), and N-alkyl (p < 0.001) and carboxyl (p < 0.010) groups with Cu adsorption. These results are valuable to develop new biosorbents based on agricultural wastes and demonstrate the high potential of SMC to adsorb heavy metals from polluted environments.     

Adsorption kinetics and intraparticulate diffusivities of Hg, As and Pb ions on unmodified and thiolated coconut fiber

As, Hg and Pb are examples of heavy metals which are present in different types of industrial effluents responsible for environmental pollution. Their removal is traditionally made by chemical precipitation, ion-exchange and so on. However, this is expensive and not completely feasible to reduce their concentrations to the levels as low as required by the environmental legislation. Biosorption is a process in which solids of natural origin are employed for binding the heavy metal. It is a promising alternative method to treat industrial effluents, mainly because of its low cost and high metal binding capacity. The kinetics was studied for biosorption experiments using coconut fiber for As (III), Hg (II) and Pb (II) ions adsorption. The specific surface area and surface charge density of the coconut fiber are 1.186×10²⁵ (m²/g) and 5.39 ×10²⁴ (meq/m²), respectively. The maximum adsorption capacity was found to be the highest for Pb (II) followed by Hg (II) and As (III). The modification of the adsorbent by thiolation affected the adsorption capacity. Equilibrium sorption was reached for the metal ions at about 60 min. The equilibrium constant and free energy of the adsorption at 30 °C were calculated. The mechanism of sorption was found to obey the particle-diffusion model. The kinetic studies showed that the sorption rates could be described by both pseudo first-order and pseudo second-order models. The pseudo second-order model showed a better fit with a rate constant value of 1.16 × 10^?4/min. for all three metal ions. Therefore, the results of this study show that coconut fiber, both modified and unmodified, is an efficient adsorbent for the removal of toxic and valuable metals from industrial effluents.