Sorption behavior of heavy metal pollutants onto shales and correlation with shale geochemistry

The sorption of lead (II) and cadmium (II) on seven shales belonging to the Proterozoic Vindhyan basin, central India, and a black cotton soil, Mumbai, India, was studied and compared with sorbent geochemistry. The sorption equilibrium studies were conducted under completely mixed conditions in batch reactors (pH=5.0 and ionic strength= 0.01 M) at room temperature. The Freundlich model provided better fits to the experimental data compared to Langmuir model. High cadmium and lead sorption was observed for the calcareous shales with greater than 5% CaCO₃. The Freundlich isotherm parameter relating to sorption capacity, i.e., K_F, yielded a strong correlation with the calcium carbonate and calcium oxide content across the various geosorbents studied. The observed sorption pattern may be attributed to complex formation of CaCO₃ with Pb²⁺ and Cd²⁺ leading to surface precipitation. Moreover, the Ca²⁺ present in the sorbents may also involve in ion exchange reaction with lead and cadmium.     

Soil sorption of caesium modelled by the Langmuir and Freundlich isotherm equations

The Langmuir and Freundlich adsorption isotherm equations were used to model Cs sorption in 6 Welsh soils. The pH (in water), of the soils ranged from 3.5 to 6.5, and the estimated organic matter (determined by loss-on-ignition) ranged from 4.8% to 46%. According to the Langmuir adsorption isotherm, highest sorption maxima,b, were displayed by the loams at 102–204 mg kg⁻¹, compared with organic soils at 37–86 mg kg⁻¹. Subsoil horizons (15–30 cm depth) did not always display higher sorption maxima than their topsoil (0–15 cm depth) counterparts. Where an improved fit to the Freundlich model was found over the Langmuir model, it was assumed that either concurrent desorption of other species, or bond-energy heterogeneity in the substrate, were significant for these soils.     

Removal of arsenic and iron from mine-tailing leachate using chitosan hydrogels synthesized by gamma radiation

Mine residue and leachate were sampled from an acid mine drainage site near Arroyo San Pedro, which is one of the oldest abandoned mine districts in San Luis Potosi, Mexico, and characterized by X-ray diffraction and inductively coupled plasma-optical emission spectroscopy, confirming the presence of Fe, As, and SO₄ ^2?. To address this problem, chitosan network (net-CS) and chitosan network-N-vinylcaprolactam/N–N-dimethylacrylamide (net-CS)-g-NVCL/DMAAm hydrogels were synthesized and used as adsorbents of the different ions present in the aforementioned leachate by batch equilibrium procedure. Kinetics, isotherms, and ions dissolved in leachate were evaluated. The gels showed the highest adsorption capacity for As and Fe ions. The adsorption capacity of the net-CS hydrogels for As (V) and Fe(III) was 0.786 and 76.85 mg/g, respectively, attained after 50 h. The surface of the hydrogels was investigated by scanning electron microscopy and Fourier transform infrared spectroscopy, before and after the adsorption process, where the presence of a bond between the hydrogels and heavy metals ions, which is commonly observed in organic groups, was observed. In addition, Freundlich and Langmuir adsorption isotherms constants were determined for the As and Fe ions, and it was found that the Freundlich isotherm, with a first-order pseudo model, better fitted the adsorption process, indicating heterogeneous sorption, and the retention process occurred by chemisorption. The results from the Geochemist´s Workbench (GWB) software program revealed that arsenates, such as H₃AsO₄, H₂AsO₄ ^?, as well as Fe⁺⁺, FeSO₄(aq) and FeOH⁺ were the common aqueous species found in the leachate at pH = 2.9.     

Sorption of Cesium on Clay Colloids: Kinetic and Thermodynamic Studies

Sorption of radionuclides onto stable colloids can significantly enhance their transport in groundwater. Batch adsorption studies were performed to evaluate the influence of various experimental parameters like initial pH, contact time, temperature and concentration of Na⁺ and Ca²⁺ ions on the sorption of Cs on clay. The sorption process is dependent on pH of the solution with distribution coefficient (K _d) found to increase with increase in pH. The kinetic experiments were carried out at different temperatures, and the results have shown that the sorption process fits well into a pseudo-second-order mechanism with apparent activation energy of 45.7?kJ/mol. The rate constant was found to decrease with increase in temperature. The thermodynamic parameters such as ?G ⁰, ?H ⁰ and ?S ⁰ were calculated. The negative value of ?H ⁰ indicates that the reaction is exothermic. The negative values obtained for ?G ⁰ indicated that the sorption of cesium on clay was spontaneous at all studied concentrations. The distribution coefficient was found to decrease with increasing concentration of Na⁺ and Ca²⁺ ions. The cesium sorption data were fitted to Freundlich, Langmuir, Temkin and Dubinin–Radushkevich (D–R) isotherms. The values of Langmuir separation factor (R _L) indicate a favorable Cs adsorption. The values of mean free energy of sorption (E) at various temperatures ranged from 10.5 to 11.1?kJ/mol, which indicates that the sorption process follows chemisorption.     

Phosphorus adsorption characteristics at the sediment–water interface and relationship with sediment properties in FUSHI reservoir, China

This study was designed to survey the reservoir sediment properties, assess the phosphorus (P) sorption isotherm, and analyze the relationship between sediment properties and sorption parameters. Physicochemical analysis indicated that sediment from the FUSHI reservoir in Zhejiang Province, China, has similar physical and chemical properties and has been contaminated by P. Sorption isotherm experiments showed that the sorption process could be described by Langmuir and Freundlich models. The parameters of Q _max (Phosphorus sorption maximum) and K (Freundlich adsorption isotherm constant) ranged from 618.98 to 825.70?mg?kg^?1 and 114.18 to 170.74?l?kg^?1, respectively. EPC₀ (zero P equilibrium concentration) ranged from 0.14 to 0.24?mg?l^?1, more than the total P concentration in the water of the reservoir. Thus, the reservoir sediment releases P into the water and acts as a ??P resource??. The clay, Fe_o, Al_t, and Fe_t?+?Al_t content were the main active components in P sorption. Q _max had a highly significant positive relationship with some properties and could be estimated by a combination of these.     

Calculation of multicomponent chemical equilibria and reaction processes in systems involving minerals,gases and an aqueous phase

The compositional characteristics of many geochemical systems which involve the interaction of natural aqueous solutions with minerals and gases are conveniently described using the following thermodynamic components: Cl^?, SO₄⁼, HS^?, CO₃⁼, H⁺, Na⁺, K⁺, Ca⁺⁺, Mg⁺⁺, Fe⁺⁺, Zn⁺⁺, Cu⁺, Al⁺⁺⁺, SiO₂ and H₂O. A set of mass balance and mass action equations equal in number to the number of components plus the number of saturated minerals (and gases) is defined for a specified temperature, pressure and bulk composition. The mass balance equations include terms for minerals, gases and the molalities of aqueous complexes and dissociated species. This set of non-linear equations can be solved with the aid of a computer using'a Newton-Raphson technique. The calculation takes account of aqueous ion complexing, oxidation-reduction equilibria, activity coefficients, non-unit water activity and solid solutions. The use of H⁺, SO₄⁼, HS^? and H₂O as components allows straightforward treatment of processes involving oxidation-reduction, evaporation, boiling and changes of total aqueous H⁺ due to hydrolysis, mineral reaction or temperature change. One product of this approach is a technique for calculating pH at high temperature from measurement of pH at room temperature.By linking a series of discrete overall heterogeneous equilibrium calculations in which incremental changes of bulk composition, temperature or pressure are made, dynamic geochemical processes can be modeled. Example calculations for two such processes are given. These are the heating of seawater from 25° to 300°C and the isothermal irreversible reaction of rhyolite with an aqueous solution at 250°C.     

Phosphate sorption desorption characteristics of some ferruginous soils of tropical region in Eastern India

Phosphate sorption and desorption experiments were conducted with four ferruginous soils (alfisols) of Eastern India, in view of the low native phosphate concentrations in tropical Indian soils. From the P-isotherm curve, standard P requirement (SPR) of the soils was determined. Phosphate sorption data were fitted to both Langmuir and Freundlich equations and mean sorption maximum values obtained for the different soil series were in the decreasing order as Matimahal > Anandapur > Mrigindih > Kashipur. The fraction of added P sorbed followed the same trend as SPR, P sorption maximum (P_max), phosphate affinity constant (K), maximum phosphate buffering capacity (MPBC), Freundlich constant K′ and phosphate desorption values. Phosphate sorption maximum was significantly correlated with MPBC, Freundlich 1/n, SPR, clay and different forms of Fe and Al. The value of K (bonding energy) was significantly correlated with MPBC, Freundlich K′ and pyrophosphate extractable Fe and Al. The MPBC was significantly correlated with Freundlich K′, Freundlich constant 1/n, clay, oxalate and dithionite extractable, amorphous and crystalline form of Fe and Al. Freundlich K′ was significantly correlated with Freundlich 1/n, pH_water, clay, dithionite extractable and crystalline form of Fe and Al. The results suggested that the soils having higher amount of extractable and reactive Fe and Al shared higher P sorbtion capacity and such soils may need higher levels of P application     

Sorption characteristics and mechanisms of ammonium by coal by-products: slag, honeycomb-cinder and coal gangue

The adsorption behaviors of ammonium from aqueous solutions were investigated for three solid coal wastes, slag, honeycomb-cinder and coal gangue. The ammonium sorption processes were well modeled by the pseudo second-order model (R ² > 0.99). The experimental data were fitted to both the Langmuir model and the Freundlich model, with the Langmuir model better representing the data. The maximum ammonium sorption capacities calculated from the Langmuir model were 3.1, 5.0 and 6.0 mg/g for the slag, honeycomb-cinder and coal gangue samples, respectively. The pH value of the solution affected the ammonium removal, and the higher uptakes found in either neutral or alkaline conditions for the three materials. The thermodynamic parameters, ΔH, were calculated to be 29.75, 25.21 and 17.91 kJ/mol for the SL, HC and CG samples, respectively, with the positive values indicating that the ammonium sorption processes were endothermic. Based on the results, it can be concluded that coal gangue may have more potential for being used as a sorbent for the ammonium removal from wastewater among the three coal by-products.     

Heavy metal biosorption potential of a Malaysian Rhodophyte (<Emphasis Type="Italic">Eucheuma denticulatum</Emphasis>) from aqueous solutions

Biosorption is a promising technology for the removal of heavy metals from industrial wastes and effluents. In the present study, biosorption of Pb²⁺, Cu²⁺, Fe²⁺ and Zn²⁺ onto the dried biomass of Eucheuma denticulatum (Rhodophyte) was investigated as a function of solution pH, contact time, temperature and initial metal ion concentration. The experimental data were evaluated by Langmuir, Freundlich, Temkin and Dubinin–Radushkevich isotherm models. The sorption isotherm data followed Langmuir and Freundlich models, and the maximum Langmuir monolayer biosorption capacity was found as 81.97, 66.23, 51.02 and 43.48 mg g^?1 for Pb²⁺, Cu²⁺, Fe²⁺ and Zn²⁺, respectively. The sorption kinetic data followed pseudo-second-order and intraparticle diffusion models. Thermodynamic study revealed feasible, spontaneous and endothermic nature of the sorption process. Fourier transform infrared analysis showed the presence of amine, aliphatic, carboxylate, carboxyl, sulfonate and ether groups in the cell wall matrix involved in metal biosorption process. A total of nine error functions were applied in order to evaluate the best-fitting models. We strongly suggest the analysis of error functions for evaluating the fitness of the isotherm and kinetic models. The present work shows that E. denticulatum can be a promising low-cost biosorbent for removal of the experimental heavy metals from aqueous solutions. Further study is warranted to evaluate its potential for the removal of heavy metals from the real environment.     

Modeling of Cs+ diffusion and retention in the DI-A2 experiment (Mont Terri). Uncertainties in sorption and diffusion parameters

In the DI-A2 experiment several non-reactive and reactive tracers were injected as a pulse in a packed-off borehole in the Opalinus Clay. Unlike the previous DI-A1 test, the design of the Teflon filter in the injection borehole forced the water to flow through the filter and the open space between the filter and the borehole wall (the filter itself did not act as a diffusion barrier between the circulating solution and the rock). The decrease in tracer concentration in the liquid phase was monitored during a period of a year. Afterwards, the borehole section was overcored and the tracer profiles in the rock were analyzed. A main interest of this experiment was to understand the chemical behavior of sorbing tracers: Cs⁺ (stable), ⁸⁵Sr²⁺, ⁶⁰Co²⁺ and Eu³⁺ (stable). The complete dataset (except for Eu³⁺ because of strong sorption to experimental equipment) was analyzed in a previous study with a 2D diffusion–reaction model and the derived diffusion and sorption parameters were compared with laboratory data. As in DI-A1, a difference by a factor of about 2 for sorption (magnitude of the Freundlich isotherm) was obtained between in situ and laboratory batch sorption experiments.Recent experimental and modeling studies have shown equivalent Cs⁺ sorption on intact and disaggregated Opalinus Clay samples. In view of these developments, new modeling of Cs⁺ diffusion and retention in the DI-A2 experiment has been performed using CrunchFlow. The calculations include transport by diffusion and a multisite cation exchange model to account for the retention of Cs⁺. The new results show that upscaling of Cs⁺ sorption from laboratory to field is no longer required. However, a difference in sorption by a factor of about 2 is still explained by the use of different versions of the same cation exchange model (a small difference in the selectivity coefficient for one type of site). This uncertainty in sorption leads to an uncertainty in the effective diffusion coefficient (D_e) for Cs⁺, also by a factor of 2 (2–4 × 10⁻¹⁰ m²/s). Clearly, the values of D_e obtained are correlated with the strength of sorption in the model, with stronger sorption leading to larger D_e values. Discrimination between the two versions of the exchange model is not possible when using only the results of the in situ test. Additionally, during early times (t < 10 days) the drop in Cs⁺ concentration in the circulation system is slower than expected. Due to the experimental setup, this slow decrease in concentration cannot be caused by the filter in the contact between borehole and rock. Poor mixing in the circulation system could explain this effect.     

Cobalt sorption–desorption behavior of calcareous soils from some Iranian soils

Little research has been done to study the role of soil parameters in cobalt (Co) retention, release and the processes involved in calcareous soils of arid and semi-arid regions. We studied the Co sorption and desorption capacity of various calcareous soils using batch technique. The sorption and desorption behavior of Co varied greatly among the studied soils. The sorbed fraction ranged from 92.3% to 97.2% and from 51.0% to 71.8%, when 5 and 200 mg Co l⁻¹, was added to the soil samples, respectively. Cobalt sorption curves were well fitted with Langmuir, Freundlich, and linear equations. The values of the distribution coefficients obtained from linear equation ranged from 9.5 l kg⁻¹ to 23.4 l kg⁻¹. Desorption experiments resulted in a Co recovery ranged from 3.6% to 11.4%, indicating a low desorption of Co from soils. The results of the geochemical modeling indicated that under low Co addition, the solutions were undersaturated with respect to Co(OH)_2(am), Co(OH)_2(c), Co₃(PO₄)_2(s), CoCl_2(s), CoHPO_4(s), CoCl₂·6H₂O_(s), and CoO_(s), whereas under higher Co addition, the solutions were undersaturated with respect to Co(OH)_2(am), CoCl_2(s), CoCl₂·6H₂O_(s), CoO_(s), CoHPO_4(s), and saturated with respect to Co₃(PO₄)_2(s), and CoCO_3(s). The hysteresis indices indicated that desorption of freshly sorbed Co with 0.01 M CaCl₂ was hysteretic in all soils and low mobility and leaching potential of freshly sorbed Co can be expected from these calcareous soils. Statistical correlations revealed that Co sorption and desorption onto the soils were influenced by the presence of CaCO₃ in soils. These findings suggested that calcareous soils are able to retain strongly Co in which the movement of Co in the soil profile would be negligible. Thus, little risk of groundwater contamination can be expected with Co in these calcareous soils.     

Sorption of Cs to micaceous subsurface sediments from the Hanford site, USA

The sorption of Cs⁺ was investigated over a large concentration range (10⁻⁹−10⁻² mol/L) on subsurface sediments from a United States nuclear materials site (Hanford) where high-level nuclear wastes (HLW) have been accidentally released to the vadose zone. The sediment sorbs large amounts of radiocesium, but expedited migration has been observed when HLW (a NaNO₃ brine) is the carrier. Cs⁺ sorption was measured on homoionic sediments (Na⁺, K⁺, Ca²⁺) with electrolyte concentrations ranging from 0.01 to 1.0 mol/L. In Na⁺ electrolyte, concentrations were extended to near saturation with NaNO_3(s) (7.0 mol/L). The sediment contained nonexpansible (biotite, muscovite) and expansible (vermiculite, smectite) phyllosilicates. The sorption data were interpreted according to the frayed edge-planar site conceptual model. A four-parameter, two-site (high- and low-affinity) numeric ion exchange model was effective in describing the sorption data. The high-affinity sites were ascribed to wedge zones on the micas where particle edges have partially expanded due to the removal of interlayer cations during weathering, and the low-affinity ones to planar sites on the expansible clays. The electrolyte cations competed with Cs⁺ for both high- and low-affinity sites according to the trend K⁺ >> Na⁺ ≥ Ca²⁺. At high salt concentration, Cs⁺ adsorption occurred only on high-affinity sites. Na⁺ was an effective competitor for the high-affinity sites at high salt concentrations. In select experiments, silver-thiourea (AgTU) was used as a blocking agent to further isolate and characterize the high-affinity sites, but the method was found to be problematic. Mica particles were handpicked from the sediment, contacted with Cs⁺_(aq), and analyzed by electron microprobe to identify phases and features important to Cs⁺ sorption. The microprobe study implied that biotite was the primary contributor of high-affinity sites because of its weathered periphery. The poly-phase sediment exhibited close similarity in ion selectivity to illite, which has been well studied, although its proportion of high-affinity sites relative to the cation exchange capacity (CEC) was lower than that of illite. Important insights are provided on how Na⁺ in HLW and indigenous K⁺ displaced from the sediments may act to expedite the migration of strongly sorbing Cs⁺ in subsurface environments.     

Removal of copper ions from aqueous solution using silica derived from rice straw: comparison with activated charcoal

The batch removal of copper(II) ions from aqueous solution under different experimental conditions using alkali-leached silica and activated charcoal was investigated in this study. The copper(II) uptake was dependent on varying time, pH, copper concentration and temperature. Copper sorption was found fast reaching equilibrium within 1 h with better performance for alkali-leached silica than charcoal. Copper sorption was low at low pH values and increased with rise in initial pH-value until 6.7. Sorption fits well the Langmuir and Freundlich equations with higher uptake by increasing temperature. According to Langmuir equation, the maximum uptake of Cu(II) ions by alkali-leached SiO₂ and charcoal was found to be 242.5 and 94.4 mmol/g at temperature 60 °C and pH 6. Thermodynamic studies confirm that the process was spontaneous and endothermic nature. Kinetic data for Cu(II) sorption was found to follow pseudo-second-order model.     

Removal of hazardous hexavalent chromium from aqueous solution using divinylbenzene copolymer resin

This paper presents the removal of hazardous hexavalent chromium from liquid waste streams using divinylbenzene copolymer resin Amberlite IRA 96. Important sorption parameters such as contact time, pH, resin dosage and initial metal concentration were studied at 30?°C. The kinetic study was conducted using pseudo-first and pseudo-second-order kinetics at 30?°C. The sorption process was found to be pH dependent. Maximum removal was obtained at pH 2 under optimized conditions. The sorption process was rapid and 99?% of the removal was achieved in first 30?min. The equilibrium data were fitted to both Langmuir and Freundlich models. The better regression coefficient (R ²) in Freundlich model suggests the multilayer sorption process. The value of Gibbs free energy for sorption process was found to be ?12.394?kJmol^?1. The negative value indicated the spontaneity of the sorption process. Scanning electron microscope and energy dispersive X-ray spectroscopy studies were conducted to find the role of surface morphology during sorption process. The Fourier transform infrared study was conducted to identify the functional groups responsible for interaction between the resin and chromium. Desorption and regeneration studies were also carried out.     

Effect of phosphorus on the attenuation of lead and chromium transport in soils

This study analyses the adsorption of Pb(II) and Cr(III) in soils. These metals are commonly found together in nature in urban wastes or industrial spillages, and the theoretical approach of the work was to evaluate the response of the soil to continuous Cr and Pb spillages to soil in terms of several physicochemical parameters. The influence of an anthropogenic input of phosphorus was evaluated. Continuous flow experiments were run in duplicates in acrylic columns (25 cm × 3.2 cm). The influent Cr(III) and Pb(II) solutions of 10 mg l^?1 and 25 mg l^?1 at pH 5 were pumped upward through the bottom of the columns to ensure saturation flow conditions. Also, successive experiments were run with the above concentrations of Cr(III) and Pb(II) and NaH₂PO₄, keeping metal to phosphorus ratio of 1:0, 1:0.1 and 1:1. Modelling parameters included Freundlich and Langmuir equations, together with the Two-site adsorption model using CXTFIT code. Results obtained allowed concluding that Pb(II) adsorption presents a certain degree of irreversibility and the continued spillages over soil increment the fraction which is not easily desorbed. Cr(III) desorption was almost complete, evidencing its high mobility in nature. The presence of an anthropogenic input of phosphorus leads to a marked increase of both Pb(II) and Cr(III) adsorption in soils. Z-potential measurements allow to discard the electrostatic attraction of Cr(III) and Pb(II) with the surface charged soil as the dominant process of metal sorption. Instead, CheaqsPro simulation allows to identify PbH₂PO₄ ⁺, PbHPO₄ (aq) and CrHPO₄ ⁺ as the dominant species which regulate Cr(III) and Pb(II) transport in soils.     

A laboratory batch study on arsenic sorption and desorption on guava orchard soils of Baruipur,West Bengal,India

Groundwater contaminated with arsenic (As), when extensively used for irrigation, causes potentially long term detrimental effects to surface soils. Such contamination can also directly affect human health when irrigated crops, such as rice, vegetable and fruits, are used for human consumption. Therefore, an understanding of the sorption and desorption behavior of As in surface soils is of high importance, because these processes regulate the bioavailability of As in the soil environment. In this study, we have collected soils from guava orchards of Baruipur, West Bengal, and characterized soil chemistry and batch sorption and desorption behavior in the laboratory. The sorption and desorption behavior of As in the soils were examined using the Langmuir and Freundlich sorption equation. Regression analysis of the soil chemical characteristics and sorption equation parameters were also performed. The results suggest that the sorption behavior of arsenate is highly dependent on soil characteristics, specifically organic carbon, clay and Al₂O₃ content of the soils. Whereas desorption behavior is critically influenced by the presence of high concentrations of amorphous and/or crystalline Fe₂O₃ in the soils. Retention of the significant portion of As in the soils (~ 84% of the total) suggests that As in the orchard soils may not be highly bioavailable to plants for uptake. However, more detailed studies will be required to ascertain the role of individual soil components on the As sorption and desorption processes.     

Diffusion and sorption of Cs, I and HTO in samples of the argillaceous Wakkanai Formation from the Horonobe URL, Japan: Clay-based modeling approach

Diffusion and sorption behaviors of cationic Cs⁺, anionic I⁻ and neutral HTO in samples of the Wakkanai Formation from the Horonobe underground research laboratory (URL), Japan, were investigated as a function of ionic strength (I) of synthetic groundwater by through-diffusion and batch sorption experiments and mechanistic modeling. The effective diffusivities (D_e) measured by through-diffusion experiments showed cation excess and anion exclusion effects, which were strongly dependent on I; D_e for Cs⁺ decreased as I increased, D_e for I⁻ showed the opposite dependency and D_e for HTO showed no dependence. The sorption of Cs⁺ measured by through-diffusion and batch sorption experiments were described by Freundlich isotherms with consistent parameters and decreased with I as a result of competitive ion exchange.Diffusion and sorption behaviors were interpreted by assuming the clay components of illite and smectite control diffusion and sorption mechanisms. The component additive (CA) sorption model, which includes illite and smectite contents and their ion exchange constants, provided a reasonable account of the Cs⁺ sorption trends measured as functions of I and Cs concentration. The diffusion model was developed by coupling the electrical double layer (EDL) model, describing the change of ionic concentrations (cation excess and anion deficit) and viscoelectric effects caused by electrostatic interaction at negatively charged clay surfaces, and a simplified pore model assuming one type of pore shape and includes their size distribution. When averaging the electrostatic effects by using the pore surface area distribution, the model could predict the cation excess and anion exclusion effects, and its dependence on I reasonably well. This result implies the nanoscale pores dominating the pore surface area can strongly impact on ionic diffusion in argillaceous rocks. The clay-based modeling approach described here provides a useful tool to predict ionic diffusion and sorption in argillaceous rocks.     

Efficient removal of hexavalent chromium from aqueous solutions using autohydrolyzed Scots Pine (Pinus Sylvestris) sawdust as adsorbent

In this work, a low-cost lignocellulosic adsorbent with high biosorption capacity is proposed, suitable for the efficient removal of hexavalent chromium from water and wastewater media. The adsorbent was produced by autohydrolyzing Scots Pine (Pinus Sylvestris) sawdust. The effect of the autohydrolysis conditions, i.e., pretreatment time and temperature, on hexavalent chromium biosorption was investigated using energy-dispersive X-ray spectroscopy (EDS) and UV–visible spectrophotometry. The Freundlich, Langmuir, Sips, Radke-Prausnitz, Modified Radke-Prausnitz, Tóth, UNILAN, Temkin and Dubinin-Radushkevich adsorption capacities and the rate constant values for pseudo-first- and pseudo-second-order kinetics indicated that the autohydrolyzed material exhibits significantly enhanced hexavalent chromium adsorption properties comparing with the untreated sawdust. The Freundlich’s adsorption capacity K _F increased from 2.276 to 8.928 (mg g^?1)(L mg^?1)^1/n , and the amount of hexavalent chromium adsorbed at saturation (Langmuir constant q _m) increased from 87.4 to 345.9 mg g^?1, indicating that autohydrolysis treatment at 240 °C for 50 min optimizes the adsorption behavior of the lignocellulosic material.     

Sorption of Ni on Na-rectorite studied by batch and spectroscopy methods

Sorption of Ni²⁺ on Na-rectorite as a function of contact time, temperature, pH and fulvic acid (FA)/humic acid (HA) was studied under ambient conditions. A pseudo-second-order rate equation was used to simulate the kinetic sorption. The removal of Ni²⁺ increased with increasing pH. The presence of FA/HA enhanced the sorption of Ni²⁺ at low pH values, whereas no drastic effect of FA/HA on Ni²⁺ uptake to rectorite was found at high pH values. The diffuse layer model (DLM) fitted the experimental data of Ni²⁺ sorption in the absence and presence of FA/HA very well with the aid of FITEQL 3.2. The Langmuir, Freundlich and Dubinin–Radushkevich (D–R) models were used to simulate the sorption isotherms of Ni²⁺ at different temperatures. The thermodynamic data (ΔH⁰, ΔS⁰, ΔG⁰) were calculated from the temperature dependent sorption isotherms and the results suggested that the sorption process of Ni²⁺ on rectorite was spontaneous and endothermic. The sorption and species of Ni²⁺ on rectorite in the presence and absence of FA/HA was also investigated and characterized by XPS. The spectroscopic analysis indicated no drastic structural changes of Na-rectorite and the sorption of Ni²⁺ mainly occurred on the surface and at the edge position of Na-rectorite.