Removal of heavy metals from paint industry’s wastewater using Leca as an available adsorbent

The ability of light expanded clay aggregate to remove lead and cadmium from paint industry’s effluents was studied at different levels of adsorbent, contact time and pH in April 2008. For this purpose, lead and cadmium removal from paint industry effluents were studied in batch reactors. lead and cadmium measurements have been taken with non-flame atomic absorption techniques and test methods were adapted from 19^th. Ed. of standard methods for the examination of water and wastewater. In this study, different amounts of Leca (1, 2, 3, 4, 5, 6, 7, 8, 9 and 10 g/L) were investigated. The amount of adsorbed lead and cadmium exposure to Leca increased from 1.41 to 3 mg/g and 0.22 to 0.75 mg/g, respectively. The maximum removal efficiency for Pb was 93.75 % at pH = 7 and exposure to 10 g/L of Leca, while for cadmium, it was nearly 89.7 % at the same condition. In this study, adsorption process of lead and cadmium was fitted with Freundlich adsorption isotherm (R² _Pb = 0.97 and R² _Cd = 0.98). The sufficient contact time was deemed 1–2 h for lead and cadmium. According to the results, Leca is recommended as a low cost and available adsorbent to remove lead and cadmium from industrial wastewater.     

Sorption behavior of the sandy residual unconsolidated materials from the sandstones of the Botucatu Formation,the main aquifer of Brazil

Pollutant transport through porous geological materials depends on the intrinsic characteristics of the materials that define the sorption behavior. This is the main environmental aspect that must be evaluated in terms of natural attenuation and retardation factor of the pollutants. Sorption is directly related to the electrostatic charge of the mineral, the organic matter, and the oxide and hydroxide contents. We assessed the sorption characteristics of the sandy residual unconsolidated material of the Botucatu Formation, which is part of the main aquifer of Brazil, using Batch Equilibrium Tests. The tests used multicomponent solutions of NaCl, KCl, ZnCl₂, and CuCl₂·H₂O with a total concentration that varied from 20 to 1,000 ppm. Different plotting systems were applied so that the isotherms better reflected the sorption behavior of the studied cations onto the unconsolidated materials. The cation Na⁺ was not sorbed. The Langmuir I and Freundlich equations adequately represent the behavior of Cu⁺⁺, the Langmuir II approximation better represented K⁺, and the Langmuir I and Freundlich equations were reasonably fitted Zn⁺⁺.     

The significance of Chara vegetation in the precipitation of lacustrine calcium carbonate

A significant portion of calcium carbonate is deposited in lake sediments as a result of biological processes related to the photosynthetic activity of phytoplankton in the pelagic realm and, in addition, macrophytes in the littoral zone. Lake Wigry, one of the largest lakes in Poland (north‐east Poland), is characterized by: (i) carbonate sediments with a CaCO₃ content exceeding 80% within the littoral zone; and (ii) large areas of submerged vegetation dominated by charophytes (macroscopic green algae, Characeae family). It is claimed that charophytes are highly effective in utilizing HCO₃^? and forming thick CaCO₃ encrustations. Thus, this study was aimed at evaluating the CaCO₃ production by dense Chara stands overgrowing the lake bottom reaching a depth of 4 m. In late July 2009, the fresh and dry mass of plants, the percentage contribution of calcium carbonate and the production of CaCO₃ per 1 m² were investigated along three transects at three depths (1 m, 2 m and 3 m, with each sample area equal to 0·0625 m²) per transect. The composition and structure of phytoplankton and the physico‐chemical properties of the water analysed in both the littoral and pelagic zones served as the environmental background and demonstrated moderately low fertility in the lake. The greatest dry plant mass exceeded 1000 g m^?2 and CaCO₃ encrustations constituted from 59% to over 76% of the charophyte dry weight. Thus, the maximum and average values of carbonates precipitated by charophytes were 685·5 and 438 g m^?2, respectively, which exceeded previously reported results. A correlation of carbonate production with the depth of Chara stands was detected, and intermediate depths offered the most favourable conditions for carbonate precipitation (589 g m^?2 on average). As precipitated carbonates are ultimately stored in bottom deposits, the results highlight the significance of charophytes in lacustrine CaCO₃ sedimentation.     

Adsorption and Desorption of Phosphate on Calcite and Aragonite in Seawater

The adsorption and desorption of phosphate on calcite and aragonite were investigated as a function of temperature (5–45 °C)and salinity (0–40) in seawater pre-equilibrated with CaCO₃. An increase in temperature increased the equilibrium adsorption; whereas an increase in salinity decreased the adsorption. Adsorption measurements made in NaCl were lower than the results in seawater. The higher values in seawater were due to the presence of Mg²⁺ and Ca²⁺ ions. The increase was 5 times greater for Ca²⁺ than Mg²⁺. The effects ofCa²⁺ and Mg²⁺ are diminished with the addition of SO₄ ^2- apparently due to the formation of MgSO₄ and CaSO₄ complexes in solution and/or SO₄ ^2- adsorption on the surface of CaCO₃. The adsorbed Ca²⁺ and Mg²⁺ on CaCO₃ (at carbonate sites) may act as bridges to PO₄ ^3- ions. The bridging effect of Ca²⁺is greater than Mg²⁺ apparently due to the stronger interactions of Ca²⁺ with PO₄ ^3-.The apparent effect of salinity on the adsorption of PO₄ was largely due to changes in the concentration of HCO₃ ^- in the solutions. An increase in the concentration of HCO₃ ^- caused the adsorption of phosphate to decrease, especially at low salinities. The adsorption at the same level of HCO₃ ^- (2 mM) was nearly independent of salinity. All of the adsorption measurements were modeled empirically using a Langmuir-type adsorption isotherm[ [PO₄]_ad = K_mC_m[PO₄]_T/(1 +K_m [PO₄]_T) , ]where [PO₄]_ad and [PO₄]_T are the adsorbed and total dissolved phosphate concentrations, respectively. The values of C_m (the maximum monolayer adsorption capacity, (mol/g) and K_m (the adsorption equilibrium constant, g/(mol) over the entire temperature (t, °C) and salinity (S) range were fitted to[ C_m = 17.067 + 0.1707t - 0.4693S + 0.0082S² ( = 0.7) ][ ln K_m = - 2.412 + 0.0165t - 0.0004St - 0.0008S² ( = 0.1) ]These empirical equations reproduce all of our measurements of[PO₄]_ad up to 14 mol/g and within ±0.7 mol/g.The kinetic data showed that the phosphate uptake on carbonate minerals appears to be a multi-step process. Both the adsorption and desorption were quite fast in the first stage (less than 30 min) followed by a much slower process (lasting more than 1 week). Our results indicate that within 24 hours aragonite has a higher sorption capacity than calcite. The differences between calcite and aragonite become smaller with time. Consequently, the mineral composition of the sediments may affect the short-term phosphate adsorption and desorption on calcium carbonate. Up to 80 % of the adsorbed phosphate is released from calcium carbonate over one day. The amount of PO₄ left on the CaCO₃ is close to the equilibrium adsorption. The release of PO₄ from calcite is faster than from aragonite. Measurements with Florida Bay sediments produced results between those for calcite and aragonite. Our results indicate that the calcium carbonate can be both a sink and source of phosphate in natural waters.     

Active ankerite cementation in the subsurface Eocene of southwest Texas

In subsurface samples of Wilcox (Eocene) sandstones, calcite cements occur above 2315 m depths, whereas ankerites occur at depths from 2560 m (temperatures 125 ° C) to at least 4650 m (temperatures 210 ° C). Microprobe analyses indicate that some shallow ankerites have appreciable excess calcium, analogous to protodomites. Ankerites at depths greater than 3200 m have compositions of about CaMg_0.5Fe_0.5(CO₃)₂.Oxygen isotope data suggests that the ankerites are similar to low temperature hydrothermal dolomites and that they have probably formed in pore fluids with higher O₁₈/O₁₆ ratios than sea water. The isotopic data also suggest that the ankerites have formed over a more limited temperature interval than they occur today.The ankerite is believed to have formed from calcite by the reaction 4CaCO₃+Fe²⁺+Mg²⁺=2CaMg_0.5Fe_0.5(CO₃)₂ +2Ca²⁺. Iron and magnesium for this reaction was apparently released by the breakdown of smectite to illite in mixed-layer clays. Bulk chemical analyses suggest that some iron was transferred from shales into sandstones. Mass balance and chemical considerations are compatible with this model.     

Adsorption of lead, zinc and cadmium ions from contaminated water onto Peganum harmala seeds as biosorbent

Peganum harmala seeds were assessed as biosorbent for removing Pb²⁺, Zn²⁺and Cd²⁺ ions from aqueous solutions. The effects of various parameters such as the aqueous solution pH, the contact time, the initial metal concentration and the amount of adsorbent in the process were investigated. The adsorption efficiencies increased with pH. It was found that about 95 % of lead, 75 % of zinc and 90 % of cadmium ions could be removed from 45 ml of aqueous solution containing 20 mg l^?1 of each cation with 2 g of adsorbent at pH 4.5 after 15 min. The quantitative desorption of cadmium from adsorbent surface was achieved using 10 ml of a 0.5 M nitric acid solution. This condition was attained for lead and zinc ions with 10 ml of 1 M hydrochloric acid solution. Kinetic investigation of the process was performed by considering a pseudo-second-order model. This model predicts the chemisorption mechanism of the process. Langmuir, Freundlich, Temkin and Dubinin–Radushkevich models were tested for describing the equilibrium data. It was found that the Freundlich model describes the experimental data resulting from the adsorption of lead ions. However for cadmium and zinc ions, the adsorption equilibria were interpreted with the Langmuir model.     

Calcium carbonate dissolution in deep sea sediments: reconciling microelectrode, pore water and benthic flux chamber results

We report the benthic fluxes of O₂, titration alkalinity (TA), Ca²⁺, NO₃⁻, PO₄³⁻, and Si(OH)₄ from in situ benthic flux chamber incubations on the Ceara Rise and Cape Verde Plateau and compare them to previously published results. We find within analytical uncertainty that the TA flux is twice the calcium flux, suggesting that dissolution/precipitation of CaCO₃ is the principal mechanism controlling benthic TA and Ca²⁺ fluxes. At sites where the sediments contain significant (>35%) CaCO₃ and the overlying waters are supersaturated with respect to CaCO₃, the ratios of the total dissolution rate to the remineralization rate are significantly less than at all other study sites. We propose that these observations can be explained by precipitation of fresh CaCO₃ at the supersaturated sediment surface followed by redissolution deeper in the sediments because of metabolically-produced CO₂. A numerical simulation is presented to demonstrate the feasibility of this explanation. In addition, surface exchange reactions in high-CaCO₃ sediments coupled with high rates of particle mixing may also impact rates of metabolic dissolution and depress chamber-derived estimates of carbonate alkalinity and calcium benthic fluxes. These results suggest that at supersaturated, high CaCO₃ locations, previous models of sediment diagenesis may have overestimated the impact of metabolic dissolution on the preservation of CaCO₃ deposited on the sea floor.     

Adsorption of copper, nickel and lead ions from synthetic semiconductor industrial wastewater by palm shell activated carbon

Granular activated carbon produced from palm kernel shell was used as adsorbent to remove copper, nickel and lead ions from a synthesized industrial wastewater.Laboratory experimental investigation was carried out to identify the effect of pH and contact time on adsorption of lead, copper and nickel from the mixed metals solution. Equilibrium adsorption experiments at ambient room temperature were carried out and fitted to Langmuir and Freundlich models. Results showed that pH 5 was the most suitable, while the maximum adsorbent capacity was at a dosage of 1 g/L, recording a sorption capacity of 1.337 mg/g for lead, 1.581 mg/g for copper and 0.130 mg/g for nickel. The percentage metal removal approached equilibrium within 30 min for lead, 75 min for copper and nickel, with lead recording 100 %, copper 97 % and nickel 55 % removal, having a trend of Pb²⁺ > Cu²⁺ > Ni²⁺. Langmuir model had higher R² values of 0.977, 0.817 and 0.978 for copper, nickel and lead respectively, which fitted the equilibrium adsorption process more than Freundlich model for the three metals.     

室温条件下青海湖水中镁离子浓度对沉淀碳酸钙同质多像类型的调控

青海湖是我国唯一报道过的现代湖底沉积物中白云石、方解石和文石等多种碳酸盐矿物共存的高原内陆咸水湖泊。以青海湖水和除菌青海湖水作为载体,以CaCl_2和MgCl_2·6 H_2O作为反应原料,在实验室常温条件下采取控制变量法制备出不同浓度Mg~(2+)参与下的钙质沉淀物,探讨Mg~(2+)浓度对沉淀物类型的影响。仅添加CaCl_2时,青海湖水中的沉淀物主要是石膏(Ca SO_4·2 H_2O)和球霰石(CaCO_3);在添加CaCl_2的同时添加MgCl_2·6 H_2O,沉淀物的石膏消失,完全转变成碳酸盐矿物,包括方解石和球霰石;当湖水中Mg~(2+)浓度为0.62 mol/L时,球霰石消失,沉淀物变为方解石和文石;随着Mg~(2+)浓度继续升高,文石含量稳步增加,方解石含量则逐渐减少,当Mg~(2+)浓度达到1.22 mol/L或更高时,方解石全部消失,沉淀物仅剩文石。实验结果表明,青海湖水中较高浓度的SO_4~(2-)对碳酸钙晶体生长有抑制作用,而额外加入的Mg~(2+)可以解除SO_4~(2-)的抑制作用,使得Ca~(2+)与HCO_3~-和CO_3~(2-)结合形成碳酸钙。此外,碳酸钙的同质多像类型也明显受到Mg~(2+)浓度的控制,随着湖水中Mg~(2+)浓度增加,方解石、球霰石不再稳定,而文石逐渐占主导地位,当Mg/Ca值达到6.1时,反应产物中仅有文石稳定存在。     

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.     

Sorption of inorganic mercury and monomethyl mercury in an iron–humus podzol soil of southern Norway studied by batch experiments

Considerable fractions of the Hg content of lake and river systems in Scandinavia are discharged from the soil of the catchments. An important soil type in Scandinavia is the iron–humus podzol. The sorption characteristics of this soil type for inorganic Hg(II) and monomethyl mercury were investigated by batch experiments. The solubility of Hg²⁺ and CH₃Hg⁺ in the soil horizons containing organic matter increases with increasing pH of the soil solution by favoring the formation of solute organic matter–mercury complexes. While the solubility of Hg²⁺ is strongly dependent on complexation to dissolved organic matter, the solubility of CH₃Hg⁺ is more dependent on ion exchange. The concentration of solute inorganic Hg(II) increased with increasing temperature probably because of an increase in the concentration of dissolved organic carbon. There was no effect of temperature on the concentration of solute CH₃Hg⁺. At pH values where inorganic mercury–hydroxo complexes are formed, inorganic Hg(II) is efficiently sorbed to the metal oxides of the mineral soil. The soil–water distributions of inorganic Hg(II) in the different soil horizons were described by Freundlich isotherms or linear isotherms for common and contaminated mercury contents in the soils.     

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.     

Limestone drains to increase pH and remove dissolved metals from acidic mine drainage

Despite encrustation by Fe and Al hydroxides, limestone can be effective for remediation of acidic mine drainage (AMD). Samples of water and limestone (CaCO₃) were collected periodically for 1 a at 3 identical limestone-filled drains in Pennsylvania to evaluate the attenuation of dissolved metals and the effects of pH and Fe- and Al-hydrolysis products on the rate of CaCO₃ dissolution. The influent was acidic and relatively dilute (pH<4; acidity <90 mg) but contained 1–4 mg·L⁻¹ of O₂, Fe³⁺, Al³⁺ and Mn²⁺. The total retention time in the oxic limestone drains (OLDs) ranged from 1.0 to 3.1 hr. Effluent remained oxic (O₂>1 mg·L⁻¹) but was near neutral (pH=6.2–7.0); Fe and Al decreased to less than 5% of influent concentrations. As pH increased near the inflow, hydrous Fe and Al oxides precipitated in the OLDs. The hydrous oxides, nominally Fe(OH)₃ and Al(OH)₃, were visible as loosely bound, orange-yellow coatings on limestone near the inflow. As time elapsed, Fe(OH)₃ and Al(OH)₃ particles were transported downflow. The accumulation of hydrous oxides and elevated pH (>5) in the downflow part of the OLDs promoted sorption and coprecipitation of dissolved Mn, Cu, Co, Ni and Zn as indicated by decreased UK concentrations of the metals in effluent and their enrichment relative to Fe in hydrous-oxide particles and coatings on limestone. Despite thick (∼1 mm) hydrous-oxide coatings on limestone near the inflow, CaCO₃ dissolution was more rapid near the inflow than at downflow points within and the OLD where the limestone was not coated. The high rates of CaCO₃ dissolution and Fe(OH₃) precipitation were associated with the relatively low pH and high Fe³⁺ concentration near the inflow. The rate of CaCO₃ dissolution decreased with increased pH and concentrations of Ca²⁺ and HCO₃⁻ and decreased Pco₂. Because overall efficiency is increased by combining neutralization and hydrolysis reactions, an OLD followed by a settling pond requires less land area than needed for a two-stage treatment system consisting of an anoxic limestone drain an oxidation-settling pond or wetland. To facilitate removal of hydrous-oxide sludge, a perforated-pipe subdrain can be installed within an OLD.     

Precipitation of amorphous CaCO3 (aragonite-like) by cyanobacteria: A STXM study of the influence of EPS on the nucleation process

An amorphous or nanocrystalline calcium carbonate (ACC) phase with aragonite-like short-range order was found to be a transient precursor phase of calcite precipitation mediated by cyanobacteria of the strain Synechococcus leopoliensis PCC 7942. Using scanning transmission X-ray microscopy (STXM), different Ca-species such as calcite, aragonite-like CaCO₃, and Ca adsorbed on extracellular polymers were discriminated and mapped, together with various organic compounds, at the 30 nm-scale. The nucleation of the amorphous aragonite-like CaCO₃ was found to take place within the tightly bound extracellular polymeric substances (EPS) produced by the cyanobacteria very close to the cell wall. The aragonite-like CaCO₃ is a type of ACC since it did not show either X-ray or electron diffraction peaks. The amount of aragonite-like CaCO₃ precipitated in the EPS was dependent on the nutrient supply during bacterial growth. Higher nutrient concentrations (both N and P) during the cultivation of the cyanobacteria resulted in higher amounts of precipitation of the aragonite-like CaCO₃, whereas the amount of Ca²⁺ adsorbed per volume of EPS was almost independent of the nutrient level. After the onset of the precipitation of the thermodynamically stable calcite and loss of supersaturation the aragonite-like CaCO₃ dissolved whereas Ca²⁺ remained sorbed to the EPS albeit at lower concentrations. Based on these observations a model describing the temporal and spatial evolution of calcite nucleation on the surface of S. leopoliensis was developed. In another set of STXM experiments the amount of aragonite-like CaCO₃ precipitated on the cell surface was found to depend on the culture growth phase: cells in the exponential growth phase adsorbed large amounts of Ca within the EPS and mediated nucleation of ACC, while cells at the stationary/death phase neither adsorbed large amounts of Ca²⁺ nor mediated the formation of aragonite-like CaCO₃. It is suggested that precipitation of an X-ray amorphous CaCO₃ layer by cyanobacteria could serve as a protection mechanism against uncontrolled precipitation of a thermodynamically stable phase calcite on their surface.     

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     

Adsorption characteristics of heavy metals in soil zones developed on spilite

Various soil zones such as Bw, C1, and C3 are developed on spilite. Montmorillonite, vermiculite and chlorite is moderately occurred in the C1 and C3 soil zones, in contrast montmorillonite and vermiculite are absent in Bw soils whereas illite and sesquioxide are relatively increased. The high cation exchange capacity (CEC) of montmorillonite and vermiculte and moderate CEC of chlorite and illite resulted in the high adsorption of heavy metals. The adsorption of the heavy metals on spilite soil zones was studied at different concentrations and pH levels. Heavy metals like lead, cadmium, and copper were selected for adsorption studies considering their contribution as toxic metals in the environment. The initial solute concentrations ranged from 7.0 × 10⁻³ to 1.0 × 10² mg/L. The sorption behavior of Cd²⁺, Pb²⁺, and Cu²⁺ on soil zones of spilite was investigated using the batch equilibrium technique at 25°C. The characteristics of the adsorption process were investigated using Scatchard plot analysis (q/C vs. q) by the batch equilibrium technique at 25°C. In the adsorption of heavy metals, deviation from linearity in the plot of q/C versus q was observed, indicating the presence of multi-model interaction and non-Langmuirean behavior. When the Scatchard plot showed a deviation from linearity, greater emphasis was placed on the analysis of the adsorption data in terms of the Freundlich model, in order to construct the adsorption isotherms of the metal(s) at particular concentration(s) in solutions. The adsorption behavior of these metal ions on spilite soil zones is expressed by the Freundlich isotherms. Adsorption constants and correlation coefficients for the Cd, Pb, and Cu on spilite soil zones were calculated from Freundlich plots.     

Sorption on Humic Acids as a Basis for the Mechanism of Primary Accumulation of Gold and Platinum Group Elements in Black Shales

In order to asses the contribution of sorption by complexation to the concentration of noble metals at early stages of the formation of their deposits in black shales, the sorption of Au(III), Pt(IV), Rd(II), Rh(III), Ru(IV), and Os(IV) ions was studied on ash-free preparations of humic acids (HA) separated from peat of the Tver region and marine sediment samples taken on the Peruvian shelf. Data on the nature and protolytic characteristics of oxygen-containing HA functional groups were obtained. It has been shown that carboxyl groups and phenol oxygroups, which ensure the HA complexation with ions of noble metals, are present in the HA structure. The dissociation constant values for HA carboxyl groups (pK_a) and the distribution function of these groups in their pK_a values have been established. It has been revealed that the pK_a value for both of the HA groups varies within two orders of magnitude: the average value is equal to 6.1 for HA from peat and 7.0 for HA from marine sediments. A fairly high and similar for both of the HA groups sorption capacity with respect to Au(III), Rd(II), Rh(III), Ru(IV), and Os(IV) ions was established in model experiments. It is equal to 320–350 mg g^–1 for Au, 100–110 mg g^–1 for Pd, 11–12 mg g^–1 for Rh, 16–19 mg g^–1 for Ru, and 23 mg g^–1 for Os. The study of platinum(IV) sorption revealed that humic acids from peat and marine sediments do not virtually sorb Pt(IV), and this observation is important for understanding genetic features of the formation of noble metal deposits in black shales. Based on sorption isotherms for Au(III), Pd(II), Rh(III), and Ru(IV), the conditional affinity constant values for HA sorption centers with respect to ions of these metals were calculated by the method of quantitative physicochemical analysis. These values prove that complex compounds forming at the HA surface possess a high strength: the log values for the Au(III)–HA, Pd(II)–HA, Rh(III)–HA, and Ru(IV)–HA compounds are equal to 6.0, 5.0, 3.2, and 3.5, respectively.     

Ni(II) sorption on natural chlorite

Sorption of Ni(II) onto chlorite surfaces was studied as a function of pH (5–10), ionic strength (0.01–0.5 M) and Ni concentration (10⁻⁸–10⁻⁶ M) in an Ar atmosphere using batch sorption with radioactive ⁶³Ni as tracer. Such studies are important since Ni(II) is one of the major activation products in spent nuclear fuel and sorption data on minerals such as chlorite are lacking. The sorption of Ni(II) onto chlorite was dependent on pH but not ionic strength, which indicates that the process primarily comprises sorption by surface complexation. The maximum sorption was at pH ∼ 8 (K_d = ∼10⁻³ cm³/g). Desorption studies over a period of 1–2 weeks involving replacement of the aqueous solution indicated a low degree of desorption. The acid–base properties of the chlorite mineral were determined by titration and described using a non-electrostatic surface complexation model in FITEQL. A 2-pK NEM model and three surface complexes, Chl_OHNi²⁺, Chl_OHNi(OH)⁺ and Chl_OHNi(OH)₂, gave the best fit to the sorption results using FITEQL. The high K_d values and low degree of desorption observed indicate that under expected groundwater conditions, a large fraction of Ni(II) that is potentially leachable from spent nuclear fuel may be prevented from migrating by sorption onto chlorite surfaces.     

Inhibiting effects of lanthanum ion on calcite formation from CaCL2-NaHCO3 solutions at 25°C

The influence of La³⁺ on calcite formation was studied using CaCl₂-NaHCO₃ solutions. We adopted a closed system, where the pH change of the solutions was monitored in a closed vessel. The closed system reduces a number of thermodynamic variables of the solution, thus enabling us to calculate the amount of CaCO₃ precipitate only from pH with the assumption of equilibria among dissolved components in solution. After the analytical inspection of the calculation and assumption on which the calculation is based on, it was applied to experiments of the calcite formation in a Teflon vessel. The mole concentration of lanthanum added in the experiments was smaller than 1/3000 of that of calcium ion in the solutions. The addition of lanthanum oxide, chloride, and nitrate caused the difference in the pH change of the solution. The decrease of pH was smaller when lanthanum reagents were added, indicating that the amount of CaCO₃ precipitate decreased. The smallest decrease was observed when lanthanum chloride or nitrate salt was added. The X-ray diffraction study showed that the CaCO₃ precipitated in any solutions were calcite. If an equilibrium is assumed, which is considered to be likely from the pH change, the ion activity product (IAP) calculated in this study increased about 6 times when lanthanum ion, whose concentration is only 1/14 000 mole of calcium ion, was present.