The mechanisms of forming iron-base metal gossan minerals

Laboratory studies of the weathering of sulphide ores have centred around using samples of ore as electrodes and accelerating the weathering processes by passing an electric current. The results of reacting 19 different ore types under varying conditions are compared with data from co-precipitating, Fe and Cu, Fe and Ni, Fe and Zn, Fe and Co, and Fe and Pb, over a pH range from 2 to 11. An electrochemical cell specially designed to fit onto an optical microscope has allowed direct observation of the changes in sulphide mineral grains as they are anodically weathered.These experiments are used to demonstrate that the pH of the environment during the weathering of sulphides to sulphates is the most important parameter in determining the initial gossan minerals that form. Factors that will cause the pH to be high are buffering from gangue and wallrock minerals, low iron content in the sulphide and a high metal to sulphur ratio in the sulphide. A low pH is favoured by the converse, namely a sulphide sufficiently massive to override the buffering effects of the wallrocks and any gangue minerals present, a high iron content in the sulphide and a low metal to sulphur ratio in the sulphide.Two mechanisms of iron hydrolysis dominate the weathering processes where iron is a major metal being released from a sulphide.

1. (1) The high pH process. Where there is sufficient buffering for the pH to remain at or above 7, most of the base metals including ferrous iron will be hydrolysed and pyroaurite type of minerals form for Ni, Zn and Co, while mixed Fe-Cu hydroxycarbonates and hydroxysulphates form for Cu, and mixed iron lead hydrocarbonates form for Pb. The iron is located in these initial compounds as a green rust where it is effectively bound as ferrous hydroxide. Subsequent oxidation of this hydroxide produces no further acid. 4Fe(OH)₂ + O₂ + 2H₂0 → 4Fe(OH)₃

2. (2) The low pH process. Where the buffering is insufficient and the pH is below 7, even though some of the ferrous iron will have precipitated as an equivalent to Fe(OH)₂, the solubility is such that sufficient Fe²⁺ will remain in solution so that further oxidation will produce acid. 4Fe²⁺ + O₂ + 1OH₂O → Fe(OH)₃ + 8H⁺ This acid will bring more of the Fe²⁺ into solution to create more acid and the pH will gradually fall even further, so that the gossan forming environment will be at a pH less than 5 and may be as low as 3. At these low pH values, the base metals are soluble and not prone to co-precipitation or adsorption with the gossan minerals. Only elements present in solution as anions, such as Se, As, Mo and Sb, are likely to be bound into gossans forming at low pH.

The results from weathering tests carried out on gossan minerals formed at higher pH show that these minerals are reasonably stable if treated with solutions that have a pH above 7, but they can break down if treated with a solution of pH 5. Thus they could be expected to be leached by rain water saturated with CO₂.When investigating a likely gossan, all aspects — the iron oxides, the silicates, the carbonates and penetrations into the footwall and hanging wall — should be examined carefully, being ever mindful of the effect that pH would have had during the formation and reworking of the minerals. The composition of gossan minerals, their adsorption properties, the solubilities of metal ions, the mechanisms of Fe precipitation, the co-precipitation of other metals with Fe, the stability of carbonates and the binding of humic materials are all pH dependent in the same way. At high pH, metals are immobilized; at low pH, they tend to be in solution.     

The adsorption of gold(I) hydrosulphide complexes by iron sulphide surfaces

The adsorption of gold by pyrite, pyrrhotite, and mackinawite from solutions containing up to 40 mg/kg (8 μm) gold as hydrosulphidogold(I) complexes has been measured over the pH range from 2 to 10 at 25°C and at 0.10 m ionic strength (NaCl, NaClO₄). The pH of point of zero charge, pH_pzc, has been determined potentiometrically for all three iron sulphides and shown to be 2.4, 2.7, and 2.9 for pyrite, pyrrhotite, and mackinawite, respectively. In solutions containing hydrogen sulphide, the pH_pzc is reduced to values below 2. The surface charge for each sulphide is therefore negative over the pH range studied in the adsorption experiments. Adsorption was from 100% in acid solutions having pH < 5.5 (pyrite) and pH < 4 (mackinawite and pyrrhotite). At alkaline pH’s (e.g., pH = 9), the pyrite surface adsorbed 30% of the gold from solution, whereas the pyrrhotite and mackinawite surfaces did not adsorb.The main gold complex adsorbed is AuHS°, as may be deduced from the gold speciation in solution in combination with the surface charge. The adsorption of the negatively charged Au(HS)₂⁻ onto the negatively charged sulphide surfaces is not favoured. The X-ray photoelectron spectroscopic data revealed different surface reactions for pyrite and mackinawite surfaces. While no change in redox state of adsorbent and adsorbate was observed on pyrite, a chemisorption reaction has been determined on mackinawite leading to the reduction of the gold(I) solution complex to gold(0) and to the formation of surface polysulphides. The data indicate that the adsorption of gold complexes onto iron sulphide surfaces such as that of pyrite is an important process in the “deposition” of gold from aqueous solutions over a wide range of temperatures and pressures.     

The mechanism of surface chemical kinetics of dissolution of minerals

This paper deals with the mechanism of dissolution reaction kinetics of minerals in aqueous solution based on the theory of surface chemistry.Surface chemical catalysis would lead to an obvous decrease in active energy of dissolution reaction of minerals.The dissolution rate of minerals is controlled by suface adsorption,surface exchange reaction and desorption,depending on pH of the solution and is directly proportional to δH^n0 ,When controlled by surface adsorption,i.e.,nθ=1,the dissolution rate will decrease with increasing pH;when controlled by surface exchane reaction,i.e.,nθ=0,the dissolution rate is independent of pH;when controlled by desorption,nθis a positive decimal between 0 and 1 in acidic solution and a negative decimal between-1 and 0 in alkaline solution.Dissolution of many minerals is controlled by surface adsorption and/or surface exchange reactions under acid conditions and by desorption under alkaline conditions.     

Cadmium and lead interaction with diatom surfaces: A combined thermodynamic and kinetic approach

This work is devoted to the physico-chemical study of cadmium and lead interaction with diatom-water interfaces for two marine planktonic (Thalassiosira weissflogii, TW; Skeletonema costatum, SC) and two freshwater periphytic species (Achnanthidium minutissimum, AMIN; Navicula minima, NMIN) by combining adsorption measurements with surface complexation modeling. Adsorption kinetics was studied as a function of pH and initial metal concentration in sodium nitrate solution and in culture media. Kinetic data were consistent with a two-step mechanism in which the loss of a water molecule from the inner coordination sphere of the metal is rate limiting. Reversible adsorption experiments, with 3 h of exposure to metal, were performed as a function of pH (2-9), metal concentration in solution (10⁻⁹-10⁻³ M), and ionic strength (10⁻³-1.0 M). While the shape of pH-dependent adsorption edge is similar among all four diatom species, the constant-pH adsorption isotherm and maximal binding capacities differ. Measurements of electrophoretic mobilities (μ) revealed negative surface potential for AMIN diatom, however, the absolute value of μ decreases with increase of [Pb²⁺]_aq suggesting the metal adsorption on negative surface sites. These observations allowed us to construct a surface complexation model (SCM) for cadmium and lead binding by diatom surfaces that postulates the Constant Capacitance of the electric double layer and considers Cd and Pb complexation with mainly carboxylic and, partially, silanol groups. In the full range of investigated Cd concentration, the SCM is able to describe the concentration of adsorbed metal as a function of [Cd²⁺]_aq without implying the presence of high affinity, low abundance sites, that are typically used to model the metal interactions with natural multi-component organic substances. At the same time, Cd fast initial reaction requires the presence of “highly reactive sites” those concentration represents only 2.5-3% of the total amount of carboxylic sites. For reversible adsorption experiments, the dominating carboxylic groups, whose concentration is allowed to vary within the uncertainty of experimental acid-base titrations, are sufficient to reproduce the metal adsorption isotherms. Results of this study strongly suggest that laboratory experiments performed in a wide range of metal to biomass ratios, represent robust and relatively simple method for assessing the distribution of metals between aqueous solution and planktonic and periphytic biomass in natural settings.     

The adsorption of aquatic humic substances by iron oxides

The interactions of humic substances from Esthwaite Water with hydrous iron oxides (α-FeOOH, α-Fe₂O₃, amorphous Fe-gel) have been examined by measuring adsorption isotherms and by microelectrophoresis. In Na⁺-Cl^?-HCO₃^?at I = 0.002 M (medium I) the extent of adsorption decreases with increasing pH. The results are consistent with a mechanism involving ligand exchange of humic anionic groups with H₂O and OH^?of surface Fe-OH₂⁺and Fe-OH groups respectively, with an increasing degree of protonation of the adsorbed humics as the adsorption density increases at constant pH.At pH 7 in a medium containing Mg²⁺, Ca²⁺ and SO₄^2?, at their Esthwaite Water concentrations and at I= 0.002 M (medium II) the adsorption capacity of goethite (α-FeOOH) is approximately twice that in medium I. Electrophoresis experiments show that the extra capacity is associated with coadsorption of Mg²⁺ and/or Ca²⁺ ions.When the iron oxides are added to samples of Esthwaite Water itself they become negatively charged and plots of electrophoretic mobility against pH for the natural water are identical to those in medium II plus humics.     

Adsorption of copper and cobalt from fresh and marine systems

The adsorption of copper and cobalt from aqueous solution on to illite and other substrates has been studied as a function of pH, solution composition and solid phase concentration. The results are interpreted in terms of a model whereby the trace metals are adsorbed in exchange for surface bound H⁺ ions. Adsorption varies with solution ionic strength and the concentrations of complex forming ligands; both of these parameters tend to reduce the trace metal adsorption. The Cu²⁺ is two orders of magnitude more reactive toward solid surfaces than Co²⁺ , which is consistent with the general reactivities of these two metal ions. It is also found that Mg₂₊ interferes with adsorption, presumably by competing with the trace metals for the surface sites. A quantitative model was developed which describes adsorption of these metals from natural waters ranging from river water to sea water as a function of pH, complexing ligands and magnesium activity.     

Experimental study of the selective adsorption of heavy metals onto clay minerals

The interaction between minerals and heavy metals has been a hot object of study in environmental science,mineralogy and soil science,Through the selective adsorption experiment of Ca-montomorillonite,illite and kaolinite to Cu2 ,Pb^2 ,Zn^2 ,Cd^2 ,and Cr^3 ions at certain conditions,it could be concluded that Cr^3 is most effectively sorbed by all the three minerals.Also,it can be found that Pb^2 shows a strong affinity for illite and kaolinite while cu^2 for montmorillonite .Based on the adsorption experiment at varying pH of solution,it can be found that the amount of heavy etals sorbed by minerals increases with increasing pH of the solution.     

Parameters controlling the partitioning of tributyltin (TBT) in aquatic systems

In the present study the distribution of TBT between solid and water phase as a function of several parameters was determined. Two types of clay minerals (Na-montmorillonite SWy and kaolinite KGa) and quartz sand were used as sorbents in conventional batch experiments. Sorption coefficients (K_d) followed the order montmorillonite (89 l/kg) > kaolinite (51 l/kg) > quartz (25 l/kg), while for sorption coefficients normalized to the surface area (Kd′) an opposite trend was observed, with the lowest value determined for montmorillonite (2.79 × 10⁻³ l/m²) and the highest for quartz sand (8.04 × 10⁻² l/m²). The results demonstrate that numerous environmental parameters influence the adsorption process of TBT, such as solid/solution ratio, clay content and salinity. Another important factor governing TBT adsorption is pH, because it affects both the TBT species in the water phase as well as the surface properties of the mineral phase. The maximum of TBT adsorption onto clays was always around pH 6–7. According to the data, it is evident that the content of organic matter in the solid phase plays an important role on TBT adsorption, either as particulate organic matter (POM) or organic matter adsorbed to mineral particles (AOM). Experiments were carried out with well characterized organic matter and the results showed a linear increase of K_d from 51 up to 2700 l/kg upon the addition of 5% of particulate organic matter to pure phased kaolinite. TBT adsorption onto mineral surfaces, which were previously enriched with adsorbed organic matter, was investigated at different pH. The present study points to the importance of identifying and characterizing sorbents and envrionmental conditions, in order to predict and model TBT distribution in natural systems.     

Experimental study on the competitive adsorption of metal ions onto minerals

The study on the competitive adsorption shows that the magnitude order of metal ions adsorbed onto oxide and silicate minerals in near-neutral solution with low ionic strength is in mole/nm² as follows: CaCO₃ > quarte > hydromuscovite > kaolinite > Ca-montmorillonite > goethite > gibbsite. These minerals can be divided into three groups according to their surface equilibrium constantsK _M of the adsorption reactions, which are the function of the dielectric constants ε of the absorbent minerals. The relationships between constantsK _M and mineral dielectric constants ε are described as follows: lgK _M ¹ = 7.813-26.15/ε lgK _M ² = 9.030-26.15/ε lgK _M ³ =11.63-26.15/ε for the adsorption reaction: >SO^- + Mⁿ⁺≥SOM^n-1)+ (n = 1, 2, 3) The first group of minerals include quartz, goethite, 1:1 phyllosilicates and other oxide minerals; the second: gibbsite, brucite and 2:1 phyllosilicates; the third: carbonate, sulphate and phosphorate minerals. The appearance reaction constants have a variation of magnitude ±0.5 for different metal ions with the same mineral. This project was financially supported by the National Natural Science Foundation of China (No. 49572091).     

Predicting the activity of Cd and Zn in soil pore water from the radio-labile metal fraction

Cadmium and zinc were added at 3 and 300 mg kg⁻¹, respectively, to 23 soils and incubated at 16°C and 80% field capacity for 818 d. Following addition of metal, changes in the radio-labile concentrations of both elements were examined on seven separate sampling occasions over 818 d. At each sample time, soil pore water was extracted using Rhizon soil solution samplers, and concentrations of Cd, Zn, dissolved organic carbon, and major cations and anions were determined. The chemical speciation program WHAM 6 was used to determine free metal ion activity, (M²⁺). Similar measurements were made on a set of historically contaminated soils from old mining areas, sewage sludge disposal facilities, and industrial sources. The two data sets were combined to give a range of values for p(Cd²⁺) and p(Zn²⁺) that covered 5 and 4 log₁₀ units, respectively. A pH-dependent Freundlich model was used to predict Zn²⁺ and Cd²⁺ ion activity in soil pore water. Total and radio-labile metal ion concentration in the solid phase was assumed to be adsorbed on the “whole soil,” humus, or free iron oxides to provide alternative model formats. The most successful models assumed that solubility was controlled by adsorption on soil humus. Inclusion of ionic strength as a model variable provided small improvements in model fit. Considering competition with Ca²⁺ and between Zn²⁺ and Cd²⁺ produced no apparent improvement in model fit. Surprisingly, there was little difference between the use of total and labile adsorbed metal as a model determinant. However, this may have been due to a strong correlation between metal lability and pH in the data set used. Values of residual standard deviation for the parameterized models using labile metal adsorbed on humus were 0.26 and 0.28 for prediction of p(Cd²⁺) and p(Zn²⁺), respectively. Solubility control by pure Zn and Cd minerals was not indicated from saturation indices. However there may have been fixation of metals to non-radio-labile forms in CaCO₃ and Ca-phosphate compounds in the soils in the higher pH range. Independent validation of the Cd model was carried out using an unpublished data set that included measurements of isotopically exchangeable Cd. There was good agreement with the parameterized model.     

ZH型重金属螯合纤维对水溶液中Sr2+的吸附行为

研究了ZH型重金属螯合纤维对水溶液中Sr~(2+)的吸附行为,考察了pH值、纤维加入量、Sr~(2+)初始浓度、作用时间等对吸附行为的影响,并采用SEM、EDS和FTIR等现代分析测试手段探讨了ZH型重金属螯合纤维对Sr~(2+)的吸附机制。结果表明,在pH值为7.0、纤维加入量为2.0 g/L、Sr~(2+)初始质量浓度为50 mg/L的条件下,纤维对Sr~(2+)的吸附在4 h左右基本达到平衡。实验条件下ZH型重金属螯合纤维对Sr~(2+)的最大吸附量可达26.22 mg/g。等温吸附拟合结果表明,ZH型重金属螯合纤维对Sr~(2+)的吸附可能是以单分子层为主的单分子层和多分子层吸附共同作用的结果。纤维对Sr~(2+)的动力学吸附过程符合准二级动力学模型。红外光谱分析表明Sr~(2+)与纤维上—NH_2和—COOH等基团进行配位络合从而吸附在纤维表面,—CH_2—和C=CH_2等基团参与此吸附过程。能谱分析表明Sr~(2+)与纤维上Na~+和Ca~(2+)还存在着离子交换作用。     

Adsorption of rare earth elements onto Carrizo sand: Experimental investigations and modeling with surface complexation

Rare earth element (REE) adsorption onto sand from a well characterized aquifer, the Carrizo Sand aquifer of Texas, has been investigated in the laboratory using a batch method. The aim was to improve our understanding of REE adsorption behavior across the REE series and to develop a surface complexation model for the REEs, which can be applied to real aquifer-groundwater systems. Our batch experiments show that REE adsorption onto Carrizo sand increases with increasing atomic number across the REE series. For each REE, adsorption increases with increasing pH, such that when pH >6.0, >98% of each REE is adsorbed onto Carrizo sand for all experimental solutions, including when actual groundwaters from the Carrizo Sand aquifer are used in the experiments. Rare earth element adsorption was not sensitive to ionic strength and total initial REE concentrations in our batch experiments. It is possible that the differences in experimental ionic strength conditions (i.e., 0.002-0.01 M NaCl) chosen were insufficient to affect REE adsorption behavior. However, cation competition (e.g., Ca, Mg, and Zn) did affect REE adsorption onto Carrizo sand, especially for light rare earth elements (LREEs) at low pH. Rare earth element adsorption onto Carrizo sand can be successfully modeled using a generalized two-layer surface complexation model. Our model calculations suggest that REE complexation with strong surface sites of Carrizo sand exceeds the stability of the aqueous complexes LnOH²⁺, LnSO₄⁺, and LnCO₃⁺, but not that of Ln(CO₃)₂^- or LnPO₄^o in Carrizo groundwaters. Thus, at low pH (<7.3), where major inorganic ligands did not effectively compete with surface sites for dissolved REEs, free metal ion (Ln³⁺) adsorption was sufficient to describe REE adsorption behavior. However, at higher pH (>7.3) where solution complexation of the dissolved REEs was strong, REEs were adsorbed not only as free metal ion (Ln³⁺) but also as aqueous complexes (e.g., as Ln(CO₃)₂^- in Carrizo groundwaters). Because heavy rare earth elements (HREEs) were preferentially adsorbed onto Carrizo sand compared to LREEs, original HREE-enriched fractionation patterns in Carrizo groundwaters from the recharge area flattened along the groundwater flow path in the Carrizo Sand aquifer due to adsorption of free- and solution-complexed REEs.     

Structure of hydrated Zn at the rutile TiO2 (110)-aqueous solution interface: Comparison of X-ray standing wave, X-ray absorption spectroscopy, and density functional theory results

Adsorption of Zn²⁺ at the rutile TiO₂ (110)-aqueous interface was studied with Bragg-reflection X-ray standing waves (XSW), polarization-dependent surface extended X-ray absorption fine structure (EXAFS) spectroscopy, and density functional theory (DFT) calculations to understand the interrelated issues of adsorption site, its occupancy, ion-oxygen coordination and hydrolysis. At pH 8, Zn²⁺ was found to adsorb as an inner-sphere complex at two different sites, i.e., monodentate above the bridging O site and bidentate between two neighboring terminal O sites. EXAFS results directly revealed a four or fivefold first shell coordination environment for adsorbed Zn²⁺ instead of the sixfold coordination found for aqueous species at this pH. DFT calculations confirmed the energetic stability of a lower coordination environment for the adsorbed species and revealed that the change to this coordination environment is correlated with the hydrolysis of adsorbed Zn²⁺. In addition, the derived adsorption locations and the occupancy factors of both sites from three methods agree well, with some quantitative discrepancies in the minor site location among the XSW, EXAFS, and DFT methods. Additional XSW measurements showed that the adsorption sites of Zn²⁺ were unchanged at pH 6. However, the Zn²⁺ partitioning between the two sites changed substantially, with an almost equal distribution between the two types of sites at pH 6 compared to predominantly monodentate occupation at pH 8.     

Mg2+ removal in the system Mg2+—amorphous SiO2—H2O by adsorption and Mg-hydroxysilicate precipitation

Two chemical processes can remove Mg²⁺ from suspensions containing amorphous silica (am-SiO₂) at low temperatures: adsorption and precipitation of a Mg-hydroxysilicate resembling sepiolite. Mg²⁺ removal from am-SiO₂ suspensions was investigated, and the relative role of the two removal processes evaluated, as a function of: pH, ionic strength, Mg²⁺ concentration, and temperature.The extent of Mg²⁺ adsorption onto am-SiO₂ decreases with increasing NaCl concentration due to displacement of Mg²⁺ by Na⁺. At NaCl concentrations of 0.05 M and above, adsorption occurs only at pH values above 8.5, where rapid dissolution of am-SiO₂ gives rise to high concentrations of dissolved silica, resulting in supersaturation with respect to sepiolite. Removal of Mg²⁺, at concentrations of 40 to 650 μM, from am-SiO₂ suspensions in 0.70 M NaCl at 25 °C occurs at pH 9.0 and above. Experiments show that under these conditions adsorption and Mg-hydroxysilicate precipitation remove Mg²⁺ at similar rates. For 0.05 M Mg²⁺, at 0.70 M ionic strength and 25 °C, measurable Mg²⁺ removal occurs down to ca. pH 7.5 but is primarily due to Mg-hydroxysilicate precipitation. For the same solution conditions at 5°C, Mg²⁺ removal occurs above pH 8.0 and is primarily due to adsorption.Assuming that increasing pressure does not greatly enhance adsorption, Mg²⁺ adsorption onto am-SiO₂ is an insignificant process in sea water. The surface charge of pristine am-SiO₂ in sea water is primarily controlled by interactions with Na⁺. The principal reaction between Mg²⁺ and am-SiO₂ in marine sediments is sepiolite precipitation.The age distribution of sepiolite in siliceous pelagic sediments is influenced by temperatures of bottom waters and by geothermal gradients.     

Adsorption of organic matter at mineral/water interfaces: I. ATR-FTIR spectroscopic and quantum chemical study of oxalate adsorbed at boehmite/water and corundum/water interfaces

The types and structures of adsorption complexes formed by oxalate at boehmite (γ-AlOOH)/water and corundum (α-Al₂O₃)/water interfaces were determined using in situ attenuated total reflectance fourier transform infrared (ATR-FTIR) spectroscopy and quantum chemical simulation methods. At pH 5.1, at least four different oxalate species were found at or near the boehmite/water interface for oxalate surface coverages (Γ_ox) ranging from 0.25 to 16.44 μmol/m². At relatively low coverages (Γ_ox < 2.47), strongly adsorbed inner-sphere oxalate species (IR peaks at 1286, 1418, 1700, and 1720 cm⁻¹) replace weakly adsorbed carbonate species, and a small proportion of oxalate anions are adsorbed in an outer-sphere mode (IR peaks at 1314 and 1591 cm⁻¹). IR peaks indicative of inner-sphere adsorbed oxalate are also observed for oxalate at the corundum/water interface at Γ_ox = 1.4 μmol/m². With increasing oxalate concentration (Γ_ox > 2.47 μmol/m²), the boehmite surface binding sites for inner-sphere adsorbed oxalate become saturated, and excess oxalate ions are present dominantly as aqueous species (IR peaks at 1309 and 1571 cm⁻¹). In addition to these adsorption processes, oxalate-promoted dissolution of boehmite following inner-sphere oxalate adsorption becomes increasingly pronounced with increasing Γ_ox and results in an aqueous Al(III)-oxalate species, as indicated by shifted IR peaks (1286 → 1297 cm⁻¹ and 1418 → 1408 cm⁻¹). At pH 2.5, no outer-sphere adsorbed oxalate or aqueous oxalate species were observed. The similarity of adsorbed oxalate spectral features at pH 2.5 and 5.1 implies that the adsorption mechanism of aqueous HOx⁻ species involves loss of protons from this species during the ligand-exchange reaction. As a consequence, adsorbed inner-sphere oxalate and aqueous Al(III)-oxalate complexes formed at pH 2.5 have coordination geometries very similar to those formed at pH 5.1.The coordination geometry of inner-sphere adsorbed oxalate species was also predicted using quantum chemical geometry optimization and IR vibrational frequency calculations. Geometry-optimized Al₈O₁₂ and Al₁₄O₂₂ clusters with the reactive surface Al site coordinated by three oxygens were used as model substrates for corundum and boehmite surfaces. Among the models considered, calculated IR frequencies based on a bidentate side-on structure with a 5-membered ring agree best with the observed frequencies for boehmite/oxalate/water samples at Γ_ox = 0.25 to 16.44 μmol/m² and pH 2.5 and 5.1, and for a corundum/oxalate/water sample at Γ_ox = 1.4 μmol/m² and pH 5.1. Based on these results, we suggest that oxalate bonding on boehmite and corundum surfaces results in 5-coordinated rather than 4- or 6-coordinated Al surface sites.     

Experimental determination of the stability and stoichiometry of sulphide complexes of silver(I) in hydrothermal solutions to 400°C

The solubility of silver sulphide (acanthite/argentite) has been measured in aqueous sulphide solutions between 25 and 400°C at saturated water vapour pressure and 500 bar to determine the stability and stoichiometry of sulphide complexes of silver(I) in hydrothermal solutions. The experiments were carried out in a flow-through autoclave, connected to a high-performance liquid chromatographic pump, titanium sampling loop, and a back-pressure regulator on line. Samples for silver determination were collected via the titanium sampling loop at experimental temperatures and pressures. The solubilities, measured as total dissolved silver, were in the range 1.0 × 10⁻⁷ to 1.30 × 10⁻⁴ mol kg⁻¹ (0.01 to 14.0 ppm), in solutions of total reduced sulphur between 0.007 and 0.176 mol kg⁻¹ and pH_T,p of 3.7 to 12.7. A nonlinear least squares treatment of the data demonstrates that the solubility of silver sulphide in aqueous sulphide solutions of acidic to alkaline pH is accurately described by the reactions0.5Ag₂S(s) + 0.5H₂S(aq) = AgHS(aq) K_s,1110.5Ag₂S(s) + 0.5H₂S(aq) + HS⁻ = Ag(HS)2− K_s,122Ag₂S(s) + 2HS⁻ = Ag₂S(HS)22− K_s,232where AgHS(aq) is the dominant species in acidic solutions, Ag(HS)2− under neutral pH conditions and Ag₂S(HS)22− in alkaline solutions. With increasing temperature the stability field of Ag(HS)2− increases and shifts to more alkaline pH in accordance with the change in the first ionisation constant of H₂S(aq). Consequently, Ag₂S(HS)22− is not an important species above 200°C. The solubility constant for the first reaction is independent of temperature to 300°C, with values in the range logK_s,111 = −5.79 (±0.07) to −5.59 (±0.09), and decreases to −5.92 (±0.16) at 400°C. The solubility constant for the second reaction increases almost linearly with inverse temperature from logK_s,122 = −3.97 (±0.04) at 25°C to −1.89 (±0.03) at 400°C. The solubility constant for the third reaction increases with temperature from logK_s,232 = −4.78 (±0.04) at 25°C to −4.57 (±0.18) at 200°C. All solubility constants were found to be independent of pressure within experimental uncertainties. The interaction between Ag⁺ and HS⁻ at 25°C and 1 bar to form AgHS(aq) has appreciable covalent character, as reflected in the exothermic enthalpy and small entropy of formation. With increasing temperature, the stepwise formation reactions become progressively more endothermic and are accompanied by large positive entropies, indicating greater electrostatic interaction. The aqueous speciation of silver is very sensitive to fluid composition and temperature. Below 100°C silver(I) sulphide complexes predominate in reduced sulphide solutions, whereas Ag⁺ and AgClOH⁻ are the dominant species in oxidised waters. In high-temperature hydrothermal solutions of seawater salinity, chloride complexes of silver(I) are most important, whereas in dilute hydrothermal fluids of meteoric origin typically found in active geothermal systems, sulphide complexes predominate. Adiabatic boiling of dilute and saline geothermal waters leads to precipitation of silver sulphide and removal of silver from solution. Conductive cooling has insignificant effects on silver mobility in dilute fluids, whereas it leads to quantitative loss of silver for geothermal fluids of seawater salinity.     

Removal of cationic dye methylene blue (MB) from aqueous solution by ground raw and base modified pine cone powder

The adsorption capacity of raw and sodium hydroxide-treated pine cone powder in the removal of methylene blue (MB) from aqueous solution was investigated in a batch system. It was found that the base modified pine cone exhibits large adsorption capacity compared with raw pine cone. The extent of adsorption capacity was increased with the increase in NaOH concentration. Overall, the extent of MB dye adsorption increased with increase in initial dye concentration, contact time, and solution pH but decreased with increase in salt concentration and temperature for both the systems. Surface characteristics of pine cone and base modified pine cone were investigated using Fourier transform infrared spectrophotometer and scanning electron microscope. Equilibrium data were best described by both Langmuir isotherm and Freundlich adsorption isotherm. The maximum monolayer adsorption capacity was found to be 129.87 mg g^?1 at solution pH of 9.02 for an initial dye concentration of 10 ppm by raw pine cone. The base modified pine cone showed the higher monolayer adsorption capacity of 142.25 mg g^?1 compared with raw pine cone biomass. The value of separation factor, R _L, from Langmuir equation and Freundlich constant, n, both give an indication of favourable adsorption. The various kinetic models, such as pseudo-first-order model, pseudo-second-order model, intraparticle diffusion model, double-exponential model, and liquid film diffusion model, were used to describe the kinetic and mechanism of adsorption process. Overall, kinetic studies showed that the dye adsorption process followed pseudo-second-order kinetics based on other models. The different kinetic parameters, including rate constant, half-adsorption time and diffusion coefficient, were determined at different physicochemical conditions. A single-stage bath adsorber design for the MB adsorption onto pine cone and modified pine cone has been presented based on the Langmuir isotherm model equation. Thermodynamic parameters, such as standard Gibbs free energy (ΔG ⁰), standard enthalpy (ΔH ⁰) and standard entropy (ΔS ⁰), were also calculated.     

The mobility of thorium in natural waters at low temperatures

Thermodynamic properties of 32 dissolved thorium species and 9 thorium-bearing solid phases have been collected from the literature, critically evaluated and estimated where necessary for 25°C and 1 atm pressure. Although the data are incomplete, especially for thorium minerals and organic complexes, some tentative conclusions can be drawn. Dissolved thorium is almost invariably complexed in natural waters. For example, based on ligand concentrations typical of ground water (ΣCl = 10 ppm, ΣF = 0.3 ppm, ΣSO₄ = 100 ppm, andΣPO₄ = 0.1 ppm), the predominant thorium species are Th(SO₄)⁰₂, ThF²⁺₂, and Th(HPO₄)₂⁰below pH ≈ 4.5; Th(HPO₄)^2?₃ from about pH 4.5 to 7.5; and Th(OH)⁰₄ above pH 7.5. Based on stability constants for thorium citrate, oxalate and EDTA complexes, it seems likely that organic complexes predominate over inorganic complexes of thorium in organic-rich stream waters, swamp waters, soil horizons, and waterlogged recent sediments. The thorium dissolved in seawater is probably present in organic complexes and as Th(OH)⁰₄. The tendency for thorium to form strong complexes enhances its potential for transport in natural waters by many orders of magnitude below pH 7 in the case of inorganic complexing, and below about pH 8 when organic complexing is important. The existence of complexes in addition to those formed with hydroxyl, is apparent from the fact that measured dissolved thorium in fresh surface waters (pH values generally 5–8) usually ranges from about 0.01 to 1 ppb and in surface seawater (pH = 8.1) is about 0.00064 ppb. This may be contrasted with the computed solubility of thorianite in pure water which is only 0.00001 ppb Th as Th(OH)⁰₄ above pH 5. Although complexing increases the solubility of thorium-bearing heavy minerals below pH 8, maximum thorium concentrations in natural waters are probably limited in general by the paucity and slow solution rate of these minerals and by sorption processes, rather than by mineral-solution equilibria.     

Sorption of phosphate onto calcite; results from batch experiments and surface complexation modeling

The adsorption of phosphate onto calcite was studied in a series of batch experiments. To avoid the precipitation of phosphate-containing minerals the experiments were conducted using a short reaction time (3 h) and low concentrations of phosphate (?50 μM). Sorption of phosphate on calcite was studied in 11 different calcite-equilibrated solutions that varied in pH, P_CO2, ionic strength and activity of Ca²⁺, and . Our results show strong sorption of phosphate onto calcite. The kinetics of phosphate sorption onto calcite are fast; adsorption is complete within 2-3 h while desorption is complete in less than 0.5 h. The reversibility of the sorption process indicates that phosphate is not incorporated into the calcite crystal lattice under our experimental conditions. Precipitation of phosphate-containing phases does not seem to take place in systems with ?50 μM total phosphate, in spite of a high degree of super-saturation with respect to hydroxyapatite (SI_HAP ? 7.83). The amount of phosphate adsorbed varied with the solution composition, in particular, adsorption increases as the activity decreases (at constant pH) and as pH increases (at constant activity). The primary effect of ionic strength on phosphate sorption onto calcite is its influence on the activity of the different aqueous phosphate species. The experimental results were modeled satisfactorily using the constant capacitance model with >CaPO₄Ca⁰ and either >CaHPO₄Ca⁺ or > as the adsorbed surface species. Generally the model captures the variation in phosphate adsorption onto calcite as a function of solution composition, though it was necessary to include two types of sorption sites (strong and weak) in the model to reproduce the convex shape of the sorption isotherms.     

Processes and kinetics of Cd2+ sorption by a calcareous aquifer sand

The rate of Cd²⁺ sorption by a calcareous aquifer sand was characterized by two reaction steps, with the first step reaching completion in 24 hours. The second step proceeded at a slow and nearly constant rate for at least seven days. The first step includes a fast adsorption reaction which is followed by diffusive transport into either a disordered surface film of hydrated calcium carbonate or into pore spaces. After 24 hours the rate of Cd²⁺ sorption was constant and controlled by the rate of surface coprecipitation, as a solid solution of CdCO₃ in CaCO₃ formed in recrystallizing material. Desorption of Cd²⁺ from the sand was slow. Clean grains of primary minerals, e.g. quartz and aluminosilicates. sorbed much less Cd²⁺ than grains which had surface patches of secondary minerals, e.g. carbonates, iron and manganese oxides. Calcite grains sorbed the greatest amount of Cd²⁺ on a weight-normalized basis despite the greater abundance of quartz. A method is illustrated for determining empirical binding constants for trace metals at in situ pH values without introducing the experimental problem of supersaturation. The binding constants are useful for solute transport models which include a computation of aqueous speciation.