Readily dispersible clay and its role in the mobility of transition metals Cd2+, Cu2+ and Zn2+ in an alkaline alluvial soil

Readily dispersible clay is the part of the clay fraction in soils that potentially disperses in water when a small amount of mechanical energy is applied to soil. Column and batch experiments were conducted to identify the effect of readily dispersible clay on the mobility of some metal ions in a disturbed soil sample. The clay fraction (<0.002 mm) was separated from an alkaline Vertisol from the Nile River Delta. X-ray diffraction technique was used to identify minerals present in the clay fraction. Clay suspensions and deionized H₂O solutions of Cd²⁺, Cu²⁺, and Zn²⁺ were prepared and used as influents in soil columns. Adsorption capability of the studied soil among the three metal ions was investigated. The results showed high adsorption capacity of Cd²⁺, Cu²⁺, but not Zn²⁺ for the studied soil. Cu²⁺ was the highest adsorbed metal by soil and its sorption increased at small equilibrium concentrations compared with Cd²⁺ and Zn²⁺. For the three studied metal ions, Langmuir model represented the best fit to the adsorption data. The concentration of Zn²⁺ and Cd²⁺ in leachates increased as the leaching solution volume increased, while Cu²⁺ showed a homogeneous distribution throughout the soil column. According to DTPA extractable metals, Zn²⁺ was appeared at greater depths than Cd²⁺, while Cu²⁺ had homogeneous distribution through the soil column.     

In situ formation of AgNPs on <Emphasis Type="Italic">S. cerevisiae</Emphasis> surface as bionanocomposites for bacteria killing and heavy metal removal

Novel bionanocomposites, S. cerevisiae–AgNPs, were synthesized by in situ formation of AgNPs on S. cerevisiae surface using fulvic acids as reductants under simulated sunlight. S. cerevisiae–AgNPs were characterized using UV–Vis spectroscopy, scanning electron microscope, transmission electron microscope and Fourier transform infrared spectroscopy. These analyses showed that AgNPs were distributed on the surface of S. cerevisiae. The application of S. cerevisiae–AgNPs in bacteria killing and heavy metal removal was studied. S. cerevisiae–AgNPs effectively inhibited the growth of E. coli with increasing concentrations of S. cerevisiae–AgNPs. E. coli was killed completely at high concentration S. cerevisiae–AgNPs (e.g., 100 or 200 µg mL^?1). S. cerevisiae–AgNPs as excellent heavy metal absorbents also have been studied. Using Cd²⁺ as model heavy metal, batch experiments confirmed that the adsorption behavior fitted the Langmuir adsorption isotherms and the Cd²⁺ adsorption capacity of S. cerevisiae–AgNPs was 15.01 mg g^?1. According to adsorption data, the kinetics of Cd²⁺ uptake by S. cerevisiae–AgNPs followed pseudo second-order kinetic model. Moreover, S. cerevisiae–AgNPs possessed ability of different heavy metals’ removal (e.g., Cr⁵⁺, As⁵⁺, Pb²⁺, Cu²⁺, Mn²⁺, Zn²⁺, Hg²⁺, Ni²⁺). The simulated contaminated water containing E. coli, Cd²⁺ and Pb²⁺ was treated using S. cerevisiae–AgNPs. The results indicated that the bionanocomposites can be used to develop antibacterial agents and bioremediation agents for water treatment.     

Assessment of raw clays from Maghnia (Algeria) for their use in the removal of Pb<Superscript>2+</Superscript> and Zn<Superscript>2+</Superscript> ions from industrial liquid wastes: a case study of wastewater treatment

Homogenized samples of raw clays resulting from two (2) different lots of natural clays from Maghnia (Algeria) have been assessed for their potential use in the removal of Pb²⁺ and Zn²⁺ ions from industrial liquid wastes (LW). Raw and acid-activated samples have been characterized by powder X-ray diffraction, FT-IR spectroscopy, electron microscopy (SEM), and X-ray fluorescence (XRF) and used as adsorbents for the removal of Pb²⁺ and Zn²⁺ ions from aqueous system using adsorption method under different conditions. The effect of factors including contact time, pH, and dosage on the adsorption properties of Pb²⁺ and Zn²⁺ ions onto clays was investigated at 25 °C. The obtained results revealed that the removal percentages of Pb²⁺ and Zn²⁺ ions, from both aqueous solution (AS) and LW, were varying between 90 and 98% for 40 min and optimal pH values ranged from 5 to 6 for Pb²⁺ and Zn²⁺ ions, respectively. The kinetics of both Pb²⁺ and Zn²⁺ ion adsorption fitted well with the pseudo-second-order model. Langmuir, Freundlich, and Temkin adsorption isotherms were used, and their constants were evaluated. The values of thermodynamic parameters, ΔH°, ΔS°, and ΔG° indicated that the adsorption of Pb²⁺ and Zn²⁺ ions was spontaneous and exothermic process in nature. The adsorption and desorption isotherms indicated that Pb²⁺ and Zn²⁺ adsorption to raw clays was reversible. The experimental results obtained showed that the raw clays from Maghnia (Algeria) had a great potential for removing Pb²⁺ and Zn²⁺ ions from industrial liquid wastes using adsorption method.     

Removal of heavy metal ions from drinking water by alginate-immobilised <Emphasis Type="Italic">Chlorella sorokiniana</Emphasis>

This paper investigates the potential of alginate-immobilised Chlorella sorokiniana for removing Cu²⁺, Ni²⁺ and Cd²⁺ ions from drinking water solutions. The effects of initial metal concentrations, contact times and temperatures on the biosorptions and removal efficiencies of the tested metals were investigated at initial pH values of 5, and pH effects were studied within the range of 3–7. When studying the effects of initial metal concentrations, the highest experimental removal yields achieved for Cu²⁺, Ni²⁺ and Cd²⁺ ions were 97.10, 50.94 and 64.61 %, respectively. The maximum biosorption capacities obtained by the Langmuir isotherm model for the biosorptions of Cu²⁺, Ni²⁺ and Cd²⁺ ions by alginate-immobilised C. sorokiniana were found to be 179.90, 86.49 and 164.50 mg/g biosorbent, respectively. The experimental data followed pseudo-second-order kinetics. At an initial metal concentration of 25 mg/L, immobilised algae could be used in at least 5 successive biosorption–desorption cycles. SEM and EDS analyses revealed that the metals bonded to the biosorbent. Bi- and multi-metal systems of Cu²⁺, Ni²⁺ and Cd²⁺ were investigated at initial metal concentrations of 30, 50 and 100 mg/L. The removal of Cd²⁺ as well as Ni²⁺ in such systems was negatively affected by the presence of Cu²⁺. The removal efficiency for Cu²⁺ in multi-metal systems decreased by 5–7 %, whilst in the cases of Cd²⁺ and Ni²⁺ the efficiencies decreased by up to 30 %. Nevertheless, the results obtained show that alginate-immobilised C. sorokiniana can efficiently remove the metals tested from polluted drinking water sources.     

Biosorption characteristics of heavy metals (Ni2+, Zn2+, Cd2+, Pb2+) from aqueous solution by Hizikia fusiformis

Heavy metal ions (Pb²⁺, Cd²⁺, Ni²⁺, and Zn²⁺) were biosorbed by brown seaweed (Hizikia fusiformis), which was collected from Jeju Island of South Korea. The metal adsorption capacity of H. fusiformis improved significantly by washing with water or by base or acid treatments. The maximum sorption by NaOH-pretreated biomass was observed near a slightly acidic pH (pH 4?6) for Pb²⁺, Cd²⁺, Ni²⁺, and Zn²⁺. This result suggests that the treatment of H. fusiformis biomass with NaOH helped increase the functional forms of carboxylate ester units. Kinetic data showed that the biosorption occurred rapidly during the first 60 min, and most of the heavy metals were bound to the seaweed within 180 min. The maximum metal adsorption capacities assumed by a Langmuir model were on the order of Pb²⁺ > Cd²⁺ > Ni²⁺ > Zn²⁺. Equilibrium adsorption data for the heavy metal ions could fit well in the Langmuir model with regression coefficients R ² > 0.97.     

Geochemical evaluation and environmental application of Yemeni natural zeolite as sorbent for Cd<Superscript>2+</Superscript> from solution: kinetic modeling,equilibrium studies,and statistical optimization

Yemeni natural zeolite was characterized by XRD, SEM, FTIR and XRF as well as its applicability as a sorbent material for Cd²⁺ ions in aqueous solutions. The zeolitic sample is clinoptilolite-K of heulandite group with intermediate Si/Al ratio. The removal% of Cd²⁺ by natural clinoptilolite was investigated as a function of contact time, zeolite dose, pH and initial concentration of Cd²⁺ ions. Kinetic experiments indicated that sorption of Cd²⁺ follows two steps: rapid ion exchange process on the outer surface is followed by slow adsorption process on the inner surface of clinoptilolite. The equilibrium was attained after 120 min, and the results were fitted well with pseudo-second order and Elovich kinetic models. The Cd²⁺ removal% is strongly dependent on pH value and increases with the increasing pH value. Equilibrium sorption isotherm of Cd²⁺ by clinoptilolite was described well using the Langmuir, Freundlich, and Temkin isotherms models. However, the data relatively well fitted with Freundlich model (R ² = 0.97) rather than by the other models. Response surface methodology in conjunction with central composite rotatable statistical design was used to optimize the sorption process. The model F-value indicated the high significance of second-order polynomial model to represent the interaction between the operating parameters. From the Design Expert’s optimization function, the predicted optimum conditions for maximum removal% of Cd²⁺ (80.77%) are 116 min contact time, 0.27 gm dose, and pH 7 at an initial Cd²⁺ concentration of 25 mg/L.     

Theoretical investigations of the local structures and the <Emphasis Type="Italic">g</Emphasis> factors for 3d<Superscript>9</Superscript> ions in CdS

The local structures and the g factors g _// and g _⊥ for the isoelectronic 3d⁹ ions Cu²⁺ and Ni⁺ in CdS are theoretically investigated from the perturbation formulas of these parameters for a 3d⁹ ion under trigonally distorted tetrahedral environments. In consideration of significant covalency of the [MS₄] combinations (M = Cu and Ni), the ligand orbital and spin–orbit coupling contributions are taken into account using the cluster approach. Based on the studies, the substitutional impurity Cu²⁺ (or Ni⁺) on Cd²⁺ site is found to undergo a small inward displacement 0.026 Å (or a slight outward shift 0.017 Å) towards (or away from) the ligand triangle along C ₃ axis. The theoretical g factors for both ions based on the above impurity displacements are in good agreement with the experimental data.     

The influence of ionic radii of cations and covalent forces on the unit cell dimensions of spinels

Fe-, Cr- and Al-spinels were synthesized and their unit cell sizes determined by means of X-rays. Differential thermal curves show that the magnetic inversion of Fe₂O₃ at 680° C accelerates the formation of the ferrites when the constituent oxides are heated together.A correlation can be made between ionic radii of cations and unit cell dimensions provided the effect of covalent forces in the lattice is taken into account. The values for ionic radii of cations as given byAhrens (1952) permit a better correlation than those ofGoldschmidt.A shrinkage of 0.01 Å in the unit cell size per 0.01 Å decrease in the ionic radius of the divalent cations was determined when spinels with the same cation arrangement in the same group were compared. A shrinkage of 0.027 Å in the unit cell size per 0.01 Å decrease in the ionic radius of the trivalent cations was determined in spinels having the same divalent cation and cation arrangement when the trivalent cations form the same type of bonds.The half-occupation of the 3d orbits in Mn²⁺ and Fe³⁺ causes abnormally high unit cell dimensions in spinels where these ions are incorporated in octahedral sites. This is attributed to the formation of electrovalent bonds by these ions. Variable forces of contraction in the lattice are revealed when the unit cell dimensions are correlated with the ionic radii of cations. The force of contraction can be satisfactorily explained as being due to covalent forces in the spinel structure. The magnitude of this force or the degree of covalence in the bonds increases in the following order of cations where these are situated in tetrahedral sites:The divalent transition element ions, Fe²⁺, Co²⁺ and Ni²⁺; the B-Sub-group element ions Cd²⁺ and Zn²⁺; Fe³⁺ in tetrahedral co-ordination.     

Biosorption an innovative tool for bioremediation of metal-contaminated municipal solid waste leachate: optimization and mechanisms exploration

Municipal solid waste poses a risk on surrounding environment and public health, mainly because of unscientific disposal and shortage of facilities for proper handling and recycling of leachate. This research article objective is to pinpoint the indigenous fungal isolates of waste leachate samples. Therefore, we carried out biosorption of Cd²⁺ tested the applicability by applying indigenous fungal isolates. The limited number of fungal isolates was found based on their ability for biosorption of Cd²⁺ metal. The fungal strains Trichoderma sp., Aspergillus niger and Aspergillus flavus were reported as potential strains for metal exclusion ability from the leachate. Among them, the Trichoderma sp. was found as excellent fungal agent for Cd²⁺ absorption. The optimum pH was 5.5 ± 1, temperature 45 °C, and spore concentration 10^?5 to achieve the maximum biosorption, and 35 days of incubation period were required by three strains. The maximum metal biosorption achieved was comparable for the three isolates: 56.34% by Trichoderma sp., 44.74 and 42.04% by A. niger and A. flavus, respectively. Concluding, the further intending application to identified potentially fungal isolates is able to improve the efficiency of metal biosorption. These strains are recommended for development of consortia could become a best technique for MSW leachate treatment if its reliability and applicability should be verified prior to technology acceptance.     

Removal of Lead,Copper, Zinc and Cadmium from Water Using Phosphate Rock

Removal of Pb^2＋, Cu^2＋, Zn^2＋ and Cd^2＋ from aqueous solutions by sorption on a natural phosphate rock （FAP） was investigated. The effects of the contact time and initial metal concentration were examined in the batch method. The percentage sorption of heavy metals from solution ranges generally between 50% and 99%. The amount of sorbed metal ions follows the order Cu〉Pb〉Cd〉Zn. Heavy metal immobilization was attributed to both surface complexation of metal ions on the surface of FAP grains and partial dissolution and precipitation of a heavy metal-containing phosphate. The very low desorption ratio of heavy metals further supports the effectiveness of FAP as an alternative and low-cost material to remove toxic Pb^2＋, Cu^2＋, Zn^2＋ and Cd^2＋ from polluted waters.     

Crystal chemistry of selenates with mineral-like structures. IV. Crystal structure of Zn(SeO<Subscript>4</Subscript>)(H<Subscript>2</Subscript>O)<Subscript>2</Subscript>, a new compound with a mixed framework of the variscite type

The crystal structure of a new compound Zn(SeO₄)(H₂O)₂ (orthorhombic, Pbca, a = 9.0411(13), b = 10.246(2), c = 10.3318(15) Å, V = 957.1(3) ų) has been solved by direct methods and refined to R ₁ = 0.033 on the basis of 1076 observed reflections with |F _hkl | ≥ 4σ|F _hkl |. The structure contains one independent Zn²⁺ cation coordinated by two water molecules and four oxygen atoms of selenate group. The only independent (SeO₄)^2? tetrahedral oxoanion is tetradentate, sharing its corners with four adjacent [Zn²⁺O₂(H₂O₄)]²⁺ octahedrons. The structure can be described as consisting of heteropolyhedral sheets parallel to the (001) plane and linked together into a three-dimensional network. The compound belongs to the variscite structure type and is the first structurally characterized selenate of this group.     

Separation of chemical elements in the atmospheres of CP stars under the action of light induced drift

A mechanism for the separation of chemical elements and isotopes in the atmospheres of chemically peculiar (CP) stars due to light-induced drift (LID) of ions is discussed. The efficiency of separation due to LID is proportional to the relative difference of the transport frequencies for collisions of ions of heavy elements located in the excited state (collision frequency ν _e ) and ground state (collision frequency ν _g ) with neutral buffer particles (hydrogen and helium), (ν _e ? ν _g )/ν _g . The known interaction potentials are used to numerically compute the relative difference (ν _e ^H ? ν _g ^H )/νg H for collisions between the ions Be⁺, Mg⁺, Ca⁺, Sr⁺, Cd⁺, Ba⁺, Al⁺, and C⁺ and hydrogen atoms. These computations show that, at the temperatures characteristic of the atmospheres of CP stars, T = 7000?20 000 K, values of |ν _e ^H ?ν _g ^H |/ν _g ^H ≈ 0.1?0.4 are obtained. With such relative differences in the transport collision frequencies, the LID rate of ions in the atmospheres of coolCP stars (T < 10000 K) can reach ~0.1 cm/s,which exceeds the drift rate due to light pressure by an order of magnitude. This means that, under these conditions, the separation of chemical elements under the action of LID of ions could be an order of magnitude more efficient than separation due to light pressure. Roughly the same manifestations of LID and light pressure are also expected in the atmospheres of hotter stars (20 000 > T > 10 000 K). LID of heavy ions is manifest only weakly in very hot stars (T > 20 000 K).     

Goethite adsorption of Cu(II), Pb(II), Cd(II), and Zn(II) in the presence of sulfate: Properties of the ternary complex

Adsorption of Cu²⁺, Zn²⁺, Cd²⁺, and Pb²⁺ onto goethite is enhanced in the presence of sulfate. This effect, which has also been observed on ferrihydrite, is not predicted by the diffuse layer model (DLM) using adsorption constants derived from single sorbate systems. However, by including ternary surface complexes with the stoichiometry FeOHMSO₄, where FeOH is a surface adsorption site and M²⁺ is a cation, the effect of SO₄²⁻ on cation adsorption was accurately predicted for the range of cation, goethite and SO₄²⁻ concentrations studied. While the DLM does not provide direct molecular scale insights into adsorption reactions there are several properties of ternary complexes that are evident from examining trends in their formation constants. There is a linear relationship between ternary complex formation constants and cation adsorption constants, which is consistent with previous spectroscopic evidence indicating ternary complexes involve cation binding to the oxide surface. Comparing the data from this work to previous studies on ferrihydrite suggests that ternary complex formation on ferrihydrite involves complexes with the same or similar structure as those observed on goethite. In addition, it is evident that ternary complex formation constants are larger where there is a stronger metal-ligand interaction. This is also consistent with spectroscopic studies of goethite-M²⁺-SO₄²⁻ and phthalate systems showing surface species with metal-ligand bonding. Recommended values of ternary complex formation constants for use in SO₄-rich environments, such as acid mine drainage, are presented.     

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.     

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.     

Biosorption of cadmium(II), lead(II) and cobalt(II) from aqueous solution by biochar from cones of larch (<Emphasis Type="Italic">Larix decidua</Emphasis> Mill. <Emphasis Type="Italic">subsp. decidua</Emphasis>) and spruce (<Emphasis Type="Italic">Picea abies</Emphasis> L. H. Karst)

Because of their physicochemical properties, biochars can be used as sorption materials for removal of toxic substances. The purpose of the present study was to determine whether biochar obtained from cones of larch (Larix decidua Mill. subsp. decidua) and spruce (Picea abies L. H. Karst) could be used as a sorbent for Cd²⁺, Pb²⁺ and Co²⁺ in aqueous solutions. So far, this feedstock had not been tested in this respect. The material was subjected to pyrolysis at 500 and 600 °C for the duration of 5, 10 and 15 min. The obtained pyrolysates were found to differ in terms of pH and the contents of the essential macroelements. The different values of these parameters were determined for varying temperature, duration of the pyrolysis process and type of feedstock. Sorption capacities of the biochars for removal of Cd²⁺, Pb²⁺ and Co²⁺ were examined using simulated contamination of aqueous solutions with salts of these metals. The findings showed the highest, nearly complete, removal for Pb²⁺ were maximum 99.7%, and almost three times lower value for Cd²⁺ and Co²⁺ (respectively, 35.7 and 24.8%). It was demonstrated that pyrolysis of conifer cones produced optimum sorption capacities when the process was conducted at a temperature of 500 °C for the duration of 5 min. It was shown that products of spruce cone pyrolysis were characterized by better sorption capacity in comparison with products of larch cone pyrolysis. The properties of conifer cone biochar create the possibility of using it as an adsorbent in water and wastewater treatment as well as in production of filters and activated carbon.     

Similar Adsorption Parameters for Trace Metals with Different Aquatic Particles

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

Influence of oxygen fugacity and temperature on the redox state of iron in natural silicic aluminosilicate melts

The influence of oxygen fugacity (fO₂) and temperature on the valence and structural state of iron was experimentally studied in glasses quenched from natural aluminosilicate melts of granite and pantellerite compositions exposed to various T-fO₂ conditions (1100–1420°C and 10^?12–10^?0.68 bar) at a total pressure of 1 atm. The quenched glasses were investigated by Mössbauer spectroscopy. It was shown that the effect of oxygen fugacity on the redox state of iron at 1320–1420°C can be described by the equation log(Fe³⁺/Fe²⁺) = k log(fO₂) + q, where k and q are constants depending on melt composition and temperature. The Fe³⁺/Fe²⁺ ratio decreases with decreasing fO₂ (T = const) and increasing temperature (fO₂ = const). The structural state of Fe³⁺ depends on the degree of iron oxidation. With increasing Fe³⁺/Fe²⁺ ≥ 1, the dominant coordination of Fe³⁺ changes from octahedral to tetrahedral. Ferrous iron ions occur in octahedral (and/or five-coordinated) sites independent of Fe³⁺/Fe²⁺.     

Thermodynamic controls on element partitioning between titanomagnetite and andesitic–dacitic silicate melts

Titanomagnetite–melt partitioning of Mg, Mn, Al, Ti, Sc, V, Co, Ni, Cu, Zn, Ga, Zr, Nb, Mo, Hf and Ta was investigated experimentally as a function of oxygen fugacity (fO₂) and temperature (T) in an andesitic–dacitic bulk-chemical compositional range. In these bulk systems, at constant T, there are strong increases in the titanomagnetite–melt partitioning of the divalent cations (Mg²⁺, Mn²⁺, Co²⁺, Ni²⁺, Zn²⁺) and Cu²⁺/Cu⁺ with increasing fO₂ between 0.2 and 3.7 log units above the fayalite–magnetite–quartz buffer. This is attributed to a coupling between magnetite crystallisation and melt composition. Although melt structure has been invoked to explain the patterns of mineral–melt partitioning of divalent cations, a more rigorous justification of magnetite–melt partitioning can be derived from thermodynamic principles, which accounts for much of the supposed influence ascribed to melt structure. The presence of magnetite-rich spinel in equilibrium with melt over a range of fO₂ implies a reciprocal relationship between a(Fe²⁺O) and a(Fe³⁺O_1.5) in the melt. We show that this relationship accounts for the observed dependence of titanomagnetite–melt partitioning of divalent cations with fO₂ in magnetite-rich spinel. As a result of this, titanomagnetite–melt partitioning of divalent cations is indirectly sensitive to changes in fO₂ in silicic, but less so in mafic bulk systems.