Reductive biotransformation of Fe in shale-limestone saprolite containing Fe(III) oxides and Fe(II)/Fe(III) phyllosilicates

A <2.0-mm fraction of a mineralogically complex subsurface sediment containing goethite and Fe(II)/Fe(III) phyllosilicates was incubated with Shewanella putrefaciens (strain CN32) and lactate at circumneutral pH under anoxic conditions to investigate electron acceptor preference and the nature of the resulting biogenic Fe(II) fraction. Anthraquinone-2,6-disulfonate (AQDS), an electron shuttle, was included in select treatments to enhance bioreduction and subsequent biomineralization. The sediment was highly aggregated and contained two distinct clast populations: (i) a highly weathered one with “sponge-like” internal porosity, large mineral crystallites, and Fe-containing micas, and (ii) a dense, compact one with fine-textured Fe-containing illite and nano-sized goethite, as revealed by various forms of electron microscopic analyses. Approximately 10-15% of the Fe(III)_TOT was bioreduced by CN32 over 60 d in media without AQDS, whereas 24% and 35% of the Fe(III)_TOT was bioreduced by CN32 after 40 and 95 d in media with AQDS. Little or no Fe²⁺, Mn, Si, Al, and Mg were evident in aqueous filtrates after reductive incubation. Mössbauer measurements on the bioreduced sediments indicated that both goethite and phyllosilicate Fe(III) were partly reduced without bacterial preference. Goethite was more extensively reduced in the presence of AQDS whereas phyllosilicate Fe(III) reduction was not influenced by AQDS. Biogenic Fe(II) resulting from phyllosilicate Fe(III) reduction remained in a layer-silicate environment that displayed enhanced solubility in weak acid. The mineralogic nature of the goethite biotransformation product was not determined. Chemical and cryogenic Mössbauer measurements, however, indicated that the transformation product was not siderite, green rust, magnetite, Fe(OH)₂, or Fe(II) adsorbed on phyllosilicate or bacterial surfaces. Several lines of evidence suggested that biogenic Fe(II) existed as surface associated phase on the residual goethite, and/or as a Fe(II)-Al coprecipitate. Sediment aggregation and mineral physical and/or chemical factors were demonstrated to play a major role on the nature and location of the biotransformation reaction and its products.     

57Fe NCR of Fe phases in “magnetic cassiterites”

A pyralspite garnet from an anomalously magnetic concentrate of a pegmatitic cassiterite ore has been investigated using ⁵⁷Fe nuclear gamma-ray resonance spectroscopy. The quadrupole splitting and isomer shift values of 3.6 mm/s and 1.4 mm/s, respectively, are among the largest observed for Fe²⁺ ions and indicate a very low covalency of the dodecahedral Fe²⁺ — O²-bonds. These data support the more recent and lower value (10.2–10.1 kcal/ mole) of White and Moore (1972) for the CFSE of the dodecahedral Fe²⁺ ion and suggest that the CFSE should be a useful approximation to the site preference energy of Fe²⁺ for this site.     

Fe Isotope Geochemistry of Hydrothermal Fe Exhalites

The sediments atop the sequence of ophiolite usually contain Fe(-Mn-Si)exhalites,chemical sediments that aremainlycomposedofamorphousFe-Mn oxy-hydroxides and chert/jasper.They were precipitated from hydrothermal fluids produced by deep leaching of basalt particularly during volcano activity or seafloor spreading.These hydrothermal Fe exhalites provide a good record for the depositional environment and the ocean environment as well.A well-preserved Phanerozoic Fe deposit,Motuosala Fe-Mn deposit,resulted from hydrothermal exhalation,was investigated for its trace element and Fe isotope geochemistry.The deposit is located in Xinjiang province,China and is hosted in a suit of Carboniferous volcano-sedimentary clastic rocks.The Fe deposit is mainly composed of massive hematite Fe oreand banded hematite-jasper ore.The hematite ore/band and jasper band were subjected to be analyzed.They are both composed mainly of Fe2O3 and Si O2,with very low contents of Al2O3 and Ti O2(1%),indicating they werechemical precipitates with little detrital contamination.They both show slightly LREE depleted or near flat PAAS-normalised REE patterns,with positive Eu anomalies and Y anomolies,indicating that they were sourced from a mixture of high-temperature fluids and seawater.Compared to the hematite Fe ore/band,the jasper band shows higher EuSN/EuSN*but lower Y/Ho values.δ56Fe values for the hematite Fe ores are clustered around-0.3‰,similar to those for high-temperature fluids.The jasper samples show heavier Fe isotope compositions varying from-0.1‰to0.5‰,indicating that they were resulted from partial Fe precipitation.For all samples,δ56Fe values are related to Y/Ho and EuSN/EuSN*values.The results indicate that the hematite Fe ore and jasper were deposited in different environments.The jasper was deposited in a more anoxic condition with higher hydrothermal fluids/seawater ratio,probably when the hydrothermal activity was more intense;while the hematite Fe ore was deposited in a more oxic condition with lower hydrothermal fluids/seawater ratio,probably when the hydrothermal activity was weaker.     

Fe2+–Fe3+ ordered distribution in chromite spinels

Mossbauer measurements have been carried out on three natural chromite minerals from different locations in China over the temperature range 50 to 750 K. The experiments showed these samples to be magnesioferrochromites. The Mossbauer spectra measured could be decomposed into three doublets: two attributed to the tetrahedral T-site Fe²⁺ ions and the third to the octahedral M-site Fe³⁺ ions. Thus for the chromite spinels the results strongly supported the ordered distribution with Fe²⁺ in the T-site and Fe³⁺ in M-site.     

Inter-mineral Fe isotope variations in mantle-derived rocks and implications for the Fe geochemical cycle

Iron isotope and major- and minor-element compositions of coexisting olivine, clinopyroxene, and orthopyroxene from eight spinel peridotite mantle xenoliths; olivine, magnetite, amphibole, and biotite from four andesitic volcanic rocks; and garnet and clinopyroxene from seven garnet peridotite and eclogites have been measured to evaluate if inter-mineral Fe isotope fractionation occurs in high-temperature igneous and metamorphic minerals and if isotopic fractionation is related to equilibrium Fe isotope partitioning or a result of open-system behavior. There is no measurable fractionation between silicate minerals and magnetite in andesitic volcanic rocks, nor between olivine and orthopyroxene in spinel peridotite mantle xenoliths. There are some inter-mineral differences (up to 0.2‰ in ⁵⁶Fe/⁵⁴Fe) in the Fe isotope composition of coexisting olivine and clinopyroxene in spinel peridotites. The Fe isotope fractionation observed between clinopyroxene and olivine appears to be a result of open-system behavior based on a positive correlation between the Δ⁵⁶Fe_{clinopyroxene-olivine} fractionation and the δ⁵⁶Fe value of clinopyroxene and olivine. There is also a significant difference in the isotopic compositions of garnet and clinopyroxene in garnet peridotites and eclogites, where the average Δ⁵⁶Fe_{clinopyroxene-garnet} fractionation is +0.32 ± 0.07‰ for six of the seven samples. The one sample that has a lower Δ⁵⁶Fe_{clinopyroxene-garnet} fractionation of 0.08‰ has a low Ca content in garnet, which may reflect some crystal chemical control on Fe isotope fractionation. The Fe isotope variability in mantle-derived minerals is interpreted to reflect subduction of isotopically variable oceanic crust, followed by transport through metasomatic fluids. Isotopic variability in the mantle might also occur during crystal fractionation of basaltic magmas within the mantle if garnet is a liquidus phase. The isotopic variations in the mantle are apparently homogenized during melting processes, producing homogenous Fe isotope compositions during crust formation.     

The role of Fe2+ and Fe3+ in synthetic Fe-substituted tetrahedrite

Summary Tetrahedrites with the composition between Cu₁₂Sb₄S₁₃ and Cu₁₀Fe₂Sb₄S₁₃ were synthesized at 457 °C and 500 °C from the elements and carefully studied by Mössbauer spectroscopy of⁵⁷Fe. Between Cu₁₂Sb₄S₁₃ and Cu₁₁Fe₁Sb₄S₁₃ iron is predominantly ferric. Between Cu₁₁Fe₁Sb₄S₁₃ and Cu₁₀Fe₂Sb₄S₁₃ iron is predominantly ferrous and occupies the tetrahedral M1-sites.

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Zusammenfassung Die Rolle von Fe²⁺ und Fe³⁺ in synthetischen Tetraedriten mit Fe-Substitution Tetraedrite mit einer Zusammensetzung zwischen Cu₁₂Sb₄S₁₃ and Cu₁₀Fe₂Sb₄S₁₃ wurden bei 457 °C und 500 °C aus den Elementen synthetisiert und sorgfdltig mit Mössbauer-Spektroskopie von⁵⁷Fe untersucht. Zwischen Cu₁₂Sb₄S₁₃ and Cu₁₁Fe₁Sb₄S₁₃ ist Eisen überwiegend dreiwertig. Zwischen Cu₁₁Fe₁Sb₄S₁₃ and Cu₁₁Fe₂Sb₄S₁₃ ist Eisen überwiegend zweiwertig und besetzt die tetraedrisch koordinierten M1-Plätze.

     

Kinetic and equilibrium Fe isotope fractionation between aqueous Fe(II) and Fe(III)

Equilibrium and kinetic Fe isotope fractionation between aqueous ferrous and ferric species measured over a range of chloride concentrations (0, 11, 110 mM Cl⁻) and at two temperatures (0 and 22°C) indicate that Fe isotope fractionation is a function of temperature, but independent of chloride contents over the range studied. Using ⁵⁷Fe-enriched tracer experiments the kinetics of isotopic exchange can be fit by a second-order rate equation, or a first-order equation with respect to both ferrous and ferric iron. The exchange is rapid at 22°C, ∼60-80% complete within 5 seconds, whereas at 0°C, exchange rates are about an order of magnitude slower. Isotopic exchange rates vary with chloride contents, where ferrous-ferric isotope exchange rates were ∼25 to 40% slower in the 11 mM HCl solution compared to the 0 mM Cl⁻ (∼10 mM HNO₃) solutions; isotope exchange rates are comparable in the 0 and 110 mM Cl⁻ solutions.The average measured equilibrium isotope fractionations, Δ_{Fe(III)-Fe(II)}, in 0, 11, and 111 mM Cl⁻ solutions at 22°C are identical within experimental error at +2.76±0.09, +2.87±0.22, and +2.76±0.06 ‰, respectively. This is very similar to the value measured by Johnson et al. (2002a) in dilute HCl solutions. At 0°C, the average measured Δ_{Fe(III)-Fe(II)} fractionations are +3.25±0.38, +3.51±0.14 and +3.56±0.16 ‰ for 0, 11, and 111 mM Cl⁻ solutions. Assessment of the effects of partial re-equilibration on isotope fractionation during species separation suggests that the measured isotope fractionations are on average too low by ∼0.20 ‰ and ∼0.13 ‰ for the 22°C and 0°C experiments, respectively. Using corrected fractionation factors, we can define the temperature dependence of the isotope fractionation from 0°C to 22°C as: where the isotopic fractionation is independent of Cl⁻ contents over the range used in these experiments. These results confirm that the Fe(III)-Fe(II) fractionation is approximately half that predicted from spectroscopic data, and suggests that, at least in moderate Cl⁻ contents, the isotopic fractionation is relatively insensitive to Fe-Cl speciation.     

Nanophase Fe0 in lunar soils

Back scattered electron and transmission electron imaging of lunar soil grains reveal an abundance of submicrometer-sized pure Fe⁰ globules that occur in the rinds of many soil grains and in the submillimeter sized vesicular glass-cemented grains called agglutinates. Grain rinds are amorphous silicates that were deposited on grains exposed at the lunar surface from transient vapors produced by hypervelocity micrometeorite impacts. Fe⁰ may have dissociated from Fe-compounds in a high temperature (>3000°C) vapor phase and then condensed as globules on grain surfaces. The agglutinitic glass is a quenched product of silicate melts, also produced by micrometeorite impacts on lunar soils. Reduction by solar wind hydrogen in agglutinitic melts may have produced immiscible droplets that solidified as globules. The exact mechanism of formation of such Fe⁰ globules in lunar soils remains unresolved.     

Effects of changing solution chemistry on Fe/Fe isotope fractionation in aqueous Fe-Cl solutions

The range in ⁵⁶Fe/⁵⁴Fe isotopic compositions measured in naturally occurring iron-bearing species is greater than 5‰. Both theoretical modeling and experimental studies of equilibrium isotopic fractionation among iron-bearing species have shown that significant fractionations can be caused by differences in oxidation state (i.e., redox effects in the environment) as well as by bond partner and coordination number (i.e., nonredox effects due to speciation).To test the relative effects of redox vs. nonredox attributes on total Fe equilibrium isotopic fractionation, we measured changes, both experimentally and theoretically, in the isotopic composition of an Fe²⁺-Fe³⁺-Cl-H₂O solution as the chlorinity was varied. We made use of the unique solubility of FeCl₄⁻ in immiscible diethyl ether to create a separate spectator phase against which changes in the aqueous phase could be quantified. Our experiments showed a reduction in the redox isotopic fractionation between Fe²⁺- and Fe³⁺-bearing species from 3.4‰ at [Cl⁻] = 1.5 M to 2.4‰ at [Cl⁻] = 5.0 M, due to changes in speciation in the Fe-Cl solution. This experimental design was also used to demonstrate the attainment of isotopic equilibrium between the two phases, using a ⁵⁴Fe spike.To better understand speciation effects on redox fractionation, we created four new sets of ab initio models of the ferrous chloride complexes used in the experiments. These were combined with corresponding ab initio models for the ferric chloride complexes from previous work. At 20 °C, 1000 ln β (β = ⁵⁶Fe/⁵⁴Fe reduced partition function ratio relative to a dissociated Fe atom) values range from 6.39‰ to 5.42‰ for Fe(H₂O)₆²⁺, 5.98‰ to 5.34‰ for FeCl(H₂O)₅⁺, and 5.91‰ to 4.86‰ for FeCl₂(H₂O)₄, depending on the model. The theoretical models predict ferric-ferrous fractionation about half as large (depending on model) as the experimental results.Our results show (1) oxidation state is likely to be the dominant factor controlling equilibrium Fe isotope fractionation in solution and (2) nonredox attributes (such as ligands present in the aqueous solution, speciation and relative abundances, and ionic strength of the solution) can also have significant effects. Changes in the isotopic composition of an Fe-bearing solution will influence the resultant Fe isotopic signature of any precipitates.     

Sign of the magnetic coupling of Fe2+ and Fe3+ in biotite

Mössbauer spectra of biotite at 4 K are reported. The biotite crystals were oriented with the c-axis parallel to the γ-ray direction and some spectra were recorded with external magnetic fields of 40 kOe applied at right angles to the c-axis. Decrease of the magnetic-hyperfine field of both Fe²⁺ and Fe³⁺ ions on application of the external field shows that both Fe³⁺-Fe³⁺ pairs and Fe²⁺-Fe²⁺ pairs are coupled ferromagnetically.     

Superoxide-mediated Fe(II) formation from organically complexed Fe(III) in coastal waters

Fe(III) complexed by organic ligands (Fe(III)L) is the primary form of dissolved Fe in marine and coastal environments. Superoxide, typically produced in biological and photochemical processes, is one of the reducing agents that contributes to transformation of Fe(III)L to bioavailable, free dissolved Fe(II) (Fe(II)′). In this work, the kinetics of superoxide-mediated Fe(II)′ formation from Fe(III)L in a simulated coastal water system were investigated and a comprehensive kinetic model was developed using citrate and fulvic acid as exemplar Fe-binding ligands. To simulate a coastal environment in laboratory experiments, Fe(III)L samples with various ligand/Fe ratios were incubated for 5 min to 1 week in seawater medium. At each ratio and incubation time, the rate of superoxide-mediated Fe(II)′ formation was determined in the presence of the strong Fe(II) binding ligand ferrozine by spectrophotometrically measuring the ferrous-ferrozine complex generated at a constant concentration of superoxide. The Fe(II)′ formation rate generally decreased with incubation time, as Fe(III)L gradually dissociated to form less reactive Fe(III) oxyhydroxide. However, when the ligand/Fe ratio was sufficiently high, the dissociation of Fe(III)L (and subsequent Fe precipitation) was suppressed and Fe(II)′ was formed at a higher rate. The rate of Fe(II)′ produced during the experiment was explained by the kinetic model. The model confirmed that both the ligand/Fe ratio and incubation time have a significant effect on the pathway via which Fe(II)′ is formed from Fe(III)-fulvic acid complexes.     

Fe2+ -F avoidance in silicates

Fe²⁺-F avoidance, reported in the literature in micas and amphiboles, can be accounted for by crystal field theory. The crystal field splitting parameter, Δ_O, of Fe²⁺ octahedrally coordinated to F^? is significantly smaller than its value when (OH)^? is the coordinating anion. Thus, the presence of Fe²⁺ is not favored at sites where F^? substitutes for (OH)^? due to smaller crystal field stabilization energy.     

57Fe mössbauer study of synthetic Fe3+-melilites

Synthetic Fe³⁺-melilites containing NaCaFe³⁺-Si₂O₇-, Ca₂Fe³⁺AlSiO₇- or Sr₂Fe³⁺AlSiO₇-components have been studied by ⁵⁷Fe Mössbauer spectroscopy. The spectrum of åkermanite containing an NaCaFe³⁺Si₂O₇-component consists of one doublet identified to belong to Fe³⁺ in T1 sites. The spectra of åkermanite and gehlenite containing Ca₂Fe³⁺ AlSiO₇- or Sr₂Fe³⁺ AlSiO₇-component consist of two doublets. The inner and outer doublets are identified to belong to Fe³⁺ in the less distorted T1 and that in the more distorted T2 sites, respectively. The area ratios of the spectra show that the site occupancy of Fe³⁺ (T1) in gehlenite is less than that in åkermanite in which the distribution of Fe³⁺ in T1 and T2 sites is apparently random. The different distributions can be explained in terms of competition between minimizing the deficiency in the electrostatic valence and the preference of Al for T1 sites which the isomer shift measurements show to be more ionic.     

Determination of [Fe2+]/[Fe3+]-ratios in arfvedsonite by Mössbauer spectroscopy

The Mössbauer absorption spectra of arfvedsonite are composed of three quadrupole doublets which are ascribed to Fe²⁺ in M₁ and M₂ sites and to Fe³⁺ in M₂ sites. The relative intensities of the resonances are a measure of the distribution of iron at the different sites, but it is necessary to correct for a difference between the recoil-free fractions. At room temperature [Fe²⁺] seems detected with an efficiency of only about 85% of that of [Fe³⁺]. Results of [Fe²⁺]/[Fe³⁺] determinations by Mössbauer spectroscopy and by wet chemical analysis of a series of arfvedsonite samples, separated from various rocks from the Ilimaussaq intrusion, south Greenland, are compared and agree reasonably well.     

The ferrozine method revisited: Fe(II)/Fe(III) determination in natural waters

The original ferrozine method has been modified to sequentially determine the Fe(II)/Fe(III) speciation in small volumes of fresh and marine water samples, at the submicromolar level. Spectrophotometric analyses of the Fe(II)–ferrozine complex are performed on a single aliquot before and after a reduction step with hydroxylamine. The procedure is calibrated using Fe(III) standards stable under normal conditions of analysis. It is shown also that the presence of high concentrations of dissolved NOM (natural organic matter) do not create any significant artifacts. The method was used to measure Fe(II) and Fe(III) depth distribution in salt marsh pore waters and in a stratified marine basin.     

Fe2+-Ti4+ charge transfer in stoichiometric Fe2+,Ti4+-minerals

Optical absorption spectra are presented for taramellite, traskite and neptunite, all of which have both Fe²⁺ and Ti⁴⁺ as major elements. The spectra of each of these minerals are dominated by a single, intense absorption band in the 415 to 460 nm region with 7000 to 9000 cm^?1 halfwidth. These transitions, assigned to Fe²⁺-Ti⁴⁺ intervalence charge transfer, showed little difference in intensity at 80 and 300 K and have molar absorptivities which range from ～100 to ～1300 M^?1 cm^?1. The Fe²⁺-Ti⁴⁺ absorptions in these standards generally compare well to other mineral spectra in which Fe²⁺ — Ti⁴⁺ intervalence absorption has previously been proposed with the exception of the most cited example, blue corundum.     

Cu and Fe chalcopyrite leach activation energies and the effect of added Fe

The leaching kinetics of chalcopyrite (CuFeS₂) concentrate in sulfuric acid leach media with and without the initial addition of Fe³⁺ under carefully controlled solution conditions (E_h 750 mV SHE, pH 1) at various temperatures from 55 to 85 °C were measured. Kinetic analyses by (i) apparent rate (not surface area normalised), and rate dependence using (ii) a shrinking core model and (iii) a shrinking core model in conjunction with Fe³⁺ activity, were performed to estimate the activation energies (E_a) for Cu and Fe dissolution.The E_a values determined for Cu and Fe leaching in the absence of added Fe³⁺ are within experimental error, 80 ± 10 kJ mol⁻¹ and 84 ± 10 kJ mol⁻¹, respectively (type iii analyses E_a are quoted unless stated otherwise), and are indicative of a chemical reaction controlled process. On addition of Fe³⁺ the initial Cu leach rate (up to 10 h) was increased and Cu was released to solution preferentially over Fe, with the E_a value of 21 ± 5 kJ mol⁻¹ (type ii analysis) suggestive of a transport controlled rate determining process. However, the rate of leaching rapidly decreased until it was consistently slower than for the equivalent leaches where Fe³⁺ was not added. The resulting E_a value for this leach regime of 83 ± 10 kJ mol⁻¹ is within experimental error of that determined in the absence of added Fe³⁺. In contrast to Cu release, Fe release to solution was consistent with a chemical reaction controlled leach rate throughout. The Fe release E_a of 76 ± 10 kJ mol⁻¹ is also within experimental error of that determined in the absence of added Fe³⁺. Where type (ii) and (iii) analyses were both successfully carried out (in all cases except for Cu leaching with added Fe³⁺, <10 h) the E_a derived are within experimental error. However, the type (iii) analyses of the leaches in the presence of added Fe³⁺ (>10 h), as compared to in the absence of added Fe³⁺, returned a considerably smaller pre-exponential factors for both Cu and Fe leach analyses commensurate with the considerably slower leach rate, suggestive of a more applicable kinetic analysis.XPS examination of leached chalcopyrite showed that the surface concentration of polysulfide and sulfate was significantly increased when Fe³⁺ was added to the leach liquor. Complementary SEM analysis revealed the surface features of chalcopyrite, most likely due to the nature of the polysulfide formed, are subtly different with greater surface roughness upon leaching in the absence of added Fe³⁺ as compared to a continuous smooth surface layer formed in the presence of added Fe³⁺. These observations suggest that the effect of Fe³⁺ addition on the rate of leaching is not due to the change in the chemical reaction controlled mechanism but due to a change in the available surface area for reaction.     

Temperature-dependent magnetic susceptibility behaviour of spinelloid and spinel solid solutions in the systems Fe2SiO4–Fe3O4 and (Fe,Mg)2SiO4–Fe3O4

The magnetic behaviour and Curie temperatures (T _C ) of spinelloids and spinels in the Fe₃O₄–Fe₂SiO₄ and Fe₃O₄–(Mg,Fe)₂SiO₄ systems have been determined from magnetic susceptibility (k) measurements in the temperature range –192 to 700 °C. Spinelloid II is ferrimagnetic at room temperature and the k measurements display a characteristic asymmetric hump before reaching a T _C at 190 °C. Spinelloid V from the Mg-free system is paramagnetic at room temperature and hysteresis loops at various low temperatures indicate a ferri- to superparamagnetic transition before reaching the T _{C .} The T _C shows a non-linear variation with composition between –50 and –183 °C with decreasing magnetite component (X _Fe3O₄). The substitution of Mg in spinelloid V further decreases T _C . Spinelloid III is paramagnetic over nearly the total temperature range. Ferrimagnetic models for spinelloid II and spinelloid V are proposed. The T _C of Fe₃O₄–Fe₂SiO₄ spinel solid solutions gradually decrease with increasing Si content. Spinel is ferrimagnetic at least to a composition of X _Fe3O₄=0.20, constraining a ferrimagnetic to antiferromagnetic transition to occur at a composition of X _Fe3O₄<0.20. A contribution of the studied ferrimagnetic phases for crustal anomalies on the Earth can be excluded because they lose their magnetization at relatively low temperatures. However, their relevance for magnetic anomalies on other planets (Mars?), where these high-pressure Fe-rich minerals could survive their exhumation or were formed by impacts, has to be considered.     

Short-range order of Fe2+ in sphalerite by 57Fe Mössbauer spectroscopy and magnetic susceptibility

An extensive study of natural and synthetic Fe-bearing sphalerites (Fe-content ranging from 0.005 afu to 0.250 afu) has been carried out through the combined investigations of the temperature dependence of the magnetic susceptibility and of the ⁵⁷Fe Mössbauer spectroscopic features. Magnetic susceptibility measurements evidence, in the low temperature regime, the presence of clustered Fe even in the most diluted samples, whereas all the Mössbauer spectra are described in terms of variable proportions of three components, namely one single and two doublets absorption, centred at the same isomer shift, relative to Fe ions and to different Fe clusters, respectively. The comparison of all the experimental results points out a self-affinity of Fe ions in sphalerite favoured by the superexchange interaction, which stabilises the formation of clusters even in diluted samples and may be related to both macroscopic inhomogeneous distribution and crystal zoning.     

Dissolution rates of metals in Fe oxides: implications for sampling ferruginous materials with significant relict Fe oxides

A study of the pattern of dissolution of synthetic and natural Fe oxides in 6 M HCl indicates that the rate of element release from synthetic Fe oxides is strongly influenced by mineralogy and the level of element incorporation. Synthetic maghemite (γ-Fe₂O₃) samples are subject to much more rapid dissolution than goethite (FeOOH) and hematite (α-Fe₂O₃). In samples dominated by hematite and maghemite, Cu, Zn and particularly Pb, in comparison to Fe, are preferentially released during the early stages of dissolution. Similar patterns are apparent from the dissolution of hematite- and maghemite-dominated samples derived from natural gossan. Comparison of XRD scans with data from the dissolution of natural gossan samples transformed by incremental heating to hematite- and maghemite-dominated assemblages suggests that the degree of crystallinity may also be a significant factor in the release of elements incorporated in the Fe oxides. Ferruginous materials made up of varying proportions of goethite, hematite, maghemite, kaolinite and quartz are important sampling materials in a range of regolith environments. These are products of complex chemical and mechanical mobilization over long periods of geological time. If the patterns of Fe oxide dissolution in 6 M HCl and the release of incorporated metals reflect stability in such weathering regimes, knowledge of the retention characteristics of incorporated metals in different Fe oxide phases, as indicated by this study, will be useful in the planning and interpretation of geochemical surveys in such regions.