Structure and stability of the Fe(II)–Fe(III) green rust “fougerite” mineral and its potential for reducing pollutants in soil solutions

Fe(II)–Fe(III) layered double hydroxysalt green rusts, GRs, are very reactive compounds with the general formula, [Fe^II_(1−x) Fe^III_x (OH)₂]^x+·[(x/n) Aⁿ⁻·(m/n) H₂O]^x−, where x is the ratio Fe^III/Fe_tot, and reflects the structure in which brucite-like layers alternate with interlayers of anions Aⁿ⁻ and water molecules. Two types of crystal structure for GRs, GR1 and GR2, represented by the hydroxychloride GR1(Cl⁻) and the hydroxysulphate GR2(SO₄²⁻) are distinguished by X-ray diffraction due to different stacking. By analogy with GR1(Cl⁻) the structure of the fougerite GR mineral, [Fe^II_(1−x) Fe^III_x (OH)₂]^x+·[x OH⁻·(1−x) H₂O]^x-  Fe(OH)_(2+x)·(1−x) H₂O, is proposed displaying interlayers made of OH⁻ ions and water molecules (in situ deprotonation of water molecules is necessary for explaining the flexibility of its composition). The space group of mineral GR1(OH⁻) would be R3̄m, with lattice parameters a≅0.32 and c≅2.25 nm. Stability conditions and the E_h-pH diagram of Fe(OH)_(2+x) (the water molecules are omitted) are determined from hydromorphic soil solution equilibria with GR mineral in Brittany (France). Computed Gibbs free energies of formation from soil solution/mineral equilibrium fit well with a regular solid solution model: μ°[Fe(OH)_(2+x)]=(1−x) μ°[Fe(OH)₂]+x μ°[Fe(OH)₃]+RT [(1−x) ln (1−x)+x ln x]+A₀ x (1−x), where μ°[Fe(OH)₂]=−492.5 kJ mol⁻¹, μ°[Fe(OH)₃]=−641 kJ mol⁻¹ and A₀=−243.9 kJ mol⁻¹ at the average temperature of 9±1°C. The upper limit of occurrence of GR mineral at x=2/3, i.e. Fe₃(OH)₈, is explained by its unstability vs. α-FeOOH and/or magnetite; Fe(OH)₃ is thus a hypothetical compound with a GR structure which cannot be observed. These thermodynamic data and E_h-pH diagrams of Fe(OH)_(2+x) can be used most importantly to predict the possibility that GR minerals reduce some anions in contaminated soils. The cases of NO₃⁻, Se(VI) or Cr(VI) are fully illustrated.     

Influence of hydrogen on Fe–Mg interdiffusion in (Mg,Fe)O and implications for Earth’s lower mantle

Interdiffusion of Fe and Mg in (Mg,Fe)O has been investigated experimentally under hydrous conditions. Single crystals of MgO in contact with (Mg_0.73Fe_0.27)O were annealed hydrothermally at 300 MPa between 1,000 and 1,250°C and using a Ni–NiO buffer. After electron microprobe analyses, the dependence of the interdiffusivity on Fe concentration was determined using a Boltzmann–Matano analysis. For a water fugacity of ∼300 MPa, the Fe–Mg interdiffusion coefficient in Fe _x Mg_1−x O with 0.01 ≤ x ≤ 0.25 can be described by with and C = −80 ± 10 kJ mol⁻¹. For x = 0.1 and at 1,000°C, Fe–Mg interdiffusion is a factor of ∼4 faster under hydrous than under anhydrous conditions. This enhanced rate of interdiffusion is attributed to an increased concentration of metal vacancies resulting from the incorporation of hydrogen. Such water-induced enhancement of kinetics may have important implications for the rheological properties of the lower mantle.

Cation exchanged Fe(II) and Sr compared to other divalent cations (Ca, Mg) in the bure Callovian–Oxfordian formation: Implications for porewater composition modelling

Iron and Sr bearing phases were thoroughly investigated by means of spectrometric and microscopic techniques in Callovian–Oxfordian (COX) samples originating from the ANDRA Underground Research Laboratory (URL) in Bure (France). Strontium was found to be essentially associated with celestite, whereas Fe was found to be distributed over a wide range of mineral phases. Iron was mainly present as Fe(II) in the studied samples (∼93% from Mössbauer results). Most of the Fe(II) was found to be in pyrite, sideroplesite/ankerite and clay minerals. Iron(III), if present, was associated with clay minerals (probably illite, illite-smectite mixed layer minerals and chlorite). No Fe(III) oxy(hydro)xide could be detected in the samples. Strontianite was not observed either. Based on these observations, it is likely that the COX porewater is in equilibrium with the following carbonate minerals, calcite, dolomite and ankerite/sideroplesite, but not with strontianite. It is shown that this equilibrium information can be combined with clay cation exchange composition information in order to give direct estimates or constraints on the solubility products of the carbonate minerals dolomite, siderite and strontianite. As a consequence, an experimental method was developed to retrieve the cation exchanged Fe(II) in very well preserved COX samples.     

Effect of confining pressure on the diffusion of HTO, 36Cl− and 125I− in a layered argillaceous rock (Opalinus Clay): diffusion perpendicular to the fabric

The through- and out-diffusion of HTO, ³⁶Cl⁻ and ¹²⁵I⁻ in Opalinus Clay, an argillaceous rock from the northern part of Switzerland, was studied under different confining pressures between 4 and 15 MPa. The direction of diffusion and the confining pressure were perpendicular to the bedding. Confining pressure had only a small effect on diffusion. An increase in pressure from 4 to 15 MPa resulted in a decrease of the effective diffusion coefficient of ∼20%. Diffusion accessible porosities were not measurably affected. The values of the effective diffusion coefficients, D_e, ranged between (5.6±0.4)×10⁻¹² and (6.7±0.4)×10⁻¹² m² s⁻¹ for HTO, (7.1±0.5)×10⁻¹³ and (9.1±0.6)×10⁻¹³ m² s⁻¹ for ³⁶Cl⁻ and (4.5±0.3)×10⁻¹³ and (6.6±0.4)×10⁻¹³ m² s⁻¹ for ¹²⁵I⁻. The rock capacity factors, α, measured were circa 0.14 for HTO, 0.040 for ³⁶Cl⁻ and 0.080 for ¹²⁵I⁻. Because of anion exclusion effects, anions diffuse slower and exhibit smaller diffusion accessible porosities than the uncharged HTO. Unlike ³⁶Cl⁻, ¹²⁵I⁻ sorbs weakly on Opalinus Clay resulting in a larger rock capacity factor. The sorption coefficient, K_d, for ¹²⁵I⁻ is of the order of 1–2×10⁻⁵ m³ kg⁻¹. The effective diffusion coefficient for HTO is in good agreement with values measured in other sedimentary rocks and can be related to the porosity using Archie's Law with exponent m=2.5.     

Evidence for xenolith–host basalt interaction from chemical patterns in Fe–Ti-oxides from mafic granulite xenoliths of the Bakony–Balaton Volcanic field (W-Hungary)

We investigate the effects of xenolith–host basalt interaction on lower crustal mafic granulite xenoliths from the Central Pannonian Basin. The xenoliths are devoid of any signs of melting, nevertheless various phenomena are identified, which indicate that the original mineralogy and chemistry of the xenoliths was modified during interaction with the host basalt. The rock-forming silicates are only slightly affected by alteration, but the Fe–Ti-oxides are overprinted to a significant extent. Complex chemical zoning patterns are detected using high-resolution element mapping in ilmenites and in lamellar titanomagnetite–ilmenite intergrowths. The chemical alteration of the Fe–Ti-oxides was diffusion-controlled and, hence, time and temperature dependent. On the basis of diffusion profiles in titanomagnetite we estimate the duration of xenolith–host basalt interaction to be at least 9–20 h. This is comparable to the time necessary for the ascent of the host basalt to the surface. It is too short to reflect alteration during granulite facies metamorphism in the deep crust. The chemical alteration of the titanomagnetite thus reflects the total duration of the xenolith–host basalt interaction.     

Carbon and hydrogen isotopic reversals in deep basin gas: Evidence for limits to the stability of hydrocarbons by Burruss and Laughrey (Organic Geochemistry 41, 1285–1296) – Discussion

This discussion reevaluates the data provided by Burruss and Laughrey (2010) (Carbon and hydrogen isotopic reversals in deep basin gas: Evidence for limits to the stability of hydrocarbons. Organic Geochemistry 41, 1285–1296). It indicates that gas diffusive migration plays an important role in regulating the isotopic reversals in samples from the Silurian and Ordovician formations in the Appalachian Basin. Carbon and hydrogen isotopic reversals in deep basin gas cannot be attributed to the stability of hydrocarbons in shale-gas and tight-sand-gas accumulations, if gas diffusive migration in the subsurface is not considered.