Hybrid films consisting of Sumecton SA smectite (SSA) and a diacetylenic two-photon absorptive dye; 1,4-bis(2,5-dimethoxy-4-{2-[4-(N-methyl)pyridinium]ethenyl}phenyl) butadiyne triflate (MPPBT) were fabricated. The MPPBT-clay composites were prepared by the cation exchange method in a dimethylsulfoxide (DMSO)-water mixed solvent. A low-light-scattering film, suitable for use in optical devices, was obtained by filtration of the dispersion of the MPPBT-clay composites. Estimation of the two-photon absorption cross-section (σ(2)) by means of the open-aperture Z-scan technique was performed using the present film. The σ(2) value of MPPBT in the film fabricated at the MPPBT loading levels vs. 20% cation exchange capacity was 1030 GM (1 GM= 1 × 1050 cm4 s photon−1 molecule−1) at an excitation wavelength of 800 nm. The value was 1.3 times greater than the maximum value of the σ(2) of MPPBT diss lved in DMSO with ut clay.

Todorokite is a common Mn oxide mineral in terrestrial and ocean-floor environments, and it is commonly synthesized from layered Na-buserite. Pyrophosphate, which is known to form strong complexes with Mn(III) at a pH range of 1–8, was added to a suspension of Na-buserite in order to sequester the available Mn(III) in Na-buserite. No Mn(III)-pyrophosphate complex was formed in solution at pH 10, and the treated Na-buserites were converted completely to todorokite. Significant transformation reductions were observed when Na-buserite was treated with pyrophosphate solution at pH 7. The presence of Mn(III) within the MnO6 octahedral sheets of Na-buserite is critical for the transformation from layered buserite to tunnel-structured todorokite at atmospheric pressure. At lower pH, two effects are combined to reduce the amount of Mn(III) in the layers: (1) the complexing power of pyrophosphate is increased; and (2) the transformation from Na-buserite to H-birnessite, which is concomitant with the migration of Mn(III) from layers to the interlayer, and the partial disproportionation of Mn(III). The results showed that Mn(III) played a key role in the transformation of layered Na-buserite to tunnel-structured todorokite at atmospheric pressure.

The behavior of mineral mixtures can be significantly different from the behavior of the individual components of the mixture due to differences between the mechanical and chemical properties of the individual minerals, and their ensuing effects on interparticle interactions and fabric formation. This study examines mixtures of kaolinite and calcium carbonate at different mass fractions using sedimentation, viscosity, and liquid-limit tests. These macroscale tests represent a wide range of solid-volume fractions and strain levels, with emphasis on high water-content conditions to magnify the effects of electrical forces. The results demonstrate that interparticle interactions depend on mineral surface-fluid effects, particle geometry, relative particle size, and solids content. With small solids contents, the kaolinite/calcium carbonate mixture behavior is a function of electrostatic interactions between oppositely charged mineral particles that promote flocculation; however, with large solids contents, the specific surface area of the minerals is the controlling factor. These results are relevant to many natural soil environments and to the possible development of engineered mineral mixtures for industrial applications.

Anisotropy in clay-rich sedimentary rocks is receiving increasing attention. Seismic anisotropy is essential in the prospecting for petroleum deposits. Anisotropy of diffusion has become relevant for environmental contaminants, including nuclear waste. In both cases, the orientation of component minerals is a critical ingredient and, largely because of small grain size and poor crystallinity, the orientation distribution of clay minerals has been difficult to quantify. A method is demonstrated that relies on hard synchrotron X-rays to obtain diffraction images of shales and applies the crystallographic Rietveld method to deconvolute the images and extract quantitative information about phase fractions and preferred orientation that can then be used to model macroscopic physical properties. The method is applied to shales from European studies which investigate the suitability of shales as potential nuclear waste repositories (Meuse/Haute-Marne Underground Research Laboratory near Bure, France, and Benken borehole and Mont Terri Rock Laboratory, Switzerland). A Callovo-Oxfordian shale from Meuse/Haute-Marne shows a relatively weak alignment of clay minerals and a random distribution for calcite. Opalinus shales from Benken and Mont Terri show strong alignment of illite-smectite, kaolinite, chlorite, and calcite. This intrinsic contribution to anisotropy is consistent with macroscopic physical properties where anisotropy is caused both by the orientation distribution of crystallites and high-aspect-ratio pores. Polycrystal elastic properties are obtained by averaging single crystal properties over the orientation distribution and polyphase properties by averaging over all phases. From elastic properties we obtain anisotropies for p waves ranging from 7 to 22%.

The provenance of clays in shaley intervals across the Permian-Triassic boundary (PTB) in the Xiakou section was investigated by X-ray diffraction (XRD), differential scanning calorimetry (DSC), and scanning electron microscopy (SEM), and the results suggest that the layers have three different provenances. The layer P267-b has a loose texture with an oriented arrangement of detrital clay particles, consisting mainly of illite and minor chlorite with irregular outlines or ragged edges. The dehydroxylation reaction of the clays in this layer is characterized by an intense overlapping endothermic effect at ∼600°C, produced by mixed-layer illite-smectite (I-S) consisting of a mixture of cis-vacant (cv)and trans-vacant (tv) octahedral sheets derived from weathering of detrital illite. Layer P259-b shows a more condensed texture with a dark color, and is composed mainly of I-S and minor illite and chlorite. Evidence for alteration of detrital materials to clay mineral aggregates was observed under SEM. Similar to layer P267-b, an intense dehydroxylation reaction occurs at ∼600°C, indicating clays consisting of a mixture of tv and cv sheets and, therefore, that the sediments were derived from a mixture of terrigenous and volcanic sources, combining the texture and the clay-mineral composition of those sediments. However, the undisturbed lamination and relatively small grain size in this bed indicate a low-energy depositional environment. The clay-mineral compositions of the other layers are mainly of I-S with minor amounts of illite and chlorite. Their endothermic dehydroxylation reaction, however, occurs mainly at ∼660°C, indicating that cv sheets are dominant in the clays, and thus, are derived from smectites of volcanic origin. Observations by SEM show that clay minerals grow at the expense of detrital materials, confirming the diagenetic alteration of volcanic ashes in marine sediments. Illite and chlorite are the detrital clay minerals in the clay layers across the PTB in the Xiakou section. The presence of detrital illite and chlorite in the sediments means that an arid climate prevailed in the region during the end-Permian and early Triassic period.

The degree of preferred orientation of mineral grains in powder X-ray diffraction (XRD) samples prepared by standard techniques has been evaluated by means of a correction model implemented in the Rietveld program, BGMN. It is demonstrated that neither front- nor side-loading of mineral powders obtained by wet grinding in a McCrone micronizing mill yield powder mounts with randomly oriented particles. Despite fine grinding, the primary sizes and shapes of mineral grains contained in multi-phase samples influence the degree of preferred orientation in XRD powder mounts. Two minerals, both of platy habit, were found to show different degrees of preferred orientation in front- and side-loaded samples. In contrast to these methods of sample preparation, the spray-drying technique yielded perfect randomness of the particles. The experiments on artificial mineral mixtures demonstrate that the model applied can effectively correct for preferred orientation allowing reliable Rietveld quantitative phase analysis of moderately textured samples prepared by standard techniques.

The sorption of nitrate ions on calcined hydrotalcite-type compounds at 550°C (HT550), 650°C (HT650), and 850°C (HT850) from pure water solution at 25°C has been studied. The influence of the temperature was also investigated for the sample calcined at 850°C by studying the sorption process at 10 and 40°C. The experimental sorption data points were fitted to the Langmuir equation in order to calculate the sorption capacities (Xm) of the samples; Xm values range from 61.7 g kg−1 (HT550 at 25°C) to 147.0 g kg−1 (HT850 at 40°C). The values for the removal efficiency (R) obtained ranged from 70.5% for HT550 at 25°C to 99.5% for HT850 at 40°C. The sorption experiments showed that the greater the calcination temperature (850°C), the more effective the removal of nitrate. The increase in the temperature from 10 to 40°C for sample HT850 also tends to increase the sorption of nitrate from 63.3 g kg−1 to 147 g kg−1 and the corresponding removal efficiency from 71.5 to 99.5%.

Stacking disorder in celadonite, a dioctahedral mica with Fe and Mg as major octahedral cations and which generally adopts the 1M stacking sequence, was investigated mainly by using transmission electron microscopy (TEM). The selected-area electron diffraction patterns with 0kl reflections along the [100] beam direction correspond to the 1M stacking but those along the [110], $\left[1\overline{1}0\right]$\$\end{document}, [010], [310], and $\left[3\overline{1}0\right]$\$\end{document} directions are frequently streaked along the [001]* direction or contain extra spots from twinned domains. Three-dimensional stacking analyses using sets of two high-resolution TEM images along different directions of the same area of one crystal indicate that all stacking faults involve only 180° layer rotations. These stacking faults produce greater peaks of 0kl reflections than expected in powder X-ray diffraction (XRD) patterns. Simulation of the XRD patterns indicated that 180° layer rotations occur at >10% of total interlayer regions in one celadonite specimen. The interlayer region of celadonite is characterized by a near-zero ditrigonal rotation angle, a small surface corrugation of the basal oxygen plane, and a small amount of Al substitution in the tetrahedral sheets. These features suggest that there is no preference for any of the six stacking angles around the interlayer region. The abundance of 180° layer rotation rather than ±60° and ±120° in the present specimens may be related to their ribbon-like morphologies elongated along the a axis.

Due to the increased importance of bionanocomposites, protamine and papain proteins were adsorbed on Na+- and on Cs+-exchanged saponite from aqueous solution. Protein analysis of equilibrium solutions and thermogravimetric analyses of biocomposites were used to prepare adsorption isotherms. Based on the isotherm shape, and on the amounts of protein adsorbed and the amounts of Na+ and Cs+ released, the initial protein sorption apparently was due to ion exchange. Additional sorbed protein was weakly retained and could be removed by washing with water. From ion exchange, the average charge of the protamine adsorbed was estimated to be +13.1 to +13.5. Similar papain measurements could not be made due to partial decomposition. Quantitatively, protamine was adsorbed at levels up to 400 mg/g on Na+-saponite and 200 mg/g on Cs+-saponite. The maximum protamine adsorption was 650 to 700 mg/g for Na+-saponite and 350–400 mg/g for Cs+-saponite. Protamine was sorbed to edge surfaces and the basal spacing of the interlamellar region of saponite was 1.75 nm. Protamine displaced only 36% of the Cs+ in Cs+-saponite and expanded the interlamellar region by 36% for a basal spacing of 1.6 nm. Papain sorption to Na+-saponite occurred by a two-step process: (1) adsorption to saponite particle external surfaces followed, (2) by partial intercalation. Quantitatively, Papain was adsorbed up to 100 mg/g for Na+-and Cs+-saponite. Greater initial papain concentrations resulted in a 450 mg/g maximum for Na+-saponite, but no increase above 100 mg/g for Cs+-saponite. Papain apparently only sorbed to external Cs+-saponite surfaces that were estimated to be 33–40 m2/g. Step-wise thermal decomposition of the saponite-protein composites occurred between 300 and 800°C.

Late Miocene clayey sediments were deposited in lake-margin and shallow-lake environments of the southeastern Central Anatolian Volcanic Province (CAVP). Yellow to red mudstone, alternating with thin beds of conglomerate and sandstone in the Mustafapaşa Formation, is overlain by altered white Cemilköy ignimbrite. Grain size fines upward in each sequence (conglomerate, sandstone, and mudstone). The occurrence of reddish coloration upward, ripple marks, desiccation cracks, plant rootlets and remnants, and the development of initial-stage paleosols in association with smectite reveal that the area underwent alternating periods of siliciclastic and volcaniclastic sediment supply (wet) and drying. Micromorphologically, the development of spongy smectite in mudstone of the Mustafapaşa Formation and vermiform kaolinite in the Cemilköy ignimbrite on resorbed detrital feldspar and devitrified glass reveals in situ precipitation driven by dissolution and precipitation mechanisms. In addition, alteration of these sediments may have resulted in the depletion of soluble alkaline elements, such as Ca, Na, and K, from the ignimbrite downward into the Mustafapaşa Formation. Alternatively, the leaching of these elements — due to the hydrologically open system of the lake environment — may have resulted in the enhancement of Al+Fe/Si-favored precipitation of kaolinite in an acidic environmental condition, namely, of the altered Cemilköy ignimbrite at the top of the profile of the Mustafapaşa Formation, and of smectite in an alkaline setting within lower-level sediments where carbonate minerals were lacking. The coexistence of smectite with accessory illite indicates that illitization occurred via release of K and Al during excess desorption of feldspar. Large Ni and Co values in mudstone samples, and Fe oxidized and partly chloritized pyroxene and hornblende, indicate that the basin was also affected by ophiolite-related supply.

To further elucidate adsorption-to-partition transitional mechanisms which have been proposed previously for organo-bentonites with different surfactant loadings, the structural characteristics of interlayer surfactant aggregates on organo-bentonite with different surfactant cetyltrimethylammonium bromide loading levels (0.20–2.56 times cation exchange capacity, CEC) have been investigated by in situ X-ray diffraction (XRD) and Fourier TransformInfrared (FTIR) spectroscopy. The sorption properties and the structure of the clay interlayers changed according to the type of surfactant, the surfactant loading level, and the state of hydration in the clays. Based on the sorption of nitrobenzene, phenol, and aniline to organobentonites, the contaminant sorption coefficients (Ksf), normalized with the organic carbon content, show a remarkable dependence on surfactant loading levels. The Ksf values first increased with surfactant loading until reaching a maximum at 1.0 to 1.2 times the CEC, and then decreased. According to the theoretical calculation of the volume fractions relating to the interlamellar space, the interlamellar microenvironment became a more hydrophobic medium, contributing to the dissolution of organic contaminants, as the surfactant loading increased from 0.20 to 2.56 times the CEC. However, the increase in packing density (ρ) for the intercalates, and induced steric hindrances both affect the result in terms of a reduction in the accessible free space where the organic contaminants can be located, which might be a negative factor in the sorption capacity.

The total specific surface area (TSSA) and smectitic layer charge (Qs) calculated from the structural formulae and unit-cell dimensions of 12 pure smectite samples were used as a reference in the design and evaluation of TSSA and Qs measurement techniques based on cation exchange capacity (CEC), H2O retention at 47% RH, and ethylene glycol monoethyl ether (EGME) retention. A thermogravimetric analysis-mass spectrometry (TGA-MS) technique was used to study the release of H2O from smectite on heating, and to introduce a correction for H2O remaining in the smectite after heating to 110°C, because the sample weight at this temperature has been used routinely as a reference in CEC and EGME sorption measurements. A temperature of 200°C was found to be the optimum reference for such measurements.

A good agreement between Qs from the structural formula and from CEC was obtained when this correction was applied. The TSSA of smectite was measured with similar accuracy (mean error of ±5–7%) by three techniques: (1) using mean H2O coverage; (2) using mean EGME coverage; and (3) using a combination of H2O coverage and CEC. A reduction of the mean error from 5–7% to 4% can be obtained by averaging these measurements, and a further reduction to 3% by introducing corrections for the dependence of H2O and EGME coverage on layer charge. The study demonstrates that Ca2+-smectite samples at 47% RH have H2O contents corresponding to 88–107% of the theoretical mass of a monolayer and offers an explanation of this variation.

Sub-micrometer clay particles are of interest in clay-polymer applications, especially when transparency is important. The scattering of light can be reduced by the adjustment of the refractive index (RI) of the clays to that of the matrix. In this study, the RI of sub-micrometer illite particles was changed by treatment with 5 M HCl for treatment times ranging between 2 and 24 h. The dissolution of Fe leads to a decrease in the RI of illite from 1.587 for the unaltered material to 1.502 after 24 h. The layer structure of the illite particles was preserved during the treatment. The RI of the sub-micrometer illite particles was determined by means of a photospectrometer measuring the light intensity passing through suspensions containing the clay particles, with varying refractive indices.

High-charge nontronites were synthesized at 75, 90, 100, 110, 125, and 150°C from a silicoferrous starting gel with Si2FeNa2O6.nH2O composition. This gel was oxidized in contact with air and then hydrothermally treated, for a period of 4 weeks, under equilibrium water pressure. The synthesized nontronites were similar to each other, regardless of the synthesis temperature. Their structural formula, obtained from chemical analysis, X-ray diffraction (XRD), and Fourier transform infrared (FTIR), Mössbauer, and X-ray absorption fine structure spectroscopies is: $\left({\text{Si}}_{3.25}{\text{Fe}}_{0.75}^{3+}\right){\text{Fe}}_2^{3+}{\text{O}}_{10}{\left(\text{OH}\right)}_2{\text{Na}}_{0.75}$$\left( {{\rm{S}}{{\rm{i}}_{3.25}}{\rm{Fe}}_{0.75}^{3 + }} \right){\rm{Fe}}_2^{3 + }{{\rm{O}}_{10}}{\left( {{\rm{OH}}} \right)_2}{\rm{N}}{{\rm{a}}_{0.75}}$. A strictly ferric end-member of the nontronite series was therefore synthesized for the first time. The uncommon chemistry of the synthesized nontronites, notably the high level of Fe-for-Si substitution, induced particular XRD, FTIR, and differential thermal analysis-thermogravimetric analysis data. The ethylene glycol expandability of the synthetic nontronites was linked to their crystallinity and depended on the nature of the interlayer cation, moving from smectite to vermiculite-like behavior. As the synthesis temperature increased, the crystallinity of the synthesized clays increased. The nontronite obtained at 150°C had the ‘best crystallinity’, which cannot be improved by increasing synthesis time or temperature.

Miocene rifting and associated rhyolitic (K-rich) volcanism resulted in the deposition of pyroclastic material in the central Simav graben, near Karacaderbent, Turkey. The pyroclastics were deposited in a lacustrine environment, altered to clinoptilolite-rich tuffs and cross-cut by several transform faults along which hydrothermal fluids circulated. Petrography and quantitative phase analysis by X-ray diffraction show that the Karacaderbent tuff consists mainly of the diagenetic products clinoptilolite, opal CT, smectite, and celadonite. Electron microprobe analyses and cation exchange capacity (CEC) measurements confirm the predominance of K-rich clinoptilolite. Near fault zones, clinoptilolite was replaced by authigenic opal CT and alkali feldspar, and the remaining clinoptilolite was enriched in Na. Silicification around fault zones was confirmed by X-ray fluorescence. Zeolitization of K-rich rhyolitic starting materials took place under mildly alkaline, low-salinity conditions, probably in a closed hydrologic system. The subsequent hydrothermal alteration along faults had only a minor impact. The homogeneous nature, large (74–87 wt.%) clinoptilolite content, large CEC, and K-rich composition of the deposit favor exploitation of this material for applications in agriculture, horticulture, and waste-water purification; as feed additives; and as pozzolans for cement production.

River-dominated delta areas are primary sites of active biogeochemical cycling, with productivity enhanced by terrestrial inputs of nutrients. Particle aggregation in these areas primarily controls the deposition of suspended particles, yet factors that control particle aggregation and resulting sedimentation in these environments are poorly understood. This study was designed to investigate the role of microbial Fe(III) reduction and solution chemistry in aggregation of suspended particles in the Mississippi Delta. Three representative sites along the salinity gradient were selected and sediments were collected from the sediment-water interface. Based on quantitative mineralogical analyses 88–89 wt.% of all minerals in the sediments are clays, mainly smectite and illite. Consumption of ${\text{SO}}_4^{2-}$\$\end{document} and the formation of H2S and pyrite during microbial Fe(III) reduction of the non-sterile sediments by Shewanella putrefaciens CN32 in artificial pore water (APW) media suggest simultaneous sulfate and Fe(III) reduction activity. The pHPZNPC of the sediments was ⩽3.5 and their zeta potentials at the sediment-water interface pH (6.9–7.3) varied from −35 to −45 mV, suggesting that both edges and faces of clay particles have negative surface charge. Therefore, high concentrations of cations in pore water are expected to be a predominant factor in particle aggregation consistent with the Derjaguin-Landau-Verwey-Overbeek (DLVO) theory. Experiments on aggregation of different types of sediments in the same APW composition revealed that the sediment with low zeta potential had a high rate of aggregation. Similarly, addition of external Fe(II) (i.e. not derived from sediments) was normally found to enhance particle aggregation and deposition in all sediments, probably resulting from a decrease in surface potential of particles due to specific Fe(II) sorption. Scanning and transmission electron microscopy (SEM, TEM) images showed predominant face-to-face clay aggregation in native sediments and composite mixtures of biopolymer, bacteria, and clay minerals in the bioreduced sediments. However, a clear need remains for additional information on the conditions, if any, that favor the development of anoxia in deep- and bottom-water bodies supporting Fe(III) reduction and resulting in particle aggregation and sedimentation.

The assignments of OH-bending bands in the infrared (IR) spectra of dioctahedral smectites (montmorillonites, ferruginous smectites, and nontronites) have been revisited using a cation mass-valence sum (CM-VS) approach to quantify octahedral cation occupancy. The CM-VS approach enabled prediction of OH-bending band positions (in wavenumbers) related to OH-sharing octahedral cation pairs that had valence sums of 4 and 5, and cation masses associated with Fe(II) and Mg. Application of rules for the relationship enabled determination of the location of OH-sharing octahedral cation pairs containing Mg and Fe(II) for which previous assignments have been considered controversial, e.g. Fe(III)Mg-OH and MgMg-OH, or for which assignments have been missing due to lack of spectroscopic evidence, e.g. AlFe(II)-OH, Fe(III)Fe(II)-OH, Fe(II)Mg-OH, and Fe(II)Fe(II)-OH. Examples of these bands from several natural ferruginous smectites and nontronites are discussed. Quantification of IR spectra was used to develop a better understanding of the octahedral cation occupancy of this important class of Fe(III)-enriched smectites. While Fe(II) contents may be somewhat overestimated by the IR technique, those for four of the six ferruginous smectites studied here agree well with data from Mössbauer spectroscopy.

The pH of aqueous bentonite suspensions is known to be influenced by carbonates present even in minor amounts. On the other hand, at high solid:liquid ratios (at standard pH measurement conditions: 2% w/w suspension), the type of exchangeable cation in the smectite is also known to determine pH (particularly Na+ or Ca2+). By cation-exchange tests we proved that exchanging the Ca2+ for Na+ results in an increase in the pH. However, this increase in pH was only found if excess salts were removed from the system (by washing or dialysis, respectively). The effect of the type of exchangeable cation can, at least partially, be explained by hydrolysis of Ca2+. On the other hand, a pronounced alkalinity of Na bentonites is observed which can, at least partially, be attributed to the hydrolysis of montmorillonite (Na+ is exchanged for H+ of water). The increase in the volume of the Stern layer, caused by increasing the degree of delamination, is also suggested to play a role. H+ and Na+ are concentrated in the Stern layer. Hence, increasing the Stern layer volume decreases the amount of H+ and Na+ in solution and thus increases pH. Unfortunately, both processes, montmorillonite hydrolysis and delamination, depend on the ionic strength. Distinguishing the processes quantitatively, therefore, is an analytical challenge, and impossible based on the data presented here.

To model the pore-water chemistry of clays and clay stones, all of the above-mentioned processes have to be considered. It is possible that other reactions, not identified in the present work, contribute toward the pH values of aqueous bentonite suspensions.

Mixed FeIIFeIII hydroxides, commonly referred to as ‘green rusts’ (GRs), are important reactive phases in both man-made and natural geochemical systems. Determinations of the standard Gibbs energy of formation of GRs are needed to understand and predict the occurrence and possible reactions of GRs in these systems. Slow acid titration of crystalline green rust sulfate (${\text{GR}}_{{\text{SO}}_4}$\$\end{document}) with the formation of magnetite was used as a novel method to determine the standard Gibbs energy of formation of ${\text{GR}}_{{\text{SO}}_4}$\$\end{document}, ${\text{Δ}}_{\text{f}}{G}^{\text{o}}\left({\text{GR}}_{{\text{SO}}_4}\right)$\$\end{document}. Aqueous suspensions of ${\text{GR}}_{{\text{SO}}_4}$\$\end{document}, with pH slightly >8, were titrated slowly with 1 M H2SO4 until pH = 3 under strict anoxic conditions. Powder X-ray diffraction and Mössbauer analysis revealed that magnetite was the only solid phase formed during the initial part of the titration, where the equilibrium pH was maintained above 7.0. The ratio of Fe2+ release to consumption of protons confirmed the stoichiometry of dissolution of ${\text{GR}}_{{\text{SO}}_4}$\$\end{document} and the formation of magnetite at equilibrium conditions. The estimate of the absolute value of ${\text{Δ}}_{\text{f}}{G}^{\text{o}}\left({\text{GR}}_{{\text{SO}}_4}\right)$\$\end{document} was −3819.43±6.44 kJ mol−1 + y × [ΔfGo(H2O(1))], where y is the number of interlayer water molecules per formula unit. The logarithm of the solubility product, log Ksp, was estimated to be −139.2±4.8 and is invariable with y. Using the new value for ${\text{Δ}}_{\text{f}}{G}^{\text{o}}\left({\text{GR}}_{{\text{SO}}_4}\right)$\$\end{document}, the reduction potentials of several ${\text{GR}}_{{\text{SO}}_4}$\$\end{document}-Fe oxide couples were evaluated, with the ${\text{GR}}_{{\text{SO}}_4}$\$\end{document}-magnetite half cell showing the smallest redox potential at pH 7 and free ion activities of 10−3.