Explore the vast range of titles available.

Americium is a highly radioactive actinide element found in used nuclear fuel. Its adsorption on aluminum (hydr)oxide minerals is important to study for at least two reasons: (i) aluminum (hydr)oxide minerals are ubiquitous in the subsurface environment and (ii) bentonite clays, which are proposed engineered barriers for the geologic disposal of used nuclear fuel, have the same ≡AlOH sites as aluminum (hydr)oxide minerals. Surface complexation modeling is widely used to interpret the adsorption behavior of heavy metals on mineral surfaces. While americium sorption is understudied, multiple adsorption studies for europium, a chemical analog, are available. In this study we compiled data describing Eu(III) adsorption on three aluminum (hydr)oxide minerals—corundum (α-Al2O3), γ-alumina (γ-Al2O3) and gibbsite (γ-Al(OH)3)—and developed surface complexation models for Eu(III) adsorption on these minerals by employing diffuse double layer (DDL) and charge distribution multisite complexation (CD-MUSIC) electrostatic frameworks. We also developed surface complexation models for Am(III) adsorption on corundum (α-Al2O3) and γ-alumina (γ-Al2O3) by employing a limited number of Am(III) adsorption data sourced from literature. For corundum and γ-alumina, two different adsorbed Eu(III) species, one each for strong and weak sites, were found to be important regardless of which electrostatic framework was used. The formation constant of the weak site species was almost 10,000 times weaker than the formation constant for the corresponding strong site species. For gibbsite, two different adsorbed Eu(III) species formed on the single available site type and were important for the DDL model, whereas the best-fit CD-MUSIC model for Eu(III)-gibbsite system required only one Eu(III) surface species. The Am(III)-corundum model based on the CD-MUSIC framework had the same set of surface species as the Eu(III)-corundum model. However, the log K values of the surface reactions were different. The best-fit Am(III)-corundum model based on the DDL framework had only one site type. Both the CD-MUSIC and the DDL model developed for Am(III)-γ-alumina system only comprised of one site type and the formation constant of the corresponding surface species was ~ 500 times stronger and ~ 700 times weaker than the corresponding Eu(III) species on the weak and the strong sites, respectively. The CD-MUSIC model for corundum and both the DDL and the CD-MUSIC models for γ-alumina predicted the Am(III) adsorption data very well, whereas the DDL model for corundum overpredicted the Am(III) adsorption data. The root mean square of errors of the DDL and CD-MUSIC models developed in this study were smaller than those of two previously-published models describing Am(III)-γ-alumina system, indicating the better predictive capacity of our models. Overall, our results suggest that using Eu(III) as an analog for Am(III) is practical approach for predicting Am(III) adsorption onto well-characterized minerals.

The suevite (polymict melt rock-bearing breccia) composing the upper peak ring of the Chicxulub impact crater is extremely heterogeneous, containing a combination of relict clasts and secondary minerals. Using scanning electron microscopy coupled with energy-dispersive X-ray spectroscopy (SEM/EDS) and electron probe microanalysis (EPMA), we investigated the nature and occurrence of primary and secondary Fe-oxide and Fe-sulfide minerals to better understand hydrothermal trends such as mineral precipitation and dissolution, and to document the remobilization of Fe and associated siderophile elements within suevites. Large primary Fe-oxides (~20–100 µm) reveal decomposition and dissolution patterns, forming sub-micrometer to micrometer Fe-oxide phases. Secondary sub-micrometer Fe-oxide crystals are also visibly concentrated within clay. The occurrence of Fe-oxide crystals within clay suggests that these likely formed at temperatures ≤100 °C, near the formation temperature of smectite. The formation of Fe-oxide minerals on clay surfaces is of interest as it may form a micro-setting, where free electrons (from the oxidation of Fe2+) and the adsorption of simple organic molecules on the surface of clay could generate reactive conditions favorable to microbial communities. Primary and secondary Fe-sulfide minerals exhibiting a variety of morphologies are present within samples, representing different formation mechanisms. Secondary Fe-sulfide minerals occur within rims of clasts and vesicles and in fractures and voids. Some secondary Fe-sulfide grains are associated with Ni- and Co-rich phases, potentially reflecting the post-impact migration of siderophile elements within the suevite of the Chicxulub crater.

Because of the nano-scale tunnel constructed by the active Mn-O octahedron in cryptomelane, cryptomelane-type manganese oxides have high activity in the oxidation of several volatile organic compounds (VOCs). Natural cryptomelane, in the form of supergene oxide manganese ore, carpets much of South China. In the lower part of the Datangpo Formation of Nanhua System on the southeastern Yangtze Platform, cryptomelane is one of the major manganese oxides in black shale of the Xiangtan manganese deposit in this deposit. Formaldehyde is a dominant indoor pollutant among volatile organic compounds (VOCs), and applications of synthetic cryptomelane have been reported to eliminate it. To study the removal capacity of naturally outcropping cryptomelane, representative samples of manganese oxide (the primary mineral component of cryptomelane) from the Xiangtan Mn deposit were analyzed in this study. The chemical composition, crystal structure and micromorphology of the manganese oxide minerals were explored using ICP-AES, XRD, EPMA, SEM and HR-TEM techniques. Fine-grained and poorly crystalline, these minerals consist primarily of cryptomelane, along with minor amounts of pyrolusite, hollandite, lithiophorite, limonite and quartz. Natural cryptomelane is a monoclinic crystal, and its cell parameters are refined. The results of catalytic tests revealed that natural cryptomelane has obvious catalytic activity in the oxidation of formaldehyde in a static environment under room temperature. This study may provide a natural mineral material as an inexpensive and efficient catalyst for the purification of formaldehyde in industrial or indoor air treatment.

PurposeThe oxidation of ferrous sulfide (FeS) causes soil acidification and the release of toxic heavy metal ions. Manganese oxides usually participate in the oxidation of FeS and affect the geochemical cycling of elemental Fe and S. Here, we studied the mechanism and influencing factors of FeS oxidation by oxygen and manganese oxides including birnessite, todorokite, and manganite. Metallic cavity electrode was used to study the kinetics of the electron transfer between FeS and manganese oxides.Materials and methodsManganese oxide minerals, including birnessite, todorokite, and manganite, were synthesized and used for the oxidation of FeS. The oxidation products were characterized by X-ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy, spectroscopy, high-performance liquid chromatography, and ion chromatography. The effects of pH and Fe(II) concentration on the oxidation rate of FeS were investigated. Metallic cavity electrodes filled with manganese oxides and FeS were respectively used as cathode and anode electrodes to study their reaction kinetics and the influence of crystal structure on the oxidation activity of manganese oxides.Results and discussionElemental sulfur, SO42−, and lepidocrocite were formed as the intermediates during the oxidation of FeS by todorokite and oxygen in air. Low pH facilitated the dissolution of manganese oxides and the oxidation of FeS. When FeS suspension was oxidized by oxygen in air, the participation of todorokite decreased the degree of crystallinity of the newly formed ferric (hydr)oxides and accelerated the oxidation of polysulfide to S0 and S0 to SO42− via rapid adsorption and oxidation of Fe(II). The formation of Fe(II)/Fe(III) redox couple promoted electron transfer and resulted in increased oxidation rate of FeS. Fe(III) worked as the dominant oxidant under acidic conditions (pH < 4.0) and oxygen in air was the dominant oxidant at higher pH (pH > 4.0) in ambient atmosphere.ConclusionsTodorokite accelerates FeS oxidation via adsorption and oxidation of Fe(II). Electrons are mainly transported by Fe(II)/Fe(III) shuttle at lower pH, and oxygen accepts electrons when pH is higher than 4.0. The oxidation activity follows the order of birnessite>todorokite>manganite. This work expands the understanding of the interactions and geochemical processes of FeS and manganese oxides, and provides a new technique to study the redox kinetics between soil mineral particles.

Ellinaite, a natural analog of the post-spinel phase β-CaCr.sub.2 O.sub.4, was discovered at the Hatrurim Basin, Hatrurim pyrometamorphic formation (the Mottled Zone), Israel, and in an inclusion within the super-deep diamond collected at the placer of the Sorriso River, Juína kimberlite field, Brazil. Ellinaite at the Hatrurim Basin is confined to a reduced rankinite-gehlenite paralava, where it occurs as subhedral grains up to 30 µm in association with gehlenite, rankinite and pyrrhotite or forms the rims overgrowing zoned chromite-magnesiochromite. The empirical formula of the Hatrurim sample is (Ca.sub.0.960 Fe0.0162+Na.sub.0.012 Mg.sub.0.003).sub.0.992 (Cr.sub.1.731 V0.1833+Ti0.0683+Al.sub.0.023 Ti0.0034+)2.008O.sub.4 . The mineral crystallizes in the orthorhombic system, space group Pnma, unit-cell parameters refined from X-ray single-crystal data: a 8.868(9), b 2.885(3), c 10.355(11) Ã, V 264.9(5) Ã.sup.3 and Z=4. The crystal structure of ellinaite from the Hatrurim Basin has been solved and refined to R.sub.1 =0.0588 based on 388 independent observed reflections. Ellinaite in the Juína diamond occurs within the micron-sized polyphase inclusion in association with ferropericlase, magnesioferrite, orthorhombic MgCr.sub.2 O.sub.4, unidentified iron carbide and graphite. Its empirical formula is Ca.sub.1.07 (Cr.sub.1.71 Fe0.063+V.sub.0.06 Ti.sub.0.03 Al.sub.0.03 Mg.sub.0.02 Mn.sub.0.02).sub.Σ1.93 O.sub.4 . The unit-cell parameters obtained from HRTEM data are as follows: space group Pnma, a 9.017, b 2.874 Ã, c 10.170 Ã, V 263.55 Ã.sup.3, Z=4. Ellinaite belongs to a group of natural tunnel-structured oxides of the general formula AB.sub.2 O.sub.4, the so-called post-spinel minerals: marokite CaMn.sub.2 O.sub.4, xieite FeCr.sub.2 O.sub.4, harmunite CaFe.sub.2 O.sub.4, wernerkrauseite CaFe23+Mn.sup.4+ O.sub.6, chenmingite FeCr.sub.2 O.sub.4, maohokite MgFe.sub.2 O.sub.4 and tschaunerite Fe(FeTi)O.sub.4 . The mineral from both occurrences seems to be crystallized under highly reduced conditions at high temperatures (1000 .sup.\" C), but under different pressure: near-surface (Hatrurim Basin) and lower mantle (Juína diamond).

Raman spectra were collected for an extensive set of well-characterized tunnel-structure Mn oxide mineral species employing a range of data collection conditions. Using various laser wavelengths, such as 785, 633, and 532 nm at low power levels (30–500 μW), as well as the comprehensive database of standard spectra presented here, it is generally possible to distinguish and identify the various tunnel structure Mn oxide minerals. The Raman mode relative intensities can vary significantly as a function of crystal orientation relative to the incident laser light polarization direction as well as laser light wavelength. Consequently, phase identification success is enhanced when using a standards database that includes multiple spectra collected for different crystal orientations and with different laser light wavelengths. For the hollandite-group minerals, the frequency of the Raman mode near 630 cm shows a strong linear correlation with the fraction of Mn in the octahedral Mn sites. With the comprehensive Raman database of well-characterized Mn oxide standards provided here (and available online as Supplemental Materials ), and use of appropriate data collection conditions, micro-Raman is a powerful tool for identification and characterization of biotic and abiotic Mn oxide phases from diverse natural settings, including on other planets.

The toxicity of arsenic (As) towards life on Earth is apparent in the dense distribution of genes associated with As detoxification across the tree of life. The ability to defend against As is particularly vital for survival in As-rich shallow submarine hydrothermal ecosystems along the Hellenic Volcanic Arc (HVA), where life is exposed to hydrothermal fluids containing up to 3000 times more As than present in seawater. We propose that the removal of dissolved As and phosphorus (P) by sulfide and Fe(III)(oxyhydr)oxide minerals during sediment–seawater interaction, produces nutrient-deficient porewaters containing < 2.0 ppb P. The porewater arsenite-As(III) to arsenate-As(V) ratios, combined with sulfide concentration in the sediment and/or porewater, suggest a hydrothermally-induced seafloor redox gradient. This gradient overlaps with changing high affinity phosphate uptake gene abundance. High affinity phosphate uptake and As cycling genes are depleted in the sulfide-rich settings, relative to the more oxidizing habitats where mainly Fe(III)(oxyhydr)oxides are precipitated. In addition, a habitat-wide low As-respiring and As-oxidizing gene content relative to As resistance gene richness, suggests that As detoxification is prioritized over metabolic As cycling in the sediments. Collectively, the data point to redox control on Fe and S mineralization as a decisive factor in the regulation of high affinity phosphate uptake and As cycling gene content in shallow submarine hydrothermal ecosystems along the HVA.

Iron oxide minerals play an important role in stabilizing organic carbon (OC) and regulating the biogeochemical cycles of OC on the earth surface. To predict the fate of OC, it is essential to understand the amount, spatial variability, and characteristics of Fe-bound OC in natural soils. In this study, we investigated the concentrations and characteristics of Fe-bound OC in soils collected from 14 forests in the United States and determined the impact of ecogeographical variables and soil physicochemical properties on the association of OC and Fe minerals. On average, Fe-bound OC contributed 37.8 % of total OC (TOC) in forest soils. Atomic ratios of OC : Fe ranged from 0.56 to 17.7, with values of 1–10 for most samples, and the ratios indicate the importance of both sorptive and incorporative interactions. The fraction of Fe-bound OC in TOC (fFe-OC) was not related to the concentration of reactive Fe, which suggests that the importance of association with Fe in OC accumulation was not governed by the concentration of reactive Fe. Concentrations of Fe-bound OC and fFe-OC increased with latitude and reached peak values at a site with a mean annual temperature of 6.6 °C. Attenuated total reflectance–Fourier transform infrared spectroscopy (ATR-FTIR) and near-edge X-ray absorption fine structure (NEXAFS) analyses revealed that Fe-bound OC was less aliphatic than non-Fe-bound OC. Fe-bound OC also was more enriched in 13C compared to the non-Fe-bound OC, but C ∕ N ratios did not differ substantially. In summary, 13C-enriched OC with less aliphatic carbon and more carboxylic carbon was associated with Fe minerals in the soils, with values of fFe-OC being controlled by both sorptive and incorporative associations between Fe and OC. Overall, this study demonstrates that Fe oxides play an important role in regulating the biogeochemical cycles of C in forest soils and uncovers the governing factors for the spatial variability and characteristics of Fe-bound OC.

In nitrogen (N)-limited boreal forests, trees depend on the decomposing activity of their ectomycorrhizal (ECM) fungal symbionts to access soil N. A large fraction of this N exists as proteinaceous compounds associated with mineral particles. However, it is not known if ECM fungi can access these mineral-associated proteins; accordingly, possible acquisition mechanisms have not been investigated. With tightly controlled isotopic, spectroscopic, and chromatographic experiments, we quantified and analyzed the mechanisms of N acquisition from iron oxide mineral-associated proteins by Paxillus involutus, a widespread ECM fungus in boreal forests. The fungus acquired N from the mineral-associated proteins. The collective results indicated a proteolytic mechanism involving formation of the crucial enzyme–substrate complexes at the mineral surfaces. Hence, the enzymes hydrolyzed the mineral-associated proteins without initial desorption of the proteins. The proteolytic activity was suppressed by adsorption of proteases to the mineral particles. This process was counteracted by fungal secretion of mineral-surface-reactive compounds that decreased the protease–mineral interactions and thereby promoted the formation of enzyme–substrate complexes. The ability of ECM fungi to simultaneously generate extracellular proteases and surface-reactive metabolites suggests that they can play an important role in unlocking the large N pool of mineral-associated proteins to trees in boreal forests.

Oxide minerals contained in ultramafic rocks are useful tools to assess the redox conditions of the rock and fluids liberated upon progressive serpentinite dehydration during subduction, as these minerals contain a relevant redox-sensitive element, iron. Previous studies have revealed that magnetite predominates across the antigorite-out reaction. However, the fate of magnetite and other oxides at higher pressure and temperature conditions has remained underexplored. We present a comprehensive petrological and geochemical study of oxide-sulfide-silicate mineral assemblages in metaperidotites beyond antigorite- and chlorite-out reactions (T = 650–850 °C and P = 1–3 GPa). Several ultramafic lenses, covering different bulk rock compositions and extents of oxidation upon oceanic serpentinization, were investigated from the Central Alps, Switzerland. Results point to two endmember scenarios: (i) Most frequently, metaperidotites have olivine with a Mg# of 89–91 (defined as molar Mg/(Mg + Fe tot ) × 100) and contain low oxide modes (0.06–1.41 vol.%), hematite is absent, and redox conditions are weakly oxidized and buffered by orthopyroxene-olivine-magnetite. (ii) Rare occurrence, high olivine Mg# > 94.5 metaperidotites display coexisting hematite and magnetite, high oxide modes (up to 4 vol.%), and redox conditions are hematite-magnetite (HM) buffered (Δlog 10 fO 2 , QFM of + 3 to + 4). Spinel displays evolving compositions from magnetite over chromite to Al-Cr-spinel, roughly correlating with increasing temperature. Most of the samples buffered by the olivine-orthopyroxene-magnetite assemblage contain coexisting pentlandite ± pyrrhotite, thus identifying stable sulfides beyond antigorite dehydration for these weakly oxidized samples (Δlog 10 fO 2 , QFM  < 2.5). No sulfides were recognized in the highly oxidized sample. The transition of magnetite to chromite at around 700 °C goes along with a shift in fO 2 to lower values. At the prevailing oxygen fugacity in the weakly oxidized metaperidotites sulfur in a coexisting fluid is always present in its reduced form. However, oxidized sulfur can be stable in the dehydration fluids released from highly oxidized serpentinites.