Association of dissolved aluminum with silica: Connecting molecular structure to surface reactivity using NMR

We studied uptake mechanisms for dissolved Al on amorphous silica by combining bulk-solution chemistry experiments with solid-state Nuclear Magnetic Resonance techniques (²⁷Al magic-angle spinning (MAS) NMR, ²⁷Al{¹H} cross-polarization (CP) MAS NMR and ²⁹Si{¹H} CP-MAS NMR). We find that reaction of Al (1 mM) with amorphous silica consists of at least three reaction pathways; (1) adsorption of Al to surface silanol sites, (2) surface-enhanced precipitation of an aluminum hydroxide, and (3) bulk precipitation of an aluminosilicate phase. From the NMR speciation and water chemistry data, we calculate that 0.20 (±0.04) tetrahedral Al atoms nm⁻² sorb to the silica surface. Once the surface has sorbed roughly half of the total dissolved Al (∼8% site coverage), aluminum hydroxides and aluminosilicates precipitate from solution. These precipitation reactions are dependent upon solution pH and total dissolved silica concentration. We find that the Si:Al stoichiometry of the aluminosilicate precipitate is roughly 1:1 and suggest a chemical formula of NaAlSiO₄ in which Na⁺ acts as the charge compensating cation. For the adsorption of Al, we propose a surface-controlled reaction mechanism where Al sorbs as an inner-sphere coordination complex at the silica surface. Analogous to the hydrolysis of , we suggest that rapid deprotonation by surface hydroxyls followed by dehydration of ligated waters results in four-coordinate (>SiOH)₂Al(OH)₂ sites at the surface of amorphous silica.     

Iron isotope fractionation in subterranean estuaries

Dissolved Fe concentrations in subterranean estuaries, like their river-seawater counterparts, are strongly controlled by non-conservative behavior during mixing of groundwater and seawater in coastal aquifers. Previous studies at a subterranean estuary of Waquoit Bay on Cape Cod, USA demonstrate extensive precipitation of groundwater-borne dissolved ferrous iron and subsequent accumulation of iron oxides onto subsurface sands. Waquoit Bay is thus an excellent natural laboratory to assess the mechanisms of Fe-isotope fractionation in redox-stratified environments and determine potential Fe-isotope signatures of groundwater sources to coastal seawater. Here, we report Fe isotope compositions of iron-coated sands and porewaters beneath the intertidal zone of Waquoit Bay. The distribution of pore water Fe shows two distinct sources of Fe: one residing in the upward rising plume of Fe-rich groundwater and the second in the salt-wedge zone of pore water. The groundwater source has high Fe(II) concentration consistent with anoxic conditions and yield δ⁵⁶Fe values between 0.3 and −1.3‰. In contrast, sediment porewaters occurring in the mixing zone of the subterranean estuary have very low δ⁵⁶Fe values down to −5‰. These low δ⁵⁶Fe values reflect Fe-redox cycling and result from the preferential retention of heavy Fe-isotopes onto newly formed Fe-oxyhydroxides. Analysis of Fe-oxides precipitated onto subsurface sands in two cores from the subterranean estuary revealed strong δ⁵⁶Fe and Fe concentration gradients over less than 2m, yielding an overall range of δ⁵⁶Fe values between −2 and 1.5‰. The relationship between Fe concentration and δ⁵⁶Fe of Fe-rich sands can be modeled by the progressive precipitation of Fe-oxides along fluid flow through the subterranean estuary. These results demonstrate that large-scale Fe isotope fractionation (up to 5‰) can occur in subterranean estuaries, which could lead to coastal seawater characterized by very low δ⁵⁶Fe values relative to river values.     

Reaction mechanism of uranyl in the presence of zero-valent iron nanoparticles

The current study provides an investigation of abiotic reduction of an oversaturated uranyl solution driven by iron nanoparticle oxidation. The reactivity of nano-scale zero-valent iron (ZVI) under mildly oxic conditions (1.2% O₂ and 0.0017% CO₂) was studied in 1000 ppm uranyl solution in the pH range 3-7, at reaction times from 10 min to 4 h. Reductive precipitation of UO₂ was observed as the main process responsible for the removal of uranium from solution with the kinetics of reaction becoming increasingly favourable at higher pH. Despite working with an oversaturated uranium solution, the precipitation of UO₂ occurred in preference to precipitation of UO₃·2H₂O (metaschoepite) at reaction times between 1 and 4 h and for uranyl solutions initially set up at pH ?5. Characterisation of both solid and solution phases was performed using X-ray photoelectron spectroscopy (XPS), focused ion beam (FIB) imaging, X-ray diffraction (XRD) and inductively coupled plasma atomic emission spectroscopy (ICP-AES).     

Anaerobic oxidation of methane (AOM) in marine sediments from the Skagerrak (Denmark): II. Reaction-transport modeling

A steady-state reaction-transport model is applied to sediments retrieved by gravity core from two stations (S10 and S13) in the Skagerrak to determine the main kinetic and thermodynamic controls on anaerobic oxidation of methane (AOM). The model considers an extended biomass-implicit reaction network for organic carbon degradation, which includes extracellular hydrolysis of macromolecular organic matter, fermentation, sulfate reduction, methanogenesis, AOM, acetogenesis and acetotrophy. Catabolic reaction rates are determined using a modified Monod rate expression that explicitly accounts for limitation by the in situ catabolic energy yields. The fraction of total sulfate reduction due to AOM in the sulfate-methane transition zone (SMTZ) at each site is calculated. The model provides an explanation for the methane tailing phenomenon which is observed here and in other marine sediments, whereby methane diffuses up from the SMTZ to the top of the core without being consumed. The tailing is due to bioenergetic limitation of AOM in the sulfate reduction zone, because the methane concentration is too low to engender favorable thermodynamic drive. AOM is also bioenergetically inhibited below the SMTZ at both sites because of high hydrogen concentrations (∼3-6 nM). The model results imply there is no straightforward relationship between pore water concentrations and the minimum catabolic energy needed to support life because of the highly coupled nature of the reaction network. Best model fits are obtained with a minimum energy for AOM of ∼11 kJ mol⁻¹, which is within the range reported in the literature for anaerobic processes.     

Fast kimberlite ascent rates estimated from hydrogen diffusion profiles in xenolithic mantle olivines from southern Africa

Fourier transform infrared spectrometry (FTIR) analyses of olivines from peridotite xenoliths found in southern African kimberlites indicate 0 to 80 ppm H₂O concentrations. OH absorbance profiles across olivine grains show homogeneous H contents from core to edge for most samples. In one sample the olivines are H-free, while another has olivines characterized by lower H contents at the grain edges compared to the cores, indicating H loss during transport of the xenolith to the surface. Flat or near-flat H profiles place severe constraints on the duration of H loss from olivine grains, with implications for kimberlite magma ascent rates. Diffusion equations were used to estimate times of H loss of about 4 h for the sample with heterogeneous olivine H contents. Resulting kimberlite ascent rates are calculated to be 5-37 m s⁻¹ minimum, although these estimates are highly dependent on volatile contents and degassing behavior of the host kimberlite magma. Xenolithic olivines from alkali basalts generally have lower H contents and more pronounced H diffusion profiles than do those from kimberlites. This difference is likely caused by higher magma temperatures and lower ascent rates of alkali basalts compared to kimberlites.     

Biotite weathering and nutrient uptake by ectomycorrhizal fungus, Suillus tomentosus, in liquid-culture experiments

Ectomycorrhiza-forming fungi (EMF) alter the nutrient-acquisition capabilities of vascular plants, and may play an important role in mineral weathering and the partitioning of products of weathering in soils under nutrient-limited conditions. In this study, we isolated the weathering function of Suillus tomentosus in liquid-cultures with biotite micas incubated at room temperature. We hypothesized that the fungus would accelerate weathering by hyphal attachment to biotite surfaces and transmission of nutrient cations via direct exchange into the fungal biomass. We combined a mass-balance approach with scanning electron microscopy (SEM) and atomic force microscopy (AFM) to estimate weathering rates and study dissolution features on biotite surfaces. Weathering of biotite flakes was about 2-3 orders of magnitude faster in shaken liquid-cultures with fungus compared to shaken controls without fungus, but with added inorganic acids. Adding fungus in nonshaken cultures caused a higher dissolution rate than in inorganic pH controls without fungus, but it was not significantly faster than organic pH controls without fungus. The K⁺, Mg²⁺ and Fe²⁺ from biotite were preferentially partitioned into fungal biomass in the shaken cultures, while in the nonshaken cultures, K⁺ and Mg²⁺ was lost from biomass and Fe²⁺ bioaccumulated much less. Fungal hyphae attached to biotite surfaces, but no significant surface changes were detected by SEM. When cultures were shaken, the AFM images of basal planes appeared to be rougher and had abundant dissolution channels, but such channel development was minor in nonshaken conditions. Even under shaken conditions the channels only accounted for only 1/100 of the total dissolution rate of 2.7 × 10⁻¹⁰ mol of biotite m⁻² s⁻¹. The results suggest that fungal weathering predominantly occurred not by attachment and direct transfer of nutrients via hyphae, but because of the acidification of the bulk liquid by organic acids, fungal respiration (CO₂), and complexation of cations which accelerated dissolution of biotite. Results further suggest that both carbohydrate source (abundant here) and a host with which nutrients are exchanged (missing here) may be required for EMF to exert an important weathering effect in soils. Unsaturated conditions and physical dispersal of nutrient-rich minerals in soils may also confer a benefit for hyphal growth and attachment, and promote the attachment-mediated weathering which has been observed elsewhere on soil mineral surfaces.     

Seasonal δS variations in two high elevation snow pits measured by S-S double spike thermal ionization mass spectrometry

δ³⁴S and sulfate concentrations were determined in snow pit samples using a thermal ionization mass spectrometric technique capable of 0.2‰ accuracy and requires ≈5 μg (0.16 μmol) natural S. The technique utilizes a ³³S-³⁶S double spike for instrumental mass fractionation correction, and has been applied to snow pit samples collected from the Inilchek Glacier, Kyrgyzstan and from Summit, Greenland. These δ³⁴S determinations provide the first high-resolution seasonal data for these sites, and are used to estimate seasonal sulfate sources. Deuterium (δD) and oxygen (δ¹⁸O) isotope data show that the Inilchek and Summit snow pit samples represent precipitation over ≈20 months.The δ³⁴S values for the Inilchek ranged from +2.6 ± 0.4‰ to +7.6 ± 0.4‰ on sample sizes ranging from 0.3 to 1.8 μmol S. δ³⁴S values for Greenland ranged from +3.6 ± 0.7‰ to +13.3 ± 5‰ for sample sizes ranging from 0.05 to 0.29 μmol S. The concentration ranged from 92.6 ± 0.4 to 1049 ± 4 ng/g for the Inilchek and 18 ± 9 to 93 ± 6 ng/g for the Greenland snow pit. Anthropogenic sulfate dominates throughout the sampled time interval for both sites based on mass balance considerations. Additionally, both sites exhibit a seasonal signature in both δ³⁴S and concentration. The thermal ionization mass spectrometric technique has three advantages compared to gas source isotopic methods: (1) sample size requirements of this technique are 10-fold less permitting access to the higher resolution S isotope record of low concentration snow and ice, (2) the double spike technique permits δ³⁴S and S concentration to be determined simultaneously, and (3) the double spike is an internal standard.     

The Fe-C system at 5 GPa and implications for Earth’s core

Earth’s core may contain C, and it has been suggested that C in the core could stabilize the formation of a solid inner core composed of Fe₃C. We experimentally examined the Fe-C system at a pressure of 5 GPa and determined the Fe-C phase diagram at this pressure. In addition, we measured solid metal/liquid metal partition coefficients for 17 trace elements and examined the partitioning behavior between Fe₃C and liquid metal for 14 trace elements. Solid metal/liquid metal partition coefficients are similar to those found in one atmosphere studies, indicating that the effect of pressure to 5 GPa is negligible. All measured Fe₃C/liquid metal partition coefficients investigated are less than one, such that all trace elements prefer the C-rich liquid to Fe₃C. Fe₃C/liquid metal partition coefficients tend to decrease with decreasing atomic radii within a given period. Of particular interest, our 5 GPa Fe-C phase diagram does not show any evidence that the Fe-Fe₃C eutectic composition shifts to lower C contents with increasing pressure, which is central to the previous reasoning that the inner core may be composed of Fe₃C.     

Geochemistry, petrology and ages of the lunar meteorites Kalahari 008 and 009: New constraints on early lunar evolution

Kalahari 008 and 009 are two lunar meteorites that were found close to each other in Botswana. Kalahari 008 is a typical lunar anorthositic breccia; Kalahari 009 a monomict breccia with basaltic composition and mineralogy. Based on minor and trace elements Kalahari 009 is classified as VLT (very-low-Ti) mare basalt with extremely low contents of incompatible elements, including the REE. The Lu-Hf data define an age of 4286 ± 95 Ma indicating that Kalahari 009 is one of the oldest known basalt samples from the Moon. It provides evidence for lunar basalt volcanism prior to 4.1 Ga (pre-Nectarian) and may represent the first sample from a cryptomare. The very radiogenic initial ¹⁷⁶Hf/¹⁷⁷Hf (εHf = +12.9 ± 4.6), the low REE, Th and Ti concentrations indicate that Kalahari 009 formed from re-melting of mantle material that had undergone strong incompatible trace element depletion early in lunar history. This unusually depleted composition points toward a hitherto unsampled basalt source region for the lunar interior that may represent a new depleted endmember source for low-Ti mare basalt volcanism. Apparently, the Moon became chemically very heterogeneous at an early stage in its history and different cumulate sources are responsible for the diverse mare basalt types.Evidence that Kalahari 008 and 009 may be paired includes the similar fayalite content of their olivine, the identical initial Hf isotope composition, the exceptionally low exposure ages of both rocks and the fact that they were found close to each other. Since cryptomaria are covered by highland ejecta, it is possible that these rocks are from the boundary area, where basalt deposits are covered by highland ejecta. The concentrations of cosmogenic radionuclides and trapped noble gases are unusually low in both rocks, although Kalahari 008 contains slightly higher concentrations. A likely reason for this difference is that Kalahari 008 is a polymict breccia containing a briefly exposed regolith, while Kalahari 009 is a monomict brecciated rock that may never have been at the surface of the Moon.Altogether, the compositions of Kalahari 008 and 009 permit new insight into early lunar evolution, as both meteorites sample lunar reservoirs hitherto unsampled by spacecraft missions. The very low Th and REE content of Kalahari 009 as well as the depletion in Sm and the lack of a KREEP-like signature in Kalahari 008 point to a possible source far from the influence of the Procellarum-KREEP Terrane, possibly the lunar farside.     

Thermodynamic model for arsenic speciation in sulfidic waters: A novel use of ab initio computations

Recent discoveries demonstrate that the chemistry of arsenic in sulfidic waters is much more complex that previously believed. One implication is that all earlier thermodynamic data on stabilities of As thioanions require revision. Previously used experimental approaches for determining As thioanion stabilities may be inadequate to deal with the full range of complexity. Here we use computational as well as empirical information to construct a provisional model for equilibrium As thioanion distributions in sulfidic waters. Whereas previous authors have argued for either As(III) or As(V) thioanions, the new model predicts that both are important and can occur simultaneously under commonly encountered pH and ΣS^−II conditions. At the order of magnitude level, the model reasonably predicts the solubility of As₂S₃ in sulfidic solutions, provides tentative peak assignments for published Raman spectroscopic data and plausibly accounts for how sulfide modifies the bacterial toxicity of As. The model yields a thermodynamic justification for how sulfide, which is usually regarded as a reducing agent, can counter-intuitively drive oxidation of As(III) to As(V), as has been observed both in the laboratory and in the field. Despite its uncertain accuracy, the model serves as a useful source of new, testable hypotheses about As geochemistry and highlights crucial experimental data needs.