Impacts of hydrous manganese oxide on the retention and lability of dissolved organic matter

Minerals constitute a primary ecosystem control on organic C decomposition in soils, and therefore on greenhouse gas fluxes to the atmosphere. Secondary minerals, in particular, Fe and Al (oxyhydr)oxides—collectively referred to as “oxides” hereafter—are prominent protectors of organic C against microbial decomposition through sorption and complexation reactions. However, the impacts of Mn oxides on organic C retention and lability in soils are poorly understood. Here we show that hydrous Mn oxide (HMO), a poorly crystalline δ-MnO₂, has a greater maximum sorption capacity for dissolved organic matter (DOM) derived from a deciduous forest composite O_i, O_e, and O_a horizon leachate (“O horizon leachate” hereafter) than does goethite under acidic (pH 5) conditions. Nonetheless, goethite has a stronger sorption capacity for DOM at low initial C:(Mn or Fe) molar ratios compared to HMO, probably due to ligand exchange with carboxylate groups as revealed by attenuated total reflectance-Fourier transform infrared spectroscopy. X-ray photoelectron spectroscopy and scanning transmission X-ray microscopy–near-edge X-ray absorption fine structure spectroscopy coupled with Mn mass balance calculations reveal that DOM sorption onto HMO induces partial Mn reductive dissolution and Mn reduction of the residual HMO. X-ray photoelectron spectroscopy further shows increasing Mn(II) concentrations are correlated with increasing oxidized C (C=O) content (r = 0.78, P < 0.0006) on the DOM–HMO complexes. We posit that DOM is the more probable reductant of HMO, as Mn(II)-induced HMO dissolution does not alter the Mn speciation of the residual HMO at pH 5. At a lower C loading (2 × 10² μg C m^?2), DOM desorption—assessed by 0.1 M NaH₂PO₄ extraction—is lower for HMO than for goethite, whereas the extent of desorption is the same at a higher C loading (4 × 10² μg C m^?2). No significant differences are observed in the impacts of HMO and goethite on the biodegradability of the DOM remaining in solution after DOM sorption reaches steady state. Overall, HMO shows a relatively strong capacity to sorb DOM and resist phosphate-induced desorption, but DOM–HMO complexes may be more vulnerable to reductive dissolution than DOM–goethite complexes.     

The synergistic effect of calcium on organic carbon sequestration to ferrihydrite

Sequestration of organic carbon (OC) in environmental systems is critical to mitigating climate change. Organo-mineral associations, especially those with iron (Fe) oxides, drive the chemistry of OC sequestration and stability in soils. Short-range-ordered Fe oxides, such as ferrihydrite, demonstrate a high affinity for OC in binary systems. Calcium commonly co-associates with OC and Fe oxides in soils, though the bonding mechanism (e.g., cation bridging) and implications of the co-association for OC sequestration remain unresolved. We explored the effect of calcium (Ca²⁺) on the sorption of dissolved OC to 2-line ferrihydrite. Sorption experiments were conducted between leaf litter-extractable OC and ferrihydrite at pH 4 to 9 with different initial C/Fe molar ratios and Ca²⁺ concentrations. The extent of OC sorption to ferrihydrite in the presence of Ca²⁺ increased across all tested pH values, especially at pH ≥ 7. Sorbed OC concentration at pH 9 increased from 8.72 ± 0.16 to 13.3 ± 0.20 mmol OC g^?1 ferrihydrite between treatments of no added Ca²⁺ and 30 mM Ca²⁺ addition. Batch experiments were paired with spectroscopic studies to probe the speciation of sorbed OC and elucidate the sorption mechanism. ATR-FTIR spectroscopy analysis revealed that carboxylic functional moieties were the primary sorbed OC species that were preferentially bound to ferrihydrite and suggested an increase in Fe-carboxylate ligand exchange in the presence of Ca at pH 9. Results from batch to spectroscopic experiments provide significant evidence for the enhancement of dissolved OC sequestration to 2-line ferrihydrite and suggest the formation of Fe–Ca-OC ternary complexes. Findings of this research will inform modeling of environmental C cycling and have the potential to influence strategies for managing land to minimize OM stabilization.     

The institutional implications of environmental ethics for fishery management in the US exclusive economic zone

The public discourse surrounding many fishery management issues suggests that ethical concerns may be an important aspect of these issues for a segment of the American public. Questions have been raised about the capacity of regional fishery management councils created under the Fishery Conservation and Management Act to be adequately responsive to different ethical values. To date, legislative efforts to broaden council membership have been unsuccessful, but pressure for institutional reform is likely to increase with the adoption of an ecosystem approach to fishery management.     

Upright crinoids of the Thornton Reef,Wenlock (Silurian) of Illinois,USA

The rare preservation of columns perpendicular to bedding may provide convincing evidence that ancient crinoids adopted an upright attitude during life. However, taphonomic and sedimentological analyses are important in determining whether such occurrences are truly in situ or represent unusual allochthonous accumulations. The Crinoid Biosome of the Thornton Reef Complex, Silurian of Illinois, USA, includes pluricolumnals preserved perpendicular to bedding, in association with more common specimens parallel or angled to bedding. Upright pluricolumnals are relatively shorter (<150 mm) than the longest non-upright specimens; they sometimes occur as imbricate accumulations and lack attachment structures (although these are preserved separately). Brachiopod valves and colonial corals may also be preserved perpendicular to bedding. These features suggest that the Thornton beds were formed as viscous mass flow deposits and that the upright crinoid columns are allochthonous or, at best, parautochthonous. © 1996 John Wiley & Sons, Ltd.     

LA‐ICP‐MS Pb isotope test of meteorite provenance: A terrestrial origin for Lovina

Lovina, classified as an ungrouped ataxite, is controversial and its identity as a meteorite has been questioned. In this work, we use Pb isotopes on targeted troilite nodules in Lovina as a test of its antiquity and provenance. Although precise ages cannot be obtained, LA‐ICP‐MS offers a rapid, straightforward procedure to establish the source of lead, whether ancient (meteoritic) or modern (terrestrial). For nine pristine, unweathered nodules in Lovina, we find a lead isotopic composition of: ²⁰⁶Pb/²⁰⁸Pb = 0.492 ± 0.003 (2σ, MSWD 0.79; 95%) and ²⁰⁷Pb/²⁰⁶Pb = 0.852 ± 0.003 (2σ, MSWD 1.09; 95%) with no detectable uranium. All lead compositions of the troilite fall in the range expected for modern environmental and mantle lead and are distinctly different from the primordial Canyon Diablo Troilite (CDT) composition of ancient meteoritic troilite. Although the origin of Lovina remains unknown, we conclude that lead in the Lovina troilite is unsupported by U decay and originated from a terrestrial source.     

Hydrogen fluence in Genesis collectors: Implications for acceleration of solar wind and for solar metallicity

NASA's Genesis mission was flown to capture samples of the solar wind and return them to the Earth for measurement. The purpose of the mission was to determine the chemical and isotopic composition of the Sun with significantly better precision than known before. Abundance data are now available for noble gases, magnesium, sodium, calcium, potassium, aluminum, chromium, iron, and other elements. Here, we report abundance data for hydrogen in four solar wind regimes collected by the Genesis mission (bulk solar wind, interstream low‐energy wind, coronal hole high‐energy wind, and coronal mass ejections). The mission was not designed to collect hydrogen, and in order to measure it, we had to overcome a variety of technical problems, as described herein. The relative hydrogen fluences among the four regimes should be accurate to better than ±5–6%, and the absolute fluences should be accurate to ±10%. We use the data to investigate elemental fractionations due to the first ionization potential during acceleration of the solar wind. We also use our data, combined with regime data for neon and argon, to estimate the solar neon and argon abundances, elements that cannot be measured spectroscopically in the solar photosphere.     

Circulation on the north central Chukchi Sea shelf

Mooring and shipboard data collected between 1992 and 1995 delineate the circulation over the north central Chukchi shelf. Previous studies indicated that Pacific waters crossed the Chukchi shelf through Herald Valley (in the west) and Barrow Canyon (in the east). We find a third branch (through the Central Channel) onto the outer shelf. The Central Channel transport varies seasonally in phase with Bering Strait transport, and is 0.2 Sv on average, although some of this might include water entrained from the outflow through Herald Valley. A portion of the Central Channel outflow moves eastward and converges with the Alaskan Coastal Current at the head of Barrow Canyon. The remainder appears to continue northeastward over the central outer shelf toward the shelfbreak, joined by outflow from Herald Valley. The mean flow opposes the prevailing winds and is primarily forced by the sea-level slope between the Pacific and Arctic oceans. Current variations are mainly wind forced, but baroclinic forcing, associated with upstream dense-water formation in coastal polynyas might occasionally be important.Winter water-mass modification depends crucially on the fall and winter winds, which control seasonal ice development. An extensive fall ice cover delays cooling, limits new ice formation, and results in little salinization. In such years, Bering shelf waters cross the Chukchi shelf with little modification. In contrast, extensive open water in fall leads to early and rapid cooling, and if accompanied by vigorous ice production within coastal polynyas, results in the production of high-salinity (>33) shelf waters. Such interannual variability likely affects slope processes and the transport of Pacific waters into the Arctic Ocean interior.     

Shapes of chondrules determined from the petrofabric of the CR2 chondrite NWA 801

The approximately spherical shapes of chondrules has long been attributed to surface tension acting on ~1 mm melt droplets that formed and cooled in the microgravity field of the solar nebula. However, chondrule shapes commonly depart significantly from spherical. In this study, 109 chondrules in a sample of CR2 chondrite NWA 801 were imaged by X-ray computed tomography and best-fitted to ellipsoids. The analysis confirms that many chondrules are indeed not spherical, and also that the chondrules’ collective shape fabric records a definite 13% compaction in the host meteorite. Dehydration of phyllosilicates within chondrules may account for that strain. However, retro-deforming all chondrules shows that a large majority were already far from spherical prior to accretion. Possible models for these initial shapes include prior deformation of individual chondrules in earlier hosts, and, as suggested by previous authors, rotation of chondrules as they were solidifying, and/or “streaming” of molten chondrules by their differential velocities with their gaseous hosts after melting. More in situ 3-D work such as this study on a variety of unequilibrated chondrites, combined with detailed structural petrography, should help further constrain these models and refine our understanding of chondrite formation.