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. 相似文献
Serpentine soils and ultramafic laterites develop over ultramafic bedrock and are important geological materials from environmental, geochemical, and industrial standpoints. They have naturally elevated concentrations of trace metals, such as Ni, Cr, and Co, and also high levels of Fe and Mg. Minerals host these trace metals and influence metal mobility. Ni in particular is an important trace metal in these soils, and the objective of this research was to use microscale (µ) techniques to identify naturally occurring minerals that contain Ni and Ni correlations with other trace metals, such as Fe, Mn, and Cr. Synchrotron based µ-XRF, µ-XRD, and µ-XAS were used. Ni was often located in the octahedral layer of serpentine minerals, such as lizardite, and in other layered phyllosilicate minerals with similar octahedral structure, such as chlorite group minerals including clinochlore and chamosite. Ni was also present in goethite, hematite, magnetite, and ferrihydrite. Goethite was present with lizardite and antigorite on the micrometer scale. Lizardite integrated both Ni and Mn simultaneously in its octahedral layer. Enstatite, pargasite, chamosite, phlogopite, and forsterite incorporated various amounts of Ni and Fe over the micrometer spatial scale. Ni content increased six to seven times within the same 500 µm µ-XRD transect on chamosite and phlogopite. Data are shown down to an 8 µm spatial scale. Ni was not associated with chromite or zincochromite particles. Ni often correlated with Fe and Mn, and generally did not correlate with Cr, Zn, Ca, or K in µ-XRF maps. A split shoulder feature in the µ-XAS data at 8400 eV (3.7 Å?1 in k-space) is highly correlated (94% of averaged LCF results) to Ni located in the octahedral sheet of layered phyllosilicate minerals, such as serpentine and chlorite-group minerals. A comparison of bulk-XAS LCF to averaged µ-XAS LCF results showed good representation of the bulk soil via the µ-XAS technique for two of the three soils. In the locations analyzed by µ-XAS, average Ni speciation was dominated by layered phyllosilicate and serpentine minerals (76%), iron oxides (18%), and manganese oxides (9%). In the locations analyzed by µ-XRD, average Ni speciation was dominated by layered phyllosilicate, serpentine, and ultramafic-related minerals (71%) and iron oxides (17%), illustrating the complementary nature of these two methods.
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 Oi, Oe, and Oa 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. 相似文献
It has been established that idealized western boundary currents, which encounter a gap in their supporting boundary, will assume one of two dominant steady states: a loop current state and a gap leaping state, and that transitions between these states display hysteresis. However, a question of whether the idealized geometries considered to date apply to the Gulf of Mexico Loop Current (LC) remained. Here, the nonlinear potential vorticity advection-diffusions equations are solved, for Gulf of Mexico topography, using Newton’s method. We demonstrate that, in application to the LC in the Gulf of Mexico, the original conclusions do hold and additionally describe peculiarities of the more realistic steady states. The existence of our numerically calculated steady LC states in the actual Gulf of Mexico are supported through analysis of historical sea surface height data, and implications of our results for LC modeling and forecasting are discussed.
A CCD photometric study is presented for the eclipsing binary system 2MASS J20004638 + 0547475. Observations of the system were obtained in the V, R and I colours with the 2Kx2K CCD attached to 1.88 m Kottamia Optical Telescope. New times of light minimum and new ephemeris were obtained. The V, R and I light curves were analyzed using the PHOEBE 0.31 program to determine geometrical and physical parameters of the system. The results show that 2MASS J20004638 + 0547475, is A-Type WUMa and is an overcontact binary with high fill-out factor = 69%. The current evolutionary status of the system indicates that the primary component lies very close to the main sequence while the secondary is evolved. The asymmetric maxima were studied and a modeling of the hot spot parameters is given. 相似文献
In the summer and fall of 2012, during the GLAD experiment in the Gulf of Mexico, the Consortium for Advanced Research on Transport of Hydrocarbon in the Environment (CARTHE) used several ocean models to assist the deployment of more than 300 surface drifters. The Navy Coastal Ocean Model (NCOM) at 1 km and 3 km resolutions, the US Navy operational NCOM at 3 km resolution (AMSEAS), and two versions of the Hybrid Coordinates Ocean Model (HYCOM) set at 4 km were running daily and delivering 72-h range forecasts. They all assimilated remote sensing and local profile data but they were not assimilating the drifter’s observations. This work presents a non-intrusive methodology named Multi-Model Ensemble Kalman Filter that allows assimilating the local drifter data into such a set of models, to produce improved ocean currents forecasts. The filter is to be used when several modeling systems or ensembles are available and/or observations are not entirely handled by the operational data assimilation process. It allows using generic in situ measurements over short time windows to improve the predictability of local ocean dynamics and associated high-resolution parameters of interest for which a forward model exists (e.g. oil spill plumes). Results can be used for operational applications or to derive enhanced background fields for other data assimilation systems, thus providing an expedite method to non-intrusively assimilate local observations of variables with complex operators. Results for the GLAD experiment show the method can improve water velocity predictions along the observed drifter trajectories, hence enhancing the skills of the models to predict individual trajectories. 相似文献
A series of consolidated-drained triaxial tests were performed on precut and polished clay specimens to measure their drained
residual strength. Two soils were tested during this research program: Rancho Solano Clay and San Francisco Bay Mud. Specimens
were tested using a specially modified triaxial compression device which was developed to minimize the effects of end-platen
restraint on the measured strengths. Special attention was paid to the influence of changing specimen area and membrane effects
during the test. Triaxial test results were compared with baseline measurements of drained residual shear strength that were
made for each of the clay soils using Bromhead ring shear tests and polished-specimen direct shear tests. Residual strength
values measured in the triaxial device were higher than the drained residual strengths measured in the Bromhead ring shear
apparatus and the direct shear device, indicating that this test approach is more challenging than the use of direct shear
tests conducted on polished slickensided surfaces. Comparison of single stage and multistage triaxial test data indicates
that multistage triaxial testing may work well for specimens that fail along a well-defined plane, provided that careful attention
is given to the effects of end platen restraint, membrane restraint, and changes in specimen area during shear. 相似文献
下载免费PDF全文