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.     

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.     

Petrologic constraints on the decompression history of magma prior to Vulcanian explosions at the Soufrière Hills volcano,Montserrat

A series of 88 Vulcanian explosions occurred at the Soufrière Hills volcano, Montserrat, between August and October, 1997. Conduit conditions conducive to creating these and other Vulcanian explosions were explored via analysis of eruptive products and one-dimensional numerical modeling of magma ascent through a cylindrical conduit. The number densities and textures of plagioclase microlites were documented for twenty-three samples from the events. The natural samples all show very high number densities of microlites, and > 50% by number of microlites have areas < 20 μm². Pre-explosion conduit conditions and decompression history have been inferred from these data by comparison with experimental decompressions of similar groundmass compositions. Our comparisons suggest quench pressures < 30 MPa (origin depths < 2 km) and multiple rapid decompressions of > 13.75 MPa each during ascent from chamber to surface. Values are consistent with field studies of the same events and statistical analysis of explosion time-series data. The microlite volume number density trend with depth reveals an apparent transition from growth-dominated crystallization to nucleation-dominated crystallization at pressures of ∼ 7 MPa and lower. A concurrent sharp increase in bulk density marks the onset of significant open-system degassing, apparently due to a large increase in system permeability above ∼ 70% vesicularity. This open-system degassing results in a dense plug which eventually seals the conduit and forms conditions favorable to Vulcanian explosions. The corresponding inferred depth of overpressure at 250–700 m, near the base of the dense plug, is consistent with depth to center of pressure estimated from deformation measurements. Here we also illustrate that one-dimensional models representing ascent of a degassing, crystal-rich magma are broadly consistent with conduit profiles constructed via our petrologic analysis. The comparison between models and petrologic data suggests that the dense conduit plug forms as a result of high overpressure and open-system degassing through conduit walls.     

Monitoring of Snow Cover Variability in Chenab Basin Using IRS AWiFS Sensor

Monitoring of seasonal snow cover is important for many applications such as melt runoff estimation, climate change studies and strategic requirements. Contribution of seasonal snow melt runoff of Chenab River is significant and important to meet hydrological requirement at foothills. Seasonal snow cover of Chandra, Bhaga, Miyar, Bhut, Warwan and Ravi, six major tributaries of Chenab River, becomes crucial to assess the water availability. In addition, altitudinal distribution of snow cover significantly influences the melt runoff which is highly sensitive to minor variations in atmospheric temperature. In this investigation, remote sensing based Normalized Difference Snow Index technique has been used to generate 10 daily snow cover product. Snow cover monitoring of all the sub-basins were carried out for 10 years from 2004–2005 to 2013–2014 during hydrological year (October to June) using Advanced Wide Field Sensor (AWiFS) of Indian remote sensing satellite (IRS). Accumulation and ablation patterns of snow cover have also been analyzed for the six sub-basins. Accumulation and ablation pattern of snow cover, from 2004 to 2014 which shows slightly increasing trend for all the sub-basins. Meteorological data of Kelong at Bhaga sub-basin was also analysed. Average monthly snow line altitude was estimated for all the sub-basins using hypsographic curve. Chandra and Bhaga sub-basins are at higher altitude and Ravi sub-basin is at lower altitude. It was also observed that areal extent of snow reaches to lower altitude during last 5 years, particularly in Ravi sub-basin.     

The ionospheric impact of the October 2003 storm event on Wide Area Augmentation System

The United States Federal Aviation Administrations (FAA) Wide-Area Augmentation System (WAAS) for civil aircraft navigation is focused primarily on the Conterminous United States (CONUS). Other Satellite-Based Augmentation Systems (SBAS) include the European Geostationary Navigation Overlay Service (EGNOS) and the Japanese Multi-transport Satellite-based Augmentation System (MSAS). Navigation using WAAS requires accurate calibration of ionospheric delays. To provide delay corrections for single frequency global positioning system (GPS) users, the wide-area differential GPS systems depend upon accurate determination of ionospheric total electron content (TEC) along radio links. Dual-frequency transmissions from GPS satellites have been used for many years to measure and map ionospheric TEC on regional and global scales. The October 2003 solar-terrestrial events are significant not only for their dramatic scale, but also for their unique phasing of solar irradiance and geomagnetic events. During 28 October, the solar X-ray and EUV irradiances were exceptionally high while the geomagnetic activity was relatively normal. Conversely, 29–31 October was geomagnetically active while solar irradiances were relatively low. These events had the most severe impact in recent history on the CONUS region and therefore had a significant effect on the WAAS performance. To help better understand the event and its impact on WAAS, we examine in detail the WAAS reference site (WRS) data consisting of triple redundant dual-frequency GPS receivers at 25 different locations within the US. To provide ground-truth, we take advantage of the three co-located GPS receivers at each WAAS reference site. To generate ground-truth and calibrate GPS receiver and transmitter inter-frequency biases, we process the GPS data using the Global Ionospheric Mapping (GIM) software developed at the Jet Propulsion Laboratory. This software allows us to compute calibrated high resolution observations of TEC. We found ionospheric range delays up to 35 m for the day-time CONUS during quiet conditions and up to 100 m during storm time conditions. For a quiet day, we obtained WAAS planar fit slant residuals less than 2 m (0.4 m root mean square (RMS)) and less than 25 m (3.4 m RMS) for the storm day. We also investigated ionospheric gradients, averaged over distances of a few hundred kilometers. The gradients were no larger than 0.5 m over 100 km for a quiet day. For the storm day, we found gradients at the 4 m level over 100 km. Similar level gradients are typically observed in the low-latitude region for quiet or storm conditions.     

Dynamics of co-ignimbrite plumes generated from pyroclastic flows of Mount St. Helens (7 August 1980)

 Four co-ignimbrite plumes were generated along the flow path of the pyroclastic flow of 7 August 1980 at Mount St. Helens. Three of the plumes were generated in discrete pulses which can be linked to changes in slope along the channel. One plume was generated at the mouth of the channel where the flow decelerated markedly as it moved onto the lower slopes of the pumice plain. Plume generation here may be triggered by enhanced mixing due to a hydraulic jump associated with an abrupt slope change. Measurements of plume ascent velocity and width show that the co-ignimbrite plumes increased in velocity with height. The plumes have initial velocities of 1–2 m/s. Two of the plumes reached a velocity maximum (4.6 and 8.8 m/s, respectively, at heights of 270 and 315 m above the flow) and thereafter decelerated. The other plumes reached velocities of 6.2 and 13 m/s. The four plumes become systematically less energetic downstream as measured by their ascent rates, which can be interpreted as a consequence of decreasing interaction of the pyroclastic flow front with the atmosphere. Theoretical models of both co-ignimbrite plumes and discrete co-ignimbrite clouds assume that there is no initial momentum, and both are able to predict the observed acceleration stage. The rising plumes mix with and heat air and sediment out particles causing their buoyancy to increase. Theoretical models agree well with observations and suggest that the initial motion of the ascending material is best described as a discrete thermal cloud which expands as it entrains air, whereas the subsequent motion of the head may become influenced by material supplied from the following plume. The models agree well with observations for an initial temperature of the ash and air mixture in the range of 500–600 K, which is in turn consistent with the measured initial ash temperature of around 920 K. Ash masses of 3.4×10⁵ to 1.8×10⁶ kg are estimated. Received: 11 January 1996 / Accepted: 7 October 1996     

Behaviour of particle-laden flows into the ocean: experimental simulation and geological implications

The behaviour of subaerial particle-laden gravity currents (e.g. pyroclastic flows, lahars, debris flows, sediment-bearing floods and jökulhlaups) flowing into the sea has been simulated with analogue experiments. Flows of either saline solution, simple suspensions of silicon carbide (SiC) in water or complex suspensions of SiC and plastic particles in methanol were released down a slope into a tank of water. The excess momentum between subaerial and subaqueous flow is dissipated by a surface wave. At relatively low density contrasts between the tank water and the saline or simple suspensions, the flow mixture enters the water and forms a turbulent cloud involving extensive entrainment of water. The cloud then collapses gravitationally to form an underwater gravity current, which progresses along the tank floor. At higher density contrasts, the subaerial flow develops directly into a subaqueous flow. The flow slows and thickens in response to the reduced density contrast, which is driving motion, and then continues in the typical gravity current manner. Complex suspensions become dense flows along the tank floor or buoyant flows along the water surface, if the mixtures are sufficiently denser or lighter than water respectively. Flows of initially intermediate density are strongly influenced by the internal stratification of the subaerial flow. Material from the particulate-depleted upper sections of the subaerial flow becomes a buoyant gravity current along the water surface, whereas material from the particulate-enriched lower sections forms a dense flow along the tank floor. Sedimentation from the dense flow results in a reduction in bulk density until the mixture attains buoyancy, lifts off and becomes a secondary buoyant flow along the water surface. Jökulhlaups, lahars and debris flows are typically much denser than seawater and, thus, will usually form dense flows along the seabed. After sufficient sedimentation, the freshwater particulate mixture can lift off to form a buoyant flow at the sea surface, leading to a decoupling of the fine and coarse particles. Flood waters with low particulate concentrations (<2%) may form buoyant flows immediately upon entering the ocean. Subaerial pyroclastic flows develop a pronounced internal stratification during subaerial run-out and, thus, a flow-splitting behaviour is probable, which agrees with evidence for sea surface and underwater flows from historic eruptions of Krakatau and Mont Pelée. A pyroclastic flow with a bulk density closer to that of sea water may form a turbulent cloud, resulting in the deposition of much of the pyroclasts close to the shore. Dense subaqueous pyroclastic flows will eventually lift off and form secondary buoyant flows, either before or after the transformation to a water-supported nature.     

The Mechanical Coupling of Fluid-Filled Granular Material Under Shear

The coupled mechanics of fluid-filled granular media controls the physics of many Earth systems, for example saturated soils, fault gouge, and landslide shear zones. It is well established that when the pore fluid pressure rises, the shear resistance of fluid-filled granular systems decreases, and, as a result, catastrophic events such as soil liquefaction, earthquakes, and accelerating landslides may be triggered. Alternatively, when the pore pressure drops, the shear resistance of these geosystems increases. Despite the great importance of the coupled mechanics of grain–fluid systems, the basic physics that controls this coupling is far from understood. Fundamental questions that must be addressed include: what are the processes that control pore fluid pressurization and depressurization in response to deformation of the granular skeleton? and how do variations of pore pressure affect the mechanical strength of the grains skeleton? To answer these questions, a formulation for the pore fluid pressure and flow has been developed from mass and momentum conservation, and is coupled with a granular dynamics algorithm that solves the grain dynamics, to form a fully coupled model. The pore fluid formulation reveals that the evolution of pore pressure obeys viscoelastic rheology in response to pore space variations. Under undrained conditions elastic-like behavior dominates and leads to a linear relationship between pore pressure and overall volumetric strain. Viscous-like behavior dominates under well-drained conditions and leads to a linear relationship between pore pressure and volumetric strain rate. Numerical simulations reveal the possibility of liquefaction under drained and initially over-compacted conditions, which were often believed to be resistant to liquefaction. Under such conditions liquefaction occurs during short compactive phases that punctuate the overall dilative trend. In addition, the previously recognized generation of elevated pore pressure under undrained compactive conditions is observed. Simulations also show that during liquefaction events stress chains are detached, the external load becomes completely supported by the pressurized pore fluid, and shear resistance vanishes.