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
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
Tropical cyclones that enter or form in the Gulf of Mexico generate storm surge and large waves that impact low-lying coastlines along the Gulf Coast. The Chandeleur Islands, located 161 km east of New Orleans, Louisiana, have endured numerous hurricanes that have passed nearby. Hurricane Katrina (landfall near Waveland MS, 29 Aug 2005) caused dramatic changes to the island elevation and shape. In this paper the predictability of hurricane-induced barrier island erosion and accretion is evaluated using a coupled hydrodynamic and morphodynamic model known as XBeach. Pre- and post-storm island topography was surveyed with an airborne lidar system. Numerical simulations utilized realistic surge and wave conditions determined from larger-scale hydrodynamic models. Simulations included model sensitivity tests with varying grid size and temporal resolutions. Model-predicted bathymetry/topography and post-storm survey data both showed similar patterns of island erosion, such as increased dissection by channels. However, the model under predicted the magnitude of erosion. Potential causes for under prediction include (1) errors in the initial conditions (the initial bathymetry/topography was measured three years prior to Katrina), (2) errors in the forcing conditions (a result of our omission of storms prior to Katrina and/or errors in Katrina storm conditions), and/or (3) physical processes that were omitted from the model (e.g., inclusion of sediment variations and bio-physical processes). 相似文献
The distribution of suspended particle size and concentration were measured along the Gironde Estuary, France, from the river seaward to the ocean. The suspended particle size and volume concentration were measured using in situ holography and onboard optical techniques utilizing special procedures in order to avoid floc breakage. Sediments discharged by the rivers coagulate upon encountering the very low salinities (0.2‰ of the upper estuary (confirmed with laboratory experiments), and are then transported and deposited by currents in the remainder of the estuary. This coagulation, coupled with estuarine circulation, produces a turbidity maximum which is offset between the surface and bottom waters. The floc size maximum is oceanward of the turbidity maximum and is, likewise, offset along the estuary by about 30 km. The estuary can be subdivided into the following zones: (1) coagulation; (2) hydrodynamic, landward of the null point; and (3) hydrodynamic, seaward of the null point. Initial coagulation appears to be completed in coagulation zone (1), and particles are transported and settled (with very little floc breakage and recoagulation) in zones (2) and (3) only. The floc settling velocities, coupled with estuarine circulation, control the concentration and size distributions of flocs in the water column, and eventually control the deposition of sediments. 相似文献
Previous data relating sea-surface temperature to heat flux across the air-sea interface were reanalyzed with a common formula for the wind-stress coefficient. An expression is proposed for the nondimensional thickness of the thermal sublayer: the expression increases with wind velocity at light winds and has a value of 7 when the wind velocity reaches 7 m s–1. 相似文献
Brachyuran crab larvae were sampled approximately monthly at four stations in the Gulf of Nicoya, a tropical estuary on the Pacific coast of Costa Rica, Central America. The gulf was divided into two regions based on physical and chemical characteristics. Larvae were identified to five families: Ocypodidae, Pinnotheridae, Portunidae, Majidae, Xanthidae. The abundance and distribution of these taxa were similar to that found in temperature estuaries of North America. Ocypodids, pinnixids, and xanthids were most common in the estuarine upper-gulf region while portunids were more common in the lower gulf. Majids were found in small numbers in the lower gulf. Only the ocypodids showed a consistent pattern in vertical distribution; larvae of this taxon were always more common in surface water. There was no consistent pattern in the seasonal abundance of the various taxa when compared among stations. 相似文献
Natural radionuclides in the uranium and thorium series were measured in solid tidal phases (suspended particles, bottom sediment, surface microlayer colloids) of a salt marsh in lower Delaware. The purpose was to identify potential processes responsible for trace element cycling (sources, redistribution and exchange) in salt water marshes and with their coastal waters. Generally, concentrations of U, Th,210Pb, and210Po on the tidal solid phases suggest a general mechanism by which tidal marshes appear to be trapping the nuclides into their interiors. The processes may include transport of enriched fine particles into the marsh, capture by salt marsh grass and chemical fixation by redox processes at the sediment surface. Specifically, the uranium contents of most of the samples are similar with activity ratios234U238U≧1, indicating a mixture of detrital and nondetrital (authigenic) uranium inputs such as seawater or ground water. Since the230Th daughter is generally deficient by about 50%, the authigenic enrichment process appears to favor uranium and is potentially linked to the extensive diagenetic sulfur redox cycle of salt marsh sediments. The210Po/210Pb activity ratio is less than one on Spartina adsorbed solids, and could suggest a general process in salt marshes which favors210Pb enrichment by atmospheric fallout over enrichment of210Po on time scales of weeks which correspond to complete tide marsh exchange. A228Th/232Th activity ratio of less than unity on the solids adsorbed onto marsh grass suggests a net process whereby diffusive loss of the intermediate daughter228Ra from the adsorbed solids to tidal waters dominates over potential228Th scavenging by suspended sediment. 相似文献
Seasonal occurrence and vertical distribution of larvae of two genera of brachyuran crab were studied in a secondary estuary flowing into Delaware Bay. Spawning in the xanthid crabRhithropanopeus harrisii occurred earlier with peak abundance of larvae in June and with a distinct decline in abundance in August. In contrast,Uca spp. larvae reached peak abundance in August. All zoeal stages ofR. harrisii were collected in the river suggesting that larvae of this species are retained in secondary estuaries near areas of prime adult habitat. Only zoea stage I larvae and megalopa ofUca spp. were collected in the river indicating that larvae of these speies may be flushed into the Delaware Bay and may not return to secondary estuaries near areas suitable for adult habitat until the megalopa stage is reached. It is not clear if this dispersal pattern is an active or passive process. *** DIRECT SUPPORT *** A01BY019 00004 相似文献
