Nano-scale spatial confinement can alter chemistry at mineral–water interfaces. These nano-scale confinement effects can lead to anomalous fate and transport behavior of aqueous metal species. When a fluid resides in a nanoporous environments (pore size under 100 nm), the observed density, surface tension, and dielectric constant diverge from those measured in the bulk. To evaluate the impact of nano-scale confinement on the adsorption of copper (Cu2+), we performed batch adsorption studies using mesoporous silica. Mesoporous silica with the narrow distribution of pore diameters (SBA-15; 8, 6, and 4 nm pore diameters) was chosen since the silanol functional groups are typical to surface environments. Batch adsorption isotherms were fit with adsorption models (Langmuir, Freundlich, and Dubinin–Radushkevich) and adsorption kinetic data were fit to a pseudo-first-order reaction model. We found that with decreasing pore size, the maximum surface area-normalized uptake of Cu2+ increased. The pseudo-first-order kinetic model demonstrates that the adsorption is faster as the pore size decreases from 8 to 4 nm. We attribute these effects to the deviations in fundamental water properties as pore diameter decreases. In particular, these effects are most notable in SBA-15 with a 4-nm pore where the changes in water properties may be responsible for the enhanced Cu mobility, and therefore, faster Cu adsorption kinetics. 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.
Estuaries act as an organic matter and nutrient filter in the transition between the land, rivers and the ocean. In the past, high nutrient and organic carbon load and low oxygen concentration made the Elbe River estuary (NW Europe) a sink for dissolved inorganic nitrogen. A recent reduction in loads and subsequent recovery of the estuary changed its biogeochemical function, so that nitrate is no longer removed on its transition towards the coastal North Sea. Nowadays in the estuary, nitrification appears to be a significant nitrate source. To quantify nitrification and determine actively nitrifying regions in the estuary, we measured the concentrations of ammonium, nitrite and nitrate, the dual stable isotopes of nitrate and net nitrification rates in the estuary on five cruises from August 2012 to August 2013. The nitrate concentration increased markedly downstream of the port of Hamburg in summer and spring, accompanied by a decrease of nitrate isotope values that was clearest in summer exactly at the location where nitrate concentration started to increase. Ammonium and nitrite peaked in the Hamburg port region (up to 18 and 8 μmol L?1, respectively), and nitrification rates in this region were up to 7 μmol L?1 day?1. Our data show that coupled re-mineralization and nitrification are significant internal nitrate sources that almost double the estuary’s summer nitrate concentration. Furthermore, we find that the port of Hamburg is a hot spot of nitrification, whereas the maximum turbidity zone (MTZ) only plays a subordinate role in turnover of nitrate. 相似文献
We developed a spatially explicit, individual-based model to analyze how hypoxia effects on reproduction, growth, and mortality of Atlantic croaker in the northwestern Gulf of Mexico lead to population-level responses. The model follows the hourly growth, mortality, reproduction, and movement of individuals on a 300 × 800 spatial grid of 1-km2 cells for 140 years. Chlorophyll-a concentration, water temperature, and dissolved oxygen (DO) were specified daily for each grid cell and repeated for each year of the simulation. A bioenergetics model was used to represent growth, mortality was assumed stage- and age-dependent, and the movement behavior of juveniles and adults was modeled based on temperature and avoidance of low DO. Hypoxia effects were imposed using exposure effect submodels that converted time-varying exposures to low DO to reduced hourly growth, increased hourly mortality, and reduced annual fecundity. Results showed that 100 years of either mild or intermediate hypoxia produced small reductions in population abundance, while repeated severe hypoxia caused a 19% reduction in long-term population abundance. Relatively few individuals were exposed to low DO each hour, but many individuals experienced some exposure. The response was dominated by a 5% average reduction in annual fecundity of individuals. Under conditions of random sequences of mild, intermediate, and severe hypoxia years occurring in proportion to their historical frequency, the model predicted a 10% decrease in the long-term population abundance of croaker. A companion paper substitutes hourly DO values from a three-dimensional water quality model for the idealized hypoxia and results in a more realistic population reduction of about 25%. 相似文献
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
River deltas along Alaska’s Beaufort Sea coast are used by hatch-year semipalmated sandpipers (Calidris pusilla) after leaving their terrestrial natal sites, but the drivers of their use of these stopover sites on the first “hop” of fall migration are unknown. We quantified sandpiper temporal distribution and abundance as related to food resources at three river deltas during the beginning of their fall migration (post-breeding period) to compare the habitat quality among these deltas. We conducted population counts, sampled invertebrates, and captured birds to collect blood samples from individuals for triglyceride and stable isotope analyses to determine fattening rates and diet. Patterns of sandpiper and invertebrate abundance were complex and varied among deltas and within seasons. River deltas were used by sandpipers from late July to late August, and peak sandpiper counts ranged from 1000 to 4000 individuals, of which 98% were hatch-year semipalmated sandpipers. Isotopic signatures from blood plasma samples indicated that birds switched from a diet of upland tundra to delta invertebrate taxa as the migration season progressed, suggesting a dependence on delta invertebrates. Despite differences in diet among deltas, we found no differences in fattening rates of juvenile sandpipers as indicated by triglyceride levels. The number of sandpipers was positively associated with abundance of Amphipoda and Oligochaeta at the Jago and Okpilak-Hulahula deltas; an isotopic mixing model indicated that sandpipers consumed Amphipoda and Oligochaeta at Jago, mostly Chironomidae at Okpilak-Hulahula and Spionidae at Canning. Regardless of the difference in sandpiper diets at the Beaufort Sea deltas, their similar fattening rates throughout the season indicate that all of these stopover sites provide a critical food resource for hatch-year sandpipers beginning their first migration. 相似文献
Evaluations of tidal wetland restoration efforts suffer from a lack of appropriate reference sites and standardized methods among projects. To help address these issues, the National Estuarine Research Reserve System (NERRS) and the NOAA Restoration Center engaged in a partnership to monitor ecological responses and evaluate 17 tidal wetland restoration projects associated with five reserves. The goals of this study were to (1) determine the level of restoration achieved at each project using the restoration performance index (RPI), which compares change in parameters over time between reference and restoration sites, (2) compare hydrologic and excavation restoration projects using the RPI, (3) identify key indicator parameters for assessing restoration effectiveness, and (4) evaluate the value of the NERRS as reference sites for local restoration projects. We found that the RPI, modified for this study, was an effective tool for evaluating relative differences in restoration performance; most projects achieved an intermediate level of restoration from 2008 to 2010, and two sites became very similar to their paired reference sites, indicating that the restoration efforts were highly effective. There were no differences in RPI scores between hydrologic and excavation restoration project types. Two abiotic parameters (marsh platform elevation and groundwater level) were significantly correlated with vegetation community structure and thus can potentially influence restoration performance. Our results highlight the value of the NERRS as reference sites for assessing tidal wetland restoration projects and provide improved guidance for scientists and restoration practitioners by highlighting the RPI as a trajectory analysis tool and identifying key monitoring parameters. 相似文献
The present paper aims at characterising Alpine anomalous basin-fan systems, in order to develop a method for hazard assessment for such fans. The review of previous studies revealed that anomalous basin-fan systems are often associated with deep-seated slope failure and present-day hazard is associated to debris flow occurrence. Taking into account these peculiarities, a modelling approach to assess the present day hazard in anomalous fans has been developed and applied to the Sernio fan (Valtellina, northern Italy). Debris flow inundation areas have been simulated by means of a numerical model (RApid Mass MovementS (RAMMS) debris flow), which includes a routine for the sediment entrainment. The range of the model parameters was defined based on previous studies, enabling a sensitivity analysis on the debris flow runout, as well as the flow height and velocity. Numerical results point out the paramount importance of entrainment phenomena on debris flow dynamic in anomalous systems, especially with reference to the bulking factor and debris yield rate that reach very high values, typical of basins with unlimited solid supply. 相似文献
Tidal marsh (re)creation on formerly embanked land is increasingly executed along estuaries and coasts in Europe and the USA, either by restoring complete or by reduced tidal exchange. Ecosystem functioning and services are largely affected by the hydro-geomorphologic development of these areas. For natural marshes, the latter is known to be steered by feedbacks between tidal inundation and sediment accretion, allowing marshes to reach and maintain an equilibrium elevation relative to the mean sea level. However, for marsh restoration sites, these feedbacks may be disturbed depending on the restoration design. This was investigated by comparing the inundation-elevation change feedbacks in a natural versus restoration site with reduced tidal exchange in the Scheldt estuary (Belgium). This study analyzes long-term (9 years) datasets on elevation change and tidal inundation properties to disentangle the different mechanisms behind this elevation-inundation feedback. Moreover, subsequent changes in sediment properties that may affect this feedback were explored. In the restoration area with reduced tidal exchange, we found a different elevation-inundation feedback than on natural marshes, which is a positive feedback on initially high sites (i.e., sediment accretion leads to increasing inundation, hence causing accelerating sediment accretion rates) and a gradual silting up of the whole area. Furthermore, there is evidence for the presence of a relict consolidated sediment layer. Consequently, shallow subsidence is less likely to occur. Although short-term ecological development of the tidal marsh was not impeded, long-term habitat development may be affected by the differences in hydro-geomorphological interactions. An increase of inundation frequency on the initially high sites may cause inhibition of habitat succession or even reversed succession. Over time, the climax state of the restoration area may be different compared to natural marshes. Moreover, sediment-related ecosystem services, such as nutrient and carbon burial, may be positively influenced because of continuing sedimentation, although flood water storage potential will decrease with increasing elevation. Depending on the restoration goals, ecosystem trajectories and delivery of ecosystem services can be controlled by adaptive management of the tidal volume entering the restoration area. 相似文献
