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81.
Pressure plays a critical role in controlling aqueous geochemical processes in deep oceans and deep ice. The putative ocean of Europa could have pressures of 1200 bars or higher on the seafloor, a pressure not dissimilar to the deepest ocean basin on Earth (the Mariana Trench at 1100 bars of pressure). At such high pressures, chemical thermodynamic relations need to explicitly consider pressure. A number of papers have addressed the role of pressure on equilibrium constants, activity coefficients, and the activity of water. None of these models deal, however, with processes at subzero temperatures, which may be important in cold environments on Earth and other planetary bodies. The objectives of this work were to (1) incorporate a pressure dependence into an existing geochemical model parameterized for subzero temperatures (FREZCHEM), (2) validate the model, and (3) simulate pressure-dependent processes on Europa. As part of objective 1, we examined two models for quantifying the volumetric properties of liquid water at subzero temperatures: one model is based on the measured properties of supercooled water, and the other model is based on the properties of liquid water in equilibrium with ice.The relative effect of pressure on solution properties falls in the order: equilibrium constants(K) > activity coefficients (γ) > activity of water (aw). The errors (%) in our model associated with these properties, however, fall in the order: γ > K > aw. The transposition between K and γ is due to a more accurate model for estimating K than for estimating γ. Only activity coefficients are likely to be significantly in error. However, even in this case, the errors are likely to be only in the range of 2 to 5% up to 1000 bars of pressure. Evidence based on the pressure/temperature melting of ice and salt solution densities argue in favor of the equilibrium water model, which depends on extrapolations, for characterizing the properties of liquid water in electrolyte solutions at subzero temperatures, rather than the supercooled water model. Model-derived estimates of mixed salt solution densities and chemical equilibria as a function of pressure are in reasonably good agreement with experimental measurements.To demonstrate the usefulness of this low-temperature, high-pressure model, we examined two hypothetical cases for Europa. Case 1 dealt with the ice cover of Europa, where we asked the question: How far above the putative ocean in the ice layer could we expect to find thermodynamically stable brine pockets that could serve as habitats for life? For a hypothetical nonconvecting 20 km icy shell, this potential life zone only extends 2.8 km into the icy shell before the eutectic is reached. For the case of a nonconvecting icy shell, the cold surface of Europa precludes stable aqueous phases (habitats for life) anywhere near the surface. Case 2 compared chemical equilibria at 1 bar (based on previous work) with a more realistic 1460 bars of pressure at the base of a 100 km Europan ocean. A pressure of 1460 bars, compared to 1 bar, caused a 12 K decrease in the temperature at which ice first formed and a 11 K increase in the temperature at which MgSO4·12H2O first formed. Remarkably, there was only a 1.2 K decrease in the eutectic temperatures between 1 and 1460 bars of pressure. Chemical systems and their response to pressure depend, ultimately, on the volumetric properties of individual constituents, which makes every system response highly individualistic.  相似文献   
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Cesium-137 derived from the explosion of the Chernobyl reactor in 1986 was preserved in anoxic sediments from a coastal environment in southern Rhode Island. Although the radioactive plume was detected in surface air samples at several locations in the United States, this is the first known record of a Chernobyl 137Cs peak in sediments from North America. The inventory of Chernobyl 137Cs that was preserved in the Pettaquamscutt River is small compared to European counterparts and should only be detectable for the next 15-20 yr. However, the presence of two 137Cs peaks (1963 and 1987) identifies a well-dated segment of the sediment column that could be exploited in understanding the decomposition and preservation of terrestrial and aquatic organic matter. Different methods for calculating the 210Pb chronology were also evaluated in this study and checked against independent varve counting. The end result is a detailed chronology of a site well suited for reconstruction of historical records of environmental change.  相似文献   
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Dense understory thickets of the native evergreen shrub Rhododendron maximum expanded initially following elimination of American chestnut by the chestnut blight, and later in response to loss of the eastern hemlock due to hemlock woolly adelgid invasion. Rhododendron thickets often blanket streams and their riparian zones, creating cool, low-light microclimates. To determine the effect of such understory thickets on summer stream temperatures, we removed riparian rhododendron understory on 300 m reaches of two southern Appalachian Mountain headwater streams, while leaving two 300 m reference reaches undisturbed. Overhead canopy was left intact in all four streams, but all streams were selected to have a significant component of dead or dying eastern hemlock in the overstory, creating time-varying canopy gaps throughout the reach. We continuously monitored temperatures upstream, within and downstream of treatment and reference reaches. Temperatures were monitored in all four streams in the summer before treatments were imposed (2014), and for two summers following treatment (2015, 2016). Temperatures varied significantly across and within streams prior to treatment and across years for the reference streams. After rhododendron removal, increases in summer stream temperatures were observed at some locations within the treatment reaches, but these increases did not persist downstream and varied by watershed, sensor, and year. Significant increases in daily maxima in treatment reaches ranged from 0.9 to 2.6°C. Overhead canopy provided enough shade to prevent rhododendron removal from increasing summer temperatures to levels deleterious to native cold-water fauna (average summer temperatures remained below 16°C), and local temperature effects were not persistent.  相似文献   
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A key to understanding Late Pleistocene megafaunal extinction dynamics is knowledge of megafaunal ecological response(s) to long-term environmental perturbations. Strategically, that requires targeting fossil deposits that accumulated during glacial and interglacial intervals both before and after human arrival, with subsequent palaeoecological models underpinned by robust and reliable chronologies. Late Pleistocene vertebrate fossil localities from the Darling Downs, eastern Australia, provide stratigraphically-intact, abundant megafaunal sequences, which allows for testing of anthropogenic versus climate change megafauna extinction hypotheses. Each stratigraphic unit at site QML796, Kings Creek Catchment, was previously shown to have had similar sampling potential, and the basal units contain both small-sized taxa (e.g., land snails, frogs, bandicoots, rodents) and megafauna. Importantly, sequential faunal horizons show stepwise decrease in taxonomic diversity with the loss of some, but not all, megafauna in the geographically-small palaeocatchment. The purpose of this paper is to present the results of our intensive, multidisciplinary dating study of the deposits (>40 dates). Dating by means of accelerator mass spectrometry (AMS) 14C (targeting bone, freshwater molluscs, and charcoal) and thermal ionisation mass spectrometry U/Th (targeting teeth and freshwater molluscs) do not agree with each other and, in the case of AMS 14C dating, lack internal consistency. Scanning electron microscopy and rare earth element analyses demonstrate that the dated molluscs are diagenetically altered and contain aragonite cements that incorporated secondary young C, suggesting that such dates should be regarded as minimum ages. AMS 14C dated charcoals provide ages that occur out of stratigraphic order, and cluster in the upper chronological limits of the technique (~40–48 ka). Again, we suggest that such results should be regarded as suspicious and only minimum ages. Subsequent OSL and U/Th (teeth) dating provide complimentary results and demonstrate that the faunal sequences actually span ~120–83 ka, thus occurring beyond the AMS 14C dating window. Importantly, the dates suggest that the local decline in biological diversity was initiated ~75,000 years before the colonisation of humans on the continent. Collectively, the data are most parsimoniously consistent with a pre-human climate change model for local habitat change and megafauna extinction, but not with a nearly simultaneous extinction of megafauna as required by the human-induced blitzkrieg extinction hypothesis. This study demonstrates the problems inherent in dating deposits that lie near the chronological limits of the radiocarbon dating technique, and highlights the need to cross-check previously-dated archaeological and megafauna deposits within the timeframe of earliest human colonisation and latest megafaunal survival.  相似文献   
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Elevated turbidity (Tn) and suspended sediment concentrations (SSC) during and following flood events can degrade water supply quality and aquatic ecosystem integrity. Streams draining glacially conditioned mountainous terrain, such as those in the Catskill Mountains of New York State, are particularly susceptible to high levels of Tn and SSC sourced from erosional contact with glacial-related sediment. This study forwards a novel approach to evaluate the effectiveness of stream restoration best management practices (BMPs) meant to reduce stream Tn and SSC, and demonstrates the approach within the Stony Clove sub-basin of the Catskills, a water supply source for New York City. The proposed approach is designed to isolate BMP effects from natural trends in Tn and SSC caused by trends in discharge and shifts in average Tn or SSC per unit discharge (Q) following large flood events. We develop Dynamic Linear Models (DLMs) to quantify how Tn-Q and SSC-Q relationships change over time at monitoring stations upstream and downstream of BMPs within the Stony Clove and in three other sub-basins without BMPs, providing observational evidence of BMP effectiveness. A process-based model, the River Erosion Model, is then developed to simulate natural, hydrology-driven SSC-Q dynamics in the Stony Clove sub-basin (absent of BMP effects). We use DLMs to compare the modelled and observed SSC-Q dynamics and isolate the influence of the BMPs. Results suggest that observed reductions in SSC and Tn in the Stony Clove sub-basin have been driven by a combination of declining streamflow and the installed BMPs, confirming the utility of the BMPs for the monitored hydrologic conditions.  相似文献   
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