Compression mechanisms of coesite

 The structure of coesite has been determined at ten pressures up to a maximum of 8.68 GPa by single-crystal X-ray diffraction. The dominant mechanism of compression is the reduction of four of the five independent Si–O–Si angles within the structure. There is no evidence of the fifth linkage, Si1–O1–Si1, deviating from 180°. Some Si–O bond distances also decrease by up to 1.6% over the pressure range studied. The pattern of Si–O–Si angle reduction amounts to a rotation of the Si2 tetrahedron around the [001] direction. This rotation induces significant internal deformation of the Si1 tetrahedron. Comparison of the experimental data with rigid-unit distance least-squares simulations of coesite suggests that this pattern of compression, the anomalous positive values of both s₂₃ and K′′ in the equation of state of coesite, its high elastic anisotropy and the unusual straight Si1–O1–Si1 linkage within the structure are all consequences of the connectivity of the tetrahedral framework. Received: 11 July 2002 / Accepted: 14 January 2003 Acknowledgements The help of Christian Baerlocher of ETH Zurich in providing both the DLS-76 software and advice in its use is gratefully acknowledged, as are discussions with Paul Ribbe of Virginia Tech and the comments of two anonymous reviewers. The data analysis was supported by the National Science Foundation under grant EAR-0105864 to N.L. Ross and R.J. Angel.     

The Mobility of Rare Earth Elements and Redox Sensitive Elements in the Groundwater/Seawater Mixing Zone of a Shallow Coastal Aquifer

The concentrations of Rare Earth Elements (REE) and Redox Sensitive Elements (RSE) were measured in groundwaters along a transect of the forest-marsh interface of a surficial aquifer system in North Inlet, SC. The well transect extended from a forest recharge area across the marsh and tidal creek to a tidal recharge area of beach ridge. The concentrations of the RSE (Fe, Mn, and U) were consistent with reducing conditions through the transect. Fe was present at concentrations ranging from a few micromolar to greater than one hundred micromolar in most wells. U was depleted with respect to salinity predicted concentrations, indicating removal with respect to the seawater endmember. Dissolved Mn concentrations were generally low in all wells, indicating no significant solid source of Mn (as MnOx) in this system. When extrapolated to a global scale, estimates of U removal during seawater exchange with the aquifer solids equaled 10–20% of the total riverine dissolved U input flux. REE concentrations in the forest recharge area were high in shallow wells, and showed a light enriched fractionation pattern, characteristic of soil leaching by Natural Organic Matter (NOM) rich waters. A decrease in REE concentration with depth in the forest wells coupled with a trend towards Heavy REE (HREE) enriched fractionation pattern indicated removal of the REE coincident with NOM and Dissolved Organic Carbon (DOC) removal. The saline waters of the beach ridge wells show a Light REE (LREE) enriched fractionation pattern and have the highest overall concentrations of the REE, indicating a significant REE source to the seawater endmember waters. The concentration gradients along the beach ridge flow path indicate a large source in the deep wells, and net export of dissolved REE to the tidal creek system and the coastal ocean. Ultrafiltration experiments indicate a transition from a colloidal dominated reservoir for the REE in the forest wells to a colloidal and dissolved reservoir in the beach ridge wells. The ultrafiltration data coupled with a correlation with Dissolved Inorganic Carbon (DIC) release suggest that there is diagenetic mobilization of an REE rich organic carbon phase in the saline endmember wells. We suggest here that degradation of this relic terrestrial organic carbon and REE rich phase results in the export of dissolved REE equal to or exceeding river inputs in this region.     

The postglacial history of three Picea species in New England, USA

Given the difficulty of separating the three Picea species—P. glauca, P. mariana, and P. rubens (white, black, and red spruce)—in the pollen record, little is known about their unique histories in eastern North America following deglaciation. Here we report the first use of a classification tree analysis (CART) to distinguish pollen grains of these species. It was successfully applied to fossil pollen from eight sites in Maine and one in Massachusetts. We focused on the late glacial/early Holocene (14,000 to 8000 cal yr B.P.) and the late Holocene (1400 cal yr B.P. to present)—the two key periods since deglaciation when Picea has been abundant in the region. The result shows a shift from a Picea forest of P. glauca and P. mariana in the late glacial to a forest of P. rubens and P. mariana in the late Holocene. The small number of P. rubens grains identified from the late glacial/early Holocene samples (<5%) suggests that that species was either absent or rare at most of the sites. The occurrence and distribution of the three species do not reveal any geographic or temporal trend during late glacial time, but the data suggest that they were distributed in local patches on the landscape. The results of this study indicate that the recent population expansion of Picea (1000 to 500 cal yr B.P.) was likely the first time since deglaciation that P. rubens was abundant in the region.     

Kinetics and Mechanism of Trithionate and Tetrathionate Oxidation at Low pH by Hydroxyl Radicals

The oxidation kinetics of trithionate (S₃O₆^2- ) and tetrathionate (S₄O ₆ ^2- ) with hydroxyl radicals (OH^*) have been investigated in systems analogous to acid mine drainage (AMD) environments. The discovery of hydroxyl radical (OH^*) formation on pyrite surfaces (Borda et al., 2003) suggests hydroxyl radicals may affect the oxidation kinetics of intermediate sulfur species such as tetrathionate. Cyclic voltammetry experiments in acidic solutions indicate that the reaction of S₄O ₆ ^2- with OH^* goes through an unknown intermediate, tentatively assigned as S₃O ₄ ^n- . An outer-sphere electron transfer mechanism for the reaction of S₄O ₆ ^2- with OH^* to form S₃O ₄ ^n- is proposed based on experimental results. Oxidation rates for trithionate and tetrathionate in the presence of Fenton's reagent (which forms hydroxyl radicals) are too fast to be directly measured using UV-Vis spectrophotometry, electrochemical, or stop-flow spectrophotometry methods. Competitive reaction kinetics within the context of the Haber—Weiss mechanism suggests that the rate constant for the oxidation of trithionate and tetrathionate with OH^* is in excess of 10⁸ M^-1 sec^-1.     

Dynamic stochastic estimation of physical variables

A fundamental problem facing the physical sciences today is analysis of natural variations and mapping of spatiotemporal processes. Detailed maps describing the space/time distribution of groundwater contaminants, atmospheric pollutant deposition processes, rainfall intensity variables, external intermittency functions, etc. are tools whose importance in practical applications cannot be overestimated. Such maps are valuable inputs for numerous applications including, for example, solute transport, storm modeling, turbulent-nonturbulent flow characterization, weather prediction, and human exposure to hazardous substances. The approach considered here uses the spatiotemporal random field theory to study natural space/time variations and derive dynamic stochastic estimates of physical variables. The random field model is constructed in a space/time continuum that explicitly involves both spatial and temporal aspects and provides a rigorous representation of spatiotemporal variabilities and uncertainties. This has considerable advantages as regards analytical investigations of natural processes. The model is used to study natural space/time variations of springwater calcium ion data from the Dyle River catchment area, Belgium. This dataset is characterized by a spatially nonhomogeneous and temporally nonstationary variability that is quantified by random field parameters, such as orders of space/time continuity and random field increments. A rich class of covariance models is determined from the properties of the random field increments. The analysis leads to maps of continuity orders and covariances reflecting space/time calcium ion correlations and trends. Calcium ion estimates and the associated statistical errors are calculated at unmeasured locations/instants over the Dyle region using a space/time kriging algorithm. In practice, the interpretation of the results of the dynamic stochastic analysis should take into consideration the scale effects.