Oxidation of pyrite during extraction of carbonate associated sulfate

The sulfur isotopic composition of carbonate associated sulfate (CAS) has been used to investigate the geochemistry of ancient seawater sulfate. However, few studies have quantified the reliability of δ³⁴S of CAS as a seawater sulfate proxy, especially with respect to later diagenetic overprinting. Pyrite, which typically has depleted δ³⁴S values due to authigenic fractionation associated with bacterial sulfate reduction, is a common constituent of marine sedimentary rocks. The oxidation of pyrite, whether during diagenesis or sample preparation, could thus adversely influence the sulfur isotopic composition of CAS. Here, we report the results of CAS extractions using HCl and acetic acid with samples spiked with varying amounts of pyrite. The results show a very strong linear relationship between the abundance of fine-grained pyrite added to the sample and the resultant abundance and δ³⁴S value of CAS. This data represents the first unequivocal evidence that pyrite is oxidized during the CAS extraction process. Our mixing models indicate that in samples with much less than 1 wt.% pyrite and relatively high δ³⁴S_pyrite values, the isotopic offset imparted by oxidation of pyrite should be much less than ? 4‰. A wealth of literature exists on the oxidation of pyrite by Fe³⁺ and we believe this mechanism drives the oxidation of pyrite during CAS extraction, during which the oxygen used to form sulfate is taken from H₂O, not O₂. Consequently, extracting CAS under anaerobic conditions would only slow, but not halt, the oxidation of pyrite. Future studies of CAS should attempt to quantify pyrite abundance and isotopic composition.     

A probabilistic framework for improving reverse geocoding output

Reverse geocoding, which transforms machine‐readable GPS coordinates into human‐readable location information, is widely used in a variety of location‐based services and analysis. The output quality of reverse geocoding is critical because it can greatly impact these services provided to end‐users. We argue that the output of reverse geocoding should be spatially close to and topologically correct with respect to the input coordinates, contain multiple suggestions ranked by a uniform standard, and incorporate GPS uncertainties. However, existing reverse geocoding systems often fail to fulfill these aims. To further improve the reverse geocoding process, we propose a probabilistic framework that includes: (1) a new workflow that can adapt all existing address models and unitizes distance and topology relations among retrieved reference data for candidate selections; (2) an advanced scoring mechanism that quantifies characteristics of the entire workflow and orders candidates according to their likelihood of being the best candidate; and (3) a novel algorithm that derives statistical surfaces for input GPS uncertainties and propagates such uncertainties into final output lists. The efficiency of the proposed approaches is demonstrated through comparisons to the four commercial reverse geocoding systems and through human judgments. We envision that more advanced reverse geocoding output ranking algorithms specific to different application scenarios can be built upon this work.     

A comparison of network model creation algorithms based on the quality of wayfinding results

Various network model creation algorithms have been introduced to demonstrate a better approximation of the actual walking pattern and to provide a better wayfinding guide. However, it is under‐investigated which algorithm creates the most appropriate indoor navigation network model in the context of wayfinding applications. Due to the lack of discussion, some studies unconsciously extended an algorithm designed for creating an outdoor navigation network model to indoor space applications. This is problematic because indoor space has different spatial contexts from outdoor space, such as non‐linear space and no‐designated walking space. Our solution is to select five well‐known algorithms that have been introduced, to reproduce the algorithm for the automated construction of the indoor navigation network model, and to evaluate the applicability of algorithms for indoor wayfinding applications. This article compares the quality of wayfinding results from the output of the indoor navigation network model against two criteria: route efficiency (i.e., length) and route simplicity (i.e., number of directions). Our statistical analysis illustrates that the visibility graph algorithm is the most appropriate for indoor wayfinding applications.     

GPS for real-time earthquake source determination and tsunami warning systems

We identify the key design aspects of a GPS-based system (and in the future, GNSS-based systems) that could contribute to real-time earthquake source determination and tsunami warning systems. Our approach is based on models of both transient and permanent displacement of GPS stations caused by large earthquakes, while considering the effect of GPS errors on inverted earthquake source parameters. Our main conclusions are that (1) the spatial pattern, magnitude, and timing of permanent displacement of GPS stations can be inverted for the earthquake source and so predict the 3D displacement field of the ocean bottom, thus providing the initial conditions for tsunami models, and (2) there are no inherently limiting factors arising from real-time orbit and positioning errors, provided sufficient near-field GPS stations are deployed. This signal could be readily exploited by GPS networks currently in place, and will be facilitated by the IGS Real-Time Project as it comes to fruition.     

Radon-222 as a tracer for mixing in the water column and benthic exchange in the southern California borderland

The concentrations of²²²Rn and²²⁶Ra in the water column and in the sediments of Santa Barbara and San Nicolas Basins have been measured semi-annually over the last four years. Approximately one-third of excess radon profiles obtained in the water column in these basins can be adequately fit with a one-dimensional eddy diffusion-decay model. Exponential profiles in the center of San Nicolas Basin yield a vertical eddy diffusivity of 26±16 cm²/s and 3.4±1.0 cm²/s for Santa Barbara Basin. The application of a two-dimensional eddy diffusion-decay model to profiles obtained in the center and on the margins of San Nicolas Basin produces a better fit than is found using a one-dimensional vertical eddy diffusivity. The two-dimensional model for San Nicolas Basin predicts a vertical eddy diffusivity of 17 cm²/s and a horizontal eddy diffusivity of 10⁵ cm²/s. These values are in reasonable agreement with those predicted from the vertical buoyancy gradient and the horizontal length scale.The vertically integrated radon excess (standing crop) in the water column of Santa Barbara Basin averages 53±23 atoms/m² s. This is in good agreement with the flux across the sediment-water interface of 60±15 atoms/m² s, calculated by measuring radon emanation in the sediments as a function of depth and applying a molecular diffusion-reaction model. Hence, one-dimensional molecular diffusion accurately predicts the flux of radon from the laminated Santa Barbara Basin sediments. In San Nicolas Basin the integrated radon excess in the water column is 376±143 atoms/m² s, but the diffusive randon flux from San Nicolas Basin sediments averages only 190±53 atoms/m² s. This descrepancy indicates that a non-diffusive process, probably macrofaunal irrigation, supplies much of the flux of radon from San Nicolas Basin sediments.     

The ilmenite/titano-magnetite assemblage: kinetics of re-equilibration

Compositions of coexisting ilmenite and titano-magnetite commonly have been used to establish the conditions of formation for igneous and metamorphic rocks (Buddington-Lindsley geothermometer/oxybarometer). Temperatures so determined for some rocks are lower than might be expected for magmatic crystallization. These low temperatures are the result of re-equilibration of the Fe-Ti oxides during slow cooling. This process is one in which titano-magnetites are oxidized and ilmenites are reduced upon cooling along a buffer curve or in the presence of a fluid of constant composition. Textural studies indicate that the reduction of the ilmenite-hematite phase may be the slower reaction consequently, the rate-controlling step of the re-equilibration.The kinetics of the reduction reactions in the two-phase region between the joins for the ilmenite-hematite and magnetite-ulvöspinel solid solution series were studied by thermogravimetric analysis at controlledf_O2. With experiments conducted near the Ni/NiO and QFM buffers, annealed ilmenite(ss) synthetic charges were reduced isothermally. The temperature range for the experiments was 900–1250°C, with total gas-flow rates of 0.35 and 1.0 cm/s. Kinetic data were collected by measuring the weight change during each experiment as a function of time. Additionally, a cooling-rate (0.5°C/hr) experiment was conducted near the QFM buffer from 1150 to 985°C starting with an ilmenite-saturated spinel phase.At 1200°C and 0.35 cm/s flow rate, the reaction mechanism is an interfacial process where mass transport of the reacting gases is the rate-controlling step. In isothermal experiments at 1100°C and lower, diffusion of reactants through a solid product layer was the controlling mechanism. The activation energy for this diffusion process is 59±6 kcal/mole. Significant enhancement of diffusion occurs along grain boundaries.Although the individual phases may re-equilibrate internally upon cooling, the Fe-Ti contents must remain unchanged for proper use of this mineral indicator-i.e. no external re-equilibration. It is imperative that the kinetics of the situation be appreciated. These preliminary kinetic experiments indicate that extreme caution must be exercised when applying this ilmenite/titano-magnetite geothermometer/oxybarometer. These phases may only truly “quench” in the parameters of formation in the case of certain hypabyssal and extrusive occurrences     

Characterizing groundwater flow in a faulted karst system using optical brighteners from septic systems as tracers

This study used optical brighteners (OB) released from septic systems to show that groundwater flow direction is largely controlled by the structural framework in a faulted karst groundwater system. Effective protection of groundwater resources requires that groundwater systems are adequately characterized and source water protection areas (SWPA) are developed for drinking water wells. Karst aquifers are among the most sensitive to contamination due to high recharge rates, and among the most difficult aquifers to characterize due to heterogeneity, and anisotropy. Because septic systems may be used to treat wastewater within SWPAs for karst aquifers there is a need to characterize these groundwater systems using tracers. The objective of this study was to characterize groundwater flow in a faulted portion of the Edwards aquifer in Bexar County, Texas using OB that are released as incidental tracers from septic systems. This study included measurement of water levels, sampling of groundwater and surface water, analysis for OB, and spatial analysis in a GIS. Results show that OB intensities were highest to the southwest of the septic area, a direction that is sub-parallel to the fault and fracture orientation and nearly perpendicular to the hydraulic gradient. This indicates that movement of OB, solutes, or non-aqueous liquids/solids in a faulted karst system can be largely controlled by fault/fracture orientation and structural relay ramps.     

Nutrient exchange across the sediment-water interface in the Potomac River estuary

The flux of ammonia, phosphate, silica and radon-222 from Potomac tidal river and estuary sediments is controlled by processes occurring at the sediment-water interface and within surficial sediment. Calculated diffusive fluxes range between 0·6 and 6·5 mmol m^?2 day^?1 for ammonia, 0·020 and 0·30 mmol m^?2 day^?1 for phosphate, and 1·3 and 3·8 mmol m^?2 day^?1 for silica. Measured in situ fluxes range between 1 and 21 mmol m^?2 day^?1 for ammonia, 0·1 and 2·0 mmol m^?2 day^?1 for phosphate, and 2 and 19 mmol m^?2 day^?1 for silica. The ratio of in situ fluxes to diffusive fluxes (flux enhancement) varied between 1·6 and 5·2 in the tidal river, between 2·0 and 20 in the transition zone, and from 1·3 to 5·1 in the lower estuary. The large flux enhancements from transition zone sediments are attributed to macrofaunal irrigation. Nutrient flux enhancements are correlated with radon flux enhancements, suggesting that fluxes may originate from a common region and that nutrients are regenerated within the upper 10–20 cm of the sediment column.The low fluxes of phosphate from tidal viver sediments reflect the control benthic sediment exerts on phosphorus through sorption by sedimentary iron oxyhydroxides. In the tidal river, benthic fluxes of ammonia and phosphate equal one-half and one-third of the nutrient input of the Blue Plains sewage treatment plant. In the tidal Potomac River, benthic sediment regeneration supplies a significant fraction of the nutrients utilized by primary producers in the water column during the summer months.