Structural controls and mechanisms of diffusion in natural silicate melts

The diffusion properties of Na, Cs, Ba, Fe and Eu ions have been determined experimentally for a pantellerite melt and of these ions plus Li, Mn and Co in pitchstone melt, using the radiotracer residual-activity method, and narrow platinum capillaries, over the temperature range 1,200–1,400° C. In addition, Eu diffusion in a basaltic and an andesitic melt was determined. Diffusion of all cations follows an Arrhenius relationship, activation energy values being high for diffusion in the pantellerite melt (e.g. Eu: 100 kcal mol^–1) except in the case of Na (24.3 kcal mol^–1). Activation energies of diffusion in the pitchstone melt are similar to values recorded earlier for andesitic and basaltic melts.The new data are used, along with previously published data for diffusion in other composition melts, to examine the compositional and structural controls on diffusion. The range of diffusivities shows a marked change with melt composition; over two orders of magnitude for a basaltic melt, and nearly four orders for a pantellerite melt (both at 1,300° C). Diffusivity of all cations (except Li and Na) correlates positively with the proportion of network modifying cations. In the case of Li and Na the correlation is negative but the diffusivity of these ions correlates positively with the proportion of Na or of Na + K ions in the bulk melt. Diffusion behaviour in the pantellerite melt departs from the relationships shown by the data for other melt compositions, which could be partly explained by trivalent ions (such as Fe) occupying network forming positions. The diffusivity of alkali metal ions is strongly dependent on ionic radius, but this is not the case with the divalent and trivalent ions; diffusivity of these ions remains relatively constant with change in radius but decreases with increase in ionic charge.A compensation diagram shows four distinct but parallel trends for the majority of the cations in four melt types but the data for Li and Na plot on a separate trend. This and the other relationships are used to elucidate possible mechanisms of diffusion. Exchange mechanisms appear to be common, with the preservation of local charge balance. Li and Na diffuse by a distinct mechanism which involves exchange of similar or identical ions. The diffusion behaviour of the smaller alkali metal ions is sufficiently distinct from all other cations to indicate that diffusion could be an important factor in the geochemical fractionation of the alkali elements.s     

Professional Technologies in Schools: The Role of Pedagogical Knowledge in Teaching With Geospatial Technologies

Preparing learners for the future requires twenty-first-century teaching that integrates professional tools in the classroom. Geospatial technologies (GST), which represent geographical professional technologies, lack robust integration in high school geography. Researchers continue to ask why educators teach about rather than with GST. Understanding teacher decisions is paramount. This mixed methods study examined commonalities among teachers who use GST using Mishra and Koehler’s (2006 Mishra, P., and M. J. Koehler. 2006. Technological pedagogical content knowledge: A framework for teacher knowledge. Teachers College Record 108 (6):1017–54.[Crossref], [Web of Science ®] , [Google Scholar]) Technological, Pedagogical, Content Knowledge (TPCK) framework as a theoretical lens. This investigation examined whether geography teachers who exhibit stronger geospatial TPCK used GST more frequently than other teachers who exhibited a less developed knowledge base.     

(Re)constructing rural–urban spaces: gendered livelihoods,migration, and natural resources in South Africa

Critical approaches to development theory and practice provide alternative perspectives that focus on counterhegemonic and discursive dimensions of the development process. Feminist development is one such approach that opens up new spaces and opportunities to promote socially progressive and sustainable economic strategies. This paper uses feminist development geography as a framework to highlight the intersection of diverse spaces and economic strategies at the household and community levels. The analysis focuses on gendered livelihoods that are linked to circular migration and use of natural resources as a way to understand the integration of rural and urban spaces of development. The empirical section of this paper examines demographic patterns and socio-economic trends in Limpopo Province, South Africa as a context for the case study of two community-based women’s producer groups. These examples illustrate how economic strategies and social identities are embedded in and integrate both rural and urban spaces. This analysis contributes to feminist and post-structural development theory and practice by highlighting the potential for progressive forms of economic and social empowerment.     

Amino acid biogeochemistry and dating of offshore Peru/Chile phosphorites

Amino acid biogeochemical results for a suite of indurated sea-floor phosphate nodules from the Peru/Chile margin confirm the youthful nature of these deposits as previously indicated by uranium-series disequilibrium dating. Isoleucine epimerization is significant in the hydrolyzed acid soluble fraction of the nodules with a range in the D-alloisoleucine/L-isoleucine ratio from 0.06 to 0.32. Amino acid compositional patterns are uniform for all nodules and are similar to unlithified surface sediments from the region suggesting that the nodules and sediments constitute a single genetic series.     

Weathering of Oil in a Surficial Aquifer

The composition of crude oil in a surficial aquifer was determined in two locations at the Bemidji, MN, spill site. The abundances of 71 individual hydrocarbons varied within 16 locations sampled. Little depletion of these hydrocarbons (relative to the pipeline oil) occurred in the first 10 years after the spill, whereas losses of 25% to 85% of the total measured hydrocarbons occurred after 30 years. The C_6‐30 n‐alkanes, toluene, and o‐xylene were the most depleted hydrocarbons. Some hydrocarbons, such as the n‐C_10–24 cyclohexanes, tri‐ and tetra‐ methylbenzenes, acyclic isoprenoids, and naphthalenes were the least depleted. Benzene was detected at every sampling location 30 years after the spill. Degradation of the oil led to increases in the percent organic carbon and in the δ ¹³C of the oil. Another method of determining hydrocarbon loss was by normalizing the total measured hydrocarbon concentrations to that of the most conservative analytes. This method indicated that the total measured hydrocarbons were depleted by 47% to 77% and loss of the oil mass over 30 years was 18% to 31%. Differences in hydrocarbon depletion were related to the depth of the oil in the aquifer, local topography, amount of recharge reaching the oil, availability of electron acceptors, and the presence of less permeable soils above the oil. The results from this study indicate that once crude oil has been in the subsurface for a number of years there is no longer a “starting oil concentration” that can be used to understand processes that affect its fate and the transport of hydrocarbons in groundwater.     

NanoSIMS isotopic analysis of small presolar grains: Search for Si3N4 grains from AGB stars and Al and Ti isotopic compositions of rare presolar SiC grains

We report isotopic ratio measurements of small SiC and Si₃N₄ grains, with special emphasis on presolar SiC grains of type Z, and new nucleosynthesis models for ²⁶Al/²⁷Al and the Ti isotopic ratios in asymptotic giant branch (AGB) stars. With the NanoSIMS we analyzed 310 SiC grains from Murchison (carbonaceous CM2 chondrite) separate KJB (diameters 0.25-0.45 μm) and 153 SiC grains from KJG (diameters 1.8-3.7 μm), 154 SiC and 23 Si₃N₄ grains from Indarch (enstatite EH4 chondrite) separate IH6 (diameters 0.25-0.65 μm) for their C and N isotopic compositions, 549 SiC and 142 Si₃N₄ grains from IH6 for their C and Si isotopic compositions, 13 SiC grains from Murchison and 66 from Indarch for their Al-Mg compositions, and eight SiC grains from Murchison and 10 from Indarch for their Ti isotopic compositions. One of the original objectives of this effort was to compare isotopic analyses with the NanoSIMS with analyses previously obtained with the Cameca IMS 3f ion microprobe. Many of the Si₃N₄ grains from Indarch have isotopic anomalies but most of these apparently originate from adjacent SiC grains. Only one Si₃N₄ grain, with ¹³C and ¹⁴N excesses, has a likely AGB origin. The C, N, and Si isotopic data show that the percentage of SiC grains of type Y and Z increase with decreasing grain size (from ∼1% for grains >2 μm to ∼5-7% for grains of 0.5 μm), providing an opportunity for isotopic analyses in these rare grains. Our measurements expand the number of Al-Mg analyses on SiC Z grains from 4 to 23 and the number of Ti analyses on Z grains from 2 to 11. Inferred²⁶Al/²⁷Al ratios of Z grains are in the range found in mainstream and Y grains and do not exceed those predicted by models of AGB nucleosynthesis. Cool bottom processing (CBP) has been invoked to explain the low ¹²C/¹³C ratios of Z grains, but this process apparently does not lead to increased ²⁶Al production in the parent stars of these grains. This finding is in contrast to presolar oxide grains where CBP is needed to explain their high ²⁶Al/²⁷Al ratios. The low ^46,47,49Ti/⁴⁸Ti ratios found in Z grains and their correlation with low ²⁹Si/²⁸Si ratios extend the trend seen in mainstream grains and confirm an origin in low-metallicity AGB stars. The relatively large excesses in ³⁰Si and ⁵⁰Ti in Z grains are predicted by our models to be the result of increased production of these isotopes by neutron-capture nucleosynthesis in low-metallicity AGB stars. However, the predicted excesses in ⁵⁰Ti (and ⁴⁹Ti) are much larger than those found. Even lowering the strength of the ¹³C pocket cannot solve this discrepancy in a consistent way.     

Dynamics of flood water infiltration and ground water recharge in hyperarid desert

A study on flood water infiltration and ground water recharge of a shallow alluvial aquifer was conducted in the hyperarid section of the Kuiseb River, Namibia. The study site was selected to represent a typical desert ephemeral river. An instrumental setup allowed, for the first time, continuous monitoring of infiltration during a flood event through the channel bed and the entire vadose zone. The monitoring system included flexible time domain reflectometry probes that were designed to measure the temporal variation in vadose zone water content and instruments to concurrently measure the levels of flood and ground water. A sequence of five individual floods was monitored during the rainy season in early summer 2006. These newly generated data served to elucidate the dynamics of flood water infiltration. Each flood initiated an infiltration event which was expressed in wetting of the vadose zone followed by a measurable rise in the water table. The data enabled a direct calculation of the infiltration fluxes by various independent methods. The floods varied in their stages, peaks, and initial water contents. However, all floods produced very similar flux rates, suggesting that the recharge rates are less affected by the flood stages but rather controlled by flow duration and available aquifer storage under it. Large floods flood the stream channel terraces and promote the larger transmission losses. These, however, make only a negligible contribution to the recharge of the ground water. It is the flood duration within the active streambed, which may increase with flood magnitude that is important to the recharge process.     

CI-Miner: semantically enhancing scientific processes

The realization of an international cyberinfrastructure of shared resources to overcome time and space limitations is challenging scientists to rethink how to document their processes. Many known scientific process requirements that would normally be considered impossible to implement a few years ago are close to becoming a reality for scientists, such as large scale integration and data reuse, data sharing across distinct scientific domains, comprehensive support for explaining process results, and full search capability for scientific products across domains. This article introduces the CI-Miner approach that can be used to aggregate knowledge about scientific processes and their products through the use of semantic annotations. The article shows how this aggregated knowledge is used to benefit scientists during the development of their research activities. The discussion is grounded on lessons learned through the use of CI-Miner to semantically annotate scientific processes in the areas of geo-sciences, environmental sciences and solar physics: A use case in the field of geo-science illustrates the CI-Miner approach in action.     

An adaptive mesh refinement algorithm for compressible two-phase flow in porous media

We describe a second-order accurate sequential algorithm for solving two-phase multicomponent flow in porous media. The algorithm incorporates an unsplit second-order Godunov scheme that provides accurate resolution of sharp fronts. The method is implemented within a block structured adaptive mesh refinement (AMR) framework that allows grids to dynamically adapt to features of the flow and enables efficient parallelization of the algorithm. We demonstrate the second-order convergence rate of the algorithm and the accuracy of the AMR solutions compared to uniform fine-grid solutions. The algorithm is then used to simulate the leakage of gas from a Liquified Petroleum Gas (LPG) storage cavern, demonstrating its capability to capture complex behavior of the resulting flow. We further examine differences resulting from using different relative permeability functions.     

Effects of seawater carbonate ion concentration and temperature on shell U, Mg, and Sr in cultured planktonic foraminifera

We investigate the sensitivity of U/Ca, Mg/Ca, and Sr/Ca to changes in seawater [CO₃²⁻] and temperature in calcite produced by the two planktonic foraminifera species, Orbulina universa and Globigerina bulloides, in laboratory culture experiments. Our results demonstrate that at constant temperature, U/Ca in O. universa decreases by 25 ± 7% per 100 μmol [CO₃²⁻] kg⁻¹, as seawater [CO₃²⁻] increases from 110 to 470 μmol kg⁻¹. Results from G. bulloides suggest a similar relationship, but U/Ca is consistently offset by ∼+40% at the same environmental [CO₃²⁻]. In O. universa, U/Ca is insensitive to temperature between 15°C and 25°C. Applying the O. universa relationship to three U/Ca records from a related species, Globigerinoides sacculifer, we estimate that Caribbean and tropical Atlantic [CO₃²⁻] was 110 ± 70 μmol kg⁻¹ and 80 ± 40 μmol kg⁻¹ higher, respectively, during the last glacial period relative to the Holocene. This result is consistent with estimates of the glacial-interglacial change in surface water [CO₃²⁻] based on both modeling and on boron isotope pH estimates. In settings where the addition of U by diagenetic processes is not a factor, down-core records of foraminiferal U/Ca have potential to provide information about changes in the ocean’s carbonate concentration.Below ambient pH (pH < 8.2), Mg/Ca decreased by 7 ± 5% (O. universa) to 16 ± 6% (G. bulloides) per 0.1 unit increase in pH. Above ambient pH, the change in Mg/Ca was not significant for either species. This result suggests that Mg/Ca-based paleotemperature estimates for the Quaternary, during which surface-ocean pH has been at or above modern levels, have not been biased by variations in surface-water pH. Sr/Ca increased linearly by 1.6 ± 0.4% per 0.1 unit increase in pH. Shell Mg/Ca increased exponentially with temperature in O. universa, where Mg/Ca = 0.85 exp (0.096*T), whereas the change in Sr/Ca with temperature was within the reproducibility of replicate measurements.