Reference Materials in Geoanalytical Research -Review for 2004 and 2005

This review gives an overview of the use and development of reference materials of geochemical and environmental interest in the literature of the years 2004 and 2005. In these years the performance of existing methods has been improved and new geochemical applications using new techniques have been developed. Accordingly, there was an increasing need for new reference materials, especially for in situ microanalysis and for precise stable isotope measurements. In addition, there was a notable trend for further characterisation of existing reference materials, mainly for the platinum-group elements. This review focuses on five topics: reference materials for platinum-group elements, reference glasses for in situ microanalysis, zircon reference materials, isotopic reference materials, and the development and certification of reference materials.     

The structure and dynamics of 2-dimensional fluids in swelling clays

The interlayer pores of swelling 2:1 clays provide an ideal 2-dimensional environment in which to study confined fluids. In this paper we discuss our understanding of the structure and dynamics of interlayer fluid species in expanded clays, based primarily on the outcome of recent molecular modelling and neutron scattering studies. Counterion solvation is compared with that measured in bulk solutions, and at a local level the cation-oxygen coordination is found to be remarkably similar in these two environments. However, for the monovalent ions the contribution to the first coordination shell from the clay surfaces increases with counterion radius. This gives rise to inner-sphere (surface) complexes in the case of potassium and caesium. In this context, the location of the negative clay surface charge (i.e. arising from octahedral or tetrahedral substitution) is also found to be of major importance. Divalent cations, such as calcium, eagerly solvate to form outer-sphere complexes. These complexes are able to pin adjacent clay layers together, and thereby prevent colloidal swelling. Confined water molecules form hydrogen bonds to each other and to the clays' surfaces. In this way their local environment relaxes to close to the bulk water structure within two molecular layers of the clay surface. Finally, we discuss the way in which the simple organic molecules methane, methanol and ethylene glycol behave in the interlayer region of hydrated clays. Quasi-elastic neutron scattering of isotopically labelled interlayer CH₃OD and (CH₂OD)₂ in deuterated clay allows us to measure the diffusion of the CH₃- and CH₂-groups in both clay and liquid environments. We find that in both the one-layer methanol solvates and the two-layer glycol solvates the diffusion of the most mobile organic molecules is close to that in the bulk solution.     

Application of the QUILF thermobarometer to the peralkaline trachytes and pantellerites of the Eburru volcanic complex, East African Rift, Kenya

The Quaternary Eburru volcanic complex in the south-central Kenya Rift consists of pantelleritic trachytes and pantellerites. The phenocryst assemblage in the trachytes is sanidine + fayalite + ferrohedenbergite + aenigmatite ± quartz ± ilmenite ± magnetite ± pyrrhotite ± pyrite. In the pantellerites, the assemblage is sanidine + quartz + ferrohedenbergite + fayalite + aenigmatite + ferrorichterite + pyrrhotite ± apatite, although fayalite, ferrohedenbergite and ilmenite are absent from more evolved rocks (e.g. with SiO₂ > 71%). QUILF temperature calculations for the trachytes range from 709 to 793 °C and for the pantellerites 668–708 °C, the latter temperatures being among the lowest recorded for peralkaline silicic magmas. The QUILF thermobarometer demonstrates that the Eburru magmas crystallized at relatively low oxidation states (ΔFMQ + 0.5 to − 1.6) for both trachytes and pantellerites. The trachytes and pantellerites evolved along separate liquid lines of descent, the trachytes possibly deriving from a more mafic parent by fractional crystallization and the pantellerites from extreme fractionation of comenditic magmas.     

Lake Sediment Core Records of Sulphur Accumulation and Sulphur Isotopic Composition in Central Ontario, Canada Lakes

Stable isotopic compositions and concentrations of total sedimentary sulphur (S) were determined in cores from 6 lakes in the acid-sensitive Muskoka-Haliburton region of south-central Ontario. The isotopic composition of S in deep sediment (> ~ 20 cm) was approximately constant in all lakes, and indicated a pre-industrial δ ³⁴S value between +4.0 and +5.3‰, which is similar to current bulk deposition. Similarly, total S concentrations in deep sediment were relatively low (1.9–5 mg S g⁻¹ dwt) and approximately constant with depth within cores. All lakes exhibited up-core increases in total S and decreases in δ ³⁴S at a depth corresponding to the beginning of industrialization in the Great Lakes region ( ~ 1900), resulting in a generally reciprocal depth pattern between total S concentration and δ ³⁴S ratios. While initial shifts in total S and δ ³⁴S were likely due to enhanced SO₄ reduction of newly available anthropogenic SO₄, both the magnitude and pattern of up-core S enrichment and shifts in δ ³⁴S varied greatly among lakes, and did not match changes in S deposition post 1900. Differences between lakes in total S and δ ³⁴S were not related to any single hydrologic (e.g., residence time) or physical (e.g., catchment-area-to-lake area ratio) lake characteristic. This work indicates that sediment cores do not provide consistent records of changes in post-industrial S deposition in this region, likely due to redox-related mobility of S in upper sediment.     

Semi-Analytic Modelling of Subsidence

This paper presents a forward model for subsidence prediction caused by extraction of hydrocarbons. The model uses combinations of analytic solutions to the visco-elastic equations, which approximate the boundary conditions. There are only a few unknown parameters to be estimated, and, consequently, calculations are very fast. The semi-analytic model is applicable to a uniform and layer-cake stratigraphy, with visco-elastic parameters changing per layer, and an arbitrary depletion pattern. By its capabilities to handle a multi-layered visco-elastic subsurface, the semi-analytic model fills the gap between the analytic single-layered elastic models available to date and the more elaborate numerical, e.g. finite element, models.     

Space-Time Intelligence Systems: Technology, applications and methods

Geographic Information System (GIS) software is constrained, to a greater or lesser extent, by a static world view that is not well-suited to the representation of time (Goodchild 2000). Space Time Intelligence System (STIS) software holds the promise of relaxing some of the technological constraints of spatial only GIS, making possible visualization approaches and analysis methods that are appropriate for temporally dynamic geospatial data. This special issue of the Journal of Geographical Systems describes some recent advances in STIS technology and methods, with an emphasis on applications in public health and spatial epidemiology.The STIS expert workshops were funded in part by grants R01CA092669 and R01CA096002 from the National Cancer Institute, and by grants R43-ES010220 and R44-ES010220 from the National Institute of Environmental Health Sciences. Gillian AvRuskin provided cheerful editorial assistance. We thank the participants at the workshops for providing invaluable expertise and critical insights.     

Impact of the North Atlantic Oscillation on Middle Eastern Climate and Streamflow

Interannual to decadal variations in Middle Eastern temperature, precipitationand streamflow reflect the far-field influence of the North Atlantic Oscillation (NAO), a dominant mode of Atlantic sector climate variability. Using a new sea surface temperature (SST) based index of the NAO and availablestreamflow data from five Middle Eastern rivers, we show that the first principal component of December through March streamflow variability reflects changes in the NAO. However, Middle East rivers have two primary flooding periods.The first is rainfall-driven runoff from December through March, regulated on interannual to decadal timescales by the NAO as reflected in local precipitation and temperature.The second period, from April through June, reflects spring snowmelt and contributes in excess of 50% of annual runoff.This period, known locally as the khamsin, displays no significantNAO connections and a less direct relationship with local climatic factors, suggesting that streamflow variability during this period reflects land-cover change, possibly related to agriculture and hydropower generation, and snowmelt.