GGR Critical Review of Analytical Developments in 2004–2005

In 2005 Geostandards and Geoanalytical Research embarked upon a new initiative for its readers. Key researchers in various fields of geoanalytical technique development and their application were identified and invited to provide reviews pertinent to their expertise. As noted in the first of these publications "…instead of revisiting the historical context or decades of development in each analytical technique, the goal here has been to capture a snapshot of "hot topics" across a range of fields as represented in the… literature" (Hergt et al . 2005). Rather than prepare an annual review, a decision was taken earlier this year to provide a biennial summary of progress and accomplishments, in this case for the years 2004–2005. The principal techniques employed in Earth and environmental sciences are covered here, and include laser ablation and multicollector ICP-MS, ICP-AES, thermal ionisation and secondary ion mass spectrometry, as well as neutron activation analysis, X-ray fluorescence and atomic absorption spectrometry. A comprehensive review of the development of reference materials, often essential to these techniques, is also provided. The contributions assembled serve both to keep readers informed of advances they may be unfamiliar with, but also as a means of showcasing examples of the breadth and depth of work being conducted in these fields.     

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.     

Assessing the Vibrational Frequencies of the Cathedral of Cologne (Germany) by Means of Ambient Seismic Noise Analysis

Ambient seismic noise measurements were conducted inside the Cathedral of Cologne (Germany) for assessing its frequencies of vibration and for checking whether these occur in the range where soil amplification is expected. If this is the case, damages may increase in case of an earthquake due to an increased structural response of the building. Analysis of the ratio between the horizontal and vertical components of the spectra recorded at stations located inside the building as well as the ratio between the corresponding components of the spectra recorded simultaneously inside the building and at a reference station placed in the basement of the cathedral indicated several modes of vibration. Facilitated by these results an assessment of the seismic vulnerability was attempted for a 2D ground motion scenario using the finite element method.     

Results from a Multi-disciplinary Sedimentary Pilot Study of Tectonic Lake Iznik (NW Turkey) – Geochemistry and Paleolimnology of the Recent Past

A limnogeological reconnaissance study was carried out on Lake Iznik, located in the southeast of the Marmara region of Turkey, involving a seismic survey and collection of short sediment cores. This lake is located on the middle branch of the North Anatolian Fault Zone (NAFZ), a transform plate boundary between the Eurasian and Anatolian Plates. It is, therefore, tectonically active and offers an opportunity to investigate the interplay of sedimentary and seismo-tectonic processes, as well as climate change and human impact in the region. Short cores of the three sub-basins, maximum length of 35.5 cm, recovered non-laminated, blackish clays and silts with varying amounts of biogenic and minerogenic (allochthonous, autochthonous) material, which documented almost the last 80 years of deposition and environmental history. High sedimentation rates in the deeper core sections are accompanied by changes in land use (conversion of woodland to farmland) in the northern areas of Lake Iznik, which caused the deposition of more weathered material (high K/Na ratios) and higher contents of Mn in the lake. A tendency towards eutrophic conditions within the last 20 years is indicated by high nutrient content (N, TOC, P), decreasing C/N-ratios, and characteristic diatom and cladoceran associations. Also increased pollution is revealed by higher Pb, Cu, and Zn contents and increased supply of human and animal faeces (high coprostanol content) during the last two decades. But simultaneous lower sedimentation rates towards the core tops complicate the reconstruction of recent and past eutrophication and pollution states of Lake Iznik. This requires an extension of the pilot study and deeper sediment cores, to recover non-anthropogenic influenced sediment levels.     

A Comparison of Sediment Varves (1950–2003 AD) in Two Adjacent Lakes in Northern Sweden

Koltjärnen and Nylandssjön are two closely situated lakes (<2 km apart) in northern Sweden. During the past century, distinct varved sediments have formed in these lakes. Nylandssjön has two varved, deep basins. Since lake and catchment characteristics superficially appear very similar for the two lakes and they are exposed to the same climate, one would expect the sediment varves to be similar. This investigation compares the varves in the two deep basins of Nylandssjön, and in the two lakes. The comparison of basins of Nylandssjön shows that varve thickness, water content and annual accumulation rates of organic matter and nitrogen are correlated for the period (1970–2003). The grey-scale curves are only clearly similar in about 50% of the varves. In the between-lake comparison varve thickness, water content and annual accumulation rates of organic matter and nitrogen are correlated for the period (1950–1996). However, the annual accumulation rates of dry mass, minerogenic matter and biogenic silica differ between the lakes, as well as within-varve successions in grey-scale. A general explanation to the differences is that the prerequisites for varve formation are not totally similar because of differences in catchment size, catchment- to-lake material fluxes, lake productivity and land-use influence. This study illustrates the complex relationships that exist between a lake, its catchment, in-lake productivity and formation of sediment varves. As a consequence, we must not apply a too simplistic view of the potential of varves as past climatic indicators, especially if the lakes are affected by land-use.     

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.