GGR Critical Review of Analytical Developments in 2006–2007

In 2005 the Geostandards and Geoanalytical Research editorial team, in the true spirit of scientific endeavour, embarked on an experiment of our own. We decided to trial a new kind of review, somewhat different from those more typically observed in journals, and one that would provide readers with a summary of analytical developments across a broad range of topics appropriate to the Earth sciences. The first contribution of this kind appeared in 2005, and reported on developments in 2003 (Hergt et al. 2005). The second, this time a biennial review, was published in 2006 and reported on highlights of the 2004 and 2005 literature (Hergt et al. 2006). Based on reprint requests, positive remarks at conferences and strong citations we consider the experiment a resounding success and proudly present here the third in this series. This comprises six individual review sections that cover the main analytical technologies and topical application fields in geoanalysis and geochemistry, including geological and environmental reference materials, ICP‐thermal and secondary ionisation‐mass spectrometry, as well as neutron activation analysis, X‐ray fluorescence and atomic absorption spectrometry.     

GGR Biennial Review: Advances in Geo‐SIMS during 2006–2007

Secondary ion mass spectrometry (SIMS or ion microprobe) remains one of the most powerful tools available to the analytical geochemist. Despite the impressive progress witnessed by other competing laboratory methods over recent years, SIMS remains unsurpassed in its combination of small sampling volumes with low analytical uncertainties. Although the current SIMS analytical design has existed for over three decades, the period 2006–2007 saw significant advances in instrumentation, analytical methodology and, not least, the characterisation of new reference materials upon which all analyses depend. As of the end of 2007 the SIMS geoscience literature was reporting total sampling masses down to the 10 fg range, spatial resolution of better than 100 nm and uncertainties on major element isotope ratio determinations of better than ± 0.2‰ (1s). This article intends to synthesise the progress made by the geo‐SIMS community during this two year period and will also highlight some specific research results that were only possible due to the unique capabilities provided by SIMS.     

1896–2006 Sahelian annual rainfall variability and runoff increase of Sahelian Rivers

Updated rainfall data to 2006 confirm that the Sahelian rainfall has increased since the end of the 1990s, but the annual average rainfall is still as low as during the drought of the 1970s. The decrease of rainfall is higher in the Northwest and lower in the Southeast Sahel. The increase of temperature over West Africa during the end of the 20th century induced an increase of Potential Evaporation, which might reduce the runoff. However, the joint effect of climate change and of human activities on land cover over more than three decades is responsible for an increase of the runoff coefficients of the West African Sahelian Rivers since the 1970s, despite the rainfall shortage during the same period, as revealed by the analysis of runoff from Mauritania, Burkina-Faso and Niger. The runoff coefficients have increased in regions with less than 750 mm of annual rainfall, under Sahelian and subdesertic climates, leading to increased flood peaks, occurring earlier in the season. Even if it is difficult to separate which part of this runoff coefficient increase is due to climate change alone or to human impact on land cover, the highest values are observed in the most inhabited areas, where land cover is dominated by cultivated areas. This climatic/human impact on land cover is so huge that it has changed since decades the hydrological regimes of the Sahelian Rivers, from the small watershed to the largest one, such as the Niger River at Niamey.     

An enlarged and updated internally consistent thermodynamic dataset with uncertainties and correlations: the system K2O–Na2O–CaO–MgO–MnO–FeO–Fe2O3–Al2O3–TiO2–SiO2–C–H2–O2

We present, as a progress report, a revised and much enlarged version of the thermodynamic dataset given earlier (Holland & Powell, 1985). This new set includes data for 123 mineral and fluid end-members made consistent with over 200 P–T–X_CO2–f_O2 phase equilibrium experiments. Several improvements and advances have been made, in addition to the increased coverage of mineral phases: the data are now presented in three groups ranked according to reliability; a large number of iron-bearing phases has been included through experimental and, in some cases, natural Fe:Mg partitioning data; H₂O and CO₂ contents of cordierites are accounted for with the solution model of Kurepin (1985); simple Landau theory is used to model lambda anomalies in heat capacity and the Al/Si order–disorder behaviour in some silicates, and Tschermak-substituted end-members have been derived for iron and magnesium end-members of chlorite, talc, muscovite, biotite, pyroxene and amphibole. For the subset of data which overlap those of Berman (1988), it is encouraging to find both (1) very substantial agreement between the two sets of thermodynamic data and (2) that the two sets reproduce the phase equilibrium experimental brackets to a very similar degree of accuracy. The main differences in the two datasets involve size (123 as compared to 67 end-members), the methods used in data reduction (least squares as compared to linear programming), and the provision for estimation of uncertainties with this dataset. For calculations on mineral assemblages in rocks, we aim to maximize the information available from the dataset, by combining the equilibria from all the reactions which can be written between the end-members in the minerals. For phase diagram calculations, we calculate the compositions of complex solid solutions (together with P and T) involved in invariant, univariant and divariant assemblages. Moreover we strongly believe in attempting to assess the probable uncertainties in calculated equilibria and hence provide a framework for performing simple error propagation in all calculations in thermocalc, the computer program we offer for an effective use of the dataset and the calculation methods we advocate.     

Tectonic features of the Lipari–Vulcano complex (Aeolian archipelago,Italy) from 10 years (1996–2006) of GPS data

The tectonic deformation of the Lipari–Vulcano complex, one of the most important active volcanic areas of the Mediterranean region, is studied here through the analysis of 10 years (1996–2006) of GPS data from both three permanent and 13 non‐permanent stations. This area can be considered crucial for the understanding of the interaction between the Eurasian and African plates in the Mediterranean area, and, in general, this work emphasizes a methodological approach, already applied in other areas worldwide ( J. Geophys. Res., 1996, 101 , 27 957 ; J. Geodyn., 1999, 27 , 213 ) where geodetic data and strain parameters maps of critical areas can help to improve our understanding of their geodynamical aspects. In this framework, this study is aimed at providing a kinematic deformation model on the basis of the dense geodetically estimated velocities of the Lipari–Vulcano complex. In particular, the observed deformation pattern can be described by a combination of (1) the main N–S regional compression and (2) a NNE–SSW compression with a small right‐lateral strike slip component acting along a tectonic structure trending N°40W between the two islands. This pattern was inspected through a simplified synthetic model.     

The stability of sapphirine + quartz: calculated phase equilibria in FeO–MgO–Al2O3–SiO2–TiO2–O

The presence in rocks of coexisting sapphirine + quartz has been widely used to diagnose conditions of ultra‐high‐temperature (UHT) metamorphism (>900 °C), an inference based on the restriction of this assemblage to temperatures >980 °C in the conventionally considered FeO–MgO–Al₂O₃–SiO₂ (FMAS) chemical system. With a new thermodynamic model for sapphirine that includes Fe₂O₃, phase equilibra modelling using thermocalc software has been undertaken in the FeO–MgO–Al₂O₃–SiO₂–O (FMASO) and FeO–MgO–Al₂O₃–SiO₂– TiO₂–O (FMASTO) chemical systems. Using a variety of calculated phase diagrams for quartz‐saturated systems, the effects of Fe₂O₃ and TiO₂ on FMAS phase relations are shown to be considerable. Importantly, the stability field of sapphirine + quartz assemblages extends down temperature to 850 °C in oxidized systems and thus out of the UHT range.     

Neutron Activation Analysis,Atomic Absorption and X‐Ray Fluorescence Spectrometry Review for 2006–2007

These mature analytical techniques do not show any change in publication level from the previous two years and AAS remains dominant in terms of the number of publications. The last two years have seen fewer technical improvements than in the previous review period. Some interesting papers dealing with uncertainty and quality assurance in INAA were published during 2006–2007. It is suggested that photon activation should be reconsidered because the source of electron accelerators has recently improved. A technique to preconcentrate Se for INAA determination has also been proposed. In the case of AAS, papers on analyte preconcentration continue to be more abundant than those relating to instrumental modification. Sample preparation for AAS is also active and ultrasound‐assisted leaching shows some promising applications. There were an unusual number of reviews concerned with AAS and those important to geological samples are cited here. A technique to preconcentrate Cr in water is presented and a new device to determine As and Se is showing some potential uses. Confocal X‐ray mapping continues to show interesting developments. One group developed a technique to perform XRF inside an oyster and an interesting application of μ‐XRF mapping of sediments is presented. Determination of platinum‐group elements (at μg g¹ concentrations) can be carried out very quickly with an improved XRF technique.