Speciation of naturally-accumulated uranium in an organic-rich soil of an alpine region (Switzerland)

Very high concentrations of uranium (up to 4000 ppm) were found in a natural soil in the Dischma valley, an alpine region in the Grisons canton in Switzerland. The goal of this study was to examine the redox state and the nature of uranium binding in the soil matrix in order to understand the accumulation mechanism. Pore water profiles collected from Dischma soil revealed the establishment of anoxic conditions with increasing soil depth. A combination of chemical extraction methods and spectroscopy was applied to characterize the redox state and binding environment of uranium in the soil. Bicarbonate extraction under anoxic conditions released most of the uranium indicating that uranium occurs predominantly in the hexavalent form. Surprisingly, the uranium redox state did not vary greatly as a function of depth. X-ray absorption near edge spectroscopy (XANES), confirmed that uranium was present as a mixture of U(VI) and U(IV) with U(VI) dominating. Sequential extractions of soil samples showed that the dissolution of solid organic matter resulted in the simultaneous release of the majority of the soil uranium content (>95%). Extended X-ray absorption fine structure (EXAFS) spectroscopy also revealed that soil-associated uranium in the soil matrix was mainly octahedrally coordinated, with an average of 1.7 axial (at about 1.76 Å) and 4.6 to 5.3 equatorial oxygen atoms (at about 2.36 Å) indicating the dominance of a uranyl-like (UO22+) structure presumably mixed with some U(IV). An additional EXAFS signal (at about 3.2 Å) identified in some spectra suggested that uranium was also bound (via an oxygen atom) to a light element such as carbon, phosphorus or silicon. Gamma spectrometric measurements of soil profiles failed to identify uranium long-life daughter products in the soil which is an indication that uranium originates elsewhere and was transported to its current location by water. Finally, it was found that the release of uranium from the soil was significantly promoted at very low pH values (pH 2) and increased with increasing pH values (between pH 5 and 9).

Climate variability-observations, reconstructions, and model simulations for the Atlantic-European and Alpine region from 1500-2100 AD

A detailed analysis is undertaken of the Atlantic-European climate using data from 500-year-long proxy-based climate reconstructions, a long climate simulation with perpetual 1990 forcing, as well as two global and one regional climate change scenarios. The observed and simulated interannual variability and teleconnectivity are compared and interpreted in order to improve the understanding of natural climate variability on interannual to decadal time scales for the late Holocene. The focus is set on the Atlantic-European and Alpine regions during the winter and summer seasons, using temperature, precipitation, and 500 hPa geopotential height fields. The climate reconstruction shows pronounced interdecadal variations that appear to “lock” the atmospheric circulation in quasi-steady long-term patterns over multi-decadal periods controlling at least part of the temperature and precipitation variability. Different circulation patterns are persistent over several decades for the period 1500 to 1900. The 500-year-long simulation with perpetual 1990 forcing shows some substantial differences, with a more unsteady teleconnectivity behaviour. Two global scenario simulations indicate a transition towards more stable teleconnectivity for the next 100 years. Time series of reconstructed and simulated temperature and precipitation over the Alpine region show comparatively small changes in interannual variability within the time frame considered, with the exception of the summer season, where a substantial increase in interannual variability is simulated by regional climate models.

PM(10) remote sensing from geostationary SEVIRI and polar-orbiting MODIS sensors over the complex terrain of the European Alpine region

The subject of this study is to investigate the capability of spaceborne remote sensing data to predict ground concentrations of PM10 over the European Alpine region using satellite derived Aerosol Optical Depth (AOD) from the geostationary Spinning Enhanced Visible and InfraRed Imager (SEVIRI) and the polar-orbiting MODerate resolution Imaging Spectroradiometer (MODIS). The spatial and temporal resolutions of these aerosol products (10 km and 2 measurements per day for MODIS, ∼ 25 km and observation intervals of 15 min for SEVIRI) permit an evaluation of PM estimation from space at different spatial and temporal scales. Different empirical linear relationships between coincident AOD and PM10 observations are evaluated at 13 ground-based PM measurement sites, with the assumption that aerosols are vertically homogeneously distributed below the planetary Boundary Layer Height (BLH). The BLH and Relative Humidity (RH) variability are assessed, as well as their impact on the parameterization. The BLH has a strong influence on the correlation of daily and hourly time series, whilst RH effects are less clear and smaller in magnitude. Despite its lower spatial resolution and AOD accuracy, SEVIRI shows higher correlations than MODIS (rSEV∼ 0.7, rMOD∼ 0.6) with regard to daily averaged PM10. Advantages from MODIS arise only at hourly time scales in mountainous locations but lower correlations were found for both sensors at this time scale (r∼ 0.45). Moreover, the fraction of days in 2008 with at least one satellite observation was 27% for SEVIRI and 17% for MODIS. These results suggest that the frequency of observations plays an important role in PM monitoring, while higher spatial resolution does not generally improve the PM estimation. Ground-based Sun Photometer (SP) measurements are used to validate the satellite-based AOD in the study region and to discuss the impact of aerosols' micro-physical properties in the empirical models. A lower error limit of 30 to 60% in the PM10 assessment from space is estimated in the study area as a result of AOD uncertainties, variability of aerosols properties and the heterogeneity of ground measurement sites. It is concluded that SEVIRI has a similar capacity to map PM as sensors on board polar-orbiting platforms, with the advantage of a higher number of observations. However, the accuracy represents a serious limitation to the applicability of satellites for ground PM mapping, especially in mountainous areas.

Stacking of discontinuous regional palaeoclimate records: Chironomid-based summer temperatures from the Alpine region

Since multi-site reconstructions are less affected by site-specific climatic effects and artefacts, regional palaeotemperature reconstructions based on a number of sites can provide more robust estimates of centennial- to millennial-scale temperature trends than individual, site-specific records. Furthermore, reconstructions based on multiple records are necessary for developing continuous climate records over time scales longer than covered by individual sequences. Here, we present a procedure for developing such reconstructions based on relatively short (centuries to millennia), discontinuously sampled records as are typically developed when using biotic proxies in lake sediments for temperature reconstruction. The approach includes an altitudinal correction of temperatures, an interpolation of individual records to equal time intervals, a stacking procedure for sections of the interval of interest that have the same records available, as well as a splicing procedure to link the individual stacked records into a continuous reconstruction. Variations in the final, stacked and spliced reconstruction are driven by variations in the individual records, whereas the absolute temperature values are determined by the stacked segment based on the largest number of records. With numerical simulations based on the NGRIP δ18O record, we demonstrate that the interpolation and stacking procedure provides an approximation of a smoothed palaeoclimate record if based on a sufficient number of discontinuously sampled records. Finally, we provide an example of a stacked and spliced palaeotemperature reconstruction 15000–90 calibrated 14C yr BP based on six chironomid records from the northern and central Swiss Alps and eastern France to discuss the potential and limitations of this approach.