Structure of Silica Xerogels Synthesized with Organoalkoxysilane Co-reactants Hints at Multiple Phase Separation

The microstructure of hybrid silica xerogels synthesized by the base-catalyzed polymerization of tetraethoxysilane (TEOS) in ethanol in the presence of 3-aminopropyltriethoxysilane (AES) and of 3-(2-aminoethylamino)- propyltrimethoxysilane (EDAS) as co-reactants, and dried in subcritical conditions, is analyzed. A thorough structural characterization of the samples is performed combining nitrogen adsorption, small-angle X-ray scattering (SAXS), and transmission electron microscopy coupled with digital image analysis. The use of these methods shows that, for both co-reactants, the xerogels are made of macropores supported by filaments, with each filament being formed of smaller structures. The quantitative impact of the additive on each structural level is assessed. The data are compared with a previous time-resolved SAXS study conducted during the formation of the gels (J. Phys. Chem. B 2004, 108, 8983-8991). The results are analyzed in the framework of a double phase separation model

GEMAS: establishing geochemical background and threshold for 53 chemical elements in European agricultural soil

The GEMAS (geochemical mapping of agricultural soil) project collected 2108 Ap horizon soil samples from regularly ploughed fields in 33 European countries, covering 5.6 million km2. The <2 mm fraction of these samples was analysed for 53 elements by ICP-MS and ICP-AES, following a HNO3/HCl/H2O (modified aqua regia) digestion. Results are used here to establish the geochemical background variation and threshold values, derived statistically from the data set, in order to identify unusually high element concentrations for these elements in the Ap samples. Potentially toxic elements (PTEs), namely Ag, B, As, Ba, Bi, Cd, Co, Cr, Cu, Hg, Mn, Mo, Ni, Pb, Sb, Se, Sn, U, V and Zn, and emerging ‘high-tech’ critical elements (HTCEs), i.e., lanthanides (e.g., Ce, La), Be, Ga, Ge, In, Li and Tl, are of particular interest. For the latter, neither geochemical background nor threshold at the European scale has been established before. Large differences in the spatial distribution of many elements are observed between northern and southern Europe. It was thus necessary to establish three different sets of geochemical threshold values, one for the whole of Europe, a second for northern and a third for southern Europe. These values were then compared to existing soil guideline values for (eco)toxicological effects of these elements, as defined by various European authorities. The regional sample distribution with concentrations above the threshold values is studied, based on the GEMAS data set, following different methods of determination. Occasionally local contamination sources (e.g., cities, metal smelters, power plants, agriculture) can be identified. No indications could be detected at the continental scale for a significant impact of diffuse contamination on the regional distribution of element concentrations in the European agricultural soil samples. At this European scale, the variation in the natural background concentration of all investigated elements in the agricultural soil samples is much larger than any anthropogenic impact

GEMAS: Cadmium distribution and its sources in agricultural and grazing land soil of Europe â\u80\u94 Original data versus clr-transformed data

Over 4000 agricultural and grazing land soil samples were collected for the â\u80\u9cGeochemical Mapping of Agricultural and Grazing Land Soil of Europeâ\u80\u9d (GEMAS) project carried out by the EuroGeoSurveys Geochemistry Expert Group. The samples were collected in 33 European countries, covering 5.6 million km2at a density of 1 sample site per 2500 km2. All samples were analysed by ICP-MS following an aqua regia extraction. The European median Cd concentration is 0.182 mg/kg in agricultural soil and 0.197 mg/kg in grazing land soil (including eastern Ukraine). The Cd map demonstrates the existence of two different geochemical background regimes in northern and southern Europe, separated by the southern limit of the Quaternary glaciation. Cadmium shows two times higher background concentrations in the older and more weathered southern European soil than in northern European soil. The spatial distribution patterns of Cd in the collected soil samples are mainly governed by geology (parent material and mineralisation), as well as weathering, soil formation and climate since the last glaciation period. Locally, in several areas, the natural anomaly pattern is overprinted by anthropogenic emissions from former mining, ore processing and related metal industries. Some Cd anomalies can be attributed to urbanisation and the use of fertilisers. A comparison of the raw data Cd concentration map with its clr-transformed counterpart and selected single element ratio maps demonstrates that substantial additional information about sources and processes governing the distribution of Cd in agricultural soil at the European scale can be obtained. Results of a PCA, carried out following the classical approach (standardised) versus a PCA based on the statistically acceptable approach, using clr-transformed data, are quite comparable

GEMAS: Source, distribution patterns and geochemical behaviour of Ge in agricultural and grazing land soils at European continental scale

Agricultural soil (Ap-horizon, 0–20 cm) and grazing land soil (Gr-horizon, 0–10 cm) samples were collected from a large part of Europe (33 countries, 5.6 million km2) as part of the GEMAS (GEochemical Mapping of Agricultural and grazing land Soil) soil mapping project. GEMAS soil data have been used to provide a general view of element mobility and source rocks at the continental scale, either by reference to average crustal abundances or to normalized patterns of element mobility during weathering processes. The survey area includes a diverse group of soil parent materials with varying geological history, a wide range of climate zones, and landscapes. The concentrations of Ge in European soil were determined by ICP-MS after an aqua extraction, and their spatial distribution patterns generated by means of a GIS software. The median values of Ge and its spatial distribution in Ap and Gr soils are almost the same (0.037 vs. 0.034 mg/kg, respectively). The majority of Ge anomalies is related to the type of soil parent material, namely lithology of the bedrock and minor influence of soil parameters such as pH, TOC and clay content. Metallogenic belts with sulphide mineralisation provide the primary source of Ge in soil in several regions in Europe, e.g. in Scandinavia, Germany, France, Spain and Balkan countries. Comparison with total Ge concentrations obtained from the Baltic Soil Survey shows that aqua regia is a very selective method with rather low-efficiency and cannot provide a complete explanation for Ge geochemical behaviour in soil. Additionally, large differences in Ge distribution are to be expected when different soil depth horizons are analysed

GEMAS: Cadmium distribution and its sources in agricultural and grazing land soil of Europe - Original data versus clr-transformed data

Over 4000 agricultural and grazing land soil samples were collected for the “Geochemical Mapping of Agricultural and Grazing Land Soil of Europe” (GEMAS) project carried out by the EuroGeoSurveys Geochemistry Expert Group. The samples were collected in 33 European countries, covering 5.6 million km² at a density of 1 sample site per 2500 km². All samples were analysed by ICP-MS following an aqua regia extraction. The European median Cd concentration is 0.182 mg/kg in agricultural soil and 0.197 mg/kg in grazing land soil (including eastern Ukraine). The Cd map demonstrates the existence of two different geochemical background regimes in northern and southern Europe, separated by the southern limit of the Quaternary glaciation. Cadmium shows two times higher background concentrations in the older and more weathered southern European soil than in northern European soil

GEMAS: Spatial distribution of the pH of European agricultural and grazing land soil

During 2008 the GEochemical Mapping of Agricultural Soils (GEMAS) project collected 2108 agricultural (ploughed soil, Ap horizon, 0–20 cm) and 2023 grazing land soil samples (Gr, 0–10 cm) evenly spread over 33 European countries and covering an area of 5.6 million km2. The pH of all samples was determined by one single laboratory applying a 0.01 M CaCl2 extraction, and following a strict quality-control procedure. The resulting pH-value distributions for European Ap and Gr soil are both bimodal. Broad acidic modes, with pH between 4 and 6, and sharp alkaline modes, with pH between 7 and 8 due to the Ca2+ buffer system, are clearly separated. The European median pH is 5.8 for the GEMAS Ap soil samples and 5.5 for the GEMAS Gr soil samples. According to the pH distribution maps, Europe is separated into two main zones: northern Europe with generally lower pH values (Ap: 5.2, Gr: 4.8), dominated by acidic soils occurring in Fennoscandia, and southern Europe with higher pH values (Ap: 6.3, Gr: 5.9), dominated by carbonate rich soils. The separation line coincides with the southern border of the sediments of the last glaciation. The dominant factors controlling pH at the European scale are thus geology (crystalline bedrock) in combination with climate (temperature and precipitation). The GEMAS pH maps mainly reflect the natural site conditions on the European scale, whilst anthropogenic impact is hardly detectable. The GEMAS results provide a unique set of homogenous and spatially representative soil pH data for the continent. The data set defines a dependable continental-scale background, and offers the possibility to calibrate studies on more detailed scales

Geochemical fingerprinting and source discrimination of agricultural soils at continental scale

2108 agricultural soil samples (Ap-horizon, 0-20cm) were collected in Europe (33 countries, area 5.6 million km2) as part of the recently completed GEMAS (GEochemical Mapping of Agricultural and grazing land Soil) soil mapping project. GEMAS soil data have been used to provide a general view of element origin and mobility with a main focus on source parent material (and source rocks) at the continental scale, either by reference to average crustal abundances or to normalized patterns of element mobility during weathering processes. The survey area covers a large territory with diverse types of soil parent materials, with distinct geological history and a wide range of climate zones, and landscapes.To normalize the chemical composition of European agricultural soil, mean values and standard deviation of the selected elements have been compared to model compositions of the upper continental crust (UCC) and mean European river suspended sediment. Some elements are enriched relative to the UCC (Al, P, Pb, Zr,) whereas others, such as Mg, Na and Sr are depleted. The concept of the UCC extended normalization pattern has been applied to selected elements. The mean values of Rb, K, Y, Ti, Al, Si, Zr, Ce and Fe are very similar to the values from the UCC model, even when standard deviations indicate slight enrichment or depletion. Zirconium has the best fit to the UCC model using both mean value and standard deviation. Lead and Cr are enriched in European soil when compared to the UCC model, but their standard deviation values span a large, particularly towards very low values, which can be interpreted as a lithological effect.GEMAS soil data have been normalized to Al and Na, taking into account the main lithologies of the UCC, in order to discriminate provenance sources. Additionally, sodium normalization highlights variations related to the soluble and insoluble behavior of some elements (e.g., K, Rb versus Ti, Al, Si, V, Y, Zr, Ba, and La, respectively), their reactivity (e.g, Fe, Mn, Zn) and association with carbonates (e.g., Ca and Sr). Maps of Europe showing the spatial distribution of normalized compositions and element ratios reveal difficulties with the use of classical element ratios because of the large lithological differences in compositions of soil parent material. The ratio maps and color composite images extracted from the GEMAS data can help to discriminate the main lithologies in Europe at the regional scale but need to be used with caution due to the complexity of superimposed processes responsible for the soil chemical composition