Graphical statistics to explore the natural and anthropogenic processes influencing the inorganic quality of drinking water, ground water and surface water

Plots of cumulative distribution functions (CDF) are a simple but powerful exploratory data analysis (EDA) tool to evaluate and compare statistical data distributions. Here, empirical CDF plots are used to compare results of four large (476 to 884 samples) national- to continental-scale inorganic water chemistry data sets: (1) European surface water, (2) European tap water, (3) European bottled waters as a proxy for groundwater and (4) Norwegian crystalline bedrock rock groundwater, all analysed at the same laboratory, albeit at different times. For many parameters (e.g., Ba, Cl-, K, SO4 2-) median values and ranges are, given the differing origins and, in some cases, treatment processes of the waters, surprisingly comparable. Unusually high concentrations of some other elements (e.g., B, Be, Br, Cs, F-, Ge, Li, Rb, Te and Zr) appear to be characteristic of deeper-seated, mature groundwaters. Other influences that can be inferred include contamination from well construction or plumbing materials (Cu, Pb, Zn – in tap waters, bottled waters and Norwegian groundwaters), water treatment (Fe, Mn – in tap- and Norwegian groundwater), bottle materials (Sb - bottled waters). The empirical CDF plots also reveal analytical issues for some elements (excessive rounding, element interferences). The best reference for natural and uncontaminated ’water’ is probably provided by the mineral water samples, representing ’deep groundwater’ at the European scale

GEMAS: colours of dry and moist agricultural soil samples of Europe

High resolution HDR colour images of all Ap samples from the GEMAS survey were acquired using a GeoTek Linescan camera. This data set will help to develop new methods for world-wide characterization and monitoring of agricultural soils which is essential for quantifying geologic and human impact on the critical zone environment

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

GEMAS: CNS concentrations and C/N ratios in European agricultural soil

A reliable overview of measured concentrations of TC, TN and TS, TOC/TN ratios, and their regional distribution patterns in agricultural soil at the continental scale and based on measured data has been missing – despite much previous work on local and the European scales. Detection and mapping of natural (ambient) background element concentrations and variability in Europe was the focus of this work. While total C and S data had been presented in the GEMAS atlas already, this work delivers more precise (lower limit of determination) and fully quantitative data, and for the first time high-quality TN data

A density-functional theory approach to the existence and stability of molybdenum and tungsten sesquioxide polymorphs

The sesquioxides of molybdenum and tungsten have been reported as thin films or on surfaces as early as 1971, but the preparation of bulk materials and their crystal structures are still unknown up to the present day. We present a systematic ab initio approach to their possible syntheses and crystal structures applying complementary methods and basis-set types. For both compounds, the corundum structure is the most stable and does not display any imaginary frequencies. Calculations targeted at a high-pressure synthesis starting from the stable oxides and metals predict a reaction pressure of 15 GPa for Mo2O3 and over 60 GPa for W2O3

GEMAS: unmixing magnetic properties of European agricultural soil

High resolution magnetic measurements provide new methods for world-wide characterization and monitoring of agricultural soil which is essential for quantifying geologic and human impact on the critical zone environment and consequences of climatic change, for planning economic and ecological land use, and for forensic applications. Hysteresis measurements of all Ap samples from the GEMAS survey yield a comprehensive overview of mineral magnetic properties in European agricultural soil on a continental scale

15 insights on the global steel transformation

15 INSIGHTS ON THE GLOBAL STEEL TRANSFORMATION 15 insights on the global steel transformation / Witecka, Wido K. (Rights reserved) ( -

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

The use of diffuse reflectance mid-infrared spectroscopy for the prediction of the concentration of chemical elements estimated by X-ray fluorescence in agricultural and grazing European soils

The aim of this study was to develop partial least-squares (PLS) regression models using diffuse reflectance Fourier transform mid-infrared (MIR) spectroscopy for the prediction of the concentration of elements in soil determined by X-ray fluorescence (XRF). A total of 4130 soils from the GEMAS European soil sampling program (geochemical mapping of agricultural soils and grazing land of Europe) were used for the development of models to predict concentrations of Al, As, Ba, Ca, Ce, Co, Cr, Cs, Cu, Fe, Ga, Hf, K, La, Mg, Mn, Na, Nb, Ni, P, Pb, Rb, Sc, Si, Sr, Th, Ti, V, Y, Zn and Zr in soil using MIR spectroscopy. The results were compared with those obtained where MIR models were developed with the same soils but using the concentration of elements extracted with aqua regia (AR). The PLS models were cross-validated against the experimental log-transformed XRF values of all the elements. The calibration models were derived from a set of 1000 randomly selected calibration samples. The rest of the samples (3130) were used as an independent validation set. According to the residual predictive deviation (RPD), predictions were classified as follows: “Good quality”, Ca (2.9), Mg (2.5), Al (2.3), Fe (2.2), Ga (2.2), Si (2.1), Na (2.0); “Indicator quality”, V (1.9), Ni (1.9), Sc (1.9), K (1.8), Ti (1.8), Rb (1.8), Zn (1.7), Co (1.7), Zr (1.6), Cr (1.6), Sr (1.6), Y (1.6), Nb (1.6), Ba (1.5), Mn (1.5), As (1.5), Ce (1.5); “Poor quality”, Cs (1.4), Th (1.4), P (1.4), Cu (1.4), Pb (1.3), La (1.2), Hf (1.1). Good agreement was observed between the RPD values obtained for the elements analysed in this study and those from the AR study. Despite the different elemental concentrations determined by the XRF method compared to the AR method, MIR spectroscopy was still capable of predicting elemental concentrations

Synthesis and characterization of metastable transition metal oxides and oxide nitrides

New routes to vanadium sesquioxide and tantalum oxide nitride (γ- and δ-phase) are presented. Phase pure V2O3 with bixbyite-type structure, a metastable polymorph, was obtained from vanadium fluoride hydrates at ~750 K. It crystallizes in the cubic crystal system in space group Ia3¯ with lattice parameter a=939.30(5) pm. The catalytical properties of the corresponding oxide nitride phases and their oxidation and reduction solid-state kinetics were investigated. The preparation of γ-TaON as a phase pure sample can be realized by ammonolysis of X-ray amorphous tantalum oxide precursors at 1073 K. This metastable tantalum oxide nitride crystallizes in the monoclinic VO2(B)-type structure in space group C2/m. The same precursors can be used to synthesize the δ-modification with an anatase-type structure at 1023 K. It crystallizes in the tetragonal crystal system in space group I41/amd. A maximum yield of 82 m % could be obtained. The fundamental band gaps of the synthesized and of other metastable TaON polymorphs were calculated from first principles using the GW method. The present results are compared to experimental data and to previous calculations at hybrid DFT level