Volume diffusion of Ytterbium in YAG: thin-film experiments and combined TEM–RBS analysis

In this study, we address volume diffusion of ytterbium in yttrium aluminum garnet (YAG) using thin-film single crystal diffusion couples. We employ analytical transmission electron microscopy (ATEM) as a tool for combined microstructural and microchemical analysis and compare the results to Rutherford backscattering (RBS) analysis. Given the high spatial resolution of the method, we focus on microstructural changes of the thin-film diffusant source during the diffusion anneal. We evaluate the potential influence of the associated changes in its transport properties on the evolution of concentration profiles in the single crystal substrate. This approach allows us to test the reliability of determination of volume diffusion coefficients from thin-film diffusion experiments. We found that for the chosen experimental setting, the influence of thin-film re-crystallization is small when compared with the experimental uncertainty and good estimates for the volume diffusion coefficients of Yb in YAG can be obtained using standard assumptions. Both Yb-concentration profiles analyzed with ATEM and with RBS give similar results. At 1,450°C and 1 bar, we infer log D _Yb (m²/s) values of −19.37 ± 0.07 (TEM) and −19.84 ± 0.02 (RBS). Although the change in thin-film transport properties associated with successive crystallization during the diffusion anneal does not play a major role for our experimental setup, this effect cannot generally be ignored.     

An evaluation of the genesis and suitability of groundwater for irrigation in the Volta Region,Ghana

Stable isotope data and concentrations of the major cations and anions of groundwater from the northern part of the Volta Region, Ghana, were used to determine the source of recharge and the suitability of groundwater in the area for irrigation. This study finds that the delta deuterium (δD) and delta Oxygen-18 (δ¹⁸O) data from the area fall along the global meteoric water line (GMWL). An equation of regression derived for the relationship between δD and δ¹⁸O bears very close semblance to the equation which describes the GMWL. On the basis of this, groundwater in the study area is probably meteoric and fresh. The apparently low salinities and sodicities of the groundwater seem to support this interpretation. The suitability of groundwater for domestic and irrigation purposes is related to its source, which determines its constitution. A plot of the sodium adsorption ratio (SAR) and electrical conductivity (EC) data on a semilog axis, suggests that groundwater serves good irrigation quality in the area. Sixty percent (60%), 20% and 20% of the 67 data points used in this study fall within the medium salinity–low sodicity (C2–S1), low salinity–low sodicity (C1–S1) and high salinity–low sodicity (C3–S1) fields, which ascribe good irrigation quality to groundwater from this area. Salinities range from 28.1 to 1,956 μS/cm, whilst SAR values fall within the range 0–3. Extremely low sodicity waters of this kind, with salinities lower than 600 μS/cm, have the tendency to affect the dispersive properties of irrigation soils when used for irrigation. About 50% of the groundwater in the study area fall within this category and need prior treatment before usage.     

Paleoproterozoic volcanic rocks in the southern margin of the North China Craton,central China:Implications for the Columbia supercontinent

The volcanic rocks of the Xiong'er Group are situated in the southern margin of the North China Craton(NCC).Research on the Xiong er Group is important to understand the tectonic evolution of the NCC and the Columbia supercontinent during the Paleoproterozoic.In this study,to constrain the age of the Xiong'er volcanic rocks and identify its tectonic environment,we report zircon LA-ICP-MS data with Hf isotope,whole-rock major and trace element compositions and Sr-Nd-Pb-Hf isotopes of the volcanic rocks of the Xiong'er Group.The Xiong'er volcanic rocks mainly consist of basaltic andesite,andesite.dacite and rhyolite,with minor basalt.Our new sets of data combined with those from previous studies indicate that Xiong'er volcanism should have lasted from 1827 Ma to 1746 Ma as the major phase of the volcanism.These volcanics have extremely low MgO.Cr and Ni contents,are enriched in LREEs and LILEs but depleted in HFSEs(Nb,Ta,and Ti),similar to arc-related volcanic rocks.They are characterized by negative zircon ε_(Hf)_(t) values of-17.4 to 8.8,whole-rock initial ~(87)Sr/~(86)Sr values of 0.7023 to 0.7177 andε_(Nd)(t) values of-10.9 to 6.4.and Pb isotopes(~(206)Pb/~(204)Pb =14.366-16.431,~(207)Pb/~(204)Pb =15.106-15.371,~(208)Pb/~(204)Pb= 32.455-37.422).The available elemental and Sr-Nd-Pb-Hf isotope data suggest that the Xiong'er volcanic rocks were sourced from a mantle contaminated by continental crust.The volcanic rocks of the Xiong'er Group might have been generated by high-degree partial melting of a lithospheric mantle that was originally modified by oceanic subduction in the Archean.Thus,we suggest that the subduction-modified lithospheric mantle occurred in an extensional setting during the breakup of the Columbia supercontinent in the Late Paleoproterozoic,rather than in an arc setting.     

The geochemistry of gem opals as evidence of their origin

Seventy-seven gem opals from ten countries were analyzed by inductively coupled plasma-mass spectrometry (ICP-MS) through a dilution process, in order to establish the nature of the impurities. The results are correlated to the mode of formation and physical properties and are instrumental in establishing the geographical origin of a gem opal. The geochemistry of an opal is shown to be dependant mostly on the host rock, at least for examples from Mexico and Brazil, even if modified by weathering processes. In order of decreasing concentration, the main impurities present are Al, Ca, Fe, K, Na, and Mg (more than 500 ppm). Other noticeable elements in lesser amounts are Ba, followed by Zr, Sr, Rb, U, and Pb. For the first time, geochemistry helps to discriminate some varieties of opals. The Ba content, as well as the chondrite-normalized REE pattern, are the keys to separating sedimentary opals (Ba > 110 ppm, Eu and Ce anomalies) from volcanic opals (Ba < 110 ppm, no Eu or Ce anomaly). The Ca content, and to a lesser extent that of Mg, Al, K and Nb, helps to distinguish gem opals from different volcanic environments. The limited range of concentrations for all elements in precious (play-of-color) compared to common opals, indicates that this variety must have very specific, or more restricted, conditions of formation. We tentatively interpreted the presence of impurities in terms of crystallochemistry, even if opal is a poorly crystallized or amorphous material. The main replacement is the substitution of Si⁴⁺ by Al³⁺ and Fe³⁺. The induced charge imbalance is compensated chiefly by Ca²⁺, Mg²⁺, Mn²⁺, Ba²⁺, K⁺, and Na⁺. In terms of origin of color, greater concentrations of iron induce darker colors (from yellow to “chocolate brown”). This element inhibits luminescence for concentrations above 1000 ppm, whereas already a low content in U (≤ 1 ppm) induces a green luminescence.     

Glacier mass balance of tropical Zongo glacier, Bolivia, comparing hydrological and glaciological methods

A glaciological program has been undertaken since 1991 on Zongo glacier in Bolivia (6000–4850 m asl, 2.4 km², 16°S). This program involves mass balance measurements, hydrological studies and energy balance investigations. On outer-tropical glaciers, melting and snow accumulation are both maximum in the wet season (austral summer), whereas the dry season (winter) is a period of low ablation. Errors on each term of the glaciological (stakes, snow-pits and integration method of the measurements) and hydrological (precipitation, discharge and runoff coefficient of free ice areas) methods are investigated to estimate the overall accuracy of the mass balance measurements. The hydrological budget is less than the glaciological one (mean difference: 60 cm w.e. per year), but both methods reproduce similar inter-annual variations. Errors in assessment of evaporation or water storage inside the glacier cannot explain the discrepancy. Errors using the glaciological method are large (around ± 40 cm w.e. per year), but no bias can explain the departure from the hydrological balance. Errors on discharge measurements are small and the uncertainty on the runoff coefficient has a minor effect on the mass balance. We concluded that hydrological budgets are too low due to the catch deficiency of rain gauges and absence of precipitation measurements at high altitudes, emphasizing the difficulty to assess snowfall distribution in high mountainous basins.     

From Predictive Mapping of Mineral Prospectivity to Quantitative Estimation of Number of Undiscovered Prospects

This paper proposes that the spatial pattern of known prospects of the deposit‐type sought is the key to link predictive mapping of mineral prospectivity (PMMP) and quantitative mineral resource assessment (QMRA). This proposition is demonstrated by PMMP for hydrothermal Au‐Cu deposits (HACD) and by estimating the number of undiscovered prospects for HACD in Catanduanes Island (Philippines). The results of analyses of the spatial pattern of known prospects of HACD and their spatial associations with geological features are consistent with existing knowledge of geological controls on hydrothermal Au‐Cu mineralization in the island and elsewhere, and are used to define spatial recognition criteria of regional‐scale prospectivity for HACD. Integration of layers of evidence representing the spatial recognition criteria of prospectivity via application of data‐driven evidential belief functions results in a map of prospective areas occupying 20% of the island with fitting‐ and prediction‐rates of 76% and 70%, respectively. The predictive map of prospective areas and a proxy measure for degrees of exploration based on the spatial pattern of known prospects of HACD were used in one‐level prediction of undiscovered mineral endowment, which yielded estimates of 79 to 112 undiscovered prospects of HACD. Application of radial‐density fractal analysis of the spatial pattern of known prospects of HACD results in an estimate of 113 undiscovered prospects of HACD. Thus, the results of the study support the proposition that PMMP can be a part of QMRA if the spatial pattern of discovered prospects of the deposit‐type sought is considered in both PMMP and QMRA.     

Investigating the Halogen Chemistry From High-Latitude Nighttime Stratospheric Measurements of OClO and NO2

Two cases of simultaneous nighttime measurements of NO₂ and OClO in the winter polar stratosphere are analyzed in order to test our present knowledge of halogen chemistry in the presence of high amount of NO₂ at low temperature. Comparisons with Lagrangian model calculations using several hypotheses are performed. First simulations, using the admitted constant rates of chemical reaction, strongly underestimate the measured OClO while the NO₂ profiles are correctly reproduced. If uncertainties in actinic fluxes calculations are taken into account, simulation results do not show a significant reduction of the underestimation. A better agreement can be achieved if the formation of unstable isomers of ClONO₂ and of BrONO₂ occurs in the cold conditions of the polar stratosphere. An approximate value of the branching ratios of the channels leading to ClONO₂ and ClOONO, and to BrONO₂ and BrOONO, necessary to reproduce both OClO and NO₂ is given and discussed.     

Spatially-Weighted Factor Analysis for Extraction of Source-Oriented Mineralization Feature in 3D Coordinates of Surface Geochemical Signal

Natural Resources Research - This contribution proposes a spatially weighted factor analysis (SWFA) to recognize effectively the underlying mineralization-related feature(s) in geochemical signals....     

http://www.sciencedirect.com/science/article/pii/S1674987111000405

This study has focused on the processes of soil degradation and chemical element concentration in tea-growing regions of Rwanda, Africa. Soil degradation accelerated by erosion is caused not only by topography but also by human activities. This soil degradation involves both the physical loss and reduction in the amount of topsoil associated with nutrient decline. Soil samples were collected from eleven tropical zones in Rwanda and from variable depth within each collecting site. Of these, Samples from three locations in each zone were analyzed in the laboratory, with the result that the pH of all soil samples is shown to be less than 5 (pH < 5) with a general average of 4.4. The elements such as iron (Fe), copper (Cu), manganese (Mn), and zinc (Zn) are present in high concentration levels. In contrast calcium (Ca) and sodium (Na) are present at low-level concentrations and carbon (C) was found in minimal concentrations. In addition, elements derived from fertilizers, such as nitrogen (N), phosphorous (P), and potassium (K) which is also from minerals such as feldspar, are also present in low-level concentrations. The results indicate that the soil in certain Rwandan tea plantations is acidic and that this level of pH may help explain, in addition to natural factors, the deficiency of some elements such as Ca, Mg, P and N. The use of chemical fertilizers, land use system and the location of fields relative to household plots are also considered to help explain why tea plantation soils are typically degraded.     

Selection of Less Biased Threshold Angles for SAM Classification Using the Real Value–Area Fractal Technique

The accuracy of classification of the Spectral Angle Mapping (SAM) is warranted by choosing the appropriate threshold angles, which are normally defined by the user. Trial‐and‐error and statistical methods are commonly applied to determine threshold angles. In this paper, we discuss a real value–area (RV–A) technique based on the established concentration–area (C–A) fractal model to determine less biased threshold angles for SAM classification of multispectral images. Short wave infrared (SWIR) bands of the Advanced Spaceborne Thermal Emission and Reflection Radiometer (ASTER) images were used over and around the Sar Cheshmeh porphyry Cu deposit and Seridune porphyry Cu prospect. Reference spectra from the known hydrothermal alteration zones in each study area were chosen for producing respective rule images. Segmentation of each rule image resulted in a RV–A curve. Hydrothermal alteration mapping based on threshold values of each RV–A curve showed that the first break in each curve is practical for selection of optimum threshold angles. The hydrothermal alteration maps of the study areas were evaluated by field and laboratory studies including X–ray diffraction analysis, spectral analysis, and thin section study of rock samples. The accuracy of the SAM classification was evaluated by using an error matrix. Overall accuracies of 80.62% and 75.45% were acquired in the Sar Cheshmeh and Seridune areas, respectively. We also used different threshold angles obtained by some statistical techniques to evaluate the efficiency of the proposed RV–A technique. Threshold angles provided by statistical techniques could not enhance the hydrothermal alteration zones around the known deposits, as good as threshold angles obtained by the RV–A technique. Since no arbitrary parameter is defined by the user in the application of the RV‐A technique, its application prevents introduction of human bias to the selection of optimum threshold angle for SAM classification.