Incorporation of silica into the goethite structure: a microscopic and spectroscopic study

Quartz and iron (hydr)oxide are reactive surface phases that are often associated with one another in soils and sediments. Despite the several studies on the coating of quartz with iron oxides, the reactivity of dissolved species (Si) leached from quartz with iron (hydr)oxides has received limited attention. In this study, goethite synthesized on quartz substrates were characterized using field emission scanning electron microscopy, X-ray diffraction (XRD), transmission electron microscopy, and Fourier-transform infrared (FT-IR) spectroscopy. The SEM characterization revealed that bundles of thin parallel aligned goethite rods were formed at pH?>?10, while large pseudohexagonal crystals of twinned goethite needles were synthesized at pH?≤?10 after dehydration and hydration in the alkaline media. TEM analysis showed expanded and distorted lattice spacing of the crystal structure of iron (hydr)oxide due to silica incorporation. The characterization showed that silica increased the crystallite size of the goethite and transformed its acicular texture to a larger, twinned needle structure. FT-IR and XRD analyses revealed band shifts in crystal bonds as well as new bond formations, which indicate the presence of changes in the chemical environment of Fe–O and Si–O bonds. Thus, the presence of sorbed silicates modifies the crystal and lattice structure of goethite.     

Use of interactive multisensor snow and ice mapping system snow cover maps (IMS) and artificial neural networks for simulating river discharges in Eastern Turkey

Basins located in Eastern Turkey are largely fed by snowmelt runoff during spring and early summer seasons. This study investigates the efficiency of artificial neural networks (ANNs) in snowmelt runoff generation. Although ANNs have been used for streamflow simulating/forecasting in the last two decades, using satellite-based snow-covered area (SCA) maps and meteorological observations as inputs to ANN provides a novel basis for estimating streamflow. The proposed methodology is implemented over Upper Euphrates River Basin in Eastern Turkey. SCA data was acquired from Interactive Multisensor Snow and Ice Mapping System (IMS) for an 8-year period from February 2004 to September 2011. Meteorological observations including daily cumulative precipitation and daily average air temperatures were obtained from Turkish State Meteorological Services. The simulation results are promising with coefficient of correlation varying from 0.67 to 0.98 among proposed models. Past days discharge was found to substantially improve the forecast accuracy. The paper presents the expected basin discharge for 2011 water year based on meteorological observations and SCA input.     

Fast wavelet-based stochastic simulation using training images

Spatial uncertainty modelling is a complex and challenging job for orebody modelling in mining, reservoir characterization in petroleum, and contamination modelling in air and water. Stochastic simulation algorithms are popular methods for such modelling. In this paper, discrete wavelet transformation (DWT)-based multiple point simulation algorithm for continuous variable is proposed that handles multi-scale spatial characteristics in datasets and training images. The DWT of a training image provides multi-scale high-frequency wavelet images and one low-frequency scaling image at the coarsest scale. The simulation of the proposed approach is performed on the frequency (wavelet) domain where the scaling image and wavelet images across the scale are simulated jointly. The inverse DWT reconstructs simulated realizations of an attribute of interest in the space domain. An automatic scale-selection algorithm using dominant mode difference is applied for the selection of the optimal scale of wavelet decomposition. The proposed algorithm reduces the computational time required for simulating large domain as compared to spatial domain multi-point simulation algorithm. The algorithm is tested with an exhaustive dataset using conditional and unconditional simulation in two- and three-dimensional fluvial reservoir and mining blasted rock data. The realizations generated by the proposed algorithm perform well and reproduce the statistics of the training image. The study conducted comparing the spatial domain filtersim multiple-point simulation algorithm suggests that the proposed algorithm generates equally good realizations at lower computational cost.     

Impacts of nutrient management and decrease in paddy field area on groundwater nitrate concentration: a case study at the Nasunogahara alluvial fan,Tochigi Prefecture,Japan

In order to help evaluate the trends in the NO₃-N concentration in groundwater with a view to preventing further degradation in water quality in the future, a distributed groundwater quality model was constructed for the Nasunogahara basin. The best fit for the groundwater table elevations by the flow component of the model was achieved with average mean absolute errors (MAEs) of 0·92 m for the calibration period and 0·83 m for the validation period. Moreover, the best fit for the NO₃-N concentration by the water quality component was achieved with average mean relative errors (MREs) of 29·8% for the calibration period and 30·3% for the validation period. After developing a robust model, various change scenarios were tested; specifically, the effects of effluent load control and a decrease in paddy field area on the NO₃-N concentration in groundwater were predicted. The most intensively farmed area contributed about 40% of the total effluent load because of livestock farming in the basin. When the effluent load from this area was decreased by 50%, the average NO₃-N concentrations at sites S1, S2 and S3 were reduced by about 15%; however, the average concentrations at S4 and S5 were reduced by only 1%. Furthermore, when the total effluent load from the concentrated livestock area was removed completely, the average groundwater NO₃-N concentrations at S1, S2 and S3 were reduced by about 30% as compared with the original calculated results. In contrast, decreasing the area of the paddy fields in the basin did not greatly influence the groundwater NO₃-N concentration. In the case of a 70% reduction in paddy field area, average NO₃-N concentrations increased by about 7% at S1, S2 and S3. Copyright © 2008 John Wiley & Sons, Ltd.     

Invariant shape solutions of the spinning three craft Coulomb tether problem

In this paper we study shape-preserving formations of three spacecraft, where the formation keeping forces arise from the electric charges deposed on each craft. Inspired by Lagrange’s 3-body problem, the general conditions that guarantee preservation of the geometric shape of the electrically charged formation are derived. While the classical collinear configuration is a solution to the problem, the equilateral triangle configuration is found to only occur with unbounded relative motion. The three collinear spacecraft problem is analyzed and the possible solutions are categorized based on the spacecraft mass–charge ratio. Precise statements on the number of solutions associated with each category are provided. Finally, a methodology is proposed to study boundedness of the collinear solution that is inspired by past understanding and results for the 3-body problem. Given the initial position and the velocity vectors of each craft along with the charges, analytical solutions are provided describing the resulting relative motion.     

Chemical Characterization of Carbonated Natural Mineral Waters Produced in Turkey: Compliance with European Water Quality Standards

In this study, a total of 100 samples from 25 brands of carbonated natural mineral waters (CNMWs) produced in Turkey were analyzed for a total of 36 water quality constituents to determine their suitability for human consumption. Parameters examined include pH, electrical conductivity, ammonia, nitrate, nitrite, sulfate, sulfite, orthophosphate, chloride, fluoride, bicarbonate, and 25 major/trace elements analyzed by inductively coupled plasma‐mass spectrometry (ICP‐MS). The presence of these constituents in this type of water was investigated considering recent concerns about their quality and the lack of trace element information on the manufacturer labels. The analytical results obtained in this study were compared to the European Union (EU) norms, labeled values on bottles, as well as values from the literature. Results of this study have shown that Turkish CNMWs may contain high concentrations of sulfite, which is a known allergen, especially for chronic asthmatic population. CNMWs surveyed in this study have also appreciable amounts of fluoride (>1.5 mg L^?1) that may have detrimental effects on health of children. The EU standards for As, Ba, Mn, and Ni were exceeded in seven CNMWs classified as “high mineral”. Compared to similar type of bottled waters from Europe and North America, CNMWs from Turkey generally contained higher elemental concentrations.     

Effects of diagenesis on paleoclimate reconstructions from modern and young fossil corals

The integrity of coral-based reconstructions of past climate variability depends on a comprehensive knowledge of the effects of post-depositional alteration on coral skeletal geochemistry. Here we combine millimeter-scale and micro-scale coral Sr/Ca data, scanning electron microscopy (SEM) images, and X-ray diffraction with previously published δ¹⁸O records to investigate the effects of submarine and subaerial diagenesis on paleoclimate reconstructions in modern and young sub-fossil corals from the central tropical Pacific. In a 40-year-old modern coral, we find secondary aragonite is associated with relatively high coral δ¹⁸O and Sr/Ca, equivalent to sea-surface temperature (SST) artifacts as large as −3 and −5 °C, respectively. Secondary aragonite observed in a 350-year-old fossil coral is associated with relatively high δ¹⁸O and Sr/Ca, resulting in apparent paleo-SST offsets of up to −2 and −4 °C, respectively. Secondary Ion Mass Spectrometry (SIMS) analyses of secondary aragonite yield Sr/Ca ratios ranging from 10.78 to 12.39 mmol/mol, significantly higher compared to 9.15 ± 0.37 mmol/mol measured in more pristine sections of the same fossil coral. Widespread dissolution and secondary calcite observed in a 750-year-old fossil coral is associated with relatively low δ¹⁸O and Sr/Ca. SIMS Sr/Ca measurements of the secondary calcite (1.96-9.74 mmol/mol) are significantly lower and more variable than Sr/Ca values from more pristine portions of the same fossil coral (8.22 ± 0.13 mmol/mol). Our results indicate that while diagenesis has a much larger impact on Sr/Ca-based paleoclimate reconstructions than δ¹⁸O-based reconstructions at our site, SIMS analyses of relatively pristine skeletal elements in an altered coral may provide robust estimates of Sr/Ca which can be used to derive paleo-SSTs.