Mercury mobility and bioavailability in soil from contaminated area

The mobility and bioavailability of mercury in the soil from the area near a plant using elemental mercury for manufacturing thermometers, areometers, glass energy switches and other articles made of technical glass has been evaluated. Mercury has been determined by sequential extraction method and with additional thermo desorption stage to determine elemental mercury. The procedure of sequential extraction involves five subsequent stages performed with the solutions of chloroform, deionized water, 0.5 M HCl, 0.2 M NaOH and aqua regia. The mean concentration of total mercury in soil was 147 ± 107 μg g⁻¹ dry mass (range 62–393), and the fractionation revealed that mercury was mainly bound to sulfides 56 ± 8% (range 45–66), one of the most biounavailable and immobile species of mercury in the environment. The fractions that brought lower contribution to the total mercury content were semi-mobile humic matter 22 ± 9% (range 11–34) and elemental mercury 17 ± 5% (range 8–23). The contributions brought by the highly mobile and toxic organomercury compounds were still lower 2.3 ± 2.7% (range 0.01–6.5). The lowest contributions brought the acid-soluble mercury 1.5 ± 1.3% (range 0.1–3.5) and water-soluble mercury 1.0 ± 0.3% (range 0.6–1.7). The surface layer of soil (0–20 cm) was characterized by higher mercury concentrations than that of the subsurface soil (60–80 cm), but the fractional contributions were comparable. The comparison of mercury fractionation results obtained in this study for highly polluted soils with results of fractionation of uncontaminated or moderately contaminated samples of soil and sediments had not shown significant statistical differences; however, in the last samples elemental mercury is usually present at very low concentrations. On the basis of obtained correlation coefficients it seems that elemental mercury soils from “Areometer” plant are contaminated; the main transformation is its vaporization to atmosphere and oxidation to divalent mercury, probably mainly mediated by organic matter, and next bound to humic matter and sulfides.     

Nanogeochemistry of hydrothermal magnetite

Magnetite from hydrothermal ore deposits can contain up to tens of thousands of parts per million (ppm) of elements such as Ti, Si, V, Al, Ca, Mg, Na, which tend to either structurally incorporate into growth and sector zones or form mineral micro- to nano-sized particles. Here, we report micro- to nano-structural and chemical data of hydrothermal magnetite from the Los Colorados iron oxide–apatite deposit in Chile, where magnetite displays both types of trace element incorporation. Three generations of magnetites (X–Z) were identified with concentrations of minor and trace elements that vary significantly: SiO₂, from below detection limit (bdl) to 3.1 wt%; Al₂O₃, 0.3–2.3 wt%; CaO, bdl–0.9 wt%; MgO, 0.02–2.5 wt%; TiO₂, 0.1–0.4 wt%; MnO, 0.04–0.2 wt%; Na₂O, bdl–0.4 wt%; and K₂O, bdl–0.4 wt%. An exception is V₂O₃, which is remarkably constant, ranging from 0.3 to 0.4 wt%. Six types of crystalline nanoparticles (NPs) were identified by means of transmission electron microscopy in the trace element-rich zones, which are each a few micrometres wide: (1) diopside, (2) clinoenstatite; (3) amphibole, (4) mica, (5) ulvöspinel, and (6) Ti-rich magnetite. In addition, Al-rich nanodomains, which contain 2–3 wt% of Al, occur within a single crystal of magnetite. The accumulation of NPs in the trace element-rich zones suggest that they form owing to supersaturation from a hydrothermal fluid, followed by entrapment during continuous growth of the magnetite surface. It is also concluded that mineral NPs promote exsolution of new phases from the mineral host, otherwise preserved as structurally bound trace elements. The presence of abundant mineral NPs in magnetite points to a complex incorporation of trace elements during growth, and provides a cautionary note on the interpretation of micron-scale chemical data of magnetite.     

Excess heat capacity and entropy of mixing in the high-structural state (K,Ca)-feldspar binary

Low- and high-temperature heat capacities were measured for a series of synthetic high-structural state (K,Ca)-feldspars (Or–An) using both a relaxation and a differential scanning calorimeter. The data were collected at temperatures between 5 and 800 K on polycrystalline samples that had been synthesised and characterised in a previous study. Below T = 300 K, Or₉₀An₁₀, and Or₈₀An₂₀ showed excess heat capacities of mixing with maximum values of ~3 J mol⁻¹ K⁻¹. The other members of this binary (An > 20 mol%) had lower excess heat capacity values of up to ~1 J mol⁻¹ K⁻¹. Above T = 300 K, some compositions exhibited negative excess heat capacities of mixing (with maximum values of −2 J mol⁻¹ K⁻¹). The vibrational entropy at 298.15 K for Or₉₀An₁₀ and Or₈₀An₂₀ deviated strongly from the behaviour of a mechanical mixture, with excess entropy values of ~3.5 J mol⁻¹ K⁻¹. More An-rich members had only small excess vibrational entropies at T = 298.15 K. The difference in behaviour between members with An > 20 mol% and those with An ≤ 20 mol% is probably a consequence of the structural state of the (K,Ca)-feldspars, i.e., (K,Ca)-feldspars with An ≤ 20 mol% have monoclinic symmetry, whereas those with An > 20 mol% are triclinic. At T = 800 K, the vibrational entropy values were found to scatter around the values expected for a mechanical mixture and, thus, correspond to a quasi-ideal behaviour. The solvus for the (K,Ca)-feldspar binary was calculated based on the entropy data from this study in combination with enthalpy and volume of mixing data from a previous study.     

Excess heat capacity and entropy of mixing along the chlorapatite–fluorapatite binary join

The heat capacity at constant pressure, C _p, of chlorapatite [Ca₅(PO₄)₃Cl – ClAp], and fluorapatite [Ca₅(PO₄)₃F – FAp], as well as of 12 compositions along the chlorapatite–fluorapatite join have been measured using relaxation calorimetry [heat capacity option of the physical properties measurement system (PPMS)] and differential scanning calorimetry (DSC) in the temperature range 5–764 K. The chlor-fluorapatites were synthesized at 1,375–1,220°C from Ca₃(PO₄)₂ using the CaF₂–CaCl₂ flux method. Most of the chlor-fluorapatite compositions could be measured directly as single crystals using the PPMS such that they were attached to the sample platform of the calorimeter by a crystal face. However, the crystals were too small for the crystal face to be polished. In such cases, where the sample coupling was not optimal, an empirical procedure was developed to smoothly connect the PPMS to the DSC heat capacities around ambient T. The heat capacity of the end-members above 298 K can be represented by the polynomials: C _p^ClAp = 613.21 − 2,313.90T ^−0.5 − 1.87964 × 10⁷ T ⁻² + 2.79925 × 10⁹ T ⁻³ and C _p^FAp = 681.24 − 4,621.73 × T ^−0.5 − 6.38134 × 10⁶ T ⁻² + 7.38088 × 10⁸ T ⁻³ (units, J mol⁻¹ K⁻¹). Their standard third-law entropy, derived from the low-temperature heat capacity measurements, is S° = 400.6 ± 1.6 J mol⁻¹ K⁻¹ for chlorapatite and S° = 383.2 ± 1.5 J mol⁻¹ K⁻¹ for fluorapatite. Positive excess heat capacities of mixing, ΔC _p^ex, occur in the chlorapatite–fluorapatite solid solution around 80 K (and to a lesser degree at 200 K) and are asymmetrically distributed over the join reaching a maximum of 1.3 ± 0.3 J mol⁻¹ K⁻¹ for F-rich compositions. They are significant at these conditions exceeding the 2σ-uncertainty of the data. The excess entropy of mixing, ΔS ^ex, at 298 K reaches positive values of 3–4 J mol⁻¹ K⁻¹ in the F-rich portion of the binary, is, however, not significantly different from zero across the join within its 2σ-uncertainty.     

A ternary feldspar-mixing model based on calorimetric data: development and application

A mixing model for high structural state ternary feldspars in the NaAlSi₃O₈–KAlSi₃O₈–CaAl₂Si₂O₈ system is presented based exclusively on calorimetric and volumetric measurements. Comparisons with existing mixing models, which are based on phase-equilibrium experiments, reveal distinct differences. The incorporation of K into Ca-rich plagioclase and of Ca into K-rich alkali feldspar is more strongly limited by our calorimetry-based model, whereas the stability field of Na-rich feldspars is broadened. Natural feldspar assemblages from well-studied magmatic and high-grade metamorphic rocks (i.e. a teschenite sill in Scotland, the Klokken syenogabbro in Greenland, and a granulite-facies metapelite in Sri Lanka) were used to test the mixing models. It was found that the new model largely eliminates discrepancies between observed and predicted feldspar compositions that were present in earlier attempts. The reasons for the problems associated with phase-equilibrium based mixing models are discussed.     

Relations between assemblages of carpological remains and modern vegetation in a shallow reservoir in southern Poland

This paper explores relations between assemblages of carpological remains and vegetation in and around a small, shallow reservoir in southern Poland. The study was conducted from 2006 to 2008. Quantity and distribution of species in the reservoir were recorded annually during the growing season. In October 2008, 40 samples of surface sediment (top 2?cm) were collected along transects at 10?m intervals. Samples of 100?cm³ were prepared for analysis of plant macroremains. Assemblages of carpological remains generally reflect local vegetation well. In some cases, however, even analysis of numerous samples failed to fully capture the species composition or reflect plant ratios in the parent phytocenosis. Reasons for this include factors that affect seed production, transport and fossilization, which differ among species. Among the best-represented macroremains were plants of the rush phytocenosis. In analysed samples, macroremains of 68.8?% of extant rushes were identified. Sixty percent of submerged and floating-leaf taxa were found in carpological samples, whereas 26.7?% of the trees and bushes were represented in sediment deposits. Species composition of phytocenoses in the reservoir and in surrounding areas was best reflected by macroremains from the nearby reed bed. Numbers of diaspores of Mentha aquatica, Hippuris vulgaris and Carex reflected well their relative abundance in phytocenoses. Chara sp., Juncus inflexus and Eupatorium cannabinum were overrepresented, whereas Typha latifolia and Sparganium minimum were poorly represented in relation to contemporary plant cover. There were no diaspores of Phragmites australis, which dominates the contemporary reed bed. Besides the shape of a reservoir, the key factor influencing diaspore numbers is distribution of plant cover. In many cases, single diaspores (Potentilla erecta, Myosotis scorpioides, Lythrum salicaria, Scutellaria galericulata), or higher concentrations (Hippuris vulgaris, Mentha aquatica, Eleocharis palustris, Schoenoplectus tabernaemontani, Chara sp.) reflected well the location of parent vegetation. The findings indicate that carpological remains in sediments can be an important source of information about plants in and around lakes. They generally reflect well local vegetation and in some cases may be used to identify taxa that dominated in the past.     

Thermodynamic mixing behavior of synthetic Ca-Tschermak–diopside pyroxene solid solutions: I. Volume and heat capacity of mixing

The unite cell parameters and heat capacities of a series of synthetic clinopyroxenes on the join Ca-Tschermak (CaTs)−diopside (Di) were measured using X-ray powder diffraction and calorimetric methods, respectively. The volume of mixing at 298 K shows a negative asymmetric deviation from ideality. A two-parameter Margules fit to the data yields W _CaTs−Di ^V = −0.29 ± 0.11 cm³ mol⁻¹ and W _Di−CaTs ^V = −1.14 ± 0.14 cm³ mol⁻¹. Heat capacities were determined between 5 and 923 K by heat-pulse at 5−302 K and differential-scanning calorimetry at 143−923 K. The precision of the low and high temperature C _p data is better than ±1%. Polynomials of the form C _p = a + bT ^−1/2 + cT ⁻² + dT ⁻³ were fitted to the C _p data in the temperature range between 250 and 925 K. Thermal entropy values [S ₂₉₈ − S ₀] and [S ₉₀₀ −S ₀] as well as enthalpies [H ₂₉₈ − H ₀] and [H ₉₀₀ − H ₀] were calculated for all members of the solid solution series. No significant deviation from ideal mixing behavior was observed.     

Archaeological objects in loesses recognized by GPR research at the site Karmanowice,Poland

The aim of the research was to examine subsurface soil layers with the use of the Ground Penetrating Radar (GPR) method. Neolithic archaeological post in Karmanowice was examined. On the basis of earlier geophysical researches and archaeological premises, eight measurement profiles had been chosen. Ground Penetrating Radar system with antenna of 500 MHz frequency was applied. The measurements were made with 30 and 60 ns time windows. The results were shown as the GPR sections. The analysis of the obtained results allowed us to outline anomalies connected with the appearance of archaeological objects in subsurface soil layers. The border between the anthropogenically changed upper layer and undisturbed loess was established, and the sections of slope wash layers were designated. Anomalies were confirmed by digging and test drillings. Additionally, 2D resistivity imaging method was used for verification of specific anthropogenic anomalies.