The effect of thermal treatment on the 57Fe Mössbauer spectrum of beryl

Mössbauer spectra (MS) of blue, green and yellow beryl (ideally Be₃Al₂Si₆O₁₈) containing approximately 1% of iron were obtained at 295 and 500 K. Room temperature (RT) spectra of both blue and green samples showed the presence of an asymmetric Fe²⁺ doublet (ΔE _Q~2.7 mm/s, δ~1.1 mm/s), with a very broad low-velocity peak. There is no clear evidence for the presence of a ferric component. The MS of the yellow sample at RT consists of an intense central absorption with parameters typical for Fe³⁺ (ΔE _Q~0.4 mm/s, δ~0.29 mm/s), plus an apparently symmetrical Fe²⁺ doublet. This sample acquires a light-blue shade upon heating in air at about 620 K. Thermal treatments at high temperatures caused no significant changes in the MS, but the green and yellow beryl acquire a blue colour. All these results are interpreted in relation to the existence of channel water and the distribution of iron among the available crystallographic sites.     

Quantification of karst aquifer discharge components during storm events through end-member mixing analysis using natural chemistry and stable isotopes as tracers

Karst aquifer components that contribute to the discharge of a water supply well in the Classical Karst (Kras) region (Italy/Slovenia) were quantitatively estimated during storm events. Results show that water released from storage within the epikarst may comprise as much as two-thirds of conduit flow in a karst aquifer following rainfall. Principal components analysis (PCA) and end-member mixing analysis (EMMA) were performed using major ion chemistry and the stable isotopes of water (δ¹⁸O, δ²H) and of dissolved inorganic carbon (δ¹³C_DIC) to estimate mixing proportions among three sources: (1) allogenic river recharge, (2) autogenic recharge, and (3) an anthropogenic component stored within the epikarst. The sinking river most influences the chemical composition of the water-supply well under low-flow conditions; however, this proportion changes rapidly during recharge events. Autogenic recharge water, released from shallow storage in the epikarst, displaces the river water and is observed at the well within hours after the onset of precipitation. The autogenic recharge end member is the second largest component of the well chemistry, and its contribution increases with higher flow. An anthropogenic component derived from epikarstic storage also impacts the well under conditions of elevated hydraulic head, accounting for the majority of the chemical response at the well during the wettest conditions.     

Environmental and health risk assessment in abandoned mining area, Zlata Idka, Slovakia

The Zlata Idka village is a typical mountainous settlement. As a consequence of more than 500 years of mining activity, its environment has been extensively affected by pollution from potentially toxic elements. This paper presents the results of an environmental-geochemical and health research in the Zlata Idka village, Slovakia. Geochemical analysis indicates that arsenic (As) and antimony (Sb) are enriched in soils, groundwater, surface water and stream sediments. The average As and Sb contents are 892 mg/kg and 818 mg/kg in soils, 195 mg/kg and 249 mg/kg in stream sediments, 0.028 mg/l and 0.021 mg/l in groundwater and 0.024 mg/l and 0.034 mg/l in surface water. Arsenic and Sb concentrations exceed upper permissible limits in locally grown vegetables. Within the epidemiological research the As and Sb contents in human tissues and fluids have been observed (blood, urine, nails and hair) in approximately one third of the village’s population (120 respondents). The average As and Sb concentrations were 16.3 μg/l and 3.8 μg/l in blood, 15.8 μg/l and 18.8 μg/l in urine, 3,179 μg/kg and 1,140 μg/kg in nails and 379 μg/kg and 357 μg/kg in hair. These concentrations are comparatively much higher than the average population. Health risk calculations for the ingestion of soil, water, and vegetables indicates a very high carcinogenic risk (>1/1,000) for as content in soil and water. The hazard quotient [HQ=average daily dose (ADD)/reference dose (RfD)] calculation method indicates a HQ>1 for groundwater As and Sb concentrations.     

Superdense CO2 inclusions in Cretaceous quartz–stibnite veins hosted in low-grade Variscan basement of the Western Carpathians, Slovakia

CO₂ inclusions with density up to 1,197 kg m⁻³ occur in quartz–stibnite veins hosted in the low-grade Palaeozoic basement of the Gemericum tectonic unit in the Western Carpathians. Raman microanalysis corroborated CO₂ as dominant gas species accompanied by small amounts of nitrogen (<7.3 mol%) and methane (<2.5 mol%). The superdense CO₂ phase exsolved from an aqueous bulk fluid at temperatures of 183–237°C and pressures between 1.6 and 3.5 kbar, possibly up to 4.5 kbar. Low thermal gradients (∼12–13°C km⁻¹) and the CO₂–CH₄–N₂ fluid composition rule out a genetic link with the subjacent Permian granites and indicate an external, either metamorphogenic (oxidation of siderite, dedolomitization) or lower crustal/mantle, source of the ore-forming fluids.According to microprobe U–Pb–Th dating of monazite, the stibnite-bearing veins formed during early Cretaceous thrusting of the Gemeric basement over the adjacent Veporic unit. The 15- to 18-km depth of burial estimated from the fluid inclusion trapping PT parameters indicates a 8- to 11-km-thick Upper Palaeozoic–Jurassic accretionary complex overlying the Gemeric basement and its Permo-Triassic autochthonous cover.     

Geometry and accuracy of reflecting points in bistatic satellite altimetry

The analysis of the time and space distribution of specular (reflecting) points in bistatic altimetry between GPS and CHAMP satellites or SAC-C (taken as examples) is extended from Wagner and Klokočník (2003 J. Geod 77: 128–138). We demonstrate a significantly higher number and density of reflecting points in bistatic altimetry in comparison with traditional monostatic altimetry. After an outline of our older accuracy assessment for the vertical position of the reflecting point, we add a new independent derivation and compare both approaches. We account for orbit errors of both the transmitters (GPS) and receiver (CHAMP) satellites, and the measurement (delay) error. We found that the accuracy of the vertical position of the reflecting point decreases only slowly with increasing off-nadir angle and that the orbit errors must be accounted for if decimeter and better accuracy is required. In this paper, we do not study errors such as state of the ocean, technical parameters of the receiving system, and atmospheric corrections.     

Groundwater-flow modeling in the Yucatan karstic aquifer, Mexico

The current conceptual model of the unconfined karstic aquifer in the Yucatan Peninsula, Mexico, is that a fresh-water lens floats above denser saline water that penetrates more than 40 km inland. The transmissivity of the aquifer is very high so the hydraulic gradient is very low, ranging from 7–10 mm/km through most of the northern part of the peninsula. The computer modeling program AQUIFER was used to investigate the regional groundwater flow in the aquifer. The karstified zone was modeled using the assumption that it acts hydraulically similar to a granular, porous medium. As part of the calibration, the following hypotheses were tested: (1) karstic features play an important role in the groundwater-flow system; (2) a ring or belt of sinkholes in the area is a manifestation of a zone of high transmissivity that facilitates the channeling of groundwater toward the Gulf of Mexico; and (3) the geologic features in the southern part of Yucatan influence the groundwater-flow system. The model shows that the Sierrita de Ticul fault, in the southwestern part of the study area, acts as a flow barrier and head values decline toward the northeast. The modeling also shows that the regional flow-system dynamics have not been altered despite the large number of pumping wells because the volume of water pumped is small compared with the volume of recharge, and the well-developed karst system of the region has a very high hydraulic conductivity. Electronic Publication     

Thermal expansion and crystal structure of FeSi between 4 and 1173 K determined by time-of-flight neutron powder diffraction

The thermal expansion and crystal structure of FeSi has been determined by neutron powder diffraction between 4 and 1173?K. No evidence was seen of any structural or magnetic transitions at low temperatures. The average volumetric thermal expansion coefficient above room temperature was found to be 4.85(5)?×?10^?5?K^?1. The cell volume was fitted over the complete temperature range using Grüneisen approximations to the zero pressure equation of state, with the internal energy calculated via a Debye model; a Grüneisen second-order approximation gave the following parameters: θ_D=445(11)?K, V ₀=89.596(8)?ų, K ₀′=4.4(4) and γ′=2.33(3), where θ_D is the Debye temperature, V ₀ is V at T=0?K, K ₀′ is the first derivative with respect to pressure of the incompressibility and γ′ is a Grüneisen parameter. The thermodynamic Grüneisen parameter, γ_th, has been calculated from experimental data in the range 4–400?K. The crystal structure was found to be almost invariant with temperature. The thermal vibrations of the Fe atoms are almost isotropic at all temperatures; those of the Si atoms become more anisotropic as the temperature increases.     

Image analysis applied to quantitative evaluation of chromatic impact generated by open-pit quarries and mines

One of the most important environmental impacts resulting from opencast mining, and especially quarries, is the visual impact. Evaluation of this impact considers two aspects: first, the area occupied by the quarry as seen by an observer from a specific place, and, second, the chromatic contrast existing between landscape and exploitation. In this study we develop a methodology to assess the chromatic impact in an objective and comparable form. To assess this impact we developed a method based on image analysis that allows us to obtain from a picture or image its equivalent as a function of chromatic impact, according to the sensibility of the human eye to different wavelengths. The methodology was applied to the Martinenca limestone quarry (Alcanar, Tarragona) and to Cerro Kori Kollo mine, La Joya district (Bolivia).     

Anhydrite-bearing rocks from the Rožná district (Moldanubian zone,Czech Republic): high-grade metamorphosed exhalites?

Several types of anhydrite-bearing rocks have been found in the amphibolite-facies metamorphosed rocks at the north-eastern margin of the Moldanubian Zone. Anhydrite either forms monomineralic bands up to 40 cm thick, or occurs in the form of disseminated grains in surrounding calc-silicate gneiss together with feldspar, scapolite, amphibole, pyroxene, epidote and pyrite. The isotopic composition of sulphur ('³⁴S=30.6 to 32.3‰) and strontium (⁸⁷Sr/⁸⁶Sr=0.70797 to 0.70781) in anhydrite may indicate a marine source of sulphate. The isotopic ratio of strontium is in the same range as that of metamorphosed strata-bound barite-sulphide ores, which have been previously described in the same area. The '³⁴S values of coexisting pyrite range from 21.4 to 22.5‰, the (³⁴S_{anhydrite-pyrite} corresponding to the metamorphic temperature of 600 to 660 °C. In contrast to many submarine-exhalative deposits, the oxygen isotopic compositions of anhydrite ('¹⁸O=9.3 to 10.2‰) are lighter than that of barite ('¹⁸O=10.4 to 13.8‰). This indicates that the both minerals are not in isotopic equilibrium. Therefore, it is probable that anhydrite and barite from the Ro—ná district were deposited from fluids that contained different proportions of seawater and hydrothermal fluids or from hydrothermal fluids that underwent variable extent of oxygen isotope exchange with seafloor rocks. The '¹³C values in calcite ('¹³C=-17.2 to -18.7‰) from anhydrite-bearing rock are lower than those in distant marbles. As graphite is absent in anhydrite- and calcite-bearing rocks, impoverishment in the ¹³C isotope cannot be attributed to the graphite-carbonate isotopic exchange during metamorphism. It is proposed that low '¹³C values in carbonates are caused by pre-metamorphic oxidation of organic matter in course of hydrothermal processes. Anhydrite and anhydrite-bearing calc-silicate gneiss from the north-eastern part of the Moldanubian Zone are interpreted to be the high-grade metamorphosed analogue of anhydrite-rich exhalites commonly found in submarine-exhalative hydrothermal deposits.