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.     

Geochemical features of re-deposited organic matter occurring in fluvioglacial sediments in the Racibórz region (Poland): A case study

The erosion of rocks rich in organic matter typically leads to the complete mineralization of the organic material. However, in some cases, it is re-deposited to become a part of sediments once more. This process should be considered to be a part of global carbon cycle, possibly much more significant than assumed to-date. The research presented here aims to characterize re-worked organic matter occurring in post-glacial sediments of southern part of Poland, in the Oder river valley (the Racibórz town region, Miocene, Pleistocene and Holocene age). Organic substances extracted from the sediments originated from organic matter that had resided in rocks eroded by glaciers. Sediments were sampled in two boreholes which sediments were correlated. Sediments were extracted and extracts analyzed with gas chromatography-mass spectrometry (GC-MS) to assess distributions of biomarker groups. Organic matter of selected samples was pre-concentrated and analyzed with Py/GC-MS. In the extracts several biomarker parameters of source/environment and thermal maturity were calculated. Organic substances in the investigated sediments come from variable re-deposited organic matter occurring in rocks eroded by glaciers. Three main parent types of re-deposited organic material are identified showing variable geochemical features: 1) organic matter of recent or almost recent age being the source of polar labile compounds; probably formed in situ, 2) re-deposited organic matter of the middle diagenesis showing features similar to lignites (huminite reflectance Rf ~ 0.25–0.35%) deriving from angiosperm remains, mainly monocotyledons and to the lower extend also deciduous trees, 3) re-deposited organic matter at the middle catagenesis (Rf ~ 0.65–0.75%) being the source of most of aromatic hydrocarbons and biomarkers such as steranes, hopanes of the more thermally advanced distribution type. Its geochemical properties and assumed directions of sediment transport indicate bituminous coals of Upper Silesian Coal Basin together with coaly shales as a possible source of this organic matter. Such mixed origin of organic matter caused large discrepancies in values of thermal maturity parameters depending on input from the particular sources and occurrence both geochemical biomarkers and their biochemical precursors in the same samples.     

Geochronology and stable isotope signature of alteration related to hydrothermal magnetite ores in Central Anatolia,Turkey

Hydrothermal iron ores at Divri?i, east Central Anatolia, are contained in two orebodies, the magnetite-rich A-kafa and the limonitic B-kafa (resources of 133.8 Mt with 56% Fe and 0.5% Cu). The magnetite ores are hosted in serpentinites of the Divri?i ophiolite at the contact with plutons of the Murmano complex. Hydrothermal biotite from the Divri?i A-kafa yield identical weighted mean plateau ages of 73.75?±?0.62 and 74.34?±?0.83 Ma (2σ). This biotite represents a late alteration phase, and its age is a minimum age for the magnetite ore. Similar magnetite ores occur at Hasançelebi and Karakuz, south of Divri?i. There, the iron ores are hosted in volcanic or subvolcanic rocks, respectively, and are associated with a voluminous scapolite ± amphibole ± biotite alteration. At Hasançelebi, biotite is intergrown with parts of the magnetite, and both minerals formed coevally. The weighted mean plateau ages of hydrothermal biotite of 73.43?±?0.41 and 74.92?±?0.39 Ma (2σ), therefore, represent mineralization ages. Hydrothermal biotite from a vein cutting the scapolitized host rocks south of the Hasançelebi prospect has a weighted mean plateau age of 73.12?±?0.75 Ma (2σ). This age, together with the two biotite ages from the Hasançelebi ores, constrains the minimum age of the volcanic host rocks, syenitic porphyry dikes therein, and the scapolite alteration affecting both rock types. Pyrite and calcite also represent late hydrothermal stages in all of these magnetite deposits. The sulfur isotope composition of pyrite between 11.5 and 17.4‰ δ³⁴S_(VCDT) points towards a non-magmatic sulfur source of probably evaporitic origin. Calcite from the Divri?i deposit has δ¹⁸O_(VSMOV) values between +15.1 and +26.5‰ and δ¹³C_(VPDB) values between ?2.5 and +2.0‰, which are compatible with an involvement of modified marine evaporitic fluids during the late hydrothermal stages, assuming calcite formation temperatures of about 300°C. The presence of evaporite-derived brines also during the early stages is corroborated by the pre-magnetite scapolite alteration at Divri?i, and Hasançelebi-Karakuz, and with paleogeographic and paleoclimatic reconstructions. The data are compatible with a previously proposed genetic model for the Divri?i deposit in which hydrothermal fluids leach and redistribute iron from ophiolitic rocks concomitant with the cooling of the nearby plutons.     

The impact of the antenna phase center models on the coordinates in the EUREF Permanent Network

GPS Solutions - Precise positioning using the signals of the Global Position System requires correcting the distance between the points of reception of the signal carrier phase and the antenna...     

The mineralogy,geochemistry, and suitability for ceramic applications of Akharım (Afyonkarahisar,W Turkey) kaolinitic clay

Kaolinitic clays associated with sedimentary rocks cover widespread in the Yeniköy formation from the Akhar?m district, (Afyonkarahisar, W Anatolia). Due to the proximity to the ceramic industry areas such as Kütahya and U?ak Province of Turkey, the clays in the Akhar?m district have been intensively exploited for the last few years. The Akhar?m kaolinitic clays were hosted by Middle-Upper Miocene-aged Yeniköy formation and divided into two parts as northeastern and southwestern via normal fault. The alteration degree increases from lower levels to surface in the NE part of deposit. Besides layered structure in their N70° W/30° SW direction and gray-beige, yellowish brown colored in SW part. This study focused on mineralogy, geochemistry, and ceramic properties of kaolinitic clays. X-ray diffraction (XRD) and scanning electron microscope (SEM) analysis, chemical, physical, and mechanical tests were conducted on studied samples from the wall of clay quarry. Akhar?m clay deposits consist of mainly kaolinite and quartz. Additionally, they include smectite, biotite, feldspar, jarosite, calcite, and hematite minerals. Akhar?m clays are characterized with their moderate plasticity (PL = 17.07–24.09), low water absorption (3.64–9.53 wt.%), low linear shrinkage (8.08–15.55 wt.%), high bending strength (17.72–32.69 N/mm²), and ideal lightness values (L* = 46.50–82.74) and color values (a* = 4.71–29.87; b* = 14.67–28.72). These properties vary related with mineralogical and geochemical features of Akhar?m clays. In conclusion, Akhar?m clays have desired specifications for floor and wall t to their mineralogical, geochemical, and ceramic properties.     

Undrained Shear Strength in Cohesive Soils Estimated by Directional Modes of In-Situ Shear Wave Velocity

The estimated undrained shear strength (s_u) is often not a unique value because it can be evaluated by various test types and/or procedures, such as different failure modes, shear strain rates, and boundary conditions. This study explores (1) the relationship between reference undrained shear strength and in situ shear wave velocity in terms of the effective overburden stress, and (2) the independent relationships to evaluate the undrained shear strength with special consideration of different directional and polarization modes (VH, HV, HH shear waves), which has not been reported. This evaluation is done via a worldwide database compiled from 43 well-documented geotechnical test sites associated with soft ground. Finally, new correlation models are proposed to estimate the undrained shear strength based on the in situ shear wave velocity as well as the plasticity index or the overconsolidation ratio. The application of the shear wave velocity–undrained shear strength relation is illustrated through two independent case studies. The proposed relationships are expected to contribute to reasonable estimates of undrained shear strength as well as offer practical guidance on even extrapolation beyond the data that is available to geotechnical engineers.     

Dasycladacean alga <Emphasis Type="Italic">Palaeodasycladus</Emphasis> in the northern Tethys (West Carpathians,Poland) and its new palaeogeographic range during the Early Jurassic

The green alga Palaeodasycladus was recognized in Lower Jurassic shallow-marine high-energy calcarenites of the Cho? Nappe (Hronicum Domain) in the Tatra Mts in Poland. This occurrence indicates the most Northern record of Palaeodasycladus as it is known mostly from the southern part of the Western Tethys. The stratigraphic range of Palaeodasycladus (Norian, Sinemurian–Pliensbachian) and the upper Pliensbachian age of the overlying calcarenites (previous data on the basis of brachiopods) suggest that the studied part of the section was deposited during the Sinemurian–early Pliensbachian. The previous and current reports on occurrences of Palaeodasycladus allowed determination of a new northern palaeogeographic range of the shallow-marine Mediterranean biota during the Early Jurassic time.     

The exceptionally stable cobalt(III)–desferrioxamine B complex

The biogeochemistry of trivalent iron, manganese, and cobalt in the oceans is dominated by soluble complexes formed with high-affinity organic ligands that are believed to be microbial siderophores or similar biogenic chelating agents. Desferrioxamine B (DFOB), a trihydroxamate siderophore found in both terrestrial and marine environments, has served as a useful model for a large class of microbial siderophores in studies of 1:1 complexes formed with trivalent iron and manganese. However, no data exist concerning DFOB complexes with Co(III), which we hypothesize should be as strong as those with Fe(III) and Mn(III) if the current picture of the ocean biogeochemistry of the three trivalent metals is accurate. We investigated the complexation reaction between DFOB and Co(III) in aqueous solution at seawater pH using base and redox titrations, and then characterized the resulting 1:1 complex Co(III)HDFOB⁺ using X-ray absorption, resonance Raman spectroscopy, and quantum mechanical structural optimizations. We found that the complex stability constant for Co(III)HDFOB⁺ (log K _{[Co(III)HDFOB⁺]} = 37.5 ± 0.4) is in fact five and seven orders of magnitude larger than that for Fe(III)HDFOB⁺ (log K_{[Fe(III)HDFOB⁺]} = 32.02) and Mn(III)HDFOB⁺ (log K_{[Mn(III)HDFOB}⁺_] = 29.9), respectively. Spectroscopic data and the supporting theoretical structural optimizations elucidated the molecular basis for this exceptional stability. Although not definitive, our results nevertheless are consistent with the evolution of siderophores as a response by bacteria to oxygenation, not only because of sharply decreasing concentrations of Fe(III), but also of Co(III).