Episodes of extreme rainwater pollution and its relationship with synoptic situation (Wielkopolski National Park,Poland)

Synoptic conditions of extreme rainwater pollution episodes, evidenced by maximum values of parameters measured in the protected area of Wielkopolski National Park (western-central Poland), were analysed in this study. Precipitation samples were tested for the following parameters: pH, electrical conductivity and the concentration of the following elements: F^-, Cl^-, NO₂^-, NO₃^-, PO₄^3-, SO₄^2- and Na⁺, NH₄⁺, K⁺, Mg²⁺, Ca²⁺. It was assumed, that in winter, western advection of Atlantic air masses was the most frequent aerosol and pollution transport scenario for the investigated area. In summer the most heavily pollution occur at the intensified meridional flow over the central Europe, indicating advection of cooler air from northern Europe and the North Sea. In most of cases, the weather conditions causing extreme concentration of examined pollutants, were determined by the movement of weather fronts over considerable parts of Poland and by precipitation caused by those fronts.     

An attempt to use LA-ICP-SMS to quantify enrichment of trace elements on pyrite surfaces in oxidizing mine tailings

Metals released from oxidation and weathering of sulphide minerals in mine tailings are to a high degree retained at deeper levels within the tailings themselves. To be able to predict what could happen in the future with these secondarily retained metals, it is important to understand the retention mechanisms. In this study an attempt to use laser ablation high-resolution ICP-MS (LA-ICP-SMS) to quantify enrichment of trace elements on pyrite surfaces in mine tailings was performed. Pyrite grains were collected from a profile through the pyrite-rich tailings at the Kristineberg mine in northern Sweden. At each spot hit by the laser, the surface layer was analyzed in the first shot, and a second shot on the same spot gave the chemical composition of the pyrite immediately below. The crater diameter for a laser shot was known, and by estimating the crater depth and total pyrite surface, the total enrichment on pyrite grains was calculated. Results are presented for As, Cd, Co, Cu, Ni and Zn. The results clearly show that there was an enrichment of As, Cd, Cu and Zn on the pyrite surfaces below the oxidation front in the tailings, but not of Co and Ni. Arsenic was also enriched on the pyrite grains that survived in the oxidized zone. Copper has been enriched on pyrite surfaces in unoxidized tailings in the largest amount, followed by Zn and As. However, only 1.4 to 3.1% of the Cd and Zn released by sulphide oxidation in the oxidized zone have been enriched on the pyrite surfaces in the unoxidized tailings, but for As and Cu corresponding figures are about 64 and 43%, respectively. There were many uncertainties in these calculations, and the results shall not be taken too literally but allowed the conclusion that enrichment on pyrite surfaces is an important process for retention of As and Cu below the oxidation front in pyrite rich tailings. Laser ablation is not a surface analysis technique, but more of a thin layer method, and gives no information on the type of processes resulting in enrichment on the pyrite surfaces. Although only pyrite grains that appeared to be fresh and without surface coatings were used in this study, the possibility that a thin layer of Fe-hydroxides occurred must be considered. Both adsorption to the pyrite directly or to Fe-oxyhydroxides may explain the enrichment of As, Cd, Cu and Zn on the pyrite surfaces, and, in the case of Cu, also the replacement of Fe(II) by Cu(II) in pyrite.     

Effects of desferrioxamine-B on the release of arsenic from volcanic rocks

Microorganisms play an important role in As mobilization into groundwater by directly influencing As speciation or indirectly inducing solubilisation from As-bearing phases, such as Fe, Mn and Al oxides. Iron oxide dissolution could also be induced by siderophores, small-molecule compounds produced by microorganisms to favour Fe uptake. Well waters exceeding the potable water limit of 10 μg As L⁻¹ (0.133 μM) have been widely reported in geothermal areas. Mechanisms responsible for these high As concentrations have not yet been thoroughly elucidated and the complexity of As mobilization in volcanic aquifers is still open to multiple interpretations. The present study was based on batch release experiments aimed at verifying and quantifying the effect of siderophores on As mobilization from volcanic rocks (lava, tuff, peperino and fallout deposit) at different pH and ligand concentration. In the experiments the siderophore trihydroxamate desferroxamine B (Dfob) was used and its effect on As release from volcanic rocks was manifest after the first days. The most favourable pH for As release was pH 6 while concentrations above 250 μM Dfob considerably enhanced As and Fe concentrations in solution. The As release from rocks was between 2.0–10% at pH 6 and 2.4–8.8% at pH 8. The As/Fe ratio in solution changed with time suggesting different release mechanisms and higher mobility of As compared to Fe during the first phase of the experiment. The presence of siderophore increased Fe dissolution rates up to 10 orders of magnitude. The As release correlated with Al, Mn, Fe, Si, V, Ga and Sb and the release of all these elements increased with increasing Dfob concentration. In alkaline environments also Cu, Zn and Pb were mobilized. The presence of siderophores represents a possible trigger for As mobilization from iron binding minerals to the water phase, with interesting implications for groundwater quality, plant uptake and bacterial communities.     

Scale and timing of Rare Earth Element redistribution in the Taconian foreland of New England

Clastic sedimentary rocks, deposited on eastern North America in response to the Taconian Orogeny, commonly have Sm/Nd isotope relationships indicating substantial isotope disturbance near or subsequent to the time of sedimentation that may be associated with severe depletion in light rare earth elements (LREE). Affected units [Normanskill Formation (Austin Glen and Pawlet Members), Frankfort Formation and Perry Mountain Formation] are widely separated both geographically (western New York to western Maine) and stratigraphically (Middle Ordovician to Silurian). A model is proposed for the most likely explanation of the observed REE and Sm/Nd isotope relationships involving a two‐stage process. In the first stage, REE are redistributed on a mineralogical scale (dissolution/precipitation on a sample scale) often with the involvement of REE‐enriched trace phases such as apatite and monazite. This stage typically takes place during diagenesis but may also take place later during metamorphism and/or recent weathering, and results in isotope re‐equilibration on a sample scale. The second stage occurs when one or more of these phases is redissolved and REE are transported on large advective scales. Where LREE‐enriched phases are involved, this gives rise to LREE depletion in whole rocks. The timing of this second stage cannot be constrained from Sm/Nd isotope data and may take place at any time subsequent to the isotope re‐equilibration. Such complex histories of REE redistribution may result in serious errors in estimating Nd model ages but not in estimating the Nd isotope composition at the age of sedimentation. Thus, Sm/Nd ratios even of unmetamorphosed sedimentary rocks have to be carefully evaluated before the calculation of depleted mantle model ages for the provenance.     

Object-oriented knowledge-based symbol selection for visualizing statistical information

Abstract

Object-oriented schemes for representing and processing knowledge concerned with cartographic sy mbolization in GIS have been suggested by a number of researchers. As a sequel to these research efforts, the problem of object-oriented knowledge representation in the domain of symbol selection for visualizing spatial statistical information is addressed in this paper, and an operational system on this domain is presented. First, the domain knowledge is specified, and the decision process for symbol selection is formulated. Then the specified knowledge is represented and processed in an object-oriented manner. Implementation issues are discussed, and results are demonstrated with examples.     

Spectral reflectance properties of carbonates from terrestrial analogue environments: Implications for Mars

Spectroscopic analysis of carbonate-bearing samples from a variety of terrestrial environments provides important insights into spectroscopy-based investigations of Mars designed to detect the presence of carbonate minerals. In order to better address the spectral detectability of carbonates on Mars, we examined the spectral reflectance properties of carbonates and carbonate-bearing lithologies from a variety of terrestrial environments, including impact structures (Haughton, St. Martin, Eagle Butte), landslides (Frank), quarrying operations (Hecla), carbonates affected by weathering (Haughton, East German Creek), and sulfide-sulfate-carbonate assemblages (Central Manitoba). The goal is to identify processes and environments that can affect spectroscopy-based carbonate detection, for more detailed follow-on studies. Common carbonates appear to be stable, from a spectroscopic perspective, to various tectonic processes. Iron oxides/hydroxides do not appear to significantly affect spectral detectability of carbonates, as the spectrum-altering effects of these phases are largely restricted to the region below ∼1 μm, while useful carbonate absorption bands occur longward of ∼1.8 μm. Carbonate detection and characterization in the 0.35-2.5-μm region is largely restricted to a single absorption feature in the 2.3-μm region, which can be problematic for robust carbonate identification. While tectonic processes and iron oxide/hydroxide staining do not appear to significantly impair carbonate detection based on the 2.3-μm region absorption band, a number of other factors can affect carbonate detection. These include the fact that this absorption band is weak compared to many other minerals, a number of other minerals also exhibit absorption bands in this wavelength region (leading to possible misidentifications), and that even small abundances of minerals that absorb strongly in this region will reduce the strength of the carbonate absorption band. Identifying the nature of accessory minerals associated with carbonates can be used to constrain possible formation environments. Ongoing research at carbonate-bearing terrestrial analogue sites will continue to provide new insights into the occurrence and detection of carbonates on Mars.     

Vertical crustal motions from differential tide gauge observations and satellite altimetry in southern Italy

Our goal is to determine vertical crustal movement rates from tide gauge and satellite altimetry measurements. Tide gauges measure sea level, but as they are fixed to the crust, they sense both sea surface height variations and vertical crustal movements. The differential sea level rates of sufficiently nearby stations are a good means to determine differential crustal movement rates, when sea level height variations can be assumed to be homogeneous. Satellite altimetric measurements determine sea surface height variations directly and can be used to separate the crustal signal from the sea surface height variations in tide gauge measurements. The correction of the tide gauge sea level rates for the sea surface height contribution requires collocation of the satellite pass and the tide gauge station. We show that even if this is not the case, the satellite altimetric observations enable correction of differential tide gauge rates for the effects of sea surface rate inhomogeneities.     

Distribution and speciation of gold in biogenic and abiogenic calcium carbonates - Implications for the formation of gold anomalous calcrete

Calcrete (pedogenic Ca carbonate) is an important sampling medium for geochemical gold (Au) exploration in semi-arid and arid regions of Australia, because it is widespread, easy to sample and calcium (Ca) shows a strong positive correlation with Au, but not with base metals, in calcrete overlying buried Au mineralization. In this study we show that the formation of Au-anomalous calcrete can be biomediated through the activity of resident microorganisms, and may not simply be the result of passive nucleation on inactive cells or evapotransporative processes. Calcified microfossils are highly abundant in calcrete from the Barns Au-prospect in South Australia. These microfossils are morphological analogues of calcified cells and biofilms formed in laboratory experiments conducted with active bacterial cultures enriched from Au-anomalous calcareous sand from the Barns prospect. Calcium carbonates precipitated by these cultures consisted mostly of calcite, which is the main carbonate mineral in calcrete. Synchrotron micro-X-ray fluorescence (S-μXRF) mapping was used to assess the distribution of Au, Zn, Ca and other metals in Ca carbonates precipitated by active bacterial cultures. On a μm-scale the distribution of Au was heterogeneous in these Ca carbonates and differed from base metal distribution, thus mimicking the spatial separation of these metals observed in calcrete. The speciation of Au in Ca carbonates precipitated by active bacteria was measured using micro-X-ray absorption near edge structure spectroscopy (μ-XANES) and resembled that observed in Au-anomalous calcrete closely. While metallic Au was observed in Au ‘hotpots’, ionic Au was detected in the halo surrounding the ‘hotspot’. In contrast, the precipitates produced in the presence of dead bacterial cells or by raising solution pH or pCO₂, i.e., hydroxylapatite, portlandite and vaterite, respectively, did not reflect the mineralogy of calcrete. Gold distribution and speciation in vaterite, formed by raising pCO₂, were homogenous and did not reproduce the variation observed in calcrete and Ca carbonates precipitated by active cells. Increasing the supersaturation with respect to Ca in solution by incremental drying of the medium produced only X-ray amorphous precipitates, or hydroxylapatite in the presence heat-killed cells. In conclusion, this study shows that active microbial processes that combine biogenic Ca carbonatogenesis with Au precipitation are likely to drive the formation of Au-anomalous calcrete.     

Comparison of the geophysical excitations of polar motion from the period: 1980.0–2009.0

In this study we compared contributions to polar motion excitation determined separately from each of three kinds of geophysical data: atmospheric pressure, equivalent water height estimated from hydrological models, and harmonic coefficients of the Earth gravity field obtained from Gravity Recovery and Climate Experiment (GRACE). Hydrological excitation function (Hydrological Angular Momentum — HAM) has been estimated from models of global hydrology, based on the observed distribution of surfacewater, snow, ice, and soil moisture. In our considerationwe used several global models of land hydrosphere and models ofAtmospheric Angular Momentum (AAM) and Oceanic Angular Momentum (OAM). All of themwere compared with observed Geodetic Angular Momentum (GAM). The spectra of the following excitation functions of polar motion: GAM, AAM+OAM, AAM+OAM+HAM, GAM-AAM-OAM residual geodetic excitation function, and HAM were computed too. The time variable spectra of geodetic, gravimetric, and the sum of atmospheric, oceanic, and hydrological excitation functions are also presented. Phasor diagrams of the seasonal components of polar motion excitation functions of all HAM excitation functions as well as of two GRACE solutions: Center for Space Research (CSR), Centre National d’Etudes Spatiales/Groupe de Recherche en Geodesie Spatiale (CNES/GRGS) were determined and discussed.