Geochemical characteristics of the macromolecular part of crude and biodesulphurised flame coal density fractions

Flame coal (Janina Mine, Poland) was an object of geochemical analyses for changes caused by the process of microbial desulphurisation. Ash content, beryllium, chromium, zinc, cobalt, lithium, manganese, copper, molybdenum, nickel, lead and vanadium concentrations were investigated in coal extracts, its macromolecular part, semi-coke and polar compound fractions of extracts and pyrolysates of crude and biodesulphurised coal density fractions. The macromolecular part of extracted density fractions was pyrolysed giving semi-coke and pyrolysate. These were separated into aliphatic hydrocarbons, aromatic and polar compounds by thin layer chromatography (TLC). Distributions of aliphatic and aromatic hydrocarbons in pyrolysates of the crude and desulphurised coal density fractions were compared by gas chromatography-mass spectrometry (GC-MS). Extracts, extracted density fractions, semi-coke and polar compound fractions were analysed for concentrations of trace elements. In the crude coal their concentrations in the macromolecular part are related only to coke. However, in the desulphurised coal the participation of the particular trace element increases in pyrolysate polar compound fractions. Its values are in the range from 1% (Mn) to 100% (Cr and Mo). These changes are the best seen in the 1.80-2.30×10³ kg/m³ density fraction. Very high concentrations of trace elements were found in pyrolysate of desulphurised coal density fraction. This can be explained by the partial decomposition of coal macromolecule resulting from desulphurisation. Significant side-cleavage of peripheral groups and lighter aromatic hydrocarbons is possible. The effects of bacterial influence were manifested by the increase of polar compounds contents both in pyrolysates and extracts of the desulphurised coal and changes in distribution of aliphatic and aromatic hydrocarbon as pyrolytical products. These effects increase with mineral substance contents. Moreover, the increase of trace element concentration in coal organic matter occurs. It is reflected by the increase of participation of coal pyrolysate polar fraction in the total concentration of analysed elements in the macromolecular part of a given density fraction. The presented results are a part of the larger research aimed to find an influence of desulphurisation on chemical and technological properties of coal.     

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.     

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.     

Unusual reaction of diatom assemblage on climate changes during the last millennium: a record from Spitsbergen lake

A sediment core from the Arctic Revvatnet (Hornsund area, SW Spitsbergen, Svalbard) provided data on environmental changes over the last 3100 years. Diatom analysis showing the domination of planktonic Cyclotella forms suggested good edaphic conditions until the middle of the nineteenth century, even during the Little Ice Age. A thermally stratified and relatively stable water column with good mixing allowed small, less heavily silicified Cyclotella sensu lato to develop during this time. The climate warming at the beginning of the twentieth century induced intensification of erosion processes in the catchment of the lake and caused an increase in the sedimentation rate. These processes have caused a lack of thermal stratification by disturbances in the water column and an increase of nutrients, consequently driving changes in the diatom species composition, which became dominated by benthic forms. In this period, almost all planktonic taxa disappeared or abruptly decreased in frequency. Higher temperatures accelerated the melting of nearby glaciers, which caused an increase in the activity of diatoms typical of running waters. Also a few Cladocera species appeared at the first time in the youngest samples.     

Effects of long term nutrient and climate variability on subfossil Cladocera in a deep,subalpine lake (Lake Garda,northern Italy)

Albeit subfossil Cladocera remains are considered as a reliable proxy for tracking historical lake development, they have been scarcely studied in large subalpine lakes south of the Alps. In this study, subfossil Cladocera remains from Lake Garda in northern Italy were analyzed to track the lake’s environmental changes since the Middle Ages. One core was retrieved from the largest sub-basin of Lake Garda (Brenzone, 350 m deep) and two cores were retrieved from the profundal and littoral zone of the smaller lake sub-basin (Bardolino, 80 and 40 m deep, respectively). The species distribution of Cladocera remains in recent sediment layers was similar to that observed in contemporary water samples. The deepest sections of the three cores were characterized by species sensitive to water temperature, which suggest a key role of major climatic events in driving the lake response during the late Holocene. The most evident change in Cladocera assemblages in the studied cores was observed during the 1960s, when planktonic taxa such as Daphnia spp. and Bosmina spp. became dominant at the expense of littoral taxa. Despite the highly coherent general pattern of subfossil Cladocera, the cores showed a set of minor differences, which were attributed to different morphological and hydrological features of the two basins forming Lake Garda. Multivariate analysis revealed a clear relation of Cladocera to climate variability during periods of low lake nutrient levels (i.e. before the 1960s). This provides additional information on past ecological responses of Lake Garda, as contrast previous data from subfossil diatom and pigment analyses did not fully capture effects of climate change during the same period. Since the 1960s shifts in assemblage composition of Cladocera and diatoms were highly coherent, in response to nutrient increase and the following, less pronounced, decrease in nutrient concentrations. During the last five decades, the response of the Cladocera to climate variability appeared to be masked by nutrient change. This work points up the potential of the multi-proxy approach for disentangling the multifaceted biological responses to multiple environmental stressors in large and deep lakes.     

A data-synthesis-driven method for detecting and extracting vague cognitive regions

Cognitive regions and places are notoriously difficult to represent in geographic information science and systems. The exact delineation of cognitive regions is challenging insofar as borders are vague, membership within the regions varies non-monotonically, and raters cannot be assumed to assess membership consistently and homogeneously. In a study published in this journal in 2014, researchers devised a novel grid-based task in which participants rated the membership of individual cells in a given region and contrasted this approach to a standard boundary-drawing task. Specifically, the authors assessed the vague cognitive regions of Northern California and Southern California. The boundary between these cognitive regions was found to have variable width, and region membership peaked not at the most northern or southern cells but at substantially less extreme latitudes. The authors thus concluded that region membership is about attitude, not just latitude. In the present work, we reproduce this study by approaching it from a computational fourth-paradigm perspective, i.e., by the synthesis of high volumes of heterogeneous data from various sources. We compare the regions which we identify to those from the human-participants study of 2014, identifying differences and commonalities. Our results show a significant positive correlation to those in the original study. Beyond the extracted regions themselves, we compare and contrast the empirical and analytical approaches of these two methods, one a conventional human-participants study and the other an application of increasingly popular data-synthesis-driven research methods in GIScience.     

The Differentiation of Point Symbols using Selected Visual Variables in the Mobile Augmented Reality System

On the basis of initial studies devoted to a better understanding of how the public user (a pedestrian in the city) perceives cartographic symbols in the mobile augmented reality system, we present an attempt to determine the threshold values of differentiation for three visual variables. The variables of size, transparency, and focus were implemented into image point symbols representing five types of objects. The set of symbols was designed in accordance with the rules of cartographic design taking into consideration an analysis of 19 professional tourist works. The symbols were presented on the screen of a mobile device in a system imitating the augmented reality system against four different backgrounds: white, a wall, and two typical urban landscapes. The results of an internet survey conducted using a tablet at four locations in Poznan (Poland) allowed us to determine the following: threshold differentiation values for the analysed variables, indication of the dependence on the type of background displayed on the mobile device in augmented reality, and the advantage of using a combination of visual variables.     

Extracting urban functional regions from points of interest and human activities on location‐based social networks

Data about points of interest (POI) have been widely used in studying urban land use types and for sensing human behavior. However, it is difficult to quantify the correct mix or the spatial relations among different POI types indicative of specific urban functions. In this research, we develop a statistical framework to help discover semantically meaningful topics and functional regions based on the co‐occurrence patterns of POI types. The framework applies the latent Dirichlet allocation (LDA) topic modeling technique and incorporates user check‐in activities on location‐based social networks. Using a large corpus of about 100,000 Foursquare venues and user check‐in behavior in the 10 most populated urban areas of the US, we demonstrate the effectiveness of our proposed methodology by identifying distinctive types of latent topics and, further, by extracting urban functional regions using K‐means clustering and Delaunay triangulation spatial constraints clustering. We show that a region can support multiple functions but with different probabilities, while the same type of functional region can span multiple geographically non‐adjacent locations. Since each region can be modeled as a vector consisting of multinomial topic distributions, similar regions with regard to their thematic topic signatures can be identified. Compared with remote sensing images which mainly uncover the physical landscape of urban environments, our popularity‐based POI topic modeling approach can be seen as a complementary social sensing view on urban space based on human activities.     

A weighted multi-attribute method for matching user-generated Points of Interest

To a large degree, the attraction of Big Data lies in the variety of its heterogeneous multi-thematic and multi-dimensional data sources and not merely its volume. To fully exploit this variety, however, requires conflation. This is a two-step process. First, one has to establish identity relations between information entities across different data sources; and second, attribute values have to be merged according to certain procedures that avoid logical contradictions. The first step, also called matching, can be thought of as a weighted combination of common attributes according to some similarity measures. In this work, we propose such a matching based on multiple attributes of Points of Interest (POI) from the Location-based Social Network Foursquare and the local directory service Yelp. While both contain overlapping attributes that can be used for matching, they have specific strengths and weaknesses that make their conflation desirable. For instance, Foursquare offers information about user check-ins to places, while Yelp specializes in user-contributed reviews. We present a weighted multi-attribute matching strategy, evaluate its performance, and discuss application areas that benefit from a successful matching. Finally, we also outline how the established POI matches can be stored as Linked Data on the Semantic Web. Our strategy can automatically match 97% of randomly selected Yelp POI to their corresponding Foursquare entities.     

Experimental studies of sublimation of highly volatile ices in relevance to the ices of the solar system

Studies of sublimation of complex ices prepared by deposition of gaseous CO, CH₄, N₂, and NH₃ molecules on a cold plate have been performed. The low pressure and low temperature system was used: 10^?9–10^?5 mbar and the lowermost temperature 10 K. Diagnostic of composition of evaporates (at an actual temperature) was done by means of the mass spectrometer. The latter allowed following simultaneously the partial pressure of five different ions or radicals escaping from the substrate. It has been found that highly volatile molecules that were used simultaneously with the low volatile ones to form the complex ices (mixtures or clathrates) present a different sublimation pattern than the sublimation of pure high-volatile ices. In particular, the high-volatile component sublimes at two or even three different temperature regimes: At low temperature that is typical for sublimation of this component, as well as at much higher temperatures. This effect seems to be important when degassing and outbursts from cometary nuclei are considered. It can be also important for modeling of cryovolcanic processes on the icy satellites.