Novel aryl polycyclic aromatic hydrocarbons: Phenylphenanthrene and phenylanthracene identification, occurrence and distribution in sedimentary rocks

Numerous reports have recognised the presence of compounds with molecular weight 254 a.m.u. in aromatic fractions. However, their unequivocal identification has not been achieved due to a lack of reference substances. In geological samples, such m/z 254 compounds could potentially be represented by a number of structural isomers of binaphthyl, phenylphenanthrene, phenylanthracene and indenofluorene with each compound type possessing several positional isomers. In this work, all these m/z 254 compounds, with the exception of the tentatively recognised indenofluorenes, have been unequivocally identified in sedimentary rocks for the first time. Comparison of the mass spectra and the gas chromatography (GC) retention times of synthesised standards with the natural compounds in rocks shows that the major components of aromatic fractions are phenylphenanthrene isomers and, to a lesser extent, binaphthyls and 9-phenylanthracene. The elution sequence expressed as standard retention indices of all these m/z 254 isomers were determined by using high resolution capillary GC with three stationary phases: 5%, 35% and 50% (mole fraction) phenyl substituted methylpolysiloxane on HP-5MS, DB-35MS and DB-17MS columns, respectively. A survey of more than 350 sedimentary rock samples of varying origins and maturity (R_r 0.3–1.4%) reveals that relative abundances of the m/z 254 isomers depend on the maturity of the organic matter. The isomers initially appear at the onset of oil generation (R_r > 0.5%) exclusively in diagenetically/catagenetically oxidised samples containing varying proportions of Types II and III kerogen. Interestingly, all five possible positional phenylphenanthrene isomers (including the most sterically hindered isomer 4-phenylphenanthrene) are present from the beginning of the oil generation window. Such a distribution suggests that low-regioselectivity reactions are likely to be involved in the formation. Interaction, during maturation, of phenyl radicals from primary cracking with aromatic moieties of more resistant terrigenic components of kerogen in an oxidising diagenetic realm is postulated to be responsible for the neoformation of phenylated aromatics in geological samples. Up to the final stages of oil generation, the evolution of the phenyl PAH distributions presumably involve 1,2-phenyl shift reactions and cyclisation, if allowed by the molecular geometry. A near thermodynamically-controlled distribution, with only 3- and 2-phenylphenanthrene and minor 2,2′-binaphthyl remaining, is approached when vitrinite reflectance reaches 1.2% (R_r). The three compounds seem to be persistent beyond the oil window as is suggested by their presence in hydrothermal oil formed at T > 300 °C.     

On the impact of rockfall catch fences on ground-based radar interferometry

Rockfalls are major natural hazards in mountainous regions and as such monitored if they pose a high risk to people or infrastructure. Ground-based radar interferometry is a relatively new technique suitable for such monitoring. It offers the potential for determining sub-mm- to mm-level displacements by remote measurements under various weather conditions. To avoid damage from smaller rocks and debris, critical surfaces are often protected by rockfall catch fences. We present an experimental investigation proving that the radar measurements are indeed significantly affected by a catch fence made of steel even if its mesh size is larger compared to that of the wavelength of the radar. A stable rock wall in a quarry was monitored by means of a ground-based synthetic aperture radar for 2 days. Different fences varying in shape, size, and density of mesh and in various geometrical configurations were erected at different locations for short periods of time during the experiment. We show that for surfaces observed through the fence, the reflected power can be reduced by 20 dB and thus the signal-to-noise ratio is significantly deteriorated. We also observed spurious interferometric phase shifts. Even parts of the rock wall not covered by the fences are affected. Side lobes and mixed pixels result, e.g., in severe loss of coherence and thus potentially mask actual displacements.     

2-D seismic tomographic and ray tracing modelling of the crustal structure across the Sudetes Mountains basing on SUDETES 2003 experiment data

The seismic data obtained during SUDETES 2003 experiment are analysed, and detailed crustal structure for profiles S02, S03 and S06 is presented using three different 2-D techniques: (1) “smooth” tomography of refracted waves travel times, (2) ray tracing of reflected and refracted waves, and (3) joint velocity and depth of reflector tomographic inversion. In spite of different interpretation techniques used, the models of the crustal structure show common characteristic features. The low velocity (V_p < 4 km/s) sedimentary layer was documented in the northeastern part of the study area. The topmost basement has in general a velocity of 5.8–6.0 km/s, and velocities at ca. 20 km depth are 6.15–6.25 km/s. The strong reflecting boundaries were found at 20–23 and 25–28 km depth with a velocity contrast about 0.4 km/s, and the highest velocities in the lowermost crust are 6.8–7.2 km/s. In general, the crust of the Bohemian Massif is slightly thicker (33–35 km) than in the northern part of the area. Velocities beneath Moho are relatively low, of 7.95 km/s. On the basis of well recorded reflected waves, mantle reflectors were discovered in the depth interval ca. 40–70 km. Apart of new results for the geology and tectonics of the area, some conclusion could be made about different techniques used. In the 2-D case the “clasical” ray tracing method with using all correlated phases gives the most adequate model of the structure, because of full, manual control of the model creation. The “smooth” first arrival travel times tomography, although very fast, is not satisfactory enough to describe the complex structure. So, the best candidate in 3-D case seems to be travel time tomography for both refracted and reflected waves in multi-layers models.     

Influence of a second satellite on the rotational dynamics of an oblate moon

The gravitational influence of a second satellite on the rotation of an oblate moon is numerically examined. A simplified model, assuming the axis of rotation perpendicular to the (Keplerian) orbit plane, is derived. The differences between the two models, i.e. in the absence and presence of the second satellite, are investigated via bifurcation diagrams and by evolving compact sets of initial conditions in the phase space. It turns out that the presence of another satellite causes some trajectories, that were regular in its absence, to become chaotic. Moreover, the highly structured picture revealed by the bifurcation diagrams in dependence on the eccentricity of the oblate body’s orbit is destroyed when the gravitational influence is included, and the periodicities and critical curves are destroyed as well. For demonstrative purposes, focus is laid on parameters of the Saturn–Titan–Hyperion system, and on oblate satellites on low-eccentric orbits, i.e. \(e\approx 0.005\).     

Holocene changes in climate and land use drove shifts in the diversity of testate amoebae in a subalpine pond

Testate amoebae that inhabit peat are sensitive indicators of water table position. In this study, we used testate amoebae in sediments from a mire in the western Alps (Lac du Thyl) to: (1) reconstruct the hydrology of the site over the last 7,000 years, (2) determine how hydrological changes affected testate amoebae diversity and (3) infer past trophic state shifts. The study site is located in one of the driest valleys of the Alps and is thus very sensitive to hydrological changes. Our study revealed that the water table depth increased (dry conditions) between 5,800 and 4,000 cal year BP. This triggered establishment of a Sphagnum-type peat and acidic conditions from 5,700 to 4,000 cal year BP. These processes were independent of ongoing transformations of the terrestrial vegetation and soil in the catchment area. After 1,690 cal year BP, the depth to the water table decreased (wetter conditions) and a minerotrophic fen developed. At the same time, the diversity of testate amoebae increased, probably as a result of deforestation that supported the expansion of grassland. Climate and land use were apparently more important factors controlling the lake hydrology than were changes in vegetation and soil in the catchment. Testate amoebae diversity was linked to land cover. Changes in pH were controlled indirectly by external forcing (climate), but more directly by fluctuations in the level of the water table (internal forcing) and autogenous expansion of Sphagnum.     

Geology,stratigraphy and palaeoenvironmental evolution of the Stephanorhinus kirchbergensis-bearing Quaternary palaeolake(s) of Gorzów Wielkopolski (NW Poland,Central Europe)

The sedimentary succession exposed in the Gorzów Wielkopolski area includes Eemian Interglacial (MIS 5e) or Early Weichselian (MIS 5d–e) deposits. The sedimentary sequence has been the object of intense interdisciplinary study, which has resulted in the identification of at least two palaeolake horizons. Both yielded fossil remains of large mammals, alongside pollen and plant macrofossils. All these proxies have been used to reconstruct the environmental conditions prevailing at the time of deposition, as well as to define the geological context and the biochronological position of the fauna. Optically stimulated luminescence dating of the glaciofluvial layers of the GS3 succession to 123.6 ± 10.1 (below the lower palaeolake) and 72.0 ± 5.2 ka (above the upper palaeolake) indicate that the site formed during the Middle–Late Pleistocene (MIS 6 – MIS 5). Radiocarbon-dating of the lacustrine organic matter revealed a tight cluster of Middle Pleniglacial Period (MIS 3) ages in the range of ~41–32 ka cal bp (Hengelo – Denekamp Interstadials). Holocene organic layers have also been found, with ¹⁴C ages within a range of 4330–4280 cal bp (Neolithic). Pollen and plant macrofossil records, together with sedimentological and geochemical data, confirm the dating to the Eemian Interglacial.     

The significance of Chara vegetation in the precipitation of lacustrine calcium carbonate

A significant portion of calcium carbonate is deposited in lake sediments as a result of biological processes related to the photosynthetic activity of phytoplankton in the pelagic realm and, in addition, macrophytes in the littoral zone. Lake Wigry, one of the largest lakes in Poland (north‐east Poland), is characterized by: (i) carbonate sediments with a CaCO₃ content exceeding 80% within the littoral zone; and (ii) large areas of submerged vegetation dominated by charophytes (macroscopic green algae, Characeae family). It is claimed that charophytes are highly effective in utilizing HCO₃^? and forming thick CaCO₃ encrustations. Thus, this study was aimed at evaluating the CaCO₃ production by dense Chara stands overgrowing the lake bottom reaching a depth of 4 m. In late July 2009, the fresh and dry mass of plants, the percentage contribution of calcium carbonate and the production of CaCO₃ per 1 m² were investigated along three transects at three depths (1 m, 2 m and 3 m, with each sample area equal to 0·0625 m²) per transect. The composition and structure of phytoplankton and the physico‐chemical properties of the water analysed in both the littoral and pelagic zones served as the environmental background and demonstrated moderately low fertility in the lake. The greatest dry plant mass exceeded 1000 g m^?2 and CaCO₃ encrustations constituted from 59% to over 76% of the charophyte dry weight. Thus, the maximum and average values of carbonates precipitated by charophytes were 685·5 and 438 g m^?2, respectively, which exceeded previously reported results. A correlation of carbonate production with the depth of Chara stands was detected, and intermediate depths offered the most favourable conditions for carbonate precipitation (589 g m^?2 on average). As precipitated carbonates are ultimately stored in bottom deposits, the results highlight the significance of charophytes in lacustrine CaCO₃ sedimentation.     

Early Cretaceous (Valanginian) sea lilies (Echinodermata, Crinoidea) from Poland

Valanginian strata in central epicratonic Poland have recently yielded crinoids, not previously recorded from the area. The fauna comprises isocrinids (Balanocrinus subteres, B. gillieroni, “Isocrinus?” lissajouxi), millericrinids (Apiocrinites sp.) and comatulids (Comatulida indet.). For comparison, a few samples of isocrinids from Valanginian strata of Hungary (Tethyan province) were also analysed. The isocrinids, cyrtocrinids and roveacrinids (sensu Rasmussen 1978 inclusive of Saccocoma sp.) were already known from the Valanginian of the southernmost Tethyan regions of Poland (Pieniny Klippen Belt and Tatra Mountains). The current study demonstrates their occurrence in central epicratonic Poland, and suggests that many Jurassic to Cretaceous stalked crinoid taxa (mainly isocrinids) predominated in the shallow-water settings of this area. Thus, the hypothesis of migration (at least from mid-Cretaceous onwards) to deep-water areas, as a response to an increase of the number of predators during the Mesozoic marine revolution, seems not to be universally applicable.     

Local regression models for spatial interpolation of urban heat island—an example from Wroc?aw, SW Poland

Geographically weighted regression algorithm (GWR) has been applied to derive the spatial structure of urban heat island (UHI) in the city of Wroc?aw, SW Poland. Seven UHI cases, measured during various meteorological conditions and characteristic of different seasons, were selected for analysis. GWR results were compared with global regression models (MLR), using various statistical procedures including corrected Akaike Information Criterion, determination coefficient, analysis of variance, and Moran’s I index. It was found that GWR is better suited for spatial modeling of UHI than MLR models, as it takes into account non-stationarity of the spatial process. However, Monte Carlo and F3 tests for spatial stationarity of the independent variables suggest that for several spatial predictors a mixed GWR–MLR approach is recommended. Both local and global models were extended by the interpolation of regression residuals and used for spatial interpolation of the UHI structure. The interpolation results were evaluated with the cross-validation approach. It was found that the incorporation of the spatially interpolated residuals leads to significant improvement of the interpolation results for both GWR and MLR approaches. Because GWR is better justified in terms of statistical specification, the combined GWR?+?interpolated regression residuals (GWR residual kriging; GWRK) approach is recommended for spatial modeling of UHI, instead of widely applied MLR models.