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.     

Enigmatic sedimentary–volcanic successions in the central European Variscides: a Cambrian/Early Ordovician age for the Wojcieszów Limestone (Kaczawa Mountains,SW Poland) indicated by SHRIMP dating of volcanic zircons

Metamorphosed volcanic and sedimentary successions in the central European Variscides are, in many areas, poorly biostratigraphically constrained, making palaeotectonic interpretations uncertain. In such instances, geochronological data are crucial. Sensitive high resolution ion microprobe (SHRIMP) dating of volcanic zircons from a quartz–white mica schist (interpreted as deformed metavolcaniclastic/epiclastic rock) within the stratigraphically controversial Wojcieszów Limestone of the Kaczawa Mountains (Sudetes, SW Poland), near to the eastern termination of the European Variscides, has yielded an age of 498 ± 5 Ma (2σ error), corresponding to late Cambrian to early Ordovician magmatism in that area and constraining the depositional age of the limestones. The new SHRIMP data are not consistent with the recent revision of the age of the Wojcieszów Limestone based on Foraminifera findings that ascribed them to a Late Ordovician—Silurian or even younger interval. They are though, consistent with sparse macrofossil data and strongly support earlier interpretations of the lower part of the Kaczawa Mountains succession as a Cambrian–Early Ordovician extensional basin‐fill with associated initial rift volcanic rocks, likely emplaced during the breakup of Gondwana. Copyright © 2008 John Wiley & Sons, Ltd.     

Natural gradient experiment on transport of jet fuel derived hydrocarbons in an unconfined sandy aquifer

This paper deals with a field experiment, combining the push–pull and tracer tests, conducted under natural gradient conditions at the international Oslo airport. The studied aquifer, showing very complex hydrogeological settings, has been contaminated by a jet fuel spill. The tracer solutes—bromide, toluene, o-xylene, 1,2,4-trimethylbenzene, 1,3,5-trimethylbenzene and naphthalene, have been injected into the plume. Their migration and changes in concentration of the electron acceptors and metabolic by-products have been monitored. Fast removal of both the non-reactive tracer as well as the aromatic organics has been observed. The tracer pulse could only be detected 2 m downgradient from the injection points. At this point, toluene and o-xylene have been completely removed, however, trimethylbenzenes and naphthalene have been detected. Their depletion, based on calculations of available electron acceptors, can, to a large extent, be accounted for intrinsic biodegradation, with Fe(III) and sulphate reductions as the major controlling processes.     

Application of electrical resistivity imaging (ERI) for the assessment of peat properties: a case study of the Całowanie Fen,Central Poland

Complex studies were carried out to recognize the fen structure and peat properties in the Ca?owanie Fen area, belonging to the Natura 2000 network. The studies were conducted in two study areas that differ significantly in terms of peat thickness. Electrical resistivity imaging (ERI) was used to identify the properties of the peat and its substrate, such as thickness and electrical resistivity. Comparison of the field studies with the laboratory tests has shown that the ash content rises electrical resistivity in peat. In addition, the study has shown that the application of non-invasive geophysical methods in protected areas is justified. The fen, as a medium containing mostly water, was a proper test area for the ERI measurements.     

Low‐Ir IAB irons from Morasko and other locations in central Europe: One fall,possibly distinct from IAB‐MG

Differences in texture and discovery location prompted us to analyze 16 irons from Morasko; one from Seeläsgen, known to have a similar composition; and a new mass found at Jankowo Dolne. These were analyzed in duplicate by instrumental neutron‐activation analysis (INAA). The results show that all 18 samples have very similar compositions, distinct from all other IAB irons except Burgavli; we conclude that they are all from a single shower. Eight of the samples were from regions with large amounts of cohenite (but were largely free of inclusions) and six were from samples with very little cohenite; we could find no resolvable difference in composition between these sets, a fact that suggests that the C contents of the metal phases were similar in the two areas. Although Morasko has been classified into the IAB main group (IAB‐MG), its Ir plots well outside the main group field on an Ir‐Au diagram. We considered the possibility that the low Ir reflected contamination by a melt from a IAB region that ponded and experienced fractional crystallization; however, because Morasko has Pt, W, and Ga values that are the same as the highest values in IAB‐MG, we rejected this model. We therefore conclude that Morasko formed from a different melt than the IAB‐MG irons; the Morasko melt was produced by impact heating, but one or more of the main Ir carriers did not melt, leaving much of the Ir in the unmelted residue. Copper is the only element that shows resolvable differences among Morasko samples. Most (13 of 18) samples have 149 ± 4 μg g^?1 Cu, but three have 213 ± 10 μg g^?1; we interpret this to mean that the low‐Cu samples have equilibrated with a Cu‐rich phase, whereas there was none of the latter phase within a few diffusion lengths of the samples with high Cu contents.     

Seismic velocity estimation from post-critical wide-angle reflections in layered structures

The travel time inversion of wide-angle seismic data is a technique commonly used in the deep seismic sounding. We propose an application of this technique to a smaller scale of a sedimentary layer, where the characteristics of seismic observations changes significantly. Field observations confirmed by synthetic analysis recognize the dominant amplitudes of wide-angle post-critical reflections. A case study is presented in this paper, of a joint interpretation of conventional reflection seismic with reflection imaging, combined with the wide-angle travel time inversion of additional full-spread observations. A joint interpretation results in a precise recognition of the seismic velocity distribution, that is further used for the seismic depth conversion with the uncertainty analysis of the depth of the reflecting horizons. Despite the salt layer in the studied structure this method is able to precisely recognize the seismic velocities of the sub-salt structures.     

Summer Floods in Central Europe – Climate Change Track?

In Central Europe, river flooding has been recently recognized as a major hazard, in particular after the 1997 Odra /Oder flood, the 2001 Vistula flood, and the most destructive 2002 deluge on the Labe/Elbe. Major recent floods in central Europe are put in perspective and their common elements are identified. Having observed that flood risk and vulnerability are likely to have grown in many areas, one is curious to understand the reasons for growth. These can be sought in socio-economic domain (humans encroaching into floodplain areas), terrestrial systems (land-cover changes – urbanization, deforestation, reduction of wetlands, river regulation), and climate system. The atmospheric capacity to absorb moisture, its potential water content, and thus potential for intense precipitation, are likely to increase in a warmer climate. The changes in intense precipitation and high flows are examined, based on observations and projections. Study of projected changes in intense precipitation, using climate models, for several areas of central Europe, and in particular, for drainage basins of the upper Labe/Elbe, Odra/Oder, and Vistula is reported. Significant changes have been identified between future projections and the reference period, of relevance to flood hazard in areas, which have experienced severe recent floodings.     

The Late Vistulian and Holocene evolution of Jezioro Lake: a record of environmental change in southern Poland found in deposits and landforms

Jezioro Lake is the only natural lake in southern Poland outside mountainous areas to have existed continuously since the Pleistocene. The record of environmental change in the Late Vistulian (Weichselian) and Holocene is preserved in the deposits and landforms around the lake. This paper presents the results of paleogeographical and paleoecological research that emabled us to reconstruct the history of the Jezioro Lake. At the end of the Vistulian period, the outlet of the lake was blocked by a parabolic dune moving in from the west. Limnic sedimentation was evident in the sediment core at all levels from the Holocene, with remains of Cladocera, Chironomidae larvae, and aquatic plants. The lake did not disappear at that time, although its area decreased by a factor of 12 by the end of the period. Paleobotanical research permitted the reconstruction of sequences of plant communities and changes in nutrient status and water level. An initial oligotrophic lake, as indicated by the presence of Iso?tes lacustris L., changed to a eutrophic lake, as indicated by the presence of Potamogeton natans L. and Nuphar sp., then the lake progressed to the present-day dystrophic lake that is surrounded by a swamp. The profile of organic deposits contains a record of environmental change at least since the Younger Dryas in southern Poland.