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Anomalous Upper Devonian mercury enrichments : comparison of Inductively Coupled Plasma – Mass Spectrometry (ICP-MS) and Atomic Absorption Spectrometry (AAS) analytical data

Racki G., Rakociński M., Marynowski L.

Geological Quarterly

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2018

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Vol. 62, No. 3

487--495

EN

Mercury geochemistry is emerging recently as a hot topic in chemostratigraphical and facies research, owing to the diagnostic character of Hg enrichments as a proxy of volcanic activity (crucial in the context of assumed causal links between volcanic cataclysms and mass extinctions). Thus, as a prerequisite to such far-reaching interpretations, reliable analytical determinations of Hg concentrations are necessary. In conventionally performed analyses in sedimentary geochemistry, Inductively Coupled Plasma – Mass Spectrometry (ICP-MS) is usually applied, as an analytical standard for trace elements, including Hg. However, with a detection limit (DL) of 10 ppb, such measured values have been questioned as a conclusive geochemical indicator of Hg anomalies, and, instead, far more accurate techniques, such as Atomic Absorption Spectrometry (AAS; DL = 0.2 ppb), are requested. As a preliminary test of this view, we present comparative analysis of 91 samples from three sections encompassing the key Frasnian-Famennian and Famennian-Tournaisian boundary intervals in Morocco (Lahmida), Germany (Kahlleite) and Uzbekistan (Novchomok), for which Hg concentrations were determined by both methods in the same samples. Despite some differences, especially at low Hg concentrations, both analytical methods reveal the same 12 extraordinarily enriched samples in excess of 1 ppm (with one exception, the determination error is <20%), as well as similar overall chemostratigraphic patterns characterized by a few prominent Hg spikes, with a top value of 5.8 ppm. The Hg concentrations determined by ICP-MS and AAS are significantly correlated, as high as r = 0.98 (Novchomok), even if the first method reveals a general tendency toward slightly heightened values (by ~15 to 30% for medians). Therefore, ICP-MS results can conclusively be used in mercury chemostratigraphy in order to recognize extraordinary volcanic (or other) signals, at least in the Devonian geological record. False Hg anomalies were not generated by these conventional ICP-MS determinations.

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Evidence of wildfires during deposition of the Upper Silesian Keuper succession, southern Poland

Kubik R., Uhl D., Marynowski L.

Annales Societatis Geologorum Poloniae

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2015

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Vol. 85, No. 4

685--696

EN

Charcoals from the Upper Triassic vertebrate-bearing clays of the Zawiercie area (Upper Silesia, S-Poland) were analyzed using petrographic methods, to reconstruct burning temperatures as well as taphonomic processes. SEM and reflected light microscopy show excellent preservation of charcoals most probable connected with early diagenetic permineralization by calcite. The charcoal was assigned to three morphotypes, probably corresponding to three different fossil taxa. Fusinite reflectance data suggest, that the highest temperature reached above 600 °C (fusinite reflectance of 3.59%), what counterparts to the lower limit crown fire temperature. The values for most of the samples are lower (ca. 1% to 2.5%) what is typical for surface fires. In many cases fusinite reflectance values depends on the measured zone within the sample. Such zonation formed due to charring tem- perature differences. In zones remote from the potential fire source, reflectance values gradually decreases. It implies that calculation of fire temperatures based on average fusinite reflectance values might be too far-reaching simplification. Occurrence of fungal hyphae within the charcoal supports the interpretation of a predomination of surface fire, consuming dead twigs and stems. The low content of micro-charcoals in charcoal-bearing rocks as well as rounded to sub-rounded shapes of large specimens indicates that they were transported after burning, deposited away from the burning area, and finally early diagenetic mineralization.

3

Vitrinite equivalent reflectance of Silurian black shales from the Holy Cross Mountains, Poland

Smolarek J., Marynowski L., Spunda K., Trela W.

Mineralogia

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2014

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Vol. 45, iss. 3/4

79--97

EN

A number of independent methods have been used to measure the thermal maturity of Silurian rocks from the Holy Cross Mountains in Poland. Black shales are characterized by diverse TOC values varying from 0.24-7.85%. Having calculated vitrinite equivalent reflectance using three different formulas, we propose that the most applicablevalues for the Silurian rocks are those based on Schmidt et al. (2015) equation. Based on this formula, the values range from % 0.71 VReqvVLR (the vitrinite equivalent reflectance of the vitrinite-like macerals) to % 1.96 VReqvVLR. Alternative, complementary methods including Rock Eval pyrolysis and parameters based on organic compounds (CPI, Pr/-C17, Ph/-C18, MPI1, and MDR) from extracts did not prove adequate as universal thermal maturity indicators. We have confirmed previous suggestions that Llandovery shales are the most likely Silurian source rocks for the generation of hydrocarbons in the HCM.

4

Perylene and other terrestrial biomarkers identified in the Middle Jurassic conifer wood and their palaeoenvironmental significance

Smolarek J., Marynowski L., Bechtel A., Philippe M., Simoneit B.R.T.

Geology, Geophysics and Environment

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2014

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Vol. 40, no. 1

129

EN

The occurrence of perylene in the Middle Jurassic fossil wood from Poland is described, along with its correlation with unsubstituted polycyclic aromatic hydrocarbons (PAHs) as well as cellulose content. Perylene is especially common in immature/low maturity organic matter (OM), largely of terrestrial origin (e.g. Louda & Baker 1984, Jiang et al. 2000, Grice et al. 2009). It has been found in diverse recent environments, such as marine and terrestrial sediments, including peats, as well as ancient deposits, including brown coal and hard coal, crude oil and sedimentary rocks (review in Marynowski et al. 2013). Here we link perylene, a product of wood-degrading fungi, to conifer biomarkers in fossil wood material of different ages. Middle Jurassic wood remnants were of relatively low maturity (ca. 0.2-0.4% vitrinite reflectance Rr), had excellent preservation of biomarkers and biomolecules and generally good preservation of anatomical structures due to early diagenetic mineralisation. The results from described (most taxonomically defined) fossil wood fragments demonstrated a negative correlation between the concentration of perylene and those of generally typical conifer biomarkers (e.g. cadalene, dehydroabietane, simonellite and retene). We defined a conifer wood degradation index as: CWDI = perylene / (perylene + cadalene + retene + simonellite + dehydroabietane); and observed a wide range of values (0.001 for less degraded wood to 0.95 for highly degraded samples). We determined similar δ13C values for perylene from the fossil wood samples (from -26.4% to -27.8%), whereas the values for the conifer biomarkers were slightly higher and varied from -25.6% to -26.6%. In contrast, pyrene was depleted in 13C (from -27.5% to -28.2%). The carbon isotope values of perylene are consistent with an origin from wood-degrading fungi.

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Organic matter sources in aerosol PM10 from Wrocław, Poland

Rybicki M., Górka M., Simoneit B.R.T., Marynowski L.

Geology, Geophysics and Environment

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2014

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Vol. 40, no. 1

122

EN

The natural and anthropogenic contributions of hydrocarbon groups (aliphatic and aromatic), as well as total organic carbon, in atmospheric PM10 dust (particulate matter < 10 (µm) collected from Wrocław (SW Poland) were assessed using combined molecular (gas chromatography-mass spectrometry GC-MS) and stable carbon isotopic (isotope-ratio mass spectrometry IR-MS) analyses. The PM10 samples were taken using the hi-flow sampler Stamplex Air Division with Whatmann quartz filter (0.06237 m2), and a constant air flow of 1.13 m3/ min in the seasonal sampling program in 2007, and represent air pollution in all months of the year. The δ13C values of the total carbon varied seasonally from -27.6 to -25.3‰. The isotopic mass balance calculations showed greater coal burning input, reaching 70.5%, in the heating season and dominant transported sources 47.0% in the vegetative season. The δ13C values of the aliphatic fractions (from -36.6‰ to -29.4‰), indicated a dominant anthropogenic origin (gasoline/diesel/ coal combustion). The n-alkane distribution with relatively low CPI (carbon preference index) values confirmed that coal combustion and petroleum product use in vehicles were important sources of the PM10 in Wroclaw. On the other hand, high values of % WNA (wax n-alkane content), especially in vegetative season, and Cmax (carbon number maximum) ≥27 in 81% of the samples suggested that the influence of biogenic sources was also significant. Petroleum and coal combustion emissions were confirmed by the presence of hopanes and moretanes. The molecular analysis of the concentrations and diagnostic ratios of the polycyclic aromatic hydrocarbons (PAHs) and the δ13C values of the aromatic fractions (from -35.4‰ to -26.8‰) indicated that the main PAH sources were also represented collectively by combustion of liquid fuels and coal. Based on PAH discrimination diagrams it is also clear that the main organic carbon source is derived from coal, biomass and petroleum combustion in both seasons. However, taking into account the PAH concentrations during the vegetative and heating seasons, coal and biomass burning seem to be their major source. The high concentration of polar organic compounds such as levoglucosan, mannosan and galactosan confirmed a significant contribution of biomass burning to the total anthropogenic input, especially in the heating season. The general conclusions derived from coupling of organic tracer analysis and carbon isotopic data of PM10 was that the total carbon (including insoluble soot) is likely derived from fossil fuel combustion, while the extractable organic matter is a mixture from different sources with significant inputs of biomass burning. We have also shown that dominant organic tracers do not always represent the major input source in aerosol PM and the unresolved part of the organic matter (soot) is important in the carbon budget.

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Ordovician Jeleniów Claystone Formation of the Holy Cross Mountains, Poland - Reconstruction of redox conditions using pyrite framboid study

Smolarek J., Marynowski L., Trela W.

Contemporary Trends in Geoscience

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2014

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Vol. 3, iss. 1

59--67

EN

The aim of this research is to reconstruct palaeoredox conditions during sedimentation of the Jeleniów Claystone Formation deposits, using framboid pyrite diameter measurements. Analysis of pyrite framboids diameter distribution is an effective method in the palaeoenvironmental interpretation which allow for a more detailed insight into the redox conditions, and thus the distinction between euxinic, dysoxic and anoxic conditions. Most of the samples is characterized by framboid indicators typical for anoxic/euxinic conditions in the water column, with average (mean) values ranging from 5.29 to 6.02 µm and quite low standard deviation (SD) values ranging from 1.49 to 3.0. The remaining samples have shown slightly higher values of framboid diameter typical for upper dysoxic conditions, with average values (6.37 to 7.20 µm) and low standard deviation (SD) values (1.88 to 2.88). From the depth of 75.5 m till the shallowest part of the Jeleniów Claystone Formation, two samples have been examined and no framboids has been detected. Because secondary weathering should be excluded, the lack of framboids possibly indicates oxic conditions in the water column. Oxic conditions continue within the Wólka Formation based on the lack of framboids in the ZB 51.6 sample.

7

Aromatic hydrocarbons from the Middle Jurassic fossil wood of the Polish Jura

Smolarek J., Marynowski L.

Contemporary Trends in Geoscience

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2013

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Vol. 2, iss. 1

82--90

EN

Aromatic hydrocarbons are present in the fossil wood samples in relatively small amounts. In almost all of the tested samples the dominating aromatic hydrocarbon is perylene and its methyl and dimethyl derivatives. The most important biomarkers present in the aromatic fraction are dehydroabietane, siomonellite and retene, compounds characteristic for conifers. The distribution of discussed compounds is highly variable due to such early diagenetic processes affecting the wood as oxidation and the activity of microorganisms. MPI1 parameter values (methylphenanthrene index) for the majority of the samples are in the range of 0.1 to 0.5, which results in the highly variable values of Rc (converted value of vitrinite reflectance) ranging from 0.45 to 0.70%. Such values suggest that MPI1 parameter is not useful as maturity parameter in case of Middle Jurassic ore-bearing clays, even if measured strictly on terrestrial organic matter (OM). As a result of weathering processes (oxidation) the distribution of aromatic hydrocarbons changes. In the oxidized samples the amount of aromatic hydrocarbons, both polycyclic as well as aromatic biomarkers decreases.

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Mezozoiczne pożary – ich rozprzestrzenienie i znaczenie w trakcie zdarzeń globalnych

Marynowski L.

Przegląd Geologiczny

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2012

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Vol. 60, nr 3

148-154

EN

The present paper summarizes the issues related with occurrence and distribution of wildfires in the Mesozoic. The main focus is put on occurrence of palaeowildfires during the Mesozoic global events, including Permian-Triassic (P/T), Triassic-Jurassic (T/J) and Cretaceous-Palaeogene (C/P) boundary. The other problems are connected with controversies over oxygene curve during Mesozoic, with special emphasis on Jurassic wildfires and theoretical predictions of low concentrations of atmospheric oxygene.

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Ocena stanu nauk mineralogicznych w Polsce

Janeczek J., Marynowski L.

Przegląd Geologiczny

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2011

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Vol. 59, nr 6

469-473

EN

Results of a survey conducted recently by the Mineralogical Sciences Committee of the Polish Academy of Sciences among Polish geochemists, mineralogists and petrologists revealed a significant increase in a number of research articles published in ISI listed journals since the political and economic transformations in 1989 owing to the unrestricted international collaboration, better funding, unlimited access to worldwide journals and data bases and easier access to modern research equipment. Introduction of the so-called parametric evaluation of the performance of research institutions in Poland further motivates scientists to publish their papers in the most prestigious journals (category I and II on the ISI list). Relatively low impact of those articles measured by their low citation, especially by the low Hirsh index with the exception of a few authors whose papers are widely red, may have resulted from focusing on solving regional problems rather than tackling issues relevant to the whole scientific community. However, recently this trend has been reversed. The major obstacles in a more dynamic progress of Polish mineralogical sciences include limited access to modern equipment (there are only two electron microprobes in Poland available to mineralogists and none of ion microprobe) and unsatisfactory funding of research projects.

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Framboidy pirytowe jako wskaźniki paleośrodowiska

Zatoń M., Rakociński M., Marynowski L.

Przegląd Geologiczny

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2008

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Vol. 56, nr 2

158-164

EN

The problemof application of pyrite framboids in reconstructions of the redox conditions is presented. The characteristics of pyrite framboids, their origin and principles of application in paleoenvironmental interpretations are given. The pyrite framboid diameter distribution as indicators of redox conditions was presented on the examples of the Middle Jurassic (Upper Bajocian-Lower Bathonian) ore-bearing clays of the Polish Jura, and Upper Devonian (Middle and Upper Famennian) dark grey and black shales from Kowala (Holy Cross Mountains). It has been shown, that during the sedimentation of the ore-bearing clays, the pyrite framboids formed in the sediment, below the oxic water column; however, some episodic oscillation around the dysoxic conditions cannot be entirely excluded. During the sedimentation of the Middle Famennian dark grey shales, the redox conditions at the sea-floor oscillated around dysoxia. In both examples, the framboids are characterized by wide range of their diameters and the presence of large, >10 "my"m, framboids. On the contrary, the Upper Famennian black shales, representing the Hangenberg event, were deposited below the euxinic conditions in the water column. It is indicated by a high frequency of small-size framboids, far below 6 "my"m in diameter, and the lack of the large ones. The overlying shales, on the other hand, show the transition to more oxic conditions. The redox conditions interpreted above are in agreement with the independent biomarker analyses and paleontological observations.

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Middle Jurassic black shales (Skrzypny Shale Formation) - palaeoenvironmental significance of one of the oldest deposits of the Pieniny Klippen Belt

Górniak K., Bahranowski K., Gaweł A., Marynowski L., Szydłak T.

Geoturystyka

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2008

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nr 2

19-24

EN

This paper deals with a fragment of geological history of Middle Jurassic black spherosideritic shales outcropping in upper part of the Homole Gorge (Skrzypny Shale Formation, Niedzica succession). These important deposits belong to the Flackenmergel facies, widespread in oceanic Tethyan deposits. This formation represents one of the oldest rocks of the Pieniny Klippen Belt. Dark colour of these rocks (total organic carbon content in them amounts to about 1 wt.%) and the occurrence of siderite concretions indicate reducing conditions of their origin but oxidizing environment of waters above them in sedimentary basin. Oxic conditions of organic matter sedimentation are confirmed by the elevated values of pristine to phytane ratio. Moreover the results based on n-alkanes indicate mixed terrestrial/marine origin of organic matter with prevalence of the last one. These information are slightly obliterated because of advanced thermal maturity of organic matter caused by post-sedimentation processes. Microstructural features of deposits of the Skrzypny Shale Formation and the composition of clay minerals occurring in them indicate late diagenetic conditions. In SEM images we observe one-directional orientation of clay minerals and rotation of mica flakes, often chloritized. Clay minerals are represented by high-illitic illite/smectite, micas, post-biotitic chlorite and subordinately kaolinite. As follows from authors studies, these macroscopically nearly "mute" clay rocks, little interesting in outcrops, particularly when they occur in such attractive geological objects as the Homole Gorge, can be the source of important information concerning the history of sedimentation basins.

PL

Praca przedstawia fragment historii geologicznej środkowojurajskich czarnych łupków sferosyderytowych ukazujących się w niewielkim odsłonięciu w górnej części wąwozu Homole (formacja lupków ze Skrzypnego, sukcesja niedzicka). Te ważne utwory należą do facji Fleckenmergiel szeroko rozpowszechnionej w oceanie Tetydy. Formacja łupków ze Skrzypnego reprezentuje jedne z najstarszych skał pienińskiego pasa skałkowego. Ciemna barwa badanych skał (zawartość całkowitego węgla organicznego około 1% wag.) oraz występowanie w nich konkrecji syderytowych, wskazują na warunki redukcyjne panujące w osadzie, natomiast na obecność natlenionych wód nad osadem w środowisku ich sedymentacji. Sedymentację substancji organicznej w warunkach raczej utleniających potwierdzają badania związków organicznych, tj. wysokie wartości stosunku pristan/fitan. Wyniki tych badań wskazują ponadto na mieszane, lądowo/morskie pochodzenie substancji organicznej z przewagą ostatniej z wymienionych. Informacje te są nieco zatarte z powodu dużej dojrzałości termicznej substancji organicznej spowodowanej procesami postsedymentacyjnymi. Cechy mikrostrukturalne utworów formacji łupków ze Skrzypnego oraz skład występujących w nich minerałów ilastych wskazują na warunki odpowiadające późnej diagenezie. W obrazach elektronomikroskopowych (SEM) widoczna jest bowiem jednokierunkowa orientacja minerałów ilastych i rotacja blaszek mik, często schlorytyzowanych. W składzie minerałów ilastych występuje zaś wysokoillitowy illit/smektyt, miki, pobiotytowy chloryt i podrzędnie kaolinit. Z przeprowadzonych badań wynika, że makroskopowo niemal "nieme" skały ilaste, niepozorne wyglądające w odsłonięciu, szczególnie jeśli występują obok atrakcyjnych obiektów geologicznych jak to ma miejsce w wąwozie Homole, są źródłem ważnych informacji dotyczących historii basenów sedymentacyjnych. Warto więc zwrócić na nie uwagę.

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Gniazdowe akumulacje szczątków fauny w środkowojurajskich iłach rudonośnych Wyżyny Krakowsko-Częstochowskiej-wnioski paleobiologiczne

Zatoń M., Salamon M. A., Marynowski L., Zatoń R.

Przegląd Geologiczny

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2007

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Vol. 55, nr 5

424-429

EN

Distinct faunal accumulations in the uppermost Bajocian/lowermost Bathonian, lowermost and Middle Bathonian of the Polish Jura (south-central Poland) have been detected. The fossils are densely packed in the centre of the accumulations and more or less dispersed in their margins. The accumulations vary in size, but all are rich in various groups of organisms, of which the molluscs (mainly bivalves) and echinoderms predominate. The echinoderms are all disarticulated, and shelly fauna occur as angular fragments with sharp edges, of random sizes and without any signs of abrasion. The different sizes of the fossil remains, from tiny echinoderm ossicles or juvenile shelly fauna to medium-sized shell fragments or belemnite rostra, exclude any transportation and thus sorting. Worth of noting is the occurrence of similar faunal groups in each accumulation. The general shape and composition of the accumulations, as well as their taphonomical features, especially the angularity of shell fragments, point to durophagous (shell-crushing) predation rather than physical processes. The various organisms may indicate that the potential predator (most probably fish) fed on various invertebrates. The indigestible particles were later regurgitated forming the accumulations discussed. The presence of various epibionts on the fossil fragments indicate,that they rested upon the sea-floor for some time-span after they had been regurgitated. Then the scavengers, as well as current action or water movements, have been responsible for dispersion of some of the fossils, as is well-visible at the margins of the investigated accumulations..

13

Rozmieszczenie strefy redukcyjnej, przejściowej i utlenionej w łupku miedzionośnym na monoklinie przedsudeckiej na podstawie wskaźników materii organicznej

Więcław D., Kotarba M. J., Pieczonka J., Piestrzyński A., Oszczepalski S., Marynowski L.

Biuletyn Państwowego Instytutu Geologicznego

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2007

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nr 423

125-138

PL

Na podstawie wyników analiz geochemicznych materii organicznej z 566 próbek łupku miedzionośnego, pobranych w obszarze kopalnianym KGHM Polska Miedź SA i w jego bezpośrednim sąsiedztwie, został wypracowany nowy sposób identyfikacji strefy redukcyjnej, przejściowej i utlenionej w tych utworach. Jako wskaźniki klasyfikacyjne przyjęto stosunek parametrów S2/S3 (HI/OI), zawartość węgla organicznego (TOC) oraz wskaźnik tlenowy (OI) z analizy Rock-Eval. Jako dodatkowe kryterium przyjęto wskaźniki dystrybucji węglowodorów aromatycznych Phen/MePhen oraz TrPI. W strefie redukcyjnej, najbogatszej w materię organiczną, udziały Cu, Ag, Pb, Zn oraz Co wykazują wyraźną zależność wprost proporcjonalną od ilości TOC i wszystkie osiągają maksymalne zawartości. Udział metali szlachetnych (Au+Pt+Pd) jest na poziomie tła geochemicznego. Utwory nowo wyznaczonej strefy przejściowej charakteryzują się zmiennymi wartościami wskaźników materii organicznej i wiążą się z porównywalnymi, jak w strefie redukcyjnej, zawartościami miedzi, srebra i kobaltu, zwiększonymi zawartościami metali szlachetnych oraz zmniejszonymi, poniżej 0,1% wag., koncentracjami niepożądanych pierwiastków, tj. ołowiu i cynku. W strefie utlenionej zawartość materii organicznej jest minimalna, podobnie jak większości metali (Cu, Ag, Pb, Zn, Mo). Koncentracje metali szlachetnych w tej strefie są o 2-3 rzędy wielkości wyższe, niż w strefie redukcyjnej.

EN

A new method of identifying reduced, transitional and oxidised zones in Kupferschiefer strata is based on the geochemical analyses of organic matter from 566 Kupferschiefer samples collected in the KGHM PM SA mining area and its immediate neighbourhood. The S2/S3 (HI/OI) ratio, total organic carbon (TOC) and oxygen index (OI) from Rock-Eval pyrolytic analysis were used as classification parameters. The aromatic hydrocarbon distribution indices Phen/MePhen and TrPI were used as additional criteria. In the reduced zone, most abundant in organic matter, the Cu, Ag, Pb, Zn and Co contents show a strong proportional dependence on TOC, obtaining their maximum concentrations. The contents of noble metals (Au+Pt+Pd) remain on the level of geochemical background. The beds of the newly determined transitional zone have varying organic matter parameters. They have the comparable Cu, Ag and Co contents, increased noble metal content and lowered concentrations of undesired elements (<0.1 wt. %), i.e. Pb and Zn. In the oxidised zone, the organic matter content is minimal, just as in the case of most of other metals (Cu, Ag, Pb, Zn and Mo). The noble metals content in this zone is 2 to 3 orders higher than in the reduced zone.

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Konkrecje hiatusowe z iłów rudonśnych Wyżyny Krakowsko-Częstochowskiej

Zatoń M., Marynowski L., Bzowska G.

Przegląd Geologiczny

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2006

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Vol. 54, nr 2

131-138

EN

Hiatus concretions are arly-diagenetic sedimentary bodies, which in their history of formation, underwent exhumation during sedimentation break and/or erosion of sea-floor. Then they were colonized by various encrusters and borers, before they were buried again. Within Middle Jurassic (Bajocian through Bathonian) clays, hiatus concretions occur in four localities in the Cracow-Częstochowa Upland (south and central Poland): Ogrodzieniec, Bugaj, Mokrsko and Krzyworzeka. Preliminary data about their mineralogy, organic geochemistry and palaeoecology is given. Mineralogical analyses showed, that except dominant high Mg-calcite (up to 87.10% of total carbonates), concretions possess minor amounts of such compounds as quartz, clay minerals (kaolinite and illite), pyrite, siderite or Mg-kutnahorite. However, high differences are observed between total organic carbon contents of concretions (TOC=0.46%) and surrounded clays (TOC = 2.16%), but their molecular composition is similar. Most of identified biomarkers are of terrestrial origin. In clay lithology, the hiatus concretions are the only sedimentary bodies that clearly mark the sedimentation pauses (hiatuses). In the investigated area, they form more or less continuous horizons. The concretions are calcitic, possessing various encrusting fauna such as bryozoans, oysters and oyster-like bivalves, serpulids, solitary corals and foraminifers. They often post-date the borings, belonging to such ichnogenera as Gastrochaenolites, Trypanites and Entobia. Some of the nodules show distinct transition from firmground (characterized by the presence of Glossifungites ichnocoenosis) to hardground (presence of Trypanites ichnocoenosis), pointing to the fact, that they formed at, or very close to, the sediment-water interface. Some concretions, like those from Bugaj and Mokrsko, are characterized by their high diversity of hard bottom communities. Those concretions are also irregular in shape; others, like those from Ogrodzieniec and Krzyworzeka, possess lower diversity. The concretions from Krzyworzeka are especially dominated by the borers, while the encrusters are sparse and not diverse. Those nodules that are wide and flat tend to be more bored on one surface only, while those that are more roundish, are bored on both sides more evenly. The degree of diversity is probably correlated with physical disturbance, causing the rolling and overturning of the exhumed concretions in the littoral zone. On the other hand, the overall diversity could be lowered due to destructive abrasion either of the shallowest borings, echinoid/gastropod scratch marks and shells of nestling bivalves, as well as more delicate epilithozoans.

15

Konzentrat-Lagerstätte-type carbonate concretions from the uppermost Bajocian (Middle Jurassic) of the Częstochowa area, South-Cental Poland

Zatoń M., Marynowski L.

Geological Quarterly

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2004

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Vol. 48, No 4

339--350

EN

Early-diagenetic calcitic concretions of latest Bajocian (parkinsoni Zone, bomfordi Subzone) age in the Polish Jura contain an extremely rich and well-preserved macrofauna. In addition to bivalves and brachiopods, there are numerous ammonites of the (sub)genera Parkinsonia, Nannolytoceras, Lissoceras (Lissoceras), L. (Microlissoceras), as well as rare representatives of Vermisphinctes, Strigoceras (Strigoceras) and Phylloceras. Carapaces of primitive prosopid crabs are found associated. Such a diverse and well-preserved fauna (previously unknown from Bajocian epicratonic deposits of the Polish Jura), is typical of Konzentrat-Lagerstätte-type deposits. The random distribution of the concretions in exposure and the small size of the fauna may suggest that all remains were concentrated by bottom-current action in small depressions on an uneven sea-floor. The presence of numerous small-sized ammonites may be regarded as reflecting post-spawning assemblages which sufferedmass-mortality. Although cause of their death remains unclear, storm events are a possibility. Such depressions acted as natural “traps” as well as constituted a size-limiting factor for the accumulating fauna. The fact that all elements are well preserved indicates brief post-mortem transport and rapid burial, followed by early diagenesis that protected them from compaction. The absence of such fossil-rich concretions higher in the Middle Jurassic sequence clearly shows that our current assessment of biotic diversity may be an underestimate. The carbonate concretions contain a predominantly terrestrial type of organic matter (OM). Samples analysed are extremely immature, but early diagenetic transformations of OM occurred prior to concretion formation.

16

Composition and source of polycyclic aromatic compounds in deposited dust from selected sites around the Upper Silesia, Poland

Marynowski L., Pięta M., Janeczek J.

Geological Quarterly

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2004

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Vol. 48, No 2

169--180

EN

About 300 polycyclic aromatic compounds were identified using the GC-MSmethod in deposited dust collected in sites located outside the industrial belt of the Upper Silesia agglomeration. Concentrations of selected polycyclic aromatic hydrocarbons (PAH) range from 6.8 mg/g dust for anthracene to 142 mg/g dust for fluoranthene. Concentrations of highly carcinogenic PAH e.g. benzo(a)pyrene, benzofluoranthenes and benzo(a)anthracene range from 49 to 145.5 mg/g of dust. Significant concentrations (up to 35 mg/g of dust) of carcinogenic C22H14 PAHs (m/z 278) and C24H14 PAHs (m/z 302) were determined in all samples. Aromatic ketones and quinones as well as aromatic nitrogen and sulphur compounds with concentrations ranging from 2 to 45 mg/g of dust, were found in the polar NSO fraction. Molecular composition of hydrocarbons in the deposited dust is characteristic of the terrestrial organicmatter, as suggested by the presence of long chain n-alkanes with odd carbon skeleton predominance. However, relatively high concentrations of steranes and distribution of homohopanes different from terrestrial organic matter suggest that part of extractable organic mattermay be from diesel engine exhausts and/or paved road dust. The origin of the organic compounds adsorbed on the deposited dust is related to not complete coal combustion and possibly to other sources, such as automobile exhaust. The occurrence of phenyl-polyaromatic hydrocarbons and polyphenyls such as terphenyls, phenylnaphthalenes and their methyl derivatives, phenylphenanthrenes, phenylfluoranthenes and/or phenylpyrenes results from the free radical phenylation of aromatics during organic matter combustion.

17

Thermal maturity and depositional environments of organic matter in the post-Variscan succession of the Holy Cross Mountains

Marynowski L., Salamon R., Narkiewicz M.

Geological Quarterly

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2002

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Vol. 46, No 1

25-36

EN

The results of GC-MS investigations of biomarkers in organic matter from the epicontinental Permian and Triassic strata of the Holy Cross Mts. indicate generally suboxic (Permian) and oxic (Triassic, except for the Middle Muschelkalk) depositional environments with accompanying intensive bacterial reworking of organic remains. The biomarker spectra found in the Middle Muschelkalk and in the Entolium discites Beds (Upper Muschelkalk) show the presence of gammacerane, an increased concentration of C34 homohopanes and a Pr/Ph ratio not exceeding 1. All these observations suggest a hypersaline sedimentary environment with water column stratification and poorly oxygenated conditions. Thermal maturity investigations were based on both vitrinite reflectance and biomarker indices. The organic matter in the Triassic succession is slightly more mature along the northern margin of the Holy Cross Mts. than along their southern part, due probably to a regional increase in the maximum burial depth during the Mesozoic. The maturity of the Permian strata at Gałęzice (southern Holy Cross Mts.) is similar to that of the Triassic rocks whereas Kajetanów (in the north) is characterised by values significantly higher and comparable to those found in wells further north. The difference cannot be accounted for solely by differential burial depths, and implies the existence of a positive thermal anomaly active before the Middle Triassic. Our investigations generally confirmed the low thermal maturity of the Triassic. However, contrary to earlier interpretations, we suggest that the maximum burial depths based on a reconstructed thickness of the post-Triassic deposits may account for the observed maturity levels, assuming that geothermal gradients in the Mesozoic were similar to today's.

18

Terfenyle - nowa grupa biomarkerów występująca w osadach paleozoiku Gór Świętokrzyskich

Marynowski L., Czechowski F.

Przegląd Geologiczny

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1999

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Vol. 47, nr 1

87-92

PL

Stwierdzono występowanie nowej grupy węglowodorów aromatycznych, mianowicie struktur terfenylowych, w ekstraktach wydzielonych z paleozoicznych skał macierzystych z obszaru Gór Świętokrzyskich. Wszystkie analizowane skały powyższego obszaru zawierały orto-, meta- i para-terfenyl. Ich analizy dokonano przy użyciu GC-MS (m/z 230), natomiast identyfikacji przez porównanie czasów retencji i spektrów masowych dla odpowiednich struktur syntetycznych. Ponadto w badanych skałach stwierdzono obecność innych nowych serii węglowodorów, tj. fenylonaftalenów i fenylofenantrenów oraz ich metylopochodnych. Postulowany jest wspólny geochemiczny proces tworzenia się powyższych struktur przez rodnikowe przyłączenie fenylu do odpowiednich WWA (bifenylu, naftalenu, fenantrenu). Wzrostowi dojrzałości kerogenu towarzyszy spadek względnej koncentracji orto--erfenylu w odniesieniu do koncentracji izomerów meta- i para-terfenylu. Zaproponowano dwa nowe parametry oceny dojrzałości kerogenu oparte o skład izomeryczny terfenyli: TrP1 = p-TrP/o-TrP, and TrP2 = (m-TrP + p-TrP)/o-TrP. Wartości tych parametrów korelują z wartościami parametrów dojrzałości opartych o skład innych biomarkerów jak np. Ts/Tm i MDR.

19

Stopień przeobrażenia termicznego materii organicznej w skałach dewonu Gór Świętokrzyskich

Marynowski L.

Przegląd Geologiczny

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1999

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Vol. 47, nr 12

1125-1129

PL

Pomiary refleksyjności witrynitu R0(%) i analiza biomarkerów pozwoliły na interpretację poziomu dojrzałości kerogenu dla rozpatrywanego obszaru. W nowym, odmiennym od dotychczasowego (Belka, 1990), obrazie stopnia przeobrażenia termicznego kerogenu, dojrzałość wzrasta w kierunku północno-zachodnim, osiągając maksimum (Rcs > 1,0) na wysokości miejscowości: Kostomłoty, Laskowa, Zachełmie i Bukowa Góra. Najniższym poziomem przeobrażenia temicznego kerogenu charakteryzują się utwory dewońskie południowo-zachodniej części Gór Świętokrzyskich (Rcs < 0,6) z minimum na wysokości odsłonięć: Kowala, Góra Łgawa, Radkowice. Obecny poziom dojrzałości ukształtowały dwa główne czynniki, tj. miąższość nadkładu skał podewońskich i waryscyjska anomalia termiczna związana prawdopodobnie z dyslokacją świętokrzyską.

20

Analiza fizykochemiczna wybranych produktów spalania węgla kamiennego i mazutu

Matuszewska A., Marynowski L., John A.

Karbo

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1999

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Nr 4

137-142

PL

Omówiono wyniki analizy organicznych pozostałości wyekstrahowanych z popiołów lotnych z elektrolitów oraz żużli pobranych z wanien odżużlaczy. Na podstawie analizy pobranych próbek podjęto próbę porównania składu tych zanieczyszczeń w zależności od stanu technicznego kotłów ( zmodemizowane i niezmodemizowane ).

EN

The article discuses the results of analyses of organic residues extracted from fly ashes from electrolytes and slag taken from slagging tanks. On the basis of analysis of selected samples an attempt was undertaking to compare the composition of these impurities de-pending on the technical condition of boilers (modernised and non modernised