Facies and geochemistry of Lower Sarmatian reefs along the northern margins of the Paratethys in Roztocze (Poland) and Medobory (Ukraine) regions: paleoenvironmental implications

The Middle Miocene (Lower Sarmatian = Middle Serravallian) carbonate buildups called “serpulid-microbialite reefs” that occur in the Medobory and Roztocze regions (Paratethys Basin, western Ukraine and southeastern Poland) are composed mainly of calcite precipitates. Skeletal organisms represented by serpulid tubes and bryozoans (in places) are of minor importance and comprise merely a few percent of the rock volume. They are overgrown with micritic peloidal microbialites that are the major reef component. The microbialites and serpulids/bryozoans make together a porous reef framework that is usually filled up with abundant synsedimentary fibrous cements and micritic internal sediments. Other biota is taxonomically impoverished but often rich in individuals and comprises few species of bivalves, gastropods, benthic foraminifers. In places, the serpulid-microbialite limestone masses are incrusted with coralline algae, bryozoans and nubeculariid foraminifers. Bivalve coquinas, bioclastic limestones, breccias and conglomerates are associated with the reefs. The synsedimentary precipitates represented by microbialites and fibrous cements have quite unusual geochemical characteristics. They are composed of Mg-calcite with 5–6 mole % MgCO3 in average with a very high content of strontium (1000–1650 ppm Sr). The precipitates are enriched in heavy oxygen and carbon isotopes. Fibrous cements exhibit the highest values (18O ca. +1.5 [PDB] and 13C 2.8 [PDB]. It is generally believed that in the Early Sarmatian the Paratethys was a brackish basin due to restricted connections to theWorld Ocean. This is indicated by taxonomically poor biotic assemblages that inhabited the basin. On the other hand, however, the predominance of calcitic precipitates (such as microbialites and synsedimentary cements) is indicative of water highly supersaturated in respect to calcite due to high carbonate alkalinity content. Oxygen isotopic composition of the precipitates indicates that the brackish water, in which the reefs originated, had to be enriched in the heavy oxygen isotope due to strong evaporation. The low Mg content in calcite (if compared to modern tropical settings) could be the result of a relatively low precipitation temperature coupled with lower Mg/Ca ratio in Miocene than today, and the elevated Sr content may be indicative of a high precipitation rate resulting from high supersaturation. It seems therefore that the origin of the serpulid-microbialite buildups is related to a peculiar interplay of regional and local controls in the Sarmatian Paratethys. First, the relative isolation of the entire Paratethys basin resulted in the brackish water environment that could be inhabited by taxonomically poor opportunistic biota only and simultaneously enabled blooming of microbial communities. Second, a strong evaporation of the brackish water with high alkalinity content caused a supersaturation in respect to calcium carbonate and consequently a widespread precipitation of calcite (including calcification of microbial mats)

Zespoły otwornic sarmackich z wypełnień kawern w badeńskich rafach Miodoborów (Połupaniwka, zachodnia Ukraina)

The Middle Miocene (Upper Badenian) coralline algal reefs of Western Ukraine contain caverns (up to 1 m across) and fissures that are filled by Sarmatian deposits: marly clays, clayey carbonate sand and bioclastic, bryozoan-rich sand. These deposits often contain abundant and very well preserved calcareous benthic foraminifera; agglutinated forms have not been recorded. Foraminiferal tests quite commonly show morphological abnormalities, e.g. twin forms or tests with irregularities in size or shape in last chambers. Each of the three analysed samples is characterized by a different foraminiferal assemblage: Elphidium aculeatum assemblage, Hauerinidae assemblage and Lobatula lobatula assemblage. These assemblages are characteristic for a shallow marine environment. Low taxonomic diversity and high dominance or monospecific foraminiferal assemblages indicate generally a restricted marine environment. It seems that the increasing salinity and very high-energy environment were the most probable factors controlling the composition of the foraminiferal assemblages.Górnobadeńskie rafy koralowe zachodniej Ukrainy posiadają kawerny o przekroju do 1 m oraz szczeliny, które obecnie są wypełnione osadami sarmackimi – iłami marglistymi i zasilonym piaskiem węglanowym i bioklastycznym, często mszywiołowym. Osady te często zawierają liczne i bardzo dobrze zachowane węglanowe otwornice bentosowe; nie stwierdzono natomiast otwornic zlepieńcowatych. Dość częste są skorupki z morfologicznymi nieprawidłowościami, np. formy bliźniacze albo skorupki z nieregularnością rozmiaru lub kształtu ostatnich komór. Każda z trzech próbek zawiera inny zespół otwornicowy: w pierwszej występuje zespół z Elphidium aculeatum, druga zawiera zespół z Hauerinidae, a trzecia – zespół z Lobatula lobatula. Wszystkie te zespoły są charakterystyczne dla środowiska płytkomorskiego. Niskie zróżnicowanie taksonomiczne i wysoka dominacja lub jednogatunkowe zespoły otwornicowe wskazują na ogólnie ograniczone środowisko morskie; wydaje się, że w takich warunkach najbardziej prawdopodobnym czynnikiem warunkującym skład zespołów otwornicowych było podwyższone zasolenie i środowisko bardzo wysokoenergetyczne

Isotopic composition of dolomite associated with Middle Miocene Badenian anhydrites in the Carpathian Foredeep Basin of SE Poland

Dolomite is a quite common, although usually minor, constituent of the Badenian sulphate deposits of the Carpathian Foredeep Basin. In the autochthonous member of the Wola Różaniecka 7 borehole (SE Poland) which contains well preserved, large anhydritic pseudo-morphs after selenitic gypsum, dolomite constitutes up to 75% of the rock volume, the rest being anhydrite. Dolomites mostly show peloidal clotted microfabrics typical of microbialites and are interpreted as products of microbially induced precipitation and/or dolomitisation at temperatures around 40°C (as interpreted from the d1813181

The Early Sarmatian bryozoan Celleporina medoborensis sp. nov. from the Medobory reefs of western Ukraine (Central Paratethys)

Moundlike, globular to hemispherical bryozoan colonies of Celleporina medoborensis sp. nov. are documented from the calcareous organodetrital, slightly marly facies of the Lower Sarmatian (Volhynian) serpulid-microbialite reefs, in the Polupanivka and Ditkivtsi quarries (Medobory Hills), located at the northeastern margin of the Carpathian Foreland Basin (Central Paratethys) in western Ukraine. The colonies of C. medoborensis are multilamellar, often with a subcircular hole and occur together with numerous cyclostome bryozoans (crisiids, tubuliporinids, branching colonies of entalophoroids) as well as schizoporellid and cryptosulid cheilostomes, accompanied by a few macro- and micro-fossil taxa. The combination of morphological characters such as: thick radial ribs in the pseudoporous, variably-shaped area of the ovicell, and one or two small adventitious oral, as well as large vicarious avicularia are the main characteristic features of species. The rich occurrence of the celleporiform colonies of C. medoborensis sp. nov. within the fine-grained calcareous sands of Polupanivka and Ditkivtsi suggests a shallow-water setting and high availability of soft substrates, probably dominated by calcareous algae upon which the bryozoans may have settled in the Medobory reef biota during the Early Sarmatian

The Role of Microstructure on the Corrosion Behaviour of as cast AlCu4MgSi and MgAl2Si Alloys

In this work, the effect of the microstructure on corrosion behavior of selected Mg- and Al-based as cast alloys, was evaluated. The electrochemical examinations were carried out, and then a morphology of corrosion products formed due to local polarization on materials surface, was analyzed. It was documented that the presence of Mg2Si phase plays an important role in the corrosion course of Mg-based alloy. A selective etching was observed in sites of Mg2Si precipitates having “Chinese script”- like morphology. Analogous situation was found for Al-based alloy, where the key role was played by cathodic θ-CuAl2 phase

Effect of Cooling Rate at the Eutectoid Transformation Temperature on the Corrosion Resistance of Zn-4Al Alloy

The main purpose of this work was to experimentally determine the effect of the cooling rate during the eutectoid transformation on the corrosion resistance of a hypoeutectic Zn-4Al cast alloy in 5% NaCl solution. This was considered in relation to the alloy microstructure. For this purpose, metallographic and electrochemical studies were performed. It was found that the faster cooling promoted the formation of finer (α + η) eutectoid structures, which translated into a higher hardness and lower corrosion current density. In the initial stage of corrosion processes the eutectoid structure in the eutectic areas were attacked. At the further stages of corrosion development, the phase η was dissolved, and the α phase appears to be protected by the formation of corrosion products

Unusual early development in a cyclostome bryozoan from the Ukrainian Miocene

P.D, Hara, U., Jasionowski, M. (2006): Unusual early development in a cyclostome bryozoan from the Ukrainian Miocene. Linzer biologische Beiträge 38 (1): 55-64, DOI: 10.5281/zenodo.543379

Impact of sulphur exploitation on geochemical features of surficial environment of sulphur deposits from Polish-Ukrainian borderland

Eksploatacja złóż siarki rodzimej prowadzi do znacznej degradacji środowiska naturalnego. Złoża siarki Basznia i Niemirów znajdujące się na północnym obrzeżu zapadliska przedkarpackiego, na pograniczu Polski i Ukrainy, eksploatowane metodą otworową, w latach 90. ubiegłego wieku zostały zamknięte. Tereny poeksploatacyjne charakteryzują się znacznym przekształceniem mechanicznym i chemicznym gleb oraz degradacją przypowierzchniowych warstw gruntu. Badania geochemiczne próbek gleby z obszaru eksploatacji wskazują na silne zakwaszenie gleby (pH zwykle 2–6) oraz podwyższoną koncentrację Ba, Ca, S i Sr na obszarze poeksploatacyjnym względem obszaru otaczającego.Native sulphur exploitation leads to strong degradation of natural environment. Sulphur deposits like Basznia and Nemyriv occurring along the northern margin of the Carpathian Foredeep in the Polish-Ukrainian borderland were exploited using method of underground melting by hot water. The exploitation was stopped in the nineties. The sulphur mine areas are characterized by strong mechanical and chemical soil transformations. Geochemical analyses of soil and subsoil material reveal that the anthropogenic changed soils are distinctly acidic (mostly pH = 2–6) and enriched Ba, Ca, S and Sr compared to adjacent forest and agriculture grounds

Polyphase dolomitization of the Wuchiapingian Zechstein Limestone (Ca1) isolated reefs (Wolsztyn Palaeo-Ridge, Fore-Sudetic Monocline, SW Poland)

Dolomitisation was the main diagenetic process in the Upper Permian Zechstein Limestone of the Wolsztyn High-dolomite cementation (“over-dolomitisation”) also occurred. The rocks studied usually have a mixed mineralogy and represent a continuous spectrum from pure limestone to pure dolomite. This is due to varying degrees of dolomitisation, dolomite cementation and dedolomitisation. There are two main types of dolomite: replacement dolomite (mostly planar unimodal dolosparite mosaics that are mainly fabric-destructive) and cement dolomite (planar isopachous rims and pore-filling non-planar saddle-dolomite crystals). The timing of dolomitisation and dolomite cementation is difficult to ascertain, but comparing petrographical and geochemical data indicates that the reef carbonates were dolomitised shortly after deposition in a near-surface sabkha/seepage-reflux and then in burial systems. It seems that many of the dolomites gain their present isotopic composition when buried in relatively high-temperature conditions, as shown by low oxygen isotopic ratios ( δ18O as low as –9‰ PDB) and the presence of saddle dolomite. No isotopic support for a water-mixing mechanism is documented

Neptunian dykes in the Middle Miocene reefs of western Ukraine : preliminary results

Neptunian dykes were recently recorded within the Middle Miocene (Upper Badenian and Lower Sarmatian) Medobory reef complex of the Carpathian Foreland in western Ukraine. The Upper Badenian reefs are cut by a regular, semi-perpendicular network of intersecting fissures that penetrate the Badenian reef limestone down for more than 10 m. The dykes are filled by several generations of Sarmatian microbialites coating the fracture walls and by bedded bioclastic sediment (including foraminifers) which is more important volumetrically. The fissure fillings containing both the Sarmatian material as well as rare clasts of Badenian rocks indicate that the fissures were open during the onset of Sarmatian deposition. They originated following the emergence and fracturing of the Badenian limestones, either due to fault tectonics at basin margins induced by basin subsidence, around the Badenian-Sarmatian boundary, or to gravitational instability of large lithified Badenian reef bodies. Only one phase of fracture opening occurred. The filling of fractures was episodic, with pulses of cementation and microbial growth and sediment injection. Four different foraminiferal assemblages recorded in the neptunian dykes indicate that the process of fracture filling was long-lasting