The presented multiproxy study sheds light on the intricate interplay between the biological and environmental factors which shaped the middle Miocene landscapes of the Paratethys region. Moreover, they highlight the diverse and dynamic nature of these ancient ecosystems. Here, we study the reasons for the predominance of nine miliolids in the Badenian and Sarmatian sediments, validate systematic and morphogroup approaches using geochemical methods, and finally reveal the bio stratigraphic potential of miliolid horizons during the Serravallian (late Badenian-Sarmatian). Trace elements (Mg/Ca, Ba/Ca, Mn/Ca) from the MZ 102 borehole and isotopic (delta 18O, delta 13C) analyses from & Scaron;VM 1 and MZ 102 were measured. On the basis of the morphogroup division, an autecological comparison, and geochemical analyses, three main (MG 1, 2, 3) and two small (SG 1, 2) miliolid groups representing distinct microhabitats were characterised. Specific faunal communities (MG 1) document the environment of arborescent algae, such as Cutleria and Fucus in detritus-rich water substrates, which can lead to suboxia or anoxia in muddy-sandy sediment layers. Other associations (MG 2) correspond to shallow marine environments of hypo/hypersaline lagoons overgrown by shortstemmed arborescent algae, such as Padina, Halopteris, and Pseudolithophyllum, as well as notable salinity fluctuations. Host faunal communities (MG 3) inhabiting the inner shelf are characterized by motile epiphytic foraminifera on algae and Posidonia rhizomes. The observable changes to the paleoenvironment can be characterized by fluctuations in salinity and the occasional depletion of oxygen at the bottom.

Some studies have used physical techniques for the assessment of bone structure and composition. However, very few studies applied multiple techniques, such as those described below, at the same time. The aim of our study was to determine the chemical and mineralogical/organic composition of bovine tibial bone samples using geophysical/geochemical reference techniques. X-ray diffraction (XRD), thermogravimetry (TG), Fourier-transform infrared spectrometry with attenuated total reflectance accessory (FTIR-ATR), inductively coupled mass spectrometry (ICP-MS) and inductively coupled optical emission spectrometry (ICP-OES) were applied to measure the organic and inorganic composition of 14 bovine bone samples. In addition, peripheral quantitative CT (QCT) was used to assess BMD in these bones. We were able to define the total composition of the studied bone samples. ICP-OES and ICP-MS techniques were used to determine the major and trace element composition. The X-ray analysis could detect inorganic crystalline compounds of bones, such as bioapatite, and its degree of ordering, indicating whether the bones belong to a younger or older individual. The total volatile content of the samples was calculated using TG and resulted in about 35 weight% (wt%). This, together with the 65 wt% total resulting from the chemical analysis (i.e., inorganic components), yielded a total approaching 100 wt%. As a large portion of the volatile content (H2O, CO2, etc.) was liberated from the organic components and, subordinately, from bioapatite, it could be concluded that the volatile-to-solid ratio of the examined bone samples was ~35:65. The FTIR-ATR analysis revealed that the organic portion consists of collagens containing amide groups, as their typical bands (OH, CH, CO, NC) were clearly identified in the infrared spectra. Numerous parameters of bone composition correlated with BMD as determined by QCT. In conclusion, we performed a complex evaluation of bovine bones to test multiple geophysical/geochemical techniques in bone research in association with QCT bone densitometry. From a medical point of view, the composition of the studied bones could be reliably examined by these methods.

The sand pit of Pécs-Danitzpuszta is one of the most important mixed Neogene vertebrate localities in Hungary, with older Miocene (Langhian – Serravallian) terrestrial and marine animal remains re-deposited into the upper Miocene (Tortonian) Lake Pannon sediments. Due to the mixed status of the Pécs-Danitzpuszta vertebrate assemblages, limited information is available about the former depositional environment and age of these fossils. However, the rare earth element (REE) composition of the fossil apatite can help to determine the stratigraphic origin and the early depositional environments of unprovenanced vertebrate remains. In this study, the REE composition of more than 60 vertebrate fossils, among them reworked and in situ remains from the Mecsek Mountain, were analysed. The results allowed separation between the Badenian, Sarmatian, and Pannonian aged fossils. The REE content and their distribution also helped us characterise the ancient depositional conditions of the investigated reworked fossils. Furthermore, several different types of vertebrate fossils were analysed, resulting in a large database that helped clarify the likely timings and mechanisms of REE uptake at this locality. Apparent variation in REE chemistry within bones (cortical vs cancellous) and teeth (enamel vs dentine) are best linked to fractionation along the REE series during their incorporation.

The N Hungarian Borzsony Mts. is part of the Neogene Inner Carpathian Volcanic Belt, composed mostly of intermediate-acidic magmatic and related volcanogenic sedimentary rocks. To our present knowledge, the central part of the Borzsony Mountains hosts precious- and basemetal bearing low sulphidation (LS) type epithermal and a weak Cu-porphyry mineralisation beneath, though their detailed deposit model is not available, yet. Siliceous and calcareous hot spring deposits, as well as clayey alterations and iron ores with unsure genesis are known on the southeastern flanks of the Borzsony Mountains. With the help of hot spring lithofacies analyses, mineralogical, petrographical, mineral chemical, whole rock geochemical and indicator mineral investigations, this work has clarified the origin of these mineralisations. We also show how reconstruction of epithermal paleosurface phenomena can help in providing a detailed deposit model and discover concealed parts of the system. The hot spring deposits are interpreted as surficial manifestations of the LS epithermal system; the native gold bearing siliceous deposit represents fluid upflow, while the unusually mixed carbonate-silica deposit represents lateral fluid outflow zones. The clay-rich limonitic iron ore is a supergene mineralisation; the presence of a concealed mineralisation beneath is proven by geochemical and indicator mineral studies.

A török kiűzését követően, a 17–18. század fordulóján a Mecsek környéki településeken is megjelentek az ipari tevékenységekben jártas németajkú telepesek, akik a Mecsek erdeiben az első üveghuták létesítési munkálatai közben felfigyeltek a környék ércindikációira is. Levéltári dokumentumok igazolják ezeket a nemesfémkutatásokat, azonban mindezidáig tényfeltáró és a történeti kutatásokat összefoglaló munka nem született annak a kérdésnek az eldöntésében, hogy valóban található-e a Mecsekben nemesfém-indikáció, illetve nemesfémérc. Amennyiben igen, a további modern szemléletű kutatások az érctípus meghatározására és genetikai modelljének pontosítására fókuszálhatók, illetve együtt a minőségi-mennyiségi paraméterek megadásával az ércesedés gazdasági jelentősége is körvonalazható. A fellelhető írott források kutatásával párhuzamosan tehát megindult a lehetséges ércindikációk felderítése a területen, mely eddig ismeretlen, a forrásokban sem említett nemesfém-ércesedés felfedezéséhez vezetett. Az elvégzett terepi és laboratóriumi vizsgálatok megerősítették, hogy az Ófalu térségében, a Mecsekalja-zónában feltáródó ópaleozoós, milonitosodott metamorf kőzetek (Studervölgyi Gneisz Formáció) olyan Au-Ag- Bi-Te szulfidos-telluridos ércesedést tartalmaznak, mely e kőzetek lepusztulásából származó miocén kavicsanyagban (Szászvári Formáció) is megtalálható. Az érces kavicsokon kívül a durvatörmelékes, folyóvízi eredetű Szászvári Formáció önálló aranyszemcséket is tartalmaz, mely szemcsék valószínű leg torlatos eredetűek. A torlatos arany zárványainak paragenezise szintén egyezést mutat az érces kavicsanyag és az Ófalu mellett kibukkanó metamorf kőzetek érces paragenezisével. A kutatási eredmények alapján tehát a Mecsekalja-zónában egy eddig teljesen ismeretlen, Au-Ag-Bi-Te elemegyüttessel jellemzett orogén aranyércesedés előfordulását azonosítottuk, melynek egy része lepusztult és áthalmozódott a Kelet-Mecsek kora miocén folyóvízi üledékgyűjtőibe.

Quartz from the stockwork zone of various Cyprus type volcanogenic massive sulfide deposits (Boccassuolo, Reppia, Campegli, Bargone and Vigonzano) from the unmetamorphosed, Jurassic Northern Apennine ophiolites was studied in order to provide details on the submarine hydrothermal conditions and the characteristics for ore formation. Our detailed SEM-CL investigation of quartz contributed to a robust characterization and interpretation of primary fluid inclusions and microthermometry data. SEM-CL imaging was also useful for reconstructing the consecutive steps of quartz precipitation. The determination of trace element contents according to growth zoning in quartz by LA-ICP-MS constrained the compositional variations of parent fluids during the hydrothermal activity. A continuously cooling fluid regime characterized each studied volcanogenic massive sulfide (VMS) occurrence although the minimum formation temperatures were different (Bargone: 110–270 °C; Boccassuolo: 60–360 °C; Campegli: 110–225 °C; Reppia: 50–205 °C; Vigonzano: 260–330 °C), the range of temperature most probably depends on the original position of sampling in relation to the centers of the hydrothermal systems. Compositional changes are reflected by variations in the methane content (0.13–0.33 mol/kg) and salinity (2.6–9.3 NaCl equiv. wt. %) in the fluid inclusions of quartz and calcite as well as a changeable Al content (11–1526 ppm) in quartz. This study demonstrates that the combined use of SEM-CL imaging and LA-ICP-MS analyses, coupled with fluid inclusion microthermometry, can constrain the different fluid conditions of ore forming and the barren stages of evolving submarine hydrothermal systems.

Az OSL (Optically Stimulated Luminescence) kormeghatározás alkalmazása a Magyar Állami Földtani Intézetben 2004-ben kezdődött, majd a jogutód Magyar Földtani és Geofizikai Intézetben folytatódott, és a Magyar Bányászati és Földtani Szolgálatban jelenleg is folyik. A felső-pleisztocén és holocén üledékek OSL kormeghatározása során tett megfigyeléseink szerint a kvarcok lumineszcens tulajdonságai és OSL kormeghatározásra való alkalmassága helyi eltéréseket mutat. Ezeknek az eltéréseknek az okait kerestük. Vizsgáltuk a kvarc eltérő forráskőzeteinek hatását olyan kvarcgazdag magmás, metamorf és idősebb üledékes képződményekből nyert kvarcszeparátumokon, amelyek hazánkban jelenleg a felszínen is előfordulnak, és anyaguk a negyedidőszaki üledékbe is bekerülhetett. Az OSL mérések mellett a kvarcszemcsék kristályrács hibáit okozó szennyeződések kimutatására LA-ICP-MS, mikro-FTIR és IR spektrometriai méréseket alkalmaztunk. A kvarcszeparátumok pontosabb jellemzéséhez fénymikroszkópos vizsgálatot, valamint termoanalitikai és röntgen-pordiffrakciós elemzéseket végeztünk. A kvarcokat befoglaló képződmények radioaktív elemtartalmát gamma-spektrometriai mérések segítségével határoztuk meg. OSL mérési eredményeink alapján az üledékes képződmények és egyes vulkáni tufák kvarcszeparátumai fényesebb, nagyobb intenzitású lumineszcenciát adtak, mint a vizsgált metamorf és mélységi magmás kőzetek. Közvetlenül, az első mállási és szállítási ciklus után az üledékekbe kerülve csupán néhány üledékes képződmény kvarcszemcséi lennének alkalmasak a kormeghatározásra. A kvarcok OSL tulajdonságait meghatározó kristályrács hibáit az LA-ICP-MS vizsgálat szerint Li, Na, Al, P, K, Ti és Ba beépülése okozhatja, és a mikro-FTIR mérésekkel kimutatott, a Si4+ iont helyettesítő Al3+ + H+, azaz AlOH szerkezeti hidroxil, valamint molekuláris víz. A nagyobb intenzitású OSL-t adó kvarcszeparátumok befoglaló képződményei kisebb K- és Th-tartalommal rendelkeznek, mint a gyengébb OSL-t kibocsátóké. A negyedidőszaki üledékek kvarcainak lumineszcens tulajdonságaiban és OSL kormeghatározásra való alkalmasságában mutatkozó helyi eltérések oka az eltérő forráskőzeteik, valamint különböző hő- és üledékes történetük lehet. A mélységi magmás és metamorf kőzetek elsődleges lepusztulásából származó kvarcok kedvezőtlen OSL tulajdonságát az eredményezheti, hogy bár magas hőmérsékleten képződve sok kristályrács hiba alakult ki bennük, de azok nagy részét lassú kihűlésük során elvesztették. Az üledékes képződmények kvarcszemcséinek kedvezőbb OSL tulajdonságai elsősorban a szállításuk és áthalmozódásuk során az ismétlődő radioaktív besugárzási, azaz OSL felépülési, és napfényen az OSL lenullázódási ciklusoknak köszönhető, melyek növelik a kvarc lumineszcens érzékenységét.

We report on sporadic fossil vertebrates from Brunei Darussalam (Borneo). Most of these isolated remains are reworked and derive from Penanjong Beach known for former coastal cliffs used to be rich in marine molluscs. Previously, the only vertebrate remains reported were shark teeth. With new material, the fish fauna is now represented by six shark and a single ray taxa, while remains of three turtle families were discovered (Trionychidae, Cheloniidae, Geoemydidae). This fauna is compared to nearby upper Miocene fossiliferous beds from where remains of cheloniid and trionychid turtles were unearthed. To assess the origin of the reworked remains, rare earth element (REE) concentrations of the fossil bioapatite were compared between the reworked and the geographically closest in-situ Ambug Hill fauna. The obtained trend in REE variations are identical, revealing similar REE uptake mechanism and early diagenetic conditions. With the additional fact that the succession outcropping at Ambug Hill cuts the coastline imply that the majority of the reworked fossils derive from the local Miocene beds. This is supported by Sr-isotope ages from reworked calcite bivalve shells ranging from 9.74 to 6.62 Ma. These turtle remains thus represent the hitherto known first Neogene fossil tetrapods from Borneo.

Effect of CO2 on the geochemical properties of carbonates DÓRA CSERESZNYÉS1, CSILLA KIRÁLY2, EDIT KIRÁLY 3, GYÖRGY CZUPPON 2, NORBERT MAGYAR4, CSABA SZABÓ1, GYÖRGY FALUS1 1Lithosphere Fluid Research Lab, Eötvös University, H-1117 Budapest, Pázmány Péter sétány 1/C. doracs@ceasar.elte.hu 2Research Centre for Astronomy and Earth Sciences, HAS, H-1112 Budapest, Budaörsi út 45. 3Mining and Geological Survey of Hungary, H-1145 Budapest, Colombus utca 17-23. 3Budapest Business School, University of Applied Sciences, H-1054 Budapest, Alkotmány utca 9-11.

The Mecsekalja Zone is a strike-slip fault zone that plays an essential role in the structural framework of South Transdanubia. The metamorphic and deformation history of the crystalline basement o...

Ignimbrite-hosted quartz phenocryst fragments contain much lower hydroxyl defect concentration than quartz in igneous rocks. Pre-eruptive and post-depositional loss of hydrogen were hypothesized as the main processes for lowering the initial magmatic concentrations of hydroxyl defects. The aim of this study was to examine the hydroxyl defect concentration of quartz phenocryst fragments from various vertical positions above the base of pyroclastic density current (PDC) deposits. It aims to record the vertical variations of hydroxyl defect concentrations to have an insight into potential post-depositional hydrogen loss of PDC deposits. Ignimbrite-hosted quartz phenocryst fragments were examined from two different ignimbrites in the Bukk Foreland Volcanic Area (North Hungary). Unpolarized micro-FTIR measurements on 23-35 unoriented crystal fragments from each sample were performed representing four different vertical positions of each site. Present results imply that hydroxyl defect concentrations show a pronounced decrease upward from the base of the deposits. The initial similar to 12 ppm hydroxyl defect concentration decreases to <3 ppm within <10 m from the base. Ignimbrites with contrasting degree of welding are characterized by different hydroxyl defect concentrations of quartz phenocryst fragments at the same height above the base. Thus, post-depositional dehydration is supposed to be the main factor causing the observed vertical decreasing trend. The modeling of post-depositional dehydration by considering typical ignimbrite emplacement temperatures (300-700 degrees C) and thicknesses (20-50 m) revealed that neither different cooling rates or different crystal diameters could cause the observed decrease in hydroxyl defect concentrations in ignimbrites. Other factors, such as contrasting pre-depositional thermal history, presence of melt- and fluid inclusion, and crack density of crystals could also play an important role in affecting the final hydroxyl defect concentrations.

Hydroxyl defect concentrations of quartz phenocryst fragments from various rhyolitic pyroclastic density current deposits from the Bukk Foreland Volcanic Area, Hungary, were determined by using micro-FTIR spectrometry. In addition trace-element analysis and SEM cathodoluminescence imaging were performed on the same crystals. Hydroxyl defect-content (expressed in water equivalent) of volcanic quartz ranges from 0.9 +/- 0.1 to 2.8 +/- 0.4 wt. ppm, which is lower than those in quartz of plutonic (granitic), metamorphic and hydrothermal origin. The incorporation of hydroxyl defect is mainly due to H+ +Al3+ substitutions into Si-tetrahedral vacancies of quartz. Furthermore, the presence of molecular water probably in (nano-)inclusions was proven. The post-eruptive diffusive loss of hydroxyl defects during cooling seems to be the main factor causing the very low concentration of hydroxyl defects. This may be also manifested in the almost homogeneous distribution of hydroxyl defects regardless of the considerable zonation in Al-content, although complete diffusive loss of hydroxyl defects was possibly hindered by the cooling effect of phreatomagmatism (interaction of excess water with magma during eruption) and deposition in a shallow submarine environment.Moreover, a reasonable linear correlation is observed between the integrated area of Si-O bands (between 2110 and 1440 cm(-1)) and sample thickness up to similar to 300 mu m by studying unoriented quartz phenocryst fragments. This may enable the quantitative analysis of hydroxyl defects in separated quartz crystals without the need for preparing oriented thin sections.

The aim of this study was to determine both ‘water’ contents (as OH− and H2O) and δD values of several clinopyroxene samples from alkaline basalts. These parameters were first obtained from five clinopyroxene samples using both the classical ‘off-line’ vacuum extraction technique and the ‘on-line’ high-temperature pyrolysis technique. Blanks measured with the ‘on-line’ gas extraction techniques were low enough to prevent any contamination by atmospheric water vapour. The comparison of data has revealed that our ‘on-line’ procedure is more effective for the extraction of ‘water’ from clinopyroxenes and, consequently, this ‘on-line’ technique was applied to ten additional clinopyroxene samples. Sample δD values cover a similar range from −95 to −45 ‰ (VSMOW) regardless of the studied locations, whereas the total ‘water’ content varies from ~115 to ~2570 ppm. The structural hydroxyl content of clinopyroxene samples measured by micro-FTIR spectrometry varies from ~0 to 476 ppm expressed in molecular water equivalent. The total ‘water’ concentrations determined by mass spectrometry differ considerably from structural hydroxyl contents constrained by micro-FTIR, thus indicating that considerable proportion of the ‘water’ may be present in (nano)-inclusions. The structural hydroxyl concentration—apart from clinopyroxenes separated from amphibole clinopyroxenite xenoliths—correlates positively with the δD values of clinopyroxene megacrysts for each locality, indicating that structurally bond hydrogen in clinopyroxenes may have δD values higher than molecular water in inclusions. This implies that there may be a significant hydrogen isotope fractionation for structural hydroxyl during crystallization of clinopyroxene, while for molecular water there may be no or only negligible isotope fractionation.

Ignimbrite-hosted quartz phenocryst fragments contain much lower hydroxyl defect than quartz in igneous rocks. Pre-eruptive and post-depositional loss of hydrogen were hypothesized as main processes for lowering the ‘original’ concentrations of hydroxyl defects. Our goal was to examine the hydroxyl defect concentration of quartz phenocryst fragments from various vertical positions above the base of pyroclastic density current – hereafter PDC – deposits. This is to monitor the vertical variations of hydroxyl defect concentrations to have an insight into potential post-depositional hydrogen loss and cooling history of PDC deposits. Ignimbrite-hosted quartz phenocryst fragments were examined from two different, thick ignimbrites in the Bukk Foreland Volcanic Area (North Hungary). Unpolarized micro-FTIR measurements on 23-35 unoriented crystal fragments from each sample were performed representing 4 different vertical positions of each site. Our results imply, that hydroxyl defect concentrations show a pronounced decrease upwards from the base of the deposits . The initial ~12 ppm hydroxyl defect concentration decreases to <3 ppm within few meters from the base. Thus, post-depositional loss of H is supposed to be the main factor causing the low hydroxyl defect concentration of quartz crystals in ignimbrites. Ignimbrites with different degree of welding are characterized by different hydroxyl defect concentrations of quartz phenocryst fragments at the same height above the base. A novel methodology which statistically evaluate the distribution of unpolarized absorbances for a given sample revealed that there may be either some accidental crystals incorporated during pyroclast transport at the base of these deposits or inhomogenities in hydroxyl defect concentrations due to non-equilibrium processes. Hydroxyl defect concentration in quartz from different vertical positions above the base is a relatively easily measurable proxy, which can provide further contribution to modeling the cooling speed, depositional temperature and original thickness of any quartz-bearing PDC deposits. We propose that ‘original’ hydroxyl defect concentration of quartz phenocrysts may only be preserved in a very thin layer (that cool very fast) at the base of PDC deposits where the cooling was instantaneous and no significant post-depositional H loss occurred. The original hydroxyl defect concentration may represent physical and chemical conditions in the magma chamber just prior to eruption.

Structural hydroxyl contents of quartz grains from various rhyolitic pyroclastic density current (PDC) deposits from the Bukk Foreland Volcanic Area, Hungary, were determined by using micro-FTIR spectrometry. Additional trace element analysis and SEM cathodoluminescence imaging were also performed. Structural hydroxyl content (expressed in water equivalent) of volcanic quartz ranges from ~2,0 to ~4,1 ppm, which is lower than those in quartz of igneous, metamorphic and hydrothermal origin. The incorporation of structural hydroxyl is mainly due to coupled H+ + Al3+ substitutions into Si-tetrahedral vacancies of quartz. In addition, the presence of molecular water is also obvious in (nano-)inclusions. The water fugacity (ƒH2O) just prior to the eruption seems to be the main factor controlling the concentration of structural hydroxyl as manifested in its almost homogeneous distribution regardless to the zonation of Al- or Ti-content. Quartz grains from the studied volcanic units are characterized by diagnostic absorption features between 3000 and 3550 cm-1, structural hydroxyl, molecular water, Al- and Ti-contents. This suggests the potential application of water content, the way of hydrogen incorporation and trace element chemistry of volcanic quartz as potential correlation tools. Moreover, a reasonable linear correlation is observed between the integrated area of Si-O bonds-related IR absorption features (between 2110 and 1440 cm-1) and sample thickness up to ~300 μm by studying unoriented quartz crystals. This may enable the analysis of separated quartz crystals without the need for preparing oriented thin sections.

Monsmedite, originally described as a unique, Tl(III)-rich mineral of Tl2O3 center dot K2O center dot 8SO(3)center dot 15H(2)O formula from Baia Sprie, Romania, was reinvestigated using authentic: specimens from the original finder of the mineral. "Monsmedite" is discredited as voltaite but the discreditation was based on specimens of unspecified origin, as the type material had been lost. Open questions related to the Tl-content and the limited scope of investigations done prior to the discreditation of "monsmedite" prompted this study. The presented results of the X-ray powder diffraction, thermoanalytical, IR-spectroscopic, Mossbauer spectroscopic, scanning electron microscopic and different kinds of chemical investigations confirmed that our "monsmedite" is Tl(I)-bearing voltaite but revealed a wide variability of Tl-content, reaching up to 7.49 wt% Tl2O. Empirical formula of "monsmedite" (from full chemical analysis of two samples) is: K-1.52-1.77Tl0.23-0.33+Fe1.79-1,912+Mn0.84-2.162+Zn0.51-0.642+Mg0.06-2.032+Fe2.63-2.823+Al1.01-1.503+(SO4)(11.92-12.16)15.52-17.72H(2)O.

(1) Eotvos Lorand University, Institute of Geography and Earth Sciences, Department of Geophysics and Space Science, Budapest, Hungary (kiralye@gmail.com), (2) Institute of Photogrammetry and Remote Sensing, Vienna University of Technology, Vienna, Austria, (3) Department of Physical Geography, Eotvos Lorand University, Budapest, Hungary, (4) Department of Numerical Analysis, Eotvos Lorand University Budapest, Hungary, (5) Geoscience Centre, Georg-August University of Gottingen, Germany