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Ikaite formation and its transformation to calcite occurs via distinct amorphous calcium carbonates (referred to as I and II) that differ in their morphology, particle size, water content and stability.

Ikaite (CaCO3*6H2O) is a cryogenic calcium carbonate phase, which forms below about 5°C. If the temperature increases above 5-7 °C ikaite transforms to calcite. Understanding the transformation process is important to interpret paleoclimatological data from glendonites, i.e., calcite pseudomorphs after ikaite in sediments. Tollefsen et al. (2020) suggested that the transformation occurs via a coupled dissolution–reprecipitation mechanism at the ikaite–calcite interface (1). In contrast, Vickers et al. (2022) proposed a quasi-solid state ikaite to calcite transformation mechanismand suggested that stable isotope data of glendonite can be used for reconstructing paleotemperatures(2). However, in sediments the majority of the ikaite to calcite transformation occurs in diagenetic environments, where ambient solutions interact with the transforming mineral.We synthesized ikaite at 2 °C in alkaline environment in order to study its transformation using organic solvents, vacuum pumping and rapid (1 min) heating from 5 to 30 °C. These experiments indicated the formation of amorphous calcium carbonate (ACC) during the ikaite to calcite transition. We also monitored the ikaite transformation by letting the 2 °C parent solution to reach room temperature (25 °C) within ~5 hours. We observed ACC and calcite formations depending on the alkalinity of the parent solution. Our experiments suggest that the ikaite to calcite transition is a two-step process consisting of the solid-state ikaite → ACC transformation and the ACC → calcite dissolution–reprecipitation mechanisms. During these transitions ikaite lost all its water but preserved its original morphology. We hypothesize that the occurrence of a transient amorphous phase during the ikaite to calcite transition implies the alteration of the isotopic data, similar to what was reported for the ACC to calcite transition (3).We acknowledge the financial support of NKFIH ANN141894 grant. References:(1) E. Tollefsen, T. Balic-Zunic, C. M. Mörth, V. Brüchert, C. C. Lee and A. Skelton, Scientific Reports, 2020, 10, 8141.(2) M. L.Vickers, M. Vickers, R. E. M. Rickaby, H. Wu, S. M. Bernasconi, C. V. Ullmann, G. Bohrmann, R. F. Spielhagen, H. Kassens, B. P. Schultz, C. Alwmark, N. Thibault and C. Korte, Geochimica et Cosmochimica Acta, 2022, 334, 201-216.(3) A. Demény, Gy. Czuppon, Z. Kern, Sz. Leél-Őssy, A. Németh, M. Z. Szabó M. Tóth, C.-C. Wu, C.-C. Shen, M. Molnár, T. Németh, P. Németh and M. Óvári, Quaternary International, 2016, 415, 25-32.

In this study, already published and new monitoring data are compiled from the Baradla and Béke caves in the Aggtelek Karst, from the Vacska Cave in the Pilis Mountains as well as from the Szemlőhegy and Pálvölgy caves in the Buda Hills. Recent investigations (2019–2020) include monitoring of climatological parameters (e.g., temperature, CO2) measured inside and outside the caves, and the chemical, trace element and stable isotopic compositions of drip waters. In the Baradla Cave, the main focus of the investigation was on the stable isotope composition and the temperature measurements of drip water. In the Vacska Cave, which belongs to the Ajándék-Ariadne cave system, CO2measurements and drip water collection were conducted in order to perform chemical and stable isotope measurements. In the Szemlőhegy and Pálvölgy caves, the chemical and stable isotope compositions of drip waters at six sites were determined. These datasets were used to characterize the studied caves and the hydrological processes taking place in the karst, and to trace anthropogenic influences. Climatological investigation revealed seasonality in CO2concentration related to outside temperature variation, indicating a variable ventilation regime in the caves. In addition, the contributions of the winter and summer precipitation to the drip water were also estimated, in order to evaluate the main infiltration period. The knowledge of these parameters plays a crucial role in constraining the carbonate precipitation within the cave. Thus, the dataset compiled in this study can provide a basis for the interpretation of speleothem-based proxies.

Speleothem formations are one of the most important and informative objects in paleoclimatological research. However, in order to interpret the data that reflect environmental conditions, we have to know the operation of the given cave, and it should be determined how the composition of the carbonate formed at the given site is related to the changes in the environmental parameters. The study presents the results of stable isotope geochemical analysis of speleothem formations and carbonate precipitated on glass plates collected in the Vacska Cave (Pilis Hills). The youngest layer of carbonate formations, formed in the last 1-2 decades, shows an isotope fractionation sign indicating strong ventilation, with the exception of a single site farthest from the entrance to the cave. The isotope shift was also accompanied by a change in carbonate fabric. Preceding the fabric change, the carbonate of the speleothem formations did not show ventilation-related shifts in the isotope compositions, suggesting that the exploration and opening of the cave areas may have caused the change. Based on this, we recommend the installation of local closures in the Vacska Cave and in the entire Ariadne cave system. The study provides a good example of how the results of basic research can be utilized in practical environmental protection, in the preservation of a strictly protected cave environment.

Societal concerns about future hydroclimate changes urge a thorough understanding of the governing processes. Here, an analysis of Middle and Late Holocene speleothem-based hydroclimate reconstructions and paleoclimate model simulations reveals sub-millennial fluctuations in the spatiotemporal variability of precipitation in the European and Mediterranean regions, that complements previous dendrochronological and pollen-based reconstructions with an improved temporal resolution. Although insolation forcing is the primary driver of Holocene hydroclimate changes in Europe on a multimillennial scale, the evaluation of the principal component analysis of speleothem records and correlations with sea surface temperature data indicates that North Atlantic ocean circulation played a significant role in the sub-millennial variation of continental moisture transport, with an increasing importance during the Late Holocene. The combined evaluation of speleothem-based data, climate simulations and sea surface temperature records therefore advances our understanding of the governing processes of Holocene hydroclimate changes in the European and Mediterranean regions.

Fluids play a crucial role in element mobility and mass transfer at the slab-mantle interface in subduction zones. However, tracing the source and chemical composition of subduction zone fluids still remains challenging. High-pressure (HP) metamorphic leucophyllites, mainly composed of quartz, muscovite/phengite and Mg-chlorite, occur in several localities in the Eastern Alps and experienced significant Mg-metasomatism at forearc depths during the Eoalpine orogeny. They thus provide a good opportunity to explore the origin of Mg-rich fluids in the continental subduction zone. The leucophyllites are rich in Mg and poor in Fe, Na, and Ca and occur as lenses and layers in the country rocks of metagranites. Both leucophyllites and metagranites show similar whole-rock REE distribution patterns, and magmatic zircons from them exhibit similar U-Pb ages of ∼271 Ma, suggesting that both types of rock have the same protolith of early Permian granite. One metagranite that preserves magmatic composition shows a low δ26Mg value of −0.64‰, suggesting a contribution of carbonate-rich sediment when granitic melts were produced. A profile of samples from metagranite through transitional gneiss to leucophyllite in Hungary shows two trends in δ26Mg values. In the Vashegy sections, δ26Mg values firstly decrease from −0.64‰ to −1.30‰ during gneiss formation, and then increase to 0.29‰ during leucophyllite formation. In a second locality, the TV tower section, the δ26Mg values firstly decrease from −0.29‰ to −0.89‰ during gneiss formation, and then remain constant during leucophyllite formation. Two leucophyllites in Austria exhibit higher δ26Mg values of 0.05 to 0.09‰ compared to their country rocks of about −0.20‰. Based on the Mg isotope systematics and their relationships to whole-rock geochemical compositions, we propose two types of fluid in the subduction zone: (1) a low δ26Mg ( 0.3‰) fluid derived from dehydration of talc-rich serpentinite. This is for the first time to find subduction zone fluids with distinct δ26Mg values at forearc depths. Both fluids possibly originated from dehydration of the sediment-serpentinite melange at the slab-mantle interface. The fluids were heterogeneous in δ26Mg values and they metasomatized slices of continental crust along shear zones. The presence of fluids with δ26Mg values as low as −1.3‰ suggests that the dissolution of Mg-rich carbonates can be significant at forearc depths. Our results provide an excellent example of tracing different sources of subduction zone fluids by coupling Mg isotopes with other petrological and geochemical variables. They may also have great implications for the generation of magmas with variable Mg isotope compositions at convergent plate boundaries.

Stable isotope-based dietary information on the tenth century CE Hungarian population serves as a valuable comparative tool to other dietary stable isotope studies in the region. This study presents a multiproxy approach involving skeletal samples with the least diagenetic alteration and the best-preserved primary signals. Dental and bone samples collected from three cemeteries in northeastern Hungary were investigated using a combination of Fourier-transform infrared spectroscopy (FTIR), stable isotope geochemistry, and strontium isotope analysis. FTIR measurements were used to detect the addition of secondary carbonate to the skeletal apatite carbonate component and to differentiate diagenetically altered samples. Our results suggest that all but the bone apatite carbonate stable isotope values and 87Sr/86Sr ratios are trustworthy and may be used to interpret the diet and migration of the researched individuals. We also determined that the inhabitants of the three tenth century CE Hungarian settlements relied primarily on C3 plants, but that C4 plants, most likely broomcorn millet (P. miliaceum), comprised a moderate portion of their plant-based diet and that animal products were generally consumed in moderate-high amounts. Coupled analyses of carbonate oxygen and strontium isotope compositions revealed that most of the bone apatite carbonate was heavily altered, whereas enamel apatite carbonate samples largely preserved their primary compositions. The bones showing the least amount of diagenetic alteration may partially preserve their primary apatite carbonate compositions, as well as show a combination of primary and secondary signals, which should be taken into consideration when bone apatite carbonate data are interpreted.

A temporary solution to massive anthropogenic CO2 emissions can be the capture of industrial CO2 from flue gas and sequestering it in geological formations. For safe and effective storage of CO2, interaction processes in the rock-pore fluid–CO2 system should be known. Investigation of natural CO2 accumulations provides valuable examples to what physical and chemical effects could be expected during CO2 influx at future CO2 storage sites. One of the key controlling factors of the processes occurring in natural CO2 reservoirs is the lithology of the storage rocks, which is primarily determined by the formation conditions of these rocks. In this respect, the lithologies of individual CO2 accumulation areas influence the processes between the host rock, the pore fluid, and the CO2 in different ways. In the current study, we focus on a well-studied natural CO2 storage reservoir, namely the Mihályi-Répcelak area, NW Hungary. We provide insight into the so far unstudied conglomerate reservoirs that represent a stratigraphically deeper reservoir unit with significantly different lithology and pore water compositions compared to the sandstone reservoirs. Our results indicate that dawsonite /NaAlCO3(OH)2/ formation also affected the conglomerate reservoirs, which indicates that at least part of the CO2 could be trapped in mineral form. An important role of salinity in reducing the CO2 mineral trapping capacity of the storage system is also demonstrated. Furthermore, H isotope analysis of diagenetic kaolinite was applied to trace the origin of the pore water that was present during the rock formation. Based on the data, dawsonite formation was induced by the flux of meteoric water that infiltrated during a warm and humid period and mixed with ascending CO2.

A stalagmitic flowstone deposit from the Beke Cave (called Nagy-tufa deposit), East-Central Europe is characterized by complex, climate related textural and geochemical records as documented from a drill core (BNT-2 core) covering the period of 4 to 1 ka cal BP. The core location was monitored in an earlier study. Based on monitoring, textural and chemical relationships, it has been hypothesized that the stable carbon isotope signal of the flowstone deposit is a regional humidity record, indicating wet periods 3.8 to 3.4, 3.0 to 2.8 and 2.0 to 1.6 ka cal BP, and a prominent dry period between 2.1 and 2.7 ka cal BP. Furthermore, stable H isotope data of inclusion-hosted water were used to reconstruct the atmospheric temperatures that fit independent regional paleotemperature records, indicating warm conditions around 2.7 ka BP and a relatively cold period between 2.5 and 1.5 ka BP. Comparisons with regional speleothem records and reconstructed North Atlantic Oscillation data indicate that the Late Holocene paleohumidity changes recorded by the BNT-2 stable carbon isotope record can be detected in the entire Western-Central European region with further links to the North Atlantic realm.

In the winter of 2017 three undisturbed sediment cores were retrieved from the Szemes Basin of Lake Balaton. The sediments were sampled for AMS 14C dating and we used 8 of the radiocarbon dates for age-depth modelling. Based on this, the investigated sediment sequence covers the entire Holocene and Late Glacial period and the bottom of the sediment is ca. ~16,000 cal yr BP old. X-ray fluorescence spectrometry (XRF) was used to reconstruct rapid changes in the element content of the lake sediment. The evaluation of the measured results makes it possible to reconstruct the changes in the discharge environment and lake water level that can be related to the climate and human impact. Based on the data, two major evaporation events can be observed at 5500 BP and 8100 BP. These results were also verified by oxygen isotope studies. To reconstruct the energy of the deposition environment, particle size analysis was performed. The obtained results confirmed that river sediments are common at the bottom of Lake Balaton sediments, while biogenic carbonate dominates in the upper, Holocene part of the sediment core. To identify each mineral phase in the sediment, X-ray diffraction (XRD) studies were used to determine the ratio of calcite to Mg-calcite. Based on our XRF measurements, focusing primarily on quantitative changes in magnesium and calcium, transmission electron microscopy (TEM) studies were performed, mainly in the Mg enrichment layer around 8100 BP. The precipitation of biogenic carbonate in Lake Balaton is still taking place, mainly in the form of calcite and Mg-calcite. Their relative proportions strongly depend on the Mg saturation of the water and the substrates on which they are separated. From our results we can draw conclusions about the possible previous deeper phases of the lake and the evaporation conditions of the water. The data obtained from transmission electron microscopy shows a good agreement with the results of the XRF measurement, the proportion of Mg-calcite increases around 8100 BP that likely indicate drier climatic conditions connectable to the well know 8.2 ka cal BP climatic reversal.

The generally cold climate of the last glacial period was interrupted by numerous abrupt shifts to warmer interstadial conditions in the North Atlantic. The effects of this Dansgaard–Oeschger (D–O) type climatic variability have been found in a number of European and Asian terrestrial paleoclimate archives, including speleothems, lakes and loess deposits. However, only very few of the already sparse precisely dated records provide quantitative information on stadial-interstadial temperature variations over this time period. This is a major impediment to resolving the cause and geographical propagation of D-O events, as well as to understanding the impact they have on continental climates and environments.Here we present carbonate clumped isotope (Δ47)-based active season paleotemperature (AST) estimates from land snails recovered from Greenland Stadial/Interstadial (GS/GI) 5 and 3 age loess at the Dunaszekcső loess site (Hungary), based on a uniquely detailed AMS 14C age dataset, alongside a new flowstone (PK-6, Bükkösd, Hungary) stable isotope-based temperature change record 230Th-dated to 30-26 ka. Stadial ASTs of the investigated periods were found to be in the range of 7–13 °C, corresponding to Tannual of 0–6 °C and TJuly of 11–17 °C, agreeing well with the range of model simulation results for the region. Interstadial AST values reconstructed for GI-5.1 and 3 (16–18 °C) indicate warm summers (TJuly: 20–22 °C) and relatively high annual mean temperatures (Tannual: 9–11 °C), matching present-day values. The PK-6 flowstone δ18Ocalcite-based temperature change estimates (~0.2 ‰ °C–1 δ18O/T gradient) reveal a 7–10 °C Tannual rise for the warmest phases of GI-3 and 4 compared to stadial temperatures, in very good agreement with the land snail TΔ47 values.Our results show that stadial-interstadial climate variability in East Central Europe was of comparable magnitude to that in Greenland. We propose that large scale ocean-atmospheric variability (NAO-AMO) imparts a major control on transmitting abrupt North Atlantic climate event signals into continental Europe during the last glacial. This study was funded by the Hungarian National Research, Development and Innovation Office to GÚ (OTKA PD-108639) and SK (OTKA KH-125584). TS is grateful for the support of the Swedish Research Council (2017-03888).

Calcite crusts from the Elephant Hill Moraine (EHM) (76°17'35" S 157°20'05" E) collected during 1983-84 were interpreted as formed in subglacial environments influenced by hydrothermalism (Faure et al., 1988). More recently, 234U enrichment in these crusts was used to suggest that during the warm MIS 11 interglacial (ca. 400 ka), the ice sheet margin at the Wilkes Basin retreated about 700 km inland (Blackburn et al., 2020). Their 234U data from separate analyses of pure calcite and pure opal crusts suggested that “connate seawater would impart marine signatures to subglacial waters” (Blackburn et al., 2020), with the former associated with massive melting during MIS 11. However, robust U-series dating by Blackburn et al (2020) was only possible on pure end members of opal and calcite, whilst other EHM crusts did not yield reliable ages and were discarded. The inferred MIS11 ice-loss was then based on a model of 234U accumulation and on those carbonate ages that fit their hypothesis that connate seawater influenced the subglacial environment. Here, we investigated the nanostructure of EMH samples that yielded unreliable U-Th ages, which were too old to fit into the 234U-based model of MIS11 connate seawater influencing subglacial waters. High-resolution transmission electron microscope images showed a complex history of precipitation, dissolution, re-precipitation, including the co-precipitation of nanocrystalline calcite and opal. Co-precipitation was documented by the inclusion of micrometre-scale opal spherules within calcite crystals whose lattice orientation does not change across the spherules and can be explained by the fluid being extremely enriched in silica. The calcite immediately surrounding the opal spherules was characterized by twins and likely a response to sub-ice sheet stress during their precipitation. The calcite-opal mixture partially replaced pre-existing calcite crystals, which appear broken, corroded and pre-date a final, pure calcite void-filling cement. Clearly, these EHM samples document several stages of crystallization, which imply repeated mobilization of chemical species. Preliminary Fluid Inclusion analyses of the crusts yielded a temperature of about 85oC, which inferred that at one stage calcite precipitation may have been influenced by hydrothermalism associated with volcanism. Our identification of complex crystallization histories for the Elephant Moraine subglacial carbonates opens up alternative formation hypotheses to that proposed by Blackburn et al. (2020) such as the existence of multiple sources of aqueous solutions. Consequently, it is fraught to infer that all the EMH formed from connate marine waters generated 400 ka without dating of multiple phases of calcite precipitation from each sample. References: Blackburn, T. et al. 2020, Nature, 583 (7817), pp.554-559. Faure, G. et al, 1988, Nature, 332(6162), pp.352-354.

Speleothems (dominated by cave-hosted carbonate deposits) are valuable archives of paleoclimate conditions. As such, they are potential targets of clumped isotope analyses that may yield quantified data about past temperature variations. Clumped isotope analyses of stalagmites, however, seldom provide useful temperature values due to various isotope fractionation processes. This study focuses on the determination of the microbially induced vital effect, i.e., the isotope fractionation processes related to bacterial carbonate production. A cave site with biologically mediated amorphous calcium carbonate precitation was selected as a natural laboratory. Calcite deposits were farmed under a UV lamp to prevent bacterial activity, as well as under control conditions. Microbiological analyses and morphological investigations using scanning electron microscopy showed that the UV lamp treatment effectively reduced the number of bacterial cells, and that bacterial carbonate production strongly influenced the carbonate’s morphology. Stable oxygen isotope analyses of calcite and drip waters, as well as clumped isotope measurements revealed that, although most of the studied carbonates formed close to oxygen isotope equilibrium, clumped isotope Δ47 values varied widely from equilibrium to strongly fractionated data. Site-specific kinetic fractionations played a dominant role in the distribution of Δ47 values, whereas bacterial carbonate production did not result in a detectable clumped isotope effect.

One of the most significant cultural transformations in European prehistory occurred in the middle of the 6th millennium BC in the heart of the Carpathian Basin. The northward expansion of Mediterranean farming groups (Starčevo-Körös-Criş cultural complex) halted and underwent a complete transformation giving rise to a new cultural group carrying an altered form of Neolithic traditions onward to Europe. This transformation is restricted to sites along a boundary found in the heart of the basin, north of which unfavorable ecological conditions hampered a long-term engagement in a Mediterranean type of agriculture. The majority of Early Neolithic Körös sites in eastern Hungary are confined to the alluvial plain of the Tisza River prone to natural biannual flooding. These wetland conditions were marginal for early farmers as it contained several elements that were hostile for herded animals and these groups were not adopted to cope with. Körös Culture pastoralists responded to these challenges posed by the new environment by complementing their diet with opportunistically exploited wild resources. This type of resilience of the first farmers seen in the alteration of traditional subsistence strategies was simply attributed to the static hostile conditions of the environment alone. Influence of dynamic changes in the hydrology has not been studied and documented so far. This paper presents a multiproxy archeomalacological approach to establish a mid-Holocene flood record in Southern Central Europe and assess the potential impacts of flood frequencies, climate change-induced higher floods on economic, societal development of the first farming groups from the heart of the Carpathian Basin. Based on our findings, intensified use of second-line subsistence resources marking resilience is coeval with intensified flooding during the second phase of cultural evolution preceding transformation. This marked transformation could have been traced regionally as well along the referred northern distribution line and is coeval with the initial phase of a minor climatic perturbation refered to as the IRD 5.b event. The southward expansion of cold waters in the North Atlantic yielded intensive cyclonic activity bringing more rain and cold weather to W Europe. In Hungary, higher continentality provided by the basin setting preserved warmer conditions. Nevertheless, increased rainfall onto the watershed of major rivers triggered heightened floods.

Several caves have been monitored along a transect stretching from the Adriatic Sea to the Aggtelek Karst (NE-Hungary) including two caves in Croatia and three caves in Hungary: 1) Cerovacke cave (~25 km far from the sea, Velebit Mt.), 2) Baraceve cave (~70 km far from the sea), 3) Csodabogyós Cave (~320 km far from the sea, Keszthely Mt.), 4) Béke and Baradla Caves (~700 km far from the sea, Aggtelek Karst). The monitoring activities in each caves included microclimate measurements, analyses of the elemental and stable isotope compositions of drip water and precipitation, as well as stable isotope measurements of modern calcite precipitates formed on light bulbs or glass plates.The stable isotope compositions of the drip waters in all cases (except one) show systematically lower values than those found in amount-weighted annual precipitation suggesting that the source of the infiltrating water dominantly derives from winter precipitation. Moreover, the relative contribution of winter precipitation can vary even within same cave system reflecting also the local morphology of the karst above the cave. The d-excess values of the drip waters show an increasing trend from the Aggtelek Karst towards to Adriatic Sea, showing higher values than 10‰ (Béke-C.: 10.3‰; Csodabogyós-C.: 11‰, Baraceve-C.: 12‰, Cerovacke: 15‰). These observations indicate significant contribution from moisture originated from the Mediterranean Basin to the infiltrating water. The monitoring of the precipitation support these findings as among the marine moisture source the Mediterranean is the most dominant even relative far from the sea.The trace element systematics in drip waters indicate that PCP likely took place during relatively dry periods. In some caves the change of the hydrological condition affected both the trace element composition of the drip water and the stable isotope composition of the modern calcite precipitates. Although the calcite-water isotope fractionations show significant scatter even within individual caves, the majority of the data fall close to the Coplen (2007) and the Tremaine et al. (2011) fractionation values in both Croatian and Hungarian caves.The research was supported by the Ministry for Innovation and Technology, the National Research, Development and Innovation Office (project No. PD 121387).

In order to use speleothems in the reconstruction of past climate and environmental changes it is necessary to understand the environmental and hydrological processes that determine the physico-chemical conditions of carbonate precipitation and hence speleothem formation. Therefore, in this study an extended monitoring program was conducted in the Béke and Baradla caves located in the Aggtelek region (Northeastern Hungary). The studied caves are rich in speleothem and flowstone occurrences with great potential for paleoclimatology studies. The monitoring activity included measurements of atmospheric and cave temperatures, CO2 concentration in cave air, as well as chemical and isotopic compositions of water samples (drip water, precipitation) and in situ carbonate precipitates. The hydrogen and oxygen isotope compositions of drip waters showed no seasonal variation at any of the collection sites, indicating a well-mixed karstic aquifer. This implies that the isotopic compositions of local speleothems were able to record multiannual isotopic changes inherited from stable isotopes in the drip water. CO2 concentration showed seasonality (high values in summer and low values in winter) in both caves, likely affecting carbonate precipitation or corrosion and consequently stalagmite growth. Systematic variations among Mg/Ca and Sr/Ca, Na/Ca, and Si/Ca element ratios were detected in the drip water suggesting Prior Calcite Precipitation (PCP). As PCP is characteristic of periods of reduced infiltration during drier weather conditions, the variations in drip water chemistry and drip rates indicate that the hydrological conditions also varied significantly during the studied period. This hydrological variability appears to affect not only trace element composition but also the isotopic composition of modern carbonate precipitates. In summary, these findings imply that the speleothems from the studied caves were able to record the hydrological changes resulting from alternating wet and dry periods, and therefore the geochemical data can be used to reconstruct past climate and environmental changes.

Natural CO2 reservoirs provide an opportunity to study long-term fluid-rock interactions, which are essential to reassure the safety of mineral storage of carbon-dioxide. The Mihalyi-Repcelak field (Pannonian Basin, Central Europe) is one of the largest natural CO2-bearing reservoirs in Europe (25 Mt). The CO2 was trapped in Neogene sandstones, which contain various carbonate minerals (dolomite, ankerite, siderite, dawsonite). To reveal the origin of the parent fluid, from which these minerals precipitated, dawsonite and siderite were separated by a new physical method to minimise the uncertainties in the analysis of their stable isotope composition. The δ13CDaw values range from +1.3‰ to +1.6‰ and the calculated δ13CCO2 values in equilibrium with dawsonite (−4.8‰ - –2.0‰) overlap with the carbon isotope compositions of the local CO2 and the European Subcontinental Lithospheric Mantle (−3.9‰ - –2.1‰). This indicates that the dawsonite-forming CO2 had a magmatic origin. The siderite data indicates that some formed from the magmatic CO2, possibly simultaneously with dawsonite (−6.0‰ - –3.9‰), whereas the rest (−8.4‰ - –6.1‰) formed either from a fractionated CO2 with magmatic origin or before the CO2 invasion. The hydrogen isotope composition of structural OH− of dawsonite (−57‰ to −74‰) was determined and was used to estimate the origin of the interacting porewater. The calculated porewater data (δD: −69‰ - –103‰ and δ18O: −1.4‰ - +4.7‰) indicate that the parent fluid was meteoric water modified by water-rock interaction. Our data allows estimation of the total amount of CO2 stored in the dawsonite-bearing sandstone reservoir to be 25 kg/m3, well in line with previous modelling works, which gives a total of 2.01 × 106 t of CO2, higher than previous estimates. We suggest that individual mineral analysis complemented by hydrogen isotope analysis is to be employed to effectively trace in-reservoir fluid-rock interactions in CO2 reservoirs and provide valuable input data for geochemical modelling for better predicting conditions for mineral storage of CO2.

This study introduces a novel approach intertwining analytics of spatial microbial distribution with chemical, mineralogical and (micro)structural related aspects in corroded concrete sewer environments. Samples containing up to 4 cm thick corrosion layers were collected from concrete manholes and analysed using hydro-geochemical, microbiological, biochemical and mineralogical methods. Opposed to the current opinion DNA and RNA indicating microbial activity were found throughout the entire deterioration layer down to the corrosion front. Elemental distributions of corresponding areas revealed a dynamic pH- and diffusion-controlled system in which a distinct succession of elemental accumulations was unequivocally correlated with responding pH levels, associated dissolution and precipitation of solids, as well as with the spatially resolved presence of microbes. Microbial activity further coincided with massive iron deposition zones, within the inner anoxic to anaerobic corrosion layers. As a possible microbial catalyst for iron oxidation and in-situ acid production in this zone, we propose Acidithiobacillus ferrooxidans which were isolated from the deteriorated concrete. Based on the data we propose a new model in which biogenic induced in-situ acid production is a decisive factor, steering high concrete corrosion rates of > 1 cm yr − 1 .

Studies on the last interglacial (LIG) can provide information on how our environment behaved in a period of slightly higher global temperatures at about 125 ± 4 ka, even if it is not the best analogue for the Holocene. The available LIG climate proxy records are usually better preserved and can be studied at a higher resolution than those of the preceding interglacials, allowing detailed comparisons. This paper presents complex stable hydrogen, carbon and oxygen isotope records obtained for carbonate (δ 13 C and δ 18 O carb ) and fluid inclusion hosted water (δD and δ 18 O w ) of a stalagmite from the Baradla Cave system in Central Europe that covers most of the LIG, as proven by U-Th dates. Comparing its C and O isotope data with records reported for other speleothem (cave-hosted carbonate) deposits from Europe revealed the complex behavior of these climate proxies, with a concerted relative increase in 18 O of carbonates from 128 to 120 ka and synchronized shifts in the opposite direction after 119 ka. The hydrogen isotope analyses of inclusion-hosted water extracted from the BAR-II stalagmite also correspond to the regional climate proxy records, with meaningful deviations from global temperature trends. Beside following the general paleotemperature pattern from the climate optimum (high δD values up to −64‰ around 120 ka) to the subsequent cooling starting at about 119 ka (low δD values down to −90‰ at about 109 ka), a period between 126.5 and 123 ka with low δD values (down to −81‰) is detected in the BAR-II stalagmite. Although the isotope shifts are muted in the C-O isotope data of carbonate due to competitive fractionation processes, the δ 13 C data show a positive relationship with the δD pattern, indicating humidity – and possibly temperature – variations. The periods with low δD values fit well to temperature and humidity changes inferred from proxy records from western Europe to the eastern Mediterranean. Spatial distributions of these variables show, that at about 125 ± 2 ka the Mediterranean region was characterized by warm, humid conditions and enhanced seasonality with elevated winter precipitation. The combined interpretation of stable isotope data revealed that the Alpine and Mediterranean regions behaved differently during Greenland Stadial 26 (GS26, ∼119 to 116.2 ka). While the Alpine records fluctuated in close agreement with the Central Greenland ice core δ 18 O data, the BAR-II stalagmite show a positive δ 18 O carb anomaly. The Baradla data indicate enhanced aridity and seasonality for a part of GS26, with the relative dominance of summer precipitation and Mediterranean moisture contribution. Following the GS26 event, the effect of long-term global cooling becomes dominant in the Baradla isotope records and leads to glacial inception at about 109 ka.

Determination of the long-term behavior of cave systems and their response to changing environmental conditions is essential for further paleoclimate analyses of cave-hosted carbonate deposits. For this purpose, four actively forming stalagmites were collected in the Baradla Cave where a three-year monitoring campaign was also conducted. Based on textural characteristics and radiocarbon analyses, the stalagmites are composed of annual laminae, whose counting was used to establish age–depth relationships. Fast and slowly growing stalagmites have different stable carbon and oxygen isotope compositions as well as trace element contents that could be attributed to differences in drip water migration pathways. The stable isotope compositions were compared with meteorological data of the last ∼100 years indicating that carbon isotope compositions of the stalagmites may reflect changes in precipitation amount, while oxygen isotope compositions are more related to temperature variations. The combined textural–geo...

Amorphous calcium carbonate (ACC) is a precursor of crystalline calcium carbonates that plays a key role in biomineralization and polymorph evolution. Here, we show that several bacterial strains isolated from a Hungarian cave produce ACC and their extracellular polymeric substance (EPS) shields ACC from crystallization. The findings demonstrate that bacteria-produced ACC forms in water-rich environment at room temperature and is stable for at least half year, which is in contrast to laboratory-produced ACC that needs to be stored in a desiccator and kept below 10 °C for avoiding crystallization. The ACC-shielding EPS consists of lipids, proteins, carbohydrates and nucleic acids. In particular, we identified large amount of long-chain fatty acid components. We suggest that ACC could be enclosed in a micella-like formula within the EPS that inhibits water infiltration. As the bacterial cells lyse, the covering protective layer disintegrates, water penetrates and the unprotected ACC grains crystallize to calcite. Our study indicates that bacteria are capable of producing ACC, and we estimate its quantity in comparison to calcite presumably varies up to 20% depending on the age of the colony. Since diverse bacterial communities colonize the surface of cave sediments in temperate zone, we presume that ACC is common in these caves and its occurrence is directly linked to bacterial activity and influences the geochemical signals recorded in speleothems.

Archaeological evidence points to substantial changes in Bronze Age societies in the European-Mediterranean region. Isotope geochemical proxies have been compiled to provide independent ancillary data to improve the paleoenvironmental history for the period of interest and support the interpretation of the archaeological observations. In addition to published compositions, in this study we gathered new H isotope data from fluid inclusion hosted water from a stalagmite of the Trio Cave, Southern Hungary, and compared the H isotope data with existing stable isotope and trace element compositions reported for the stalagmite. Additionally, animal bones and freshwater bivalve shells (Unio sp.) were collected from Bronze Age archaeological excavations around Lake Balaton and their stable C and O isotope compositions were measured in order to investigate climate changes and lake evolution processes during this period. The data indicate warm and humid conditions with elevated summer precipitation around 3.7 cal ka BP (Before Present, where present is 1950 CE), followed by a short-term deterioration in environmental conditions at about 3.5 cal ka BP. The environment became humid and cold with winter precipitation dominance around 3.5 to 3.4 cal ka BP, then gradually changed to drier conditions at ∼3.2 cal ka BP. Significant cultural changes have been inferred for this period on the basis of observations during archaeological excavations. The most straightforward consequences of environmental variations have been found in changes of settlement structure. The paleoclimatological picture is well in line with other East-Central European climate records, indicating that the climate fluctuations took place on a regional scale.

The Dachstein platform was an extensive carbonate platform developed on the westernmost shelf of the Neotethys during the Late Triassic, now preserved in various tectonic units disrupted during the Alpine orogeny. Despite being the focus of a multitude of sedimentological, paleontological and other studies, the demise of this platform remains controversial, with contrasting views on the timing and causes of cessation of its growth, the duration of the gap above, which at many places includes the Triassic-Jurassic boundary (TJB), and the depositional environment of overlying strata. Here we present new carbonate sedimentological, stable isotope and cyclostratigraphic data from sections in the Transdanubian Range (Hungary) which capture the termination of uppermost Triassic Dachstein Limestone and the onset of Hettangian (Early Jurassic) sedimentation following a hiatus. Previously, the TJB in the Transdanubian Range was regarded as a textbook case of a tectonically-driven platform drowning event or, alternatively, cessation of carbonate production due to emergence caused by a significant sea level fall at the TJB. However, recognition of global biotic change and environmental perturbations at the TJB calls for an assessment of their possible role in the demise of the Dachstein platform. Oxygen and carbon isotopic composition of bulk carbonates were measured in sections at Kőris-hegy (Bakony Mts.), Tata (Tata Horst), and Voroshid (Gerecse Mts.) Paleogeographically, these three sections represent a proximal to distal platform transect. Other sections at Pisznice and Tolgyhat (Gerecse Mts.) yielded additional sedimentological data. The sharp surface separating the Dachstein Limestone from the overlying Jurassic formations carries no or only minimal relief at outcrop scale. Thin section studies reveal small-scale irregularities, stylolites, microborings with ferruginous filling, or a thin clay-rich layer at the TJB, indicative of a submarine, or perhaps polygenetic, hardground. In the first meters of the lowermost Jurassic beds abundant ooids occur, and crinoids become common. In each of the studied sections, an abrupt negative carbon isotope shift is recorded at the TJB, and a gradual rebound to more positive values characterizes the lowermost Jurassic strata. Chemostratigraphy allows correlation with sections elsewhere. In the Transdanubian Range, the initial carbon isotope excursion and at least the first part of the purported main carbon isotope excursion are not preserved due to the gap at the TJB. Combined bio- and cyclostratigraphy of lowermost Jurassic strata permits an astrochronologic duration estimate of the early Hettangian hiatus that was not longer than a few hundreds of thousand years. Our results highlight the role of submarine erosion, perhaps partly related to acidification, and point to an abrupt change in carbonate production related to the end-Triassic extinction of several groups in the platform system. “Unreefing”, the ecological collapse of reefs, led to a regime shift, the transformation of the rimmed platform to a carbonate ramp, with a significant gap in production and preservation of carbonate sediment. This model is not uniformly applicable to Late Triassic platforms as several of them, unlike the Dachstein platform, survived with unrimmed architecture in the Early Jurassic elsewhere on the Neotethyan shelf. However, the model may explain features of the carbonate platform sedimentary record across other events with reef collapse.

The combined use of the stable isotope compositions of speleothem carbonate and inclusion-hosted water presents great potential in paleotemperature reconstructions, due to the various temperature-dependent isotope fractionations detected in cave systems and their environment. This paper evaluates the applicational possibilities of hydrogen and oxygen isotope measurements of inclusion-hosted water and its host calcite, in three different approaches: i) direct determination of calcite-water oxygen isotope fractionation by measuring inclusion water and carbonate compositions, ii) calculation of water oxygen isotope composition from hydrogen isotope data and of temperature from the inferred calcite-water fractionation, and iii) calculation of formation temperature from measured hydrogen isotope data and its temperature dependence in the modern precipitation water. Fluid inclusion oxygen and hydrogen isotope compositions as well as calcite oxygen isotope compositions were determined for five speleothem occurrences in Hungary. Although the background processes are not resolved, calculations involving measured calcite and water oxygen isotope compositions yielded unrealistic paleotemperatures, likely because of syn-formation isotope fractionation processes and diagenetic alterations. The hydrogen isotope data may yield realistic temperatures, provided that long-term isotopic composition - temperature relationships are known and the stable hydrogen isotope composition of the precipitation waters in the study area is temperature-controlled. Winter half-year and annual isotope-temperature relationships (δ2H/T gradients) were calculated using multidecadal isotope composition records from the Global Network of Isotopes in Precipitation (GNIP), gridded surface temperatures, and precipitation amounts from the E-OBS 21.0e database. The calculations yielded a paleotemperature record for the last ~250 ka, with average precisions ranging from ±0.6 °C for interglacial to ±2.4 °C for glacial periods. Clumped isotope analyses of cave-hosted flowstones support the inferred formation temperatures based on gradients, while detection of kinetic fractionations by combined hydrogen and oxygen isotope analyses of calcite and inclusion water lead to filtering clumped isotope (Δ47) data and more coherent Δ47-temperature relationships.

In the Transdanubian Range (Hungary), dolostone and dolomitic limestone appear in a number of sedimentary successions formed from the Late Permian to the Late Triassic in various depositional settings and under various diagenetic conditions, whereas only a negligible amount of dolomite was detected in the post-Triassic formations. Seven dolomite-bearing units representing ramp, small and large carbonate platforms, and intraplatform basin settings are presented in this synopsis. In most cases, multi-stage and polygenetic dolomitization was inferred. The main mass of the dolostones was formed via near-surface diagenetic processes, which were commonly preceded by the formation of synsedimentary dolomite. Accordingly, surficial conditions that prevailed during sediment deposition controlled the dolomite-forming processes and thus the lateral extension and the time span of dolomitization. The area of episodic subaerial exposure was a critical controlling factor of the lateral extension of the near-surface dolomite genesis, whereas its temporal extension was mostly governed by climate. Burial diagenesis usually resulted in only moderate dolomitization, either in connection with compactional fluid flow or via thermal convection. The Triassic fault zones provided conduits for fluid flow that led to both replacive dolomitization and dolomite cement precipitation. In the Late Triassic extensional basins, synsedimentary fault-controlled dolomitization of basinal deposits was reconstructed.

This study is intended to clarify the depositional environment of a 180-m-thick, immature, limy Middle Miocene oil source rock interval, cored in the Zala Basin, western Hungary. For this purpose, a highly interdisciplinary approach was applied combining simple, standard micropaleontological, isotopic, and organic geochemical methods, rarely applied together. Foraminifera were studied for estimating bottom oxygenation and water depth, while nannoplankton biostratigraphy permitted for estimating the rate of sedimentation. The studied source rocks were deposited in a rather shallow sea, below well-oxygenated bottom water. The abundant epiphytic foraminiferal fauna proves that the bottom was densely inhabited by benthic algae, while the high δ13Corg (>–22‰) clearly indicates massive benthic algal contribution to the kerogen. Mass accumulation rate of the limy upper part of the NN5 nannoplankton biozone, the oil source interval included, was very high (551 t/m2/Ma). In spite of moderate productivity and good ...

The end-Triassic extinction is one of the major Phanerozoic mass extinctions and it appears to have been linked to coeval rapid and severe environmental change, thought to be triggered by volcanism in the Central Atlantic Magmatic Province (CAMP). However, direct stratigraphic evidence to substantiate this linkage and to help develop scenarios for the cascade of events is still scarce. Mercury is an increasingly widely used proxy to trace the volcanic activity associated with large igneous provinces (LIPs) in distal sedimentary sections, but so far Hg records are available from only a handful of Triassic–Jurassic boundary (TJB) sections. One of the few well-studied marine sedimentary sections with a continuous sedimentary record across the TJB is located at Csővar (Hungary) and it exposes an extended succession of carbonates deposited in an intraplatform basin on the western Tethyan shelf. Previously, this section yielded one of the first convincing records of carbon isotope excursions (CIEs) across the TJB, albeit from low-resolution sampling. Here we report a new, high-resolution δ13Ccarb curve, supplemented with Hg measurements. A series of successive negative carbon isotope excursions (termed NCIE-1 to 6) attests to carbon cycle perturbations in the TJB interval. Four excursions appear significant after statistical smoothing. Of these, NCIE-3 exhibits the highest amplitude and is biostratigraphically constrained to the topmost Triassic, hence reliably correlated with the initial CIE, a globally recognised excursion closely preceding the TJB, and coincident with the end-Triassic extinction (ETE) horizon. The Hg concentration data provide the longest record available to date from a single section across the TJB. It shows very low values below NCIE-3 that are interpreted as the pre-volcanic background, followed by a prominent Hg peak that is nearly coincident with the most significant carbon isotope spike (NCIE-3). The slight lag suggests that onset of a major extrusive phase of CAMP (marked by a significant rise in Hg) closely followed the very onset of carbon cycle perturbation at that time (expressed by an abrupt change in the δ13Ccarb signal), possibly from biogenic methane release. Subsequent and recurring smaller Hg psuggest a pulsatory nature of prolonged volcanic activity. Organic content in the section is consistently low and sedimentary Hg concentrations are therefore normalized against Fe content, a reliable proxy in the lack of significant lithological changes. The maximum sedimentary Hg concentration at Csővar is greater than that in any other TJB section, although not unprecedented if other events are considered. Three hypotheses are explored to explain the high values; i) the hit-or-miss model could suggest that deposition of the sampled beds was fortuitously coincident with major eruptions, ii) the presence and preservation of cryptotephra could account for the unusually high sedimentary Hg enrichment, and iii) changes in the proportion of Hg-carrier phases throughout the studied succession, e.g. from magnetite to pyrite dominance, could have enhanced the potential of Hg capture and deposition. Collectively, the new data provide direct stratigraphic and geochemical evidence for the link between CAMP volcanism and carbon cycle perturbations and strengthen the case of their causal relationship with the end-Triassic extinction.

The Lower Triassic succession of the Transdanubian Range in Hungary comprises limestones, dolomite, marl, sandstones and siltstones, deposited in tidal flat, lagoon and ooid shoal environments on the marginal ramp of the western Neotethys. Seven cores were chosen for petrographic and stable isotope investigations aiming to reconstruct the paragenetic sequence with special regard to the dolomitization and hydrothermal events. Five lithotypes were differentiated: (i) dolomite, (ii) sandy, silty, clayey dolomite, and dolomarl, (iii), dolomitic siltstone and sandstone, (iv) dolomitic limestone, and (v) limestone. In these lithotypes, three types of dolomites are present: non-ferroan replacive, ferroan replacive, and ferroan cement. Fabric retentive and fabric destructive non-ferroan replacive dolomitization are interpreted to have occurred by seepage reflux. Supporting evidence includes the presence gypsum and anhydrite in the Lower Triassic beds. Stable isotope values of the ferroan dolomite (δ18O of −10.7 to −4.2‰ and δ13C of −4.8 to 4.7‰) suggest dolomitization by fluids of relatively high temperature. The similar stable isotope values (δ18O of −9.3 to −5.8‰ and δ13C of −1.9 to 2.5‰) of the non-ferroan dolomite phase suggest that the reflux dolomite was overprinted by this second dolomitization event. Traces of exotic minerals, such as barite, chalcopyrite, galena and sulphosalts were found as fillings of vugs and fractures in the dolomite-cemented sandstone. The metals could have been sourced from the underlying Permian red sandstone beds. The heterogeneous sediment composition had profound impact on the diagenesis of these sedimentary successions.

The region of Eastern Europe & Turkey contributed to the SISAL (Speleothem Isotopes Synthesis and AnaLysis) global database with stable carbon- and oxygen isotope time-series from 18 entities from 14 cave systems. The currently available oldest record from this region is the ABA-2 flowstone record (Abaliget Cave; Hungary) reaching back to MIS 6. The temporal distribution of the compiled 18 entities points out a ~20-kyr-long period, centering around 100 ka, lacking speleothem stable isotope record in the region. The regional subset of SISAL_v1 records displays a continuous coverage for the past ~90 kyr for both δ18O and δ13C, with a mean temporal resolution of ~12 yr for the Holocene, and >50 yr for the pre-Holocene period. The highest temporal resolution both for the Holocene and the pre-Holocene was achieved in the So-1 record (Sofular Cave; Turkey). Assessing the data, an important split was found regarding the climatic interpretation of speleothem δ18O. While the oxygen isotope composition of more continental formations is thought to reflect mainly temperature variations and changes in moisture transport trajectories, it may strongly reflect fluctuations of precipitation amount in the southern part of the region. Variations of δ13C primarily interpreted as humidity changes reflecting dry/wet periods across the region. Elevation gradients from three non-overlapping time periods from the region - for the last 5kyr - indicated systematically prevailing elevational gradients around -0.26‰100m-1 in δ18O. The regional comparison of SISAL_v1 speleothem δ18O and the temporal distribution of coarsely crystalline cryogenic cave carbonate occurrences back to 45ka does not appear to confirm the finding that occurrence of the latter coincides with the warming from stadial to interstadial conditions.

Monoclinic aragonite (mAra) is a naturally occurring nanocrystalline precursor of metastable aragonite., Despite its thermodynamical metastability at near-surface conditions, aragonite is widespread in marine and terrestrial sediments. It abundantly forms in living organisms, and its abiotic formation is favored in waters of a Mg2+/Ca2+ ratio > 1.5. Here, we provide crystallographic evidence of a nanocrystalline CaCO3 polymorph, which precipitates before aragonite in a cave. The new phase, which we term monoclinic aragonite (mAra), is crystallographically related to ordinary, orthorhombic aragonite. Electron diffraction tomography combined with structure determination demonstrates that mAra has a layered aragonite structure, in which some carbonates can be replaced by hydroxyls and up to 10 atomic % of Mg can be incorporated. The diagnostic electron diffraction features of mAra are diffuse scattering and satellite reflections along aragonite {110}. Similar features have previously been reported—although unrecognized—from biogenic aragonite formed in stromatolites, mollusks, and cyanobacteria as well as from synthetic material. We propose that mAra is a widespread crystalline CaCO3 that plays a hitherto unrecognized key role in metastable aragonite formation.

Uneven spacing is a common feature of sedimentary paleoclimate records, in many cases causing difficulties in the application of classical statistical and time series methods. Although special statistical tools do exist to assess unevenly spaced data directly, the transformation of such data into a temporally equidistant time series which may then be examined using commonly employed statistical tools remains, however, an unachieved goal. The present paper, therefore, introduces an approach to obtain evenly spaced time series (using cubic spline fitting) from unevenly spaced speleothem records with the application of a spectral guidance to avoid the spectral bias caused by interpolation and retain the original spectral characteristics of the data. The methodology was applied to stable carbon and oxygen isotope records derived from two stalagmites from the Baradla Cave (NE Hungary) dating back to the late 18th century. To show the benefit of the equally spaced records to climate studies, their coherence with climate parameters is explored using wavelet transform coherence and discussed. The obtained equally spaced time series are available at https://doi.org/10.1594/PANGAEA.875917.