Lovel Kukuljan

Speleothems have proven to be one of the most reliable terrestrial archives for palaeoclimate research. However, due to the complexity of karst systems, long-term monitoring and high-resolution analyses of the cave atmosphere and water geochemistry have become essential to better constrain the factors that control calcite growth and how geochemical palaeoclimate proxies are encoded into speleothems. While calcite precipitation incorporates the palaeoclimate signals into the speleothem fabric, certain conditions in caves can favour dissolution, which may form hiatuses or even destroy these signals. In extreme cases, in-cave dissolution by dripwater can form cup-shaped features (i.e., corrosion cups), which were the main focus of this study. The study site in Postojna Cave, Slovenia was investigated through cave climate monitoring and drip and cup water sampling, which took place during 2017–2021. We found that the cups are fed by low-calcium drips as the consequence of the thin rock overburden above the cave. Due to the specific configuration of the airflow pathways, the study site accumulates high levels of CO₂ (>10,000 ppm), which shifts low-calcium dripwater into undersaturation. This causes dissolution on the rock surfaces and speleothems on the cave floor. The results of this study have broader significance in addressing the suitability of cave environments and speleothems used in paleoclimate research.

Speleothems have proven to be one of the most reliable terrestrial archives for palaeoclimate research. However, due to the complexity of karst systems, long-term monitoring and high-resolution analyses of the cave atmosphere and water geochemistry have become essential to better constrain the factors that control calcite growth and how geochemical palaeoclimate proxies are encoded into speleothems. While calcite precipitation incorporates the palaeoclimate signals into the speleothem fabric, certain conditions in caves can favour dissolution, which may form hiatuses or even destroy these signals. In extreme cases, in-cave dissolution by dripwater can form cup-shaped features (i.e., corrosion cups), which were the main focus of this study. The study site in Postojna Cave, Slovenia, was investigated through cave climate monitoring and drip and cup water sampling, which took place during 2017–2021. We found that the cups are fed by low calcium drips as the consequence of the thin vadose zone above the cave. Due to the specific configuration of airflow pathways, the study site accumulates high levels of CO2 (>10,000 ppm), which shifts low calcium dripwater into undersaturation. This causes dissolution on rock surfaces and speleothems on the cave floor. The results of this study have broader significance in addressing the suitability of cave environments and speleothems used in paleoclimate research.

Understanding the dynamics and distribution of CO₂ in the subsurface atmosphere of carbonate karst massifs provides important insights into dissolution and precipitation processes, the role of karst systems in the global carbon cycle, and the use of speleothems for paleoclimate reconstructions. We discuss long-term microclimatic observations in a passage of Postojna Cave, Slovenia, focusing on high spatial and temporal variations of pCO₂. We show (1) that the airflow through the massif is determined by the combined action of the chimney effect and external winds and (2) that the relationship between the direction of the airflow, the geometry of the airflow pathways, and the position of the observation point explains the observed variations of pCO₂. Namely, in the terminal chamber of the passage, the pCO₂ is low and uniform during updraft, when outside air flows to the site through a system of large open galleries. When the airflow reverses direction to downdraft, the chamber is fed by inlets with diverse flow rates and pCO₂, which enter via small conduits and fractures embedded in a CO₂-rich vadose zone. If the spatial distribution of inlets and outlets produces minimal mixing between low and high pCO₂ inflows, high and persistent gradients in pCO₂ are formed. Such is the case in the chamber, where vertical gradients of up to 1000 ppm/m are observed during downdraft. The results presented in this work provide new insights into the dynamics and composition of the subsurface atmosphere and demonstrate the importance of long-term and spatially distributed observations.

Density-driven chimney effect airflow is the most common form of cave ventilation, allowing gas exchange between the outside and the karst subsurface. However, cave ventilation can also be driven by other mechanisms, namely winds. We discuss the mechanism and dynamics of wind-driven ventilation using observations in Postojna Cave, Slovenia. We show how seasonal airflow patterns driven by the chimney effect are substantially modified by outside winds. Wind flow over irregular topography forms near-surface air pressure variations and thus pressure differences between cave entrances at different locations. These pressure differences depend on wind speed and direction and their relationship to surface topography and the location of cave entrances. Winds can act in the same or opposite direction as the chimney effect and can either enhance, diminish or even reverse the direction of the density-driven airflows. To examine the possibility of wind-driven flow, we used a computational fluid dynamics model to calculate the wind pressure field over Postojna Cave and the pressure differences between selected points for different configurations of wind speed and direction. We compared these values with those obtained from airflow measurements in the cave and from simple theoretical considerations. Despite the simplicity of the approach and the complexity of the cave system, the comparisons showed satisfactory agreement. This allowed a more general assessment of the relative importance of wind pressure for the subsurface ventilation. We are certain that this example is not unique and that the wind-driven effect needs to be considered elsewhere to provide better insights into the dynamics of cave climate, air composition or dripwater geochemistry.

The synthesis and crystal structures of 1-(5-methyl-1H-indol-6-yl)ethan-1-one (7), C₁₁H₁₁NO, and 1-{3-[(dimethylamino)methyl]-5-methyl-1H-indol-6-yl}ethan-1-one (8), C₁₄H₁₈N₂O, are reported. The synthesis is based on the Diels–Alder cycloaddition of a substituted 2H-pyran-2-one derivative, followed by an acid-catalyzed cyclization and concomitant deprotection (the last two steps were carried out as a one-pot domino process) yielding substituted indole 7, which was further derivatized via Mannich reaction to the gramine derivative 8. Both structures 7 and 8 were determined on the basis of IR, ¹H NMR and mass spectroscopy, as well as by the elemental analysis and melting point determination. According to the single-crystal X-Ray diffraction analysis, the structure 7 has a single unique molecule in the asymmetric unit whereas the structure 8 contains four unique molecules in the asymmetric unit. Molecules 7 are linked via N­–H···O hydrogen bonds between the secondary amine group and carbonyl moiety of the acetyl group of adjacent molecules, whereas molecules 8 are linked via N–H···N hydrogen bonds between the secondary and tertiary amine groups of adjacent molecules. Both structures are further stabilized by weak C–H···O, C–H···π and π···π interactions.