Duvalo “Volcano” (North Macedonia): A Purely Tectonic‐related CO2 Degassing System

Duvalo “volcano” is a site of anomalous geogenic degassing close to Ohrid (North Macedonia) not related to volcanic activity, despite its name. CO2 flux measurements made with the accumulation chamber (321 sites over ∼50,000 m2) showed fluxes up to nearly 60,000 g m-2 d-1, sustaining a total output of ∼67 t d-1. Soil gas samples were taken at 50 cm depth from sites with high CO2 fluxes and analyzed for their chemical and isotope composition. The gas is mainly composed by CO2 (> 90%) with significant concentrations of H2S (up to 0.55 %) and CH4 (up to 0.32 %). The isotope compositions of He (R/RA 0.10) and of CO2 (δ13C ∼0‰) exclude significant mantle contribution, while δ13C-CH4 (∼ -35‰) and δ2H-CH4 (∼ -170‰) suggest a thermogenic origin for CH4. The area is characterized by intense seismic activity and Duvalo corresponds to an active tectonic structure bordering the Ohrid graben. The production of H2S within the stratigraphic sequence may be explained by thermochemical reduction of sulfate. The uprising H2S is partially oxidized to sulfuric acid that, reacting with carbonate rocks, releases CO2. The tectonic structure of the area favors fluid circulation, sustaining H2S production and oxidation, CO2 production and allowing the escape of the gases to the atmosphere. In the end, Duvalo represents a tectonic-related CO2 degassing area whose gases originate mostly, if not exclusively, in the shallowest part of the crust (<10 km). This finding highlights that even systems with trivial mantle contribution may sustain intense CO2 degassing (> 1000 t km-2 d-1)

Geogenic degassing from active tectonic areas of the Balkan Peninsula

During the last decades, great interest of the scientific community has been addressed to the estimation of geogenic Carbon degassing from tectonically active areas (Tamburello et al., 2018). Due to its high solubility in water, CO2 can be dissolved, transported and released to the atmosphere by groundwater. The quantity released by such process is probably of the same order of magnitude as that directly emitted from active volcanoes. The quantification of this contribution has a substantial implication for the modelling of the global atmospheric carbon cycle. The Balkan peninsula, one of the geodynamically most active regions in Europe, is characterized by intense geogenic degassing. Until now, only scarce data exist about the chemical and isotope composition of the gas emissions of this area (Nisi et al., 2013; Kis et al., 2017; Daskalopoulou et al., 2019). Aim of this PhD research is to investigate the possible presence of deep CO2 degassing and its possible impact on regional aquifers of the Balkans. Here, we present the results of a preliminary geochemical characterization of gas manifestations from the main geothermal fields of the Republic of North Macedonia. Gas samples are dominated by either N2 (up to 989,000 μmol/mol) or CO2 (up to 998,000 μmol/mol). The highest CO2 values are found along major fault lines, suggesting a deep source of gases. Only few samples have also significant CH4 concentrations (up to 20,200 μmol/mol). Helium shows a prevailing crustal source (R/RA = 0.1-1.6), however a low but significant mantle contribution was found in most samples. Similarly, δ13CCO2 displays a wide range (-15.7 to +1.0 ‰ vs. V-PDB) and the CO2/3He ratio suggests a prevailing carbonate source together with a small mantle contribution. δ13CCH4 and δ2HCH4 values indicate a mainly thermogenic source; few samples may be related to an abiotic source or be the result of secondary oxidation processes

Guano-related phosphate-rich minerals in European caves

Guano is a typical deposit found in caves derived from the excretions of bats and in minor cases of birds. These organic deposits decompose and form a series of acid fluids and gases that can interact with the minerals, sediments, and rocks present in the cave. Over sixty phosphates are known and described from caves, but guano decay also often leads to the formation of nitrates and sulfates. In this study twenty-two European caves were investigated for their guano-related secondary minerals. Using various analytical techniques, seventeen phosphates, along with one sulfate (gypsum), were recognized as secondary products of guano decay. Among those minerals, some are very rare and result from the interaction of guano leachates with clays, fluvial deposits, or pyrite. Some of these minerals are even found only in the studied caves (spheniscidite, robertsite). The most common minerals belong to the apatite group. The common mineral association present in fresh decaying guano is brushite-ardealite-gypsum, minerals that usually are not present in older deposits because of their higher solubility. Most minerals are in hydrated form because of the wet cave environment; however, some specific dry conditions may favor the presence of dehydrated minerals, such as berlinite, formed during guano combustion. Investigation on the acidity of guano piles shows pH values as low as 3.5 with an increase of acidity with age and depth. Finally, cave guano deposits should be better studied in the future because of their role in paleoenvironmental and paleoclimatic reconstructions and because it is important to better understand the origin of guano-related minerals, especially the phosphates and sulfates. Among all of the caves studied, Corona ’e sa Craba (Italy) and Domica-Baradla Cave (Slovakia-Hungary) are considered to be outstanding sites with respect to their phosphate mineralogy