Search

T he Duvalo locality is located in the SW of the Republic of North Macedonia, in the Ohrid region, near the village of Kosel. It is an area of strong soil degassing, called “volcano” by the local people despite volcanic activity has never been documented in the recent geologic history of the area [1]. A large area (thousands of sqm) shows signs of strong alteration and is devoid of vegetation. Until the 19thcentury sulphur was mined from this area [1]. In August 2019, a campaign of soil CO2 flux measurements and soil gas sampling was made. Duvalo is sometimes referred to as an active geothermal feature but no signs of enhanced geothermal gradient were found and the soil temperatures at 50 cm depth in this campaign were always within the range of local mean air temperatures. Soil CO2 flux values ranged from 1.3 to 59,000 g/m2/d and can be modelled with the overlapping of 3 or 4 flux populations. A possible biological background is estimated in 6.8±1.8 g/m2/d while the other populations are characterized by an anomalous average flux ranging from 180 to 33,000 g/m2/d. The CO2 total emission, estimated both with a statistical and geostatistical approach, provided similar values in the order of 50 t/d. This has to be considered as a minimum value because only areas with evident signs of alteration have been investigated. Nevertheless, the estimated output is quite high for an area unrelated with recent volcanism or geothermal activity. The chemical composition of soil gases shows: CO2 (96.6%), N2 (1.8%), H2S (0.6%) and CH4 (0.3%) as the main gases. The present composition is almost indistinguishable from previous analyses made in 1957 and 1977 [1] pointing to a stability of the system in last decades. The isotope compositions indicate for CO2 (δ13C -0.2 ‰) a pure carbonate rock origin, for CH4 (δ13C -34.4 ‰ and δ2H -166 ‰) a thermogenic origin and for He (R/RA 0.10) a pure crustal origin. The H2S released at Duvalo may be produced by either microbial or thermochemical sulphate reduction favoured by hydrocarbons whose presence can be inferred by the uprise of thermogenic methane. Partial oxidation of H2S during its upflow, producing sulphuric acid, may be responsible of the production of abundant CO2 through dissolution of carbonate rocks. Similar processes have been evidenced also in other parts of North Macedonia [2]. These gases rise up through the N–S trending normal faults bordering the seismically active Ohrid basin graben [3] being released to the atmosphere through the soils of Duvalo “volcano”.

Like most of the Balkan Peninsula, North Macedonia is a geodynamically active area. As such it has many hydrothermal features and gas manifestations. Until now, no systematic study about the geochemical characterization of the geogenic gases was made before in this country. In August 2019, 24 gas samples were collected in the study area. All, except one collected at Duvalo (soil gas), are gases bubbling or dissolved in thermomineral waters (temperatures from 12 to 66 °C). They were analysed in the laboratory for their chemical (He, Ne, Ar, O2 , N2 , H2 , H2S, CH4 and CO2) and isotopic composition (δ13C-CO2, δ13C-CH4, δ2H-CH4 and R/RA). Most of the gases have CO2 as the main component (400-998,000 ppm) while the remaining are enriched in N2 (1300-950,000 ppm). Helium ranges from 0.3 to 2560 ppm while CH4 from 1.6 to 20,200 ppm. R/RA and 4He/20Ne ratios indicate a generally low atmospheric contamination, a prevailing crustal contribution and mantle contributions between 1 and 20% considering a MORB endmember. The highest mantle contributions are found in the SE part of the country very close to the sites that show the highest R/RA values in continental Greece [1]. This area is characterised by extensional tectonics and Plio-Pleistocene volcanism. A quite high mantle contribution (about 15%) is also found in two manifestations in the NW part of the country along a main normal fault system. With the exception of the sample of Smokvica, which has very low CO2 (1400 ppm) and δ13C-CO2 (-15.7 ‰ V-PDB), all free gases show a relatively narrow range in δ13C-CO2 values (-4.6 to +1.0 ‰ V-PDB) indicating the mixing between a mantle and a carbonate rock source. The isotope composition allows us to assign the CH4 origin to three sources. The largest group can be attributed to a hydrothermal origin (δ13C-CH4 around -20 ‰ V-PDB and δ2H-CH4 around -100‰). Three samples collected in the SW part of the country have a thermogenic origin (δ13C-CH4 around -35 ‰ V-PDB and δ2H-CH4 around -160‰ V-SMOW). Finally, one sample (Smokvica) with the highest values (δ13C-CH4 -7.2 ‰ V-PDB and δ2H-CH4 -80‰ V-SMOW) may be attributed to abiotic processes in a continental serpentinization environment or to methane oxidation.This research was funded by the DCO Grant n. 10881-TDB “Improving the estimation of tectonic carbon flux”, GINOP-2.3.2-15-2016-00009 ‘ICER’ project and PO FSE Sicilia 2014 – 2020 (CUP: G77B17000200009).References:[1] Daskalopoulou et al., 2018 – Chemical Geology, 479, 286-301