Mud volcanoes and methane seeps in Romania: main features and gas flux

Romania is one of the European countries with the most vigorous natural seepage of methane, uprising from pressurised natural gas and petroleum reservoirs through deep faults. The largest seepage zone is represented by large mud volcanoes, with CH4 >80% v/v, occurring on the Berca-Arbanasi hydrocarbon-bearing faulted anticline, in the Carpathian Foredeep. Smaller mud volcanoes have been identified in other areas of the Carpathian Foredeep, in the Transylvanian Depression and on the Moldavian Platform. New surveys carried out in Transylvania allowed us to discover the richest N2 mud volcano zone in the world (N2>90% v/v), with a remarkably high He content and a helium isotopic signature which highlights a contribution of mantle-derived source. The large mud volcanoes are generally quiescent, with rare explosive episodes and provide a methane flux in the order of 102-103 t km?2 y?1. Independently from mud volcanism, a remarkable dry macroseepage, however, has been found, with a degassing rate up to three orders of magnitude higher than that of mud volcanoes (i.e. 103-105 t km?2 y?1). The total gas flux from all investigated macroseepage zones in Romania is estimated in the range of 1500-2500 t y?1. The emission from microseepage, pervasively occurring throughout the hydrocarbon-prone basins, has yet to be assessed and added to the total gas output to the atmosphere

Facultative methanotrophs are abundant at terrestrial natural gas seeps

Background: Natural gas contains methane and the gaseous alkanes ethane, propane and butane, which collectively influence atmospheric chemistry and cause global warming. Methane-oxidising bacteria, methanotrophs, are crucial in mitigating emissions of methane as they oxidise most of the methane produced in soils and the subsurface before it reaches the atmosphere. Methanotrophs are usually obligate, i.e. grow only on methane and not on longer chain alkanes. Bacteria that grow on the other gaseous alkanes in natural gas such as propane have also been characterised, but they do not grow on methane. Recently, it was shown that the facultative methanotroph Methylocella silvestris grew on ethane and propane, other components of natural gas, in addition to methane. Therefore, we hypothesised that Methylocella may be prevalent at natural gas seeps and might play a major role in consuming all components of this potent greenhouse gas mixture before it is released to the atmosphere. Results: Environments known to be exposed to biogenic methane emissions or thermogenic natural gas seeps were surveyed for methanotrophs. 16S rRNA gene amplicon sequencing revealed that Methylocella were the most abundant methanotrophs in natural gas seep environments. New Methylocella-specific molecular tools targeting mmoX (encoding the soluble methane monooxygenase) by PCR and Illumina amplicon sequencing were designed and used to investigate various sites. Functional gene-based assays confirmed that Methylocella were present in all of the natural gas seep sites tested here. This might be due to its ability to use methane and other short chain alkane components of natural gas. We also observed the abundance of Methylocella in other environments exposed to biogenic methane, suggesting that Methylocella has been overlooked in the past as previous ecological studies of methanotrophs often used pmoA (encoding the alpha subunit of particulate methane monooxygenase) as a marker gene. Conclusion: New biomolecular tools designed in this study have expanded our ability to detect, and our knowledge of the environmental distribution of Methylocella, a unique facultative methanotroph. This study has revealed that Methylocella are particularly abundant at natural gas seeps and may play a significant role in biogeochemical cycling of gaseous hydrocarbons

High potential for CH4 emission mitigation from oil infrastructure in one of EU's major production regions

Ambitious methane (CH4) emission mitigation represents one of the most effective opportunities to slow the rate of global warming over the next decades. The oil and gas (O&G) sector is a significant source of methane emissions, with technically feasible and cost-effective emission mitigation options. Romania, a key O&G producer within the EU, with the second highest reported annual CH4 emissions from the energy sector in the year 2020 (Greenhouse Gas Inventory Data - Comparison by Category, 2022), can play an important role towards the EU's emission reduction targets. In this study, we quantify CH4 emissions from onshore oil production sites in Romania at source and facility level using a combination of ground- and drone-based measurement techniques. Measured emissions were characterized by heavily skewed distributions, with 10% of the sites accounting for more than 70% of total emissions. Integrating the results from all site-level quantifications with different approaches, we derive a central estimate of 5.4 kg h-1 per site of CH4 (3.6 %-8.4 %, 95% confidence interval) for oil production sites. This estimate represents the third highest when compared to measurementbased estimates of similar facilities from other production regions. Based on our results, we estimate a total of 120 kt CH4 yr-1 (range: 79-180 kt yr-1) from oil production sites in our studied areas in Romania. This is approximately 2.5 times higher than the reported emissions from the entire Romanian oil production sector for 2020. Based on the source-level characterization, up to three-quarters of the detected emissions from oil production sites are related to operational venting. Our results suggest that O&G production infrastructure in Romania holds a massive mitigation potential, specifically by implementing measures to capture the gas and minimize operational venting and leaks

Inventory of Onshore Hydrocarbon Seeps in Romania (HYSED-RO Database)

Seeps are the expression of the migration of hydrocarbons from subsurface accumulations to the surface in sedimentary basins. They may represent an important indication of the presence of petroleum (gas and oil) reservoirs and faults, and are a natural source of greenhouse gas (methane) and atmospheric pollutants (ethane, propane) to the atmosphere. Romania is one of the countries with the largest number of seeps in the world, due to the high petroleum potential and active tectonics. Based on a review of the available literature, and on the field surveys performed by the authors during the last 17 years, we report the first comprehensive GIS-based inventory of 470 seeps in Romania (HYSED-RO), including gas seeps (10.4% of the total), oil seeps (11.7%), mud volcanoes (50.4%), gas-rich springs (12.6%), asphalt (solid) seeps (4.3%), unclassified manifestations (4.0%), and uncertain seeps (6.6%). Seeps are typically located in correspondence with major faults and vertical and fractured stratigraphic contacts associated to petroleum reservoirs (anticlines) in low heat flow areas, and their gas-geochemistry reflects that of the subsurface reservoirs. The largest and most active seeps occur in the Carpathian Foredeep, where they release thermogenic gas, and subordinately in the Transylvanian Basin, where gas is mainly microbial. HYSED-RO may represent a key reference for baseline characterization prior to subsurface petroleum extraction, for environmental studies, and atmospheric greenhouse gas emission estimates in Romania.Published396A. Geochimica per l'ambienteJCR Journa

In-situ analysis of the gas-emissions of the Eastern Carpathians (Romania) using the Multi-Gas instrument

The Multi-Gas instrument is an important tool for the investigations and monitoring of volcanic systems world- wide, because it can be easily placed on a volcano and can provide real-time data on the compositional changes of the fluids that are released (Aiuppa et al., 2005, Shinohara et al., 2005). We used a specially designed Multi-Gas to gather in situ compositional information about low-temperature, CO2-rich gases, emerging from different manifestations like dry gas emissions (mofettes), bubbling pools and springs. The instrument is equipped with two IR sensors for CO2 (0-100%) and CH4 (0-7%) and one electrochemical sensor for H2S (0-200 ppm). The Multi-Gas was used during several field surveys between September-November 2018 across the Eastern Carpathians area, where a total of 69 gas emissions were investigated for their CO2, CH4 and H2S concentrations. Concentrations of the different gas-species varied according to the geological context. The CO2 concentrations varied between 0.96 and 98.08 %. The highest values were measured in the the volcanic area of Ciomadul, the youngest volcano of the Eastern Carpathians (32 kyr, Harangi et al., 2015), characterized by high CO2 gas output up to 8700 t/year (Kis et al., 2017). High values were measured also in the thrusted and folded area of the Carpathian Flysch and, suggesting the tectonic control over the appearance of the gas emissions. The CH4 concentrations ranged between 0.21 and 6.76% and were higher at hydrocarbon-prone areas, such as the sedimentary deposits of the Transylvanian Basin and Carpathian Flysch. In these cases the CO2 concentrations were low (up to 4.6%). The concentrations of H2S were higher at the volcanic area of Ciomadul, reaching values above the detection limit (∼200 ppm). The Multi-Gas proved to be useful tool in the in-situ investigation of cold gas emissions of the Eastern Carpathians, being efficient especially for the measurement of the H2S concentrations that are very sensitive for oxidation processes. This research belongs to the scientific project supported by the OTKA, K116528 (Hungarian National Re- search Fund), the EU and Hungary, co-[U+FB01]nanced by the European Regional Development Fund in the project GINOP-2.3.2-15-2016-00009 ‘ICER’, New York Hungarian Scientific Society and the Deep Carbon Observatory. Aiuppa, A., Federico, C., Giudice, G., Gurrieri, S. 2005, Chemical mapping of fumarolic field: La Fossa Crater, Vulcano Island (AeolianIslands, Italy), Geophysical Research Letters, Vol. 32, LI3309 Harangi, Sz., Lukács, R., Schmitt, A.K., Dunkl, I., Molnár, K., Kiss, B., Seghedi, I., Á. Novothny, Molnár, M. 2015, Constraints on the timing of Quaternary volcanism and duration of magma residence at Ciomadul volcano, east-central Europe, from combined U-Th/He and U-Th zircon geochronology, Journal of Volcanology and Geothermal Research, 301, 66-80 Kis B.M. , Ionescu, A., Cardellini, C., Harangi, Sz., Baciu, C., Caracausi,C. & Viveiros, F. 2017, Quan- tification of carbon dioxide emissions of Ciomadul, the youngest volcano of the Carpathian-Pannonian Region (Eastern-Central Europe, Romania), Journal of Volcanology and Geothermal Research, 341, 119–130 Shinohara, H. 2005, A new technique to estimate volcanic gas composition: plume measurements with a portable multi-sensorsystem, Journal of Volcanology and Geothermal Research, 143, 319– 33

Geochemistry of dissolved gases from the Eastern Carpathians - Transylvanian Basin boundary

We show the results of a study on the volatiles dissolved in mineral waters discharged over a 200km-long transect along the Rodna-Bârgău area and Călimani-Gurghiu-Harghita volcanic chain (Eastern Carpathians, Romania). All of the collected mineral water samples carry dissolved gas with carbon dioxide content up to 1.99cm3STP/gH2O, and helium content up to 2.3×10-5 cm3STP/gH2O. Carbon (δ13CTDIC total dissolved inorganic carbon, ranging from -15.6 to 5.32‰ vs. VPDB), He systematics (He isotopes in the range of 0.38-0.99 Ra, Ra=air-normalized 3He/4He ratio) and CO2/3He ratio spanning over four orders of magnitude from MORB-like values of 2.92×109 to crustal-type values of 3.02×1013, coherently indicate the presence of fluids from different crustal sources (e.g. sediments, hydrocarbon reservoirs) besides minor, but detectable contributions of mantle/magmatic-derived fluids (up to 16.45%). Our investigations show that the wide range of chemical and isotopic composition can be explained in terms of mixings among different gas sources feeding the groundwater and the contemporary occurrence of gas-water interactions like degassing and deposition of carbonates, affecting the circulating waters after their infiltration. © 2016