Record of ³H and ³⁶Cl from the Fukushima nuclear accident recovered from soil water in the unsaturated zone at Koriyama

The opportunity to measure the concentrations of ³H and ³⁶Cl released by the Fukushima nuclear accident in 2011 directly in rain was lost in the early stage of the accident. We have, however, been able to reconstruct the deposition record of atmospheric ³H and ³⁶Cl following the accident using a bore hole that was drilled in 2014 at Koriyama at a distance of 60 km from the accident. The contributions of ³H and ³⁶Cl from the accident are 1.4 × 10¹³ and 2.0 × 10¹² atoms m⁻² respectively at this site. Very high concentrations of both ³H (46 Bq L⁻¹) and ³⁶Cl (3.36 × 10¹¹ atoms L⁻¹) were found in the unsaturated soil at depths between 300 and 350 cm. From these, conservative estimates for the ³H and ³⁶Cl concentrations in the precipitation in the ～ 6 weeks following the accident were 607 Bq L⁻¹ and 4.74 × 10¹⁰ atoms L⁻¹, respectively. A second hole drilled in 2016 showed that ³H concentrations in the unsaturated soil and shallow groundwater had returned to close to natural levels, although the ³⁶Cl concentrations were still significantly elevated above natural levels

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)

Preliminary geochemical characterization of gas manifestations in North Macedonia

L ike 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 \ub0C). They were analysed in the laboratory for their chemical (He, Ne, Ar, O2 , N2 , H2 , H2S, CH4 and CO2) and isotopic composition (\u3b413C-CO2, \u3b413C-CH4, \u3b42H-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 \u3b413C-CO2 (-15.7 \u2030 V-PDB), all free gases show a relatively narrow range in \u3b413C-CO2 values (-4.6 to +1.0 \u2030 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 (\u3b413C-CH4 around -20 \u2030 V-PDB and \u3b42H-CH4 around -100\u2030). Three samples collected in the SW part of the country have a thermogenic origin (\u3b413C-CH4 around -35 \u2030 V-PDB and \u3b42H-CH4 around -160\u2030 V-SMOW). Finally, one sample (Smokvica) with the highest values (\u3b413C-CH4 -7.2 \u2030 V-PDB and \u3b42H-CH4 -80\u2030 V-SMOW) may be attributed to abiotic processes in a continental serpentinization environment or to methane oxidation

Cesium, iodine and tritium in NW Pacific waters - a comparison of the Fukushima impact with global fallout

Radionuclide impact of the Fukushima Dai-ichi nuclear power plant accident on the distribution of radionuclides in seawater of the NW Pacific Ocean is compared with global fallout from atmospheric tests of nuclear weapons. Surface and water column samples collected during the <i>Ka'imikai-o-Kanaloa</i> (<i>KOK</i>) international expedition carried out in June 2011 were analyzed for ¹³⁴Cs, ¹³⁷Cs, ¹²⁹I and ³H. The ¹³⁷Cs, ¹²⁹I and ³H levels in surface seawater offshore Fukushima varied between 0.002–3.5 Bq L⁻¹, 0.01–0.8 μBq L⁻¹, and 0.05–0.15 Bq L⁻¹, respectively. At the sampling site about 40 km from the coast, where all three radionuclides were analyzed, the Fukushima impact on the levels of these three radionuclides represents an increase above the global fallout background by factors of about 1000, 50 and 3, respectively. The water column data indicate that the transport of Fukushima-derived radionuclides downward to the depth of 300 m has already occurred. The observed ¹³⁷Cs levels in surface waters and in the water column are compared with predictions obtained from the ocean general circulation model, which indicates that the Kuroshio Current acts as a southern boundary for the transport of the radionuclides, which have been transported from the Fukushima coast eastward in the NW Pacific Ocean. The ¹³⁷Cs inventory in the water column is estimated to be about 2.2 PBq, what can be regarded as a lower limit of the direct liquid discharges into the sea as the seawater sampling was carried out only in the area from 34 to 37° N, and from 142 to 147° E. About 4.6 GBq of ¹²⁹I was deposited in the NW Pacific Ocean, and 2.4–7 GBq of ¹²⁹I was directly discharged as liquid wastes into the sea offshore Fukushima. The total amount of ³H released and deposited over the NW Pacific Ocean was estimated to be 0.1–0.5 PBq. These estimations depend, however, on the evaluation of the total ¹³⁷Cs activities released as liquid wastes directly into the sea, which should improve when more data are available. Due to a suitable residence time in the ocean, Fukushima-derived radionuclides will provide useful tracers for isotope oceanography studies on the transport of water masses during the next decades in the NW Pacific Ocean

The link between lithospheric scale deformations and deep fluid emanations: Inferences from the Southeastern Carpathians, Romania

Understanding the formation, migration and emanation of deep CO2, H2O and noble gases (He–Ne) in deep-seated deformation settings is crucial to understand the complex relationship between deep-originated fluids and lithospheric deformation. To gain a better insight into these phenomena, we studied the origin of H2O, CO2 and noble gases of gas-rich springs found in the Târgu Secuiesc Basin located in the southeasternmost part of the Carpathian-Pannonian region of Europe. This study area is one of the best natural examples to understand the connection between the deep sources of gas emanations and deep-seated deformation zones, providing an excellent analogue for regions worldwide with similar tectonic settings and fluid emanation properties. We studied the δ2H and δ18O stable isotopic ratios of the spring waters, and the δ13C, He and Ne stable isotopic ratio of the emanating CO2-rich gases dissolved in the mineral spring waters in Covasna town and its vicinity. Based on the δ2H, δ13C, δ18O stable isotopic ratios, the spring waters and the majority of the gases are released through two consecutive fluid infiltration events. The preservation of the metamorphic signal of the upwelling H2O is linked to the local groundwater flow and fault abundancy. Furthermore, the noble gas isotopic ratios show a high degree of atmospheric contamination in the dissolved water gasses that is most likely related to the local hydrogeology. Nevertheless, the elevated corrected helium stable isotopic ratios (Rc/Ra) of our filtered data suggest that part of the emanating gases have a potential upper mantle source component. Beneath the Southeastern Carpathians, mantle fluids can have multiple origin including the dehydration of the sinking slab hosting the Vrancea seismogenic zone, the local asthenospheric upwelling and the lithospheric mantle itself. The flux of the mantle fluids is enhanced by lithospheric scale deformation zones that also support the fluid inflow from the upper mantle into the lower crust. The upwelling CO2–H2O mantle fluids may induce the release of crustal fluids by shifting the pore fluid composition (X(CO2)) and, consequently, initiating decarbonisation and devolatilization metamorphic reactions as a result of carbonate and hydrous mineral destabilisation in the crust. Based on the p-T-X(CO2) conditions of calc-silicates and the local low geotherm, we emphasise the importance of the upwelling fluids in the release and upward migration of further H2O and CO2 in the shallower lower and upper crust. Our observations in the Southeastern Carpathians show a strong similarity to other deep-seated deformation zones worldwide (e.g., Himalayas, Alps, San Andreas Fault). We infer that migration of deep fluids may also play an important role in addition to temperature control on the generation of crustal fluids in deep-seated deformation zones

Noble gas and carbon isotope systematics at the seemingly inactive Ciomadul volcano (Eastern‐Central Europe, Romania): evidence for volcanic degassing

Ciomadul is the youngest volcano in the Carpathian-Pannonian Region, Eastern-Central Europe, which last erupted 30 ka. This volcano is considered to be inactive, however, combined evidence from petrologic and magnetotelluric data, as well as seismic tomography studies suggest the existence of a subvolcanic crystal mush with variable melt content. The volcanic area is characterized by high CO2 gas output rate, with a minimum of 8.7 × 103 t yr-1. We investigated 31 gas emissions at Ciomadul to constrain the origin of the volatiles. The δ13C-CO2 and 3He/4He compositions suggest the outgassing of a significant component of mantle-derived fluids. The He isotope signature in the outgassing fluids (up to 3.10 Ra) is lower than the values in the peridotite xenoliths of the nearby alkaline basalt volcanic field (R/Ra 5.95Ra±0.01) which are representative of a continental lithospheric mantle and significantly lower than MORB values. Considering the chemical characteristics of the Ciomadul dacite, including trace element and Sr- Nd and O isotope compositions, an upper crustal contamination is less probable, whereas the primary magmas could have been derived from an enriched mantle source. The low He isotopic ratios could indicate a strongly metasomatized mantle lithosphere. This could be due to infiltration of subduction-related fluids and postmetasomatic ingrowth of radiogenic He. The metasomatic fluids are inferred to have contained subducted carbonate material resulting in a heavier carbon isotope composition (13C is in the range of -1.4 to -4.6 ‰) and an increase of CO2/3He ratio. Our study shows the magmatic contribution to the emitted gases

CO2-DRIVEN COLD WATER GEYSERING WELL IN TRANSYLVANIA – BĂILE CHIRUI

Co2-Driven Cold Water Geysering Well in Transylvania – Băile Chirui. Cold water “geyser” or geysering well is the internationally used term of such phenomenon where cold water is erupting from a hydrogeological well due to CO2 movement. Until now there have been reported 14 geysering wells all over the World (Glennon & Pfaff, 2004). Through this article we would like to add a “new” cold water “geyser” to the above mentioned list, the so called Chirui Geyser. Investigations on Chirui Geyser were carried out several times during 2007 – 2013. Compared with the others, Chirui Geyser has the longest erupting phase with its minimum 38 hours of activity. Switching from the active to the inactive phase or vice versa the values of different parameters of the water are also changing. There has been described an oscillating phase before the water falls back into the pipe. Such activity has not been reported at other cold water geysering wells. Chirui Geyser is located in a post-volcanic area where most probably CO2 has a volcanic origin. In the South Harghita region there are several hydrogeological drillings that reached CO2 rich mineral water aquifers. Many of them could possibly have geysering activity

Tracing the Source of Hydrothermal Fluid in Ophiolite-Related Volcanogenic Massive Sulfide Deposits: A Case Study from the Italian Northern Apennines

The Italian Northern Apennines contain several Fe-Cu-Zn-bearing, Cyprus-type volcanogenic massive sulfide (VMS) deposits, which significantly contribute to the Cu resources of Italy. The massive sulfide lenses and related stockwork mineralizations are hosted by several levels (from basalt to serpentinite) of the unmetamorphosed ophiolitic series; therefore, this region offers perfect locations to study the ore-forming hydrothermal system in detail. A combination of fluid inclusion microthermometry, Raman spectroscopy, electron probe analyses (chlorite thermometry) and stable and noble gas isotope geochemistry was used to determine the fluid source of the VMS system at Bargone, Boccassuolo, Campegli, Casali–Monte Loreto, Corchia, Reppia and Vigonzano. This question of the fluid source is the focus of modern VMS research worldwide, as it has a direct influence on the metal content of the deposit. The obtained temperature and compositional data are both in the typical range of VMS systems and basically suggest evolved seawater origin for the mineralizing fluid. Modification of seawater was most commonly due to fluid–rock interaction processes, which happened during long-lasting circulation in the crust. The role of a small amount of magmatic fluid input was traced only at the lower block of Boccassuolo, which may be responsible for its higher ore grade. This fluid origin model is evidenced by O, H and C stable isotopic as well as He, Ne and Ar noble gas isotopic values