Deep Fluid Research Articles

Assessment of oil-and-gas-bearing capacity of pre-jurassic and jurassic deposits of the central part of the West Siberian plate

There were examined the issues of studying the features of the lithological and petrographic composition and the formation of oil deposits within the fields of the Surgut dome fold and the Frolov megadepression. It was noted that the formation of deposits of the sedimentary cover is associated with the peculiarities of the geological structure and the oil-bearing capacity of the basement rocks. In the considered territory, a high level of oil-bearing sedimentary cover is observed within the central part of the Surgut dome fold, and the deposits of the Pre-Jurassic part of the section can be additional sources of intensification of hydrocarbons in the Lower-Middle Jurassic deposits. The presence of zones of deep snaps is a search criterion for the detection of secondary reservoirs in them both — in destruction zones, basement, and in the Lower-Middle Jurassic deposits, therefore, deposits can be formed due to the vertically ascending migration of deep fluids through faults that cross the basement and horizons of the sedimentary cover.There were examined the issues of the prospects for the oil and gas content of the Lower-Middle Jurassic deposits, which must be associated with both granitoid massifs and the details of identifying the conditions of sedimentation and the establishment of contact zones of the sedimentary cover with the underlying formations.

Genesis of Significance of Carbonated Thermal Water Springs in Xining Basin, China

There are 30 carbonate hot springs in Yaoshuitan geothermal field, Xining Basin, China, with a temperature of 18~41.5 °C; and there are 10 carbonate hot springs in Qijiachuan geothermal field, with a temperature of 10~19.5 °C. Both geothermal fields are carbonate hot springs containing large amounts of CO2 gas. In order to reveal the origin of the carbonated hot springs in Yaoshuitan and Qijiachuan of Xining Basin, this paper offers a comprehensive study of the regional deep geology, tectonic setting, total analysis of carbonated hot springs, δ2H, δ18O, δ13C isotopes, main gas composition, and geochemical characteristics of travertine dating, travertine δ13C, and rare earth elements. The geological process of carbonated hot spring formation and the evolution of H+ content from deep to shallow is revealed, and the genetic mechanism of the carbonated hot spring in Xining Basin is systematically summarized. The results show that: (1) The characteristics of δ2H and δ18O isotopes indicate that the recharge source of carbonated thermal water springs in Xining Basin is mainly atmospheric precipitation. The age of carbonated thermal water springs at 14C is more than 20 ka, indicating that some of them may come from deep fluid (gas) sources. The R/Ra in carbonated thermal water springs is mostly less than 1, indicating that the helium in geothermal water is mainly crustal source helium, and there is no deep mantle source material. (2) The Piper three-plot indicates that the direction of groundwater evolution from the recharge area at the edge of Xining Basin to Yaoshuitan and Qijiachuan carbonated thermal water spring area near the edge of the basin is opposite to the normal path of groundwater evolution in the basin, which is due to the large amount of CO2 gas mixed in the deep fault along the northern margin of Laji Mountain. The ratio of (Ca2+ + Mg2+) and (HCO3− + SO42−) in the Potan and Qijiachuan carbonated thermal water springs is close to 1, and the ratio of (Na+ + K+)/HCO3− is less than 1. It indicates that the chemical composition of the Yaoshuitan carbonated thermal water spring and the Qijiachuan carbonated thermal water spring in Xining Basin is dominated by the dissolution of calcite, dolomite, and gypsum in deep carbonate reservoirs, supplemented by the dissolution of silicate minerals. The relationship between the volume fraction of CO2 and the δ13C value of carbon isotope of CO2 indicates that the source of CO2 is inorganic, which is mainly formed by metamorphism and decomposition of deep carbonate and marble. The δEu < 1 and δCe > 1 of the rare earth elements in the calcium center of the carbonated thermal water springs indicate that the groundwater supplying the travertine material has been in the acidic environment receiving CO2 from the deep crust for a long time. (3) A series of tectonic activities, such as late collision and post-collision between the Indian and Eurasian plates, has led to the uplift, asthenosphere upwelling, and thermal invasion of the northern Tibetan Plateau and other deep dynamic processes. The deep faults in the northern margin of the Laji Mountain and other deep faults with obvious neotectonic activity have provided channels for the up-invasion of deep thermal materials, and local geothermal anomalies were formed near the deep faults. The hidden carbonate rocks and silicate rocks with large thickness undergo thermal metamorphism under high temperature and high pressure in the deep geothermal anomaly area and form a large amount of CO2, which is dissolved in water and enhances the acidity of water. At the same time, the dissolution reaction of acidic water to carbonate rocks consumes H+, which keeps the carbonated thermal water spring weakly acidic. (4) The composition of travertine in carbonated thermal water springs is dominated by calcite, indicating that travertine may be formed in a deep geological environment with a temperature of 150~200 °C, indicating that there are abnormal heat sources in shallow carbonate strata with a burial depth of 3000~4000 m. The abnormal heat source may be caused by the deep fault in the northern margin of Laji Mountain, as well as other deep and large faults channeled in the deep crust and mantle heat source, indicating that the deep fault in the northern margin of Laji Mountain has an obvious heat-controlling effect, and there is a good prospect of geothermal resources exploration near the fault.

Genesis and Evolution of Hydrothermal Fluids in the Formation of the High-Grade Hishikari Gold Deposit: Carbon, Oxygen, and Sulfur Isotopic Evidence

The Hishikari low-sulfidation epithermal gold (Au) deposit in Kyushu, Japan, is world-famous for its premium ore. It has been hypothesized that magmatic contributions to the hydrothermal fluid during early stages of mineralization is possible, even if the hydrothermal fluids for many Au occurrences near the Hishikari deposit are of meteoric origin and are influenced by basement sedimentary rocks. The purpose of this study is to obtain constraints on the genesis and evolution of hydrothermal fluids in the formation of the high-grade Hishikari Au deposit by carbon and oxygen isotope ratios of calcite-bearing samples. Since the microanalysis of carbon and oxygen isotope ratios in every 12 μm of the calcite-bearing sample along the growth direction (corresponding to 10 years of the Hishikari mineralization) scatter in a particular range, the fluid evolution might not be a gradual change from a magmatic to a meteoric origin. Alternatively, a rapid turnover of two fluids might be happening locally. The average sulfur isotope ratio of hydrothermal pyrite is similar to that of the adjacent magma. However, according to the secondary ion mass spectrometry (SIMS) microanalysis, local pyrite with extremely low sulfur isotope ratios may interact with basement sedimentary rocks. Unlike other epithermal Au deposits in the vicinity, rapid local mixing of the magmatic-origin deep fluid and meteoric-origin fluid reacted with organic matter containing basement sedimentary rocks might cause gold precipitation at the Hishikari deposit.

Fluoride presence in drinking water along the southeastern part of El Bajío Guanajuatense, Guanajuato, Mexico: sources and health effects.

Drinking water with a high natural concentration of fluoride (F-) has serious consequences for the health of the rural population in the state of Guanajuato, Mexico, where the water contains levels of F- that are not allowed by national and international regulations (1.5mg/L). This health problem is very common in multiple states throughout Mexico where drinking water is generally extracted from aquifers that are hosted in fractured volcanic rocks of the Tertiary. These aquifers show similar geological characteristics: deep basins that formed as a result of felsic eruptive events and the extensional deformation of the Basin and Range and are now filled with unconsolidated sediments. In this study, we assessed the occurrence of F in volcanic rocks collected at 11 sampling sites along the Sierra de Codornices in Guanajuato (ranging between 0.01299 and 0.146 wt%, average 0.039 wt%, and SD = 0.039 wt%; n = 10), a region where both rural and urban communities consume drinking water with a high F- content (up to 7.1 (mg/L). The F content is dispersed in volcanic rocks, and the highest levels are present in felsic rocks. The statistical and hydrogeochemical results of a sampling campaign of 32 wells in the Juventino Rosas (JR) and Villagran (Vill) municipalities in 2019 suggest that F- mobilization in groundwater is the product of silicate weathering and the dissolution of volcanic glass, alkaline desorption in the surfaces of F-containing minerals, and possibly ion exchange of minerals and clays or deep fluids enriched with F-, in addition to the precipitation of carbonates that decrease the Ca2+ concentration in groundwater. All of these processes can be accelerated by groundwater geothermal characteristics within the study area. The hydrogeochemical, fluoride exposure risk, and fluoride pollution index (FPI) results, as well as the epidemiological survey, indicate that teenagers and older adults from Praderas de la Venta are at risk of exposure to F- due to the high concentrations ingested over a long period, the toxicity of the element, and its ability to accumulate in the bones. Extended exposure to elevated levels increases the risk. This work allows us to observe how the populations of JR and Vill can be exposed to high F- contents in drinking water due to the geological characteristics of the region.

Gravity yearly transient change around the epicenter of 2022 MS 6.9 Menyuan earthquake, China and seismotectonic implications

The MS 6.9 Menyuan earthquake occurred in the northeastern Tibetan Plateau on 8 January 2022. High-precision absolute gravity observations provide a unique perspective on seismotectonic feature of strong continental earthquakes. An obvious and coincident gravity increase about 5 years before the Menyuan earthquake with the rate up to 3.94 μGal/yr is observed at four absolute gravity stations within 350 km away from the epicenter. These four stations have been carried out repeat gravity observations by the Crustal Movement Observation Network of China (CMONOC) for more than a decade. The observed gravity changes could not be reasonably explained by the land water storage change nor crustal vertical deformation and thus might be related to the processes in the crust. A disc-shaped equivalent source region with a radius of 175 km is then modeled, based on the residual gravity rates. We find that the seismicity increases gradually in the modeled source region from about 2017 to 2021, similar to the pattern of absolute gravity change. Furthermore, the spatiotemporal distribution of epicenters is consistent with the fluids diffusion model, indicating that this could be related to the redistribution of deep fluid mass. With consideration of the near-surface processes, regional crustal structure, and seismicity, multiple lines of evidence consistently refer to the presence of deep fluids migration before the Menyuan earthquake. Our results suggest that high-precision absolute gravimetry can be used to monitor crustal fluid environment and determine mass changes in the source regions of potential large earthquakes.

The Role of Deep Fluids in Crustal Subsidence of the Cratonic Interior: The Moscow Sedimentary Basin during the Late Devonian

The Role of Deep Fluids in Crustal Subsidence of the Cratonic Interior: The Moscow Sedimentary Basin during the Late Devonian

Delineating a volcanic aquifer using groundwater-induced gravity changes in the Tatun Volcano Group, Taiwan

The Tatun Volcanic Group (TVG) is an active volcanic system that poses potential volcanic hazards to northern Taiwan. Groundwater migration can be sensitive to volcanic activities and can induce temporal gravity changes. Here we conducted four gravity measurement campaigns in 2012 with two CG5 relative gravimeters at a total of 31 gravity monitoring sites to probe the spatiotemporal groundwater variability in the TVG area. With careful adjustments to the gravity measurements, the standard point gravity error was approximately 8 μGal on average. The observed gravity changes were compared with the groundwater-induced gravity variations derived from two hydrological models: the continuous flow model that consisted of one permeable layer (Model A) and a dynamic groundwater flow model that used the hydrological solver MODFLOW (Model B). The results show that only gravity observations in the central TVG match the simulated gravity pattern, i.e., the hydrology in the central TVG follows free groundwater flows within the interconnected and porous strata. On the other hand, inconsistencies between simulated and observed gravity changes range from + 40 to – 80 μGal. The discrepancies were located at the eastern and western areas in the TVG and showed opposite variations over time. This pattern of temporal variability cannot be attributed to the use of shallow aquifer models that merely reflect the surface recharges and discharges. We infer that the pattern stems from deep flows, such as hydrothermal fluids alternately replenishing aquifers to the east and west of the TVG, i.e., deep fluid conduits may have developed to the east and west of the TVG and bypassed the central area.

Geochemistry of fluorine in halo waters of ore fields of the southeastern part of the Dnipro-Donetsk avlakogen

The geochemical features of fluorine and its possible sources in the waters of the hydrothermal ore fields of the Dnipro-Donetsk avlakogen (DDA) are considered. It was established that the formation of anomalies occurs due to the interaction of infiltration waters of the zone of free water exchange and waters of deep formation, which are unloaded along the zones of deep faults. It is substantiated that the water migration of fluorine is determined by the geochemical type of groundwater, the degree of its mineralization, acid-base (pH) and oxidation-reduction (Eh) potentials, the presence of complex-forming elements with which fluorine forms mobile complex compounds, etc. Formulation of the problem. Fluorine is a typomorphic chemical element that is widely present in groundwater. It forms large-scale, contrasting hydrogeochemical anomalies in various types of hydrothermal ore fields, which are controlled by zones of deep faults - fluorite, mercury, polymetallic, and others. Presenting main material. Anomalies of the element are also formed in those fault zones, where the processes of modern heat and mass transfer are observed, manifested in the upward discharge of endogenous fluids against the background of increased intensity of the geothermal field. This indicates the probable arrival of fluorine in endogenous fluid flows, which are mixed with formation waters during their upward migration. The most contrasting aureoles of fluorine scattering are established in the zone of hypergenic weathering of fluorite of the Pokrovo-Kyreevsky deposit and in the aureole waters of the Mykytiv mercury ore field, in the rocks of which fluorite mineralization is absent. In them, fluorine, together with other trace elements, forms multicomponent anomalies and is part of the hydrogeochemical association of elements-indicators of hidden mercury mineralization - Hg, As, B, F, (Sb). Conclusions. 1. Geochemical features of fluorine in the processes of hydrothermal mineralization are caused by both hypogenic and hypergenic factors of its migration and concentration in the hydrolithosphere of the Dnipro-Donetsk avlakogen. 2. The high migration activity of fluorine in fluid systems and, in particular, in groundwater, is determined by numerous mobile forms of the element that exist under different geochemical conditions - in the form of gas, simple anions, complex compounds with metals, silicon, manganese, boron and other chemical elements Fluorine migrates best in alkaline sodium bicarbonate and sodium chloride waters, in which Сl–, Na+ and ОН– ions not only act as a complexing agent, but also provide high ionic strength of aqueous solutions. 3. The high content of fluorine in the waters of the Pokrovo-Kyreivsky fluorite deposit is provided by two different geochemical processes: a) hypergenic physicochemical destruction of CaF2 by gravitational infiltration waters of the zone of free water exchange; b) the influx of fluorine into deep formation waters together with endogenous fluids that are discharged along fault structures at the post-hydrothermal stage of their tectonic activation. 4. Abnormally high concentrations of fluorine in the hydrothermal mercury ore fields of the Mykytivskyi and Druzhkivsko-Kostiantynivskyi deposits, in the rocks of which there is practically no fluorite mineralization, are due to the influx of the element into the mineralization zones from deep fluid flows and underground waters of deep horizons. 5. The main natural sources of fluorine in the waters of hydrothermal deposits of the region are: a) products of hypergenic weathering of hydrothermal mineralization of fluorite; b) flows of endogenous postheterothermal fluids; c) pore solutions of sedimentary rocks of marine origin.

Термодинамическая модель глубинного происхождения нефти и ее фазового «замерзания»

Based on the deep inorganic concept of the origin of oil and gas deposits, the evolution of these petrogenic reservoirs in the lithosphere is considered. The analysis of phase diagrams and experimental data made it possible to determine two trends in the evolution of non-methane hydrocarbons in the Earth's interior. In the upper mantle, the "metastability" of heavy (with a lower H/C ratio) hydrocarbons increases with depth. However, at temperatures and pressures corresponding to the surface mantle-crustal hydrothermal conditions, the “relative metastability” of heavy hydrocarbons increases with approach to the surface. When deep HCs fluids rise to the surface, petrogenic oil reservoirs are formed as a result of a drop in hydrogen fugacity and a gas → liquid oil phase transition. Under the physical and chemical conditions of an oil reservoir, metastable reversible phase equilibria are established between liquid oil, gas hydrocarbons and CO2 and solid (pseudocrystalline) "mature" and "immature" kerogens of "oil source" rocks. A decrease in hydrogen pressure and temperature leads to a stoichiometric phase transition (“freezing”) of liquid oil into solid kerogens. This occurs as a result of oil dehydrogenation in the processes of high-temperature CO2 fixation and low-temperature hydration of oil hydrocarbons, which are the main geochemical pathways for its transformation into kerogen. Thus, the formation of carbon matter in petrogenic reservoirs is the result of regressive metamorphism of deep hydrocarbon fluids, natural gas, liquid oil, and emerging accumulations of naphthides.

Shallow portion of an active geothermal system revealed by multidisciplinary studies: The case of Le Biancane (Larderello, Italy)

The natural park of Le Biancane is located in the southern sector of the Larderello-Travale geothermal field (LTGF). It extends over an approximately 100,000 m2 area where the impermeable caprock is locally absent and deep fluids may directly reach the surface. Through a multidisciplinary approach including measurements of soil CO2 flux (total output of 11.5 t day−1), soil temperature (average 34.4 °C), stable isotope and chemical data on fluids from fumaroles (dominated by a mixture of geothermal gases and air or gases from air-saturated meteoric water), and structural analysis of the formation outcropping, we found that anomalous CO2 emissions are positively correlated with shallow temperature anomalies. These are in restricted locations adjacent to vents and fumaroles, where a network of well-connected fractures (preferentially NW-SE and NE-SW orientated and with steep dips) drains efficiently allowing upward migration of the deep fluids and the energy toward the surface.

Evaluation of proppant injection based on a data-driven approach integrating numerical and ensemble learning models

Injecting proppant to prop open fluid-driven fractures in subsurface reservoirs is one of the key missions of hydraulic fracturing. However, quantitative evaluation of the distribution of successfully propped fractures is limited due to the infeasibility of direct measurement. This work defines an indexing parameter for field practice to estimate the proportion of proppant-filled fractures in the reservoir – the proppant filling index (PFI). A new data-driven workflow, combining numerical models and an ensemble learning algorithm, is proposed and trained on field records of both screen-out and near screen-out cases and is then applied to predict PFIs for regular cases. The algorithm performance is promoted via variable importance measure (VIM) analyses and a backward elimination strategy. Four screen-out and twelve regular cases are presented to demonstrate the predicted PFI and highlight its potential utilizations. The new PFI and workflow evaluate the proppant injection quantitatively and reveal any mismatch between proppant injection and underground fractures, which may be essential for post-fracturing analyses and reservoir characterization to improve both oil & gas recovery, the sequestration of CO2, storage then recovery of H2 and the recovery of deep geothermal fluids as important components in enabling the energy transition.

Structural and fluid-migration control on hill-hole pair formation: Evidence from high-resolution 3D seismic data from the SW Barents Sea

Hill-hole pairs are subglacial landforms consisting of thrust-block hills and associated source depressions. Formed by evacuation of material where ice sheets have been locally frozen to the substrate, they give insights into paleo-ice-sheet dynamics. The aim of this study was to document the relationships between ancient hill-hole pairs identified on a buried glacial unconformity with the structure of the underlying sedimentary deposits, and then to determine if the basin geology and glacial fluid migration pathways promoted local subglacial freeze-on during the hill-hole pair formation. The study is based on seismic geomorphological interpretation of four high-resolution 3D seismic cubes covering an area of 800 km2 in the SW Barents Sea, and fluid seepage data from 37 gravity cores.The seismic datasets allowed the identification of 55 hill-hole pairs along the buried unconformity. The hills are characterized by chaotic to homogenous seismic facies forming up to 19 m high mounds, each covering areas of 2000–644,000 m2. The holes form depressions between 1 and 44 m deep and 2000–704,000 m2 in areal extent, which cut into preglacial Mesozoic bedrock and later infilled by glacial till. The holes are often found above fault terminations. High-amplitude reflections identified along the faults and in the strata below the holes are interpreted as shallow gas migrating upward towards the glacial unconformity. Geochemical data of the seabed sediment cores further indicates an association between hill-hole pair occurrence and present-day thermogenic hydrocarbon seepage.The hill-hole pairs geometries were also used to identify five paleo-ice-flow directions along the glacial unconformity. These ice flows exhibit polythermal regimes, and four of them are parallel to ice-stream flow sets interpreted from glacial lineations. The integrated interpretation supports localized fault-related basal freezing of the Barents Sea Ice Sheet which resulted in the formation of hill-hole pairs when the ice sheet moved. In this context, the faults functioned as migration pathways for deep thermogenic fluids, possibly sourced from leaking Jurassic reservoirs.This study highlights the importance of the underlying geology for ice-sheet dynamics: While hill-hole pairs above glacial till appear to be commonly associated with dispersed gas hydrates, hill-hole pairs above bedrock additionally indicate a link to underlying fault systems and hydrocarbon reservoirs. Freeze-on of underlying bedrock to the basal ice along the strike of faults in sedimentary bedrock explains deeper hill-hole pairs with smaller extents along the glacial unconformity compared to areally larger but shallow hill-hole pairs detected above glacial till on modern seabeds. Such close association between paleo-thermogenic gas seepage and the location of hill-hole pairs strongly support that hill-hole pairs are excellent markers revealing exit points of fluid migration pathways in petroleum system models.

Identification of water–rock interaction of surface thermal water in Songwe medium temperature geothermal area, Tanzania

The Songwe geothermal prospect is situated in western Tanzania in the Rukwa Rift of the western branch of the East African Rift System. Thermal springs discharge along NW–SE oriented fracture zones in two separate areas: in the main Songwe graben (Iyola, Main springs, Rambo and Kaguri) and eastern Songwe graben (Ikumbi). Lithologies forming and filling the Songwe graben are metamorphic gneiss and shist as basement rocks, overlain by the Karoo sandstones, and Red sandstones, both silt- and sandstones with a carbonatic matrix. In some areas of the graben, volcanic rocks intruded these formations forming basalt outflows. The discharge temperatures of springs are between 37 and 85 °C with Na-HCO3 type fluids. Carbonate deposits surround most of the springs. Using previous geophysical, geological studies and historical fluid geochemical data and mineral data, the Songwe geothermal system interpretation was updated, including new reservoir fluid temperature, fluid flow pathway and water–rock interaction models. The classical geothermometers of K-Mg and Na-K-Ca (Mg correction) were used to predict the reservoir fluid temperature and show that fluid emerging in the Songwe area reaches temperatures between 125 and 148 °C. Reservoir fluid characteristics are reconstructed based on the geothermometer calculation and a PHREEQC model in which the deep fluid reacts with certain lithologies. Minerals precipitating at the surface and reservoir depth were used to calibrate the models. The models run at surface temperature were calibrated with minerals precipitating around the springs and suggest that Songwe thermal fluids interact with Red sandstone only, while Ikumbi spring water is the only spring that interacts with all lithologies (simplified referred to as: metamorphic rocks, Karoo and Red sandstone). The model run at reservoir temperature indicates that rising water is also in contact with Karoo sandstones and Ikumbi spring water composition is again influenced by the contact with all lithologies in the graben. Our conceptual model summarizes all data showing the meteoric origin of the fluids, the travel through the basement, rising along the Mbeya fault and the main reaction with sandstones through a lateral travel towards the hot springs. The proposed models reinforce the idea that carbonate dissolution from the sandstone layers is the most common water–rock interaction. Our model is supported by carbonate deposition observed in all springs, dominated by HCO3 and Na.

Hydrogeochemical temporal variations related to the recent volcanic eruption at the Cumbre Vieja Volcano, La Palma, Canary Islands

From October 2017, as a response to the occurrence of several seismic swarms on La Palma (Canary Islands, Spain), we strengthened the volcano monitoring of the Cumbre Vieja system by carrying out periodic hydrogeochemical sampling at different points of interest. Two galleries—Peña Horeb (PH) and Trasvase Oeste (TO)—and one well—Las Salinas (LS)—were selected with this objective. Significant temporal variations in the pH, EC, ion content (HCO3−, F−, Cl−, Br−, SO42-, Na+, Ca2+, and Mg2+), partial pressure of carbon dioxide (pCO2), and isotopic signature of dissolved CO2 (δ13C-CO2) were observed throughout the study period. These changes were observed in both chemical and isotopic compositions and were related to the interaction between deep volcanic fluids and groundwaters. They coincided with the occurrence of different seismic swarms, leading to the final Tajogaite volcano eruption, which occurred in Cumbre Vieja from 19 September to 13 December 2021. This work highlights the usefulness of monitoring the chemical and isotopic composition of the groundwaters related to active volcanic systems as they can provide important information about the magmatic gas input in the aquifers.

Sources and migration pathways of methane and light hydrocarbons in the subsurface of the Southern Po River Basin (Northern Italy)

This paper presents new chemical and isotopic data on gases from deep oil and gas fields, bubbling gases, dissolved gases in groundwaters and dry seeps of the Southern Po River Basin (Emilia-Romagna, Italy), aiming to (i) characterize and differentiate the various types of deep natural gases; (ii) identify the source(s) of methane and light hydrocarbons in shallow aquifers and surface gas-rich emissions; (iii) propose a conceptual model of natural fluid migration pathways in the sedimentary prism of the Southern Po River Basin. Based on the isotopic composition of CH4 and C2–C4 n-alkanes, CH4/(C2H6+C3H8) ratio, relative proportion of the C7 hydrocarbons and relative concentration of cyclic compounds with respect to the total cyclic abundance, three main deep reservoirs of hydrocarbons are identified in the subsurface of the Southern Po River Basin: (1) microbial gas hosted in Pliocene-Pleistocene marine sediments, (2) thermogenic gas hosted in Miocene deposits and (3) thermogenic gas produced in Triassic carbonates. Helium isotopes of these deep fluids indicate an almost pure crustal origin (Rc/Ra values = 0.014–0.04), with negligible contributions from mantle-derived helium. A variable contribution of atmosphere-derived fluids is highlighted by low 4He/20Ne (down to 5.42) and 40Ar/36Ar (≤319.5) values. Comparison of chemical and isotopic signatures of deep and surficial hydrocarbon occurrences suggests that methane in shallow groundwaters or gas seeps is sourced by microbial gas migrating upward from deep Plio-Pleistocene reservoirs, with no detectable contributions of Triassic or Miocene thermogenic hydrocarbons. At shallow depths (roughly around 20–50 m.b.g.l.), Plio-Pleistocene microbial methane appears to be mainly stored in anoxic aquifers. However, where CH4 further migrates upwards and reaches aerobic environments (e.g., aquifers or soils), it readily undergoes a process of exothermic microbial oxidation mediated by methanotrophic bacteria. Where the structural architecture of the sedimentary sequence favors the migration of fluids, the methanotrophic biofilter is bypassed and CH4 is discharged through soil diffuse degassing or gas bubbling at water wells. We argue that microbial consumption might be able to bio-sequester significant amounts of Plio-Pleistocene deep-sourced methane in the form of CO2 and biomass. Such process might be widespread in the subsurface of the Southern Po River Basin and, possibly, in other foreland basins worldwide.

Exact solutions for viscous Marangoni spreading.

When surface-active molecules are released at a liquid interface, their spreading dynamics is controlled by Marangoni flows. Though such Marangoni spreading was investigated in different limits, exact solutions remain very few. Here we consider the spreading of an insoluble surfactant along the interface of a deep fluid layer. For two-dimensional Stokes flows, it was recently shown that the nonlinear transport problem can be exactly mapped to a complex Burgers equation[D. Crowdy, SIAM J. Appl. Math. 81, 2526 (2021)]SMJMAP0036-139910.1137/21M1400316. We first present a very simple derivation of this equation. We then provide fully explicit solutions and find that varying the initial surfactant distribution-pulse, hole, or periodic-results in distinct spreading behaviors. By obtaining the fundamental solution, we also discuss the influence of surface diffusion. We identify situations where spreading can be described as an effective diffusion process but observe that this approximation is not generally valid. Finally, the case of a three-dimensional flow with axial symmetry is briefly considered. Our findings should provide reference solutions for Marangoni spreading that may be tested experimentally with fluorescent or photoswitchable surfactants.

Interlaboratory test for chemical analysis of geothermal fluids: A new approach to determine deep geothermal reservoir fluid composition with uncertainty propagation

A representative fluid sampling of surface geothermal manifestations and its analytical data quality assurance and quality control (QA/QC) are challenging aspects of understanding the geothermal reservoir processes. To achieve these goals, an interlaboratory test for the chemical analyses of ten water samples: one synthetic water, two lake waters (i.e., duplicated), one stream water, and six water samples from two geothermal wells of Los Azufres Geothermal field (LAGF), Michoacan, Mexico, was conducted. The geothermal wells were sampled at four points: (1) total discharge of condensed fluid at the wellhead, (2) separate liquid condensed in the well separator, (3) flushed liquid at the weir box, and (4) separated vapor condensed at the well-separator (data taken from Verma et al., 2022). Sixteen laboratories from ten countries reported their results.The pH, electrical conductivity, Ca2+, Li+, SO42−, B, and Si-total measurements were 8.35 ± 0.04, 12.25 ± 0.53 mS/cm, 25 ± 1 mg/l, 18 ± 1 mg/l, 569 ± 33 mg/l, 320 ± 21 mg/l, and 20.5 ± 0.7 mg/l, which are close to the conventional true values, 8.40, 12.31 mS/cm, 23 mg/l, 19 mg/l, 647 mg/l, 330 mg/l, and 20.0 mg/l, respectively. Analytical errors for major ions, Na+, Cl− and CO2-Total are 17, 21, and 42 percent, respectively; however, the analytical uncertainties are relatively lower, except for CO2-Total (19%). Similarly, the analytical uncertainty for CO2-Total measurements of the lake water sample is 18%. Thus, the analytical method of individual laboratories for CO2-Total measurements needs revision.The NIST Uncertainty Machine web app was used for the stepwise geothermal reservoir fluid composition calculation with uncertainty propagation from the samples collected at different points of a geothermal well. The wellhead fluid sample does not represent the geothermal reservoir fluid, including the sample collected by connecting a portable separator at the wellhead. The samples collected at points 2 and 3 represent equally well for non-volatile species; however, the sample collected at point 2 is a better representative of geothermal reservoir fluid in analyzing the pH and alkalinity values. It is associated with considering the effect of non-condensable gases (CO2, H2S, etc.) liberated at the silencer of the weir box. The geothermal reservoir fluid pH uncertainty, an essential parameter for geochemical modeling, is three to four times the measured fluid pH uncertainty due to the propagation process. Thus, the alkalinity measurement and its calculation procedure of geothermal fluid need revision to understand its correction for the boric, silicic, and other alkalinities.

Earthquakes control the impulsive nature of crustal helium degassing to the atmosphere

Deep fluids play active roles during the preparatory phases of large earthquakes and, through their chemical signature, carry information about deep processes within the seismogenic crust. Due to its inertness and isotopic signature, helium (the lightest noble gas) is a useful tracer for investigating the processes of storage and transfer of fluids through the crust, including those prior to hazardous earthquakes. Here we analyse a 12-year earthquake catalogue from the Irpinia Fault Zone, Italy, to compute the 4He outputs from the seismogenetic fault zones (from 104 to 106 mol y−1 with an annual tenfold variability) and compare these with estimates of long-term helium flux. We find that low-magnitude earthquakes (M < 4) efficiently contribute to variations of the crustal helium output into the atmosphere which supports the impulsive nature of He degassing in tectonically active continental regions. We conclude that there is a quantitative relationship between crustal helium outputs and the volume of fault zones, and suggest variations in helium flux may represent a gauge of changes in the stress field that are related to the nucleation of earthquakes.

Role of crustal fluids and thermo-mechanical structure for lower crustal seismicity: The Gargano Promontory (southern Italy)

Several regions around the globe are characterized by a seismically active lower crust, at depths where lithological and thermal conditions suggest stress release by ductile flow. The Gargano Promontory (GP, southern Italy) is an example where a recently installed seismic network has recorded an intense seismic activity at depths between 20 and 30 km, i.e. in the lower crust. The GP is located in proximity of the Gargano-Dubrovnik lineament, a seismogenic zone separating the central and southern Adriatic basins. These two basins constitute sites of sediments accumulation since Tertiary times. Another important basin in the region is represented by the Apennine foredeep, that includes the Candelaro area. We analyze the possible mechanisms controlling the distribution of seismicity in the GP to identify the factors that make the lower crust seismically active. To this aim, we construct a thermo-rheological model of a layered continental crust, calibrated on the basis of geometrical, lithological and thermal constraints. The model takes into account various crustal lithologies, the presence of fluids in the crystalline basement, lateral variations of geotherm and stress field. The numerical simulations show that the presence of fluids is a key factor controlling the cluster of seismicity in the lower crust. Moreover, the presence of water in the upper crystalline basement and sedimentary cover provides a plausible explanation for upper crustal seismicity in a zone of very high heat flow SW of the GP. The distribution of the seismicity is probably affected by the composition of the crystalline basement, with mafic bodies injected into the crust during the Paleocene magmatic phase that affected the Mediterranean region. In addition, fluid accumulation and overpressure may occur along detachment levels in the lower crust, leading to clustering of the earthquakes. Based on our findings, we hypothesize that the presence of hydrous diapiric upwelling(s) in the upper mantle can feed a deep fluid circulation system, inducing lower crustal seismicity. • A thermo-rheological model to explain lower crustal seismicity in the Gargano Promontory (Italy) is presented. • Fluid presence controls the Gargano seismic activity in the lower crust. • The Gargano crust is injected by mafic bodies at various depths.

Fluid Pressure Changes Recorded by Trace Elements in Quartz

AbstractFluid pressure is a key parameter in earthquake mechanics, controlling seismic failure and plate coupling in convergent zones. Yet fluid pressure is also extremely difficult to quantify at seismogenic depth, which limits our knowledge of the stress state in accretionary prisms. Here, we show that the geochemical record of exhumed hydrothermal quartz veins may be used to place quantitative bounds on fluid pressure variations in subduction zones. The studied veins come from sediments accreted and exhumed by plate convergence in southwestern Japan. Quartz in veins displays growth rims of contrasted bright blue/dark brown cathodoluminescence (CL) colors, high/low Al concentrations, and low/high fluid inclusion abundance. Because Si‐Al substitution (and charge compensation by Li) strongly depends on the rate of quartz precipitation and Si solubility, Al‐Li concentrations must be sensitive to fluid pressure. This is confirmed by fluid inclusions, the density of which, converted into trapping pressures, record fluid pressure drops by up to ∼70 MPa from CL‐brown, Al‐Li‐poor rims to CL‐blue, Al‐Li‐rich quartz rims. CL‐blue rims grow at a fast rate, high Si supersaturation and low fluid pressure whereas CL‐brown rims grow at a slower pace, lower Si supersaturation, and higher fluid pressure. Quartz trace element chemistry thus offers a promising tool to quantify deep fluid pressure variations and their relationships to earthquakes.