CO2 Degassing Research Articles

Calcium isotopic geochemistry of geothermal systems in the tectonically active southeastern Tibetan Plateau

The global Calcium (Ca) cycle is closely coupled to the carbon cycle, and Ca isotopes have potential in tracing it. Even though groundwater is one of the main reservoirs of Ca at the Earth's surface, few data are available for groundwater, and the behavior of Ca and its isotopes in geothermal systems remains unknown. Here we analysed the stable Ca and radiogenic Sr isotope compositions of thermal waters distributed along the Jinsha and Yalong river valleys in the southeastern Tibetan Plateau. The Ca isotopic composition of the thermal water ranges from 0.45 to 2.16 ‰ (δ44/40Ca values relative to SRM 915a). The thermal waters collected from carbonate aquifers have higher δ44/40Ca values than bedrocks, which was attributed to secondary carbonate precipitation accompanied by CO2 degassing. In contrast, δ44/40Ca values in thermal waters collected from clastic and igneous rocks are similar to bedrock. Despite some thermal waters undergoing secondary silicates formation and CaNa ion exchange, such processes maybe not play a significant role in governing the Ca isotopic composition of these thermal waters. This suggests that Ca isotopes can be used to trace secondary carbonate precipitation driven by CO2 degassing (e.g. travertine) in geothermal systems located in tectonically active areas.

Volatile characteristics and fluxes of He-CO2 systematics in the southeastern Tibetan Plateau: Constraints on regional seismic activities

The spatial and temporal evolutionary mechanisms of volatile components at plate boundaries and their potential as earthquake precursors are not well understood. Based on observations of He–CO2 from 19 hot-spring gases in the Lancang River fault zone, Yunnan Province, the results show that the volatiles mainly come from the crust. The combined He isotope, He–CO2 relationships, and δ13C–CO2 values of the hot-spring volatiles indicate that it is a mixture of mantle and crustal fluids. These are related to the radiogenic He production caused by crustal U and Th elements with <5% mantle-derived He, whereas C is mainly from the metamorphic decarbonization of Tethyan marine carbonate rocks. Based on the He–CO2 isotopic relationship, crustal volatiles flux with a significant proportion were determined within a non-volcanic area, which was estimated to be 9–132 mol a−1, and CO2 degassing was estimated to be 2–120 × 109 mol a−1. These results are comparable to those of some volcanic areas and large seismically-active fault zones (such as the San Andreas Fault zone). The compressional stress field of the rigid crust near the study area leads to the low permeability of large faults and CO2 degassing from the hydrothermal system, resulting in chemical precipitation that further blocks the shallow crust conduits and deduced overpressure below the hydrothermal reservoir, which may be the cause of the presence of earthquakes with magnitudes greater than 7 in the Lancang River fault zone. The results are significant for elements cycling of converging plate boundaries and earthquake hazards monitoring.

Carbon dynamics at the river–estuarine transition: a comparison among tributaries of Chesapeake Bay

Abstract. Sources and transformation of carbon (C) were quantified using mass balance and ecosystem metabolism data for the upper segments of the James, Pamunkey and Mattaponi estuaries. The goal was to assess the role of external (river inputs and tidal exchange) vs. internal (metabolism) drivers in influencing the forms and fluxes of C. C forms and their response to river discharge differed among the estuaries based on their physiographic setting. The James, which receives the bulk of inputs from upland areas (Piedmont and Mountain), exhibited a higher ratio of inorganic to organic C and larger inputs of particulate organic C (POC). The Pamunkey and Mattaponi receive a greater proportion of inputs from lowland (Coastal Plain) areas, which were characterized by low dissolved inorganic C (DIC) and POC and elevated dissolved organic C (DOC). I anticipated that transport processes would dominate during colder months when discharge is elevated and metabolism is low and that biological processes would predominate in summer, leading to attenuation of C throughputs via degassing of CO2. Contrary to expectations, the highest retention of organic C occurred during periods of high throughput, as elevated discharge resulted in greater loading and retention of POC. In summer, internal cycling of C via production and respiration was large in comparison to external forcing despite the large riverine influence in these upper-estuarine segments. The estuaries were found to be net heterotrophic based on retention of organic C, export of DIC, low primary production relative to respiration and a net flux of CO2 to the atmosphere. In the James, greater contributions from phytoplankton production resulted in a closer balance between production and respiration, with autochthonous production exceeding allochthonous inputs. Combining the mass balance and metabolism data with bioenergetics provided a basis for estimating the proportion of C inputs utilized by the dominant metazoan. The findings suggest that invasive catfish utilize 15 % of total organic C inputs and up to 40 % of allochthonous inputs to the James.

Interplay between abiotic and microbial biofilm-mediated processes for travertine formation: Insights from a thermal spring (Piscine Carletti, Viterbo, Italy).

Active hydrothermal travertine systems are ideal environments to investigate how abiotic and biotic processes affect mineralization mechanisms and mineral fabric formation. In this study, a biogeochemical characterization of waters, dissolved gases, and microbial mats was performed together with a mineralogical investigation on travertine encrustations occurring at the outflow channel of a thermal spring. The comprehensive model, compiled by means of TOUGHREACT computational tool from measured parameters, revealed that mineral phases were differently influenced by either abiotic conditions or microbially driven processes. Microbial mats are shaped by light availability and temperature gradient of waters flowing along the channel. Mineralogical features were homogeneous throughout the system, with euhedral calcite crystals, related to inorganic precipitation induced by CO2 degassing, and calcite shrubs associated with organomineralization processes, thus indicating an indirect microbial participation to the mineral deposition (microbially influenced calcite). The microbial activity played a role in driving calcite redissolution processes, resulting in circular pits on calcite crystal surfaces possibly related to the metabolic activity of sulfur-oxidizing bacteria found at a high relative abundance within the biofilm community. Sulfur oxidation might also explain the occurrence of gypsum crystals embedded in microbial mats, since gypsum precipitation could be induced by a local increase in sulfate concentration mediated by S-oxidizing bacteria, regardless of the overall undersaturated environmental conditions. Moreover, the absence of gypsum dissolution suggested the capability of microbial biofilm in modulating the mobility of chemical species by providing a protective envelope on gypsum crystals.

Fluid origin and critical ore-forming processes for the giant gold mineralization in the Jiaodong Peninsula, China: Constraints from in situ elemental and oxygen isotopic compositions of quartz and LA–ICP–MS analysis of fluid inclusions

The Jiaodong Peninsula, China, is one of the largest gold provinces in the world. During a short time interval in the Early Cretaceous, over 5000 t of gold were accumulated there. The mechanisms controlling the focused Au deposition and the origins of massive amounts of auriferous fluids are still controversial. Quartz–sulfide lode mineralization (Linglong-type) and disseminated/stockwork mineralization (Jiaojia-type) are the two major mineralization styles in the Jiaodong Peninsula. Herein, we conducted in situ textural, elemental and oxygen isotopic analyses using scanning electron microscopy (SEM), laser ablation-inductively coupled plasma-mass spectrometry (LA–ICP–MS) and secondary ion mass spectrometry (SIMS) on quartz from different hydrothermal stages and depths for three representative Linglong-type (Linglong deposit) and Jiaojia-type (Xiadian and Jiangjiayao deposits) gold deposits in the northwestern Jiaodong Peninsula, with the aim to constrain the ore-forming processes. The LA–ICP–MS analysis of individual fluid inclusions was also conducted to unravel the origin of the auriferous fluids. The results show that from the pre-mineralization to the ore-forming stages in the Linglong-type mineralization, the homogenization temperatures and salinities of fluid inclusions and the δ18Oquartz values change slightly, but the Al concentrations of quartz decrease continuously. Combined with the coexistence of CO2- and H2O-rich fluid inclusion endmembers, these trends indicate the increase of pH induced by CO2 degassing (fluid–fluid unmixing), which led to focused Au deposition. The quartz grains from the Jiaojia-type mineralization typically show a homogeneous texture with well-correlated lithophile elements (e.g., K, Al and Rb), which are distinct from those of the Linglong-type that are characterized by oscillatory zoning with much higher Al concentrations and δ18Oquartz values. These phenomena indicate that enhanced fluid–rock interaction occurred in the Jiaojia-type mineralization. In addition, the δ18Oquartz values show an increase from deep to shallow depths. In combination with thermodynamic modelling, it suggests decreasing fluid–rock interaction with decreasing depth. The above results corroborate that multiple mechanisms led to the efficient Au deposition in the Jiaodong Peninsula. Fluid–fluid unmixing typically occurred in the Linglong-type mineralization, while fluid–rock interaction was dominant in the Jiaojia-type mineralization. The different mechanisms might render mining challenging due to the changeable locations of favorable Au unloading.The LA–ICP–MS results of fluid inclusions suggest that the ore-forming fluids are metamorphic fluids rather than magmatic–hydrothermal fluids. In combination with the isotopic compositions of ores showing considerable mantle affinities and large-scale mafic underplating occurring beneath the study region, we propose a new genetic model that accounts for the origin of the auriferous fluids. The new model invokes the devolatilization of previously emplaced H2O- and Au-rich amphibole cumulates through amphibolite- to granulite-facies metamorphism in the middle–lower crust. It suggests an alternative way to generate the ‘orogenic-like’ gold deposits.

Rare Time Series of Hydrothermal Fluids for a Submarine Volcano: 14 Years of Vent Fluid Compositions for Brothers Volcano, Kermadec Arc, New Zealand

AbstractHydrothermal vent fluids from Brothers submarine arc volcano were previously collected in 2004, 2005, and 2017. We present new data from 2018 along with a unique time series of a submarine volcano hosting two distinct types of hydrothermal venting to better understand subsurface processes and how they evolve over time. Samples were collected from known venting locations along the NW Caldera, the Upper and Lower Cone sites, and the newly sampled Upper Caldera site. The NW Caldera wall and Upper Caldera vent fluid compositions are controlled by high-temperature water-rock interactions and phase separation between 2004 and 2018. Fe/Mn molar values suggest that the magmatic impact on all fields has been increasing over time. The Upper Cone has varying influences, including short-term pulses of magmatic degassing, as revealed in K-Mg-SO4 ternary diagrams, Fe/Mn values, and δD and δ18O data. The Lower Cone is dominated by low temperatures and CO2 degassing and shows a pulse in magmatic influence in 2017, followed by a decrease toward earlier conditions in 2018. The 2017 pulse was accompanied by the increase of an enigmatic, soluble MgSO4 phase, potentially due to the “mining” of a magmatic brine sequestered inside the cone. Stable isotope data across the sites indicate pulses of magmatic waters in 2004 and 2017, immediately followed by episodes of more seawater-dominated fluids in 2005 and 2018. Magmatic degassing, phase separation, permeability, and mineral solubility all strongly influence changes in vent fluid composition. This study highlights the dynamic nature of the Brothers volcano hydrothermal system and the changes in fluid chemistry that may affect resultant mineralization.

Olivine in Kimberlites: Magma Evolution from Deep Mantle to Eruption

Abstract Elucidating the origin, composition and physical properties of primary kimberlite melts is crucial to our understanding of their source, petrogenesis, ascent mechanisms and ultimately the origin of diamonds. Recently, there has been a growing interest in the study of olivine, which is one of the most abundant minerals in kimberlites with xenocrystic, metamorphic (mantle) and magmatic origins. Olivine is one of the earliest minerals to crystallise in kimberlite magmas, and the presence of ubiquitous zoning (e.g. cores, internal zones, transitional zones, rims, rinds, outmost rinds) and different generations (i.e. primary, pseudosecondary and secondary) of crystal/melt/fluid inclusions in euhedral olivine grains has been shown to provide fundamental insights into the composition and evolution of kimberlite melts. In this contribution, we review and evaluate the following: (1) the widely accepted notion that kimberlite olivine has two distinct origins—xenocrystic and magmatic. We present detailed electron microprobeX-ray element maps of well-preserved and zoned euhedral olivine microcrysts from the Koala and Mark (Lac de Gras, Canada) and Udachnaya-East (Siberia, Russia) kimberlites to show that the cores of olivine occasionally adopt euhedral shapes, which is commonly defined by the distribution of Ni. We present a scenario in which mantle olivine was recrystallised by the early (or proto-) kimberlite melt/fluid infiltrating through the lithospheric mantle to form euhedral ‘pyrocrysts’ (i.e. olivine that formed via re-crystallisation in the mantle in the presence of a melt), which in turn become cores for the subsequent crystallisation of magmatic olivine during kimberlite magma ascent and emplacement. (2) The evolution of ideas using different geochemical, petrological, experimental and melt inclusion approaches to constrain the composition of the primary/parental kimberlite melt. Based on our assessment of available data, in particular using melt inclusions, we propose that kimberlites originated from melts that were initially Si-poor, and Na-K-F-Cl-P-S-bearing and Ca-Mg-carbonate-rich. With this model composition for the primary/parental kimberlite melt considered, we emphasise the implications for the evolution of olivine and its role in the kimberlite petrogenesis. Furthermore, we present a comprehensive model outlining the key stages involved in the petrogenesis of kimberlites, ranging from the generation of the proto kimberlite melt in the mantle, its interaction with mantle silicates during ascent, the role of liquid immiscibility in driving magma differentiation and CO2 degassing and its emplacement and modification in the crust. Finally, we discuss prospective directions that may further guide the future of kimberlite petrological research.

Eruption of Nyiragongo Volcano in May 2021 degassing of CO2 before and after eruption in the atmosphere

The Nyiragongo volcano is located in the western part of the African Rift. The deep fractures allow the upwelling of gases before and after the eruption, especially carbon dioxide (CO2). We want to understand the behaviour of carbon dioxide before and after the eruption of the Nyiragongo volcano on 22 May 2021. The Nyiragongo volcano erupted on the evening of Saturday 22 May 2021 at 18:15 local time in Goma, about 20 km north of the city of Goma. The lava flowed in two directions from the flanks of the volcano, one flow coming to a halt in the northeastern suburbs of Goma, The other flow cut off one kilometre of the national road 4 linking Goma to Butembo, a major regional road vital for the supply of the city of Goma, causing 32 victims, the production of several volatile gases in the atmosphere, the destruction of 17 villages in the territory of Nyiragongo and the cracking of the ground in the city of Goma and Gisenyi. The Nyiragongo Volcano is infamous for its extremely fluid lava that flows like water when the lava lake flows, which is monitored by the scientific community of the Goma Volcanological Observatory (O.V.G), the lava lake is the seat of an intense gas production. CO2 is a gas that is heavier than air, asphyxiating, and deadly at a concentration of 15%. The variation of CO2 in the different sites allows us to study the behaviour of the Nyiragongo Volcano, one Month before the eruption, the CO2 showed an increasing trend in some sites and a few Months after the eruption we observed a slight decrease in all the CO2 monitoring sites. Nyiragongo is an important contributor of CO2 and SO2 to the troposphere. This 2021 eruption is similar to the one of 17 January 2002, which caused the death of about 100 people and the evacuation of several people. The most deadly eruption of Nyiragongo was in 1977, when more than 600 people died.Post-eruption seismic activity was characterised by a large number of earthquakes of magnitude 3.5 or more. A few earthquakes of magnitudes greater than 3.5 have been recorded by global seismic networks (USGS), the strongest of which had a magnitude of 5.2 in 2002.Compared to other eruptions that Nyiragongo volcano has experienced, the seismic activity before the eruption of 22 May 2021 was not too alarming. This is because there were no strong earthquakes (greater than or equal to 3.5) that preceded the eruption a few months before, as had been noted in previous eruptions. After eruption, exceptional seismic activity was noticed. Many earthquakes of magnitudes greater than or equal to 3.5 were recorded by the local seismographic network. These earthquakes were felt, the strongest having a magnitude of 5.2

Successive Modes of Carbonate Precipitation in Microbialites along the Hydrothermal Spring of La Salsa in Laguna Pastos Grandes (Bolivian Altiplano)

Interpreting the paleoecosystems of ancient microbialites relies on our understanding of how modern microbialites form in relation with the bio-physico-chemical conditions of their environment. In this study, we investigated the formation of modern carbonate microbialites in the hydrothermal system of La Salsa in Laguna Pastos Grandes (Bolivia), which spans a wide range of physicochemical conditions and associated microbial communities. By combining dissolved inorganic carbon (DIC) isotope mass balance modeling, analysis of carbonates solubility diagram, and imaging of the microorganisms–mineral assemblages within microbial mats, we found that several modes of carbonate precipitation dominate in distinct portions of the hydrothermal system. (1) In high-[DIC] waters, undersaturated to slightly saturated with respect to calcite, cyanobacterial calcification is promoted by CO2 degassing and photosynthetic activity within the microbial mats. (2) In alkaline waters undergoing sustained evaporation, the precipitation of an amorphous calcium carbonate phase seems to control the water a(Ca2+)/a(CO32−) ratio and to serve as a precursor to micritic calcite formation in microbial mats. (3) In saline ephemeral ponds, where the carbonate precipitation is the highest, calcite precipitation probably occurs through a different pathway, leading to a different calcite texture, i.e., aggregates of rhombohedral crystals.

Hydrogeochemical characteristics and processes of groundwater in an over 2260 year irrigation district: A comparison between irrigated and nonirrigated areas

A comprehensive understanding of groundwater chemistry and its evolution in irrigation districts is essential for irrigation management. In this study, with emphasis on a comparison between irrigated and nonirrigated areas, the groundwater chemistry and hydrogeochemical processes of a typical irrigation district with an irrigation history of over 2260 years were studied to clarify the effects of long-term irrigation on groundwater quality. Based on 107 water samples collected from across the study area, a comprehensive analysis was conducted using multivariate statistics, stable isotope analysis, and hydrogeochemical modeling. The results showed that the variation range and average concentrations of almost all the ions in the irrigation district are much greater than those in the nonirrigated areas. The groundwater in the nonirrigated areas could be characterized by low TDS and HCO3 or HCO3·SO4 types, whereas the groundwater in the irrigation district could be characterized by complex water types and high TDS. Stable isotopes of hydrogen and oxygen indicated that the groundwater in the irrigation district experienced strong evaporation. The calculated groundwater residence time showed that it takes approximately 2180 years for the groundwater to flow through the irrigation district. Some old irrigation water was present, and it influenced the current groundwater chemistry in the study area. The processes forming the current groundwater chemistry in the irrigation district can be formulated as: mixing → evaporation → water–rock interaction. For mixing, the proportions of rainfall, irrigation water from the Jing River, and lateral recharge from the nonirrigated areas were found to be approximately 30%, 49%, and 21%, respectively. For evaporation, the ratio based on the TDS was 3.83 when comparing the groundwater in the irrigation district with the mixed water after evaporation. Hydrogeochemical modeling showed that the irrigation area is a potential carbon source. The dissolution of halite and gypsum, the precipitation of calcite and dolomite, CO2 degassing and Na-Ca exchange are the main chemical reactions in the geochemical evolution of groundwater. The lesson learned from this irrigation district is that long-term irrigation will lead to salinization and complexity of the groundwater. Hence, in the water resource management of irrigation districts, attention should not only be paid to the balance of water quantity, but also to the balance of salts and the hydrochemical evolution of groundwater.

Origin of the Devonian carbonate-hosted Banbianjie Ge-Zn deposit, Guizhou Province, South China: Geological, mineralogical and geochemical constraints

This paper investigates the origin of the newly discovered Devonian carbonate-hosted Banbianjie Ge-Zn deposit in South China. This deposit is rich in Ge (>900 t @ 110 ppm Ge) and contains 7.7 Mt of sulfide ores at a mean grade of 5.1 wt% Zn. The mineralization is stratabound or veined and is structurally controlled by the E-W trending Huangsi fault. Sulfide ores are dominated by sphalerite and dolomite with subsidiary pyrite, marcasite, and calcite, and minor galena. The mineralization forms massive, veined, brecciated, and disseminated structures and the hydrothermal minerals present in the deposit have colloform, fibrous, granular, and acicular textures. The hydrothermal dolomite has positive Ce (δCe = 1.13–1.20) and negative Eu (δEu = 0.43–0.68) anomalies that are indicative of formation in a weakly acidic, reduced, and low-temperature environment. The δ13CPDB and δ18OSMOW values of the dolomite range from −0.97‰ to −0.24‰ and +13.89‰ to +21.84‰, respectively, indicating that the dissolution of carbonate wall rocks was involved in the formation of hydrothermal dolomite. Theoretical C-O isotopic calculations further suggest that the hydrothermal dolomite formed as a result of water/rock (W/R) interaction and CO2 degassing. The δ34S values of the sulfides (−11.23‰ to −4.95‰) are markedly lower than those of the Devonian seawater sulfate and sulfate from evaporates in the Devonian strata (+21.9‰ to +25.9‰), suggesting that the reduced sulfur was derived from evaporates within the ore-hosting sedimentary rocks by bacterial sulfate reduction (BSR). The Banbianjie sulfides have an upper crustal Pb isotopic affinity, as demonstrated by their 206Pb/204Pb (18.335–18.343), 207Pb/204Pb (15.725–15.735), and 208Pb/204Pb (38.288–38.326) ratios, suggesting the metals were derived from metamorphosed basement rocks. These data suggest that: i) the Banbianjie deposit formed as a result of a combination of weakly acidic, reduced, and epigenetic low temperature mineralized fluids, trap structures, and favorable lithologies; ii) W/R interaction and CO2 degassing caused the precipitation of hydrothermal dolomite, whereas mixing of metals and S2− was the main formation mechanism of the sulfides; and iii) the Banbianjie Ge-Zn deposit is a typical Mississippi Valley-type (MVT) deposit.

Factors controlling the geometry of travertine mounds: Insights from Heinitang (China)

AbstractTravertine mounds are common spring‐constructed landforms with highly variable geometries, but factors controlling their development have not yet been fully understood. To investigate processes linked with their lateral and vertical growth, this study investigated travertine mounds at Heinitang (China) and compared them with typical mounds around the world. Calcium concentration variation modelling and height evaluation of travertine mounds were also performed. The lateral extent of travertine mounds was found to be mainly controlled by Ca2+ and concentrations and water discharge: relatively small metre‐scale mounds, like those from Heinitang, are largely the products of Ca2+‐deficiency (&lt;150 mg L−1, commonly &lt;100 mg L−1) or ‐deficiency (&lt;500 mg L−1) springs with low discharges (&lt;0.1 L s−1), whereas springs with higher Ca2+ and concentrations and discharges give rise to the formation of wider mounds. Additional factors affecting mound lateral development include infiltration, evaporation, micro‐organisms, water cooling, CO2 degassing and flow paths. Height of travertine mounds cannot be simply considered to represent the piezometric surface, because the vertical growth of travertine mounds is also influenced by the water table change triggered by tectonic pulses and climate fluctuations, and the closing of conduits induced by self‐sealing. The extinction of travertine mounds at Heinitang is, for example, probably caused by the water table lowering triggered by earthquakes or climate drying after 4 kyr bp. These findings offer new inputs for the better understanding of factors controlling travertine mound development and might assist in the reconstruction of fluid properties, hydrodynamics, tectonics and climate fluctuations in fossil geothermal systems with travertine mounds.

The impact of outgassing of CO2 and prior calcium precipitation to the isotope composition of calcite precipitated on stalagmites. Implications for reconstructing climate information from proxies

Degassing of CO2 and precipitation of calcite to the surface of stalagmites can strongly impact isotope signals imprinted into the calcite of these speleothems. Here, we show that in all the variety of conditions occurring in nature only two distinct types of degassing exist. First, when a thin film of calcareous solution comes in contact to cave air, which has a lower pCO2 value than that of the aqueous CO2 in the water, molecular CO2 escapes by physical diffusion in several seconds. In a next step lasting several ten seconds, pH and DIC in the solution achieve chemical equilibrium with respect to the CO2 in the cave atmosphere. This solution becomes supersaturated with respect to calcite. During precipitation for each unit CaCO3 deposited one molecule of CO2 is generated and escapes from the solution. This precipitation driven degassing is active during precipitation only. We show that all variations of out gassing proposed in the literature are either diffusive outgassing or precipitation driven degassing and that diffusive outgassing has no influence on the isotope composition of the HCO3− pool and consequently on that of calcite. Its isotope imprint is determined solely by precipitation driven degassing in contrast to most explanations in the literature. We present a theoretical model of δ13C and δ18O that explains the contributions of various parameters such as changes in temperature, changes of pCO2 in the cave atmosphere, and changes in the drip intervals to the isotope composition of calcite precipitated to the apex of the stalagmite. We use this model to calculate quantitatively changes of δ13C and δ18O observed in field experiments (Carlson et al., 2020) in agreement to their experimental data. We also apply our model to prior calcite precipitation (PCP) in the field as reported by Mickler et al. (2019). We discuss how PCP influences isotope composition signals. In summary, we present a transparent method based on few commonly accepted equations that allows calculation of the isotope composition δ13C and δ18O of CaCO3 under various temperatures, pCO2 in the cave air, degrees of PCP, and concentrations cCao of the water entering the cave.

Addressing the root cause of calcite precipitation that leads to energy loss in geothermal systems

Geothermal sources are an essential energy resource in many cities around the world, in which a deep hot water reservoir has two energetic bases: thermal and hydraulic. The use of this energy can produce both electricity and heat. A geothermal well is a way in which the energy flows from the reservoir to the surface. A known operational problem can directly consume hydraulic energy and indirectly consume thermal energy. Calcium carbonate (CaCO3) precipitation and scaling can reduce and even block the flow area of a geothermal well, deferring, degrading, or even closing the production of water, steam, heat, and power. CO2 degassing, which is intrinsic to the deepwater system, is often the cause of this problem. This relationship is evident in the chemical balance: Ca2+(aq) + 2 HCO3–(aq) ⇆ H2O + CaCO3(s) + CO2(aq). With the head loss provided by the water flow, CO2(aq) changes to the gaseous state (CO2(aq) → CO2(g)), which disfavors the CaCO3 dissolution and implies its mineralization. The CO2(aq) closely links the two mentioned chemical reactions and makes them mutually dependent. Therefore, two causes favor the CaCO3 precipitation: changes in thermodynamic conditions (pressure and temperature) and CO2 exsolution. It takes place even if the hot water is not boiling or flashing. This paper aims to quantify these two causes by applying our techniques in some geothermal fields in different locations in the world. In all scenarios investigated, the release of CO2 contributes from 66.1% to 92.6% of the CaCO3 precipitation. These results can lead engineers to adequately remedy the problem and suitably design and operate a geothermal system as a whole.

Dispersed Carbon in Basalts of the Altered Oceanic Crust: Isotope Composition and Mechanisms of Formation

Carbon contents and isotopic compositions were compared in the basalt groundmass of the oceanic crust of different age in the zone of the East Pacific Rise. In samples the basalt groundmass of the ancient oceanic crust (~270 Ma, ODP Site 801C) in which a carbonate phase was found, the isotopic composition of the oxidized carbon (δ13C = ±1.5‰) indicates that this carbon was formed by the precipitation of seawater dissolved inorganic carbon (DIC). In the samples in which no carbonate phase was identified, the low concentration (<0.1 wt % CO2) of oxidized dispersed carbon and its isotopic composition (δ13C < –7‰) are in the range of values typical of carbon dissolved in basalt glasses without crystallinity. This makes it possible to relate the oxidized dispersed carbon to residual carbon dissolved in the magmatic melt after CO2 degassing. The precipitation of DIC results in a positive correlation between the concentration of total carbon and its δ13C values, along with the formation of a carbonate phase. The application of this criterion to basalt groundmass samples of the young crust (~15 Ma, ODP Site 1256D) showed that oxidized dispersed carbon in the young oceanic crust groundmass was not formed by the precipitation of DIC, contradicting the generally accepted paradigm. Constant concentration and δ13C values of the reduced dispersed carbon in the basalt groundmass of the young and ancient oceanic crusts, including lithological zones where microbial activity has not been recorded, indicate that the most probable model is high-temperature abiogenic generation of reduced dispersed carbon near the ridge axis. The Fischer–Tropsch synthesis and/or Bell–Boudouard reaction provide a possible basis for the abiogenic model. The Bell–Boudouard reaction 2CO = C + CO2 leads to the formation of an adsorbed layer of elemental carbon on the fresh surfaces of minerals during background alteration of the oceanic basalt crust. The CO2–CO gas-phase equilibrium maintains the necessary depletion of the newly formed elemental carbon in the 13C isotope to δ13C < –20‰. Abiogenic models for the origin of the isotopically light reduced dispersed carbon in the basalt groundmass do not assume the presence of carbon depleted in the heavy 13C isotope in the magmatic melt.

Chemical and isotopic composition of CO2-rich magnesium-sodium-bicarbonate-sulphate-type mineral waters from volcanoclastic aquifer in Rogaška Slatina, Slovenia.

Bottled natural mineral waters from an andesitic aquifer in Slovenia are enriched in magnesium (1.1 g/l), sulphate (2.2 g/l) and dissolved inorganic carbon (204 g/l). We analysed major ions, trace elements, tritium activity, 14C, δ18OH2O, δ2HH2O, δ13CDIC, gas composition and noble gases in six wells. In addition, 87Sr//86Sr, δ34SSO4 and δ11B were analysed here for the first time. Stable isotopes with δ18O = −11.97 to −10.30‰ and δ2H = −77.3 to −63.8 confirm meteoric origin. CO2 degassing is evident at three wells, causing the oxygen shift of about −1.3‰. Tritium activity was detectable only in the shallowest well, where the freshwater component was dated to the 1960s. δ13CDIC in five waters is −1.78 to + 1.33‰, typical of carbonate dissolution. Radiocarbon is low, 1.03–5.16 pMC. Chemical correction with bicarbonate concentration and δ13C correction methods gave best mean residence times, slightly longer than previously published. Sulphate has δ34S 26.6–28.9‰ and δ18O 8.9–11.1‰ due to dissolution of evaporites in carbonate rocks. Boron at concentrations of 1.2–6.1 mg/l has two origins: δ11B = 11.3–16.4‰ from hydrothermal alteration and δ11B = 26.6–31.7‰ from carbonate dissolution. Strontium at concentrations of 0.5–22.0 mg/l has 87Sr//86Sr, indicating three sources: 0.7106 for Miocene clastic rocks, 0.7082 for Triassic carbonates and 0.7070 for Lower Oligocene andesitic rocks. CO2 represents the majority of the dissolved (> 98.84 vol%) and separated gas (> 95.23 vol%). Methane is only found in two wells with a max. of 0.30 vol%. All waters show excess helium and 16–97% of mantle-derived helium. Since all show subsurface degassing, the paleo-infiltration temperature could not be calculated.

Deciphering the hydroclimatic significance of dripwater δ13CDIC variations in monsoonal China based on modern cave monitoring

Stable carbon isotopic composition (δ13C) of speleothems has often been recognized as a proxy of vegetation and soil processes in many climatic regimes. In monsoonal regions, the speleothem δ13C records are thought to be able to document changes in local and/or regional precipitation as well. Due to the complexity of carbon isotopic evolution within heterogeneous karst aquifers, accurate interpretations of this proxy are challenging. It is essential to carry out detailed monitoring of cave dripwater δ13CDIC to disentangle various processes governing carbon isotopic evolution and decipher the hydroclimatic constraints. Here, we reported the results of a five-year monitoring of the δ13CDIC as well as hydrochemical compositions of dripwaters in the Maomaotou Big Cave, Guilin, South China. Great spatiotemporal variations in the dripwater δ13CDIC values were observed: (i) seepage flow-fed drips commonly had lower δ13CDIC values, with smaller temporal variation; (ii) the lowest δ13CDIC values were found at fracture-fed drips that had a large supply of soil CO2, whereas the fracture-fed drips with less, episodic CO2 recharge had much more positive δ13CDIC; (iii) the δ13CDIC exhibits remarkable season changes, particularly at fracture-fed drips where higher δ13CDIC values were observed in winter seasons; and (iv) an increasing trend in mean value of δ13CDIC at individual sites during 2015–2019 was found. Both hydrochemical and isotopic analyses revealed that the dripwater δ13CDIC is mainly controlled by spatiotemporal variations in water-CO2-rock interactions in association with hydrological processes, coupled with soil CO2 dynamics, which are closely linked to changes in local rainfall at monthly to annual timescales. Prior calcite precipitation (PCP) along the flow path above the cave could also affect the δ13CDIC of fracture-fed dripwaters in dry periods. Comparisons of the dripwater δ13CDIC records with local climate showed that the change of summer monsoonal rainfall, particularly the August-September-October precipitation, significantly influences the annual mean δ13CDIC value of dripwaters in caves of South China. Further comparison analyses of dripwater δ13CDIC records from both southern and northern China suggested that variations of dripwater δ13CDIC could reflect changes of regional monsoonal precipitation over inter-annual (and maybe decadal) timescale. This demonstrates that the δ13C of speleothems, if precipitated at isotopic equilibrium and not greatly influenced by the CO2 degassing, is likely to be a valuable proxy of monsoon rainfall variability across East Asia.

Microbial contribution to early marine cementation

AbstractThe origin of early marine cements is still being debated as either abiotic, triggered by evaporation and CO2 degassing, or microbially‐mediated. In particular, micritic envelopes and micritic meniscus cements have been proposed to be microbially‐mediated but the microbial community and the resulting organomineralization processes have rarely been documented. Herein, scanning electron microscopy and thin section analyses of samples from the Bahamas and Hamelin Pool, Australia, provide evidence that early cements in intergranular areas are the result of organomineralization processes driven by both active (microbial metabolism) and passive mechanisms influenced by mucilaginous extracellular polymeric substances and/or microbial cell walls acting as matrices for crystal nucleation and growth. Signatures of biogenicity are supported by the conspicuous presence of early micritic cements in association with dense filamentous fabrics and entombed microbial forms. Most importantly, the prolific colonization of metabolically active communities, many of which assist in carbonate precipitation, trapping, binding and encrustation of the grains, testifies to the contribution of microbes in early cementation processes. The extent and ubiquity of mucilaginous extracellular polymeric substances and its concomitant association with amorphous calcium carbonate nanograins indicates that passive organomineralization via an intermediary amorphous phase is the other leading process for the generation of micrite and fine mesh of aragonite needle‐like crystals. Furthermore, the conspicuous occurrence of microbially‐mediated micrite, meniscus and bridging cements, as well as microcrystalline Mg‐calcite cement in the marine phreatic realm challenges the widespread notion that these fabrics are indicative of marine vadose or quiet marine phreatic environments. All analyzed samples show a remarkable similarity in early cement fabrics and a consistent superposition of prismatic cements on the micrite meniscus and bridging cements. These microbially‐mediated micritic cements represent the first generation of marine cements upon which aragonite and high‐Mg calcite develop.

Fluid inclusion and C-O isotopic constrains on the origin and evolution of ore-forming fluids of the Badaguan Cu-Mo deposit, Inner Mongolia

The Badaguan porphyry Cu–Mo deposit is located in the Derbugan metallogenic belt. Aqueous (W-type), CO2-rich (WC-type), vapor-rich (V-type), and daughter mineral–bearing inclusions (S-type) were recognized in the hydrothermal quartz. Fluid inclusions in the early stage show high homogenization temperatures (247–374 ℃) and high pressures (66–191 MPa), with salinities of 0.95–12.15 wt% NaCl equiv. The presence of anhydrite in veins and phenocrysts suggests high oxygen fugacity conditions. The veins in the Mo- and Cu mineralization stages were formed by immiscible fluids at temperatures of 244–366 ℃ and 183–342 ℃, and pressures of 39–137 MPa and 30–98 MPa, respectively. They yielded salinities of 1.69–10.52 and 0.35–6.85 wt% NaCl equiv, respectively. Homogenization temperatures of fluid inclusions in late stage range from 194 to 269 ℃ with a salinity of 0.6–5.88 wt% NaCl equiv. It is concluded that the ore-forming fluids in the early stage were magmatic in origin, then gradually diluted and cooled by meteoric water. During this process, fluid immiscibility and CO2 release induced by pressure drop and oxygen fugacity decrease resulted in Mo mineralization, while temperature drop was the main trigger for the precipitation of chalcopyrite. Laser-Raman analyses suggest that the fluid inclusions of the Badaguan porphyry Cu-Mo deposit in Inner Mongolia are rich in CO2. Minor CH4 occurs in the Mo- and Cu-mineralization stage, which may be generated during water–rock interaction. The hybrid carbon isotope compositions of the fluid inclusions, mainly representing CO2, show a very depleted δ13CPDB (−21‰ to −28.3‰), which can be explained by the joint influence of ~ 0.5% subducted oceanic sedimentary contamination in the mantle and carbon isotope fractionation induced by 35–80% CO2 degassing. Petrographic observation, previous studies on the geochemical and isotopic characteristics of ore-causative rocks rule out the possibility of contamination of ascending magma with reducing wall rocks. The large variations in δ18Owater (−6.6‰ to +2.4‰) for quartz and calcite suggest the participation of meteoric water during water–rock interaction.

Aquifer (Hydrogeological) Study of Southern Areas of Prayagraj, India

The physical and chemical characteristics of spring and well water samples were studied for two years to assess the origin of groundwater and determine the factors driving the geochemical composition. The ionic speciation and mineral dissolution/precipitation were calculated. Water wells, characterising groundwater circulation at shallow depths are moderate to high mineralised waters of Na-HCO3 type. In contrast to the shallow environment, the CO2-rich, deeper water is of the Ca-HCO3-SO4 type and undergoes significant changes in the baseline chemistry along flow lines with increasing residence time. The main factors controlling the groundwater composition and its seasonal variations are the geology, because of the presence of carbonate formations, the elevation and the rate of karst development. In both groups, the carbonate chemistry was a diagnostic approach. The super-saturation with respect to calcite indicates CO2 degassing, occurring either inside the aquifer in open conduits or at the outlet in reservoirs. Interaction between groundwater and surrounding rocks is believed to be the main process responsible for the observed chemical characteristics of groundwater in the study area. Mathematical equations were also derived involving the hydro geological variables for better prediction of the aquifer.