Fluid-rock Interaction Research Articles

Evaluation of rock-fluid interaction in a carbonate reservoir: Backflow test and reactive transport simulations

Water injection is one of the most used secondary oil recovery methods. However, when injected into a carbonate reservoir, it disturbs the equilibrium between the porous rock and the formation water, altering the geochemical system. The aim of this work is to evaluate the rock-fluid chemical interaction associated with seawater injection into a carbonate reservoir, based on field flow tests and flow simulations using COORES™ and ARXIM. Though previous studies were carried out under laboratory conditions, in this work, for the first time, rock-fluid interaction was observed and quantified during a field test in a high-temperature and high-pressure reservoir. Chemical analysis of produced water during the flow test showed that calcium and alkalis concentrations were higher than those calculated by the simple mixture of injected and formation waters, confirming the existence of chemical reactions under reservoir conditions. Reactive transport simulations were used to determine kinetic parameters related to calcite dissolution and dolomite precipitation in the reservoir. The results of this study enhance the understating of chemical interactions between injected fluids and carbonate reservoirs and provide data for more reliable simulations. These could lead to more accurate predictions regarding produced water composition and pH, anticipating the likelihood of reservoir collapse and scaling issues.

Fluid–rock interaction in the basement granitoids: A plausible answer to recurring seismicity

The Koyna–Warna Seismogenic Region in the western part of the Indian Subcontinent has been recognized as one of the most significant sites of Reservoir–Triggered–Seismicity (RTS) during the last five decades. The basement granitoids, overlain by the porous and vesicular Deccan Trap basalt, contain numerous interconnecting fractures which act as the ascending and descending pathways of fluid flow. As a result of this fluid flow along fractures, the host rock has been subjected to significant chemical alteration along with the subsequent formation of some new minerals at the expense of a few other pre–existing mineral phases. Mesoscopic observations followed by Optical microscopy in the core samples of the basement rocks upto 1.5 km depth retrieved from the borehole KBH1 near Rasati (about 4.7 km from the Koyna Dam) have revealed the presence of chlorite and the precipitation of calcite, whereas the bulk mineralogical XRD has reaffirmed the presence of chlorite, calcite along with illite at a certain depth. This entire secondary mineral assemblage resembles the propylitic kind of hydrothermal alteration at temperatures < 350°C under acid–to–neutral solution conditions and also indicates water channelization up to the deeper level in the basement granitoids (>1.5 km). In addition, the presence of the hydrophilic clay minerals along fault and fracture zones may be responsible for triggering the seismicity in the Koyna Seismogenic Region as their absorption of water reduces the shear strength of faults and their low frictional strength accelerates the fault weakening process causing the generation of slip surfaces. Thus, in addition to several seismotectonic features, fault geometry and existing stress pattern, the clay mineralisation along the pre–existing faults and fractures of the basement rocks may also be a factor behind the recurring seismicity in this region.

Lithium enrichment processes in sedimentary formation waters

Reservoirs exploited for oil, gas, or geothermal energy in sedimentary basins may represent an alternative lithium resource to salars and hard rocks. Similarities in the geochemical characteristics of the basins were searched using a database of 2400 water analyses available from more than 40 sedimentary basins worldwide, notably a selection of representative geochemical trends on 13 basins. The objective was to understand better the factors controlling Li concentrations and the potentiality of such basins for the Li-recovery. Considering LiCl and MgCl relationships, major cation (Na/K, Na/Ca) and halogen (Cl/Br) ratios, Li concentrations are monitored in several basins by mixing processes between low salinity recharge waters, seawater and brines. Lithium concentrations span three orders of magnitude in brines between evaporated seawater that has passed saturation with halite and a particularly Li-enriched pole. In the latter, significant Li-enrichment is obtained when brines are primary, in equilibrium with halite, and then enriched in Li through fluid-rock interaction processes. Li-rich lithologies such as volcanic rocks, Li-enriched clay formations, or Li-phyllosilicates dispersed in siliciclastic rocks or the underlying crystalline basement probably act as the primary Li sources. Finally, Li extraction is promoted by the rise in temperature, which explains the high Li concentrations in the waters of geothermal systems. Therefore, favourable reservoirs for Li-rich brines are characterised by a brine collection from evaporites during tectonic events, such as compressive events or salt tectonics, at a relatively short distance from the present reservoir. They must be preserved from convection and surface water ingress via recharge zones to prevent dilution and Li depletion.

Disseminated gold mineralization under varied redox conditions: Constraints from microscopic observation, geochemistry, and thermodynamic modeling on fluid-rock interactions in lamprophyres, Zhenyuan gold deposit

The controls of fluid redox states on disseminated gold mineralization remain ambiguous. To address this, this study compared the hydrothermal alteration and auriferous pyrite geochemistry in lamprophyres, Zhenyuan gold deposit, which were infiltrated by fluids with varied redox states. Vein-A, vein-B, and vein-C were distinguished and they contain different sulfur-bearing minerals, i.e. pyrite, pyrite and barite, and barite, respectively. This suggests the gradual oxidzing formation conditions from vein-A to vein-C. Alteration halos enveloping vein-A and vein-B develop disseminated pyrite. In the vein-A halos, alteration minerals transit from pyrite to Fe‑carbonates outwards, which was well replicated by the thermodynamic simulation of the successive reaction of H2O-CO2-H2S-Au-bearing fluid with lamprophyres. The precipitation of pyrite grains in vein-B halos is farther from vein-B, suggesting progressive fluid-rock interaction (FRI) first induced the reduction of oxidized S followed by the pyrite precipitation. Additionally, δ34S values of pyrite are more scattered in vein-B halos (−8.0 to 4.7‰) than in vein-B, vein-A, and vein-A halos, implying the sulfate-sulfide disequilibrium. Pyrite in vein-B halos displays higher As concentrations than that in vein-A halos due to the strong redox dependence of As partition from fluids to pyrite. Au and Au/As of halo-hosted pyrite grains decrease outwards, and pyrite in vein-B halos has low Au and Au/As (below 93.93 ppm and 0.005, respectively) compared to that in vein-A halos (below 1597.08 ppm and 0.031, respectively). It is thus suggested that Au concentrations in ore fluids decreased during outwards FRI, and the lack of pyrite grains in proximal alteration zones results in lower gold concentration in pyrite under relatively oxidized conditions. This study reveals that the fluid redox conditions can affect As concentrations and spatial distribution of pyrite in alteration halos, which directly controls invisible gold precipitation.

Multiwell Fiber Optic Sensing Reveals Effects of CO2 Flow on Triggered Seismicity

Abstract Induced seismicity is one of the main risks for gigaton-scale geological storage of carbon dioxide (CO2). Thus, passive seismic monitoring is often recommended as a necessary component of the monitoring systems for CO2 storage projects, with a particular forcus on risk mitigation. We present the first field study, CO2CRC Otway Project Stage 3 (Victoria, Australia), where distributed acoustic sensing (DAS) enabled high-precision tracking of the induced seismicity triggered by a small CO2 injection and also informed the reservoir models. In 610 days of passive seismic monitoring of the Stage 3 injection, we detected 17 microseismic events (maximum moment magnitude Mw 0.1) using five deep boreholes equipped with enhanced-sensitivity optical fiber. The DAS array has sensitivity sufficient for detection and location of induced events with Mw∼−2 in a monitoring borehole located up to 1500 m away. Thanks to the dense spatial sampling by the DAS, we were able to estimate the focal mechanisms for events with Mw>−1.5; although the monitoring boreholes provided very limited angular coverage. The main cluster of the events has the same location and source mechanism as the one triggered by the previous CO2 injection at the Otway Project site, Stage 2C. Surprizingly, the Stage 2C and Stage 3 events closely followed the actual movement of the CO2 saturation plume front (not the pressure front), as observed using controlled-source reflection seismic images. The nature of the plume-fault interaction remains unclear, but some alteration of the fault gouge by CO2 might be responsible for the faults’ reactivation by the pressure perturbation. Importantly, the seismogenic fault could not be identified in the seismic images and was only revealed by DAS observations, which also demonstrated the signature of fluid–rock interaction, that may control the CO2 flow.

Early diagenetic mobilization of rare earth elements and implications for the Ce anomaly as a redox proxy

The Rare Earth Elements (REE) archived in carbonate rocks retain a wealth of information on paleo-seawater chemistry and local-regional redox conditions. However, interpretations are often ambiguous due to the potential for REE remobilization in marine environments. In this regard, many carbonate rocks that retain primary seawater isotopic signatures exhibit non-seawater-like REE patterns, implying either unusual REE behaviour in seawater or diagenetic overprinting of otherwise well-preserved rock samples. Here, we apply sequential leaching to constrain the possible effects of different REE-bearing phases on measured carbonate REE patterns in order to address this quandary. Our results show that the exchangeable phase contains negligible REE, but could be an important host phase for other elements such as Sr, Ba and K. The acidified hydroxylamine hydrochloride leach is shown here not only to dissolve Fe–Mn oxides but also phosphate minerals, which induces middle REE enrichment in corresponding leachates of dolostone samples in our study. The demonstrable Fe–Mn oxide phase in limestone samples is characterized by middle and/or light REE enrichment and positive Eu anomalies, which are attributed to hydrothermal processes and continuing exchange with marine fluids after initial precipitation. The non-seawater-like REE patterns observed in the carbonate phase of otherwise well-preserved limestones resemble those of the co-existing Fe–Mn oxide fraction, and are interpreted to reflect the dissolution of REE carrier phases during early diagenesis. This view is supported by fluid-rock interaction modelling, which shows how REE can be mobilized at relatively low fluid/rock ratios in shallow porewaters. Non-seawater-like REE patterns may therefore be caused by the incorporation of REE from shallow porewaters before final lithification due to an elevated flux of particulate REE carrier phases, e.g. Fe–Mn oxides and organic matter, to the seafloor. In spite of the sensitivity of carbonate REE patterns to early diagenetic exchange, the co-occurrence of non-seawater-like patterns with primary strontium and carbon isotope values suggests that REE should not be viewed as a general indicator for the preservation of other geochemical proxies. Importantly, Ce anomalies of the carbonate phase will also be affected by porewaters, masking primary seawater values. Our results favour a reevaluation of redox interpretations by taking into account REE patterns as a whole.

Genesis of Tertiary Akçakışla vein-type Pb-Zn-Cu mineralisation (Central Anatolia, Turkey): Evidence from fluid inclusion and O, H, S, Pb-isotope compositions

The Akçakışla Pb–Zn–Cu vein type deposit is one of the active mining deposits located in the Akdağmadeni (Yozgat) metallogenic province in Turkey. The sulfide vein deposit, trending E-W, is hosted by calcschist of the Akçakışla and Topaktaş formations of Akdağmadeni metamorphites, which are intruded by the Central Anatolian granitoids and overlain by sedimentary and Tertiary volcanic rocks. Microthermometric measurements indicate that the Pb-Zn-Cu deposit formed by hydrothermal fluids containing dissolved CaCl2, MgCl2 and NaCl. A mixing of fluids with greatly varying salinities and temperatures is shown by the wide range of calculated salinity (0.2–10.4%) and temperature (170–400 °C) values. Isotope ratios of oxygen (δ18OH2O = −5.09 to +4.71‰) and hydrogen (δD = −67‰ and −82‰) suggest that water in hydrothermal fluid might be either mixing of meteoric and magmatic waters or meteoric water that oxygen isotope composition was modified by fluid-rock interaction. Sulphide minerals exhibit δ34S values ranging from 5.51‰ to 8.40‰, which assume a magmatic sulphur source modified by assimilation of upper crustal material (possibly the host metamorphites). In galena from the studied Akçakışla Pb–Zn–Cu deposit ratios of 206Pb/204Pb (18.783–18.821),207Pb/204Pb (15.654–15.700) and 208Pb/204Pb (38.874–39.039) suggest a mixture of lead sources from orogenic-upper crust materials. We assume that hydrothermal fluids dissolved the sulphur from the intruded granitoids and the lead from the host metamorphites. The galena Pb model ages values point out two different ore forming ages; suggesting initial formation in upper Cretaceous (87 Ma) and highly reworking in Eocene–Oligocene (23 and 39 Ma).

Magnesium–oxygen isotope constraints on the origin of rodingites in oceanic lithosphere

Rodingite is produced by Ca-rich fluid metasomatism of mafic igneous rocks in oceanic lithosphere. Despite its importance for the composition of subduction zone magmas, its formation mechanism still remains obscure. To address this issue, we investigated the major-trace element and Mg–O–Sr–Nd isotope compositions of rodingites in serpentinites from the Xigaze ophiolite, southern Tibet. Coexisting gabbros and rodingites show consistently depleted SrNd isotope compositions, suggesting their formation in a mid-ocean ridge setting. The rodingites exhibit variable δ26Mg values from −0.61‰ to −0.14‰, with an average of −0.37‰ ± 0.28‰ (n = 19; 2 SD), mostly lower than those of −0.26‰ to −0.13‰ for the protolith gabbros. Compared to the relatively homogeneous δ18O values of 6.1‰–6.7‰ for the gabbros, the rodingites show highly variable δ18O values from 3.8‰ to 9.4‰. The rodingites can be subdivided into two groups based on mineral assemblages and formation conditions. Group I rodingite is prehnite-dominated and hydrogarnet-free, formed at temperatures of 200–300 °C, and has higher δ18O values of 8.1‰ ± 1.4‰ (n = 15) and δ26Mg values of −0.32‰ ± 0.19‰ (n = 12). Group II rodingite consists mainly of hydrogarnet and clinopyroxene, formed at temperatures of 300–400 °C, and has lower δ18O values of 5.4‰ ± 2.5‰ (n = 7) and δ26Mg values of −0.44‰ ± 0.35‰ (n = 7). Modeling of the fluid–rock interactions between the protolith gabbro and fluid was undertaken using the MgO isotope compositions of the serpentinizing fluid inferred from the associated serpentinites. Based on the modeling results, we propose that the metasomatism of gabbros by Ca-rich, low-δ26Mg fluids produced during serpentinization would result in the MgO isotope compositions of the rodingites. Such rodingites with low δ26Mg values would generate the geochemical heterogeneity in the mantle wedge overlying the subducting oceanic lithosphere and eventually give rise to Ca-rich, low-δ26Mg basaltic magmas. The results indicate that low δ26Mg values of basaltic rocks cannot be unambiguously ascribed to carbonated mantle sources.

Triple-halogen (Cl-Br-I) fluid inclusion LA-ICP-MS microanalysis to unravel iodine behavior and sources during marine fluid infiltration into the basement in unconformity settings

Halogen signatures of hydrothermal fluids are a powerful tool for deciphering fluid provenance and reconstruction of key ore-forming mechanisms such as fluid mixing processes. Analytical protocols for LA-ICP-MS fluid inclusion analysis of Cl and Br concentrations have existed for over 10 years, but Br/Cl ratios alone do not provide unambiguous evidence of fluid provenance. However, recent methodological advances now allow also for quantification of I by LA-ICP-MS analysis in single fluid inclusions, significantly expanding the applicability of halogens for unambiguous fluid provenance analysis. However, owing to the novelty of the fluid inclusion triple-halogen LA-ICP-MS method, and due to the notorious difficulties caused by the generally low I concentrations in hydrothermal fluids, reference Cl-Br-I data of many crustal fluid types remains scarce, even when including data from bulk analytical techniques. Single fluid inclusion halogene analytics as are used here are vital due to the lack of sampling bias inherent to bulk analytical techniques that narrow the analyzed compositional range.The evaluation of Cl, Br and I systematics of fluid inclusions from unconformity-related hydrothermal veins in the Schwarzwald, Germany, provides new insight into the behavior of I and the evolution and source of the fluids involved in formation of unconformity-type vein deposits in central Europe during the Triassic to Cretaceous. While the variation in Br/Cl (molar ratio: 0.1 × 10−3–8.3 × 10−3) is consistent with previously established models of mixing processes between two fluids with a salinity source in seawater evaporation (modified bittern brine) and halite dissolution (modified halite dissolution brine), respectively, the large scattering of I/Cl (molar ratio: 1.4 × 10−6–330 × 10−6) cannot be attributed to the salinity source alone. Instead, I must have been derived from interaction with organic matter, which appears to have been more pronounced within the modified bittern brine fluid endmember. During fluid infiltration into the basement and associated fluid-rock interaction, I/Cl and Br/Cl acted conservatively on analytically detectable scales and large inhomogeneities in source I signatures remained intact. This finding also presents direct evidence of local fluid composition inhomogeneity and absence of internal mixing of basement reservoirs for long time periods (more than 100 Ma).

A DFN-based framework for probabilistic assessment of groundwater contamination in fractured aquifers

It is challenging to conduct groundwater contamination risk assessment in fractured aquifers containing a large number of complex fractures, especially in a situation where the uncertainty of massive fractures and fluid-rock interactions is inevitable. In this study, a novel probabilistic assessment framework based on discrete fracture network (DFN) modeling is proposed to assess the uncertainty of groundwater contamination in fractured aquifers. The Monte Carlo simulation technique is employed to quantify the uncertainty of fracture geometry, and the environmental and health risks of the contaminated site are probabilistically analyzed in conjunction with the water quality index (WQI) and hazard index (HI). The results show that the contaminant transport behavior in fractured aquifers can be strongly affected by the distribution of the fracture network. The proposed framework of groundwater contamination risk assessment is capable of practically accounting for the uncertainties involved in the mass transport process and effectively assessing the contamination risk of fractured aquifers.

Mineralogy and Geochemistry of Nepheline Syenite From the Bang Phuc Massif of the Alkaline Cho Don Complex in North-Eastern Vietnam—Implications for Magma Evolution and Fluid–Rock Interactions

Abstract The alkaline Cho Don complex in NE Vietnam comprises several mafic-felsic suites related to the widespread magmatism developed during the early Permian–late Triassic. The contribution explores the petrogenesis of nepheline syenite from the Bang Phuc massif and its petrogenetic relationship with cogenetic scapolite-rich gabbro. The nepheline syenite formed through fractional crystallization of pristine mantle-derived basaltic melt modified by subduction-related components (chiefly sediment-derived melts), as shown by, e.g. low Ba/Th and high Th/Nb ratios of the rocks. The transition from gabbro to syenite follows a within-plate enrichment trend (e.g. increasing Ta/Yb, Nb/Yb, and Th/Yb ratios) that might reflect switch from post-orogenic to intra-plate regimes, accompanied by subduction–collision–extension events related to the Indosinian Orogeny. Furthermore, magma evolution involved the progressive contribution of asthenospheric-derived melts that resulted in the appearance of OIB-like signatures (e.g. high Nb/La ratios) in the nepheline syenite. Fractional crystallization of fluorapatite and mafic phases, as well as assimilation of carbonate wall rocks ultimately led to the decrease of LREE contents and/or modification of Zr/Hf ratios. Magmatic phases of the nepheline syenite include nepheline, sodalite, oligoclase, orthoclase, and annite, as well as accessory fluorapatite, fluorite, and minor amounts of zircon and metamict allanite-Ce. The nepheline equilibrated at temperatures ranging between 850°C and 700°C, which reflects protracted residence at a higher temperature. Later, it has been locally altered to cancrinite, dawsonite, and natrolite via CO2- and alkali-rich fluid influx. The fluid–rock interactions were also manifested by the presence of chessboard-twinned albite and coarsening of braid-perthite into patch-perthite, as well as recrystallization of primary orthoclase into microcline. The orthoclase→microcline conversion, albeit fairly indiscrete under a polarizing microscope and confirmed by Raman micro-spectroscopy, is followed by the change of cathodoluminescence colours, i.e. from light-blue (activated by Ti4+ and/or Al-O—Al centres) in orthoclase towards brownish and/or greenish (activated by Mn2+ and structural defects) in microcline.

Multistage fluorite mineralization in the southern Black Forest, Germany: evidence from rare earth element (REE) geochemistry

Abstract. The Black Forest hosts a wide range of hydrothermal mineralization, including fluorite–barite vein deposits. In a detailed investigation of the Finstergrund and Tannenboden deposits in the Wieden mining district (southern Black Forest), the diversity, geochemical evolution and relative chronology of multistage fluorite precipitation is tracked on the basis of rare earth element (REE) geochemistry, geologic field relationships and crystal zoning. Geochemical discrimination and mathematical λ coefficients suggest a total of seven fluorite REE groups, at least three distinguishable post-Variscan fluid mobilization events and independent formation histories for the deposits despite their spatial proximity. Fluorite vein mineralization at the Finstergrund deposit evolved over three fluid generations, was derived from gneissic source aquifers and comprises five distinct fluorite REE groups: the first fluid generation is characterized by fluorite precipitation above 200 ∘C (“group III”), below 200 ∘C (“group I”) and after fractional crystallization (“group IV”); the second generation comprises remobilized fluorite (“group II”); and the third generation revealed fluorite precipitation by meteoric water mixing (“group V”). Fluorite vein formation at the Tannenboden deposit is associated with two distinct fluorite REE patterns derived from the same fluid generation: fluorite precipitation above 200 ∘C (“group VII”) and after cooling below 200 ∘C (“group VI”). Its fluid source aquifer lithology best matches migmatites contrary to previous models that suggest either gneissic or granitic aquifer rocks for fluorite vein precipitation in the Black Forest. The decoupled formation history between the deposits is tectonically controlled as suggested by a new genetic model for the Wieden mining district. The model argues for a change in the local fluid percolation network and the termination of hydrothermal activity at the Tannenboden deposit after the first fluid mobilization event. The geochemical evolution of multistage fluorite mineralization, as exemplified by the Tannenboden and Finstergrund deposits in combination with other fluorite mineralizations in the Black Forest, provides unique insights into the lithospheric origin and precipitation behaviour of fluorite by various fluid–rock interaction processes occurring in large hydrothermal systems. The local diversity of REE patterns emphasizes the need for detailed investigations of individual hydrothermal vein deposits.

Trace element geochemistry of magnetite from Mabianshan skarn iron deposit in the Lu-Zong volcanic basin, Eastern China

The composition of host rocks is essential in determining the composition of hydrothermal magnetite formed via fluid-rock interactions in skarn deposits. The HuangLong ore field in the Luzong volcanic basin, Eastern China, hosts several stratabound iron (Fe) skarn deposits, including Mabianshan and Longqiao. In this paper, we analyse the composition of different lithologies of carbonate strata and trace element concentrations in magnetite from Mabianshan, which has complex lithology carbonate strata, and compare it with magnetite from Longqiao, which has uniform lithology carbonate strata. The objective is to investigate the influence of lithology variation on magnetite trace elements and enhance the indicative significance of magnetite trace elements in prospecting and exploration. Our results demonstrate that the lithology of ore-bearing carbonate strata varies greatly due to inversion and different degrees of denudation in the ore field, resulting in variations of Al, Si, Mg, Mn, and Ca in the protolith across different areas. The alteration mineral assemblage of the Mabianshan deposit primarily included epidote, chlorite, and magnetite, while only a few diopside-magnetite relatively high-temperature assemblages developed in the southeastern part of the deposit. Moreover, higher concentrations of Ti and V in magnetite samples from the southeastern area of the deposit suggest that the heat sources related to Fe mineralization may be located there. Compared with the regular spatial variations of Mg, Mn, Al, and Si in the magnetite from Longqiao, the magnetite from Mabianshan does not show evident spatial variations due to the complex lithology of the magnetite protolith in different regions. The protolith lithology of magnetite from Longqiao is relatively stable, mainly dolomitic limestone. However, the protolith lithology of magnetite from Mabianshan is complex and includes dolomitic marlstone, dolomitic limestone, dolomite, and Fe-Mn bearing dolomite, resulting in a significant increase of Si, Al, Mg, and Mn in magnetite. Therefore, it is difficult to effectively trace the temporal-spatial evolution of the hydrothermal fluids using these elements in magnetite. Special attention should be paid to the uniformity of the protolith lithology of the ore when using these elements in magnetite to trace the fluid source.

The genetic association between vein and skarn type tungsten mineralization in the Yaogangxian tungsten deposit, South China: Constraints from LA-ICP-MS analysis of individual fluid inclusion

The large-scale Yaogangxian W deposit, located in central of the Nanling metallogenic belt, South China, comprises independent quartz vein-type and skarn-type W mineralization. Wolframite-bearing quartz veins occur invariably in metasandstone and slate to the northwest of the Yaogangxian granitic intrusion, whereas scheelite-skarn are mainly hosted by the limestone to the east. The vertical extension of single wolframite-bearing quartz vein can reach up to 1000 m and we focused on the vein samples collected from the deepest level (26 level) which likely recorded early magmatic fluids. For skarn mineralization, two scheelite precipitation stages were recognized, namely scheelite-1 in retrograde stage and scheelite-2 from sulfide-stage. To reveal the fluid sources and characteristics of two mineralizing systems, detailed petrography and microthermometry analyses were carried out on fluid inclusion assemblages (FIA) in scheelite, wolframite and their coexisting quartz. Fluid compositions were obtained from individual fluid inclusion (FI) in ore and gangue minerals via laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) analysis. These data aid elucidation on the source and nature of fluids in the two distinct W mineralization styles. The chemical compositions of FIs hosted in wolframite and scheelite points to a common magmatic source. The fluid in the scheelite ore section exhibits lower As and B than the wolframite ore section, indicating that boiling may have occurred at early skarn stage. Fluid evolution in the two mineralizing systems suggest that formation of diverse W mineralization styles is mainly controlled by different host lithology and fluid processes. In the wolframite ore section, ore-forming fluid recorded in the deepest level of vein show elevated As, B, K and Rb contents than previously reported ore-forming fluid obtained from the tip of the vein. This likely indicate absence of intensive fluid immiscibility in the deep during wolframite formation, which may rather be accompanied by fluid-rock interaction. In the scheelite ore section, constant injection of meteoric water is revealed. FI hosted in scheelite-1 and 2 exhibit similar compositions, and the lower K content in scheelite-2 fluid is thought to be caused by sericitization in the retrograde stage skarn. The Mo content of scheelite decreased from the retrograde stage to sulfide-stage, indicating a decrease in oxygen fugacity. Based on these conclusion and previous geological and geochronological studies, we propose a metallogenic model of the coupled wolframite-quartz vein and scheelite-skarn mineralization.

A Practical and Innovative Workflow to Support the Numerical Simulation of CO2 Storage in Large Field-Scale Models

Summary Numerical simulation of the CO2 storage process in porous media, such as in hydrocarbon (gas or oil) depleted reservoirs and in saline aquifers, has been the most indicated tool due to its ability to represent CO2 capacity and the different trapping mechanisms that retain CO2 in the subsurface. Given the complexity of the physicochemical phenomena involved, the modeling needs to incorporate multiphase flow, complex representation of fluids, rock, and rock-fluid interaction properties. These include CO2 reactions with aqueous species and with reservoir rock minerals, in addition to the structural and stratigraphic aspects of the reservoir heterogeneity. These phenomena need to be represented on suitable temporal and spatial scales for accurate predictions of their impacts. Currently, many studies are focused on simulating submodels or sectors of the reservoir, where using finer grids is still practical. This level of grid refinement can be prohibitive, in terms of simulation times, for modeling the entire reservoir. To address this challenge, we propose a new and practical workflow to simulate CO2 storage projects in large field-scale models. When the proposed workflow is applied in both synthetic and real field cases, simulation time is reduced by up to 96% compared to that of the fine-grid model, preserving the same results in representing the aforementioned mechanisms. The workflow is based on classical and standard approaches to handle the high simulation time, but in this study, they are structured and sequenced in three steps. The first one considers the most relevant mechanisms for CO2 storage, ranked from a high-resolution sector model. With the mechanisms prioritized in the previous step, a single-phase upscaling of petrophysical properties can be applied in the field-scale model, followed by adopting a grid with dynamic sizing. The proposed methodology is applied to saline aquifer models in this study, but it can be extended for storage in depleted hydrocarbon reservoirs.

Red or green: Overprinting of the climatic signal in Miocene sediments, South China Sea (IODP Expedition 368, Site U1502)

AbstractSedimentary beds of alternating red and green colour are commonly interpreted to reflect orbitally‐forced cyclic climatic, syn‐depositional conditions, although colour changes caused by post‐depositional fluids are also documented. Results from IODP Hole U1502A marine sediments in the South China Sea exemplify post‐depositional reducing fluid–rock interactions that locally changed the sediment colour from red to green. Petrographic, rock magnetic and paleomagnetic data on cores show that the red colouration originates from an early, basin‐wide, pervasive diagenetic oxidation event (forming haematite), whereas the green colouration results from subsequent fluid‐driven reduction (forming pyrrhotite‐magnetite). The dense sulfidic stockwork in the basaltic basement underlying these sediments was the likely source of reducing fluids. Drilling deep holes into marine basin basements can thus provide useful information on fluid transfer from the basement to the overlying sedimentary layers.

Interstitial carbonates in pillowed metabasaltic rocks from the Pilbara Craton, Western Australia: A vestige of Archean seawater chemistry and seawater-rock interactions

Calcites hosted in the interpillow void spaces of extremely well preserved, 3.47–3.12 Ga pillow lavas of the Archean Pilbara Craton, Australia, provide new geochemical insights into the composition of Archean seawater and its interaction with basaltic crust. We present a comprehensive dataset of major and trace elements, radiogenic 147Sm-143Nd, 87Rb-87Sr, and stable C-O isotopes for these calcites.Based on their elemental composition and Post-Archean Australian Shale-normalized rare earth element and yttrium (REYPAAS) patterns, two types of calcites can be distinguished. Type I (n = 9) are coarse-grained calcites with elevated Mn concentrations (478–14,790 ppm) and high REY concentrations that match the basaltic host rock compositions. Petrographic textures in combination with geochemical data indicate precipitation from boiling seawater trapped between pillows during basalt eruption. Small light-REYPAAS depletions, only slightly super-chondritic Y/Ho (34.5–39.1), and low δ18O(VSMOW2) (9.25–16.66 ‰) suggest relatively high fluid-rock interactions of boiling seawater with the basaltic host rock. These characteristics are similar to those of interstitial carbonates found in modern mid-ocean ridge basalts. Type II carbonates (n = 6) are fine-grained, low-Mn (13.7–420 ppm) calcites that exhibit comparably high Sr concentrations (825–2,516 ppm) and anoxic modern seawater-like REYPAAS patterns, strong super-chondritic Y/Ho (39.1–55.8) and δ18O(VSMOW2) values of 9.10–13.18 ‰. These features hint to direct calcite precipitation from seawater within the degassing space with little fluid-rock interaction.Almost all (Type I and Type II) of the calcites investigated here, combined with their respective host rocks, yield well-defined Sm-Nd isochron ages for the Apex (3,466 ± 23 Ma), Euro (3,365 ± 43 Ma), Honeyeater (3,187 ± 33 Ma), and Bradley (3,131 ± 24 Ma) formations. Only calcites from the Mt. Ada Basalt and their associated host rocks show a ∼ 100 Ma younger Sm-Nd isochron age (3,361 ± 22 Ma) compared to the U-Pb zircon age of formation.Highly radiogenic initial Sr isotope compositions of the high-Mn calcites (Type I) and low Sr concentrations, suggest Sr remobilization for these calcites. In contrast, the low-Mn calcite (Type II) exhibit higher Sr concentrations and lower 87Sr/86Sr(i) of 0.7010–0.7011 at 3.34 Ga and 0.70137 at 3.12 Ga, suggesting increasing influence of crustal weathering on the composition of Paleoarchean seawater through time, and progressive decoupling from the Archean mantle (87Sr/86Sr(i) = 0.7003–0.7007).

Strain shadow “megapores” in mid-crustal ultramylonites

AbstractMylonitic shear zones are important fluid conduits in the Earth’s crust. They host transient and permeable porosity that facilitates fluid transfer and controls fluid-rock interaction. Here we present microstructural observations from a mid-crustal ultramylonite with very large pores that occupy the strain shadows of albite porphyroclasts. Our non-invasive three-dimensional X-ray microtomographic data show that the largest of these strain shadow megapores have substantial volumes of as much as ∼1.7 × 105 µm3. Given that the sample shows no signs of retrogressive overprint or weathering, these pores must be synkinematic. Importantly, the close proximity of the pores to creep cavities in dynamically recrystallized quartz ribbon grains suggests a potential hydraulic link between fluid in the strain shadow megapores and fluid in the creeping rock matrix. The evolving megapores constitute very large syndeformational local fluid reservoirs in mylonites that likely fed into the granular fluid pump established by the dynamically evolving creep cavities. Our findings add to an emerging picture of the dynamic transport properties of ultramylonitic shear zones, where the formation and destruction of porosity are intrinsically linked to microscale deformation processes. They also suggest that despite many studies on porphyroclast systems, open questions remain, especially concerning the interaction of clasts with their matrix.

Hydrothermal ferromanganese oxides around a petit-spot volcano on old and cold oceanic crust

Areas of old and cold oceanic plate lack conventional volcanism and have been assumed to be devoid of submarine hydrothermal activity. However, petit-spot volcanoes are common in areas of flexure of such oceanic plates. Here, we report hydrothermal ferromanganese oxides dredged from the vicinity of a petit-spot volcano at 5.7 km water depth in an area of oceanic plate flexure east of the Japan Trench. The bulk chemical, lead isotopic and mineralogical compositions of the samples indicate their formation by low-temperature hydrothermal activity, which can be interpreted as being caused by fluid–rock interactions at <200 °C. We propose that interaction of local marine sediments with volatile-rich petit-spot magmas may produce hydrothermal fluids containing not only iron and manganese but also enough amounts of carbon dioxide and methane to have implications for the global carbon cycle. However, contemporary hydrothermal activities at petit-spot volcanoes have not been confirmed yet.

Barium isotope behavior during interaction between serpentinite-derived fluids and metamorphic rocks in the continental subduction zone

Serpentinites in subduction zones are important fluid reservoirs for crust-mantle interaction and arc magma formation. The serpentinite-derived fluids can carry fluid-mobile elements such as Ba and potentially affect the geochemical composition of the metamorphic rocks in the subduction zones. However, the Ba isotope behavior during interaction between serpentinite-derived fluids and metamorphic rocks is still poorly understood. The whiteschists of the Dora-Maira Massif in the Western Alps have experienced fluid infiltration by serpentinite-derived fluids during deep subduction. Here we report the Ba isotope data of the whiteschist and its protolith metagranite to investigate the Ba isotope behavior during fluid-rock interaction. The metagranites, which have experienced ultrahigh-pressure metamorphism, have a small variation of δ138Ba (−0.25 to 0.26‰), while the whiteschists display a large Ba isotope variation from −0.99‰ to 0.48‰. Such a large variation in whiteschists cannot be explained by chemical weathering, protolith heterogeneity, or kinetic effects. Instead, considering the negative correlations of δ138Ba with Ba and other fluid-mobile elements (e.g., Sr, Cs, Zn, and Cu) and the geochemical composition features of serpentinite-derived fluids, the large Ba isotope variation in whiteschists is inferred to be induced by the interaction between serpentinite-derived fluid and metagranite during intense fluid infiltration. This is consistent with the observation that the whiteschists with low Ba contents tend to exhibit heavier Mg-Fe isotope compositions but lighter Li isotope compositions, which indicates that the related fluids were derived from the dehydration of mantle wedge serpentinite. The fluid infiltrating process is well explained by a numerical model with high fluid-rock ratios of 4 to 12. Our modeling further suggests that serpentinite-derived fluid has a distinctly higher δ138Ba value than the depleted upper mantle. During fluid-rock interaction, heavy Ba isotopes prefer to be infiltrated into fluids with an apparent fractionation factor (Δ138Barock-fluid) of mostly −0.5‰ to −0.1‰ but can be down to −0.8‰ to −0.7‰ required for a few samples. A two-stage dehydration and metasomatism model at different depths can well explain the formation of Dora-Maira whiteschists. Whereas the Ba isotope composition of mantle wedge serpentinite is mainly dictated by crust-derived fluids from the subducting slab, an interaction between the serpentinite-derived fluids and the metagranite protolith resulted in a large Ba isotope variation of whiteschists. In case of a general involvement of serpentinites in subduction zones, serpentinite-derived fluids would significantly affect the Ba isotope compositions of subarc mantle peridotites and also arc lavas.