Anhydrite Precipitation Research Articles

High-Ca vent fluids discharged from the Lutao arc volcanic hydrothermal system are associated with albitization and recycling of marine carbonate

The chemical and isotopic characteristics of calcium (Ca) in subduction zones are closely related to the budget of Ca and carbon cycles. Here we investigate the ultra-high Ca concentrations that characterize the hydrothermal fluids discharged from two types of vents, named the Zhudanqu brine vent (ZDQ) and the Huwaichi vapor spring (HWC), in the Lutao hydrothermal system at the north Luzon arc. The Ca concentrations of up to 159 mM and Ca/Cl ratio of up to 0.26 in the ZDQ vent fluids are possibly the highest ever reported for Ca enrichment in global seawater-circulated hydrothermal/geothermal systems. The differences in chemical compositions between the ZDQ and the HWC vent fluids are primary controlled by subcritical phase separation. The brine phase constitutes the ZDQ vent fluids, while the HWC vent fluids represent mixtures of the vapor phase and seawater. Both the vapor and the brine phases exhibit similar δ44/40Ca values (0.72 ± 0.05‰), suggesting no significant Ca isotope fractionation has occurred during phase separation.The hydrothermal endmember before phase separation (the “Lutao endmember”) presents depletions of 213 ± 15 mM of Na, 24.4 ± 0.4 mM of SO42−, and 10.2 mM of K, and enrichment of 130.2 ± 5.5 mM of Ca with respect to the percolated seawater. The total gained Ca is 154.6 ± 5.9 mM with a δ44/40Ca value of 0.67‰ – 0.77‰ (0.72 ± 0.05‰), considering anhydrite precipitation during hydrothermal circulation. The Holocene raised coral reef is unlikely to contribute substantial Ca into the Lutao system. Much of the gained Ca (111.6 ± 7.5 mM) is produced by high-degree albitization of the Lutao host rock, which is promoted by the low water/rock ratio (~ 2), slightly alkaline conditions, and relatively lower temperature of the Lutao system with respect to most mid-ocean ridge hydrothermal systems. Ca derived from this process inherits the Ca isotopes of plagioclase in the Lutao host rocks (δ44/40Ca = 0.82 ± 0.06‰). According to mass and isotopic balances, the recycled marine carbonate is proposed to contribute 43 ± 13.4 mM Ca with a δ44/40Ca value of 0.46−0.63+0.35‰ into the Lutao system. Such isotopically lighter Ca is derived from either pore fluids expulsed from underlying Philippine Sea sediments, or more probably, carbonate-bearing subduction fluids from the subducting South China Sea sediments and slab. The carbonate solubility in the subduction fluids could maintain at 600 mM near the reaction zone. The carbonate-rich fluids were subsequently migrated into the Lutao reaction zone and released an additional 43 ± 13.4 mM Ca via dolomitization. A small amount (~ 9%) addition of carbonate-rich fluids would not significantly change the budgets of Na, Mg, and Cl but could generate substantial Ca enrichment and Ca isotopic variations.

Compositional and diagenetic evolution of a siltstone, with implications for reservoir quality; an example from the Lower Triassic Montney Formation in western Canada

Diagenetic models for silt-rich mudstone (siltstone) are less advanced than those for sandstone and clay-rich mudstone. In addition, the influences of diagenetic processes on reservoir quality in siltstone formations are poorly understood. Here we examine the roles of depositional facies, detrital composition, and diagenetic processes in the compositional evolution and reservoir quality of the Lower Triassic Montney Formation, a prominent siltstone-dominated reservoir in western Canada with very large reserves of oil, gas-liquids and natural gas. We applied advanced, high-resolution petrographic methods including SEM (SE, BSE, EDX and SEM-CL), XRD, and QEMSCAN technologies, as well as He-pycnometry on samples from 17 different locations within the basin that represent a range of depths and thermal maturities. Cross-cutting and overgrowth relationships and volumes of authigenic phases demonstrate massive precipitation of quartz, feldspar, dolomite, calcite and anhydrite cements at shallow burial depths, leading to compositional homogeneity among different lithofacies. We propose that the precipitation of large volumes of cement resulted from high fluid flux through the formation at shallow depth, possibly driven by reflux of concentrated seawater in nearshore saltpans. Siltstones preserve relatively high porosity and permeability at shallow burial depths, differing from clay-rich mudstones. In contrast to sandstones, deep burial diagenesis played a relatively minor role in the compositional evolution of the Montney Formation siltstone and is expressed in the form of pressure solution and minor amounts of fibrous illite precipitation.

Evaluation of NaCl and MgCl2 heat exchange fluids in a deep binary geothermal system in a sedimentary halite formation

Halite formations are attractive geothermal reservoirs due to their high heat conductivity, resulting in higher temperatures than other formations at similar depths. However, halite formations are highly reactive with undersaturated water. An understanding of the geochemical reactions that occur within halite-saturated formation waters can inform decision making regarding well construction, prevention of well clogging, formation dissolution, and thermal short-circuiting. Batch reaction and numerical 3-D flow and equilibrium reactive transport modeling were used to characterize the produced NaCl-brine in a well targeting a halite-saturated formation. The potential for inhibition of precipitation and dissolution using an MgCl2-brine and NaCl + MgCl2-brine were also investigated. Within the injection well, heating of an NaCl-brine from 70 to 120 °C caused the solubility of halite to decrease, resulting in the potential dissolution of 0.479 mol kg−1 halite at the formation. Conversely, cooling from 120 to 100 °C in the production well resulted in potential precipitation of 0.196 mol kg−1 halite. Concurrent precipitation of anhydrite is also expected. Introduction of MgCl2 into the heat exchange brine, which has a common Cl− ion, resulted in a decreased potential for dissolution by 0.290 mol kg−1 halite within the formation, as well as decreased precipitation within the production well, compared to the NaCl-brine. The halite solubility was altered by changes in pressure up to 0.045 mol kg−1. This indicates that designing and monitoring the composition of heat exchange fluids in highly saline environments is an important component in geothermal project design.

Numerical Simulation‐Based Clarification of a Fluid‐Flow System in a Seafloor Hydrothermal Vent Area in the Middle Okinawa Trough

AbstractDespite many studies on seafloor hydrothermal systems conducted to date, the generation mechanism of seafloor massive sulfide (SMS) deposits is not yet fully understood. To elucidate this mechanism, this study clarifies the three‐dimensional regional temperature distribution and fluid flow of a seafloor hydrothermal system of the Iheya North Knoll, middle Okinawa Trough. Lateral flow and boiling of hydrothermal fluids below a caprock were the main features found by the simulation. A caprock formation generated by anhydrite precipitation and hydrothermal alteration is the most plausible cause of these features, because caprocks can increase the temperature and induce boiling of fluids by preventing seawater inflow. Such a formation also gradually makes the top of the conduit less permeable; thus, lateral flow occurs. Consequently, vapor‐rich hydrothermal fluids poor in metals are discharged from vents as white smokers, whereas liquid‐dominated hydrothermal fluids rich in metals flow laterally below the caprocks, forming subseafloor SMS deposits.

Reservoir characteristics and genesis of the Ordovician M54−1a in the central and eastern parts of the Ordos Basin, China

M54−1a is a new natural gas exploration target of the Ordovician in the Ordos Basin and is expected to have large-scale reserves and a production increasing area after M51 and M52 weathering crust gas reservoir. Based on the data of the drilling core, thin section, cathodoluminescence, physical properties, and geochemical characteristics, a study has been conducted about the genesis and distribution of the M54−1a reservoir in the central and eastern parts of the Ordos Basin. The study results showed the following: (1) The M54−1a reservoir is composed of fine-silt-crystalline dolomite containing anhydrite nodules in lithology. The reservoir storage space is mainly the moldic pores of anhydrite nodules with a small amount of anhydrite crystal moldic pores and micro-fractures. The average porosity is 5.54%, and the average permeability is 1.53 × 10−3μm2. (2) The reservoir pores have experienced anhydrite precipitation, atmospheric freshwater dissolution, mesocrystalline calcite filling, quartz filling, medium-coarse crystal dolomite filling, megacryst calcite filling, and cataclasis. (3) Differential dissolution and differential filling influenced by paleogeomorphology controlled the planar distribution of the reservoir. The results of the comprehensive analysis indicate that the superimposed area between the high part of sedimentary paleogeomorphology and the karst slope at the west of Yulin-Jingbian-Yanan as well as the Hongdunjie-Qingyangcha area are high-quality reservoir distribution areas with strong dissolution and low filling degree. The study results provide the theoretical basis for the next exploration and well deployment.

Anhydrite‐Assisted Hydrothermal Metal Transport to the Ocean Floor—Insights From Thermo‐Hydro‐Chemical Modeling

AbstractHigh‐temperature hydrothermal venting has been discovered on all modern mid‐ocean ridges at all spreading rates. Although significant strides have been made in understanding the underlying processes that shape such systems, several first‐order discrepancies between model predictions and observations remain. One key paradox is that numerical experiments consistently show entrainment of cold ambient seawater in shallow high permeability ocean crust causing a temperature drop that is difficult to reconcile with high vent temperatures. We investigate this conundrum using a thermo‐hydro‐chemical model that couples hydrothermal fluid flow with anhydrite‐ and pyrite‐forming reactions in the shallow subseafloor. The models show that precipitation of anhydrite in warming seawater and in cooling hydrothermal fluids during mixing results in the formation of a chimney‐like subseafloor structure around the upwelling, high‐temperature plume. The establishment of such anhydrite‐sealed zones reduces mixing between the hydrothermal fluid and seawater and results in an increase in vent temperature. Pyrite subsequently precipitates close to the seafloor within the anhydrite chimney. Although anhydrite thus formed may be dissolved when colder seawater circulates through the crust away from the spreading axis, the inside pyrite walls would be preserved as veins in present‐day metal deposits, thereby preserving the history of hydrothermal circulation through shallow oceanic crust.

Colmatage of Reservoir Rocks in Oil Field Exploitation as a Result of Cation Exchange

The study of the change in the composition of the seawater injected for reservoir pressure maintenance (RPM) to the anhydrous granitoid reservoir of the White Tiger oil field, in which the cracks are partially filled with calcium minerals (calcite and laumontite), has shown that these minerals interact with injected seawater. Hydrogeochemical modeling of this process has revealed that the seawater cations (first sodium and then magnesium) displace calcium from the laumontite exchange complex, which leads to precipitation of anhydrite and a small amount of calcite. The incoming water dissolves the anhydrite and precipitates it downstream, forming a gradually expanding annular region with a constant increase in the amount of precipitated anhydrite. As a result, there is a decrease in the permeability of the fractured medium due to the anhydrite filling of the cracks. A large amount of calcium in the produced waters upon their rise to the surface causes the calcite precipitation in the production wells and the surface equipment. The transition of drilling to greater depth, where the rocks contain laumontite almost everywhere, requires considering the phenomena of cation exchange between the injected water and the rock in the predictions of scaling.

Colmatation of reservair rocks in the operation of oil fields as a result of cation exchange

By analyzing the changes in seawater pumped to maintain reservoir pressure (FPD), the anhydrous granitoid reservoir of the White Tiger deposit, in which the cracks are partially filled with calcium minerals (calcite and lomontite), shows that these minerals interact with the injected seawater. Hydrogeochemical modeling of this process showed that cations of seawater are first sodium and then magnesium displace calcium from the lomonite exchange complex, which leads to precipitation of anhydrite and a small amount of calcite. The incoming water dissolves the anhydrite and precipitates it downstream, forming a gradually expanding annular region with a constant increase in the amount of precipitated anhydrite. As a result, there is a decrease in the permeability of the fracture medium due to the filling of the cracks with anhydrite. A large amount of calcium in the associated waters when they rise to the surface causes the precipitation of calcite in the production wells and surface equipment. The transition of drilling to ever greater depths, where the rocks contain lomontite almost everywhere, requires taking into account the phenomena of cation exchange between the injected water and the rock in the predictions of scaling.

Impact of Temperature on Scale Formation in Chalk Reservoirs

Summary Operators are collecting abundant produced-water data that are often underused. Produced-water-composition data provide clues related to the geochemical reactions that are occurring in the subsurface. This information can be useful for monitoring interwell connectivity and predicting and managing oilfield scale resulting from brine supersaturation. Coupling thermodynamic calculations with produced-water analysis helps to identify geochemical effects that could affect oil recovery. This work addresses the difference that reservoir temperature has on geochemical reactions in carbonate reservoirs by comparing data from two offshore fields and identifying the rock/brine and brine/brine reactions that will affect scale management. Two seawater-flooded chalk fields located near each other were selected as candidates for comparison. The temperature of one field is 130°C, whereas for the other field, it is 90°C. Produced-water samples (a total of 6,800) from these two fields were analyzed, and the compositional trends were plotted to identify the deviation from conservative (nonreacting) behavior. The compositional trends were then grouped to identify if there were common features between wells. This analysis was complemented by 1D reactive-transport modeling to identify the reactions that would be consistent with the observed trends. Two groups of wells were identified within each reservoir on the basis of the produced-brine compositional behavior. Each well group exhibits a distinct ion-trend behavior, especially with respect to barium, calcium, strontium, and magnesium concentrations—because these are divalent cations that are abundant in the formation brines. The breakthrough of sulfate, a component primarily introduced during seawater flooding, varies very significantly between the two groups in each case. In one grouping, the sulfate is barely retarded, and it breaks through at seawater fractions lower than 10%. In the other grouping, however, sulfate does not break through until the seawater fraction in the produced brine exceeds 75%. This retardation of sulfate occurs most strongly in the hotter reservoir, and this might be attributed to the lower solubility of the calcium sulfate mineral anhydrite at a higher temperature. The retardation of sulfate then means that barium is produced at higher concentrations because barite precipitation in the reservoir is thus restricted, caused by sulfate being the limiting ion. However, some sulfate stripping does occur in the cooler reservoir, despite the higher solubility of anhydrite. Furthermore, in all cases, magnesium is retarded, with some groupings exhibiting the complete stripping of magnesium from the injected seawater. The magnesium-stripping behavior is reproduced in the reactive-transport models when calcium- and magnesium-replacement reactions are allowed. This phenomenon has been observed elsewhere in coreflood experiments, and it also contributes to the sulfate stripping through the promotion of anhydrite precipitation within the rock. This process, which is beneficial in terms of reducing the scale risk, is more pronounced at higher temperatures. Therefore, higher-temperature chalk reservoirs might act as natural sulfate-reduction plants, reducing scaling, souring risks and, thus, operating costs of the fields.

Comment on the papers by Hovland et al. (2018) “Large salt accumulations as a consequence of hydrothermal processes associated with 'Wilson cycles': A review” (part 1 and 2)

Abstract The geological model of large hydrothermal salt accumulations linked to Wilson cycles as reviewed by Hovland and Coworkers, un-adequately addressed: (1) the lack of well exposed submarine volcanogenic hydrothermal feeder zone, (2) the sequential precipitation of different hydrothermal evaporite minerals and (3) the absence of hydrothermal alteration mineralogy around the major evaporites. These aforementioned points are the main classical features to be linked to the hydrothermal model of evaporites. Experimentally, heating seawater during submarine volcanism firstly results in precipitation of anhydrite followed by halite, other evaporite minerals, serpentine, brucite, talc, metallic sulfides-oxides and related hydrothermal alterations. In this regard, Mg/Ca – Cl, Mg/Ca – SO4, Mg/Ca – Na/Cl and Mg/Ca - TDS biplots show that hydrothermal brines of riftogenic and subduction zone settings plot in a separate field than the subduction-related Andean Salars as well as seawater. This indicates that the hydrothermal serpentinization of basaltic oceanic crust and mantle peridotites removes magnesium from seawater and incorporates the Mg into serpentine, brucite and other hydrous Mg-silicates rather than the hydrothermal brines. Finally, our comment arose from a recent global classification of the most distinguished marine, non-marine and exhalative hydrothermal evaporites.

Salt dissolution and permeability in the Western Canada Sedimentary Basin

Extensive dissolution of evaporites has occurred in the Williston Basin, Canada, but it is unclear what effect this has had on bulk permeability. The bulk of this dissolution has occurred from the Prairie Evaporite Formation, which is predominantly halite and potash. However, minor evaporite beds and porosity infilling have also been removed from the overlying Dawson Bay and Souris River formations, which are predominantly carbonates. This study examines whether permeability values in the Dawson Bay and Souris River formations have been affected by dissolution, by analyzing 142 drillstem tests from those formations. For both the Dawson Bay and Souris River formations, the highest permeabilities were found in areas where halite dissolution had occurred. However, the mean permeabilities were not statistically different in areas of halite dissolution compared to those containing connate water. Subsequent precipitation of anhydrite is known to have clogged pore spaces and fractures in some instances. Geochemical relationships found here support this idea but there is no statistically significant relationship between anhydrite saturation and permeability. Geomechanical effects, notably closure of fractures due to collapse, could be a mitigating factor. The results indicate that coupling dissolution and precipitation to changes in permeability in regional flow models remains a significant challenge.

Sulfate minerals control dissolved rare earth element flux and Nd isotope signature of buoyant hydrothermal plume (EMSO-Azores, 37°N Mid-Atlantic Ridge)

While hydrothermal vents are now thought to be a major source of dissolved iron to the oceans, they have always been considered to be a sink for the dissolved rare-earth elements (DREEs). However, true dissolved REE observations in hydrothermal plumes are still lacking. Here we report for the first time the DREE concentrations and neodymium isotopic compositions (DεNd) of buoyant hydrothermal fluids at Lucky Strike (Mid-Atlantic Ridge). We find that 27 to 62% of total hydrothermal DREEs are rapidly scavenged by anhydrite precipitation at the onset of buoyant plume formation. After this initial loss, all DREEs behave quasi-conservatively within the buoyant plume. Dissolved phase εNd (DεNd) in the evolving plume are identical to black smoker DεNd of +9.0 and contrast radically with DεNd of the local deep water mass at −12.0. Plume DεNd as low as +6.6 may be reconciled by dissolution of newly formed barite in the local environment and carrying seawater DεNd signature. We find, based on the first plume DREE observations, that hydrothermal plumes are in fact a source of DREE to the North Atlantic Deep Water. Precipitation/dissolution processes of hydrothermally-derived minerals, i.e. sulfates in the buoyant plume and Fe oxy-hydroxide in the non-buoyant plume, will likely affect the fate of other trace metals and their isotopic composition.

Shale-brine-CO2 interactions and the long-term stability of carbonate-rich shale caprock

The success of geological carbon storage (GCS) depends on the sealing properties of caprocks, typically mudrocks, and their laminated variety – shales. In this study, we examined mineralogical changes in carbonate-rich Mancos Shale and corresponding changes in micro-mechanical properties following the reaction with carbon dioxide (CO2). Mineralogical changes of Mancos Shale depended on the pressure of CO2 during its exposure to the CO2-brine mixtures for up to 8 weeks. Dedolomitization was observed in the reactors pressurized with 100 psi of CO2, combined with the precipitation of gypsum. In the reactor pressurized with 2500 psi of CO2, the complete dissolution of calcite, partial dissolution of dolomite, and precipitation of magnesite and anhydrite were observed. Localized mechanical weakening was observed only for dolomite-muscovite-illite-rich laminae following whole shale puck alteration at 2500 psi of CO2, and a decrease of up to 50 ± 20% in scratch toughness was observed. The quartz-calcite-rich laminae did not exhibit a measurable difference in scratch toughness before and after reaction in CO2-rich brine. The predicted changes in mineralogy, porosity, density, and hardness of Mancos Shale are limited, according to the geochemical models describing alteration of shale by CO2-rich brine lasting for 5000 years. This study illustrates a coupled and localized chemical-mechanical response of caprock to the injection of CO2.

Gypsum, bassanite, and anhydrite at Gale crater, Mars

Analyses by the CheMin X-ray diffraction instrument on Mars Science Laboratory show that gypsum, bassanite, and anhydrite are common minerals at Gale crater. Warm conditions (∼6 to 30 °C) within CheMin drive gypsum dehydration to bassanite; measured surface temperatures and modeled temperature depth profiles indicate that near-equatorial warm-season surface heating can also cause gypsum dehydration to bassanite. By accounting for instrumental dehydration effects we are able to quantify the in situ abundances of Ca-sulfate phases in sedimentary rocks and in eolian sands at Gale crater. All three Ca-sulfate minerals occur together in some sedimentary rocks and their abundances and associations vary stratigraphically. Several Ca-sulfate diagenetic events are indicated. Salinity-driven anhydrite precipitation at temperatures below ∼50 °C may be supported by co-occurrence of more soluble salts. An alternative pathway to anhydrite via dehydration might be possible, but if so would likely be limited to warmer near-equatorial dark eolian sands that presently contain only anhydrite. The polyphase Ca-sulfate associations at Gale crater reflect limited opportunities for equilibration, and they presage mixed salt associations anticipated in higher strata that are more sulfate-rich and may mark local or global environmental change. Mineral transformations within CheMin also provide a better understanding of changes that might occur in samples returned from Mars.

Experimental partitioning of Ca isotopes and Sr into anhydrite: Consequences for the cycling of Ca and Sr in subseafloor mid-ocean ridge hydrothermal systems

The elemental and isotopic mass balance of Ca and Sr between seawater and the oceanic crust at mid-ocean ridge (MOR) hydrothermal systems integrates various physiochemical processes in the subseafloor, such as dissolution of primary silicate minerals, formation of secondary minerals, and phase separation in the subseafloor. In particular, the precipitation and recrystallization of anhydrite are recognized as important processes controlling the Ca and Sr elemental and isotope composition of high temperature vent fluids and coexisting ocean crust, and yet, little experimental data exist to constrain the mechanism and magnitude of these critical geochemical effects. Thus, this study experimentally examines Sr/Ca partitioning, Ca isotope fractionation, and the rate of exchange between anhydrite and dissolved constituents. These experimental constraints are then compared with Sr/Ca and Ca isotope compositions of anhydrite and vent fluids sampled from the TAG hydrothermal system. Accordingly, anhydrite precipitation and recrystallization experiments were performed at 175, 250, and 350 °C and 500 bar at chemical conditions characteristic of active MOR hydrothermal systems. Experimental data suggest that upon entrainment and recharge of seawater into MOR hydrothermal systems anhydrite will rapidly precipitate with a Ca isotopic composition that is depleted in the heavy isotope compared to the hydrothermal fluid. The magnitude of the Ca isotope fractionation, Δ44/40Ca(Anh-Fluid), is temperature dependent, −0.45, −0.22, and −0.02‰, for 175, 250, and 350 °C, respectively, but likely indicative of kinetic effects. Utilization of a 43Ca spike in solution was implemented to quantify the time-dependent extent of isotope exchange during anhydrite recrystallization at chemical equilibrium. These data indicate that the rate of exchange is a function of temperature, where 12, 46, and 45% exchange occurred within 1322, 867, 366 h at 175, 250, and 350 °C, respectively. The partitioning of Sr/Ca between anhydrite and constituent dissolved species during precipitation depends greatly on the saturation state of the hydrothermal fluid with respect to anhydrite at each experimental temperature, KD(Anh-Fluid) = 1.24–0.55 at 175–350 °C, broadly similar to results of earlier experimental observations by Shikazono and Holland (1983). Equilibrium KD(Anh-Fluid) values were estimated by taking explicit account of time dependent magnitude of exchange, yielding values of 0.43, 0.36, 0.29 at 175, 250, and 350 °C, respectively. Coupling these experimental constraints with the temperature gradient inferred for high temperature MOR hydrothermal systems suggests that the Ca isotope and Sr elemental composition of anhydrite formed near the seafloor will retain the composition derived upon initial formation conditions, which is indicative of disequilibrium. In contrast, at greater depths and at higher temperatures, anhydrite will reflect close to equilibrium Sr/Ca partitioning and Ca isotope fractionation conditions. The experimental and natural data presented in this study can be used to further understand the effect of anhydrite precipitation during hydrothermal circulation in the oceanic crust and on the chemical and isotopic composition of seawater on geologic timescales.

Impacts of SO2 gas impurity within a CO2 stream on reservoir rock of a CCS pilot site: Experimental and modelling approach

In order to evaluate chemical impacts of SO2 impurity on reservoir rock during CO2 capture and storage in deep saline aquifers, several batch reactor experiments were performed on laboratory scale using core rock samples from the pilot CO2 injection site in Heletz. In this experiment, the samples were exposed to pure N2(g), pure CO2(g), and CO2(g) with an impurity of 1.5% SO2(g) under reservoir conditions for pressure and temperature (14.5 MPa, 60 °C). Based on the set-up and the obtained experimental results, a batch chemical model was established using the numerical simulation program TOUGHREACT V3.0-OMP. Comparing laboratory and simulation data provides a better understanding of the rock-brine-gas interactions. In addition, it offers an evaluation of the capability of the model to predict chemical interactions in the target injection reservoir during exposure to pure and impure CO2. The best match between the geochemical model and experimental data was achieved when the reactive surface area of minerals in the model was adjusted in order to calibrate the kinetic rates of minerals. The simulations indicated that SO2(g) tends to dissolve rather quickly and oxidizes under a kinetic control. Hence, it has a stronger effect on the acidity of the brine than pure CO2(g) and as a result, increased mineral dissolution and caused the precipitation of sulfate and sulfide minerals. Ankerite, dolomite, and siderite, the most abundant carbonates in the sandstone rock sample, are subject to stronger dissolution in the presence of SO2 gas. The performed simulations confirmed a slower dissolution rate for ankerite and siderite than for dolomite. The model reproduced the precipitation of pyrite and anhydrite as observed in the laboratory. The dissolution of dolomite observed in the batch reaction test with pure N2 is assumed to be due to slight contamination with oxygen and modelling supported this. The inclusion of SO2 increased the porosity over that of the pure CO2 case, and is thus considered to increase the permeability and injectivity of the reservoir as well. Exposure to SO2 also increased the concentration of trace elements. The calibrated kinetic parameters determined in this study will be used to model the injection and long-term behavior of CO2 at the Heletz field site, and may be used for similar geologic reservoirs.

Prediction of the Deposition of Sulfate Salts Taking the Content of Strontium during the Exploitation of Oil Fields into Account

Based on the experience of developing an oil field on the Caspian Sea shelf, which was initially exploited with injection of seawater into the oil-bearing beds to maintain reservoir pressure, the deposition of sulfate salts under reservoir conditions is predicted. The prediction of sulfate deposition is made in two ways: analytical calculations according to the method of J.E. Oddo and M.B. Thomson and computer modeling. The prediction took the strontium content in the formation waters of the oil-field into account, which is usually ignored in production practice. It has been established that the prediction by computer modeling is more accurate; in particular, it considerably expands the temperature limits of anhydrite precipitation. The amount of potentially precipitable sulfate salts found by computer modeling has shown that the mass of deposited calcium and strontium sulfates is rather large, which can significantly reduce the permeability of the reservoir.

Forecast of the deposition of sulfate salts, taking into account the content of strontium, in the exploitation of oil deposits

Based on the experience of developing an oil fieled on the Caspian Sea shelf, which was initially operated with injection of seawater into oil-bearing seams to maintain reservoir pressure, a forecast was made for the deposition of sulfate salts in reservoir conditions. The forecast of sulphate deposition is carried out in two ways: analytical calculations by the method of J.E. Oddo and M.B. Thomson and computer modeling. The prognosis took into account the strontium content in the reservoir waters of the deposit, which is usually ignored in oilfield practice. It has been established that computer modeling gives a more accurate prediction, in particular, considerably expands the temperature limits of anhydrite precipitation. The determination of the amount of potentially sulphate salts potentially found in computer simulations has shown that the mass of deposited calcium and strontium sulfates is large enough that it can significantly reduce the permeability of the reservoir.

Unraveling multiple phases of sulfur cycling during the alteration of ancient ultramafic oceanic lithosphere

Ultramafic-hosted hydrothermal systems – characterized by ongoing serpentinization reactions – exert an important influence on the global sulfur cycle. Extensive water-rock interaction causes elemental exchange between seawater and the oceanic lithosphere, effectively removing sulfate from seawater through both abiogenic and biogenic processes. Here, we use bulk rock multiple sulfur isotope signatures (32S, 33S, 34S) and in situ sulfide analyses together with petrographic observations to track the sulfur cycling processes and the hydrothermal evolution of ancient peridotite-hosted hydrothermal systems. We investigate serpentinized peridotites from the Northern Apennine ophiolite in Italy and the Santa Elena ophiolite in Costa Rica and compare those with the Iberian Margin (Ocean Drilling Program (ODP) Leg 149 and 173) and the 15°20′N Fracture Zone along the Mid-Atlantic Ridge (ODP Leg 209).In situ measurements of sulfides in the Northern Apennine serpentinites preserve a large range in δ34Ssulfide of −33.8 to +13.3‰ with significant heterogeneities within single sulfide grains and depending on mineralogy. Detailed mineralogical investigation and comparison with bulk rock Δ33Ssulfide and in situ δ34Ssulfide data implies a thermal evolution of the system from high temperatures (∼350 °C) that allowed thermochemical sulfate reduction and input of hydrothermal sulfide to lower temperatures (<120 °C) that permitted microbial activity. The change in temperature regime is locally preserved in individual samples and correlates with the progressive uplift and exposure of mantle rock associated with detachment faulting along a mid-ocean ridge spreading center. The Santa Elena peridotites preserve distinct signatures for fluid circulation at high temperatures with both closed system thermochemical sulfate reduction and input of mafic-derived sulfur. In addition, the peridotites provide strong evidence that low Ca2+ concentrations in peridotite-hosted systems can limit sulfate removal during anhydrite precipitation at temperatures above 150 °C. This may play a central role for the availability of sulfate to microbial communities within these systems. Overall, the combined application of in situ and bulk rock multiple sulfur isotope measurements with petrographic observations allows us to resolve the different episodes of sulfur cycling during alteration of the oceanic lithosphere and the temporal changes between abiogenic and biogenic processes that control the sulfur cycling in these systems.

Reactivity of supercritical sulfur dioxide and carbon dioxide in a carbonate reservoir: An experimental investigation of supercritical fluid-brine-rock interactions relevant to the Madison Limestone of Southwest Wyoming

Managing impure carbon dioxide produced by fossil fuel-based generation of electricity is required for successful implementation of carbon capture, utilization, and storage. Impurities in carbon dioxide, particularly [Formula: see text] and [Formula: see text], are geochemically more reactive than the carbon dioxide and may adversely impact a carbon dioxide storage reservoir by generating additional acidity. Hydrothermal experiments are performed to evaluate geochemical and mineralogic effects of injecting [Formula: see text]-[Formula: see text] fluid into a carbonate reservoir. The experimental design is based on a natural carbon dioxide reservoir, the Madison Limestone on the Moxa Arch of Southwest Wyoming, which serves as a natural analog for geologic cosequestration of sulfur dioxide and carbon dioxide. Idealized Madison Limestone ([Formula: see text]) and [Formula: see text] brine ([Formula: see text], initial [Formula: see text]) reacted at reservoir conditions (110°C and 25 MPa) for approximately 165 days (3960 h). Carbon dioxide fluid containing 500 ppmv sulfur dioxide was injected and the experiment continued for approximately 55 days (1326 h). Sulfur dioxide partitions out of the supercritical carbon dioxide phase and dissolves into coexisting brine on the time scale of the experiments (55 days). Injecting supercritical [Formula: see text]-[Formula: see text] or pure supercritical carbon dioxide into a brine-limestone system produces the same in situ pH (4.6) and ex situ pH (6.4–6.5), as measured 28 h after injection because dissolution of calcite buffers in situ pH. Precipitation of anhydrite sequesters injected sulfur and, coupled with dissolution of calcite, effectively buffers the amount of dissolved calcium to the same concentrations measured in limestone-brine experiments injected with pure carbon dioxide. Supercritical [Formula: see text]-[Formula: see text] does not enhance the sequestration potential of a carbonate reservoir relative to pure supercritical carbon dioxide. Our results substantiate predictions from natural analog studies of the Madison Limestone that anhydrite traps sulfur and carbonate minerals ultimately reprecipitate and mineralize carbon in carbonate reservoirs.