Fluid Chemistry Research Articles

Wellbore Stability Analysis in Oil and Gas Drilling by Mechanical, Chemical and Thermal Coupling (Case Study in the South of Iran)

Inadequate wellbore stability has always been the most important issue during drilling and can cause many drilling complications. The most important tools for studying this phenomenon are the use of geomechanical modeling and failure criteria. Drilling fluid temperature and chemical interactions between drilling fluid and wellbore are also significant factors in wellbore stability. Decreasing the fluid temperature changes the concentration of induced stresses around the well, influencing the wellbore's safe mud window. This study considered a vertical well drilled in a field in southwest of Iran to determine the mud window and find out the optimal path under different conditions. The upper and lower bound of the mud window were calculated separately and simultaneously with three criteria, namely Mohr–Coulomb Failure, Hoek–Brown, and modified Lade. In the modified Lade failure criterion that gives more realistic results, the lower bound under the initial conditions is 7.81–10.51 ppg; by applying the thermal effect, it is 7.68–10.48 ppg, and with a fluid chemistry effect, it is 8.47–10.69 ppg. Given these two factors simultaneously, the lower bound of the mud window changed to 8.34–10.66 ppg. The optimal path in all failure criteria is horizontal drilling of well and maximum in horizontal stress direction. Furthermore, the upper bound of the mud window under mechanical conditions was 21.36–31.13 ppg, and with the effect of temperature was reduced to 21.09–30.84 ppg. Moreover, after applying the chemical effect, it increased to 21.29–31.05 ppg and converted to 21.02–30.76 ppg simultaneously.

Comparative geochemistry of flowback chemistry from the Utica/Point Pleasant and Marcellus formations

Flowback/Produced fluid samples were collected from several wells from two Utica/Point Pleasant (UPP) sites (UPPW and UPPS) in Ohio, and one Marcellus (Marcellus Shale Energy and Environment Laboratory (MSEEL)) site in West Virginia over a period of approximately two years. Although these formations have different ages, depositional environments, diagenetic histories, and geochemical and mineralogical compositions (i.e. the UPP is significantly more carbonate rich than the Marcellus which is more siliceous), analysis of trends in fluid species over time shows that, overall, the TDS and major solubilized elements (Na, Ca, Cl) in the UPP and Marcellus brines are remarkably similar. Total dissolved solutes (TDS) in these brines ranged from approximately 40 to 250 g/L salt, and in general, concentrations increased with time elapsed since natural gas well completion and stimulation. The behavior of Na, Br, and Cl suggests that the produced water signatures from these formations are largely derived from the native formational brines which display evidence of originating from evaporated seawater. There is a strong correlation between Cl and Br, indicating that both species behave conservatively, and the similarity among each of these brines suggests no appreciable contribution of salt from halite dissolution because Br is excluded from the halite structure. Cl/Br ratios in the brines range from ~80 to 120 (mg/L/mg/L). Other elements, such as K, which readily reacts between fluids and ion exchange sites on clays, generally exhibit conservative behavior for an individual site, but show significant variations among each of the different well pads.The concentrations of Sr and Ba vary dramatically among well sites, and increase with respect to Cl− over time, suggesting increasing solubilization, presumably from desorption from clay minerals or dissolution of carbonates or sulfates from the source formation(s). The UPPW well site has very low Ba due to high-sulfate input fluid, which resulted in precipitation of barite/celestite in the brines. In contrast the UPPS well site had elevated Sr (~ 3500 mg/L), presumably due to the use of Sr-rich recycled brine used in hydraulic fracturing. The Marcellus site had the highest Ba concentrations (up to 10 g/L) and highest Ba/Sr ratios in the fluids, due to the high concentration of barium in the Marcellus target (~ 1000 ppm, as compared to ~200 ppm in the UPP). These observations suggest that solutes in the FP fluids are derived from native brines, water-rock interactions that have occurred over geologic time scales, as well as some contribution from contemporaneous reactions in the subsurface. The results also show that the composition of the injected fluid can influence flowback fluid chemistry and possibly production efficiency.

Fracture Sustainability in Enhanced Geothermal Systems: Experimental and Modeling Constraints

Abstract Enhanced geothermal systems (EGS) offer the potential for a much larger energy source than conventional hydrothermal systems. Hot, low-permeability rocks are prevalent at depth around the world, but the challenge of extracting thermal energy depends on the ability to create and sustain open fracture networks. Laboratory experiments were conducted using a suite of selected rock cores (granite, metasediment, rhyolite ash-flow tuff, and silicified rhyolitic tuff) at relevant pressures (uniaxial loading up to 20.7 MPa and fluid pressures up to 10.3 MPa) and temperatures (150–250 °C) to evaluate the potential impacts of circulating fluids through fractured rock by monitoring changes in fracture aperture, mineralogy, permeability, and fluid chemistry. Because a fluid in disequilibrium with the rocks (deionized water) was used for these experiments, there was net dissolution of the rock sample: this increased with increasing temperature and experiment duration. Thermal-hydrological-mechanical-chemical (THMC) modeling simulations were performed for the rhyolite ash-flow tuff experiment to test the ability to predict the observed changes. These simulations were performed in two steps: a thermal-hydrological-mechanical (THM) simulation to evaluate the effects of compression of the fracture, and a thermal-hydrological-chemical (THC) simulation to evaluate the effects of hydrothermal reactions on the fracture mineralogy, porosity, and permeability. These experiments and simulations point out how differences in rock mineralogy, fluid chemistry, and geomechanical properties influence how long asperity-propped fracture apertures may be sustained. Such core-scale experiments and simulations can be used to predict EGS reservoir behavior on the field scale.

A Critical Review of the Physicochemical Impacts of Water Chemistry on Shale in Hydraulic Fracturing Systems.

Hydraulic fracturing of unconventional hydrocarbon resources involves the sequential injection of a high-pressure, particle-laden fluid with varying pH's to make commercial production viable in low permeability rocks. This process both requires and produces extraordinary volumes of water. The water used for hydraulic fracturing is typically fresh, whereas "flowback" water is typically saline with a variety of additives which complicate safe disposal. As production operations continue to expand, there is an increasing interest in treating and reusing this high-salinity produced water for further fracturing. Here we review the relevant transport and geochemical properties of shales, and critically analyze the impact of water chemistry (including produced water) on these properties. We discuss five major geochemical mechanisms that are prominently involved in the temporal and spatial evolution of fractures during the stimulation and production phase: shale softening, mineral dissolution, mineral precipitation, fines migration, and wettability alteration. A higher salinity fluid creates both benefits and complications in controlling these mechanisms. For example, higher salinity fluid inhibits clay dispersion, but simultaneously requires more additives to achieve appropriate viscosity for proppant emplacement. In total this review highlights the nuances of enhanced hydrogeochemical shale stimulation in relation to the choice of fracturing fluid chemistry.

Quantification of mineral accessible surface area and flow-dependent fluid-mineral reactivity at the pore scale

Accessible surface areas (ASAs) of individual rock-forming minerals exert a fundamental control on the maximum mineral reactivity with formation fluids. Notably, ASA efficiency during fluid-rock reactions can vary by orders of magnitude, depending on the inflow fluid chemistry and the velocity field. Due to the lack of adequate quantification methods, determining the mineral-specific ASAs and their reaction efficiency still remain extremely difficult. Here, we first present a novel joint method that appropriately calculates ASAs of individual minerals in a multi-mineral sandstone. This joint method combines SEM-image processing results and Brunauer-Emmett-Teller (BET) surface area measurements by a Monte-Carlo algorithm to derive scaling factors and ASAs for individual minerals at the resolution of BET measurements. Using these atomic-scale ASAs, we then investigate the impact of flow rate on the ASA efficiency in mineral dissolution reactions during the injection of CO2-enriched brine. This is done by conducting a series of pore-scale reactive transport simulations, using a two-dimensional (2D) scanning electron microscopy (SEM) image of this sandstone. The ASA efficiency is determined employing a domain-averaged dissolution rate and the effective surface area of the most reactive phase in the sandstone (dolomite). As expected, the dolomite reactivity is found to increase with the flow rate, due to the on average high fluid reactivity. The surface efficiency increases slightly with the fluid flow rate, and reaches a relatively stable value of about 1%. The domain averaged method is then compared with the in-out averaged method (i.e the “Black-box” approach), which is often used to analyzed the experimental observations. The in-out averaged method yields a considerable overestimation of the fluid reactivity, a small underestimation of the dolomite reactivity, and a considerable underestimation of the ASA efficiency. The discrepancy between the two methods is becoming smaller when the injection rate increases. Our comparison suggests that the result interpretation of the in-out averaged method should be contemplated, in particular, when the flow rate is small. Nonetheless, our proposed ASA determination method should facilitate accurate calculations of fluid-mineral reactivity in large-scale reactive transport simulations, and we advise that an upscaling of the ASA efficiency needs to be carefully considered, due to the low surface efficiency.

Ion-species in pore fluids with opposite effects on limestone fracturing

At ten percent of sedimentary rocks, limestones are common geo-energy reservoirs. Being highly soluble, limestones are prone to fluid-assisted deformation and their mechanical behaviour likely susceptible to fluid chemistry. In this study, we saturated limestone samples with 0.4 M MgSO4 or 0.4 M Na2SO4 CaCO3-saturated solutions (naturally present in many reservoirs) or a reference CaCO3-saturated solution for 1, 50 or 200 days prior to mechanical testing. Triaxial deformation tests were then performed at 7, 30, and 70 MPa of confining pressure room temperature, under drained conditions. Our results show that exposure to one different cation impacts the strength of this rock (up to 12 of dry rock strength) and its failure dynamics, associated with different microstructural damage distribution. A 200 day exposure to MgSO4 promotes strengthening whilst similar exposure to Na2SO4 leads to weakening. We posit that these strength changes may be related to changes in surface charges on the mineral surfaces. More data on fluid–rock interaction will be key to fully understand fracture propagation in natural carbonate formations.

Thermal stress reduces pocilloporid coral resilience to ocean acidification by impairing control over calcifying fluid chemistry.

The combination of thermal stress and ocean acidification (OA) can more negatively affect coral calcification than an individual stressors, but the mechanism behind this interaction is unknown. We used two independent methods (microelectrode and boron geochemistry) to measure calcifying fluid pH (pHcf) and carbonate chemistry of the corals Pocillopora damicornis and Stylophora pistillata grown under various temperature and pCO2 conditions. Although these approaches demonstrate that they record pHcf over different time scales, they reveal that both species can cope with OA under optimal temperatures (28°C) by elevating pHcf and aragonite saturation state (Ωcf) in support of calcification. At 31°C, neither species elevated these parameters as they did at 28°C and, likewise, could not maintain substantially positive calcification rates under any pH treatment. These results reveal a previously uncharacterized influence of temperature on coral pHcf regulation-the apparent mechanism behind the negative interaction between thermal stress and OA on coral calcification.

Heat stress differentially impacts key calcification mechanisms in reef-building corals

Coral reefs are increasingly threatened by climate change, mass bleaching events and ocean acidification (OA). Coral calcification, a process that is critical to build and maintain the structure of tropical coral reefs, is highly sensitive to both warming and acidifying oceans. However, in contrast to the impacts of OA on coral calcification, significant knowledge gaps remain regarding how coral biomineralization mechanisms are impacted by heat stress and bleaching. Using a combined physiological and geochemical approach, we investigated how a marine heatwave impacted coral symbiotic status (chlorophyll a, algal symbiont density), the carbonate chemistry of the coral calcifying fluid (via δ11B and B/Ca) and skeletal trace element composition in the branching coral Acropora aspera. Importantly, we recorded in situ temperature throughout the bleaching event and recovery as well as coral symbiotic status during peak bleaching and after 7 months of recovery. We show that heat-stressed Acropora corals continued to upregulate the pH of their calcifying fluid (cf); however, dissolved inorganic carbon upregulation inside the cf was significantly disrupted by heat stress. Similarly, we observed suppression of the typical seasonality in the trace element (TE) temperature proxies Sr/Ca, Mg/Ca, Li/Ca and Li/Mg, indicating disruption of important calcification mechanisms, Rayleigh fractionation and reduced growth rates. Anomalies in TE/Ca ratios were still observed 7 months after peak bleaching, even though algal symbiont densities and chlorophyll a concentrations were fully restored at this point. Interestingly, the biomineralization response to heat stress did not differ between thermally distinct reef habitats harbouring coral populations with different heat tolerance, nor between heat-stressed colonies with different severity of bleaching. Our findings suggest that coral biomineralization mechanisms in Acropora are highly sensitive to heat stress, showing similar patterns of biogeochemical stress response as other coral taxa.

Dolomitization of a Miocene-Pliocene progradational carbonate platform by mesohaline brines: Re-examination of the reflux model on Bonaire Island

Neogene dolomites are common in island settings, and they have been used to understand the complex processes of dolomitization. The island of Bonaire was one of the first locations where the concept of reflux dolomitization was applied. Given this historical significance, here we re-evaluate the importance and nature of reflux using a previously unstudied set of outcrops in Bonaire. Mio-Pliocene units in Seru Grandi in northwestern Bonaire show well-defined bodies of dolomite that extend along clinoform surfaces beneath a subhorizontal erosional unconformity. The dolomite distribution suggests early dolomitization as a result of fluids moving downwards through a succession of subtidal facies, as expected from the reflux model. However, non-stoichiometric compositions, weak 18O enrichment, low trace element concentrations and the sedimentological context of the dolomites suggest that refluxing fluid was more likely to be mesohaline in composition rather than hypersaline as previously proposed. In addition, our findings suggest that the fluids did not dolomitize the succession uniformly, but rather elongate bodies of dolomite were developed within selected clinoforms through different events. This variability may be due to temporal changes in the flux, chemistry of reactive fluids and textural changes of original sediment, whereas downdip trends may reflect evolution of magnesium exchange efficiency with distance from the brine source and reactivity of the rock.

Delamination of single layer hollow fiber membranes induced by bi-directional phase separation

Structural delamination across the hollow fiber wall is a major challenge for the fabrication of dual-layer hollow fiber membranes. Delamination may also exist in single-layer hollow fiber membranes because the dope solution undergoes phase separation at both inner and outer surfaces. Different phase inversion mechanisms and rates at the inner and outer surfaces result in hollow fibers with different morphologies across the wall and may lead to delamination between the layers. In this work, the origins of delamination for single-layer hollow fiber membranes are investigated. The effects of dope composition, bore fluid chemistry as well as spinning conditions on delamination are disclosed. Among these parameters, bore fluid composition has the most profound impact on fiber delamination. With carefully designed spinning conditions (e.g. high air gap and take-up speed), the occurrence of fiber delamination can be mitigated. A membrane with a delaminated inner layer often possesses a highly porous inner surface with an improved permeance for water filtration. This work offers feasible solutions to resolve structural delamination of hollow fiber membranes during spinning. It may also provide a new method to fabricate high-flux hollow fiber membranes by producing fiber delamination intentionally.

In situ observation of chrysotile decomposition in the presence of NaCl-bearing aqueous fluid up to 5 GPa and 400 °C

Natural occurrence of chrysotile, a rock-forming serpentine mineral, is largely associated with fluid-rich environments, thus making the fluid chemistry an important factor governing chrysotile growth and stability. Paper examines the effect of alkali chlorides, lowering the H2O activity in fluid, on chrysotile stability at high pressure. The behavior of natural chrysotile (Thetford) in the presence of concentrated NaCl-H2O fluids was studied up to 5 GPa and 400 °C using in-situ Raman spectroscopy and X-ray diffraction combined with resistively heated diamond anvil cell. Reference experiments were also performed on salt-free samples. In salt-free H2O-saturated conditions, chrysotile is stable within the whole temperature range at 1.5–5 GPa. The presence of NaCl in the fluid at XNaCl = mole NaCl/(NaCl+H2O) ≈ 0.1–0.15 strongly suppresses the temperature of chrysotile dehydration at 2–4 GPa to 380 °C, which is about 170 °C lower compared to the equilibrium data for H2O-saturated salt-free system. Talc/talc-like phase only crystallizes at HP-HT conditions as product of the reaction “chrysotile → forsterite + talc”, whereas forsterite appears after the P,T release. This indicates an enhanced solubility of forsterite in supercritical NaCl-H2O fluid at HP-HT conditions. Chrysotile shows disordering/amorphization at unusually low temperature of 150 °C. The shift of the chrysotile dehydration to lower temperatures in saline environment makes this process more operable in natural metamorphic processes in serpentinites. This effect can be extended to other serpentine minerals, including antigorite, a common participant of HP-HT metamorphic reactions in subduction zones.

Using Shale as a Barrier Simplifies Well Abandonment

This article, written by JPT Technology Editor Chris Carpenter, contains highlights of paper SPE 199654, “Simplifying Well Abandonments Using Shale as a Barrier,” by Eric van Oort, SPE, and Maria Juenger, The University of Texas at Austin, and Munir Aldin, SPE, Metarock Laboratories, et al., prepared for the 2020 IADC/SPE International Drilling Conference and Exhibition, Galveston, Texas, 3-5 March. The paper has not been peer reviewed. The complete paper presents the results of an investigation into the creep behavior of North Sea shales and their ability to form effective annular barriers. The large-scale laboratory results show that Lark-Horda shales will form competent low-permeability annular barriers when left uncemented, as confirmed using pressure-pulse-decay measurements. Experimental conditions were found to influence the rate of barrier formation. Higher effective stress, higher temperature, and beneficial manipulation of annular fluid chemistry all have a significant effect. Introduction An alternative to traditional plug-and-abandonment techniques presented it-self more than a decade ago, with observations that formations such as mobile salts and shales could creep into uncemented annular spaces and form competent annular barriers that could be identified on sonic and ultrasonic bond logs and verified using pressure testing. Shale particularly has the necessary characteristics that several guidelines require of a good barrier, being largely impermeable, nonshrinking, ductile, and resistant to chemicals and substances, all of which help provide long-term integrity. Shales that appeared to be particularly well-suited to beneficial annular creep behavior were characterized by low strength and high ductility, high clay content with relatively high smectite content, low levels of quartz and carbonate cementation, relatively high porosity and low compressional wave velocity, and a tendency to yield wellbore instability problems while being drilled. Mechanisms other than creep were considered for the annular blockage behavior observed, but the mounting body of evidence indicates that the predominant mechanism is indeed creep (i.e., the viscoplastic behavior of argillaceous rocks). In the laboratory and field work published to date, stimulation of shale barriers through accelerated creep by pressure and temperature manipulation has received the most attention. The authors investigate barrier activation not only by temperature and pressure activation but also by chemical activation, because it offers practical advantages and reduces risks associated with temperature and pressure activation. Temperature has a significant effect on the viscoplastic behavior of shale, but heating a long shale section (with a minimum barrier length of 50 m) through casing with an effective downhole heater presents considerable practical challenges. Pressure reduction in the annulus through reduction of the hydrostatic head in the wellbore brings with it well-control concerns, particularly when no functional annular barrier is in place. By contrast, circulating a chemical solution in place in an annular space through casing perforations with a workstring and packer arrangement is relatively straightforward and is routine when practicing the perforate, wash, and cement technique in the field.

Advantages of a fast-scanning quadrupole for LA-ICP-MS analysis of fluid inclusions

Fast-scanning quadrupoles more representatively record LA-ICP-MS transient fluid inclusion signals. This allows to (1) target smaller inclusions than before; (2) accurately record polyphase inclusion signals; (3) better characterise fluid chemistry.

Carbonate Replacement as the Principal Ore Formation Process in the Proterozoic McArthur River (HYC) Sediment-Hosted Zn-Pb Deposit, Australia

AbstractThe McArthur River (HYC) Zn-Pb-Ag deposit in the Carpentaria Zn belt, northern Australia, is one of the world’s largest and most studied sediment-hosted base metal deposits, owing to its lack of deformation and preservation of sedimentary and ore textures. However, the ore formation process (syngenetic vs. epigenetic) is still a subject of controversy. In this paper we focus on key characteristics of the HYC deposit that remain unexplained: preservation of sedimentary carbonate (dolomite) and its association with Zn, and the role of thallium (Tl) and manganese (Mn) distribution in the orebody.Our findings demonstrate a sequence of events during ore formation: Tl is hosted almost exclusively within euhedral pyritic overgrowths around early diagenetic pyrite; sphalerite mineralization occurred after Tl-bearing pyrite overgrowths, in association with acid dissolution (replacement) of laminated and nodular dolomite across the subbasin; and outer rims are enriched in Mn on preserved dolomite at the dissolution reaction front in contact with sphalerite. New thermodynamic fluid chemistry modeling demonstrates the metal distribution and paragenesis can be explained by acidic, oxidized ore fluids entering the pyrite-dolomite host lithology, allowing reduction and pH buffering by acid carbonate dissolution, resulting in stepwise metal deposition in an evolving fluid.We argue this represents strong evidence for epigenetic ore formation at HYC. Furthermore, the primary control on ore deposition is not synsedimentary faulting in the subbasin; rather, the chemical potential of sedimentary carbonate within reduced, sulfidic lithologies appears to be of critical importance to precipitation of sphalerite.

Geochemical element mobilisation by interaction of Bowland shale with acidic fluids

Hydraulic fracturing is widely used to exploit unconventional hydrocarbon sources, to enhance exploitation of geothermal energy and to aid in carbon sequestration through underground storage of captured CO2. The hydraulic fracturing fluids, which are commonly acidic, cause dissolution of minerals and desorption of elements which can lead to groundwater contamination. Batch reactor experiments were conducted to explore the interaction of simulated fracturing fluids with two end member compositions of basinal shales of the Bowland-Hodder unit (Carboniferous, UK) whereby the impact of temperature, fluid acidity, and rock/fluid ratio conditions were investigated. The results demonstrate that the fluid acidity is mainly controlled by the oxidative dissolution of pyrite and the dissolution of calcite, impacting mobilisation and fate of major and trace elements. The dissolution of calcite and pyrite significantly dominates the leaching of Sr and As, respectively. Generally, increased fluid acidity and temperature facilitate element mobilisation due to enhanced mineral dissolution and ion desorption, whereas higher rock/fluid ratio (higher mass of carbonate minerals) raises the buffering capacity and may promote the immobilisation of some metal ions by adsorption and precipitation (e.g. Ba, Pb, Fe, Al, and Mn). Moreover, the surface topography of different minerals in polished shale sample sections after fluid-rock interaction indicates that mineralogical compositions may play an important role in determining the pore structure. This research identifies chemical reaction pathways of geochemical elements (including contaminants) in fracturing fluids over a range of fluid chemistries and environmental conditions, and helps to evaluate element mobilisation from shale reservoirs with differing mineralogies.

Understanding controls on hydrothermal dolomitisation: insights from 3D reactive transport modelling of geothermal convection

Abstract. The dominant paradigm for petrogenesis of high-temperature fault-controlled dolomite, widely known as “hydrothermal dolomite” (HTD), invokes upwelling of hot fluid along faulted and fractured conduits from a deep over-pressured aquifer. However, this model has several inherent ambiguities with respect to fluid sources and their dolomitisation potential, as well as mechanisms for delivering enough of these reactive fluids to form substantial volumes of dolomite. Here, we use generic 2D and 3D reactive transport simulations of a single transmissive fault system to evaluate an alternative conceptual model whereby dolomitisation is driven by seawater being drawn down into the subsurface and heated. We examine the evolution of fluid chemistry and the distribution of diagenetic alteration, including predictions of the rate, distribution, and temperature of HTD formation, and consider the possible contribution of this process to the Mg budget of the world's oceans. The simulations suggest that it is possible for convection of seawater along the fault damage zone to form massive dolomite bodies that extend hundreds of metres vertically and along the fault within a timescale of a few tens of thousands of years, with no significant alteration of the country rock. Dolomitisation occurs as a gradient reaction by replacement of host limestones and minor dolomite cementation, and it results in the discharge of Mg2+-poor, Ca2+-rich fluids to the sea floor. Fluids sourced from the basement contribute to the transport of heat that is key for overcoming kinetic limitations to dolomitisation, but the entrained seawater provides the Mg2+ to drive the reaction. Dolomite fronts are sharper on the “up-flow” margin where Mg2+-rich fluids first reach the threshold temperature for dolomitisation, and the “down-flow” dolomite front tends to be broader as the fluid is depleted in Mg2+ by prior dolomitisation. The model demonstrates spatial contrasts in the temperature of dolomitisation and the relative contribution of seawater and basement-derived fluids which are also commonly observed in natural fault-controlled dolomites. In the past, such variations have been interpreted in terms of major shifts in the system driving dolomitisation. Our simulations demonstrate that such changes may also be a product of emergent behaviour within a relatively stable system, with areas that are dolomitised more slowly recording the effect of changes in fluid flow, heat, and solute transport that occur in response to diagenetic permeability modification. Overall, our models robustly demonstrate that high-temperature fault-controlled dolomite bodies can form from mixed convection and act as a sink for Mg in the circulating seawaters. In addition, comparison of our 3D simulations with simplifications to 2D indicate that 2D models misrepresent critical aspects of the system. This has important implications for modelling of systems ranging from geothermal resources and mineralisation to carbonate diagenesis, including hydrothermal karstification and ore genesis as well as dolomitisation.

Antimony in quartz as a vector to mineralization: A statistical approach from five Variscan Sb occurrences (France)

Using in-situ LA-ICP-MS, the trace-element composition of hydrothermal quartz from five Sb mineralized Variscan districts, from different parts of France, were compared. Each of these districts is characterized by the presence of stibnite, with quartz being a ubiquitous gangue mineral. The resulting dataset was processed using a set of multivariate statistical analyses (i.e. principal component analysis, hierarchical cluster analysis, and permutational multivariate analysis of variance). This approach highlights differences in ore-forming processes (e.g., fluid chemistry), recorded in the trace-element pattern of gangue minerals. Using this methodology, we could distinguish different mineralizing events with intricate paragenesis, such as those in the Sioule nappe, which appear to have recorded two different events of Sb precipitation. Results indicate that Sb incorporation in quartz is weakly correlated to other trace elements, but that its contents increase sharply in quartz from stibnite-bearing veins. In this case, Sb shows values >10 ppm and up to 200 ppm, considerably higher than the values measured in quartz unrelated to Sb mineralization (mainly ≤1 ppm). Intermediate Sb contents in quartz would point to the potential for a fluid to precipitate Sb ore. It is concluded that incorporation of Sb in quartz can be confidentially correlated to its content in the mineralizing fluid. Based on our data from five Sb districts in the French Variscan belt, supplemented by published Sb trace-element data in quartz from a number of other Sb deposits around the world, this study highlights the strong potential of the Sb content of quartz as a proxy for tracing Sb mineralization.

Metal bioaccessibility in synthetic body fluids – A way to consider positive and negative alloying effects in hazard assessments

Hazard classification of metal alloys is today generally based on their bulk content, an approach that seldom reflects the extent of metal release for a given environment. Such information can instead be achieved via bioelution testing under simulated physiological conditions. The use of bioelution data instead of bulk contents would hence refine the current hazard classification of alloys and enable grouping. Bioelution data have been generated for nickel (Ni) and cobalt (Co) released from several stainless steel grades, one low-alloyed steel, and Ni and Co metals in synthetic sweat, saliva and gastric fluid, for exposure periods from 2 to 168 h. All stainless steel grades with bulk contents of 0.11–10 wt% Ni and 0.019–0.24 wt% Co released lower amounts of Ni (up to 400-fold) and Co (up to 300-fold) than did the low-alloyed steel (bulk content: 0.034% Ni, 0.015% Co). They further showed a relative bioaccessibility of Ni and Co considerably less than 1, while the opposite was the case for the low-alloyed steel. Surface oxide- and electrochemical corrosion investigations explained these findings in terms of the high passivity of the stainless steels related to the Cr(III)-rich surface oxide that readily adapted to the fluid acidity and chemistry.

Chemistry of Reservoir Fluids in the Aspect of CO2 Injection for Selected Oil Reservoirs in Poland

Worldwide experiences related to geological CO2 storage show that the process of the injection of carbon dioxide into depleted oil reservoirs (CCS-EOR, Carbon Capture and Storage—Enhanced Oil Recovery) is highly profitable. The injection of CO2 will allow an increasing recovery factor (thus increasing CCS process profitability) and revitalize mature reservoirs, which may lead to oil spills due to pressure buildups. In Poland, such a solution has not yet been implemented in the industry. This work provides additional data for analysis of the possibility of the CCS-EOR method’s implementation for three potential clusters of Polish oil reservoirs located at a short distance one from another. The aim of the work was to examine the properties of reservoir fluids for these selected oil reservoirs in order to assure a better understanding of the physicochemical phenomena that accompany the gas injection process. The chemical composition of oils was determined by gas chromatography. All tested oils represent a medium black oil type with the density ranging from 795 to 843 g/L and the viscosity at 313 K, varying from 1.95 to 5.04 mm/s. The content of heavier components C25+ is up to 17 wt. %. CO2–oil MMP (Minimum Miscibility Pressure) was calculated in a CHEMCAD simulator using the Soave–Redlich–Kwong equation of state (SRK EoS). The oil composition was defined as a mixture of n-alkanes. Relatively low MMP values (ca. 8.3 MPa for all tested oils at 313 K) indicate a high potential of the EOR method, and make this geological CO2 storage form more attractive to the industry. For reservoir brines, the content of the main ions was experimentally measured and CO2 solubility under reservoir conditions was calculated. The reservoir brines showed a significant variation in properties with total dissolved solids contents varying from 17.5 to 378 g/L. CO2 solubility in brines depends on reservoir conditions and brine chemistry. The highest calculated CO2 solubility is 1.79 mol/kg, which suggest possible CO2 storage in aquifers.

MARHYS (MARine HYdrothermal Solutions) Database: A Global Compilation of Marine Hydrothermal Vent Fluid, End Member, and Seawater Compositions

AbstractWe introduce a database of hydrothermal vent fluid compositions extracted from peer‐reviewed publications. The database includes general fluid parameters (e.g., temperature, salinity, and pH) as well as major‐, minor‐, and trace‐element concentrations (including rare earth elements) of dissolved cations, anions, reduced carbon compounds, and gases. In addition, isotopic compositions of elements and molecules are included. Each parameter in the database is given in a uniform unit and enables direct intercomparison of data from the incorporated sources. The database provides detailed information about geographic location, the date of sampling, and a broad set of supplementary information that enables clear identification of each individual sample and the original data source. This type of metadata was used to merge compositional data for discrete vent fluid samples that originate from different publications. Hence, the database provides a more complete set of compositional parameters than the original sources do. To facilitate operability, the database is provided as ®Excel sheet, which enables users to visualize, sort, filter, and evaluate the database in a straightforward way. The sample information metadata enables extraction of available vent fluid data for specific regions, tectonic settings, host rock types, etc. The database will be a useful tool in determining (1) mechanisms that set fluid chemistry, as well as (2) regional and global geochemical fluxes across the seabed. To demonstrate the extent of the database, we examine the global distribution of magnesium, chloride, and sodium concentrations in vent fluid samples that are incorporated in MARHYS Database.