Experimental investigation of carbon dioxide trapping due to capillary retention in saline aquifers

Capillary trapping is a physical mechanism by which carbon dioxide (CO₂) is naturally immobilized in the pore spaces of aquifer rocks during geologic carbon sequestration operations, and thus a key aspect of estimating geologic storage potential. Here, we studied capillary trapping of supercritical carbon dioxide (scCO₂), and the effect of initial scCO₂ saturation and flow rate on the storage/trapping potential of Berea sandstone. We performed two‐phase, scCO₂‐brine displacements in two samples, each subject to four sequential drainage–imbibition core‐flooding cycles to quantify end‐point saturations of scCO₂ with the aid of micro‐ and macro‐computed tomography imaging. From these experiments, we found that between 51% and 75% of the initial CO₂ injected can be left behind after the brine injection. We also observed that the initial scCO₂ saturation influenced the residual scCO₂ saturation to a greater extent than the rate of brine injection under the experimental conditions examined. In spite of differences in the experimental conditions tested, as well as those reported in the literature, initial and residual saturations were found to follow a consistent relationship.     

Low‐temperature catalytic CO2 hydrogenation with geological quantities of ruthenium: a possible abiotic CH4 source in chromitite‐rich serpentinized rocks

Metal‐catalysed CO₂ hydrogenation is considered a source of methane in serpentinized (hydrated) igneous rocks and a fundamental abiotic process germane to the origin of life. Iron, nickel, chromium and cobalt are the catalysts typically employed in hydrothermal simulation experiments to obtain methane at temperatures >200°C. However, land‐based present‐day serpentinization and abiotic gas apparently develop below 100°C, down to approximately 40–50°C. Here, we document considerable methane production in thirteen CO₂ hydrogenation experiments performed in a closed dry system, from 20 to 90°C and atmospheric pressure, over 0.9–122 days, using concentrations of non‐pretreated ruthenium equivalent to those occurring in chromitites in ophiolites or igneous complexes (from 0.4 to 76 mg of Ru, equivalent to the amount occurring approximately in 0.4–760 kg of chromitite). Methane production increased with time and temperature, reaching approximately 87 mg CH₄ per gram of Ru after 30 days (2.9 mgCH₄/g_ru/day) at 90°C. At room temperature, CH₄ production rate was approximately three orders of magnitude lower (0.003 mgCH₄/g_ru/day). We report the first stable carbon and hydrogen isotope ratios of abiotic CH₄ generated below 100°C. Using initial δ¹³C_CO2 of ‐40‰, we obtained room temperature δ¹³C_CH4 values as ¹³C depleted as ?142‰. With time and temperature, the C‐isotope separation between CO₂ and CH₄ decreased significantly and the final δ¹³C_CH4 values approached that of initial δ¹³C_CO2. The presence of minor amounts of C₂‐C₆ hydrocarbons is consistent with observations in natural settings. Comparative experiments at the same temperatures with iron and nichel catalysts did not generate CH₄. Ru‐enriched chromitites could potentially generate methane at low temperatures on Earth and on other planets.     

Real‐time quadrupole mass spectrometer analysis of gas in borehole fluid samples acquired using the U‐tube sampling methodology

Sampling of fluids in deep boreholes is challenging because of the necessity of minimizing external contamination and maintaining sample integrity during recovery. The U‐tube sampling methodology was developed to collect large volume, multiphase samples at in situ pressures. As a permanent or semi‐permanent installation, the U‐tube can be used for rapidly acquiring multiple samples or it may be installed for long‐term monitoring applications. The U‐tube was first deployed in Liberty County, TX to monitor crosswell CO₂ injection as part of the Frio CO₂ sequestration experiment. Analysis of gases (dissolved or separate phase) was performed in the field using a quadrupole mass spectrometer, which served as the basis for determining the arrival of the CO₂ plume. The presence of oxygen and argon in elevated concentrations, along with reduced methane concentration, indicates sample alteration caused by the introduction of surface fluids during borehole completion. Despite producing the well to eliminate non‐native fluids, measurements demonstrate that contamination persists until the immiscible CO₂ injection swept formation fluid into the observation wellbore.     

Chemical and isotopic signatures of Na/HCO3/CO2‐rich geofluids,North Portugal

Geochemical and isotopic studies have been undertaken to assess the origin of CO₂‐rich waters issuing in the northern part of Portugal. These solutions are hot (76°C) to cold (17°C) Na–HCO₃ mineral waters. The δ²H and δ¹⁸O signatures of the mineral waters reflect the influence of altitude on meteoric recharge. The lack of an ¹⁸O‐shift indicates there has been no high temperature water–rock interaction at depth, corroborating the results of several chemical geothermometers (reservoir temperature of about 120°C). The low ¹⁴C activity (up to 9.9 pmC) measured in some of the cold CO₂‐rich mineral waters (total dissolved inorganic carbon) is incompatible with the presence of ³H (from 1.7 to 4.1 TU) in those waters, which indicates relatively short subsurface circulation times. The δ¹³C values of CO₂ gas and dissolved inorganic carbon range between ?6‰ and ?1‰ versus Vienna‐Peedee Belemnite, indicating that the total carbon in the recharge waters is being diluted by larger quantities of CO₂ (¹⁴C‐free) introduced from deep‐seated (upper mantle) sources, masking the ¹⁴C‐dating values. The differences in the ⁸⁷Sr/⁸⁶Sr ratios of the studied thermal and mineral waters seem to be caused by water–rock interaction with different granitic rocks. Chlorine isotope signatures (?0.4‰ < δ³⁷Cl < +0.4‰ versus standard mean ocean chloride) indicate that Cl in these waters could be derived from mixing of a small amount of igneous Cl from leaching of granitic rocks.     

The role of the stress regime on microseismicity induced by overpressure and cooling in geologic carbon storage

Fluid injection in deep geological formations usually induces microseismicity. In particular, industrial‐scale injection of CO₂ may induce a large number of microseismic events. Since CO₂ is likely to reach the storage formation at a lower temperature than that corresponding to the geothermal gradient, both overpressure and cooling decrease the effective stresses and may induce microseismicity. Here, we investigate the effect of the stress regime on the effective stress evolution and fracture stability when injecting cold CO₂ through a horizontal well in a deep saline formation. Simulation results show that when only overpressure occurs, the vertical total stress remains practically constant, but the horizontal total stresses increase proportionally to overpressure. These hydro‐mechanical stress changes result in a slight improvement in fracture stability in normal faulting stress regimes because the decrease in deviatoric stress offsets the decrease in effective stresses produced by overpressure. However, fracture stability significantly decreases in reverse faulting stress regimes because the size of the Mohr circle increases in addition to being displaced towards failure conditions. Fracture stability also decreases in strike slip stress regimes because the Mohr circle maintains its size and is shifted towards the yield surface a magnitude equal to overpressure minus the increase in the horizontal total stresses. Additionally, cooling induces a thermal stress reduction in all directions, but larger in the out‐of‐plane direction. This stress anisotropy causes, apart from a displacement of the Mohr circle towards the yield surface, an increase in the size of the Mohr circle. These two effects decrease fracture stability, resulting in the strike slip being the least stable stress regime when cooling occurs, followed by the reverse faulting and the normal faulting stress regimes. Thus, characterizing the stress state is crucial to determine the maximum sustainable injection pressure and maximum temperature drop to safely inject CO₂.     

Are rocks still water‐wet in the presence of dense CO2 or H2S?

The various modes of acid gas storage in aquifers, namely structural, residual, and local capillary trapping, are effective only if the rock remains water‐wet. This paper reports an evaluation, by means of the captive‐bubble method, of the water‐wet character in presence of dense acid gases (CO₂, H₂S) of typical rock‐forming minerals such as mica, quartz, calcite, and of a carbonate‐rich rock sampled from the caprock of a CO₂ storage reservoir in the South‐West of France. The method, which is improved from that previously implemented with similar systems by Chiquet et al. (Geofluids 2007; 7 : 112), allows the advancing and receding contact angles, as well as the adhesion behavior of the acid gas on the mineral substrate, to be evaluated over a large range of temperatures (up to 140°C), pressures (up to 150 bar), and brine salinities (up to NaCl saturation) representative of various geological storage conditions. The water‐receding (or gas‐advancing) angle that controls structural and local capillary trapping is observed to be not significantly altered in the presence of dense CO₂ or H₂S. In contrast, some alteration of the water‐advancing (or gas‐receding) angle involved in residual trapping is observed, along with acid gas adhesion, particularly on mica. A spectacular wettability reversal is even observed with mica and liquid H₂S. These results complement other recent observations on similar systems and present analogies with the wetting behavior of crude oil/brine/mineral systems, which has been thoroughly studied over the past decades. An insight is given into the interfacial forces that govern wettability in acid gas‐bearing aquifers, and the consequences for acid gas geological storage are discussed along with open questions for future work.     

Fluid dynamics and fluid‐structural relationships in the Red Lake mine trend,Red Lake greenstone belt,Ontario, Canada

The Red Lake mine trend, a deformation zone in the Archean Red Lake greenstone belt that hosts the world‐class Campbell‐Red Lake gold deposit, is characterized by abundant foliation‐parallel iron‐carbonate ± quartz veins with banded colloform‐crustiform structures and cockade breccias overprinted by silicification and gold mineralization. There is an apparent incompatibility between the cavity‐fill structures of the veins and breccias (typically developed at shallow crustal depths) and the upper greenschist to lower amphibole facies metamorphic conditions recorded in the host rocks (indicating relatively deep environments). This, together with the development of veins along the foliation plane, represents an enigmatic problem that may be related to the interplay between fluid dynamics and stress field. We approach this problem through systematic study of fluid inclusion planes (FIPs) in the vein minerals, including the orientations of the FIPs and the pressure–temperature conditions inferred from fluid inclusion microthermometry. We find that fluid inclusions in the main stage vein minerals (pregold mineralization ankerite and quartz and syn‐ore quartz) are predominantly carbonic without a visible aqueous phase, whereas many inclusions in the postore stage contain an aqueous phase. Most FIPs are subvertical, and many are subparallel to the foliation. High fluid pressure coupled with the high wetting angles of the water‐poor, carbonic fluids may have been responsible for the abundance of brittle deformation features. The development of subvertical FIPs is interpreted to indicate episodic switching of the maximum principal compressive stress (σ₁) from subhorizontal (perpendicular to the foliation) to subvertical (parallel to the foliation) orientation. The subvertical σ₁ is favorable for the formation of foliation‐parallel veins, as fractures are preferentially opened along the foliation in such a stress regime, the origin of which may be linked to the fluid source.     

Simulation of the impact of faults on CO2 injection into sandstone reservoirs

Numerical simulations of multiphase CO₂ behavior within faulted sandstone reservoirs examine the impact of fractures and faults on CO₂ migration in potential subsurface injection systems. In southeastern Utah, some natural CO₂ reservoirs are breached and CO₂‐charged water flows to the surface along permeable damage zones adjacent to faults; in other sites, faulted sandstones form barriers to flow and large CO₂‐filled reservoirs result. These end‐members serve as the guides for our modeling, both at sites where nature offers ‘successful’ storage and at sites where leakage has occurred. We consider two end‐member fault types: low‐permeability faults dominated by deformation‐band networks and high‐permeability faults dominated by fracture networks in damage zones adjacent to clay‐rich gouge. Equivalent permeability (k) values for the fault zones can range from <10^?14 m² for deformation‐band‐dominated faults to >10^?12 m² for fracture‐dominated faults regardless of the permeability of unfaulted sandstone. Water–CO₂ fluid‐flow simulations model the injection of CO₂ into high‐k sandstone (5 × 10^?13 m²) with low‐k (5 × 10^?17 m²) or high‐k (5 × 10^?12 m²) fault zones that correspond to deformation‐band‐ or fracture‐dominated faults, respectively. After 500 days, CO₂ rises to produce an inverted cone of free and dissolved CO₂ that spreads laterally away from the injection well. Free CO₂ fills no more than 41% of the pore space behind the advancing CO₂ front, where dissolved CO₂ is at or near geochemical saturation. The low‐k fault zone exerts the greatest impact on the shape of the advancing CO₂ front and restricts the bulk of the dissolved and free CO₂ to the region upstream of the fault barrier. In the high‐k aquifer, the high‐k fault zone exerts a small influence on the shape of the advancing CO₂ front. We also model stacked reservoir seal pairs, and the fracture‐dominated fault acts as a vertical bypass, allowing upward movement of CO₂ into overlying strata. High‐permeability fault zones are important pathways for CO₂ to bypass unfaulted sandstone, which leads to reduce sequestration efficiency. Aquifer compartmentalization by low‐permeability fault barriers leads to improved storativity because the barriers restrict lateral CO₂ migration and maximize the volume and pressure of CO₂ that might be emplaced in each fault‐bound compartment. As much as a 3.5‐MPa pressure increase may develop in the injected reservoir in this model domain, which under certain conditions may lead to pressures close to the fracture pressure of the top seal.     

DNA FROM HUMAN ANCIENT BACTERIA: A NOVEL SOURCE OF GENETIC EVIDENCE FROM ARCHAEOLOGICAL DENTAL CALCULUS

We report a molecular methodology to obtain and analyse ancient bacterial DNA from archaeological dental calculus. Recent and archaeological DNA samples, as old as 4000 bp , were successfully extracted and amplified with species‐specific PCR primers. We propose this approach in order to: detect the presence of specific bacterial species infecting past human populations; compare the composition of ancient oral microbiomes among human populations; and analyse the genetic variability and covariation of bacteria and human host populations. Genomic analysis of bacteria from dental calculus is a promising source of evidence for palaeopathological and micro‐evolutionary studies, focused either on micro‐organisms or their human hosts.     

Melian obsidian in NW Turkey: Evidence for early Neolithic trade

Abstract

Archaeological investigations carried out at the Early Neolithic coastal site of Co?kuntepe in northwestern Turkey yielded an assemblage of 110 obsidian artifacts displaying the macroscopic characteristics of the well-known obsidian deposits on the Cycladic island of Melos. Analysis of three samples from this homogeneous obsidian assemblage using both X-Ray Fluorescence and Laser Ablation High Resolution Inductively Coupled Plasma Mass Spectrometry confirmed that these artifacts were derived from Melos. The presence of these Melian obsidian artifacts at Co?kuntepe, along with a few pieces with central Anatolian macroscopic characteristics, is intriguing because intensive production of tools made of local flint was also identified at the site through the analysis of surface scatters. This finding raises the question of the status of obsidian and associated procurement systems. The presence of obsidian can be also used to argue that certain coastal villages acted as nodes of exchange for Aegean seafarers at times in the late 7th millennium B.C.