Carbonation of borehole seals: comparing evidence from short-term laboratory experiments and long-term natural analogues

It is crucial that the engineered seals of boreholes in the vicinity of a deep storage facility remain effective for considerable timescales if the long-term geological containment of stored CO2 is to be effective. These timescales extend beyond those achievable by laboratory experiments or industrial experience. Study of the carbonation of natural Ca silicate hydrate (CSH) phases provides a useful insight into the alteration processes and evolution of cement phases over long-timescales more comparable with those considered in performance assessments. Samples from two such natural analogues in Northern Ireland have been compared with samples from laboratory experiments on the carbonation of Portland cement. Samples showed similar carbonation reaction processes even though the natural and experimental samples underwent carbonation under very different conditions and timescales. These included conversion of the CSH phases to CaCO3 and SiO2, and the formation of a well-defined reaction front. In laboratory experiments the reaction front is associated with localised Ca migration, localised matrix porosity increase, and localised shrinkage of the cement matrix with concomitant cracking. Behind the reaction front is a zone of CaCO3 precipitation that partly seals porosity. A broader and more porous/permeable reaction zone was created in the laboratory experiments compared to the natural samples, and it is possible that short-term experiments might not fully replicate slower, longer-term processes. That the natural samples had only undergone limited carbonation, even though they had been exposed to atmospheric CO2 or dissolved in groundwater for several thousands of years, may indicate that the limited amounts of carbonate mineral formation may have protected the CSH phases from further reaction

Determining noble gas partitioning within a CO2–H2O system at elevated temperatures and pressures

Quantifying the distribution of noble gases between phases is essential for using these inert trace gases to track the processes controlling multi-phase subsurface systems. Here we present experimental data that defines noble gas partitioning for two phase CO2–water systems. These are at the pressure and temperature range relevant for engineered systems used for anthropogenic carbon capture and geological storage (CCS) technologies, and CO2-rich natural gas reservoirs (CO2 density range 169–656 kg/m3 at 323–377 K and 89–134 bar). The new partitioning data are compared to predictions of noble gas partitioning determined in low-pressure, pure noble gas–water systems for all noble gases except neon and radon. At low CO2 density there was no difference between measured noble gas partitioning and that predicted in pure noble gas–water systems. At high CO2 density, however, partition coefficients express significant deviation from pure noble gas–water systems. At 656 kg/m3, these deviations are −35%, 74%, 113% and 319% for helium, argon, krypton and xenon, respectively. A second order polynomial fit to the data for each noble gas describes the deviation from the pure noble gas–water system as a function of CO2 density. We argue that the difference between pure noble gas–water systems and the high density CO2–water system is due to an enhanced degree of molecular interactions occurring within the dense CO2 phase due to the combined effect of inductive and dispersive forces acting on the noble gases. As the magnitude of these forces are related to the size and polarisability of each noble gas, xenon followed by krypton and argon become significantly more soluble within dense CO2. In the case of helium repulsive forces dominate and so it becomes less soluble as a function of CO2 density

Note: a dual temperature closed loop batch reactor for determining the partitioning of trace gases within CO2-water systems

An experimental approach is presented which can be used to determine partitioning of trace gases within CO2-water systems. The key advantages of this system are (1) The system can be isolated with no external exchange, making it ideal for experiments with conservative tracers. (2) Both phases can be sampled concurrently to give an accurate composition at each phase at any given time. (3) Use of a lower temperature flow loop outside of the reactor removes contamination and facilitates sampling. (4) Rapid equilibration at given pressure/temperature conditions is significantly aided by stirring and circulating the water phase using a magnetic stirrer and high-pressureliquid chromatography pump, respectively

A review of developments in carbon dioxide storage

Carbon capture and storage (CCS) has been identified as an urgent, strategic and essential approach to reduce anthropogenic CO2 emissions, and mitigate the severe consequences of climate change. CO2 storage is the last step in the CCS chain and can be implemented mainly through oceanic and underground geological sequestration, and mineral carbonation. This review paper aims to provide state-of-the-art developments in CO2 storage. The review initially discussed the potential options for CO2 storage by highlighting the present status, current challenges and uncertainties associated with further deployment of established approaches (such as storage in saline aquifers and depleted oil and gas reservoirs) and feasibility demonstration of relatively newer storage concepts (such as hydrate storage and CO2-based enhanced geothermal systems). The second part of the review outlined the critical criteria that are necessary for storage site selection, including geological, geothermal, geohazards, hydrodynamic, basin maturity, and economic, societal and environmental factors. In the third section, the focus was on identification of CO2 behaviour within the reservoir during and after injection, namely injection-induced seismicity, potential leakage pathways, and long-term containment complexities associated with CO2-brine-rock interaction. In addition, a detailed review on storage capacity estimation methods based on different geological media and trapping mechanisms was provided. Finally, an overview of major CO2 storage projects, including their overall outcomes, were outlined. This review indicates that although CO2 storage is a technically proven strategy, the discussed challenges need to be addressed in order to accelerate the deployment of the technology. In addition, beside the necessity of techno-economic aspects, public acceptance of CO2 storage plays a central role in technology deployment, and the current ethical mechanisms need to be further improved

Notch/Delta signaling constrains reengineering of pro-T cells by PU.1

PU.1 is essential for early stages of mouse T cell development but antagonizes it if expressed constitutively. Two separable mechanisms are involved: attenuation and diversion. Dysregulated PU.1 expression inhibits pro-T cell survival, proliferation, and passage through β-selection by blocking essential T cell transcription factors, signaling molecules, and Rag gene expression, which expression of a rearranged T cell antigen receptor transgene cannot rescue. However, Bcl2 transgenic cells are protected from this attenuation and may even undergo β-selection, as shown by PU.1 transduction of defined subsets of Bcl2 transgenic fetal thymocytes with differentiation in OP9-DL1 and OP9 control cultures. The outcome of PU.1 expression in these cells depends on Notch/Delta signaling. PU.1 can efficiently divert thymocytes toward a myeloid-like state with multigene regulatory changes, but Notch/Delta signaling vetoes diversion. Gene expression analysis distinguishes sets of critical T lineage regulatory genes with different combinatorial responses to PU.1 and Notch/Delta signals, suggesting particular importance for inhibition of E proteins, Myb, and/or Gfi1 (growth factor independence 1) in diversion. However, Notch signaling only protects against diversion of cells that have undergone T lineage specification after Thy-1 and CD25 up-regulation. The results imply that in T cell precursors, Notch/Delta signaling normally acts to modulate and channel PU.1 transcriptional activities during the stages from T lineage specification until commitment

Red-bed bleaching in a CO2 storage analogue: insights from Entrada Sandstone fracture-hosted mineralization

Improving our ability to predict the interactions between CO2 and reservoir rocks at geological time scales is of key importance if carbon capture and storage (CCS) is to have a role in climate-change mitigation, particularly in the light of likely regulatory requirements. Understanding and identifying the relevant geological processes over long time scales can be obtained only at natural-analogue sites. At one such site, in the Salt Wash Graben area of Utah, USA, widespread bleaching affects the Middle Jurassic red-bed “wet dune” Entrada Sandstone. Previous work has proposed a genetic link between the bleaching and spatially concomitant recent and modern CO2-rich fluids. The results presented here challenge some of the previous models and come from a detailed petrographic examination of mineralized fractures in the Entrada Sandstone that are centered in vertical extensions to the bleaching. These fractures typically contain complex mineralization assemblages. Pyrite was a paragenetically early phase, identifiable from common pseudomorphs of mixed iron oxides and oxyhydroxides that rarely contain relict pyrite. The pyrite contains up to 3 wt% arsenic. The volume of fracture-adjacent bleached sandstone is sufficient to have been the source of iron for the pyrite originally present in the fracture. The pyrite pseudomorphs occur at the center of fracture- and pore-filling cements that comprise intergrowths of hematite–goethite–jarosite–gypsum, an assemblage that suggests that their formation resulted from the oxidative alteration of pyrite, a genetic link supported by the arsenic present in the iron-bearing minerals. The presence of jarosite and proximal removal of earlier, sandstone-hosted carbonates are consistent with, and indicative of, the low-pH conditions associated with pyrite oxidation reactions. Calcite- and gypsum-cemented fractures crosscut, and contain fragments of, the pyrite-pseudomorphic and -oxidation assemblages, proving that they postdate pyrite formation and its subsequent oxidation, and that pyrite oxidation was not a result of modern weathering reactions. In outcrop, some calcite- and gypsum-cemented fractures link with travertine deposits associated with the modern and recent CO2-rich fluids. The mineral assemblages observed here, and the paragenetic sequence that we have inferred, suggest that the fracture-associated bleaching patterns result from the fracture-fed movement of sulfur-bearing reducing fluids, with hydrogen sulfide the most likely bleaching agent. We conclude that bleaching adjacent to fractures is not genetically related to modern CO2-bearing fluids despite the spatial relationship. The bleaching was already present when the modern fluids utilized the same fracture-based fluid pathways. We suggest that the more widespread regional bleaching formed contemporaneously with the fracture bleaching and followed similar mechanisms. This study highlights the complexity of interpreting analogue sites and the importance of using field and petrographic observations to unravel textures and events that are juxtaposed spatially but not temporally

Empowering Teachers as Leaders: A Hard Sell

Despite emphasis on preparing teachers as leaders, teacher educators realize that the transition of classroom practitioners into school leaders is fraught with many obstacles. This session addresses some of these obstacles, describes strategies and opportunities that we have used in our graduate master’s degree programs for teachers that support professionals as they make this change. The session will present evidence on the results of our efforts in terms of teachers’ performances within their programs and in the field after they graduate

Trash removal methods for improved mechanical emptying of pit latrines using a screw auger

Trash in pit latrines is one of the largest challenges facing pit emptying technologies, including the powered auger (the Excrevator), developed for improved emptying in lower- and lower-middle income countries. This study focused on two trash removal methods in conjunction with pit emptying by the Excrevator: (1) simultaneous removal of trash with sludge and (2) manual trash removal prior to sludge removal. Simultaneous removal was tested by adding to the inlet of the Excrevator system two cutting heads designed to reduce the size of trash particles before entering the pipe and auger. Laboratory testing indicated that the auger will not provide the rotational speeds necessary for proper maceration of fibrous materials such as clothing, indicating that a separate maceration unit with higher rotational methods may be more appropriate. Four manual trash removal mechanisms were designed to improve on existing manual trash ‘fishing’ tools such as iron rods with fixed hooks. Two of these tools (the ‘claw’ and the ‘hook’) showed promising laboratory results and were subsequently field tested in Mzuzu, Malawi. Both tools proved more efficient than the current tools used in the field and have potential for use in Malawi

Assessment of the impact of CO 2 storage in sandstone formations by experimental studies and geochemical modeling: the case of the Mesohellenic Trough, NW Greece

Representative sandstone samples from Mesohellenic Trough (NW Greece) were selected to investigate the geochemical reactions that occur when they come in contact with CO2 under representative in-situ conditions (T = 70 °C, P = 150 bar, 6 months reaction in batch experiments). Those sandstones consisted of predominant calcite and quartz, with lesser amounts of feldspars, chlorite, ankerite, dolomite, kaolinite, montmorillonite and muscovite. After reaction with CO2, the brine became acidic and was enriched in cations as a result of mineral dissolution. Minor mineralogical changes were observed that involved: a) the dissolution of carbonate minerals and b) the incongruent dissolution of chlorite to form clays and silica. The results related to these, have been linked with geochemical modelling using the PHREEQC code. Simulation results for a 10 ka time period predicted that chlorite was expected to dissolve completely within 100 years, leading to boehmite growth and increasing the mass of dolomite. Feldspars were expected to react at a later stage in the reaction sequence. Sensitivity tests were run to access the effect of various adjustable parameters on the outcome results. The geochemical experiments and modelling lend support to the view that Pentalofos and Tsotyli sandstone formations of the Mesohellenic Trough are suitable for the long-term storage of CO2 produced in the neighbouring lignite-fired power plants, at least in terms of mineralogy and geochemistry

Evolution of the mineralogy, pore structure and transport properties of Nordland Shale following exposure to supercritical carbon dioxide

The Nordland shale forms the caprock of the Utsira sands of the Sleipner reservoir currently used for carbon dioxide sequestration. The long-term exposure of shale rocks to supercritical carbon dioxide (scCO2), or scCO2-brine mixtures, may lead to structural and chemical changes in shale that lead to increases in permeability of inter-layers and caprocks, that may mean changes to plume migration behaviour and/or loss of seal efficiency of caprocks. A detailed study has been made of the initial pore structure of Nordland shale and the changes following accelerated treatment with scCO2. Gas sorption scanning curves have suggested that the void space of the original shale consisted of a Network (denoted 1) of micropores and smaller mesopores that is thermodynamically independent of a Network (2) of larger mesopores and macropores. This work introduces a new iodononane pre-adsorption technique to map the macroscopic (>microns) spatial distribution of micropores (<2 nm) and smaller mesopores in shales using CXT. CXT imaging of shale samples with iodononane pre-adsorbed in Network 1, or with entrapped mercury confined to only Network 2, suggested that both small- and large-sized pore networks were pervasive through the shale and associated with the continuous illite matrix phase. The feldspar and quartz grains did not form part of either network, though inter-particle macropores were found surrounding these mineral grains from CXT imaging of mercury entrapped there. Kinetic gas uptake experiments conducted on samples before and after filling Network 1 with iodononane suggested that the smaller mesopores were, despite their small size and thermodynamic independence from the macropores, still critical to mass transport, with the diffusion flux being funnelled through them. Shale surface areas obtained using the homotattic patch adsorption model were found more physically realistic than those determined via the ISO BET method since multi-linear regression of only the logarithm of the former, together with that of the Network 1 pore volume, predicted the gas-phase mass transport coefficient following treatment. This work demonstrated the need for the novel characterisation methods and data analysis presented here to properly understand the structure-transport relationship in shales exposed to scCO2