The Influence of Water-rock Reactions and O Isotope Exchange with CO2 on Water Stable Isotope Composition of CO2 Springs in SE Australia

Monitoring injected CO2 in CCS sites using oxygen isotopes of water has been demonstrated in field and laboratory experiments. Here, we examine natural CO2-rich springs in the Daylesford-Hepburn region, South East Australia, which show water 18O depletion compared to local precipitation. Geochemical modelling shows that water-rock reactions are unlikely to have a significant effect on the observed δ18O values, which can only be explained by isotopic exchange with CO2. The water δ18O shift can be used for monitoring CO2 impact on shallow groundwater aquifers, provided that there is sufficient CO2 and distinction between water and CO2 δ18O values exists

Stepping into the Same River Twice: Field Evidence for the Repeatability of a CO2 Injection Test

A single well characterisation test was conducted at the CO2CRC Otway storage site in Victoria, Australia, in 2011 and repeated in 2014. The near-well permeability was found to have declined nearly 60% since the 2011 test, while the residual saturation inferred from a variety of techniques was lower in 2014. There was a significant change in water chemistry, suggesting an alteration of near-well reservoir properties. Possible reasons for these changes are explored, and the implications for other field tests are discussed

Using oxygen isotopes to quantitatively assess residual CO2 saturation during the CO2CRC Otway Stage 2B Extension residual saturation test

Residual CO2 trapping is a key mechanism of secure CO2 storage, an essential component of the Carbon Capture and Storage technology. Estimating the amount of CO2 that will be residually trapped in a saline aquifer formation remains a significant challenge. Here, we present the first oxygen isotope ratio (δ18O) measurements from a single-well experiment, the CO2CRC Otway 2B Extension, used to estimate levels of residual trapping of CO2. Following the initiation of the drive to residual saturation in the reservoir, reservoir water δ18O decreased, as predicted from the baseline isotope ratios of water and CO2, over a time span of only a few days. The isotope shift in the near-wellbore reservoir water is the result of isotope equilibrium exchange between residual CO2 and water. For the region further away from the well, the isotopic shift in the reservoir water can also be explained by isotopic exchange with mobile CO2 from ahead of the region driven to residual, or continuous isotopic exchange between water and residual CO2 during its back-production, complicating the interpretation of the change in reservoir water δ18O in terms of residual saturation. A small isotopic distinction of the baseline water and CO2 δ18O, together with issues encountered during the field experiment procedure, further prevents the estimation of residual CO2 saturation levels from oxygen isotope changes without significant uncertainty. The similarity of oxygen isotope-based near-wellbore saturation levels and independent estimates based on pulsed neutron logging indicates the potential of using oxygen isotope as an effective inherent tracer for determining residual saturation on a field scale within a few days

The influence of oxygen isotope exchange between CO2 and H2O in natural CO2-rich spring waters: implications for geothermometry

Oxygen isotope ratio (δ18O) value deviations from the Meteoric Water Line with no significant change in the hydrogen isotope (δ2H) composition have been reported in naturally occurring CO2-rich waters from around the world. Here we review the effects of oxygen isotope exchange with CO2, high temperature equilibration with bedrock minerals and mineral dissolution and precipitation reactions on the CO2-rich water isotopic composition. We present two case studies from Daylesford (Australia) and Pah Tempe (Utah, USA) mineral springs, where we use a numerical geochemical modelling approach to resolve the influence of low temperature water-rock interactions and CO2 equilibration on the observed oxygen isotope ranges observed in the mineral waters. In both cases, we find that mineral dissolution – precipitation reactions are unlikely to have a significant effect on the groundwater isotopic compositions, and that the observed δ18O values in natural CO2 springs can be simply explained by equilibrium fractionation between water and free phase CO2. Traditionally, the interaction of CO2 and water in a natural CO2-rich groundwater setting has only been associated with water 18O depletion and this is the first study to consider 18O enrichment. We establish that in a natural setting, CO2 and water equilibration can result in water 18O depletion or enrichment, and that the change in the oxygen isotope composition ultimately depends on the initial CO2 and water δ18O values. Our new conceptual model therefore provides a mechanism to explain water 18O enrichment at ambient temperatures. This finding is critical for the use of δ18O in groundwater geothermometry and for the interpretation of natural water circulation depths: we argue that in some cases, natural waters previously interpreted as geothermal based on their oxygen isotope composition may actually have acquired their isotopic signature through interaction with CO2 at ambient temperatures

Glacial-to-interglacial changes in nitrate supply and consumption in the subarctic North Pacific from microfossil-bound N isotopes at two trophic levels

Reduced nitrate supply to the subarctic North Pacific (SNP) surface during the last ice age has been inferred from coupled changes in diatom-bound delta N-15 (DB-delta N-15), bulk sedimentary delta N-15, and biogenic fluxes. However, the reliability of bulk sedimentary and DB-delta N-15 has been questioned, and a previously reported delta N-15 minimum during Heinrich Stadial 1 (HS1) has proven difficult to explain. In a core from the western SNP, we report the foraminifera-bound delta N-15 (FB-delta N-15) in Neogloboquadrina pachyderma and Globigerina bulloides, comparing them with DB-delta N-15 in the same core over the past 25 kyr. The delta N-15 of all recorders is higher during the Last Glacial Maximum (LGM) than in the Holocene, indicating more complete nitrate consumption. N. pachyderma FB-delta N-15 is similar to DB-delta N-15 in the Holocene but 2.2% higher during the LGM. This difference suggests a greater sensitivity of FB-delta(15)NZ to changes in summertime nitrate drawdown and delta N-15 rise, consistent with a lag of the foraminifera relative to diatoms in reaching their summertime production peak in this highly seasonal environment. Unlike DB-delta N-15, FB-delta N-15 does not decrease from the LGM into HS1, which supports a previous suggestion that the HS1 DB-delta N-15 minimum is due to contamination by sponge spicules. FB-delta N-15 drops in the latter half of the Bolling/Allerod warm period and rises briefly in the Younger Dryas cold period, followed by a decline into the mid-Holocene. The FB-delta N-15 records suggest that the coupling among cold climate, reduced nitrate supply, and more complete nitrate consumption that characterized the LGM also applied to the deglacial cold events

Oxygen isotopes as a tool to quantify reservoir-scale CO2 pore-space saturation

Structural and residual trapping of carbon dioxide (CO2) are two key mechanisms of secure CO2 storage, an essential component of Carbon Capture and Storage technology. Estimating the amount of CO2 that is trapped by these two mechanisms is a vital requirement for accurately assessing the secure CO2 storage capacity of a formation, but remains a key challenge. Here, we review recent field and laboratory experiment studies and show that simple and relatively inexpensive measurements of oxygen isotope ratios in both the injected CO2 and produced water can provide an assessment of the amount of CO2 that is stored by residual and structural trapping mechanisms. We find that oxygen isotope assessments provide results that are comparable to those obtained by geophysical techniques. For the first time we assess the advantages and potential limitations of using oxygen isotopes to quantify CO2 pore-space saturation based on a comprehensive review of oxygen isotope measurements from reservoir waters and various global CO2 injection test sites. We further summarise the oxygen isotope composition of captured CO2 in order to establish the controls on this fingerprint