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Abstract: We present a semi-empirical thermodynamic model with uncertainties that encompasses the full range of compositions in H2O–CO2–NaCl mixtures in the range of 10–380°C and 1–3500bars. For binary H2O–CO2 mixtures, the activity–composition model is built from solubility experiments. The parameters describing interactions between H2O and CO2 are independent of the absolute thermodynamic properties of the end-members and vary strongly non-linearly with pressure and temperature. The activity of water remains higher than 0.88 in CO2-saturated solutions across the entire pressure–temperature range. In the H2O–NaCl system, it is shown that the speciation of aqueous components can be accounted for by a thermodynamic formalism where activities are described by interaction parameters varying with intensive properties such as pressure and temperature but not with concentration or ionic strength, ensuring consistency with the Gibbs–Duhem relation. The thermodynamic model reproduces solubility experiments of halite up to 650°C and 10kbar, and accounts for ion pairing of aqueous sodium and chloride ions with the use of associated and dissociated aqueous sodium chloride end-members whose relative proportions vary with salinity. In the H2O–CO2–NaCl system, an activity–composition model reproduces the salting-out effect with interactions parameters between aqueous CO2 and the aqueous species created by halite dissolution. The proposed thermodynamic properties are compatible with the THERMOCALC database (Holland and Powell, 2011) and the equations used to retrieve the activity model in H2O–CO2 can be readily applied to other systems, including minerals. [Copyright &y& Elsevier]

Abstract: Secure storage of anthropogenic carbon dioxide (CO2) in geological reservoirs requires predicting gas–water–rock interactions over millennial timescales. Noble gases and carbon isotope measurements can be used to shed light on the nature of competing dissolution—precipitation processes over different timescales, from the fast dissolution of gaseous CO2 in groundwater to more sluggish reactions involving dissolution and precipitation of newly formed minerals in the reservoir. Here we study a compilation of gas analyses including noble gases and δ13C of CO2 from nine different natural CO2 reservoirs. Amongst these reservoirs, the Bravo Dome CO2 field (New Mexico, USA) shows distinct geochemical trends which are explained by degassing of noble gases from groundwater altering the composition of the gas phase. This groundwater degassing is synchronous with the dissolution of CO2 in groundwater. Progressive creation of alkalinity via CO2-promoted mineral dissolution is required to explain the observed positive correlation between CO2/3He and δ13C of the gas phase, a unique feature of Bravo Dome. The differences between Bravo Dome and other natural CO2 reservoirs are likely explained by the more recent filling of Bravo Dome, reflecting CO2–water–rock interactions over thousands of years rather than over millions of years in older reservoirs. [Copyright &y& Elsevier]

Analysis of 87Sr/86Sr ratios and modelling of formation water, injection water and produced water compositions from the CO2CRC Otway Research Facility in Victoria, Australia are used to test tracer behaviour and response in push-pull experiments. Such experiments are an essential pre-requisite to understanding the controls imposed by reservoir heterogeneities on CO 2 dissolution rates which may be an important stabilising mechanism for geological carbon storage. The experiments (Otway stage 2B extension in 2014) comprised two sequential tests in which ~100 t of CO 2 -saturated water was injected with combinations of Sr and Br or Li and Fluorescein tracers, each injection being followed by two staged extractions of ~10 t and a final extraction of ~50 t all spaced at ~10 day intervals. Analysis of the 87Sr/86Sr ratios of the produced fluids from the first injection, spiked with SrCl 2 and NaBr, is consistent with Sr behaving conservatively. This contrasts with previous interpretations in which Br was argued to have behaved conservatively while Sr, which dilutes ~three times as fast as Br, was thought to be lost to a mineral phase. Such Sr-loss cannot explain the evolution of 87Sr/86Sr ratios. The analysis of 87Sr/86Sr ratios in the waters produced after the second injection episode, spiked with LiCl and Fluorescein tracers, allows calculation of the fractions of the formation waters and the injection waters from both tests 1 and 2. The Sr, Li and SO 4 tracers (the later formed by oxidation of formation sulphide) all indicate similar rates of dilution that is consistent with conservative behaviour. The results of the two injection episodes with spaced extractions are compared with two subsequent push-pull injections in which the produced waters, spiked with methanol, were extracted continuously. These continuous extraction experiments exhibited significantly less dilution over the same range of produced to injected water volumes (up to only ~0.6) than the earlier experiments with spaced extractions. This implies that some process related to the pauses in extraction enhances mixing of injected and formation waters. Achieving the objective of using push-pull experiments to assess reservoir heterogeneities and CO 2 dissolution rates will require better assessment of the various tracers to establish which behave conservatively followed a proper understanding of the causes of the variations in mixing as fluids are extracted from the formations. • 87Sr/86Sr ratios are consistent with conservative behaviour of Sr at the CO2CRC Otway site. • 87Sr/86Sr ratios and Sr concentrations allow calculation of 3 components. • Suggestions for improvements in experimental protocols are presented. [ABSTRACT FROM AUTHOR]