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Abstract: Chemical tracers have been used in various C capture and storage (CCS) projects worldwide primarily to provide information regarding subsurface migration of CO2 and to verify CO2 containment. Understanding the movement and interactions of CO2 in the subsurface is a challenging task considering the variety of states in which it exists (i.e. gas, liquid, supercritical, dissolved in water) and the range of possible storage mechanisms (i.e. residual or capillary trapping, dissolved in water, structural trapping or incorporation into minerals). This paper critically reviews several chemical tracer applications and case studies for CCS projects. In many instances, there are parallels (e.g. tracer classes and applications) between tracers in the oil and gas industry and in CCS. It has been shown that chemical tracers can complement geophysical measurements (e.g. seismic) in understanding the formation behaviour of CO2. Although tracers have been successfully used in many CCS projects, some fundamental information, for example partitioning and adsorption, about the behaviour of tracers is still lacking and this can be an issue when interpreting tracer data (e.g. determining leakage rates). In this paper the deployment and recovery of chemical tracers and their use on various CCS projects are described. [Copyright &y& Elsevier]

Abstract: The mechanisms for storage of CO2 in rock formations include structural/stratigraphic, mineral, solubility and residual trapping. Residual trapping is very important in terms of both containment security and storage capacity. However, to date, the contribution from residual trapping (i.e. immobilisation of supercritical fluid via capillarity in pore spaces) is still relatively difficult to quantify accurately. Using a laboratory-based testing program, this study demonstrates the feasibility of using reactive ester tracers (i.e. triacetin, propylene glycol diacetate and tripropionin), which partition between a mobile water phase and a stationary supercritical CO2 phase, to quantify the residual CO2 saturation, Sgr , of a rock formation. The proposed single-well test involves injecting these tracers into the subsurface, followed by CO2 saturated water, where the ester tracers slowly hydrolyse to form products with differing partition coefficients. After a suitable period of time, allowing for partial hydrolysis, water containing the tracer mixture is produced from the subsurface and analysed using gas chromatography mass spectrometry (GCMS). A numerical simulator of the tracer behaviour in a reservoir is used to explain the differential breakthrough of these tracer compounds during water production to estimate Sgr . Computer modelling suggests that the use of esters tracers to determine CO2 residual saturation is a potentially robust method. The supercritical CO2/water partition coefficients directly dictate the amount of time that each tracer spends in the CO2 and water phases. As such for modelling of tracer behaviour and estimating Sgr , knowing the tracer partition coefficient is essential; in this paper, the first laboratory study to determine the partition coefficients of these reactive ester tracers is described. [Copyright &y& Elsevier]