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The oxidation of pyrite is often one of the main drivers affecting groundwater quality during managed aquifer recharge in deep aquifers. Data and techniques that allow detailed identification and quantification of pyrite oxidation are therefore crucial for assessing and predicting the adverse water quality changes that may be associated with this process. In this study, we explore the benefits of combining stable sulphur isotope analysis with reactive transport modelling to improve the identification and characterisation of pyrite oxidation during an aquifer storage and recovery experiment in a chemically and physically heterogeneous aquifer. We characterise the stable sulphur isotope signal (634S) in both the ambient groundwater and the injectant as well as its spatial distribution within the sedimentary sulphur species. The identified stable sulphur isotope signal for pyrite was found to vary between 32 and +34%o, while the signal of the injectant ranged between +9.06 and +14.45%0 during the injection phase of the experiment. Both isotope and hydrochemical data together suggest a substantial contribution of pyrite oxidation to the observed, temporally variable delta S-34 signals. The variability of the delta S-34 signal in pyrite and the injectant were both found to complicate the analysis of the stable isotope data. However, the incorporation of the data into a numerical modelling approach allowed to successfully employ the delta S-34 signatures as a valuable additional constraint for identifying and quantifying the contribution of pyrite oxidation to the redox transformations that occur in response to the injection of oxygenated water. (C) 2017 Elsevier B.V. All rights reserved.
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