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Iron and manganese reduction driven by organic matter and mixing of fresh and saline groundwater in the Fraser River delta aquifer, Vancouver, Canada Jia, Kun

Abstract

We present results of field investigations of the biogeochemistry of an aquifer a few km from the ocean adjacent to the Fraser River in Vancouver, Canada. At the site, a wedge of relatively dense saline ocean water enters the aquifer in the hyporheic zone at the river bottom, migrates away from the river along the base of the aquifer to a maximum distance of approximately 500m inland, where it overturns and mixes with fresh groundwater. The mixed saline - fresh water then flows back under a regional freshwater gradient and eventually discharges to the river at the top of the saline wedge. Pore waters show iron concentrations peak at over 300 mg/L (5.4 mM) and manganese at 7 mg/L (0.13 mM) at the upper mixing zone - the interface between terrestrial recharge and top of the overturned saline groundwater. The reducible concentrations on the sediment are approximately 784-2,576 mg/kg (14-46 mM/kg) iron and 110-330 mg/kg (2-6mM/kg) manganese. The dominant process is the reductive dissolution of iron and manganese oxide minerals via organic matter oxidation, although acid-volatile sulfide and methane measurements show that both sulfate reduction and methanogenesis are also occurring. Dissolved organic matter (DOM) concentrations ranged between 5 and 30 mg/L. Excitation – emission fluorescence spectroscopy is used to help identify the distinct sources of DOM, which include terrestrial from fresh recharge, detrital from sediments and from inflowing ocean water. One-dimensional kinetic reactive-transport modeling that includes primary mineral redox reactions and secondary mineral precipitation was used to: i) interpret the role of mixing of fresh and saline water, ii) to constrain reduction-rate parameters and metabolic activity levels from field data, including the oxidation rate of organic matter by iron and manganese oxides, probably accompanied with sulfate reduction and methanogenesis; iii) to understand how other secondary minerals further control aqueous ferrous iron and manganese concentrations through mineral precipitation/dissolution processes; v) to gain insight into the long-term evolution of the geochemistry at the site.

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Attribution-NonCommercial-NoDerivs 2.5 Canada