title: Thermal intensification of microbial Fe(II)/Fe(III) redox cycling in a pristine shallow sand aquifer on the Canadian Shield.
abstract: This investigation evaluates spatial relationships between summer (July) groundwater temperatures and Fe(II)/Fe(III) biogeochemical cycling over a five year period in a shallow pristine sand aquifer at Meilleurs Bay near Deep River, Ontario, Canada. A warm subsurface thermal island of 12.5-16.1 °C, compared to background conditions of 10-11 °C, was manifest in contour maps of average groundwater temperature over the study period. The warm zone coincided with an area of convergent groundwater flow, implicating horizontal heat transfer by advective convection as the reason for elevated temperatures. Additionally, high concentrations of dissolved Fe(II) and Fe(III) overlapped the warm thermal island, indicative of increased rates of bacterial Fe(II)-oxidation and Fe(III)-reduction. A depletion in the modal abundance of Fe(II)-bearing minerals, notably amphibole and biotite, inside the area of the warm thermal island was also observed, suggesting enhanced mineral dissolution owing to chemoautotrophic Fe(II)-oxidation coupled to the reduction and fixation of dissolved inorganic carbon as biomass. Throughout the aquifer, redox conditions were poised in terms of Eh and pH close to equilibrium with respect to the Fe(II)/Fe(OH)3couple, feasibly enabling simultaneous bacterial Fe(II)-oxidation and Fe(III)-reduction with an adequate supply of electron acceptors and donors, respectively. The significance of higher groundwater temperature as a determinant of elevated dissolved Fe(II) and Fe(III) concentrations induced by thermal intensification of microbial biogeochemical activities yielded Pearson product-moment correlations in which temperature alone, as a single independent variable, explains almost 30 to nearly 60 percent of the variation in the measured dissolved Fe(II) and Fe(III) concentrations in the groundwater. These results emphasize the important influence of thermal conditions on biogeochemical processes in aquifers coupled to the development of steep gradients in groundwater quality over short distances in shallow unconfined groundwater systems.
authors: Department of Earth Sciences, University of Toronto, 22 Russell Street, M5S 3B1, Toronto, Ontario, Canada.
authors: V L
authors: VL
authors: Shirokova
authors: Department of Earth Sciences, University of Toronto, 22 Russell Street, M5S 3B1, Toronto, Ontario, Canada.
authors: A M L
authors: AML
authors: Enright
authors: Department of Earth Sciences, University of Toronto, 22 Russell Street, M5S 3B1, Toronto, Ontario, Canada.
authors: C B
authors: CB
authors: Kennedy
authors: Department of Earth Sciences, University of Toronto, 22 Russell Street, M5S 3B1, Toronto, Ontario, Canada. Electronic address: grant.ferris@utoronto.ca.
authors: F G
authors: FG
authors: Ferris
mesh_terms: D002170:Canada; D005290:Ferric Compounds; D005296:Ferrous Compounds; D060587:Groundwater; D010084:Oxidation-Reduction; D014874:Water Pollutants, Chemical
chemical_list: D005290:Ferric Compounds; D005296:Ferrous Compounds; D014874:Water Pollutants, Chemical
keywords: Bacterial; Biogeochemical cycling; Fe(II)/Fe(III); Groundwater; Mineral weathering; Oxidation-reduction; Temperature