Landslide-induced iron mobilisation shapes benthic accumulation of nutrients, trace metals and REE fractionation in an oligotrophic alpine stream

Large alpine landslides that entrain substantial organic material below the water table and create suspended floodplains may have long-term consequences for the mobilisation of redox sensitive elements, such as Fe, into streamwaters. In turn, the cycling of iron in aquatic systems can influence the fate of nutrients, alter primary productivity, enhance accumulation of trace metals and induce fractionation of rare earth elements (REE). In this study we examine a reach of a pristine oligotrophic alpine stream bracketing a 30year-old landslide and explore the consequences of landslide-induced Fe mobilisation for aqueous geochemistry and the composition of benthic stream cobble biofilm. Elevated Fe2+ and Mn in landslide zone stream waters reflect inputs of circumneutral groundwater from the landslide debris-zone floodplain. Geochemical characteristics are consistent with reductive dissolution being a primary mechanism of Fe2+ and Mn mobilisation. Stream cobble biofilm in the landslide zone is significantly (P<0.01) enriched in poorly crystalline Fe(III) (∼10–400 times background) and Mn (∼15–150 times background) (1M HCl extractable; Fe(III)Ab). While the landslide zone accounts for less than ∼9% of the total stream length, we estimate it is responsible for approximately 60–80% of the stream’s benthic biofilm load of poorly crystalline Fe(III) and Mn. Biofilm Fe(III) precipitates are comprised mainly of ferrihydrite, lepidocrocite and an organic-Fe species, while precipitate samples collected proximal to hyporheic seeps contain abundant sheath structures characteristic of the neutrophilic Fe(II)-oxidising bacteria Leptothrix spp. Stream-cobble Fe(III)-rich biofilm is accumulating PO43− (∼3–30 times background) and behaving as a preferential substrate for photosynthetic periphyton, with benthic PO43−, chlorophyll a, organic carbonHCl and total N all significantly positively correlated with Fe(III)Ab and significantly elevated within the landslide zone (P<0.01). P K-edge XANES indicates P is associated with both ferric and Ca-phosphate minerals, while SEM-EDX elemental mapping of Fe(III) precipitates reveal strong spatial associations between P, Ca and Fe. Cobble Fe(III)-rich biofilm is also sorbing and accumulating multiple trace metals and REE. Within the landslide zone there are significant (P<0.01) enrichments (up to ∼10–100 times background) for most trace metals examined here and metals display significant positive linear correlations with Fe(III)Ab on a log transformed basis. Stream cobble biofilm also exhibits distinct REE fractionation along the flow path, with light REE (La, Ce, Nd, Pr) preferentially partitioning to the Fe(III) and Mn-rich biofilm within the landslide zone. Accumulation of PO43− and trace metals in this relatively environmentally labile form may have implications for their bioavailability and downstream transport, but further research is required to assess possible ecological consequences. This study demonstrates the potential for large alpine landslides to encourage reach-scale circumneutral Fe mobilisation in adjacent streams, thereby shaping multiple aspects of benthic stream geochemistry for many years after the landslide event itself.