Glaciated environments have been highlighted as important sources of bioavailable nutrients, with inputs of glacial meltwater potentially influencing productivity in downstream ecosystems. However, it is currently unclear how riverine nutrient concentrations vary across a spectrum of glacial cover, making it challenging to accurately predict how terrestrial fluxes will change with continued glacial retreat. Using 40 rivers in Chilean Patagonia as a unique natural laboratory, we investigate how glacial cover affects riverine Si and Fe concentrations, and infer how exports of these bioessential nutrients may change in the future. Dissolved Si (as silicic acid) and soluble Fe (<0.02 μm) concentrations were relatively low in glacier-fed rivers, whereas concentrations of colloidal-nanoparticulate (0.02-0.45 μm) Si and Fe increased significantly as a function of glacial cover. These colloidal-nanoparticulate phases were predominately composed of aluminosilicates and Fe-oxyhydroxides, highlighting the need for size-fractionated analyses and further research to quantify the lability of colloidal-nanoparticulate species. We also demonstrate the importance of reactive particulate (>0.45 μm) phases of both Si and Fe, which are not typically accounted for in terrestrial nutrient budgets but can dominate riverine exports. Dissolved Si and soluble Fe yield estimates showed no trend with glacial cover, suggesting no significant change in total exports with continued glacial retreat. However, yields of colloidal-nanoparticulate and reactive sediment-bound Si and Fe were an order of magnitude greater in highly glaciated catchments and showed significant positive correlations with glacial cover. As such, regional-scale exports of these phases are likely to decrease as glacial cover disappears across Chilean Patagonia, with potential implications for downstream ecosystems. Glacial weathering processes have been identified to be particularly important in the generation of potentially bioavailable iron (Fe) (

Subglacial Lake Whillans lies below around 800 m of Antarctic ice and is isolated from fresh sources of photosynthetic organic matter to sustain life. The diverse microbial ecosystems within the lake and underlying sediments are therefore dependent on a combination of relict, overridden, marine-derived organic matter and mineral-derived energy. Here, we conduct experiments to replicate subglacial erosion involving both gentle and high-energy crushing of Subglacial Lake Whillans sediments and the subsequent addition of anoxic water. We find that substantial quantities of reduced species, including hydrogen, methane, acetate and ammonium and oxidised species such as hydrogen peroxide, sulfate and carbon dioxide are released. We propose that the concomitant presence of both hydrogen and hydrogen peroxide, alongside high concentrations of mineral surface radicals, suggests that the splitting of water on freshly abraded mineral surfaces increases the concentrations of redox pairs from rock-water reactions and could provide a mechanism to augment the energy available to microbial ecosystems.

Abstract. Glaciers and ice sheets are renowned for their abrasive power, yet little is known of the mechanochemical reactions which are initiated by abrasion in these environments and their effect on subglacial biogeochemistry. Here, we use sedimentary rocks representative of different subglacial environments and from a previously glaciated terrain, along with subglacial sediments, to investigate the potential for subglacial erosion to generate H2O2 and to release bio-utilisable organic carbon and nutrients (N, Fe). Samples were crushed using a ball mill, water was added to rock powders within gastight vials, and samples were incubated in the dark at 4 ∘C. Headspace and water samples were taken immediately after the addition of water and then again after 5 and 25 h. Samples generated up to 1.5 µmol H2O2 g−1. The total sulfur content, a proxy for the sulfide content, did not correlate with H2O2 generation, suggesting that the pyrite content was not the sole determinant of net H2O2 production. Other factors including the presence of carbonates, Fe-driven Fenton reactions and the pH of the solution were also likely to be important in controlling both the initial rate of production and subsequent rates of destruction of H2O2. Further, we found that erosion can provide previously unaccounted sources of bio-utilisable energy substrates and nutrients, including up to 880 nmol CH4 g−1, 680 nmol H2 g−1, volatile fatty acids (up to 1.7 µmol acetate g−1) and 8.2 µmolNH4+g-1 to subglacial ecosystems. These results highlight the potentially important role that abrasion plays in providing nutrient and energy sources to subglacial microbial ecosystems underlain by sedimentary rocks.

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Abstract. Glaciers and ice-sheets are renowned for their abrasive power, yet little is known of the mechanochemical reactions which are initiated by abrasion in these environments and their effect on subglacial biogeochemistry. Here, we use sedimentary rocks representative of different subglacial environments and from a previously glaciated terrain to investigate the potential for subglacial erosion to generate H2O2 and release bio-utilisable organic carbon and nutrients (N, Fe). Samples were crushed using a ball mill, water added to rock powders within gastight vials, and samples incubated in the dark at 4 °C. Headspace and water samples were taken immediately after the addition of water and then again after 5 and 25 h. Samples generated up to 1.5 µmol H2O2 g-1. The total sulphur content, a proxy for the sulphide content, did not correlate with H2O2 generation, suggesting that the pyrite content was not the sole determinant of net H2O2 production. Other factors, including the presence of carbonates, Fe-driven Fenton reactions and the pH of the solution were also likely to be important in controlling both the initial rate of production and subsequent rates of destruction of H2O2. Further, we found erosion can provide previously unaccounted sources of bio-utilisable energy substrates and nutrients, including up to 880 nmol CH4 g-1, 680 nmol H2 g-1, volatile fatty acids (up to 1.7 µmol acetate g-1) and 8.2 µmol NH4+ g-1 to subglacial ecosystems. These results highlight the potentially important role that abrasion plays in providing nutrient and energy sources to subglacial microbial ecosystems underlain by sedimentary rocks.