Description: Incipient warming of peatlands at high latitudes is expected to modify soil drainage and hence the redox conditions, which has implications for Fe export from soils. This study uses Fe isotopes to assess the processes controlling Fe export in a range of Icelandic soils including peat soils derived from the same parent basalt, where Fe isotope variations principally reflect differences in weathering and drainage. In poorly weathered, well-drained soils (non-peat soils), the limited Fe isotope fractionation in soil solutions relative to the bulk soil (Δ57Fesolution-soil = -0.11 ± 0.12 ‰) is attributed to proton-promoted mineral dissolution. In the more weathered poorly drained soils (peat soils), the soil solutions are usually lighter than the bulk soil (Δ57Fesolution-soil = -0.41 ± 0.32 ‰), which indicates that Fe has been mobilised by reductive mineral dissolution and/or ligand-controlled dissolution. The results highlight the presence of Fe-organic complexes in solution in anoxic conditions. An additional constraint on soil weathering is provided by Si isotopes. The Si isotope composition of the soil solutions relative to the soil (Δ30Sisolution-soil = 0.92 ± 0.26 ‰) generally reflects the incorporation of light Si isotopes in secondary aluminosilicates. Under anoxic conditions in peat soils, the largest Si isotope fractionation in soil solutions relative to the bulk soil is observed (Δ30Sisolution-soil = 1.63 ± 0.40 ‰) and attributed to the cumulative contribution of secondary clay minerals and amorphous silica precipitation. Si supersaturation in solution with respect to amorphous silica is reached upon freezing when Al availability to form aluminosilicates is limited by the affinity of Al for metal-organic complexes. Therefore, the precipitation of amorphous silica in peat soils indirectly supports the formation of metal-organic complexes in poorly drained soils. These observations highlight that in a scenario of decreasing soil drainage with warming high latitude peatlands, Fe export from soils as Fe-organic complexes will increase, which in turn has implications for Fe transport in rivers, and ultimately the delivery of Fe to the oceans.

Description: Understanding the biogeochemical cycle of magnesium (Mg) is not only crucial for terrestrial ecology, as this element is a key nutrient for plants, but also for quantifying chemical weathering fluxes of Mg and associated atmospheric CO2 consumption, requiring distinction of biotic from abiotic contributions to Mg fluxes exported to the hydrosphere. Here, Mg isotope compositions are reported for parent basalt, bulk soils, clay fractions, exchangeable Mg, seasonal soil solutions, and vegetation for five types of volcanic soils in Iceland in order to improve the understanding of sources and processes controlling Mg supply to vegetation and export to the hydrosphere. Bulk soils (δ26Mg = -0.40±0.11‰) are isotopically similar to the parent basalt (δ26Mg = -0.31‰), whereas clay fractions (δ26Mg = -0.62±0.12‰), exchangeable Mg (δ26Mg = -0.75 ± 0.14 ‰), and soil solutions (δ26Mg = -0.89 ± 0.16 ‰) are all isotopically lighter than the basalt. These compositions can be explained by a combination of mixing and isotope fractionation processes on the soil exchange complex. Successive adsorption-desorption of heavy Mg isotopes leads to the preferential loss of heavy Mg from the soil profile, leaving soils with light Mg isotope compositions relative to the parent basalt. Additionally, external contributions from sea spray and organic matter decomposition result in a mixture of Mg sources on the soil exchange complex. Vegetation preferentially takes up heavy Mg from the soil exchange complex (Δ26Mgplant-exch = +0.50±0.09‰), and changes in δ26Mg in vegetation reflect changes in bioavailable Mg sources in soils. This study highlights the major role of Mg retention on the soil exchange complex amongst the factors controlling Mg isotope variations in soils and soil solutions, and demonstrates that Mg isotopes provide a valuable tool for monitoring biotic and abiotic contributions of Mg that is bioavailable for plants and is exported to the hydrosphere.

Description: Molybdenum isotope fractionation accompanying soil development is studied across three pedogenic gradients encompassing a range of controlling factors. These factors include variable redox conditions, organic matter content, Fe and Mn oxy(hydr)oxide content, mineral composition, degree of weathering, pH, type and amount of atmospheric inputs, age, climate, and underlying rock type. Soil profiles from the island of Maui (Hawaii) along a precipitation gradient ranging from 850 to 5050 mm mean annual precipitation show a decrease in average soil δ98Mo from -0.04±0.11‰ at the driest, most oxic site, which is indistinguishable from the basalt parent material (-0.09±0.08‰), to -0.33±0.10‰ at the wettest, most reducing site. A suite of 6 Icelandic soils display a broad trend with heavier δ98Mo values (up to +1.50±0.09‰) in soil horizons that are more weathered and have higher organic matter content. Selective extractions of Mo from different soil components indicate that the association with organic matter and silicate or Ti-oxide residue dominates retention of Mo in these soils, with adsorption on Fe and Mn oxy(hydr)oxides playing a lesser role. Across all basaltic soils, δ98Mo values are lighter in soils that exhibit the most net Mo loss relative to the parent material, and δ98Mo values are heavier in soils that exhibit net Mo gains. A well-drained regolith profile in the Luquillo Mountains of Puerto Rico developed on quartz diorite shows heavier δ98Mo values than the parent material (up to +0.71±0.10‰ with an integrated profile average of +0.28±0.10‰) in soil and shallower saprolite, despite overall moderate loss of 28% of Mo relative to the bedrock. However, the deeper saprolite is unfractionated from bedrock (-0.01±0.10‰, quartz diorite bedrock) indicating that rock weathering dissolution processes and secondary clay formation do not fractionate Mo isotopes. Our data suggest that the Mo mass balance and isotope composition of soils are controlled by redox conditions, organic matter, and atmospheric inputs. In this way Mo isotopes have the potential to react to and record climate driven changes in the weathering environment. The presence of both isotopically light and heavy Mo (relative to parent material) across all sites and within individual soil profiles suggests that it is normal for multiple fractionation mechanisms to operate under the open-system conditions of soils.

Description: Soil thickness and residence time are regulated by a dynamic interplay between soil formation and lateral transport of soil particles and solutes. To unravel this interplay and infer patterns and rates of chemical weathering, soil physical and chemical properties can be used. Here, we present an integrated approach combining numerical modeling with field measurements to assess the impact of slope gradient on soil thickness and chemical weathering at a regional scale. We first perform a number of synthetic model runs simulating soil formation, weathering, erosion, and deposition, which show that soil thickness and weathering degree decline with increasing slope gradient. We then evaluate how those functional relationships compare to soil‐landscape data observed in the field. Soils are sampled at 100 midslope positions under varying slope gradient. The weathering degree is determined using three chemical weathering indices: ratio of iron oxides to total iron (Fed/Fet), chemical index of alteration (CIA), and total reserve in bases (TRB). Finally, we calibrate the Be2D model to our field data to constrain soil residence times and chemical weathering rates. The modeled weathering rates decrease with increasing soil residence time and decreasing slope gradient. The application of the soil‐landscape evolution model in Southern Brazil shows that weathering rates can vary up to 2 orders of magnitude and depend on hillslope gradient. Notwithstanding model limitations and data uncertainties, we demonstrate the potential of an integrated approach, where field data and numerical modeling are integrated to unravel the timescale of soil weathering along transport over hillslopes.

Description: Silicon (Si) is an essential macronutrient for diatoms, an important component of lacustrine primary productivity that represents a link between the carbon and silicon cycles. Reconstructions of lake silicon cycling thus provide an underexploited window onto lake and catchment biogeochemistry. Silicon isotope geochemistry has potential to provide these reconstructions, given the competing source and process controls can be deconvolved. The silica-rich volcanic and hydrothermal systems in Yellowstone National Park are a great source of dissolved silicon into Yellowstone Lake, a system with high silicon, and thus carbon, export rates and the formation of diatom–rich sediment. Yellowstone Lake sediments should be an archive of past silicon biogeochemistry, although the effect of sublacustrine hydrothermal activity or hydrothermal explosion events is unclear. Here, we analysed lake water, tributaries, and hydrothermal vent fluids from Yellowstone Lake for their dissolved Si concentrations, isotope composition ( ) and Ge/Si ratios to evaluate the sources of variability in the lake's Si cycle. Bulk elemental composition and biogenic ( ) content, together with and Ge/Si ratios from a single diatom species, Stephanodiscus yellowstonensis, were analysed in two sediment cores spanning the last 9880 cal. yr BP. We investigate these datasets to identify long term Holocene changes in hydrothermal activity and effects of large and short-term events i.e., hydrothermal and a volcanic eruption. Combinations of , and Ge/Si with XRF and lithology data revealed that Yellowstone Lake has a resilient biogeochemical system: hydrothermal explosions are visible in the lithology but have no identifiable impact on accumulation or on the signature. Both cores show similarities that suggest a stable and homogeneous dSi source across the entire lake. A narrow range of and Ge/Si values suggests that the productive layer of the lake was well mixed and biogeochemically stable, with consistently high hydrothermal inputs of Si throughout the Holocene to buffer against the disturbance events. Variation in concentration through time is weakly correlated with an increase towards younger sediment in the fossil diatom record in both cores. This increase mirrors that seen in ocean records, and follows changes known in summer insolation, summer temperatures and lake water-column mixing since the deglaciation. This suggests that climate forcing, and soil formation ultimately govern the silicon isotope record, which we suggest is via a combination of changes in weathering stoichiometry, diatom production, and relative proportion of dSi sources.