The sedimentary fingerprint of an open-marine iron shuttle

We present iron (Fe) concentration and Fe isotope data for a sediment core transect across the Peru upwelling area, which hosts one of the ocean's most pronounced oxygen minimum zones (OMZs). The lateral progression of total Fe to aluminum ratios (FeT/Al) across the continental margin indicates that sediments within the OMZ are depleted in Fe whereas sediments below the OMZ are enriched in Fe relative to the lithogenic background. Rates of Fe loss within the OMZ, as inferred from FeT/Al ratios and sedimentation rates, are in agreement with benthic flux data that were calculated from pore water concentration gradients. The mass of Fe lost from sediments within the OMZ is within the same order of magnitude as the mass of Fe accumulating below the OMZ. Taken together, our data are in agreement with a shuttle scenario where Fe is reductively remobilized from sediments within the OMZ, laterally transported within the anoxic water column and re-precipitated within the more oxic water below the OMZ. Sediments within the OMZ have increased 56Fe/54Fe isotope ratios relative to the lithogenic background, which is consistent with the general notion of benthic release of dissolved Fe with a relatively low 56Fe/54Fe isotope ratio. The Fe isotope ratios increase across the margin and the highest values coincide with the greatest Fe enrichment in sediments below the OMZ. The apparent mismatch in isotope composition between the Fe that is released within the OMZ and Fe that is re-precipitated below the OMZ implies that only a fraction of the sediment-derived Fe is retained near-shore whereas another fraction is transported further offshore. We suggest that a similar open-marine shuttle is likely to operate along many ocean margins. The observed sedimentary fingerprint of the open-marine Fe shuttle differs from a related transport mechanism in isolated euxinic basins (e.g., the Black Sea) where the laterally supplied, reactive Fe is quantitatively captured within the basin sediments. We suggest that our findings are useful to identify OMZ-type Fe cycling in the geological record.

Long term low latitude and high elevation cosmogenic 3He production rate inferred from a 107 ka-old lava flow in northern Chile; 22°S-3400 m a.s.l

Available geological calibration sites used to estimate the rate at which cosmogenic 3He is produced at the Earth’s surface are mostly clustered in medium to high latitudes. Moreover, most of them have exposure histories shorter than tens of thousands of years. This lack of sites prevents a qualitative assessment of available production models used to convert cosmogenic 3He concentrations into exposure ages and/or denudation rates. It thus limits our ability to take into account the atmospheric, geomagnetic and solar modulation conditions that might have affected the production of cosmogenic nuclides in the past for longer exposure histories and in low latitude regions. We present the cosmogenic 3He production rate inferred from a new geological calibration site located in northern Chile. Five samples were collected on the surface of the largest and best-preserved lava flow of the San Pedro volcano (21.934°S-68.510°W- 3390 m a.s.l), which displays pristine crease-structure features. 40Ar/39Ar dating yield a reliable plateau age of 107±12 ka for the eruption of this lava flow. Eight pyroxene aliquots separated from the surface samples yield a weighted average cosmogenic 3He concentration of 99.3±1.2 Mat.g-1 from which a local cosmogenic 3He production rate of 928±101 at.g-1.yr-1 is calculated. The local production rate is then scaled to a sea level high latitude (SLHL) reference position using different combinations of geographic spatialization schemes, atmosphere models and geomagnetic field reconstructions, yielding SLHL production rates between 103±11 and 130±14 at.g-1.yr-1 consistent with the most recent estimates available from the literature. Finally, we use the same scaling frameworks to re-evaluate the mean global-scale cosmogenic 3He production rate in olivine and pyroxene minerals at 120±16 at.g-1.yr-1 from the compilation of previously published calibration datasets.

Experimental determination of barium isotope fractionation during diffusion and adsorption processes at low temperatures

Variations in barium (Ba) stable isotope abundances measured in low and high temperature environments have recently received increasing attention. The actual processes controlling Ba isotope fractionation, however, remain mostly elusive. In this study, we present the first experimental approach to quantify the contribution of diffusion and adsorption on mass- dependent Ba isotope fractionation during transport of aqueous Ba2+ ions through a porous medium. Experiments have been carried out in which a BaCl2 solution of known isotopic composition diffused through u-shaped glass tubes filled with silica hydrogel at 10 C and 25 C for up to 201 days. The diffused Ba was highly fractionated by up to -2.15‰ in d137/134Ba, despite the low relative difference in atomic mass. The time-dependent isotope fractionation can be successfully reproduced by a diffusive transport model accounting for mass-dependent differences in the effective diffusivities of the Ba isotope species (D137Ba/D134Ba = (m134/m137)^b). Values of b extracted from the transport model were in the range of 0.010–0.011. Independently conducted batch experiments revealed that adsorption of Ba onto the surface of silica hydrogel favoured the heavier Ba isotopes (a = 1.00015 ± 0.00008). The contribution of adsorption on the overall isotope fractionation in the diffusion experiments, however, was found to be small. Our results contribute to the understanding of Ba isotope fractionation pro- cesses, which is crucial for interpreting natural isotope variations and the assessment of Ba isotope ratios as geochemical proxies.