Drought recorded by Ba/Ca in coastal benthic foraminifera

Increasing occurrences of extreme weather events, such as the 2018 drought over northern Europe, are a concerning issue under global climate change. High resolution archives of natural hydroclimate proxies, such as rapidly accumulating sediments containing biogenic carbonates, offer the potential to investigate the frequency and mechanisms of such events in the past. Droughts alter the barium (Ba) concentration of near-continent seawater through the reduction in Ba input from terrestrial runoff, which in turn may be recorded as changes in the chemical composition (Ba/Ca) of foraminiferal calcium carbonates accumulating in sediments. However, so far the use Ba/Ca as a discharge indicator has been restricted to planktonic foraminifera, despite the high relative abundance of benthic species in coastal, shallow-water sites. Moreover, benthic foraminiferal Ba/Ca has mainly been used in open ocean records as a proxy for paleo-productivity. Here we report on a new geochemical dataset measured from living (CTG-labelled) benthic foraminiferal species to investigate the capability of benthic Ba/Ca to record changes in river runoff over a gradient of contrasting hydroclimatic conditions. Individual foraminifera (Bulimina marginata, Nonionellina labradorica) were analyzed by laser-ablation ICP-MS over a seasonal and spatial gradient within Gullmar Fjord, Swedish west coast during 2018–2019. The results are compared to an extensive meteorological and hydrological data set, as well as sediment and pore-water geochemistry. Benthic foraminiferal Ba/Ca correlates significantly to riverine runoff, however, the signals contain both spatial trends with distance to Ba-source, and species-specific influences such as micro-habitat preferences. We deduce that shallow-infaunal foraminifera are especially suitable as proxy for terrestrial Ba input and discuss the potential influence of water-column and pore-water Ba cycling. While distance to Ba-source, water depth, pore-water geochemistry, and species-specific effects need to be considered in interpreting the data, our results demonstrate confidence in the use of Ba/Ca of benthic foraminifera from near-continent records as proxy for past riverine discharge and to identify periods of drought.

A gateway for ion transport on gas bubbles pinned onto solids

Gas bubbles grown on solids are more than simple vehicles for gas transport. They are charged particles with surfaces populated with exchangeable ions. We here unveil a gateway for alkali metal ion transport between oxygen bubbles and semi-conducting (iron oxide) and conducting (gold) surfaces. This gateway was identified by electrochemical impedance spectroscopy using an ultramicroelectrode in direct contact with bubbles pinned onto these solid surfaces. We show that this gateway is naturally present at open circuit potentials, and that negative electric potentials applied through the solid enhance ion transport. In contrast, positive potentials or contact with an insulator (polytetrafluoroethylene) attenuates transport. We propose that this gateway is generated by overlapping electric double layers of bubbles and surfaces of contrasting (electro)chemical potentials. Knowledge of this ion transfer phenomenon is essential for understanding electric shielding and reaction overpotential caused by bubbles on catalysts. This has especially important ramifications for predicting processes including mineral flotation, microfluidics, pore water geochemistry, and fuel cell technology.

Vivianite formation in ferruginous sediments from Lake Towuti, Indonesia

Ferruginous lacustrine systems, such as Lake Towuti, Indonesia, are characterized by a specific type of phosphorus cycling in which hydrous ferric iron (oxyhydr)oxides trap and precipitate phosphorus to the sediment, which reduces its bioavailability in the water column and thereby restricts primary production. The oceans were also ferruginous during the Archean, thus understanding the dynamics of phosphorus in modern-day ferruginous analogues may shed light on the marine biogeochemical cycling that dominated much of Earth's history. Here we report the presence of large crystals (>5 mm) and nodules (>5 cm) of vivianite – a ferrous iron phosphate – in sediment cores from Lake Towuti and address the processes of vivianite formation, phosphorus retention by iron and the related mineral transformations during early diagenesis in ferruginous sediments. Core scan imaging, together with analyses of bulk sediment and pore water geochemistry, document a 30 m long interval consisting of sideritic and non-sideritic clayey beds and diatomaceous oozes containing vivianites. High-resolution imaging of vivianite revealed continuous growth of crystals from tabular to rosette habits that eventually form large (up to 7 cm) vivianite nodules in the sediment. Mineral inclusions like millerite and siderite reflect diagenetic mineral formation antecedent to the one of vivianite that is related to microbial reduction of iron and sulfate. Together with the pore water profiles, these data suggest that the precipitation of millerite, siderite and vivianite in soft ferruginous sediments stems from the progressive consumption of dissolved terminal electron acceptors and the typical evolution of pore water geochemistry during diagenesis. Based on solute concentrations and modeled mineral saturation indices, we inferred vivianite formation to initiate around 20 m depth in the sediment. Negative δ56Fe values of vivianite indicated incorporation of kinetically fractionated light Fe2+ into the crystals, likely derived from active reduction and dissolution of ferric oxides and transient ferrous phases during early diagenesis. The size and growth history of the nodules indicate that, after formation, continued growth of vivianite crystals constitutes a sink for P during burial, resulting in long-term P sequestration in ferruginous sediment.

Vivianite formation in ferruginous sediments from Lake Towuti, Indonesia

Ferruginous lacustrine systems, such as Lake Towuti, Indonesia, can experience restricted primary production due to phosphorus trapping by hydrous ferric iron (oxyhydr)oxides that reduce P concentrations in the water column. The oceans were also ferruginous during the Archean, so understanding the dynamics of phosphorus in modern-day ferruginous analogues may shed light on the marine biogeochemical cycling that dominated much of Earth's history. Here we report the presence of large crystals (> 5 mm) and nodules (> 5 cm) of vivianite – a ferrous iron phosphate – in sediment cores from Lake Towuti, and address the processes of phosphorus retention and iron mineral transformations during diagenesis in ferruginous sediments. Core scans together with analyses of bulk sediment and pore water geochemistry document a 30 m long interval consisting of beds of sideritic and non-sideritic clays and diatomaceous oozes containing diagenetic vivianites. High-resolution imaging of vivianite revealed continuous growth of crystals from tabular to rosette habits that eventually form large (up to 7 cm) vivianite nodules in the sediment. Mineral inclusions like millerite and siderite reflect antecedent diagenetic mineral formation that is related to microbial reduction of iron and sulfate. This implies the formation and growth of vivianite crystals under reducing conditions during diagenesis. Negative ð56Fe values of vivianite indicated reductive dissolution of ferric oxides as the source of Fe in the vivianites with incorporation of microbially fractionated light Fe2+ into the crystals. The size and growth history of the nodules indicate that, after formation, continued growth of vivianite may constitute a significant sink for P in these sediments.