ALBERT

Description: The correlation between concentrations of dissolved barium (dBa) and silicon (dSi) in the modern ocean supports the use of Ba as a paleoceanographic proxy. However, the mechanisms behind their linkage and the exact processes controlling oceanic Ba cycling remain enigmatic. To discern the extent to which this association arises from biogeochemical processes versus physical mixing, we examine the behavior of Ba and Si at the Congo River-dominated Southeast Atlantic margin where active biological processes and large boundary inputs override the large-scale ocean circulation. Here we present the first combined measurements of dissolved stable Ba (δ138Ba) and Si (δ30Si) isotopes as well as Ba and Si fluxes estimated based on 228Ra from the Congo River mouth to the northern Angola Basin. In the surface waters, river-borne particle desorption or dissolution and shelf inputs lead to non-conservative additions of both dBa and dSi to the Congo-shelf-zone, with the Ba flux increasing more strongly than that of Si across the shelf. In the epipelagic and mesopelagic layers, Ba and Si are decoupled likely due to different depths of in situ barite precipitation and biogenic silica production. In the deep waters of the northern Angola Basin, we observe large enrichment of dBa, likely originating from high benthic inputs from the Congo deep-sea fan sediments. Our results reveal different mechanisms controlling the biogeochemical cycling of Ba and Si and highlight a strong margin influence on marine Ba cycling. Their close association across the global ocean must therefore mainly be a consequence of the large-scale ocean circulation. Key Points Stronger enrichment of dissolved barium (dBa) than silicon (dSi) observed in the shelf-zone of the Congo plume Diatom silica production has negligible effect on dissolved Ba isotopic compositions in large river plumes Strong dBa enrichment (up to 24 nM) in the deep water of the northern Angola Basin likely originates from high benthic inputs

Description: Key Points: - Bio-essential element concentrations in surface waters decreased from spring to summer with removal ratios reflecting biological uptake - Effects of volcanic inputs from Eyjafjallajökull in spring 2010 were pronounced for Al, Mn and Zn but returned to typical levels in summer - Deep winter convection dominated trace element supply to surface waters with minor contributions from atmospheric and diffusive mixing We present dissolved and total dissolvable trace elements for spring and summer cruises in 2010 in the high latitude North Atlantic. Surface and full depth data are provided for Al, Cd, Co, Cu, Mn, Ni, Pb, Zn in the Iceland and Irminger Basins, and consequences of biological uptake and inputs by the spring Eyjafjallajökull volcanic eruption are assessed. Ash from Eyjafjallajökull resulted in pronounced increases in Al, Mn and Zn in surface waters in close proximity to Iceland during the eruption, whilst 3 months later during the summer cruise levels had returned to more typical values for the region. The apparent seasonal removal ratios of surface trace elements were consistent with biological export. Assessment of supply of trace elements to the surface mixed layer for the region, excluding volcanic inputs, indicated that deep winter mixing was the dominant source, with diffusive mixing being a minor source (between 13.5% (dissolved Cd (DCd)) and ‐2.43% (DZn) of deep winter flux), and atmospheric inputs being an important source only for DAl and DZn (DAl up to 42% and DZn up to 4.2% of deep winter+diffusive fluxes) and typically less than 1% for the other elements. Elemental supply ratios to the surface mixed layer through convection were comparable to apparent removal ratios we calculated between spring and summer. Given that deep mixing dominated nutrient and trace element supply to surface waters, predicted increases in water column stratification in this region may reduce supply, with potential consequences for primary production and the biological carbon pump.

Description: The Congo River supplies vast quantities of trace metals (TMs) to the South Atlantic Ocean, but TM budgets for the Congo plume derived using radium isotopes for GEOTRACES cruise GA08 suggest additional input other than the river outflow. Considering the tight correlations between most dissolved TMs and salinity in the plume and the high rainfall during the wet season over the Congo shelf, we hypothesized that wet atmospheric deposition is a TM source to the Congo plume. Observed TM concentrations in rainwaters across the Congo shelf were mostly comparable to values from previous work in the North Atlantic and Mediterranean Sea. Wet deposition contributed the equivalent of 43% dCd, 21% dCu, 20% dPb and 68% dZn of the Congo River fluxes. Our findings show an important role of wet deposition in supplying TMs to the South Atlantic overlapping with the region that receives substantial TM fluxes from the Congo River. Key Points The Congo River is an important source of trace metals (TMs) to the South Atlantic Ocean revealed by data from GEOTRACES cruise GA08 Wet deposition (rainfall) is identified as an additional TM source to the Congo plume by concurrently considering river and rain data Rainfall supplies anthropogenic dTMs (Cd, Cu, Pb and Zn) with fluxes equivalent to 20%–68% of those from the Congo River on the Congo shelf Plain Language Summary The Congo River has the second largest freshwater discharge volume globally and creates an extensive near-equatorial plume into the Atlantic Ocean. The Congo plume constitutes an important source of trace metals (TMs) to the ocean, which impacts biogeochemical cycles in the tropical and subtropical ocean. However, existing work suggests a discrepancy within the TM budgets in the Congo plume and points to unknown source other than the Congo River or shelf sediments. Most TM concentrations across the Congo plume remain tightly correlated with salinity, suggesting that any additional sources are likely also freshwater-derived or enter the ocean at the river mouth coincidently with direct riverine TM inputs. Here, TM concentrations in ocean, river and rainwater collected during the GEOTRACES GA08 cruise are combined to suggest that wet deposition augmented some Congo TM fluxes to the ocean. Fluxes of anthropogenic Cd, Cu, Pb and Zn to the Congo shelf from wet deposition are of the same order of magnitude as the Congo River. Concentrations of these elements in rainwater are similar to prior observations reported for the North Atlantic and Mediterranean Sea, suggesting that a large fraction of the global range of rainwater concentrations over the ocean has been captured in our observations.

Description: Radium isotopes are produced by decay of an isotope of thorium, a highly particle reactive element. Radium is relatively soluble in seawater such that once a thorium isotope in suspended or bottom sediments decays, a fraction of the produced radium isotope may be released to solution. 224Ra (3.7-day half-life) and 223Ra (11.4-day half-life) are used extensively as tracers for interaction on the shelf and for submarine groundwater discharge (SGD). 228Ra is strongly enriched in shelf waters and in the Transpolar Drift (TPD) and its half-life (5.8 years) is well suited to study the fate of this shelf-derived water in the central Arctic. This dataset collected in the framework of GEOTRACES during PS94 in 2015 shows that the input of 228Ra in the TPD has increased since previous studies in 2007 and 2011. The distribution of 228Ra-daughter 228Th (1.9 y half-life) and the 228Th/228Ra ratio are measured to trace particle fluxes. The accumulation of 226Ra (1620 y half-life) in the deep Makarov Basin can be used as a measure of basin ventilation time.

Description: Radium isotopes are produced by decay of an isotope of thorium, a highly particle reactive element. Radium is relatively soluble in seawater such that once a thorium isotope in suspended or bottom sediments decays, a fraction of the produced radium isotope may be released to solution. 224Ra (3.7-day half-life) and 223Ra (11.4-day half-life) are used extensively as tracers for interaction on the shelf and for submarine groundwater discharge (SGD). 228Ra is strongly enriched in shelf waters and in the Transpolar Drift (TPD) and its half-life (5.8 years) is well suited to study the fate of this shelf-derived water in the central Arctic. This dataset collected in the framework of GEOTRACES during PS94 in 2015 shows that the input of 228Ra in the TPD has increased since previous studies in 2007 and 2011. The distribution of 228Ra-daughter 228Th (1.9 y half-life) and the 228Th/228Ra ratio are measured to trace particle fluxes. The accumulation of 226Ra (1620 y half-life) in the deep Makarov Basin can be used as a measure of basin ventilation time.

Description: Radium isotopes are produced by decay of an isotope of thorium, a highly particle reactive element. Radium is relatively soluble in seawater such that once a thorium isotope in suspended or bottom sediments decays, a fraction of the produced radium isotope may be released to solution. 228Ra is strongly enriched in shelf waters and in the Transpolar Drift (TPD) and its half-life (5.8 years) is well suited to study the fate of this shelf-derived water in the central Arctic. The 228Th/228Ra ratio in the subsurface water column can be used to trace particle fluxes. In previous studies up to PS94 (2015) we had identified the strong and increasing 228Ra signal in the Transpolar Drift. During PS100 we studied the distribution of 228Ra in Fram Strait to investigate how this 228Ra signal in the TPD is changed by dilution and decay on its way to the East Greenland Current. Water from in situ pumps was filtered and passed over MnO2-coated cartridges to absorb the Ra and Th. On board, short-lived Radium isotopes and 228Th were analysed using RaDeCC counting. In the lab, the cartridges were leached in refluxing HCl and long-lived Radium isotopes were measured by gamma spectroscopy. At depths where in situ pumps were deployed with two cartridges in series, the Ra adsorption efficiency was determined from the ratio of the Ra activities in the two cartridges. At depths where only one cartridge was mounted, we used the average collection efficiency of all other cartridge pairs, corrected after a mass spectrometric analysis of 226Ra activities in discrete samples (Vieira et al., 2021, doi:10.1002/lom3.10428) (82 ± 8%).