The Chukchi Sea is a primary site for shelf-ocean exchange in the Arctic region and modifies Pacific-sourced water masses as they transit via the Bering Strait into the Arctic Ocean. The aim of this study was to use radium and trace metal distributions to improve our understanding of biogeochemical cycles in the Bering and Chukchi Seas, and evaluate their potential response to future changes in the Arctic. We investigated the distributions of dissolved and total dissolvable trace metals (Cd, Fe, Ni, Cu, Zn, Mn, Co, and Pb) in the Bering and Chukchi Seas during spring. In addition, the long-lived radium isotopes ( 226 Ra and 228 Ra) were measured as tracers of benthic trace metal inputs. Trace metal concentrations, especially Fe and Mn, were highly elevated in Chukchi shelf waters compared with the open Arctic Ocean and Bering Strait. Trace metal, nutrient, and Ra patterns suggested that Fe, Mn, and Co concentrations were predominantly controlled by reductive benthic inputs, whereas the other trace metals were influenced by biological uptake and release processes. We propose that Fe, Mn, and Co in the Chukchi Sea are supplied from shelf sediments during winter overturning, and we combine the 228 Ra fluxes with the distributions of Fe, Mn, and Co to provide a first estimate of their benthic fluxes in the region. The average benthic flux of 228 Ra was 1.49 x 10 8 atoms m -2 d -1 , which is among the highest rates reported globally. Estimated dissolved Fe (D-Fe) flux from the sediments was 2.5 µmol m -2 d -1 , whereas D-Mn and D-Co fluxes were 8.0 µmol m -2 d -1 and 0.2 µmol m -2 d -1, respectively. The off-shelf transport of D-Fe to the Arctic Ocean is estimated to be about 10-25% of the benthic Fe flux, with the remainder retained on the shelf due to scavenging and/or phytoplankton uptake. Our results highlight the importance of the Chukchi Sea as a major source of the micro-nutrients to the Arctic Ocean, thereby supporting primary production. Long-term changes in factors that affect cross-shelf mixing, such as the observed reduction in ice cover, may therefore enhance shelf nutrient inputs and primary productivity in the Arctic.
Rivers are a major supplier of particulate and dissolved material to the ocean, but their role as sources of bio-essential dissolved iron (dFe) is thought to be limited due to rapid, efficient Fe removal during estuarine mixing. Here, we use trace element and radium isotope data to show that the influence of the Congo River margin on surface Fe concentrations is evident over 1000 km from the Congo outflow. Due to an unusual combination of high Fe input into the Congo-shelf-zone and rapid lateral transport, the Congo plume constitutes an exceptionally large offshore dFe flux of 6.8 ± 2.3 × 108 mol year−1. This corresponds to 40 ± 15% of atmospheric dFe input into the South Atlantic Ocean and makes a higher contribution to offshore Fe availability than any other river globally. The Congo River therefore contributes significantly to relieving Fe limitation of phytoplankton growth across much of the South Atlantic.
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, and 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, while 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.
The precise determination of radium-226 ( 226 Ra) in environmental samples is challenging due to its low concentration. Seawater typically contains between 0.03 and 0.1 fg g −1 226 Ra. Thus, this work addresses the need for an easy and precise methodology for 226 Ra determination in seawater that may be applied routinely to a large number of samples. For this reason, a new analytical approach has been developed for the quantification of 226 Ra in seawater via inductively coupled plasma mass spectrometry (ICP-MS). Analysis by single collector sector-field ICP-MS was shown to be convenient and reliable for this purpose once potential molecular interferences were excluded by a combination of chemical separation and intermediate mass resolution analysis. The proposed method allows purification of Ra from the sample matrix based on preconcentration by MnO 2 precipitation, followed by two-column separation using a cation exchange resin and an extraction chromatographic resin. The method can be applied to acidified and unacidified seawater samples. The recovery efficiency for Ra ranged between 90% and 99.8%, with precision of 5%, accuracy of 95.7% to 99.9%, and a detection limit of 0.033 fg g −1 (referring to the original concentration of seawater). The method has been applied to measure 226 Ra concentrations from the North Sea and validated by analyzing samples from the central Arctic (GEOTRACES GN04). Samples from a crossover station (from GEOTRACES GN04 and GEOTRACES GN01 research cruises) were analyzed using alternative methods, and our results are in good agreement with published values.
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