Beschreibung: The Amazon River has the largest drainage basin in the world, making it a major source of trace elements and dissolved organic matter (DOM) to the Atlantic Ocean. However, despite the increasing anthropogenic impacts to the Amazon basin, few recent studies exist quantifying trace element data in this region. The aim of the study was to analyze the input and removal processes that influence the transport of Ni and Co species in the Amazon and Pará River estuaries and mixing zone. Toward this goal, this work provides a comprehensive mixing and speciation study for the trace elements Ni and Co. Samples were collected during a period of high river discharge on the RV Meteor cruise M147 (Amazon – GEOTRACES process study GApr11) in the Amazon and Pará River outflow regions, as well as the aging mixing plume to the north, a mangrove belt to the southeast and the North Brazil Current (NBC) seawater endmember. Here we present the results for labile particulate (〉0.2 μm), labile and total dissolved (〈0.2 μm), large colloidal (0.015–0.2 μm), soluble (〈0.015 μm) and ultrafiltered (〈1 and 〈 10 kDa) fractions of Ni and Co in surface waters (towed-fish) and along the water column at different depths (CTD) samples using comparative approaches by adsorptive cathodic stripping voltammetry (AdCSV) and inductively coupled plasma-mass spectrometry (ICP-MS). We observed good agreement between AdCSV and ICP-MS measurements for Ni, and to a lesser extent Co. In general, dissolved and soluble Ni and Co decreased with increasing salinity, however additional non-conservative removal was also observed and attributed to possible biological uptake and colloidal flocculation. Shipboard AdCSV measurements showed that dissolved Ni was present mostly in the “reactive” form as weak complexes, suggesting high bioavailability, while reactive dissolved Co was absent, indicating the presence of strong organic Co complexes. In both Ni and Co, an elevated colloidal fraction was observed at low salinity, suggesting removal of dissolved Ni and Co via colloidal flocculation upon seawater mixing, while the soluble species were transported to the Atlantic Ocean. At depth, the soluble phase dominated, and we observed concentration maxima at 500–1000 m, indicating the presence of Antarctic Intermediate Water (AIW) and possible biological regeneration. We also observed unique source signatures in dissolved and labile particulate Ni and Co species from the Amazon and Pará River outflow regions, in addition to a contribution from mangrove belt-associated groundwater.

Beschreibung: Ultratrace concentrations of Ti were determined by catalytic differential pulse adsorptive stripping voltammetry (cDPAdSV) in samples collected in the Pará and Amazon estuaries and plume into the Atlantic Ocean. Different end members including rivers Tocantins, Amazon and Pará and Atlantic seawater were sampled as well as the salinity gradients in the mixing zone between the river outflows and waters from the North Brazil Current during several transects. The Mangrove Belt southeast of the Pará river mouth with its extensive groundwater discharge was also sampled. Most samples were taking during cruise M147 (GEOTRACES process study GApr11) during the high discharge period in April and May 2018. In addition to high resolution determination of dissolved Ti distributions in this region, size fractionation was investigated by using several filtration steps with pore sizes (0.2 μm, and 0.015 μm) and ultrafiltration (10 kDa and 1 kDa) at four selected stations. Dissolved Ti varied significantly between different river end members and showed a non-conservative behavior along the mixing gradients with strong removal at low salinities and some enrichments at higher salinity ranges. The results suggest that there was both adsorption and desorption of Ti from suspended particles from both riverine and marine sources or flocculation and aggregation of colloids and particulate matter from end member rivers as well as resuspension at particular salinity ranges. The 0.015 μm filtered and 10 kDa and 1 kDa ultrafiltered aliquots showed variable distributions of Ti in the different size fractions, depending on the sampling zone. This very complex behavior of Ti along the mixing gradient and the dynamic system of the Amazon estuary, which comprises a fifth of the global freshwater flux into the ocean, is the key to controlling the fluxes of Ti into the Atlantic.