Description: Highlights • First comprehensive seawater Nd isotope and REE data for the Laptev Sea. • Dissolved Nd isotopes, salinity and stable oxygen isotopes trace water masses. • No evidence for REE release from particles of the organic-rich Siberian Rivers. • Preferential estuarine LREE removal follows increasing salinity from 10 to 34. • Formation and melting of sea ice redistribute REEs within water column. Abstract Marine neodymium (Nd) isotope and rare earth element (REE) compositions are valuable tracers for present and past ocean circulation and continental inputs. Yet their supply via high latitude estuaries is largely unknown. Here we present a comprehensive dissolved Nd isotope (expressed as εNd values) and REE data set together with seawater stable oxygen isotope ( O) compositions of samples from the Laptev Sea recovered in two Arctic summers and one winter. The Laptev Sea is a shallow Siberian Shelf sea characterized by extensive river-runoff, sea-ice production and ice transport into the Arctic Ocean. The large variability in εNd (−6 to −17), REE concentrations (16 to 600 pmol/kg for Nd) and REE patterns is controlled by freshwater supply from distinct riverine sources and open ocean Arctic Atlantic Water. Strikingly and contrary to expectations, except for cerium no evidence for significant release of REEs from particulate phases is found, which is attributed to low amounts of suspended particulate matter and high dissolved organic carbon concentrations present in the contributing rivers. Essentially all shelf waters are depleted in light (L)REEs, while the distribution of the heavy REEs shows a deficiency at the surface and a pronounced excess in the bottom layer. This distribution is consistent with REE removal through coagulation of riverine nanoparticles and colloids starting at salinities near 10 and resulting in a drop of all REE concentrations by ∼30%. With increasing salinity preferential LREE removal is observable reaching ∼75% for Nd at a salinity of 34. Although the delayed onset of dissolved REE removal contrasts with most previous observations from other estuarine environments, it agrees remarkably well with results from recent experiments simulating estuarine mixing of seawater with organic-rich river waters. In addition, melting and formation of sea ice leads to further REE depletion at the surface and strong REE enrichment near the shelf bottom as a function of ice melting and brine transfer, respectively. The ice-related processes significantly affect the distribution of dissolved REEs in high-latitude estuaries and likely also similarly contribute to the redistribution of other dissolved seawater constituents.

Description: The water masses passing the Fram Strait are mainly responsible for the exchange of heat and freshwater between the Nordic Seas and the Arctic Ocean (the Arctic Mediterranean, AM). Disentangling their exact sources, distribution and mixing, however, is complex. This work provides new insights based on a detailed geochemical tracer inventory including dissolved Nd isotope (εNd), rare earth element (REE) and stable oxygen isotope (δ18O) data along a full water depth section across Fram Strait. We find that Nd isotope and REE distributions in the open AM primarily reflect lateral advection of water masses and their mixing. Seawater-particle interactions exert important control only above the shelf regions, as observed above the NE Greenland Shelf. Advection of northward flowing warm Atlantic Water (AW) is clearly reflected by an εNd signature of -11.7 and a Nd concentration ([Nd]) of 16 pmol/kg in the upper ∼500 m of the eastern and central Fram Strait. Freshening and cooling of the AW on its way trough the AM are accompanied by a continuous change towards more radiogenic εNd signatures (e.g. -10.4 of dense Arctic Atlantic Water). This mainly reflects mixing with intermediate waters but also admixture of dense Kara Sea waters and Pacific-derived waters. The more radiogenic εNd signatures of the intermediate and deep waters (reaching -9.5) are mainly acquired in the SW Nordic Seas through exchange with basaltic formations of Iceland and SE Greenland. Inputs of Nd from Svalbard are not observed and surface waters and Nd on the Svalbard shelf originate from the Barents Sea. Shallow southward flowing Arctic-derived waters (〈 200 m) form the core of the East Greenland Current above the Greenland slope and can be traced by their relatively radiogenic εNd (reaching -8.8) and elevated [Nd] (21 to 29 pmol/kg). These properties are used together with δ18O and standard hydrographic tracers to define the proportions of Pacific-derived (〈 ∼30 % based on Nd isotopes) and Atlantic-derived waters, as well as of river waters (〈 ∼8 %). Shallow waters (〈 150 m) on the NE Greenland Shelf share some characteristics of Arctic-derived waters, but exhibit less radiogenic εNd values (reaching -12.4) and higher [Nd] (up to 38 pmol/kg) in the upper ∼100 m. This suggests local addition of Greenland freshwater of up to ∼6 %. In addition to these observations, this study shows that the pronounced gradients in εNd signatures and REE characteristics in the upper water column provide a reliable basis for assessments of shallow hydrological changes within the AM.

Description: Highlights • First systematic dissolved neodymium isotope distributions in Angola and Cape Basins. • Deep water neodymium isotopes dominated by conservative mixing in study area. • Neodymium isotopes trace surface waters from Mozambique Channel in Angola Basin. • Cape Basin bottom water neodymium isotopes are unaffected by neodymium from sediments. • Glacial Cape Basin bottom waters may show effects of sedimentary neodymium inputs. Abstract In contrast to the vigorous deep ocean circulation system of the north- and southwestern Atlantic Ocean, no systematically sampled datasets of dissolved radiogenic neodymium (Nd) isotope signatures exist to trace water mass mixing and provenance for the more restricted and less well ventilated Angola Basin and the Cape Basin in the southeastern Atlantic Ocean, where important parts of the return flow of the Atlantic Meridional Overturning Circulation are generated. Here, to improve our understanding of water mass mixing and provenance, we present the first full water column Nd isotope (expressed as εNd values) and concentration data for a section across the western Angola Basin from 3° to 30° S along the Zero Meridian and along an E-W section across the northern Cape Basin at 30° S sampled during GEOTRACES cruise GA08. Compared with the southwestern Atlantic basin we find overall less radiogenic εNd signatures reaching −17.6 in the uppermost 200 m of the Angola and Cape basins. In the western Angola Basin these signatures are the consequence of the admixture of a coastal plume originating near 13° S and carrying an unradiogenic Nd signal that likely resulted from the dissolution of Fe-Mn coatings of particles formed in river estuaries or near the West African coast. The highly unradiogenic Nd isotope signatures in the upper water column of the northern Cape Basin, in contrast, originate from old Archean terrains of southern Africa and are introduced into the Mozambique Channel via rivers like the Limpopo and Zambezi. These signatures allow tracing the advection of shallow waters via the Agulhas and Benguela currents into the southeastern Atlantic Ocean. The Nd isotope compositions of the deep water masses in both basins primarily reflect conservative water mass mixing with the only exception being the central Angola Basin, where the signatures are significantly overprinted by terrestrial inputs. Bottom waters of the Cape Basin show excess Nd concentrations of up to 6 pmol/kg (20%), originating from resuspended bottom sediments and/or dissolution of dust, but without significantly changing the isotopic composition of the waters due to similar εNd values of particles and bottom waters ranging between −9.6 and −10.5. Given that bottom waters within the Cape Basin today are enriched in Nd, non-conservative Nd isotopic effects may have been resolvable under past glacial boundary conditions when bottom waters were more radiogenic.

Description: Highlights • First comprehensive seawater Nd isotope and REE data set for the Barents Sea • Water masses traced with Nd isotopes, salinity and stable oxygen isotopes • No release of particulate REEs to the dissolved load except for cerium • Transformation of Atlantic Water accompanied by pronounced REE removal from the dissolved phase Abstract Nearly half the inflow of warm and saline Atlantic Water (AW) to the Arctic Ocean is substantially cooled and freshened in the Barents Sea, which is therefore considered a key region for water mass transformation in the Arctic Mediterranean. Numerous studies have focused on this transformation and the increasing influence of AW on Arctic climate and biodiversity, yet geochemical investigations of these processes have been scarce. Using the first comprehensive data set of the distributions of dissolved radiogenic neodymium (Nd) isotopes (expressed as ɛNd), rare earth elements (REE) and stable oxygen isotope (δ18O) compositions from this region we are able to constrain the transport and transformation of AW in the Barents Sea and to investigate which processes change the chemical composition of the water masses beyond what is expected from circulation and mixing. Inflowing AW and Norwegian Coastal Water (NCW) both exhibit distinctly unradiogenic ɛNd signatures of −12.4 and −14.5, respectively, whereas cold and dense Polar Water (PW) has considerably more radiogenic ɛNd signatures reaching up to −8.1. Locally formed Barents Sea Atlantic Water (BSAW) and Barents Sea Arctic Atlantic Water (BSAAW) are encountered in the northeastern Barents Sea and have intermediate ɛNd values resulting from admixture of PW containing small amounts of riverine freshwater from the Ob (〈~1.1%) to AW and NCW. Similar to the Laptev Sea, the dissolved Nd isotope composition in the Barents Sea seems to be mainly controlled by water mass advection and mixing despite its shallow water depth. Strikingly, the BSAW and BSAAW are marked by the lowest REE concentrations reaching 11 pmol/kg for Nd ([Nd]), which in contrast to the Nd isotopes, cannot be attributed to the admixture of REE-rich Ob freshwater to AW or NCW ([Nd] = 16.7, and 22 pmol/kg, respectively) and instead reflects REE removal from the dissolved phase with preferential removal of the light over the heavy REEs. The REE removal is, however, not explainable by estuarine REE behavior alone, suggesting that scavenging by (re)suspended (biogenic) particles occurs locally in the Barents Sea. Regardless of the exact cause of REE depletion, we show that AW transformation is accompanied by geochemical changes independent of water mass mixing. This article is part of a special issue entitled: Conway GEOTRACES - edited by Tim M. Conway, Tristan Horner, Yves Plancherel, and Aridane G. González.

Description: Highlights • First dissolved Nd/Hf isotope and REE data from the Congo River Plume. • High REE and Hf fluxes from the Congo River to the southeast Atlantic. • Conservative river and surface seawater mixing of Nd/Hf isotopes and REEs/Hf at S 〉 23. • Congo River particles impact intermediate and deep water signals of NE Angola Basin. Abstract The Congo River is the second largest river by discharge in the world and a major source of element inputs into the South Atlantic Ocean. Yet, the element fluxes and transport mechanisms across and beyond its estuary and their impacts on the marine distribution and cycling of many major and trace elements are not well understood. We present the first combined dissolved neodymium (Nd) and hafnium (Hf) isotope and rare earth element (REE) concentration distributions following the Congo River plume along its flow path off the West African coast and along a connected offshore latitudinal section at 3°S. The Congo River freshwater itself is characterized by extraordinarily high Nd and Hf concentrations of up to 4000 pmol/kg and 54 pmol/kg, and by Nd (εNd) and Hf (εHf) isotope compositions that range between −15.6 and −16.4 and between 0.35 and −1.4, respectively. Our near- and offshore data indicate that at salinities above 23 conservative mixing of Congo-derived Nd and Hf concentrations and isotopic signatures with ambient surface seawater occurs for at least 1000 km to the northwest of the river mouth. This demonstrates a large spatial extent of the influence of the Congo plume on trace metal distributions in the eastern south Atlantic surface waters. A comparison between dissolved Nd and Hf fluxes from the Congo River and the shelf zone estimated based on radium isotope compositions indicate that release from Congo-derived particulate phases likely balances strong estuarine REE and Hf removal in the low salinity zone. The combined riverine and shelf zone flux for Nd is almost twice as high as that estimated for the Amazon River, despite that the Amazon discharge is about five times higher than that of the Congo River. Even the offshore Nd flux estimated for the 3 °S transect based on radium isotope compositions still corresponds to ∼40% of the Congo-shelf-zone flux and reaches 150 ± 50 Mg/year for Nd. Moreover, intermediate waters below the plume are strongly affected by exchange with particulate inputs from the Congo River given that Nd isotope signatures are inconsistent with values expected from large-scale water mass mixing and instead support unradiogenic Nd release either from sinking or deposited Congo-derived detrital material. Deep and bottom water isotopic signatures are also slightly affected by interaction with particles and benthic Nd release.