Description: The chemical and isotopic composition of foraminiferal shells (so-called proxies) reflects the physico-chemical properties of the seawater. In current day paleoclimate research, the reconstruction of past seawater carbonate system to infer atmospheric CO2 concentrations is one of the most pressing challenges and a variety of proxies have been investigated, such as foraminiferal U/Ca. Since in natural seawater and traditional CO2 perturbation experiments, the carbonate system parameters co-vary, it is not possible to determine the parameter of the carbonate system causing e.g. changes in U/Ca, complicating the use of the latter as a carbonate system proxy. We overcome this problem, by culturing the benthic foraminifer Ammonia sp. at a range of carbonate chemistry manipulation treatments. Shell U/Ca values were determined to test sensitivity of U incorporation to various parameters of the carbonate system. We argue that [CO32-] is the parameter affecting the U/Ca ratio and consequently, the partitioning coefficient for U in Ammonia sp DU. We can confirm the strong potential of foraminiferal U/Ca as a [CO32-] proxy.

Description: Highlights: • We coupled LA-ICP-MS Me/Ca single-chamber composition of four planktonic foraminifera with eddy induced hydrographic changes • The Mg/Ca-based temperature difference between N. dutertrei and G. scitula are likely to be an eddy proxy suitable for down-core application • Near-surface dwelling species inhabit well oxygenated surface waters and show lower test Mn/Ca values, compared to deeper dwelling species • Planktonic foraminifera Mn/Ca test values are in line with water column variability in dissolved Mn concentrations Hydrographic conditions in the Mozambique Channel are dominated by the passing of large anticyclonic eddies, propagating poleward into the upstream Agulhas area. Further south, these eddies have been found to control the shedding of Agulhas rings into the Atlantic ocean, thereby playing a key role in Indo-Atlantic Ocean exchange. The element composition of several planktonic foraminifera species collected from sediment trap samples, was compared to in situ water column data from the Mozambique Channel. Single-chamber trace element composition of these foraminifera reveals a close coupling with hydrographic changes induced by anticyclonic eddies. Obtained Mg/Ca values for the surface dwelling Globigerinoides ruber as well as the thermocline dwelling Neogloboquadrina dutertrei follow temperature changes and reduced temperature stratification during eddy conditions. At greater depth. Globorotalia scitula and Pulleniatina obliquiloculata record stable temperatures and thus respond to hydrographic changes with a deepening in habitat depth. Furthermore, test Mn/Ca values indicate a close relationship between water column oxygenation and Mn incorporation in these planktonic foraminiferal species

Description: We constructed a high-resolution Mg/Ca record on the planktonic foraminifer Globigerinoides sacculifer in order to explore the change in sea surface temperature (SST) due to the shoaling of the Isthmus of Panama as well as the impact of secondary factors like diagenesis and large salinity fluctuations. The study covers the latest Miocene and the early Pliocene (5.6–3.9 Ma) and was combined with δ18O to isolate changes in sea surface salinity (SSS). Before 4.5 Ma, SSTMg/Ca and SSS show moderate fluctuations, indicating a free exchange of surface ocean water masses between the Pacific and the Atlantic. The increase in δ18O after 4.5 Ma represents increasing salinities in the Caribbean due to the progressive closure of the Panamanian Gateway. The increase in Mg/Ca toward values of maximum 7 mmol/mol suggests that secondary influences have played a significant role. Evidence of crystalline overgrowths on the foraminiferal tests in correlation with aragonite, Sr/Ca, and productivity cyclicities indicates a diagenetic overprint on the foraminiferal tests. Laser ablation inductively coupled plasma–mass spectrometry analyses, however, do not show significantly increased Mg/Ca ratios in the crystalline overgrowths, and neither do calculations based on pore water data conclusively result in significantly elevated Mg/Ca ratios in the crystalline overgrowths. Alternatively, the elevated Mg/Ca ratios might have been caused by salinity as the δ18O record of Site 1000 has been interpreted to represent large fluctuations in SSS, and cultivating experiments have shown an increase in Mg/Ca with increasing salinity. We conclude that the Mg/Ca record 〈4.5 Ma can only reliably be considered for paleoceanographical purposes when the minimum values, not showing any evidence of secondary influences, are used, resulting in a warming of central Caribbean surface water masses after 4.5 Ma of ∼2°C.

Description: Highlights • Fe-binding ligands associated with primary productivity together with ligands from the Arctic Ocean are the main sources of Fe-binding ligands in surface waters of Fram Strait. • Fe-binding ligands are present in a high concentrations in front of the glacier terminus, but the ligands have a relatively low binding capacity, thus less reactive. • Low binding strength coupled with low competing strength of ligands result in a higher inorganic Fe concentration, causing Fe to precipitate or scavenged. Abstract There is a paucity of data on Fe-binding ligands in the Arctic Ocean. Here we investigate the distribution and chemical properties of natural Fe-binding ligands in Fram Strait and over the northeast Greenland shelf, shedding light on their potential sources and transport. Our results indicate that the main sources of organic ligands to surface waters of Fram Strait included primary productivity and supply from the Arctic Ocean. We calculated the mean total Fe-binding ligand concentration, [Lt], in Polar Surface Water from the western Fram Strait to be 1.65 ± 0.4 nM eq. Fe. This value is in between reported values for the Arctic and North Atlantic Oceans, confirming reports of north to south decreases in [Lt] from the Arctic Ocean. The differences between ligand sources in different biogeochemical provinces, resulted in distinctive ligand properties and distributions that are reflected in [Lt], binding strength (log KFe'L′) and competing strength (log αFe'L) of ligands. Higher [Lt] was present near the Nioghalvfjerdsfjorden (79 N) Glacier terminus and in the Westwind Trough (median of [Lt] = 2.17 nM eq. Fe; log KFe'L′ = 12.3; log αFe'L = 3.4) than in the Norske Trough (median of [Lt] = 1.89 nM eq. Fe; log KFe'L′= 12.8; log αFe'L = 3.8) and in Fram Strait (median of [Lt] = 1.38 nM eq. Fe; log KFe'L′ = 13; log αFe'L= 3.9). However, organic ligands near the 79 N Glacier terminus and in the Westwind Trough were weaker, and therefore less reactive than organic ligands in the Norske Trough and in Fram Strait. Our findings reveal the fundamental mechanism that underpin transport of dissolved-Fe (DFe) from the 79 N Glacier to Fram Strait, less reactive ligands will reduce Fe solubility. Accordingly, a portion of the glacial DFe will not be transported over the shelf into the ocean. The lower ligand binding strength in the outflow results in a higher inorganic Fe concentration, [Fe´], which is more prone to precipitation and/or scavenging than Fe complexed with stronger ligands. Ongoing changes in the Arctic and sub-Arctic Oceans will influence both terrestrially derived and in-situ produced Fe-binding ligands, and therefore will have consequences for Fe solubility and availability to microbial populations and Fe cycling in Fram Strait.