We diagnose the relative influences of local-scale biogeochemical cycling and regional-scale ocean circulation on Atlantic barium cycling by analysing four new depth profiles of dissolved Ba concentrations and isotope compositions from the South and tropical North Atlantic. These new profiles exhibit systematic vertical, zonal and meridional variations that reflect the influence of both local-scale barite cycling and large-scale ocean circulation. Epipelagic decoupling of dissolved Ba and Si reported previously in the tropics is also found to be associated with significant Ba isotope heterogeneity. As such, we contend that this decoupling originates from the depth segregation of opal and barite formation but is exacerbated by weak vertical mixing. Zonal influence from isotopically-'heavy' water masses in the western North Atlantic evidence the advective inflow of Ba-depleted Upper Labrador Sea Water, which is not seen in the eastern basin or the South Atlantic. Meridional variations in Atlantic Ba isotope systematics below 2000 m appear entirely controlled by conservative mixing. Using an inverse isotopic mixing model, we calculate the Ba isotope composition of the Ba-poor northern end-member as +0.45 ‰ and the Ba-rich southern end-member +0.26 ‰, relative to NIST SRM 3104a. The near-conservative behaviour of Ba below 2000 m indicates that Ba isotopes can serve as an independent tracer of the provenance of northern-versus southern-sourced water masses in the deep Atlantic Ocean. This finding may prove useful in palaeoceanographic studies, should appropriate sedimentary archives be identified, and offers new insights into the processes that cycle Ba in seawater.

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Biogeochemical cycling in high-latitude regions has a disproportionate impact on global nutrient budgets. Here, we introduce a holistic, multidisciplinary framework for elucidating the influence of glacial meltwaters, shelf currents, and biological production on biogeochemical cycling in high-latitude continental margins, with a focus on the silica cycle. Our findings highlight the impact of significant glacial discharge on nutrient supply to shelf and slope waters, as well as surface and benthic production in these regions, over a range of timescales from days to thousands of years. Whilst biological uptake in fjords and strong diatom activity in coastal waters maintains low dissolved silicon concentrations in surface waters, we find important but spatially heterogeneous additions of particulates into the system, which are transported rapidly away from the shore. We expect the glacially-derived particles-together with biogenic silica tests-to be cycled rapidly through shallow sediments, resulting in a strong benthic flux of dissolved silicon. Entrainment of this benthic silicon into boundary currents may supply an important source of this key nutrient into the Labrador Sea, and is also likely to recirculate back into the deep fjords inshore. This study illustrates how geochemical and oceanographic analyses can be used together to probe further into modern nutrient cycling in this region, as well as the palaeoclimatological 3 approaches to investigating changes in glacial meltwater discharge through time, especially during periods of rapid climatic change in the Late Quaternary.

Reconstruction of silica cycling in the oceans is key to a thorough understanding of past climates because of the inherent links between the biogeochemistry of silicifiers and sequestration of organic carbon. Diatoms are one of the most important phytoplankton groups in determining export production from surface waters, and rely largely on upwelling deeper waters as a source of dissolved silicon, an essential nutrient for their growth. Quantification of changes in deep water dissolved silicon concentrations in the past allows a more robust understanding of changes in surface nutrient supply and whole-ocean silicon cycling, but cannot be achieved using surfacederived geochemical archives. In the last few years, there has been increasing focus on the use of geochemical archives in siliceous skeletal elements, or spicules, from seafloor-dwelling sponges to fill this gap. The stable silicon isotopic composition of spicules has been shown to be a function of ambient dissolved silicon, providing a potential archive for past changes in bottom water nutrients. However, biomineralisation processes impact silicon isotope fractionation and silica formed by atypical processes (derived from carnivorous sponges, hypersilicified spicules, and giant basal spicules) result in anomalous geochemical signatures. Furthermore, there is considerable scatter in the calibration between spicule silicon isotopes and dissolved silicon in seawater, even when the atypical groups have been removed. Here, we explore this variability further, by examining aggregation and assemblage-level differences in isotopic fractionation, using silicon isotopic measurements of specimens from two monospecific sponge groups (Pheronema carpenteri and Vazella pourtalesi), and one mixed-species population (genus Geodia) from the North Atlantic. Our new data reveal that variability within the monospecific aggregations is less than mixed-species assemblage, pointing towards a genetic control in isotopic fractionation. However, there is still variability within the monospecific aggregations, which cannot be explained by macroscale environmental differences: such variability is likely a reflection of the physiological health of the individuals, or highly localised heterogeneities in sponge habitats. Other challenges remain in the interpretation of spicule silicon isotopes as proxies for dissolved silicon changes through time, especially when investigating periods of Earth history that extend back considerably further than the residence time of dissolved silicon in the oceans. Despite all the questions still surrounding the use of sponge silicon isotopes in palaeoceanographic applications, they are still the only known archive of bottom water dissolved silicon. Continued efforts to understanding sponge biomineralisation and to incorporate silicon isotopes into oceanic models will help to improve further the reliability of the archive.

We assessed preference for video or in vivo modeling using a concurrent-chains arrangement with 3 children with autism. The two modeling conditions produced similar acquisition rates and no differential selection (i.e., preference) for all 3 participants.