ALBERT

Description: Dissolved free amino acids (DFAA) in seawater are a form of nitrogen (N) available for marine microbes. In oligotrophic environments where N-containing nutrients are the limiting factor for microbial growth, N nutrition from DFAA could be crucial, but as yet it is poorly resolved. Measurements of individual DFAA are challenging as concentrations are typically in the low nmol L− 1 range. Here we report modifications to methodology using o-phthaldialdehyde (OPA) derivatization and reversed phase high performance liquid chromatography (HPLC) that provide a 30-fold improvement in sensitivity enabling the detection of 15 amino acids in seawater with a limit of detection as low as 10 pmol L− 1 with accuracy and precision of better than 10%. This analytical methodology is now suitable for the challenging quantitation of DFAA in oligotrophic seawaters. The method was successfully applied to a suite of seawater samples collected on a cruise crossing the South Atlantic Ocean, where concentrations of DFAAs were generally low (sub nmol L− 1), revealing basin-scale features in the oceanographic distributions of DFAA. This unique dataset implies that DFAAs are an important component of the N cycle in both near-coastal and open oceans. Further calculations suggest that the proportions of organic N originating from DFAA sources were significant, contributing between 0.2 and 200% that of NH4 + and up to 77% that of total inorganic nitrogen in the upper 400 m in some regions of the transect.

Description: The GEOTRACES Intermediate Data Product 2017 (IDP2017) is the second publicly available data product of the international GEOTRACES programme, and contains data measured and quality controlled before the end of 2016. The IDP2017 includes data from the Atlantic, Pacific, Arctic, Southern and Indian oceans, with about twice the data volume of the previous IDP2014. For the first time, the IDP2017 contains data for a large suite of biogeochemical parameters as well as aerosol and rain data characterising atmospheric trace element and isotope (TEI) sources. The TEI data in the IDP2017 are quality controlled by careful assessment of intercalibration results and multi-laboratory data comparisons at crossover stations. The IDP2017 consists of two parts: (1) a compilation of digital data for more than 450 TEIs as well as standard hydrographic parameters, and (2) the eGEOTRACES Electronic Atlas providing an on-line atlas that includes more than 590 section plots and 130 animated 3D scenes. The digital data are provided in several formats, including ASCII, Excel spreadsheet, netCDF, and Ocean Data View collection. Users can download the full data packages or make their own custom selections with a new on-line data extraction service. In addition to the actual data values, the IDP2017 also contains data quality flags and 1-σ data error values where available. Quality flags and error values are useful for data filtering and for statistical analysis. Metadata about data originators, analytical methods and original publications related to the data are linked in an easily accessible way. The eGEOTRACES Electronic Atlas is the visual representation of the IDP2017 as section plots and rotating 3D scenes. The basin-wide 3D scenes combine data from many cruises and provide quick overviews of large-scale tracer distributions. These 3D scenes provide geographical and bathymetric context that is crucial for the interpretation and assessment of tracer plumes near ocean margins or along ridges. The IDP2017 is the result of a truly international effort involving 326 researchers from 22 countries. This publication provides the critical reference for unpublished data, as well as for studies that make use of a large cross-section of data from the IDP2017.

Description: Highlights • Cu speciation was investigated for the first time in the South-East Atlantic using CLE-AdCSV. • [Cu2+] were mostly below the putative biolimiting threshold of various marine microorganisms. • Cu speciation parameters showed a poor correlation with assessed biogeochemical parameters. • Spatial differences in Cu speciation parameters suggest that biogeochemical processes and sources strongly influence Cu speciation. Organic ligands play a key role in the marine biogeochemical cycle of copper (Cu), a bio-essential element, regulating its solubility and bioavailability. However, the sources, abundance, and distribution of these ligands are still poorly understood. In this study, we examined vertical Cu speciation profiles from the South-East Atlantic (GEOTRACES section GA08). Profiles were collected from a range of ocean conditions, including the Benguela upwelling region, the oligotrophic South Atlantic Gyre, and the Congo River outflow. In general, the lack of a significant correlation between most of the parameters assessed here with Cu speciation data obscures the provenance of Cu-binding ligands, suggesting that Cu speciation in the South-East Atlantic is influenced by a complex interplay between biotic and abiotic processes. Nevertheless, the total dissolved Cu (CuT) illustrated an allochthonous origin in the working area, while Cu-binding ligands showed both an allochthonous and a biogenic, autochthonous origin. Pigment concentrations showed that the phylogeography of different microorganisms influenced the spatial features of the Cu-binding ligand pool in the South-East Atlantic. Allochthonous Cu-binding ligand sources in the upper water column are likely associated with dissolved organic matter which originated from the Congo River and the Benguela upwelling system. Deep water ligand sources could include refractory dissolved organic carbon (DOC), resuspended benthic inputs, and lateral advected inputs from the shelf margin. The degradation of L1-type ligands and/or siderophores in low oxygen conditions may also be a source of L2-type ligands in the deep. Free Cu ion levels (1.7 to 156 fM), the biologically available form of CuT, were below the putative biolimiting threshold of many marine organisms. Two classes of ligands were found in this study with total ligand concentrations ([LT]) ranging from 2.5 to 283.0 nM and conditional stability constants (logKCuL, Cu2+cond) ranging from 10.7 to 14.6. The Cu speciation values were spatially variable across the three subregions, suggesting that biogeochemical processes and sources strongly influence Cu speciation. Highlights • Cu speciation was investigated for the first time in the South-East Atlantic using CLE-AdCSV. • [Cu2+] were mostly below the putative biolimiting threshold of various marine microorganisms. • Cu speciation parameters showed a poor correlation with assessed biogeochemical parameters. • Spatial differences in Cu speciation parameters suggest that biogeochemical processes and sources strongly influence Cu speciation.

Description: Highlights • Oceanic nutrient supply from seabird guano is poorly constrained by field observations. • This was assessed for guano from caught-and-released North Atlantic seabirds. • Guano released nutrients and relieved in situ phytoplankton nutrient limitation. • Guano was modelled to potentially be a major nutrient supply term in summer. • Declining pelagic seabird populations will impact this function. Abstract Nutrients supplied via seabird guano increase primary production in some coastal ecosystems. A similar process may occur in the open ocean. To investigate this directly, we first measured bulk and leachable nutrient concentrations in guano sampled in the North Atlantic. We found that guano was strongly enriched in phosphorus, which was released as phosphate in solution. Nitrogen release was dominated by reduced forms (ammonium and urea) whilst release of nitrate was relatively low. A range of trace elements, including the micronutrient iron, were released. Using in-situ bioassays, we then showed that supply of fresh guano to ambient seawater increases phytoplankton biomass and photochemical efficiencies. Based on these results, modelled seabird distributions, and known defecation rates, we estimate that on annual scales guano is a minor source of nutrients for the surface North Atlantic. However, on shorter timescales in late spring/summer it could be much more important: Estimates of upper-level depositions of phosphorus by seabirds were three orders of magnitude higher than modelled aerosol deposition and comparable to diffusion from deeper waters.

Description: Here we demonstrate enhanced natural community APase activity following iron amendment within the low zinc and moderately low iron Western North Atlantic. In contrast we find no evidence for trace metal limitation of APase activity beneath the Saharan dust plume in the Eastern Atlantic. Such intermittent iron limitation of microbial phosphorus acquisition provides an additional facet in the argument for iron controlling the coupling between oceanic nitrogen and phosphorus cycles.

Description: Iron (Fe), cobalt (Co), and vitamin B12 addition experiments were performed in the eastern Equatorial Pacific/Peruvian upwelling zone during the 2015 El Niño event. Near the Peruvian coastline, apparent photosystem II photochemical efficiencies (Fv/Fm) were unchanged by nutrient addition and chlorophyll-a tripled in untreated controls over two days, indicating nutrient replete conditions. Conversely, Fe amendment further away from the coastline in the high nitrate, low Fe zone significantly increased Fv/Fm and chlorophyll-a concentrations. Mean chlorophyll-a was further enhanced following supply of Fe+Co and Fe+B12 relative to Fe alone, but this was not statistically significant; further offshore, reported Co depletion relative to Fe could enhance responses. The persistence of Fe limitation in this system under a developing El Niño, as previously demonstrated under non-El Niño conditions, suggests that diminished upwelled Fe is likely an important factor driving reductions in offshore phytoplankton productivity during these events.

Description: Nutrient limitation of oceanic primary production exerts a fundamental control on marine food webs and the flux of carbon into the deep ocean1. The extensive boundaries of the oligotrophic sub-tropical gyres collectively define the most extreme transition in ocean productivity, but little is known about nutrient limitation in these zones1,2,3,4. Here we present the results of full-factorial nutrient amendment experiments conducted at the eastern boundary of the South Atlantic gyre. We find extensive regions in which the addition of nitrogen or iron individually resulted in no significant phytoplankton growth over 48 hours. However, the addition of both nitrogen and iron increased concentrations of chlorophyll a by up to approximately 40-fold, led to diatom proliferation, and reduced community diversity. Once nitrogen–iron co-limitation had been alleviated, the addition of cobalt or cobalt-containing vitamin B12 could further enhance chlorophyll a yields by up to threefold. Our results suggest that nitrogen–iron co-limitation is pervasive in the ocean, with other micronutrients also approaching co-deficiency. Such multi-nutrient limitations potentially increase phytoplankton community diversity.