Continental margins are disproportionally important for global primary production, fisheries and CO2 uptake. However, across the Northeast Atlantic shelves, there has been an ongoing summertime decline of key biota—large diatoms, dinoflagellates and copepods—that traditionally fuel higher tropic levels such as fish, sea birds and marine mammals. Here, we combine multiple time series with in situ process studies to link these declines to summer nutrient stress and increasing proportions of picophytoplankton that can comprise up to 90% of the combined pico‐ and nanophytoplankton biomass in coastal areas. Among the pico‐fraction, it is the cyanobacterium Synechococcus that flourishes when iron and nitrogen resupply to surface waters are diminished. Our field data show how traits beyond small size give Synechococcus a competitive edge over pico‐ and nanoeukaryotes. Key is their ability to grow at low irradiances near the nutricline, which is aided by their superior light‐harvesting system and high affinity to iron. However, minute size and lack of essential biomolecules (e.g. omega‐3 polyunsaturated fatty acids and sterols) render Synechococcus poor primary producers to sustain shelf sea food webs efficiently. The combination of earlier spring blooms and lower summer food quantity and quality creates an increasing period of suboptimal feeding conditions for zooplankton at a time of year when their metabolic demand is highest. We suggest that this nutrition‐related mismatch has contributed to the widespread, ~50% decline in summer copepod abundance we observe over the last 60 years. With Synechococcus clades being prominent from the tropics to the Arctic and their abundances increasing worldwide, our study informs projections of future food web dynamics in coastal and shelf areas where droughts and stratification lead to increasing nutrient starvation of surface waters.

Shelf sediments underlying temperate and oxic waters of the Celtic Sea (NW European Shelf) were found to have shallow oxygen penetrations depths from late spring to late summer (2.2-5.8 mm below seafloor) with the shallowest during/after the spring-bloom (mid-April to mid-May) when the organic carbon content was highest. Sediment porewater dissolved iron (dFe,\0.15 lm) mainly ([85%) consisted of Fe(II) and gradually increased from 0.4 to 15 lM at the sediment surface to *100-170 lM at about 6 cm depth. During the late spring this Fe(II) was found to be mainly present as soluble Fe(II) ([85% sFe, \0.02 lm). Sub-surface dFe(II) maxima were enriched in light isotopes (d 56 Fe -2.0 to -1.5%), which is attributed to dissimilatory iron reduction (DIR) during the bacterial decomposition of organic matter. As porewater Fe(II) was oxidised to insoluble Fe(III) in the surface sediment layer, residual Fe(II) was further enriched in light isotopes (down to -3.0%). Ferrozine-reactive Fe(II) was found in surface porewaters and in overlying core top waters, and was highest in the late spring period. Shipboard experiments showed that depletion of bottom water Responsible Editor: Martin Solan.Electronic supplementary material The online version of this article (doi:10.1007/s10533-017-0309-x) contains supplementary material, which is available to authorized users. 49-67 DOI 10.1007/s10533-017-0309-x oxygen in late spring can lead to a substantial release of Fe(II). Reoxygenation of bottom water caused this Fe(II) to be rapidly lost from solution, but residual dFe(II) and dFe(III) remained (12 and 33 nM) after [7 h. Iron(II) oxidation experiments in core top and bottom waters also showed removal from solution but at rates up to 5-times slower than predicted from theoretical reaction kinetics. These data imply the presence of ligands capable of complexing Fe(II) and supressing oxidation. The lower oxidation rate allows more time for the diffusion of Fe(II) from the sediments into the overlying water column. Modelling indicates significant diffusive fluxes of Fe(II) (on the order of 23-31 lmol m -2 day -1 ) are possible during late spring when oxygen penetration depths are shallow, and pore water Fe(II) concentrations are highest. In the water column this stabilised Fe(II) will gradually be oxidised and become part of the dFe(III) pool. Thus oxic continental shelves can supply dFe to the water column, which is enhanced during a small period of the year after phytoplankton bloom events when organic matter is transferred to the seafloor. This input is based on conservative assumptions for solute exchange (diffusion-reaction), whereas (bio)physical advection and resuspension events are likely to accelerate these solute exchanges in shelf-seas.

Anthropogenic activities have resulted in enhanced lead (Pb) emissions to the environment over the past century, mainly through the combustion of leaded gasoline. Here we present the first combined dissolved (DPb), labile (LpPb), and particulate (PPb) Pb data set from the Northeast Atlantic (Celtic Sea) since the phasing out of leaded gasoline in Europe. Concentrations of DPb in surface waters have decreased by fourfold over the last four decades. We demonstrate that anthropogenic Pb is transported from the Mediterranean Sea over long distances (>2,500 km). Benthic DPb fluxes exceeded the atmospheric Pb flux in the region, indicating the importance of sediments as a contemporary Pb source. A strong positive correlation between DPb, PPb, and LpPb indicates a dynamic equilibrium between the phases and the potential for particles to “buffer” the DPb pool. This study provides insights into Pb biogeochemical cycling and demonstrates the potential of Pb in constraining ocean circulation patterns.

Our study followed the seasonal cycling of soluble (SFe), colloidal (CFe), dissolved (DFe), total dissolvable (TDFe), labile particulate (LPFe), and total particulate (TPFe) iron in the Celtic Sea (NE Atlantic Ocean). Preferential uptake of SFe occurred during the spring bloom, preceding the removal of CFe. Uptake and export of Fe during the spring bloom, coupled with a reduction in vertical exchange, led to Fe deplete surface waters (<0.2 nM DFe; 0.11 nM LPFe, 0.45 nM TDFe, and 1.84 nM TPFe) during summer stratification. Below the seasonal thermocline, DFe concentrations increased from spring to autumn, mirroring NO3− and consistent with supply from remineralized sinking organic material, and cycled independently of particulate Fe over seasonal timescales. These results demonstrate that summer Fe availability is comparable to the seasonally Fe limited Ross Sea shelf and therefore is likely low enough to affect phytoplankton growth and species composition.

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