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.

Highlights:  Seasonal phosphorus uptake and dissolved organic release examined in the Central Celtic Sea  Uptake highest in spring bloom, with biomass-normalised uptake equal in spring and summer  Release high in November and late spring, with efficient P-retention in summer  Strong phytoplankton influence on spring P-uptake, whilst bacteria influential in summer  Relatively C-rich uptake in November and late April, strongly P-rich in summer Abstract The seasonal cycle of resource availability in shelf seas has a strong selective pressure on phytoplankton diversity and the biogeochemical cycling of key elements, such as carbon (C) and phosphorus (P). Shifts in carbon consumption relative to P availability, via changes in cellular stoichiometry for example, can lead to an apparent 'excess' of carbon production. We made measurements of inorganic P (P i) uptake, in parallel to C-fixation, by plankton communities in the Central Celtic Sea (NW European Shelf) in spring (April 2015), summer (July 2015) and fall (November 2014). Short-term (<6 h) P i-uptake coupled with dissolved organic phosphorus (DOP) release, in parallel to net (24 h) primary production (NPP), were all measured across an irradiance gradient designed to typify vertically and seasonally varying light conditions. Rates of P i-uptake were highest during spring and lowest in light-limited fall conditions, although biomass-normalised P i-uptake was similar in spring and summer. The release of DOP was highest in November and declined to low levels in July, indicative of efficient utilization and recycling of the low levels of P i available. Examination of turnover times of the different particulate pools, including phytoplankton and bacteria, indicated a differing seasonal influence of autotrophs and heterotrophs in P-dynamics, with summer conditions associated with a strong bacterial influence and early spring with fast growing phytoplankton. These seasonal changes in plankton composition, coupled with changes in resource availability (P i , light) resulted in seasonal changes in the stoichiometry of NPP to P i-uptake (C:P ratio); from relatively C-rich uptake in November and late April, to P-rich uptake in early April and July. Overall these results highlight how the entire plankton community, both autotrophs and heterotrophs, influence the relative uptake of C and P and that any excess C-consumption relative to the P-rich uptake must be balanced by C-rich process such as the heterotrophic remineralisation and/or consumption of organic material.

Continental shelf sediments are globally important for biogeochemical activity. Quantification of shelf-scale stocks and fluxes of carbon and nutrients requires the extrapolation of observations made at limited points in space and time. The procedure for selecting exemplar sites to form the basis of this upscaling is discussed in relation to a UK-funded research programme investigating biogeochemistry in shelf seas. A three-step selection process is proposed in which (1) a target area representative of UK shelf sediment heterogeneity is selected, (2) the target area is assessed for spatial heterogeneity in sediment and habitat type, bed and water column structure and hydrodynamic forcing, and (3) study sites are selected within this target area encompassing the range of spatial heterogeneity required to address key scientific questions regarding shelf scale biogeochemistry, and minimise confounding variables. This led to the selection of four sites within the Celtic Sea that are significantly different in terms of their sediment, bed structure, and macrofaunal, meiofaunal and microbial community structures and diversity, but have minimal variations in water depth, tidal and wave magnitudes and directions, temperature and salinity. They form the basis of a research cruise programme of observation, sampling and experimentation encompassing the spring bloom cycle. Typical variation in key biogeochemical, sediment, biological and hydrodynamic parameters over a pre to post bloom period are presented, with a discussion of anthropogenic influences in the region. This methodology ensures the best likelihood of site-specific work being useful for up-scaling activities, increasing our understanding of benthic biogeochemistry at the UK-shelf scale.

Shelf sediments play a vital role in global biogeochemical cycling and are particularly important areas of oxygen consumption and carbon mineralisation. Total benthic oxygen uptake, the sum of diffusive and faunal mediated uptake, is a robust proxy to quantify carbon mineralisation. However, oxygen uptake rates are dynamic, due to the diagenetic processes within the sediment, and can be spatially and temporally variable. Four benthic sites in the Celtic Sea, encompassing gradients of cohesive to permeable sediments, were sampled over four cruises to capture seasonal and spatial changes in oxygen dynamics. Total oxygen uptake (TOU) rates were measured through a suite of incubation experiments and oxygen microelectrode profiles were taken across all four benthic sites to provide the oxygen penetration depth and diffusive oxygen uptake (DOU) rates. The difference between TOU and DOU allowed for quantification of the fauna mediated oxygen uptake and diffusive uptake. High resolution measurements showed clear seasonal and spatial trends, with higher oxygen uptake rates measured in cohesive sediments compared to the permeable sediment. The significant differences in oxygen dynamics between the sediment types were consistent between seasons, with increasing oxygen consumption during and after the phytoplankton bloom. Carbon mineralisation in shelf sediments is strongly influenced by sediment type and seasonality.

This study used microelectrodes to record pH profiles in fresh shelf sea sediment cores collected across a range of different sediment types within the Celtic Sea. Spatial and temporal variability was captured during repeated measurements in 2014 and 2015. Concurrently recorded oxygen microelectrode profiles and other sedimentary parameters provide a detailed context for interpretation of the pH data. Clear differences in profiles were observed between sediment type, location and season. Notably, very steep pH gradients exist within the surface sediments (10-20 mm), where decreases greater than 0.5 pH units were observed. Steep gradients were particularly apparent in fine cohesive sediments, less so in permeable sandier matrices. We hypothesise that the gradients are likely caused by aerobic organic matter respiration close to the sediment-water interface or oxidation of reduced species at the base of the oxic zone (NH 4 ? , Mn 2? , Fe 2? , S -). Statistical analysis suggests the variability in the depth of the pH minima is controlled spatially by the oxygen penetration depth, and seasonally by the input and remineralisation of deposited organic phytodetritus. Below the pH minima the observed pH remained consistently low to maximum electrode penetration (ca. 60 mm), indicating an absence of sub-oxic processes generating H ? or balanced removal processes within this layer. Thus, a climatology of sediment surface porewater pH is provided against which to examine biogeochemical processes. This enhances our understanding of benthic pH processes, particularly in the context of human impacts, seabed integrity, and future climate changes, providing vital information for modelling benthic response under future climate scenarios.

The Croker Carbonate Slabs, in the UK sector of the Irish Sea, has shallow (70 to 100 m) water, strong (> 2 knot) tidal currents, coarse mobile surficial sediments and the most extensive methane-derived authigenic carbonate (MDAC) known in European waters. Multi-disciplinary studies (2004 to 2015) were commissioned specifically to document the benthic habitat, and have resulted in the designation of this site as a Marine Protected Area (MPA) under the European Commission’s Habitats Directive as an example of “Submarine structures formed by leaking gases”. However, this paper is focussed on the geoscience aspects of the site: the mineralogy and isotopic composition of the MDAC, its formation and age. It considers the implications of these findings with respect to the timing of the deglaciation of the area since the Last Glacial Maximum (LGM), and the environmental implications of the seepage of methane from the site over a period of at least 17,000 years. Carbon isotope ratios (δ13 C − 34 to − 54‰) confirm that the carbonate minerals (high-Mg calcite and aragonite) result from the anaerobic oxidation of methane. Widespread shallow gas within post-glacial sediments is sourced from underlying coal-bearing Carboniferous strata. Geophysical (side-scan sonar and multi-beam echo sounder) and visual surveys show that the MDAC occurs as isolated lumps, continuous pavements, and cliffs < 6 m tall, which post-date the post-glacial sediments, but are in places covered by a veneer of coarse mobile surficial sediments. U-Th dates (17,000 ± 5500 to 4000 ± 200 BP) suggest continual MDAC formation since the last glacial maximum, and constrain the postglacial sea level rise in this part of the Irish Sea; the site must have been submarine before MDAC formation started, whether or not methane was escaping. Visual and acoustic evidence of gas seepage is limited, but methane concentrations in the water are high (< 21.4 nmol l−1) and suggest present-day export to the atmosphere. It is also implied that significant methane release to the atmosphere occurred immediately after the retreat of the ice that covered the site during the LGM until 21.9 to 20.7 ka BP.

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