Phosphorus dynamics in the Barents Sea

The Barents Sea is considered a warming hotspot in the Arctic; elevated sea surface temperatures have been accompanied with increased inflow of Atlantic water onto the shelf sea. Such hydrodynamic changes and a concomitant reduction of sea ice coverage enables a prolonged phytoplankton growing season, which will inevitably affect nutrient stoichiometry and the controls on primary production. During the summer of 2018, we investigated the role of phosphorus in mediating primary production in the Barents Sea. Dissolved inorganic phosphorus (DIP), its most bioavailable form, had an average net turnover time of 9.4�4.8 d. The most southern Atlantic influenced station accounted for both the highest rates of primary production (655 mg C m2 d−1) and shortest net DIP turnover (2.8�0.5 d). The fraction of assimilated DIP released as dissolved organic phosphorus (DOP) at this station was < 4% compared to an average of 21% at all other stations. We observed significant differences between phytoplankton communities in Arctic and Atlantic waters within the Barents Sea. Slower DIP turnover and greater release of DOP was associated with Phaeocystis pouchetii dominated communities in Arctic waters. Faster turnover rates and greater phosphorus retention occurred among the Atlantic phytoplankton communities dominated by Emiliania huxleyi. Thesefindings provide baseline measurements of P utilization in the Barents Sea, and suggest increased Atlantic intrusion of this region could be accompanied by more rapid DIP turnover, possibly leading to future P limitation (rather than N limitation) on primary productio

Seasonal organic matter dynamics in a temperate shelf sea

Organic matter (OM) plays an important role in productive shelf seas and their contribution to global carbon (C) and nutrient cycles. We investigated dissolved and particulate OM (DOM and POM, respectively) dynamics over a seasonal cycle in the Celtic Sea. The quantity of OC was largest during the spring bloom and lowest in autumn. DOM was always C rich relative to the POM pool and the Redfield ratio (106C:16N:P). There was clear decoupling between C, N and P and the response of OM composition to different seasons and nutrient statuses of the microbial community. The C:P stoichiometry was much more variable than the C:N stoichiometry, which was near constant. Downward OC fluxes were dominated by POM during bloom events and DOM during the stratified summer. In terms of partitioning, 92–96% of OC was in the DOM pool throughout sampling, which given its high C:N (12.4–17) suggests it was an efficient vehicle for potential off-shelf export of C during winter mixing

Terrestrial dissolved organic matter distribution in the North Sea

The flow of terrestrial carbon to rivers and inland waters is a major term in the global carbon cycle. The organic fraction of this flux may be buried, remineralized or ultimately stored in the deep ocean. The latter can only occur if terrestrial organic carbon can pass through the coastal and estuarine filter, a process of unknown efficiency. Here, data are presented on the spatial distribution of terrestrial fluorescent and chromophoric dissolved organic matter (FDOM and CDOM, respectively) throughout the North Sea, which receives organic matter from multiple distinct sources. We use FDOM and CDOM as proxies for terrestrial dissolved organic matter (tDOM) to test the hypothesis that tDOM is quantitatively transferred through the North Sea to the open North Atlantic Ocean. Excitation emission matrix fluorescence and parallel factor analysis (EEM-PARAFAC) revealed a single terrestrial humic-like class of compounds whose distribution was restricted to the coastal margins and, via an inverse salinity relationship, to major riverine inputs. Two distinct sources of fluorescent humic-like material were observed associated with the combined outflows of the Rhine, Weser and Elbe rivers in the south-eastern North Sea and the Baltic Sea outflow to the eastern central North Sea. The flux of tDOM from the North Sea to the Atlantic Ocean appears insignificant, although tDOM export may occur through Norwegian coastal waters unsampled in our study. Our analysis suggests that the bulk of tDOM exported from the Northwest European and Scandinavian landmasses is buried or remineralized internally, with potential losses to the atmosphere. This interpretation implies that the residence time in estuarine and coastal systems exerts an important control over the fate of tDOM and needs to be considered when evaluating the role of terrestrial carbon losses in the global carbon cycle

Seasonal and spatial variability in the optical characteristics of DOM in a temperate shelf sea

The Celtic Sea is a productive temperate sea located on the Northwest European Shelf. It is an important pathway for the delivery of land-derived material to the North Atlantic Ocean, including dissolved organic matter (DOM). The aim of this study was to determine the seasonal and spatial variability in the magnitude, source and composition of DOM at three sites representing on shelf, central shelf and shelf edge regions in the Celtic Sea, using observations collected during the UK Shelf Sea Biogeochemistry (SSB) research programme (November 2014 – August 2015). The concentration of dissolved organic carbon (DOC) alongside DOM absorbance and fluorescence indices were measured and fluorescence Excitation and Emission Matrices (EEMs) combined with Parallel Factor Analysis (PARAFAC) were used to assess DOM composition and lability. The PARAFAC model identified four unique fluorescent components for autumn (November 2014), winter (March 2015), spring (April 2015) and summer (July 2015) consisting of two humic-like components attributed to terrestrial (C1) and marine sources (C2), and two protein components identified as tyrosine-like (C3) and tryptophan-like (C4) attributed to in situ production. DOC varied seasonally and there were strong cross shelf trends. The protein components (C3 and C4) exhibited large seasonal and within season variability particularly during productive periods. In contrast, there were persistent cross shelf gradients in the CDOM absorption coefficient at 305 nm (a305), the UV specific absorbance at 280 nm (SUVA280), the humification index (HIX), and the humic-like fluorescent components (C1 and C2), which were higher in the on shelf region and decreased towards the shelf edge. The humic-like components and the slope ratio (SR) were significantly correlated with salinity throughout all seasons, indicating a strong influence of terrestrially-derived organic matter in the Celtic Sea, with potentially up to 35% of DOC in the central shelf during winter originating from terrestrial inputs. Results from this study illustrate the importance of monitoring DOM quantitatively and qualitatively for a better understanding of the supply, production, cycling and export of this dynamic organic carbon pool in shelf seas

GO-SHIP Repeat Hydrography Nutrient Manual: The Precise and Accurate Determination of Dissolved Inorganic Nutrients in Seawater, Using Continuous Flow Analysis Methods

The GO-SHIP nutrient manual covers all aspects of nutrient analysis from basic sample collection and storage, specifically for Continuous Flow analysis using an Auto-Analyzer, and describes some specific nutrient methods for Nitrate, Nitrite, Silicate, Phosphate and Ammonium that are in use by many laboratories carrying out at-sea analysis and repeat hydrography sections across the world. The focus is on segmented flow analyzers not flow injection analyzers. It also covers laboratory best practices including quality control and quality assurance (QC/QA) procedures to obtain the best results, and suggests protocols for the use of reference materials (RM) and certified reference materials (CRMs)

Report from an International Nutrient Workshop focusing on Phosphate Analysis

A practical analytical workshop at NIOZ (Royal Netherlands Institute for Sea Research), The Netherlands, was held on 12-15 November 2012. The aim of the workshop was to gain information from the global nutrient analytical community about general problems which arise when measuring nutrients, and then to attempt to investigate these problems in the laboratory, with a small select representative group of International nutrient analysts conducting the lab work. 18 experts were participated and worked simultaneously on four different PO4 gas segmented CFA systems. This report documents the finding of the workshop and describes recommendations based on group consensus which can hopefully assist the larger community of labs worldwide participating in the Inter-Laboratory Comparison RMNS 2012 studies organized by MRI in Japan

Sensitivity of Modeled CO2 Air–Sea Flux in a Coastal Environment to Surface Temperature Gradients, Surfactants, and Satellite Data Assimilation

This work evaluates the sensitivity of CO2 air–sea gas exchange in a coastal site to four different model system configurations of the 1D coupled hydrodynamic–ecosystem model GOTM–ERSEM, towards identifying critical dynamics of relevance when specifically addressing quantification of air–sea CO2 exchange. The European Sea Regional Ecosystem Model (ERSEM) is a biomass and functional group-based biogeochemical model that includes a comprehensive carbonate system and explicitly simulates the production of dissolved organic carbon, dissolved inorganic carbon and organic matter. The model was implemented at the coastal station L4 (4 nm south of Plymouth, 50°15.00’N, 4°13.02’W, depth of 51 m). The model performance was evaluated using more than 1500 hydrological and biochemical observations routinely collected at L4 through the Western Coastal Observatory activities of 2008—2009. In addition to a reference simulation (A), we ran three distinct experiments to investigate the sensitivity of the carbonate system and modeled air–sea fluxes to (B) the sea-surface temperature (SST) diurnal cycle and thus also the near-surface verticalgradients,(C)biologicalsuppressionofgasexchangeand(D)dataassimilationusingsatellite Earth observation data. The reference simulation captures well the physical environment (simulated SST has a correlation with observations equal to 0.94 with a p > 0.95). Overall, the model captures the seasonal signal in most biogeochemical variables including the air–sea flux of CO2 and primary production and can capture some of the intra-seasonal variability and short-lived blooms. The model correctlyreproducestheseasonalityofnutrients(correlation>0.80forsilicate,nitrateandphosphate), surface chlorophyll-a (correlation > 0.43) and total biomass (correlation > 0.7) in a two year run for 2008–2009. The model simulates well the concentration of DIC, pH and in-water partial pressure of CO2 (pCO2) with correlations between 0.4–0.5. The model result suggest that L4 is a weak net source of CO2 (0.3–1.8 molCm−2 year−1). The results of the three sensitivity experiments indicate that both resolving the temperature profile near the surface and assimilation of surface chlorophyll-a significantlyimpacttheskillofsimulatingthebiogeochemistryatL4andallofthecarbonatechemistry related variables. These results indicate that our forecasting ability of CO2 air–sea flux in shelf seas environments and their impact in climate modeling should consider both model refinements as means of reducing uncertainties and errors in any future climate projections

Increasing picocyanobacteria success in shelf waters contributes to long-term food web degradation

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

Field assessment of the potential for small scale co-cultivation of seaweed and shellfish to regulate nutrients and plankton dynamics

This is the final version. Available on open access from Elsevier via the DOI in this recordData Availability; Data will be made available on request.The co-cultivation of seaweed alongside shellfish has the potential to regulate local dissolved nutrient concentrations and consequently affect plankton dynamics. Evidence for this has until now come largely from computational modelling and laboratory studies, rather than field studies. Here we report on weekly/bi-weekly profiling of inorganic nutrient concentrations (nitrate, nitrite, ammonium, phosphate, and silicate) over two years (2019–2020) at three sampling stations across a small-scale (16 ha) kelp and mussel farm in Porthallow Bay, Cornwall, UK. Nutrient concentrations were measured in conjunction with a range of related environmental variables, including water temperature, salinity, clarity, and phyto- and zoo- plankton abundance, biomass and community composition. These environmental data were also supplemented with river discharge data. Our results indicate typical seasonal variations in chemical (nutrient), physical (hydrographic), and biological (plankton) parameters across all three sampling stations and no significant reductions in inorganic nutrient concentrations in the water column downstream from the integrated kelp and shellfish farm. We conclude that the effectiveness of nutrient regulation by integrating seaweed and shellfish aquaculture will depend on local climatic and hydro-geochemical conditions (affecting background nutrient inputs), as well as the design and scale of integrated multi–trophic aquaculture (IMTA) systems.Natural Environment Research Council (NERC)European Maritime and Fisheries FundFishmongers' Company's Charitable Trust, UKCornish Seaweed CompanyWestcountry Mussels of FoweyCornwall Inshore Fisheries Conservation AuthorityUKR

Fluorescence studies on new potential antitumoral benzothienopyran-1-ones in solution and in liposomes

Fluorescence properties of four new potential antitumoral compounds, 3-arylbenzothieno[2,3-c]pyran-1-ones, were studied in solution and in lipid membranes of dipalmitoyl phosphatidylcholine (DPPC), egg yolk phosphatidylcholine (Egg-PC) and dioctadecyldimethylammonium bromide (DODAB). The 3-(4-methoxyphenyl)benzothieno[2,3-c]pyran-1-one (1c) exhibits the higher fluorescence quantum yields in all solvents studied. All compounds present a solvent sensitive emission, with significant red shifts in polar solvents for the methoxylated compounds. The results point to an ICT character of the excited state, more pronounced for compound 1c. Fluorescence (steady-state) anisotropy measurements of the compounds incorporated in liposomes of DPPC, DODAB and Egg-PC indicate that all compounds have two different locations, one due to a deep penetration in the lipid membrane and another corresponding to a more hydrated environment. In general, the methoxylated compounds prefer hydrated environments inside the liposomes. The 3-(4- fluorophenyl)benzothieno[2,3-c]pyran-1-one (1a) clearly prefers a hydrated environment, with some molecules located at the outer part of the liposome interface. On the contrary, the preferential location of 3-(2-fluorophenyl)benzothieno[2,3-c]pyran-1-one (1b) is in the region of lipid hydrophobic tails. Compounds with a planar geometry (1a and 1c) have higher mobility in the lipid membranes when phase transition occurs.Portugal and FEDER (Fundo Europeu de Desenvolvimento Regional), for financial support through Centro de Física (CFUM) and Centro de Química (CQ-UM) of University of Minho and through the Project PTDC/QUI/81238/2006. M.S.D. Carvalho and R.C. Calhelha acknowledge FCT for their PhD grants SFRH/BD/47052/2008 and SFRH/BD/29274/2006, respectively.Fundação para a Ciência e a Tecnologia (FCT