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15 pages, 5 figures, 2 tables.-- This work is distributed under the Creative Commons Attribution 4.0 License., The characteristics of the CISE-LOCEAN seawater isotope dataset (δ18O, δ2H, referred to as δD) are presented (https://doi.org/10.17882/71186; Waterisotopes-CISE-LOCEAN, 2021). This dataset covers the time period from 1998 to 2021 and currently includes close to 8000 data entries, all with δ18O, three-quarters of them also with δD, associated with a date stamp, space stamp, and usually a salinity measurement. Until 2010, samples were analyzed by isotopic ratio mass spectrometry and since then mostly by cavity ring-down spectroscopy (CRDS). Instrumental uncertainty in this dataset is usually as low as 0.03 ‰ for δ18O and 0.15 ‰ for δD. An additional uncertainty is related to the isotopic composition of the in-house standards that are used to convert data to the Vienna Standard Mean Ocean Water (VSMOW) scale. Different comparisons suggest that since 2010 the latter have remained within at most 0.03 ‰ for δ18O and 0.20 ‰ for δD. Therefore, combining the two uncertainties suggests a standard deviation of at most 0.05 ‰ for δ18O and 0.25 ‰ for δD. For some samples, we find that there has been evaporation during collection and storage, requiring adjustment of the isotopic data produced by CRDS, based on d-excess (δD − 8×δ18O). This adjustment adds an uncertainty in the respective data of roughly 0.05 ‰ for δ18O and 0.10 ‰ for δD. This issue of conservation of samples is certainly a strong source of quality loss for parts of the database, and “small” effects may have remained undetected. The internal consistency of the database can be tested for subsets of the dataset when time series can be obtained (such as in the southern Indian Ocean or North Atlantic subpolar gyre). These comparisons suggest that the overall uncertainty of the spatially (for a cruise) or temporally (over a year) averaged data is less than 0.03 ‰ for δ18O and 0.15 ‰ for δD. However, 18 comparisons with duplicate seawater data analyzed in other laboratories or with other datasets in the intermediate and deep ocean suggest a larger scatter. When averaging the 18 comparisons done for δ18O, we find a difference of 0.082 ‰ with a standard error of 0.016 ‰. Such an average difference is expected due to the adjustments applied at LOCEAN to saline water data produced either by CRDS or isotope ratio mass spectrometry (IRMS), but the scatter found suggests that care is needed when merging datasets from different laboratories. Examples of time series in the surface North Atlantic subpolar gyre illustrate the temporal changes in water isotope composition that can be detected with a carefully validated dataset, The WAPITI project received funding from the European Research Council (ERC) under the European Union's Horizon 2020 research and innovation program (grant agreement 637770). The Antarctic Circumnavigation Expedition was made possible by funding from the Swiss Polar Institute and Ferring Pharmaceuticals, and F. Alexander Haumann was supported by SNSF grant numbers P2EZP2_175162 and P400P2_186681

The characteristics of the CISE-LOCEAN sea water isotope data set (δ18O, δ2H, later designed as δD) are presented. This data set covers the time period from 1998 to 2021 and currently includes close to 8000 data entries, all with δ18O, three quarters of them also with δD, associated with a time and space stamp and usually a salinity measurement. Until 2010, samples were analysed by isotopic ratio mass spectrometry, and since then mostly by cavity ring-down spectroscopy (CRDS). Instrumental uncertainty on individual data in this dataset is usually with a standard deviation as low as 0.03 / 0.15 ‰ for δ18O and δD. An additional uncertainty is related to uncertain isotopic composition of the in-house standards that are used to convert daily data into the VSMOW scale. Different comparisons suggest that since 2010 the latter have remained within at most 0.03 / 0.20 ‰ for δ18O and δD. Therefore, combining the two suggests a standard deviation of at most 0.05 / 0.25 ‰ for δ18O / δD. Finally, for some samples, we find that there has been evaporation during collection and storage, requiring adjustment of the isotopic data produced by CRDS, based on d-excess. This adds an uncertainty on the adjusted data of roughly 0.05 / 0.10 ‰ on δ18O and δD. This issue of conservation of samples is certainly a strong source of quality loss for parts of the database, and ‘small’ effects may have remained undetected. The internal consistency of the database can be tested for subsets of the dataset, when time series can be obtained (such as in the southern Indian Ocean or North Atlantic subpolar gyre). These comparisons suggest that the overall uncertainty of the spatially (for a cruise) or temporally (over a year) averaged data is on the order of or less than 0.03 / 0.15 ‰ for δ18O / δD. On the other hand, 17 comparisons with duplicate sea water data analysed in other laboratories or with other data sets in deep regions suggest a larger scatter. When averaging the 17 comparisons done for δ18O, we find a difference close to the adjustment applied at LOCEAN to convert salty water data from the activity to the concentration scale. Such a difference is expected, but the scatter found suggests that care is needed when merging datasets from different laboratories. Examples of time series in the surface North Atlantic subpolar gyre illustrate the temporal changes in water isotope composition that can be detected with a carefully validated dataset.

Microfluidic reagent-based nutrient sensors offer a promising technology to address the global undersampling of ocean chemistry but have so far not been shown to operate in the deep sea (>200 m). We report a new family of miniaturized lab-on-chip (LOC) colorimetric analyzers making in situ nitrate and phosphate measurements from the surface ocean to the deep sea (>4800 m). This new technology gives users a new low-cost, high-performance tool for measuring chemistry in hyperbaric environments. Using a combination of laboratory verification and field-based tests, we demonstrate that the analyzers are capable of in situ measurements during profiling that are comparable to laboratory-based analyses. The sensors feature a novel and efficient inertial-flow mixer that increases the mixing efficiency and reduces the back pressure and flushing time compared to a previously used serpentine mixing channel. Four separate replicate units of the nitrate and phosphate sensor were calibrated in the laboratory and showed an average limit of detection of 0.03 μM for nitrate and 0.016 μM for phosphate. Three on-chip optical absorption cell lengths provide a large linear range (to >750 μM (10.5 mg/L-N) for nitrate and >15 μM (0.47 mg/L-P) for phosphate), making the instruments suitable for typical concentrations in both ocean and freshwater aquatic environments. The LOC systems automatically collected a series of deep-sea nitrate and phosphate profiles in the northeast Atlantic while attached to a conductivity temperature depth (CTD) rosette, and the LOC nitrate sensor was attached to a PROVOR profiling float to conduct automated nitrate profiles in the Mediterranean Sea.

Ocean biological processes play an important role in the global carbon cycle via the production of organic matter and its subsequent export. Often, this flux is assumed to be in steady state; however, it is dependent on nutrients introduced to surface waters via multiple mechanisms, some of which are likely to exhibit both intra‐annual and interannual variability leading to comparable variability in ocean carbon uptake. Here we test this variability using surface (5 m) inorganic nutrient concentrations from voluntary observing ships and satellite‐derived estimates of chlorophyll and net primary production. At lower latitudes, the seasonality is small, and the monthly averages of nitrate:phosphate are lower than the canonical 16:1 Redfield ratio, implying nitrogen limitation, a situation confirmed via a series of nutrient limitation experiments conducted between Bermuda and Puerto Rico. The nutrient seasonal cycle is more pronounced at higher latitudes, with clear interannual variability. Over a large area of the midlatitude North Atlantic, the winters of 2009/2010 and 2010/2011 had nitrate values more than 1μmol L−1 higher than the 2002–2017 average, suggesting that during this period, the system may have shifted to phosphorus limitation. This nitrate increase meant that, in the region between 31° and 39° N, new production calculated from nitrate uptake was 20.5g C m−2 in 2010, more than four times higher than the median value of the whole observing period. Overall, we suggest that substantial variability in nutrient concentrations and biological carbon uptake occurs in the North Atlantic with interannual variability apparent over a number of different time scales.

Previous work has not led to a clear understanding of the causes of spatial pattern in global surface ocean dissolved inorganic carbon (DIC), which generally increases polewards. Here, we revisit this question by investigating the drivers of observed latitudinal gradients in surface salinity-normalized DIC (nDIC) using the Global Ocean Data Analysis Project version 2 (GLODAPv2) database. We used the database to test three different hypotheses for the driver producing the observed increase in surface nDIC from low to high latitudes. These are (1) sea surface temperature, through its effect on the CO2 system equilibrium constants, (2) salinity-related total alkalinity (TA), and (3) high-latitude upwelling of DIC- and TA-rich deep waters. We find that temperature and upwelling are the two major drivers. TA effects generally oppose the observed gradient, except where higher values are introduced in upwelled waters. Temperature-driven effects explain the majority of the surface nDIC latitudinal gradient (182 of the 223 µmol kg−1 increase from the tropics to the high-latitude Southern Ocean). Upwelling, which has not previously been considered as a major driver, additionally drives a substantial latitudinal gradient. Its immediate impact, prior to any induced air–sea CO2 exchange, is to raise Southern Ocean nDIC by 220 µmol kg−1 above the average low-latitude value. However, this immediate effect is transitory. The long-term impact of upwelling (brought about by increasing TA), which would persist even if gas exchange were to return the surface ocean to the same CO2 as without upwelling, is to increase nDIC by 74 µmol kg−1 above the low-latitude average.

Knowledge of the surface ocean dynamics and the underlying controlling mechanisms is critical to understand the natural variability of the ocean and to predict its future response to climate change. In this paper, we highlight the potential use of Volunteer Observing Ship (VOS), as carrier for automatic underway measuring system and as platform for sample collection, to enhance the observing capacity for the surface ocean. We review the concept, history, present status and future development of the VOS-based in situ surface ocean observation. The successes of various VOS projects demonstrate that, along with the rapid advancing sensor techniques, VOS is able to improve the temporal resolution and spatial coverage of the surface ocean observation in a highly cost-effective manner. A sustained and efficient marine monitoring system in the future should integrate the advantages of various observing platforms including VOS.

Until the 1980s, the deep sea was generally considered to be a particularly stable environment, free from major temporal variations (Sanders, 1968). Studies in the abyssal northeast Atlantic by Billett et al. (1983), and subsequently Lampitt (1985) discovered seasonal pulses of surface primary production-derived particulate organic matter (phytodetritus), and hence carbon, at abyssal depths. These early observations were subsequently extended to the central oceanic region of the NE Atlantic (Pfannkuche, 1993; Thiel et al., 1989), and prompted the establishment of more concerted time series studies in the Porcupine Abyssal Plain area. Today, the Porcupine Abyssal Plain Sustained Observatory (PAP–SO) is a multidisciplinary open-ocean time series site in the NE Atlantic (48°50′N 16°30′W, 4850 m water depth; Fig. 1), focused on the study of connections between the surface and deep ocean. In situ measurements of climatically and environmentally relevant variables have been made for more than 30 years. This represents an exceptionally long time series - a recent compilation of biological time series data, across terrestrial, freshwater, and marine realms, indicates an average duration of only 13-years (Dornelas et al., 2018). Long-term time series in the deep sea are rare, particularly those collecting data from surface to seabed. The PAP-SO is one of two abyssal long-term time series sites globally (Smith et al. 2015), the other being a thirty-year time series at Station M in the northeastern Pacific Ocean (34°50′N, 123°00′W, ~4000 m water depth), maintained by the Monterey Bay Aquarium Research Institute (Smith et al., 2020). This ‘sibling’ abyssal time series site also aims to understand the connections between the surface ocean and the seabed, using many similar techniques (Smith et al., 2017), facilitating comparisons between the two sites (e.g. Durden et al., 2019; Durden et al., 2020a; Laguionie-Marchais et al., 2013; Smith et al., 2009). Another source of extended comparison is the 21 year time series Long-Term Ecological Research Observatory HAUSGARTEN, Frontiers in Arctic Marine Monitoring (FRAM) in the Fram Strait between the North Atlantic and the central Arctic Ocean (78.5°N–80°N, 05°W–11°E, 250–5500 m water depth), maintained by the Alfred Wegener Institute for Polar and Marine Research (Soltwedel et al., 2016; Soltwedel et al., 2005). Much of our understanding of temporal variation in the deep sea, and connections between the surface ocean and the seabed have been derived from research conducted at these observatories.

Since 1750, land-use change and fossil fuel combustion has led to a 46% increase in the atmospheric carbon dioxide (CO2) concentrations, causing global warming with substantial societal consequences. The Paris Agreement aims to limit global temperature increases to well below 2°C above preindustrial levels. Increasing levels of CO2 and other greenhouse gases (GHGs), such as methane (CH4) and nitrous oxide (N2O), in the atmosphere are the primary cause of climate change. Approximately half of the carbon emissions to the atmosphere are sequestered by ocean and land sinks, leading to ocean acidification but also slowing the rate of global warming. However, there are significant uncertainties in the future global warming scenarios due to uncertainties in the size, nature, and stability of these sinks. Quantifying and monitoring the size and timing of natural sinks and the impact of climate change on ecosystems are important information to guide policy-makers’ decisions and strategies on reductions in emissions. Continuous, long-term observations are required to quantify GHG emissions, sinks, and their impacts on Earth systems. The Integrated Carbon Observation System (ICOS) was designed as the European in situ observation and information system to support science and society in their efforts to mitigate climate change. It provides standardized and open data currently from over 140 measurement stations across 12 European countries. The stations observe GHG concentrations in the atmosphere and carbon and GHG fluxes between the atmosphere, land surface, and the oceans. This article describes how ICOS fulfills its mission to harmonize these observations, ensure the related long-term financial commitments, provide easy access to well-documented and reproducible high-quality data and related protocols and tools for scientific studies, and deliver information and GHG-related products to stakeholders in society and policy.

12 pages, 5 figures, supporting information https://doi.org/10.1073/pnas.1918943117.-- Data Availability. Our published databases are publicly accessible for readers, and they are deposited at the NOAA NCEI at https://data.nodc.noaa.gov/cgi-bin/iso?id=gov.noaa.nodc:0171017.-- Correction for Lebrato et al., Global variability in seawater Mg:Ca and Sr:Ca ratios in the modern ocean; Proceedings of the National Academy of Sciences of the USA 118(49): e2119099118 (2021); doi: 10.1073/pnas.2119099118; http://hdl.handle.net/10261/258054.-- This is Pacific Marine Environmental Laboratory contribution number 5046, Seawater Mg:Ca and Sr:Ca ratios are biogeochemical parameters reflecting the Earth–ocean–atmosphere dynamic exchange of elements. The ratios’ dependence on the environment and organisms' biology facilitates their application in marine sciences. Here, we present a measured single-laboratory dataset, combined with previous data, to test the assumption of limited seawater Mg:Ca and Sr:Ca variability across marine environments globally. High variability was found in open-ocean upwelling and polar regions, shelves/neritic and river-influenced areas, where seawater Mg:Ca and Sr:Ca ratios range from ∼4.40 to 6.40 mmol:mol and ∼6.95 to 9.80 mmol:mol, respectively. Open-ocean seawater Mg:Ca is semiconservative (∼4.90 to 5.30 mol:mol), while Sr:Ca is more variable and nonconservative (∼7.70 to 8.80 mmol:mol); both ratios are nonconservative in coastal seas. Further, the Ca, Mg, and Sr elemental fluxes are connected to large total alkalinity deviations from International Association for the Physical Sciences of the Oceans (IAPSO) standard values. Because there is significant modern seawater Mg:Ca and Sr:Ca ratios variability across marine environments we cannot absolutely assume that fossil archives using taxa-specific proxies reflect true global seawater chemistry but rather taxa- and process-specific ecosystem variations, reflecting regional conditions. This variability could reconcile secular seawater Mg:Ca and Sr:Ca ratio reconstructions using different taxa and techniques by assuming an error of 1 to 1.50 mol:mol, and 1 to 1.90 mmol:mol, respectively. The modern ratios’ variability is similar to the reconstructed rise over 20 Ma (Neogene Period), nurturing the question of seminonconservative behavior of Ca, Mg, and Sr over modern Earth geological history with an overlooked environmental effect, This study was developed under a grant from the Federal Ministry of Education and Research to D.G.-S. under contract 03F0722A, by the Kiel Cluster of Excellence “The Future Ocean” (D1067/87) to A.O. and M.L., and by the “European project on Ocean Acidification” (European Community’s Seventh Framework Programme FP7/2007-2013, grant agreement 211384) to A.O. and M.L. Additional funding was provided from project DOSMARES CTM2010-21810-C03-02, by the UK Natural Environment Research Council, to the National Oceanography Centre, With the funding support of the ‘Severo Ochoa Centre of Excellence’ accreditation (CEX2019-000928-S), of the Spanish Research Agency (AEI)

Shelf seas play an important role in the global carbon cycle, absorbing atmospheric carbon dioxide (CO2) and exporting carbon (C) to the open ocean and sediments. The magnitude of these processes is poorly constrained, because observations are typically interpolated over multiple years. Here, we used 298500 observations of CO2 fugacity (fCO2) from a single year (2015), to estimate the net influx of atmospheric CO2 as 26.2 ± 4.7 Tg C yr−1 over the open NW European shelf. CO2 influx from the atmosphere was dominated by influx during winter as a consequence of high winds, despite a smaller, thermally-driven, air-sea fCO2 gradient compared to the larger, biologically-driven summer gradient. In order to understand this climate regulation service, we constructed a carbon-budget supplemented by data from the literature, where the NW European shelf is treated as a box with carbon entering and leaving the box. This budget showed that net C-burial was a small sink of 1.3 ± 3.1 Tg C yr−1, while CO2 efflux from estuaries to the atmosphere, removed the majority of river C-inputs. In contrast, the input from the Baltic Sea likely contributes to net export via the continental shelf pump and advection (34.4 ± 6.0 Tg C yr−1).

Ocean acidification (OA), the anthropogenic carbon dioxide-induced changes in seawater carbonate chemistry, is likely to have a significant impact on calcifying plankton. Most planktonic studies on OA are based on “one-off” cruises focused on offshore areas while observations from inshore waters are scarce. This study presents the first analysis on the shell integrity of pelagic gastropods (holoplanktonic pteropods and planktonic larvae of otherwise benthic species) at the Scottish Coastal Observatory monitoring site at Stonehaven on the east coast of Scotland. The shell integrity of archived pelagic gastropods specimens from 2011 to 2013 was examined using Scanning Electron Microscopy and the relationship with OA (pH and aragonite saturation, Ωarg) and other environmental parameters was investigated. Evidence of shell dissolution was detected in all analysed taxa even though the seawater was supersaturated with respect to aragonite. The shell condition matched the temporal pattern observed in Ωarg, with higher proportion of dissolution associated with decreasing Ωarg, suggesting that the seasonality component of carbonate chemistry might affect the shell integrity of pelagic gastropods. The proportion of shell dissolution differed significantly between larvae and adult stages of pteropods, supporting the hypothesis that early-life stages would be more vulnerable to OA-induced changes. Our data also suggest that sensitivity to OA may differ even between closely related taxonomic groups. The strong interannual variability revealed by the year-to-year shell dissolution and Ωarg illustrates the difficulty in assessing the plankton response to OA in the field and the value of time series studies.

Highlights • Seawater dissolved inorganic carbon and nutrients measured for 1.5 seasonal cycles. • Inventories not in steady state from one winter to the next (e.g. 10% nitrate loss) • Significant fraction of annual production stored in long-lived organic matter pool. • Organic matter could provide mechanism for “continental shelf pump” carbon export. Abstract Continental shelf seas may have a significant role in oceanic uptake and storage of carbon dioxide (CO2) from the atmosphere, through a ‘continental shelf pump’ mechanism. The northwest European continental shelf, in particular the Celtic Sea (50°N 8°W), was the target of extensive biogeochemical sampling from March 2014 to September 2015, as part of the UK Shelf Sea Biogeochemistry research programme (UK-SSB). Here, we use the UK-SSB carbonate chemistry and macronutrient measurements to investigate the biogeochemical seasonality in this temperate, seasonally stratified system. Following the onset of stratification, near-surface biological primary production during spring and summer removed dissolved inorganic carbon and nutrients, and a fraction of the sinking particulate organic matter was subsequently remineralised beneath the thermocline. Water column inventories of these variables throughout 1.5 seasonal cycles, corrected for air-sea CO2 exchange and sedimentary denitrification and anammox, isolated the combined effect of net community production (NCP) and remineralisation on the inorganic macronutrient inventories. Overall inorganic inventory changes suggested that a significant fraction (>50%) of the annual NCP of around 3 mol-C m–2 yr–1 appeared to be stored within a long-lived organic matter (OM) pool with a lifetime of several months or more. Moreover, transfers into and out of this pool appeared not to be in steady state over the one full seasonal cycle sampled. Accumulation of such a long-lived and potentially C-rich OM pool is suggested to be at least partially responsible for the estimated net air-to-sea CO2 flux of ∼1.3 mol-C m–2 yr–1 at our study site, while providing a mechanism through which a nutrient-conserving continental shelf pump for CO2 could potentially operate in this and other similar regions.

The oceans play a key role in global issues such as climate change, food security, and human health. Given their vast dimensions and internal complexity, efficient monitoring and predicting of the planet’s ocean must be a collaborative effort of both regional and global scale. A first and foremost requirement for such collaborative ocean observing is the need to follow well-defined and reproducible methods across activities: from strategies for structuring observing systems, sensor deployment and usage, and the generation of data and information products, to ethical and governance aspects when executing ocean observing. To meet the urgent, planet-wide challenges we face, methods across all aspects of ocean observing should be broadly adopted by the ocean community and, where appropriate, should evolve into “Ocean Best Practices.” While many groups have created best practices, they are scattered across the Web or buried in local repositories and many have yet to be digitized. To reduce this fragmentation, we introduce a new open access, permanent, digital repository of best practices documentation (oceanbestpractices.org) that is part of the Ocean Best Practices System (OBPS). The new OBPS provides an opportunity space for the centralized and coordinated improvement of ocean observing methods. The OBPS repository employs user-friendly software to significantly improve discovery and access to methods. The software includes advanced semantic technologies for search capabilities to enhance repository operations. In addition to the repository, the OBPS also includes a peer reviewed journal research topic, a forum for community discussion and a training activity for use of best practices. Together, these components serve to realize a core objective of the OBPS, which is to enable the ocean community to create superior methods for every activity in ocean observing from research to operations to applications that are agreed upon and broadly adopted across communities. Using selected ocean observing examples, we show how the OBPS supports this objective. This paper lays out a future vision of ocean best practices and how OBPS will contribute to improving ocean observing in the decade to come.

In 2014–5 the UK NERC sponsored an 18 month long Shelf Sea Biogeochemistry research programme which collected over 1500 nutrient and carbonate system samples across the NW European Continental shelf, one of the largest continental shelves on the planet. This involved the cooperation of 10 different Institutes and Universities, using 6 different vessels. Additional carbon dioxide (CO2) data were obtained from the underway systems on three of the research vessels. Here, we present and discuss these data across 9 ecohydrodynamic regions, adapted from those used by the EU Marine Strategy Framework Directive (MSFD). We observed strong seasonal and regional variability in carbonate chemistry around the shelf in relation to nutrient biogeochemistry. Whilst salinity increased (and alkalinity decreased) out from the near-shore coastal waters offshore throughout the year nutrient concentrations varied with season. Spatial and seasonal variations in the ratio of DIC to nitrate concentration were seen that could impact carbon cycling. A decrease in nutrient concentrations and a pronounced under-saturation of surface pCO2 was evident in the spring in most regions, especially in the Celtic Sea. This decrease was less pronounced in Liverpool Bay and to the North of Scotland, where nutrient concentrations remained measurable throughout the year. The near-shore and relatively shallow ecosystems such as the eastern English Channel and southern North Sea were associated with a thermally driven increase in pCO2 to above atmospheric levels in summer and an associated decrease in pH. Non-thermal processes (such as mixing and the remineralisation of organic material) dominated in winter in most regions but especially in the northwest of Scotland and in Liverpool Bay. The large database collected will improve understanding of carbonate chemistry over the North-Western European Shelf in relation to nutrient biogeochemistry, particularly in the context of climate change and ocean acidification.

Lack of information about carbonate chemistry in inshore waters is a ‘knowledge gap’ in assessing the impacts of changing carbonate chemistry on the marine environment. Assessing the response of calcifying phytoplankton to this changing carbonate chemistry requires a greater understanding of temporal variation. This study provides a description of the variability of carbonate parameters at a monitoring site in the eastern coast of Scotland. Four-years of monthly data were analysed to assess the diversity, abundance and morphometrics of coccolithophores in relation to carbonate chemistry and environmental variables. The seasonality in carbonate parameters reflected the seasonal cycle in phytoplankton activity, with higher total alkalinity concentrations and pH and lower dissolved inorganic carbon concentrations during the growing season. The dominant coccolithophore at the site was Emiliania huxleyi which showed a clear seasonal pattern, being more abundant in mid-summer when warmer and nutrient-depleted conditions restricted the annual diatom bloom. This study revealed the presence of three morphotypes of E. huxleyi, type A, type A overcalcified (type AO) and type B, which were seasonally distributed throughout the year. The less calcified form was mainly observed in spring while heavily calcified morphotypes overlapped during summer. Autumn and winter months were dominated by the most calcified form (type AO). These results indicate that the seasonal pattern of E. huxleyi morphotypes was not related to the carbonate concentration at the site. This study reflects the strong interannual variability in carbonate chemistry and the complexity associated with coccolithophore calcification, and highlights the need of long-term data to understand the potential impact of ocean acidification on calcifying phytoplankton.

The magnitude of marine plankton net community production (NCP) is indicative of both the biologically driven exchange of carbon dioxide between the atmosphere and the surface ocean and the export of organic carbon from the surface ocean to the ocean interior. In this study the seasonal variability in the NCP of five biogeochemical regions in the North Atlantic was determined from measurements of surface water dissolved oxygen and dissolved inorganic carbon (DIC) sampled from a Volunteer Observing Ship (VOS). The magnitude of NCP derived from dissolved oxygen measurements (NCPinline image) was consistent with previous geochemical estimates of NCP in the North Atlantic, with an average annual NCPinline image of 9.5 ± 6.5 mmol O2 m−2 d−1. Annual NCPinline image did not vary significantly over 35° of latitude and was not significantly different from NCP derived from DIC measurements (NCPDIC). The relatively simple method described here is applicable to any VOS route on which surface water dissolved oxygen concentrations can be accurately measured, thus providing estimates of NCP at higher spatial and temporal resolution than currently achieved.

International audience; A detailed analysis of the internal stoichiometry of a temperate latitude shelf sea system is presented which reveals strong vertical and horizontal gradients in dissolved nutrient and particulate concentrations and in the elemental stoichiometry of those pools. Such gradients have implications for carbon and nutrient export from coastal waters to the open ocean. The mixed layer inorganic nutrient stoichiometry shifted from balanced N:P in winter, to elevated N:P in spring and to depleted N:P in summer, relative to the Redfield ratio. This pattern suggests increased likelihood of P limitation of fast growing phytoplankton species in spring and of N limitation of slower growing species in summer. However, as only silicate concentrations were below potentially limiting concentrations during summer and autumn the stoichiometric shifts in inorganic nutrient N:P are considered due to phytoplankton nutrient preference patterns rather than nutrient exhaustion. Elevated particulate stoichiometries corroborate non-Redfield optima underlying organic matter synthesis and nutrient uptake. Seasonal variation in the stoichiometry of the inorganic and organic nutrient pools has the potential to influence the efficiency of nutrient export. In summer, when organic nutrient concentrations were at their highest and inorganic nutrient concentrations were at their lowest, the organic nutrient pool was comparatively C poor whilst the inorganic nutrient pool was comparatively C rich. The cross-shelf export of these pools at this time would be associated with different efficiencies regardless of the total magnitude of exchange. In autumn the elemental stoichiometries increased with depth in all pools revealing widespread carbon enrichment of shelf bottom waters with P more intensely recycled than N, N more intensely recycled than C, and Si weakly remineralized relative to C. Offshelf carbon fluxes were most efficient via the inorganic nutrient pool, intermediate for the organic nutrient pool and least efficient for the particulate pool. N loss from the shelf however was most efficient via the dissolved organic nutrient pool. Mass balance calculations suggest that 28% of PO43-, 34% of NO3- and 73% of Si drawdown from the mixed layer fails to reappear in the benthic water column thereby indicating the proportion of the nutrient pools that must be resupplied from the ocean each year to maintain shelf wide productivity. Loss to the neighbouring ocean, the sediments, transference to the dissolved organic nutrient pool and higher trophic levels are considered the most likely fate for these missing nutrients.

The North Atlantic is characterized by diatom-dominated spring blooms that results in significant transfer of carbon to higher trophic levels and the deep ocean. These blooms are terminated by limiting silicate concentrations in summer. Numerous regional studies have demonstrated phytoplankton community shifts to lightly-silicified diatoms and non-silicifying plankton at the onset of silicate limitation. However, to understand basin-scale patterns in ecosystem and climate dynamics, nutrient inventories must be examined over sufficient temporal and spatial scales. Here we show, from a new comprehensive compilation of data from the subpolar Atlantic Ocean, clear evidence of a marked pre-bloom silicate decline of 1.5-2 mu M throughout the winter mixed layer during the last 25 years. This silicate decrease is primarily attributed to natural multi-decadal variability through decreased winter convection depths since the mid-1990s, a weakening and retraction of the subpolar gyre and an associated increased influence of nutrient-poor water of subtropical origin. Reduced Arctic silicate import and the projected hemispheric-scale climate change-induced weakening of vertical mixing may have acted to amplify the recent decline. These marked fluctuations in pre-bloom silicate inventories will likely have important consequences for the spatial and temporal extent of diatom blooms, thus impacting ecosystem productivity and ocean-atmosphere climate dynamics., This work was initiated through the Nordic Council of Ministers project (AEG-11323). H.H. is supported by the European Union 7th Framework Programme (n. 308299 NACLIM www.naclim.eu), the EU Horizon 2020 Blue-Action project (BG-10-2016, www.blue-action.eu) and the Danish project NAACOS 10-093903/DSF. R.S. is supported by a Marie Curie Clarin Cofund Grant (ACB-1431). S.P. was funded by the Danish government through the research center 'Climate and oceanographic changes in the marine area between Greenland and Faroes - Influences on plankton and fish'. C.J. was funded under the European Union's Horizon 2020 research and innovation under grant agreement No. 678760 (ATLAS). This output reflects only the author's view and the European Union cannot be held responsible for any use that may be made of the information contained therein. Funding information on the model simulations and the observation programs is given in the Supplementary Information 1. The model simulations were supported by the co-operative project "RACE - Regional Atlantic Circulation and Global Change" funded by the German Federal Ministry for Education and Research (BMBF). We thank Solva Jacobsen for providing the Faroe Shelf silicate record.

A key challenge in oceanography is to capture and quantify processes that happen on short time scales, seasonal changes and inter-annual variations. To address this problem the P&O European Ferries Ltd. Ship MV Pride of Bilbao was fitted with a FerryBox from 2002 to 2010 and data returned to NOC in real time providing near continuous measurements between UK (Portsmouth) and Spain (Bilbao) of temperature, salinity, chlorophyll-fluorescence and oxygen. Additional monthly samples were collected on manned crossings. Over 6000 samples were analysed for nitrate (nitrate and nitrite) concentrations. The timing of nitrate concentration increases (with winter mixing) and decreases (with the spring bloom) are different on and off shelf and in autumn nitrate concentrations remain high on the shelf. Off shelf in the Bay of Biscay, the mixed layer depth assessed using Argo floats, was found to vary from 212 m in relatively mild winters (such as 2007/2008) to 476 m in cold winters (2009/2010). Years with deeper mixing were associated with an increase in nitrate concentrations in the surface waters (~3 µmol l-) and the increased vertical nutrient supply resulted in higher productivity the following spring. Bloom progression could be seen through the increase in oxygen anomaly and decrease in nitrate concentrations off shelf prior to changes further north on the shelf and phytoplankton growth was initiated as shoaling begins. The full dataset demonstrates that ships of opportunity, particularly ferries with consistently repeated routes, can deliver high quality in situ measurements over large time and space scales that currently cannot be delivered in any other way.

During the final year (2010) of the MV Pride of Bilbao (PoB) ferry operation between Portsmouth (UK) and Bilbao (Spain) a comprehensive phytoplankton data set was collected based on pigments and taxonomy measurements. The work was in support of the EU project ProTool (http://www.protool-project.eu) that aimed to develop an automated system for measuring primary productivity from ships of opportunity. Not unexpectedly, the biological patterns relate to the hydrographic conditions and in general, pigment distributions are indicative of the taxonomy. A predominately diatom bloom was observed in the Bay of Biscay in April, with a mixed population of diatoms, dinoflagellates and coccolithophores throughout the spring and summer, and a very distinctive bloom, which contained a large proportion of the dinoflagellate Karenia Mikimotoi, to the stratified side of the Ushant Front in mid-July.

The principle, application, and assessment of the membrane-based ProOceanus CO2-Pro sensor for partial pressure of CO2 (pCO2) are presented. The performance of the sensor is evaluated extensively under field and laboratory conditions by comparing the sensor outputs with direct measurements from calibrated pCO2 measuring systems and the thermodynamic carbonate calculation of pCO2 from discrete samples. Under stable laboratory condition, the sensor agreed with a calibrated water-air equilibrator system at –3.0 ± 4.4 μatm during a 2-month intercomparison experiment. When applied in field deployments, the larger differences between measurements and the calculated pCO2 references (6.4 ± 12.3 μatm on a ship of opportunity and 8.7 ± 14.1 μatm on a mooring) are related not only to sensor error, but also to the uncertainties of the references and the comparison process, as well as changes in the working environments of the sensor. When corrected against references, the overall uncertainties of the sensor results are largely determined by those of the pCO2 references (± 2 and ± 8 μatm for direct measurements and calculated pCO2, respectively). Our study suggests accuracy of the sensor can be affected by temperature fluctuations of the detector optical cell and calibration error. These problems have been addressed in more recent models of the instrument through improving detector temperature control and through using more accurate standard gases. Another interesting result in our laboratory test is the unexpected change in alkalinity which results in significant underestimation in the pCO2 calculation as compared to the direct measurement (up to 90 μatm).

Dissolved oxygen (DO) in the ocean is a tracer for most ocean biogeochemical processes including net community production and remineralization of organic matter which in turn constrains the biological carbon pump. Knowledge of oxygen dynamics in the North Atlantic Ocean is mainly derived from observations at the Bermuda Atlantic Time-series Study (BATS) site located in the western subtropical gyre which may skew our view of the biogeochemistry of the subtropical North Atlantic. This study presents and compares a 15 yr record of DO observations from ESTOC (European Station for Time-Series in the Ocean, Canary Islands) in the eastern subtropical North Atlantic with the 20 yr record at BATS. Our estimate for net community production of oxygen was 2.3±0.4 mol O2 m−2 yr−1 and of oxygen consumption was −2.3±0.5 mol O2 m−2 yr−1 at ESTOC, and 4 mol O2 m−2 yr−1 and −4.4±1 mol m−2 yr−1 at BATS, respectively. These values were determined by analyzing the time-series using the Discrete Wavelet Transform (DWT) method. These flux values agree with similar estimates from in-situ observational studies but are higher than those from modeling studies. The difference in net oxygen production rates supports previous observations of a lower carbon export in the eastern compared to the western subtropical Atlantic. The inter-annual analysis showed clear annual cycles at BATS whereas longer cycles of nearly 4 years were apparent at ESTOC. The DWT analysis showed trends in DO anomalies dominated by long-term perturbations at a basin scale for the consumption zones at both sites, whereas yearly cycles dominated the production zone at BATS. The long-term perturbations found are likely associated with ventilation of the main thermocline, affecting the consumption and production zones at ESTOC.

Best, Mairi M.R. ... et. al.-- 8 pages, 4 figures, The European Multidisciplinary Seafloor and water-column Observatory (EMSO) European Research Infrastructure Consortium (ERIC) provides power, communications, sensors, and data infrastructure for continuous, high-resolution, (near-)real-time, interactive ocean observations across a multidisciplinary and interdisciplinary range of research areas including biology, geology, chemistry, physics, engineering, and computer science, from polar to subtropical environments, through the water column down to the abyss. Eleven deep-sea and four shallow nodes span from the Arctic through the Atlantic and Mediterranean, to the Black Sea. Coordination among the consortium nodes is being strengthened through the EMSOdev project (H2020), which will produce the EMSO Generic Instrument Module (EGIM). Early installations are now being upgraded, for example, at the Ligurian, Ionian, Azores, and Porcupine Abyssal Plain (PAP) nodes. Significant findings have been flowing in over the years; for example, high-frequency surface and subsurface water-column measurements of the PAP node show an increase in seawater pCO2 (from 339 μatm in 2003 to 353 μatm in 2011) with little variability in the mean air-sea CO2 flux. In the Central Eastern Atlantic, the Oceanic Platform of the Canary Islands open-ocean canary node (aka ESTOC station) has a long-standing time series on water column physical, biogeochemical, and acidification processes that have contributed to the assessment efforts of the Intergovernmental Panel on Climate Change (IPCC). EMSO not only brings together countries and disciplines but also allows the pooling of resources and coordination to assemble harmonized data into a comprehensive regional ocean picture, which will then be made available to researchers and stakeholders worldwide on an open and interoperable access basis

We present over 900 carbonate system observations collected over four years (2007–2010) in the Western English Channel (WEC). We determined CO2 partial pressure (pCO2), Total Alkalinity (TA) and Dissolved Inorganic Carbon (DIC) along a series of 40 km transects, including two oceanographic stations (L4 and E1) within a sustained coastal observatory. Our data follow a seasonal pattern of CO2 undersaturation from January to August, followed by supersaturation in September–October and a return to near-equilibrium thereafter. This pattern is explained by the interplay of thermal and biological sinks in winter and spring–summer, respectively, followed by the breakdown of stratification and mixing with deeper, high-CO2 water in autumn. The drawdown of DIC and inorganic N between March and June with a C:N ratio of 8.7–9.5 was consistent with carbon over-consumption during phytoplankton growth. Monthly mean surface pCO2 was strongly correlated with depth integrated chlorophyll a highlighting the importance of subsurface chlorophyll a maxima in controlling C-fluxes in shelf seas. Mixing of seawater with riverine freshwater in near-shore samples caused a reduction in TA and the saturation state of calcite minerals, particularly in winter. Our data show that the L4 and E1 oceanographic stations were small, net sinks for atmospheric CO2 over an annual cycle (−0.52±0.66 mol C m−2 y−1 and −0.62±0.49 mol C m−2 y−1, respectively).

Hartman, S. E., Lampitt, R. S., Larkin, K. E., Pagnani, M., Campbell, J., Gkritzalis, T., Jiang, Z.-P., Pebody, C. A., Ruhl, H. A., Gooday, A. J., Bett, B. J., Billett, D. S. M., Provost, P., McLachlan, R., Turton, J. D., and Lankester, S. 2012. The Porcupine Abyssal Plain fixed-point sustained observatory (PAP-SO): variations and trends from the Northeast Atlantic fixed-point time-series. – ICES Journal of Marine Science, 69: 776–783. The Porcupine Abyssal Plain sustained observatory (PAP-SO) in the Northeast Atlantic (49°N 16.5°W; 4800 m) is the longest running open-ocean multidisciplinary observatory in the oceans around Europe. The site has produced high-resolution datasets integrating environmental and ecologically relevant variables from the surface to the seabed for >20 years. Since 2002, a full-depth mooring has been in place with autonomous sensors measuring temperature, salinity, chlorophyll-a fluorescence, nitrate, and pCO2. These complement ongoing mesopelagic and seabed observations on downward particle flux and benthic ecosystem structure and function. With national and European funding, the observatory infrastructure has been advanced steadily, with the latest development in 2010 involving collaboration between the UK's Meteorological Office and Natural Environment Research Council. This resulted in the first simultaneous atmospheric and ocean datasets at the site. All PAP-SO datasets are open access in near real time through websites and as quality-controlled datasets for a range of remote users using ftp sites and uploaded daily to MyOcean and the global telecommunications system for use in modelling activities. The combined datasets capture short-term variation (daily–seasonal), longer term trends (climate-driven), and episodic events (e.g. spring-bloom events), and the data contribute to the Europe-wide move towards good environmental status of our seas, driven by the EU's Marine Strategy Framework Directive (http://ec.europa.eu/environment/water/marine).

A critical factor controlling changes in the acidity of coastal waters is the alkalinity of the water. Concentrations of alkalinity are determined by supply from rivers and by in situ processes such as biological production and denitrification. A 2-year study based on 15 cruises in Liverpool Bay followed the seasonal cycles of changing concentrations of total alkalinity (TA) and total dissolved inorganic carbon (DIC) in relation to changes caused by the annual cycle of biological production during the mixing of river water into the Bay. Consistent annual cycles in concentrations of nutrients, TA and DIC were observed in both years. At a salinity of 31.5, the locus of primary production during the spring bloom, concentrations of NO x decreased by 25 ± 4 μmol kg−1 and DIC by 106 ± 16 μmol kg−1. Observed changes in TA were consistent with the uptake of protons during primary biological production. Concentrations of TA increased by 33 ± 8 μmol kg−1 (2009) and 33 ± 15 μmol kg−1 (2010). The impact of changes in organic matter on the measured TA appears likely to be small in this area. Thomas et al. (2009) suggested that denitrification may enhance the CO2 uptake of the North Sea by 25%, in contrast we find that although denitrification is a significant process in itself, it does not increase concentrations of TA relative to those of DIC and so does not increase buffer capacity and potential uptake of CO2 into shelf seawaters. For Liverpool Bay historical data suggest that higher concentrations of TA during periods of low flow are likely to contribute in part to the observed change in TA between winter and summer but the appropriate pattern cannot be identified in recent low-frequency river data. On a wider scale, data for the rivers Mersey, Rhine, Elbe and Weser show that patterns of seasonal change in concentrations of TA in river inputs differ between river systems.

This paper presents data for the temporal and spatial distribution of nutrients in Liverpool Bay between 2003 and 2009 and an analysis of inputs of nutrients from the major rivers. The spatial distribution of winter nutrient concentrations are controlled by the region of freshwater influence (ROFI) in Liverpool Bay through the mixing of riverine freshwater and Irish Sea water, with strong linear relationships between nutrient concentration and salinity between December and February. The location of highest spring and summer phytoplankton biomass reflects the nutrient distributions as controlled by the ROFI. Analysis of 7 years of data showed that the seasonal cycle of winter maximum nutrient concentrations in February and drawdown in April/May is a recurrent feature of this location, with the timing of the drawdown varying by several weeks between years. A comparison of observed nutrient concentrations in Liverpool Bay with those predicted from inputs from rivers has been presented. Nutrient concentrations in the rivers flowing into Liverpool Bay were highly variable and there was reasonable agreement between predicted freshwater nutrient concentrations using data from this study and riverine nutrient concentrations weighted on the basis of river flow, although the exact nature of mixing between the rivers could not be determined. Predicted Irish Sea nutrient concentrations in the winter were lower than those reported for the input waters of the North Atlantic, supporting findings from previous work that nitrogen is lost through denitrification in the Irish Sea.

At 3000 m depth the downward flux of particulate matter shows substantial seasonal and interannual variation. Complete annual records for eight of the past 14 years have been examined in the light of mixing depths derived from the OCCAM general circulation model and euphotic zone chlorophyll concentration and productivity, which were derived from the SeaWiFS satellite colour sensor. The annual flux was particularly high in 2001 due to a late summer deposition exceeding previous records several fold and this year was also characterised by very early shoaling of the mixing depth in spring and a very high surface spring chlorophyll concentration. Other years that were somewhat unusual in having either high or low flux at depth were not in general associated with unusual patterns of mixing or productivity. The percentage of the annual organic carbon primary production which reaches 3000 m varies from 0.6 to 1.2% except in 2001 when it reached 3.4%. A mechanistic relationship between upper-ocean processes and deep-ocean particle flux remains elusive and various explanations are suggested for this which need now to be addressed. In the spring, the timing of first shoaling of mixing, enhancement of productivity and increased particle flux at depth have all advanced during the 14 years of study by about 2 days per year, suggesting a similar trend as has been observed for surface phytoplankton, mesozooplankton, fish and seabirds probably caused by wide-scale environmental changes.

We present a 3-year multidisciplinary biogeochemical data set taken in situ at the Porcupine Abyssal Plain (PAP) time-series observatory in the Northeast Atlantic (49°N, 16.5°W; water depth not, vert, similar4850 m) for the period 2003 to 2005. The high-resolution year-round autonomous measurements include temperature, salinity, chlorophyll-a (derived from in situ chlorophyll-fluorescence) and inorganic nitrate, all at a nominal depth of 30 m on an Eulerian observatory mooring. This study compares these in situ time-series data with satellite chlorophyll-a data, regional data from a ship of opportunity, mixed-layer depth measurements from profiling Argo floats and lateral advection estimates from altimetry. This combined and substantial data set is used to analyse seasonal and inter-annual variability in hydrography and nitrate concentrations in relation to convective mixing and lateral advection. The PAP observatory site is in the inter-gyre region of the North Atlantic where convective mixing ranges from 25 m in the summer to over 400 m in winter when nutrients are supplied to the surface. Small inter-annual changes in the winter mixed layer can result in large changes in nitrate supply and productivity. However the decrease in maximum winter nitrate over the three-year period, from 10 to 7 mmol m?3, cannot be fully explained by convective mixing. Trajectories leading to the PAP site, computed from altimetry-derived geostrophic velocities, confirm that lateral advection cannot be ignored at this site and may be an important process along with convective mixing. Over the three years, there is an associated decrease in new production calculated from nitrate assimilation from 85.4 to 40.3±4.3 gCm?2 a?1. This confirms year-to-year variability in primary production seen in model estimates for the region. The continuous in situ dataset also shows inter-annual variation in the timing of the spring bloom due to variations in heat flux; the 2005 bloom occurred earlier than in 2004.

Unusually high chlorophyll values (~ 14 mg chl m-3 at 5 m depth), recorded on a ship of opportunity (SOO) in July 2010, indicated the occurrence of a potential Harmful Algal Bloom (HAB) in the Western approaches of the English Channel. This bloom, located at 49.7°N, 3.2°W was observed via complementary datasets. These included data from samples collected for microscopic phytoplankton identification, information from satellite maps to follow geographical bloom development and in situ data to identify hydrographic factors related to bloom initiation. The relationships between chlorophyll-fluorescence, temperature, salinity and wind speed were examined. The intense summer bloom predominantly consisted of the dinoflagellate Karenia mikimotoi and followed an increase in sea surface temperature (to 18.5 °C). A mid-channel bloom of this magnitude along the SOO route was last seen in 2003. In both years the peak biomass was associated with Karenia mikimotoi blooms, which occurred at the same location and coincided with the least saline, warmest water and lowest wind speeds. This study demonstrates that ships of opportunity are a useful tool to identify and track HAB events through continuous in situ measurements and for the frequent sampling opportunities that they provide.

The variability of total alkalinity (TA) and its relationship with salinity in the tropical and subtropical surface ocean were examined using data collected in various marine environments from a ship of opportunity. In the open ocean regions of the Atlantic, Pacific, and Indian Oceans, sea surface TA variability was observed to be mainly controlled by the simple dilution or concentration (SDC) effect of precipitation and evaporation, and the measured concentrations of TA agreed well with those predicted from salinity and temperature. Non-SDC changes in alkalinity in ocean margins and inland seas were examined by comparing the salinity-normalized alkalinity with that of the open ocean end-member. Non-SDC alkalinity additions to the western North Atlantic margin, eastern North Pacific margin, and Mediterranean Sea were identified, which mainly resulted from river inputs and shelf currents. In contrast, removal of TA through formation and sedimentation of calcium carbonate was observed to be an important control in the Red Sea. The concentration of the river end-member can only be reliably derived from the y intercept of TA-S regression (TA(S0)) in river-dominated systems such as estuaries and river plumes. In coastal regions where other processes (evaporation, shelf currents, upwelling, calcification, etc.) are more influential, TAS0 can significantly deviate from the river water concentration and hence be an unreliable indicator of it. Negative values of TAS0 can result from non-SDC TA removal at the low salinity end (relative to the salinity of the oceanic end-member) and/or non-SDC TA addition at high salinities (as occurs in the Mediterranean Sea).

A 2-year record of mixed layer measurements of CO2 partial pressure (pCO2), nitrate, and other physical, chemical, and biological parameters at a time series site in the northeast Atlantic Ocean (49N/16.5W) is presented. The data show average undersaturation of surface waters with respect to atmospheric CO2 levels by about 40 ± 15 matm, which gives rise to a perennial CO2 sink of 3.2 ± 1.3 mol m2 a1. The seasonal pCO2 cycle is characterized by a summer minimum (winter maximum), which is due to the dominance of biological forcing over physical forcing. Our data document a rapid transition from deep mixing to shallow summer stratification. At the onset of shallow stratification, up to one third of the mixed layer net community production during the productive season had already been accomplished. The combination of high prestratification productivity and rapid onset of tratification appears to have caused the observed particle flux peak early in the season. Mixed layer deepening during fall and winter reventilated CO2 from subsurface respiration of newly exported organic matter, thereby negating more than one third of the carbon drawdown by net community production in the mixed layer. Chemical signatures of both net community production and respiration are indicative of carbon overconsumption, the effects of which may be restricted, though, to the upper ocean. A comparison of the estimated net community production with satellite-based estimates of net primary production shows fundamental discrepancies in the timing of ocean productivity.

In 2002 a robust minimum maintenance system to measure temperature, conductivity, and chlorophyll fluorescence was installed on a ferry running twice weekly between Portsmouth, UK and Bilbao, Spain. Logged data are transferred from the engine room to an Orbcom satellite communicator on the bridge. On shore data enters an SQL database with access from a public web page. Data from the Iberian margin is linked to monthly surveys by IEO. Target work includes:the structure, transport of and seasonal devel- opment of water masses, and scaling of patchiness of plankton blooms in regions with different hydrographic characteristics.

Two autonomous systems were used to record plankton blooms with reduced aliasing of timing and peak biomass in two different hypernutrified systems—a “FerryBox” and a “SmartBuoy”. Temperature, salinity, fluorescence, turbidity and position were measured on the ferry, plus nutrients on the SmartBuoys. A significant spring bloom occurred at both sites in 2001. This is a typical pattern of bloom development for the two sites and can be related to environmental conditions (nutrients, light and net heat flux). Chloro- phyll levels, however, remained low at both sites in 2002. This atypical year challenges our understanding of these systems as tidal and weather conditions were similar to 2001. The low values may be due to a combination of storm events at the end of 2001 and low winter nutrient values in 2002.

Pyrene substituents covalently bounded to polyelectrolytes show not only excited-state interactions but also unique ground-state interactions in aqueous solution. The pyrene moieties in pyrenesubstituted ionic molecules also show these interactions when aqueous solutions of these molecules are treated with polyelectrolytes or surfactants well below their critical micelle concentrations. These hydrophobic interactions are revealed by changes in absorption, fluorescence, and excitation spectra. The well-resolved vibrational bands in the absorption and excitation spectra of pyrene become somewhat diffuse, whereas monomer fluorescence is reduced and replaced by excimer fluorescence. The rationale for these results is that the pyrene moieties in these ionic solutions seek out hydrophobic locations on the polyelectrolytes or surfactants, where pyrene aggregation is responsible for these interactions and the corresponding changes in spectra.

The microenvironment of charged molecules can be significantly altered in the presence of ionic molecules such as surfactants, lipids, and polyelectrolytes. Such a change in the microenvironment of aromatic hydrocarbon chromophores can be conveniently studied spectroscopically.