Parameterization of air–sea gas fluxes at extreme wind speeds

Air–sea flux measurements of O₂ and N₂ obtained during Hurricane Frances in September 2004 [D'Asaro, E. A. and McNeil, C. L., 2006. Measurements of air–sea gas exchange at extreme wind speeds. Journal Marine Systems, this edition.] using air-deployed neutrally buoyant floats reveal the first evidence of a new regime of air–sea gas transfer occurring at wind speeds in excess of 35 m s^− 1. In this regime, plumes of bubbles 1 mm and smaller in size are transported down from near the surface of the ocean to greater depths by vertical turbulent currents with speeds up to 20−30 cm s^− 1. These bubble plumes mostly dissolve before reaching a depth of approximately 20 m as a result of hydrostatic compression. Injection of air into the ocean by this mechanism results in the invasion of gases in proportion to their tropospheric molar gas ratios, and further supersaturation of less soluble gases. A new formulation for air–sea fluxes of weakly soluble gases as a function of wind speed is proposed to extend existing formulations [Woolf, D.K, 1997. Bubbles and their role in gas exchange. In: Liss, P.S., and Duce, R.A., (Eds.), The Sea Surface and Global Change. Cambridge University Press, Cambridge, UK, pp. 173–205.] to span the entire natural range of wind speeds over the open ocean, which includes hurricanes. The new formulation has separate contributions to air–sea gas flux from: 1) non-supersaturating near-surface equilibration processes, which include direct transfer associated with the air–sea interface and ventilation associated with surface wave breaking; 2) partial dissolution of bubbles smaller than 1 mm that mix into the ocean via turbulence; and 3) complete dissolution of bubbles of up to 1 mm in size via subduction of bubble plumes. The model can be simplified by combining “surface equilibration” terms that allow exchange of gases into and out of the ocean, and “gas injection” terms that only allow gas to enter the ocean. The model was tested against the Hurricane Frances data set. Although all the model parameters cannot be determined uniquely, some features are clear. The fluxes due to the surface equilibration terms, estimated both from data and from model inversions, increase rapidly at high wind speed but are still far below those predicted using the cubic parameterization of Wanninkhof and McGillis [Wannikhof, R. and McGillis, W.R., 1999. A cubic relationship between air–sea CO₂ exchange and wind speed. Geophysical Research Letters, 26:1889–1892.] at high wind speed. The fluxes due to gas injection terms increase with wind speed even more rapidly, causing bubble injection to dominate at the highest wind speeds.     

The combined effect of rain and wind on air–water gas exchange: A feasibility study

A series of experiments were conducted at University of Delaware's Air–Sea Interaction Laboratory to examine the combined effects of rain and wind on air–water gas exchange. During this study, ASIL WRX I, a combination of 3 rain rates and 4 wind speeds were used, for a total of 12 different environmental conditions. The SF₆ evasion method was used to determine the bulk gas transfer velocities, and airside profiles of wind and CO₂ were used to estimate flux–profiles of momentum and carbon dioxide. In addition to measurements of fluxes with and without rain in a wind–wave boundary layer, measurements of wave properties were also obtained. Rain is shown to alter the wind profile in the flume, and dampen surface waves. Also, SF₆ evasion indicates that with the present experimental setup, for most of the experimental conditions, rain and wind combine linearly to influence air–water gas exchange. Flux–profile relationships for marine atmospheric boundary layers, which were performed to scale up to field measurements, were explored by a comparison between SF₆-derived bulk fluxes and airside CO₂ profile measurements.     

An approach to estimation of near-surface turbulence and CO2 transfer velocity from remote sensing data

The air–sea CO₂ exchange is primarily determined by the boundary-layer processes in the near-surface layer of the ocean since it is a water-side limited gas. As a consequence, the interfacial component of the CO₂ transfer velocity can be linked to parameters of turbulence in the near-surface layer of the ocean. The development of remote sensing techniques provides a possibility to quantify the dissipation of the turbulent kinetic energy in the near-surface layer of the ocean and the air–sea CO₂ transfer velocity on a global scale. In this work, the dissipation rate of the turbulent kinetic energy in the near-surface layer of the ocean and its patchiness has been linked to the air–sea CO₂ transfer velocity with a boundary-layer type model. Field observations of upper ocean turbulence, laboratory studies, and the direct CO₂ flux measurements are used to validate the model. The model is then forced with the TOPEX POSEIDON wind speed and significant wave height to demonstrate its applicability for estimating the distribution of the near-surface turbulence dissipation rate and gas transfer velocity for an extended (decadal) time period. A future version of this remote sensing algorithm will incorporate directional wind/wave data being available from QUIKSCAT, a now-cast wave model, and satellite heat fluxes. The inclusion of microwave imagery from the Special Sensor Microwave Imager (SSM/I) and the Synthetic Aperture Radar (SAR) will provide additional information on the fractional whitecap coverage and sea surface turbulence patchiness.     

Seasonal and interannual variation of physical and biological processes during 1994–2001 in the Sea of Japan/East Sea: A three-dimensional physical–biogeochemical modeling study

A Pacific basin-wide physical–biogeochemical model has been used to investigate the seasonal and interannual variation of physical and biological fields with analyses focusing on the Sea of Japan/East Sea (JES). The physical model is based on the Regional Ocean Model System (ROMS), and the biogeochemical model is based on the Carbon, Si(OH)₄, Nitrogen Ecosystem (CoSiNE) model. The coupled ROMS–CoSiNE model is forced with the daily air–sea fluxes derived from the National Centers for Environmental Prediction (NCEP) and the National Center for Atmospheric Research (NCAR) reanalysis for the period of 1994 to 2001, and the model results are used to evaluate climate impact on nutrient transport in Mixed Layer Depth (MLD) and phytoplankton spring bloom dynamics in the JES.The model reproduces several key features of sea surface temperature (SST) and surface currents, which are consistent with the previous modeling and observational results in the JES. The calculated volume transports through the three major straits show that the Korea Strait (KS) dominates the inflow to the JES with 2.46 Sv annually, and the Tsugaru Strait (TS) and the Soya Strait (SS) are major outflows with 1.85 Sv and 0.64 Sv, respectively. Domain-averaged phytoplankton biomass in the JES reaches its spring peak 1.8 mmol N m^− 3 in May and shows a relatively weak autumn increase in November. Strong summer stratification and intense consumption of nitrate by phytoplankton during the spring result in very low nitrate concentration at the upper layer, which limits phytoplankton growth in the JES during the summer. On the other hand, the higher grazer abundance likely contributes to the strong suppression of phytoplankton biomass after the spring bloom in the JES. The model results show strong interannual variability of SST, nutrients, and phytoplankton biomass with sudden changes in 1998, which correspond to large-scale changes of the Pacific Decadal Oscillation (PDO). Regional comparisons of interannual variations in springtime were made for the southern and northern JES. Variations of nutrients and phytoplankton biomass related to the PDO warm/cold phase changes were detected in both the southern and northern JES, and there were regional differences with respect to the mechanisms and timing. During the warm PDO, the nutrients integrated in the MLD increased in the south and decreased in the north in winter. Conversely, during the cold PDO, the nutrients integrated in the MLD decreased in the south and increased in the north. Wind divergence/convergence likely drives the differences in the southern and northern regions when northerly and northwesterly monsoon dominates in winter in the JES. Subjected to the nutrient change, the growth of phytoplankton biomass appears to be limited neither by nutrient nor by light consistently both in the southern and northern regions. Namely, the JES is at the transition zone of the lower trophic-level ecosystem between light-limited and nutrient-limited zones.     

Carbonate chemistry dynamics and carbon dioxide fluxes across the atmosphere–ice–water interfaces in the Arctic Ocean: Pacific sector of the Arctic

Climatic changes in the Northern Hemisphere have led to remarkable environmental changes in the Arctic Ocean, which is surrounded by permafrost. These changes include significant shrinking of sea-ice cover in summer, increased time between sea-ice break-up and freeze-up, and Arctic surface water freshening and warming associated with melting sea-ice, thawing permafrost, and increased runoff. These changes are commonly attributed to the greenhouse effect resulting from increased atmospheric carbon dioxide (CO₂) concentration and other non-CO₂ radiatively active gases (methane, nitrous oxide). The greenhouse effect should be most pronounced in the Arctic where the largest air CO₂ concentrations and winter–summer variations in the world for a clean background environment were detected. However, the air–land–shelf interaction in the Arctic has a substantial impact on the composition of the overlying atmosphere; as the permafrost thaws, a significant amount of old terrestrial carbon becomes available for biogeochemical cycling and oxidation to CO₂. The Arctic Ocean's role in determining regional CO₂ balance has been ignored, because of its small size (only  4% of the world ocean area) and because its continuous sea-ice cover is considered to impede gaseous exchange with the atmosphere so efficiently that no global climate models include CO₂ exchange over sea-ice. In this paper we show that: (1) the Arctic shelf seas (the Laptev and East-Siberian seas) may become a strong source of atmospheric CO₂ because of oxidation of bio-available eroded terrestrial carbon and river transport; (2) the Chukchi Sea shelf exhibits the strong uptake of atmospheric CO₂; (3) the sea-ice melt ponds and open brine channels form an important spring/summer air CO₂ sink that also must be included in any Arctic regional CO₂ budget. Both the direction and amount of CO₂ transfer between air and sea during open water season may be different from transfer during freezing and thawing, or during winter when CO₂ accumulates beneath Arctic sea-ice; (4) direct measurements beneath the sea ice gave two initial results. First, a drastic pCO₂ decrease from 410 μatm to 288 μatm, which was recorded in February–March beneath the fast ice near Barrow using the SAMI-CO₂ sensor, may reflect increased photosynthetic activity beneath sea-ice just after polar sunrise. Second, new measurements made in summer 2005 beneath the sea ice in the Central Basin show relatively high values of pCO₂ ranging between 425 μatm and 475 μatm, values, which are larger than the mean atmospheric value in the Arctic in summertime. The sources of those high values are supposed to be: high rates of bacterial respiration, import of the Upper Halocline Water (UHW) from the Chukchi Sea (CS) where values of pCO₂ range between 400 and 600 μatm, a contribution from the Lena river plume, or any combination of these sources.     

Application of new parameterizations of gas transfer velocity and their impact on regional and global marine CO2 budgets

One of the dominant sources of uncertainty in the calculation of air–sea flux of carbon dioxide on a global scale originates from the various parameterizations of the gas transfer velocity, k, that are in use. Whilst it is undisputed that most of these parameterizations have shortcomings and neglect processes which influence air–sea gas exchange and do not scale with wind speed alone, there is no general agreement about their relative accuracy.The most widely used parameterizations are based on non-linear functions of wind speed and, to a lesser extent, on sea surface temperature and salinity. Processes such as surface film damping and whitecapping are known to have an effect on air–sea exchange. More recently published parameterizations use friction velocity, sea surface roughness, and significant wave height. These new parameters can account to some extent for processes such as film damping and whitecapping and could potentially explain the spread of wind-speed based transfer velocities published in the literature.We combine some of the principles of two recently published k parameterizations [Glover, D.M., Frew, N.M., McCue, S.J. and Bock, E.J., 2002. A multiyear time series of global gas transfer velocity from the TOPEX dual frequency, normalized radar backscatter algorithm. In: Donelan, M.A., Drennan, W.M., Saltzman, E.S., and Wanninkhof, R. (Eds.), Gas Transfer at Water Surfaces, Geophys. Monograph 127. AGU,Washington, DC, 325–331; Woolf, D.K., 2005. Parameterization of gas transfer velocities and sea-state dependent wave breaking. Tellus, 57B: 87–94] to calculate k as the sum of a linear function of total mean square slope of the sea surface and a wave breaking parameter. This separates contributions from direct and bubble-mediated gas transfer as suggested by Woolf [Woolf, D.K., 2005. Parameterization of gas transfer velocities and sea-state dependent wave breaking. Tellus, 57B: 87–94] and allows us to quantify contributions from these two processes independently.We then apply our parameterization to a monthly TOPEX altimeter gridded 1.5° × 1.5° data set and compare our results to transfer velocities calculated using the popular wind-based k parameterizations by Wanninkhof [Wanninkhof, R., 1992. Relationship between wind speed and gas exchange over the ocean. J. Geophys. Res., 97: 7373–7382.] and Wanninkhof and McGillis [Wanninkhof, R. and McGillis, W., 1999. A cubic relationship between air−sea CO2 exchange and wind speed. Geophys. Res. Lett., 26(13): 1889–1892]. We show that despite good agreement of the globally averaged transfer velocities, global and regional fluxes differ by up to 100%. These discrepancies are a result of different spatio-temporal distributions of the processes involved in the parameterizations of k, indicating the importance of wave field parameters and a need for further validation.     

Surface CO2 measurements in the English Channel and Southern Bight of North Sea using voluntary observing ships

Ships of opportunity have been used to investigate ocean–atmosphere CO₂ fluxes in the English Channel and Southern Bight of the North Sea. Continuous underway measurements of the fugacity of seawater carbon dioxide (fCO₂^sw), chlorophyll, temperature and salinity have been performed along 26 transects during the spring and autumn periods. The spatial fCO₂^sw distribution along the Channel and Southern Bight is modulated by the photosynthetic activity, temperature changes and water mixing between inputs from the North Atlantic Ocean and riverine discharges. The seasonal variability of fCO₂^sw is assessed and discussed in terms of the biology and temperature effects, these having similar impacts. The variation of fCO₂^sw shows similar interannual patterns, with lower values in spring. The annual average of air–sea CO₂ fluxes places the English Channel as neutral area of CO₂ uptake. The spring and autumn data allow differentiating between distal and proximal continental areas. The Southern Bight shows a tendency towards net CO₂ uptake on the distal continental shelf, whereas the Scheldt and Thames Plumes show a CO₂ source behaviour on the proximal continental shelves.     

Annual uptake of atmospheric CO2 by the Weddell Sea derived from a surface layer balance, including estimations of entrainment and new production

Data from two cruises, one in April/May 1996 and one in December/January 1993, covering the same wide area in the offshore Weddell Sea, were used to derive the annual extent of entrainment and the capacity of the biological pump. The former property was obtained with the help of dissolved oxygen data, whereas the latter was approximated with nutrients. Especially the data from April/May, representing the initial state of the winter surface layer, were crucial to assess the annual extent of these processes. The results were applied to our carbon dioxide data. The annual increase of the Total CO₂ (TCO₂) concentration in the surface layer due to vertical transport amounts to 16.3 μmol kg⁻¹. An entrainment rate of deep water in the surface layer amounting to 35±10 m yr⁻¹ was deduced. The compensating, biologically mediated TCO₂ reduction was calculated to be larger than the TCO₂ increase due to vertical transport. Since the balance of these two processes determines whether the Weddell Sea is a source or a sink of CO₂, this indicates that the Weddell Sea, albeit upwelling area, is definitely a sink for atmospheric CO₂ on an annual basis. This conclusion is further supported by contemplations that the biological drawdown of CO₂ in the Weddell Sea as a whole is probably underestimated by our calculations. The new production for the Weddell Sea on a per unit area basis was found to be much higher than that for the Antarctic Ocean, when the latter value is being obtained by traditional biological methods. On the other hand, the CO₂ uptake by the Weddell Sea on a per unit area basis is somewhat smaller than the CO₂ uptake by the world ocean.     

On the relation between organic and inorganic carbon in the Weddell Sea

Carbon cycling in the Weddell Sea was investigated during the ANT X/7 cruise with `FS Polarstern' December 1992–January 1993. Samples were taken on a cross section from Kapp Norvegia to Joinville Island, and on a section from the Larsen Ice Shelf to the northeast. The following quantities were measured: total carbon dioxide (TCO₂), fluorescence from humic substances and total organic carbon. The distribution of TCO₂ was strongly positively correlated to the time elapsed since the various water masses were last ventilated. In general, humic substance fluorescence was positively correlated with TCO₂, with the exception of the productive part of the western Weddell Sea, where the correlation was negative in the surface mixed layer. The increased fluorescence at the surface is suggested to be a result of biological production. The distribution of total organic carbon showed less structure, since this quantity includes a particulate component, which is subject to dispersion processes different from those of the dissolved components TCO₂ and humic substances. The mean total organic carbon concentration below the surface mixed layer was 50 μmol l⁻¹. At some stations, a steep TOC maximum around 2000 m depth was observed. This was interpreted to result from mass sinking of phytoplankton blooms. Total organic carbon had a maximum in surface water, and at some stations also a second subsurface maximum. In the Warm Deep Water (WDW), TCO₂ and fluorescence had their maximum values, while total organic carbon tended to be low. In low productivity surface water in the eastern part of the Kapp Norvegia–Joinville Island section, the lowest flourescence was found. Surface water is eventually formed from Warm Deep Water, which had the highest fluorescence values, and therefore it is concluded that humic substances were removed in situ from surface water. In the central area of the Weddell Sea, TCO₂ and fluorescence showed the highest Warm Deep Water maxima, while total organic carbon was low. The Warm Deep Water in this area is part of the so-called Central Intermediate Water which circulates for a long time within the Weddell Gyre. Reduced total organic carbon, which coincides with the most pronounced Central Intermediate Water characteristics, and high TCO₂ can thus both be accounted for by continued degradation of organic matter in this water mass. The associated fluorescence maximum implies that humic substances are also produced during mineralisation. Recently formed bottom water, by contrast, could be seen as patches of low TCO₂, low fluorescence and high total organic carbon along the western slope of the Weddell Sea.     

Effect of wave boundary layer on sea-to-air dimethylsulfide transfer velocity during typhoon passage

A full-spectral third-generation ocean wind–wave model (Wavewatch-III) implemented in the South China Sea is used to investigate the effects of the wave boundary layer on the drag coefficient and the sea-to-air transfer velocity of dimethylsulfide (DMS) during passage of Typhoon Wukong (September 5–11, 2000) with a maximum sustained wind speed of 38 m s^− 1. The model is driven by the reanalyzed surface winds (1° × 1°, four times daily) from the National Centers for Environmental Prediction. It is found that the wave boundary layer evidently enhances (16.5%) the drag coefficient (in turn increases the momentum flux across the air–sea interface), and reduces (13.1%) the sea-to-air DMS transfer velocity (in turn decreases the sea-to-air DMS flux). This indicates the possibility of important roles of wave boundary layer in atmospheric DMS contents and global climate system.     

Study of the seasonal cycle of the biogeochemical processes in the Ligurian Sea using a 1D interdisciplinary model

A one-dimensional coupled physical–biogeochemical model has been built to study the pelagic food web of the Ligurian Sea (NW Mediterranean Sea). The physical model is the turbulent closure model (version 1D) developed at the GeoHydrodynamics and Environmental Laboratory (GHER) of the University of Liège. The ecosystem model contains 19 state variables describing the carbon and nitrogen cycles of the pelagic food web. Phytoplankton and zooplankton are both divided in three size-based compartments and the model includes an explicit representation of the microbial loop including bacteria, dissolved organic matter, nano-, and microzooplankton. The internal carbon/nitrogen ratio is assumed variable for phytoplankton and detritus, and constant for zooplankton and bacteria. Silicate is considered as a potential limiting nutrient of phytoplankton's growth. The aggregation model described by Kriest and Evans in (Proc. Ind. Acad. Sci., Earth Planet. Sci. 109 (4) (2000) 453) is used to evaluate the sinking rate of particulate detritus. The model is forced at the air–sea interface by meteorological data coming from the “Côte d'Azur” Meteorological Buoy. The dynamics of atmospheric fluxes in the Mediterranean Sea (DYFAMED) time-series data obtained during the year 2000 are used to calibrate and validate the biological model. The comparison of model results within in situ DYFAMED data shows that although some processes are not represented by the model, such as horizontal and vertical advections, model results are overall in agreement with observations and differences observed can be explained with environmental conditions.     

Biogenic silica cycle in surface sediments of the Greenland Sea

In contrast to several investigations of biogenic silica (BSi) content and recycling in surface sediments of the Southern Ocean, little is known about the benthic cycle of BSi in high northern latitudes. Therefore, we investigated the silicic acid concentration of pore water and BSi content of surface sediments from the Greenland Sea. Low BSi contents of less than 2% were observed. High-resolution (2–5 mm) BSi profiles and comparisons to trap studies suggest that only relatively dissolution-resistant siliceous components reach the seafloor. Pore water investigations reveal BSi fluxes of more than 300 mmol m⁻² a⁻¹ only for a few sites on the shelf. A statistically significant relationship between water depth and BSi rain rate reaching the seafloor was not observed. Sampling along a transect perpendicular to the marginal ice zone (MIZ) revealed no enhanced rain rate of BSi reaching the seafloor in the vicinity of the ice edge. Although the MIZ of the Greenland Sea is characterized by the enhanced export of biogenic particles from surface waters, this feature is not reflected in the benthic cycle of biogenic silica. The lack of such a relationship, which is in contrast to observations of shelf and continental margin sediments in the southern South Atlantic, is probably caused by the enhanced dissolution of BSi in the water column and highly dynamic ice conditions in the Greenland Sea.     

Bacterial production and microbial food web structure in a large arctic river and the coastal Arctic Ocean

Globally significant quantities of organic carbon are stored in northern permafrost soils, but little is known about how this carbon is processed by microbial communities once it enters rivers and is transported to the coastal Arctic Ocean. As part of the Arctic River-Delta Experiment (ARDEX), we measured environmental and microbiological variables along a 300 km transect in the Mackenzie River and coastal Beaufort Sea, in July–August 2004. Surface bacterial concentrations averaged 6.7 × 10⁵ cells mL^− 1 with no significant differences between sampling zones. Picocyanobacteria were abundant in the river, and mostly observed as cell colonies. Their concentrations in the surface waters decreased across the salinity gradient, dropping from 51,000 (river) to 30 (sea) cells mL^− 1. There were accompanying shifts in protist community structure, from diatoms, cryptophytes, heterotrophic protists and chrysophytes in the river, to dinoflagellates, prymnesiophytes, chrysophytes, prasinophytes, diatoms and heterotrophic protists in the Beaufort Sea.Size-fractionated bacterial production, as measured by ³H–leucine uptake, varied from 76 to 416 ng C L^− 1 h^− 1. The contribution of particle-attached bacteria (> 3 µm fraction) to total bacterial production decreased from > 90% at the Mackenzie River stations to < 20% at an offshore marine site, and the relative importance of this particle-based fraction was inversely correlated with salinity and positively correlated with particulate organic carbon concentrations. Glucose enrichment experiments indicated that bacterial metabolism was carbon limited in the Mackenzie River but not in the coastal ocean. Prior exposure of water samples to full sunlight increased the biolability of dissolved organic carbon (DOC) in the Mackenzie River but decreased it in the Beaufort Sea.Estimated depth-integrated bacterial respiration rates in the Mackenzie River were higher than depth-integrated primary production rates, while at the marine stations bacterial respiration rates were near or below the integrated primary production rates. Consistent with these results, P_CO2 measurements showed surface water supersaturation in the river (mean of 146% of air equilibrium values) and subsaturation or near-saturation in the coastal sea. These results show a well-developed microbial food web in the Mackenzie River system that will likely convert tundra carbon to atmospheric CO₂ at increasing rates as the arctic climate continues to warm.     

Determination of anthropogenic CO2 in the North Atlantic Ocean using water mass ages and CO2 equilibrium chemistry

A new method to calculate the anthropogenic CO₂ (ΔDIC_ant) within the water column of the North Atlantic Ocean is presented. The method exploits the equilibrium chemistry of the carbonate system with reference to temperature, salinity and the partial pressure of atmospheric CO₂ (pCO_2,atm). ΔDIC_ant is calculated with reference to the ventilation ages of water masses derived from tracer data and to the time history of pCO_2,atm. The method is applied to data recorded during the WOCE program on the WHP A1/E transect in the North Atlantic Ocean, where we characterise six key water masses by their relationships of dissolved inorganic carbon (DIC) and apparent oxygen utilisation (AOU). The error in determining ΔDIC_ant is reduced significantly by minimising the number of values referred to, especially by avoiding any use of remineralisation ratios of particulate organic matter. The distribution of ΔDIC_ant shows highest values of up to 45 μmol kg⁻¹ in the surface waters falling to 28–33 μmol kg⁻¹ in the Irminger Sea west of the Mid-Atlantic Ridge. The eastern basin is imprinted by older water masses revealing decreasing values down to 10 μmol kg⁻¹ ΔDIC_ant in the Antarctic Bottom Water. These findings indicate the penetration of the whole water column of the North Atlantic Ocean by anthropogenic CO₂.     

Fluxes of dissolved inorganic carbon in three estuarine systems of the Cantabrian Sea (north of Spain)

The diffusive and in situ fluxes of dissolved inorganic carbon (DIC) and total alkalinity (TA) have been measured and an estimation has been made of the water–atmosphere fluxes of CO₂ in three estuarine systems of the Cantabrian Sea during the spring of 1998. Each of these systems undergoes a different anthropogenic influence. The diffusive fluxes of dissolved inorganic carbon and total alkalinity obtained present values ranging between 0.54–2.65 and 0.0–2.4 mmol m⁻² day⁻¹, respectively. These ranges are in agreement with those of other coastal systems. The in situ fluxes are high and extremely variable (35–284 mmol TA m⁻² day⁻¹, 43–554 mmol DIC m⁻² day⁻¹ and 22–261 mmol dissolved oxygen (DO) m⁻² day⁻¹), because the systems studied are very heterogeneous. The values of the ratio of the in situ fluxes of TA and DIC show on average that the rate of dissolution of CaCO₃ is 0.37 times that of organic carbon oxidation. Equally, the interval of variation of the relationship between the benthic fluxes of inorganic carbon and oxygen (F_DIC/F_DO) is very wide (0.3–13.9), which demonstrates the different contributions made by the processes of aerobic and anaerobic degradation of the organic matter, as well as by the dissolution–precipitation of CaCO₃. The water–atmosphere fluxes of CO₂ present a clear dependence on the salinity. The brackish water of these systems (salinity<20), where maximum fluxes of 989 mmol m⁻² day⁻¹ have been estimated, act as a source of CO₂ to the atmosphere. The more saline zones of the estuary (salinity>30) act as a sink of CO₂, with fluxes between −5 and −10 mmol m⁻² day⁻¹.     

Identification and quantification of plankton bloom events in the Baltic Sea by continuous pCO2 and chlorophyll a measurements on a cargo ship

Continuous measurements of the surface water CO₂ partial pressure (pCO₂) and the chlorophyll a fluorescence were performed in the Baltic Sea using a fully automated measurement system deployed on a cargo ship. The ship commuted regularly at two day intervals between the Mecklenburg Bight (Luebeck) and the Gulf of Finland (Helsinki). The pCO₂ data collected during June 2003 and September 2004 were used to identify biological production events such as the spring bloom and the midsummer cyanobacteria bloom in five different sub-regions. To quantify the net biomass production, the decrease of the total CO₂, ^NC_T (normalized to a uniform alkalinity), during the production periods was calculated using the pCO₂, temperature and salinity records and the mean alkalinity. Taking into account the CO₂ air/sea exchange and the formation of dissolved organic carbon, a simple mass balance yielded the net production of particulate organic carbon which represents the total biomass. The chlorophyll a concentrations obtained from the fluorescence data showed peaks that in most cases coincided with the production maxima and thus supported the interpretation of the pCO₂ data. The production during both the spring bloom (2004) and the midsummer nitrogen fixation period (2003) increased by a factor of about three from the southwest to the northeast. For the spring bloom our estimates were significantly higher than those based on the winter nutrient supply and Redfield C / N and C / P ratios. This indicated the existence of additional nutrient sources such as dissolved organic nitrogen, early nitrogen fixation and preferential P mineralization. Midsummer ^NC_T minima were observed only in 2003 and used to quantify the nitrogen fixation activity and to characterize its interannual variability.     

Seasonal variability in sea surface oceanographic conditions in the Aegean Sea (Eastern Mediterranean): an overview

Seasonal variability and the spatial distribution of sea surface temperatures (SST) and salinities (SSS) are reviewed, in relation to the prevailing climatological conditions, heat fluxes, water budget and general water circulation patterns. Within this context, consideration is given to: sea surface temperatures; air temperatures; precipitation; evaporation; wind speeds and directions; freshwater (mainly riverine) discharges throughout the Aegean; and the exchange of water masses with the Black Sea and eastern Mediterranean Sea. The investigation of satellite images, covering a 6-yr period (1988–1994), has enabled a synthesis of the monthly sea surface thermal distribution to be established.The climate of the Aegean Sea is characterised by annual air temperatures of 16–19.5°C, precipitation of about 500 mm yr⁻¹ and evaporation of some 4 mm d⁻¹. The Aegean has a negative heat budget (approximately −25 W m⁻²) and positive water balance (+ 1.0 m yr⁻¹), when inflow from the Black Sea is considered. During the summer, the (northerly) Etesians are the dominant winds over the Sea.Mean monthly sea surface temperatures (SST) vary from 8°C in the north during winter, up to 26°C in the south during summer. SST depends mainly upon air temperature; there is a month's delay between the former and latter maxima. The sea surface salinity (SSS) varies also spatially and seasonally, ranging from less than 31 psu, in the north, to more than 39 psu, in the southeast; lower values (< 25 psu) occur adjacent to the river mouths. SSSs present their maximum differences during summer, whilst during winter and autumn the distribution of SSS is more uniform. The overall spatial SST and SSS distribution pattern is controlled by: distribution of the (colder) Black Sea Waters; advection of the (warmer) Levantine Waters, from the southeastern part of the Aegean; upwelling and downwelling; and, to a lesser extent, but locally important, freshwater riverine inflows.     

Modelling the silica pump in the Permanently Open Ocean Zone of the Southern Ocean

A coupled 1D physical–biogeochemical model has been built to simulate the cycles of silicon and of nitrogen in the Indian sector of the Permanently Open Ocean Zone of the Southern Ocean. Based on a simplified trophic network, that includes two size classes of phytoplankton and of zooplankton, and a microbial loop, it has been calibrated by reference to surface physical, chemical and biological data sets collected at the KERFIX time-series station (50°40′S–68°25′E). The model correctly reproduces the high nutrient low chlorophyll features typical of the studied area. In a region where the spring–summer mixed layer depth is usually deeper than 60 m, the maximum of chlorophyll never exceeds 1.5 mg m⁻³, and the annual primary production is only 68 g C m⁻² year⁻¹. In the surface layer nitrate is never exhausted (range 27–23.5 mmoles m⁻³) while silicic acid shows strong seasonal variations (range 5–20 mmoles m⁻³). On an annual basis 71% of the primary production sustained by nanophytoplankton is grazed by microzooplankton. Compared to North Atlantic, siliceous microphytoplankton is mainly prevented from blooming because of an unfavourable spring–summer light-mixing regime. Silicic acid limitation (high half saturation constant for Si uptake: 8 mmoles m⁻³) also plays a major role on diatom growth. Mesozooplankton grazing pressure excerpts its influence especially in late spring. The model illustrates the efficiency of the silica pump in the Southern Ocean: up to 63% of the biogenic silica that has been synthetized in the photic layer is exported towards the deep ocean, while only 11% of the particulate organic nitrogen escapes recycling in the surface layer.     

Lengthscales of motions that control air–water gas transfer in grid-stirred turbulence

The relationship between the gas transfer velocity and turbulent lengthscales is investigated experimentally in a grid-stirred turbulent flow. The horizontal velocity field at the water surface is measured using particle image velocimetry (PIV). The gas transfer velocity for oxygen is obtained through reaeration experiments. In addition, the gas transfer process by surface-renewal eddies is visualized using laser-induced fluorescence (LIF) technique, in which carbon dioxide is used as the tracer gas. The definition of the Taylor microscale holds that the root-mean-square (RMS) of the surface divergence is expressed by the square root of the turbulent kinetic energy divided by the Taylor microscale. Experimentally obtained data support this scaling. They show the gas transfer velocity to be proportional to the square root of the RMS of the surface divergence. These experimental results imply that the Taylor microscale is an important parameter for gas transfer velocity at the air–water interface. These relations indicate that a nondimensional gas transfer velocity is proportional to the − 1/4 power of a turbulent-macroscale Reynolds number, which is similar to a small-eddy model, assuming that turbulent eddies with the Kolmogorov scale control the gas transfer process. However, this Reynolds number dependence does not necessarily mean the superiority of turbulent eddies with the Kolmogorov scale in the gas transfer. The LIF visualizations in horizontal and vertical planes close to the air–water interface indicate that the horizontal CO₂-concentration field has a fine spatial pattern, which resembles that of the surface divergence field, and that surface-renewal motions observed in the vertical plane have a larger lengthscale than the Kolmogorov scale. We infer from both PIV and LIF results that the Taylor microscale is an important lengthscale for air–water gas transfer.     

Large-scale physical controls on phytoplankton growth in the Irminger Sea, Part II: Model study of the physical and meteorological preconditioning

The upper water column in the Irminger Sea is characterized by cold fresh arctic and subarctic waters and warm saline North Atlantic waters. In this study the local physical and meteorological preconditioning of the phytoplankton development over an annual cycle in the upper water column in four physical zones of the Irminger Sea is investigated. Data from four cruises of the UK's Marine Productivity programme are combined with results from a coupled biological–physical nitrogen–phytoplankton–zooplankton–detritus model run using realistic forcing. The observations and model predictions are compared and analyzed to identify the key parameters and processes which determine the observed heterogeneity in biological production in the Irminger Sea. The simulations show differences in the onset of the bloom, in the time of the occurrence of the maximum phytoplankton biomass and in the length of the bloom between the zones. The longest phytoplankton bloom of 90 days duration was predicted for the East Greenland Current of Atlantic origin zone. In contrast, for the Central Irminger Sea zone a phytoplankton bloom with a start at the beginning of May and the shortest duration of only 70 days was simulated. The latest onset of the phytoplankton bloom in mid May and the latest occurrence of the maximum biomass (end of July) were predicted for the Northern Irminger Current zone. Here the bloom lasted for 80 days. In contrast the phytoplankton bloom in the Southern Irminger Current zone started at the same time as in Central Irminger Sea, but peaked end of June and lasted for 80 days. For all four zones relatively low daily (0.3–0.5 g C m^− 2d^− 1) and annual primary production was simulated, ranging between 35.6 g C m^− 2y^− 1 in the East Greenland Current of Atlantic origin zone and 45.6 g C m^− 2y^− 1 in the Northern Irminger Current zone. The model successfully simulated the observed regional and spatial differences in terms of the maximum depth of winter mixing, the onset of stratification and the development of the seasonal thermocline, and the differences in biological characteristics between the zones. The initial properties of the water column and the seasonal cycle of physical and meteorological forcing in each of the zones are responsible for the observed differences during the Marine Productivity cruises. The timing of the transition from mixing to stratification regime, and the different prevailing light levels in each zone are identified as the crucial processes/parameters for the understanding of the dynamics of the pelagic ecosystem in the Irminger Sea.