Methane release and coastal environment in the East Siberian Arctic shelf

In this paper we present 2 years of data obtained during the late summer period (September 2003 and September 2004) for the East Siberian Arctic shelf (ESAS). According to our data, the surface layer of shelf water was supersaturated up to 2500% relative to the present average atmospheric methane content of 1.85 ppm, pointing to the rivers as a strong source of dissolved methane which comes from watersheds which are underlain with permafrost. Anomalously high concentrations (up to 154 nM or 4400% supersaturation) of dissolved methane in the bottom layer of shelf water at a few sites suggest that the bottom layer is somehow affected by near-bottom sources. The net flux of methane from this area of the East Siberian Arctic shelf can reach up to 13.7 × 10⁴ g CH₄ km^− 2 from plume areas during the period of ice free water, and thus is in the upper range of the estimated global marine methane release. Ongoing environmental change might affect the methane marine cycle since significant changes in the thermal regime of bottom sediments within a few sites were registered. Correlation between calculated methane storage within the water column and both integrated salinity values (r = 0.61) and integrated values of dissolved inorganic carbon (DIC) (r = 0.62) suggest that higher concentrations of dissolved methane were mostly derived from the marine environment, likely due to in-situ production or release from decaying submarine gas hydrates deposits. The calculated late summer potential methane emissions tend to vary from year to year, reflecting most likely the effect of changing hydrological and meteorological conditions (temperature, wind) on the ESAS rather than riverine export of dissolved methane. We point out additional sources of methane in this region such as submarine taliks, ice complex retreat, submarine permafrost itself and decaying gas hydrates deposits.     

Atmospheric CO2 measurements and error analysis on seasonal air–sea CO2 fluxes in the Bay of Biscay

Atmospheric molar fraction of CO₂ (xCO₂^atm) measurements obtained on board of ships of opportunity are used to parameterize the seasonal cycle of atmospheric xCO₂ (xCO₂^atm) in three regions of the eastern North Atlantic (Galician and French offshore and Bay of Biscay). Three selection criteria are established to eliminate spurious values and identify xCO₂^atm data representative of atmospheric background values. The filtered data set is fitted to seasonal curve, consisting of an annual trend plus a seasonal cycle. Although the fitted curves are consistent with the seasonal evolution of xCO₂^atm data series from land meteorological stations, only ship-board measurements can report the presence of winter xCO₂^atm minimum on Bay of Biscay. Weekly air–sea CO₂ flux differences (mmol C·m^− 2 day^− 1) produced by the several options of xCO₂^atm usually used (ship-board measurements, data from land meteorological stations and annually averaged values) were calculated in Bay of Biscay throughout 2003. Flux error using fitted seasonal curve relative to on board measurements was minimal, whereas land stations and annual means yielded random (− 0.2 ± 0.3 mmol C·m^− 2·day^− 1) and systematic (− 0.1 ± 0.4 mmol C·m^− 2 day^− 1), respectively. The effect of different available sources of sea level pressure, wind speed and transfer velocity were also evaluated. Wind speed and transfer velocity parameters are found as the most critical choice in the estimate of CO₂ fluxes reaching a flux uncertainty of 7 mmol C·m^− 2·day^− 1 during springtime. The atmospheric pressure shows a notable relative effect during summertime although its influence is quantitatively slight on annual scale (0.3 ± 0.2 mmol C·m^− 2·day^− 1). All results confirms the role of the Bay of Biscay as CO₂ sink for the 2003 with an annual mean CO₂ flux around − 5 ± 5 mmol C m^− 2 day^− 1.     

Seasonal study of dissolved CH4, CO2 and N2O in a shallow tidal system of the bay of Cádiz (SW Spain)

During 2004, 10 samplings were performed in order to measure dissolved methane (CH₄), carbon dioxide (CO₂) and nitrous oxide (N₂O) in the surface waters of Río San Pedro, a tidal creek in the salt marsh area of the Bay of Cádiz (SW Spain). The inner partvs of the creek is affected by the inputs coming from an intensive fish farm and the drainage of an extensive salt marsh area.Dissolved CH₄, CO₂ and N₂O concentrations ranged from 11 to 88 nM, 36 to 108 μM and 14 to 50 nM, respectively. Surface waters were in all cases oversaturated with respect to the atmosphere, reaching values of up to 5000% for CH₄, 1240% for CO₂ and 840% for N₂O. Dissolved CH₄, CO₂ and N₂O showed a significant tidal and seasonal variability. Over a tidal cycle, concentrations were always highest during low tide, which points to the influence of the inputs from the fish farm effluent and the drainage of the adjacent salt marsh area, as well as in situ production within the system. Dissolved CH₄, CO₂ and N₂O seasonal patterns were similar and showed maximum concentrations in summer conditions. Using four different parameterizations to calculate the gas transfer coefficients [Liss, P.S. and Merlivat, L., 1986. Air-sea exchange rates: introduction and synthesis. In P. Buat-Ménard (Ed.), The Role of Air-Sea Exchanges in Geochemical Cycling. Reidel, Dordrecht, The Netherlands, p. 113–127.; Clark, J.F., Schlosser, P., Simpson, H.J., Stute, M., Wanninkhof, R., and Ho, D.T., 1995. Relationship between gas transfer velocities and wind speeds in the tidal Hudson River determined by the dual tracer technique. In: B. Jähne and E. Monahan (Eds.), Air-Water Gas Transfer: AEON Verlag and Studio, Hanau, Germany, pp. 785–800.; Carini, S., Weston, N., Hopkinson, G., Tucker, J., Giblin, A. and Vallino, J., 1996. Gas exchanges rates in the Parker River estuary, Massachusetts. Biol. Bull., 191: 333–334.; Kremer, J.N., Reischauer, A. and D'Avanzo, C., 2003. Estuary-specific variation in the air-water gas exchange coefficient for oxygen. Estuaries, 26: 829–836.], the averaged air–water fluxes of CH₄, CO₂ and N₂O from the creek to the atmosphere ranged between 34 and 150 μmol CH₄ m^− 2 day^− 1, 73 and 177 mmol CO₂ m^− 2 day^− 1 and 24 and 62 μmol N₂O m⁻² day⁻¹, respectively.     

The biogeochemical cycling of methane in Ria de Vigo, NW Spain: Sediment processing and sea–air exchange

Methane (CH₄) concentrations were measured in the water column, in sediment porewaters, and in atmospheric air, in the Ría de Vigo, NW Spain, during both the onset (April 2003) and at the end of (September 2004) seasonal upwelling. In addition, CH₄ concentration and stable isotopic signatures (δ¹³CH₄) were measured in porewaters, and sediment methanogenesis and aerobic oxidation of CH₄ were determined in sediment incubations. Surface water column CH₄ (2 m depth) was in the range 3–180 nmol l^− 1 (110–8500% saturation) and followed a generally landward increase but with localised maxima in both the inner and middle Ría. These maxima were consistent with CH₄ inputs from underlying porewaters in which CH₄ concentrations were up to 3 orders of magnitude higher (maximum 350 μmol l^− 1). Surface water CH₄ concentrations were approximately three times higher in September than in April, consistent with a significant benthic CH₄ flux driven by enhanced sediment methanogenesis following the summer productivity maximum. CH₄ and δ¹³CH₄ in sediment porewaters and in incubated sediment slurries (20 °C) revealed significant sediment CH₄ oxidation, with an apparent isotopic fractionation factor (r_c) of  1.004. Using turbulent diffusion models of air–sea exchange we estimate an annual emission of atmospheric CH₄ from the Ría de Vigo of 18–44 × 10⁶ g (1.1–2.7 × 10⁶ mol). This estimate is approximately 1–2 orders of magnitude lower than a previous estimate based on a bubble transport model.     

CO2 partial pressure in Northeast Atlantic and adjacent shelf waters: Processes and seasonal variability

CO₂ partial pressure in surface water was measured in the Northeast Atlantic and in the Hebride Shelf/North Sea area during a cruise with R.V. Poseidon in June 1991. A mean p_CO2 of 303 μatm was found in the Atlantic between 50°N and 60°N. For an atmospheric CO₂ content of 357.5 ppm(v) this corresponds to a partial pressure difference of −55 μatm. This supports the view that the subarctic Atlantic is a significant sink within the CO₂ cycle between the ocean and the atmosphere. A comparison of our measurements with other data reveals that the p_CO2 distribution changes significantly during May/June. This explained by seasonal warming, CO₂ exchange with the atmosphere and biomass production. The contribution by each of these processes to the seasonal variations is calculated. It was found that during a plankton bloom the production of biomass is the dominating factor and may lower seawater p_CO2 by almost 100 μatm. The shelf areas are charactrized by strong p_CO2 gradients which are explained by water exchange with the Atlantic, temperature effects and biomass production.     

Air–sea CO2 fluxes in the Caribbean Sea from 2002–2004

Air–sea fluxes in the Caribbean Sea are presented based on measurements of partial pressure of CO₂ in surface seawater, pCO_2sw, from an automated system onboard the cruise ship Explorer of the Seas for 2002 through 2004. The pCO_2sw values are used to develop algorithms of pCO_2sw based on sea surface temperature (SST) and position. The algorithms are applied to assimilated SST data and remotely sensed winds on a 1° by 1° grid to estimate the fluxes on weekly timescales in the region. The positive relationship between pCO_2sw and SST is lower than the isochemical trend suggesting counteracting effects from biological processes. The relationship varies systematically with location with a stronger dependence further south. Furthermore, the southern area shows significantly lower pCO_2sw in the fall compared to the spring at the same SST, which is attributed to differences in salinity. The annual algorithms for the entire region show a slight trend between 2002 and 2004 suggesting an increase of pCO_2sw over time. This is in accord with the increasing pCO_2sw due the invasion of anthropogenic CO₂. The annual fluxes of CO₂ yield a net invasion of CO₂ to the ocean that ranges from − 0.04 to − 1.2 mol m^− 2 year^− 1 over the 3 years. There is a seasonal reversal in the direction of the flux with CO₂ entering into the ocean during the winter and an evasion during the summer. Year-to-year differences in flux are primarily caused by temperature anomalies in the late winter and spring period resulting in changes in invasion during these seasons. An analysis of pCO_2sw before and after hurricane Frances (September 4–6, 2004), and wind records during the storm suggest a large local enhancement of the flux but minimal influence on annual fluxes in the region.     

Winter–spring dynamics in sea-ice carbon cycling in the coastal Arctic Ocean

An understanding of microbial interactions in first-year sea ice on Arctic shelves is essential for identifying potential responses of the Arctic Ocean carbon cycle to changing sea-ice conditions. This study assessed dissolved and particulate organic carbon (DOC, POC), exopolymeric substances (EPS), chlorophyll a, bacteria and protists, in a seasonal (24 February to 20 June 2004) investigation of first-year sea ice and associated surface waters on the Mackenzie Shelf. The dynamics of and relationships between different sea-ice carbon pools were investigated for the periods prior to, during and following the sea-ice-algal bloom, under high and low snow cover. A predominantly heterotrophic sea-ice community was observed prior to the ice-algal bloom under high snow cover only. However, the heterotrophic community persisted throughout the study with bacteria accounting for, on average, 44% of the non-diatom particulate carbon biomass overall the study period. There was an extensive accumulation of sea-ice organic carbon following the onset of the ice-algal bloom, with diatoms driving seasonal and spatial trends in particulate sea-ice biomass. DOC and EPS were also significant sea-ice carbon contributors such that sea-ice DOC concentrations were higher than, or equivalent to, sea-ice-algal carbon concentrations prior to and following the algal bloom, respectively. Sea-ice-algal carbon, DOC and EPS-carbon concentrations were significantly interrelated under high and low snow cover during the algal bloom (r values ≥ 0.74, p < 0.01). These relationships suggest that algae are primarily responsible for the large pools of DOC and EPS-carbon and that similar stressors and/or processes could be involved in regulating their release. This study demonstrates that DOC can play a major role in organic carbon cycling on Arctic shelves.     

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.     

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.     

Characterization of fall–winter upwelling recurrence along the Galician western coast (NW Spain) from 2000 to 2005: Dependence on atmospheric forcing

Upwelling events driving ENACW (Eastern North Atlantic Coastal Water) into the Galician western coast rias had been considered typical spring–summer processes, according to the research developed in this area. However, they can also be observed in fall or winter under northerly winds blowing at shelf. Six different upwelling events were analyzed in the Ria of Pontevedra during the wet season (NDJF) from 2000 to 2005. These events were characterized by means of the zonal Ekman transport (Q_x) at four control points in front of the western rias (locally known as Rias Baixas) and thermohaline variables measured at a fixed station in the main mouth of the Ria of Pontevedra. The duration of the upwelling events ranged from 27 days (during February and March 2002) to 69 days (during November–December 2004 and January 2005). Upwelling events studied in the Ria of Pontevedra from 2000 to 2005 showed the similarity in upwelling features during both seasons (similar wind forcing and upwelled water). Finally, Q_x was correlated with the most representative atmospheric patterns in the Northern Hemisphere (EA, NAO, EA/WR, POL and SCA) from 1966 to 2005. The winter EA pattern has the most influence on Q_x showing an annual evolution with a prevalence of the positive phase from 1976 on. This positive phase is directly correlated with a prevalence of positive values of Q_x which are upwelling unfavorable in the Rias Baixas.     

Evaluating transfer velocity-wind speed relationship using a long-term series of direct eddy correlation CO2 flux measurements

Long-term observations of the marine atmospheric boundary layer were performed by an eddy correlation system, which was set-up on a platform in the Baltic Sea. In this experiment the three-dimensional wind vector and the turbulent fluxes of momentum, sensible and latent heat and CO₂ were measured for one and a half years. Simultaneously the CO₂ partial pressure p_CO2 in surface water was measured by a submersible autonomous moored instrument for CO₂ at the platform in 7-m depth. The high-resolution eddy correlation measurements of the atmospheric CO₂ flux F_CO2, together with the measurements of the CO₂ partial pressure differences between air and sea Δp_CO2 led to a long-term data set which provided the possibility to investigate the parameterization of the CO₂ transfer velocity k as a function of 10-m wind speed u in a statistical manner. From half-hour mean CO₂ fluxes and CO₂ partial pressure differences, k was calculated using k = F_CO2 / (K₀Δp_CO2), with K₀ the CO₂ solubility. The half-hour mean data points, used for the determination of the k–u parameterization, show large scatter. However, assuming a linear, quadratic dependency the analysis yields: k₆₆₀ = 0.365u² + 0.46u (k at 20 °C and salinity 35 psu) with a correlation coefficient of r² = 0.81. The large scatter indicates that the kinetics of the air–sea CO₂ transfer velocity is not only a function of the wind speed alone, but might also be controlled by other environmental parameters and mechanisms, such as sea state and surface coverage with surfactants.     

Nutrient and organic matter patterns across the Mackenzie River, estuary and shelf during the seasonal recession of sea-ice

Suspended material, nutrients and organic matter in Mackenzie River water were tracked along a 300 km transect from Inuvik (Northwest Territories, Canada), across the estuarine salinity gradient in Kugmallit Bay, to offshore marine stations on the adjacent Mackenzie Shelf. All particulates measured (SPM, POC, PN, PP) declined by 87–95% across the salinity gradient and levels were generally below conservative mixing. Organic carbon content of suspended material decreased from 3.1% in the river to 1.7% in shelf surface waters while particulate C:N concurrently decreased from 17.1 to 8.6. Nitrate and silicate concentrations declined by more than 90% across the salinity gradient, with nitrate concentrations often below the conservative mixing line. Phosphate concentrations increased from 0.03 μmol/L in the river to 0.27 μmol/L over shelf waters, thereby changing the inorganic nutrient regime downstream from P to N limitation. Dissolved organic carbon decreased conservatively offshore while dissolved organic N and P persisted at high levels in the Mackenzie plume relative to river water, increasing 2.7 and 25.3 times respectively. A deep chlorophyll-a maximum was observed at two offshore stations and showed increases in most nutrients, particulates and organic matter relative to the rest of the water column. During river passage through the Mackenzie estuary, particulate matter, dissolved organic carbon and inorganic nutrients showed sedimentation, dilution and biological uptake patterns common to other arctic and non-arctic estuaries. Alternatively, inorganic content of particles increased offshore and dissolved organic N and P increased substantially over the shelf, reaching concentrations among the highest reported for the Arctic Ocean. These observations are consistent with the presence of a remnant ice-constrained (‘stamukhi’) lake from the freshet period and a slow flushing river plume constrained by sea-ice in close proximity to shore. Nutrient limitation in surface shelf waters during the ARDEX cruise contributed to the striking deep chlorophyll-a maximum at 21 m where phytoplankton communities congregated at the margin of nutrient-rich deep ocean waters.     

pH variability and CO2 induced acidification in the North Sea

A coupled carbonate system–marine ecosystem–hydrodynamic model is used to simulate the temporal and spatial variability in pH across the southern North Sea as it relates to the environmental and biological processes affecting CO₂, namely, photosynthesis and respiration, riverine boundary conditions and atmospheric CO₂ concentrations. Annual pH ranges are found to vary from < 0.2 in areas of low biological activity to > 1.0 in areas influenced by riverine signals, consistent with observations and previous studies. It is shown that benthic, as well as pelagic, activity is an important factor in this variability. The acidification of the region due to increased fluxes of atmospheric CO₂ into the marine system is calculated and shown to exceed, on average, 0.1 pH units over the next 50 years and result in a total acidification of 0.5 pH units below pre-industrial levels at atmospheric CO₂ concentrations of 1000 ppm. The potential for measurable changes in biogeochemistry are demonstrated by simulating the observed inhibition of pelagic nitrification with decreasing pH. However, we conclude that there is a lack of knowledge of how acidification might affect the complex interaction of processes that govern marine biogeochemical cycles and a consequent need for further research and observations.     

Influence of the Mackenzie River plume on the sinking export of particulate material on the shelf

We examined the influence of the Mackenzie River plume on sinking fluxes of particulate organic and inorganic material on the Mackenzie Shelf, Canadian Arctic. Short-term particle interceptor traps were deployed under the halocline at 3 stations across the shelf during fall 2002 and at 3 stations along the shelf edge during summer 2004. During the two sampling periods, the horizontal patterns in sinking fluxes of particulate organic carbon (POC) and chlorophyll a (chl a) paralleled those in chl a biomass within the plume. Highest sinking fluxes of particulate organic material occurred at stations strongly influenced by the river plume (maximum POC sinking fluxes at 25 m of 98 mg C m^− 2 d^− 1 and 197 mg C m^− 2 d^− 1 in 2002 and 2004, respectively). The biogeochemical composition of the sinking material varied seasonally with phytoplankton and fecal pellets contributing considerably to the sinking flux in summer, while amorphous detritus dominated in the fall. Also, the sinking phytoplankton assemblage showed a seasonal succession from a dominance of diatoms in summer to flagellates and dinoflagellates in the fall. The presence of the freshwater diatom Eunotia sp. in the sinking assemblage directly underneath the river plume indicates the contribution of a phytoplankton community carried by the plume to the sinking export of organic material. Yet, increasing chl a and BioSi sinking fluxes with depth indicated an export of phytoplankton from the water column below the river plume during summer and fall. Grazing activity, mostly by copepods, and to a lesser extent by appendicularians, appeared to occur in a well-defined stratum underneath the river plume, particularly during summer. These results show that the Mackenzie River influences the magnitude and composition of the sinking material on the shelf in summer and fall, but does not constitute the only source of material sinking to depth at stations influenced by the river plume.     

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.     

Linking mercury exposure to habitat and feeding behaviour in Beaufort Sea beluga whales

Mercury (Hg) levels in the Beaufort Sea beluga population have been increasing since the 1990's. Ultimately, it is the Hg content of prey that determines beluga Hg levels. However, the Beaufort Sea beluga diet is not understood, and little is known about the diet Hg sources in their summer habitat. During the summer, they segregate into social groups based on habitat use leading to the hypothesis that they may feed in different food webs explaining Hg dietary sources. Methyl mercury (MeHg) and total mercury (THg) levels were measured in the estuarine-shelf, Amundsen Gulf and epibenthic food webs in the western Canadian Arctic collected during the Canadian Arctic Shelf Exchange Study (CASES) to assess their dietary Hg contribution. To our knowledge, this is the first study to report MeHg levels in estuarine fish and epibenthic invertebrates from the Arctic Ocean. Although the Mackenzie River is a large source of Hg, the estuarine-shelf prey items had the lowest MeHg levels, ranging from 0.1 to 0.27 μg/g dry weight (dw) in arctic cisco (Coregonus autumnalis) and saffron cod (Eleginus gracilis) respectively. Highest MeHg levels occurred in fourhorn sculpin (Myoxocephalus quadricornis) (0.5 μg/g dw) from the epibenthic food web. Beluga hypothesized to feed in the epibenthic and Amundsen Gulf food webs had the highest Hg levels matching with high Hg levels in associated food webs, and estuarine-shelf belugas had the lowest Hg levels (2.6 μg/g dw), corresponding with the low food web Hg levels, supporting the variation in dietary Hg uptake. The trophic level transfer of Hg was similar among the food webs, highlighting the importance of Hg sources at the bottom of the food web as well as food web length. We propose that future biomagnification studies incorporate predator behaviour with food web structure to assist in the evaluation of dietary Hg sources.     

Air–sea gas exchange at extreme wind speeds measured by autonomous oceanographic floats

Measurements of the air–sea fluxes of N₂ and O₂ were made in winds of 15–57 m s^− 1 beneath Hurricane Frances using two types of air-deployed neutrally buoyant and profiling underwater floats. Two “Lagrangian floats” measured O₂ and total gas tension (GT) in pre-storm and post-storm profiles and in the actively turbulent mixed layer during the storm. A single “EM-APEX float” profiled continuously from 30 to 200 m before, during and after the storm. All floats measured temperature and salinity. N₂ concentrations were computed from GT and O₂ after correcting for instrumental effects. Gas fluxes were computed by three methods. First, a one-dimensional mixed layer budget diagnosed the changes in mixed layer concentrations given the pre-storm profile and a time varying mixed layer depth. This model was calibrated using temperature and salinity data. The difference between the predicted mixed layer concentrations of O₂ and N₂ and those measured was attributed to air–sea gas fluxes F_BO and F_BN. Second, the covariance flux F_CO(z) = wO₂′(z) was computed, where w is the vertical motion of the water-following Lagrangian floats, O₂′ is a high-pass filtered O₂ concentration and (z) is an average over covariance pairs as a function of depth. The profile F_CO(z) was extrapolated to the surface to yield the surface O₂ flux F_CO(0). Third, a deficit of O₂ was found in the upper few meters of the ocean at the height of the storm. A flux F_SO, moving O₂ out of the ocean, was calculated by dividing this deficit by the residence time of the water in this layer, inferred from the Lagrangian floats. The three methods gave generally consistent results. At the highest winds, gas transfer is dominated by bubbles created by surface wave breaking, injected into the ocean by large-scale turbulent eddies and dissolving near 10-m depth. This conclusion is supported by observations of fluxes into the ocean despite its supersaturation; by the molar flux ratio F_BO/F_BN, which is closer to that of air rather than that appropriate for Schmidt number scaling; by O₂ increases at about 10-m depth along the water trajectories accompanied by a reduction in void fraction as measured by conductivity; and from the profile of F_CO(z), which peaks near 10 m instead of at the surface.At the highest winds O₂ and N₂ are injected into the ocean by bubbles dissolving at depth. This, plus entrainment of gas-rich water from below, supersaturates the mixed layer causing gas to flux out of the near-surface ocean. A net influx of gas results from the balance of these two competing processes. At lower speeds, the total gas fluxes, F_BO, F_BN and F_CO(0), are out of the ocean and downgradient.     

Silicon dynamics in the Oder estuary, Baltic Sea

Studies on dissolved silicate (DSi) and biogenic silica (BSi) dynamics were carried out in the Oder estuary, Baltic Sea in 2000–2005. The Oder estuary proved to be an important component of the Oder River–Baltic Sea continuum where very intensive seasonal DSi uptake during spring and autumn, but also BSi regeneration during summer take place. Owing to the regeneration process annual DSi patterns in the river and the estuary distinctly differed; the annual patterns of DSi in the estuary showed two maxima and two minima in contrast to one maximum- and one minimum-pattern in the Oder River. DSi concentrations in the river and in the estuary were highest in winter (200–250 μmol dm^− 3) and lowest (often less than 1 μmol dm^− 3) in spring, concomitant with diatom growth; such low values are known to be limiting for new diatom growth. Secondary DSi summer peaks at the estuary exit exceeded 100 μmol dm^− 3, and these maxima were followed by autumn minima coinciding with the autumn diatom bloom. Seasonal peaks in BSi concentrations (ca. 100 μmol dm^− 3) occurred during the spring diatom bloom in the Oder River. Mass balance calculations of DSi and BSi showed that DSi + BSi import to the estuary over a two year period was 103.2 kt and that can be compared with the DSi export of 98.5 kt. The difference between these numbers gives room for ca. 2.5 kt BSi to be annually exported to the Baltic Sea. Sediment cores studies point to BSi annual accumulation on the level of 2.5 kt BSi. BSi import to the estuary is on the level of ca. 10.5 kt, thus ca. 5 kt of BSi is annually converted into the DSi, increasing the pool of DSi that leaves the system. BSi concentrations being ca. 2 times higher at the estuary entrance than at its exit remain in a good agreement with the DSi and BSi budgeting presented in the paper.     

Inorganic carbon fluxes through the boundaries of the Greenland Sea Basin based on in situ observations and water transport estimates

A carbon budget for the exchange of total dissolved inorganic carbon C_T between the Greenland Sea and the surrounding seas has been constructed for winter and summer situations. An extensive data set of C_T collected over the years 1994–1997 within the European Sub-polar Ocean Programmes (ESOP1 and ESOP2) are used for the budget calculation. Based on these data, mean values of C_T in eight different boxes representing the inflow and outflow of water through the boundaries of the Greenland Sea Basin are estimated. The obtained values are then combined with simulated water transports taken from the ESOP2 version of the Miami Isopycnic Coordinate Ocean Model (MICOM). The fluxes of inorganic carbon are presented for three layers; a surface mixed layer, an intermediate layer and a deep layer, and the imbalance in the fluxes are attributed to air–sea exchange, biological fixation of inorganic carbon, and sedimentation. The main influx of carbon is found in the surface and the deep layers in the Fram Strait, and in the surface waters of direct Atlantic origin, whereas the main outflux is found in the surface layer over the Jan Mayen Fracture Zone and the Knipovich Ridge, transporting carbon into the Atlantic Ocean via the Denmark Strait and towards the Arctic Ocean via the Norwegian Sea, respectively. The flux calculation indicates that there is a net transport of carbon out of the Greenland Sea during wintertime. In the absence of biological activity, this imbalance is attributed to air sea exchange, and requires an oceanic uptake of CO₂ of 0.024±0.006 Gt C yr⁻¹. The flux calculations from the summer period are complicated by biological fixation of inorganic carbon, and show that data on organic carbon is required in order to estimate the air–sea exchange in the area.