Carbon dioxide flux techniques performed during GasEx-98

A comprehensive study of air–sea interactions focused on improving the quantification of CO₂ fluxes and gas transfer velocities was performed within a large open ocean CO₂ sink region in the North Atlantic. This study, GasEx-98, included shipboard measurements of direct covariance CO₂ fluxes, atmospheric CO₂ profiles, atmospheric DMS profiles, water column mass balances of CO₂, and measurements of deliberate SF₆–³He tracers, along with air–sea momentum, heat, and water vapor fluxes. The large air–sea differences in partial pressure of CO₂ caused by a springtime algal bloom provided high signals for accurate CO₂ flux measurements. Measurements were performed over a wind speed range of 1–16 m s⁻¹ during the three-week process study. This first comparison between the novel air-side and more conventional water column measurements of air–sea gas transfer show a general agreement between independent air–sea gas flux techniques. These new advances in open ocean air–sea gas flux measurements demonstrate the progress in the ability to quantify air–sea CO₂ fluxes on short time scales. This capability will help improve the understanding of processes controlling the air–sea fluxes, which in turn will improve our ability to make regional and global CO₂ flux estimates.     

Seasonal and interannual variability of the air–sea CO2 flux in the Atlantic sector of the Barents Sea

The seasonal and interannual variability of the air–sea CO₂ flux (F) in the Atlantic sector of the Barents Sea have been investigated. Data for seawater fugacity of CO₂ (fCO₂^sw) acquired during five cruises in the region were used to identify and validate an empirical procedure to compute fCO₂^sw from phosphate (PO₄), seawater temperature (T), and salinity (S). This procedure was then applied to time series data of T, S, and PO₄ collected in the Barents Sea Opening during the period 1990–1999, and the resulting fCO₂^sw estimates were combined with data for the atmospheric mole fraction of CO₂, sea level pressure, and wind speed to evaluate F.The results show that the Atlantic sector of the Barents Sea is an annual sink of atmospheric CO₂. The monthly mean uptake increases nearly monotonically from 0.101 mol C m^− 2 in midwinter to 0.656 mol C m^− 2 in midfall before it gradually decreases to the winter value. Interannual variability in the monthly mean flux was evaluated for the winter, summer, and fall seasons and was found to be ± 0.071 mol C m^− 2 month^− 1. The variability is controlled mainly through combined variation of fCO₂^sw and wind speed. The annual mean uptake of atmospheric CO₂ in the region was estimated to 4.27 ± 0.68 mol C m^− 2.     

One-dimensional modelling of convective CO2 exchange in the Tropical Atlantic

Diurnal changes in seawater temperature affect the amount of air–sea gas exchange taking place through changes in solubility and buoyancy-driven nocturnal convection, which enhances the gas transfer velocity. We use a combination of in situ and satellite derived radiometric measurements and a modified version of the General Ocean Turbulence Model (GOTM), which includes the National Oceanic and Atmospheric Administration Coupled-Ocean Atmospheric Response Experiment (NOAA-COARE) air–sea gas transfer parameterization, to investigate heat and carbon dioxide exchange over the diurnal cycle in the Tropical Atlantic. A new term based on a water-side convective velocity scale (w_*w) is included, to improve parameterization of convectively driven gas transfer. Meteorological data from the PIRATA mooring located at 10°S10°W in the Tropical Atlantic are used, in conjunction with cloud cover estimates from Meteosat-7, to calculate fluxes of longwave, latent and sensible heat along with a heat budget and temperature profiles during February 2002. Twin model experiments, representing idealistic and realistic conditions, reveal that over daily time scales the additional contribution to gas exchange from convective overturning is important. Increases in transfer velocity of up to 20% are observed during times of strong insolation and low wind speeds (<6 m s⁻¹); the greatest enhancement from w_*w to the CO₂ flux occurs when diurnal warming is large. Hence, air–sea fluxes of CO₂ calculated using simple parameterizations underestimate the contribution from convective processes. The results support the need for parameterizations of gas transfer that are based on more than wind speed alone and include information about the heat budget.     

Time series of carbonate system variables off Otaru coast in Hokkaido, Japan

We report several biogeochemical parameters (dissolved inorganic carbon (DIC), total alkalinity (TA), dissolved oxygen (DO), phosphate (PO₄), nitrate + nitrite (NO₃ + NO₂), silicate (Si(OH)₄)) in a region off Otaru coast in Hokkaido, Japan on a “weekly” basis during the period of April 2002–May 2003. To better understand the long-term temporal variations of the main factors affecting CO₂ flux in this coastal region and its role as a sink/source of atmospheric CO₂, we constructed an algorithm of DIC and TA using other hydrographic properties. We estimated the CO₂ flux across the air–sea interface by using the classical bulk method. During 1998–2003 in our study region, the estimated fCO_2sea ranged about 185–335 μatm. The maximum of fCO_2sea in the summer was primarily due to the change of water temperature. The minimum of fCO_2sea in the early spring can be explained not only by the change of water temperature but also the change of nutrients and chlorophyll-a. To clarify the factors affecting fCO_2sea (water temperature, salinity, and biological activity), we carried out a sensitivity analysis of these effects on the variation of fCO_2sea. In spring, the biological effect had the largest effect for the minimum of fCO_2sea (40%). In summer, the water temperature effect had the largest effect for the maximum of fCO_2sea (25%). In fall, the water temperature effect had the largest effect for the minimum of fCO_2sea (53%). In winter, the biological effect had the largest effect for the minimum of fCO_2sea (35%).We found that our study region was a sink region of CO₂ throughout a year (−0.78 mol/m²/yr). Furthermore, we estimated that the increase of fCO_2sea was about 0.56 μatm/yr under equilibrium with the atmospheric CO₂ content for the period 1998–2003, with the temporal changes in the variables (T, S, PO₄) on fCO_2sea, thus as the maximum trend of each variable on fCO_2sea was 0.22 μatm/yr, and the trend of residual fCO₂ including gas exchange was 0.34 μatm/yr. This result suggests that interaction among variables would affect gas exchange between air and sea effects on fCO_2sea. We conclude that this study region as a representative coastal region of marginal seas of the North Pacific is special because it was measured, but there is no particular significance in comparison to any other area.     

Short-term variability of fCO2 in seawater and air–sea CO2 fluxes in a coastal upwelling system (Ría de Vigo, NW Spain)

Coastal upwelling systems are regions with highly variable physical processes and very high rates of primary production and very little is known about the effect of these factors on the short-term variations of CO₂ fugacity in seawater (fCO₂^w). This paper presents the effect of short-term variability (<1 week) of upwelling–downwelling events on CO₂ fugacity in seawater (fCO₂^w), oxygen, temperature and salinity fields in the Ría de Vigo (a coastal upwelling ecosystem). The magnitude of fCO₂^w values is physically and biologically modulated and ranges from 285 μatm in July to 615 μatm in October. There is a sharp gradient in fCO₂^w between the inner and the outer zone of the Ría during almost all the sampling dates, with a landward increase in fCO₂^w.CO₂ fluxes calculated from local wind speed and air–sea fCO₂ differences indicate that the inner zone is a sink for atmospheric CO₂ in December only (−0.30 mmol m⁻² day⁻¹). The middle zone absorbs CO₂ in December and July (−0.05 and −0.27 mmol·m⁻² day⁻¹, respectively). The oceanic zone only emits CO₂ in October (0.36 mmol·m⁻² day⁻¹) and absorbs at the highest rate in December (−1.53 mmol·m⁻² day⁻¹).     

Deep ocean fluxes and their link to surface ocean processes and the biological pump

Intense studies of upper and deep ocean processes were carried out in the Northwestern Indian Ocean (Arabian Sea) within the framework of JGOFS and related projects in order to improve our understanding of the marine carbon cycle and the ocean’s role as a reservoir for atmospheric CO₂. The results show a pronounced monsoon-driven seasonality with enhanced organic carbon fluxes into the deep-sea during the SW Monsoon and during the early and late NE Monsoon north of 10°N. The productivity is mainly regulated by inputs of nutrients from subsurface waters into the euphotic zone via upwelling and mixed layer-deepening. Deep mixing introduces light limitation by carrying photoautotrophic organisms below the euphotic zone during the peak of the NE Monsoon. Nevertheless, deep mixing and strong upwelling during the SW Monsoon provide an ecological advantage for diatoms over other photoautotrophic organisms by increasing the silica concentrations in the euphotic zone. When silica concentrations fall below 2 μmol l⁻¹, diatoms lose their dominance in the plankton community. During diatom-dominated blooms, the biological pathway of uptake of CO₂ (the biological pump) appears to be more efficient than during blooms of other organisms, as indicated by organic carbon to carbonate carbon (rain) ratios. Due to the seasonal alternation of diatom and non-diatom dominated exports, spatial variations of the annual mean rain ratios are hardly discernible along the main JGOFS transect.Data-based estimates of the annual mean impact of the biological pump on the fCO₂ in the surface water suggest that the biological pump reduces the increase of fCO₂ in the surface water caused by intrusion of CO₂-enriched subsurface water by 50–70%. The remaining 30 to 50% are attributed to CO₂ emissions into the atmosphere. Rain ratios up to 60% higher in river-influenced areas off Pakistan and in the Bay of Bengal than in the open Arabian Sea imply that riverine silica inputs can further enhance the impact of the biological pump on the fCO₂ in the surface water by supporting diatom blooms. Consequently, it is assumed that reduced river discharges caused by the damming of major rivers increase CO₂ emission by lowering silica inputs to the Arabian Sea; this mechanism probably operates in other regions of the world ocean also.     

Alkalinity changes in the Sargasso Sea: geochemical evidence of calcification?

Strong seasonal patterns in upper ocean total carbon dioxide (TCO₂), alkalinity (TA) and calculated pCO₂ were observed in a time series of water column measurements collected at the US Joint Global Ocean Flux Study (JGOFS) BATS site (31 °50′N, 64 °10′W) in the Sargasso Sea. TA distribution was a conservative function of salinity. However, in February 1992, a non-conservative decrease in TA was observed, with maximum depletion of 25–30 μmoles kg⁻¹ occuring in the surface layer and at the depth of the chlorophyll maximum (˜ 80–100 m). Mixed-layer TCO₂ also decreased, while surface pCO₂ increased by 25–30 μatm. We suggest these changes in carbon dioxide species resulted from open-ocean calcification by carbonate-secreting organisms rather than physical processes. Coccolithophore calcification is the most likely cause of this event although calcification by foraminifera or pteropods cannot be ruled out. Due to the transient increase in surface pCO₂, the net annual transfer of CO₂ into the ocean at BATS was reduced. These observations demonstrate the potential importance of open-ocean calcification and biological community structure in the biogeochemical cycling of carbon.     

Nitrogen and oxygen isotopic composition of N2O from suboxic waters of the eastern tropical North Pacific and the Arabian Sea—measurement by continuous-flow isotope-ratio monitoring

Nitrous oxide (N₂O) is a trace gas that is increasing in the atmosphere. It contributes to the greenhouse effect and influences the global ozone distribution. Recent reports suggest that regions such as the Arabian Sea may be significant sources of atmospheric N₂O.In the ocean, N₂O is formed as a by-product of nitrification and as an intermediary of denitrification. In the latter process, N₂O can be further reduced to N₂. These processes, which operate on different source pools and have different magnitudes of isotopic fractionation, make separate contributions to the ¹⁵N and¹⁸O isotopic composition of N₂O. In the case of nitrification in oxic waters, the isotopic composition of N₂O appears to depend mainly on the ¹⁵N/¹⁴N ratio of NH⁺₄ and the ¹⁸O/¹⁶O ratio of O₂ and H₂O. In suboxic waters, denitrification causes progressive ¹⁵N and ¹⁸O enrichment of N₂O as a function of degree of depletion of nitrate and dissolved oxygen. Thus the isotopic signature of N₂O should be a useful tool for studying the sources and sinks for N₂O in the ocean and its impact on the atmosphere.We have made observations of N₂O concentrations and of the dual stable isotopic composition of N₂O in the eastern tropical North Pacific (ETNP) and the Arabian Sea. The stable isotopic composition of N₂O was determined by a new method that required only 80–100 nmol of N₂O per sample analysis. Our observations include determinations across the oxic/suboxic boundaries that occur in the water columns of the ETNP and Arabian Sea. In these suboxic waters, the values of δ¹⁵N and δ¹⁸O increased linearly with one another and with decreasing N₂O concentrations, presumably reflecting the effects of denitrification. Our results suggest that the ocean could be an important source of isotopically enriched N₂O to the atmosphere.     

Interannual variations of the Antarctic Ocean CO2 uptake from 1986 to 1994

The interannual variations of CO₂ sources and sinks in the surface waters of the Antarctic Ocean (south of 50°S) were studied between 1986 and 1994. An existing, slightly modified one-dimensional model describing the mixed-layer carbon cycle was used for this study and forced by available satellite-derived and climatological data. Between 1986 and 1994, the mean Antarctic Ocean CO₂ uptake was 0.53 Pg C year⁻¹ with an interannual variability of 0.15 Pg C year⁻¹.Interannual variation of the Antarctic Ocean CO₂ uptake is related to the Antarctic Circumpolar Wave (ACW), which affects sea surface temperature (SST), wind-speed and sea-ice extent. The CO₂ uptake in the Antarctic Ocean has increased from 1986 to 1994 by 0.32 Pg C. It was found that over the 9 years, the surface ocean carbon dioxide fugacity (fCO₂) increase was half that of the atmospheric CO₂ increase inducing an increase of the air–sea fCO₂ gradient. This effect is responsible for 60% of the Antarctic Ocean CO₂ uptake increase between 1986 and 1994, as the ACW effect cancels out over the 9 years investigated.     

Intercomparison of shipboard and moored CARIOCA buoy seawater fCO2 measurements in the Sargasso Sea

The ocean is an important sink for carbon and heat, yet high-resolution measurements of biogeochemical properties relevant to global climate change are being made only sporadically in the ocean at present. There is a growing need for automated, real-time, long-term measurements of CO₂ in the ocean using a network of sensors, strategically placed on ships, moorings, free-drifting buoys and autonomous remotely operated vehicles. The ground-truthing of new sensor technologies is a vital component of present and future efforts to monitor changes in the ocean carbon cycle and air–sea exchange of CO₂.A comparison of a moored Carbon Interface Ocean Atmosphere (CARIOCA) buoy and shipboard fugacity of CO₂ (fCO₂) measurements was conducted in the western North Atlantic during two extended periods (>1 month) in 1997. The CARIOCA buoy was deployed on the Bermuda Testbed Mooring (BTM), which is located 5 km north of the site of the US Joint Global Ocean Flux Study (JGOFS) Bermuda Atlantic Time-series Study (BATS). The high frequency of sampling revealed that temperature and fCO₂ responded to physical forcing by the atmosphere on timescales from diurnal to 4–8 days. Concurrent with the deployments of the CARIOCA buoy, frequent measurements of surface fCO₂ were made from the R/V Weatherbird II during opportunistic visits to the BTM and BATS sites, providing a direct calibration of the CARIOCA buoy fCO₂ data. Although, the in situ ground-truthing of the CARIOCA buoy was complicated by diurnal processes, sub-mesoscale and fine-scale variability, the CARIOCA buoy fCO₂ data was accurate within 3±6 μatm of shipboard fCO₂ data for periods up to 50 days. Longer-term assessments were not possible due to the CARIOCA buoy breaking free of the BTM and drifting into waters with different fCO₂-temperature properties. Strategies are put forward for future calibration of other in situ sensors.     

Distribution and air-sea fluxes of carbon dioxide on the Chukchi Sea shelf

This article presents the results of long-term studies of the dynamics of carbonate parameters and air–sea carbon dioxide fluxes on the Chukchi Sea shelf during the summer. As a result of the interaction of physical and biological factors, the surface waters on the west of Chukchi Sea were undersaturated with carbon dioxide when compared with atmospheric air; the partial pressure of CO₂ varied in the range from 134 to 359 μatm. The average value of CO₂ flux in the Chukchi Sea per unit area varied in the range from–2.4 to–22.0 mmol /(m² day), which is significantly higher than the average value of CO₂ flux in the World Ocean. It has been estimated that the minimal mass of C absorbed by the surface of Chukchi Sea from the atmosphere during ice-free season is 13 × 10¹² g; a great part of this carbon is transported to the deeper layers of sea and isolated from the atmosphere for a long period of time. The studies of the carbonate system of the Chukchi Sea, especially of its western part, will provide some new data on the fluxes of carbon dioxide in the Arctic Ocean and their changes. Our analysis can be used for an interpretation of the satellite assessment of CO₂ fluxes and dissolved CO₂ distribution in the upper layers of the ocean.     

Seasonal and inter-annual variability of air–sea CO2 fluxes and seawater carbonate chemistry in the Southern North Sea

A 3D coupled biogeochemical–hydrodynamic model (MIRO-CO₂&CO) is implemented in the English Channel (ECH) and the Southern Bight of the North Sea (SBNS) to estimate the present-day spatio-temporal distribution of air–sea CO₂ fluxes, surface water partial pressure of CO₂ (pCO₂) and other components of the carbonate system (pH, saturation state of calcite (Ω_ca) and of aragonite (Ω_ar)), and the main drivers of their variability. Over the 1994–2004 period, air–sea CO₂ fluxes show significant inter-annual variability, with oscillations between net annual CO₂ sinks and sources. The inter-annual variability of air–sea CO₂ fluxes simulated in the SBNS is controlled primarily by river loads and changes of biological activities (net autotrophy in spring and early summer, and net heterotrophy in winter and autumn), while in areas less influenced by river inputs such as the ECH, the inter-annual variations of air–sea CO₂ fluxes are mainly due to changes in sea surface temperature and in near-surface wind strength and direction. In the ECH, the decrease of pH, of Ω_ca and of Ω_ar follows the one expected from the increase of atmospheric CO₂ (ocean acidification), but the decrease of these quantities in the SBNS during the considered time period is faster than the one expected from ocean acidification alone. This seems to be related to a general pattern of decreasing nutrient river loads and net ecosystem production (NEP) in the SBNS. Annually, the combined effect of carbon and nutrient loads leads to an increase of the sink of CO₂ in the ECH and the SBNS, but the impact of the river loads varies spatially and is stronger in river plumes and nearshore waters than in offshore waters. The impact of organic and inorganic carbon (C) inputs is mainly confined to the coast and generates a source of CO₂ to the atmosphere and low pH, of Ω_ca and of Ω_ar values in estuarine plumes, while the impact of nutrient loads, highest than the effect of C inputs in coastal nearshore waters, also propagates offshore and, by stimulating primary production, drives a sink of atmospheric CO₂ and higher values of pH, of Ω_ca and of Ω_ar.     

High-resolution measurement of Southern Ocean CO2 and O2/Ar by membrane inlet mass spectrometry

This paper evaluates the simultaneous measurement of dissolved gases (CO₂ and O₂/Ar ratios) by membrane inlet mass spectrometry (MIMS) along the 180° meridian in the Southern Ocean. The calibration of pCO₂ measurements by MIMS is reported for the first time using two independent methods of temperature correction. Multiple calibrations and method comparison exercises conducted in the Southern Ocean between New Zealand and the Ross Sea showed that the MIMS method provides pCO₂ measurements that are consistent with those obtained by standard techniques (i.e. headspace equilibrator equipped with a Li–Cor NDIR analyser). The overall MIMS accuracy compared to Li–Cor measurements was 0.8 μatm. The O₂/Ar ratio measurements were calibrated with air-equilibrated seawater standards stored at constant temperature (0 ± 1 °C). The reproducibility of the O₂/Ar standards was better than 0.07% during the 9 days of transect between New Zealand and the Ross Sea.The high frequency, real-time measurements of dissolved gases with MIMS revealed significant small-scale heterogeneity in the distribution of pCO₂ and biologically-induced O₂ supersaturation (ΔO₂/Ar). North of 65°S several prominent thermal fronts influenced CO₂ concentrations, with biological factors also contributing to local variability. In contrast, the spatial variation of pCO₂ in the Ross Sea gyre was almost entirely attributed to the biological utilization of CO_2, with only small temperature effects. This high productivity region showed a strong inverse relationship between pCO₂ and biologically-induced O₂ disequilibria (r² = 0.93). The daily sea air CO₂ flux ranged from − 0.2 mmol/m² in the Northern Sub-Antarctic Front to − 6.4 mmol/m² on the Ross Sea shelves where the maximum CO₂ influx reached values up to − 13.9 mmol/m². This suggests that the Southern Ocean water (south of 58°S) acts as a seasonal sink for atmospheric CO₂ at the time of our field study.     

Air–sea carbon dioxide fluxes in the coastal southeastern tropical Pacific

Comprehensive sea surface surveys of the partial pressure of carbon dioxide (pCO₂) have been made in the upwelling system of the coastal (0–200 km from shore) southeastern tropical Pacific since 2004. The shipboard data have been supplemented by mooring and drifter based observations. Air–sea flux estimates were made by combining satellite derived wind fields with the direct sea surface pCO₂ measurements. While there was considerable spatial heterogeneity, there was a significant flux of CO₂ from the ocean to the atmosphere during all survey periods in the region between 4° and 20° south latitude. During periods of strong upwelling the average flux out of the ocean exceeded 10 moles of CO₂ per square meter per year. During periods of weaker upwelling and high productivity the CO₂ evasion rate was near 2.5 mol/m²/yr. The average annual fluxes exceed 5 mol/m²/yr. These findings are in sharp contrast to results obtained in mid-latitude upwelling systems along the west coast of North America where the average air–sea CO₂ flux is low and can often be from the atmosphere into the ocean. In the Peruvian upwelling system there are several likely factors that contribute to sea surface pCO₂ levels that are well above those of the atmosphere in spite of elevated primary productivity: (1) the upwelling source waters contain little pre-formed nitrate and are affected by denitrification, (2) iron limitation of primary production enhanced by offshore upwelling driven by the curl of the wind stress and (3) rapid sea surface warming. The combined carbon, nutrient and oxygen dynamics of this region make it a candidate site for studies of global change.     

fCO2 variability at the CARIACO tropical coastal upwelling time series station

Monthly seawater pH and alkalinity measurements were collected between January 1996 and December 2000 at 10°30′N, 64°40′W as part of the CARIACO (CArbon Retention In A Colored Ocean) oceanographic time series. One key objective of CARIACO is to study temporal variability in Total CO₂ (TCO₂) concentrations and CO₂ fugacity (fCO₂) at this tropical coastal wind-driven upwelling site. Between 1996 and 2000, the difference between atmospheric and surface ocean CO₂ concentrations ranged from about − 64.3 to + 62.3 μatm. Physical and biochemical factors, specifically upwelling, temperature, primary production, and TCO₂ concentrations interacted to control temporal variations in fCO₂. Air–sea CO₂ fluxes were typically depressed (0 to + 10 mmol C m^{− 2} day^{− 1}) in the first few months of the year during upwelling. Fluxes were higher during June–November (+ 10 to 20 mmol C m^{− 2} day^{− 1}). Fluxes were generally independent of the slight changes in salinity normally seen at the station, but low positive flux values were seen in the second half of 1999 during a period of anomalously heavy rains and land-derived runoff. During the 5 years of monthly data examined, only two episodes of negative air–sea CO₂ flux were observed. These occurred during short but intense upwelling events in March 1997 (−10 mmol C m^{− 2} day^{− 1}) and March 1998 (− 50 mmol C m^{− 2} day^{− 1}). Therefore, the Cariaco Basin generally acted as a source of CO₂ to the atmosphere in spite of primary productivity in excess of between 300 and 600 g C m^{− 2} year^{− 1}.     

Uptake of atmospheric carbon dioxide in Arctic shelf seas: evaluation of the relative importance of processes that influence pCO2 in water transported over the Bering–Chukchi Sea shelf

The uptake of atmospheric carbon dioxide in the water transported over the Bering–Chukchi shelves has been assessed from the change in carbon-related chemical constituents. The calculated uptake of atmospheric CO₂ from the time that the water enters the Bering Sea shelf until it reaches the northern Chukchi Sea shelf slope (1 year) was estimated to be 86±22 g C m⁻² in the upper 100 m. Combining the average uptake per m³ with a volume flow of 0.83×10⁶ m³ s⁻¹ through the Bering Strait yields a flux of 22×10¹² g C year⁻¹. We have also estimated the relative contribution from cooling, biology, freshening, CaCO₃ dissolution, and denitrification for the modification of the seawater pCO₂ over the shelf. The latter three had negligible impact on pCO₂ compared to biology and cooling. Biology was found to be almost twice as important as cooling for lowering the pCO₂ in the water on the Bering–Chukchi shelves. Those results were compared with earlier surveys made in the Barents Sea, where the uptake of atmospheric CO₂ was about half that estimated in the Bering–Chukchi Seas. Cooling and biology were of nearly equal significance in the Barents Sea in driving the flux of CO₂ into the ocean. The differences between the two regions are discussed. The loss of inorganic carbon due to primary production was estimated from the change in phosphate concentration in the water column. A larger loss of nitrate relative to phosphate compared to the classical ΔN/ΔP ratio of 16 was found. This excess loss was about 30% of the initial nitrate concentration and could possibly be explained by denitrification in the sediment of the Bering and Chukchi Seas.     

Dynamics of dissolved organic carbon in the northwestern Indian Ocean

We report here the non-conservative behaviour of DOC in the northwestern Indian Ocean by studying this parameter together with other carbon and nitrogen components. This contrasts with earlier reports of conservative behaviour. Concentrations of DOC, 3–4 times higher than those reported earlier, were found to decrease northward from the equator. Total carbon dioxide (TCO₂) increases in proportion of the oxygen utilized, thus revealing the dominant biological role in the carbon turnover. The CO₂ added through dissolution of biogenic debris is found to decrease southward, in general. Decomposition of organic material contributes at least 64% to the CO₂ addition that increases southward, the rest being from dissolution of skeletal material. Evidence is provided for the utilization of oxygen and nitrate for DOC oxidative decomposition. Accumulation of DOC without its complete oxidation to CO₂ could be the main reason for the TCO₂ decrease in southern Arabian Sea. Relationships of DOC with nitrification and denitrification processes show that the microbial population plays a major role in regulating the DOC contents in the seawater of this region. Consumption/decomposition by denitrifying bacteria and other micro-organisms responsible for nitrogen cycling in the sea are found to be intimately related to the DOC dynamics and are responsible for decreased DOC concentrations in the north. DOC accumulation in the southern Arabian Sea seems to facilitate bacterio-particulate aggregate formation and consequent nitrification, which results in excess nitrate. Application of a one-dimensional advection-diffusion model to the present data set provides evidence for the non-conservative nature of DOC in the Arabian Sea.     

Daily variability of dissolved inorganic radiocarbon at three sites in the surface ocean

We report radiocarbon measurements of dissolved inorganic carbon (DIC) in surface water samples collected daily during cruises to the central North Pacific, the Sargasso Sea and the Southern Ocean. The ranges of Δ¹⁴C measurements for each cruise (11–30‰) were larger than the total uncertainty (7.8‰, 2-sigma) of the measurements. The variability is attributed to changes in the upper water mass that took place at each site over a two to four week period. These results indicate that variability of surface Δ¹⁴C values is larger than the analytical precision, because of patchiness that exists in the DIC Δ¹⁴C signature of the surface ocean. This additional variability can affect estimates of geochemical parameters such as the air–sea CO₂ exchange rate using radiocarbon.     

Annual cycle of fCO2 under sea-ice and in open water in Prydz Bay, East Antarctica

The annual cycle of dissolved nutrients and the fugacity of CO₂ (fCO₂), calculated from the concentration of dissolved inorganic carbon (DIC) and pH, was studied over a 14-month long period (December 1993 to February 1995) at a site in Prydz Bay near Davis Station, Vestfold Hills, East Antarctica. Significant spring decreases in fCO₂ began under the sea-ice in mid-October, when both water column and sea-ice algal activity resulted in the removal of nutrients and DIC and increased pH. Minimum fCO₂ (<100 μatm) and lowest nutrient and DIC concentrations occurred in December and January. The low summer fCO₂ values were clearly the result of biological activity. The seasonal depletion of dissolved nitrate reached 85% in mid-summer when chlorophyll-a concentrations exceeded 15 mg m⁻³. Oceanic uptake of carbon dioxide from the atmosphere, calculated from the fugacity difference and daily wind speeds, averaged more than 30 mmol m⁻² day⁻¹ during the summer ice-free period. This exchange replaced approximately half of the DIC consumed by biological activity. Apparent nutrient utilisation ratios (C/N/P) were close to Redfield values. In autumn fCO₂ began to rise, continuing slowly well into winter, and reaching a maximum close to modern atmospheric values between July and September. This increase can be attributed to a combination of local remineralisation of organic carbon in the water column and the steady increase in the mixing depth of the water column. At first glance, this suggests that air–sea equilibration occurred in winter despite the sea-ice cover, perhaps by horizontal circulation from regions outside the pack ice, or through openings in the ice. However, the persistent 15 to 20% undersaturation of dissolved oxygen throughout the winter suggests an alternate explanation. The late winter fCO₂ level may represent a characteristic established by global circulation, so that as a result of increasing atmospheric CO₂ concentrations, these Antarctic waters are in transition from being a winter-time source of CO₂ to the atmosphere to becoming a sink. Our fCO₂ observations emphasize the need to address seasonal variations in assessing Antarctic contributions to the oceanic control of atmospheric CO₂.     

The Western North Pacific Playing a Key Role in Global Biogeochemical Fluxes

The oceanic biogeochemical fluxes in the North Pacific, especially its northwestern part, are discussed to prove their importance on a global scale. First, the air-sea exchange processes of chemical substances are considered quantitatively. The topics discussed are sea salt particles transported to land, sporadic transport of soil dust to the ocean and its role in the marine ecosystem, the larger gas transfer velocity of CO₂ indicating the effect of bubbles, and DMS and greenhouse gases other than CO₂. Next, chemical tracers are utilized to reveal the water circulation systems in the region, which are the Pacific Deep Water including its vertical eddy diffusivity, the North Pacific Intermediate Water and the Japan Sea Deep Water. Thirdly, the particulate transport process of chemical substances through the water column is clarified by analyzing the distribution of insoluble radionuclides and the results obtained from sediment trap experiments. Fourthly, the northern North Pacific is characterized by stating the site decomposing organic matter and Si playing a key role in the marine ecosystem. Both are induced by the upwelled Pacific Deep Water. Fifthly, the oceanic CO₂ system related to global warming is presented by clarifying the distribution of anthropogenic CO₂ in the western North Pacific, and roles of the upwelled Pacific Deep Water and the continental shelf zone in the absorption of atmospheric CO₂. Finally, Mn and other chemical substances in sediments are discussed as recorders of the early diagenesis and indicators of low biological productivity during glacial ages in the northwestern North Pacific. It is concluded that the western North Pacific is characterized mainly by the Pacific Deep Water bringing nutrients to the northern North Pacific, located at the exit of the global deep water circulation and, therefore, the region plays a key role in the global biogeochemical fluxes. This revised version was published online in August 2006 with corrections to the Cover Date.