Summer and winter air–sea CO2 fluxes in the Southern Ocean

The seasonal variability of the carbon dioxide (CO₂) system in the Southern Ocean, south of 50°S, is analysed from observations obtained in January and August 2000 during OISO cruises conducted in the Indian Antarctic sector. In the seasonal ice zone, SIZ (south of 58°S), surface ocean CO₂ concentrations are well below equilibrium during austral summer. During this season, when sea-ice is not obstructing gas exchange at the air–sea interface, the oceanic CO₂ sink ranges from −2 to −4 mmol/m²/d in the SIZ. In the permanent open ocean zone, POOZ (50–58°S), surface oceanic fugacity fCO₂ increases from summer to winter. The seasonal fCO₂ variations (from 10 to 30 μatm) are relatively low compared to seasonal amplitudes observed in the subtropics or the subantarctic zones. However, these variations in the POOZ are large enough to cross the atmospheric level from summer to winter. Therefore, this region is neither a permanent CO₂ sink nor a permanent CO₂ source. In the POOZ, air–sea CO₂ fluxes calculated from observations are about −1.1 mmol/m²/d in January (a small sink) and 2.5 mmol/m²/d in August (a source). These estimates obtained for only two periods of the year need to be extrapolated on a monthly scale in order to calculate an integrated air–sea CO₂ flux on an annual basis. For doing this, we use a biogeochemical model that creates annual cycles for nitrate, inorganic carbon, total alkalinity and fCO₂. The changing pattern of ocean CO₂ summer sink and winter source is well reproduced by the model. It is controlled mainly by the balance between summer primary production and winter deep vertical mixing. In the POOZ, the annual air–sea CO₂ flux is about −0.5 mol/m²/yr, which is small compared to previous estimates based on oceanic observations but comparable to the small CO₂ sink deduced from atmospheric inverse methods. For reducing the uncertainties attached to the global ocean CO₂ sink south of the Polar Front the regional results presented here should be synthetized with historical and new observations, especially during winter, in other sectors of the Southern Ocean.     

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.     

Surface water carbon dioxide in the southwest Indian sector of the Southern Ocean: a highly variable CO2 source/sink region in summer

Measurements of partial pressure of carbon dioxide (pCO₂), total dissolved inorganic carbon (TCO₂), total alkalinity (TA) and chlorophyll a (Chl a) have been made in surface water in the southwestern Indian sector of the Southern Ocean (20–85°E) in the austral summer (INDIVAT V cruise, January-February 1987). Between Antarctica and Africa, pCO₂ distribution was linked to the oceanic frontal zones and Chi a variations. The pCO₂ spatial structure was very close to that explored in summer 1967 in the same region but the pCO₂ differences between the ocean and the atmosphere were smaller in 1987 than 20 years ago. At all latitudes we found strongly contrasting surface pCO₂ characteristics between eastern (around 80°E) and western (around 25°E) regions; C02 sources were mainly in the west and CO₂ sinks in the east. South of 60°S, the contrast could be due to biological activity. Between 60°S and the Antarctic Polar Front, intensification of upwelling might be responsible for the higher _pCO₂ values in the west.     

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.     

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.     

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}.     

Doubled CO2 impact on subarctic marine carbon cycle: a case study at Ocean Station P

Along with meteorological observations, complementary and systematic oceanographic observations of various physical, biological and chemical parameters have been made at Ocean Station P (OSP) (50°N, 145°W) since the early 1950s. These decadal time scale data have contributed to a better understanding of the physical, biological and chemical processes in the surface layer of the northeastern subarctic region of the Pacific Ocean. These data have demonstrated the importance of the North Pacific in the global carbon cycle and, in particular, the role of biological/chemical processes in the net exchange of CO₂ across the air–sea interface. Although we do not fully comprehend how climatic variations influence marine communities or marine biogeochemistry, previous studies have provided some basic understanding of the mechanisms controlling the seasonal and inter-annual variations of biological and chemical parameters (such as phytoplankton, bacteria, nitrate/ammonium concentration) at OSP, and how they affect the carbon cycling in the subarctic North Pacific. In this study, we investigate how these mechanisms might alter the seasonal variations of these parameters at OSP under a 2XCO₂ condition. We examine these influences using a new biological model calibrated by the climatological data from OSP. For the 2XCO₂ simulation, the biological model is driven off line (i.e., no feedback to the ocean/atmospheric model components) by the climatology plus 2XCO₂−1XCO₂ outputs from a global surface ocean model and the Canadian GCM. Under the 2XCO₂ condition, the upper layer ocean shows an increase in the entrainment rate at the bottom of the mixed layer for OSP during the late autumn and winter seasons, resulting in an increase in the f-ratio. Although there is an overall increase in the primary production (PP) by 3–18%, a decrease in the biomass of small phytoplankton and microzooplankton (due to mesozooplankton grazing) lowers the concentration of dissolved organic matter (DOM) by 4–25%. The model also predicts a significant increase in the concentrations of nitrate and ammonium, and in bacterial production during July and August. Doubling of the atmospheric CO₂ from 330 to 660 ppm forces the marine pCO₂ to increase by about 63%, much of which is driven by an increased flux of CO₂ from the atmosphere to the oceans.     

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.     

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).     

Variability of the partial pressure of CO2 on a daily-to-seasonal time scale in a shallow coastal system affected by intensive aquaculture activities (Bay of Cadiz, SW Iberian Peninsula)

The present study describes the temporal variability of the water fCO₂ as well as the different driving forces controlling this variability, on time scales from daily to seasonal, in the Rio San Pedro, a tidal creek located in a salt marsh area in the Bay of Cadiz (SW Iberian Peninsula). This shallow tidal creek system is affected by effluents of organic matter and nutrients from the surrounding marine fish farms. Continuous pCO₂, salinity and temperature were recorded for four periods of approximately one month, between February and September in 2004.Major processes controlling the CO₂ variability are related to three different time scales. Daily variations in fCO₂ are controlled by tidal advection and mixing of the water from within the creek and the seawater that enters from the Bay of Cadiz. Significant cyclical variations of the fCO₂ have been observed with the maximum values occurring at low tide. On a fortnightly time scale, the amplitude of the daily variability of fCO₂ is modulated by the variations in the residence time of the water within the creek, which are related to the spring–neap tide sequence.On a third time scale, high seasonal variability is observed for the temperature, salinity and fCO₂. Maximum and minimum values for fCO₂ were 380 µatm and 3760 µatm for February and July respectively. Data suggest that seasonal variability is related to the seasonal variability in discharges from the fish farm and to the increase with temperature of organic matter respiratory processes in the tidal creek. The fCO₂ values observed are in the same range as several highly polluted European estuaries or waters surrounding mangrove forests. From the air–water CO₂ flux computed, it can be concluded that the Rio San Pedro acts as a source of CO₂ to the atmosphere throughout the year, with the summer accounting for the higher average monthly flux.     

Increase of anthropogenic CO2 in the Pacific Ocean over the last two decades

The multiple-parameter linear regression method (Monitoring global ocean carbon inventories. Ocean Observing System Development Panel, Texas A&M University, College Station, TX, 1995, 54pp; Global Biogeochem. Cycles 13 (1999) 179) is used to compare inorganic carbon data from the GEOSECS CO₂ survey in the Pacific Ocean in 1973 to the WOCE/JGOFS global CO₂ survey in the 1990s. A model of total dissolved inorganic carbon (DIC) as a function of five variables (AOU, θ, S, Si, and PO₄) has been developed from the recent CO₂ survey data (namely CGC91 and CGC96) in the Pacific Ocean. After correcting for a systematic DIC offset of −30.3±7 μmol kg⁻¹ from the GEOSECS data, the residual DIC based on this model as computed from GEOSECS data has been used to estimate the anthropogenic CO₂ penetration in the Pacific Ocean. In the Northeast Pacific, we obtained an increase of CO₂ of 21.3±7.9 mol m⁻² over the period from GEOSECS in 1973 to CGC91 in 1991. This gives a mean anthropogenic CO₂ uptake rate of 1.3±0.5 mol m⁻² yr⁻¹ over this 17 year time period. In the South Pacific, north of 50°S between 180° and 120°W region, the integrated anthropogenic CO₂ inventory is estimated to be 19.7±5.7 mol m⁻² over the period from GEOSECS in 1974 to CGC96 in 1996. The equivalent mean CO₂ uptake rate is estimated to be 0.9±0.3 mol m⁻² yr⁻¹ over the 22 years. These results are compared with the isopycnal method (Nature 396 (1998) 560) to estimate the anthropogenic CO₂ signal in the Northeast Pacific (30°N, 152°W) at the crossover region between CGC91 and GEOSECS. The results of the isopycnal method are consistent with those derived from the MLR method. Both methods show an increase in anthropogenic CO₂ inventory in the ocean over two decades that is consistent with the increase expected if the ocean uptake has kept pace with the atmospheric CO₂ increase.     

Distribution of the CO2 partial pressure along an Atlantic meridional transect

Atmospheric and oceanic pCO₂ were measured continuously along an Atlantic Meridional transect (50°N–50°S) in September–October 1995 and 1996 (U.K. to the Falklands Islands) and in April–May 1996 (Falklands Islands to the UK). The Atlantic ocean was a net sink for atmospheric CO₂ for all 3 transects. The largest sinks were located at high latitudes, in regions of high wind speed, where strong CO₂ undersaturations, associated with high biological activity, were observed. In these regions the partial pressure difference between the ocean and the atmosphere reached −110 μatm. A CO₂ source occurred in the equatorial region between 0° and 10°S, where ΔpCO₂ of up to 40 μatm was found. Another source was in the northern subtropical gyre where its extension varied according to the season. Along the whole transect the October cruises exhibited similar pCO₂ distributions suggesting a dominance of the seasonal variability and small year to year changes.     

A seasonal carbon budget for the sub-Antarctic Ocean, South of Australia

Changes from winter (July) to summer (February) in mixed layer carbon tracers and nutrients measured in the sub-Antarctic zone (SAZ), south of Australia, were used to derive a seasonal carbon budget. The region showed a strong winter to summer decrease in dissolved inorganic carbon (DIC;  45 µmol/kg) and fugacity of carbon dioxide (fCO₂;  25 µatm), and an increase in stable carbon isotopic composition of DIC (δ¹³C_DIC;  0.5‰), based on data collected between November 1997 and July 1999.The observed mixed layer changes are due to a combination of ocean mixing, air–sea exchange of CO₂, and biological carbon production and export. After correction for mixing, we find that DIC decreases by up to 42 ± 3 µmol/kg from winter (July) to summer (February), with δ¹³C_DIC enriched by up to 0.45 ± 0.05‰ for the same period. The enrichment of δ¹³C_DIC between winter and summer is due to the preferential uptake of ¹²CO₂ by marine phytoplankton during photosynthesis. Biological processes dominate the seasonal carbon budget (≈ 80%), while air–sea exchange of CO₂ (≈ 10%) and mixing (≈ 10%) have smaller effects. We found the seasonal amplitude of fCO₂ to be about half that of a study undertaken during 1991–1995 [Metzl, N., Tilbrook, B. and Poisson, A., 1999. The annual fCO₂ cycle and the air–sea CO₂ flux in the sub-Antarctic Ocean. Tellus Series B—Chemical and Physical Meteorology, 51(4): 849–861.] for the same region, indicating that SAZ may undergo significant inter-annual variations in surface fCO₂. The seasonal DIC depletion implies a minimum biological carbon export of 3400 mmol C/ m² from July to February. A comparison with nutrient changes indicates that organic carbon export occurs close to Redfield values (ΔP:ΔN:ΔC = 1:16:119). Extrapolating our estimates to the circumpolar sub-Antarctic Ocean implies a minimum organic carbon export of 0.65 GtC from the July to February period, about 5–7% of estimates of global export flux. Our estimate for biological carbon export is an order of magnitude greater than anthropogenic CO₂ uptake in the same region and suggests that changes in biological export in the region may have large implications for future CO₂ uptake by the ocean.     

Spatial variability in the partial pressures of CO2 in the northern Bering and Chukchi seas

In the summers of 1999 and 2003, the 1st and 2nd Chinese National Arctic Research Expeditions measured the partial pressure of CO₂ in the air and surface waters (pCO₂) of the Bering Sea and the western Arctic Ocean. The lowest pCO₂ values were found in continental shelf waters, increased values over the Bering Sea shelf slope, and the highest values in the waters of the Bering Abyssal Plain (BAP) and the Canadian Basin. These differences arise from a combination of various source waters, biological uptake, and seasonal warming. The Chukchi Sea was found to be a carbon dioxide sink, a result of the increased open water due to rapid sea-ice melting, high primary production over the shelf and in marginal ice zones (MIZ), and transport of low pCO₂ waters from the Bering Sea. As a consequence of differences in inflow water masses, relatively low pCO₂ concentrations occurred in the Anadyr waters that dominate the western Bering Strait, and relatively high values in the waters of the Alaskan Coastal Current (ACC) in the eastern strait. The generally lower pCO₂ values found in mid-August compared to at the end of July in the Bering Strait region (66–69°N) are attributed to the presence of phytoplankton blooms. In August, higher pCO₂ than in July between 68.5 and 69°N along 169°W was associated with higher sea-surface temperatures (SST), possibly as an influence of the ACC. In August in the MIZ, pCO₂ was observed to increase along with the temperature, indicating that SST plays an important role when the pack ice melts and recedes.     

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.     

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.     

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.     

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.     

Temperature dependence of CO2 fugacity in seawater

Ideally, the correction of the measured CO₂ fugacity (fCO₂) at temperature T_m to fCO₂ at the in-situ temperature T_in should be made by using at least 2 known parameters (pH-A_T, C_T-A_T,…) and the reliable constants for carbonic acid. In practice however, a measured CO₂ property pair is not always available. When fCO₂ is measured alone, one must make an estimate of the effect of temperature on seawater fCO₂ from the accurate knowledge of seawater salinity and temperature and the approximate knowledge of the carbonate parameters. In this paper we present an empirical relationship that can be used to estimate the effect of temperature on fCO₂. The equation is of the form:

ƒCO_2[t] − ƒCO_2[20]=A + Bt + Ct² + Dt³ + Et⁴

where fCO_2[t] and fCO_2[20] represent fCO₂ at temperatures t°C and 20°C, respectively; the parameters A, B, etc. are functions of the ratio X = C_T/A_T:

E = e₀ + e₁X + e₂X²ln(X) + e₃exp(X) + e₄/ln(X)

where the parameters a_i, b_i, etc. are functions of salinity.The 25-parameter equation is fitted by the values of fCO₂ calculated using the constants of Goyet and Poisson (1989), when X varies from 0.8 to 1.0, t varies from −1dgC to 40°C, and S varies from 30 to 40. For T_m - T_in within ± 10°C, direct measurements of fCO₂ as a function of the temperature (from −I to 30°C verify this equation within less than ±5 μatm.