Description: The partial pressure of CO2 (pCO2) was measured during the 1995 South-West Monsoon in the Arabian Sea. The Arabian Sea was characterized throughout by a moderate supersaturation of 12–30 µatm. The stable atmospheric pCO2 level was around 345 µatm. An extreme supersaturation was found in areas of coastal upwelling off the Omani coast with pCO2 peak values in surface waters of 750 µatm. Such two-fold saturation (218%) is rarely found elsewhere in open ocean environments. We also encountered cold upwelled water 300 nm off the Omani coast in the region of Ekman pumping, which was also characterized by a strongly elevated seawater pCO2 of up to 525 µatm. Due to the strong monsoonal wind forcing the Arabian Sea as a whole and the areas of upwelling in particular represent a significant source of atmospheric CO2 with flux densities from around 2 mmol m−2 d−1 in the open ocean to 119 mmol m−2 d−1 in coastal upwelling. Local air masses passing the area of coastal upwelling showed increasing CO2 concentrations, which are consistent with such strong emissions.

Description: The penetration of anthropogenic or “excess” CO2 into the North Atlantic Ocean was studied along WOCE‐WHP section A2 from 49°N/11°W to 43°N/49°W using hydrographic data obtained during the METEOR cruise 30–2 in October/November 1994. A backcalculation technique based on measurements of temperature, salinity, oxygen, alkalinity, and total dissolved inorganic carbon was applied to identify the excess CO2. Everywhere along the transect surface water contained almost its full component of anthropogenic CO2 ( ∼62 μmol kg−1). Furthermore, anthropogenic CO2 has penetrated through the entire water column in the western basin of the North Atlantic Ocean. Even in the deepest waters (5000 m) of the western basin a mean value of 10.4 μmol kg−1 excess CO2 was calculated. The maximum penetration depth of excess CO2 in the eastern basin of the North Atlantic Ocean was ∼3500 m with values falling below 5 μmol kg−1 in greater depths. These results compare well with distributions of carbontetrachloride. They are also in agreement with the current understanding of the role of the “global ocean conveyor belt” for the uptake of anthropogenic CO2 into the deep ocean.

Description: Data on the carbonate system of the Northwestern Indian Ocean obtained on a cruise of F.S. Meteor during SW monsoon in July/August 1995 were compared with those of George et al. [George, M.D., Kumar, M.D., Naqvi, S.W.A., Banerjee, S., Narvekar, P.V., de Sousa, S.N., Jayakumar, D.A., 1994. A study of the carbon dioxide system in the northern Indian Ocean during premonsoon. Mar. Chem. 47, 243–254] collected during intermonsoon. In general, deep water values agreed well between the two expeditions. Surface waters, however, showed a substantial increase in dissolved inorganic carbon (CT) in the coastal regions due to strong upwelling in the SW monsoon. This was also accompanied by very high CO2 partial pressures in surface waters. The north–south gradients in vertical profiles of the measured parameters in the Arabian Sea are discussed by comparing profiles from the oligotrophic equatorial region with those from the highly productive central Arabian Sea. The effect of denitrification on regenerated CT and AT is minor, with contributions of 〈9 and 〈8 μmol kg−1, respectively, to the total amount regenerated also utilizing oxygen. The dissolution of biogenic carbonates is discussed; different approaches to define the depth, where the dissolution starts (lysocline(s), carbonate critical depth (CCrD)), are compared together with the calculation of saturation depth from carbonate concentrations. It is shown, that small differences in measured CT and AT (found between our data and those measured during GEOSECS) and different calculation approaches to the CO2 system (different dissociation constants for species involved and taking into account phosphate and silicate concentrations) can produce pronounced differences in the calculated saturation depths. However, CT and AT data suggest substantial dissolution of biogenic carbonate in the water column even above the calcite lysocline, irrespective of the procedures followed to calculate this horizon.

Description: We show the distribution of nutrients, oxygen, total dissolved inorganic carbon (CT) and total alkalinity (AT) along three sections close to the Canary Islands, between 18°W and the African coast during Meteor 37/2 cruise (January 1997). From the thermohaline properties of Eastern North Atlantic Central Water (ENACW), Mediterranean Water (MW), Antarctic Intermediate Water (AAIW) and North Atlantic Deep Water (NADW), a mixing model has been established based on the water mass description. It can explain most of the variabilities found in the distribution of the chemical variables, including the carbon system, and it is validated through the use of conservative chemical variables like ‘NO.’ From nutrients, oxygen, AT and CT, the chemical characterisation of the water masses was performed by calculating the concentration of these variables in the previously defined thermohaline end-members. The relative variation of nutrient concentrations, resulting from the regeneration of organic matter, was estimated. Close to the African shelf-break, a poleward undercurrent conveying as much as a 11% of AAIW was observed only in the southern section (28.5°N). From the chemical and thermohaline properties of the end-members, a comparison with data from other oceanic regions was made in respect to conservative chemical variables (‘NO’). In addition, a north–south gradient in the ventilation pattern of water masses is observed from the residuals of the model.

Description: A coulometrically-based SOMMA system for the determination of total dissolved carbon dioxide (TCO2) in a continuous mode was designed and tested at sea. The new continuous technique approached the same high accuracy and reliability associated with prior discrete TCO2 measurements. During three cruises encompassing more than 19 weeks and 6000 continuous TCO2 measurements none of the three different systems tested exhibited any hardware-related failures. We found that coulometer cell lifetimes can greatly exceed prior expectations with many of the titration cells in the continuous mode remaining accurate for up to 72 h at carbon ages exceeding 50 mg C. We suggest a practical definition based on the CRM analyses for changing coulometer cells in the continuous mode. Systematic deviations of the SOMMA pipette volume from a theoretical temperature dependence were identified both from field data comparisons and pipette calibrations. Hence pipettes should be kept at constant temperature or they must be gravimetrically calibrated over the expected temperature range. Comparison of the continuous TCO2 data together with simultaneously measured additional CO2 system parameters showed that the refitted “Mehrbach” dissociation constants for carbonic acid best-represent fCO2 when calculated from TCO2 and alkalinity over a wide range of sea-surface temperatures and salinities. Some remaining systematic differences of calculated–measured fCO2 of up to 9 μatm likely reflect uncertainty in the temperature-dependence of the “Mehrbach” constants as well as possible uncertainty in the alkalinity–salinity relationship used to estimate alkalinity in the consistency checks.

Description: The ‘International Intercomparison Exercise of fCO2 Systems’ was carried out in 1996 during the R/V Meteor Cruise 36/1 from Bermuda/UK to Gran Canaria/Spain. Nine groups from six countries (Australia, Denmark, France, Germany, Japan, USA) participated in this exercise, bringing together 15 participants with seven underway fugacity of carbon dioxide (fCO2) systems, one discrete fCO2 system, and two underway pH systems, as well as systems for discrete measurement of total alkalinity and total dissolved inorganic carbon. Here, we compare surface seawater fCO2 measured synchronously by all participating instruments. A common infrastructure (seawater and calibration gas supply), different quality checks (performance of calibration procedures for CO2, temperature measurements) and a common procedure for calculation of final fCO2 were provided to reduce the largest possible amount of controllable sources of error. The results show that under such conditions underway measurements of the fCO2 in surface seawater and overlying air can be made to a high degree of agreement (±1 μatm) with a variety of possible equilibrator and system designs. Also, discrete fCO2 measurements can be made in good agreement (±3 μatm) with underway fCO2 data sets. However, even well-designed systems, which are operated without any obvious sign of malfunction, can show significant differences of the order of 10 μatm. Based on our results, no “best choice” for the type of the equilibrator nor specifics on its dimensions and flow rates of seawater and air can be made in regard to the achievable accuracy of the fCO2 system. Measurements of equilibrator temperature do not seem to be made with the required accuracy resulting in significant errors in fCO2 results. Calculation of fCO2 from high-quality total dissolved inorganic carbon (CT) and total alkalinity (AT) measurements does not yield results comparable in accuracy and precision to fCO2 measurements.

Description: Two newly designed underway systems for the measurement of CO2 partial pressure (pCO2) in seawater and the atmosphere are described. Results of an intercomparison experiment carried out in the North Sea are presented. A remarkable agreement between the two simultaneously measured (pCO2) data sets was observed even though the spatial variability in surface pCO2 was high. The average difference of all l -min averages of the seawater pCO2 was as low as 0.15 μatm with a standard deviation of 1.2 μatm indicating that no systematic difference is present. A closer examination of the profiles shows that differences tend to be highest during maxima of the pCO2 gradient (up to 14 μatm/min). The time constants of both systems were estimated from laboratory experiments to 45 s, respectively, 75 s thus quantitatively underlining their capability of a fast response to pCO2 changes

Description: We compare estimates of the anthropogenic CO2 content of seawater samples from the subpolar North Atlantic Ocean calculated on the basis of a back-calculation technique with measurements of the chlorofluorocarbon CFC-11. Estimated anthropogenic CO2 concentrations are in the range 10–80 µmol kg-1, while CFC-11 concentrations cover the full range from below detection limit to 〉 5 pmol kg-1 in waters at atmospheric equilibrium. The majority of the data points show a linear correlation between anthropogenic CO2 concentrations and CFC-11 saturation, which can only be explained by the strongly advective nature of the North Atlantic Ocean. Only deep eastern basin samples deviate from this general observation in that they show still significant concentrations of anthropogenic CO2 where CFC-11 is no longer detectable. In order to remove the influence of the Revelle factor reflected in the anthropogenic CO2 concentrations we have calculated 'excess' pCO2, showing an even tighter linear correlation with atmospheric equilibrium concentrations of CFC-11.

Description: Redfield stoichiometry has proved a robust paradigm for the understanding of biological production and export in the ocean on a long-term and a large-scale basis. However, deviations of carbon and nitrogen uptake ratios from the Redfield ratio have been reported. A comprehensive data set including all carbon and nitrogen pools relevant to biological production in the surface ocean (DIC, DIN, DOC, DON, POC, PON) was used to calculate seasonal new production based on carbon and nitrogen uptake in summer along 20°W in the northeast Atlantic Ocean. The 20°W transect between 30 and 60°N covers different trophic states and seasonal stages of the productive surface layer, including early bloom, bloom, post-bloom and non-bloom situations. The spatial pattern has elements of a seasonal progression. We also calculated exported production, i.e., that part of seasonal new production not accumulated in particulate and dissolved pools, again separately for carbon and nitrogen. The pairs of estimates of `seasonal new production’ and `exported production’ allowed us to calculate the C : N ratios of these quantities. While suspended particulate matter in the mixed layer largely conforms to Redfield stoichiometry, marked deviations were observed in carbon and nitrogen uptake and export with progressing season or nutrient depletion. The spring system was characterized by nitrogen overconsumption and the oligotrophic summer system by a marked carbon overconsumption. The C : N ratios of seasonal new as well as exported production increase from early bloom values of 5–6 to values of 10–16 in the post-bloom/oligotrophic system. The summertime accumulation of nitrogen-poor dissolved organic matter can explain only part of this shift.