Ludger Mintrop

At-sea intercomparison of two newly designed underway pCO2 systems — encouraging results

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

The international at-sea intercomparison of fCO2 systems during the R/V Meteor Cruise 36/1 in the North Atlantic Ocean

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.

On the penetration of anthropogenic CO2 into the North Atlantic Ocean

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.

Mixing analysis of nutrients, oxygen and inorganic carbon in the Canary Islands region

Abstract We show the distribution of nutrients, oxygen, total dissolved inorganic carbon ( C T ) and total alkalinity ( A T ) 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, A T and C T , 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.

The carbon dioxide system in the northwestern Indian Ocean during south–west monsoon

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.

The International Intercomparison Exercise of Underway fCo2 Systems During the R/V Meteor Cruise 36/1 in the North Atlantic Ocean

Measurements of the fugacity of carbon dioxide (fCO2) in surface seawater are an important part of studies of the global carbon cycle and its anthropogenic perturbation. An important step toward the thorough interpretation of the vast amount of available fCO2 data is the establishment of a database system that would make sure measurements more widely available for use in understanding the basin- and global-scale distribution of fCO2 and its influence on the oceanic uptake of anthropogenic CO2. Such an effort, however, is based on knowledge of data sets from different laboratories. Currently, however, there is not much known about this subject.