ALBERT

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: 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: Temporal trends in oceanic dissolved inorganic carbon (DIC) and δ13C-DIC were reconstructed along five isopycnals in the upper 1000 m of the North Atlantic Ocean using a back-calculation approach. The mean anthropogenic DIC increase was 1.21 ± 0.07 μmol kg−1 yr−1 and the mean 13C decrease was −0.026 ± 0.002‰ yr−1, both in good agreement with the results from previous studies. The observed δ13C-DIC perturbation ratio is −0.024 ± 0.003‰ (μmol kg−1)−1. Our results indicate that the North Atlantic is able to maintain equilibrium with the anthropogenic perturbation for DIC and follows it with decadal time lag for δ13C. A CFC-calibrated one-dimensional isopycnal advection-diffusion model is used to evaluate temporal DIC and δ13C trends and perturbation ratios of the reconstructions. We investigate the time history of the air-sea CO2 and 13C disequilibria in the North Atlantic and discuss the importance of physical and biological processes in maintaining them. We find evidence that the North Atlantic Ocean is characterized by enhanced uptake of anthropogenic CO2. Also, we use the model to examine how the time rate of change of δ13C depends on changes in the temporal evolution of δ13C in the atmosphere. The model evolution explains the curious result that the time rate of change of surface water δ13C in the North Atlantic Ocean can exceed that observed concurrently in the atmosphere. Finally we introduce a powerful way of estimating the global air-sea pCO2 disequilibrium based on the oceanic δ13C-DIC perturbation ratio.

Description: The results of 1 year of automated pCO2 measurements in 2002/2003 onboard the car carrier M/V Falstaff are presented and analyzed with regard to the driving forces that change the seawater pCO2 in the midlatitude North Atlantic Ocean. The pCO2 in surface seawater is controlled by thermodynamics, biology, air-sea gas exchange, and physical mixing. Here we estimate the effects on the annual cycle of pCO2 and relate this property to parameters like SST, nitrate, and chlorophyll. On the basis of the amplitude in seawater pCO2 for all 4° × 5° grid boxes, this region can be separated into an eastern and western basin. The annual pCO2 cycle in the eastern basin (10°W–35°W) is less variable, which can be related to the two counteracting effects of temperature and biology; air-sea gas exchange plays a minor role when using climatological MLD. In the western basin (36°W–70°W) the pCO2 amplitude is more variable and strongly follows the thermodynamic forcing, since the biological forcing (as derived from nitrate concentrations) is decreased. Biology and air-sea exchange strongly depend on the MLD and therefore also include physical mixing effects. The pCO2 data of the analyzed region between 34°N and 52°N compare well to the Takahashi et al. [2002] climatology except for regions north of 45°N during the wintertime where the bias is significant.

Description: Seawater was sampled from different depths in the North Atlantic Ocean (Canary Islands region) and distributed among three different labs for the determination of titration alkalinity. Analysis was performed by potentiometric methods, involving titration in a closed cell, titration in an open cell and a two end-point acid addition method. The precision, which is the sample reproducibility taken from the mean standard deviation for replicate measurements, was between 0.45 and 0.90 µmol kg(-1) for the individual labs. Accuracy, here taken as the deviation for the values of a lab from the mean of all three, was mostly below 1 µmol kg(-1) and never exceeded 0.1% of the sample value. Mean standard deviation for all labs and all samples was 0.87 µmol kg(-1), once the individual methods were calibrated using certified reference material (CRM). Without CRM calibration, the mean standard deviation would increase to 2.8 µmol k(-1). The conclusion is that current high precision methods for alkalinity measurements calibrated with CRMs are able to reach similar accuracy as the measurement of total dissolved inorganic carbon by coulometry and therefore allow for the precise determination of the oceanic carbon dioxide system by using the two measured parameters.

Description: Redfield ratios of remineralization are calculated based on chemical data analysis on isopycnal surfaces. The concentrations of dissolved inorganic carbon used in this study were corrected for the anthropogenic CO2 content as estimated with a back-calculation technique. The corrections increased the apparent carbon remineralization by 25-30%, thus proving important for the reliable estimation of Redfield carbon ratios in the presence of anthropogenic CO2. Best estimates from this study largely confirm the more recently published Redfield ratios of remineralization. The following results were obtained for the latitude range 3-41°N along 20-29°W in the Northeast Atlantic Ocean: Corg: P ratio = 123 ± 10; Corg : N ratio = 7.2 ± 0.8; -O2 :Corg ratio = 1.34 ± 0.06; -O2 : P ratio = 165 ± 15; N: P ratio = 17.5 ± 2.0. These ratios are in close agreement with the average composition of phytoplankton and represent respiration of organic matter consisting on average of 52% protein, 36% polysaccharide, and 12% lipid.

Description: A newly designed system for high quality discrete spectrophotometric measurements of pHT using a low-cost CCD detector is described. Considerations and requirements for the choice of spectrophotometers with a CCD detector instead of scanning spectrophotometers with photomultiplier detector are elucidated. The presented system is evaluated in the laboratory for system accuracy and short-term precision and at-sea for long-term precision and at-sea capability. Derived system characteristics are a (1s) short-term precision of ± 0.0012 pH units and a (1s) long-term precision at-sea of ± 0.0032 pH units based on Certified Reference Materials (CRM). Such long-term precision is equivalent to a deviation of ± 1.1 to 2.2 µmol kg-1 in total dissolved inorganic carbon (TCO2) and ± 1.4 to 2.1 µmol kg-1 in total alkalinity (TA), depending on temperature and the TCO2/TA ratio. Over-determination of the CO2 system (TCO2, TA, pHT) from surface-to-deep water profiles support the accuracy and precision assessment in comparison to earlier data. With careful design and testing low-cost CCD spectrophotometers can be used for high accuracy pH-measurements.

Description: Recent measurements and model studies have consistently identified a decreasing trend in the concentration of dissolved O2 in the ocean over the last several decades. This trend has important implications for our understanding of anthropogenic climate change. First, the observed oceanic oxygen changes may be a signal of the beginning of a reorganization of large-scale ocean circulation in response to anthropogenic radiative forcing. Second, the repartitioning of oxygen between the ocean and the atmosphere requires a revision of the current atmospheric carbon budget and the estimates of the terrestrial and oceanic carbon sinks as calculated by the Intergovernmental Panel on Climate Change (IPCC) from measurements of atmospheric O2/N2.