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: 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: 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: 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.