ALBERT

Description: Highly accurate and precise measurements of marine carbon components are required in the study of the marine carbon cycle, particularly when investigating the causes for its variability from seasonal to interannual timescales. This is especially true in the investigation of the consequences of anthropogenic influences. The analysis of any marine carbon component requires elaborate instrumentation, most of which is currently used onboard ships, either in manual or automated mode. Technological developments result in more and more instruments that have sufficient long-term reliability so that they can be deployed on commercial ships, surface moorings, and buoys, whilst the great technological and operational challenges mean that only few sensors have been developed that can be used for sub-surface in situ measurements on floats, robots, or gliders. There is a special need for autonomous instruments and sensors that are able to measure a combination of different components, in order to increase the spatial and temporal coverage of marine carbon data. This paper describes analytical techniques used for the measurement of the marine dissolved carbon components, both inorganic and organic: the fugacity of CO2, total dissolved inorganic carbon, pH, alkalinity, and dissolved organic carbon. By pointing out advantages, disadvantages, and/or challenges of the techniques employed in the analysis of each component, we aim to aid non-carbon marine scientists, sensor developers and technologists, in the decision of which challenges to address in further development.

Description: Highly accurate and precise measurements of marine carbon components are required in the study of the marine carbon cycle, particularly when investigating the causes for its variability from seasonal to interannual timescales. This is especially true in the investigation of the consequences of anthropogenic influences. The analysis of any component requires elaborate instrumentation, most of which is currently used onboard ships, either in manual mode or autonomous mode. Technological developments result in more and more instruments that have long-term reliability so that they can be deployed on surface moorings and buoys, whilst the great technological and operational challenges mean that only few sensors have been developed that can be used for sub-surface in situ measurements on floats, robots, or gliders. There is a special need for autonomous instruments and sensors that are able to measure a combination of different components, in order to increase the spatial and temporal coverage of marine carbon data. This paper describes analytical techniques used for the detection of the marine dissolved carbon components, both inorganic and organic: the fugacity of CO2, total dissolved inorganic carbon, pH, alkalinity, and dissolved organic carbon. By pointing out advantages, disadvantages, and challenges of the techniques employed in the analysis of each component, we aim to aid non-carbon marine scientists, sensor developers and technologists, in the decision where to tackle the challenges of further development.

Description: In the CARINA project, a new dataset with many previously unpublished hydrographic data from the Atlantic, Arctic and Southern Ocean was assembled and subjected to careful quality control (QC) procedures. In this paper, we present the dissolved oxygen measurements in the Atlantic region of the database and describe in detail the secondary QC procedures that aim to ensure optimal consistency between different cruises in order to permit studies of long-term change. The secondary QC is based on a cross-over analysis, i.e. the comparison of deep ocean data at places that were sampled by different cruises at different times. Initial adjustments to the individual cruises were then determined by an inverse procedure that computes a set of adjustments that requires the minimum amount of adjustment and at the same time reduces the offsets in an optimal manner. The initial adjustments were then reviewed by the CARINA members, and only those that passed the following two criteria were adopted: (i) the region not subject to substantial temporal variability, and (ii) the adjustment must be based on at least three stations from each cruise. No adjustment was recommended for cruises that did not fit these criteria. The final CARINA-Oxygen database has 113005 oxygen samples from 9535 stations obtained during 98 cruises covering three decades. The sampling density of the oxygen data is particularly good in the North Atlantic north of about 40° N especially after 1987. In contrast, the sample density in the South Atlantic is much lower. Some cruises appear to have poor data quality, and were subsequently omitted from the adjusted data base. Of the data included in the adjusted data base, 20% were adjusted with a mean adjustment of 2%.

Description: In the CARINA (Carbon dioxide in the Atlantic Ocean) project, a new dataset with many previously unpublished hydrographic data from the Atlantic, Arctic and Southern Ocean was assembled and subjected to careful quality control (QC) procedures. Here, we present the dissolved oxygen measurements in the Atlantic region of the dataset and describe in detail the secondary QC procedures that aim to ensure that the data are internally consistent. This is achieved by a cross-over analysis, i.e. the comparison of deep ocean data at places that were sampled by different cruises at different times. Initial adjustments to the individual cruises were then determined by an inverse procedure that computes a set of adjustments that requires the minimum amount of adjustment and at the same time reduces the offsets in an optimal manner. The initial adjustments were then reviewed by the CARINA members, and only those that passed the following two criteria were adopted: (i) the region is not subject to substantial temporal variability, and (ii) the adjustment must be based on at least three stations from each cruise. No adjustment was recommended for cruises that did not fit these criteria. The final CARINA-Oxygen dataset has 103414 oxygen samples from 9491 stations obtained during 98 cruises covering three decades. The sampling density of the oxygen data is particularly good in the North Atlantic north of about 40° N especially after 1987. In contrast, the sample density in the South Atlantic is much lower. Some cruises appear to have poor data quality, and were subsequently omitted from the adjusted dataset. Of the data included in the adjusted dataset, 20% were adjusted with a mean adjustment of 2%. Due to the achieved internal consistency, the resulting product is well suited to produce an improved climatology or to study long-term changes in the oxygen content of the ocean. However, the adjusted dataset is not necessarily better suited than the unadjusted data to address questions that require a high level of accuracy, such as the computation of the saturation state.

Description: Water column data of carbon and carbon-relevant hydrographic and hydrochemical parameters from 188 previously non-publicly available cruise data sets in the Arctic, Atlantic and Southern Ocean have been retrieved and merged into a new database: CARINA (CARbon IN the Atlantic). The data have gone through rigorous quality control procedures to assure the highest possible quality and consistency. The data for the pertinent parameters in the CARINA database were objectively examined in order to quantify systematic differences in the reported values, i.e. secondary quality control. Systematic biases found in the data have been corrected in the data products, i.e. three merged data files with measured, calculated and interpolated data for each of the three CARINA regions, i.e. Arctic, Atlantic and Southern Ocean. Ninety-eight of the cruises in the CARINA database were conducted in the Atlantic Ocean, defined here as the region south of the Greenland-Iceland-Scotland Ridge and north of about 30° S. Here we present an overview of the Atlantic Ocean synthesis of the CARINA data and the adjustments that were applied to the data product. We also report details of the secondary QC for salinity for this data set. Procedures of quality control – including crossover analysis between stations and inversion analysis of all crossover data – are briefly described. Adjustments to salinity measurements were applied to the data from 10 cruises in the Atlantic Ocean region. Based on our analysis we estimate the internal accuracy of the CARINA-ATL salinity data to be 4.1 ppm. With these adjustments the CARINA database is consistent both internally as well as with GLODAP data, an oceanographic data set based on the World Hydrographic Program in the 1990s (Key et al., 2004), and is now suitable for accurate assessments of, for example, oceanic carbon inventories and uptake rates and for model validation.

Description: Here we present monthly, basin-wide maps of the partial pressure of carbon dioxide (pCO2) for the North Atlantic on a 1° latitude by 1° longitude grid for years 2004 through 2006 inclusive, constructed using a neural network technique which reconstructs the non-linear relationships between 3 biogeochemical parameters and marine pCO2. A self organizing map (SOM) neural network has been trained using the SeaWiFS-MODIS chlorophyll a concentration, the NCEP/NCAR reanalysis sea surface temperature, and the FOAM mixed layer depth. 389 000 such triplets were used. The trained SOM was labelled with 137 000 underway pCO2 measurements collected in situ during 2004, 2005 and 2006 in the North Atlantic, which span the range of 208 and 437 μatm. The root mean square (RMS) deviation of the neural network fits from the data is 11.55 μatm, which equals to just above 3 per cent of an average pCO2 value in the in situ dataset. The seasonal pCO2 cycle as well as the interannual variability estimates in the major biogeochemical provinces is presented and spatial and temporal variability of the estimated fields is discussed. High resolution combined with basin-wide cover makes the maps a useful tool for several applications such as monitoring of basin-wide air-sea CO2 fluxes or improvement of seasonal and interannual marine CO2 cycles in future model predictions. The method itself is a valuable alternative to traditional statistical modelling techniques used in geosciences.

Description: Here we present monthly, basin-wide maps of the partial pressure of carbon dioxide (pCO2) for the North Atlantic on a 1° latitude by 1° longitude grid for years 2004 through 2006 inclusive. The maps have been computed using a neural network technique which reconstructs the non-linear relationships between three biogeochemical parameters and marine pCO2. A self organizing map (SOM) neural network has been trained using 389 000 triplets of the SeaWiFS-MODIS chlorophyll-a concentration, the NCEP/NCAR reanalysis sea surface temperature, and the FOAM mixed layer depth. The trained SOM was labelled with 137 000 underway pCO2 measurements collected in situ during 2004, 2005 and 2006 in the North Atlantic, spanning the range of 208 to 437 μatm. The root mean square error (RMSE) of the neural network fit to the data is 11.6 μatm, which equals to just above 3 per cent of an average pCO2 value in the in situ dataset. The seasonal pCO2 cycle as well as estimates of the interannual variability in the major biogeochemical provinces are presented and discussed. High resolution combined with basin-wide coverage makes the maps a useful tool for several applications such as the monitoring of basin-wide air-sea CO2 fluxes or improvement of seasonal and interannual marine CO2 cycles in future model predictions. The method itself is a valuable alternative to traditional statistical modelling techniques used in geosciences.

Description: We investigate the significance of in situ dissolution of calcium carbonate above its saturation horizons using observations from the open subpolar North Atlantic [sNA] and to a lesser extent a 3-D biogeochemical model. The sNA is particularly well suited for observation-based detections of in situ, i.e. shallow-depth CaCO3 dissolution [SDCCD] as it is a region of high CaCO3 production, deep CaCO3 saturation horizons, and precisely-defined pre-formed alkalinity. Based on the analysis of a comprehensive alkalinity data set we find that SDCCD does not appear to be a significant process in the open sNA. The results from the model support the observational findings by indicating that there is not a significant need of SDCCD to explain observed patterns of alkalinity in the North Atlantic. Instead our investigation points to the importance of mixing processes for the redistribution of alkalinity from dissolution of CaCO3 from below its saturation horizons. However, mixing has recently been neglected for a number of studies that called for SDCCD in the sNA and on global scale.

Description: Here we present an equation for the estimation of nitrate in surface waters of the North Atlantic Ocean (40° N to 52° N, 10° W to 60° W). The equation was derived by multiple linear regression (MLR) from nitrate, sea surface temperature (SST) observational data and model mixed layer depth (MLD) data. The observational data were taken from merchant vessels that have crossed the North Atlantic on a regular basis in 2002/2003 and from 2005 to present. It is important to find a robust and realistic esitmate of MLD because the deepening of the mixed layer is crucial for nitrate supply to the surface. We compared model data from two models (FOAM and Mercator) with MLD derived from float data (using various criteria). The Mercator model gives a MLD estimate that is close to the MLD derived from floats. MLR was established using SST, MLD from Mercator, time and latitude as predictors. Additionally a neural network was trained with the same dataset and the results were validated against both model data as a "ground truth" and an independent observational dataset. This validation produced RMS errors of the same order for MLR and the neural network approach. We conclude that it is possible to estimate nitrate concentrations with an uncertainty of ±1.5 μmol L−1 in the North Atlantic.

Description: We investigate the significance of in situ dissolution of calcium carbonate above its saturation horizons. The study relies on observations from the open subpolar North Atlantic [sNA] and on a 3-D biogeochemical model. The sNA is particularly well suited for observation-based detections of in situ, i.e. shallow depth CaCO3 dissolution [SDCCD] as it is a region of high CaCO3 production, deep CaCO3 saturation horizons, and precisely-defined pre-formed alkalinity. Based on the analysis of a comprehensive alkalinity data set we find that SDCCD does not appear to be a significant process in the open sNA. The results from the model support the observational findings and do not indicate a significant need of SDCCD to explain observed patterns of alkalinity in the North Atlantic. Instead our investigation points to the importance of mixing processes for the redistribution of alkalinity from dissolution of CaCO3 from below its saturation horizons. However, mixing has recently been neglected for a number of studies that called for SDCCD in the sNA and on global scale.