ALBERT

Beschreibung: This paper presents a detailed quality assessment of a novel underwater sensor for the measurement of CO2 partial pressure (pCO2) based on surface water field deployments carried out between 2008 and 2011. The commercially available sensor, which is based on membrane equilibration and nondispersive IR (NDIR) spectrometry is small and can be integrated into mobile platforms. It is calibrated in water against a proven flow-through pCO2 instrument within a custom-built calibration setup. The aspect of highest concern with respect to achievable data quality of the sensor is the compensation for signal drift inevitably connected to absorption measurements. Three means are used to correct for drift effects: (i) a filter correlation or dual-beam setup, (ii) regular zero gas measurements realized automatically within the sensor, and (iii) a zero-based transformation of two sensor calibrations flanking the time of sensor deployment. Three sensors were tested against an underway pCO2 system during two major research cruises, providing an in situ temperature range from 7.4° to 30.1°C and pCO2 values between 289 and 445 μatm. The average difference between sensor and reference pCO2 was found to be −0.6 ±3.0 μatm with an RMSE of 3.7 μatm.

Beschreibung: Changes in the ventilation of the oxygen minimum zone (OMZ) of the tropical North Atlantic are studied using oceanographic data from 18 research cruises carried out between 28.5° and 23°W during 1999–2008 as well as historical data referring to the period 1972–85. In the core of the OMZ at about 400-m depth, a highly significant oxygen decrease of about 15 μmol kg−1 is found between the two periods. During the same time interval, the salinity at the oxygen minimum increased by about 0.1. Above the core of the OMZ, within the central water layer, oxygen decreased too, but salinity changed only slightly or even decreased. The scatter in the local oxygen–salinity relations decreased from the earlier to the later period suggesting a reduced filamentation due to mesoscale eddies and/or zonal jets acting on the background gradients. Here it is suggested that latitudinally alternating zonal jets with observed amplitudes of a few centimeters per second in the depth range of the OMZ contribute to the ventilation of the OMZ. A conceptual model of the ventilation of the OMZ is used to corroborate the hypothesis that changes in the strength of zonal jets affect mean oxygen levels in the OMZ. According to the model, a weakening of zonal jets, which is in general agreement with observed hydrographic evidences, is associated with a reduction of the mean oxygen levels that could significantly contribute to the observed deoxygenation of the North Atlantic OMZ.

Beschreibung: CO2 emissions are leading to an acidification of the oceans. Predicting marine community vulnerability towards acidification is difficult, as adaptation processes cannot be accounted for in most experimental studies. Naturally CO2 enriched sites thus can serve as valuable proxies for future changes in community structure. Here we describe a natural analogue site in the Western Baltic Sea. Seawater pCO2 in Kiel Fjord is elevated for large parts of the year due to upwelling of CO2 rich waters. Peak pCO2 values of 〉230 Pa (〉2300 μatm) and pHNBS values of 〈7.5 are encountered during summer and autumn, average pCO2 values are ~70 Pa (~700 μatm). In contrast to previously described naturally CO2 enriched sites that have suggested a progressive displacement of calcifying auto- and heterotrophic species, the macrobenthic community in Kiel Fjord is dominated by calcifying invertebrates. We show that blue mussels from Kiel Fjord can maintain control rates of somatic and shell growth at a pCO2 of 142 Pa (1400 μatm, pHNBS = 7.7). Juvenile mussel recruitment peaks during the summer months, when high water pCO2 values of ~100 Pa (~1000 μatm) prevail. Our findings indicate that calcifying keystone species may be able to cope with surface ocean pHNBS values projected for the end of this century when food supply is sufficient. However, owing to non-linear synergistic effects of future acidification and upwelling of corrosive water, peak seawater pCO2 in Kiel Fjord and many other productive estuarine habitats could increase to values 〉400 Pa (〉4000 μatm). These changes will most likely affect calcification and recruitment, and increase external shell dissolution.

Beschreibung: As a response to public demand for a well-documented, quality controlled, publically available, global surface ocean carbon dioxide (CO2) data set, the international marine carbon science community developed the Surface Ocean CO2 Atlas (SOCAT). The first SOCAT product is a collection of 6.3 million quality controlled surface CO2 data from the global oceans and coastal seas, spanning four decades (1968–2007). The SOCAT gridded data presented here is the second data product to come from the SOCAT project. Recognizing that some groups may have trouble working with millions of measurements, the SOCAT gridded product was generated to provide a robust, regularly spaced CO2 fugacity (fCO2) product with minimal spatial and temporal interpolation, which should be easier to work with for many applications. Gridded SOCAT is rich with information that has not been fully explored yet (e.g., regional differences in the seasonal cycles), but also contains biases and limitations that the user needs to recognize and address (e.g., local influences on values in some coastal regions).

Beschreibung: A well documented, publicly available, global data set of surface ocean carbon dioxide (CO2) parameters has been called for by international groups for nearly two decades. The Surface Ocean CO2 Atlas (SOCAT) project was initiated by the international marine carbon science community in 2007 with the aim of providing a comprehensive, publicly available, regularly updated, global data set of marine surface CO2, which had been subject to quality control (QC). Many additional CO2 data, not yet made public via the Carbon Dioxide Information Analysis Center (CDIAC), were retrieved from data originators, public websites and other data centres. All data were put in a uniform format following a strict protocol. Quality control was carried out according to clearly defined criteria. Regional specialists performed the quality control, using state-of-the-art web-based tools, specially developed for accomplishing this global team effort. SOCAT version 1.5 was made public in September 2011 and holds 6.3 million quality controlled surface CO2 data points from the global oceans and coastal seas, spanning four decades (1968–2007). Three types of data products are available: individual cruise files, a merged complete data set and gridded products. With the rapid expansion of marine CO2 data collection and the importance of quantifying net global oceanic CO2 uptake and its changes, sustained data synthesis and data access are priorities

Beschreibung: Autonomous sensors are required for a comprehensive documentation of the changes in the marine carbon system and thus to differentiate between its natural variability and anthropogenic impacts. Spectrophotometric determination of pH – a key variable of the seawater carbon system – is particularly suited to achieve precise and drift-free measurements. However, available spectrophotometric instruments are not suitable for integration into automated measurement systems (e.g. FerryBox) since they do not meet the major requirements of reliability, stability, robustness and moderate cost. Here we report on the development and testing of a~new indicator-based pH sensor that meets all of these requirements. This sensor can withstand the rough conditions during long-term deployments on ships of opportunity and is applicable to the open ocean as well as to coastal waters with a complex matrix and highly variable conditions. The sensor uses a high resolution CCD spectrometer as detector connected via optical fibers to a custom-made cuvette designed to reduce the impact of air bubbles. The sample temperature can be precisely adjusted (25 °C ± 0.006 °C) using computer-controlled power supplies and Peltier elements thus avoiding the widely used water bath. The overall setup achieves a measurement frequency of 1 min−1 with a precision of ±0.0007 pH units, an average offset of +0.0005 pH units to a reference system, and an offset of +0.0081 pH units to a certified standard buffer. Application of this sensor allows monitoring of seawater pH in autonomous underway systems, providing a key variable for characterization and understanding of the marine carbon system.

Beschreibung: Water column data of carbon and carbon-relevant hydrographic and hydrochemical parameters from 188 previously non-publicly available cruise data sets in the Arctic Mediterranean Seas, Atlantic and Southern Ocean have been retrieved and merged into a new database: CARINA (CARbon dioxide IN the Atlantic Ocean). 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 three data products: merged data files with measured, calculated and interpolated data for each of the three CARINA regions, i.e. the Arctic Mediterranean Seas, the Atlantic and the Southern Ocean. These products have been corrected to be internally consistent. 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 the details of the secondary QC (Quality Control) 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 consistency of the CARINA-ATL salinity data to be 4.1 ppm. With these adjustments the CARINA data products are consistent both internally as well as with GLODAP data, an oceanographic data set based on the World Hydrographic Program in the 1990s, and is now suitable for accurate assessments of, for example, oceanic carbon inventories and uptake rates and for model validation.

Beschreibung: A new system for continuous, highly-resolved oceanic and atmospheric measurements of N2O, CO and CO2 is described. The system is based upon off-axis integrated cavity output spectroscopy (OA-ICOS) and a non-dispersive infrared analyzer (NDIR) both coupled to a Weiss-type equilibrator. Performance of the combined setup was evaluated by testing its precision, accuracy, long-term stability, linearity and response time. Furthermore, the setup was tested during two oceanographic campaigns in the equatorial Atlantic Ocean in order to explore its potential for autonomous deployment onboard voluntary observing ships (VOS). Improved equilibrator response times for N2O (2.5 min) and CO (45 min) were achieved in comparison to response times from similar chamber designs used by previous studies. High stability of the OA-ICOS analyzer was demonstrated by low optimal integration times of 2 and 4 min for N2O and CO respectively, as well as detection limits of 〈 40 ppt and precision better than 0.3 ppb Hz−1/2. Results from a direct comparison of the method presented here and well-established discrete methods for oceanic N2O and CO2 measurements showed very good consistency. The favorable agreement between underway atmospheric N2O, CO and CO2 measurements and monthly means at Ascension Island (7.96°S 14.4°W) further suggests a reliable operation of the underway setup in the field. The potential of the system as an improved platform for measurements of trace gases was explored by using continuous N2O and CO2 data to characterize the development of the seasonal equatorial upwelling in the Atlantic Ocean during two RV/ Maria S. Merian cruises. A similar record of high-resolution CO measurements was simultaneously obtained offering for the first time the possibility of a comprehensive view on the distribution and emissions of these climate relevant gases on the area. The relatively simple underway N2O/CO/CO2 setup is suitable for long-term deployment on board of research and commercial vessels although potential sources of drift such as cavity temperature and further technical improvements towards automation still need to be addressed.