ALBERT

Description: Due to its accurate and precise character, spectrophotometric pH detection is a common technique applied in measurement methods for carbonate system parameters. However, impurities in the used pH indicator dyes can influence the measurements quality. During our work described here, we focused on impacts of impurities in the pH indicator dye bromocresol green (BCG) on spectrophotometric seawater total alkalinity (AT) measurements. In order to evaluate the extent of such influences, purified BCG served as a reference. First, a high-performance liquid chromatography (HPLC) purification method for BCG was developed as such a method did not exist at the time of this study. An analysis of BCG dye from four different vendors with this method revealed different types and quantities of impurities. After successful purification, AT measurements with purified and unpurified BCG were carried out using the novel autonomous analyzer CONTROS HydroFIA® TA. Long-term measurements in the laboratory revealed a direct influence of impurity types and quantities on the drift behavior of the analyzer. The purer the BCG, the smaller was the AT increase per measurement. The observed drift is generally caused by deposits in the optical pathway mainly generated by the impurities. However, the analyzers drift behavior could not be fully overcome. Furthermore, we could show that a certain impurity type in some indicator dyes changed the drift pattern from linear to nonlinear, which can impair long-term deployments of the system. Consequently, such indicators are impractical for these applications. Laboratory performance characterization experiments revealed no improvement of the measurement quality (precision and bias) by using purified BCG as long as the impurities of the unpurified dye do not exceed a quantity of 2 % (relationship of peak areas in the chromatogram). However, BCG with impurity quantities higher than 6 % provided AT values which failed fundamental quality requirements. In conclusion, to gain optimal AT measurements especially during long-term deployments, an indicator purification is not necessarily required as long as the purchased dye has a purity level of at least 98 % and is free of the named impurity type. Consequently, high-quality AT measurements do not require pure but the purest BCG that is purchasable.

Description: Over recent decades, observations based on merchant vessels (Ships of Opportunity—SOOP) equipped with sensors measuring the CO2 partial pressure (pCO2) in the surface seawater formed the backbone of the global ocean carbon observation system. However, the restriction to pCO2 measurements alone is one severe shortcoming of the current SOOP observatory. Full insight into the marine inorganic carbon system requires the measurement of at least two of the four measurable variables which are pCO2, total alkalinity (TA), dissolved inorganic carbon (DIC), and pH. One workaround is to estimate TA values based on established temperature-salinity parameterizations, but this leads to higher uncertainties and the possibility of regional and/or seasonal biases. Therefore, autonomous SOOP-based TA measurements are of great interest. Our study describes the implementation of a novel autonomous analyzer for seawater TA, the CONTROS HydroFIAⓇ TA system (-4H-JENA engineering GmbH, Germany) for unattended routine TA measurements on a SOOP line operating in the North Atlantic. We present the installation in detail and address major issues encountered with autonomous measurements using this analyzer, e.g., automated cleaning and stabilization routines, and waste handling. Another issue during long-term deployments is the provision of reference seawater in large-volume containers for quality assurance measurements and drift correction. Hence, a stable large-volume seawater storage had to be found. We tested several container types with respect to their suitability to store seawater over a time period of 30 days without significant changes in TA. Only one gas sampling bag made of polyvinylidene fluoride (PVDF) satisfied the high stability requirement. In order to prove the performance of the entire setup, we compared the autonomous TA measurements with TA from discrete samples taken during the first two trans-Atlantic crossings. Although the measurement accuracy in unattended mode (about ± 5 μmol kg^-1) slightly deteriorated compared to our previous system characterization, its overall uncertainty fulfilled requirements for autonomous TA measurements on SOOP lines. A comparison with predicted TA values based on an established and often used parameterization pointed at regional and seasonal limitations of such TA predictions. Consequently, TA observations with better coverage of spatiotemporal variability are needed, which is now possible with the method described here.

Description: Innovation and improvement report on the extension of capabilities to measure emerging EOVs including metagenomics across different observational platforms with links to MicroB3 best practice.

Description: High‐quality seawater total alkalinity (AT) measurements are essential for reliable ocean carbon and acidification observations. Well‐established manual multipoint potentiometric titration methods already fulfill these requirements. The next step in the improvement of these observations is the increase of the spatial and temporal measuring resolution with minimal personnel and instrumental effort. For this, a rapid, automated underway analyzer meeting the same high requirements as the traditional method is necessary. In this study, we carried out a comprehensive characterization of the flow‐through analyzer CONTROS HydroFIA® TA (Kongsberg Maritime Contros GmbH, Kiel, Germany) for automated seawater AT measurements in the laboratory and in field with overall more than 5000 measurements. Under laboratory conditions, the analyzer featured a precision of ± 1.5 μmol kg−1 and an accuracy of ± 1.0 μmol kg−1, combined in an uncertainty of 1.6 – 2.0 μmol kg−1. High precision (± 1.1 μmol kg−1) and accuracy (−0.3 ± 2.8 μmol kg−1), and low uncertainty (2.0 – 2.5 μmol kg−1) were also achieved during field trials of 4 and 6 weeks duration. Although a linear drift appears to be the typical behavior of the system, this can be corrected for by regular reference measurements giving consistent measurement results. Another advantage of regular reference measurements is the early detection of any kind of malfunction due to its direct impact on the measurement performance. Based on the present study, recommendations for automated long‐term deployments are provided in order to gain optimal performance characteristics, aiming at the requirements for AT measurements.

Description: Over recent decades, observations based on merchant vessels (Ships of Opportunity—SOOP) equipped with sensors measuring the CO2 partial pressure (pCO2) in the surface seawater formed the backbone of the global ocean carbon observation system. However, the restriction to pCO2 measurements alone is one severe shortcoming of the current SOOP observatory. Full insight into the marine inorganic carbon system requires the measurement of at least two of the four measurable variables which are pCO2, total alkalinity (TA), dissolved inorganic carbon (DIC), and pH. One workaround is to estimate TA values based on established temperature-salinity parameterizations, but this leads to higher uncertainties and the possibility of regional and/or seasonal biases. Therefore, autonomous SOOP-based TA measurements are of great interest. Our study describes the implementation of a novel autonomous analyzer for seawater TA, the CONTROS HydroFIAⓇ TA system (-4H-JENA engineering GmbH, Germany) for unattended routine TA measurements on a SOOP line operating in the North Atlantic. We present the installation in detail and address major issues encountered with autonomous measurements using this analyzer, e.g., automated cleaning and stabilization routines, and waste handling. Another issue during long-term deployments is the provision of reference seawater in large-volume containers for quality assurance measurements and drift correction. Hence, a stable large-volume seawater storage had to be found. We tested several container types with respect to their suitability to store seawater over a time period of 30 days without significant changes in TA. Only one gas sampling bag made of polyvinylidene fluoride (PVDF) satisfied the high stability requirement. In order to prove the performance of the entire setup, we compared the autonomous TA measurements with TA from discrete samples taken during the first two trans-Atlantic crossings. Although the measurement accuracy in unattended mode (about ± 5 μmol kg^-1) slightly deteriorated compared to our previous system characterization, its overall uncertainty fulfilled requirements for autonomous TA measurements on SOOP lines. A comparison with predicted TA values based on an established and often used parameterization pointed at regional and seasonal limitations of such TA predictions. Consequently, TA observations with better coverage of spatiotemporal variability are needed, which is now possible with the method described here.

Description: Since around the mid of the 18th century, the global atmospheric carbon dioxide (CO2) concentration has significantly increased due to anthropogenic activities. For 2018, around 11.5 GtC yr−1 were emitted by fossil fuel combustion and cement production, and land use changes. A sink for the atmospheric CO2 is the ocean, which has taken up around 2.6 GtC yr−1 in 2018. The relative good understanding of the current global mean oceanic uptake of anthropogenic CO2 is contrasted by a lack of knowledge how the natural carbon cycle will respond regionally to changes introduced by anthropogenic CO2 emissions, like global warming, ocean acidification or ocean deoxygenation. In view of the central role of the oceanic CO2 sink and its vulnerability to these changes, extensive ocean carbon observations are necessary. Over several years, the Ships of Opportunity (SOOP) network provides high-quality CO2 partial pressure (p(CO2)) data of the surface ocean, and, therefore, forms the backbone of the global observation system for the oceanic CO2 sink. However, to get full insight into the marine CO2 system, at least two of the four measurable carbonate variables are required, which are p(CO2), total alkalinity (AT), dissolved inorganic carbon (CT) and pH. The so far common workaround is the prediction of AT by using established temperature-salinity based parameterizations. However, compared with direct measurements, this procedure leads to higher uncertainties and spatiotemporal biases. Therefore, autonomous SOOP-based AT measurements are of great interest and, in the end, should enhance ocean carbon observations. In order to achieve this enhancement, this thesis goals to provide an example of a successful implementation of a novel autonomous analyzer for seawater AT, the CONTROS HydroFIA TA (-4H-JENA engineering GmbH, Germany), on a Carbon-SOOP station operating in the subpolar North Atlantic (together with fundamental guidelines and recommendations leading to high-quality AT data).

Description: Due to its accurate and precise character, spectrophotometric pH detection is a common technique applied in measurement methods for carbonate system parameters. However, impurities in the used pH indicator dyes can influence the measurements quality. During our work described here, we focused on impacts of impurities in the pH indicator dye bromocresol green (BCG) on spectrophotometric seawater total alkalinity (AT) measurements. In order to evaluate the extent of such influences, purified BCG served as a reference. First, a high-performance liquid chromatography (HPLC) purification method for BCG was developed as such a method did not exist at the time of this study. An analysis of BCG dye from four different vendors with this method revealed different types and quantities of impurities. After successful purification, AT measurements with purified and unpurified BCG were carried out using the novel autonomous analyzer CONTROS HydroFIA® TA. Long-term measurements in the laboratory revealed a direct influence of impurity types and quantities on the drift behavior of the analyzer. The purer the BCG, the smaller was the AT increase per measurement. The observed drift is generally caused by deposits in the optical pathway mainly generated by the impurities. However, the analyzers drift behavior could not be fully overcome. Furthermore, we could show that a certain impurity type in some indicator dyes changed the drift pattern from linear to nonlinear, which can impair long-term deployments of the system. Consequently, such indicators are impractical for these applications. Laboratory performance characterization experiments revealed no improvement of the measurement quality (precision and bias) by using purified BCG as long as the impurities of the unpurified dye do not exceed a quantity of 2 % (relationship of peak areas in the chromatogram). However, BCG with impurity quantities higher than 6 % provided AT values which failed fundamental quality requirements. In conclusion, to gain optimal AT measurements especially during long-term deployments, an indicator purification is not necessarily required as long as the purchased dye has a purity level of at least 98 % and is free of the named impurity type. Consequently, high-quality AT measurements do not require pure but the purest BCG that is purchasable.

Description: The need to cover established and emerging Essential Ocean Variables (EOVs) as defined by the Global Ocean Observing System (GOOS) calls for the development and refinement of the available sensors and samplers, specifically for biogeochemical and biology/ecosystem observations. For several of these EOVs as well as for microplastics as a relatively novel variable of particular societal concern, technological progress has been made as part of AtlantOS. This involves the samplers and sensors and the platforms to use them from as such as well as the required methodologies for obtaining relevant and well-validated results and disseminate data according to the FAIR principles. For biological observations, a main focus was on automated sampling of particles and water samples. While active, pump-based samplers for particles in the water column have been available for many years, it turned out that they were not yet fully mature for operational sampling of zooplankton, microorganisms (e.g., bacteria, archaea, phytoplankton and other eukaryotic unicellular organisms), and microplastics. AtlantOS partners joined forces with manufacturers to overcome limitations with respect to quantitative filtering without leakage, avoidance of plastic contamination and the option for preservation with appropriate agents. Technical solutions were identified and partly tested but could not in all cases be fully implemented in the time frame of the project. Technologies for automated water sampling proved to be more mature and samplers could already be successfully included in observation programs. For both water and particle samples only very few manufacturers offer off-the-shelf solutions which slows down innovation and adaption to user’s needs and may impede successful implementation of appropriate instruments on a larger scale. Particle traps are well-established and operational passive samplers of sinking particles that are widely used for phytoplankton and particulate matter observations based on microscopic sorting and chemical analyses. Using legacy samples collected in the Arctic it could be demonstrated that the same samples can also be used for omics-based observations allowing to address the emerging EOV ‘Microbe biomass and diversity’ and also contributing to the ‘Phytoplankton biomass and diversity’ EOV. Applied to legacy samples also from other sites, this holds the potential to assess past microbial communities of the Atlantic that could serve as a baseline for comparisons to recent communities that are subject to global change. Significant progress was achieved in building capacities for the implementation of omics-based observations of marine organisms into recent and future observation programs. The feasibility of samplers and different preservation agents was tested and a comparison of different methods for omics-based investigations of microbial communities was conducted. The Global Omics Observatory Network (GLOMICON) was established to better connect the institutes and initiatives that are active in the field. As part of GLOMICON, solutions were implemented that allow for a registration of omics observatories and for the sharing of protocols and bioinformatics code. Irrespective of these achievements, major steps still need to be taken to consolidate and standardize approaches in this rapidly evolving field and to establish operational and well-integrated omics-observations as part of an Atlantic Ocean Observation System. For biogeochemical observations, the focus was placed on sensors for oxygen and marine CO2 system parameters (pCO2, total alkalinity) and their readiness for integration into classical as well as emerging biogeochemical observation platforms. For oxygen, the situation is very favourable as the oxygen optode technology and the best practices routines developed around it can be considered fully operational. There are no obstacles for the D3.17 „OceanSITES Innovation Report“ 5 integration of oxygen optodes into the full range of autonomous ocean observation platforms (mooring, drifter, glider, wave gliders, floats, voluntary observing ship etc.). For marine CO2 system parameters, work carried out in AtlantOS focussed the CO2 partial pressure (pCO2) and total alkalinity (TA). With respect to pCO2 it can be stated, that the membraneequilibration sensors with NDIR detection have clearly matured to a level that they can be used routinely on a range of platforms (mooring, wave glider, voluntary observing ship) with an accuracy of ~1% under well-constrained operation conditions and with rigorous data processing routines. Major limitations still exist, however, for this sensor technology on moving platforms (long sensor response time) and platforms with stringent payload and energy limitations (float, glider etc.). In contrast, the pCO2 (as well as pH) optode technology, in which significant hopes lie, has not been forthcoming and existing products still do not meet the quality requirements for open ocean applications. For TA, our intensive testing both in the laboratory and in the field has led to significant improvement of the commercially available system, which now can be considered operational. It allows high-quality autonomous bench-top measurements (e.g., on voluntary observing ships). Ideas for a submersible version of the system are in early stages and would need significant design and testing efforts. With respect to the possibilities of oxygen and carbon measurements from novel autonomous observation platforms, our work in AltantOS has shown very promising applications on profiling Argo floats, submersible winch systems with upper ocean profilers as well as wave gliders. On all these platforms, we were able to successfully implement oxygen and carbon measurements for high-quality observations.