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  • 1
    Publication Date: 2020-04-27
    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.
    Print ISSN: 1812-0784
    Electronic ISSN: 1812-0792
    Topics: Geosciences
    Published by Copernicus on behalf of European Geosciences Union.
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  • 2
    Publication Date: 2017-04-27
    Description: The temporal evolution of the physical and biogeochemical structure of an oxygen-depleted anticyclonic modewater eddy is investigated over a 2-month period using high-resolution glider and ship data. A weakly stratified eddy core (squared buoyancy frequency N2  ∼  0.1  ×  10−4 s−2) at shallow depth is identified with a horizontal extent of about 70 km and bounded by maxima in N2. The upper N2 maximum (3–5  ×  10−4 s−2) coincides with the mixed layer base and the lower N2 maximum (0.4  ×  10−4 s−2) is found at about 200 m depth in the eddy centre. The eddy core shows a constant slope in temperature/salinity (T∕S) characteristic over the 2 months, but an erosion of the core progressively narrows down the T∕S range. The eddy minimal oxygen concentrations decreased by about 5 µmol kg−1 in 2 months, confirming earlier estimates of oxygen consumption rates in these eddies. Separating the mesoscale and perturbation flow components reveals oscillating velocity finestructure ( ∼  0.1 m s−1) underneath the eddy and at its flanks. The velocity finestructure is organized in layers that align with layers in properties (salinity, temperature) but mostly cross through surfaces of constant density. The largest magnitude in velocity finestructure is seen between the surface and 140 m just outside the maximum mesoscale flow but also in a layer underneath the eddy centre, between 250 and 450 m. For both regions a cyclonic rotation of the velocity finestructure with depth suggests the vertical propagation of near-inertial wave (NIW) energy. Modification of the planetary vorticity by anticyclonic (eddy core) and cyclonic (eddy periphery) relative vorticity is most likely impacting the NIW energy propagation. Below the low oxygen core salt-finger type double diffusive layers are found that align with the velocity finestructure. Apparent oxygen utilization (AOU) versus dissolved inorganic nitrate (NO3−) ratios are about twice as high (16) in the eddy core compared to surrounding waters (8.1). A large NO3− deficit of 4 to 6 µmol kg−1 is determined, rendering denitrification an unlikely explanation. Here it is hypothesized that the differences in local recycling of nitrogen and oxygen, as a result of the eddy dynamics, cause the shift in the AOU : NO3− ratio. High NO3− and low oxygen waters are eroded by mixing from the eddy core and entrain into the mixed layer. The nitrogen is reintroduced into the core by gravitational settling of particulate matter out of the euphotic zone. The low oxygen water equilibrates in the mixed layer by air–sea gas exchange and does not participate in the gravitational sinking. Finally we propose a mesoscale–submesoscale interaction concept where wind energy, mediated via NIWs, drives nutrient supply to the euphotic zone and drives extraordinary blooms in anticyclonic mode-water eddies.
    Print ISSN: 1726-4170
    Electronic ISSN: 1726-4189
    Topics: Biology , Geosciences
    Published by Copernicus on behalf of European Geosciences Union.
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  • 3
    Publication Date: 2018-12-10
    Description: There is a need for cost-efficient tools to explore deep ocean ecosystems to collect baseline biological observations on pelagic fauna (zooplankton and nekton) and establish the vertical ecological zonation in the deep sea. The Pelagic In situ Observation System (PELAGIOS) is a 3000 m-rated slowly (0.5 m/s) towed camera system with LED illumination, an integrated oceanographic sensor set (CTD-O2) and telemetry allowing for online data acquisition and video inspection (Low Definition). The High Definition video is stored on the camera and later annotated using the VARS annotation software and related to concomitantly recorded environmental data. The PELAGIOS is particularly suitable for open ocean observations of gelatinous fauna, which is notoriously undersampled by nets and/or destroyed by fixatives. In addition to counts, diversity and distribution data as a function of depth and environmental conditions (T, S, O2), in situ observations of behavior, orientation and species interactions are collected. Here we present an overview of the technical setup of the PELAGIOS as well as example observations and analyses from the eastern tropical North Atlantic. Comparisons to MOCNESS net sampling and data from the Underwater Vision Profiler are provided and discussed.
    Print ISSN: 1812-0806
    Electronic ISSN: 1812-0822
    Topics: Geosciences
    Published by Copernicus on behalf of European Geosciences Union.
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  • 4
    Publication Date: 2017-01-13
    Description: Oxygen optode measurements on floats and gliders suffer from a slow time response and various sources of drift in the calibration coefficients. Based on two dual-O2 Argo floats, we show how to post-correct for the effect of the optode's time response and give an update on optode in situ drift stability and in-air calibration. Both floats are equipped with an unpumped Aanderaa 4330 optode and a pumped Sea-Bird SBE63 optode. Response times for the pumped SBE63 were derived following Bittig et al. (2014) and the same methods were used to correct the time response bias. Using both optodes on each float, the time response regime of the unpumped Aanderaa optode was characterized more accurately than previously possible. Response times for the pumped SBE63 on profiling floats are in the range of 25–40 s, while they are between 60 and 95 s for the unpumped 4330 optode. Our parameterization can be employed to post-correct the slow optode time response on floats and gliders. After correction, both sensors agree to within 2–3 µmol kg−1 (median difference) in the strongest gradients (120 µmol kg−1 change over 8 min or 20 dbar) and better elsewhere. However, time response correction is only possible if measurement times are known, i.e., provided by the platform as well as transmitted and stored with the data. The O2 in-air measurements show a significant in situ optode drift of −0.40 and −0.27 % yr−1 over the available 2 and 3 years of deployment, respectively. Optode in-air measurements are systematically biased high during midday surfacings compared to dusk, dawn, and nighttime. While preference can be given to nighttime surfacings to avoid this in-air calibration bias, we suggest a parameterization of the daytime effect as a function of the Sun's elevation to be able to use all data and to better constrain the result. Taking all effects into account, calibration factors have an uncertainty of 0.1 %. In addition, in-air calibration factors vary by 0.1–0.2 % when using different reanalysis models as a reference. The overall accuracy that can be achieved following the proposed correction routines is better than 1 µmol kg−1.
    Print ISSN: 1812-0784
    Electronic ISSN: 1812-0792
    Topics: Geosciences
    Published by Copernicus on behalf of European Geosciences Union.
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  • 5
    Publication Date: 2017-11-13
    Description: Accurate assessment of anthropogenic carbon dioxide (CO2) emissions and their redistribution among the atmosphere, ocean, and terrestrial biosphere – the "global carbon budget" – is important to better understand the global carbon cycle, support the development of climate policies, and project future climate change. Here we describe data sets and methodology to quantify the five major components of the global carbon budget and their uncertainties. CO2 emissions from fossil fuels and industry (EFF) are based on energy statistics and cement production data, respectively, while emissions from land-use change (ELUC), mainly deforestation, are based on land-cover change data and bookkeeping models. The global atmospheric CO2 concentration is measured directly and its rate of growth (GATM) is computed from the annual changes in concentration. The ocean CO2 sink (SOCEAN) and terrestrial CO2 sink (SLAND) are estimated with global process models constrained by observations. The resulting carbon budget imbalance (BIM), the difference between the estimated total emissions and the estimated changes in the atmosphere, ocean, and terrestrial biosphere, is a measure of our imperfect data and understanding of the contemporary carbon cycle. All uncertainties are reported as ±1σ. For the last decade available (2007–2016), EFF was 9.4 ± 0.5 GtC yr−1, ELUC 1.3 ± 0.7 GtC yr−1, GATM 4.7 ± 0.1 GtC yr−1, SOCEAN 2.4 ± 0.5 GtC yr−1, and SLAND 3.0 ± 0.8 GtC yr−1, with a budget imbalance BIM of 0.6 GtC yr−1 indicating overestimated emissions and/or underestimated sinks. For year 2016 alone, the growth in EFF was approximately zero and emissions remained at 9.9 ± 0.5 GtC yr−1. Also for 2016, ELUC was 1.3 ± 0.7 GtC yr−1, GATM was 6.1 ± 0.2 GtC yr−1, SOCEAN was 2.6 ± 0.5 GtC yr−1 and SLAND was 2.7 ± 1.0 GtC yr−1, with a small BIM of −0.3 GtC. GATM continued to be higher in 2016 compared to the past decade (2007–2016), reflecting in part the higher fossil emissions and smaller SLAND for that year consistent with El Niño conditions. The global atmospheric CO2 concentration reached 402.8 ± 0.1 ppm averaged over 2016. For 2017, preliminary data indicate a renewed growth in EFF of +2.0 % (range of 0.8 % to 3.0 %) based on national emissions projections for China, USA, and India, and projections of Gross Domestic Product corrected for recent changes in the carbon intensity of the economy for the rest of the world. For 2017, initial data indicate an increase in atmospheric CO2 concentration of around 5.3 GtC (2.5 ppm), attributed to a combination of increasing emissions and receding El Niño conditions. This living data update documents changes in the methods and data sets used in this new global carbon budget compared with previous publications of this data set (Le Quéré et al., 2016; 2015b; 2015a; 2014; 2013). All results presented here can be downloaded from https://doi.org/10.18160/GCP-2017.
    Electronic ISSN: 1866-3591
    Topics: Geosciences
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  • 6
    Publication Date: 2017-09-13
    Description: Numerous studies have been conducted on the effect of ocean acidification on calcifiers inhabiting nearshore benthic habitats, such as the blue mussel Mytilus edulis. The majority of these experiments was performed under stable CO2 partial pressure (pCO2), carbonate chemistry and oxygen (O2) levels, reflecting present or expected future open ocean conditions. Consequently, levels and variations occurring in coastal habitats, due to biotic and abiotic processes, were mostly neglected, even though these variations largely override global long-term trends. To highlight this hiatus and guide future research, state-of-the-art technologies were deployed to obtain high-resolution time series of pCO2 and [O2] on a mussel patch within a Zostera marina seagrass bed, in Kiel Bay (western Baltic Sea) in August and September 2013. Combining the in situ data with results of discrete sample measurements, a full seawater carbonate chemistry was derived using statistical models. An average pCO2 more than 50 % (~ 640 µatm) higher than current atmospheric levels was found right above the mussel patch. Diel amplitudes of pCO2 were large: 765 ± 310 (mean ± SD). Corrosive conditions for calcium carbonates (Ωarag and Ωcalc 
    Print ISSN: 1810-6277
    Electronic ISSN: 1810-6285
    Topics: Biology , Geosciences
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  • 7
    Publication Date: 2014-08-07
    Description: Ocean observations carried out in the framework of the Collaborative Research Center 754 (SFB 754) "Climate-Biogeochemistry Interactions in the Tropical Ocean" are used to study (1) the structure of tropical oxygen minimum zones (OMZs), (2) the processes that contribute to the oxygen budget, and (3) long-term changes in the oxygen distribution. The OMZ of the eastern tropical North Atlantic (ETNA), located between the well-ventilated subtropical gyre and the equatorial oxygen maximum, is composed of a deep OMZ at about 400 m depth with its core region centred at about 20° W, 10° N and a shallow OMZ at about 100 m depth with lowest oxygen concentrations in proximity to the coastal upwelling region off Mauritania and Senegal. The oxygen budget of the deep OMZ is given by oxygen consumption mainly balanced by the oxygen supply due to meridional eddy fluxes (about 60%) and vertical mixing (about 20%, locally up to 30%). Advection by zonal jets is crucial for the establishment of the equatorial oxygen maximum. In the latitude range of the deep OMZ, it dominates the oxygen supply in the upper 300 to 400 m and generates the intermediate oxygen maximum between deep and shallow OMZs. Water mass ages from transient tracers indicate substantially older water masses in the core of the deep OMZ (about 120–180 years) compared to regions north and south of it. The deoxygenation of the ETNA OMZ during recent decades suggests a substantial imbalance in the oxygen budget: about 10% of the oxygen consumption during that period was not balanced by ventilation. Long-term oxygen observations show variability on interannual, decadal and multidecadal time scales that can partly be attributed to circulation changes. In comparison to the ETNA OMZ the eastern tropical South Pacific OMZ shows a similar structure including an equatorial oxygen maximum driven by zonal advection, but overall much lower oxygen concentrations approaching zero in extended regions. As the shape of the OMZs is set by ocean circulation, the widespread misrepresentation of the intermediate circulation in ocean circulation models substantially contributes to their oxygen bias, which might have significant impacts on predictions of future oxygen levels.
    Print ISSN: 1810-6277
    Electronic ISSN: 1810-6285
    Topics: Biology , Geosciences
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  • 8
    Publication Date: 2016-03-11
    Description: The physical (temperature, salinity, velocity) and biogeochemical (oxygen, nitrate) structure of an oxygen depleted coherent, baroclinic, anticyclonic mode-water eddy (ACME) is investigated using high-resolution autonomous glider and ship data. A distinct core with a diameter of about 70 km is found in the eddy, extending from about 60 to 200 m depth and. The core is occupied by fresh and cold water with low oxygen and high nitrate concentrations, and bordered by local maxima in buoyancy frequency. Velocity and property gradient sections show vertical layering at the flanks and underneath the eddy characteristic for vertical propagation (to several hundred-meters depth) of near inertial internal waves (NIW) and confirmed by direct current measurements. A narrow region exists at the outer edge of the eddy where NIW can propagate downward. NIW phase speed and mean flow are of similar magnitude and critical layer formation is expected to occur. An asymmetry in the NIW pattern is seen that possible relates to the large-scale Ekman transport interacting with ACME dynamics. NIW/mean flow induced mixing occurs close to the euphotic zone/mixed layer and upward nutrient flux is expected and supported by the observations. Combing high resolution nitrate (NO3−) data with the apparent oxygen utilization (AOU) reveals AOU:NO3− ratios of 16 which are much higher than in the surrounding waters (8.1). A maximum NO3− deficit of 4 to 6 µmol kg−1 is estimated for the low oxygen core. Denitrification would be a possible explanation. This study provides evidence that the recycling of NO3−, extracted from the eddy core and replenished into the core via the particle export, may quantitatively be more important. In this case, the particulate phase is of keys importance in decoupling the nitrogen from the oxygen cycling.
    Print ISSN: 1810-6277
    Electronic ISSN: 1810-6285
    Topics: Biology , Geosciences
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  • 9
    Publication Date: 2016-01-26
    Description: The occurrence of mesoscale eddies that develop an extreme low oxygen environment at shallow depth (about 40 to 100 m) has recently been reported for the eastern tropical North Atlantic (ETNA). Their hydrographic structure suggests that the water mass inside the eddy is well isolated from ambient waters supporting the development of severe near-surface oxygen deficits. So far, hydrographic and biogeochemical characterization of these eddies was limited to a few autonomous surveys, using moorings, underwater gliders and profiling floats. In this study we present results from the first dedicated biogeochemical survey of one of these eddies conducted in March 2014 near the Cape Verde Ocean Observatory (CVOO). At the time of the survey the eddy core showed lowest oxygen concentrations of less than 5 μmol kg−1 and a pH of approx. 7.6 at the lower boundary of the euphotic zone. Correspondingly, the aragonite saturation level dropped to 1 thereby creating unfavorable conditions for calcifying organisms at this shallow depth. To our knowledge, such enhanced acidity within near-surface waters has never been reported before for the open Atlantic Ocean. Vertical distributions of particulate and dissolved organic matter (POM, DOM) generally show elevated concentrations in the surface mixed layer, but particularly DOM also accumulates beneath the oxygen minimum. Considering reference data from the upwelling region where these eddies are formed, we determined the oxygen consumption through remineralization of organic matter and found an enhancement of apparent oxygen utilization rates (aOUR, 0.26 μmol kg−1 d−1) by almost one order of magnitude when compared with typical values for the open North Atlantic. Computed downward fluxes for particulate organic carbon (POC) at 100 m were about 0.19 to 0.23 g C m−2 d−1 which clearly exceed fluxes typical for an oligotrophic open ocean setting. The observations support the view that the oxygen depleted eddies can be viewed as isolated, westwards propagating upwelling systems as their own.
    Print ISSN: 1810-6277
    Electronic ISSN: 1810-6285
    Topics: Biology , Geosciences
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  • 10
    Publication Date: 2009-11-10
    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.
    Print ISSN: 1812-0784
    Electronic ISSN: 1812-0792
    Topics: Geosciences
    Published by Copernicus on behalf of European Geosciences Union.
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