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: 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.

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.

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.

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.

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 

Description: 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.

Description: This study investigated the effect of hydrostatic pressure of up to 6000 dbar on Aanderaa and Sea-Bird oxygen optodes both in the laboratory and in the field. The overall pressure response is a reduction in the O2 reading by 3%–4% per 1000 dbar, which is closely linear with pressure and increases with temperature. Closer inspection reveals two superimposed processes with an opposite effect: an O2-independent pressure response on the luminophore that increases optode O2 readings and an O2-dependent change in luminescence quenching that decreases optode O2 readings. The latter process dominates and is mainly due to a shift in the equilibrium between the sensing membrane and seawater under elevated pressures. If only the dominant O2-dependent process is considered, then the Aanderaa and Sea-Bird optodes differ in their pressure response. Compensation of the O2-independent process, however, yields a uniform O2 dependence for Aanderaa optodes with standard foil and fast-response foil as well as for Sea-Bird optodes. A new scheme to calculate optode O2 from raw data is proposed to account for the two processes. The overall uncertainty of the optode pressure correction amounts to 0.3% per 1000 dbar, which is mainly due to variability between the sensors.