ALBERT

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: 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 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 high fossil emissions and the small SLAND consistent with El Niño conditions. The global atmospheric CO2 concentration reached 402.8 ± 0.1 ppm averaged over 2016. For 2017, preliminary data for the first 6–9 months 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 (GDP) corrected for recent changes in the carbon intensity of the economy for the rest of the world. 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, a, 2014, 2013). All results presented here can be downloaded from https://doi.org/10.18160/GCP-2017 (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 〈 1) centered on sunrise were found, but the investigated habitat never experienced hypoxia throughout the study period. It is estimated that mussels experience conditions limiting calcification for 12–15 h per day, based on a regional calcium carbonate concentration physiological threshold. Our findings call for more extensive experiments on the impact of fluctuating corrosive conditions on mussels. We also stress the complexity of the interpretation of carbonate chemistry time series data in such dynamic coastal environments.

Description: Localized open-ocean low-oxygen “dead zones” in the eastern tropical North Atlantic are recently discovered ocean features that can develop in dynamically isolated water masses within cyclonic eddies (CE) and anticyclonic mode-water eddies (ACME). Analysis of a comprehensive oxygen dataset obtained from gliders, moorings, research vessels and Argo floats reveals that “dead-zone” eddies are found in surprisingly high numbers and in a large area from about 4 to 22° N, from the shelf at the eastern boundary to 38° W. In total, 173 profiles with oxygen concentrations below the minimum background concentration of 40 µmol kg−1 could be associated with 27 independent eddies (10 CEs; 17 ACMEs) over a period of 10 years. Lowest oxygen concentrations in CEs are less than 10 µmol kg−1 while in ACMEs even suboxic (〈 1 µmol kg−1) levels are observed. The oxygen minimum in the eddies is located at shallow depth from 50 to 150 m with a mean depth of 80 m. Compared to the surrounding waters, the mean oxygen anomaly in the core depth range (50 and 150 m) for CEs (ACMEs) is −38 (−79) µmol kg−1. North of 12° N, the oxygen-depleted eddies carry anomalously low-salinity water of South Atlantic origin from the eastern boundary upwelling region into the open ocean. Here water mass properties and satellite eddy tracking both point to an eddy generation near the eastern boundary. In contrast, the oxygen-depleted eddies south of 12° N carry weak hydrographic anomalies in their cores and seem to be generated in the open ocean away from the boundary. In both regions a decrease in oxygen from east to west is identified supporting the en-route creation of the low-oxygen core through a combination of high productivity in the eddy surface waters and an isolation of the eddy cores with respect to lateral oxygen supply. Indeed, eddies of both types feature a cold sea surface temperature anomaly and enhanced chlorophyll concentrations in their center. The low-oxygen core depth in the eddies aligns with the depth of the shallow oxygen minimum zone of the eastern tropical North Atlantic. Averaged over the whole area an oxygen reduction of 7 µmol kg−1 in the depth range of 50 to 150 m (peak reduction is 16 µmol kg−1 at 100 m depth) can be associated with the dispersion of the eddies. Thus the locally increased oxygen consumption within the eddy cores enhances the total oxygen consumption in the open eastern tropical North Atlantic Ocean and seems to be an contributor to the formation of the shallow oxygen minimum zone.

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.