ALBERT

Description: We elaborate the need for a quality-controlled chemical speciation model for seawater and related natural waters, work which forms the major focus of SCOR Working Group 145. Model development is based on Pitzer equations for the seawater electrolyte and trace components. These equations can be used to calculate activities of dissolved ions and molecules and, in combination with thermodynamic equilibrium constants, chemical speciation. The major tasks to be addressed are ensuring internal consistency of the Pitzer model parameters (expressing the interactions between pairs and triplets of species, which ultimately determines the calculated activities), assessing uncertainties, and identifying important data gaps that should be addressed by new measurements. It is recognized that natural organic matter plays an important role in many aquatic ecosystems, and options for including this material in a Pitzer-based model are discussed. The process of model development begins with the core components which include the seawater electrolyte and the weak acids controlling pH. This core model can then be expanded by incorporating additional chemical components, changing the standard seawater composition and/or broadening the range of temperature and pressure, without compromising its validity. Seven important areas of application are identified: open ocean acidification; micronutrient biogeochemistry and geochemical tracers; micronutrient behavior in laboratory studies; water quality in coastal and estuarine waters; cycling of nutrients and trace metals in pore waters; chemical equilibria in hydrothermal systems; brines and salt lakes.

Description: The Equatorial Deep Jets (EDJs) are an ubiquitous feature of the equatorial oceans; in the Atlantic Ocean, they are the dominant mode of interannual variability of the zonal flow at intermediate depth. On the basis of more than 10 years of moored observations of zonal velocity at 23°W, the vertically propagating EDJs are best described as superimposed oscillations of the 13th to the 23th baroclinic modes with a dominant oscillation period for all modes of 1650 days. This period is close to the resonance period of the respective gravest equatorial basin mode for the dominant vertical modes 16 and 17. It is argued that since the equatorial basin mode is composed of linear equatorial waves, a linear reduced gravity model can be employed for each baroclinic mode, driven by spatially homogeneous zonal forcing oscillating with the EDJ period. The fit of the model solutions to observations at 23°W yields a basin wide reconstruction of the EDJs and the associated vertical structure of their forcing. From the resulting vertical profile of mean power input and vertical energy flux on the equator, it follows that the EDJs are locally maintained over a considerable depth range, from 500-2500 m, with the maximum power input and vertical energy flux at 1300 m. The strong dissipation closely ties the apparent vertical propagation of energy to the vertical distribution of power input and, together with the EDJs’ prevailing downward phase propagation, require the phase of the forcing of the EDJs to propagate downward.

Description: The pH of aqueous solutions is known to impact the chemical speciation of trace metals. In this study we conducted titrations of coastal seawaters with iron and copper at pH 7.91, 7.37 and 6.99 (expressed on the total pH scale). Changes in the concentration of iron and copper that complexed with the added ligands 1-nitroso-2-napthol and salicylaldoxime respectively were determined by adsorptive cathodic stripping voltammetry - competitive ligand equilibrium (AdCSV-CLE). Interpretation of the results, assuming complexation by a low concentration of discrete ligands, showed that conditional stability constants for iron complexes increased relative to inorganic iron complexation as pH decreased by approximately 1 log unit per pH unit, whilst those for copper did not change. No trend was observed for concentrations of iron and copper complexing ligands over the pH range examined. We also interpreted our titration data by describing chemical binding and polyelectrolytic effects using non-ideal competitive adsorption in Donnan-like gels (NICA-Donnan model) in a proof of concept study. The NICA-Donnan approach allows for the development of a set of model parameters that are independent of ionic strength and pH, and thus calculation of metal speciation can be undertaken at ambient sample pH or the pH of a future, more acidic ocean. There is currently a lack of basic NICA-Donnan parameters applicable to marine dissolved organic matter (DOM) so we assumed that the measured marine dissolved organic carbon could be characterized as terrestrial fulvic acids. Generic NICA-Donnan parameters were applied within the framework of the software program visual MINTEQ and the metal –added ligand concentrations [MeAL] calculated for the AdCSV-CLE conditions. For copper, calculated [MeAL] using the NICA-Donnan model for DOM were consistent with measured [MeAL], but for iron an inert fraction with kinetically inhibited dissolution was required in addition to the NICA-Donnan model in order to approximate the trends observed in measured [MeAL]. We calculated iron and copper speciation in Northwest European shelf water samples at ambient alkalinity and projected increased pCO2 concentrations as a demonstration of the potential of the approach.

Description: Greenland’s ice sheet is the second largest on Earth, and is under threat from a warming Arctic climate. An increase in freshwater discharge from Greenland has the potential to strongly influence the composition of adjacent water masses with the largest impact on marine ecosystems likely to be found within the glaciated fjords. Here we demonstrate that physical and chemical estuarine processes within a large Greenlandic fjord are critical factors in determining the fate of meltwater derived nutrients and particles, especially for non-conservative elements such as Fe. Concentrations of Fe and macronutrients in surface waters along Godthåbsfjord, a southwest Greenlandic fjord with freshwater input from 6 glaciers, changed markedly between the onset and peak of the meltwater season due to the development of a thin (〈10 m), outflowing, low-salinity surface layer. Dissolved (〈0.2 µm) Fe concentrations in meltwater entering Godthåbsfjord (200 nM), in freshly melted glacial ice (mean 38 nM) and in surface waters close to a land terminating glacial system (80 nM) all indicated high Fe inputs into the fjord in summer. Total dissolvable (unfiltered at pH 〈2.0) Fe was similarly high with concentrations always in excess of 100 nM throughout the fjord and reaching up to 5.0 µM close to glacial outflows in summer. Yet, despite the large seasonal freshwater influx into the fjord, Fe concentrations near the fjord mouth in the out-flowing surface layer were similar in summer to those measured before the meltwater season. Furthermore, turbidity profiles indicated that sub-glacial particulate Fe inputs may not actually mix into the outflowing surface layer of this fjord. Emphasis has previously been placed on the possibility of increased Fe export from Greenland as meltwater fluxes increase. Here we suggest that in-fjord processes may be effective at removing Fe from surface waters before it can be exported to coastal seas.

Description: Downward wave coupling occurs when an upward propagating planetary wave from the troposphere decelerates the flow in the upper stratosphere, and forms a downward reflecting surface that redirects waves back to the troposphere. To test this mechanism and potential factors influencing the downward wave coupling, three 145-year sensitivity simulations with NCAR’s Community Earth System Model (CESM-WACCM), a state-of-the-art high-top chemistry-climate model, are analyzed. The results show that the QBO and SST variability significantly impact downward wave coupling. Without the QBO, the occurrence of downward wave coupling is significantly suppressed. In contrast, stronger and more persistent downward wave coupling occurs when SST variability is excluded. The above influence on the occurrence of downward wave coupling is mostly due to a direct influence of the QBO and SST variability on stratospheric planetary wave source and propagation. The strengths of the tropospheric circulation and surface responses to a given downward wave coupling event, however, behave differently. The surface anomaly is significantly weaker (stronger) in the experiment with fixed SSTs (without QBO), even though the statistical signal of downward coupling is strongest (weakest) in this experiment. This apparent mismatch is explained by the differences in the strength of the synoptic-scale eddy-mean flow feedback and the possible contribution of SST anomalies in the North Atlantic during DWC event. The weaker synoptic-scale eddy-mean flow feedback, and the absence of the positive NAO-related SST-tripole pattern in the fixed SST experiment are consistent with a weaker tropospheric response in this experiment. The results highlight the importance of synoptic-scale eddies in setting the tropospheric response to downward wave coupling.

Description: There is evidence that the strengthened stratospheric westerlies arising from the Antarctic ozone hole–induced cooling cause a polar mesospheric warming and a subsequent cooling in the lower thermosphere. While previous studies focus on the role of nonresolved (gravity) wave drag filtering, here the role of resolved (planetary) wave drag and radiative forcing on the Antarctic mesosphere and lower thermosphere (MLT) is explored in detail. Using simulations with NCAR’s Community Earth System Model, version 1 (Whole Atmosphere Community Climate Model) [CESM1(WACCM)], it is found that in late spring and early summer the anomalous polar mesospheric warming induced by easterly nonresolved wave drag is dampened by anomalous dynamical cooling induced by westerly resolved wave drag. This resolved wave drag is attributed to planetary-scale wave (k = 1–3) activity, which is generated in situ as a result of increased instability of the summer mesospheric easterly jet induced by the ozone hole. On the other hand, the anomalous cooling in the polar lower thermosphere induced by westerly nonresolved wave drag is enhanced by anomalous dynamical cooling due to westerly resolved wave drag. In addition, radiative effects from increased greenhouse gases during the ozone hole period contribute partially to the cooling in the polar lower thermosphere. The polar MLT temperature response to the Antarctic ozone hole is, through thermal wind balance, accompanied by the downward migration of anomalous zonal-mean wind from the lower thermosphere to the stratopause. The results highlight that a proper accounting of both dynamical and radiative effects is required in order to correctly attribute the causes of the polar MLT response to the Antarctic ozone hole.

Description: This study investigates the interaction of the Quasi-Biennial Oscillation (QBO) and the El Niño-Southern Oscillation (ENSO) in the troposphere separately for the North Pacific and North Atlantic region. Three 145-year model simulations with NCAR’s Community Earth Sytem Model (CESM-WACCM) are analyzed where only natural and no anthropogenic forcings are considered. These long simulations allow us to obtain statistically reliable results from an exceptional large number of cases for each combination of the QBO (westerly and easterly) and ENSO phases (El Niño and La Niña). Two different analysis methods were applied to investigate where nonlinearity might play a role in QBO-ENSO interactions. The analyses reveal that the stratospheric equatorial QBO anomalies extend down to the troposphere over the North Pacific during Northern hemisphere winter only during La Niña and not during El Niño events. The Aleutian low is deepened during QBO westerly (QBOW) as compared to QBO easterly (QBOE) conditions, and the North Pacific subtropical jet is shifted northward during La Niña. In the North Atlantic, the interaction of QBOW with La Niña conditions (QBOE with El Niño) results in a positive (negative) North Atlantic Oscillation (NAO) pattern. For both regions, nonlinear interactions between the QBO and ENSO might play a role. The results provide potential to enhance the skill of tropospheric seasonal predictions in the North Atlantic and North Pacific region.

Description: Seasonal variability of the tropical Atlantic circulation is dominated by the annual cycle, but semi-annual variability is also pronounced, despite weak forcing at that period. Here we use multi-year, full-depth velocity measurements from the central equatorial Atlantic to analyze the vertical structure of annual and semi-annual variations of zonal velocity. A baroclinic modal decomposition finds that the annual cycle is dominated by the 4th mode and the semi-annual cycle by the 2nd mode. Similar local behavior is found in a high-resolution general circulation model. This simulation reveals that the annual and semi-annual cycles of the respective dominant baroclinic modes are associated with characteristic basin-wide structures. Using an idealized linear reduced-gravity model to simulate the dynamics of individual baroclinic modes, it is shown that the observed circulation variability can be explained by resonant equatorial basin modes. Corollary simulations of the reduced-gravity model with varying basin geometry (i.e. square basin versus realistic coastlines) or forcing (i.e. spatially uniform versus spatially variable wind) show a structural robustness of the simulated basin modes. A main focus of this study is the seasonal variability of the Equatorial Undercurrent (EUC) as identified in recent observational studies. Main characteristics of the observed EUC including seasonal variability of transport, core depth, and maximum core velocity can be explained by the linear superposition of the dominant equatorial basin modes as obtained from the reduced-gravity model.

Description: At the Black Sea chemocline, oxygen- and sulfide-rich waters meet and form a niche for thiotrophic pelagic bacteria. Here we investigated an area of the Northwestern Black Sea off Crimea close to the shelf break, where the chemocline reaches the seafloor at around 150–170 m water depth, to assess whether thiotrophic bacteria are favored in this zone. Seafloor video transects were carried out with the submersible JAGO covering 20 km2 on the region between 110 and 200 m depth. Around the chemocline we observed irregular seafloor depressions, covered with whitish mats of large filamentous bacteria. These comprised 25–55% of the seafloor, forming a belt of 3 km width around the chemocline. Cores from the mats obtained with JAGO showed higher accumulations of organic matter under the mats compared to mat-free sediments. The mat-forming bacteria were related to Beggiatoa-like large filamentous sulfur bacteria based on 16S rRNA sequences from the mat, and visual characteristics. The microbial community under the mats was significantly different from the surrounding sediments and enriched with taxa affiliated with polymer degrading, fermenting and sulfate reducing microorganisms. Under the mats, higher organic matter accumulation, as well as higher remineralization and radiotracer-based sulfate reduction rates were measured compared to outside the mat. Mat-covered and mat-free sediments showed similar degradability of the bulk organic matter pool, suggesting that the higher sulfide fluxes and subsequent development of the thiotrophic mats in the patches are consequences of the accumulation of organic matter rather than its qualitative composition. Our observations suggest that the key factors for the distribution of thiotrophic mat-forming communities near to the Crimean shelf break are hypoxic conditions that (i) repress grazers, (ii) enhance the accumulation and degradation of labile organic matter by sulfate-reducers, and (iii) favor thiotrophic filamentous bacteria which are adapted to exploit steep gradients in oxygen and sulfide availability; in addition to a specific seafloor topography which may relate to internal waves at the shelf break.