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The extracellular concentration of H2O2 in surface aquatic environments is controlled by a balance between photochemical production and the microbial synthesis of catalase and peroxidase enzymes to remove H2O2 from solution. In any kind of incubation experiment, the formation rates and equilibrium concentrations of reactive oxygen species (ROSs) such as H2O2 may be sensitive to both the experiment design, particularly to the regulation of incident light, and the abundance of different microbial groups, as both cellular H2O2 production and catalase–peroxidase enzyme production rates differ between species. Whilst there are extensive measurements of photochemical H2O2 formation rates and the distribution of H2O2 in the marine environment, it is poorly constrained how different microbial groups affect extracellular H2O2 concentrations, how comparable extracellular H2O2 concentrations within large-scale incubation experiments are to those observed in the surface-mixed layer, and to what extent a mismatch with environmentally relevant concentrations of ROS in incubations could influence biological processes differently to what would be observed in nature. Here we show that both experiment design and bacterial abundance consistently exert control on extracellular H2O2 concentrations across a range of incubation experiments in diverse marine environments. During four large-scale (>1000 L) mesocosm experiments (in Gran Canaria, the Mediterranean, Patagonia and Svalbard) most experimental factors appeared to exert only minor, or no, direct effect on H2O2 concentrations. For example, in three of four experiments where pH was manipulated to 0.4–0.5 below ambient pH, no significant change was evident in extracellular H2O2 concentrations relative to controls. An influence was sometimes inferred from zooplankton density, but not consistently between different incubation experiments, and no change in H2O2 was evident in controlled experiments using different densities of the copepod Calanus finmarchicus grazing on the diatom Skeletonema costatum (<1 % change in [H2O2] comparing copepod densities from 1 to 10 L−1). Instead, the changes in H2O2 concentration contrasting high- and low-zooplankton incubations appeared to arise from the resulting changes in bacterial activity. The correlation between bacterial abundance and extracellular H2O2 was stronger in some incubations than others (R2 range 0.09 to 0.55), yet high bacterial densities were consistently associated with low H2O2. Nonetheless, the main control on H2O2 concentrations during incubation experiments relative to those in ambient, unenclosed waters was the regulation of incident light. In an open (lidless) mesocosm experiment in Gran Canaria, H2O2 was persistently elevated (2–6-fold) above ambient concentrations; whereas using closed high-density polyethylene mesocosms in Crete, Svalbard and Patagonia H2O2 within incubations was always reduced (median 10 %–90 %) relative to ambient waters.

Although it has been demonstrated that the speed and magnitude of the recent Arctic sea ice decline is unprecedented for the past 1450 years, few records are available to provide a paleoclimate context for Arctic sea ice extent. Bromine enrichment in ice cores has been suggested to indicate the extent of newly formed sea ice areas. Despite the similarities among sea ice indicators and ice core bromine enrichment records, uncertainties still exist regarding the quantitative linkages between bromine reactive chemistry and the first-year sea ice surfaces. Here we present a 120 000-year record of bromine enrichment from the RECAP (REnland ice CAP) ice core, coastal east Greenland, and interpret it as a record of first-year sea ice. We compare it to existing sea ice records from marine cores and tentatively reconstruct past sea ice conditions in the North Atlantic as far north as the Fram Strait (50–85∘ N). Our interpretation implies that during the last deglaciation, the transition from multi-year to first-year sea ice started at ∼17.5 ka, synchronously with sea ice reductions observed in the eastern Nordic Seas and with the increase in North Atlantic ocean temperature. First-year sea ice reached its maximum at 12.4–11.8 ka during the Younger Dryas, after which open-water conditions started to dominate, consistent with sea ice records from the eastern Nordic Seas and the North Icelandic shelf. Our results show that over the last 120 000 years, multi-year sea ice extent was greatest during Marine Isotope Stage (MIS) 2 and possibly during MIS 4, with more extended first-year sea ice during MIS 3 and MIS 5. Sea ice extent during the Holocene (MIS 1) has been less than at any time in the last 120 000 years.

Bottom trawling in the deep sea is one of the main drivers of sediment resuspension, eroding the seafloor and altering the content and composition of sedimentary organic matter (OM). The physical and biogeochemical impacts of bottom trawling were studied on the continental slope of the Gulf of Castellammare, Sicily (southwestern Mediterranean), through the analysis of two triplicate sediment cores collected at trawled and untrawled sites (∼550 m water depth) during the summer of 2016. Geochemical and sedimentological parameters (excess 210Pb, excess 234Th, 137Cs, dry bulk density, and grain size), elemental (organic carbon and nitrogen) and biochemical composition of sedimentary OM (proteins, carbohydrates, lipids), as well as its freshness (phytopigments) and degradation rates were determined in both coring locations. The untrawled site had a sedimentation rate of 0.15 cm yr−1 and presented a 6 cm thick surface mixed layer that contained siltier sediment with low excess 210Pb concentrations, possibly resulting from the resuspension, posterior advection, and eventual deposition of coarser and older sediment from adjacent trawling grounds. In contrast, the trawled site was eroded and presented compacted century-old sediment highly depleted in OM components, which were between 20 % and 60 % lower than those in the untrawled site. However, the upper 2 cm of the trawled site consisted of recently accumulated sediments enriched in excess 234Th, excess 210Pb, and phytopigments, while OM contents were similar to those from the untrawled core. This fresh sediment supported protein turnover rates of 0.025 d−1, which doubled those quantified in surface sediments of the untrawled site. The enhancement of remineralization rates in surface sediment of the trawled site was associated with the arrival of fresh particles on a chronically trawled deep-sea region that is generally deprived of OM. We conclude that the detrimental effects of bottom trawling can be temporarily and partially abated by the arrival of fresh and nutritionally rich OM, which stimulate the response of benthic communities. However, these ephemeral deposits are likely to be swiftly eroded due to the high trawling frequency over fishing grounds, highlighting the importance of establishing science-based management strategies to mitigate the impacts of bottom trawling.

We present a Lagrangian convective transport scheme developed for global chemistry and transport models, which considers the variable residence time that an air parcel spends in convection. This is particularly important for accurately simulating the tropospheric chemistry of short-lived species, e.g., for determining the time available for heterogeneous chemical processes on the surface of cloud droplets. In current Lagrangian convective transport schemes air parcels are stochastically redistributed within a fixed time step according to estimated probabilities for convective entrainment as well as the altitude of detrainment. We introduce a new scheme that extends this approach by modeling the variable time that an air parcel spends in convection by estimating vertical updraft velocities. Vertical updraft velocities are obtained by combining convective mass fluxes from meteorological analysis data with a parameterization of convective area fraction profiles. We implement two different parameterizations: a parameterization using an observed constant convective area fraction profile and a parameterization that uses randomly drawn profiles to allow for variability. Our scheme is driven by convective mass fluxes and detrainment rates that originate from an external convective parameterization, which can be obtained from meteorological analysis data or from general circulation models. We study the effect of allowing for a variable time that an air parcel spends in convection by performing simulations in which our scheme is implemented into the trajectory module of the ATLAS chemistry and transport model and is driven by the ECMWF ERA-Interim reanalysis data. In particular, we show that the redistribution of air parcels in our scheme conserves the vertical mass distribution and that the scheme is able to reproduce the convective mass fluxes and detrainment rates of ERA-Interim. We further show that the estimated vertical updraft velocities of our scheme are able to reproduce wind profiler measurements performed in Darwin, Australia, for velocities larger than 0.6 m s−1. SO2 is used as an example to show that there is a significant effect on species mixing ratios when modeling the time spent in convective updrafts compared to a redistribution of air parcels in a fixed time step. Furthermore, we perform long-time global trajectory simulations of radon-222 and compare with aircraft measurements of radon activity.

The paper investigates the wintertime dynamics of the coastal northeastern Adriatic Sea and is based on numerical modelling and in situ data collected through field campaigns executed during the winter and spring of 2015. The data were collected with a variety of instruments and platforms (acoustic Doppler current profilers, conductivity–temperature–depth probes, glider, profiling float) and are accompanied by the atmosphere–ocean ALADIN/ROMS modelling system. The research focused on the dense-water formation (DWF), thermal changes, circulation, and water exchange between the coastal and open Adriatic. According to both observations and modelling results, dense waters are formed in the northeastern coastal Adriatic during cold bora outbreaks. However, the dense water formed in this coastal region has lower densities than the dense water formed in the open Adriatic due to lower salinities. Since the coastal area is deeper than the open Adriatic, the observations indicate (i) balanced inward–outward exchange at the deep connecting channels of denser waters coming from the open Adriatic DWF site and less-dense waters coming from the coastal region and (ii) outward flow of less-dense waters dominating in the intermediate and surface layers. The latter phenomenon was confirmed by the model, even if it significantly underestimates the currents and transports in the connecting channels. The median residence time of the coastal area is estimated to be approximately 20 days, indicating that the coastal area may be renewed relatively quickly by the open Adriatic waters. The data that were obtained represent a comprehensive marine dataset that can be used to calibrate atmospheric and oceanic numerical models and point to several interesting phenomena to be investigated in the future.

We present a 2700-year annually resolved chronology and snow accumulation history for the Roosevelt Island Climate Evolution (RICE) ice core, Ross Ice Shelf, West Antarctica. The core adds information on past accumulation changes in an otherwise poorly constrained sector of Antarctica. The timescale was constructed by identifying annual cycles in high-resolution impurity records, and it constitutes the top part of the Roosevelt Island Ice Core Chronology 2017 (RICE17). Validation by volcanic and methane matching to the WD2014 chronology from the WAIS Divide ice core shows that the two timescales are in excellent agreement. In a companion paper, gas matching to WAIS Divide is used to extend the timescale for the deeper part of the core in which annual layers cannot be identified. Based on the annually resolved timescale, we produced a record of past snow accumulation at Roosevelt Island. The accumulation history shows that Roosevelt Island experienced slightly increasing accumulation rates between 700 BCE and 1300 CE, with an average accumulation of 0.25±0.02 m water equivalent (w.e.) per year. Since 1300 CE, trends in the accumulation rate have been consistently negative, with an acceleration in the rate of decline after the mid-17th century. The current accumulation rate at Roosevelt Island is 0.210±0.002 m w.e. yr−1 (average since 1965 CE, ±2σ), and it is rapidly declining with a trend corresponding to 0.8 mm yr−2. The decline observed since the mid-1960s is 8 times faster than the long-term decreasing trend taking place over the previous centuries, with decadal mean accumulation rates consistently being below average. Previous research has shown a strong link between Roosevelt Island accumulation rates and the location and intensity of the Amundsen Sea Low, which has a significant impact on regional sea-ice extent. The decrease in accumulation rates at Roosevelt Island may therefore be explained in terms of a recent strengthening of the ASL and the expansion of sea ice in the eastern Ross Sea. The start of the rapid decrease in RICE accumulation rates observed in 1965 CE may thus mark the onset of significant increases in regional sea-ice extent.

Computer models are necessary for understanding and predicting marine ice sheet behaviour. However, there is uncertainty over implementation of physical processes at the ice base, both for grounded and floating glacial ice. Here we implement several sliding relations in a marine ice sheet flow-line model accounting for all stress components and demonstrate that model resolution requirements are strongly dependent on both the choice of basal sliding relation and the spatial distribution of ice shelf basal melting.Sliding relations that reduce the magnitude of the step change in basal drag from grounded ice to floating ice (where basal drag is set to zero) show reduced dependence on resolution compared to a commonly used relation, in which basal drag is purely a power law function of basal ice velocity. Sliding relations in which basal drag goes smoothly to zero as the grounding line is approached from inland (due to a physically motivated incorporation of effective pressure at the bed) provide further reduction in resolution dependence.A similar issue is found with the imposition of basal melt under the floating part of the ice shelf: melt parameterisations that reduce the abruptness of change in basal melting from grounded ice (where basal melt is set to zero) to floating ice provide improved convergence with resolution compared to parameterisations in which high melt occurs adjacent to the grounding line.Thus physical processes, such as sub-glacial outflow (which could cause high melt near the grounding line), impact on capability to simulate marine ice sheets. If there exists an abrupt change across the grounding line in either basal drag or basal melting, then high resolution will be required to solve the problem. However, the plausible combination of a physical dependency of basal drag on effective pressure, and the possibility of low ice shelf basal melt rates next to the grounding line, may mean that some marine ice sheet systems can be reliably simulated at a coarser resolution than currently thought necessary.

A maximum in the strength of Agulhas leakage has been registered at the interface between the Indian and South Atlantic oceans during glacial Termination II (T-II). This presumably transported the salt and heat necessary for maintaining the Atlantic circulation at rates similar to the present day. However, it was never shown whether these waters were effectively incorporated into the South Atlantic gyre, or whether they retroflected into the Indian and/or Southern oceans. To resolve this question, we investigate the presence of paleo Agulhas rings from a sediment core on the central Walvis Ridge, almost 1800 km farther into the Atlantic Basin than previously studied. Analysis of a 60 yr data set from the global-nested INALT01 model allows us to relate density perturbations at the depth of the thermocline to the passage of individual rings over the core site. Using this relation from the numerical model as the basis for a proxy, we generate a time series of variability of individual Globorotalia truncatulinoides δ18O. We reveal high levels of pycnocline depth variability at the site, suggesting enhanced numbers of Agulhas rings moving into the South Atlantic Gyre around T-II. Our record closely follows the published quantifications of Agulhas leakage from the east of the Cape Basin, and thus shows that Indian Ocean waters entered the South Atlantic circulation. This provides crucial support for the view of a prominent role of the Agulhas leakage in the shift from a glacial to an interglacial mode of the Atlantic circulation.

The boron isotopic composition (δ11B) of marine carbonates (e.g. corals) is increasingly utilised as a proxy for paleo-pH, with the strong correlation between δ11B of marine calcifiers and seawater pH now well documented. However, the potential roles of other environmental parameters that may also influence both the boron isotopic composition and boron concentration into coral aragonite are poorly known. To overcome this, the tropical scleractinian coral Acropora sp. was cultured under 3 different temperatures (22, 25 and 28 °C) and two light conditions (200 and 400 μmol photon m−2 s−1). The δ11B indicates an increase in internal pH that is dependent on the light conditions. Changes in light intensities from 200 to 400 μmol photon m−2 s−1 seem to indicate an apparent decrease in pH at the site of calcification, contrary to what is expected in most models of light-enhanced calcification. Thus, variations in light conditions chosen to mimic average annual variations of the natural environments where Acropora sp. colonies can be found could bias pH reconstructions by about 0.05 units. For both light conditions, a significant impact of temperature on δ11B can be observed between 22 and 25 °C, corresponding to an increase of about 0.02 pH-units, while no further δ11B increase can be observed from 25 to 28 °C. This non-linear temperature effect complicates the determination of a correction factor. B / Ca ratios decrease with increasing light, consistent with the decrease in pH at the site of calcification under enhanced light intensities. When all the other parameters are constant, boron concentrations in Acropora sp. increase with increasing temperatures and increasing carbonate ion concentrations. These observations contradict previous studies where B / Ca in corals was found to vary inversely with temperature, suggesting that the controlling factors driving boron concentrations have not yet been adequately identified and might be influenced by other environmental variables and/or species-specific responses.

Laboratory experiments were performed to study the dynamics of three- dimensional mechanically generated waves propagating over an oblique current in partial opposition. The flow velocity varied along the mean wave direction of propagation with an increasing trend between the wave-maker and the centre of the tank. Tests with regular wave packets traversing the area of positive current gradient showed that the concurrent increase of wave steepness triggered modulational instability on otherwise stable wave trains and hence induced the development of very large amplitude waves. In random directional wave fields, the presence of the oblique current resulted in a weak reinforcement of wave instability with a subsequent increase of the probability of occurrence of extreme events. This seems to partially compensate the suppression of strongly non-Gaussian properties due to directional energy distribution.