ALBERT

Description: Ocean alkalinity enhancement (OAE) is a negative emissions technology (NET) that shows significant potential for climate change mitigation. By increasing the bicarbonate ion concentration in ocean water, OAE could enhance long-term carbon storage and mitigate ocean acidification. However, the side effects and/or potential co-benefits of OAE on natural planktonic communities remain poorly understood. To address this knowledge gap, a mesocosm experiment was conducted in the oligotrophic waters of Gran Canaria. A CO2-equilibrated total alkalinity (TA) gradient was employed in increments of 300 µmol L−1, ranging from ∼ 2400 to ∼ 4800 µmol L−1. This study represents the first attempt to evaluate the potential impacts of OAE on planktonic communities under natural conditions. The results show that net community production (NCP), gross production (GP), community respiration (CR) rates, and the metabolic balance (GP:CR) did not exhibit a linear response to the whole alkalinity gradient. Instead, significant polynomial and linear regression models were observed for all rates up to ΔTA 1800 µmol L−1, in relation to the dissolved inorganic carbon (DIC) concentrations. Notably, the ΔTA 1500 and 1800 µmol L−1 treatments showed peaks in NCP shifting from a heterotrophic to an autotrophic state, with NCP values of 4 and 8 µmol O2 kg−1 d−1, respectively. These peaks and the optimum curve were also reflected in the nanoplankton abundance, size-fractionated chlorophyll a, and 14C uptake data. Furthermore, abiotic precipitation occurred in the highest treatment after day 21, but no impact on the measured parameters was detected. Overall, a damaging effect of CO2-equilibrated OAE in the range applied here on phytoplankton primary production, community metabolism, and composition could not be inferred. In fact, a potential co-benefit to OAE was observed in the form of the positive curvilinear response to the DIC gradient up to the ΔTA 1800 treatment. Further experimental research at this scale is key to gain a better understanding of the short- and long-term effects of OAE on planktonic communities.

Description: Upwelling of nutrient-rich deep waters make eastern boundary upwelling systems (EBUSs), such as the Humboldt Current system, hot spots of marine productivity. Associated settling of organic matter to depth and consecutive aerobic decomposition results in large subsurface water volumes being oxygen depleted. Under these circumstances, organic matter remineralisation can continue via denitrification, which represents a major loss pathway for bioavailable nitrogen. Additionally, anaerobic ammonium oxidation can remove significant amounts of nitrogen in these areas. Here we assess the interplay of suboxic water upwelling and nitrogen cycling in a manipulative offshore mesocosm experiment. Measured denitrification rates in incubations with water from the oxygen-depleted bottom layer of the mesocosms (via 15N label incubations) mostly ranged between 5.5 and 20 nmol N2 L−1 h−1 (interquartile range), reaching up to 80 nmol N2 L−1 h−1. However, actual in situ rates in the mesocosms, estimated via Michaelis–Menten kinetic scaling, did most likely not exceed 0.2–4.2 nmol N2 L−1 h−1 (interquartile range) due to substrate limitation. In the surrounding Pacific, measured denitrification rates were similar, although indications of substrate limitation were detected only once. In contrast, anammox (anaerobic ammonium oxidation) made only a minor contribution to the overall nitrogen loss when encountered in both the mesocosms and the Pacific Ocean. This was potentially related to organic matter C / N stoichiometry and/or process-specific oxygen and hydrogen sulfide sensitivities. Over the first 38 d of the experiment, total nitrogen loss calculated from in situ rates of denitrification and anammox was comparable to estimates from a full nitrogen budget in the mesocosms and ranged between ∼ 1 and 5.5 µmol N L−1. This represents up to ∼  20 % of the initially bioavailable inorganic and organic nitrogen standing stocks. Interestingly, this loss is comparable to the total amount of particulate organic nitrogen that was exported into the sediment traps at the bottom of the mesocosms at about 20 m depth. Altogether, this suggests that a significant portion, if not the majority of nitrogen that could be exported to depth, is already lost, i.e. converted to N2 in a relatively shallow layer of the surface ocean, provided that there are oxygen-deficient conditions like those during coastal upwelling in our study. Published data for primary productivity and nitrogen loss in all EBUSs reinforce such conclusion.

Description: This study contributes to the inaugural exploration of non-equilibrated Ocean Alkalinity Enhancement (OAE). The manipulation of Total Alkalinity (TA), involving silicate and calcium-based ∆TA gradients ranging from 0 to 600 µmol · L-1, was conducted without prior CO2 sequestration, under natural conditions and at a mesocosm scale (~60 m3). The resulting impact included an increase in pH and a decrease in pCO2, sustained across the experiment, as full natural equilibration via sea-gas exchange did not occur. Implemented in a neritic system under post-bloom conditions, a midway mixing event was simulated. Following an inorganic nutrient addition, discernible delays in bloom formation, as indicated by the Gross Production (GP) and Net Community Production (NCP) rates, as well as by the chlorophyll-a (Chla) concentrations, in relation to the ∆TA gradient, were observed. Notably, the delay was more pronounced for the calcium treatment set compared to the silicate one, where low TA treatments exhibited earlier responses than high TA ones. This delay is likely attributed to the previously documented, species-specific negative relationships between high pH/lowCO2 levels and phytoplankton growth rates. This study underscores the need for further investigation into the implications of this response pattern in terms of trophic transfer and seasonal suitability. Further, it is anticipated that a wider delay in bloom formation would be evident with a larger non equilibrated TA gradient. Thus, highlighting the importance of exploring variations in TA limits for a comprehensive understanding of the OAE’s impacts.

Description: Observed oxygen minimum zones (OMZs) in the tropical Pacific Ocean are located above intermediate-depth waters (IDWs), defined here as the 500–1500 m water layer. Typical climate models do not represent IDW properties well and are characterized by OMZs that are too deep-reaching. We analyze the role of the IDW in the misrepresentation of oxygen levels in a heterogeneous subset of ocean models characterized by a horizontal resolution ranging from 0.1 to 2.8∘. First, we show that forcing the extratropical boundaries (30∘ S and N) to observed oxygen values results in a significant increase in oxygen levels in the intermediate eastern tropical region. Second, we highlight the fact that the Equatorial Intermediate Current System (EICS) is a key feature connecting the western and eastern part of the basin. Typical climate models lack in representing crucial aspects of this supply at intermediate depth, as the EICS is basically absent in models characterized by a resolution lower than 0.25∘. These two aspects add up to a “cascade of biases” that hampers the correct representation of oxygen levels at intermediate depth in the eastern tropical Pacific Ocean and potentially future OMZ projections.

Description: In this study we look beyond the previously studied effects of oceanic CO2 injections on atmospheric and oceanic reservoirs and also account for carbon cycle and climate feedbacks between the atmosphere and the terrestrial biosphere. Considering these additional feedbacks is important since backfluxes from the terrestrial biosphere to the atmosphere in response to reducing atmospheric CO2 can further offset the targeted reduction. To quantify these dynamics we use an Earth system model of intermediate complexity to simulate direct injection of CO2 into the deep ocean as a means of emissions mitigation during a high CO2 emission scenario. In three sets of experiments with different injection depths, we simulate a 100-year injection period of a total of 70 GtC and follow global carbon cycle dynamics over another 900 years. In additional parameter perturbation runs, we varied the default terrestrial photosynthesis CO2 fertilization parameterization by ±50 % in order to test the sensitivity of this uncertain carbon cycle feedback to the targeted atmospheric carbon reduction through direct CO2 injections. Simulated seawater chemistry changes and marine carbon storage effectiveness are similar to previous studies. As expected, by the end of the injection period avoided emissions fall short of the targeted 70 GtC by 16–30 % as a result of carbon cycle feedbacks and backfluxes in both land and ocean reservoirs. The target emissions reduction in the parameter perturbation simulations is about 0.2 and 2 % more at the end of the injection period and about 9 % less to 1 % more at the end of the simulations when compared to the unperturbed injection runs. An unexpected feature is the effect of the model's internal variability of deep-water formation in the Southern Ocean, which, in some model runs, causes additional oceanic carbon uptake after injection termination relative to a control run without injection and therefore with slightly different atmospheric CO2 and climate. These results of a model that has very low internal climate variability illustrate that the attribution of carbon fluxes and accounting for injected CO2 may be very challenging in the real climate system with its much larger internal variability.

Description: The addition of carbonate minerals to seawater through an artificial ocean alkalinity enhancement (OAE) process increases the concentrations of hydroxide, bicarbonate, and carbonate ions. This leads to changes in the pH and the buffering capacity of the seawater. Consequently, OAE could have relevant effects on marine organisms and in the speciation and concentration of trace metals that are essential for their physiology. During September and October 2021, a mesocosm experiment was carried out in the coastal waters of Gran Canaria (Spain), consisting on the controlled variation of total alkalinity (TA). Different concentrations of carbonate salts (NaHCO3 and Na2CO3) previously homogenized were added to each mesocosm to achieve an alkalinity gradient between Δ0 to Δ2400 µmol L−1. The lowest point of the gradient was 2400 µmol kg−1, being the natural alkalinity of the medium, and the highest point was 4800 µmol kg−1. Iron (Fe) speciation was monitored during this experiment to analyse total dissolved iron (TdFe, unfiltered samples), dissolved iron (dFe, filtered through a 0.2 µm pore size filter), soluble iron (sFe, filtered through a 0.02 µm pore size filter), dissolved labile iron (dFe′), iron-binding ligands (LFe), and their conditional stability constants () because of change due to OAE and the experimental conditions in each mesocosm. Observed iron concentrations were within the expected range for coastal waters, with no significant increases due to OAE. However, there were variations in Fe size fractionation during the experiment. This could potentially be due to chemical changes caused by OAE, but such an effect is masked by the stronger biological interactions. In terms of size fractionation, sFe was below 1.0 nmol L−1, dFe concentrations were within 0.5–4.0 nmol L−1, and TdFe was within 1.5–7.5 nmol L−1. Our results show that over 99 % of Fe was complexed, mainly by L1 and L2 ligands with ranging between 10.92 ± 0.11 and 12.68 ± 0.32, with LFe ranging from 1.51 ± 0.18 to 12.3 ± 1.8 nmol L−1. Our data on iron size fractionation, concentration, and iron-binding ligands substantiate that the introduction of sodium salts in this mesocosm experiment did not modify iron dynamics. As a consequence, phytoplankton remained unaffected by alterations in this crucial element.

Description: The Weddell Sea Polynya (WSP) is a large opening within the sea ice cover of the Weddell Sea sector. It has been a rare event in the satellite period, appearing between 1973 and 1976 and again in 2016/2017. Coupled modelling studies have suggested that there may be a large-scale atmospheric response to the WSP. Here, the direct atmospheric response to the WSP is estimated from atmosphere-only numerical experiments. Three different models, the HadGEM3 UK Met Office model, the ECHAM5 Max Planck Institute model, and the OpenIFS ECMWF model, each at two different resolutions, are used to test the robustness of our results. The use of large ensembles reduces the weather variability and isolates the atmospheric response. Results show a large (∼100-200 Wm-2) turbulent air-sea flux anomaly above the polynya. The response to the WSP is local and of short duration (barely outlasting the WSP) with a similar magnitude and spatial pattern of lower-tropospheric warming and increase in precipitation in all six configurations. All models show a weak decrease in surface pressure over the WSP, but this response is small (∼2 hPa) in comparison to internal variability. The dynamic response is inconsistent between models and resolutions above the boundary layer, suggesting a weak or null response that is covered by internal variability aloft. The higher resolution does not alter the pattern of the response but increases its magnitude by up ∼50% in two of the three models. The response is influenced by natural variability in the westerly jet. The models perform well against ERA5 reanalysis data for the 1974 WSP in spatial response and magnitude, showing a turbulent heat flux of approximately 150 W m-2.

Description: In September 2021, volcanic aerosol (mainly freshly formed sulfate plumes) originating from the eruption of Cumbre Vieja on La Palma, Canary Islands, Spain, crossed Cabo Verde at altitudes below 2 km. On 24 September 2021, an extraordinary large aerosol optical depth (AOD) close to 1 (daily mean at 500 nm) was observed at Mindelo, Cabo Verde. This event provided favorable conditions to obtain lidar-derived profiles of extinction and backscatter coefficients, lidar ratio, and depolarization ratio at 355, 532 and 1064 nm in the sulfate aerosol plume. A novel feature of the lidar system operated at Mindelo is the availability of extinction, lidar ratio and depolarization measurements at 1064 nm in addition to the standard wavelengths of 355 and 532 nm. Having measurements of these parameters at all three wavelengths is a major advantage for the aerosol characterization and in aerosol typing efforts as the lidar ratio and the particle linear depolarization ratio are key parameters for this purpose. In this article, we present the key results of the lidar observations obtained on one specific day, namely on 24 September 2021 at 04:38-05:57 UTC, including the first ever measurements of the particle extinction coefficient, the lidar ratio and the depolarization ratio at 1064 nm for volcanic sulfate, and discuss the findings in terms of aerosol optical properties and mass concentrations by comparison with a reference observation (16 September 2021) representing the typical background conditions before the start of the eruptions. We found an unusual high particle extinction coefficient of 721 +/- 51, 549 +/- 38 and 178 +/- 13 Mm - 1 , as well as an enhanced lidar ratio of 66.9 +/- 10.1, 60.2 +/- 9.2 and 30.8 +/- 8.7 sr at 355, 532 and 1064 nm, respectively, in the sulfate-dominated planetary boundary layer (PBL). The particle linear depolarization ratio was 〈= 0.9 % at all respective wavelengths. It is the first time that lidar-derived intensive aerosol optical properties could be derived for volcanic sulfate at all three wavelengths, and thus it is a highly valuable data set for global aerosol characterization. The lidar analysis also revealed a sulfate-related AOD of about 0.35 +/- 0.03 at 532 nm of the total PBL-related AOD of 0.43. The rest of the AOD contribution was caused by a lofted Saharan dust layer extending from 1.4 to 5 km and leading to a total AOD of 0.79 at 532 nm. Volcanic ash contribution to the observed aerosol plumes could be mostly excluded based on trajectory analysis and the observed optical properties. Peak mass concentration was 178.5 +/- 44.6 mu g m - 3 in the volcanic-influenced and sulfate-dominated polluted PBL, showing the hazardous potential of such sulfate plumes to significantly worsen local air quality even at remote locations.

Description: Nitrous oxide (N2O) is a long-lived potent greenhouse gas and stratospheric ozone-depleting substance, which has been accumulating in the atmosphere since the pre-industrial period. The mole fraction of atmospheric N2O has increased by nearly 25 % from 270 parts per billion (ppb) in 1750 to 336 ppb in 2022, with the fastest annual growth rate since 1980 of more than 1.3 ppb yr-1 in both 2020 and 2021. As a core component of our global greenhouse gas assessments coordinated by the Global Carbon Project (GCP), we present a global N2O budget that incorporates both natural and anthropogenic sources and sinks, and accounts for the interactions between nitrogen additions and the biochemical processes that control N2O emissions. We use Bottom-Up (BU: inventory, statistical extrapolation of flux measurements, process-based land and ocean modelling) and Top-Down (TD: atmospheric measurement-based inversion) approaches. We provide a comprehensive quantification of global N2O sources and sinks in 21 natural and anthropogenic categories in 18 regions between 1980 and 2020. We estimate that total annual anthropogenic N2O emissions increased 40 % (or 1.9 Tg N yr-1) in the past four decades (1980–2020). Direct agricultural emissions in 2020, 3.9 Tg N yr−1 (best estimate) represent the large majority of anthropogenic emissions, followed by other direct anthropogenic sources (including ‘Fossil fuel and industry’, ‘Waste and wastewater’, and ‘Biomass burning’ (2.1 Tg N yr−1), and indirect anthropogenic sources (1.3 Tg N yr−1). For the year 2020, our best estimate of total BU emissions for natural and anthropogenic sources was 18.3 (lower-upper bounds: 10.5–27.0) Tg N yr-1, close to our TD estimate of 17.0 (16.6–17.4) Tg N yr-1. For the period 2010–2019, the annual BU decadal-average emissions for natural plus anthropogenic sources were 18.1 (10.4–25.9) Tg N yr-1 and TD emissions were 17.4 (15.8–19.20 Tg N yr-1. The once top emitter Europe has reduced its emissions since the 1980s by 31 % while those of emerging economies have grown, making China the top emitter since the 2010s. The observed atmospheric N2O concentrations in recent years have exceeded projected levels under all scenarios in the Coupled Model Intercomparison Project Phase 6 (CMIP6), underscoring the urgency to reduce anthropogenic N2O emissions. To evaluate mitigation efforts and contribute to the Global Stocktake of the United Nations Framework Convention on Climate Change, we propose establishing a global network for monitoring and modeling N2O from the surface through the stratosphere. The data presented in this work can be downloaded from https://doi.org/10.18160/RQ8P-2Z4R (Tian et al. 2023).

Description: Fjord-like estuaries are hotspots of biogeochemical cycling due to steep physicochemical gradients. The spatiotemporal distribution of nitrous oxide (N2O) within many of these systems is poorly described, especially in the southern hemisphere. The goal of this study is to describe the spatiotemporal distribution of N2O within a southern hemisphere fjord-like estuary, describe the main environmental drivers of this distribution, the air/sea flux of N2O, and the main drivers of N2O production. Cruises were undertaken in Macquarie Harbour, Tasmania to capture N2O concentrations and water column physicochemical profiles in winter (July 2022), spring (October 2022), summer (February 2023), and autumn (April 2023). N2O samples were collected at one depth at system end members, and at 5 depths at 4 stations within the harbour. Results indicate that N2O is consistently supersaturated (reaching 170 % saturation) below the system’s freshwater lens where oxygen concentrations are often hypoxic, but infrequently anoxic. In the surface lens, levels of N2O saturation vary with estimated river flow and with proximity to the system’s main freshwater endmember. The linear relationship between AOU and ΔN2O saturation indicates that nitrification is the process generating N2O in the system. When river flow was high (July and October 2022), surface water N2O was undersaturated (as low as 70 %) throughout most of the harbour. When river flow was low (February and April 2023) N2O was observed to be supersaturated at most stations. Calculated air/sea fluxes of N2O indicated that the system is generally a source of N2O to the atmosphere under weak river flow conditions and a sink during strong river flow conditions. The diapycnal flux was a minor contributor to surface water N2O concentrations, and subhalocline N2O is intercepted by the riverine surface lens and transported out of the system to the ocean during strong river flow conditions. In a changing climate, Western Tasmania is expected to receive higher winter rainfall and lower summer rainfall which may augment the source and sink dynamics of this system by enhancing the summer / autumn efflux of N2O to the atmosphere. This study is the first to report observations of N2O distribution, generation processes, and estimated diapycnal / surface N2O fluxes from this system.

Description: Numerical models are a powerful tool for investigating the dynamic processes in the interior of the Earth and other planets, but the reliability and predictive power of these discretized models depends on the numerical method as well as an accurate representation of material properties in space and time. In the specific context of geodynamic models, particle methods have been applied extensively because of their suitability for advection-dominated processes and have been used in applications such as tracking the composition of solid rock and melt in the Earth's mantle, fluids in lithospheric- and crustal-scale models, light elements in the liquid core, and deformation properties like accumulated finite strain or mineral grain size, along with many applications outside the Earth sciences.There have been significant benchmarking efforts to measure the accuracy and convergence behavior of particle methods, but these efforts have largely been limited to instantaneous solutions, or time-dependent models without analytical solutions. As a consequence, there is little understanding about the interplay of particle advection errors and errors introduced in the solution of the underlying transient, nonlinear flow equations. To address these limitations, we present two new dynamic benchmarks for transient Stokes flow with analytical solutions that allow us to quantify the accuracy of various advection methods in nonlinear flow. We use these benchmarks to measure the accuracy of our particle algorithm as implemented in the ASPECT geodynamic modeling software against commonly employed field methods and analytical solutions. In particular, we quantify if an algorithm that is higher-order accurate in time will allow for better overall model accuracy and verify that our algorithm reaches its intended optimal convergence rate. We then document that the observed increased accuracy of higher-order algorithms matters for geodynamic applications with an example of modeling small-scale convection underneath an oceanic plate and show that the predicted place and time of onset of small-scale convection depends significantly on the chosen particle advection method.Descriptions and implementations of our benchmarks are openly available and can be used to verify other advection algorithms. The availability of accurate, scalable, and efficient particle methods as part of the widely used open-source code ASPECT will allow geodynamicists to investigate complex time-dependent geodynamic processes such as elastic deformation, anisotropic fabric development, melt generation and migration, and grain damage.

Description: Tectonics play a significant role in shaping the morphology of submarine canyons, which form essential links in source-to-sink (S2S) systems. It is difficult, however, to investigate the resulting morphodynamics over the long term. For this purpose, we propose a novel experimental approach that can generate submarine canyons and hanging-wall fans on continuously evolving active faults. We utilize morphometric analysis and morphodynamic models to understand the response of these systems to fault slip rate (Vr) and inflow discharge (Q). Our research reveals several key findings. Firstly, the fault slip rate controls the merging speed of submarine canyons and hanging-wall fans, which in turn affects their quantity and spacing. Additionally, the long profile shapes of submarine canyons and hanging-wall fans can be decoupled into a gravity-dominated breaching process and an underflow-dominated diffusion process, which can be described using a constant-slope relationship and a morphodynamic diffusion model, respectively. Furthermore, both experimental and simulated submarine canyon–hanging-wall fan long profiles exhibit strong self-similarity, indicating that the long profiles are scale independent. The Hack's scaling relationship established through morphometric analyses serves as an important link between different scales in S2S systems, bridging laboratory-scale data to field-scale data and submarine-to-terrestrial relationships. Lastly, for deep-water sedimentary systems, we propose an empirical formula to estimate fan volume using canyon length, and the data from 26 worldwide S2S systems utilized for comparison show a strong agreement. Our geomorphic experiments provide a novel perspective for better understanding of the influence of tectonics on deep-water sedimentary processes. The scaling relationships and empirical formulas we have established aim to assist in estimating volume information that is difficult to obtain during long-term landscape evolution processes.

Description: The distribution of water masses, and the ventilation rates of these, are of significance to the thermohaline circulation and biogeochemistry of the world oceans. The distribution of the main water masses in the Atlantic Ocean is published in a companion study (Liu and Tanhua, 2021), their ages and ventilation time-scales are reported here by using observations of the transient tracers, CFC-12 and SF6. Two different definitions of water mass ages are presented; the mean-age representing an average age of a water mass, and the mode-age that better represents the advective time-scale. In general, ages increase with pressure and along the pathway of a water mass. The central waters in the upper layer obtain the mean-ages of up to ~100 years and the mode-ages of up to ~30 years. In the intermediate layer, the Antarctic Intermediate Water (AAIW) and the Mediterranean Water (MW) show gradients of water mass ages in the meridional and zonal direction respectively. The AAIW obtains the highest mean-age of ~300 years and mode-age of ~80 years at 30° N, while the MW shows the highest mean-age of ~400 years and mode-age of ~100 years in the equator region. As the dominant water mass in the deep and overflow layer, the North Atlantic Deep Water (NADW) from high northern latitudes obtains the highest mean-age of ~600 years and mode-age of ~100 years in the Antarctic Circumpolar Current (ACC) region at 50° S. In the bottom layer, the Antarctic Bottom Water (AABW) from the Weddell Sea obtains the highest mean-age of ~600 years and mode-age of ~100 years in the equator. As the continuation of AABW, the Northeast Atlantic Bottom Water (NEABW) obtains the highest mean-age of ~800 years and mode-age of ~120 years at 50° N. The mode-age increases with the transport distance from formation area, accompanied by significant differences between the eastern and western basins. The mode-age is used to calculate the oxygen utilization rate (OUR) with apparent oxygen utilization (AOU) during the active transport in water masses. The western basin exhibits lower mode-age with higher oxygen (low AOU) due to the better ventilation. The OUR shows similar distribution to dissolved oxygen (DO), indicating higher oxidation rate in the high oxygen region.

Description: Spatial predictions of total organic carbon (TOC) concentrations and stocks are crucial for understanding marine sediments’ role as a significant carbon sink in the global carbon cycle. In this study, we present a geospatial prediction of TOC concentrations and stocks at a 5 x 5 arc minute grid scale, using a deep learning model — a novel machine learning approach based on a new compilation of over 22,000 global TOC measurements and a new set of predictors, such as seafloor lithologies, grain size distribution, and an alpha-chlorophyll satellite data. In our study, we compared the predictions and discuss the limitations from various machine learning methods. Our findings reveal that the neural network approach outperforms methods such as k Nearest Neighbors and random forests, which tend to overfit to the training data, especially in highly heterogeneous and complex geological settings. We provide estimates of mean TOC concentrations and total carbon stock in both continental shelves and deep sea settings across various marine regions and oceans. Our model suggests that the upper 10 cm of oceanic sediments harbors approximately 171 Pg of TOC stock and has a mean TOC concentration of 0.68 %. Furthermore, we introduce a standardized methodology for quantifying predictive uncertainty using Monte Carlo dropout and present a map of information gain, that measures the expected increase in model knowledge achieved through in-situ sampling at specific locations which is pivotal for sampling strategy planning.

Description: Nitric oxide (NO) is an intermediate of various microbial nitrogen cycle processes and the open ocean and coastal areas are generally a source of NO in the atmosphere. However, our knowledge about its distribution and the main production processes in coastal areas and estuaries is rudimentary at best. To this end, dissolved NO concentrations were measured for the first time in surface waters along the lower Elbe Estuary and Hamburg Port area in July 2021. The discrete surface water samples were analyzed using a chemiluminescence detection method. The NO concentrations ranged from below the limit of detection (9.1 × 10−12 mol L−1) to 17.7 × 10−12 mol L−1, averaging at 12.5 × 10−12 mol L−1 and were supersaturated in the surface layer of both the lower Elbe Estuary and the Hamburg Port area, indicating that the study site was a source of NO to the atmosphere during the study period. On the basis of a comprehensive comparison of NO concentrations with parallel nutrient, oxygen, and nitrous oxide concentration measurements, we conclude that the observed distribution of dissolved NO was most likely resulting from microbial nitrogen transformation processes, particularly nitrification in the coastal-brackish and limnic zones of the lower Elbe Estuary and nitrifier-denitrification in the Hamburg Port area.

Description: Phytoplankton form the base of the marine food web by transforming CO2 into organic carbon via photosynthesis. Despite the importance of phytoplankton for marine ecosystems and global carbon cycling, projections of phytoplankton biomass in response to climate change differ strongly across Earth system models, illustrating uncertainty in our understanding of the underlying processes. Differences are especially large in the Southern Ocean, a region that is notoriously difficult to represent in models. Here, we argue that total (depth-integrated) phytoplankton biomass in the Southern Ocean is projected to largely remain unchanged under climate change by the Coupled Model Intercomparison Project Phase 6 (CMIP6) multi-model ensemble because of a shifting balance of bottom-up and top-down processes driven by a shoaling mixed-layer depth. A shallower mixed layer is projected on average to improve growth conditions, consequently weaken bottom-up control, and confine phytoplankton closer to the surface. An increase in the phytoplankton concentration promotes zooplankton grazing efficiency, thus intensifying top-down control. However, large differences across the model ensemble exist, with some models simulating a decrease in surface phytoplankton concentrations. To reduce uncertainties in projections of surface phytoplankton concentrations, we employ an emergent constraint approach using the observed sensitivity of surface chlorophyll concentration, taken as an observable proxy for phytoplankton, to seasonal changes in the mixed-layer depth as an indicator for future changes in surface phytoplankton concentrations. The emergent constraint reduces uncertainties in surface phytoplankton concentration projections by around one-third and increases confidence that surface phytoplankton concentrations will indeed rise due to shoaling mixed layers under global warming, thus favouring intensified top-down control. Overall, our results suggest that while changes in bottom-up conditions stimulate enhanced growth, intensified top-down control opposes an increase in phytoplankton and becomes increasingly important for the phytoplankton response to climate change in the Southern Ocean.

Description: Events of extreme precipitation pose a hazard to many parts of Europe but are typically not well represented in climate models. Here, we evaluate daily extreme precipitation over Europe during 1982–2019 in observations (GPCC), reanalysis (ERA5) and a set of atmosphere-only simulations at low- (100 km), medium- (50 km) and high- (25 km) horizontal resolution with identical vertical resolutions using OpenIFS (version 43r3). We find that both OpenIFS simulations and reanalysis underestimate the rates of extreme precipitation compared to observations. The biases are largest for the lowest resolution (100 km) and decrease with increasing horizontal resolution (50 and 25 km) simulations in all seasons. The sensitivity to horizontal resolution is particularly high in mountain regions (such as the Alps, Scandinavia, Iberian Peninsula), likely linked to the sensitivity of vertical velocity to the representation of topography. The sensitivity of precipitation to model resolution increases dramatically with increasing percentiles, with modest biases in the 70th–80thpercentile range and large biases above the 99th percentile range. We also find that precipitation above the 99th percentile mostly consists of large-scale precipitation (~80 %) in winter, while in summer it is mostly large-scale precipitation in Northern Europe (~70 %) and convective precipitation in Southern Europe (~70 %). Compared to ERA5, the OpenIFS overestimates large-scale precipitation extremes in winter, but underestimates in summer. The discrepancy between OpenIFS and ERA5 decreases with increasing horizontal resolutions. We also examine the sensitivity of extreme precipitation to model time step and find that the convective contribution to extreme precipitation is more sensitive to the model time step than the horizontal resolution. This is likely due to the sensitivity of convective activity to model time step. On the other hand, the large-scale contribution to extreme precipitation is more sensitive to horizontal resolution than the model time step, which may be due to sharper fronts and steeper topography at higher horizontal resolution.

Description: The Peruvian Upwelling System hosts an extremely high productive marine ecosystem. Observations show that the Peruvian Upwelling System is the only Eastern Boundary Upwelling Systems (EBUS) with an out-of-phase relationship of seasonal surface chlorophyll concentrations and upwelling intensity. This "seasonal paradox" triggers the questions: (1) what is the uniqueness of the Peruvian Upwelling System compared with other EBUS that leads to the out of phase relationship; (2) how does this uniqueness lead to low phytoplankton biomass in austral winter despite strong upwelling and ample nutrients? Using observational climatologies for four EBUS we diagnose that the Peruvian Upwelling System is unique in that intense upwelling coincides with deep mixed layers. We then apply a coupled regional ocean circulation-biogeochemical model (CROCO-BioEBUS) to assess how the interplay between mixed layer and upwelling is regulating the seasonality of surface chlorophyll in the Peruvian Upwelling System. The model recreates the "seasonal paradox" within 200 km off the Peruvian coast. We confirm previous findings that deep mixed layers, which cause vertical dilution and stronger light limitation, mostly drive the diametrical seasonality of chlorophyll relative to upwelling. In contrast to previous studies, reduced phytoplankton growth due to enhanced upwelling of cold waters and lateral advection are second-order drivers of low surface chlorophyll concentrations. This impact of deep mixed layers and upwelling propagates up the ecosystem, from primary production to export efficiency. Our findings emphasize the crucial role of the interplay of the mixed layer and upwelling and suggest that surface chlorophyll may increase along with a weakened seasonal paradox in response to shoaling mixed layers under climate change.

Description: The University of Victoria Earth system climate model of intermediate complexity has been a useful tool in recent assessments of long-term climate changes including paleo-climate modelling. Since the last official release of the UVic ESCM 2.9, and the two official updates during the last decade, a lot of model development has taken place in multiple groups. The new version 2.10 of the University of Victoria Earth System Climate Model (UVic ESCM), to be used in the 6th phase of the coupled model intercomparison project (CMIP6), presented here combines and brings together multiple model developments and new components that have taken place since the last official release of the model. To set the foundation of its use, we here describe the UVic ESCM 2.10 and evaluate results from transient historical simulations against observational data. We find that the UVic ESCM 2.10 is capable of reproducing well changes in historical temperature and carbon fluxes, as well as the spatial distribution of many ocean tracers, including temperature, salinity, phosphate and nitrate. This is connected to a good representation of ocean physical properties. For the moment, there remain biases in ocean alkalinity and dissolved inorganic carbon, which will be addressed in the next updates to the model.

Description: To better understand possible reasons for the diverse modeling results and large discrepancies of the detected solar fingerprints, we took one step back and assessed the "initial" solar signals in the middle atmosphere based on large ensemble simulations with multiple climate models — FOCI, EMAC, and MPI-ESM-HR. Consistent with previous work, we find that the 11-year solar cycle signals in the short wave heating rate (SWHR) and ozone anomalies are robust and statistically significant in all three models. These "initial" solar cycle signals in SWHR, ozone, and temperature anomalies are sensitive to the strength of the solar forcing. Correlation coefficients of the solar cycle with the SWHR, ozone, and temperature anomalies linearly increase along with the enhancement of the solar cycle amplitude, and this reliance becomes more complex when the solar cycle amplitude exceeds a certain threshold. In addition, the cold bias in the tropical stratopause of EMAC dampens the subsequent results of the "initial" solar signal. The warm pole bias in MPI-ESM-HR leads to a weak polar night jet (PNJ), which may limit the top-down propagation of the initial solar signal. Although FOCI simulated a so-called top-down response as revealed in previous studies in a period with large solar cycle amplitudes, its warm bias in the tropical upper stratosphere results in a positive bias in PNJ and can lead to a "reversed" response in some extreme cases. We suggest a careful interpretation of the single model result and further re-examination of the solar signal based on more climate models.

Description: In the framework of a changing climate, it is useful to devise methods capable of effectively assessing and monitoring the changing landscape of air-sea CO2 fluxes. In this study, we developed an integrated machine learning tool to objectively classify and track marine carbon biomes under seasonally and interannually changing environmental conditions. The tool was applied to the monthly output of a global ocean biogeochemistry model at 0.25° resolution run under atmospheric forcing for the period 1958–2018. Carbon biomes are defined as regions having consistent relations between surface CO2 fugacity (fCO2) and its main drivers (temperature, dissolved inorganic carbon, alkalinity). We detected carbon biomes by using an agglomerative hierarchical clustering (HC) methodology applied to spatial target-driver relationships, whereby a novel adaptive approach to cut the HC dendrogram based on the compactness and similarity of the clusters was employed. Based only on the spatial variability of the target-driver relationships and with no prior knowledge on the cluster location, we were able to detect well-defined and geographically meaningful carbon biomes. A deep learning model was constructed to track the seasonal and interannual evolution of the carbon biomes, wherein a feed-forward neural network was trained to assign labels to detected biomes. We find that the area covered by the carbon biomes responds robustly to seasonal variations in environmental conditions. A seasonal alternation between different biomes is observed over the North Atlantic and Southern Ocean. Long-term trends in biome coverage over the 1958–2018 period, namely a 10 % expansion of the subtropical biome in the North Atlantic and a 10 % expansion of the subpolar biome in the Southern Ocean, are suggestive of long-term climate shifts. Our approach thus provides a framework that can facilitate the monitoring of the impacts of climate change on the ocean carbon cycle and the evaluation of carbon cycle projections across Earth System Models.

Description: In this paper we describe the implementation of the carbon isotopes 13C and 14C (radiocarbon) into the marine biogeochemistry model REcoM3. The implementation is tested in long-term equilibrium simulations where REcoM3 is coupled with the ocean general circulation model FESOM2.1, applying a low-resolution configuration and idealized climate forcing. Focusing on the carbon-isotopic composition of dissolved inorganic carbon (δ13CDIC and Δ14CDIC), our model results are largely consistent with reconstructions for the pre-anthropogenic period. Our simulations also exhibit discrepancies, e.g. in upwelling regions and the interior of the North Pacific. Some of these differences are due to the limitations of our ocean circulation model setup, which results in a rather shallow meridional overturning circulation. We additionally study the accuracy of two simplified modelling approaches for dissolved inorganic 14C, which are faster (15 % and about a factor of five, respectively) than the complete consideration of the marine radiocarbon cycle. The accuracy of both simplified approaches is better than 5 %, which should be sufficient for most studies of Δ14CDIC.

Description: Laboratory experiments showed that the isotopic fractionation of δ13C and of δ18O during calcite formation of planktic foraminifera are species-specific functions of ambient CO concentration. This effect became known as the carbonate ion effect (CIE), whose role for the interpretation of marine sediment data will be investigated here in an in-depth analysis of the 13C cycle. For this investigation, we constructed new 160 kyr long mono-specific stacks of changes in both δ13C and δ18O from either the planktic foraminifera Globigerinoides ruber (rub) or Trilobatus sacculifer (sac) from 112 and 40 marine records, respectively, from the wider tropics (latitudes below 38°). Both mono-specific time series Δ(δ13Crub) and Δ(δ13Csac) are very similar to each other, and a linear regression through a scatter plot of both data sets has a slope of ∼ 0.99 – although the laboratory-based CIE for both species differs by a factor of nearly 2, implying that they should record distinctly different changes in δ13C, if we accept that the carbonate ion concentration changes on glacial–interglacial timescales. For a deeper understanding of the 13C cycle, we use the Solid Earth version of the Box model of the Isotopic Carbon cYCLE (BICYLE-SE) to calculate how surface-ocean CO should have varied over time in order to be able to calculate the potential offsets which would by caused by the CIE quantified in culture experiments. Our simulations are forced with atmospheric reconstructions of CO2 and δ13CO2 derived from ice cores to obtain a carbon cycle which should at least at the surface ocean be as close as possible to expected conditions and which in the deep ocean largely agrees with the carbon isotope ratio of dissolved inorganic carbon (DIC), δ13CDIC, as reconstructed from benthic foraminifera. We find that both Δ(δ13Crub) and Δ(δ13Csac) agree better with changes in simulated δ13CDIC when ignoring the CIE than those time series which were corrected for the CIE. The combination of data- and model-based evidence for the lack of a role for the CIE in Δ(δ13Crub) and Δ(δ13Csac) suggests that the CIE as measured in laboratory experiments is not directly transferable to the interpretation of marine sediment records. The much smaller CIE-to-glacial–interglacial-signal ratio in foraminifera δ18O, when compared to δ13C, prevents us from drawing robust conclusions on the role of the CIE in δ18O as recorded in the hard shells of both species. However, theories propose that the CIE in both δ13C and δ18O depends on the pH in the surrounding water, suggesting that the CIE should be detectable in neither or both of the isotopes. Whether this lack of role of the CIE in the interpretation of planktic paleo-data is a general feature or is restricted to the two species investigated here needs to be checked with further data from other planktic foraminiferal species.

Description: An increasing number of climate model simulations is becoming available for the transition from the Last Glacial Maximum to the Holocene. Assessing the simulations' reliability requires benchmarking against environmental proxy records. To date, no established method exists to compare these two data sources in space and time over a period with changing background conditions. Here, we develop a new algorithm to rank simulations according to their deviation from reconstructed magnitudes and temporal patterns of orbital and millennial-scale temperature variations. The use of proxy forward modeling allows for accounting for non-climatic processes that affect the temperature reconstructions. It further avoids the need to reconstruct gridded fields or regional mean temperature time series from sparse and uncertain proxy data. First, we test the reliability and robustness of our algorithm in idealized experiments with prescribed deglacial temperature histories. We quantify the influence of limited temporal resolution, chronological uncertainties, and non-climatic processes by constructing noisy pseudo-proxies. While model–data comparison results become less reliable with increasing uncertainties, we find that the algorithm discriminates well between simulations under realistic non-climatic noise levels. To obtain reliable and robust rankings, we advise spatial averaging of the results for individual proxy records. Second, we demonstrate our method by quantifying the deviations between an ensemble of transient deglacial simulations and a global compilation of sea surface temperature reconstructions. The ranking of the simulations differs substantially between the considered regions and timescales, which suggests that optimizing for agreement with the temporal patterns of a small set of proxies might be insufficient for capturing the spatial structure of the deglacial temperature variability. We attribute the diversity in the rankings to more regionally confined temperature variations in reconstructions than in simulations, which could be the result of uncertainties in boundary conditions, shortcomings in models, or regionally varying characteristics of reconstructions such as recording seasons and depths. Future work towards disentangling these potential reasons can leverage the flexible design of our algorithm and its demonstrated ability to identify varying levels of model–data agreement. Additionally, the algorithm can be applied to variables like oxygen isotopes and climate transitions such as the penultimate deglaciation and the last glacial inception.

Description: Oxygen isotopes in biogenic silica (δ18OBSi) from lake sediments allow for quantitative reconstruction of past hydroclimate and proxy-model comparison in terrestrial environments. The signals of individual records have been attributed to different factors, such as air temperature (Tair), atmospheric circulation patterns, hydrological changes, and lake evaporation. While every lake has its own local set of drivers of δ18O variability, here we explore the extent to which regional or even global signals emerge from a series of paleoenvironmental records. This study provides a comprehensive compilation and combined statistical evaluation of the existing lake sediment δ18OBSi records, largely missing in other summary publications (i.e. PAGES network). For this purpose, we have identified and compiled 71 down-core records published to date and complemented these datasets with additional lake basin parameters (e.g. lake water residence time and catchment size) to best characterize the signal properties. Records feature widely different temporal coverage and resolution, ranging from decadal-scale records covering the past 150 years to records with multi-millennial-scale resolution spanning glacial–interglacial cycles. The best coverage in number of records (N = 37) and data points (N = 2112) is available for Northern Hemispheric (NH) extratropical regions throughout the Holocene (roughly corresponding to Marine Isotope Stage 1; MIS 1). To address the different variabilities and temporal offsets, records were brought to a common temporal resolution by binning and subsequently filtered for hydrologically open lakes with lake water residence times 〈 100 years. For mid- to high-latitude (〉 45° N) lakes, we find common δ18OBSi patterns among the lake records during both the Holocene and Common Era (CE). These include maxima and minima corresponding to known climate episodes, such as the Holocene Thermal Maximum (HTM), Neoglacial Cooling, Medieval Climate Anomaly (MCA) and the Little Ice Age (LIA). These patterns are in line with long-term air temperature changes supported by previously published climate reconstructions from other archives, as well as Holocene summer insolation changes. In conclusion, oxygen isotope records from NH extratropical lake sediments feature a common climate signal at centennial (for CE) and millennial (for Holocene) timescales despite stemming from different lakes in different geographic locations and hence constitute a valuable proxy for past climate reconstructions.

Description: We present transient simulations of the last glacial inception using the Earth system model CLIMBER-X with dynamic vegetation, interactive ice sheets, and visco-elastic solid Earth responses. The simulations are initialized at the middle of the Eemian interglacial (125 kiloyears before present, ka) and run until 100 ka, driven by prescribed changes in Earth's orbital parameters and greenhouse gas concentrations from ice core data. CLIMBER-X simulates a rapid increase in Northern Hemisphere ice sheet area through MIS5d, with ice sheets expanding over northern North America and Scandinavia, in broad agreement with proxy reconstructions. While most of the increase in ice sheet area occurs over a relatively short period between 119 and 117 ka, the larger part of the increase in ice volume occurs afterwards with an almost constant ice sheet extent. We show that the vegetation feedback plays a fundamental role in controlling the ice sheet expansion during the last glacial inception. In particular, with prescribed present-day vegetation the model simulates a global sea level drop of only ∼ 20 m, compared with the ∼ 35 m decrease in sea level with dynamic vegetation response. The ice sheet and carbon cycle feedbacks play only a minor role during the ice sheet expansion phase prior to ∼ 115 ka but are important in limiting the deglaciation during the following phase characterized by increasing summer insolation. The model results are sensitive to climate model biases and to the parameterization of snow albedo, while they show only a weak dependence on changes in the ice sheet model resolution and the acceleration factor used to speed up the climate component. Overall, our simulations confirm and refine previous results showing that climate–vegetation–cryosphere feedbacks play a fundamental role in the transition from interglacial to glacial states characterizing Quaternary glacial cycles.

Description: The glacial–interglacial cycles of the Quaternary exhibit 41 kyr periodicity before the Mid-Pleistocene Transition (MPT) around 1.2–0.8 Myr ago and ∼ 100 kyr periodicity after that. From the viewpoint of dynamical systems, proposed mechanisms generating these periodicities are broadly divided into two types: (i) nonlinear forced responses of a mono- or multi-stable climate system to the astronomical forcing or (ii) synchronization of internal self-sustained oscillations to the astronomical forcing. In this study, we investigate the dynamics of glacial cycles simulated by the Earth system model of intermediate complexity CLIMBER-2 with a fully interactive carbon cycle, which reproduces the MPT under gradual changes in volcanic-CO2 degassing and regolith cover. We report that, in this model, the dominant frequency of glacial cycles is set in line with the principle of synchronization. It is found that the model exhibits self-sustained oscillations in the absence of astronomical forcing. Before the MPT, glacial cycles synchronize to the 41 kyr obliquity cycles because the self-sustained oscillations have periodicity relatively close to 41 kyr. After the MPT the timescale of internal oscillations becomes too long to follow every 41 kyr obliquity cycle, and the oscillations synchronize to the 100 kyr eccentricity cycles that modulate the amplitude of climatic precession. The latter synchronization occurs with the help of the 41 kyr obliquity forcing, which enables some terminations and glaciations to occur robustly at their right timing. We term this phenomenon vibration-enhanced synchronization because of its similarity to the noise-enhanced synchronization known in nonlinear science. While we interpret the dominant periodicities of glacial cycles as the result of synchronization of internal self-sustained oscillations to the astronomical forcing, the Quaternary glacial cycles show facets of both synchronization and forced response.

Description: Ocean alkalinity enhancement (OAE) seeks to increase the alkalinity of seawater for carbon dioxide removal (CDR). Following numerous propositions to trial, test, or upscale OAE for CDR, multiple social considerations have begun to be identified. To ensure that OAE research is responsible (is attentive to societal priorities) and successful (does not prematurely engender widespread social rejection), it will be critical to understand how OAE might be perceived as risky or controversial and under what conditions it might be regarded by relevant social groups as most worthy of exploration. To facilitate the answering of these questions, this chapter does the following: (1) characterizes what is known to date about public perceptions of OAE, (2) provides methodological suggestions on how to conduct social science research and public engagement to accompany OAE field research, and (3) addresses how knowledge gained from social research and public engagement on OAE can be integrated into ongoing scientific, siting, and communications work.

Description: Black shale sediments from the Barremian to Aptian South Atlantic document intense and widespread burial of marine organic carbon during the initial stages of seafloor spreading between Africa and South America. The enhanced sequestration of atmospheric CO2 makes these young ocean basins potential drivers of the Early Cretaceous carbon cycle and climate perturbations. The opening of marine gateways between initially restricted basins and related circulation and ventilation changes are a commonly invoked explanation for the transient formation and disappearance of these regional carbon sinks. However, large uncertainties in paleogeographic reconstructions limit the interpretation of available paleoceanographic data and prevent any robust model-based quantifications of the proposed circulation and carbon burial changes. Here, we present a new approach to assess the principal controls on the Early Cretaceous South Atlantic and Southern Ocean circulation changes under full consideration of the uncertainties in available boundary conditions. Specifically, we use a large ensemble of 36 climate model experiments to simulate the Barremian to Albian progressive opening of the Falkland Plateau and Georgia Basin gateways with different configurations of the proto-Drake Passage, the Walvis Ridge, and atmospheric CO2 concentrations. The experiments are designed to complement available geochemical data across the regions and to test circulation scenarios derived from them. All simulations show increased evaporation and intermediate water formation at subtropical latitudes that drive a meridional overturning circulation whose vertical extent is determined by the sill depth of the Falkland Plateau. Densest water masses formed in the southern Angola Basin and potentially reached the deep Cape Basin as Walvis Ridge Overflow Water. Paleogeographic uncertainties are as important as the lack of precise knowledge of atmospheric CO2 levels for the simulated temperature and salinity spread in large parts of the South Atlantic. Overall temperature uncertainties are up to 15 °C and increase significantly with water depth. The ensemble approach reveals temporal changes in the relative importance of geographic and radiative forcings for the simulated oceanographic conditions and, importantly, nonlinear interactions between them. Progressive northward opening of the highly restricted Angola Basin increased the sensitivity of local overturning and upper ocean stratification to atmospheric CO2 concentrations due to large-scale changes in the hydrological cycle, while the chosen proto-Drake Passage depth is critical for the ocean dynamics and CO2 response in the southern South Atlantic. Finally, the simulated processes are integrated into a recent carbon burial framework to document the principal control of the regional gateway evolution on the progressive shift from the prevailing saline and oxygen-depleted subtropical water masses to the dominance of ventilated high-latitude deep waters.

Description: Combining proxy information and climate model simulations reconciles these sources of information about past climates. This, in turn, strengthens our understanding of past climatic changes. The analogue or proxy surrogate reconstruction method is a computationally cheap data assimilation approach, which searches in a pool of simulated climate states the best fit to proxy data. We use the approach to reconstruct European summer mean temperature from the 13th century until present using the Euro 2k set of proxy records and a pool of global climate simulation output fields. Our focus is on quantifying the uncertainty of the reconstruction, because previous applications of the analogue method rarely provided uncertainty ranges. We show several ways of estimating reconstruction uncertainty for the analogue method, which take into account the non-climate part of the variability in each proxy record. In general, our reconstruction agrees well at multi-decadal timescales with the Euro 2k reconstruction, which was conducted with two different statistical methods and no information from model simulations. In both methodological approaches, the decades around the year 1600 CE were the coldest. However, the approaches disagree on the warmest pre-industrial periods. The reconstructions from the analogue method also represent the local variations of the observed proxies. The diverse uncertainty estimates obtained from our analogue approaches can be locally larger or smaller than the estimates from the Euro 2k effort. Local uncertainties of the temperature reconstructions tend to be large in areas that are poorly covered by the proxy records. Uncertainties highlight the ambiguity of field-based reconstructions constrained by a limited set of proxies.

Description: The climate science community aims to improve our understanding of climate change due to anthropogenic influences on atmospheric composition and the Earth's surface. Yet not all climate interactions are fully understood and diversity in climate model experiments persists as assessed in the latest Intergovernmental Panel on Climate Change (IPCC) assessment report. This article synthesizes current challenges and emphasizes opportunities for advancing our understanding of climate change and model diversity. The perspective of this article is based on expert views from three multi-model intercomparison projects (MIPs) – the Precipitation Driver Response MIP (PDRMIP), the Aerosol and Chemistry MIP (AerChemMIP), and the Radiative Forcing MIP (RFMIP). While there are many shared interests and specialisms across the MIPs, they have their own scientific foci and specific approaches. The partial overlap between the MIPs proved useful for advancing the understanding of the perturbation-response paradigm through multi-model ensembles of Earth System Models of varying complexity. It specifically facilitated contributions to the research field through sharing knowledge on best practices for the design of model diagnostics and experimental strategies across MIP boundaries, e.g., for estimating effective radiative forcing. We discuss the challenges of gaining insights from highly complex models that have specific biases and provide guidance from our lessons learned. Promising ideas to overcome some long-standing challenges in the near future are kilometer-scale experiments to better simulate circulation-dependent processes where it is possible, and machine learning approaches for faster and better sub-grid scale parameterizations where they are needed. Both would improve our ability to adopt a smart experimental design with an optimal tradeoff between resolution, complexity and simulation length. Future experiments can be evaluated and improved with sophisticated methods that leverage multiple observational datasets, and thereby, help to advance the understanding of climate change and its impacts.

Description: The presented pilot for the Synthesis Product for Ocean Time Series (SPOTS) includes data from 12 fixed ship-based time-series programs. The related stations represent unique open-ocean and coastal marine environments within the Atlantic Ocean, Pacific Ocean, Mediterranean Sea, Nordic Seas, and Caribbean Sea. The focus of the pilot has been placed on biogeochemical essential ocean variables: dissolved oxygen, dissolved inorganic nutrients, inorganic carbon (pH, total alkalinity, dissolved inorganic carbon, and partial pressure of CO2), particulate matter, and dissolved organic carbon. The time series used include a variety of temporal res- olutions (monthly, seasonal, or irregular), time ranges (10–36 years), and bottom depths (80–6000 m), with the oldest samples dating back to 1983 and the most recent one corresponding to 2021. Besides having been harmo- nized into the same format (semantics, ancillary data, units), the data were subjected to a qualitative assessment in which the applied methods were evaluated and categorized. The most recently applied methods of the time- series programs usually follow the recommendations outlined by the Bermuda Time Series Workshop report (Lorenzoni and Benway, 2013), which is used as the main reference for “method recommendations by prevalent initiatives in the field”. However, measurements of dissolved oxygen and pH, in particular, still show room for improvement. Additional data quality descriptors include precision and accuracy estimates, indicators for data variability, and offsets compared to a reference and widely recognized data product for the global ocean: the GLobal Ocean Data Analysis Project (GLODAP). Generally, these descriptors indicate a high level of continuity in measurement quality within time-series programs and a good consistency with the GLODAP data product, even though robust comparisons to the latter are limited. The data are available as (i) a merged comma-separated file that is compliant with the World Ocean Circulation Experiment (WOCE) exchange format and (ii) a format dependent on user queries via the Environmental Research Division’s Data Access Program (ERDDAP) server of the Global Ocean Observing System (GOOS). The pilot increases the data utility, findability, accessibility, interoperability, and reusability following the FAIR philosophy, enhancing the readiness of biogeochemical time series. It facilitates a variety of applications that benefit from the collective value of biogeochemical time-series observations and forms the basis for a sustained time-series living data product, SPOTS, complementing relevant products for the global interior ocean carbon data (GLobal Ocean Data Analysis Project), global surface ocean carbon data (Surface Ocean CO2 Atlas; SOCAT), and global interior and surface methane and nitrous oxide data (MarinE MethanE and NiTrous Oxide product). Aside from the actual data compilation, the pilot project produced suggestions for reporting metadata, im- plementing quality control measures, and making estimations about uncertainty. These recommendations aim to encourage the community to adopt more consistent and uniform practices for analysis and reporting and to update these practices regularly. The detailed recommendations, links to the original time-series programs, the original data, their documentation, and related efforts are available on the SPOTS website. This site also pro- vides access to the data product (DOI: https://doi.org/10.26008/1912/bco-dmo.896862.2, Lange et al., 2024) and ancillary data.

Description: A natural plankton community from oligotrophic subtropical waters of the Atlantic near Gran Canaria, Spain, was subjected to varying degrees of ocean alkalinity enhancement (OAE) to assess the potential physiological effects, in the context of the application of ocean carbon dioxide removal (CDR) techniques. We employed 8.3 m3 mesocosms with a sediment trap attached to the bottom, creating a gradient in total alkalinity (TA). The lowest point on this gradient was 2400 μmol · L-1, which corresponded to the natural alkalinity of the environment, and the highest point was 4800 μmol · L-1. Over the course of the 33-day experiment, the plankton community exhibited two distinct phases. In phase-I (days 5–20), a notable decline in the photosynthetic efficiency (Fv/Fm) was observed. This change was accompanied by substantial reductions in the abundances of picoeukaryotes, small size nanoeukaryotes (nanoeukaryotes-1), and microplankton. The cell viability of picoeukaryotes, as indicated by fluorescein-di-acetate hydrolysis by cellular esterases (FDA- green fluorescence), slightly increased by the end of phase-I whilst the viability of nanoeukaryotes 1 and Synechococcus spp . did not change. Reactive oxygen species levels (ROS-green fluorescence) showed no significant changes for any of the functional groups. In contrast, in phase-II (days 21–33), a pronounced community response was observed. Increases in Fv/Fm in the intermediate OAE treatments of ∆900 to ∆1800 μmol · L-1 and in chlorophyll-a (Chl-a), chlorophyll-c2 (Chl-c2) , fucoxanthin and divinyl-Chl-a were attributed to the emergence of blooms of large size nanoeukaryotes (nanoeukaryotes-2) from the genera Chrysochromulina, as well as picoeukaryotes. Synechococcus spp. also flourished towards the end of this phase. In parallel, we observed a total 20 % significant change in the metaproteome of the phytoplankton community. This is considered a significant alteration in protein expression, having substantial impacts on cellular functions and the physiology of the organisms. Medium levels of ∆TA showed more upregulated and less downregulated proteins than higher ∆TA treatments. Under these conditions, cell viability significantly increased in pico and nanoeukaryotes-1 in intermediate alkalinity levels, while in Synechococcus spp., nanoeukaryotes-2 and microplankton remained stable. ROS levels did not significantly change in any functional group. The pigment ratios DD+DT : FUCO, and DD+DT : Chl-a increased in medium ∆TA treatments, supporting the idea of nutrient deficiency alleviation and the absence of physiological stress. Taken all data together, this study shows that there is minimal evidence indicating a harmful impact of high alkalinity on the plankton community. The OAE treatments did not result in physiological fitness impairment, thus OAE did not cause cellular stress in the phytoplankton community studied.

Description: Marine particles of different nature are found throughout the global ocean. The term "marine particles" describes detritus aggregates and fecal pellets as well as bacterioplankton, phytoplankton, zooplankton and nekton. Here, we present a global particle size distribution dataset obtained with several Underwater Vision Profiler 5 (UVP5) camera systems. Overall, within the 64 mu m to about 50 mm size range covered by the UVP5, detrital particles are the most abundant component of all marine particles; thus, measurements of the particle size distribution with the UVP5 can yield important information on detrital particle dynamics. During deployment, which is possible down to 6000 m depth, the UVP5 images a volume of about 1 L at a frequency of 6 to 20 Hz. Each image is segmented in real time, and size measurements of particles are automatically stored. All UVP5 units used to generate the dataset presented here were inter-calibrated using a UVP5 high-definition unit as reference. Our consistent particle size distribution dataset contains 8805 vertical profiles collected between 19 June 2008 and 23 November 2020. All major ocean basins, as well as the Mediterranean Sea and the Baltic Sea, were sampled. A total of 19 % of all profiles had a maximum sampling depth shallower than 200 dbar, 38 % sampled at least the upper 1000 dbar depth range and 11 % went down to at least 3000 dbar depth. First analysis of the particle size distribution dataset shows that particle abundance is found to be high at high latitudes and in coastal areas where surface productivity or continental inputs are elevated. The lowest values are found in the deep ocean and in the oceanic gyres. Our dataset should be valuable for more in-depth studies that focus on the analysis of regional, temporal and global patterns of particle size distribution and flux as well as for the development and adjustment of regional and global biogeochemical models. The marine particle size distribution dataset (Kiko et al., 2021) is available at https://doi.org/10.1594/PANGAEA.924375.

Description: Changes in stratospheric ozone concentrations and increasing concentrations of greenhouse gases (GHGs) alter the temperature structure of the atmosphere and drive changes in the atmospheric and oceanic circulation. We systematically investigate the impacts of ozone recovery and increasing GHGs on the atmospheric and oceanic circulation in the Southern Hemisphere during the twenty-first century using a unique coupled ocean–atmosphere climate model with interactive ozone chemistry and enhanced oceanic resolution. We use the high-emission scenario SSP5-8.5 for GHGs under which the springtime Antarctic total column ozone returns to 1980s levels by 2048 in our model, warming the lower stratosphere and strengthening the stratospheric westerly winds. We perform a spatial analysis and show for the first time that the austral spring stratospheric response to GHGs exhibits a marked planetary wavenumber 1 (PW1) pattern, which reinforces the response to ozone recovery over the Western Hemisphere and weakens it over the Eastern Hemisphere. These changes, which imply an eastward phase shift in the PW1, largely cancel out in the zonal mean. The Southern Hemisphere residual circulation strengthens during most of the year due to the increase in GHGs and weakens in spring due to ozone recovery. However, we find that in November the GHGs also drive a weakening of the residual circulation, reinforcing the effect of ozone recovery, which represents another novel result. At the surface, the westerly winds weaken and shift equatorward due to ozone recovery, driving a weak decrease in the transport of the Antarctic Circumpolar Current and in the Agulhas leakage and a cooling of the upper ocean, which is most pronounced in the latitudinal band 35–45∘ S. The increasing GHGs drive changes in the opposite direction that overwhelm the ozone effect. The total changes at the surface and in the oceanic circulation are nevertheless weaker in the presence of ozone recovery than those induced by GHGs alone, highlighting the importance of the Montreal Protocol in mitigating some of the impacts of climate change. We additionally compare the combined effect of interactively calculated ozone recovery and increasing GHGs with their combined effect in an ensemble in which we prescribe the CMIP6 ozone field. This second ensemble simulates a weaker ozone effect in all the examined fields, consistent with its weaker increase in ozone. The magnitude of the difference between the simulated changes at the surface and in the oceanic circulation in the two ensembles is as large as the ozone effect itself. This shows the large uncertainty that is associated with the choice of the ozone field and how the ozone is treated.

Description: Nitrogen (N) is a crucial limiting nutrient for phytoplankton growth in the ocean. The main source of bioavailable N in the ocean is delivered by N2-fixing diazotrophs in the surface layer. Since field observation of N2 fixation are spatially and temporally sparse, the fundamental processes and mechanisms controlling N2 fixation are not well understood and constrained. Here, we implement benthic denitrification in an Earth System Model of intermediate complexity (UVic-ESCM 2.9) coupled to an optimality-based plankton ecosystem model (OPEM v1.1). Benthic denitrification occurs mostly in coastal upwelling regions and on shallow continental shelves, and is the largest N-loss process in the global ocean. We calibrate our model against three different combinations of observed Chl, NO3-, PO43-, O2 and N* = NO3- −16PO43- +2.9. The inclusion of N* provides a powerful constraint on biogeochemical model behavior. Our new model version including benthic denitrification simulates higher global rates of N2 fixation with a more realistic distribution extending to higher latitudes that are supported by independent estimates based on geochemical data. Oxygen deficient zone volume and water column denitrification rates are reduced in the new version, indicating that including benthic denitrification may improve global biogeochemical models that commonly overestimate anoxic zones. With the improved representation of the ocean N cycle, our new model configuration also yields better global net primary production (NPP) when compared to the independent datasets not included in the calibration. Benthic denitrification plays an important role shaping N2 fixation and NPP throughout the global ocean in our model, and should be considered when evaluating and predicting their response to environmental change.

Description: Since a pH sensor has become available that is principally suitable for use on demanding autonomous measurement platforms, the marine CO2 system can be observed independently and continuously by Biogeochemical Argo floats. This opens the potential to detect variability and long-term changes in interior ocean inorganic carbon storage and quantify the ocean sink for atmospheric CO2. In combination with a second parameter of the marine CO2 system, pH can be a useful tool to derive the surface ocean CO2 partial pressure (pCO2). The large spatiotemporal variability in the marine CO2 system requires sustained observations to decipher trends and study the impacts of short-term events (e.g., eddies, storms, phytoplankton blooms) but also puts a high emphasis on the quality control of float-based pH measurements. In consequence, a consistent and rigorous quality control procedure is being established to correct sensor offsets or drifts as the interpretation of changes depends on accurate data. By applying current standardized routines of the Argo data management to pH measurements from a pH / O2 float pilot array in the subpolar North Atlantic Ocean, we assess the uncertainties and lack of objective criteria associated with the standardized routines, notably the choice of the reference method for the pH correction (CANYON-B, LIR-pH, ESPER-NN, and ESPER-LIR) and the reference depth for this adjustment. For the studied float array, significant differences ranging between ca. 0.003 pH units and ca. 0.04 pH units are observed between the four reference methods which have been proposed to correct float pH data. Through comparison against discrete and underway pH data from other platforms, an assessment of the adjusted float pH data quality is presented. The results point out noticeable discrepancies near the surface of 〉 0.004 pH units. In the context of converting surface ocean pH measurements into pCO2 data for the purpose of deriving air–sea CO2 fluxes, we conclude that an accuracy requirement of 0.01 pH units (equivalent to a pCO2 accuracy of 10 µatm as a minimum requirement for potential future inclusion in the Surface Ocean CO2 Atlas, SOCAT, database) is not systematically achieved in the upper ocean. While the limited dataset and regional focus of our study do not allow for firm conclusions, the evidence presented still calls for the inclusion of an additional independent pH reference in the surface ocean in the quality control routines. We therefore propose a way forward to enhance the float pH quality control procedure. In our analysis, the current philosophy of pH data correction against climatological reference data at one single depth in the deep ocean appears insufficient to assure adequate data quality in the surface ocean. Ideally, an additional reference point should be taken at or near the surface where the resulting pCO2 data are of the highest importance to monitor the air–sea exchange of CO2 and would have the potential to very significantly augment the impact of the current observation network.

Description: We examine the impact of horizontal resolution and model time step on the climate of the OpenIFS version 43r3 atmospheric general circulation model. A series of simulations for the period 1979–2019 are conducted with various horizontal resolutions (i.e. ∼100, ∼50, and ∼25 km) while maintaining the same time step (i.e. 15 min) and using different time steps (i.e. 60, 30, and 15 min) at 100 km horizontal resolution. We find that the surface zonal wind bias is significantly reduced over certain regions such as the Southern Ocean and the Northern Hemisphere mid-latitudes and in tropical and subtropical regions at a high horizontal resolution (i.e. ∼25 km). Similar improvement is evident too when using a coarse-resolution model (∼100 km) with a smaller time step (i.e. 30 and 15 min). We also find improvements in Rossby wave amplitude and phase speed, as well as in weather regime patterns, when a smaller time step or higher horizontal resolution is used. The improvement in the wind bias when using the shorter time step is mostly due to an increase in shallow and mid-level convection that enhances vertical mixing in the lower troposphere. The enhanced mixing allows frictional effects to influence a deeper layer and reduces wind and wind speed throughout the troposphere. However, precipitation biases generally increase with higher horizontal resolutions or smaller time steps, whereas the surface air temperature bias exhibits a small improvement over North America and the eastern Eurasian continent. We argue that the bias improvement in the highest-horizontal-resolution (i.e. ∼25 km) configuration benefits from a combination of both the enhanced horizontal resolution and the shorter time step. In summary, we demonstrate that, by reducing the time step in the coarse-resolution (∼100 km) OpenIFS model, one can alleviate some climate biases at a lower cost than by increasing the horizontal resolution.

Description: Here we present a confocal Fe K-edge μ-XANES method (where XANES stands for X-ray absorption near-edge spectroscopy) for the analysis of Fe oxidation state in heterogeneous and one-side-polished samples. The new technique allows for an analysis of small volumes with high spatial 3D resolution of 〈100 µm3. The probed volume is restricted to that just beneath the surface of the exposed object. This protocol avoids contamination of the signal by the host material and minimizes self-absorption effects. This technique has been tested on a set of experimental glasses with a wide range of Fe3+  ΣFe ratios. The method was applied to the analysis of natural melt inclusions trapped in forsteritic to fayalitic olivine crystals of the Hekla volcano, Iceland. Our measurements reveal changes in Fe3+  ΣFe from 0.17 in basaltic up to 0.45 in dacitic melts, whereas the magnetite–ilmenite equilibrium shows redox conditions with Fe3+  ΣFe ≤0.20 (close to FMQ, fayalite–magnetite–quartz redox equilibrium) along the entire range of Hekla melt compositions. This discrepancy indicates that the oxidized nature of glasses in the melt inclusions could be related to the post-entrapment process of diffusive hydrogen loss from inclusions and associated oxidation of Fe in the melt. The Fe3+  ΣFe ratio in silicic melts is particularly susceptible to this process due to their low FeO content, and it should be critically evaluated before petrological interpretation.

Description: We conducted extensive sediment trap experiments in the Benguela Upwelling System (BUS) in the south-eastern Atlantic Ocean to study the influence of zooplankton on the flux of particulate organic carbon (POC) through the water column and its sedimentation. Two long term moored and sixteen short term free-floating sediment trap systems were deployed. The mooring experiments were conducted for several years and the sixteen drifters were deployed on three different research cruises between 2019 and 2021. Zooplankton was separated from the trapped material and divided into 8 different zooplankton groups. In contrast to zooplankton which actively carries POC into the traps in the form of biomass (active POC flux), the remaining fraction of the trapped material was assumed to fall passively into the traps along with sinking particles (passive POC flux). The results show, in line with other studies, that copepods dominate the active POC flux, with the active POC flux in the southern BUS (sBUS) being about three times higher than in the northern BUS (nBUS). In contrast, the differences between the passive POC fluxes in the nBUS and sBUS were small. Despite large variations, which reflected the variability within the two subsystems, the mean passive POC fluxes from the drifters and the moored traps could be described using a common POC flux attenuation equation. However, the almost equal passive POC flux, on the one hand, and large variations in the POC concentration in the surface sediments between the nBUS and sBUS, on the other hand, imply that factors others than the POC supply exert the main control on POC sedimentation in the BUS. The varying intensity of the near-bottom oxygen minimum zone (OMZ), which is more pronounced in the nBUS than in the sBUS, could in turn explain the differences in the sediments, as the lack of oxygen reduces the POC degradation. Hence, globally expanding OMZs might favour POC sedimentation in regions formerly exposed to oxygenated bottom water but bear the risk of increasing the frequency of anoxic events in the oxygen-poor upwelling systems. Apart from associated release of CH4, which is a much more potent greenhouse gas than CO2, such events pose a major threat to the pelagic ecosystem and fisheries.

Description: Total alkalinity (AT) and dissolved inorganic carbon (CT) in the oceans are important properties with respect to understanding the ocean carbon cycle and its link to global change (ocean carbon sinks and sources, ocean acidification) and ultimately finding carbon-based solutions or mitigation procedures (marine carbon removal). We present a database of more than 44 400 AT and CT observations along with basic ancillary data (spatiotemporal location, depth, temperature and salinity) from various ocean regions obtained, mainly in the framework of French projects, since 1993. This includes both surface and water column data acquired in the open ocean, coastal zones and in the Mediterranean Sea and either from time series or dedicated one-off cruises. Most AT and CT data in this synthesis were measured from discrete samples using the same closed-cell potentiometric titration calibrated with Certified Reference Material, with an overall accuracy of ±4 µmol kg−1 for both AT and CT. The data are provided in two separate datasets – for the Global Ocean and the Mediterranean Sea (https://doi.org/10.17882/95414, Metzl et al., 2023), respectively – that offer a direct use for regional or global purposes, e.g., AT–salinity relationships, long-term CT estimates, and constraint and validation of diagnostic CT and AT reconstructed fields or ocean carbon and coupled climate–carbon models simulations as well as data derived from Biogeochemical-Argo (BGC-Argo) floats. When associated with other properties, these data can also be used to calculate pH, the fugacity of CO2 (fCO2) and other carbon system properties to derive ocean acidification rates or air–sea CO2 fluxes.

Description: The upper wind-driven circulation in the tropical Atlantic Ocean plays a key role in the basin-wide distribution of water mass properties and affects the transport of heat, freshwater, and biogeochemical tracers such as oxygen or nutrients. It is crucial to improve our understanding of its long-term behaviour, which largely relies on model simulations and applied forcing due to sparse observational data coverage, especially before the mid-2000s. Here, we apply two different forcing products, the Coordinated Ocean-ice Reference Experiments (CORE) v2 and the Japanese 55-year Reanalysis (JRA55-do) surface dataset, to a high-resolution ocean model. Where possible, we compare the simulated results to long-term observations. We find large discrepancies between the two simulations regarding the wind and current field. In the CORE simulation, strong, large-scale wind stress curl amplitudes above the upwelling regions of the eastern tropical North Atlantic seem to cause an overestimation of the mean and seasonal variability in the eastward subsurface current just north of the Equator. The wind stress curl of JRA55-do forcing shows much finer structures, and the JRA55-do simulation is in better agreement with the mean and intraseasonal fluctuations in the subsurface current found in observations. The northern branch of the South Equatorial Current flows westward at the surface just north of the Equator. On interannual to decadal timescales, it shows a high correlation of R=0.9 with the zonal wind stress in the CORE simulation but only a weak correlation of R=0.35 in the JRA55-do simulation. We also identify similarities between the two simulations. The strength of the eastward-flowing North Equatorial Counter Current located between 3 and 10° N covaries with the strength of the meridional wind stress just north of the Equator on interannual to decadal timescales in the two simulations. Both simulations present a comparable mean, seasonal cycle and trend of the eastward off-equatorial subsurface current south of the Equator but underestimate the current strength by half compared to observations. In both simulations, the eastward-flowing Equatorial Undercurrent weakened between 1990 and 2009. In the JRA simulation, which covers the modern period of observations, the Equatorial Undercurrent strengthened again between 2008 to 2018, which agrees with observations, although the simulation underestimates the strengthening by over a third. We propose that long-term observations, once they have reached a critical length, need to be used to test the quality of wind-driven simulations. This study presents one step in this direction.

Description: The increasing pCO2 in seawater is a serious threat for marine calcifiers and alters the biogeochemistry of the ocean. Therefore, the reconstruction of past-seawater properties and their impact on marine ecosystems is an important way to investigate the underlying mechanisms and to better constrain the effects of possible changes in the future ocean. Cold-water coral (CWC) ecosystems are biodiversity hotspots. Living close to aragonite-undersaturation, these corals serve as living laboratories as well as archives to reconstruct the boundary conditions of their calcification under the carbonate system of the ocean. We investigated the reef-building CWC Lophelia pertusa as a recorder of intermediate ocean seawater pH. This species-specific field calibration is based on a unique sample set of live in-situ collected L. pertusa and corresponding seawater samples. These data demonstrate that uranium speciation and skeletal incorporation for azooxanthellate scleractinian CWCs is pH dependent. However, this also indicates that internal pH up-regulation of the coral does not play a role in uranium incorporation into the majority of the skeleton of L. pertusa. This study suggests L. pertusa provides a new archive for the reconstruction of intermediate water mass pH and hence may help to constrain tipping points for ecosystem dynamics and evolutionary characteristics in a changing ocean.

Description: Here we present a comprehensive attempt to correlate aragonitic Na∕Ca ratios from Desmophyllum pertusum (formerly known as Lophelia pertusa), Madrepora oculata and a caryophylliid cold-water coral (CWC) species with different seawater parameters such as temperature, salinity and pH. Living CWC specimens were collected from 16 different locations and analyzed for their Na∕Ca ratios using solution-based inductively coupled plasma-optical emission spectrometry (ICP-OES) measurements. The results reveal no apparent correlation with salinity (30.1–40.57 g kg−1) but a significant inverse correlation with temperature (−0.31±0.04  mmolmol−1∘C−1). Other marine aragonitic organisms such as Mytilus edulis (inner aragonitic shell portion) and Porites sp. exhibit similar results highlighting the consistency of the calculated CWC regressions. Corresponding Na∕Mg ratios show a similar temperature sensitivity to Na∕Ca ratios, but the combination of two ratios appears to reduce the impact of vital effects and domain-dependent geochemical variation. The high degree of scatter and elemental heterogeneities between the different skeletal features in both Na∕Ca and Na∕Mg, however, limit the use of these ratios as a proxy and/or make a high number of samples necessary. Additionally, we explore two models to explain the observed temperature sensitivity of Na∕Ca ratios for an open and semi-enclosed calcifying space based on temperature-sensitive Na- and Ca-pumping enzymes and transport proteins that change the composition of the calcifying fluid and consequently the skeletal Na∕Ca ratio.

Description: Hyrrokkin sarcophaga is a parasitic foraminifera that is commonly found in cold-water coral reefs where it infests the file clam Acesta excavata and the scleractinian coral Desmophyllum pertusum (formerly known as Lophelia pertusa). Here, we present measurements of the trace element and isotopic composition of these parasitic foraminifera, analyzed by inductively coupled optical emission spectrometry (ICP-OES), electron probe microanalysis (EPMA) and mass spectrometry (gas-source MS and inductively-coupledplasma MS). Our results reveal that the geochemical signature of H. sarcophaga depends on the host organism it infests. Sr / Ca ratios are 1.1 mmol mol 1 higher in H. sarcophaga that infest D. pertusum, which could be an indication that dissolved host carbonate material is utilized in shell calcification, given that the aragonite of D. pertusum has a naturally higher Sr concentration compared to the calcite of A. excavata. Similarly, we measure 3.1 parts per thousand lower delta C-13 and 0.25 parts per thousand lower delta O-18 values in H. sarcophaga that lived on D. pertusum, which might be caused by the direct uptake of the host's carbonate material with a more negative isotopic composition or different pH regimes in these foraminifera (pH can exert a control on the extent of CO2 hydration/hydroxylation) due to the uptake of body fluids of the host. We also observe higher Mn / Ca ratios in foraminifera that lived on A. excavata but did not penetrate the host shell compared to specimen that penetrated the shell, which could be interpreted as a change in food source, changes in the calcification rate, Rayleigh fractionation or changing oxygen conditions. While our measurements provide an interesting insight into the calcification process of this unusual foraminifera, these data also indicate that the geochemistry of this parasitic foraminifera is unlikely to be a reliable indicator of paleoenvironmental conditions using Sr / Ca, Mn / Ca, delta O-18 or delta C-13 unless the host organism is known and its geochemical composition can be accounted for.

Description: Amino acids (AAs) mainly bound in proteins are major constituents of living biomass and non-living organic material in the oceanic particulate and dissolved organic matter pool. Uptake and cycling by heterotrophic organisms lead to characteristic changes in AA composition so that AA-based biogeochemical indicators are often used to elucidate processes of organic matter cycling and degradation. We analyzed particulate AA in a large sample set collected in various oceanic regions covering sinking and suspended particles in the water column, sediment samples, and dissolved AA from water column and pore water samples. The aim of this study was to test and improve the use of AA-derived biogeochemical indicators as proxies for organic matter sources and degradation and to better understand particle dynamics and interaction between the dissolved and particulate organic matter pools. A principal component analysis (PCA) of all data delineates diverging AA compositions of sinking and suspended particles with increasing water depth. A new sinking particle and sediment degradation indicator (SDI) allows a fine-tuned classification of sinking particles and sediments with respect to the intensity of degradation, which is associated with changes of stable isotopic ratios of nitrogen (δ15N). This new indicator is furthermore sensitive to sedimentary redox conditions and can be used to detect past anoxic early diagenesis. A second indicator emerges from the AA spectra of suspended particulate matter (SPM) in the epipelagic and that of the meso- and bathypelagic ocean and is a residence time indicator (RTI). The characteristic changes in AA patterns from shallow to deep SPM are recapitulated in the AA spectra of the dissolved organic matter (DOM) pool, so that deep SPM is more similar to DOM than to any of the other organic matter pools. This implies that there is equilibration between finely dispersed SPM and DOM in the deep sea, which may be driven by microbial activity combined with annealing and fragmentation of gels. As these processes strongly depend on physico-chemical conditions in the deep ocean, changes in quality and degradability of DOM may strongly affect the relatively large pool of suspended and dissolved AA in the ocean that amounts to 15 Pg amino acid carbon (AAC) and 89 ± 29 Pg AAC, respectively.

Description: Identification of seismically active fault zones and the definition of sufficiently large respect distances from these faults which enable avoiding the damaged rock zone surrounding the ruptured ground commonly are amongst the first steps to take in the geoscientific evaluation of sites suitable for nuclear waste disposal. In this work we present a GIS-based approach, using the earthquake-epicentre locations from the instrumental earthquake record of South-Korea to identify potentially active fault zones in the country, and compare different strategies for fault zone buffer creation as originally developed for site search in the high seismicity country Japan, and the low-to-moderate seismicity countries Germany and Sweden. In order to characterize the hazard potential of the Korean fault zones, we moreover conducted slip tendency analysis, here for the first time covering the fault zones of the entire Korean Peninsula. For our analyses we used the geo-spatial information from a new version of the Geological map of South-Korea, containing the outlines of 11 rock units, which we simplified to distinguish between 4 different rock types (granites, metamorphic rocks, sedimentary rocks and igneous rocks) and the surface traces of 1,528 fault zones and 6,654 lineaments identified through years of field work and data processing, a rich geo-dataset which we will publish along with this manuscript. Our approach for identification of active fault zones was developed without prior knowledge of already known seismically active fault zones, and as a proof of concept the results later were compared to a map containing already identified active fault zones. The comparison revealed that our approach identified 16 of the 21 known seismically active faults and added 472 previously unknown potentially active faults. The 5 seismically active fault zones which were not identified by our approach are located in the NE- and SW-sectors of the Korean Peninsula, which haven’t seen much recent seismic activity, and thus are not sufficiently well covered by the seismic record. The strike directions of fault zones identified as active are in good agreement with the orientation of the current stress field of the peninsula and slip tendency analysis provided first insights into subsurface geometry such as the dip angles of both active and inactive fault zones. The results of our work are of major importance for the early-stage seismic hazard assessment that has to be conducted in support of the nuclear waste disposal siting in South-Korea. Moreover, the GIS-based methods for identification of active fault zones and buffering of respect areas around fault zone traces presented here, are applicable also elsewhere.

Description: Ocean alkalinity enhancement (OAE) is considered one of the most promising approaches to actively remove carbon dioxide (CO2) from the atmosphere by accelerating the natural process of rock weathering. This approach involves introducing alkaline substances sourced from natural mineral deposits such as olivine, basalt, and carbonates or obtained from industrial waste products such as steel slags, into seawater and dispersing them over coastal areas. Some of these natural and industrial substances contain trace metals, which would be released into the oceans along with the alkalinity enhancement. The trace metals could serve as micronutrients for marine organisms at low concentrations, but could potentially become toxic at high concentrations, adversely affecting marine biota. To comprehensively assess the feasibility of OAE, it is crucial to understand how the phytoplankton, which forms the base of marine food webs, responds to ocean alkalinization and associated trace metal perturbations. In this study, we investigated the toxicity of nickel on three representative phytoplankton species across a range of Ni concentrations (from 0 to 100 µmol L-1 with 12 µmol L-1 synthetic organic ligand). The results showed that the growth of the tested species was impacted differently. The low growth inhibition and high IC50 (concentration to inhibit growth rate by 50 %) revealed that both the coccolithophore Emiliania huxleyi and the dinoflagellate Amphidinium carterae were mildly impacted by the increase in Ni concentrations while the rapid response to exposure of Ni, high growth rate inhibition, and low IC50 of Thalassiosira weissflogii indicate low tolerance to Ni in this species. In conclusion, the variability in phytoplankton sensitivity to Ni suggests that for OAE applications with Ni-rich materials caution is required and critical toxic thresholds for Ni must be avoided.

Description: The central Arctic Ocean (CAO) plays an important role in the global carbon cycle, but the current and future exchange of the climate-forcing trace gases methane (CH4) and carbon dioxide (CO2) between the CAO and the atmosphere is highly uncertain. In particular, there are very few observations of near-surface gas concentrations or direct air–sea CO2 flux estimates and no previously reported direct air–sea CH4 flux estimates from the CAO. Furthermore, the effect of sea ice on the exchange is not well understood. We present direct measurements of the air–sea flux of CH4 and CO2, as well as air–snow fluxes of CO2 in the summertime CAO north of 82.5∘ N from the Synoptic Arctic Survey (SAS) expedition carried out on the Swedish icebreaker Oden in 2021. Measurements of air–sea CH4 and CO2 flux were made using floating chambers deployed in leads accessed from sea ice and from the side of Oden, and air–snow fluxes were determined from chambers deployed on sea ice. Gas transfer velocities determined from fluxes and surface-water-dissolved gas concentrations exhibited a weaker wind speed dependence than existing parameterisations, with a median sea-ice lead gas transfer rate of 2.5 cm h−1 applicable over the observed 10 m wind speed range (1–11 m s−1). The average observed air–sea CO2 flux was −7.6 ..., and the average air–snow CO2 flux was −1.1 . Extrapolating these fluxes and the corresponding sea-ice concentrations gives an August and September flux for the CAO of −1.75 ... , within the range of previous indirect estimates. The average observed air–sea CH4 flux of 3.5 ..., accounting for sea-ice concentration, equates to an August and September CAO flux of 0.35 , lower than previous estimates and implying that the CAO is a very small (≪ 1 %) contributor to the Arctic flux of CH4 to the atmosphere.

Description: Probability density functions (PDFs) provide information about the probability of a random variable taking on a specific value. In geoscience, data distributions are often expressed by a parametric estimation of their PDF, such as, for example, a Gaussian distribution. At present there is growing attention towards the analysis of non-parametric estimation of PDFs, where no prior assumptions about the type of PDF are required. A common tool for such non-parametric estimation is a kernel density estimator (KDE). Existing KDEs are valuable but problematic because of the difficulty of objectively specifying optimal bandwidths for the individual kernels. In this study, we designed and developed a new implementation of a diffusion-based KDE as an open source Python tool to make diffusion-based KDE accessible for general use. Our new diffusion-based KDE provides (1) consistency at the boundaries, (2) better resolution of multimodal data, and (3) a family of KDEs with different smoothing intensities. We demonstrate our tool on artificial data with multiple and boundary-close modes and on real marine biogeochemical data, and compare our results against other popular KDE methods. We also provide an example for how our approach can be efficiently utilized for the derivation of plankton size spectra in ecological research. Our estimator is able to detect relevant multiple modes and it resolves modes that are located closely to a boundary of the observed data interval. Furthermore, our approach produces a smooth graph that is robust to noise and outliers. The convergence rate is comparable to that of the Gaussian estimator, but with a generally smaller error. This is most notable for small data sets with up to around 5000 data points. We discuss the general applicability and advantages of such KDEs for data–model comparison in geoscience.

Description: Many benthic organisms show aggregated distribution patterns due to the spatial heterogeneity of niches or food availability. In particular, high-abundance patches of benthic foraminifera have been reported that extend from centimetres to metres in diameter in salt marshes or shallow waters. The dimensions of spatial variations of shelf or deep-sea foraminiferal abundances have not yet been identified. Therefore, we studied the distribution of Globobulimina turgida dwelling in the 0–3 cm surface sediment at 118 m water depth in the Alsbäck Deep, Gullmar Fjord, Sweden. Standing stock data from 58 randomly replicated samples depicted a log-normal distribution of G. turgida with weak evidence for an aggregated distribution on a decimetre scale. A model simulation with different patch sizes, outlines, and impedances yielded no significant correlation with the observed variability of G. turgida standing stocks. Instead, a perfect match with a random log-normal distribution of population densities was obtained. The data–model comparison revealed that foraminiferal populations in the Gullmar Fjord were not moulded by any underlying spatial structure beyond 10 cm diameter. Log-normal population densities also characterise data from contiguous, gridded, or random sample replicates reported in the literature. Here, a centimetre-scale heterogeneity was found and interpreted to be a result of asexual reproduction events and restricted mobility of juveniles. Standing stocks of G. turgida from the Alsbäck Deep temporal data series from 1994 to 2021 showed two distinct cohorts of samples of either high or low densities. These cohorts are considered to represent two distinct ecological settings: hypoxic and well-ventilated conditions in the Gullmar Fjord. Environmental forcing is therefore considered to impact the population structure of benthic foraminifera rather than their reproduction dynamics.

Description: Estuaries are an important contributor to the global carbon budget, facilitating carbon removal, transfer, and transformation between land and the coastal ocean. Estuaries are susceptible to global climate change and anthropogenic perturbations. We find that a long-term significant mid-estuary increase in dissolved inorganic carbon (DIC) of 6–21 µmol kg−1 yr−1 (1997–2020) in a temperate estuary in Germany (Elbe Estuary) was driven by an increase in upper-estuary particulate organic carbon (POC) content of 8–14 µmol kg−1 yr−1. The temporal POC increase was due to an overall improvement in water quality observed in the form of high rates of primary production and a significant drop in biological oxygen demand. The magnitude of mid-estuary DIC gain was equivalent to the increased POC production in the upper estuary, suggesting that POC is effectively remineralized and retained as DIC in the mid-estuary, with the estuary acting as an efficient natural filter for POC. In the context of this significant long-term DIC increase, a recent extended drought period (2014–2020) significantly lowered the annual mean river discharge (468 ± 234 m3 s−1) compared to the long-term mean (690 ± 441 m3 s−1, 1960–2020), while the late spring internal DIC load in the estuary doubled. The drought induced a longer dry season, starting in May (earlier than normal), increased the residence time in the estuary and allowed for a more complete remineralization period of POC. Annually, 77 %–94 % of the total DIC export was laterally transported to the coastal waters, reaching 89 ± 4.8 Gmol C yr−1, and thus, between 1997 and 2020, only an estimated maximum of 23 % (10 Gmol C yr−1) was released via carbon dioxide (CO2) evasion. Export of DIC to coastal waters decreased significantly during the drought, on average by 24 % (2014–2020: 38 ± 5.4 Gmol C yr−1), compared to the non-drought period. In contrast, there was no change in the water–air CO2 flux during the drought. We have identified that seasonal changes in DIC processing in an estuary require consideration when estimating both the long-term and future changes in water–air CO2 flux and DIC export to coastal waters. Regional and global carbon budgets should therefore take into account carbon cycling estimates in estuaries, as well as their changes over time in relation to impacts of water quality changes and extreme hydrological events.

Description: Circulation anomalies accompanying Sudden Stratospheric Warmings (SSWs) can have a significant impact on the troposphere. This surface response is observed for some but not all SSWs, and their downward coupling is not fully understood. We use an existing classification method to separate downward- and non-propagating SSWs (d/nSSWs) in ERA5 reanalysis data for the years 1979–2019. The differences in SSW downward propagation in composites of spatial patterns clearly show that dSSWs dominate the surface regional impacts following SSWs. During dSSWs, the upper-tropospheric jet stream is significantly displaced equatorward. Wave activity analysis shows remarkable differences between d/nSSWs for planetary and synoptic-scale waves. Enhanced stratospheric planetary eddy kinetic energy (EKE) and heat fluxes around the central date of dSSWs are followed by increased synoptic-scale wave activity and even surface coupling for synoptic-scale EKE. An observed significant reduction in upper-tropospheric synoptic-scale momentum fluxes following dSSWs confirms the important role of tropospheric eddy feedbacks for coupling to the surface. Our findings emphasize the role of the lower stratosphere and synoptic-scale waves in coupling the SSW signal to the surface and agree with mechanisms suggested in earlier modeling studies.

Description: Ocean alkalinity enhancement (OAE) is considered for the long-term removal of gigatons of carbon dioxide (CO2) from the atmosphere to achieve our climate goals. Little is known, however, about the ecosystem-level changes in biogeochemical functioning that may result from the chemical sequestration of CO2 in seawater, and how stable the sequestration is. We studied these two aspects in natural plankton communities under carbonate-based, CO2-equilibrated OAE in the nutrient-poor North Atlantic. During a month-long mesocosm experiment, the majority of biogeochemical pools, including inorganic nutrients, particulate organic carbon and phosphorus as well as biogenic silica, remained unaltered across all OAE levels of up to a doubling of ambient alkalinity (+2400 µeq kg-1). Noticeable exceptions were a minor decrease in particulate organic nitrogen and an increase in the carbon to nitrogen ratio (C:N) of particulate organic matter in response to OAE. Thus, in our nitrogen limited system, nitrogen turnover processes appear more susceptible than those of other elements leading to decreased food quality and increased organic carbon storage. However, alkalinity and chemical CO2 sequestration were not stable at all levels of OAE. Two weeks after alkalinity addition, we measured a loss of added alkalinity and of the initially stored CO2 in the mesocosm where alkalinity was highest (+2400 µeq kg-1, Ωaragonite ~10). The loss rate accelerated over time. Additional tests showed that such secondary precipitation can be initiated by particles acting as precipitation nuclei and that this process can occur even at lower levels of OAE. In conclusion, on the one hand, our study under carbonate-based OAE where the carbon is already sequestered, the risk of major and sustained impacts on biogeochemical functioning may be low in the nutrient-poor ocean. On the other hand, the durability of carbon sequestration using OAE could be constrained by alkalinity loss in supersaturated waters with precipitation nuclei present. Our study provides evaluation of ecosystem impacts of an idealised OAE deployment for monitoring, reporting and verification (MRV) in an oligotrophic system. Whether biogeochemical functioning is resilient to more technically simple and economically more viable approaches that induce stronger water chemistry perturbations remains to be seen.

Description: Future change in sea surface temperature may influence climate via various air-sea feedbacks and pathways. In this study, we investigate the influence of surface seawater biogeochemical composition on the temperature dependence of sea spray number emission fluxes. Dependence of sea spray fluxes was investigated in different water masses (i.e. subantarctic, subtropical and frontal bloom) with contrasting biogeochemical properties across a temperature range from ambient (13–18 °C) to 2 °C, using seawater circulating in a plunging jet sea spray generator. We observed sea spray total concentration to increase significantly at temperatures below 8 °C, with an average 4-fold increase at 2 °C relative to initial concentration at ambient temperatures. This temperature dependence was more pronounced for smaller size sea spray particles (i.e. nucleation and Aitken modes). Moreover, temperature dependence varied with water mass type and so biogeochemical properties. While the sea spray flux at moderate temperatures (8–11 °C) was highest in frontal bloom waters, the effect of low temperature on the sea spray flux was highest with subtropical seawaters. The temperature dependence of sea spray flux was also inversely proportional to the seawater cell abundance of the cyanobacterium Synechococcus, which facilitated parameterization of temperature dependence of sea spray emission fluxes as a function of Synechococcus for future implementation in modelling exercises.

Description: Ocean alkalinity enhancement (OAE) stands as a promising carbon dioxide removal technology. Yet, this solution to climate change entails shifts in water chemistry with unknown consequences for marine fish that are critical to ecosystem health and food security. With a laboratory and mesocosm experiment, we show that early life stages of fish can be resistant to OAE. We examined metabolic rate, swimming behavior, growth and survival in Atlantic herring (Clupea harengus) and other temperate coastal fish species. Neither direct physiological nor indirect food web-mediated impacts of OAE were apparent. This was despite non-CO2-equilibrated OAE (ΔTA = +600 µmol kg-1) that induces strong perturbations (ΔpH = +0.7, pCO2 = 75 µatm) compared to alternative deployment scenarios. Whilst our results give cause for optimism regarding the large-scale application of OAE, other life history stages (embryos) and habitats (open ocean) may prove more vulnerable. Still, our study across ecological scales (organism to community) and exposure times (short- to long-term) suggests that some fish populations, including key fisheries species, may be resilient to the carbonate chemistry changes under OAE.

Description: Geomorphic and sedimentologic data indicate that the climate of today's hyper-arid Atacama Desert (northern Chile) was more humid during the mid-Pliocene to Late Pliocene. The processes, however, leading to increased rainfall in this period are largely unknown. To uncover these processes we use both global and regional kilometre-scale model experiments for the mid-Pliocene (3.2 Ma). We found that the PMIP4–CMIP6 (Paleoclimate Modelling Intercomparison Project–Coupled Model Intercomparison Project) model CESM2 (Community Earth System Model 2) and the regional model WRF (Weather Research and Forecasting) used in our study simulate more rainfall in the Atacama Desert for the mid-Pliocene in accordance with proxy data, mainly due to stronger extreme rainfall events in winter. Case studies reveal that these extreme winter rainfall events during the mid-Pliocene are associated with strong moisture conveyor belts (MCBs) originating in the tropical eastern Pacific. For present-day conditions, in contrast, our simulations suggest that the moisture fluxes rather arise from the subtropical Pacific region and are much weaker. A clustering approach reveals systematic differences between the moisture fluxes in the present-day and mid-Pliocene climates, both in strength and origins. The two mid-Pliocene clusters representing tropical MCBs and occurring less than 1 d annually on average produce more rainfall in the hyper-arid core of the Atacama Desert south of 20∘ S than what is simulated for the entire present-day period. We thus conclude that MCBs are mainly responsible for enhanced rainfall during the mid-Pliocene. There is also a strong sea-surface temperature (SST) increase in the tropical eastern Pacific and along the Atacama coast for the mid-Pliocene. It suggests that a warmer ocean in combination with stronger mid-tropospheric troughs is beneficial for the development of MCBs leading to more extreme rainfall in a +3 ∘C warmer world like in the mid-Pliocene.

Description: Riverine nutrient export is an important process in marine coastal biogeochemistry and also impacts global marine biology. The nitrogen cycle is a key player here. Internal feedbacks regulate not only nitrogen distribution, but also primary production and thereby oxygen concentrations. Phosphorus is another essential nutrient and interacts with the nitrogen cycle via different feedback mechanisms. After a previous study of the marine nitrogen cycle response to riverine nitrogen supply, we here additionally include phosphorus from river export with different phosphorus burial scenarios and study the impact of phosphorus alone and in combination with nitrogen in a global 3-D ocean biogeochemistry model. Again, we analyse the effects on near coastal and open ocean biogeochemistry. We find that the addition of bio-available riverine phosphorus alone or together with nitrogen affects marine biology on millennial timescales more than riverine nitrogen alone. Biogeochemical feedbacks in the marine nitrogen cycle are strongly influenced by the additional phosphorus. Where bio-available phosphorus is increased by river input, nitrogen concentrations increase as well, except for regions with high denitrification rates. High phosphorus burial rates decrease biological production significantly. Globally, riverine phosphorus leads to elevated primary production rates in the coastal and open oceans.

Description: Ectoenzymatic activity, prokaryotic heterotrophic abundances and production were determined in the Mediterranean Sea. Sampling was carried out in the sub-surface, the deep chlorophyll maximum layer (DCM), the core of the Levantine intermediate waters and in the deeper part of the mesopelagic layers. Michaelis–Menten kinetics were assessed using a large range of concentrations of fluorogenic substrates (0.025 to 50 µM). As a consequence, Km (Michaelis–Menten half-saturation constant) and Vm (maximum hydrolysis velocity) parameters were determined for both low- and high-affinity enzymes for alkaline phosphatase, aminopeptidase (LAP) and β-glucosidase (βGLU). Based on the constant derived from the high-LAP-affinity enzyme (0.025–1 µM substrate concentration range), in situ hydrolysis of N proteins contributed 48 % ± 30 % to the heterotrophic bacterial nitrogen demand within the epipelagic layers and 180 % ± 154 % in the Levantine intermediate waters and the upper part of the mesopelagic layers. The LAP hydrolysis rate was higher than bacterial N demand only within the deeper layer and only when considering the high-affinity enzyme. Based on a 10 % bacterial growth efficiency, the cumulative hydrolysis rates of C proteins and C polysaccharides contributed on average 2.5 % ± 1.3  % to the heterotrophic bacterial carbon demand in the epipelagic layers sampled (sub-surface and DCM). This study clearly reveals potential biases in current and past interpretations of the kinetic parameters for the three enzymes tested based on the fluorogenic-substrate concentration used. In particular, the LAP / βGLU enzymatic ratios and some of the depth-related trends differed between the use of high and low concentrations of fluorogenic substrates.

Description: An oxygen decrease of the intermediate-depth low-oxygen zones (300 to 700 m) is seen in time series for selected tropical areas for the period 1960 to 2008 in the eastern tropical Atlantic, the equatorial Pacific and the eastern tropical Indian Ocean. These nearly 5-decade time series were extended to 68 years by including rare historic data starting in 1950 and more recent data. For the extended time series between 1950 and 2018, the deoxygenation trend for the layer 300 to 700 m is similar to the deoxygenation trend seen in the shorter time series. Additionally, temperature, salinity, and nutrient time series in the upper-ocean layer (50 to 300 m) of these areas were investigated since this layer provides critical pelagic habitat for biological communities. Due to the low amount of data available, the results are often not statistically significant within the 95 % confidence interval but nevertheless indicate trends worth discussing. Generally, oxygen is decreasing in the 50 to 300 m layer, except for an area in the eastern tropical South Atlantic. Nutrients also showed long-term trends in the 50 to 300 m layer in all ocean basins and indicate overlying variability related to climate modes. Nitrate increased in all areas. Phosphate also increased in the Atlantic Ocean and Indian Ocean areas, while it decreased in the two areas of the equatorial Pacific Ocean. Silicate decreased in the Atlantic and Pacific areas but increased in the eastern Indian Ocean. Hence, oxygen and nutrients show trends in the tropical oceans, though nutrients trends are more variable between ocean areas than the oxygen trends; therefore, we conclude that those trends are more dependent on local drivers in addition to a global trend. Different positive and negative trends in temperature, salinity, oxygen and nutrients indicate that oxygen and nutrient trends cannot be completely explained by local warming.

Description: We resolve a previously unrecognized shallow subducting seamount from a re-processed multichannel seismic depth image crossing the 1994 M7.8 Java tsunami earthquake slip area. Seamount subduction is related to the uplift of the overriding plate by lateral shortening and vertical thickening, causing pronounced back-thrusting at the landward slope of the forearc high and the formation of splay faults branching off the landward flank of the subducting seamount. The location of the seamount in relation to the 1994 earthquake hypocentre and its co-seismic slip model suggests that the seamount acted as a seismic barrier to the up-dip co-seismic rupture propagation of this moderate size earthquake. The wrapping of the co-seismic slip contours around the seamount indicates that it diverted rupture propagation, documenting the control of forearc structures on seismic rupture.

Description: During the early part of the last glacial termination (17.2-15 ka) and coincident with a ∼ 35 ppm rise in atmospheric CO2, a sharp 0.3‰-0.4‰ decline in atmospheric δ13CO2 occurred, potentially constraining the key processes that account for the early deglacial CO2 rise. A comparable δ13C decline has also been documented in numerous marine proxy records from surface and thermocline-dwelling planktic foraminifera. The δ13C decline recorded in planktic foraminifera has previously been attributed to the release of respired carbon from the deep ocean that was subsequently transported within the upper ocean to sites where the signal was recorded (and then ultimately transferred to the atmosphere). Benthic δ13C records from the global upper ocean, including a new record presented here from the tropical Pacific, also document this distinct early deglacial δ13C decline. Here we present modeling evidence to show that rather than respired carbon from the deep ocean propagating directly to the upper ocean prior to reaching the atmosphere, the carbon would have first upwelled to the surface in the Southern Ocean where it would have entered the atmosphere. In this way the transmission of isotopically light carbon to the global upper ocean was analogous to the ongoing ocean invasion of fossil fuel CO2. The model results suggest that thermocline waters throughout the ocean and 500-2000m water depths were affected by this atmospheric bridge during the early deglaciation.

Description: The northern margin of the Ligurian Basin shows notable seismicity at the Alpine front, including frequent magnitude 4 events. Seismicity decreases offshore towards the Basin centre and Corsica, revealing a diffuse distribution of low magnitude earthquakes. We analyse data of the amphibious AlpArray seismic network with focus on the offshore component, the AlpArray OBS network, consisting of 24 broadband ocean bottom seismometers deployed for eight months, to reveal the seismicity and depth distribution of micro-earthquakes beneath the Ligurian Sea. Two clusters occurred between ~10 km to ~16 km depth below sea surface, within the lower crust and uppermost mantle. Thrust faulting focal mechanisms indicate compression and an inversion of the Ligurian Basin, which is an abandoned Oligocene rift basin. The Basin inversion is suggested to be related to the Africa-Europe plate convergence. The locations and focal mechanisms of seismicity suggest reactivation of pre-existing rift structures. Slightly different striking directions of faults in the basin centre compared to faults further east and hence away from the abandoned rift may mimic the counter-clockwise rotation of the Corsica-Sardinia block during ~20–16 Ma. The observed cluster events support the hypothesis of strengthening of crust and uppermost mantle during rifting related extension and thinning of continental crust.

Description: Oceans play a major role on the exchange of carbon with the atmosphere and thereby on past climates with glacial/interglacial variations of the CO2 concentration. The melting of ice sheets during deglaciations lets the sea level rise which leads to the flooding of coastal land areas resulting in the transfer of terrestrial organic matter to the ocean. However, the consequences of such fluxes on the ocean biogeochemical cycle and uptake/release of CO2 are poorly constrained. Moreover, this potentially important exchange of carbon at the land-sea interface is not represented in most Earth System Models. We present here the implementation of terrestrial organic matter fluxes into the ocean at the transiently changing land-sea interface in the Max Planck Institute for Meteorology Earth System Model (MPI-ESM) and investigate their effect on the biogeochemistry during the last deglaciation. Our results show that during the deglaciation, most of the terrestrial organic matter inputs to the ocean occurs during Meltwater Pulse 1a (between 15–14 ka) which leads to additional 21.2 GtC of terrestrial origin (mostly originating from wood and humus). Although this additional organic matter input is relatively small in comparison to the global ocean inventory (0.06 %) and thus doesn’t have an impact on the global CO2 flux, the terrestrial organic matter fluxes initiate oceanic outgassing at regional hotspots like in Indonesia for a few hundred years. Finally, sensitivity experiments highlight that terrestrial organic matter fluxes are the drivers of oceanic outgassing in flooded coastal regions during Meltwater Pulse 1a. Furthermore, the magnitude of outgassing is rather insensitive to higher carbon to nutrients ratios of the terrestrial organic matter. Our results provide a first estimate of the importance of terrestrial organic matter fluxes in a transient deglaciation simulation. Moreover, our model development is an important step towards a fully coupled carbon cycle in an Earth System Model applicable for simulations of glacial/interglacial cycles.

Description: In this study, we analyzed a large seismological dataset from temporary and permanent networks in the southern and eastern Alps to establish high-precision hypocenters and 1-D VP and VP/VS models. The waveform data of a subset of local earthquakes with magnitudes in the range of 1–4.2 ML were recorded by the dense, temporary SWATH-D network and selected stations of the AlpArray network between September 2017 and the end of 2018. The first arrival times of P and S waves of earthquakes are determined by a semi-automatic procedure. We applied a Markov chain Monte Carlo inversion method to simultaneously calculate robust hypocenters, a 1-D velocity model, and station corrections without prior assumptions, such as initial velocity models or earthquake locations. A further advantage of this method is the derivation of the model parameter uncertainties and noise levels of the data. The precision estimates of the localization procedure is checked by inverting a synthetic travel time dataset from a complex 3-D velocity model and by using the real stations and earthquakes geometry. The location accuracy is further investigated by a quarry blast test. The average uncertainties of the locations of the earthquakes are below 500 m in their epicenter and ∼ 1.7 km in depth. The earthquake distribution reveals seismicity in the upper crust (0–20 km), which is characterized by pronounced clusters along the Alpine frontal thrust, e.g., the Friuli-Venetia (FV) region, the Giudicarie–Lessini (GL) and Schio-Vicenza domains, the Austroalpine nappes, and the Inntal area. Some seismicity also occurs along the Periadriatic Fault. The general pattern of seismicity reflects head-on convergence of the Adriatic indenter with the Alpine orogenic crust. The seismicity in the FV and GL regions is deeper than the modeled frontal thrusts, which we interpret as indication for southward propagation of the southern Alpine deformation front (blind thrusts).

Description: The recent development of ambient noise tomography, in combination with the increasing number of permanent seismic stations and dense networks of temporary stations operated during passive seismic experiments, provides a unique opportunity to build the first high-resolution 3-D shear wave velocity (vS) model of the entire crust of the Bohemian Massif (BM). This paper provides a regional-scale model of velocity distribution in the BM crust. The velocity model with a cell size of 22 km is built using a conventional two-step inversion approach from Rayleigh wave group velocity dispersion curves measured at more than 400 stations. The shear velocities within the upper crust of the BM are ∼0.2 km s−1 higher than those in its surroundings. The highest crustal velocities appear in its southern part, the Moldanubian unit. The Cadomian part of the region has a thinner crust, whereas the crust assembled, or tectonically transformed in the Variscan period, is thicker. The sharp Moho discontinuity preserves traces of its dynamic development expressed in remnants of Variscan subductions imprinted in bands of crustal thickening. A significant feature of the presented model is the velocity-drop interface (VDI) modelled in the lower part of the crust. We explain this feature by the anisotropic fabric of the lower crust, which is characterised as vertical transverse isotropy with the low velocity being the symmetry axis. The VDI is often interrupted around the boundaries of the crustal units, usually above locally increased velocities in the lowermost crust. Due to the north-west–south-east shortening of the crust and the late-Variscan strike-slip movements along the north-east–south-west oriented sutures preserved in the BM lithosphere, the anisotropic fabric of the lower crust was partly or fully erased along the boundaries of original microplates. These weakened zones accompanied by a velocity increase above the Moho (which indicate an emplacement of mantle rocks into the lower crust) can represent channels through which portions of subducted and later molten rocks have percolated upwards providing magma to subsequently form granitoid plutons.

Description: Accurate subsurface velocity models are crucial for geological interpretations based on seismic depth images. Seismic reflection tomography is an effective iterative method to update and refine a preliminary velocity model for depth imaging. Based on residual move-out analysis of reflectors in common image point gathers an update of the velocity is estimated by a ray-based tomography. To stabilize the tomography, several preconditioning strategies exist. Most critical is the estimation of the depth error to account for the residual move-out of the reflector in the common image point gathers. Because the depth errors for many closely spaced image gathers must be picked, manual picking is extremely time-consuming, human biased, and not reproducible. Data-driven picking algorithms based on coherence or semblance analysis are widely used for hyperbolic or linear events. However, for complex-shaped depth events, pure data-driven picking is difficult. To overcome this, the warping method named Non-Rigid Matching is used to estimate a depth error displacement field. Warping is used, e.g., to merge photographic images or to match two seismic images from time-lapse data. By calculating the displacements between an offset to its neighbouring offset in the common image point domain, a locally smooth-shaped displacement field is defined for each data sample. Depending on the complexity of the subsurface, sample tracking through the displacement field along predefined horizons or on a simple regular grid yields discrete depth error values for the tomography. The application to a multi-channel seismic line across the Sunda subduction zone offshore Lombok island, Indonesia, illustrates the approach and documents the advantages of the method to estimate a detailed velocity structure in a complex tectonic regime. By incorporating the warping scheme into the reflection tomography, we demonstrate an increase in the velocity resolution and precision by improving the data-driven accuracy of depth error picks with arbitrary shapes. This approach offers the possibility to use the full capacities of tomography and further leads to more accurate interpretations of complex geological structures.

Description: Direct comparison between paleo oceanic δ13C records and model results facilitates assessing simulated distributions and properties of water masses in the past. To accomplish this, we include a new representation of the stable carbon isotope 13C into the HAMburg Ocean Carbon Cycle model (HAMOCC), the ocean biogeochemical component of the Max Planck Institute Earth System Model (MPI-ESM). 13C is explicitly resolved for all existing oceanic carbon pools. We account for fractionation during air-sea gas exchange and for biological fractionation εp associated with photosynthetic carbon fixation during phytoplankton growth. We examine two εp parameterisations of different complexity: εpPopp varies with surface dissolved CO2 concentration (Popp et al., 1989), while εpLaws additionally depends on local phytoplankton growth rates (Laws et al., 1995). When compared to observations of δ13C in dissolved inorganic carbon (DIC), both parameterisations yield similar performance. However, with regard to δ13C in particulate organic carbon εpPopp shows a considerably improved performance than εpLaws, because the latter results in a too strong preference for 12C. The model also well reproduces the oceanic 13C Suess effect, i.e. the intrusion of the isotopically light anthropogenic CO2 into the ocean, based on comparison to other existing 13C models and to observation-based oceanic carbon uptake estimates over the industrial period. We further apply the approach of Eide et al. (2017a), who derived the first global oceanic 13C Suess effect estimate based on observations, to our model data that has ample spatial and temporal coverage. With this we are able to analyse in detail the underestimation of 13C Suess effect by this approach as it has been noted by Eide et al. (2017a). Based on our model we find underestimations of 13C Suess effect at 200 m by 0.24 ‰ in the Indian Ocean, 0.21 ‰ in the North Pacific, 0.26 ‰ in the South Pacific, 0.1 ‰ in the North Atlantic and 0.14 ‰ in the South Atlantic. We attribute the major sources of the underestimation to two assumptions in Eide et al. (2017a)'s approach: a spatially-constant preformed component of δ13CDIC in year 1940 and neglecting 13C Suess effect in CFC-12 free water.

Description: A hierarchy of global 1/4° (ORCA025) and Atlantic Ocean 1/20° nested (VIKING20X) ocean/sea-ice models is described. It is shown that the eddy-rich configurations performed in hindcasts of the past 50–60 years under CORE and JRA55-do atmospheric forcings realistically simulate the large-scale horizontal circulation, the distribution of the mesoscale, overflow and convective processes, and the representation of regional current systems in the North and South Atlantic. The representation, and in particular the long-term temporal evolution, of the Atlantic Meridional Overturning Circulation (AMOC) strongly depends on numerical choices for the application of freshwater fluxes. The interannual variability of the AMOC instead is highly correlated among the model experiments and also with observations, including the 2010 minimum observed by RAPID at 26.5° N pointing at a dominant role of the forcing. Regional observations in western boundary current systems at 53° N, 26.5° N and 11° S are explored in respect to their ability to represent the AMOC and to monitor the temporal evolution of the AMOC. Apart from the basin-scale measurements at 26.5° N, it is shown that in particular the outflow of North Atlantic Deepwater at 53° N is a good indicator of the subpolar AMOC trend during the recent decades, if the latter is provided in density coordinates. The good reproduction of observed AMOC and WBC trends in the most reasonable simulations indicate that the eddy-rich VIKING20X is capable in representing realistic forcing-related and ocean-intrinsic trends.

Description: This paper presents a modelling study on the fate of CHBr3 and its product gases in the troposphere within the context of tropical deep convection. A cloud-scale case study was conducted along the west coast of Borneo, where several deep convective systems were triggered on the afternoon and early evening of 19 November 2011. These systems were sampled by the Falcon aircraft during the field campaign of the SHIVA project and analysed using a simulation with the cloud-resolving meteorological model C-CATT-BRAMS at 2x2 km resolution that represents the emissions, transport by large-scale flow, convection, photochemistry, and washout of CHBr3 and its product gases (PGs). We find that simulated CHBr3 mixing ratios and the observed values in the boundary layer and the outflow of the convective systems agree. However, the model underestimates the background CHBr3 mixing ratios in the upper troposphere, which suggests a missing source at the regional scale. An analysis of the simulated chemical speciation of bromine within and around each simulated convective system during the mature convective stage reveals that 〉 85% of the bromine derived from CHBr3 and its PGs is transported vertically to the point of convective detrainment in the form of CHBr3 and that the remaining small fraction is in the form of organic PGs, principally insoluble brominated carbonyls produced from the photo-oxidation of CHBr3. The model simulates that within the boundary layer and free troposphere, the inorganic PGs are only present in soluble forms, i.e. HBr, HOBr, and BrONO2, and, consequently, within the convective clouds, the inorganic PGs are almost entirely removed by wet scavenging. We find that HBr is the most abundant PG in background lower-tropospheric air and that this prevalence of HBr is a result of the relatively low background tropospheric ozone levels at the regional scale. Contrary to a previous study in a different environment, for the conditions in the simulation, the insoluble Br-2 species is hardly formed within the convective systems and therefore plays no significant role in the vertical transport of bromine. This likely results from the relatively small quantities of simulated inorganic bromine involved, the presence of HBr in large excess compared to HOBr and BrO, and the relatively efficient removal of soluble compounds within the convective column.

Description: Improved quantification techniques of natural sources is needed to explain variations in atmospheric methane. In polar regions, high uncertainties in current estimates of methane release from the seabed remain. We present two unique 10 and 3 months long time-series of bottom water measurements of physical and chemical parameters from two autonomous ocean observatories deployed at separate intense seabed methane seep sites (91 and 246 m depth) offshore Western Svalbard from 2015 to 2016. Results show high short term (100–1000 nmol L-1 within hours) and seasonal variation, as well as higher (2–7 times) methane concentrations compared to previous measurements. Rapid variability is explained by uneven distribution of seepage and changing ocean current directions. No overt influence of tidal hydrostatic pressure or water temperature variations on methane concentration was observed, but an observed negative correlation with temperature at the 246 site fits with hypothesized seasonal blocking of lateral methane pathways in the sediments. Negative correlation between bottom water methane concentration/variability and wind forcing, concomitant with signs of weaker water column stratification, indicates increased potential for methane release to the atmosphere in fall/winter. We highlight uncertainties in methane inventory estimates based on discrete water sampling and present new information about short- and long-term methane variability which can help constrain future estimates of seabed methane seepage.

Description: Earth system and climate modelling involves the simulation of processes on a wide range of scales and within and across various compartments of the Earth system. In practice, component models are often developed independently by different research groups, adapted by others to their special interests and then combined using a dedicated coupling software. This procedure not only leads to a strongly growing number of available versions of model components and coupled setups but also to model- and high-performance computing (HPC)-system-dependent ways of obtaining, configuring, building and operating them. Therefore, implementing these Earth system models (ESMs) can be challenging and extremely time consuming, especially for less experienced modellers or scientists aiming to use different ESMs as in the case of intercomparison projects. To assist researchers and modellers by reducing avoidable complexity, we developed the ESM-Tools software, which provides a standard way for downloading, configuring, compiling, running and monitoring different models on a variety of HPC systems. It should be noted that ESM-Tools is not a coupling software itself but a workflow and infrastructure management tool to provide access to increase usability of already existing components and coupled setups. As coupled ESMs are technically the more challenging tasks, we will focus on coupled setups, always implying that stand-alone models can benefit in the same way. With ESM-Tools, the user is only required to provide a short script consisting of only the experiment-specific definitions, while the software executes all the phases of a simulation in the correct order. The software, which is well documented and easy to install and use, currently supports four ocean models, three atmosphere models, two biogeochemistry models, an ice sheet model, an isostatic adjustment model, a hydrology model and a land-surface model. Compared to previous versions, ESM-Tools has lately been entirely recoded in a high-level programming language (Python) and provides researchers with an even more user-friendly interface for Earth system modelling. ESM-Tools was developed within the framework of the Advanced Earth System Model Capacity project, supported by the Helmholtz Association.

Description: The past and future evolution of the Antarctic Ice Sheet is largely controlled by interactions between the ocean and floating ice shelves. To investigate these interactions, coupled ocean and ice sheet model configurations are required. Previous modelling studies have mostly relied on high-resolution configurations, limiting these studies to individual glaciers or regions over short timescales of decades to a few centuries. We present a framework to couple the dynamic ice sheet model PISM (Parallel Ice Sheet Model) with the global ocean general circulation model MOM5 (Modular Ocean Model) via the ice shelf cavity model PICO (Potsdam Ice-shelf Cavity mOdel). As ice shelf cavities are not resolved by MOM5 but are parameterized with the PICO box model, the framework allows the ice sheet and ocean components to be run at resolutions of 16 km and 3∘ respectively. This approach makes the coupled configuration a useful tool for the analysis of interactions between the Antarctic Ice Sheet and the global ocean over time spans of the order of centuries to millennia. In this study, we describe the technical implementation of this coupling framework: sub-shelf melting in the ice sheet component is calculated by PICO from modelled ocean temperatures and salinities at the depth of the continental shelf, and, vice versa, the resulting mass and energy fluxes from melting at the ice–ocean interface are transferred to the ocean component. Mass and energy fluxes are shown to be conserved to machine precision across the considered component domains. The implementation is computationally efficient as it introduces only minimal overhead. Furthermore, the coupled model is evaluated in a 4000 year simulation under constant present-day climate forcing and is found to be stable with respect to the ocean and ice sheet spin-up states. The framework deals with heterogeneous spatial grid geometries, varying grid resolutions, and timescales between the ice and ocean component in a generic way; thus, it can be adopted to a wide range of model set-ups.

Description: The skill of global ocean biogeochemical models, and the earth system models in which they are embedded, can be improved by systematic calibration of the parameter values against observations. However, such tuning is seldom undertaken as these models are computationally very expensive. Here we investigate the performance of DFO-LS, a local, derivative-free optimisation algorithm which has been designed for computationally expensive models with irregular model–data misfit landscapes typical of biogeochemical models. We use DFO-LS to calibrate six parameters of a relatively complex global ocean biogeochemical model (MOPS) against synthetic dissolved oxygen, phosphate and nitrate “observations” from a reference run of the same model with a known parameter configuration. The performance of DFO-LS is compared with that of CMA-ES, another derivative-free algorithm that was applied in a previous study to the same model in one of the first successful attempts at calibrating a global model of this complexity. We find that DFO-LS successfully recovers five of the six parameters in approximately 40 evaluations of the misfit function (each one requiring a 3000-year run of MOPS to equilibrium), while CMA-ES needs over 1200 evaluations. Moreover, DFO-LS reached a “baseline” misfit, defined by observational noise, in just 11–14 evaluations, whereas CMA-ES required approximately 340 evaluations. We also find that the performance of DFO-LS is not significantly affected by observational sparsity, however fewer parameters were successfully optimised in the presence of observational uncertainty. The results presented here suggest that DFO-LS is sufficiently inexpensive and robust to apply to the calibration of complex, global ocean biogeochemical models.

Description: An increasing number of dead zoning (hypoxia) has been reported as a consequence of declining levels of dissolved oxygen in coastal oceans all over the globe. Despite substantial efforts a quantitative description of hypoxia up to a level enabling reliable predictions has not been achieved yet for most regions of societal interest. This does also apply to Eckernförde Bight (EB) situated in the Baltic Sea, Germany. The aim of this study is to dissect underlying mechanisms of hypoxia in EB, to identify key sources of uncertainties, and to explore the potential of existing monitoring programs to predict hypoxia by developing and documenting a workflow that may be applicable to other regions facing similar challenges. Our main tool is an ultra-high spatially resolved general ocean circulation model based on a code framework of proven versatility in that it has been applied to various regional and even global simulations in the past. Our model configuration features a spacial horizontal resolution of 100 m (unprecedented in the underlying framework which is used in both global and regional applications) and includes an elementary representation of the biogeochemical dynamics of dissolved oxygen. In addition, we integrate artificial “clocks” that measure the residence time of the water in EB along with timescales of (surface) ventilation. Our approach relies on an ensemble of hindcast model simulations, covering the period from 2000 to 2018, designed to cover a range of poorly known model parameters for vertical background mixing (diffusivity) and local oxygen consumption within EB. Feed-forward artificial neural networks are used to identify predictors of hypoxia deep in EB based on data at a monitoring site at the entrance of EB. Our results consistently show that the dynamics of low (hypoxic) oxygen concentrations in bottom waters deep inside EB is, to first order, determined by the following antagonistic processes: (1) the inflow of low-oxygenated water from the Kiel Bight (KB) – especially from July to October – and (2) the local ventilation of bottom waters by local (within EB) subduction and vertical mixing. Biogeochemical processes that consume oxygen locally are apparently of minor importance for the development of hypoxic events. Reverse reasoning suggests that subduction and mixing processes in EB contribute, under certain environmental conditions, to the ventilation of the KB by exporting recently ventilated waters enriched in oxygen. A detailed analysis of the 2017 fish-kill incident highlights the interplay between westerly winds importing hypoxia from KB and ventilating easterly winds which subduct oxygenated water.

Description: Climate-relevant trace gas air-sea exchange exerts an important control on air quality and climate, especially in remote regions of the planet such as the Southern Ocean. It is clear that polar regions exhibit seasonal trends in productivity and biogeochemical cycling, but almost all of the measurements there are skewed to summer months. If we want to understand how the Southern Ocean effects the balance of climate through trace gas air-sea exchange, it is essential to expand our measurement database over greater temporal and spatial scales, including all seasons. Therefore, in this study, we report measured concentrations of dimethylsulphide (DMS, and related sulphur compounds) and isoprene in the Atlantic sector of the Southern Ocean during the winter to understand the spatial and temporal distribution in comparison to current knowledge and climatological calculations for the Southern Ocean. The observations of isoprene are the first in the winter season in the Southern Ocean. We find that concentrations and fluxes of DMS and isoprene in the investigated area are generally lower than those presented or calculated in currently used climatologies and models. More data is urgently needed to better interpolate climatological values and validate process-oriented models, as well as to explore how finer measurement resolution, both spatially and temporally, can influence air-sea flux calculations.

Description: The Leeuwin Current flowing southward along West Australia is an important conduit for the poleward heat transport and interocean water exchange between the tropical and the subantarctic ocean areas. Its past development, and its relationship to Southern Ocean change and to Australian ecosystem response, however is largely unknown. We here reconstruct sea surface and thermocline temperatures and salinities from foraminiferal-based Mg/Ca and stable oxygen isotopes from offshore southwest and southeast Australia reflecting the Leeuwin Current dynamics over the last 60 kyrs. Its variability resembles the biomass burning development in Australasia from ~60–20 ka BP implying that climate-modulated changes related to the Leeuwin Current most likely affected Australian vegetational and fire regimes. In particular during ~60–43 ka BP, warmest thermocline temperatures point to a strongly developed Leeuwin Current during Antarctic cool periods when the Antarctic Circumpolar Current weakened. The pronounced centennial-scale variations in Leeuwin Current strength appear in line with the migrations of the Southern Hemisphere frontal system and are captured by prominent changes in the Australian megafauna biomass. We argue that the concerted action of a rapidly changing Leeuwin Current, the ecosystem response in Australia, and human interference since ~50 BP enhanced the ecological stress on the Australian megafauna until a tipping point was reached at ~43 ka BP, after which faunal recuperation no longer took place. While being weakest during the last glacial maximum, the deglacial Leeuwin Current intensified at times of poleward migrations of the Subtropical Front. During the Holocene, the thermocline off South Australia was considerably shallower compared to the short-term glacial and deglacial periods of Leeuwin Current intensification.

Description: We describe and test a new model of biological marine silicate cycling, implemented in the Kiel Marine Biogeochemical Model version 3 (KMBM3), embedded in the University of Victoria Earth System Climate Model (UVic ESCM) version 2.9. This new model adds diatoms, which are a key component of the biological carbon pump, to an existing ecosystem model. This new model combines previously published parameterizations of a diatom functional type, opal production and export with a novel, temperature-dependent dissolution scheme. Modelled steady-state biogeochemical rates, carbon and nutrient distributions are similar to those found in previous model versions. The new model performs well against independent ocean biogeochemical indicators and captures the large-scale features of the marine silica cycle to a degree comparable to similar Earth system models. Furthermore, it is computationally efficient, allowing both fully coupled, long-timescale transient simulations and “offline” transport matrix spinups. We assess the fully coupled model against modern ocean observations, the historical record starting from 1960 and a business-as-usual atmospheric CO2 forcing to the year 2300. The model simulates a global decline in net primary production (NPP) of 1.4 % having occurred since the 1960s, with the strongest declines in the tropics, northern midlatitudes and Southern Ocean. The simulated global decline in NPP reverses after the year 2100 (forced by the extended RCP8.5 CO2 concentration scenario), and NPP returns to 98 % of the pre-industrial rate by 2300. This recovery is dominated by increasing primary production in the Southern Ocean, mostly by calcifying phytoplankton. Large increases in calcifying phytoplankton in the Southern Ocean offset a decline in the low latitudes, producing a global net calcite export in 2300 that varies only slightly from pre-industrial rates. Diatom distribution moves southward in our simulations, following the receding Antarctic ice front, but diatoms are outcompeted by calcifiers across most of their pre-industrial Southern Ocean habitat. Global opal export production thus drops to 75 % of its pre-industrial value by 2300. Model nutrients such as phosphate, silicate and nitrate build up along the Southern Ocean particle export pathway, but dissolved iron (for which ocean sources are held constant) increases in the upper ocean. This different behaviour of iron is attributed to a reduction of low-latitude NPP (and consequently, a reduction in both uptake and export and particle, including calcite scavenging), an increase in seawater temperatures (raising the solubility of particulate iron) and stratification that “traps” the iron near the surface. These results are meant to serve as a baseline for sensitivity assessments to be undertaken with this model in the future.

Description: The region around the town Albstadt, SW Germany, was struck by four damaging earthquakes with magnitudes greater than 5 during the last century. These earthquakes occurred along the Albstadt Shear Zone (ASZ), which is characterized by more or less continuous microseismicity. As there are no visible surface ruptures that may be connected to the fault zone, we study its characteristics by its seismicity distribution and faulting pattern. We use the earthquake data of the state earthquake service of Baden-Württemberg from 2011 to 2018 and complement it with additional phase picks beginning in 2016 at the AlpArray and StressTransfer seismic networks in the vicinity of the ASZ. This extended data set is used to determine new minimum 1-D seismic vp and vs velocity models and corresponding station delay times for earthquake relocation. Fault plane solutions are determined for selected events, and the principal stress directions are derived. The minimum 1-D seismic velocity models have a simple and stable layering with increasing velocity with depth in the upper crust. The corresponding station delay times can be explained well by the lateral depth variation of the crystalline basement. The relocated events align about north–south with most of the seismic activity between the towns of Tübingen and Albstadt, east of the 9∘ E meridian. The events can be separated into several subclusters that indicate a segmentation of the ASZ. The majority of the 25 determined fault plane solutions feature an NNE–SSW strike but NNW–SSE-striking fault planes are also observed. The main fault plane associated with the ASZ dips steeply, and the rake indicates mainly sinistral strike-slip, but we also find minor components of normal and reverse faulting. The determined direction of the maximum horizontal stress of 140–149∘ is in good agreement with prior studies. Down to ca. 7–8 km depth SHmax is bigger than SV; below this depth, SV is the main stress component. The direction of SHmax indicates that the stress field in the area of the ASZ is mainly generated by the regional plate driving forces and the Alpine topography.

Description: As one of Earth's most productive marine ecosystems, the Peruvian upwelling system transports large amounts of biogenic matter from the surface to the deep ocean. Whilst particle sinking velocity is a key factor controlling the biological pump, thereby affecting carbon sequestration and O2-depletion, it has not yet been measured in this system. During a 50 d mesocosm experiment in the surface waters off the coast of Peru, we assessed particle sinking velocities and their biogeochemical and physical drivers. We further characterized the general properties of exported particles under different phytoplankton communities and nutritional states. Average sinking velocities varied between size classes and ranged from 12.8 ± 0.7 m d−1 (particles 40–100 µm) to 19.4 ± 0.7 m d−1 (particles 100–250 µm) and 34.2 ± 1.5 m d−1 (particles 250–1000 µm) (± 95 % CI). Despite a distinct plankton succession from diatoms to dinoflagellates with concomitant 5-fold drop in opal ballasting, substantial changes in sinking velocity were not observed. This illustrates the complexity of counteracting factors driving the settling behaviour of marine particles. In contrast, we found higher sinking velocities with increasing particle size and roundness and decreasing porosity. Size had by far the strongest influence among these physical particle properties, despite a high amount of unexplained variability. Our study provides a detailed analysis of the drivers of particle sinking velocity in the Peruvian upwelling system, which allows modellers to optimize local particle flux parameterization. This will help to better project oxygen concentrations and carbon sequestration in a region that is subject to substantial climate-driven changes.

Description: We developed a new version of the Alfred Wegener Institute Climate Model (AWI-CM3), which has higher skills in representing the observed climatology and better computational efficiency than its predecessors. Its ocean component FESOM2 (Finite-volumE Sea ice-Ocean Model) has the multi-resolution functionality typical of unstructured-mesh models while still featuring a scalability and efficiency similar to regular-grid models. The atmospheric component OpenIFS (CY43R3) enables the use of the latest developments in the numerical-weather-prediction community in climate sciences. In this paper we describe the coupling of the model components and evaluate the model performance on a variable-resolution (25-125 km) ocean mesh and a 61 km atmosphere grid, which serves as a reference and starting point for other ongoing research activities with AWI-CM3. This includes the exploration of high and variable resolution and the development of a full Earth system model as well as the creation of a new sea ice prediction system. At this early development stage and with the given coarse to medium resolutions, the model already features above-CMIP6-average skills (where CMIP6 denotes Coupled Model Intercomparison Project phase 6) in representing the climatology and competitive model throughput. Finally we identify remaining biases and suggest further improvements to be made to the model.

Description: Large amounts of methane (CH4) could be released as a result of the gradual or abrupt thawing of Arctic permafrost due to global warming. Once available, this potent greenhouse gas is emitted into the atmosphere or transported laterally into aquatic ecosystems via hydrologic connectivity at the surface or via groundwaters. While high northern latitudes contribute up to 5 % of total global CH4 emissions, the specific contribution of Arctic rivers and streams is largely unknown. We analyzed high-resolution continuous CH4 concentrations measured between 15 and 17 June 2019 (late freshet) in a ∼120 km transect of the Kolyma River in northeast Siberia. The average partial pressure of CH4 (pCH4) in tributaries (66.8–206.8 µatm) was 2–7 times higher than in the main river channel (28.3 µatm). In the main channel, CH4 was up to 1600 % supersaturated with respect to atmospheric equilibrium. Key sites along the riverbank and at tributary confluences accounted for 10 % of the navigated transect and had the highest pCH4 (41 ± 7 µatm) and CH4 emissions (0.03 ± 0.004 ) compared to other sites in the main channel, contributing between 14 % to 17 % of the total CH4 flux in the transect. These key sites were characterized by warm waters (T〉14.5 ∘C) and low specific conductivities (κ〈88 µS cm−1). The distribution of CH4 in the river could be linked statistically to T and κ of the water and to their proximity to the shore z, and these parameters served as predictors of CH4 concentrations in unsampled river areas. The abundance of CH4-consuming bacteria and CH4-producing archaea in the river was similar to those previously detected in nearby soils and was also strongly correlated to T and κ. These findings imply that the source of riverine CH4 is closely related with sites near land. The average total CH4 flux density in the river section was 0.02 ± 0.006 , equivalent to an annual CH4 flux of 1.24×107 g CH4 yr−1 emitted during a 146 d open water season. Our study highlights the importance of high-resolution continuous CH4 measurements in Arctic rivers for identifying spatial and temporal variations, as well as providing a glimpse of the magnitude of riverine CH4 emissions in the Arctic and their potential relevance to regional CH4 budgets.

Description: Global biogeochemical ocean models help to investigate the present and potential future state of the ocean, its productivity and cascading effects on higher trophic levels such as fish. They are often subjectively tuned against data sets of inorganic tracers and surface chlorophyll and only very rarely against organic components such as particulate organic carbon or zooplankton. The resulting uncertainty in biogeochemical model parameters (and parameterisations) associated with these components can explain some of the large spread of global model solutions with regard to the cycling of organic matter and its impacts on biogeochemical tracer distributions, such as oxygen minimum zones (OMZs). A second source of uncertainty arises from differences in the model spin-up length as, so far, there seems to be no agreement on the required simulation time that should elapse before a global model is assessed against observations. We investigated these two sources of uncertainty by optimising a global biogeochemical ocean model against the root-mean-squared error (RMSE) of six different combinations of data sets and different spin-up times. Besides nutrients and oxygen, the observational data sets also included phyto- and zooplankton, as well as dissolved and particulate organic phosphorus (DOP and POP, respectively). We further analysed the optimised model performance with regard to global biogeochemical fluxes, oxygen inventory and OMZ volume. Following the optimisation procedure, we evaluated the RMSE for all tracers located in the upper 100 m (except for POP, for which we considered the entire vertical domain), regardless of their consideration during optimisation. For the different optimal model solutions, we find a narrow range of the RMSE, between 14 % of the average RMSE after 10 years and 24 % after 3000 years of simulation. Global biogeochemical fluxes, global oxygen bias and OMZ volume showed a much stronger divergence among the models and over time than RMSE, indicating that even models that are similar with regard to local surface tracer concentrations can perform very differently when assessed against the global diagnostics for oxygen. Considering organic tracers in the optimisation had a strong impact on the particle flux exponent (Martin b) and may reduce much of the uncertainty in this parameter and the resulting deep particle flux. Independent of the optimisation setup, the OMZ volume showed a particularly sensitive response with strong trends over time, even after 3000 years of simulation time (despite the constant physical forcing); a high sensitivity to simulation time; and the highest sensitivity to model parameters arising from the tuning strategy setup (variation of almost 80 % of the ensemble mean). In conclusion, calibration against observations of organic tracers can help to improve global biogeochemical models even after short spin-up times; here especially, observations of deep particle flux could provide a powerful constraint. However, a large uncertainty remains with regard to global OMZ volume and its evolution over time, which can show very dynamic behaviour during the model spin-up, which renders temporal extrapolation to a final equilibrium state difficult if not impossible. Given that the real ocean shows variations on many timescales, the assumption of observations representing a steady-state ocean may require some reconsideration.

Description: The Peruvian upwelling system is a highly productive ecosystem with a large oxygen minimum zone (OMZ) close to the surface. In this work, we carried out a mesocosm experiment off Callao, Peru, with the addition of water masses from the regional OMZ collected at two different sites simulating two different upwelling scenarios. Here, we focus on the pelagic remineralization of organic matter by the extracellular enzyme activity of leucine aminopeptidase (LAP) and alkaline phosphatase activity (APA). After the addition of the OMZ water, dissolved inorganic nitrogen (N) was depleted, but the standing stock of phytoplankton was relatively high, even after N depletion (mostly 〉 4 µg chlorophyll a L−1). During the initial phase of the experiment, APA was 0.6 nmol L−1 h−1 even though the PO concentration was 〉 0.5 µmol L−1. Initially, the dissolved organic phosphorus (DOP) decreased, coinciding with an increase in the PO concentration that was probably linked to the APA. The LAP activity was very high, with most of the measurements in the range of 200–800 nmol L−1 h−1. This enzyme hydrolyzes terminal amino acids from larger molecules (e.g., peptides or proteins), and these high values are probably linked to the highly productive but N-limited coastal ecosystem. Moreover, the experiment took place during a rare coastal El Niño event with higher than normal surface temperatures, which could have affected enzyme activity. Using a nonparametric multidimensional scaling analysis (NMDS) with a generalized additive model (GAM), we found that biogeochemical variables (e.g., nutrient and chlorophyll-a concentrations) and phytoplankton and bacterial communities explained up to 64 % of the variability in APA. The bacterial community best explained the variability (34 %) in LAP. The high hydrolysis rates for this enzyme suggest that pelagic N remineralization, likely driven by the bacterial community, supported the high standing stock of primary producers in the mesocosms after N depletion.

Description: As Earth's atmospheric temperatures and human populations increase, more people are becoming vulnerable to natural and human-induced disasters. This is particularly true in Central America, where the growing human population is experiencing climate extremes (droughts and floods), and the region is susceptible to geological hazards, such as earthquakes and volcanic eruptions, and environmental deterioration in many forms (soil erosion, lake eutrophication, heavy metal contamination, etc.). Instrumental and historical data from the region are insufficient to understand and document past hazards, a necessary first step for mitigating future risks. Long, continuous, well-resolved geological records can, however, provide a window into past climate and environmental changes that can be used to better predict future conditions in the region. The Lake Izabal Basin (LIB), in eastern Guatemala, contains the longest known continental records of tectonics, climate, and environmental change in the northern Neotropics. The basin is a pull-apart depression that developed along the North American and Caribbean plate boundary ∼ 12 Myr ago and contains 〉 4 km of sediment. The sedimentological archive in the LIB records the interplay among several Earth System processes. Consequently, exploration of sediments in the basin can provide key information concerning: (1) tectonic deformation and earthquake history along the plate boundary; (2) the timing and causes of volcanism from the Central American Volcanic Arc; and (3) hydroclimatic, ecologic, and geomicrobiological responses to different climate and environmental states. To evaluate the LIB as a potential site for scientific drilling, 65 scientists from 13 countries and 33 institutions met in Antigua, Guatemala, in August 2022 under the auspices of the International Continental Scientific Drilling Program (ICDP) and the US National Science Foundation (NSF). Several working groups developed scientific questions and overarching hypotheses that could be addressed by drilling the LIB and identified optimal coring sites and instrumentation needed to achieve the project goals. The group also discussed logistical challenges and outreach opportunities. The project is not only an outstanding opportunity to improve our scientific understanding of seismotectonic, volcanic, paleoclimatic, paleoecologic, and paleobiologic processes that operate in the tropics of Central America, but it is also an opportunity to improve understanding of multiple geological hazards and communicate that knowledge to help increase the resilience of at-risk Central American communities.

Description: Biogeochemical cycling of carbon (C) and nitrogen (N) in the ocean depends on both the composition and activity of underlying biological communities and on abiotic factors. The Southern Ocean is encircled by a series of strong currents and fronts, providing a barrier to microbial dispersion into adjacent oligotrophic gyres. Our study region straddles the boundary between the nutrient-rich Southern Ocean and the adjacent oligotrophic gyre of the South Indian Ocean, providing an ideal region to study changes in microbial productivity. Here, we measured the impact of C- and N- uptake on microbial community diversity, contextualized by hydrographic factors and local physico-chemical conditions across the Southern Ocean and South Indian Ocean. We observed that contrasting physico-chemical characteristics led to unique microbial diversity patterns, with significant correlations between microbial alpha diversity and primary productivity (PP). However, we detected no link between specific PP (PP normalized by chlorophyll a concentration) and microbial alpha and beta diversity. Prokaryotic alpha and beta diversity were correlated with biological N2 fixation, itself a prokaryotic process, and we detected measurable N2 fixation to 60° S. While regional water masses have distinct microbial genetic fingerprints in both the eukaryotic and prokaryotic fractions, PP and N2 fixation vary more gradually and regionally. This suggests that microbial phylogenetic diversity is more strongly bounded by physical oceanographic features, while microbial activity responds more to chemical factors. We conclude that concomitant assessments of microbial diversity and activity is central in understanding the dynamics and complex responses of microorganisms to a changing ocean environment.

Description: We present an ensemble of last glacial inception (LGI) simulations for the Northern Hemisphere that captures a significant fraction of inferred ice volume changes within proxy uncertainties. This ensemble was performed with LCice 1.0, a coupled ice sheet and climate model, varying parameters of both climate and ice sheet components, as well as the coupling between them. Certain characteristics of the spatiotemporal pattern of ice growth and subsequent retreat in both North America (NA) and Eurasia (EA) are sensitive to parameter changes while others are not. We find that the initial inception of ice over NA and EA is best characterized by the nucleation of ice at high-latitude and high-elevation sites. Subsequent spreading and merger along with large-scale conversion of snowfields dominate in different sectors. The latter plays an important role in the merging of eastern and western ice regions in NA. The inception peak ice volume in the ensemble occurs approximately at 111 ka and therefore lags the summer 60∘ N insolation minimum by more than 3 kyr. Ice volumes consistently peak earlier over EA than NA. The inception peak in North America is characterized by a merged Laurentide and Cordilleran ice sheet, with the Davis Strait covered in ice in ∼80 % of simulations. Ice also bridges Greenland and Iceland in all runs by 114 ka and therefore blocks the Denmark Strait. This latter feature would thereby divert the East Greenland Current and Denmark Strait overflow with a potentially significant impact on ocean circulation. The Eurasian ice sheet at its inception peak varies across ensemble runs between a continuous ice sheet and multiple smaller ice caps. In both continents, the colder high latitudes (i.e. Ellesmere and Svalbard) tend to grow ice through the entire simulation (to 102 ka), while lower latitudes lose ice after ∼110 ka. We find temperature decreases over the initial phases of the inception lead to the expansion of NA ice sheet area and that subsequent precipitation increases contribute to its thickening. EA ice sheet area also expands with decreasing temperatures, but sea ice limits any increases in precipitation, leading to an earlier retreat away from the EA maximum ice sheet volume. We also examine the extent to which the capture of both LGI ice growth and retreat constrains the coupled ice–climate model sensitivity to changing atmospheric pCO2. The 55-member sub-ensemble that meets our criteria for “acceptable” ice growth and retreat has an equilibrium climate sensitivity lower bound that is 0.3 ∘C higher than that of the full ensemble. This suggests some potential value of fully coupled ice–climate modelling of the last glacial inception to constrain future climate change.

Description: Open-ocean oxygen minimum zones (OMZs) occur in regions with high biological productivity and weak ventilation. They restrict marine habitats and alter biogeochemical cycles. Global models generally show a large model–data misfit with regard to oxygen. Reliable statements about the future development of OMZs and the quantification of their interaction with climate change are currently not possible. One of the most intense OMZs worldwide is located in the Arabian Sea (AS). We give an overview of the main model deficiencies with a detailed comparison of the historical state of 10 climate models from the 5th Coupled Model Intercomparison Project (CMIP5) that present our present-day understanding of physical and biogeochemical processes. Most of the models show a general underestimation of the OMZ volume in the AS compared to observations that is caused by an overly shallow layer of oxygen-poor water in the models. The deviation of oxygen values in the deep AS is the result of oxygen levels that are too high simulated in the Southern Ocean formation regions of Indian Ocean Deep Water in the models compared to observations and uncertainties in the deepwater mass transport from the Southern Ocean northward into the AS. Differences in simulated water mass properties and ventilation rates of Red Sea Water and Persian Gulf Water cause different mixing in the AS and thus influence the intensity of the OMZ. These differences in ventilation rates also point towards variations in the parameterizations of the overflow from the marginal seas among the models. The results of this study are intended to foster future model improvements regarding the OMZ in the AS.

Description: Marine particulate organic carbon-13 stable isotope ratios (δ13CPOC) provide insights in understanding carbon cycling through the atmosphere, ocean, and biosphere. They have been used to trace the input of anthropogenic carbon in the marine ecosystem due to the distinct isotopically light signature of anthropogenic emissions. However, δ13CPOC is also significantly altered during photosynthesis by phytoplankton, which complicates its interpretation. For such purposes, robust spatio-temporal coverage of δ13CP OC observations is essential. We collected all such available data sets, merged and homogenized them to provide the largest available marine δ13CPOC data set (Verwega et al., 2021). The data set consists of 4732 data points covering all major ocean basins beginning in the 1960s. We describe the compiled raw data, compare different observational methods, and provide key insights in the temporal and spatial distribution that is consistent with previously observed patterns. The main different sample collection methods (bottle, intake, net, trap) are generally consistent with each other when comparing within regions. An analysis of 1990s mean δ13CP OC values in an meridional section accross the Atlantic Ocean shows relatively high values (≥ −22 ‰) in the low latitudes (〈 30°) trending towards lower values in the Arctic Ocean (∼ −24 ‰) and Southern Ocean (≤ −28 ‰). The temporal trend since the 1960s shows a decrease of mean δ13CPOC by more than 3 ‰ in all basins except for the Southern Ocean which shows a weaker trend but contains relatively poor multi-decadal coverage.

Description: Permafrost degradation in the catchment of major Siberian rivers, combined with higher precipitation in a warming climate, could increase the flux of terrestrially derived dissolved organic matter (tDOM) into the Arctic Ocean (AO). Each year, ∼ 7.9 Tg of dissolved organic carbon (DOC) is discharged into the AO via the three largest rivers that flow into the Laptev Sea (LS) and East Siberian Sea (ESS). A significant proportion of this tDOM-rich river water undergoes at least one freeze–melt cycle in the land-fast ice that forms along the coast of the Laptev and East Siberian seas in winter. To better understand how growth and melting of land-fast ice affect dissolved organic matter (DOM) dynamics in the LS and ESS, we determined DOC concentrations and the optical properties of coloured dissolved organic matter (CDOM) in sea ice, river water and seawater. The data set, covering different seasons over a 9-year period (2010–2019), was complemented by oceanographic measurements (T, S) and determination of the oxygen isotope composition of the seawater. Although removal of tDOM cannot be ruled out, our study suggests that conservative mixing of high-tDOM river water and sea-ice meltwater with low-tDOM seawater is the major factor controlling the surface distribution of tDOM in the LS and ESS. A case study based on data from winter 2012 and spring 2014 reveals that the mixing of about 273 km3 of low-tDOM land-fast-ice meltwater (containing ∼ 0.3 Tg DOC) with more than 200 km3 of high-tDOM Lena River water discharged during the spring freshet (∼ 2.8 Tg DOC yr−1) plays a dominant role in this respect. The mixing of the two low-salinity surface water masses is possible because the meltwater and the river water of the spring freshet flow into the southeastern LS at the same time every year (May–July). In addition, budget calculations indicate that in the course of the growth of land-fast ice in the southeastern LS, ∼ 1.2 Tg DOC yr−1 (± 0.54 Tg) can be expelled from the growing ice in winter, together with brines. These DOC-rich brines can then be transported across the shelves into the Arctic halocline and the Transpolar Drift Current flowing from the Siberian Shelf towards Greenland. The study of dissolved organic matter dynamics in the AO is important not only to decipher the Arctic carbon cycle but also because CDOM regulates physical processes such as radiative forcing in the upper ocean, which has important effects on sea surface temperature, water column stratification, biological productivity and UV penetration.

Description: The organic mass fraction from sea spray aerosol (SSA) is currently a subject of intense research. The majority of this research is dedicated to measurements in ambient air. However a number of studies have recently started to focus on nascent sea spray aerosol. This work presents measurements collected during a 5-week cruise in May and June 2017 in the central and western Mediterranean Sea, an oligotrophic marine region with low phytoplankton biomass. Surface seawater was continuously pumped into a bubble-bursting apparatus to generate nascent sea spray aerosol. Size distributions were measured with a differential mobility particle sizer (DMPS). Chemical characterization of the submicron aerosol was performed with a time-of-flight aerosol chemical speciation monitor (ToF-ACSM) operating with 10 min time resolution and with filter-based chemical analysis on a daily basis. Using positive matrix factorization analysis, the ToF-ACSM non-refractory organic matter (OMNR) was separated into four different organic aerosol types, identified as primary OA (POANR), oxidized OA (OOANR), methanesulfonic acid type OA (MSA-OANR), and mixed OA (MOANR). In parallel, surface seawater biogeochemical properties were monitored providing information on phytoplankton cell abundance and seawater particulate organic carbon (1 h time resolution) and seawater surface microlayer (SML) dissolved organic carbon (DOC) (on a daily basis). Statistically robust correlations (for n〉500) were found between MOANR and nanophytoplankton cell abundance, as well as between POANR, OOANR, and particulate organic carbon (POC). Parameterizations of the contributions of different types of organics to the submicron nascent sea spray aerosol are proposed as a function of the seawater biogeochemical properties for use in models.

Description: The science guiding the EUREC4A campaign and its measurements is presented. EUREC4A comprised roughly 5 weeks of measurements in the downstream winter trades of the North Atlantic – eastward and southeastward of Barbados. Through its ability to characterize processes operating across a wide range of scales, EUREC4A marked a turning point in our ability to observationally study factors influencing clouds in the trades, how they will respond to warming, and their link to other components of the earth system, such as upper-ocean processes or the life cycle of particulate matter. This characterization was made possible by thousands (2500) of sondes distributed to measure circulations on meso- (200 km) and larger (500 km) scales, roughly 400 h of flight time by four heavily instrumented research aircraft; four global-class research vessels; an advanced ground-based cloud observatory; scores of autonomous observing platforms operating in the upper ocean (nearly 10 000 profiles), lower atmosphere (continuous profiling), and along the air–sea interface; a network of water stable isotopologue measurements; targeted tasking of satellite remote sensing; and modeling with a new generation of weather and climate models. In addition to providing an outline of the novel measurements and their composition into a unified and coordinated campaign, the six distinct scientific facets that EUREC4A explored – from North Brazil Current rings to turbulence-induced clustering of cloud droplets and its influence on warm-rain formation – are presented along with an overview of EUREC4A's outreach activities, environmental impact, and guidelines for scientific practice. Track data for all platforms are standardized and accessible at https://doi.org/10.25326/165 (Stevens, 2021), and a film documenting the campaign is provided as a video supplement.