ALBERT

Description: The distribution of the main water masses in the Atlantic Ocean are investigated with the Optimal Multi-Parameter (OMP) method. The properties of the main water masses in the Atlantic Ocean are described in a companion article; here these definitions are used to map out the general distribution of those water masses. Six key properties, including conservative (potential temperature and salinity) and non-conservative (oxygen, silicate, phosphate and nitrate), are incorporated into the OMP analysis to determine the contribution of the water masses in the Atlantic Ocean based on the GLODAP v2 observational data. To facilitate the analysis the Atlantic Ocean is divided into four vertical layers based on potential density. Due to the high seasonal variability in the mixed layer, this layer is excluded from the analysis. Central waters are the main water masses in the upper/central layer, generally featuring high potential temperature and salinity and low nutrient concentrations and are easily distinguished from the intermediate water masses. In the intermediate layer, the Antarctic Intermediate Water (AAIW) from the south can be detected to ~30°N, whereas the Subarctic Intermediate Water (SAIW), having similarly low salinity to the AAIW flows from the north. Mediterranean Overflow Water (MOW) flows from the Strait of Gibraltar as a high salinity water. NADW dominates the deep and overflow layer both in the North and South Atlantic. In the bottom layer, AABW is the only natural water mass with high silicate signature spreading from the Antarctic to the North Atlantic. Due to the change of water mass properties, in this work we renamed to North East Antarctic Bottom Water NEABW north of the equator. Similarly, the distributions of Labrador Sea Water (LSW), Iceland Scotland Overflow Water (ISOW), and Denmark Strait Overflow Water (DSOW) forms upper and lower portion of NADW, respectively roughly south of the Grand Banks between ~50 and 66°N. In the far south the distributions of Circumpolar Deep Water (CDW) and Weddell Sea Bottom Water (WSBW) are of significance to understand the formation of the AABW.

Description: The northeast Atlantic encompasses archetypal examples of volcanic rifted margins. Twenty-five years after the last ODP (Ocean Drilling Program) leg on these volcanic margins, the reasons for excess melting are still disputed with at least three competing hypotheses being discussed. We are proposing a new drilling campaign that will constrain the timing, rates of volcanism, and vertical movements of rifted margins. This will allow us to parameterise geodynamic models that can distinguish between the hypotheses. Furthermore, the drilling-derived data will help us to understand the role of breakup magmatism as a potential driver for the Palaeocene–Eocene thermal maximum (PETM) and its influence on the oceanographic circulation in the earliest phase of the northeast Atlantic Ocean formation. Tackling these questions with a new drilling campaign in the northeast Atlantic region will advance our understanding of the long-term interactions between tectonics, volcanism, oceanography, and climate and the functioning of subpolar northern ecosystems and climate during intervals of extreme warmth.

Description: The El Niño Southern Oscillation (ENSO) with its warm (El Niño) and cold (La Niña) phase has strong impacts on marine ecosystems off Peru. This influence extends from changes in nutrient availability to productivity and oxygen levels. While several studies have demonstrated the influence of ENSO events on biological productivity, less is known about their impact on oxygen concentrations. In situ observations along the Peruvian and Chilean coast have shown a strong water column oxygenation during the 1997/1998 strong El Niño event. These observations suggest a deepening of the oxygen minimum zone (OMZ) along the continental shelf. However, due to reduced spatial coverage of the existing in situ observations, no studies have yet demonstrated the OMZ response to El Niño events in the whole Eastern Tropical South Pacific (ETSP). Furthermore, most studies have focused on El Niño events. Much less attention was given to the oxygen dynamics under La Niña influence. Here, we provide a comprehensive analysis of the ENSO influence on OMZ dynamics. Interannual variability of the OMZ during the period 1990–2010 is derived from a regional coupled physical-biogeochemical model forced with realistic atmospheric and lateral boundary conditions. Our results show a reduction of the vertical extent and a deepening of suboxic waters (SW) during the El Niño phase. During the La Niña phase, there is a vertical expansion of SW. These fluctuations in OMZ extent are due to changes in oxygen supply into its core depth mainly from lateral margins. During the El Niño phase, the enhanced lateral oxygen supply from the subtropics is the main reason for the reduction of SW in both coastal and offshore regions. During the La Niña phase, the oxygenated subtropical waters are blocked by the poleward transport along the southern margin of the OMZ. Consequently, oxygen concentrations within the OMZ are reduced and suboxic conditions expand during La Niña. The detailed analysis of transport pathways presented here provides new insights into how ENSO variability affects the oxygen-sensitive marine biogeochemistry of the ETSP.

Description: Oxygen minimum zones (OMZs) in the open ocean occur below the surface in regions of weak ventilation and high biological productivity. Very low levels of dissolved oxygen affect marine life and alter biogeochemical cycles. One of the most intense but least understood OMZs in the world is located in the Arabian Sea in a depth range between 300 to 1000 m. Within the last decades observations suggest a decreasing oxygen trend. Thus, an improved understanding of the crucial processes is necessary for a reliable assessment of the future development of the Arabian Sea OMZ. This study uses a combination of observational data as well as reanalysis velocity fields from the ocean model Hycom (Hybrid Coordinate Ocean Model) to explore the ventilation dynamics of the Arabian Sea OMZ. Our results show that the OMZ features a strong seasonal cycle with regional differences that is correlated with the monsoon system: In the eastern basin, the OMZ is strongest during the winter monsoon with a core thickness of 1000 m depth and oxygen values of less than 5 µmol/kg. Ventilation during that phase is dominated by Persian Gulf water, that clockwise circles the perimeter of the basin and enters the OMZ from the north. During the summer monsoon ventilation from the southeast leads to higher oxygen values indicating a reverse flow along the Indian coast in the intermediate layer compared to the southeastward surface currents. The seasonal cycle in the western basin has the same seasonality as the one in the eastern basin with a core thickness of 900 m during the winter monsoon. The oxygen supply during the summer monsoon is weaker compared to the eastern basin and correlates with the ventilation of Persian Gulf (Red Sea) water during the summer monsoon (autumn inter-monsoon) phase. As the interior exchange between the eastern and western basin is weak, the more pronounced OMZ in the eastern basin is explained by prolonged ventilation time scales. For the eastern (western) basin Persian Gulf water needs 2–3 (1–2) years and Red Sea water 7–8 (3–4) years to ventilate the OMZ.

Description: Ice sheet numerical modeling is an important tool to estimate the dynamic contribution of the Antarctic ice sheet to sea level rise over the coming centuries. The influence of initial conditions on ice sheet model simulations, however, is still unclear. To better understand this influence, an initial state intercomparison exercise (initMIP) has been developed to compare, evaluate, and improve initialization procedures and estimate their impact on century-scale simulations. initMIP is the first set of experiments of the Ice Sheet Model Intercomparison Project for CMIP6 (ISMIP6), which is the primary Coupled Model Intercomparison Project Phase 6 (CMIP6) activity focusing on the Greenland and Antarctic ice sheets. Following initMIP-Greenland, initMIP-Antarctica has been designed to explore uncertainties associated with model initialization and spin-up and to evaluate the impact of changes in external forcings. Starting from the state of the Antarctic ice sheet at the end of the initialization procedure, three forward experiments are each run for 100 years: a control run, a run with a surface mass balance anomaly, and a run with a basal melting anomaly beneath floating ice. This study presents the results of initMIP-Antarctica from 25 simulations performed by 16 international modeling groups. The submitted results use different initial conditions and initialization methods, as well as ice flow model parameters and reference external forcings. We find a good agreement among model responses to the surface mass balance anomaly but large variations in responses to the basal melting anomaly. These variations can be attributed to differences in the extent of ice shelves and their upstream tributaries, the numerical treatment of grounding line, and the initial ocean conditions applied, suggesting that ongoing efforts to better represent ice shelves in continental-scale models should continue.

Description: We present here the first results, for the preindustrial and mid-Holocene climatological periods, of the newly developed isotope-enhanced version of the fully coupled Earth system model MPI-ESM, called hereafter MPI-ESM-wiso. The water stable isotopes H162O, H182O and HDO have been implemented into all components of the coupled model setup. The mid-Holocene provides the opportunity to evaluate the model response to changes in the seasonal and latitudinal distribution of insolation induced by different orbital forcing conditions. The results of our equilibrium simulations allow us to evaluate the performance of the isotopic model in simulating the spatial and temporal variations of water isotopes in the different compartments of the hydrological system for warm climates. For the preindustrial climate, MPI-ESM-wiso reproduces very well the observed spatial distribution of the isotopic content in precipitation linked to the spatial variations in temperature and precipitation rate. We also find a good model–data agreement with the observed distribution of isotopic composition in surface seawater but a bias with the presence of surface seawater that is too 18O-depleted in the Arctic Ocean. All these results are improved compared to the previous model version ECHAM5/MPIOM. The spatial relationships of water isotopic composition with temperature, precipitation rate and salinity are consistent with observational data. For the preindustrial climate, the interannual relationships of water isotopes with temperature and salinity are globally lower than the spatial ones, consistent with previous studies. Simulated results under mid-Holocene conditions are in fair agreement with the isotopic measurements from ice cores and continental speleothems. MPI-ESM-wiso simulates a decrease in the isotopic composition of precipitation from North Africa to the Tibetan Plateau via India due to the enhanced monsoons during the mid-Holocene. Over Greenland, our simulation indicates a higher isotopic composition of precipitation linked to higher summer temperature and a reduction in sea ice, shown by positive isotope–temperature gradient. For the Antarctic continent, the model simulates lower isotopic values over the East Antarctic plateau, linked to the lower temperatures during the mid-Holocene period, while similar or higher isotopic values are modeled over the rest of the continent. While variations of isotopic contents in precipitation over West Antarctica between mid-Holocene and preindustrial periods are partly controlled by changes in temperature, the transport of relatively 18O-rich water vapor near the coast to the western ice core sites could play a role in the final isotopic composition. So, more caution has to be taken about the reconstruction of past temperature variations during warm periods over this area. The coupling of such a model with an ice sheet model or the use of a zoomed grid centered on this region could help to better describe the role of the water vapor transport and sea ice around West Antarctica. The reconstruction of past salinity through isotopic content in sea surface waters can be complicated for regions with strong ocean dynamics, variations in sea ice regimes or significant changes in freshwater budget, giving an extremely variable relationship between the isotopic content and salinity of ocean surface waters over small spatial scales. These complicating factors demonstrate the complexity of interpreting water isotopes as past climate signals of warm periods like the mid-Holocene. A systematic isotope model intercomparison study for further insights on the model dependency of these results would be beneficial.

Description: Probabilistic spatial reconstructions of past climate states are valuable to quantitatively study the climate system under different forcing conditions because they combine the information contained in a proxy synthesis into a comprehensible product. Unfortunately, they are subject to a complex uncertainty structure due to complicated proxy–climate relations and sparse data, which makes interpolation between samples difficult. Bayesian hierarchical models feature promising properties to handle these issues, like the possibility to include multiple sources of information and to quantify uncertainties in a statistically rigorous way. We present a Bayesian framework that combines a network of pollen and macrofossil samples with a spatial prior distribution estimated from a multi-model ensemble of climate simulations. The use of climate simulation output aims at a physically reasonable spatial interpolation of proxy data on a regional scale. To transfer the pollen data into (local) climate information, we invert a forward version of the probabilistic indicator taxa model. The Bayesian inference is performed using Markov chain Monte Carlo methods following a Metropolis-within-Gibbs strategy. Different ways to incorporate the climate simulations into the Bayesian framework are compared using identical twin and cross-validation experiments. Then, we reconstruct the mean temperature of the warmest and mean temperature of the coldest month during the mid-Holocene in Europe using a published pollen and macrofossil synthesis in combination with the Paleoclimate Modelling Intercomparison Project Phase III mid-Holocene ensemble. The output of our Bayesian model is a spatially distributed probability distribution that facilitates quantitative analyses that account for uncertainties.

Description: Large calderas are among the Earth's major volcanic features. They are associated with large magma reservoirs and elevated geothermal gradients. Caldera-forming eruptions result from the withdrawal and collapse of the magma chambers and produce large-volume pyroclastic deposits and later-stage deformation related to post-caldera resurgence and volcanism. Unrest episodes are not always followed by an eruption; however, every eruption is preceded by unrest. The Campi Flegrei caldera (CFc), located along the eastern Tyrrhenian coastline in southern Italy, is close to the densely populated area of Naples. It is one of the most dangerous volcanoes on Earth and represents a key example of an active, resurgent caldera. It has been traditionally interpreted as a nested caldera formed by collapses during the 100–200 km3 Campanian Ignimbrite (CI) eruption at ∼39 ka and the 40 km3 eruption of the Neapolitan Yellow Tuff (NYT) at ∼15 ka. Recent studies have suggested that the CI may instead have been fed by a fissure eruption from the Campanian Plain, north of Campi Flegrei. A MagellanPlus workshop was held in Naples, Italy, on 25–28 February 2017 to explore the potential of the CFc as target for an amphibious drilling project within the International Ocean Discovery Program (IODP) and the International Continental Drilling Program (ICDP). It was agreed that Campi Flegrei is an ideal site to investigate the mechanisms of caldera formation and associated post-caldera dynamics and to analyze the still poorly understood interplay between hydrothermal and magmatic processes. A coordinated onshore–offshore drilling strategy has been developed to reconstruct the structure and evolution of Campi Flegrei and to investigate volcanic precursors by examining (a) the succession of volcanic and hydrothermal products and related processes, (b) the inner structure of the caldera resurgence, (c) the physical, chemical, and biological characteristics of the hydrothermal system and offshore sediments, and (d) the geological expression of the phreatic and hydromagmatic eruptions, hydrothermal degassing, sedimentary structures, and other records of these phenomena. The deployment of a multiparametric in situ monitoring system at depth will enable near-real-time tracking of changes in the magma reservoir and hydrothermal system.

Description: The international endeavour to retrieve a continuous ice core, which spans the middle Pleistocene climate transition ca. 1.2–0.9 Myr ago, encompasses a multitude of field and model-based pre-site surveys. We expand on the current efforts to locate a suitable drilling site for the oldest Antarctic ice core by means of 3-D continental ice-sheet modelling. To this end, we present an ensemble of ice-sheet simulations spanning the last 2 Myr, employing transient boundary conditions derived from climate modelling and climate proxy records. We discuss the imprint of changing climate conditions, sea level and geothermal heat flux on the ice thickness, and basal conditions around previously identified sites with continuous records of old ice. Our modelling results show a range of configurational ice-sheet changes across the middle Pleistocene transition, suggesting a potential shift of the West Antarctic Ice Sheet to a marine-based configuration. Despite the middle Pleistocene climate reorganisation and associated ice-dynamic changes, we identify several regions conducive to conditions maintaining 1.5 Myr (million years) old ice, particularly around Dome Fuji, Dome C and Ridge B, which is in agreement with previous studies. This finding strengthens the notion that continuous records with such old ice do exist in previously identified regions, while we are also providing a dynamic continental ice-sheet context.

Description: While nonlinear stochastic partial differential equations arise naturally in spatiotemporal modeling, inference for such systems often faces two major challenges: sparse noisy data and ill-posedness of the inverse problem of parameter estimation. To overcome the challenges, we introduce a strongly regularized posterior by normalizing the likelihood and by imposing physical constraints through priors of the parameters and states. We investigate joint parameter-state estimation by the regularized posterior in a physically motivated nonlinear stochastic energy balance model (SEBM) for paleoclimate reconstruction. The high-dimensional posterior is sampled by a particle Gibbs sampler that combines a Markov chain Monte Carlo (MCMC) method with an optimal particle filter exploiting the structure of the SEBM. In tests using either Gaussian or uniform priors based on the physical range of parameters, the regularized posteriors overcome the ill-posedness and lead to samples within physical ranges, quantifying the uncertainty in estimation. Due to the ill-posedness and the regularization, the posterior of parameters presents a relatively large uncertainty, and consequently, the maximum of the posterior, which is the minimizer in a variational approach, can have a large variation. In contrast, the posterior of states generally concentrates near the truth, substantially filtering out observation noise and reducing uncertainty in the unconstrained SEBM.

Description: We present a software toolbox that allows the efficient collection, management and maintenance of larger paleoceanographic data sets. The program combines a graphical user interface (GUI) with a simple document-based database and functionality for visualization, stratigraphy (visual alignment and radiocarbon calibration), age modelling and efficient ensemble time-series generation to create larger homogenous data compilations. Data can be imported from Excel or text files, are stored locally in netCDF format and can be easily exchanged between collaborating scientists. Within a data collection, data can be imported either to proxy-specific sub-collections or to a multi-proxy (“miscellaneous”) sub-collection that allows the import and management of any downcore data. A single age model is shared among all proxies of a core within a collection. The stand-alone software can be used with Windows and macOS and does not require web access. Installers of the current version for both Windows 10 and macOS including the C++ code can be downloaded from https://www.marum.de/Stefan-Mulitza/PaleoDataView.html (last access: 5 December 2019) along with a detailed user guide.

Description: Combining ocean general circulation models with proxy data via data assimilation is a means to obtain estimates of past ocean states that are consistent with model physics as well as with proxy data. The climate during the Last Glacial Maximum (LGM, 19–23 ka) was substantially different from today. Even though boundary conditions are comparatively well known, the large-scale patterns of the ocean circulation during this time remain uncertain. Previous efforts to combine ocean models with proxy data have shown dissimilar results regarding the state of the ocean, in particular of the Atlantic Meridional Overturning Circulation. Here, we present a new LGM ocean state estimate that extents previous estimates by using global benthic as well as planktic data on the oxygen isotopic composition of calcite. It is further constrained by global seasonal and annual sea surface temperature (SST) reconstructions. The estimate shows an Atlantic Ocean that is similar to the Late Holocene Atlantic Ocean but with a reduced formation of Antarctic Bottom Water, in contrast to results of previous studies. The results indicate that SST and oxygen isotopic data alone do not require the presence of a shallower North Atlantic Deep Water and a more extensive Antarctic Bottom Water, and highlight the need for more proxy data of different types to obtain reliable ocean state estimates. Additional adjoint sensitivity experiments reveal that data from the deep North Atlantic and from the global deep Southern Ocean are most important to constrain the Atlantic Meridional Overturning Circulation.

Description: The species composition of many groups of marine plankton appears well predicted by sea surface temperature (SST). Consequently, fossil plankton assemblages have been widely used to reconstruct past SST. Most applications of this approach make use of the highest possible taxonomic resolution. However, not all species are sensitive to temperature, and their distribution may be governed by other parameters. There are thus reasons to question the merit of including information about all species, both for transfer function performance and for its effect on reconstructions. Here we investigate the effect of species selection on planktonic foraminifera transfer functions. We assess species importance for transfer function models using a random forest technique and evaluate the performance of models with an increasing number of species. Irrespective of using models that use the entire training set (weighted averaging) or models that use only a subset of the training set (modern analogue technique), we find that the majority of foraminifera species does not carry useful information for temperature reconstruction. Less than one-third of the species in the training set is required to provide a temperature estimate with a prediction error comparable to a transfer function that uses all species in the training set. However, species selection matters for paleotemperature estimates. We find that transfer function models with a different number of species but with the same error may yield different reconstructions of sea surface temperature when applied to the same fossil assemblages. This ambiguity in the reconstructions implies that fossil assemblage change reflects a combination of temperature and other environmental factors. The contribution of the additional factors is site and time specific, indicating ecological and geological complexity in the formation of the sedimentary assemblages. The possibility of obtaining multiple different reconstructions from a single sediment record presents a previously unrecognized source of uncertainty for sea surface temperature estimates based on planktonic foraminifera assemblages. This uncertainty can be evaluated by determining the sensitivity of the reconstructions to species pruning.

Description: Basalt weathering is one of many relevant processes balancing the global carbon cycle via land–ocean alkalinity fluxes. The CO2 consumption by weathering can be calculated using alkalinity and is often scaled with runoff and/or temperature. Here, it is tested if the surface age distribution of a volcanic system derived by geological maps is a useful proxy for changes in alkalinity production with time. A linear relationship between temperature normalized alkalinity fluxes and the Holocene area fraction of a volcanic field was identified using information from 33 basalt volcanic fields, with an r2=0.93. This relationship is interpreted as an aging function and suggests that fluxes from Holocene areas are ∼10 times higher than those from old inactive volcanic fields. However, the cause for the decrease with time is probably a combination of effects, including a decrease in alkalinity production from material in the shallow critical zone as well as a decline in hydrothermal activity and magmatic CO2 contribution. The addition of fresh reactive material on top of the critical zone has an effect in young active volcanic settings which should be accounted for, too. A comparison with global models suggests that global alkalinity fluxes considering Holocene basalt areas are ∼60 % higher than the average from these models imply. The contribution of Holocene areas to the global basalt alkalinity fluxes is today however only ∼5 %, because identified, mapped Holocene basalt areas cover only ∼1 % of the existing basalt areas. The large trap basalt proportion on the global basalt areas today reduces the relevance of the aging effect. However, the aging effect might be a relevant process during periods of globally intensive volcanic activity, which remains to be tested.

Description: Dynamic vegetation models simulate global vegetation in terms of fractional coverage of a few plant functional types (PFTs). Although these models often share the same concept, they differ with respect to the number and kind of PFTs, complicating the comparability of simulated vegetation distributions. Pollen-based vegetation reconstructions are initially only available in the form of time series of individual taxa that are not distinguished in the models. Thus, to evaluate simulated vegetation distributions, the modelling results and pollen-based vegetation reconstructions have to be converted into a comparable format. The classical approach is the method of biomisation, but hitherto PFT-based biomisation methods were only available for individual models. We introduce and evaluate a simple, universally applicable technique to harmonise PFT distributions by assigning them into nine mega-biomes, using only assumptions on the minimum PFT cover fractions and few bioclimatic constraints (based on the 2 m temperature). These constraints mainly follow the limitation rules used in the classical biome models (here BIOME4). We test the method for six state-of-the-art dynamic vegetation models that are included in Earth system models based on pre-industrial, mid-Holocene and Last Glacial Maximum simulations. The method works well, independent of the spatial resolution or the complexity of the models. Large biome belts (such as tropical forest) are generally better represented than regionally confined biomes (warm–temperate forest, savanna). The comparison with biome distributions inferred via the classical biomisation approach of forcing biome models (here BIOME1) with the simulated climate states shows that the PFT-based biomisation is even able to keep up with the classical method. However, as the new method considers the PFT distributions actually calculated by the Earth system models, it allows for a direct comparison and evaluation of simulated vegetation distributions which the classical method cannot do. Thereby, the new method provides a powerful tool for the evaluation of Earth system models in general.

Description: The sedimentary stable nitrogen isotope compositions of bulk organic matter (δ15Nbulk) and silicon isotope composition of diatoms (δ30SiBSi) both mainly reflect the degree of past nutrient utilization by primary producers. However, in ocean areas where anoxic and suboxic conditions prevail, the δ15Nbulk signal ultimately recorded within the sediments is also influenced by water column denitrification causing an increase in the subsurface δ15N signature of dissolved nitrate (δ15NO3−) upwelled to the surface. Such conditions are found in the oxygen minimum zone off Peru, where at present an increase in subsurface δ15NO3− from North to South along the shelf is observed due to ongoing denitrification within the pole-ward flowing subsurface waters, while the δ30Si signature of silicic acid (δ30Si(OH)4) at the same time remains unchanged. Here, we present three new δ30SiBSi records between 11° S and 15° S and compare these to previously published δ30SiBSi and δ15Nbulk records from Peru covering the past 600 years. We present a new approach to calculate past subsurface δ15NO3− signatures based on the correlation of δ30SiBSi and δ15Nbulk signatures at a latitudinal resolution for different time periods. Our results show source water δ15NO3− compositions during the last 200 years, the Current Warm Period (CWP) and during short-term arid events prior to that, which are close to modern values increasing southward from 7 to 10 ‰ (between 11° S and 15° S). In contrast, humid conditions during the Little Ice Age (LIA) reflect consistently low δ15NO3− values between 6 and 7.5‰. Furthermore, we are able to relate the short-term variability in both isotope compositions to changes in the ratio of nutrients (NO3− : Si(OH)4) taken up by different dominating phytoplankton groups (diatoms and non-siliceous phytoplankton) under the variable climatic conditions of the past 600 years.

Description: The open ocean is a major source of nitrous oxide (N2O), an atmospheric trace gas attributable to global warming and ozone depletion. Intense sea-to-air N2O fluxes occur in major oceanic upwelling regions such as the eastern tropical South Pacific (ETSP). The ETSP is influenced by the El Niño–Southern Oscillation that leads to inter-annual variations in physical, chemical, and biological properties in the water column. In October 2015, a strong El Niño event was developing in the ETSP; we conduct field observations to investigate (1) the N2O production pathways and associated biogeochemical properties and (2) the effects of El Niño on water column N2O distributions and fluxes using data from previous non-El Niño years. Analysis of N2O natural abundance isotopomers suggested that nitrification and partial denitrification (nitrate and nitrite reduction to N2O) were occurring in the near-surface waters; indicating that both pathways contributed to N2O effluxes. Higher-than-normal sea surface temperatures were associated with a deepening of the oxycline and the oxygen minimum layer. Within the shelf region, surface N2O supersaturation was nearly an order of magnitude lower than that of non-El Niño years. Therefore, a significant reduction of N2O efflux (75 %–95 %) in the ETSP occurred during the 2015 El Niño. At both offshore and coastal stations, the N2O concentration profiles during El Niño showed moderate N2O concentration gradients, and the peak N2O concentrations occurred at deeper depths during El Niño years; this was likely the result of suppressed upwelling retaining N2O in subsurface waters. At multiple stations, water-column inventories of N2O within the top 1000 m were up to 160 % higher than those measured in non-El Niño years, indicating that subsurface N2O during El Niño could be a reservoir for intense N2O effluxes when normal upwelling is resumed after El Niño.

Description: The early Eocene (56 to 48 million years ago) is inferred to have been the most recent time that Earth's atmospheric CO2 concentrations exceeded 1000 ppm. Global mean temperatures were also substantially warmer than present day. As such, study of early Eocene climate provides insight into how a super-warm Earth system behaves and offers an opportunity to 10 evaluate climate models under conditions of high greenhouse gas forcing. The Deep Time Model Intercomparison Project (DeepMIP) is a systematic model-model and model-data intercomparison of three early Paleogene time slices: latest Paleocene, Paleocene-Eocene thermal maximum and early Eocene climatic optimum. A previous article outlined the model experimental design for climate model simulations. In this article, we outline the methodologies to be used for the compilation and analysis of climate proxy data, primarily proxies for temperature and CO2. This paper establishes the protocols for a concerted and 15 coordinated effort to compile the climate proxy records across a wide geographic range. The resulting climate "atlas" will be used to constrain and evaluate climate models for the three selected time intervals, and provide insights into the mechanisms that control these warm climate states. We provide version 0.1 of this database, in anticipation that this will be expanded in subsequent publications.

Description: Sea surface salinity is one of the most important parameters to reconstruct in paleoclimatology, reflecting amongst others the hydrological cycle, paleo-density, ice volume, and regional and global circulation of water masses. Recent culture studies and a Red Sea field study revealed a significant positive relation between salinity and Na incorporation within benthic and planktonic foraminiferal shells. However, these studies reported varying partitioning of Na between and within the same species. The latter could be associated with ontogenetic variations, most likely spine loss. Varying Na concentrations were observed in different parts of foraminiferal shells, with especially spines and regions close to the primary organic sheet being enriched in Na. In this study, we unravel the Na composition of different components of the planktonic foraminiferal shell wall using Electron Probe Micro Analysis (EPMA) and solution-ICP-MS. A model is presented to interpret EPMA data for spines and spine bases to quantitatively assess differences in composition and contribution to whole shell Na/Ca signals. The same model can also be applied to other spatial inhomogeneities observed in foraminiferal shell chemistry, like elemental (e.g. Mg, Na, S) banding and/or hotspots. The relative contribution of shell calcite, organic linings, spines and spine bases to whole shell Na chemistry is considered quantitatively. This study shows that whereas the high Na areas may be susceptible to taphonomy, the Na chemistry of the shell itself seems relatively robust. Comparing both shell and spine Na/Ca values with salinity shows that shell chemistry records salinity, albeit with a very modest slope.

Description: Due to its remoteness, the deep-sea floor remains an understudied ecosystem of our planet. The patchiness of existing data sets makes it difficult to draw conclusions about processes that apply to a wider area. In our study we show how different settings and processes determine sediment heterogeneity on small spatial scales. We sampled solid phase and porewater from the upper 10 m of an approximately 7.4×13 km2 area in the Peru Basin, in the southeastern equatorial Pacific Ocean, at 4100 m water depth. Samples were analyzed for trace metals, including rare earth elements and yttrium (REY), as well as for particulate organic carbon (POC), CaCO3, and nitrate. The analyses revealed the surprisingly high spatial small-scale heterogeneity of the deep-sea sediment composition. While some cores have the typical green layer from Fe(II) in the clay minerals, this layer is missing in other cores, i.e., showing a tan color associated with more Fe(III) in the clay minerals. This is due to varying organic carbon contents: nitrate is depleted at 2–3 m depth in cores with higher total organic carbon contents but is present throughout cores with lower POC contents, thus inhibiting the Fe(III)-to-Fe(II) reduction pathway in organic matter degradation. REY show shale-normalized (SN) patterns similar to seawater, with a relative enrichment of heavy REY over light REY, positive LaSN anomaly, negative CeSN anomaly, and positive YSN anomaly and correlate with the Fe-rich clay layer and, in some cores, also correlate with P. We therefore propose that Fe-rich clay minerals, such as nontronite, as well as phosphates, are the REY-controlling phases in these sediments. Variability is also seen in dissolved Mn and Co concentrations between sites and within cores, which might be due to dissolving nodules in the suboxic sediment, as well as in concentration peaks of U, Mo, As, V, and Cu in two cores, which might be related to deposition of different material at lower-lying areas or precipitation due to shifting redox boundaries.

Description: Global climatologies of the seawater CO2 chemistry variables are necessary to assess the marine carbon cycle in depth. The climatologies should adequately capture seasonal variability to properly address ocean acidification and similar issues related to the carbon cycle. Total alkalinity (A(T)) is one variable of the seawater CO2 chemistry system involved in ocean acidification and frequently measured. We used the Global Ocean Data Analysis Project version 2.2019 (GLODAPv2) to extract relationships among the drivers of the A(T) variability and A(T) concentration using a neural network (NNGv2) to generate a monthly climatology. The GLODAPv2 quality-controlled dataset used was modeled by the NNGv2 with a root-mean-squared error (RMSE) of 5.3 mu mol kg(-1). Validation tests with independent datasets revealed the good generalization of the network. Data from five ocean time-series stations showed an acceptable RMSE range of 3-6.2 mu mol kg(-1). Successful modeling of the monthly A(T) variability in the time series suggests that the NNGv2 is a good candidate to generate a monthly climatology. The climatological fields of A(T) were obtained passing through the NNGv2 the World Ocean Atlas 2013 (WOA13) monthly climatologies of temperature, salinity, and oxygen and the computed climatologies of nutrients from the previous ones with a neural network. The spatiotemporal resolution is set by WOA13: 1 degrees x 1 degrees in the horizontal, 102 depth levels (0-5500 m) in the vertical and monthly (0-1500 m) to annual (1550-5500 m) temporal resolution. The product is distributed through the data repository of the Spanish National Research Council (CSIC; https://doi.org/10.20350/digitalCSIC/8644, Broullon et al., 2019).

Description: The flow (flux) of climate-critical gases, such as carbon dioxide (CO2), between the ocean and the atmosphere is a fundamental component of our climate and an important driver of the biogeochemical systems within the oceans. Therefore, the accurate calculation of these air–sea gas fluxes is critical if we are to monitor the oceans and assess the impact that these gases are having on Earth's climate and ecosystems. FluxEngine is an open-source software toolbox that allows users to easily perform calculations of air–sea gas fluxes from model, in situ, and Earth observation data. The original development and verification of the toolbox was described in a previous publication. The toolbox has now been considerably updated to allow for its use as a Python library, to enable simplified installation, to ensure verification of its installation, to enable the handling of multiple sparingly soluble gases, and to enable the greatly expanded functionality for supporting in situ dataset analyses. This new functionality for supporting in situ analyses includes user-defined grids, time periods and projections, the ability to reanalyse in situ CO2 data to a common temperature dataset, and the ability to easily calculate gas fluxes using in situ data from drifting buoys, fixed moorings, and research cruises. Here we describe these new capabilities and demonstrate their application through illustrative case studies. The first case study demonstrates the workflow for accurately calculating CO2 fluxes using in situ data from four research cruises from the Surface Ocean CO2 ATlas (SOCAT) database. The second case study calculates air–sea CO2 fluxes using in situ data from a fixed monitoring station in the Baltic Sea. The third case study focuses on nitrous oxide (N2O) and, through a user-defined gas transfer parameterisation, identifies that biological surfactants in the North Atlantic could suppress individual N2O sea–air gas fluxes by up to 13 %. The fourth and final case study illustrates how a dissipation-based gas transfer parameterisation can be implemented and used. The updated version of the toolbox (version 3) and all documentation is now freely available.

Description: Climate reconstructions are means to extract the signal from uncertain paleo-observations, so-called proxies. It is essential to evaluate these reconstructions to understand and quantify their uncertainties. Similarly, comparing climate simulations and proxies requires approaches to bridge the temporal and spatial differences between both and to address their specific uncertainties. One way to achieve these two goals is so-called pseudoproxies. These are surrogate proxy records within the virtual reality of a climate simulation. They in turn depend on an understanding of the uncertainties of the real proxies including the noise characteristics disturbing the original environmental signal. Common pseudoproxy approaches so far concentrate on data with high temporal resolution over the last approximately 2000 years. Here we provide a simple but flexible noise model for potentially low-resolution sedimentary climate proxies for temperature on millennial timescales, the code for calculating a set of pseudoproxies from a simulation, and one example of pseudoproxies. The noise model considers the influence of other environmental variables, a dependence on the climate state, a bias due to changing seasonality, modifications of the archive (for example bioturbation), potential sampling variability, and a measurement error. Model, code, and data allow us to develop new ways of comparing simulation data with proxies on long timescales. Code and data are available at https://doi.org/10.17605/OSF.IO/ZBEHX (Bothe et al., 2018).

Description: Atmospheric deposition is an important source of micronutrients to the ocean, but atmospheric deposition fluxes remain poorly constrained in most ocean regions due to the limited number of field observations of wet and dry atmospheric inputs. Here we present the distribution of dissolved aluminium (dAl), as a tracer of atmospheric inputs, in surface waters of the Atlantic Ocean along GEOTRACES sections GA01, GA06, GA08, and GA10. We used the surface mixed layer concentrations of dAl to calculate atmospheric deposition fluxes using a simple steady state model. We have optimized the aerosol Al fractional solubility, dAl residence time within the surface mixed layer and depth of the surface mixed layer for each separate cruise to calculate the atmospheric deposition fluxes. We calculated the lowest deposition fluxes of 0.15 ± 0.1 and 0.27 ± 0.13 g m−2 yr−1 for the South and North Atlantic Ocean (〉 40° S and 〉 40° N), respectively, and highest fluxes of 2.67 ± 1.96 and 3.82 ± 2.72 g m−2 yr−1 for the South East Atlantic and tropical Atlantic Ocean, respectively. Overall, our estimations are comparable to atmospheric dust deposition model estimates and reported field-based atmospheric deposition estimates. We note that our estimates diverge from atmospheric dust deposition model flux estimates in regions influenced by riverine Al inputs and in upwelling regions. As dAl is a key trace element in the GEOTRACES Programme, the approach presented in this study allows calculations of atmospheric deposition fluxes at high spatial resolution for remote ocean regions.

Description: The nature of the Ionian Sea crust has been the subject of scientific debate for more than 30 years, mainly because seismic imaging of the deep crust and upper mantle of the Ionian Abyssal Plain (IAP) has not been conclusive to date. The IAP is sandwiched between the Calabrian and Hellenic subduction zones in the central Mediterranean. To univocally confirm the proposed oceanic nature of the IAP crust as a remnant of the Tethys ocean and to confute its interpretation as a strongly thinned part of the African continental crust, a NE-SW oriented 131 km long seismic refraction and wide-angle reflection profile consisting of eight ocean bottom seismometers and hydrophones was acquired in 2014. A P-wave velocity model developed from travel time forward modelling is refined by gravimetric data and synthetic modelling of the seismic data. A roughly 6km thick crust with velocities ranging from 5.1km/s to 7.2km/s, top to bottom, can be traced throughout the IAP. In the vicinity of the Medina Seamounts at the southern IAP boundary, the crust thickens to about 9km and seismic velocities decrease to 6.8km/s at the crust-mantle boundary. The seismic velocity distribution and depth of the crust-mantle boundary in the IAP document its oceanic nature, and support the interpretation of the IAP as a remnant of the Tethys oceanic lithosphere formed during the Permian and Triassic period.

Description: We describe the development of the “Paleoclimate PLASIM-GENIE emulator” PALEO-PGEM and its application to derive a downscaled high-resolution spatiotemporal description of the climate of the last five million years. The 5-million-year time frame is interesting for a range of paleo-environmental questions, not least because it encompasses the evolution of humans. However, the choice of time-frame was primarily pragmatic; tectonic changes can be neglected to first order, so that it is reasonable to consider climate forcing restricted to the Earth's orbital configuration, ice-sheet state and the concentration of atmosphere CO2. The approach uses the Gaussian process emulation of the singular value decomposition of boundary-condition ensembles of the intermediate complexity atmosphere-ocean GCM PLASIM-GENIE. Spatial fields of bioclimatic variables of surface air temperature (warmest and coolest seasons) and precipitation (wettest and driest seasons) are emulated at 1,000 year intervals, driven by time-series of scalar boundary-condition forcing (CO2, orbit and ice-volume), and assuming the climate is in quasi-equilibrium. Paleoclimate anomalies at climate model resolution are interpolated onto the observed modern climatology to produce a high-resolution spatiotemporal paleoclimate reconstruction of the Pliocene-Pleistocene.

Description: Long-term measurements of volcanic gas emissions conducted during the recent decade suggest that under certain conditions the magnitude or chemical composition of volcanic emissions exhibits periodic variations with a period of about two weeks. A possible cause of such a periodicity can be attributed to the Earth tidal potential. The phenomenology of such a link has been debated for long, but no quantitative model has yet been proposed. The aim of this paper is to elucidate whether a causal link from the tidal forcing to variation in the volcanic degassing can be traced analytically. We model the response of a simplified magmatic system to the local tidal gravity variations and derive a periodical vertical magma displacement in the conduit with an amplitude of 0.1–1 m, depending on geometry and physical state of the magmatic system. We find that while the tide-induced vertical magma displacement has presumably no significant direct effect on the volatile solubility, the differential magma flow across the radial conduit profile may result in a significant increase of the bubble coalescence rate in a depth of several kilometres by up to several ten percent. Because bubble coalescence facilitates separation of gas from magma and thus enhances volatile degassing, we argue that the derived tidal variation may propagate to a manifestation of varying volcanic degassing behaviour. The presented model provides a first basic framework which establishes an analytical understanding of the link between the Earth tides and volcanic degassing.

Description: Ground-based atmospheric observations of CO2, δ(O2∕N2), N2O, and CH4 were used to make estimates of the air–sea fluxes of these species from the Lüderitz and Walvis Bay upwelling cells in the northern Benguela region, during upwelling events. Average flux densities (±1σ) were 0.65±0.4 µmol m−2 s−1 for CO2, −5.1±2.5 µmol m−2 s−1 for O2 (as APO), 0.61±0.5 nmol m−2 s−1 for N2O, and 4.8±6.3 nmol m−2 s−1 for CH4. A comparison of our top-down (i.e., inferred from atmospheric anomalies) flux estimates with shipboard-based measurements showed that the two approaches agreed within ±55 % on average, though the degree of agreement varied by species and was best for CO2. Since the top-down method overestimated the flux density relative to the shipboard-based approach for all species, we also present flux density estimates that have been tuned to best match the shipboard fluxes. During the study, upwelling events were sources of CO2, N2O, and CH4 to the atmosphere. N2O fluxes were fairly low, in accordance with previous work suggesting that the evasion of this gas from the Benguela is smaller than for other eastern boundary upwelling systems (EBUS). Conversely, CH4 release was quite high for the marine environment, a result that supports studies that indicated a large sedimentary source of CH4 in the Walvis Bay area. These results demonstrate the suitability of atmospheric time series for characterizing the temporal variability of upwelling events and their influence on the overall marine greenhouse gas (GHG) emissions from the northern Benguela region.

Description: The atmospheric CO2 concentration increased by about 20ppm from 6000BCE to the pre-industrial period (1850CE). Several hypotheses have been proposed to explain mechanisms of this CO2 growth based on either ocean or land carbon sources. Here, we apply the Earth system model MPI-ESM-LR for two transient simulations of climate and carbon cycle dynamics during this period. In the first simulation, atmospheric CO2 is prescribed following ice-core CO2 data. In response to the growing atmospheric CO2 concentration, land carbon storage increases until 2000BCE, stagnates afterwards, and decreases from 1CE, while the ocean continuously takes CO2 out of the atmosphere after 4000BCE. This leads to a missing source of 166Pg of carbon in the ocean-land-atmosphere system by the end of the simulation. In the second experiment, we applied a CO2 nudging technique using surface alkalinity forcing to follow the reconstructed CO2 concentration while keeping the carbon cycle interactive. In that case the ocean is a source of CO2 from 6000 to 2000BCE due to a decrease in the surface ocean alkalinity. In the prescribed CO2 simulation, surface alkalinity declines as well. However, it is not sufficient to turn the ocean into a CO2 source. The carbonate ion concentration in the deep Atlantic decreases in both the prescribed and the interactive CO2 simulations, while the magnitude of the decrease in the prescribed CO2 experiment is underestimated in comparison with available proxies. As the land serves as a carbon sink until 2000BCE due to natural carbon cycle processes in both experiments, the missing source of carbon for land and atmosphere can only be attributed to the ocean. Within our model framework, an additional mechanism, such as surface alkalinity decrease, for example due to unaccounted for carbonate accumulation processes on shelves, is required for consistency with ice-core CO2 data. Consequently, our simulations support the hypothesis that the ocean was a source of CO2 until the late Holocene when anthropogenic CO2 sources started to affect atmospheric CO2.

Description: The stable isotopic composition of particulate organic carbon (δ13CPOC) in the surface waters of the global ocean can vary with the aqueous CO2 concentration ([CO2(aq)]) and affects the trophic transfer of carbon isotopes in the marine food web. Other factors such as cell size, growth rate and carbon concentrating mechanisms decouple this observed correlation. Here, the variability in δ13CPOC is investigated in surface waters across the south subtropical convergence (SSTC) in the Atlantic Ocean, to determine carbon isotope fractionation (ϵp) by phytoplankton and the contrasting mechanisms of carbon uptake in the subantarctic and subtropical water masses. Our results indicate that cell size is the primary determinant of δ13CPOC across the Atlantic SSTC in summer. Combining cell size estimates with CO2 concentrations, we can accurately estimate "p within the varying surface water masses in this region. We further utilize these results to investigate future changes in "p with increased anthropogenic carbon availability. Our results suggest that smaller cells, which are prevalent in the subtropical ocean, will respond less to increased [CO2(aq)] than the larger cells found south of the SSTC and in the wider Southern Ocean. In the subantarctic water masses, isotopic fractionation during carbon uptake will likely increase, both with increasing CO2 availability to the cell, but also if increased stratification leads to decreases in average community cell size. Coupled with decreasing δ13C of [CO2(aq)] due to anthropogenic CO2 emissions, this change in isotopic fractionation and lowering of δ13CPOC may propagate through the marine food web, with implications for the use of δ13CPOC as a tracer of dietary sources in the marine environment.

Description: The amount of additional future temperature change following a complete cessation of CO2 emissions is a measure of the unrealized warming to which we are committed due to CO2 already emitted to the atmosphere. This "zero emissions commitment" (ZEC) is also an important quantity when estimating the remaining carbon budget - a limit on the total amount of CO2 emissions consistent with limiting global mean temperature at a particular level. In the recent IPCC Special Report on Global Warming of 1.5 degrees C, the carbon budget framework used to calculate the remaining carbon budget for 1.5 degrees C included the assumption that the ZEC due to CO2 emissions is negligible and close to zero. Previous research has shown significant uncertainty even in the sign of the ZEC. To close this knowledge gap, we propose the Zero Emissions Commitment Model Intercomparison Project (ZECMIP), which will quantify the amount of unrealized temperature change that occurs after CO2 emissions cease and investigate the geophysical drivers behind this climate response. Quantitative information on ZEC is a key gap in our knowledge, and one that will not be addressed by currently planned CMIP6 simulations, yet it is crucial for verifying whether carbon budgets need to be adjusted to account for any unrealized temperature change resulting from past CO2 emissions. We request only one top-priority simulation from comprehensive general circulation Earth system models (ESMs) and Earth system models of intermediate complexity (EMICs) - a branch from the 1% CO2 run with CO2 emissions set to zero at the point of 1000 PgC of total CO2 emissions in the simulation - with the possibility for additional simulations, if resources allow. ZECMIP is part of CMIP6, under joint sponsorship by C4MIP and CDR-MIP, with associated experiment names to enable data submissions to the Earth System Grid Federation. All data will be published and made freely available.

Description: Mining of polymetallic nodules in abyssal seafloor sediments promises to address the growing worldwide demand for metallic minerals. Given that prospective mining operations are likely to have profound impacts on deep seafloor communities, industrial investment has been accompanied by scientific involvement for the assessment of baseline conditions and provision of guidelines for environmentally sustainable mining practices. Benthic meiofaunal communities were studied in four prospective mining areas of the Clarion–Clipperton Zone (CCZ) in the eastern Pacific Ocean, arranged in a southeast–northwest fashion coinciding with the productivity gradient in the area. Additionally, samples were collected from the Area of Particular Environmental Interest no. 3 (APEI-3) in the northwest of the CCZ, where mining will be prohibited and which should serve as a “source area” for the biota within the larger CCZ. Total densities in the 0–5 cm upper layer of the sediment were influenced by sedimentary characteristics, water depth and nodule density at the various sampling locations, indicating the importance of nodules for meiofaunal standing stock. Nematodes were the most abundant meiobenthic taxon, and their assemblages were typically dominated by a few genera (generally 2–6) accounting for 40 %–70 % of all individuals, which were also widely spread along the CCZ and shared among all sampled license areas. However, almost half of the communities consisted of rare genera, each contributing less than 5 % to the overall abundances and displaying a distribution which was usually restricted to a single license area. The same observations (dominant and widely spread versus rare and scattered) could be made for the species of one of the dominant genera, Halalaimus, implying that it might be mainly these rare genera and species that will be vulnerable to mining-induced changes in their habitat.

Description: Chloromethane (CH3Cl) is the most important natural input of reactive chlorine to the stratosphere, contributing about 16 % to stratospheric ozone depletion. Due to the phase-out of anthropogenic emissions of chlorofluorocarbons, CH3Cl will largely control future levels of stratospheric chlorine. The tropical rainforest is commonly assumed to be the strongest single CH3Cl source, contributing over half of the global annual emissions of about 4000 to 5000 Gg (1 Gg = 109 g). This source shows a characteristic carbon isotope fingerprint, making isotopic investigations a promising tool for improving its atmospheric budget. Applying carbon isotopes to better constrain the atmospheric budget of CH3Cl requires sound information on the kinetic isotope effects for the main sink processes: the reaction with OH and Cl in the troposphere. We conducted photochemical CH3Cl degradation experiments in a 3500 dm3 smog chamber to determine the carbon isotope effect (ε=k13C/k12C−1 ) for the reaction of CH3Cl with OH and Cl. For the reaction of CH3Cl with OH, we determined an ε value of (−11.2±0.8) ‰ (n=3) and for the reaction with Cl we found an ε value of (−10.2±0.5 ) ‰ (n=1), which is 5 to 6 times smaller than previously reported. Our smaller isotope effects are strongly supported by the lack of any significant seasonal covariation in previously reported tropospheric δ13C(CH3Cl) values with the OH-driven seasonal cycle in tropospheric mixing ratios. Applying these new values for the carbon isotope effect to the global CH3Cl budget using a simple two hemispheric box model, we derive a tropical rainforest CH3Cl source of (670±200) Gg a−1, which is considerably smaller than previous estimates. A revision of previous bottom-up estimates, using above-ground biomass instead of rainforest area, strongly supports this lower estimate. Finally, our results suggest a large unknown CH3Cl source of (1530±200) Gg a−1.

Description: Nitric oxide (NO) is a short-lived compound of the marine nitrogen cycle; however, our knowledge about its oceanic distribution and turnover is rudimentary. Here we present the measurements of dissolved NO in the surface and bottom layers at 75 stations in the Bohai Sea (BS) and the Yellow Sea (YS) in June 2011. Moreover, NO photoproduction rates were determined at 27 stations in both seas. The NO concentrations in the surface and bottom layers were highly variable and ranged from below the limit of detection (i.e., 32 pmol L−1) to 616 pmol L−1 in the surface layer and 482 pmol L−1 in the bottom layer. There was no significant difference (p〉0.05) between the mean NO concentrations in the surface (186±108 pmol L−1) and bottom (174±123 pmol L−1) layers. A decreasing trend of NO in bottom-layer concentrations with salinity indicates a NO input by submarine groundwater discharge. NO in the surface layer was supersaturated at all stations during both day and night and therefore the BS and YS were a persistent source of NO to the atmosphere at the time of our measurements. The average flux was about 4.5×10−16 mol cm−2 s−1 and the flux showed significant positive relationship with the wind speed. The accumulation of NO during daytime was a result of photochemical production, and photoproduction rates were correlated to illuminance. The persistent nighttime NO supersaturation pointed to an unidentified NO dark production. NO sea-to-air flux densities were much lower than the NO photoproduction rates. Therefore, we conclude that the bulk of the NO produced in the mixed layer was rapidly consumed before its release to the atmosphere.

Description: The Arctic marine climate system is changing rapidly, which is seen in the warming of the ocean and atmosphere, decline of sea ice cover, increase in river discharge, acidification of the ocean, and changes in marine ecosystems. Socio-economic activities in the coastal and marine Arctic are simultaneously changing. This calls for the establishment of a marine Arctic component of the Pan-Eurasian Experiment (MA-PEEX). There is a need for more in situ observations on the marine atmosphere, sea ice, and ocean, but increasing the amount of such observations is a pronounced technological and logistical challenge. The SMEAR (Station for Measuring Ecosystem–Atmosphere Relations) concept can be applied in coastal and archipelago stations, but in the Arctic Ocean it will probably be more cost-effective to further develop a strongly distributed marine observation network based on autonomous buoys, moorings, autonomous underwater vehicles (AUVs), and unmanned aerial vehicles (UAVs). These have to be supported by research vessel and aircraft campaigns, as well as various coastal observations, including community-based ones. Major manned drifting stations may occasionally be comparable to terrestrial SMEAR flagship stations. To best utilize the observations, atmosphere–ocean reanalyses need to be further developed. To well integrate MA-PEEX with the existing terrestrial–atmospheric PEEX, focus is needed on the river discharge and associated fluxes, coastal processes, and atmospheric transports in and out of the marine Arctic. More observations and research are also needed on the specific socio-economic challenges and opportunities in the marine and coastal Arctic, and on their interaction with changes in the climate and environmental system. MA-PEEX will promote international collaboration; sustainable marine meteorological, sea ice, and oceanographic observations; advanced data management; and multidisciplinary research on the marine Arctic and its interaction with the Eurasian continent.

Description: Phytoplankton calcifiers contribute to global carbon cycling through their dual formation of calcium carbonate and particulate organic carbon (POC). The carbonate might provide an efficient export pathway for the associated POC to the deep ocean, reducing the particles' exposure to biological degradation in the upper ocean and increasing the particle settling rate. Previous work has suggested ballasting of POC by carbonate might increase in a warming climate, in spite of increasing carbonate dissolution rates, because calcifiers benefit from the widespread nutrient limitation arising from stratification. We compare the biogeochemical responses of three models containing (1) a single mixed phytoplankton class, (2) additional explicit small phytoplankton and calcifiers, and (3) additional explicit small phytoplankton and calcifiers with a prognostic carbonate ballast model, to two rapid changes in atmospheric CO2. The first CO2 scenario represents a rapid (151-year) transition from a stable icehouse climate (283.9 ppm) into a greenhouse climate (1263 ppm); the second represents a symmetric rapid transition from a stable greenhouse climate into an icehouse climate. We identify a slope change in the global net primary production response with a transition point at about 3.5 ∘C global mean sea surface temperature change in all models, driven by a combination of physical and biological changes. We also find that in both warming and cooling scenarios, the application of a prognostic carbonate ballast model moderates changes in carbon export production, suboxic volume, and nitrate sources and sinks, reducing the long-term model response to about one-third that of the calcifier model without ballast. Explicit small phytoplankton and calcifiers, and carbonate ballasting, increase the physical separation of nitrate sources and sinks through a combination of phytoplankton competition and lengthened remineralization profile, resulting in a significantly higher global nitrate inventory in this model compared to the single phytoplankton type model (15 % and 32 % higher for icehouse and greenhouse climates). Higher nitrate inventory alleviates nitrate limitation, increasing phytoplankton sensitivity to changes in physical limitation factors (light and temperature). This larger sensitivity to physical forcing produces stronger shifts in ocean phosphate storage between icehouse and greenhouse climates. The greenhouse climate is found to hold phosphate and nitrate deeper in the ocean, despite a shorter remineralization length scale than the icehouse climate, because of the longer residence times of the deep water masses. We conclude the global biogeochemical impact of calcifiers extends beyond their role in global carbon cycling, and that the ecological composition of the global ocean can affect how ocean biogeochemistry responds to climate forcing.

Description: The coastal upwelling regime off Peru in December 2012 showed considerable vertical concentration gradients of dissolved nitrous oxide (N2O) across the top few meters of the ocean. The gradients were predominantly downward, i.e., concentrations decreased toward the surface. Ignoring these gradients causes a systematic error in regionally integrated gas exchange estimates, when using observed concentrations at several meters below the surface as input for bulk flux parameterizations – as is routinely practiced. Here we propose that multi-day near-surface stratification events are responsible for the observed near-surface N2O gradients, and that the gradients induce the strongest bias in gas exchange estimates at winds of about 3 to 6 m s−1. Glider hydrographic time series reveal that events of multi-day near-surface stratification are a common feature in the study region. In the same way as shorter events of near-surface stratification (e.g., the diurnal warm layer cycle), they preferentially exist under calm to moderate wind conditions, suppress turbulent mixing, and thus lead to isolation of the top layer from the waters below (surface trapping). Our observational data in combination with a simple gas-transfer model of the surface trapping mechanism show that multi-day near-surface stratification can produce near-surface N2O gradients comparable to observations. They further indicate that N2O gradients created by diurnal or shorter stratification cycles are weaker and do not substantially impact bulk emission estimates. Quantitatively, we estimate that the integrated bias for the entire Peruvian upwelling region in December 2012 represents an overestimation of the total N2O emission by about a third, if concentrations at 5 or 10 m depth are used as surrogate for bulk water N2O concentration. Locally, gradients exist which would lead to emission rates overestimated by a factor of two or more. As the Peruvian upwelling region is an N2O source of global importance, and other strong N2O source regions could tend to develop multi-day near-surface stratification as well, the bias resulting from multi-day near-surface stratification may also impact global oceanic N2O emission estimates.

Description: The coastal waters of the Baltic Sea are subject to high variations in environmental conditions, triggered by natural and anthropogenic causes. Thus, in situ measurements of water parameters can be strategic for our understanding of the dynamics in shallow water habitats. In this study we present the results of a monitoring program at low water depths (1–2.5 m), covering 13 stations along the Baltic coast of Schleswig-Holstein, Germany. The provided dataset consists of records for dissolved inorganic nutrient concentrations taken twice a month and continuous readings at 10 min intervals for temperature, salinity and oxygen content. Data underwent quality control procedures and were flagged. On average, a data availability of 〉90 % was reached for the monitoring period within 2016–2018. The obtained monitoring data reveal great temporal and spatial variabilities of key environmental factors for shallow water habitats in the southwestern Baltic Sea. Therefore the presented information could serve as realistic key data for experimental manipulations of environmental parameters as well as for the development of oceanographic, biogeochemical or ecological models.

Description: Eddy covariance measurements show gas transfer velocity suppression at medium to high wind speed. A wind-wave interaction described by the transformed Reynolds number is used to characterize environmental conditions favoring this suppression. We take the transformed Reynolds number parameterization to review the two most cited wind speed gas transfer velocity parameterizations: Nightingale et al. (2000) and Wanninkhof (1992, 2014). We propose an algorithm to adjust k values for the effect of gas transfer suppression and validate it with two directly measured dimethyl sulfide (DMS) gas transfer velocity data sets that experienced gas transfer suppression. We also show that the data set used in the Nightingale 2000 parameterization experienced gas transfer suppression. A compensation of the suppression effect leads to an average increase of 22% in the k vs. u relationship. Performing the same correction for Wanninkhof 2014 leads to an increase of 9.85 %. Additionally, we applied our gas transfer suppression algorithm to global air-sea flux climatologies of CO2 and DMS. The global application of gas transfer suppression leads to a decrease of 11% in DMS outgassing. We expect the magnitude of Reynolds suppression on any global air-sea gas exchange to be about 10%

Description: Industrial interest in deep-sea mineral extraction began decades ago and today it is at an all-time high, accelerated by global demand for metals. Several seafloor ecosystem disturbance experiments were performed beginning in the 1970’s, including the DISturbance and reCOLonization experiment (DISCOL) conducted in the Peru Basin in 1989. A large seafloor disturbance was created by repeatedly plowing the seafloor over an area of ~ 10.8 km2. Though a number of studies in abyssal mining regions have evaluated megafaunal biodiversity and ecosystem responses, few have included quantitative and detailed data on fishes or scavengers despite their ecological importance as top predators. We used towed camera transects and baited camera data to evaluate the fish community at the DISCOL site. The abyssal fish community was relatively diverse with 16 taxa dominated by Ipnops meadi. Fish density was lower in ploughed habitat during the several years following disturbance but thereafter increased over time in part due to changes in regional environmental conditions. 26 years post disturbance there were no differences in overall total fish densities between reference and experimental areas, but the dominant fish, I. meadi, still exhibited much lower densities in ploughed habitat suggesting only partial fish community recovery. The scavenging community was dominated by eelpouts (Pachycara spp), hermit crabs (Probeebei mirabilis) and shrimp. The large contribution of hermit crabs appears unique amongst abyssal scavenger studies worldwide. The abyssal fish community at DISCOL was similar to that in the more northerly Clarion Clipperton Zone, though some species have only been observed at DISCOL thus far. Also, further species level identifications are required to refine this assessment. Additional studies across the polymetallic nodule provinces of the Pacific are required to further evaluate the environmental drivers of fish density and diversity and species biogeographies, which will be important for the development of appropriate management plans aimed at minimizing human impact from deep-sea mining.

Description: The eastern tropical South Pacific (ETSP) hosts the Peruvian upwelling system, which represents one of the most productive areas in the world ocean. High primary production followed by rapid heterotrophic utilization of organic matter supports the formation of one of the most intense oxygen minimum zones (OMZs) in the world ocean, where dissolved oxygen (O2) concentrations reach less than 1 µmol kg−1. The high productivity leads to an accumulation of dissolved organic matter (DOM) in the surface layers that may serve as a substrate for heterotrophic respiration. However, the importance of DOM utilization for O2 respiration in the Peruvian upwelling system in general and for shaping the upper oxycline in particular remains unclear so far. This study reports the first estimates of diapycnal fluxes and supply of O2, dissolved organic carbon (DOC), dissolved organic nitrogen, dissolved hydrolysable amino acids (DHAA) and dissolved combined carbohydrates (DCCHO) for the ETSP off Peru. Diapycnal flux and supply estimates were obtained by combining measured vertical diffusivities and solute concentration gradients. They were analysed together with the molecular composition of DCCHO and DHAA to infer the transport of labile DOM into the upper OMZ and the potential role of DOM utilization for the attenuation of the diapycnal O2 flux that ventilates the OMZ. The observed diapycnal O2 flux (50 mmol O2 m−2 d−1 at maximum) was limited to the upper 80 m of the water column; the O2 supply of ∼1 µmol kg−1 d−1 was comparable to previously published O2 consumption rates for the North and South Pacific OMZs. The diapycnal DOM flux (31 mmol C m−2 d−1 at maximum) was limited to ∼30 m water depth, suggesting that the labile DOM is extensively consumed within the upper part of the shallow oxycline off Peru. The analyses of DCCHO and DHAA composition support this finding, suggesting that DOM undergoes comprehensive remineralization within the upper part of the oxycline, as the DOM within the core of the OMZ was found to be largely altered. Estimated by a simple equation for carbon combustion, aerobic respiration of DCCHO and DHAA, supplied by diapycnal mixing (0.46 µmol kg−1 d−1 at maximum), could account for up to 38 % of the diapycnal O2 supply in the upper oxycline, which suggests that DOM utilization plays a significant role for shaping the upper oxycline in the ETSP.

Description: Increasing industrial metal demands due to rapid technological developments may drive the prospection and exploitation of deep-sea mineral resources such as polymetallic nodules. To date, the potential environmental consequences of mining operations in the remote deep sea are poorly known. Experimental studies are scarce, especially with regard to the effect of sediment and nodule debris depositions as a consequence of seabed mining. To elucidate the potential effects of the deposition of crushed polymetallic nodule particles on abyssal meiobenthos communities, a short (11 d) in situ experiment at the seafloor of the Peru Basin in the south-east Pacific Ocean was conducted in 2015. We covered abyssal, soft sediment with approx. 2 cm of crushed nodule particles and sampled the sediment after 11 d of incubation at 4200 m water depth. Short-term ecological effects on the meiobenthos community were studied including changes in their composition and vertical distribution in the sediment as well as nematode genus composition. Additionally, copper burden in a few similar-sized but randomly selected nematodes was measured by means of micro X-ray fluorescence (µXRF). At the end of the experiment, 46±1 % of the total meiobenthos occurred in the added crushed nodule layer, while abundances decreased in the underlying 2 cm compared to the same depth interval in undisturbed sediments. Densities and community composition in the deeper 2–5 cm layers remained similar in covered and uncovered sediments. The migratory response into the added nodule material was particularly seen in polychaetes (73±14 %, relative abundance across all depth layers) copepods (71±6 %), nauplii (61±9 %) and nematodes (43±1 %). While the dominant nematode genera in the added nodule material did not differ from those in underlying layers or the undisturbed sediments, feeding type proportions in this layer were altered, with a 9 % decrease of non-selective deposit feeders and an 8 % increase in epistrate feeders. Nematode tissue copper burden did not show elevated copper toxicity resulting from burial with crushed nodule particles. Our results indicate that burial with a 2 cm layer of crushed nodule particles induces changes in the vertical structure of meiobenthos inside the sediment and an alteration of nematode feeding type proportions within a short time frame of 11 d, while nematode tissue copper burden remains unchanged. These findings considerably contribute to the understanding of the short-term responses of meiobenthos to physical disturbances in the deep sea.

Description: The westerlies and trade winds over the South Atlantic and Indian Ocean are important drivers of the regional oceanography around southern Africa, including features such as the Agulhas Current, the Agulhas leakage, and the Benguela upwelling. Agulhas leakage constitutes a fraction of warm and saline water transport from the Indian Ocean into the South Atlantic. The leakage is stronger during intensified westerlies. Here, we analyze the wind stress of different observational and modeled atmospheric data sets (covering the last 2 millennia, the recent decades, and the 21st century) with regard to the intensity and position of the southeasterly trades and the westerlies. The analysis reveals that variations of both wind systems go hand in hand and that a poleward shift of the westerlies and trades and an intensification of westerlies took place during the recent decades. Furthermore, upwelling in South Benguela is slightly intensified when trades are shifted poleward. Projections for strength and position of the westerlies in the 21st century depend on assumed CO2 emissions and on their effect relative to the ozone forcing. In the strongest emission scenario (RCP8.5) the simulations show a further southward displacement, whereas in the weakest emission scenario (RCP2.6) a northward shift is modeled, possibly due to the effect of ozone recovery dominating the effect of anthropogenic greenhouse forcing. We conclude that the Agulhas leakage has intensified during the last decades and is projected to increase if greenhouse gas emissions are not reduced. This will have a small impact on Benguela upwelling strength and may also have consequences for water mass characteristics in the upwelling region. An increased contribution of Agulhas water to the upwelling water masses will import more preformed nutrients and oxygen into the upwelling region.

Description: Accurate assessment of anthropogenic carbon dioxide (CO2) emissions and their redistribution among the atmosphere, ocean, and terrestrial biosphere – the “global carbon budget” – is important to better understand the global carbon cycle, support the development of climate policies, and project future climate change. Here we describe data sets and methodology to quantify the five major components of the global carbon budget and their uncertainties. Fossil CO2 emissions (EFF) are based on energy statistics and cement production data, while emissions from land use change (ELUC), mainly deforestation, are based on land use and land use change data and bookkeeping models. Atmospheric CO2 concentration is measured directly and its growth rate (GATM) is computed from the annual changes in concentration. The ocean CO2 sink (SOCEAN) and terrestrial CO2 sink (SLAND) are estimated with global process models constrained by observations. The resulting carbon budget imbalance (BIM), the difference between the estimated total emissions and the estimated changes in the atmosphere, ocean, and terrestrial biosphere, is a measure of imperfect data and understanding of the contemporary carbon cycle. All uncertainties are reported as ±1σ. For the last decade available (2009–2018), EFF was 9.5±0.5 GtC yr−1, ELUC 1.5±0.7 GtC yr−1, GATM 4.9±0.02 GtC yr−1 (2.3±0.01 ppm yr−1), SOCEAN 2.5±0.6 GtC yr−1, and SLAND 3.2±0.6 GtC yr−1, with a budget imbalance BIM of 0.4 GtC yr−1 indicating overestimated emissions and/or underestimated sinks. For the year 2018 alone, the growth in EFF was about 2.1 % and fossil emissions increased to 10.0±0.5 GtC yr−1, reaching 10 GtC yr−1 for the first time in history, ELUC was 1.5±0.7 GtC yr−1, for total anthropogenic CO2 emissions of 11.5±0.9 GtC yr−1 (42.5±3.3 GtCO2). Also for 2018, GATM was 5.1±0.2 GtC yr−1 (2.4±0.1 ppm yr−1), SOCEAN was 2.6±0.6 GtC yr−1, and SLAND was 3.5±0.7 GtC yr−1, with a BIM of 0.3 GtC. The global atmospheric CO2 concentration reached 407.38±0.1 ppm averaged over 2018. For 2019, preliminary data for the first 6–10 months indicate a reduced growth in EFF of +0.6 % (range of −0.2 % to 1.5 %) based on national emissions projections for China, the USA, the EU, and India and projections of gross domestic product corrected for recent changes in the carbon intensity of the economy for the rest of the world. Overall, the mean and trend in the five components of the global carbon budget are consistently estimated over the period 1959–2018, but discrepancies of up to 1 GtC yr−1 persist for the representation of semi-decadal variability in CO2 fluxes. A detailed comparison among individual estimates and the introduction of a broad range of observations shows (1) no consensus in the mean and trend in land use change emissions over the last decade, (2) a persistent low agreement between the different methods on the magnitude of the land CO2 flux in the northern extra-tropics, and (3) an apparent underestimation of the CO2 variability by ocean models outside the tropics. This living data update documents changes in the methods and data sets used in this new global carbon budget and the progress in understanding of the global carbon cycle compared with previous publications of this data set (Le Quéré et al., 2018a, b, 2016, 2015a, b, 2014, 2013). The data generated by this work are available at https://doi.org/10.18160/gcp-2019 (Friedlingstein et al., 2019).

Description: The ice–substrate interface is an important boundary condition for ice sheet modelling. The substrate affects the ice sheet by allowing sliding through sediment deformation and accommodating the storage and drainage of subglacial water. We present three datasets on a 1 : 5 000 000 scale with different geological parameters for the region that was covered by the ice sheets in North America, including Greenland and Iceland. The first dataset includes the distribution of surficial sediments, which is separated into continuous, discontinuous and predominantly rock categories. The second dataset includes sediment grain size properties, which is divided into three classes: clay, silt and sand, based on the dominant grain size of the fine fraction of the glacial sediments. The third dataset is the generalized bedrock geology. We demonstrate the utility of these datasets for governing ice sheet dynamics by using an ice sheet model with a simulation that extends through the last glacial cycle. In order to demonstrate the importance of the basal boundary conditions for ice sheet modelling, we changed the shear friction angle to account for a weaker substrate and found changes up to 40 % in ice thickness compared to a reference run. Although incorporation of the ice–bed boundary remains model dependent, our dataset provides an observational baseline for improving a critical weakness in current ice sheet modelling (https://doi.org/10.1594/PANGAEA.895889, Gowan et al., 2018b).

Description: Enclosed topographic depressions are characteristic of karst landscapes on Earth. The developmental relationship between depression types, such as sinkholes (dolines) and uvalas, has been the subject of debate, mainly because the long developmental timescales in classical limestone karst settings impede direct observation. Here we characterize the morphometric properties and spatio-temporal development of ∼1150 sinkholes and five uvalas formed from ∼1980 to 2017 in an evaporite karst setting along the eastern coast of the hypersaline Dead Sea (at Ghor Al-Haditha, Jordan). The development of sinkhole populations and individual uvalas is intertwined in terms of onset, evolution and cessation. The sinkholes commonly develop in clusters, within which they may coalesce to form compound or nested sinkholes. In general, however, the uvalas are not defined by coalescence of sinkholes. Although each uvala usually encloses several clusters of sinkholes, it develops as a larger-scale, gentler and structurally distinct depression. The location of new sinkholes and uvalas shows a marked shoreline-parallel migration with time, followed by a marked shoreline-perpendicular (i.e. seaward) growth with time. These observations are consistent with theoretical predictions of karstification controlled by a laterally migrating interface between saturated and undersaturated groundwater, as induced by the 35 m fall in the Dead Sea water level since 1967. More generally, our observations indicate that uvalas and the sinkhole populations within them, although morphometrically distinct, can develop near-synchronously by subsidence in response to subsurface erosion.

Description: Proxy records from climate archives provide evidence about past climate changes, but the recorded signal is affected by non-climate-related effects as well as time uncertainty. As proxy-based climate reconstructions are frequently used to test climate models and to quantitatively infer past climate, we need to improve our understanding of the proxy record signal content as well as the uncertainties involved. In this study, we empirically estimate signal-to-noise ratios (SNRs) of temperature proxy records used in global compilations of the middle to late Holocene (last 6000 years). This is achieved through a comparison of the correlation of proxy time series from nearby sites of three compilations and model time series extracted at the proxy sites from two transient climate model simulations: a Holocene simulation of the ECHAM5/MPI-OM model and the Holocene part of the TraCE-21ka simulation. In all comparisons, we found the mean correlations of the proxy time series on centennial to millennial timescales to be low (R〈0.2), even for nearby sites, which resulted in low SNR estimates. The estimated SNRs depend on the assumed time uncertainty of the proxy records, the timescale analysed, and the model simulation used. Using the spatial correlation structure of the ECHAM5/MPI-OM simulation, the estimated SNRs on centennial timescales ranged from 0.05 – assuming no time uncertainty – to 0.5 for a time uncertainty of 400 years. On millennial timescales, the estimated SNRs were generally higher. Use of the TraCE-21ka correlation structure generally resulted in lower SNR estimates than for ECHAM5/MPI-OM. As the number of available high-resolution proxy records continues to grow, a more detailed analysis of the signal content of specific proxy types should become feasible in the near future. The estimated low signal content of Holocene temperature compilations should caution against over-interpretation of these multi-proxy and multisite syntheses until further studies are able to facilitate a better characterisation of the signal content in paleoclimate records.

Description: Upwelling systems play a key role in the global carbon and nitrogen cycles and are also of local relevance due to their high productivity and fish resources. To capture and understand the high spatial and temporal variability in physical and biogeochemical parameters found in these regions, novel measurement techniques have to be combined in an interdisciplinary manner. Here we use high-resolution glider-based physical–biogeochemical observations in combination with ship-based underwater vision profiler, sensor and bottle data to investigate the drivers of oxygen and nitrate variability across the shelf break off Mauritania in June 2014. Distinct oxygen and nitrate variability shows up in our glider data. High-oxygen and low-nitrate anomalies were clearly related to water mass variability and probably linked to ocean transport. Low-oxygen and high-nitrate patches co-occurred with enhanced turbidity signals close to the seabed, which suggests locally high microbial respiration rates of resuspended organic matter near the sea floor. This interpretation is supported by high particle abundance observed by the underwater vision profiler and enhanced particle-based respiration rate estimates close to the seabed. Discrete in situ measurements of dissolved organic carbon and amino acids suggest the formation of dissolved organic carbon due to particle dissolution near the seabed fueling additional microbial respiration. During June an increase in the oxygen concentration on the shelf break of about 15 µmol kg−1 was observed. These changes go along with meridional circulation changes but cannot be explained by typical water mass property changes. Thus our high-resolution interdisciplinary observations highlight the complex interplay of remote and local physical–biogeochemical drivers of oxygen and nitrate variability off Mauritania, which cannot be captured by classical shipboard observations alone.

Description: Particle sinking is a major form of transport for photosynthetically fixed carbon to below the euphotic zone via the biological carbon pump (BCP). Oxygen (O2) depletion may improve the efficiency of the BCP. However, the mechanisms by which O2 deficiency can enhance particulate organic matter (POM) vertical fluxes are not well understood. Here, we investigate the composition and vertical fluxes of POM in two deep basins of the Baltic Sea (GB: Gotland Basin and LD: Landsort Deep). The two basins showed different O2 regimes resulting from the intrusion of oxygen-rich water from the North Sea that ventilated the water column below 140 m in GB, but not in LD, during the time of sampling. In June 2015, we deployed surface-tethered drifting sediment traps in oxic surface waters (GB: 40 and 60 m; LD: 40 and 55 m), within the oxygen minimum zone (OMZ; GB: 110 m and LD: 110 and 180 m) and at recently oxygenated waters by the North Sea inflow in GB (180 m). The primary objective of this study was to test the hypothesis that the different O2 conditions in the water column of GB and LD affected the composition and vertical flux of sinking particles and caused differences in export efficiency between those two basins. The composition and vertical flux of sinking particles were different in GB and LD. In GB, particulate organic carbon (POC) flux was 18 % lower in the shallowest trap (40 m) than in the deepest sediment trap (at 180 m). Particulate nitrogen (PN) and Coomassie stainable particle (CSP) fluxes decreased with depth, while particulate organic phosphorus (POP), biogenic silicate (BSi), chlorophyll a (Chl a) and transparent exopolymeric particle (TEP) fluxes peaked within the core of the OMZ (110 m); this coincided with the presence of manganese oxide-like (MnOx-like) particles aggregated with organic matter. In LD, vertical fluxes of POC, PN and CSPs decreased by 28 %, 42 % and 56 %, respectively, from the surface to deep waters. POP, BSi and TEP fluxes did not decrease continuously with depth, but they were higher at 110 m. Although we observe a higher vertical flux of POP, BSi and TEPs coinciding with abundant MnOx-like particles at 110 m in both basins, the peak in the vertical flux of POM and MnOx-like particles was much higher in GB than in LD. Sinking particles were remarkably enriched in BSi, indicating that diatoms were preferentially included in sinking aggregates and/or there was an inclusion of lithogenic Si (scavenged into sinking particles) in our analysis. During this study, the POC transfer efficiency (POC flux at 180 m over 40 m) was higher in GB (115 %) than in LD (69 %), suggesting that under anoxic conditions a smaller portion of the POC exported below the euphotic zone was transferred to 180 m than under reoxygenated conditions present in GB. In addition, the vertical fluxes of MnOx-like particles were 2 orders of magnitude higher in GB than LD. Our results suggest that POM aggregates with MnOx-like particles formed after the inflow of oxygen-rich water into GB, and the formation of those MnOx–OM-rich particles may alter the composition and vertical flux of POM, potentially contributing to a higher transfer efficiency of POC in GB. This idea is consistent with observations of fresher and less degraded organic matter in deep waters of GB than LD.

Description: Surface melting is a major driver of Greenland's mass loss. Yet, the mechanisms that trigger melt are still insufficiently understood because seasonally based studies blend processes initiating melt with positive feedbacks. Here, we focus on the triggers of melt by examining the synoptic atmospheric conditions associated with 313 rapid melt increases, detected in a satellite-derived melt extent product, equally distributed throughout the year over the period 1979–2012. By combining reanalysis and weather station data, we show that melt is initiated by a cyclone-driven, southerly flow of warm, moist air, which gives rise to large-scale precipitation. A decomposition of the synoptic atmospheric variability over Greenland suggests that the identified, melt-triggering weather pattern accounts for ∼40 % of the net precipitation, but increases in the frequency, duration and areal extent of the initiated melting have shifted the line between mass gain and mass loss as more melt and rainwater run off or accumulate in the snowpack. Using a regional climate model, we estimate that the initiated melting more than doubled over the investigated period, amounting to ∼28 % of the overall surface melt and revealing that, despite the involved mass gain, year-round precipitation events are participating in the ice sheet's decline.

Description: We present consistent annual mean atmospheric histories and growth rates for the mainly anthropogenic halogenated compounds HCFC-22, HCFC-141b, HCFC-142b, HFC-134a, HFC-125, HFC-23, PFC-14 and PFC-116, which are all potentially useful oceanic transient tracers (tracers of water transport within the ocean), for the Northern and Southern Hemisphere with the aim of providing input histories of these compounds for the equilibrium between the atmosphere and surface ocean. We use observations of these halogenated compounds made by the Advanced Global Atmospheric Gases Experiment (AGAGE), the Scripps Institution of Oceanography (SIO), the Commonwealth Scientific and Industrial Research Organization (CSIRO), the National Oceanic and Atmospheric Administration (NOAA) and the University of East Anglia (UEA). Prior to the direct observational record, we use archived air measurements, firn air measurements and published model calculations to estimate the atmospheric mole fraction histories. The results show that the atmospheric mole fractions for each species, except HCFC-141b and HCFC-142b, have been increasing since they were initially produced. Recently, the atmospheric growth rates have been decreasing for the HCFCs (HCFC-22, HCFC-141b and HCFC-142b), increasing for the HFCs (HFC-134a, HFC-125, HFC-23) and stable with little fluctuation for the PFCs (PFC-14 and PFC-116) investigated here. The atmospheric histories (source functions) and natural background mole fractions show that HCFC-22, HCFC-141b, HCFC-142b, HFC-134a, HFC-125 and HFC-23 have the potential to be oceanic transient tracers for the next few decades only because of the recently imposed bans on production and consumption. When the atmospheric histories of the compounds are not monotonically changing, the equilibrium atmospheric mole fraction (and ultimately the age associated with that mole fraction) calculated from their concentration in the ocean is not unique, reducing their potential as transient tracers. Moreover, HFCs have potential to be oceanic transient tracers for a longer period in the future than HCFCs as the growth rates of HFCs are increasing and those of HCFCs are decreasing in the background atmosphere. PFC-14 and PFC-116, however, have the potential to be tracers for longer periods into the future due to their extremely long lifetimes, steady atmospheric growth rates and no explicit ban on their emissions. In this work, we also derive solubility functions for HCFC-22, HCFC-141b, HCFC-142b, HFC-134a, HFC-125, HFC-23, PFC-14 and PFC-116 in water and seawater to facilitate their use as oceanic transient tracers. These functions are based on the Clark–Glew–Weiss (CGW) water solubility function fit and salting-out coefficients estimated by the poly-parameter linear free-energy relationships (pp-LFERs). Here we also provide three methods of seawater solubility estimation for more compounds. Even though our intention is for application in oceanic research, the work described in this paper is potentially useful for tracer studies in a wide range of natural waters, including freshwater and saline lakes, and, for the more stable compounds, groundwaters.

Description: We present Nemo-Nordic, a Baltic and North Sea model based on the NEMO ocean engine. Surrounded by highly industrialized countries, the Baltic and North seas and their assets associated with shipping, fishing and tourism are vulnerable to anthropogenic pressure and climate change. Ocean models providing reliable forecasts and enabling climatic studies are important tools for the shipping infrastructure and to get a better understanding of the effects of climate change on the marine ecosystems. Nemo-Nordic is intended to be a tool for both short-term and long-term simulations and to be used for ocean forecasting as well as process and climatic studies. Here, the scientific and technical choices within Nemo-Nordic are introduced, and the reasons behind the design of the model and its domain and the inclusion of the two seas are explained. The model's ability to represent barotropic and baroclinic dynamics, as well as the vertical structure of the water column, is presented. Biases are shown and discussed. The short-term capabilities of the model are presented, especially its capabilities to represent sea level on an hourly timescale with a high degree of accuracy. We also show that the model can represent longer timescales, with a focus on the major Baltic inflows and the variability in deep-water salinity in the Baltic Sea.

Description: Thriving benthic communities were observed in the oxygen minimum zones along the southwestern African margin. On the Namibian margin, fossil cold-water coral mounds were overgrown by sponges and bryozoans, while the Angolan margin was characterized by cold-water coral mounds covered by a living coral reef. To explore why benthic communities differ in both areas, present-day environmental conditions were assessed, using conductivity–temperature–depth (CTD) transects and bottom landers to investigate spatial and temporal variations of environmental properties. Near-bottom measurements recorded low dissolved oxygen concentrations on the Namibian margin of 0–0.15 mL L−1 (≜0 %–9 % saturation) and on the Angolan margin of 0.5–1.5 mL L−1 (≜7 %–18 % saturation), which were associated with relatively high temperatures (11.8–13.2 ∘C and 6.4–12.6 ∘C, respectively). Semidiurnal barotropic tides were found to interact with the margin topography producing internal waves. These tidal movements deliver water with more suitable characteristics to the benthic communities from below and above the zone of low oxygen. Concurrently, the delivery of a high quantity and quality of organic matter was observed, being an important food source for the benthic fauna. On the Namibian margin, organic matter originated directly from the surface productive zone, whereas on the Angolan margin the geochemical signature of organic matter suggested an additional mechanism of food supply. A nepheloid layer observed above the cold-water corals may constitute a reservoir of organic matter, facilitating a constant supply of food particles by tidal mixing. Our data suggest that the benthic fauna on the Namibian margin, as well as the cold-water coral communities on the Angolan margin, may compensate for unfavorable conditions of low oxygen levels and high temperatures with enhanced availability of food, while anoxic conditions on the Namibian margin are at present a limiting factor for cold-water coral growth. This study provides an example of how benthic ecosystems cope with such extreme environmental conditions since it is expected that oxygen minimum zones will expand in the future due to anthropogenic activities.

Description: The aim of the GEOVIDE cruise (May–June 2014, R/V Pourquoi Pas?) was to provide a better understanding of trace metal biogeochemical cycles in the North Atlantic Ocean. As marine particles play a key role in the global biogeochemical cycle of trace elements in the ocean, we discuss the distribution of particulate iron (PFe), in relation to the distribution of particulate aluminium (PAl), manganese (PMn), and phosphorus (PP). Overall, 32 full vertical profiles were collected for trace metal analyses, representing more than 500 samples. This resolution provides a solid basis for assessing concentration distributions, elemental ratios, size fractionation, and adsorptive scavenging processes in key areas of the thermohaline overturning circulation. Total particulate iron concentrations ranged from as low as 9 pmol L−1 in surface waters of the Labrador Sea to 304 nmol L−1 near the Iberian margin, while median PFe concentrations of 1.15 nmol L−1 were measured over the sub-euphotic ocean interior. Within the Iberian Abyssal Plain, the ratio of PFe to PAl was identical to the continental crust molar ratio (0.21 mol mol−1), indicating the important influence of crustal particles in the water column. Overall, the lithogenic component explained more than 87% of PFe variance along the section. Within the Irminger and Labrador basins, the formation of biogenic particles led to an increase in the PFe∕PAl ratio (up to 0.64 mol mol−1) compared to the continental crust ratio. Continental margins induce high concentrations of particulate trace elements within the surrounding water masses (up to 10 nmol L−1 of PFe). For example, horizontal advection of PFe was visible more than 250 km away from the Iberian margin. Additionally, several benthic nepheloid layers were observed more than 200 m above the seafloor along the transect, especially in the Icelandic, Irminger, and Labrador basins, suspending particles with high PFe content of up to 89 nmol L−1.

Description: This study introduces the Monash Simple Climate Model (MSCM) experiment database. The simulations are based on the Globally Resolved Energy Balance (GREB) model to study three different aspects of climate model simulations: (1) understanding processes that control the mean climate, (2) the response of the climate to a doubling of the CO2 concentration, and (3) scenarios of external forcing (CO2 concentration and solar radiation). A series of sensitivity experiments in which elements of the climate system are turned off in various combinations are used to address (1) and (2). This database currently provides more than 1300 experiments and has an online web interface for fast analysis and free access to the data. We briefly outline the design of all experiments, give a discussion of some results, put the findings into the context of previously published results from similar experiments, discuss the quality and limitations of the MSCM experiments, and also give an outlook on possible further developments. The GREB model simulation is quite realistic, but the model without flux corrections has a root mean square error in the mean state of the surface temperature of about 10 ∘C, which is larger than those of general circulation models (2 ∘C). It needs to be noted here that the GREB model does not simulate circulation changes or changes in cloud cover (feedbacks). However, the MSCM experiments show good agreement to previously published studies. Although GREB is a very simple model, it delivers good first-order estimates, is very fast, highly accessible, and can be used to quickly try many different sensitivity experiments or scenarios. It builds a basis on which conceptual ideas can be tested to first order and it provides a null hypothesis for understanding complex climate interactions in the context of response to external forcing or interactions in the climate subsystems.

Description: River water is the main source of dissolved organic carbon (DOC) in the Arctic Ocean. DOC plays an important role in the Arctic carbon cycle, and its export from land to sea is expected to increase as ongoing climate change accelerates permafrost thaw. However, transport pathways and transformation of DOC in the land-to-ocean transition are mostly unknown. We collected DOC and aCDOM(λ) samples from 11 expeditions to river, coastal and offshore waters and present a new DOC–aCDOM(λ) model for the fluvial–marine transition zone in the Laptev Sea. The aCDOM(λ) characteristics revealed that the dissolved organic matter (DOM) in samples of this dataset are primarily of terrigenous origin. Observed changes in aCDOM(443) and its spectral slopes indicate that DOM is modified by microbial and photo-degradation. Ocean colour remote sensing (OCRS) provides the absorption coefficient of coloured dissolved organic matter (aCDOM(λ)sat) at λ=440 or 443 nm, which can be used to estimate DOC concentration at high temporal and spatial resolution over large regions. We tested the statistical performance of five OCRS algorithms and evaluated the plausibility of the spatial distribution of derived aCDOM(λ)sat. The OLCI (Sentinel-3 Ocean and Land Colour Instrument) neural network swarm (ONNS) algorithm showed the best performance compared to in situ aCDOM(440) (r2=0.72). Additionally, we found ONNS-derived aCDOM(440), in contrast to other algorithms, to be partly independent of sediment concentration, making ONNS the most suitable aCDOM(λ)sat algorithm for the Laptev Sea region. The DOC–aCDOM(λ) model was applied to ONNS-derived aCDOM(440), and retrieved DOC concentration maps showed moderate agreement to in situ data (r2=0.53). The in situ and satellite-retrieved data were offset by up to several days, which may partly explain the weak correlation for this dynamic region. Satellite-derived surface water DOC concentration maps from Medium Resolution Imaging Spectrometer (MERIS) satellite data demonstrate rapid removal of DOC within short time periods in coastal waters of the Laptev Sea, which is likely caused by physical mixing and different types of degradation processes. Using samples from all occurring water types leads to a more robust DOC–aCDOM(λ) model for the retrievals of DOC in Arctic shelf and river waters.

Description: There is a need for cost-efficient tools to explore deep-ocean ecosystems to collect baseline biological observations on pelagic fauna (zooplankton and nekton) and establish the vertical ecological zonation in the deep sea. The Pelagic In situ Observation System (PELAGIOS) is a 3000 m rated slowly (0.5 m s−1) towed camera system with LED illumination, an integrated oceanographic sensor set (CTD-O2) and telemetry allowing for online data acquisition and video inspection (low definition). The high-definition video is stored on the camera and later annotated using software and related to concomitantly recorded environmental data. The PELAGIOS is particularly suitable for open-ocean observations of gelatinous fauna, which is notoriously under-sampled by nets and/or destroyed by fixatives. In addition to counts, diversity, and distribution data as a function of depth and environmental conditions (T, S, O2), in situ observations of behavior, orientation, and species interactions are collected. Here, we present an overview of the technical setup of the PELAGIOS as well as example observations and analyses from the eastern tropical North Atlantic. Comparisons to data from the Multiple Opening/Closing Net and Environmental Sensing System (MOCNESS) net sampling and data from the Underwater Vision Profiler (UVP) are provided and discussed.

Description: Measurements of seismic velocity as a function of depth are generally restricted to borehole locations and are therefore sparse in the world's oceans. Consequently, in the absence of measurements or suitable seismic data, studies requiring knowledge of seismic velocities often obtain these from simple empirical relationships. However, empirically derived velocities may be inaccurate, as they are typically limited to certain geological settings, and other parameters potentially influencing seismic velocities, such as depth to basement, crustal age, or heatflow, are not taken into account. Here, we present a machine learning approach to predict seismic p-wave velocity (vp) as a function of depth (z) for any marine location. Based on a training dataset consisting of vp(z) data from 333 boreholes and 38 geological and spatial predictors obtained from publically available global datasets, a prediction model was created using the Random Forests method. In 60 % of the tested locations, the predicted seismic velocities were superior to those calculated empirically. The results indicate a promising potential for global prediction of vp(z) data, which will allow improving geophysical models in areas lacking first-hand velocity data.

Description: Diatoms account for 40 % of marine primary production and are considered to be key players in the biological carbon pump. Ocean acidification (OA) is expected to affect diatoms primarily by changing the availability of CO2 as a substrate for photosynthesis or through altered ecological interactions within the marine food web. Yet, there is little consensus how entire diatom communities will respond to increasing CO2. To address this question, we synthesized the literature from over a decade of OA-experiments with natural diatom communities to uncover: 1) if and how bulk diatom communities respond to elevated CO2; 2) if shifts within the diatom communities could be expected and how they are expressed with respect to taxonomic affiliation and size structure. We found that diatom communities responded to high CO2 in ~60 % of the experiments and in this case more often positively (56 %) than negatively (32 %; 12 % did not report the direction of change). Shifts among different diatom species were observed in 65 % of the experiments. Our synthesis supports the hypothesis that high CO2 particularly favors larger species as 12 out of 13 experiments which investigated cell size found a shift towards larger species. Unraveling winners and losers with respect to taxonomic affiliation was difficult due to a limited database, but there is evidence that the genus Pseudo-nitzschia could be among the losers. We conclude that OA-induced changes in diatom competitiveness and assemblage structure must be classified as a “risk for ecosystem services” due to the pivotal role diatoms play in trophic transfer and biogeochemical cycles.

Description: Ballast water treatment is required for vessels to prevent the introduction of potentially invasive neobiota. Some treatment methods use chemical disinfectants which produce a variety of halogenated compounds as disinfection by-products (DBPs). One of the most abundant DBP from oxidative ballast water treatment is bromoform (CHBr3) where we find an average concentration of 894±560nmolL-1 (226±142μgL-1) in the undiluted ballast water from measurements and literature. Bromoform is a relevant gas for atmospheric chemistry and ozone depletion, especially in the tropics where entrainment into the stratosphere is possible. The spread of DBPs in the tropics over months to years is assessed here for the first time. With Lagrangian trajectories based on the NEMO-ORCA12 model velocity field, we simulate DBP spread in the sea surface and try to quantify the oceanic bromoform concentration and emission to the atmosphere from ballast water discharge at major harbours in the tropical region of Southeast Asia. The exemplary simulations of two important regions, Singapore and the Pearl River Delta, reveal major transport pathways of the DBPs and the anthropogenic bromoform concentrations in the sea surface. Based on our simulations, we expect DBPs to spread into the open ocean, along the coast and also an advection with monsoon-driven currents into the North Pacific and Indian Ocean. Furthermore, anthropogenic bromoform concentrations and emissions are predicted to increase locally around large harbours. In the sea surface around Singapore we estimate an increase in bromoform concentration by 9% compared to recent measurement. In a moderate scenario where 70% of the ballast water is chemically treated bromoform emissions to the atmosphere can locally exceed 1000pmolm-2h-1 and double climatological emissions. In the Pearl River Delta all bromoform is directly outgassed which leads to an additional bromine (Br) input into the atmosphere of 495kmolBr (∼42tCHBr3) a-1. From Singapore ports the additional atmospheric Br input is calculated as 312kmolBr (∼26tCHBr3) a-1. We estimate the global anthropogenic Br input from ballast water into the atmosphere of up to 13Mmola-1. This is 0.1% global Br input from background bromoform emissions and thus probably not relevant for stratospheric ozone depletion.

Description: Recent observational and modeling studies suggest that stratospheric ozone depletion not only influences the surface climate in the Southern Hemisphere (SH), but also impacts Northern Hemisphere (NH) spring, which implies a strong interaction between dynamics and chemistry. Here, we systematically analyze the importance of interactive chemistry with respect to the representation of stratosphere–troposphere coupling and in particular the effects on NH surface climate during the recent past. We use the interactive and specified chemistry version of NCAR's Whole Atmosphere Community Climate Model coupled to an ocean model to investigate differences in the mean state of the NH stratosphere as well as in stratospheric extreme events, namely sudden stratospheric warmings (SSWs), and their surface impacts. To be able to focus on differences that arise from two-way interactions between chemistry and dynamics in the model, the specified chemistry model version uses a time-evolving, model-consistent ozone field generated by the interactive chemistry model version. We also test the effects of zonally symmetric versus asymmetric prescribed ozone, evaluating the importance of ozone waves in the representation of stratospheric mean state and variability. The interactive chemistry simulation is characterized by a significantly stronger and colder polar night jet (PNJ) during spring when ozone depletion becomes important. We identify a negative feedback between lower stratospheric ozone and atmospheric dynamics during the breakdown of the stratospheric polar vortex in the NH, which contributes to the different characteristics of the PNJ between the simulations. Not only the mean state, but also stratospheric variability is better represented in the interactive chemistry simulation, which shows a more realistic distribution of SSWs as well as a more persistent surface impact afterwards compared with the simulation where the feedback between chemistry and dynamics is switched off. We hypothesize that this is also related to the feedback between ozone and dynamics via the intrusion of ozone-rich air into polar latitudes during SSWs. The results from the zonally asymmetric ozone simulation are closer to the interactive chemistry simulations, implying that under a model-consistent ozone forcing, a three-dimensional (3-D) representation of the prescribed ozone field is desirable. This suggests that a 3-D ozone forcing, as recommended for the upcoming CMIP6 simulations, has the potential to improve the representation of stratospheric dynamics and chemistry. Our findings underline the importance of the representation of interactive chemistry and its feedback on the stratospheric mean state and variability not only in the SH but also in the NH during the recent past.

Description: The Agulhas Current, the western boundary current of the South Indian Ocean, has been shown to play an important role in the connectivity between the Indian and Atlantic oceans. The greater Agulhas Current system is highly dominated by mesoscale dynamics. To investigate their influence on the regional and global circulations, a family of high-resolution ocean general circulation model configurations based on the NEMO code has been developed. Horizontal resolution refinement is achieved by embedding “nests” covering the South Atlantic and the western Indian oceans at 1/10∘ (INALT10) and 1/20∘ (INALT20) within global hosts with coarser resolutions. Nests and hosts are connected through two-way interaction, allowing the nests not only to receive boundary conditions from their respective host but also to feed back the impact of regional dynamics onto the global ocean. A double-nested configuration at 1/60∘ resolution (INALT60) has been developed to gain insights into submesoscale processes within the Agulhas Current system. Large-scale measures such as the Drake Passage transport and the strength of the Atlantic meridional overturning circulation are rather robust among the different configurations, indicating the important role of the hosts in providing a consistent embedment of the regionally refined grids into the global circulation. The dynamics of the Agulhas Current system strongly depend on the representation of mesoscale processes. Both the southward-flowing Agulhas Current and the northward-flowing Agulhas Undercurrent increase in strength with increasing resolution towards more realistic values, which suggests the importance of improving mesoscale dynamics as well as bathymetric slopes along this narrow western boundary current regime. The exploration of numerical choices such as lateral boundary conditions and details of the implementation of surface wind stress forcing demonstrates the range of solutions within any given configuration.

Description: The northward flow of the upper limb of the Atlantic Meridional Overturning Circulation (AMOC) is fed by waters entering the South Atlantic from the Indian Ocean mainly via the Agulhas Current (AC) system and by waters entering from the Pacific through Drake Passage (DP), commonly referred to as the “warm” and “cold” water routes, respectively. However, there is no final consensus on the relative importance of these two routes for the upper limb's volume transport and thermohaline properties. In this study we revisited the AC and DP contributions by performing Lagrangian analyses between the two source regions and the North Brazil Current (NBC) at 6∘ S in a realistically forced high-resolution (1∕20∘) ocean model. Our results agree with the prevailing conception that the AC contribution is the major source for the upper limb transport of the AMOC in the tropical South Atlantic. However, they also suggest a non-negligible DP contribution of around 40 %, which is substantially higher than estimates from previous Lagrangian studies with coarser-resolution models but now better matches estimates from Lagrangian observations. Moreover, idealized analyses of decadal changes in the DP and AC contributions indicate that the ongoing increase in Agulhas leakage indeed may have induced an increase in the AC contribution to the upper limb of the AMOC in the tropics, while the DP contribution decreased. In terms of thermohaline properties, our study highlights the fact that the AC and DP contributions cannot be unambiguously distinguished by their temperature, as the commonly adopted terminology may imply, but rather by their salinity when entering the South Atlantic. During their transit towards the NBC the bulk of DP waters experiences a net density loss through a net warming, whereas the bulk of AC waters experiences a slight net density gain through a net increase in salinity. Notably, these density changes are nearly completely captured by Lagrangian particle trajectories that reach the surface mixed layer at least once during their transit, which amount to 66 % and 49 % for DP and AC waters, respectively. This implies that more than half of the water masses supplying the upper limb of the AMOC are actually formed within the South Atlantic and do not get their characteristic properties in the Pacific and Indian Oceans.

Description: Previous studies have suggested that enhanced weathering and benthic phosphorus (P) fluxes, triggered by climate warming, can increase the oceanic P inventory on millennial timescales, promoting ocean productivity and deoxygenation. In this study, we assessed the major uncertainties in projected P inventories and their imprint on ocean deoxygenation using an Earth system model of intermediate complexity for the same business-as-usual carbon dioxide (CO2) emission scenario until the year 2300 and subsequent linear decline to zero emissions until the year 3000. Our set of model experiments under the same climate scenarios but differing in their biogeochemical P parameterizations suggest a large spread in the simulated oceanic P inventory due to uncertainties in (1) assumptions for weathering parameters, (2) the representation of bathymetry on slopes and shelves in the model bathymetry, (3) the parametrization of benthic P fluxes and (4) the representation of sediment P inventories. Considering the weathering parameters closest to the present day, a limited P reservoir and prescribed anthropogenic P fluxes, we find a +30 % increase in the total global ocean P inventory by the year 5000 relative to pre-industrial levels, caused by global warming. Weathering, benthic and anthropogenic fluxes of P contributed +25 %, +3 % and +2 %, respectively. The total range of oceanic P inventory changes across all model simulations varied between +2 % and +60 %. Suboxic volumes were up to 5 times larger than in a model simulation with a constant oceanic P inventory. Considerably large amounts of the additional P left the ocean surface unused by phytoplankton via physical transport processes as preformed P. In the model, nitrogen fixation was not able to adjust the oceanic nitrogen inventory to the increasing P levels or to compensate for the nitrogen loss due to increased denitrification. This is because low temperatures and iron limitation inhibited the uptake of the extra P and growth by nitrogen fixers in polar and lower-latitude regions. We suggest that uncertainties in P weathering, nitrogen fixation and benthic P feedbacks need to be reduced to achieve more reliable projections of oceanic deoxygenation on millennial timescales.

Description: Nitrous oxide (N2O) and methane (CH4) are atmospheric trace gases which play important roles in the climate and atmospheric chemistry of the Earth. However, little is known about their emissions from rivers and estuaries, which seem to contribute significantly to the atmospheric budget of both gases. To this end concentrations of N2O and CH4 were measured in the Rajang, Maludam, Sebuyau and Simunjan rivers draining peatland in northwestern (NW) Borneo during two campaigns in March and September 2017. The Rajang River was additionally sampled in August 2016 and the Samunsam and Sematan rivers were additionally sampled in March 2017. The Maludam, Sebuyau, and Simunjan rivers are typical “blackwater” rivers with very low pH (3.7–7.8), very high dissolved organic carbon (DOC) concentrations (235–4387 mmol L−1) and very low O2 concentrations (31–246 µmol L−1; i.e. 13 %–116 % O2 saturation). The spatial and temporal variability of N2O and CH4 concentrations (saturations) in the six rivers or estuaries was large and ranged from 2.0 nmol L−1 (28 %) to 41.4 nmol L−1 (570 %) and from 2.5 nmol L−1 (106 %) to 1372 nmol L−1 (57 459 %), respectively. We found no overall trends of N2O with O2 or NO−3, NO−2 or NH+4, and there were no trends of CH4 with O2 or dissolved nutrients or DOC. N2O concentrations showed a positive linear correlation with rainfall. We conclude, therefore, that rainfall is the main factor determining the riverine N2O concentrations since N2O production or consumption in the blackwater rivers themselves seems to be low because of the low pH. CH4 concentrations were highest at salinity = 0 and most probably result from methanogenesis as part of the decomposition of organic matter under anoxic conditions. CH4 in the concentrations in the blackwater rivers showed an inverse relationship with rainfall. We suggest that CH4 oxidation in combination with an enhanced river flow after the rainfall events might be responsible for the decrease in the CH4 concentrations. The rivers and estuaries studied here were an overall net source of N2O and CH4 to the atmosphere. The total annual N2O and CH4 emissions were 1.09 Gg N2O yr−1 (0.7 Gg N yr−1) and 23.8 Gg CH4 yr−1, respectively. This represents about 0.3 %–0.7 % of the global annual riverine and estuarine N2O emissions and about 0.1 %–1 % of the global riverine and estuarine CH4 emissions. Therefore, we conclude that rivers and estuaries in NW Borneo – despite the fact their water area covers only 0.05 % of the global river/estuarine area – contribute significantly to global riverine and estuarine emissions of N2O and CH4.

Description: We investigate the climate mitigation potential and collateral effects of direct injections of captured CO2 into the deep ocean as a possible means to close the gap between an intermediate CO2 emissions scenario and a specific temperature target, such as the 1.5 ∘C target aimed for by the Paris Agreement. For that purpose, a suite of approaches for controlling the amount of direct CO2 injections at 3000 m water depth are implemented in an Earth system model of intermediate complexity. Following the representative concentration pathway RCP4.5, which is a medium mitigation CO2 emissions scenario, cumulative CO2 injections required to meet the 1.5 ∘C climate goal are found to be 390 Gt C by the year 2100 and 1562 Gt C at the end of simulations, by the year 3020. The latter includes a cumulative leakage of 602 Gt C that needs to be reinjected in order to sustain the targeted global mean temperature. CaCO3 sediment and weathering feedbacks reduce the required CO2 injections that comply with the 1.5 ∘C target by about 13 % in 2100 and by about 11 % at the end of the simulation. With respect to the injection-related impacts we find that average pH values in the surface ocean are increased by about 0.13 to 0.18 units, when compared to the control run. In the model, this results in significant increases in potential coral reef habitats, i.e., the volume of the global upper ocean (0 to 130 m depth) with omega aragonite 〉 3.4 and ocean temperatures between 21 and 28 ∘C, compared to the control run. The potential benefits in the upper ocean come at the expense of strongly acidified water masses at depth, with maximum pH reductions of about −2.37 units, relative to preindustrial levels, in the vicinity of the injection sites. Overall, this study demonstrates that massive amounts of CO2 would need to be injected into the deep ocean in order to reach and maintain the 1.5 ∘C climate target in a medium mitigation scenario on a millennium timescale, and that there is a trade-off between injection-related reductions in atmospheric CO2 levels accompanied by reduced upper-ocean acidification and adverse effects on deep-ocean chemistry, particularly near the injection sites.

Description: The availability of the micronutrient iron (Fe) in surface waters determines primary production, N2 fixation, and microbial community structure in large parts of the world's ocean, and thus it plays an important role in ocean carbon and nitrogen cycles. Eastern boundary upwelling systems and the connected oxygen minimum zones (OMZs) are typically associated with elevated concentrations of redox-sensitive trace metals (e.g., Fe, manganese (Mn), and cobalt (Co)), with shelf sediments typically forming a key source. Over the last 5 decades, an expansion and intensification of OMZs has been observed and this trend is likely to proceed. However, it is unclear how trace-metal (TM) distributions and transport are influenced by decreasing oxygen (O2) concentrations. Here we present dissolved (d; 〈0.2 µm) and leachable particulate (Lp; 〉0.2 µm) TM data collected at seven stations along a 50 km transect in the Mauritanian shelf region. We observed enhanced concentrations of Fe, Co, and Mn corresponding with low O2 concentrations (〈50 µmol kg−1), which were decoupled from major nutrients and nutrient-like and scavenged TMs (cadmium (Cd), lead (Pb), nickel (Ni), and copper (Cu)). Additionally, data from repeated station occupations indicated a direct link between dissolved and leachable particulate Fe, Co, Mn, and O2. An observed dFe (dissolved iron) decrease from 10 to 5 nmol L−1 coincided with an O2 increase from 30 to 50 µmol kg−1 and with a concomitant decrease in turbidity. The changes in Fe (Co and Mn) were likely driven by variations in their release from sediment pore water, facilitated by lower O2 concentrations and longer residence time of the water mass on the shelf. Variations in organic matter remineralization and lithogenic inputs (atmospheric deposition or sediment resuspension; assessed using Al as indicator for lithogenic inputs) only played a minor role in redox-sensitive TM variability. Vertical dFe fluxes from O2-depleted subsurface-to-surface waters (0.08–13.5 µmol m−2 d−1) driven by turbulent mixing and vertical advection were an order of magnitude larger than atmospheric deposition fluxes (0.63–1.43 µmol m−2 d−1; estimated using dAl inventories in the surface mixed layer) in the continental slope and shelf region. Benthic fluxes are therefore the dominant dFe supply to surface waters on the continental margins of the Mauritanian upwelling region. Overall, our results indicated that the projected future decrease in O2 concentrations in OMZs may result in increases in Fe, Mn, and Co concentrations.

Description: The state of a population of planktic foraminifers at a certain time reflects multiple processes in the upper ocean, including environmental conditions to which the population was exposed during its growth, the age of the cohorts, and spatiotemporal patchiness. We carried out depth-stratified (0–60, 60–100m) replicated sampling off Puerto Rico in autumn 2012, revisiting three stations previously sampled in autumn 1994 and spring 1995, in order to analyze seasonal and interannual variability of planktic foraminifers and the stable isotopic composition of their tests. The merged dataset from all three sampling campaigns allows us to assess short- and long-term changes in foraminiferal population dynamics and the spatial assemblage coherency along the shelf edge. All three sample series cover more than 2 weeks during either spring (1995) or autumn (1994, 2012) and include the time of the full moon when reproduction of some surface-dwelling planktic foraminifers has been postulated to take place. Our analyses indicate that interannual variability affected the faunal composition,andbothautumnassemblageswerecharacterizedbyoligotrophictropicalspecies,dominatedbyTrilobatus sacculifer and Globigerinoides ruber (white and pink variety). However, G. ruber (white) had a higher abundance in 1994 (37%) than in 2012 (3.5%), which may be partially due to increasing sea surface temperatures sincethe1990s.Between60and100mwaterdepth,adifferentfaunalcompositionwithaspecificstableoxygen isotope signature provides evidence for the presence of the Subtropical Underwater at the sampling site. MeasurementsonT.sacculifersampledinautumn2012revealedthattestsize,calcificationandincidenceofsac-like chamberscontinuedtoincreaseafterfullmoon,andthusnorelationtothesynodiclunarreproductioncyclewas recognized.Duringautumn2012,outerbandsofhurricaneSandypassedtheGreaterAntillesandlikelyaffected the foraminifers. Lower standing stocks of living planktic foraminifers and lower stable carbon isotope values from individuals collected in the mixed layer likely indicate the response to increased rainfall and turbidity in the wake of the hurricane.

Description: Nitrous oxide (N2O) is a potent greenhouse gas, and it is involved in stratospheric ozone depletion. Its oceanic production is mainly influenced by dissolved nutrient and oxygen (O2) concentrations in the water column. Here we examined the seasonal and annual variations in dissolved N2O at the Boknis Eck (BE) Time Series Station located in Eckernförde Bay (southwestern Baltic Sea). Monthly measurements of N2O started in July 2005. We found a pronounced seasonal pattern for N2O with high concentrations (supersaturations) in winter and early spring and low concentrations (undersaturations) in autumn when hypoxic or anoxic conditions prevail. Unusually low N2O concentrations were observed during October 2016–April 2017, which was presumably a result of prolonged anoxia and the subsequent nutrient deficiency. Unusually high N2O concentrations were found in November 2017 and this event was linked to the occurrence of upwelling which interrupted N2O consumption via denitrification and potentially promoted ammonium oxidation (nitrification) at the oxic–anoxic interface. Nutrient concentrations (such as nitrate, nitrite and phosphate) at BE have been decreasing since the 1980s, but oxygen concentrations in the water column are still decreasing. Our results indicate a close coupling of N2O anomalies to O2 concentration, nutrients, and stratification. Given the long-term trends of declining nutrient and oxygen concentrations at BE, a decrease in N2O concentration, and thus emissions, seems likely due to an increasing number of events with low N2O concentrations.

Description: It is an open question how localized elevated emissions of bromoform (CHBr3) and other very short-lived halocarbons (VSLHs), found in coastal and upwelling regions, and low background emissions, typically found over the open ocean, impact the atmospheric VSLH distribution. In this study, we use the Lagrangian dispersion model FLEXPART to simulate atmospheric CHBr3 resulting from assumed uniform background emissions, and from elevated emissions consistent with those derived during three tropical cruise campaigns. The simulations demonstrate that the atmospheric CHBr3 distributions in the uniform background emissions scenario are highly variable with high mixing ratios appearing in regions of convergence or low wind speed. This relation holds on regional and global scales. The impact of localized elevated emissions on the atmospheric CHBr3 distribution varies significantly from campaign to campaign. The estimated impact depends on the strength of the emissions and the meteorological conditions. In the open waters of the western Pacific and Indian oceans, localized elevated emissions only slightly increase the background concentrations of atmospheric CHBr3, even when 1∘ wide source regions along the cruise tracks are assumed. Near the coast, elevated emissions, including hot spots up to 100 times larger than the uniform background emissions, can be strong enough to be distinguished from the atmospheric background. However, it is not necessarily the highest hot spot emission that produces the largest enhancement, since the tug-of-war between fast advective transport and local accumulation at the time of emission is also important. Our results demonstrate that transport variations in the atmosphere itself are sufficient to produce highly variable VSLH distributions, and elevated VSLHs in the atmosphere do not always reflect a strong localized source. Localized elevated emissions can be obliterated by the highly variable atmospheric background, even if they are orders of magnitude larger than the average open ocean emissions.

Description: Oceanic emissions of the climate-relevant trace gases carbonyl sulfide (OCS) and carbon disulfide (CS2) are a major source to their atmospheric budget. Their current and future emission estimates are still uncertain due to incomplete process understanding and therefore inexact quantification across different biogeochemical regimes. Here we present the first concurrent measurements of both gases together with related fractions of the dissolved organic matter (DOM) pool, i.e., solid-phase extractable dissolved organic sulfur (DOSSPE, n=24, 0.16±0.04 µmol L−1), chromophoric (CDOM, n=76, 0.152±0.03), and fluorescent dissolved organic matter (FDOM, n=35), from the Peruvian upwelling region (Guayaquil, Ecuador to Antofagasta, Chile, October 2015). OCS was measured continuously with an equilibrator connected to an off-axis integrated cavity output spectrometer at the surface (29.8±19.8 pmol L−1) and at four profiles ranging down to 136 m. CS2 was measured at the surface (n=143, 17.8±9.0 pmol L−1) and below, ranging down to 1000 m (24 profiles). These observations were used to estimate in situ production rates and identify their drivers. We find different limiting factors of marine photoproduction: while OCS production is limited by the humic-like DOM fraction that can act as a photosensitizer, high CS2 production coincides with high DOSSPE concentration. Quantifying OCS photoproduction using a specific humic-like FDOM component as proxy, together with an updated parameterization for dark production, improves agreement with observations in a 1-D biogeochemical model. Our results will help to better predict oceanic concentrations and emissions of both gases on regional and, potentially, global scales.

Description: Particle aggregation determines the particle flux length scale and affects the marine oxygen concentration and thus the volume of oxygen minimum zones (OMZs) that are of special relevance for ocean nutrient cycles and marine ecosystems and that have been found to expand faster than can be explained by current state-of-the-art models. To investigate the impact of particle aggregation on global model performance, we carried out a sensitivity study with different parameterisations of marine aggregates and two different model resolutions. Model performance was investigated with respect to global nutrient and oxygen concentrations, as well as extent and location of OMZs. Results show that including an aggregation model improves the representation of OMZs. Moreover, we found that besides a fine spatial resolution of the model grid, the consideration of porous particles, an intermediate-to-high particle sinking speed and a moderate-to-high stickiness improve the model fit to both global distributions of dissolved inorganic tracers and regional patterns of OMZs, compared to a model without aggregation. Our model results therefore suggest that improvements not only in the model physics but also in the description of particle aggregation processes can play a substantial role in improving the representation of dissolved inorganic tracers and OMZs on a global scale. However, dissolved inorganic tracers are apparently not sufficient for a global model calibration, which could necessitate global model calibration against a global observational dataset of marine organic particles.

Description: We present the first forcing interpretation of the future anthropogenic aerosol scenarios of CMIP6 with the simple plumes parameterisation MACv2-SP. The nine scenarios for 2015 to 2100 are based on anthropogenic aerosol emissions for use in CMIP6 (Riahi et al., 2017; Gidden et al., 2018). We use the emissions to scale the observationally informed anthropogenic aerosol optical properties and the associated effect on the cloud albedo of present-day (Fiedler et al., 2017; Stevens et al., 2017) into the future. The resulting scenarios in MACv2-SP are then ranked according to their strength in forcing magnitude and spatial asymmetries for anthropogenic aerosol. All scenarios, except SSP3-70 and SSP4-60, show a decrease in anthropogenic aerosol by 2100 with a range from 108 % to 36 % of the anthropogenic aerosol optical depth in 2015. We estimate the radiative forcing of anthropogenic aerosol from high- and low-end scenarios in the mid-2090s by performing ensembles of simulations with the atmosphere-only configuration of MPI-ESM1.2. MACv2-SP translates the CMIP6 emission scenarios for inducing anthropogenic aerosol forcing. With the implementation in our model, we obtain forcing estimates for both the shortwave instantaneous radiative forcing (RF) and the effective radiative forcing (ERF) of anthropogenic aerosol relative to 1850. Here, ERF accounts for rapid atmospheric adjustments and natural variability internal to the model. The ERF of anthropogenic aerosol for the mid-2090s ranges from −0.15 W m−2 for SSP1-19 to −0.54 W m−2 for SSP3-70, i.e. the mid-2090s ERF is 30 %–108 % of the value in the mid-2000s due to differences in the emission pathway alone. Assuming a stronger Twomey effect changes these ERFs to −0.39 and −0.92 W m−2, respectively, which are similar to estimates obtained from models with complex aerosol parameterisations. The year-to-year standard deviations around 0.3 W m−2 associated with natural variability highlight the necessity to average over sufficiently long time periods for estimating ERF; this is in contrast to RF that is typically well constrained after simulating just 1 year. The scenario interpretation of MACv2-SP will be used within the framework of CMIP6 and other cutting-edge scientific endeavours.

Description: This study assesses the change in anthropogenic aerosol forcing from the mid-1970s to the mid-2000s. Both decades had similar global-mean anthropogenic aerosol optical depths but substantially different global distributions. For both years, we quantify (i) the forcing spread due to model-internal variability and (ii) the forcing spread among models. Our assessment is based on new ensembles of atmosphere-only simulations with five state-of-the-art Earth system models. Four of these models will be used in the sixth Coupled Model Intercomparison Project (CMIP6; Eyring et al., 2016). Here, the complexity of the anthropogenic aerosol has been reduced in the participating models. In all our simulations, we prescribe the same patterns of the anthropogenic aerosol optical properties and associated effects on the cloud droplet number concentration. We calculate the instantaneous radiative forcing (RF) and the effective radiative forcing (ERF). Their difference defines the net contribution from rapid adjustments. Our simulations show a model spread in ERF from −0.4 to −0.9 W m−2. The standard deviation in annual ERF is 0.3 W m−2, based on 180 individual estimates from each participating model. This result implies that identifying the model spread in ERF due to systematic differences requires averaging over a sufficiently large number of years. Moreover, we find almost identical ERFs for the mid-1970s and mid-2000s for individual models, although there are major model differences in natural aerosols and clouds. The model-ensemble mean ERF is −0.54 W m−2 for the pre-industrial era to the mid-1970s and −0.59 W m−2 for the pre-industrial era to the mid-2000s. Our result suggests that comparing ERF changes between two observable periods rather than absolute magnitudes relative to a poorly constrained pre-industrial state might provide a better test for a model's ability to represent transient climate changes.

Description: Throughout the last few decades and in the near future CO2–induced ocean acidification is potentially a big threat to marine calcite-shelled animals (e.g., brachiopods, bivalves, corals and gastropods). Despite the great number of studies focusing on the effects of acidification on shell growth, metabolism, shell dissolution and shell repair, the consequences on biomineral formation remain poorly understood, and only few studies addressed contemporarily the impact of acidification on shell microstructure and geochemistry. In this study, a detailed microstructure and stable isotope geochemistry investigation was performed on nine adult brachiopod specimens of Magellania venosa (Dixon, 1789), grown in the natural environment as well as in controlled culturing experiments at different pH conditions (ranging 7.35 to 8.15±0.05) over different time intervals (214 to 335 days). Details of shell microstructural features, such as thickness of the primary layer, density and size of endopunctae and morphology of the basic structural unit of the secondary layer were analysed using scanning electron microscopy (SEM). Stable isotope compositions (δ13C and δ18O) were tested from the secondary shell layer along shell ontogenetic increments in both dorsal and ventral valves. Based on our comprehensive dataset, we observed that, under low pH conditions, M. venosa produced a more organic-rich shell with higher density of and larger endopunctae, and smaller secondary layer fibres, when subjected to about one year of culturing. Also, increasingly negative δ13C and δ18O values are recorded by the shell produced during culturing and are related to the CO2–source in the culture setup. Both the microstructural changes and the stable isotope results are similar to observations on brachiopods from the fossil record and strongly support the value of brachiopods as robust archives of proxies for studying ocean acidification events in the geologic past.

Description: Anthropogenic emissions of greenhouse gases such as CO2 and N2O impinge on the Earth system, which in turn modulates atmospheric greenhouse gas concentrations. The underlying feedback mechanisms are complex and, at times, counterintuitive. So-called Earth system models have recently matured to standard tools tailored to assess these feedback mechanisms in a warming world. Applications for these models range from being targeted at basic process understanding to the assessment of geo-engineering options. A problem endemic to all these applications is the need to estimate poorly known model parameters, specifically for the biogeochemical component, based on observational data (e.g., nutrient fields). In the present study, we illustrate with an Earth system model that through such an approach biases and other model deficiencies in the physical ocean circulation model component can reciprocally compensate for biases in the pelagic biogeochemical model component (and vice versa). We present two model configurations that share a remarkably similar steady state (based on ad hoc measures) when driven by historical boundary conditions, even though they feature substantially different configurations (parameter sets) of ocean mixing and biogeochemical cycling. When projected into the future the similarity between the model responses breaks. Metrics such as changes in total oceanic carbon content and suboxic volume diverge between the model configurations as the Earth warms. Our results reiterate that advancing the understanding of oceanic mixing processes will reduce the uncertainty of future projections of oceanic biogeochemical cycles. Related to the latter, we suggest that an advanced understanding of oceanic biogeochemical cycles can be used for advancements in ocean circulation modules.

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: In order to better understand the role of fluids during subduction and subsequent exhumation, we have investigated whole-rock and mineral chemistry (major and trace elements) and Li, B as well as O, Sr, Nd, Pb isotopes on selected continuous drill-core profiles through contrasting lithological boundaries from the Chinese Continental Scientific Drilling Program (CCSD) in Sulu, China. Four carefully selected sample sets have been chosen to investigate geochemical changes as a result of fluid mobilization during dehydration, peak metamorphism, and exhumation of deeply subducted continental crust. Our data reveal that while O and Sr-Nd-Pb isotopic compositions remain more or less unchanged, significant Li and/or B isotope fractionations occur between different lithologies that are in close contact during various metamorphic stages. Samples that are supposed to represent prograde dehydration as indicated by veins formed at high pressures (HP) are characterized by element patterns of highly fluid-mobile elements in the veins that are complementary to those of the host eclogite. A second sample set represents a UHP metamorphic crustal eclogite that is separated from a garnet peridotite by a thin transitional interface. Garnet peridotite and eclogite are characterized by a 〉10% difference in MgO, which, together with the presence of abundant hydroxyl-bearing minerals and compositionally different clinopyroxene grains demonstrate that both rocks have been derived from different sources that have been tectonically juxtaposed during subduction, and that hydrous silicate-rich fluids have been added from the subducting slab to the mantle. Two additional sample sets, comprising retrograde amphibolite and relatively fresh eclogite, demonstrate that besides external fluids, internal fluids can be responsible for the formation of amphibolite. Li and B concentrations and isotopic compositions point to losses and isotopic fractionation during progressive dehydration. On the other hand, fluids with isotopically heavier Li and B are added during retrogression. On a small scale, mantle-derived rocks may be significantly metasomatized by fluids derived from the subducted slab. Our study indicates that during high-grade metamorphism, Li and B may show different patterns of enrichment and of isotopic fractionation.

Description: The Itajaí Basin located in the southern border of the Luís Alves Microplate is considered as a peripheral foreland basin related to the Dom Feliciano Belt. It presents an excellent record of the Ediacaran period, and its upper parts display the best Brazilian example of Precambrian turbiditic deposits. The basal succession of Itajaí Group is represented by sandstones and conglomerates (Baú Formation) deposited in alluvial and deltaic-fan systems. The marine upper sequences correspond to the Ribeirão Carvalho (channelized and non-channelized proximal silty-argillaceous rhythmic turbidites), Ribeirão Neisse (arkosic sandstones and siltites), and Ribeirão do Bode (distal silty turbidites) formations. The Apiúna Formation felsic volcanic rocks crosscut the sedimentary succession. The Cambrian Subida leucosyenogranite represents the last felsic magmatic activity to affect the Itajaí Basin. The Brusque Group and the Florianópolis Batholith are proposed as source areas for the sediments of the upper sequence. For the lower continental units the source areas are the Santa Catarina, São Miguel and Camboriú complexes. The lack of any oceanic crust in the Itajaí Basin suggests that the marine units were deposited in a restricted, internal sea. The sedimentation started around 600 Ma and ended before 560 Ma as indicated by the emplacement of rhyolitic domes. The Itajaí Basin is temporally and tectonically correlated with the Camaquã Basin in Rio Grande do Sul and the Arroyo del Soldado/Piriápolis Basin in Uruguay. It also has several tectono-sedimentary characteristics in common with the African-equivalent Nama Basin.

Description: Most studies dealing with material properties of sandstones are based on a small data set. The present study utilizes petrographical and petrophysical data from 22 selected sandstones and ~300 sandstones from the literature to estimate/predict the material and weathering behaviour of characteristic sandstones. Composition and fabric properties were determined from detailed thin section analyses. Statistical methods applied consist of data distributions with whisker plots and linear regression with confidence regions for the petrophysical and weathering properties. To identify similarities between individual sandstones and to define groups of specific sandstone types, principal component and cluster analyses were applied. The results confirm an interaction between the composition, depositional environment, stratigraphic association and diagenesis, which leads to a particular material behaviour of sandstones. Three different types of pore radii distributions are observed, whereby each is derived from different pore space modifications during diagenesis and is associated with specific sandstone types: (1) bimodal with a maximum in capillary and micropores, (2) unimodal unequal with a maximum in smaller capillary pores and (3) unimodal equable with a maximum in larger capillary pores. Each distribution shows specific dependencies to water absorption, salt loading and hygric dilatation. The strength–porosity relationship shows dependence on the content of unstable lithic fragments, grain contact and type of pore radii distribution, cementation and degree of alteration. Sandstones showing a maximum of capillary pores and micropores (bimodal) exhibit a distinct hygric dilatation and low salt resistance. These sandstones are highly immature sublitharenites–litharenites, characterized by altered unstable rock fragments, which show pointed-elongated grain contacts, and some pseudomatrix. Quartz arenites and sublitharenites–litharenites which are strongly compacted and cemented, show unimodal unequal pore radii distributions, low porosity, high strength and a high salt resistance. The presence of swellable clay minerals in sublitharenites–litharenites leads to a medium to high hygric dilatation, whereas quartz arenites show little hygric dilatation. Sandstones with unimodal equal pore radii distribution mostly belong to weakly compacted and cemented mature quartz arenites. These are characterized by high water absorption and high porosity, low to medium strength and a low salt resistance. The data compiled in this study are used to create a sandstone quality catalogue. Since material properties are dependent on many different parameters of influence, the transition between different lithotypes is fluent.

Description: The lattice-preferred orientation (LPOs) of two late-Variscan granitoids, the Meissen monzonite and the Podlesí dyke granite, were determined from high-resolution time-of-flight neutron diffraction patterns gained at the diffractometer SKAT in Dubna, Russia. The results demonstrate that the method is suitable for the LPO analysis of polyphase, relatively coarse-grained (0.1–6 mm) rocks. The Meissen monzonite has a prominent shape-preferred orientation (SPO) of the non-equidimensional minerals feldspar, mica and amphibole, whereas SPO of the Podlesí granite is unapparent at the hand-specimen scale. The neutron diffraction data revealed distinct LPOs in both granitoids. The LPO of the non-equidimensional minerals feldspar, mica and amphibole developed mainly during magmatic flow. In the case of the Meissen monzonite, the magmatic flow was superimposed by regional shear tectonics, which, however, had no significant effect on the LPOs. In both samples, quartz shows a weak but distinct LPO, which is atypical for plastic deformation and different in the syn-kinematic Meissen monzonite and the post-kinematic Podlesí granite. We suggest that, first of all, the quartz LPO of the Meissen monzonite is the result of oriented growth in an anisotropic stress field. The quartz LPO of the Podlesí granite, which more or less resembles a deformational LPO in the flattening field of the local strain field, developed during magmatic flow, whereby the rhombohedral faces of the quartz crystals adhered to the (010) faces of aligned albite and to the (001) faces of zinnwaldite. Due to shape anisotropy of their attachments, the quartz crystals were passively aligned by magmatic flow. Thus, magmatic flow and oriented crystal growth are the major LPO-forming processes in both granitoids. For the Meissen monzonite, the solid-state flow was too weak to cause significant crystallographic re-orientation of the minerals aligned by magmatic flow. Finally, the significance of our results for the evaluation of the regional tectonic environment during magma emplacement is discussed. The discussion on the regional implications of the more methodologically oriented results provides the basis for future, more regionally aimed studies in view of the fabric characteristics of such plutons and their developing mechanisms.

Description: The Eastern Sierras Pampeanas were structured by three main events: the Ediacaran to early Cambrian (580–510 Ma) Pampean, the late Cambrian–Ordovician (500–440 Ma) Famatinian and the Devonian-Carboniferous (400–350 Ma) Achalian orogenies. Geochronological and Sm–Nd isotopic evidence combined with petrological and structural features allow to speculate for a major rift event (Ediacaran) dividing into two Mesoproterozoic major crustal blocks (source of the Grenvillian age peaks in the metaclastic rocks).This event would be coeval with the development of arc magmatism along the eastern margin of the eastern block. Closure of this eastern margin led to a Cambrian active margin (Sierra Norte arc) along the western margin of the eastern block in which magmatism reworked the same crustal block. Consumption of a ridge segment (input of OIB signature mafic magmas) which controlled granulite-facies metamorphism led to a final collision (Pampean orogeny) with the western Mesoprotrozoic block. Sm–Nd results for the metamorphic basement suggest that the TDM age interval of 1.8–1.7 Ga, which is associated with the less radiogenic values of εNd(540) (−6 to −8), can be considered as the mean average crustal composition for the Eastern Sierras Pampeanas. Increasing metamorphic grade in rocks with similar detrital sources and metamorphic ages like in the Sierras de Córdoba is associated with a younger TDM age and a more positive εNd(540) value. Pampean pre-540 Ma granitoids form two clusters, one with TDM ages between 2.0 and 1.75 Ga and another between 1.6 and 1.5 Ga. Pampean post-540 Ma granitoids exhibit more homogenous TDM ages ranging from 2.0 to 1.75 Ga. Ordovician re-activation of active margin along the western part of the block that collided in the Cambrian led to arc magmatism (Famatinian orogeny) and related ensialic back-arc basin in which high-grade metamorphism is related to mid-crustal felsic plutonism and mafic magmatism with significant contamination of continental crust. TDM values for the Ordovician Famatinian granitoids define a main interval of 1.8–1.6, except for the Ordovician TTG suites of the Sierras de Córdoba, which show younger TDM ages ranging from 1.3 to 1.0 Ga. In Devonian times (Achalian orogeny), a new subduction regime installed west of the Eastern Sierras Pampeanas. Devonian magmatism in the Sierras exhibit process of mixing/assimilation of depleted mantle signature melts and continental crust. Achalian magmatism exhibits more radiogenic εNd(540) values that range between 0.5 and −4 and TDM ages younger than 1.3 Ga. In pre-Devonian times, crustal reworking is dominant, whereas processes during Devonian times involved different geochemical and isotopic signatures that reflect a major input of juvenile magmatism.

Description: The expansion processes that develop in building stones upon changes of moisture content may be an important contributing factor for their deteriorations. Until recently, few data could be found in the literature concerning this parameter and weathering processes. Moreover, the processes that may be responsible for the moisture related expansion of natural building stones are not yet completely understood. To further elucidate this process, extensive mineralogical, petrophysical and fabric investigations were performed on eight German sandstones in order to obtain more information regarding the weathering process and its dependence on the rock fabric. The analysed sandstones show a wide range of pore size distributions and porosities. A positive correlation with the fabric and the pore space can be found for all studied petrophysical parameters. The intensity of the expansion and related swelling pressure cannot be attributed only to the swelling of clay minerals. The investigations suggest that the micropores and the resulting disjoining pressure during wet/dry cycles also play an important role. The results obtained suggest that the mechanism is related to the presence of liquid water within the porous material.

Description: The profitable production of dimension stone mainly depends on the extractable block size. The regularity and volume of the blocks are of critical importance, and are controlled by the three-dimensional pattern of the discontinuity system. Therefore, optimization of block size has to be the aim when quarrying for natural stone. This is mainly connected to the quantification of joints and fractures, i.e., their spacing and orientation. The problem of finding unfractured blocks within arbitrarily oriented and distributed planes can be solved effectively by a numerical algorithm. The main effects of joint orientations on block sizes and shapes will be presented in this article. Quantification of unfractured blocks with the aim of optimization is illustrated by detailed studies on several quarries. The algorithm used in this study can be applied as a powerful tool in the planning of a quarry and the future exploitation of dimension stone. Application of the described approach is demonstrated on practical examples of quarrying natural stones, namely, sandstone, granite, rhyolite, etc. Block quarrying can be optimized by using the new 3D-BlockExpert approach. The quantification of unfractured rock masses is also shown to contribute to a more ecological protection and the sustainable use of natural resources.

Description: Damages to natural building stones induced by the action of frost are considered to be of great importance. Commonly, the frost resistance of building stones is checked by standardised freeze–thaw tests before using. Corresponding tests normally involve 30–50 freeze–thaw action cycles. In order to verify the significance of such measurements, we performed long-term tests on four selected rocks over 1,400 freeze–thaw action cycles. Additionally, numerous petrophysical parameters were analysed to compare the behaviour of rocks in the weathering tests according to the current explanatory models of stress formation by growing ice crystals in the pore space. The long-term tests yield more information about the real frost sensibility of the rocks. A clear deterioration cannot be determined in most cases until 50 weathering cycles have been completed. In the freeze–thaw tests, the samples are also stressed by changing temperature and moisture, indicating that different decay mechanisms can interfere with each other. Thus, thermohygric and moisture expansion are important damage processes.

Description: Owing to its long building history, different types of building stones comprised the construction of the Cologne Cathedral. Severe damage is observed on the different stones, e.g., sandstones, carbonate, and volcanic rocks, especially when the different stone materials neighbor the medieval “Drachenfels trachyte” from the “Siebengebirge”. The question arises, “Is the insufficient compatibility of the implemented building materials causatively related to the strong decay of the Drachenfels trachyte?” The present investigations focus on the petrography and mineralogical composition of eight different stones from the Cologne Cathedral. Petrophysical data, i.e., phase content, moisture and thermal characteristics as well as strength properties are determined and discussed in correlation to each other, showing that not only in terms of lithology great differences exist, but also the petrophysical properties strongly diverge. The ascertained parameters are discussed in view of the deterioration behavior and decay mechanisms of the different stones. To evaluate the compatibility of original, replacement and modern building materials, the properties of the investigated stones are compared to those of Drachenfels trachyte by means of constraints given in the literature. Besides optical properties, petrophysical criteria are also defined as well as strength values. It could be shown that primarily moisture properties, i.e., capillary and sorptive water uptake, water saturation, drying processes and moisture dilatation can be addressed to the deterioration processes.

Description: The range of substrates that the bone-eating marine worm Osedax is able to consume has important implications for its evolutionary history, especially its potential link to the rise of whales. Once considered a whale specialist, recent work indicates that Osedax consumes a wide range of vertebrate remains, including whale soft tissue and the bones of mammals, birds and fishes. Traces resembling those produced by living Osedax have now been recognized for the first time in Oligocene whale teeth and fish bones from deep-water strata of the Makah, Pysht and Lincoln Creek formations in western Washington State, USA. The specimens were acid etched from concretions, and details of the borehole morphology were investigated using micro-computed tomography. Together with previously published Osedax traces from this area, our results show that by Oligocene time Osedax was able to colonize the same range of vertebrate remains that it consumes today and had a similar diversity of root morphologies. This supports the view that a generalist ability to exploit vertebrate bones may be an ancestral trait of Osedax.

Description: The formation of ring faults yields important implications for understanding the structural and dynamic evolution of collapse calderas and potentially associated ash-flow eruptions. Caldera collapse occurred in 2000 at Miyakejima Island (Japan) in response to a lateral intrusion. Based on geophysical data it is inferred that a set of caldera ring faults was propagating upward. To understand the kinematics of ring-fault propagation, linkage, and interaction, we describe new laboratory sand-box experiments that were analyzed through Digital Image Correlation (DIC) and post-processed using 2D strain analysis. The results help us gain a better understanding of the processes occurring during caldera subsidence at Miyakejima. We show that magma chamber evacuation induces strain localization at the lateral chamber margin in the form of a set of reverse faults that sequentially develops and propagates upwards. Then a set of normal faults initiates from tension fractures at the surface, propagating downwards to link with the reverse faults at depth. With increasing amounts of subsidence, interaction between the reverse- and normal-fault segments results in a deactivation of the reverse faults, while displacement becomes focused on the outer normal faults. Modeling results show that the area of faulting and collapse migrates successively outward, as peak displacement transfers from the inner ring faults to later developed outer ring faults. The final structural architecture of the faults bounding the subsiding piston-like block is hence a consequence of the amount of subsidence, in agreement with other caldera structures observed in nature. The experimental simulations provide an analogy to the observations and seismic records of caldera collapse at Miyakejima volcano, but are also applicable to caldera collapse in general.

Description: Forests in lowland Bolivia suffer from severe deforestation caused by different types of agents and land use activities. We identify three major proximate causes of deforestation. The largest share of deforestation is attributable to the expansion of mechanized agriculture, followed by cattle ranching and small-scale agriculture. We utilize a spatially explicit multinomial logit model to analyze the determinants of each of these proximate causes of deforestation between 1992 and 2004. We substantiate the quantitative insights with a qualitative analysis of historical processes that have shaped land use patterns in the Bolivian lowlands to date. Our results suggest that the expansion of mechanized agriculture occurs mainly in response to good access to export markets, fertile soil, and intermediate rainfall conditions. Increases in small-scale agriculture are mainly associated with a humid climate, fertile soil, and proximity to local markets. Forest conversion into pastures for cattle ranching occurs mostly irrespective of environmental determinants and can mainly be explained by access to local markets. Land use restrictions, such as protected areas, seem to prevent the expansion of mechanized agriculture but have little impact on the expansion of small-scale agriculture and cattle ranching. The analysis of future deforestation trends reveals possible hotspots of future expansion for each proximate cause and specifically highlights the possible opening of new frontiers for deforestation due to mechanized agriculture. Whereas the quantitative analysis effectively elucidates the spatial patterns of recent agricultural expansion, the interpretation of long-term historic drivers reveals that the timing and quantity of forest conversion are often triggered by political interventions and historical legacies.

Description: The Mantiqueira Province represents a series of supracrustal segments of the South-American counterpart formed during the Gondwana Supercontinent agglutination. In this crustal domain, the process of escape tectonics played a conspicuous role, generating important NE–N–S-trending lineaments. The oblique component of the motions of the colliding tectonic blocks defined the transpressional character of the main suture zones: Lancinha-Itariri, Cubatão-Arcádia-Areal, Serrinha-Rio Palmital in the Ribeira Belt and Sierra Ballena-Major Gercino in the Dom Feliciano Belt. The process as a whole lasted for ca. 60 Ma, since the initial collision phase until the lateral escape phase predominantly marked by dextral and subordinate sinistral transpressional shear zones. In the Dom Feliciano Belt, southern Brazil and Uruguay, transpressional event at 630–600 Ma is recognized and in the Ribeira Belt, despite less coevally, the transpressional event occurred between 590 and 560 Ma in its northern-central portion and between ca. 625 and 595 Ma in its central-southern portion. The kinematics of several shear zones with simultaneous movement in opposite directions at their terminations is explained by the sinuosity of these lineaments in relation to a predominantly continuous westward compression.

Description: The Sierras Pampeanas in central and north-western Argentina constitute a distinct morphotectonic feature between 27°S and 33°S. The last stage of uplift and deformation in this area are interpreted to be closely related to the Andean flat-slab subduction of the Nazca plate beneath the South American plate. K–Ar fault gouge dating and low-temperature thermochronology along two transects within the Sierra de Comechingones reveal a minimum age for the onset of brittle deformation about 340 Ma, very low exhumation rates since Late Paleozoic time, as well as a total exhumation of about 2.3 km since the Late Cretaceous. New Ar–Ar ages (7.54–1.91 Ma) of volcanic rocks from the San Luis volcanic belt support the eastward propagation of the flat-slab magmatic front, confirming the onset of flat-slab related deformation in this region at 11.2 Ma. Although low-temperature thermochronology does not clearly constrain the signal of the Andean uplift, it is understood that the current structural relief related to the Comechingones range has been achieved after the exhumation of both fault walls (circa 80–70 Ma).

Description: The Palaeogene was the most recent greenhouse period on Earth. Especially for the Late Palaeocene and Early Eocene, several superimposed short-term hyperthermal events have been described, including extremes such as the Palaeocene–Eocene Thermal Maximum. Major faunal and floral turnovers in the marine and terrestrial realms were recorded in association with these events. High-resolution palynological analysis of the early Middle Eocene maar lake sediments at Messel, near Darmstadt, Germany, provides an insight into the dynamics of a climax vegetation during the Middle Eocene greenhouse climate in a time span without significant climatic excursions. Numerical techniques like detrended correspondence analysis and wavelet analysis have been applied to recognize cyclic fluctuations and long-term trends in the vegetation through a time interval of approximately 640 kyr. Based on the numerical zoning of the pollen diagram, three phases in the development of the vegetation may be distinguished. Throughout these phases, the climax vegetation did not change substantially in qualitative composition, but a trend towards noticeably less humid conditions probably in combination with a drop of the water level in the lake may be recognized. A shift in algal population from the freshwater dinoflagellate cyst Messelodinium thielepfeifferae to a dominance of Botryococcus in the uppermost part of the core is interpreted as a response to changes in acidity and nutrient availability within the lake. Time series analyses of pollen assemblages show that variations in the Milankovitch range of eccentricity, obliquity and precession can be distinguished. In addition, fluctuations in the sub-Milankovitch range are indicated. This demonstrates that floral changes during steady depositional conditions in the Middle Eocene of Messel were controlled by orbital forcing.

Description: In the presented case study, ascomycete fungi and green algae on a marble monument were identified by comparisons of the 18S rRNA gene sequences, which were obtained from DNA either from environmental samples or from enrichment cultures. The organisms were found to be responsible for either black or green surface coverings on different areas of the monument surface. Most fungi were related to plant-inhabiting genera, corresponding to a heavy soiling of the marble surface with honeydew. Whereas green algae of the genera Stichococcus, Chloroidium and Apatococcus were found to be dominant in all samples, isolates of two additional genera were recovered only from enrichment cultures. A reference strain of Apatococcus lobatus and an isolate of Prasiolopsis sp. were investigated with respect to putative surface adhesive structures of the cell envelope. The Prasiolopsis cell walls were covered with a thin adhesive exopolysaccharide layer involved in biofilm formation.

Description: Bowing is a well-known phenomenon seen in marbles used as building veneers. This form of rock weathering occurs as a result of external factors such as temperature, humidity, the system for anchoring the marble slabs or the panel dimensions. Under the same external conditions, many factors will determine the degree of deformation including petrography, thermal properties and residual locked stresses. The usual way to solve the problem of bowed marble slabs is to replace them with other materials, such as granites, in which the deformation still exists but is less common. In this study, eight ornamental granites with different mineralogy, grain size, grain shape, porosity and fabric were tested in a laboratory to assess their susceptibility to bowing. Three slabs of granite, each cut with a different orientation, were studied under different conditions of temperature (90 and 120°C) and water saturation (dry and wet) to investigate the influence of these factors together with that of anisotropy. At 90°C, only the granite with the coarsest grain size and low porosity exhibited deformation under wet conditions. At 120°C and wet conditions, three of the granites showed evident signs of bowing. Again, the granite with the coarsest grain size was the most deformed. It was concluded that the wide grain size distribution influences microcracking more than other expected factors, such as the quartz content of the rock. Also, mineral shape-preferred orientation and porosity play an important role in the bowing of the studied granites.

Description: The emplacement of the Mesoproterozoic Götemar Pluton into Paleoproterozoic granitoid host rocks of the Transscandinavian Igneous Belt is re-examined by microfabric analysis, including cathodoluminescence microscopy. Field data on the pluton-host rock system are used to strengthen the model. The Götemar Pluton, situated on the Baltic Shield of SE Sweden, is a horizontally zoned tabular structure that was constructed by the intrusion of successive pulses of magma with different crystal/melt ratios, at an estimated crustal depth of 4–8 km. Initial pluton formation involved magma ascent along a vertical dike, which was arrested at a mechanical discontinuity within the granitoid host rocks; this led to the formation of an initial sill. Subsequent sill stacking and their constant inflation resulted in deformation and reheating of existing magma bodies, which also raised the pluton roof. This multi-stage emplacement scenario is indicated by complex dike relationships and the occurrence of several generations of quartz (Si-metasomatism). The sills were charged by different domains of a heterogeneous magma chamber with varying crystal/melt ratios. Ascent or emplacement of magma with a high crystal/melt ratio is indicated by syn-magmatic deformation of phenocrysts. Complex crystallization fabrics (e.g. oscillatory growth zoning caused by high crystal defect density, overgrowth and replacement features, resorbed and corroded crystal cores, rapakivi structure) are mostly related to processes within the main chamber, that is repeated magma mixing or water influx.