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Photodegradation of plastic consumer products is known to accelerate weathering and facilitate the release of chemicals and plastic particles into the aquatic environment. However, these processes are complex. In our presented pilot study, eight plastic consumer products were leached in distilled water under strong ultraviolet (UV) light simulating eight months of Central European climate and compared to their respective dark controls (DCs). The leachates and formed plastic particles were exploratorily characterized using a range of chemical analytical tools to describe degradation and leaching processes. These techniques covered (a) microplastic analysis, showing substantial liberation of plastic particles further increased under UV exposure, (b) non-targeted mass spectrometric characterization of the leachates, revealing several hundreds of chemical features with typically only minor agreement between the UV exposure and the corresponding DCs, (c) target analysis of 71 organic analytes, of which 15 could be detected in at least one sample, and (d) metal(loid) analysis, which revealed substantial release of toxic metal(loid)s further enhanced under UV exposure. A data comparison with the US-EPA’s ToxVal and ToxCast databases showed that the detected metals and organic additives might pose substantial health and environmental concerns, requiring further study and comprehensive impact assessments.

Quantification of the diffusive methane fluxes between the coastal ocean and atmosphere is important to constrain the atmospheric methane budget. The determination of the fluxes in coastal waters is characterized by a high level of uncertainty. To improve the accuracy of the estimation of coastal methane fluxes, high temporal and spatial sampling frequencies of dissolved methane in seawater are required, as well as the quantification of atmospheric methane concentrations, wind speed and wind direction above the ocean. In most cases, these atmospheric data are obtained from land-based atmospheric and meteorological monitoring stations in the vicinity of the coastal ocean methane observations.In this study, we measured wind speed, wind direction and atmospheric methane directly on board three research vessels in the southern North Sea and compared the local and remote atmospheric and meteorological measurements on the quality of the flux data. In addition, we assessed the source of the atmospheric methane measured in the study area in the German Bight using air mass back-trajectory assessments.The choice of the wind speed data source had a strong impact on the flux calculations. Fluxes based on wind data from nearby weather stations amounted to only 58 ± 34 % of values based on in situ data. Using in situ data, we calculated an average diffusive methane sea-to-air flux of 221 ± 351 µmol m−2 d−1 (n = 941) and 159 ± 444 µmol m−2 d−1 (n = 3028) for our study area in September 2019 and 2020, respectively. The area-weighted diffusive flux for the entire area of Helgoland Bay (3.78 × 109 m2) was 836 ± 97 and 600 ± 111 kmol d−1 for September 2019 and 2020, respectively. Using the median value of the diffusive fluxes for these extrapolations resulted in much lower values compared to area-weighted extrapolations or mean-based extrapolations.In general, at high wind speeds, the surface water turbulence is enhanced, and the diffusive flux increases. However, this enhanc

An insufficient supply of the micronutrient iron (Fe) limits phytoplankton growth across large parts of the ocean. Ambient Fe speciation and solubility are largely dependent on seawater physico-chemical properties. We calculated the apparent Fe solubility (SFe(III)app) at equilibrium for ambient conditions, where SFe(III) app is defined as the sum of aqueous inorganic Fe(III) species and Fe(III) bound to organic matter formed at a free Fe 3+ concentration equal to the solubility of Fe hydroxide. We compared the SFe(III) app to measured dissolved Fe (dFe) in the Atlantic and Pacific Oceans. The SFe(III) app was overall ∼2–4-fold higher than observed dFe at depths less than 1,000 m, ∼2-fold higher than the dFe between 1,000 and 4,000 m and ∼3-fold higher than dFe below 4,000 m. Within the range of used parameters, our results showed that there was a similar trend in the vertical distributions of horizontally averaged SFe(III) app and dFe. Our results suggest that vertical dFe distributions are underpinned by changes in SFe(III)app, which are driven by relative changes in ambient pH and temperature. Since both pH and temperature are essential parameters controlling ambient Fe speciation, these should be accounted for in investigations of changing Fe dynamics, particularly in the context of ocean acidification and warming.

Nutrient and carbon dynamics within the river-estuary-coastal water systems are key processes in understanding the flux of matter from the terrestrial environment to the ocean. Here, we analysed those dynamics by following a sampling approach based on the travel time of water and an advanced calculation of nutrient fluxes in the tidal part. We started with a nearly Lagrangian sampling of the river (River Elbe, Germany; 580 km within 8 days). After a subsequent investigation of the estuary, we followed the plume of the river by raster sampling the German Bight (North Sea) using three ships simultaneously. In the river, we detected intensive longitudinal growth of phytoplankton connected with high oxygen saturation and pH values and an undersaturation of CO2, whereas concentrations of dissolved nutrients declined. In the estuary, the Elbe shifted from an autotrophic to a heterotrophic system: Phytoplankton died off upstream of the salinity gradient, causing minima in oxygen saturation and pH, supersaturation of CO2, and a release of nutrients. In the shelf region, phytoplankton and nutrient concentrations were low, oxygen was close to saturation, and pH was within a typical marine range. Over all sections, oxygen saturation was positively related to pH and negatively to pCO2. Corresponding to the significant particulated nutrient flux via phytoplankton, flux rates of dissolved nutrients from river into estuary were low and determined by depleted concentrations. In contrast, fluxes from the estuary to the coastal waters were higher and the pattern was determined by tidal current. Overall, the approach is appropriate to better understand land-ocean fluxes, particularly to illuminate the importance of these fluxes under different seasonal and hydrological conditions, including flood and drought events.

Mercury (Hg) in seawater is subject to interconversions via (photo)chemical and (micro)biological processes that determine the extent of dissolved gaseous mercury (DGM) (re)emission and the production of monomethylmercury. We investigated Hg speciation in the South Atlantic Ocean on a GEOTRACES cruise along a 40°S section between December 2011 and January 2012 (354 samples collected at 24 stations from surface to 5250 m maximum depth). Using statistical analysis,concentrations of methylated mercury (MeHg, geometric mean 35.4 fmol L −1) were related to seawater temperature, salinity , and fluorescence. DGM concentrations (geometric mean 0.17 pmol L −1) were related to water column depth, concentrations of macronutrients and dissolved inorganic carbon (DIC). The first-ever observed linear correlation between DGM and DIC obtained from high-resolution data indicates possible DGM production by organic matter remineralization via biological or dark abiotic reactions. DGM concentrations projected from literature DIC data using the newly discovered DGM–DIC relationship agreed with published DGM observations.

The Arctic Ocean is considered a source of micronutrients to the Nordic Seas and the North Atlantic Ocean through the gateway of Fram Strait (FS). However, there is a paucity of trace element data from across the Arctic Ocean gateways, and so it remains unclear how Arctic and North Atlantic exchange shapes micronutrient availability in the two ocean basins. In 2015 and 2016, GEOTRACES cruises sampled the Barents Sea Opening (GN04, 2015) and FS (GN05, 2016) for dissolved iron (dFe), manganese (dMn), cobalt (dCo), nickel (dNi), copper (dCu) and zinc (dZn). Together with the most recent synopsis of Arctic-Atlantic volume fluxes, the observed trace element distributions suggest that FS is the most important gateway for Arctic-Atlantic dissolved micronutrient exchange as a consequence of Intermediate and Deep Water transport. Combining fluxes from FS and the Barents Sea Opening with estimates for Davis Strait (GN02, 2015) suggests an annual net southward flux of 2.7 ± 2.4 Gg·a−1 dFe, 0.3 ± 0.3 Gg·a−1 dCo, 15.0 ± 12.5 Gg·a−1 dNi and 14.2 ± 6.9 Gg·a−1 dCu from the Arctic toward the North Atlantic Ocean. Arctic-Atlantic exchange of dMn and dZn were more balanced, with a net southbound flux of 2.8 ± 4.7 Gg·a−1 dMn and a net northbound flux of 3.0 ± 7.3 Gg·a−1 dZn. Our results suggest that ongoing changes to shelf inputs and sea ice dynamics in the Arctic, especially in Siberian shelf regions, affect micronutrient availability in FS and the high latitude North Atlantic Ocean.

We used a combined ion pairing - organic matter speciation model (NICA-Donnan) to predict the organic complexation of iron (Fe) at ambient pH and temperature in the Celtic Sea. We optimized our model by direct comparison with Fe speciation determined by Adsorptive Cathodic Stripping Voltammetry using the added Fe-binding ligand 1-nitroso-2-naphthol (HNN) in the presence and absence of natural organic matter. We compared determined Fe speciation with simulated titrations obtained via application of the NICA-Donnan model with four different NICA parameter sets representing a range of binding site strengths and heterogeneities. We tested the assumption that binding sites scale to dissolved organic carbon (DOC) concentrations in marine waters. We found that a constant low DOC concentration resulted in an improved fit of our titration data to the simulated titrations, suggesting that inputs of autochthonous marine DOM may not increase the heterogeneity or concentrations of Fe binding sites. Using the optimal parameter set, we calculated pFe(III)´ (−log(∑Fe (OH)i3−i)) and apparent Fe(III) solubility (SFe(III)app) at ambient pH andtemperature in the water column of the Celtic Sea. SFe(III) app was defined as the sum of aqueous inorganic Fe(III) species and Fe(III) bound to DOM formed at a free Fe (Fe3+)concentration equal to the limiting solubility of Fe hydroxide (Fe(OH) 3(s)). SFe(III)app was within range of the determined dissolved Fe concentrations observed after winter mixing on the shelf and in waters >1500 m depth at our most offshore stations. Our study supports the hypothesis that the ocean dissolved Fe inventory is controlled by the interplay between Fe solubility and Fe binding by organic matter, although the overall number of metal binding sites in the marine environment may not be directly scalable to DOC concentrations.

Approximately half of the freshwater discharged from the Greenland and Antarctic Ice Sheets enters the ocean subsurface as a result of basal ice melt, or runoff draining via the grounding line of a deep ice shelf or marine-terminating glacier. Around Antarctica and parts of northern Greenland, this freshwater then experiences prolonged residence times in large cavities beneath floating ice tongues. Due to the inaccessibility of these cavities, it is unclear how they moderate the freshwater associated supply of nutrients such as iron (Fe) to the ocean. Here, we show that subglacial dissolved Fe export from Nioghalvfjerdsbrae (the ‘79°N Glacier’) is decoupled from particulate inputs including freshwater Fe supply, likely due to the prolonged ~162-day residence time of Atlantic water beneath Greenland’s largest floating ice-tongue. Our findings indicate that the overturning rate and particle-dissolved phase exchanges in ice cavities exert a dominant control on subglacial nutrient supply to shelf regions.

Around the Greenlandic and Antarctic coastlines, sediment plumes associated with glaciers are significant sources of lithogenic material to the ocean. These plumes contain elevated concentrations of a range of trace metals, especially in particle bound phases, but it is not clear how these particles affect dissolved (<0.2 µm) metal distributions in the ocean. Here we show, using transects in 8 glacier fjords, trends in the distribution of dissolved iron, cobalt, nickel and copper (dFe, dCo, dNi, dCu). Following rapid dFe loss close to glacier outflows, dFe concentrations in particular showed strong similarities between different fjords. Similar dFe concentrations were also observed between seasons/years when Nuup Kangerlua (SW Greenland) was revisited in spring, mid- and late-summer. Dissolved Cu, dCo and dNi concentrations were more variable and showed different gradients with salinity depending on the fjord, season and year. The lack of consistent trends for dCu and dNi largely reflects less pronounced differences contrasting the concentration of inflowing shelf waters with fresher glacially-modified waters. Particles also made only small contributions to total dissolvable Cu (dCu constituted 83 ± 28% of total dissolvable Cu) and Ni (dNi constituted 86 ± 28% of total dissolvable Ni) within glacier plumes. For comparison, dFe was a lower fraction of total dissolvable Fe; 3.5 ± 4.8%. High concentrations of total dissolvable Fe in some inner-fjord environments, up to 77 µM in Ameralik (SW Greenland), may drive enhanced removal of scavenged type elements, such as Co. Further variability may have been driven by local bedrock mineralogy, which could explain high concentrations of dNi (25–29 nM) and dCo (6–7 nM) in one coastal region of west Greenland (Kangaatsiaq). Our results suggest that dissolved trace element distributions in glacier fjords are influenced by a range of factors including: freshwater concentrations, local geology, drawdown by sca

Competitive ligand exchange – adsorptive cathodic stripping voltammetry (CLE-AdCSV) is a widely used technique to determine dissolved iron (Fe) speciation in seawater, and involves competition for Fe of a known added ligand (AL) with natural organic ligands. Three different ALs were used, 2-(2-thiazolylazo)-p-cresol (TAC), salicylaldoxime (SA) and 1-nitroso-2-napthol (NN). The total ligand concentrations ([Lt]) and conditional stability constants (log K′Fe’L) obtained using the different ALs are compared. The comparison was done on seawater samples from Fram Strait and northeast Greenland shelf region, including the Norske Trough, Nioghalvfjerdsfjorden (79N) Glacier front and Westwind Trough. Data interpretation using a one-ligand model resulted in[Lt]SA (2.72 ± 0.99 nM eq Fe) > [Lt] TAC (1.77 ± 0.57 nM eq Fe) > [Lt]NN (1.57 ± 0.58 nM eq Fe); with the mean of log K′Fe’L being the highest for TAC (log ′KFe’L(TAC) = 12.8 ± 0.5), followed by SA (log K′Fe’L(SA) = 10.9 ± 0.4) and NN (log K′Fe’L(NN) = 10.1 ± 0.6). These differences are only partly explained by the detection windows employed, and are probably due to uncertainties propagated from the calibration and the heterogeneityof the natural organic ligands. An almost constant ratio of [Lt] TAC/[Lt]SA = 0.5 – 0.6 was obtained in samples over the shelf, potentially related to contributions of humicacid-type ligands. In contrast, in Fram Strait [Lt] TAC/[Lt]SA varied considerably from 0.6 to 1, indicating the influence of other ligand types, which seemed to be detected to a different extent by the TAC and SA methods. Our results show that even though the SA, TAC and NN methods have different detectionwindows, the results of the one ligand model captured a

A thorough and reliable assessment of changes in sea surface water temperatures is essential for understanding the effects of global warming on long-term trends in marine ecosystems and their communities. The first long-term temperature measurements were established almost a century ago, especially in coastal areas, and some of them are still in operation. However, while in earlier times these measurements were done by hand every day, current environmental long-term observation stations (ELTOS) are often fully automated and integrated in cabled underwater observatories (UWOs). With this new technology, year-round measurements became feasible even in remote or difficult to access areas, such as coastal areas of the Arctic Ocean in winter, where measurements were impossible just a decade ago. In this context, there is a question over what extent the sampling frequency and accuracy influence results in long-term monitoring approaches. In this paper, we address this with a combination of lab experiments on sensor accuracy and precision and a simulated sampling program with different sampling frequencies based on a continuous water temperature dataset from Svalbard, Arctic, from 2012 to 2017. Our laboratory experiments showed that temperature measurements with 12 different temperature sensor types at different price ranges all provided measurements accurate enough to resolve temperature changes over years on a level discussed in the literature when addressing climate change effects in coastal waters. However, the experiments also revealed that some sensors are more suitable for measuring absolute temperature changes over time, while others are more suitable for determining relative temperature changes. Our simulated sampling program in Svalbard coastal waters over five years revealed that the selection of a proper sampling frequency is most relevant for discriminating significant long term temperature changes from random daily, seasonal, or interannual fluctuations. Whil

The Fram Strait is the only deep connection between the Arctic and Atlantic Oceans. The main water and mercury (Hg) fluxes between these oceans occur via the Fram Strait and Barents Sea Opening. Several Hg mass balance studies indicated a net Hg export from the Arctic to the Atlantic Ocean. However, in the absence of Hg measurements in the Fram Strait and Barents Sea Opening, these estimates were based on North Atlantic and central Arctic Ocean data alone. Here, we refine the Arctic total Hg (tHg) and methylated Hg (MeHg) mass budgets using new data acquired during the 2015 GEOTRACES (section GN04) TransArcII cruise in the Barents Sea Opening and the 2016 GEOTRACES (section GN05) GRIFF cruise, which covered the Fram Strait and Northeast Greenland Shelf. Total Hg increased westward along the Fram Strait transect, reaching the highest concentrations on the Northeast Greenland Shelf. Concentrations of tHg averaged 1.29 ± 0.43 pM in the East Greenland Current, while core waters of the West Spitsbergen Current had average values of 0.80 ± 0.26 pM. Using our new data, we estimate that 43 ± 9 Mg y-1 of tHg is transported to the Arctic Ocean in the core of the West Spitsbergen Current, while 54 ± 13 Mg y-1 of tHg is exported from the Arctic Ocean in the East Greenland Current and Recirculated Atlantic Water. This results in a net tHg export of 11 ± 8 Mg y−1 via the Fram Strait. We find a shallow MeHg maximum (at 150 m depth) in the East Greenland Current, in agreement to what was reported for the central Arctic Ocean and Canadian Arctic Archipelago. The West Spitsbergen Current is characterized by lower MeHg concentrations and a deeper MeHg maximum, that is located at approximately 1000 m depth. We estimate a net MeHg export of 6 ± 2 Mg y-1 from the Arctic Ocean via the Fram Strait, which is nearly half of the exported tHg. Most of the exported MeHg is in the form of DMHg (2:1 ratio of dimethylmercury to monomethylme

Freshwater discharge from glaciers is increasing across the Arctic in response to anthropogenic climate change, which raises questions about the potential downstream effects in the marine environment. Whilst a combination of long-term monitoring programmes and intensive Arctic field campaigns have improved our knowledge of glacier–ocean interactions in recent years, especially with respect to fjord/ocean circulation, there are extensive knowledge gaps concerning how glaciers affect marine biogeochemistry and productivity. Following two cross-cutting disciplinary International Arctic Science Committee (IASC) workshops addressing the importance of glaciers for the marine ecosystem, here we review the state of the art concerning how freshwater discharge affects the marine environment with a specific focus on marine biogeochemistry and biological productivity. Using a series of Arctic case studies (Nuup Kangerlua/Godthåbsfjord, Kongsfjorden, Kangerluarsuup Sermia/Bowdoin Fjord, Young Sound and Sermilik Fjord), the interconnected effects of freshwater discharge on fjord–shelf exchange, nutrient availability, the carbonate system, the carbon cycle and the microbial food web are investigated. Key findings are that whether the effect of glacier discharge on marine primary production is positive or negative is highly dependent on a combination of factors. These include glacier type (marine- or land-terminating), fjord–glacier geometry and the limiting resource(s) for phytoplankton growth in a specific spatio-temporal region (light, macronutrients or micronutrients). Arctic glacier fjords therefore often exhibit distinct discharge–productivity relationships, and multiple case-studies must be considered in order to understand the net effects of glacier discharge on Arctic marine ecosystems.

Large national and international observational efforts over recent decades have provided extensive and invaluable datasets of a range of ocean variables. Compiled large datasets, structured, or unstructured, are a powerful tool that allow scientists to access and synthesize data collected over large spatial and temporal scales. The data treatment approaches for any element in the ocean could lead to new global perspectives of their distribution patterns and to a better understanding of large-scale oceanic processes and their impact on other biogeochemical cycles, which may not be evident otherwise. Ocean chemistry Big Data analysis may not just be limited to distribution patterns, but may be used to assess how sampling efforts and analytical methodologies can be improved. Furthermore, a systematic global scale assessment of data is important to evaluate the gaps in knowledge and to provide avenues for future research. In this context, here we provide an extensive compilation of oceanic aluminum (Al) concentration data from global ocean basins, including data available in the GEOTRACES Intermediate Data product (Schlitzer et al., 2018), but also thus far unpublished data.

Marine phytoplankton growth at high latitudes is extensively limited by iron availability. Icebergs are a vector transporting the bioessential micronutrient iron into polar oceans. Therefore, increasing iceberg fluxes due to global warming have the potential to increase marine productivity and carbon export, creating a negative climate feedback. However, the magnitude of the iceberg iron flux, the subsequent fertilization effect and the resultant carbon export have not been quantified. Using a global analysis of iceberg samples, we reveal that iceberg iron concentrations vary over 6 orders of magnitude. Our results demonstrate that, whilst icebergs are the largest source of iron to the polar oceans, the heterogeneous iron distribution within ice moderates iron delivery to offshore waters and likely also affects the subsequent ocean iron enrichment. Future marine productivity may therefore be not only sensitive to increasing total iceberg fluxes, but also to changing iceberg properties, internal sediment distribution and melt dynamics.

Gravitational sinking of photosynthetically fixed particulate organic carbon (POC) constitutes a key component of the biological carbon pump. The fraction of POC leaving the surface ocean depends on POC sinking velocity (SV) and remineralization rate (Cremin), both of which depend on plankton community structure. However, the key drivers in plankton communities controlling SV and Cremin), are poorly constrained. In fall 2014, we conducted a 6‐week mesocosm experiment in the subtropical NE Atlantic Ocean to study the influence of plankton community structure on SV and Cremin), . Oligotrophic conditions prevailed for the first 3 weeks, until nutrient‐rich deep water injected into all mesocosms stimulated diatom blooms. SV declined steadily over the course of the experiment due to decreasing CaCO3 ballast and—according to an optical proxy proposed herein—due to increasing aggregate porosity mostly during an aggregation event after the diatom bloom. Furthermore, SV was positively correlated with the contribution of picophytoplankton to the total phytoplankton biomass. Cremin), was highest during a Synechococcus bloom under oligotrophic conditions and in some mesocosms during the diatom bloom after the deep water addition, while it was particularly low during harmful algal blooms. The temporal changes were considerably larger in Cremin), (max. fifteenfold) than in SV (max. threefold). Accordingly, estimated POC transfer efficiency to 1,000 m was mainly dependent on how the plankton community structure affected Cremin), . Our approach revealed key players and interactions in the plankton food web influencing POC export efficiency thereby improving our mechanistic understanding of the biological carbon pump.

The diversity of life in the sea is critical to the health of ocean ecosystems that support living resources and therefore essential to the economic, nutritional, recreational, and health needs of billions of people. Yet there is evidence that the biodiversity of many marine habitats is being altered in response to a changing climate and human activity. Understanding this change, and forecasting where changes are likely to occur, requires monitoring of organism diversity, distribution, abundance, and health. It requires a minimum of measurements including productivity and ecosystem function, species composition, allelic diversity, and genetic expression. These observations need to be complemented with metrics of environmental change and socio-economic drivers. However, existing global ocean observing infrastructure and programs often do not explicitly consider observations of marine biodiversity and associated processes. Much effort has focused on physical, chemical and some biogeochemical measurements. Broad partnerships, shared approaches, and best practices are now being organized to implement an integrated observing system that serves information to resource managers and decision-makers, scientists and educators, from local to global scales. This integrated observing system of ocean life is now possible due to recent developments among satellite, airborne, and in situ sensors in conjunction with increases in information system capability and capacity, along with an improved understanding of marine processes represented in new physical, biogeochemical, and biological models., biodiversity, ecosystem health, habitat suitability indices, indicators, thresholds, essential ocean variables, essential biodiversity variables, omics

About a quarter of anthropogenic CO2 emissions are currently taken up by the oceans, decreasing seawater pH. We performed a mesocosm experiment in the Baltic Sea in order to investigate the consequences of increasing CO2 levels on pelagic carbon fluxes. A gradient of different CO2 scenarios, ranging from ambient ( ∼ 370 µatm) to high ( ∼ 1200 µatm), were set up in mesocosm bags ( ∼ 55 m3). We determined standing stocks and temporal changes of total particulate carbon (TPC), dissolved organic carbon (DOC), dissolved inorganic carbon (DIC), and particulate organic carbon (POC) of specific plankton groups. We also measured carbon flux via CO2 exchange with the atmosphere and sedimentation (export), and biological rate measurements of primary production, bacterial production, and total respiration. The experiment lasted for 44 days and was divided into three different phases (I: t0–t16; II: t17–t30; III: t31–t43). Pools of TPC, DOC, and DIC were approximately 420, 7200, and 25 200 mmol C m−2 at the start of the experiment, and the initial CO2 additions increased the DIC pool by ∼ 7 % in the highest CO2 treatment. Overall, there was a decrease in TPC and increase of DOC over the course of the experiment. The decrease in TPC was lower, and increase in DOC higher, in treatments with added CO2. During phase I the estimated gross primary production (GPP) was ∼ 100 mmol C m−2 day−1, from which 75–95 % was respired, ∼ 1 % ended up in the TPC (including export), and 5–25 % was added to the DOC pool. During phase II, the respiration loss increased to ∼ 100 % of GPP at the ambient CO2 concentration, whereas respiration was lower (85–95 % of GPP) in the highest CO2 treatment. Bacterial production was ∼ 30 % lower, on average, at the highest CO2 concentration than in the controls during phases II and III. This resulted in a higher accumulation of DOC and lower reduction in the TPC pool in the elevated CO2 treatments at the end of phase II extending throughout phase III

Anthropogenic emissions completely overwhelmed natural marine lead (Pb) sources duringthe past century, predominantly due to leaded petrol usage. Here, based on Pb isotopemeasurements, we reassess the importance of natural and anthropogenic Pb sources to thetropical North Atlantic following the nearly complete global cessation of leaded petrol use.Significant proportions of up to 30–50% of natural Pb, derived from mineral dust, areobserved in Atlantic surface waters, reflecting the success of the global effort to reduceanthropogenic Pb emissions. The observation of mineral dust derived Pb in surface waters isgoverned by the elevated atmospheric mineral dust concentration of the North African dustplume and the dominance of dry deposition for the atmospheric aerosol flux to surfacewaters. Given these specific regional conditions, emissions from anthropogenic activities willremain the dominant global marine Pb source, even in the absence of leaded petrolcombustion.

Global climate change involves an increase in oceanic CO2 concentrations as well as thermal stratification of the water column, thereby reducing nutrient supply from deep to surface waters. Changes in inorganic carbon (C) or nitrogen (N) availability have been shown to affect marine primary production, yet little is known about their interactive effects. To test for these effects, we conducted continuous culture experiments under N limitation and exposed the bloom-forming dinoflagellate species Scrippsiella trochoidea and Alexandrium fundyense (formerly A. tamarense) to CO2 partial pressures (pCO2) ranging between 250 and 1000 µatm. Ratios of particulate organic carbon (POC) to organic nitrogen (PON) were elevated under N limitation, but also showed a decreasing trend with increasing pCO2. PON production rates were highest and affinities for dissolved inorganic N were lowest under elevated pCO2, and our data thus demonstrate a CO2-dependent trade-off in N assimilation. In A. fundyense, quota of paralytic shellfish poisoning toxins were moreover lowered under N limitation, but the offset to those obtained under N-replete conditions became smaller with increasing pCO2. Consequently, cellular toxicity under N limitation was highest under elevated pCO2. All in all, our observations imply reduced N stress under elevated pCO2, which we attribute to a reallocation of energy from C to N assimilation as a consequence of lowered costs in C acquisition. Such interactive effects of ocean acidification and nutrient limitation may favor species with adjustable carbon concentrating mechanisms and have consequences for their competitive success in a future ocean.

Climate change has significant implications for biodiversity and ecosystems. With slow progress towards reducing greenhouse gas emissions, climate engineering (or ‘geoengineering’) is receiving increasing attention for its potential to limit anthropogenic climate change and its damaging effects. Proposed techniques, such as ocean fertilization for carbon dioxide removal or stratospheric sulfate injections to reduce incoming solar radiation, would significantly alter atmospheric, terrestrial and marine environments, yet potential side-effects of their implementation for ecosystems and biodiversity have received little attention. A literature review was carried out to identify details of the potential ecological effects of climate engineering techniques. A group of biodiversity and environmental change researchers then employed a modified Delphi expert consultation technique to evaluate this evidence and prioritize the effects based on the relative importance of, and scientific understanding about, their biodiversity and ecosystem consequences. The key issues and knowledge gaps are used to shape a discussion of the biodiversity and ecosystem implications of climate engineering, including novel climatic conditions, alterations to marine systems and substantial terrestrial habitat change. This review highlights several current research priorities in which the climate engineering context is crucial to consider, as well as identifying some novel topics for ecological investigation.

The uptake of anthropogenic atmospheric CO2 by the oceans causes a shift in the carbonate chemistry system which includes a lowering of pH; this process has been termed ocean acidification. Our understanding of the specific effects of ocean acidification on chemical speciation of trace metals, in particular on organic–metal interactions, is limited. In this study we have experimentally determined the effects of changing pH from 8.3 to 6.8 (on the NBS scale) on the speciation of iron and copper in estuarine waters. Our experimental results indicated that complexation of iron and copper would decrease and inorganic iron and copper concentrations increase, as pH decreased, although it was not possible to confidently quantify changes in speciation at lower pH due to constraints of the analytical technique. In addition to our experimental approach, we used a non-ideal competitive adsorption (NICA)–Donnan model to determine the chemical speciation of iron and copper as a function of pH. The NICA–Donnan model was optimised in order to produce similar metal binding characteristics to those observed in our sample across the pH range examined in our study. The model allowed for simultaneous modelling of solubility and organic complexation. Model results indicated that a decrease in iron and copper binding by organic matter at lower pH, coupled with increased solubility (for iron), resulted in a 3 fold increase in inorganic iron concentration and a 6 fold increase in inorganic copper concentration at pH of 7.41 compared to a pH of 8.18 (expressed on the total scale). This compared to a 10 fold increase in inorganic iron concentration, and a 5 fold increase in inorganic copper concentration, obtained at pH 8.18, when the dissolved organic carbon (DOC) concentration was halved. Variability in DOC might thus be expected to have a greater impact on metal speciation in seawater, than projected variability in pH resulting from increases in atmospheric CO2. Our study therefore sugges

The North Atlantic receives the largest dust loading of any of the world's oceans due to its proximity to North African deserts and prevailing wind patterns. The supply of biologically important trace elements and nutrients via aerosols has an important influence on biogeochemical processes and ecosystems in this ocean region. In this study we continuously sampled aerosols between July 2007 and July 2008 at the Cape Verde Atmospheric Observatory (CVAO), which is situated on an island group close to the North African continent and under the Saharan/Sahelian dust outflow path. The aim of our work was to investigate temporal variations in aerosol concentration, composition and sources in the Cape Verde region over a complete seasonal cycle, and for this purpose we undertook mineralogical and chemical (42 elements) analyses of the aerosol samples and air mass back-trajectory calculations. Aerosol samples were also collected during a research cruise in the (sub-) tropical Northeast Atlantic Ocean in January 2008.The concentration of atmospheric Al, a proxy for mineral aerosol concentration, at CVAO was in the range of 0.01–66.9 µg m- 3 (maximum on 28–30 January 2008) with a geometric mean of 0.76 µg m- 3. It showed distinct seasonal variations, with enhanced Al concentrations in winter (geometric mean 1.3 µg m- 3), and lower concentrations in summer (geometric mean 0.48 µg m- 3). These observations have been attributed to dust transport occurring in higher altitude air layers and mainly north of the Cape Verde during summer, while in winter the dust transport shifts south and occurs in the lower altitude trade winds with consequent greater influence on the Cape Verde region. The elemental composition of the aerosols closely agreed with mean upper crustal abundances, with the exception of elements with pronounced anthropogenic sources (e.g. Zn and Pb) and major constituents of sea water (Na and Mg). Mineral analysis showed that clays were the most abundant mineral fractio

The ongoing oceanic uptake of anthropogenic carbon dioxide (CO2) is significantly altering the carbonate chemistry of seawater, a phenomenon referred to as ocean acidification. Experimental manipulations have been increasingly used to gauge how continued ocean acidification will potentially impact marine ecosystems and their associated biogeochemical cycles in the future; however, results amongst studies, particularly when performed on natural communities, are highly variable, which in part likely reflects inconsistencies in experimental approach. To investigate the potential for identification of more generic responses and greater experimentally reproducibility, we devised and implemented a series of highly replicated (n = 8), short term (2–4 days) multi-level (≥ 4 conditions) carbonate chemistry/nutrient manipulation experiments on a range of natural microbial communities sampled in Northwest European shelf seas. Carbonate chemistry manipulations and resulting biological responses were found to be highly reproducible within individual experiments and to a lesser extent between geographically different experiments. Statistically robust reproducible physiological responses of phytoplankton to increasing pCO2, characterized by a suppression of net growth for small sized cells (< 10 μm), were observed in the majority of the experiments, irrespective of nutrient status. Remaining between-experiment variability was potentially linked to initial community structure and/or other site-specific environmental factors. Analysis of carbon cycling within the experiments revealed the expected increased sensitivity of carbonate chemistry to biological processes at higher pCO2 and hence lower buffer capacity. The results thus emphasize how biological-chemical feedbacks may be altered in the future ocean.

Coccolithophores are a key functional group in terms of the pelagic production of calcium carbonate (calcite), although their contribution to shelf sea biogeochemistry, and how this relates to environmental conditions, is poorly constrained. Measurements of calcite production (CP) and coccolithophore abundance were made on the north-west European shelf to examine trends in coccolithophore calcification along natural gradients of carbonate chemistry, macronutrient availability and plankton composition. Similar measurements were also made in three bioassay experiments where nutrient (nitrate, phosphate) and pCO2 levels were manipulated. Nanoflagellates (< 10 μm) dominated chlorophyll biomass and primary production (PP) at all but one sampling site, with CP ranging from 0.6 to 9.6 mmol C m−2 d−1. High CP and coccolithophore abundance occurred in a diatom bloom in fully mixed waters off Heligoland, but not in two distinct coccolithophore blooms in the central North Sea and Western English Channel. Coccolithophore abundance and CP showed no correlation with nutrient concentrations or ratios, while significant (p < 0.01) correlations between CP, cell-specific calcification (cell-CF) and irradiance in the water column highlighted how light availability exerts a strong control on pelagic CP. In the experimental bioassays, Emiliania-huxleyi-dominated coccolithophore communities in shelf waters (northern North Sea, Norwegian Trench) showed a strong response in terms of CP to combined nitrate and phosphate addition, mediated by changes in cell-CF and growth rates. In contrast, an offshore diverse coccolithophore community (Bay of Biscay) showed no response to nutrient addition, while light availability or mortality may have been more important in controlling this community. Sharp decreases in pH and a rough halving of calcite saturation states in the bioassay experiments led to decreased CP in the Bay of Biscay and northern North Sea, but not the Norwegian Trench. These decrea

We present here a high resolution surface water pH dataset obtained in the Northwest European shelf seas in summer 2011. This is the first time that pH has been measured at such a high spatial resolution (10 measurements h–1) in this region. The aim of our paper is to investigate the carbonate chemistry dynamics of the surface water using pH and ancillary data. The main processes controlling the pH distribution along the ship's transect, and their relative importance, were determined using a statistical approach. The study highlights the impact of biological activity, temperature and riverine inputs on the carbonate chemistry dynamics of the shelf seas surface water. For this summer cruise, the biological activity formed the main control of the pH distribution along the cruise transect. Variations in chlorophyll and nutrients explained 29% of the pH variance along the full transect and as much as 68% in the northern part of the transect. In contrast, the temperature distribution explained ca. 50% of the pH variation in the Skagerrak region. Riverine inputs were evidenced by high dissolved organic carbon (DOC) levels in the Strait of Moyle (northern Irish Sea) and the southern North Sea with consequent remineralisation processes and a reduction in pH. The DOC distribution described 15% of the pH variance along the full transect. This study highlights the high spatial variability of the surface water pH in shelf seawaters where a range of processes simultaneously impacts the carbonate chemistry.

In this study we report diapycnal diffusive fluxes of dissolved iron (dFe), dissolved aluminium (dAl) and the major macronutrients to the surface waters of the North Atlantic subpolar gyre. Turbulent diffusivities at the base of the summer mixed layer ranged from 0.01 to 0.5 (median 0.07) cm2 s−1 and daily macronutrient fluxes into the surface mixed layer typically represented < 0.5% of integrated mixed layer inventories, although fluxes were highly variable. Elevated nutrient fluxes of up to 4% of mixed layer inventories were identified on the Greenland Shelf, where integrated nutrient pools were lowest due to localised shoaling of the mixed layer. Diffusive fluxes of dFe and dAl were typically <0.1% of mixed layer inventories but were also highly variable between stations. Approximations of daily phytoplankton nutrient and Fe uptake indicate that the diffusive flux may at best represent <10% of phytoplankton macronutrient uptake, and only 1% of daily phytoplankton Fe uptake. The daily turbulent diffusive flux of dFe was comparable in magnitude to coincident estimates of aeolian Fe supply but despite shallower than normal convective mixing in winter 2010 the diffusive supply was 22 and 59 times smaller than the annual convective supply of Fe to the Irminger and Iceland basins respectively. The general picture obtained from this study is one of small magnitude diffusive nutrient and Fe fluxes to the subpolar North Atlantic during the period of annual nutrient minima and indicates that the diffusive supply mechanism is unlikely to alleviate the recently identified presence of seasonal iron limitation within the North Atlantic subpolar gyre; a condition exacerbated by low dFe:NO3− ratios in subsurface source waters.

Particulate organic carbon (POC) generated by primary production and exported to depth, is an important pathway for carbon transfer to the abyss, where it is stored over climatically significant timescales. These processes constitute the biological carbon pump. A spectrum of particulate sinking velocities exists throughout the water column, however numerical models often simplify this spectrum into suspended, fast and slow sinking particles. Observational studies suggest the spectrum of sinking speeds in the ocean is strongly bimodal with >85% POC flux contained within two pools with sinking speeds of <10 m day−1 and >350 m day−1. We deployed a Marine Snow Catcher (MSC) to estimate the magnitudes of the suspended, fast and slow sinking pools and their fluxes at the Porcupine Abyssal Plain site (48°N, 16.5°W) in summer 2009. The POC concentrations and fluxes determined were 0.2 μg C L−1 and 54 mg C m−2 day−1 for fast sinking particles, 5 μg C L−1 and 92 mg C m−2 day−1 for slow sinking particles and 97 μg C L−1 for suspended particles. Our flux estimates were comparable with radiochemical tracer methods and neutrally buoyant sediment traps. Our observations imply: (1) biomineralising protists, on occasion, act as nucleation points for aggregate formation and accelerate particle sinking; (2) fast sinking particles alone were sufficient to explain the abyssal POC flux; and (3) there is no evidence for ballasting of the slow sinking flux and the slow sinking particles were probably entirely remineralised in the twilight zone.