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The discovery of atmospheric micro(nano)plastic transport and ocean-atmosphere exchange points to a highly complex marine plastic cycle, with negative implications for human and ecosystem health. Yet, observations are currently limited. In this Perspective, we quantify the processes and fluxes of the marine-atmospheric micro(nano)plastic cycle, with the aim of highlighting the remaining unknowns in atmospheric micro(nano)plastic transport. Between 0.013 and 25 million metric tons per year of micro(nano)plastics are potentially being transported within the marine atmosphere and deposited in the oceans. However, the high uncertainty in these marine-atmospheric fluxes is related to data limitations and a lack of study intercomparability. To address the uncertainties and remaining knowledge gaps in the marine-atmospheric micro(nano)plastic cycle, we propose a future global marine-atmospheric micro(nano)plastic observation strategy, incorporating novel sampling methods and the creation of a comparable, harmonized and global data set. Together with long-term observations and intensive investigations, this strategy will help to define the trends in marine-atmospheric pollution and any responses to future policy and management actions. Atmospheric transport of microplastics could be a major source of plastic pollution to the ocean, yet observations currently remain limited. This Perspective quantifies the known budgets of the marine-atmospheric micro(nano)plastic cycle and proposes a future global observation strategy.

Accounting guidelines exist for the recording of carbon flows in terrestrial and coastal ecosystems. Shelf sea sediments, while considered an important carbon store, have yet to receive comparable scrutiny. Here, we explore whether effective management of carbon stocks accumulating in shelf seas could contribute towards a nation’s greenhouse gas emissions reduction targets. We review the complexities of carbon transport and fate in shelf seas, and the geopolitical challenges of carbon accounting in climate governance because of the transboundary nature of carbon flows in the marine environment. New international accounting guidance and governance frameworks are needed to prompt climate action., Accounting guidelines exist for carbon flows in terrestrial and coastal ecosystems, but not shelf sea sediments. In this Review, the authors explore whether effective management of carbon stocks accumulating in shelf seas could contribute to a nation’s greenhouse gas emissions reduction targets.

Reaction with iodide (I-) at the sea surface is an important sink for atmospheric ozone, and causes sea-air emission of reactive iodine which in turn drives further ozone destruction. To incorporate this process into chemical transport models, improved understanding of the factors controlling marine iodine speciation, and especially sea-surface iodide concentrations, is needed. The oxidation of I- to iodate (IO3-) is the main sink for oceanic I-, but the mechanism for this remains unknown. We demonstrate for the first time that marine nitrifying bacteria mediate I- oxidation to IO3-. A significant increase in IO3- concentrations compared to media-only controls was observed in cultures of the ammonia-oxidising bacteria Nitrosomonas sp. (Nm51) and Nitrosoccocus oceani (Nc10) supplied with 9-10 mM I-, indicating I- oxidation to IO3-. Cell-normalised production rates were 15.69 (+/- 4.71) fmol IO3- cell(-1) d(-1) for Nitrosomonas sp., and 11.96 (+/- 6.96) fmol IO3- cell(-1) d(-1) for Nitrosococcus oceani, and molar ratios of iodate-to-nitrite production were 9.2 +/- 4.1 and 1.88 +/- 0.91 respectively. Preliminary experiments on nitrite-oxidising bacteria showed no evidence of I- to IO3- oxidation. If the link between ammonia and I oxidation observed here is representative, our ocean iodine cycling model predicts that future changes in marine nitrification could alter global sea surface I fields with potential implications for atmospheric chemistry and air quality.

To mark the publication of the special collection in honor of Robert (Bob) A. Duce in the Journal of the Atmospheric Sciences, we have summarized his most important contributions to the subject of biogeochemical coupling between the atmosphere and ocean. Here we have divided these contributions into four themes—deposition from the atmosphere and its effects on the oceans, volatile elements emitted from the oceans, sea surface biology and aerosol formation, and marine aerosols and clouds. It is our intent that this summary along with the papers in this special collection provide an overview of the enormous contributions that Bob Duce has made to the subject during his distinguished scientific career.

We present new data on the rates of sedimentary denitrification and its component processes (canonical denitrification, anammox and dissimilatory nitrate reduction to ammonium) for intertidal and subtidal sites in the North Sea using nitrogen isotope addition methods. We find overall average denitrification rates of 6.3 (range 0.4–10.6) µmol m−2 h−1, similar to those previously reported for this region and other temperate shelf environments. We find canonical denitrification to be the dominant (>90%) process of the three. At the subtidal sites, most of the denitrification is supported by nitrate generated within the sediments, while at the intertidal site the main source is from the water column. We go on to consider the impact of these rates on nitrogen cycling within the North Sea region and compare the sediment core incubation rate results to estimates derived from modelling approaches. Model rates are somewhat higher than those directly measured and we consider possible reasons for this.

Dissolved organic matter (DOM) plays an important role in freshwater biogeochemistry. To investigate the influence of catchment character on the quality and quantity of DOM in freshwaters, 45 sampling sites draining subcatchments of contrasting soil type, hydrology, and land cover within one large upland‐dominated and one large lowland‐dominated catchment were sampled over a 1‐yr period. Dominant land cover in each subcatchment included: arable and horticultural, blanket peatland, coniferous woodland, and improved, unimproved, acid, and calcareous grasslands. The composition of the C, N, and P pool was determined as a function of the inorganic nutrient species (NO3−, NO2−, NH4+, and PO43−) and dissolved organic nutrient (dissolved organic carbon [DOC], dissolved organic nitrogen [DON], and dissolved organic phosphorus [DOP]) concentrations. DOM quality was assessed by calculation of the molar DOC : DON and DOC : DOP ratios and specific ultraviolet absorbance (SUVA254). In catchments with little anthropogenic nutrient inputs, DON and DOP typically composed > 80% of the total dissolved nitrogen (TDN) and total dissolved phosphorus (TDP) concentrations. By contrast, in heavily impacted agricultural catchments DON and DOP typically comprised 5–15% of TDN and 10–25% of TDP concentrations. Significant differences in DOC : DON and DOC : DOP ratios were observed between land cover class with significant correlations observed between both the DOC : DON and DOC : DOP molar ratios and SUVA254 (rs = 0.88 and 0.84, respectively). Analysis also demonstrated a significant correlation between soil C : N ratio and instream DOC : DON/DOP (rs = 0.79 and 0.71, respectively). We infer from this that soil properties, specifically the C : N ratio of the soil organic matter pool, has a significant influence on the composition of DOM in streams draining through these landscapes.

Evidence shows that habitats with potential to mitigate against greenhouse gases emissions, by taking up and storing CO2, are being lost due to the effects of on-going human activities and climate change. The carbon storage by terrestrial habitats (e.g. tropical forests) and the role of coastal habitats (‘Blue Carbon’) as carbon storage sinks is well recognised. Offshore shelf sediments are also a manageable carbon store, covering ∼9% of global marine area, but not currently protected by international agreements to enable their conservation. Through a scenario analysis, we explore the economic value of the damage of human activities and climate change can inflict on UK marine habitats, including shelf sea sediments. In a scenario of increased human and climate pressures over a 25-year period, we estimate damage costs up to US$12.5 billion from carbon release linked to disturbance of coastal and shelf sea sediment carbon stores. It may be possible to manage socio-economic pressure to maintain sedimentary carbon storage, but the trade-offs with other global social welfare benefits such as food security will have to be taken into account. To develop effective incentive mechanisms to preserve these valuable coastal and marine ecosystems within a sustainability governance framework, robust evidence is required.

Iodine is a critical trace element involved in many diverse and important processes in the Earth system. The importance of iodine for human health has been known for over a century, with low iodine in the diet being linked to goitre, cretinism and neonatal death. Research over the last few decades has shown that iodine has significant impacts on tropospheric photochemistry, ultimately impacting climate by reducing the radiative forcing of ozone (O 3 ) and air quality by reducing extreme O 3 concentrations in polluted regions. Iodine is naturally present in the ocean, predominantly as aqueous iodide and iodate. The rapid reaction of sea-surface iodide with O 3 is believed to be the largest single source of gaseous iodine to the atmosphere. Due to increased anthropogenic O 3 , this release of iodine is believed to have increased dramatically over the twentieth century, by as much as a factor of 3. Uncertainties in the marine iodine distribution and global cycle are, however, major constraints in the effective prediction of how the emissions of iodine and its biogeochemical cycle may change in the future or have changed in the past. Here, we present a synthesis of recent results by our team and others which bring a fresh perspective to understanding the global iodine biogeochemical cycle. In particular, we suggest that future climate-induced oceanographic changes could result in a significant change in aqueous iodide concentrations in the surface ocean, with implications for atmospheric air quality and climate.

Changing atmospheric acidity alters the delivery of nutrients to the ocean and affects marine productivity and ecology., Anthropogenic emissions to the atmosphere have increased the flux of nutrients, especially nitrogen, to the ocean, but they have also altered the acidity of aerosol, cloud water, and precipitation over much of the marine atmosphere. For nitrogen, acidity-driven changes in chemical speciation result in altered partitioning between the gas and particulate phases that subsequently affect long-range transport. Other important nutrients, notably iron and phosphorus, are affected, because their soluble fractions increase upon exposure to acidic environments during atmospheric transport. These changes affect the magnitude, distribution, and deposition mode of individual nutrients supplied to the ocean, the extent to which nutrient deposition interacts with the sea surface microlayer during its passage into bulk seawater, and the relative abundances of soluble nutrients in atmospheric deposition. Atmospheric acidity change therefore affects ecosystem composition, in addition to overall marine productivity, and these effects will continue to evolve with changing anthropogenic emissions in the future.

An ocean iodine cycling model is presented, which predicts upper ocean iodine speciation. The model comprises a three-layer advective and diffusive ocean circulation model of the upper ocean, and an iodine cycling model embedded within this circulation. The two primary reservoirs of iodine are represented, iodide and iodate. Iodate is reduced to iodide in the mixed layer in association with primary production, linked by an iodine to carbon (I:C) ratio. A satisfactory model fit with observations cannot be obtained with a globally constant I:C ratio, and the best fit is obtained when the I:C ratio is dependent on sea surface temperature, increasing at low temperatures. Comparisons with observed iodide distributions show that the best model fit is obtained when oxidation of iodide back to iodate is associated with mixed layer nitrification. Sensitivity tests, where model parameters and processes are perturbed, reveal that primary productivity, mixed layer depth, oxidation, advection, surface fresh water flux and the I:C ratio all have a role in determining surface iodide concentrations, and the timescale of iodide in the mixed layer is sufficiently long for non-local processes to be important. Comparisons of the modelled iodide surface field with parameterisations by other authors shows good agreement in regions where observations exist, but significant differences in regions without observations. This raises the question of whether the existing parameterisations are capturing the full range of processes involved in determining surface iodide, and shows the urgent need for observations in regions where there are currently none.

Marine iodine speciation has emerged as a potential tracer of primary productivity, sedimentary inputs, and ocean oxygenation. The reaction of iodide with ozone at the sea surface has also been identified as the largest deposition sink for tropospheric ozone and the dominant source of iodine to the atmosphere. Accurate incorporation of these processes into atmospheric models requires improved understanding of iodide concentrations at the air-sea interface. Observations of sea surface iodide are relatively sparse and are particularly lacking in the Indian Ocean basin. Here we examine 127 new sea surface (≤10 m depth) iodide and iodate observations made during three cruises in the Indian Ocean and the Indian sector of the Southern Ocean. The observations span latitudes from ∼12°N to ∼70°S, and include three distinct hydrographic regimes: the South Indian subtropical gyre, the Southern Ocean and the northern Indian Ocean including the southern Bay of Bengal. Concentrations and spatial distribution of sea surface iodide follow the same general trends as in other ocean basins, with iodide concentrations tending to decrease with increasing latitude (and decreasing sea surface temperature). However, the gradient of this relationship was steeper in subtropical waters of the Indian Ocean than in the Atlantic or Pacific, suggesting that it might not be accurately represented by widely used parameterizations based on sea surface temperature. This difference in gradients between basins may arise from differences in phytoplankton community composition and/or iodide production rates. Iodide concentrations in the tropical northern Indian Ocean were higher and more variable than elsewhere. Two extremely high iodide concentrations (1241 and 949 nM) were encountered in the Bay of Bengal and are thought to be associated with sedimentary inputs under low oxygen conditions. Excluding these outliers, sea surface iodide concentrations ranged from 20 to 250 nM, with a median of 61 nM. Controls on sea surface iodide concentrations in the Indian Ocean were investigated using a state-of-the-art iodine cycling model. Multiple interacting factors were found to drive the iodide distribution. Dilution via vertical mixing and mixed layer depth shoaling are key controls, and both also modulate the impact of biogeochemical iodide formation and loss processes.

Reaction with iodide (I) at the sea surface is an important sink for atmospheric ozone, and causes sea-air emission of reactive iodine which in turn drives further ozone destruction. To incorporate...

24 pages, 1 table, 5 figures.-- This is an open-access article distributed under the terms of the Creative Commons Attribution License (CC BY), The marine dissolved organic carbon (DOC) pool is an important player in the functioning of marine ecosystems. DOC is at the interface between the chemical and the biological worlds, it fuels marine food webs, and is a major component of the Earth’s carbon system. Here, we review the research showing impacts of global change stressors on the DOC cycling, specifically: ocean warming and stratification, acidification, deoxygenation, glacial and sea ice melting, changed inflow from rivers, changing ocean circulation and upwelling, and wet/dry deposition. A unified outcome of the future impacts of these stressors on the global ocean DOC production and degradation is not possible, due to regional differences and differences in stressors impacts, but general patterns for each stressor are presented, Thanks are due to FCT/MCTES for the financial support to CESAM (UIDP/50017/2020 + UIDB/50017/2020), through national funds. CC was supported by Fundação para a Ciência e a Tecnologia (FCT; SFRH/BPD/117746/2016). XÁ-S was funded by the Spanish MICINN (CTM2015-69392-C3-2-R), co-funded by FEDER

Surface ocean biogeochemistry and photochemistry regulate ocean–atmosphere fluxes of trace gases critical for Earth's atmospheric chemistry and climate. The oceanic processes governing these fluxes are often sensitive to the changes in ocean pH (or p CO 2 ) accompanying ocean acidification (OA), with potential for future climate feedbacks. Here, we review current understanding (from observational, experimental and model studies) on the impact of OA on marine sources of key climate-active trace gases, including dimethyl sulfide (DMS), nitrous oxide (N 2 O), ammonia and halocarbons. We focus on DMS, for which available information is considerably greater than for other trace gases. We highlight OA-sensitive regions such as polar oceans and upwelling systems, and discuss the combined effect of multiple climate stressors (ocean warming and deoxygenation) on trace gas fluxes. To unravel the biological mechanisms responsible for trace gas production, and to detect adaptation, we propose combining process rate measurements of trace gases with longer term experiments using both model organisms in the laboratory and natural planktonic communities in the field. Future ocean observations of trace gases should be routinely accompanied by measurements of two components of the carbonate system to improve our understanding of how in situ carbonate chemistry influences trace gas production. Together, this will lead to improvements in current process model capabilities and more reliable predictions of future global marine trace gas fluxes.

The marine iodine cycle has significant impacts on air quality and atmospheric chemistry. Specifically, the reaction of iodide with ozone in the top few micrometres of the surface ocean is an important sink for tropospheric ozone (a pollutant gas) and the dominant source of reactive iodine to the atmosphere. Sea surface iodide parameterisations are now being implemented in air quality models, but these are currently a major source of uncertainty. Relatively little observational data is available to estimate the global surface iodide concentrations, and this data has not hitherto been openly available in a collated, digital form. Here we present all available sea surface (, Measurement(s)iodideTechnology Type(s)digital curationFactor Type(s)sampling time and placeSample Characteristic - Environmentsea water • oceanSample Characteristic - LocationEarth (planet) Machine-accessible metadata file describing the reported data: 10.6084/m9.figshare.10130129

We briefly review the role of atmospheric deposition measurements within the Atlantic Meridional Transect (AMT) programme and then go on to present new data on the soluble concentrations of a range of trace metals (Fe, Al, Mn, Ti, Zn, V, Ni and Cu) and major ions in aerosols collected along the AMT transect. The results allow us to identify emission sources of the trace metals particularly in terms of the relative importance of anthropogenic versus crustal sources. We identify strong gradients in concentrations and deposition for both crustal and anthropogenically sourced metals with much higher inputs to the North Atlantic compared to the South Atlantic, reflecting stronger land based emission sources in the Northern Hemisphere. We suggest anthropogenic sources of Ni and V may include an important component from shipping. We consider the extent to which these gradients are reflected in surface water concentrations of these metals based on the GEOTRACES water column trace metal data. We find there is a clear difference in the concentrations of surface water dissolved Al and Fe between the north and south Atlantic gyres reflecting atmospheric inputs. However for Mn, V or Ni, higher inputs to the North Atlantic compared to the South Atlantic are not clearly reflected in their water column concentrations.

The role ships play in atmospheric, oceanic, and biogeochemical observations is described with a focus on measurements made within 100 m of the ocean surface. Ships include merchant and research vessels, cruise liners and ferries, fishing vessels, coast guard, military, and other government-operated ships, yachts, and a growing fleet of automated surface vessels. The present capabilities of ships to measure essential climate/ocean variables and the requirements from a broad community to address operational, commercial, and scientific needs are described. Following the guidance from the OceanObs'19 organizing committee, the authors provide a vision to expand observations needed from ships to understand and forecast the exchanges across the ocean-atmosphere interface. The vision addresses (1) recruiting vessels to improve both spatial and temporal sampling, (2) conducting multi-variate sampling on ships, (3) raising technology readiness levels of automated shipboard sensors and ship-to-shore data communications, (4) advancing quality evaluation of observations, and (5) developing a unified data management approach for observations and metadata that meets the needs of a diverse user community. Recommendations are made focusing on integrating private and autonomous vessels into the observing system, investing in sensor and communications technology development, developing an integrated data management structure that includes all types of ships, and moving towards a quality evaluation process that will result in a subset of ships being defined as mobile reference ships that will support climate studies. We envision a future where commercial, research, and privately-owned vessels are making multivariate observations using a combination of automated and human-observed measurements. All data and metadata will be documented, tracked, evaluated, distributed, and archived to benefit users of marine data. This vision looks at ships as a holistic network, not a set of disparate commercial, research, and/or third-party activities working in isolation, to bring these communities together for the mutual benefit of all.

Air pollution creates high Fe solubility in pyrogenic aerosols, raising the flux of biologically essential Fe to the oceans., Atmospheric deposition is a source of potentially bioavailable iron (Fe) and thus can partially control biological productivity in large parts of the ocean. However, the explanation of observed high aerosol Fe solubility compared to that in soil particles is still controversial, as several hypotheses have been proposed to explain this observation. Here, a statistical analysis of aerosol Fe solubility estimated from four models and observations compiled from multiple field campaigns suggests that pyrogenic aerosols are the main sources of aerosols with high Fe solubility at low concentration. Additionally, we find that field data over the Southern Ocean display a much wider range in aerosol Fe solubility compared to the models, which indicate an underestimation of labile Fe concentrations by a factor of 15. These findings suggest that pyrogenic Fe-containing aerosols are important sources of atmospheric bioavailable Fe to the open ocean and crucial for predicting anthropogenic perturbations to marine productivity.

We present the distribution and C:N stoichiometry of dissolved organic matter (DOM) in the North Sea in two summers (August 2011 and August 2012), with supporting data from the intervening winter (January 2012). These data demonstrate local variability superimposed on a general pattern of decreasing DOM with increasing distance from land, suggesting concentrations of DOM are controlled on large spatial scales by mixing between the open North Atlantic and either riverine sources or high DOM productivity in nearshore coastal waters driven by riverine nutrient discharge. Given the large size and long residence time of water in the North Sea, we find concentrations are commonly modified from simple conservative mixing between two endmembers. We observe differences in dissolved organic carbon (DOC) and dissolved organic nitrogen (DON) concentrations and land–ocean gradients between the two summers, leading to an estimated 10–20 Tg difference in the DOC inventory between the two years, which is of the same order of magnitude as the annual uptake of atmospheric CO2 by the North Sea system, and thus significant for the carbon budget of the North Sea. This difference is not consistent with additional terrestrial loading and is more likely to be due to balancing of mixing and in situ production and loss processes across the North Sea. Differences were particularly pronounced in the bottom layer of the seasonally stratifying northern North Sea, with higher DOC and C:N ratio in 2011 than in 2012. Using other data, we consider the extent to which these differences in the concentrations and C:N ratio of DOM could be due to changes in the biogeochemistry or physical circulation in the two years, or a combination of both. The evidence we have is consistent with a flushing event in winter 2011/12 exchanging DOM-rich, high C:N shelf waters, which may have accumulated over more than 1 year, with deep North Atlantic waters with lower DOC and marginally higher DON. We discuss the implications of these observations for the shelf sea carbon pump and the export of carbon-rich organic matter off the shelf and hypothesise that intermittent flushing of temperate shelf systems may be a key mechanism in the maintenance of the continental shelf pump, via the accumulation and subsequent export of carbon-rich DOM.

The nature of atmospheric transport of aerosol particles from land to the ocean is described. The magnitude and significance for ocean biogeochemistry is then discussed for the atmospheric deposition of some particular components—nutrients (nitrogen, phosphorus, and iron), some trace metals, organic matter generally and then some specific organic compounds.

Dust is produced primarily in desert regions and transported long distances through the atmosphere to the oceans. Upon deposition of dust, its dissolution can provide an important source of a range of nutrients, particularly iron, to microbes living in open ocean surface waters. The dust supply is greatest nearest to deserts, hence in the Northern Hemisphere. The Southern Ocean region is farthest from these dust sources and shows clear evidence that phytoplankton primary production is limited, at least in part, by the rate of supply of iron. Iron is also essential for nitrogen fixation. In regions of high atmospheric iron supply, such as the tropical North Atlantic, stimulation of nitrogen fixation drives the phytoplankton population toward a state in which phosphorus supply rates limit primary production. Atmospheric deposition is also an important source of nitrogen to the low latitude ocean, where it stimulates primary production. In this review we consider the sources, transport, and deposition of atmospheric dust/iron and nitrogen to the oceans and their impacts on plankton systems. In conclusion, we suggest key areas for future research.

Total and soluble trace metal concentrations were determined in atmospheric aerosol and rainwater samples collected during seven cruises in the south-east Atlantic. Back trajectories indicated that the samples all represented remote marine air masses, consistent with climatological expectations. Aerosol trace metal loadings were similar to previous measurements in clean, marine air masses. Median total Fe, Al, Mn, V, Co and Zn concentrations were 206, 346, 5, 3, 0.7 and 11 pmol m− 3 respectively. Solubility was operationally defined as the fraction extractable using a pH 4.7 ammonium acetate leach. Median soluble Fe, Al, Mn, V, Co, Zn, Cu, Ni, Cd and Pb concentrations were 6, 55, 1, 0.7, 0.06, 24, 2, 1, 0.05 and 0.3 pmol m− 3 respectively. Large ranges in fractional solubility were observed for all elements except Co; median solubility values for Fe, Al and Mn were below 20% while the median for Zn was 74%. Volume weighted mean rainwater concentrations were 704, 792, 32, 10, 3, 686, 25, 0.02, 0.3 and 10 nmol L− 1 for Fe, Al, Mn, V, Co, Zn, Cu, Ni, Cd and Pb respectively (n = 6). Wet deposition fluxes calculated from these values suggest that rain makes a significant contribution to total deposition in the study area for all elements except perhaps Ni.

New production (New P, the rate of net primary production (NPP) supported by exogenously supplied limiting nutrients) and net community production (NCP, gross primary production not consumed by community respiration) are closely related but mechanistically distinct processes. They set the carbon balance in the upper ocean and define an upper limit for export from the system. The relationships, relative magnitudes and variability of New P (from 15 NO 3 – uptake), O 2 : argon-based NCP and sinking particle export (based on the 238 U : 234 Th disequilibrium) are increasingly well documented but still not clearly understood. This is especially true in remote regions such as polar marginal ice zones. Here we present a 3-year dataset of simultaneous measurements made at approximately 50 stations along the Western Antarctic Peninsula (WAP) continental shelf in midsummer (January) 2012–2014. Net seasonal-scale changes in water column inventories (0–150 m) of nitrate and iodide were also estimated at the same stations. The average daily rates based on inventory changes exceeded the shorter-term rate measurements. A major uncertainty in the relative magnitude of the inventory estimates is specifying the start of the growing season following sea-ice retreat. New P and NCP(O 2 ) did not differ significantly. New P and NCP(O 2 ) were significantly greater than sinking particle export from thorium-234. We suggest this is a persistent and systematic imbalance and that other processes such as vertical mixing and advection of suspended particles are important export pathways. This article is part of the theme issue ‘The marine system of the west Antarctic Peninsula: status and strategy for progress in a region of rapid change’.

We demonstrate that land reclamation in estuaries is resulting in very large-scale loss of intertidal area and disconnection of stored sediment with the water column. This process is not just causing loss of estuarine ecosystem services, it is also having a major deleterious impact on the ability of estuaries to retain nutrients and trace metals. The global scale of loss of estuarine wetlands and subtidal sediments has reached the point where the impact of this loss of estuarine retention is likely to be affecting coastal seas worldwide and possibly global element cycles.

The Ross Sea polynya is one of the most productive regions in the Southern Ocean. However, limited access and high spatio-temporal variability of physical and biological processes limit the use of conventional oceanographic methods to measure early season primary productivity. High-resolution observations from two Seagliders provide insights into the timing of a bloom in the southern Ross Sea polynya in December 2010. Changes in chlorophyll and oxygen concentrations are used to assess bloom dynamics. Using a ratio of dissolved oxygen to carbon, net primary production is estimated over the duration of the bloom showing a sensitive balance between net autotrophy and heterotrophy. The two gliders, observing spatially distinct regions during the same period, found net community production rates of -0.9±0.7 and 0.7±0.4 g C m-2 d-1. The difference highlights the spatial variability of biological processes and is probably caused by observing different stages of the bloom. The challenge of obtaining accurate primary productivity estimates highlights the need for increased observational efforts, particularly focusing on subsurface processes not resolved using surface or remote observations. Without an increased observational effort and the involvement of emerging technologies, it will not be possible to determine the seasonal trophic balance of the Ross Sea polynya and quantify the shelf’s importance in carbon export.

We present the distribution and C : N stoichiometry of dissolved organic matter (DOM) in the North Sea in 2 summers (August 2011 and August 2012), with supporting data from the intervening winter (January 2012). This data demonstrates local variability superimposed on a general pattern of decreasing DOM with increasing salinity, suggesting strong control over broad scale concentrations by mixing between riverine sources and the open North Atlantic. We observe differences in DOC and DON concentrations and gradients between the two summers, leading to an estimated 10–20 Tg difference in the DOM carbon inventory between the 2 years, which is of the same order as the annual uptake of atmospheric CO2 by the North Sea system, and thus significant for the carbon budget of the North Sea. Differences were particularly pronounced in the bottom layer of the seasonally stratifying Northern North Sea, with higher DOC and lower DON in 2011 and lower C : N ratio and more moderate concentrations of DOC and DON in 2012. Using other data we consider the extent to which these differences in the concentrations and C : N ratio of DOM could be due to differences in the biogeochemistry or physical circulation in the 2 years, or a combination of both. We discuss the implications of these observations for the shelf sea carbon pump and the export of carbon rich organic matter off the shelf.

We report a new synthesis of best estimates of the inputs of fixed nitrogen to the world ocean via atmospheric deposition and compare this to fluvial inputs and dinitrogen fixation. We evaluate the scale of human perturbation of these fluxes. Fluvial inputs dominate inputs to the continental shelf, and we estimate that about 75% of this fluvial nitrogen escapes from the shelf to the open ocean. Biological dinitrogen fixation is the main external source of nitrogen to the open ocean, i.e., beyond the continental shelf. Atmospheric deposition is the primary mechanism by which land-based nitrogen inputs, and hence human perturbations of the nitrogen cycle, reach the open ocean. We estimate that anthropogenic inputs are currently leading to an increase in overall ocean carbon sequestration of ~0.4% (equivalent to an uptake of 0.15 Pg C yr−1 and less than the Duce et al. (2008) estimate). The resulting reduction in climate change forcing from this ocean CO2 uptake is offset to a small extent by an increase in ocean N2O emissions. We identify four important feedbacks in the ocean atmosphere nitrogen system that need to be better quantified to improve our understanding of the perturbation of ocean biogeochemistry by atmospheric nitrogen inputs. These feedbacks are recycling of (1) ammonia and (2) organic nitrogen from the ocean to the atmosphere and back, (3) the suppression of nitrogen fixation by increased nitrogen concentrations in surface waters from atmospheric deposition, and (4) increased loss of nitrogen from the ocean by denitrification due to increased productivity stimulated by atmospheric inputs.

We consider here first the nature of nutrient transport through estuaries and in particular the capacity of estuaries to modify that flux. We then focus particularly on the Wash system in the UK as an example of a particular type of “small estuary”, and also consider some tropical estuarine systems in Malaysia. We present nutrient budgets for the Wash system now and create estimates of these budgets 3000 years ago. These show that currently the system is a small sink for fluvial nitrate (∼30% removal) largely due to denitrification and dissolved inorganic phosphorus (∼24%) by burial. 3000 years ago, prior to large scale human intervention to reclaim wetlands for agriculture, the Wash system was much bigger and operated as a sink for all terrestrial nitrogen (albeit with much lower inputs) and also a sink for nitrate from the North Sea, predominantly via organic nitrogen burial. A similar change with time is evident in the phosphorus flux. We suggest that this change in function of this estuarine system has been replicated in many other estuarine systems. Given the key role of benthic processes of burial and denitrification we go on to suggest that the classification of estuaries in terms of area and river flow may offer a route to a typology of estuarine nutrient retention efficiency.

The atmospheric deposition of both macronutrients and micronutrients plays an important role in driving primary productivity, particularly in the low-latitude ocean. We report aerosol major ion measurements for five ship-based sampling campaigns in the western Pacific from similar to 25 degrees N to 20 degrees S and compare the results with those from Atlantic meridional transects (similar to 50 degrees N to 50 degrees S) with aerosols collected and analyzed in the same laboratory, allowing full incomparability. We discuss sources of the main nutrient species (nitrogen (N), phosphorus (P), and iron (Fe)) in the aerosols and their stoichiometry. Striking north-south gradients are evident over both basins with the Northern Hemisphere more impacted by terrestrial dust sources and anthropogenic emissions and the North Atlantic apparently more impacted than the North Pacific. We estimate the atmospheric supply rates of these nutrients and the potential impact of the atmospheric deposition on the tropical western Pacific. Our results suggest that the atmospheric deposition is P deficient relative to the needs of the resident phytoplankton. These findings suggest that atmospheric supply of N, Fe, and P increases primary productivity utilizing some of the residual excess phosphorus (P*) in the surface waters to compensate for aerosol P deficiency. Regional primary productivity is further enhanced via the stimulation of nitrogen fixation fuelled by the residual atmospheric iron and P*. Our stoichiometric calculations reveal that a P* of 0.1 mu mol L-1 can offset the P deficiency in atmospheric supply for many months. This study suggests that atmospheric deposition may sustain similar to 10% of primary production in both the western tropical Pacific.

Iron has been found to limit primary productivity in high nutrient, low chlorophyll regions of the oceans, including the Southern Ocean. Here we assess the relative magnitudes and geographical distributions of the sources of iron (sedimentary, atmospheric, icebergs and sea ice) to the Southern Ocean, and their impact on productivity. We present an iron cycling model, based on the assumptions of iron and light limitation of primary production, which is embedded in an eddy resolving ocean general circulation model. We find that the injection depth of the various iron inputs determines their availability for driving production because dissolved iron may be scavenged prior to it entering the illuminated mixed layer where it can drive primary production. The model suggests that production is predominantly regulated by sediment-derived iron sources rather than icebergs, sea ice or atmospheric dust. We note non-linear response in productivity to changes in the strength of one or more iron sources due to scavenging. Sea ice influences productivity by modifying the timing of iron supply to the euphotic zone. We also show that in the Scotia Sea the majority of productivity is driven by sediment-sourced iron from the Antarctic Peninsula, with additional local hotspots driven by island sources.

Recent studies have highlighted the impact of sea surface iodide concentrations on the deposition of ozone to the sea surface and the sea to air flux of reactive iodine. The use of models to predict this flux demands accurate, spatially distributed sea surface iodide concentrations, but to date, the observational data required to support this is sparse and mostly arises from independent studies conducted on small geographical and temporal scales. We have compiled the available measurements of sea surface iodide to produce a data set spanning latitudes from 69°S to 66°N, which reveals a coherent, large scale distribution pattern, with highest concentrations observed in tropical waters. Relationships between iodide concentration and more readily available parameters (chlorophyll, nitrate, sea surface temperature, salinity, mixed layer depth) are evaluated as tools to predict iodide concentration. Of the variables tested, sea surface temperature is the strongest predictor of iodide concentration. Nitrate was also strongly inversely associated with iodide concentration, but chlorophyll-a was not.

This paper reviews atmospheric inputs of trace elements and nutrients to the oceans in the context of the GEOTRACES programme and provides new data from two Atlantic GEOTRACES cruises. We consider the deposition of nitrogen to the oceans, which is now dominated by anthropogenic emissions, the deposition of mineral dust and related trace elements, and the deposition of other trace elements which have a mixture of anthropogenic and dust sources. We then consider the solubility (as a surrogate for bioavailability) of the various elements. We consider briefly the sources, atmospheric transport and transformations of these elements and how this results in strong spatial deposition gradients. Solubility of the trace elements also varies systematically between elements, reflecting their sources and cycling, and for some trace elements there are also systematic gradients in solubility related to dust loading. Together, these effects create strong spatial gradients in the inputs of bioavailable trace elements to the oceans, and we are only just beginning to understand how these affect ocean biogeochemistry. This article is part of the themed issue ‘Biological and climatic impacts of ocean trace element chemistry’.

Dissolved iron (dFe) distributions and atmospheric and vertical subduction fluxes of dFe were determined in the upper water column for two meridional transects of the Atlantic Ocean. The data demonstrate the disparity between the iron biogeochemistry of the North and South Atlantic Ocean and show well-defined gradients of size fractionated iron species in surface waters between geographic provinces. The highest dFe and lowest mixed layer residence times (0.4–2.5 years) were found in the northern tropical and subtropical regions. In contrast, the South Atlantic Gyre had lower dFe concentrations ( 5 years), presumably due to lower atmospheric inputs and more efficient biological recycling of iron in this region. Vertical input fluxes of dFe to surface waters ranged from 20 to 170 nmol m–2 d–1 in the North Atlantic and tropical provinces, whereas average fluxes of 6–13 nmol m–2 d–1 were estimated for the South Atlantic. Our estimates showed that the variable dFe distribution over the surface Atlantic ( 50% of total vertical Fe flux to surface waters) rather than upwelling or vertical mixing. This demonstrates the strength of the connection between land-derived atmospheric Fe fluxes and the biological cycling of carbon and nitrogen in the Atlantic Ocean.

Atmospheric inputs of mineral dust supply iron and other trace metals to the remote ocean and can influence the marine carbon cycle due to iron's role as a potentially limiting micronutrient. Dust generation, transport, and deposition are highly heterogeneous, and there are very few remote marine locations where dust concentrations and chemistry (e.g., iron solubility) are routinely monitored. Here we use aerosol and rainwater samples collected during 10 large-scale research cruises to estimate the atmospheric input of iron, aluminum, and manganese to four broad regions of the Atlantic Ocean over two 3month periods for the years 2001-2005. We estimate total inputs of these metals to our study regions to be 4.2, 17, and 0.27Gmol in April-June and 4.9, 14, and 0.19Gmol in September-November, respectively. Inputs were highest in regions of high rainfall (the intertropical convergence zone and South Atlantic storm track), and rainfall contributed higher proportions of total input to wetter regions. By combining input estimates for total and soluble metals for these time periods, we calculated overall percentage solubilities for each metal that account for the contributions from both wet and dry depositions and the relative contributions from different aerosol types. Calculated solubilities were in the range 2.4%-9.1% for iron, 6.1%-15% for aluminum, and 54%-73% for manganese. We discuss sources of uncertainty in our estimates and compare our results to some recent estimates of atmospheric iron input to the Atlantic.

Results from extensive cruises in the years 2000 and 2001 throughout distinct ecohydrodynamic regions of the central and southern North Sea are presented and used to generate estimates of gross primary production and new production. An undulating CTD fitted with a fluorometer was towed over a distance of 12,000 kms. Fluorescence data were used to determine the chlorophyll distribution and derive estimates of phytoplankton biomass. These results were combined with estimates of primary production (new and regenerated) from experiments from one cruise in order to estimate gross production for a greater geographical extent. Results from repeat inter-annual transects showed that the strength of the thermocline and the associated deep chlorophyll maximum were variable. However, when the primary production was integrated over the 15–40 m depth, the variability between years was low. While the depth and strength of the deep chlorophyll maximum varied across the region, a deep chlorophyll maximum (DCM) is a consistent and widespread feature of this region at around 30 m depth. In 2001 the calculated average primary production rate in summer for the whole area surveyed was 0.91 g C m−2 day−1. This daily production equates to ~130 g C m−2 for the summer stratified period. In the offshore stratified regions around the Dogger Bank and Eastern Central North Sea primary production of 64 g C m−2 associated with the deep chlorophyll maximum (15–40 m) accounted for 60 % of total primary production during the summer stratified period (after the spring bloom). Approximately 66 % of new production in these areas occurred in the DCM. This study shows the extent of the DCM in the North Sea and demonstrates its importance in sustaining primary production after the spring bloom.

The results of fine mode ( 2 or methane sulphonic acid (MSA). Using our estimates of marine biogenic sulphate and measurements of MSA concentrations we confirm that the ratio of MSA/sulphate from DMS oxidation increases systematically from low to high latitudes, consistent with the laboratory measurements, inferences from field studies and modelling predictions of others.

Trace elements serve important roles as regulators of ocean processes including marine ecosystem dynamics and carbon cycling. The role of iron, for instance, is well known as a limiting micronutrient in the surface ocean. Several other trace elements also play crucial roles in ecosystem function and their supply therefore controls the structure, and possibly the productivity, of marine ecosystems. Understanding the biogeochemical cycling of these micronutrients requires knowledge of their diverse sources and sinks, as well as their transport and chemical form in the ocean. Much of what is known about past ocean conditions, and therefore about the processes driving global climate change, is derived from trace-element and isotope patterns recorded in marine deposits. Reading the geochemical information archived in marine sediments informs us about past changes in fundamental ocean conditions such as temperature, salinity, pH, carbon chemistry, ocean circulation and biological productivity. These records provide our principal source of information about the ocean's role in past climate change. Understanding this role offers unique insights into the future consequences of global change. The cycle of many trace elements and isotopes has been significantly impacted by human activity. Some of these are harmful to the natural and human environment due to their toxicity and/or radioactivity. Understanding the processes that control the transport and fate of these contaminants is an important aspect of protecting the ocean environment. Such understanding requires accurate knowledge of the natural biogeochemical cycling of these elements so that changes due to human activity can be put in context. Despite the recognised importance of understanding the geochemical cycles of trace elements and isotopes, limited knowledge of their sources and sinks in the ocean and the rates and mechanisms governing their internal cycling, constrains their application to illuminating the problems outlined above. Marine geochemists are poised to make significant progress in trace-element biogeochemistry. Advances in clean sampling protocols and analytical techniques provide unprecedented capability for high-density sampling and measurement of a wide range of trace elements and isotopes which can be combined with new modelling strategies that have evolved from the World Ocean Circulation Experiment (WOCE) and Joint Global Ocean Flux Study (JGOFS) programmes. A major new international research programme, GEOTRACES, has now been developed as a result of community input to study the global marine biogeochemical cycles of trace elements and their isotopes. Here, we describe this programme and its rationale

We report aerosol ammonium 15 N signatures for samples collected from research cruises on the South Atlantic and Caribbean using a new high sensitivity method. We confirm a pattern of isotopic signals from generally light (δ 15 N −5 to −10‰), for aerosols with very low ( −3 ) ammonium concentrations from the remote high latitude ocean, to generally heavier values (δ 15 N +5 to +10‰), for aerosols collected in temperate and tropical latitudes and with higher ammonium concentrations (>2 nmol m −3 ). We discuss whether this reflects a mixing of aerosols from two end-members (polluted continental and remote marine emissions), or isotopic fractionation during aerosol transport.

In stratified shelf seas, oxygen depletion beneath the thermocline is a result of a greater rate of biological oxygen demand than the rate of supply of oxygenated water. Suitably equipped gliders are uniquely placed to observe both the supply through the thermocline and the consumption of oxygen in the bottom layers. A Seaglider was deployed in the shallow (≈ 100 m) stratified North Sea in a region of known low oxygen during August 2011 to investigate the processes regulating supply and consumption of dissolved oxygen below the pycnocline. The first deployment of such a device in this area, it provided extremely high-resolution observations, 316 profiles (every 16 min, vertical resolution of 1 m) of conductivity, temperature, and depth (CTD), dissolved oxygen concentrations, backscatter, and fluorescence during a 3-day deployment.The high temporal resolution observations revealed occasional small-scale events (< 200 m or 6 h) that supply oxygenated water to the bottom layer at a rate of 2 ± 1 µmol dm−3 day−1. Benthic and pelagic oxygen sinks, quantified through glider observations and past studies, indicate more gradual background consumption rates of 2.5 ± 1 µmol dm−3 day−1. This budget revealed that the balance of oxygen supply and demand is in agreement with previous studies of the North Sea. However, the glider data show a net oxygen consumption rate of 2.8 ± 0.3 µmol dm−3 day−1, indicating a localized or short-lived (The glider proved to be an excellent tool for monitoring shelf sea processes despite challenges to glider flight posed by high tidal velocities, shallow bathymetry, and very strong density gradients. The direct observation of these processes allows more up to date rates to be used in the development of ecosystem models.

Mineral dust is a complex entity containing a range of iron minerals including poorly crystalline to crystalline iron oxides to clay minerals. Important progress has been made to characterize iron mineralogical compositions in the dust recently. These include the quantification of the content of crystalline hematite and goethite, which appear to show a regional variation in North Africa as a result of the differences in the degree of chemical weathering. Fractional Fe solubility (dissolved to total iron, FFS) in the atmospheric aerosols has been reported to range from 0.1% to 80%. However, FFS is usually less than 0.5% in the non-atmospherically-processed dust, suggesting that FFS can be enhanced by atmospheric processes. One of the atmospheric processes, gravitational settling of dust, which has been previously hypothesized to cause the abovementioned enhancement of FFS during dust transport has been shown to be insignificant. Cycling of dust particles in the clouds, in which pH is usually higher than 4, and in the aerosol phase, in which pH is usually substantially lower, can significantly affect iron speciation and FFS. Laboratory experiments showed that a significant amount of iron (>0.5%) can only be solubilized in the dust when pH is lower than 4. These laboratory data suggest that acid processing rather than cloud processing might be a prime mechanism to cause an increase in FFS in the dust during transport. Further laboratory studies, field measurements, and modelling are needed to increase the ability of models to quantify the atmospheric processing of iron in the dust. (c) 2012 Elsevier B.V. All rights reserved.

The Cefas SmartBuoy network provides a unique insight into the biogeochemical dynamics of the Northern European shelf seas, particularly the North Sea, through high-resolution automated offshore water sampling. We present total dissolved nitrogen and dissolved organic nitrogen (DON) from the Dowsing SmartBuoy site (53.531° N, 1.053° E) from January to October 2010, the first high resolution seasonal (winter-autumn) cycle of DON from the open North Sea. On top of a refractory background DON concentration of approximately 5 μM, a rapid increase in DON of a further ∼5 μM is observed over the course of the spring bloom. This rapidly produced DON declines at an estimated net decay rate of between 0.6 and 1.8 μM month−1. The slow decay suggests that the majority of the additional DON produced during the spring bloom is of semi-labile nature and has a lifetime of weeks to months. The dataset allows us to tightly constrain the budget for water column nitrogen over the winter, spring and summer of 2010 and clearly demonstrates the ‘sawtooth’ nature of the seasonal cycle of DON in the open North Sea, which has been impossible to resolve with a more traditional ship-based mode of operation. This work highlights the importance of autonomous sampling approaches in better understanding shelf sea biogeochemistry in the future.

Reactive nitrogen (Nr) compounds have different fates in the atmosphere due to differences in governing processes of physical transport, deposition and chemical transformation. Nr compounds addressed here include reduced nitrogen (NHx: ammonia (NH3) and its reaction product ammonium (NH4+)), oxidized nitrogen (NOy: nitrogen monoxide (NO) + nitrogen dioxide (NO2) and their reaction products) as well as organic nitrogen compounds (organic N). Pollution abatement strategies need to take into account these differences in the governing processes of these compounds when assessing their impact on ecosystem services, biodiversity, human health and climate. NOx (NO + NO2) emitted from traffic affects human health in urban areas where the presence of buildings increases the residence time in streets. In urban areas this leads to enhanced exposure of the population to NOx concentrations. NOx emissions have little impact on nearby ecosystems because of the small dry deposition rates of NOx. These compounds need to be converted into nitric acid (HNO3) before removal through deposition is efficient. HNO3 sticks quickly to any surface and is thereby either dry deposited or incorporated into aerosols as nitrate (NO3−). In contrast to NOx compounds, NH3 has potentially high impacts on ecosystems near the main agricultural sources of NH3 because of its large ground-level concentrations along with large dry deposition rates. Aerosol phase NH4+ and NO3− contribute significantly to background PM2.5 and PM10 (mass of aerosols with a diameter of less than 2.5 and 10 μm, respectively) with an impact on radiation balance as well as potentially on human health. Little is known quantitatively and qualitatively about organic N in the atmosphere, other than that it contributes a significant fraction of wet-deposited N, and is present in both gaseous and particulate forms in the atmosphere. Further studies are needed to characterize the sources, air chemistry and removal rates of organic N emissions.