Observation- and model-based estimates of particulate dry nitrogen deposition to the oceans

Anthropogenic nitrogen (N) emissions to the atmosphere have increased significantly the deposition of nitrate (NO− 3 ) and ammonium (NH+ 4 ) to the surface waters of the open ocean, with potential impacts on marine productivity and the global carbon cycle. Global-scale understanding of the impacts of N deposition to the oceans is reliant on our ability to produce and validate models of nitrogen emission, atmospheric chemistry, transport and deposition. In this work, ∼ 2900 observations of aerosol NO− 3 and NH+ 4 concentrations, acquired from sampling aboard ships in the period 1995–2012, are used to assess the performance of modelled N concentration and deposition fields over the remote ocean. Three ocean regions (the eastern tropical North Atlantic, the northern Indian Ocean and northwest Pacific) were selected, in which the density and distribution of observational data were considered sufficient to provide effective comparison to model products. All of these study regions are affected by transport and deposition of mineral dust, which alters the deposition of N, due to uptake of nitrogen oxides (NOx ) on mineral surfaces. Assessment of the impacts of atmospheric N deposition on the ocean requires atmospheric chemical transport models to report deposition fluxes; however, these fluxes cannot be measured over the ocean. Modelling studies such as the Atmospheric Chemistry and Climate Model Intercomparison Project (ACCMIP), which only report deposition flux, are therefore very difficult to validate for dry deposition. Here, the available observational data were averaged over a 5◦×5 ◦ grid and compared to ACCMIP dry deposition fluxes (ModDep) of oxidised N (NOy ) and reduced N (NHx ) and to the following parameters from the Tracer Model 4 of the Environmental Chemical Processes Laboratory (TM4): ModDep for NOy , NHx and particulate NO− 3 and NH+ 4 , and surface-level particulate NO− 3 and NH+ 4 concentrations. As a model ensemble, ACCMIP can be expected to be more robust than TM4, while TM4 gives access to speciated parameters (NO− 3 and NH+ 4 ) that are more relevant to the observed parameters and which are not available in ACCMIP. Dry deposition fluxes (CalDep) were calculated from the observed concentrations using estimates of dry deposition velocities. Model–observation ratios (RA,n), weighted by gridcell area and number of observations, were used to assess the performance of the models. Comparison in the three study regions suggests that TM4 overestimates NO− 3 concentrations (RA,n = 1.4–2.9) and underestimates NH+ 4 concentrations (RA,n = 0.5–0.7), with spatial distributions in the tropical Atlantic and northern Indian Ocean not being reproduced by the model. In the case of NH+ 4 in the Indian Ocean, this discrepancy was probably due to seasonal biases in the sampling. Similar patterns were observed in the various comparisons of CalDep to ModDep (RA,n = 0.6–2.6 for NO− 3 , 0.6–3.1 for NH+ 4 ). Values of RA,n for NHx CalDep– ModDep comparisons were approximately double the corresponding values for NH+ 4 CalDep–ModDep comparisons due to the significant fraction of gas-phase NH3 deposition incorporated in the TM4 and ACCMIP NHx model products. All of the comparisons suffered due to the scarcity of observational data and the large uncertainty in dry deposition velocities used to derive deposition fluxes from concentrations. These uncertainties have been a major limitation on estimates of the flux of material to the oceans for several decades. Recommendations are made for improvements in N deposition estimation through changes in observations, modelling and model–observation comparison procedures. Validation of modelled dry deposition requires effective comparisons to observable aerosol-phase species’ concentrations, and this cannot be achieved if model products only report dry deposition flux over the ocean

Atmospheric Organic Material and the Nutrients Nitrogen and Phosphorus It Carries to the Ocean

[1] The global tropospheric budget of gaseous and particulate non‐methane organic matter (OM) is re‐examined to provide a holistic view of the role that OM plays in transporting the essential nutrients nitrogen and phosphorus to the ocean. A global 3‐dimensional chemistry‐transport model was used to construct the first global picture of atmospheric transport and deposition of the organic nitrogen (ON) and organic phosphorus (OP) that are associated with OM, focusing on the soluble fractions of these nutrients. Model simulations agree with observations within an order of magnitude. Depending on location, the observed water soluble ON fraction ranges from ∼3% to 90% (median of ∼35%) of total soluble N in rainwater; soluble OP ranges from ∼20–83% (median of ∼35%) of total soluble phosphorus. The simulations suggest that the global ON cycle has a strong anthropogenic component with ∼45% of the overall atmospheric source (primary and secondary) associated with anthropogenic activities. In contrast, only 10% of atmospheric OP is emitted from human activities. The model‐derived present‐day soluble ON and OP deposition to the global ocean is estimated to be ∼16 Tg‐N/yr and ∼0.35 Tg‐P/yr respectively with an order of magnitude uncertainty. Of these amounts ∼40% and ∼6%, respectively, are associated with anthropogenic activities, and 33% and 90% are recycled oceanic materials. Therefore, anthropogenic emissions are having a greater impact on the ON cycle than the OP cycle; consequently increasing emissions may increase P‐limitation in the oligotrophic regions of the world\u27s ocean that rely on atmospheric deposition as an important nutrient source

Observation- and model-based estimates of particulate dry nitrogen deposition to the oceans

Anthropogenic nitrogen (N) emissions to the atmosphere have increased significantly the deposition of nitrate (NO3-) and ammonium (NH4+) to the surface waters of the open ocean, with potential impacts on marine productivity and the global carbon cycle. Global-scale understanding of the impacts of N deposition to the oceans is reliant on our ability to produce and validate models of nitrogen emission, atmospheric chemistry, transport and deposition. In this work, ~2900 observations of aerosol NO3- and NH4+ concentrations, acquired from sampling aboard ships in the period 1995 - 2012, are used to assess the performance of modelled N concentration and deposition fields over the remote ocean. Three ocean regions (the eastern tropical North Atlantic, the northern Indian Ocean and northwest Pacific) were selected, in which the density and distribution of observational data were considered sufficient to provide effective comparison to model products. All of these study regions are affected by transport and deposition of mineral dust, which alters the deposition of N, due to uptake of nitrogen oxides (NOx) on mineral surfaces. Assessment of the impacts of atmospheric N deposition on the ocean requires atmospheric chemical transport models to report deposition fluxes, however these fluxes cannot be measured over the ocean. Modelling studies such as the Atmospheric Chemistry and Climate Model Intercomparison Project (ACCMIP), which only report deposition flux are therefore very difficult to validate for dry deposition. Here the available observational data were averaged over a 5° x 5° grid and compared to ACCMIP dry deposition fluxes (ModDep) of oxidised N (NOy) and reduced N (NHx) and to the following parameters from the TM4-ECPL (TM4) model: ModDep for NOy, NHx and particulate NO3- and NH4+, and surface-level particulate NO3- and NH4+ concentrations. As a model ensemble, ACCMIP can be expected to be more robust than TM4, while TM4 gives access to speciated parameters (NO3- and NH4+) that are more relevant to the observed parameters and which are not available in ACCMIP. Dry deposition fluxes (CalDep) were calculated from the observed concentrations using estimates of dry deposition velocities. Model – observation ratios, weighted by grid-cell area and numbers of observations, (RA,n) were used to assess the performance of the models. Comparison in the three study regions suggests that TM4 over-estimates NO3- concentrations (RA,n = 1.4 – 2.9) and under-estimates NH4+ concentrations (RA,n = 0.5 – 0.7), with spatial distributions in the tropical Atlantic and northern Indian Ocean not being reproduced by the model. In the case of NH4+ in the Indian Ocean, this discrepancy was probably due to seasonal biases in the sampling. Similar patterns were observed in the various comparisons of CalDep to ModDep (RA,n = 0.6 – 2.6 for NO3-, 0.6 – 3.1 for NH4+). Values of RA,n for NHx CalDep - ModDep comparisons were approximately double the corresponding values for NH4+ CalDep - ModDep comparisons due to the significant fraction of gas-phase NH3 deposition incorporated in the TM4 and ACCMIP NHx model products. All of the comparisons suffered due to the scarcity of observational data and the large uncertainty in dry deposition velocities used to derive deposition fluxes from concentrations. These uncertainties have been a major limitation on estimates of the flux of material to the oceans for several decades. Recommendations are made for improvements in N deposition estimation through changes in observations, modelling and model – observation comparison procedures. Validation of modelled dry deposition requires effective comparisons to observable aerosol-phase species concentrations and this cannot be achieved if model products only report dry deposition flux over the ocean

The geochemical cycling of reactive chlorine through the marine troposphere

Heterogeneous reactions involving sea‐salt aerosol in the marine troposphere are the major global source for volatile inorganic chlorine. We measured reactant and product species hypothesized to be associated with these chemical transformations as a function of phase, particle size, and altitude over the North Atlantic Ocean during the summer of 1988. Concentrations of HCl were typically less than 1.0 ppbv near the sea surface and decreased with altitude and with distance from the U.S. east coast. Concentrations of Cl volatilized from aerosols were generally equivalent to the corresponding concentrations of HCl and ranged from less than detection limits to 125 nmol m−3 STP. Highest absolute and percentage losses of particulate Cl were typically associated with elevated concentrations of anthropogenic combustion products. Concentrations of product nss SO42− and N03− in coarse aerosol fractions indicate that on average only 38% of measured Cl− deficits could be accounted for by the combined effects of acid‐base desorption and reactions involving nonacidic N gases. We hypothesize a mechanism for the Cl loss initiated by reaction of O3 at sea‐salt aerosol surfaces, generating Cl2 followed by rapid photochemical conversion of Cl2 to HCl via Cl atoms (Cl˙) and eventual recapture of HCl by the aerosol. Simulations with a zero‐dimension (0‐D) photochemical model suggest that oxidation by Cl˙ may be an important tropospheric sink for dimethyl sulfide and hydrocarbons. Under low‐NOx conditions, the rapid cycling of reactive Cl would provide a catalytic loss mechanism for O3, which would possibly explain the low O3 concentrations often observed above the world\u27s oceans

Pyrogenic iron: The missing link to high iron solubility in aerosols

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

Microplastics and nanoplastics in the marine-atmosphere environment

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.Peer reviewe

Changing atmospheric acidity as a modulator of nutrient deposition and ocean biogeochemistry

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

Quantification of myelin loss in frontal lobe white matter in vascular dementia, Alzheimer's disease, and dementia with Lewy bodies

The aim of this study was to characterize myelin loss as one of the features of white matter abnormalities across three common dementing disorders. We evaluated post-mortem brain tissue from frontal and temporal lobes from 20 vascular dementia (VaD), 19 Alzheimer’s disease (AD) and 31 dementia with Lewy bodies (DLB) cases and 12 comparable age controls. Images of sections stained with conventional luxol fast blue were analysed to estimate myelin attenuation by optical density. Serial adjacent sections were then immunostained for degraded myelin basic protein (dMBP) and the mean percentage area containing dMBP (%dMBP) was determined as an indicator of myelin degeneration. We further assessed the relationship between dMBP and glutathione S-transferase (a marker of mature oligodendrocytes) immunoreactivities. Pathological diagnosis significantly affected the frontal but not temporal lobe myelin attenuation: myelin density was most reduced in VaD compared to AD and DLB, which still significantly exhibited lower myelin density compared to ageing controls. Consistent with this, the degree of myelin loss was correlated with greater %dMBP, with the highest %dMBP in VaD compared to the other groups. The %dMBP was inversely correlated with the mean size of oligodendrocytes in VaD, whereas it was positively correlated with their density in AD. A two-tier regression model analysis confirmed that the type of disorder (VaD or AD) determines the relationship between %dMBP and the size or density of oligodendrocytes across the cases. Our findings, attested by the use of three markers, suggest that myelin loss may evolve in parallel with shrunken oligodendrocytes in VaD but their increased density in AD, highlighting partially different mechanisms are associated with myelin degeneration, which could originate from hypoxic–ischaemic damage to oligodendrocytes in VaD whereas secondary to axonal degeneration in AD