Organic nitrogen in aerosols and precipitation at Barbados and Miami: Implications regarding sources, transport and deposition to the western subtropical North Atlantic

The deposition of anthropogenic nitrogen (N) species is believed to have a significant impact on the oligotrophic North Atlantic, but the magnitude of ecological effects remains uncertain because the deposition of water soluble organic N (WSON) is poorly quantified. Here we present measurements of water soluble inorganic N (WSIN) and WSON in aerosol and rain at two subtropical North Atlantic time series sites: Barbados and Miami. WSON total deposition rates ranged from 17.9 mmol m−2 yr−1 to 49.6 mmol m−2 yr−1, contributing on average only 6–14% of total N deposition, less than half the poorly constrained global average which is typically cited as 30%. On an event basis, biomass burning and dust events yielded the largest concentrations of WSON. However, biomass burning was relatively infrequent and highly variable in composition, and much of the organic N associated with dust appeared to be externally adsorbed from pollution sources. Conversely, in Miami pollution made relatively small contributions of WSON on an event basis, but impacts were relatively frequent, making pollution one of the largest sources of WSON during the year. The largest contributor to WSON was volatile basic organic N (VBON) species, which were present at concentrations 1–2 times higher than particulate WSON. Despite VBON inputs, samples associated with pollution-source trajectories yielded much more inorganic N than WSON. Consequently, we would expect that in the future as anthropogenic N emissions increase, inorganic nitrogen will remain the dominant form of N that is deposited to the western North Atlantic

Aerosol Indirect Effects on the Nighttime Arctic Ocean Surface from Thin, Predominantly Liquid Clouds

Aerosol indirect effects have potentially large impacts on the Arctic Ocean surface energy budget, but model estimates of regional-scale aerosol indirect effects are highly uncertain and poorly validated by observations. Here we demonstrate a new way to quantitatively estimate aerosol indirect effects on a regional scale from remote sensing observations. In this study, we focus on nighttime, optically thin, predominantly liquid clouds. The method is based on differences in cloud physical and microphysical characteristics in carefully selected clean, average, and aerosol-impacted conditions. The cloud subset of focus covers just approximately 5 % of cloudy Arctic Ocean regions, warming the Arctic Ocean surface by approximately 1-1.4 W m(exp -2) regionally during polar night. However, within this cloud subset, aerosol and cloud conditions can be determined with high confidence using CALIPSO and CloudSat data and model output. This cloud subset is generally susceptible to aerosols, with a polar nighttime estimated maximum regionally integrated indirect cooling effect of approximately 0.11 W m(exp 2) at the Arctic sea ice surface (approximately 8 % of the clean background cloud effect), excluding cloud fraction changes. Aerosol presence is related to reduced precipitation, cloud thickness, and radar reflectivity, and in some cases, an increased likelihood of cloud presence in the liquid phase. These observations are inconsistent with a glaciation indirect effect and are consistent with either a deactivation effect or less-efficient secondary ice formation related to smaller liquid cloud droplets. However, this cloud subset shows large differences in surface and meteorological forcing in shallow and higher-altitude clouds and between sea ice and open-ocean regions. For example, optically thin, predominantly liquid clouds are much more likely to overlay another cloud over the open ocean, which may reduce aerosol indirect effects on the surface. Also, shallow clouds over open ocean do not appear to respond to aerosols as strongly as clouds over stratified sea ice environments, indicating a larger influence of meteorological forcing over aerosol microphysics in these types of clouds over the rapidly changing Arctic Ocean

Anthropogenic nitrogen inputs and impacts on oceanic N2O fluxes in the northern Indian Ocean: The need for an integrated observation and modelling approach

Anthropogenically-derived nitrogen input to the northern Indian Ocean has increased significantly in recent decades, based on both observational and model-derived estimates This external nutrient source is supplied by atmospheric deposition and riverine fluxes, and has the potential to affect the vulnerable biogeochemical systems of the Arabian Sea and Bay of Bengal, influencing productivity and oceanic production of the greenhouse-gas nitrous-oxide (N2O). We summarize current estimates of this external nitrogen source to the northern Indian Ocean from observations and models, highlight implications for regional marine N2O emissions using model-based analyses, and make recommendations for measurement and model needs to improve current estimates and future predictions of this impact. Current observationally-derived estimates of deposition and riverine nitrogen inputs are limited by sparse measurements and uncertainties on accurate characterization of nitrogen species composition. Ocean model assessments of the impact of external nitrogen sources on regional marine N2O production in the northern Indian Ocean estimate potentially significant changes but also have large associated uncertainties. We recommend an integrated program of basin-wide measurements combined with high-resolution modeling and more detailed characterization of nitrogen-cycle process to address these uncertainties and improve current estimates and predictions

Methods for the sampling and analysis of marine aerosols: results from the 2008 GEOTRACES aerosol intercalibration experiment

Atmospheric deposition of trace elements and isotopes (TEI) is an important source of trace metals to the open ocean, impacting TEI budgets and distributions, stimulating oceanic primary productivity, and influencing biological community structure and function. Thus, accurate sampling of aerosol TEIs is a vital component of ongoing GEOTRACES cruises, and standardized aerosol TEI sampling and analysis procedures allow the comparison of data from different sites and investigators. Here, we report the results of an aerosol analysis intercalibration study by seventeen laboratories for select GEOTRACES-relevant aerosol species (Al, Fe, Ti, V, Zn, Pb, Hg, NO3-, and SO42-) for samples collected in September 2008. The collection equipment and filter substrates are appropriate for the GEOTRACES program, as evidenced by low blanks and detection limits relative to analyte concentrations. Analysis of bulk aerosol sample replicates were in better agreement when the processing protocol was constrained (+/- 9% RSD or better on replicate analyses by a single lab, n = 7) than when it was not (generally 20% RSD or worse among laboratories using different methodologies), suggesting that the observed variability was mainly due to methodological differences rather than sample heterogeneity. Much greater variability was observed for fractional solubility of aerosol trace elements and major anions, due to differing extraction methods. Accuracy is difficult to establish without an SRM representative of aerosols, and we are developing an SRM for this purpose. Based on these findings, we provide recommendations for the GEOTRACES program to and macro-nutrients to the open ocean (Okin et al. 2011) and is a key component of the international GEOTRACES program (GEOTRACES Planning Group 2006). A priority of the GEOTRACES program is to quantify both major and trace elements (e. g., Al, Fe, Ti, V, Zn, Pb, and Hg) and species such as nitrate and sulfate in marine aerosols. Therefore, marine aerosol samples collected during GEOTRACES cruises must follow sampling protocols that permit the collection and analysis of as many elements and compounds as possible, while meeting the constraints associated with basin-wide oceanographic cruises (e. g., space limitations, high-frequency sampling, etc.)

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

US SOLAS Science Report

The Surface Ocean – Lower Atmosphere Study (SOLAS) (http://www.solas-int.org/) is an international research initiative focused on understanding the key biogeochemical-physical interactions and feedbacks between the ocean and atmosphere that are critical elements of climate and global biogeochemical cycles. Following the release of the SOLAS Decadal Science Plan (2015-2025) (Brévière et al., 2016), the Ocean-Atmosphere Interaction Committee (OAIC) was formed as a subcommittee of the Ocean Carbon and Biogeochemistry (OCB) Scientific Steering Committee to coordinate US SOLAS efforts and activities, facilitate interactions among atmospheric and ocean scientists, and strengthen US contributions to international SOLAS. In October 2019, with support from OCB, the OAIC convened an open community workshop, Ocean-Atmosphere Interactions: Scoping directions for new research with the goal of fostering new collaborations and identifying knowledge gaps and high-priority science questions to formulate a US SOLAS Science Plan. Based on presentations and discussions at the workshop, the OAIC and workshop participants have developed this US SOLAS Science Plan. The first part of the workshop and this Science Plan were purposefully designed around the five themes of the SOLAS Decadal Science Plan (2015-2025) (Brévière et al., 2016) to provide a common set of research priorities and ensure a more cohesive US contribution to international SOLAS.This report was developed with federal support of NSF (OCE-1558412) and NASA (NNX17AB17G)