Earth, Wind, Fire, and Pollution: Aerosol Nutrient Sources and Impacts on Ocean Biogeochemistry.

A key Earth system science question is the role of atmospheric deposition in supplying vital nutrients to the phytoplankton that form the base of marine food webs. Industrial and vehicular pollution, wildfires, volcanoes, biogenic debris, and desert dust all carry nutrients within their plumes throughout the globe. In remote ocean ecosystems, aerosol deposition represents an essential new source of nutrients for primary production. The large spatiotemporal variability in aerosols from myriad sources combined with the differential responses of marine biota to changing fluxes makes it crucially important to understand where, when, and how much nutrients from the atmosphere enter marine ecosystems. This review brings together existing literature, experimental evidence of impacts, and new atmospheric nutrient observations that can be compared with atmospheric and ocean biogeochemistry modeling. We evaluate the contribution and spatiotemporal variability of nutrient-bearing aerosols from desert dust, wildfire, volcanic, and anthropogenic sources, including the organic component, deposition fluxes, and oceanic impacts.

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.

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.

Evaluation of global simulations of aerosol particle and cloud condensation nuclei number, with implications for cloud droplet formation.

A total of 16 global chemistry transport models and general circulation models have participated in this study; 14 models have been evaluated with regard to their ability to reproduce the near-surface observed number concentration of aerosol particles and cloud condensation nuclei (CCN), as well as derived cloud droplet number concentration (CDNC). Model results for the period 2011-2015 are compared with aerosol measurements (aerosol particle number, CCN and aerosol particle composition in the submicron fraction) from nine surface stations located in Europe and Japan. The evaluation focuses on the ability of models to simulate the average across time state in diverse environments and on the seasonal and short-term variability in the aerosol properties. There is no single model that systematically performs best across all environments represented by the observations. Models tend to underestimate the observed aerosol particle and CCN number concentrations, with average normalized mean bias (NMB) of all models and for all stations, where data are available, of -24% and -35% for particles with dry diameters > 50 and > 120nm, as well as -36% and -34% for CCN at supersaturations of 0.2% and 1.0%, respectively. However, they seem to behave differently for particles activating at very low supersaturations (< 0.1 %) than at higher ones. A total of 15 models have been used to produce ensemble annual median distributions of relevant parameters. The model diversity (defined as the ratio of standard deviation to mean) is up to about 3 for simulated N3 (number concentration of particles with dry diameters larger than 3 nm) and up to about 1 for simulated CCN in the extra-polar regions. A global mean reduction of a factor of about 2 is found in the model diversity for CCN at a supersaturation of 0.2% (CCN0.2) compared to that for N3, maximizing over regions where new particle formation is important. An additional model has been used to investigate potential causes of model diversity in CCN and bias compared to the observations by performing a perturbed parameter ensemble (PPE) accounting for uncertainties in 26 aerosol-related model input parameters. This PPE suggests that biogenic secondary organic aerosol formation and the hygroscopic properties of the organic material are likely to be the major sources of CCN uncertainty in summer, with dry deposition and cloud processing being dominant in winter. Models capture the relative amplitude of the seasonal variability of the aerosol particle number concentration for all studied particle sizes with available observations (dry diameters larger than 50, 80 and 120 nm). The short-term persistence time (on the order of a few days) of CCN concentrations, which is a measure of aerosol dynamic behavior in the models, is underestimated on average by the models by 40% during winter and 20% in summer. In contrast to the large spread in simulated aerosol particle and CCN number concentrations, the CDNC derived from simulated CCN spectra is less diverse and in better agreement with CDNC estimates consistently derived from the observations (average NMB -13% and -22% for updraft velocities 0.3 and 0.6 ms-1, respectively). In addition, simulated CDNC is in slightly better agreement with observationally derived values at lower than at higher updraft velocities (index of agreement 0.64 vs. 0.65). The reduced spread of CDNC compared to that of CCN is attributed to the sublinear response of CDNC to aerosol particle number variations and the negative correlation between the sensitivities of CDNC to aerosol particle number concentration (∂N d/∂N a) and to updraft velocity (∂N d/∂w). Overall, we find that while CCN is controlled by both aerosol particle number and composition, CDNC is sensitive to CCN at low and moderate CCN concentrations and to the updraft velocity when CCN levels are high. Discrepancies are found in sensitivities ∂N d/∂N a and ∂N d/∂w; models may be predisposed to be too "aerosol sensitive" or "aerosol insensitive" in aerosol-cloud-climate interaction studies, even if they may capture average droplet numbers well. This is a subtle but profound finding that only the sensitivities can clearly reveal and may explain inter-model biases on the aerosol indirect effect.

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° × 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.

Understanding the nature of atmospheric acid processing of mineral dusts in supplying bioavailable phosphorus to the oceans.

Acidification of airborne dust particles can dramatically increase the amount of bioavailable phosphorus (P) deposited on the surface ocean. Experiments were conducted to simulate atmospheric processes and determine the dissolution behavior of P compounds in dust and dust precursor soils. Acid dissolution occurs rapidly (seconds to minutes) and is controlled by the amount of H+ ions present. For H+ < 10-4 mol/g of dust, 1-10% of the total P is dissolved, largely as a result of dissolution of surface-bound forms. At H+ > 10-4 mol/g of dust, the amount of P (and calcium) released has a direct proportionality to the amount of H+ consumed until all inorganic P minerals are exhausted and the final pH remains acidic. Once dissolved, P will stay in solution due to slow precipitation kinetics. Dissolution of apatite-P (Ap-P), the major mineral phase in dust (79-96%), occurs whether calcium carbonate (calcite) is present or not, although the increase in dissolved P is greater if calcite is absent or if the particles are externally mixed. The system was modeled adequately as a simple mixture of Ap-P and calcite. P dissolves readily by acid processes in the atmosphere in contrast to iron, which dissolves more slowly and is subject to reprecipitation at cloud water pH. We show that acidification can increase bioavailable P deposition over large areas of the globe, and may explain much of the previously observed patterns of variability in leachable P in oceanic areas where primary productivity is limited by this nutrient (e.g., Mediterranean).