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Mineral dust is the major source of external micro-nutrients such as iron (Fe) to the open ocean. However, large uncertainties in model estimates of Fe emissions and aerosol-bearing Fe solubility (i.e., the ratio of labile Fe (LFe) to total Fe (TFe)) in the Southern Hemisphere (SH) hampered accurate estimates of atmospheric delivery of bioavailable Fe to the Southern Ocean. This study applied an inverse modeling technique to a global aerosol chemistry transport model (IMPACT) in order to optimize predictions of mineral aerosol Fe concentrations based on recent observational data over Australian coastal regions (110°E–160°E and 10°S–41°S). The optimized (a posteriori) model did not only better capture aerosol TFe concentrations downwind from Australian dust outbreak but also successfully reproduced enhanced Fe solubility (7.8 ± 8.4%) and resulted in much better agreement of LFe concentrations with the field measurements (1.4 ± 1.5 vs. 1.4 ± 2.3 ng Fe m–3). The a posteriori model estimates suggested that bushfires contributed a large fraction of LFe concentrations in aerosols, although substantial contribution from missing sources (e.g., coal mining activities, volcanic eruption, and secondary formation) was still inferred. These findings may have important implications for the projection of future micro-nutrient supply to the oceans as increasing frequency and intensity of open biomass burning are projected in the SH.

International audience; 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. Expected final online publication date for the Annual Review of Marine Science, Volume 14 is January 2022. Please see http://www.annualreviews.org/page/journal/pubdates for revised estimates.

Droughts and climate-change-driven warming are leading to more frequent and intense wildfires1,2,3, arguably contributing to the severe 2019–2020 Australian wildfires4. The environmental and ecological impacts of the fires include loss of habitats and the emission of substantial amounts of atmospheric aerosols5,6,7. Aerosol emissions from wildfires can lead to the atmospheric transport of macronutrients and bio-essential trace metals such as nitrogen and iron, respectively8,9,10. It has been suggested that the oceanic deposition of wildfire aerosols can relieve nutrient limitations and, consequently, enhance marine productivity11,12, but direct observations are lacking. Here we use satellite and autonomous biogeochemical Argo float data to evaluate the effect of 2019–2020 Australian wildfire aerosol deposition on phytoplankton productivity. We find anomalously widespread phytoplankton blooms from December 2019 to March 2020 in the Southern Ocean downwind of Australia. Aerosol samples originating from the Australian wildfires contained a high iron content and atmospheric trajectories show that these aerosols were likely to be transported to the bloom regions, suggesting that the blooms resulted from the fertilization of the iron-limited waters of the Southern Ocean. Climate models project more frequent and severe wildfires in many regions1,2,3. A greater appreciation of the links between wildfires, pyrogenic aerosols13, nutrient cycling and marine photosynthesis could improve our understanding of the contemporary and glacial–interglacial cycling of atmospheric CO2 and the global climate system. Analyses of satellite aerosol observations used in this study were produced with the Giovanni online data system, developed and maintained by the NASA GES DISC. We thank SeaWiFS and MODIS mission scientists and associated NASA personnel for the production of the data used in this research effort. The BGC-Argo data were collected and made freely available by the International Argo Program and the national programs that contribute to it (http://www.argo.ucsd.edu, http://argo.jcommops.org). The Argo Program is part of the Global Ocean Observing System (https://doi.org/10.17882/42182). W.T. is supported by the Harry H. Hess Postdoctoral Fellowship from Princeton University. N.C. is supported by the “Laboratoire d’Excellence” LabexMER (ANR‐10‐LABX‐19) and co-funded by a grant from the French government under the program “Investissements d’Avenir”. S.B. acknowledges the AXA Research Fund for the support of the long-term research line on Sand and Dust Storms at the Barcelona Supercomputing Center (BSC) and CAMS Global Validation (CAMS-84). P.G.S., J.L., M.M.G.P. and A.R.B. are supported by the Australian Research Council Discovery Projects scheme (DP190103504). P.G.S. and J.W. are supported by the Australian Research Council Centre of Excellence for Climate Extremes (CLEX: CE170100023). J.L. is supported by the European Union’s Horizon 2020 research and innovation programme under the Marie Skłodowska-Curie grant agreement no. 754433. A.R.B. is supported by the Australian Research Council Future Fellowship scheme (FT130100037). R.M. is supported by the CSIRO Decadal Climate Forecasting Project. We thank M. Strzelec, M. East, T. Holmes, M. Corkill, S. Meyerink and the Wellington Park Management Trust for help with installation and sampling the Tasmanian aerosol time-series station; A. Townsend for iron aerosol analyses by ICPMS at the University of Tasmania; and A. Benedetti and S. Remy for providing insights on the validation of aerosol reanalysis. Peer Reviewed "Article signat per 15 autors/es: Weiyi Tang, Joan Llort, Jakob Weis, Morgane M. G. Perron, Sara Basart, Zuchuan Li, Shubha Sathyendranath, Thomas Jackson, Estrella Sanz Rodriguez, Bernadette C. Proemse, Andrew R. Bowie, Christina Schallenberg, Peter G. Strutton, Richard Matear & Nicolas Cassar"

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.

Droughts and climate-change-driven warming are leading to more frequent and intense wildfires

Aerosols from Western Australia supply micronutrient trace elements including Fe into the western shelf of Australia and further afield into the Southern and Indian Oceans. However, regional observations of atmospheric trace metal deposition are limited. Here, we applied a series of leaching experiments followed by total analysis of bulk aerosol samples to a unique time-series of aerosol samples collected in Western Australia to determine atmospheric concentrations and solubilities of Fe and V, Mn, Co, Zn, and Pb. Positive matrix factorisation analysis indicated that mineral dust, biomass burning particulates, sea salt, and industrial emissions were the major types of aerosols. Overall, natural sources dominated Fe deposition. Higher atmospheric concentrations of mineral dust (sixfold) and biomass burning emissions were observed in warmer compared to cooler months. The fraction of labile Fe (0.6&ndash, 6.0%) was lower than that reported for other regions of Australia. Bushfire emissions are a temporary source of labile Fe and may cause a peak in the delivery of its more easily available forms to the ocean. Increased labile Fe deposition may result in higher ocean productivity in regions where Fe is limiting, and the effect of aerosol deposition on ocean productivity in this region requires further study.

Biomass burning (BB) emissions are a significant source of particles to the atmosphere, especially in the Southern Hemisphere, where the occurrence of anthropogenic and natural wild fires is common. These emissions can threaten human health through increased exposure, whilst simultaneously representing a significant source of trace metals and nutrients to the ocean. One well known method to track BB emissions is through monitoring the atmospheric concentration of specific monosaccharide anhydrides (MAs), specifically levoglucosan and its isomers, mannosan and galactosan. Herein, a new method for the determination of levoglucosan and its isomers in marine and terrestrial aerosol samples is presented, which delivers both high selectivity and sensitivity, through the coupling of ion chromatography and triple quadrupole tandem mass spectrometry. Optimal chromatographic conditions, providing baseline separation for target anhydrosugars in under 8 min, were obtained using a Dionex CarboPacⓇ PA-1 column with an electrolytically generated KOH gradient. To improve the ionisation efficiency for MS detection, an organic make-up solvent was fed into the IC column effluent before the ESI source, and to further increase both sensitivity and selectivity, cationisation of levoglucosan was investigated by adding salts into the make-up solvent, namely, sodium, ammonium and lithium salts. Using positive lithium cationisation with 0.5 mM lithium chloride in methanol as the make-up solvent, delivered at a flow rate of 0.02 mL min–1, the levoglucosan response was improved by factors of 100 and 10, comparing to negative ionisation and positive sodium cationisation, respectively. Detection was carried out in SRM mode for quantitation and identification, achieving an instrumental LOD of 0.10, 0.12 and 0.5 µg L−1 for levoglucosan, mannosan and galactosan, respectively. Finally, the method was applied to the analysis of 41 marine and terrestrial aerosol samples from Australia, its surrounding coastal waters and areas within the remote Southern Ocean, covering a large range of BB marker concentrations.

Atmospheric deposition of aerosols to the ocean provides an important pathway for the supply of vital micronutrients, including trace metals. These trace metals are essential for phytoplankton growth, and therefore their delivery to marine ecosystems can strongly influence the ocean carbon cycle. The solubility of trace metals in aerosols is a key parameter to better constrain their potential impact on phytoplankton growth. To date, a wide range of experimental approaches and nomenclature have been used to define aerosol trace metal solubility, making data comparison between studies difficult. Here we investigate and discuss several laboratory leaching protocols to determine the solubility of key trace metals in aerosol samples, namely iron, cobalt, manganese, copper, lead, vanadium, titanium and aluminium. Commonly used techniques and tools are also considered such as enrichment factor calculations and air mass back-trajectory projections and recommendations are given for aerosol field sampling, laboratory processing (including leaching and digestion) and analytical measurements. Finally, a simple 3-step leaching protocol combining commonly used protocols is proposed to operationally define trace metal solubility in aerosols. The need for standard guidelines and protocols to study the biogeochemical impact of atmospheric trace metal deposition to the ocean has been increasingly emphasised by both the atmospheric and oceanographic communities. This lack of standardisation currently limits our understanding and ability to predict ocean and climate interactions under changing environmental conditions.

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.

Australia is a major source of Fe-laden dust to the anemic marine phytoplankton in the Southern Ocean and to Southern Hemisphere (SH) low latitudes diazotrophic bacteria. However, the paucity of observations and laboratory experiments on SH aerosols biases model predictions of atmospheric Fe deposition to the southern oceans and the subsequent response of ocean productivity. As a result of an extensive shipboard aerosol sampling effort, this study presents laboratory measurements of aerosol Fe concentrations, solubilities and fluxes and analysis of chemical tracers, highlighting the large heterogeneity between aerosol Fe sources in 5 coastal regions around Australia. While dust-sourced high Fe loadings and low Fe solubilities (5%) aerosols dominate the atmospheric burden of the western coasts of Australia, much lower Fe concentrations but greater Fe solubilities (10.5% and 13%) were measured in aerosols along the east coast which was attributed to solubility-enhancing atmospheric reactions with anthropogenic pollutants. Surprisingly high aerosol Fe solubilities (>20%) in northern Australia aerosols were associated with direct emissions or atmospheric reactions with bushfire emissions at tropical latitudes, which accounted for 49% of the total (sum) atmospheric dry deposition flux of labile Fe measured across the continent's surrounding seawaters in this study.

This work reports on the current status of global modelling of iron (Fe) deposition fluxes and atmospheric concentrations and analyses of the differences between models, as well as between models and observations. A total of four global 3-D chemistry-transport (CTMs) and general circulation (GCMs) models have participated in this intercomparison, in the framework of the United Nations Joint Group of Experts on the Scientific Aspects of Marine Environmental Protection (GESAMP) Working Group 38, The Atmospheric Input of Chemicals to the Ocean. The global total Fe (TFe) emissions strength in the models is equal to ~ 72 Tg-Fe yr−1 (38–134 Tg-Fe yr−1) from mineral dust sources and around 2.1 Tg-Fe yr−1 (1.8–2.7 Tg-Fe yr−1) from combustion processes (sum of anthropogenic combustion/biomass burning and wildfires). The mean global labile Fe (LFe) source strength in the models, considering both the primary emissions and the atmospheric processing, is calculated to be 0.7 (±0.3) Tg-Fe yr−1, accounting for mineral dust and combustion aerosols together. The multi model ensemble global TFe and LFe deposition fluxes into the global ocean are calculated to be ~ 15 Tg-Fe yr−1 and ~ 0.3 Tg-Fe yr−1, respectively. The model intercomparison analysis indicates that the representation of the atmospheric Fe cycle varies among models, in terms of both the magnitude of natural and combustion Fe emissions as well as the complexity of atmospheric processing parametrizations of Fe-containing aerosols. The model comparison with aerosol Fe observations over oceanic regions indicate that most models overestimate surface level TFe mass concentrations near the dust source regions and tend to underestimate the low concentrations observed in remote ocean regions. All models are able to simulate the tendency of higher Fe loading near and downwind from the dust source regions, with the mean normalized bias for the Northern Hemisphere (~ 14), larger than the Southern Hemisphere (~ 2.4) for the ensemble model mean. This model intercomparison and model–observation comparison study reveals two critical issues in LFe simulations that require further exploration: 1) the Fe-containing aerosol size distribution and 2) the relative contribution of dust and combustion sources of Fe to labile Fe in atmospheric aerosols over the remote oceanic regions.