Widespread phytoplankton blooms triggered by 2019-2020 Australian wildfires.

Droughts and climate-change-driven warming are leading to more frequent and intense wildfires1-3, 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 aerosols5-7. Aerosol emissions from wildfires can lead to the atmospheric transport of macronutrients and bio-essential trace metals such as nitrogen and iron, respectively8-10. 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 regions1-3. 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.

Comparing levoglucosan and mannosan ratios in sediments and corresponding aerosols from recent Australian fires.

The monosaccharide anhydrides levoglucosan, mannosan, and galactosan are known as 'fire sugars' as they are powerful proxies used to trace fire events. Despite their increasing use, their application is not completely understood, especially in the context of tracing past fire events using sediment samples. There are many uncertainties about fire sugar formation, partitioning, transport, complexation, and stability along all stages of the source-to-sink pathway. While these uncertainties exist, the efficacy of fire sugars as fire tracers remains limited. This study compared high-resolution fire sugar fluxes in freshwater sediment cores to known fire records in Tasmania, Australia. Past fire events correlated with fire sugar flux increases down-core, with the magnitude of the flux inversely proportional to the distance of the fires from the study site. For the first time, fire sugar ratios (levoglucosan/mannosan, L/M) in aerosols were compared with those in sediments from the same time-period. The L/M ratio in surface sediments (1.42-2.58) were significantly lower than in corresponding aerosols (5.08-15.62). We propose two hypotheses that may explain the lower average L/M of sediments. Firstly, the degradation rate of levoglucosan is higher than mannosan in the water column, sediment-water interface, and/or sediment. Secondly, the L/M ratio of non-atmospheric emissions during fires may be lower than that of atmospheric emissions from the same fire. Due to the uncertainties about transport partitioning (atmospheric versus non-atmospheric emissions) and fire sugar degradation along all stages of the source-to-sink pathway, we advise caution when inferring vegetation type (e.g. softwood, hardwood, or grasses) based purely on fire sugar ratios in sediments (e.g. L/M ratio). Future investigations are required to increase the efficacy of fire sugars as a complimentary, or standalone, fire tracer in sediments.

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.

Assessment of leaching protocols to determine the solubility of trace metals in aerosols.

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.

Analysis of levoglucosan and its isomers in atmospheric samples by ion chromatography with electrospray lithium cationisation - Triple quadrupole tandem mass spectrometry.

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.

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.