A fast and simple extraction method for analysing levoglucosan and its isomers in sediments by ion chromatography tandem mass spectrometry.

The ability to trace current and past biomass burning events is important for understanding the links between human activity, fire frequency, and climate. One method of tracing biomass burning is to measure the concentrations of certain monosaccharides anhydrides (MAs), specifically levoglucosan (LEV) and its isomers, mannosan (MAN) and galactosan (GAL), which are products of cellulose and hemicellulose pyrolysis. This work presents a simple extraction method allowing for the rapid, sensitive, and selective determination of MAs in sediments. MAs detection was performed using suppressed ion chromatography with electrospray - triple-stage quadrupole tandem mass spectrometry (IC-TSQ-MS). The extraction method involves ultrasound probe sonication using water as the solvent. Extraction time, amplitude, and sonication mode were optimised. Recoveries higher than 86% for all MAs tested were achieved by applying 70% amplitude in continuous mode for 60 s. Analytical performance of the method included instrumental LODs of 0.10, 0.12 and 0.50 µg L-1 for LEV, MAN and GAL, respectively. No carryover issues, no matrix effect and no co-elution of targeted MAs with other sugars likely present in sediments samples were observed. The developed extraction method was further validated by the analysis of LEV and MAN in NIST® 1649b urban dust reference material and the resulting concentrations were in excellent agreement with previously reported values. MAs quantification in 70 lake sediment samples were carried out with concentrations found to range from 0.009 to 0.390 µg g-1 for LEV and from 0.009 to 0.194 µg g-1 for MAN. Plotting MAs concentrations versus approximate sediment age allowed the reconstruction of recent fire events impacting two locations in the Central Highlands of Tasmania, Australia.

Salinity-driven ecology and diversity changes of heterocytous cyanobacteria in Australian freshwater and coastal-marine microbial mats.

N2 -fixing heterocytous cyanobacteria are considered to play a minor role in sustaining coastal microbial mat communities developing under normal marine to hypersaline conditions. Here, we investigated microbial mats growing under different salinities from freshwater mats of Giblin River (Tasmania) to metahaline and hypersaline mats of Shark Bay (Western Australia). Analyses of genetic (rRNA and mRNA) and biological markers (heterocyte glycolipids) revealed an unexpectedly large diversity of heterocytous cyanobacteria in all the studied microbial mat communities. It was observed that the taxonomic distribution as well as abundance of cyanobacteria is strongly affected by salinity. Low salinity favoured the presence of heterocytous cyanobacteria in freshwater mats, while mats thriving in higher salinities mainly supported the growth unicellular and filamentous non-heterocytous genera. However, even though mRNA transcripts derived from heterocytous cyanobacteria were lower in Shark Bay (<6%) microbial mats, functional analyses revealed that these diazotrophs were transcribing a substantial proportion of the genes involved in biofilm formation and nitrogen fixation. Overall, our data reveal an unexpectedly high diversity of heterocytous cyanobacteria (e.g. Calothrix, Scytonema, Nodularia, Gloeotrichia, Stigonema, Fischerella and Chlorogloeopsis) that had yet to be described in metahaline and hypersaline microbial mats from Shark Bay and that they play a vital role in sustaining the ecosystem functioning of coastal-marine microbial mat systems.

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.

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.

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.

Stromatolites on the rise in peat-bound karstic wetlands.

Stromatolites are the oldest evidence for life on Earth, but modern living examples are rare and predominantly occur in shallow marine or (hyper-) saline lacustrine environments, subject to exotic physico-chemical conditions. Here we report the discovery of living freshwater stromatolites in cool-temperate karstic wetlands in the Giblin River catchment of the UNESCO-listed Tasmanian Wilderness World Heritage Area, Australia. These stromatolites colonize the slopes of karstic spring mounds which create mildly alkaline (pH of 7.0-7.9) enclaves within an otherwise uniformly acidic organosol terrain. The freshwater emerging from the springs is Ca-HCO3 dominated and water temperatures show no evidence of geothermal heating. Using 16 S rRNA gene clone library analysis we revealed that the bacterial community is dominated by Cyanobacteria, Alphaproteobacteria and an unusually high proportion of Chloroflexi, followed by Armatimonadetes and Planctomycetes, and is therefore unique compared to other living examples. Macroinvertebrates are sparse and snails in particular are disadvantaged by the development of debilitating accumulations of carbonate on their shells, corroborating evidence that stromatolites flourish under conditions where predation by metazoans is suppressed. Our findings constitute a novel habitat for stromatolites because cool-temperate freshwater wetlands are not a conventional stromatolite niche, suggesting that stromatolites may be more common than previously thought.

A multi-isotope approach for estimating industrial contributions to atmospheric nitrogen deposition in the Athabasca oil sands region in Alberta, Canada.

Industrial nitrogen (N) emissions in the Athabasca oil sands region (AOSR), Alberta, Canada, affect nitrate (NO3) and ammonium (NH4) deposition rates in close vicinity of industrial emitters. NO3-N and NH4-N open field and throughfall deposition rates were determined at various sites between 3 km and 113 km distance to the main oil sand operations between May 2008 and May 2009. NO3 and NH4 were analyzed for δ(15)N-NO3, δ(18)O-NO3, Δ(17)O-NO3 and δ(15)N-NH4. Marked differences in the δ(18)O and Δ(17)O values between industrial emissions and background deposition allowed for the estimation of minimum industrial contributions to atmospheric NO3 deposition. δ(15)N-NH4 values also allowed for estimates of industrial contributions to atmospheric NH4 deposition. Results revealed that particularly sites within ~30 km radius from the main oil sands developments are significantly affected by industrial contributions to atmospheric NO3 and NH4 deposition.

Concentration measurements and isotopic composition of airborne molybdenum collected in an urban environment.

Here, we report the first measurements of the molybdenum (Mo) isotopic composition of aerosols collected on Teflon air filters. Mo concentrations and isotopic compositions were measured at selected locations in the city of Calgary, Canada, including a residence, the isotope laboratory at the University of Calgary, the University of Calgary weather station, and the City of Calgary Transit bus garage. Concentrations ranged from 0.07 ng/m(3) in the laboratory to 19.0 ng/m(3) in the bus garage. The concentrations of Mo in the air samples collected in the bus garage were the highest measured in this study. To date, there are no reported data for the Mo isotopic composition of airborne Mo. In this study, the δ(98/95)Mo values measured for the different urban sampling sites and reported relative to SRM 3134, ranged from -0.18 to +0.94 ‰. The results of this investigation suggest that measurements of Mo concentrations and isotopic compositions have the potential to trace anthropogenic emissions in an urban environment.