RESUMEN
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.
RESUMEN
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 8â¯min, were obtained using a Dionex CarboPacâ 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 0.5â¯mM lithium chloride in methanol as the make-up solvent, delivered at a flow rate of 0.02â¯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⯵g 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.