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The SAFIRED (Savannah Fires in the Early Dry Season) campaign took place from 29 May until 30 June 2014 at the Australian Tropical Atmospheric Research Station (ATARS) in the Northern Territory, Australia. The purpose of this campaign was to investigate emissions from fires in the early dry season in northern Australia. Measurements were made of biomass burning aerosols, volatile organic compounds, polycyclic aromatic carbons, greenhouse gases, radon, speciated atmospheric mercury and trace metals. Aspects of the biomass burning aerosol emissions investigated included; emission factors of various species, physical and chemical aerosol properties, aerosol aging, micronutrient supply to the ocean, nucleation, and aerosol water uptake. Over the course of the month-long campaign, biomass burning signals were prevalent and emissions from several large single burning events were observed at ATARS.Biomass burning emissions dominated the gas and aerosol concentrations in this region. Dry season fires are extremely frequent and widespread across the northern region of Australia, which suggests that the measured aerosol and gaseous emissions at ATARS are likely representative of signals across the entire region of north Australia. Air mass forward trajectories show that these biomass burning emissions are carried north-west over the Timor Sea and could influence the atmosphere over Indonesia and the tropical atmosphere over the Indian Ocean. Here we present characteristics of the biomass burning observed at the sampling site and provide an overview of the more specific outcomes of the SAFIRED campaign.

The vast majority of Australia's fires occur in the tropical north of the continent during the dry season. These fires are a significant source of aerosol and cloud condensation nuclei (CCN) in the region, providing a unique opportunity to investigate the biomass burning aerosol (BBA) in the absence of other sources. CCN concentrations at 0.5 % supersaturation and aerosol size and chemical properties were measured at the Australian Tropical Atmospheric Research Station (ATARS) during June 2014. CCN concentrations reached over 104 cm−3 when frequent and close fires were burning – up to 45 times higher than periods with no fires. Both the size distribution and composition of BBA appeared to significantly influence CCN concentrations. A distinct diurnal trend in the proportion of BBA activating to cloud droplets was observed, with an activation ratio of 40 ± 20 % during the night and 60 ± 20 % during the day. BBA was, on average, less hygroscopic during the night (κ = 0. 04 ± 0.03) than during the day (κ = 0.07 ± 0.05), with a maximum typically observed just before midday. Size-resolved composition of BBA showed that organics comprised a constant 90 % of the aerosol volume for aerodynamic diameters between 100 and 200 nm. While this suggests that the photochemical oxidation of organics led to an increase in the hygroscopic growth and an increase in daytime activation ratios, it does not explain the decrease in hygroscopicity after midday. Modelled CCN concentrations assuming typical continental hygroscopicities produced very large overestimations of up to 200 %. Smaller, but still significant, overpredictions up to ∼ 100 % were observed using aerosol mass spectrometer (AMS)- and hygroscopicity tandem differential mobility analyser (H-TDMA)-derived hygroscopicities as well as campaign night and day averages. The largest estimations in every case occurred during the night, when the small variations in very weakly hygroscopic species corresponded to large variations in the activation diameters. Trade winds carry the smoke generated from these fires over the Timor Sea, where aerosol–cloud interactions are likely to be sensitive to changes in CCN concentrations, perturbing cloud albedo and lifetime. Dry season fires in northern Australia are therefore potentially very important in cloud processes in this region.

There is a lack of knowledge of how biomass burning aerosols in the tropics age, including those in the fire-prone Northern Territory in Australia. This paper reports chemical characterization of fresh and aged aerosols monitored during the 1-month-long SAFIRED (Savannah Fires in the Early Dry Season) field study, with an emphasis on the chemical signature and aging of organic aerosols. The campaign took place in June 2014 during the early dry season when the surface measurement site, the Australian Tropical Atmospheric Research Station (ATARS), located in the Northern Territory, was heavily influenced by thousands of wild and prescribed bushfires. ATARS was equipped with a wide suite of instrumentation for gaseous and aerosol characterization. A compact time-of-flight aerosol mass spectrometer was deployed to monitor aerosol chemical composition. Approximately 90 % of submicron non-refractory mass was composed of organic material. Ozone enhancement in biomass burning plumes indicated increased air mass photochemistry. The diversity in biomass burning emissions was illustrated through variability in chemical signature (e.g. wide range in f44, from 0.06 to 0.18) for five intense fire events. The background particulate loading was characterized using positive matrix factorization (PMF). A PMF-resolved BBOA (biomass burning organic aerosol) factor comprised 24 % of the submicron non-refractory organic aerosol mass, confirming the significance of fire sources. A dominant PMF factor, OOA (oxygenated organic aerosol), made up 47 % of the sampled aerosol, illustrating the importance of aerosol aging in the Northern Territory. Biogenic isoprene-derived organic aerosol factor was the third significant fraction of the background aerosol (28 %).

Few studies have investigated nocturnal new particle formation (NPF) events, and none of them were conducted in urban environments. Nocturnal NPF can potentially be a significant source of particles in urban areas, and studying them would improve our understanding of nucleation mechanisms. To address this, our study was conducted in an urban environment to investigate the physical characteristics of NPF events, with a particular focus on nocturnal events and the differences between them and the daytime NPF events. Particle number size distribution (PNSD) was measured for 2 weeks at each of 25 sites across an urban environment. A new method was proposed to automatically categorise NPF events based on growth rate (GR) in order to remove the bias related to the manual procedure. Out of 219 observed events, 118 and 101 were categorised into class I and II respectively and 73 happened during the nighttime which included more than 30 % of the events. GR and condensation sink (CS) were calculated and a slight negative relationship between GR and CS was observed. Nocturnal events displayed higher GRs compared to daylight ones which were on average about 10 %. Back trajectory analysis was also conducted to estimate the locations of the sources of daylight and nocturnal precursors. While the precursors related to daylight events originated from different locations with no particular pattern, back-trajectory analysis showed many air masses associated with nocturnal NPF events were transported from over the ocean. Overall, nocturnal NPF events were found to be a significant source of particles in the studied environment with different physical characteristics and/or sources compared to daylight events.

Biomass burning (BB) plumes were measured at the Cape Grim Baseline Air Pollution Station during the 2006 Precursors to Particles campaign, when emissions from a fire on nearby Robbins Island impacted the station. Measurements made included non-methane organic compounds (NMOCs) (PTR-MS), particle number size distribution, condensation nuclei (CN) > 3 nm, black carbon (BC) concentration, cloud condensation nuclei (CCN) number, ozone (O3), methane (CH4), carbon monoxide (CO), hydrogen (H2), carbon dioxide (CO2), nitrous oxide (N2O), halocarbons and meteorology. During the first plume strike event (BB1), a 4 h enhancement of CO (max ~ 2100 ppb), BC (~ 1400 ng m-3) and particles > 3 nm (~ 13 000 cm-3) with dominant particle mode of 120 nm were observed overnight. A wind direction change lead to a dramatic reduction in BB tracers and a drop in the dominant particle mode to 50 nm. The dominant mode increased in size to 80 nm over 5 h in calm sunny conditions, accompanied by an increase in ozone. Due to an enhancement in BC but not CO during particle growth, the presence of BB emissions during this period could not be confirmed. The ability of particles > 80 nm (CN80) to act as CCN at 0.5 % supersaturation was investigated. The ΔCCN / ΔCN80 ratio was lowest during the fresh BB plume (56 ± 8 %), higher during the particle growth period (77 ± 4 %) and higher still (104 ± 3 %) in background marine air. Particle size distributions indicate that changes to particle chemical composition, rather than particle size, are driving these changes. Hourly average CCN during both BB events were between 2000 and 5000 CCN cm-3, which were enhanced above typical background levels by a factor of 6–34, highlighting the dramatic impact BB plumes can have on CCN number in clean marine regions. During the 29 h of the second plume strike event (BB2) CO, BC and a range of NMOCs including acetonitrile and hydrogen cyanide (HCN) were clearly enhanced and some enhancements in O3 were observed (ΔO3 / ΔCO 0.001–0.074). A short-lived increase in NMOCs by a factor of 10 corresponded with a large CO enhancement, an increase of the NMOC / CO emission ratio (ER) by a factor of 2–4 and a halving of the BC / CO ratio. Rainfall on Robbins Island was observed by radar during this period which likely resulted in a lower fire combustion efficiency, and higher emission of compounds associated with smouldering. This highlights the importance of relatively minor meteorological events on BB emission ratios. Emission factors (EFs) were derived for a range of trace gases, some never before reported for Australian fires, (including hydrogen, phenol and toluene) using the carbon mass balance method. This provides a unique set of EFs for Australian coastal heathland fires. Methyl halide EFs were higher than EFs reported from other studies in Australia and the Northern Hemisphere which is likely due to high halogen content in vegetation on Robbins Island. This work demonstrates the substantial impact that BB plumes can have on the composition of marine air, and the significant changes that can occur as the plume interacts with terrestrial, aged urban and marine emission sources.

In the prospect of limited energy resources and climate change, effects of alternative biofuels on primary emissions are being extensively studied. Our two recent studies have shown that biodiesel fuel composition has a significant impact on primary particulate matter emissions. It was also shown that particulate matter caused by biodiesels was substantially different from the emissions due to petroleum diesel. Emissions appeared to have higher oxidative potential with the increase in oxygen content and decrease of carbon chain length and unsaturation levels of fuel molecules. Overall, both studies concluded that chemical composition of biodiesel is more important than its physical properties in controlling exhaust particle emissions. This suggests that the atmospheric aging processes, including secondary organic aerosol formation, of emissions from different fuels will be different as well. In this study, measurements were conducted on a modern common-rail diesel engine. To get more information on realistic properties of tested biodiesel particulate matter once they are released into the atmosphere, particulate matter was exposed to atmospheric oxidants, ozone and ultra-violet light; and the change in their properties was monitored for different biodiesel blends. Upon the exposure to oxidative agents, the chemical composition of the exhaust changes. It triggers the cascade of photochemical reactions resulting in the partitioning of semi-volatile compounds between the gas and particulate phase. In most of the cases, aging lead to the increase in volatility and oxidative potential, and the increment of change was mainly dependent on the chemical composition of fuels as the leading cause for the amount and the type of semi-volatile compounds present in the exhaust.

The dicarbonyls glyoxal and methylglyoxal have been measured with 2,4-dinitrophenylhydrazine (2,4-DNPH) cartridges and high-performance liquid chromatography (HPLC), optimised for dicarbonyl detection, in clean marine air over the temperate Southern Hemisphere (SH) oceans. Measurements of a range of dicarbonyl precursors (volatile organic compounds, VOCs) were made in parallel. These are the first in situ measurements of glyoxal and methylglyoxal over the remote temperate oceans. Six 24 h samples were collected in summer (February–March) over the Chatham Rise in the south-west Pacific Ocean during the Surface Ocean Aerosol Production (SOAP) voyage in 2012, while 34 24 h samples were collected at Cape Grim Baseline Air Pollution Station in the late winter (August–September) of 2011. Average glyoxal mixing ratios in clean marine air were 7 ppt at Cape Grim and 23 ppt over Chatham Rise. Average methylglyoxal mixing ratios in clean marine air were 28 ppt at Cape Grim and 10 ppt over Chatham Rise. The mixing ratios of glyoxal at Cape Grim are the lowest observed over the remote oceans, while mixing ratios over Chatham Rise are in good agreement with other temperate and tropical observations, including concurrent Multi-Axis Differential Optical Absorption Spectroscopy (MAX-DOAS) observations. Methylglyoxal mixing ratios at both sites are comparable to the only other marine methylglyoxal observations available over the tropical Northern Hemisphere (NH) ocean. Ratios of glyoxal : methylglyoxal > 1 over Chatham Rise but < 1 at Cape Grim suggest that a different formation and/or loss processes or rates dominate at each site. Dicarbonyl precursor VOCs, including isoprene and monoterpenes, are used to calculate an upper-estimate yield of glyoxal and methylglyoxal in the remote marine boundary layer and explain at most 1–3 ppt of dicarbonyls observed, corresponding to 10% and 17% of the observed glyoxal and 29 and 10% of the methylglyoxal at Chatham Rise and Cape Grim, respectively, highlighting a significant but as yet unknown production mechanism. Surface-level glyoxal observations from both sites were converted to vertical columns and compared to average vertical column densities (VCDs) from GOME-2 satellite retrievals. Both satellite columns and in situ observations are higher in summer than winter; however, satellite vertical column densities exceeded the surface observations by more than 1.5 × 1014 molecules cm−2 at both sites. This discrepancy may be due to the incorrect assumption that all glyoxal observed by satellite is within the boundary layer, or it may be due to challenges retrieving low VCDs of glyoxal over the oceans due to interferences by liquid water absorption or the use of an inappropriate normalisation reference value in the retrieval algorithm. This study provides much-needed data to verify the presence of these short-lived gases over the remote ocean and provide further evidence of an as yet unidentified source of both glyoxal and also methylglyoxal over the remote oceans.

The aim of this study was to characterise the new particle formation events in a subtropical urban environment in the Southern Hemisphere. The study measured the number concentration of particles and its size distribution in Brisbane, Australia during 2009. The variation of particle number concentration and nucleation burst events were characterised as well as the particle growth rate which was first reported in urban environment of Australia. The annual average NUFP, NAitken and NNuc were 9.3×103, 3.7×103 and 5.6×103 cm−3, respectively. Weak seasonal variation in number concentration was observed. Local traffic exhaust emissions were a major contributor of the pollution (NUFP) observed in morning which was dominated by the Aitken mode particles, while particles formed by secondary formation processes contributed to the particle number concentration during afternoon. Overall, 65 nucleation burst events were identified during the study period. Nucleation burst events were classified into two groups, with and without particles growth after the burst of nucleation mode particles observed. The average particle growth rate of the nucleation events was 4.6 nm h−1 (ranged from 1.79–7.78 nm h−1). Case studies of the nucleation burst events were characterised including (i) the nucleation burst with particle growth which is associated with the particle precursor emitted from local traffic exhaust emission, (ii) the nucleation burst without particle growth which is due to the transport of industrial emissions from the coast to Brisbane city or other possible sources with unfavourable conditions which suppressed particle growth and (iii) interplay between the above two cases which demonstrated the impact of the vehicle and industrial emissions on the variation of particle number concentration and its size distribution during the same day.

The influence of biogenic particle formation on climate is a well recognised phenomenon. To understand the mechanisms underlying the biogenic particle formation, determining the chemical composition of the new particles and therefore the species that drive the particle production is of utmost importance. Due to the very small amount of mass involved, indirect approaches are frequently used to infer the composition. We present here the results of such an indirect approach by simultaneously measuring volatile and hygroscopic properties of newly formed particles in a forest environment. It is shown that the particles are composed of both sulphates and organics, with the amount of sulphate component strongly depending on the available gas-phase sulphuric acid, and the organic components having the same volatility and hygroscopicity as photo-oxidation products of a monoterpene such as α-pinene. Our findings agree with a two-step process through nucleation and cluster formation followed by simultaneous growth by condensation of sulphates and organics that take the particles to climatically relevant sizes.

The volatile and hygroscopic properties of ammonium sulphate seeded and unseeded secondary organic aerosol (SOA) derived from the photo-oxidation of atmospherically relevant concentrations of α-pinene were studied. The seed particles were electrospray generated ammonium sulphate ((NH4)2SO4) having diameters of approximately 33 nm with a quasi-mono-disperse size distribution (geometric standard deviation σg=1.3). The volatile and hygroscopic properties of both seeded and unseeded SOA were simultaneously measured with a VH-TDMA (volatility – hygroscopicity tandem differential mobility analyzer). VH-TDMA measurements of unseeded SOA show a decrease in the hygroscopic growth (HGF) factor for increased volatilisation temperatures such that the more volatile compounds appear to be more hygroscopic. This is opposite to the expected preferential evaporation of more volatile but less hygroscopic material, but could also be due to enhanced oligomerisation occurring at the higher temperature in the thermodenuder. In addition, HGF measurements of seeded SOA were measured as a function of time at two relative humidities, below (RH 75%) and above (RH 85%) the deliquescence relative humidity (DRH) of the pure ammonium sulphate seeds. As these measurements were conducted during the onset phase of photo-oxidation, during particle growth, they enabled us to find the dependence of the HGF as a function of the volume fraction of the SOA coating. HGF's measured at RH of 85% showed a continuous decrease as the SOA coating thickness increased. The measured growth factors show good agreements with ZSR predictions indicating that, at these RH values, there are only minor solute-solute interactions. At 75% RH, as the SOA fraction increased, a rapid increase in the HGF was observed indicating that an increasing fraction of the (NH4)2SO4 is subject to a phase transition, going into solution, with an increasing volume fraction of SOA. To our knowledge this is the first time that SOA derived from photo-oxidised α-pinene has been shown to affect the equilibrium water content of inorganic aerosols below their DRH. For SOA volume fractions above ~0.3 the measured growth factor followed roughly parallel to the ZSR prediction based on fully dissolved (NH4)2SO4 although with a small difference that was just larger than the error estimate. Both incomplete dissolution and negative solute-solute interactions could be responsible for the lower HGF observed compared to the ZSR predictions.