Investigation of the effect of organics on the water uptake of marine aerosols

Water uptake refers to the ability of atmospheric particles to take up water vapour from the surrounding atmosphere. This is an important property that affects particle size and phase and therefore influences many characteristics of aerosols relevant to air quality and climate. However, the water uptake properties of many important atmospheric aerosol systems, including those related to the oceans, are still not fully understood. Therefore, the primary aim of this PhD research program was to investigate the water uptake properties of marine aerosols. In particular, the effect of organics on marine aerosol water uptake was investigated. Field campaigns were conducted at remote coastal sites on the east coast of Australia (Agnes Water; March-April 2007) and west coast of Ireland (Mace Head; June 2007), and laboratory measurements were performed on bubble-generated sea spray aerosols. A combined Volatility-Hygroscopicity-Tandem Differential Mobility Analyser (VH-TDMA) was employed in all experiments. This system probes the changes in the hygroscopic properties of nanoparticles as volatile organic components are progressively evaporated. It also allows particle composition to be inferred from combined volatility-hygroscopicity measurements. Frequent new particle formation and growth events were observed during the Agnes Water campaign. The VH-TDMA was used to investigate freshly nucleated particles (17-22.5 nm) and it was found that the condensation of sulphate and/or organic vapours was responsible for driving particle growth during the events. Aitken mode particles (~40 nm) were also measured with the VH-TDMA. In 3 out of 18 VH-TDMA scans evaporation of a volatile, organic component caused a very large increase in hygroscopicity that could only be explained by an increase in the absolute water uptake of the particle residuals, and not merely an increase in their relative hygroscopicity. This indicated the presence of organic components that were suppressing the hygroscopic growth of mixed particles on the timescale of humidification in the VH-TDMA (6.5 secs). It was suggested that the suppression of water uptake was caused by either a reduced rate of hygroscopic growth due to the presence of organic films, or organic-inorganic interactions in solution droplets that had a negative effect on hygroscopicity. Mixed organic-inorganic particles were rarely observed by the VH-TDMA during the summer campaign conducted at Mace Head. The majority of particles below 100 nm in clean, marine air appeared to be sulphates neutralised to varying degrees by ammonia. On one unique day, 26 June 2007, particularly large concentrations of sulphate aerosol were observed and identified as volcanic emissions from Iceland. The degree of neutralisation of the sulphate aerosol by ammonia was calculated by the VH-TDMA and found to compare well with the same quantity measured by an aerosol mass spectrometer. This was an important verification of the VH-TMDA‘s ability to identify ammoniated sulphate aerosols based on the simultaneous measurement of aerosol volatility and hygroscopicity. A series of measurements were also conducted on sea spray aerosols generated from Moreton Bay seawater samples in a laboratory-based bubble chamber. Accumulation mode sea spray particles (38-173 nm) were found to contain only a minor organic fraction (< 10%) that had little effect on particle hygroscopicity. These results are important because previous studies have observed that accumulation mode sea spray particles are predominantly organic (~80% organic mass fraction). The work presented here suggests that this is not always the case, and that there may be currently unknown factors that are controlling the transfer of organics to the aerosol phase during the bubble bursting process. Taken together, the results of this research program have significantly improved our understanding of organic-containing marine aerosols and the way they interact with water vapour in the atmosphere.

Influence of medium range transport of particles from nucleation burst on particle number concentration within the urban airshed

An elevated particle number concentration (PNC) observed during nucleation events could play a significant contribution to the total particle load and therefore to the air pollution in the urban environments. Therefore, a field measurement study of PNC was commenced to investigate the temporal and spatial variations of PNC within the urban airshed of Brisbane, Australia. PNC was monitored at urban (QUT), roadside (WOO) and semi-urban (ROC) areas around the Brisbane region during 2009. During the morning traffic peak period, the highest relative fraction of PNC reached about 5% at QUT and WOO on weekdays. PNC peaks were observed around noon, which correlated with the highest solar radiation levels at all three stations, thus suggesting that high PNC levels were likely to be associated with new particle formation caused by photochemical reactions. Wind rose plots showed relatively higher PNC for the NE direction, which was associated with industrial pollution, accounting for 12%, 9% and 14% of overall PNC at QUT, WOO and ROC, respectively. Although there was no significant correlation between PNC at each station, the variation of PNC was well correlated among three stations during regional nucleation events. In addition, PNC at ROC was significantly influenced by upwind urban pollution during the nucleation burst events, with the average enrichment factor of 15.4. This study provides an insight into the influence of regional nucleation events on PNC in the Brisbane region and it the first study to quantify the effect of urban pollution on semi-urban PNC through the nucleation events. © 2012 Author(s).

Particle nucleation in urban subtropical atmosphere

New particle formation (NPF) and growth have been observed in different environments all around the world and NPF affects the environment by forming cloud condensation nuclei (CCN). Detailed characterisation of NPF events in a subtropical urban environment is the main aim of this study. Particle size distribution (PSD) of atmospheric aerosol particles in range 9-414 nm were measured using a Scanning Mobility Particle Sizer (SMPS), within the framework of the “Ultrafine Particles from Traffic Emissions and Children’s Health” (UPTECH) study, which seeks to determine the relationship between exposure to traffic related ultrafine particles and children’s health (http://www.ilaqh.qut. edu.au/Misc/UPTECH%20Home.htm). The UPTECH study includes measurements of air quality, meteorological and traffic parameters in 25 randomly selected state primary school within the Brisbane metropolitan area, in Queensland, Australia. Measurements at 17 schools have been completed so far.

An investigation of nucleation events in a coastal urban environment in the southern hemisphere

The occurrence of and conditions favourable to nucleation were investigated at an industrial and commercial coastal location in Brisbane, Australia during five different campaigns covering a total period of 13 months. To identify potential nucleation events, the difference in number concentration in the size range 14-30 nm (N14-30) between consecutive observations was calculated using first-order differencing. The data showed that nucleation events were a rare occurrence, and that in the absence of nucleation the particle number was dominated by particles in the range 30-300 nm. In many instances, total particle concentration declined during nucleation. There was no clear pattern in change in NO and NO2 concentrations during the events. SO2 concentration, in the majority of cases, declined during nucleation but there were exceptions. Most events took place in summer, followed by winter and then spring, and no events were observed for the autumn campaigns. The events were associated with sea breeze and long-range transport. Roadside emissions, in contrast, did not contribute to nucleation, probably due to the predominance of particles in the range 50-100 nm associated with these emissions.

New particle formation and growth at a remote, sub-tropical coastal location

A month-long intensive measurement campaign was conducted in March/April 2007 at Agnes Water, a remote coastal site just south of the Great Barrier Reef on the east coast of Australia. Particle and ion size distributions were continuously measured during the campaign. Coastal nucleation events were observed in clean, marine air masses coming from the south-east on 65% of the days. The events usually began at ~10:00 local time and lasted for 1-4 hrs. They were characterised by the appearance of a nucleation mode with a peak diameter of ~10 nm. The freshly nucleated particles grew within 1-4 hrs up to sizes of 20-50 nm. The events occurred when solar intensity was high (~1000 W m-2) and RH was low (~60%). Interestingly, the events were not related to tide height. The volatile and hygroscopic properties of freshly nucleated particles (17-22.5 nm), simultaneously measured with a volatility-hygroscopicity-tandem differential mobility analyser (VH-TDMA), were used to infer chemical composition. The majority of the volume of these particles was attributed to internally mixed sulphate and organic components. After ruling out coagulation as a source of significant particle growth, we conclude that the condensation of sulphate and/or organic vapours was most likely responsible for driving particle growth during the nucleation events. We cannot make any direct conclusions regarding the chemical species that participated in the initial particle nucleation. However, we suggest that nucleation may have resulted from the photo-oxidation products of unknown sulphur or organic vapours emitted from the waters of Hervey Bay, or from the formation of DMS-derived sulphate clusters over the open ocean that were activated to observable particles by condensable vapours emitted from the nutrient rich waters around Fraser Island or Hervey Bay. Furthermore, a unique and particularly strong nucleation event was observed during northerly wind. The event began early one morning (08:00) and lasted almost the entire day resulting in the production of a large number of ~80 nm particles (average modal concentration during the event was 3200 cm-3). The Great Barrier Reef was the most likely source of precursor vapours responsible for this event.

Particle and gaseous emissions from commercial aircraft at each stage of the landing and takeoff cycle

A novel technique was used to measure emission factors for commonly used commercial aircraft including a range of Boeing and Airbus airframes under real world conditions. Engine exhaust emission factors for particles in terms of particle number and mass (PM2.5), along with those for CO2, and NOx were measured for over 280 individual aircraft during the various modes of landing/takeoff (LTO) cycle. Results from this study show that particle number, and NOx emission factors are dependant on aircraft engine thrust level. Minimum and maximum emissions factors for particle number, PM2.5, and NOx emissions were found to be in the range of 4.16×1015-5.42×1016 kg-1, 0.03-0.72 g.kg-1, and 3.25-37.94 g.kg-1 respectively for all measured airframes and LTO cycle modes. Number size distributions of emitted particles for the naturally diluted aircraft plumes in each mode of LTO cycle showed that particles were predominantly in the range of 4 to 100 nm in diameter in all cases. In general, size distributions exhibit similar modality during all phases of the LTO cycle. A very distinct nucleation mode was observed in all particle size distributions, except for taxiing and landing of A320 aircraft. Accumulation modes were also observed in all particle size distributions. Analysis of aircraft engine emissions during LTO cycle showed that aircraft thrust level is considerably higher during taxiing than idling suggesting that International Civil Aviation Organization (ICAO) standards need to be modified as the thrust levels for taxi and idle are considered to be the same (7% of total thrust) [1].

Long-term trends in fine particle number concentrations in the urban atmosphere of Brisbane : the relevance of traffic emissions and new particle formation

The measurement of submicrometre (< 1.0 m) and ultrafine particles (diameter < 0.1 m) number concentration have attracted attention since the last decade because the potential health impacts associated with exposure to these particles can be more significant than those due to exposure to larger particles. At present, ultrafine particles are not regularly monitored and they are yet to be incorporated into air quality monitoring programs. As a result, very few studies have analysed their long-term and spatial variations in ultrafine particle concentration, and none have been in Australia. To address this gap in scientific knowledge, the aim of this research was to investigate the long-term trends and seasonal variations in particle number concentrations in Brisbane, Australia. Data collected over a five-year period were analysed using weighted regression models. Monthly mean concentrations in the morning (6:00-10:00) and the afternoon (16:00-19:00) were plotted against time in months, using the monthly variance as the weights. During the five-year period, submicrometre and ultrafine particle concentrations increased in the morning by 105.7% and 81.5% respectively whereas in the afternoon there was no significant trend. The morning concentrations were associated with fresh traffic emissions and the afternoon concentrations with the background. The statistical tests applied to the seasonal models, on the other hand, indicated that there was no seasonal component. The spatial variation in size distribution in a large urban area was investigated using particle number size distribution data collected at nine different locations during different campaigns. The size distributions were represented by the modal structures and cumulative size distributions. Particle number peaked at around 30 nm, except at an isolated site dominated by diesel trucks, where the particle number peaked at around 60 nm. It was found that ultrafine particles contributed to 82%-90% of the total particle number. At the sites dominated by petrol vehicles, nanoparticles (< 50 nm) contributed 60%-70% of the total particle number, and at the site dominated by diesel trucks they contributed 50%. Although the sampling campaigns took place during different seasons and were of varying duration these variations did not have an effect on the particle size distributions. The results suggested that the distributions were rather affected by differences in traffic composition and distance to the road. To investigate the occurrence of nucleation events, that is, secondary particle formation from gaseous precursors, particle size distribution data collected over a 13 month period during 5 different campaigns were analysed. The study area was a complex urban environment influenced by anthropogenic and natural sources. The study introduced a new application of time series differencing for the identification of nucleation events. To evaluate the conditions favourable to nucleation, the meteorological conditions and gaseous concentrations prior to and during nucleation events were recorded. Gaseous concentrations did not exhibit a clear pattern of change in concentration. It was also found that nucleation was associated with sea breeze and long-range transport. The implications of this finding are that whilst vehicles are the most important source of ultrafine particles, sea breeze and aged gaseous emissions play a more important role in secondary particle formation in the study area.

Investigation into submicrometer particle and gaseous emissions from airport ground running procedures

Emissions from airport operations are of significant concern because of their potential impact on local air quality and human health. The currently limited scientific knowledge of aircraft emissions is an important issue worldwide, when considering air pollution associated with airport operation, and this is especially so for ultrafine particles. This limited knowledge is due to scientific complexities associated with measuring aircraft emissions during normal operations on the ground. In particular this type of research has required the development of novel sampling techniques which must take into account aircraft plume dispersion and dilution as well as the various particle dynamics that can affect the measurements of the aircraft engine plume from an operational aircraft. In order to address this scientific problem, a novel mobile emission measurement method called the Plume Capture and Analysis System (PCAS), was developed and tested. The PCAS permits the capture and analysis of aircraft exhaust during ground level operations including landing, taxiing, takeoff and idle. The PCAS uses a sampling bag to temporarily store a sample, providing sufficient time to utilize sensitive but slow instrumental techniques to be employed to measure gas and particle emissions simultaneously and to record detailed particle size distributions. The challenges in relation to the development of the technique include complexities associated with the assessment of the various particle loss and deposition mechanisms which are active during storage in the PCAS. Laboratory based assessment of the method showed that the bag sampling technique can be used to accurately measure particle emissions (e.g. particle number, mass and size distribution) from a moving aircraft or vehicle. Further assessment of the sensitivity of PCAS results to distance from the source and plume concentration was conducted in the airfield with taxiing aircraft. The results showed that the PCAS is a robust method capable of capturing the plume in only 10 seconds. The PCAS is able to account for aircraft plume dispersion and dilution at distances of 60 to 180 meters downwind of moving a aircraft along with particle deposition loss mechanisms during the measurements. Characterization of the plume in terms of particle number, mass (PM2.5), gaseous emissions and particle size distribution takes only 5 minutes allowing large numbers of tests to be completed in a short time. The results were broadly consistent and compared well with the available data. Comprehensive measurements and analyses of the aircraft plumes during various modes of the landing and takeoff (LTO) cycle (e.g. idle, taxi, landing and takeoff) were conducted at Brisbane Airport (BNE). Gaseous (NOx, CO2) emission factors, particle number and mass (PM2.5) emission factors and size distributions were determined for a range of Boeing and Airbus aircraft, as a function of aircraft type and engine thrust level. The scientific complexities including the analysis of the often multimodal particle size distributions to describe the contributions of different particle source processes during the various stages of aircraft operation were addressed through comprehensive data analysis and interpretation. The measurement results were used to develop an inventory of aircraft emissions at BNE, including all modes of the aircraft LTO cycle and ground running procedures (GRP). Measurements of the actual duration of aircraft activity in each mode of operation (time-in-mode) and compiling a comprehensive matrix of gas and particle emission rates as a function of aircraft type and engine thrust level for real world situations was crucial for developing the inventory. The significance of the resulting matrix of emission rates in this study lies in the estimate it provides of the annual particle emissions due to aircraft operations, especially in terms of particle number. In summary, this PhD thesis presents for the first time a comprehensive study of the particle and NOx emission factors and rates along with the particle size distributions from aircraft operations and provides a basis for estimating such emissions at other airports. This is a significant addition to the scientific knowledge in terms of particle emissions from aircraft operations, since the standard particle number emissions rates are not currently available for aircraft activities.

Particle emissions, volatility, and toxicity from an ethanol fumigated compression ignition engine

Particle emissions, volatility, and the concentration of reactive oxygen species (ROS) were investigated for a pre-Euro I compression ignition engine to study the potential health impacts of employing ethanol fumigation technology. Engine testing was performed in two separate experimental campaigns with most testing performed at intermediate speed with four different load settings and various ethanol substitutions. A scanning mobility particle sizer (SMPS) was used to determine particle size distributions, a volatilization tandem differential mobility analyzer (V-TDMA) was used to explore particle volatility, and a new profluorescent nitroxide probe, BPEAnit, was used to investigate the potential toxicity of particles. The greatest particulate mass reduction was achieved with ethanol fumigation at full load, which contributed to the formation of a nucleation mode. Ethanol fumigation increased the volatility of particles by coating the particles with organic material or by making extra organic material available as an external mixture. In addition, the particle-related ROS concentrations increased with ethanol fumigation and were associated with the formation of a nucleation mode. The smaller particles, the increased volatility, and the increase in potential particle toxicity with ethanol fumigation may provide a substantial barrier for the uptake of fumigation technology using ethanol as a supplementary fuel.

Characterization of particle number concentrations and PM2.5 in a school : influence of outdoor air pollution on indoor air

Background, Aim and Scope The impact of air pollution on school children’s health is currently one of the key foci of international and national agencies. Of particular concern are ultrafine particles which are emitted in large quantities, contain large concentrations of toxins and are deposited deeply in the respiratory tract. Materials and methods In this study, an intensive sampling campaign of indoor and outdoor airborne particulate matter was carried out in a primary school in February 2006 to investigate indoor and outdoor particle number (PN) and mass concentrations (PM2.5), and particle size distribution, and to evaluate the influence of outdoor air pollution on the indoor air. Results For outdoor PN and PM2.5, early morning and late afternoon peaks were observed on weekdays, which are consistent with traffic rush hours, indicating the predominant effect of vehicular emissions. However, the temporal variations of outdoor PM2.5 and PN concentrations occasionally showed extremely high peaks, mainly due to human activities such as cigarette smoking and the operation of mower near the sampling site. The indoor PM2.5 level was mainly affected by the outdoor PM2.5 (r = 0.68, p<0.01), whereas the indoor PN concentration had some association with outdoor PN values (r = 0.66, p<0.01) even though the indoor PN concentration was occasionally influenced by indoor sources, such as cooking, cleaning and floor polishing activities. Correlation analysis indicated that the outdoor PM2.5 was inversely correlated with the indoor to outdoor PM2.5 ratio (I/O ratio) (r = -0.49, p<0.01), while the indoor PN had a weak correlation with the I/O ratio for PN (r = 0.34, p<0.01). Discussion and Conclusions The results showed that occupancy did not cause any major changes to the modal structure of particle number and size distribution, even though the I/O ratio was different for different size classes. The I/O curves had a maximum value for particles with diameters of 100 – 400 nm under both occupied and unoccupied scenarios, whereas no significant difference in I/O ratio for PM2.5 was observed between occupied and unoccupied conditions. Inspection of the size-resolved I/O ratios in the preschool centre and the classroom suggested that the I/O ratio in the preschool centre was the highest for accumulation mode particles at 600 nm after school hours, whereas the average I/O ratios of both nucleation mode and accumulation mode particles in the classroom were much lower than those of Aitken mode particles. Recommendations and Perspectives The findings obtained in this study are useful for epidemiological studies to estimate the total personal exposure of children, and to develop appropriate control strategies for minimizing the adverse health effects on school children.

Vertical particle concentration profiles around urban office buildings

Despite its role in determining both indoor and outdoor human exposure to anthropogenic particles, there is limited information describing vertical profiles of particle concentrations in urban environments, especially for ultrafine particles. Furthermore, the results of the few studies performed have been inconsistent. As such, this study aimed to assess the influence of vehicle emissions and nucleation formation on particle characteristics (particle number size distribution-PNSD and PM 2.5 concentration) at different heights around three urban office buildings located next to busy roads in Brisbane, Australia, and place these results in the broader context of the existing literature. Two sets of instruments were used to simultaneously measure PNSD, particle number (PN) and PM 2.5 concentrations, respectively, for up to three weeks at each building. The results showed that both PNSD and PM 2.5 concentration around building envelopes were influenced by vehicle emissions and new particle formation, and that they exhibited variability across the three different office buildings. During nucleation events, PN concentration in size range of <30 nm and total PN concentration increased (7-65% and 5-46%, respectively), while PM 2.5 concentration decreased (36-52%) with height. This study has shown an under acknowledged role for nucleation in producing particles that can affect large numbers of people, due to the high density and occupancy of urban office buildings and the fact that the vast majority of people's time is spent indoors. These findings highlight important new information related to the previously overlooked role of particle formation in the urban atmosphere and its potential effects on selection of air intake locations and appropriate filter types when designing or upgrading mechanical ventilation systems in urban office buildings. The results also serve to better define particle behaviour and variability around building envelopes, which has implications for studies of both human exposure and particle dynamics. © 2012 Author(s).

Observation of new particle formation in subtropical urban environment

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 x 103, 3.7 x 103 and 5.6 x 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 hr-1 (ranged from 1.79 – 7.78 nm hr-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.

Nucleation experiments in a microgravity environment

A simple experimental apparatus is described in which a wide variety of vapor phase nucleation studies of refractory materials could be performed aboard NASA's KC-135 Research Aircraft. The chief advantage of a microgravity environment for these studies is the expected absence of thermally driven convective motions in the gas. The absence of convection leads to much more accurate knowledge of both the temperature distribution in the system and the time evolution of the refractory vapor concentration as a function of distance from the crucible.The evolution of the apparatus will be described as more experience is gained with the microgravity environment. Such experiments will be used to prepare for similar ones carried out aboard either the shuttle or Space Station where considerably longer duration experiments are possible.

Particle formation and interaction

A wide variety of experiments that involve the physics of small particles (μm to cm in size) of planetary significance can be conducted on the Space Station. Processes of interest include nucleation and condensation of particles from a gas, aggregation of small particles into larger ones, and low velocity collisions of particles. Only experiments relevant to planetary processes will be discussed in detail here.

Composition and morphology of particle emissions from in-use aircraft during takeoff and landing

In order to provide realistic data for air pollution inventories and source apportionment at airports, the morphology and composition of ultrafine particles (UFP) in aircraft engine exhaust were measured and characterized. For this purpose, two independent measurement techniques were employed to collect emissions during normal takeoff and landing operations at Brisbane Airport, Australia. PM1 emissions in the airfield were collected on filters and analyzed using the particle-induced X-ray emission (PIXE) technique. Morphological and compositional analyses of individual ultrafine particles in aircraft plumes were performed on silicon nitride membrane grids using transmission electron microscopy (TEM) combined with energy-dispersive X-ray microanalysis (EDX). TEM results showed that the deposited particles were in the range of 5 to 100 nm in diameter, had semisolid spherical shapes and were dominant in the nucleation mode (18 – 20 nm). The EDX analysis showed the main elements in the nucleation particles were C, O, S and Cl. The PIXE analysis of the airfield samples was generally in agreement with the EDX in detecting S, Cl, K, Fe and Si in the particles. The results of this study provide important scientific information on the toxicity of aircraft exhaust and their impact on local air quality.