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.

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.

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.

Study of new particle formation in subtropical urban environment in Brisbane, Australia

Atmospheric ultrafine particles play an important role in affecting human health, altering climate and degrading visibility. Numerous studies have been conducted to better understand the formation process of these particles, including field measurements, laboratory chamber studies and mathematical modeling approaches. Field studies on new particle formation found that formation processes were significantly affected by atmospheric conditions, such as the availability of particle precursors and meteorological conditions. However, those studies were mainly carried out in rural areas of the northern hemisphere and information on new particle formation in urban areas, especially those in subtropical regions, is limited. In general, subtropical regions display a higher level of solar radiation, along with stronger photochemical reactivity, than those regions investigated in previous studies. However, based on the results of these studies, the mechanisms involved in the new particle formation process remain unclear, particularly in the Southern Hemisphere. Therefore, in order to fill this gap in knowledge, a new particle formation study was conducted in a subtropical urban area in the Southern Hemisphere during 2009, which measured particle size distribution in different locations in Brisbane, Australia. Characterisation of nucleation events was conducted at the campus building of the Queensland University of Technology (QUT), located in an urban area of Brisbane. Overall, the annual average number concentrations of ultrafine, Aitken and nucleation mode particles were found to be 9.3 x 103, 3.7 x 103 and 5.6 x 103 cm-3, respectively. This was comparable to levels measured in urban areas of northern Europe, but lower than those from polluted urban areas such as the Yangtze River Delta, China and Huelva and Santa Cruz de Tenerife, Spain. Average particle number concentration (PNC) in the Brisbane region did not show significant seasonal variation, however a relatively large variation was observed during the warmer season. Diurnal variation of Aitken and nucleation mode particles displayed different patterns, which suggested that direct vehicle exhaust emissions were a major contributor of Aitken mode particles, while nucleation mode particles originated from vehicle exhaust emissions in the morning and photochemical production at around noon. A total of 65 nucleation events were observed during 2009, in which 40 events were classified as nucleation growth events and the remainder were nucleation burst events. An interesting observation in this study was that all nucleation growth events were associated with vehicle exhaust emission plumes, while the nucleation burst events were associated with industrial emission plumes from an industrial area. The average particle growth rate for nucleation events was found to be 4.6 nm hr-1 (ranging from 1.79-7.78 nm hr-1), which is comparable to other urban studies conducted in the United States, while monthly particle growth rates were found to be positively related to monthly solar radiation (r = 0.76, p <0.05). The particle growth rate values reported in this work are the first of their kind to be reported for the subtropical urban area of Australia. Furthermore, the influence of nucleation events on PNC within the urban airshed was also investigated. PNC was simultaneously measured at urban (QUT), roadside (Woolloongabba) and semi-urban (Rocklea) sites in Brisbane during 2009. Total PNC at these sites was found to be significantly affected by regional nucleation events. The relative fractions of PNC to total daily PNC observed at QUT, Woolloongabba and Rocklea were found to be 12%, 9% and 14%, respectively, during regional nucleation events. These values were higher than those observed as a result of vehicle exhaust emissions during weekday mornings, which ranged from 5.1-5.5% at QUT and Woolloongabba. In addition, PNC in the semi-urban area of Rocklea increased by a factor of 15.4 when it was upwind from urban pollution sources under the influence of nucleation burst events. Finally, we investigated the influence of sulfuric acid on new particle formation in the study region. A H2SO4 proxy was calculated by using [SO2], solar radiation and particle condensation sink data to represent the new particle production strength for the urban, roadside and semi-urban areas of Brisbane during the period June-July of 2009. The temporal variations of the H2SO4 proxies and the nucleation mode particle concentration were found to be in phase during nucleation events in the urban and roadside areas. In contrast, the peak of proxy concentration occurred 1-2 hr prior to the observed peak in nucleation mode particle concentration at the downwind semi-urban area of Brisbane. A moderate to strong linear relationship was found between the proxy and the freshly formed particles, with r2 values of 0.26-0.77 during the nucleation events. In addition, the log[H2SO4 proxy] required to produce new particles was found to be ~1.0 ppb Wm-2 s and below 0.5 ppb Wm-2 s for the urban and semi-urban areas, respectively. The particle growth rates were similar during nucleation events at the three study locations, with an average value of 2.7 ± 0.5 nm hr-1. This result suggested that a similar nucleation mechanism dominated in the study region, which was strongly related to sulphuric acid concentration, however the relationship between the proxy and PNC was poor in the semi-urban area of Rocklea. This can be explained by the fact that the nucleation process was initiated upwind of the site and the resultant particles were transported via the wind to Rocklea. This explanation is also supported by the higher geometric mean diameter value observed for particles during the nucleation event and the time lag relationship between the H2SO4 proxy and PNC observed at Rocklea. In summary, particle size distribution was continuously measured in a subtropical urban area of southern hemisphere during 2009, the findings from which formed the first particle size distribution dataset in the study region. The characteristics of nucleation events in the Brisbane region were quantified and the properties of the nucleation growth and burst events are discussed in detail using a case studies approach. To further investigate the influence of nucleation events on PNC in the study region, PNC was simultaneously measured at three locations to examine the spatial variation of PNC during the regional nucleation events. In addition, the impact of upwind urban pollution on the downwind semi-urban area was quantified during these nucleation events. Sulphuric acid was found to be an important factor influencing new particle formation in the urban and roadside areas of the study region, however, a direct relationship with nucleation events at the semi-urban site was not observed. This study provided an overview of new particle formation in the Brisbane region, and its influence on PNC in the surrounding area. The findings of this work are the first of their kind for an urban area in the southern hemisphere.

Investigation into chemistry of new particle formation and growth in subtropical urban environment

The role of different chemical compounds, particularly organics, involved in the new particle formation (NPF) and its consequent growth are not fully understood. Therefore, this study was conducted to investigate the chemistry of aerosol particles during NPF events in an urban subtropical environment. Aerosol chemical composition was measured along with particle number size distribution (PNSD) and several other air quality parameters at five sites across an urban subtropical environment. An Aerodyne compact Time-of-Flight Aerosol Mass Spectrometer (c-TOF-AMS) and a TSI Scanning Mobility Particle Sizer (SMPS) measured aerosol chemical composition and PNSD, respectively. Five NPF events, with growth rates in the range 3.3-4.6 nm, were detected at two sites. The NPF events happened on relatively warmer days with lower humidity and higher solar radiation. Temporal percent fractions of nitrate, sulphate, ammonium and organics were modelled using the Generalised Additive Model (GAM), with a basis of penalised spline. Percent fractions of organics increased after the NPF events, while the mass fraction of ammonium and sulphate decreased. This uncovered the important role of organics in the growth of newly formed particles. Three organic markers, factors f43, f44 and f57, were calculated and the f44 vs f43 trends were compared between nucleation and non-nucleation days. f44 vs f43 followed a different pattern on nucleation days compared to non-nucleation days, whereby f43 decreased for vehicle emission generated particles, while both f44 and f43 decreased for NPF generated particles. It was found for the first time that vehicle generated and newly formed particles cluster in different locations on f44 vs f43 plot and this finding can be used as a tool for source apportionment of measured particles.

Atmospheric visibility and PM10 as indicators of new particle formation in an urban environment

It is well-known that new particle formation (NPF) in the atmosphere is inhibited by pre-existing particles in the air that act as condensation sinks to decrease the concentration and, thus, the supersaturation of precursor gases. In this study, we investigate the effects of two parameters - atmospheric visibility, expressed as the particle back-scatter coefficient (BSP), and PM10 particulate mass concentration, on the occurrences of NPF events in an urban environment where the majority of precursor gases originate from motor vehicle and industrial sources. This is the first attempt to derive direct relationships between each of these two parameters and the occurrence of NPF. NPF events were identified from data obtained with a neutral cluster and air ion spectrometer over 245 days within a calendar year. Bayesian logistic regression was used to determine the probability of observing NPF as functions of BSP and PM10. We show that the BSP at 08 h on a given day is a reliable indicator of an NPF event later that day. The posterior median probability of observing an NPF event was greater than 0.5 (95%) when the BSP at 08 h was less than 6.8 Mm-1.

Experiments on homogeneous nucleation and physicochemical properties related to atmospheric new particle formation

Aerosol particles play a role in the earth ecosystem and affect human health. A significant pathway of producing aerosol particles in the atmosphere is new particle formation, where condensable vapours nucleate and these newly formed clusters grow by condensation and coagulation. However, this phenomenon is still not fully understood. This thesis brings an insight to new particle formation from an experimental point of view. Laboratory experiments were conducted both on the nucleation process and physicochemical properties related to new particle formation. Nucleation rate measurements are used to test nucleation theories. These theories, in turn, are used to predict nucleation rates in atmospheric conditions. However, the nucleation rate measurements have proven quite difficult to conduct, as different devices can yield nucleation rates with differences of several orders of magnitude for the same substances. In this thesis, work has been done to have a greater understanding in nucleation measurements, especially those conducted in a laminar flow diffusion chamber. Systematic studies of nucleation were also made for future verification of nucleation theories. Surface tensions and densities of substances related to atmospheric new particle formation were measured. Ternary sulphuric acid + ammonia + water is a proposed candidate to participate in atmospheric nucleation. Surface tensions of an alternative candidate to nucleate in boreal forest areas, sulphuric acid + dimethylamine + water, were also measured. Binary compounds, consisting of organic acids + water are possible candidates to participate in the early growth of freshly nucleated particles. All the measured surface tensions and densities were fitted with equations, thermodynamically consistent if possible, to be easily applied to atmospheric model calculations of nucleation and subsequent evolution of particle size.

Numerical approaches to new particle formation and growth in the atmosphere

Aerosols impact the planet and our daily lives through various effects, perhaps most notably those related to their climatic and health-related consequences. While there are several primary particle sources, secondary new particle formation from precursor vapors is also known to be a frequent, global phenomenon. Nevertheless, the formation mechanism of new particles, as well as the vapors participating in the process, remain a mystery. This thesis consists of studies on new particle formation specifically from the point of view of numerical modeling. A dependence of formation rate of 3 nm particles on the sulphuric acid concentration to the power of 1-2 has been observed. This suggests nucleation mechanism to be of first or second order with respect to the sulphuric acid concentration, in other words the mechanisms based on activation or kinetic collision of clusters. However, model studies have had difficulties in replicating the small exponents observed in nature. The work done in this thesis indicates that the exponents may be lowered by the participation of a co-condensing (and potentially nucleating) low-volatility organic vapor, or by increasing the assumed size of the critical clusters. On the other hand, the presented new and more accurate method for determining the exponent indicates high diurnal variability. Additionally, these studies included several semi-empirical nucleation rate parameterizations as well as a detailed investigation of the analysis used to determine the apparent particle formation rate. Due to their high proportion of the earth's surface area, oceans could potentially prove to be climatically significant sources of secondary particles. In the lack of marine observation data, new particle formation events in a coastal region were parameterized and studied. Since the formation mechanism is believed to be similar, the new parameterization was applied in a marine scenario. The work showed that marine CCN production is feasible in the presence of additional vapors contributing to particle growth. Finally, a new method to estimate concentrations of condensing organics was developed. The algorithm utilizes a Markov chain Monte Carlo method to determine the required combination of vapor concentrations by comparing a measured particle size distribution with one from an aerosol dynamics process model. The evaluation indicated excellent agreement against model data, and initial results with field data appear sound as well.

Experimental studies on new particle formation and ions

Atmospheric aerosol particles have significant climatic effects. Secondary new particle formation is a globally important source of these particles. Currently, the mechanisms of particle formation and the vapours participating in this process are, however, not truly understood. The recently developed Neutral cluster and Air Ion Spectrometer (NAIS) was widely used in field studies of atmospheric particle formation. The NAIS was calibrated and found to be in adequate agreement with the reference instruments. It was concluded that NAIS can be reliably used to measure ions and particles near the sizes where the atmospheric particle formation begins. The main focus of this thesis was to study new particle formation and participation of ions in this process. To attain this objective, particle and ion formation and growth rates were studied in various environments - at several field sites in Europe, in previously rarely studied sites in Antarctica and Siberia and also in an indoor environment. New particle formation was observed at all sites were studied and the observations were used as indicatives of the particle formation mechanisms. Particle size-dependent growth rates and nucleation mode hygroscopic growth factors were examined to obtain information on the particle growth. It was found that the atmospheric ions participate in the initial steps of new particle formation, although their contribution was minor in the boundary layer. The highest atmospheric particle formation rates were observed at the most polluted sites where the role of ions was the least pronounced. Furthermore, the increase of particle growth rate with size suggested that enhancement of the growth by ions was negligible. Participation of organic vapours in the particle growth was supported by laboratory and field observations. It was addressed that secondary new particle formation can also be a significant source of indoor air particles. These results, extending over a wide variety of environments, give support to previous observations and increase understanding on new particle formation on a global scale.

Coupling an aerosol box model with one-dimensional flow: a tool for understanding observations of new particle formation events

Field observations of new particle formation and the subsequent particle growth are typically only possible at a fixed measurement location, and hence do not follow the temporal evolution of an air parcel in a Lagrangian sense. Standard analysis for determining formation and growth rates requires that the time-dependent formation rate and growth rate of the particles are spatially invariant; air parcel advection means that the observed temporal evolution of the particle size distribution at a fixed measurement location may not represent the true evolution if there are spatial variations in the formation and growth rates. Here we present a zero-dimensional aerosol box model coupled with one-dimensional atmospheric flow to describe the impact of advection on the evolution of simulated new particle formation events. Wind speed, particle formation rates and growth rates are input parameters that can vary as a function of time and location, using wind speed to connect location to time. The output simulates measurements at a fixed location; formation and growth rates of the particle mode can then be calculated from the simulated observations at a stationary point for different scenarios and be compared with the ‘true’ input parameters. Hence, we can investigate how spatial variations in the formation and growth rates of new particles would appear in observations of particle number size distributions at a fixed measurement site. We show that the particle size distribution and growth rate at a fixed location is dependent on the formation and growth parameters upwind, even if local conditions do not vary. We also show that different input parameters used may result in very similar simulated measurements. Erroneous interpretation of observations in terms of particle formation and growth rates, and the time span and areal extent of new particle formation, is possible if the spatial effects are not accounted for.

On the diurnal cycle of urban aerosols, black carbon and the occurrence of new particle formation events in springtime Sao Paulo, Brazil

Large conurbations are a significant source of the anthropogenic pollution and demographic differences between cities that result in a different pollution burden. The metropolitan area of Sao Paulo (MASP, population 20 million) accounts for one fifth of the Brazilian vehicular fleet. A feature of MASP is the amount of ethanol used by the vehicular fleet, known to exacerbate air quality. The study describes the diurnal behaviour of the submicron aerosol and relies on total particle number concentration, particle number size distribution, light scattering and light absorption measurements. Modelled planetary boundary layer (PBL) depth and air mass movement data were used to aid the interpretation. During morning rush-hour, stagnant air and a shallow PBL height favour the accumulation of aerosol pollution. During clear-sky conditions, there was a wind shift towards the edge of the city indicating a heat island effect with implications on particulate pollution levels at the site. The median total particle number concentration for the submicron aerosol typically varied in the range 1.6 x 10(4)-3.2 x 10(4) cm(-3) frequently exceeding 4 x 10(4) cm-3 during the day. During weekdays, nucleation-mode particles are responsible for most of the particles by numbers. The highest concentrations of total particle number concentrations and black carbon (BC) were observed on Fridays. Median diurnal values for light absorption and light scattering (at 637 nm wavelength) varied in the range 12-33 Mm(-1) and 21-64 Mm(-1), respectively. The former one is equal to 1.8-5.0 mu g m(-3) of BC. The growth of the PBL, from the morning rush-hour until noon, is consistent with the diurnal cycle of BC mass concentrations. Weekday hourly median single-scattering albedo (omega(0)) varied in the range 0.59-0.76. Overall, this suggests a top of atmosphere (TOA) warming effect. However, considering the low surface reflectance of urban areas, for the given range of omega(0), the TOA radiative forcing can be either positive or negative for the sources within the MASP. On the average, weekend omega(0) values were 0.074 higher than during weekdays. During 11% of the days, new particle formation (NPF) events occurred. The analysed events growth rates ranged between 9 and 25 nm h(-1). Sulphuric acid proxy concentrations calculated for the site were less than 5% of the concentration needed to explain the observed growth. Thus, other vapours are likely contributors to the observed growth.