Effect of atmospheric ageing on volatility and ROS of biodiesel exhaust nano-particles

Generally, the magnitude of pollutant emissions from diesel engines is ultimately coupled to the structure of fuel molecules. The presence of oxygen, level of unsaturation and the carbon chain length of respective molecules influence the combustion chemistry. It is speculated that increased oxygen content in the fuel may lead to the increased oxidative potential (Stevanovic, S. 2013). Also, upon the exposure to UV and ozone in the atmosphere, the chemical composition of the exhaust is changed. The presence of an oxidant and UV is triggering the cascade of photochemical reactions as well as the partitioning of semi-volatile compounds between the gas and particle phase. To gain an insight into the relationship between the molecular structures of the esters, their volatile organic content and the potential toxicity of diesel exhaust particulate matter, measurements were conducted on a modern common rail diesel engine. This research also investigates the contribution of atmospheric conditions on the transfer of semi-volatile fraction of diesel exhaust from the gas phase to the particle phase and the extent to which semi-volatile compounds (SVOCs) are related to the oxidative potential, expressed through the concentration of reactive oxygen species (ROS) (Stevanovic, S. 2013)...

Marine aerosol hygroscopicity and volatility, measured on the Chatham Rise (New Zealand)

The Surface Ocean Aerosol Production (SOAP) study was undertaken in February/March 2012 in the biologically active waters of the Chatham Rise, NZ. Aerosol hygroscopicity and volatility were examined with a volatility hygroscopicity tandem differential mobility analyser. These observations confirm results from other hygroscopicity-based studies that the dominant fraction of the observed remote marine particles were non-sea salt sulfates. Further observations are required to clarify the influences of seawater composition, meteorology and analysis techniques seasonally across different ocean basins.

Viability of Pseudomonas aeruginosa in cough aerosols generated by persons with cystic fibrosis

Background Person-to-person transmission of respiratory pathogens, including Pseudomonas aeruginosa, is a challenge facing many cystic fibrosis (CF) centres. Viable P aeruginosa are contained in aerosols produced during coughing, raising the possibility of airborne transmission. Methods Using purpose-built equipment, we measured viable P aeruginosa in cough aerosols at 1, 2 and 4 m from the subject (distance) and after allowing aerosols to age for 5, 15 and 45 min in a slowly rotating drum to minimise gravitational settling and inertial impaction (duration). Aerosol particles were captured and sized employing an Anderson Impactor and cultured using conventional microbiology. Sputum was also cultured and lung function and respiratory muscle strength measured. Results Nineteen patients with CF, mean age 25.8 (SD 9.2) years, chronically infected with P aeruginosa, and 10 healthy controls, 26.5 (8.7) years, participated. Viable P aeruginosa were detected in cough aerosols from all patients with CF, but not from controls; travelling 4 m in 17/18 (94%) and persisting for 45 min in 14/18 (78%) of the CF group. Marked inter-subject heterogeneity of P aeruginosa aerosol colony counts was seen and correlated strongly (r=0.73–0.90) with sputum bacterial loads. Modelling decay of viable P aeruginosa in a clinic room suggested that at the recommended ventilation rate of two air changes per hour almost 50 min were required for 90% to be removed after an infected patient left the room. Conclusions Viable P aeruginosa in cough aerosols travel further and last longer than recognised previously, providing additional evidence of airborne transmission between patients with CF.

Air ion concentrations under overhead power lines

Corona discharge is responsible for the flux of small ions from overhead power lines, and is capable of modifying the ambient electrical environment, such as the air ion concentrations at ground level. Once produced, small ions quickly attach to aerosol particles in the air, producing ‘large ions’, approximately 1 nm to 1 µm in diameter. However, very few studies have measured air ion concentrations directly near high voltage transmission lines. The present study involved the simultaneously measurement of small ion concentration and net large ion concentration using air ion counters and an aerosol electrometer at four power line sites. Both positive and negative small ion concentration (<1.6nm), net large ion concentration (2nm-5μm) and particle number concentration (10nm-2μm) were measured using air ion counters and an aerosol electrometer at four power line sites. Measurements at sites 1 and 2 were conducted at both upwind and downwind sides. The results showed that total ion concentrations on the downwind side were 3-5 times higher than on the upwind side, while particle number concentrations did not show a significant difference. This result also shows that a large number of ions were emitted from the power lines at sites 1 and 2. Furthermore, both positive and negative ions were observed at different power line sites. Dominant positive ions were observed at site 1, with a concentration of 4.4 x 103 ions cm-3, which was 10 times higher than on the upwind side. Contrary to site 1, sites 2 to 4 showed negative ion emissions, with concentrations of -1.2 x 103, -460 and -410 ions cm-3, respectively. These values were higher than the background urban negative ion concentration of 400 cm-3. At site 1 and site 2, the net ion concentration and net particle charge concentration on downwind side of the lines showed same polarities. Further investigations were also conducted into the correlation between net ion concentration and net charge particle concentration 20 m downwind of the power lines at site 2. The two parameters showed a correlation coefficient of 0.72, indicating that a substantial number of ions could attach to particles and affect the particle charge status within a short distance from the source.

Comparison of particle number concentrations between different environments

Particle number concentrations vary significantly with environment and, in this study, we attempt to assess the significance of these differences. Towards this aim, we reviewed 85 papers that have reported particle number concentrations levels at 126 sites covering different environments. We grouped the results into eight categories according to measurement location including: road tunnel, on-road, road-side, street canyon, urban, urban background, rural, and clean background. Median values were calculated for each category. This review was restricted to papers that presented concentrations numerically. The majority of the reports were based on either CPC or SMPS measurements, with a limited number of papers reporting results from both instruments at the same site. Hence there were several overlaps between the number of CPC and SMPS measuring sites. Most of the studies reported multiple measurements at a given study site, while some studies included results from more than one site. From these reports, the overall median value for each location category was calculated...

Assessment and application of clustering techniques to atmospheric particle number size distribution for the purpose of source apportionment

Long-term measurements of particle number size distribution (PNSD) produce a very large number of observations and their analysis requires an efficient approach in order to produce results in the least possible time and with maximum accuracy. Clustering techniques are a family of sophisticated methods which have been recently employed to analyse PNSD data, however, very little information is available comparing the performance of different clustering techniques on PNSD data. This study aims to apply several clustering techniques (i.e. K-means, PAM, CLARA and SOM) to PNSD data, in order to identify and apply the optimum technique to PNSD data measured at 25 sites across Brisbane, Australia. A new method, based on the Generalised Additive Model (GAM) with a basis of penalised B-splines, was proposed to parameterise the PNSD data and the temporal weight of each cluster was also estimated using the GAM. In addition, each cluster was associated with its possible source based on the results of this parameterisation, together with the characteristics of each cluster. The performances of four clustering techniques were compared using the Dunn index and Silhouette width validation values and the K-means technique was found to have the highest performance, with five clusters being the optimum. Therefore, five clusters were found within the data using the K-means technique. The diurnal occurrence of each cluster was used together with other air quality parameters, temporal trends and the physical properties of each cluster, in order to attribute each cluster to its source and origin. The five clusters were attributed to three major sources and origins, including regional background particles, photochemically induced nucleated particles and vehicle generated particles. Overall, clustering was found to be an effective technique for attributing each particle size spectra to its source and the GAM was suitable to parameterise the PNSD data. These two techniques can help researchers immensely in analysing PNSD data for characterisation and source apportionment purposes.

Effect of atmospheric aging on volatility and reactive oxygen species of biodiesel exhaust nano-particles

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.

Traffic and nucleation events as main sources of ultrafine particles in high-insolation developed world cities

Road traffic emissions are often considered the main source of ultrafine particles (UFP, diameter smaller than 100 nm) in urban environments. However, recent studies worldwide have shown that - in high-insolation urban regions at least - new particle formation events can also contribute to UFP. In order to quantify such events we systematically studied three cities located in predominantly sunny environments: Barcelona (Spain), Madrid (Spain) and Brisbane (Australia). Three long term datasets (1-2 years) of fine and ultrafine particle number size distributions (measured by SMPS, Scanning Mobility Particle Sizer) were analysed. Compared to total particle number concentrations, aerosol size distributions offer far more information on the type, origin and atmospheric evolution of the particles. By applying k-Means clustering analysis, we categorized the collected aerosol size distributions in three main categories: “Traffic” (prevailing 44-63% of the time), “Nucleation” (14-19%) and “Background pollution and Specific cases” (7-22%). Measurements from Rome (Italy) and Los Angeles (California) were also included to complement the study. The daily variation of the average UFP concentrations for a typical nucleation day at each site revealed a similar pattern for all cities, with three distinct particle bursts. A morning and an evening spike reflected traffic rush hours, whereas a third one at midday showed nucleation events. The photochemically nucleated particles burst lasted 1-4 hours, reaching sizes of 30-40 nm. On average, the occurrence of particle size spectra dominated by nucleation events was 16% of the time, showing the importance of this process as a source of UFP in urban environments exposed to high solar radiation. On average, nucleation events lasting for 2 hours or more occurred on 55% of the days, this extending to >4hrs in 28% of the days, demonstrating that atmospheric conditions in urban environments are not favourable to the growth of photochemically nucleated particles. In summary, although traffic remains the main source of UFP in urban areas, in developed countries with high insolation urban nucleation events are also a main source of UFP. If traffic-related particle concentrations are reduced in the future, nucleation events will likely increase in urban areas, due to the reduced urban condensation sinks.

Dimethyl sulfide and other biogenic volatile organic compound emissions from branching coral and reef seawater: Potential sources of secondary aerosol over the Great Barrier Reef

Volatile organic compounds (VOCs) in the headspace of bubble chambers containing branches of live coral in filtered reef seawater were analysed using gas chromatography with mass spectrometry (GC-MS). When the coral released mucus it was a source of dimethyl sulfide (DMS) and isoprene; however, these VOCs were not emitted to the chamber headspace from mucus-free coral. This finding, which suggests that coral is an intermittent source of DMS and isoprene, was supported by the observation of occasional large pulses of atmospheric DMS (DMSa) over Heron Island reef on the southern Great Barrier Reef (GBR), Australia, in the austral winter. The highest DMSa pulse (320 ppt) was three orders of magnitude less than the DMS mixing ratio (460 ppb) measured in the headspace of a dynamically purged bubble chamber containing a mucus-coated branch of Acropora aspera indicating that coral reefs can be strong point sources of DMSa. Static headspace GC-MS analysis of coral fragments identified mainly DMS and seven other minor reduced sulfur compounds including dimethyl disulfide, methyl mercaptan, and carbon disulfide, while coral reef seawater was an indicated source of methylene chloride, acetone, and methyl ethyl ketone. The VOCs emitted by coral and reef seawater are capable of producing new atmospheric particles < 15 nm diameter as observed at Heron Island reef. DMS and isoprene are known to play a role in low-level cloud formation, so aerosol precursors such as these could influence regional climate through a sea surface temperature regulation mechanism hypothesized to operate over the GBR.

Airborne particulate matter at a bus station : concentration levels and governing parameters

Traffic emissions are an important contributor to ambient air pollution, especially in large cities featuring extensive and high density traffic networks. Bus fleets represent a significant part of inner city traffic causing an increase in exposure to general public, passengers and drivers along bus routes and at bus stations. Limited information is available on quantification of the levels, and governing parameters affecting the air pollution exposure at bus stations. The presented study investigated the bus emissions-dominated ambient air in a large, inner city bus station, with a specific focus on submicrometer particles. The study’s objectives were (i) quantification of the concentration levels; (ii) characterisation of the spatio-temporal variation; (iii) identification of the parameters governing the emissions levels at the bus station and (iv) assessment of the relationship between particle concentrations measured at the street level (background) and within the bus station. The results show that up to 90% of the emissions at the station are ultrafine particles (smaller than 100 nm), with the concentration levels up to 10 times the value of urban ambient air background (annual) and up to 4 times the local ambient air background. The governing parameters affecting particle concentration at the station were bus flow rate and meteorological conditions (wind velocity). Particle concentration followed a diurnal trend, with an increase in the morning and evening, associated with traffic rush hours. Passengers’ exposure could be significant compared to the average outdoor and indoor exposure levels.

On the efficiency of impingers with fritted nozzle tip for collection of ultrafine particles

The aim of this study was to determine the collection efficiency of ultrafine particles into an impinger fitted with a fritted nozzle tip as a means to increase contact surface area between the aerosol and the liquid. The influence of liquid sampling volume, frit porosity and the nature of the sampling liquid was explored and it was shown that all impact on the collection efficiency of particles smaller than 220 nm. Obtained values for overall collection efficiency were substantially higher (~30–95%) than have been previously reported, mainly due to the high deposition of particles in the fritted nozzle tip, especially in case of finer porosity frits and smaller particles. Values for the capture efficiency of the solvent alone ranged from 20 to 45%, depending on the type and the volume of solvent. Additionally, our results show that airstream dispersion into bubbles improves particle trapping by the liquid and that there is a difference in collection efficiencies based on the nature and volume of the solvent used.

Size distribution and sites of origin of droplets expelled during expiratory activities

A new Expiratory Droplet Investigation System (EDIS) was used to conduct the most comprehensive program of study to date, of the dilution corrected droplet size distributions produced during different respiratory activities.----- Distinct physiological processes were responsible for specific size distribution modes. The majority of particles for all activities were produced in one or more modes, with diameters below 0.8 µm. That mode occurred during all respiratory activities, including normal breathing. A second mode at 1.8 µm was produced during all activities, but at lower concentrations.----- Speech produced particles in modes near 3.5 µm and 5 µm. The modes became most pronounced during continuous vocalization, suggesting that the aerosolization of secretions lubricating the vocal chords is a major source of droplets in terms of number.----- Non-eqilibrium droplet evaporation was not detectable for particles between 0.5 and 20 μm implying that evaporation to the equilibrium droplet size occurred within 0.8 s.