Nanoparticles in European cities and associated health impacts

Atmospheric nanoparticles are one of those pollutants currently unregulated through ambient air quality standards. The aim of this chapter is to assess the environmental and health impacts of atmospheric nanoparticles in European environments. The chapter begins with the conventional information on the origin of atmospheric nanoparticles, followed by their physical and chemical characteristics. A brief overview of recently published review articles on this topic is then presented to guide those readers interested in exploring any specific aspect of nanoparticles in greater detail. A further section reports a summary of recently published studies on atmospheric nanoparticles in European cities. This covers a total of about 45 sampling locations in 30 different cities within 15 European countries for quantifying levels of roadside and urban background particle number concentrations (PNCs). Average PNCs at roadside and urban background sites were found to be 3.82±3.25 ×104 cm–3 and 1.63±0.82 ×104 cm–3, respectively, giving a roadside to background PNC ratio of ~2.4. Engineered nanoparticles are one of the key emerging categories of airborne nanoparticles, especially for the indoor environments. Their ambient concentrations may increase in future due to widespread use of nanotechnology integrated products. Evaluation of their sources and probable impacts on air quality and human health are briefly discussed in the following section. Respiratory deposition doses received by the public exposed to roadside PNCs in numerous European locations are then estimated. These were found to be in the 1.17–7.56 1010 h–1 range over the studied roadside European locations. The following section discusses the potential framework for airborne nanoparticle regulations in Europe and, in addition, the existing control measures to limit nanoparticle emissions at source. The chapter finally concludes with a synthesis of the topic areas covered and highlights important areas for further work.

Aerosol mass spectrometric analysis of the chemical composition of non- refractory PM1 samples from school environments in Brisbane, Australia

Long term exposure to vehicle emissions has been associated with harmful health effects. Children are amongst the most susceptible group and schools represent an environment where they can experience significant exposure to vehicle emissions. However, there are limited studies on children’s exposure to vehicle emissions in schools. The aim of this study was to quantify the concentration of organic aerosol and in particular, vehicle emissions that children are exposed to during school hours. Therefore an Aerodyne compact time-of-flight aerosol mass spectrometer (TOF-AMS) was deployed at five urban schools in Brisbane, Australia. The TOF-AMS enabled the chemical composition of the non- refractory (NR-PM1) to be analysed with a high temporal resolution to assess the concentration of vehicle emissions and other organic aerosols during school hours. At each school the organic fraction comprised the majority of NR-PM1 with secondary organic aerosols as the main constitute. At two of the schools, a significant source of the organic aerosol (OA) was slightly aged vehicle emissions from nearby highways. More aged and oxidised OA was observed at the other three schools, which also recorded strong biomass burning influences. Primary emissions were found to dominate the OA at only one school which had an O:C ratio of 0.17, due to fuel powered gardening equipment used near the TOF-AMS. The diurnal cycle of OA concentration varied between schools and was found to be at a minimum during school hours. The major organic component that school children were exposed to during school hours was secondary OA. Peak exposure of school children to HOA occurred during school drop off and pick up times. Unless a school is located near major roads, children are exposed predominately to regional secondary OA as opposed to local emissions during schools hours in urban environments.

Analysis of organic aerosols collected on filters by Aerosol Mass Spectrometry for source identification

Aerosol mass spectrometers (AMS) are powerful tools in the analysis of the chemical composition of airborne particles, particularly organic aerosols which are gaining increasing attention. However, the advantages of AMS in providing on-line data can be outweighed by the difficulties involved in its use in field measurements at multiple sites. In contrast to the on-line measurement by AMS, a method which involves sample collection on filters followed by subsequent analysis by AMS could significantly broaden the scope of AMS application. We report the application of such an approach to field studies at multiple sites. An AMS was deployed at 5 urban schools to determine the sources of the organic aerosols at the schools directly. PM1 aerosols were also collected on filters at these and 20 other urban schools. The filters were extracted with water and the extract run through a nebulizer to generate the aerosols, which were analysed by an AMS. The mass spectra from the samples collected on filters at the 5 schools were found to have excellent correlations with those obtained directly by AMS, with r2 ranging from 0.89 to 0.98. Filter recoveries varied between the schools from 40 -115%, possibly indicating that this method provides qualitative rather than quantitative information. The stability of the organic aerosols on Teflon filters was demonstrated by analysing samples stored for up to two years. Application of the procedure to the remaining 20 schools showed that secondary organic aerosols were the main source of aerosols at the majority of the schools. Overall, this procedure provides accurate representation of the mass spectra of ambient organic aerosols and could facilitate rapid data acquisition at multiple sites where AMS could not be deployed for logistical reasons.

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.

Spatial distribution of aerosol black carbon over India during pre-monsoon season

Aerosol black carbon (BC) mass concentrations ([BC]), measured continuously during a multi-platform field experiment, Integrated Campaign for Aerosols gases and Radiation Budget (ICARB, March-May 2006), from a network of eight observatories spread over geographically distinct environments of India, (which included five mainland stations, one highland station, and two island stations (one each ill Arabian Sea and Bay of Bengal)) are examined for their spatio-temporal characteristics. During the period of study, [BC] showed large variations across the country, with values ranging from 27 mu g m(3) over industrial/urban locations to as low as 0.065 mu g m(-3) over the Arabian Sea. For all mainland stations, [BC] remained high compared to highland as well as island stations. Among the island stations, Port Blair (PBR) had higher concentration of BC, compared to Minicoy (MCY), implying more absorbing nature of Bay of Bengal aerosols than Arabian Sea. The highland station Nainital (NTL), in the central Himalayas, showed low values of [BC], comparable or even lower than that of the island station PBR, indicating the prevalence of cleaner environment over there. An examination of the changes in the mean temporal features, as the season advances from winter (December-February) to pre-monsoon (March-May), revealed that: (a) Diurnal variations were pronounced over all the mainland stations, with all afternoon low and a nighttime high: (b) At the islands, the diurnal variations, though resembled those over the mainlands, were less pronounced; and (c) In contrast to this, highland station showed an opposite pattern with an afternoon high and a late night or early morning low. The diurnal variations at all stations are mainly caused by the dynamics of local Atmospheric Boundary Layer (ABL), At the entire mainland as well as island stations (except HYD and DEL), [BC] showed a decreasing trend from January to May, This is attributed to the increased convective mixing and to the resulting enhanced vertical dispersal of species in the ABL. In addition, large short-period modulations were observed at DEL and HYD, which appeared to be episodic, An examination of this in the light of the MODIS-derived fire count data over India along with the back-trajectory analysis revealed that advection of BC from extensive forest fires and biomass-burning regions upwind were largely responsible for this episodic enhancement in BC at HYD and DEL.

Vertical structure and horizontal gradients of aerosol extinction coefficients over coastal India inferred from airborne lidar measurements during the Integrated Campaign for Aerosol, Gases and Radiation Budget (ICARB) field campaign

Quantitative estimates of the vertical structure and the spatial gradients of aerosol extinction coefficients have been made from airborne lidar measurements across the coastline into offshore oceanic regions along the east and west coasts of India. The vertical structure revealed the presence of strong, elevated aerosol layers in the altitude region of similar to 2-4 km, well above the atmospheric boundary layer (ABL). Horizontal gradients also showed a vertical structure, being sharp with the e(-1) scaling distance (D-0H) as small as similar to 150 km in the well-mixed regions mostly under the influence of local source effects. Above the ABL, where local effects are subdued, the gradients were much shallower (similar to 600-800 km); nevertheless, they were steep compared to the value of similar to 1500-2500 km reported for columnar AOD during winter. The gradients of these elevated layers were steeper over the east coast of India than over the west coast. Near-simultaneous radio sonde (Vaisala, Inc., Finland) ascents made over the northern Bay of Bengal showed the presence of convectively unstable regions, first from surface to similar to 750-1000 m and the other extending from 1750 to 3000 m separated by a stable region in between. These can act as a conduit for the advection of aerosols and favor the transport of continental aerosols in the higher levels (> 2 km) into the oceans without entering the marine boundary layer below. Large spatial gradient in aerosol optical and hence radiative impacts between the coastal landmass and the adjacent oceans within a short distance of < 300 km (even at an altitude of 3 km) during summer and the premonsoon is of significance to the regional climate.

Improved assessment of aerosol absorption using OMI-MODIS joint retrieval

The Ozone Monitoring Instrument (OMI) aboard EOS-Aura and the Moderate Resolution Imaging Spectroradiometer (MODIS) onboard EOS-Aqua fly in formation as part of the A-train. Though OMI retrieves aerosol optical depth (AOD) and aerosol absorption, it must assume aerosol layer height. The MODIS cannot retrieve aerosol absorption, but MODIS aerosol retrieval is not sensitive to aerosol layer height and with its smaller pixel size is less affected by subpixel clouds. Here we demonstrate an approach that uses MODIS-retrieved AOD to constrain the OMI retrieval, freeing OMI from making an a priori estimate of aerosol height and allowing a more direct retrieval of aerosol absorption. To predict near-UV optical depths using MODIS data we rely on the spectral curvature of the MODIS-retrieved visible and near-IR spectral AODs. Application of an OMI-MODIS joint retrieval over the north tropical Atlantic shows good agreement between OMI and MODIS-predicted AODs in the UV, which implies that the aerosol height assumed in the OMI-standard algorithm is probably correct. In contrast, over the Arabian Sea, MODIS-predicted AOD deviated from the OMI-standard retrieval, but combined OMI-MODIS retrievals substantially improved information on aerosol layer height (on the basis of validation against airborne lidar measurements). This implies an improvement in the aerosol absorption retrieval, but lack of UV absorption measurements prevents a true validation. Our study demonstrates the potential of multisatellite analysis of A-train data to improve the accuracy of retrieved aerosol products and suggests that a combined OMI-MODIS-CALIPSO retrieval has large potential to further improve assessments of aerosol absorption.

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.

How Good is the Assumption About Visible Surface Reflectance in MODIS Aerosol Retrieval Over Land? A Comparison With Aircraft Measurements Over an Urban Site in India

In this paper, we discuss the measurements of spectral surface reflectance (rho(s)(lambda)) in the wavelength range 350-2500 nm measured using a spectroradiometer onboard a low-flying aircraft over Bangalore (12.95 degrees N, 77.65 degrees E), an urban site in southern India. The large discrepancies in the retrieval of aerosol propertiesover land by the Moderate-Resolution Imaging Spectroradiometer (MODIS), which could be attributed to the inaccurate estimation of surface reflectance at many sites in India and elsewhere, provided motivation for this paper. The aim of this paper was to verify the surface reflectance relationships assumed by the MODIS aerosol algorithm for the estimation of surface reflectance in the visible channels (470 and 660 nm) from the surface reflectance at 2100 nm for aerosol retrieval over land. The variety of surfaces observed in this paper includes green and dry vegetations, bare land, and urban surfaces. The measuredreflectance data were first corrected for the radiative effects of atmosphere lying between the ground and aircraft using the Second Simulation of Satellite Signal in the Solar Spectrum (6S) radiative transfer code. The corrected surface reflectance in the MODIS's blue (rho(s)(470)), red (rho(s)(660)), and shortwave-infrared (SWIR) channel (rho(s)(2100)) was linearly correlated. We found that the slope of reflectance relationship between 660 and 2100 nm derived from the forward scattering data was 0.53 with an intercept of 0.07, whereas the slope for the relationship between the reflectance at 470 and 660 nm was 0.85. These values are much higher than the slope (similar to 0.49) for either wavelengths assumed by the MODIS aerosol algorithm over this region. The reflectance relationship for the backward scattering data has a slope of 0.39, with an intercept of 0.08 for 660 nm, and 0.65, with an intercept of 0.08 for 470 nm. The large values of the intercept (which is very small in the MODIS reflectance relationships) result in larger values of absolute surface reflectance in the visible channels. The discrepancy between the measured and assumed surface reflectances could lead to error in the aerosol retrieval. The reflectance ratio (rho(s)(660)/rho(s)(2100)) showed a clear dependence on the N D V I-SWIR where the ratio increased from 0.5 to 1 with an increase in N V I-SWIR from 0 to 0.5. The high correlation between the reflectance at SWIR wavelengths (2100, 1640, and 1240 nm) indicated an opportunity to derive the surface reflectance and, possibly, aerosol properties at these wavelengths. We need more experiments to characterize the surface reflectance and associated inhomogeneity of land surfaces, which play a critical role in the remote sensing of aerosols over land.