Ultrafine particle fluxes above four major European cities

Little information is known about the behaviour of ultrafine particles (UFP) on a citywide scale. Total particle number flux, dominated by UFP, and other meteorological parameters were collected from tower sites in Manchester, London, Edinburgh and Gothenburg between 1999 and 2006 using the eddy covariance technique. Averaged diurnal cycles were produced for particle number flux, concentration, sensible heat flux, emission velocity, friction velocity, wind speed and temperature. UFP flux cycles showed clear diurnal trends which were linked to traffic activity and local sources. Wind sector analysis showed contributions to flux from local heavily urbanised areas. A simple parameterised model linking UFP flux to traffic activity, sensible heat and friction velocity above the city was produced.     

Assessment of source apportionment by Positive Matrix Factorization analysis on fine and coarse urban aerosol size fractions

This study was conducted in order to investigate the differences observed in source profiles in the urban environment, when chemical composition parameters from different aerosol size fractions are subjected to factor analysis. Source apportionment was performed in an urban area where representative types of emission sources are present. PM₁₀ and PM₂ samples were collected within the Athens Metropolitan area and analysed for trace elements, inorganic ions and black carbon. Analysis by two-way and three-way Positive Matrix Factorization was performed, in order to resolve sources from data obtained for the fine and coarse aerosol fractions. A difference was observed: seven factors describe the best solution in PMF3 while six factors in PMF2. Six factors derived from PMF3 analysis correspond to those described by the PMF2 solution for the fine and coarse particles separately. These sources were attributed to road dust, marine aerosol, soil, motor vehicles, biomass burning, and oil combustion. The additional source resolved by PMF3 was attributed to a different type of road dust. Combustion sources (oil combustion and biomass burning) were correctly attributed by PMF3 solely to the fine fraction and the soil source to the coarse fraction. However, a motor vehicle's contribution to the coarse fraction was found only by three-way PMF. When PMF2 was employed in PM₁₀ concentrations the optimum solution included six factors. Four source profiles corresponded to the previously identified as vehicles, road dust, biomass burning and marine aerosol, while two could not be clearly identified. Source apportionment by PMF2 analysis based solely on PM₁₀ aerosol composition data, yielded unclear results, compared to results from PMF2 and PMF3 analyses on fine and coarse aerosol composition data.     

Night-time radical chemistry during the TORCH campaign

We present one of the most comprehensive studies of night-time radical chemistry to date, from the Tropospheric ORganic CHemistry experiment (TORCH) in the summer of 2003. TORCH provided a wealth of measurements with which to study the oxidizing capacity of the atmosphere. The measurements provided input to a zero-dimensional box model which has been used to study night-time radical chemistry during the campaign. Average night-time predicted concentrations of OH (2.6 × 10⁵ molecule cm^?3), HO₂ (2.9 × 10⁷ molecule cm^?3) and [HO₂+ΣRO₂] radicals (2.2 × 10⁸ molecule cm^?3) were an order of magnitude smaller than those predicted during the daytime. The model under-predicted the night-time measurements of OH, HO₂ and [HO₂+ΣRO₂] radicals, on average by 41%, 16% and 8% respectively. Whilst the model captured the broad features of night-time radical behaviour, some of the specific features that were observed are hard to explain. A rate of radical production assessment was carried out for the whole campaign between the hours of 00:00 and 04:00. Whilst radical production was limited owing to the absence of photolytic reactions, production routes via the reactions of alkenes with O₃ provided an effective night-time radical source. Nitrate radical concentrations were predicted to be 0.6 ppt on average with a peak of 18 ppt on August 9th during a polluted heat wave period. Overall, the nitrate radical contributes about a third of the total initiation via RO₂, mostly through reaction with alkenes.     

Analysis of cloud and precipitation chemistry at Whiteface Mountain,NY

Federal and state programs over the past two decades have resulted in the reduction of emissions of precursors of acid rain. Concomitant with these changes, measured concentrations of acidity in precipitation and in watersheds have shown a downward trend or improvement. However, another pathway for these precursors is through cloud and fog events that often tend to occur at high-elevation regions affecting the fauna and flora as well. In this study we report on long-term measurements of cloud water and precipitation chemistry made from 1994 onwards at a high-elevation location, Whiteface Mountain NY, in the northeastern United States. Trends and inter-relationship between the ions were examined along with ambient SO₂ measurements and Adirondack lakes chemistry data.     

Investigating the chemical nature of humic-like substances (HULIS) in North American atmospheric aerosols by liquid chromatography tandem mass spectrometry

The high-molecular weight water-soluble organic compounds present in atmospheric aerosols underwent functional-group characterization using liquid chromatography tandem mass spectrometry (LC-MS/MS), with a focus on understanding the chemical structure and origins of humic-like substances (HULIS) in the atmosphere. Aerosol samples were obtained from several locations in North America at times when primary sources contributing to organic aerosol were well-characterized: Riverside, CA, Fresno, CA, urban and peripheral Mexico City, Atlanta, GA, and Bondville, IL. Chemical analysis targeted identification and quantification of functional groups, such as aliphatic, aromatic, and bulk carboxylic acids, organosulfates, and carbohydrate-like substances that comprise species with molecular weights (MW) 200–600 amu. Measured high-MW functional groups were compared to modeled primary sources with the purpose of identifying associations between aerosol sources, high-MW aerosol species, and HULIS. Mobile source emissions were linked to high-molecular weight carboxylic acids, especially aromatic acids, biomass burning was associated with carboxylic acids and carbohydrate-like substances, and secondary organic aerosol (SOA) correlated well with the total amount of HULIS measured, whereas organosulfates showed no correlation with aerosol sources and exhibited unique spatial trends. These results suggested the importance of motor vehicles, biomass burning, and SOA as important sources of precursors to HULIS. Structural characteristics of atmospheric HULIS were compared to terrestrial humic and fulvic acids and revealed striking similarities in chemical structure, with the exception of organosulfates which were unique to atmospheric HULIS.     

Characterization of PM2.5-bound polycyclic aromatic hydrocarbons in Atlanta—Seasonal variations at urban,suburban, and rural ambient air monitoring sites

Twenty-eight polycyclic aromatic hydrocarbons (PAH) and methylated PAHs (Me-PAH) were measured in daily PM_2.5 samples collected at an urban site, a suburban site, and a rural site in and near Atlanta during 2004 (5 samples/month/site). The suburban site, located near a major highway, had higher PM_2.5-bound PAH concentrations than did the urban site, and the rural site had the lowest PAH levels. Monthly variations are described for concentrations of total PAHs (∑PAHs) and individual PAHs. PAH concentrations were much higher in cold months than in warm months, with average monthly ∑PAH concentrations at the urban and suburban-highway monitoring sites ranging from 2.12 to 6.85 ng m^?3 during January–February and November–December 2004, compared to 0.38–0.98 ng m^?3 during May–September 2004. ∑PAH concentrations were found to be well correlated with PM_2.5 and organic carbon (OC) within seasons, and the fractions of PAHs in PM_2.5 and OC were higher in winter than in summer. Methyl phenanthrenes were present at higher levels than their un-substituted homologue (phenanthrene), suggesting a petrogenic (unburned petroleum products) input. Retene, a proposed tracer for biomass burning, peaked in March, the month with the highest acreage and frequency of prescribed burning and unplanned fires, and in December, during the high residential wood-burning season, indicating that retene might be a good marker for burning of all biomass materials. In contrast, potassium peaked only in December, indicating that it might be a more specific tracer for wood-burning.     

Investigations of an intense aerosol loading during 2007 cyclone SIDR – A study using satellite data and ground measurements over Indian region

Tropical cyclones are prominent weather systems characterized by high atmospheric pressure gradients and wind speeds. Intense tropical cyclones occur in India during the pre-monsoon (spring), early monsoon (early summer), or post-monsoon (fall) periods. Originating in both the Bay of Bengal (BoB) and the Arabian Sea (AS), these tropical cyclones often attain velocities of more than 100 km h^?1 and are notorious for causing intense rain and storm surge as they cross the Indian coast. In this study, we examine the changes in the aerosol properties associated with an intense tropical cyclone “SIDR”, that occurred during 11–16 November 2007 over BoB. This cyclone, accompanied with very strong surface winds reaching 223 km h^?1, caused extensive damage over Bangladesh. Ground-based measurements of Aerosol Optical Depth (AOD) in the neighboring urban environment of Hyderabad, India, showed significant variations due to changes in wind velocity and direction associated with the cyclone passage. The Terra-MODIS and AVHRR satellite images showed prevalence of dust particles mixed with emissions from anthropogenic sources and biomass-burning AS, while the aerosol loading over BoB was significantly lower. The positive values of Aerosol index (AI) obtained from the Ozone Monitoring Instrument (OMI) suggested the presence of an elevated aerosol layer over the West coast of India, AS and Thar Desert during and after the cyclone episode. Meteorological parameters from the MM5 mesoscale model were used to study the variations in winds associated with the cyclonic activity. Particulate matter loading over the region during the cyclone period increased by ～45% with an accompanying decrease in columnar aerosol optical depth. The variations in Angstrom parameters suggested coarse-mode particle loading due to dust aerosols as observed in satellite data.     

Effect of typhoon on atmospheric particulates in autumn in central Taiwan

Previous studies have suggested that the ongoing global climate change will likely increase the intensity and frequency of extreme weather, such as typhoons. Since the beginning of global warming, it has become necessary to understand the influence of typhoons on air quality. Rare data, especially particulate measurements data could be used to establish the relationship between the air pollution and typhoons. One of main limiting factors is that most of the previous chemical analyses of particulates used a relatively long sampling time, which could dilute the temporal impact of particulate characteristics and their sources. This work, depending more time-resolved measurements, focus on the characteristics and sources of high particulate matter levels and the influence of typhoons and the Pacific high system. Depending on the measurements, two pollutant groups were clearly identified in this work. The first pollutant group was the emissions from neighboring riverbeds under the strong circulation of the typhoon in the driest season and characterized as high coarse particle concentrations with high mass fraction of Ca²⁺. The second pollutant group was characterized as the formation and transport of secondary particles with prevalent ions of NH₄⁺, NO₃^?, and SO₄^2? and occurred in the sea-land breeze circulation under the influence the Pacific high system.     

Organic aerosol characterization by complementary measurements of chemical bonds and molecular fragments

Organic aerosol chemical markers from normalized concentrations of independent measurements of mass fragments (using Aerosol Mass Spectrometry, AMS) are compared to bond-based functional groups (from Fourier Transform Infrared spectroscopy, FTIR) during eight field projects in the western hemisphere. Several field projects show weak correlations between alcohol group fractions and m/z 60 fractions, consistent with the organic hydroxyl groups and the fragmentation of saccharides, but the weakness of the correlations indicate chemical differences among the relationships for ambient aerosols in different regions. Carboxylic acid group fractions and m/z 44 fractions are correlated weakly for three projects, with correlations expected for aerosols dominated by di-acid compounds since their fragmentation is typically dominated by m/z 44. Despite differences for three projects with ratios of m/z 44 to m/z 57 fragments less than 10, five projects showed a linear trend between the project-average m/z 44 to m/z 57 ratio and the ratio of acid and alkane functional groups. While this correlation explains only a fraction of the fragment and bond variability measured, the consistency of this relationship at multiple sites indicates a general agreement with the interpretation of the relative amount of m/z 44 as a carboxylic acid group marker and m/z 57 as an alkane group marker.     

High time-resolved measurements of organic air toxics in different source regimes

High time-resolved (HTR) measurements can provide significant insight into sources and exposures of air pollution. In this study, an automated instrument was developed and deployed to measure hourly concentrations of 18 gas-phase organic air toxics and 6 volatile organic compounds (VOCs) at three sites in and around Pittsburgh, Pennsylvania. The sites represent different source regimes: a site with substantial mobile-source emissions; a residential site adjacent to a heavily industrialized zone; and an urban background site. Despite the close proximity of the sites (less than 13 km apart), the temporal characteristic of outdoor concentrations varied widely. Most of the compounds measured were characterized by short periods of elevated concentrations or plume events, but the duration, magnitude and composition of these events varied from site to site. The HTR data underscored the strong role of emissions from local sources on exposure to most air toxics. Plume events contributed more than 50% of the study average concentrations for all pollutants except chloroform, 1,2-dichloroethane, and carbon tetrachloride. Wind directional dependence of air toxic concentrations revealed that emissions from large industrial facilities affected concentrations at all of the sites. Diurnal patterns and weekend/weekday variations indicated the effects of the mixing layer, point source emissions patterns, and mobile source air toxics (MSATs) on concentrations. Concentrations of many air toxics were temporally correlated, especially MSATs, indicating that they are likely co-emitted. It was also shown that correlations of the HTR data were greater than lower time resolution data (24-h measurements). This difference was most pronounced for the chlorinated pollutants. The stronger correlations in HTR measurements underscore their value for source apportionment studies.