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Spatial variation in particle number size distributions in a large metropolitan area

Air quality studies have indicated that particle number size distribution (NSD) is unevenly spread in urban air. To date, these studies have focussed on differences in concentration levels between sampling locations rather than differences in the underlying geometries of the distributions. As a result, the existing information on the spatial variation of the NSD in urban areas remains incomplete. To investigate this variation in a large metropolitan area in the southern hemisphere, NSD data collected at nine different locations during different campaigns of varying duration were compared using statistical methods. The spectra were analysed in terms of their modal structures (the graphical representation of the number size distribution function), cumulative distribution and number median diameter (NMD). The study found that with the exception of one site all distributions were bimodal or suggestive of bimodality. In general, peak concentrations were below 30 nm and NMDs below 50 nm, except at a site dominated by diesel trucks, where it shifted to around 50 and 60 nm respectively. Ultrafine particles (UFPs (<100 nm)) contributed to 82–90% of the particle number, nanoparticles (<50 nm) to around 60–70%, except at the diesel traffic site, where their contribution dropped to 50%. Statistical analyses found that the modal structures heterogeneously distributed throughout Brisbane whereas it was not always the case for the NMD. The discussion led to the following site classification: (1) urban sites dominated by petrol traffic, (2) urban sites affected by the proximity to the road and (3) an isolated site dominated by diesel traffic. Comparisons of weekday and weekend data indicated that, the distributions were not statistically different. The only exception occurred at one site, where there is a significant drop in the number of diesel buses on the weekend. The differences in sampling period between sites did not affect the results. The statistics instead suggested variations in traffic composition. However, the relative contribution of petrol vehicle emissions at each site could not be assessed due to the limited traffic information available.
Lagrangian transport modelling for CO2 using two different biosphere models

In this work, the performance of the Framework for Atmosphere-Canopy Exchange Modelling (FACEM: Pieterse et al., 2007) coupled to a Lagrangian atmospheric transport model is evaluated for carbon dioxide. Before incorporating FACEM into the Lagrangian COMET model (Vermeulen et al., 2006), its performance for the European domain is compared with the Simple Biosphere model (SiB3: Sellers et al., 1996). Overall, FACEM is well correlated to SiB3 (R2≥0.60), but shows less variability for regions with predominantly bare soil. There is no significant overall bias between the models except for the winter conditions and in general for the Iberian peninsula. When coupled to the COMET transport model, both biosphere models yield similar correlations (R2≥0.60) and bias relative to the 1-hourly concentration measurements for the year 2002, performed at three different sites in Europe; Cabauw (Netherlands), Hegyhatsal (Hungary) and Mace Head (Ireland). The overall results indicate that FACEM is comparable to SiB3 in terms of its applicability for atmospheric modelling studies.
The ozonolysis of primary aliphatic amines in fine particles

The oxidative processing by ozone of the particulate amines octadecylamine (ODA) and hexadecylamine (HDA) is reported. Ozonolysis of these amines resulted in strong NO2– and NO3– ion signals that increased with ozone exposure as monitored by photoelectron resonance capture ionization aerosol mass spectrometry. These products suggest a mechanism of progressive oxidation of the particulate amines to nitroalkanes. Additionally, a strong ion signal at 125 m/z is assigned to the ion NO3– (HNO3). For ozonized mixed particles containing ODA or HDA + oleic acid (OL), with pO3≥3×10–7 atm, imine, secondary amide, and tertiary amide products were measured. These products most likely arise from reactions of amines with aldehydes (for imines) and stabilized Criegee intermediates (SCI) or secondary ozonides (for amides) from the fatty acid. The routes to amides via SCI and/or secondary ozonides were shown to be more important than comparable amide forming reactions between amines and organic acids, using azelaic acid as a test compound. Finally, direct evidence is provided for the formation of a surface barrier in the ODA + OL reaction system that resulted in the retention of OL at high ozone exposures (up to 10−3 atm for 17 s). This effect was not observed in HDA + OL or single component OL particles, suggesting that it may be a species-specific surfactant effect from an in situ generated amide or imine. Implications to tropospheric chemistry, including particle bound amines as sources of oxidized gas phase nitrogen species (e.g.~NO2, NO3), formation of nitrogen enriched HULIS via ozonolysis of amines and source apportionment are discussed.
Calibration and measurement uncertainties of a continuous-flow cloud condensation nuclei counter (DMT-CCNC): CCN activation of ammonium sulfate and sodium chloride aerosol particles in theory and experiment

Experimental and theoretical uncertainties in the measurement of cloud condensation nuclei (CCN) with a continuous-flow thermal-gradient CCN counter from Droplet Measurement Technologies (DMT-CCNC) have been assessed by model calculations and calibration experiments with ammonium sulfate and sodium chloride aerosol particles in the diameter range of 20–220 nm. Experiments have been performed in the laboratory and during field measurement campaigns, covering a wide range of instrument operating conditions (650–1020 hPa pressure, 293–303 K inlet temperature, 4–34 K m−1 temperature gradient, 0.5–1.0 L min−1 flow rate). For each set of conditions, the effective water vapor supersaturation (Seff, 0.05–1.4%) was determined from the measured CCN activation spectra (dry particle activation diameters) and Köhler model calculations. High measurement precision was achieved under stable laboratory conditions, where the relative standard deviations of Seff were as low as ±1%. During field measurements, however, the relative deviations increased to about ±5%, which can be mostly attributed to variations of the CCNC column top temperature with ambient temperature. The observed dependence of Seff on temperature, pressure, and flow rate was compared to the CCNC flow model of Lance et al. (2006). At high Seff the relative deviations between flow model and experimental results were mostly less than 10%, but at Seff≤0.1% they exceeded 40%. Thus, careful experimental calibration is required for high-accuracy CCN measurements – especially at low Seff. A comprehensive comparison and uncertainty analysis of the various Köhler models and thermodynamic parameterizations commonly used in CCN studies showed that the relative deviations between different approaches are as high as 25% for (NH4)2SO4 and 12% for NaCl. The deviations were mostly caused by the different parameterizations for the activity of water in aqueous solutions of the two salts. To ensure comparability of results, we suggest that CCN studies should always report exactly which Köhler model equations and parameters were used. Provided that the Aerosol Inorganics Model (AIM) can be regarded as an accurate source of water activity data for highly dilute solutions of (NH4)2SO4 and NaCl, only Köhler models that are based on the AIM or yield similar results should be used in CCN studies involving these salts and aiming at high accuracy. Experiments with (NH4)2SO4 and NaCl aerosols showed that the conditions of particle generation and the shape and microstructure of NaCl particles are critical for their application in CCN activation experiments (relative deviations up to 18%).
Radiative forcing from modelled and observed stratospheric ozone changes due to the 11-year solar cycle

Three analyses of satellite observations and two sets of model studies are used to estimate changes in the stratospheric ozone distribution from solar minimum to solar maximum and are presented for three different latitudinal bands: Poleward of 30° north, between 30° north and 30° south and poleward of 30° south. In the model studies the solar cycle impact is limited to changes in UV fluxes. There is a general agreement between satellite observation and model studies, particular at middle and high northern latitudes. Ozone increases at solar maximum with peak values around 40 km. The profiles are used to calculate the radiative forcing (RF) from solar minimum to solar maximum. The ozone RF, calculated with two different radiative transfer schemes is found to be negligible (a magnitude of 0.01 Wm−2 or less), compared to the direct RF due to changes in solar irradiance, since contributions from the longwave and shortwave nearly cancel each other. The largest uncertainties in the estimates come from the lower stratosphere, where there is significant disagreement between the different ozone profiles.
Basin-scale wind transport during the MILAGRO field campaign and comparison to climatology using cluster analysis

The MILAGRO field campaign was a multi-agency international collaborative project to evaluate the regional impacts of the Mexico City air pollution plume as a means of understanding urban impacts on the global climate. Mexico City lies on an elevated plateau with mountains on three sides and has complex mountain and surface-driven wind flows. This paper asks what the wind transport was in the basin during the field campaign and how representative it was of the climatology. Surface meteorology and air quality data, radiosondes and radar wind profiler data were collected at sites in the basin and its vicinity. Cluster analysis was used to identify the dominant wind patterns both during the campaign and within the past 10 years of operational data from the warm dry season. Our analysis shows that March 2006 was representative of typical flow patterns experienced in the basin. Six episode types were identified for the basin-scale circulation providing a way of interpreting atmospheric chemistry and particulate data collected during the campaign. Decoupling between surface winds and those aloft had a strong influence in leading to convection and poor air quality episodes. Hourly characterisation of wind circulation during the MILAGRO, MCMA-2003 and IMADA field campaigns enables the comparisons of similar air pollution episodes and the evaluation of the impact of wind transport on measurements of the atmospheric chemistry taking place in the basin.
Does the threshold representation associated with the autoconversion process matter?

Different ad hoc threshold functions associated with the autoconversion process have been arbitrarily used in atmospheric models. However, it is unclear how these ad hoc functions impact model results. Here systematic investigations of the sensitivities of climatically-important properties: CF (cloud fraction), LWP (liquid water path), and AIE (aerosol indirect effect) to threshold functions have been performed using a 3-D cloud-resolving model. It is found that the effect of threshold representations is larger on instantaneous values than on daily averages; and the effect depends on the percentage of clouds in their transitional stages of converting cloud water to rain water. For both the instantaneous values and daily averages, the sensitivity to the specification of critical radius is more significant than the sensitivity to the "smoothness" of the threshold representation (as embodied in the relative dispersion of droplet size distribution) for drizzling clouds. Moreover, the impact of threshold representations on the AIE is stronger than that on CF and LWP.
Real-time characterization of particle-bound polycyclic aromatic hydrocarbons in ambient aerosols and from motor-vehicle exhaust

A photo-electric aerosol sensor, a diffusion charger, an Aethalometer, and a continuous particle counter were used along with other real-time instruments to characterize the particle-bound polycyclic aromatic hydrocarbon (p-PAH) content, and the physical/chemical characteristics of aerosols collected a) in Wilmington (CA) near the Los Angeles port and close to 2 major freeways, and b) at a dynamometer testing facility in downtown Los Angeles (CA), where 3 diesel trucks were tested. In Wilmington, the p-PAH, surface area, particle number, and "black" carbon concentrations were 4-8 times higher at 09:00–11:00 a.m. than between 17:00 and 18:00 p.m., suggesting that during rush hour traffic people living in that area are exposed to a higher number of diesel combustion particles enriched in p-PAH coatings. Dynamometer tests revealed that the p-PAH emissions from the "baseline" truck (no catalytic converter) were up to 200 times higher than those from the 2 vehicles equipped with advanced emission control technologies, and increased when the truck was accelerating. In Wilmington, integrated filter samples were collected and analyzed to determine the concentrations of the most abundant p-PAHs. A correlation between the total p-PAH concentration (μg/m3) and the measured photo-electric aerosol sensor signal (fA) was also established. Estimated ambient p-PAH concentrations (Average=0.64 ng/m3; Standard deviation=0.46 ng/m3 were in good agreement with those reported in previous studies conducted in Los Angeles during a similar time period. Finally, we calculated the approximate theoretical lifetime (70 years per 24-h/day) lung-cancer risk in the Wilmington area due to inhalation of multi-component p-PAHs and "black" carbon. Our results indicate that the lung-cancer risk is highest during rush hour traffic and lowest in the afternoon, and that the genotoxic risk of the considered p-PAHs does not seem to contribute to a significant part of the total lung-cancer risk attributable to "black" carbon.
Source apportionment of fine organic aerosol in Mexico City during the MILAGRO experiment 2006

Organic carbon (OC) comprises a large fraction of fine particulate matter (PM2.5) in Mexico City. Daily and select 12-h PM2.5 samples were collected in urban and peripheral sites in Mexico City from 17–30 March 2006. Samples were analyzed for OC and elemental carbon (EC) using thermal-optical filter-based methods. Real-time water-soluble organic carbon (WSOC) was collected at the peripheral site. Organic compounds, particularly molecular markers, were quantified by soxhlet extraction with methanol and dichloromethane, derivitization, and gas chromatography with mass spectrometric detection (GCMS). A chemical mass balance model (CMB) based on molecular marker species was used to determine the relative contribution of major sources to ambient OC. Motor vehicles, including diesel and gasoline, consistently accounted for 49% of OC in the urban area and 32% on the periphery. The daily contribution of biomass burning to OC was highly variable, and ranged from 5–26% at the urban site and 7–39% at the peripheral site. The remaining OC unapportioned to primary sources showed a strong correlation with WSOC and was considered to be secondary in nature. Comparison of temporally resolved OC showed that contributions from primary aerosol sources during daylight hours were not significantly different from nighttime. This study provides quantitative understanding of the important sources of OC during the MILAGRO 2006 field campaign.
Validation of water vapour profiles from the Atmospheric Chemistry Experiment (ACE)

The Atmospheric Chemistry Experiment (ACE) mission was launched in August 2003 to sound the atmosphere by solar occultation. Water vapour (H2O), one of the most important molecules for climate and atmospheric chemistry, is one of the key species provided by the two principal instruments, the infrared Fourier Transform Spectrometer (ACE-FTS) and the MAESTRO UV-Visible spectrometer (ACE-MAESTRO). The first instrument performs measurements on several lines in the 1362–2137 cm−1 range, from which vertically resolved H2O concentration profiles are retrieved, from 7 to 90 km altitude. ACE-MAESTRO measures profiles using the water absorption band in the near infrared part of the spectrum at 926.0–969.7 nm. This paper presents a comprehensive validation of the ACE-FTS profiles. We have compared the H2O volume mixing ratio profiles with space-borne (SAGE II, HALOE, POAM III, MIPAS, SMR) observations and measurements from balloon-borne frostpoint hygrometers and a ground based lidar. We show that the ACE-FTS measurements provide H2O profiles with small retrieval uncertainties in the stratosphere (better than 5% from 15 to 70 km, gradually increasing above). The situation is unclear in the upper troposphere, due mainly to the high variability of the water vapour volume mixing ratio in this region. A new water vapour data product from the ACE-MAESTRO (Measurement of Aerosol Extinction in the Stratosphere and Troposphere Retrieved by Occultation) is also presented and initial comparisons with ACE-FTS are discussed.