Measurement of gas-phase total peroxides at the summit of Mount Tai in China

Measurement of ambient gas-phase total peroxides was performed at the summit of Mount Tai (Mt. Tai, 1534 m above sea level) in central-eastern China during March 22–April 24 and June 16–July 20, 2007. The hourly averaged concentration of peroxides was 0.17 ppbv (± 0.16 ppbv, maximum: 1.28 ppbv) and 0.55 ppbv (± 0.67 ppbv, maximum: 3.55 ppbv) in the spring and summer campaigns, respectively. The average concentration of peroxides at Mt. Tai, which is in a heavily polluted region, was much lower than hydrogen peroxide measurements made at some rural mountain sites, suggesting that significant removal processes took place in this region. An examination of diurnal variation and a correlation analysis suggest that these removal processes could include chemical suppression of peroxide production due to the scavenging of peroxy and hydroxy radicals by high NO_x, wet removal by clouds/fogs rich in dissolved sulfur dioxide which reacts quickly with peroxides, and photolysis. These sinks competed with photochemical sources of peroxides, resulting in different mean concentrations and diurnal pattern of peroxides in the spring and summer. A principal component analysis was conducted to quantify the major processes that influenced the variation of peroxide concentrations. This analysis shows that in the spring photochemical production was an important source of peroxides, and the major sink was scavenging during upslope transport of polluted and humid air from the lower part of the planetary boundary layer (PBL) and wet removal by synoptic scale clouds. During the summer, highly polluted PBL air (with high NO_x) was often associated with very low peroxides due to the chemical suppression of HO₂ by high NO_x and wet-removal by clouds/fogs in this sulfur-rich atmosphere, especially during the daytime. Higher concentrations of peroxides, which often appeared at mid-nighttime, were mainly associated with subsidence of air masses containing relatively lower concentrations of NO_y.     

Ultrafine particles near a major roadway in Raleigh,North Carolina: Downwind attenuation and correlation with traffic-related pollutants

Ultrafine particles (UFPs, diameter < 100 nm) and co-emitted pollutants from traffic are a potential health threat to nearby populations. During summertime in Raleigh, North Carolina, UFPs were simultaneously measured upwind and downwind of a major roadway using a spatial matrix of five portable industrial hygiene samplers (measuring total counts of 20–1000 nm particles). While the upper sampling range of the portable samplers extends past the defined “ultrafine” upper limit (100 nm), the 20–1000 nm number counts had high correlation (Pearson R = 0.7–0.9) with UFPs (10–70 nm) measured by a co-located research-grade analyzer and thus appear to be driven by the ultrafine range. Highest UFP concentrations were observed during weekday morning work commutes, with levels at 20 m downwind from the road nearly fivefold higher than at an upwind station. A strong downwind spatial gradient was observed, linearly approximated over the first 100 m as an 8% drop in UFP counts per 10 m distance. This result agreed well with UFP spatial gradients estimated from past studies (ranging 5–12% drop per 10 m). Linear regression of other vehicle-related air pollutants measured in near real-time (10-min averages) against UFPs yielded moderate to high correlation with benzene (R² = 0.76), toluene (R² = 0.49), carbon monoxide (R² = 0.74), nitric oxide (R² = 0.80), and black carbon (R² = 0.65). Overall, these results support the notion that near-road levels of UFPs are heavily influenced by traffic emissions and correlate with other vehicle-produced pollutants, including certain air toxics.     

A validated 2-D diffusion–advection model for prediction of drift from ground boom sprayers

Correct field drift prediction is a key element in environmental risk assessment of spraying applications. A reduced order drift prediction model based on the diffusion–advection equation is presented. It allows fast assessment of the drift potential of specific ground boom applications under specific environmental wind conditions that obey the logarithmic wind profile. The model was calibrated based on simulations with a validated Computational Fluid Dynamics (CFD) model. Validation of both models against 38 carefully conducted field experiments is successfully performed for distances up to 20 m from the field edge, for spraying on flat pasture land. The reduced order model succeeded in correct drift predictions for different nozzle types, wind velocities, boom heights and spray pressures. It used 4 parameters representing the physical aspects of the drift cloud; the height of the cloud at the field edge, the mass flux crossing the field edge, the settling velocity of the droplets and the turbulence. For the parameter set and range considered, it is demonstrated for the first time that the effect of the droplet diameter distribution of the different nozzle types on the amount of deposition spray drift can be evaluated by a single parameter, i.e., the volume fraction of droplets with a diameter smaller than 191 μm. The reduced order model can be solved more than 4 orders of magnitude faster than the comprehensive CFD model.     

Influence of air mass source region on nanoparticle events and hygroscopicity in central Virginia,U.S.

During autumn, 2006, variation in the frequency of aerosol nucleation events, as inferred from nanoparticle growth events, and associated hygroscopicity were investigated as a function of air mass transport history at a mixed deciduous forest in central Virginia, U.S. Above-canopy size distributions of aerosols between 0.012 and 0.700 μm diameter, size-resolved particle hygroscopicity at eight dry diameters between 0.012 and 0.400 μm, and cloud condensation nuclei (CCN) activity were characterized. Air mass back trajectories were clustered to identify source regions. Growth events were most frequent in fast-moving air masses (mean = 9 m s^?1) that originated over the north central U.S. Under these flow regimes, mean values for preexisting sub-μm aerosol number concentrations (4700 cm^?3), corresponding surface area (142 μm² cm^?3), air temperature (6.2 °C), and relative humidity (RH, 49.4%) were relatively low compared to other regimes. Under stagnant flow conditions (mean = 3 m s^?1), mean number concentrations were higher (>6000 cm^?3) and size fractions <0.1 μm diameter exhibited enhanced hygroscopicity compared to other source regions. These results indicate that precursors emitted into relatively clean, cold, and dry air transported over the southeastern U.S. reacted to form condensable intermediates that subsequently produced new aerosols via nucleation and growth. This pathway was an important source for CCN. During events in October, nanoparticles were produced in greater numbers and grew more rapidly compared to November and December.     

Characterization and sources assignation of PM2.5 organic aerosol in a rural area of Spain

The results from a year-long study of the organic composition of PM2.5 aerosol collected in a rural area influenced by a highway of Spain are reported. The lack of prior information related to the organic composition of PM2.5 aerosol in Spain, concretely in rural areas, led definition of the goals of this study. As a result, this work has been able to characterize the main organic components of atmospheric aerosols, including several compounds of SOA, and has conducted a multivariate analysis in order to assign sources of particulate matter. A total of 89 samples were taken between April 2004 and April 2005 using a high-volume sampler. Features and abundance of n-alkanes, polycyclic aromatic hydrocarbons (PAHs), alcohols and acids were separately determined using gas chromatography/mass spectrometry and high performance liquid chromatography analysis. The Σn-alkane and ΣPAHs ranged from 3 to 81 ng m^?3 and 0.1 to 6 ng m^?3 respectively, with higher concentrations during colder months. Ambient concentrations of Σalcohols and Σacids ranged from 21 to 184 ng m^?3 and 39 to 733 ng m^?3, respectively. Also, several components of secondary organic aerosol have been quantified, confirming the biogenic contribution to ambient aerosol. In addition, factor analysis was used to reveal origin of organic compounds associated to particulate matter. Eight factors were extracted accounting more than 83% of the variability in the original data. These factors were assigned to a typical high pollution episode by anthropogenic particles, crustal material, plant waxes, fossil fuel combustion, temperature, microbiological emissions, SOA and dispersion of pollutants by wind action. Finally, a cluster analysis was used to compare the organic composition between the four seasons.     

Assessing spatial variability of SO2 field as detected by an air quality network using Self-Organizing Maps,cluster, and Principal Component Analysis

In Bilbao (Spain), an air quality network measures sulphur dioxide levels at 4 locations. The objective of this paper is to develop a practical methodology to identify redundant sensors and evaluate a network's capability to correctly follow and represent SO₂ fields in Bilbao, in the frame of a continuous network optimization process.The methodology is developed and tested at this particular location, but it is general enough to be useable at other places as well, since it is not tied neither to the particular geographical characteristics of the place nor to the phenomenology of the air quality over the area.To assess the spatial variability of SO₂ measured at 4 locations in the area, three different techniques have been used: Self-Organizing Maps (SOMs), cluster analysis (CA) and Principal Component Analysis (PCA). The results show that the three techniques yield the same results, but the information obtained via PCA can be helpful not only for that purpose but also to throw light on the major mechanisms involved. This might be used in future network optimization stages. The main advantage of cluster analysis and SOMs is that they provide readily interpretable results. All the calculations have been carried out using the freely available software R.     

Further studies on the uptake of persistent organic pollutants (POPs) by polyurethane foam disk passive air samplers

Passive air samplers (PAS) can be used to monitor semi-volatile organic compounds in the atmosphere. Polyurethane foam (PUF) disks are a popular sampling medium because they have a high retention capacity for such compounds. This paper reports a highly time-resolved uptake study, to derive uptake rate data under field conditions, and investigate the effects of using different foam densities on the uptake rate. PUF disks were deployed alongside an active sampler, for periods of up to 12 weeks. The uptake rates were measured for a range of gas- and particle-bound persistent organic pollutants (polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs)), of different properties, to explore whether gas–particle partitioning affected uptake rate. Uptake rates for two different densities of foam (0.021 and 0.035 g cm^?3) were not statistically significantly different from each other. Uptake rates of light PCBs averaged ～6.5 m³ day^?1, somewhat higher than in previous studies; higher wind speeds and lower temperatures in this study are the likely reason for this difference. The study showed: i) the uptake rate of the compound with lowest K_OA considered in this study (PCB-28/31) declined in the later weeks, indicating an approach to equilibrium; ii) uptake rates of lighter BDEs and heavier PCBs (compounds of intermediate K_OA in this study) remain similar throughout the study period, indicating that they are not approaching equilibrium during the 12-week-study; iii) uptake rates were typically: ～8 m³ day^?1 for PCB-52; ～9.5 m³ day^?1 for PCB-95; ～11 m³ day^?1 for BDE-28 and ～2 m³ day^?1 BDE-99. The latter compound has an important particle-bound component and this lowers the sampling rate compared to predicted uptake rates for compounds which are in the gas phase only. It is shown that knowledge of gas–particle partitioning is needed to correct for this effect, and to improve predicted uptake rates.     

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.     

Evaluating inter-continental transport of fine aerosols:(2) Global health impact

In this second of two companion papers, we quantify for the first time the global impact on premature mortality of the inter-continental transport of fine aerosols (including sulfate, black carbon, organic carbon, and mineral dust) using the global modeling results of (Liu et al., 2009). Our objective is to estimate the number of premature mortalities in each of ten selected continental regions resulting from fine aerosols transported from foreign regions in approximately year 2000. Our simulated annual mean population-weighted (P-W) concentrations of total PM2.5 (aerosols with diameter less than 2.5 μm) are highest in East Asia (EA, 30 μg m^?3) and lowest in Australia (3.6 μg m^?3). Dust is the dominant component of PM2.5 transported between continents. We estimate global annual premature mortalities (for adults age 30 and up) due to inter-continental transport of PM2.5 to be nearly 380 thousand (K) in 2000. Approximately half of these deaths occur in the Indian subcontinent (IN), mostly due to aerosols transported from Africa and the Middle East (ME). Approximately 90K deaths globally are associated with exposure to foreign (i.e., originating outside a receptor region) non-dust PM2.5. More than half of the premature mortalities associated with foreign non-dust aerosols are due to aerosols originating from Europe (20K), ME (18K) and EA (15K); and nearly 60% of the 90K deaths occur in EA (21K), IN (19K) and Southeast Asia (16K). The lower and higher bounds of our estimated 95% confidence interval (considering uncertainties from the concentration–response relationship and simulated aerosol concentrations) are 18% and 240% of the estimated deaths, respectively, and could be larger if additional uncertainties were quantified. We find that in 2000 nearly 6.6K premature deaths in North America (NA) were associated with foreign PM2.5 exposure (5.5K from dust PM2.5). NA is least impacted by foreign PM2.5 compared to receptors on the Eurasian continent. However, the number of premature mortalities associated with foreign aerosols in NA (mostly occurring in the U.S.) is comparable to the reduction in premature mortalities expected to result from tightening the U.S. 8-h O₃ standard from 0.08 ppmv to 0.075 ppmv. International efforts to reduce inter-continental transport of fine aerosol pollution would substantially benefit public health on the Eurasian continent and would also benefit public health in the United States.     

Temperature dependence of secondary organic aerosol

Temperature was found to have a dramatic effect on secondary organic aerosol formation from two ozonolysis systems, cyclohexene and α-pinene. Isothermal experiments were conducted for both systems where the lowest temperature, 278 K, formed approximately 2.5–3 times and 5–6 times the SOA formed at 300 K and 318 K, respectively. Changing the cyclohexene system temperature to a different isothermal experimental set point after completion of SOA formation did not lead to sufficient condensation/evaporation to reproduce the SOA formation at other temperature set points. When the system temperature was cycled between two set points at the end of an experiment, the α-pinene system showed reversibility between the initial temperature 318 K and 300 K. For temperature cycles between the initial temperature of 300 K–318 K, an irreversible loss of mass is observed after the first heating cycle with reversibility observed between subsequent temperature cycles. The SOA formed at 278 K was reversible over a 22 K range but was unable to evaporate sufficiently to match the SOA mass formed at 300 K. Hygroscopicity measurements, taken after the completion of SOA formation, indicate that hygroscopicity of the aerosol is also a function of temperature and that the aerosol does not continue to be oxidized after initial growth is complete. The differing hygroscopicity of the semi-volatile component of the aerosol is evident during system temperature changes after completion of the experiment.