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Identifying the sources driving observed PM2.5 temporal variability over Halifax, Nova Scotia, during BORTAS-B

The source attribution of observed variability of total PM2.5 concentrations over Halifax, Nova Scotia, was investigated between 11 July and 26 August 2011 using measurements of PM2.5 mass and PM2.5 chemical composition (black carbon, organic matter, anions, cations and 33 elements). This was part of the BORTAS-B (quantifying the impact of BOReal forest fires on Tropospheric oxidants using Aircraft and Satellites) experiment, which investigated the atmospheric chemistry and transport of seasonal boreal wildfire emissions over eastern Canada in 2011. The US EPA Positive Matrix Factorization (PMF) receptor model was used to determine the average mass (percentage) source contribution over the 45 days, which was estimated to be as follows: long-range transport (LRT) pollution: 1.75 μg m−3 (47%); LRT pollution marine mixture: 1.0 μg m−3 (27.9%); vehicles: 0.49 μg m−3 (13.2%); fugitive dust: 0.23 μg m−3 (6.3%); ship emissions: 0.13 μg m−3 (3.4%); and refinery: 0.081 μg m−3 (2.2%). The PMF model describes 87% of the observed variability in total PM2.5 mass (bias = 0.17 and RSME = 1.5 μg m−3). The factor identifications are based on chemical markers, and they are supported by air mass back trajectory analysis and local wind direction. Biomass burning plumes, found by other surface and aircraft measurements, were not significant enough to be identified in this analysis. This paper presents the results of the PMF receptor modelling, providing valuable insight into the local and upwind sources impacting surface PM2.5 in Halifax and a vital comparative data set for the other collocated ground-based observations of atmospheric composition made during BORTAS-B.
Dynamics of nitrogen oxides and ozone above and within a mixed hardwood forest in northern Michigan

The dynamic behavior of nitrogen oxides (NOx = NO + NO2) and ozone (O3) above and within the canopy at the University of Michigan Biological Station AmeriFlux (UMBS Flux) site was investigated by continuous multi-height vertical gradient measurements during the summer and the fall of 2008. A daily maximum in nitric oxide (NO) mixing ratios was consistently observed during the morning hours between 06:00 and 09:00 EST above the canopy. Daily NO maxima ranged between 0.1 and 2 ppbv (with a median of 0.3 ppbv), which were 2 to 20 times above the atmospheric background. The sources and causes of the morning NO maximum were evaluated using NOx and O3 measurements and synoptic and micrometeorological data. Numerical simulations with a multi-layer canopy-exchange model were done to further support this analysis. The observations indicated that the morning NO maximum was caused by the photolysis of NO2 from non-local air masses, which were transported into the canopy from aloft during the morning breakup of the nocturnal boundary layer. The analysis of simulated process tendencies indicated that the downward turbulent transport of NOx into the canopy compensates for the removal of NOx through chemistry and dry deposition. The sensitivity of NOx and O3 concentrations to soil and foliage NOx emissions was also assessed with the model. Uncertainties associated with the emissions of NOx from the soil or from leaf-surface nitrate photolysis did not explain the observed diurnal behavior in NOx (and O3) and, in particular, the morning peak in NOx mixing ratios. However, a ~30% increase in early morning NOx and NO peak mixing ratios was simulated when a foliage exchange NO2 compensation point was considered. This increase suggests the potential importance of leaf-level, bidirectional exchange of NO2 in understanding the observed temporal variability in NOx at UMBS.
Aerosol and precipitation chemistry in the southwestern United States: spatiotemporal trends and interrelationships

This study characterizes the spatial and temporal patterns of aerosol and precipitation composition at six sites across the United States Southwest between 1995 and 2010. Precipitation accumulation occurs mostly during the wintertime (December–February) and during the monsoon season (July–September). Rain and snow pH levels are usually between 5–6, with crustal-derived species playing a major role in acid neutralization. These species (Ca2+, Mg2+, K+, Na+) exhibit their highest concentrations between March and June in both PM2.5 and precipitation due mostly to dust. Crustal-derived species concentrations in precipitation exhibit positive relationships with SO42−, NO3−, and Cl−, suggesting that acidic gases likely react with and partition to either crustal particles or hydrometeors enriched with crustal constituents. Concentrations of particulate SO42− show a statistically significant correlation with rain SO42− unlike snow SO42−, which may be related to some combination of the vertical distribution of SO42− (and precursors) and the varying degree to which SO42−-enriched particles act as cloud condensation nuclei versus ice nuclei in the region. The coarse : fine aerosol mass ratio was correlated with crustal species concentrations in snow unlike rain, suggestive of a preferential role of coarse particles (mainly dust) as ice nuclei in the region. Precipitation NO3− : SO42− ratios exhibit the following features with potential explanations discussed: (i) they are higher in precipitation as compared to PM2.5; (ii) they exhibit the opposite annual cycle compared to particulate NO3− : SO42− ratios; and (iii) they are higher in snow relative to rain during the wintertime. Long-term trend analysis for the monsoon season shows that the NO3− : SO42− ratio in rain increased at the majority of sites due mostly to air pollution regulations of SO42− precursors.
Corrigendum to "Evaluated kinetic and photochemical data for atmospheric chemistry: Volume V – heterogeneous reactions on solid substrates" published in Atmos. Chem. Phys. 10, 9059–9223, 2010
CO, NOx and 13CO2 as tracers for fossil fuel CO2: results from a pilot study in Paris during winter 2010

Measurements of the mole fraction of the CO2 and its isotopes were performed in Paris during the MEGAPOLI winter campaign (January–February 2010). Radiocarbon (14CO2) measurements were used to identify the relative contributions of 77% CO2 from fossil fuel consumption (CO2ff from liquid and gas combustion) and 23% from biospheric CO2 (CO2 from the use of biofuels and from human and plant respiration: CO2bio). These percentages correspond to average mole fractions of 26.4 ppm and 8.2 ppm for CO2ff and CO2bio, respectively. The 13CO2 analysis indicated that gas and liquid fuel contributed 70% and 30%, respectively, of the CO2 emission from fossil fuel use. Continuous measurements of CO and NOx and the ratios CO/CO2ff and NOx/CO2ff derived from radiocarbon measurements during four days make it possible to estimate the fossil fuel CO2 contribution over the entire campaign. The ratios CO/CO2ff and NOx/CO2ff are functions of air mass origin and exhibited daily ranges of 7.9 to 14.5 ppb ppm−1 and 1.1 to 4.3 ppb ppm−1, respectively. These ratios are consistent with different emission inventories given the uncertainties of the different approaches. By using both tracers to derive the fossil fuel CO2, we observed similar diurnal cycles with two maxima during rush hour traffic.
Changes in particulate matter physical properties during Saharan advections over Rome (Italy): a four-year study, 2001–2004

Particulate matter mass concentrations measured in the city of Rome (Italy) in the period 2001–2004 have been cross-analysed with concurrent Saharan dust advection events to infer the impact these natural episodes bear on the standard air quality parameter PM10 observed at two city stations and at one regional background station. Natural events such as Saharan dust advections are associated with a definite health risk. At the same time, the Directive 2008/50/EC allows subtraction of PM exceedances caused by natural contributions from statistics used to determine air quality of EU sites. In this respect, it is important to detect and characterise such advections by means of reliable, operational techniques. To assess the PM10 increase we used both the "regional-background method" suggested by EC Guidelines and a "local background" method, demonstrated to be most suited to this central Mediterranean region. In terms of exceedances, the two approaches provided results within ~20% of each other at background sites, and at ~50% of each other in traffic conditions. The sequence of Saharan advections over the city has been either detected by Polarization Lidar (laser radar) observations or forecast by the operational numerical regional mineral dust model BSC-DREAM8b of the Barcelona Supercomputing Centre. Lidar observations were also employed to retrieve the average physical properties of the dust clouds as a function of height. Over the four-year period, Lidar measurements (703 evenly distributed days) revealed Saharan plumes transits over Rome on 28.6% of the days, with minimum occurrence in wintertime. Dust was observed to reach the ground on 17.5% of the days totalling 88 episodes. Most (90%) of these advections lasted up to 5 days, averaging to ~3 days. Median time lag between advections was 7 days. Typical altitude range of the dust plumes was 0–6 km, with the centre of mass at ~3 km a.g.l. BSC-DREAM8b model simulations (1461 days) predicted Lidar detectable (532 nm extinction coefficient > 0.005 km−1) dust advections on 25.9% of the days, with ground contacts on 13% of the days. As in the Lidar case, the average dust centre of mass was forecast at ~3 km. Along the 703 day Lidar dataset, model forecast and Lidar detection of the presence of dust coincided on 80% of the cases, 92% coincidences are found within a ±1 day window. Combination of the BSC-DREAM8b and Lidar records leads to about 21% of the days being affected by presence of Saharan dust at the ground. This combined dataset has been used to compute the increase in PM with respect to dust-unaffected previous days. This analysis has shown Saharan dust events to exert a meaningful impact on the PM10 records, causing average increases of the order of 11.9 μg m−3. Conversely, PM10 increases computed relying only on the Lidar detections (i.e., presence of dust layers actually observed) were of the order of 15.6 μg m−3. Both analyses indicate the annual average contribution of dust advections to the city PM10 mass concentrations to be of the order of 2.35 μg m−3. The number of exceedances attributable to Saharan advections at the three station types addressed in this study (urban traffic, urban background and regional background) were found to be 25%, 30% and 43%, respectively. These results confirm Saharan advections in the central Mediterranean as important modulators of PM10 loads and exceedances.
Positive matrix factorization of PM2.5 – eliminating the effects of gas/particle partitioning of semivolatile organic compounds

Gas-phase concentrations of semi-volatile organic compounds (SVOCs) were calculated from gas/particle (G/P) partitioning theory using their measured particle-phase concentrations. The particle-phase data were obtained from an existing filter measurement campaign (27 January 2003–2 October 2005) as a part of the Denver Aerosol Sources and Health (DASH) study, including 970 observations of 71 SVOCs (Xie et al., 2013). In each compound class of SVOCs, the lighter species (e.g. docosane in n alkanes, fluoranthene in PAHs) had higher total concentrations (gas + particle phase) and lower particle-phase fractions. The total SVOC concentrations were analyzed using positive matrix factorization (PMF). Then the results were compared with source apportionment results where only particle-phase SVOC concentrations were used (particle only-based study; Xie et al., 2013). For the particle only-based PMF analysis, the factors primarily associated with primary or secondary sources (n alkane, EC/sterane and inorganic ion factors) exhibit similar contribution time series (r = 0.92–0.98) with their corresponding factors (n alkane, sterane and nitrate + sulfate factors) in the current work. Three other factors (light n alkane/PAH, PAH and summer/odd n alkane factors) are linked with pollution sources influenced by atmospheric processes (e.g. G/P partitioning, photochemical reaction), and were less correlated (r = 0.69–0.84) with their corresponding factors (light SVOC, PAH and bulk carbon factors) in the current work, suggesting that the source apportionment results derived from particle-only SVOC data could be affected by atmospheric processes. PMF analysis was also performed on three temperature-stratified subsets of the total SVOC data, representing ambient sampling during cold (daily average temperature <10 °C), warm (≥10 °C and ≤20 °C) and hot (>20 °C) periods. Unlike the particle only-based study, in this work the factor characterized by the low molecular weight (MW) compounds (light SVOC factor) exhibited strong correlations (r = 0.82–0.98) between the full data set and each sub-data set solution, indicating that the impacts of G/P partitioning on receptor-based source apportionment could be eliminated by using total SVOC concentrations.
Drivers of hemispheric differences in return dates of mid-latitude stratospheric ozone to historical levels

Chemistry-climate models (CCMs) project an earlier return of northern mid-latitude total column ozone to 1980 values compared to the southern mid-latitudes. The chemical and dynamical drivers of this hemispheric difference are investigated in this study. The hemispheric asymmetry in return dates is a robust result across different CCMs and is qualitatively independent of the method used to estimate return dates. However, the differences in dates of return to 1980 levels between the southern and northern mid-latitudes can vary between 0 and 30 yr across the range of CCM projections analyzed. Positive linear trends in ozone lead to an earlier return of ozone than expected from the return of Cly to 1980 levels. This forward shift is stronger in the Northern than in the Southern Hemisphere because (i) trends have a larger effect on return dates if the sensitivity of ozone to Cly is lower and (ii) the trends in the Northern Hemisphere are stronger than in the Southern Hemisphere. An attribution analysis performed with two CCMs shows that chemically-induced changes in ozone are the major driver of the earlier return of ozone to 1980 levels in northern mid-latitudes; therefore transport changes are of minor importance. This conclusion is supported by the fact that the spread in the simulated hemispheric difference in return dates across an ensemble of twelve models is only weakly related to the spread in the simulated hemispheric asymmetry of trends in the strength of the Brewer–Dobson circulation. The causes for chemically-induced asymmetric ozone trends relevant for the total column ozone return date differences are found to be (i) stronger increases in ozone production due to enhanced NOx concentrations in the Northern Hemisphere lowermost stratosphere and troposphere, (ii) stronger decreases in the destruction rates of ozone by the NOx cycle in the Northern Hemisphere lower stratosphere linked to effects of dynamics and temperature on NOx concentrations, and (iii) an increasing efficiency of heterogeneous ozone destruction by Cly in the Southern Hemisphere mid-latitudes as a~result of decreasing lower stratospheric temperatures.
Ozone photochemistry in boreal biomass burning plumes

We present an analysis of ozone (O3) photochemistry observed by aircraft measurements of boreal biomass burning plumes over eastern Canada in the summer of 2011. Measurements of O3 and a number of key chemical species associated with O3 photochemistry, including non-methane hydrocarbons (NMHCs), nitrogen oxides (NOx) and total nitrogen containing species (NOy), were made from the UK FAAM BAe-146 research aircraft as part of the "quantifying the impact of BOReal forest fires on Tropospheric oxidants over the Atlantic using Aircraft and Satellites" (BORTAS) experiment between 12 July and 3 August 2011. The location and timing of the aircraft measurements put BORTAS into a unique position to sample biomass burning plumes from the same source region in Northwestern Ontario with a range of ages. We found that O3 mixing ratios measured in biomass burning plumes were indistinguishable from non-plume measurements, but evaluating them in relationship to measurements of carbon monoxide (CO), total alkyl nitrates (ΣAN) and the surrogate species NOz (= NOy-NOx) revealed that the potential for O3 production increased with plume age. We used NMHC ratios to estimate photochemical ages of the observed biomass burning plumes between 0 and 10 days. The BORTAS measurements provided a wide dynamic range of O3 production in the sampled biomass burning plumes with ΔO3/ΔCO enhancement ratios increasing from 0.020 ± 0.008 ppbv ppbv−1 in plumes with photochemical ages less than 2 days to 0.55 ± 0.29 ppbv ppbv−1 in plumes with photochemical ages greater than 5 days. We found that the main contributing factor to the variability in the ΔO3/ΔCO enhancement ratio was ΔCO in plumes with photochemical ages less than 4 days, and that was a transition to ΔO3 becoming the main contributing factor in plumes with ages greater than 4 days. In comparing O3 mixing ratios with components of the NOy budget, we observed that plumes with ages between 2 and 4 days were characterised by high aerosol loading, relative humidity greater than 40%, and low ozone production efficiency (OPE) of 7.7 ± 3.5 ppbv ppbv−1 relative to ΣAN and 1.6 ± 0.9 ppbv ppbv−1 relative to NOz. In plumes with ages greater than 4 days, OPE increased to 472 ± 28 ppbv ppbv−1 relative to ΣAN and 155 ± 5 ppbv ppbv−1 relative to NOz. From the BORTAS measurements we estimated that aged plumes with low aerosol loading were close to being in photostationary steady state and O3 production in younger plumes was inhibited by high aerosol loading and greater production of ΣAN relative to O3. The BORTAS measurements of O3 photochemistry in boreal biomass burning plumes were found to be consistent with previous summertime aircraft measurements made over the same region during the Arctic Research of the Composition of the Troposphere (ARCTAS-B) in 2008 and Atmospheric Boundary Layer Experiment (ABLE 3B) in 1990.
Observations of fluorescent and biological aerosol at a high-altitude site in central France

Total bacteria, fungal spore and yeast counts were compared with ultraviolet-light-induced fluorescence (UV-LIF) measurements of ambient aerosol at the summit of the Puy de Dôme (PdD) mountain in central France (1465 m a.s.l), which represents a background elevated site. Bacteria, fungal spores and yeast were enumerated by epifluorescence microscopy (EFM) and found to number 2.2 to 23 L−1 and 0.8 to 2 L−1, respectively. Bacteria counts on two successive nights were an order of magnitude larger than in the intervening day. A wide issue bioaerosol spectrometer, version 3 (WIBS-3) was used to perform UV-LIF measurements on ambient aerosol sized 0.8 to 20 μm. Mean total number concentration was 270 L−1 (σ = 66 L−1), found predominantly in a size mode at 2 μm for most of the campaign. Total concentration (fluorescent + non-fluorescent aerosol) peaked at 500 L−1 with a size mode at 1 μm because of a change in air mass origin lasting around 48 h. The WIBS-3 features two excitation and fluorescence detection wavelengths corresponding to different biological molecules, although non-biological interferents also contribute. The mean fluorescent particle concentration after short-wave (280 nm; associated with tryptophan) excitation was 12 L−1 (σ = 6 L−1), and did not vary much throughout the campaign. In contrast, the mean concentration of particles fluorescent after long-wave (370 nm; associated with NADH) excitation was 95 L−1 (σ = 25 L−1), and a nightly rise and subsequent fall of up to 100 L−1 formed a strong diurnal cycle in the latter. The two fluorescent populations exhibited size modes at 3 μm and 2 to 3 μm, respectively. A hierarchical agglomerative cluster analysis algorithm was applied to the data and used to extract different particle factors. A cluster concentration time series representative of bacteria was identified. This was found to exhibit a diurnal cycle with a maximum peak appearing during the day. Analysis of organic mass spectra recorded using an aerosol mass spectrometer (AMS; Aerodyne Inc.) suggests that aerosol reaching the site at night was more aged than that during the day, indicative of sampling the residual layer at night. Supplementary meteorological data and previous work also show that PdD lies in the residual layer/free troposphere at night, and this is thought to cause the observed diurnal cycles in organic-type and fluorescent aerosol particles. Based on the observed disparity between bacteria and fluorescent particle concentrations, fluorescent non-PBA is likely to be important in the WIBS-3 data and the surprisingly high fluorescent concentration in the residual layer/free troposphere raises questions about a ubiquitous background in continental air during the summer.