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Mass yields of secondary organic aerosols from the oxidation of α-pinene and real plant emissions

Biogenic volatile organic compounds (VOCs) are a significant source of global secondary organic aerosol (SOA); however, quantifying their aerosol forming potential remains a challenge. This study presents smog chamber laboratory work, focusing on SOA formation via oxidation of the emissions of two dominant tree species from boreal forest area, Scots pine (Pinus sylvestris L.) and Norway spruce (Picea abies), by hydroxyl radical (OH) and ozone (O3). Oxidation of α-pinene was also studied as a reference system. Tetramethylethylene (TME) and 2-butanol were added to control OH and O3 levels, thereby allowing SOA formation events to be categorized as resulting from either OH-dominated or O3-initiated chemistry. SOA mass yields from α-pinene are consistent with previous studies while the yields from the real plant emissions are generally lower than that from α-pinene, varying from 1.9% at an aerosol mass loading of 0.69 μg m−3 to 17.7% at 26.0 μg m−3. Mass yields from oxidation of real plant emissions are subject to the interactive effects of the molecular structures of plant emissions and their reaction chemistry with OH and O3, which lead to variations in condensable product volatility. SOA formation can be reproduced with a two-product gas-phase partitioning absorption model in spite of differences in the source of oxidant species and product volatility in the real plant emission experiments. Condensable products from OH-dominated chemistry showed a higher volatility than those from O3-initiated systems during aerosol growth stage. Particulate phase products became less volatile via aging process which continued after input gas-phase oxidants had been completely consumed.
Coincident measurements of PMSE and NLC above ALOMAR (69° N, 16° E) by radar and lidar from 1999–2008

Polar Mesosphere Summer Echoes (PMSE) and Noctilucent Clouds (NLC) have been routinely measured at the ALOMAR research facility in Northern Norway (69° N, 16° E) by lidar and radar, respectively. 2900 h of lidar measurements by the ALOMAR Rayleigh/Mie/Raman lidar were combined with almost 18 000 h of radar measurements by the ALWIN VHF radar, all taken during the years 1999 to 2008, to study simultaneous and common-volume observations of both phenomena. PMSE and NLC are known from both theory and observations to be positively linked. We quantify the occurrences of PMSE and/or NLC and relations in altitude, especially with respect to the lower layer boundaries. The PMSE occurrence rate is with 75.3% considerably higher than the NLC occurrence rate of 19.5%. For overlapping PMSE and NLC observations, we confirm the coincidence of the lower boundaries and find a standard deviation of 1.26 km, hinting at very fast sublimation rates. However, 10.1% of all NLC measurements occur without accompanying PMSE. Comparison of occurrence rates with solar zenith angle reveals that NLC without PMSE mostly occur around midnight indicating that the ice particles were not detected by the radar due to the reduced electron density.
Sensitivity of stratospheric Bry to uncertainties in very short lived substance emissions and atmospheric transport

We evaluate the sensitivity of Bry entering the stratosphere with a simplified model that allows calculations over a wide parameter range for parameters that are currently poorly quantified. The model examines the transport process uncertainties in the source concentrations and lifetimes, in the convective parameterization and in the inorganic bromine washout process due to dehydration. Source concentrations at the surface and lifetimes were found to have a slight effect on the resultant Bry (1 ppt), however this was highly dependent upon, with increasing significance, the BL component of convectively delivered air. Efficiency of convective delivery of boundary layer (BL) air to the tropical tropopause layer (TTL) along with washout at the CPT were found to substantially affect Bry at 400 K – altering the delivered Bry by 3.3 ppt and 2.9 ppt, respectively. We find that the results critically depend on free tropospheric bromine source gas concentrations due to dilution of convective updrafts, and the processes that control free tropospheric bromine source gas concentrations require further attention.
Spatial variability of POPs in European background air

Passive air samplers (PAS) were deployed at 86 European background sites during summer 2006 in order (i) to gain further insight into spatial patterns of persistent organic pollutants (POPs) in European background air and, (ii) to evaluate PAS as an alternative sampling technique under EMEP (Co-operative programme for monitoring and evaluation of the long-range transmissions of air pollutants in Europe). The samples were analyzed for selected PCBs, HCHs, DDTs, HCB, PAHs and chlordanes, and air concentrations were calculated on the basis of losses of performance reference compounds. Air concentrations of PCBs were generally lowest in more remote areas of northern Europe with elevated levels in more densely populated areas. γ-HCH was found at elevated levels in more central parts of Europe, whereas α-HCH, β-HCH and DDTs showed higher concentrations in the south-eastern part. There was no clear spatial pattern in the concentrations for PAHs, indicative of influence by local sources, rather than long range atmospheric transport (LRAT). HCB was evenly distributed across Europe, while the concentrations of chlordanes were typically low or non-detectable. A comparison of results obtained on the basis of PAS and active air sampling (AAS) illustrated that coordinated PAS campaigns have the potential serve as useful inter-comparison exercises within and across existing monitoring networks. The results also highlighted limitations of the current EMEP measurement network with respect to spatial coverage. We finally adopted an existing Lagrangian transport model (FLEXPART) as recently modified to incorporate key processes relevant for POPs to evaluate potential source regions affecting observed concentrations at selected sites. Using PCB-28 as an example, the model predicted concentrations which agreed within a factor of 3 with PAS measurements for all except 1 out of the 17 sites selected for this analysis.
First long-term study of particle number size distributions and new particle formation events of regional aerosol in the North China Plain

Atmospheric particle number size distributions (size range 0.003–10 μm) were measured between March 2008 and August 2009 at Shangdianzi (SDZ), a rural research station in the North China Plain. These measurements were made in an attempt to better characterize the tropospheric background aerosol in Northern China. The mean particle number concentrations of the total particle, as well as the nucleation, Aitken, accumulation and coarse mode were determined to be 1.2 ± 0.9 × 104, 3.6 ± 7.9 × 103, 4.4 ± 3.4 × 103, 3.5 ± 2.8 × 103 and 2 ± 3 cm−3, respectively. A general finding was that the particle number concentration was higher during spring compared to the other seasons. The air mass origin had an important effect on the particle number concentration and new particle formation events. Air masses from northwest (i.e. inner Asia) favored the new particle formation events, while air masses from southeast showed the highest particle mass concentration. Significant diurnal variations in particle number were observed, which could be linked to new particle formation events, i.e. gas-to-particle conversion. During particle formation events, the number concentration of the nucleation mode rose up to maximum value of 104 cm−3. New particle formation events were observed on 36% of the effective measurement days. The formation rate ranged from 0.7 to 72.7 cm−3 s−1, with a mean value of 8.0 cm−3 s−1. The value of the nucleation mode growth rate was in the range of 0.3–14.5 nm h−1, with a mean value of 4.3 nm h−1. It was an essential observation that on many occasions the nucleation mode was able to grow into the size of cloud condensation nuclei (CCN) within a matter of several hours. Furthermore, the new particle formation was regularly followed by a measurable increase in particle mass concentration and extinction coefficient, indicative of a high abundance of condensable vapors in the atmosphere under study.
Carbonaceous aerosols contributed by traffic and solid fuel burning at a polluted rural site in Northwestern England

The experiment presented in this paper was conducted at the Holme Moss site, which is located in the southern Pennines region in Northwestern England during November–December 2006. The strong southwesterly wind during the experimental period, which enhanced the transport of urban pollutants from the conurbations of Greater Manchester and Liverpool, in addition to the seasonally increased nearby residential heating activities, made this site a receptor for pollutants from a range of sources. A factor analysis is applied to the mass spectra of organic matter (OM) measured by the Aerodyne Aerosol Mass Spectrometer (AMS) to attribute the pollutant sources. Besides the oxygenated organic aerosol (OOA), this site was found to contain a considerable fraction of primary organic aerosols (POA, mass fraction 50–70% within total mass of OM). The POA sources are attributed to be traffic emission and solid fuel burning, which are identified as hydrocarbon-like organic aerosol (HOA) and solid fuel organic aerosol (SFOA) respectively. There were strongly combined emissions of black carbon (BC) particles from both sources. The refractory BC component (rBC) was characterized by a single particle soot photometer. This site began to be influenced during the late morning by fresh traffic emissions, whereas solid fuel burning became dominant from late afternoon until night. A covariance analysis of rBC and POA was used to derive source specific emission factors of 1.61 μgHOA/μgrBC and 1.96 μgHOA/μgrBC. The absorbing properties of aerosols were characterized at multiple wavelengths (λ), and a stronger spectral dependence of absorption was observed when this site was significantly influenced by solid fuel burning. The rBC was estimated to contribute 3–16% of submicron aerosol mass. The single scattering albedo at λ = 700 nm (SSA700 nm) was significantly anti-correlated with the rBC mass fraction, but also associated with the BC mixing state. The BC incorporation/removal process therefore may play a role in modulating the radiative properties of aerosols at the site under the influence of fresh sources. Given that traffic and residential combustion of solid fuels are significant contributors of carbonaceous aerosols over Europe, these results provide important source-specific information on modeling the anthropogenic carbonaceous aerosols.
Characterization of the sources and processes of organic and inorganic aerosols in New York city with a high-resolution time-of-flight aerosol mass apectrometer

Submicron aerosol particles (PM1) were measured in-situ using a High-Resolution Time-of-Flight Aerosol Mass Spectrometer during the summer 2009 Field Intensive Study at Queens College in New York, NY. Organic aerosol (OA) and sulfate are the two dominant species, accounting for 54% and 24%, respectively, of the total PM1 mass. The average mass-based size distribution of OA presents a small mode peaking at ~150 nm (Dva) and an accumulation mode (~550 nm) that is internally mixed with sulfate, nitrate, and ammonium. The diurnal cycles of both sulfate and OA peak between 01:00–02:00 p.m. EST due to photochemical production. The average (±σ) oxygen-to-carbon (O/C), hydrogen-to-carbon (H/C), and nitrogen-to-carbon (N/C) ratios of OA in NYC are 0.36 (±0.09), 1.49 (±0.08), and 0.012 (±0.005), respectively, corresponding to an average organic mass-to-carbon (OM/OC) ratio of 1.62 (±0.11). Positive matrix factorization (PMF) of the high resolution mass spectra identified two primary OA (POA) sources, traffic and cooking, and three secondary OA (SOA) components including a highly oxidized, regional low-volatility oxygenated OA (LV-OOA; O/C = 0.63), a less oxidized, semi-volatile SV-OOA (O/C = 0.38) and a unique nitrogen-enriched OA (NOA; N/C = 0.053) characterized with prominent CxH2x + 2N+ peaks likely from amino compounds. Our results indicate that cooking and traffic are two distinct and mass-equivalent POA sources in NYC, together contributing ~30% of the total OA mass during this study. The OA composition is dominated by secondary species, especially during high PM events. SV-OOA and LV-OOA on average account for 34% and 30%, respectively, of the total OA mass. The chemical evolution of SOA in NYC appears to progress with a continuous oxidation from SV-OOA to LV-OOA, which is further supported by a gradual increase of O/C ratio and a simultaneous decrease of H/C ratio in total OOA. Detailed analysis of NOA (5.8% of OA) presents evidence that organic nitrogen species such as amines might have played an important role in the atmospheric processing of OA in NYC, likely involving both acid-base chemistry and photochemistry. In addition, analysis of air mass trajectories and satellite imagery of aerosol optical depth (AOD) indicates that the high potential source regions of secondary sulfate and aged OA are mainly located in regions to the west and southwest of the city.
Source contributions to Northern Hemisphere CO and black carbon during spring and summer 2008 from POLARCAT and START08/preHIPPO observations and MOZART-4

Anthropogenic pollution and wildfires are main producers of carbon monoxide (CO) and black carbon (BC) in the Northern Hemisphere. High concentrations of these compounds are transported into the Arctic troposphere, influencing the ecosystem in high northern latitudes and the global climate. The global chemical transport model MOZART-4 is used to quantify the seasonal evolution of the contribution of CO and BC from different source regions in spring and summer 2008 by tagging their emissions. Aircraft observations from the POLARCAT experiments, in particular NASA ARCTAS, NOAA ARCPAC, POLARCAT-France, DLR GRACE and YAK-AEROSIB, as well as the NSF START08/preHIPPO experiments during Spring-Summer 2008 are combined to quantify the representation of simulated tracer characteristics in anthropogenic and fire plumes. In general, the model reproduces CO and BC well. Based on aircraft measurements and FLEXPART back-trajectories, the altitude contribution of emissions coming from different source regions is well captured in the model. Uncertainties of the MOZART-4 model are identified by comparing the data with model results on the flight tracks and using MOPITT satellite observations. Anthropogenic emissions are underestimated by about 10% in high northern latitudes in spring, and shortcomings exist in simulating fire plumes. The remote impact of East-Siberian fire emissions is underestimated for spring, whereas the impact of Southeast Asian fire emissions to mid-latitude CO values is overestimated by the model. In summer, mid-latitude CO values agree well between model and observations, whereas summer high latitude East-Siberian fire emissions in the model are overestimated by 20% in comparison to observations in the region. On the other hand, CO concentrations are underestimated by about 30% over Alaska and Canada at altitudes above 4 km. BC values are overestimated by the model at altitudes above 4 km in summer. Based on MOZART-4, with tagged CO and BC tracers, anthropogenic emissions of Asia, Europe and the US have the largest contribution to the CO and BC in mid- and high latitudes in spring and summer. Southeast Asian, Chinese and Indian fires have a large impact on CO pollution in spring in low latitudes with a maximum between 20° and 30°, whereas Siberian fires contribute largely to the pollution in high latitudes, up to 10% in spring and up to 30% in summer. The largest contributions to BC values in high latitudes are from anthropogenic emissions (about 70%). CO and BC have larger mass loadings in April than in July, as a result of photochemistry and dynamics.
Assessing the regional surface influence through Backward Lagrangian Dispersion Models for aircraft CO2 vertical profiles observations in NE Spain

In this study the differences in the measured atmospheric CO2 mixing ratio at three aircraft profiling sites in NE Spain separated by 60 km are analyzed in regard to the variability of the surface fluxes in the regional surface influence area. First, the Regional Potential Surface Influence (RPSI) for fifty-one days in 2006 is calculated to assess the vertical, horizontal and temporal extent of the surface influence for the three sites at the regional scale (104 km2) at different altitudes of the profile (600, 1200, 2500 and 4000 meters above the sea level, m a.s.l.). Second, three flights carried out in 2006 (7 February, 24 August and 29 November) following the Crown Atmospheric Sampling (CAS) design are presented to study the relation between the measured CO2 variability and the Potential Surface Influence (PSI) and RPSI concepts. At 600 and 1200 m a.s.l. the regional signal is confined up to 50 h before the measurements whereas at higher altitudes (2500 and 4000 m a.s.l.) the regional surface influence is only recovered during spring and summer months. The RPSI from sites separated by 60 km overlap by up to 70% of the regional surface influence at 600 and 1200 m a.s.l., while the overlap decreases to 10–40% at higher altitudes (2500 and 4000 m a.s.l.). The scale of the RPSI area is suitable to understand the differences in the measured CO2 concentration in the three vertices of the CAS, as CO2 differences are attributed to local surrounding fluxes (February) or to the variability of regional surface influence as for the August and November flights. For these two flights, the variability in the regional scale influences the variability measured in the local scale. The CAS sampling design for aircraft measurements appears to be a suitable method to cope with the variability of a typical grid for inversion models as measurements are intensified within the PBL and the background concentration is measured every ~102 km.
Impact of the East Asian summer monsoon on long-term variations in the acidity of summer precipitation in Central China

The acidity of precipitation has been observed at stations of the Acid Rain Monitoring Network run by the China Meteorological Administration (CMA-ARMN) since 1992. Previous studies have shown that different long-term trends exist in different regions but detailed analysis of the causes of these is lacking. In this paper, we analyze summertime precipitation acidity data from the CMA-ARMN during 1992–2006 using EOFs and show that the summertime pH in China had different trends before and after 2000. The most significant decrease of pH is found in Central China. To investigate the causes of this decrease of pH in summer, we explore the relationship between changes in the pH value, the East Asian summer monsoon index, rainfall data, and pollutants emissions. We find that the East Asian summer monsoon can significantly affect the acidity of summer precipitation in Central China. In strong monsoon years, the pH in Central China is about 0.33 lower than that in weak monsoon years. Chemical transport model simulations using fixed emissions indicate that about 65% of the pH value difference (i.e., 0.22) is related to the summer monsoon, and constitutes 18–36% of the observed pH change (0.6&sim;1.2) in Central China during 1992–2006. Further studies reveal a relationship between the pH in Central China and the rainfall in the middle and lower reaches of the Yangtze River (MLYR), which can explain about 24% of the variance of pH in Central China. Simulations using an annually varying emission inventory show that at least 60% of the variation in precipitation acidity in Central China can be attributed to changes in pollutant emissions. Therefore, the increase in emissions of acidic species is the most important cause for the observed decrease of pH in Central China, and changes in meteorological factors, such as rainfall and other parameters related to the East Asian summer monsoon, play a less important but still significant role.