Atmospheric Environment (v.158, #C)

Effect of micro-scale wind on the measurement of airborne pollen concentrations using volumetric methods on a building rooftop by Kenji Miki; Shigeto Kawashima; Toshio Fujita; Kimihito Nakamura; Bernard Clot (1-10).
Evaluating airborne pollen concentrations is important for the understanding of the spatiotemporal dispersion of pollen grains. Using two identical pollen monitors in parallel, we performed two experiments in order to study the influences of a) the physical characteristics (orientation) of the air inlet and b) the presence of obstacles in proximity to the monitors on airborne pollen concentration data. The first experiment consisted of an evaluation of airborne pollen concentrations using two different types of orifices; 1) a vertically oriented inlet and 2) a wind vane intake, both attached to the same type of automatic pollen sampler. The second experiment investigated the relationship between vertical wind speed and horizontal wind direction around an obstacle with the goal of studying the impact of micro-scale wind on pollen sampling efficiency. The results of the two experiments suggest that the wind path near an obstacle might be redirected in a vertical direction before or after the wind flows over the obstacle, which causes measurement errors of airborne pollen concentrations that are proportional to the vertical wind speed, especially when a vertically oriented inlet is used.Display Omitted
Keywords: Micro-scale wind; Pollen sampler; Funnel inlet; Wind vane intake;

Investigating African trace gas sources, vertical transport, and oxidation using IAGOS-CARIBIC measurements between Germany and South Africa between 2009 and 2011 by U.R. Thorenz; A.K. Baker; E.C. Leedham Elvidge; C. Sauvage; H. Riede; P.F.J. van Velthoven; M. Hermann; A. Weigelt; D.E. Oram; C.A.M. Brenninkmeijer; A. Zahn; J. Williams (11-26).
Between March 2009 and March 2011 a commercial airliner equipped with a custom built measurement container (IAGOS-CARIBIC observatory) conducted 13 flights between South Africa and Germany at 10–12 km altitude, traversing the African continent north-south. In-situ measurements of trace gases (CO, CH4, H2O) and aerosol particles indicated that strong surface sources (like biomass burning) and rapid vertical transport combine to generate maximum concentrations in the latitudinal range between 10°N and 10°S coincident with the inter-tropical convergence zone (ITCZ). Pressurized air samples collected during these flights were subsequently analyzed for a suite of trace gases including C2-C8 non-methane hydrocarbons (NMHC) and halocarbons. These shorter-lived trace gases, originating from both natural and anthropogenic sources, also showed near equatorial maxima highlighting the effectiveness of convective transport in this region. Two source apportionment methods were used to investigate the specific sources of NMHC: positive matrix factorization (PMF), which is used for the first time for NMHC analysis in the upper troposphere (UT), and enhancement ratios to CO. Using the PMF method three characteristic airmass types were identified based on the different trace gas concentrations they obtained: biomass burning, fossil fuel emissions, and “background” air. The first two sources were defined with reference to previously reported surface source characterizations, while the term “background” was given to air masses in which the concentration ratios approached that of the lifetime ratios. Comparison of enhancement ratios between NMHC and CO for the subset of air samples that had experienced recent contact with the planetary boundary layer (PBL) to literature values showed that the burning of savanna and tropical forest is likely the main source of NMHC in the African upper troposphere (10–12 km). Photochemical aging patterns for the samples with PBL contact revealed that the air had different degradation histories depending on the hemisphere in which they were emitted. In the southern hemisphere (SH) air masses experienced more dilution by clean background air whereas in the northern hemisphere (NH) air masses are less diluted or mixed with background air still containing longer lived NMHC. Using NMHC photochemical clocks ozone production was seen in the BB outflow above Africa in the NH.
Keywords: Africa; Biomass burning; NMHC; Trace gas emissions; UTLS; Aircraft observation;

On the source inversion of fugitive surface layer releases. Part II. Complex sources by V. Sanfélix; A. Escrig; A. López-Lilao; I. Celades; E. Monfort (27-35).
The experimental measurement of fugitive emissions of particulate matter entails inherent complexity because they are usually discontinuous, of short duration, may be mobile, and are affected by weather conditions. Owing to this complexity, instead of experimental measurements, emission factors are used to inventory such emissions. Unfortunately, emission factor datasets are still very limited at present and are insufficient to identify problematic operations and appropriately select control measures. To extend these datasets, a source inversion methodology (described in Part I of this work) was applied to field campaigns in which operation-specific fugitive particulate matter emission factors were determined for several complex fugitive sources, some of which were mobile. Mobile sources were treated as a superposition of instantaneous sources. The experimental campaigns were conducted at ports (bulk solids terminals), aggregate quarries, and cement factories, encompassing powder handling operations and vehicle circulation on paved and unpaved roads. Emission factors were derived for the operations and materials involved in these scenarios and compared with those available in the emission factor compilations. Significant differences were observed between the emission factors obtained in the studied handling operations. These differences call into question the use of generic emission factors and highlight the need for more detailed studies in this field.
Keywords: Fugitive emissions; Emission factor; Particulate matter; Handling operations; Unpaved roads;

Daily ambient air pollution metrics for five cities: Evaluation of data-fusion-based estimates and uncertainties by Mariel D. Friberg; Ralph A. Kahn; Heather A. Holmes; Howard H. Chang; Stefanie Ebelt Sarnat; Paige E. Tolbert; Armistead G. Russell; James A. Mulholland (36-50).
Spatiotemporal characterization of ambient air pollutant concentrations is increasingly relying on the combination of observations and air quality models to provide well-constrained, spatially and temporally complete pollutant concentration fields. Air quality models, in particular, are attractive, as they characterize the emissions, meteorological, and physiochemical process linkages explicitly while providing continuous spatial structure. However, such modeling is computationally intensive and has biases. The limitations of spatially sparse and temporally incomplete observations can be overcome by blending the data with estimates from a physically and chemically coherent model, driven by emissions and meteorological inputs. We recently developed a data fusion method that blends ambient ground observations and chemical-transport-modeled (CTM) data to estimate daily, spatially resolved pollutant concentrations and associated correlations. In this study, we assess the ability of the data fusion method to produce daily metrics (i.e., 1-hr max, 8-hr max, and 24-hr average) of ambient air pollution that capture spatiotemporal air pollution trends for 12 pollutants (CO, NO2, NOx, O3, SO2, PM10, PM2.5, and five PM2.5 components) across five metropolitan areas (Atlanta, Birmingham, Dallas, Pittsburgh, and St. Louis), from 2002 to 2008.Three sets of comparisons are performed: (1) the CTM concentrations are evaluated for each pollutant and metropolitan domain, (2) the data fusion concentrations are compared with the monitor data, (3) a comprehensive cross-validation analysis against observed data evaluates the quality of the data fusion model simulations across multiple metropolitan domains. The resulting daily spatial field estimates of air pollutant concentrations and uncertainties are not only consistent with observations, emissions, and meteorology, but substantially improve CTM-derived results for nearly all pollutants and all cities, with the exception of NO2 for Birmingham. The greatest improvements occur for O3 and PM2.5. Squared spatiotemporal correlation coefficients range between simulations and observations determined using cross-validation across all cities for air pollutants of secondary and mixed origins are R2 = 0.88–0.93 (O3), 0.81–0.89 (SO4), 0.67–0.83 (PM2.5), 0.52–0.72 (NO3), 0.43–0.80 (NH4), 0.32–0.51 (OC), and 0.14–0.71 (PM10).Results for relatively homogeneous pollutants of secondary origin, tend to be better than those for more spatially heterogeneous (larger spatial gradients) pollutants of primary origin (NOx, CO, SO2 and EC). Generally, background concentrations and spatial concentration gradients reflect interurban airshed complexity and the effects of regional transport, whereas daily spatial pattern variability shows intra-urban consistency in the fused data. With sufficiently high CTM spatial resolution, traffic-related pollutants exhibit gradual concentration gradients that peak toward the urban centers. Ambient pollutant concentration uncertainty estimates for the fused data are both more accurate and smaller than those for either the observations or the model simulations alone.Display Omitted
Keywords: Air quality; Spatiotemporal; Fusion; Blending; CMAQ;

Phragmites australis is a common invasive reed of North American coastal marshes, and efforts to control or eradicate it often are included in coastal marsh restoration efforts. While much research has tested impacts of P. australis removal on plant and faunal communities, less is known about biogeochemical responses to P. australis removal. Since coastal marshes are valued for their robust carbon sequestration, understanding the effect of P. australis removal on marsh carbon cycling dynamics is important. Temporary P. australis aboveground biomass clearing conducted as part of a restoration effort provided an opportunity to evaluate changes in fluxes of the greenhouse gases (GHGs) carbon dioxide (CO2) and methane (CH4) during P. australis removal and recovery. In Experiment 1 (2014 growing season), GHG fluxes were compared between a P. australis stand cleared mechanically and recovered within months of initial removal and an uncleared stand in the same marsh system. CO2 uptake increased dramatically in the cleared stand as P. australis regrew, but CH4 emissions remained unchanged, demonstrating that P. australis did not directly contribute to CH4 emission. In Experiment 2 (2015 manipulations), to test mechanisms of P. australis’ impact on GHG fluxes, fluxes (light and dark) were compared between unimpacted P. australis plots, cut P. australis plots with litter, and cleared P. australis plots without litter. P. australis cutting (independent of litter removal) resulted in increased CO2 and CH4 emissions. Recovery of P. australis directly drove the rapid recovery of CO2 uptake, and did not increase (and possibly attenuated) CH4 emissions. Results of this study suggest that at this site, P. australis removal, in the absence of native vegetation recovery, may exacerbate GHG emission of coastal marshes in the short term, and that longer-term impacts warrant investigation.
Keywords: Carbon dioxide; Methane; Ecosystem services; Invasive species; Restoration;

Physical and chemical characterization of urban winter-time aerosols by mobile measurements in Helsinki, Finland by Liisa Pirjola; Jarkko V. Niemi; Sanna Saarikoski; Minna Aurela; Joonas Enroth; Samara Carbone; Karri Saarnio; Heino Kuuluvainen; Anu Kousa; Topi Rönkkö; Risto Hillamo (60-75).
A two-week measurement campaign by a mobile laboratory van was performed in urban environments in the Helsinki metropolitan area, Finland, in winter 2012, to obtain a comprehensive view on aerosol properties and sources. The abundances and physico-chemical properties of particles varied strongly in time and space, depending on the main sources of aerosols. Four major types of winter aerosol were recognized: 1) clean background aerosol with low particle number (Ntot) and lung deposited surface area (LDSA) concentrations due to marine air flows from the Atlantic Ocean; 2) long-range transported (LRT) pollution aerosol due to air flows from eastern Europe where the particles were characterized by the high contribution of oxygenated organic aerosol (OOA) and inorganic species, particularly sulphate, but low BC contribution, and their size distribution possessed an additional accumulation mode; 3) fresh smoke plumes from residential wood combustion in suburban small houses, these particles were characterized by high biomass burning organic aerosol (BBOA) and black carbon (BC) concentrations; and 4) fresh emissions from traffic while driving on busy streets in the city centre and on the highways during morning rush hours. This aerosol was characterized by high concentration of Ntot, LDSA, small particles in the nucleation mode, as well as high hydrocarbon-like organic aerosol (HOA) and BC concentrations. In general, secondary components (OOA, NO3, NH4, and SO4) dominated the PM1 chemical composition during the LRT episode accounting for 70–80% of the PM1 mass, whereas fresh primary emissions (BC, HOA and BBOA) dominated the local traffic and wood burning emissions. The major individual particle types observed with electron microscopy analysis (TEM/EDX) were mainly related to residential wood combustion (K/S/C-rich, soot, other C-rich particles), traffic (soot, Si/Al-rich, Fe-rich), heavy fuel oil combustion in heat plants or ships (S with V-Ni-Fe), LRT pollutants (S/C-rich secondary particles) and sea salt (Na/Cl-rich). Tar balls from wood combustion were also observed, especially (∼5%) during the LRT pollution episode.
Keywords: Mobile laboratory; Traffic; Wood burning; Size distribution; Black carbon; AMS;

The denitrification-decomposition (DNDC) model is a useful tool for integrating the effects of agricultural practices and climate change on soil nitrous oxide (N2O) emissions from agricultural ecosystems. In this study, the DNDC model was evaluated against observations and used to simulate the effect of plastic mulching on soil N2O emissions and crop growth. The DNDC model performed well in simulating temporal variations in N2O emissions and plant growth during the observation period, although it slightly underestimated the cumulative N2O emissions, and was able to simulate the effects of plastic mulching on N2O emissions and crop yield. Both the observations and simulations demonstrated that the application of plastic film increased cumulative N2O emissions and cotton lint yield compared with the non-mulched treatment. The sensitivity test showed that the N2O emissions and lint yield were sensitive to changes in climate and management practices, and the application of plastic film made the N2O emissions and lint yield less sensitive to changes in temperature and irrigation. Although the simulations showed that the beneficial impacts of plastic mulching on N2O emissions were not gained under high fertilizer and irrigation scenarios, our simulations suggest that the application of plastic film effectively reduced soil N2O emissions while promoting yields under suitable fertilizer rates and irrigation. Compared with the baseline scenario, future climate change significantly increased N2O emissions by 15–17% without significantly influencing the lint yields in the non-mulched treatment; in the mulched treatment, climate change significantly promoted the lint yield by 5–6% and significantly reduced N2O emissions by 14% in the RCP4.5 and RCP8.5 scenarios. Overall, our results demonstrate that the application of plastic film is an efficient way to address increased N2O emissions and simultaneously enhance crop yield in the future.
Keywords: DNDC; N2O emissions; Lint yield; Plastic film mulching; Climate change;

European emissions of the powerful greenhouse gases hydrofluorocarbons inferred from atmospheric measurements and their comparison with annual national reports to UNFCCC by F. Graziosi; J. Arduini; F. Furlani; U. Giostra; P. Cristofanelli; X. Fang; O. Hermanssen; C. Lunder; G. Maenhout; S. O'Doherty; S. Reimann; N. Schmidbauer; M.K. Vollmer; D. Young; M. Maione (85-97).
Hydrofluorocarbons are powerful greenhouse gases developed by industry after the phase-out of the ozone depleting chlorofluorocarbons and hydrochlorofluorocarbons required by the Montreal Protocol. The climate benefit of reducing the emissions of hydrofluorocarbons has been widely recognised, leading to an amendment of the Montreal Protocol (Kigali Amendment) calling for developed countries to start to phase-down hydrofluorocarbons by 2019 and in developing countries to follow with a freeze between 2024 and 2028. In this way, nearly half a degree Celsius of warming would be avoided by the end of the century. Hydrofluorocarbons are also included in the basket of gases controlled under the Kyoto Protocol of the United Nations Framework Convention on Climate Change. Annex I parties to the Convention submit annual national greenhouse gas inventories based on a bottom-up approach, which relies on declared anthropogenic activities. Top-down methodologies, based on atmospheric measurements and modelling, can be used in support to the inventory compilation. In this study we used atmospheric data from four European sites combined with the FLEXPART dispersion model and a Bayesian inversion method, in order to derive emissions of nine individual hydrofluorocarbons from the whole European Geographic Domain and from twelve regions within it, then comparing our results with the annual emissions that the European countries submit every year to the United Nations Framework Convention on Climate Change, as well as with the bottom-up Emissions Database for Global Atmospheric Research. We found several discrepancies when considering the specific compounds and on the country level. However, an overall agreement is found when comparing European aggregated data, which between 2008 and 2014 are on average 84.2 ± 28.0 Tg-CO2-eq·yr−1 against the 95.1 Tg-CO2-eq·yr−1 reported by UNFCCC in the same period. Therefore, in agreement with other studies, the gap on the global level between bottom-up estimates of Annex I countries and total global top-down emissions should be essentially due to emissions from non-reporting countries (non-Annex I).
Keywords: F-gases; Montreal Protocol; Kyoto Protocol; Emission verifications; Inverse modelling; Atmospheric measurements;

Meteorological constraints on characteristics of daily dustfall in Xi'an by Yan Yan; Hongyun Chen; Lianji Liang; Long Ma; Xingxing Liu; Haijiao Liu; Youbin Sun (98-104).
Dust deposition is a crucial link of dust cycle that is less constrained in model studies. This study acquired profiles of flux and size distribution of daily dustfall from 2012 to 2013 in Xi'an on the southern Chinese Loess Plateau. On this basis, we made quantitative estimates of dust contribution from particular sources and processes, which provides important boundary conditions for model studies. Regrouping the data into transport- and source-limited deposition scenarios, we revealed that besides precipitation extreme wind speed and average relative humidity are the primary meteorological constraints in the transport- and source-limited scenarios, respectively. Stronger extreme wind speed promotes higher flux and deposition of dust >16 μm, corroborating previous interpretations of variation of flux and grain size of aeolian deposits. However, higher average relative humidity favors lower flux and deposition of dust <16 μm, which is a deposition process not recognized before, and is possibly due to hygroscopicity of mineral dust or the influence of water vapor on air convection. Elucidating this process in future studies might substantially improve model performance on dust deposition.
Keywords: Dustfall; Dust deposition; Chinese Loess Plateau; Meteorological constraint;

The secondary organic aerosol (SOA) concentration is generally underestimated by models. Recent studies suggest that the underprediction is related to underestimations of aromatic volatile organic compound (VOC) emissions and SOA yields in current models. Here, the impacts of these two factors in China were investigated with the regional air quality modeling system RAMS-CMAQ, referring to field observations during the episode from October 14 to November 14, 2014. Comparisons between the observed and modeled SOA of four sensitivity simulation cases indicated the significant impacts of the two underestimated factors on the SOA output. By considering these two aspects, the simulated mean SOA concentrations significantly increased by nearly 4 times with a good representation of the intensively temporal variations of concentrations, which were largely controlled by photochemical processes rather than meteorological conditions. The improvement in SOA compensated for the underestimations by approximately 23.5% and contributed to the mean fraction of SOA to organic aerosol (OA) by increasing the fraction from less than 7% to more than 25%, which was closer to the observed result. These results suggested a more reasonable and more realistic representation of SOA formation in the model after allowing for the two factors. Due to the better simulation of SOA, predictions of OA were correspondingly improved when the correlation coefficient increased from 0.57 to 0.73 and other bias parameters were reduced, which indicated the improved ability of our model to trace the temporal variations of OA. Based on the improved simulation throughout the episode, the mean SOA concentration was obviously higher in eastern China than in the west. The highest concentration appeared in the Sichuan Basin and Pearl River Delta (PRD) areas, with values of 6–11 μg/m3 and 8–17 μg/m3, respectively. Over the wide regions of central and eastern China, the dominant component in SOA was formed from anthropogenic sources (ASOA), generally accounting for more than 60%.
Keywords: Secondary organic aerosol; Volatile organic compounds; RAMS-CMAQ; Fine particles; China;

An assessment of 10-year NOAA aircraft-based tropospheric ozone profiling in Colorado by Mark Leonard; Irina Petropavlovskikh; Meiyun Lin; Audra McClure-Begley; Bryan J. Johnson; Samuel J. Oltmans; David Tarasick (116-127).
The Global Greenhouse Gas Reference Network Aircraft Program at NOAA has sampled ozone and other atmospheric trace constituents in North America for over a decade (2005-present). The method to derive tropospheric ozone climatology from the light aircraft measurements equipped with the 2B Technology instruments is described in this paper. Since ozone instruments at most of aircraft locations are flown once a month, this raises the question of whether the sampling frequency allows for deriving a climatology that can adequately represent ozone seasonal and vertical variability over various locations. Here we interpret the representativeness of the tropospheric ozone climatology derived from these under-sampled observations using hindcast simulations conducted with the Geophysical Fluid Dynamics Laboratory chemistry-climate model (GFDL-AM3). We first focus on ozone measurements from monthly aircraft profiles over the Front Range of Colorado and weekly ozonesondes launched in Boulder, Colorado. The climatology is presented as monthly values separated in 5th, 25th, 50th, 75th, 95th percentiles, and averaged at three vertical layers: lower (1.6–3 km), middle (3–6 km), and upper (6–8 km) troposphere. The aircraft-based climatology is compared to the climatology derived from the nearest located ozonesondes launched from Boulder, Colorado, from GFDL-AM3 co-sampled in time with in-situ observations, and from GFDL-AM3 continuous 3-h samples. Based on these analyses, we recommend the sampling frequency to obtain adequate representation of ozone climatology in the free troposphere. The 3-h sampled AM3 model is used as a benchmark reference for the under-sampled time series. We find that the minimal number of soundings required per month for the all altitude bins (1.6–3, 3–6, and 6–8 km) to sufficiently match the 95% confidence level of the fully sampled monthly ozone means vary between 3 and 5 sounding per month, except in August with a minimum of 6 soundings per month. The middle altitude bin required the least number of samplings per month. We determine the reasonably good agreement between the ozonesondes and aircraft measurements near Boulder suggest that valuable climatologies could be developed from the aircraft sites where no ozonesondes exist even though the aircraft measurements are more limited in number than the ozonesondes. When averaged over a number of years the aircraft data provide valuable information. More frequent sampling could tell us more but the measurements given would indicate that they can provide interesting climatological results.
Keywords: Tropospheric ozone; Climatology; Model analysis; Aircraft observations; Validation; Ozone variability;

Chemical composition, sources and secondary processes of aerosols in Baoji city of northwest China by Y.C. Wang; R.-J. Huang; H.Y. Ni; Y. Chen; Q.Y. Wang; G.H. Li; X.X. Tie; Z.X. Shen; Y. Huang; S.X. Liu; W.M. Dong; P. Xue; R. Fröhlich; F. Canonaco; M. Elser; K.R. Daellenbach; C. Bozzetti; I. El Haddad; A.S.H. Prévôt; M.R. Canagaratna; D.R. Worsnop; J.J. Cao (128-137).
Particulate air pollution is a severe environmental problem in China, affecting visibility, air quality, climate and human health. However, previous studies focus mainly on large cities such as Beijing, Shanghai, and Guangzhou. In this study, an Aerodyne Aerosol Chemical Speciation Monitor was deployed in Baoji, a middle size inland city in northwest China from 26 February to 27 March 2014. The non-refractory submicron aerosol (NR-PM1) was dominated by organics (55%), followed by sulfate (16%), nitrate (15%), ammonium (11%) and chloride (3%). A source apportionment of the organic aerosol (OA) was performed with the Sofi (Source Finder) interface of ME-2 (Multilinear Engine), and six main sources/factors were identified and classified as hydrocarbon-like OA (HOA), cooking OA (COA), biomass burning OA (BBOA), coal combustion OA (CCOA), less oxidized oxygenated OA (LO-OOA) and more oxidized oxygenated OA (MO-OOA), which contributed 20%, 14%, 13%, 9%, 23% and 21% of total OA, respectively. The contribution of secondary components shows increasing trends from clean days to polluted days, indicating the importance of secondary aerosol formation processes in driving particulate air pollution. The formation of LO-OOA and MO-OOA is mainly driven by photochemical reactions, but significantly influenced by aqueous-phase chemistry during periods of low atmospheric oxidative capacity.
Keywords: ACSM; Chemical composition; Organic aerosol; Source apportionment; Secondary formation processes;

Volatility of source apportioned wintertime organic aerosol in the city of Athens by Evangelos E. Louvaris; Kalliopi Florou; Eleni Karnezi; Dimitrios K. Papanastasiou; Georgios I. Gkatzelis; Spyros N. Pandis (138-147).
The volatility distribution of ambient organic aerosol (OA) and its components was measured during the winter of 2013 in the city of Athens combining a thermodenuder (TD) and a High Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS). Positive Matrix Factorization (PMF) analysis of both the ambient and the thermodenuder AMS-spectra resulted in a four-factor solution for the OA, namely: hydrocarbon-like OA (HOA), biomass burning OA (BBOA), cooking OA (COA), and oxygenated OA (OOA). The thermograms of the four factors were analyzed and the corresponding volatility distributions were estimated using the volatility basis set (VBS). All four factors included compounds with a wide range of effective volatilities from 10 to less than 10−4 μg m−3 at 298 K. Almost 40% of the HOA consisted of low-volatility organic compounds (LVOCs) with the semi-volatile compounds (SVOCs) representing roughly 30%, while the remaining 30% consisted of extremely low volatility organic compounds (ELVOCs). BBOA was more volatile than the HOA factor on average, with 10% ELVOCs, 40% LVOCs, and 50% SVOCs. 10% of the COA consisted of ELVOCs, another 65% LVOCs, and 50% SVOCs. Finally, the OOA was the least volatile factor and included 40% ELVOCs, 25% LVOCs, and 35% SVOCs. Combining the volatility distributions and the O:C ratios of the various factors, we placed our results in the 2D-VBS analysis framework of Donahue et al. (2012). HOA and BBOA are in the expected region but also include an ELVOC component. COA is in similar range as HOA, but on average is half an order of magnitude more volatile. The OOA in these wintertime conditions had a moderate O:C ratio and included both semi-volatile and extremely low volatility components. The above results are sensitive to the assumed values of the effective vaporization enthalpy and the accommodation coefficient. A reduction of the accommodation coefficient by an order of magnitude or the reduction of the vaporization enthalpy by 20 kJ mol−1 results in the increase of the average volatility by half an order of magnitude.
Keywords: Source apportionment; Volatility; Thermodenuder;

Role of organic aerosols in CCN activation and closure over a rural background site in Western Ghats, India by V. Singla; S. Mukherjee; P.D. Safai; G.S. Meena; K.K. Dani; G. Pandithurai (148-159).
The cloud condensation nuclei (CCN) closure study was performed to exemplify the effect of aerosol chemical composition on the CCN activity of aerosols at Mahabaleshwar, a high altitude background site in the Western Ghats, India. For this, collocated aerosol, CCN, Elemental Carbon (EC), Organic Carbon (OC), sub-micron aerosol chemical speciation for the period from 3rd June to 19th June 2015 was used. The chemical composition of non-refractory particulate matter (<1 μm) as measured by Time of Flight – Aerosol Chemical Speciation Monitor (ToF-ACSM) was dominated by organics with average concentration of 3.81 ± 1.6, 0.32 ± 0.06, 0.15 ± 0.02, 0.13 ± 0.03 and 0.95 ± 0.12 μg m−3 for organics, ammonium, chloride, nitrate and sulphate, respectively. The PM1 number concentration as obtained by Wide Range Aerosol Spectrometer (WRAS) varied from 750 to 6480 cm−3. The average mass concentration of elemental carbon (EC) as measured by OC-EC analyzer was 1.16 ± 0.4 μg m−3. The average CCN concentrations obtained from CCN counter (CCNC) at five super-saturations (SS's) was 118 ± 58 cm−3 (0.1% SS), 873 ± 448 cm−3 (0.31% SS), 1308 ± 603 cm−3 (0.52% SS), 1610 ± 838 cm−3 (0.73% SS) and 1826 ± 985 cm−3 (0.94% SS). The CCN concentrations were predicted using Köhler theory on the basis of measured aerosol particle number size distribution, size independent NR-PM1 chemical composition and calculated hygroscopicity. The CCN closure study was evaluated for 3 scenarios, B-I (all soluble inorganics), B-IO (all soluble organics and inorganics) and B-IOOA (all soluble inorganic and soluble oxygenated organic aerosol, OOA). OOA component was derived from the positive matrix factorization (PMF) analysis of organic aerosol mass spectra. Considering the bulk composition as internal mixture, CCN closure study was underestimated by 16–39% for B-I and overestimated by 47–62% for B-IO. The CCN closure result was appreciably improved for B-IOOA where the knowledge of OOA fraction was introduced and uncertainty reduced to within 8–10%.Display Omitted
Keywords: ACSM; NR-PM1; PMF; OOA; Köhler theory; CCN closure;

Lidar observations revealing transport of O3 in the presence of a nocturnal low-level jet: Regional implications for “next-day” pollution by John T. Sullivan; Scott D. Rabenhorst; Joel Dreessen; Thomas J. McGee; Ruben Delgado; Laurence Twigg; Grant Sumnicht (160-171).
Remotely sensed profiles of ozone (O3) and wind are presented continuously for the first time during a nocturnal low-level jet (NLLJ) event occurring after a severe O3 episode in the Baltimore-Washington D.C. (BW) urban corridor throughout 11–12 June 2015. High-resolution O3 lidar observations indicate a well-mixed and polluted daytime O3 reservoir, which decayed into a contaminated nocturnal residual layer (RL) with concentrations between 70 and 100 ppbv near 1 km above the surface. Observations indicate the onset of the NLLJ was responsible for transporting polluted O3 away from the region, while simultaneously affecting the height and location of the nocturnal residual layer. High-resolution modeling analyses and next-day (12 June) lidar, surface, and balloon-borne observations indicate the trajectory of the NLLJ and polluted residual layer corresponds with “next-day” high O3 at sites throughout the southern New England region (New York, Connecticut, Massachusetts). The novel O3 lidar observations are evidence of both nocturnal advection (via high NLLJ wind fields) and entrainment of the polluted residual layer in the presence of the “next-day” convectively growing boundary layer. In the greater context, the novel observational suite described in this work has shown that the chemical budget in areas downwind of major urban centers can be altered significantly overnight during transport events such as the NLLJ.Display Omitted
Keywords: O3 transport; Low-level jet; Air quality; Remote sensing; TOLNet;

Modeling spatial patterns of link-based PM2.5 emissions and subsequent human exposure in a large canadian metropolitan area by Weeberb J. Requia; Ron Dalumpines; Matthew D. Adams; Altaf Arain; Mark Ferguson; Petros Koutrakis (172-180).
Understanding the relationship between mobile source emissions and subsequent human exposure is crucial for emissions control. Determining this relationship over space is fundamental to improve the accuracy and precision of public policies. In this study, we evaluated the spatial patterns of link-based PM2.5 emissions and subsequent human exposure in a large Canadian metropolitan area - the Greater Toronto and Hamilton Area (GTHA). This study was performed in three stages. First, we estimated vehicle emissions using transportation models and emission simulators. Then we evaluated human exposure to PM2.5 emissions using the Intake fraction (iF) approach. Finally, we applied geostatistical methods to assess spatial patterns of vehicle emissions and subsequent human exposure based on three prospective goals: i) classification of emissions (Global Moran's I test), ii) level of emission exposure (Getis-Ord General G test), and; iii) location of emissions (Anselin Local Moran's I). Our results showed that passenger vehicles accounted for the highest total amount of PM2.5 emissions, representing 57% emissions from all vehicles. Examining only the emissions from passenger vehicles, on average, each person in the GTHA inhales 2.58 × 10−3 ppm per day. Accounting the emissions from buses and trucks, on average each person inhales 0.12 × 10−3 and 1.91 × 10−3 ppm per day, respectively. For both PM2.5 emissions and human exposure using iF approach, our analysis showed Moran's Index greater than 0 for all vehicle categories, suggesting the presence of significant clusters (p-value <0.01) in the region. Our study indicates that air pollution control policy must be developed for the whole region, because of the spatial distribution of housing and businesses centers and inter-connectivity of transportation networks across the region, where a policy cannot simply be based on a municipal or other boundaries.
Keywords: Air pollution; Traffic emissions; Human exposure; Spatial patterns; PM2.5; Intake fraction approach;

A cost-effective method for simulating city-wide air flow and pollutant dispersion at building resolving scale by Antoine Berchet; Katrin Zink; Clive Muller; Dietmar Oettl; Juerg Brunner; Lukas Emmenegger; Dominik Brunner (181-196).
A cost-effective method is presented allowing to simulate the air flow and pollutant dispersion in a whole city over multiple years at the building-resolving scale with hourly time resolution. This combination of high resolution and long time span is critically needed for epidemiological studies and for air pollution control, but still poses a great challenge for current state-of-the-art modelling techniques. The presented method relies on the pre-computation of a discrete set of possible weather situations and corresponding steady-state flow and dispersion patterns. The most suitable situation for any given hour is then selected by matching the simulated wind patterns to meteorological observations in and around the city. The catalogue of pre-computed situations corresponds to different large-scale forcings in terms of wind speed, wind direction and stability. A meteorological model converts these forcings into realistic mesoscale flow patterns accounting for the effects of topography and land-use contrasts in a domain covering the city and its surroundings. These mesoscale patterns serve as boundary conditions for a microscale urban flow model which finally drives a Lagrangian air pollutant dispersion model. The method is demonstrated with the modelling system GRAMM/GRAL v14.8 for two Swiss cities in complex terrain, Zurich and Lausanne. The mesoscale flow patterns in the two regions of interest, dominated by land-lake breezes and driven by the partly steep topography, are well reproduced in the simulations matched to in situ observations. In particular, the combination of wind measurements at different locations around the city appeared to be a robust approach to deduce the stability class for the boundary layer within the city. This information is critical for predicting the temporal variability of pollution concentration within the city, regarding their relationship with the intensity of horizontal and vertical dispersion and of turbulence. In the vicinity of sources, the 5 m resolution chosen in our set-up is not always sufficient to reproduce the very steep concentration gradients, pointing at additional cost optimisations in the method required to make higher resolutions affordable. Nevertheless, the catalogue-based methodology allows reproducing concentration variability very consistently further away from emission sources, hence for most parts of the city.
Keywords: Urban pollution; Pollutant dispersion; CFD modelling;

Multi-seasonal pattern in 5-year record of stable H, O and S isotope compositions of precipitation (Wrocław, SW Poland) by Maciej Górka; Grzegorz Skrzypek; Stanisław Hałas; Mariusz-Orion Jędrysek; Dariusz Strąpoć (197-210).
Sulphur dioxide is still a major industrial pollutant in the atmosphere. However, its origin is not always easily traceable, particularly at regional scale where numerous sulphur sources coexist. Geochemical tracers, such as the stable sulphur (δ34S) and oxygen (δ18O) isotopic compositions of sulphates in precipitation, have been successfully applied for estimation of the S-contribution from multiple sources to the atmosphere. However, the majority of previous studies conducted over relatively short time spans have revealed a short-term seasonal trends only and were unable to capture multi seasonal systematics. Here, we present results from a five-year monitoring program conducted in Wrocław (SW Poland). We have determined the Local Meteoric Water Line of δ2H= (6.91 ± 0.25) × δ18O + (2.39 ± 2.43) and sulphates stable sulphur (δ34S(SO4) 0.3–5.4‰) and oxygen (δ18O(SO4) 4.7–19.1‰) isotope composition in precipitation. The stable sulphur isotope results confirm that sulphates in precipitation primarily originate from high temperature (minimum mean over sampling period 680 °C) combustion of fuels with δ34S signatures ≤4.4‰. The stable oxygen isotope composition of sulphates and precipitation water indicates that the primary sulphate (generated directly by industrial processes) contribution was <49% during the whole study period, with a mean of ∼20% during the non-heating and ∼40% during the heating periods. The δ34S(SO4) value for precipitation displays multi-seasonal oscillations with an amplitude of about 2‰, which has not been previously reported. The mechanism driving the oscillation needs further investigation in order to reveal possible associations between this phenomenon and climatic patterns or changes in fossil fuel use. This new evidence from 5-year-long records needs to be taken into consideration when analysing trends from shorter-term observations.
Keywords: Sulphates; Wrocław; Precipitation; Oxygen; Isotope; Pollutants;

A high-resolution (0.1° × 0.1°) inventory of methane emissions from Canadian and Mexican oil and gas systems by Jian-Xiong Sheng; Daniel J. Jacob; Joannes D. Maasakkers; Melissa P. Sulprizio; Daniel Zavala-Araiza; Steven P. Hamburg (211-215).
Canada and Mexico have large but uncertain methane emissions from the oil/gas industry. Inverse analyses of atmospheric methane observations can improve emission estimates but require accurate source patterns as prior information. In order to serve this need, we develop a 0.1° × 0.1° gridded inventory of oil/gas emissions in Canada for 2013 and Mexico for 2010 by disaggregating national emission inventories using best available data for production, processing, transmission, and distribution. Results show large differences with the EDGAR v4.2 gridded global inventory used in past inverse analyses. Canadian emissions are concentrated in Alberta (gas production and processing) and Mexican emissions are concentrated along the east coast (oil production).
Keywords: Methane; Natural gas; Oil; Inverse modeling;

For a common household wood stove and a pellet stove we investigated the dependence of emission factors for various gaseous and particulate pollutants on burning phase, burning condition, and fuel. Ideal and non-ideal burning conditions (dried wood, under- and overload, small logs, logs with bark, excess air) were used. We tested 11 hardwood species (apple, ash, bangkirai, birch, beech, cherry, hickory, oak, olive, plum, sugar maple), 4 softwood species (Douglas fir, pine, spruce, spruce/fir), treated softwood, beech and oak wood briquettes, paper briquettes, brown coal, wood chips, and herbaceous species (miscanthus, Chinese silver grass) as fuel. Particle composition (black carbon, non-refractory, and some semi-refractory species) was measured continuously. Repeatability was shown to be better for the pellet stove than for the wood stove. It was shown that the user has a strong influence on wood stove emission behavior both by selection of the fuel and of the burning conditions: Combustion efficiency was found to be low at both very low and very high burn rates, and influenced particle properties such as particle number, mass, and organic content in a complex way. No marked differences were found for the emissions from different wood species. For non-woody fuels, much higher emission factors could be observed (up to five-fold increase). Strongest enhancement of emission factors was found for burning of small or dried logs (up to six-fold), and usage of excess air (two- to three-fold). Real world pellet stove emissions can be expected to be much closer to laboratory-derived emission factors than wood stove emissions, due to lower dependence on user operation.Display Omitted
Keywords: Residential wood combustion; Log wood; Pellets; Emission factors; Burning condition;

Oxidative potential of gas phase combustion emissions - An underestimated and potentially harmful component of air pollution from combustion processes by S. Stevanovic; A. Vaughan; F. Hedayat; F. Salimi; M.M. Rahman; A. Zare; R.A. Brown; R.J. Brown; H. Wang; Z. Zhang; X. Wang; S.E. Bottle; I.A. Yang; Z.D. Ristovski (227-235).
The oxidative potential (OP) of the gas phase is an important and neglected aspect of environmental toxicity. Whilst prolonged exposure to particulate matter (PM) associated reactive oxygen species (ROS) have been shown to lead to negative health effects, the potential for compounds in gas phase to cause similar effects is yet to be understood.In this study we describe: the significance of the gas phase OP generated through vehicle emissions; discuss the origin and evolution of species contributing to measured OP; and report on the impact of gas phase OP on human lung cells. The model aerosol for this study was exhaust emitted from a Euro III Common-rail diesel engine fuelled with different blends of diesel and biodiesel. The gas phase of these emissions was found to be potentially as hazardous as the particle phase. Fuel oxygen content was found to negatively correlate with the gas phase OP, and positively correlate with particle phase OP. This signifies a complex interaction between reactive species present in gas and particle phase. Furthermore, this interaction has an overarching effect on the OP of both particle and gas phase, and therefore the toxicity of combustion emissions.

Time-resolved analysis of primary volatile emissions and secondary aerosol formation potential from a small-scale pellet boiler by Hendryk Czech; Simone M. Pieber; Petri Tiitta; Olli Sippula; Miika Kortelainen; Heikki Lamberg; Julija Grigonyte; Thorsten Streibel; André S.H. Prévôt; Jorma Jokiniemi; Ralf Zimmermann (236-245).
Small-scale pellet boilers and stoves became popular as a wood combustion appliance for domestic heating in Europe, North America and Asia due to economic and environmental aspects. Therefore, an increasing contribution of pellet boilers to air pollution is expected despite their general high combustion efficiency. As emissions of primary organic aerosol (POA) and permanent gases of pellet boilers are well investigated, the scope of this study was to investigate the volatile organic emissions and the formation potential of secondary aerosols for this type of appliance. Fresh and aged emissions were analysed by a soot-particle aerosol time-of-flight mass spectrometry (SP-AMS) and the molecular composition of the volatile precursors with single-photon ionisation time-of-flight mass spectrometry (SPI-TOFMS) at different pellet boiler operation conditions. Organic emissions in the gas phase were dominated by unsaturated hydrocarbons while wood-specific VOCs, e.g. phenolic species or substituted furans, were only detected during the starting phase. Furthermore, organic emissions in the gas phase were found to correlate with fuel grade and combustion technology in terms of secondary air supply. Secondary organic aerosols of optimised pellet boiler conditions (OPT, state-of-the-art combustion appliance) and reduced secondary air supply (RSA, used as a proxy for pellet boilers of older type) were studied by simulating atmospheric ageing in a Potential Aerosol Mass (PAM) flow reactor. Different increases in OA mass (55% for OPT, 102% for RSA), associated with higher average carbon oxidation state and O:C, could be observed in a PAM chamber experiment. Finally, it was found that derived SOA yields and emission factors were distinctly lower than reported for log wood stoves.Display Omitted
Keywords: VOC; Photoionization; SP-AMS; PAM flow reactor; Wood combustion; SOA;

Observations of trace gases, photolysis rate coefficients and model simulations over semi-arid region, India by A.P. Lingaswamy; S. Md Arafath; G. Balakrishnaiah; K. Rama Gopal; N. Siva Kumar Reddy; K. Raja Obul Reddy; R.R. Reddy; T. Chakradhar Rao (246-258).
Continuous ground-based measurements of CO, SO2 and NO2 were carried out in a semi-arid rural area, Anantapur [14.62 0N, 77.65 0E], Southern India, for the period January 2012–December 2012. The maximum CO concentration was observed in winter (310 ± 17 ppbv) followed by summer (180 ± 21 ppbv) and post monsoon (174 ± 20 ppbv), while the minimum in monsoon (72 ± 9 ppbv). Seasonal mean NO2/NOx ratios for monsoon, post monsoon, winter and summer were about 0.88, 0.91, 0.76 and 0.80 respectively, indicating a higher conversion of NO to NO2 over the measurement site. Monthly mean low SO2 mixing ratio was found (0.46 ± 0.02 ppbv) in monsoon and high (2.42 ± 0.21 ppbv) in winter. Keeping the emissions aside, the levels of CO, SO2 and NO2 were influenced by meteorology, urban effects and trans-boundary transport in the lower troposphere. Atmospheric boundary layer (ABL) had the good correlation coefficient (R = 0.76) with solar radiation during daytime, while it was mainly correlated with wind speed during night time (R = 0.42). Diurnal trend of atmospheric visibility was found to be maximum during noon times at around (14:00–16:00 h) about 76 k.m. and minimum during morning periods (06:00–08:00 h) about 45 k.m. A strong positive correlation was observed between BC and CO (R = 0.71) with an average slope, suggesting common or proximate sources likely to be traffic emissions contribution for the production of BC and CO. The SO2/NOx and CO/NOx study were strongly suggested that mobile sources were larger contributors over the site and the evidence of transport of emissions from other surrounding regions. Tropospheric Ultraviolet Visible (TUV) radiative transfer model was used to calculate the Photolysis rate coefficients (J(O3), J(NO2)). Chemical box model (NCAR-MM) was used to simulate diurnal variation of CO and the results were reported.
Keywords: Trace gases; Source approximation; Visibility; Photolysis rate coefficients; Radiative transfer model;

An approach to mitigating soil CO2 emission by biochemically inhibiting cellulolytic microbial populations through mediation via the medicinal herb Isatis indigotica by Hong-Sheng Wu; Su-Yun Chen; Ji Li; Dong-Yang Liu; Ji Zhou; Ya Xu; Xiao-Xia Shang; Dong-yang Wei; Lu-ji Yu; Xiao-hang Fang; Shun-yi Li; Ke-ke Wang (259-269).
Greenhouse gases (GHGs, particularly carbon dioxide (CO 2 )) emissions from soil under wheat production are a significant source of agricultural carbon emissions that have not been mitigated effectively. A field experiment and a static incubation study in a lab were conducted to stimulate wheat growth and investigate its potential to reduce CO 2 emissions from soil through intercropping with a traditional Chinese medicinal herb called Isatis indigotica. This work was conducted by adding I. indigotica root exudates based on the quantitative real-time PCR (qPCR) analysis of the DNA copy number of the rhizosphere or bulk soil microbial populations. This addition was performed in relation to the CO 2 formation by cellulolytic microorganisms (Penicillium oxalicum, fungi and Ruminococcus albus) to elucidate the microbial ecological basis for the molecular mechanism that decreases CO 2 emissions from wheat fields using I. indigotica.The results showed that the panicle weight and full grains per panicle measured through intercropping with I. indigotica (NPKWR) increased by 39% and 28.6%, respectively, compared to that of the CK (NPKW). Intercropping with I. indigotica significantly decreased the CO 2 emissions from soil under wheat cultivation. Compared with CK, the total CO 2 emission flux during the wheat growth period in the I. indigotica (NPKWR) intercropping treatment decreased by 29.26%. The intensity of CO 2 emissions per kg of harvested wheat grain declined from 7.53 kg CO 2 /kg grain in the NPKW (CK) treatment to 5.55 kg CO 2 /kg grain in the NPKWR treatment.The qPCR analysis showed that the DNA copy number of the microbial populations of cellulolytic microorganisms (P. oxalicum, fungi and R. albus) in the field rhizosphere around I. indigotica or in the bulk soil under laboratory incubation was significantly lower than that of CK. This finding indicated that root exudates from I. indigotica inhibited the activity and number of cellulolytic microbial populations, which led to decreased CO 2 emissions, suggesting this plant's potential role in mitigating agricultural GHGs and in supporting agroecology.
Keywords: CO 2 reduction; Winter wheat soil; Wheat intercropping Isatis indigotica; Root exudates; qPCR analysis; Cellulolytic microbial population;

Real-time chemical characterization of atmospheric particulate matter in China: A review by Yong Jie Li; Yele Sun; Qi Zhang; Xue Li; Mei Li; Zhen Zhou; Chak K. Chan (270-304).
Atmospheric particulate matter (PM) pollution has become a major health threat accompanying the rapid economic development in China. For decades, filter-based offline chemical analyses have been the most widely adopted means to investigate PM and have provided much information for understanding this type of pollution in China. However, offline analyses have low time resolutions and the chemical information thus obtained fail to reflect the dynamic nature of the sources and the rapid processes leading to the severe PM pollution in China. In recent years, advances in real-time PM chemical characterization have created a new paradigm for PM studies in China. In this review, we summarize those advances, focusing on the most widely used mass spectrometric and ion chromatographic techniques. We describe the findings from those studies in terms of spatiotemporal variabilities, degree of neutralization and oxygenation, source apportionment, secondary formation, as well as collocated measurements of the chemical and physical (hygroscopic and optical) properties of PM. We also highlight the new insights gained from those findings and suggest future directions for further advancing our understanding of PM pollution in China via real-time chemical characterization.