Fresh Emissions Research Articles

Characterization of parent and oxygenated-polycyclic aromatic hydrocarbons (PAHs) in Xi’an, China during heating period: An investigation of spatial distribution and transformation

Polycyclic aromatic hydrocarbons (PAHs) and its oxygenated derivatives (OPAHs) are toxins in PM2.5. Little information has been known for their transformation in the ambient airs. In this study, PM2.5 samples were collected at 19 sampling sites in Xi’an, China during the heating period, which is classified into: urban residential, university, commercial area, suburban region, and industry. Organic compounds including PAHs, OPAHs, hopanes and cholestanes were quantified. The average of total quantified PAHs and OPAHs concentrations were 196.5 ng/m3 and 29.4 ng/m3, respectively, which were consistent with other northern cities in China. Statistical analyses showed that there were significant differences on the distributions of PAHs between urban and suburban regions. The industry also had distinguishable profiles compared with urban residential and commercial area for OPAHs. The greater diversity of OPAHs than PAHs might be due to different primary emission sources and transformation and degradation pathways. The ratios of OPAHs to the corresponding parent PAHs, including 9-fluorenone/fluorene, anthraquinone/anthracene, benz[a]anthracene-7,12-dione/benzo[a]anthracene were 6.2, 12.7, and 1.4, respectively, which were much higher than those for the fresh emissions from coal combustion and biomass burning. These prove the importance of secondary formation and transformation of OPAHs in the ambient airs. Biomarkers such as retene, cyclopenta[CD]pyrene and αα-homohopane were characterized for the source apportionment. With Positive Matrix Factorization (PMF) model analysis, biomass burning was recognized as the most dominant pollution sources for PAHs during the heading period, which accounted for a contribution of 37.1%. Vehicle emission (22.8%) and coal combustion (22.6%) were also contributors in Xi’an.

Anthropogenic non-methane volatile hydrocarbons at Mt. Cimone (2165 m a.s.l., Italy): Impact of sources and transport on atmospheric composition

To advance our understanding of the factors that affect pollution in mountainous areas, long-term, high frequency measurements of thirteen Non Methane Volatile Organic Compounds (NMVOCs) have been carried out at the atmospheric observatory on the top of Mt. Cimone (2165 m a.s.l.), whose location is ideal for sampling both aged air masses representing the regional background and polluted air masses coming from nearby sources of anthropogenic pollution.An analysis of the NMVOC time series available at Mt. Cimone during 2010–2014 was used to examine the influence of transport processes on NMVOC atmospheric composition and to derive information on the emission sources. We performed a multifactor principal component analysis whose results allowed us to identify the source categories emitting the NMVOCs measured at Mt. Cimone as well as to assess transport ranges in winter and summer. Aged air masses, due to long-range transport and related to vehicular traffic exhaust emissions accounted for 78% of the NMVOC variability in winter and 62% in summer, whereas evaporative emissions, likely to be associated with fresh emissions from nearby sources, accounted for 12% of the NMVOC variability and 24% in winter and summer, respectively. Such results have been confirmed by a further analysis in which the NMVOC variability as a function of their atmospheric lifetimes has been evaluated. The ratios of alkane isomers potentially provides a metric to investigate seasonal changes in NMVOCs composition and in the emission fields of butanes and pentanes, suggesting that during the summer the butanes are originating mainly from the European domain and that for pentanes non-anthropogenic sources may be contributing to the measured concentrations.

Polycyclic aromatic hydrocarbons (PAHs) and their derivatives (oxygenated-PAHs, nitrated-PAHs and azaarenes) in size-fractionated particles emitted in an urban road tunnel

A sampling campaign of size segregated particulate matter (PM0.5, PM0.5–1, PM1–2.5 and PM2.5–10) was carried out at two sites, one in a road tunnel (Braga, Portugal) and another at an urban background location in the neighbourhood. Particle-bound polycyclic aromatic compounds were extracted with organic solvents and analysed by gas chromatography–mass spectrometry. Twenty six parent and alkyl-polycyclic aromatic hydrocarbons (PAHs), 4 azaarenes (AZAs), 15 nitrated and 15 oxygenated derivatives (NPAHs and OPAHs) were analysed. On average, submicron particles (PM1) in the tunnel comprised 93, 91, 96 and 71% of the total PAHs, OPAHs, NPAHs and AZAs mass in PM10, respectively. Tunnel to outdoor PAH concentration ratios between 10 and 14 reveal the strong contribution of fresh exhaust emissions to the PM loads. The dominant PAHs in the tunnel were pyrene, retene and benzo[ghi]perylene, accounting for 20, 17 and 8% of the total PAH levels in PM10, respectively. Isomer ratios indicated the importance of unburnt fuel as a significant PAH source. The only NPAH consistently present in all samples was 5-nitroacenaphthene. Indanone and 1,8-naphthalic anhydride were the most abundant OPAHs, accounting for 25 and 17% of the total concentrations of this organic class, respectively. Other abundant OPAHs were 1,4-naphthoquinone, 9-fluorenone, 1,2-acenaphthylenequinone and 7H-benz[de]anthracene-7-one. Individual emission factors (μg veh−1km−1) were estimated and compared with those obtained in other tunnel studies.

Rapidly evolving ultrafine and fine mode biomass smoke physical properties: Comparing laboratory and field results

AbstractCombining field and laboratory results, we present biomass smoke physical properties. We report sub‐0.56 µm diameter (Dp) particle sizing (fast mobility particle sizer, FMPS) plus light absorption and scattering at 870 nm (photoacoustic extinctiometer). For Dp < 200 nm, the FMPS characterized sizing within ±20% compared to standards. As compared to the traditional scanning mobility particle sizer, the FMPS responded most accurately to single‐mode polydispersions with mean Dp < 200 nm, which characterized the smoke sampled here. Smoke was measured from laboratory fresh emissions (seconds to hours old), the High Park Fire (hours to < 1 day), and from regional biomass burning (several days). During a High Park Fire episode, light extinction rapidly reached a maximum of σep = 569 ± 21 Mm−1 (10 min) with aerosol single scattering albedo peaking at ω = 0.955 ± 0.004. Concurrently, number concentration and size peaked with maximum Dp = 126 nm and a unimodal distribution with σg = 1.5. Long‐range transported smoke was substantially diluted (Ntot factor of 7 lower) and shifted larger (maximum Dp = 143) and wider (σg = 2.2). We compared ambient data to laboratory burns with representative western U.S. forest fuels (coniferous species Ponderosa pine and Alaska black spruce). Smoldering pine produced an aerosol dominated by larger, more strongly light scattering particles (Dp > 100 nm), while flaming combustion produced very high number concentrations of smaller (Dp ~ 50 nm) absorbing particles. Due to smoldering and particle growth processes, Dp approached 100 nm within 3 h after emission. Increased particle cross‐sectional area and Mie scattering efficiency shifted the relative importance of light absorption (flaming maximum) and light scattering (smoldering maximum), increasing ω over time. Measurements showed a consistent picture of smoke properties from emission to aging.

Vertical and horizontal variability in airborne nanoparticles and their exposure around signalised traffic intersections

We measured size–resolved PNCs in the 5–560 nm range at two different types (4– and 3–way) of TIs in Guildford (Surrey, UK) at fixed sites (∼1.5 m above the road level), sequentially at 4 different heights (1, 1.5, 2.5 and 4.7 m), and along the road at five different distances (10, 20, 30, 45 and 60 m). The aims were to: (i) assess the differences in PNCs measured at studied TIs, (ii) identify the best fit probability distribution curves for the PNCs, (iii) determine vertical and horizontal decay profiles of PNCs, (iv) estimate particle number emission factors (PNEFs) under congested and free–flow traffic conditions, and (v) quantify the pedestrian exposure in terms of respiratory deposition dose (RDD) rates at the TIs. Daily averaged particle number distributions at TIs reflected the effect of fresh emissions with peaks at 5.6, 10 and 56 nm. Despite the relatively high traffic volume at 3–way TI, average PNCs at 4–way TI were about twice as high as at 3–way TI, indicating less favourable dispersion conditions. Generalised extreme value distribution fitted well to PNC data at both TIs. Vertical PNC profiles followed an exponential decay, which was much sharper at 4–way TI than at 3–way TI, suggesting ∼40% less exposure for people at first floor (4.7 m) to those at ground floor around 4-way TI. Vertical profiles indicated much sharper (∼132–times larger) decay than in horizontal direction, due to close vicinity of road vehicles during the along-road measurements. Over an order of magnitude higher PNEFs were found during congested, compared with free–flow, conditions due to frequent changes in traffic speed. Average RDD rate at 4–way TI during congested conditions were up to 14–times higher than those at 3–way TI (0.4 × 1011 h−1). Findings of this study are a step forward to understand exposure at and around the TIs.

On the effectiveness of nitrogen oxide reductions as a control over ammonium nitrate aerosol

Abstract. Nitrogen oxides (NOx) have fallen steadily across the US over the last 15 years. At the same time, NOx concentrations decrease on weekends relative to weekdays, largely without co-occurring changes in other gas-phase emissions, due to patterns of diesel truck activities. These trends taken together provide two independent constraints on the role of NOx in the nonlinear chemistry of atmospheric oxidation. In this context, we interpret interannual trends in wintertime ammonium nitrate (NH4NO3) in the San Joaquin Valley of California, a location with the worst aerosol pollution in the US and where a large portion of aerosol mass is NH4NO3. Here, we show that NOx reductions have simultaneously decreased nighttime and increased daytime NH4NO3 production over the last decade. We find a substantial decrease in NH4NO3 since 2000 and conclude that this decrease is due to reduced nitrate radical-initiated production at night in residual layers that are decoupled from fresh emissions at the surface. Further reductions in NOx are imminent in California, and nationwide, and we make a quantitative prediction of the response of NH4NO3. We show that the combination of rapid chemical production and efficient NH4NO3 loss via deposition of gas-phase nitric acid implies that high aerosol days in cities in the San Joaquin Valley air basin are responsive to local changes in NOx within those individual cities. Our calculations indicate that large decreases in NOx in the future will not only lower wintertime NH4NO3 concentrations but also cause a transition in the dominant NH4NO3 source from nighttime to daytime chemistry.

Radiative absorption enhancement from coatings on black carbon aerosols

The radiative absorption enhancement of ambient black carbon (BC), by light-refractive coatings of atmospheric aerosols, constitutes a large uncertainty in estimates of climate forcing. The direct measurements of radiative absorption enhancement require the experimentally-removing the coating materials in ambient BC-containing aerosols, which remains a challenge. Here, the absorption enhancement of the BC core by non-absorbing aerosol coatings was quantified using a two-step removal of both inorganic and organic matter coatings of ambient aerosols. The mass absorption cross-section (MAC) of decoated/pure atmospheric BC aerosols of 4.4±0.8m2g−1 was enhanced to 9.6±1.8m2g−1 at 678-nm wavelength for ambiently-coated BC aerosols at a rural Northern China site. The enhancement of MAC (EMAC) rises from 1.4±0.3 in fresh combustion emissions to ~3 for aged ambient China aerosols. The three-week high-intensity campaign observed an average EMAC of 2.25±0.55, and sulfates were primary drivers of the enhanced BC absorption.

Composition, potential emissions and agricultural value of pig slurry from Spanish commercial farms

Pig slurry is a valuable fertilizer for crop production but at the same time its management may pose environmental risks. Slurry samples were collected from 77 commercial farms of four animal categories (gestating and lactating sows, nursery piglets and growing pigs) and analyzed for macronutrients, micronutrients, heavy metals and volatile fatty acids. Emissions of ammonia (NH3) and biochemical methane potential (BMP) were quantified. Slurry electrical conductivity, pH, dry matter content and ash content were also determined. Data analysis included an analysis of correlations among variables, the development of prediction models for gaseous emissions and the analysis of nutritional content of slurries for crop production. Descriptive information is provided in this work and shows a wide range of variability in all studied variables. Animal category affected some physicochemical parameters, probably as a consequence of different slurry management and use of cleaning water. Slurries from gestating sows and growing pigs tended to be more concentrated in nutrients, whereas the slurry from lactating sows and nursery piglets tended to be more diluted. Relevant relationships were found among slurry characteristics expressed in fresh basis and gas emissions. Predictive models using on-farm measurable parameters were obtained for NH3 (R2 = 0.51) and CH4 (R2 = 0.76), which suggests that BMP may be estimated in commercial farms from easily determined slurry characteristics. Finally, slurry nutrient composition was highly variable. Therefore, complete analyses of slurries should be performed for an effective and environmental friendly land application.

Characterization of water-soluble organic matter in urban aerosol by 1H-NMR spectroscopy.

The functional and 13C isotopic compositions of water-soluble organic carbon (WSOC) in atmospheric aerosol were determined by nuclear magnetic resonance (1H-NMR) and isotope ratio mass spectrometry (IRMS) in an urban location in the Southern Mississippi Valley. The origin of WSOC was resolved using the functional distribution of organic hydrogen, δ13C ratio, and positive matrix factorization (PMF). Three factors were retained based on NMR spectral bins loadings. Two factors (factors 1 and 3) demonstrated strong associations with the aliphatic region in the NMR spectra and levoglucosan resonances. Differences between the two factors included the abundance of the aromatic functional group for factor 1, indicating fresh emissions and, for factor 3, the presence of resonances attributed to secondary ammonium nitrate and low δ13C ratio values that are indicative of secondary organic aerosol. Factors 1 and 3 added 0.89 and 1.08 μgC m-3, respectively, with the highest contribution in the summer and fall. Factor 2 retained resonances consistent with saccharides and was attributed to pollen particles. Its contribution to WSOC varied from 0.22 μgC m-3 in winter to 1.04 μgC m-3 in spring.

Fine particles sampled at an urban background site and an industrialized coastal site in Northern France — Part 1: Seasonal variations and chemical characterization

The chemical composition of particulate matter sampled at two French Northern sites (Douai, DO – urban background; Grande-Synthe, GS – industrialized coastal site) was investigated during two summer and winter field campaigns at each site. Measurements of the major chemical species (organic, sulfate, nitrate, ammonium, chloride) in the non-refractory submicron aerosols (NR-PM1) were carried out by a High Resolution Time-of-Flight Aerosol Mass Spectrometer. Black Carbon in PM2.5 was monitored using an Aethalometer, while the OC and EC fractions and some targeted chemical organic families (polycyclic aromatic hydrocarbons, PAHs; dicarboxylic acids, DCAs) were quantified by the simultaneous collection of PM2.5 on filters followed by offline analyses. The seasonal trends and winter-to-summer (W/S) concentration ratios are discussed in this paper. Results indicate that the total average mass concentrations of PM2.5 varied between 20.5μgm−3 and 32.6μgm−3 in DO and between 10.6μgm−3 and 29.9μgm−3 in GS during summer and winter, respectively. Similar concentration patterns were found for PAHs and Organic Carbon (OC, representing ~80% of the total carbon) with highest concentrations in winter at the urban site. DCA concentrations showed less seasonal variations, although the highest value also appeared during winter. Total NR-PM1 presented concentrations in summer lower by a factor of 4 (for DO) and 10 (for GS) than those observed in winter. Organics and nitrates dominated the NR-PM1 in DO for both seasons and during winter in GS while sulfates and nitrates were the most dominant species in summer in GS. Average chloride concentrations were slightly more important in GS than those in DO related to its use in industrial processes and no significant seasonal trend was observed. The size-resolved chemical composition showed that aerosols sampled in DO in winter are more aged than those collected in GS where fresh emissions of sulfate from the industrial sector were observed.

Impacts of Combustion Conditions and Photochemical Processing on the Light Absorption of Biomass Combustion Aerosol.

The aim was to identify relationships between combustion conditions, particle characteristics, and optical properties of fresh and photochemically processed emissions from biomass combustion. The combustion conditions included nominal and high burn rate operation and individual combustion phases from a conventional wood stove. Low temperature pyrolysis upon fuel addition resulted in "tar-ball" type particles dominated by organic aerosol with an absorption Ångström exponent (AAE) of 2.5-2.7 and estimated Brown Carbon contributions of 50-70% to absorption at the climate relevant aethalometer-wavelength (520 nm). High temperature combustion during the intermediate (flaming) phase was dominated by soot agglomerates with AAE 1.0-1.2 and 85-100% of absorption at 520 nm attributed to Black Carbon. Intense photochemical processing of high burn rate flaming combustion emissions in an oxidation flow reactor led to strong formation of Secondary Organic Aerosol, with no or weak absorption. PM1 mass emission factors (mg/kg) of fresh emissions were about an order of magnitude higher for low temperature pyrolysis compared to high temperature combustion. However, emission factors describing the absorption cross section emitted per kg of fuel consumed (m(2)/kg) were of similar magnitude at 520 nm for the diverse combustion conditions investigated in this study. These results provide a link between biomass combustion conditions, emitted particle types, and their optical properties in fresh and processed plumes which can be of value for source apportionment and balanced mitigation of biomass combustion emissions from a climate and health perspective.

Legacy and currently used pesticides in the atmospheric environment of Lake Victoria, East Africa

The Lake Victoria watershed has extensive agricultural activity with a long history of pesticide use but there is limited information on historical use or on environmental levels. To address this data gap, high volume air samples were collected from two sites close to the northern shore of Lake Victoria; Kakira (KAK) and Entebbe (EBB). The samples, to be analyzed for pesticides, were collected over various periods between 1999 and 2004 inclusive (KAK 1999–2000, KAK 2003–2004, EBB 2003 and EBB 2004 sample sets) and from 2008 to 2010 inclusive (EBB 2008, EBB 2009 and EBB 2010 sample sets). The latter sample sets (which also included precipitation samples) were also analyzed for currently used pesticides (CUPs) including chlorpyrifos, chlorthalonil, metribuzin, trifluralin, malathion and dacthal. Chlorpyrifos was the predominant CUP in air samples with average concentrations of 93.5, 26.1 and 3.54ngm−3 for the EBB 2008, 2009, 2010 sample sets, respectively. Average concentrations of total endosulfan (ΣEndo), total DDT related compounds (ΣDDTs) and hexachlorocyclohexanes (ΣHCHs) ranged from 12.3–282, 22.8–130 and 3.72–81.8pgm−3, respectively, for all the sample sets. Atmospheric prevalence of residues of persistent organic pollutants (POPs) increased with fresh emissions of endosulfan, DDT and lindane. Hexachlorobenzene (HCB), pentachlorobenzene (PeCB) and dieldrin were also detected in air samples. Transformation products, pentachloroanisole, 3,4,5-trichloroveratrole and 3,4,5,6-tetrachloroveratrole, were also detected. The five most prevalent compounds in the precipitation samples were in the order chlorpyrifos>chlorothalonil>ΣEndo>ΣDDTs>ΣHCHs with average fluxes of 1123, 396, 130, 41.7 and 41.3ngm−2sample−1, respectively. PeCB exceeded HCB in precipitation samples. The reverse was true for air samples. Backward air trajectories suggested transboundary and local emission sources of the analytes. The results underscore the need for a concerted regional vigilance in management of chemicals.

Analysis of size-segregated winter season aerosol data from New Delhi, India

Size distributions of particulate matter and twelve constituent elements were measured at a high traffic site in New Delhi, India during winter 2013. While PM was found to be trimodal, individual elements showed varying size distribution patterns. Three key types of size distributions were observed including unimodal with peaks either in the coarse (Al, Si) or fine (Pb) modes, bimodal with peaks in the fine range (S) and multimodal with peaks in accumulation and coarse (Cu, Sb) modes. Elements such as Al, Si and Fe were found to be in predominantly in the coarse range while Cu, Zn, Pb and Sb were found to be in the fine size range. Two modes dominate the size distribution. One is coarse (ca. 3 μm) and contains mainly crustal elements and hence arises from sources such as soil, road dust, construction dust and possible coal fly ash. The other, more intense mode is fine (ca. 0.6 μm) and appears to comprise sulphate and anthropogenic trace metals which have entered the droplet mode through hygroscopic particle growth in the very high humidity conditions of the Delhi winter. A third, less intensive mode ca. at 0.2 μm probably arises from relatively fresh anthropogenic emissions which have not grown into the droplet mode.

Road tunnel, roadside, and urban background measurements of aliphatic compounds in size-segregated particulate matter

Particulate matter samples were collected in a road tunnel in Lisbon (PM0.5, PM0.5–1, PM1–2.5, and PM2.5–10) and at two urban locations representing roadside and background stations (PM2.5 and PM2.5–10). Samples were analysed for organic and elemental carbon (OC and EC), n-alkanes, n-alkenes, hopanes, some isoprenoid compounds, and steranes. Particulate matter concentrations in the tunnel were 17–31 times higher than at roadside in the vicinity, evidencing an aerosol origin almost exclusively in fresh vehicle emissions. PM0.5 in the tunnel comprised more than 60% and 80% of the total OC and EC mass in PM10, respectively. Concentrations of the different aliphatic groups of compounds in the tunnel were up to 89 times higher than at roadside and 143 times higher than at urban background. Based on the application of hopane-to-OC or hopanes-to-EC ratios obtained in the tunnel, it was found that vehicle emissions are the dominant contributor to carbonaceous particles in the city but do not represent the only source of these triterpenic compounds. Contrary to what has been observed in other studies, the Σhopane-to-EC ratios were higher in summer than in winter, suggesting that other factors (e.g. biomass burning, dust resuspension, and different fuels/engine technologies) prevail in relation to the photochemical decay of triterpenoid hydrocarbons from vehicle exhaust.

Impact of primary and secondary organic sources on the oxidative potential of quasi-ultrafine particles (PM0.25) at three contrasting locations in the Los Angeles Basin

To investigate the changing contribution of primary and secondary sources on the oxidative potential of particulate matter (PM) in a real-world urban atmosphere, 7 sets of quasi-ultrafine particles (PM0.25) were collected at three contrasting locations in the Los Angeles Basin, California, USA. Samples were collected in the coastal area of Long Beach during the morning rush hour period, representing fresh primary emissions from nearby freeways and the LA port; in central Los Angeles during midday, representing a mixture of fresh primary emissions and early products of photochemical secondary organic aerosol (SOA) formation; and at a downwind site (Upland) during afternoon, when the impacts of photochemically aged secondary PM are significant. Chemical composition showed distinctive trends, with the lowest fraction of water soluble organic carbon (WSOC) and other organic tracers of SOA formation (e.g. organic acids) at Long Beach, and the lowest abundance of organic tracers of primary vehicular emissions (such as polycyclic aromatic hydrocarbons and hopanes) at Upland. A molecular marker-based chemical mass balance (MM-CMB) model indicated that 72% of the total organic carbon at Long Beach was comprised of primary vehicular sources (combined heavy duty and light duty vehicles), while the vehicular fraction was found to be 50% and 39% at Los Angeles and Upland, respectively. Regression analysis suggested that at Long Beach, the variation in oxidative potential of PM0.25 (quantified using a macrophage-based reactive oxygen species (ROS) assay) was mainly driven by mobile vehicular emissions and the water-insoluble fraction of the organic carbon. In contrast, at Upland, where photochemical processing and secondary aerosol formation was the highest, WSOC and secondary organics were the major drivers of the oxidative potential variation. The multivariate regression analysis also indicated that as much as 58% of the overall spatial and temporal variation in the oxidative potential of PM0.25 at these three locations can be explained by mobile emissions and SOA.

Diurnal and seasonal variation of the PM2.5 apparent particle density in Beijing, China

To characterize the features of particle apparent density and its correlation with chemical composition and meteorological conditions, continuous measurements of particle number size distributions and particle mass concentrations were conducted in the winter and summer periods in Beijing using a Scanning Mobility Particle Sizer and a Tapered Element Oscillating Microbalance with a Filter Dynamic Measurement System. The apparent density, as determined by the particle mass to volume ratios, showed strong seasonal and diurnal variations, with higher values were observed during the warm season (1.60 ± 0.43 g cm−3, July to September 2014) compared to the cold season (1.41 ± 0.40 g cm−3, November 2013 to January 2014). A minimum in the morning and afternoon rush hours was observed in both seasons, representing fresh primary aerosol emissions, which were related to soot particles with low density due to their agglomerate structure, especially observed in the late afternoon hours of the cold season (approximately 1.3 g cm−3) when traffic emissions combined with the coal combustion for heating supply. The highest values were found during midday (approximately 1.8 g cm−3) in the warm season, likely due to increased secondary particle production and the presence of more aged particles with a build-up of the convectively mixed boundary layer. The apparent particle density has the potential to serve as a crude tracer for chemical composition and atmospheric processing and might play an important role when considering the associations between health effects and ambient particles.

Trace gases at a semi-arid urban site in western India: variability and inter-correlations

Continuous measurements of O3, CO, NOx and SO2 were made in Ahmedabad, a semi-arid, urban region in western India, during May-October, 2011 to study their levels, variability and inter-relationships during this period of changing meteorological conditions. The levels of CO and SO2 observed in Ahmedabad were in general not very high compared to other major urban regions in India. On the other hand, NOx levels, impacted by vehicular emissions, were found to be substantially elevated. However, these values are still lower than levels in megacities like Beijing, Hong-Kong, Mexico etc. A sudden increase in trace gas levels was observed during post-monsoon months due to a concurrent change in prevailing winds. The levels, variability as well as diurnal amplitudes for all the gases were particularly high during October. While the primary pollutants were negatively correlated with wind speed, O3 interestingly showed a positive association. Low slope and relatively lower correlation between O3 and CO in Ahmedabad indicate incomplete photochemical processes in the ambient air. Despite an overall inverse relationship between O3 and NOx, daytime O3 was found to be positively correlated with night-time NOx as well as night-time CO. Levels of CO, NOx and SO2 showed unique relationships with wind direction depending on source locations. Low CO-NOx slope for Ahmedabad indicate relatively fresh emissions from local sources. SO2 values as well as SO2/NOx ratios were higher when wind was from the eastern sector of the city, which contains a thermal power station and a few industrial clusters. The SO2/NOx slope for point sources in Ahmedabad is estimated to be 0.4 while for mobile sources, it is 0.026.

High time and mass resolved PTR-TOF-MS measurements of VOCs at an urban site of India during winter: Role of anthropogenic, biomass burning, biogenic and photochemical sources

This study is based on the high mass and time-resolved measurements of seven VOCs using a PTR-TOF-MS instrument at an urban site of India during winter 2013. Daily levels of OVOCs and aromatics were in the ranges of 3.5–37ppbv and 0.85–23ppbv, respectively with OVOCs accounted for up to 80% of total measured VOCs. The impact of long-range transport from the polluted Indo-Gangetic Plain and clean Thar desert was observed during the episodes of high and low VOCs, respectively. VOCs exhibited strong diurnal variations with peaks during morning and evening hours and lowest in the afternoon. Relatively elevated aromatics during evening hours coincided with the lowest-OVOCs indicating influence of fresh vehicular emissions. Emission ratios of isoprene and OVOCs with respect to benzene followed the diurnal cycles of temperature and solar flux indicating role of biogenic and photochemical processes, respectively. Correlation study of VOCs with benzene suggests major contribution from anthropogenic and also from biogenic and secondary sources to some extent. The higher emission ratios of ∆methanol/∆acetonitrile correspond to the episodes of long-range transport from biomass burning sources located in the Indo-Gangetic Plain (IGP). In addition to the pattern of emission, the diurnal and day-to-day variations of VOCs were influenced by the local meteorological conditions and depth of planetary boundary layer (PBL).

Impact of isoprene and HONO chemistry on ozone and OVOC formation in a semirural South Korean forest

Abstract. Rapid urbanization and economic development in East Asia in past decades has led to photochemical air pollution problems such as excess photochemical ozone and aerosol formation. Asian megacities such as Seoul, Tokyo, Shanghai, Guangzhou, and Beijing are surrounded by densely forested areas, and recent research has consistently demonstrated the importance of biogenic volatile organic compounds (VOCs) from vegetation in determining oxidation capacity in the suburban Asian megacity regions. Uncertainties in constraining tropospheric oxidation capacity, dominated by hydroxyl radical, undermine our ability to assess regional photochemical air pollution problems. We present an observational data set of CO, NOx, SO2, ozone, HONO, and VOCs (anthropogenic and biogenic) from Taehwa research forest (TRF) near the Seoul metropolitan area in early June 2012. The data show that TRF is influenced both by aged pollution and fresh biogenic volatile organic compound emissions. With the data set, we diagnose HOx (OH, HO2, and RO2) distributions calculated using the University of Washington chemical box model (UWCM v2.1) with near-explicit VOC oxidation mechanisms from MCM v3.2 (Master Chemical Mechanism). Uncertainty from unconstrained HONO sources and radical recycling processes highlighted in recent studies is examined using multiple model simulations with different model constraints. The results suggest that (1) different model simulation scenarios cause systematic differences in HOx distributions, especially OH levels (up to 2.5 times), and (2) radical destruction (HO2 + HO2 or HO2 + RO2) could be more efficient than radical recycling (RO2 + NO), especially in the afternoon. Implications of the uncertainties in radical chemistry are discussed with respect to ozone–VOC–NOx sensitivity and VOC oxidation product formation rates. Overall, the NOx limited regime is assessed except for the morning hours (8 a.m. to 12 p.m. local standard time), but the degree of sensitivity can significantly vary depending on the model scenarios. The model results also suggest that RO2 levels are positively correlated with oxygenated VOCs (OVOCs) production that is not routinely constrained by observations. These unconstrained OVOCs can cause higher-than-expected OH loss rates (missing OH reactivity) and secondary organic aerosol formation. The series of modeling experiments constrained by observations strongly urge observational constraint of the radical pool to enable precise understanding of regional photochemical pollution problems in the East Asian megacity region.

Source apportionment of airborne nanoparticles in a Middle Eastern city using positive matrix factorization.

Airborne nanoparticles have been studied worldwide, but little is known about their sources in the Middle East region, where hot, arid and dusty climatic conditions generally prevail. For the first time in Kuwait, we carried out size-resolved measurements of particle number distributions (PNDs) and concentrations (PNCs) in the 5-1000 nm size range. Measurements were made continuously for 31 days during the summer months of May and June 2013 using a fast-response differential mobility spectrometer (Cambustion DMS500) at a sampling rate of 10 Hz. Sources and their contributions were identified using the positive matrix factorization (PMF) approach that was applied to the PND data. Simultaneous measurements of gaseous pollutants (i.e., O3, NO, NOx, SO2 and CO), PM10, wind speed and direction were also carried out to aid the interpretation of the PMF results through the conditional probability function plots and Pearson product-moment correlations. Six major sources of PNCs were identified, contributing ∼46% (fresh traffic emissions), 27% (aged traffic emissions), 9% (industrial emissions), 9% (regional background), 6% (miscellaneous sources) and 3% (Arabian dust transport) of the total PNCs. The sources of nanoparticles and their PND profiles identified could serve as reference data to design more detailed field studies in the future and treat these sources in dispersion modelling and health impact assessment studies.