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Urban environments are recognized as main anthropogenic contributors to greenhouse gas (GHG) emissions, characterized by unevenly distributed emission sources over the urban environments. However, spatial GHG distributions in urban regions are typically obtained through monitoring at only a limited number of locations, or through model studies, which can lead to incomplete insights into the heterogeneity in the spatial distribution of GHGs. To address such information gap and to evaluate the spatial representation of a planned GHG monitoring network, a custom-developed atmospheric sampler was deployed on a UAV platform in this study to map the CO2 and CH4 mixing ratios in the atmosphere over Zhengzhou in central China, a megacity of nearly 13 million people. The aerial survey was conducted along the main roads at an altitude of 150 m above ground, covering a total distance of 170 km from the city center to the suburbs. The spatial distributions of CO2 and CH4 mixing ratios in Zhengzhou exhibited distinct heterogeneities, with average mixing ratios of CO2 and CH4 at 439.2 ± 10.8 ppm and 2.12 ± 0.04 ppm, respectively. A spatial autocorrelation analysis was performed on the measured GHG mixing ratios across the city, revealing a spatial correlation range of approximately 2 km for both CO2 and CH4 in the urban area. Such a spatial autocorrelation distance suggests that the urban GHG monitoring network designed for emission inversion purposes need to have a spatial resolution of 4 km to characterize the spatial heterogeneities in the GHGs. This UAV-based measurement approach demonstrates its capability to monitor GHG mixing ratios across urban landscapes, providing valuable insights for GHG monitoring network design.
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Monitoring of volatile organic compounds (VOCs) in air is crucial for understanding their atmospheric impacts and advancing their emission reduction plans. This study presents an innovative integrated methodology suitable for achieving semireal-time high spatiotemporal resolution three-dimensional measurements of VOCs from ground to hundreds of meters above ground. The methodology integrates an active AirCore sampler, custom-designed for deployment from unmanned aerial vehicles (UAV), a proton-transfer-reaction mass spectrometry (PTR-MS) for sample analysis, and a data deconvolution algorithm for improved time resolution for measurements of multiple VOCs in air. The application of the deconvolution technique significantly improves the signal strength of data from PTR-MS analysis of AirCore samples and enhances their temporal resolution by 4 to 8 times to 4-11 s. A case study demonstrates that the methodology can achieve sample collection and analysis of VOCs within 45 min, resulting in >120-360 spatially resolved data points for each VOC measured and achieving a horizontal resolution of 20-55 m at a UAV flight speed of 5 m/s and a vertical resolution of 5 m. This methodology presents new possibilities for acquiring 3-dimensional spatial distributions of VOC concentrations, effectively tackling the longstanding challenge of characterizing three-dimensional VOC distributions in the lowest portion of the atmospheric boundary layer.
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Contaminantes Atmosféricos , Monitoreo del Ambiente , Compuestos Orgánicos Volátiles , Compuestos Orgánicos Volátiles/análisis , Monitoreo del Ambiente/métodos , Contaminantes Atmosféricos/análisis , Espectrometría de Masas/métodos , Algoritmos , AeronavesRESUMEN
Cold heavy oil production with sand (CHOPS) is an extraction process for heavy oil in Canada, with the potential to lead to higher CH4 venting than conventional oil sites, that have not been adequately characterized. In order to quantify CH4 emissions from CHOPS activities, a focused aerial measurement campaign was conducted in the Canadian provinces of Alberta and Saskatchewan in June 2018. Total CH4 emissions from each of 10 clusters of CHOPS wells (containing 22-167 well sites per cluster) were derived using a mass balance computation algorithm that uses in situ wind data measurement on board aircraft. Results show that there is no statistically significant difference in CH4 emissions from CHOPS wells between the two provinces. Cluster-aggregated emission factors (EF) were determined using correspondingly aggregated production volumes. The average CH4 EF was 70.4 ± 36.9 kg/m3 produced oil for the Alberta wells and 55.1 ± 13.7 kg/m3 produced oil for the Saskatchewan wells. Using these EF and heavy oil production volumes reported to provincial regulators, the annual CH4 emissions from CHOPS were estimated to be 121% larger than CHOPS emissions extracted from Canada's National Inventory Report (NIR) for Saskatchewan. The EF were found to be positively correlated with the percentage of nonpiped production volumes in each cluster, indicating higher emissions for nonpiped wells while suggesting an avenue for methane emission reductions. A comparison with recent measurements indicates relatively limited effectiveness of regulations for Saskatchewan compared to those in Alberta. The results of this study indicate the substantial contribution of CHOPS operations to the underreporting observed in the NIR and provide measurement-based EF that can be used to develop improved emissions inventories for this sector and mitigate CH4 emissions from CHOPS operations.
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To understand the characteristics of atmospheric pollution above the urban canopy in warm seasons, the characteristics of sub-micron aerosol (PM1) was studied based on high-altitude observations at the Beijing 325 m meteorological tower. The PM1 at 260 m was 34, 29 and 21 µg m-3 in May 2015, June 2015, and June 2017, respectively, indicating a reduction in PM1 pollution above the urban canopy. Meanwhile, an overall decrease was also observed in the concentrations of all PM1 chemical species (excluding Chl and BC) and organic aerosol (OA) factors. Previous instances of heavy haze in Beijing often coincided with high humidity and stagnant weather conditions. However, the heightened pollution episodes in June 2017 were accompanied by high wind speeds and low relative humidity. Compared to May 2015, the contribution of secondary components to PM1 in June 2017 was more prominent, with the total proportion of SNA (sulfate, nitrate, and ammonium) and more-oxidized oxygenated OA (MO-OOA) to PM1 increased by approximately 10 %. Secondary species of NH4NO3, (NH4)2SO4, and MO-OOA, as well as black carbon, collectively contributed the vast majority of aerosol extinction coefficient (bext), with the four species contributing a total of ≥96 % to bext at 260 m. Hydrocarbon-like OA, cooking OA, and less-oxidized oxygenated OA have undergone significant reductions, so continued emphasis on controlling local sources to reduce these three aerosol species and addressing regional sources to further mitigate overall aerosol species is imperative. In lower pollution situation, the diurnal variation of PM was smoother, and its pollution sources were more regionally uniform, which might be attributed to the reduced diversity and complexity in the physical and chemical processes in air pollution.
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Forest fire research over the last several decades has improved the understanding of fire emissions and impacts. Nevertheless, the evolution of forest fire plumes remains poorly quantified and understood. Here, a Lagrangian chemical transport model, the Forward Atmospheric Stochastic Transport model coupled with the Master Chemical Mechanism (FAST-MCM), has been developed to simulate the transport and chemical transformations of plumes from a boreal forest fire over several hours since their emission. The model results for NOx (NO and NO2), O3, HONO, HNO3, pNO3 and 70 VOC species are compared with airborne in-situ measurements within plume centers and their surrounding portions during the transport. Comparisons between simulation results and measurements show that the FAST-MCM model can properly reproduce the physical and chemical evolution of forest fire plumes. The results indicate that the model can be an important tool used to aid the understanding of the downwind impacts of forest fire plumes.
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Particle number size distribution (PNSD) is of importance for understanding the mechanisms of particle growth, haze formation and climate impacts. However, the measurements of PNSD aloft in megacities are very limited. Here we report the first simultaneous winter measurements of size-resolved particle number concentrations along with collocated gaseous species and aerosol composition at ground level and 260 m in Beijing. Our study showed that the vertical differences of particle number concentrations between ground level and aloft varied significantly as a function of particle size throughout the study. Further analysis illustrated the impacts of boundary dynamics and meteorological conditions on the vertical differences of PNSD. In particular, the temperature and relative humidity inversions were one of the most important factors by decoupling the boundary layer into different sources and processes. Positive matrix factorization analysis identified six sources of PNSD at both ground level and city aloft. The local source emissions dominantly contributed to Aitken-mode particles, and showed the largest vertical gradients in the city. Comparatively, the regional particles were highly correlated between ground level and city aloft, and the vertical differences were relatively stable throughout the day. Our results point towards a complex vertical evolution of PNSD due to the changes in boundary layer dynamics, meteorological conditions, sources, and processes in megacities.
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Contaminantes Atmosféricos , Aerosoles/análisis , Contaminantes Atmosféricos/análisis , Beijing , China , Monitoreo del Ambiente , Tamaño de la Partícula , Material Particulado/análisis , Estaciones del AñoRESUMEN
Extensive studies on aerosol chemistry have been carried out in megacities in China, however, aerosol characterization in Central China Plain (CCP) is limited. Here we conducted real-time measurements of fine particle composition with a time-of-flight aerosol chemical speciation monitor in Kaifeng, Henan province in October 2019. Our results showed that nitrate and organics constituted the major fraction of non-refractory PM2.5 for the entire study, on average accounting for 34% and 33%, respectively. However, aerosol composition was substantially different among four periods due to different meteorological conditions and chemical processing. For instance, nitrate presented the lowest contribution during the first period due to evaporative loss associated with high temperature (T), and then rapidly increased during polluted periods as a function of relative humidity (RH). Positive matrix factorization analysis showed the dominance of secondary organic aerosol (SOA) in OA, and also the changes in OA composition under different T and RH levels. In addition, this study is unique with two periods of local emission controls. Back trajectory and coefficient of divergence analysis showed that air pollution in CCP was overall homogeneously distributed. As a result, the effectiveness of local emission controls in this region was strongly affected by meteorological conditions and regional transport. We found that one of the periods with emission control even showed the highest concentrations for the entire study. Our results point towards the limited effect of local emission controls in mitigating air pollution in CCP, and highlight the importance of joint emission controls under unfavorable meteorological conditions.
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Contaminantes Atmosféricos , Material Particulado , Aerosoles/análisis , Contaminantes Atmosféricos/análisis , China , Ciudades , Monitoreo del Ambiente , Material Particulado/análisisRESUMEN
Vertical measurements are essential for the characterization of aerosol and boundary layer interactions; yet, our knowledge of vertical profiles of primary and secondary aerosol species in megacities is limited. Here, we conducted comprehensive vertical measurements of aerosol particle composition on a 325 m meteorological tower with two aerosol chemical speciation monitors in winter in urban Beijing. The simultaneous measurements at ground level, 140, and 240 m illustrated similar aerosol bulk composition at these three heights. However, the vertical ratios varied significantly among different aerosol species. Particularly, the vertical ratios of the aqueous phase and photochemical-related secondary organic aerosol (SOA) (aqOOA/OOA) decreased significantly, accompanied by the increases in ratios of secondary to primary OA, highlighting different chemical properties of OA between ground level and aloft, and the large impacts of vertical changes in meteorology and gaseous precursors on SOA formation. The vertical changes in NO3/SO4 ratios, however, were mostly insignificant, likely due to the low relative humidity and aerosol water content that inhibited nocturnal heterogeneous reactions in the residual layer. Considerable increases in the ratios of 240 m to ground level in the early morning were also observed for most aerosol species, demonstrating impact of residual layer on the air pollution of 2nd day.
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Contaminantes Atmosféricos , Aerosoles/análisis , Contaminantes Atmosféricos/análisis , Beijing , Monitoreo del Ambiente , MeteorologíaRESUMEN
The light absorption black carbon (BC) and brown carbon (BrC) are two important sources of uncertainties in radiative forcing estimate. Here we investigated the light absorption enhancement (Eabs) of BC due to coated materials at an urban (Beijing) and a rural site (Gucheng) in North China Plain (NCP) in winter 2019 by using a photoacoustic extinctiometer coupled with a thermodenuder. Our results showed that the average (±1σ) Eabs was 1.32 (±0.15) at the rural site, which was slightly higher than that at the urban site (1.24 ± 0.15). The dependence of Eabs on coating materials was found to be relatively limited at both sites. However, Eabs presented considerable increases as a function of relative humidity below 70%. Further analysis showed that Eabs during non-heating period in Beijing was mainly caused by secondary components, while it was dominantly contributed by enhanced primary emissions in heating season at both sites. In particular, aerosol particles mixed with coal combustion emissions had a large impact on Eabs (>1.40), while the fresh traffic emissions and freshly oxidized secondary OA (SOA) had limited Eabs (1.00-1.23). Although highly aged or aqueous-phase processed SOA coated on BC showed the largest Eabs, their contributions to the bulk absorption enhancement were generally small. We also quantified the absorption of BrC and source contributions. The results showed the BrC absorption at the rural site was nearly twice that of urban site, yet absorption Ångström exponents were similar. Multiple linear regression analysis highlighted the major sources of BrC being coal combustion emissions and photochemical SOA at both sites with additional biomass burning at the rural site. Overall, our results demonstrated the relatively limited winter light absorption enhancement of BC in different chemical environments in NCP, which needs be considered in regional climate models to improve BC radiative forcing estimates.
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Secondary organic aerosol (SOA) produced by atmospheric oxidation of primary emitted precursors is a major contributor to fine particulate matter (PM2.5) air pollution worldwide. Observations during winter haze pollution episodes in urban China show that most of this SOA originates from fossil-fuel combustion but the chemical mechanisms involved are unclear. Here we report field observations in a Beijing winter haze event that reveal fast aqueous-phase conversion of fossil-fuel primary organic aerosol (POA) to SOA at high relative humidity. Analyses of aerosol mass spectra and elemental ratios indicate that ring-breaking oxidation of POA aromatic species, leading to functionalization as carbonyls and carboxylic acids, may serve as the dominant mechanism for this SOA formation. A POA origin for SOA could explain why SOA has been decreasing over the 2013-2018 period in response to POA emission controls even as emissions of volatile organic compounds (VOCs) have remained flat.
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We characterized the aerosol composition and sources of particulate matter (PM) in Sanmenxia, a polluted city located in the Fen-Wei Plain region of Central China. The PM2.5 concentration decreased by 18% from 72 µg m-3 in 2014 to 59 µg m-3 in 2019. All chemical species presented pronounced seasonal variations, with their highest concentrations in winter due to enhanced emissions and the frequent stagnant meteorological conditions. Nitrate was the major fraction of PM2.5 during all seasons (35-41%) except summer (25%), while sulfate was a dominant species in summer (29%) compared to other seasons (16-18%) from July 2018 to June 2019. The detailed analysis of a wintertime severe haze episode that lasted for approximately half a month demonstrated that secondary aerosols, including secondary organic aerosol, sulfate, nitrate, and ammonium, contributed 89% to non-refractory PM1 (NR-PM1), indicating the remarkable role of secondary aerosol formation in air pollution in Sanmenxia. Positive matrix factorization analysis further showed considerably enhanced low-volatility oxygenated organic aerosol (OA) and hydrocarbon-like OA during severe haze episodes, while significant contributions in semi-volatile oxygenated OA and coal combustion OA during clean periods. Severe pollution events in the city were generally associated with air masses from the southwest, and we also found that aerosol species, especially secondary aerosol species, showed distinct forenoon increases that were caused by the subsidence of air pollutants aloft. Our results highlight that future air quality improvement would benefit substantially from a more efficient control of gaseous precursors, particularly the NOx emissions from industry and vehicle emissions.
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Aerosoles/análisis , Contaminantes Atmosféricos/análisis , Contaminación del Aire/estadística & datos numéricos , Contaminación del Aire/análisis , China , Ciudades , Carbón Mineral/análisis , Monitoreo del Ambiente/métodos , Contaminantes Ambientales/análisis , Contaminación Ambiental/análisis , Hidrocarburos/química , Nitratos/análisis , Óxidos de Nitrógeno/análisis , Material Particulado/análisis , Estaciones del Año , Emisiones de Vehículos/análisisRESUMEN
Water-soluble organic aerosol (WSOA) constitutes a large fraction of OA and plays an important role in formation of secondary OA (SOA). Here we characterized the sources and molecular composition of WSOA in summer in Beijing using high-resolution aerosol mass spectrometer and orbitrap mass spectrometer equipped with electrospray ionization. Our results showed that WSOA was the major fraction of OA on average accounting for 69% in summer, which is much higher than that (47%) in winter. However, the oxidation degree of WSOA was comparable between summer and winter (O/C = 0.62 vs. 0.63). Positive matrix factorization analysis showed that SOA contributed dominantly to WSOA (72%) indicating that WSOA was mainly from secondary formation. The two water-soluble SOA factors that are associated with regional processing (OOA-1) and photochemical production (OOA-2), respectively, showed very different behaviors throughout the study. OOA-2 showed much enhanced contribution during polluted periods with low relative humidity (RH), while OOA-1 played a more important role during high RH periods. Molecular composition analysis of WSOA revealed a high diversity of CHO (compounds only containing carbon, hydrogen and oxygen) and CHOS (sulfur-containing organics) in WSOA in summer. Particularly, the relative intensity fraction of CHOS- compounds was increased by 42% from clean to polluted days which was associated with large increases (20%) in organosulfates (OSs) with lower O∗/C (0.1-0.4), and OOA-1. These results suggest the formation of more unsaturated OSs in OOA-1 during polluted days in summer. Comparatively, the biogenic-derived OSs remained relatively stable (24-31%) for the entire study highlighting the ubiquitous importance of biogenic SOA in summer.
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Aerosoles/análisis , Contaminantes Atmosféricos/análisis , Monitoreo del Ambiente , Beijing , Humedad , Espectrometría de Masas , Oxidación-Reducción , Estaciones del Año , Agua/análisisRESUMEN
Black carbon (BC) exerts a large impact on climate radiative forcing and public health, and such impacts depend strongly on chemical composition and mixing state. Here a single particle aerosol mass spectrometry (SPA-MS) along with an aerosol chemical speciation monitor was employed to characterize the composition and mixing state of BC-containing particles in summer and winter in Beijing. Approximately 2 million BC-containing particles were chemically analyzed, and the particles were classified into nine and eight different types in summer and winter, respectively, according to mass spectral signatures and composition. The BC-containing particles in summer were dominated by the type of nitrate-related BC (BC-N, 56.7%), while in winter the BC mixed with organic carbon (OC) and sulfate (BCOC-S), and OC and nitrate (BCOC-N) were two dominant types accounting for 44.9% and 16.6%, respectively. The number fractions of BC-N in summer, and BCOC-N and BC-SN in winter increased largely during periods with severe air pollution, suggesting the enhanced secondary formation on BC-containing particles. We also found that the primary emissions of the biomass burning and coal combustion can affect BC mixing state substaintially as indicated by the considerable fraction of BC mixed with levoglucosan and polycyclic aromatic hydrocarbons in winter. Bivariate polar plots and back trajectory analysis indicated that the sulfate-associated BC-containing particles were mostly from regional transport while the nitrate-related type was more from local production. The optical parameter of absorbing Ångström exponents (AAE) of BC was 1.2 and 1.5 in summer and winter, respectively, and the AAE dependence of BC mixing state was also different in the two seasons. While higher fractions of BC-N were observed during lower AAE periods in summer, the variations of dominant OC-related BC-containing particles in winter were fairly stable as a function of AAE.
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Contaminantes Atmosféricos/análisis , Aerosoles/análisis , Beijing , Carbono/análisis , Monitoreo del Ambiente , Material Particulado/análisis , Estaciones del AñoRESUMEN
Land surface temperature (LST) is defined as an important indicator in the formation and evolution of climate. In some cases, changes in landscape patterns affect LST, even more than the contribution of greenhouse gases. Although much work has been done with respect to the correlations between urban development and thermal environment dynamics, the related questions regarding relationships between LST and landscape patterns in arid regions are not thoroughly considered. Understanding these questions is important in climate change and land planning. The objective of this study was to explore the spatiotemporal variations of LST by distribution index (DI) and Mann-Kendall mutation analysis method and to quantify the relationships between landscape patterns, climatic factors, topographic factors, and the land surface thermal environment (LSTE) by the ordinary linear regressions (OLS) model. The landscape patterns dataset, which was validated by a field trip, was extracted from the Land satellite (Landsat) TM/OLI images by the Random Forest methodology in ArcGIS software. The MODIS/LST product was validated by the "Monthly dataset of China's surface climate" and a field trip. Annual LST increased by 0.54 °C (23.15 °C in 2000 and 23.79 °C in 2015). In different landscape patterns, the percentage of areas with a high level of LST showed a significant difference. In barren land, the highest area proportion for the high LST level was larger than in other landscape patterns. Meanwhile, the area of low LST was mainly concentrated in water bodies. Considerable changes have occurred in landscape patterns, in which the most noteworthy was cultivated land encroaching on grass land (3708.44 km2). The composition of landscape patterns was more important than distribution in determining the region's LST. These findings provide valuable information for land planners dealing with climate change and ecosystem conservation in arid regions.
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Despite substantial mitigation of particulate matter (PM) pollution during the past decade in Beijing, the response of aerosol chemistry to clean air action and meteorology remains less understood. Here we characterized the changes in aerosol composition as responses to emission reductions by using two-year long-term measurements in 2011/2012 and 2017/2018, and WRF-Chem model. Our results showed substantial decreases for all aerosol species except nitrate from 2011/2012 to 2017/2018. Chloride exhibited the largest decrease by 65-89% followed by organics (37-70%), mainly due to reductions in coal combustion emissions in winter and agriculture burning in June. Primary and secondary organic aerosol (SOA) showed comparable decreases by 61-70% in fall and winter, and 34-63% in spring and summer, suggesting that reductions in primary emissions might also suppress SOA formation. The changes in nitrate were negligible and even showed increases due to less reductions in NOx emissions and increased formation potential from N2O5 heterogeneous reactions. As a result, nitrate exceeded sulfate and became the major secondary inorganic aerosol species in PM with the contribution increasing from 14-21% to 22-32%. Further analysis indicated that the reductions in aerosol species from 2011/2012 to 2017/2018 were mainly caused by the decreases of severely polluted events (PM1â¯>â¯100⯵gâ¯m-3). WRF-Chem simulations suggested that the decreases in OA and sulfate in fall and winter were mainly resulted from emission reductions (27-36% and 25-43%) and favorable meteorology (4-10% and 19-30%), while they were dominantly contributed by emission changes in spring and summer. Comparatively, the changes in nitrate were mainly associated with meteorological variations while the contributions of emissions changes were relatively small. Our results highlight different chemical responses of aerosol species to emission changes and meteorology, suggesting that future mitigation of air pollution in China needs species-targeted control policy.
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Aerosoles/análisis , Contaminantes Atmosféricos/análisis , Contaminación del Aire/estadística & datos numéricos , Monitoreo del Ambiente , Material Particulado/análisis , Contaminación del Aire/análisis , Beijing , China , Óxidos de Nitrógeno/análisis , Estaciones del Año , Sulfatos/análisisRESUMEN
Atmospheric aerosols over polar regions have attracted considerable attention for their pivotal effects on climate change. In this study, temporospatial variations in single-particle-based depolarization ratios (δ: s-polarized component divided by the total backward scattering intensity) were studied over the Northwest Pacific and the Arctic Ocean using an optical particle counter with a depolarization module. The δ value of aerosols was 0.06 ± 0.01 for the entire observation period, 61 ± 10% lower than the observations for coastal Japan (0.12 ± 0.02) ( Pan et al. Atmos. Chem. Phys. 2016 , 16 , 9863 - 9873 ) and inland China (0.19 ± 0.02) ( Tian et al. Atmos. Chem. Phys. 2018 , 18 , 18203 - 18217 ) in summer. The volume concentration showed two dominant size modes at 0.9 and 2 µm. The supermicrometer particles were mostly related to sea-salt aerosols with a δ value of 0.09 over marine polar areas, â¼22% larger than in the low-latitude region because of differences in chemical composition and dry air conditions. The δ values for fine particles (<1 µm) were 0.05 ± 0.1, 50% lower than inland anthropogenic pollutants, mainly because of the complex mixtures of submicrometer sea salts. High particle concentrations in the Arctic Ocean could mostly be attributed to the strong marine emission of sea salt associated with deep oceanic cyclones, whereas long-range transport pollutants from the continent were among the primary causes of high particle concentrations in the Northwest Pacific region.
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Contaminantes Atmosféricos , Aerosoles , Regiones Árticas , China , Monitoreo del Ambiente , Japón , Océanos y Mares , Océano Pacífico , Tamaño de la PartículaRESUMEN
To understand the temporal characteristics and vertical distributions of ammonia (NH3) and ammonium (NH4) in urban Beijing, we conducted ground-based and tower-based measurements of gaseous NH3 and submicron aerosol composition. The average mixing ratio of NH3 was 16.5⯱â¯7.4â¯ppb, ranging from 3.8 to 36.9â¯ppb. Gas-to-particle partitioning of NHx (=NH3â¯+â¯NH4) played a significant role on NH3 concentration as the molar ratio of NH3 to NHx decreased as a function of NH4 concentration. The NH3 concentrations increased as a function of PM1 at lower levels (<125⯵gâ¯m-3), but remained relatively constant at higher PM and NH4 levels, indicating an enhanced gas-to-particle conversion of NH3 during highly polluted conditions. The potential sources of NHx were found to include fossil fuel combustion and biomass burning. Regional transport could also play an important role on NH3 concentration during the formation stage of haze episodes due to particle-to-gas conversion. Four distinctive types of vertical profiles (87% of the time) of both NH3 and fine particle light extinction coefficient (bext) were observed and they were associated with well-mixed atmosphere, fast accumulation of local emissions, regional transport aloft, and the formation of low urban boundary layer, respectively. However, the vertical profiles of NH3 typically (96% of the time) showed a more homogeneous characteristic than those of bext below 260â¯m, except periods with both strong temperature inversion and large aerosol gradient, the formation of urban boundary layer shall cause a significant transition in the vertical distribution of NH3 below 260â¯m. During highly polluted situations (PM1â¯>â¯125⯵gâ¯m-3), the strong effect of gas-to-particle partitioning of NHx sometimes (7% of the time) caused opposite trends in vertical profiles of NH3 and bext.
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Refractory black carbon (rBC) aerosol is an important climate forcer, and its impacts are greatly influenced by the species associated with rBC cores. However, relevant knowledge is particularly lacking at the Tibetan Plateau (TP). Here we report, for the first time, highly time-resolved measurement results of rBC and its coating species in central TP (4730 m a.s.l), using an Aerodyne soot particle aerosol mass spectrometer (SP-AMS), which selectively measured rBC-containing particles. We found that the rBC was overall thickly coated with an average mass ratio of coating to rBC (RBC) of â¼7.7, and the coating species were predominantly secondarily formed by photochemical reactions. Interestingly, the thickly coated rBC was less oxygenated than the thinly coated rBC, mainly due to influence of the transported biomass burning organic aerosol (BBOA). This BBOA was relatively fresh but formed very thick coating on rBC. We further estimated the "lensing effect" of coating semiquantitatively by comparing the measurement data from a multiangle absorption photometer and SP-AMS, and found it could lead to up to 40% light absorption enhancement at RBC > 10. Our findings highlight that BBOA can significantly affect the "lensing effect", in addition to its relatively well-known role as light-absorbing "brown carbon."
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Aerosoles , Contaminantes Atmosféricos , Hollín , Biomasa , Carbono , TibetRESUMEN
Brown carbon (BrC) has recently received much attention because of its light absorption features. The chemical compositions, optical properties, and sources of fine aerosol at a high-elevation mountain observatory (4730 m a.s.l.) in the central Tibetan Plateau were measured between 31 May and 1 July 2015. A low flow-rate sampler was used to collect 24-h average fine particulate matter (PM2.5) filter samples. Water-soluble ions, organic carbon (OC), elemental carbon, water-soluble organic carbon (WSOC), and light absorption by water-soluble BrC were determined for 26 filter samples. The mean (± 1σ) OC and WSOC concentrations were 0.76 ± 0.43 and 0.39 ± 0.15 µgC/m3, respectively, and the mean WSOC/OC mass ratio was 0.59 ± 0.22. The OC and WSOC concentrations were relatively higher (0.59-1.80 and 0.33-0.83 µgC/m3, respectively) during the pre-monsoon period (2-13 June) and were relatively lower (0.27-0.77 and 0.12-0.50 µgC/m3, respectively) during the monsoon period (14 June to 1 July), probably because of wet scavenging of aerosols during long-range transport and the presence of cleaner marine air masses during the monsoon period. The absorption spectra of PM2.5 water extracts smoothly increase from visible range to ultraviolet range. The absorption Ångström exponent, which describes the wavelength dependence of water-soluble BrC, was 2.74-10.61 (mean 6.19 ± 1.70), and its value was similar in the pre-monsoon period (6.57 ± 0.56) to that in the monsoon period (5.91 ± 2.14). The water-soluble BrC mass absorption efficiency, 0.38 ± 0.16 m2/(g C), was much lower than those observed in most urban areas but similar to those in other remote sites. Absorption coefficient at 365 nm, typically used as a proxy for water-soluble BrC, correlated well with the WSOC concentration (R 2 = 0.57), K+ concentration (R 2 = 0.75), and organic aerosol biomass burning markers characterized by an Aerodyne aerosol mass spectrometer (C2H4O2+ + C3H5O2+, R 2 = 0.60). It can be inferred that biomass burning was an important source of water-soluble BrC in the study area combined with air mass back trajectory analysis using the NOAA HYSPLIT as well as MODIS data of fire dots and aerosol optical depths. The water-soluble BrC to BC light absorption (at 365 nm) coefficient ratios were 9-27%.