The Yangtze River Delta (YRD) is one of the most densely populated regions in China with severe air quality issues that have not been fully understood. Thus, in this study, based on 1-year (2013) ...continuous measurement at a National Reference Climatological Station (NRCS, 30.22° N, 120.17° E; 41.7 m a.s.l.) in the center of Hangzhou in the YRD, we investigated the seasonal characteristics, interspecies relationships, and the local emissions and the regional potential source contributions of trace gases (including O3, NOx, NOy, SO2, and CO) and particulate matter (PM2.5 and PM10). Results revealed that severe two-tier air pollution (photochemical and haze pollution) occurred in this region, with frequent exceedances in O3 (38 days) and PM2.5 (62 days). O3 and PM2.5 both exhibited distinct seasonal variations with reversed patterns: O3 reaching a maximum in warm seasons (May and July) but PM2.5 reaching a maximum in cold seasons (November to January). The overall results from interspecies correlation indicated a strong local photochemistry favoring the O3 production under a volatile organic compound (VOC)-limited regime, whereas it moved towards an optimum O3 production zone during warm seasons, accompanied by the formation of secondary fine particulates under high O3. The emission maps of PM2.5, CO, NOx, and SO2 demonstrated that local emissions were significant for these species on a seasonal scale. The contributions from the regional transport among inland cities (Zhejiang, Jiangsu, Anhui, and Jiangxi Province) on a seasonal scale were further confirmed to be crucial to air pollution at the NRCS site by using backward trajectory simulations. Air masses transported from the offshore areas of the Yellow Sea, East Sea, and South Sea were also found to be highly relevant to the elevated O3 at the NRCS site through the analysis of potential source contribution function (PSCF). Case studies of photochemical pollution (O3) and haze (PM2.5) episodes both suggested the combined importance of local atmospheric photochemistry and synoptic conditions during the accumulation (related with anticyclones) and dilution process (related with cyclones). Apart from supplementing a general picture of the air pollution state in the city of Hangzhou in the YRD region, this study specifically elucidates the role of local emission and regional transport, and it interprets the physical and photochemical processes during haze and photochemical pollution episodes. Moreover, this work suggests that cross-regional control measures are crucial to improve air quality in the YRD region, and it further emphasizes the importance of local thermally induced circulation for air quality.
Secondary aerosol (SA) frequently drives severe haze formation on the North China Plain. However, previous studies mostly focused on submicron SA formation, thus our understanding of SA formation on ...supermicron particles remains poor. In this study, PM2.5 chemical composition and PM10 number size distribution measurements revealed that the SA formation occurred in very distinct size ranges. In particular, SA formation on dust-dominated supermicron particles was surprisingly high and increased with relative humidity (RH). SA formed on supermicron aerosols reached comparable levels with that on submicron particles during evolutionary stages of haze episodes. These results suggested that dust particles served as a medium for rapid secondary organic and inorganic aerosol formation under favorable photochemical and RH conditions in a highly polluted environment. Further analysis indicated that SA formation pathways differed among distinct size ranges. Overall, our study highlights the importance of dust in SA formation during non-dust storm periods and the urgent need to perform size-resolved aerosol chemical and physical property measurements in future SA formation investigations that are extended to the coarse mode because the large amount of SA formed thereon might have significant impacts on ice nucleation, radiative forcing, and human health.
Six World Meteorological Organization (WMO)/Global Atmosphere Watch (GAW) stations are located at background sites in China, which constitute a network for monitoring surface ozone, including its ...long-term temporal variation. In this study, we evaluated the seasonal variation in surface ozone simulated by the ECHAM/MESSy Atmospheric Chemistry (EMAC) general circulation model with the measurements made at these WMO/GAW background stations for the period of 2010–2012, and investigated the regional representativeness of each station with respect to the seasonal variation in surface ozone. We determined the contributions of ozone originating from various tropospheric and stratospheric latitude bands based on EMAC simulations using a tagged tracer approach. The results showed that the predominant contribution to surface ozone was from the troposphere in northern middle-high and tropical latitudes. For each station there was a large surrounding area in which the yearly ozone maximum occurred in the same month as it did at the station, reflecting the regional characteristics of the seasonal variation in surface ozone recorded at the WMO/GAW background stations. Surface ozone in China was found to generally peak in summer over non-monsoon and mid-latitude monsoon regions and in spring over low-latitude monsoon regions, indicating that the regional representativeness of ozone variability in China is significantly influenced by the Asian summer monsoon.
•The EMAC model is evaluated against surface ozone measured at the WMO/GAW background stations in China.•The contributions of ozone originating from various latitude bands simulated by EMAC are analyzed.•Regional representativeness of surface ozone variation at the six Chinese WMO/ GAW stations is investigated.
Both peroxyacetyl nitrate (PAN) and ozone (O3) are key photochemical products in the atmosphere. Most of the previous in situ observations of both gases have been made in polluted regions and at ...low-altitude sites. Here we present the first simultaneous measurements of PAN and O3 at Nam Co (NMC; 30°46′ N, 90°57′ E, 4745 m a.s.l.), a remote site in the central Tibetan Plateau (TP). The observations were made during summer periods in 2011 and 2012. The PAN levels averaged 0.36 ppb (range: 0.11–0.76 ppb) and 0.44 ppb (range: 0.21–0.99 ppb) during 17–24 August 2011 and 15 May to 13 July 2012, respectively. The O3 level varied from 27.9 to 96.4 ppb, with an average of 60.0 ppb. Profound diurnal cycles of PAN and O3 were observed with minimum values around 05:00 LT, steep rises in the early morning, and broader platforms of high values during 09:00–20:00 LT. The evolution of the planetary boundary layer (PBL) played a key role in shaping the diurnal patterns of both gases, particularly the rapid increases of PAN and O3 in the early morning. Air entrainment from the free troposphere into the PBL seemed to cause the early-morning increase and be a key factor for sustaining the daytime high concentrations of both gases. The days with higher daytime PBL (about 3 km) showed stronger diurnal variations in both gases and were mainly distributed in the drier pre-monsoon period, while those with shallower daytime PBL (about 2 km) showed minor diurnal variations and were mainly distributed in the humid monsoon period. Episodes of higher PAN levels were occasionally observed at NMC. These PAN episodes were caused either by rapid downward transport of air masses from the middle/upper troposphere or by long-range transport of PAN plumes from north India, north Pakistan, and Nepal. The maximum PAN level in the downward transport cases ranged from 0.5 to 0.7 ppb. In the long-range transport case, the PAN level varied in the range of 0.3–1.0 ppb, with an average of 0.6 ppb. This long-range transport process influenced most of the western and central TP region for about a week in early June 2012. Our results suggest that polluted air masses from South Asia can significantly enhance the PAN level over the TP. As PAN acts as a reservoir of NOx, the impacts of pollution transport from South Asia on tropospheric photochemistry over the TP region deserve further studies.
Inter-annual variability and long-term trends in tropospheric ozone are both
environmental and climate concerns. Ozone measured at Mt Waliguan
Observatory (WLG, 3816 m a.s.l.) on the Tibetan Plateau ...over the period of
1994–2013 has increased significantly by 0.2–0.3 ppbv yr−1 during
spring and autumn but shows a much smaller trend in winter and no
significant trend in summer. Here we explore the factors driving the observed
ozone changes at WLG using backward trajectory analysis, chemistry–climate
model hindcast simulations (GFDL AM3), a trajectory-mapped ozonesonde data
set,
and several climate indices. A stratospheric ozone tracer implemented in
GFDL AM3 indicates that stratosphere-to-troposphere transport (STT) can
explain ∼ 60 % of the simulated springtime ozone increase at WLG,
consistent with an increase in the NW air-mass frequency inferred from the
trajectory analysis. Enhanced STT associated with the strengthening of the
mid-latitude jet stream contributes to the observed high ozone anomalies at
WLG during the springs of 1999 and 2012. During autumn, observations at WLG
are more heavily influenced by polluted air masses originating from South East
Asia than in the other seasons. Rising Asian anthropogenic emissions of ozone
precursors are the key driver of increasing autumnal ozone observed at WLG, as
supported by the GFDL AM3 model with time-varying emissions, which captures
the observed ozone increase (0.26 ± 0.11 ppbv yr−1). AM3
simulates a greater ozone increase of 0.38 ± 0.11 ppbv yr−1 at
WLG in autumn under conditions with strong transport from South East Asia and
shows no significant ozone trend in autumn when anthropogenic emissions are
held constant in time. During summer, WLG is mostly influenced by easterly
air masses, but these trajectories do not extend to the polluted regions of
eastern China and have decreased significantly over the last 2 decades,
which likely explains why summertime ozone measured at WLG shows no
significant trend despite ozone increases in eastern China. Analysis of the
Trajectory-mapped Ozonesonde data set for the Stratosphere and Troposphere
(TOST) and trajectory residence time reveals increases in direct ozone
transport from the eastern sector during autumn, which adds to the autumnal
ozone increase. We further examine the links of ozone variability at WLG to
the quasi-biennial oscillation (QBO), the East Asian summer monsoon (EASM), and the sunspot cycle. Our
results suggest that the 2–3-, 3–7-, and 11-year periodicities are linked
to the
QBO, EASM index, and sunspot cycle, respectively. A multivariate regression
analysis is performed to quantify the relative contributions of various
factors to surface ozone concentrations at WLG. Through an observational and
modelling analysis, this study demonstrates the complex relationships between
surface ozone at remote locations and its dynamical and chemical influencing
factors.
The unknown daytime source of HONO has been extensively investigated due to unexplained atmospheric oxidation capacity and current modelling bias, especially during cold seasons. In this study, ...abrupt morning increases in atmospheric HONO at a rural site in the North China Plain (NCP) were observed almost on daily basis, which were closely linked to simultaneous rises in atmospheric water vapor content and NH3 concentrations. Dew and guttation water formation was frequently observed on wheat leaves, from which water samples were taken and chemically analyzed for the first time. Results confirmed that such natural processes likely governed the daily nighttime deposition and daytime release of HONO and NH3, which have not been considered in the numerous HONO budget studies investigating its large missing daytime source in the NCP. The dissolved HONO and NH3 in leaf surface water droplets reached 1.4 and 23 mg L−1 during the morning on average, resulting in averaged atmospheric HONO and NH3 increases of 0.89 ± 0.61 and 43.7 ± 29.3 ppb during morning hours, with relative increases of 186 ± 212 % and 233 ± 252 %, respectively. The high atmospheric oxidation capacity contained within HONO was stored in near surface liquid water (such as dew, guttation and soil surface water) during nighttime, which prevented its atmospheric dispersion after sunset and protected it from photodissociation during early morning hours. HONO was released in a blast during later hours with stronger solar radiation, which triggered and then accelerated daytime photochemistry through the rapid photolysis of HONO and subsequent OH production, especially under high RH conditions, forming severe secondary gaseous and particulate pollution. Results of this study demonstrate that global ecosystems might play significant roles in atmospheric photochemistry through nighttime dew formation and guttation processes.
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•Daily strong HONO morning peaks greatly added to daytime oxidation capacity, promoting secondary air pollution formation•Authentic dew and guttation water samples revealed great contribution to nighttime storage and daytime emissions of HONO•Dew and guttation water impact on HONO lacks consideration in models leading to atmospheric oxidation capacity underestimates
Hydroxymethanesulfonate (HMS), a key marker species of aqueous-phase processing, plays a significant role in sulfur budget in atmosphere. Here we have a comprehensive characterization of HMS at urban ...and rural sites in North China Plain (NCP) by using the real-time measurements from a high-resolution aerosol mass spectrometer (AMS) and a single-particle AMS together with offline filter analysis. Our results showed much higher winter concentration of HMS at the rural site (average±1σ: 2.58 ± 2.56 μg m−3) than that (1.70 ± 2.68 μg m−3) in Beijing due to the more frequent fog events, low particle acidity and high concentration of precursors. The HMS on average contributed 6.3% and 5.2% to organic aerosol (OA), and 16% and 12% to the total particulate sulfur, at the rural and urban sites, respectively. HMS was highly correlated with aqueous-phase secondary OA and sulfate, and its contribution to the total particulate sulfur increased significantly as a function of relative humidity demonstrating the effective HMS production from aqueous-phase processing. Single-particle analysis showed that HMS-containing particles were mainly mixed with amine-related compounds. In addition, we found that organosulfur compounds (OS) estimated from sulfur-containing fragments of AMS correlated well with HMS at both urban and rural sites. While OS at the rural site was dominated by HMS, other types of OS were also important in urban area. The high HMS also affected the estimation of particle acidity using the AMS measured and predicted ammonium, particularly during severe haze episodes. Overall, our results demonstrated the importance of HMS in winter in NCP, and it could be more important in total particulate sulfur budget as the continuous decrease in sulfate in the future.
•HMS plays an important role in sulfur budget in winter in North China Plain.•Higher HMS concentrations in rural areas than urban sites were observed.•Organosulfur compounds can be estimated with AMS sulfur-containing ions.
Tropospheric ozone (O3) and peroxyacetyl nitrate (PAN) are both photochemical pollutants harmful to the ecological environment and human health. In this study, measurements of O3 and PAN as well as ...their precursors were conducted from May to July 2019 at Nam Co station (NMC), a highly pristine high-altitude site in the southern Tibetan Plateau (TP), to investigate how distinct transport processes and photochemistry contributed to their variations. Results revealed that, despite highly similar diurnal variations with steep morning rises and flat daytime plateaus that were caused by boundary layer development and downmixing of free-tropospheric air, day-to-day variations in O3 and PAN were in fact controlled by distinct physicochemical processes. During the dry spring season, air masses rich in O3 were associated with high-altitude westerly air masses that entered the TP from the west or the south, which frequently carried high loadings of stratospheric O3 to NMC. During the summer monsoon season, a northward shift of the subtropical jet stream shifted the stratospheric downward entrainment pathway also to the north, leading to direct stratospheric O3 entrainment into the troposphere of the northern TP, which traveled southwards to NMC within low altitudes via northerly winds in front of ridges or closed high pressures over the TP. Westerly and southerly air masses, however, revealed low O3 levels due to the overall less stratospheric O3 within the troposphere of low-latitude regions. PAN, however, was only rich in westerly or southerly air masses that crossed over polluted regions such as northern India, Nepal or Bangladesh before entering the TP and arriving at NMC from the south during both spring and summer. Overall, the O3 level at NMC was mostly determined by stratosphere–troposphere exchange (STE), which explained 77 % and 88 % of the observed O3 concentration in spring and summer, respectively. However, only 0.1 % of the springtime day-to-day O3 variability could be explained by STE processes, while 22 % was explained during summertime. Positive net photochemical formation was estimated for both O3 and PAN based on observation-constrained box modeling. Near-surface photochemical formation was unable to account for the high O3 level observed at NMC, nor was it the determining factor for the day-to-day variability of O3. However, it was able to capture events with elevated PAN concentrations and explain its day-to-day variations. O3 and PAN formation were both highly sensitive to NOx levels, with PAN being also quite sensitive to volatile organic compound (VOC) concentrations. The rapid development of transportation networks and urbanization within the TP may lead to increased emissions and loadings in NOx and VOCs, resulting in strongly enhanced O3 and PAN formation in downwind pristine regions, which should be given greater attention in future studies.
The NO–NO2 cycle determines the formation of O3 and hence plays a critical role in the oxidizing capacity of troposphere. Traditional view concluded that the heterogeneous oxidation of NO to NO2 was ...negligible due to the weak reactivity of NO on aerosols, compared to the homogeneous oxidation process. However, the results here reported for the first time that SO2 can greatly promote the heterogeneous transformation of NO into NO2 and HONO on MgO particles under ambient conditions. The uptake coefficients of NO were increased by 2–3 orders of magnitudes on SO2-aged MgO, compared to the fresh sample. Based on spectroscopic characterization and density functional theory (DFT) calculations, the active sites for the adsorption and oxidation of NO were determined to be sulfates, where an intermediate SO4–NO complex was formed during the adsorption. The decomposition of this species led to the formation of NO2 and the change of sulfate configuration. The formed NO2 could further react with surface sulfite to form HONO and sulfate. The conversion of NO to NO2 and HONO on the SO2-aged MgO surface under ambient conditions contributes a new formation pathway of NO2 and HONO and could be quite helpful for understanding the source of atmospheric oxidizing capacity as well as the formation of air pollution complexes in polluted regions such as the northern China.
The study of atmospheric nitrous acid (HONO), which is the primary source of OH radicals, is crucial with respect to understanding atmospheric photochemistry and heterogeneous chemical processes. ...Heterogeneous NO2 chemistry under haze conditions has been identified as one of the missing sources of HONO on the North China Plain, and also produces sulfate and nitrate. However, controversy exists regarding the various proposed HONO production mechanisms, mainly regarding whether SO2 directly takes part in the HONO production process and what roles NH3 and the pH value play. In this paper, never before seen explosive HONO production was reported and evidence was found – for the first time in field measurements during fog (usually with 4< pH < 6) and haze episodes under high relative humidity (pH ≈4) – that NH3 was the key factor that promoted the hydrolysis of NO2, leading to the explosive growth of HONO and nitrate under both high and relatively lower pH conditions. The results also suggest that SO2 plays a minor or insignificant role in HONO formation during fog and haze events, but was indirectly oxidized upon the photolysis of HONO via subsequent radical mechanisms. Aerosol hygroscopicity significantly increased with rapid inorganic secondary aerosol formation, further promoting HONO production as a positive feedback. For future photochemical and aerosol pollution abatement, it is crucial to introduce effective NH3 emission control measures, as NH3-promoted NO2 hydrolysis is a large daytime HONO source, releasing large amounts of OH radicals upon photolysis, which will contribute largely to both atmospheric photochemistry and secondary aerosol formation.
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