skip to main content
US FlagAn official website of the United States government
dot gov icon
Official websites use .gov
A .gov website belongs to an official government organization in the United States.
https lock icon
Secure .gov websites use HTTPS
A lock ( lock ) or https:// means you've safely connected to the .gov website. Share sensitive information only on official, secure websites.

Explore Research Products in the PAR
It may take a few hours for recently added research products to appear in PAR search results.


Title: Isotopic constraints on heterogeneous sulfate production in Beijing haze
Abstract. Discerning mechanisms of sulfate formation during fine-particle pollution (referred to as haze hereafter) in Beijing is important for understanding the rapid evolution of haze and for developing cost-effective air pollution mitigation strategies. Here we present observations of the oxygen-17 excess of PM2.5 sulfate (Δ17O(SO42−)) collected in Beijing haze from October 2014 to January 2015 to constrain possible sulfate formation pathways. Throughout the sampling campaign, the 12-hourly averaged PM2.5 concentrations ranged from 16 to 323µg m−3 with a mean of (141  ±  88 (1σ))µg m−3, with SO42− representing 8–25% of PM2.5 mass. The observed Δ17O(SO42−) varied from 0.1 to 1.6‰ with a mean of (0.9  ±  0.3)‰. Δ17O(SO42−) increased with PM2.5 levels in October 2014 while the opposite trend was observed from November 2014 to January 2015. Our estimate suggested that in-cloud reactions dominated sulfate production on polluted days (PDs, PM2.5  ≥  75µg m−3) of Case II in October 2014 due to the relatively high cloud liquid water content, with a fractional contribution of up to 68%. During PDs of Cases I and III–V, heterogeneous sulfate production (Phet) was estimated to contribute 41–54% to total sulfate formation with a mean of (48  ±  5)%. For the specific mechanisms of heterogeneous oxidation of SO2, chemical reaction kinetics calculations suggested S(IV) ( = SO2 ⚫H2O+HSO3−  +  SO32−) oxidation by H2O2 in aerosol water accounted for 5–13% of Phet. The relative importance of heterogeneous sulfate production by other mechanisms was constrained by our observed Δ17O(SO42−). Heterogeneous sulfate production via S(IV) oxidation by O3 was estimated to contribute 21–22% of Phet on average. Heterogeneous sulfate production pathways that result in zero-Δ17O(SO42−), such as S(IV) oxidation by NO2 in aerosol water and/or by O2 via a radical chain mechanism, contributed the remaining 66–73% of Phet. The assumption about the thermodynamic state of aerosols (stable or metastable) was found to significantly influence the calculated aerosol pH (7.6  ±  0.1 or 4.7  ±  1.1, respectively), and thus influence the relative importance of heterogeneous sulfate production via S(IV) oxidation by NO2 and by O2. Our local atmospheric conditions-based calculations suggest sulfate formation via NO2 oxidation can be the dominant pathway in aerosols at high-pH conditions calculated assuming stable state while S(IV) oxidation by O2 can be the dominant pathway providing that highly acidic aerosols (pH ≤ 3) exist. Our local atmospheric-conditions-based calculations illustrate the utility of Δ17O(SO42−) for quantifying sulfate formation pathways, but this estimate may be further improved with future regional modeling work.  more » « less
Award ID(s):
1644998 1645062
PAR ID:
10087854
Author(s) / Creator(s):
; ; ; ; ; ; ; ; ; ; ;
Date Published:
Journal Name:
Atmospheric Chemistry and Physics
Volume:
18
Issue:
8
ISSN:
1680-7324
Page Range / eLocation ID:
5515 to 5528
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. ; ; ; ; ; ; ; ; ; ; et al (, Journal of Geophysical Research: Atmospheres)
    Abstract Studies of wintertime air quality in the North China Plain (NCP) show that particulate‐nitrate pollution persists despite rapid reduction in NOxemissions. This intriguing NOx‐nitrate relationship may originate from non‐linear nitrate‐formation chemistry, but it is unclear which feedback mechanisms dominate in NCP. In this study, we re‐interpret the wintertime observations of17O excess of nitrate (∆17O(NO3−)) in Beijing using the GEOS‐Chem (GC) chemical transport model to estimate the importance of various nitrate‐production pathways and how their contributions change with the intensity of haze events. We also analyze the relationships between other metrics of NOychemistry and [PM2.5] in observations and model simulations. We find that the model on average has a negative bias of −0.9‰ and −36% for ∆17O(NO3−) and [Ox,major] (≡ [O3] + [NO2] + [p‐NO3−]), respectively, while overestimating the nitrogen oxidation ratio ([NO3−]/([NO3−] + [NO2])) by +0.12 in intense haze. The discrepancies become larger in more intense haze. We attribute the model biases to an overestimate of NO2‐uptake on aerosols and an underestimate in wintertime O3concentrations. Our findings highlight a need to address uncertainties related to heterogeneous chemistry of NO2in air‐quality models. The combined assessment of observations and model results suggest that N2O5uptake in aerosols and clouds is the dominant nitrate‐production pathway in wintertime Beijing, but its rate is limited by ozone under high‐NOx‐high‐PM2.5conditions. Nitrate production rates may continue to increase as long as [O3] increases despite reduction in [NOx], creating a negative feedback that reduces the effectiveness of air pollution mitigation. 
    more » « less
  2. ; ; ; ; ; ; ; ; ; ; et al (, Atmospheric Chemistry and Physics)
    Abstract. Airborne and ground-based measurements of aerosol concentrations, chemicalcomposition, and gas-phase precursors were obtained in three valleys innorthern Utah (USA). The measurements were part of the Utah Winter FineParticulate Study (UWFPS) that took place in January–February 2017. Totalaerosol mass concentrations of PM1 were measured from a Twin Otteraircraft, with an aerosol mass spectrometer (AMS). PM1 concentrationsranged from less than 2µgm−3 during clean periods to over100µgm−3 during the most polluted episodes, consistent withPM2.5 total mass concentrations measured concurrently at groundsites. Across the entire region, increases in total aerosol mass above∼2µgm−3 were associated with increases in theammonium nitrate mass fraction, clearly indicating that the highest aerosolmass loadings in the region were predominantly attributable to an increase inammonium nitrate. The chemical composition was regionally homogenous fortotal aerosol mass concentrations above 17.5µgm−3, with 74±5% (average±standard deviation) ammonium nitrate, 18±3%organic material, 6±3% ammonium sulfate, and 2±2%ammonium chloride. Vertical profiles of aerosol mass and volume in the regionshowed variable concentrations with height in the polluted boundary layer.Higher average mass concentrations were observed within the first few hundredmeters above ground level in all three valleys during pollution episodes. Gas-phase measurements of nitric acid (HNO3) and ammonia (NH3) duringthe pollution episodes revealed that in the Cache and Utah valleys, partitioningof inorganic semi-volatiles to the aerosol phase was usually limited by theamount of gas-phase nitric acid, with NH3 being in excess. The inorganicspecies were compared with the ISORROPIA thermodynamic model. Total inorganicaerosol mass concentrations were calculated for various decreases in totalnitrate and total ammonium. For pollution episodes, our simulations of a50% decrease in total nitrate lead to a 46±3% decrease in totalPM1 mass. A simulated 50% decrease in total ammonium leads to a36±17%µgm−3 decrease in total PM1 mass, over the entirearea of the study. Despite some differences among locations, ourresults showed a higher sensitivity to decreasing nitric acid concentrationsand the importance of ammonia at the lowest total nitrate conditions. In theSalt Lake Valley, both HNO3 and NH3 concentrations controlledaerosol formation. 
    more » « less
  3. ; (, Fossil Record)
    Abstract. Physiological aspects like heat balance, gas exchange, osmoregulation, and digestion of the early Permian aquatic temnospondyl Archegosaurus decheni, which lived in a tropical freshwater lake, are assessed based on osteological correlates of physiologically relevant soft-tissue organs and by physiological estimations analogous to air-breathing fishes. Body mass (M) of an adult Archegosaurus with an overall body length of more than 1m is estimated as 7kg using graphic double integration. Standard metabolic rate (SMR) at 20°C (12kJh−1) and active metabolic rate (AMR) at 25°C (47kJh−1) were estimated according to the interspecific allometry of metabolic rate (measured as oxygen consumption) of all fish (VO2 = 4. 8M0. 88) and form the basis for most of the subsequent estimations. Archegosaurus is interpreted as a facultative air breather that got O2 from the internal gills at rest in well-aerated water but relied on its lungs for O2 uptake in times of activity and hypoxia. The bulk of CO2 was always eliminated via the gills. Our estimations suggest that if Archegosaurus did not have gills and released 100% CO2 from its lungs, it would have to breathe much more frequently to release enough CO2 relative to the lung ventilation required for just O2 uptake. Estimations of absorption and assimilation in the digestive tract of Archegosaurus suggest that an adult had to eat about six middle-sized specimens of the acanthodian fish Acanthodes (ca. 8cm body length) per day to meet its energy demands. Archegosaurus is regarded as an ammonotelic animal that excreted ammonia (NH3) directly to the water through the gills and the skin, and these diffusional routes dominated nitrogen excretion by the kidneys as urine. Osmotic influx of water through the gills had to be compensated for by production of dilute, hypoosmotic urine by the kidneys. Whereas Archegosaurus has long been regarded as a salamander-like animal, there is evidence that its physiology was more fish- than tetrapod-like in many respects. 
    more » « less
  4. ; ; ; ; ; ; (, Biogeosciences)
    Abstract. Heterotrophic prokaryotic production (BP) was studied in the western tropical South Pacific (WTSP) using the leucine technique, revealing spatial and temporal variability within the region. Integrated over the euphotic zone, BP ranged from 58 to 120mg Cm−2d−1 within the Melanesian Archipelago, and from 31 to 50mg Cm−2d−1 within the western subtropical gyre. The collapse of a bloom was followed during 6 days in the south of Vanuatu using a Lagrangian sampling strategy. During this period, rapid evolution was observed in the three main parameters influencing the metabolic state: BP, primary production (PP) and bacterial growth efficiency. With N2 fixation being one of the most important fluxes fueling new production, we explored relationships between BP, PP and N2 fixation rates over the WTSP. The contribution of N2 fixation rates to bacterial nitrogen demand ranged from 3 to 81%. BP variability was better explained by the variability of N2 fixation rates than by that of PP in surface waters of the Melanesian Archipelago, which were characterized by N-depleted layers and low DIP turnover times (TDIP<100h). This is consistent with the fact that nitrogen was often one of the main factors controlling BP on short timescales, as shown using enrichment experiments, followed by dissolved inorganic phosphate (DIP) near the surface and labile organic carbon deeper in the euphotic zone. However, BP was more significantly correlated with PP, but not with N2 fixation rates where DIP was more available (TDIP>100h), deeper in the Melanesian Archipelago, or within the entire euphotic zone in the subtropical gyre. The bacterial carbon demand to gross primary production ratio ranged from 0.75 to 3.1. These values are discussed in the framework of various assumptions and conversion factors used to estimate this ratio, including the methodological errors, the daily variability of BP, the bacterial growth efficiency and one bias so far not considered: the ability for Prochlorococcus to assimilate leucine in the dark. 
    more » « less
  5. ; ; ; ; ; ; ; ; (, Atmospheric Chemistry and Physics)
    Abstract. Recent studies have revealed a significant influx of anthropogenic aerosol from South Asia to the Himalayas and Tibetan Plateau (TP) during pre-monsoon period. In order to characterize the chemical composition, sources, and transport processes of aerosol in this area, we carried out a field study during June 2015 by deploying a suite of online instruments including an Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-AMS) and a multi-angle absorption photometer (MAAP) at Nam Co station (90°57′E, 30°46′N; 4730ma.s.l.) at the central of the TP. The measurements were made at a period when the transition from pre-monsoon to monsoon occurred. The average ambient mass concentration of submicron particulate matter (PM1) over the whole campaign was  ∼ 2.0µgm−3, with organics accounting for 68%, followed by sulfate (15%), black carbon (8%), ammonium (7%), and nitrate (2%). Relatively higher aerosol mass concentration episodes were observed during the pre-monsoon period, whereas persistently low aerosol concentrations were observed during the monsoon period. However, the chemical composition of aerosol during the higher aerosol concentration episodes in the pre-monsoon season was on a case-by-case basis, depending on the prevailing meteorological conditions and air mass transport routes. Most of the chemical species exhibited significant diurnal variations with higher values occurring during afternoon and lower values during early morning, whereas nitrate peaked during early morning in association with higher relative humidity and lower air temperature. Organic aerosol (OA), with an oxygen-to-carbon ratio (O∕C) of 0.94, was more oxidized during the pre-monsoon period than during monsoon (average O∕C ratio of 0.72), and an average O∕C was 0.88 over the entire campaign period, suggesting overall highly oxygenated aerosol in the central TP. Positive matrix factorization of the high-resolution mass spectra of OA identified two oxygenated organic aerosol (OOA) factors: a less oxidized OOA (LO-OOA) and a more oxidized OOA (MO-OOA). The MO-OOA dominated during the pre-monsoon period, whereas LO-OOA dominated during monsoon. The sensitivity of air mass transport during pre-monsoon with synoptic process was also evaluated with a 3-D chemical transport model. 
    more » « less
  • Citation Formats
  • MLA
  • APA
  • Chicago
  • BibTeX
  • Save / Share this Record
  • Send to Email