Chemical characteristics of dicarboxylic acids and related organic compounds in PM2.5 during biomass-burning and non-biomass-burning seasons at a rural site of Northeast China

Cao, Fang; Zhang, Shichun; Kawamura, Kimitaka; Liu, Xiaoyan; Yang, Chi; Xu, Zufei; Fan, Mei-Yi; Zhang, Wenqi; Bao, Mengying; Chang, Yunhua; Song, Wenhuai; Liu, Shoudong; Lee, Xuhui; Li, Jun; Zhang, Gan; Zhang, Yanlin

doi:10.1016/j.envpol.2017.08.045

Cited by 81 publications

(45 citation statements)

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“…After 6 h and 63 km of transport, a noticeable increase in the overall chemical oxidation was observed. Rapid oxidation was also observed in studies of biomass burning organic aerosol in Africa (Capes et al, 2008;Vakkari et al, 2014), over the Mediterranean Sea (Bougiatioti et al, 2014), and Hyytiälä, Finland Vogel et al, 2013). Other studies focused on the oxidation of molecular tracers such as levoglucosan have shown that they can be degraded rapidly after emission, depending on the atmospheric conditions (Lai et al, 2014;Slade et al, 2014;Arrangio et al, 2015;Bertrand et al, 2018).…”

Section: Introductionmentioning

confidence: 85%

“…Studies of transported biomass burning aerosol are typically performed using instrumentation either on board aircraft (Capes et al, 2008) or located at low altitude (Bougiatioti et al, 2014;Vakkari et al, 2014) and continental mountain (Laing et al, 2016) sites. Aircraft measurements have the advantage of sampling aerosol over wide spatial and altitudinal ranges, but they are limited to short time periods, typically of a few days to a week (Capes et al, 2008;Dunlea et al, 2009). Ground sites are less constricted by time, but low-altitude sites are less often affected by pyro-convective wildfire plumes due to the high injection heights of wildfires (Val Martin et al, 2008a).…”

Section: Introductionmentioning

confidence: 99%

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Molecular and physical characteristics of aerosol at a remote free troposphere site: implications for atmospheric aging

et al. 2018

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Aerosol properties are transformed by atmospheric processes during long-range transport and play a key role in the Earth's radiative balance. To understand the molecular and physical characteristics of free tropospheric aerosol, we studied samples collected at the Pico Mountain Observatory in the North Atlantic. The observatory is located in the marine free troposphere at 2225 m above sea level, on Pico Island in the Azores archipelago. The site is ideal for the study of long-range-transported free tropospheric aerosol with minimal local influence. Three aerosol samples with elevated organic carbon concentrations were selected for detailed analysis. FLEXPART retroplumes indicated that two of the samples were influenced by North American wildfire emissions transported in the free troposphere and one by North American outflow mainly transported within the marine boundary layer. Ultrahigh-resolution Fourier transform ion cyclotron resonance mass spectrometry was used to determine the detailed molecular composition of the samples. Thousands of molecular formulas were assigned to each of the individual samples. On average ∼ 60 % of the molecular formulas contained only carbon, hydrogen, and oxygen atoms (CHO), ∼ 30 % contained nitrogen (CHNO), and ∼ 10 % contained sulfur (CHOS). The molecular formula compositions of the two wildfire-influenced aerosol samples transported mainly in the free troposphere had relatively low average O/C ratios (0.48 ± 0.13 and 0.45 ± 0.11) despite the 7-10 days of transport time according to FLEXPART. In contrast, the molecular composition of the North American out-flow transported mainly in the boundary layer had a higher average O/C ratio (0.57±0.17) with 3 days of transport time. To better understand the difference between free tropospheric transport and boundary layer transport, the meteorological conditions along the FLEXPART simulated transport pathways were extracted from the Global Forecast System analysis for the model grids. We used the extracted meteorological conditions and the observed molecular chemistry to predict the relative-humidity-dependent glass transition temperatures (T g ) of the aerosol components. Comparisons of the T g to the ambient temperature indicated that a majority of the organic aerosol components transported in the free troposphere were more viscous and therefore less susceptible to oxidation than the organic aerosol components transported in the boundary layer. Although the number of observations is limited, the results suggest that biomass burning organic aerosol injected into the free troposphere is more persistent than organic aerosol in the boundary layer having broader implications for aerosol aging.

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Section: Introductionmentioning

confidence: 85%

Section: Introductionmentioning

confidence: 99%

Molecular and physical characteristics of aerosol at a remote free troposphere site: implications for atmospheric aging

et al. 2018

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“…The extracts were then filtered (0.22 µm) and analyzed the next day. N and O isotope analyses of the extracted/dissolved aerosol nitrate ( 15 N/ 14 N, 18 O/ 16 O) were performed using the denitrifier method (Sigman et al, 2001;Casciotti et al, 2002). Briefly, sample NO − 3 is converted to nitrous oxide (N 2 O) by denitrifying bacteria that lack N 2 O reductase activity (Pseudomonas chlororaphis ATCC 13985; formerly Pseudomonas aureofaciens, referred to below as such).…”

Section: Laboratory Analysismentioning

confidence: 99%

Nitrogen isotope fractionation during gas-to-particle conversion of NOx to NO3− in the atmosphere – implications for isotope-based NOx source apportionment

et al. 2018

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Abstract. Atmospheric fine-particle (PM2.5) pollution is frequently associated with the formation of particulate nitrate (pNO3−), the end product of the oxidation of NOx gases (NO + NO2) in the upper troposphere. The application of stable nitrogen (N) (and oxygen) isotope analyses of pNO3− to constrain NOx source partitioning in the atmosphere requires knowledge of the isotope fractionation during the reactions leading to nitrate formation. Here we determined the δ15N values of fresh pNO3− (δ15N–pNO3−) in PM2.5 at a rural site in northern China, where atmospheric pNO3− can be attributed exclusively to biomass burning. The observed δ15N–pNO3− (12.17±1.55 ‰; n = 8) was much higher than the N isotopic source signature of NOx from biomass burning (1.04±4.13 ‰). The large difference between δ15N–pNO3− and δ15N–NOx (Δ(δ15N)) can be reconciled by the net N isotope effect (εN) associated with the gas–particle conversion from NOx to NO3−. For the biomass burning site, a mean εN( ≈ Δ(δ15N)) of 10.99±0.74 ‰ was assessed through a newly developed computational quantum chemistry (CQC) module. εN depends on the relative importance of the two dominant N isotope exchange reactions involved (NO2 reaction with OH versus hydrolysis of dinitrogen pentoxide (N2O5) with H2O) and varies between regions and on a diurnal basis. A second, slightly higher CQC-based mean value for εN (15.33±4.90 ‰) was estimated for an urban site with intense traffic in eastern China and integrated in a Bayesian isotope mixing model to make isotope-based source apportionment estimates for NOx at this site. Based on the δ15N values (10.93±3.32 ‰; n = 43) of ambient pNO3− determined for the urban site, and considering the location-specific estimate for εN, our results reveal that the relative contribution of coal combustion and road traffic to urban NOx is 32 % ± 11 % and 68 %± 11 %, respectively. This finding agrees well with a regional bottom-up emission inventory of NOx. Moreover, the variation pattern of OH contribution to ambient pNO3− formation calculated by the CQC module is consistent with that simulated by the Weather Research and Forecasting model coupled with Chemistry (WRF-Chem), further confirming the robustness of our estimates. Our investigations also show that, without the consideration of the N isotope effect during pNO3− formation, the observed δ15N–pNO3− at the study site would erroneously imply that NOx is derived almost entirely from coal combustion. Similarly, reanalysis of reported δ15N–NO3− data throughout China and its neighboring areas suggests that NOx emissions from coal combustion may be substantively overestimated (by > 30 %) when the N isotope fractionation during atmospheric pNO3− formation is neglected.

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“…Inorganic ions (including SO4 2-, NO3 -, Cl -, NH4 + , K + , Ca 2+ , Mg 2+ , and Na + ), as well as 125 levoglucosan, a specific tracer of biomass burning, in cloudwater samples were analyzed using a Dionex TM ICS-5000 + system (ThermoFisher Scientific, Sunnyvale, USA). Detailed information regarding sample processing, pre-treatment, chemical analyses, analytical protocol adaption, detection limits, and method errors/reproducibility can be found elsewhere (Cao et al, 2016(Cao et al, , 2017.…”

Section: Chemical and Isotopic Analysismentioning

confidence: 99%

Isotopic Constraints on the Atmospheric Sources and Formation of Nitrogenous Species in Biomass-Burning-Influenced Clouds

Chang

Zhang

et al. 2018

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The interpretation of tropospheric cloud formation rests on understanding the sources and processes affecting aerosol constituents of the atmosphere that are preserved in cloudwater. 25 However, this challenge is difficult to be quantitatively addressed based on the sole use of bulk chemical properties. Nitrogenous aerosols, mainly ammonium (NH4 + ) and nitrate (NO3 -), play an important role in tropospheric cloud formation. Here we collected cloudwater samples at the summit of Mt. Tai (1545 m above sea level) in Eastern China during a long-lasting biomass burning (BB) event, and measured for the first time the isotopic compositions (mean ± 1σ) of 30 cloudwater nitrogen species (δ 15 N-NH4 + = -6.53 ± 4.96‰, δ 15 N-NO3 -= -2.35 ± 2.00‰, δ 18 O-NO3 -= 57.80 ± 4.23‰), allowing insights into their sources and potential transformation mechanism within the clouds. Large contributions of BB to the cloudwater NH4 + (32.9 ± 4.6%) and NO3 -(28.2 ± 2.7%) inventories were confirmed through a Bayesian isotopic mixing model, coupled with our newly-developed computational quantum chemistry module. Despite an overall reduction in total 35 anthropogenic NOx emission due to effective emission control actions and stricter emission standards for vehicles, the observed cloud δ 15 N-NO3values suggest that NOx emissions from transportation may have exceeded emissions from coal combustion. δ 18 O-NO3values imply that the reaction of OH with NO2 is the dominant pathway of NO3formation (57 ± 11%), yet the Atmos. Chem. Phys. Discuss., https://doi.

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Chemical characteristics of dicarboxylic acids and related organic compounds in PM2.5 during biomass-burning and non-biomass-burning seasons at a rural site of Northeast China

Cited by 81 publications

References 41 publications

Molecular and physical characteristics of aerosol at a remote free troposphere site: implications for atmospheric aging

Molecular and physical characteristics of aerosol at a remote free troposphere site: implications for atmospheric aging

Nitrogen isotope fractionation during gas-to-particle conversion of NO<sub><i>x</i></sub> to NO<sub>3</sub><sup>−</sup> in the atmosphere – implications for isotope-based NO<sub><i>x</i></sub> source apportionment

Isotopic Constraints on the Atmospheric Sources and Formation of Nitrogenous Species in Biomass-Burning-Influenced Clouds

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Chemical characteristics of dicarboxylic acids and related organic compounds in PM2.5 during biomass-burning and non-biomass-burning seasons at a rural site of Northeast China

Cited by 81 publications

References 41 publications

Molecular and physical characteristics of aerosol at a remote free troposphere site: implications for atmospheric aging

Molecular and physical characteristics of aerosol at a remote free troposphere site: implications for atmospheric aging

Nitrogen isotope fractionation during gas-to-particle conversion of NO&lt;sub&gt;&lt;i&gt;x&lt;/i&gt;&lt;/sub&gt; to NO&lt;sub&gt;3&lt;/sub&gt;&lt;sup&gt;−&lt;/sup&gt; in the atmosphere – implications for isotope-based NO&lt;sub&gt;&lt;i&gt;x&lt;/i&gt;&lt;/sub&gt; source apportionment

Isotopic Constraints on the Atmospheric Sources and Formation of Nitrogenous Species in Biomass-Burning-Influenced Clouds

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Nitrogen isotope fractionation during gas-to-particle conversion of NO<sub><i>x</i></sub> to NO<sub>3</sub><sup>−</sup> in the atmosphere – implications for isotope-based NO<sub><i>x</i></sub> source apportionment