"Chemical composition of pre-monsoon air in the Indo-Gangetic Plain measured using a new PTR-MS and air quality facility: high surface ozone and strong influence of biomass burning",
Atmos. Chem. Phys.
, vol. 14, pp. 5921-5941, 2014.
<p>One seventh of the world population lives in the Indo–Gangetic Plain (IGP) and the fertile region sustains agricultural food crop production for much of South Asia. Yet it remains one of the most under-studied regions of the world in terms of atmospheric composition and chemistry. In particular, the emissions and chemistry of volatile organic compounds (VOCs) that form surface ozone and secondary organic aerosol through photochemical reactions involving nitrogen oxides is not well understood. In this study, ambient levels of VOCs such as methanol, acetone, acetaldehyde, acetonitrile and isoprene were measured for the first time in the IGP. A new atmospheric chemistry facility that combines India's first high sensitivity proton transfer reaction mass spectrometer, an ambient air quality station and meteorological station, was used to quantify in-situ levels of several VOCs and air pollutants in May 2012 at a suburban site in Mohali (N. W. IGP). Westerly winds arriving at high wind speeds (5–20 m s−1) in the pre-monsoon season at the site, were conducive for chemical characterization of regional emission signatures. Average levels of VOCs and air pollutants in May 2012 ranged from 1.2–1.7 nmol mol−1 for aromatic VOCs, 5.9–37.4 nmol mol−1 for the oxygenated VOCs, 1.4 nmol mol−1 for acetonitrile, 1.9 nmol mol−1 for isoprene, 567 nmol mol−1 for carbon monoxide, 57.8 nmol mol−1 for ozone, 11.5 nmol mol−1 for nitrogen oxides, 7.3 nmol mol−1 for sulphur dioxide, 104 μg m−3 for PM2.5 and 276 μg m−3 for PM10. By analyzing the one minute in-situ data with meteorological parameters and applying chemical tracers (e.g. acetonitrile for biomass burning) and inter-VOC correlations, we were able to constrain major emission source activities on both temporal and diel scales. Wheat residue burning activity caused massive increases (> 3 times of baseline values) for all the measured VOCs and primary pollutants. Other forms of biomass burning at night were also a significant source for oxygenated VOCs and isoprene (r2 with acetonitrile ≥ 0.5 for night-time data), which is remarkable in terms of atmospheric chemistry implications. Surface ozone exceeded the 8 h national ambient air quality limit of 100 μg O3 m−3 on a daily basis, except for 17 May 2012, when a severe dust storm event (PM2.5 > 800 μg m−3; PM10 > 2700 μg m−3) characterized by long range transport from the west impacted the site. The novel dataset and results point to occurrence of high primary emissions of reactive VOCs. They also highlight the urgent need for establishing more comprehensive observational facilities in the IGP to constrain the spatial and seasonal variability of atmospheric chemical constituents. Such efforts will enable mechanistic level understanding of the in-situ chemical processes controlling formation of surface ozone, a necessary step for effective ozone mitigation and improvement of the regional air quality.</p>
[Sinha2008] "The Comparative Reactivity Method–a new tool to measure total OH Reactivity in ambient air",
Atmospheric Chemistry and Physics
, vol. 8, no. 8: Copernicus GmbH, pp. 2213–2227, 2008.
[Sinha2012a] "Constraints on instantaneous ozone production rates and regimes during DOMINO derived using in-situ OH reactivity measurements",
Atmospheric Chemistry and Physics
, vol. 12, no. 15: Copernicus GmbH, pp. 7269–7283, 2012.
In this study air masses are characterized in terms of their total OH reactivity which is a robust measure of the "reactive air pollutant loading". The measurements were performed during the DOMINO campaign (Diel Oxidant Mechanisms In relation to Nitrogen Oxides) held from 21/11/2008 to 08/12/2008 at the Atmospheric Sounding Station – El Arenosillo (37.1° N–6.7° W, 40 m a.s.l.). The site was frequently impacted by marine air masses (arriving at the site from the southerly sector) and air masses from the cities of Huelva (located NW of the site), Seville and Madrid (located NNE of the site). OH reactivity values showed strong wind sector dependence. North eastern "continental" air masses were characterized by the highest OH reactivities (average: 31.4 ± 4.5 s−1; range of average diel values: 21.3–40.5 s−1), followed by north western "industrial" air masses (average: 13.8 ± 4.4 s−1; range of average diel values: 7–23.4 s−1) and marine air masses (average: 6.3 ± 6.6 s−1; range of average diel values: below detection limit −21.7 s−1), respectively. The average OH reactivity for the entire campaign period was 18 s−1 and no pronounced variation was discernible in the diel profiles with the exception of relatively high values from 09:00 to 11:00 UTC on occasions when air masses arrived from the north western and southern wind sectors. The measured OH reactivity was used to constrain both diel instantaneous ozone production potential rates and regimes. Gross ozone production rates at the site were generally limited by the availability of NOx with peak values of around 20 ppbV O3 h−1. Using the OH reactivity based approach, derived ozone production rates indicate that if NOx would no longer be the limiting factor in air masses arriving from the continental north eastern sector, peak ozone production rates could double. We suggest that the new combined approach of in-situ fast measurements of OH reactivity, nitrogen oxides and peroxy radicals for constraining instantaneous ozone production rates, could significantly improve analyses of upwind point sources and their impact on regional ozone levels.