Seasonal Variability of O3 and NOy* and emission characteristics of CO and NOy* derived from one year of in-situ measurements

Vinod Kumar, 1Chinmoy Sarkar and 1Vinayak Sinha*

Department of Chemical sciences, IISER Mohali, SAS Nagar, Manauli, Punjab Email vsinha@iisermohali.ac.in

Abstract: - CO, NOy*( NOy* = NO + NO2 + PAN + organic nitrates + HNO3 + N2O5 + ...), O3 were measured for one year at a suburban site(76.726oN 30.679oE) at the northern Indo Gangetic plain. We have tried to sniff out point sources and to understand the seasonality and the day time and night time CO/NO y* emission characteristics in different seasons. Excellent positive correlation was found between CO and NO y* arriving from urban sector at receptor site in night time during winter and polluted post monsoon seasons(r=0.91 and r=0.83 respectively) with [CO]/[NOy*] = 29.120.07 ppmV/ppbV and 22.470.09ppbV/ppbV respectively, which is quite different from other inventories from previous studies.

Introduction Tropospheric ozone has been centre of atmospheric chemistry research from past few decades. It is a potential greenhouse gas and has adverse effects on human being and crop productivity. NO and NO2 are also key pollutants but main interest for their study is to determine the O3 distribution. Very few studies have reported long term high temporal resolution measurements and emission characteristics of these species over indogangetic plain. It is required to quantify the concentrations of these key species in order to access the environmental impacts and mitigation steps. Emission ratio is a representation of emission characteristics of different inventories and has been used extensively for different atmospheric chemistry models. In this paper we report the seasonal variability and [CO]/[NOy*] emission ratio for one year of 1 minute time resolution dataset. Our measurement site is a complex site as it is surrounded by different type of emission sources in different directions. We have tried to identify the NOy* emission signature of different sources using a receptor based approach. The [CO]/[NOy*] emission ratio is found to be quite different in the current

study as compared to previous known inventories and more work is required to explain it. Materials and Methods All the measurements were performed at atmospheric chemistry measurement facility at IISER Mohali (76.726oN 30.679oE, ~20m above ground level). The wind sector 310o to 100o, is the urban sector where the cities of Chandigarh, Mohali and Panchkula lie. 100o to 170o is mixed industrial and urban sector whereas 180o to 310o is the agricultural sector. NOx(NO + NO2) was measured using a commercial instrument(Thermo Fisher Scientific, Model No 42i), based on chemiluminescence reaction between NO and O3. A molybdenum converter heated at 325oC is employed inside the instrument to convert NO2 to NO. Previous studies have shown that this also converts peroxy acetyl nitrates (PAN), HNO3, N2O5, HONO and other organic nitrates to NO. Thus the instrument measures the total reactive nitrogen and henceforth we refer it as NOy* The detection limit of instrument is 0.05ppbV and the 1 minute time resolution data has an uncertainty of 7%(at 10ppbV, smaller uncertainty at higher mixing

ratios).Ozone was measured using a UVPhotometric analyzer(Thermo Fisher Scientific, Model No 49i). It has a detection limit of 1ppbV and uncertainty of 6 %( at 25ppbV) for 1 minute data. Carbon monoxide (CO) was measured using a non-dispersive infra red (NDIR) filter correlation spectroscopy based instrument (Thermo Fisher Scientific, Model No 48i). The detection limit of the analyzer is 40ppbV and uncertainty of 1 minute time resolution data is 7 %( at 100ppbv).Wind speed and Wind direction were measure using sensors manufacture by Met-One instruments. Solar radiation was measured using a pyranometer(met one instruments, Model No 095) which measures total radiation in 285nm to 2800nm wavelength window. All the data for which wind speed was less than 1m/s were filtered out to exclude any strong local contribution. Results and Discussions For better analysis of data, the one year period as divided into 5 different seasons based on meteorological parameters and anthropogenic activities. These are winter (10.12.2011 to 29.02.2012), summer (01.03.2012 to 01.07.2012), monsoon (02.07.2012 to 18.09.2012), clean post monsoon (CPM) (19.09.2012 to 07.10.2012) and polluted post monsoon (PPM) (08.10.2012 to 09.12.2012). As clear from figure 1, we can easily see season differences in daytime (solar radiation>50 Watt/m2) and night time (solar radiation<25 Watt/m2) levels of O3, NO and NO2. Summer seasons has long day time hours and higher regional ozone production. Very high night time ozone in summer can be explained by enhanced advection and transport. Monsoon season is characterized by dense cloud coverage; less continuous solar radiation and more wet deposition of O3 production precursors, and hence average O 3 levels are even smaller than those of winter seasons. There is enhanced crop residue burning in the polluted post monsoon season and other biomass burning in the winter season leading lo high ambient levels of NO x. Overall, the ambient levels of Ozone is found to be very high as compared to previous studies.The wind rose plot and diel profile of O3 and NOx for different sectors in different seasons helps to understand the chemistry of Ozone at this site in a better way. We have also calculated the [CO]/[NO y*] emission ratio for airmass coming from the urban sector in different seasons. The intercept of the fit between CO and NOy* gives the background CO levels which are always higher than 200ppV.

Figure 1 Daily average and variability (shaded region-1) of O3, NO and NO2 for one year. Topday time and BottomNight time Table 1 Season *O3 (Mean1) 40.518.0 20.411.7 66.819.7 36.815.6 33.214.6 15.712.3 53.621.8 28.713.3 52.622.3 22.014.8 *NO2 (Mean1) 14.79.3 20.720.3 8.47.2 12.49.2 5.63.8 8.05.5 6.24.2 7.13.4 10.87.1 18.316.4
#

[CO]/[NOy *] urban(r)

Winter (day) (night) Summer (day) (night) Monsoon (day) (night) CPM (day) (night) PPM (day) (night)

29.10.1(0.74) 22.40.2(0.91) 7.40.1(0.34) 17.80.1(0.67) 6.20.2(0.39) 21.90.3(0.73) 13.40.2(0.63) 19.20.2(0.71) 18.60.2(0.61) 22.50.1(0.83)

*in ppbv ; # in ppbv/ppbv

The [CO]/[NOy*] emission ratio is smaller than those reported in wang et. al, but are significantly higher than some other similar studies. Interestingly the summer time emission ratio is smaller in day time as compared to that in night time which is exactly reverse than previously reported studies. Currently work is going on for further analysis of this fact. Acknowledgement V.S. thanks IISER Mohali and MHRD, India for institutional support and funding without which this work would not have been possible. C.S. acknowledges the Max Planck-DST India Partner Group on Tropospheric OH reactivity and VOCs for a PhD fellowship. V.K acknowledges DST INSPIRE Fellowship program. References

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