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Tropospheric Ozone Variability in Delhi During Pre & Post Monsoon Periods: Decoding Influence of Seasonal Variation, Diurnal Variation, Short Range and Long-Range Transport
Tropospheric Ozone Variability in Delhi During Pre & Post Monsoon Periods: Decoding Influence of Seasonal Variation, Diurnal Variation, Short Range and Long-Range Transport
Tropospheric Ozone Variability in Delhi During Pre & Post Monsoon Periods: Decoding Influence of Seasonal Variation, Diurnal Variation, Short Range and Long-Range Transport
7 * mukeshk@civil.iitd.ac.in, +91-11-2659-1212
9 Abstract
10 This study examines the contribution of various monitoring sites of Delhi categorized as Green Areas, Urban
11 Areas, Industrial/Commercial Areas, Traffic Areas, and Residential Areas. The mean hourly O3
12 concentration during the pre-monsoon season varies from 2630 to 8569 g/m3 and in post-monsoon
13 season varies from 1348 to 4958 g/m3. Maximum O3 concentration is found at sites categorized as Green
14 Areas and minimum at Industrial/Commercial Areas for both the pre-and post-monsoon seasons. The
15 contribution of O3 from short-and long-range transport, downward draft, biogenic emissions are found to be
16 maximum at green Areas which act as a sink for the O3. HYSPLIT cluster analysis was done to see the
17 influence of long-range transport on the O3 concentration across all sites. The air masses originating from
18 3500m or above contributed more to O3 in green Areas only. Air masses originating from S-W during pre-
19 monsoon and East during post-monsoon contributed to high concentration events in industrial/commercial
20 Areas only. The stubble burning episode in N-W contributed to high concentration events in urban areas
21 and residential areas. The contribution of O3 in Residential Areas can be attributed to long-range transport
22 from the N-W direction with air-masses originating at height <1500 m and the local influences.
23 Keywords: Tropospheric Ozone, HYSPLIT back trajectory analysis, Long-range transport, short-range
25
26 1.0 Introduction
28 on human health and is also linked to climate change (Kumari et al., 2020; Ghude et al., 2016; Londhe et al.,
29 2008). The concentration of O3 in ambient air is continuously increasing due to growing consumption of fossil
30 fuels for transportation, increase in power generation and industries (Chand & Lal, 2004; Debaje & kakade, 2006).
31 The concentration of O3 in ambient air is increasing at a rate 1-2% per year for the O3 present in troposphere as
32 well as the O3 near the earth surface (Lal et al., 1999; Kumari et al., 2020; Verma et al., 2017).
33 The O3 levels present in the troposphere are majorly attributed to two phenomena, one, stratosphere to troposphere
34 exchange of the O3 and two, photochemical generation from precursors such as CH4, CO, and VOCs, in presence
35 of NOx from anthropogenic and natural processes. Further, long-range transport of O3 may also be one of the
36 reasons for O3-rich air masses. The contribution of O3 from the stratosphere to troposphere exchange is 23%; and
37 the contribution of O3 production from the photochemical generation is the major source of O3 in ambient air
38 (Verma et al., 2017; Yadav et al., 2016; Sinha et al., 2021; Lal et al., 2017, Mahapatra et al., 2014). The
39 concentration of O3 in ambient air is either dependent on VOCs or NOx. The areas where the concentration of O3
40 in ambient air is dependent on VOCs, termed as VOCs-sensitive regime; where the concentration of O3 is
41 dependent on the NOx concentration, termed as NOx-sensitive regime. However, In India, it is considered to be
42 NOx limited for the photochemical production of O3 because anthropogenic emissions of NOx from combustion
43 activities are dominant (Verma et al., 2018; Debaje & kakade, 2006). The increase in the O3 levels can be attributed
44 to various reasons such as the meteorological conditions, the ventilation coefficient, the precursor emissions,
45 decreased O3 titration due to limited NOx emissions, and rapid production of ozone due to the local photochemical
46 reactions in warm and calm wind conditions. Further, the long-range transport of O3 at regional scale may also be
47 possible if wind speeds are higher resulting into its advective transport to the local receptor (Pont & Fontan, 2001;
48 Verma et al., 2017; Yadav et al., 2016; Mahapatra et al., 2012; Kumari et al., 2020). Further, it has been observed
49 that the concentrations of O3 during weekends are relatively higher than those on weekdays. It may be due to
50 lower ambient concentration of particulate matter during weekends, which results in less absorption of sunlight
51 and so enhanced concentration of O3 during weekends. Besides, the heavy-duty vehicles number are higher on
52 weekends as there is no peak hour time restrictions which leads to higher NOx concentrations resulting into higher
53 O3 production (Dreher & Harley, 1998; Marr & Harley, 2002a, b; Debaje & kakade, 2006).
54 Ozone is also a major source of OH radical in the troposphere. The self-cleansing mechanism of the atmosphere
55 is also dependent on the OH radical (Mahapatra et al., 2018). The NO2 present in the air acts as a catalyst, which
56 dissociates photochemically to form NO and atomic oxygen, O(3P) (Eq. 1) in the presence of solar radiation. In
58 2004; Yadav et al., 2016; Biswas et al., 2019; Kumari et al., 2020 Nelson et al., 2021):
60 The reaction between the oxygen atom and oxygen molecule leads to the formation of O3 (Eq. 2). The NO
61 produced in Eq. 1 reacts with HO2 radical and converts back into NO2 (Eq. 3), which acts as a catalyst for the O3
62 production process.
65 However, in the absence of sunlight i.e., at night, O3 reacts with NO2 to form nitrate radical (NO3) (Eq. 4) in the
66 ambient air, which in turn aids in the removal of NOx from the atmosphere.
67 𝑂3 + 𝑁𝑂2→𝑁𝑂3 (E4)
68
69 The present study includes analysis and description of O3 ambient concentrations at 23 different locations of the
70 Delhi city, having different land use characteristics, and traffic density during the periods, February – June 2018
71 (pre-monsoon) and October 2018 – January 2019 (post-monsoon). Besides, the source identification has also been
72 carried out using backward trajectory cluster analysis at few selected sites.
73
74 2.0 Materials and Methods
76 The study region is the National Capital Territory (NCT) of Delhi, NCT comprises the capital city of Delhi and
77 surrounding cities in states of Haryana, Uttar Pradesh, and Rajasthan (Figure 2). It is located at an altitude of 215m
78 above mean sea level and is among the 132 declared non-attainment cities (NCAP, 2021). It is landlocked by state
79 of Haryana and Punjab from the west side, where crop burning activities are maximum during the months of
80 October-November and state of Uttar Pradesh which is the most populated state of India from east side (Kalbande
81 et al., 2021). As per the WHO (2018) report, the cities with high ambient air pollution levels across the world,
82 India has thirteen cities in it including Delhi. Delhi ranks highest in the economic loss per capita due to premature
84 Delhi has semi-arid climate and experiences four major seasons Winter (Dec-Feb), Summer (Mar-May), Monsoon
85 (Jun-Aug) and Post-Monsoon (Sep-Nov) (Sharma et al., 2021; Kumar et al., 2017). During summer the city is
86 influenced by the dry weather, during the season with temperature reaching up to as high as 500C. This season is
88 in West. The dry season can be categorized into two periods, i.e., summer, and post-monsoon, during which the
89 solar radiation is high (Sinha et al., 2021). The rainfall experienced during the monsoon season comprises of the
90 80% of the annual rainfall (500-800 mm) of the city, it begins with the arrival of southwestern winds travelling
91 from the Arabian sea (Sharma et al., 2021; Perrino et al., 2011). The southwest monsoon is dominant over this
92 region during the monsoon season, precipitation, heavy rainfall, and high humidity is common during this season.
93 After the post-monsoon season, the air masses originate from the west and northwest direction as there is shift of
94 the southwest to northwest monsoon (Sinha et al., 2021). Comparative assessment of temperature and relative
95 humidity (RH) for pre- and post-monsoon season are given in Table 1. During pre-monsoon, the temperature of
96 the city reached up to 460C or sometimes more with mean-minimum temperature 150C during the month of March
97 and mean maximum temperature of 450C during the month of May (Warmest-month of Identified period); during
98 post-monsoon the temperature of the city goes down to 30C or sometimes less with mean minimum temperature
99 5.160C for the month of December (coldest month of the identified period) and mean maximum temperature 260C
100 for the same month due to frequent ground-based inversion conditions; the cold winds travel from the Himalayas
101 in the North-West (N-W) during post-monsoon season. The occurrence of haze, several fog and poor visibility
102 is common during this season. The high contrast in the summer and winter temperatures are attributes of the
103 Delhi’s Climate (Kalbande et al., 2021; Sharma et al., 2021; Kumar et al., 2017). The average RH during post-
104 monsoon was 43%, with 6% as the mean-minimum RH and 96% as the mean-maximum RH of all sites; the
105 average RH during post-monsoon was 66%, with 20% as the mean-minimum RH and 95% as the mean-maximum
107 Table 1: Seasonal comparative assessment of Temperature and Relative Humidity for pre-monsoon, and post-
109
110 Figure 1 shows the diurnal variation of Solar Radiation (SR) in pre- and post-monsoon seasons, the mean-
111 maximum SR was 720 Wm-2 and mean-minimum SR of all sites was 4 Wm-2 during the pre-monsoon season; the
(a) (b)
114 Figure 1: Diurnal variation assessment of Solar Radiation (SR) for (a) pre-Monsoon, and (b) post-Monsoon
115 season
117 The local air quality is influenced by the local emission sources contributions of the long-range transport,
118 meteorology, topographical factors, and Land use (Tombette and Sportisse, 2007; Mensink et al., 2007; Vautard
119 et al., 2007); which directly influences the concentration of pollutant across different locations. The ambient air
120 quality stations are categorized into different categories based on the location of the station to see the influence of
121 local sources on to the concentration of pollutant. In various studies, the average concentration of a specific
122 pollutant across all the stations is considered as the city average; however, it is not the case as the stations installed
123 are disproportionately located. The selected stations for this study are scattered throughout the city having
124 different surrounding environment. The sites selected for the analysis comprises of different types of areas such
125 as urban areas, industrial/commercial areas, traffic areas, residential areas, and green areas. The sites are selected
126 to compare the concentration of O3 in different types of areas and inter-comparison of O3 concentration in same
127 type of areas. The selection of monitoring stations was done based on data availability of O3, temperature, wind
128 speed (WS), wind direction (WD), relative humidity (RH), & solar radiation (SR). Continuous hourly average
129 data for all the selected parameters were selected from the whole datasets to assess the effect of meteorological
130 parameters at different sites on the O3 concentration. The missing values in the dataset are removed from the
131 analysis to properly understand the relationship of all meteorological variables with O3, replacing the missing
132 values with the median values will trade the original value of the relation between all variables. The outliers are
133 not removed from the study to understand about the influence of variables and location characteristics on to the
134 pollutant concentration. Table A1 describes the ambient air quality stations and their characteristics based on their
136 analysis.
137
138 Figure 2: Selected Delhi CAAQMS sites with varying characteristics
140 Hybrid Single-Particle Lagrangian Integrated Trajectory (HYSPLIT) model was used to understand the role of
141 transport of O3. The origin of air parcels can be discovered using the back trajectory analysis and these simulations
142 can be used for understanding the relationship between source and receptor by demarking the transport path to
143 monitoring locations (Draxler and Hess, 2004). The Global Assimilation Data System (GDAS 10) met-file was
144 included in the simulation for the back trajectory analysis, and simulations was done for 96-h back trajectory
145 arriving at the monitoring sites. These back trajectories provide a 3D air parcel path into the receptor sites as
146 derived from 3D gridded wind/pressure field. Single trajectories do not provide clear understanding of the
147 pathways for air parcel reaching the receptor locations, however, clustering of the trajectories using k-means
148 clustering provides better understanding and a better continuous delineation of the pathways can be achieved by
149 including large number of trajectories (Camalier et al., 2007; Saini et al., 2014; Verma et al., 2017; Kaspargolu et
150 al., 2018; Mukherjee et al., 2018). The monthly back trajectory cluster analysis was performed at height of 50 m
151 through vertical velocity model to understand the influence of long-range transport on the monitoring sites (Tu et
152 al., 2007; Mahapatra et al., 2012). The monthly back trajectory cluster is given in figures 3 and 4.
3 ( 13%) 40
at 28.67 N 77.13 E
at 28.67 N 77.13 E
40
50
55
55
60 2 ( 20%) 35 4 ( 7%) 60 35
65 65 90
70 2 ( 36%) 70 75 80 85
75 80
130
( 35%)
1 ( 59%)
30
3 ( 23%)
Source
Source
25
25
4 ( 8%)
20
Meters AGL
Meters AGL
3000
3000 2500
2000
2000 1500
1000 1000
500
50 50
12 24 36 48 60 72 84 96 12 24 36 48 60 72 84 96
March April
40
at 28.67 N 77.13 E
40 30
2 ( 34%)
50
455
( 7%) 60 90
70 803 ( 36%)
60 35
65 90
70 75 80 85 20
2 ( 55%)
3 ( 16%)
30
1 ( 16%)
Source
Source
1 ( 22%) 10
25 4 ( 14%)
0
Meters AGL
Meters AGL
3000 1500
2500
2000 1000
1500
1000 500
500 50
50 12 24 36 48 60 72 84 96
12 24 36 48 60 72 84 96
May June
153 Figure 3: Month wise HYSPLIT Back Trajectory Cluster Analysis for Pre-Monsoon Season
154 Figure 3 shows the month wise back trajectory cluster analysis for the pre-monsoon season which shows that the
155 predominant wind direction for the month of March, April and May is N-W with sometimes air masses originating
156 at height more than 3000m. During April and May, the influence of air masses originating from Indo-Gangetic
157 Plain (East (IGP)) at height of less than 500m and reaching the study location can be observed. The cluster analysis
158 for the month of June reveals that the air masses originating from South-West and East i.e., IGP at height of less
159 than 500m; and air masses from N-W originating at height of 1000m, are equally distributed i.e., South-West
161 Figure 4 shows the month wise back trajectory cluster analysis for the post-monsoon season which shows that the
162 predominant wind direction for the month of October, November and January is N-W with air masses originating
163 at height of 1500m for few clusters in October and January, and at height of 2500m for few clusters in November.
164 The influence of air masses originating from east i.e., IGP at height of less than 500m and reaching the study
166 reaching the study site is composed of various clusters, majorly from N-W direction and east for the month of
167 December. Further, it has been observed that for most of the clusters, the air masses originating at height of 2000m
168 or less except cluster 1 which originates at a height of more than 3500m and contributes almost 8% of the total air
at 28.67 N 77.13 E
1 ( 41%) 32
34
74 80 82
76 78 68 70
2 ( 26%) 72 74 76 78 80
30
32
2 ( 50%)
3 ( 26%)
Source
Source
4 ( 9%)
28 30
28
26
Meters AGL
Meters AGL
1500 2500
1000 2000
1500
500
1000
50 500
12 24 36 48 60 72 84 96 50
12 24 36 48 60 72 84 96
October November
Cluster means - Standard
Cluster means - Standard 646 backward trajectories
646 backward trajectories GDAS Meteorological Data
GDAS Meteorological Data 34
1 ( 53%)
40
1 ( 8%)
at 28.67 N 77.13 E
at 28.67 N 77.13 E
3 ( 17%)
65
70 75 80 85
32
35 72 74 76 78 80
4 ( 15%)
6 ( 11%)
7 ( 23%) 2
30( 30%)
Source
Source
3 ( 24%)
2 ( 7%)
30
8 ( 7%) 5 ( 6%) 28
Meters AGL
3500
Meters AGL
3000
2500 1500
2000
1500 1000
1000
500 500
50
12 24 36 48 60 72 84 96 50
12 24 36 48 60 72 84 96
December January
170 Figure 4: Month wise HYSPLIT Back Trajectory Cluster Analysis for Post-Monsoon Season
171
172 3.0 Results and Discussions
173
174 3.1 O3 concentrations in pre-monsoon season and post-monsoon season
175 Boxplots for the O3 concentration (in g/m3) for pre-monsoon and post-monsoon season for all 23 sites are given
176 in Figure 5. The mean concentration of O3 during the pre-monsoon season (2630 to 8569 g/m3) is higher than
178 concentration is observed in areas categorized as green areas as compared to the other areas. The reasons for high
179 O3 concentration at green areas may be due to (i) green areas act as sink for the O3 emissions from urban
180 areas/traffic areas/commercial areas/residential areas due to higher vehicular activities and combustion sources,
181 (ii) O3 has a longer lifetime and it is possible that the higher concentration at green areas could be attributed to the
182 long-range or short-range transport of O3 from the precursor locations, (iii) the biogenic volatile organic
183 compounds (VOCs) emitting from the flora contributing to the formation of O3, as they are more reactive than
184 anthropogenic VOCs (Paoletti, 2009; Verma et al., 2017; Yadav et al., 2016; Sinha et al., 2021; Lal et al., 2017,
185 Mahapatra et al., 2014). The mean O3 concentration in traffic areas is low, but high concentration events are
186 observed in these areas during both day and night. (Yadav et al., 2016; Verma et al., 2017; Sharma et al., 2021;
187 Sinha et al., 2021). The lower concentration of O3 during the post-monsoon season can be attributed to low mixing
188 layer height during these months, low solar radiation as compared to the pre-monsoon season, low average
189 temperature and high relative humidity (Mahapatra et al., 2012; Sinha et al., 2021).
190
191 Figure 5: Boxplot for hourly O3 concertation for pre-monsoon (left) and post-monsoon (right) season
192
193 3.2 Correlation Analysis of ozone and meteorological parameters
194
195 The correlation between the hourly O3 concentration and meteorological parameters on different sites for pre-
196 monsoon and post-monsoon season are given in figure 6. The hourly O3 concentration shows positive correlation
197 with the wind speed, temperature & solar radiation for both seasons, however, the relative humidity shows
198 negative correlation with the hourly O3 concentration. The wind direction has not much influence on the hourly
200 variables for different sites across Delhi city. All the sites categorized as green areas show strong positive
201 correlation with temperature & solar radiation, and strong negative correlation with the relative humidity for both
202 the pre-monsoon (Temp: 0.18-0.73, RH: (-0.43) - (-0.72), SR: 0.57-0.69) and post-monsoon season (Temp: 0.14-
203 0.76, RH: (-0.19) - (-0.77), SR: 0.15-0.70); the correlation for industrial/commercial correlation for post-monsoon
204 (Temp: 0.38-0.71, RH: (-0.41) - (-0.78), SR: 0.39-0.62) is season is stronger than that of pre-monsoon season
205 (Temp: 0.40-0.58, RH: (-0.38) - (-0.57), SR: 0.48-0.64); in urban areas the correlation for pre-monsoon (Temp:
206 0.46-0.67, RH: (-0.41) - (-0.78), SR: 0.42-0.69) and post-monsoon season (Temp: 0.43-0.67, RH: (-0.47) - (-
207 0.74), SR: 0.42-0.76), positive correlation between temperature & solar radiation with O3, and relative humidity
208 shows a strong negative correlation, Weak positive correlation is observed between wind speed and O3
209 concentration (0.08 - 0.56); in traffic areas Anand Vihar site do not show correlation with any of the
210 meteorological parameters (Temp: 0.17 - 0.20, RH: (-0.063) - (-0.24), SR: 0.11 – 0.12), the lower correlation with
211 solar radiation indicates the high nighttime O3 concentrations. Nehru Nagar site shows correlation similar to that
212 of urban areas; in residential areas the correlation for pre-monsoon (Temp: 0.37-0.65, RH: (-0.35) - (-0.61), SR:
213 0.44-0.67) and post-monsoon season (Temp: 0.25 - 0.65, RH: (-0.34) - (-0.74), SR: 0.33-0.54), the strong positive
214 correlation between temperature & solar radiation with O3 and strong negative correlation with relative humidity
215 is observed, except Punjabi Bagh site during pre-monsoon season and R. K. Puram during post-monsoon and the
216 correlation between wind speed and O3 concentration (0.22 – 0.54) on residential sites is better than all other sites
(a) (b)
217 Figure 6: Correlation plot between Ozone and meteorological Parameters for (a) pre-monsoon, and (b) post-
219
10
221 0.54), but during post-monsoon season the wind speed and O3 shows no correlation or weak correlation (0.088-
222 0.44) due to less wind speed during the post-monsoon season. All sites categorized as green areas show similar
223 trend between O3 and meteorological parameters except Mandir Marg (figure 2 & table A1). Mandir Marg is in
224 New Delhi with most of the surrounding areas are covered by forests; however, a connecting road between two
225 major roads is in proximity which experiences heavy traffic during peak hours; NOx and particulate matter from
226 vehicles can influence the concentration of O3 on this site. The dispersion of pollutants in the post-monsoon is
227 limited due to lower pressure gradient which indicates minimal horizontal mixing (Verma et al., 2017).
228
229 3.3 Diurnal & Seasonal Variation of Ozone
230 The mean O3 concentration varied from 29-85 g/m3 during the pre-monsoon season and 23-49 g/m3 during
231 post-monsoon season in green areas; 49-72 g/m3 during the pre-monsoon season and 20-39 g/m3 during post-
232 monsoon season in urban areas; 26-48 g/m3 during the pre-monsoon season and 13-40 g/m3 during post-
233 monsoon season in industrial/commercial areas; 38-67 g/m3 during the pre-monsoon season and 31 g/m3 on
234 both sites (Anand Vihar & Nehru Nagar) during post-monsoon season in traffic areas; 33-59 g/m3 during the
235 pre-monsoon season and 24-41 g/m3 during post-monsoon season in residential areas. The seasonal, diurnal,
236 monthly and day-wise variation of O3 for pre- and post-monsoon season are given in figure 7 and further in A1-
238 Mean monthly maximum O3 concentration was observed in month of May for pre-monsoon season for all areas
239 except for Anand Vihar and Punjabi Bagh site (figure 2 & table A1). Anand Vihar site is dominated by traffic and
240 diurnal pattern at this site is entirely different from all other sites; thus, high concentration is observed during
241 month of April. Punjabi Bagh site experiences very high concentration in month of March as compared to other
242 sites. Mean monthly maximum O3 concentration was observed in month of October for post-monsoon season for
243 all areas except residential areas. Apart from Dwarka and Jahangirpuri (figure 2 & table A1) all other sites have
244 maxima during different months. While R. K. Puram (figure 2 & table A1) site has maxima during month of
245 December, Punjabi Bagh and Rohini site had maxima in month of November and January respectively. The
246 seasonal variation suggests that the ozone at these areas is influenced more by the local sources, as visualized
247 using the polar plots given in figure A19 & A20.
248 The diurnal pattern of ozone concentration during pre-monsoon season shows a unimodal peak which is consistent
249 with the finding from Varshney and Aggarwal, 1992; the high O3 concentration for pre-monsoon season was
11
251 around 13:00-14:00 h for all areas except traffic and residential areas. Residential areas show bimodal peak with
252 another peak during the night-time between 00:00-5:00 h. At traffic areas the maximum hourly concentration is
253 observed during 11:00 - 18:00 h, 21:00 – 23:00 h, and 00:00 - 03:00 h; it shows a trimodal peak. Anand Vihar
254 (traffic area) is located in east Delhi; it is in close vicinity to an Inter State Bus Terminus (ISBT) with heavy traffic
255 load mostly consisting of Light Commercial Vehicles (LCVs), and Heavy Commercial Vehicles (HCVs), mainly
256 buses. The site is in neighborhood of Industrial and Commercial Areas and lies on the border of Delhi and Uttar
257 Pradesh (Goyal et al., 2019). The maxima during the night hours at Anand Vihar site can be due to the presence
258 of high vehicular activity that increases the NO titration effect and reduces the O3 concentration during night.
259 High concentration events are observed for few days every month in pre-monsoon season. However, during post-
260 monsoon season the high nighttime concentration events are attenuated in the month of October and December.
261 The Lower O3 concentrations during nighttime allows for the downdraft at night, which gets associated with the
262 surface to the lower troposphere and brings down air with high O3. This is more distinct during the night than in
264 The O3 concentration for post-monsoon season also shows unimodal peak feature, the high O3 concentration was
265 observed between 12:00-15:00 h; it starts increasing after 09:00-10:00 h and the maximum concentration is
266 observed around 14:00 h for all sites except traffic and residential areas. Traffic & Residential areas show bimodal
267 peak feature with another peak during the night-time between 01:00-06:00 h & 00:00-5:00 h, respectively. The
268 unusual peaks during the early morning hours can be due to urban heat island effect and carry over of O3, the
269 reduction in NO from vehicles leading to dilution of titration effect, and downdraft at night (Betts et al., 2002;
270 Matt and Harley, 2002; Taha 2008; Mahapatra et al., 2012).
271 It is interesting to note that the mean monthly O3 concentration at Mundka site for the month of June is
272 approximately 10 g/m3 which is 80% less than the month of May and 73% less than the average pre-monsoon
273 concentration on the site. The mean monthly O3 concentration of Okhla during the month of November is 5 g/m3,
274 which is 75% less than the concentration in month of October and 62% less than the average of post-monsoon
275 season. The sudden change in the monthly mean concentration at these are a matter of intensive investigation. The
276 mean monthly O3 concentration of Industrial/commercial sites is least during the pre-monsoon season followed
277 by urban areas, residential areas, traffic areas and green areas, respectively. However, during post-monsoon the
278 mean monthly O3 concentration at Industrial/commercial sites is equivalent to that of urban areas followed by
12
282
283 3.4.1 Green Areas
284 The bivariate polar plots for O3 in green areas have been shown in figures A3 & A4. The bivariate polar plots
285 show that during the pre- and post-monsoon seasons, the high O3 concentration is associated with higher wind
286 speeds (>2 m/s), indicating regional movement of O3 to the monitoring sites except at the Mandir Marg site
287 (Mukherjee et al., 2018; Grange et al., 2016). The long-range transport of O3 and emission of biogenic VOCs
288 from the vegetation in urban green areas lead to the formation of O3 in green areas. The relative high concentration
289 of O3 in green areas qualify the role of vegetation as the sink for O3 (Manes et al., 2008).
290 Figure 7 shows the variation of ozone at Dr. Karni Singh shooting range site for the pre-monsoon (Fig. 7(a)) and
291 post-monsoon season (Fig. 7(c)) along with the bivariate polar plots for pre-monsoon (Fig. 7(b)) and post-
292 monsoon season (Fig. 7(d)). Figure 7(e) shows the ozone air mass concentration Hysplit plots for the month of
293 march, indicating that maximum concentration episodes are attributed to cluster 1 (shown in figure 3) originating
294 from N-W direction at a height of approximately 1000m. However, Cluster 3 (13%) is also contributing high
295 concentration episodes as a result of the air masses originating from N-W direction at an approximate height of
296 4000m. Figure 7(f) shows the ozone air mass concentration Hysplit plots for the month of December. It clearly
297 shows the maximum concentration episodes are attributed to cluster 1, cluster 4 and cluster 7. Cluster 1 contributes
298 8%, cluster 4 contributes 15%, and cluster 7 contributes 7% (figure 4). The plots for remaining sites are given in
300 The prevailing wind direction is similar as the respective sites for both seasons, especially for the low-
301 concentration events indicating that the locally originated O3 is similar for both seasons. The contribution of short-
302 range and long-range transport of O3 is higher than locally sourced O3. The 96-h back trajectory cluster analysis
303 for the month of December reveals that the O3 concentration events linked with air masses originating from N-W
304 more than 3500 m height are relatively higher than any other cluster, indicating the contribution of ozone from
305 long-range transport (Jain et al., 2007; Verma et al., 2017). Further, air masses originating from cluster 3 (13%)
306 during the month of March clearly shows the contribution of O3 episodes at the site. The polar plots also confirm
307 this fact (figure 7, A3 & A4). The hysplit plots show high-concentration events occurring during nights due to NO
308 titration. During daytime the tropospheric O3 concentration becomes considerably less due to dominance of
309 convective transfer (Betts et al., 2002; Khaiwal et al., 2019; Saxena et al., 2020).
13
c. d.
e. f.
310 Figure 7: (a) & (b) Time variation and Bivariate plots for ozone at Dr. Karni Singh Shooting Range site for
311 pre-monsoon season, (c) & (d) Time variation and Bivariate plots at Dr. Karni Singh Shooting Range site
312 for post-monsoon season, (e) & (f) Ozone Air mass concentration split plots for the month of March (Pre-
315 The bivariate polar plots for O3 in urban areas are given in figures A7 & A8. The bivariate polar plots show that
316 during the pre- and post-monsoon season the high O3 concentration is associated with low wind speeds (< 2 m/s)
317 indicating the presence of locally sourced O3 at the monitoring sites. The high concentration at lower wind speed
318 indicates that the dispersion of pollutants is lacking at the urban sites (Grange et al. 2016). The contribution of
14
320 long-range transport at urban areas during the pre-monsoon and post-monsoon is limited, except for few high-
321 concentration events as shown in figures A21-A28. During the month of May, the air masses originating from N-
322 W at height above 3000m is contributing to the high concentration events. During the post-monsoon season, the
323 contribution of O3 is linked with air-masses originating from N-W direction in the month of October, November
324 and January. The concentration of O3 at urban sites is higher in the month of October and November due to stubble
325 burning in N-W regions. The releases of VOCs during the stubble burning i.e., Benzene and Toluene increase the
326 O3 formation potential in Delhi and result in higher concentrations (Kalbande et al., 2021). However, it has been
327 observed that during the month of December, the air masses originating from east i.e., IGP, and N-W region is
328 affecting the concentration of O3 at urban areas. The wind speeds are higher resulting into its advective transport
329 to the local receptor (Pont & Fontan, 2001; Chelani, 2013).
331 The bivariate polar plots for O3 in industrial/commercial areas are given in figures A11 & A12. The bivariate
332 polar plots show that during the pre-monsoon season the high concentration of episodes are linked with high wind-
333 speeds except at the Okhla site, whereas in post-monsoon season the higher concentration of O3 is associated with
334 both high and low wind speeds, indicating the transport of pollutants to the monitoring site and locally sourced
335 O3, respectively. The predominant wind direction during the pre-monsoon season were North, North-East or N-
336 W, whereas during the post-monsoon season all the sites had different predominant wind direction indicating
337 contribution of diffused local sources to O3 (Ramli et al., 2010). During the pre-monsoon season the contribution
338 of air-masses originating from the N-W direction is higher in the month of March, April, and May. However,
339 during the month of June the air masses originating from the Arabian sea in South-West direction influence the
340 O3 concentration. In the month of October, the air masses originating from east i.e., IGP at a height <500 m is
341 contributing more to the high O3 concentration events, as this region is also influenced by the stubble burning
342 (Kalbande et al., 2021). In the month of January, the contribution of long-range transport is negligible as shown
343 in figures A21-S28. It can be due to lower mixing height during the month and very high humidity. The ozone
344 formed near the ground can be assorted into the higher levels of mixing height during the day, or ozone trapped
345 upwards in the residual layer during the night. Alternatively, it can be appropriated downwards into the ground
346 level on the succeeding day (Singh et al., 1997; Pont & Fontan, 2001; Kim et al., 2007; Chelani, 2013 ; Mahaptra
348
15
350 The bivariate polar plots for O3 in traffic areas are given in figures A15 & A16. These show high concentration
351 episodes at the Anand Vihar site (figure 2 and Table A1) during the pre- and post-monsoon season, linked with
352 high wind-speeds transporting pollutants to the monitoring site. The contribution of pollutants during high-
353 concentration events from N-W is predominant during pre-monsoon season, however, the direction changes to
354 South-East during post-monsoon. The contribution of O3 at Nehru Nagar site (figure 2 and Table A1) from
355 localized sources is more as compared to transport of pollutants from other areas. The predominant wind direction
356 during the pre- and post-monsoon season were same i.e., East or N-W. N-W direction is associated with high
357 concentration events whereas East direction is associated with low-concentration events signifying a common
358 source during both the seasons which can be vehicles as this area is traffic dominated. The trend shown at this site
359 is different from Anand Vihar site, since it is not much impacted by LCVs and HCVs. The back trajectory cluster
360 analysis and O3 air mass concentration hysplit plots (Figures A21-A28), during the pre-monsoon season show that
361 the major contribution is locally sourced at the sites. During the post-monsoon season, the contribution of O3 via
362 long-range transport is similar as observed in urban areas (section 3.4.2) having major contribution of O3 from
365 The bivariate polar plots for O3 in residential areas are given in figures A19 & A20. All the sites have mostly one
366 predominant direction of O3 during pre-monsoon season except Punjabi Bagh (figure 2 and Table A1), where the
367 high-concentration and low-concentration events are both linked by two different directions 1800 opposite of each
368 other i.e., South-West and North-East. During post-monsoon season only R. K. Puram site (figure 2 and Table
369 A1) experienced O3 from the locally sources whereas all the other sites attribute high-concentration events during
370 high wind speeds implying the contribution of O3 via advective transport (Mukherjee et al., 2018). The air mass
371 O3 concentration split plots show that during the pre-monsoon season the high O3 concentration event are linked
372 with air masses originating from N-W direction and east i.e., IGP. The O3 contributing air masses originate from
373 heights <1500m during all the months. During the months of October and November, the residential site
374 experiences high O3 concentration events when the air masses are originating from the N-W region. It can also be
375 linked with the stubble burning during October and November months. Further, the contribution of O3 during the
376 months of December and January is associated with air masses originating from N-W and local sources.
16
379 traffic areas, and residential areas show different O3 concentrations and are influenced by various sources ranging
380 from locally sourced to long-range transport. The O3 concentration shows strong positive correlation with
381 temperature and solar radiation; strong negative correlation with relative humidity; and weak positive correlation
382 with wind speed. There is no evidence of any relationship between wind direction and O3 concentration. Almost
383 all the sites show similar correlations with the meteorological factors except the Anand Vihar site (figure 2 and
385 The O3 concentration are highest on the stations categorized as green areas. These stations experience high O3
386 concentration during both pre- and post-monsoon seasons. The lowest O3 concentration is observed at
387 industrial/commercial areas. The O3 concentration at green areas are primarily due to long-range & short-range
388 transport as well as local biogenic sources. The back trajectory cluster analysis also this. Further, the green areas
389 act as a sink for O3 as well. Besides, the stubble burning in Haryana-Punjab regions (N-W) influences the O3
390 concentration in urban and residential areas. Whereas the stubble burning in east i.e., IGP, influences the O3
391 concentration in industrial/commercial areas. The traffic areas are not much influenced by the long-range
392 transport of O3. The high concentration at night in traffic areas can be attributed to the downdraft of O3.
393
394 Acknowledgements
395 The author/authors gratefully acknowledge the ozone and meteorological data provided by the Delhi Pollution
398
399 References
400
401 Agrawal, S. B., Singh, A., & Rathore, D. (2005). Role of ethylene diurea (EDU) in assessing impact of ozone
402 on Vigna radiata L. plants in a suburban area of Allahabad (India). Chemosphere, 61(2), 218-228.
403 Betts, A. K., Gatti, L. V., Cordova, A. M., Dias, M. A. S., & Fuentes, J. D. (2002). Transport of ozone to the
404 surface by convective downdrafts at night. Journal of Geophysical Research: Atmospheres, 107(D20), LBA-
405 13.
17
407 observations of nitrogen dioxide, formaldehyde and ozone in the Indo-Gangetic Plain. Aerosol and Air
409 Camalier, L., Cox, W., & Dolwick, P. (2007). The effects of meteorology on ozone in urban areas and their
411 Chand, D., & Lal, S. (2004). High ozone at rural sites in India. Atmospheric Chemistry and Physics
413 Chelani, A.B., 2013. Study of extreme CO, NO2 and O3 concentrations at a traffic site in Delhi: Statistical
414 persistence analysis and source identification. Aerosol and Air Quality Research, 13(1), pp.377-384.
415 Debaje, S. B., & Kakade, A. D. (2006). Measurements of surface ozone in Rural site of India. Aerosol and
417 Debaje, S. B., & Kakade, A. D. (2006). Weekend ozone effect over rural and urban site in India. Aerosol and
419 Dreher, D. B., & Harley, R. A. (1998). A fuel-based inventory for heavy-duty diesel truck emissions. Journal
421 Elkamel, A., Abdul-Wahab, S., Bouhamra, W., & Alper, E. (2001). Measurement and prediction of ozone
422 levels around a heavily industrialized area: a neural network approach. Advances in environmental
424 Escudero, M., Lozano, A., Hierro, J., del Valle, J., & Mantilla, E. (2014). Urban influence on increasing
425 ozone concentrations in a characteristic Mediterranean agglomeration. Atmospheric Environment, 99, 322-
426 332.
427 Ghude, S. D., Chate, D. M., Jena, C., Beig, G., Kumar, R., Barth, M. C., ... & Pithani, P. (2016). Premature
428 mortality in India due to PM2. 5 and ozone exposure. Geophysical Research Letters, 43(9), 4650-4658.
429 Gorai, A. K., Tchounwou, P. B., & Mitra, G. (2017). Spatial variation of ground level ozone concentrations
430 and its health impacts in an urban area in India. Aerosol and air quality research, 17(4), 951.
431 Goyal, P., Gulia, S., Goyal, S. K., & Kumar, R. (2019). Assessment of the effectiveness of policy
432 interventions for Air Quality Control Regions in Delhi city. Environmental Science and Pollution
18
435 bivariate correlation and regression statistics. Atmospheric Environment, 145, 128-134.
436 Jain, S. L., Arya, B. C., Kumar, A., Ghude, S. D., & Kulkarni, P. S. (2005). Observational study of surface
437 ozone at New Delhi, India. International Journal of Remote Sensing, 26(16), 3515-3524.
438 Kalbande, R., Bano, S., & Beig, G. (2021). Benzene and Toluene from Stubble Burning and Their
439 Implications for Ozone Chemistry and Human Health in the Indo-Gangetic Plain Region. ACS Earth and
441 Kasparoglu, S., Incecik, S., & Topcu, S. (2018). Spatial and temporal variation of O3, NO and NO2
442 concentrations at rural and urban sites in Marmara Region of Turkey. Atmospheric Pollution Research, 9(6),
443 1009-1020.
444 Khemani, L. T., Momin, G. A., Rao, P. S. P., Vijayakumar, R., & Safai, P. D. (1995). Study of surface ozone
445 behaviour at urban and forested sites in India. Atmospheric Environment, 29(16), 2021-2024.
446 Kumar, P., Gulia, S., Harrison, R. M., & Khare, M. (2017). The influence of odd–even car trial on fine and
448 Kumari, S., Lakhani, A., & Kumari, K. M. (2020). First observation-based study on surface O3 trend in Indo-
449 Gangetic Plain: Assessment of its impact on crop yield. Chemosphere, 255, 126972.
450 Lal, S., Naja, M., & Subbaraya, B. H. (2000). Seasonal variations in surface ozone and its precursors over an
452 Lal, S., Venkataramani, S., Naja, M., Kuniyal, J. C., Mandal, T. K., Bhuyan, P. K., ... & Kumar, M. K. S.
453 (2017). Loss of crop yields in India due to surface ozone: an estimation based on a network of
455 Li, L., An, J., Huang, L., Yan, R., Huang, C., & Yarwood, G. (2019). Ozone source apportionment over the
456 Yangtze River Delta region, China: Investigation of regional transport, sectoral contributions and seasonal
458 Londhe, A. L., Jadhav, D. B., Buchunde, P. S., & Kartha, M. J. (2008). Surface ozone variability in the urban
459 and nearby rural locations of tropical India. Current science, 1724-1729.
460 Mahapatra, P. S., Jena, J., Moharana, S., Srichandan, H., Das, T., Chaudhury, G. R., & Das, S. N. (2012).
461 Surface ozone variation at Bhubaneswar and intra-corelationship study with various parameters. Journal of
19
464 ozone reduction event over eastern India by integrating in situ and satellite measurements with WRF-Chem
466 Mahapatra, P. S., Panda, S., Walvekar, P. P., Kumar, R., Das, T., & Gurjar, B. R. (2014). Seasonal trends,
467 meteorological impacts, and associated health risks with atmospheric concentrations of gaseous pollutants at
468 an Indian coastal city. Environmental Science and Pollution Research, 21(19), 11418-11432.
469 Manes, F., Salvatori, E., La Torre, G., Villari, P., Vitale, M., Biscontini, D., & Incerti, G. (2008). Urban green
470 and its relation with air pollution: ecological studies in the Metropolitan area of Rome. italian Journal of
472 Marr, L. C., & Harley, R. A. (2002). Modeling the effect of weekday− weekend differences in motor vehicle
473 emissions on photochemical air pollution in central California. Environmental science & technology, 36(19),
474 4099-4106.
475 Marr, L. C., & Harley, R. A. (2002). Spectral analysis of weekday–weekend differences in ambient ozone,
476 nitrogen oxide, and non-methane hydrocarbon time series in California. Atmospheric Environment, 36(14),
477 2327-2335.
478 Mukherjee, A., Agrawal, S. B., & Agrawal, M. (2018). Intra-urban variability of ozone in a tropical city—
479 characterization of local and regional sources and major influencing factors. Air Quality, Atmosphere &
481 Nelson, B. S., Stewart, G. J., Drysdale, W. S., Newland, M. J., Vaughan, A. R., Dunmore, R. E., ... & Lee, J.
482 D. (2021). In situ ozone production is highly sensitive to volatile organic compounds in the Indian megacity
484 Paoletti, E., (2009). O3 and urban forests in Italy. Environmental pollution, 157(5), pp.1506-1512.
485 Perrino, C., Tiwari, S., Catrambone, M., Dalla Torre, S., Rantica, E., & Canepari, S. (2011). Chemical
486 characterization of atmospheric PM in Delhi, India, during different periods of the year including Diwali
488 Pont, V. and Fontan, J., 2001. Comparison between weekend and weekday ozone concentration in large cities
20
491 precursors and prediction of O3 using multiple linear regressions. Malaysian Journal of Environmental
493 Ravindra, K., Singh, T., Mor, S., Singh, V., Mandal, T.K., Bhatti, M.S., Gahlawat, S.K., Dhankhar, R., Mor,
494 S. and Beig, G., 2019. Real-time monitoring of air pollutants in seven cities of North India during crop residue
495 burning and their relationship with meteorology and transboundary movement of air. Science of the total
497 Saini, R., Singh, P., Awasthi, B. B., Kumar, K., & Taneja, A. (2014). Ozone distributions and urban air quality
498 during summer in Agra–a world heritage site. Atmospheric Pollution Research, 5(4), 796-804.
499 Saxena, P., Srivastava, A., Verma, S., Singh, L. and Sonwani, S., 2020. Analysis of atmospheric pollutants
500 during fireworks festival ‘Diwali’at a residential site Delhi in India. In Measurement, analysis and
502 Sharma, A., Sharma, S. K., & Mandal, T. K. (2021). Ozone sensitivity factor: NOX or NMHCs?: a case study
503 over an urban site in Delhi, India. Urban Climate, 39, 100980.
504 Singh, A., Sarin, S.M., Shanmugam, P., Sharma, N., Attri, A.K. and Jain, V.K., 1997. Ozone distribution in
505 the urban environment of Delhi during winter months. Atmospheric Environment, 31(20), pp.3421-3427.
506 Sinha, P., Singh, S., Saroj, P., Beig, G., & Murthy, B. S. (2021). Study of surface ozone (O3) and its
507 relationship with NO, NO2, NOx, OX and CO at five different locations in New Delhi, India from 2013 to
508 2019.
509 Taha, H. (2008). Meso-urban meteorological and photochemical modeling of heat island
511 Tu, J., Xia, Z. G., Wang, H., & Li, W. (2007). Temporal variations in surface ozone and its precursors and
512 meteorological effects at an urban site in China. Atmospheric Research, 85(3-4), 310-337.
513 Varshney, C.K. and Aggarwal, M., 1992. Ozone pollution in the urban atmosphere of Delhi. Atmospheric
515 Verma, N., Lakhani, A., & Kumari, K. M. (2017). High ozone episodes at a semi-urban site in India:
517 Verma, N., Satsangi, A., Lakhani, A., & Kumari, K. M. (2018). Characteristics of surface ozone in Agra, a
518 sub-urban site in Indo-Gangetic Plain. Journal of Earth System Science, 127(3), 1-16..
21
520 meteorology in seasonal variation of surface ozone and its precursors at an urban site in India. Atmospheric
522 Zhu, X., Ma, Z., Qiu, Y., Liu, H., Liu, Q., & Yin, X. (2020). An evaluation of the interaction of morning
523 residual layer ozone and mixing layer ozone in rural areas of the North China Plain. Atmospheric
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