Influence of Oxides of Nitrogen, Carbon Monoxide and Sulpher Dioxide on Surface Ozone Level in Diffe...

Ram Chhavi Sharma, Niharika Sharma

American Journal of Environmental Protection

Influence of Oxides of Nitrogen, Carbon Monoxide and Sulpher Dioxide on Surface Ozone Level in Different Meteorological Seasons in Haryana State, Northern India

Ram Chhavi Sharma1,, Niharika Sharma2

1Department of Physics, Faculty of Physical Sciences, Shree Guru Gobind Singh Tricentenary (SGT) University Gurgaon, Haryana, India

2Department of Chemistry, Government Senior Secondary School Kakoria Rewari, Haryana, India

Abstract

Surface Ozone concentrations are valuable indicators of possible health and environmental impacts. Increasing concentration of Tropospheric ozone (O3) is a serious air pollution problem faced commonly by the urban people. In the present study ozone (O3), Oxides of Nitrogen (NOx) Carbon monoxide (CO) and Sulpher dioxide (SO2) data were collected for a period of one year (January 01, 2015 to December 31, 2015) at three ambient air quality monitoring stations (Gurgaon now Gurugram, Rohtak and Panchkula) in Haryana state in Northern India. The O3, NOx CO, and SO2 data were collected by Haryana State Pollution Control Board. The concentration of O3 is correlated with the concentration of NOx, CO, and SO2 in different meteorological seasons. The regression correlation analysis has been performed between NOx, CO, SO2 and O3 to investigate the relationship between them. It was found that the variation in concentration of NOx, CO and SO2 influenced the changes in the concentration of O3 in different seasons of the year. The investigation data showed that NOx, CO and SO2 had the important influence on O3 concentration variations in monsoon session (r2 = -0.256, -0.322, -0.137 for Gurgaon, r2= 0.997, -0.829 and 0.843 for Rohtak and r2= – 0.854, -0.829 and 0.262 for Panchkula). The influence of SO2 on O3 concentration has been observed to be different from NOx and CO. O3 and NOx were observed to be inversely related in most of the seasons (r2= 0.124, 0.389, -0.256 and -0.694 in Gurgaon, r2 = -0.797, -0.819, 0.997 and -0.797 in Rohtak & r2=0.971,-0.074, -0.854 & 0.784 in Panchkula for spring, pre-monsoon, monsoon and post monsoon season respectively). The regression equations have been obtained which correlates O3 with NOx, CO and SO2.

Cite this article:

  • Ram Chhavi Sharma, Niharika Sharma. Influence of Oxides of Nitrogen, Carbon Monoxide and Sulpher Dioxide on Surface Ozone Level in Different Meteorological Seasons in Haryana State, Northern India. American Journal of Environmental Protection. Vol. 5, No. 1, 2017, pp 1-8. http://pubs.sciepub.com/env/5/1/1
  • Sharma, Ram Chhavi, and Niharika Sharma. "Influence of Oxides of Nitrogen, Carbon Monoxide and Sulpher Dioxide on Surface Ozone Level in Different Meteorological Seasons in Haryana State, Northern India." American Journal of Environmental Protection 5.1 (2017): 1-8.
  • Sharma, R. C. , & Sharma, N. (2017). Influence of Oxides of Nitrogen, Carbon Monoxide and Sulpher Dioxide on Surface Ozone Level in Different Meteorological Seasons in Haryana State, Northern India. American Journal of Environmental Protection, 5(1), 1-8.
  • Sharma, Ram Chhavi, and Niharika Sharma. "Influence of Oxides of Nitrogen, Carbon Monoxide and Sulpher Dioxide on Surface Ozone Level in Different Meteorological Seasons in Haryana State, Northern India." American Journal of Environmental Protection 5, no. 1 (2017): 1-8.

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1. Introduction

Air Pollution is a challenging problem as it would hinder sustainable development all over the globe [1]. The factors responsible for occurrence of air pollution include meteorological factors, earth surface topographic features and released air pollutants from various sources. Meteorological factors such as wind velocity, wind direction, temperature, and relative humidity together with earth surface roughness are effective agents for mixture of air pollutants. The most important role of meteorology is in the dispersion, transformation and removal of air pollutants from atmosphere. The wind speeds determine the amount of dispersion of pollutants while temperature contributes transformation of pollutants in the atmosphere. The topography and solar heating of region surrounding a particular pollution source affects the concentration. High pollution levels can be expected during fair weather conditions resulting local wind system and strong temperature inversions in cities situated in mountainous region. Air pollution may be classified into two types according to the nature of formation: primary pollutants which are emitted from their sources directly to the atmosphere such as industry, traffic, domestic heating in winter season and secondary pollutants which results from the chemical reaction between the primary pollutants. Examples of primary pollutants are oxides of nitrogen (NOx), carbon monoxide (CO) and sulphur dioxide (SO2). Examples of secondary pollutants are photochemical oxidants and ozone (O3).

Oxides of Nitrogen in the atmosphere originate either from natural processes or anthropogenic activity. In the lower atmosphere, nitric oxide (NO) is converted to nitrogen dioxide (NO2) by reaction with proxy-radicals (RO2) or O3. The NO2 generated is then undergoes photo dissociation in the atmosphere and the atomic oxygen released combines with molecular oxygen to form O3 [2]. The life time of NOx (NO+NO2) in the troposphere ranges from less than one day in summer to several days in the absence of active photochemistry.

Carbon monoxide is an important trace gas in the earth’s atmosphere, which performs several important roles in the troposphere. There are a variety of sources, both natural and anthropogenic, for ambient CO. Natural sources include oxidation of methane and natural hydrocarbons, ocean emissions, and emissions from vegetation. In rural areas, these are the most dominant sources; therefore, in a remote location, CO is one of the most dominant precursors for photo-chemical ozone production. In urban areas, however anthropogenic sources including fossil fuel combustion, industrial activities, motor vehicles, biomass burning, and oxidation of anthropogenic hydrocarbons, contribute far more to the concentration of CO than natural sources. The lifetime of CO is approximately 1-3 months, representing the slow rate of mixing and the consumption by reaction with OH. In the troposphere, a significant CO background concentration exists based on continuous CO production from the oxidation of methane and its long lifetime [2].

Sulfur dioxide is a major air pollutant and has significant impacts upon human health. Sulfur dioxide emissions are a precursor to acid rain and atmospheric particulates. It influenced O3 formation. Role of SO2 in O3 formation is dependent on HO2 produced from SO2 [3]. The utmost anthropogenic sources of SO2 consequences are from the burning of fossil fuels and from the smelting sulphide ores [4]. Among man made sources fuel combustion, industry and transportation are the main contributors. A significant feature of SO2 is that, once it is emitted from the atmosphere, it can be converted through complex oxidation reactions in to fine particulate sulphate and removed from the atmosphere by wet or dry deposition [5, 6].

Ozone is a major environmental concern because of its adverse impact on human health [7, 8] and also because of its impacts on crops and forest ecosystems [9, 10]. Tropospheric O3 may originate by interchange with the stratosphere and/or photochemical production. In the urban atmosphere, NOx and volatile organic compounds may either increase or decrease O3 concentrations. O3 formation is closely related to meteorological parameters such as temperature, solar radiation, and wind speed [11].

A thorough understanding of the relationship among O3, NOx, SO2 and CO under various atmospheric conditions is urgently needed to improve our understanding of the chemical coupling among these pollutants [12, 13, 14, 15, 16]. Seasonal variation effects on gaseous pollutants are of great significance to the life span and cycle of any pollutant in the lower atmosphere [17].

In the present study, the levels of air pollutants NOx, CO, SO2 and O3 were measured at three urban locations (Gurgaon, Rohtak and Panchkula) in Haryana state (Figure 1) for a period of one year from January 01,2015 to December 31, 2015. The concentrations of NOx, CO and SO2 were statistically correlated with concentration of O3 using regression analysis in spring, pre-monsoon, monsoon and post monsoon seasons. The regression equations have been obtained which correlates O3 with NOx, CO and SO2.

Figure 1. Map of Haryana state showing study area: Gurgaon (now Gurugram), Rohtak and Panchkula

2. Description of the Study Area

Haryana is the 20th state of India that came into being on 1st November 1966. It is situated in the North Western region surrounded by Himachal Pradesh from North, Uttrakhand from North East, Rajasthan from the South, U.P and Delhi from East and Punjab from North West. Three districts, Gurgaon, Rohtak and Panchkula of Haryana state have been selected for the present study. The brief information’s about sampling sites are given in Table 1.

Table 1. Information on Monitoring sites

Gurgaon district falls in the southern most region of the state of Haryana. To its advantage of being situated in vicinity of Delhi, Gurgaon falls under National Capital Region. It lies in between the 27° 39’ and 28° 32’25’’ latitude, and 76° 39’ 30’’ and 77° 20’ 45’’ longitude. Gurgaon is the sixth largest city of Haryana State and is situated on both sides of National highway 8. It accommodates a population of 1514432 (2011 Population census figures), 5.97 percent of the state population. Its density according to 2011 population census is 1204 persons per Sq. km. against 573 in the state, which get further compounded due to migration of people from different part of country in search of job. It has been on the faster pace of the development and emerged as the industrial and financial hub of Haryana. Rapid urbanization, increasing industrialization and enhanced men made perturbations added excess pollutants in the atmosphere resulting environmental degradation and climate change [18].

Rohtak district is located in southeastern part of Haryana State (30o 1’N, 75o 17’E) and constitutes a major part of eastern Haryana plain. The climate of Rohtak district is sub-tropical, semi arid, Continental and monsoon type. Thus, it has hot summers, cool winters and small rainy season. Due to less rainfall and its short duration the agricultural activities is mostly dependent upon canal irrigation and Tube wells. According to the 2011 census Rohtak district has a population of 1,058,683[1]. The district has a population density of 607 inhabitants per square kilometer. Its population growth rate over the decade 2001-2011 was 12.61%.The district has witnessed rapid industrialization, urbanization, diversification in agriculture and change in occupation structure. The district is situated on the National Highway No. 10.

Panchkula (30o41’ N and 76o52’ E) district has a sub tropical continental monsoon climate having, hot summers, cool winters, good monsoon rainfall. It has great variation in temperature (-1 °C to 43 °C). Sometimes winter frost occurs during December and January. The district also receives winter rains from the western disturbance. The rainfall is mostly received in the monsoon. Morni hills constitute the highest point of the district as well as of Haryana. The Ghaggar is the only perennial river, which is very shallow outside of the monsoon. Generally the slope of the district is from north east to south west and in this direction, most of the rivers/streams rain-fed torrents flow down and spread much gravel and pebbles in their beds. The soils in the district are mainly light loam. The district lies in the Himalayas boundary fault zones and earthquakes of moderate to high intensity have occurred in the past. According to 2011 census of India, it was the least populous district of Haryana and had a population of 558890.The district has a population density of 622 inhabitants per square kilometer. Its population growth rate over the decade 2001-2011 was 19.32% [18, 19].

3. Methods & Materials

For the present study, we used ambient air quality data collected by the Haryana State Pollution Control Board (HSPCB) using Ozone analyzer (O-342M), NOx analyzer (AC-32M), CO analyzer (CO-12M), and SO2 analyzer (AF-22M) [20] for a period of one year from January 01, 2015 to December 31, 2015. The NOx, CO, SO2 and O3 samples were collected by the HSPCB using their respective analyzers which could be operated up to 28 hrs and the sampling duration was 24 hrs as accepted by the Environmental Protection Agency (EPA) of the U.S.A. and the Central Pollution Control Board (CPCB) of India. Oxides of nitrogen analyzer use proven chemi-luminescence technology to measure NOx in ambient air quality. The CO analyzer works on the principle of non-dispersive absorption and SO2 analyzer operates on the principle of light absorption, where the SO2 molecules are excited by absorbing light at one wavelength and later decay to a lower energy state by emitting UV light at a different wavelength which is proportional to SO2 concentration. The O3 analyzer also works on the absorption principle i.e. O3 molecules absorbs UV light at 254nm wavelength. The degree of absorption is directly related to O3 concentration as described by Beer-Lambert law [21, 22, 23]. O3 measurements are automatically corrected for gas temperature / pressure changes and can be displayed in units of ppm, µg/m3 or mg/m3. In this study the regression correlation analysis has been performed between O3 & NOx, CO and SO2 for different meteorological seasons to investigate the relationships between them. This analysis will give an idea about which season and meteorological conditions play a major role in regulating O3, CO, SO2 and NOx concentrations over the sampling sites and also how SO2, NOx and CO concentration affects O3 under different meteorological conditions.

4. Results and Discussion

In this study, we have analyzed and correlated the NOx, CO and SO2 data with O3 concentrations obtained at three sites in Haryana State in Northern India for spring, pre-monsoon, monsoon and post-monsoon seasons for the period from January 01, 2015 to December 31, 2015. The NOx, CO and SO2 variations and their influences on concentration of O3 in the ambient air were analyzed using regression analysis. The graphs are presented in Figure 2-Figure 10 and the results of regression analysis are presented in Table 2 - Table 4. A comparison of coefficient of determination for NOx, CO and SO2 with O3 at Gurgaon, Rohtak and Panchkula for spring, pre-monsoon, monsoon and post monsoon seasons is presented in Figure 11.

4.1. Influence of NOx, CO and SO2 on Concentration of O3 in Gurgaon

The NOx, CO and SO2 variations and their influences on concentration of O3 in the ambient air for Gurgaon are presented in Figure 2, Figure 3 & Figure 4 and the results of regression analysis are presented in Table 2.

It can be seen that the monthly mean concentration of O3 was observed to be maximum in the month of September and minimum in the month of July while NOx, CO and SO2 observed to be maximum in the month of April, June and June respectively and minimum in the months of November, September and August respectively. Low O3 concentration (17.5 µg m-3 in the month of July) was observed in monsoon due to the strong winds that dilute air by carrying O3 precursors away from the site. The observed results of O3 can be attributed to lower vertical mixing due to lower planetary boundary layer height, stronger titration by NOx due to higher emission related to heating and lower photochemical production due to lower temperature and solar radiations. The observed low values of NOx can be attributed to stronger vertical mixing due to higher planetary boundary layer height, faster transition from NOx to O3 due to higher temperature and higher wet deposition due to precipitation [24]. The observed winter increase of NOx may be attributed to weaker vertical mixing due to particularly low planetary boundary layer height, slowest chemical loss due to the lowest temperature, solar radiation and oxidant concentration and particularly much higher anthropogenic emission in winter [25, 26]. Since Gurgaon is on faster pace of development and thickly populated and so this area has an envelope of dust and pollutants gases which in turn slow down photo oxidation of NOx. The observed peak in CO and SO2 in pre-monsoon season may be due to enhanced incomplete combustion of fuels, enhanced vehicular emission and chemical transformation of interacting gases in dry season [27].

Table 2. Correlation coefficient and the regression equation between NOx, CO, SO2 and O3 in Gurgaon

Regression analysis reveals that O3 is negatively correlated with NOx in spring (r2= -0.124), monsoon (r2 = -0.256) and Post monsoon seasons (r2 = -0.694) and positively correlated during pre-monsoon season (r2 = 0.389) [23]. CO showed negative correlation with O3 during pre-monsoon (r2 =-0.999) and monsoon (r2 = -0.322) seasons and positive correlation during spring (r2=0.980) and post monsoon (r2=0.356) seasons. SO2 showed weak negative correlation with O3 in monsoon (r2= -0.137) season and positive correlation during spring (r2 =0.506), pre-monsoon (r2=0.605) and post monsoon (r2=0.922) seasons. It can be seen that during monsoon season, NOx, CO and SO2 showed weak negative correlation with O3 in Gurgaon [28]. During spring, the influence of CO & SO2 on O3 is opposite to that of NOx while in pre-monsoon season, the influence of NOx and SO2 is opposite to that of CO. In post monsoon season, the influence of CO & SO2 on O3 is opposite to that of NOx. However, the degree of correlation is different in different seasons. Negative correlation between NOx and O3 concentrations suggested that NOx is not the only factor contributed to elevated O3 concentrations [29].

4.2. Influence of NOx, CO and SO2 on Concentration of O3 in Rohtak

The NOx, CO and SO2 variations and their influences on concentration of O3 in the ambient air in Rohtak are presented in Figure 5, Figure 6 & Figure 7 and the results of regression analysis are presented in Table 3.

It can be seen that the monthly mean concentration of O3 was observed to be maximum in the month of September and minimum in the month of July while NOx, CO and SO2 observed to be maximum in the month of July, January and February respectively and minimum in the months of November, October and July respectively.

Table 3. Correlation coefficient and the regression equation between NOx, CO, SO2 and O3 in Rohtak

The maxima of NOx and minima of O3 in month of July is significant and justify the chemistry of O3 in the atmosphere in comparatively less polluted and less rainfall plain area[30].

Regression analysis results shows that, O3 is negatively correlated with NOx in spring (r2= -0.797), pre-monsoon (r2= -0.819) and Post monsoon (r2= -0.797) seasons and positively correlated during monsoon (r2= 0.997) season. It may be due to low rainfall in Rohtak in the year 2015. CO showed negative correlation with O3 during monsoon (r2=- 0.829) season and positive correlation during spring (r2= 0.991), pre-monsoon (r2=0.721) and post monsoon (r2=0.997) seasons. SO2 showed weak negative correlation with O3 in pre-monsoon (r2= - 0.148) season and positive correlation during spring (r2=0.155), monsoon (r2=0.843) and post monsoon (r2=0.967) seasons. During monsoon season, NOx and SO2 showed positive correlation with O3 while CO negative correlation. In spring and post monsoon, the influence of CO and SO2 is opposite to that of NOx while in pre-monsoon, the influence of NOx and CO on O3 is opposite to that of SO2.

4.3. Influence of NOx, SO2 and CO on Concentration of O3 in Panchkula

The NOx, CO and SO2 variations and their influences on concentration of O3 in the ambient air in Panchkula are presented in Figure 8, Figure 9 & Figure 10 and the results of regression analysis are presented in Table 4. It can be seen that the monthly mean concentration of O3 was observed to be maximum in the month of September and minimum in the month of December while NOx, CO and SO2 observed to be maximum in the month of October, April and November respectively and minimum in the months of August, July and July respectively. The averaged O3 concentrations were lower in plains area compared with the mountainous area may be due to the titration effects of high NOx emissions in urban areas and summer O3 production in the plains and mountainous areas are found to be sensitive to NOx.

Table 4. Correlation coefficient and the regression equation between NOx, CO, SO2 and O3 in Panchkula

Since Panchkula is situated in Hilly area and characterized with comparatively high rainfall, high peak temperature and less population density and so influence of NOx, CO and SO2 on O3 is observed to be different from Gurgaon and Rohtak. The variation trends of O3 & NOx and O3 & CO observed to be similar but of O3 & SO2 observed to be different in post monsoon season.

Regression analysis shows that O3 is negatively correlated with NOx in pre- monsoon (r2= - 0.074) and monsoon (r2= -0.854) seasons and positively correlated during spring (r2=0.971) and post monsoon (r2=0.784) seasons. CO showed negative correlation with O3 during monsoon (r2= - 0.829) season and positive correlation during spring (r2=0.991), pre-monsoon (r2=0.0.721) and post monsoon (r2=0.997) seasons. SO2 showed negative correlation with O3 in spring (r2= - 0.965) and post monsoon (r2= - 0.917) seasons and positive correlation during pre-monsoon (r2=0.484) and monsoon (r2=0.262) seasons. During monsoon season, NOx and CO showed negative correlation with O3.while SO2 positive correlation. In spring, pre-monsoon and post monsoon, the influence of NOx and CO on O3 is opposite to that of SO2, however the nature of correlation reverses. These results are graphically shown in Figure 11.

Figure 11. Correlation Coefficient between O3, CO and SO2 at three measuring sites

From above results, it can be seen that the seasonal effects plays significant role in regulating the concentration of O3, NOx, CO and SO2 [31, 32, 33, 34]. Change of season reverses the sign of correlation. The influence of NOx and CO concentration on O3 concentration observed to be similar for spring and post monsoon seasons but not for SO2, The effect of rainfall in regulating the concentration of NOx, CO and SO2 and their influence in regulating the concentration of O3 are of significance.

5. Conclusions

The influences of NOx, CO and SO2 concentrations on concentration of O3 were evaluated for spring, pre-monsoon, monsoon and post monsoon seasons of 2015 in Gurgaon, Rohtak and Panchkula using regression analysis and the findings are stated below.

(i) In Gurgaon, O3 is negatively correlated with NOx in spring (r2= -0.124), monsoon (r2 = -0.256) and Post monsoon seasons (r2 = -0.694) and positively correlated during pre-monsoon season (r2 = 0.389). CO showed negative correlation with O3 during pre-monsoon (r2 =-0.999) and monsoon (r2 = -0.322) seasons and positive correlation during spring (r2=0.980) and post monsoon (r2=0.356) seasons. SO2 showed weak negative correlation with O3 in monsoon (r2= -0.137) season and positive correlation during spring (r2 =0.506), pre-monsoon (r2=0.605) and post monsoon (r2=0.922) seasons. During monsoon season, NOx, CO and SO2 showed negative correlation with O3.

(ii) In Rohtak, O3 is negatively correlated with NOx in spring (r2= -0.797), pre-monsoon (r2= -0.819) and Post monsoon (r2= -0.797)seasons and positively correlated during monsoon (r2= 0.997) season. CO showed negative correlation with O3 during monsoon (r2=- 0.829) season and positive correlation during spring (r2= 0.991), pre-monsoon (r2=0.721) and post monsoon (r2=0.997) seasons. SO2 showed weak negative correlation with O3 in pre-monsoon (r2= - 0.148) season and positive correlation during spring (r2=0.155), monsoon (r2=0.843) and post monsoon (r2=0.967) seasons. During monsoon season, NOx and SO2 showed positive correlation with O3 while CO negative correlation.

(iii) In Panchkula, O3 is negatively correlated with NOx in pre- monsoon (r2= - 0.074) and monsoon (r2= -0.854) seasons and positively correlated during spring (r2=0.971) and post monsoon (r2=0.784) seasons. CO showed negative correlation with O3 during monsoon (r2= - 0.829) season and positive correlation during spring (r2=0.991), pre-monsoon (r2=0.0.721) and post monsoon (r2=0.997) seasons. SO2 showed negative correlation with O3 in spring (r2= - 0.965) and post monsoon (r2= - 0.917) seasons and positive correlation during pre-monsoon (r2=0.484) and monsoon (r2=0.262) seasons. During monsoon season, NOx and CO showed negative correlation with O3.while SO2 positive correlation.

(iv) Seasonal effects plays significant role in regulating the concentration of O3, NOx, CO and SO2.

Change of season reverses the sign of correlation. The influence of NOx and CO concentration on O3 concentration observed to be similar for spring and post monsoon seasons but not for SO2, The effect of rainfall in regulating the concentration of NOx, CO and SO2 and their influence in regulating the concentration of O3 are of significance.

The results of this study will be useful for further research on interactions between atmospheric pollutants and Ozone in other region of Haryana and adjoining states in India.

Acknowledgements

The authors thank the Haryana State Pollution Control Board for providing the O3, NOx, CO and SO2 data for the measuring sites Gurgaon, Rohtak and Panchkula. & Envirotech Online Equipments Pvt. Ltd for providing necessary information’s about measuring devices. The author Dr. Ram Chhavi Sharma is grateful to Shree Guru Gobind Singh Tricentenary (SGT) University Gurgaon for providing an excellent research environment and encouragement during the course of this work.

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