Objective of the study
The present work is done to find out the relation between the meteorological parameters that affect the tropospheric ozone concentration. Since tropospheric ozone is toxic in nature, the present study is relevant so that remedies can be taken for reducing the ozone concentration. Ozone in the lower atmosphere is mainly produced by anthropogenic pollutions such as from automobiles and fossil fuel burning. So its concentration will be large in cities like New Delhi, Calcutta, Chennai, Mumbai etc. Here the objective of the study is to get an idea about the vertical profile of ozone concentration over Mumbai and its concentration. To find out whether there is any relation between the meteorological parameters such as temperature and relative humidity vertical profiles of these parameters can be plotted and hence the relation can be concluded.

The atmosphere is a thin layer of air that surrounds our planet, the Earth. On a small model of the earth its thickness would be hardly noticeable, not thicker than the skin of an apple. But its weight at the ground level gives us the air pressure under which we and all land living creatures evolved. The higher up we go, the thinner the atmosphere becomes. At a height of several hundred kilometers, it fades away into the vacuum space. The atmosphere is a mixture of gases, mainly composed of nitrogen, oxygen, and argon, which together constitute the major gases of the atmosphere. The remaining gases are often referred to as trace gases, among which are the greenhouse gases such as water vapor, carbon dioxide, methane, nitrous oxide, and ozone. Filtered air includes trace amounts of many other chemical compounds. Many natural substances may be present in tiny amounts in an unfiltered air sample, including dust, pollen and spores, sea spray, and volcanic ash. Various industrial pollutants also may be present, such as chlorine (elementary or in compounds), fluorine compounds, elemental mercury, and sulfur compounds such as sulfur dioxide [SO2].

Composition of dry atmosphere, by volume Gas Volume Nitrogen (N2) 780,840 ppmv (78.084%) Oxygen (O2) 209,460 ppmv (20.946%) Argon (Ar) 9,340 ppmv (0.9340%) Carbon dioxide (CO2) 390 ppmv (0.039%) Neon (Ne) 18.18 ppmv (0.001818%) Helium (He) 5.24 ppmv (0.000524%) Methane (CH4) 1.79 ppmv (0.000179%) Hydrogen (H2) 0.55 ppmv (0.000055%) Nitrous oxide (N2O) 0.3 ppmv (0.00003%) Carbon monoxide (CO) 0.1 ppmv (0.00001%) Ozone (O3) 0.0 to 0.07 ppmv (0 to 7 × 10í6%)

. The vertical temperature profile www. (Source: . The ozone layer.edu).040% over full atmosphere Components of atmosphere (source: Wikipedia) Mixing ratio of any gas is defined as the ratio of the number density of that species to the number density of the air.2. with in this region absorbs much of the insolation.engr. Most military and long distant aircraft operate in this region. The top of the troposphere is a theoretical boundary called the tropopause. from earth surface to 120 km. It¶s height from the ground level varies from 10-16 Km from the poles to the equator. The atmosphere can be divided into a number of layers in accordance with the temperature variation as illustrated in the figure 1. All the physical activities that affect the weather takes place in this region.2 Not included in above dry atmosphere: Water vapor (H2O) ~0. This layer that extends about up to 50 km is called the stratosphere. where the temperature is merely constant with height. so that the temperature is quite high in this region.colostate. The lowermost layer is called the troposphere. Above tropopause. temperature is increasing with height.

Atmospheric gases are so thin in this layer that the protons of the solar wind can easily pass through. but not in the equatorial region. Ozone Ozone is a tri molecule of oxygen which is naturally formed by the photolysis of normal oxygen by UV radiation. By the formation process the UV radiation will be blocked from entering into the lower atmosphere (below tropopause). Low level ozone (or tropospheric ozone) is an atmospheric pollutant [15]. This circulation is called as Brewer Dobson circulation. Beyond its upper boundary. carbon monoxide (CO) and volatile organic compounds (VOCs) react in the atmosphere in the presence of sunlight. The upper portion of the thermosphere called exosphere. mainly in stratosphere. but not in summer and the lowest is observed during autumn not in winter. the highest ozone concentration is seen in the polar region. Mesosphere is characterized by a decrease in temperature with altitude. Also the maximum concentration is observed during spring. mesopause. ozone present in the stratosphere acts as an umbrella that prevents the UV to enter into the surface. The majority of tropospheric ozone formation occurs when nitrogen oxides (NOx). The velocity of this circulation is only about 9m/day. So the kinetic energy of the third particle increases and there by the temperature over that region also increases.the upper limit of the stratosphere. Since UV radiation is harmful to life in the earth. Since the UV is almost shielded in the stratosphere itself. In addition. react in the . So due to this circulation. ozone will not be produced in the troposphere by photochemical reactions. Ozone production in the stratosphere was first explained by Sidney Chapman as follows O2 + photon (< 240 nm) 2O O + O2 + M O3 + M O3 + O 2 O2 The energy gained by the ozone molecule by the absorption of UV radiation will be immediately transferred to other molecules which are not directly involved in the ozone reaction. which is infact toxic to living organisms (bad ozone). There is a slow meridional circulation seen in the stratosphere that leads to the transport of newly produced ozone from the equatorial mid stratosphere to the lower polar stratosphere. This ionization takes place in the lower parts of the atmosphere. reaching about 180 K at 80 Km. causing the temperature to rise. the solar wind removes electrons from atoms to form ions. such as xylene.3 Above stratopause. The majority of tropospheric ozone formation occurs when nitrogen oxides (NOx). It is not emitted directly by car engines or by industrial operations. which extends up to about 80 kms.lies the mesosphere. carbon monoxide (CO) and volatile organic compounds (VOCs). but formed by the reaction of sunlight on air containing hydrocarbons and nitrogen oxides that react to form ozone directly at the source of the pollution or many kilometers down wind. here the atmospheric gases are so thin that a gas molecule travels an average distance of 650 km before hitting another molecule. Aurora are created in this region of higher latitudes. This drop in temperature is due to a decrease in ozone concentration and an increase in distance from the warm surface of the Earth. But it is still thick enough for meteorites to burn up as they pass through. The atmospheric atoms and molecules hit by these protons move faster. and the mesosphere give rise to thermosphere.

NOx. Commonly used unit for ozone measurement is Dobson unit.4 atmosphere in the presence of sunlight. if all these ozone is compressed to the earth surface at STP. winds can carry NOx hundreds of kilometers. CO. a VOC whose atmospheric concentration has increased tremendously during the last century. its thickness will be 3mm only. instruments have evolved from ground based spectrometers to balloons. I. and chemical solvents are the major anthropogenic sources of these chemicals. Another source is windshield washer fluid. The reactions involved in this process are illustrated here with CO but similar reactions occur for VOC as well. . causing ozone formation to occur in less populated regions as well. 1 DU = 2.01 mm thick at STP (0 °C and 1 atmospheric pressure) per unit area. Although these precursors often originate in urban areas. The chemistry involving VOCs is much more complex but the same reaction of peroxy radicals oxidizing NO to NO2 is the critical step leading to ozone formation. The chemical reactions involved in tropospheric ozone formation are a series of complex cycles in which carbon monoxide and VOCs are oxidised to water vapour and carbon dioxide. In situations where this exclusion of methane from the VOC group of substances is not obvious. industrial emissions. and VOCs are called ozone precursors. Motor vehicle exhaust. Ozone measurement techniques Scientists have been studying the concentration of ozone in the atmosphere since the 1920s. Oxidation begins with the reaction of CO with the hydroxyl radical. Since then. the term Non-Methane VOC (NMVOC) is often used. contributes to ozone formation but on a global scale rather than in local or regional photochemical smog episodes.69×1016 molecules /square centimeter The average ozone concentration over the earth atmosphere is about 300 DU. It is defined as the number of molecule required to create a pure layer of ozone of 0. The hydrogen atom formed by this reacts rapidly with oxygen to give a peroxy radical HO2 OH + CO H + CO2 H + O2 HO2 Peroxy radicals then go on to react with NO to give NO2 which is photolysed to give atomic oxygen and through reaction with oxygen a molecule of ozone: HO2 + NO OH + NO2 NO2 + h NO + O O + O2 O3 The net effect of these reactions is: CO + 2O2 CO2 + O3 This cycle involving HOx and NOx is terminated by the reaction of OH with NO2 to form nitric acid or by the reaction of peroxy radicals with each other to form peroxides. Methane.e.

The filter wedge gradually blocks more and more light until the intensity of the 325 nm and 305 nm light are equal. The ratio between the two intensities are determined by an R-dial located on the top of the Dobson spectrophotometer. Balloons. the filter wedge increasingly blocks out more light. At 0 degrees the wedge does not block out any light. The Dobson spectrophotometer was designed by Gordon Dobson in the 1930's. The Total Ozone Mapping Spectrometer (TOMS) aboard Nimbus-7 and Meteor-3 provided global measurements of total column ozone on a daily basis and together provide a complete data set of daily ozone from November 1978 . but only over a small area. Ozonesonde Ozonesonde contains two small chambers containing KI solutions of different concentration. The R-dial is calibrated with the filter wedge. Instruments that are commonly used to measure overhead ozone from the ground are the Dobson spectrophotometer and Light Detection and Ranging (LIDAR). whereas the other wavelength is not absorbed by ozone (325 nm). Therefore the ratio between the two light intensities is a measure of the amount of ozone in the light path from the sun to the observing spectrophotometer. By taking the R-dial reading when the intensities of the two wavelengths are equal. One of the wavelengths used to measure ozone is absorbed strongly by ozone (305 nm). However. their ratio is determined. Titration of ozone in a potassium iodide (KI) solution according the redox reaction: . After an eighteen month period when the program had no on-orbit capability. 1997. The Dobson spectrophotometer measures ultraviolet light from the Sun at 2 to 6 different wavelengths from 305 to 345 nm. At 300 degrees. Dobson spectrometer The Dobson spectrophotometer is a ground-based instrument that measures the amount of ozone present in the atmosphere. 1996 and provided data until June 29. the amount of ozone can be calculated. ADEOS TOMS was launched on August 17.5 aircraft. rockets. the wedge nearly blocks all of the light. Airborne measurements of ozone provide a direct (or in situ) method of determining ozone concentrations in the atmosphere. The sample air is pumped into one of the chamber so that the following reaction takes place. resulting in the most accurate and detailed methods of measuring ozone. Ground stations have been measuring ozone levels for most of this century. rockets. The simple animation below demonstrates how the filter wedge works. As the R-dial rotates from 0 to 300 degrees. They provide long term data of both total column ozone and ozone distribution with altitude.December 1994. and aircraft carry instruments into the atmosphere. so that the original intensity of the 325nm light can be determined from the R-dial reading. the measurements are made only over localized regions and cannot provide a global picture of ozone distribution. By measuring UV light at two different wavelengths. The R-dial controls a filter wedge that gradually blocks out the 325 nm light. Developments in ozone instrumentation have enabled measurements to expand from the atmosphere above an isolated ground station to daily global coverage and profiles of ozone in the atmosphere. and satellites.

6 2 KI + O3 + H2O p I2 + O2 + 2 KOH Ozonesonde(source: www. The iodine makes contact with a platinum cathode and is reduced back to iodide ions by the uptake of 2 electrons per molecule of iodine: I2 + 2 e.[cathode reaction] The two chambers are connected by an metallic bridge so that electrons can move through it. So for a long time observation it cannot be used. This flow of electrons through the cell¶s external circuit can be measured and is directly proportional to the partial pressure of the ozone content in the sample air.iup. .uni-bremen.on Pt p 2 I.de/) Measurement of "free" iodine (I2) in electrochemical reaction cell(s). PV = i t K T / 2e Where P= Partial pressure of ozone e= Charge of electron K= Boltzmann constant t=Time period of pumping T= Temperature in Kelvin i= Current measured the life span of an Ozonesonde is only 3-4 hrs.

7 UV photometer A sample air is pumped into the chamber. A simplified layout of the ozone analyzer showing the working principle of the system.7 nm passes through the chamber and the intensity is detected when comes out. (Source: Research thesis. Lokesh Sahu) By Beer Lamberts law where . A mercury lamp flashes UV radiation of 253.

Case studies of Ozone profiles over Mumbai The wind pattern over India is changing for each winter and summer. Typically north easterly wind prevails during winter and in summer it reverses completely to become south westerly. which translates into a vertical resolution of 30 m. Data and methodology In the present study the data used is ozone concentration in ppbv. 22 July 1998. ozone concentration and the relative humidity are plotted by using Sigma plot. This south . provided by MOZAIC program. Measurements are taken during both take off and landing of the aircraft to get a vertical profile data over the airports. This data is available from a height of 75 m from the ground to about 10 km at a vertical interval about 50 m. MOZAIC data combined with meteorological data is used to 1)establish quasi global climatology of the large scale distribution of ozone and water vapor in the troposphere. The response time of the instrument is 4s. Compared to the Ozonesonde. The data used for this study are 27 august 1997. The strength of each temperature inversion is estimated and corresponding to that the change in the ozone concentration and the relative humidity are calculated. Then these values are compared with the other days and concluded for a general result. The vertical profile of temperature.8 Then the experiment is repeated with air but without any ozone. Then the layers of temperature inversions in graphs of each day are recognized. the life time of the instrument is very high so that in MOZAIC program UV photometer is used. relative humidity in percentage. then Then From this we can calculate the number density of ozone in the sample air. 2)establish the temporal and vertical distribution of O3 and H2O and 3) to validate the chemistry and transport models 4) investigate the seasonal and geographical variations in the relations to their natural and anthropogenic sources. The ozone analyzer is a dual beam UV absorption instrument which has a detection limit of 2ppbv. 20 may 1998. The relative humidity and temperature are measured with a capacitive sensor and a platinum resistance sensor. temperature in 0C in different heights. 08 July 1998. 11 September 1998. MOZAIC program (Measurements of ozone and water vapor by airbus in service aircraft) In this program the ozone and water vapor sensors are installed in airlines which take the measurements at the scheduled flight times. 28 may 1998.

7 cm. sometimes exhibiting marked stratification. Most of this summer monsoon rain will be getting all over the western coastal area of India.9 westerly wind brings moisture from the Indian Ocean leading to the summer monsoon rain almost all over India. RH and temperature over Bombay is shown in the figure .2 °C). the wind reaching over Mumbai is from the central India so that the wind will be dry. and the average annual precipitation is 216.7 °C. At the 400 hPa level. Longitude 72º 50' east. At 700 hPa level an anticyclone circulation is seen over Andhrapradesh and so that the wind reaching over Mumbai at this level is from that region. . In the City. During winter time. Since surface ozone is mainly formed due to photochemical and dynamical processes. the average maximum temperature is 31. as south westerly. with a single or multiple peaks. In this study. At 400 hPa level the wind over Mumbai is purely westerly that comes from North Atlantic Ocean through the northern Africa. At 250 hPa level also the wind pattern is same as that at 400 hPa.59734 (Western India Automobile Association . the vertical profile of ozone shows large diurnal and seasonal variability. The organic and inorganic pollutants released from the vehicles have an important role in the production of the ozone. the eastern coast of India. While the north east monsoon rain is very low compared to the SW monsoon rain and is prominently obtained over the eastern coast of India.WIAA ). At the 250 hPa level the wind reaching over Mumbai is purely easterly and which actually originated over eastern India and blow through the Bay of Bengal. so that the air will be more humid.2 °C. the average wind pattern shows that the wind reaching over Mumbai at 925 hPa level is from the Southern Indian Ocean via Arabian Sea. The average annual temperature is 27. (Source: L K Sahu et la) Mumbai is a metro city in India which is located at 18º 53' North. The magnitude of variability can change significantly with altitude. The vehicle population in Mumbai during 1997-1998 is about 8. 27 August 1997 The vertical profile of ozone. while the average minimum temperature is 23. During the summer time. At 700 hPa level the wind is coming from Pakistan via Arabian Sea. the average wind pattern over India (1996-2001) shows that at 925 hPa level the wind is coming from the Pakistan region in a curved path covering Rajasthan and Gujarat. the observed features of ozone are studied along with relative humidity and temperature in the troposphere.

wind blowing from the sea will reduce the ozone concentration and increases the relative humidity.2 km. A temperature inversion is seen at 2. Then a steep increase in seen showing two peaks of 73 ppbv at 6km and 81 ppbv at 6. Two minimum value peaks are observed at 4. Then the concentration reduces to 61 ppbv at 5.175 km. The ozone concentration then increases to 92 ppbv at 7. a maximum peak of ozone will be corresponds to a minimum relative humidity value and vice versa.65 and the ozone concentration shows a steep increase of 18 ppbv. The average lapse rate of this temperature profile is about 6.59K/km. August includes in the summer monsoon period so that the relative humidity is seen high.e. All these values show an opposite correspondence with the ozone concentration.93 K. Then the concentration decreased with height up to 8 km. The strength of this inversion is only 2. The relative humidity is seen maximum §83 % up to about 2 km and then shows a steep decrease.5 km and 6.75 km.5 km. Here the relative humidity shows a steep decrease of magnitude 53.6 km altitude.75 km. i. It is seen almost constant up to 1.10 The minimum ozone value of 11 ppbv is observed at the ground and its concentration is almost constant § 17 ppbv up to 2 km. from there a steep increase seen upto3. Since Mumbai is a coastal city. .8 km (78 ppbv). 20 May 1998 The surface ozone concentration on this day is about 3 ppbv.

Temperature inversion is seen in two heights. Then a maximal peak is seen at 5. Then it reduces to 16% at 3. It again increases and a 43% is seen at 4 km. 61%.07 km ozone shows an increase of 13 ppbv and the relative humidity shows abrupt decrease of 70%.11 In an inverse manner relative humidity is maximum from the surface to 1 km. about 82 5. 1.2 km and then shows a peak at 1. 63 ppbv. 79 %. The strength of these inversions is 1. 95%.3 km.5 km.75 km ozone shows an increase of 55 ppbv and the relative humidity shows abrupt decrease of 43%. Then after a steady concentration with height again it shows a peak at 6.975 km. 78 ppbv.07 km.75 km. Then the value again reduces and is nearly a constant with height up to 9 km and the relative humidity is about 11.4 K/km. At 1.45 K respectively.7 km and 6. And then also the ozone concentration is almost constant with height up to 9.5%. The average lapse rate of this profile is about 7. Then the value reduces and shows a steady value of about 10% with height. 20%. 28 May 1998 The ozone concentration is almost constant up to 1.75 K and 3. At 6. . The surface relative humidity is 76% which increases with height and shows a maximum at 0. Then it reduces and shows a minimal value at 2.25 km.75 km (35 ppbv). The next peak is seen at 5 km.3 km.

At 2.8 km. at 6.5 K respectively. The strength of these inversions is 2. .66 K/km.1 km and 70 ppbv at 7. A maximum of 78 ppbv at 5.12 In this vertical profile also two temperature inversions are seen. The average lapse rate is about 7.2 km a minimum value of 70% and at 8.75 K and 0.27 km the ozone concentration increases by 26 ppbv and the relative humidity shows an abrupt decrease of 60 % .5 km and 2 minimal peaks of 66 ppbv at 5.7 km. the relative humidity reduces to 53% and remains almost constant up to 4. The at 7. 2 maximum peak values and minimum peak values are seen in the figure.125 km.2 km a maximum of 101 % RH is recorded.5 km. The atmosphere is seen supersaturated up to 2.9 km.7 km and 29 ppbv at 7.275 km and at 4. At 1. 08 July 1998 The surface ozone concentration is about 12 ppbv in this day and which is almost a constant up to 4 km. at 1.2 km the atmosphere is again supersaturated and the RH is 129%.

19 K/km.775 km. The average lapse rate is about 7. one at 7 km (54 ppbv) and the other at 7. the ozone concentration increases by 10 ppbv and the relative humidity decreases by 82%.7 km. A minimum value of 44 ppbv is seen at layer of 6. the strength of the inversion is about 2.375 km the ozone concentration reduces by 17 ppbv where as the relative humidity reduces by 43 %. At 2. At 2.42. Very abrupt changes of relative humidity and the ozone concentrations can be seen in the inversion layers.13 Two significant temperature inversions are seen in this graph.775 km. 22 July 1998 The vertical profile of ozone shows a very low variability on this day.4 km the strength is also 1.54 K and at 6. Even after that level also the ozone shows low variation with height. .6 km (52 ppbv). two maximal peaks. Its surface concentration is only about 1 ppbv. At 6. It shows a gradual steady increase up to 5.5 km.

While temperature inversion is not seen at that time of observation. The surface ozone concentration is about 10 ppbv only and is seen linearly increasing with height. The average lapse rate is 6.7 K/km 11 September 1998 The ozone concentration and the relative humidity show high variability with height in this graph.6 km a peak of 92 % is seen and a minimum peak of 29% is seen in 6.1 km (75 ppbv) during this observation.25 K). as it is a typical summer monsoon rainy day. Maximal values of peaks are seen at 3. A very slight temperature inversion is seen at 1. it seem to be isothermal with height and so it does not show much impacts on ozone concentration (an increase of 4 ppbv) and on the relative humidity (14%).14 The relative humidity is seen super saturated up to 1 km.5 km. Since its strength is too small (0.875 km. At 8.5 km (53 ppbv) and at7. .

9 km relative humidity peaks as 113% and 87% respectively.77 K/km.5 km minimal value of humidity layers are observed as 65 % and 45 %.15 The atmosphere was super saturated about up to 1. At 5 km and 7. .1 km and 7. At 6.9 km. The lapse rate of this day is 5.

This leads to a large temporal and special variation of ozone in the troposphere. Since Bombay is a coastal station. From the present study it can be clearly concluded that ozone concentration undergoes a marked increase when temperature inversion occurs. Also when the humidity of the atmosphere increases it causes in the ozone concentration variation also. . humid air frequently blows to the land area due to sea breeze.16 Conclusion of the case studies Table showing the variation of ozone concentration and the relative humidity corresponding to temperature inversion. This variation seems to be dependent on the strength of the inversion as well as the concentration of ozone below the inversion layer.

17 References L K Sahu. S Lal : Climatology of the tropospheric ozone and water vapour over Chennai: a study based on MOZAIC measurement over India. Ozone measurement techniques www.edu. (State University of Albany) . 2010.albany.