Environ Monit Assess DOI 10.

1007/s10661-011-2284-3

Chemical characteristics of aerosols and trace gas distribution over North and Central India
Khem Singh & D. P. Singh & C. K. Dixit & Nahar Singh & C. Sharma & S. Sahai & Arvind K. Jha & Z. H. Khan & Prabhat K. Gupta

Received: 6 January 2011 / Accepted: 27 July 2011 # Springer Science+Business Media B.V. 2011

Abstract A field campaign on aerosol chemical properties and trace gases measurements was carried out along the DelhiHyderabadDelhi road corridor (spanning about 3,200 km) in India, during February 129, 2004. Aerosol particles were collected on quartz and cellulose filters using high volume (PM10) sampler at various locations along the route (i.e., urban, semi-urban, rural, and forest areas) and have been characterized for major cations (Na+, Ca2+, Mg2+, K+, and NH4+), anions (Cl, NO3, and SO42), and heavy metals (Cu, Cd, Fe, Zn, Mn, and Pb). Simultaneously, we measured NO2 and SO2 gases. These species show large spatial and temporal variations. The ambient PM10 concentration has been observed to be the highest (554 g m3) near semiurban areas followed by forest areas (482 g m3) and in rural areas (4422 g m3). The concentrations of NOx (NO2+NO) and SO2 ranged from 16 to 69 g m3 and 4 to 11 g m3, respectively. Among anions, NO3 and SO42 are the major constituents of PM10. The urban and semi-urban sites
K. Singh : D. P. Singh : C. K. Dixit : N. Singh : C. Sharma : S. Sahai : A. K. Jha : P. K. Gupta (*) National Physical Laboratory-CSIR, Dr. K. S. Krishnan Marg, New Delhi 110012, India e-mail: prabhat@mail.nplindia.ernet.in Z. H. Khan Department of Physics, Jamia Millia Islamia, New Delhi 110025, India

showed enhanced concentrations of Fe, Zn, Mn, Cd, and Pb. This study provide information about atmospheric concentrations of various species in the northern to central India, which may be important for policy makers to better understand the air quality of the region. Keywords PM10 . Cations . Anion . NOx and SO2 . Heavy metals

Introduction Aerosol particles of different sizes and composition play an important role in the control of many atmospheric processes, e.g., cloud formation, visibility, solar radiation transfer (Bodhaine 1983; Pueschal et al. 1986; Shaw 1987), deposition of different compounds, acidification of rain, smog, fog, etc., which affect the climate, water, and human health (Dockery et al. 1993). Airborne particles with an aerodynamic diameter of <10 m (PM10 or respirable suspended particulate matter) are considered as inhalable particles and have been found to be widely associated with respiratory health problems in human. Gases and particulate matter, both contribute to deterioration of air quality (Parmar et al. 2001). Water-soluble ionic compounds contribute more to fine aerosol, indicating more health-related risk (Bencs et al. 2008). Aerosols are largely spread over long regions (Chan et al. 1997; Wakamatsu et al. 1996) because fine aerosols are

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lighter in mass and remain suspended in air for several days (Wojicik and Chang 1997). Gas-phase SO2 and NO2 released into the environment due to natural or anthropogenic processes are oxidized mainly to particulate phase, sulfate, and nitrate, respectively, and also such trace gases pose health-related problems (Dockery et al. 1993). Secondary aerosols are considered to be very important when atmospheric nutrient loading of a water body is considered (Horemans et al. 2009). Acidic aerosols can react with gaseous ammonia (NH3) to form ammonia salts (Koutrakis et al. 1988), which have impact on atmospheric processes and human health (Vincent 1989). In this paper, we present the results of a field campaign funded by Indian Space Research Organisation to study the atmospheric compositions along the DelhiHyderabad-Delhi road corridor route (Northern and Central India) during the period February 129, 2004. The latitudinal and longitudinal coverage for this campaign was from 17.3o to 28.6oN and 77.2o to 78.2oE, respectively, and the route covered several diverse ecosystems like urban (U), semi-urban (SU), rural (R), and forest (F) areas. The results of this case study, i.e., chemical characterizations of aerosols and trace gases for various locations along the DelhiHyderabadDelhi road corridor in India can be useful for policy maker to better understand the air quality issues.

by the thick Teak (tall Asian tree) forest. Sampling at Sagar site was done about 15 km away from the main city, which is situated on the foothills of Vidhyanchal mountain ranges and Jabalpur site surrounded by hills and some villages within the radius of 12 km. Agricultural fields surrounded the Nirmal site. Kurai site is situated in the south of Jabalpur and was about 4 km inside the forest. Sampling site in Nagpur was located inside the campus of National Environmental and Engineering Research Institute (NEERI), which is near to the residential area. Sugarcane trash burning activities was observed at Ramampeth (rural site). ShadnagarHyderabad (Hyd) site is located 80 km towards the south of Hyderabad, where the measurement was made round the clock (i.e., 06001800 0600 hours) continuously for 5 days, i.e., from February 1621, 2004. There was a fire event on February 19, 2004 in the city area and is considered as an episodic event day. Meteorological parameters (Fig. 2), i.e., average ambient temperature, pressure, and wind speed and direction, for each sampling sites were recorded from in situ measurements, and also taken from the Indian Metrological Department for one or two locations where we missed the recording of meteorological data. Relative humidity was observed to be low at most of the sites. Aerosol and trace gas sampling and chemical characterization Aerosol samples were collected on pre-heated, preweighed, and desiccated Whatman Quartz micro-fiber (QM-A) and Cellulose Whatman 41 filter papers (size, 203254 mm) at various sites using a high volume sampler (Model: HVS/R, Netel Chromatographs), which can collect particles <10 m (PM10) at a flow rate of 1.00.2 m3 min1. Sampling duration varied from 4 to 6 h at all sites except measurement made at Hyd because of the logistic arrangement. Gas-phase NOx (NO+NO2), NO2, and SO2 were collected by passing ambient air at a flow rate of about 1 Lmin1 through the glass impingers placed in sequence containing sodium arsenite (0.008 M), sodium hydroxide (0.1 M) solution (Jacob and Hocheisser 1958), and potassium tetra-chloromercurate solution (0.04 M; West and Gaeke 1956), respectively, and determined by the colorimetric method by an UVvisible spectrophotometer. Further, for NO2 sampling, ambient air was passed via chromic acid (CrO3) trap to oxidize ambient NO

Methodology Sampling sites Samplings were done at different sites representing diverse ecosystems (Fig. 1) along DelhiHyderabad Delhi road (National Highway), which covers nearly 3,200 km and passes through five States, i.e., Uttar Pradesh, Rajasthan, Madhya Pradesh, Maharashtra, and Andhra Pradesh (Table 1). All sampling locations (11 sites) were about 200 to 500 m away from the highway (wind direction was from site to road side) to avoid traffic influence. Among these sites, Hyderabad and Nagpur are big cities (urban areas) with population of 3.69 million and 4.05 million, respectively (2001 census). Kosi site lies about 2 km away upwind the highway. Dholpur is in the arid regions of Rajasthan, whereas Khajuraho represents a semiurban environment, and Orchha site is surrounded

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Fig. 1 Sampling sites along the DelhiHyderabadDelhi road corridor route

into NO2 (Levaggi et al. 1974). NO is calculated as a difference between NOx and NO2. Each aerosol loaded filter was folded in half face to face and preserved. Filters were equilibrated in desiccators for 48 h before weighing and chemical analysis. The mass of aerosols collected was obtained

gravimetrically using a micro-electronic balance (OHAUS, Model: GA 200D; range max, 110 g; accuracy, 0.1 g). Chemical characterization of aerosols has been done for cations and anions of water-soluble aerosol components, and acid soluble trace heavy metals.

Table 1 Description of the sampling sites Sampling site Chhatha/Kosi Kalan Orchha Sanuda/Sagar Tikaria/Jabalpur Pipertutha/Kurai Bussapur/Nirmal Shadnagar/Hyderabad Ramampetha Nagpura Achnar/Khajurahoa Sagarpada/Dholpur
a

Period 2 Feb 4 Feb 7 Feb 9 Feb 11 Feb 14 Feb 1621 Feb 22 Feb 23 Feb 27 Feb 29 Feb

Latitude/longitude 2749N7725E 2418N7737E 2353N7854E 2322N8004E 2146N7931E 1857N7823E 171.7N7811.3E 1807N7827E 2107N7904E 2452N7956E 2640N7754E

Ecosystem type SU F R R F R SU R U SU SU

Meteorological conditions observed during sampling Clear atmosphere, medium wind River basin, stony area, moderate wind Stony soil, clear sky, medium winds Vegetation, clear sky, slow wind with dust Inside forest, clear sky, slow wind Clear sky, wind with sand particles Clear sky, normal winds Sugarcane trash burning, clear sky, medium wind Thick vegetation and buildings Hilly area Near Chambal river, arid area

U urban, SU semi-urban, R rural, F forest

a

Indicates return journey sites

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Temperature

Fig. 2 Average meteorological parameters with standard deviation at sampling sites

50
0

C 0

Humidity %
Wind Dir, degree

100 50 0
400 200 0

Wind speed,

6 ms 4 2 0
-1

Pressure, mmHg

765 760 755 Kurai Orchha Khajuraho Jabalpur Nirmal Delhi Kosi Sagar Hdy Hdy Hdy Dholpur Ramampeth Hdy Hdy

Location

Water-soluble chemical species Water-soluble aerosol components from filter cut area of 25 cm2 were extracted with 20 ml deionized water for 30 min by ultrasonication (model: Elma, Transonic 700/H). The extracted volume, after filtration through Whatman 41 cellulose filters, was made up to 50 ml with deionized water and kept in pre-washed polyethylene bottles after little addition of thymol (Gillet et al. 1992; Granat et al. 1992) as preservative and stored in refrigerator. Major cations, i.e., Na+, Ca2+, Mg2+, and K+, in the extract were analyzed by flame atomic absorption spectrophotometer (FAAS, Analytik Jena Vario, Germany), whereas Cl, NO3, and SO42 were analyzed by ion chromatography (Dionex 761) with METROSEP column of size 3.0150 mm. Ammonium (NH4+) was determined before adding thymol, by indophenol blue method (Weatherburn 1967) using

a UVVIS Spectrophotometer (Model Lambda 3b, Perkin Elmer). The quality assurance in determination for various species as above was done by using certified reference materials or Bhartiya Nirdeshak Dravyas of National Physical Laboratory, India and National Institute of Standards and Technology, USA traceable standards. The extraction of trace heavy metals was done from each filter sample cut area of 25 cm2 (including filter blank), with 20 ml of 5% HNO3 solution ultrasonically for 2 h (Ho et al. 2003) and filtered through Whatman 41 cellulose filters, diluted to 50 ml with deionized water and stored in polyethylene bottles in the refrigerator until their chemical analysis. FAAS was used to determine Fe, Zn, and Mn, while Cu, Cd, Al, and Pb were analyzed using graphite furnace atomic absorption spectrophotometer (GFAAS, Analytik Jena, Germany).

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Results and discussion The spatial variation of PM10 mass concentrations of aerosols at each sampling site are discussed elsewhere (Gupta et al. 2007) and was found to be in the range of 27 to 75 g m3. It has been found that PM10 loadings of different ecosystems are 545 g m3 for urban areas, 482 g m3 for forest areas, and 44 22 g m3 for rural areas, respectively. The PM10 levels at Nagpur and Hyderabad were 40 and 51 g m3, respectively, which are comparatively lower than the values observed earlier at these sites, i.e., 79 and 73 g m3, respectively (NEERI 2000). Major ionic species Figure 3a, b, c shows spatial variation in the concentrations of the major cations, anions, and heavy metals in PM10 aerosol samples from different locations. Figure 4 shows that the ratio of total soluble ions species (cations + anions) to PM10 is higher at Sagar (85%) than that of other sites. The ratio of sea salt fraction (Na++Cl) to total soluble ions species varies from 13% to 72% with the maximum value found at Jabalpur. Whereas Na+ and Cl were found to be in the range of 0.13 to 1.69 and 1.16 to 13.10 g m3, respectively, and the range of molar ratio of Na+/Cl is from 0.02 to 0.65. The other species are SO42 (16% to 83%) with the maximum at Hyderabad, whereas NO3 (13% to 31%), followed by NH4+, Cl, Ca2+, and Mg2+ having the maximum at Ramampeth. It has been found that anions concentrations (Cl, SO42, and NO3) are higher at semi-urban sites (Kosi, Cl 13.1 g m3 and Hyderabad, SO42 10 g m3) as compared to rural sites, i.e., Sagar, Jabalpur, Nirmal, and Ramampeth (Fig. 3a). Among these, Sagar site has a higher total ionic concentration value of 27.3 g m3, which shows dominance of industrial sources. Cl has been found to be higher at Kosi and lower at Nirmal (1.2 g m3), indicating dominance of industrial sources at Kosi, which has an industrial area with large industries that are in function. The Cl value at Hyderabad and Nagpur has been observed to be 2.6 and 1.4 g m3, respectively, which are much lower than 11.1 and 10.8 g m3, respectively, observed in a previous study during February 1996 (NEERI 2000). SO42 concentration varies from 2.7 to 10 g m3 with the maximum concentration of 10 g m3 observed at Hyderabad. NO3 is also one of the major constituents of the urban

atmospheric aerosols (Hidy et al. 1975). Particulate nitrate is largely produced through the photo-oxidation of NO2, derived from combustion of fossil fuels (Logan 1983). In Nagpur, it accounts for only a small portion of the PM10 mass concentrations (3%). The variation observed for NO3 in the PM10 is from 1.2 to 6.8 g m 3 with the minimum at Khajuraho (1.4 g m3) and the maximum at Hyderabad (6.8 g m3; Fig. 3a). The concentration of NO3 at Nagpur (1.2 g m3) was lower than the reported values in a previous study (2.8 g m3) in February 1996 (NEERI 2000), whereas the value at Hyderabad in daytime (6.8 g m3) was found to be higher than the earlier reported values, i.e., 1.55 g m3 (NEERI 2000). Na+, Ca2+, and Mg2+ that originated from natural sources, like sea salts, were found to be dominantly distributed in aerosols (Khare et al. 2004). Figure 3b shows that the concentration of Ca2+ has been found to be the highest at Sagar and minimum at Jabalpur, while Mg2+ has been observed to be higher at Ramampeth and lowest at Kurai. The higher value of Ca2+ and Mg2+ can be due to sea salt and suspension of local soil dust (Horemans et al. 2009). The value of K+ has been observed to be the maximum at Ramampeth and minimum at Orchha, which may be due to sugarcane trash burning at farming site, though the value of PM10 is higher at Orchha as compared to Ramampeth, indicating the greater contribution of natural sources at Orchha. The biomass burning contributes to enhanced the concentration of K+ (Echalar et al. 1995; Cooper 1980; Kleinman et al. 1979). NH 4 + concentration was found to be 0.09 g m3 at Dholpur and 0.01 g m3 at Nagpur. Heavy metals The concentrations of heavy metals in the PM10 aerosol samples collected at different sites are shown in Fig. 3c. Al is normally used as the crustal indicator element and the enrichment factor (EFcrust) is calculated according to following equation (Chester et al. 2000), EFcrust Cxp =CAl =Cxc =CAlc ; Where Cxp and CAl are the concentrations of an element x and Al, respectively, in aerosol, and Cxc and CAlc are their concentrations in an average crustal material (Murthy et al. 1982). By convention, an

Environ Monit Assess Fig. 3 Spatial variation in a anions, b cations, and c metals concentration at different sampling sites

a
Concentration, g m -3

15 12 9 6 3 0
Khajuraho Dholpur

Cl

NO3

SO4

Nagpur

Ramampeth

Location

b 4.0
Concentration, g m -3
3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0

Na

Ca

Mg

NH4

Ramampeth

Sagar

Orchha

Nagpur

Kurai

Hyd Night
Hyd Night

Jabalpur

Hyd Day

Location

c
Mn, Cu, Cd, Pb, Al (ng m )

Dholpur

Khajuraho

Orchha

Ramampeth

Location

arbitrary EFcrust value of <10 indicates that a trace metal in aerosol has a significant crustal source termed as non-enriched elements and EFcrust >10 is considered to indicate a non-crustal source, termed as the anomalously enriched elements (AEEs; Peirson et al. 1974; Fig. 5).

At Dholpur, higher concentrations of Fe (2.29 103 ng m3), Zn (1.45103 ng m3), Mn (0.26 103 ng m3), and Pb (0.02103 ng m3) have been observed, whereas at Kosi, Cd (0.31103 ng m3) and at Nagpur, Cu (0.14103 ng m3) showed the highest concentrations (Fig. 3c). The lowest concentration of

Hyd Night Hyd Episodic

Kosi

Nirmal

Kurai

Jabalpur

Hyd Day

Sagar

Nagpur

350 300 250 200 150 100 50 0

Mn

Cu

Cd

Pb

Al

Fe

Zn

2700 2200 1700 1200 700 200 Fe, Zn (ng m )

-3

-3

Hyd Episodic Event

Khajuraho

Kosi

Dholpur

Jabalpur

Hyd Day

Nirmal

Hyd Episodic

Orchha

Nirmal

Kurai

Sagar

Kosi

Environ Monit Assess Fig. 4 Spatial variation in fraction of major ions with respect to PM10

90

Soluble ions fraction in PM10, %

80 70 60 50 40 30 20 10 0

Na+Cl NO3 SO4 Ca+Mg+K+NH4 Total soluble ions

Orchha

Dholpur

Nagpur

Ramampeth

Khajuraho

Sagar

Jabalpur

Kurai

Kosi

Hyd Day

Hyd Night

Location
Al, Fe, Mn, Cu, Zn, Cd, and Pb has been observed at all the rural sites. No significantly higher value of EFcrust for Pb was observed at any sites Fig. 5. Ionic enrichment factor To indicate the extent of the contribution of sources other than sea salts to the particulate concentration of the ion, EF has been calculated by considering Na+ from sea water (Duce et al. 1983). It can be seen from Table 2 that for most of the ions, EFs are higher at all the sites, except at Ramampeth and Hyderabad, which show comparatively lower values of Cl. Anthropogenic activities and crustal sources may be responsible for higher EFs. At all the sites, a significant fraction of Ca2+ and Fe may also be emitted from anthropogenic activities such as industries, fossil fuel combustion, etc. (CUPS 19811982; CUPS 1987). The heterogeneous reactions of gaseous SO2 and HNO3 might have also contributed in the observed values. The SO42 and NO3 may be attributed to form from gaseous absorption of SO2 and HNO3 on preexisting particles by heterogeneous reaction. We have observed a good correlation (r2 =0.77) between SO42 and SO42+SO2, which suggest that SO42 may have been largely produced by secondary processes. Similarly, NO3 is also suggested to form through secondary processes. However, in our case the correlation between NO3 and NO3+NOx is poor (r2 =0.03), which possibly due to evaporation losses of NO3 during atmospheric high humidity conditions. An increase in the air temperature may lead to the biodegradation of ammonium salts present and the low humidity may result in NH3 emissions in the gas phase. The transformation of NH3 into particulate NH4Cl and NH4NO3 increases with decreases in temperature (Allen et al. 1989; Tanaka et al. 1987). The concentration of NH4+ has been found to be higher at Dholpur, Nirmal, and Hyderabad. From this study, it is observed that a decrease in air temperature results in an increase in the concentration of particulate NH4+. NH4+ particles in the atmosphere are believed to be existed largely as (NH4)2SO4 and NH4NO3. Both are hygroscopic in nature; however, evaporation losses of NH4NO3 particles are reported widely. In our study, the NH4+ show good correlation with NO3 (r2 =0.59) and non-sea salt (nss) SO42 (r2 =0.50). When considering the variation of NH4+, the contribution of NH4Cl in addition to (NH4)2SO4 and NH4NO3 should be taken into the account. NH4Cl can be formed at low temperature by the reaction of NH3 and HCl (Pio and Harrison 1987) as per the following equation. NH3 gas HCl gas NH4 Cl particle The maximum amount of NH4Cl can be estimated by excess of Cl after determining the amount of sea salt Cl. The excess value of Cl (denoted as Cl)

Hyd Episodic

Nirmal

Environ Monit Assess Fig. 5 Enrichment factor indicating crustal and non-crustal source for heavy metals

70 60 50

Cu

Fe

Zn

Mn

Cd

Pb

EFcrust

40 30 20 10 0 Hyd Episodic Khajuraho Kosi Orchha Ramampet Hyd Night Dholpur Sagar Kurai Jabalpur Hyd Day Nirmal Nagpur

Location

beyond the values of the sea salt in aerosols were calculated using Na+ concentration as an indicator of sea salt. Cl (= Clobs Clsea, where Clobs and Clsea denote the observed and sea salt ratio of Cl concentration in PM10 aerosols, respectively) is a useful indicator to find out anthropogenic and sea salt contributions. The positive value of Cl in most of

the sites reveals that contribution may be primarily due to anthropogenic sources, whereas the negative value shows dominance of the sea salt contribution. Some fractions of the emitted SO2, through the heterogeneous reactions, are oxidized to sulfate aerosols (Cheng et al. 2000). Using Na+ as a tracer of sea salt, excess sulfate (nss SO42) was calculated as below (Millero and Sohn 1992). nss SO4 2 SO4 2 0:251Na The factor of 0.251 is the average molar ratio of SO42 to Na+ in bulk sea water. More than 90% of the sulfate observed in the PM10 is nss SO42 at all the sites (Fig. 6). It is found that the SO42 concentration at the semi-urban site is larger than the rural and forest sites except at Sagar and Nirmal, which are rural sites. The formation of secondary SO42 can be explained by calculating the fs value, which is the mole fraction of nss SO42 in total sulfur oxides, and is determined by fs nss SO4 2 = SO2 SO4 2 As mentioned by Ohta and Okita (1990), fs>0.1 suggests the occurrence of SO42 formation in the atmosphere. At all the sites, the values of fs exceed 0.1 with the maximum values observed at Dholpur and Hyderabad (Fig. 6). The higher value of SO42 at

Table 2 Ionic enrichment factors with respect to Na for different sampling sites Location Enrichment Factor Cl Kosi Dholpur Khajuraho Orchha Sagar Jabalpur Nirmal Kurai Nagpur Ramampeth Hyd Day Hyd Night Hyd Episodic 15.9 23.9 1.9 3.3 3.7 8.5 5.1 9.0 5.8 0.9 1.2 1.8 1.0 SO42 54.9 169.5 7.3 14.6 17.1 19.5 221.6 48.7 142.7 5.3 24.0 32.8 26.2 Ca2+ 16.6 66.4 4.5 3.4 28.9 3.7 20.7 6.9 41.5 14.1 15.1 20.3 14.1 K+ 15.6 108.2 1.6 1.8 2.0 3.2 18.3 7.7 115.8 43.8 18.0 23.2 38.9 Mg2+ 2.9 12.6 0.7 1.0 0.5 1.4 8.8 2.0 6.4 1.3 0.7 1.1 0.9

Environ Monit Assess Fig. 6 Secondary SO 4 2 (fs) and excess sulfate (SO42 excess) concentration variation at different sampling sites
-3

12 10 g m 8 6 4 2 nss SO4 0 Khajuraho Jabalpur Ramampeth Sagar Hyd Day Hyd Night Orchha Nagpur Hyd Episodic Kosi Dholpur Nirmal Kurai fs

0.6 0.5 0.4 0.3 0.2 0.1 0.0 fs

nss SO 4

2-

Location

Ca / SO4 Ca / PM 10

2+

Fig. 7 Ratios of a Ca2+/SO42, b Ca2+/PM10, c SO42/SO2, and d SO42/PM10

50 40 30 20 10 0 0.04 0.03 0.02 0.01 0.00 1.4 1.2 1.0 0.8 0.6 0.4 0.25 0.20 0.15 0.10 0.05 0.00

SO4 /PM 10

2-

SO4 / SO2

2-

2+

2-

-Kosi Dholpur Khajuraho Orchha Sagar Jabalpur Nirmal Kurai Nagpur Ramampeth Hyd Day Hyd Night Hyd Episodic Location

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all site may be explained with the movements of diesel vehicles during sampling periods or long range transport of sulfur can also be possible reason (Bencs et al. 2008). SO42PM10Ca2 correlation SO42 to Ca2+ (Fig. 7) ratio ranged from 0.02 to 0.08 with exception at Sagar (0.16) and Ramampeth (0.29). High correlations (r2 = 0.580.78) were observed among crustal elements (Al, Ca2+, Fe, and Mg2+) at all sites. However, elemental species related to anthropogenic sources, such as Pb and Zn, are found to be accumulated in PM10 particles. The Ca2+ concentrations at Sagar have been observed to be 1.23 g m3. Ca2+ to PM10 ratio is found to be lower at all locations other than Sagar and Ramampeth. SO2SO42PM10 correlation SO2 is oxidized to SO42 and accounted for particulate sulfate (Novakov et al. 1974). Figure 7 shows the comparative ratio of SO42 to SO2 for various locations of this study. According to Ohta and Okita (1990) SO42 originates only from primary sources, if fs<0.1, whereas SO42 is substantially formed by
Fig. 8 Spatial variations in trace gases concentrations at different sites
-3

photochemical oxidation, in the smaller size fractions (Horemans et al. 2009). SO42 to PM10 ratio is comparable at most of the locations. The ratio of SO42/SO2 at different locations varies from 0.50 to 1.39. The possible reason for the lower ratio at Kurai and Jabalpur site includes lower levels of PM10 and SO2, which possibly represents the equilibrium background concentration at which appreciable conversion of SO2 may not take place as in the case of other sites. SO42 levels at Dholpur (Near Agra city) have been found to be comparable to values observed earlier at nearby Agra (14.67 g m3; Kulshrestha et al. 1995). Trace gases Figure 8 shows the variation of short lived trace gases, e.g., NO, NO2, NOx, and SO2, observed at different sites. The nitrogen oxides (NOx) concentrations at different sites varied from 15.9 to 69.2 g m3 with lowest value at Nirmal (15.9 g m3) and the highest at Nagpur (69.2 g m3). The concentration of NO2 observed at Nagpur (63.6 g m3) was higher than the earlier reported value (8 g m3; NEERI 2000), but for Hyderabad, the concentration of NO2 (19.4 g m3) showed similarity with previously reported value

80 70

NOx

NO2

NO

SO2

12 10 8 6 4 2 0

Concentration, g m

60

NOx, NO2 & NO

40 30 20 10 0 Khajuraho Orcha Sagar Kurai Nagpur Ramampeth Hyd Fire Event Kosi Dholpur Hyderabad Jabalpur Nirmal

Location

SO2 g m

50

-3

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(20 g m3; NEERI 2000). The NO showed variations from 0.1 to 5.6 g m3 at Sagar and Nagpur, respectively. SO2 concentrations at different sites varied from 3.9 to 11 g m3 with lowest value at Ramampeth and the highest at Sagar.

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Conclusions An intensive ground-based measurement campaign for the study of ambient aerosols and trace gases was performed in February 129, 2004 along the Delhi Hyderabad road corridor covering urban, rural, and forest sites. At some places industrial sources also seem to contribute to the aerosol loading. Aerosol chemical composition data shows large spatial and temporal variations in concentrations of various ionic and metal species. SO42 and NO3 are the major constituents of PM10. SO42 levels correlate positively with SO2, PM10, and Ca2+. The non-sea salt sulfate fractions in PM10 are over 90% of the total sulfate at most of the sites. The urban and semi-urban sites show evidence of enhanced concentrations of Fe, Zn, Mn, Cd, and Pb. In contrast, the rural sites have lower concentrations of trace metal. Trace metal concentration varied at the urban (Nagpur), semi-urban (Kosi and Dholpur), and rural sites. Aerosol chemical composition expressed on the basis of the EFcrust indicates a crustal source. There is a general uniformity of composition of the AEEs for Zn and Fe in aerosols, whereas Mn, Cu, Cd, and Pb are non-enriched elements. NOx and SO2 show the variation from 16 to 69 and 4 to 11 g m3, respectively, for different sites. These background measurements may provide better understanding about the nature and sources of aerosols in rural and urban sites to undertake appropriate policy measure for improvement of the ambient air quality.

Acknowledgments Authors wish to thank Director NPL and late Dr. A. P. Mitra for guidance and continuous encouragements. Authors thank the funding support of ISRO-GBP. The authors are also thankful to Dr. R. Sridharan, Dr. C.B.S. Dutt, and Dr. Shyam Lal for the organizational support during the field campaign. The authors are thankful to Dr. Shankar G. Aggarwal, scientist, NPL, New Delhi for his editorial support. Thanks are also to the Director CRRI and Dr. A. Shukla of CRRI Delhi for providing meteorological data of campaign route.

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