Fine particulate phase PAHs in ambient atmosphere of ... - Springer Link

Environ Sci Pollut Res (2011) 18:764–771 DOI 10.1007/s11356-010-0423-y

RESEARCH ARTICLE

Fine particulate phase PAHs in ambient atmosphere of Chennai metropolitan city, India Rangaswamy Mohanraj & Govindaraj Solaraj & Selvaraj Dhanakumar

Received: 2 September 2010 / Accepted: 23 November 2010 / Published online: 7 December 2010 # Springer-Verlag 2010

Abstract Background Airborne fine particulates (PM 2.5) and its associated polycyclic aromatic hydrocarbons (PAHs) are reportedly hazardous in urban environment due to the presence of multiple emission sources. Methods In this study, fine particulates collected from fourth largest metropolitan city of India, Chennai, were extracted and analyzed for 11 PAHs by high-performance liquid chromatography equipped with a fluorescence detector. Results PM 2.5 values varied between 27.2 and 190.2 μg/m3, while average concentration of particle-associated PAHs determined was in the range from 325.7 to 790.8 ng/m3, which signaled an alarming pollution level in Chennai. Conclusions Factor analysis suggested vehicular emissions inclusive of petrol- and diesel-driven engines as probable sources. Keywords PM 2.5 . Polyaromatic hydrocarbons . Vehicular emissions . Urban area

1 Introduction Air quality in Asian cities is getting worse as the population, traffic, industrialization, and energy use are increasing rapidly. Even with the introduction of advanced

Responsible editor: Philippe Garrigues R. Mohanraj (*) : G. Solaraj : S. Dhanakumar Department of Environmental Management, Bharathidasan University, Tiruchirappalli, 620024 Tamil Nadu, India e-mail: [email protected]

emission control technologies, motor vehicles remain the dominant sources of urban air pollution. Among the persistent toxic pollutants, polycyclic aromatic hydrocarbons (PAHs) consisting a large group of over 100 different chemical compounds with 2 to 7 aromatic rings (Sharma and Tripathi 2009; Stanley et al. 2003) are classified as critically hazardous. Large quantities of such compounds are released into atmospheric environment by various human activities particularly due to incomplete combustion of petroleum products (Lim et al. 1999; Larsen and Baker 2003). PAHs are also produced in all combustion process and burning of any organic material such as garbage wood, tobacco, medical wastes, rubber, and cotton (Oamh et al. 1999; Zimmermann et al. 1999). Aviation exercises are also likely to increase PAH concentrations 10–25 times higher in the atmospheric vicinity (Childers et al. 2000). PAHs have claimed serious concern worldwide since the inhalation exposure to high concentrations is linked to carcinogenic or cocarcinogenic risk (Bostrom et al. 2002), interference with hormone systems, and their potential effects on reproduction and immunity reduction (USATSDR 1995). Benzo(a)pyrene, a potent PAH carcinogen, induces a decrease in the cell viability and damages DNA (Park et al. 2006). Most PAHs on reaction with air, sunlight, and other pollutants (e.g., O3, NOx, and SO2) in the atmosphere form PAH derivatives such as nitro-PAHs and oxygenated derivatives, which are more toxic. Reports also indicated that dinitropyrenes are responsible for most of the direct acting mutagenicity (Heflich et al. 1985; Moller et al. 1993; Moller 1994). High levels of ambient atmospheric PAHs were observed in developing countries particularly in India (Marr et al. 2004; Sharma et al. 2007). The annual PAH emissions from Asian countries were 290 Gg year−1, with China and India contributing 114 and 90 Gg year−1, respectively. The

Environ Sci Pollut Res (2011) 18:764–771

proportion of high molecular weight PAH emission from India (3.60%) was significantly higher than the global average. Reports on PAH content in the coarse particulate matter are scarcely available for few cities in India (Raiyani et al. 1993; Chattopadhyay et al. 1998; Kulkarni and Venkataraman 2000); however, the literature on fine particulate-bound PAHs is extremely limited. In that context, current investigation is carried out to assess the PM 2.5 fraction in ambient air of Chennai metropolitan city, PAHs in PM 2.5 with emphasis on source apportionment analysis.

2 Materials and methods 2.1 Study area Chennai, the capital city of Tamil Nadu state, is the fourth largest megacities in India. The city lies between latitude 12° 57′30″–13°8′50″N and longitude 80°12′10″–80°18′20″E. The city extends over 1,180 km2 and has a population of 4.2 million as per 2001 census. There was a notable increase in population from 1951 to 2001 (20% decadal variation). Chennai has more than 1,400 industries. Most of these industries are situated in the northern part, particularly Manali, Ennore, Ambattur, and Thiruvottriyur. The major groups of industries are electronic materials, rubber, plastic manufacturing, petroleum processing, metal product manufacturing, etc. In Chennai, the total number of vehicles registered with the “Regional Transport Authority” was 2,052,275 as of 2006– 2007. For the current study, four sampling stations such as Ambathur (B1), Kolathur (B2), Saidapet (B3), and Egmore (B4), representing urban, commercial, urban-residential, and industrial regions were selected for airborne PAH study (Fig. 1 and Table 1). The meteorological parameters for the study period are given in Table 2.

765

PM 2.5-laden PTFE membrane filters obtained after 24-h air sampling were subjected to PAH analysis. Several analytical techniques that have been used earlier were carefully considered for extraction efficiency, accuracy, detection limits, and cost, and finally, an appropriate method was evaluated (Sikalos et al. 2002; Vasconcellos et al. 2003; Bourottea et al. 2005; Ryno et al. 2006; Rajput and Lakhani 2009). In the present investigation, PAH extraction and analysis were carried out as per modified Colombini et al. (1998) method. PTFE membrane filter carrying PM 2.5 was ultrasonically extracted by dichloromethane:methanol (60:40) mixture in a dark bottle for 2–3 times. The extracted solution was filtered through 0.2-μm PTFE filter and then redissolved in acetonitrile for high-performance liquid chromatography (HPLC) analysis. PAH standards obtained from SUPELCO were used to generate standard chromatogram for 11 PAH compounds. After required dilution, a standard was injected in HPLC (Make: Waters, USA) with PAH C18 column (5 μm 4.6× 250 mm), and the compounds are determined in fluorescence detector (model: 2475). After standardization, the samples were injected for PAH analysis. Chromatographic peaks were identified by comparing retention times of samples with those of reference PAH compounds. List of PAHs analyzed is as follows: phenanthrene (PHENAN), anthracene (ANTH), fluoranthene (FLT), pyrene (PYR), benzo(a)anthracene (BaA), chrysene (CHRY), benzo(b) fluoranthene (BbF), benzo(k)fluoranthene (BkF), benzo(a) pyrene (BaP), indeno 1, 2, 3-cd pyrene (IcdP), and benzo (ghi)perylene (BghiP; Supelco, USA). Results of PM 2.5 and particulate-bound PAH concentrations were subjected to statistical analysis including analysis of variance (ANOVA) and principal component analysis (PCA) using SPSS 11.0.

3 Results and discussion

2.2 Fine particulate sampling and PAH analysis

3.1 Fine particulate matter and PAH

Fine particulate matter (PM 2.5) was collected using a Fine Particulate Sampler (Model: APM 550, Make: Envirotech, New Delhi, India) from March 2009 to February 2010 at monthly intervals. Ambient air enters the FPS 550 system through an omnidirectional inlet designed to provide a clean aerodynamic cut-point for particles greater than 10 μm. Particles in the air stream finer than 10 μm proceed to a second impactor that has an aerodynamic cut-point at 2.5 μm. The air sample and fine particulates exiting from the PM 2.5 impactor are passed through a 47-mm-diameter PTFE filters that retain the PM 2.5. The Envirotech APM 550 system allows removal of the PM 2.5 impactor from the sample stream. The sampling rate of the system was held constant at 1 m3/h by a suitable critical orifice for 24 h.

PM 2.5 values in Chennai varied between 27.2 and 190.2 μg/m3 with an annual average of 91.8 μg/m3 (Table 3). It is alarming to note that PM 2.5 values at Chennai exceeded the National Ambient Air Quality Standards (NAAQS; India) of 40 μg/m3 and USEPA standard of 15 μg/m3 on annual basis. Excluding Ambathur industrial station (B1), which recorded value of 27.2 μg/m3 during the month of June, all the sampling stations exceeded the 24-h standard limit of US-NAAOS. A maximum level of 190.2 μg/m3 PM 2.5 was recorded in an urban location at B4 (Egmore) during the month of April. Saidapet (B3), another sampling station in southward of the city with high traffic, also experienced high levels of PM 2.5 ranging from 64.8 to 143.8 μg/m3. Suburban

766


Fig. 1 Map showing air sampling locations at Chennai City, India

location B2 (Kolathur) also recorded PM 2.5 in the range of 41.1 to 170 μg/m3. Comparatively lower PM 2.5 recorded in some sampling stations during certain months was probably attributable to the rainfall. ANOVA attempted for fine particulate matter concentrations between sampling sites and seasons revealed no statistically significant difference. Annual average of the sum of 11 PAH concentrations observed in four sampling stations, i.e., Ambathur, Kolathur, Saidapet, and Egmore, was of 582.9, 325.7, 330.7, and 790.8 ng/m3, respectively. The maximum total PAH level of 790.8 ng/m3 was recorded at Egmore (urban commercial area) followed by industrial site Ambathur (582.9 ng/m3). Egmore is identified as one of the hubs in Chennai with the presence of railway junction. High

vehicular traffic often witnessed in Egmore throughout the day was probably the major emission source. Moreover, presence of large number of hotels in the proximity and their kitchen emissions were also likely to contribute to ambient PAH. Ambathur, a major industrial region in Chennai having the second highest PAH concentration among the sampling stations, indicates industrial operations as another source for PAH. Ambathur Industrial Estate, spread over an area of 4.9 km2, is the biggest small scale industrial estate in South

Table 1 Sampling site characteristics

March April May June July August September October November December January February

Sample number

Sampling point

Site characteristics

Latitude and longitude

B1

Ambathur

Industrial site and national highway

B2

Kolathur

Urban-residential

B3

Saidapet

Urban commercial and busiest urban hub

B4

Egmore

Urban commercial and busiest urban hub

N 13o06′14.8″ E 80o09′26.4″ N 13o07′23.0″ E 80o13′29.0″ N 13o01′18.6″ E 80o13′34.7″ N 13o4′38.3″ E 80o15′41.4″

Table 2 Meteorological conditions in Chennai during the study period (March 2009–February 2010) Month

Temperature (°C)

Humidity (%)

Wind speed (km/h)

Rain fall (cm)

28.86 30.33 34.00 33.17 32.83 31.14 30.29 29.50 26.67 25.50 75.00 28.50

64.57 3.71 50.67 47.33 41.67 62.14 65.86 62.50 84.83 74.00 4.50 67.50

3.71 2.83 9.00 9.83 10.67 5.71 4.29 2.67 2.67 2.67 0.07 5.00

0.00 0.00 0.00 0.00 0.08 0.01 0.47 0.00 1.58 0.00 0.00 0.00


767

Table 3 Seasonal variation of PM 2.5 concentrations in four sampling points in Chennai, India (n=48) Sampling points

Winter season Kolathur Ambathur Saidapet Egmore Summer season Kolathur Ambathur Saidapet Egmore Southwest monsoon Kolathur Ambathur Saidapet Egmore Northeast monsoon Kolathur Ambathur Saidapet Egmore

Fine particulate matter (μg/m3) Minimum

Maximum

Mean

70.0 27.2 71.5 65.1

93.5 114.9 143.8 93.1

85.1 76.5 116.6 82.3

89.5 84.7 64.9 148.3

92.4 106.1 78.9 190.2

91.0 95.2 70.1 170.2

60.9 59.2 72.7 78.8

170.0 90.4 74.5 119.5

113.5 69.8 73.3 102.4

41.1 59.9 69.9 59.2

67.4 99.8 120.5 114.5

52.5 84.8 96.9 88.8

Asia. Metal-based industries, use of diesel generators during industrial operations, fabricating industries, etc. were identified as prominent sources in Ambathur. Prime sources of atmospheric PAHs in urban air as reported in earlier studies were motor vehicles (especially diesel engine vehicles), factories, industrial-oil burning, and home heating (Hayakawa et al. 1995; Mittal and Grieken 2001; Ho and Lee 2002; Park et al. 2002; Yang et al. 2002). Predominant PAHs in all sampling stations were PHENAN, ANTH, and BghiP with maximum levels recording up to

771.5, 727.7, and 210 ng/m3, respectively. Higher concentrations of PHENAN and ANTH in the urban air suggest substantial contribution from traffic emissions. Average concentration of BaP in four sampling stations varied between 6.8 and 16.4 ng/m3, exceeding the NAAQS (NAAQS 2009) annual average of 1 ng/m3. According to the unit risk estimate of the WHO, the exposure to BaP that will cause an excess lifetime cancer risk of 1/100,000 is 0.1 ng/m3 (WHO 2001). Comparisons of mean and range of PAH concentration in this study with those reported for other major cities are reported in Table 4. PAH observed in Chennai is as high as some of the major cities, namely Taiyuan, China (1504.7 ng/m3) and Delhi, India (669.9 ng/m3). Seasonal mean analysis of PAH concentrations at four sampling sites revealed comparatively higher values during winter season than monsoonal seasons (Table 5). Lower PAH levels were recorded during northeast monsoon (440.9 ng/m3) followed by southwest monsoon (463.1 ng/m3). Earlier studies also reported 1.5–10-fold higher concentration of PAHs during winter than that in summer (Baek et al. 1991; Harrison et al. 1996; Caricchia et al. 1999; Ohura et al. 2004). In Egmore and Ambathur, high mean concentration of majority of PAHs (FLT, PYR, CHRY, BghiP, and IcdP) during winter indicates the influences of urban structures and microclimatic conditions. In addition, during winter, an increase in atmospheric emissions due to residential heating was also denoted for higher levels of BaA, BbF, BkF, Ind, and CHRY (Sklorz et al. 2007; Binkova et al. 2003). Apart from that, lower temperature, weaker radiation strength, and additional emission sources during winter are also probable factors for higher level of PAHs (Karar and Gupta 2006; Hong et al. 2007). Mixing height of pollutants also reportedly decreases with a fall in temperature (Ravindra et al. 2008). 3.2 Principal component analysis PCA is the widely used multivariate statistical technique in atmospheric sciences. By grouping variables with similar

Table 4 Mean and total PAH concentration in various cities of the world Study area Taiyuan, China Coimbatore, India Mexico City, Mexico Delhi, India Beijing, China Tehran, Iran Shenzhen, South China Agra, India Seoul, South Korea Chennai, India

Number of PAHs

ΣPAHs (ng/m3)

Mean level (ng/m3)

8 13 11 12 16 16 16 18 15 11

696.6–2,765.4 20–172 60–910 176.7–1,201.3 5.9–362.1 2.1–410.3 110–190 8–97.9 11–350 121.1–1,370.5

1,504.7 90.4 310 669.9 28.5 44.2 128 42.3 89.3 517.1

References Peng et al. (2003) Mohanraj and Azeez (2003) Marr et al. (2004) Sharma et al. (2007) Liu et al. (2007) Halek et al. (2010) Liu et al. (2010) Masih et al. (2010) Park et al. (2002) The present study

PHENAN

ANTH

BDL below detectable level, LOD limit of detection

Summer season (March to May) Kolathur 111.0 BDL Ambathur 53.1 BDL Saidapet 35.5 5.9 Egmore 328.3 96.7 Southwest monsoon (June to August) Kolathur 28.7 37.5 Ambathur 38.8 48.0 Saidapet 17.7 52.1 Egmore 98.9 114.3 Northeast monsoon (September to November) Kolathur 6.9 116.4 Ambathur 57.4 224.2 Saidapet 18.7 108.4 Egmore 20.6 211.4 Limit of detection of PAHs (μg/ml) LOD 0.0042 0.0014 74.1 94.0 90.8 135.4

8.1 8.5 8.2 7.9 0.0092

50.9 82.1 55.2 47.7

78.8 100.3 78.2 100.5

0.0078

55.0 39.6 23.3 41.4

46.9 118.6 159.1 78.8

PYR

64.4 115.8 63.1 49.9

117.6 237.1 162.7 200.6

FLT

Mean PAH concentrations (ng/m3)

Winter season (December to February) Kolathur 50.6 BDL Ambathur 75.5 BDL Saidapet 19.6 32.7 Egmore 91.0 363.8

Sampling sites

Table 5 Seasonal variation of PAH concentrations in Chennai City, India (n=48)

0.0060

26.4 81.2 33.4 62.6

27.8 18.3 29.1 68.6

25.4 58.7 34.4 53.5

19.2 62.3 10.2 11.3

BaA

0.0068

6.0 36.3 8.2 14.6

33.8 44.4 16.3 67.9

38.4 62.9 43.9 39.5

46.3 71.3 17.0 81.0

CHRY

0.0056

6.0 41.2 10.2 16.3

21.0 20.7 13.7 68.6

14.0 52.3 16.4 46.3

18.9 20.6 2.9 32.7

BbF

0.0072

2.0 12.4 2.6 3.1

6.2 8.0 4.2 18.8

3.4 7.1 6.8 55.0

7.8 10.1 2.1 19.8

BkF

0.0095

3.8 18.4 5.4 7.6

7.4 10.6 2.5 26.3

10.3 25.6 6.2 8.5

6.5 8.1 16.2 24.4

BaP

0.0088

7.5 92.1 12.0 32.3

24.8 57.8 38.7 94.2

24.0 83.6 50.9 131.9

38.7 62.8 15.9 53.4

BghiP

0.0065

6.1 9.7 8.0 7.3

10.0 27.6 6.2 48.6

14.5 52.1 7.6 112.9

12.8 15.4 9.6 36.5

IcdP

–

263.2 675.4 306.1 519.0

327.1 456.6 314.0 754.5

360.4 550.8 293.9 963.9

365.2 681.8 448.1 993.4

TPAHs

768 Environ Sci Pollut Res (2011) 18:764–771


769

Fig. 2 Factor analysis of PAH for summer season Fig. 4 Factor analysis of PAH for northeast monsoon season

characteristics into factors, PCA transforms the set of variables into a smaller set of linear combinations that retain the original information as much as possible. The number of significant factors was considered only those with an Eigen value >1.0. In order to assess the PAH source variation, PCA was applied to all four seasons. In summer season (Fig. 2), the total variability was explained by three factors accounting for 81.35%. Factor 1, accounted for total variance of 39.77%, was loaded with FLT, BaA, CHRY, BkF, and BaP. This combination suggested vehicular emissions inclusive of petrol- and diesel-driven engines as the major sources (Caricchia et al. 1999; Kulkarni and Venkataraman 2000; Lin et al. 2002; Hong et al. 2007). Factor 2 accounting for 22.64% of the total variance inferred emissions from dieseldriven heavy trucks as probable sources for PHENAN,

Fig. 3 Factor analysis of PAH for winter season

BkF, and BghiP (Rajput and Lakhani 2009). Factor 3 accounted for 18.94% of the total variance with ANTH and IcdP which could be contributed from wood and rubbish combustion. For winter season (Fig. 3), PCA identified four complex factors accounting for 97.1% of total variance. Factor 1 loaded with PHENAN, CHRY, BbF, and BkF accounted for 38.33% of variance. Emissions from diesel- and gasoline-powered vehicles were identified as probable sources of these PAHs (Venkataraman et al. 1994; Randolph and Joel 2003). Factor 2 consisted of BaA and BghiP with representation of 23.15% of total variance. Factor 3 accounted for 21.5% variance with loadings of ANTH, BaP, and IcdP is attributed to diesel-powered vehicular emission. Factor 4 yielded 14.11% of total variance with loadings of FLT and PYR.

Fig. 5 Factor analysis of PAH for southwest monsoon season

770

In northeast monsoon season (Fig. 4), the total variance of 88.62% was explained by three factors. Factor 1 was highly loaded with PHENAN, BaA, CHRY, BbF, BkF, BaP, and BghiP accounting for 58.08% total variability. It mainly consisted of the multiring PAHs, which are common in the particulate phase. Factor 2 was loaded with ANTH and PYR. This factor indicated wood combustion source. Factor 3 loaded with IcdP represented 12.53% of total variance, suggesting contribution from spark ignition engines (Harrison et al. 1996; Miguel et al. 1998). In southwest monsoon, among the total variance of 83.86%, factor 1 accounted for 48.07% total variability with PHENAN, ANTH, BbF, BaP, BghiP, and IcdP (Fig. 5). This factor could be attributed to the gasoline and diesel vehicle emissions with high molecular weight PAHs. The second factor with 35.79% total variance grouped as FLT, BaA, CHRY, and BkF. It is worthy to mention that during 1984–2008, Chennai experienced a remarkable 21-fold increase in vehicular traffic from 0.12 million to 2.51 million. According to the CMDA (2008) report, daily average person trips in Chennai raised from 7.45 million to 9.59 million during 1992 and 2005, respectively. The report also highlights sharp decline in the share of public transport and cycle over the years. This trend suggests increasing vehicular ownership and stagnancy in public transportation growth. Furthermore, an average of 1,780 new vehicles is introduced on roads every day without parallel raise in road space (only 4% of the total area). With the rapid rise in special economic industrial zones and establishments of multinational companies, vehicular recruitment is expected to increase manifold in Chennai. Moreover, the increasing number of sports utility vehicles and fleet changes is also likely to make significant PAH emissions.

4 Conclusions In Chennai metropolitan city, India, both airborne fine particulates (PM 2.5) and its associated polycyclic aromatic hydrocarbons are present at alarming levels. Benzo(a) pyrene, which serves as an indicator of carcinogenic risk, ranged from 6.8 to 16.4 ng/m3, exceeding the NAAQS annual average of 1 ng/m3. Highest mean concentration of 11 PAHs (790.8 ng/m3) was recorded at Egmore (urban commercial area) followed by industrial site Ambathur (582.9 ng/m3). The principal component analysis suggested vehicular emissions followed by off-road combustion sources such as wood, solid waste, and other rubbish as major sources for airborne PAHs. Seasonal comparative analysis of PAHs at four sampling sites unveiled comparatively higher values during winter season than monsoonal seasons. Lower PAH levels were recorded during northeast monsoon (440.9 ng/m3) followed by southwest monsoon (463.1 ng/m3). The study hints that if the current trend in


urbanization and vehicular growth continues at the same pace, a major exercise in planning infrastructure, fuel quality, road network, and abatement of industrial emissions will be highly essential to maintain the air quality. Acknowledgments The authors would like to thank the Defence Research and Developmental Organization (DRDO), Government of India, for financial support.

References Baek SO, Goldstone ME, Kirk PWW, Lester JN, Perry R (1991) Phase distribution and particle size dependency of polycyclic aromatic hydrocarbons in the urban environment. Chemosphere 22:503–520 Binkova B, Cerna M, Pastorkova A, Jelinek R, Benes I, Novak J (2003) Biological activities of organic compounds adsorbed onto ambient air particles: comparison between the cities of Teplice and Prague during the summer and winter seasons 2000–2001. Mutat Res 525:43–59 Bostrom CE, Gerde P, Hanberg A, Jenstrom B, Johansson C, Kyrklund T, Rannug A, Tornqvist M, Victorin K, Westerholm R (2002) Cancer risk assessment, indicators, and guidelines for polycyclic aromatic hydrocarbons in the ambient air. Environ Health Perspect 110:451–488 Bourottea C, Fortic MC, Taniguchid S, Bıcegod MC, Lotufoa PA (2005) A wintertime study of PAHs in fine and coarse aerosols in Sao Paulo city, Brazil. Atmos Environ 39:3799–3811 Caricchia M, Chiavarini S, Pezza M (1999) Polycyclic aromatic hydrocarbons in the urban atmospheric particulate matter in the city of Naples (Italy). Atmos Environ 33:3731–3738 Chattopadhyay G, Samanta G, Chatterjee S, Chakraborti D (1998) Determination of particulate polycyclic aromatic hydrocarbons in ambient air of Calcutta for three years during winter. Environ Technol 19:873–882 CMDA (2008) Chennai Metropolitan Development Authority; Highlights of the Recommendations of the state level committee on road connectivity & traffic improvements in Chennai. Government of Tamilnadu, India Childers JW, Witherspoon CL, Smith LB, Joachim D (2000) Realtime and integrated measurement of potential human exposure to particle-bound polycyclic aromatic hydrocarbons (PAHs) from aircraft exhaust. Environ Health Perspect 108:53–862 Colombini MP, Fuoco R, Giannarelli S, Termine M, Abete C, Vincentini M, Berti S (1998) Particulate samples by HPLC with fluorescence detection: a field application. Microchem J 59:228–238 Halek F, Kianpour-Rad M, Kavousirahim A (2010) Seasonal variation in ambient PM mass and number concentrations (case study: Tehran, Iran). Environ Monit Assess 169:501–507 Harrison RM, Smith DJT, Luhana L (1996) Source apportionment of atmospheric polycyclic aromatic hydrocarbons collected from an urban location in Birmingham, UK. Environ Sci Technol 30:825–832 Hayakawa KT, Murahashi M, Butoh M, Miyazaki M (1995) Determination of 1, 3-, 1, 6-and 1, 8-dinitropyrenes and 1nitropyrene in urban air by high-performance liquid chromatography using chemiluminescence detection. Environ Sci Technol 29:928–932 Heflich RH, Fifer EK, Djuric Z, Beland FA (1985) DNA adduct formation and mutation induction by nitropyrenes in Salmonella and Chinese hamster ovary cells: relationships with nitroreduction and acetylation. Environ Health Perspect 62:135–143 Ho KF, Lee SC (2002) Identification of atmospheric volatile organic compounds (VOCs), polycyclic aromatic hydrocarbons (PAHs)

Environ Sci Pollut Res (2011) 18:764–771 and carbonyl compounds in Hong Kong. Sci Total Environ 289:145–158 Hong HS, Yin HL G, Wang XH, Ye CX (2007) Seasonal variation of PM10-bound PAHs in the atmosphere of Xiamen, China. Atmos Res 85:429–441 Karar K, Gupta AK (2006) Seasonal variations and chemical characterization of ambient PM10 at residential and industrial sites of an urban region of Kolkata (Calcutta), India. Atmos Res 81:36–53 Kulkarni P, Venkataraman C (2000) Atmospheric polycyclic aromatic hydrocarbons in Mumbai, India. Atmos Environ 34:2785–2790 Larsen RK, Baker JE (2003) Source apportionment of polycyclic aromatic hydrocarbons in the urban atmosphere: a comparison of three methods. Environ Sci Technol 37:1873–1881 Lim LH, Harrison RM, Harrad S (1999) The contribution of traffic to atmospheric concentrations of polycyclic aromatic hydrocarbons. Environ Sci Technol 33:3538–3542 Lin TC, Chang FH, Hsieh JH, Chao HR, Chao MR (2002) Characteristics of polycyclic aromatic hydrocarbons and total suspended particulates in indoor and outdoor atmosphere of a Taiwanese temple. J Hazard Mater 95:1–12 Liu Y, Tao S, Yang Y, Doua H, Yang Y, Coveney RM (2007) Inhalation exposure of traffic police officers to polycyclic aromatic hydrocarbons (PAHs) during the winter in Beijing, China. Sci Total Environ 383:1–3 Liu G, Tong Y, Luon JHT, Zhang H, Sun H (2010) A source study of atmospheric polycyclic aromatic hydrocarbons in Shenzhen, South China. Environ Monit Assess 163:599–606 Marr LC, Grogan HW, Molina LT, Molina MJ (2004) Vehicle traffic as a source of polycyclic aromatic hydrocarbons exposure in the Mexico City Metropolitan Area. Environ Sci Technol 38:2584– 2592 Masih A, Saini R, Singhvi R, Taneja A (2010) Concentrations, sources, and exposure profiles of polycyclic aromatic hydrocarbons (PAHs) in particulate matter (PM10) in the north central part of India. Environ Monit Assess 163:421–431 Miguel AH, Kirchstetter TW, Harley RA, Hering SV (1998) On-road emissions of particulate polycyclic aromatic hydrocarbons and black carbon from gasoline and diesel vehicles. Environ Sci Technol 32:450–455 Mittal R, Grieken AKV (2001) Health risk suspended particulate matter with special reference to PAHs: a review. Rev Environ Health 16:169–189 Mohanraj R, Azeez PA (2003) Polycyclic aromatic hydrocarbons in air and their toxic potency. Reson J Sci Educ 8:20–27 Moller L (1994) In vivo metabolism and genotoxic effects of nitrated polycyclic aromatic hydrocarbons. Environ Health Perspect 102:139–146 Moller L, Lax I, Eriksson LC (1993) Nitrated polycyclic aromatic hydrocarbons: a risk assessment for the urban citizen. Environ Health Perspect 101:309–315 NAAQS (National Ambient Air Quality Standards) (2009) Ministry of forest and environment. Government of India, New Delhi Oamh NT, Reutergardh LB, Dung NT (1999) Emission of polycyclic aromatic hydrocarbons and particulate matter from domestic combustion of selected fuels. Environ Sci Technol 33:2703–2709 Ohura T, Amagai T, Fusaya M, Matsushita H (2004) Polycyclic aromatic hydrocarbons in indoor and outdoor environments and factors affecting their concentrations. Environ Sci Technol 38:77–83 Park SS, Kim YJ, Kang CH (2002) Atmospheric polycyclic aromatic hydrocarbons in Seoul, Korea. Atmos Environ 36:2917–2924 Park SY, Lee SM, Ye SK, Yoon SH, Chung MH, Choi J (2006) Benzo [a]pyrene-induced DNA damage and p53 modulation in human hepatoma HepG2 cells for the identification of potential

771 biomarkers for PAH monitoring and risk assessment. Toxicol Lett 167:27–33 Peng L, Zeng FG, Chen M (2003) Distribution characteristics and source analysis of n-alkanes (C14∼31) and PAHs in total suspended particulates in urban area of Taiyuan city. Rock Miner Anal 22:206–210 Raiyani CV, Jani JP, Desai NM, Shaha JA, Kashyap SK (1993) Levels of PAHs in ambient environment of Ahmedabad city. Indian J Environ Prot 13:206–221 Rajput N, Lakhani A (2009) Measurements of polycyclic aromatic hydrocarbons at an industrial site in India. Environ Monit Assess 150:273–284 Randolph KL III, Joel EB (2003) Source apportionment of polycyclic aromatic hydrocarbons in the urban atmosphere: a comparison of three methods. Environ Sci Technol 37:1873–1881 Ravindra K, Wauters E, Grieken RV (2008) Variation in particulate PAHs levels and their relation with the transboundary movement of the air masses. Sci Total Environ 396:100–110 Ryno M, Rantanen L, Papaioannou E, Konstandopoulos AG, Koskentalod T, Savela K (2006) Comparison of pressurized fluid extraction, Soxhlet extraction and sonication for the determination of polycyclic aromatic hydrocarbons in urban air and diesel exhaust particulate matter. J Environ Monit 8:488–493 Sharma AP, Tripathi BD (2009) Assessment of atmospheric PAHs profile through Calotropis gigantea R.Br. leaves in the vicinity of an Indian coal-fired power plant. Environ Monit Assess 149:477–482 Sharma H, Jain VK, Khan ZH (2007) Characterization and source identification of PAH in the urban environment of Delhi. Chemosphere 66:302–310 Sikalos TI, Paleologos EK, Karayannis MI (2002) Monitoring of time variation and effect of some meteorological parameters in polynuclear aromatic hydrocarbons in Ioannina, Greece with the aid of HPLC-fluorescence analysis. Talanta 58:497–510 Sklorz M, Schnelle-Kreis J, LiuY OJ, Zimmermann R (2007) Daytime resolved analysis of polycyclic aromatic hydrocarbonsin urban aerosol samples—impact of sources and meteorological conditions. Chemosphere 67:934–943 Stanley S, Percival CJ, Auer M, Braithwaite A, Newton MI, McHale G, Hayes W (2003) Detection of polycyclic aromatic hydrocarbons using quartz crystal microbalances. Anal Chem 75:1573–1577 US-ATSDR (United States-Agency for Toxic Substances and Disease Registry), 1995. Toxicology Profile for Polycyclic Aromatic Hydrocarbons. US Department of Health and Human Services, Atlanta, G.A. http://www.atsdr.cdc.gov/toxprofiles/tp69.pdf. Accessed 20 March 2010 Vasconcellos PC, Zacariasa D, Pires MAF, Pool CS, Carvalho LRF (2003) Measurements of polycyclic aromatic hydrocarbons in airborne particles from the metropolitan area of Sao Paulo City, Brazil. Atmos Environ 37:3009–3018 Venkataraman C, Lyons JM, Friedlander SK (1994) Size distributions of polycyclic aromatic hydrocarbons and elemental carbon. 1. Sampling, measurement methods, and source characterization. Environ Sci Technol 28:555–562 WHO (World Health Organization) (2001) Air quality guidelines for Europe. http://www.euro.who.int/document/e71922.pdf. Accessed 8 June 2010 Yang HH, Lai SO, Hsieh LT, Hsueh HJ, Chi TW (2002) Profiles of PAH emission from steel and iron industries. Chemosphere 48:1061–1074 Zimmermann R, Heger HJ, Kettrup A (1999) On-line monitoring of traces of aromatic, phenolic, and chlorinated components in flue gases of industrial scale incinerators and cigarette smoke by direct-inlet laser ionization mass spectrometry (REMPI-TOFMS). Fresenius J Anal Chem 363:720–730