ARTICLE IN PRESS

Chemosphere xxx (2006) xxx–xxx

www.elsevier.com/locate/chemosphere

Polycyclic aromatic hydrocarbons (PAHs) concentrations and

related carcinogenic potencies in soil at a semi-arid region of India
Amit Masih, Ajay Taneja *

School of Chemical Sciences, Department of Chemistry, St. Johns College, Agra, Uttar Pradesh 282 002, India

Received 10 August 2005; received in revised form 7 December 2005; accepted 25 January 2006

Abstract

A study of polycyclic aromatic hydrocarbons in surface soil was conducted at selected locations in Agra (semi-arid region of India) for
a span of one year in order to ascertain the contamination levels. The concentrations of PAH were measured at four locations in the city
of Agra, which covers industrial, residential, roadside and agricultural areas. The samples were extracted with hexane by ultrasonic agi-
tation. The extracts were then fractioned on a silica-gel column and the aromatic fraction was subjected to HPLC. The average concen-
tration of total PAH in all samples was 12.1 lg g1 and the range was from 3.1 lg g1 to 28.5 lg g1. The maximum concentrations of
PAHs were found to be in winter season. The concentration of PAH decreased in the order chrysene > benzo(b)fluoranthene > fluoranth-
ene. Factor analysis suggests that the mixed signature of all the sources are intermediate between vehicular and combustion activities.
Ó 2006 Elsevier Ltd. All rights reserved.

Keywords: HPLC; Polycyclic aromatic hydrocarbon; Semi-arid region; Surface soil

1. Introduction ally soot particles, by adsorption or condensation upon

Polycyclic aromatic hydrocarbons (PAHs) are chemicals
containing two or more fused benzene rings in a linear,
angular or cluster arrangement. PAH contain only carbon
and hydrogen. They are usually generated under inefficient
combustion conditions, such as insufficient oxygen (Soren-
sen, 1994; Nam et al., 2003) by primary natural sources
which are forest fires and volcanic activity, but most of
the PAHs released into the environment arise from anthro-
pogenic sources such as burning of fossil fuels, petroleum
refinery, industrial processes, as a constituent of coal tar
and motor vehicle exhaust. The lighter PAH (2–3 rings),
which are generally not carcinogenic, are mostly found in
the gas phase while the heavier ones are mainly associated
with airborne particles. Heavier PAH (with more than
three rings) are rapidly attached to existing particles, usu-
*
Corresponding author. Tel.: +91 562 2800882.
E-mail address: ataneja5@hotmail.com (A. Taneja).
cooling of fuel gas (Kamens et al., 1995). The environmen-
tal occurrence of PAHs has been associated with adverse
effects on public health (Grimmer et al., 1983; Yang
et al., 1991; Rost and Loibner, 2002). Persistent organic
pollutants (POPs) are transported in the atmosphere at
over short and long distances in both gaseous and particu-
late forms. Although some POPs are released slowly into
the atmosphere (Harner et al., 1995), these omnipresent
compounds are subject to redistribution and transforma-
tion processes (Reilley et al., 1996; Massei and Ollivon,
2004). Atmospheric deposition constitutes the main input
of semi-volatile organic compounds to soil (Tremolada
et al., 1996). Once entered in the soil they accumulate in
horizons rich in organic matter where they are likely to
be retained for many years due to their persistence and
hydrophobicity (Krauss et al., 2000). Consequently, soils
are an important reservoir for these compounds (Ockenden
et al., 2003) and exchanges between soils and the atmo-
sphere is a widely studied process (Bidleman and McCon-
nell, 1995; Wania and Mackay, 1996). With the increase

0045-6535/$ - see front matter Ó 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.chemosphere.2006.01.062
 ARTICLE IN PRESS
2 A. Masih, A. Taneja / Chemosphere xxx (2006) xxx–xxx
in fossil fuel combustion, resulting from the industrial
expansion, traffic and population growth, over last few dec-
ades, the atmospheric concentrations of PAH in Asian
countries are expected to be high. Thus it is important to
acquire information about this environmental compart-
ment and its role in micro pollutant cycle.
In India, few studies have reported ambient PAH con-
centration in Ahmedabad (Raiyani and Shah, 1993), Mum-
bai (Sahu et al., 2001), Delhi (Kannan and Kapoor, 2004).
To our knowledge there has been a shortage of soil PAH
studies. Since PAHs are one of the most serious pollutants
because of their carcinogenicity and mutagenicity (IARC,
1983; Yang et al., 1991; Massei and Ollivon, 2004) which
have drawn attention of the scientific community, it is
important to determine the amounts of PAHs in soil as
their concentration in soil correlates significantly with the
corresponding levels in air (Vogt et al., 1987; Nam et al.,
2003; Massei and Ollivon, 2004) and is a good indicator
of the surrounding air pollution and the proximity of
sources. The aim of this study was to determine soil con-
tamination by PAHs and to identify sources based on vari-
ations in PAHs profiles between the sites as well as to assess
the carcinogenic potencies related to PAHs.
2. Materials and methods
2.1. Regional site description
Agra, the city of Taj Mahal (27°10 0 N 78°02 0 E) is located
in the north central part of India about 200 kms South of
Delhi in the Indian state of Uttar Pradesh. Agra is consid-
ered as a semi-arid zone as two third of its boundary are
surrounded by the Thar desert of Rajasthan. Three high-
ways are crossing the city. The climate during summer is
hot and dry with temperature ranging from 32 °C to
48 °C. In winter the temperature ranges from 5.5 °C to
30.5 °C. The down ward wind is south–south-east i.e.
SSE 29% and north-east i.e. NE 6% in summers and it is
west–north-west i.e. WNW 9.4% and north–north-west
i.e. NNW 11.8% in winters. The atmospheric pollution
load is high because of the down ward wind; pollutants
may be transported to the different areas mainly from an
oil refinery situated in Mathura (50 kms from the center
of Agra City). Agra has 1 271 000 of population. 3 86 635
vehicles are registered and 32 030 generator sets are used.
It has been indicated earlier that in Agra, 60% pollution
is due to vehicles (CPCB, Amar Ujala, 2005). St. John’s
College, which is situated in the heart of Agra city, is con-
sidered as a roadside area. It lies by the side of a road that
carries a maximum traffic density of about 105 vehicles per
day, which results in production of smoke, and total sus-
pended particulate matter by engine idling and gear
changes. Nunhai has being considered as an industrial zone
because large number of diesel generator sets plants, iron
processing and tanning industries are there. Towards the
north is located Dayalbagh which is exclusively agricul-
tural area. The Taj trapezium (area surrounding the Taj
Mahal 10 400  km2) located to the south of the site is con-
sidered to be a residential area, which is totally a green belt.
2.2. Sample collection
For the purpose of sample collection Agra city was
divided into four parts based on industrial, roadside, agri-
cultural and residential locations. Samples were collected
with the help of an auger from 0 to 6 cm of topsoil. A total
of 319 soil samples were collected (80 from each location)
for analysis. The collected samples were sieved through
20-mesh sieve and stored in polybags in a refrigerator.
2.3. Extraction and analysis of PAHs
Twenty gram of soil sample was extracted for 45 min
with hexane (30 ml) in an ultrasonic bath extractor. The
extract was decanted at the rate of 3300 rpm in a decanter
(Supelco) and then passed through silica-gel column for the
purification (EPA, 1994). The obtained extract was evapo-
rated by a flow of nitrogen and redissolved in 1 ml of Ace-
tonitrile. The extract was analysed for PAH’s by using the
HPLC with UV visible detector (Shimadzu LC-10AD). The
analytical column was of 250 mm length and 4.6 mm i.d;
packed with totally porous spherical RP-18 material (Par-
ticle size 5 lm) preceded by a guard column (10 mm long
and 4.6 mm i.d.). Acetonitrile–water mixture (70:30) was
used as mobile phase at a flow rate of 1.5 ml min1. Sam-
ples of 100 ll (0.1 ml) were injected into the column
through the sample loop. For the detection of compounds
UV detector was set at 254 nm for analysis. The data was
processed with a CR7A chromatopac data processor.
Standards were obtained individually (as the solids) from
polyscience Chemical Company, USA. The following
compounds were quantified: naphthalene, acenaphthene,
acenaphthylene, fluorene, phenanthrene, anthracene, fluo-
ranthene, pyrene, benzo(a)anthracene, chrysene, benzo(b)
fluoranthene, benzo(k)fluoranthene benzo(a)pyrene and
benzo(ghi)perylene. All these compounds are on the
USEPA priority pollutants list. The procedure described
above has been checked for recovery efficiencies using
spiked PAH standards. Recoveries range between 30%
and 70%, with the lower values corresponds to the lower
molecular weight PAH compounds. Presented data are cor-
rected accordingly with the means of triplicate analyses.
Replicated analyses give an error between ±10% and
±20% for PAH in soils.
3. Results and discussion
3.1. PAHs in soil particles
The average and standard deviation of individual PAH
concentrations measured in soils at the various sites are pre-
sented in Table 1. The total PAH (t-PAH) concentrations
were 13.72, 12.98, 9.37 and 6.73 lg g1 at industrial, road-
side, residential and agricultural sites respectively. The
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A. Masih, A. Taneja / Chemosphere xxx (2006) xxx–xxx 3

Table 1
Mean concentration with SD of PAHs at different locations of Agra (lg g1)
PAHs Industrial Roadside Residential Agricultural
Mean ± SD Mean ± SD Mean ± SD Mean ± SD
NAP 1.18 ± 1.11 1.07 ± 1.84 0.90 ± 1.16 0.69 ± 0.77
ACY 0.62 ± 0.54 0.47 ± 0.62 0.33 ± 0.57 0.42 ± 0.61
ACE + FLU 1.06 ± 1.72 0.97 ± 1.88 0.82 ± 1.20 0.63 ± 0.60
PHE 0.43 ± 0.51 0.32 ± 0.37 0.47 ± 0.66 0.14 ± 0.31
ANT 1.29 ± 1.12 1.02 ± 0.66 0.57 ± 0.39 0.36 ± 0.21
FLT 1.72 ± 1.02 1.29 ± 1.17 0.89 ± 1.11 0.58 ± 0.32
PYR ND 1.23 ± 1.41 ND ND
B(a)A 0.81 ± 1.06 0.56 ± 0.45 0.45 ± 0.31 0.26 ± 0.21
CHR 4.07 ± 2.26 3.19 ± 2.36 3.03 ± 2.91 2.19 ± 2.18
B(b)F 1.53 ± 1.47 1.32 ± 1.20 1.27 ± 1.41 0.92 ± 1.42
B(k)F ND 0.30 ± 0.83 ND ND
B(a)P ND 0.39 ± 0.36 ND ND
B(ghi)P 1.01 ± 1.09 0.85 ± 0.72 0.64 ± 0.79 0.54 ± 0.43
Total 13.72 ± 11.90 12.98 ± 13.87 9.37 ± 10.46 6.73 ± 7.12
NAP—Naphthalene, ACY—Acenapthylene, ACE—Acenapthene, FLU—Fluorene, PHE—Phenanthrene, ANT—Anthracene, FLT—Fluoranthene,
PYR—pyrene, B(a)A—Benzo(a)fluoranthene, CHY—Chrysene, B(b)F—Benzo(b)fluoranthene, B(k)F—Benzo(k)fluoranthene, B(a)P—Benzo(a)pyrene,
B(ghi)P—Benzo(ghi)perylene.

mean concentration of t-PAH was 12.14 lg g1 for all sites Table 2
together. The industrial sites had the highest total PAH Soil PAH concentrations compiled from literature data
concentration followed by roadside, residential and agricul- Study area PAH Number Reference
tural site. High concentrations at industrial site can be due concentration of PAH
(lg g1)
to the location of the site, which is well known for generator
manufacturing, tanning and iron casting industries. Con- Agricultural (rural)
Brazil 0.096 20 Wilcke et al. (1999a)
centrations at roadside may result from the proximity of
UK 0.19 12 Wild and Jones (1995)
the busy road, which has very intense automobile traffic Germany 1.90 06 Tebaay et al. (1993)
about 105 vehicles per day. Trapido (1999) estimated India 6.7 11 Present study
PAH content at agricultural site about 0.10 lg g1 which Residential (urban)
was considered as background value for PAH. Observed Bangkok 0.38 20 Wilcke and Muller (1999b)
value (6.70 lg g1) of PAH at agricultural site is higher than Brazil 0.39 20 Wilcke et al. (1999a)
the background levels may be due to the atmospheric trans- Germany 1.80 06 Tebaay et al. (1993)
port of PAH from sources to remote sites. These results also UK 4.20 12 Wild and Jones (1995)
India 9.3 11 Present study
indicate that PAH concentration are strongly linked to the
land use of the site. The trends of the concentrations of the Roadside (urban)
Australia 3.30 14 Yang et al. (1991)
major PAH found in present study were chrysene > fluo-
USA 58.68 14 Rogge et al. (1993)
ranthene > benzo(b)fluoranthene at industrial site, chry- India 12.9 14 Present study
sene > benzo(b)fluoranthene > fluoranthene at roadside
Industrial (urban)
and chrysene > benzo(b)fluoranthene > naphthalene at res-
UK 4.50 12 Wild and Jones (1995)
idential and agricultural sites. In all the sites chrysene and Germany 16.00 06 Tebaay et al. (1993)
benzo(b)fluoranthene were the predominant compounds. Austria 79.00 18 Weiss et al. (1994)
This might be due to industrial-oil burning, wood combus- India 13.7 11 Present study
tion and emission coming from diesel powered vehicles
(Ravindra et al., 2001).
Table 2 shows a worldwide comparison of PAH concen- much difference between each other. In the present data,
tration with the present study. The PAH concentration in contamination in the urban industrial area appears to be
soil of industrial (13.72 lg g1) and roadside (12.98 lg g1) two times higher than in agricultural areas; similar results
area of Agra is less than the concentration found in Austria/ have been reported in earlier studies (Tremolada et al.,
Germany (79.00/16.00 lg g1) and USA (58.60 lg g1), 1996; Wagrowski and Hites, 1997).
respectively, whereas residential (9.37 lg g1) and agricul- Fig. 1 shows the relative contribution of 2-, 3-, 4-, 5-,
tural (6.73 lg g1) sites concentrations of PAH were found and 6-ring PAHs in the soils of different locations investi-
to be higher than in UK (4.20 lg g1) and Germany gated in this study. The average percentage of t-PAH based
(1.90 lg g1), respectively. As evident from the Table 2 on the rings were 9.15% (2 ring), 23.1% (3 ring), 47% (4
the concentrations measured in soils of various sites at Agra ring), 13.4% (5 ring), and 7.15% (6 ring). The Fig. 1 also
(industrial, roadside, residential and agricultural) show illustrates that 4-ring and 3-ring PAHs were found to be
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4 A. Masih, A. Taneja / Chemosphere xxx (2006) xxx–xxx

the higher concentration of PAH at this season. While dur-

ing the months of monsoon season the region is generally
experienced with the frequent rain showers and washout
effects of pollutants. In addition to dry deposition, wet
deposition (rain) of PAH may also occur at soil surface
in this season and should have resulted in higher soil
PAH concentration. In contrast, the concentration of soil
PAH was observed to be lower in monsoon. Lower concen-
tration of PAH during the monsoon season in this region
can be explained due to the percolation of PAH into the
inner depth of the soil. Although, percolation of PAH
depends on several factors like PAH molecular structure,
water solubility, Henry’s constant, mode of transport and
flow rate. The total PAH ratios of winter and Monsoon
(W/M) seasons varied from 1.8 to 2.8 with the maximum
(W/M) ratios observed for industrial followed by agricul-
Fig. 1. Distribution of PAHs in the soil of different locations of Agra. ture, residential and roadside. Lower (W/M) ratios of
PAH at roadside soil may be due to the high vehicular
emissions and the continuous deposition of PAH on road-
dominant in the soils of Agra region having 47% and 23.1% side at all seasons.
of the t-PAH whereas 5-ring compounds including ben-
zo(a)pyrene (considered to be most carcinogenic com- 3.3. Factor analysis
pound) contributes only 13.4% of the t-PAH.
A varimax rotated factor analysis was performed to
3.2. Seasonal variation identify the main sources influencing the PAH concentra-
tion at the sampling sites. In this statistical method a set
The climate of Agra can be broadly classified into three of multiple inter correlated variables is replaced by small
seasons, winter (November–February), summer (March– number of independent variables (factors) by orthogonal
June) and monsoon (July–October). Table 4 summarizes transformations (rotations). This is achieved by diagnosing
the seasonally averaged concentrations of all measured the correlation matrix of the variable i.e. by computing
PAH in soil at four sites of Agra; i.e. industrial, roadside, their Eigen values and Eigen vectors. Factor loadings
residential and agricultural. The concentrations of PAH obtained after the rotation called varimax rotation gives
in winter, summer and monsoon are dominating in indus- the correlation between the variables and the factors. Each
trial area i.e. 20.45, 13.43 and 7.28 lg g1, respectively, variable was also evaluated for its KMO value (Keiser
whereas the lowest concentrations of PAH are formed to Mayer Olvin), which gives sampling adequacy, and data
be in agricultural area i.e. 10.18, 6.21 and 3.80 lg g1, was included in the matrix only if it had Eigen values
respectively. The concentrations of PAH in roadside as well greater than one. The varimax procedure was adopted
as residential sites were found to be 17.07 and 13.04 lg g1 for rotation of the factor matrix to transfer the initial
in winter, 12.12 and 9.25 lg g1 in summer and 9.75 and matrix into one that was easier to interpret. In the present
5.82 lg g1 in monsoon. The differences in PAH concentra-
tion in soil is due to the characteristics of individual sites. Table 3
Although the trend of seasonal variation of all PAH at Mean, range and TEFs of PAHs with BAP exposure at Agra (lg g1)
all the sites is similar in nature i.e. maximum concentration PAHs Mean Range TEFsa BAPexposure
of PAH were found to be in winter followed by summer
NAP 0.96 0.27–2.06 0.001 0.00096
and monsoon seasons. This trend can be easily visualized ACY 0.46 0.09–1.56 0.001 0.00046
in Fig. 2. Differences in concentration of PAH in soil can ACE + FLU 0.87 0.10–1.90 0.001 0.00087
be explained with the different meteorological conditions PHE 0.34 0.06–0.96 0.001 0.00034
of these seasons. Temperature of soil is a very important ANT 0.81 0.10–1.88 0.01 0.0081
factor in determining the leachability or mobility of soil FLT 1.12 0.38–2.98 0.001 0.00112
PYR 1.23 0.49–3.07 0.001 0.00123
PAH. In this region, summer is generally characterized B(a)A 0.52 0.12–1.61 0.1 0.052
by high temperature ranging from 35 °C to 47 °C. The CHR 3.12 0.99–6.44 0.01 0.0312
leaching concentration of PAH at present site increases B(b)F 1.26 0.34–2.64 0.1 0.126
with increasing temperature as biodegradation and volatil- B(k)F 0.30 0.04–0.71 0.1 0.030
ity accompanied by rising temperature (Kim and Osako, B(a)P 0.39 0.07–0.94 1 0.39
B(ghi)P 0.76 0.14–1.79 0.01 0.0076
2003), resulting the lower PAH in the summer than in win-
ter season. In contrast, in the winter season at low temper- Total 12.14 3.19–28.54 1.33 0.65
a
ature microbial breakdown of PAH is decreased resulting TEFs compiled by Tsai and Shih (2004).
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A. Masih, A. Taneja / Chemosphere xxx (2006) xxx–xxx 5

Table 4
Seasonal average concentrations of PAHs in soil at different sites of Agra (lg g1)
PAHs Industrial Roadside Residential Agricultural
S M W S M W S M W S M W
NAP 1.28 0.63 1.63 0.92 0.87 1.42 0.83 0.74 1.13 0.66 0.49 0.92
ACY 0.59 0.41 0.86 0.41 0.27 0.73 0.32 0.21 0.46 0.36 0.12 0.78
ACE + FLU 1.14 0.72 1.32 0.83 0.72 1.36 0.73 0.68 1.05 0.53 0.39 0.97
PHE 0.22 0.45 0.62 0.28 0.14 0.54 0.41 0.37 0.63 0.12 0.08 0.22
ANT 1.31 0.79 1.77 0.91 0.89 1.26 0.57 0.32 0.82 0.28 0.21 0.59
FLT 1.61 0.68 2.87 1.24 1.12 1.51 0.80 0.78 1.09 0.55 0.40 0.79
PYR ND ND ND 1.19 1.11 1.31 ND ND ND ND ND ND
B(a)A 0.56 0.84 1.03 0.53 0.36 0.79 0.44 0.32 0.59 0.22 0.14 0.42
CHR 4.23 1.62 6.36 3.21 2.24 4.12 3.39 1.08 4.62 2.09 0.92 3.56
B(b)F 1.53 0.79 2.27 1.12 0.87 1.97 1.17 0.81 1.83 0.91 0.66 1.19
B(k)F ND ND ND 0.25 0.15 0.50 ND ND ND ND ND ND
B(a)P ND ND ND 0.39 0.31 0.47 ND ND ND ND ND ND
B(ghi)P 0.96 0.35 1.72 0.84 0.70 1.01 0.59 0.51 0.82 0.49 0.39 0.74
Total 13.43 7.28 20.45 12.12 9.75 17.07 9.25 5.82 13.04 6.21 3.80 10.18
S—summer, M—monsoon, W—winter.

INDUSTRIAL ROADSIDE

SUMMER MONSOON WINTER SUMMER MONSOON WINTER

14 12
12
Concentration

10
Concentration

10 8
(µg g-1)
(µg g-1)

8
6
6
4
4
2 2
0 0
FLT
ACE+FLU

B(ghi)P
NAP
ACY

PHE
ANT

PYR
B(a)A

B(b)F
B(k)F
B(a)P
CHR
FLT
ACE+FLU

B(ghi)P
PYR
B(a)A

B(b)F
B(k)F
B(a)P
NAP
ACY

PHE
ANT

CHR

PAHs PAHs

RESIDENTIAL AGRICULTURAL

SUMMER MONSOON WINTER SUMMER MONSOON WINTER

10 7
Concentration
Concentration

8 6
5
(µg g-1)

(µg g-1)

6 4
4 3
2
2
1
0 0
FLT

B(ghi)P
PYR
B(a)A

B(b)F
B(k)F
B(a)P
NAP
ACY

PHE
ANT

CHR
ACE+FLU
FLT

B(ghi)P
NAP
ACY

PHE
ANT

PYR
B(a)A

B(b)F
B(k)F
B(a)P
CHR
ACE+FLU

PAHs PAHs

Fig. 2. Seasonal trends of PAH at different sites.

study, the SPSS (version 7.5) computer software was used icant. As presented in Table 5, at all the sites only one
to perform factor analysis. factor is extracted except that of industrial site which is
Results obtained by varimax rotated factor analysis are having two factors. Agricultural, residential and roadside
given in Table 5. Shown results in the table have load- contributed 89.9%, 91.6%, 86.6%, variance of data set,
ing > 0.5, because they are deemed to be statistically signif- respectively, whereas at the industrial site total of 98.8%
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6 A. Masih, A. Taneja / Chemosphere xxx (2006) xxx–xxx

Table 5
Results of factor analysis with varimax rotation on PAHs in soil of Agra
PAHs Agricultural Residential Roadside Industrial
Factor 1 Factor 1 Factor 1 Factor 1 Factor 2
NAP 0.95 0.89 0.96 0.99 0.01
ACY 0.98 0.95 0.97 0.91 0.34
ACE + FLU 0.97 0.97 0.96 0.99 0.01
PHE 0.84 0.97 0.97 0.19 0.97
ANT 0.96 0.96 0.95 0.97 0.19
FLT 0.95 0.95 0.95 0.94 0.31
PYR – – 0.93 – –
B(a)A 0.94 0.94 0.95 0.96 0.97
CHR 0.98 0.92 0.81 0.98 0.18
B(b)F 0.97 0.99 0.98 0.97 0.25
B(k)F – – 0.97 – –
B(a)P – – 0.71 – –
B(ghi)P 0.89 0.98 0.91 0.96 0.20
Eigen value 8.9 9.1 11.2 8.1 1.7
% of variance 89.9 91.6 86.6 81.8 17.0
Cumulative % 89.9 91.6 86.6 81.8 98.8
Predicted sources Incineration Oil burning and incineration Vehicular activities Coal combustion Oil combustion activities
Loading greater than 0.5 is significant.

data is extracted with the two factors, 81.8% and 17% load-
ing of each group. In agricultural areas, incineration may
be the main source of PAH in soil. Because all wastes are
dumped out of the city which are very close to these agri-
cultural sites and this dumped waste is incinerated time
to time. Moreover, pumping sets is also used for the irriga-
tion purpose, which is run by diesel. Similarly, in residen-
tial areas incineration as well as diesel burning might be
the source of soil PAH. Diesel generators are used to gen-
erate electricity because of erratic supply of electricity in
the residential areas. Whereas in roadside soil, the main
source of PAH is vehicular activities. Number of the diesel
and petrol vehicles especially two and three wheelers is used
for local transportation of the public (traffic density is
about 105 vehicles per day). In addition, ratios between
pairs of individual PAH have also been calculated. A ratio
of 1 for Flt/Pyr and 1–2 for B(a)A/B(a)P indicated the
PAH origin is likely to be from combustion and motor
vehicles exhaust, respectively (Yang et al., 1991; Nam
et al., 2003). Concentration of Pyr and B(a)P are found
to be below detection levels at residential, agricultural
and industrial site, therefore ratios of these sites are not cal-
culated. In the present study, Flt/Pyr and B(a)A/B(a)P
ratios are found to be 1.0 and 2.4 at only roadside site,
which is similar to the reported data by Nam et al.
(2003) and Yang et al. (1991). Thus, it would be appear
that at roadside site motor vehicle exhausts are the domi-
nant source of PAH in the soil of Agra. In industrial area,
coal burning and oil combustion may be the major source
of PAH’s as they are used for heating the furnaces etc. In
above all, Mathura refinery is situated at about 40 km of
the Agra city. The unit must be emit significant amount
of the PAH’s which can probably get transported to the
Agra city. Thus, obtained results of factor analysis suggest
that the mixed signature of all the sources are intermediate
between vehicular and combustion activities.
3.4. Assessing PAH exposure profiles
Yet, occupational exposure limit for total-PAHs has not
been established because of the complexity of PAHs in
their chemical composition. Several PAH species including
benzo(a)pyrene (as most carcinogenic compound) have
been classified into probable (2A) or possible (2B) human
carcinogens by the International Agency for Research on
Cancer (IARC, 1987). BaP is a five ring (C20H12) com-
pound, which is mutagenic for human cells in culture
(Osborne and Crosby, 1987) and carcinogenic in whole ani-
mal assays (Cerna et al., 2000). According to the literature,
the toxic equivalent factor for BaP is one (1), which is high-
est among all the PAHs. One approach in estimating the
carcinogenic potency associated with the exposure of a
given PAH compound can be obtained by calculating its
BaPeq for each individual PAH species. In order to calcu-
late the carcinogenic potencies associated with the total
PAH exposures from soil; we pragmatically used the sum
of each individual BaPeq (i.e., total-BaPeq) as a surrogate
indicator. Therefore in the present study toxic equivalent
factor (TEF) of the given species relative to BaP carcino-
genic potency have been used. The above method has the
main advantage of being relatively easy to apply in the
environments affected by human sources, however, may
underestimate risk due to not all PAH, but only limited
compounds, are considered (WHO/IPCS, 1998). For prag-
matic purpose, the list of TEFs compiled by Tsai and Shih
(2004) was adopted in this study. Table 3 shows the con-
centrations of PAHs in soil which is below than 1 lg g1
indicating that soil PAH exposure is not carcinogenic at
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A. Masih, A. Taneja / Chemosphere xxx (2006) xxx–xxx
present level of emissions in Agra. It should be noted that
the above inference was based on the exposure of soil to
each individual PAH compound not for t-PAHs.
4. Conclusion
Out of 16 EPA priority PAHs, 14 PAHs were found in
the surface soils of Agra. The t-PAH concentrations were
found to be 13.72, 12.98, 9.37 and 6.73 lg g1 at industrial,
roadside, residential and agricultural sites, respectively.
The mean concentration of t-PAH was 12.14 lg g1 for
all sites together. In all the sites chrysene and benzo(b)flu-
oranthene were the predominant compounds as a result of
anthropogenic activities. The industrial sites had the high-
est t-PAH concentration followed by roadside, residential
and agricultural site. The average percentage of t-PAH
based on the rings were 9.15%, 23.1%, 47%, 13.4%, and
7.15% for 2, 3, 4, 5 and 6 rings, respectively. The concentra-
tions of PAH in winter, summer and monsoon are domi-
nating in industrial area i.e. 20.45, 13.43 and 7.28 lg g1,
respectively, whereas the lowest concentrations of PAH
are formed to be in agricultural area i.e. 10.18, 6.21 and
3.80 lg g1, respectively. Results obtained by varimax
rotated factor analysis are found to be statistically signifi-
cant. The carcinogenic potency of PAH compounds were
calculated and found to be insignificant at the present level
of emissions in Agra.
Acknowledgements
We thank Dr. F.M. Prasad, Principal, St. John’s College
for his encouragement. We also thank Dr. Ashok Kumar,
(Head) Department of Chemistry, St. John’s College, Agra
for providing us the necessary facilities and Dr. G.S. Sats-
angi for her valuable suggestions.
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