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Occurrence and Risk Assessment of Polycyclic Cyclic Aromatic Hydrocarbons (PAHs) and
Their Nitrated Derivatives (NPAHs) at Nile River and Esmailia Canal in Egypt
Hossam F. Nassar a,b, Ning Tang a, Akira Toriba a , Fagr Kh. Abdel-Gawadb , Kazuichi Hayakawa aaGraduate School of Natural Science and Technology, Kanazawa University, Kakuma-machi, Kanazawa 920-1192, Japan.

bEnvironmental Research Division, Water Pollution Research Department, National Research Center, El Dokki, Cairo, Egypt.

Abstract- Fresh water samples at three sites in Nile River (NR1, NR2 and NR3) and two sites in
Esmailia canal (E1 and E2) in Egypt were collected. Concentrations of soluble and particulate phases ofpolycyclic aromatic hydrocarbons (PAHs) and nitrated derivatives (NPAHs) were determined by using
HPLC with florescence detection and HPLC with chemilumnecence detection, respectively. The total
average concentrations of the fifteen PAHs having two to six rings at NR1, NR2 and NR3 in summer
and winter seasons were ranged from 2.47 × 103 to 3.20 × 103, 0.99 × 103 to 1.27 × 103 and 1.19 × 103
to 1.43 × 103 ng/l, respectively, while those at E1 and E2 were ranged from 6.17 × 103 to 7.55 × 103

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and 1.27 × 104 to 1.73 × 104 ng/l, respectively. The concentrations of benzo[a]pyrene (BaP) at Nile
River and Esmailia canal sites were varied from 26.4 to 83.2 ng/l. The total average concentrations ofeight NPAHs having three to five rings at the same sites in summer and winter seasons were varied
from 7.5 to 11.2, 5.2 to 7.0 and 5.7 to 8.0 ng/l at NR1, NR2 and NR3 respectively, and varied from 7.6
to 11.8 and 16.0 to 20.0 ng/l at E1 and E2 respectively. The major sources of PAHs and NPAHs inwater environment were discussed based on the most widely used diagnostic ratios of PAH pairs andmono-NPAHs to their parent PAHs, indicating a mixed contamination sources with the predominanceof petrogenic source origin at Nile River sites, and pyrogenic source origin at Esmailia canal sites inboth summer and winter seasons.
BaP-equivalent carcinogenic power (BaPE) values for PAHs at Nile River and Esmailia canal sites insummer and winter seasons were varied from 19.9 to 81.3 ng/l, and from 87.7 to 378.9 ng BaPE /l,respectively. The indirect mutagenicity values calculated by PAH concentrations at Nile River andEsmailia canal sites in both seasons were varied from 26.4 to 83.2 and from 179.5 to 538.1 revertants/l,
respectively. The direct mutagenicity at Nile River and Esmailia canal sites were varied from 14.0 to
25.9 and from 22.3 to 49.8 revertants/l, respectively in both seasons. The tendency that carcinogenicity
and mutagenicity at Esmailia canal sites were much higher than those at Nile River sites was inaccordance with the fact that Esmailia canal is more polluted with PAHs and NPAHs than Nile River.

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Index Terms- Polycyclic aromatic hydrocarbons, Nitrated Polycyclic aromatic hydrocarbons waterpollution, Nile River, Esmailia canal.

1

INTRODUCTION
Water pollution by toxic organic compounds is a topic of worldwide concern. Polycyclic aromatichydrocarbons (PAHs) and nitropolycyclic aromatic hydrocarbons (NPAHs), hydrocarbons containing
two or more fused benzene rings, are ubiquitous pollutants in the environment. Due to their ubiquitous
occurrence, recalcitrance properties and suspected carcinogenicity and mutagenicity to humans andbiota, PAHs are included in the priority lists of pollutants of the U.S. Environmental Protection Agency(EPA) and the European Union. The US EPA fixed 16 PAHs having two to six rings as priority
pollutants, the latest being effective from 1997 [2], [22], [30], [36] some of PAHs and NPAHs are
considered to be possible or probable human carcinogens. The endocrine disrupting properties of PAHs

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have been recently reported [31], [15], [5], [14]. The distribution in the environment and potential
human health risks have thus become the focus of much attention.

Because of their hydrophobicity and low solubility, PAHs and NPAHs in the aquatic environment
rabidly become associated with organic and inorganic suspended particles [11] and subsequentdeposition in sediments. PAHs and NPAHs partition between truly dissolved, colloidal and particulate
phases, which subsequently influences their mobility and availability in watersheds [19]. Because thesecontaminants have low water solubility, they are primarily associated to particles. Their mobility
between phases depends not only on intrinsic physico-chemical properties of individual compounds(e.g., solubility, vapour pressure) [49] but also relies on environmental variables such as the amount of
rainfall and morphological characteristics of drainage basins [24].
The introduction of wastewater effluent into drinking water aquifers and surface waters is becoming
more common throughout the world [8].
PAHs emitted to the air can be transported over long distances before they are deposited withatmospheric precipitation on soils, vegetation or sea and inland waters [47], [41], [50]. The presence of
PAHs and NPAHs in all these elements of the environment may create a risk not only to humans but toall living organisms.
Although some PAHs are naturally occurring, the majorities are anthropogenic and enter theenvironment through release of petroleum products (petrogenic sources) or by combustion of organic
matter (pyrogenic sources) [34]. Recent studies have shown that pyrogenic sources predominate in
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urban settings and that the proﬁle of PAHs in urban storm water resembles that of atmosphericdeposition [7], [2], [23], [20]. However the NPAHs in the two phases have not been compared.
The discharge of PAHs from urban watersheds is exacerbated in arid regions. Arid urban watersheds
have a tremendous number of sources. Moreover, the long antecedent periods without rain in arid
regions potentially enhance the dry deposition of PAHs to urban landscapes from these atmosphericsources. When rainfall does occur, the precipitation is often short but intense. Runoff from these largely
impervious urban surfaces efﬁciently mobilizes deposited material, including PAHs, in the resulting
surface runoff [30], [35].
Water resources in Egypt are becoming scarce. Surface-water resources originating mainly from the
Nile River are now fully exploited, while groundwater sources are being brought into full production.
Egypt is facing increasing water needs, demanded by a rapidly growing population, increased
urbanization, higher standards of living and an agricultural policy that emphasizes expanded productionin order to feed the growing population. The population is currently increasing by more than one

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million people a year. One of the greatest water-related challenges facing Egypt is the pollution of its
surface water resources from agricultural, domestic and industrial sources [25].

In Egypt, there is a lack of published data on the distribution of certain contaminants such as PAHs
and almost no published data about NPAHs in aquatic environment. The main purposes of this workare (i) to investigate the seasonal concentrations of PAHs and NPAHs in the Nile River and Esmailia
canal, (ii) to determine the source origin of PAHs and NPAHs at the aquatic environment in Egypt, and(iii) to evaluate the risk assessment of such pollutants in the Egyptian fresh water environment.
These data gaps prompted the current investigation to evaluate the levels and distribution of PAHs in
the Egyptian aquatic environment. Moreover, this is the first report to discuss the NPAHs in water
system not only in Egypt but also in all African continent.

2 MATERIALS and METHODS
2.1 Chemicals
EPA610 PAH Mixture, containing

naphthalene (Nap), acenaphthalene (Ace), fluorine (Fle),anthracene (Ant), phenanthrene (Phe), fluoranthene (Frt), pyrene (Pyr), benz[a]anthacene (BaA),
chrysene (Chr), benzo[b]fluoranthene (BbF), benzo[k]fluoranthene (BkF), benzo[a]pyrene (BaP),
dibenz[a,h]anthracene (DBA), benzo[ghi]perylene (BghiPe) and indo[1,2,3-cd]pyrene (IDP) werepurchased as a PAH standard solution from Supleco (Bellefonte, PA, U.S.A). Five deuterated PAHs
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1986(Nap-d8, Ace-d10, Phe-d10, Pyr-d10 and BaP-d12) were purchased from Wako Pure Chemical (Osaka,
Japan) as internal standards and they were dissolved in acetonitrile (Kanto Chemical, Tokyo, Japan).
While 1-nitropyrene (1-NP), 2-nitrofluorene (2-NF), 9-nitro- anthracene (9-NA), 3-nitroflourancene (3NFR) and 2-fluoro-7-nitrofluorene (FNF, internal standard) were purchased from Aldrich Chemical(Milwaukee, WI, U.S.A.). 9-Nitrophenantherene (9-Nph) and 7-nitrobenz[a]anthracene (7-NBaA) werepurchased from Accustandard Inc. (New Haven, CT, U.S.A). 6-Nitrobenzo[a]pyrene (6-NBaP) and 6nitrochrysene (6-NC) were kindly provided by Dr. Nobuyuki Sera of Fukuoka Institute of Health andEnvironmental Science (Fukuoka, Japan). All other chemicals used were of analytical-reagent grade.

2.2 Sampling sites description
2.2.1 Nile River sampling sites
The Nile River is about 6,670 km (4,160 miles) in length and is the longest river in the world.
Although it is generally associated with Egypt, only 22% of the Nile’s course runs through Egypt.

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Three sites were selected to represent different sectors in Nile River (Fig. 1). The first site was Greater
Cairo (NR1) at the intake of a drinking water treatment plant. At this location the electrical power
station, ship maintenance center and Nile transportation discharged their wastewater into the River.
This site is considered downstream of most Greater Cairo activities. The second site was Banha (NR2)(North Egypt) in the north part of Nile River at the beginning of delta area. This was a residential site
affected mainly by agricultural waste loaded with different chemicals and toxic organic nutrients. The
third site was Beni-Suif (NR3) (Upper Egypt) in the south part of River Nile. This site was affected byurbanization, traffic and some industries like cement and fertilizers facilities.
2.2.2 Esmailia canal sampling sites
Esmailia canal is 130 km long; it is a branch of Nile River which goes East to Greater Cairo to ElSharquia governorate till Esmailia governorate in the Eastern part of Egypt. After that Esmailia canal is
subdivided into two canals; Port-Said branch which goes to north to the Port-Said governorate and Suez
branch which goes to the south to Suez governorate (Fig. 1).
Esmailia canal is one of the water sources for drinking and irrigation in North Greater Cairo and Suez
canal area which includes Suez, Esmailia and Port-Said governorates. As well as it is the water source
for El-Ameria and Mostorod in Greater Cairo and some parts in El-Sharquia governorate. AlthoughEsmailia canal is a branch from Nile River in the north of Cairo, the quality of water is very different

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from the River Nile water. Esmailia canal water is very polluted especially in the first 10 km in Greater
Cairo area due to presence of a lot of industries and oil companies.
Two sites were selected along the Esmailia canal, the first site (E1) located after 10 Km from the
beginning of the canal so it was affected only by the urban activity and traffic emissions.
The other site (E2) located after 5 km from the beginning of the canal which affected by several kindsof pollutants come from different factories like paper, food, petroleum and petroleum derivatives
industries that discharge their wastewater without treatment to Esmailia canal.

2.3 Sampling and extraction
Narrow neck glass bottles (previously washed with dichloromethane) were used to collect two liters
surface water samples. Just after sampling, 100 ml (5%) of methanol were added to each sample. The
solutions were filtered through a glass fiber filter paper (GC-50, 0.45 µm poor size) followed by using a

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3M embore disc filtration (C18, 47 mm poor size). C18 discs were extracted using dichloromethane
followed by super sonication twice, filtration through a glass filter paper, addition of 100 µm DMSO,
evaporation followed by dissolving in 900 µl ethanol and then evaporation. Finally the sample solution
was filtered through a membrane filter (HLC-DISK13). Other conditions were the same as in ourprevious paper [38], [39], [13], [26] [27]. In this study, the average concentrations of total PAHs and
NPAHs were calculated from the eighteen grab water samples collected at three different sites (sixsamples from each site) in both seasons along the Nile River sites (NR1, NR2 and NR3) in summer andwinter seasons (September, 2011 and February, 2012) . As well as twelve grab water samples werecollected at two sites along Esmailia canal (E1 and E2) and also six samples at each site in bothsummer and winter seasons.

2.4 Analysis
Fifteen PAHs were analyzed by using HPLC with fluorescence detection. The system consisted of two
HPLC pumps (LC-10A, Shimadzu, Kyoto, Japan), a fluorescence detector (RF-10A, Shimadzu), a
system controller (SCL-10A, Shimadzu), an integrator (Chromatopac C-R7Ae, Shimadzu), a degasser(DGU-14A, Shimadzu), an auto sample injector (SIL-10A, Shimadzu), a column oven (CTO-10AS,
Shimadzu), a guard column (Inertsil ODS-P, 4.0 i.d. × 10 mm, GL Sciences Inc., Tokyo, Japan) and ananalytical column (Inertsil ODS-P, 4.6 i.d. × 250 mm, GL Sciences Inc., Tokyo, Japan). The mobile
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phase was a mixture of acetonitrile and water with a gradient concentration mode of acetonitrile. The
flow rate was 1 ml/min. The time program of the fluorescence detector was set to detect at optimum
excitation and emission wavelength for each PAH. NPAHs were analyzed by using HPLC withchemiluminescence detection with several modifications according to our laboratory detection method[37], [38].
The HPLC system consisted of two analytical columns (both Cosmosil 5C18-MS, 4.6 i.d. × 10 mm,
Nacalai Tesque, Kyoto, Japan), two mobile phase pumps (LC-10A, Shimadzu, Kyoto, Japan), a
chemiluminescence reagent solution pump (DMX-2000, Sanuki, Tokyo, Japan), a chemiluminescence
detector (CLD-10A, Shimadzu, Kyoto, Japan), a system controller (SCL-10A, Shimadzu, Kyoto,
Japan), a chromatopac integrator (C-R4A, Shimadzu, Kyoto, Japan), a degasser (DGU-14A, Shimadzu,
Kyoto, Japan), an auto sample injector (SIL-10A, Shimadzu, Kyoto, Japan), a column oven (CTO10AC, Shimadzu, Kyoto, Japan) and a guard column (Cosmosil 5C18-MS, 4.6 i.d. × 10 mm, Nacalai
Tesque, Kyoto, Japan). The mobile phase was imidazole–perchloric acid buffer (pH 7.6)–acetonitrile

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acetonitrile solution containing 0.04 mM bis(2,4,6-trichlorophenyl) oxalate and 15 mM hydrogen
peroxide at a flow rate of 1.0 ml/ min.

The validity of this method were already confirmed through our previous published reports showing
the recoveries varied from 87 to 104%, limits of detection (S/N = 3) varied from 0.25 to 1.5 x 10-15 mol,and limits of quantification (S/N = 10) varied from 10 -15 to 10-12 mol (over two orders) and showed agood linearity (r2 ≥ 0.899) [38], [13].

3 RESULTS
In this study, the seasonal concentrations of PAHs and NPAHs at Nile River and Esmaila canal sites
were determined . The total average concentrations of the fifteen PAHs in NR1, NR2 and NR3 insummer and winter seasons were ranged from 2.47 × 103 to 3.20 × 103, 0.99 × 103 to 1.27 × 103 and1.19 × 103 to 1.43 × 103 ng/l , respectively, while those for E1 and E2 were ranged from 6.17 × 103 to
7.55 × 103 and 1.27 × 104 to 1.73 × 104 ng/l, respectively. And the total average concentrations of theseven selected NPAHs at the designated sites in summer and winter seasons were varied from 7.5 to
11.2, 5.2 to 7.0 and 5.7 to 8.0 ng/l at NR1, NR2 and NR3, respectively, and varied from 7.6 to 11.8 and
16.0 to 20.0 ng/l, at E1 and E2, respectively. The individual PAH and NPAH concentrations showed

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higher values at Esmailia canal sites (E1 and E2) than those at Nile River sites (NR1, NR2 and NR3)
with the decreasing order of E2 > E1 >> NR1 > NR3 > NR2 (Tables 1 and 2).
The PAH and NPAH levels at all investigated sites in Nile River and Esmailia canal showed that low
molecular weight (LMW) (2-3 ring) PAHs (Nap, Ace, Fle and Phe) and medium molecular weight(MMW) (4 ring) PAHs (Frt, Pyr, BaA and Chr) have higher concentrations over the high molecularweight (HMW) (5-6 ring) PAHs (Bb, BKF, Ba, DBA, Bghipe and IDP). Whereas, the LMW (2-3 ring)
NPAHs (2-NF, 9-Nph and 9-NA) and MMW (4 ring) NPAHs (3-NFR, 1-NP, 6-NC and 7-NBaA) havehigher concentrations over the HMW (5 ring) NPAHs (6-NBaP) (Table 3).

4 DISCUSSION
4.1 Seasonal variation of PAHs and NPAHs
The average concentrations of PAHs and NPAHs were much higher at Esmailia canal sampling sites(E1 and E2) than those at Nile River sampling sites (NR1, NR2 and NR3) in both summer and winter

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seasons as shown in Tables 1 and 2. The significant high levels at the former sites might be attributed tothe presence of many industrial facilities along the canal including petroleum and petroleum derivatives
industries discharging their wastewater without treatment to the Esmailia canal [18].
The seasonal variation pattern (winter > summer) might be attributed to the following four factors; (i)The atmospheric fallout from vehicle exhaust can cause a significant accumulation of PAHs and
NPAHs in the aquatic environment, where the meteorological conditions greatly influence fallout,
particularly local fallout. So, the atmospheric winds in winter season are able to bring fallout over large
areas. (ii) The inputs of PAHs and NPAHs to water environment increase because of increasing the
agricultural burning for waste disposal in winter season. (iii) The warming activities, that emit PAHs
and NPAHs, especially in rural areas increase also in winter at low temperatures. (iv) PAHs and
NPAHs are easily decomposed at high temperatures and photo chemically degraded in the presence ofsunlight in summer season [12], [27].
The ring distribution of PAHs in summer and winter season over all Nile River and Esmailia canalsites showed that the LMW PAHs and NPAHs were the predominant components in both summer andwinter seasons. PAHs ring distribution followed the order of 3-ring > 2-ring > 4-ring > 5-ring > 6-ring,
except for NR1 and NR2 in winter season the order was 3-ring > 4-ring > 2-ring > 5-ring > 6-ring.
Whereas NPAHs had the order of 3-ring > 4-ring > 5-ring. These results can be attributed to (i) the

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lower concentrations of HMW PAHs and NPAHs in the atmosphere and (ii) the lower solubility of
HMW PAHs and NPAHs in water environment (Figs. 2A, B, C and D).
The concentration ratios of [LMW]/[HMW] PAHs and NPAHs in winter season were higher thanthose in summer season at all investigated sampling sites (Figs. 3A and B) that might be due to thefollowing three reasons: (i) The lower degrees of water temperature in winter season exhibits higher
concentration values. These higher levels correspond to the increase in the dissolved PAHs and
NPAHs, which probably as a consequence of the atmospheric condensation. (ii) PAHs and NPAHs areeasily photo chemically degraded in the presence of sunlight in summer [33], [42]. The seasonal degreeof temperature in Egypt were varied from (8 – 22 oC) in winter and from (28 – 45 oC) in summer season,and the average sunlight hours in winter season is about 9 hours, whereas, it is about 13 hours insummer season [48].
The seasonal average concentrations of PAH and NPAH at Nile River sites showed higher values at

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NR1 site over the other two sampling sites NR2 and NR3, this can be due to the heavy traffic density as
well as the close of this site to the industrial areas in Shubra El Kheima, that may lead to huge amountof PAH emissions. Whereas, at Esmailia canal sites, E2 had higher PAH and NPAH values over E1,
this also can be attributed to the presence of many industrial facilities as well as oil companies
discharging their waste to the Esmailia canal near to this site.

4.2 Source identification and molecular diagnostic ratios

In recent years, several diagnostic ratios and multivariate statistical analysis methods have been used
to identify possible emission sources of PAHs and NPAHs in the atmosphere [28], [3], [13]. The mostwidely used diagnostic ratios are Frt/Pyr, Frt/Pyr+Frt, 1-NP/Pyr and 6-NC/Chr. This is the first report
to discuss the PAH and NPAH source origin in the water environment in Egypt. We compared themolecular diagnostic ratios of the water sites in this study with atmospheric sites El Dokki and El
Teppen in our previous study [27] (Table 4).
Where, [Frt]/[Frt + Pyr] < 0.4 indicates petrogenic source, while [Frt]/[Frt + Pyr] > 0.4 indicates
crude oil and/or wood/grass/coal combustion sources [6], [4]. For the Nile River sites (NR1, NR2 andNR3), [Frt]/[Frt+Pyr] were around 0.3 to 0.4 in both summer and winter seasons, indicating mainly
petrogenic source contribution in both seasons. Whereas, those for Esmailia canal sites (E1 and E2)
were around 0.6 to 0.7, indicating a mixed source contribution.
The concentration ratios of mono-NPAHs to their corresponding PAHs such as [1-NP]/[Pyr] and [6NC]/[Chr] were effectively used to investigate the source origin in the following increasing order,
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wood particulates < CEP < DEP (Tang et al., 2005). The [1-NP]/[Pyr] for Nile River sites were ranged
from 3 × 10-3 to 4 × 10-3 and from 3 × 10-4 to 2 × 10-3 in summer and winter seasons, respectively. The
relatively lower values of Esmailia canal sites over Nile River sites indicating a mixed contamination of
CEP with petroleum sources at Esmailia canal and petrogenic sources contaminated with CEP (open air
burning) inputs at Nile River sites. [Frt]/[Pyr] (m = 202) were used to differentiate between pyrogenic
and petrogenic sources [6], [34]. Sicre et al. (1987) found that a [Frt]/[Pyr] < 1 was attributed topetrogenic sources and values greater than 1 were obviously related to a pyrolytic origin.
[Frt]/[Pyr]values for Nile River sites were slightly lower than 1 indicating a combined contamination of
petrogenic source origin polluted with pyrogenic source with the predominance of petrogenic sources at
River Nile sites, whereas for Esmailia canal sites [Frt]/[Pyr] values were slightly higher than 1,
indicating a predominance of pyrogenic source origin contaminated with petrogenic source at Esmailia
canal sites, these values are in agreement with our above mentioned investigations.

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Since an abundance of HMW PAH (e.g 5- and 6-ring) species is typically a characteristic ofpyrogenic origin while LMW PAHs (e.g. 2- and 3-ring species) are more abundant in petroleum source,
ratios of low molecular weight (LMW)/high molecular weight (HMW) were calculated to further
distinguish petroleum from combustion source inputs. LMW/HMW ratios >1 indicate petroleum source
while values <1 imply combustion [43], [26].

In this study, the concentration ratios of [LMW]/[HMW] PAHs and NPAHs in summer andwinter seasons were ˃1 referring to the abundance of LMW PAHs and petrogenic source contamination(Figs. 3A and B), but also there were considerable amounts of HMW compounds indicating an inputsof both petrogenic and pyrogenic origin with the predominance of petrogenic sources as a combined
origin from both petrogenic and pyrogenic sources. These results are in agreement with Chen et al.,(2005) and Aichner et al., (2007).

4.3 Risk assessment of potential toxic fraction of PAHs and mutagenic activity of PAHs and
NPAHs in the water environment
BaP has been regarded as the compound with the most important consequences for human healthbecause of its potent carcinogenicity that classified in group 1 [17]. BaP is considered to be a sufficientindex for PAH carcinogenicity. This compound has been widely used as an indicator for theenvironmental quality and for overall PAH carcinogenicity [45], [46]. The average concentrations of
BaP at Nile River sites were varied from 18.8 to 56.8 ng/l. Whereas, at Esmailia canal sites they varied
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from 71.6 to 242.1 ng/l in both seasons indicating high inputs of organic contaminants to Esmailia
canal sites over Nile River sites in both summer and winter seasons.
The carcinogenicity classifications verified by EPA carcinogenicity risk assessment endeavor workgroup [16], [40] showed that BaA, BbF, BaP, DPA and IND are considered possibly humancarcinogens that classified in group 2B, whereas other PAHs are not yet classified as promoters of thesame health risk. For the carcinogenic PAH compounds the following formula was introduced [9] tocalculate the BaP-equivalent carcinogenic power (BaPE):

BaPE = BaA * 0.06 + BbF * 0.07 + BaP + DBA * 0.6 + IND * 0.08

(1)

In this study, the BaPE values were ranged from 65.6 to 81.3, 19.9 to 37.9 and 26.2 to 20.5 ng/l for
NR1, NR2 and NR3 respectively in summer and wither seasons. The seasonal concentrations of BaBE

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were higher at NR1 (Cairo) site over the other two sampling sites along Nile River (NR2 and NR3).
Whereas, they ranged from 87.7 to 136.7 and 342.8 to 378.9 for E1 and E2 respectively, showing
higher BaPE values at E2 over E1 in both summer and winter seasons. These values indicate thedominance of BaPE values in winter than in summer season at all the investigated sites. In addition,these results underline and confirm the importance of BaP as a surrogate compound for PAHs mixture.
Since BaP and BaPE can be applied only to evaluate the risk assessment for PAHs and not for
NPAHs. However NPAHs are considered to be the main causes of the direct acting mutagenicity [51].
So, in this study we investigate the total mutagenicity for PAHs and NPAHs to confirm our finding ofrisk assessment from BaP and BaPE. The total mutagenicity values can be obtained from the following
equation:

Total mutagenicity = f × c(2)

where f is the mutagenicity factor and c is the concentration of each PAH or NPAH

For all sampling sites, the total indirect and direct mutagenicity values in winter season calculated by
PAHs and NPAHs, respectively, were higher than those in summer at all investigated sites. The indirect
mutagenicity values calculated by PAHs at Nile River sites NR1, NR2 and NR3 at summer and winterseasons were varied from 65.6 to 83.2,

from 26.4 to 38.2 and from 33.3 to 33.4 revertants/l,

respectively. However those for the direct mutagenicity values calculated by NPAHs were varied fromIJSER © 2015
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22.7 to 25.9, from 14.8 to 17.6 and from 14.0 to 16.5 revertants/l, respectively in summer and winterseasons. For Esmailia canal sites E1 and E2, the PAH indirect mutagenicity in summer and winterseasons were varied from 179.5 to 222.3 and from 412.9 to 538.1 revertants/l, respectively. Whereas,
those for NPAH direct mutagenicity were varied from 22.3 to 25.9 and from 40.3 to 49.8 revertants/l,
respectively, in summer and winter seasons. The highest PAH and NPAH mutagenicity along Nileriver sites were detected at NR1, whereas E2 showed higher values over E1 at Esmailia canal sites. The
seasonal values of the both indirect and direct mutagenicity for both Nile River and Esmailia canal sites
showed the same order as follow:
In summer: E2 ˃ E1 ˃ NR1 ˃ NR3 ˃ NR2; in winter: E2 ˃ E1 ˃ NR1 ˃ NR2 ˃ NR3.
These results indicated that the risk assessment of the mutagenic compounds PAHs and NPAHs inwinter season were higher than that in summer season at all investigated sites, and these results werematched with those obtained from the atmospheric sampling sites El Dokki and El Teppen [27] that areclose to these water sampling sites specially NR1, E1 and E2.

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5 CONCLOSION►

Fifteen PAHs and eight NPAHs were determined at three sites along Nile River (NR1, NR2 andNR3) and other two sampling sites along Esmailia canal (E1 and E2) in summer and winter seasons.
►

The concentrations of PAHs and NPAHs were higher in winter than in summer at all sites.

►

The concentration order for all sampling sites was E1 > E1 >> NR1 > NR3 > NR2.

►

Ring distribution of PAHs was in the order of: 3-ring > 2-ring > 4-ring > 5-ring > 6-ring. Whereas,

NPAHs are in the order of 3-ring > 4-ring > 5-ring, at all investigated sites in summer and winterseasons, indicating the predominance of LMW (2-3 ring) compounds over the HMW (5-6 ring)compounds.
► The ratios of [Frt]/[Frt + Pyr], [Frt]/[Pyr] and [1-NP]/[Pyr] indicated the predominance of

petrogenic

source origin contaminated with pyogenic source at Nile River sites, whereas at Esmailia canal sites
there was a predominance of pyrogenic source origin contaminated with petrogenic source in bothsummer and winter seasons.
►

BaP equivalent carcinogenic power of PAHs and mutagenic activities of PAHs and NPAHs showed

higher values in winter than in summer season at all the investigated sites.
► The seasonal indirect and direct mutagenicity calculated by PAHs and NPAHs respectively at Nile

River and Esmailia canal sites showed the same order as follow:
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International Journal of Scientific & Engineering Research, Volume 6, Issue 8, August-2015
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1994

In summer: E2 ˃ E1 ˃ NR1 ˃ NR3 ˃ NR2; in winter: E2 ˃ E1 ˃ NR1 ˃ NR2 ˃ NR3.

6 ACKNOWLEDGEMENT
This research was supported in part by a Grant in Aid for scientific Research (Nos. 21256001 and21590132) from the Ministry of Education, Culture, Sports, Science and Technology, Japan.

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[50] Yang, X.-Y., Okada, Y., Tang, N., Matsunaga, S., Tamura, K., Lin, J-M., Kameda, T., Toriba, A.,
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1999

Port
Said

E1

NR2

Esmailia

Banha

Suez
E2

Greater
NR1

0

E

IJSER

5 km

NR3

Fig 1. Sampling sites along the Nile River and Esmailia canal.

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2000

SummerA

2-Ring3-Ring14000
PAH ng/l

4-Ring12000
5-Ring
10000
6-Ring
8000
6000
4000
2000
0
NR1

NR2

NR3

PAH ng/l

14,000E2

IJSER
WinterB

16,000E1

2-Ring3-Ring12,0004-Ring10,0005-Ring8,000

6-Ring

6,000
4,000
2,000
0
NR1

NR2

NR3

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E1

E2

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SummerC

3-ring18

4-ring16

5-ring

NPAH, ng/l

14
12
10
8
6
4
2
0
NR1

D
18
16

NPAHs ng/l

14
12
10
8

NR2

NR3

E1

E2

IJSER
Winter3-ring4-ring5-ring

6

4
2
0
NR1

NR2

NR3

E1

E2

Figs. 2. Comparison of ring number distributions of PAHs and NPAHs at Nile River and Ismailia
canal sites in summer and winter seasons.
A, summer PAHs; B, winter PAHs; C, summer NPAHs; D, winter NPAHs

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International Journal of Scientific & Engineering Research, Volume 6, Issue 8, August-2015
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25

A

2002

Summer
Winter[LMW]/[HMW]

20

15

10

5

0
NR1

600

[LMW]/[HMW]

500
400

B

NR2

NR3

E1

E2

IJSER

Summer
Winter

300
200
100
0
NR1

NR2

NR3

E1

E2

Fig. 3. Comparison of [LMW]/[HMW] ratios of PAHs and NPAHs at Nile River and Esmailia canalsites in summer and winter.
(A) PAHs, (B) NPAHs.
LMW PAHs = Nap , Ace , Fle , Ant , Phe , Frt, Pyr, BaA and Chr .
HMW PAHs = BbF , BkF , BaP , Bghipe and IDP.
LMW NPAHs = 2-NF , 9-Nph , 9-NA , 3-NFR , 1-NP , 6-NC and 7-NBaA .
HMW NPAHs = 6-NBaB.
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Table 1.
PAH and NPAH concentrations values at Nile River and Esmailia canal sites in summer season.
NR 1

NR 2

NR 3

E1

E2

min

Max

ave

std

min

max

ave

std

min

max

ave

std

Min

Max

ave

std

min

Max

ave

std

Nap

228.3

483.5

329.0

158.0

89.0

145.0

115.5

47.1

96.5

198.5

152.9

69.0

860.0

1380.0

998.6

371

1256

1992

1528.6

705

Ace
Fle
Phe
Ant

614.0
71.0
611.0
1.9

1012.0186.4.3
1121.0
5.2

808.8
129.9
930.2
3.6

288.0
59.0
298.0
1.3

221.0
30.1
299.0
0.8

427.0
78.0
481.0
3.8

320.4
46.1
391.0
2.0

144.6
19.6
188.0
0.8

277.0
21.0
298.0
1.0

636.0
77.8
514.0
4.7

424.7
52.8
432.9
2.1

179.0
17.0
166.0
0.8

1050.0410.0
1780.012.6

1713.0781.0
2259.033.1

1401.3668.32058.5
20.4

511
293
989
9.1

3900
787
2110
18.2

5119
1314
4321
44.9

4516.31058.13671.5
35.8

1980
402
1311
15.1

Frt
Pyr
BaA
Chr

23.5
42.5
3.3
7.1

52.6
77.0
15.0
16.4

37.5
56.8
8.0
11.8

13.2
21.2
3.0
4.5

13.6
19.1
4.0
0.8

33.0
44.9
11.2
5.4

18.3
30.6
7.2
2.9

9.2
11.8
2.6
1.1

11.9
18.4
3.9
2.1

33.6
54.9
16.1
8.6

22.5
32.0
9.2
5.2

7.0
11.3
3.7
2.0

198.0
188.0
23.5
59.0

405.7
302.0
51.7
101.0

300.4
240.1
37.4
80.9

123
102
14.2
27.4

407
182
36.9
59.6

690.5
331.2
90.7
131.2

518.1
272.2
68.5
98.6

211
114
30.2
41

BbF
BkF
BaP
DBA

10.1
1.3
31.5
17.1

23.0
4.8
66.0
38.0

16.9
3.7
45.5
27.0

6.0
1.3
15.3
9.8

3.5
0.9
14.0
ND

16.1
4.5
31.1
ND

10.2
2.2
18.8
ND

2.9
0.9
9.0
ND

5.3
ND
11.2
ND

20.1
6.1
33.2
ND

13.0
3.1
24.7
ND

4.1
1.2
10.0
ND

92.0
13.8
42.0
ND

167.5
55.0
94.6
ND

135.5
31.3
71.6
ND

59.2
12.3
30.2
ND

113
36.1
187
89

314.3
99.2
301
152.1

237.1
67.1
242.1
121.7

109
28.9
99.6
49.8

BghiPe
IDP
Tot

18.0
15.3

49.5
40.8

35.0
27.4
2471.2

12.0
11.0
901.6

9.8
ND

39.0
ND

23.3
ND
988.4

9.3
ND
416.9

4.1
ND

26.5
ND

14.6
ND
1189.6

6.5
ND
437.6

38.0
38.7

91.0
77.0

70.0
54.9
6168.8

28.6
20.1
2509

94.5
46.8

177.3
131

140.0
96.0
12671.7

56.7
41.1
5094.4

2-NF
9-Nph
9-NA

1.33
0.97
ND

3.45
1.74
0.38

2.75
1.18
0.24

1.32
0.63
0.15

0.68
0.50
ND

2.43
1.61
0.26

1.98
0.99
0.17

1.10
0.42
0.06

ND
0.40
0.05

3.98
1.65
0.22

2.13
0.91
0.15

1.20
0.44
0.06

1.46
0.68
ND

4.71
2.56
0.51

2.78
1.10
0.23

1.22
0.56
0.11

2.23
1.21
0.20

8.98
4.05
0.76

6.69
2.31
0.42

2.99
1.21
0.22

3-NFR
1-NP
6-NC
7-NBaA

1.33
0.06
0.22
0.05

3.1
0.18
0.88
0.21

2.51
0.11
0.52
0.15

1.22
0.05
0.21
0.05

0.91
0.02
0.19
0.09

1.98
0.11
0.48
0.28

1.46
0.06
0.36
0.18

0.65
0.03
0.16
0.06

1.12
0.04
0.19
0.10

2.43
0.23
0.61
0.44

1.81
0.09
0.42
0.20

0.86
0.04
0.25
0.12

1.88
ND
0.20
0.03

3.45
0.16
0.85
0.24

2.82
0.07
0.50
0.13

1.32
0.03
0.26
0.06

3.48
0.15
0.38
0.16

7.32
0.44
1.78
0.68

5.01
0.24
1.08
0.30

2.42
0.15
0.60
0.66

6-NBaP

0.03

0.12

0.08

0.03

ND

0.08

0.03

0.02

ND

0.18

0.05

0.02

ND

1.01

0.03

0.01

0.04

0.16

0.09

0.04

7.54

3.2

5.23

2.1

5.71

2.4

7.62

3.3

15.96

7.1

PAH (ng/l)2-ring3-ring4-ring5-ring6-ring

NPAH (ng/l)3-ring4-ring5-ringTot.
ND; not detected

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International Journal of Scientific & Engineering Research, Volume 6, Issue 8, August-2015
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2004

Table 2.
PAH and NPAH concentration values at Nile River and Esmailia canal sites in winter season.
NR 1

NR 2

min

max

ave

std

min

max

Nap

341.2

618.0

481.8

202.0

108.0

178.6

Ace
Fle
Phe
Ant

905.7
211.5
897.9
3.8

1211.0302.61168.38.3

1073.0259.91012.5
5.3

435.9
111.2
369.1
2.1

365.2
38.5
386.5
0.4

547.8
78.7
491.2
5.8

Frt
Pyr
BaA
Chr

29.1
38.9
6.7
11.9

61.5
89.6
15.7
27.3

45.1
69.9
9.6
14.7

21.0
29.3
3.4
5.6

9.5
24.1
4.3
1.6

BbF
BkF
BaP
DBA

9.2
3.6
28.7
12.8

43.0
11.5
77.9
51.5

20.3
6.0
56.8
33.8

8.7
2.4
21.9
14.6

BghiPe
IDP
Tot

41.0
8.6

98.5
40.8

87.5
27.4
3203.6

2.03
0.95
0.06

7.81
2.81
0.39

1.77
0.09

ave

NR 3

E1

E2

std

min

max

ave

std

min

max

ave

std

min

max

ave

std

60.2

122.4

218.5

176.1

71.8

978.0

1630.51322.6621.2

2011.42822.02575.41100.3449. 2
59.4
436.3
2.6

200.7
21.9
199.5
1.2

389.0
59.1
411.0
1.2

654.5
128.7
641.3
4.6

504.5
91.0
510.3
2.4

200.5
39.0
199.2
1.1

1223.4605.2
1961.2
14.3

1995.6990.62419.432.1

1753.7872.5
2247.3
24.6

800.0
410.3
1006.310.2

3120.5
1995.64780.234.5

3951.22516.05931.479.3

3683.52305.65400.261.3

1220.0980.82055.2
25.1

29.1
60.2
10.6
6.2

18.8
37.8
7.2
3.7

8.7
16.5
3.0
1.5

8.3
22.5
2.9
1.2

40.2
54.5
17.5
7.4

22.5
34.9
8.0
3.7

9.9
14.5
3.1
1.9

385.4
205.3
28.6
69.5

506.2
298.1
59.5
122.4

424.3
251.8
33.4
98.6

198.4
109.0
13.7
40.2

681.6
411.8
49.7
189.5

1121.7
700.3
132.0
281.1

976.2
528.3
105.1
247.2

400.2
211.4
42.9
110.5

12.1
3.1
16.2
9.0

34.3
12.0
44.8
29.5

19.2
6.7
25.0
16.9

9.8
3.1
12.0
7.7

5.5
1.4
10.8
ND

28.6
11.0
29.5
ND

13.5
6.0
17.9
ND

6.0
2.7
7.9
ND

98.6
16.5
41.5
32.8

167.7
49.8
95.1
91.3

149.0
34.3
73.3
74.4

62.5
13.9
29.8
25.9

231.2
88.5
125.9
130.0

413.4
139.1
242.7
265.2

345.4
117.0
203.5
216.3

135.1
49.9
91.6
98.5

38.1
12.2
1177.5

11.0
3.6

44.8
18.5

21.5
12.2
1266.4

11.2
7.1
464.1

7.6
ND

44.5
28.7

23.3
13.7
1427.9

10.5
5.6
473.7

65.1
57.0

128.0
100.5

105.0
82.3
7547.142.1
32.5
3116.2

198.5
141.5

355.7
257.3

303.4
205.8
17274.2

129.1
97.5
5748.1

6.24
1.27
0.27

3.02
0.67
0.13

1.21
0.47
ND

4.81
1.55
0.27

3.66
0.89
0.19

1.71
0.42
0.10

1.68
0.76
0.05

5.07
1.72
0.21

3.99
1.02
0.17

1.92
0.60
0.05

2.75
0.54
0.12

8.69
1.43
0.38

7.04
1.19
0.26

3.02
0.62
0.14

3.98
1.77
0.28

9.47
3.12
0.79

8.59
2.43
0.54

4.21
1.25
0.21

3.11
0.32

2.73
0.18

1.31
0.06

1.01
ND

1.98
0.22

1.52
0.14

0.71
0.06

1.13
0.04

2.48
0.23

1.82
0.14

0.82
0.05

1.69
0.06

3.18
0.25

2.41
0.17

1.15
0.60

3.01
0.24

7.88
0.56

6.32
0.35

3.1
0.17

0.21
0.14

0.59
0.39

0.46
0.22

0.21
0.13

0.18
0.07

0.55
0.31

0.37
0.20

0.17
0.11

ND
0.10

0.68
0.24

0.31
0.19

0.21
0.10

0.26
0.15

0.69
0.29

0.44
0.22

0.25
0.12

0.44
0.31

1.37
0.59

0.95
0.46

0.43
0.26

ND

0.09

0.03
11.18

0.02
5.1

ND

0.10

0.04
6.99

0.02
3.2

0.01

0.03

0.02
8.01

0.01
3.4

ND

0.05

0.03
11.76

0.18
5.1

0.02

0.10

0.06
19.96

0.03
8.9

PAH (ng/l)2-Ring3-Ring4-Ring5-ring6-Ring

NPAHs (ng/l)

3-Ring4-Ring5-Ring

2-NF
9-Nph
9-NA
3-NFR
1-NP
6-NC
7-NBaA
6-NBaPTot.
ND; not detected

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International Journal of Scientific & Engineering Research, Volume 6, Issue 8, August-2015
ISSN 2229-5518

2005

Table 3.
Percentage of LMW, MMW and HMW PAH compounds at Nile River and Esmailia canal sites in summer and winter seasons.
NR1

Compound

NR2

NR3

E1

E2

Summer%

Winter%Summer%

Winter%Summer%

Winter%Summer%

Winter%Summer%

Winter

%LMW

2201.589.0

2832.6

88.0

875.0

88.0

1092.986.0

1065.489.0

1284.390.0

5146.783.0

6220.7

81.0

10810

85.0

14026.0

81.0

MMW

207.0

8.0

256.1

7.0

90.2

10.0

135.3

11.0

109.6

9.0

106.5

7.0

897.2

14.0

1139.0

16.0

HMW

62.4

3.0

115.0

LMW

4.96

65.0

6.80

MMW

2.58

34.0

3.94

HMW

0.08

1.0

0.06

PAHs

NPAHs

LMW, 2-3 ring; MMW, 4-5 ring; HMW, 6- ring

1625.312.0

2739.0

14.0

5.0

23.3

2.0

33.7

3.0

14.6

1.0

37.1

3.0

124.9

3.0

187.3

3.0

236.1

3.0

509.2

5.0

61.0

3.14

64.0

4.50

59.0

3.39

59.0

5.28

67.0

4.11

61.0

8.05

68.0

9.42

59.0

11.06

55.0

34.5

2.00

39.5

2.48

29.0

2.20

29.0

2.58

32.7

2.65

38.0

3.70

31.0

6.43

40.5

9.00

44.0

0.5

0.03

0.3

0.03

3.0

0.05

4.0

0.05

0.5

0.03

1.0

0.07

1.0

0.09

0.3

0.20

4.0

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IJSER © 2015
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International Journal of Scientific & Engineering Research, Volume 6, Issue 8, August-2015
ISSN 2229-5518

2006

Table 4.
Molecular diagnostic ratios at sampling sites (El dokki and El Teppen) and water sampling sites (NR1, NR2, NR3, E1 and E2) in summer andwinter seasons.
SummerSampleSamplingsite[Frt]/[Pyr]Airborn* Dokki* Tepen

0.9
1.7** NR1** NR2** NR3
** E1
** E2

0.8
0.6
0.8
1.6
2.6

Water

[Frt/[Frt]+ [Pyr][1-NP]/[Pyr]Winter[6-NC]/[Chr][Frt]/[Pyr][Frt/[Frt]+ [Pyr][1-NP]/[Pyr]IJSER[6-NC]/[Chr]

0.5
0.6

5 x 10-3
6 x 10-4

1 x 10-3
1 x 10-3

0.8
1.4

0.3
0.7

3 x 10-2
3x 10-2

3 x 10-2
1 x 10-2

0.3
0.3
0.4
0.6
0.6

3 x 10-3
4 x 10-3
4 x 10-3
6 x 10-4
7 x 10-3

3 x 10-2
11 x 10-2
8 x 10-2
4 x 10-3
4 x 10-3

0.8
0.7
0.9
1.3
1.9

0.4
0.1
0.4
0.6
0.8

2 x 10-3
3 x 10-3
3 x 10-4
1 x 10-3
2 x 10-3

2 x 10-2
12 x 10-2
17 x 10-2
1 x 10-2
1 x 10-2(*) Air borne particulate sampling site(**) Water sampling site

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