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Determination of Polycyclic Aromatic Hydrocarbons by Gas Chromatography–

Mass Spectrometry in Soils from Southeastern Romania

Article in Microchemical Journal · January 2012

DOI: 10.1016/j.microc.2011.08.006

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 Microchemical Journal 100 (2012) 36–41

Contents lists available at SciVerse ScienceDirect

Microchemical Journal
journal homepage: www.elsevier.com/locate/microc

Determination of polycyclic aromatic hydrocarbons by gas chromatography–mass

spectrometry in soils from Southeastern Romania
Antoaneta Ene a,⁎, Oleg Bogdevich b, Alina Sion a, Thomas Spanos c
a
“Dunărea de Jos” University of Galati, Faculty of Sciences and Environment, Department of Chemistry, Physics and Environment, 47 Domneasca St., 800008 Galati, Romania
b
Laboratory of Geochemistry, Institute of Geology and Seismology, Academy of Sciences of Moldova, 3 Academy St., Chisinau, MD-2028, Republic of Moldova
c
Kavala Institute of Technology, Department of Sciences, St. Lukas, 654 04 Kavala, Greece

a r t i c l e i n f o a b s t r a c t

Article history: Gas chromatography–mass spectrometry was used for the determination of 16 priority polycyclic aromatic
Received 26 August 2011 hydrocarbons (PAHs) in surface soils from seventeen areas in Southeast Romania, including sites placed in
Accepted 28 August 2011 the vicinity of Galati iron and steel plant and Lower Prut Meadow natural reserve in Galati County. The
Available online 2 September 2011
total concentration of PAHs (TPAHs) in the investigated soils ranges from 0.003 mg/kg to 38.524 mg/kg dry
weight. According to Romanian legislation for trace organic compounds in soils of different uses, the amounts
Keywords:
Gas chromatography–mass spectrometry
of PAHs in soils from the industrial zone exceed the normal values for the majority of individual PAHs. The
Soils lowest concentrations were found in soils sampled from the protected area of Lower Prut Meadow natural
Polycyclic aromatic hydrocarbons reserve and the highest near a zootechnique farm in the Prut River basin, where the alert levels exceeded
SE Romania for the less sensitive area in the case of TPAHs and benzo[b]fluoranthene and for the sensitive area in the
case of chrysene, benz[a]anthracene, benzo[k]fluoranthene and benzo[g,h,i]perylene. The sources of PAH
contaminating soils are complex, being of both pyrogenic and petrogenic origins.
© 2011 Elsevier B.V. All rights reserved.

1. Introduction Region of Romania (also including Braila, Buzau, Constanta, Vrancea

Polycyclic aromatic hydrocarbons (PAHs) are a considerable
source of soil contamination from natural and anthropogenic emis-
sions [1–3]. They are ubiquitous products of the incomplete combus-
tion of organic materials [4–7] resulting from burning of fossil fuels
(coal, petroleum), waste incineration, wood processing, vehicular
emissions, domestic heating [2,5,8–10], iron and steelmaking emis-
sions [11–15], landfill [2,6] and forest [17] fires etc. These compounds
are a class of pollutants of significant environmental concern due to
their stability which delays their degradation [18] and tendency to ac-
cumulate in food chains favored by their affinity for fatty tissues [8].
Many individual PAHs, especially those with high molecular weight
such as benzo[a]pyrene have been demonstrated to cause carcino-
genic and mutagenic actions [5,7]. Some, while not carcinogenic,
may act as synergists [5] and lighter PAHs also have toxic equivalency
factors [14]. Most studies focused on 16 PAHs listed by the US Envi-
ronmental Protection Agency (EPA) and the European Community
as priority pollutants [1,5,8,19].
Galati is an industrialized town, Romania's 7th largest one, located
on the banks of Danube River at the confluence of Danube with its
tributaries Siret and Prut Rivers, being the biggest port on the mari-
time Danube. Galati County is part of the South-East Development
⁎ Corresponding author. Tel.: + 40 336 130251; fax: + 40 236 461353.
E-mail address: aene@ugal.ro (A. Ene).
and Tulcea counties) and of the Lower Danube Euroregion (along
with several districts of the Republic of Moldova and Ukraine).
The information in literature regarding PAH levels in soils from
Romania is very scarce. The aim of this paper is to determine the
baseline concentrations and pattern distribution of priority PAHs
in soils collected from several industrial and rural areas from SE
Romania, and to compare them with Romanian guidelines and
values reported for other countries. Emphasis was made on locali-
ties placed nearby Iron and Steel Integrated Works (ISIW) at Galati
[20], one of the most important metallurgical complexes in the
South-East of Europe with activity lasting from 1965, and Lower
Prut Meadow in Galati County, which is a transboundary area be-
tween Romania and Moldova, included from 2004 in the group of
protected natural areas in the Lower Danube Euroregion, with eco-
logical importance recognized at international level.
2. Experimental
2.1. Sample collection and preparation
Surface soil samples were collected on April 2009 from 17 different
points in SE Romania. Approximately 0.5–1 kg of samples was taken
from the top 5 cm of the soil, and after removal of stones, large parti-
cles and organic debris, they were placed in plastic bags and stored in a
freezer.

0026-265X/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.microc.2011.08.006
 A. Ene et al. / Microchemical Journal 100 (2012) 36–41 37

Sampling points were chosen in: a) the industrial region (n = 9) of of hexane–acetone (proportion 1:2, 20 mL). After cooling down, the ex-
the iron-steel plant ISIW, in sites potential to be affected by industrial tracts were collected in the glass condenser and concentrated in n-
emissions due to their locations and prevailing wind directions, in hexane to a volume of 1 mL. The extracts were cleaned up on adsorption
8 rural localities from Galati (GL) and Braila (BR) counties — Vadeni chromatography columns filled up with 1 g of silica gel activated at a tem-
(sites S1–S3), Sendreni (S4, S5), Movileni-Sendreni (S6), Mihail perature of 135 °C for 16 h. The column was conditioned with 5 mL of
Kogalniceanu-Smardan (S7) and Smardan (S8) and Galati town hexane. Interested PAHs were eluted from column with 5 mL of n-
(S9), and b) in a farm location in the Prut River basin in Foltesti hexane, followed by 5 mL of n-hexane/dichloromethane mixture (1:1).
(S11) and six sites in Lower Prut Meadow natural reserve in the Final elutes were evaporated in argon flow to 1 mL.
rural localities Vadeni–Cavadinesti (S12, S13), Rogojeni-Suceveni
(S14), Oancea (S15) and Vladesti (S16) in Galati County, Romania. 2.3. GC–MS measurements
Control samples were also collected from rural sites located far from
traffic and industrial units, one from the north of Galati County, in Gas chromatography–mass spectrometry (GC–MS) is an established
Adam-Draguseni in the vicinity of a forest (S10), and the second analytical method used to a great extent for trace organic compounds
from Bugeac-Ostrov in the south of Constanta (CT) County (S17). [3,4,15,21–25]. GC–MS measurements were carried out at the Laborato-
The GPS coordinates and characteristics of the investigated sites are ry of Geochemistry (GEOLAB), Institute of Geology and Seismology,
given in Table 1. The nearest sites from steel complex ISIW are: S6 Academy of Sciences of Moldova, for 16 priority PAH determination:
(0.6–1 km south from coke plant blast furnaces, sinter plant and tar naphthalene (Nap), acenaphthylene (Acy), acenaphthene (Ace), fluor-
preparation plant), S8 (0.5–1 km north from converter steel plant, ene (Flu), phenanthrene (Phe), anthracene (Ant), fluoranthene (Fln),
hot rolling mills and burnt lime factory), S7 (3 km north-west from pyrene (Pyr), chrysene (Chr), benz[a]anthracene (BaA), benzo[b]fluor-
S8), S5 (near slag dump, at 1.5–2 km west from blast furnaces, electric anthene (BbF), benzo[k]fluoranthene (BkF), benzo[a]pyrene (BaP),
steel plant and power plant), S9 (4 km east from ISIW) and S1 (5 km dibenzo[a,h]anthracene (DahA), benzo[g,h,i]perylene (BghiP) and
south-west from ISIW, in the predominant wind direction). indeno[1,2,3-cd]pyrene (InP).
PAH analyses were performed on an Agilent 6890 gas chromato-
2.2. Extraction and clean up graph equipped with Agilent 5973 Network mass spectrometer,
split–splitless injector and HP-5MS capillary column. Experimental
Soils were dried, homogenized and sieved at 250 μm particle size. conditions used in this study are presented in Table 2. The mass spec-
Prior to the extraction, the soil samples (1 g) were spiked with 1 mL of trometer was operating in the electron ionization mode with electron
the solution of Semivolatile Internal Standards Mix (Acenaphthene-d10, energy of 70 eV and quadrupole temperature of 150 °C. Detection of
Chrysene-d12, 1,4-Dichlorobenzene-d4, Naphthalene-d8, Perylene-d12, PAHs was based on the selected ion monitoring system (SIM) of mo-
Phenanthrene-d10) of appropriate concentration in the final solution. Ex- lecular ion peaks (Table 3) and associated characteristic fragment ion
traction was carried out by Microwave Extraction System in the mixture peaks. Mass spectrometer was tuned using the ChemStation program
and Perfluorotributylamine (PFTBA) solution as a calibration sub-
Table 1
stance to meet the target mass-intensity criteria for 69 m/z, 219 m/z
GPS coordinates and characteristics of the investigated sites in SE Romania. and 502 m/z and their respective isotopes. PAHs were confirmed by
a comparison of the intensity for characteristic ions of compounds
Site Latitude Longitude Characteristics
in the sample with the reference spectrum in a standard solution
no.
and the similarities in retention times between the compound of in-
1 45°23′ 27°57′ Vadeni — south-west from ISIW, in the prevailing
terest and appropriate standard compound.
4.6″ 38.3″ wind direction, the closest point of locality to steel
complex, BR All reagents of pesticide grade (solvents, standard solutions and
2 45°22′ 27°56′ Vadeni — center, 150 m from railroad, BR anhydrous sodium sulfate) and pure gasses were purchased from
27.6″ 32.3″ Sigma-Aldrich, Supelco and Merck companies.
3 45°22′ 27°54′ Vadeni — near European road E87, BR PAH concentrations in soil samples were calculated using the in-
9.0″ 17.5″
ternal standard method according to appropriate normative docu-
4 45°25′ 27°55′ Sendreni — south from ISIW, near cultivated zone, GL
50.6″ 24.3″ ments ISO 18287:2006 and EPA Method 8270D. Calibration curves
5 45°24′ 27°56′ Sendreni — near the slag dump (west from ISIW), GL were checked by recalculating the middle calibration standard and
49.8″ 27.2″ the results were compared with the nominal values. Instrument cali-
6 45°24′ 27°58′ Sendreni (Movileni village) — near ISIW South gate
bration parameters included calculation of the sensitivity (ISE) as the
31.3″ 36.3″ and a major traffic artery, GL
7 45°28′ 27°55′ Smardan (Mihail Kogalniceanu village) — north from
slope of calibration curve at P-value b0.05, linearity (ILI) as a correla-
31.4″ 44.6″ ISIW, GL tion coefficient for the calibration regression line, and the instrument
8 45°27′ 27°58′ Smardan — near ISIW North gate, GL
19.4″ 22.5″
9 45°25′ 28°2′ Galati town — residential area, east from ISIW, at Table 2
19.5″ 11.2″ 200 m from Danube River, GL Experimental conditions for PAH determination by GC–MS 6890/5973 in this study.
10 46°01′ 27°43′ Draguseni (Adam village) — control site near a forest
System Method parameters
27.90″ 45.55″ in the north part of the county, GL
elements
11 45°44′ 28°04′ Foltesti — near a zootechnique farm and cultivated
36.3″ 37.73″ zone, at 5 km from Prut River banks, GL Injection Autosampler Agilent 7683 B
12 46°03′ 28°05′ Cavadinesti (Vadeni village) — at 0.04 km from Prut Injection Split/splitless inlet; injection — splitless (keeping the split closed
38.09″ 22.74″ River banks, GL ports for 1.0 min), 1 μL, inlet temperature of 300 °C
13 46°03′ 28°05′ Cavadinesti (Vadeni village) — at 0.02 km from Prut Column HP-5MS: 30 m length, 320 μm internal diameter, 0.25 μm film
33.81″ 18.18″ River banks, GL thickness, maximum temperature of 325 °C
14 45°58′ 28°05′ Suceveni (Rogojeni village) — at 0.02 km from Prut Carrier gas Helium, 1.5 mL min−1 or average velocity of 46 cm/s, constant flow
43.04″ 51.53″ River banks, GL Oven First ramp: 120 °C (hold 1 min) to 200 °C at a rate of 20 °C min−1;
15 45°56′ 28°06′ Oancea — between Sovarca Lake and Prut River, near second ramp: 220 °C (hold 1 min) to 290 °C at a rate of 5 °C min−1,
23.14″ 54.91″ cultivated zone, at 0.01 km from Prut River banks, GL hold time 2 min
16 45°51′ 28°06′ Vladesti — near Vladesti Lake, at 0.24 km from Prut Detector Mass detector, electron impact energy of 70 eV, quadrupole
32.23″ 04.05″ River banks, GL temperature of 150 °C, SIM
17 44°5′ 27°25′ Ostrov (Bugeac village) — between Danube River and Data ChemStation software
56.5″ 48.3″ Bugeac Lake, South of Romania, CT collection
38 A. Ene et al. / Microchemical Journal 100 (2012) 36–41

Table 3 S11), and near the south gate of steel complex and traffic (site S6),
GC–MS calibration parameters for PAH determination. being 38.524 mg/kg and 9.113 mg/kg, respectively. These values ex-
No. PAH Abbreviation Ion mass ISE ILI IDL, ng/g ceed the ALLS (25 mg/kg) and ALS (7.5 mg/kg) alert levels. The min-
imum contents of TPAHs, lower than NV (b0.1 mg/kg), were
1 Naphtalene Nap 128 2.71 0.999 1.0
2 Acenaphtylene Acy 152 3.01 0.999 2.0 encountered in the sites S12–S16 located in the Lower Prut Meadow
3 Acenaphtene Ace 152 2.57 0.999 1.0 natural reserve (0.003–0.072 mg/kg) and in the control site at Adam
4 Fluorene Flu 166 2.15 0.999 1.0 (S10) near a forest in Galati County (0.076 mg/kg). The other investi-
5 Phenanthrene Phe 178 3.03 0.999 1.0
gated sites exhibit TPAH levels higher than NV, ranging from 0.140 to
6 Anthracene Ant 178 3.05 0.999 1.0
7 Fluoranthene Fln 202 3.41 0.999 2.0 2.041 mg/kg. Of these, values exceeding 20, 15, 12 and 8 times the
8 Pyrene Pyr 202 3.49 0.999 2.0 upper limit of NV were obtained in the industrial area for sites S8
9 Chrysene Chr 228 3.28 0.999 2.0 and S7 near the north gate of steel complex (localities of Smardan
10 Benz[a]anthracene BaA 228 3.22 0.999 2.0 commune), S5 near the slag dump (Sendreni commune) and S9 in
11 Benzo[b]fluoranthene BbF 252 3.51 0.999 3.0
the residential area of Galati town, respectively.
12 Benzo[k]fluoranthene BkF 252 3.86 0.999 2.0
13 Benzo[a]pyrene BaP 252 3.33 0.999 2.0 Normal values are exceeded for the majority of individual PAHs in
14 Benzo[g,h,i]perylene BghiP 276 3.26 0.999 2.0 the soils from industrial sites and farm site S11. Moreover, S11 is the
15 Dibenzo[a,h]anthracene DahA 278 4.14 0.999 2.0 most contaminated location, the alert level ALS being exceeded for
16 Indeno[1,2,3-cd]pyrene InP 276 3.70 0.999 2.0
Chr, BaA, BkF, BghiP and ALLS for BbF. In the rural control sites higher
levels than NV are found for Phe in site S10 and Fln, Chr, BkF and
BghiP in the site S17 (Bugeac, Constanta County). Acy concentrations
were below the detection limit and Ace has minimum concentrations
detection limit (IDL) corresponding to 3 SD (standard deviation) of in all the samples. In the site S16 from Lower Prut Meadow the only
five replications of the lowest standard solution (Table 3). Range of detected compound was Flu, in the lowest amount (0.003 mg/kg).
standards used for PAH analysis was 0.05–0.30 μg/mL. Of the lower molecular weight PAHs (molecular weight b 252)
(LMW) Phe has the largest contribution (15.9–73.9%) to the total
3. Results and discussion amount of PAHs in the majority of samples, with the exception of in-
dustrial sites S6–S8 close to the ISIW and the rural site S11 (farm),
The concentrations of USEPA 16 priority PAHs obtained for the in- where the order of concentrations is on average Fln N Pyr N Chr N Phe.
vestigated soils in SE Romania, in mg/kg dry weight (dw), are pre- Of the higher molecular weight PAHs (HMW) the dominant com-
sented in Table 4, together with the Romanian guidelines [26] for pounds in TPAHs are BghiP (9.6–20.0%) and BbF (10.2–19.0%). In
trace organic compounds in soils of different types of use — normal Fig. 1 is presented the distribution in each location of the concentra-
value (NV), alert levels in the sensitive and less sensitive area (ALS tions of LMW, HMW and TPAHs (Fig. 1 a) and the ratios to total
and ALLS, respectively) and intervention thresholds in the sensitive PAHs of the sum of 3-, 4-, 5- and 6-ring PAH concentrations (Fig. 1
and less sensitive area (ITS and ITLS, respectively). b). From Table 4 and Fig. 1a it can be observed that the order of site
The total concentration of PAHs (TPAHs) varies widely depending contamination with PAHs is: S11 ≫ S6 N S8 N S7 N S5 N S9.
on the sample location and ranges from 0.003 mg/kg to 38.524 mg/kg It is known that a HMW/LMW ratio between the sums of amounts
dw (Table 4). The highest values for TPAHs were found in Galati of the two groups of PAHs greater than unity indicates the predomi-
County, in the vicinity of the zootechnique farm in Foltesti (site nance of pyrogenic sources (combustion residues) of PAHs and a

Table 4
PAH concentrations in soil samples from SE Romania, in mg/kg dw, and the Romanian soil regulatory levels [26].

Site Nap Acy Ace Flu Phe Ant Fln Pyr Chr BaA BbF BkF BaP BghiP DahA InP TPAHs

S1 nd nd 0.002 nd 0.115 0.010 0.062 0.059 0.040 0.038 0.080 0.039 0.041 0.054 0.006 0.016 0.562
S2 0.023 nd nd 0.011 0.107 0.009 0.068 0.069 0.042 0.037 0.102 0.040 0.059 0.080 0.005 0.021 0.673
S3 0.017 nd nd 0.008 0.063 0.002 nd nd nd nd 0.031 nd nd 0.031 nd 0.011 0.163
S4 nd nd 0.001 0.014 0.082 0.005 nd nd nd nd nd nd nd 0.028 nd 0.010 0.140
S5 0.018 nd nd 0.012 0.159 0.018 0.112 0.097 0.087 0.089 0.208 0.113 0.078 0.188 0.026 0.047 1.252
S6 nd nd 0.002 0.012 0.606 0.107 1.197 1.078 0.826 0.667 1.415 0.668 0.960 1.206 0.106 0.263 9.113
S7 0.018 nd 0.002 0.008 0.106 nd 0.217 0.211 0.113 0.107 0.210 0.142 0.153 0.213 0.026 0.048 1.574
S8 0.001 nd 0.002 0.013 0.247 0.035 0.272 0.256 0.161 0.129 0.241 0.135 0.202 0.251 0.036 0.060 2.041
S9 0.002 nd 0.003 0.015 0.139 0.027 0.098 0.094 0.053 0.053 0.083 0.058 0.085 0.079 nd 0.023 0.812
S10 nd nd nd 0.008 0.068 nd nd nd nd nd nd nd nd nd nd nd 0.076
S11 nd nd 0.004 0.033 1.345 0.194 4.886 4.611 3.685 2.696 5.939 2.948 4.688 5.972 0.407 1.116 38.524
S12 nd nd nd 0.006 0.042 nd nd nd nd nd nd nd nd nd 0.012 nd 0.060
S13 nd nd 0.002 0.004 0.017 nd nd nd nd nd nd nd nd nd nd nd 0.023
S14 0.002 nd nd 0.021 0.045 0.002 nd nd nd nd nd nd nd nd 0.002 nd 0.072
S15 0.001 nd 0.002 0.007 0.027 nd nd nd nd nd nd nd nd nd nd nd 0.037
S16 nd nd nd 0.003 nd nd nd nd nd nd nd nd nd nd nd nd 0.003
S17 0.001 nd 0.002 0.007 0.067 0.004 0.039 0.049 0.025 0.011 0.014 0.017 0.025 0.030 nd 0.009 0.300

Romanian normative

Nap Acy Ace Flu Phe Ant Fln Pyr Chr BaA BbF BkF BaP BghiP DahA InP TPAHs

NV b 0.02 – – – b0.05 b0.05 b0.02 b0.5 b0.02 b 0.02 b 0.02 b 0.02 b 0.02 b 0.02 – b 0.02 b0.1
ALS 2 – – – 2 5 5 5 2 2 2 2 2 5 – 2 7.5
ALLS 5 – – – 5 10 10 10 5 5 5 5 5 10 – 5 25
ITS 5 – – – 5 10 10 10 5 5 5 5 5 10 – 5 15
ITLS 50 – – – 50 100 100 100 50 50 50 50 10 100 – 50 150

nd = not detected; – = not specified;

NV = normal value; ALS, ALLS = alert levels in the sensitive and less sensitive area; ITS, ITLS = intervention thresholds in the sensitive and less sensitive areas.
 A. Ene et al. / Microchemical Journal 100 (2012) 36–41 39

a 4

3.5 LMW
HMW

Concentration (mg/kg)
3 TPAHs

2.5

1.5

0.5

0
S1 S2 S3 S4 S5 S6* S7 S8 S9 S10 S11** S12 S13 S14 S15 S16 S17
Site (*concentration divided to 5; **concentration divided to 10)

b
1.0
3 rings
0.9
4 rings
0.8 5 rings
6 rings
Ratio to total PAHs

0.7

0.6

0.5

0.4

0.3

0.2

0.1

0.0
S1 S2 S3 S4 S5 S6 S7 S8 S9 S10 S11 S12 S13 S14 S15 S16 S17
Site

Fig. 1. Distribution of the concentrations of LMW, HMW and TPAHs (a) and the ratios to total PAHs of the sum of 3-, 4-, 5- and 6-ring PAH concentrations (b).

ratio smaller than unity indicates a petrogenic source (fresh liquid
fuels) [4,27]. The soils from the industrial sites S5–S7 and from the
farm S11 contain a considerable amount of HMW PAHs, but are also
abundant in LMW PAHs (Fig. 1 a), indicating the input of both pyro-
genic and petrogenic origins [28], with predominance of the pyrogen-
ic one. Combined origin of PAHs also exists in the sites S1–S4, S8, S9
and S17 which exhibit LMW/HMW ratios greater than unity, but
both groups of PAHs are encountered. On average, two patterns of
PAH accumulation in these soils with complex sources of contamina-
tion are observed from Fig. 1 b, as function of number of aromatic
rings: I) 4-ring N 5-ring N 6-ring N 3-ring for the most contaminated lo-
cations (industrial sites close to the steel complex and farm site) and
II) 4-ring N 5-ring N 3-ring N 6-ring for industrial sites (rural and urban)
relatively far from the steel complex and CT control site. Exception is
made in the rural sites S3 (near a road) and S4 (agricultural site)
where 4-ring PAHs were not detected; in S4 also 5-ring PAHs were
not detected. A difference in TPAH concentrations exists between
sites S1 (0.564 mg/kg) and S2 (0.672 mg/kg): although they belong
to the same locality (Vadeni, Braila County) and S1 is closer to ISIW,
in S2 TPAH level is higher, and probably the railway transport is the
source of soil supplementary contamination [18,25]. In soils from
Galati control zone (site S10) and Lower Prut Meadow (sites S12–
S16) 3-ring LMW PAHs prevail (80–100%), with a depletion of
HMW (Fig. 1 a,b) and in this case a calculated LMW/HMW ratio
much greater than unity (N4) could be associated with a petrogenic
origin [28].
The sources of PAHs may be identified using diagnostic ratios. It was
reported in the literature that a Phe/Ant ratio N15 and a Flu/Pyr ratio b1
indicate crude oil sources, while Phe/Ant b10 and Flu/Pyr N1 indicate
combustion sources [6,15,27,29,30]. The complex pollution sources are
pointed by these ratios in the present study. Thus, Phe/Ant ratio was cal-
culated for 11 samples; 5 samples (S5, S6, S8, S9, S11) have ratio values
in the interval of 5.7–8.8 (average 6.7), 4 samples (S3, S4, S14, S17) N15.0
(average 21.8) and 2 samples (S1, S2) have ratio values of 11.5 and 11.9,
indicating combustion, petrogenic and mixed source (with pyrogenic
prevalence) respectively. Approximately the same result was found
using Ant/(Ant+Phe) ratio N0.1 for combustion and b0.1 for petrogenic
source [17,28,31], our results being in the range of 0.10–0.16 for the sites
S5, S6, S8, S9 and S11 and 0.03–0.08 for S3, S4, S14, S17, S1 and S2. The
ratios Flu/Pyr are in the interval of 0–0.16 (average 0.077), which indi-
cate a crude oil pollution in all sites.
PAHs are often found to coexist with heavy metals due to simi-
lar pollution sources [1,25,29]. In a recent study of soil contamina-
tion with heavy metals in Galati industrial zone [20], the highest
amounts of As, Cr, Cu, Ni, Pb, V and Zn were registered in the
sites located near the factories of ISIW, strengthening the above-
mentioned conclusion.
Depending on TPAH content, the soil pollution classes assigned in
Poland [18,25] are: (0) ≤ 200 μg/kg (unpolluted-natural content;
background level), (I) = 200–600 μg/kg (unpolluted-increased con-
tent), (II) = 600–1000 μg/kg (slightly polluted), (III) = 1000–
5000 μg/kg (polluted), (IV) = 5000–10,000 μg/kg (heavily polluted)
and (V) ≥ 10,000 μg/kg (very heavily polluted). Based on this soil clas-
sification, our results show that soils from nine rural sites (S3, S4, S10,
S12–S16) are unpolluted (natural content), two rural sites (S1 — far
from steel complex and S17) are in the first pollution band (unpol-
luted, with increased PAHs content), two sites (S2 — near railroad
and S9 — Galati town) are slightly polluted, three industrial sites
40 A. Ene et al. / Microchemical Journal 100 (2012) 36–41
close to the steel complex (S5, S7, S8) are polluted, one site near the
south gate of ISIW and close to traffic (S6) is heavily polluted and
one site near an agricultural farm (S11) is very heavily polluted. The
excessively high contamination of the site S11 may be linked to
open burning of agricultural residues (characterized by LMW PAHs),
which is a common practice in rural areas, and to accidental inputs
of fossil fuel such as diesel from vehicles used for various farm prac-
tices (combustion-derived HMW PAHs) or use of generators [19].
Compared to other values cited in the literature, higher concentra-
tions than those obtained in this study were mentioned in the review
[5] for 14 and 18 PAHs in urban areas from USA and Austria, of
58.68 μg/g (roadside) and 79.0 μg/g (industrial) respectively. Also, in
[19] values of TPAHs in the ranges 830–3880 μg/kg (16 PAHs), 11.2–
153,000 μg/kg (11 PAHs) and 366–27,825 μg/kg (16 PAHs) were
reported for agricultural soils in India (Delhi), and urban soils in Estonia
and China respectively. Similar amounts with our findings were
obtained for TPAHs in urban soils from Katmandu, Nepal (107–
9234 μg/kg) [4]; urban, industrial and agricultural soils from Poland
(382–3411 μg/kg, 1085.1–12,194 μg/kg and 81–645 μg/kg respectively)
[32]; arable soils from Czech Republic (139.4–2436.0 μg/kg; median
value 729.9 μg/kg) [33]; vegetable (42–3077 μg/kg) [28], farmland irri-
gated (5.1–297 μg/kg) [6] and agricultural (3.26–91 μg/kg) [30] soils
from China; soils inside a landfill following a large scale fire
(1475 μg/kg) and surrounding rural soils (11.2–28.1 μg/kg) in Greece
[16] and iron-steel industrial soils (4192 μg/kg, average of n = 17
sites) [15].
4. Conclusions
Gas chromatographic technique coupled with mass spectrometry
was found to be suitable for very low level analysis of PAHs. Results
indicate that the level of PAH contamination in the analyzed soils
from some industrial (iron and steelmaking) and agricultural zones
in SE Romania is high according to the Romanian soil pollution legis-
lation. Most of these stations exhibited the presence of predominant-
ly four to six ring PAHs. The unexpectedly high amounts of PAHs, in a
rural site near a zootechnique farm at a relative small distance from
the Prut River natural transboundary zone between Romania and
Moldova, are of great environmental concern and measures must be
taken to remediate the area because LMW PAHs with high atmo-
spheric mobility could reach other places through medium or long-
range atmospheric transport. The lowest PAH concentrations were
found in Lower Prut Meadow natural protected area and a rural site
near a forest in Galati County and in these locations three ring PAHs
had the major contribution to total PAH concentrations.
Evaluation of several diagnostic ratios suggests that the PAHs con-
taminating soils in industrial region and agricultural farm are derived
both from combustion (iron-steel industry and transportation emis-
sions; biomass burning) and petrogenic sources, while in unpolluted
soils with natural level of PAHs, these are mainly of petrogenic origin.
Future work and in progress involving the distribution of persis-
tent organic pollutants in these areas at lower depths will be reported
in due course.
Acknowledgments
This work was funded in part by National Plan II Research Project
No. 72-172/1.10.2008 (2008–2011) in Romania and in part by the
Agreement Co-operation Contract No. 30500/7.12.2009 (2009–
2014), between “Dunarea de Jos” University of Galati and the Institute
of Geology and Seismology, Academy of Sciences of Moldova (coordi-
nators: Antoaneta Ene and Oleg Bogdevich). The work of PhD student
Alina Sion (Bosneaga) was supported by Project SOP HRD-SIMBAD
6853, 1.5/S/15-01.10.2008.
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