Proceedings of the 7th World Congress on Mechanical, Chemical, and Material Engineering (MCM'21)
Prague, Czech Republic Virtual Conference – August, 2021
Paper No. ICCPE 111
DOI: 10.11159/iccpe21.111

The Determination of Some Organic Pollutants in the Waters of the
Seman Basin
Valbona HOXHA1, Albana JANO1, Kozeta VASO2, Aurel NURO2, Enkela PORO1
Faculty of Mathematical Engineering and Physical Engineering,
Polytechnic University of Tirana
v.hoxha@fimif.edu.al, a.jano@fimif.edu.al2
Faculty of Natural Sciences, University of Tirana
Bulevardi "Zogu I" Tirana Albania kozeta.vaso@fshn.edu.al1

Abstract - This article presents the results of the analysis of some organic pollutants in the surface waters of the Seman River. The
organic pollutants studied were polychlorinated biphenyls (PCB), polyaromantic hydrocarbons (PAH), and chloro-organic pesticides(OPC). These pollutants were determined in 6 stations taken into study during two expeditions in April 2019 and May 2019.
For the determination of PAH, the extraction was performed with the liquid-liquid method in the presence of hexane as the extracting
solvent and the chemical analyzes were performed by the gas chromatography technique using a flame ionization detector (GC/FID).
For the determination of chloro-organic pesticides and PCB, the extraction was performed by the liquid-liquid method using hexane as
the extraction solvent.
The determination of organochlorine pesticides was based on the EPA 8081 standard using the external standard method, by a gas
chromatography technique and electron capture detector (GC/ECD).
The determination of PCBs was based on the standard with 7 markers, donated by IAEA/MEL, Monaco, Monte-Carlo, using themethod with an external standard in the gas chromatography technique with an electron capture detector (GC/ECD).
The presence of all organic pollutants was identified in all samples studied. The concentration values of these pollutants, with the
exception of those of station M2 and M6, do not exceed allowed EU norms.
Therefore, we say that the studied waters, except the waters of the M2 station (river channel Hoxhara) and M6 (Mbrostar thebridge at the entrance of Fier) belong to good environmental quality.
Keywords: Seman basin, PCB, PAH, OPC, GC, ECD, FID.

Introduction

Semani is one of the main rivers of the hydrographic territory of Albania. The catchment area of this river is locatedin Central Albania. With the main flow direction from east to west, Semani is formed by the confluence of the Devoll
River and the Osum River. Its total catchment area is 5949 km2, with a length of 281 km, an average annual flow whichreaches 96 m3 / sec and a location at 863 m above sea level. [5] From previous studies it has been noticed that the monthwith the lowest temperature in the hydrographic network of the Seman River is January with a temperature of 2 ºC - 7.6ºC
while the month with the highest temperature is August with a temperature of 16 ºC - 25ºC. In terms of seasonal
distribution, the lowest water temperatures in the Seman hydrographic network are observed in winter (3 ºC - 7.4ºC) andspring (7.3 ºC - 14.5ºC), while the highest temperatures in autumn (9.8 ºC - 16.7 ºC) and summer (14.7 .C - 24.5ºC). [5]The Devoll River feeds the Seman River with about 88% of its waters. Due to the basic geological characteristics of thebasin (e.g. limestone, karst) during river flow, the Seman River has a relatively high content of mineral components. Water
mineralization occurs inversely related to the total volume of water flow and varies during different months of the year,
almost synchronously with the monthly distribution of water inflows itself. The average mineralization of the waters of the
Devoll River is 334 mg / l, while that of the Osum River is 345mg / l. Based on the classification of natural waters, thewaters of these two rivers are included in the category of waters with medium mineralization. After the confluence of the

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waters of Osum with those of Devoll and up to the discharge of the waters of Seman in the Adriatic Sea, the mineralization
increases having an average value higher than 370 mg / l.
Chloro-organic pesticides PCBs and PAHs are organic pollutants prevalent in many ecosystems worldwide Pesticides
are substances used to prevent, destroy, inhibit or tame any pests ranging from insects, animals, fungi, bacteria and viruses.
Pesticides are grouped into three main classes: insecticides, herbicides and fungicides, which are characterized by very
different physico-chemical properties, important differences in polarity, volatility and environmental stability.[10]In Albania, organic chlorine pesticides were used in significant quantities before the 90s. Their usage has been
primarily as insecticides. The most common have been DDT, Lindane and HCB (Hexachlor Benzene). Most are imported
from other countries, however lindane is produced in Albania, in the industrial area of Porto-Romano, an area where theenvironmental impact of this pesticide is still felt.
PCB-s are organic compounds, which are obtained by the chlorination of biphenyl in the presence of a suitable
catalyst. The presence of PCBs in Albania is especially related to their atmospheric deposits, because their uses are very
low, mainly as oils of electric transformers after the 90s (Koci, 2000). The same properties which make PCBs interestingfor industrial use cause adverse effects on reproduction, development, and endocrine function [4]; [9]Polycyclic aromatic hydrocarbons (PAHs) include a large group of organic compounds characterized by at least twobenzene rings joined together.
PAHs can be found almost everywhere, in the air, on land, water from a natural or an anthropogenic source. Natural
sources that release PAHs into the environment are volcanoes, forest fires and biosynthesis from plants andmicroorganisms. Anthropogenic sources of PAHs can be classified into two categories: stationary sources and mobile(diffuse) sources. In mobile sources, the main contribution comes from the fuel of vehicle engines, as well as from diesel
engines. While in stationary sources, the main contribution belongs to combustion processes including industrial activities.
[2]
Human exposure to organic pollutants can cause serious health effects such as congenital defects, damage to theimmune and respiratory systems, dysfunction of the hormonal and reproductive systems, sexual disorders and shorteningof lactation in women, increased risk of some cancers and even lowering the level of intelligence. [6]; [8]; [11]Materials and Methods•

Sampling and Transportation of Water Samples

Water sampling was carried out with the help of teflon containers at different points of the Seman River. The sampling
method is based on [7]. For analysis, water samples were taken at 6 stations during two expeditions in April 2019 and May
2019. Water samples were transported at +4oC. The water sampling stations are shown in the map below. (figure 1)

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Fig 1. Water sampling stations•

GC/ECD Method for Chloro-Organic Pesticides Determination•

GC/ECD Method for PCB Marker Determination

Chlorinated pesticides in water samples were extracted using liquid-liquid extraction assisted with Hexane solvent. 1
L of water and 20 ml Hexane as an extraction solvent was added in a separatory funnel. After shaking, the organic phase
was collected in a beaker where 5 g of anhydrous Na2SO4 was added for removing water. After their concentration in 1 ml
Hexane, the samples were injected directly to GC/ECD for the stimulation of chlorinated pesticides. Separation of chloroorganic pesticides was performed in the column Rtx-5 with dimensions 30m x0.25mm x0.25μm. The determination oforganic chloride pesticides was based on the EPA 8081 standard using the external standard method in the GC/ECD
apparatus.
Gas chromatographic analyses were conducted with a Varian 450 GC instrument equipped with two PTV injectors
and an ECD detector and with a 63Ni electron-capture detector. The column used for the isolation of PCBs
(simultaneously) was a Rtx-5 (30m x0.33mm x0.2μm) capillary column. The injector and detector temperatures were set at
280°C and 300°C, respectively. Carrier gas was He at 1 ml/min and make-up gas was nitrogen 25 ml/min. The initial oventemperature was kept at 70°C for 1min, which was increased to 200°C with 7°C/min, held for 7 min, and then increased to
280°C with 4°C/min for 20min. The temperature was finally increased to 300°C, at 10°C/min, for 7min. Injection volume
was 1μl, when splitless injections were made. [1]Calibration curves for 19 organochlorine pesticides and 7 marking PCBs were constructed with six calibration points
using solutions with concentrations of 5 ng/ml, 10ng/ml, 25 ng/ml, 50 ng/ml, 100 ng/mL and 250 ng/mL. To evaluate theworking method, a set of bi-distilled spiking water solutions with 10 μL of 10 nL/mL standard solution of EPA 8081A wasinitially used. White tests were used regularly during the analysis of water samples and also recovered (82.7 ± 12.6%),
reproducibility (96.4 ± 7.3%), repeatability (92.8 ± 13.5%), LOD (0.03 - 0.05 ng / ml), LOQ (0.1 - 0.15 ng/ml) of themethod used for each of the organochlorinated pesticides.

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•GC/FID Method for PAH determination

Preparation of water samples for PAH analyzes: PAH in water samples was extracted using liquid-liquid extraction
assisted with a n – hexane solvent. 1L of water and 40 ml n-hexane as the extract solvent was added in a separatory funnel.
After shaking, the organic phase was collected in a beaker where 10 g of anhydrous Na2SO4 was added for removing
water. The solvent was evaporated using Kuderna-Danish up to 2 ml and injected into the Varian 450 gas chromatographapparatus equipped with a FID detector.
A VF-1ms capillary column (30m x 0.33mm x 0.25μm) was used to isolate and determine PAH compounds inseparate injections. The temperature for FID was held at 280°C. Nitrogen was used as a carrier and make-up gas for bothanalyses. Hydrogen and air were flame detector gases with 30 ml/min and 300 ml/min, respectively. The quantification of
PAH was based on the EPA 525 standard, using an external standard method.
Calibration curves for 13 PAHs according to EPA 525 were constructed with five calibration points using solutions
with concentrations of 12.5 μg / ml, 25 μg/ mL, 50 μg / ml, 100 μg / ml and 250 μg / ml. A set of bi-distilled spiking water
solutions with 10 μl of 12.5 μl / ml standard solution of EPA 525 was initially used to evaluate the working method. White
tests were regularly used during the analysis of water samples and also calculated recovery (78.1 ± 21.5%), reproducibility(90.5 ± 11.3%), repeatability (85.4 ± 18.9%), LOD (0.3 - 0.5 μg / μl), LOQ (1.0 - 1.5 μg / ml) and methods used for each of
PAH.

Results and Discussions

The analysis of organic pollutants in water samples on the Seman Basin was conducted during the April - May 2019
period, in two expeditions at 6 sampling stations. Chlorinated organic pollutants pesticides (OPC), their residues and PCBs
were determined by the GC/ECD technique. PAHs were determined by a capillary column with the GC/FID technique.
OCPs, PCBs and PAHs were extracted using liquid-liquid extraction.
Figure 2 shows the total of organochlorine pesticides in water samples of Seman Basin analyzed in April May, 2019.

300
250
200
150
100
50
0

M1

M2
a-HCH
d-HCH
Heptachlor epoxide
4,4'-DDE
4,4'-DDD
Endosulfan Sulfat
Endrin keton

M3

M4

b-HCH
Heptachlor
Endosulfan I
Endrin4,4'-DDT
Endrin Aldehid

M5

M6

LindaneAldrina-Klordan
Dieldrin
Endosulfan II
Methoxychlor

Fig 2. Total of organochlorine pesticides (ng/L) in water samples of Seman Basin April – May, 2019

The organochlorine pesticides detected were HCB, HCHs (alpha-, beta-, gama- and delta-isomers) and the DDTrelated chemicals (p,p-DDE, p,p-DDD, p,p-DDT), Aldrines (Aldrine, Dieldrine, Endrine) and Heptachlors. Referring to the

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total concentration values of OPC, it is visible that the lowest value for the total concentration of this class is 164.25 ng/l instation M6, and the highest level of these pollutants was found in the samples taken at station M1, with a total value of
270.645 ng /l. The highest value of the OPC concentration for Endrine is 91.49 ng /l in the water samples of station M1.
Figure 3 shows the profile of organochlorine pesticides in water samples of the Seman Basin

100
50
0
a-HCH
AldrinEndrinEndosulfan Sulfat

b-HCH
Heptachlor epoxide
Dieldrin
Endrin Aldehid

LindaneEndosulfan I
4,4'-DDD
Methoxychlord-HCH
a-Klordan
4,4'-DDT
Endrin keton

Heptachlor
4,4'-DDE
Endosulfan II

Fig 3. Profile of organochlorine pesticides (ng/L) in water samples of Seman Basin, April - May 2019

The presence of almost all OPCs taken in the study is noticed. The profile of organochlorine pesticides in the Seman
Basen was: Endrine > Endosulfan I > 4,4'-DDT > Endosulphane Sulphate >Endosulphan II >Dieldrine >d-HCH> Lindane>b-HCH. This profile of pesticides is associated with their previous uses in agricultural areas near the upper-stream andlower-stream of the Seman basin.
In all water samples taken for analysis the levels of organochlorine pesticides do not exceed the levels allowed under
EU Directive 98/83 / EC [3]. (the allowed value of pesticides is 100ng/L).
The total of PCB (ng/L) values in the water samples of the Seman basin, is shown in Figure 4.
700
600
500
400
300
200
100
0

M1

M2
PCB 28PCB 52

M3
PCB 101

M4
PCB 118

PCB 153

M5
PCB138

M6
PCB 180

Fig 4. Total of PCB (ng/L) values in water samples of the Seman Basin, April - May 2019

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What is noticed is that these pollutants were found in almost all samples analyzed. The Seman and Gjanica riverlevels, as well as different discharges, are important factors which have an impact on the levels and the types of thesepollutants in the river.
Figure 5 shows the profile of PCBs in the water samples of the Seman basin.

600
500
400
300
M5

200
M3

100
0

M1
PCB 28 PCB 52 PCB 101 PCB 118 PCB 153 PCB 138 PCB 180
M1

M2

M3

M4

M5

M6

Fig 5. Profile of PCB (ng/L) in water samples of Seman Basin, April - May 2019

The profile is built from PCB28> PCB52> PCB153> PCB138> PCB118> PCB180> PCB101. High PCB 28 values
are observed at station M2. PCB 28 was found to be more abundant than other PCBs in all samples studied. Also, PCB 52
and PCB 153 with significant values were detected, the origin of which may be from point sources from lands near theriver. This is mainly related to uncontrolled wastewater discharges into the Seman basin.
Compared to international standards (98/83 / EU Directives) [3] we can say that the studied waters, with the exceptionof those of station M2, fulfill these standards by classifying them as waters of good environmental quality.
Figure 6, shows the total concentrations of PAHs (μg/L) in the water samples of the Seman basin.
1.5
1
0.5
0

M1
Acenaphtalene
Anthracene
Cryzene,Benzo [a] pyrene
Benzo [g,h,i] Perilene

M2

M3

M4

Fluorene
PyreneBenzo [b] fluoranthrene
Dibenzo [a,h] anthracene

M5

M6
Phenanthrene
Benzo [a] anthracene
Benzo [k] fluoranthrene
Indeo [1,2,3,-cd] pyrene

Fig 6. Total of PAH (μg/L) in the water samples of Seman Basin, April - May 2019

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In all the samples the presence of PAH was detected. The highest level of total PAH content was detected in the M6
station samples (1.178 μg/L) and the lowest values of concentrations were in the water samples of the M1 station (0.45 μg /L). The profile of PAH individuals is shown in Figure 7.

Fig 7. Profile of PAH (μg/L) in water samples of the Seman Basin, April - May2019

This profile is constructed as follows:
Acenaphthalene > Pyrene > Anthracene > Phenanthrene > Fluorene> Benzo [b] Fluorantrene > Benzo [k]Fluorantrenine. Other PAHs were not detected in any water samples of the stations taken in the study. PAH levels and theirprofile in the waters of the Seman basin can be explained by the discharges of industrial waters in one of its branches,
Gjanica, which collects all industrial waters of the district of Fier and the Ballsh area, an area in which also has the largest
concentration of oil wells.
However, it is worth noting that in all samples taken in the analysis the PAH levels do not exceed the levels allowed
under EU Directive 98/83 / EC.

Conclusions

The below conclusions were drawn from this study:• The presence of almost all organochlorine pesticides (OPC) was detected in the surface waters of the Seman basin.
In all water samples taken for analysis the levels of organochlorine pesticides do not exceed the levels allowed
under EU Directive 98/83 / EC. (the allowed value of pesticides is 100ng / L).
• Marker PCBs were found in almost all samples analyzed, but are under the allowed level of EU norms or underthe method detection limits therefore are not a current pollution concern, with the exception of those of station M2.
Areas with the highest concentration of PCBs are the ones closest to inhabited centers with developed agriculturalactivity. (such as station M2 of the Hoxhara channel which pours into the Adriatic Sea on the beach of Seman)This channel also brings all the discharge of the Ballsh oil industry making it a very polluted channel. The Seman
and Gjanica river levels, as well as different discharges, are important factors which have an impact on the levels
and the types of pollutants in the river.
• PAH levels and profile in the waters of the Seman basin can be explained by the discharges of industrial waters in
one of its branches, Gjanica, which collects all industrial waters of the district of Fier and the Ballsh area, an area
in which also has the largest concentration of oil wells. However, it is worth noting that in all samples taken in theanalysis the PAH levels do not exceed the levels allowed under EU Directive 98/83 / EC.

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From this study we recommend:• Continuous control of the environmental condition of the studied waters to have further details on the condition ofthis river basin.
• Creating a database of different discharges along the basin.
• Taking legal measures via local government bodies to minimize the causes of pollutants by controlling the usageof prohibited organic pollutants.
• Increasing the awareness of citizens about the protection of the aquatic environment and informing them about thehealth risks of organic pollutants to humans.

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