Environmental Technology & Innovation 23 (2021) 101680

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Environmental Technology & Innovation

journal homepage: www.elsevier.com/locate/eti

+Study of metallic contamination of Oued Sebou sediments,

Morocco
∗
Saadia El Hajjami a , , Nor-edine Abriak c,d , Salah Souabi a , Mohammed El Alami b
a
Hassan II University of Casablanca- Faculty of Sciences and Techniques of Mohammedia, Department of Process Engineering and
Environment Mohammedia, Morocco
b
Water Quality Control Department, ONEE-Branch-Water, Rabat, Morocco
c
IMT Lille Douai, GCE, 764 Bd Lahure, BP 10838, 59508 Douai, France
d
Université Lille Nord de France, LGCgE, Villeneuve d’Ascq, France

article info a b s t r a c t

Article history: The water of Oued Sebou has known for several years, an alteration in its quality. This
Received 8 February 2021 is due to the discharge of pollutants of different natures and origins, which come
Received in revised form 6 June 2021 from domestic, agricultural or industrial activities. In this study, we will try to carry
Accepted 8 June 2021
out a spatiotemporal evaluation of the contamination of the sediments of the river in
Available online 15 June 2021
question by metallic trace elements. This assessment will focus on zinc, chromium, lead,
Keywords: copper, mercury, cadmium and nickel. To carry out this study, we selected a set of
Oued Sebou twelve sampling sites. Thanks to the ICP-MS method, or analysis by mass spectrometry
Pollution coupled to an inductive plasma, the results obtained allowed us to quantify the degree of
Metallic trace elements pollution by the aforementioned elements. We found an increase during the dry period
Evaluation in the concentrations of TME compared to the winter period. This applies to all metals
ICP-MS except chromium. Indeed, the concentrations of this element obtained during the dry
Morocco
period are lower than those which concern the winter period. The acceleration of work
at the tanneries in the city of Fez after Aïd al-Adha (August) in 2018 seems to us a
logical explanation for this observation.
In the evaluation of the pollution index of Cr, values between 6.65 in August and
9.1 in December were observed, thus indicating contamination by this element. The
pollution indices which concern the other TME vary between 0.38 and 2.5 indicating a
normal situation in relation to the reference station S1.
© 2021 Elsevier B.V. All rights reserved.

1. Introduction

In Morocco, water resources are very limited due to prolonged periods of drought, which can cause chronic water stress.
Also, pollution by substances such as metallic trace elements from these resources causes their qualitative degradation.
Thus, good management and quality control remain effective tools for safeguarding these water resources by determining
the sources and nature of pollutants, and managing and monitoring the quality of aquatic systems (Khamar et al., 2000).
In this sense, the present work is carried out on Oued Sebou which belongs to a basin with the same name. This basin is
among the most important watersheds in Morocco. It is characterized by a very diverse geography, made up of mountains

∗ Correspondence to: Faculté des Sciences et Techniques de Mohammedia, Laboratoire génie des procédés et environnement, BP 146
Mohammedia 28806, Morocco.
E-mail addresses: saadia.elhajjami@etu.fstm.ac.ma (S. El Hajjami), nor-edine.abriak@imt-lille-douai.fr (N.-e. Abriak), salah.souabi@gmail.com,
s_souabi@yahoo.fr (S. Souabi), melalami@onee.ma (M. El Alami).

https://doi.org/10.1016/j.eti.2021.101680
2352-1864/© 2021 Elsevier B.V. All rights reserved.
S. El Hajjami, N.-e. Abriak, S. Souabi et al. Environmental Technology & Innovation 23 (2021) 101680

to the north and south, the Saïss plateau in the center, and the alluvial plain of Gharb downstream and which opens
onto the Atlantic coast (Bennasser et al., 1997; ABHs, 2015). Economically, it has one of the most important agricultural
activities in Morocco, in addition to a developed industry, particularly in the textile and automotive sector (Giorgetti
et al., 2011; Haddout et al., 2015; ABHs, 2015). Consequently, a large part of the pollutants generated by these activities
introduced into rivers accumulate in the sediments deposited at their bottoms (Blinda et al., 2013; Onivogui et al., 2013;
Han et al., 2018). In the short and long term, metallic trace elements accumulate and can migrate or be released into
water following changes in physicochemical parameters, such as temperature, redox potential, and hydrogen potential
(Khadhar et al., 2013). During transport, heavy metals can undergo many changes in their speciation due to phenomena
of dissolution, precipitation, sorption and complexation, which affect their behavior and bioavailability (Islam et al.,
2015). Depending on limnological conditions, these sediments are considered to be a reservoir and a long-term source of
contamination and can also play the role of carriers of contaminants in rivers. Therefore, the study and evaluation of the
pollution of river sediments by metals is necessary to provide a history of the evolution of pollutants in time and space
(Varol and Şen, 2012; El Hmaidi et al., 2017; Bounouira et al., 2018).
Indeed, there are many studies which aim to evaluate the metallic contamination of the sediments of the river in
question ‘‘Sebou’’. They all testify to a significant contamination of this watercourse by, above all, chromium (Cr), lead (Pb),
copper (Cu), nickel (Ni), zinc (Zn), mercury (Hg) and cadmium (Cd) (Derwich et al., 2011; Foudeil et al., 2013). This excess
of metallic elements poses a serious risk to the environment, and therefore to human health, fish and aquatic ecosystems
in general. By diffusing pollution through the soil, these elements can also have a negative impact on groundwater (Centre
Ecotox, 2012).
The present study aims to assess the pollution of the sediments of the Oued Sebou by some of these metallic trace
elements, namely, Cr, Pb, Cu, Zn, Ni, Cd and Hg. It falls within the framework of the evaluation and research on the main
pollutants of water resources in Morocco, in particular those which are hardly or not biodegradable, since self-purification
has proved unable to remedy this problem.

2. Materials and methods

2.1. Study site

The Sebou basin is located between the 3◦ 50′ and 6◦ 40′ W meridians and the 33◦ and 55◦ parallels. It has an area of
40,000 km2 and includes 1/3 of Morocco’s surface water resources. It is drained by the Sebou River, which is considered
one of the main rivers in Morocco. It travels about 500 km from the Middle Atlas to reach the Atlantic Ocean near Kénitra
(Lamhasni et al., 2013).
The Oued Sebou (Fig. 1) constitutes the area of our study. Being, as we said, among the main rivers in Morocco, it
receives a high polluting load given the industrial and domestic discharges it receives.
S1: located 20 km before the city of Fez; S2: located 4 km after the confluence of Oued Fès and Sebou; S4: located
downstream from Fez at Douar Zroula; S5: located in Hamria, before the Sebou Bridge; S7: Kariat-Ba-Mohamed; S8:
located in Mkansa ; S9: located in Mechra Bel ksiri ; S10: located in Souk Tlet ; S11: located in Sidi Allal Tazi. ; S12:
located 54 km (Moghrane) after the confluence between Sebou and the Beht valley. It is located upstream from the town
of Kenitra ; S13: located in the town of Ouled Berjal at 11 km, immediately downstream from the town of Kenitra (Kenitra
landfill) ; S14: located at the mouth of Sebou, at the port of Mehdia.

2.2. Sampling and methods of analysis

For taking sediment samples successively in August and December 2018. The choice of these stations is made on the
basis of their proximity to industrial and domestic wastewater discharge points, and their accessibility.
An S1 reference station was chosen upstream of the river and far from any human activity. Samples were taken using
a 7 cm diameter corer from the top 10 cm of the surface layer of the water/sediment interface. Plastic bags collected these
sediments and we then proceeded to mix them until a homogeneous mixture was obtained corresponding to each station
studied. These samples are stored in refrigeration between 0 and 6 ◦ C without adding any preservative. We have ensured
that the retention period between the time of sampling and the analysis does not exceed 6 months (CEAEQ, 2014).
The determination of the concentrations of metallic trace elements (MTE) in the sediments which are the subject of this
study is carried out by the ICP-MS analysis technique (analysis by mass spectrometry coupled with an inductive plasma).
This multi-elemental technique makes it possible to determine the concentrations of elements in trace and ultra-trace
states (Balcaen et al., 2015).

2.3. Sieve analysis

The sediment samples from Oued Sebou (collected in August 2018) are dried at 60 ◦ C for 2 days.
For the samples from the mud stations, 200 g of sediment are washed on a 63 µm sieve in freshwater, then dried. The
residue is returned to the oven until dehydration and weighed again (the difference between the two weighings allows
the weight of the pelitic fraction to be deduced), and then this residue is passed through a series of columns of 13 AFNOR
type sieves. (From 63 µm to 2000 µm). These sieves are divided into two columns placed on a vibrating table and vibrate
at 30 m s−1 for 20 min. The residues collected on each sieve are weighed on a balance. For samples of sandy origin, a
quantity of 100 g is dry sieved, on the same series of 13 sieves.
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S. El Hajjami, N.-e. Abriak, S. Souabi et al. Environmental Technology & Innovation 23 (2021) 101680

Fig. 1. Location of sampling stations on Oued Sebou.

2.4. Mineralization methods

Before the analysis step, the dissolution of the soils in contact with acids is accelerated by an additional ‘‘digestion’’
step. This step is very important because it largely conditions the yield of MTE extraction from the soil. Indeed, without
digestion, the simple contact of acids would not be enough to ‘‘dissolve’’ the soils. Extraction by acid attack, in a closed
environment, is recommended to avoid the loss of volatile elements (mercury, arsenic, lead or cadmium) (Hébrard-Labit
and Meffray, 2019).
0.5 g of the sediment previously homogenized, dried at 105 ◦ C and ground is taken, 10 ml of 50% HNO3 (V/V) are
added. Then reflux is carried out on a hot plate for 15 min (without boiling), then 5 ml of nitric acid is added, the beaker
is covered and the heating is carried out under reflux on a hot plate for 30 min (CEAEQ, 2014). Then 2 ml of water and
3 ml of 30% H2 O2 (V/V) are added. 5 ml of hydrochloric acid and 10 ml of water are added. Cover the beaker and heat at
reflux for 15 min (without boiling) (CEAEQ, 2014).
The hotplate should be placed in a hood and pre-set to provide a reflux temperature of about 95 ◦ C (U.S. EPA, 1994).
It is filtered through 0.45 µm filter paper (CEAEQ, 2014). The proportions of acids between HNO3 and HCl acids should
be 1: 3. (Chen and Ma, 2001).
For Mercury: put 1.0 g of the previously homogenized non-dried sediment in a tube (50 ml), add 10 ml of water, 150
µl of a 100 mg/l solution of gold, then add 4 ml of HCl, 2 ml of HNO3 and 2.5 ml of 30% H2 O2 . Cover the tube and wait
10 min, then place the tubes in the block at 105 ◦ C and heat at reflux for 60 min. After cooling to room temperature,
make up with 50 ml water (CEAEQ, 2014).

2.5. ICP-MS analysis method

The analysis of MTE by ICP-MS proceeds as follows: First the sample is treated so as to solubilize the metals contained in
the matrix. The assay is then performed by an argon plasma ionizing source mass spectrometer. The sample is introduced
into the argon plasma by a peristatic pump and a nebulizer. The metals in the sample are atomized and ionized in the
plasma. The ions produced are introduced into the chamber of the mass spectrometer where they are directed by a series
of charged metal plates, separated by a quadrupole one or a hexapole allowing the separation of the ions according to
their m/z ratios, to be finally captured by an electron multiplier (a detector) that transforms ionic signals into electrical
pulses. The concentration of an element of a specific mass is determined by comparing the quantities of ions captured
relating to the sample and those of the standard solutions (CEAEQ, 2014; Aceto, 2016).
This analysis technique is among the most sensitive, precise and reliable techniques. It is characterized by its low
detection limits and can detect a large number of elements in a short analysis time (Cengiz et al., 2017).
The concentration in mg/L of extract obtained from the instrument must then be converted into mg/kg dry weight of
the sample by the following formula:
C (mg/kg) = C 0 (mg/l) ∗ V (ml)/P (g)
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S. El Hajjami, N.-e. Abriak, S. Souabi et al. Environmental Technology & Innovation 23 (2021) 101680

Fig. 2. Cumulative grain size curves of the sediments collected at the 12 stations of Oued Sebou.

Or:
C: final concentration in mg/kg
C0: measured concentration in mg/l
V: final dosed in ml
P: dry weight of the sample analyzed in g

2.6. limite de détection et de quantification

Limit of detection of the analytical method (LDM) in (µg/l):

Cr (0.005); Ni (0.040); Cu (0.040); Zn (0.500); Cd (0.006); Pb (0.003); Hg (0.003)
Limit of quantification of the analytical method (LQM) in (µg/l):
Cr (0.020); Ni (0.180); Cu (0.160); Zn (5.410); Cd (0.020); Pb (0.021); Hg (0.0077)

3. Results and discussions

3.1. Particle size analysis

The study of the quality of water sediments requires taking into account the effect of grain size. The latter is one of the
most important factors controlling the ability of the sediment to adsorb heavy metals. Indeed, the MTE concentrations
increase with the decrease of the sediment particle size (Noppe, 1996).
The particle size analyzes of the sediments studied made it possible to draw the curves of the cumulative percentages
(Fig. 2).
According to the particle size analysis of the sediments collected, the Oued Sebou contains 4 sedimentary fractions
(Cherkaoui, 2006):
– Pelites < 63 µm, 63 µm < fine sands < 500 µm, 500 µm < Coarse sand < 2000 µm, and 2000 µm < Gravel
Cumulative curves were established using the weight of each sieve residue weighed and its percentage.

3.2. Sedimentary fractions

From Fig. 3, it can be seen that there is a predominance of the fine sands fraction with a percentage exceeding 50% at
the level of stations S5, S7, S8, S9, S10, S11, S12, S13, and S14 of which the greatest value is recorded at station 14 with
a rate exceeding 86%.
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S. El Hajjami, N.-e. Abriak, S. Souabi et al. Environmental Technology & Innovation 23 (2021) 101680

Fig. 3. Evolution in percentage (%) of the sediment fractions of the 12 stations studied.

Stations S1, S2, and S4 represent a rate of the pelitic fraction which varies between 81% (S1) and 68% (S4) whose grain
size is < 63 µm. We note the absence of the predominance of the coarse sand and gravel fraction, the highest value is
recorded at station 14 with a rate of 13%.

3.3. Metal trace elements

The Canadian limits for trace metal elements in freshwater sediments in mg kg−1 (Laliberté and Tremblay, 2002):
− RPQS (Provisional Recommendations for the Quality of Freshwater Sediments)
Cd: 0.6 mg kg−1 , Cr: 37.3 mg kg−1 , Cu: 35.7 mg kg−1 , Hg: 0.17 mg kg−1 , Ni: 35.0 mg kg−1 , Pb: 35.0 mg kg−1 , and Zn:
123.0 mg kg−1 .
− CEP (Concentrations producing a Likely Effect)
Cd: 3.5 mg kg-1, Cr: 90.0 mg kg-1, Cu: 197.0 mg kg-1, Hg: 0.486 mg kg−1 , Ni: 61.0 mg kg−1 , Pb: 91.3 mg kg−1 , and
Zn: 315.0 mg kg−1 .

3.3.1. Chromium
The values obtained for Chromium during the winter period are higher than those obtained during the summer period.
This can be explained by the large quantity of cattle skins collected after the festival of ‘‘Eid al-Adha August 2018’’ and the
intensive work at the tanneries during the winter season (December 2018). The chromium concentrations are very high
in stations S2, and S10 with the respective values of 651.23 mg kg−1 in August 2018 and 784.70 mg kg−1 in December
2018 for station S2, and 35.74 mg kg−1 in August 2018, and 264.23 mg kg−1 in December 2018 for S10 (Fig. 4A). If we
take station S1 as a reference (far from all releases), we can say that there is strong contamination at station S2 (sixty
times compared to the reference station). The average Cr contents in stations S1, S4, S5, S7, S8 and S14 remain lower
than RPQS, while the average contents in the other stations are always higher than RPQS and sometimes higher than CEP
(stations S2 and S10). Therefore, the Cr contents vary between 13.20 and 784.70 mg kg−1 with an average concentration
of 101.71 mg kg−1 . The Cr contents in the study area exceed the contents cited by Fekhaoui et al. (1993), Amri et al.
(2007), Palma et al. (2012), Foudeil et al. (2013) at the level of Oued Sebou and Hamzeh et al. (2014), Nahli et al. (2016),
respectively at the level of the Estuary rivers of Seine-France, and Oued Hassar. This can be explained by the effect of
the accumulation of Chromium in the sediments, especially at the neighboring stations of the city of Fez, given the use
of this element in the tanneries. PH, temperature, and dissolved oxygen play a very important role in the oxidation,
adsorption and transport of chromium in rivers. Generally, in aquatic systems, the exchanges between solid, aqueous and
biotic phases allow the distribution of TME between sediment, water and living organisms, which can result in adverse
effects on aquatic life. Generally, in aquatic systems, the exchanges between solid, aqueous and biotic phases allow the
distribution of TME between sediment, water and living organisms, which can result in adverse effects on aquatic life
(Smatti et al. PH, temperature, and dissolved oxygen play a very important role in the oxidation, adsorption and transport
of chromium in rivers. Generally, in aquatic systems, the exchanges between solid, aqueous and biotic phases allow the
distribution of TME between sediment, water and living organisms, which can result in adverse effects on aquatic life.
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S. El Hajjami, N.-e. Abriak, S. Souabi et al. Environmental Technology & Innovation 23 (2021) 101680

Fig. 4. Spatio-temporal evolution of Cr (A), Cu (B), Zn (C), Ni (D), Pb (E), Hg (F), and Cd (G) contents in the sediments of Oued Sebou.

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S. El Hajjami, N.-e. Abriak, S. Souabi et al. Environmental Technology & Innovation 23 (2021) 101680

3.3.2. Copper
For Copper, the concentrations obtained during the summer period are higher than those obtained during the winter
period. According to Fig. 4B, the maximum value was recorded at station S10 in August with a concentration of 113.41
mg kg−1 (above the RPQS); while the lowest concentration is obtained at station S7 and varies around 5 mg kg−1 , with an
average concentration of 38.4 mg kg−1 . The average contents in the stations S1, S2, S4, S5, S7, S8, S9, and S14 remain lower
than the RPQS, whereas the average contents in the other stations (S10, S11, S12, and S13) exceed the RPQS. The lower
Sebou part is characterized by high copper contents compared to other regions, which is probably due to the leaching of
agricultural lands, and the geological nature of the soil. In addition, Cu binds strongly to organic materials and minerals,
so it does not move very far from their original contaminated site (Qaouiyid et al., 2016).
The Cu contents in this studied area remain lower than the contents cited by Amri et al. (2007), Hamzeh et al. (2014),
Nahli et al. (2016), at the level of the rivers Oued Sebou, and Estuary of Seine-France, Oued Hassar respectively. Whereas,
these Cu values exceed the values cited by Tahiri et al. (2005), El Morhit et al. (2008), Palma et al. (2012), and Djeddi
et al. (2018) for the rivers: Bouregreg, Loukkos, Sebou, and Beni Haroun dam – Algeria respectively.

3.3.3. Zinc
The evaluation of the Zinc concentrations in the sediments indicates the absence of contamination at all the stations
studied except stations S10 and S14 where the Zinc values exceed RPQS (123 mg kg−1 ) with, concentrations of 185.5 mg
kg−1 and 187.1 mg kg−1 in August respectively (Fig. 4C).
The variations in Zn during the dry period were greater than those obtained during the wet period. Zn concentrations
undergo an increasing gradient from upstream (Fez region) to downstream (Mehdia port) even though the upstream part
is the most populated and most industrialized part. This can be explained by the use of fertilizers and pesticides rich in
Zn in the Gharb (from station S9 to station S14) region and the bioaccumulation of Zn in the sediments.
Like many other metal cations, zinc is more mobile when the environment is more acid (Panfili, 2004). Whereas, this is
not the case for Oued Sebou, where the environment is basic (El Hajjami et al., 2020), therefore the migration hypothesis
of this element is weak.
The Zn contents in Oued Sebou remain lower than the contents cited by Fekhaoui et al. (1993), Amri et al. (2007),
Palma et al. (2012), Foudeil et al. (2013) at the level of Oued Sebou. The Zn concentrations decrease over time. Thus,
these contents also remain lower than the contents reported byEl Morhit et al. (2008), Hamzeh et al. (2014), and Djeddi
et al. (2018), in the rivers: Loukkos, Estuary of the Seine- France, and Beni Haroun Dam – Algeria respectively.

3.3.4. Nickel
Nickel presents toxicity to aquatic organisms. The main sources of Ni are metallurgical industries, the combustion of
fossil fuels, and wastewater. Nickel from natural origins has a low potential mobility and a low ecological risk; whereas
the nickel from human origin has a higher mobility (Szarek-Gwiazda et al., 2011).
The Ni concentrations vary between 15.05 mg kg−1 recorded in station 7 and 34.6 mg kg−1 recorded in station 2
(Fig. 4.D). These values remain below RPQS (35 mg kg−1 ) and below the CEP (61 mg kg−1 ). Like zinc, the nickel values
detected during the dry period are greater than those during the wet period.
The average Ni concentration in Oued Sebou exceeds the average content cited by Palma et al. (2012) at Oued Sebou,
while it remains below the concentrations cited by Amri et al. (2007), Hamzeh et al. (2014) at Sebou level and Estuary of
Seine-France respectively.

3.3.5. Lead
The (Fig. 4E) shows that the levels of Lead in the analyzed sediment samples indicate contamination at station
S10 in August with a concentration of 52.1 mg kg−1 which presents a value higher than the RPQS (35 mg kg−1 ). The
concentrations in the other stations are below the concentrations producing a probable effect and also the RPQS.
The lead concentrations during the summer period are higher than the concentrations obtained during the winter
period except station S11. The relatively high values in a few samples can be explained by leaching of agricultural land,
road traffic, and industrial discharges. The average Pb content of the samples analyzed remains lower than the levels
found by Bouabdli et al. (2005), Tahiri et al. (2005), Amri et al. (2007), El Morhit et al. (2008), Hamzeh et al. (2014),
Djeddi et al. (2018) respectively at Moulouya, Bouregreg, Sebou, Loukkos, Estuary of the Seine- France, and Beni Haroun
Dam – Algeria.

3.3.6. Mercury
Mercury is a highly toxic element for human health and ecosystems. The mercury levels in the analyzed sediments vary
between 1 µg kg−1 recorded in station S7 in December and 15 µg kg−1 recorded in station S1 in August (Fig. 4.F), although
these values remain lower than the RPQS (0.17 mg kg−1 ) and below the CEP (0.486 mg kg−1 ). The concentrations obtained
at stations S1 and S12 remain close to the RPQS with values of 0.15 mg kg−1 in August and 0.1 mg kg−1 in December for
S1, and 0.14 mg kg−1 in August and 0.13 mg kg−1 in December for S12. This can be explained by the use of fertilizers or
phytosanitary products in agriculture. In a basic or neutral environment, this is the case for Oued Sebou (El Hajjami et al.,
2020), mercury can be trapped by iron hydroxide (Thomassin and Touzé, 2003), subsequently, these mercurial species
can either stored in sediments or assimilated by aquatic organisms, which in the long term constitutes a source of Hg
(Dutra Maia, 2008). The average Hg content found by this study is similar to that cited by Palma et al. (2012) with stable
Mercury content in the Oued Sebou.
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S. El Hajjami, N.-e. Abriak, S. Souabi et al. Environmental Technology & Innovation 23 (2021) 101680

Fig. 5. (A) The spatio-temporal evolution of the average pollution index, (B) the pollution index for each metal.

3.3.7. Cadmium
In this study, the Cd detected in the different stations presents values between 0.09 mg kg−1 recorded at station S8
and 0.3 mg kg−1 recorded at station S10 (Fig. 4.G). These values remain lower than the RPQS (0.6 mg kg−1 ) and the CEP
(3.5 mg kg−1 ).
The difference in the concentrations of the metallic trace elements between the two sampling periods (wet and dry) can
be explained by their settling and trapping in sediments . This trapping can be temporary because after a sudden change
in the environmental conditions, the MTEs can undergo a migration, a dilution or a release as in the winter period. These
phenomena of MTE release or trapping in aquatic ecosystems are uncontrolled (Tahiri et al., 2005). Therefore, the risk
of toxicity and mobilization of these elements has an exponential relationship with the physico-chemical conditions of
the environment. The Cd contents in the studied area are always lower than the values reported by Amri et al. (2007),
Hamzeh et al. (2014), Nahli et al. (2016) in Oued Sebou, Oued Hassar, and Estuary of Seine-France respectively.

3.4. Pollution degree

The results obtained made it possible to calculate the pollution index (PI) of the sediments of Oued Sebou by
comparison with the reference values S1 as follows (Belamie et al., 1982; Emenike et al., 2020).
IP = measured concentration/reference concentration
If IP < 3: normal situation;
3 < IP < 9: suspicious situation;
PI > 9: certain pollution (Bernoussi, 2013).
Station 1 is the site that is far from any industrial
∑ or domestic spill.
The average pollution index (IPm): IPm = IP/n (n being the number of metals analyzed).
From Fig. 5A all the stations have an average pollution index greater than 1, which indicates the presence of
anthropogenic inputs.
IPm of stations S2 and S10 in August is between 3 and 9, which means a suspect situation. Whereas the other stations
in this period have an IPm lower than 3, thus showing a normal situation. In December, the IPm of station 2 is 9.37,
which indicates certain contamination while the S10 station presents, as August, an IPm between 3 and 9 which means
a suspicious situation. The other stations have always an IPm lower 3.
The pollution index for chromium is 5.65 in August and 9.1 in December, which means the contamination of Oued
Sebou by this element. The other metallic trace elements have indices varying between 0.38 and 2.5.
According to Table 1, the sediments of the stations studied can be classified by parameter and by season into
moderately polluted and highly polluted unpolluted sediments (Table 2).
Regarding chromium, the sediments analyzed vary between moderately polluted and highly polluted sediments in the
two wet and dry periods for stations S2 and S10, on the other hand the sediments of the other stations are characterized by
a quality which varies from average to good. Concerning the Copper element, the sediments studied are classified between
unpolluted and moderately polluted in the wet period, on the other hand in the dry period most of these stations are
moderately polluted by Cu. For nickel in wet periods, all the stations are classified as not polluted by this metallic trace
element except the S5 and S12 stations which are classified as of average quality. On the other hand, in the dry period,
most of these stations are classified as moderately polluted sites. For zinc, the sediments analyzed are considered to be
unpolluted in the two periods (dry and wet) with the exception of the sediments from the two stations S10 and S14,
which are classified as moderately polluted in the dry period. For the other metallic trace elements (Cd, Hg and Pb), the
sediments studied are found to be unpolluted.
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S. El Hajjami, N.-e. Abriak, S. Souabi et al. Environmental Technology & Innovation 23 (2021) 101680

Table 1
Classification of sediments according to the Threshold Effect Concentration (TEC) and Probable Effect Concentration (PEC) values proposed by
Macdonald et al. (2000) in mg/kg (Centre Ecotox, 2012).
Metallic trace elements Not polluted Moderately polluted Very polluted
‘‘Good quality’’ ‘‘Medium quality’’ ‘‘Bad quality’’ Probable
toxicity risk
Cd <0.99 0.99–4.98 >4.98
Cr <43.4 43.4–111 >111
Cu <31.6 31.6–149 >149
Pb <35.8 35.8–128 >128
Hg <0.18 0.18–1.06 >1.06
Ni <22.7 22.7–48.6 >48.6
Zn <121 121–459 >459

Table 2
Classification of the pollution status of Oued Sebou sediments by metallic element and by season.
Parameter Not polluted Moderately polluted Very polluted
Winter Summer Winter Summer Winter Summer
Cd S1, S2, S4, S5,S7, S8, S9, S1, S2, S4, S5,S7, S8, S9,
S10, S11, S12, S13,S14 S10, S11, S12, S13,S14
Cr S1, S4, S5, S7, S8, S9, S14 S1, S4, S5, S7, S8, S9, S11, S12, S13 S12 S2, S10 S2
S10, S11, S13, S14
Cu S1, S2, S4, S5, S7, S8, S9, S1, S2, S7, S14 S11 S4, S5, S8, S9, S10, S11,
S10, S12, S13, S14 S12, S13
Pb S1, S2, S4, S5,S7, S8, S9, S1, S2, S4, S5,S7, S8, S9, S10
S10, S11, S12, S13,S14 S11, S12, S13, S14
Hg S1, S2, S4, S5,S7, S8, S9, S1, S2, S4, S5,S7, S8, S9,
S10, S11, S12, S13, S14 S10, S11, S12, S13, S14
Ni S1, S2, S4, S7, S8, S9, S10, S1, S11 S5, S12 S2, S4, S5, S7, S8, S9,
S11, S13, S14 S10, S12, S13, S14
Zn S1, S2, S4, S5,S7, S8, S9, S1, S2, S4, S5,S7, S8, S9, S10, S14
S10, S11, S12, S13, S14 S11, S12, S13

Table 3
Correlation coefficient between the metallic trace elements studied.
Cr Ni Cu Zn Cd Hg Pb
Cr 1
Ni 0,329 1
Cu −0,070 −0,092 1
Zn 0,001 −0,098 0,391 1
Cd 0,195 −0,146 0,768 0,694 1
Hg −0,126 0,148 0,200 −0,113 0,099 1
Pb 0,093 −0,210 0,633 0,748 0,885 −0,040 1

3.5. Data analysis

Data analysis will be carried out by PCA (principal component analysis), to study the different correlations between
the sampling stations and the average concentrations of metallic trace elements in the sediments of Oued Sebou. This
statistical method makes it possible to establish correlations between complex quantitative data and to determine the
links between the different MTEs in the sediments analyzed (Benkaddour, 2018).

3.5.1. Correlation coefficients

Table 3 presents the matrix of correlation coefficients of metallic trace elements in the sediments of the study area.
According to the matrix (Table 3), very significant positive correlations are observed between Cd/Cu, Cd/Zn, Pb/Cu,
Pb/Zn, Pb/Cd, with values greater than 0.6, indicating their possible common sources from anthropogenic activities,
whether industrial or urban, as well as comparable behavior in the sediment. On the other hand, the other correlations
are not important. We also notice that the correlations between Cr/Cu, Cr/Hg, Ni/Cu, Ni/Zn, Ni/Cd, Ni/Pb, Zn/Hg and Hg/Pb
are anti-correlated (negative correlation coefficient) with relatively low coefficients.

3.5.2. Principal Component Analysis (PCA)

This factorial analysis was applied to the mean values of the metallic elements studied, to make a projection of the
initial variables in this study on a factorial plane of two dimensions constituted by F1 and F2 (the first two factors). Fig. 6
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S. El Hajjami, N.-e. Abriak, S. Souabi et al. Environmental Technology & Innovation 23 (2021) 101680

Fig. 6. (A) Projection of stations on the plane of factors F1. F2, and (B) the Correlations between MTE and factors F1 and F2.

indicate that the F1 axis exhibits 44.61% of the variability while the F2 axis exposes 19.1%, so the factorial design F1.F2
explains 63.7% of the variability in the data.
Fig. 6. A expresses the distribution of the sites studied with respect to the determined metallic trace elements.
According to this figure of the spatial projection, the stations S1, S7, S8, S9, and S13, are positioned in the negative part
of the axis F1. These stations are characterized by low levels of Cr, Ni, Cd, Hg, and Pb. Thus, stations S10 and S11 occupy
the positive part on the F1 axis. These stations are located in the Gharb aquifer downstream from the industrial units of
Machraa Bel aksiri. Station S2 occupies the positive part on the F2 axis, which means that S2 receives significant quantities
of pollutants from the city of Fez. According to Fig. 6B, the metallic element Ni is an unrelated variable with other heavy
metals, while the metallic elements Cd, Zn, Pb, and Cu are correlated. On the F1 axis, the contamination gradient follows
the following order: Cd, then Pb, Zn, and Cu. The metallic trace elements Cr and Ni correlate very strongly with the F2
axis. The length of the vector for Hg is short so the quality of representation of this element in the factorial plane F1.F2
is poor.

4. Conclusion

In the light of the results obtained from the granulometric analysis of the sediments collected from Oued Sebou, it can
be seen that there is a predominance of the fine sands fraction, with a percentage greater than 50% at stations S5, S7, S8, S9,
S10, S11, S12, S13 and S14. Stations S1, S2 and S4 are characterized by a rate of the pelitic fraction which varies between
81% (S1) and 68% (S4). This study also shows that the Oued Sebou experienced chromium pollution especially downstream
of the city of Fez (S2) with a concentration of 651.23 mg/kg in August and 784.70 mg/kg in December, which may be due
intensive work in tanneries. For copper, the Blower Sebou (Gharb region) is characterized by high concentrations of this
metallic element which can reach 113.41 mg/kg. It should also be noted that the copper concentrations obtained during
the summer period are higher than those obtained during the winter period, which is probably due to the leaching of
agricultural land. As for the variations of Zn and Ni during the dry period, they are more important than those during
the wet period. The Zn concentrations in stations S10 and S14 exceed the RPQS (123 mg/kg) with the respective values
of 185.5 mg/kg and 187.1 mg/kg in August. The Zn concentration undergoes an increasing gradient from upstream (Fez
region) to downstream (Mehdia port) even if the upstream part is the most populated and most industrialized part. This
can be explained by the migration of Zn from upstream to downstream or by the use of fertilizers rich in zinc in the
Gharb region. The Pb concentration in station S10 which is 52.1 mg/kg shows significant contamination of this sampling
point. Likewise, the lead concentrations during the summer period are higher than the concentrations obtained during
the winter period with the exception of station S11. The relatively high values of some samples can be explained by
leaching of agricultural land, road traffic and industrial discharges. The mercury and cadmium contents in the analyzed
sediments remain lower than the RPQS (0.17 and 0.6 mg kg-1 respectively for Hg and Cd) and the CEP (0.486 and 3.5
mg kg-1 respectively for Hg and Cd). The calculation of the pollution index of the sediments collected at the level of the
studied site shows a suspected pollution in the two stations S2 and S10 in August, while in December pollution is certain
in the S2 station with a pollution index of 9.37. For the other stations, the situation is normal since the IPm is less than
3. The classification of the sediments analyzed for each parameter indicates that these sediments are of average to good
quality for most of the metallic trace elements, except Cr. Moreover, the correlation coefficients obtained reveal strong
correlations between Cd/Cu, Cd/Zn, Pb/Cu, Pb/Zn, Pb/Cd.
10
S. El Hajjami, N.-e. Abriak, S. Souabi et al. Environmental Technology & Innovation 23 (2021) 101680

CRediT authorship contribution statement

Saadia El Hajjami: Participated in the planning, Supervised the work, Carried out the sampling and analysis of the
samples, Processed and interpreted the experimental data, Writing - original draft, Designed the figures. Nor-edine
Abriak: Processed and interpreted the experimental data, Writing - original draft, Designed the figures. Salah Souabi:
Participated in the planning, Supervised the work, Processed and interpreted the experimental data, Writing - original
draft, Designed the figures. Mohammed El Alami: Participated in the planning, Supervised the work, Processed and
interpreted the experimental data, Writing - original draft, Designed the figures.

Declaration of competing interest

The authors declare that they have no known competing financial interests or personal relationships that could have
appeared to influence the work reported in this paper.

Acknowledgment

All of the authors discussed the results and commented on the manuscript.

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