Ecotoxicology and Environmental Safety 144 (2017) 464–474

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Ecotoxicology and Environmental Safety

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

Pollution and ecological risk assessment of heavy metals in the soil-plant MARK
system and the sediment-water column around a former Pb/Zn-mining area
in NE Morocco
⁎
Abdellah El Azharia, , Ali Rhoujjatia, Moulay Laârabi El Hachimib, Jean-paul Ambrosic
a
Laboratoire Géoressources, Unité Associée au CNRST (URAC 42), Faculté des Sciences et Techniques Marrakech, BP. 549, Bd Abdelkarim Khattabi, 40000 Guéliz
Marrakech, Morocco
b
CRMEF, Laboratoire de géologie BP.6210, Madinat Al Irfane, Rabat 10000, Morocco
c
Centre Européen de Recherche et d′Enseignement des Géosciences de l′Environnement, (UMR CNRS 6635/UMR IRD 161), Aix-Marseille Université, Université Paul
Cézanne, BP 80, 13545 Aix en Provence Cedex 4, France

A R T I C L E I N F O A B S T R A C T

Keywords: This study discussed the environmental fate and ecological hazards of heavy metals in the soil-plant system and
Heavy metals sediment-water column around the former Pb-Zn mining Zeïda district, in Northeastern Morocco. Spatial dis-
Pollution assessment tribution, pollution indices, and cluster analysis were applied for assessing Pb, Zn, As, Cu and Cd pollution levels
Cluster analysis and risks. The geo-accumulation index (Igeo) was determined using two different geochemical backgrounds: i)
Soil-plant system
the commonly used upper crust values, ii) local geochemical background calculated with exploratory data
Sediment-water column
analysis. The soils in the vicinity of the tailings, as well as the sediments downstream of the latter, displayed
much higher metal concentrations, Igeo, and potential ecology risk coefficient values than other sites, classifying
these sites as highly contaminated and severely hazardous. The concentrations of Pb in contaminated sediment
samples also exceeded the PEC limits and are expected to cause harmful effects on sediment-dwelling organisms.
Based on the comparison with the toxicity limits, the most contaminated plant samples were found around the
tailings piles. The metal concentrations in both raw and filtrated water samples were overall below the drinking
water standards in samples upstream and downstream of the mining center, indicating that heavy metals levels
in the Moulouya River surface waters were not affected by the tailings spill. Cluster analysis suggest that: i) Pb
and Zn in sediments were derived from the abandoned tailings and are mainly stored and transported as particle-
bound to the bedload, ii) Pb, Zn, and Cu in the soil-plant system were related to the dispersion of tailings
materials while As and Cd originated primarily from natural geological background in both the soil-plant and the
water-sediment systems.

1. Introduction
Mining activities are regarded as a primary source of heavy metals
in the environment (Razo et al., 2004). The impacts of the mining
wastes on the environment are related to the physicochemical char-
acteristics of materials, the method of storage, the rehabilitation pro-
cedures (Silva et al., 2009) and the climate in which the wastes are
exposed (Razo et al., 2004). Among all mining wastes, tailings are
considered as the greatest threat to the aquatic system and soil ecolo-
gical stability due to their high content of heavy metals and to their fine
particle granulometry resulting from the ore processing. Heavy metals
contained in tailings can reach nearby environments as particle-bound
or in aqueous solution (Audry, 2003), and can accumulate in excessive
amounts in soils (Zhuang et al., 2013) and sediments (Prusty et al.,
1994). Soil heavy metal contamination has received a great concern,
not only because of its toxicity to microorganisms, plants, and animals
but also because of its persistence and accumulation in soil constituents
(McGrath and Lane, 1989). According to Lenart-Boroń and Boroń
(2014), the impact of heavy metals in soils can be devastating to the
living microorganism activities, by replacing essential metal ions, pre-
venting vital functional groups, modifying the conformations of mole-
cules and in some cases by preventing soil respiration (Giller et al.,
1998). Heavy metals can reach human food chain via direct intake of
heavy metals by plants from soils (Kabata-Pendias and Mukherjee,
2007); the extensive root system and its ability to absorb ionic com-
pounds even at low concentrations make the absorption of metals
highly effective (Furini, 2012). River sediments are essential sources for
evaluating the unnatural contamination (Martin, 2000). Heavy metals

⁎
Corresponding author.
E-mail address: Abdelah.Elazhari@gmail.com (A. El Azhari).

http://dx.doi.org/10.1016/j.ecoenv.2017.06.051
Received 10 March 2017; Received in revised form 19 June 2017; Accepted 20 June 2017
Available online 28 June 2017
0147-6513/ © 2017 Elsevier Inc. All rights reserved.
A. El Azhari et al.
reach the aquatic systems mainly bound to suspended particulate
matter and sediments (Calmano et al., 1990) and tend to accumulate in
sedimentary environments (Bidone et al., 1993). Sediments often act
simultaneously as a carrier and as secondary sources of pollutants in the
aquatic system (Ma et al., 2015).
Preliminary studies about waste physicochemical properties, espe-
cially their heavy metals content and the environmental fate of these
latter is crucial to discuss future remediation or preventive procedures
to reduce the associated ecological damage (Acosta et al., 2011). An
effective land management and rehabilitation methods are related to
the determination of the spatial variability and the level of con-
tamination of heavy metals that can be achieved through geostatistical
analysis using the geographical information system (GIS) as a useful
tool in environmental monitoring (Li et al., 2004; Acosta et al., 2011;
Sun et al., 2012; Khalil et al., 2013). The contamination process is re-
lated to the spatial heterogeneity of the wastes and the soil physico-
chemical properties (Acosta et al., 2011) in addition to the differences
between natural (e,g. geochemical background values) and anomalous
elements concentrations (Martínez et al., 2007). In geochemical studies,
the evaluation of interrelationships among heavy metals is commonly
performed using multivariate statistical methods (Acosta et al., 2011;
Varol, 2011; Yuan et al., 2013; Arslan and Turan, 2015) such as Cluster
analysis (CA) used by numerous authors to indicate relations between
heavy metals as well as the typology and sources pollution in the soil-
plant system and the sediment-water column (Soares et al., 1999;
Casado-Martinez et al., 2009; Guo et al., 2012; Varol, 2011; Martín-
Crespo et al., 2012; Karim et al., 2014).
The present work primary objectives were (i) to evaluate the con-
centrations of Pb, As, Cu, Zn and Cd and the spatial distribution of these
elements in soils/plants and waters/sediments around the abandoned
Zeïda mining district, (ii) to establish local geochemical background
using normal Q-Q plots, (iii) to assess the contamination levels using
the geo-accumulation index (Igeo) and the risk associated with the
heavy metals concentrations with the potential ecological risk index
(Eir) and the sediment quality guidelines (SQGs), (iv) comparison of
elements concentrations with the regional main rock types contents and
geological spatial variation as a potential approach in debating the
source of heavy metals, (v) to discuss the relations between heavy
metals in the soil-plant system and sediment-water column using cluster
analysis (CA).
2. Material and methods
2.1. Research area
The High Moulouya Sub-basin is characterized by a semi-arid cli-
mate and affected by a severe water stress due to low annual pre-
cipitations ( < 300 mm). The Moulouya is the longest river in Morocco
with a total length of 600 km and is the primary water collector along
the Moulouya basin. To satisfy the High Moulouya population domestic
and irrigation needs in water resources, the Hassan II Dam was con-
structed with 400 Mm3 total storage capacity at around 16 km down-
stream of the abandoned mining district Zeïda. The soils in the study
area are mainly calcimagnesic and immature while the vegetation cover
consists primarily of Alfa steppes and wormwood steppes. Winds can
reach speeds higher than 50 m/s, as dominant directions WSW and ENE
(Fig. 1). The High Moulouya displays a particular geological environ-
ment (Annex 1), the Palaeozoic basement is composed of Hercynian
granitoids and metamorphic schist (Dagallier and Charoy, 1991),
overlapped by a Mesozoic formation, which base is represented by
Permo-Triassic arkoses. The quaternary cover is composed of clays,
sandstones, and granites Emberger (1965). The Pb concentrations at
Zeïda are mostly associated with the nature and the properties of the
arkoses cement enriched by silicate, the mineralization was hosted in
Triassic arkoses and sandstones and consists mainly of Cerussite
(PbCO3) (Dagallier and Charoy, 1991). The Zeïda mining center was
465
Ecotoxicology and Environmental Safety 144 (2017) 464–474
the site of an intense Pb mining activities that lasted from 1972 to 1985
leaving at open air more than 12 Mt of materials disposed as three piles
of tailings on the banks of the Moulouya River. The studied tailings are
mainly composed of Cerussite (0.5%), Barite (7.5%), Quartz (49.5%),
K-Feldspars (29.4%), Plagioclases (6.7%), clay minerals (4.1%) and
fluorite (2.4%) (Iavazzo et al., 2012).
2.2. Sample collection
Soil and sediment samples (Fig. 1) were collected and stored in
clean polyethylene bags, labelled and then transported to the labora-
tory: i) 20 surface soil samples (0–1 cm) were sampled in December
2014, this depth can be useful to assess recent material deposit, but
also, the surface particles are more sensitive to inter-rill and rill erosion
which can play a significant role in the transport of contaminated
particles from soil to the aquatic system. The plant samples correspond
to the same sampling point of soils. The plants were carefully removed
to maintain the integrity of the root and stem and then stored in clean
polyethylene bags. In a view to getting rid of the attaching substrate
materials, all plants were washed carefully with tap water, rinsed with
distilled water twice, and finally air-dried (Liu et al., 2006; Boularbah
et al., 2006). The entire plant sample was milled in a metal-free mill
then passed through a 0.15 mm sieve, the resultant biomass was then
preserved in polyethylene flask until analysis (Liu et al., 2006), ii) 23
sediment samples (0–10 cm) were taken, each sample was air dried
then sieved through a 2 mm mesh to remove plant fragments and
stones. The samples destined to chemical analysis were milled to a
powder and kept in glass flasks until analysis. Water samples corre-
spond to the same sampling point for sediments. Two types of water
samples were obtained: raw water samples and filtrated water samples
through 0.20 µm filters. The raw water samples were collected in situ
using 50 ml polyethylene narrow-mouth bottles and acidified using
high purity HNO3. River water for filtration was collected using washed
plastic bottles. These samples were then transported and filtered in a
few hours through prewashed 0.20 µm nylon membrane disc filters
(PALL, 0.2 µm, 47 mm) using an air pump. Due to the large sampling
area and for a better visualization of the study objectives, some of the
sampling sites were not shown in the sampling map: Sediment/water
samples ZM1 and ZM2, located at around 40 km and 5 km upstream of
the tailings, respectively; soil/plant reference samples S-R1 and S-R2
taken in the NE (4.5 km) and the SW (15 km) of the tailings, corre-
spondingly.
2.3. Analytical methods
Soil and sediment characterization was conducted as follow: Grain
size distribution (through wet sieving between 0.5 and 2.0 mm AFNOR
sieves, a laser diffraction particle size analyser (LA-300-Horiba) was
used to analyse the fraction smaller than 500 µm due to the detection
range limits; Electrical conductivity was determined following the
method described by Rayment and Higginson (1992). The pH mea-
surements were carried out following the technique defined by Petard
(1993); carbonate content (percentage of CaCO3), by the calcimeter
method following the standard (AFNOR NF P94-048, 1996). Pawliszyn
(2002) protocol was adapted for the measurement of the redox poten-
tial. The determination of Pb, Cd, Zn, Cu and As was carried on the total
sample for both soils and sediments (< 2 mm), the following section
displays the methodological approach used in testing the pseudototal
contents of heavy metals in all solid samples:1 g of dry matter was
placed in a 50 ml plastic tube and mixed with ultrapure water up to
25 ml. 3 ml of concentrated nitric acid and 9 ml of hydrochloric acid are
added to the mix. The tube is then placed into a DIGIPREP digestion
system (SCP Science). After decanting, 6.25 ml of concentrated nitric
acid is added to the tube and replaced in the digestion system. The
obtained dissolved sample is then placed in a flask. The concentrations
of Pb, Zn, Cd, As and Cu were afterward determined by atomic emission
A. El Azhari et al.
spectroscopy with inductively coupled plasma (ICP-AES, HORIBA Jobin
Yvon Ultima 2). A blank test on a sample of 25 ml of ultrapure water
was carried out in parallel under the same conditions using the same
reagents quantities. Similarly, an earth reference sample is dissolved in
the same terms as the samples from the Technical Support Units for
Scientific Research of Morocco (UATRS, CNRST). Differences among
the measured and certified heavy metal concentrations values are
below 5%, and analytical accuracy for duplicate samples is within ±
5%. All used chemicals did not undergo any extra purification.
Water physicochemical parameters, namely pH, conductivity and
redox potential were measured on site using HANNA Test kits (Hanna
Instrument Ltd., Germany), the multifunction probe was rinsed with
deionized water between each field measurement. The water samples
collected, including both the raw and the filtrated through 0.2 µm
membrane filters, were analyzed at the European Center for Research
and Education in Environmental Geosciences (Aix-en-Provence, France)
using an ICP-MS Perkin Elmer NexIon 300 X for their total concentra-
tions in heavy metals. The description of the used material, mixtures
and quality control methods are exposed in Annex 2. Half the detection
limit was set as the value for data below the analytical detection limits
to perform the statistical analysis (Yang et al., 2014).
2.4. Assessment methods of sediment and soil pollution
2.4.1. Geo-accumulation index (Igeo)
The geo-accumulation index is widely used to assess heavy metal
contamination in soils and sediments (Wei et al., 2011; Varol, 2011;
Zhuang et al., 2013; Zhenwu et al., 2015), this method evaluates the
enrichment of metal levels above baseline or background values. The
geo-accumulation index is calculated via the equation: Igeo = log2 [Cn/
1.5Bn] (Müller, 1969). Cn corresponds to the measured metal con-
centration (mg/kg), Bn is the background value of the investigated
metal (mg/kg). The heavy metal pollution level is based on the ob-
tained geo-accumulation index value (Müller, 1969). Unpolluted:
Igeo < 0; unpolluted to moderately polluted: 0 < Igeo ≤ 1; moderately
polluted: 1 < Igeo ≤ 2; moderately to heavily polluted: 2 < Igeo ≤3;
heavily polluted: 3 < Igeo ≤ 4; heavily to extremely polluted: 4 < Igeo
≤ 5 and extremely polluted: Igeo > 5. In this study, the geo-accumu-
lation index is calculated based on two different approaches, the first
and widely used is to adopt the upper continental crust (UCC) levels of
metals (mg/kg) as background values (Rudnick and Gao, 2003), with As
(4.8), Cd (0.09), Zn (67), Pb (17) Cu (28); the second approach is the
466
Ecotoxicology and Environmental Safety 144 (2017) 464–474
Fig. 1. Geographical localisation of the study area
and the sampling points of soil/plant and water/se-
diment. The wind rose represents data from June
2013 to June 2014.
use of the calculated local geochemical background for both soils and
sediments based on the established normal Q_Q plots, since no geo-
chemical background was ever calculated for the studied area. The use
of various background values is necessary due to the lithogenic differ-
ences that can have a significant impact on the concentrations of heavy
metals in natural conditions (Matys Grygar and Popelka, 2016).
2.4.2. Risk associated with heavy metals
2.4.2.1. Potential ecological risk index (Eir). To discuss the potential
hazard of the obtained heavy metals concentration on the ecological
systems (Hakanson, 1980), the potential ecological risk index (Eir) was
calculated for soil and sediment samples via the equation Eir = Tif*Cif.
Cif stands for the calculated contamination factor while Tif corresponds
to the toxic response of the heavy metal. Cif is obtained by dividing the
concentration of each element by its baseline value. In this study, the
baseline values were calculated from the mean concentrations of heavy
metals in uncontaminated soils and sediments of the study area, since
using the earth crust levels can be inappropriate due to geogenic
differences (Matys Grygar and Popelka, 2016). According to Xu et al.
(2008), the toxic response factors of the studied heavy metals are 5 for
Cu and Pb, 1 for Zn, 10 for As and 30 for Cd. The ecological risk degree
of the trace metal corresponds to the obtained potential ecological risk
Eir value (Hakanson, 1980), where Eir < 40 indicates low risk; 40 < Eir
≤ 80 is moderate risk; 80 < Eir ≤ 160 is high ecology risk; 160 < Eir ≤
320 is serious ecology risk and Eir > 320 is severe ecology risk.
2.4.2.2. Sediment quality guidelines (SQGs). In recent years, the use of
sediment quality guidelines as powerful assessment tools for the
sediment contamination by heavy metals increased significantly
(Varol, 2011). This evaluation can be achieved by comparison of the
obtained heavy metals concentrations with previously standard
sediment quality guidelines known as PEL "probable effect level"
which above serious biological effects can affect the sediment-
dwelling organisms, and TEL "threshold effect level" below which the
obtained metals concentrations does not have any biological effects.
The PEL and TEL values for the studied heavy metals are shown in
Table 2 (MacDonald et al., 2000).
2.4.3. Statistical analysis and spatial presentation
Multivariate statistical analysis was based on clustering analysis
using Ward's method with Euclidean distances as a measure of simi-
larity (Ward, 1963) CA was performed to discuss relationships between
A. El Azhari et al. Ecotoxicology and Environmental Safety 144 (2017) 464–474

Table 1
Descriptive statistics of the physicochemical parameters of soils and sediments from the High Moulouya Valley.

Statistic pH Eh (mV) E.C (µs/cm) CaCO3 (%) Clay (%) Silt (%) Very fine sand (%) Fine sand (%) Coarse sand (%)

Tailings and soil samples (N = 20) Minimum 7.8 −117.2 34.4 0.4 6 15 7 3 0
Maximum 8.8 −62.7 526 65.2 45 58 38 44 29
25% 8.3 −110.4 54.5 0.9 10.8 22.3 14 10.3 0
Median 8.5 −96.5 70.2 2.4 19.5 29.5 18.5 25.5 3
75% 8.7 −89.4 122.2 17.9 24 42.5 20.8 33.8 12.8
Mean 8.5 −96.2 110.8 11.9 18.7 32.4 18.7 23.3 7.2
Std. d. 0.3 15.9 111 17.3 9.4 13.9 6.5 13.5 9
CV 0 −0.2 1 1.4 0.5 0.4 0.3 0.6 1.2
Sediment samples (N = 23) Minimum 7.9 −115.7 76.4 3.3 3.8 11.5 0.0 0 0
Maximum 8.8 −67.7 859 50.7 88.4 55.1 24.5 23 66.6
25% 8.2 −97 141.6 22.2 36.1 25.6 0.8 0 0
Median 8.3 −85.9 234.3 31.6 52.6 38 5.2 0.4 0
75% 8.5 −81.3 365 38.5 61.8 43.7 9.6 3.5 2.6
Mean 8.3 −88.8 287.3 30.1 50.4 35.7 6.3 2.6 5.1
Std. d. 0.2 13.3 195.1 12.7 19.8 11.8 6.5 5 14.2
CV 0 −0.1 0.7 0.4 0.4 0.3 1 1.9 2.7

the different groups of variables, which in our study can be common
sources and similar chemical properties of heavy metals (Varol, 2011;
Yuan et al., 2013; Arslan and Turan, 2015). Box plots that represent six
parameters namely the minor limit, first quartile, average, third quar-
tile, higher limit and extreme values were elaborated to present various
parameters. The software SPSS v.22.0 (IBM, Chicago, IL) was used in
the previous applications. The geography information system software
ArcGIS 10.1 was used to obtain the geochemical maps of heavy metals.
Inverse distance weighting (IDW) module (Burrough and McDonnell,
1998) was applied to interpolate the soil heavy metals concentrations to
produce the geochemical distribution maps.
3. Results and discussion
3.1. Physicochemical characteristics of soils
The descriptive statistics of the physicochemical characteristics of
surface soils are displayed in Table 1. The soil samples revealed an
alkaline pH between 7.8 and 8.8. High pH values often promote pre-
cipitation and adsorption of most metals (Ma et al., 2015). However,
the toxicity of many metals such as Pb increases with increasing pH
(Esbaugh et al., 2013). The high pH values and the overall moderate
conductivities (average of 110.8 µs/cm) were essentially due to the
limestone environment. The Eh results, with an average of −96.2 mV
indicated relatively reducing soils. The tailing samples (S-T1, S-T2, and
S-T3) and their nearby soils (S4 and S5) had a very abundant silt-clay
fraction reaching around 80%. Moreover, the abundance of fine and
coarse sand fractions in these samples was very limited with a com-
parison to other samples toward the Hassan II Dam. Tuo et al. (2014)
found that the wind and water erosion of the surface soil (0–1 cm)
engender the decrease in fine particles ( < 0. 01 mm) and the increase
in coarse particles ( > 0. 05 mm) causing an increase in finer particles
content in the sediment. Thus suggesting that the studied tailings soils
could be mobilized to the nearby environment under erosion due to
their abundant silt-clay fraction. The fine granulometry in the tailing
soil samples reflects the ore processing methods, which in Zeïda mine
were mainly gravimetric and flotation procedures. The low carbonate
contents in tailings can be attributed to the granite and sandstone
composition of the host rock. Furthermore, the schist and granite
abundance in the geological outcrops of the sampling area can explain
the relatively low contents of carbonates in most surface soils.
3.2. Physicochemical characteristics of sediments
The descriptive statistics of the physicochemical characteristics of
surface sediments are displayed in Table 1. pH of the sediments was
between 7.9 and 8.8, indicating that the sediments were alkaline. The
high pH values, the moderate to high conductivity values (reaching up
to 859 µs/cm) and the abundance of calcium carbonate in sediment
samples (average 30%) were mainly attributed to the limestone and
dolomitic substrate of the Upper Moulouya. The granulometry of the
studied sediments was dominated by the silt-clay fraction, with content
surpassing 80% for most samples indicating a very fine sediments
granulometry. The Eh values ranged between −115.7 mV and
−67.7 mV, depicting suitably reducing sediments. Overall, the studied
sediments offer favorable conditions for heavy metals accumulation,
not only because of their physicochemical properties but also due to the
chemical behavior of heavy metals in such conditions. For instance,
high pH values enhance the precipitation of heavy metals through the
formation of insoluble carbonates (Sposito, 1989). The mobility of
heavy metals can also be limited due to the reducing conditions and to
the decreases of redox potentials (Kelderman and Osman, 2007).
3.3. Heavy metal pollution assessment in soils and sediments
3.3.1. Geochemical background and anomalous values
Since no geochemical background was previously defined for the
study area, soil and sediment local geochemical backgrounds were
defined using the normality curves method (Martínez et al., 2007). The
inflection point of each curve allows classifying the different popula-
tions within the experimental data distribution (Annex 3). The mean
values obtained for the first population characterized by low values and
for the second population characterized by high values correspond re-
spectively to geochemical and anomalous values (Martínez et al.,
2007). The obtained mean values are then compared to their corre-
sponding guidelines (Table 2) and their natural occurrence in the
geological outcrops main rock types (Annex 4). During this study, the
determination of the geochemical background based on the sediments
and soils concentrations was necessary; the sediments being potentially
derived from materials eroded from various geological outcrops and
multiple rock types, while the soils sampled are derived from shale and
granite substrates. Thus, the natural heavy metal occurrence in both
soil and sediment can be different. The results indicated that the geo-
chemical background values of Pb, As, Cu, Cd, and Zn in both soil and
sediment followed the order Zn > Pb > Cu > As > Cd, and were below
the used references. Additionally, comparison of the obtained geo-
chemical background values with the concentration of the studied
heavy metals in the main rock types of the Upper Moulouya showed
that the geochemical background values are within their natural oc-
currence ranges, signifying that in natural conditions, the heavy metals
in soils and sediments are mainly derived from geogenic sources at low
concentrations and are not expected to cause any hazardous effect.

467
A. El Azhari et al. Ecotoxicology and Environmental Safety 144 (2017) 464–474

Table 2
Background and anomalous values (mg/kg) obtained for the High Moulouya surface soils and sediments.

Elements Samples from the High Moulouya Geochemical background Anomalous concentrations Guidelines

N Mean Median N Mean Median N Mean Median Limit valuesa Grade IIb

Surface soils As 20 21.8 3.7 16 5.3 3.3 4 87.6 37.2 12 30

Pb 20 1935.7 28.6 14 24.4 21.7 6 6395.5 5122.3 70 - 600 300
Cd 20 0.4 0.3 18 0.3 0.3 2 1.1 1.1 1.4 - 22 0.3
Cu 20 26.2 13.5 18 15.9 12.9 2 118.7 118.7 63 − 91 100
Zn 20 47.0 23.8 16 26.8 21.3 4 127.6 137.6 200 − 360 250

Surface sediments N Mean Median N Mean Median N Mean Median TELc PELd
As 23 6.7 6.3 19 5.9 6.1 4 10.3 9.3 9.79 33
Pb 23 94.4 33.7 18 32.6 28.7 5 317.0 150.9 35.8 128
Cd 23 0.3 0.3 19 0.2 0.3 4 0.4 0.4 0.99 4.98
Cu 23 29 27.9 15 24.1 25.1 8 38.1 37.9 31.6 149
Zn 23 73.5 70.6 19 64.2 66.9 4 117.7 90.5 121 459

a
Agriculture – Industrial limit values (CCME, 2006).
b
Grade II values for protecting human health (CMEP, 1995).
c
TEL: Threshold effect level.
d
PEL: Probable effect level (MacDonald et al., 2000).

However, the geochemical background values order was different from
the order of these elements in the upper continental crust with Zn >
Cu > Pb > As > Cd, which is due to higher concentration of Pb than Cu
in the geochemical background of the study area soils and sediments
that can be related to lithological differences and the natural abundance
of Pb in the geogenic formations. The calculated anomalous values in
soils for Pb (6395.5 mg/kg) and As (87.6 mg/kg), and in sediments for
Pb (317 mg/kg) exceeded both the natural occurrence of these elements
in the main rock types of the study area and the used guidelines.
3.3.2. Heavy metals spatial distribution in soils and sediments
The spatial distribution of heavy metals in the Upper Moulouya soils
was analyzed using GIS mapping technique based on geostatistics
(IDW). According to the geochemical maps (Fig. 2), the concentrations
of the five heavy metals show a similar spatial distribution in soil
sampling sites with the highest values of Pb, Zn, Cd, Cu and As detected
in the vicinity of the tailings impoundment. The heavy metal con-
centrations decreased with distance from the tailings, with the lowest
values observed near the Hassan II Dam. Soils around the mining wastes
are characterized by very high levels of Pb reaching up to 14,270 mg/
kg, significantly exceeding the established geochemical background for
Pb (24.4 mg/kg). The origin of Pb in the mine Zeïda wastes was cer-
ussite (Iavazzo et al., 2012) which was present in the mineral para-
genesis of the High Moulouya Valley (Margoum et al., 2015). For se-
diments (Annex 5), the highest concentrations of Pb, Zn, Cu, Cd and As
are observed downstream of the tailings. However, the spatial variation
is the most marked for Pb and Zn, which shows significant difference
along the Moulouya River stream, particularly downstream of the
sample ZM5 located at the crossing point of the Moulouya River with
the tailings impoundments. The order of the total heavy metal con-
centrations in soils and sediments was similar with Pb > Zn > Cu >
As > Cd. The obtained order, except for Pb, reflect the relative abun-
dances of these elements in the upper continental crust and the geo-
chemical background for soils and sediments.
The wide ranges of Pb contents in soils (6.2–14,270.2 mg/kg) and in
sediments (2.7–822.2 mg/kg) along with the high coefficient of varia-
tion value in soils (2.2) and sediments (1.8) suggests a multiplicity of Pb
sources (Yongming et al., 2006). Furthermore, and based on the spatial
distribution of Pb, Cd, As, Zn and Cu, the highest concentrations of
these metals were detected around the tailings. All these heavy metals
are widely known for being extremely hazardous not only to humans
but also to the fauna and flora of aquatic and non-aquatic environments
(Adriano, 2001). Therefore, the assessment of the ecological hazard of
the studied heavy metals in both soils and sediments as well as their
possible mobility from tailings to the surrounding environments is
necessary for future remediation protocols or advanced environmental
monitoring studies. To further discuss the local enrichment, con-
tamination and ecological risk associated with the studied heavy me-
tals, several methods were applied and discussed in the following sec-
tions.
3.3.3. Geo-accumulation index (Igeo) evaluation of heavy metals
The geo-accumulation indices based on both the average crust levels
and the local geochemical background are displayed in Annex 6 for
soils and sediments. The geo-accumulation indices calculated based on
the local geochemical background for Pb, Cd and As were inferior to
those obtained by applying the continental crust levels, while for Zn
and Cu the results were comparable. This difference can be crucial and
misleading in assessing the pollution levels. The assessment of the
heavy metal contamination was therefore performed based on the re-
sults obtained through using local geochemical background values for
both soils and sediments. Soils contamination ranged from un-
contaminated (Igeo < 0) to heavily contaminated for As (Igeo = 4.9) and
from uncontaminated to extremely contaminated for Pb (Igeo = 8.6). Cu
and Zn showed low to moderate contamination with Igeo < 3 while the
Cd contamination was low with Igeo < 2 in all soil samples. The pol-
lution levels of soils followed the spatial distribution of the total con-
centrations of heavy metals. The polymetallic contamination was the
most noticeable in tailings soil samples (S-T1, S-T2, and S-T3). How-
ever, the samples S4, S5 and S6 exhibited a heavy to extreme pollution
by Pb with Igeo > 3, suggesting that there was an actual dispersal of
contaminated materials from the tailings to the proximate soils.
Sediments contamination levels also followed the spatial distribu-
tion of the heavy metals total concentration, with the highest Igeo values
detected downstream of the abandoned tailings. According to the Igeo
results, Pb is the primary contaminant in the studied sediments with a
maximum value of 4.1 in the ZM5 sample; this contamination reaches
the sample ZM8 (Igeo = 3) located at around 9 km downstream of the
tailings. The contamination level of As, Cu, Cd, and Zn were low to
moderate in sediment samples from the Moulouya River, Hassan II
Dam, and the Ansegmir tributary with Igeo ≤1 in most sites.
3.3.4. Potential ecological risk (Eir) of heavy metals in soil and surface
sediment
Despite being contaminated, it is important to discuss if the mea-
sured concentrations of heavy metals in soil and sediment samples
would threaten the soil and sediment biota. For that reason, the po-
tential ecological risk (Eir) was applied. The (Eir) values for Pb in the
tailings samples were all higher than 160 with a maximum value of
1944.7, suggesting serious to severe ecological risk (Fig. 3). The serious

468
A. El Azhari et al. Ecotoxicology and Environmental Safety 144 (2017) 464–474

Fig. 2. Soils geochemical maps for Pb, Zn, Cd, Cu and As.

ecological risk extends from the tailings to the soil sites S4 and S5, thus
suggesting that the contamination and the risk associated with Pb
concentrations are not only limited to the tailings impoundments, but
also to their nearby soils. The studied tailings are consequently not only
considered as a potential point source of contaminant but also as a
serious threat to the surrounding ecological systems. The tailings im-
poundments ecological risk is aggravated due to the high As and Cd Eir
values with respectively 128 in the S-T1 and 116 in the S-T2 samples,
both indicating a high ecological risk. The ecological risk of Pb, Cd, As,
Cu and Zn in other samples toward the Hassan II Dam were low with
Eir < 80.
Sediment samples from the Moulouya River were found to have
moderate to serious ecological risk (Fig. 3). The highest hazards were
observed for Pb in samples downstream of the tailings with respectively
150.3 (ZM5) and 70.6 (ZM8), indicating that the concentrations of Pb in
these samples may have a hazardous effect on the sediment-dwelling
organisms. The Eir values for Cd, Zn, As and Cu were below 60, in-
dicating a low ecological risk associated with these heavy metals in
sediments. Nevertheless, the highest Eir values for these elements were
observed downstream of the abandoned tailings. The sediments con-
tamination was also assessed through comparison with the SQGs for
each heavy metal. The obtained results were in agreement with the Eir

Fig. 3. Box plots for the potential ecological risk (Eir) of selected elements in soil (a) and sediment (b).

469
A. El Azhari et al. Ecotoxicology and Environmental Safety 144 (2017) 464–474

results for As, Cu, Cd, and Zn, since the concentrations of these ele-
ments were overall inferior to the PEL or between the PEL and TEL.
Though, four samples exceeded the PEL for Pb concentration, namely
ZM5, ZM7, ZM8 and ZM10, reaching respectively 822.2 mg/kg,
151 mg/kg, 386.3 mg/kg and 130 mg/kg, thus exceeding the PEL for
Pb fixed at 128 mg/kg (MacDonald et al., 2000). These results indicated
that the Pb concentrations in sediments downstream of the fluvial
system are likely to cause frequent hazardous effects on the sediment-
dwelling organisms.
It is evident that riverine sediment and surface soil were severely
polluted, especially by Pb, the contamination was highest in soils near
and sediments downstream of the abandoned tailings impoundments.
The critical ecological risk associated with Pb concentrations require
immediate intervention through the development of an adequate re-
mediation procedure to decrease contamination and dispersion of
heavy metals to nearby soils and sediments downstream of the ex-
ceedingly polluted tailings. To discuss the potential transport through
the Moulouya River of heavy metals either as particle-bound or dis-
solved in waters, raw and filtrated waters contamination was also in-
vestigated.
3.4. Physicochemical characteristics of waters and quality assessment
All waters were relatively alkaline with pH values ranging from 6.9
to 8.7. The conductivity values ranged between 287 µs/cm and 420 µs/
cm with an average of 356 µs/cm. The moderate conductivity and the
high pH are mainly due to the geological features of the Upper
Moulouya; the studied rivers drain limestone and dolomite outcrops all
along their course. Based on the potential redox results, the waters offer
an oxidizing environment with positive potential redox values ranging
from 96 to 129 mV. Raw and 0.2 µm filtrated water are usually used to
assess the abundance and the contamination risk of trace elements in
continental waters (Gaillardet et al., 2003; Yang et al., 2014). The de-
scriptive statistics of the trace element concentrations in the raw and
filtrated water samples are shown in Table 3. The raw water samples
comprise the acid-extractable forms from the suspended matter, trace
elements absorbed in the coatings and carbonates as well as those
dissolved in the water (Yang et al., 2014). The trace elements con-
centrations in the raw water samples were compared to their
corresponding guidelines for drinking and freshwater life protection,
while the filtrated water samples contamination was assessed using the
background values of the world average based on the 0.20 µm filtrated
waters data compiled by Gaillardet et al. (2003). In raw waters, the
maximum concentrations of Pb, Cu, As and Cd did not exceed their
corresponding toxicity limits neither for drinking purposes nor for
protecting the aquatic life. These metals levels were also comparable to
the world background values in the filtrated waters. Zn showed higher
levels than Pb, Cu, Cd and As in both raw and filtrated waters, still, its
maximum levels were inconsequential in comparison to the conforming
guidelines. Based on the previous results, there was no apparent evi-
dence of any heavy metals carriage at anomalous levels through the
Moulouya River since they presented low coefficients of variation and
did not surpass their corresponding environmental and drinking limits.
3.5. Heavy metal contents in plants and toxicity assessment
The plant samples collected from the study area, even if they belong
to the same species (Stipa tenacissima L.), had different metal con-
centrations. All the studied metals are observed in every plant. The
plant (S1), corresponding to the tailings sample, highlighted the max-
imal Pb content of 1332.7 mg/kg. The Pb concentrations in the plants
near the tailings exceeded the toxicity limit value (300 mg/kg) with
493.2 mg/kg and 852.5 mg/kg for the S4 and the S5 plant samples,
respectively. The maximum concentrations of As (6.1 mg/kg), Cd
(0.8 mg/kg), Cu (58.8 mg/kg) and Zn (150.5 mg/kg) did not exceed the
toxicity limit values (Kabata-Pendias and Pendias, 2001) correspond-
ingly fixed at (20 mg/kg), (30 mg/kg), (100 mg/kg) and (400 mg/kg),
in all analyzed plant samples.
4. Cluster analysis
To discuss the sources and mobility of the contaminants between
the different studied environments, e.g. soils, plants, waters and sedi-
ments, cluster analysis (Euclidean Ward linkage dendrograms) was
used. Tailings samples were excluded from the data set to discuss their
possible contribution properly. The Ansegmir samples were also ex-
cluded since they are not directly affected by tailings spill. The re-
lationships between Pb, Cd, Zn, Cu and As were therefore investigated

Table 3
Descriptive statistics of chemical elements in the raw and 0.20 µm filtrated water samples.

Raw Filtrated

Element (μg/l) Pb Zn Cu As Cd Pb Zn Cu As Cd

Moulouya River (n = 17) Minimum 0.94 9.91 3.01 1.60 0.03 0.03 0.00 0.79 0.47 0.00
25% 1.23 18.83 3.91 1.83 0.04 0.04 0.00 1.82 0.98 0.00
Mean 4.84 61.47 5.97 2.22 0.10 0.06 5.77 2.76 1.06 0.01
75% 8.06 33.24 7.42 2.23 0.12 0.07 4.22 2.67 1.21 0.01
Maximum 15.44 424.48 13.82 3.80 0.30 0.10 60.54 9.37 1.34 0.02
Median 3.15 23.93 4.91 2.04 0.07 0.05 1.48 2.22 1.14 0.01
Std. d 4.41 103.76 2.88 0.65 0.08 0.02 14.54 2.03 0.22 0.00
CV 0.88 1.64 0.47 0.28 0.73 0.38 2.44 0.71 0.20 0.60
Ansegmir tributary (n = 6) Minimum 0.97 7.74 3.50 1.56 0.05 0.02 < DL 0.61 0.29 0.00
25% 4.26 27.17 9.33 2.59 0.15 0.03 < DL 0.89 0.32 0.00
Mean 10.88 66.12 17.79 4.28 0.28 0.03 3.66 1.13 0.49 0.00
75% 12.77 93.76 22.87 5.17 0.29 0.03 2.64 1.28 0.38 0.01
Maximum 25.37 145.16 34.22 7.38 0.79 0.06 17.53 1.77 1.29 0.01
Median 12.17 61.94 19.55 4.82 0.18 0.03 0.67 1.10 0.33 0.01
Std. d. 8.95 52.13 11.48 2.21 0.27 0.02 6.90 0.40 0.39 0.00
CV 0.75 0.72 0.59 0.47 0.87 0.43 0.33 1.72 0.72 0.46
Guidelines Drinking water quality (Raw waters) 15a 5000a 1300b 10b 3b 0.079e 0.60e 1.48e 0.62e 0.08e
Freshwater life protection 65c 120d 13d 340d 2d

a
USEPA (2009).
b
WHO (2004).
c
(www.epa.gov).
d
USEPA (2006).
e
Background values (Gaillardet et al., 2003).

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A. El Azhari et al. Ecotoxicology and Environmental Safety 144 (2017) 464–474

50 a) Soils 50 b) Sediments
45 45
40 40
35 35
30 30
Distance

Distance
25 25
20 20
15 15
10 10
5 5
0 0
Cd

Cu

Cu

Cd
As

As
Zn

Zn
Pb

Pb
160 c) Waters and sediments 70 d) Soils and plants
140
60
120
50
100
Distance

80 Distance 40

60 30
40
20
20
10
0
Cu sedim
Cd Raw

Cu Raw
As Raw

Zn Raw
Pb Raw
Cd Dis
Cu Dis

As sedi
As Dis
Cd sedi

Pb sedi
Zn sedi
Zn Dis

Pb Dis

0
Cd-P
Cd-S

Cu-S
Cu-P
As-S
As-P

Zn-S

Zn-P
Pb-S
Pb-P
Fig. 4. Dendrograms (distance: Euclidean) showing the clustering of the analyzed metals in: a) Soil samples. b) Sediment Samples. c) Water and sediment samples (Dis: dissolved, sedi:
sediments). d) Soils (S) and plants (P).

in soils and plants toward the Hassan II Dam (Fig. 4a; Fig. 4d), as well as
surface waters and sediments collected from the Moulouya River
(Fig. 4b; Fig. 4c).
CA performed on the soil and sediment data sets rendered com-
parable dendrograms (Fig. 4-a) and (Fig. 4-b), where the five studied
heavy metals were clustered into two significant groups. For both
dendrograms, the first group includes Pb and Zn. In Zeïda, the exploited
ore body consisted mainly of cerussite (70%) and galena (30%). Zn-
containing ores from diverse Moroccan mines were also stored and
treated in the Zeïda district (Iavazzo et al., 2012). Therefore, Pb can be
considered as the metallic signature of the Zeïda tailings. The first
cluster can consequently represent contaminants derived from both
anthropogenic source (Tailings impoundments) and geogenic sources,
also confirmed by the maximum concentrations and Igeo values of Pb
and Zn being detected in sediment and soil samples near the studied
tailings. Cluster 2 contains As, Cd and Cu, these elements showed lower
concentrations than Pb and Zn in most soils and sediments and also had
smaller spatial variabilities (Annex 5), suggesting that these elements
originated principally from natural sources. Nevertheless, the max-
imum levels of As, Cu and Cd were observed in soils near and sediments
downstream of the tailings.
CA was also performed on the water (filtrated and raw) and sedi-
ment data sets to discuss the potential mobility and relationships among
heavy metals in the sediment/water-column, all variables were grouped
into three different clusters (Fig. 4c). Cluster 1 regroups Pb and Zn in
sediments, the association of these elements is likely due, in addition to
their sources diversity as discussed above, to their comparable spatial
distribution and their higher concentrations along the Moulouya River.
Zn in raw waters and Cu in sediments were reordered in the second
cluster. Zn had higher levels in the raw waters compared to Cu, Cd, As
and Pb while Cu in sediments had relatively higher levels than As and
Cd, but much lower than Pb and Zn (Annex 5). Zn in raw water and Cu
in sediments association with Pb and Zn in sediments suggests that they
were derived from both anthropogenic and natural sources. However,
Zn concentrations in the raw waters did not exceed its permitted limits
while Cu displayed low Igeo indices values (Igeo < 1) in all sediment
samples. Therefore, the potential Zn and Cu inputs from the tailings do
not significantly contribute to the metallic contamination of the Mou-
louya River water and sediments. Cluster 3 regroups the remaining
elements in the raw waters (Cu, Cd, As and Pb), filtrated waters (Zn, Pb,
Cd, Cu and As) and sediments (Cd and As), suggesting that the studied
elements in waters, as well as Cd and As in sediments, are principally
derived from geogenic sources with no evident anthropogenic con-
tribution.
Based on the previous results, it can be concluded that none of the
studied elements are transported in dissolved forms through the
Moulouya River at non-standard concentrations, which means that in
the study area, neutral and acid mine drainage does not occur, and are
not expected to happen if the environmental conditions do not drasti-
cally change. The clastic transport in surface waters is also very limited
since the studied elements do not travel at high concentrations as
particle-bound in the raw waters. Thus assuming that the releases from
the tailings impoundments, deposits as sediments rather than being
transported by the surface waters. The obtained results are in complete

471
A. El Azhari et al.
agreement with the environmental conditions of the study area, which
promotes very low solubility of heavy metals. Pb, being the primary
contaminant, is considered as a low mobile element and mainly found
associated with particles, its transport is relatively limited in neutral
and alkaline environments due to the formation of carbonates
(Gaillardet et al., 2003). Zn, associated to Pb in both soils and sediments
dendrograms, hydrolysate and is consequently absorbed by carbonates,
oxides and clays (McLean and Bledsoe, 1992), Zn is also subjected to
the processes of sorption mainly on oxy-hydroxides of iron and man-
ganese and clayey minerals (Buatier et al., 2001). Thus, the natural
environmental conditions prevent the transport of Pb and Zn as dis-
solved in the waters and instead promotes their accumulation in riv-
erine sediments.
The long distance contamination of Moulouya River sediments by
Pb, exceeding the PEC limits in the samples ZM10 (located at around
13 km downstream of the tailings impoundments) can consequently be
related to the transport of Pb as adsorbed into the sedimentary parti-
cles. Three major transport modes of sedimentary particles can occur
simultaneously or independently (Hickin, 1995); dissolved load and
suspended sediments load, these transport modes do not contribute in
the dispersion of contaminants through the Moulouya River since the
studied heavy metals transport via solution and as particle-bound is
very limited due to their very low concentration in these phases. Bed-
load is the third transport mode where the particulate material moves
through the channel entirely sustained by the canal bed itself. However,
this transport mode is rather related to gravel and sand fractions. The
studied sediments granulometry is characterized by the abundance of
the silt-clay fraction, with very high clay percentages. Though, the most
abundant metals in sediments (e.g. Pb and Zn), have high density with
respectively 11.35 g/cm3 and 7.13 g/cm3. These high densities of Pb
and Zn could restrict the resuspension of the particle-bound heavy
metals. Abbasi (2014) demonstrated that the settling velocities of Pb
and Zn are directly influenced by their respective densities. Further-
more, the semi-arid climate of the study area and the low flow rate of
the Moulouya River does not favorite the resuspension of the sediments
particles. All these factors combined highly suggests that the dispersed
tailings materials will be preferentially accumulated in sediments and
transported as bedload, rather than being carried through the surface
waters. The Igeo results showed that the Igeo value of Pb in the distant
ZM8 sample (Igeo = 3) was higher than that in the ZM6 (Igeo = 0.2) and
ZM7 (Igeo = 1.6) samples located closer to the tailings. The three
samples had comparable physicochemical parameters but different
metal elements concentrations (Annex 5). The abnormal Igeo values in
the ZM6 and ZM7 samples could be related to the flow velocity varia-
tions along the Moulouya River. The diminution of flow velocity is
caused by reductions in discharge or a change in the grade of the stream
(Thorpe, 2011). In a slow flow rate environment, most of metals dis-
charged from the mining wastes would deposit after entering the river
channel (Sin et al., 2001; Hudson-Edwards et al., 2008). The elevation
drops along the Moulouya stream from the ZM5 (1440 m) to the ZM8
(1378 m) sampling site can explain the low contamination level in the
ZM6 and ZM7 samples, since dispersed materials from the tailings were
potentially transported and deposited downstream of the river due to
the diminution of the river flow rate (Day et al., 2008). This spatial
distribution can also be related to the flash floods of the Moulouya
River that can cause significant sediment carriage and deposit down-
stream of the fluvial system (Foody et al., 2003; Di Francesco et al.,
2016).
In this study, and based on the spatial distribution, the geo-accu-
mulation indices and the clustering of As and Cd results, these elements
were not related to the dispersals from the tailings to their nearby soils.
This low mobility can be related to the physicochemical properties of
the studied tailings piles and the corresponding chemical behavior of
these heavy metals. The mobility of As is rather limited and is hardly
leached by Percolating water due to its adsorption on clay and hydro-
xides (Kabata-Pendias and Pendias, 1992). According to Rollin et al.
472
Ecotoxicology and Environmental Safety 144 (2017) 464–474
(2006), the behavior of Cd is strongly related to pH; the solubility of Cd
increases at pH < 6, and undergoes a slight adsorption by colloids of
the soil, hydroxides or organic matter, at pH > 6, cadmium is absorbed
by the solid phase or precipitates, the absorbed Cd is not easily mobi-
lized (Kabata-Pendias and Pendias, 2001). The mobility of Cd and As in
studied water is also limited. At high pH values, Cd is mainly found in
insoluble forms that are immobile and deposits and get absorbed by
sediments (ATSDR, 2007), while the As is often removed from hydro-
logic systems through precipitation and association with sulfides,
sorption on clay minerals, and carbonates (Henke, 2009).
The relation between heavy metals in soils and plants was also in-
vestigated. Cluster analysis rendered a dendrogram (Fig. 4d) where
heavy metals in soils and plants were grouped into two groups. The
dendrogram showed a strong relation between the concentration of Pb,
Cd, Zn, Cu and As in soils and their levels in plants that can be related to
the common sources of metals. The relation between Cu and Zn with Pb
could signify that these elements were derived from the tailings in
addition to their natural occurrence. However, the plant contamination
was only associated with the high Pb concentrations, while Zn and Cu
were detected at levels below their corresponding toxicity limits. Nu-
merous studies suggested that the main pathway by which plants ac-
cumulate Pb is through root uptake from soils (Seregin et al., 2004; Uzu
et al., 2009) and that the Pb concentrations of plants grown in miner-
alized areas are highly correlated with the Pb content in soil (Jung and
Thornton, 1996; Kabata-Pendias and Pendias, 2001). Thus suggesting
that the Pb contamination is not only limited to the studied soils depth
but extends deeper in the soil reaching the subsoil horizon, which re-
quires further investigations. The high content of Pb in our studied
plant samples could also be attributed to the Pb chemical behavior,
since it can inhibit the uptake and transport of additional cations like
Zn and Cu, by either binding them to ion carriers, or by changing the
permeability and activity membranes (Patra et al., 2004). As and Cd
were grouped in the second cluster, proposing that these elements
originated principally from natural sources, also confirmed by their low
geo-accumulation values in soils and their levels below the toxicity
limits in plants. Nevertheless, the studied plant (Stipa tenacissima L.)
was found to be able to accumulate Pb at high concentrations, the use of
this plant as a potential tool for phytostabilization of the contaminated
tailings and phytoextraction of Pb from contaminated soils is to be
considered and studied in future remediation researches. The stabili-
zation of the studied tailings can reduce their particulate spill con-
siderably to nearby soils and fluvial systems, considered as the main
dispersion pathway of heavy metals in the study area.
This study demonstrated that the studied heavy metals are mainly
transported as particle-bound from the tailings, deposits as sediments in
the Moulouya River, and are afterward carried downstream of the
tailings piles. The wind transport of contaminated particles, and based
on the soils geochemical maps, is limited to the tailings impoundments
area and does not play a principal role in the dispersion of contaminants
toward the Hassan II Dam despite the semi-arid conditions and the fine
particle-size distribution of the studied tailings soils, but does however,
feasibly contribute in the dispersion of contaminated materials from the
tailings to the Moulouya River fluvial system.
5. Conclusion
The purpose of this study was to assess the levels of Pb, Zn, Cu, Cd
and As in the soil-plant system and the sediment-water column as well
as discussing the environmental fate of those metals around the aban-
doned Pb-Zn Zeïda mining district. The results indicated that the
abandoned tailings piles exhibited the highest concentrations of Pb, Cd,
Cu, As and Zn. The soils geochemical maps showed that the levels of
heavy metals decreased with distance from the tailings. Based on the
geo-accumulation index results, soils from and near the tailings im-
poundments, as well as sediments of the downstream fluvial system, are
highly enriched and contaminated by Pb, while the As, Cu, Cd and Zn
A. El Azhari et al.
contamination is bounded in the tailings piles area. The contaminated
soil and sediment samples also had a significant ecological risk based on
the high potential ecological risk indices results for Pb. Comparison of
the heavy metals concentrations in assessed sediment samples with the
consensus-based sediment quality guidelines was also conducted. The
results revealed that the Pb concentrations in contaminated sites might
cause hazardous effects to the sediment-dwelling organisms. Heavy
metals in the raw and the filtrated water samples from the Moulouya
River originated mainly from lithogenic sources and did not show any
abnormal values, indicating that the heavy metals derived from the
tailings accumulate in sediments, and are transported afterward as
particle-bound to the bedload. In this study, cluster analysis was used.
CA results suggest that: i) Pb and Zn concentrations in sediments were
affected by additions from the tailings impoundments, ii) Pb, Zn, and
Cu were potentially derived in soils and plants from the tailings in
addition to their natural occurrence, iii) As and Cd originated primarily
from the natural geological background.
This study indicated that soils, sediments, and plants were heavily
polluted by Pb, the soils and plants pollution was highest at sites closest
to the tailings piles, while the sediments contamination extended sev-
eral kilometers downstream of the fluvial system. The dispersion of
contaminants as particle-bound is highly suspected of being the main
dispersion pathway of heavy metals from the tailings piles towards the
surrounding environments. These results can help in the development
of future remediation strategies that will primary aim to cease solid
material discard from the tailings.
Appendix A. Supplementary material
Supplementary data associated with this article can be found in the
online version at http://dx.doi.org/10.1016/j.ecoenv.2017.06.051.
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