Evaluation by X-ray fluorescence (XRF) of major and trace elements accumulated in Xanthoria parietina (L.) Th. Fr. (1860) indicating levels of pollution in Blida area(Algeria)

Abstract

The purpose of this study consists of the biomonitoring of air pollution in the Blida area in Algeria. Samples of the cosmopolitan lichen Xanthoria parietina were collected from trees
situated in different sites through 14 surrounding districts. The observation of lichen under SEM improved our understanding that lichens have a porous structure that accumulates mineral elements more than plants, which have on their epidermis a protective cuticle.
We used the XRF analysis technique to view the multi-element aspect in our project. A total of 14 elements were measured and approved by QA/QC procedures. The maximum and minimum values of the 5 major elements are: Al (4351-15616), Cl (119-701),Fe (2397-5493), K (2068-4437),and P (519-1486) μg/g. And the values for the nine trace elements are: Br (11-61), Cr (4-10), Cu (6-80), Mn (24-161), Pb (13-244), Rb (12-60), Sr (15-103), V (8-19) and Zn (26-416) μg/g. Mapping registers high values in some areas due to local emissions of industrial facilities, road traffic, waste, and urbanization regardless of the environment. Even theforest area, including the Chréa National Park, is affected due to repeated fires, high frequency of traffic, and due to the tracks management

Full text

Algerian Journal of Environmental Science and Technology
December edition. Vol.5. No4. (2019)
ISSN : 2437-1114
www.aljest.org
ALJEST
Copyright © 2019, Algerian Journal of Environmental Science and Technology, All rights reserved
Evaluation by X-ray fluorescence (XRF) of major and trace
elements accumulated in Xanthoria parietina (L.) Th. Fr.
(1860) indicating levels of pollution in Blida area(Algeria)
L.Kouadri1, M.E.A. Benamar1, 2,*, A. Benkhalifa3
1 Laboratory of Fundamental and Applied Physics Faculty of Sciences University of Blida1
PB 270 Blida Algeria
2University Center of Tamanrasset, PO Box 10034, 11000, Algérie
3Ethnobotany and Natural Substances Laboratory, ENS El-Ibrahimi Kouba, Algiers PB 52
Kouba, Algiers 16050, Algeria
*Corresponding author email: benamardz64dz@gmail.com ; Tel.: +213 6619581956; Fax: +21325438320
ARTICLE INFO
ABSTRACT/RESUME
Article History :
Received : 17/03/2019
Accepted : 13/10/2019
Abstract: The purpose of this study consists of the biomonitoring of
air pollution in the Blida area in Algeria. Samples of the
cosmopolitan lichen Xanthoria parietina were collected from trees
situated in different sites through 14 surrounding districts. The
observation of lichen under SEM improved our understanding that
lichens have a porous structure that accumulates mineral elements
more than plants, which have on their epidermis a protective cuticle.
We used the XRF analysis technique to view the multi-element aspect
in our project. A total of 14 elements were measured and approved
by QA/QC procedures. The maximum and minimum values of the 5
major elements are: Al (4351-15616), Cl (119-701),Fe (2397-5493),
K (2068-4437),and P (519-1486) μg/g. And the values for the nine
trace elements are: Br (11-61), Cr (4-10), Cu (6-80), Mn (24-161),
Pb (13-244), Rb (12-60), Sr (15-103), V (8-19) and Zn (26-416) μg/g.
Mapping registers high values in some areas due to local emissions
of industrial facilities, road traffic, waste, and urbanization
regardless of the environment. Even theforest area, including the
Chréa National Park, is affected due to repeated fires, high frequency
of traffic, and due to the tracks management.
Key Words:
Biomonitoring; major and
trace elements; Xanthoria
parietina; X-fluorescence
(XRF); Blida.
I. Introduction
Atmospheric pollution constitutes a public health
hazard. The pollutants do not remain near their
emission source but may be carried on long
distances and create environmental issues. The
study of the atmospheric pollution of Blida and its
surroundings constitutes a good opportunity to
understand this phenomenon. Blida is surrounded
by urban and suburban areas and is located at the
foot of the Blidian Atlas, which rises over 1500
meters above sea level. It is where the natural cedar
(Cedrusatlantica) forest of Algeria is located, with
its specific biodiversity represented by some rare
and endemic species (Macacasylvanus,
Taxusbaccata). The National Park of Chréa was
created in 1926 and was registered officially by the
Algerian area after independence in 1983, in order
to protect the natural forest area. The Blida area
spreads out over the best part of the most important
plain of Metidja, which is marshy in winter and
subjected to severe drought in the summer. It is
located in an area devoted to agriculture but
invaded by accelerated and uncontrolled
urbanisation and industrialisation. The development
and intensification of the means of communication
and transport in particular require the thinking of
tracking devices for the air quality. Environmental
surveys are necessary to measure the emission of
heavy metals into the atmosphere with special
regard to the threat presented for the health of the
population.
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A number of studies [1, 2, 3] have shown the
heterogeneity of the targets of the metallic trace
element in the human organism, as well as their
toxicity (neurological, cardiovascular, respiratory or
renal impairments), and even their carcinogenicity
[4, 5, 6, 7]. The environmental monitoring becomes
a necessity to identify the potential danger to
human health and present ecosystems, and would
be at the basis of preventive or curative appropriate
measures [3, 8]. In this scope, the use of living
organisms in the monitoring of the air quality
(biomonitoring) constitutes an important research
field that develops into ambitious applications [9,
10, 11]. This method complements the other means
of environmental monitoring [12]. The advantage is
that it is fast and relatively simple to implement,
and is less expensive compared to chemical
methods or other physical measurements requiring
technical installations and the involvement of
qualified personnel. Bioaccumulation is a reliable
method for estimating cumulative effects over time
and synergy between pollutants [6, 13, 14].
Recently, a novel technique based on gold
nanomaterial and biological molecules was
developed for sensitive lead detection in
environmental monitoring [15, 16]. Lichens are
considered as bioindicators, and their advantage lies
in using them as sensors for the long term. They
will be able to retrace the historical reasons for
human habits and to monitor current human actions
in general, and the impact of industrial facilities in
particular. Lichens are particularly suitable
organisms for the study of atmospheric pollutants
[9, 17, 18, 19, 20, 21, 22, 23]. With a very slow
metabolism, lichens accumulate substances over a
long period of time and are able to trap very fine
particles [14, 21]. According to atmospheric
modifications, they are therefore sensitive to the
fallout of pollutants present in both dry and wet
deposition. Lichens have been used for more than
40 years [14, 17, 20] to monitor the contamination
of the environment by metallic trace elements and
are able to accumulate large quantities of these
elements [20,24]. They are good carriers for
measuring metal elements using their fully
atmospheric-dependent feed ways [20,25]. Lichens
are relevant to diagnose the impact of atmospheric
pollution and its spatial distribution. They
constitute an approach and a complement that can
be interesting to use in physicochemical
measurements, statistical studies, and to establish
mapping and modelling of air quality [17,18].
Several works have been published dealing with the
topic of air pollution using various lichen species
[26, 27, 28]. Xanthoria parietina (L.) Th. Fr. has a
cosmopolitan distribution even at high altitudes and
it is the most widely available lichen that is
moderately tolerant to air pollution [19, 29]. This
species is considered to have a moderate resistance
to atmospheric metals pollution [30].
Xanthoria parietina persists inside and outside
cities, where the pollution is accentuated but not at
extreme degrees. It can be observed on house roofs
and stuck on trees and even on road sides. Thus,
this species of lichen constitutes a favourable
choice to monitor the air quality before it arrives at
extreme levels of pollution, damaging human health
and leading to the collapse of the environment. On
the basis of this principle, we must measure the
quantities of heavy metals and trace elements
accumulated within the thallus of the lichen to
certify real levels reached in order to know with
more certainty the reality of the quality of the air.
Then, we can clarify how to stop the progression or
to enhance an expected quality if sources of
emission are detected and controlled.
In this study, our goal consist of analyzing lichen
samples in order to determine how Xanthoria
parietina accumulates detected concentrations of
major and trace elements by XRF analysis in the
location of the urban districts in the Blida area, in
comparison with the forest area of the Chréa
National Park. We also plan to compare data
between districts and with other cases both in
Algeria and throughout the world
II. Materials and methods
II.1. Presentation of the species Xanthoria
parietina (L.) Th. Fr. (1860)
Xanthoria parietina or Xanthorea is foliose lichen,
quite abundant in many parts of the world. Its toxic
tolerance index is 7, which qualifies it as a
moderately tolerant species for air pollution [31].
The advantage of this species is: easy identification,
availability for sampling in various environments,
and resistance to a certain degree of pollution. Its
cosmopolitan trait reduces costs in biomonitoring,
particularly in developing countries (see Figure.1).
Xanthoria
parietina at
Suomenlinna
Island (Finland) in
a non-polluted
environment,
September 1,
2016.
Xanthoria
parietina in a
slightly polluted
environment in
Chiffa (Blida),
Algeria, October
24, 2016
Xanthoria parietina in a
moderately
polluted environment in
Oued Alleug (Blida),
Algeria, October 24,
2016
Figure1.Presence of Xanthoria parietina in
different environments.
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II.2. Presentation of the study area
Blida is located 50 km south of the capital,
Algiers. The area of the study (Figure 2) includes
the central and western part of the area. This area is
located between the latitudes 36° 23.818' and 36°
37.137' north and longitudes 2° 36.360' and 3°
02.685 east. The altitude varies between 63 m from
sea level and 1629 m (highest point) in the Chréa
National Park. Administratively, the area of Blida
is divided into 25 districts, of which 15 were
prospected: Ain Romana, Benkhelil, BeniTamou,
Blida, BouarfaBoufarik, Bouinan, Chebli, Chiffa,
Chréa, El-Affroun, Guerrouaou, Mouzaia, Oued El
Alleug, and Soumaa (Figure 2).
Figure 2. Positioning of the sampling sites in Blida
and its surroundings on the administrative districts
map of the Blida area (National Institute of
Cartography and Teledetection, 2016)
II.2.1 Repartition of the industry and landfills
Industries:
Although the Blida area is devoted to agriculture, it
has reached a significant industrial development,
thus expanding its industrial network by the gradual
establishment of several industrial units working in
varied fields. The industrial infrastructure consists
of 4,258 production units characterized by an agro-
food industry followed by metallurgical, chemical
and glass industries distributed as shown above in
Table 1(see Figure 3).
Table 1: The industrial network in the Blida area
Field of activity
The main activity
Number of production units
%
Food
● Cheese dairy-flour mill- beverage
● Bakeries- industrial confectionery
● Confectionary-cookie factories-dairies
1 768
43
Metallic and Electrical
Industries
● Electrical appliances-manufacturing
● Industrial-metal frame and foundry
383
9
Textiles, Shoes and Leather
● Garment-socks making
● Fabric-leather-mattress bags
356
8
Chemistry and
Plastic
● Chemicals and cosmetics
● Plastic packaging- plastic processing
● Cleaning products
294
7
Materials of Construction
and the Glass Industry
● Concrete blocks, tiles, cement
● Mirror-Glazier-Ceramic-Sanitary Products
182
4
Printing Houses
Stationery
Wood and Tobacco
● Joinery-furniture manufacturing
● Wooden packaging and notebooks
● Paper transformation
134
3
Services
● Services provided to businesses
● Non-market services provided to the community
● Services and works tankers
● Market services provided to households
1 141
27
Total
4258
100
Landfills:
It appears from the comprehensive inventory of
landfills in the various districts of the Blida area
that the most dominant type of landfill remains the
uncontrolled dumping site(see Figure 3). With the
exception of the following districts that dump their
household waste at the BeniMered composting
plant: Blida, OuledYaich, BeniMered, Guerrouaou
and Chréa.It is important to note that the majority
of these uncontrolled landfills are located mostly in
the Mitidja plain and along areas known as Oueds
(riverbeds) including: Oued El-Harrach,
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OuedChiffa, OuedBou-Roumi, OuedDjemaa and
Oued El-Had. Landfills have become a potential
pollution source for rivers and streams in these
areas, affecting population health.
Figure 3. Geographical distribution of the types of
industries and landfills in the study area (Blida and
its surrounding districts)
II.2.2. The climat
The average annual rainfall is about 646 mm/year
and more than 1500 mm/year at Chréa[32]. The
areas of snow during the winter are particularly
those of the Blidian Atlas chain, the mountains of
Chréa, and Mouzaia. The monthly average
temperatures range from M = 43.20°C in the
hottest month (July 2015) to M=1.5°C in the
coldest month (February 2015). The records are
m'=-3.2°C and m'=44.6°C for the recorded period
from the years 2000 to 2016. The prevailing winds
during the sampling period of May, June and July
2015 were recorded as follows: calm wind 42.93%,
NE: 22.37% (National Office of Metrology,2016).
The most likely hypothesis concerning the direction
of the fallout of the pollutants under the industrial
atmospheric incidence must be oriented towards the
direction of the north-east wind, without neglecting
possible pollution towards the caps at 90° (8.68%)
and 315° (8.53%).
(a) Aridity
index of the Blida
Station
(b) Ombrothermic
diagram and dry period in
Boufarik
(c) Ombrothermic
diagram and dry period in
Blida
(d) Ombrothermic diagram
and dry period in Chréa
Figure 4. (a) Aridity index, dry periods and
ombrothermic diagrams of the stations in
(b)Boufarik, (c) Blida, (d)Chréa
Aridity indices and calculation of dry periods:
The ombrothermic diagrams of Boufarik, Blida and
Chréa stations show two main periods (Figure
4).The first period is from November to May and
consists of fresh coolness, brought about by the
winter rains and during which temperatures are low.
And the second is from May to October, consisting
of rather dry conditions, with peak dryness seen in
July and August, even for the station of Chréa,
which has an altitude of over 1500 m.
This dry period coincided with the collection period
of lichen samples for this study.
II .2.3. Location of sampling sites
Samples were chosen only from trees and not from
roofs of houses or other facilities. The sampling
sites were from natural environments such as
forests, cultivated fields, or roadside trees. The aim
was to cover areas of different pollution levels.
Samples were picked close to industrial activities
and urban areas, while others were taken near roads
that are exposed to different traffic intensities.
Some samples were also picked in forest
environments in the Chréa National Park.
Forty-two (42) samples were collected during the
period from May to July in 2015, targeting
locations near industries, roads and landfills (Figure
3). Lichen samples were taken separately, so as to
limit contamination and loss. For each collected
sample, we recorded the following aspects of the
data: sampling time, date, name, GPS coordinates
(longitude and latitude), and the altitude of the
location. Lichen samples were codified and were
stored in paper envelopes on the same day.
Collecting of lichen Xanthoria parietina was from
trees throughout the 15 districts during the period of
three months: May, June and July. This period is
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characterized by hot and dry climatic conditions as
shown in Figure 4.
II.3. Sample preparation
For drying the samples we used the protocol
method developed by [33]. The samples were
washed with distilled water thrice to remove any
residue from the surface of the lichen. After that,
the samples were thoroughly dried in an oven at
60°C for 2 hours, removing any existing moisture.
They were ground with a ceramic mortar to obtain a
more or less homogeneous powder with a particle
size of less than 63µm. Powdered samples of lichen
were transferred into plastic bottles and irradiated at
the Nuclear Research Center of Algiers (CRNA) by
a source of cobalt (Co60) with a dose of 25Gy in
order to preserve them.
The treated samples and the IAEA-336 lichen
standard underwent the same treatment and were
placed in plastic capsules on a 4 μm-thick mylar
support.
II.4 XRF analysis device
The device used consists mainly of a PANalytical
X-ray tube delivering a voltage of 50 kV and a
current of up to 3.0 mA, which makes it possible to
define specific excitation conditions for an
optimized application, with a silver primary target
and a Peltier Silicon Detector (SDD) with a
resolution of 132.6 KeV for K_α-Mn-Xray
[Epsilon].
The deconvolution of the X spectra is carried out by
the Epsilon3 XL spectrometer software.
II.4.1. Measurement of concentrations of major
and trace elements
The measurements of the element concentrations of
major elements (Al, Cl,Fe, K,and P) and trace
elements (Br, Cr, Cu , Mn, Pb, Rb, Sr, V and Zn)
were carried out with the help of X-ray
fluorescence (XRF) with Peltier-based silicon drift
detectors (SDD), at 132.6 keV resolution for Kα-
Mn X-rays and X-ray tube excitation (PANalytical,
Ag primary target, 50 kV).
The characteristic X-rays are identified thanks to
the Epsilon 3XL software. The yields of
characteristic X-ray peaks (Kα-Al, Kα-P, Kα-Cl,
Kα-K, Kα-V, Kα-Cr, Kα-Mn, Kα-Fe, Kα-Cu, Kα-
Zn, Kα -Br, Kα-Rb, Kα-Sr, Lα-Pb) are measured
after the adjustment and the subtraction of the
background interference.
The concentrations of the elements were
determined with the use of the Omnian procedure
with several filters (Ti, Al-50, Al-200 and Ag, Cu
300) in triplicate of the Lichen samples. The
elements were analysed in an air environment with
the exception of aluminium which was done in a
helium atmosphere to reduce the absorption effects.
II.4.2. Quality Assurance and Quality Control
Procedures (QA/QC)
In our analysis procedure and for the QA/QC ratio
of the XRF technique, we used the Lichen epiphyte
biological matrix IAEA-336 as a standard
reference.
The objective is to assess the quality of the results
obtained. Statistical assessment was performed to
determine the performance of the analyses and the
significance of the results. Three statistical
parameters: Z-score, U-score and Relative Bias
(RB,%) are the most commonly used [34]. The
evaluation using U-score includes measurement
uncertainties and the uncertainty of the value found.
In this study, the following equations were used in
the calculations:
(1)
Where:
xLab, μLab, xRef and μRefare the results of
laboratory measurements, overall/combined
standard uncertainties, assigned values and standard
uncertainties, respectively.
(2)
Where the performance of the laboratory equipment
is deemed satisfactory if zscore≤ 2,questionable
for2•zscore• 3 and unsatisfactory for zscore≥ 3.
(3)
The evaluation of the quality of our work was
carried out through the results of the relative bias,
Z-score and U-score.
The comparison of our measured data with the
recommended value is shown in Table 2.
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Table 2. Concentrations (μg/g) of the 14 elements in the reference samples (Epiphytic lichen IAEA-336)
Element
Measured value
± s* (**)
Value
Certified
RB (%)
Z-score
U-score
Al
580,82±18.16 (5)
680±126.12(15)
-14.59
0.79
0.77
Cl
2026,85±11.89 (14)
1900±377.41(13)
6.68
0.34
0,34
Fe
407,71±1.91 (14)
430±35.02(35)
-5.18
0.64
0.64
K
1949,84±4.8 (14)
1840±172.57(24)
5.97
0,64
0.64
P
516,48±27.95 (12)
610±159.27(12)
-15.33
0.59
0.58
Br
11,89±0.21 (14)
12.9±1.74(18)
-7.86
0.58
0.58
Cr
1,09±0.19 (14)
1.06±0.15(22)
3.10
0.22
0.18
Cu
4,10±0.08 (7)
3.6±0.47(21)
13.89
1.06
1.05
Mn
60,31±0.37 (14)
63±5.42 (29)
-4.27
0.50
0.5
Pb
4,37±0.20 (6)
4.9±0.53(23)
-10.88
1.01
0.93
Rb
1,55±0.19 (13)
1.76±0.24(16)
-11.71
0.86
0.77
Sr
8,59±0.23 (14)
9.3±1.09(19)
-7.60
0.65
0.64
V
1,49±0.25 (10)
1.47±0.39 (8)
1.36
0.05
0.05
Zn
27,97±0.31 (5)
30.4±2.26(38)
-8.88
1.18
1.18
* s: Standard deviation (SD) ** (number of analysis test)
The results of the analyzed elements were in
agreement with the recommended value of lichen
epiphyte IAEA-336. The results of relative bias
(%), Z-score and U-score were satisfactory.
We discuss the results through the statistical
evaluation where the RB, Z-score and U-score are
accepted or rejected according to the previous
conditions. This evaluation shows excellent quality
of the results obtained in this study.
II.5. Mapping techniques
In our study, the Kriging modelling method [35, 36]
was used to trace the mapping of major and trace
elements in the Blida area and to highlight the
spatial distribution in the concentration of these
metals. They are averaged with ArcGIS 10.4.
software based on the Kriging method and carried
on location maps for each measured element.
III. Results and discussion
III.1. Anatomical structure of Xanthoria
parietina
In order to clarify how the structure of Xanthoria
parietina is made and to know how it accumulates
aerosols, we proceeded to do anatomical checking
using the Scanning Electron Microscope (SEM).
The presence of the foliose thallus with lobes and
rich in apothecia was noticed.
Figure 5. Cross-section of the lichen Xanthoria
parietina observed with the SEM QUANTA 650
FUNDAPL microscopes.
(a): Thallus and apothecium on the surface of
Xanthoria parietina (scale 1mm);
(b): Vertical section of apothecium of Xanthoria
parietina (scale 100 μm) :
①
Epithecium ,
②
Thecium (paraphyse + spores),
③
Medulla ,
④
Upper Layer
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Through the detailed SEM examination (Figure 5a),
we can observe the anatomy of the upper and lower
layers of the thallus and also the appearance of the
apothecia (Apothecium sing) (Apothecia and
thalli); the shape and the size of the asci, the spores,
the shape of the hyphae and their
compartmentalized arrangement (Figure 5b). It is
noted that the epithecium has a fissured structure on
which particles of telluric origin or airborne
particles can be deposited and which can, through
moisture or rain, enter the cavities of the thecium
and the remains in the thallus, and then pass into
the cavities of the medulla. The porous structure
makes it possible to trap soluble and even solid
particles that are in suspension in the atmosphere.
The lichen is different from the leaves of plants,
which are usually covered with a cuticle. It is
possible to distinguish the existence of solid
particles suspended in the atmosphere, clumped on
the surface of the thallus or in its cavities.
III.2. Distribution of major elements and trace
elements concentrations.
The average values of the concentrations obtained
for the major elements (Al, Cl, Fe, K and P) and the
trace elements (Br, Cr, Cu, Mn, Pb, Rb, Sr, V and
Zn) analyzed by the XRF technique are given,
respectively, in
Table 3 and Table 4 for the forty-two (42) sampling
sites picked in the 15 districts of Blida. The
maximum, minimum and the mean values are
reported.
Table 3. Concentration values of major elements (Al, Cl., Fe, K., P.) in μg/g in the lichen Xanthoria parietina in
Blida and its surroundings.
Sites
District
Al
Cl
Fe
K
P
B1
El-Afroun
5905
231
2397
2068
681
B28
El-Afroun
10977
243
4162
3567
794
B4
OuedAlleug
5324
380
2579
3837
984
B5
OuedAlleug
11644
233
5100
2877
607
B6
OuedAlleug
10145
319
4048
2658
697
B3
Benkhelil
8777
613
3672
2990
935
B24
BeniTamou
6718
287
3534
3126
853
B7
Mouzaia
12136
316
4594
2886
754
B8
Mouzaia
12318
563
4155
4188
897
B29
Mouzaia
8885
264
3244
3252
694
B30
Ain Romana
10989
271
3787
3822
1126
B9
Chiffa
10351
353
4556
3736
690
B26
Bouarfa
7353
437
3439
4049
768
B27
Blida
11868
296
4340
3159
712
B33
Blida
8915
226
3779
3786
762
B34
Blida
9772
162
4176
3634
827
B35
Blida
5685
315
2677
4437
815
B18
Guerrouaou
15616
227
5188
3022
581
B19
Boufarik
11807
317
4982
3236
741
B21
Boufarik
8900
416
2756
2528
615
B22
Boufarik
7942
398
2895
3120
771
B23
Boufarik
7870
415
3781
3259
798
B2
Boufarik
4351
701
2586
3795
1192
B25
Boufarik
10354
318
3808
2994
658
B17
Soumaa
12411
460
4422
3781
1486
B15
Bouinan
14514
228
5493
2902
692
B16
Bouinan
5795
556
2813
2874
885
B10
Chebli
10632
331
4843
3842
1017
B11
Chebli
5744
491
3556
3483
884
B12
Chebli
10356
256
4001
3136
1059
B13
Chebli
10883
389
5471
3008
751
B14
Chebli
9079
363
4742
3158
744
B20
Chebli
11288
324
4556
3123
658
B31
Chréa
10935
119
5225
2679
709
B32
Chréa
11440
198
4090
3385
647
1161

L.Kouadri et al
Copyright © 2019, Algerian Journal of Environmental Science and Technology, All rights reserved
B36
Chréa
9186
221
4053
2893
602
B37
Chréa
9716
299
3684
3672
720
B38
Chréa
9850
285
4193
3921
716
B39
Chréa
12399
217
4461
2984
519
B40
Chréa
9633
376
3710
3475
682
B41
Chréa
8177
236
2935
3567
714
B42
Chréa
11195
294
3526
2202
658
Min
4351
119
2397
2068
519
Mean
9710
332
3953
3288
788
Max
15616
701
5493
4437
1486
Table 4. Concentrations of trace elements (Br, Cr, Cu, Mn, Pb, Rb, Sr, V and Zn) in μg/g in the lichen Xanthoria
parietina in Blida and its surroundings
Station
Districts
Br
Cr
Cu
Mn
Pb
Rb
Sr
V
Zn
B1
El-Afroun
17
4
6
24
13
12
16
8
31
B28
Al-Afroun
32
8
28
47
25
33
87
14
57
B4
OuedAlleug
16
5
8
33
51
23
53
9
37
B5
OuedAlleug
49
9
18
76
244
43
103
13
63
B6
OuedAlleug
25
7
10
41
40
31
54
14
45
B2
Boufarik
22
5
10
34
88
13
28
8
53
B3
Benkhelil
57
6
13
43
52
29
51
13
56
B24
BeniTamou
11
6
10
46
26
14
46
10
289
B7
Mouzaia
31
8
11
58
61
33
45
15
49
B8
Mouzaia
22
7
80
56
55
31
30
14
91
B29
Mouzaia
17
6
30
47
24
31
41
12
42
B30
Ain Romana
43
7
10
48
64
40
43
14
49
B9
Chiffa
29
8
13
50
69
28
30
15
48
B26
Bouarfa
61
6
15
36
70
39
53
14
55
B27
Blida
34
8
16
54
74
29
43
15
64
B33
Blida
43
7
8
49
80
42
33
14
41
B34
Blida
29
7
8
51
30
35
32
15
41
B35
Blida
22
5
8
161
33
26
15
9
30
B18
Guerrouaou
34
10
13
59
82
46
59
18
78
B19
Boufarik
36
9
16
63
108
43
61
15
79
B21
Boufarik
20
5
21
32
32
21
39
10
416
B22
Boufarik
31
5
9
29
30
22
56
9
101
B23
Boufarik
35
9
31
52
228
30
74
10
90
B25
Boufarik
25
7
12
42
47
31
79
13
91
B17
Soumaa
21
9
11
44
65
48
51
16
57
B15
Bouinan
34
10
61
78
56
60
44
19
68
B16
Bouinan
12
5
20
39
27
24
41
9
152
B10
Chebli
29
9
10
50
34
31
42
16
60
B11
Chebli
19
6
10
42
21
16
32
12
51
B12
Chebli
22
7
8
55
23
27
40
14
53
B13
Chebli
32
9
18
65
47
38
101
16
64
B14
Chebli
16
9
10
76
75
31
73
15
48
B20
Chebli
33
8
11
54
60
34
41
16
56
B31
Chréa
29
8
8
140
21
44
32
17
33
B32
Chréa
33
7
8
50
24
37
32
15
45
B36
Chréa
44
7
7
55
40
35
30
14
32
B37
Chréa
31
6
7
47
20
32
26
12
51
B38
Chréa
38
8
8
59
29
33
34
14
55
B39
Chréa
39
8
12
81
32
35
40
17
255
B40
Chréa
45
6
7
65
35
39
25
13
34
B41
Chréa
31
5
6
51
16
31
18
9
26
1162

Algerian Journal of Environmental Science and Technology
December edition. Vol.5. No4. (2019)
ISSN : 2437-1114
www.aljest.org
ALJEST
Copyright © 2019, Algerian Journal of Environmental Science and Technology, All rights reserved
B42
Chréa
47
6
7
52
34
30
38
13
35
Min
11
4
6
24
13
12
15
8
26
Mean
31
7
15
56
54
32
46
13
76
Max
61
10
80
161
244
60
103
19
416
The distribution maps of major and trace elements
are shown in figure 6 to 19.
Figure 6. Geographical Distribution of the
Aluminium Concentrations
Figure 7.Geographical Distribution of Chlorine
Concentrations
Figure8.Geographical Distribution of Iron
Concentrations
Figure 9. Geographical Distribution of Potassium
Concentrations
Figure10 .Geographical Distribution of
Phosphorus Concentrations.
Figure11. Geographical Distribution of Bromine
Concentrations
1163

L.Kouadri et al
Copyright © 2019, Algerian Journal of Environmental Science and Technology, All rights reserved
Figure12.Geographical Distribution of Chromium
Concentrations
Figure 13.Geographical Distribution of Copper
Concentrations
Figure14.Geographical Distribution of Manganese
Concentrations
Figure 15.Geographical Distribution of Lead
Concentrations.
Figure 16.Geographical Distribution of Rubidium
Concentrations
Figure 17. Geographical Distribution of Strontium
Concentrations
Figure 18.Geographical Distribution of Vanadium
Concentrations
Figure 19. Geographical Distribution of Zinc
Concentrations
1164

Algerian Journal of Environmental Science and Technology
December edition. Vol.5. No4. (2019)
ISSN : 2437-1114
www.aljest.org
ALJEST
Copyright © 2019, Algerian Journal of Environmental Science and Technology, All rights reserved
Iron and Aluminum:
According to [37], the high concentration of iron
and aluminium in the lichen Xanthoria parietina
may be related to several local factors. The telluric
origin and the proximity of the wastes generated by
industrial activities are the most likely causes. In
addition, forest fires and roadtraffic [38,39] are
also an emission source of the iron, mainly from
transport exhaust fumes from diesel fuel vehicles.
Catalytic converters [29, 40, 41] are also registered
as important sources of iron emission. Building
materials can also affect iron concentrations in the
air [42].
Aluminium concentrations are the highest in all
districts, followed by iron concentrations. This is
most likely due to these elements’ origin from the
surrounding rocks and soil. The iron concentration
values accumulated by Xanthoria parietina are
between 2397 μg /g and 5493 μg /g with an average
value of 3953 μg/g. The aluminium concentration
values accumulated by Xanthoria parietina are
between 4351 μg/g and 15616 μg/g with an average
value of 9710 μg/g. According to [37], the high
concentration of iron and aluminium in lichen
Xanthoria parietina may be related to local factors.
The telluric origin and the proximity of the wastes
generated by the industrial activities are the most
likely causes concerning this study case.
Chlorine:
The chlorine concentrations accumulated by the
lichen Xanthoria parietina record values between
119 μg/g and 701μg/g with an average value of
332μg/g. The origin can be accounted for from the
species itself or from the sea. Xanthones derived
from lichexanthone and norlichexanthone are very
often chlorinated [43].
Potassium:
In our case, the concentration content of potassium
is in third position after that of aluminium and iron.
The potassium concentration values accumulated by
Xanthoria parietina ranges from 2068 μg/g and
4437μg/g with an average value of 3288 μg/g.
which is comparable to the background values for
potassium in lichens (500 to 5000 ppm), whereas
enriched levels in lichens are 5,000 to 9,500 ppm
[44]. This rate is explained by the proximity of the
sampling points of agricultural areas containing a
fertilization activity, and intense road traffic; as
well as the proximity of this region to the sea. [38,
39, 42] give forest fires and road traffic as the
emission sources.
Phosphorus:
The phosphorus concentration values accumulated
by Xanthoria parietina are between 519 μg/g and
1486 μg/g with an average value of 788μg/g. The
terrigenous aerosols and their use in agriculture and
industry constitute the main source [45].
Bromine:
The bromine concentration values accumulated by
lichen Xanthoria parietina are between 11μg/g and
61 μg/g with an average value of 31 μg/g. [46]
demonstrated that a bromoperoxidase is present in
this lichen. Purified enzymes from this lichen
contain vanadium, which is essential for its activity.
The elevation of bromine concentration can be
related to the use of pesticide.
Chromium:
[29]gives volcanic activities and aerosol as the
natural origin of chromium in the air, and the iron
and steel industries (glass, cement and paper), as
well as transport, agriculture, energy, and waste as
the anthropogenic sources. Chromium is often
higher in soils of ultramafic regions [47]. The
values for lichen are between 0 and 10 ppm [44].
Although, [44] indicate that improved levels of as
low as 4 ppm have been observed near industrial
areas. According to [26], an average chromium
concentration level is 7 (5-10) ppm, and may be
higher near urban/industrial areas with levels of 25
to 130 ppm.
Copper:
In our study, the copper concentration values
accumulated by lichen Xanthoria parietina are
between 6 μg/g and 80μg/g with an average value
of 15 μg/g.
The natural origin of copper in the air is possible
from terrigenous aerosols, marine, volcanic
activities, and also vegetation. Anthropogenic
activities which enhance those values are transport,
industry, metallurgy, waste, agriculture[29, 48, 49],
vehicular exhaust fumes, and wear of vehicles
brakes [40, 50, 51].
According to [44], the average copper concentration
is 20.5 (8-31) ppm and the values for lichens are 1
to 50 ppm. More ranges of 15 to 1100 ppm and
levels as low as 13.5 ppm can be observed in
bryophytes [52]. The high copper concentration is
due to the proximity of the sampling points to
industrial activity areas, which include the
metallurgical and chemical industries, to the
presence of CET, and to intense road traffic
releasing copper from the exhaust fumes of the
vehicles and the wearing of the vehicular brakes.
Manganese:
The manganese concentrations accumulated in the
lichen Xanthoria parietina samples are in the order
of 24 μg/g and 161 μg/g with an average of 56 μg/g.
The principal sources of manganese areterrigenous
aerosols, vegetation and forest fires [29]. However
non-natural sources are metallurgy, energy (coal),
exhaust fumes from gasoline-powered vehicles,
vehicle brake wear and road traffic [48, 40, 39, 53,
38]. Background values for lichens are between 10
1165

L.Kouadri et al
Copyright © 2019, Algerian Journal of Environmental Science and Technology, All rights reserved
to 130 ppm [26], which proves that our values are
within acceptable limits.
Lead:
The principal source of lead is due to industry,
metallurgy, intensity of road traffic, and waste and
energy processing[29, 54, 55].The lead
concentrations accumulated by lichen Xanthoria
parietina are between 13 μg/g and 244 μg/g with an
average value of 54 μg/g.
Rubidium:
The main known source of rubidium is waste
incineration[45]. The rubidium values registered in
this study are between 12 μg/g and 60 μg/g with an
average value of 32 μg/g. Our values are similar to
those recorded in Slovenia but higher than those in
Brazil.
Strontium:
[29]gives two sources of emission for this metal.
The natural source is from terrigenous aerosols and
the non natural sources are from the energy of oil,
fuel of vehicles, and coal as well as waste. In our
study, the strontium concentrations accumulated by
lichen Xanthoria parietina range between 15 μg/g
and 103 μg/g with an average value of 46 μg/g. The
average value in our findings is three times higher
than the values recorded in France.
Vanadium:
The origin of vanadium can be natural from
volcanic activities and also terrigenous and marine
aerosols. The non-natural sources are energy
processing and oil, transport, waste as well as
particular extraction of copper and zinc [29] and
from the exhaust fumes from diesel vehicles [48].
The Vanadium concentration values accumulated
by lichen Xanthoria parietina range from 8 μg/g and
19 μg/g with an average value of 13μg/g. The
vanadium is associated with the enzyme
bromoperoxidase in Xanthoria parietina[46].
Zinc:
The natural origin of zinc can be terrigenous
aerosols, volcanic activities, vegetation and forest
fires. And the non-natural sources are from the
metallurgical industry, energy (coal), wastes,
transport, and agriculture [29, 38], as well as
vehicular exhaust, and engine and tire wear [48, 50,
56, 57].
The zinc concentration values accumulated by
lichen Xanthoria parietina are between 26 μg/g and
416 μg/g with an average value of 76 μg/g.
III.3. Statistical analysis
III.3.1. Inter-element correlation
The study of inter-element linear correlations by the
use of the Pearson coefficient with a risk α = 0.01,
reveals two correlation groups. The first has
correlation coefficients that are higher than 0.3932,
more exactly corresponding to a ddl = 41, unlike
the second group, where they are lower than
0.3932. The values of correlation coefficients for
major and trace element respectively are shown in
Table 5 and Table 6.
Table 5. Inter-element correlation matrix for major elements (R)
Variables
Al
Cl
Fe
K
P
Al
1
-0,4211
0,8117
-0,1719
-0,2356
Cl
-0,4211
1
-0,3558
0,2320
0,4985
Fe
0,8117
-0,3558
1
-0,1027
-0,1828
K
-0,1719
0,2320
-0,1027
1
0,4502
P
-0,2356
0,4985
-0,1828
0,4502
1
A strong correlation is observed for the elements
Al-Fe (r = 0.8117), P-Cl (r =0.4985) and K-P(r
=0.4502). The presence of a linear correlation
between iron and aluminium is due to their sharing
the same origin of air enrichment, which can be
strongly related to the soil. The second correlation
between chlorine and phosphorus may be explained
by coastal upwellings containing chlorine[58].The
third correlation registered between phosphorus and
potassium is due probably to their addition to
agricultural soil and from industries
Table 6. Inter-element correlation matrix for trace elements (R).
Variables
Br
Cr
Cu
Mn
Pb
Rb
Sr
V
Zn
Br
1
0,2269
-0,0829
0,0490
0,3147
0,4975
0,1493
0,3482
-0,2444
Cr
0,2269
1
0,2569
0,2700
0,4525
0,7065
0,5171
0,8243
-0,1230
Cu
-0,0829
0,2569
1
0,0253
0,1869
0,2503
0,1396
0,1855
0,1317
Mn
0,0490
0,2700
0,0253
1
0,0472
0,3498
-0,0793
0,2775
-0,1451
Pb
0,3147
0,4525
0,1869
0,0472
1
0,2543
0,5415
0,0325
-0,0585
1166

Algerian Journal of Environmental Science and Technology
December edition. Vol.5. No4. (2019)
ISSN : 2437-1114
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ALJEST
Copyright © 2019, Algerian Journal of Environmental Science and Technology, All rights reserved
Rb
0,4975
0,7065
0,2503
0,3498
0,2543
1
0,2585
0,7712
-0,2618
Sr
0,1493
0,5171
0,1396
-0,0793
0,5415
0,2585
1
0,2180
0,0635
V
0,3482
0,8243
0,1855
0,2775
0,0325
0,7712
0,2180
1
-0,1571
Zn
-0,2444
-0,1230
0,1317
-0,1451
-0,0585
-0,2618
0,0635
-0,1571
1
Significantly, Pearson’s coefficient is shown
between the couples Cr-V (r=0.82), Cr-Rb (r=0.71)
and Cr-Sr (r=0.52), and remarkably, the strontium
is moderately linked with lead (r=0,54).
III.3.2. Statistical concentration analysis for
Blida area
The relationship dendrogram based on the major
elements is presented in Figure 20and constitutes of
the two main groups. The first group (GM1), which
includes B15 (Bouinan) and B18 (Guerouaou), is
characterized by the highest values in aluminium
and iron concentrations.
The second group (GM2) consists of two
subgroups:
The subgroup (GM2a), consisting of B1 (El-
Affroun), B2 (Boufarik), B3 (Benkhelil), B11
(Chebli), B16 (Bouinan), B24 (BeniTamou) and
B35 (Blida), is characterized by lower values in
aluminium and iron. The site B35 (Blida), situated
at only 8m from the road leading to the center of
Blida, is distinguished by the high concentration of
potassium compared to other sites of the subgroup.
On the contrary, the lowest concentrations of the
major elements are found in the western and
northern parts near B1 (El-Affroun). Other factors
such as the congested weekend traffic, the landfills,
and the frequent forest fires can be potential causes
of the increased potassium concentrations
The highest chlorine values are located in the north
of the study area at Benkhelil (B3) and Boufarik
(B2), and are explained by the proximity of the
sampling points to a chemical industrial plant.
These points are also located about fifteen
kilometres from the sea, increasing their chances of
chlorine exposure. The highest chlorine
concentration is recorded at the B26 (Bouarfa) site,
which is linked to its proximity to the East-West
Highway (about 8m) and an agricultural area. These
two elements are strongly correlated (R2 = 0.81).
The tendency in this occurrence is related to the
nature of the soil present in this area.
The subgroup (GM2b), consists of two populations.
The first has the points B31, B32, B39 and B42
(Chréa), B8 (Mouzaia), B17 (Soumaa), B9 (Chiffa),
B10, B13, B20 (Chebli), B30 (Ain Romana), B28
(El-Affroun), B5 (OuedAlleug), B19 (Boufarik),
B27 (Blida), and B7 (Mouzaia). It is also
characterized by high values of aluminium and iron
but a low concentration of chlorine. These areas are
probably less exposed to marine influence. The
increased concentration of potassium in B8
(Mouzaia) is due to the fact that it is located in the
middle of an agricultural area famous for its
intensive use of chemical fertilizers and its nearness
to forests and potential fires. The highest
phosphorus concentrations are in Soumaa (B17).
This explains the influence of local activities. The
B17 sampling point at Soumaa is in the middle of
agricultural fields and the high phosphorus
concentration could be due to fertilizers.
The second population consists on the one hand of
the sampling points B21, B23 (Boufarik), B26
(Bouarfa),and B41 (Chrea), all of which have
moderate values in the elements aluminium,
chlorine, iron and phosphorus. On the other hand,
the sampling stations consist of points at B12
(Chebli), B6 (OuedAlleug), B25 (Boufarik), which
have moderate levels in aluminium; and B37, B38
and B40 (Chréa), and B34 (Blida), which are rich in
iron, potassium and phosphorus, and B14 (Chebli),
B36 (Chréa), B33 (Blida), B29 (Mouzaia), and B3
(Benkhelif), which have moderate values in
aluminium and iron due to the nature of the
surrounding soil, but with a high cumulative
concentration of iron and potassium. The increased
concentrations of potassium and phosphorus in the
area are influenced by the agriculture activities and
the chlorine effect from the sea, which contributes
to the segregation of the two groups.
Figure20.Dendrogram relationships of districts
based on major elements in the districts of Blida
The dendrogram relationships based on the trace
elements is presented in Figure 21.
1167

L.Kouadri et al
Copyright © 2019, Algerian Journal of Environmental Science and Technology, All rights reserved
The first group (GT1), constituted by B21
(Boufarik), B24 (BeniTamou) and B39 (Chréa), and
is characterized by a high concentration in zinc.
This high concentration of zinc originates due to the
proximity of the sampling point located 300 m from
the road leading to the agglomerations, and 250 m
from the East-West Highway, which experiences
significant traffic. The concentration is also affected
by the existence of a metallurgical industry nearby
and emission released by the residual sector
(domestic heating) without neglecting the presence
of landfills and coinciding with the predominant
direction of the north-east wind. Those more
polluted sites are probably affected by local
emission.
The second group (GT2) constituted by two
subgroups:
The subgroup (GT2a): The lead with a high
concentration individualizes two sites; B5 (Oued
El-Alleug) and B23 (Boufarik). Those two most
polluted sites by lead also exhibit high values in
strontium. For the B23 site’s values, the situation
can be explained by the very large road traffic on
the East-West Highway and the soot discharged by
jet engines at the military airport, as well as the fuel
from vehicles coming from a station, in addition to
the metallurgical and chemical industries along the
highway south of the sampling site and coinciding
with the predominant direction of the north-east
wind.
For the B5 site, the high concentration of lead
seems to come from the traffic of the RN 4
Highway connecting the agglomerations to the west
(distance of 250 m), to the east (from 140 m), and
to the north (from 310 m), in addition to the two
service stations and the existence of an incinerator
south of this sampling point.
The subgroup (GT2b): B31 (Chrea) and B35
(Blida) in the high altitude part of Blida stand out
from the other subgroups bythe high level
concentrations of manganese, probably influenced
by forest fire. B16 (Bouinan) is also isolated from
the rest because of its elevated concentration of
zinc. Being near an industrial activity zone housing
chemical and metallic industries and an
uncontrolled landfill, B8 (Mouzaia) and B15
(Bouinan) are the two sites most affected by a high
concentration level of copper.
Figure21.Dendrogram relationships of districts
based on trace elements
The presence of high manganese concentrations
characterized B31 (Chréa) and B35 in the high
altitude part of Blida which are not so far from each
other and are probably affected by forest fires. B16
(Bouinan) is also isolated from the rest because of
its elevated concentration of zinc. B8 (Mouzaia)
and B15 (Bouinan) are the two sites most affected
by high levels of copper.
Strontium is found with the highest values at B13
(Chebli), B25 (Boufarik), B28 (El-Afroun) and it
can be attributed to car fuel, coal burning, and
waste mismanagement in these areas.
What remains is divided in two populations. The
first part constitutes sites with moderate values of
lead, with a concentration of more than 50 μg/g due
to the high traffic in the area and and probably more
waste. Related sites are B2, B19 (Boufarik), B3
(Benkhelil), B26 (Bouarfa), B17 (Soumaa), B27,
B33 (Blida), B9 (Chiffa), B30 (Ain Romana), B7
(Mouzaia), B20 (Chebli), B14 (Chebli), B18
(Gueroaou). Between them, B3 (Benkhelil) and
B26 (Bouarfa) are the two sites most affected by
bromine. The second part constitutes 15 sites: B1
(Al-Afroun), B4, B6 (OuedAlleug), B10, B11, B12
(Chebli), B29 (Mouzaia), B34 (Blida), B32, B36,
B37, B38, B40 B41, B42 (Chréa). They have the
lowest concentrations of lead, which do not exceed
50 μg/g. These are the areas least affected by trace
elements.
The sites B15 (Bouinan) and B18 (Gueroaou) have
the highest values in chromium, rubidium and
vanadium, like in location B39 (Chrea). These
elements are strongly correlated but do not show
formulation of the same group in the dendrogram,
which is dominated by high values’ isolation effect
of zinc, lead, manganese, and strontium.
1168

Algerian Journal of Environmental Science and Technology
December edition. Vol.5. No4. (2019)
ISSN : 2437-1114
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ALJEST
Copyright © 2019, Algerian Journal of Environmental Science and Technology, All rights reserved
III.4. Statistical concentration analysis for Chrea
natural Park
The average values, min, max and SD of
concentrations obtained for the major elements (Al,
Cl, Fe, K and P) and from trace elements (Al, P, Cl,
K, V, Cr, Mn, Fe, Cu, Zn, Br, Rb, Sr et Pb) are
given in Table 7 for the thirty-three (33) sites
sampled in the urban zones surrounding the Blida
district and the nine sites from the natural forest
areas, including the Chréa National Park, for
reference. The ANOVA One-Way technique was
applied for the two populations of urban and
reference zones for each analyzed element and it
indicates that Cl, P, Sr, are significant. The chlorine
ratio shows the proximity of urban sampled sites to
the sea. The phosphorus and strontium ratios are
probably influenced by the coal waste in this
urban area.
Table 7.Min, average, max, SD, and ANOVA One-way test on concentrations values of major elements (Al, Cl,
Fe, K and P) and trace elements (Al, P, Cl, K, V, Cr, Mn, Fe, Cu, Zn, Br, Rb, Sr et Pb) in μg/g obtained from the
lichen Xanthoria parietina in the urban districts of Blida compared with the forest area represented by the
Chréa National Park
Region
Al
Cl
Fe
K
P
Br
Cr
Cu
Mn
Pb
Rb
Sr
V
Zn
Blida (33 sites)
Min
4351
162
2397
2068
581
11
4
6
24
13
12
15
8
30
Average
9554,7
354,
5
3943,
4
3313,
1
822,
1
29,
1
7,
2
17,
1
52,
5
61,
6
31,
3
49,
6
13,
2
78,
9
Max
15616
701
5493
4437
1486
61
10
80
161
244
60
103
19
416
SD
2700
124
877
511
190
12
2
15
23
50
11
21
3
76
Median
10145
319
4001
3159
768
29
7
11
49
52
31
44
14
56
Chréa (9 Sites)
Min
8177
119
2935
2202
519
29
5
6
47
16
30
18
9
26
Average
10281,2
249,
4
3986,
3
3197,
6
663,
0
37,
4
6,
8
7,8
66,
7
27,
9
35,
1
30,
6
13,
8
62,
9
Max
12399
376
5225
3921
720
47
8
12
140
40
44
40
17
255
SD
1305,9
73,7
642,5
547,2
67,0
6,8
1,
1
1,7
29,
4
8,1
4,4
6,8
2,5
72,
7
Median
9850,0
236,
0
4053,
0
3385,
0
682,
0
38,
0
7,
0
7,0
55,
0
29,
0
35,
0
32,
0
14,
0
35,
0
Urban Sites/Natural sites
0,9
1,4
1,0
1,0
1,2
0,8
1,
1
2,2
0,8
2,2
0,9
1,6
1,0
1,3
ANOVA Test
NS
S
NS
NS
S
NS
N
S
NS
NS
NS
NS
S
NS
NS
NS: Non-significative S: Significative
The ratio for both copper (Cu) and lead (Pb) is
more than two (2). This difference of concentration
between the urban and the natural populations may
be explained by the negative shift between median
and average values in the urban area.
III.5. Comparison with other cases in the world
The average (min and max) concentrations of the
major and trace elements (Al, P, Cl, K, V, Cr, Mn,
Fe, Cu, Zn, Br, Rb, Sr and Pb) in μg/g obtained in
the lichen Xanthoria parietina in Blida compared to
other cases in the world is given in Table 8.
According to [5], there are no established standards
for trace element concentrations in lichens to
interpret the results. The values used to compare
results obtained in this study with reference values
defined from the works of the literature.
The comparison values max with other cases in
Algeria and elsewhere in the world is presented in
Table 8
1169

L.Kouadri et al
Copyright © 2019, Algerian Journal of Environmental Science and Technology, All rights reserved
●Chromium (Cr): The max value in Blida
(Algeria) is comparable to the max value of Val
Sambre (France), but it is 14x less than the max
value in Sétif (Algeria), 6x lower than the max
value of Romania, 117x less than the max value of
Dunkerque (France), and 120x less than the max
value of Northeast Morocco. The average value
and also max are not so far from the standard values
given in literature. However, this low relative value
is more than the value of Cr in Biel and Nabel
Switzerland.
●Manganese (Mn): Max value in Blida (Algeria)
is similar with the Setubal peninsula (Portugal), but
is 4x more than in Lille (France), 6x less than in
Kocaeli (Turkey), 10x less than in Luxembourg,
and 8x less than BordjBouArreridj (Algeria). The
average value in the forest area is relatively less
than what is measured in the urban sites in Blida
and its surrounding districts.
●Iron (Fe): Max value in Blida (Algeria) is 5x less
than Fos-sur-Mer (France) and Luxembourg, but
1.5x more than in Northeast Morocco, 2x more than
in Biel and Nabel (Switzerland), and 3x more than
in the Aegean (Turkey).
●Copper (Cu): the value max in Blida (Algeria) is
6x more than in Setif (Algeria), 3x more than in
Northeast Morocco, 2x more than in Biel and Nabel
(Switzerland), but 3x less than the registered max
values in the Setubal peninsula (Portugal), in Lille
(France), and 9x less than in Kocaeli (Turkey).
●Zinc (Zn): The max value in Blida (Algeria) is 2x
more than in Sétif and Algiers (Algeria), 3x more
than in Northeast Morocco, 3x more than in
Romania, 3x more than in Kosovo (Slovenia) and
4x more in the forest areas of France, 7x more than
in CollineMetallifere (Italy), 5x more than in
Singapore, 9x more than in Canada, 11x more than
in Greenland, 14x more than in Norilsk (Russia),
but 1.5 less than in Fos-sur-Mer (France), 6x less
than in Dunkerque (France) and 4x less than in
Lille (France).
●Lead (Pb): the max value concentration of lead in
Blida (Algeria) is 56x more than in Greenland, 42x
more than in Russia, 21x more than in
CollineMetallifere (Italy), 21x more than in
Canada, 7x more than in Veneto (Italy), 14x more
than in Singapore, 8x more than in the Setubal
peninsula (Portugal), 3-4x more than in Fos-sur-er
and the forest areas of France, 2x more than in
Romania, and 2x more than in Luxembourg. Max
values are similar to Tiaret(Algeria) and Kosovo.
However, Blida is 3.5x less than the critical cases
of Lille (France), Dunkerque (France), Morocco,
and 4x less than BordjBouArreridj (Algeria), 2x
less than Rabat (Morocco), 1.5x less than
Dunkerque (France),and than the Kocaeli province
(Turkey).
●Vanadium (V): The max value concentration in
Blida (Blida) is similar to the Kocaeliprovince
(Turkey) and 5x more than in Tuscany (Italy), 4-5x
less than DunkequeHarbore in France, 2x more
than in Val de Sambre in France
●Bromine (Br): The concentration registered in
Blida is 3x more than in São Paulo (Brazil) and
Slovenia.
●Rubidium (Rb): The max values found in Blida
(Algeria) are similar with those found in Slovenia
but 2x more than the max value registered in Sao
Paulo (Brazil).
●Stronsium (Sr): The max value concentration in
Blida (Algeria) is 2x more than in the forest areas
of France the unique value having been obtained in
the literature.
1170

Algerian Journal of Environmental Science and Technology
December edition. Vol.5. No4. (2019)
ISSN : 2437-1114
www.aljest.org
ALJEST
Copyright © 2019, Algerian Journal of Environmental Science and Technology, All rights reserved
Table 8. The average (min and max) concentrations of the major elements (Al, P, Cl, K, Fe) and trace elements
in μg/g obtained in the lichen Xanthoria parietinainBlida compared to other cases in the world
Country (region)
Al
Cl
Fe
K
P
Br
Cr
Cu
Mn
Pb
Rb
Sr
V
Zn
Refere
nces
Romania
(412-
6071)
(5,08-
64,47)
(2,66-
34,08)
(5-75)
(5-156)
[33]
Kosovo
8,67(9,
1-
282,1)
149,5(8-272)
[59]
Russia-Norilsk
1,26(0,
78-
5,79)
20,05(9,73-
29,6)
[60]
Italy (CollineMetallifere)
3,88(0,
68-
11,20)
25,9-57,7
[61]
Canada
(Barrenbdlands,Nunavut)
6,44(0,
76-
19,70)
22(15-44)
[62]
Greenland
1,72(0,
32-
4,29)
17,65(6,48-
36,9)
[63]
Italy (Vaneto)
7,66(0,
8-34,1)
33,56(20-99)
[27]
Singapore
11,86(2
,83-
16,59)
65,58(44,17-
83,16)
[64]
Italy (Tuscany)
2,235(0,
36-
10,70)
3,44(0,
9-
27,66)
1,13(0,32-
4,02)
30,15(5,5-80,5)
[65]
Turkey (Aegean)
1170(270
-18930)
3490(220-
13930)
25(8,8-
350)
4,2(0,2
8-170)
[42]
Turkey (Kocaeli-
Province)
1500(700
-5300)
3075(128
0-13550)
4550(2000-
6200)
15,9(7,
74-694)
90(40-
1022)
40(8,15
-394)
9,5(3-23)
166(64,8-1678)
[66]
France (forest areas)
1058,4(2
25,8-
3605,5)
616,1(12
7,6-
2226,50)
1,8(0,4-
6,1)
5,2(2,1-
12,4)
61,4(16
,8-
626,8)
3,1(0,7-
58,1)
15,2(2,9
-63,6)
2(0,4-6,8)
30,9(9,7-114,3)
[67]
France (Fos-sur-Mer)
3807(934
-12861)
7334(184
4-25399)
18(4-61)
21(9,3-
49)
221(47-
1019)
24(3,4-
75)
15(2,8-40)
178(36-625)
[68]
France (Dunkerque)
1504(349
-6681,7)
38,3(2,6
-1172,4)
19(5,1-
95,5)
556,9(4
5,4-
6305)
32,7(3-
371,9)
13,2(2,6-
102)
178,9(40,4-
2407,9)
[5]
France (Lille)
1092,9(2
21-
8745,7)
4,6(1-
45,1)
19,1(4,
7-
259,2)
54(16-
309)
31,1(1,
3-873)
3,6(0,3-18)
112,8(27,9-
1582,7)
[5]
France (Val de Sambre)
730,7(16
1-1933)
3,8(0,9-
11)
9,5(3,9-
22,1)
57,3(20
-165)
11,5(2,
4-55)
3(0,7-8,2)
74,4(23,3-
267,4)
[5]
Portugal (Setubal
peninsula)
2739,5(4
27,6-
8358,4)
3973,08(13
58,13-
6970,41)
107,09(2
,82-
345,99)
34,9(6,
9-
213,2)
50,7(22
,22-
174,15)
7,73(0,
83-
29,82)
132,58(23,83-
1045,14)
[69]
Slovenia
3878(2304-
6188)
10,92(4,
62-
22,35)
3,67(1,1
1-35,85)
16,54(3,
12-
57,10)
95,33(45,63-
182,52)
[70]
Brazil (São Paulo)
529-
1052
3195-5712
5,52-
19,89
9,2-27
31,9-765,5
[71]
France (Z.
PortaireDunkerque 2002)
41,05(1
,5-190)
14,98(1-79)
185,93(7,2-590)
[72]
France (Z.
PortaireDunkerque2009)
32,32(7
,3-110)
18,83(3,3-
110)
164,56(27-490)
[72]
Luxembourg
769-3258
1239-
27816
31-
1613
4-107
[73]
Switzerland (Biel and
Nabel)
387-696
1143-
1159
590-2208
3216-4908
1043-
3296
2,68-
8,22
9,67-
34,31
31-178
85-179
[74]
Morocco (Rabat – Salé)
29,3-
415,45
42,5-129,3
[75]
Morocco (Northeast)
479,976-
8422,018
21,589-
1242,32
6
4,065-
22,524
4,065-
42,05
22,027-218,994
[76]
Algeria (Algiers)
31,67-
254,06
60,97-260,87
[77]
Algeria (Tiaret)
76,31-
208,30
[78]
Algeria (SidiBelAbbès)
1,3 -
10,66
[79]
Algeria (Setif)
87,74(26
,4-
143,08)
2,9(0,6-
13,6)
91,7(38,98-
184,70)
[80]
Algeria(Tlemcen)
378.96-
1192,13
[81]
Algeria (Bordj Bou
Arreridj)
43184(70
00-
73000)
313(127,
9-472,1)
49,8(23
-87)
671,9(3
00 –
1300)
98,4 (6-
208)
476,6(323,9 –
983,5)
[82 ]
Algeria (Blida)This
study
9710(435
1-15616)
332,1(11
8,7-
701,3)
3953(239
7-5493)
3288(2068-
4437)
788(51
8,9-
1486)
30,94(11
,47-
61,22)
7,11(4,0
8-10,05)
15,05(5
,83-
79,86)
55,62(2
4,3-
161,3)
54,31(1
2,8-
243,51)
32,16(12
,02-
60,35)
45,53(15
,44-
103,40)
13,33(7,85-
19,29)
75,51(25,53-
415,91)
This
study
1171

L.Kouadri et al
Copyright © 2019, Algerian Journal of Environmental Science and Technology, All rights reserved
IV. CONCLUSION
This study is the first of its kind carried out in
Algeria in the Blida area, the second largest city
near the capital, with over a million inhabitants and
which has basic, natural and agricultural vocations.
For the biomonitoring of air quality, samples of the
lichen Xanthoria parietina were collected from trees
in 42 sites situated in Blida and its surrounding
districts. Five (5) major elements: Al, P, Cl, Fe, K.,
and nine (9) trace elements: V, Cr, Mn, Fe, Cu, Zn,
Br, Rb, Sr, Pb were analyzed by X-ray fluorescence
and have been validated.
The 42 prospected sites can be classified as below:
five (5) sites are affected by high level of Zn with a
concentration of more than 100μg/g, 200μg/g, and
400μg/g in various areas. Even the forest area is
affected, with more than 200 μg/g of Zn. Two other
sites are affected by high levels of copper with a
concentration of more than 60μg/g. Two other sites
have concentration values > 100μg/g in strontium
and three others are affected by both strontium and
lead. Two sites in the forest area are affected by
manganese, with a concentration level of more than
100μg/g. There are two (2) sites affected strongly
by a concentration of more than 200μg/g in lead,
and thirteen other sites that have lead concentration
levels exceeding 50 μg/g. Only fifteen (15) sites
have lower than 50μg/g concentration values of
lead. All prospected districts are actually affected
by at least of one or two element ratios at higher
than normal concentrations due to the effervescence
of industrial activities and the intensification of
traffic on roads. Poor waste disposal systems are, in
general, suspected of contributing factors, hence the
situation should be improved in the future if proper
waste collecting and incineration procedures are
adopted and generalized. Even the forest area,
including the Chréa National Park, is affected due
to recurring fires and high traffic frequency. This
situation requires more efforts and facilities to
manage the flux of visitors to the park throughout
the year.
Mapping elements shows that propagation is under
dominant wind influence. While chlorine is under
maritime influence, others elements are clearly
affected by local emission and require more
attention. The vocation should be respected because
only 43% of the industry is devoted to agriculture
and food transformation. New tendencies are
registered in other industrial fields. If not
controlled, the environmental quality will regress
under the effect of urbanisation and roads
intensification. Lichens constitute a nature-offered
sensor to enhance air quality. Obtained values of
heavy metals and trace elements should be
considered as a basic data and quantifying their
levels in soils and water remains an urgent matter.If
not controlled, the environmental quality will
regress under the effects of urbanisation and roads
intensification.
Lichens constitute a nature-offered sensor to
monitor air quality. Obtained values of heavy
metals and trace elements should be considered as a
first step in measuring our air quality; and
quantifying their levels in soils and water should
remain an urgent task because lichen are absent in
highly populated urban sites.
The use of Xanthoria parietina confirms moderate
air pollution. It will be interesting to explore sites
where these lichen despair, indicating extreme
degrees of environmental alteration, as well as the
impact of pollution emission on soil and in aquatic
ecosystems (rivers and irrigation systems). The
intensification of measurement sites and adoption
of new techniques are necessary to help
management programs. The urbanization plan, the
location of industrial zones, and the public landfills
must be reconsidered urgently to stop the regression
of the quality of the area.
The results of this study show that Blida and its
surroundings are experiencing increasingly strong
urbanization and industrialization. And even if the
district of Chréa is set apart because of the national
park headquarters, all other districts are not spared
the excessive use of fertilizers and pesticides.
Another major problem remains that of waste and
fire management. Also, the hypothesis that the park
of Chréa is a reference zone of weak human and
industrial activity is questioned, in particular for the
lead. Other elements such as aluminum and iron are
certainly related to the nature of the earth's
substrate. As for zinc and manganese, forest fires
are probably the main cause.
However, the practical value of biomonitoring lies
in the ease of its being realized quickly and cheaply
compared to a city or even to the scale of a region.
In suburban or industrial areas, where sensors are
lacking, as is the case in Blida, biomonitoring
remains an opportunity to measure atmospheric
pollution caused by major and trace elements. The
mapping of the 14 elements shows a general trend
that proves their displacement away from their
sources of emission. At the level of the districts
surveyed, and whatever their vocation, the sources
of emission are of various origins. Agricultural
activity is also not to be neglected. The industrial
network, the installation of equipment, and road
access are one part of the equation; and the
management of the waste generated both
industrially and domestically is another, and affects
almost all the townships. It is appropriate to review
the need to respect the communal vocations and
revise its industrial policy. The question becomes:
Should we continue to provide all districts with
zones of industrial activities without prescribing
rules and restrictions? It is imperative to relocate
polluting industries, monitor their emissions, and
eradicate landfills located on the edge of the
townships and close to agglomerations, to reduce
the risk of air pollution as well as that of surface
1172

Algerian Journal of Environmental Science and Technology
December edition. Vol.5. No4. (2019)
ISSN : 2437-1114
www.aljest.org
ALJEST
Copyright © 2019, Algerian Journal of Environmental Science and Technology, All rights reserved
water and groundwater, thus protecting water
resources, the health of the general population and
animals, and the sustainable state of ecosystems in
general.
Finally, it should be noted that this study concerns
only the points where Xanthoria parietina were
taken. There is no doubt that heavy metal
concentrations are higher in downtown Blida where
there are no more lichens that can withstand
pollution. The listing (of sampling sites codifying
the districts) is here as a proof of the need to direct
the environmental management towards the
classification of the districts prospected and to
widen the samples to the other non-prospected
districts.On the local level, we recommend,in order
to stop the ill-effects of urbanization, the
administrative borders of districts should be revised
to take into consideration the impact of pollution.
On a global level, the cosmopolitan nature of the
species makes it an indicator of economic pollution
worldwide compared to other aerosol collection
modes. The QC/QA procedure has shown that the
XRF technique is suitable for use ingeneral
pollution monitoring.
Acknowledgements
First and foremost, I would like to thank all
members of Fundamental and Applied Physics
laboratory (FUNDAPL) for their help and
encouragement.Special thanks to my husband for
his support as well as his valuable contribution in
the sample collection.I also place on record my
sense of gratitude to everyone and anyone who,
directly or indirectly, have lent their hand in this
venture.
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Copyright © 2019, Algerian Journal of Environmental Science and Technology, All rights reserved
Please cite this Article as:
Kouadri L., Benamar M.EA., Benkhalifa A., Evaluation by X-ray fluorescence (XRF) of major and trace
elements accumulated in Xanthoria parietina (L.) Th. Fr. (1860) indicating levels of pollution in Blida area
(Algeria), Algerian J. Env. Sc. Technology, 5:4 (2019) 1155-1176
1176