ASSESSMENT OF SEDIMENTS POLLUTION WITH HEAVY ELEMENTS USING GEO-ACCUMULATION INDEX (I-GEO) IN AL-CHIBAYISH MARSH , SOUTHERN OF IRAQ

Abstract

Sediments Samples from Al-Chibayish marsh were collected seasonally from four stations during August, 2017 to April,2018 , to determine the concentration of some heavy elements (Cadmium(Cd), Chromium(Cr), Nickel (Ni) and Lead(Pb)) in the exchangeable and residual phases of sediments .geo-accumulation Index (I-geo) was calculated as an indicator for sediments pollution with heavy elements , in addition to that the grain size and Total Organic Carbon (TOC) % were measured in the sediments samples. Results show that the concentrations of these elements in the exchangeable phase of sediments were (0.41 , 19.70 , 46.37, 25.20) µg/g-dry weight, respectively ,while in the residual phase were (0.27, 82.95 ,75.32, 14.41) µg/g-dry weight, respectively. According to Igeo values ,the sediments of Al-Chibayish marsh can be classified as unpolluted with Cd and Pb , while unpolluted to moderately polluted with Cr , and moderate to strongly polluted with Ni .In sediments grain size analysis show that the range of sand (1-24)% ,silt (59-86)% ,clay (7-25)% , while the range values of (TOC) were 9.93% to 13.49%.

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Hamid et al.,
ASSESSMENT OF SEDIMENTS POLLUTION WITH HEAVY ELEMENTS USING GEO-
ACCUMULATION INDEX (I-GEO) IN AL- CHIBAYISH MARSH , SOUTHERN OF IRAQ.
Rehab SalimKhazaal Al-Atbee ., MakiaM.Al-Hejuje & Hamid T.Al-Saad
Marine Chemistry Department - Marine Scince Center – University of Basrah ,Basrah , Iraq.
Ecology Department –College of Science – University of Basrah ,Basrah , Iraq.
College of Marine Scince – University of Basrah ,Basrah , Iraq.
ABSTRACT
Sediments Samples from Al- Chibayish marsh were collected seasonally from four stations
during August, 2017 to April,2018 , to determine the concentration of some heavy
elements (Cadmium(Cd), Chromium(Cr), Nickel (Ni) and Lead(Pb) ) in the exchangeable
and residual phases of sediments .geo-accumulation Index (I-geo) was calculated as an
indicator for sediments pollution with heavy elements , in addition to that the grain size
and Total Organic Carbon (TOC) % were measured in the sediments samples. Results
show that the concentrations of these elements in the exchangeable phase of sediments
were (0.41 , 19.70 , 46.37, 25.20) µg/g-dry weight, respectively ,while in the residual phase
were (0.27, 82.95 ,75.32, 14.41) µg/g-dry weight, respectively . According to Igeo values
,the sediments of Al- Chibayish marsh can be classified as unpolluted with Cd and Pb ,
while unpolluted to moderately polluted with Cr , and moderate to strongly polluted with
Ni .In sediments grain size analysis show that the range of sand (1-24)% ,silt (59-86)% ,clay
(7-25)% , while the range values of (TOC) were 9.93% to 13.49%.
Keyword: sediment ,heavy metals, pollution, AL-Chibayishmarshes,Iraq
No: of Figures : 1 No: of Tables: 5 No: of References: 34

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INTRODUCTION
The southern Iraqi marshes , freshwater wetland is unique ecosystem .Marshes are
frequently or consistently overflowed wetlands characterized by emergent herbaceous
vegetation adjusted to immersed soil condition, changing water streams, and mineral
soil,they cover an area about 15000-20000 km2 (Bedairet al.,2006 ;USEPA, 2008).
Iraqi southern marshes form large triangular region restricted by three major southern
cities: Thi-Qar to the west, Maysan to the northeast and Basrah to the south. They are vast
open zone that includes both permanent and seasonal marshes (Al-Ansari and Knutsson,
2011).
The central marshes are the heart of Iraq's southern marshes, are located at the top of the
concourse of the Tigris and Euphrates rivers. The Central Marshes cover an area of 3,000
km2 and can expand to 4,000 km 2 during the flood season (UNEP, 2006).
In natural system, marshes sediment accumulate types of chemicals that enter the water
through natural and anthropogenic activities (Mitsch and Gosselink, 2007;Lu et al., 2011).
Marshes system can act as a sink of chemicals either through sedimentation or bio-
concentration.The most important and harmful pollutants of the aquatic environment
heavy elements that affect the water with its dissolved phase, particulate, organisms and
sediments (Al-Saadet al, 2009).
Heavy elements which have specific gravity more than 5g/ cm3 and have negative
effects on the environment when over-utilizes and also influence the health of humans,
animals and plants .These compounds are often called trace elements because of they
are present in low concentrations in the earth's crust up to 0.1%(Minkoff and Baker, 2001).
In sediments, there are six different geochemical types of elements associated with
sediments. In the first one, these elements are connected with the sediment in the most
labile obtained mode; these are known as exchangeable elements. The second form
extracts are joint mainly with carbonates and are highly sensitive to pH variations. In the
third, the elements attached to Mn oxide and partly amorphous Fe oxide and in the
fourth type, to amorphous and poorly crystalline Fe oxide. In the fifth, the elements
associated with the organic matter and sulfides are released. Finally, the residual portion,
a fraction of elementsare strongly united to the lithogenic minerals of the sediments (
Hassan ,2007 ; Al-Haidarey, 2009; Al-Hejuje,2014).Sediments have a high level of
accumulation and retention of elements and pollutants, however sediments may
become a source of water contamination when their surfaces are saturated with heavy
elements. This effect is most distinct at high temperatures, speed water flow and small
sediment particles ( Hassan et al., 2010(
Measuring the concentration of heavy elements in sediments gives a clear perception
of the level of contaminations in the aquatic environment ,these elements bound to
particulate materials, which finally settle down to the sediments (Laluraj and Nair, 2006).

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Hamid et al.,
The present study aimed to determined the pollutants levels including the accumulation
of some heavy elements (Cadmium , Chromium , Nickel and Lead ) in sediments of Al-
Chibayish marsh as well as to estimate the organic matter and texture of sediments.
Material and Methods :
Study area :
Central marshes (Al- Chibayish ) is bordered to the north by the Amara road, the Tigris
River to the east, the Gharaf river to the west and the Chibayish road adjacent to the
Euphrates River in the south. Hor al-Chibayish is one of the most famous of the central
marshes. Hor al-Chibayishis located north of the Euphrates and in the middle of the
central marshes, before the drying, it was supplied with water from the Tigris but after the
rehabilitation in 2003, it became supplied from the Euphrates river (UNEP,2002;
Hussain,2014).
Four stations were selected at Central marshes (Al- Chibayish), sampling points were geo-
located using geographical positioning system (GPS) at the following coordinates: 31˚ 00-
34.7= N and 47˚ 01- 50.3= E (station 1); 31˚ 01- 57.5= N and 47˚ 02- 7.7= E (station 2); N 31˚
02- 58.4= and 47˚ 00- 57= E (station 3); 31˚ 04- 32.4= N and 47˚ 00- 58.5= E (station 4) .
Sediments samples :
Sediments samples were taken seasonally from four station inAl-Chibayishmarsh using
a van veen grab sampler, the water was allowed to drain off, using polyethylene bags
for the samples preserved, then the samples were placed in an ice box until reaching the
lab.
The sediments samples were dried in an oven at 50 °C for approximately 3 days , grind
finely using an electrical mortar and sieved through a 63 µm mesh sieve ,and stored in
polyethylene bags until analysis.
Total Organic Carbon (TOC %(
Amount of total organic Carbon in sediments were measured according to burning
method (Ball,1964).taking 2 gm of dried and sieved sediments were placed in pre-
weighted crucible and burned at 550ᵒC for period 48hrs.then placed in desiccators and
weighted more than one to reach constant weight, The difference in mass of crucible
and sediments sample before and after burning was calculated as TOC.
Grain size analysis(%)
Mean grain size analysis was carried out using 20 g of dried sediments ,and using the
pipette method for silt and clay grains and standard sieves (63µm pore size )for sand
grains then the triangle texture had been applied to determine the percentage of
particles in sediments, these techniques according to Folk (1974) .
Extraction the exchangeable elements from sediments:
From the fraction of the grinded and sieved sediments, put (1 g) in 50 ml polyethylene
tube. The exchangeable heavy metals were extracted by added 30 ml HCl(0.5N) for

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Hamid et al.,
over night in an orbital shaker with 300 rpm ,then the solution was centrifuged at 5000
rpm for 20 minute, thesupernatant was filtered using filter paper (Watman No. 1). The
filtrate was stored in tightly stopper polyethylene vials to be ready for analysis using
Atomic Absorption spectrophotometer (AAS). (Chester and Voutsinou, 1981).
Extraction the residual elements fromsediments :
The residue from the above mentioned steps was washed by 40 ml deionized water, then
centrifuge for 20 minutes to remove the residual of the exchangeable phase. Then
samples were digested with 5 ml concentrated HNO3 acid in Polyethylene Tri Fluro
Ethane(PTFE) beaker at 70ᵒ C on hot plate near dryness state. The digestion was further
proceeded with 1:1 mixture of concentrated HClO4and HF acids , digested near dryness
state . The residue was dissolved in 30 ml of 0.5NHCl, put on hot plate at 70ᵒ C and then
made up to 30 ml with deionized water ,filtered by filter paper (Watman No. 1). The
samples were stored in tightly stopper polyethylene vials to be ready for analysis using AAS
(Sturgen, et al. 1982).
Geoaccumulation Index ( I - geo)
The geo accumulation index (Igeo) ,as introduced by Müller (1969) to assessment the
pollution in sediments,as follows:
I-geo = log 2(Cn / 1.5 Bn(
Where:
Cn : the element concentration ( n) which measured in the sediments.
Bn :is the background concentration to the element ( n(
Table (1) : The classification of sediments pollution according to I-geo values
I-geo
Pollution Sediments Case
≤ 0
unpolluted
0 ≤Igeo≤ 1
unpolluted to moderately
1 ≤Igeo≤ 2
moderately polluted
2 ≤Igeo≤ 3
moderately polluted to polluted
3 ≤Igeo≤ 4
strongly polluted
4 ≤Igeo≤ 5
strongly to extremely polluted
Igeo≥ 5
extremely polluted
Statistical Analysis:
Analysis Of Variance (One –Way ANOVA) was applied by minitabver 16.1 software to
identify the existence of spatial and temporal significant differences The relationship
between the parameters and indices was tested using the Parsons correlation coefficients
.
Results and Dissection :
Sediments consider as the final recipient of pollutants from natural and anthropogenic
origin in aquatic environments (Hassan et al.,2010). Thus, theyare represent as a good
bio-indicator for aquatic environment pollution. Also, the accumulation of elements in the

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Hamid et al.,
sediment that result of long term exposure ,while the concentration of element in the
water as dissolved is mainly result of recent contamination (Brankovicet al. ,2011).
A major part of the heavy elements, which enter the aquatic environment eventually
settle down in the sediment, therefore the sediment act as archives for many pollutants
such as heavy elements (Al-Khafaji ,2010). The high concentrations in sediments than in
water is due to the strong binding affinity of heavy elements to the sediments (Al-Hejuje
,2014).
Table ( 2 )the concentrations of heavy elements in both the exchangeable and residual phases
of sediments
Stations
Heavy
elements
Exchangeablephase
Residual phase
Total
Station 1
Cd
0.464±0.137
0.257±0.149
0.721
Cr
19.558±9.165
97.67±25.92
117.226
Ni
61.96±17.30
85.97±18.79
147.927
Pb
26.460±3.447
14.783± 3.556
41.243
Station 2
Cd
0.351±0.152
0.284±0.169
0.635
Cr
11.554±5.755
67.76±19.65
79.312
Ni
26.42±11.90
65.80±14.77
92.222
Pb
24.008±4.364
13.539±4.068
37.547
Station 3
Cd
0.401±0.168
0.250±0.150
0.651
Cr
30.400±11.231
91.06±25.77
121.458
Ni
58.25±16.42
79.71±15.89
137.963
Pb
24.674±3.745
15.267±4.052
34.941
Station 4
Cd
0.434±0.065
0.310±0.197
0.743
Cr
17.283±9.847
75.32±25.16
92.608
Ni
38.86±20.37
69.82±17.78
108.679
Pb
25.678±1.450
14.053±4.501
39.735
The concentrations of cadmium in the exchangeable phase was ranged from (0.351μg/g
dry weight) at station 2 to (0.464μg/g dry weight) at station 1. Non-significant differences
(P>0.05) were found among stations. In the residual phase of sediments it's ranged from
(0.250 μg/g d. w) at station 3 to (0.3106μg/g d. w) at station 4.Also,non-significant
differences (P>0.05) were found among stations (Table2).
In sediments ,the concentrations of chromium in the exchangeable phase ranged from (
11.554µg/g d. w) at station 2 to (30.400µg/g d. w) at station 3. Significant differences
(P<0.01) were found among stations. The concentrations of chromium in the residual
phase of sediments ranged from (67.76 µg/g d. w) at station 2 to (97.67 µg/g dry weight)
at station 1, significant differences (P<0.05) were found among stations (Table 2) .
In sediments, the concentrations of nickel in the exchangeable phase ranged from
(26.42μg/g d. w) at station 2 to (61.96μg/g d. w) at station 1. Significant differences
(P<0.01) were found among stations. The concentrations of nickel in the residual phase of
sediments was ranged from (65.80μg/g dry weight) at station 2 to (85.97μg/g dry weight)
at station 1. Significant differences (P<0.05) were found among stations (Table 2 ) .
The concentrations of lead in the exchangeable phase of sediments ranged from
(24.008μg/g dry weight) at station 2 to (26.460μg/g dry weight) at station 1. Non-
significant differences (P>0.05) were found among stations. The concentrations of lead in
the residual phase of sediments ranged from (13.539μg/g dry weight) at station 2 to
(15.267μg/g dry weight) at station 3. Non-significant differences (P>0.05) were found
among stations.

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The results shown that the concentrations of Cd and Pb in the exchangeable phase of
sediments were higher than those in the residual phase of sediments(Table2),this finding
could be a good evidence that there is an anthropogenic origin of pollutants which
incorporated into the sediment from water column by processes such as adsorption ,
organic complication and precipitation to sediments, this finding was in agreement with
(Habeeb , 2015). Significant correlations between heavy elements in the sediments (Table
3) suggested that they had the same geochemical origin or behaviors (Song et al. , 2010 ;
Manojet al. , 2012).
Most heavy element in sediment positively correlated with clay particles and negatively
correlation with the sand (Table 3) , this could be attributed to the sediment particles size
which play an important role in the concentration and distribution of heavy element .
Small particle size which have a large surface area ,such as clay and silt has an ability to
accumulate higher concentration of heavy element because of these particles allowed
to adsorption of element into their surface (Bentivegnaet al. ,2004) .
Moreover, high concentrations of heavy elements in sediment may be due to the
increasing plant abundant at these stations in marshes which played an important role
to increasing the heavy elements in the sediments(Al-Atbee,2018 unpublished data ).
Plants work to reduce flow rate of water and this leads to deposit of suspended matter
,which containing high concentrations of heavy elements, to the sediments, this finding
was in agreement with Mashkool (2012).
Table ( 3 ): The Perasons correlation coefficients between total heavy metals in sediments
and the related environmental variable measured in Al-Chibayish marsh .
Variables
Cd
Cr
Ni
Pb
Cd
1
Cr
0.66 **
1
Ni
0.33 **
0.78 **
1
Pb
0.88 **
0.70 **
0.37 NS
1
Sand %
-0.05 NS
-0.24 NS
-0.49 NS
-0.15 NS
Silt %
-0.09 NS
-0.05 NS
0.21 NS
-0.07 NS
Clay %
0.22 NS
0.40 NS
0.34 NS
0.32 NS
TOC %
0.09 NS
0.14 NS
0.16 NS
-0.04 NS
** : Significant correlation at P<0.01 ; NS: Non- Significant correlation(P>0.05)
The terms clay, silt , and sand represents the soil particles( Balasim, 2013).The grain size of
Al-Chibayish marsh different in their percentage from station to another according to the
geological origin and the effluent dischargesat each station . Generally, according to the
texture compounds percentage (Fig 1), the sediments of Al-Chibayish marsh can be
considered as silt-clay sediments .

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Fig (1) Grain size (%)in the sediments of the studied area
In sediments,the wastes of human and animal play an important role to increasing the
content of organic carbon(Al-Hejuje,2014 ). The chemical and biological processes that
take place in sediment greatly affect the proportion of organic carbon ( Balasim , 2013).
The highest values which recorded during winter (Table 4 ) related to high precipitation
ratio of dead aquatic plants during winter, while the lowest values during summer at some
stations may be due to the rise of temperature which stimulate microbial enzymes
activities , therefore the biodegradation processes generally increases with the increasing
temperature (Foghtet al ., 1996) . TOC values showed negative significant correlation
with water temperatures (r=- 0.627,p<0.01) .Result of the present study were in agreement
with (Al-Abadi ,2011;Maskhool,2012).

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Table(4) Total Organic Carbon (TOC %) during the studied period in the studied area
sediments
Stations
Season
TOC %
(Mean ± SD)
Station 1
Summer
10.58 ±0.23
Autumn
11.84 ±0.47
Winter
12.68 ± 1.21
Spring
12.26 ± 0.16
Station 2
Summer
9.93 ± 1.43
Autumn
10.32 ± 0.20
Winter
12.62 ± 0.12
Spring
11.61 ± 0.17
Station 3
Summer
10.26 ± 0.64
Autumn
10.06 ± 0.32
Winter
11.14 ± 1.39
Spring
11.43 ± 1.51
Station 4
Summer
11.49 ± 4.99
Autumn
11.65 ± 0.22
Winter
13.49 ± 0.16
Spring
13.18 ±1.37
The Geo-accumulation Index ( I geo) :
The I-geo values can be used effectively to determining the extent of heavy element
accumulation in sediments .The I-geo grades for the surface sediments in the present
study differ from element to element and from station to station . According the I-geo
values the sediments at all the studied stations were considered as unpolluted with Cd
and Pb ,but unpolluted to moderately polluted with Cr , and moderate to moderat-
strongly polluted with Ni .This could be due to the high concentrations of these elements
in surface sediments that exceeded the world surface rock average according to
CBSQG(2003) values .The present result was in agreement with Al-Sabah and Aldhahi
(2017)who found that the sediments of Auda marsh was unpolluted with Zn , Fe, Cu and
Pb ,While disagreement with Al-Haidareyet al.,2010 found that the sediments of Al-
Hawizeh Marshes were suffering from moderately to strongly contaminate with the As
,Cd, Cr, Co ,Cu and Pb according to I-geo values. The different in results may be due to
the different in the studied areas characteristics and different the studies periods.
The values of I-geo in sediments for cadmium ranged from (-4.09, unpolluted) at station 3
in Spring to(-0.61 , unpolluted ) at station 4 in Winter (Table5) . Non- significant differences

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(P>0.05) were found among stations .While significant differences (P<0.01) were found
among seasons, the lowest mean value (-2.87 unpolluted ) was found in Spring , but the
highest mean value (-0.90unpolluted) was found in Winter .
The values of I-geo in sediments for chromium ranged from ( -0.44 , unpolluted) at
station 2 in Spring to( 1.29 , moderately polluted ) at station 3 in Winter (Table5) .
Significant differences (P<0.01) were found among seasons , thelowest mean value( 0.02
unpolluted to moderately ) was found in spring , but the highest mean value(1.07
moderately polluted) was found in Winter .Also significant differences (P<0.01) were found
among stations, the lowest mean value( 0.25 unpolluted to moderately ) was found at
station 2 , but the highest mean value(0.86 moderately polluted) was found at station 3.
The values of I-geo in sediments for nickel ranged from ( 1.00 , moderately polluted) at
station 4 in autumn to( 2.22 , moderate to strongly polluted) at station 1 in winter (Table5) .
Significant differences (P<0.05) were found among seasons , the lowest mean value( 1.55
t moderately polluted ) was found in autumn, but the highest mean value(1.97
moderately polluted) was found in winter .Also significant differences (P<0.01) were found
among stations, the lowest mean value( 1.41 moderately polluted ) was found at station 2
, but the highest mean value(2.1 moderate to strongly polluted) was found at station 1.
The values of I-geo in sediments for lead ranged from ( -1.07 , unpolluted) at station 2 in
spring to( -0.20 , unpolluted) at station 1 in autumn (Table5) . Significant differences
(P<0.01) were found among seasons , the lowest mean value( -0.91 unpolluted ) was
found in spring, but the highest mean value(-0.29 unpolluted) was found in winter .Non-
significant differences (P>0.05) were found among stations.
Table( 5 ):The I-geo values and descriptions the status of sediments pollution at the studied
stations during periods of the study.
Statio
ns
Season
I-geo Cd
value
Descriptions
I-geo Cr
value
Descriptions
I-geo Ni
value
Descriptions
I-geo Pb
value
Descriptions
Statio
n 1
Summer
-1.06
unpolluted
0.72
U-MPolluted
2.17
M –S polluted
-0.48
unpolluted
Autumn
-0.77
unpolluted
0.85
U-MPolluted
2.00
M –S polluted
-0.20
unpolluted
Winter
-0.89
unpolluted
1,27
Moderately
2.22
M –S polluted
-0.28
unpolluted
Spring
-2.06
unpolluted
0.21
U-MPolluted
1.93
Moderately
-0.79
unpolluted
Statio
n 2
Summer
-1.09
unpolluted
0.32
U-MPolluted
1.45
Moderately
-0.69
unpolluted
Autumn
-0.92
unpolluted
0.17
U-MPolluted
1.31
Moderately
-0.32
unpolluted
Winter
-1.08
unpolluted
0.72
U-MPolluted
1.62
Moderately
-0.30
unpolluted
Spring
-3.28
unpolluted
-0.44
Unpolluted
1.18
Moderately
-1.07
unpolluted
Statio
n 3
Summer
-0.86
unpolluted
1.00
Moderately
2.10
M –S polluted
-0.42
unpolluted
Autumn
-0.99
unpolluted
0.81
U-MPolluted
1.89
Moderately
-0.22
unpolluted
Winter
-1.02
unpolluted
1.29
Moderately
2.17
M –S polluted
-0.35
unpolluted

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Spring
-4.09
unpolluted
0.08
U-MPolluted
1.70
Moderately
-1.06
unpolluted
Statio
n 4
Summer
-0.77
unpolluted
0.73
U-MPolluted
1.82
Moderately
-0.46
unpolluted
Autumn
-1.21
unpolluted
-0.21
Unpolluted
1.00
Moderately
-0.46
unpolluted
Winter
-0.61
unpolluted
0.98
U-MPolluted
1.87
Moderately
-0.25
unpolluted
Spring
-2.09
unpolluted
0.21
U-MPolluted
1.82
Moderately
-0.71
unpolluted
U-M :unpolluted –moderately
M-S :moderate – strongly polluted
Conclusion :
Sediment pollution in the present study was assessed using geoaccumulation index
(Igeo).According to Igeo values, the surface sedimentsof Al-Chibayish marsh can be
classified as unpolluted with Cd and Pb , while unpolluted to moderately polluted with Cr
, and moderate to moderate- strongly polluted with Ni .
The results shown that the concentrations of Cd and Pb in the exchangeable phase of
sediments were higher than those in the residual phase of sediments .According to the
texture compounds percentage , the sediments of Al-Chibayish marsh can be
considered as silt-clay sediments .
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