Environmental Assessment ofAl-Hammar Marsh, SouthernIraq
Environmental Assessment ofAl-Hammar Marsh, SouthernIraq
Environmental Assessment ofAl-Hammar Marsh, SouthernIraq
29 September 2016
Revised:
Environmental assessment of
27 January 2017
Accepted:
16 February 2017
Al-Hammar Marsh, Southern
Heliyon 3 (2017) e00256 Iraq
Hind Fadhil Abdullah Al-Gburi * , Balsam Salim Al-Tawash, Hadi Salim Al-Lafta
Department of Geology, College of Science, University of Baghdad, Baghdad, Iraq
* Corresponding author.
E-mail address: hind_fadhil84@yahoo.com (H.F.A. Al-Gburi).
Abstract
Aim: (a) To determine the spatial distributions and levels of major and minor
elements, as well as heavy metals, in water, sediment, and biota (plant and fish) in
Al-Hammar Marsh, southern Iraq, and ultimately to supply more comprehensive
information for policy-makers to manage the contaminants input into the marsh so
that their concentrations do not reach toxic levels. (b) to characterize the seasonal
changes in the marsh surface water quality. (c) to address the potential
environmental risk of these elements by comparison with the historical levels
and global quality guidelines (i.e., World Health Organization (WHO) standard
limits). (d) to define the sources of these elements (i.e., natural and/or
anthropogenic) using combined multivariate statistical techniques such as
Principal Component Analysis (PCA) and Agglomerative Hierarchical Cluster
Analysis (AHCA) along with pollution analysis (i.e., enrichment factor analysis)
Methods: Water, sediment, plant, and fish samples were collected from the marsh,
and analyzed for major and minor ions, as well as heavy metals, and then compared
to historical levels and global quality guidelines (WHO guidelines). Then,
multivariate statistical techniques, such as PCA and AHCA, were used to
determine the element sourcing.
Results: Water analyses revealed unacceptable values for almost all physio-
chemical and biological properties, according to WHO standard limits for drinking
water. Almost all major ions and heavy metal concentrations in water showed a
distinct decreasing trend at the marsh outlet station compared to other stations. In
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general, major and minor ions, as well as heavy metals exhibit higher
concentrations in winter than in summer. Sediment analyses using multivariate
statistical techniques revealed that Mg, Fe, S, P, V, Zn, As, Se, Mo, Co, Ni, Cu, Sr,
Br, Cd, Ca, N, Mn, Cr, and Pb were derived from anthropogenic sources, while Al,
Si, Ti, K, and Zr were primarily derived from natural sources. Enrichment factor
analysis gave results compatible with multivariate statistical techniques findings.
Analysis of heavy metals in plant samples revealed that there is no pollution in
plants in Al-Hammar Marsh. However, the concentrations of heavy metals in fish
samples showed that all samples were contaminated by Pb, Mn, and Ni, while
some samples were contaminated by Pb, Mn, and Ni.
Discussion and conclusions: Decreasing of Tigris and Euphrates discharges
during the past decades due to drought conditions and upstream damming, as well
as the increasing stress of wastewater effluents from anthropogenic activities, led
to degradation of the downstream Al-Hammar Marsh water quality in terms of
physical, chemical, and biological properties. As such properties were found to
consistently exceed the historical and global quality objectives. However, element
concentration decreasing trend at the marsh outlet station compared to other
stations indicate that the marsh plays an important role as a natural filtration and
bioremediation system. Higher element concentrations in winter were due to runoff
from the washing of the surrounding Sabkha during flooding by winter rainstorms.
Finally, the high concentrations of heavy metals in fish samples can be attributed to
bioaccumulation and biomagnification processes.
1. Introduction
Wetlands are among the most productive ecosystems on Earth [1], and provide
many important services to human society [2]. A rare aquatic landscape in a desert
milieu, the Mesopotamian marshlands (hereafter “the Marshes”) is home to ancient
communities rooted in the dawn of human history [3]. These marshes were once
the largest wetlands in Southwest Asia and covered more than 15,000 km2 [4].
Originally covering considerable parts of the Mesopotamian Plain, which
developed along the Euphrates and Tigris Rivers [5], Iraqi marshes are important
as they have economic, social, and biodiversity value. They support coastal
fisheries, which endows them with a truly global dimension, and they represent a
permanent habitat for many unique species of plants, fish, invertebrate, and birds,
and a flyway for millions of birds migrating between Siberia and Africa [6]. The
Marshes and their inhabitants have witnessed three wars and were subjected to
drying operations from the early 1980s, involving massive drainage works and
upstream damming, and as a result were almost totally dry by 1991 [7, 8]. These
drying operations have resulted in drastic changes in the marshes environment,
which are still suffered today (e.g., creeping of the sand dunes towards ex-marsh
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areas, dryness of the land, increasing of Sabkha, degradation of flora and fauna,
and migration of the local people) [9]. After 2003 the marshes were refilled but the
degradation in water quality and ecosystem still endures.
Al-Hammar Marsh, one of the three biggest marshes in Iraq, is situated to the south of
the Euphrates River (30 45'–30° 59' N, 46° 25'–47° 15' E) and has an area ranging
from 2800 km2 of contiguous permanent marsh to 4500 km2 during flooding periods.
The marsh that is fed mainly by the Euphrates River, Tigris River, the Central
Marshes, and groundwater recharge drains ultimately into the Shatt Al-Arab River,
which empties into the Arabian Gulf [10]. Al-Hammar Marsh had been desiccated for
more than a decade; however, the marsh was restored to around half of its original size
in 2005 after a policy was initiated to restore the marshes in 2003 [9].
While some studies have addressed the water quality and environmental status of Al-
Hammar Marsh [4, 6, 11], few studies have applied new tools to investigate the
possible sources of pollution and the impact of such pollution on aquatic life in the
marsh. Therefore, the aim of the study is to address the distribution, levels, and
sources of contaminants in both water and sediments in the marsh, in order to evaluate
their environmental impacts and effects on the aquatic life, and, eventually, how to
manage the contaminant input into the marsh so that their concentrations do not reach
toxic levels. Furthermore, a joint initiative between the United Nations Environment
Program (UNEP) and United Nations Educational, Scientific and Cultural
Organization (UNESCO) has been established to ensure sustainable development
of the Iraqi Marshes by introducing them into the World Heritage List, as these unique
wetlands represent a region of outstanding universal historical, cultural, environmen-
tal, hydrological, and socio-economic value [12]. Therefore, we hope that the current
study contributes to the management process, which not only meets the technical
requirements of the World Heritage Convention, but will also give new impetus to
efforts that aim to preserve the environment in the Mesopotamian Marshes.
2. Methods
2.1. Ethical clearance
Permission was obtained from the Iraqi Ministry of Environment prior to
conducting the current study.
2.2. Sampling
2.2.1. Water sampling
The water samples were collected from Al-Hammar Marsh water during two
seasons. Twelve water samples were taken from the marsh in January (represents
winter season) 2014 and nine water samples in July (represents summer season)
2014 (Table 1 and Fig. 1).
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Table 1. Locations of the water, sediment, plants, and fish samples that were collected from Al-Hammar Marsh.
Station No. Water samples Sediment samples Plant samples Fish samples Coordinates Site name Province
N E
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*
Dry sediments.
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[(Fig._1)TD$IG]
Fifteen fish samples from three fish species of Liza abu (F1, F3, F4, F5, F8),
Tilapia zilli (F1, F2, F3, F5, F8), and Carassius carassius (F3, F4, F5, F8, F9) were
gathered from seven sampling stations in the Al- Hammar Marsh (Table 1).
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previously calibrated, while the other physical and chemical characteristics of the
water samples were analyzed in the lab according to the methods of the American
Public Health Association (APHA) [13]. The gravimetric method [14], five −day
Biological Oxygen Demand (BOD) test [15], and Colorimetric method [16] were
used to determine Total Dissolved Solids (TDS), BOD, and NO2−, respectively.
Ca2+, Mg2+, and Total Hardness (TH) were determined using Ethylenediaminete-
traacetic acid (EDTA) method. Flame Photometry method was used to determine
Na+ and K+ ions [17]. HCO3− was determined via titration method using indicator
titrated with HCl. SO42− was determined via the Turbidimetric method [18]. C1−
was determined via Silver Nitrate method [19]. NO3− was determined via
Ultraviolet Spectrophotometry method [20]. PO43− was determined via Ascorbic
Acid method using a spectrophotometer.
Heavy metals in water samples were sent to the ALS Laboratory Group in north
Vancouver, Canada to be analyzed by Inductively Coupled Plasma Mass
Spectrometry (ICP-MS) type Agilent device. The samples were analyzed directly
on the device without dilution and the result was corrected for any spectral
interferences. Organic Matter percentage (OM%) in the sediment samples was
determined by reducing the potassium dichromate (K2CrO7) by OC compound and
subsequent determination of the unreduced dichromate by oxidation-reduction
titration with ferrous ammonium sulfate [21]. Then, OM% was converted to
percent total organic carbon (TOC%). Traditionally, for soils, a conversion factor
of 1.724 is used to convert organic matter to organic carbon based on the
assumption that organic matter contains 58% organic carbon (i.e., g organic matter/
1.724 = g organic carbon) [22].
Concentrations of major and minor ions, as well as heavy metals, for thirteen
sediment samples were measured using Bench XRF Spectrometer/SPECTRO
XEPOS-2006 device at the Iraqi-German Laboratory at the University of Baghdad.
Samples were seived in a 2 mm seive, then powdered to 0.063 μm, and 5.0 g of
each sample was used to determine the element concentrations.
Ten of heavy metals (Hg, Co, Cr, Cu, Cd, Pb, Fe, Ni, Mn, and Zn) were measured
in plant and fish tissues. Dry tissue of plant and fish samples (in triplicate, each 0.2
g) were put into digestion flasks with 5 ml nitric acid (Merck) and 2 ml perchloric
acid, and then heated at 90 °C until all the materials were dissolved. After
digestion, the samples were diluted with deionized water to a volume of 10 ml and
then filtered. The resulting solutions were analyzed using flame atomic absorption
spectrophotometer [23].
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JMP 8.0 (SAS System) to determine the sources of major, minor, and heavy metals
in sediment samples from Al-Hammar Marsh.
EF = (Cx/Cy)S/(Cx/Cy)RS
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Table 2. Results of chemical analysis (in mg/kg) of sediments for the winter season in Al-Hammar Marsh.
St1 7.69 4.59 2.66 201190 99751 27884 26888 19584 12618 6981 3395 1995 1883 977 650 191 137 86 71 60 36.0 32.90 28.04 11.63 11.60 3.79 3.60 3.00 0.2 0.1 <1
St2 7.72 4.05 2.35 135311 191445 37705 41592 5302 52591 10535 4428 828 1155 520 1029 300 189 117 117 78 32.0 34.30 39.22 11.88 9.80 4.73 0.90 23.75 0.2 0.04 <1
St3 7.60 4.56 2.65 164403 133146 36229 27593 2599 35115 10652 4435 2255 2932 471 741 259 166 107 112 78 35.0 28.20 34.43 10.30 6.60 3.29 0.90 16.83 0.2 0.07 <1
St5 7.50 4.62 2.68 173052 130762 38153 22786 5647 35354 8999 3958 2269 1150 804 843 174 185 101 90 83 34.0 21.50 39.78 12.63 11.00 3.60 1.10 36.57 0.2 0.04 <1
St7 7.45 4.13 2.39 178914 131043 33655 24517 4017 33353 9664 5324 2245 973 717 694 211 160 100 95 76 30.0 18.90 31.95 10.95 7.60 2.88 0.87 12.27 0.2 0.09 <1
St9 7.73 4.35 2.52 126948 182842 43099 41001 5250 51082 9988 4110 1098 1294 505 963 302 179 115 120 75 28.0 33.80 39.54 10.68 14.40 4.81 1.90 19.74 0.3 0.04 <1
St10 7.86 4.17 2.42 166476 168537 35432 37744 1465 46610 11025 4219 661 1782 420 706 216 160 92 107 79 24.0 12.80 34.99 10.95 8.90 3.26 1.10 20.13 0.4 0.08 <1
St11 7.57 4.63 2.68 133024 145629 43938 24427 4341 39894 10610 4417 2564 833 543 840 214 215 134 105 91 31.0 30.90 45.21 12.72 9.00 5.79 1.30 50.65 0.6 0.06 <1
St12 7.56 4.68 2.71 162759 135203 36719 24916 3426 34988 10809 4154 2314 1385 513 760 216 186 66 106 81 29.0 18.10 43.22 10.68 7.90 0.46 1.00 12.66 0.4 0.05 <1
*
S3 7.90 5.30 3.07 134239 170126 20077 19186 14573 29304 9124 4085 2198 188 454 527 934 74 67 89 41 35.0 1.70 13.26 8.17 7.10 2.42 <0.10 7.00 <0.5 0.24 <1
*
S2 8.07 5.10 2.96 175482 120664 34026 29457 6576 31966 10278 4019 2161 11180 588 682 174 154 78 171 72 38.0 54.89 30.92 10.12 9.00 2.12 <1 11.17 <0.5 0.18 <1
*
S6 7.69 4.65 2.70 136026 133427 37566 33221 6788 35999 11465 4092 2409 21180 462 702 180 178 100 98 89 40.0 88.60 35.15 11.23 6.80 3.03 1.10 15.10 <0.5 0.29 <1
*
S3B 7.72 4.95 2.87 137598 133520 38846 27093 3007 35496 10793 4169 2282 15460 447 637 200 185 91 104 79 41.0 117.20 36.83 11.79 8.60 9.80 <1 13.76 <0.5 0.26 <1
Mean 7.70 4.60 2.67 155802 144315 35641 29263 6352 36490 10071 4216 1945 4723 571 752 275 167 96 107 76 33 37.98 34.81 11.06 9.10 3.84 1.38 18.66 0.30 0.12
SD 0.17 0.37 0.21 23227 26313 6188 7064 5107 10184 1175 427 637 6745 165 137 203 34 20 23 13 5 32.03 8.08 1.19 2.20 2.23 0.84 12.67 0.14 0.09
*
[26] 13700 330000 38000 6300 850 71300 13600 4600 800 450 300 850 200 40 100 300 50 20 5 20 17 2 5 1.8 8 0.4 0.35 <1
**
[42] 238 91 71 54 16 6 0.2
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Italic values represent concentrations that exceed [42] values.
*
Elements distribution limits in world soil according to [26].
**
Background mean values of trace elements in Mesopotamia soil and sediments according to [42].
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Table 3. Physiochemical parameters for water samples in Al-Hammar Marsh for winter (W) and summer (S) seasons.
Station No. Water depth (m) Turbidity (NTU) TDS (mg/l) EC (dS/cm) TH (mg/l) pH DO (mg/l) BOD COD (mg/l)
W S W S W S W S W S W S W S W S W S
St1 2.5 2.5 17.65 78.4 13602 10298 17.5 11.1 6353 2600 7.90 8.30 8.30 1.50 8.30 30.0 78 90
St2 2 1.2 9.88 29.2 6834 2384 7.9 3.5 1950 970 7.65 8.10 8.33 1.90 7.60 13.0 61 18
St3 2 1.5 45.91 11.3 9980 4000 16.7 6.1 3300 1668 9.00 8.10 8.85 0.34 8.17 1.6 106 40
St4 2 1.2 18.80 54.0 7140 6890 11.3 3.3 2450 2231 8.37 8.10 8.60 7.80 6.45 3.1 104 30
St5 1.5 1.0 10.90 28.0 5732 3142 6.6 4.0 1700 1076 8.25 8.00 8.81 4.10 6.46 5.0 44 32
St6 >4 1.0 10.31 34.0 5532 3076 7.3 4.0 950 1241 8.31 8.00 8.88 0.02 6.48 10.0 66 41
St7 >4 NM 6.10 NM 3090 NM 4.6 NM 1100 NM 8.36 NM 8.95 NM 6.60 NM 55 NM
St8 >4 >4 5.63 13.0 2744 3068 4.0 4.3 900 1164 8.27 8.30 8.30 3.00 5.21 5.5 59 32
St9 1.5 1.2 11.70 99.1 9666 1698 11.2 2.3 2200 728 8.30 8.30 7.70 5.20 6.16 2.5 78 42
St10 >4 NM 10.50 NM 7646 NM 9.6 NM 2000 NM 8.26 NM 8.43 NM 7.80 NM 84 NM
St11 2.5 NM 10.80 NM 3963 NM 6.2 NM 2010 NM 7.67 NM 4.69 NM NM NM 48 NM
St12 >4 NM 13.50 NM 6170 NM 9.3 NM 3320 NM 8.57 NM 8.98 NM NM NM 96 NM
St13 NM 4.0 NM 15.4 NM 4000 NM 6.3 NM 679 NM 8.00 NM 3.10 NM 1.6 NM 37
SD 0.98 10.22 29.2 2983 2531 4.11 2.5 1424 627 0.36 0.13 1.13 2.32 0.95 8.59 21 19
Mean 1.6 14.3 40.3 6841 4284 9.3 4.9 2352 1373 8.28 8.09 8.23 2.99 6.51 8.0 73 40
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NM: Not Measured.
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decrease in summer, which is due to the poor ability of water to hold oxygen at
high temperatures, as a result of higher rates of microbial metabolism [31, 32]
(Table 3). On the other hand, BOD levels were found to be higher in summer than
in winter (Table 3). This inverse relation between DO and BOD is expected, as
high BOD levels indicate high levels of organic contaminants in water, and the
microbes are working intensely to break it down, consequently consuming more
oxygen and resulting in low DO levels in water [33]. All concentrations of Ca2+
for both seasons were beyond acceptable levels [29], excluding St2, St6, St13, and
St9 for the summer season, which were within limits (Table 4). All Mg2+
concentrations were beyond the acceptable limits (WHO, 2008) except St8, St11,
and St12 for the winter season, and St9 and St13 for summer season (Table 4). In
general, all Na+ concentration values for both seasons exceeded WHO limits [29]
(Table 4). The concentration values of K+ exceeded the allowable limits in both
winter and summer seasons, except at station St5 in the winter season and St9 in
Table 4. Ions concentrations (mg/l) in Al-Hammar Marsh water for two sampling seasons for current study,
mean concentrations of these ions for a previous study by [35], and [29] standard limits.
Station Ca2+ Mg2+ Na+ K+ Cl− HCO3− SO42− PO43− NO3− NO2−
W S W S W S W S W S W S W S W S W S W S
St1 655 460 920 348 2300 1520 78 45 4050 3122 243 224 3700 1800 0.28 0.15 9.1 3.1 0.11 0.09
St2 320 150 276 137 930 325 25 15 1622 675 307 174 1750 800 0.12 0.28 1.6 2.5 0.09 0.10
St3 460 200 510 270 2170 560 55 18 2890 1120 222 235 3000 1250 0.15 0.18 5.3 3.3 0.10 0.10
St4 360 254 372 369 1875 1390 50 43 2850 2587 217 130 1440 1500 0.15 0.21 3.9 4.2 0.10 0.10
St5 220 169 276 151 1533 605 12 19 2375 1035 266 143 1800 760 0.12 0.30 3.3 4.7 0.10 0.10
St6 240 146 204 202 992 565 26 21 1662 1021 251 172 1322 900 0.15 0.34 3.5 3.7 0.09 0.13
St7 200 144 496 15 860 259 875 0.21 3.8 0.09
St8 180 177 108 166 488 635 13 23 665 1030 254 121 910 900 0.18 0.34 4.4 4.0 0.09 0.10
St9 320 96 336 113 1695 280 45 11 2375 405 231 139 2800 500 0.18 0.28 3.8 2.3 0.09 0.13
St10 300 300 1373 38 2137 246 2300 0.15 3.4 0.10
St11 240 99 956 66 1330 232 967 0.55 0.4 0.12
St12 270 90 1433 74 2230 272 1200 0.7 0.3 0.09
St13 119 87 760 26 1105 122 865 0.28 2.7 0.10
SD 132 108 231 101 598 434 23 11.9 942 897 24 42 921 407 0.19 0.07 2.33 0.82 0.01 0.01
Mean 314 197 303 205 1353 738 41 24.4 2087 1344 250 162 1839 1031 0.25 0.26 3.6 3.4 0.10 0.11
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summer season, which were within the allowable limits (Table 4). Cl−
concentrations exceeded the allowable limits in both seasons, though they were
lower for summer season than winter season (Table 4). All detected values of
SO42− exceeded the allowable limits (Table 4). The high levels of TDS, TH, and
major ions (i.e., Ca2+, Mg2+, Na+, K+, Cl−, and SO42−) in the current study can be
attributed to the high salinity of Al-Hammar Marsh feeders, agriculture runoff,
livestock manure (such as buffalo manure) that is widely applied in the area,
domestic sewage effluents, and washing of the surrounding Sabkha during flooding
from rain storms (as occurs winter and will be discussed later (Table 4)).
PO43−, NO3−, and NO2− concentrations were within acceptable standards limits
[29]. Although these nutrients (i.e., PO43−, NO3−, and NO2−) have relatively high
concentrations at the marsh inlet area, stagnation of Al-Hammar Marsh water can
increase the opportunity for plants and aquatic organisms to remove such nutrients
from the water [34].
Comparison between the results from the current study and the study of [35] and
[29] standard limits showed a considerable increase in concentrations of major ions
(Table 4), indicating that the impact of desiccation on water quality, even after 12
years of inundation, still exists and that the marsh conditions are still departing
from desirable or historical levels. The findings are consistent with other studies
[e.g.,3] that noted that some water chemistry parameters of Al-Hammar Marsh,
when compared with historical surveys completed before drainage [36, 37, 38, 39],
revealed high increases. This considerable increase in ion concentrations is
probably related to a rise in salinity in the main feeder of the marsh (e.g., the
Euphrates River) and to increased flux into the water column of ions concentrated
in the soil after more than a decade of drainage and evaporation [10].
Heavy metals analyses revealed ions such as Pb, Al, B, Fe, and Mn have
concentrations that generally exceed Maximum Contaminant Level (MCL)
standards [40] (Table 5). Analyses also revealed that all heavy metals in the
current study showed an increase in concentrations at station St1 (marsh inlet),
while nearly all these metals exhibited a distinct decrease in their concentrations at
St8 (marsh outlet), indicating that the marsh works as a filtering sink for metals
(Table 5).
In general major and minor ions, as well as heavy metals exhibit higher
concentrations in winter than in summer (Tables 4, 5). Such increasing pattern in
ion concentrations at most stations in the winter season was due to runoff from
washing of the surrounding Sabkha during flooding by rainstorms. Additionally,
the Iraqi Ministry of Water Resource orchestrates a systematic release of water into
the marsh, which is usually low in winter and high in summer, resulting in
increased dilution in summer and thus lower solute concentrations.
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Table 5. Heavy metal concentrations (in μg/l) in water samples for winter (W) and summer (S) seasons for Al-Hammar Marsh.
Station As Cd Cr Cu Hg Pb Se Zn Al B Be Co Fe Li Mn Mo Ni U V Sr
W S W S W S W S W S W S W S W S W S W S W S W S W S W S W S W S W S W S W S W S
St1 20 20 1.3 0.1 58 8 30.2 36.9 2.8 <0.2 16.4 3.5 30 30 167 28 240 700 >1000 >1000 0.3 <0.3 1.8 2.3 1750 990 60 120 26 651 36 29 37.9 19.5 11.7 9.47 9 22 >1000 >1000
St2 10 10 0.6 <0.1 22 3 31.4 9.5 1 <0.2 43.1 0.5 10 10 132 36 800 70 >1000 850 <0.3 <0.3 3.5 0.2 1520 90 50 30 68.9 111 41 11 37.3 5.4 16.4 4.1 19 8 >1000 >1000
St3 10 <10 0.1 <0.1 5 23 18.7 7.3 0.3 0.3 9.8 0.8 20 10 64 53 100 140 >1000 >1000 <0.3 <0.3 2 0.3 2190 330 110 50 43.8 53.1 28 10 37.9 12.6 6.38 1.13 6 2 >1000 >1000
St4 10 <10 0.1 <0.1 6 10 22.3 8.1 <0.2 <0.2 23.4 1.9 10 20 88 31 1390 480 >1000 >1000 2.4 <0.3 3.1 0.8 3610 650 90 70 47.4 30.6 25 13 46.5 10.7 5.17 4.11 32 5 >1000 >1000
St5 10 <10 0.2 <0.1 5 <1 46.4 2.1 <0.2 <0.2 50.5 0.4 10 10 189 8 600 230 >1000 920 <0.3 <0.3 3.8 0.1 2040 <20 60 30 45.6 10.5 35 13 47.7 2.8 7.83 4.51 14 8 >1000 >1000
St6 10 10 <0.1 0.1 6 12 36.2 4.7 <0.2 0.3 48.6 0.7 10 10 145 47 340 80 1000 870 <0.3 <0.3 3.2 0.3 1700 180 60 40 56.6 8.7 22 10 37.1 11.1 3.88 2.34 8 9 >1000 >1000
St7 <10 <0.1 4 18.6 0.2 17.8 10 68 160 610 <0.3 2 920 40 20.7 11 31.9 2.67 7 >1000
St8 <10 <10 <0.1 <0.1 5 7 6.2 6.2 0.2 <0.2 <0.2 1.4 <10 10 27 36 <50 <50 470 600 <0.3 <0.3 0.5 0.3 640 240 40 40 8 42.1 10 7 25.5 5.7 2.53 2.12 6 5 >1000 >1000
St9 10 <10 0.3 <0.1 10 20 70.6 5.4 <0.2 0.3 71.9 1 20 <10 168 86 420 110 >1000 390 <0.3 <0.3 4.2 0.4 5440 250 80 40 96 16.2 40 10 49.6 13 5.2 1.65 8 7 >1000 >1000
St13 10 10 0.1 <0.1 6 2 35.7 8.3 0.3 <0.2 23.6 0.4 10 10 439 16 230 60 >1000 >1000 <0.3 <0.3 2.7 0.2 1270 60 240 40 32.2 149 18 12 32.6 3.6 4.82 2.45 7 6 >1000 >1000
Mean 12.7 10.6 31.6 9.8 33.9 1.17 14.4 14.3 149 38 475 233 2.7 0.5 2108 348 83 51 44.5 119 26.6 12.8 38 9.4 6.65 3.54 11.6 8 >1000 >1000
SD 16.8 7.5 17.8 10.4 20.6 1 7.3 7.9 115 22.8 408 233 1.1 0.7 1425 316 59 28 25 205 11.3 6.4 7.6 5.4 4.3 2.5 8.3 5.7
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94.77% of the data variation (Table 6). The first principal component PC1, which
has strong factor loading of K (0.96), Zn (0.89), Ti (0.82), Fe (0.77), Ni (0.76), and
moderate factor loading of Cu (0.71), Co (0.57), Se (0.69), Al (0.71), Zr (0.66)
accounts for 36.07% of the variance and can be explained as anthropogenic and
Table 6. PCA loadings of major and trace elements on varimax rotated principal
components.
Element Component
1 2 3 4
*
Significant variable.
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natural sources. Zn, Fe, Ni, Cu, Co, and Se can result from agriculture activities and
wastes from oil extraction, whereas Al, K, Ti, and Zr can be derived from natural
deposits. PC2, which has strong factor loadings of Mg (0.94), Cr (0.86), Mn (0.77)
and Si (0.79), accounts for 28.02% of the variance. Si originates from erosion of
crustal material, while Mg, Cr, and Mn can be considered of anthropogenic origin
being derived from agriculture runoff from farmland. PC3, which has strong factor
loading of Br (0.96), Cd (0.80), Cl (0.79), and moderate factor loading of N (0.73) and
TOC% (0.58) and accounts for 15.44% of the variance, can be considered to represent
anthropogenic sources. Fertilizers, human sewage and livestock manure are known to
be a significant source of these elements [51]. PC4 has a strong factor loading of Pb
(0.97) and moderate loading of Co (0.72), V (0.61), and As (0.60) accounts for
15.23% of the variance. Elements in PC4 have the same source, which are fertilizers
and waste from oil extraction processes.
[(Fig._2)TD$IG]
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b- Cluster analysis
By applying the Ward method, AHCA was performed on the results of element
concentrations in sediment samples from Al-Hammar Marsh. AHCA highlighted
four specific element response patterns (R1, R2, R3, and R4). The distance cluster
represents the degree of association between elements, where clusters with smaller
or shorter distances between them are more similar to each other than clusters with
larger or longer distances between [52]. Here, cluster R2 has the shortest distance
(6.98) and highest similarity to cluster R1, whereas cluster R3 is the least similar
and has the greatest distance to R1 (19.33) (Fig. 2).
Elements clustering in R1 (Mg, Al, Si, Cr, Mn, K, Ti, and Zr) that dominate in the
PC2 indicate natural and anthropogenic sources. Al, Si, Ti, K, and Zr are lithophile
elements according to Goldschmidt’s classification of geochemical elements [53].
Lithophile elements are those showing an affinity for silicate phases and are
concentrated in the silicate portion (crust and mantle) of the Earth [53].
Concentration results of Mg, Cr, and Mn show pollution of Al-Hammar Marsh
sediments by these elements, which may come from fertilizers that are known to be
a significant source of these elements [43, 44, 51, 54]. V, Fe, Ni, Cu, Co, Zn, Se,
[(Fig._3)TD$IG]
Fig. 3. Enrichment Factor (EF) for elements. The middle horizontal thick lines represent the mean EF
while the dotted horizontal thin lines represent EFs of 2 and 5. An EF of 2 is a threshold between natural
and possible anthropogenic element sourcing while an EF of 5 represents a threshold between possible
anthropogenic and significant anthropogenic element sourcing.
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Table 7. Heavy metal concentrations (mg/kg) in plant samples with critical concentrations of trace metals in plant tissues.
P1 Schoenoplectus litoralis 0.014 0.506 0.329 55.41 0.051 0.325 0.075 5.217 14.10 30.56
P6 Schoenoplectus litoralis 0.010 0.425 0.350 50.68 0.057 0.209 0.081 4.845 13.56 28.91
P10 Schoenoplectus litoralis 0.019 0.563 0.293 54.20 0.046 0.371 0.070 5.461 13.09 33.74
P2 Phragmites australis 0.261 0.869 0.415 61.72 0.105 1.021 0.094 6.821 15.90 48.02
P7 Phragmites australis 0.300 0.728 0.468 68.10 0.096 0.902 0.210 7.069 16.65 41.79
P8 Phragmites australis 0.232 0.895 0.386 64.63 0.124 1.040 0.155 6.598 15.78 44.61
P3 Typha domingensis 0.190 1.021 0.501 63.23 0.092 1.036 0.134 6.715 14.91 43.16
P4 Typha domingensis 0.210 0.925 0.465 58.60 0.079 0.811 0.097 5.966 14.46 38.97
P9 Typha domingensis 0.105 1.169 0.492 61.74 0.110 0.935 0.201 7.011 15.38 41.50
P2 Ceratophyllum demersum 0.062 0.723 0.213 48.15 0.031 0.431 0.054 5.353 14.34 25.34
P5 Ceratophyllum demersum 0.011 0.641 0.165 43.33 0.011 0.729 0.072 4.503 13.81 36.22
P7 Ceratophyllum demersum 0.017 0.583 0.180 46.01 0.018 0.656 0.064 4.764 13.25 33.65
Mean 0.119 0.754 0.354 56.31 0.068 0.705 0.108 5.860 14.602 37.20
SD 0.11 0.22 0.12 7.97 0.04 0.30 0.05 0.95 1.13 6.94
* * * * * ** * * * **
Critical concentrations in plants 0.5–1 10–20 1–2 300–600 20–30 30–300 5–10 15–20 150–200 400–1000
*
[60].
**
[44].
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[(Fig._4)TD$IG]
Table 8. Heavy metals concentration (mg/kg) in fish species in Al-Hammar Marsh water with the
Maximum Permitted Concentration (MPC). Bold values represent concentrations that exceed MPC.
F1 Liza abu 0.126 0.365 0.202 7.96 55.63 0.039 36.45 22.31 6.31 26.30
F4 Liza abu 0.146 0.418 0.193 8.47 56.52 0.046 43.45 14.41 8.21 25.78
F3 Liza abu 0.506 0.396 0.186 10.72 60.51 0.048 38.40 21.10 10.86 32.21
F5 Liza abu 0.825 0.508 0.352 9.83 63.73 0.063 40.12 29.20 13.45 27.46
F8 Liza abu 0.195 0.482 0.211 9.82 57.36 0.039 38.10 13.14 9.51 31.51
F1 Tilapia zilli 0.080 0.223 0.150 8.87 53.24 0.021 30.02 11.41 1.95 21.21
F2 Tilapia zilli 0.021 0.195 0.141 7.21 56.62 0.016 34.16 14.12 2.38 17.56
F3 Tilapia zilli 0.698 0.511 0.346 10.98 65.36 0.058 41.23 28.39 14.74 31.10
F5 Tilapia zilli 0.014 0.262 0.185 8.11 57.10 0.034 33.20 13.46 4.28 18.65
F8 Tilapia zilli 0.071 0.185 0.212 10.09 58.21 0.023 31.41 15.12 3.34 23.82
F3 Carassius carassius 0.463 0.431 0.206 11.57 62.20 0.052 33.30 16.13 6.45 30.04
F4 Carassius carassius 0.036 0.224 0.206 9.43 55.75 0.030 32.36 11.39 0.09 20.13
F5 Carassius carassius 0.246 0.471 0.282 7.94 62.13 0.045 35.11 18.26 11.56 28.32
F8 Carassius carassius 0.767 0.506 0.391 11.21 69.05 0.065 37.41 25.15 16.38 29.66
F9 Carassius carassius 0.065 0.167 0.173 7.88 61.34 0.026 35.60 12.33 5.23 21.09
Mean 0.286 0.358 0.220 9.40 59.62 0.040 35.97 17.83 7.64 25.92
SD 0.29 0.13 0.080 1.39 4.30 0.02 3.80 6.06 4.97 4.94
* ** * * ** * *** ** * *
MPC 0.5 0.04–0.26 1 30 18.5–72.3 0.5 5 0.01–2.78 0.5 150
*
[62].
**
[63].
***
[64].
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[(Fig._5)TD$IG]
As, and Mo clustered in R2 (dominating in the PC1 and PC4) are indicative of
anthropogenic sources (i.e., agricultural and petroleum production activities),
which the Environmental Protection Agency reported as sources of contaminants
[55], along with [56] who referred to some of these trace metals being released
from fertilizers and from oil refineries. P, TOC%, N, Cl, Cd, and Br clustered in R3
(dominating in the PC3) can result from agricultural sources according to [57].
Nitrate-N, ammonium-N, phosphate-P, and C are the most common contaminants
derived from unregulated animal waste disposal practices. These four chemicals
are usually found at concentrations ranging from 1,000 to 50,000 mg/kg (elemental
form) in animal wastes [58]. Cd and Br can also be from agricultural sources [44].
Elements in R4 (i.e., S, Ca, Sr, and U) are mainly of anthropogenic origin.
Fertilizers can be a source for S, Ca [43, 59], Sr, and U [44].
c- Pollution analysis
The results of EF calculations for Al-Hammar Marsh sediment samples show that
EF values for S, Ca, U and Sr (clustered in R4) show a general enrichment and
have mean EF values of 18.82, 33.54, 3.35 and 5.73, respectively (Fig. 3D). This
enrichment indicates that anthropogenic activity is a remarkable source for these
elements. P, N, Cl, Cd, and Br (clustered in R3) have mean EF values of 7.19, 2.68,
15.94, 1.00, and 21.58, respectively (Fig. 3C), and indicate a predominantly
anthropogenic source. V, Fe, Ni, Cu, Co, Zn, Se, As, Pb, and Mo (clustered in R2)
have mean EF values of 2.81, 2.69, 12.03, 5.01, 6.67, 4.36, 2.19, 2.25, 1.91, and
13.33, respectively (Fig. 3B), indicating the anthropogenic input of these elements
in sediments in Al-Hammar Marsh. Elements Mg, Al, Si, Cr, Mn, K, and Ti,
(clustered in R1) have mean EF values of 13.33, 1.45, 1.27, 4.10, 2.55, 2.13, and
2.67, respectively (Fig. 3A), indicating that sediments are significantly polluted by
Mg and Mn, minimally polluted by Cr, and not polluted by Al, K, Ti and Si. It is
worth mentioning that this pollution analysis is in good agreement with both
AHCA and PCA analyses in determining the elemental sourcing (i.e., natural and/
or anthropogenic).
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4. Conclusions
1- Decreasing of Tigris and Euphrates discharges during the past decades due to
drought conditions and upstream damming, as well as the increasing stress of
wastewater effluents from agricultural, residential, and industrial (mainly oil
extraction) activities, led to degradation of the downstream Al-Hammar Marsh
water quality in terms of physical, chemical, and biological properties. As such
properties were found to consistently exceed the historical objectives as well as
WHO objectives.
2- The Marsh works as a natural filtration and bioremediation system, as nearly all
observed major ions and heavy metals in water showed a distinct decreasing
trend at the marsh outlet station compared to other stations.
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Declarations
Author contribution statement
H.F.A. Al-Gburi: Conceived and designed the experiments; Performed the
experiments; Analyzed and interpreted the data; Contributed reagents, materials,
analysis tools or data; Wrote the paper.
B.S. Al-Tawash, H.S. Al-Lafta: Analyzed and interpreted the data; Contributed
reagents, materials, analysis tools or data; Wrote the paper.
Funding statement
This research did not receive any specific grant from funding agencies in the
public, commercial, or not-for-profit sectors.
Additional information
No additional information is available for this paper.
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