Environmental Assessment ofAl-Hammar Marsh, SouthernIraq

Download as pdf or txt
Download as pdf or txt
You are on page 1of 26

Received:

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

http://dx.doi.org/10.1016/j.heliyon.2017.e00256
2405-8440/© 2017 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY license
(http://creativecommons.org/licenses/by/4.0/).
Article No~e00256

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.

Keywords: Environmental science, Geochemistry, Biogeochemistry

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

2 http://dx.doi.org/10.1016/j.heliyon.2017.e00256
2405-8440/© 2017 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY license
(http://creativecommons.org/licenses/by/4.0/).
Article No~e00256

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).

3 http://dx.doi.org/10.1016/j.heliyon.2017.e00256
2405-8440/© 2017 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY license
(http://creativecommons.org/licenses/by/4.0/).
4
(http://creativecommons.org/licenses/by/4.0/).
2405-8440/© 2017 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY license
http://dx.doi.org/10.1016/j.heliyon.2017.e00256

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

1 St1 St1 P1 F1 30°53'49.38” 46°29'47.87” Suk Al-Shuyukh Thiqar


2 St2 St2 P2 F2 30°48'5.24” 46°35'3.87” Al-Sinaf Thiqar
3 St3 St3 P3 F3 30°50'42.55” 46°58'37.14” Hor Abu tina Thiqar
4 St4 St4 P4 F4 30°39'20.99” 47°38'25.15” Naggarah Basra
5 St5 St5 P5 F5 30°56'48.73” 46°46'1.99” Al-Chibayish Thiqar
6 St6 St6 P6 30°40'29.96” 47°28'25.99” Shilaychiya Basra
7 St7 St7 P7 30°35'43.87” 47°41'51.25” Qarmat Ali Basra
8 St8 P8 F8 30°34'43.61” 47°44'16.73” Qarmat Ali Basra
9 St9 St9 P9 F9 30°49'26.51” 47°29'46.61” Al-Shafi Basra
10 St10 St10 P10 30°38'39.11” 47°41'6.39” Al-Mashab Basra
11 St11 St11 30°49'8.03” 46°37'1.36” Kirmashia Thiqar
12 St12 St12 30°42'6.99” 47°35'3.43” Al-Barga Basra
13 St13 30°50'44.87” 46°43'9.48” Al-Bithij Thiqar
*
14 S1 30°38'20.83” 47°40'40.87” Al-Hartha Basra
*
15 S2 30°38'24.79” 47°42'35.32” Al-Hartha Basra
*
16 S3 30°41'0.66” 47° 7'27.70” Rumillah oil field Basra
*
17 S3A 30°39'26.59” 47°35'32.93” Al-Hartha Basra
*
18 S3B 30°40'44.72” 47°36'24.34” Al-Hartha Basra
*
19 S6 30°36'43.88” 47°40'1.31” Al-Hartha Basra

Article No~e00256
*
Dry sediments.
Article No~e00256

[(Fig._1)TD$IG]

Fig. 1. Map of field sampling stations in Al-Hammar Marsh.

2.2.2. Sediments sampling


Seventeen samples from Al- Hammar Marsh sediments were collected during the
winter season (Table 1 and Fig. 1).

2.2.3. Plants and fish sampling


Twelve different plant samples of Phragmites australis (P2, P7, P8), Typha
domingensis (P3, P4, P9), Schoenoplectus litoralis (P1, P6, P10), and Ceratophyllum
demersum (P2, P5, P7) species were gathered from Al- Hammar Marsh from ten
sampling stations (Table 1). The parts sampled from the plants were stems and leaves.

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).

2.3. Sample analyses


Water depth, turbidity, Electrical Conductivity (EC), and Dissolved Oxygen (DO)
of marsh water was measured in the field with a portable multimeter, which was

5 http://dx.doi.org/10.1016/j.heliyon.2017.e00256
2405-8440/© 2017 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY license
(http://creativecommons.org/licenses/by/4.0/).
Article No~e00256

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].

2.4. Statistical analysis


Multivariate statistical techniques, such as Principal Component Analysis (PCA)
and Agglomerative Hierarchal Cluster Analysis (AHCA), were performed using

6 http://dx.doi.org/10.1016/j.heliyon.2017.e00256
2405-8440/© 2017 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY license
(http://creativecommons.org/licenses/by/4.0/).
Article No~e00256

JMP 8.0 (SAS System) to determine the sources of major, minor, and heavy metals
in sediment samples from Al-Hammar Marsh.

2.5. Pollution analysis


Pollution indices, such as Enrichment Factor (EF), are powerful tools for
processing, analyzing, and conveying raw environmental information to decision
makers, managers, technicians, and the public [24].

The formula to calculate EF is:

EF = (Cx/Cy)S/(Cx/Cy)RS

Where Cx is the measured concentration of the examined metal in the sediment


sample (mg/kg), and Cy is concentration of immobile element in the sample
(zirconium here), and (Cx/Cy)RS is the concentration of element X to immobile
element ratio in the selected reference sample [25].

In order to evaluate whether the content of a chemical element in the sediment is


derived from natural or anthropogenic sources, the EF was calculated for all
studied sediment samples using zirconium as the reference element. The EF is the
relative abundance of a chemical element in a sediment sample compared to the
bedrock. Zirconium is generally considered to mainly originate from natural
lithogenic sources (rock weathering of mineral zircon), and has no significant
anthropogenic source. Total elemental concentrations (ppm) in the world soil,
according to [26] (Table 2), are considered to calculate EF. An EF < 2 shows
deficiency to low enrichment and can be considered in the range of natural
variability. 2 < EF < 5 shows low enrichment (i.e., some enrichment caused by
anthropogenic input). 5 < EF < 20 is a clear indication of human influence
(significant enrichment caused by anthropogenic inputs). An EF 20 to 40
represents very high enrichment and an EF > 40 represents extremely high
enrichment [27, 28].

3. Results and discussion


3.1. Water analysis
High turbidity values that exceed WHO standard limits for drinking water [29]
(Table 3) observed in the current study due to the high turbidity of Al-Hammar
Marsh feeders (e.g., Euphrates River), as these water supplies carry large quantities
of clay, silt, plankton and other microscopic organisms [30]. All TDS and TH
values in water samples were considered unacceptable according to WHO standard
limits for drinking water [29] (Table 3). The pH values were within the acceptable
limits of WHO standards (i.e., 6.5–8.5) with the exception of St3, which was
beyond acceptable limits in the winter season. DO levels showed a considerable

7 http://dx.doi.org/10.1016/j.heliyon.2017.e00256
2405-8440/© 2017 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY license
(http://creativecommons.org/licenses/by/4.0/).
8
(http://creativecommons.org/licenses/by/4.0/).
2405-8440/© 2017 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY license
http://dx.doi.org/10.1016/j.heliyon.2017.e00256

Table 2. Results of chemical analysis (in mg/kg) of sediments for the winter season in Al-Hammar Marsh.

Station pH OM% TOC% Ca Si Fe Mg S Al K Ti P CI Sr Mn Cr Ni V Zr Zn N Br Cu Pb Mo As U Co Se Cd Hg

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

Bold values represent concentrations that exceed [26] values.

Article No~e00256
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].
9
(http://creativecommons.org/licenses/by/4.0/).
2405-8440/© 2017 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY license
http://dx.doi.org/10.1016/j.heliyon.2017.e00256

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

WHO (2008) 5 1000 250 500 6.5–8.5 4

Article No~e00256
NM: Not Measured.
Article No~e00256

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

[35] 89 100 289 7 487 64 247

[29] 100 125 200 12 250 250 0.4 50 3

10 http://dx.doi.org/10.1016/j.heliyon.2017.e00256
2405-8440/© 2017 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY license
(http://creativecommons.org/licenses/by/4.0/).
Article No~e00256

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.

11 http://dx.doi.org/10.1016/j.heliyon.2017.e00256
2405-8440/© 2017 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY license
(http://creativecommons.org/licenses/by/4.0/).
12
(http://creativecommons.org/licenses/by/4.0/).
2405-8440/© 2017 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY license
http://dx.doi.org/10.1016/j.heliyon.2017.e00256

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

MCL 10 5 100 1300 2 15 50 5000 50–200 500 4 50 300 700 50 70 70 30 9 4000

Bold values represent concentrations that exceed MCL.

Article No~e00256
Article No~e00256

3.2. Sediment analysis


3.2.1. Chemical analysis
Analysis results of pH showed that all sediment samples from Al-Hammar Marsh
were alkaline. This is due to the high content of calcium and magnesium carbonates. In
the current study, TOC% in marsh sediments is <5%, which is concordant with [41],
who assumed that TOC% of <5% is mainly restricted to brackish-water lakes and
marshes. Low TOC levels in this study were due to the high salinity of marsh water.

The mean concentrations of elements in Al-Hammar Marsh sediments were


compared with the natural occurrences of trace elements in world soil (Table 2).
Compared to [26], Al-Hammar Marsh sediments, in general, have higher mean
concentrations of Ca, Mg, S, P, Cl, Sr, Cr, Ni, Zn, N, Br, Cu, Mo, and Co (Table 2).
Furthermore, elements in Al-Hammar Marsh sediments were compared with the
mean value of their natural abundance in Iraqi soil, according to [42]. The mean
concentrations of Cr, Ni, V, Zn, Cu, and Pb in this study exceeded the mean
concentrations of their background values reported by [42] (Table 2).

Applications of fertilizers, such as Nitrogen-Phosphorus-Potassium (NPK),


Nitrogen-Phosphorus (NP), Monoammonium Phosphate (MAP), and Triple
superphosphate (TSP) that are produced and used in Iraq may contribute to a
considerable increase of some heavy metals, such as Ca, Mg, S, P, Cr, Ni, Zn, N,
Cu, Mo, and Co [43], and Sr [44]. Additionally, the region of southern Iraq is well
known for oil extraction activities and such activities can contribute to high
sediment pollution of Pb, Cr, Cd, Co [45], Pb, V [46], and Br [47].

3.2.2. Statistical analysis


a- Principal Component Analysis

PCA technique was performed by VARIMAX rotation. VARIMAX rotation was


employed because orthogonal rotation minimizes the number of variables with a
high loading on each component and therefore facilitates the interpretation of PCA
results [48]. This technique clusters variables into groups such that variables
belonging to one group are highly correlated with one another and assumes that
highly correlated compounds come from the same source [49]. Eigen values in
PCA indicate the significance of the components. The component with the highest
Eigen value is taken to be the most significant. Eigen values should be ≥1 for
proper consideration during PCA [50]. Factor loadings values of >0.75, between
0.75 and 0.5, and between 0.5 and 0.3 are classified as strong, moderate, and weak,
respectively, based on their absolute values [50].

By applying PCA to the results of the chemical analyses, four principal


components with Eigen values greater than 1 were extracted, which explained

13 http://dx.doi.org/10.1016/j.heliyon.2017.e00256
2405-8440/© 2017 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY license
(http://creativecommons.org/licenses/by/4.0/).
Article No~e00256

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

Mg 0.089 0.926* 0.350 –0.655


Al 0.655 *
0.747 0.098 –0.089
Si 0.551 0.791 *
–0.209 0.153
P –0.091 –0.939 0.260 0.116
S –0.972 –0.172 0.083 –0.047
CI 0.118 –0.463 0.797* –0.296
K 0.970 *
0.124 0.186 –0.038
Ca –0.756 –0.510 –0.204 –0.342
V 0.434 0.561 –0.217 0.610*
Cd –0.003 –0.513 0.802* –0.278
Cr 0.345 0.861 *
–0.311 0.063
Mn 0.350 0.772* –0.361 0.348
Fe 0.771 *
0.399 –0.023 0.481
Co 0.576 *
0.184 –0.308 0.720*
Ni 0.762* 0.203 –0.056 0.603
Cu 0.716* 0.284 –0.246 0.561
Zn 0.897 *
–0.059 0.026 0.420
As 0.083 0.325 0.664 0.602*
Se 0.700* –0.020 –0.176 0.498
Br 0.052 –0.192 0.967* –0.012
Sr –0.923 –0.294 –0.199 0.064
Mo –0.533 0.070 –0.215 0.283
Pb –0.089 0.007 –0.058 0.976*
U –0.975 –0.060 0.109 0.027
Ti 0.820 *
0.099 –0.334 –0.021
Zr 0.661 *
0.269 0.225 –0.432
pH –0.008 –0.911 0.064 –0.310
TOC% –0.209 –0.741 0.582* –0.053
N –0.318 –0.557 0.730 *
–0.122
Variance explained by component % 36.074 28.022 15.435 15.234
Cumulative variance explained by component % 36.074 64.096 79.531 94.765

*
Significant variable.

14 http://dx.doi.org/10.1016/j.heliyon.2017.e00256
2405-8440/© 2017 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY license
(http://creativecommons.org/licenses/by/4.0/).
Article No~e00256

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]

Fig. 2. Dendrogram of elements measured and pH using Ward method.

15 http://dx.doi.org/10.1016/j.heliyon.2017.e00256
2405-8440/© 2017 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY license
(http://creativecommons.org/licenses/by/4.0/).
Article No~e00256

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.

16 http://dx.doi.org/10.1016/j.heliyon.2017.e00256
2405-8440/© 2017 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY license
(http://creativecommons.org/licenses/by/4.0/).
17
(http://creativecommons.org/licenses/by/4.0/).
2405-8440/© 2017 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY license
http://dx.doi.org/10.1016/j.heliyon.2017.e00256

Table 7. Heavy metal concentrations (mg/kg) in plant samples with critical concentrations of trace metals in plant tissues.

Station No. Plant species Hg Co Cr Fe Ni Pb Cd Cu Zn Mn

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].

Article No~e00256
Article No~e00256

[(Fig._4)TD$IG]

Fig. 4. Distribution of heavy metals in plant sample.

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.

Station No. Fish species Cd Co Cr Cu Fe Hg Mn Ni Pb Zn

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].

18 http://dx.doi.org/10.1016/j.heliyon.2017.e00256
2405-8440/© 2017 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY license
(http://creativecommons.org/licenses/by/4.0/).
Article No~e00256

[(Fig._5)TD$IG]

Fig. 5. Distribution of heavy metals in fish samples.

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).

19 http://dx.doi.org/10.1016/j.heliyon.2017.e00256
2405-8440/© 2017 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY license
(http://creativecommons.org/licenses/by/4.0/).
Article No~e00256

3.3. Plant analysis


In the current study, investigation of plant pollution by studying heavy metals content
in plant tissue provides useful information on the status of Al-Hammar Marsh
environment. Pollution for four plant species of Schoenoplectus litoralis, Phragmites
australis, Typha domingensis, and Ceratophyllum demersum was investigated by
examining ten heavy metals (Hg, Co, Cr, Ni, Pb, Cd, Cu, Zn, Mn, and Fe). Results of
plant analysis show that the mean concentration of heavy metals are in the order of Fe
> Mn > Zn > Cu > Co > Pb > Cr > Hg > Cd > Ni (Table 7 and Fig. 4), and all heavy
metals detected in plant samples were much greater than those detected in water
samples at same sampling stations; however, all were below the permissible limits.

3.4. Fish analysis


Fish are often used to study their body burdens and the transfer of pollutants in the
food web [61]. They can be good indicators of the bioaccumulation resulting from
the contamination of the environment [61]. In the present study, fifteen fish
samples of three fish species were analyzed for their heavy metals content. This
study was carried out to evaluate the effect of water and sediment pollution on fish
living in Al-Hammar Marsh water. Results show that mean concentrations of
heavy metals was in the order of Fe > Mn > Zn > Ni > Cu > Pb > Co > Cd > Cr
> Hg (Table 8 and Fig. 5), and the concentrations of heavy metals were several
times higher than their concentrations in water samples; this is a clear indication of
bioaccumulation of heavy metals in fish tissues. It appears that Co, Cr, Cu, Fe, and
Hg concentrate in Carassius carassius more than Tilapia zilli and Liza Abu, while
Cd, Mn, Ni, Pb and Zn concentrate in Liza Abu more than Carassius carassius, and
Tilapia zilli. The heavy metals analysis of fish samples shows that Cd and Co
levels exceeded permissible limits in some fish samples, while Mn, Ni, and Pb
concentrations were above the permissible limits in all fish species (Table 8).

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.

20 http://dx.doi.org/10.1016/j.heliyon.2017.e00256
2405-8440/© 2017 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY license
(http://creativecommons.org/licenses/by/4.0/).
Article No~e00256

3- The applied multivariate statistical techniques, such as PCA and AHCA,


identified the possible sources of contaminants in sediments: some solutes are
of anthropogenic sources (mainly fertilizers and petroleum extraction wastes),
and others are from natural sources. Moreover, EF analysis which was used
along with PCA and AHCA to support the element sourcing gave results
compatible with PCA and AHCA findings.
4- Heavy metals detected in plant species were within acceptable limits, however,
heavy metal concentrations in fish samples showed that some fish samples were
contaminated by Cd and Co, and all of them were contaminated by Pb, Mn, and
Ni. This is a clear indication of bioaccumulation and biomagnification of heavy
metals in fish tissues.

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.

Competing interest statement


The authors declare no conflict of interest.

Additional information
No additional information is available for this paper.

References
[1] A. Ghermandi, J.C.J.M. Van den Bergh, L.M. Brander, H.L.F. de Groot, P.A.
L.D. Nunes, The economic value of wetland conservation and creation: A
meta-analysis, 13th Coalition Theory Network Workshop, the Fondazione
Eni Enrico Mattei (FEEM), Venice Italy, 2008 24–25 January.

[2] P. Ten Brink, T. Badura, A. Farmer, D. Russi, The Economics of Ecosystem


and Biodiversity for Water and Wetlands: A Briefing Note, Institute for
European Environmental Policy, London, 2012, pp. 9.

21 http://dx.doi.org/10.1016/j.heliyon.2017.e00256
2405-8440/© 2017 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY license
(http://creativecommons.org/licenses/by/4.0/).
Article No~e00256

[3] C.J. Richardson, P. Reiss, N.A. Hussain, A.J. Alwash, D.J. Pool, The
Restoration Potential of the Mesopotamian Marshes of Iraq, Science 307
(5713) (2005) 1307–1311. http://www.sciencemag.org/.

[4] C.J. Richardson, N.A. Husain, Restoration the Garden of Eden: an ecological
assessment of the Marshes of Iraq, BioScience 56 (6) (2006).

[5] P. Buringh, Soil and Soil Conditions of Iraq, Ministry of Agriculture, D.G.,
Agric. Res. and Projects, Baghdad, Iraq, 1960, pp. 322.

[6] E. Maltby, An Environmental and Ecological Study of the Marshlands of


Mesopotamia Wetland Ecosystem, Research Group, University of Exeter,
London, 1994.

[7] H. Partow, The Mesopotamian Marshlands: Demise of an Ecosystem. Nairobi


(Kenya): Division of Early Warning and Assessment, United Nations
Environment Programme. UNEP publication UNEP/DEWA/TR, 2001,
pp. 1–3.

[8] UNEP, Environment in Iraq: UNEP Progress Report, Geneva, 2003.

[9] M.F. Abdul Jabbar, A.F. Al-Ma'amar, A.T. Shehab, Change detections in
marsh areas, south Iraq, using remote sensing and GIS applications, Iraqi
Bulletin of Geology and Mining 6 (2) (2010) 17–39. http://www.iasj.net/iasj?
func=issues&jId=225&uiLanguage=en.

[10] A. Al-Saboonchi, A.M. Mohamed, A.M. Alobaidy, H.S. Abid, B.K.


Maulood, On the Current and Restoration Conditions of the Southern Iraqi
Marshes: Application of the CCME WQI on East Hammar Marsh, J. Environ.
Prot. 2 (2011) 316–322.

[11] A.C. Al-Shammary, M.F. Al-Ali, K.H. Yonuis, Assessment of Al-Hammar


marsh water by uses Canadian water quality index (WQI), Mesop. Environ. J
1 (2) (2015) 26–34.

[12] UNEP-DTIE-IETC, C, UNEP-UNESCO project and World Heritage


Programme: Project overview, Kick-off meeting, Natural Cultural Manage-
ment of the Iraqi Marshlands as World Heritage, Amman, Jordan, 2009.

[13] APHA, Standard Methods, The Examination of Water and Wastewater,


Twentysecond ed., (2012), pp. 1496.

[14] D. Harvey, Modern Analytical Chemistry, McGraw-Hill, New York, 2000.

[15] J.C. Young, G.N. Mcdermott, D. Jenkins, Alterations in the bod procedure for
the 15th edition of standard methods for the examination of water and
wastewater, J. Water pollut. Control fed. 53 (1981) 1253.

22 http://dx.doi.org/10.1016/j.heliyon.2017.e00256
2405-8440/© 2017 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY license
(http://creativecommons.org/licenses/by/4.0/).
Article No~e00256

[16] J.H. Margeson, W.J. Mitchell, J.C. Suggs, M.R. Midgett, Integrated Sampling
and Analysis Methods for Determining NOX Emissions at Electric Utility
Plants. U.S. Environmental Protection Agency, Research Triangle Park, NC,
J. Air Pollut. Control Assoc. 32 (1982) 1210–1215.

[17] D.C. Harris, Chapter 21, Quantitative Chemical Analysis, Fourth ed., W.H
Freeman and Company, New York, 1995.

[18] R. Raghavan, S. Raha, A rapid turbidimetric method for the determination of


total sulphur in zinc concentrate, Talanta 38 (1991) 525–528.

[19] D.A. Skoog, D.M. West, F.J. Holler, Fundamentals of Analytical Chemistry,
Seventh edi., Thomson Learning, Inc, USA, 1996.

[20] F.A.J. Armstrong, Determination of nitrate in water by ultraviolet


spectrophotometry, Anal. Chem. (1963) 35–1292.

[21] A. Walkley, Acritical examination of a rapid method for determining organic


carbon in soils: Effect of variations in digestion conditions and inorganic soil
constituent, Soil Sci. 63 (4) (1974) 251–264.

[22] B.A. Schumacher, Methods for the determination of total organic carbon
(TOC) in soils and sediments, EPA National Exposure Research Laboratory,
office of Research and Development (ORD), 1-23, 2002.

[23] UNEP/FAO/IAEA/IOC, Sampling of selected marine organisms and sample


preparation for trace metal analysis, Reference method for marine pollution
studies 7 (2) (1984) 19.

[24] S. Caeiro, M.N. Costa, T.B. Ramos, F. Fernandes, N. Silveira, A. Coimbra,


G. Medeiros, M. Painho, Assessing heavy metal contamination in Sado
Estuary sediment: an index analysis approach, Ecol. Indic. 5 (2005) 151–169.

[25] L.P. Zhang, X. Ye, H. Feng, Heavy Metal Contamination in Western Xiamen
Bay Sediments and Its Vicinity China, Mar. Pollut. Bull. 54 (2007) 974–982.

[26] A.P. Vinogradov, The Geochemistry of Rare and Dispersed Chemical


Elements in Soils, Second ed., Consultants Bureau Enterprises, New York,
1959, pp. 209.

[27] L. Hernandez, A. Probst, J.L. Probst, E. Urich, Heavy metal distribution in


some French Forest soils: Evidence for atmospheric contamination, Sci. Total
Environ. 312 (1–3) (2003) 195–219.

[28] F.T. Fong, P.S. Chee, A.A. Mahmood, N.M. Tahir, Possible Source and
Pattern distribution of heavy metals content in urban soil at Terengganu Town
Center, Malaysia, Journal Analysis Science, Malaysian Journal of Analytical
Sciences 12 (2) (2008) 458–467. http://www.ukm.my/mjas/new_mjas.

23 http://dx.doi.org/10.1016/j.heliyon.2017.e00256
2405-8440/© 2017 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY license
(http://creativecommons.org/licenses/by/4.0/).
Article No~e00256

[29] WHO, Guidelines for drinking water quality recommendations, Volume 1,


recommendations, Third ed., World Health Organization, Geneva, 2008,
pp. 51.

[30] E. Al-Heety, A. Turky, E. Al-Othman, Physico-Chemical Assessment of


Euphrates River between Heet and Ramadi Cities: Iraq, J. Water Resource
Prot. 3 (2011) 812–823.

[31] M. Singh, S.K. Singh, Impact of Seasonal Variation on Physicochemical


Parameters of Mansi Ganga, Radha and Shyam Kund, Mathura, Microbiology
4 (8) (2014).

[32] K.O. Joseph, J.P. Srivastava, Heavy Metal Load in Edible Oyster,
Crassoskrea madrasensis (Fres ton) from the Ennore Estuary in Madras, J.
Environ. Biol. 14 (2) (1993) 121–127.

[33] S. Kaur, J. Kaur, Assessment of Seasonal variations in oxygen demanding


parameters (DO, BOD, COD) along Sirhind Canal passing through Moga,
Punjab India, International Journal of Innovative Science, Engineering &
Technology 2 (5) (2015). www.ijiset.com.

[34] C.B. Andersen, G.P. Lewis, K.A. Sargent, Influence of wastewater treatment
effluent on concentrations and fluxes of solutes in the Bush River, South
Carolina, during extreme drought conditions, Environ. Geosci. 11 (1) (2004)
28–41. http://eg.geoscienceworld.org/content/11/1/28.

[35] M.B. Abdullah, Sedimentology, Petrography, Geochemistry and Hydro-


chemistry of the recent sediments of Hor Al- Hammar in Southern Iraq,
College of Science, University of Baghdad (in Arabic), Iraq, 1982, pp. 192
(Unpublished) M. Sc. Thesis.

[36] B.K. Maulood, G.C.F. Hinton, B.A. Whitton, H.A. Al-Saadi, On the Algal
Ecology of the Lowland Iraqi-Marshe, Hydrobiologia 80 (3) (1981) 269–276.

[37] B.K. Maulood, G.C.F. Hinton, H.S. Kamees, F.A.K. Saleh, A.A. Shaban, S.
M.H. AlShahwani, An Ecological Survey of Some Aquatic Ecosystems in
Southern Iraq, Trop. Ecol. 20 (1) (1979) 27–40.

[38] T.I. Qassim, Ecological Study on Benthic Algae of Some Area in Southern
Iraqi Marshes, College of Science, University of Basrah, 1986, pp. 203 M. Sc.
Thesis.

[39] K.M. Banat, F.M. Howari, M.B. Abdullah, Mineralology and Hydrochemical
Characteristics of the Late Marshes and Swamps of Hor Al-Hammar,
Southern Iraq, J. Arid Environ. 65 (2005) 400–419.

24 http://dx.doi.org/10.1016/j.heliyon.2017.e00256
2405-8440/© 2017 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY license
(http://creativecommons.org/licenses/by/4.0/).
Article No~e00256

[40] EPA, Current National Recommended Water Quality Criteria, Environmental


Protection Agency, United States, 2009.

[41] A.A.M. Aqrawi, The nature and preservation of organic matter in the
lacustrine/deltaic sediments of southern Mesopotamia, J. Petrol. Geol. 20
(1997) 69–90.

[42] K.S. Al-Bassam, M.A. Yousif, Geochemical distribution and background


values of some minor and trace elements in Iraqi soils and recent sediments,
Iraqi Bulletin of Geology and Mining 10 (2) (2014) 109–156. http://www.iasj.
net/iasj?func=issues&jId=225&uiLanguage=en.

[43] N.A. Al-Qaraghuli, Contents of nutrient elements (Total, water soluble and
available) in the fertilizers (TSP, MAP, NP & NPK) produced from Al-Qaim
plant, Iraq, Iraqi J. Agr. Sci. 36 (5) (2005) 35–41. http://www.iasj.net/iasj?
func=issues&jId=4&uiLanguage=en.

[44] A. Kabata-Pendias, Trace Elements in Soils and Plants, Fourth ed., CRC
Press, Boca Raton, FL, 2011, pp. 505.

[45] K. Khwedim, H. Al-Anssari, K. Al-Bassam, Study of Distribution of Some


Heavy Metals in The Soil of Basra City- South Of Iraq, Iraqi Journal of
Science 50 (4) (2009) 533–542.

[46] S. Fiedler, C. Siebe, A. Herre, B. Roth, S. Cram, K. Stahr, Contribution of Oil


Industry Activities to Environmental Loads of Heavy Metals in the Tabasco
Lowlands, Mexico, Water Air Soil Pollut. 197 (2009) 35.

[47] J. Rieuwerts, The Elements of Environmental Pollution, Routledge,


New York, 2015, 711 Third Avenue, NY 10017.

[48] A. Chandrasekaran, R. Ravisankar, N. Harikrishnan, K.K. Satapathy, M.V.R.


Prasad, K.V. Kanagasabapathy, Multivariate statistical analysis of heavy
metal concentration in soils of Yelagiri Hills Tamilnadu. India Spectro-
scopical approach, Spectrochim. Acta A: Mol. Biomol. Spectrosc. 137 (2014)
589–600.

[49] I.T. Jolliffe, Principal Component Analysis Series, Second ed., Springer
Series in Statistics, 2002, pp. 488.

[50] I.V. Nair, K. Singh, M. Arumugam, K. Gangadhar, D. Clarson, Trace metal


quality of Meenachil River at Kottayam, Kerala (India) by principal
component analysis, World Appl. Sci. J. 9 (10) (2010) 1100–1107. https://
www.idosi.org/wasj/wasj.htm.

[51] E.R. Weiner, Applications of Environmental Aquatic Chemistry A Practical


Guide, Second ed., CRC Press: Taylor & Francis Group, USA, 2008.

25 http://dx.doi.org/10.1016/j.heliyon.2017.e00256
2405-8440/© 2017 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY license
(http://creativecommons.org/licenses/by/4.0/).
Article No~e00256

[52] H. Yongming, D. Peixuan, C. Junji, E.S. Posmentier, Multivariate analysis of


heavy metal contamination in urban dusts of Xian, Central China, Sci. Total
Environ. 355 (1-3) (2006) 176–186.

[53] B. Mason, C.B. Moore, Principle of Geochemistry, Fourth ed., Wiley, New
York, 1982, pp. 46–177.

[54] R. Mikkelsen, Soil and Fertilizer Magnesium, Better Crops 94 (2) (2010)
26–28. http://nap.ipni.net/article/NAP-3062.

[55] EPA, Current National Recommended Water Quality Criteria, Environmental


Protection Agency, United States, 1999.

[56] C.W. Montgomery, Environmental Geology, Seventh ed., McGraw Hill


Companies Inc., Boston, 2006, pp. 346.

[57] P.S. Hooda, Trace Elements in Soils, John Wiley & Sons Ltd, London, 2010,
pp. 596.

[58] I. Pepper, C. Gerba, M. Brusseau, Environmental and pollution science,


Second ed., Elsevier Academic Press, 628, 2006.

[59] M.A. Cunningham, B.W. Saigo, W.P. Cunningham, Environmental Science:


A Global Concern, Ninth ed., (2007), pp. 620.

[60] A. Kloke, D.R. Sauerbeck, H. Vetter, The contamination of plants and soils
with heavy metals and the transport of metals in terrestrial food chains, in
Changing Metal Cycles and Human Health, In: J.O. Nriagu (Ed.), Springer-
Verlag, Dahlem, Berlin, 2017, pp. 113–141, Konferenzen.

[61] P.S. Rainbow, C. Amiard-Triquet, Environmental Assessment of Estuarine


Ecosystems: a case study, CRC Press, Taylor & Francis Group, 2009,
pp. 355.

[62] FAO, Compilation of legal limits for hazardous substances in fish and fishery
products, FAO Fish Circ. No. 464, Food and Agriculture Organization, 1983,
pp. 5–100.

[63] M. Turkmen, A. Turkmen, Y. Tepe, Metal contaminations in five fish species


from black, Marmara, Aegan and Mediterranean Seas, J. Chil. Chem. Soc. 53
(1) (2008).

[64] FEPA, Guidelines to standard for Environment Pollution Control in Nigeria,


Federal Environment Protection Agency, Lagos, Nigeria, 1991.

26 http://dx.doi.org/10.1016/j.heliyon.2017.e00256
2405-8440/© 2017 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY license
(http://creativecommons.org/licenses/by/4.0/).

You might also like