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Application of geoaccumulation index and enrichment factor for

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Reserve, Iran

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 Geoaccumulation index and enrichment factor assess metal contamination

Chemical Speciation and Bioavailability (2014), 26(2) 99

Application of geoaccumulation index and enrichment

factor for assessing metal contamination in the
sediments of Hara Biosphere Reserve, Iran
Mohsen Nowrouzi* and Alireza Pourkhabbaz
Department of Environmental Sciences, Faculty of Agriculture, University of Birjand, Iran
*E-mail: [email protected]

ABSTRACT

Surface sediments from the Hara Biosphere Reserve of the Persian Gulf were collected to evaluate the contamination of
metals including Pb, Cd, Ni and Fe. The sediment samples were subjected to a total digestion technique and analysed
by atomic absorption spectrometer for metals including Pb, Cd, Ni and Fe. The concentration of heavy metals in the
surface sediments was determined in grain size fractions, 2–1, 1–0.25, 0.25–0.063 and <0.063 mm. The highest mean
concentration of heavy metals was observed in the <0.063 mm fraction and decreased with increasing size fraction, also
metal concentrations in the 0.063 mm fraction represented the next decreasing order Fe>Ni>Pb>Cd. Cd had a higher
enrichment factor than the other metals, and the Igeo value for Cd in the most stations was classified as uncontaminated to
moderately contaminated and moderately to strongly contaminated. This, combined with the average of Igeo of Cd as 1.36 ±
0.22, suggested that surface sediments of Hara Biosphere Reserve were moderately polluted by this metal. The results also
showed that industrial activities around Hara Biosphere Reserve were the most important agents for releasing heavy metals
in the area under study. Pearson correlation indicated that there were significant positive associations between Cd–Pb
(r=0.523, P< 0.01) in the <0.063 mm fraction.

Keywords: metals, pollution load index, industrial activity, mangrove ecosystem, Persian Gulf

INTRODUCTION Sediments serve as a pool of metals that could be released

to the overlying water from natural and anthropogenic
Mangroves are woody plants growing at the interface processes such as bioturbation and dredging, resulting in
between land and sea in tropical and subtropical latitudes potential adverse health effects (Kim et al., 2009). Also the
(Kathiresan and Bingham, 2001). Mangroves ecosystems presence of heavy metals in sediments is affected by the
are among the most productive coastal ecosystems in the particle size of the sediments. This trend is predominantly
world. They are confined to the tropics and subtropics, attributed to sorption, co-precipitation and complexing of
which dominate approximately 75% of the world’s coastline metals on particle surfaces and coatings (Sakai et al., 1986;
between 25° N and 25° S and are estimated to cover an area of Krishna and Mohan, 2013).
1.7 to 2.0×105 km2 (Ranjan et al., 2008). Mangrove wetlands Heavy metals have great ecological significance due to
provide a good nursery ground for a number of commercially their toxicity and tendency to accumulate in both sediment
important aquatic organisms (Raman et al. 2007). They are and biota. These elements are not biodegradable and undergo
also important to humans for a variety of reasons, including a global ecological cycle (Ahmadipour et al., 2014). Metals
aquaculture, agriculture, forestry, protection against shoreline like copper, zinc and nickel are essential metals since they
erosion, as a source of firewood and building material, and play an important role in biological systems, while some
other local subsistence use (Walters et al. 2008). Because others such as cadmium and lead are non essential metals;
of their proximity to population centres and industrialised as they have no known role in biological systems (Norouzi
regions, mangrove habitats have often received inputs of et al., 2012). Pb and Cd are relatively rare metals and no
heavy metals, and the sediments may show significant metal essential biological functions and are highly toxic to plants
contamination (Tam and Yao, 1998). and animals (Mohammadnabizadeh et al., 2012; Nogueirol

Doi: 10.3184/095422914X13951584546986
www.chemspecbio.co.uk
100 Geoaccumulation index and enrichment factor assess metal contamination

and Alleoni, 2013). Ni is one of the most oil components have taken place, as well as oil transportation, commercial
and it can demonstrate oil pollution in the Hara Biosphere ship and recreational boat traffic in the study area, which all
Reserve. Also Fe has been used as a conservative tracer to produce and release substantial amount of contaminants such
differentiate natural from anthropogenic components (Schiff as heavy metals into the study area.
and Weisberg, 1999; Baptista Neto et al., 2000; Ghrefat et
al., 2011).
The main objectives of the current study are: (1) to assess Sediments sampling and analysis
the extent and degree of metals, and the origin of these metals,
Surface sediment samples were collected from nine sites in
using the enrichment factor and the geoaccumulation index
three replicates using a garb sampler based on ecological
of the metals; and (2) to estimate the potential availability
conditions and human activities in the Hara Biosphere
of metals contained in grain size fractions of the surface
Reserve in the summer of 2010 (Figure 1) and placed in clean
sediments.
plastic bags and kept frozen prior to analysis. The samples
were transported to the laboratory, dried to constant weight at
MATERIAL AND METHODS 80°C (Ismail, 1993) and sieved through a stainless steel sieve
into four grain size (<0.063, 0.063–0.25, 0.25–1 and 1–2 mm)
Study area for studying the effects of sediments size on metals uptake
(Zöllmer and Irion, 1993; Calmano and Wellerhaus, 1982).
Hara Biosphere Reserve in the southern Hormozgan To avoid possible contamination, all glassware and equipment
province comprising 85,686 ha is located in the middle of used were acid washed. The analysis of metals in the solutions
the Mehran and Gourzin river deltas between Bandar Khamir was carried out by a graphite furnace atomic absorption
and Queshm Island. The Hara Biosphere contains a 100,000 spectrometer (model AA3030 PerkinElmer, Germany). The
ha international wetland and lies at 26°45’ to 26°58’N and detection limits of Pb, Cd, Ni and Fe were 0.002, 0.009, and
55°30’ to 55°50’E of the Persian Gulf (Figure 1). The variety 0.010 μg g-1, respectively. The accuracy of the analytical
of the biosphere with its unique mangrove trees provides a procedures for total metal determinations was checked using
diverse habitat for birds like egrets, herons, pelicans, and CRM 320 (sediment reference material). Replicate analysis
plovers. It also provides a breeding and spawning habitat for of this CRM showed good accuracy, with recovery rates for
fish, shrimp and other crustaceans. During the last decades, metals between 94 and 103%.The recovery rates for heavy
construction and development of highly polluting industries metals in the standard reference material were between 97 and
such as refineries, the lead and zinc Queshm factory, the Al- 108%. In order to determine the precision of the analytical
Mahdi aluminum factory and the Hormozgan cement factory processes, three samples were analysed in triplicate. The

C2

C3
C5
C1
Industries located in the study area C4
C1 Khamir Cement Factory
C2 Industrial special zone port complex C6
C3 Laft Port C7
C4 Gorzin village C8
C5 Gorzin Gas refinery
C6 Soheili harbour
C7 Tabl harbour
C8 Goran village

Figure 1 Map of the sampling sites in the Hara Biosphere Reserve of Southern Iran.
 Mohsen Nowrouzi and Alireza Pourkhabbaz 101

average values of the variation coefficients obtained (in this study (Table 1). According to Zhang and Liu (2002), EF
general, less than 10%) can be considered satisfactory for values between 0.5 and 1.5 indicate the metal is entirely from
environmental analysis. About 1g of each dried sample was crustal materials or natural processes, whereas EF values
weighted and digested in a concentration composed of nitric greater than 1.5 suggest that the sources are more likely to be
acid 69% and percholoric acid 60% in the ratio of 4:1 first at anthropogenic.
a low temperature 40 °C for 1 h. Then, the temperature was Geochemical index (Igeo) was originally stated by Muller
increased to 140 °C for at least 3 h (Ismail, 1993).The digested (1969) in order to determine and define metal contamination
samples were diluted to an exact volume with double distilled in sediments by comparing current concentrations with pre-
water (DDW) and filtered using a 0.45-μm nitrocellulose
industrial levels, Igeo is calculated as follows:
membrane filter. After filtration, metal concentrations were
determined in the prepared samples.
Igeo = log2 [Cn/1.5Bn] (2)
The environmental impact of metals and the pollution
level in the sediments can be determined with the help of two where Cn is the measured concentration in the sediment
parameters; the enrichment ratio (ER) and geoaccumulation for the metal n, Bn is the background value for the metal n
index (Igeo). The enrichment factor (EF), due to its universal (Turekian and Wedepohl, 1961), and the factor 1.5 is used
formula, is a relatively simple and easy tool for assessing
because of possible variations of the background data due to
the enrichment degree and comparing the contamination of
lithological variations. The quantity Igeo is calculated using
different environmental media (Benhaddya and Hadjel, 2013).
the global average shale data from Turekian and Wedepohl
The ER is a normalisation method proposed by Simex and Helz
(1961). In this study, we used the EF and Igeo index using Fe
(1981) to assess the concentration of the metals. It normalises
and grain fraction <0.063 mm according to González-Macías
metal concentration as a ratio to another constituent of the
et al. (2006). Muller determined the descriptive classes for
sediments. Rubio et al. (2000) stated that there is no consensus
increasing Igeo values (Muller, 1969) which are given in Table
about the most appropriate sediment constituent to be used
2. Pearson’s correlation coefficients (r) were used to calculate
for normalisation. Among those used have been Al, Fe, total
correlations between concentrations of heavy metals in the
organic carbon, and grain size. The constituent chosen for
sediment. To determine the significant differences at different
this purpose should also be associated with finer particles
sampling sites, a one-way analysis of variance (ANOVA),
(related to grain size) and its concentration should not be
anthropogenically altered (Ackerman, 1980). Therefore, in the Tukey’s honest significant difference test was employed,
present study, it has chosen to normalise metal concentrations because of normalisation of the data. All statistical analyses
using Fe. The EF is defined as follows (Ergin et al., 1991): were computed by using Package for Social Science (SPSS)
𝑀𝑀 version 16.
(𝐹𝐹𝐹𝐹 )𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆 (1)
EF = 𝑀𝑀
( )𝐵𝐵𝐵𝐵𝐵𝐵𝐵𝐵𝐵𝐵𝐵𝐵𝐵𝐵𝐵𝐵𝐵𝐵𝐵𝐵
𝐹𝐹𝐹𝐹
RESULTS AND DISCUSSION
where (M/Fe) Sample is the ratio of metal and Fe concentrations
in the sample, and (M/Fe) Background is the ratio of metal and Fe Metal concentrations in four grain size fraction sediments
concentrations of the background. The world average shale from nine sites are shown in Figure 2. The highest mean
and the world average soil are among the materials often used concentration of Pb, Cd, Ni and Fe were observed in the 0.063
to provide background metal levels. Thus, the background mm fraction and measured at site 6 (45.16 μg g−1), 3 (5.17 μg
concentrations of Pb, Cd, Ni, and Fe in the average shale g−1), 1 (108.44 μg g−1) and 7 (52346.23 μg g−1). Therefore,
obtained from Turekian and Wedepohl (1961) are used in the mean concentrations of metals in the 0.063 mm fraction
Table 1 Means and SD of metal concentrations in the Hara Biosphere Reserve compared to average shale (μg g−1) and other parts of the Persian Gulf
Pb Cd Ni Fe Reference
Persian Gulf, Hara Biosphere Reserve
36.65±7.32 3.54±0.51 79.86±17.11 46261±2124 This study
(0.063 mm grained sediment)
Persian Gulf, Khor Ahmadi 2.59 0.64 51.22 – Safahieh et al. (2011)
Persian Gulf, Khor Gazale 4.70 0.49 64.89 – Safahieh et al. (2011)
Persian Gulf, Khor Ghanam 2.14 0.42 18.96 – Safahieh et al. (2011)
North Persian Gulf 344 4.38 37.4 – Pourang et al. (2005)
Persian Gulf, Qatar 3.16 0.08 20.8 – De Morsa et al. (2004)
Persian Gulf,Bahrain 99 0.18 23.2 – De Morsa et al. (2004)
Persian Gulf, Qaruh Island 1.03 0.77 15.00 2792 Price et al. (1994)
Persian Gulf, Al Malikiyah 0.64 0.21 19.60 4811 Price et al. (1994)
Persian Gulf, Ras Al Khafji 1.70 0.14 13.80 5454 Price et al. (1994)
Average shale 20 0.3 68 47,000 Turekian and Wedepoh (1961)
102 Geoaccumulation index and enrichment factor assess metal contamination

Table 2 Contamination categories based on geoaccumulation index (Igeo) and enrichment factor (EF)
Geoaccumulation index Enrichment factor
Class Value Classification Level Value Categorisation
0 <0 Uncontaminated I EF<1 No enrichment
1 0–1 Uncontaminated to moderately contaminated II EF=1–3 Minor enrichment
2 1–2 Moderately contaminated III EF=3–5 Moderate enrichment
3 2–3 Moderately to strongly contaminated IV EF=5–10 Moderately severe enrichment
4 3–4 Strongly contaminated V EF=10–25 Severe enrichment
5 4–5 Strongly to extremely strongly contaminated VI EF=25–50 Very severe enrichment
6 >5 Extremely contaminated VII EF>50 Extremely severe enrichment

Figure 2 Heavy metal concentrations (μg g−1) in four grain size fraction sediments from nine stations in the Hara Biosphere Reserve
(mean ± SD).

size were compared with the results from other studies. The Cd and Ni in the Hara Biosphere Reserve. In contrast, the
mean concentration of total metals were in descending order: locations studied had Fe concentrations less than those for
smaller than 0.063>0.063–0.25>0.25–1>1–2 and in 0.063 mm average shale, which indicates that there are no major sources
fraction represented the next decreasing order Fe>Ni>Pb>Cd. of pollution for Fe in the study area (Ghrefat et al., 2011).
Observed metal contents in the surface sediments of the Hara According to Bowen (1979), the levels of Fe, Ni, Pb, and Cd
Biosphere Reserve are compared with similar studies in the in uncontaminated sediments and soils are 26,000, 19, 19 and
other parts of Persian Gulf in Table 1. The results showed 0.35 ppm respectively.
that the levels of Pb, Cd and Ni in Hara Biosphere Reserve Inter-element relationships in sediment provide
were higher than those in Khor Ahmadi, Khor Gazale, Khor information on metal sources and pathways in the
Ghanam (Safahieh et al., 2011), coastal sediments of Qatar geoenvironment (Dragovi et al., 2008). According to the
(De Morsa et al., 2004) and Qaruh Island (Price et al., values of Pearson correlation coefficient for Pb, Cd, Ni and
1994), as well as Fe concentration in this study was higher Fe in the four grain fraction sediments of the Hara Biosphere
than those in coastal sediments Qaruh Island, Al Malikiyah Reserve, there was a positive correlation between Cd–Pb
and Ras Al Khafji in the Persian Gulf (Price et al., 1994). A in <0.063 mm grain sediment (r=0.523, P< 0.01), Ni–Pb
comparison of the mean metal concentrations in the 0.063- in 0.063–0.25 mm grain sediment (r=0.732, P< 0.01), and
mm fraction surface sediments with the corresponding values Cd–Pb in 0.25–1 mm grain sediment (r=0.417, P< 0.05).
of these metals in the average shale (Turekian and Wedepohl, The significantly positive correlation indicates that the
1961) reveals that surface sediments are polluted with Pb, elements were derived from similar sources and also moving
 Mohsen Nowrouzi and Alireza Pourkhabbaz 103

together (Bhuiyan et al., 2009), also there was no significant indicate that Pb has minor to moderate enrichment and Ni
correlation between Fe with other metals and it suggested has minor enrichment. Generally, the stations which are
that Pb, Cd and Ni were not strongly controlled by natural located closer to the different industries have a higher EF. The
weathering processes in the study area (Zhang et al., 2009). difference in EF values for the different metals in the surface
Comparison between sampling sites using one-way analysis sediments may be due to the difference in the magnitude of
of variance are presented in Table 3. The extent of metals input input for each metal in the sediment and/or the difference in
and the physico-chemical characteristics of sediment could the removal rate of each metal from the sediment (Ghrefat et
have a core role in the inter-sites accumulation of the heavy al., 2011). The EF results in the other regions exhibit different
metals (Zhang et al., 2009; Sohrabi et al., 2010). There were degrees of metals enrichment. The values of EF in the Hara
no decreasing nor increasing trends for metal concentrations Biosphere Reserve were similar those found by Ghrefat et
among the stations. It may be due to their inherent physical and al. (2011) and were higher than the EF in the Wadi Al-Arab
chemical properties, mangrove muds have an extraordinary Sediment (Ghrefat and Yusuf, 2006). The Seyhan sediments
capacity to accumulate materials discharged to the near shore are treated as having a moderately severe enrichment of Cd
marine environment (Harbison, 1986). Also most factories (Cevik et al., 2009) and the sediments of the Ziqlab Dam
which located around the Hara Biosphere Reserve such as Al- are enriched with Pb and Cd by 1.07 and 2.16 respectively,
Mahdi aluminium factory, lead and zinc Queshm factory and while Ni is depleted in the sediments (Abu-Rukah, 2001). EF
Hormozgan Cement factory were discharged to the Persian values greater than 1 suggest that the sources are more likely
Gulf and the Hara Biosphere Reserve directly, without any to be anthropogenic (Ghrefat et al., 2011).
remediation; only a simple physical screening was being The geoaccumulation index results indicate that the
performed; It consisted of lots of toxic metals like Pb, Cd, surface sediments were uncontaminated to moderately
Ni, Vn and Cr. As well as oil tankers, commercial ship and contaminated with respect to Pb. The Igeo values for Cd in most
recreational boat traffic within the study area released large stations are high which can be classified as uncontaminated
amounts of Pb, Cd and Ni-containing compounds into the to moderately contaminated and moderately to strongly
water and sediments (Nowrouzi et al. 2012); so this area contaminated, and the average of the geoaccumulation index
contains many sources of pollution at each station. of Cd suggested that surface sediments of Hara Biosphere
The resulting EF values demonstrate that Pb, Cd and Ni Reserve were moderately polluted by this metal, whereas
are enriched in the surface sediments of the Hara Biosphere the average of the geoaccumulation indexes of Ni were
Reserve (Table 4). The EF values for Cd are the highest among uncontaminated by this metal (Table 4). The contents of Pb
the metals and it has a heavy enrichment. The EF values also and Cd increase as a result of some anthropogenic activities

Table 3 Analysis of variance (ANOVA) of Cd, Ni, Pb, and Fe concentration in sediment at nine sampling sites
Sediment Pb Cd Ni Fe
(mm) F value P value F value P value F value P value F value P value
<0.063 120.48 NS 1.01 NS 1906.58 <0.01 43271 <0.05
0.063–0.25 61.20 <0.01 0.80 <0.01 1354.99 <0.01 36512 <0.01
0.25–1 48.71 <0.01 0.50 <0.01 1107.80 <0.01 29874 <0.01
1–2 34.12 <0.05 0.22 NS 942.21 <0. 01 25361 NS

P, significance level; NS, not significant

Table 4 EF and Igeo values for sediments from the Hara Biosphere Reserve
Pb Cd Ni
No Station
Igeo EF Igeo EF Igeo EF
C1 Saline River 0.26 1.93 0.95 14.07 0.22 2.20
C2 Persian Gulf Bridge 0.18 1.71 0.77 13.38 –0.33 1.20
C3 Opposite of Khoran Strait 0.14 1.82 2.05 22.27 –0.14 1.92
C4 Opposite of Laft Port 0.39 2.97 1.57 17.63 –0.37 1.75
C5 Gorzin 0.34 3.54 0.86 13.14 –1.47 1.17
C6 Khamir Port 0.49 4.13 1.82 21.38 –0.29 1.47
C7 Tar e Khoran 0.40 3.75 1.91 20.85 –0.43 1.99
C8 Opposite of Goran Port 0.28 2.33 1.22 14.32 –0.47 1.38
C9 Opposite of Larak island 0.08 2.11 1.08 15.16 –0.39 1.52
Mean 0.28 2.70 1.36 16.91 –0.41 1.62
Min 0.08 1.71 0.77 13.14 –1.47 1.17
Max 0.49 4.13 2.05 22.27 0.22 2.20
SD – 0.90 – 5.64 – 0.54
104 Geoaccumulation index and enrichment factor assess metal contamination

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