Marine Pollution Bulletin 111 (2016) 456462

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Marine Pollution Bulletin

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Baseline

Seasonal distribution and geochemical fractionation of heavy metals from

surface sediment in a tropical estuary of Jeneberang River, Indonesia
Najamuddin a,, Tri Prartono b, Harpasis S. Sanusi b, I Wayan Nurjaya b
a
b

Marine Science Study Program, Khairun University, Ternate 97719, Indonesia

Department of Marine Science and Technology, Bogor Agricultural University, Bogor 16680, Indonesia

a r t i c l e

i n f o

Article history:
Received 2 February 2016
Received in revised form 19 June 2016
Accepted 28 June 2016
Available online 4 July 2016
Keywords:
Pb and Zn
Geochemical fractionation
Sediment
Jeneberang River estuary

a b s t r a c t
Lead (Pb) and zinc (Zn) concentrations from surface sediments were determined at 17 stations in riverine, estuarine, and marine environments during the wet and dry seasons. The geochemical fractionations were obtained
by a sequential extraction procedure in ve geochemical forms: exchangeable, bound to carbonate, ironmanganese oxide, organic, and residual fractions. The concentrations of Pb and Zn in the water were higher during the
wet season than the dry season and higher in the riverine and marine samples than the estuarine samples. Following geochemical fractionation, the metals were found mainly in the residual fraction. The results indicated
that the concentrations were inuenced by season, with the sources of Pb and Zn derived mainly from rivers
and natural sources. The contamination status in the estuary of the Jeneberang River was classied as weak to
moderate pollution and the risk level to aquatic biota attributed was no risk to low risk.
2016 Elsevier Ltd. All rights reserved.

Heavy metals are derived from natural and anthropogenic

sources. In most cases, heavy metals of anthropogenic origin are released from urban and industrial areas adjacent to rivers and estuaries. Heavy metal contamination in the coastal marine environment
has become a serious problem in Asian coastal megacities as they undergo rapid economic growth and industrialization (Jiang et al.,
2015). Makassar, as the largest city in eastern Indonesia, is undergoing rapid economic growth and industrialization. The Jeneberang
River ows through Makassar City, including the upstream area in
the Bawakaraeng Mountains, Gowa district and the downstream
area in the Makassar Strait. The Jeneberang River ows through village and city regions and therefore has the potential for contamination by various metals from agricultural, domestic, and
transportation sources. There is also potential intake of metals from
marine sources such as the Makassar international seaport, ship
docking and manufacturing, hospital, and industrial sectors
(Samawi, 2007; Taueq, 2010, Werorilangi et al., 2013).
Heavy metals in river water are a concern due to their persistence in
the environment, bioaccumulation, and high levels of toxicity (Hu et al.,
2013; Wang et al., 2015). Assessment of heavy metal concentrations in
sediment are useful to determine pollution levels in estuarine and marine environments and to provide basic information for determination
of environmental health risks (Hu et al., 2013). In sediments, heavy

Corresponding author.
E-mail address: najamuddin313@gmail.com (Najamuddin).

http://dx.doi.org/10.1016/j.marpolbul.2016.06.106
0025-326X/ 2016 Elsevier Ltd. All rights reserved.

metals can exist in various chemical forms, which exhibit different

physical and chemical behaviors with respect to their chemical interactions, mobility, biological availability, and potential toxicity (He et al.,
2009). Heavy metals interact with sediment matrices and exhibit different binding mechanisms with carbonates, iron (Fe) manganese (Mn)
oxides, organic matter, and the lattices of refractory crystalline minerals
such as silicates (Gao and Li, 2012). Determination of the geochemical
fractionation of heavy metals in sediments is important to assess their
potential toxicity, threat to the ecosystem, and source (natural processes or anthropogenic sources). The accumulation of heavy metals in the
resistant fraction is an indication that they originate from natural processes, while accumulation in the non-resistant fraction indicates they
originate from anthropogenic sources (Liu et al., 2015).
Several studies on the distribution and geochemical fractionation of
heavy metals in sediment have been published (Armid et al., 2014;
Takarina et al., 2004); however, limited information is available due to
seasonal effects. The concentrations of heavy metals during all four seasons have been reported in the Gulf of Aqaba, Jordan (Al-Najjar et al.,
2008), southeast coast of the Caspian Sea (Bastami et al., 2015), and Yellow Sea (Jiang et al., 2015); however, these locations are not tropical.
A seasonal study is needed, because the seasons differentially inuence the physico-chemical parameters within the environment. Changes in environmental conditions, such as pH, temperature, and redox
potential (Eh), could inuence metal release from the solid to liquid
phases that transformed sediments from the metal main sink to the
sources for the overlying waters (Wang et al., 2015).

Najamuddin et al. / Marine Pollution Bulletin 111 (2016) 456462

The objectives of this study were to investigate the distribution and

geochemical fractionation of heavy metals in surface sediments during
different seasons (wet and dry) to identify the possible sources of
heavy metals and to assess the pollution levels and ecological risks associated with lead (Pb) and zinc (Zn).
A total of 17 surface sediment samples were collected from riverine,
estuarine, and marine waters during January and August 2015, which
represent the wet and dry seasons, respectively. The riverine water
zone contained sampling stations R1R3, the estuarine zone contained
sampling stations E1E7, and the coastal (marine) zone contained sampling stations CS1CS7. Sample locations were determined by a global
positioning system (Fig. 1). The surface sediments were sampled using
an Ekman grab sampler. At each sampling site, the top 010 cm of sediment were collected using a plastic spatula, and each sample was
packed in a new polyethylene zipper bag. After collection, the samples
were stored and transported to the laboratory in a cooler box with ice
packs and then stored in a fridge at 4 C prior to analysis. In the laboratory, samples were rst sieved through a 2 mm nylon sieve to remove
coarse debris and shell fragments, ground using an agate mortar and
pestle in a fume cupboard, and then sieved through a 0.5 mm sieve to
remove large particles and homogenize the mixture.
The geochemical fraction of heavy metals was determined using sequential extraction procedure (Tessier et al., 1979). This method provides the exchangeable, bound to carbonates, bound to Fe\\Mn
oxides, bound to organic matter and residual fractions with the following procedures;
i. Exchangeable (F1). The sediment was extracted at room temperature for 1 h with 8 mL of either magnesium chloride solution (1 M
MgCl2, pH 7.0) or sodium acetate solution (1 M NaOAc, pH 8.2)
with continuous agitation.
ii. Bound to carbonates (F2). The residue from (i) was leached at room
temperature with 8 mL of 1 M NaOAc adjusted to pH 5.0 with acetic

457

acid (HOAc). Continuous agitation was maintained and the time

necessary for complete extraction was evaluated.
iii. Bound to Fe\\Mn oxides (F3). The residue from (ii) was extracted
with 20 mL of either 0.3 M Na2S2O4 + 0.175 M Na-citrate
+ 0.025 M H-citrate or 0.04 M NH2OH\\HCl in 25% (v/v) HOAc.
The latter experiments were performed at 96 3 C with occasional
agitation and the time needed for complete dissolution of the free
iron oxides was evaluated.
iv. Bound to organic matter (F4). The residues from (iii) were added
3 mL of 0.02 M HNO3 and 5 mL of 30% H2O2 adjusted to pH 2 with
HNO3, and the mixture was heated to 85 2 C for 2 h with occasional agitation. A second 3-mL aliquot of 30% H2O2 (pH 2 with
HNO3) was then added and the sample was heated again to 85
2 C for 3 h with intermittent agitation. After cooling, 5 mL of
3.2 M NH4OAc in 20% (v/v) HNO3 was added and the sample was diluted to 20 mL and agitated continuously for 30 min. The addition of
NH4OAc is designed to prevent adsorption of extracted metals onto
the oxidized sediment.
v. Residual (F5). The residue from (iv) was digested with a HF\\HClO4
mixture according to the procedure described below for total metal
analysis.

The selective extractions were conducted in centrifuge tubes

(polypropylene, 50 mL) to minimize losses of solid material. Between
each successive extraction, separation was effected by centrifuging at
10,000 rpm (12,000 g) for 30 min. The supernatant was removed with
a pipet and analyzed for trace metals, whereas the residue was washed
with 8 mL of deionized water; after centrifugation for 30 min, this second supernatant was discarded. The volume of rinse water used was
kept to a minimum to avoid excessive solubilization of solid material,
particularly organic matter. Deionized water used in preparing stock solutions and in each step of the leaching procedure was obtained from a

Fig. 1. Location of sample sites.

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Najamuddin et al. / Marine Pollution Bulletin 111 (2016) 456462

Millipore Milli-Q3RO/Milli-Q2 system. All glassware used for the experiments was previously soaked in 14% HNO3 (v/v) and rinsed with deionized water.
For total or residual metal analysis, the solid was digested with a 5:l
mixture of hydrouoric and perchloric acids. For a 1-g (dry weight)
sample, the sediment was rst digested in a platinum crucible with a solution of concentrated HClO4 (2 mL) and HF (10 mL) to near dryness;
subsequently a second addition of HClO4 (1 mL) and HF (10 mL) was
made and again the mixture was evaporated to near dryness. Finally,
HC104 (1 mL) alone was added and the sample was evaporated until
the appearance of white fumes. The residue was dissolved in 12 N HCl
and diluted to 25 mL. All of the above metal-containing solutions were
subsequently analyzed by graphite furnace atomic absorption spectrometry (Shimudzu-AA 7000).
In order to guarantee the analytical data quality, laboratory quality
control and quality assurance were implemented by utilizing standard
operating procedures, calibration with standards, analysis of reagent
blanks, recovery of spiked samples and analysis of replicates. The precision and accuracy of the analytical procedures were checked by recovery
tests on spiked sediment samples. Adopted analytical procedures indicated 91% to 110% recoveries of the spiked metals and marine sediment reference material (NMIJ CRM 7302-a) were achieved from the tested
samples, which agreed with certied values. The average differences between the certied and measured results were within 11% variability.
Background correction and matrix interference were monitored through
the analysis calibration checks. All analyses were duplicated to ensure the
representativeness of the quantitative results, and the ultimate results
were expressed as the mean and standard deviation. All reagents used
in the experiment were analytical-reagent grade or better. All glassware
and plastic were pre-cleaned by soaking in 10% HNO3 (v/v) for overnight.
The texture of dry sediment samples was analyzed using a pipet procedure (after passing through a 63 m sieve). Grain sizes from 2000 m
to 62.5 m were classied as sand, those from 62.5 m to 3.9 m as silt,
and those b3.9 m as clay. The organic carbon (OC) content was analyzed using the Walkley-Black procedure and expressed as a weight
percentage following sample combustion in a Loss on Ignition test.
The suspended particulate matter (SPM) was measured using a gravimetric procedure, and the Eh of the sediment was measured using a
portable Eh meter. The sediment texture (clay, silt, and sand), OC, Eh,
and SPM properties are shown in Table 1.
Assessment of heavy metals pollution was analyzed by
geoaccumulation index and risk assessment code. The geoaccumulation
index (Igeo) is expressed as the following equation (Mller, 1969):
Igeo log2 Cn =1; 5 Bn

where Cn is the measured concentration of metal n in the sediment, and

Bn is the geochemical background value of the metal n. Factor 1.5 compensates for possible uctuations in the background values for a given
substance in the environment, as well as very small anthropogenic inuences. Mller dened seven classes in the geoaccumulation index:
Igeo 0 is class 0 (unpolluted);
0 b Igeo 1 is class 1 (weakly polluted);
1 b Igeo 2 is class 2 (moderately polluted);
2 b Igeo 3 is class 3 (moderately to strongly polluted);
3 b Igeo 4 is class 4 (strongly polluted);
4 b Igeo 5 is class 5 (strongly to extremely polluted);
Igeo N 5 is class 6 and extremely polluted.
Risk Assessment Code (RAC) is an assessment index of the risk of
heavy metal existence on the aquatic environment based on the geochemical fraction of heavy metal interaction with sediment particle
which is potentially absorbed by the organisms. Risk assessment index
was obtained by calculating the percentage of exchangeable and carbonate fraction in sediment (Honglei et al., 2008; Sundaray et al.,
2011). The index can be dened in ve classes:
RAC b 1 (not risky);
1 b RAC 10 (light risk);
11 b RAC 30 (medium risk);
31 b RAC 50 (high risk);
RAC N 50 (very high risk).
Sediment texture was dominated by sand in the river and estuary
zone, but in the marine zone it was dominated by clay. There was a
high water ow in the river and estuary from the upstream region, especially during the wet season, which led to turbulence in the estuary,
where larger particles (e.g., sand) deposited on the bottom. The SPM
and OC concentrations and Eh were higher during the wet season
than the dry season. The strong ow of water mass during the wet season provided a large oxygen supply to the sediments, and the Eh tended
to increase. The increasing concentration of SPM in the water column
was inuenced by the high levels of erosion and water runoff during
the wet season. SPM binds to organic matter, and with greater levels
of erosion, the OC concentration in sediments increases. A seaward decrease in Eh was caused by an increase in pH and the weak ow of the
water mass. The decrease in Eh caused the number of electrons in sediment to decrease. The number of electrons was directly proportional to
the Eh. This is in accordance with Rhoads (1974), who reported a strong

Table 1
Surcial sediment properties during wet and dry season in the estuary of Jeneberang River.
Sampling

sites

R1
R2
R3
E1
E2
E3
E4
E5
E6
E7
CS1
CS2
CS3
CS4
CS5
CS6
CS7

Riverine
Riverine
Riverine
Estuarine
Estuarine
Estuarine
Estuarine
Estuarine
Estuarine
Estuarine
Marine
Marine
Marine
Marine
Marine
Marine
Marine

Clay (%)

Silt (%)

Sand (%)

OC (%)

Eh (mv)

SPM (mg/l)

Wet

Dry

Wet

Dry

Wet

Dry

Wet

Dry

Wet

Dry

Wet

Dry

6
19
8
32
35
11
15
18
16
35
34
24
20
16
60
60
59

28
27
18
20
15
19
18
10
10
11
13
12
23
29
76
77
74

29
12
22
5
5
10
8
7
7
2
3
6
2
45
4
5
2

19
17
3
25
26
2
4
2
5
7
24
20
68
68
11
13
15

65
69
70
63
60
79
77
75
77
63
63
70
78
39
36
35
39

53
56
79
55
59
79
78
88
85
82
63
68
9
3
13
10
11

2.24
2.29
2.25
2.64
2.15
2.45
2.74
2.25
2.38
2.89
2.14
2.67
2.90
3.04
2.87
2.75
2.62

2.07
2.05
2.03
2.31
1.21
1.14
1.10
1.01
1.13
105
1.18
1.10
2.74
3.46
2.64
2.33
1.60

23.43
17.37
17.10
10.52
9.15
8.73
8.43
8.18
7.95
8.52
2.20
2.35
2.33
-11.17
13.53
13.75
14.13

71.37
73.50
87.71
31.56
33.30
27.45
59.80
49.31
33.60
59.70
71.60
72.95
96.73
98.90
80.85
92.21
90.73

160.0
154.0
146.0
293.0
261.0
204.0
133.0
202.0
253.0
182.0
97.0
141.0
137.5
62.5
33.5
32.5
32.5

16.0
14.0
11.0
14.0
13.0
13.0
12.0
16.5
16.0
20.5
23.0
28.5
25.0
12.0
12.0
12.0
10.0

Wet = wet season; Dry = dry season.

Najamuddin et al. / Marine Pollution Bulletin 111 (2016) 456462

correlation between pH and Eh. Based on the Eh, the study area was determined to be a reducing zone (anaerobic conditions).
The concentrations of Pb and Zn in sediment around the estuary of
the Jeneberang River during the wet and dry seasons are shown in
Fig. 2. The highest Pb and Zn concentrations were found in the riverine
(R1) and marine (CS4) zones, while lower concentrations were found in
the estuarine zone (E1). The Pb and Zn concentrations were higher during the wet season than the dry season. The distributions of Pb and Zn in
this study were similar to the general distribution of elements in the
aquatic environment (Lim et al., 2012; Bibby and Webster-Brown,
2006). The higher Pb and Zn concentrations during the wet season
were inuenced by the intake of particulate heavy metals, which tended
to be higher during the wet season. The increased concentration of
suspended particles during the wet season was due to the higher levels
of erosion and water runoff, which entered the river basin and increased
the concentration of elements in downstream sediments. In addition,
the high level of erosion during the wet season increases the aluminum
silicate and Fe oxide content of particles, thus increasing the levels of Pb
and Zn compounds bound to the particle surfaces (Bibby and WebsterBrown, 2006). During the dry season, the suspended particle concentration in the water body was quite low, because the only source was from
the deposition of atmospheric dust particles, with the elemental intake
from erosion and water runoff signicantly reduced. The higher Pb and
Zn concentrations of riverine and marine sediments indicated that the
pollutants in sediment were derived from the mainland (entering the
river basin mainly in particulate form and then settling and accumulating on the bottom) and marine sources (both dissolved and particulate
forms) (Najamuddin et al., 2016; Samawi, 2007; Werorilangi et al.,
2013).
The low concentrations of heavy metals in sediment were attributed
to the following two factors. (1) The dam restricted the ow of the river,
leading to a reduction in water mass ow; therefore, most particulate
heavy metals were deposited along the dam, with only small amounts
entering the estuary. (2) There was turbulent water ow in the estuary,
which decreased the deposition rate of the particles. The turbulence led
to sediment resuspension, resulting in metal desorption from the sediment to the water column. Consequently, the concentrations of
dissolved metals were higher in this zone than in the riverine environment. Sediment resuspension has previously been reported to cause desorption or the release of heavy metals from the particle surface to the
water column (Lenzi, 2010; Tengeberg et al., 2003).
The heavy metal distribution was also inuenced by the sediment
characteristics. This was demonstrated by a correlation analysis of

459

metal concentrations in the sediment, sediment characteristics, and

the SPM. A strong correlation was found, as shown in Table 2. Heavy
metal concentrations in the sediment were not only dependent on
rock weathering but were also inuenced by sediment deposition, the
redox status, the OC concentration, and sediment texture. The results
showed that the levels of SPM had a strong correlation with metal concentrations during the wet season, while the OC concentration was
more strongly correlated with metal concentrations during the dry
season.
The measurement of the total metal concentration is a fundamental
aspect of sediment quality assessment. However, the geochemical fractionation of the metals is crucial, because the chemical form will inuence the mobility, migration ability, and chemical behavior. Therefore,
a sequential extraction procedure was proposed to evaluate the
strength of the association between metals and sediments (Wang et
al., 2015). The distributions of heavy metals in different sediment fractions in the estuary Jeneberang River, expressed as mean percentages,
are shown in Fig. 3.
The higher mean percentage of the residual fraction during the wet
season compared with the dry season was attributed to a naturally increased intake of sediment particles from soil erosion and rock
weathering on the mainland as a consequence of the high rainfall intensity. This was supported by data conrming that the suspended particle
concentration was higher during the wet season than the dry season.
Most of the Pb and Zn in surface sediments was strongly retained in
the residual fraction during both the wet and dry seasons. Our results
indicate that the metals were strongly bound to the crystal lattices of
minerals and thus had relatively low mobility, bioavailability, and toxicity. Therefore, the existence of this fraction in sediments is not harmful
to organisms. The heavy metal complexes can be broken down when
the sediments are decomposed (Teixeira et al., 2003; Wang et al.,
2015). The resistant fractions of Pb and Zn were found to be dominant
in the estuary, indicating that the main sources of Pb and Zn were
from natural processes, such as rock weathering or soil erosion on the
mainland and runoff entering the waters. The resistant components
comprise the non-labile fraction that can only be disrupted by strong
acids (Trujillo-Crdenas et al., 2010).
The metal content in the labile fractions (organic, Fe\\Mn oxides,
carbonate, and exchangeable) was lower during the wet season than
the dry season, because the high water mass ow during the wet season
affected metal intake from anthropogenic sources (presumably originating from seaport activities, transportation, the hospital, and industrial sites along the northern shore of the Jeneberang River estuary). Due

Fig. 2. Concentration distribution of heavy metals Pb and Zn from surface sediment during wet and dry season in the estuary of Jeneberang River.

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Najamuddin et al. / Marine Pollution Bulletin 111 (2016) 456462

Table 2
Pearson's correlation coefcient between Pb, Zn, clay, silt, sand, OC, Eh, and SPM during wet and dry season in the estuary of Jeneberang River.

Wet season

Dry season

Pb

Zn

Clay

Silt

Sand

OC

Eh

SPM

Pb
Zn
Clay
Silt
Sand
OC
Eh
SPM

1
0.832
0.144
0.458
0.507
0.136
0.252
0.712

1
0.163
0.634
0.285
0.002
0.037
0.469

1
0.512
0.768
0.316
0.753
0.499

1
0.157
0.058
0.126
0.145

1
0.406
0.772
0.681

1
0.609
0.426

1
0.711

Pb
Zn
Clay
Silt
Sand
OC
Eh
SPM

1
0.719
0.248
0.002
0.188
0.174
0.311
0.053

1
0.041
0.241
0.189
0.590
0.545
0.189

1
0.008
0.757
0.457
0.519
0.464

1
0.647
0.682
0.457
0.276

1
0.794
0.694
0.173

1
0.612
0.244

1
0.052

Correlation is signicant at the 0.01 level (2-tailed).

Correlation is signicant at the 0.05 level (2-tailed).

to the stronger currents during the wet season, the metals also tended
to be present in the water column rather than deposited on the water
bottom. The metals were considered to have been desorbed from the
surface of the particles, due to the strong water turbulence. This is in accordance with Lenzi (2010) and Tengeberg et al. (2003), who both reported that sediment resuspension leads to elemental desorption into
the water column. The small percentage of labile materials in the carbonate and exchangeable fractions found in this study indicated that
the pollutant intake derived from human activity (anthropogenic

sources) was lower than that from natural sources. This is in accordance
with Teixeira et al. (2003) and Rodrigues and Formoso (2006), who reported that the labile fractions associated with sediments commonly
originate from anthropogenic sources, while the non-labile fractions
commonly originate from natural processes.
Most metals introduced by human activity are present in the exchangeable and carbonate fractions. The metals in the acid-soluble fraction are considered to be bound the weakest, and therefore the most
mobile metals, in sediments and are dened as the exchangeable and

Fig. 3. Percentage of geochemical fraction of Pb and Zn during wet and dry season in the estuary of Jeneberang River.

Najamuddin et al. / Marine Pollution Bulletin 111 (2016) 456462

461

Table 3
Pearson's correlation coefcient between geochemical fractionation of Pb with sediment properties during wet and dry season in the estuary of Jeneberang River.
F1
Wet season

Dry season

F1
F2
F3
F4
F5
Clay
Silt
Sand
OC
Eh

F1
F2
F3
F4
F5
Clay
Silt
Sand
OC
Eh

1
0.508
0.894
0.727
0.870
0.578

a
a
a
a
a
a
a
a
a

0.372
0.684
0.315
0.616

F2
1
0.317
0.037
0.135
0.273
0.261
0.120
0.521
0.336
1
0.347
0.450
0.339
0.335
0.024
0.240
0.127
0.257

F3

F4

1
0.029
0.179
0.400
0.066
0.410
0.315
0.626

1
0.976
0.186
0.331
0.461
0.422
0.426

1
0.582
0.801
0.333
0.405
0.519
0.294
0.590

1
0.937
0.581
0.034
0.421
0.063
0.391

F5

Clay

1
0.305
0.263
0.547

1
0.512
0.768

0.556
0.593

0.316
0.753

1
0.562
0.163
0.535

1
0.008
0.757

0.210
0.608

0.457
0.519

Silt

Sand

OC

Eh

1
0.157
0.058
0.126

1
0.406
0.772

1
0.609

1
0.794
0.694

1
0.612

1
0.647
0.682
0.457

Cannot be computed because the variables is zero.

Correlation is signicant at the 0.01 level (2-tailed).
Correlation is signicant at the 0.05 level (2-tailed).

carbonate fractions. Metals in these fractions have greater bioavailability. This situation poses a higher risk to the environment. The reducible
(Fe\\Mn oxide) and oxidizable (organic) phases act as a metal sink.
The metals bound to these fractions can be mobilized by increasing/reducing oxidizing conditions in the environment (Wang et al., 2015).
Werorilangi et al. (2013) classied the geochemical fractionation of
samples around the Makassar coast as either acid soluble (exchangeable
and carbonate fractions), reducible (Mn\\Fe oxide fraction), or oxidizable (organic fraction). In their report, the mean percentages of Pb in
the acid soluble, reducible, and oxidizable phases were 07, 6478,
and 1633%, respectively. The mean percentages of the Zn fraction in
the acid soluble, reducible, and oxidizable phases were 055, 39100,
and 025%, respectively. Arin and Fadhlina (2009) reported that the
Pb labile fraction from Jakarta Bay was dominated by the oxidizable
(8.5593.77), reducible (0.1725.99%), and easily leachable and

exchangeable phases (08.16%). Moreover, the percentage of Pb in the

non-labile fraction ranged from 0 to 92.66%.
The correlations between the geochemical fractionations of Pb and
Zn and the sediment properties are shown in Tables 3 and 4. The results
of the correlation analysis indicated strong correlations between fractions F1 and F2 and the sediment texture. These fractions are weakly
bound to clay, silt, and sand on the surface of the sediments, and the
compositions of these fractions were determined prior to their assessment using Pearson's correlation coefcient values. Fraction F3 was
strongly correlated with the Eh of the sediment, because this fraction
was formed under reducing conditions. Fraction F4 was not correlated
with any of the sediment properties. This provides an explanation for
why OC, which plays a role in the formation of this fraction, was distributed relatively homogenously throughout the study area. Fraction F5
was strongly correlated with the sediment texture, because this

Table 4
Pearson's correlation coefcient between geochemical fractionation of Zn with sediment properties during wet and dry season in the estuary of Jeneberang River.
F1
Wet season

Dry season

F1
F2
F3
F4
F5
Clay
Silt
Sand
OC
Eh

F1
F2
F3
F4
F5
Clay
Silt
Sand
OC
Eh

F2

1
0.940
0.238
0.818

1
0.170
0.728

0.862
0.706

0.782
0.623

0.198
0.668
0.253
0.631

0.181
0.593
0.137
0.599

Cannot be computed because the variables is zero.

Correlation is signicant at the 0.01 level (2-tailed).
Correlation is signicant at the 0.05 level (2-tailed).

F3

F4

F5

Clay

Silt

Sand

OC

Eh

1
0.718
0.454
0.449
0.305
0.289
0.389
0.639

1
0.294
0.429
0.010
0.486
0.334
0.472

1
0.067
0.407
0.226
0.106
0.273

1
0.512
0.768
0.316
0.753

1
0.157
0.058
0.126

1
0.406
0.772

1
0.609

1
0.554
0.328
0.112
0.031
0.106
0.272
0.174

1
0.968
0.426
0.361
0.561
0.299
0.554

1
0.522
0.416
0.670
0.417
0.681

1
0.008
0.757
0.457
0.519

1
0.647
0.682
0.457

1
0.794
0.694

1
0.612

462

Najamuddin et al. / Marine Pollution Bulletin 111 (2016) 456462

component represents a chemical complex of metals in the crystalline

mineral matrices within sediment particles.
The assessment of Pb and Zn pollution levels was conducted using
the geoaccumulation index (Igoe) and risk assessment code (RAC).
The Igoe was calculated by comparing the heavy metal concentrations
with the natural concentrations in sediments. The RAC was determined
by calculating the total metal content percentage in the carbonate and
exchangeable fractions of the sediments.
The range of the Igoe of Pb was 0.0110.070 during the wet season
and 0.0040.037 during the dry season, which was classied as weak
pollution. The range of the Igoe of Zn was 0.9291.658 during the wet
season and 0.6220.728 during the dry season, which was classied as
weak to moderate pollution. The RAC of Pb was 2.6444.533 during
the wet season and 9.27115.604 during the dry season, which was
classied as a light to medium risk. The RAC of Zn was 0 during the
wet season and 0.000.466 during the dry season, which was classied
as no risk. The higher RAC of Pb indicated that the anthropogenic source
of this pollutant was larger than that of Zn. The RAC of Zn was not a
threat to aquatic biota, because the majority of the Zn was in non-labile
or residual fractions.
There are potential hazards to marine biota caused by Pb due to the
increased levels of this pollutant in the labile fraction in sediments along
the coast of the Jeneberang River estuary, and this is a potential focus for
future research and monitoring.
Acknowledgements
This research was supported by General Directorate for Resources of
Research-Technology and High Education (003/PEN-DD/PL/2015) with
the grant program of research and public services.
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