ASSESSMENT OF Pb METAL CONCENTRATIONS ON
WATER COLUMN, SEDIMENT AND ORGANISMS AT
KAYANGAN ISLAND WATERS OF MAKASSAR CITY
Akbar Tahir@, Yeis Pairunan and Masrul Jaya
Department of Marine Science, Faculty of Marine Science and Fisheries, University of
Hasanuddin, Tamalanrea Campus, Makassar-INDONESIA
@
Contact Person : e-mail: Akbar_Tahir@mar-sci.unhas.ac.id Ph/Fax : +62 411-587000.
Abstract
Research on heavy metal analysis in water column, sediment and organisms at Kayangan Island Makassar City, was conducted. Samples from water column, sediment, macrozoobenthos, sponge,
stony and soft corals were collected from four stations around Khayangan Island for analysis of
their lead (Pb) content. Kayangan Island is one of established domestic tourist destinations and is
part of Spermonde archipelago located at Northern part of Makassar. The island is within the
vicinity of Makassar City, which is one of a densely populated city in Eastern Indonesia, surrounded
by Makassar Sea Port and Ship Industry Area (PT. IKI), and relatively influenced by Tallo River
mouth where Makassar Industrial Estates (PT. KIMA) drained their wastewater. With this
circumstance, Kayangan Island surrounding waters is suspected to be heavily loaded with pollutants
from human activities. Concentrations of Pb from all samples were measured with Atomic
Absorbance Spectrophotometer. Data analysis on Pb concentration from all sampling stations of
sponge, stony and soft corals, and macrozoobenthos (predominated with polychaeta) resulted in no
significant differences within organism. However, Significant differences of Pb concentration were
found between organisms, with positive correlation of Pb concentrations between water column and
sediments. Overall results showed there is a consistent pattern of Pb accumulation at all sampling
stations.
Keywords: Lead, sediment, benthos, Spermonde, pollution.
I. INTRODUCTION
Environmental pollutants from varied sources contaminated water, soil and
air, provoked human and environment to a wide range of risks. Globally, thousands
of chemicals posed serious threats to human health and ecosystem. In particular to
development nations, like Indonesia, citizens are faced to a higher risk due to the
lack of knowledge and understanding, absence of pro-people regulation,
inconsistent in law enforcement and inadequate capital for cleaner technology
access. All of these making members of society in poor developing countries were
unable to protect themselves from hazard of high risks pollutants.
Marine environment, including estuary, with high water quality turn out to be
a major determinant in maintaining healthy condition of both human and
environment as resources provider. However, as chemical waste disposal increased
from manufacture, agriculture, atmospheric input, direct waste disposal and others,
have made up aquatic environment filled with toxic chemical substances, including
heavy metals. Important heavy metals in the context of aquatic pollutions are Zn,
Cu, Pb, Cd, Hg, Ni and Cr. Metals like Pb, Hg and Cd do not have advantage in
biological functions and toxic to organisms. Lead (Pb) is one of the most common
metals found in aquatic environment (Clark, 1997) as a result of waste disposal and
atmospheric input, notably those from vehicles using fuels with ‘tetraethyl lead’
additive.
For that reason, it is important to monitor the occurrence of Pb in aquatic
environment through integrated analysis of its concentrations in water column,
sediment and sessile organisms so as to obtain complete pictures of metals load in
waters, those precipitated in sediment and accumulated by organisms.
Kayangan island is belong to Spermonde archipelago (Fig. 1), about 0.9 km
from Makassar city (population  1.5 million), established as domestic tourist
destination since 1960’s with total area ca. 1.5 ha. The island could be reached in 15
min using a motorized boat from Makassar. The island is completed with lodgings,
restaurant, music stage, mini hall, kids playing area, fishing platform, and sport
facilities. Kayangan island is laid on northern part Ujung Tanah District of
Makassar City, with Makassar Sea Port and Makassar Shipyard Industry nearby to
the east. Densely populated housing area and traditional wooden ship port around
Tallo estuary is only 2.3 km to northern-east site of the island. Moreover, to the
west and south part of the island are busy traffics of sea transportation from day to
day with different purposes and destinations. In addition, the coral reef ecosystem
at the island is already degraded, but various kinds of benthic organisms, such as
stony coral, soft coral, algae, sponges, macrozoobenthos (predominated with
polychaeta), fish and other animals were still found frequently, although not
abundantly.
II. MATERIALS AND METHODS
A wooden boat was hired from local fishermen to collect samples, using GPS
to denotes four sampling locations with 3 sub-stations each (as replication). With
basic diving gears stony coral, soft coral and sponges were collected at respective
stations, whilst sediment and macrozoobenthos were sampled with bottom grab
sampler or polyvinyl pipe with Ø 2 inch, where applicable. All samples were put
into appropriate sample bags with respective information, placed in a cool box and
directly transported to the laboratory.
Figure 1. Research location with sampling stations (annotated with red flags and alphabets).
2.1. Metal analysis on water column
Metal extraction procedure from water column was performed with wetdestruction method according to Indonesian National Standard method (SNI 066989.38-2005). Into 50 ml of filtered sea water sample (Whatman #41, pore size
0.45 µm) was added 5 ml 65% HNO3, leaved on a hot plate until the volume only
15-20 ml. Another 5 ml HNO3 was then added and covered with Pyrex watch-glass
and put on the hot plate again until all metals were finely dissolved with white color
sediment and the solute became clear. This was followed by the addition of 2 ml
HNO3 and leave in oven at 300o C for ± 10 min. Samples were then transferred into
measuring glass, filled with double distilled water to measure 50 ml.
2.2. Metals analysis on sediment, corals, sponge and macrozoobenthos
Metal extraction procedure from sediment, polyps of stony and soft corals,
sponge and macrozoobenthos were performed with wet-destruction method
according to Indonesian National Standard method (SNI 06-06992.8-2004). Prior to
the extraction process, all samples were washed with distilled water and dried at
room temperature for 10-14 days, then dried in oven at 80o C for 16 h. Coral polyps,
sponge and polychaeta samples were dried in oven at 60o C for 48 h. Sediment and
organisms samples were weigh for 3 g respectively, then put into beaker glass with
15 ml distilled water added to be homogenized with stone mortar. Into the solution
was then added 10 ml HNO3, covered with watch-glass and put on the top of hot
plate at 105o – 120o C, until the volume left only ± 10 ml. Samples were then left to
cool in room temperature. Into the samples were then added 5 ml HNO3 (Nitric
Acid 65%) and 1 – 3 ml HClO4 (Perchlorate Acid 70%) drop by drop through the
wall of beaker glass, then homogenized. Samples were then heated on the hot plate
until white smoke occurred and the solute became clear. Boiling the samples were
the continued for 30 min and left to cool. Samples were then filtered with pore size
8 µm (Whatman #40). Filtrates were then transferred into a measuring glass and
filled with double distilled water to measure 50 ml, then further homogenized.
Lead metal concentrations in water column, sediment, stony and soft corals,
sponge and macrozoobenthos were then measured with Atomic Absorption
Spectrophotometer (AAS) Shimadzu AA-7000 Tandem with Graphite Furnace.
Results are expressed in µg/g (ppm).
2.3. Data Analysis
One Way ANOVA was used to look at differences in average values of Pb
metal in water column, sediment, stony and soft coral, sponges and
macrozoobenthos between the sampling stations. Pearson’s correlation was used to
look for any correlation of Pb metal concentrations between sampling stations
(Bengen, 2000).
III. RESULTS AND DISCUSSION
Highest concentration of Pb was found in stations I and II (Fig. 2), where
there is no significant differences. The concentrations from both stations were
significantly different with those from stations III and IV (P < 0.05). Differences in
Pb content of water column most likely due to the position of the first two stations
are very close to sources of pollutants, such as Makassar Sea Port where ship
traffics are busy, dry docking location where ships were painted and repaired, direct
waste disposal from the ship, industrial and commercial waste disposals, and
enormous amounts of automotive vehicles smokes from adjacent city of Makassar.
Lead entered aquatic environment through several routes, such as industrial waste
disposal, leaking from ship paint with Pb in their base material intended as anticorrosive and anti-fouling agents (Marganof et al., 2003), and as fuel additive so
called ‘tetraethyl lead’ (e.g. Palar, 2004). As Pb is widely used for various
applications, sooner or later it will exaggerate diverse effects on the quality of
aquatic environment and organisms. Lead concentrations in water column of
Kayangan island are exceeding the maximum value indicated by Indonesian
Ministry of Environmental Affairs/KMNLH, i.e. 0.08 ppm (KMNLH decree No.
51/2004).
Concentrations of Pb in sediment, was found significantly higher at stations
II and I, compared to stations III and IV (Fig. 3). High sediment concentration of Pb
clearly indicated that these stations had received substantial amount of waste
containing Pb metal. This concentration is consistent with Pb level of the stations in
the water column and presumably came from similar sources of lead containing
wastes which in turn to remain and accumulated at sediment. Sediment
concentration of Pb metal had exceed the maximum level of 33 ppm (Febries and
Werner, 1994) and is undoubtedly due to the sediment capability in accumulating
and absorbing substantial load of Pb metal, which well known to have a poor water
solubility (Marganof et al., 2003).
0.6
a
Pb concentrations (ppm)
a
Water column
b
0.5
b
0.4
0.3
0.54
0.49
0.35
0.42
0.2
0.1
0
I
II
III
Sampling stations
IV
Figure 2. Pb metal concentrations in water column at all sampling stations. Values are mean of 3 replication from sub-station
samples  SD. Different alphabets annotated significant differences.
Pb concentrations (ppm)
60
50
Sediment
b
a
40
d
c
30
20
10
44.7
51.7
23.6
31.7
III
IV
0
I
II
Sampling stations
Pb concentrations (ppm)
Figure 3. Pb metal concentrations in sediment at all sampling stations. Values are mean of 3 replication from sub-station
samples  SD. Different alphabets annotated significant differences.
18
16
14
12
10
8
6
4
2
0
Stony coral
a
a
a
a
14
10.3
10.2
III
IV
9.0
I
II
Sampling stations
Figure 4. Pb metal concentrations in stony coral at all sampling stations. Values are mean of 3 replication from sub-station
samples  SD. Similar alphabets annotated no significant differences.
Metal Pb concentrations in all sample organisms were not differed
significantly within the same organism at all sampling stations, indicating a
proportional absorption of Pb by each kind of animal (Figs 4-7). The high Pb
concentration in all benthos is presumbaly due to the central position of Kayangan
island in the context of sea transportation at South Sulawesi capital, Makassar city.
Busy traffics of both fishermen and commercial boats and ships, have made almost
all sides of the island were affected by Pb containing waste from various human
activities at the nearby city.
Stony coral, soft coral, sponge and macrozoobenthos are amongst marine
organisms which usually found to inhabit coral reef ecosystem, albeit that they
would also be found live in solitair at extreme waters condition. These benthic
animals are known to have a high adaptation and tolerance to rapid change of
aquatic environmetal condition compared to other organisms, even with
consequences of easily accumulating nasty substances in their body tissues.
At the Kayangan island waters, lowest concentration of Pb was found in
stony coral, whist the highest concentration was observed in sponge (stony coral <
macrozoobenthos < soft coral < sponge). This low concentration Pb metal in stony
coral (Fig. 4) is certainly related to their body skeleton characteristics that consisted
by massive calcium carbonate (CaCO3) which made the accumulation of metal gone
slowly, concomitant with their slow growth rate (Supriharyono, 2007). However,
Pb concentration in stony coral of Kayangan island had exceeded maximum value
of 0.08 ppm (Mukhtasor, 2007). Lead concentration in stony coral could be used as
a good indicator for levels of pollution in certain area due to the ability of their
calcareous exoskeleton to assimilate metals for a long period, upto hundreds of
years (Ramos et al., 2004).
Pb concentrations (ppm)
25
a
Macrozoobenthos
a
20
a
a
15
18.6
14.9
10
15.7
15.1
5
0
I
II
III
IV
Sampling stations
Figure 5. Pb metal concentrations in macrozoobenthos at all sampling stations. Values are mean of 3 replication from substation samples  SD. Similar alphabets annotated no significant differences.
As an animal lived and search for food inside the sediment, macrozoobenthos
is generally found lived inside or dwell upon sediment. Therefore, high
concentration of metal Pb in macrozoobenthos as a resultant of bioaccumulation
from their surroundings. Animals with burrowing, dwelling and spent almost their
entire live in sediment would accumulate metals in high concentration due to
persistent exposure of such pollutants in their entire live (Connel and Gregory,
1995). There is no significant different of the Pb concentrations in
macrozoobenthos (Fig. 5).
Pb concentrations in (ppm)
Soft coral
34
a
a
a
33
32
a
31
30
29
32.1
28
31.7
27
30.5
29.6
26
25
I
II
III
Sampling stations
IV
Figure 6. Pb metal concentrations in soft coral at all sampling stations. Values are mean of 3 replication from sub-station
samples  SD. Similar alphabets annotated no significant differences.
Lead metal concentrations found in soft coral are consistently high at all
sampling sites (Fig. 6), although still lower compared to those found in sponge. Pb
concentrations in soft coral is second to sponge, which unquestionably is due to
their soft body structure which facilitated water pollutants to accumulate through
their filter feeder and sessile living characteristics. This soft structure ease direct
absorption of metals from environment to their body surface (Connel and Gregory,
1995).
Sponge
a
Pb concentrations (ppm)
40
a
a
a
35
30
25
35.2
34.6
34.8
20
32.7
15
10
5
0
I
II
III
IV
Sampling stations
Figure 7. Pb metal concentrations in sponge at all sampling stations. Values are mean of 3 replication from sub-station
samples  SD. Similar alphabets annotated no significant differences.
Data analysis resulted with sponge as organism containing highest
concentration of metal Pb. This data clearly demonstrated that sponge as the most
permeable animal, with enormous numbers of pores on sponge entire bodyconnected to channels and internal cavities have enabled the sponge to filter of
more than 10,000 gallon of sea water per-day for their nutrient and oxygen
requirements (Munifah et al., 2008). This feeding habit is favorable for the
ingestion of various pollutants, including Pb, into the sponge body which finally
accumulated and resided in their tissues.
Univariate ANOVA on stony coral, macrozoobenthos, soft coral and sponge
data have revealed significant differences (P = 0.00) on their Pb metal
concentrations. This value clearly showed that Pb concentrations in stony coral, soft
coral, macrozoobenthos and sponge are significantly different which means that
there is a diferences in Pb metal absorption and accumulation between those
organisms. However, Tukey test showed that there is no differences between soft
coral and sponge in their Pb metal concentrations.
Pearson’s correlation analysis to look at possibility of relationship in lead
metal amounts at all samples resulted in a rather weak correlation between Pb metal
concentrations in sediment and water column (Fig. 8). Likewise, there is no
correlation between benthic organisms Pb contents both with sediment and water
column concentrations (Fig. 9 and 10).
Pb in sediment (ppm)
60
y = 133.76x - 22.029
R² = 0.7276
50
40
30
20
10
0
0
0.2
0.4
0.6
Pb in water column (ppm)
18
16
14
12
10
8
6
4
2
0
y = 0.0079x + 10.58
R² = 0.0014
0
20
Pb in soft coral (ppm)
Pb in stony coral (ppm)
Figure 8. Correlation between Pb concentrations in sediment and water column.
40
60
40
35
30
25
20
15
10
5
0
y = -0.0063x + 31.236
R² = 0.0009
0
40
60
25
45
40
35
30
25
20
15
10
5
0
y = 0.0675x + 31.782
R² = 0.0769
0
20
40
Pb in sediment (ppm)
60
Pb Macrozoobenthos (ppm)
Pb in Sponge (ppm)
20
Pb in sediment (ppm)
Pb in sediment (ppm)
20
15
y = 0.0332x + 14.816
R² = 0.0331
10
5
0
0
20
40
Pb in sediment (ppm)
Figure 9. Correlation between Pb concentrations in sediment and benthic organisms.
60
Pb in soft coral (ppm)
Pb in stony coral (ppm)
18
16
14
12
10
8
6
4
2
0
y = 13.905x + 4.6468
R² = 0.1804
0
0.2
0.4
40
35
30
25
20
15
10
5
0
y = 2.7243x + 29.775
R² = 0.007
0
0.6
0.4
0.6
Pb in water column (ppm)
25
45
40
35
30
25
20
15
10
5
0
Pb in Macrozoobentos (ppm)
Pb in Sponge (ppm)
Pb in water column (ppm)
0.2
y = 11.096x + 29.37
R² = 0.0844
0
0.2
0.4
Pb in water column (ppm)
0.6
y = 12.969x + 10.259
R² = 0.2062
20
15
10
5
0
0
0.2
0.4
0.6
Pb in water column (ppm)
Figure 10. Correlation between Pb concentrations in water column and benthic organisms.
IV. CONCLUSION
Based on AAS measurement and statistical analysis of lead metal
concentrations in water column, sediment and benthic organisms collected at four
stations of the Kayangan island waters, it is concluded that the surrounding waters
and the sediment underneath (where benthic organisms dwell) are already
profoundly polluted with Pb metal. Significant differences of Pb concentrations
were found between organisms, with positive correlation between Pb in water
column and sediment. Overall results showed there is a consistent pattern of Pb
accumulation at all sampling stations.
With respect to the current state of Kayangan island as a domestic tourist
destination, pertaining to highly polluted waters usages for activities such as
swimming and snorkeling, it is of high risks to the visitors, for both possibilities of
being swallowed through water and absorbed by the skin.
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