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ENVIRONMENTAL TOXICOLOGY (MMS4000)

2013/2014

ASSESSMENT OF HEAVY METAL

NURUL ADHA BINTI UJANG


(UK28913)
LIYANA BINTI YAMIN
(UK 28942)

PROGRAMME
BACHELOR OF APPLIED SCIENCE
CONSERVATION AND MANAGEMENT OF BIODIVERSITY

LECTURER
DR. HING LEE SHING

FIELD TRIP
SETIU WETLAND

INTRODUCTION
Heavy metals contaminations have cause a great concern due to its stable and
environmental persistence characteristics especially in aquatic environment (Alkarkhi
et al., 2009). Heavy metal basically occur naturally in earth, however due to human
involvement, it become concentrated eventually leading to this type of contamination.
Heavy metals pollutants such as Cadmium and Lead can cause toxicity to the living
organism once they exceed the concentration limit (MacFarlane & Burchett 2000).
Thus, it is required to perform some assessment of heavy metal for caution.
In assessing the heavy metal pollution in the aquatic environment, chemical,
toxicological and ecological approaches have been done extensively. Much research
emphasize the use of invertebrate organism as the pollution bioindicator as their
ability to accumulate contaminants .This is due to their nature as filter feeders that
are immobile making them suitable for monitoring changes in chemical
concentrations at fixed locations (Astudillo, 2005).
The study on the sediments for heavy metal pollutants assessment also had been
done widely. Sediments usually represent as one of the ultimate sinks for heavy
metals discharged into environment (Hollert et al. 2003). The sediments
characteristics such as the grain size and amount of organic matter allow them to
determine the presence of the heavy metal pollutants (Sauve et al., 2000) thus also
making them important as heavy metal contamination indicators.
The main objectives of this study is to determine the heavy metal concentrations on
sediment and oyster of the Setiu lagoon. This study also took into account the water
quality parameter of the lagoon. In this study, a comparison were made to identify
whether the oyster from the Setiu Lagoon are safe for consumption.

METHODOLOGY
The study area revolves at Setiu Wetland, a lagoon estuary system that was
investigated which extends from N 05o41.031 to 05o40.801 . Samples were taken
from 5 different locations with three replicates in Setiu Wetlands.

Site 1

Site 2

Site 3
Site 4

Site 5

Figure 1 Site location map

Sediment samples were taken using a ponar grab. The physio-chemical parameters
of water (pH, dissolved oxygen, temperature and salinity) were measured using Multi
Probe Systems at near surface and near bottom of the water. Then oyster samples
were collected at a nearby aquaculture farm.

After collecting all the samples, all samples were brought back to the lab for further
analysis. The samples first were dried out to get the dry mass. The oysters then were
grinded using mortar and pestle to break up the particles. The next step is shafting to
ensure the particles was fine. The weight of the sample were taken and were put into
selected digestion tubes. 5mL of concentrated nitric acid were added to each test
tube. Later on, the plate were heated at at 95C for 3 hours. The fume colour were
observed as it was cooled down slowly. 1mL of hydrogen peroxide was added
subsequently. The samples were heated again until no fume were observed. After
digestion was completed, the test tubes were let to cool down at room temperature.

Digested sample were transferred to 50mL of centrifuge tube. Then the samples
were diluted with mili Q water. Solution were then filtered to separate the coarse
particles in oyster solution. And lastly, the heavy metal readings of the diluted
samples were recorded.
Second major step is the sediment process using microwave acid digestion. Firstly,
the sediments are grinded using mortar and pestle to break up the particles. Then
the particles were placed in a shaft to ensure we only get the finest particle. The
particles were then placed into TFM vessel and placed on a balance. The vessel was
first tare and weighted. TFW vessel was introduced into HTC safety shield.
Perchloric acid, nitric acid and hydrogen peroxide were added at a ration of 1:6:1.
The vessel was closed and sample was introduced to the rotor segment. It was then
tightened by torque wrench. The segment was inserted to microwave cavity where
the temperature sensor was connected. The microwave program was run until
completion at 200C (T1) and 110C (T2) for 15 minutes for 2 times. The rotor was
then cooled by air and water until the solution reach room temperature. The vessel
was opened and the solution was then transferred to marked flask. Later on, the
solution was filtered in order to separate coarse particles in sediment solution. Finally
the heavy metals reading in the sediment were recorded.

RESULT
The result for the water parameter obtained from the lagoon from the five sampling
sites are presented in the Table 1. Each of the value for the water parameter was
obtained using the hydrolab. The temperature for all the sites were considered at
average, while the dissolve oxygen have a slight difference between sites. The pH of
the water at the sampling sites was almost basic and the salinity of the water at the
lagoon
The result of analysis of the Certified Reference Materials was shown at the Table 2.
In table 3, it can be seen that most high concentration of the heavy metal
concentration present in the sediment is chromium, followed by copper, cadmium
and lastly lead. The concentration of the lead and cadmium from sediment sample
taken from most of the sites cannot be determined.

Table 1 Water Quality Parameter from Setiu Lagoon


Top
Site 1
Site 2
Site 3
Site 4
Site 5

Temperature()

DO (mg/ml)

30.61+0.05
30.27+0.01
30.8 + 0.07

3.97+0.76
0.2+0.01
4.53+0.15

7.82+0.02
7.63+0.01
7.78+0.02

31.73+0.00

5.78+0.28

7.98+0.00

Bottom
Site 1
30.59 + 0.06
4.83+0.21
Site 2
30.46+0.05
3.91+0.15
Site 3
30.88+0.36
4.47+0
Site 4
Site 5
31.76+0.05
5.93+0.19

Mean values and


standard deviation.

pH

Salinity

7.80+0.005
7.60+0.06
7.86+0

31.34+0.17
18.62+0.07
30.87+0.16

31.34+0.09
30.84+0.24
31.09+0.36

7.97+0.00

Table 2: Recoveries of metals from estuarine sediment certified reference materials


Element
Cd
Cu
Pb
Cr

Certified values
0.148 0.007
10.01 0.34
11.7 1.2
40.9 1.9

Analyse value
0.142

Percentage
recovery
96.12

0.019

94.91

11.16

95.44

0.073

89.24

Table 2. : The heavy metal concentration in sediment and oyster.


Cr (ppm)

Cu (ppm)

Cd (ppm)

Pb (ppm)

30.00 5.29
39.33 6.11

7.33 1.15
13.33 2.31

ND

ND

5.33 1.15
13.33 1.15

5.33 2.31
ND

Site 4

28.00 3.46
54.00 3.46

1.33 2.31
0.80 0.00

Site 5

51.33 4.16

4.67 1.15

2.00 0.00
2.67 1.15

0.67 1.15
ND

13.89 2.55
10.44 8.57

43.89 0.96
52.78 0.96

2.78 0.96
11.67 1.67

ND

16.11 1.92
25.00 1.67

51.11 0.96
52.22 3.85

5.00 0.00
10.00 1.67

ND

Sediment
Site 1
Site 2
Site 3

Oyster
Site 1
Site 2
Site 3
Site 4

ND
ND

Site 5

40.00 4.41

44.44 0.96

7.22 0.96

ND

ND Not detected

Graph of concentration against heavy metal at site 1


Sediment

Concentration (ppm)

50
45
40
35
30
25
20
15
10
5
0

Cr

Oyster

Cu

Cd

Pb

Type of Heavy Metal

Graph of concentration against heavy metal at site 2


Sediment

Oyster

60
50
40
Concentration (ppm) 30
20
10
0

Cr

Cu

Cd

Type of heavy metals

Pb

Graph of concentration against heavy metal at site 3


Sediment

Oyster

60
50
40
concentration (ppm) 30
20
10
0

Cr

Cu

Cd

Pb

type of heavy metal

Graph of concentration against heavy metal at site 4


60
50
40
concentration (ppm) 30
20
10
0

Cr

Cu

Cd

type of heavy metal

Pb

Graph of concentration against heavy metal at site 5


60
50
40
concentration (ppm) 30
20
10
0

Cr

Cu

Cd

Pb

type of heavy metal


Figure 1 Comparison of heavy metal concentration in the sediment and oyster at each
sampling sites. The bars and vertical lines represent the mean and standard deviation,
respectively.

However, the concentration of copper is the highest in the oysters, followed by


chromium, cadmium and finally lead. From the Figure 1, from most of the sites, there
are significant difference in the concentration of heavy metals between the sediment
and the oysters. The concentration for each type of heavy metal is higher in oysters
than in the sediment, except for the chromium where it is higher in concentration in
the sediment than in the oysters.

DISCUSSION
From the result of analysis of estuarine sediment CRM were found to have ranging
values between 89% to 97% which means it is not necessery to perform correction
on the sample value.
The chromium seems to have the highest value in the sediment as the chromium
levels are naturally high in local soils and sedment (Astudillo, 2005). As most
chromium that released into water will ultimately deposited in the sediment (U.S.
Department Of Health And Human Services, 2012). Most cadmium and lead value
could not be determine in the sediment may due to the fact that the concentration is
too low.
The concentration of oyster and sediment differ significantly. Metabolism of oyster
influenced the heavy metal accumulation in oyster thus make them highly selective
on the type of heavy metal. Copper has high value in oyster as it is essential to the
oyster. The amount of cadmium in oyster is high compared to the sediment.
Cadmium is not necessery for the oyster metabolism, but as cadmium has similar

geochemical properties to Calcium, which is an essential element for oyster, it


probably enters oyster tissue as substitue for calcium (Huanxin, 1999).
Generally, marine shellfish had low tedency to accumulate chromium (Chong, 2001).
This explains the low concentration of chromium in oyster compared to the sediment.
Besides, the physiology of oyster allows it to discriminate chromium (Huanxin,1999).
As for the maximum permitted level for the consumption of oyster, using the
Malaysian Food Regulations 1985, cadmium, copper and chromium concentration
had exceeded the permitted levels for consumption.

CONCLUSION
This study provide the information for the heavy metal concentration in the sediment
and oyster from the Setiu Lagoon. The high level of heavy metal concentration that
can exceed the permitted level of international standards should be further discuss
and more research about the assessment of heavy metal in Setiu Lagoon should be
conducted to analyse about this matter more deeply

FIELD TRIP
Pasar Payang
INTRODUCTION
Heavy metals in definition are metallic chemical element that has a relatively high
density and are toxic or poisonous at low concentrations. Although living organism
require some amount of heavy metals for their metabolism and growth, it is still
considered dangerous as heavy metals tend to bioaccumulate. (Irwandi & Farida,
2009). Any organism that exceed the permitted level for consumption, it will have
deleterious effect on human.
Exposure of cadmium in a low level for a long period of time can induce toxicity
which will effect the kidney and human bones (U.S. Department Of Health And
Human Services, 2012). Although copper is essential for the metabolism, high
exposure to copper may lead to anemia, liver and kidney damage (Lenntech, 2004).
Lead, being a neuro- toxicant, can enter human body following the same pathway of
calcium and iron (Lanphear 1t al., 2003).
It is important to emphasize on the study of heavy metal in food to make sure it is
safe for comsumption. Especially food that came from organism that tend to
bioaccumulate such as fish which accumulate large amounts of heavy metals from
water (Cid et al., 2001).
Upon considering this issues, this study was conducted to determine the heavy
metal concentration on the three type of food bought from Pasar Payang; fish, fruit
and vegetables. It also conducted to determine whether the food bought from this
market are safe for consumption.

METHODOLOGY
Fish, fruits and vegetables was purchased from Pasar Payang. In order to make
analysis for these sample, preparation of sample were made. The fish samples were
cleaned, and the muscle tissue were used for analysis. All the samples; fish, fruits,
and vegetables were further dissected and dried until it reached constant weight.
These samples then were grinded using mortar and pestle. The next method involve
acid digestion. Weight of the samples were recorded and put into digestion tube.
About 5 ml of concentrated nitric acid were added in each tube. The tubes were put
on top of a plate and further heated for 3 hours at 95C. The fume colour were
observed as it was cooled down slowly. 1mL of hydrogen peroxide was added
subsequently. The samples were heated again until no fume were observed. After
digestion was completed, the test tubes were let to cool down at room temperature.
Digested sample were transferred to 50mL of centrifuge tube. Then the samples
were diluted with distilled water. And lastly, the heavy metal readings of the diluted
samples were recorded using AAS machine.

RESULT
Table 1. Recovery of heavy metals from certified materials.

Peach leaves

Element

Certified values

Cd

0.026 0.003
3.7 1.4

0.025
3.5

95.07

0.88

101.33

20.4

83.95

Cu

0.87 0.03
24.3 0.8
31.2 1.1

29.3

93.91

Pb

0.16

0.14

87.50

Cu
Pb
Cr
Cd

Dog fish

Cr

0.04

Analyse value

Percentage
recovery
97.45

Copper

Concentration (ppm)

0.09
0.08
0.07
0.06
0.05
0.04
0.03
0.02
0.01
0
Mango

Kundang

Guava

Type of fruits

Cadmium
0.06
0.05
0.04
Concentration (ppm)

0.03
0.02
0.01
0
Mango

Kundang
Type of fruits

Guava

Lead
0.7
0.6
0.5
0.4
Concentration (ppm)

0.3
0.2
0.1
0
Mango

Kundang

Guava

Type of fruits

Chromium

Concentration (ppm)

0.05
0.05
0.04
0.04
0.03
0.03
0.02
0.02
0.01
0.01
0
Mango

Kundang

Guava

Type of fruits

Figure 1. Heavy metal concentration in each type of fruits. The bars represent the
mean.

Copper
0.03
0.02
0.02
0.01
Concentration (ppm)

0.01
0

Fish species

Cadmium

Concentration (ppm)

0.02
0.02
0.01
0.01
0.01
0.01
0.01
0
0
0

Fish species

Lead

Concentration (ppm)

0.07
0.06
0.05
0.04
0.03
0.02
0.01
0

Fish Species

Chromium

Cconcentration (ppm)

0.02
0.02
0.01
0.01
0.01
0.01
0.01
0
0
0

Fish species

Figure 2. Heavy metal concentration in each fish species. The bars represent the
mean.

Copper
0.09
0.08
0.07
0.06
0.05
0.04
0.03
0.02
0.01
0
Ccocentration (ppm)

Type of vegetables

Cadmium
0.01
0.01
0
0
0
0
0
Concentration (ppm)

Type of vegetables

Lead
0.01
0.01
0.01
0.01
0
0
0
Concentration (ppm)

Type of vegetables

Figure 3. Heavy metals concentration in each type of vegetables. The bars represent
mean.
*Chromium value for each type of vegetables cannot be determined.

DISCUSSION
Table 1 represent the result analysis for vegetables and fish CRM. It found to have
ranging values between 83% 102% . This means, it is not required to perform
correction on each sample value.
In Figure 1, it shows copper present at each type of the fruits and the values are
quite high. However, it still did not exceed the maximum permitted level for
consumption, which is 10ppm (Kumar et al,2007). The high level of copper is due to
its important in the growth of fruits and vegetables. This also explains the high level
of copper in the vegetables (Figure 3). The level of cadmium, lead, chromium for
each type of fruits differ significantly. But still, they did not exceed the permitted level
for consumption. Cadmium, may present in fruit to balance the sugar level
(Bernard,2008). Chromium concentration in each fruits also did not exceed the
maximum permitted level which is 1ppm.
Most of the fish species shows accumulation of heavy metals in their tissue (Figure
2). Fish, being one of the top in the aquatic food chain, concentrate large of heavy
metal from water that build up by their ingestion (Ismaniza & Idaliza, 2012). The
highest concentration of heavy metal in each fish is the lead. Pb, being a cumulative
toxin, may present in the fish tissue due to the constant bioaccumulation
(Kamaruzzaman et al.,2011). However, the concentration did not exceed the 0.3ppm
permitted level for the safe human consumption (WHO,2001).
Besides lead, other heavy metals such as copper, cadmium, and chromium, the
concentration of each heavy metals in each species, all did not exceed the permitted
level.

CONCLUSION
The heavy metal concentrations in each type of food bought from Pasar Payang was
determined. This information provided can be used to indicate that these types of
food bought from Pasar Payang are safe for human consumption.

REFERENCES

Alkarkhi, A.F.M., Ismail, N., Ahmed, A., Easa, A.M. (2009). Analysis of heavy metal
concentrations in sediments of selected estuaries of Malaysiaa statistical
assessment. Environ Monit Assess. 153: 179 185
Macfarlane, G. R., & Burchett, M. D. (2000). Cellular distribution of Cu, Pb and Zn in
the grey mangrove Avicennia marina. Aquatic Botany 68: 4559
Astudillo, R. D., Yen, I.C., & Bekele, I.(2005) Heavy metals in sediments, mussels
and oysters from Trinidad and Venezuela L. Rev. Biol. Trop. 53 :41-53
Hollert, H., Keiter, S., Konig, N., Rudolf, , Ulrich, M., & Braumbeck, T. (2003). A new
sediment contact assay to assess particular-bound pollutants using zebrafish (Danio
rerio) embryos. Journal of Soils and Sediments. 3: 197 207
Sauve S., Hendershot W., Allen H.E. (2000) Solid-solution partitioning of metals in
contaminated soils: dependence of pH, total metal burden and organic matter.
Environ Sci Tech 34. 7:11251131
Huanxin Z. & Lejun, BJ. (2003) Bioaccumulation of heavy metals in oyster
(Crassostrea virginica) tissue and shell. Presley
Environmental Geology.
39(11):1216 1225
Chong, K. & Wang, W.X. (2001). Comparative studies on the biokinetics of Cd, Cr
and Zn in the green mussel Perna viridis and the Manila clam Ruditapes
philippinarum. Environ. Pollut. 115: 107-121.
Irwandi, J. & Farida, O. (2009) Mineral and heavy metal contents of marine fin fish in
Langkawi island, Malaysia. International Food Research Journal. 16: 105-112
Ismaniza, I., Idaliza M.S. (2012). Analysis Of Heavy Metals In Water And Fish
(Tilapia Sp.) Samples From Tasik Mutiara, Puchong. The Malaysian Journal of
Analytical Sciences. 16: 346 - 352

APPENDIX

CALCULATION FOR

(CONCENTRATION OF AAS x 50)


MASS OF DRY SAMPLE

For sediment:
Site 1
Chromium (Cr):
0.17 X 50
0.25

0.12 X 50
0.25

R1 =

0.04 X 50
=8
0.25

= 24

R2 =

0.16 X 50
= 32
0.25

R3 =

R2 =

0.03 X 50
=6
0.25

R3 =

= 34

Copper (Cu):
0.04 X 50
0.25

R1 =

= 34

Cadmium (Cd):

R1 = ND

R2 = ND

R3 =ND

Lead (Pb):

R1 = ND

R2 = ND

R3 =ND

Site 2:
Chromium (Cr):
0.17 X 50
0.25

0.23 X 50
0.25

= 46

R2 =

0.19 X 50
= 38
0.25

R3 =

R1 =

0.06 X 50
= 12
0.25

R2 =

0.06 X 50
= 12
0.25

R3 =

= 34

Copper (Cu):
0.08 X 50
0.25

R1 =

= 16

Cadmium (Cd):

R1 = ND

R2 = ND

R3 =

0.002 X 50
0.25

=4
Lead (Pb):
0.02 X 50
0.25

0.04 X 50
0.25

=8

R1 =

0.12 X 50
0.25

= 24

R1 =

R1 =

R1 =

R2 =

0.02 X 50
0.25

=4

R3 =

=4

Site 3:
Chromium (Cr):
0.15 X 50
0.25

R3 =

0.03 X 50
=6
0.25

R2 =

0.03 X 50
=6
0.25

R3 =

0.04 X 50
=8
0.25

R2 =

0.04 X 50
=8
0.25

R3 =

=4

Cadmium (Cd):
0.04 X 50
0.25

0.15 X 50
= 30
0.25

= 30

Copper (Cu):
0.02 X 50
0.25

R2 =

=8

Lead (Pb):

R1 = ND

R2 = ND

R3 =ND

Site 4:
Chromium (Cr):
0.28 X 50
0.25

= 56

R1 =

0.28 X 50
0.25

= 56

R2 =

0.25 X 50
= 50
0.25

R3 =

Copper (Cu):
0.07 X 50
0.25

0.07 X 50
= 14
0.25

R2 =

0.06 X 50
= 12
0.25

R3 =

R1 =

0.01 X 50
=2
0.25

R2 =

0.01 X 50
=2
0.25

R3 =

= 14

Cadmium (Cd):
0.01 X 50
0.25

R1 =

=2

Lead (Pb):

R1 = ND

R2 =

0.01 X 50
0.25

=2

R3 =ND

Site 5:
Chromium (Cr):
0.28 X 50
0.25

Lead (Pb):

R1 =

0.07 X 50
= 14
0.25

R2 =

0.06 X 50
= 12
0.25

R3 =

R1 =

0.01 X 50
=2
0.25

R2 =

0.01 X 50
=2
0.25

R3 =

=4

R2 =

0.25 X 50
= 50
0.25

R3 =

= 14

Cadmium (Cd):
0.01 X 50
0.25

0.24 X 50
0.25

= 56

Copper (Cu):
0.07 X 50
0.25

R1 =

=2

R1 = ND

R2 =

0.01 X 50
0.25

=2

R3 =ND

OYSTER:
Site 1:
Chromium (Cr):
0.08 X 50
0.3

0.10 X 50
0.3

= 16.67

R2 =

0.07 X 50
= 11.67
0.3

R3 =

= 13.33

Copper (Cu):
0.26 X 50
0.3

R1 =

R1 =

0.27 X 50
= 45
0.3

R2 =

0.26 X 50
= 43.33
0.3

0.01 X 50
= 1.67
0.3

R2 =

0.02 X 50
= 3.33
0.3

R2 =

0.01 X 50
0.25

R3 =

= 43.33

Cadmium (Cd): R1 =

R3 =

0.02 X 50
= 3.33
0.3

Lead (Pb):

R1 = ND

=2

R3 =ND

Site 2:
Chromium (Cr):
0.08 X 50
0.3

R1 =

= 1.33

R2 =

0.11 X 50
= 18.33
0.3

R3 =

= 11.67

Copper (Cu): R1 =
0.32 X 50
0.3

0.08 X 50
0.3

= 53.33

0.31 X 50
= 53.33
0.3

R2 =

0.31 X 50
= 51.67
0.3

R3 =

0.07 X 50
= 11.67 R2 =
0.3

Cadmium (Cd): R1 =
0.08 X 50
0.3

0.06 X 50
= 10
0.3

R3 =

= 13.33

Lead (Pb):

R1 = ND

R2 =

ND

R3 =ND

Site 3:
Chromium (Cr):
0.09 X 50
0.3

R1 =

Lead (Pb):

Site 4:

R2 =

0.09 X 50
= 15
0.3

R3 =

0.30 X 50
= 50
0.3

R2 =

0.31 X 50
= 51.67
0.3

R3 =

= 51.67

Cadmium (Cd): R1 =
0.03 X 50
0.3

= 18.33

= 15

Copper (Cu): R1 =
0.31 X 50
0.3

0.11 X 50
0.3

0.03 X 50
=5
0.3

R2 =

0.03 X 50
=5
0.3

R3 =

=5

R1 = ND

R2 =

ND

R3 =ND

Chromium (Cr):
0.15 X 50
0.3

R1 =

0.33 X 50
= 56.67 R2 =
0.3

0.30 X 50
= 50
0.3

R3 =

= 52.22
0.07 X 50
= 11.67 R2 =
0.3

Cadmium (Cd): R1 =
0.06 X 50
0.3

0.14 X 50
= 23.33 R3 =
0.3

= 26.67 R2 =

= 25

Copper (Cu): R1 =
0.29 X 50
0.3

0.16 X 50
0.3

0.05 X 50
= 8.33 R3 =
0.3

= 10

Lead (Pb):

R1 = ND

R2 =

ND

R3 =ND

Site 5:
Chromium (Cr):
0.26 X 50
0.3

R1 =

= 18.33

R2 =

0.21 X 50
= 15
0.3

R3 =

= 15

Copper (Cu): R1 =
0.27 X 50
0.3

0.25 X 50
0.3

= 51.67

0.29 X 50
= 50
0.3

R2 =

0.26 X 50
= 51.67
0.3

R3 =

Cadmium (Cd): R1 =
0.04 X 50
0.3

Lead (Pb):

0.04 X 50
=5
0.3

R2 =

0.05 X 50
=5
0.3

R3 =

ND

R3 =

=5

R1=

0.01 X 50
=5
0.3

R2 =

ND