Heavy metals in langkawi corals

Presented by:

MASRISAZLIN BINTI BAKRI 2010729369

FSG650

INTRODUCTION

1.1 Background of Study

1.2 Problem Statement

1.3 Significant of Study

1.4 Aim of Study

1.5 Objectives of Study

1.1 Background of Study

Heavy Metals:

Metals and metalloids.

Conservative in nature.

Deemed serious pollutants because of toxicity, persistence and non-biodegradability in the environment (Pekey, 2006).

Cd, Cr, Cu, Ni, Pb, and Zn are considered potentially hazardous to the human health and the environment (Lata & Rohindra, 2002).

Coral colonies integrate calcium carbonate and the rate depends on the growth and environment conditions.

Forms annual bands within coral reefs.

Skeletal growth: linear extension, density, and calcification.

Carries independent information and assessment of coral growth.

Bands provide information about coral growth rates and about how fast corals grow in different environments.

Figure 1: The radiograph X-Ray image of Coral growth rate.

Sources: Stephen E. Lewis, G. A. (2006).

Thus, these study will tracing the heavy metals in each of 5 years growth rate bands of Diploria

Labyrinthiformis sp. and Favia Pallida sp. corals.

The study also will to observe the trend and correlationships of the three heavy metals

in the bands of the coral slab.

1.2 Problem StatementCoral reefs;

Undergoing degradation due to bleaching events as a result of high sea surface temperature (SST).

Essential for the livelihood of people living around coastal areas as well as for the economy of Langkawi.

Figure 2: Beras BasahIsland

A major attraction for tourists and the economy of the country is boosted through its fishery resources.

People depend on it as a source of food and income generation.

The major issues affect Langkawi’s coral reefs including :

Loss of water quality in estuaries and lagoons as a result of poor land-use practices, elevated levels of sediments and nutrients, crown of thorns starfish

outbreaks and coral bleaching.

“Considering the importance of the healthy coral reef ecosystems to Langkawi’s economy as well as to the

global coral reef biodiversity”

1.3 Significant of Study

The focus of this study was on determining the level of heavy metal contamination in each of 5 years growth rate bands in Diploria Labyrinthiformis and Favia Pallida corals.

Observe the trend of heavy metal accumulation within the corals.

Estimate the metal pollution index of DiploriaLabyrinthiformis and Favia Pallida corals.

Useful for further research as reference in relation to heavy metal contamination in Diploria Labyrinthiformis andFavia Pallida corals and this study area in future.

1.4 Aim of Study

Present study is aim to evaluate the level of pollution index in Diploria Labyrinthiformis and Favia Pallida corals and sediments by determine the accumulation of Cadmium (Cd), Copper (Cu), and Lead (Pb), concentration by using metal assessment index analysis of Metal Pollution Index (MPI).

AAS was used for the heavy metal extraction analysis.

Pearson’s correlation coefficient and Two-Way ANOVA statistical analysis were applied to determine the significance difference of result gather for corals and depths in five different growth rate bands.

Figure 6: Atomic Absorption Spectrometer

1.5 Objectives of Study

1) To determine the concentrations of Cadmium (Cd), Copper (Cu), and Lead (Pb) in the bands of coral slab sampled from Langkawi waters by using Atomic Absorption Spectrometer (AAS).

2) To observe the trend and correlationships of the three heavy metals in the bands of the coral slab.

LITERATURE REVIEW

2.1 Heavy Metals in Marine

Environment

2.2 Hard Corals as Bio-indicator

2.1 Heavy Metals in Marine EnvironmentHeavy Metals in Marine According to Elder (1988), the fractionation of

heavy metals depends on many factors including organic matter composition, pH, salinity and binding affinities of heavy metals.

In the other hand, a research done by Al-Rousanet al,. (2007) has founded that corals can be exposed to high metal concentrations as a result of human activities such as harbor dredging or sewage discharge.

Heavy metal accumulation occur in the coral skeleton as a result of structural incorporation of the metals in the aragonite (Goreau, 1977), inclusion of particulate materials in skeletal cavities (Howard & Brown, 1984), surface adsorption onto the exposed skeleton (St John 1974, Brown et al 1991) and chelating with the organic matrix of the skeleton (Mitterer, 1978).

Linton and Warner, 2003 Corals are thought to be good indicators of the metal content in the marine environment. An important fraction of the metals in the marine environment is associated with particulate organic matter.

Corals incorporate organic material in the pores of their skeleton. In so doing they incorporate seawater contaminants such as trace metals and phosphorus into their skeleton during normal growth, making them faithful long-term recorders of environmental water quality.

Khaled et al., 2003 Corals and especially their skeleton have beenused as proxy tools to record environmental pollution such as trace metal.

The trace metal concentration in skeletonphase of corals can be used to monitor changes in environmental metal loads at different investigated sites which attributed to inputs from pollution associated with contaminated river water and estuary, offshore and near-shore mining, shipping and oil spills accidents anduncontrolled and regulated developments on the reefs surroundings.

Mazlin et al,. 2000 The research conducted a similar study to this. They used coral heads of Porites lutea to assess the level of heavy metal contamination from Pulau Payar waters, Langkawi. Results show that the levels detected were low and reflected the clean environment of Pulau Payar Marine Park

Concentrations of the metals in sediment and coral samples were low and similar in magnitude (as compared to metals in corals already studied in other parts of Malaysia and other countries), and these indicated the clean state of the PulauPayar Marine Park waters.

No clear temporal and spatial variations have been demonstrated by results of the present study except for Pb which showed an increasing concentration trend towards the oldest bands, and this is perhaps indicative of increasing number of boats that landed at jetty of the PulauPayar Marine Park.

METHODOLOGY

3.1 Study Area

3.2 Sample Collection and Preparation

3.3 Samples Digestion

3.4 Statistical Analysis and Assessment Index

3.1 Study Area

Figure 7:Location of BerasBasahIsland, Langkawi.

Longitude: 6° 21’ N

Latitude:99° 48’ E

Scientific MethodologySamples Collection

Corals:Diploria Labyrinthiformis sp.

& Favia Pallida sp.

Run experiment Using AAS

Data Analysis

Results & Discussion

Conclusion

3.2 Sample collection and preparation

Put in the plastic bag

Fragment, label & frozen

3.2.1 Quality control

Equipments and materials used were

immersed in 5% HNO3

acid wash for overnight

only use stainlesssteel equipment

Was cleaned using acetone

3.2.2 Standard Solution Preparation

Mix 100 mg CdMetal +4.0 ml HNO3

Another HNO3 wasadded to become 10 ml

Transfered into 100 ml of volumetric flask. Dilute with Milli-Q water to up 1000 ml

Mix 100 mg Cu Metal +2.0 ml HNO3

Mix 159.8 mgLead (II) Nitrate +1:1 HNO3

3.2.3 Sample Preservation

Corals were rinsed with distilled

water

Thawed & rinsed with 2% Ammonium Citrate

Put in plastic container & cover with Ammonium Citrate

Sonicate for 5-8 hours

Rinsed with deionizedwater

72 hours at 80˚C

Cut each growth rate bands for 5 years bands Samples were

grounded

100˚C for 2 hours

10 ml of 1:1 HNO3 + H2O2

10 mL test tube

1.0 g of dried coral sample

3 hours refluxed

3.3.1 Corals Digestion

2 ml of HCl was added

30 minutes refluxed

Made up to 50 ml with deionised water

3.4 Statistical Analysis

Hypothesis test for difference between two species means. The Two-Way ANOVA:

The assumption were,

H0 : There is no significant difference between the two species of corals.

H1 : There is significant difference between the two species of corals.


H0 : There is no significant difference between every depth.

H1 : There is significant difference between every depth.

3.4 Statistical Analysis Two-Way ANOVA had indicated no significant difference between the

two species and also parameter (different depths of coral slabs) for Cd, Cu, and Pb.

The possible explanation for the analysis was because both species are brain corals and their ability in accumulating the heavy metal is about the same.

Brain corals can incorporate trace metals by a variety of mechanisms which are from dissolved trace metal species can migrate into crystal lattices, and trace metal particulates may become trapped within skeletal cavities by the uptake of trace metals from coral tissue.

Similarly with each depth showed no significant difference between all the depths because the higher accumulation generally occurred at the surface of corals.

The Pearson’s Correlation Coefficient:



The assumption was,

H0 : There is no significant correlation of heavy metals concentration between two possible elements.

H1 : There is significant correlation of heavy metals concentration between two possible elements.

It is consider to be significant statistically when P-value is less than 0.05

RESULT & DISCUSSION4.1 Heavy Metal Concentration

in corals

4.2 Relationships

4.3 Comparison with other study

4.4 Assessment Index

4.1.1

Elements Profile

Cadmium (Cd)

(mg/L)

Copper (Cu)

(mg/L)

Lead (Pb)

(mg/L)

Depth

(cm)

*Species A *Species

B

Species A Species B Species

A

Species B

3 0.01 0.017 0.0248 0.0181 0 0.0319

6 0.01 0.017 0.0319 0.0418 0.0256 0.1455

9 0.011 0.017 0.0357 0.0437 0.1143 0.2203

12 0.014 0.023 0.0436 0.0671 0.1878 0.2944

15 0.014 0.026 0.0833 0.2698 0.2694 0.3963

Average 0.0118

±0.002

0.01716

±0.02

0.04385

±0.11

0.0881

±0.004

0.11942

±0.1

0.21768

±0.14

(HKEP

D,

1997)

2.00 2.00 6.00

MPI Species A:

0.058 ± 0.062

Species B:

0.088 ± 0.052

4.1.2 Concentration of Cd

The trend concentration of Cadmium is considered decreased from the bottom (oldest) to the surface (youngest) layer of the Diploria Labyrinthiformis and Favia Pallida samples.

Levels of Cd depend on industrial activities, fishing landing ports, domestic sewage.

Field observation showed that a lot of boats that bring passengers and tourist pass through the area everyday which might influence the Cd load in the environment.

Besides this fact, Cd is a component of petrol’s, diesel fuels and lubricating oil.

4.1.2 Concentration of Cd

4.1.3 Concentration of Cu The trend concentration of Copper is decreased

gradually from the bottom (oldest) to the surface (youngest) layer of the both species samples.

Loading and offloading fishes from fisherman, cleaning of boats and maintenance, antifouling paint applications, and fueling activity.

4.1.3 Concentration of Cu Lafarge Cement Sdn. Bhd. manufactures cement was

founded in 1984 and is based in Teluk Ewa, LangkawiIsland

Copper is often found as trace element in common metal sulfides pyrite (FeS2), zinc blende (ZnS), galena (PbS) present as secondary minerals in most of the raw materials.

Figure 4.1.3 The location of Lafarge Cement Sdn. Bhd with Pulau Beras Basah

4.1.3 Concentration of Cu

4.1.3 Concentration of Pb The trend concentration of Lead is increased gradually

from the surface (youngest) to bottom (oldest) layer of the Diploria Labyrinthiformis and Favia Pallidasamples.

Construction leads to deforestation as more trees and forests are leveled to make way for buildings in Langkawi Island.

4.1.4 Concentration of Pb

4.2

Relationships Based on

Analytical Statistic

Correlation Matrix

Cd Cu Pb

Cd 1

Cu 0.785618 1

Pb 0.944967 0.902783 1

Cd Cu Pb

Cd 1

Cu 0.863105 1

Pb 0.875287 0.8204 1

Figure 4.2a:Correlation Matrix for Diploria

labyrinthiformis

Figure 4.2b:Correlation Matrix for Favia

Pallida

Relationships

Both species showed more than 0.7 values for correlation.

The values of correlation obtained were more than 0.7 indicates strong positive relationships.

There were linear relationship between Cd and Cu, Cd and Pb, and also between Cu and Pb.

Thus, the linear regression line is significant. This shows that Cd, Cu, and Pb come from the same source.

4.3

Comparison

with other studies

Study Area Species Cd Cu Pb Author

Pulau Beras Basah Diploria

Labyrinthiformis

0.01 – 0.014

mg/L

0.0248 –

0.0833 mg/L

0 – 0.2694 Present Study

Pulau Beras Basah Favia Pallida 0.017 –

0.026 mg/L

0.0181 –

0.2698 mg/L

0.0319 –

0.3963 mg/L

Present Study

Surat Thani

Province, Thailand

Porites Lutea 0.04 – 0.16

mg/Kg

1.53 – 4.42

mg/Kg

0.57 – 1.53

mg/Kg Sirianansakul et

al., 2007

Favia Speciosa 0.15 – 0.37

mg/Kg

1.61 – 5.40

mg/Kg

1.87 – 2.48

mg/Kg

Goniastrea Pectinata 0.05 – 0.19

mg/Kg

2.17 – 3.35

mg/Kg

1.62 – 3.75

mg/Kg


Hong Kong,

China

Porites Andrewsi 0.16 ±

0.08

mg/Kg

N/A 13.0 ±

0.02

mg/Kg

Ramos et al.,

2004

Lakshadweep

Archipelago

Acropora 0.81

mg/L

0.60 mg/L 9.64 mg/L Anu Gopinath,

2002

Namoussoukro Labophyllia

Corymbosa

N/A 0.008 –

0.019

mg/L

0.015 –

0.021

mg/L

Sadat et al.,

2012


Papan Island,

Sabah

Hydnophora

Microconus

1.8 ±

0.008

mg/Kg

6.7 ±

0.57

mg/Kg

N/A Mazlin et

al., 2012

Favia

Speciosa

2.0 ±

0.04

mg/Kg

7.5 ±

0.74

mg/Kg

N/A

Porites Lobata 1.5 ±

0.09

mg/Kg

6.4 ±

0.73

mg/Kg

N/A

Jordan Gulf Porites Lobata 0.61

mg/Kg

0.32

mg/Kg

3.61

mg/Kg

Nedal Al

Ouran,

2005

Mazlin et al., 2000

(Porites lutea)

Present Study (Diploria

Labyrinthiformis)

Present Study (Favia

Pallida)

Cadmium

5 1 0.014 0.026

4 1 0.014 0.023

3 1 0.011 0.017

2 1 0.01 0.017

1 <1 0.01 0.017

Copper

5 N/A 0.0833 0.2698

4 N/A 0.0436 0.0671

3 N/A 0.0357 0.0437

2 N/A 0.0319 0.0418

1 N/A 0.0248 0.0181

Lead (Pb)

5 19 0.2694 0.3963

4 15 0.1878 0.2944

3 14 0.1143 0.2203

2 14 0.0256 0.1455

1 14 0 0.0319

4.4 Heavy metal assessment index

Depth (cm) Diploria

labyrynthiformis

(mg/L)

Favia Pallida

(mg/L)

3 0 0.02

6 0.02 0.14

9 0.04 0.06

12 0.16 0.08

15 0.07 0.14

Average 0.058 ± 0.062 0.088 ± 0.052

CONCLUSION &

RECOMMENDATION

Conclusion

The main objectives of this study to determine the concentrations of Cadmium (Cd), Copper (Cu), and Lead (Pb) in the bands of coral slab sampled from Langkawi waters by using Atomic Absorption Spectrometer (AAS), and to observe the trend and correlationships of the three heavy metals in the bands of the coral slab were achieved.

Conclusion

Concentrations of the heavy metals in both coral species samples were low and this indicated the clean state of the Pulau Beras Basah waters.

The trend and correlationships of the Cd, Cu, and Pbin the bands coral slab showed the increasing trend of concentration which were increased gradually from the surface (youngest) to bottom (oldest) layer for the samples.

Recommendation

More research work regarding the tracing of heavy metals in growth rate bands is needed in Malaysia as to date there is only few data available for Malaysia corals.

Emphasis has to be paid on the following recommendation:

Recommendation Make a baseline study of other coral species within

Malaysia waters.

Coral species has to be analyzed from different depths and after occurrence of natural disasters if possible.

Coral colonies have to be selected from varying depths in order to determine the environmental impact on coral generally and to another marine life specifically.

Cited References Carys L. Mitchelmore, E. A. (2007). Uptake and partitioning of copper and cadmium. Aquatic

Toxicology 85 (2007), 48-56.

Derya Karaa, A. F. (2008). Determination of trace heavy metals in soil and sediments by atomic spectrometry following preconcentration with Schiff bases on Amberlite XAD-4. Journal of Hazardous Materials 165 (2009), 1165-1169.

McDonald, J. (2004). Stable isotopic and Trace Metal Analysis of Two Porites Lobata Colonies.

Mokhtar, M. (2000). Trace Metals in Langkawi Coral and Sediment: A study using AAS and XRF. Malaysian Journal of Analytical Sciences, Vol. 7, No. 1 (2001) 189-196, 189-196.

Sabdono, A. (2009). AN ASSESSMENT OF HEAVY METAL CONCENTRATIONS IN THE SCLERACTINIAN CORAL TISSUES OF KARIMUNJAWA ARCHIPELAGO, INDONESIA. Journal of Coastal Development Volume 13, Number 1, October 2009, 9-17.

Shah, S. B. (2008). Study of heavy metal accumulation in Sclerectinian Corals of Viti Levu , Fiji Islands.Suva, Fiji Islands: School of Marine Sciences Faculty of Islands and Oceans.

Shen, G. T. (1979). Lead and cadmium geochemistry of corals: Reconstruction of Historic perturbations in the upper ocean. S.B, Massachusetts Institute of Technology.

Stephen E. Lewis, G. A. (2006). A multi-trace element coral record of land-use changes in the. Palaeogeography, Palaeoclimatology, Palaeoecology 246 (2007), 471-487.

Heavy metals in langkawi corals

Environment

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