Project Title: Occurrence, levels and sources of PAHs, PCBs, PBDEs and Dioxins in Malaysianmangrove sediments and their possible ecotoxicological implications

Report Title: An assessment on the pollution levels of PCBs and PBDEs in mangrove
sediments in Peninsular Malaysia

Principle Investigator (Malaysia): Prof. Dr. Narayanan Kannan
Affiliation: Postgraduate Research and Innovation and Strategic Development, Taylor’s University(Lakeside Campus), No.1, Jalan Taylor’s, 47500, Subang Jaya, Selangor Darul Ehsan, Malaysia.

Research Fellow: Han Yeong Kaw
Affiliation: Key Laboratory of Natural Resource of the Changbai Mountain and Functional Molecular(Yanbian University), Ministry of Education, Park Road 977, Yanji City, Jilin Province, 133002, China.

Introduction

Mangrove forests are regarded as one of the most unique ecosystem in the world. Mangroves play asignificant role in protecting coastlines against erosive waves, remove toxic compounds throughnatural filtering processes, provide abundant natural resources and act as an important breeding
ground for a variety of marine animals (WWF-Malaysia, 2016). There is approximately 641,886
hectare of mangrove forest in Malaysia, which is the second largest mangrove forest coverage inSouth-East Asia. Peninsular Malaysia accounts for about 17% of the total mangroves in Malaysia (Abd.
Shukor, 2004), and 70% of it are categorised as permanent reserve forest (Kamaruzaman and Dahlan,2009) (Figure 1). Unfortunately, the mangrove ecosystem in Peninsular Malaysia, particularly in thewest coast along the Strait of Malacca with high anthropogenic activity succumb to pollution. Suchpollution arising from urbanisation and development affect mangrove forests severely, at rates fasterthan their regeneration capacity (Bosire et al., 2003). According to a recent ecotoxicological study
conducted by Krishnan et al. (2016) on mangrove sediments collected from various locations in
Peninsular Malaysia using tetrazolium salt reduction (MTT) assays, mangrove ecosystem is underheavy toxic pressure.

Figure 1. Map showing some of the major mangrove forest reserves in Malaysia. 1:Merbok; 2:Matang;
3:Rungkup and Bernam; 4:Klang; 5:Sepang and Lukut; 6:Pulai; 7:Sungai Johor; 8:Sungai Sarawak;
9:Kampung Tian; 10:Rajang; 11:Kuala Sibuti; 12:Menumbok; 13:Kudat and Marudu Bay; 14:Bengkoka;
15:Sungai Sugut and Sungai Paitan; 16:Trusan Kinabatangan; 17:Kuala Segama and Kuala Maruap;
18:Lahat Datu; 19:Segarong and Semporna; 20:Umas-umas, Tawau and Batumapun (Chong, 2006).

Methodology

Study Area
Nine mangrove areas in Peninsular Malaysia that located at the coastline facing the Strait of Malaccain the west and facing the South China Sea in the east were selected for investigation. The sediment
sampling was carried out during May 2015 until July 2015 under low tide. At each location threesub-samples were taken at a distance of 15 to 40 meters. Figure 2 and Table 1 shows the latitude andthe longitude of the sampling locations.

Figure 2. Location of the mangrove forests selected in this study.

Table 1. Details of the sampling sites
SiteLocation

StateLongitude

LatitudeSurrounding activities

1

Larut Matang

Perak4.84358

100.63317

Eco-tourism

2

Lumut

Perak

4.21846100.64486

Residential area

3

MerbokKedah

5.68183

100.46875

Fisheries

4

Tanjung Pelepas

Johor

1.34829103.56989

Domestic dumping site

5

Tanjung Agas

Johor

2.05510102.56932

Industrial, commercial

6

LukutNegeri Sembilan

2.58571101.82659

Industrial, fisheries

7Pulau IndahSelangor

2.94469

101.35795

Residential, industrial

8

Tanjung Lumpur

Pahang3.80583

103.33459

Commercial, dumping site

9Kuala Terengganu

Terengganu

5.32084

103.10193

Fisheries, boating

Sample Collection
Triplicate top surface sediment samples (1-5cm) were collected using stainless steel spoon at each of
the nine mangrove forests in Peninsular Malaysia. The scrapped surface sediment samples wereoimmediately transferred into amber glass container and stored at -20 C until further analysis. All thesampling tools and apparatus were soaked in acid for at least 24 hours and rinsed with distilled water
before use to avoid contamination. All sediment samples were freeze dried before chemical analysis.

Chemical Analysis

Approximately 7g of the freeze-dried sediments samples were extracted with a mixture ofacetone/hexane (1:1 v/v) using a rapid solvent extractor (SE100, Mitsubishi Chemical Analytech) at a-1o13
flow rate of 6ml min at 35 C for one hour. The extract was spiked with C-labelled standards for
PCBs and PBDEs. The spiked extract was treated with hexane-washed sulphuric acid (98%) and passed®
through a multi-layer silica gel column packed in a bottom-up order with deactivated silica (Wakogel
DX, Wako, 0.5g), KOH-impregnated silica (Wako, 3% KOH, 3g), deactivated silica (0.5g), and sulphuric
acid-impregnated silica (Wako, 44% Sulphuric acid, 2g and 22% sulphuric acid, 6g), with hexane/DCM(3:1 v/v, 150ml) as eluant. The extract was then subjected to activated silica column clean up stepusing 5% DCM/Hexane (1:19 v/v, 80ml) as eluant. The extract was being treated with copper and thensubjected to GC-MS quantification (Agilent 7890A GC; Agilent 5975C inert XL MSD).
Congener specific analysis of 31 PCBs (CB18, CB28, CB33, CB22, CB37, CB52, CB49, CB44, CB74, CB70,CB77, CB95, CB101, CB99, CB87, CB110, CB118, CB105, CB151, CB149, CB153, CB138, CB158, CB128,CB167, CB156, CB183, CB177, CB180, CB170, CB209) and 16 PBDEs (BDE28, BDE49, BDE47, BDE100,BDE99, BDE154, BDE153, BDE183, BDE201, BDE197, BDE203, BDE196, BDE208, BDE207, BDE206,BDE209) were carried out on sediment samples. Analysis of PAHs and Dioxins was not carried out onthese samples as proposed in the original proposal due to time restriction, availability trainers,
availability of research fellow’s training schedule and finally on the availability instruments.

Result and discussion

The concentrations ofLevels (ng/g dry weight) of PCBs and PBDEs determined in mangrove sediments collected from
Puninsular Malaysia are shown in figure 3. The highest value of PCBs concentration was recorded insediments samples from site 6 (Lukut - 16.5 ng/g dry weight) and the lowest PCBs concentration was
found at site 3 (Merbok). At site 8 (Tanjung Lumpur) and site 9 (Kuala Terengganu) no PCBs weredetected. On the other hand, relatively higher concentration of PBDEs (169 ng/g dry weight) was
found at site 5 (Tanjung Agas), followed by site 7 (Pulau Indah) and the lowest value was recorded atsite 4 (Tanjung Pelepas). A map was generated to compare PCBs and PBDEs concentrations ofmangrove sediments analysed in Malaysia. It is obvious that the concentration of PBDEs in all sites
were higher than PCBs concentrations, particularly at Tanjung Agas, Lukut and Pulau Indah. ThePBDEs were several magnitudes higher than PCBs. PCB-containing electrical equipment are not
manufactured in Malaysia and the import has stopped on June 1998 (Hashim, 2003) Hence it isreasonable to observe low PCBs concentration than PBDEs. On the other hand, flame retardants(PBDEs) are used widely on electronic devices whose consumption increases constantly in Malaysia. In2014, the electronic components sub-sector became the largest sub-sector with an approved
investments of RM 5.8 billion (MIDA 2017). The most dominant PBDEs among the 16 PBDEs studies
was PBDE 209, the deca PBDE. According to Kwan (2013) the sedimentary BDE-209 concentrations inAsia showed a trend toward higher concentrations in the more industrialized Asian countries, andwere similar to or higher than those reported for highly urbanized and industrialized countries
worldwide. Thailand, Cambodia, India, the Philippines and Malaysia are possible hot spot areas ofPBDE pollution.

Figure 3. Maps showing PCBs concentration (left) and PBDEs concentrations (right) of mangrove
sediment samples collected in Peninsular Malaysia.

Figure 4. Comparison of the PCBs and PBDEs concentrations of mangrove sediment samples collectedin Peninsular Malaysia.

The concentrations of PCBs and PBDEs in mangrove sediments collected from Peninsular Malaysia arecompared with similar studies conducted elsewhere in Table 2. PCBs concentrations in Hong Kong andSingapore are comparable, however Indonesia shows several fold higher concentration. The PBDEs
trend is similar to Malaysia. Kaw and Kannan (2016) observe that substantial studies on thesechemicals in Malaysia need to be conducted to compare and assess the pollution level and impact.

Table 2. Comparison of the concentration of PCBs and PBDEs in surface sediments collected frommangroves in Peninsular Malaysia and other countries.
Site

LocationPCBs(ng/g dw)

PBDEs
(ng/g dw)

Reference1

Larut Matang

0.252

1.90

This study

2

Lumut

0.773

8.03

This study

3

Merbok00.63

This study

4

Tanjung Pelepas

0.690

0.56

This study

5

Tanjung Agas0.107169

This study

6Lukut16.5

39.5

This study

7Pulau Indah

1.433

47.3

This study

8

Tanjung Lumpur

00.877This study

9Kuala Terengganu

05.1This study

Singapore

0.59-1.86<1Bayen et al. (2005)

Hong Kong-

14.4/2.10*

Zhu et al. (2014)

Indonesia

0.07-420

0.17-35

Ilyas et al. (2011)*Concentration of PBDEs at two different mangrove areas in Hong Kong.

Conclusion
This project has initiated a research collaboration between Japan and Malaysia using LaMer, Ehime
University, Matsuyama, Japan. Sediment samples were collected from Mangrove ecosystem andanalyzed for PCBs and PBDEs. The analytical results indicated low PCBs levels but an increasing PBDEs,
particularly Deca BDE. This trend needs to be established in the future, if samples of other matrices
are collected and analyzed.

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