Xinhong Wang1, Heyang Li2, Yusheng Zhang2

1
Reconstruction of Contamination History for PAHs
and Organochlorine Pesticides in the Marine
Sediment Cores from Andaman sea, Malaysia

• Xinhong Wang1, Heyang Li2, Yusheng Zhang2
• 1. Environmental Science Research Center, Xiamen
  University, Xiamen, 361005, P.R.China
• 2. Third Institute of Oceanography, State Oceanic
  Administration, Xiamen, 361005, China

2

• PAHs and OCs are hydrophobic, potentially toxic
  and persistent pollutants, which are ubiquitous
  in the environment. Once produced, they enter the
  environment through air transportation or stream
  pathway and accumulate in the sediment
  eventually.
• The profile of organic pollutants concentrations
  in an undisturbed sediment core can be used as
  temporal indicator to study the trends of the
  past and present variations of their inflow and
  usage.

3

• Malaysia is a major producer of primary
  commodities
• Malaysia has a dominant world position in rubber,
  palm oil and cocoa Concomitant with the emphasis
  on agricultural development in the 1960s and
  1970s.
• Develop history emphasis on agricultural
  development in the 1960s and 1970s, pollution
  from the agro-based industries accounted for
  approximately 90 of the industrial pollution
  load and was the largest source of water
  pollution during a period when there were
  inadequate provisions for regulating the
  discharge of effluents (Abdul Rani
  Abdullah,1995).

4

• The wide use and spread of pesticides has
  resulted in detrimental effects on aquatic
  resources.
• The 2004 Indian Oceanic Tsunami has caused
  considerable changes in the marine ecosystem by
  polluting the marine environment with high
  turbidity
• and damaging the coastal zones.

5
Objectives

• To reconstruct the usage history of PAHs and OCs.
• To trace the sources of pollution.
• To compare the concentrations and variations of
  PAHs and OCs in sediment cores to evaluate the
  influence of Tsunami on the sediment.

6
Sampling
WC02
KM24
Sediment Rate WC02 0.5 cm/ year covered the
past 100 years. KM24
0.76 cm/year and covered the past 80 years.
7
PAHs and OCs analysis
16 PAHs Naphthalene (Na)
Acenaphthylene (Ace), Acenaphthene (Acen),
Fluorene (Flu), Phenanthrene (Phen), Anthracene
(An) Fluoranthene (Fluo), Pyrene (Py),
Benzo(a)Anthracene (BaA), Chrysene (Chry)
Benzo(b)Fluoranthene (B(b)FA), Benzo(k)Fluoranthen
e (B(k)FA), Benzo(a)Pyrene (B(a)P),
Dibenz(a,h)Anthracene (DiBaA) Indeno(1,2,3-cd)Pyr
ene (Indeo), Benzo(ghi)Perylene (B(ghi)P).
25 or 17 organochloriated pesticides
(a-HCH?HCB?ß-HCH??-HCH?d-HCH?Heptachlor?Aldrin?Iso
drin?Heptachlor epoxide A?oxychlordane?Heptachlor
epoxide B?Chlordane A?OP-DDE?Endosulfate??Chlorda
ne B?Dieldrin?PP'-DDE?OP'-DDD?Endrin?Endosulfate
??PP'-DDD?OP'-DDT?PP'-DDT?Methoxychlone?Mirex)
8

• PAHs were performed on an Agilent 6890 GC MSD
  using an HP-5 MS column (30 m 0.25 mm 0.25
  mm).

OCs were performed by Agilent 5890 GC-ECD
using an HP-5 column (60m 0.32 mm 0.25 µm ).
9

• PAHs Agilent 6890 GC-5973 MSD operating in
  selective ion monitoring mode using an HP-5 MS
  column (30 m 0.25 mm 0.25 mm ). Samples were
  injected in splitless mode with the injector
  temperature at 280?. Helium was used as carrier
  gas at a flow rate of 1 mL /min. Oven start at 90
  ? with 1 min hold, ramp to 160 ? at 15?/min, and
  then to 290 ? at 8 ?/min with a final hold of 8
  min.
• OCs Agilent5890 GC-ECD using an HP-5 column
  (60m 0.32 mm 0.25 µm )High purity nitrogen
  was used as carrier gas Samples were injected in
  splitless modeThe injector and detector
  temperature was 250?and 320?, respectively. Oven
  start at 90? with 1min hold,rampt to 210? at the
  rate of 10?/min with 1min holdand then to 230?
  at 1 ?/min with 10 min holdfinally, it increased
  to 250? at 1?/min.

10
QA/QC

• Deuterated PAH compounds (naphthalene-d8,
  acenaphthene-d10, phenathrene-d10, chrysene-d12
  and perylene-d12) , as well as PCB166?PCB209?2,4,5
  ,6-tetrachlore-oxyl-dioxin were used for
  surrogates and internal standards, which were
  spiked in the samples prior to extraction for
  quantifications .
• The recoveries of PAHs ranged from 65 to 125
  and from 50.4 to 124 for OCs.

11
Figure 1. PAHs variations in sediment cores.
PAHs
WC02
Phenathrene was prevalent component in most
samples, accounting for 836 .
KM24
WC02 13.25 to 60.11 (the mean 18.09 ) ng/g
KM24 24.39 to 327.40 (the mean 78.24) ng/g.
12
Table 1 Comparison of PAHs contamination with
other sites in the World

• That means that the environment at these area
  were not impacted by human activity heavily and
  PAHs contamination was not much seriously. In
  some degree, it is impact by anthropogenic
  activities at KM24.

13

Figure 3. Depth profile of PAH concentrations in
sediment core-KM24
14
Figure 4. Depth profile of PAH concentrations in
sediment core-WC02
15
Sources of PAHs
Anthropogenic PAHs originate mainly from
combustion of biomass and fossil fuels and oil
spillage. Isomeric ratios of PAHs are classical
indices for apportioning sources of PAHs in the
environment.
Indeo/(Indeo t BgP) lt 0.2, and Fluo/(Fluo t Py) lt
0.4 implies petrogenic PAHs, while ratios of
both greater than Indeo/(Indeo t BgP) gt 0.5,
Fluo/(Fluo t Py) gt 0.5 suggest PAHs origin from
combustion of coal and biomass. 0.2ltIndeo/(Indeo
t BgP) lt0.5, Fluo/(Fluo t Py)gt0.4 implies PAHs
originate from petroleum (vehicle fuels and crude
oil) combustion.
16
WC02
17
incomplete combustion
Petrogenic
KM24
18
OCs
KM24
WC02 0.11 to 111.04 (the mean 16.60 ) ng/g
KM24 23.13216.57 (the mean 66.71) ng/g.
WC02
Figure 7. OCs variations in sediment cores.
19
Figure 8. Component of HCHs and DDTs in sediment
core-KM24
?HCHs0.5724.36 ng/g(mean5.79 ng/g),2.2129.73
of total organochlorine pesticides?DDTs
0.9952.99 ng/g (mean 6.34 ng/g), 1.9229.62
(mean 7.52),with a peak at 56 cm (the year of
2001).
20
Figure 9. Component of HCHs in sediment core-WC02
?HCHs0.2254.86 ng/g?DDTs 018.20 ng/g,with a
peak at 56 cm (the year of 2001). Garma-HCH and
p,p-DDT were dominant in WC02.
21
Figure 10. Vertical variations of OCP
concentrations in sediment core-KM24 .
Total OCs level were generally lower below
the depth of 20cm ( lt10 ng/g ) compare with the
uper layer (more than 100 ng/g )of the sediment
cores. From 20cm to 8cm (1980s-2000s), the
concentrations of OCs especially for HCHs varied
slightly from 18-50cm, the variation of total
OCs include HCHs and DDTs did not show
significantly difference.
22
Figure 11. Depth profile of OCs concentrations in
sediment core-WC02
OCs changed very slightly below 10cm before the
year of 1990s. From 6cm to the surface, the sum
of OC compounds showed changeable, which also
indicated that OCs begin input to the sea after
1990s.
23
Conclusion

• Sedimentary records of PAHs and DDTs
  in Malaysia sea reflected the economic
  development in Malaysia over one hundred years.
• 1. There could be find the environment
  background of PAHs in this area before
• 1980s in core KM24 and before 1920s in
  core WC02.
• 2. KM24 were contaminated by PAHs more
  serious than that in WC02, which
• indicates the impact of human activities
  especially for sewage discharge and ship
• activities in the marine coastal
  environment.
• 3. Sediments originate predominantly from
  combustion of coal and biomass, or the mixture.
• 4. Based on the vertical distribution of OCs
  in the sediment cores, it were found
• that manufactured pollutants input the
  sea mainly after 1980s. The total OCs still
• increase, DDTs concentration decreased
  in recent ten to twenty years.
• 5. The results can not really evaluate the
  impact of Indian Ocean Tsunami on the
• sediment from Malaysis for the limit
  data and suitable samples in these area.

24
Thank You!
25
(No Transcript)
26
(No Transcript)