Concentration
of Persistent Organic Pollutants in the coastal hydrosphere of Thailand
Ruchaya.
Boonyatumanond, Suthib. Srilachai,
Sukanya.Boonchalermkit,
Yuwadee In-na,
Environmental
Research and Training Center,
Technopolis,
Tambon Klong 5, Amphoe Klong Luang,
Pathumthani
12120, Thailand
Department
of Environmental Quality Promotion,
Ministry of Natural Resource and
Environment
Abstract
The
mornitoring program on persistent organic pollutants (POPs) was started from
April 2002-March 2003. For forty-eight water samples from 4 main rivers and
coastal water along the Gulf of Thailand were analysed for POPs in dry season
and wet season by UNU method. The result indicated that the water
quality for POPs of river and sea water sample from the coastal area of
Thailand is not polluted from POPs. The concentration of POPs residues were
detected at the range of 4.2-13.9 ng/L (ppt) with 13C12 recovery
85-95%. The concentration of POPs residues in water samples are lower than
Water Quality Standard by Notification of the National Environmental
Board, No. 7-8, B.E. 2537 (1994 ).
Introduction
Persistent Organic Pollutants (POPs) are
toxic substances of organic (carbon-based) chemical compounds and
mixtures. They are dioxin, furans, polychlorinated biphenyls (PCBs), DDT,
chlordane, heptachlor, toxaphene, hexachlorobenzene, aldrin, dieldrin, endrin
and mirex. These chemicals are products and by-products of human
industrial activities that are relatively recent in origin. POPs are persistent
in the environment. This means that the substances resist photolytic,
chemical and biological degradation . They are general
semi-volatile. They are also subject to global distillation. They
can travel with the potential to injure human health and /or the environment ( Stephen
1994; Kannon et al., 1994 ; Kannon et al., 1995) . They generally have
low water solubility and high lipid solubility. They tend to bioaccummulate
in fatty tissues of living organisms. In the environment, concentrations
of these substances can magnify by factors of many thousands as they move up
the food chain (Sericano, et al., 1995; Boonyatumanond et al., 2000 and 2002; ).
These chemical find their way into everything (i.e. air, soil, water and food)
(Ogaki et al., 1994; Iwata et al., 1993 ). These facts suggest the significant
atmospheric transport tpo persistent organochlorines to the Actric from lower lateitudes.
In spites of regulation or prohibition on the chemicals imposed in the
most-developed nations since the 1970s , their usage and disposal are still
continuing or increasing in developing countries near tropical regions (Forget
1991). ( For the listed POPs pesticides use as alternatives are made available
for the small number of remaining recognized uses such as aldrin, dieldrin,
chlordane and DDT . For the listed POP industrial chemicals there is need to
phase out, over time such as PCBs and HCB.
Polychlorinated
Biphenyls (PCBs) used for a variety industrial uses, including in electrical
transformers and large capacitors as heat exchange fluid, as paint additives
and carbon-free copy and in plastics. The chemical properties primarily
responsible for many of the industrial applications of PCBs, that is their
inflammability, chemical stability, and miscibility with organic
compounds (i.e., lopophilicity), also are the same properties that have
contributed to their environmental problems. These compounds
preferentially bioaccumulate and biomagnify in higher tropic levels of the food
chain. (Hansen ., 1987)
POPs
are highly toxic and have the potential to injure human health and the
environment at low concentrations. Damage caused to humans and other species by
POPs is well-documented and includes the pathologies of cancer and tumors at
multiple sites, reproductive disorder, neurobehavioral impairment including
immune system dysfunction , lack of development in various body system (
Ohanjanyan et al., 1999).
Thailand
has benefited from the availability of the growing pest control
chemicals. To support agricultural product in our countries and export
product, many kinds of pesticide were imported such as insecticide, fungicide ,
and herbicide, etc. Because there are resistant chemicals and toxic, the government
enforce to decrease and limit using it. In order to understand the distribution
of the chemicals residues remain in environment, the fresh water from 4 main
river and sea water from the coastal area were analyzed .
Material and method
The monitoring programme started from
April-December 2002. Fourty eight samples of water were collected at 24
stations from four main rivers namely, The Chao Phraya river, The Mae-Klong
river, The Bang Pa-kong river and The Tha-Chin river including the coastal area
along the gulf of Thailand and Andaman sea side as showned in Figure 2, Figure
2 and information of sampling as shown in Table 1.
The Chao Phraya river is the most important
river in Thailand, flow through several cities including Bangkok. There are
industrial located along the river and a large number of inhabitants live along
the river banks. The river, which discharges into the upper Gulf at Samutprakran
province, has an average discharge varying from 8,000 x 106 to
34,000 x 106 m3/year. The Bang pakong is the river
received domestic sewage from several cities, and effluent from agro-industrials
which has a flow of 3,000 x 106 m3/year. The Tha-chin
river which flow and discharges into the upper Gulf at Samut Sakhorn at a
rate about 1,500 x 106 m3/year. The Mae-kong river which
discharges into the upper Gulf of Thailand at Samutsongkram from 9,000 to
16,000 x 106 m3/year. The wastewaters generated
from these industries in Chonburi and Samut Prakharn province such as sugar,
metal plating, paper mill and food industrial located along the river at
a distance about 100 km upstream from the Gulf.
The sample were collected in dry season
(April-May) and wet season (October-December) and were analysed for Persistent
Organic Pollutants (POPs) namely chlordane hexachlorobenzene, aldrin, dieldrin,
endrin and DDT-isomers by UNU method. The water samples were
kept at 4 °C
Apparatus
A) Gas-Chromatograph-model
17-A (Shimadzu) equipped with Mass Spectrometer model QP-5050A (Shimadzu )
B) Rotary
Vacuum evaporator-type Rotavapor RE-111 (Buchi)
C) Laboratory
sharking machine-type Recipro (II-RW)
Figure 1
Map of sampling stations (coastal area)
Figure 2
Map of sampling stations (River Basin)
Reagent
a) Solvent-Ultra
high pure grade (J.T. Baker Chemical Inc.U.S.A.)
b) Silica-gel
cartridge 500mg (Varian)
c) Organochlorine
pesticides standard ( AccuStandard Inc. and Wako chemical industrial Ltd. )
-
HCB
-
heptachlor
-
p,p¢-DDE
-
p,p¢-DDT
-
p,p'-DDD
-
trans-chlordane
-
cis-chlordane
-
aldrin
-
dieldrin
-
endrin
10 mg of each standard was weighted accurately on an
analytical balance, put it in volumetric flask with 100ml and dissolve with
100ml n-hexane-acetone for stock solution.
d) sodium
sulfate ( Merck,U.S.A. )
e) sodium
chloride (Merck,U.S.A. )
Sample preparation for POPs
1 liter of water sample added 30 g of
sodium chloride, was extracted with 50 ml of n-hexane for 10 minutes by
shaker. The hexane was transferred to erlenmeyer flask. The water sample
was extracted repeatedly with 50ml of n-hexane. The extractant was
transferred into the same flask. The hexane was dehydrated with sodium
sulfate before it was reduced the volume into 1ml.It was transferred to silica
gel cartridge for cleanup. The cartridge was washed with 5 ml of acetone
and 15ml of n-hexane. POPs residues was eluted with 7ml of 2% acetone/n-hexane
and was injected into GC/MS for measurement. This method and QA/QC were
followed the UNU manual 1999.
GC-MS confirmation
Mass
fragmentation data were obtained with Gas Chromatograph model GC-17A (Shimadzu)
and interface equipped with Mass Spectrometer model QP-5000 (Shimadzu) and
Electron impact mode (ion energy was 70 EV). The chromatography column
bonded DB-51fuse silica column (30m x 0.32mm id x 0.25mm film thickness) was
used. The condition for POPs compounds is:
The injection method was splitless 2 min,
injection volume was 2 ml and injection inlet temperature
was 250 °C. The carrier gas was helium with a flow
rate of 2 ml/min. The temperature program of column was followed: The initial
column temperature was 70°C(1min) and increase at 20°C/min to
130°C, increase at 5 °C/min to 210 °C and
increase at 15 °C/min to 300 °C(4min).
Interface temperature at 270°C
Result and discussion
For
48 water samples from eleven stations of four main river which flow to the
upper Gulf of Thailand namely The Chao Phraya river, The Mae Klong river, The
Bang Pakong river and The Tha-Chin river and thirteen stations of coastal areas
have been selected for monitoring and analysis.
Aldrin
and dieldrin usually used for crops like corn and cotton. Also used for termite
control. In this study found aldrin and dieldrin at the range of 4.6-12.9
ng/L (ppt) and 4.2-10.2 ng/L (ppt) in dry season and wet season,
respectively . In wet season, a lot of watershed from upstream drain to
river and pass to coastal area around September-November.
Endrin
used mainly on field crops such as cottons and grains. Used as
rodenticide to control mice. Heptachlor used against soil insects and termites
and also against cotton insects.Hexachlorobenzene (HCB) is a fungicide for seed
treatment especially for control of bunt of wheat. It also byproduct of the
manufacture of industrial chemicals including carbon tetrachloride. HCB is very
high persistent. Hexachlorobenzene used for seed treatment, especially for
treatment for wheat, onion and found as impurity in several pesticide
formulations. In addition, an industrial chemical used to make firework,
ammunition, synthetic rubber and also a byproduct of the manufacture of
industrial chemicals including carbon tetrachloride, perchlorethylene,
trichloroethylene and pentachlorobenzene.
Chlordane is a broad spectrum contact
insecticide that has been used on agricultural crops including vegetables small
grains, other oilseeds, potatoes, sugarcane, nuts and fruits. It has been used
extremely in the control termites. This study were not found endrin, chlordane,
HCB, and heptachlor in water samples.
The concentration of p,p-ddt residues in
water samples were found only 2 in 48 stations at the range of 5.6-12.2 ng/L
atSMMP-2 and CH4-2.
The concentration of all pollutants are
under the surface water and seawater quality standard by Notification of the
National Environmental Board, No. 7-8, B.E. 2537 (1994 ). Thai government take
action to introduce the necessary legislation for the regulation, including
registration of pesticides and make provisions for its effective
and enforcement, including the establishment of appropriate educational,
advisory, extension and health-care services
Conclusion
During April 2002-March 2003, The
Environmental Research and Training Center of Thailand has cooperation with The
United Nations University to monitor POPs. In this study can indicate that the
situation of POPs in Thailand such as organochlorine pesticide compounds. In
case of Thailand need to monitor river water sample couple with sea water
because characteristic of country such tropical climate and
topography. Thailand have a lot of watershed and huge amount of water
loading can discharge to coastal area where may be have effected to coastal
environment. However, The result of concentration of POPs in river and sea
water along the Gulf of Thailand found very low . It may be because of
climate in tropical area. The tropical climatic conditions favor rapid
volatilization of the residues from the soil and heavy rain fall also
facilitates the loss of residue, through water run off from the source
area. The contamination of coastal species by pesticides in the tropical
countries are not higher when compared to those of developed countries.
Table 3 concentration of POPs in
river water and sea water (dry season)
|
Sample ID
|
Compound
|
Observed Value
|
Units
|
Value Description
|
|
CH1-1
|
nd
|
|
ppt
|
ppt :
ng/L
|
|
CH2-1
|
dieldrin
|
4.2
|
ppt
|
|
|
CH3-1
|
nd
|
|
ppt
|
|
|
CH4-1
|
aldrin
|
13.9
|
ppt
|
|
|
CH5-1
|
nd
|
|
ppt
|
|
|
MK1-1
|
nd
|
|
ppt
|
|
|
MK2-1
|
aldrin
|
7.9
|
ppt
|
|
|
TR1-1
|
dieldrin
|
8.5
|
ppt
|
|
|
TR2-1
|
aldrin
|
4.6
|
ppt
|
|
|
BP1-1
|
nd
|
|
ppt
|
|
|
BP2-1
|
nd
|
|
ppt
|
|
|
TRAD-1
|
nd
|
|
ppt
|
|
|
CHONB-1
|
aldrin
|
6.3
|
ppt
|
|
|
SMP-1
|
dieldrin
|
5.5
|
ppt
|
|
|
PATTANI-1
|
nd
|
|
ppt
|
|
|
PETC-1
|
nd
|
|
ppt
|
|
|
CHUMP-1
|
aldrin
|
12.9
|
ppt
|
|
|
SURAT-1
|
nd
|
|
ppt
|
|
|
RANONG-1
|
nd
|
|
ppt
|
|
|
TRUNG-1
|
nd
|
|
ppt
|
|
|
PUNGGA-1
|
nd
|
|
ppt
|
|
|
KRABI-1
|
nd
|
|
ppt
|
|
|
NAKHORN-1
|
nd
|
|
ppt
|
|
|
PRACHUB-1
|
nd
|
|
ppt
|
|
Table 4 concentration of POPs in
river water and sea water (wet season)
|
Sample ID
|
Compound
|
Observed Value
|
Units
|
Value Description
|
|
CH1-2
|
nd
|
|
ppt
|
|
|
CH2-2
|
nd
|
|
ppt
|
|
|
CH3-2
|
nd
|
|
ppt
|
|
|
CH4-2
|
p,p'-ddt
|
12.2
|
ppt
|
|
|
CH5-2
|
dieldrin
|
10.2
|
ppt
|
|
|
MK1-2
|
nd
|
|
ppt
|
|
|
MK2-2
|
nd
|
|
ppt
|
|
|
TR1-2
|
nd
|
|
ppt
|
|
|
TR2-2
|
nd
|
|
ppt
|
|
|
BP1-2
|
nd
|
|
ppt
|
|
|
BP2-2
|
nd
|
|
ppt
|
|
|
TRAD-2
|
nd
|
|
ppt
|
|
|
CHONB-2
|
aldrin
|
7.2
|
ppt
|
|
|
SMP-2
|
p,p'-ddt
|
5.6
|
ppt
|
|
|
PATTANI-2
|
nd
|
|
ppt
|
|
|
PETC-2
|
nd
|
|
ppt
|
|
|
CHUMP-2
|
nd
|
|
ppt
|
|
|
SURAT-2
|
nd
|
|
ppt
|
|
|
RANONG-2
|
nd
|
|
ppt
|
|
|
TRUNG-2
|
nd
|
|
ppt
|
|
|
PUNGGA-2
|
nd
|
|
ppt
|
|
|
KRABI-2
|
p,p'-ddt
|
6.2
|
ppt
|
|
|
NAKHORN-2
|
nd
|
|
ppt
|
|
|
PRACHUB-2
|
nd
|
|
ppt
|
|
Remark:
Sample ID -1 : dry season
Sample ID-2 : wet season
nd : non detectable
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