Monitoring of persistent organochlorine pesticides and phenols in the coastal hydrosphere of Thailand
R.
Boonyatumanond, A. Jaksakul, S.Boonchalermkit,
P.Puncharoen, M.S. Tabucanon
Environmental Research and
Training Center,
Technopolis,
Tambon Klong 5, Amphoe Klong Luang,
Pathumthani 12120, Thailand
Department of Environmental
Quality Promotion,
Ministry of Science,
Technology and Environment
ABSTRACT
The monitoring programme has been started from 2000 to 2001
with the cooperation between The Environmental Research and Training Center and
The United Nations University (UNU) entitled: Endocrine Disrupter Compounds
(EDC) pollution in the East Coastal Hydrosphere. Forty-eight samples of river water and sea water were collected
in the four main rivers and in the coastal area of the gulf of Thailand. The samples were analysed organochlorine
pesticides and phenol residues by UNU method.
The result of monitoring has indicated that organochlorine
pesticide residues were detected at low concentration and lower than our
detection limit. The detection limit is
at the range of 0.10-0.30 ng/l(ppt)
with 79-83 % recovery. The phenol
residues were detected at the range of 4.35-0.02 ng ml-1 (ppb). The
detected limit of phenol compounds is at the range of 0.01-0.06 ng ml-1 (ppb)
with 71-99 % recovery. The highest frequency of phenol detected in river water
sample and sea water sample is 4-t-butylphenol. The highest concentration of
river water sample is 4-nonylphenol(1.9 ng ml-1) at the Tha-chin
river station and for sea water sample is 2,4 dichlorophenol(19 ng ml-1) at Ranong station.
INTRODUCTION
With the cooperation of the Environmental Research and
Training Center and the project on United Nations University on Environmental
and Governance, Endocrine Disrupter Compounds (EDC) pollution in the East
Coastal Hydrosphere. This project is focuses on Endocrine Disrupter Compounds
(EDC) pollutants such as organochlorine pesticides and phenol. The objective of the project is to know the
status of environment and water quality around the coastal area of each
country. This paper has presented the result of monitoring of water sample in
2000.
The point of view on Endocrine
Disrupter Compounds such as organochlorine pesticides have been used for long
times in Thailand. The contamination of chemicals have transferred to the
environment because human being tries to increase many productions to serve the
people in country and world people. In
Thailand, people still use lindane and endosulfan . As we know, Thailand, like
others developing countries uses many chemicals as raw materials in industrial
factories. Phenol is mainly a man-made chemical. It is widely used in the manufacturing process and in many
products such as resins, plastic, insecticide, explosives, dye and detergent,
etc. Therefore, the exposure of phenol can pass through human being and raises
concern to impact on the environment. There can been found in the air, drinking
water, surface water, food, and groundwater, etc.
For
example, Bisphenol-A used in the manufacture of a variety of plastics. The
Bisphenol-A is expected to exist almost entirely in the particulate phase in
the atmosphere [1]. Nonylphenol ethoxylates which used as an ingredient of
surfactant in various industrial and household application. 4-nonylphenol is
used as a biodegradation product of nonylphenol ethoxylates . Nonyl products
are use in the preparation of lubricating oil additive, resins, surface active
agent, antioxidants for rubber and plastic [2]. Nonylphenol will bioconcentrate
in the aquatic organisms and 4-nonylphenol should occur rapidly in water.
2,4-Dichlorophenol's production used in
organic synthesis may result in its release to the environment through various
waste streams.2,4-Dichlorophenol has been detected in waste waters from
bleaching process at pulp mills [3].
MATERIALS AND METHOD
The monitoring programme has started from May 2000 to
February 2001. Twenty-two river water samples from 11 stations were collected
at four main rivers, namely the Chao Praya River, the Mae-klong River, the
Bangpakong River and the Tha-chin River.
Twenty-six sea water samples from 13 stations were collected from the
West side of the Gulf of Thailand where connects with the Andamun sea and the
east side of the Gulf of Thailand as showed in Table 1. The water sample for
organochlorine pesticide analyses were keep at 4°C and especially the sample
for phenol analyses were preserved with hydrochloric acid to pH 2-3 in site and
were kept at the same temperature.
Figure
1 Map of sampling stations (coastal area)
Figure 2 Map of sampling stations (River Basin)
Table 1 Sampling
collection information for EDC in water samples
|
Number of sample |
Code number |
Name of station |
Remark |
|
1 |
CH1 |
The Chao Praya
river |
-1 : dry season |
|
2 |
CH2 |
The Chao Praya
river |
-2 : wet season |
|
3 |
CH3 |
The Chao Praya
river |
|
|
4 |
CH4 |
The Chao Praya
river |
|
|
5 |
CH5 |
The Chao Praya
river |
|
|
6 |
MK1 |
The Mae Klong river |
|
|
7 |
MK2 |
The Mae Klong river |
|
|
8 |
TR1 |
The Tha Chin river |
|
|
9 |
TR2 |
The Tha Chin river |
|
|
10 |
BP1 |
The Bang pakong
river |
|
|
11 |
BP2 |
The Bang pakong
river |
|
|
12 |
TRAD |
Trad province |
|
|
13 |
CHONB |
Chonburi province |
|
|
14 |
SMP |
Samutprakarn
province |
|
|
15 |
PATTANI |
Pattani province |
|
|
16 |
PETC |
Petchaburi province |
|
|
17 |
CHUMP |
Chumporn province |
|
|
18 |
SURAT |
Surat-thani province |
|
|
19 |
RANONG |
Ranong province |
|
|
20 |
TRUNG |
Trung province |
|
|
21 |
PUNGGA |
Pang-ga province |
|
|
22 |
KRABI |
Krabi province |
|
|
23 |
NAKHORN |
Nakhorn-Srithammarat
province |
|
|
24 |
PRACHUB |
Prachub-kirikhan
province |
|
APPARATUS
A)
Gas-Chromatograph-model
17-A (Shimadzu) equipped with Mass Spectrometer model QP-5000 (Shimadzu )
B)
Rotary Vacuum evaporator-type Rotavapor
RE-111 (Buchi)
C)
Laboratory sharking machine-type Recipo
shaker SR-IIW
(Taitec corperation)
D)
Chromatographic column-capillary 30m x 0.32
mm id x 0.25 mm of film thickness DB5 ( J&W )
E)
Vortex-type
model GENIE 2 G-560E (Scientific Inc., U.S.A.)
F)
Glassware-Separatory
funnel 2000ml with glass stopper; glass funnel 90 mm id; cylinder graduated
50ml; Erlenmeyer flask (Pyrex)
REAGENTS
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. )
-
a-HCH
-
b-HCH
-
g-HCH
-
d-HCH
-
p,p¢-DDE
-
p,p¢-DDT
-
p,p'-DDD
-
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)
Internal
standard solution ( Cambridge isotope
laboratory, Inc )
-
Phenanthrene
d10
-
Pyrene
d10
-
Naphthalene
d8
e)
Phenol
standard (Wako chemical industrial Ltd.,)
-
4-t-Butylphenol
-
2,4-Dichlorophenol
-
4-n-Butylphenol
-
4-n-Pentylphenol
-
4-n-Hexylphenol
-
4-n-Heptylphenol
-
4-t-Octylphenol
-
4-n-nonyltylphenol
-
4-n-Octylphenol
-
Pentachlorophenol
-
Bisphenol-A
-
Bisphenol-A
d14
f)
sodium
sulfate ( Merck,U.S.A. )
g)
sodium
chloride (Merck,U.S.A. )
Sample preparation for (organochlorine pesticides)
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. After shaking,
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.
Organochlorine pesticide residues was eluted with 5ml of 5% acetone/n-hexane
and was injected into GC/MS for measurement. This method and QA/QC were
followed the UNU manual 1999.
Sample preparation for (phenol compounds)
500ml of water sample was adjusted pH condition at pH 2-3
by using hydrochloric acid and add 30 g sodium chloride into separatory funnel
The sample was added 100 ml of 1ppm of surrogate
compound (Bisphenol-A d16) and was extracted with 25 ml of dichloromethane by
shaker for 10 min . The organic layer was transferred to
erlenmeyer flask and the water was repeatedly extracted again with 25 ml
dichloromethane. The organic layer was
transferred into the same flask. The extractant was dehydrated with sodium
sulfate and concentrated to 0.5 ml by rotary evaporator and nitrogen. The extracting was added 100 ml BSTFA and stay for 1 hour at room
temperature and added 100 ml of internal standard
before inject into GC/MS.
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-5 fuse silica column (30m x 0.32mm id x 0.25mm film thickness) was
used. The condition for organochlorine
pesticide compounds is:
The
injection method was splitless 2 min, injection volume was 2 ml and injection inlet temperature was 280 °C. The carrier gas was helium with a flow
rate of 2 ml/min. The temperature programme of column was followed: The initial
column temperature was 70°C(2min) and increase at 20°C/min to 150°C, increase at 5 °C/min to 220 °C and increase at 15 °C/min to 300 °C. Interface temperature at
280°C
The
condition of phenol compounds is:
The
injection method was splitless 2 min, injection volume was 2 ml and injection inlet temperature was 300 °C.
The temperature programme of column was followed: the initial column
temperature was 50 °C (2 min) and increase at 20°C/min to 200°C, increase at 20°C/min to 300°C (8 min). Interface
temperature at 270°C
RESULTS AND DISCUSSION
The
water samples were analysed by UNU methods including the quality control and
quality assurance in laboratory. The optimum detection limit depends on the
chemical structure of the pesticide. Thus, a single same sample could be used
to determine the rang of chemical structure of the pesticides. The recovery
experiments were performed by spiking the surrogate standard (Bisphenol-A d14)
for phenol compounds. The detection limit is at the range of 0.01-0.06 ng ml-1.
The blank test was used tap water in laboratory room with stainless steel
pipeline. The blank were found 4-t-Butylphenol 0.006 ng ml-1 and
bisphenol-A 0.02 ng ml-1. The detection limit of organochlorine pesticides is at the range of 3.0-17 ng l-1.
The concentrations of organochlorine residues in river
water sample and sea water from Thailand are showed in Table 2.1-2.4. DDTs could be detected only one station,
Krabi station 18 ng l-1 and 20 ng l-1 in dry season and wet season, respectively.
The aldrin were detected in the range
of 5-20 ng l-1 at dry season. The highest concentration of aldrin is
20 ng l- 1 at Chumporn but the lowest concentration is 5.0 ng l-1
at The Chao Praya River at CH4 station.
The concentration of HCH and its isomer ( a-HCH, b-HCH, g-HCH and d-HCH ) were found only three stations which were 10 ng l-1at Pattani
station,15 ng l-1at Chumporn station and 17 ng l-1at Pangga
station . It is noticed that the concentration of the organochlorine
pesticide is not relevant to the seasonal variation, wet or dry season. It is
probably due to the residues concentration is very low. Although the persistent
of organochlorine was one of prospective issue 15 years ago. But now the
residues concentration found in the river and sea water are very lower than
they have been found in the former times.
The concentration of phenol
residues was analysed by using Gas Chromatography-Mass Spectrometer. The river water and sea water samples were
monitored for 11 phenol compounds in dry season and wet season. The results
were showed in Table 3.1-3.4. The
concentration could be detected in the range of 0.01-19 ng ml-1. The
highest frequency was found that they were 4-Nonylphenol, 4-t-Butylphenol,
Bisphenol-A and 2,4-Dichlorophenol, respectively.
The
concentration of 4-Nonylphenol ranged from 0.02 to 1.9 ng ml-1. The
highest concentration of 4-Nonylphenol was found at the value of 1.9 ng ml-1
in dry season and wet season at Tha Chin-2 station. It is found that the
residues level in dry season was detected higher than the residues level in wet
season.It is assumed that the decrease of water in dry season can concentrate
the chemicals existing in the areas. As we know that 4-nonylphenol was used as
an ingredient of surfactant in various industrial and household application. In
this study, it can detect 4-nonylphenol with in 72% of 48 samples.
The 4-t-Butylphenol was
detected at the range of 0.02-15 ng ml-1.
The highest concentration
was 15 ng ml-1 at Ranong station in dry season. The frequency of
detection was not distinguish from dry and wet season.
The
concentration of Bisphenol-A was detected at the range of 0.02-0.21 ng ml-1.
The highest concentration was 0.21 ng ml-1 at Chumporn station at
dry season. The source of bisphenol-A may come from manufacturing and use
facilities where it is used in the manufacture of epoxy, polycarbonate and
polysulfone resins [4]. The result has showed that the concentration of sample
in dry season is higher than those in wet season, especially in sea water
sample.
The
2,4-Dichlorophenol was detected in river water and sea water samples from 20
stations in dry season and 3 station in wet season. The concentration range is
0.01-19 ng ml-1.The highest concentration was19 ng ml-1 at
Ranong in dry season. Although the data
showed that many water samples have phenol residues, the concentration is lower
than the limit of the water quality standard in Thailand which is limit <0.005 mg l-1 or
5 ng ml-1.
The
result of phenol concentration in water sample is very low because behavior of
phenol is heavier than water and it can sinks to the bottom. It dissolves
slowly and continues to form toxic solution even when dilute. In addition to
phenol has high vapor pressure, is meaning that phenol can vapor into the air
and was oxidized by photooxidation [5]. The oxidation process involving
hydroxyl radical which have their potential to destroy toxic organic compounds
in wastewater [6]. The radical may be
produced by combining ozone with ultraviolet [7]. There is roughly 90% degradation in surface water in approximate
7 days (standing water). However, Phenol can be use as basis parameters for providing
information on the situation of chemicals concentration in surface waters.