The UNU Project on:
ENVIRONMENTAL MANAGEMENT CENTER
INDONESIA
2002
A survey on water pollution by Endocrine
Disrupter Compounds:
Dewi Ratnaningsih, M Helmy, Bagus BE, Nety W, Heni P.
Environmental Management Center
Kawasan PUSPIPTEK Serpong Tangerang
Indonesia
ABSTRACT
Monitoring of Endocrine Disrupter compounds (EDCs) in the coastal hydrosphere of Indonesia was carried out to investigate environmental water contamination by persistent organochlorine insecticides, phenols and phthalate compounds. Surface river and sea water from four cities in Jawa Island including Jakarta, Bogor, Semarang and Surabaya were selected as sampling locations. 13 river water samples and 6 sea water samples were collected in August 2001 represented dry season and similar sampling location with the same sample amount were collected in November 2001 as represented rainy season. The target compounds for analysis consist of a group of organochlorine insecticides including a-BHC, g-BHC, d-BHC Heptachlor, Aldrin, Dieldrin, Endrin, op-DDE, pp-DDE, op-DDD, pp-DDD , op-DDT, pp-DDT; a group of phenol compounds including 4-t-Butylphenol, 2-4-Dichlorophenol, 4-n-Butylphenol, 4-n-Pentylphenol, 4-n-Hexylphenol, 4-t-Octylphenol, 4-n-Heptylphenol, 4-n-Nonylphenol, 4-n-Octylphenol, Pentachlorophenol, Bhisphenol-A and a group of phthalate compounds including Diethyl phthalates, Di n-butyl phthalate, Di 2-ethyl hexyl adipate, Di 2-ethyl hexyl phthalate.
The monitoring result indicated that some organochlorine compounds, phenols and phthalates were detected in river and sea water samples in trace level amount. For Heptachlor, d-BHC, Aldrin and DDE were mostly undetected in many samples neither in river nor sea water. DDT and its derivates were still detected with the value varied from nd to 122 ppt. The other organochlorine compounds were detected with the highest value was 23.37 ppt. Phenol compounds were also detected in almost all of sampling locations. The highest value for each location was mostly detected in the form of nonylphenol. The range of nonylphenol concentration were detected from nd to 8659 ppt. Bhisphenol-A was detected with the range from 0.06 to 230 ppt. Other phenol compounds had a range from nd to 44.24 ppt. Phthalates were also detected in almost all of sampling sites with the value ranged between nd and 12.92 ppb Diethyl phthalate and Di-2-etyl hexyl adipate were found to be higher mostly in dry season. Although the result indicated that the concentration of EDCs in the river and sea water were relatively low, it is necessary to continue this monitoring activities in order to obtain the trend of EDCs pollutant level in the coastal hydrosphere of Indonesia .
INTRODUCTION
The uses of toxic organic compounds for industrial and agricultural activities result in the discharge of such contaminants to the environment. The potential adverse impact to living organisms, particularly human being is of particular concern due to the existence of these organic pollutants.
The pollution by Endocrine Disrupter Compounds such as organochlorine, phenol and phthalate compounds in the environment should be paid more attention. Since rivers are still used as the final discharge of the wastes from domestic and industrial activities , therefore the existence of such compound should be awared due to the negative impact to the environment and human health. The multipurpose function of the river for human needs also lead to some necessary action to be made in order to prevent more dangerous chemical from entering the river body, considering some major rivers are still used as the source of water supply system.
In Indonesia, organochlorine compounds had been banned since more than 10 years ago. However, the residue of organochlorine still exist in the environment due to the persistent characteristic of this compound. The previous survey indicated that several organochlorine compounds had contaminated the river in ppt level and sediment or soil in ppb level. Phenol and phthalate compounds also contribute as the potential pollutant to the water, because those source of compounds are still used to fulfill human needs either for domestic or industrial activities.
The objective of this monitoring is to identify the current level of several organic pollutants in the river and sea water. The target compounds for analysis consist of a group of organochlorine insecticides including a-BHC, g-BHC, d-BHC Heptachlor, Aldrin, Dieldrin, Endrin, op-DDE, pp-DDE, op-DDD, pp-DDD , op-DDT, pp-DDT; a group of phenol compounds including 4-t-Butylphenol, 2-4-Dichlorophenol, 4-n-Butylphenol, 4-n-Pentylphenol, 4-n-Hexylphenol, 4-t-Octylphenol, 4-n-Heptylphenol, 4-n-Nonylphenol, 4-n-Octylphenol, Pentachlorophenol, Bhisphenol-A and a group of phthalate compounds
including Diethyl phthalates, Di n-butyl phthalate, Di 2-ethyl hexyl adipate, Di 2-ethyl hexyl phthalate. Continuous monitoring is necessary to be carried out in order to get representative data for assessing organic pollutant condition in the environment.
METHODOLOGY
The monitoring activities on organochlorines, phthalates and phenols contamination in environment were carried out from August 2001 to November 2001. Thirty eight- samples were collected from five cities which consisted of river and sea water samples. Four main rivers in Java Island and a secondary river located in industrial area were selected for sampling point. Other samples were collected from sea water which was taken in Jakarta Bay, Madura Strait Surabaya and Jawa Sea Semarang. The main river selected for sampling point included Ciliwung River at Bogor-Jakarta city, Banjir Kanal Barat and Banjir kanal Timur River at Semarang and Surabaya River as well as Rungkut River at Surabaya. Sampling data sheet information was shown in the appendix. After collecting the samples, then were placed in the dark glass bottle and kept at cooling room at 4 oC.
Apparatus
1. GCMS QP-5000 (Shimadzu) equipped with chromatographic column-capillary DB-1, 30m x 0.32 mm id x 0.25 mm of film thickness
2. Rotary evaporator
3. Shaker
4. Separatory funnel 1000, 2000 ml
5. Erlenmeyer flask
Reagents
1. Hexane for residue analyses grade
2. Acetone for residue analyses grade
3. Dichloromethane
4. Silica-gel cartridge 500 mg (varian)
5. Sodium Sulfate Anhydrous
6. Sodium Chloride
7. Organochlorine insecticides standard including a-HCH, g-HCH, d-HCH, Aldrin, Heptachlor, Endrin, Dieldrin, Metoxichlor, o,p’-DDD, p,p’-DDD, o,p’-DDE, p,p’-DDE, o,p’-DDT, p,p’-DDT.
8. Phenol standards including 4-t-Butylphenol, 2,4-Dichlorophenol, 4-n-Butylphenol, 4-n-Pentylphenol, 4-n-Hexylphenol, 4-n-Heptylphenol, 4-t-Octylphenol, 4-n-nonyl-phenol, 4-n-Octylphenol, Pentachlorophenol, Bhisphenol-A, Bhisphenol-A d14.
9. Phthalates Standards including Diethyl phthalates, Di n-butyl phthalate, Di 2-ethyl hexyl adipate, Di 2-ethyl hexyl phthalate.
Sample Extraction for Organochlorine compounds.
1L water sample was placed into 2 L separating funnel and added by 30 g of sodium chloride. For extraction purpose, water sample was added by 50 ml of n- hexane and shaken for 10 minutes by shaker. The hexane layer was transferred to erlenmeyer flask. The water layer was re-extracted with 50 ml-n-hexane. The extract result was added by sodium sulfate anhydrous in order to eliminate water content from organic layer. The extraction layer was concentrated and cleaned-up by using sep-pack cartridge J-18. The solution was added by IS and adjusted up to 1 ml and then analyzed by using GCMS.
Sample Extraction for Phenol
compounds.
500 ml of water sample was placed into 1 L of separating funnel and
adjusted pH at value 2-3. For extraction
purpose, 50 ml Dichloromethane and 30 g of sodium chloride were added and then
shaken for 10 minutes. Extraction was
performed two times. Surrogate compound
was included for quality control purposes.
The organic layer resulted from extraction process was transferred to erlenmeyer flask and removed the water content by adding
sodium sulfate anhydrous. The organic
layer was concentrated until the volume less than 0.5 ml and added by 100 ml BSTFA for
derivative reaction. Solution was
allowed to stand for 1 hour and added by IS and filled up into 1 ml by
dichloromethane. Than 2 ml solution was
injected into GCMS.
Sample Extraction for Phthalate
compounds.
100 ml water sample was placed into 100 ml volumetric flask and added by 5 ml hexane. Surrogate and Internal Standard were included for quality control. For extraction purpose, water sample was shaken for 1 minute and then transferred to 1 ml of hexane layer from volumetric flask into vial for auto sampler. 2 ml of solution was injected into GCMS for determination of phthalate concentration.
RESULT AND DISCUSSION
Quality control for analysis was assessed by conducting recovery test for each parameter. The recovery test was performed by spiking each standard solution for phthalates, phenols and organochlorines in distillate water and then analyzed for each compound. The recovery test result for group of phthalates showed that value ranged between 94 and102 % ; For group of phenol between 90 and 106 %; and for group of organochlorine between 77 and 101%.
River and sea water samples were analyzed to identify the existence of EDCs including phthalate, organochlorine, and phenol compounds in environment. The concentration of phthalate compounds in river and sea water in Indonesia are shown in table 1.
Table 1. Concentration of Phthalate Compounds in River and Sea Water in Indonesia
|
SAMPLING SITES |
COMPONENT AND CONCENTRATION
( ppb ) |
|||||||||
|
City |
Code |
|
Diethyl phthalate ( DEP)
|
Di n-butyl phthalate (DBP) |
Di 2-ethyl hexyl adipate (DOA) |
Di 2-ethyl hexyl phthalate (DEHP) |
||||
|
Dry season |
Wet season |
Dry season |
Wet season |
Dry season |
Wet season |
Dry season |
Wet season |
|||
|
B O G O R-J A K A R T A |
WC1 |
Ciawi-Bogor |
0.70 |
0.19 |
0.72 |
0.38 |
0.52 |
0.30 |
0.64 |
0.78 |
|
WC2 |
Tajur-Bogor |
0.64 |
0.17 |
1.24 |
0.13 |
0.81 |
0.38 |
1.64 |
2.28 |
|
|
WC3 |
Botanical Garden-Bogor |
3.54 |
0.71 |
1.94 |
0.40 |
0.34 |
0.34 |
1.37 |
1.47 |
|
|
WC4 |
Kalibata-Jakarta |
1.00 |
1.36 |
1.30 |
3.34 |
0.15 |
0.81 |
2.46 |
2.09 |
|
|
WC5 |
Gn. Sahari
-Jakarta |
1.49 |
12.92 |
1.24 |
4.40 |
0.17 |
0.25 |
1.42 |
5.52 |
|
|
SC6 |
Marina Beach-Jakarta |
0.43 |
0.15 |
0.36 |
2.24 |
0.24 |
0.24 |
0.43 |
3.19 |
|
|
SP1 |
Tanjung Priuk
Harbour. |
0.95 |
0.20 |
0.80 |
1.05 |
0.59 |
0.23 |
1.89 |
4.11 |
|
|
S U R A B A Y A |
WR1 |
Rungkut |
0.51 |
1.65 |
3.67 |
1.03 |
0.34 |
0.32 |
6.89 |
1.31 |
|
WB1 |
Gunungsari |
1.37 |
0.13 |
11.77 |
0.91 |
0.43 |
nd |
6.35 |
1.04 |
|
|
WB2 |
Wonokromo |
2.53 |
0.19 |
10.88 |
0.92 |
0.52 |
nd |
4.55 |
0.74 |
|
|
WB3 |
Jembatan Merah |
1.82 |
0.62 |
6.10 |
1.08 |
2.25 |
0.29 |
5.42 |
3.14 |
|
|
SB4 |
T. Perak
Harbour |
0.59 |
0.03 |
1.88 |
2.21 |
0.08 |
0.36 |
2.57 |
4.57 |
|
|
SJ1 |
Kenjeran Beach |
0.53 |
0.03 |
3.08 |
1.27 |
0.17 |
nd |
3.82 |
1.72 |
|
|
S E M A R A N G |
WT1 |
BKT Mojopahit
up |
4.83 |
3.97 |
2.07 |
2.27 |
nd |
0.47 |
1.86 |
2.86 |
|
WT2 |
BKT down |
6.72 |
1.23 |
2.61 |
2.07 |
0.04 |
0.32 |
2.79 |
2.11 |
|
|
WK1 |
PDAM(BKB) up |
0.51 |
0.92 |
1.59 |
3.56 |
nd |
0.59 |
2.44 |
3.24 |
|
|
WK2 |
Katamso (BKB) |
0.41 |
0.41 |
1.26 |
3.39 |
0.12 |
0.25 |
1.16 |
2.23 |
|
|
SK3 |
Marina Beach |
0.66 |
0.28 |
1.73 |
1.45 |
0.12 |
nd |
4.70 |
1.24 |
|
|
SM1 |
Tanjung Emas |
0.73 |
0.16 |
2.91 |
1.53 |
0.36 |
nd |
2.52 |
0.86 |
|
Note:
I : dry season W : river water nd : not detected
II :
Rainy season S : sea water
Phthalate compounds were detected in almost all of river and sea water samples. The concentrations were varied from nd to 12.92 ppb. Dietyl phthalate (DEP) were detected in dry season with the concentration ranged from 0.41 to 6.72 ppb. In wet season, those compounds were found with the range from 0.03 to 12.92 ppb. The highest value of DEP (12.92 ppb) was detected at sampling site WC5 (Ciliwung river) located in downtown of Jakarta city. This sampling site was located at downstream of Ciliwung river about 5 km up stream from the river mouth of Jakarta bay. Mostly, the highest concentration of several phthalates including DBP and DEHP were detected in those sampling sites, particularly in rainy season. This fact can probably be explained that during rainy season, contaminated sediment or soil entered to the river water which was resulted from heavy rainfall. Therefore, some of the phthalates which were trapped in the soil and sediment will be then flown to the surface river water. Additionally, dense activities of human being at downtown area had generated wastes which would flow into the river and eventually be accumulated in downstream.
Table 2. Comparison of the Concentration Average of Phthalate Compounds in Dry
and Rainy Season
|
|
PHTHALATE COMPOUNDS (ppb) |
|||||||
|
DEP |
DBP |
DOA |
DEHP |
|||||
|
Range |
mean |
Range |
mean |
Range |
mean |
Range |
mean |
|
|
DRY |
0.41-6.72 |
1.58 |
0.36-11.77 |
3.01 |
nd-2.25 |
0.38 |
0.43-6.89 |
2.89 |
|
RAINY |
0.03-12.92 |
1.28 |
0.13-4.40 |
1.77 |
nd-0.81 |
0.27 |
0.74-5.52 |
2.34 |
DBP was found with the minimum concentration 0.36 ppb and maximum value 11.77 ppb in dry season, while the concentration of DBP varied from 0.13 to 4.40 ppb in wet season.. DOA was detected lower than other phthalate compounds with the average value 0.38 ppb in dry season and 0.27 ppb in rainy season. Meanwhile DEHP had concentration ranged between 0.43 and 6.89 ppb in dry season and 0.74 to 5.52 ppb in rainy season. Eventhough, the highest concentration of phthalates was detected in rainy season, from the average value (table 2) it can be assumed that phthalate concentration were relatively higher in dry season than in rainy season. It is correspondent to the assumption that in the rainy season, the river water will be diluted due to the rainfall, consequently the concentration will be lower in rainy season. For the compound which was detected in traceable amount there was no significantly different result between dry and rainy season. In general, the result of phthalate compounds in surface water sample were detected in relatively low concentration, partly because of both physical-chemical and biological degradation factors.
Table 3. Concentration of Organochlorine Compounds in the River and Sea Water in
Indonesia
|
SAMPLING SITES |
COMPONENT AND CONCENTRATION ( ppt
) |
||||||||||||||
|
City |
CODE |
a-HCH |
g-HCH |
d-HCH |
Hep-tachlor |
Al- drin |
Die-ldrin |
En-drin |
o-p’ DDE |
p-p’ DDE |
o,p-DDD |
p,p-DDD |
o,p-DDT |
p,p-DDT |
Metoxi-chlor |
|
S U R A B A Y A |
WR1-I |
3.29 |
4.75 |
nd |
5.29 |
nd |
nd |
3.31 |
nd |
nd |
0.32 |
2.90 |
3.01 |
3.49 |
4.61 |
|
WR1-II |
4.68 |
3.79 |
nd |
nd |
nd |
nd |
0.51 |
nd |
nd |
0.51 |
0.86 |
3.88 |
1.61 |
nd |
|
|
WB1-I |
nd |
4.18 |
nd |
nd |
nd |
1.06 |
4.83 |
nd |
97.63 |
29.97 |
21.81 |
114.9 |
121.6 |
13.93 |
|
|
WB1-II |
nd |
2.24 |
nd |
nd |
nd |
nd |
nd |
nd |
nd |
0.72 |
0.75 |
2.97 |
1.32 |
nd |
|
|
WB2-I |
nd |
2.86 |
nd |
nd |
nd |
0.58 |
nd |
nd |
nd |
0.50 |
2.87 |
nd |
3.41 |
4.53 |
|
|
WB2-II |
nd |
2.65 |
nd |
nd |
nd |
nd |
nd |
nd |
nd |
0.51 |
0.94 |
9.75 |
1.70 |
2.73 |
|
|
WB3-I |
2.22 |
5.58 |
nd |
nd |
nd |
nd |
3.03 |
nd |
0.04 |
0.61 |
2.84 |
3.42 |
3.20 |
4.81 |
|
|
WB3-II |
2.14 |
2.87 |
nd |
nd |
nd |
nd |
nd |
nd |
nd |
0.55 |
0.79 |
4.24 |
1.48 |
nd |
|
|
SB4-I |
nd |
3.22 |
nd |
nd |
1.09 |
nd |
nd |
nd |
nd |
0.54 |
3.17 |
2.48 |
3.40 |
nd |
|
|
SB4-II |
nd |
1.33 |
nd |
nd |
nd |
nd |
nd |
nd |
nd |
nd |
0.67 |
0.74 |
1.32 |
2.68 |
|
|
SJ1-I |
1.30 |
3.94 |
nd |
nd |
nd |
nd |
nd |
nd |
0.48 |
nd |
2.80 |
2.34 |
3.48 |
4.45 |
|
|
SJ1-II |
nd |
2.15 |
nd |
nd |
nd |
nd |
nd |
nd |
nd |
0.51 |
0.65 |
0.83 |
1.62 |
nd |
|
|
S E M A R A N G |
WT1-I |
12.08 |
4.69 |
nd |
nd |
nd |
0.17 |
4.85 |
nd |
0.08 |
0.61 |
3.89 |
2.91 |
nd |
nd |
|
WT1-II |
7.73 |
2.32 |
3.81 |
nd |
nd |
nd |
0.77 |
nd |
nd |
0.57 |
1.02 |
0.92 |
nd |
nd |
|
|
WT2-I |
7.03 |
15.69 |
nd |
nd |
1.54 |
nd |
nd |
nd |
nd |
0.90 |
3.47 |
3.60 |
nd |
nd |
|
|
WT2-II |
4.88 |
18.21 |
nd |
nd |
nd |
nd |
4.92 |
nd |
nd |
0.61 |
0.75 |
0.85 |
nd |
nd |
|
|
WK1-I |
1.51 |
4.66 |
nd |
nd |
nd |
nd |
nd |
nd |
nd |
0.36 |
2.75 |
nd |
3.14 |
4.48 |
|
|
WK1-II |
0.38 |
2.58 |
nd |
nd |
nd |
nd |
nd |
nd |
nd |
0.70 |
2.38 |
0.80 |
1.87 |
nd |
|
|
WK2-I |
1.63 |
4.21 |
nd |
nd |
2.05 |
nd |
nd |
nd |
nd |
0.38 |
2.81 |
nd |
nd |
nd |
|
|
WK2-II |
0.74 |
2.50 |
nd |
nd |
nd |
nd |
nd |
nd |
nd |
0.48 |
0.73 |
0.55 |
1.81 |
2.87 |
|
|
SK3-I |
1.21 |
6.16 |
nd |
nd |
nd |
nd |
3.43 |
nd |
nd |
0.39 |
2.82 |
nd |
3.17 |
nd |
|
|
SK3-II |
0.46 |
3.63 |
nd |
nd |
nd |
nd |
0.01 |
nd |
nd |
0.51 |
0.70 |
0.60 |
nd |
2.76 |
|
|
SM1-I |
nd |
nd |
nd |
nd |
nd |
nd |
nd |
nd |
nd |
nd |
nd |
nd |
nd |
nd |
|
|
SM1-II |
0.64 |
2.12 |
nd |
nd |
nd |
nd |
5.04 |
nd |
nd |
0.53 |
0.72 |
0.55 |
1.48 |
nd |
|
|
B O G O R & J A K A R T A |
WC1-I |
1.49 |
5.43 |
nd |
nd |
1.51 |
nd |
nd |
nd |
nd |
0.92 |
2.94 |
2.73 |
3.37 |
4.50 |
|
WC1-II |
nd |
1.34 |
nd |
nd |
nd |
nd |
nd |
nd |
0.10 |
1.22 |
1.19 |
0.79 |
1.68 |
2.90 |
|
|
WC2-I |
1.79 |
7.19 |
nd |
nd |
nd |
nd |
5.08 |
nd |
0.57 |
1.86 |
2.99 |
3.68 |
nd |
nd |
|
|
WC2-II |
0.04 |
1.89 |
nd |
nd |
nd |
nd |
nd |
nd |
nd |
0.47 |
0.70 |
0.57 |
1.29 |
nd |
|
|
WC3-I |
4.34 |
7.34 |
nd |
nd |
nd |
nd |
nd |
nd |
nd |
0.69 |
3.26 |
2.57 |
3.76 |
4.71 |
|
|
WC3-II |
0.53 |
1.36 |
nd |
nd |
nd |
nd |
nd |
nd |
nd |
0.53 |
0.72 |
0.60 |
1.39 |
nd |
|
|
WC4-I |
3.02 |
13.67 |
nd |
nd |
nd |
0.29 |
3.56 |
nd |
nd |
0.97 |
3.04 |
4.05 |
6.24 |
nd |
|
|
WC4-II |
2.96 |
0.68 |
3.25 |
nd |
nd |
nd |
nd |
nd |
nd |
0.51 |
0.68 |
0.66 |
nd |
nd |
|
|
WC5-I |
19.99 |
6.64 |
nd |
nd |
nd |
0.32 |
2.79 |
nd |
0.18 |
1.77 |
3.11 |
4.12 |
3.30 |
nd |
|
|
WC5-II |
23.37 |
nd |
3.33 |
nd |
nd |
nd |
nd |
nd |
0.68 |
1.01 |
0.85 |
2.22 |
nd |
nd |
|
|
SC6-I |
1.47 |
7.37 |
nd |
nd |
nd |
nd |
nd |
nd |
nd |
0.85 |
3.28 |
2.53 |
3.49 |
4.76 |
|
|
SC6-II |
0.09 |
1.82 |
nd |
nd |
nd |
nd |
nd |
nd |
nd |
0.46 |
0.71 |
0.73 |
1.38 |
nd |
|
|
SP1-I |
1.15 |
4.71 |
nd |
nd |
1.19 |
nd |
2.57 |
nd |
nd |
0.74 |
|||||