2002

 

A survey on water pollution by Endocrine Disrupter Compounds:

Monitoring of Organochlorine Pesticides, Phenols and Phthalates  In The Coastal Hydrosphere of Indonesia

 

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