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ENVIRONMENTAL MONITORING AND GOVERNANCE

POPs POLLUTION IN THE EAST ASIAN

COASTAL HYDROSPHERE

MONITORING OF PERSISTENT ORGANIC POLLUTANTS (POPs) IN THE COASTAL HYDROSPHERE OF INDONESIA

ENVIRONMENTAL MANAGEMENT CENTER

INDONESIA

2003

Monitoring of Persistent Organic Pollutants In The Coastal Hydrosphere of Indonesia

Environmental Management Center

Kawasan PUSPIPTEK Serpong Tangerang

Indonesia

ABSTRACT

Monitoring of Persistent Organic Pollutants (POPs) in the coastal hydrosphere of Indonesia was carried out to investigate environmental water contamination by some POP compounds. River from four cities in Jawa Island including Jakarta, Bogor, Semarang and Surabaya were selected as sampling location. Water samples were collected in June to September 2002 represented dry season and as representating rainy season water samples were collected in January to February 2003. Some sediment and soil samples were also collected from similar location of water sampling sites. The target compounds for analysis consist of a group of POP compounds including Hexachlorobenzene (HCB), Heptachlor, Aldrin, Endrin, Dieldrin, Mirex, Chlordane, DDT and for additional some other organochlorine insecticides (OCs) including a group of Hexachlorocyclohexane (HCH: α-HCH, β-HCH, δ-HCH, γ-HCH) and methoxychlor were also investigated.

Samples were analyzed by using GCMS QP 2010. The monitoring result indicated that some POP and OC compounds were detected in river water, sediment and soil samples in trace level concentration. POPs and OCs were detected at lower concentration in water (ppt level) than in sediment or soil (ppb level). The concentration of POPs in water samples were in the range of 0.13 to 361 ppt, in sediment samples were in the range of 0.10 to 160 ppb and in soil samples were in the range of 0.10 to 964 ppb. The highest concentration of POPs compounds in water samples was detected for t-Chlordane with the value 361 ppt and for sediment and soil samples, the highest concentration were detected for endrin with the value respectively 160 ppb and 964 ppb. Organochlorine compounds were detected in the range of 0.10 to 390 ppt in water, 0.10 to 433 ppb in sediment and 0.10 to 1259 ppb in soil. The highest concentration of organochlorine in water, sediment and soil were detected for α -HCH with the value respectively are 390 ppt, 433 ppb and 1259 ppb. The existence of rainy and dry season in tropical areas results the fluctuation in river water quality caused by the fluctuation in water level. Therefore, mostly water concentration of POPs and OCs detected in dry season were not detected in rainy season. Meanwhile, concentration of POPs in sediment and soil were not quite different between dry and rainy season spesificaly for DDT and its metabolite, but it was still significantly different for organochlorines.

INTRODUCTION

Global contamination by Persistent Organic Pollutants (POPs) is now being concern internationally. It is related to the negative impact of POPs to the environment. After release into the environment, POPs disperse widely across environmental compartment, and may endanger significant part of the biosphere including human being. Their global transportation make every place in the world has possibility to be polluted by POPs and the world’s ocean gradually become the largest reservoir of the most persistent chemical. Their resistance to degradation and the high bioaccumulative capacity jeopardize the health of biological organism incapable of metabolizing or excreting these synthetic compounds. High-ranking members of food chains such as fish-eating bird , marine mammals including human being are most seriously threatened.

Indonesia used to be producing and making use some of chemicals listed for POPs. This chemicals were used by several sector mainly agriculture, forestry, health, industry, mining etc. Eventhough the application of POPs specifically POPs insecticides has been banned for agricultural purposes since 1970’s, the residue might be present in the environment because of its persistency. On the other hand, DDT was still used for certain purpose in controlling mosquito carrying malaria diseases. This chemicals has not used for malaria control program since 1993.

In order to eliminate the use, release and emission of POPs from environment, Indonesia also involved in the signed of Stockholm convention. Due to many fundamental constraints and weaknesses the government has to work hard to enhance and strengthen the national capacity of infrastructures and institution to implement this convention. Nowadays the government also starting to implement those convention by inventory the existence of POPs in Indonesia. Those inventory is also involving in the monitoring of residue POPs in the environment especially in the place which is suspected to be polluted source of POPs.

The target compounds for analysis consist of a group of POPs including Hexachlorobenzene (HCB), Heptachlor, Aldrin, Endrin, Dieldrin, Mirex, Chlordane, DDT and for additional some other organochlorine insecticides (OCs) including a group of Hexachlorocyclohexane (HCH: α-HCH, β-HCH, δ-HCH, γ-HCH) and methoxychlor. The objective of this monitoring is to identify the current level of POPs contamination in the environment. Continuous monitoring is necessary to be carried out in order to get representative data for assessing POPs condition in the environment.

METHODOLOGY

The monitoring activities on POPs and OCs contamination in environment were carried out from June 2002 to February 2003. Samples were collected from three capital cities located in Java Island including Surabaya, Semarang and Jakarta. Bogor city was also selected as sampling location since upstream of the targeted river in Jakarta was located in Bogor. Eighteen location was determined for the river sampling sites and five location were determined for coastal sampling sites. Coastal site was determined at Madura Strait Surabaya, Jakarta Bay, Java Sea Semarang. The main river selected for sampling point included Ciliwung River at Bogor and Jakarta city, Banjir Kanal Barat and Banjir kanal Timur River at Semarang and Surabaya River, Tributary of Surabaya River and Rungkut River at Surabaya. Beside water samples, river sediment and soil from the river bank were also collected for analyzing POPs and OCs. Sampling data sheet information was shown in the appendices. After collecting the samples, then were placed in the dark glass bottle and kept at cooling room at 4 ^oC.

Apparatus

1. GCMS QP-2010 (Shimadzu) equipped with chromatographic column-capillary DB-5, 30m x 0.32 mm id x 0.25 mm of film thickness

2. Rotary evaporator

3. Shaker

4. Separatory funnel 250, 500, 2000 ml

5. Erlenmeyer flask

6. Evapotary flask

Reagents

1. Hexane for residue analyses grade

2. Acetone for residue analyses grade

3. Hexane Gr

4. Acetone Gr

5. Silica-gel cartridge 500 mg (Varian)

6. Florisil

7. Sodium Sulfate Anhydrous

8. Sodium Chloride

9. Internal Standard

10. Surrogate Compound

11. POPs standar including Hexachlorobenzene (HCB), Heptachlor, Aldrin, Endrin, Dieldrin, Mirex, Chlordane, DDT.

12. Organochlorine insecticides (OCs) standard including a group of Hexachlorocyclohexane (HCH: α-HCH, β-HCH, δ-HCH, γ-HCH) and methoxychlor.

Sample Extraction for POPs and OCs in Water.

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 florisil. The solution was added by IS and adjusted up to 1 ml and then analyzed by using GCMS.

Sample Extraction for POPs and OCs in Sediment and Soil.

20 gram sediment or soil was extracted by 50 ml acetone twice. The acetone layer from the first and second extraction were placed into evaporating flask and evaporated up to 30 ml. The evaporation result was added by sodium chloride solution and re-extract two times by 50 ml hexane. The hexane layer was concentrated and cleaned-up by florisil coloum. The solution was filled up to 1 ml and analyzed by using GCMS.

RESULT AND DISCUSSION

Recovery test was conducted by spiking surrogate compound into the samples and analyzed it. The recovery result from 24 samples were in the range of 78.5% to 105% with coefficient variation (CV) of 10.2.

Concentration of POPs and OCs in water samples collected in Surabaya, Semarang and Bogor-Jakarta are shown in Table 1. In Surabaya, water samples were collected from Surabaya River, Tributary of Surabaya River and Rungkut River. There are seven sampling sites in Surabaya. Five sites in Surabaya river, others in tributary of Surabaya River and Rungkut River.

The monitoring result indicated that some POPs including heptachlor, aldrin, chlordane, Dieldrin, Endrin and DDT were still scarcely detected in water in the range of 0.13 to 361 ppt. The highest concentration for POPs were in the form of t-chlordance detected at site WB3-I (tributary of Surabaya River located in Jagir Wonokromo). Major compound founded in water Surabaya was Endrin, (detected in six sampling sites) with the concentration range of 3.56 to 49.6 ppt, followed by dieldrin and trans-chlordane (each compound detected in 4 sampling sites) with the range respectively of 3.35 to 81.3 ppt and 0.28 to 361 ppt.

During dry season, organochlorine compounds including α-HCH, β-HCH, δ-HCH, γ-HCH and methoxychlor were detected in all Surabaya water samples with the concentration range of 0.10 to 390 ppt. α-HCH were detected higher in all Surabaya sampling sites than other locations. The range of α -HCH detected in Surabaya river during dry season was varied from 16 to 390 ppt, other OCs were detected in the range of 0.10 to 47.8 ppt. In rainy season, POPs and OCs were not detected in most all sampling sites meanwhile Mirex, HCB and heptachlor epoxide were not found in all Surabaya water samples neither in dry nor in rainy season.

In Semarang, four sampling sites were determined at Banjir Kanal Timur River and Banjir Kanal Barat River. Each river determined 2 sites which assumed to be upstream and downstream. In additional 2 sites were also determined in coastal water at Marina Beach and Tanjung Mas Harbor Semarang. The concentration of POP compound in Semarang were varied from 0.31 to 237 ppt. Major POPs detected in Semarang was Endrin followed by Dieldrin and t-chlordane with the value range respectively 3.54 to 237ppt; 3.34 to 27.8 ppt and 0.31 to 0.78 ppt. The highest concentration was detected for Endrin collected at site WT2 downstream of Banjir Kanal Timur River. DDT and it metabolite almost not detected in Semarang water samples.

Table 1. Concentration of POPs and OCs in the River and Sea Water in Indonesia.

SAMPLING SITES

COMPONENT AND CONCENTRATION ( ppt )

a-HCH

g-HCH

d-HCH

β-HCH

metoxichlor

Hep-tachlor

Al- drin

t-Chlordane

c-Chlordane

Dieldrin

En-drin

p-p’ DDE

p,p-DDD

o,p-DDT

p,p-DDT

mirex

WR1-I

12.9

0.10

8.11

21.9

1.26

81.3

49.6

WR1-II

WB2-I

337

10.7

10.1

6.02

41.8

3.56

0.24

0.15

WB2-II

0.29

WB3-I

264

9.81

5.49

2.91

6.14

WB3-II

3.35

3.67

WB4-I

301

14.9

14.1

9.58

3.88

361

WB4-II

WB5-I

390

23.1

47.8

19.4

4.48

13.0

2.06

2.92

32.4

WB5-II

WB6-I

85.2

9.87

4.47

4.75

4.93

11.2

0.13

WB6-II

0.21

1.29

WB7-I

144

4.41

3.7

7.27

4.62

1.54

1.87

19.6

WB7-II

0.12

2.0

1.10

1.61

WB8-II

1.38

WT1-I

34.7

75.6

0.47

2.90

0.31

51.3

0.67

WT1-II

0.96

WT2-I

16.8

25.1

0.52

17.2

2.92

0.78

27.8

237

WT2-II

0.62

0.81

WK3-I

4.0

4.93

0.26

2.82

10.7

26.2

WK3-II

WK4-I

2.69

1.31

0.83

1.57

4.39

3.34

6.70

WK4-II

2.02

3.54

WK5-I

7.01

1.99

1.64

8.66

2.71

WM6-II

0.29

WC1-I

5.80

0.12

1.69

3.73

1.74

WC1-II

1.24

0.43

WC2-I

4.80

5.96

3.50

3.44

0.21

3.17

WC2-II

3.07

1.86

0.78

WC3-I

7.67

1.35

4.87

1.69

12.9

33.5

WC3-II

WC4-I

3.63

7.06

11.1

2.78

0.81

9.57

WC4-II

0.66

0.56

0.20

1.62

1.43

WC5-I

2.44

1.38

3.96

0.61

14.8

4.0

WC5-II

2.81

0.61

WC6-I

16.5

5.57

0.39

5.10

1.0

45.9

WC6-II

0.74

14.8

4.08

0.84

1.57

1.88

WC7-I

58.7

12.1

7.29

6.75

70.2

133

4.17

WC7-II

1.83

0.92

0.64

0.90

WC8-I

WP9-I

3.97

9.04

0.56

2.25

3.24

61.9

17.2

WP9-II

0.72

3.0

1.43

0.76

Note I : Dry Season II : Rainy Season

Low concentration of methoxychlor and group of HCH were also detected in Semarang water samples during dry season with the range of 0.26 to 75.6 ppt. Meanwhile six chemicals including HCB, Heptachlor, heptachlor epoxide, ppDDE and ppDDD and mirex were not detected neither in dry and rainy season.

The main river selected as the target for POPs and OCs monitoring in Jakarta was Ciliwung River. Ciliwung River is one of the main river descends from near Bogor in west Java, down through Jakarta to Jakarta Bay. During dry season water level of Ciliwung River in upstream (Bogor) frequently decrease in significant level. On the contrary, in rainy season this river tend to contribute high water level in upstream and seriously those water could be overflows in downstream area or in Jakarta city. Flood was frequently happened during rainy season. High level and flow of river water during rainy season also make difficulty in collecting sediment sample. Due to the river condition, at present the function of Ciliwung river tend to be quite changed because of increasing pollutant come from domestic or even industrial waste enter to the river body.

There are 8 point determined as sampling sites in Ciliwung River which is stretched along upstream in Bogor to downstream in Jakarta. POPs were detected scarcely in Ciliwung River with the value range of 0.20 to 133 ppt. Only HCB and heptachlor epoxide were not detected in Ciliwung River. Organochlorine were also detected scarcely in Ciliwung river with the concentration range varied from 0.39 to 58.7 ppt.

Concerning to the water contaminated by POPs and OCs, it could be said that POPs only detected scarcely in water samples. Based on the water monitoring data, there is tendency that POPs was rare detected neither in wet nor dry season but most OCs were still detected only in dry season. In rainy season OCs were undetected. HCB and heptachlor epoxide were not detected in all water samples collected either in Surabaya, Semarang or Bogor-Jakarta. α-HCH was detected higher level in Surabaya than in Semarang or Bogor - Jakarta

For additional data, sediment and soil located in the similar water sampling site were also investigated for the contamination of POPs and OCs. The monitoring result of POPs and OCs in sediment were shown in Table 2. Most POPs and OCs in sediment sample were detected in all sampling site. The concentration of POPs detected on sediment sample were varied in the range of 0.10 ppb to 160 ppb. The highest concentration was detected for Endrin in Surabaya sediment. DDT and its metabolites were detected in most sampling site with the range of 0.24 to 51.1 ppb. Other POPs detected in most Surabaya sediment were Aldrin, t-chlordane and Dieldrin (each detected in 5 sites) followed by endrin (detected in 3 sites) with the concentration range respectively 0.16 to 2.04 ppb; 0.26 to 8,73 ppb; 7.67 to 46 ppb; and 20.8 to 50.3 ppb. HCB and Mirex which was not detected in all Surabaya water samples were detected in Surabaya sediment at very low concentration, with the range respectively of 0.10 to 1.01 ppb and 0.81 to 1.49 ppb. Heptachlor only detected in two site with the value 0.44 and 4.64 ppb. Besides in water, heptachlor epoxide were also undetected in sediment collected from Surabaya.

Table 2. Concentration of POPs and OC s in River Sediment in Indonesia.

SAMPLING SITES

COMPONENT AND CONCENTRATION ( ppb )

a-HCH

g-HCH

d-HCH

β-HCH

mehtoxychlor

HCB

Hep-tachlor

Hep-tachlor.epoxide

Al- drin

t-Chlordane

c-Chlordane

Dieldrin

En-drin

p-p’ DDE

p,p-DDD

o,p-DDT

p,p-DDT

mirex

SURABAYA

SR1-II

12.5

11.5

1.20

1.71

SB2-I

417

60.6

2.45

2.11

1.41

0.32

0.44

2.04

8.73

46.0

23.9

1.0

7.38

5.85

3.65

0.93

SB2-II

6.48

8.83

8.10

SB3-I

433

17.5

0.45

10.4

1.60

0.55

0.38

17.0

0.88

0.84

2.49

SB3-II

1.49

SB4-I

302

3.25

55.9

4.57

0.96

0.26

7.71

50.3

0.28

1.36

0.74

1.94

SB4-II

0.30

1.18

0.24

3.49

0.90

SB5-I

258

1.89

0.30

23.5

2.35

0.16

0.64

7.67

0.52

1.71

2.97

3.43

SB5-II

71.8

0.10

44.9

51.1

SB6-I

229

4.55

2.11

28.8

4.76

1.01

1.92

0.77

37.4

20.8

1.27

4.06

1.18

10.0

0.81

SB6-II

0.54

1.98

2.70

SB7-II

3.37

4.64

11.9

ST1-I

12.3

9.83

0.24

6.21

4.16

0.78

7.25

10.6

1.41

7.37

ST1-II

2.95

7.73

ST2-I

15.8

10.7

0.50

3.76

4.81

0.45

7.12

0.94

0.10

8.66

ST2-II

1.29

1.38

SK3-I

0.71

2.66

4.05

2.12

0.43

0.94

2.86

0.39

0.17

0.18

3.01

SK3-II

0.92

SK4-I

1.85

2.91

2.41

0.22

4.06

0.10

2.28

SK4-II

0.81

0.92

SC1-I

9.83

2.16

0.83

0.36

1.82

0.12

2.82

SC1-II

0.32

1.86

SC2-I

5.99

1.15

1.21

1.97

11.8

17.5

0.17

0.25

SC2-II

0.60

0.24

0.30

0.29

SC3-I

213

6.84

7.87

0.79

0.15

12.3

31.2

0.38

1.03

4.13

SC4-I

15.5

4.72

0.10

6.11

0.14

1.23

12.0

28.0

0.27

0.35

4.31

SC4-II

3.18

0.27

0.86

0.84

SC5-I

54.1

3.35

2.18

1.60

0.49

0.76

0.84

3.28

104

0.56

1.91

0.57

2.84

1.16

SC5-II