Nutrients, Trace Metals, and Organic Contaminants in Banten Bay, Indonesia

Nutrients, Trace Metals, and Organic Contaminants in Banten Bay, Indonesia

Marine Pollution Bulletin Edited by Bruce J. Richardson The objective of BASELINE is to publish short communications on di€erent aspects of pollutio...

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Marine Pollution Bulletin

Edited by Bruce J. Richardson

The objective of BASELINE is to publish short communications on di€erent aspects of pollution of the marine environment. Only those papers which clearly identify the quality of the data will be considered for publication. Contributors to Baseline should refer to `BaselineÐThe New Format and Content' (Mar. Pollut. Bull. 42, 703±704). Marine Pollution Bulletin Vol. 42, No. 11, pp. 1187±1190, 2001 Ó 2001 Elsevier Science Ltd. All rights reserved Printed in Great Britain 0025-326X/01 $ - see front matter

PII: S0025-326X(01)00214-4

Nutrients, Trace Metals, and Organic Contaminants in Banten Bay, Indonesia KEES BOOIJ*, M. THEO J. HILLEBRAND, ROB F. NOLTING and JAN VAN OOIJEN Netherlands Institute for Sea Research, P.O. Box 59, 1790 AB Den Burg, Netherlands Banten Bay is a 10  15 km large, shallow (<20 m) embayment on the north-west coast of Java, Indonesia (Figs. 1 and 2). Extensive industrialisation is planned for the area west of the bay. It is expected therefore, that signi®cant changes in the levels of nutrients, trace metals and organic contaminants will occur in the near future. In November 1995, a ®eld survey was made to establish the pre-industrialisation baseline for Banten Bay water quality. The Ujung River is the primary source of fresh water in this area, discharging some 10 km east of Banten Bay. An estimated 15% of the Ujung River discharge ¯ows directly into the bay via the former delta. During the ®eld survey (at the end of the dry season) little or no discharge from the delta was observed, but in February 1996 (wet season) the out¯ow was signi®cant (Hoekstra, personal communication). Rivers of secondary importance are the Banten River and the Kamayung River, discharging in the south and south-west part of the bay. In addition, 11 smaller rivers discharge into the bay. Following the redirection of the out¯ow of Ujung River

*Corresponding author. Tel.: +31-222-369-463; fax: +31-222-319674. E-mail address: [email protected] (K. Booij).

in the ®rst half of the 20th century, the former delta at the north-east end of Banten Bay has been eroding, and extensive sedimentation has taken place in the southern and eastern region of the bay (Van Maren, 2000). Tidal currents are mainly diurnal, with ¯ow rates of between 20 and 100 cm (Van Maren, 2000). Human activities in the area include agriculture (rice), industry (steel, paper, metallurgy, leather, building materials, automobile workshops, textile, plastic), mariculture and ®sheries (Heun, 1996). Water samples were taken with a Postma Water Sampler or a Niskin bottle. The water phase was analysed for nutrients, pH, salinity, temperature and dissolved oxygen. Sediment samples were collected using a Van Veen or MacIntyre grab. Sub-samples for the metal analysis were dried at 60 °C within a day after sampling, and were stored in sealed, plastic petri dishes. The samples were analysed for total Fe, Al, Ca, Zn, Cu, Cd, Pb, Ni, Cr after digestion with aqua regia and ¯uoric acid in a microwave oven, using ¯ame AAS and graphite furnace AAS. Results for the analysis of certi®ed reference materials (BCR141 and BCR142) typically deviated 3% (Al, Fe, Ca) to 15% (other metals) from the certi®ed values. Sub-samples for the analysis of organic contaminants (10±20 g ww) were extracted with dichloromethane/methanol/water for 5 min using the extraction method of Bligh and Dyer (1959). Organic sulphur was removed by the addition of sodium sulphite prior to extraction. Internal standards (CB112, pyrene-D10, perylene-D12) were also added prior to extraction. After isolation of the dichloromethane layer 1 ml of 2,2,4-trimethylpentane was added, and the dichloromethane was evaporated. Clean-up was carried out with alumina (16% water, elution with 15 ml 4% diethyl ether in hexane). Samples were separated in a non-polar and a polar fraction using silica adsorption chromatography (6% water, elution with 8 ml hexane (®rst fraction), and 10 ml 10% diethylether in hexane (second fraction)). The ®rst fraction contained PCBs, chlorobenzenes and p; p0 -DDE, and the second fraction contained PAHs and p; p0 -DDT. Both fractions were concentrated to 100 ll. The non-polar fraction was analysed for PCBs, HCB, and p; p0 -DDE using GC-ECD. The polar fraction was analysed for non-alkylated PAHs and p; p0 -DDT using GC-MS (EI 70 eV, selected ion recording of the molecular ions). Six procedure blanks were processed to assess the quantitation limits (LOQ ˆ average blank value ‡ 10  the standard deviation in the blank values). LOQ values amounted to 0.01 ng/g for PCBs, HCB, and p; p0 -DDE, 0.7 ng/g for PAHs, and 0.02 ng/g for p; p0 -DDT. Results for the analysis of certi®ed reference material IAEA142 typically deviated 27% from the certi®ed values for PCBs, and 46% for PAHs, but generally fell within the con®dence limits of the certi®ed values for this reference material. A 1187

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Fig. 1 Location of the study area (rectangle in the north-west corner of Java).

Fig. 2 Distributions of typical analyte concentrations in Banten Bay: (a) CB153; (b) Cd; (c) phosphate; and (d) HCB. The surface area of the circles is proportional to the analyte concentration. The station clusters that appeared in the statistical analysis of the data are separated by a dotted line.

summary of analyte concentrations is given in Table 1 for Banten Bay and for Banten, Kamayung, and Ujung Rivers. 1188

The distribution of nutrients, trace metals, and organic contaminants was assessed by principal component analysis (PCA) after normalising trace metal concentrations to aluminium, and normalising organic contaminant concentrations to organic carbon (Fig. 3). The ®rst and second principal component explain 76% of the total variance in the data. The third and fourth principal component account for a further 13% and 5% of the variance, respectively. Three clusters of analytes can be identi®ed in Fig. 3: organic contaminants, trace elements and nutrients. Distribution patterns for typical representatives from these clusters are shown in Figs. 2(a) (CB153), (b) (Cd), and (c) (phosphate). The major sources for these analytes can be identi®ed as the Ujung River, the Banten River, and the Kamayung River, respectively. The distribution of the analyte concentrations in the bay is fairly uniform, although locations in the western and eastern part are slightly separated, with western locations more enriched with trace metals than eastern locations. The variance in HCB concentrations is poorly described by the ®rst two principal components, as indicated by the short HCB vector in the biplot (Fig. 3). The deviating behaviour of HCB is illustrated by its distribution shown in Fig. 2(d). Except for the river stations, few di€erences were observed for water column parameters in the sampling area. Salinities attained an average value of 32:4  0:1 and water temperature was approximately 29 °C. Dissolved oxygen levels were 6:8  0:8 mg=l, which is close to the equilibrium value of 6.4 mg/l. Values for pH were approximately 8:23  0:03. These observations indicate that the water mass within the bay was well mixed. Nutrient concentrations in the bay were similar to sea surface values found by Van der Weijden et al. (1989) for the Kau Bay, and by Wetsteyn et al. (1990) for the Banda Sea and the Arafura Basin, with the exception of silicate which was higher by a factor of 6. Nutrient concentrations in the Ujung River and the Kamayung River were higher than in the bay by 1±3 orders of magnitude, but concentrations decreased rapidly to background values within 1 km of the river mouth. It appears that the ¯ushing rate of the bay is large compared to the river input rate. The absence of east-west gradients along the north-eastern corner of the bay indicates that the main stream of the Ujung River does not contribute signi®cantly to the nutrient concentrations in the bay. The distribution of urea was studied because of its application in shrimp mariculture plants located near the eastern and southern part of the bay, but no appreciable urea gradients were observed. The sedimentary organic carbon content was approximately 1:0  0:3%. Except for hexachlorobenzene, few gradients were observed within the bay. PCB concentrations were two to three orders of magnitude smaller than in a number of North-Western European rivers (Duinker, 1986). Compared to concentrations observed in the Dutch Wadden Sea and the Scheldt estuary, hexachlorobenzene and p; p0 -DDE concentrations

Volume 42/Number 11/November 2001 TABLE 1 Summary of concentrations of nutrients (surface water), metals (surface sediments, dry weight basis) and organc contaminants (surface sediments, dry weight basis) in Banten Bay and three rivers discharging into the bay. Abbrieviation in Fig. 3 Oxygen Temperature Salinity pH Organic C Phosphate Ammonium Nitrite Nitrate Silicate Urea Hexachlorobenzene p; p0 -DDT p; p0 -DDE CB 28 CB 52 CB 70 CB 101 CB 138 CB 149 CB 153 CB 170 CB 180 Phenanthrene Fluoranthene Pyrene Benzo[a]anthracene Chrysene Benzo[b]¯uoranthene Benzo[e]pyrene Benzo[a]pyrene Indeno[1,2,3-c,d]pyrene Benzo[g,h,i]perylene Fe Al Ca Zn Cu Cd Pb Ni Cr

P NH4 NO2 NO3 Si HCB

PHEN FLUO PYR BaA CHR BbFLUO BeP BaP IP BPER

Unit

Bay average

Banten River

Ujung River

Kamayung River

(mg/l) (°C) (±) (±) (%) …lM† …lM† …lM† …lM† …lM† …lM† (ng/g) (ng/g) (ng/g) (ng/g) (ng/g) (ng/g) (ng/g) (ng/g) (ng/g) (ng/g) (ng/g) (ng/g) (ng/g) (ng/g) (ng/g) (ng/g) (ng/g) (ng/g) (ng/g) (ng/g) (ng/g) (ng/g) (%) (%) (%) (ug/g) (ug/g) (ug/g) (ug/g) (ug/g) (ug/g)

6.82 29.0 32.4 8.23 1.0 0.08 0.06 0.03 0.04 7 0.5 0.06 0.1 0.28 0.04 0.02 0.01 0.01 0.03 0.03 0.03 0.01 0.01 7 8 9 5 6 14 7 6 6 6 4 8 3 73 11 0.4 19 15 26

7.80 28.7 32.4 8.26 1.4 0.06 0.00 0.02 0.00 11 0.4 0.01 0.5 1.51 0.04 0.02 0.02 0.04 0.12 0.07 0.12 0.03 0.05 4 22 26 15 16 25 15 21 12 14 4 4 1 81 16 2.1 25 11 10

± 26.5 ± ± 1.0 0.39 1.31 0.25 15.36 400 1.4 0.09 12.6 5.72 ± 0.06 0.11 0.08 0.20 0.27 0.20 0.06 0.14 358 181 226 142 170 266 122 106 80 99 4 9 1 76 13 0.1 17 10 20

2.84 28.0 31.5 7.46 1.6 1.08 10.53 1.70 32.30 524 1.6 0.01 0.4 1.38 0.16 0.02 0.02 0.04 0.09 0.05 0.10 0.03 0.06 36 85 94 81 53 195 71 99 78 80 4 9 1 80 15 0.2 26 7 11

in the bay were of similar magnitude, the concentration of CB153 was 1±2 orders of magnitude lower and the concentration of benzo[a]pyrene was one order of magnitude lower. PCB concentrations were in line with the observations for suspended matter in the coastal waters around East Java (Hillebrand et al., 1989). Concentrations of p; p0 -DDE were about an order of magnitude lower than in Jakarta Bay (Williams et al., 2000). Organic contaminant concentrations were dominated by polyaromatic hydrocarbons, followed by p; p0 -DDE, p; p0 -DDT, hexachlorobenzene and PCBs. Relatively high concentrations of hexachlorobenzene were found at the north-western part of the bay (Fig. 2(d)), possibly originating from industrial sources in this area. Concentrations of trace metals were similar to values found for unpolluted areas such as the Lena River estuary and the Laptev Sea (Nolting et al., 1996). The metal/Al ratios were much smaller than for the Rhone delta (Nolting and Van Hoogstraten, 1993). Trace metal

concentrations were similar to the values found by Middelburg et al. (1989) for the Kau Bay, with the exception of Cr and Ni, which were lower by one order of magnitude. Concentrations of Ni, Pb, and Zn were also similar to the values found for Jakarta Bay (Williams et al., 2000). Trace metal concentrations in the western part of the bay were slightly elevated compared to the eastern side of the bay, which may be attributed to local sources in the western part of the bay, or to the higher sedimentation in the eastern part as a result of the erosion of the former Ujung delta. Based on the present (dry season) data, Banten Bay may be considered relatively pristine from the viewpoint of nutrient levels and concentrations of trace metals, PCBs, PAHs and several pesticides. Elevated concentrations that were found in the river entrances into the bay dropped to background levels within a short distance. This indicates that the bay is well ¯ushed, and that signi®cant mixing takes place between contaminated 1189

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Fig. 3 Biplot of the PCA of contaminant concentrations in Banten Bay. The orthogonal projection of the stations (circles) on each analyte vector (or its elongation) approximates the standardised analyte concentration for these stations (i.e., the extent to which the concentration is above or below average). The length of the analyte vectors indicates the reliablity of this approximation.

river-borne particles and sea-borne particles or particles that originate from the eroding former Ujung delta. This study was carried out within the framework of the Teluk Banten Research Programme on Coastal Zone Management. It was supported by a grant from the Foundation for the Advancement of Tropical Research (WOTRO) of the Netherlands Organization for Scienti®c Research (NWO). This is NIOZ publication 3550.

Marine Pollution Bulletin Vol. 42, No. 11, pp. 1190±1193, 2001 Ó 2001 Elsevier Science Ltd. All rights reserved Printed in Great Britain 0025-326X/01 $ - see front matter

PII: S0025-326X(01)00217-X

Metallic Elements and Metal Poisoning Among White-tailed Sea Eagles from the Baltic South Coast J. FALANDYSZ *, H. ICHIHASHIà, K. SZYMCZYK ,1, S. YAMASAKI§ and T. MIZERA  

*Corresponding author. 1 Present address: University of Warmia and Mazury, Plac è odzki (Kortowo) PL 10-957 Olsztyn, Poland.

1190

Bligh, E. G. and Dyer, W. J. (1959) A rapid method of total lipid extraction and puri®cation. Canadian Journal of Physiology 37, 911±917. Duinker, J. C. (1986) The role of small, low density particles on the partition of selected PCB congeners between water and suspended matter (North Sea area). Netherlands Journal of Sea Research 20, 229±238. Heun, J. C. (1996) Domestic and Industrial Waste Water Load on the Banten Bay. A Preliminary Estimate. Institute for Hydraulic Engineering, Delft, Netherlands. Hillebrand, M. Th. J., Everaarts, J. M., Razak, H., Moelyo, D., Stolwijk, L. and Boon, J. P. (1989) Input of selected chlorinated hydrocarbons into the coastal area of East Java and adjacent waters: distribution patterns in the dissolved and suspended phase. Netherlands Journal of Sea Research 23, 359±368. Middelburg, J. J., de Lange, G. J., Van der Weijden, C. H. and Sho®yah, S. (1989) Sediment chemistry of Kau Bay, Halmaheira (Eastern Indonesia). Netherlands Journal of Sea Research 24, 607± 613. Nolting, R. F. and Van Hoogstraten, R. J. (1993) Diagenesis and the vertical distribution of metals in sediments of the Gulf of Lions. Water pollution research report 30. Commission of the European Communities, Brussels, EROS 2000, pp. 237±242. Nolting, R. F., Van Dalen, M. and Helder, W. (1996) Distribution of trace and major elements in sediments and pore waters of the Lena Delta and Laptev Sea. Marine Chemistry 53, 285±299. Van der Weijden, C. H., de Lange, G. J., Middelburg, J. J., Van der Sloot, H.A., Hoede, D. and Sho®yah, S. (1989) Geochemical characteristics of Kau Bay water. Netherlands Journal of Sea Research, 24, 583±589. Van Maren, D. S. (2000) Three-Dimensional Flow Patterns and Sediment Dispersal in Teluk Banten. 56 pp. Institute for Marine and Atmospheric Research, Utrecht, Netherlands. Wetsteyn, F. J., Ilahude, A. G. and Baars, M. A. (1990) Nutrient distribution in the upper 300 m of the eastern Banda Sea and northern Arafura sea during and after the upwelling season, August 1984 and February 1985. Netherlands Journal of Sea Research 25, 449±464. Williams, T. M., Rees, J. G. and Setiapermana, D. (2000) Metal and trace organic compounds in sediments and waters of Jakarta Bay and the Pulan Seribu complex, Indonesia. Marine Pollution Bulletin 40, 277±284.

 Department of Environmental Chemistry and Ecotoxicology, University of Gda nsk, ul. Sobieskiego 18, PL 80-952 Gda nsk, Poland àDivision of Environment Conservation, Hydrochemistry Section, National Research Institute of Fisheries and Environment of Inland Sea, Maruishi 2-17-5, Ohno-cho, Hiroshima 739-0452, Japan §Faculty of Agriculture, Tohoku University, Sendai, Japan   Department of Zoology, Agricultural University, Al. Wojska Polskiego 71C, PL 60-625 Pona n, Poland White-tailed sea eagles (Haliaeetus albicilla) are an endangered species. However, due to e€orts in the past four decades to protect the species in Europe, the population of H. albicilla has improved recently both in Poland and in certain other European countries (Mizera, 1999). Mercury, lead and particular rodenticides are reported as causes of acute or sub-acute poisonings and deaths among white-tailed sea eagles (Oehme, 1981; Falandysz et al., 1988; Kenntner et al., 1998; Mizera,