First comprehensive screening of lipophilic organic ...

MPB-07478; No of Pages 11 Marine Pollution Bulletin xxx (2016) xxx–xxx

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Marine Pollution Bulletin journal homepage: www.elsevier.com/locate/marpolbul

First comprehensive screening of lipophilic organic contaminants in surface waters of the megacity Jakarta, Indonesia L. Dsikowitzky a,⁎, M. Sträter a, Dwiyitno a,b, F. Ariyani b, H.E. Irianto c, J. Schwarzbauer a a

Institute of Geology and Geochemistry of Petroleum and Coal, RWTH Aachen University, Lochnerstrasse 4-20, 52056 Aachen, Germany Research and Development Center for Marine and Fisheries Product Processing and Biotechnology (BBP4KP), Ministry of Marine Affairs and Fisheries, Jl. K.S. Tubun, Petamburan VI, Jakarta Pusat 10260, Indonesia c Research Center for Fisheries Management and Conservation, Ministry of Marine Affairs and Fisheries, Gedung Balitbang-2, Jl. Pasir Putih II, Ancol Timur, Jakarta 14430, Indonesia b

a r t i c l e

i n f o

Article history: Received 29 September 2015 Received in revised form 28 January 2016 Accepted 4 February 2016 Available online xxxx Keywords: Tropical rivers Municipal sewage Municipal markers Pharmaceutical drugs Megacities

a b s t r a c t Jakarta is an Indonesian coastal megacity with over 10 million inhabitants. The rivers flowing through the city receive enormous amounts of untreated wastewaters and discharge their pollutant loads into Jakarta Bay. We utilized a screening approach to identify those site-specific compounds that represent the major contamination of the cities' water resources, and detected a total number of 71 organic contaminants in Jakarta river water samples. Especially contaminants originating from municipal wastewater discharges were detected in high concentrations, including flame retardants, personal care products and pharmaceutical drugs. A flame retardant, a synthetic fragrance and caffeine were used as marker compounds to trace the riverine transport of municipal wastewaters into Jakarta Bay. These markers are also appropriate to trace municipal wastewater discharges to other tropical coastal ecosystems. This application is in particular useful to evaluate wastewater inputs from land-based sources to habitats which are sensitive to changing water quality, like coral reefs. © 2016 Elsevier Ltd. All rights reserved.

1. Introduction Indonesia is the world's fourth most populous country and a center of marine biodiversity (Roberts et al., 2002). As in many other emerging economies, the rapid economic growth is accompanied by a migration towards the cities. The greater Jakarta area, Jabodetabek, is the main center of the Indonesian economic activity. It accounts for 12% of the GNP, 61% of the country's financial activities and 31% of the domestic industrial output. Moreover, Jabodetabek is the largest concentration of urban population in Indonesia (Nur et al., 2001). The rapid growth of this coastal megacity strongly enhanced the usage of freshwater resources for domestic and industrial purposes. The 13 rivers which flow through Jakarta City and discharge into Jakarta Bay receive wastewaters from N 10 million inhabitants. Wastewaters from flush lavatories are collected in septic tanks and disposed separately. A large proportion of the other wastewaters remains untreated and flows directly from the households into open channels which are connected with the rivers/channels. The Jakarta river systems therefore receive large amounts of untreated or partially treated municipal wastewaters and transport the contaminant loads towards Jakarta Bay.

⁎ Corresponding author. E-mail address: [email protected] (L. Dsikowitzky).

The occurrence of some organic contaminant groups in water, sediments and economic important mussel species from Jakarta Bay was previously studied. This includes polycyclic aromatic hydrocarbons (PAHs), DDT (bis(chlorophenyl)trichloroethane) and DDT-metabolites, polychlorinated biphenyls (PCBs), tributyltin (TBT), polybrominated diphenyl ethers (PBDEs), hexachlorocyclohexanes (HCHs) and linear alkylbenzenes (LABs) (Williams et al., 2000; Monirith et al., 2003; Sudaryanto et al., 2007a, b, Rinawati et al., 2012; Harino et al., 2012; Falahudin et al., 2013). Dsikowitzky et al. (2014a) reported exceptionally high concentrations of the insect repellent N,N-diethyl-m-toluamide (DEET) in river water samples from Jakarta City and also showed the presence of this contaminant in seawater samples taken in the Jakarta Bay. In contrast to the many studies about organic contaminants in Jakarta Bay, the river pollution in Jakarta City regarding organic contaminants was less intensively investigated. The present study therefore provides the first comprehensive survey of organic contaminants occurring in the rivers receiving wastewaters from the tropical megacity Jakarta. The contaminant spectrum in surface waters of Jakarta City might be completely different from that known from industrial nations of the northern hemisphere. Therefore, we made use of a non-target GC/MS (gas chromatography–mass spectrometry) screening which allows for the identification of a wide range of lipophilic organic contaminants. This allows the identification of those site-specific compounds that represent the major and most harmful contamination

http://dx.doi.org/10.1016/j.marpolbul.2016.02.019 0025-326X/© 2016 Elsevier Ltd. All rights reserved.

Please cite this article as: Dsikowitzky, L., et al., First comprehensive screening of lipophilic organic contaminants in surface waters of the megacity Jakarta, Indonesia, Marine Pollution Bulletin (2016), http://dx.doi.org/10.1016/j.marpolbul.2016.02.019

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L. Dsikowitzky et al. / Marine Pollution Bulletin xxx (2016) xxx–xxx

of the cities' water resources. The compound spectrum detectable with this approach is restricted to volatile, low-molecular weight non-polar to semi-polar organic substances. In specific, we addressed the following objectives: i) identification of the most relevant organic contaminants in Jakarta river water in terms of detection frequency and concentrations and assessment of the contamination sources, ii) comparison of the detected contaminant spectrum to that of other urban areas, and iii) assessment of the distribution of selected contaminants in Jakarta coastal waters to identify pollution hotspots and to track the riverine contribution to the pollution of the Jakarta Bay. 2. Experimental 2.1. Study area and sampling The study area has a tropical monsoon climate. The Northwest monsoon (October–March) brings rainfall to the Jakarta area, whereas the Southeast monsoon (April–September) coincides with the dry season. 13 rivers flow through the greater Jakarta region (called Jabodetabek) and discharge into the relatively shallow Jakarta Bay, of which the Ciliwung River, Citarum River and Cisadane River have the biggest catchment areas (Fig. 1). Modelling results revealed an average total discharge of the rivers entering Jakarta Bay of 204.8 ± 97.4 m³ s−1 in 2012. The water circulation within the Jakarta bay shows a counter clockwise pattern with water masses leaving in north-eastern direction (van der Wulp et al., 2016). Water samples from the rivers flowing into Jakarta Bay were taken on October 6–7, 2012 (Fig. 1). Water samples were also taken at 22 stations in Jakarta Bay on October 2–4, 2012. The samples were stored at 4 °C at BBP4KP in Jakarta and transported cooled within three days to Germany. At RWTH Aachen University, the samples were stored at 4 °C and processed within three weeks. 2.2. Chemicals, blanks and recovery experiments Reference materials of the identified compounds were purchased from Sigma-Aldrich, Germany. Blank analyses (n = 2) were run to determine background concentrations of the investigated compounds. They revealed that none of the compounds considered for this study were detected in the blank. Recoveries (n = 3) were determined by spiking 1 L high-purity water (Lichrosolv, Merck, Germany) with concentrations of 5 μg of the respective reference compounds and subsequent execution of the analytical procedure as described in Section 2.3. The experimental results are presented in Table 1 and

illustrate the uncertainties associated with the quantitation of the target analytes. Caffeine exhibited a low recovery rate of 23 ± 1% with our method (Table 1). This result would have been better by solvent extraction from an alkalized aqueous matrix. Nevertheless, we included the quantitative data of caffeine because of the good reproducibility of the quantitative results. 2.3. Water sample extraction Prior to extraction, the samples were filtered through pre-cleaned MNGF-6 glass fiber filters (pore width 0.45 μm). After filtration, 1 L-aliquots of water samples were extracted according to Dsikowitzky et al. (2002), a method that was optimized for the identification and quantitation of a wide range of organic contaminants. Briefly, n-pentane (1st fraction), dichloromethane (2nd fraction) and dichloromethane after acidification to pH 2 (3rd fraction) were used for the sequential extraction in a separation funnel. Acidic compounds in the third fractions were methylated by addition of a methanolic diazomethane solution. Thereafter, the 3rd fractions were further separated in two subfractions by liquid chromatography on activated silica gel and by using 2 mL dichloromethane and 2 mL methanol as eluents, respectively. The first two fractions of the water samples were spiked with a surrogate standard solution containing d34-hexadecane (6.0 ng μL−1) and decafluorobenzophenone (7.0 ng μL−1). 200 μL of a surrogate standard containing 4-fluoroacetophenone (14.4 ng μL− 1) was added to the third fractions. Prior to GC/MS-analyses, all fractions were concentrated to final volumes of 50 μL (first two fractions) and 200 μL (third fractions). 2.4. Gas chromatography–mass spectrometry (GC/MS) GC/MS analyses were performed as single measurements with a Trace MS mass spectrometer linked to a Trace GC, scanning at a rate of 2.5 scans second− 1. Carrier gas (helium) velocity was 42 cm s− 1. A ZB-XLB fused silica capillary column was used for gas chromatographic separation (30 m × 0.25 mm ID × 0.25 μm film thickness). Chromatographic conditions were: split/splitless injection (injector temperature 270 °C), splitless time 60 s, GC oven was 3 min. at 60 °C, then programmed from 60 to 310 °C at a rate of 3 °C min-1 and kept at 310 °C for 20 min. The mass spectrometer was operated in electron impact ionization mode (70 eV), source temperature 200 °C, scanning from 35 to 700 amu. Identification of the individual compounds was based on comparison of EI + mass spectra with those of data bases (NIST, Wiley), and was verified with mass spectra of purchased reference compounds

Fig. 1. Schematic sketch of the study area with sampling stations.



3

Table 1 Compounds used for quantification of organic contaminants, their characteristic ion fragments, compound average recoveries (n = 3) and standard deviation (s) of recovery experiments. Compound Naphthalene Anthracene/Phenanthrene Triclosan, 5-chloro-2-(2,4-dichlorophenoxy)phenol Chloroxylenol, 4-chloro-3,5-dimethylphenol TXIB, 2,2,4-trimethyl-1,3-pentanedioldiisobutyrate Triethylcitrate Oxybenzone, 2-hydroxy-4-methoxybenzophenone Irgacure 184, 1-hydroxycyclohexyl-phenylmethanone DMPA, 2,2-dimethoxy-2-phenylacetophenone TMDD, 2,4,7,9-tetramethyl-5-decyne-4,7-diol Bisphenol A, 4,4'-(propane-2,2-diyl)diphenol Bumetrizole, 2-tert.-butyl-6-(5-chlorobenzotriazol-2-yl)-4-methylphenol Indole Methylindole TCEP, tris-2-chloroethyl phosphate TPPO, triphenylphosphinoxide NBBS, N-butylbenzenesulfonamide NMBS, N-ethyl-4-methylbenzenesulfonamide Benzothiazole 2-Methylthiobenzothiazole DEET, N,N-diethyl-m-toluamide Caffeine, 1,3,7-trimethylpurine-2,6-dione Nicotine, (S)-3-[1-Methylpyrrolidin-2-yl]pyridine Propyphenazone, 1,5-dimethyl-2-phenyl-4-propan-2-yl-pyrazol-3-one Diclofenac, 2-[2-[(2,6-dichlorophenyl)amino]phenyl]acetic acid, derivatized and detected as methylester Ibuprofen, (RS)-2-(4-(2-methylpropyl)phenyl)propanoic acid, derivatized and detected as methylester Mefenamic acid, 2-(2,3-dimethylphenyl)aminobenzoic acid, derivatized and detected as methylester Chlorpyrifos, O,O-Diethyl O-3,5,6-trichloropyridin-2-yl phosphorothioate Carbofuran, 2,2-dimethyl-2,3-dihydro-1-benzofuran-7-ylmethylcarbamate Isoprocarb, 2-isopropylphenylmethylcarbamate HHCB, 1,3,4,6,7,8-Hexahydro-4,6,6,7,8,8hexamethylcyclopenta[g]-2-benzopyrane AHTN, 7-acetyl-1,1,3,4,4,6-hexamethyl-1,2,3,4-tetrahydronaphthalene DIPN, di-iso-propylnaphthalenes Phenylmethoxynaphthalene 1,2-Diphenoxyethane

Characteristic ions used for quantification [m/z] 128 178 288,290 121, 156 71 157,203 151,227 99,105 151, 225 109, 151 213, 228 272, 300 90 130,131 249,251 199,277 141, 170 155, 184 108, 135 148, 181 91, 190 109, 194 84, 133 215, 230 214, 242

Reference compound used for quantification (if different)

Chlorocresol

Recovery rate [%] 50 ± 7 90 ± 7 58 ± 17 54 ± 4 72 ± 7 96 ± 3 57 ± 13 83 ± 24 88 ± 23 41 ± 6 71 ± 12 91 ± 8 87 ± 7 76 ± 9 92 ± 14 84 ± 10 102 ± 15 89 ± 4 75 ± 19 97 ± 9 87 ± 17 23 ± 1 60 ± 12 61 ± 11

Recovery rate of mefenamic acid considered

220

79 ± 8

208

65 ± 3

314 149, 164 136

Not determined 76 ± 16 66 ± 21

243, 258

94 ± 7

243, 258 197, 212 91 121, 214

93 ± 7 88 ± 2 76 ± 17 94 ± 11

considering also gas chromatographic retention times and elution orders (for details see Table 2). Compounds for which no reference material was available, were tentatively identified. Identified compounds were screened in all samples. Quantitative data were obtained by integration of selected ion chromatograms extracted from the total ion current. The ions used for quantification are given in Table 1. GC/MS response factors for the quantified compounds were determined from four-point linear regression functions based on calibration measurements with different compound concentrations. The concentrations ranged within the expected concentrations of the compounds in the samples and within the linear detection range. For correction of injection volume and sample volume inaccuracies the surrogate standard was used. The details of the identification and quantification procedure are given in Dsikowitzky et al. (2015).

3. Results and discussion 3.1. Identified water contaminants in Jakarta river water and the role of the different contamination sources The applied non-target screening approach allowed for the identification of 71 organic contaminants in river water samples from Jakarta. The compounds were listed in Table 2 and grouped according to principal substance classes. Pharmaceutical drugs and stimulants, pesticides, synthetic fragrances and technical additives were listed as extra groups. Selected compounds with specific applications, high detection

frequency and/or compounds of environmental concern were quantified and the results are also depicted in Table 2. In the following, the identified compounds are discussed according to their application. This helps to elucidate the origin of the detected contaminants and to attribute them to different contamination sources. Compounds without a specific application or that are useful as environmental indicators are discussed in Section 3.1.1. Most identified compounds, however, have a specific application and were assigned to five groups: i) compounds used for industrial manufacturing, ii) plasticizers, flame retardants, antioxidants and vulcanization accelerators, iii) personal care products, disinfectants and surfactant residues, iv) pharmaceutical drugs and stimulants, and v) pesticides. They are discussed in Section 3.1.2. 3.1.1. Identified compounds without specific application Polycyclic aromatic compounds (nos. 1–8, Table 2) are formed during the incomplete combustion of organic material or stem from petrogenic contamination, e.g. with fossil fuels. Dichloroaniline (no. 10) is used as educt for a wide range of industrial syntheses and occurs in industrial wastewaters (Dsikowitzky et al., 2014b). It is also formed during the degradation of diclofenac (Maier et al., 2014) and hence might occur in municipal wastewaters. Dehydroabietic acid (no.12) is a wood constituent and is frequently found in paper industry wastewaters. Trimethoxybenzoic acid (no. 15) occurs in plants and is an educt for the synthesis of pharmaceutical drugs. Benzophenone (no. 20) is used as photoinitiator for the production of special papers and is widely employed as stabilizer. It is also a constituent of sunscreen


4

No.

Organic compound

Polycyclic aromatic compounds, PACs 1 NaphthaleneR 2 C1-C4-NaphthalenesR 3 BiphenylR 4 C1-Fluorene 5 C1-Dibenzofuran 6 DibenzothiopeneR 7 C1-Dibenzothiopene 8 Phenanthrene/AnthraceneR Chlorinated compounds 9 TriclosanR 10 DichloroanilineR 11 ChloroxylenolR Aromatic carboxylic acids 12 Dehydroabietic acidm 13 3,5-Di-tert.-butyl-4-hydroxybenzoic acidm 14 Salicylic acidm 15 3,4,5-Trimethoxybenzoic acidm Esters 16 TXIBR 17 TriacetineR 18 TriethylcitrateR Aldehydes and ketones 19 3,5- Di-tert.-butyl-4-hydroxybenzaldehyde 20 BenzophenoneR 21 OxybenzoneR 22 Irgacure 184R 23 Aminoacetophenone 24 DMPAR

Sampling station R01

R02

R03

R04

R05

R06

R07

R08

R09

R10

R11

R12

R13

R14

R15

R16

R17

R18

450 X X

1600 X X

1400 X X X

3100 X X X

8300 X X X

1200 X X

2400 X X

50 X

170 X X

220 X X

340 X X

20 X X

1300 X X X

3400 X X

50 X

2300 X X X

160 X X

X

X

X

X

X

X X

120

140

100

200

700

140

170

3800 X X X X X X 500

120

50 X 730

X 850

10 60

X 270

X X

X X

X

20

100

X 20

30

10

X X X X

X

780

1200

180

X X

X X X X

X X

X

10

160

190

50

X X 90

1100

90

330

40

30

X X

280

60

X X

X X

X X

X X

X X

X X X X

X X

X X

X X

1600 X

1400 X 70

1800 X 50

2100 X 180

6000 X 170

2400 X 240

3300 X 350

1700 X

340 X

740 X 160

900 X

1100 X

570 X

1500 X 90

1800 X 290

280 X 60

1200 X 150

640 X 40

X X

X X

X X 210

X X 330 190 X

X X 1100

X X

X X 80

X X

X X

X X

X X

X X 430

X X

X X

X X

X

X X 330 160 X

X X 50

70 X

X X 30 70 X

X

X 110

X

X

X

X 40

X

1000 X

1800 X

1600

3500

600 X

670

190

X 70 X

X X X X 80 X

X X X X 110 X

X 80 X

X

X

X

Alcohols 25 TMDDR 26 Diphenylmethanol

870 X

800 X

1000 X

2200 X

1900 X

2500 X

3200 X

1200

Phenols 27 C1-PhenolR 28 C2-PhenolR 29 C3-PhenolR 30 4-Propoxyphenol 31 Bisphenol AR 32 Nonylphenol technical mixtureR

X X X X 420 X

X

X

X X 90 X

X X 130 X

X X X X 310 X

X X X X 70 X

X X X X 100 X

X X X X 170 X

X X X X 120 X

Nitrogen containing compounds 33 BumetrizoleR 34 Porofor 57, Azobis(methylpropionitrile) 35 IndoleR 36 Skatol, 3-MethylindoleR 37 DEETR

X

10 300 920 1300

270

1400

30

1100

X

X 50

X 20 X

X 830

X 60

X 50

10 1300 1200 5000

700 2100

2200 8300 18000

6000 6500 22800

2600 1200 10900

10 3500 3100 24000

760 1600 17600

6000 800

3800

X 450 30 1900

X 1200 110

30

4000 4900 23900

X 410 1400

12000 1300 5700

50 240 30



Table 2 Organic contaminants identified in river water sampled in the Greater Jakarta City area, Indonesia. All stations are indicated in Fig. 1. A cross marks that the compound was detected in the sample. Empty spaces in the table indicate that the compound was not detected in this particular sample. Selected source-specific compounds or compounds of environmental concern were quantified and the concentrations are given in ng L-1.

Sulphur containing compounds 41 NBBS, N-butylbenzenesulfonamideR 42 NMBS, N-ethyl-4-methylbenzenesulfonamideR 43 LAS, Linear alkylbenzenesulfonatesR Heterocyclic compounds 44 BenzothiazoleR 45 MTB, 2-MethylthiobenzothiazoleR 46 Isoquinoline 47 Quinaldine, 2-Methylquinoline Terpenoids 48 TerpineolR 49 Menthol 50 CamphorR 51 Eugenol, Caribethol 52 Neoisomenthol 53 BorneolR 54 Methyldihydrojasmonate Pharmaceutical drugs and stimulants 55 CaffeineR 56 NicotineR 57 PropyphenazoneR 58 Diclofenacm R 59 Ibuprofenm R 60 Mefenamic acidm R

X 200

X 1100

X 1200

X 4700

10 50 X

90 X

X X

X X X X

X X X X

X

X X

850 70

4100 230

90 80

290 350

470 X

70 240 X

X

X

3000 80 40 190

X 1300

X 2800 60

X 3000

X 580

10

20

20 250 X

70 X

X

X

1100 X X

1200

600

X X X X X X X

X X X X X X X

X X X

7800 430 50 b10 1700 3700

1300 1500 30 b10 950 1600

7200 140

X

X X

b10 590 950

X 70

440

X X X X X X X

X X X X

8900 1300 40 b10 1400 2600

2000

390 50

190 50

120

X 640

X 740

X 1000

20 270

20 140

20

10

20

20

X

120 1000 X X

Pesticides 61 ChlorpyrifosR 62 CarbofuranR 63 IsoprocarbR

X 780

X X

X X

X

100 X

90 150

X X

X

X 1100

X 610

10 60 X

150 X

410 X

100

160

X X

X X X

X

X X X

X

X X X

X

X

X

X

X X

360

770

1800

280

1300

7600

2200

6200

980

20

10

20

20

10

30

340 460

50 10 90 110

40 100 690 1600

20 b10 1300 2800

30 10 130 180

40

230 260

30 10 70 100

1600 20

20

b10 140

230

Synthetic fragrances 64 HHCBR 65 AHTNR HHCB/AHTN

1100 110 10

3100 270 12

3400 270 13

5100 450 11

15000 1400 11

3700 310 12

5200 400 13

5900 210 28

60 b10 n.a.

2900 190 15

860 80 11

50 b10 n.a.

120 b10 n.a.

3800 290 13

8900 680 13

630 60 11

2400 180 13

1100 80 14

Technical additives 66 DIPNR 67 PhenylmethoxynaphthaleneR 68 1,2-DiphenoxyethaneR

370 780 b10

1700 150 b10

120

10

290

540

1500

600

240

3600 270

130 10

3800 100

110

520

90

50

2800

b10

b10

1800 50 b10

X X

X X X

X X X

X X

X

X X

X X X

X X

X

X

X

X X

X X

Miscellaneous 69 Orthorhombic sulfur 70 OPEC, 4-tert.-Octylphenolmonoethoxycarboxylate 71 OP2EC, 4-tert.-Octylphenoldiethoxycarboxylate

X

X X



Phosphorus containing compounds 38 TributylphosphateR 39 TCEP, Tris(1-chloroethyl)phosphateR 40 TPPO, TriphenylphosphineoxideR

X

m Derivatized and detected as methylester. n.a. not applicable. R Identified using reference materials; all other compounds were identified using mass spectrum libraries. The full chemical names of the quantified compounds are given in Table 1.

5

6


agents (Richardson, 2009). C1–C3-phenols (nos. 27–29) are used as educts for industrial syntheses and as disinfection agents. 4propoxyphenol (no. 30) is used as polymerization inhibitor of vinyl and acrylic monomers, as stabilizer, as intermediate to manufacture other stabilizers, dyes, pharmaceuticals and plasticizers. It is also formed during the degradation of chlorinated phenols (Matafonova et al., 2008). Quinolines (nos. 46, 47) are natural plant constituents and are used in the manufacture of dyes, paints, insecticides and antifungals. Furthermore, isoquinoline and methylquinoline occur in coke plant wastewaters (Li et al., 2003). Indole and skatol (nos. 35, 36) are formed during the anaerobic decomposition of amino acids, along with cresol (e.g. Barker, 1981). The occurrence of indole and skatole therefore can be regarded as indicative for putrefaction processes. In addition, we identified orthorhombic sulfur (no. 69). Elemental sulfur is found in anoxic environments as an intermediate of the sulfur cycle. From this it follows that anaerobic conditions prevail in the water column at stations R1, R2, R4–R8, R15 and R17 (Table 2), where indole, skatol and orthorhombic sulfur cooccurred. The highest concentrations of indole and skatol where found at stations R4–R8, R15 and R17, located in the central part of Jakarta City (Fig. 1). Anoxic conditions in the water column imply that no higher animals are able to survive in these stream pools. 3.1.2. Identified compounds with specific applications 3.1.2.1. Compounds used for industrial manufacturing. Two of the identified compounds are employed for industrial polymer manufacturing: Irgacure 184 (no. 22) and Porofor 57 (no. 34) are used as initiators for polymer syntheses (Gudeman and Peppas, 1995). Both compounds were only detected at some stations (Table 2), but the occurrence does not coincide with the location of the industrial centers (Fig. 1). DMPA (no. 24), TMDD (no. 25), bisphenol A (no. 31), DIPN (no. 66), phenylmethoxynaphthalene (no. 67) and diphenoxyethane (no. 68) (Table 2), were previously reported as constituents of paper industry wastewaters (Dsikowitzky et al., 2015). DMPA is a photoinitiator for the production of paper coatings and TMDD a dispersing agent in printing inks. Bisphenol A, DIPN, phenylmethoxynaphthalene and diphenoxyethane are chemicals used for the manufacturing of thermal papers. The appearance of phenylmethoxynaphthalene and DIPN in water sampled at the outfall of paper-recycling facilities was proven (Terasaki et al., 2008). High concentrations of bisphenol A, DIPN, DMPA and phenylmethoxynaphthalene were found at station R11, the river receiving wastewaters from the biggest industrial area in Indonesia, Bekasi, where many paper production sites are located (Table 2, Fig. 1). But overall, the occurrence of the paper industry contaminants does not coincide with the location of industrial sites. Instead, TMDD and bisphenol A for example were found at nearly all sampling stations (190–3500 ng L−1 and 20–830 ng L−1, respectively). Although both contaminants also occur in municipal wastewaters, discharges of the paper and paint industry were found to be the main sources of TMDD and bisphenol A fluxes into the environment (Fürhacker et al., 2000; Guedez and Püttmann, 2014). However, it was reported that extremely high loads of municipal wastewaters are discharged into small rivers and channels in Jakarta City, leading to exceptionally high contaminant concentrations (Dsikowitzky et al., 2014a). This can explain the relative high TMDD and bisphenol A levels at most river stations. Furthermore, leaching of dumped wastepaper could contribute to the pollution with paper contaminants, because waste dumping into surface waters is a big problem in West Java. Bisphenol A is also used as plasticizer and could therefore partly stem from plastic leaching. It was shown that leakage and seepage water of waste deposits contained up to 25 mg L−1 bisphenol A (Schwarzbauer et al., 2002; Dsikowitzky et al., 2014b). Exposure experiments with the freshwater snail Marisa cornuarietis revealed adverse effects on reproduction and survival at EC10 13.9 ng L−1 (concentration with response of 10% of the members of the tested population) (Oehlmann et al., 2006). The authors observed

that the adverse effect of bisphenol A was at least partially masked at 27 °C (EC10 998 ng L−1) when compared with 20 °C (EC10 14.8 ng L−1). The bisphenol A concentrations we detected in Jakarta river water did not exceed 998 ng L−1 (Table 2). Triphenylphosphineoxide was found at three river stations (no. 40, Table 2). It is a byproduct of the Wittig-synthesis which is carried out for the industrial production of alkenes and is known as byproduct of other industrial syntheses. The compound is a constituent of petrochemical effluents (Botalova et al., 2009), and therefore could stem from petrochemical facilities. 3.1.2.2. Plasticizers, flame retardants, antioxidants and vulcanization accelerators. TXIB (no. 16), triacetine (no. 17) and triethylcitrate (no. 18) are common plasticizers and were frequently detected in Jakarta river water samples (Table 2). Triethycitrate is also employed as food additive. Noteworthy, TXIB occurred in high concentrations of up to 6000 ng L− 1, whereas the highest triethylcitrate concentration was only 350 ng L−1. The plasticizers NBBS (no. 41) and NMBS (no. 42) occurred occasionally, and on a much lower concentration level than TXIB. These two compounds are probably used in lesser amounts or are more rapidly degraded than TXIB. Tributylphosphate (no. 38) and TCEP (no. 39) were found in nearly all Jakarta river water samples (Table 2) and are well known environmental contaminants that are produced in high quantities for the usage as flame retardants. Schreder and La Guardia (2014) tracked flame retardants from their origin in households, in dust and laundry wastewaters, to municipal wastewater treatment plants. The highest TCEP concentrations in Jakarta river water samples (4700 ng L−1) exceed by far the maximum TCEP concentrations detected in water samples from 139 US streams taken in 1999–2000 (540 ng L−1) (Kolpin et al., 2002). Butylated hydroxytoluene (BHT) is an antioxidant in packaging materials, in adhesives, cosmetics, personal care products and pharmaceuticals. 3,5-Di-tert.-butyl-4-hydroxybenzoic acid (no. 13) and 3,5-di-tert.-butyl-4-hydroxybenzaldehyde (no. 19) that were present in nearly all Jakarta river water samples (Table 2), are BHT metabolites (e.g. Rodil et al., 2010). All plasticizers, flame retardants and the antioxidant BHT are part of industrial products (e.g. packaging, plastic bottles) that are used in large quantities in households. They therefore originate mainly from municipal wastewater discharges. Industrial wastewater discharges and leaching of dumped solid waste are supposable further sources. Benzothiazole (no. 44) and methylthiobenzothiazole (no. 45) were found in several water samples from Jakarta. The concentrations ranged from 90 to 120 ng L− 1 and from 100 to 1200 ng L− 1, respectively (Table 2). Benzothiazoles are in use as vulcanization accelerators during tire production, and benzothiazole has also further industrial applications. Ni et al. (2008) demonstrated that tire-wear particles and scrap tires are the dominant sources of benzothiazoles in the environment. The two compounds therefore originate from urban runoff of tire abrasion, but may also partly stem from additional industrial inputs. 3.1.2.3. Personal care products, disinfectants and surfactant residues. Personal care products, disinfectants and surfactants are consumed in households and the active ingredients in these products are frequently detected constituents of municipal wastewaters. Triclosan (no. 9) is in use as antimicrobial in various personal care products (e.g. in toothpaste), whereas oxybenzone (no. 21), diphenylmethanol (= benzhydrol, no. 26) and bumetrizole (no. 33) are UV adsorbers in sunscreen agents. Salicyclic acid (no. 14) is employed in cosmetic products for treatments against blemished skin. Chloroxylenol (no. 11) is an antimicrobial compound applied in hospitals and households for disinfection and sanitation. It is an ingredient of antibacterial soaps, wound-cleansing applications and household antiseptics. Triclosan, bumetrizole and salicyclic acid occurred only in some water samples from Jakarta, and triclosan exhibited low concentrations



ranging between 10 and 50 ng L− 1 (Table 2). Oxybenzone, diphenylmethanol and chloroxylenol in contrast occurred in more samples and are probably used in higher amounts or are more slowly degraded. These compounds are therefore relevant water contaminants in Jakarta stemming from the usage of personal care products. It has to be taken into account that diphenylmethanol could also be released to a minor extent from industrial emissions, because it is also an educt for the synthesis of pharmaceutical drugs, a fixative in perfumery and a terminating group in polymerization reactions. The oxybenzone and chloroxylenol concentrations in Jakarta river water (up to 1100 ng L−1and 1200 ng L−1, respectively) were higher than those of personal care products ingredients in European natural waters (Tanwar et al., 2015). DEET (no. 37) is the active ingredient in insect repellents and is known as persistent environmental contaminant. The DEET concentrations in Jakarta river water were previously discussed in Dsikowitzky et al. (2014a). Terpenoids (nos. 48, 49, 51-54) were detected in many Jakarta river water samples. They occur naturally in small amounts in essential oils. These compounds are manufactured in large quantities to be employed as fragrances in personal care products and/or as food flavors. Camphor (no. 50) is used as plasticizer, and is an ingredient of medical formulations and of mothballs. HHCB and AHTN (nos. 64, 65) were found in all river water samples at concentrations of up to 15,000 ng L−1 (Table 2). The two compounds are cheap synthetic substitutes of the natural musk flavor and are ingredients of personal care products and washing powders. The usage of these compounds has decreased in some countries, because there is concern about the high bioaccumulation potential and persistence in the environment (e.g. Dsikowitzky et al., 2002). Interestingly, Ricking et al. (2003) showed that the HHCB/AHTN ratios in surface water samples and sewage treatment plant effluent samples from Europe and Canada ranged between 0.8 and 5.3, whereas we determined a ratio of 10 or higher in the water samples from Jakarta (Table 2). This is possibly due to a different formulation of Indonesian personal care products, with a higher proportion of HHCB. The higher photodegradation rate of AHTN as compared to HHCB (Buerge et al., 2003) can also explain the high HHCB/AHTN ratios. Previous studies reported HHCB and AHTN concentrations in surface waters ranging between 64–12,470 ng L−1 and 52–6780 ng L−1, and median concentrations of 160 ng L−1 and 88 ng L−1, respectively, as reviewed by Brausch and Rand (2011). The HHCB concentrations we determined in Jakarta surface waters (Table 2) are very high, as compared to the median level calculated from earlier studies. Surfactants are constituents of a variety of industrial and domestic products such as cleaning agents, degreasers and detergents. These substances are key components of washing powders and liquids, dishwashing products, and multipurpose cleaners used in households. A number of surfactant residues were found in this study including nonylphenol technical mixture (no. 32), octylphenolethoxycarboxylates (nos. 70, 71) and linear alkylbenzenesulfonates (LAS) (no. 43) (Table 2). The technical nonylphenol mixture is utilized for the industrial manufacturing of the common surfactants nonylphenolpolyethoxylates. Nonylphenolethoxylates are degraded to a variety of products including nonylphenols, as demonstrated in many studies (e.g. Ahel et al., 1994). Octylphenolethoxycarboxylates are degradation products of octylphenolethoxylates, which are also in use as surfactants (e.g. Tubau et al., 2010). LAS are worldwide among the most applied surfactants since the early 1960s. Nonylphenols and LAS were not found at the easternmost stations located in a rural area (R11–R13), but at all stations in the central part of Jakarta (Table 2, Fig. 1). This suggests that the compounds mainly originate from the usage of cleaning products and detergents in households. Aminoacetophenone (no. 23) was found in nearly all water samples (Table 2). It is known as an intermediate product resulting from the aerobic degradation of nonlyphenol (Yuan et al., 2004). However, the compound is also used as educt for industrial chemical syntheses.

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3.1.2.4. Pharmaceutical drugs and stimulants. Pharmaceutical drugs and stimulants are intensively used by humans and these compounds are frequently detected constituents of municipal wastewaters. The number of studies on pharmaceutical drugs and stimulants as water contaminants has increased during the last decade, with the majority of studies focusing on wastewater analyses (Mompelat et al., 2009). The existing studies were mainly carried out in Europe, the Unites States, Australia, China, Japan and Korea. There is a lack of data about the contamination of surface waters with pharmaceuticals and stimulants in developing and emerging countries. Caffeine (no. 55) was present in 17 of 18 water samples from Jakarta at concentrations of up to 8900 ng L−1 (Table 2). These concentrations are comparable with the highest caffeine concentrations that were reported from US streams (6000 ng L-1) and from European streams (40,000 ng L− 1) (Kolpin et al., 2002; Loos et al., 2009). Nicotine (no. 56) exhibited lower concentrations of up to 1500 ng L− 1, and was only found at stations R1 to R7 (Table 2, Fig. 1). Besides its occurrence in municipal wastewaters, nicotine was also reported as characteristic compound in leakage waters of municipal waste disposal sites (Schwarzbauer et al., 2002). Four pharmaceutical drugs were detected in this study: propyphenazone (no. 57), diclofenac (no. 58), ibuprofen (no. 59) and mefenamic acid (no. 60). They are in use as pain relievers and antiinflammatories. Previous studies published between 2006 and 2009 revealed the following concentration ranges of these compounds in river water samples from Europe, the Unites States, Asia and Australia: 1.1 to 82 ng L− 1 diclofenac, 14 to 360 ng L−1 ibuprofen and b 0.1 to 169 ng L−1 mefenamic acid, as reviewed by Pal et al. (2010). In surface water from Berlin City, Germany, the highest propyphenazone concentration was 110 ng L−1 (Zuehlke et al., 2004). Diclofenac concentrations in our study ranged between b10 and 100 ng L− 1 and those of propyphenazone between 10 and 50 ng L−1 (Table 2), which is comparable to these earlier studies. In contrast, ibuprofen concentrations in Jakarta river water were higher and ranged between 30 and 1700 ng L−1 (Table 2). As yet, a maximum concentration of 1000 ng L − 1 ibuprofen was reported from US streams (Mompelat et al., 2009). Among the pharmaceutical drugs, mefenamic acid was present in the highest concentrations in Jakarta surface waters (80 to 3700 ng L− 1, Table 2). At five stations, more than 1600 ng L− 1 mefenamic acid were found. This is one magnitude higher than the maximum values (up to 169 ng L − 1 ) reported in many previous studies conducted in Europe, the United States, Australia and Asia (Al-Odaini et al., 2010; Mompelat et al., 2009; Pal et al., 2010; Sim et al., 2010; Wang et al., 2010). Noteworthy, the marketing of mefenamic acid (trade names “Ponstel”, “Ponstan”) is not licensed in all countries, for example it is not sold in Germany. Considering the high concentration levels in river water, mefenamic acid and ibuprofen are very frequently used pharmaceutical drugs in the study area.

3.1.2.5. Pesticides. Three pesticides were identified in the river water samples: the organophosphate insecticide chlorpyrifos (no. 61), and the carbamate insecticides carbofuran (no. 62) and isoprocarb (no. 63) (Table 2). In contrast to chlorpyrifos, carbofuran and isoprocarb are not approved for usage in agriculture in the European Union (EU pesticides database, 2015). However, chlorpyrifos, carbofuran and isoprocarb are very commonly used pesticides for the culturing of paddy rice in tropical zones (e.g. Rola and Pingali, 1993). Chlorpyrifos and isoprocarb occurred only occasionally in the samples and at low concentration levels (b10 to 20 ng L−1). They are therefore of little account in our study area. Carbofuran also only occurred in 3 of 18 samples, but at concentrations of up to 1600 ng L− 1. Thus, this compound could be a relevant water contaminant in Indonesian rural areas.


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Fig. 2. Concentrations (ng L−1) of the synthetic musk fragrance HHCB (1,3,4,6,7,8-Hexahydro-4,6,6,7,8,8-hexamethylcyclopenta[g]-2-benzopyrane) in water samples taken in October 2012 from rivers flowing through the megacity Jakarta, Indonesia, and from Jakarta Bay, Java Sea.

3.2. Comparison of the contaminant spectrum in Jakarta river water with that of surface waters of other large urban areas Most of the organic contaminants identified in Jakarta river water with specific applications are used in households (Section 3.1.2). The plasticizers, flame retardants, antioxidants, ingredients of personal care products, disinfectants, surfactant residues, pharmaceutical drugs and stimulants, which we detected in our study, were previously reported as constituents of municipal wastewaters (Dsikowitzky et al., 2004a; Loraine and Pettigrove, 2006; Bueno et al., 2012; Rodil et al., 2012). They are, consequently, relevant and known contaminants of urban surface waters. The contaminant spectrum in Jakarta river water is, therefore, not significantly different from that of other large urban areas. Pharmaceuticals, ingredients of personal care products,

plasticizers, surfactants and flame retardants were reported as water contaminants of the urban water cycles of the megacities Beijing, Shanghai and Mexico City (Heeb et al., 2012; Félix–Cañedo et al., 2013; Pal et al., 2014). Specific for the study area is the occurrence of mefenamic acid, a pharmaceutical that is not licensed in all countries. The industrial production and usage of some of the detected compounds are decreasing in the European Union, because they were listed as priority hazardous substances (Annex II of Directive 2008/105/EC) and/or listed as substances of very high concern (SVHCs) by the European Chemical Agency. This applies to nonylphenol and TCEP. It can be expected that the concentrations of these compounds in urban surface waters of the European Union is declining, but they will remain relevant substances in Indonesian surface waters unless they fall under future environmental legislation.

Fig. 3. Concentrations (ng L−1) of the flame retardant TCEP (tris-2-chloroethyl phosphate) in water samples taken in October 2012 from rivers flowing through the megacity Jakarta, Indonesia, and from Jakarta Bay, Java Sea.



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Fig. 4. Concentrations (ng L−1) of the stimulant caffeine (1,3,7-trimethylpurine-2,6-dione) in water samples taken in October 2012 from rivers flowing through the megacity Jakarta, Indonesia, and from Jakarta Bay, Java Sea.

A further specific feature were the exceptionally high concentrations of municipal contaminants in Jakarta river water as compared to other studies (see Section 3.1.2). Chloroxylenol, oxybenzone, DEET, TCEP, caffeine, nicotine, ibuprofen, mefenamic acid, HHCB and AHTN concentrations exceeded 1 μg L−1 (Table 2). The high DEET concentrations were previously discussed in detail in Dsikowitzky et al. (2014a). They are by far the highest concentrations of this compound that were detected in surface waters worldwide. This was attributed to the high usage rate of DEET by more than 10 million inhabitants of Jakarta City and consequently the occurrence of high amounts of this compound in untreated or partially treated household wastewaters, which are discharged into the relatively small river systems in Jakarta City. This explanation also applies to the other above-mentioned contaminants from municipal wastewaters.

3.3. Spatial distribution of selected contaminants in Jakarta coastal waters Section 3.2 highlighted the high concentration levels of some contaminants originating from municipal wastewaters in Jakarta river water as compared to other river systems. In this section, we assess the spatial distribution of some of these source-specific compounds in the Jakarta City district as well as in the coastal ecosystem impacted by the riverine discharges from Jakarta, the Jakarta Bay. This is done to identify pollution hotspots in the city and to assess the relevance of the riverine pollutant discharges for the water quality of the bay. We selected the synthetic fragrance HHCB, the flame retardant TCEP and the stimulant caffeine for this assessment. All three compounds occurred in high concentrations in nearly all river water samples from

Fig. 5. Source-specific compounds from municipal wastewaters that were detected in Jakarta river water samples and the concentration ranges of the quantified compounds.


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Jakarta. It was demonstrated that these three organic contaminants are useful as markers to track municipal wastewater inputs in aquatic systems (Standley et al., 2000; Dsikowitzky et al., 2004b), due to their i) source specificity, (ii) massive usage, and (iii) environmental persistence, according to the criteria developed by Takada and Eganhouse (1998). The spatial distribution of the pharmaceuticals ibuprofen and mefenamic acid was not considered, although they are source-specific and occurred in high concentrations in the river water samples. Both pharmaceuticals only occurred in low concentrations in seawater (mostly less than 30 ng L−1), and were not present in all samples (ibuprofen: 17 of 22 seawater samples, mefenamic acid: 5 of 22 seawater samples). Figs. 2, 3 and 4 show the spatial distribution of HHCB, TCEP and caffeine in the study area (location of sampling stations see Fig. 1). The highest concentrations of all compounds were found at the river stations situated within the Jakarta city boundaries, especially at the river mouths. The high concentrations in the city reflect the usage of high amounts of all three compounds in the urban households. Lower concentrations were found outside Jakarta, at the two easternmost river stations (R12 and R13) located in rural areas. However, station R11 east of the city (Fig. 1) exhibited contaminant concentrations that were comparable to the values inside the Jakarta City boundaries. This river is impacted by municipal discharges from the urban and industrial area Bekasi located in the southeast of Jakarta. The spatial distribution of HHCB, TCEP and caffeine in the Jakarta Bay mirrors the riverine inputs, with higher concentrations in the western and central part of the bay and lower values in the eastern part. This spatial distribution is very similar to that of DEET that was earlier reported in Dsikowitzky et al. (2014a). HHCB, TCEP and caffeine were detectable at nearly all stations in the Jakarta Bay, even at stations in the central part, which is ~10 km seaward. This indicates that the contaminants are transported in the aqueous phase over a distance of several kilometers. The ubiquitous occurrence and the relative high concentration levels in the seawater of up to 0.1 μg L−1 show that HHCB, TCEP and caffeine besides DEET are highly relevant organic contaminants in the studied coastal ecosystem. In contrast, the municipal markers ibuprofen and mefenamic acid were less frequently detected and occurred in lower concentrations. Overall, the widespread distribution of appropriate municipal marker compounds in the bay reveals that the water quality of the whole Jakarta Bay ecosystem is affected by riverine inputs of municipal wastewaters.

4. Summary and conclusions Applying non-target screening analyses, we identified a broad spectrum of volatile, non-polar to semi-polar organic contaminants in river water samples from Jakarta City. Most of the identified compounds are used in households. Only a few compounds were found which could unequivocally be attributed to an application in agriculture or to the usage for industrial manufacturing. Consequently, if regarding organic contaminants in surface waters of Jakarta City, municipal wastewater discharges are most relevant for the water quality. In some cases, as for the compounds used for paper manufacturing, as well as for plasticizers, flame retardants and technical antioxidants, no sharp discrimination between municipal and industrial sources is possible, as these compounds may stem from both sources. We conclude that some plasticizers and contaminants related to paper manufacturing (e.g. bisphenol A) may also originate from the leaching of solid waste (leaching of dumped waste-papers and plastic materials). In terms of concentrations and detection frequency, the flame retardant TCEP, the disinfectant chloroxylenol, the personal care product ingredients oxybenzone, DEET, HHCB and AHTN, the stimulants caffeine and nicotine, and the pain reliever ibuprofen and mefenamic acid were the most important source-specific compounds from municipal sources, as summarized in Fig. 5. These compounds occurred in exceptionally high concentrations as compared to studies of other river systems.

The spectrum of contaminants from municipal sources as detected in Jakarta is similar to that reported from municipal wastewaters of other regions. Specific for the study area was only the occurrence of mefenamic acid, a pharmaceutical drug that is not licensed in all countries. We conclude that the globalized industrial production and marketing is leading to the consumption of the same types of pharmaceuticals and industrial products in urban areas across the globe. The most relevant compounds originating from municipal wastewaters identified in Jakarta river water are therefore also relevant for the contamination of other tropical coastal ecosystems that are polluted by riverine inputs from urban areas. The flame retardant TCEP, the synthetic musk substitute HHCB and the stimulant caffeine were used as markers to trace the riverine discharges of municipal wastewaters in the Jakarta Bay. They occurred widespread and in relative high concentration levels of up to 0.1 μg L−1 in the seawater. These compounds could also be used as appropriate markers to trace municipal wastewater discharges in other tropical coastal ecosystems. This application is useful to evaluate if wastewater inputs from land-based sources are influencing tropical coastal habitats which are sensitive to changing water quality, like e.g. coral reefs. Our results indicate that the contamination has implications for the studied ecosystem. The occurrence of molecular putridity indicators revealed anoxic conditions in the water column. Concurrent effects of the contamination on macrobenthic invertebrate and fish species should be addressed in future studies. Acknowledgments This study is part of the Indonesian–German SPICE Program (Science for the Protection of Indonesian Coastal Marine Ecosystems), funded by the German Federal Ministry of Education and Research (BMBF, grant no. 03F0641E) and supported institutionally by the Indonesian Research and Development Center for Marine and Fisheries Product Processing and Biotechnology and the Indonesian Research Center for Fisheries Management and Conservation. References Ahel, M., Giger, W., Schaffner, C., 1994. Behaviour of alkylphenol polyethoxylate surfactants in the aquatic environment—II. Occurrence and transformation in rivers. Water Res. 28 (5), 1143–1152. Al-Odaini, N.A., Zakaria, M.P., Yaziz, M.I., Surif, S., 2010. Multi-residue analytical method for human pharmaceuticals and synthetic hormones in river water and sewage effluents by solid-phase extraction and liquid chromatography–tandem mass spectrometry. J. Chromatogr. A 1217 (44), 6791–6806. Barker, H.A., 1981. Amino acid degradation by anaerobic bacteria. Annu. Rev. Biochem. 50 (1), 23–40. Botalova, O., Schwarzbauer, J., Frauenrath, T., Dsikowitzky, L., 2009. Identification and chemical characterization of specific organic constituents of petrochemical effluents. Water Res. 43 (15), 3797–3812. Brausch, J.M., Rand, G.M., 2011. A review of personal care products in the aquatic environment: environmental concentrations and toxicity. Chemosphere 82 (11), 1518–1532. Bueno, M.M., Gomez, M.J., Herrera, S., Hernando, M.D., Agüera, A., Fernández-Alba, A.R., 2012. Occurrence and persistence of organic emerging contaminants and priority pollutants in five sewage treatment plants of Spain: two years pilot survey monitoring. Environ. Pollut. 164, 267–273. Buerge, I.J., Buser, H.R., Müller, M.D., Poiger, T., 2003. Behavior of the polycyclic musks HHCB and AHTN in lakes, two potential anthropogenic markers for domestic wastewater in surface waters. Environ. Sci. Technol. 37 (24), 5636–5644. Dsikowitzky, L., Schwarzbauer, J., Littke, R., 2002. Distribution of polycyclic musks in water and particulate matter of the Lippe River (Germany). Org. Geochem. 33 (12), 1747–1758. Dsikowitzky, L., Schwarzbauer, J., Kronimus, A., Littke, R., 2004a. The anthropogenic contribution to the organic load of the Lippe River (Germany). Part I: qualitative characterisation of low-molecular weight organic compounds. Chemosphere 57 (10), 1275–1288. Dsikowitzky, L., Schwarzbauer, J., Littke, R., 2004b. The anthropogenic contribution to the organic load of the Lippe River (Germany). Part II: quantification of specific organic contaminants. Chemosphere 57 (10), 1289–1300. Dsikowitzky, L., Dwiyitno, Heruwati, E., Ariyani, F., Irianto, H.E., Schwarzbauer, J., 2014a. Exceptionally high concentrations of the insect repellent N, N-diethyl-m-toluamide (DEET) in surface waters from Jakarta, Indonesia. Environ. Chem. Lett. 12 (3), 407–411.


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