Environ Sci Pollut Res

DOI 10.1007/s11356-017-0164-2

RESEARCH ARTICLE

Complex organic pollutant mixtures originating from industrial

and municipal emissions in surface waters of the megacity
Jakarta—an example of a water pollution problem in emerging
economies
Larissa Dsikowitzky 1 & Lukas Hagemann 1 & Dwiyitno 1,2 & Farida Ariyani 2 &
Hari Eko Irianto 2 & Jan Schwarzbauer 1

Received: 6 March 2017 / Accepted: 7 September 2017

# Springer-Verlag GmbH Germany 2017

Abstract During the last decades, the global industrial pro-
duction partly shifted from industrialized nations to emerging
and developing countries. In these upcoming economies, the
newly developed industrial centers are generally located in
densely populated areas, resulting in the discharge of often
only partially treated industrial and municipal wastewaters
into the surface waters. There is a huge gap of knowledge
about the composition of the complex organic pollutant mix-
tures occurring in such heavily impacted areas. Therefore, we
applied a non-target screening to comprehensively assess river
pollution in a large industrial area located in the megacity
Jakarta. More than 100 structurally diverse organic contami-
nants were identified, some of which were reported here for
the first time as environmental contaminants. The concentra-
tions of paper manufacturing chemicals in river water—for
example, of the endocrine-disrupting compound bisphenol A
(50–8000 ng L−1)—were as high as in pure untreated paper
industry wastewaters. The non-target screening approach is
the adequate tool for the identification of water contaminants
Responsible editor: Ester Heath
Electronic supplementary material The online version of this article
(https://doi.org/10.1007/s11356-017-0164-2) contains supplementary
material, which is available to authorized users.
* Larissa Dsikowitzky
loga-pub@emr.rwth-aachen.de
1
Institute of Geology and Geochemistry of Petroleum and Coal,
RWTH Aachen University, Lochnerstrasse 4-20,
52056 Aachen, Germany
2
Research and Development Center for Marine and Fisheries Product
Processing and Biotechnology (BBP4BKP), Ministry of Marine
Affairs and Fisheries, Jl. K.S. Tubun, Petamburan VI, Central
Jakarta 10260, Indonesia
in the new global centers of industrial manufacturing—as the
first crucial step towards the evaluation of as yet unrecognized
environmental risks.
Keywords GC/MS non-target screening . Industrial
wastewaters . Tropical rivers . Organic pollutants
Introduction
The world’s industrial manufacturing output and gross domes-
tic product constantly increased since the 1960s, and in the
early twenty-first century, more industrial goods than ever
before were produced. The locations of the most important
countries for industrial manufacturing broadened. While in
1990, only 24% of the manufacturing took place outside the
more economically developed countries, in 2010, this propor-
tion reached 41%. The list of the Bmanufacturing-capable
countries^ is now much longer and includes also emerging
and developing economies (Marsh 2012). This global shift
of the industrial manufacturing centers to emerging and devel-
oping countries is associated with environmental risks, which
have as yet not adequately been addressed by scientific
investigations.
It is striking that nearly all previous studies about the oc-
currence of industrial organic contaminants in surface waters
were conducted in the more industrialized nations of the
northern hemisphere. Two early publications were ground-
breaking in this respect, as they showed the complex compo-
sition and high concentrations of organic contaminants in in-
dustrial wastewaters and some basic principles of their fate in
the environment (Jungclaus et al. 1978; Lopez-Avila and Hites
1980). A chemical manufacturing unit producing, e.g., pesti-
cides, optical brighteners, and surfactants, in the USA was

investigated. The chemical composition of the river water
reflected that of the discharged wastewaters from the facility,
and the aqueous concentrations followed the rule of simple
dilution. The compounds with high KO/W values were found
to be associated with the riverine particulate matter and were
transported over long distances. Some of the compounds were
observed to be evaporated or degraded, for example, phenols
were oxidized to quinones. Along the river stretch impacted
by the industrial discharges, a lack of biota was observed
(Jungclaus et al. 1978; Lopez-Avila and Hites 1980). A recent
review about industrial organic contaminants emphasized the
heterogenic composition of industrial wastewaters, even from
the same industry types. As yet, only limited attempts were
made to address this problem and to trace the broad spectrum
of structurally diverse industrial organic contaminants in the
environment (Dsikowitzky and Schwarzbauer 2013).
Although some industrial organic contaminants might be sta-
ble in the hydrosphere and are toxicologically relevant, there
is a huge gap of knowledge about the occurrence and fate of
these compounds in surface waters. This poses so far unrec-
ognized risks to the safety of water and fishery resources, to
aquatic diversity, and, ultimately, to human health. This ap-
plies in particular to the industrial emissions in emerging and
developing countries, from which scientific investigations on
the composition of organic contaminants originating from in-
dustrial wastewaters are missing. In these countries, the sur-
face waters may be contaminated by complex mixtures of
organic pollutants from industrial and municipal emissions,
due to insufficient source control and a lack of adequate
wastewater treatment facilities.
The aim of this study was therefore a comprehensive survey
of river contamination in an industrial manufacturing center
located in a densely populated area of an emerging country. A
gas chromatography-mass spectrometry (GC/MS) non-target
screening was applied, which allows for the detection of well-
known organic pollutants and of emerging contaminants, for
which the risk potential for the environment has not been in-
vestigated yet. Previous studies demonstrated that the non-
target screening approach is an effective tool for the identifica-
tion of a wide range of organic pollutants in aquatic systems
(e.g., Franke et al. 1995; Grigoriadou and Schwarzbauer 2011).
The compound spectrum that is detectable by a GC/MS
non-target screening as applied in this study is restricted to
volatile, low-molecular-weight non-polar to semi-polar organ-
ic substances. The detectable compound spectrum could be
further extended by applying high-resolution mass spectrom-
etry combined with gas chromatography and liquid chroma-
tography (e.g., Hernández et al. 2014, 2015). Moreover, a
combination of the non-target screening approach with bioas-
say investigations would have been of high value as it reveals
additional information on the toxicity profiles of the sample
set (e.g., Brack et al. 2005; Scheurell et al. 2007). However,
these approaches were beyond the scope of this work.
Environ Sci Pollut Res
As study site, the main industrial manufacturing center of
Indonesia was selected. Indonesia is the largest emerging
economy in Southeast Asia. The share of Indonesia in the
global manufacturing output increased in the period 1990–
2010 from 0.7 to 1.8% (Marsh 2012). This recent rapid eco-
nomic growth induced a migration towards the cities and the
settling of large-scale industrial production facilities, a trend
also visible in other emerging and developing economies. The
main Indonesian industrial manufacturing center is located in
the densely populated Greater Jakarta metropolitan area. In the
numerous industrial facilities located here, a wide spectrum of
modern consumer goods is produced, some of which by
worldwide operating transnational companies, as in other
large industrial centers across the globe. Industrial and munic-
ipal wastewaters in this area are discharged after little treat-
ment into a small river/canal system that is connected to the
coast (Fig. 1).
In detail, the following objectives were pursued: (i) identi-
fication of a wide range of organic contaminants in river water
and sediments applying a non-target screening, (ii) source
apportionment of the identified compounds to disentangle
the contributions from different industrial branches and the
urban emissions to the river contamination, (iii) assessment
of the spatial distribution of the river contamination and the
impact of the emissions on the water quality, and (iv) identi-
fication of source-specific organic contaminants which could
be useful as markers to trace similar emissions in other
regions.
Experimental
Study area and sampling
The biggest Indonesian industrial manufacturing center is lo-
cated in Bekasi Regency and Bekasi City in the Greater
Jakarta metropolitan area and has a population of ~ 5.7 mio
inhabitants (BPS 2014). The industrial branches include in
detail steel manufacturing, glass manufacturing, automotive
industry, electrical industry, computer manufacturing, chemi-
cal industry (polymer synthesis), personal care product
manufacturing, toy industry, and paper industry.
The industrial wastewaters of the facilities are discharged
into a system of small streams/canals that flow into the Jakarta
Bay (Fig. 1). These streams/canals are crossed by the West
Tarum Canal, an artificial channel of 70-km length designed
for irrigation and to serve the largest part of the public water
supply of Jakarta City (Fares and Ikhwan 2001). This canal
originates at the Curug weir, downstream the Jatiluhur
Reservoir, which is fed by the Citarum River (Fig. 1).
The study area has a tropical monsoon climate. The north-
west monsoon (October–March) brings rainfall, whereas the
southeast monsoon (April–September) coincides with the dry
Environ Sci Pollut Res
Jakarta Bay
Java Sea
JB2
R7
JB1 Citarum River
Bekasi
River
Cikarang
River
Jakarta City
R6
West Tarum
Canal R5 R4
7 km N R3
R2
Ciliwung River
Fig. 1 Schematic sketch of the working area in West Java Province,
Indonesia, and the positions of the water and surface sediment sampling
stations. The location of the industrial area, from which the river system
season. During the rainy season, sometimes exceptionally
high river runoff leads to a partial flooding of the urban areas.
Seven stations at the river/channel system of the industrial
area were sampled. Water samples were assessed, because the
surface waters in the area are used for irrigation and the public
water supply. Sediment samples were analyzed because lipo-
philic compounds that are preferentially attached to particulate
matter have a strong bioaccumulation tendency. Water and
surface sediment samples were taken at three stations up-
stream the industrial area at the West Tarum Canal (R1–R3),
where some smaller industrial facilities are located. Three sta-
tions located directly in the industrial area were sampled (R4–
R6), as well as one downstream station (R7). Additionally,
samples were taken at two stations in the Jakarta Bay located
in the vicinity of the river entry into the bay (JB1 and JB2) (see
Fig. 1). Sampling was carried out on May 18–19, 2013 (be-
ginning of the dry season), and on October 19–21, 2013 (be-
ginning of the rainy season).
The grab water samples were scooped up from below the
water surface from midstream by using a pre-cleaned metal
bucket. The samples were bottled without air bubbles in pre-
cleaned aluminum flasks. Surface sediment samples were tak-
en with a stainless steel Van Veen grab. The top layer of the
sampled sediment (0–5 cm) was filled in pre-cleaned metal
cans. Water samples were stored dark at 4 °C and sediment
samples at − 20 °C in Jakarta and transported within 3 days to
Germany. During transport, the samples were stored in cool
Indonesia
Curug weir
Industrial area
Tapping point for public water
supply of Jakarta City
R1
Curug weir Jakarta City center boundaries
Jatiluhur
Reservoir
receives untreated or partially treated wastewaters, is marked. It is located
in the Greater Jakarta metropolitan area
boxes and cooled with ice packs. At RWTH Aachen
University, water samples were stored dark at 4 °C and proc-
essed within 3 weeks. Sediment samples were stored dark at
– 20 °C until analysis. The cooling of the samples minimizes
degradation processes. Nevertheless, not fully stable pollut-
ants might undergo degradation to a small extent. The quan-
titative results, therefore, have to be regarded as minimum
values.
Chemicals, blanks, and recovery experiments
In order to minimize sample contamination, only glass, metal,
and PTFE equipment were used. The equipment was rinsed
with high-purity acetone and n-hexane before usage. All sol-
vents were purchased from Merck, Germany, and distilled
over a 0.5-m packed column (reflux ratio approximately
1:25). Their purity was tested by gas chromatographic analy-
ses. Anhydrous granulated Na2SO4 and hydrochloric acid
needed for the analytical procedures were cleaned with pure
solvents before usage. Hydrochloric acid was cleaned sequen-
tially by shaking 500 mL HCl for 5 min with 50 mL n-hexane
in a separatory funnel. Thereafter, the two phases were sepa-
rated, and the procedure was repeated with 50 mL dichloro-
methane. Na2SO4 was cleaned by soxhlet extraction with n-
hexane and acetone. Blank analyses (n = 2) were run to deter-
mine background concentrations of the investigated

compounds. They revealed that none of the identified com-
pounds were detected in the blank.
Reference materials of the identified compounds were pur-
chased from Sigma-Aldrich, Germany. Recoveries (n = 3) of
the water sample extraction method were determined by spik-
ing 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 de-
scribed in the BWater sample extraction^ section. The exper-
imental results are presented in the supplementary material
(Table S1) 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 S1). This
result would have been better with solvent extraction from an
alkalized aqueous matrix. Nevertheless, the quantitative data
of caffeine were included because of the good reproducibility
of the quantitative results.
Water sample extraction
Prior to extraction, the samples were filtered through pre-
cleaned MNGF-6 glass fiber filters (Macherey-Nagel,
Düren, Germany, pore width 0.45 μm). After filtration, 1 L
aliquots of river water samples and 2 L aliquots of seawater
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 (first fraction), dichloromethane (second
fraction), and dichloromethane after acidification to pH 2
(third fraction) were used for the sequential extraction in a
separatory funnel. Acidic compounds in the third fractions
were methylated by addition of a methanolic diazomethane
solution. The diazomethane solution was prepared as follows:
Approximately 500 mg methylnitronitrosoguanidine (CAS
No. 70-25-7) was placed in the inner glass reaction chamber
of an Aldrich® diazomethane generator apparatus, and 2 mL
methanol was filled in the outer chamber. The apparatus was
cooled with liquid nitrogen, and 40% NaOH solution was
added dropwise to the methylnitronitrosoguanidine. The third
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 from the first
sampling campaign were spiked with the surrogate standard
solution A containing d34-hexadecane (6.0 ng μL−1) and
decafluorobenzophenone (7.0 ng μL−1). Two hundred micro-
liters of a surrogate standard containing 4-fluoroacetophenone
(14.4 ng μL−1) was added to the third fractions. The first two
fractions of the water samples from the second sampling cam-
paign were spiked with 50 μL of the newly developed surro-
gate standard solution D containing d 34 -hexadecane
(6.0 ng μL−1) and d10-benzophenone (6.3 ng μL−1). Two hun-
dred microliters of this standard was added to the third
Environ Sci Pollut Res
fractions. Prior to GC/MS analyses, all fractions were concen-
trated to final volumes of 50 μL (first two fractions) and
200 μL (third fractions).
Sediment sample extraction
Aliquots of approximately 20-g fresh wet sediment were ex-
tracted according to the method described in Schwarzbauer
et al. (2000) with a high-speed dispersion tool (Ultra-Turrax
T25 Basic, IKA-Werke, Staufen, Germany) using mixtures of
acetone and n-hexane. After concentration by rotary evapora-
tion, the extract was dried with anhydrous granulated Na2SO4,
and elemental sulfur was removed by addition of activated
copper powder. Thereafter, the obtained raw extract was sep-
arated into six fractions by column chromatography with ac-
tivated silica gel using mixtures of n-pentane, dichlorometh-
ane, and methanol. For the column chromatography, 8-mL
glass microcolumns (J.T. Baker, Avantor Performance
Materials B.V., Netherlands) and 2-g silica gel for flash chro-
matography (J.T. Baker, Avantor Performance Materials B.V.,
Netherlands) were used. Fractions 1–5 were spiked with
50 μL of the surrogate standard solution A. Acidic com-
pounds in the sixth fractions were treated as described in the
BWater sample extraction^ section, and 200 μL of the standard
solution D was added. Prior to analysis with GC/MS, fractions
1–5 were concentrated to final volumes of 50 μL and the sixth
fractions to 200 μL.
Gas chromatography-mass spectrometry
GC/MS analyses of water sample extracts were performed as
single measurements with a quadrupole ThermoQuest Trace
MS mass spectrometer linked to a ThermoQuest Trace GC
(ThermoQuest, Germany). 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 as follows: 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 oper-
ated in electron impact ionization mode (70 eV), source tem-
perature 200 °C, scanning from 35 to 700 amu at a rate of
2.5 scans s−1. GC/MS analyses of sediment extracts were per-
formed as single measurements under the same conditions as
described above on a quadrupole Finnigan Trace MS (Thermo
Finnigan, Germany) linked to HRGC-5160 Mega Series
(Carlo Erba, Italy) gas chromatograph. Carrier gas (He) veloc-
ity was 40 cm s−1. A ZB-Multiresidue-2 column was used for
the analysis of the sediment extracts (30 m × 0.25-mm
ID × 0.25-μm film thickness).
Environ Sci Pollut Res
Compound identification and quantification
Identification of the individual compounds was based on com-
parison of EI+ mass spectra with those of databases (NIST,
Wiley) and was verified with mass spectra of purchased ref-
erence compounds considering also gas chromatographic re-
tention times and elution orders. 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
the supplementary material (Table S1). GC/MS response fac-
tors for the quantified compounds were determined from four-
point linear regression functions based on calibration mea-
surements with different compound concentrations (4–
40 ng μL−1, injection of 1 μL). 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 sur-
rogate standard was used. For GC/MS analyses of the refer-
ence compounds, the limit of quantitation was ~0.1 ng (signal
to noise ratio 10:1). In the water samples, concentrations of
10 ng L−1 resulted in similar signal to noise ratios due to
matrix effects. Therefore, this value was defined as limits of
quantitation for this study. All details of the identification and
quantification procedure are described in Dsikowitzky et al.
(2015).
Results and discussion
Identified organic contaminants and their apportionment
to individual emission sources
The GC/MS non-target screening approach allowed for the
identification of 51 organic contaminants in the surface sedi-
ment samples and of 93 organic contaminants in the water
samples. The compounds were listed in Tables S2 and S3 in
the supplementary material of this article and were arranged
according to principle substance classes or according to their
application. The compounds identified in sediment (s)
(Table S2) and/or in water (w) (Table S3) were numbered
and in the following, we will refer to these compound
numbers.
The spectrum of contaminants identified in the aqueous
phase was different from that in the surface sediments.
Whereas most contaminants found in the sediment samples
were polycyclic aromatic compounds (PACs) (Table S2), only
eight PACs were found in the water samples. Many water
contaminants belonged to the substance classes of esters, al-
dehydes, and ketones (Table S3). Detailed information about
the usage of the identified compounds was compiled in the
supplementary material (Table S4). The following discussion
is focused on characteristic compounds representing the
different sources of organic contamination. This was done to
identify and to disentangle the contributions from different
industrial branches as well as from urban and possible further
sources to the contamination of the studied river.
Contaminants that have different applications and could there-
fore not be assigned unambiguously to a specific pollution
source were tagged with BN^ (non-specific origin) in
Table S4 and are discussed in the BOrganic contaminants not
assignable to a specific pollution source^ section.
Contaminants that were assigned to municipal sewage inputs
(tagged with BM^), which originate from street runoff (tagged
with BSR^), from an application in agriculture (tagged with
BA^), or which were assigned to industrial wastewater inputs
(tagged with BI^ in Table S4) are discussed in the BOrganic
contaminants originating from urban emissions, BOrganic
contaminants originating from agriculture,^ and BOrganic
contaminants originating from industrial emissions^ sections.
Organic contaminants not assignable to a specific pollution
source
Most compounds identified in the sediments (s1–s25) and
eight compounds identified in the water samples (w1–w8)
were PACs, originating from fossil fuels or from the incom-
plete combustion of organic matter. Due to their different or-
igin, a clear attribution to individual emission sources is not
feasible. Many further identified compounds are used for dif-
ferent purposes or are degradation products of unspecific com-
pounds and can therefore originate from both industrial and
municipal wastewater inputs. This applies, for example, to the
identified plasticizers and flame retardants (w15, w17, w20–
21, w23, w54–57, w59–60). These are constituents of prod-
ucts intensively used in households. However, the presence of
plasticizers and flame retardants in industrial wastewaters was
also reported (e.g., Castillo et al. 1997). In this study, where
massive inputs of industrial wastewaters and municipal sew-
age in combination with the studied river are expected, the
flame retardants and plasticizers were treated as compounds
with ambiguous origin.
Nonylphenols (w46, s39) are employed for the manufactur-
ing of the detergents nonylphenolethoxylates that have an in-
dustrial application (e.g., Soares et al. 2008). In addition,
nonylphenols are, like octylphenolethoxycarboxylates (w91–
92), degradation products of detergents used in households. In
this study, these detergent residues were therefore numbered
among the contaminants without specific input source.
Further identified organic compounds are used by humans
but are also known to occur in natural organic matter. They
could either originate from an anthropogenic and/or a biogenic
source. This applies for example to trimethoxybenzoic acid
(w12), phenylacetic acid (w13), benzoic acid (w14), benzal-
dehyde (s33), and hexathiepane (w61). Indole (w52) and

skatol (w53) are molecular indicators for anoxic conditions in
the water column (Table S4).
Another set of compounds identified in the river water is
educts for industrial polymer manufacturing. The
photoinitiators methyl-2-(benzoyl)benzoate (w22),
methylbenzophenone (w25), benzophenone (w26), Irgacure
184 (w29), Michler’s ketone (w31), and Irgacure 907 (w63)
that were identified in the river water samples are constituents
of UV-curable resins and/or food contact materials. These
photoinitiators were detected in household dust and in sewage
sludge from wastewater treatment plants all over China (Liu
et al. 2016). Despite the municipal sources, industrial facilities
manufacturing the commercial products containing these
chemicals are a probable further source, which has to be con-
firmed in future studies. Due to the intensive usage of
photoinitiators and their predicted toxic properties (Liu et al.
2016), photoinitiators could be a new relevant class of emerg-
ing contaminants in aquatic systems.
Since all the aforementioned compounds are not clearly
attributable to one major emission source, in this study, they
were classified as non-specific and tagged with BN^ in
Table S4.
Organic contaminants originating from urban emissions
Contaminants assigned to municipal sewage inputs (tagged
with BM^ in Table S4) had to fulfill the following criteria: (i)
known as ingredient of products used more or less exclusively
in households and (ii) previously reported as constituent of
municipal sewage. The fragrances (w24, w33, w70–72, w74–
75, w87–88), the insect repellent N,N-diethyl-m-toluamide
(DEET) (w76), the antimicrobial chloroxylenol (w9), and the
antimicrobial degradation product methyltriclosan (s31) fulfill
these criteria. They are ingredients of personal care products
(Table S4), and they were previously described as constituents
of municipal wastewaters (Eriksson et al. 2003; Oppenheimer
et al. 2007; Klaschka et al. 2013). This also applies to the
detected pharmaceutical drugs and stimulants (w77–w81). All
of them are in use for human medication and were previously
analyzed in municipal sewage (e.g., Rosal et al. 2010). Finally,
the detergent residues linear alkylbenzenes (LABs, s45) are
well-known characteristic constituents of municipal sewage
(e.g., Takada and Eganhouse 1998).
All these compounds identified in the present study in sam-
ples from the industrial area were previously detected in the
rivers flowing through the megacity Jakarta (Dsikowitzky
et al. 2016). Entire sections of this megacity lack an appropri-
ate sewage system (e.g., Cybriwsky and Ford 2001), and the
river systems in Jakarta thus receive large amounts of untreat-
ed or partially treated municipal wastewaters. Therefore, there
are likely relevant water contaminants in all Indonesian urban
areas without adequate sewage treatment facilities.
Hydroxybiphenyl (w40) was not previously found in the
Environ Sci Pollut Res
Jakarta rivers. It is applied as preservative in personal care
products and as household pesticide (Table S4). It was identi-
fied as one of the compounds with estrogenic activity in mu-
nicipal sewage (Körner et al. 2000).
Typical contaminants from municipal sewage were present
at all stations of the study area, as can be seen from the distri-
bution of LABs (s45, Table S2), pharmaceutical drugs (w78–
81, Table S3), and synthetic fragrances (w87–88, Table S3).
Interestingly, several typical compounds from municipal
sources, which were found to be dominant aquatic contami-
nants in other countries, were searched for but not detected in
the study area. This applies, e.g., to the pharmaceutical drug
carbamazepine and the flame retardant tris(2-chloro-1-
methylethyl) phosphate (TCPP) which are abundant in
European surface waters (Loos et al. 2009, Regnery and
Püttmann 2010). It is likely that these compounds are not
intensively used in the study area.
The major sources of benzothiazoles in the environment
are tire wear particles and scrap tires (Ni et al. 2008).
Benzothiazoles were proposed as indicators of the contribu-
tion of street runoff in urban areas (Spies et al. 1987). The
detected thiazoles (w64–66) as well as methylbenzofuranone
(w32), a compound previously identified in gasoline exhausts,
were therefore assigned to street runoff as input source
(marked with BSR^ in Table S4). Contaminants from this
source were present in the whole working area (Table S3).
Organic contaminants originating from agriculture
The carbamate pesticides carbofuran (w84) and isoprocarb
(w85) are commonly used insecticides in tropical regions
(marked with BA^ in Table S4) and were detectable in the
whole study area. Interestingly, the organochlorine pesticides
chlorazine (w82) and 2,4-D (w86) were only sporadically
found in the water samples (Table S3).
The DDT metabolite DDD (s46) and chlorpyrifos
(s47) in the sediment (Table S2) could stem from a
(past) application in agriculture or from a municipal
source. DDT was used for indoor residual spraying in
Indonesia to eradicate the malaria disease and as pesti-
cide in agriculture. Since the late 1990s, the use of all
organochlorine pesticides in Indonesia is prohibited
(Sudaryanto et al. 2006). Besides the agricultural appli-
cation in paddy rice cultivation, chlorpyrifos is used as
household insecticide in Indonesia. According to their
application, DDT and chlorpyrifos, therefore, have to
be considered as pesticides and/or biocides and an un-
ambiguous elucidation of their origin is not possible.
Organic contaminants originating from industrial emissions
Most source-specific contaminants were assigned to an indus-
trial input (tagged with BI^ in Table S4), according to the
Environ Sci Pollut Res
following criteria: (i) known as educt, by-product or, interme-
diate of industrial syntheses and (ii) previously reported as
constituent of industrial wastewaters.
Several contaminants identified in the river water from
the industrial area were previously reported as typical con-
stituents of wastewaters from modern paper industry facili-
ties, i.e., facilities where no chlorine is used for bleaching.
Bis(methylethyl)naphthalenes (w89, s48; see also mass
spectrum in Fig. S5) and phenylmethoxynaphthalene (w90,
s49) are employed as color sensitizers for thermal paper
manufacturing and were present in the wastewaters of
Japanese paper-producing facilities (Terasaki et al. 2008).
Moreover, 2,2-dimethoxy-2-phenylacetophenone (DMPA,
w39), 2,4,7,9-tetramethyl-5-decyne-4,7-diol (TMDD)
(w41), bisphenol A (w44), and 1,2-diphenoxyethane (w93)
were found to be characteristic constituents in process waters
and untreated effluents of several modern German paper
production sites, whereas methyldehydroabietate (w19) was
only present in the process waters of one facility. The pres-
ence of DIPN, phenylmethoxynaphthalene, DMPA, and
diphenoxyethane in the studied river points to the input of
untreated or insufficiently treated paper industry wastewa-
ters, as these four contaminants were reported to occur only
in untreated wastewaters. TMDD and bisphenol A in con-
trast are typical constituents of untreated and treated paper
industry wastewaters and are therefore indicators for paper
industry inputs in general (Dsikowitzky et al. 2015).
Although both compounds might also occur in small
amounts in municipal wastewaters, discharges of paper-
and paint-producing facilities are the main sources of
TMDD and bisphenol A fluxes into the environment
(Fürhacker et al. 2000; Guedez and Püttmann 2014).
Contaminants related to paper production were found at all
sampling stations (Tables S2 and S3).
Compounds related to the inputs of different chemical in-
dustry branches were also detected in the whole study area
( Ta b l e S 3 ) . E t h y l - 4 - e t h o x y b e n z o a t e ( w 1 8 ) a n d
triphenylphosphinoxide (TPPO, w58) that are related to olefin
production were previously identified in effluents from the
petrochemical industry (Castillo et al. 1999; Botalova et al.
2009). Di-tert-butylphenol (w45) was reported as a constitu-
ent of effluents from the petrochemical industry and from
rubber and tire production facilities (Castillo and Barceló
1999; Worawit 2006). Interestingly, the structurally related
DBQ (s37) was found in the sediments (Table S2). It is prob-
ably a degradation product of di-tert-butylphenols (Jungclaus
et al. 1978). Di-tert-butylhydroxybenzoic acid (w11) and
bisphenol A (w44) were previously detected in textile industry
wastewaters and isophorone (w38) in rubber and tire produc-
tion wastewaters (Jungclaus et al. 1976; Castillo and Barceló
2001; Loos et al. 2007).
Several further contaminants identified in this study are
known as educts, by-products, or intermediates of industrial
syntheses or as constituents of high-tech lubricants, but have
as yet not been described as industrial wastewater constitu-
ents. They were tagged with BI^ in the supplementary material
(Table S4). Whether they are relevant constituents of industri-
al wastewaters, in terms of detection frequencies and concen-
trations, has to be confirmed in future studies. Among these
compounds, to our knowledge, 1-phenylpent-1-en-3-one
(w34), 2-hydroxy-3-methyl-1,4-naphthoquinone (s38),
dibutylformacetamide (w50), and trichloroethylphenyl acetate
(s50) are reported here for the first time as environmental
contaminants.
In conclusion to the discussion above, the organic contam-
inant spectrum in the studied river section reflects the inputs of
untreated or partially treated paper industry wastewaters. In
addition, an input from the petrochemical industry and of one
or more other chemical industry branches was evident. For the
latter, an unambiguous assignment of the contaminants to a
specific chemical manufacturing branch was not possible.
Spatial distribution of the contamination and the impact
of the emissions on the water quality
In the sediment samples, mainly contaminants not assignable
to a specific pollution source were found (BOrganic contami-
nants not assignable to a specific pollution source^ section).
Therefore, to assess the spatial distribution of the contamina-
tion along the studied river section, the focus was on the water
contamination. Among the water contaminants, compounds
acting as indicator for the individual types of emission sources
were selected for quantification. Some further contaminants
without specific origin have been considered, because they
exhibit environmentally interesting structural moieties (in par-
ticular S- or Cl-containing substances) or relevant technical
applications (e.g., 2,2,4-trimethyl-1,3-pentane-
dioldiisobutyrate (TXIB) and MBB). The results are presented
in Table 1 (sampling in May, (beginning of the dry season, and
in October, beginning of the rainy season).
Among the compounds without specific origin, TXIB
(w15) and tris(1-chloroethyl)phosphate (TCEP, w56) were
present in the highest concentrations of up to 1900 and
1000 ng L−1, respectively. The maximum concentrations of
both compounds were found in the industrial area (stations
R4–R6, Table 1).
Fragrances and physiologically effective compounds were
chosen as indicators for municipal sewage inputs (w9, w33,
w76-w81, w87–88). The concentration levels of these com-
pounds did not show a clear seasonal trend (Table 1). DEET
(w76), caffeine (w77), ibuprofen (w80), and mefenamic acid
(w 81) were found to have the highest concentrations among
the municipal contaminants, pointing to their intensive usage
in Indonesia. Regarding the concentration profiles along the
river, the highest concentrations in both seasons were found in
the industrial area (stations R4–R6). In this area,
 Environ Sci Pollut Res

Table 1 Concentrations [ng L−1] of organic contaminants in surface water samples taken in May 2013 and in October 2013

No. Compound Sampling stations

Upstream stations Industrial/urban area River mouth Jakarta Bay

R1 R2 R3 R4 R5 R6 R7 JB1 JB2

Chlorinated compounds
w9 Chloroxylenol May 2013 n.d. n.d. n.d. 30 20 n.d. n.d. 20 30
Oct 2013 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.
Esters
w15 TXIB, 2,2,4-trimethyl-1,3-pentane-dioldiisobutyrate May 2013 550 880 260 610 1300 1900 580 740 410
Oct 2013 770 740 640 1700 810 1100 310 840 60
w22 MBB, methyl 2-benzoylbenzoate May 2013 n.d. n.d. n.d. n.d. 350 420 n.d. n.d. n.d.
Oct 2013 n.d. n.d. n.d. 20 50 n.d. n.d. n.d. n.d.
Aldehydes and ketones
w33 Coumarin May 2013 n.d. n.d. n.d. n.d. 250 280 n.d. n.d. n.d.
Oct 2013 n.d. n.d. n.d. 220 120 210 n.d. 110 n.d.
w39 DMPA, 2,2-dimethoxy-2-phenylacetophenone May 2013 20 40 20 150 530 300 100 80 20
Oct 2013 40 20 40 760 690 920 20 n.d. n.d.
Alcohols
w41 TMDD, 2,4,7,9-tetramethyl-5-decyne-4,7-diol May 2013 460 260 200 2000 18,000 13,000 950 1300 890
Oct 2013 240 260 330 27,000 2400 6300 2500 990 110
Phenols
w44 Bisphenol A May 2013 n.d. n.d. 10 50 7500 8000 n.d. 10 260
Oct 2013 30 30 n.d. 150 1300 2600 n.d. 1300 60
Nitrogen-containing compounds
w47 Bumetrizole May 2013 70 70 n.d. 100 n.d. 70 n.d. n.d. n.d.
Oct 2013 n.d. n.d. n.d. n.d. n.d. n.d. 20 20 20
Phosphorus-containing compounds
w56 TCEP, tris(1-chloroethyl)phosphate May 2013 60 80 60 410 60 100 150 100 120
Oct 2013 110 140 110 1000 100 50 240 110 10
w58 TPPO, triphenylphosphinoxide May 2013 10 10 10 160 270 230 60 n.d. 20
Oct 2013 n.d. n.d. n.d. 40 70 80 60 50 n.d.
Heterocyclic compounds
w65 MTB, 2-methylthiobenzothiazole May 2013 20 n.d. 20 270 240 220 180 1200 1600
Oct 2013 160 70 70 6700 330 370 540 4100 n.d.
Sulfur-containing compounds
w59 NBBS, N-butylbenzene-sulfonamide May 2013 < 10 < 10 < 10 20 30 50 < 10 < 10 10
Oct 2013 10 10 10 10 20 20 10 30 20
w60 NMBS, N-ethyl-p-toluenesulfonamide May 2013 n.d. n.d. n.d. 360 290 410 n.d. 40 70
Oct 2013 n.d. 20 20 n.d. n.d. 130 50 n.d. n.d.
w62 Diphenylsulfone May 2013 n.d. n.d. n.d. n.d. 310 400 10 40 30
Oct 2013 n.d. n.d. 10 n.d. 530 630 60 140 n.d.
Physiologically effective compounds
w76 DEET, N,N-diethyl-m-toluamide May 2013 180 470 90 10 3700 5900 30 470 40
Oct 2013 230 250 30 3000 1000 1800 n.d. 1100 130
w77 Caffeine May 2013 n.d. n.d. 180 2600 1300 1900 330 340 1300
Oct 2013 60 50 160 1300 490 370 n.d. 710 90
w78 Propyphenazone May 2013 10 10 20 30 70 100 20 < 10 20
Oct 2013 10 10 30 20 440 340 20 30 < 10
w79 Diclofenac May 2013 n.d. n.d. n.d. 20 290 90 n.d. n.d. n.d.
Oct 2013 n.d. n.d. n.d. 10 n.d. 30 n.d. 10 n.d.
Environ Sci Pollut Res

Table 1 (continued)

No. Compound Sampling stations

Upstream stations Industrial/urban area River mouth Jakarta Bay

R1 R2 R3 R4 R5 R6 R7 JB1 JB2

w80 Ibuprofen May 2013 n.d. 30 n.d. 230 480 520 80 240 50
Oct 2013 40 10 820 270 3000 1600 90 230 n.d.
w81 Mefenamic acid May 2013 n.d. n.d. 20 260 4200 1200 110 90 n.d.
Oct 2013 40 < 10 270 250 10 90 10 n.d. n.d.
Pesticides
w83 Ametryn May 2013 n.d. n.d. n.d. 120 n.d. n.d. 20 n.d. n.d.
Oct 2013 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.
w84 Carbofuran May 2013 < 10 < 10 20 40 20 20 < 10 < 10 10
Oct 2013 210 n.d. 250 570 520 370 2000 200 n.d.
w85 Isoprocarb May 2013 < 10 10 30 160 20 n.d. 70 10 10
Oct 2013 20 20 20 n.d. 20 20 20 n.d. n.d.
Synthetic fragrances
w87 HHCB, galaxolide May 2013 80 420 310 830 310 330 430 1300 690
Oct 2013 670 230 430 6000 1200 1700 620 1800 60
w88 AHTN, tonalide May 2013 10 40 30 60 40 40 50 100 80
Oct 2013 80 20 50 520 150 170 60 240 10
HHCB/AHTN ratio May 2013 8.0 10.5 10.3 13.8 7.8 8.3 8.6 13.0 8.6
Oct 2013 8.4 11.5 8.6 11.5 8.0 10.0 10.3 7.5 6.0
Technical additives
w89 DIPN May 2013 n.d. n.d. 80 n.d. 770 1200 100 350 280
Oct 2013 n.d. n.d. 220 n.d. 7400 8500 180 1000 n.d.
w90 Phenylmethoxy-naphthalene May 2013 10 40 40 50 1800 1400 80 120 250
Oct 2013 50 n.d. 70 80 6200 8500 60 490 n.d.
w93 1,2-Diphenoxyethane May 2013 n.d. n.d. n.d. n.d. 250 220 n.d. n.d. n.d.
Oct 2013 n.d. n.d. n.d. 3300 1000 n.d. n.d. 160 n.d.

The quantified organic contaminants were selected from the set of compounds identified in the aqueous phase due to their source specificity and/or
environmentally interesting structural moieties. The compound numbers refer to the numbering in Table S3 of the supplementary material. A complete
list of the chemical names is given in the supplementary material S1
n.d. not detected

concentrations in the microgram-per-liter range were detected.
For example, the galaxolide (HHCB) concentrations in river
water from the industrial area in October 2013 ranged between
1200 and 6000 ng L−1 (Table 1). Such high values are usually
found in pure untreated municipal sewage (e.g., Horii et al.
2007).
MTB (methylthiobenzothiazole, w65) was chosen as a
marker for street runoff inputs. In both seasons, higher MTB
concentrations in the industrial area (R4–R6) than upstream
(R1–R3) were found (Table 1). Concentrations measured in
May, at the beginning of the dry season, were generally lower
as compared to October. This might be the result of a flushing
out of street dust during the period of strong rain and flooding
events, leading to lower concentrations in the river water in the
period after these events. Interestingly, the MTB
concentrations in samples from Jakarta Bay were among the
highest detected in the study area. This bay receives water
from 13 rivers/channels that transport the street runoff from
the whole megacity Jakarta into the bay. Hence, here, an ac-
cumulation process might be observed.
The concentrations of three pesticides (w83–w85),
representing the agricultural contaminant inputs, did not show
a specific distribution pattern along the river (Table 1). The
carbofuran concentrations were much higher in October, at the
beginning of the rainy season (up to 2000 ng L−1), than in May
(up to 40 ng L−1). Carbofuran pesticides like Furadan 3G are
widely used during rice cultivation, a typical crop of the rainy
season (Pingali and Roger 1995).
TPPO (w58), a typical constituent of petrochemical efflu-
ents, and paper industry contaminants (w39, w41, w44, w89–
 Environ Sci Pollut Res

90, w93) were selected to assess the spatial distribution of
industrial inputs. During both samplings, TPPO showed the
same distribution pattern, with very low concentrations or not
detectable upstream the industrial area (R1–R3), and en-
hanced concentrations in the industrial area (R4–R6)
(Table 1). Likewise, this pattern was found for all paper in-
dustry contaminants during both seasons (see Fig. 2). In the
river water from the industrial area, the concentrations of the
paper industry contaminants DMPA (w39), TMDD (w41),
bisphenol A (w44), DIPN (w89), phenylmethoxynaphthalene
(w90), and diphenoxyethane (w93) were similar to those pre-
viously reported from process waters of a German paper pro-
duction site (Dsikowitzky et al. 2015).
The contaminant concentrations at stations R1–R3 along the
Western Tarum Canal, especially of those with an industrial ori-
gin, were significantly lower than in the industrial area (R4–R6,
Table 1). However, the contaminants from municipal sources
exhibited high concentrations in October 2013, for example, the
pharmaceuticals ibuprofen (820 ng L−1) and mefenamic acid
(270 ng L−1). This is concerning regarding the importance of
clean water resources in this artificial channel that feeds the public
water supply of Jakarta. The extremely high concentrations of
contaminants with municipal and industrial origins in the indus-
trial area during both seasons are striking. The concentrations in
the river water were as high as in untreated municipal sewage or
in raw process waters from the paper industry. An explanation for
this extreme river pollution is the discharge of immense amounts
of untreated or only partly treated wastewaters into the small
river/channel system in the industrial area. Some of the contam-
inants from the industrial point sources are subject to transport
into the coastal waters. DMPA (w39), TMDD (w41), TPPO
(w58), DIPN (w89), and phenylmethoxynaphthalene (w90) were
detectable in the water samples from station R7 (Table 1), which
is located ~ 30 km downstream the industrial discharges (see Fig.

Upstream stations Industrial/Urban River Jakarta Bay

area mouth
30000

Water concentrations ng L-1

May
2013
20000

10000

0
R1 R2 R3 R4 R5 R6 R7 JB2 JB1

October
Water concentrations ng L-1

2013 30000

20000

10000

0
R1 R2 R3 R4 R5 R6 R7 JB2 JB1
Stations
Fig. 2 Concentrations of contaminants related to paper production in DIPN, bis(methylethyl)naphthalenes Phenylmethoxynaphthalene
May and October 2013 in water samples from the river system
receiving discharges from the main industrial manufacturing center of DMPA, 2,2-dimethoxy-2-phenylacetophenone 1,2-
Indonesia located in the Greater Jakarta Jakarta metropolitan area. A Diphenoxyethane
schematic sketch of the working area is depicted in Fig. 1.
TMDD, 2,4,7,9-tetramethyl-5-decyne-4,7-diol Bisphenol A.
Environ Sci Pollut Res
1). These contaminants are obviously persistent enough to be
transported in the aqueous phase over a distance of several kilo-
meters and are therefore relevant for the water quality of the
whole river section downstream the industrial area. All of them
were also detectable in the seawater samples from stations JB1
and JB2 in Jakarta Bay, where the river that transports the pollut-
ant loads from the industrial discharges into the bay (Fig. 1).
Hence, the paper industry discharges contribute to the contami-
nation of the coastal ecosystem. However, regarding the pollution
of the bay and the rivers, it has to be taken into account that
leaching of dumped wastepaper might be a further source of
paper contaminants.
DIPN (w89, s48) and phenylmethoxynaphthalene (w90,
s49) were present in the aqueous phase as well as in the sed-
iments downstream the industrial area and in Jakarta Bay
(Table 1). The accumulation of these particle-associated con-
taminants in economic important mussel and fish species from
Jakarta Bay was previously reported (Dwiyitno et al. 2016).
From this, it follows that the paper industry contributes to the
contamination of fishery resources in the coastal waters. A
comparison with toxicity thresholds shows that the bisphenol
A concentrations in river water from the industrial area pose a
threat to macrobenthic invertebrates. Exposure experiments
with the freshwater snail Marisa cornuarietis revealed adverse
effects of bisphenol A on reproduction and survival at EC10
13.9 ng L−1 (concentration with response of 10% of the mem-
bers of the tested population). This effect was at least partially
masked at 27 °C (EC10 998 ng L−1), when compared with
20 °C (EC10 14.8 ng L−1) (Oehlmann et al. 2006). At stations
R5 and R6, the bisphenol A concentrations were higher than
the determined effect value of 998 ng L−1 (Table 1). In
October 2013, also at one station in the Jakarta Bay, a value
higher than 998 ng L−1 was detected (Table 1).
Potential of the identified compounds to trace river
pollution in other densely populated industrial areas
The potential of the physiologically effective compounds
(w76–81) and synthetic fragrances (w87–88) that were de-
tected in high concentrations in the industrial area
(BSpatial distribution of the contamination and the impact
of the emissions on the water quality^ section) for use as
municipal markers in tropical urban areas was already
discussed in Dsikowitzky et al. (2016).
Moreover, our quantitative assessment showed the environ-
mental relevance (BSpatial distribution of the contamination
and the impact of the emissions on the water quality^ section)
of contaminants that were just recently reported as typical
constituents of wastewaters from modern paper industry facil-
ities (Terasaki et al. 2008). Whether these compounds are also
applicable to trace the large-scale distribution of paper industry
wastewaters in aquatic systems is dependent on the criteria
developed for suitable molecular markers by Takada and
Eganhouse (1998): (i) massive usage, (ii) environmental per-
sistence, and (iii) source specificity. The typical paper industry
contaminants reported in this study fulfill the criterion of mas-
sive usage, but their source specificity is questionable. There
might be further sources such as leaching of dumped waste-
paper. Previous studies demonstrated that thermal paper con-
tains up to 17 mg g−1 bisphenol A and that household paper
products contain up to 0.98 μg g−1 TMDD (Mendum et al.
2011; Guedez and Püttmann 2014).
Whether the typical paper industry contaminants are per-
sistent enough to be used as molecular markers has to be
proved in future studies. Previous results showed that
bisphenol A is rapidly degraded in the aquatic environment
(half-lives 2.5 to 4 days, Staples et al. 1998). For the other
compounds, a comprehensive investigation on their environ-
mental stability is missing. We therefore suggest to account
the combined presence of DMPA (w39), DIPN (w89, s48),
phenylmethoxynaphthalene (w90, s49), and diphenoxyethane
(w93) in water in high concentrations as alarm indicator for
the input of insufficiently treated paper industry wastewaters
in the affected river section on a small spatial scale. The lack
of adequate wastewater treatment is often a problem in emerg-
ing and developing countries. The combined presence of
TMDD (w41) and bisphenol A (w44) in high concentrations
far above the level upstream and downstream the affected
river section can be used as indicator for inputs of paper in-
dustry wastewaters in general—treated or untreated (see also
BOrganic contaminants originating from industrial emissions^
section).
TPPO (w58) is a by-product of the olefin production and
therefore originates from petrochemical syntheses. However,
this compound is also a by-product or an educt of other indus-
trial syntheses (Table S4). Whether these other industrial
sources are also relevant is as yet unknown. TPPO was reported
as constituent of petrochemical effluents in several studies
(BOrganic contaminants originating from industrial emissions^
section), demonstrating its frequent occurrence in this type of
industrial effluents. This compound has rarely been reported as
an aquatic contaminant, and its environmental stability has to
our knowledge not been studied to date. TPPO could have the
potential for the use as a marker to trace petrochemical waste-
water inputs in aquatic systems.
Conclusions
In this study, a complex mixture of organic contaminants com-
prising more than 100 structurally heterogenic compounds
was detected in a river affected by discharges from a large
industrial manufacturing center and from municipal sources.
With the conventional approach to assess selected contami-
nant groups including PAHs (polycyclic aromatic hydrocar-
bons), PCBs (polychlorinated biphenyls), DDT
 Environ Sci Pollut Res

(bis(chlorophenyl)trichloroethane) and its metabolites, and
further priority pollutants, the largest part of this contamina-
tion, would have remained undetected and—consequently—
uncontrolled. The non-target screening approach applied in
this study therefore functions as the adequate tool for the com-
prehensive evaluation of water pollution in areas affected by
emissions from multiple sources. It is the first crucial step
before associated risks for the environment and for human
health can be addressed.
The application of all detected compounds was also
assessed, in order to identify and to disentangle the contribu-
tions from different industrial branches and the urban emis-
sions to the contamination of the studied river. In this respect,
the industrial wastewaters were the source of most of the de-
tected compounds. Among the compounds found in excep-
tionally high concentrations in the industrial area, several in-
dicative compounds for paper industry and petrochemical in-
dustry wastewater inputs were determined, which are present-
ed in Table 2. From the economic point of view, the paper
industry and the petrochemical industry are major industrial
branches across the globe. They are also among the most
significant industrial branches contributing to water pollution.
It is likely that in many other emerging economies with
strongly increasing industrialization and ineffective pollution
source control, untreated or partially treated wastewaters of
these industrial branches are discharged. Therefore, the indi-
cator compounds depicted in Table 2 can serve as a tool to
trace river pollution in those regions where wastewater inputs
from these two industrial sources are suspected.
Some compounds known as educts, by-products, or inter-
mediates of industrial chemical syntheses were discovered in
this study as environmental contaminants for the first time. An
unambiguous assignment of these contaminants to a specific
chemical manufacturing branch was not possible. More stud-
ies about the composition of wastewaters from chemical
manufacturing facilities are urgently required, because they
would help to assign such compounds to their respective in-
dustrial sources. This applies in particular to industrial

Table 2 Organic compounds identified in river water and sediments from the industrial area that were assignable to paper industry or petrochemical
industry wastewater inputs
Chemical name Structural Bioconcen- Log EC50, Daphnia Water References
formular tration factor KO/W magna [mg L-1] solubility
[mg L-1]

Alarm indicators for inputs of insufficiently treated paper industry wastewaters

O

DMPA,
2,2-Dimethoxy-2- 230 2.95 128.3 66.3 CCR database
O

phenylacetophenone

O GESTIS-
1,2-Diphenoxyethane O 3.81 Stoffdatenbank 2017

DIPN,
CCR database
Bis(methylethyl)naphthalenes 2600 6.08 0.01 0.120 ECHA database

Phenylmethoxynaphthalene 100 4.46

O

Sigma Aldrich 2006

Indicators for treated and untreated paper industry wastewaters

OH OH CCR database
TMDD,
Guedez and Püttmann
2,4,7,9-Tetramethyl-5-decyne- 2.01 2.8 12.04 1,700 2014 and references
4,7-diol therein
US EPA 2006

Staples et al., 1998 and

Bisphenol A <100 3.3 8.91 120 references therein
CCR database
HO OH
EnviChem database

Indicator for discharges from petrochemical facilities

Sternbeck et al. 2012
TPPO, UBA Österreich 2009
<60 2.8 62.8
Triphenylphosphinoxide TOXNET 2017

These compounds could be useful as indicators to track inputs from these industrial pollution sources in other aquatic systems. Information from
chemical data bases were obtained from http://www.echemportal.org
EC50 concentration of a chemical which induces a defined response of 50% of the members of a tested population after a specified test duration
Environ Sci Pollut Res
facilities producing modern consumer goods (e.g., packagings
and other plastic products, technical products such as com-
puters, personal care products) and the chemicals needed for
the manufacturing of these goods (e.g., polymers, coatings,
inks, dyes, crystal liquids for computer screens, sunscreen
agents).
The rapid industrialization in emerging and developing
countries, where in many cases an ineffective source control
and wastewater treatment prevail, has led to as yet unrecog-
nized threats to the quality of water and fishery resources in
these countries. It is urgently required that further studies ad-
dress these recent economic developments and the related
environmental problems.
Acknowledgments This study is part of the Indonesian-German
SPICE Program (Science for the Protection of Indonesian Coastal
Marine Ecosystems), funded by the BMBF, and supported institutionally
by the Indonesian Research and Development Center for Marine and
Fisheries Product Processing and Biotechnology. Special thanks go to
Mrs. Yvonne Esser who supported the quantification of the organic con-
taminants.
Funding information This study is funded by the German Federal
Ministry of Education and Research (BMBF, Grant No. 03F0641E).
References
Botalova O, Schwarzbauer J, Frauenrath T, Dsikowitzky L (2009)
Identification and chemical characterization of specific organic con-
stituents of petrochemical effluents. Water Res 43:3797–3812
BPS (Badan Pusat Statistik) (2014) Population of Bekasi Regency based
on gender. Statistic of Bekasi Regency 2014 and Statistic of Bekasi
City 2014. http://bekasikab.bps.go.id
Brack W, Schirmer K, Erdinger L, Hollert H (2005) Effect-directed anal-
ysis of mutagens and ethoxyresorufin-O-deethylase inducers in
aquatic sediments. Environ Toxicol Chem 24:2445–2458
Castillo M, Barceló D (2001) Characterisation of organic pollutants in
textile wastewaters and landfill leachate by using toxicity-based
fractionation methods followed by liquid and gas chromatography
coupled to mass spectrometric detection. Anal Chim Acta 426:253–
264
Castillo M, Alpendurada MF, Barceló D (1997) Characterization of or-
ganic pollutants in industrial effluents using liquid chromatography–
atmospheric pressure chemical ionization–mass spectrometry. J
Mass Spectrom 32:1100–1110
Castillo M, Barcelo D, Pereira AS, Neto FA (1999) Characterization of
organic pollutants in industrial effluents by high-temperature gas
chromatography–mass spectrometry. TrAC 18:26–36
Castillo M, Barceló D (1999) Identification of polar toxicants in industrial
wastewaters using toxicity-based fractionation with liquid
chromatography/mass spectrometry. Anal Chem 71:3769–3776
Cybriwsky R, Ford LR (2001) City profile: Jakarta. Cities 18:199–210
Dsikowitzky L, Schwarzbauer J, Littke R (2002) Distribution of polycy-
clic musks in water and particulate matter of the Lippe River
(Germany). Organic Geochem 33:1747–1758
Dsikowitzky L, Schwarzbauer J (2013) Organic contaminants from in-
dustrial wastewaters: identification, toxicity and fate in the environ-
ment. In Pollutant Diseases, Remediation and Recycling (pp. 45-
101). Springer
Dsikowitzky L, Botalova O, Illgut S, Bosowski S, Schwarzbauer J (2015)
Identification of characteristic organic contaminants in wastewaters
from modern paper production sites and subsequent tracing in a
river. J Hazard Mater 300:254–262
Dsikowitzky L, Sträter M, Dwiyitno AF, Irianto HE, Schwarzbauer J
(2016) First comprehensive screening of lipophilic organic contam-
inants in surface waters of the megacity Jakarta, Indonesia. Mar
Pollut Bull 110:654–664
Dwiyitno D, Nordhaus L, Andarwulan I, Irianto N, H E, Lioe HN,
Ariyani F, Kleinertz S, Schwarzbauer J (2016) Accumulation pat-
terns of lipophilic organic contaminants in surface sediments and in
economic important mussel and fish species from Jakarta Bay,
Indonesia. Mar Pollut Bull 110:767–777
Eriksson E, Auffarth K, Eilersen AM, Henze M, Ledin A (2003)
Household chemicals and personal care products as sources for xe-
nobiotic organic compounds in grey wastewater. Water SA 29:135–
146
Fares YR, Ikhwan M (2001) Conceptual modeling for Management of
the Citarum/Ciliwung basins, Indonesia. J environ Hydrol 9: paper
10
Franke S, Hildebrandt S, Schwarzbauer J, Link M, Francke W (1995)
Organic compounds as contaminants of the Elbe river and its tribu-
taries. Fresen J Anal Chem 353:39–49
Fürhacker M, Scharf S, Weber H (2000) Bisphenol A: emissions from
point sources. Chemosphere 41:751–756
GESTIS-Stoffdatenbank (2017) http://www.dguv.de/ifa%3B/gestis/
gestis-stoffdatenbank, accessed in June 2017
Grigoriadou A, Schwarzbauer J (2011) Non-target screening of organic
contaminants in sediments from the industrial coastal area of Kavala
City (NE Greece). Water Air Soil Poll 214:623–643
Guedez AA, Püttmann W (2014) Printing ink and paper recycling sources
of TMDD in wastewater and rivers. Sci Total Environ 468:671–676
Hernández F, Ibáñez M, Bade R, Bijlsma L, Sancho JV (2014)
Investigation of pharmaceuticals and illicit drugs in waters by liquid
chromatography-high-resolution mass spectrometry. TrAC 63:140–
157
Hernández F, Ibáñez M, Portolés T, Cervera MI, Sancho JV, López FJ
(2015) Advancing towards universal screening for organic pollut-
ants in waters. J Hazard Mater 282:86–95
Horii Y, Reiner JL, Loganathan BG, Kumar KS, Sajwan K, Kannan K
(2007) Occurrence and fate of polycyclic musks in wastewater treat-
ment plants in Kentucky and Georgia, USA. Chemosphere 68:
2011–2020
Jungclaus GA, Games LM, Hltes RA (1976) Identification of trace or-
ganic compounds in tire manufacturing plant wastewaters. Anal
Chem 48:1894–1896
Jungclaus G, Avila V, Hites R (1978) Organic compounds in an industrial
wastewater: a case study of their environmental impact. Environ Sci
Technol 12:88–96
Klaschka U, von der Ohe PC, Bschorer A, Krezmer S, Sengl M, Letzel M
(2013) Occurrences and potential risks of 16 fragrances in five
German sewage treatment plants and their receiving waters.
Environ Sci Pollut R 20:2456–2471
Körner W, Bolz U, Süßmuth W, Hiller G, Schuller W, Hanf V,
Hagenmaier H (2000) Input/output balance of estrogenic active
compounds in a major municipal sewage plant in Germany.
Chemosphere 40:1131–1142
Liu R, Lin Y, Hu F, Liu R, Ruan T, Jiang G (2016) Observation of
emerging photo-initiator additives in household environment and
sewage sludge in China. Environ Sci Technol 50:97–104
Loos R, Hanke G, Umlauf G, Eisenreich SJ (2007) LC–MS–MS analysis
and occurrence of octyl-and nonylphenol, their ethoxylates and their
carboxylates in Belgian and Italian textile industry, waste water
treatment plant effluents and surface waters. Chemosphere 66:
690–699

Loos R, Gawlik BM, Locoro G, Rimaviciute E, Contini S, Bidoglio G
(2009) EU-wide survey of polar organic persistent pollutants in
European river waters. Environ Pollut 157:561–568
Lopez-Avila V, Hites RA (1980) Organic compounds in an industrial
wastewater. Their transport into sediments. Environ Sci Technol
14:1382–1390
Marsh P (2012) The new industrial revolution: consumers, globalization
and the end of mass production. Yale University Press, New Haven
and London, United Kingdom, 311 pp
Mendum T, Stoler E, VanBenschoten H, Warner JC (2011) Concentration
of bisphenol A in thermal paper. Green Chem Letters and Reviews
4:81–86
Ni HG, Lu FH, Luo XL, Tian HY, Zeng EY (2008) Occurrence, phase
distribution, and mass loadings of benzothiazoles in riverine runoff
of the Pearl River Delta, China. Environ Sci Technol 42:1892–1897
Oehlmann J, Schulte-Oehlmann U, Bachmann J, Oetken M, Lutz I, Kloas
W, Ternes TA (2006) Bisphenol a induces superfeminization in the
ramshorn snail Marisa Cornuarietis (Gastropoda: Prosobranchia) at
environmentally relevant concentrations. Environ Health Persp 114:
127–133
Oppenheimer J, Stephenson R, Burbano A, Liu L (2007) Characterizing
the passage of personal care products through wastewater treatment
processes. Water Environ Res 79:2564–2577
Pingali PL, Roger PA (1995) Impact of pesticide on farmer health and the
rice environment. Kluwer academic publishers: Norwell,
Massachusetts, USA and international Rice research institute
(IRRI): Los Baños, Laguna, the Philippines, 664 pp.
Regnery J, Püttmann W (2010) Occurrence and fate of organophosphorus
flame retardants and plasticizers in urban and remote surface waters
in Germany. Water Res 44:4097–4104
Rosal R, Rodríguez A, Perdigón-Melón JA, Petre A, García-Calvo E et al
(2010) Occurrence of emerging pollutants in urban wastewater and
their removal through biological treatment followed by ozonation.
Water Res 44:578–588
Scheurell M, Franke S, Hühnerfuss H (2007) Effect-directed analysis: a
powerful tool for the surveillance of aquatic systems. Int J Environ
An Ch 87:401–413
Schwarzbauer J, Littke R, Weigelt V (2000) Identification of specific
organic contaminants for estimating the contribution of the Elbe
river to the pollution of the German bight. Organic Geochem 31:
1713–1731
Environ Sci Pollut Res
Sigma Aldrich (2006) Sicherheitsdatenblatt Benzyl 2-naphthyl ether,
S646210, http://www.sigmaaldrich.com, accessed in June 2017
Soares A, Guieysse B, Jefferson B, Cartmell E, Lester JN (2008)
Nonylphenol in the environment: a critical review on occurrence,
fate, toxicity and treatment in wastewaters. Environ Int 34:1033–
1049
Spies RB, Andresen BD, Rice DW Jr (1987) Benzthiazoles in estuarine
sediments as indicators of street runoff. Nature 327:697–699
Staples CA, Dome PB, Klecka GM, Oblock ST, Harris LR (1998) A
review of the environmental fate, effects, and exposures of bisphenol
a. Chemosphere 36:2149–2173
Sternbeck J, Österås AH, Woldergiorgis A (2012) REPORT screening of
TPPO. In: TMDD and TCEP, three polar pollutants. Swedish
Environmental Protection Agency, Report, 48pp
Sudaryanto A, Kunisue T, Kajiwara N, Iwata H, Adibroto TA,
Hartono P, Tanabe S (2006) Specific accumulation of organ-
ochlorines in human breast milk from Indonesia: levels, dis-
tribution, accumulation kinetics and infant health risk.
Environ Pollut 139:107–117
Takada H, Eganhouse RP (1998) Molecular markers of anthropogenic
waste. In: Meyers RA (Ed.) encyclopedia of environmental analyses
and remediation. Wiley: 2883-2940
Terasaki M, Fukazawa H, Tani Y, Makino M (2008) Organic pollutants in
paper-recycling process water discharge areas: first detection and
emission in aquatic environment. Environ Pollut 151:53–59
Toxnet (2017) Toxicology data network, US National Library of
Medicine, data sheet Triphenylphsophine oxide, https://chem.nlm.
nih.gov/chemidplus/rn/791-28-6, accessed in June 2017
UBA (Umweltbundesamt) Österreich (2009) Zulassungspflicht
fürbesonders besorgniserregende Stoffe, Österreichische
Kandidatenstoffe nach REACH 59 (3). Report REP-0241:102 pp.
http://www.umweltbundesamt.at/
US EPA (Environmental Protection Agency) (2006) Inert Ingredient re-
assessment for 2,4,7,9-tetramethyl-5-decyn-4,7-diol (CAS Reg. No.
126–86-3) and 3,6-dimethyl-4-octyn-3,6-diol (CAS Reg. No. 78–
66-0), https://www.epa.gov/sites/production/files/2015-04/
documents/diols.pdf
Worawit W (2006) Characterization and fenton treatment of hazardous or-
ganic substances in Para rubber industrial wastewater in Southern
Thailand. Ph.D. thesis, Chulalongkorn University, doi:123456789/8327