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IERI Procedia 5 (2013) 216 – 222

2013 International Conference on Agricultural and Natural Resources Engineering

Screening of emerging pollutants in the mangrove of Segara


Anakan Nature Reserve, Indonesia
Agung Dhamar Syaktia,*, Moussa Mahdi Ahmedb, Nuning Vita Hidayatia, Endang
Hilmia, Isdy Sulystyoa, Anne Piramb, Pierre Doumenqb
a
Fisheries and Marine Sciences Department-Jenderal Soedirman University, Kampus Perikanan Unsoed Karangwangkal, Jl dr. Suparno,
Purwokerto, 53123, Indonesia.
b
Aix Marseille Université, CNRS, LCE, FRE 3416, équipe MPO. Europôle de l’Arbois-Bâtiment Villemin BP80-13545 Aix-en-Provence
Cedex 4, France

Abstract

107 compounds have been qualitatively identified in the water of the Segara Anakan Nature Reserve, Indonesia, using
liquid chromatography - mass spectrometry (LC-MS), and specially, using time-of-flight (TOF) mass analyzer. Ten
stations represented both anthropogenic (oil refinery site) types and natural (riverine, lagoon, marine) were considered.
Dimecrotic acid, hymechromone, valeryl salycilate, and phthalic acid mono-2-ethylhexyl ester were discovered at all
station indicating apportionment from certain administered medications and from using ubiquitous plastic.

© 2013The
© 2013 The Authors.
Authors. Published
Published by B.V.
by Elsevier Elsevier B.V.under CC BY-NC-ND license.
Open access
Selection
Selection andand
peerpeer review
review under responsibility
under responsibility of Engineering
of Information Information Engineering
Research Institute Research Institute

Keywords: Environmental chemistry; River basin;Emerging organic compounds; Agricultural and industrial effluents; Mangrove

1. Introduction

Segara Anakan Nature Reserve (SANR) is a unique wetland in Java, Indonesia which is made up of a

* Corresponding author. Tel.: +62-81173827; fax:+62-281-638793.


E-mail address: [email protected]

2212-6678 © 2013 The Authors. Published by Elsevier B.V. Open access under CC BY-NC-ND license.
Selection and peer review under responsibility of Information Engineering Research Institute
doi:10.1016/j.ieri.2013.11.095
Agung Dhamar Syakti et al. / IERI Procedia 5 (2013) 216 – 222 217

mangrove-fringed lagoon in Cilacap coastal area. In recent decades, such ecological resources have been
degraded by anthrophogenic activities and uncontrolled discharge of environmental pollutants. [1,2] This study
focus on the “new and recently recognized” environmental pollutants, called emerging contaminants (ECs).
ECs are known because of their potential adverse impact on environmental health even human health. ECs
include lots of chemicals such as personal and pharmaceutical products, such as disrupting endocrine
chemicals (estrogens and steroid hormones), industrial chemicals, biological metabolites, perfluoroalkylated
surfactants, and nanoparticles.[3,4] In SANR, ECs can enter the environment directly via non-point source
discharge such as fisheries, and agricultural activities ,domestic waste, and partly via point-source discharge
of industrial effluents. In view of the current situation, preventive measures must be taken for the ecosystem
protection. Therefore, it is important for us to establish pollution baseline levels as a reference for future
studies. liquid chromatography - mass spectrometry using quadrupole time-of-flight mass analyzer (LC-
QTOF -MS) is used in this study to preliminary screen the ECs since it can provide molecular mass
measurements in high precision (<5 ppm) which is, comparing with available databases of accurate masses,
the identification of an unknown compounds from its empirical formula is possible.[5] The novelty of the study
lies in the investigation of the screened non-target emerging contaminants in the aquatic environment in
SARN, which has been carried out for the first time in the studied area, as well as in Indonesia.

2. Materials and methods

2.1 Sampling

Sampling was conducted in Lagoon and estuary of Segara Anakan which is located on the south coast of
Java in Indonesia. The sites (Fig. 1) included 10 stations with different representative land cover and land uses
such as marine stations (MR1 and MR2), riverine stations (Citanduey, R1; Cibeureum, R2), lagoon stations
(SA1-SA3), and three stations impacted by different human activities respectively, i.e., agriculture,
urbanization and industry (A1-A3). Surface water samples were collected using a bottle sampler and directly
filtered up to 0.45 μm with membrane filters provided by Millipore (Molsheim, France) and reserve at 4 °C.
218 Agung Dhamar Syakti et al. / IERI Procedia 5 (2013) 216 – 222

Fig. 1. Map showing details of the sampling sites in the Segara Anakan Nature Reserve, Indonesia

2.2. Sample preparation


[6]
The samples extraction was based on the research previously described by Mehdi Ahmed and co-authors.

2.3. Liquid chromatography–tandem mass spectrometry


ECs could be discovered with the use of liquid chromatography and quadrupole time-of-flight mass
spectrometry (LC-QTOF-MS, Agilent 6530 series) in the positive ionization mode. Chromatography
condition and analysis were conducted according to the method of Piram and co-authors.[7]

3. Results and Discussion


Table 1 shows a list of 107 compounds that have been qualitatively identified in SANR water using liquid
chromatography - mass spectrometry, and using time-of-flight (TOF) mass analyzers. around 60 compounds
have detected at the human-impacted stations (A1-A3), and our particular interest was in valeryl salycilate,
which had been found at most stations. This compound known as a chemicals used in a laboratories and in
manufacturing. This substance is not classified as dangerous by the Directive 67/548/EEC, but we believed its
ubiquitous presence could be of concern in the future. As reported by Kristensen and co-authors,[8] such a
compound has a structural similarity with phthalates, which is an endocrine modulating chemicals. Other
compounds found ubiquitously were, hymecromone, dimecrotic acid, and phthalic acid mono-2-ethylhexyl
ester. Hymecromone is produced from coumarins, an important compound in the synthesis of insecticides.
Agung Dhamar Syakti et al. / IERI Procedia 5 (2013) 216 – 222 219

The hymecromones, 7-hydroxy-4-methyl-2H-benzo[b]-pyran-2-one or 7-hydroxy-4 methylcoumarin are used


commercially as laser dyes, also a raw materials for the production of certain insecticides.[9] Dimecrotic acid
is used as an one active compound in antimalarial and toxoplasmic drug formulations.[10,11] The compound can
be understood by the long history of malaria, which is endemic in this area. In the other hand, phthalic acid
mono-2-ethylhexyl ester arises from phthalate metabolites from a synthetic plasticizer as believed.[12]
For station A1-3 which indicate the anthropogenic of the local population of 2.000.000, explanation of the
origins of all of the compounds within the listed in Table 1 would be too laborious. We have limited the
discussion to compound that are environmentally relevant. For instance, we note the presence of
imazamethabenz, which is a herbicide used with Roundup in the area.

Table 1. Identification and occurrence of screened compounds in surface water from SANR
^ƚĂƚŝŽŶƐ
EŽ ŽŵƉŽƵŶĚƐ
ϭ Ϯ ϯ DZϭ DZϮ Zϭ ZϮ ^ϭ ^Ϯ ^ϯ
ϭ ϮϬͲŽdžŽͲŚĞŶĞŝĐŽƐĂŶŽŝĐĂĐŝĚ ǀ
Ϯ ƚŚLJůĚŝďƵŶĂƚĞ ǀ
ϯ dŚŝŽƌŝĚĂnjŝŶĞ ǀ
ϰ DĞƚŝƚĞƉŝŶĞ ǀ
ϱ ϮZͲĂŵŝŶŽŚĞdžĂĚĞĐĂŶŽŝĐĂĐŝĚ ǀ
ϲ ĂƉƐĂŝĐŝŶ ǀ
ϳ ,LJĚƌŽŵŽƌƉŚŽŶĞ ǀ
ϴ E͕EͲŝĞƚŚLJůͲϯͲŵĞƚŚLJůďĞŶnjĂŵŝĚĞ;dͿ ǀ
ϵ ĂŝĚnjĞŝŶ ǀ
ϭϬ ŚƌLJƐŽƉŚĂŶŽů ǀ
ϭϮ ϯͲĞŽdžLJǀŝƚĂŵŝŶϯ ǀ ǀ ǀ
ϭϯ ĂůƉŚĂͲ<ĞƚŽƉĂŶƚŽŝĐĂĐŝĚ ǀ ǀ ǀ ǀ
ϭϰ Ϯϲ͕ϮϳͲĚŝŶŽƌǀŝƚĂŵŝŶϯ ǀ
ϭϱ ϯ͕ϯΖͲŝŚLJĚƌŽdžLJĚŝďƵƚLJůĞƚŚĞƌ ǀ ǀ ǀ ǀ
ϭϲ ϲͲŚLJĚƌŽdžLJͲϮͲŚĞdžLJŶŽŝĐĂĐŝĚ ǀ ǀ ǀ ǀ
ϭϳ ĐĞďƵƌŝĐĂĐŝĚ ǀ ǀ ǀ ǀ ǀ
ϭϴ ŽĐŽƐĂŶĞĚŝŽŝĐĂĐŝĚ ǀ ǀ ǀ ǀ ǀ ǀ
ϭϵ ϱͲŽĐƚĂĚĞĐLJůĞŶŝĐĂĐŝĚ ǀ ǀ ǀ ǀ ǀ ǀ ǀ
ϮϬ ;ϮͲŚůŽƌŽƉŚĞŶLJůͿĚŝƉŚĞŶLJůŵĞƚŚĂŶĞ ǀ ǀ ǀ ǀ ǀ ǀ ǀ
Ϯϭ /ŵĂnjĂŵĞƚŚĂďĞŶnj ǀ ǀ ǀ ǀ ǀ ǀ ǀ ǀ ǀ
ϮϮ ϮͲŵĞƚŚLJůͲƚƌŝĚĞĐĂŶĞĚŝŽŝĐĂĐŝĚ ǀ
Ϯϯ KƌƚŚŽƚŚLJŵŽƚŝŶŝĐĂĐŝĚ ǀ ǀ ǀ ǀ ǀ ǀ ǀ ǀ ǀ
Ϯϰ WŚƚŚĂůŝĐĂĐŝĚDŽŶŽͲϮͲĞƚŚLJůŚĞdžLJůƐƚĞƌ ǀ
Ϯϱ sĂůĞƌLJůƐĂůLJĐŝůĂƚĞ ǀ ǀ ǀ ǀ ǀ ǀ ǀ ǀ ǀ ǀ
Ϯϲ ŝŵĞĐƌŽƚŝĐĂĐŝĚ ǀ ǀ ǀ ǀ ǀ ǀ ǀ ǀ ǀ ǀ
Ϯϳ ,LJŵĞĐƌŽŵŽŶĞ ǀ ǀ ǀ ǀ ǀ ǀ ǀ ǀ ǀ ǀ
Ϯϴ njůŽĐŝůůŝŶ ǀ
Ϯϵ ϭͲŽĐƚĂĚĞĐĂŶŽLJůͲƌĂĐͲŐůLJĐĞƌŽů ǀ
ϯϬ ƵƚLJůͲϰͲŚLJĚƌŽdžLJďĞŶnjŽĂƚĞ ǀ
ϯϭ ĞdžĂŵĨĞƚĂŵŝŶ ǀ
ϯϮ ŶƉŝƉƌĂnjŽůĞ ǀ ǀ
ϯϯ ůĚŝŵŽƌƉŚ ǀ ǀ
ϯϰ ϯͲŵĞƚŚLJůͲƚĞƚƌĂĚĞĐĂŶĞĚŝŽŝĐĂĐŝĚ ǀ ǀ
ϯϱ ϭϭͲďƌŽŵŽͲĚŽĚĞĐĂŶŽŝĐĂĐŝĚ ǀ ǀ
ϯϲ ϮϰͲĚŝŚLJĚƌŽdžLJͲϮϮͲŽdžĂǀŝƚĂŵŝŶϯ ǀ ǀ ǀ
ϯϳ ϭͲ;ϭϭͲŽĐƚĂĚĞĐĞŶŽLJůͿͲƌĂĐͲŐůLJĐĞƌŽů ǀ ǀ ǀ ǀ ǀ ǀ
ϯϴ ϭϬͲŚLJƌŽdžLJͲϴͲĞĐĞŶĞͲϮ͕ϰ͕ϲͲƚƌŝLJŶŽŝĐĂĐŝĚ ǀ ǀ ǀ ǀ ǀ ǀ
220 Agung Dhamar Syakti et al. / IERI Procedia 5 (2013) 216 – 222

ϯϵ ϲ͕ϵ͕ϭϮŚĞdžĂĚĞĐĂƚƌŝĞŶŽŝĐĂĐŝĚ ǀ ǀ ǀ ǀ ǀ ǀ ǀ ǀ
ϰϬ >ĞǀƵůŝŶŝĐĂĐŝĚ͕ϯďĞŶnjLJůŝĚĞŶLJů ǀ ǀ ǀ ǀ ǀ ǀ ǀ
ϰϭ WŚĂƚŚĂůŝĐĂĐŝĚDŽŶŽͲϮͲĞƚŚLJůŚĞdžLJůƐƚĞƌ ǀ ǀ ǀ ǀ ǀ ǀ ǀ ǀ ǀ ǀ
ϰϮ WĞƌŝŶĚŽƉƌŝůĂƚ ǀ
ϰϯ ǀŽĐĂĚĞŶĞĂĐĞƚĂƚĞ ǀ
ϰϰ ĐLJĐůŽƉĞŶƚĂŶĞŚĞdžĂŶŽŝĐĂĐŝĚ ǀ
ϰϱ ϭϰͲŚLJĚƌŽdžLJͲϭϮͲƚĞƚƌĂĚĞĐĞŶŽŝĐĂĐŝĚ ǀ
ϰϲ ϯ͕ϳ͕ϭϮͲdƌŝŽdžŽĐŚŽůĂͲϭ͕ϰͲĚŝĞŶͲϮϰͲŽŝĐĂĐŝĚ ǀ ǀ
ϰϳ ϰ͕ϴͲĚŝŵĞƚŚLJůͲĚŽĚĞĐĂŶŽŝĐĂĐŝĚ ǀ ǀ
ϰϴ ϭϳͲŵĞƚŚLJůͲϲͲŽĐƚĂĚĞĐĞŶŽŝĐĂĐŝĚ ǀ ǀ ǀ
ϰϵ ϭϬͲŵĞƚŚLJůͲŚĞdžĂĚĞĐĂŶŽŝĐĂĐŝĚ ǀ ǀ ǀ
ϱϬ ϮͲƉƌŽƉLJůͲƚƌŝĚĞĐĂŶŽŝĐĂĐŝĚ ǀ ǀ ǀ
ϱϭ ŝƐŽƉĞŶƚĂĚĞĐLJůŝĐĂĐŝĚ ǀ ǀ ǀ
ϱϮ Ϯ͕ϲͲĚŝŵĞƚŚLJůͲƵŶĚĞĐĂŶŽŝĐĂĐŝĚ ǀ ǀ ǀ
ϱϯ ƌŽĐĂŝŶŝĚĞ ǀ ǀ ǀ ǀ
ϱϰ WĂůŵŝƚŝĐĂĐŝĚŐůLJĐĞƌŽůĞƐƚĞƌ ǀ ǀ ǀ ǀ ǀ
ϱϱ ϳͲƉĂůŵŝƚŽůĞŝĐĂĐŝĚ ǀ ǀ ǀ ǀ ǀ
ϱϲ ŝŽdžŽĐŚŽůĂͲϭ͕ϰ͕ϵ;ϭϭͿͲƚƌŝĞŶͲϮϰͲŽŝĐĐŝĚ ǀ
ϱϳ WƌĞŐŶĂŶŽůŽŶĞƐƵůĨĂƚĞ ǀ
ϱϴ ϭϲ^ƉŚŝŶŐĂŶŝŶĞ ǀ
ϱϵ ^ƵůƚƌŽƉĞŶ ǀ
ϲϬ ůůŽƉƌĞŐŶĂŶŽůŽŶĞ ǀ ǀ
ϲϭ ^ƵůĨĂŵĞƚŚĂnjŝŶĞ ǀ ǀ ǀ
ϲϮ ^ĞƌŵĞƚĂĐŝŶ ǀ
ϲϯ ŝĐLJĐůŽŵŝŶĞ ǀ
ϲϰ ŶĚƌŽƐƚĞƌŽŶĞ ǀ
ϲϱ >ĂƌŝdžŽůĂĐĞƚĂƚĞ ǀ
ϲϲ sŝŽůĂdžĂŶƚŚŝŶ ǀ
ϲϳ ĞŚLJĚƌŽĂďŝĞƚŝĐĂĐŝĚ ǀ
ϲϴ DĞƚŽŐĞƐƚ ǀ
ϲϵ WŝŵĞůŝĐĂĐŝĚ ǀ
ϳϬ ϳͲŚLJĚƌŽdžLJͲϱͲŚĞƉƚLJŶŽŝĐĂĐŝĚ ǀ
ϳϭ ĂŶŶĂďŝŐĞƌŽů ǀ ǀ ǀ
ϳϮ ϯď͕ϭϳďͲŝŚLJĚƌŽdžLJĞƚŝŽĐŚŽůĂŶĞ ǀ ǀ
ϳϯ ŝŶŽƌǀŝƚĂŵŝŶϯ ǀ ǀ ǀ ǀ
ϳϰ ϭϯ͕ϭϳͲŽĐƚĂĚĞĐĂĚŝĞŶŽŝĐĂĐŝĚ ǀ
ϳϱ ĐƚŝŶŽďŽůŝŶ ǀ
ϳϲ ĂƌĂĐŚŝĚŽŶŽLJůĂŵŝŵĞ ǀ ǀ
ϳϳ ϵͲŚĞƉƚĂĚĞĐLJůĞŶŝĐĂĐŝĚ ǀ ǀ ǀ ǀ
ϳϴ EͲ;ϯͲ/ŶĚŽůLJůĂĐĞƚLJůͿͲ>ͲŝƐŽůĞƵĐŝŶĞ ǀ ǀ ǀ ǀ
ϳϵ WĞŶƚĂŐĞƐƚƌŽŶĞĂĐĞƚĂƚĞ ǀ
ϴϬ EŽƌǀŝƚĂŵŝŶϯ ǀ
ϴϭ ŶĂŶĚĂŵŝĚĞ;ϮϬ͗Ϯ͕ŶͲϲͿ ǀ
ϴϮ ŝŐŝŶĂƚŝŶ ǀ
ϴϯ W'&ϮĂůƉŚĂŝƐŽƉƌŽƉLJůĞƐƚĞƌ ǀ
ϴϰ ĞŶƚĂnjĞƉĂŵ ǀ
ϴϱ &ůƵŵŝŽdžĂnjŝŶ ǀ
ϴϲ /ůŽƉƌŽƐƚ ǀ
ϴϳ ŝƉŚĞŶLJůŵĞƚŚLJůƉŚŽƐƉŚŝŶĞŽdžŝĚĞ ǀ ǀ ǀ
ϴϴ ĞƌďĂŵŝŶĞ ǀ
ϴϵ EͲ;ϮͲŚLJĚƌŽdžLJĞƚŚLJůͿŚĞƉƚĂĚĞĐĂŶĂŵŝĚĞ ǀ ǀ
ϵϬ ϭͲŚĞdžĂĚĞĐĂŶŽLJůͲƐŶͲŐůLJĐĞƌŽů ǀ
ϵϭ /ƐŽƉƌŽƉLJůƉĂůŵŝƚĂƚĞ ǀ ǀ ǀ
ϵϮ ^ƚĞƌĐƵůŝĐĂĐŝĚ ǀ ǀ
ϵϯ ϭϳĂͲƐƚƌĂĚŝŽů ǀ
ϵϰ ŚůŽƌŽdžĂŶƚŚŝŶ ǀ ǀ ǀ
ϵϱ YƵŝŶĞƐƚƌŽů ǀ
Agung Dhamar Syakti et al. / IERI Procedia 5 (2013) 216 – 222 221

ϵϲ ϭϴͲŽdžŽͲŶŽŶĂĚĞĐĂŶŽŝĐĂĐŝĚ ǀ
ϵϳ DĞƚŚŽƉƌĞŶĞ ǀ
ϵϴ ŝĐŽƐĂŶĞĚŝŽŝĐĂĐŝĚ ǀ
ϵϵ ϭϮ^ͲŚLJĚƌŽdžLJͲϭϲͲŚĞƉƚĂĚĞĐLJŶŽŝĐĂĐŝĚ ǀ
ϭϬϬ ϴ͕ϭϭϭϰͲŚĞƉƚĂĚĞĐĂƚƌŝĞŶŽŝĐĂĐŝĚ ǀ ǀ
ϭϬϭ ŝĂǀĞƌŝĚŝŶ ǀ
ϭϬϮ ϭϭͲŵĞƚLJůͲŽĐƚĂĚĞĐĂŶŽŝĐĂĐŝĚ ǀ
ϭϬϯ dĞƚƌĂĐŽƐŽŶĂů ǀ
ϭϬϰ ϭϳ͕ϮϬͲŚĞdžĂĐŽƐĂĚŝĞŶŽŝĐĂĐŝĚ ǀ
ϭϬϱ WƌĞŐŶĞŶŽůŽŶĞ ǀ
ϭϬϲ ŽĐŽƐĂŚĞdžĂĞŶŽLJůͿͲƐŶͲŐůLJĐĞƌŽů ǀ
ϭϬϳ ϭϳ^ƉŚŝŶŐĂŶŝŶĞ ǀ

Drug metabolites were also detected such as dexamphetamine, thioridazine metitepine and enpiprazole
which arise from the most widely used drugs in the treatment of psychiatric patients, azlocillin, a penicillin-
class antibiotic used for veterinary purposes, as well as hydromorphone is known to replace morphine for the
management of pain according to the results of previous studies. Unfortunately there is a lack of information
on how these compounds can be detected in this area. Additionally, the high consumption of chili spice in the
region may explain the presence of capsaicin, which also demonstrated the anthropogenic contamination of
the aquatic environment.

4. Conclusions
The analysis using the LC-QTOF-MS technique for surface water from SANR allows the detection of a broad
range of emerging pollutants, which are detected by using the positive ion mode. To better mitigate potential
health and environmental hazards, future work in SARN should focus on quantitative determination of a
short-list of priority emerging contaminants.

Acknowledgements The authors especially thank G. Tirtawidjaya and M. Cahyadi, who participated in the
sampling trips. The research was financially supported by grants-in-aid from the National Ministry of
Education of Indonesia (DIKTI and BPKLN Kemdiknas Grants) and the Laboratory of Environmental
Chemistry, Aix-Marseille University. We acknowledge the support of the Institut Français d’Indonésie in the
form of an International Travel Grant. We also thank the anonymous reviewers for their constructive
comments and the authors of referred papers including whose ideas not be marked out in detail.

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