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2331 SH Diplomash PDF
2331 SH Diplomash PDF
Presented by:
Muhammad Lukman
Bremen, 2010
Distribution and Sources of Polycyclic Aromatic Hydrocarbons in
Sediments, Suspended Particulate Matter and Waters from the Siak River
System, Estuary and Coastal Area of Sumatra, Indonesia
A dissertation submitted for the degree of Doktor der Naturwissenschaften (Dr. rer. nat.)
at the Faculty of Biology/Chemistry, the University of Bremen, Germany
Presented by:
Muhammad Lukman
First of all, I would like to express my sincerely and great gratitude to Prof. Dr. Wolfgang
Balzer (FB 2, Marine Chemistry, University of Bremen) for his remarkable role in pouring me
with lots of insight, motivation, and supervision throughout my PhD work. I do very much
appreciate for his willingness to offer and provide me the possibility to do PhD in his working
group as well as to join the SPICE Cluster 3.1. (Science for the Protection of Indonesian Coastal
Ecosystem) Project in Riau, Sumatra, Indonesia. Secondly, I am grateful to DAAD (Deutscher
Akademischer Austausch Dienst or German Academic Exchange Service) in providing me a
great support to do my PhD in Germany during the period of 2004 2007.
I would like to thank Prof. Dr. Wolfram Thiemann as the second referee, Prof. Dr.
Gerhard Kattner and Prof. Dr. Venugopalan Ittekkot as the examiners, and all the colleagues
and those previous colleagues in the marine chemistry working group, University of Bremen:
Dr. Uwe Schler, Dr. Wolfgang Barkmann, Immo Becker, Olaf Wilhelm, Timo Daberkow,
Xiaoliang Tang, Jun Fu, Bjrn Bach, Dominique Schobes, Sonia Tambou for their valuable
assistances and discussion in laboratory and analytical aspects, as well as Mrs. Ute Wolpmann
who faithfully helps me with administrative matters during my stay in Bremen.
I would like to extent my appreciation to all my SPICE Cluster 3.1. colleagues: Dr. Tim
Rixen, Dr. Antje Baum (ZMT Bremen), Dr. Herbert Siegel (IOW Warnemuende), Dr. Thomas
Pohlmann (University of Hamburg), Dr. Ralf Woestmann (Terramare, Wilhemshaven), and to
ZMT staffs Dorothee Dasbach and Matthias Birkicht for all their countless assistances, advices
and critics, as well as to Nathan Giles for improving the English.
Also, I would like to thank to Prof. Dr. Gerd Liebezeit (Terramare, University of
Oldenburg) to all insights, advices and discussion. Also, to all Indonesian SPICE colleagues in
University of Riau, Riau during sampling campaigns, particularly Dr. Joko Samiaji, Dr.
Christine Jose, Dewi Kristina, friends at Hasanuddin University, Makassar, and many others. I
thank you so much for your supports.
Last but not least, very special thanks I dedicate to my wife, Rahmawati Yusuf, to my
family my Mother, Father, Sister and Brothers -, and to my all relatives - who always inspire
me during hard time. Finally, I would like to dedicate this work to my country Indonesia and to
those who are fond of better environment.
Kurzfassung
Die vorliegende Arbeit untersucht Ursprung und Verteilung von Polycyclischen Aromatischen
Kohlenwasserstoffen (PAKs) als Indikator fr anthropogene Verschmutzung in den Ksten- und
Flussregionen der Insel Sumatra in Indonesien. Im Vordergrund steht dabei die Analyse der 16 PAK-
Priorittsverbindungen, von denen Referenzmaterial gem der USA-EPA priority pollutants Liste
vorliegt. Untersucht wurden Proben in der Lsung und von Oberflchensedimenten und
Schwebstoffen (SPM) des Siak-Flusses, seiner Flussmndung und des Riau Kstenbereichs in
Sumatra.
Die Untersuchungen ergaben, dass sowohl der Flusslauf als auch Flussmndung und Kstenbereich
des Siak-Flusses erheblich mit PAKs belastet sind. Die Untersuchungsergebnisse weisen auf krftige
pyrogene Stoffquellen hin, insbesondere auf die Verbrennung von Biomasse und Erdl. Sie knnen
daher als Nachweis fr grorumiges, lnger anhaltendes und intensives Verbrennen
landwirtschaftlicher Nutzflchen im Zusammenhang mit krftigen Wald- und Torf-Feuern, die ber
die letzten Jahrzehnte stattfanden, angesehen werden. In diesen von Buschfeuern heimgesuchten
Gegenden bilden die PAK-Verteilungen zwischen Grob- und Feinfraktion an der Kste und in der
Flussmndung ein deutliches Muster, das von den Verteilungen blicher Kstenbereiche deutlich
abweicht. Ein Vergleich der PAK-Verteilungen in den beiden Grenfraktionen in den Sedimenten
der Siak-Kste mit den Kstenbereichen von Wenchang und Wanquan in China deutet darauf hin,
dass die PAKs der Kstengewsser um Sumatra hauptschlich mit den hohen kohleartigen
Materialien wie Ru und verbranntem Torf assoziiert sind. Wie die Untersuchungen zeigen, knnen
auch andere relevante Stoffquellen wie andauernde Erdlverschmutzung in den Gewssern um die
Stdte, in den industriellen Vororten von Perawang, der lstadt Dumai und der Erdlraffinerien im
Gebiet der Flussmndung fr die Belastung mit PAKs verantwortlich sein.
Als Zusammenfassung der Ergebnisse der Einzeluntersuchungen wurden die folgenden drei
Manuskripte erstellt, die an begutachtete wissenschaftliche Zeitschriften zu versenden sind.
Eine Partitionierung der PAKs zwischen Schwebstoffen und Lsung wurde durchgefhrt, um ein
besseres Verstndnis des Verlaufs der Anreicherung dieser Schadstoffe in den Gewssern zu
bekommen. Die gemessenen Partitionskoeffizienten (KD) zeigen eine betrchtliche Streuung zwischen
den beprobten Stationen. Der mittlere KD-Wert im Flusslauf und in der Flussmndung variiert
zwischen 4 und 5 auf der logarithmischen Skala, an der Kste hat er dann einen Wert von 6 erreicht.
Normalisiert auf den organischen Kohlenstoff bewegt sich der Partitionskoeffizient (KOC) zwischen 2
und 4 im Fluss und an der Mndung und zwischen 3 und 5 an der Kste. Diese Variation deutet auf
eine unterschiedliche Qualitt des partikulren organischen Materials hin, in der Ruablagerungen
eine bedeutende Rolle spielen knnen. Anscheinend erhht die Zunahme des Salzgehalts und
eventuell des pH-Wertes den Koeffizienten KD. Auf der anderen Seite hat die Zunahme des gelsten
organischen Kohlenstoffs (DOC) einen umgekehrten Effekt. Dies deutet auf eine wichtige Rolle des
DOC fr die Erhaltung schwerer PAKs in der Lsung hin, was auch eine Erleichterung ihres
Transports beinhaltet.
Ein Vergleich zwischen den Messungen am Siak-stuar (torfhaltiger Boden) und denen
an den Wenchang und Wanquan Flussmndungen (sandiger Boden) (Manuskript III,
Kapitel VI)
Die Verteilung der PAK-Konzentrationen in den Sedimentfraktionen der Siak-Flussmndung und des
Kstengebietes wurde mit den Messungen an den Wenchang (WW)- und Wanquan (WQ)-
Flussmndungen in Hainan, China verglichen. Die Gebiete zeichnen sich durch ihre unterschiedliche
Bodenformation aus: torfhaltig am Siak-Fluss und eher mineralisch oder huminstoffarmer Boden auf
Hainan. Wie oben erwhnt, sind die PAK-Konzentrationen in den Siak-Sedimenten durch einen
hohen Anteil von PAKs und organischem Material in der Grobfraktion charakterisiert. Dieses Muster
wurde nicht in den WW/WQ-Sedimenten gefunden, in denen die PAKs hauptschlich in der
Feinfraktion zu finden sind. Die gemessenen PAK-Konzentrationen der 15 US EPA priority pollutants
(ausgenommen Acenaphthylen) bewegen sich in der Siak-Flussmndung zwischen 0,13 g/g TG und
1,83 g/g TG (median m = 0,69 g/g TG) in der Grobfraktion und zwischen 0,09 g/g TG und 0,43
g/g TG (m = 0,20 g/g TG) in der Feinfraktion. Dagegen wurden PAK-Werte in der Grobfraktion
der WW/WQ-Sedimente zwischen 0,11 g/g TG und 0,39 g/g TG (m = 0,19 g/g TG) und in der
Feinfraktion zwischen 0,09 g/g TG und 0,68 g/g TG (m = 0,47 g/g TG) gefunden. Die relativ
hohe PAK-Konzentration in der Grobfraktion der torfreichen Bodenformation von Sumatra konnte
den hohen Konzentrationen der kohlenstoffhaltigen Materialien wie Ru, Torf und
Pflanzenablagerungen zugeordnet werden, welche zur Anreicherung der PAKs an den Materialien
beitragen. In den WW/WQ-Sedimenten wurden diese hohen Kohlenstoffkonzentrationen nicht
gefunden. In beiden Gebieten gab es keine Unterschiede in den Molekularverteilungen zwischen
Grob- und Feinfraktion, was als Hinweis gewertet werden kann, dass die PAK-Verunreinigungen von
hnlichen Quellen stammen. Dagegen deuten die Isomerenverhltnisse, die fr die
Quellenbestimmung hinzugezogen wurden, darauf hin, dass die PAKs der Siak-Flussmndung durch
Buschfeuer und hnliche Verbrennungen entstanden sind, wohingegen die PAKs der WW/WQ-
Sedimente aus der Kohle- und lverbrennung stammen. Die Konzentration der gelsten PAKs in den
kstennahen stuaren von WW/WQ war relativ gering. Die PAKs waren zwischen 7,36 und 16,2 ng
L-1. Im Gegensatz dazu war die Konzentration im Siak-stuar sowie an der Kste erheblich hher. Sie
betrug zwischen 121 und 619 ng L-1. Huminstoffe in den berliegenden Wasserschichten spielen
ebenfalls eine Rolle fr die Verteilung der PAKs in den Sedimentfraktionen. So enthlt die Siak-
Flussmndung und die Kstenregion signifikante Mengen an DOC, die in den beprobten WW/WQ-
Gebieten nicht gefunden wurden (Balzer, unverffentlichte Daten). Die Verteilungskoeffizienten
Sediment-Wasser der einzelnen PAKs im Siak-stuar ergaben Werte (auf der logarithmischen Skala)
zwischen 2,22 und 5,58 (Median m = 3,37) fr die Grobfraktion und zwischen 1,53 und 5,03 (m =
3,01) in der Feinfraktion. So liegen die KD-Werte im Siak-stuar niedriger als in den WW/WQ-
stuaren, zwischen 1,12 und 5,89 (m = 3,93) fr die Grobfraktion und zwischen 2,58 und 5,85 (m =
4,40) fr die Feinfraktion. Dies lsst vermuten, dass die hohe DOC-Konzentration in der Wassersule
des Siak eine Adsorption an die organischen Sedimentbestandteile behindert.
SUMMARY
This study examined the overall distribution and sources of polycyclic aromatic hydrocarbons
(PAHs), particularly the 16 parent PAHs of the US Environmental Protection Agency priority
pollutant, as an indicator for anthropogenic pollution, in the surface sediments, suspended
particulate matter (SPM) and water solution of the Siak river system, its estuary and the Riau coast,
Sumatra, Indonesia.
The PAHs were determined by high performance liquid chromatography with reverse phase
octadecyl column (RP-C18-HPLC) using ultraviolet and programmable fluorescence detectors.
Method analysis included various sampling techniques for the individual phases, sample preparation,
extraction, work-up procedures and HPLC quantification. Analysis of PAHs in sediment was
focused on the content distribution among two size-fractions: sand/coarse (2 mm - 63 m) and
mud/fine (< 63 m). The particulate PAHs were those embedded in suspended materials retained
by 0.7 m glass fiber filter (GF/F). Dissolved PAHs were obtained from the filtered water-solution,
using an octadecyl solid phase extraction (SPE) system. Quality control measures included the use
of procedural blanks and surrogate standards in order to optimize and validate procedural accuracy,
efficiency and the reproducibility of results. Source apportionment of PAHs was carried out by
applying existing indices of molecular weights and specific isomer ratios.
In general, the results show that PAHs significantly impact the Siak river, the estuary and the
coastal waters. Source apportionment indicated intense signatures of pyrogenic sources, particularly
biomass burnings and petroleum combustion. The results might be evidence of the effects of
widespread, long-term and intense agricultural burnings coupled with multitudinous forest/peat
swamp fires which have occurred frequently over the last decades. In such burning-affected
estuaries and coastal waters, distribution of PAH between the size-fraction in sediments showed
distinctive patterns to those of other coastal areas. Comparison of distribution of PAH in the coarse
and fine fractions between the Siak Sumatra and the Wenchang and Wanquan coastal estuaries of
Hainan China indicates that PAH transferred to the coastal waters of Sumatra were mostly
associated with high carbonaceous materials the burning product particles such as black carbon
and peat. However, the apportionment also showed that another relevant source of PAHs was
chronic petroleum pollution centred in the waters around cities, the industrial estates of Perawang,
oil city of Dumai, and the oil refinery located in the estuary area.
Summarizing the different results the following three manuscripts were produced which are
sent to scientific journals with a referee system.
1
(sand/coarse: 2 mm 63 m and mud/fine: <63 m on the Wentworth scale). The second
manuscript evaluates the concentration, spatial distribution and sources of anthropogenic PAH
contamination on SPM and dissolved PAHs in surface waters of the given study areas (Chapter
V). The last manuscript deals with the character differentiation of PAHs in surficial sediments
from peat- and non-peatland aquatic systems, which is a comparative study of the Siak estuary
of Sumatra and Wenchang/Wanquan estuaries of Hainan, China (Chapter VI).
The work undertaken in this study was an integrated part of Cluster 3.1. of the SPICE
Project (German-Indonesian Science for the Protection Indonesia Coastal Ecosystem) - a
research collaboration on marine biogeoscience carried out between 2004 and 2007. The general
theme of Cluster 3.1 was "coastal ecosystem health: the transfer of natural and anthropogenic
materials from land to the coastal sea", focusing in particular on the Siak River in Riau
Province, Sumatra, Indonesia. It is fully recognized that there has been no analogous study
undertaken for the particular areas mentioned above up to the present. This, of course, brings
with it the added difficulty of comparing the magnitude of contaminants in Indonesia with those
in other areas of the world. The nature of this study is important, because it presents initial
scientific data as part of the first comprehensive study on PAH distribution for this region. In
this respect, the results can serve as a starting point for discussion and reference for the future
analogous studies attempting to further refine the knowledge in this area.
1.1.1. Definition
Polycyclic aromatic hydrocarbons (PAHs), also called polyaromatic hydrocarbons or
polynuclear aromatic hydrocarbons, refer to a group of organic arene compounds composed of
two or more fused aromatic benzene rings. These compounds contain various configurations of
molecular ring structures, however the base-unit rings do not have heteroatoms within the rings.
PAHs are therefore explicitly associated with their parent compounds. A fused ring results from
the sharing of two or three specific carbon atoms by two/three connected aromatic rings. The
carbon-sharing rings lead to the formation of a virtually single-planed structure composed
entirely of carbon and hydrogen atoms (Neff, 1979). This planar structure allows for large and
highly-diverse molecules, which can be constructed with different numbers and positions of the
aromatic rings.
There are possibly hundreds of PAH compounds occurring in an extremely complex
mixture in the environment. For the purposes of this study, however, we restricted ourselves to
the sixteen parent PAH compounds listed by the US Environmental Protection Agency on its
priority pollutant list (the 16 US EPA). These compounds are among those which have been
frequently used for the purposes of environmental quality assessments. The base structures of
2
the sixteen parent compounds are composed of 2-6 aromatic rings with molecular masses
ranging from 128 Dalton to 278 Dalton (Fig. 1.1). They include naphthalene (NAPH),
acenaphthylene (ACYN), acenaphthene (ACEN), fluorene (FLU), phenanthrene (PHEN),
anthracene (ANTH), fluoranthene (FLA), pyrene (PYR), benzo(a)anthracene (BaA), chrysene
(CHRY), benzo(b)fluoranthene (BbFLA), benzo(k)fluoranthene (BkFLA), benzo(a)pyrene
(BaP), dibenzo(a,h)anthracene (DANTH), benzo(g,h,i)perylene (BPERY) and indeno(1,2,3-
c,d)pyrene (IPYR).
3
2001). PAH compounds are characterized by broad ultraviolet absorbance spectra. In addition,
most PAHs are fluorescent and emit light when excited, with the exception of acenaphthylene.
BPERY IPYR
Benzo(g,h,i)perylene Indeno(1,2,3-c,d)pyrene
C22 H 12 C22 H 12
MW=276,34 MW=276,34
Fig. 1.1. The molecular structures and masses of the 16 parent PAHs as listed in the US EPA priority
pollutant list. The structures are listed by the number of increasing ring groups (from 2 to 6 rings).
4
1.2. PAH contamination in the aquatic environments: background to
environmental problems
5
scientists, including the formation of dihydrodiol epoxide. This mechanism turns out to be the
most frequent pathway, which is often called the "bay region dihydrodiol epoxides pathway"
(Xue & Warshawsky, 2005). In this fashion, PAHs are oxidized by P450 enzymes in the initial
step in the activation process. This then produces reactive electrophilic metabolites which are
capable of interacting with cellular macromolecules, in particular with nucleic acids and
proteins. A review of the mechanisms of metabolic activation of PAHs exerting carcinogenicity
was provided by Xue & Warshawsky (2005).
Although it is still an area of intensive epidemiological study, toxicological profiles of
PAHs have already been introduced (e.g. ATSDR, 1995 see www.atsdr.crc.gov). The
International Agency for Research on Cancer (IARC), an institute within the World Health
Organization, has classified the carcinogenicity of individual PAH compounds in several of the
parent groups (Table 1.1.). This classification was based on the strength of evidence derived
from studies in humans and experimental animals (http://monographs.iarc.fr). However, even
those individual substances which could not be positively identified as carcinogens may act
synergistically (Wenzl et al., 2006). High molecular mass (HMW) PAHs tend to be more
carcinogenic, but less acutely toxic than their cousins with lower molecular masses (LMW).
Benzo(a)pyrene (BaP) in particular has revealed itself to be the most prominent carcinogen
(Group 1 of IARC) and is often used as a hazard index for PAH exposure (Bofetta et al., 1997;
Ravindra et al., 2008, Rappaport et al., 2004). However, even the LMW compounds like
naphthalene and acenaphthene have been shown to exert carcinogenic effects on animals and
may also carry potential risk for humans (Long et al., 1995; Rappaport et al., 2004).
As a consequence of increasing concentrations of PAHs in the environment, the
likelihood of human exposure could raise. Human exposure can occur through inhalation,
absorption/adsorption (skin), and ingestion (Bofetta et al., 1997; ATSDR, 1995). Inhalation and
skin contact have been proven to be important pathways for atmospheric PAH to enter the
human organism. Both of these routes of entry into the body are strongly related to specific
occupations, such as aluminum and coke production, coal gasification, iron and steel foundry
work, tar distillation, petroleum cracking, shale oil extraction, wood impregnation, roofing, road
paving and carbon production (Bofetta et al., 1997). However, ingestion through food and
drinking remains the most significant route for PAH contamination in humans. As much as 90%
of the total daily intake of persistent pollution compounds into the human organism could result
solely from diet (Binelli & Provini, 2004; Wenzl et al., 2006). In this context, animal food
sources play a significant role, particularly fish and seafood.
6
Table 1.1. List of priority PAHs and their carcinogenicity classification, water and sediment
quality guidelines (content in g/L for water and ng/g dry sediment weight).
Carcinogenicity Water Quality
Compounds Classification* Standard** Sediment Quality Guidelines***
(group) ERL ERM
Acenaphthene b,c,d 3 16 500
Acenaphthylene b,c,d NI 44 640
Anthracene a,b,c,d 3 0.006** 85.3 1100
Benz[a]anthracene b,c,d 2B 261 1600
Benzo[a]pyrene a,b,c,d 1 0.001e 430 1600
Benzo[b]fluoranthene a,b,c,d 2B 0.001e
Benzo[e]pyrene d 3
Benzo[g,h,i]perylene a,b,c,d 3 0.001e
Benzo[j]fluoranthene d 2B
Benzo[k]fluoranthene a,b,c,d 2B 0.001e
Chrysene b,c,d 2B 384 2800
Dibenz[a,h]anthrancene b,c,d 2A 63.4 260
Fluoranthene a,b,c,d 3 0.01** 600 5100
Fluorene b,c,d 3 19 540
Indeno[1,2,3-c,d]pyrene a,b,c,d 2B 0.001e
Naphthalene a,b,c 2B 0.01** 160 2100
Phenanthrene b,c,d 3 240 1500
Pyrene b,c,d 3 665 2600
a
EU WFD, 2000/60/EC in Annex X (http://europa.eu/scadplus/leg/en/lvb/l28108.htm);
b
the US EPA (http://www.epa.gov/epaoswer/hazwaste/minimize/chemlist.htm);
c
NPI Australia;
d
Canadian NPRI Substance 2007;
e
Priority & hazardous substances based on the decision # 2455/2001/CE of the European Parliament
* IARC: http://monographs.iarc.fr/ENG/Classification/index.php. Group 1: Carcinogenic to humans; Group 2A: probably
carcinogenic to humans; Group 2B: possibly carcinogenic to humans; Group 3: not classifiable as to carcinogenicity to humans;
Group 4: probably not carcinogenic to humans;
** Maggi et al 2008;
*** adopted from Long et al., 1995: ERL= the effects range-low, ERM= the effects range-median
NI = information not available
7
It has been suggested that the higher the trophic level, the more and various food types are
consumed. As a result, higher trophic levels are more susceptible to pollutant magnification.
However, in aquatic systems benthic organisms such as mussels and clams accumulate more
PAHs than the carnivorous fish which use these organisms as prey. Mart-Cid et al. (2007)
found that shellfish (mussels & clams) and shrimp can contain higher concentrations of PAHs
than fish such as tuna, mackerel and salmon, due to a low capacity to biotransform
contaminants. Physiologically, mollusks do not metabolize PAHs as quickly as fishes. Instead,
they tend to accumulate these toxins.
Bioconcentration/biomagnification is determined by bioavailability of the compounds in
the water phase. Low molecular mass PAHs (those with 2-3 rings) indicated high levels of
bioavailability in benthic organisms such as mussels and clams when compared to high
molecular mass compounds (e.g. Baumard et al., 1999a; Baumard et al., 1999b; Kayal &
Connell, 1995). This is due to the fact that those compounds are highly water-soluble. On the
other hand, HMW PAHs (4-6 rings) have been proven to be relatively non-bioavailable when
compared to the lighter compounds. Baumard et al. (1998) found low concentrations of heavier
PAHs in mussel, despite bottom sediments containing high levels of various pyrogenic-PAHs.
Thorsen et al. (2004) observed that petrogenic PAHs are more bioavailable than pyrogenic
PAHs.
However, the bioavailability of the compounds is also determined by water and sediment
properties i.e. organic matter content, SPM and sediment grain-size. Organic matter found in
both water and sediment affects the bioavailability of PAHs to a large extent. One notable
review of the effects of dissolved organic matter (DOM) on the bioconcentration of several
organic contaminants (PAHs, chlorinated hydrocarbons, and TBT) in aquatic organisms,
including water fleas, mussels, amphipods and fish, was given by Haitzer et al. (1998). The
authors reviewed the lack of bioavailability of DOM-bound chemicals, which would in turn lead
to a decrease in their bioaccumulation. However, at low level of DOM (~10 mg/L),
bioconcentration of pollutant could be enhanced up to 300% (Haitzer et al., 1998). Moreover,
the extent to which DOM affects PAHs is further determined by factors including the quality
and quantity of DOM, the contact time between humic substances and the chemicals before
exposure, and the overall exposure time. Data might therefore differ from place to place
according to environment-specific characteristics.
Further factors such as the presence of suspended particulate matter and the fineness of
sediment grain-sizes are also important for the bioaccumulation of organic pollutants, especially
in filter/suspension-feeding and detritivorous organisms such as bivalves. Baumard et al. (1998)
found a significant bioconcentration of PAHs on organisms living in close contact with
sediments compared to carnivorous organisms. The latter might be exposed to a much lesser
extent to sedimentary particles. Menon & Menon (1999) found in a 10-day experiment that the
8
bioaccumulation of PAHs in clams exposed to sediment in suspension increased almost two-
fold when compared to clams tested in undisturbed sediments. This indicates that higher
sediment levels in aqueous suspensions can result in an increased PAH content in the
surrounding water. Such conditions are important in dynamic systems such as those found in
rivers, estuaries and coastal waters. High turbidity should be expected to increase the
concentration of carcinogenic, high molecular weight PAHs in benthic organisms (e.g. Baumard
et al., 1999b). Such benthic invertebrates are important prey (food) for many carnivorous fishes.
Therefore, increased bioaccumulation can also be extrapolated for higher trophic levels of
organisms found in the food webs of these aquatic systems.
9
compounds (>4 rings). The latter are more recalcitrant when it comes to undergoing chemical
changes (Juhaz & Naidu, 2000). However, a great deal of research has confirmed the microbial
degradation in sediment-bound PAHs. Xia et al. (2006) concluded that an increase in the
population of PAH-degrading bacteria and desorption of PAHs from the solid phase increases
the rate of contact between PAH and bacteria. This can subsequently enhance biodegradation
rates. Some of PAH-degrading bacteria are mentioned in the work of Samanta et al. (2002).
However, it is important to note that biodegradation is generally a relatively slow process
(Mnnist et al., 1996).
In addition to being used as indicators for anthropogenic pollutants, the presence and
amount of PAHs often serve as measures for estimating overall environmental quality. This
includes factors such as the degree of toxicity (e.g. Bihari et al., 2006; Cachot et al., 2006),
environmental and human health risk assessment (e.g. Galloway 2006) and petroleum pollution
(e.g. Requejo et al., 1996).
In conclusion, PAHs are regulated not only for food and drink, but also for environmental
aspects, due to their toxicity and carcinogenic properties, confirmed bioaccumulation and
biomagnification and their persistence over longer periods of time. Examples of legal directives
regulating PAHs are: the European Union Water Framework Directory (the EU WFD,
2000/60/EC in Annex X), the US EPA list of priority pollutants, the National Pollutant
Inventory (NPI) for Australia, and the European Scientific Committee on Food (2002) (see
Stolyhwo & Sikorski, 2005). Despite these efforts, PAHs have still not been specifically
mentioned in the list of twelve POPs (Persistent Organic Pollutants) under the Stockholm
Convention, which has so far been signed and ratified by more than 150 countries including
Indonesia (http://chm.pops.int/).
10
magnitude of chemicals found in aquatic systems. These sources become especially important
for aquatic systems in regions where economic development has been significantly and rapidly
taking place, areas of the world such as Southeast Asia. Accordingly, the presence of pollution
in the rivers, estuaries and coastal waters of these regions represents one of the key
environmental challenges facing humanity today. Schwarzenbach et al. (2006) estimated that
anthropogenic fluxes of organic pollutants stemming from fertilizers, pesticides, synthetic
organic chemical productions and accidental oil spills annually contribute ca. 450 million tons
worldwide to aquatic systems.
Scientists have established the global significance of the rivers draining southern Asia,
which flush large amounts of terrestrial materials into the world ocean. On a global scale, recent
estimation of the annual total sediment load flowing from rivers into the global ocean is ca. 20
Gigatons, suspended sediment load contributes 90%, and the rest is mainly from bed sediment
load (Syvitski et al., 2003).
Asia and Oceania are the largest producers of fluvial sediment, with around 70% of the
overall annual sediment loads coming from these regions (Milliman et al., 1999). In comparison
with the globe's largest landmasses, including Africa, Asia, Europe, North America, and South
America, the region containing Oceania and Indonesia produces the world's highest sediment
yield, as defined in terms of sediment load divided by total drainage area (Syvitski et al., 2005).
In fact, these two regions accounted for ca. 800 and 543 tons of sediment per square kilometer
per annum, respectively. Milliman et al. (1999) pointed out the particular importance of the
rivers in Sumatra, Java, Borneo, Sulawesi, Timor and the New Guinean islands (Fig. 1.2). They
estimated that these six large islands alone significantly discharge about 4.2 Gt of sediment per
year, despite the fact that they constitute only 2% of the world's total land area which drains into
the global ocean. The rivers located on these islands are responsible for about 20-25 % of global
sediment export. Sumatra alone contributes 498 Megatons through fluvial transport per annum,
an amount which makes it the second largest source in this group of six islands (Milliman et al.
1999). Even though some of the larger river basins in Sumatra such as the Siak, Kampar,
Rokan, Indragiri and Batanghari might not have been included in the above-mentioned
calculations, further estimates suggest that the sediment volumes are substantial.
Most of rivers and estuaries in the eastern coast of Sumatra drain large area of peatland
which are characterized by high humic substance of black water masses. Therefore, the
environmental state of the tropical peatlands has attracted a big concern for pollutant transport
and climate change. Page et al. (2002) reveal that the stability of tropical peatlands is
particularly relevance for the climate change because these peatlands are one of the largest near-
surface reserves of terrestrial organic carbon estimated for ca. 26 50 Gt. They also remain that
persistence environmental change in the tropical peatlands owing to drainage and forest clearing
have threaten the stability of ca. 20-m thick of peat deposit, and make the peatlands being
11
susceptible to fires. In Indonesia, peatland fires have long been an environmental problem (see
section 1.3.2. for further explanation). The worst peatland fire episode occurred during severe El
Nio event (1997/1998) damaging of ca. 6.8 Mha (or 34%) of Indonesia peatland, and emitted
up to 2.57 Gt Carbon in 1997 (Page et al., 2002). It is relatively similar to the global net
emission of CO2 from land-use change was recently estimated for 2.4 Gt y-1 (IPCC, 2000). The
environmental and health effects of the haze and smoke had been widely recognized ever since
(e.g. Langmann et al., 2007; Fang et al., 1999; Parameswaran et al. 2004). Of particularly
important is that the peatland fires are mostly anthropogenic as part of land clearance activities
before establishing crops (Page et al., 2002).
Unfortunately, the magnitude of organic pollutants, particularly that of PAHs the
burning by products - found in Indonesia's rivers, estuaries and coastal areas has only been
superficially evaluated at best. To date there have been no long-term or in-depth studies carried
out, especially ones covering extremely large surface areas or multiple islands in this region.
Nevertheless, the significance of organic pollution fluxes stemming from Indonesian rivers can
be assumed to be directly proportional to the significance of material fluxes previously
mentioned by the above literature sources. It is therefore reasonable to assume that increasing
levels of "flushing out" SPM from these river systems will eventually contribute to an increase
in the magnitude of pollutants in the coastal zone, given that suspended particulate matter
(SPM) is a significant carrier for most organic pollutant such as PAHs (e.g. Kayal & Connell,
1989; Ollivon et al, 1995; Deng et al., 2006; Law et al., 1997; Fernandes et al., 1999; Heemken
et al., 2000; Witt & Siegel 2000; Kowalewska et al., 2003; Ross & Oros, 2004 and Cao et al.,
2005), polychlorinated biphenyls (PCBs) (e.g. Mai et al., 2002; Telli-Karako et al., 2002),
polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) (e.g.
Ishaq et al., 2003). The coastal zone of Sumatra can thus be viewed as being very susceptible to
organic contaminants. Conversely, dissolved organic matter such as dissolved humic substances
has been shown to enhance the solubility of dissolved PAHs in aqueous solution (e.g. Liu &
Amy, 1993). The implication of this additional factor is that the residence times of PAHs in the
aqueous phase will be increased, which in turn promotes more far-reaching transport towards
and into the open ocean. The relevance of Sumatran rivers, which often drain peat bogs and
other humic soils, for the transport of dissolved organic matter into the open ocean has already
been recognized (e.g. Baum et al., 2007).
12
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Fig. 1.2. Sediment discharge (106 T y-1) from the six East Indies islands. Arrow widths are proportional to
the annual load. The letters S, J, B, C, T and NG refer to Sumatra, Java, Borneo, Sulawesi (Celebes),
Timor and New Guinea, respectively. Shaded areas represent water depths of less than 1000 m, although
most of these areas are in less than 100 m of water depth (adopted from Milliman et al., 1999).
13
mainly drain large areas of low-laying land characterized by widespread peat swamps, which
are scattered among various landscapes, including huge palm-oil plantations, forests and
secondary swamp-forests. These areas account for ~53%, ~23%, and ~11% of catchment land-
use coverage, respectively (BPDAS, 2004). The main river correspondingly receives large
amounts of water input stemming from smaller channels and tributaries along its course.
Moreover, the main river basin is sparsely inhabited. It nevertheless drains some highly-
urbanized centers, such as the Riau Province capital of Pekanbaru, the smaller city of Siak Sri
Indrapura, a pulp-paper industry estate located in Perawang, and an oil refinery in the Siak river
mouth, thus making it inevitable that urban and industrial discharges will enter the river's water.
The Siak River and its estuary dump their waters in the coastal channel located between
Bengkalis Island and the Sumatra mainland.
Adjacent to the Malacca Strait, the coastal areas are constricted and range from Dumai
City in the northwest of the River down to the Selat Panjang channel in the southwest. The
coastal waters are characterized by observable plumes of suspended particulate materials. These
plumes stem mainly from the Siak River and some other neighboring rivers (such as the Rokan
and Kampar River in the northwest and southwest, respectively) and many smaller streams
emerging along the coast (Fig. 1.5.). The Siak River plume is caused by dark-colored peat
materials and stands out distinctively from the plumes of other rivers. The Siak's current pushes
river water through the channel and into the Malacca strait during the low tide. Its plume pulls
back during high tide. The tide is semi-diurnal, meaning that two high tides and one ebb tide
occur during one day, however, the high tides arrive with differing magnitudes. Unfortunately,
there is no information available on the residence times of the coastal water masses.
14
MALAYSIA
Riau Coast
Bengkalis Island
Siak Estuary
Siak River
Riau Province,
Sumatra, INDONESIA
Fig. 1.3. An overview map of the Siak river mouth (satellite image provided by H. Siegel (2004), Baltic
Sea Research Institute (IOW) Warnemuende, Rostock, Germany). The Siak River stretches over ca. 300
km up to the estuary (the mouth). The coastal areas extend to far northwest of the mouth and to southwest
of the coastal channel between the offshore islands and the Sumatra mainland.
A B
Fig. 1.4. (a) Surface runoff of organic-rich black water from a small waterway entering the Siak River
around a palm-oil plantation, (b) typical small water channel found in the estuary. These are typical water
inputs feeding the Siak River (source: courtesy of SPICE).
15
Rokan River Siak Estuary
Siak River
Sumatra,
INDONESIA Kampar River
Fig. 1.5. Plumes of SPM and dissolved humic material from several rivers: the Rokan, Siak and Kampar
River (as seen from northwest to southwest) into the Malacca strait. At low tide the plume is flushed
outwards by the Siak River and at high tide it is pushed backwards. Image from H. Siegel (2004), Baltic
Sea Research Institute (IOW) Warnemuende, Rostock, Germany using MODIS Terra, Data: NASA-RRS.
With regards to PAH pollution, there are two potential sources which have their roots in
the expanding economic development of the Province. Riau is well-known for its oil production
industry. Oil-related facilities such as various plants, refineries and ridges are scattered all along
the river, the estuary and coastal areas (Fig. 1.5). Oil spills might appear along the Siak River,
the estuary and the coast, and most likely stem from boats, oil-transporting vessels, harbor
facilities, and many other petroleum-related activities.
Fig. 1.6. Some oil-related activities observed in the studied areas. Refineries are mainly located in the
coast of Dumai city (left), ridges (middle) in the channel (Panjang Strait), and typical port activities in the
Siak River (source: courtesy of SPICE).
16
Moreover, oil industries can also be found in surrounding areas of two neighboring
countries, Malaysia and Singapore (the biggest oil refinery center in Asia). Malacca Strait is
likely destined to become one of the busiest straits in the world, one which is highly susceptible
to oil pollution. Zakaria et al. (2000) found that oil pollution levels detected in the Strait were
due mainly to spillage (through accidents or routine tanker operations such as ballast-water
discharges) from the tens of thousands of vessels transporting crude oil and other petroleum
products.
The region's second-largest industry, plantations for palm-oil production, covers more
than 50% of the total catchment area. The studied areas were affected by high levels of organic
material combustion, in particular anthropogenic, slash-and-burn agriculture and intense
instances of naturally-occurring forest and swamp fires. Especially important for this region is
the documented fact that uncontrolled agricultural burning for purposes such as land clearing
has worsened overall air quality for over a decade.
Fig. 1.7 shows the trend of hotspots from 1996-2006 and Fig. 1.8 shows an example of a
daily hotspot distribution. Data was extracted from the hotspot daily observation provided by
the Indonesian Ministry of Forestry (www.dephut.go.id). Elevated numbers of hotspots were
observed during the severe El Nio event of 1997-1998. It is not to extrapolate that the numbers
of hotspots correlated directly with El Nio, because high numbers have also occurred during
2005 and 2006, which did not fall under the pronounced effects of El Nio. Severe burning
happening during 1997/1998 resulted in a strong impact on the distribution of aerosols over
Sumatra and the neighboring counties (e.g. Fang et al., 1999) and the effects even reached into
the Indian Ocean. Parameswaran et al. (2004) observed a large aerosol plume which formed
over the eastern equatorial (5oN to 10oS) and eventually reached 60o E latitude during
September-November of 1997. This plume was directly tied with the large-scale fires occurring
in Southeast Asia, particularly Indonesia, at the time of a severe drought caused by an El Nio
event. Unfortunately, the observed number of annual hotspots has remained at a level of >3000
ever since then and has recently become even worse. The occurrence of agricultural burning is
most likely during the dry season, the period between March and September. Nonetheless, (as
can be seen in the Fig. 1.7b), large numbers of hotspot have been observed even in the assumed
rainy season. This is to say that forest and swamp fires, added to uncontrolled agricultural
burning, are potentially the largest source of PAH contamination in the studied areas.
17
A
20000 18645 18959
18000 17090
16000
Numbers of hotspot observed
14000
12000 13711
10000 9360
7587
8000
7323
7818
6000
6077
4000 4865
El Nio 3780 SPICE
2000
Sampling
0
1996 1997 1998 1999 2000 2001 2002 2003 2004 2005 2006
6000 >9000
5000
number of burning hotspot
4000
1997
2002
3000
2004
2000 2005
2006
1000
0
May Jun Jul Aug Sep Oct Nov Dec Jan Feb Mar Apr
Fig. 1.7. (a) The number of hotspots (forest/swamp/agricultural fires) observed over the period from
1996-2006 in Riau Province. (b) Monthly distributions of hotspots for selected years. Unexpected raised
number of hotspots during wet season was observed in 2002 and 2005. (Data were extracted from
PUSDALKARHUTLA Riau Province for 1996-2001; and DEPHUT online publications for 2003-2006,
which were calculated from daily available information: www.dephut.go.id).
18
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Fig. 1.8. An example of daily observation of hotspot distribution, provided by the ministry of Forestry
Indonesia (image source: www.dephut.go.id ). This picture shows intensive burning (red dots) around the
catchment areas of Siak River, estuary and some other rivers on June 19th, 2004.
19
II. SOURCES, DISTRIBUTION AND FATE OF PAHs IN AQUATIC
COMPARTMENTS: A SHORT REVIEW
2.1. Introduction
This chapter briefly reviews and elaborates upon various aspects of PAH sources,
distributions and fates in an aquatic environment. The sources are grouped around the PAH
formation process, magnitude, and composition with respect to the unsubstituted PAH
compounds and their alkyl homologues. This review focusses on PAH genesis which is related
to anthropogenic processes (mainly combustion), rather than discussing natural, early diagenetic
processes. This is because the former is the primary subject of this study. A comparison of
various anthropogenic sources, including their composition, is also provided for the 16 PAHs
defined by the US EPA priority pollutant list (hereafter called PAH16). Distribution of PAHs in
the aquatic environment is discussed based on their existence in sediment, suspended particulate
matter and water solution, whereas the fate of PAHs is elaborated upon based on their solid-
water phase partitioning.
PAHs in aquatic environments stem from a wide range of natural and anthropogenic
sources. The latter is of serious concern to humans, due to the fact that PAHs are by-products of
literally hundreds of different combustion processes from human civilization. These range from
residential heating systems to industrial processes like power generation, incineration,
manufacturing, agricultural burning and petroleum combustion for transportation, among many
others (e.g. Kakareka & Kukharchyk, 2003; Conde et al., 2005; Westerholm et al., 1992;
Zielinska et al., 2004; Yang et al., 2007). Recent global estimates of the atmospheric emission
of PAH16 substances in 2004 (520 Gg per year) showed that biofuels (56.7%), wildfires (17.0%)
and consumer product usage (6.9%) were the three most important sources (Zhang & Tao,
2009). In addition, such PAHs can be delivered into the environment from direct petroleum
discharges and spillages (e.g. Requejo et al., 1996).
PAHs stem from organic matter and are primarily constructed through three major
transformation processes: 1) rapid, early diagenesis ("natural" PAHs), 2) incomplete, high-
temperature combustion ("pyrogenic" PAHs), and (3) catagenetic geological alterations which
result in petroleum ("petrogenic" PAHs).
20
PAHs mainly refer to those substances resulting from the early diagenetic processing of
biogenic precursors (also called "diagenic" PAHs). The term "early diagenetic processes" refers
to any chemical, physical or biological post-depositional transformation which changes a
biogenic precursor over a relatively short-geological period (Berner, 1980; Libes, 1992). These
PAHs are limited to few groups of compounds which are derived mainly from terpenes, steroids
and pigments via aromatization processes. Wakeham et al. (1980a) observed five common
groupings of natural PAHs that occur in sediments: 1) a series of tetra- and pentacyclic PAHs
derived from pentacyclic triterpenes of the amyrin type, 2) tetra- and pentacyclic PAHs
stemming from pentacyclic triterpenes with five-membered E-rings (see Fig. 2.1), 3) retene and
pimanthrene with diterpenes as their parent materials, 4) an extended series of phenanthrene
homologues, and 5) perylene. These PAHs are commonly used for identification of natural
PAHs in the sediment (e.g. Lipiatou & Saliot, 1991; Silliman et al., 1998). Fig. 2.1 shows an
example of the transformation of triterpenoids precursors such as lupeol (five-membered E-
rings) and -amyrin (six-membered E-rings) into pentacyclic hydrocarbons by A-ring cleavage
and aromatization proposed by LaFlamme & Hites (1979). The natural PAHs occur mostly in
the form of alkyl homologues, and can also be intermediates in diagenetic transformations. For
example, simonellite (1,1,-dimethyl-7-isopropyl-1,2,3,4-tetrahydrophenanthrene) is an
intermediate compound which results from the diagenetic transformation of higher plant
diterpene abiatic acid into retene (Wakeham et al., 1980b).
These PAHs are primarily enriched in deeper, anoxic sediments, indicating a distinct
vertical profile when compared to anthropogenic PAHs. Siliman et al. (1998) distinguished
between natural PAHs, i.e. perylene, and other anthropogenics found in Lake Ontario in three
ways. First, the concentration of perylene in the surface sediment was significantly lower than
those for other anthropogenic PAHs. Second, the perylene concentration peak is found at an age
much older than the earliest industrial times. Third, concentrations of anthropogenic PAHs were
close to zero in sediment layers laid down before 1900. This kind of profile has also been
recognized in many studies performed in widely differing locations (e.g. Wakeham et al.,
1980a; Jiang et al., 2000).
21
A B
Fig. 2.1. A hypothetical aromatization scheme for natural precursors: (a) -amyrin, (b) lupeol (adopted
from LaFlamme & Hites., 1979).
22
heavy molecular weight PAHs (500 1000 Da), 2) nucleation or inception of nascent soot
particles (ca. 2000 Da, effective 1.5 nm), 3) particle mass growth due to the addition of gas
phase molecules including PAH radicals and 4) coagulation involving reactive particle-particle
collisions.
Fig. 2.2. Proposed mechanism of pyrosynthesis starting with ethane (adopted from Ravindra et al., 2008).
The production of PAHs is closely related to soot formation. Bockholn (1994) previously
proposed a schematic concept for the production of PAHs in which they were actually
precursors for soot and black carbon formation (Fig. 2.3). In principle, Bockholn's scheme
includes the aforementioned pyrolysis and pyrosynthesis processes of an organic fuel. This
results in small hydrocarbon radicals being created, from which acetylene (C2H2) is formed
under fuel-rich conditions. These radicals grow and form aromatic rings. Subsequently, the
formation of larger aromatic rings occurs when a surplus of acetylene molecules is present.
Formation of black carbon results from the coagulation of larger aromatic structures which form
primary soot particles. The growth of black carbon in size and its increase in concentration are
determined both by coagulation (which switches the molecular-length scale into the
macroscopic, particle dimension) and surface growth (which snatches molecules out of the gas
phase), respectively. In this respect, coagulation is responsible for the highly irregular,
disordered structure of soot particles.
At the onset of black carbon formation, the concentrations of PAHs in the flame would
therefore be reduced (Lima et al., 2005). But not all PAHs are transformed into soot particles, as
is evidenced by considerable amounts of PAH residues remaining in both the gas and particulate
phases, and/or adsorbed directly onto the black carbon itself (e.g. Butler & Crossley, 1981;
Koelmans et al., 2006).
23
Fig. 2.3. A conceptual picture proposed for soot formation in homogeneous mixture (adopted from
Bockhorn, 1994).
24
fractions (Yan et al., 2004). Likewise, biomass fuels - in particular wood - also contain high
percentages of aromatic ring components (as polyphenolic compounds in lignin). Phenol
compounds are potential precursors for PAHs (Sharma & Hajaligol, 2003). In addition, aromatic
fuels (represented by benzene) have been observed to emit PAH compounds up to 100 times
larger than those produced by aliphatic ones (acetylene) under the same burning conditions as
reviewed by Richter and Howard (2000). On the other hand, petroleum - which is largely made
up of aliphatic structures will produce low weight PAH16 compounds upon combustion as
compared to the other groups.
High temperature (plus oxidant level) decreases the overall emissions of PAHs (e.g.
Jenkins et al., 1996). Pyrogenic PAHs can be formed in a wide range of temperatures, stretching
from relatively low (ca. 300oC) to high (~1000oC), depending on how condensed the structure
of the precursors is. The more solid the precursors, the higher the temperature needed to crack
the precursors. Several studies have attempted to calculate a scale showing the optimal
conditions under which PAHs are produced. For example, a pyrolysis of cellulose (vegetation)
to produce PAHs occurs optimally between 300 650oC (McGrath et al., 2003). Combustion of
paper emits maximal PAHs at ~300oC (Yang et al., 2005). Neff's review (1973) showed that the
PAHs produced in the series of compounds from naphthalene to coronene are optimally
generated at 780oC. Bituminous coal combustion was shown to release an optimal emission of
PAHs at 800oC (Liu et al., 2000). McGrath et al. (2001) observed that increasing the burn
temperature from 800 to 850 oC lead to significant increases in PAHs resulting from burning
chlorogenic acid and cellulose; beyond this temperature the emission decreased. Khalfi et al.
(2000) observed that PAHs are optimally emitted from wood waste incinerators at 900 - 954 oC.
Jenkins et al. (1996) observed from the experimental burnings of biomass (wood and cereals)
that the magnitude of PAH emission depends also on the flame type. They found that fewer
PAHs are emitted in a vigorous flame, whereas the levels produced were much higher in both
smoldering stages and less robust flames.
25
10000
Emission Factor of PAHs
1000
PAH16 (mg/Kg)
100
10
1
Coal Biomass Petroleum
Combustions Burnings Combustions
Fig. 2.4. Emission factors for the 16 PAHs on the EPA's priority list. Results taken from the combustion
of various organic matter classified as coal, biomass or petroleum. Data were evaluated from various
literature sources (see Appendix 2.1. for details to the references).
26
characterizes different sources. In addition, the literature data from Sumatra's peatland burning
episode in 2005 (mean values, after See et al., 2007) is also presented for a comparison. These
figures are particularly important, since they provide information on the conditions in the area
where this study took place.
The results shows that the compositions of PAH16 stemming from pyrogenic sources is
relatively similar with respect to high levels (>30%) of naphthalene (NAPH) and low levels
(<5%) of high molecular weight compounds (Fig. 2.5a). This suggests that all biomass, coal and
petroleum combustions emit a significant amount of naphthalene. This is particularly true in the
case of petroleum combustion, in which NAPH comprises roughly 65% of the emitted PAH16.
However, the ring-group composition shows a different pattern for petroleum and biomass-coal
combustion, particularly in their relative compositions of 2 and 3 ring compounds (Fig. 2.6.a).
The decreased levels of 3-ring groups from petroleum combustion is due to a lack of
acenapthylene (ACYN) and acenaphthene (ACEN) produced. In contrast, the high levels of 3-
ring PAHs for biomass and coal combustion are mainly caused by phenanthrene (PHEN) and
acenaphthylene (ACYN). Within the biomass group, wood burnings emit more ACYN than
grass burnings (Fig. 2.5b). Therefore, the relative compositions of the 2- and 3-ring groups can
probably be used to distinguish between petroleum and biomass-coal combustion simply by
comparing the mass ratios of these ring groups. As far as ring-groups are concerned (Fig. 2.6a),
the patterns emitted by biomass and coal combustion are quite similar, thus making it quite
difficult to differentiate between them. Therefore, the composition of individual compounds
such as fluorene (FLU), fluoranthene (FLA) and pyrene (PYR) and most of the other high
molecular weight compounds can be used as additional clues during separation, due to their
unique signatures and patterns. For example, the ratio of the relative composition of FLA to
PYR for biomass burnings is three-fold higher than that of coal combustion. Therefore, any
mass ratio between those compounds can be developed to help provide clues for source
differentiation.
In comparison to biomass burnings, Fig. 2.5b shows the relative compositions of
individual PAH compounds between two distinct locations. Dumai and Pekanbaru (the capital
city of Riau province) were affected by the tremendous volumes of smoke stemming from
peatland burnings in 2005. It shows that Sumatran peatland burnings emit less NAPH and
ACYN. The relative composition of the PAH16 between Dumai and Pekanbaru is also
significantly different. This is particularly true for the composition of PHEN, ANTH, PYR, as
well as benzo(b)fluoranthene (BbFLA), benzo(k)fluoranthene (BkFLA), benzo(a)pyrene (BaP),
dibenzo(a,h)anthracene (DANTH), and indeno(1,2,3-c,d)pyrene (IPYR). Although there is only
a brief discussion on the composition of PAH16 provided here by the authors, the evidence
suggests that PAHs derived from the peatland smoke experienced alterations due to
27
decomposition or additions from local sources. This data can therefore be a useful aid in
comparison for PAH assessments in aquatic systems of those particular studied areas.
A B
35 65,1% Pyrogenic PAHs 40
Biomass Burnings
Relative Composition (%)
C
35 Sumatra Peatland Burnings in 2005
Relative Composition (%)
30 Dumai
25 Pekanbaru
20
15
10
5
0
Fig. 2.5. Relative composition of 16 individual PAHs of the EPA priority list from (A) common
pyrogenic sources including coal, biomass and petroleum combustion (median values) (see Appendix 2
for references); (B) a subset of biomass burning sources comprising wood and grass burnings; and (C)
Sumatra peatland burnings (mean values, after *See et al., 2007). Note: the y-axis for graph A and B is
different.
A B
80 80 Sumatra Peatland Burnings in 2005*
Pyrogenic PAHs
70 70
Relative Composition (%)
Biomass Dumai
60 60
Burnings
50 50
Pekanbaru
Coal
40 Combustions 40
30 Petroleum 30
20 Combustions 20
10 10
0 0
2 rings 3 rings 4 rings 5 rings 6 rings 2 rings 3 rings 4 rings 5 rings 6 rings
Fig. 2.6. Relative composition of the ring groups of the 16 PAHs on the EPA priority list from (A)
common pyrogenic sources including coal, biomass and petroleum combustion (median values) (see
Appendix 2 for references); (B) Sumatra peatland burnings (mean values, after *See et al., 2007).
28
2.2.3. Petrogenic PAHs
PAHs are substantial components of crude oil and its petroleum products. They are
considered to be the toxic fraction. Components of petroleum hydrocarbons are generally
grouped into four class: the saturates (n- and branched-chain alkanes and cycloparaffins), the
aromatics (mono-, di-, and polynuclear aromatic compounds containing alkyl side chains and/or
fused cycloparaffin rings), the resins (pyridines, quinolines, carbazoles, thiophenes, sulfoxides,
and amides), and the asphaltenes (extended polyaromatics, naphthenic acids, suifides,
polyhydric phenols, fatty acids, and metalloporphyrins) (Sugiura et al., 1997; Leahy & Colwell,
1990). The other significant components of the aromatic hydrocarbons found in petroleum are
monoaromatic (single-ring) compounds including Benzene, Toluene (or methylbenzene),
Ethylbenzene and Xylene (all isomers of dimethylbenzene), or so-called BTEX. PAHs and
BTEX are two aromatic components which are generally used to identify and characterize
sources of petroleum, in particular PAH compounds (Wang et al., 1999).
The aromatic fraction varies among different types of crude oil, but it can reach up to
50% of the total weight of the petroleum. Neff (1979) published a review showing that the
aromatic content of mineral oils varies from 7 % 34 %. Ryder et al. (2002) reported that
aromatic values ranged from 18% to 41% for BP crude oil samples. Heavy oil fuel transported
by the sunken tanker Prestige consisted of 50% aromatic hydrocarbons (Saco-lvarez et al.
2008). However, PAHs normally make up a more modest part (up to 20%) of the overall
aromatic fraction. Requejo et al. (1996) calculated that PAHs constituted somewhere between
1% and 20% of the total C12+ aromatic fraction in various marine crude oils. Stated otherwise, if
we assume PAHs to be roughly 20% of the aromatic fraction (which is about 50% of the
petroleum), the total PAH fraction in the oil would only be about 10% of the mass. However,
PAHs are in fact found to be largely variable in different sorts of petroleum, reaching values of
up to 13%. For instance, Neff (1979) found that the total tri- to hexacyclic PAHs varied only
from 0.2 - 7.4%, while Requejo et al (1996) estimated that PAHs constitute up to 12.9% of oil
originating from three marine source rocks: carbonates, marine shales and fluvio-deltaic oils.
Therefore, any oil spills which occur would add significant amounts of PAHs to the aquatic
environment.
In contrast with pyrogenic origins, the composition of petrogenic PAHs is notably
characterized as having an abundance of alkyl-homologue PAHs (substituted) as compared to
the parent (un-substituted) forms (Youngblood & Blumer, 1975; Lafamme & Hites, 1978; Neff,
1979). This abundance of alkylated PAHs is due to lower formation temperatures during the
catagenic process, which takes place over geological periods. Alkyl-substituted PAHs may
comprise 80 90% of the total PAHs in crude oil (Saravanabhavan et al., 2007) and be used for
chemically fingerprinting the source of PAHs in oil spills (e.g. Boehm et al., 1997). Wang et al.
(1999) reviewed oil spill identification attempts, showing that the ratios between the total of 3-6
29
ring parent PAHs and the total alkylated PAH homologues were 5%. This data was drawn
from PAH analysis performed on over 60 different crude oils and petroleum products, including
Arabian crude oils, California oils, UK Brent oil, Alaska Cook Inlet 1-3, Iranian Heavy oil,
Russia Komi, Norway Statfjord Oil, Terra Nova, jet fuel, diesel, Bunker C and many others.
Fig. 2.7 shows a typical bell curve distribution for alkyl homologues relative to their
parent compounds in several types of oil (adopted from Wang et al., 1999). The alkyl group
substitutes range mostly from one (methyl-) to four (tetraalkyl-) carbon atoms, often denoted as
C1-C4. In most cases, the degree of alkylation is presented as the sum of all isomers
corresponding to a given level of alkylation (total C1, total C2, and so on). For example, total
C2-fluorene is the sum of all possible isomers including 1-Ethylfluorene, 1,2-Dimethylfluorene,
1,5-Dimethylfluorene, and 1,6-Dimethylfuorene. Alkyl group substitution is usually used to
distinguish the petroleum sources for PAHs, including (C1-C4)-naphthalenes, (C1-C3)-
fluorenes, (C1-C4)-phenanthrenes, (C1-C3)- dibenzothiophenes, C1-fluoranthene/pyrene, and
(C1-C4)-chrysenes (Wang et al., 1999). However, the level of alkylation is often represented
differently in different studies. Some apply only a few, limited alkyl homologues, which
effectively turn out to be the same as total C1, C2 and so on. Due to this, the degree of
alkylation should be carefully interpreted to avoid mistakes in classification.
The composition of the PAH16 compounds is quite different between crude oil and oil
spills from tanker accidents (Fig. 2.8). The main differences are that the crude oils are
dominated by NAPH, while 46 ring compounds in crude compose only relatively small
percentages. Wang et al. (1999) found that naphthalene and its alkyl-homologues (C1-C4)
comprised up to 86% of total PAHs in Diesel No.2 and up to 99% in Jet B fuel. In contrast, oil
spills experience increasing compositions of primarily 4-ring compounds. It is most likely that
oil spills evidence contamination by pyrogenic PAHs. For example, Wang et al (2004)
demonstrated a clear signature of pyrogenic PAH input in the Detroit oil spills of 2002. These
pyrogenic inputs were attributed to combustion and motor lubrication processes. The lube oil
tested in the samples was waste lube oil.
30
homologues Bell Shape distribution
Fig. 2.7. An example of a bell-shaped distribution (red dashed line): alkylated homologues PAHs and
other EPA priority PAHs in ASMB crude, three oil products, and a tarball sample from British Columbia
(adopted and modified from Wang et al., 1999).
A B
80
30 55,5% Petrogenic PAHs
70
Relative Composition (%)
Relative Composition (%)
25 60
Oil Spills Oil Spills
20 50
Crude Oil**
Crude Oil** 40
15
30
10
20
5 10
0 0
2 rings 3 rings 4 rings 5 rings 6 rings
Fig. 2.8. Relative composition of (A) the individual and (B) the ring groups of the 16 PAHs of the EPA
priority from petrogenic sources including oil spills and crude oils. The crude oil data represents mean
values (after ** Requejo et al., 1996).
31
2.2.4. Source Apportionment
This section elaborates the source apportionments of anthropogenic PAHs based on
molecular weight ratios and isomeric ratios. Source apportionment of anthropogenic PAHs in
the aquatic environment is very challenging. This is due to that fact that anthropogenic PAHs,
particularly those of unsubstituted compounds, coexist with substances from various sources.
Also, the relative composition of the individual PAHs experience transformation processes such
as photo-oxidation and oxidation leading to changes in pattern from sources to pools (Soclo et
al., 2000). However, source apportionment is possible due to specific characteristics of
particular molecular weight isomer ratios as a fingerprint from two main anthropogenic
petrogenic and pyrogenic sources, as reviewed by Yunker et al. (2002). PAHs ratios have
been widely applied (e.g. Budzinski et al., 1997; De Luca et al., 2005). But, the interpretation in
most studies is limited to infer sources as to major categories: petrogenic and pyrogenic.
32
sediment profiles can also be expected to differ somewhat from those of SPM (Fernandes &
Sicre, 1999). They will tend to favor HMWs due to the complex sedimentary degradation
processes which take place. LMW compounds are very susceptible to biodegradation due to
their high solubility. However, HMWs are strongly associated with carrier sediment particles, a
relationship which can to a large extent retard microbial attack of particles adsorbed upon their
surfaces. As a direct consequence, an increase in the ratio of LMW/HMW would be
expected in the sediment.
33
Table 2.1. Diagnostic mass ratios for identification of petrogenic and pyrogenic sources
ANTH/(ANTH+PHEN) FLA/(FLA+PYR) BaA/(BaA+CHRY) IPYR/(IPYR+BPERY)
LMW/HMW
MW 178 MW 202 MW228 MW 276
Identification
Values a
Petrogenic >1 <0.1 <0.4 <0.2 <0.2
Combustion <1 >0.1 >0.5 >0.35 >0.5
Mixture
petrogenic/ 0.2 0.35
combustion
Petroleum
0.4 0.5 0.2 0.5
combustion
a
The ratio of MW178, 202, 228, 276 after Yunker et al. (2002)
For a better overview of the application of those values, various ratios of PAH isomers
from common classes stemming from different sources are presented here. The emission of
fossil fuel combustion and biomass burning as well as crude oil and spillage events, for
example, are evaluated from various literature sources (see Appendix 2). In this evaluation,
different data from the literature are classified into the four major groups described earlier,
including crude oil and spillage (petrogenic sources), coal and petroleum combustion,
wood/bamboo burnings and biomass and peat burnings (pyrogenic sources).
The ratios of MW178, 202, 228 and 276 for those major groups of sources from the
literature generally lies within the expected range of petrogenic and pyrogenic values. This
suggests that these ratios can be used to distinguish petrogenic versus pyrogenic sources (Fig.
2.9 & 2.10). For the petrogenic sources, the ratios with MW178, 202, and 228 are more
sensitive than MW 276. It is due to the fact that the concentration of HMW PAHs in crude oil
and spillages are relatively low. Therefore, differences between the isomers must not be large in
order to lower the ratio quite drastically. Likewise, the ratios for MW 178, 202 and 228 clearly
separate the values of wood/bamboo and biomass burnings from those found for petrogenic
sources. This also suggests that these values are acceptable for partitioning pyrogenic and
petrogenic sources. However, there are several data which do not follow suit, as seen in Fig. 2.9.
First, in the crude oil and spillage groups the ratios of MW202 and 228 for Detroit oil spills
(after Wang et al., 2004) are higher than the same ratios of the other crude oil and spills. They
even lie in the pyrogenic data region. Wang et al. (2004) explained the pyrogenic signature of
the spill by attributing it to combustion and motor lubricant processes, stating that the lube oil in
the spill samples was waste lube oil. Second, these combustions produced PAHs whose the
ratios also fall in the region of petrogenic sources, for example, coal (MW202) and diesel
(MW178) combustion, paper combustion (MW 178 and 228), and the burning of corn grasses
(MW 178). These disagreements between apportionment values indicate that application should
be carefully interpreted with respect to those sources. Because there may be diverse sources of
PAHs in the aquatic compartment, these ratios should therefore be complementarily applied.
34
To achieve this, the best way to represent the comprehensive analysis of the above-
mentioned ratios is through the use of cross-plot graphs, which allow for optimal discrimination
ability between both petrogenic and pyrogenic sources and within the pyrogenic sources
(petroleum vs. wood/biomass burnings). One possible combination is a cross plot between
MW202 (x-axis) to the other remaining ratios (y-axis). The primary consideration here is that
compounds with a molecular mass of 202 have been proven to possess a large thermal range of
stability with respect to their formation by heat (Yunker et al., 2002). The axes are arbitrary.
Fig. 2.11 shows the cross-plot graphs of the given isomer ratios are a useful tool for
apportioning petrogenic vs. pyrogenic sources. We can see that each of the ratio cross-plots
(MW202 vs. MW178, 228, and 276) shows a relatively clear segregation between oil (left
quadrant) and combustion sources (right quadrant), although a tendency still is likely for the
values to lie in the mixture area. Interestingly, a clear segregation between fossil fuel
combustion and biomass burning is given by the plot of the ratios of MW202 vs. MW178.
However, the application of such cross-plots must be comprehensively and carefully interpreted
within the context of the specific environmental conditions found at a given site.
35
1,00 Alaskan North Slope
A Crude
Crude Oil and Spillages
0,90 Oil spills "Oil Tanker
0,80 Enrika"
Oil spills "Enrika"
0,70 Beach Sample1
0,60 Oil spills "Enrika"
Beach Sample2
0,50 Detroil Oil Spill_1
0,40
Detroil Oil Spill_2
0,30
0,10 Pyrogenic
0,00
Petrogenic
MW 178 MW 202 MW 228 MW 276
0,80 Charcoal
Fig. 2.9. Mass ratio distribution of specific PAH isomers from various (A) petrogenic (crude oil and
spillages) and (B) pyrogenic of coal and petroleum combustion. The lines represent reference values used
for apportionment petrogenic (dashed lines) and pyrogenic (solid lines) sources (after Yunker et al.,
2002). The ratio values were calculated from many sources (see: Fig. 2.4 including the references).
36
1,00 Almond
A Wood/Bamboo Burnings
Walnut
0,90
Chinese clay woodstoves
0,80 Pine-domestic heating
Fir
0,70
Eucalyptus wood 1
0,60 Wood, Domesting Heating
Oak Wood
0,50
Lao trad. woodstoves
0,40 Thai bucket woodstoves
0,30 Cambodian trad. Woodstoves
Vietnam trad. Woodstoves
0,20
Eucalyptus wood 2
0,10 Paper
Bamboo
0,00
Pyrogenic
MW 178 MW 202 MW 228 MW 276
Petrogenic
B 1,00 Sugarcane
Biomass and Peat Burnings
0,90
Pampas grass
0,80
Mixed ryegrass
0,70
Rice grasses
0,60
Corn grasses
0,50
Fig. 2.10. Mass ratio distribution of specific PAH isomers from other various pyrogenic sources of (A)
wood/bamboo and (B) biomass and peat burning sources. The lines represent reference values used for
apportionment petrogenic (dashed lines) and pyrogenic (solid lines) sources (after Yunker et al., 2002).
The ratio values were calculated from many sources (see: Fig. 2.4 including the references).
37
Petroleum
Combustion Grass/Wood/Coal
Petroleum Combustion
1,0
0,9
0,8 Grass/Wood/Coal
IPYR/(IPYR+BPERY)
0,7 Combustion
0,6
0,5
0,4 Petroleum
0,3 Combustion
0,2
0,1 Petroleum
0,0
0,0 0,1 0,2 0,3 0,4 0,5 0,6 0,7 0,8 0,9 1,0
1,0
0,9
0,8
Combustion
BaA/(BaA+CHRY)
0,7
0,6
0,5
0,4
0,3
Mixed Sources
0,2
0,1
Petroleum
0,0
0,0 0,1 0,2 0,3 0,4 0,5 0,6 0,7 0,8 0,9 1,0
1,0
0,9
0,8
ANTH/(ANTH+PHEN)
0,7
0,6
0,5 Combustion
0,4
0,3
0,2
0,1
Petroleum
0,0
0,0 0,1 0,2 0,3 0,4 0,5 0,6 0,7 0,8 0,9 1,0
FLA/(FLA+PYR)
Fig. 2.11. Common cross plots of the mass ratio of 202 vs. 178, 228, 276 and the determination end-
member values (dashed line) for source apportionment (after Yunker et al., 2002). The literature values
from various petrogenic (blue triangles) and pyrogenic sources: coal and petroleum combustion (red
circles); wood/bamboo burnings (gray circles); biomass and peat combustion (green circles) are plotted to
ascertain the extent of which the plots compromise the variability of environmental data. These cross
plots show that combination of MW 178, 202, and 228 plots are able to generally separate substances
with petrogenic (crude oil) and pyrogenic origins.
38
2.3. Distribution in Aquatic Compartments
PAHs evidence widespread distribution in the hydrosphere of rivers, estuaries and coastal
areas (e.g. Gschwend & Hites, 1981; Mitra et al., 1999; Golomb et al., 2001; Woodhead et al,
1999) where the sources are mostly concentrated. This also holds true for far-distance and
remote aquatic systems such as mountain lakes (e.g. Fernndez et al., 1996, 2002; Vilanova et
al., 2001) and the Southern Ocean (e.g. Valero-Navarro et al 2007; Mazerra et al 2000). In the
aquatic system itself, PAHs were observed in most compartments either as truly dissolved
substances or as being associated with dissolved organic matter. This section briefly elaborates
upon PAH distribution in the main aquatic compartments of sediment, SPM and the water
solution, with a particular focus on rivers, estuaries and coastline areas.
39
and high organic carbon content (Karickhoff et al., 1979; Maruya et al., 1996; Tolosa et al.,
2004).
Fig. 2.12. A conceptual model for the sequestration of hydrophobic organic contaminant by geosorbents.
NAPL= nonaqueous-phase liquids; SOM= sorbent organic matter. Sorption mechanisms include (A)
absorption into amorphous or soft natural organic matter or NAPL; (B) absorption onto condensed or
hard organic polymeric matter or combustion residue (e.g. soot); (C) adsorption onto water-wet organic
solvent (e.g. soot); (D) adsorption onto exposed water-wet mineral surfaces (e.g. quartz); (E) adsorption
onto microvoids or microporous mineral (e.g. zeolites) with porous surface at water saturation <100%
(adopted from Luthy et al., 1997).
PAHs in surface sediments are, in fact, heterogeneously distributed among the various
particle-size fractions (e.g. Maruya et al., 1996; Budzinski et al., 1997; Tolosa et al., 2004; Prahl
& Carpenter, 1983; Simpson et al., 1998; Wang et al 2001; Rockne et al., 2002; Ahrens &
Depree, 2004). PAH enrichment is not found solely in the mud fraction. It has also been
observed in the sand fraction, which can also carry significant loads of various PAHs. For
example, Rockne et al. (2002) found that PAH levels tend to increase with increasing grain size
in sediment samples taken from Piles Creek and Newton Creek in the New York/New Jersey
harbor area. Similar trends were reported by many other studies (e.g. Ahrens & Depree, 2004;
Oen et al., 2006; Simpson et al., 1998). Therefore, in this study we chose to investigate the PAH
distributions in two general groups of sediment sizes as classified using the Wentworth-Udden
scale: sand (coarse) 2 mm 63m; and mud (fine) <63m, which includes the silk and clay
fractions.
Sedimentary organic matter (SOM) controls the distribution of PAH in those fractions.
The PAH sorption capacity of SOM depends both on its structure and composition (Grathwohl,
1990; Huang & Weber, 1997; Johnson et al., 2001). Structure and composition vary among
40
sources e.g. peat, fragmented plant materials, black carbon, and kerogen (Grathwohl, 1990). But
SOM is essentially the product of diverse geochemical alterations, ranging from biopolymer
precursors (e.g. carbohydrate, protein, lipids, lignin, tannin and pigments) to geopolymers (e.g.
fulvic, humic, humin substances and kerogen) through complex diagenesis processes. During
diagenesis, SOM experiences compositional changes in polarity and aromatic carbon content
which controls its reactivity with hydrophobic organic compounds (Garbarini & Lion, 1986;
Gauthier et al., 1987; Luthy et al., 1997; Chiou et al., 1998). Therefore, a correlation between
PAH and SOM is often helpful for pinpointing the significant role of organic matter (e.g.
Karickhoff et al., 1979; Means et al., 1980; Kim et al., 1999; Guinan et al., 2001; Maskaoui et
al., 2002; Viguri et al., 2002). Such a correlation applied to sediment size fractions can help
elaborate the preferential particle associations of PAHs (e.g. Prahl and Carpenter, 1983).
Coarse and fine sediment fractions contain different types of organic matter which affect
PAH distributions. Increasing PAH content for the coarse sediment fraction has been
acknowledged, due to the presence of organic particles that have a high affinity for PAH
sorption. This is despite the fact that the OM fraction normally represents only a tiny portion of
the total sediment mass. Ghosh et al. (2003) petrographically examined carbonaceous particles
(coal, coke, charcoal, pitch, cenospheres, and wood). These particles are typically in the size
range of 250m1mm and comprise only about 5-7% of the total mass, however, they account
for 90% of adsorbed PAHs. Oen et al. (2006) emphasized that the presence of decomposed
vegetable debris and shiny black particles dramatically increases the PAH content of the sand
fraction. Since combustion processes leave behind soot and black carbon materials as residue, it
is entirely possible that PAHs have already been adsorbed onto those particles before they ever
reach the sediment. Therefore, examining the PAH content of the various sediment size
fractions can provide important information on the mode of PAH transportation into the aquatic
environment. On the other hand, humic substances are organic matter specifically associated
with the fine fraction. This is due to the fact that the sorption of humic substances (normally in
the form of dissolved organic matter, DOM) onto the fine fraction is typically a direct function
of uptake onto its exceedingly large surface area. However, PAHs may be reluctant to associate
with fine fraction-OM in the presence of combustion-derived OM (e.g. Prahl & Carpenter,
1983). Furthermore, different sources of SOM in the fractions have also been recognized. Evans
et al. (1990) illuminated two different types of organic materials which were responsible for
bimodal distribution of PAHs in coarse (>250m 2mm) and fine (<63 m) fractions. First,
fragmented plant materials are assumed to be responsible for high levels of organic matter (OM)
in the coarse fraction. This is in addition to combustion-associated particles such as coal, soot or
black carbon. Second, condensed organic matter (humic substances) is mostly associated with
the fine fractions. Therefore, PAH enrichment in the sand fraction might be an indication of a
strong anthropogenic source for PAHs. An investigation of these PAH-sized fraction
41
associations would provide us with significant additional information about PAH delivery
modes into aquatic environments, whether as a result of combustion-derived particle association
or from the sorption equilibrium on the surface of fine sediments.
42
processes, resulting in such materials as humic substances, carbonates and both iron and
manganese oxides. They occur either as coatings or discrete phases. Biogenic particles include
those stemming from microorganisms, plankton and the decaying remains of macroorganisms
and terrestrial plant debris. Bio-particles can also refer to those derived from proteins,
carbohydrates, lipids and pigments. Anthropogenic particles consist mainly of combustion by-
products such as dust and fly ash, but also include other widely varied synthetic materials such
as plastic, tar, solvents and surfactants (Turner & Millward, 2002). However, SPM particles are
often divided into inorganic and organic particles based on their chemical properties. Particulate
inorganic material (PIM) includes lithogenous matter (minerals and insoluble salts), whereas
particulate organic materials (POM) are composed of a rather broad mixture of hydrogenous,
biogenic and anthropogenic particles. PIM and POM are straightforward measures for the
overall SPM composition in a sample. The latter also acts as an effective sorbent for
hydrophobic organic pollutants.
The molecular composition of PAHs in particulate matter is somewhat different from that
of those found in sediments. Luo et al. (2006) concluded that SPM samples taken from the Pearl
River estuary contained large amounts of both 2- and 3-ring PAHs. On the other hand, these
sediments were also characterized by high levels of 5- and 6-ring PAHs. Similar findings have
been reported for other riverine and estuarine systems (e.g. Witt, 1995; Shi et al., 2005). These
patterns were driven by the fact that the SPM was continually receiving fresh PAH inputs, either
from the atmospheric deposition of combustion by-products or from direct oil spills, which are
predominantly characterized by low molecular weight compounds (see 2.1.2). However, this is
not always the case in every situation. PAH profiles in SPM samples represent the local
conditions where the transfer of high molecular weight molecules into the aquatic environment
occurs. This can also be mainly derived from land-water interactions. For instance, Witt &
Siegel (2000) observed that the distribution of PAHs resulting from Oder River floods were
characteristic of high-combustion profiles, which are predominated by HMW compounds. On
the other hand, the concentration of LMW PAHs in the water column and sediments was subject
to great variation due to differing degradation processes (photonic and microbial). Therefore,
examination of a specific PAH profile in SPM yields clues to the fate of PAHs in a particular
environmental setting.
43
substantial. This is due to the fact that the fate of truly dissolved PAHs is appreciably controlled
by the existence of dissolved organic matter (DOM) as a geosorbent. Schlautman & Morgan
(1993) observed in an experiment that PAH-DOM binding could be completed within a
timeframe of only 3 minutes. As a consequence, the free fraction in natural waters is unstable
and is readily associated with DOM. Thus, it is quite challenging in terms of analytical
techniques to effectively separate these two aqueous fractions. And this is despite the
availability of various analytical techniques such as fluorescence quenching, purging or
sparging techniques, solid-phase microextracion (SPME), equilibrium dialysis, solubility
enhancement, ultrafiltration, size exclusion chromatography, and liquid-liquid extraction
(Burkhard, 2000 and references therein). This study simply considers these two fractions of
PAHs as the "dissolved phase", which operationally defines dissolved PAHs as those passing
through the GF/F. The most popular extraction techniques for determining dissolved PAHs are
solid phase extraction (SPE) and stir bar microextraction (SBME) (Falcon et al., 2004;
Fernndez-Gonzles et al., 2007; Poerschmann et al., 1997).
The composition of unsubstituted PAHs in the dissolved phase depends on the solubility
and hydrophobicity (Kow) of a given compound. The former decreases as molecular weight
increases and the latter increases with increasing molecular weight (see Appendix 1). With
regard to a compounds solubility, we can expect a predominance of low molecular weight
PAHs (2 and 3 rings) as compared to HMW compounds in the absence of DOM, salinity and
pH effects. The opposite also holds true. Furthermore, angular compounds are more soluble
than corresponding linear isomers, such as phenanthrene (1.18 mg/L) compared to anthracene
(0.08 mg/L) or fluoranthene (0.26 mg/L) compared to pyrene (0.14 mg/L). With regards to Kow,
we might assume that the presence of DOM should increase the concentration of HMW PAHs
in the dissolved phase. However, interactions between PAHs and DOM prove themselves to be
DOM source-dependent (Liu & Amy, 1993). Therefore, examining the concentration and
composition of materials in the dissolved phase can reveal the relevance of particular
environmental settings on the fate of particular PAHs.
2.4. The fate of PAHs in the water: a partitioning concept and the role of
natural organic matter
The fate of hydrophobic organic pollutants in aquatic systems has been widely studied,
including which factors control their distribution in two immiscible phases (particulate and
water solution). This is due to the fact that transfer from the water solution onto particulate
matter can possibly act to retard these molecules from degradation, volatilization and desorption
(Mackay & Powers, 1987).
44
One way to understand the fate of the hydrophobic chemicals is to evaluate their partition
coefficients (e.g. Hellou et al., 2005; Ko & Baker, 1995; Wang et al., 2001; Zhou et al., 1999).
This partitioning involves complex dynamic sorption interactions between the molecules of
solutes, solvents and sorbents, which act in concert. Weber Jr. et al. (1991) explained that the
partitioning of a given chemical into two phases is a result of its relative affinities for sorbate
molecules and both the solvent and sorbent phases competing for thermodynamic balance.
Therefore, partition represents an equilibrium condition between molecules in two phases. Thus,
the concentration of given compounds in the solid phase depends on its concentration in the
water solution, which is often described as the sorption isotherm.
There are three mathematical models that have been widely called upon to quantify and
interpret the partition of hydrophobic organic contaminants between the aqueous and solid
phases, namely the Linear, Langmuir, and Freundlich models as reviewed by Voice & Weber Jr
(1983), Weber Jr. et al. (1991), and more recently by Huang et al. (2003). The Linear model is
built upon the hypothesis that the sediment organic matter has no limitation of sites and surface
space for sorption. It assumes that sedimentary organic matter will therefore act as a gel- or
liquid-like phase. The Langmuir model was originally developed for the adsorption of gases
onto solids, and generally assumes that (1) the energy of adsorption is constant and independent
of surface coverage, (2) adsorption occurs only on localized sites and there is no interaction
between adsorbed molecules and (3) the maximum adsorption possible is that of a complete
monolayer (Voice & Weber Jr., 1983). However, this model does not properly fit the sorption
patterns of hydrophobic molecules on soil and sediments (Huang et al., 2003). The Freundlich
model is the most commonly used model, due to the fact that it provides information about the
heterogeneity of a given sorbents sorptivity. Fig. 2.13 shows three types of Freundlich isotherm
linearity parameters (n < 1, n = 1, n > 1), where "n" is an indicator of the site energy
heterogeneity. A value of n < 1, a concave down shape curve, means the presence of specific
sorption sites, which limits sorption as the solute concentration increases. The case n = 1
indicates that the sorptive site is homogeneous, thus sorption is a linear function of increasing
solute concentration in the aqueous phase. The case n > 1, a concave up shape curve, suggests
that the sorptivity of the solid phase increases as the sorbate concentration increases.
45
Fig. 2.13. Three types of observed relationship between concentration of a chemical in the sorbed state,
Cs, and the dissolved state, Cw. All can be fit with a relationship of the form Cs = K Cwn where K and n
are constants (adopted from Schwarzenbach et al., 2003).
46
III. METHODS OF ANALYSIS
3.1. Introduction
This analytical method was intended to determine the 16 PAHs (see Chapter 1.1. for the
compounds) in three environmental compartments: sediment size-fractions, suspended
particulate matter (SPM) and water solution as dissolved PAHs, using wide-pore octadecyl (C18
) reverse phase column with high performance liquid chromatography (RP-C18-HPLC) detected
by ultraviolet (UV) and programmable fluorescence detectors (FLD). The use of HPLC
UV/FLD has been well-recognized for PAHs instead of gas chromatography mass spectrometer
(GC/MS) (e.g. Grope, 2001; ICES, 1997; Wise et al., 1990). Even, EPA Method 610 suggests
that HPLC is the best used for the 16 PAHs of the EPA priority list as GC/MS can hardly
resolve four pair of isomer compounds: Anthracene and phenanthrene; chrysene and
benzo(a)anthracene; benzo(b)fluoranthene and benzo(k)fluoranthene; dibenzo(a,h)anthracene
and indeno(1,2,3-cd)pyrene.
The methods involved (1) sample collection and treatments including sediment grain-size
fractionation; (3) extraction with organic solvent percolation for sediment and SPM, and solid
phase extraction (SPE) for dissolved PAHs; (4) work-up procedures including clean-up,
concentration and matrix-exchange; and finally (5) determination of PAHs using HPLC
UV/FLD. The method performance was subject to quality control procedures using spiked
perdeuterated PAHs, procedural blank and spiked reference standards.
47
passing through the 63-m sieve at 1500 rpm for 20 minutes. Those sediment fractions were
then stored frozen until analysis.
48
The molecular interaction between the PAHs as target analytes and the sorbent
stationary phase of the SPE has been generally acknowledged as non-polar interactions taking
place between alkyl group of the sorbent and the analytes. The most typical alkyl groups
developed for the non-polar interaction are C18- or C8- (e.g. Macherey-Nagel GmbH, Duren,
Germany). However, environmental sample matrix, in particular humic substances, also plays a
significant role in determining the reproducibility and recovery of the analytes. Jeanneau et al
(2007) observed negative effects of humic substances in the natural water sample which is
virtually a clogging phenomenon that induces a competition between organic macromolecules
and organic micropollutant for the available sorption site. Therefore, for rich-humic substance
water like the Siak water sample (Baum et al., 2007) we applied a specific dual phase
aminopropyl and octadecyl- (NH2/C18) - cartridge for the extraction of PAHs. The polar group
of NH2 -modified silica is intended to provide surface interaction with polar compounds of the
complex macromolecules of humic substances. The C18 group is then to retain PAHs. SPE
Cartridge used in this study was Chromabond NH2/C18 (6 ml, 500 mg/1000 mg), obtained
from Macherey-Nagel GmbH (Dueren, Germany). The extraction was undertaken using a solid
phase extraction vacuum manifolds (VisiprepTM, SUPELCO).
Prior to extraction, the cartridges were sequentially conditioned with 10 ml hexane, 20 ml
methanol, and 20 ml Milli-Q water. To run the cartridge dried during conditioning process was
avoided. Slight film of water was left above the phase, and the cartridge was ready to be
aspirated. 500 ml to 1 L filtrated water sample was prepared. Methanol was added 2-5% of the
filtrates volume. Adding organic solvents (as a surfactant) such as methanol or 2-propanol to
the sample prior to extraction would partially overcome the clogging problem, as well as
increase the solubility of PAH (Marce & Borrull, 2000). Surrogate deuterated standards (d10-
fluoranthene and d12-perylene) were spiked to accomplish procedural efficiency and data
correction from any losses during extraction and work-up procedure. Then, the prepared water
sample was aspirated through the cartridge at flow rate of ca. 5 ml/min. The flow rate was
controlled by adjusting the pressure of the manifolds. After all of the filtrate was aspirated, the
cartridge was then again washed with Milli-Q water. Finally slight film (ca. 0.5 ml) of the
remaining water was left on the top of the cartridge. Then, the column was firmly topped with
foil, sealed with a paraffin film, and stored cool until analysis. Sample was collected in
duplicate.
49
3.3. Determination of Polycyclic Aromatic Hydrocarbons using High
Performance Liquid Chromatograph coupled with Ultraviolet and
Fluorescence Detectors (HPLC UV/FLD)
Sediment Extraction
50
was experimentally extracted with aceton/hexane (1/9) for 4 hours. The results confirmed no
peaks.
The result is presented on a dry-weight basis (weight/weight). Therefore other portion
(aliquot) of each fraction was prepared for dry/wet coefficient for moist-sediment weight
correction at the same time as for analytical ones. The sample aliquots were dried in the oven at
60 80oC until dried condition achieved (no change in weight after 3 minute on the balance).
Sediment dry-weight (d.w.) was corrected by the ratio of dry/wet weight of each aliquot. Water
portion in sediment ranged between ca. 1% - 3%.
SPM Extraction
Unlike sediment, extraction system for SPM-borne PAHs was using only a mixture of
acetone/hexane (1/9 ; v/v). The filter was air-dried in a clean-fumed cupboard for 24 hours prior
to extraction. The extraction efficiency was confirmed with the surrogate standards. The
accuracy of extraction system was tested with PAH standards spiking method to the blank filter
(see section 3.4.). The extraction procedure for the filter was principally similar to those of
sediment. The extraction time was ca. 6 hours at boiling position.
51
out for two steps: (1) evaporation for dichloromethane with the pressure of 250 400 mbar and
the bath temperature of 30 - 35oC, and (2) evaporation of hexane with pressure of 500 600
mbar and the bath temperature of 50-60oC. The final volume attained ca. 1 ml. The loss of
analytes during concentration was confirmed with the surrogate standard for procedural
efficiency (section 3.4.).
3.3.2.2. Drying and Alumina/Silica (Al2O3 / SiO2) column for clean-up of polar mixtures
Following the first concentration process, the extracts were subject to clean-up process
using an Al2O3 / SiO2 column. This column was tapped with a drying agent of sodium sulfate
(Na2SO4) due to co-extracted water. Prior to use, anhydrous granular Na2SO4 was heated at
250oC for overnight, and stored at 150oC until use. One to three grams of Na2SO4 was placed on
the top of aluminum oxide phase in a column used for clean-up.
Clean-up procedure becomes a critical part in the sample work-up as any other co-
extracted compounds (interferences) may render difficulties in identification and lead to error in
quantification. Surface sediment and suspended particulate matter may contain a great variety of
polar and non-polar compounds which is inevitably co-extracted such as sulfur-containing
compounds and pigments (ICES, 1997; Wise et al., 1995). A combination of 1:2 (w/w)
deactivated (10%) Al2O3 / (3%) SiO2 column was used to clean-up the polar extract (ICES,
1997; Smedes & de Boer, 1997). Solvents used to eluate the extract were hexane and a mixture
of (3/7 : v/v) dichloromethane/hexane. A test fractionation was carried out by spiking 16 PAHs
standard in hexane matrix. The elution was divided by four fractions. Each of them was eluted
with 20 ml. The first fraction was eluted with hexane; the second and third fractions were eluted
by dichloromethane/hexane (3/7 : v/v). The fourth fraction was again eluted by hexane. The
PAHs were mainly detected in the second fraction, and slightly in the third fraction. The clean-
up column was checked first with blank run, and with spiked 16 PAHs mixture standard. One
column was prepared for one batch of extraction which contained 6 samples, and conditioned
between the samples by dichloromethane/hexane as much as two times of the columns volume
(ca. 40 ml).
52
3.3.4. PAH determination: High Performance Liquid Chromatography with ultraviolet
and fluorescence detectors (HPLC UV/FLDs)
3.3.4.1. Baseline separation with reverse phase octadecyl (RP-C18) column chromatography
Baseline separation and quantification of the PAHs were performed using a reverse phase
wide-pore octadecyl -RP-C18- column (250 mm x 46 mm, 5 m, 300 ) obtained from
BAKERBOND, J.T. Baker Inc (Phillipsburg, New Jersey, USA) with a high performance
solvent delivery pump (LKB Bromma 2249 Gradient Pump) for HPLC. The sample injection
loop was 20 l. The mobile phase or elution system was a mixture of water (Milli-Q) and
acetonitrile (CH3CN, HPLC grade), and set in a normal gradient elution mode. The normal
gradient mode means that solvent A (water), B (acetonitrile, ACN) and C (any others if
necessary) can be mixed at any ratio giving the sum of percentage equal to 100% (%A + %B +
%C = 100%). The elution program was a combination of isocratic elution and binary gradient of
water (A) and acetonitrile (B) that set off from 55% to 100% ACN with 1 ml/min flow rate for
45 minutes plus 5 minutes to conditioning (equilibrium) for the next run (Table 3.1.). Optimum
separation was exercised for PAH reference standard containing a mixture of the same 16 PAHs
compounds (16 PAH Mix 61), as well as for perdeuterated PAH standards. All reference
standards were obtained from Dr. Ehrenstorfer GmbH, Augsburg, Germany. Instead of
acenaphthene and fluorene which were not baselinely resolved, all the remaining target PAH
compounds were completely separated (Fig. 3.1). All HPLC run was performed at room
temperature (mean standard deviation = 24oC 1.1oC, N = 49, measured from June to Sept
08).
53
amplification factor, PMTGAIN = 11; the flash frequency, LAMP = 1, 1.25 W / 55 Hz; and data
reduction interval, RESPONSETIME = 4, 1000 msec.
Table 3.2. Selective pairs of fluorometric wavelength and retention time (minute) of the PAHs
and the surrogate standards with the given elution mode.
No. Analyte Wavelength Retention Time (minute)
UVD 254 nm (N=17) FLD (N=31)
Target Analytes ex / em Mean SD RSD Mean SD RSD
nm (%) (%)
1 Naphthalene, NAPH 250 / 341 7,72 0,04 0,49 7,88 0,03 0,41
2 Acenaphthylene, ACYN 9,09 0,05 0,52
3 Acenaphthene, ACEN 250 / 341 11,7 0,07 0,63 11,8 0,06 0,48
4 Fluorene, FLU 250 / 341 12,4 0,09 0,72 12,6 0,07 0,55
5 Phenanthrene, PHEN 250 / 341 14,9 0,12 0,79 15,2 0,10 0,66
6 Anthracene, ANTH 254 / 400 17,4 0,12 0,68 17,6 0,10 0,58
7 Fluoranthene, FLA 254 / 400 19,7 0,11 0,57 19,9 0,10 0,48
8 Pyrene, PYR 254 / 400 21,0 0,11 0,52 21,2 0,10 0,48
9 Benzo(a)anthracene, BaA 254 / 400 25,7 0,12 0,48 25,8 0,13 0,49
10 Chrysene, CHRY 254 / 400 26,6 0,14 0,52 26,7 0,14 0,52
11 Benzo(b)fluoranthene, BbFLA 254 / 400 29,6 0,15 0,50 29,8 0,14 0,48
12 Benzo(k)fluoranthene, BkFLA 254 / 400 30,7 0,13 0,62 31,3 0,16 0,51
13 Benzo(a)pyrene, BaP 254 / 400 31,2 0,17 0,53 32,3 0,16 0,49
14 Dibenzo(a,h)anthracene, DANTH 254 / 400 34,5 0,19 0,56 34,6 0,18 0,53
15 Benzo(g,h,i)perylene, BPERY 254 / 400 35,0 0,18 0,52 35,1 0,17 0,48
16 Indeno(1,2,3-c,d)pyrene, IPYR 246 / 488 36,1 0,23 0,62 36,3 0,19 0,54
Surrogate Standards N = 10 N = 10
d10-phenanthrene 250 / 341 13,6 0,23 1,73 13,7 0,24 1,76
d10-fluoranthene 254 / 400 18,9 0,15 0,78 19,1 0,15 0,80
6methylchrysene 254 / 400 27,6 0,15 0,54 27,6 0,15 0,54
d12-perylene 254 / 400 28,9 0,20 0,68 29,0 0,19 0,67
54
100 100
Elution program: from 55% ACN to 100% ACN
55
5 min 10 15 20 25 30 35 40
BaP
BkFLA
ANTH
BbFLA
BaA
BPERY
ACEN
CHRY
6 Methylchrysene
NAPH
DANTH
FLU
PHEN D10
PHEN
PYR
IPYR
PERY D12
ACYN
FLA D10
FLA
Fig. 3.1. Comparison of chromatograms for 16 PAHs between UV 254 (red) and FLD (black) with the
deuterated PAHs (blue).
55
Appendix 3.1. Limit of detection (LoD) are provided in the table 3.4. It was obtained from
repeated analysis of a sample with a very low content of the analytes (after Huber, 2003).
BaP
6 Methylchrysene
DANTH
BkFLA
BbFLA
PERY D12
BPERY
IPYR
PHEN D10
CHRY
BaA
ANTH
PHEN
PYR
ACEN
FLA D10
NAPH
FLU
FLA
Fig. 3.2. An example of peaks identification using retention time of the standards (black) and
confirmation on the shift in the retention time using the deuterated standards. The chromatograms were
derived from fluorescence detector. The red chromatogram was an extract of mud fraction of sediment at
S142 Siak estuary.
Table 3.3. Repeatability of the peak area of the PAHs measured for the reference standards
(Cal#6, see Appendix 3.1.).
Peak Area (N = 10)
No. PAHs
Mean SD RSD (%)
56
Table 3.4. Limit of detection (LoD) for the PAHs
Absolute
Conc. of
No. PAHs amount
LoD (ng/l)
(pg)
Table 3.5. Recovery of spiked deuterated PAHs to the samples for procedural efficiency and
reproducibity. Data were driven from ultraviolet detectors (see Appendix 3.2 for detail).
Sediment SPM Water
Compounds N = 51 N = 32 N = 10
Mean SD Mean SD Mean SD
57
Procedural efficiency was also checked with 16-PAH standard spiked method. 16 PAHs
were spiked into the thimble blank for sediment and SPM, and Milli-Q water for dissolved
PAHs. These spiked standards then proceeded through the step of procedural analysis. For the
dissolved PAHs, the standard was spiked into 1000 ml of Milli-Q water plus 1% Methanol
(solubility enhancement). The spiked waters were then aspirated through the SPE cartridges,
and performed the step of analysis. The results were shown in the table 3.6 and 3.7. The
recovery of spiked standards ranged from 63% (BaP) to 105% (ANTH) for the thimbles, and
from 49% (BaP) to 96% (PHEN) for the water.
Table 3.6. Recovery of spiked PAH standards (16 PAH Mix 61) into the blank thimbles for
sediment and SPM analysis. The data was calculated from the peak area of the ultraviolet
detector response.
Compounds Spiked Mass Recovery Test (%)
(ng) 1 2 3 Mean
Naphthalene 500 111 89 101 100
Acenaphthylene 1000 101 109 99 103
Acenaphthene 500 108 96 83 96
Fluorene 100 98 94 89 94
Phenanthrene 50 93 98 89 93
Anthracene 50 96 119 101 105
Fluoranthene 100 87 98 94 93
Pyrene 50 76 138 95 103
Benzo(a)anthracene 50 85 107 82 91
Chrysene 50 93 101 85 93
Benzo(b)fluoranthene 100 93 95 93 94
Benzo(k)fluoranthene 50 114 91 91 99
Benzo(a)pyrene 50 35 49 104 63
Dibenzo(a,h)anthracene 100 93 90 100 94
Benzo(g,h,i)perylene 100 94 83 119 98
Indeno(1,2,3-c,d)pyrene 50 96 94 123 104
Table 3.7. Recovery of spiked PAH standards into the blank Milli-Q water for dissolved PAH
analysis. The data was calculated from the peak area of the ultraviolet detector response.
Compounds Spiked Mass Recovery Test (%)
(ng) 1 2 3 Mean
Naphthalene 30000 47 82 88 72
Acenaphthylene 60000 92 96 99 95
Acenaphthene 30000 84 91 95 90
Fluorene 6000 102 100 103 101
Phenanthrene 3000 98 93 97 96
Anthracene 3000 108 106 112 109
Fluoranthene 6000 97 86 95 93
Pyrene 3000 93 83 93 90
Benzo(a)anthracene 3000 101 68 75 81
Chrysene 3000 94 64 66 75
Benzo(b)fluoranthene 6000 102 63 66 77
Benzo(k)fluoranthene 3000 74 44 48 55
Benzo(a)pyrene 3000 58 42 46 49
Dibenzo(a,h)anthracene 6000 106 53 53 71
Benzo(g,h,i)perylene 6000 104 52 53 70
Indeno(1,2,3-c,d)pyrene 3000 100 56 59 72
58
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68
IV. DISTRIBUTION AND SOURCE OF POLYCYCLIC AROMATIC
HYDROCARBONS (PAHs) IN SURFACE SEDIMENTS FROM THE
SIAK RIVER, ITS ESTUARY AND THE ADJACENT COASTAL AREA
OF RIAU PROVINCE, INDONESIA
Abstract
The distribution and sources of polycyclic aromatic hydrocarbons (PAHs) were examined
in sediments from the Siak river, its estuary and the Riau coast of Sumatra, Indonesia. PAH
concentrations were determined by HPLC with UV and fluorimetric detectors in two size
fractions (sand: 2 mm 63m; mud: <63 m). The sum of the 16 PAH selected by EPA
(PAHs) ranged from 126 5474 ng g-1 d.w. In general, the coarse fraction (164 to 5474 ng g-1
d.w., median = 837 ng/g d.w.) contained circa twice as much PAH as the mud fraction (126 to
1314 ng g-1 d.w., median = 517 ng/g d.w.). The concentrations were higher than in similar
systems in Asia suggesting a link to land use change and peat burning practices. Organic carbon
contents varied greatly from 0.01% to 24% in the sand, but only slightly in the mud from 0.34%
to 3.70%. The composition of PAHs in both fractions was largely similar to each other with 3-,
4- and 5-ringed PAHs being most abundant. Molecular-weight ratios and isomer ratios for
source apportionment indicated a dominance of pyrogenic PAHs, but petrogenic origins showed
significant signatures in the vicinity of residential and industrial areas.
69
4.1. Introduction
Polycyclic aromatic hydrocarbons (PAHs) are a class of toxic and carcinogenic organic
pollutants containing two or more fused aromatic rings, produced mainly through the burning of
biomass and the incomplete combustion of fossil fuels (Neff, 1979; IARC, 1987). In addition,
they constitute a substantial fraction crude oil and its petroleum products (Requejo et al., 1996;
Wang et al., 1999). Concern over these compounds worldwide is not only due to their
carcinogenic properties, but also to their ubiquity and persistence in the aquatic environments
which increase potential exposures. Human exposure is therefore a possibility through
consumption of contaminated food in which PAHs experienced bio-concentration and bio-
magnification, and inhalation (Hellou et al., 2005; Ribeiro et al 2005; Bai et al., 2009).
Land use change in Indonesia by peatland burnings particularly in Sumatra and
Kalimantan, is a major source of pollutants, particularly the emission of PAHs in addition to
CO2 causing climate change. The worst peatland fire episode occurred during a severe El Nio
event (1997/1998), which emitted up to 2.57 Gt Carbon in 1997 during the damage of ca. 6.8
Mha (or 34%) of Indonesian peatland (Page et al., 2002). In comparison, the global net emission
of CO2 from land-use change was recently estimated at 2.4 Gt y-1 and 50% of this flux came
from tropical Asia (IPCC, 2000). The environmental and health effects of haze and smoke have
been widely recognized ever since (e.g. Langmann et al., 2007; Fang et al., 1999; Parameswaran
et al. 2004). PAHs are inevitable products of peatland and biomass burnings. During another
severe fire episode in 2005 in Sumatra, See et al. (2007) observed ca. 561 ng m-3 of the total 16
PAHs on the US EPA priority pollutant list in the emission after peatland burnings around
Dumai. In comparison Pekanbaru (a city affected by the haze) showed a concentration of ca.
135 ng m-3. The latter was even higher than that (ca. 116 ng m-3) of polluted urban areas in
Beijing, China (Zhou et al., 2005). Thus, it can be expected that peatland and biomass burnings
in Sumatra over decades have produced a significant amount of PAHs which have polluted the
surrounding lands and aquatic systems. However, PAH investigation on the aquatic systems in
Sumatra has not been comprehensively undertaken.
Sediment is a well-known pollutant recorder which integrates not only temporal and
spatial pollutant loads of modern settings, but also envoys history of the past. The capacity of
sediments to concentrate and retain elements and hydrophobic organic compounds results from
two inter-correlated sets of physical (grain size) and chemical (organic and mineral
composition) properties (Horowitz & Elrick, 1987). The level of total PAH in the sediment
greatly varied ranging from a few ng g-1 up to hundreds of g g-1 for highly oil contaminated
intertidal sediments (e.g. Sauer et al., 1998). In most studies, PAH assessments have focused on
the bulk sediment content. However, it is becoming increasingly common to differentiate
between grain sizes for better understanding of the pollutant distribution. Furthermore, the
70
assessment of grain size content may help in designing remediation efforts (Ahrens & Depree,
2004).
Like many other pollutants, the PAHs distribute among grain size fractions (e.g. Maruya
et al., 1996; Budzinski et al., 1997; Tolosa et al., 2004; Prahl & Carpenter, 1983; Simpson et al.,
1998; Wang et al 2001; Rockne et al., 2002; Ahrens & Depree, 2004). Enrichment in a
particular fraction, e.g. in coarse (sand: 2mm 63m) or fine (mud: <63m), is strongly related
to specific PAH-geosorbent interactions reflecting the state of environmental conditions.
Several studies showed that in most polluted areas PAHs are enriched in the coarse fraction and
especially in carbonaceous particles such as coal, charcoal, soot or black carbon and plant debris
(e.g. Prahl & Carpenter, 1983; Simpson et al., 1998; Wang et al 2001; Ghosh et al., 2000,
Rockne et al., 2002). In most cases, these particles constitute a minor part of the bulk dry weight
mass, but provide strong affinity for PAHs. Therefore, the PAH enrichment in the coarse
fraction suggests that PAHs and those carbonaceous particles are from the same sources. On the
other hand, the fine (silt/clay) fraction is expected to accumulate more PAHs due to a larger
surface area to mass ratio provided for adsorption (e.g. Karickhoff et al., 1979; Maruya et al.,
1996). Charlesworth et al. (2002) revealed the importance of the fraction <63m in assessing
the distribution of PAHs in areas distant from direct input, and vice versa.
This study aimed (1) to examine the PAH distribution between two size fractions of
surface sediments from the Siak river, its estuary and the adjacent Riau coastal areas of Riau,
Sumatra, Indonesia; (2) to appoint the possible sources; and (3) to understand the role of
sedimentary organic matter for each fraction in PAH distribution, for which the very
humic-rich condition of the Siak river system appear to be especially suited.
71
1999; Quah 2002). In addition, oil discharges from routine river-boat transports as well as from
oil industry related activities (production, transportation and disposals of residues) are
observable.
S269 S227
S226
S267
S228
S 266
Sumatra S253
S230
S251
S 250
INDONESIA S231
S138
S142 S232
S143
S145
S101
S42
S104 S116
S105
S20 S24
S35
The samples were analyzed for 16 PAHs priority pollutants selected by US EPA
including naphthalene (NAPH), acenaphthylene (ACYN), acenaphthene (ACEN), fluorene
(FLU), phenanthrene (PHEN), anthracene (ANTH), fluoranthene (FLA), pyrene (PYR),
benzo(a)anthracene (BaA), chrysene (CHRY), benzo(b)fluoranthene (BbFLA),
benzo(k)fluoranthene (BkFLA), benzo(a)pyrene (BaP), dibenzo(a,h)anthracene (DANTH),
benzo(g,h,i)perylene (BPERY) and indeno(1,2,3-c,d)pyrene (IPYR). Baseline separation and
72
quantification of these analytes were performed on a reverse phase RP-C18 column (250 x 4.6
mm, 5m, BAKERBOND, J.T. Baker Inc) by using a high performance liquid chromatograph
(HPLC LKB 2249 Broma) with ultraviolet (2151 Variable Wavelength Monitor, LKB Bromma)
and programmable fluorescence detectors (Hawlett-Packard 1046A). The mobile phase was a
combination of isocratic and a linear binary gradient elution of acetonitrile(ACN)/water,
programmed from 55% to 100% ACN at a constant flow rate of 1 mL min-1, which set for a
total of 45 minutes.
Sample extraction and work-up procedure were as follows. 10 g of the sediment fractions
were spiked with three surrogate perdeuterated PAH standards: d10-phenanthrene (PHEN D10),
d10-fluoranthene (FLA D10) and d12-perylene (PERY D12), and extracted in Soxhlet-modified
extractors (SoxTec) with solvents suggested by the ICES Method (ICES, 1997) for 6 8 hours:
the first cycle was extracted by acetone followed by a mixture of acetone/hexane (1/9 ; v/v) in
the second cycle. The extracts were then combined and reduced to ca. 1 mL by a rotary
evaporator. A 1:2 (w/w) deactivated Al2O3 (10%) / SiO2 (3%) column plus anhydrous Na2SO4
on the top to remove the co-extracted water, was used for cleaning-up the extract. During the
clean-up process the extracts were eluted with 40 mL of degassed 3/7 (v/v)
dichloromethane/hexane. The excess solvent of the clean extracts was removed by evaporator to
ca. 1 mL. Then, the extracts were subject to solvent exchange into ACN for HPLC analysis.
HPLC grade acetonitrile and analytical grade solvents (acetone, dichloromethane and
hexane) obtained from Fischer Scientific were used throughout the analytical procedures. A
certified mixture of 16 PAHs standards (purchased from Dr. Ehrenstorfer GmbH, Germany)
were used to identify and quantify the analytes. Detector limit of detection ranged from 0.4
ng/mL (BaP) to 12 ng/mL (NAPH) for fluorescence detection, and 38 ng/mL for ACYN with
UV detection. The three perdeuterated surrogate PAHs were used to accomplish the procedural
efficiency, reproducibility and data correction from the evaporative losses during extraction and
work-up procedures. The recovery ranged respectively from 40.6% to 114% (mean = 82.8%),
69.4% to 141% (m = 97.5%), and from 73.9% to 121% (m = 94.6%) for for PHEN D10, FLA
D10 and PERY D12 with their relative standard deviations (RSD) of 15.2%, 14.6% and 12.6%.
Sedimentary organic carbon (OC) and organic nitrogen (ON) content were determined
using a Vario EL III CHNOS Elemental Analyser at 1800oC (during combustion) at the
GeoScience laboratory at the University of Bremen. 20 - 25 mg of the homogenized sediment
fraction were placed in a silver boat, treated with 30 L of 1 M HCl to remove inorganic carbon
and dried at 40oC. This process was repeated 2 3 times to make sure that all carbonates were
transformed into carbon dioxide. The relative standard deviation of the method was 5.9 %.
73
4.3. Results & Discussion
74
carbon). These sources were likely to reach the aquatic environment through soil washout or
land abrasion during high precipitation.
75
6000
5000
Sand
Mud
4000
PAHs (ng/g d.w.)
Bulk
3000
2000
1000
0
S 116
S 101
S 104
S 105
S 145
S 143
S 142
S 138
S 134
S 252
S 125
S 250
S 251
S 269
S 226
S 227
S 228
S 267
S 266
S 253
S 230
S 231
S 232
S 24
S 20
S 35
S 42
Fig. 2. Distribution of PAHs in sand and mud fractions of surface sediments from the Siak River, estuary
and the coastal areas. Stations are arranged downstream from the Siak tributaries over the estuary to the
coastal region.
A bulk PAH content (PAHBulk) was calculated for each station from the content for each
fraction and the proportion on the total sediment dry mass. PAHBulk of all aquatic systems
ranged from 145 to 1234 ng g-1 d.w.(Table 2). The coastal sediments turn out to contain the
highest PAHBulk with a median of 577 ng g-1 d.w., followed by the river and the estuary of 484
and 443 ng g-1 d.w., respectively. This calculation placed S42, S138, S253 and S269 as stations
having the highest PAHBulk (>1000 ng g-1 d.w.). In addition, these locations were also
identified as having the highest PAH concentration within the sand fraction alone. The spatial
distribution of PAHBulk as well as PAHs for the sand and the mud fractions did not show a
clear pattern between sampling locations towards the river mouth of the estuary area suggesting
various local inputs (Fig 2). However, the highest PAHBulk contamination was found in the
vicinity of urban and industrial centres (S42, S226, S269, and S253). In contrast, the lowest
PAHBulk contents were detected at the river upstream (S104) and in the estuary (S125).
Because most studies in the literature considered only the bulk assessment, the PAHBulk
could bring comparable information on their pollution level. Values of PAH >1000 ng/g d.w.
mostly represent chronically polluted industrialized areas and harbours (Baumard et al., 1998;
Tolosa et al., 2004). Therefore, the river sediment around the capital city of Pekanbaru (S42),
the coastal sediments in the vicinity of Dumai (S269, S226) and in the mouth of Selat Panjang
(S253) can be considered highly polluted, while the other locations show moderate pollution.
76
Direct comparison to those of other studies is somewhat difficult due to variation in numbers of
studied-PAHs (not all studies investigated all the 16 US EPA compounds), the analytical
performances and the background conditions. However, for a general idea of the PAH level,
relevant information from studies in several Asian and European countries are presented in
Table 3. The median values of PAH Bulk in surface sediments of Riau aquatic environments
were higher by a factor of two or more than those on the opposite side of the Malacca Strait
(Zakaria et al., 2002), the industrialized Gulf of Thailand (Boonyatumanond et al., 2006), and
the Pearl River Estuary plus its adjacent coastal areas of China (Luo et al., 2006). Higher PAH
in sediments from this study than in areas from the neighboring countries are assumed to be due
to greater inputs of PAHs from widespread, intense plantation and peat burnings. These sources
produced significant amount of PAH compared to other pyrogenic sources such as combustion
of fossil fuels which are typical sources of sedimentary PAH in urban and industrial
environments (e.g. Kakareka & Kukharchyk, 2003; Miguel et al., 1998).
77
particle surface area, it could be then assumed that the low C/N ratio of the fine fraction would
represent the condition of dissolved organic matter (DOM). Kalbitz & Geyer (2002) observed
that low C/N ratio of DOM is one characteristic property of a degraded peatland. Prahl and
Carpenter (1983) also observed evidences for a lack of correlation between PAHs and humic
substances that were enriched in the fine (<64m) fraction of the sediment samples from the
Washington coastal region, although no specific reason was mentioned.
To sum up, this PAH-OC association could suggest three modes of which the PAH
integrated into the aquatic systems. First, the PAH entered the aquatic environment favorably
binding to the OM with high affinity for PAH (i.e. black particles, vascular plant debris, or peat)
as found in S42, S116, S143, S138, S250, S232. Second, the PAH-OM came together from
similar sources, as present in the coarse fraction comprised of low OC content and low total
sediment weight. It was observed at the S230, S231, S269, and probably S226, and S253. Third,
the PAHs were unfavorable associated with the fine fraction due to uncondensed, less aromatic
fraction of the humic substances from the degraded peatland.
6000
5000
Sand Fraction
PAHs (ng/g d.w.)
4000
PAHs = 295.4*OC + 349.1
R2 = 0.7
3000
S253: the Coast
S269: Dumai Port
2000
1000
Estuarine S142
Sediment
0
0 5 10 15 20 25
OC (%)
Fig. 3. Correlation between PAHs and the organic carbon contents in the sand (
) and mud () fractions
of the sediments from the Siak River, the estuary and the coast (N=24, R2 =0.70 for the sand fraction, =
outliers).
78
A 3000
PAH vs OC <1%
2500
1500
1000
500
0
0.0 0.1 0.2 0.3 0.4 0.5
B 6000
PAH vs OC >1%
5000
PAHs (ng/g d.w.)
4000
3000
y = 351.24x - 128.98
2000 R = 0.78
1000
0
0.0 2.0 4.0 6.0 8.0 10.0 12.0 14.0 16.0
OC (%)
Fig. 4. Specific type of PAH-OC correlations for both fractions: (a) PAHs to low (<1%) OC content
suggesting that the PAH and the OC entered the aquatic systems from the same sources, and (b) PAHs
to high (>1%) OC indicating that the PAH sorption to the organic matter was a function of the OC
content and composition.
79
The other prevalent groups were the 4- and 5-ringed PAHs. The relative composition of
both groups greatly varied among the stations in all environments ranging on average from
10.6% to 21.0% for the 4-ringed PAHs, and from 9.12% to 32.7% for the 5-ringed PAHs. These
groups had a tendency to concentrate around the urban centres of Pekanbaru and Dumai cities.
However, the Siak tributaries of Tapung Kanan and Tapung Kiri Rivers were dominated by the
5-ringed PAH suggesting a potential repository for the high molecular PAHs.
Dibenzo(a,h)anthracene is the most abundant compound of the 5-ringed PAH in almost all the
stations. This compound was particularly pronounced in the Siak tributaries, in the estuary
(S143, S138, S134) and the Siak Kecil (S250), and in the coast (S253), where it made up ca.
50% to 90% of the relative composition of the 5-ringed PAH. Since those stations commonly
surrounded by large plantation and peatland, we assumed that biomass and peat burnings
occurring in the surrounded land could be the source of this compound. If this is true, increased
contents of DANTH and other 5-ring PAHs could become signatures of peat-generated PAHs.
However, further investigations (field and laboratory) on profiles of peat-generated PAHs from
this area are needed. Widespread distribution of 4- and 5-ringed PAH in the areas strongly
suggests invasive pyrogenic non-point sources which were most likely introduced to the aquatic
environments through soil washout and atmospheric deposition.
It is widely accepted that anthropogenic PAHs stem from two general sources: pyrogenic
and petrogenic, which in most cases co-exist in aquatic sediments. In identifying which source
is dominant, the apportionment for the PAH in many studies make use of specific characteristics
of low over high molecular weight ratio (LMW/HMW), and specific isomeric ratios such as
ANTH/(ANTH + PHEN), FLA/(FLA + PYR), BaA/(BaA+CHRY) (Neff 1979; Budzinski et
al., 1997; Yunker et al., 2002; De Luca et al., 2005; Soclo et al., 2000). Petrogenic origin from
maturation organic matters is typically marked by a high proportion of LMW (2 and 3 ring)
over HMW (4 to 6 rings) PAHs. For instance, naphthalene (2 rings) contributes more than half
of the total non-alkylated polyaromatic compounds in crude oil, followed by three-ring
substances, PHEN and FLU (Requejo et al., 1996).
The specific isomer ratios have often been used due to their molecular stability against
the increase temperature during pyrolysis. For example, phenanthrene is known to be
thermodynamically more stable than the kinetically-stable isomer anthracene (Budzinski et al.,
1997). The proportion of anthracene increases as processes involve higher temperatures. PAHs
from combustion sources have typical values for the ratio ANTH / (ANTH + PHEN) > 0.1;
FLA/(FLA-PYR) >0.5, and BaA/(BaA+CHRY) > 0.35. In contrast, PAHs associated with
petroleum e.g. crude oil, have typical values of those corresponding isomeric ratios of <0.1,
<0.4, and <0.2 respectively (Yunker et al., 2002). For instance, Alascan Crude Oil had for the
80
respective ratios values of 0.03, 0.26 and 0.10 (Requeojo et al., 1996). However, the boundaries
between the assigned values are not clear-cut, and any value falling between those determining
values is usually considered as mixtures of petroleum and combustion sources.
These ratios were applied in this study, and the assignment was carried out for both
fractions. The values of the isomeric ratios were cross-plotted to get a tendency of the data (Fig.
5). Our results showed that the ratio of LMW/HMW for most of the stations was < 1 clearly
indicating combustion sources, except for S104 and S105 in the upstream area of the River,
S125 in the river mouth and S251 the mouth of Siak Kecil, and S267 in the northern mouth of
the Bengkalis canal. The ratio of ANTH/(ANTH+PHEN) was respectively 0.1 0.05 (mean
standard deviation, n=9), 0.22 0.18 (n=8), and 0.2 0.2 (n=10) in the River, the estuary and
the coast confirming predominance of combustion sources. Likewise, the ratio of FLA/(FLA-
PYR) was respectively 0.48 0.24, 0.65 0.13, and 0.69 0.17. High values of this ratio (>
0.5) indicate typical biomass burnings such as grasses, wood, or agricultural debris. The ratio of
BaA/(BaA + CHRY) was 0.36 0.13, 0.36 0.15, and 0.47 0.17 for the River, the estuary
and the coast. These values were slightly larger than those of petroleum-combustion sources
(upper limit 0.35).
All ratios clearly showed that pyrogenic sources were dominant, mainly from biomass
(vegetation) with a small contribution from petroleum combustion (Fig. 5). These results could
be attributed to widespread and intensive agricultural burnings and forest/peat swamp fires that
occurs frequently in those areas particularly since the last severe outbreak of the El Nio.
Accordingly, pyrogenic PAHs, which were primarily formed during dry seasons and especially
during burn-episodes, were delivered to the river and the estuary through soil washout,
intensified during high rain and flood seasons. The widespread signature of pyrogenic PAHs
might also reflect the significance of atmospheric (wet/dry) deposition.
However, the signatures of petrogenic PAHs were also observed in the river, the estuary
and the coast. The river sediments are to a great extent contaminated by petrogenic sources,
which is particularly observable in the Siak upper tributaries (S101) and around the capital city
of Pekanbaru (S35, S116), the Siak Kecil River (S250), Dumai port (S269), and the mouth of
Bengkalis canal (S267). The petrogenic PAHs in the upstream river might stem from petroleum
discharges from many local small boats which were observable during the sampling. In general,
the petroleum contamination observed in the other stations could be attributed to oil discharges
from ships operation, regular transportation and cargo activities along the river as the study area
is one of the biggest oil-production sites in Sumatra. Strong petrogenic signatures were also
reported from estuarine and coastal sediments of the neighboring country, Malaysia (Zakaria et
al., 2002).
81
Petroleum Biomass Combustion
1.0
0.9
0.8
BaA / (BaA + CHRY)
Combustion
0.7
0.6
0.5
0.4
0.3
0.2
0.1 Petroleum
0.0
0.7
ANTH / (ANTH + PHEN)
0.6
Combustion
0.5
0.4
0.3
0.2
0.1
Petroleum
0.0
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
FLA / (FLA + PYR)
Fig. 5. Cross plot of PAH isomeric ratios of the sand and mud sediment fractions from the Siak River (),
the estuary (
) and the coast ( ).
4.4. Conclusion
The sediments contained PAHs at moderate to high level. The sand/coarse fraction
generally contained higher PAHs and OC content than did the mud/fine fraction. A PAH-OC
linear correlation was shown only by the sand fraction. Enriched PAHs in the high-OC sand
fraction plus the linear correlation indicated the existence of particular organic matter with high-
affinity for PAHs, such as black carbon, vascular plant, and peat. The spatial distribution
showed no clear pattern in distance to the river mouth. But, increased content of the PAHs was
centered at urban and industrial areas. The high molecular weight was widespread predominant
and the molecular ratios for source apportionment provide further evidences for pyrogenic
sources: biomass and petroleum combustions. PAHs were delivered to those aquatic system by
both land-water and air-water transports.
82
Acknowledgments
This study is part of the German-Indonesian SPICE Project Cluster 3.1., funded by the
Federal German Ministry of Education, Science, Research and Technology (BMBF, Bonn), and
supported by the German Academic Exchange Service (DAAD), and we thank you for all
supports. Also, we would like to extent our grateful to scientists and students from University of
Riau, Indonesia, and to SPICE German colleagues for their contribution during sampling
campaigns and discussion. Furthermore, we appreciate the help of our colleagues Dipl. Eng.
Immo Becker (Marine Science working group, Dept. of Biology/Chemistry, University of
Bremen) and Ms. Dominique Schobes for laboratory assistances, and Ms. Hella Buschhoff
(Department of Geoscience, University of Bremen) for organic carbon measurement. Last but
not least, we thank all reviewers for their constructive critics and comments.
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85
V. POLYCYCLIC AROMATIC HYDROCARBONS IN SURFACE
WATERS OF THE SIAK RIVER, ITS ESTUARY AND THE
COASTAL AREAS OF RIAU PROVINCE, INDONESIA:
DISTRIBUTION AND SOURCES
Abstract
Polycyclic aromatic hydrocarbons (PAHs) were studied both in water solution and in suspended
particulate matter (SPM) of the Siak river, including its estuary and the coastal areas of
Sumatra, Indonesia. Concentration of dissolved 16 PAHs according to the EPA selection
(PAHs) varied greatly in river, estuary and coastal water samples ranging from 129 to 5140 ng
L-1 (median = 824 ng L-1), 320 to 619 ng L-1 (m = 385 ng L-1), and 121 to 130 ng L-1 (m = 130
ng L-1), respectively. The PAHs in the SPM samples for those three aquatic systems ranged
from 1475 to 59050 ng g-1 (median = 5286 ng g-1), 156 to 7669 ng g-1 (m = 758 ng g-1), and 326
to 10234 ng g-1 (m = 1572 ng g-1), respectively. Two- to four-ring PAHs were predominant in
the water and particulate samples. PAH source apportionment was estimated using specific
isomer ratios in combination with the ratio of low and high PAH molecular weights. The
signatures of petrogenic and pyrogenic sources were found in all water systems, but biomass
burning signatures were more prominent. This might be evidence for palm-oil plantation and
peatland burnings which occurred frequently in the region since the last decades. The chemical
signatures of petroleum spillages were mainly observed around the River mouth and in the coast
north of the River, as well as close to the capital city of Pekanbaru, the industrial area Perawang
and Dumai city.
Keywords: PAHs; Suspended Particulate Matter; Water, Siak River; Estuary; Riau Coast
86
5.1. Introduction
87
5.2. Materials and Methods
S318 S317
S225 S227 S229 Malacca Strait
Dumai S228
S324
S226 S267
S266
Bengkalis
Bukit Batu River S233
Sumatra S124
S230
S251
Siak Kecil River S316S125
INDONESIA S132, S133 S128
S130, S126 S314 S231
S134
S305
S231
S139
Panjang
Strait
S 305 S 301
Upstream Segment Siak Sri Indrapura
Perawang S307
S216
S9
Tapung Kiri River S291
S 115
S17 S 370
S102 S10
S205
Pekanbaru
S105
S272
A S218 B C
Fig. 1. Map of the sampling locations for water (triangles) and suspended particulate matter (cycles). The
Siak River was sampled for three segments (dash-line boxes): (A) upstream; (B) Pekanbaru; (C)
Perawang.
During the three-year study (2004 2006), a total of 30 sampling stations along the river,
the estuary and the coastal areas were selected for particulate and 10 stations for dissolved PAH
assessments. Due to the large spatial scale, we selected sampling locations which represent a
variety of anthropogenic pressures which follow. First, the Siak River was sampled for (i) the
upstream region of the Siak including the Tapung Kanan and Tapung Kiri Rivers, which are
representative of agricultural sections surrounded by large palm-oil plantations, ii) the city
region around the capital Pekanbaru, and (iii) the downstream region enclosing the industrial
area of Perawang and the population centre of Siak Sri-Indrapura. Secondly, the estuary zone
88
was sampled following the salinity gradient from low (0 10 practical salinity unit, psu), over
medium (10 25 psu) and to high (> 25 psu) salinity. Finally, the coastal area was sampled
from the oil-industry city of Dumai in the north to the coastal channel between Bengkalis and
Sumatra Islands, and to Panjang Strait in the south of the Siak river, where several offshore oil-
ridges are located.
89
Milli-Q water. Thin film of water was left above the phase to avoid drying. The sample was
then aspirated through the cartridge at flow rate of ca. 5 mL/min controlled by adjusting the
pressure. After all of the sample was emptied, the cartridge was again washed with Milli-Q
water, and a little bit of water was left on top of the cartridge to avoid drying. Then, the column
was firmly wrapped with foil, sealed with a paraffin film, and stored at -4 oC until analysis.
The steps of the work-up procedure for the retained PAHs on the cartridge were relatively
simple compared to those for the SPM. Prior to elution, the cartridges were gently dried by a
stream of N2. Then, the PAHs were eluted with 4 mL of dichloromethane (DCM) (repeated
three times) at flow rate of 5 mL/min. The use of DCM for elution of PAH for SPE system has
been suggested (Sargenti & McNail, 1998). The elutes were reduced to a dry state by by N2
blow down, then 300 L of acetonitrile was added prior to analysis with high performance
liquid chromatography (HPLC).
90
D10) and 88.8% 9.9% (PERY D12), while for the SPM were 95.3% 10.1%, 96.8% 9.8%,
and 95.7% 8.9% for PHEN D10, FLA D10 and PERY D12, respectively.
91
5.3.2. PAHs in the SPM
The PAHs in the SPM samples from the Siak River ranged from 1475 to 59050 ng g-1
d.w (Table 2a). Very high contents (>15000 ng g-1 d.w) were detected in March 2004 in all river
segments (Fig. 2). The content of the PAHs generally decreased ever since, except in the
upstream segment where increased content was observed in September 2004. Monthly samples
(see: inset Fig. 2) taken at the upstream segment in 2004 showed that the contents of PAHs
remained very high until the wet season (September). It suggests that the upstream segment was
a potential repository for the particulate PAHs. Since the upstream segment is surrounded by
vast palm-oil plantations having experienced frequent burnings, it is expected that the high
content of PAHs was attributed to the burnings. Likewise the dissolved PAHs, NAPH, ACYN,
PHEN, FLA and PYR generally dominated the relative composition of individual PAH in all
segments.
60000 60000
PAHs (ng/g d.w.)
50000
PAHs (ng/g d.w.)
50000 40000
30000
40000 20000
10000
30000 0
Mar 04 May 04 Jun 04 Aug 04 Sep 04 Jul 05
20000
10000
0
Mar 2004 Sep 04 Jul 05 Mar 06
Upstream Tributaries Pekanbaru Perawang
Fig. 2. Seasonal distribution of particulate PAHs from Siak River waters. Inset: monthly
variation of the particulate PAHs from the upstream segment.
Fig. 3 illustrates the relative composition of the ring group PAH between dry and wet
seasons. It shows that the profile of the ring-group composition in the upstream part is similar
with 4-ring PAHs (i.e. FLA, PYR) being predominant. FLA and PYR accounted for ca. 48%
and ca. 24% of the individual composition. It confirms that PAHs stemmed from the same
sources throughout the year, most possibly from the burnings from palm-oil plantation and
92
peatland. The higher content in the wet season (2004) than in the dry season (2005) might
suggest that land runoffs (land-water interfaces), by which burning residues were flushed out to
the River, were more significant sources of particulate PAHs than atmospheric deposition (air-
water interfaces). However, there is a clear seasonal modification of the ring group composition
in the city of Pekanbaru and the industrial area of Perawang. The 3-ring PAHs (ACYN and
PHEN) were very dominant in the wet season in both segments. ACYN and PHEN contribute
ca. 40% and 20% of the individual relative composition, respectively. Instead of biomass
burnings, the PAHs were possibly derived from observable oil discharges during the samplings.
Oil discharges to the aquatic systems are not strictly monitored. In the dry season the
composition profile was shared among 3, 4, 5 and 6 rings. It suggests many various sources of
PAHs, possibly including urban and industrial wastewater runoffs and urban atmospheric
fallouts in addition to smokes from the plantation and peatland burnings during 2005.
70 Pekanbaru S272
Perawang S216
60
50
40
30
20
10
Upstream S102
70 Pekanbaru S105
60 Perawang S115
50
40
30
20
10
0
Fig. 3. The relative composition of the ring groups of the PAHs in the Siak River during (a) dry and (b)
wet seasons. The dash lines illustrate the ring-group profiles.
93
In the estuary, the PAHs in the SPM samples vary also greatly ranging between 156 and
7669 ng g-1 d.w. with a median of 758 ng g-1 d.w. (Table 2b). The PAHs was lower by an
order of magnitude than those of the River. The highest level (7669 ng g-1 d.w.) was observed at
S134 around Sungai Apit in the mouth of the River. The high content was partly due to another
potential input from the Channel connecting the blackwater Siak Kecil River and the Siak River.
There is no clear trend of distribution towards the coast (Fig. 4). As to individual PAHs, the
relative composition of PAHs was shared among NAPH, ACYN, PHEN, FLA, and DANTH. In
general, the 4-ring PAHs are dominant, followed by the 3- and 5-ring PAHs (Fig. 5).
12000
Particulate PAHs (ng/g d.w.)
10000
8000
6000
4000
2000
0
S139
S140
S137
S134
S132
S124
S133
S225
S226
S227
S228
S229
S267
S266
S233
S251
S230
S231
S232
S130
S126
S125
S128
The Siak Estuary (Sep 04) The Riau Coast (Jul 05)
Fig. 4. Spatial distribution of particulate PAHs in the Estuary and the Coast.
The PAHs in the coastal SPM was higher than those of the estuary extending from 326
to 10234 ng g-1 d.w., with a median of 1572 ng g-1 d.w. (Table 2c). The high values at S267 and
S266 were possibly due to an accumulation of PAH-rich particle plumes from blackwater
streams in the area including the Siak River, the Siak Kecil River and Bukit Batu River. In
addition, significant plumes of humic substances from those three blackwater streams into the
Malacca Strait have been recognized (Siegel et al., 2009). The relative composition of the ring
group PAHs was dominated by 4-ring PAH mainly FLA and PYR (Fig. 6). The high portion of
4-ring PAH were also shared by the estuarine SPM and the upstream segment of the River SPM.
It might indicate the common sources (i.e. palm-oil plantation and peatland burnings). The
profile of coastal plume and Malacca strait (at blue water stations) is slightly different in which
the relative composition of 6-ring PAHs increased in the Malacca Strait (Fig. 6a). It is most
likely due to diesel and gasoline combustion derived from vast ships along the Strait. Diesel and
94
gasoline combustion emit relatively high proportion of high molecular PAHs (e.g. Riddle et al.,
2007). NAPH was higher in the coastal than in the estuarine SPM. Increase in 2-ring PAH in
the coast might partly stem from oil discharges since the coastal areas are being the main
transport pathway for oil cargos. It suggests a chronic petroleum contamination around the river
mouth and the coast. Furthermore, a proportion of 2- to 3-ring compounds were more
pronounced along the coast north of the river mouth (including Bengkalis and Dumai Strait)
than the coast south of the river mouth or Panjang Strait (Fig. 6b). It suggests that the north of
the river mouth was more affected by petroleum sources.
A
45 Dry Season (July 2005) The Estuary
40 The Coast
Relative Composition (%)
35
The Malacca Strait
30 (S229)
25
20
15
10
5
0
B
45 The Coast
Dry Season (July 2005) Northern part
40
Relative Composition (%)
35 Southern part
30
25
20
15
10
5
0
2 rings 3 rings 4 rings 5 rings 6 rings
Fig. 5. The relative composition of the ring groups of the PAHs. The dash lines illustrate the ring-group
profiles. (a) the profiles in the estuary (median value, n=10), the coast (median value, n=11) and the
Malacca Strait (at S229), (b) the profiles in northern and southern (of the Siak River mouth) parts of the
coast.
On a volume basis, the concentration of particulate PAHs ranged from 62.5 to 694 ng
L , 25.4 to 293 ng L-1, and 11.7 to 147 ng L-1 in the River, the estuary and the coast,
-1
95
respectively. The concentration decreased towards the coastal waters similar to those of
dissolved PAHs (Fig. 6). But, the volume concentration of the particulate PAHs was lower by
up to one order magnitude compared to the dissolved PAHs. The decrease from the river to the
coast suggests entrapment and dilution effect of sea water. In comparison to other river, estuary
and coastal systems in Asia and Europe (Table 3), the content of PAHs in this study was
comparable to those rivers in industrial city of Tianjin, China (Shi et al., 2005), Seine River in
France (Fernandes et al., 1997), and Elbe River at Dessau (Heemken et al., 2000). Even, they
were higher than the Pearl River and Estuary, China (Luo et al., 2006).
800
600
Particulate 6PAHs (ng/L)
400
200
Fig. 6. Concentration of the particulate PAHs on volume base (ng/L) in Siak River (n=12), estuarine
(n=11) and coastal waters (n=12).
96
value in the coastal water is the highest. The partition of PAH is expected to increase as salinity
increases (Brunk et al., 1997; Turner & Rawling, 2001; Tremblay et al., 2006). However, the KD
values in the estuary were lower than those of Siak River (Fig. 7a). It means that increased
salinity did not automatically increase the sorption coefficients of PAHs suggesting other
factors enhancing their solubility. Dissolved organic matter (DOM) in the water solution
enhances the solubility of PAHs (Liu & Amy, 1993; McGroddy & Farrington, 1995).
a 6.0
b 8.0 Samples from Mar 2006 (mean values)
7.0
5.0
NAPH
Log KOC
Log KD
6.0
4.0 PHEN River (n=5)
FLA 5.0 Estuary (n=3)
BaP Coast (n=3)
3.0 Koc = Kow
BPERY 4.0
2.0 3.0
3.0 4.0 5.0 6.0 7.0
River Estuary Coast
Log KOW
c 8.0
6.0
5.0
4.0
BaP
3.0
0.0 5.0 10.0 15.0 20.0
DOC (mg/L)
Fig. 7. (a) Distribution coefficient (KD) of selected PAHs in the Siak River, its estuary and the Riau coast
(mean log values); (b) a cross plot of organic-carbon normalized distribution coefficient (KOC) vs.
compounds octanol-water distribution coefficient (KOW, the values taken from Williamson, et. al., 2002),
a measure of hydrophobicity; (c) a cross plot of Log KOC vs. DOC for BaP suggesting the role of
dissolved organic matter in enhancing the solubility of PAHs. DOC data was provided by Dr. A. Baum
and Dr. T. Rixen from ZMT Bremen, Germany.
To understand the effect of particulate organic matter (POM) on the distribution, organic
carbon normalized partition coefficient (KOC = KD /fOC) is evaluated, where fOC is the SPM
fraction of organic carbon. The results showed that the KOC was variable, and showed no
correlation between KD and fOC. It means that the KD is not dependent on the content of the
organic matter, but on the quality. The POM in the SPM had different affinity for PAH. Many
studies pointed out that in natural water the KOC of PAH compounds is higher than its
hydrophobicity (KOW) due to strong sorption of PAHs onto the combustion-derived organic
97
matter such as soot or black carbon (e.g. Jonkers & Koelmans, 2002; Gustafsson et al., 1997).
However, although the Siak water systems are severely affected by biomass burnings, the KOC
values is not all exceed the KOW (Fig. 7b). It might suggest a significant role of DOM enriched
in colloidal fraction from leaching peatland that maintained the PAH in the dissolved phase as
shown by an inverse correlation between KOC and DOC (Fig. 7c). Also, it might suggest that
the PAHs stemmed from non-combustion sources (e.g. Zhu et al., 2008).
98
On the other hand, the ratios FLA/(FLA+PYR) and the BaA/(BaA+CHRY) in all studied
areas show important pyrogenic sources, particularly biomass burning and petroleum
combustion. The FLA/(FLA+PYR) were 0.53 0.14 (mean SD), 0.49 0.18, and 0.39 0.10
in the River, the estuary and the coast. The respective values of the BaA/(BaA+CHRY) was
0.44 0.16, 0.38 0.21, and 0.48 0.11. As been applied in the many studies, cross plots of
FLA/(FLA-PYR) vs. ANTH/(ANTH+PHEN) and BaA/(BaA+CHRY) shows that pyrogenic
the dominant sources (Fig. 8). The ratios in the river water point more to biomass burning
signatures which were most possibly palm-oil plantation and peatland burnings, while mixtures
of sources between biomass burnings, petroleum combustion, and oil discharges were assigned
in the estuary and the coast.
Petroleum Biomass Combustion
1.0
0.9
Peat Burning
Combustion
0.8 Dumai light-duty diesel
BaA / (BaA + CHRY)
Agricultural vehicles
0.7
SPM after forest debris
0.6 fires Weat grasses
0.5
Rice grasses
0.4
0.3 Oil spills "Tanker Charcoal Bituminous coal
Enrika"
Petroleum
0.2
Estuary S137
0.1 Alaskan crude oil
Estuary S139
0.0
0.4
Bituminous coal
0.4
ANTH / (ANTH + PHEN)
Combustion
0.3
Agricultural
debris
0.3 Charcoal
0.2 Oil spills
"Tanker Enrika" Weat grasses
0.2 Rice grasses
Peat Burning
Petroleum
0.0
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
FLA / (FLA + PYR)
Fig. 8. Cross plots of isomer ratios for the source apportionment of PAHs in the Siak River (unfilled
triangles), the estuary (black squares), and the coast (black cycles) (discrimination values dash lines -
after Yunker et al., 2002). For comparison, literature data illustrates petrogenic and pyrogenic sources
(grey cycles). References: petrogenic sources: Alaskan Crude Oil (Requojo et al. 1996); Oil-spill Tanker
Enrika (Baars et al., 2002); pyrogenic sources: Bituminous coal (Liu et al 2009); Charcoal (Oanh et al.,
1999); Agricultural debris (Kakareka & Kukharchyk, 2003); Rice & Weat grasses (Jenkins et al.,1996);
light-duty diesel vehicle (de Abrantes et al 2004); Sumatra peatland burning-Dumai (See et al., 2007);
SPM after forest fire (grey triangle: Vila-Escale et al 2007).
99
5.4. Conclusion
The Siak River, its estuary and the coastal waters of Riau Province are highly
contaminated by PAHs. Enrichment of PAHs was centred at waters around residential and
industrial areas. Two- to four-ring PAHs were dominant in the both dissolved and particulate
phases. Source apportionment indicated petroleum and biomass burning sources in all studied
areas. This reflects the decisive effects of biomass burnings and swamp/forest fires, as well as
oil discharges from vessel, port activities, urban and industry.
Acknowledgments
This study is part of the German-Indonesian SPICE Project Cluster 3.1., funded by the
Federal German Ministry of Education, Science, Research and Technology (BMBF, Bonn), and
supported by the German Academic Exchange Service (DAAD). We would like to show our
gratitude to scientists and students from University of Riau, Indonesia, the crew of RSV
Senangin, and to SPICE German colleagues for their contribution during sampling campaigns
and discussion. Last but not least, we thank all reviewers for their constructive critics and
comments.
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103
VI. A COMPARISON OF POLYCYCLIC AROMATIC HYDROCARBONS
(PAHs) IN PEATLAND AND NON-PEATLAND AQUATIC SYSTEM
SURFACE SEDIMENTS: A STUDY OF THE SIAK ESTUARY,
SUMATRA, INDONESIA AND OF THE WENCHANG AND
WANQUAN ESTUARIES, HAINAN ISLAND, CHINA
Abstract
104
6.1. Introduction
105
systems, including their distribution in sediments. The characterization of PAHs in sediment
taken from humic-rich aquatic systems containing degraded peatland is also relevant for a better
environmental management.
This study aims to compare the PAH distributions in surface sediments for two
Wentworth size fractions: coarse (2mm 63m) and fine (<63m). Samples were taken from
both a typical peatland- and a non-peatland aquatic system. This case study links two
international research projects analyzing land-borne material transfer. The first is the Science
for the Protection of Indonesian Coastal Marine Ecosystem (SPICE) program, a cooperative
German-Indonesian research effort. The second is the Land-Sea Interactions along Coastal
Ecosystems of Tropical China: Hainan (LANCET) program, a German-Chinese cooperative
research project. The sediments collected were examined for their total PAH content, their PAH
compositions, and their sources. The two sampling areas were the Siak River estuary in
Sumatra, Indonesia and the Wenchang/Wanquan Estuaries in Hainan, China. The main
difference between the two aquatic systems is comparably very high level of dissolved (humic)
organic carbon (DOC) in the Siak estuary. Thus, one aim of the present study is to investigate
whether a high dissolved humic content stabilize the PAHs in the water column and prevent it
from transfer to the sediment.
106
and July 2007 LANCET sampling campaigns. The samples were collected directly from a boat
using a sediment grab sampler. They were immediately homogenized before being placed in
closed aluminum jars and brown glass containers. During homogenization, foreign objects such
as large sticks, stones or any other synthetic waste were removed. The samples were kept cool
(ca. 4oC) during transport to the laboratory, where they were frozen (-20oC) and stored until
further treatment. Fractionation was performed by wet sieving the material to separate the
coarse fraction (2 mm - 63 m). The fine fraction (< 63m) was collected by centrifuging the
remaining sample.
Sumatra
S253
S230
S 250
INDONESIA S134 S231
S138
S232
S143
107
B CHINA
Wenchang
Hainan
Wanquan
BOAO CITY
CC02-1/07
BB4/07
K/06 Aquaculture
WW8/07
WRB/06
H/06
Wanquan WENCHANG
CITY WW10/07
Coastal Estuary
Wenchang
Coastal Estuary
Fig. 1. The maps of the sampling stations: (A) the Siak estuary (crossed cycles), Sumatra, Indonesia; (B)
the Wenchang and Wanquan Estuaries (black cycles), Hainan, China.
Up to 10g of the sediment fractions were spiked with three surrogate perdeuterated PAH
standards: d10-phenanthrene (PHEN D10), d10-fluoranthene (FLA D10) and d12-perylene
(PERY D12), then extracted in a Soxhlet-modified extractors (SoxTec) with solvents suggested
by the ICES Method (ICES, 1997) for 6 8 hours. The first cycle was extracted using acetone,
followed by a mixture of acetone/hexane (1/9 ; v/v) in the second cycle. The extracts were then
combined and reduced to ca. 1 mL by a rotary evaporator. A 1:2 (w/w) deactivated
alumina/silica (10% / 3%) column, including dried anhydrous Na2SO4 to remove the co-
extracted water, was used to clean up the extract. During the cleanup process the extracts were
eluted with 40 mL of degassed 3/7 (v/v) dichloromethane/hexane. Excess solvent in the clean
extracts was removed by the evaporator, resulting in sample volumes of ca. 1 mL. Then, the
extracts were subjected to solvent exchange into acetonitrile (ACN) to allow high performance
liquid chromatography (HPLC) analysis.
Dissolved PAHs were obtained by filtering the water samples with GF/F, and the filtrate
was extracted using a SPE cartridge (Chromabond NH2/C18) obtained from Macherey-Nagel
GmbH (Dueren, Germany) at flow rate of ca. 5 mL/min controlled by adjusting the pressure.
Methanol (2% of the filtrates volume) was added to 0.5 to 1 L of the filtrate in order to enhance
108
the recovery. Deuterated surrogate standards were spiked into the sample to compensate the
procedural efficiency and reproducibility from any losses during extraction and work-up
procedure. The SPE cartridges were sequentially conditioned with 5 mL hexane and 10 mL
methanol, then washed with ca. 100 mL Milli-Q water before using. After all of the sample was
aspirated, the cartridge was again washed with Milli-Q water. Then, the column was firmly
wrapped with foil, sealed with a paraffin film, and stored at -4 oC until analysis. Prior to eluting
the retained PAHs, the cartridges were gently dried by a stream of N2. Then, the PAHs were
eluted with 4 mL of dichloromethane (DCM) (repeated three times) at flow rate of 5 mL/min.
The use of DCM for elution of PAH for SPE system has been suggested (e.g. Sargenti &
McNair, 1998). The elutes were reduced to a dry state by gently dried by N2 blow down, then
matrix was changed into ACN for HPLC analysis.
The samples were analyzed for 15 out of the 16 PAHs priority pollutants listed by the US
EPA, including naphthalene (NAPH), acenaphthene (ACEN), fluorene (FLU), phenanthrene
(PHEN), anthracene (ANTH), fluoranthene (FLA), pyrene (PYR), benzo(a)anthracene (BaA),
chrysene (CHRY), benzo(b)fluoranthene (BbFLA), benzo(k)fluoranthene (BkFLA),
benzo(a)pyrene (BaP), dibenzo(a,h)anthracene (DANTH), benzo(g,h,i)perylene (BPERY) and
indeno(1,2,3-c,d)pyrene (IPYR); the EPA priority PAH acenaphthylene was not analyzed.
Baseline separation and quantification of those compounds was performed using a reverse phase
RP-C18 column (250 x 4.6 mm, 5m) and high performance liquid chromatograph (HPLC LKB
2249 Broma) with ultraviolet and programmable fluorescence detectors. Elution was 55%
acetonitrile (ACN) : 45% water for 10 min at the beginning of the elution program (isocratic),
55% to 100% ACN (a linear gradient at 2.25% ACN/min.) for 20 min, and 100% ACN for 10
min at the last program before the composition of the elution was set back to 55% ACN for 5
min. The elution was programmed at a constant flow rate of 1 mL min-1 for in total of 45
minutes.
HPLC grade acetonitrile and analytical-grade solvents (acetone, dichloromethane and
hexane) were used throughout the analytical procedures. A certified mixture of 16 PAHs
standards (purchased from Dr. Ehrenstorfer GmbH, Germany) were used to identify and
quantify the analytes. The limit of detection ranged from 0.4 ng/mL (BaP) to 12 ng/mL (NAPH)
for fluorescence detection. The three perdeuterated surrogate PAHs were used to achieve
procedural efficiency, reproducibility and data correction from any losses during the extraction
and work-up procedures. The recovery ranged respectively from 64.5% to 114% (mean =
87.8%), 67.3% to 119% (m = 93.2%), and 61.6 to 121% (m = 92.8%) for PHEN D10, FLA D10
and PERY D12 with their relative standard deviations (RSD) of 16.1%, 13.5% and 14.3%. The
109
mean recovery standard deviation of the deuterated surrogates for the SPE was 100% 16.1%
(PHEN D10), 90.6% 4.55% (FLA D10) and 93.4% 10.7% (PERY D12).
6.3. Results
110
did not exactly follow the pattern emerged, showing variation between the stations. BPERY
was the only compound which was mainly enriched in the fine fraction from the Siak samples.
In the WW/WQ sediments, only the sample taken from Wanquan station B/06 showed a
similar distribution pattern as those for most of the Siak samples.
With respect to total PAH content, Fig. 2 compares the distributions for the Siak
sediments and the WW/WQ sediments. In general, there was a large difference in PAH
distributions between the two distinct environmental settings. The total content of PAHs tended
to be higher in the coarse fraction (m = 689 ng/g d.w.) for Siak sediments than it was in
WW/WQ sediments. On the other hand, the fine fraction of the Siak sediments contained less
PAHs (m = 202 ng/g d.w.) than that of similar WW/WQ sediments (m = 430 ng/g d.w.). This
pattern of PAH distribution correlates well with the pattern of OC contents. As a proxy, the C/N
ratios suggest dissimilar sources for the organic matter isolated from the coarse and fine
fractions. The C/N ratios for the coarse sediments generally tended to be higher than those of
the fine fractions for both the Siak and the WW/WQ sediments. They ranged from 12.4 to 47.9
with a mean ratio of 23.3 and from 10.1 to 88.2 (mean = 38.8), respectively. On the other hand,
the fine fraction C/N ratios ranged from 8.85 to 20.4 (mean = 16.2) for the Siak and from 11.6
to 52.3 (mean = 19.0) for the WW/WQ sediments. As a point of reference, C/N end-member
values of ca. 7 and higher than 20 are commonly used to define marine and terrigenous origins,
respectively (Meyer, 1994; Holtvoeth et al., 2005). Values between 6-12 suggest a mixture
dominated by marine-originated organic matter (Ruttenberg & Goi, 1997).
2000
A Siak - SUMATRA
1800
1600 Coarse
PAH15 (ng/g d.w.)
1400
Fine
1200
1000
800
600
400
200
0
S 143 S 138 S 134 S 250 S 253 S 230 S 231 S 232
500
400
300
200
100
0
Fig. 2. Distribution patterns of PAHs (as PAH15) in the coarse and fine fractions of the Siak sediments
(A) and the Wenchang and Wanquan sediments (B).
111
6.3.2. Relative Composition of PAHs
The relative composition of PAH compounds was largely identical between the fractions
in both studied areas, as can be seen by both the individual and the ring-group compositions
(Fig. 4 and Fig. 5). However, there was a significant difference in the proportions between the
two areas. In the Siak estuary and coast, the relative composition of the PAH compounds was
shared almost evenly by the compounds, except for NAPH and DANTH (m = > 15%). Even,
the relative composition of DANTH reached up to 30% in the coarse fraction. For the WW
estuary and coast, the PAHs were dominated by PHEN, FLA, PYR, and BbFLA with median
values of the relative composition of those compounds > 12%, except for FLA (m = 5.93%) in
the coarse fraction.
The ring-group compositions (Fig. 5) classified as 2 ring (NAPH), 3 rings (ACEN, FLU,
PHEN, ANTH), 4 rings (FLA, PYR, BaA, CHRY), 5 rings (BbFLA, BkFLA, BaP, DANTH),
and 6 rings (BPERY, IPYR) also showed a distinct pattern. The significant difference between
the studied areas was that the presence of 5-ring PAHs was high for the Siak sediments with a
median relative composition > 30%, whereas the WW/WQ sediments were generally dominated
by 3- and 4-ring structures (m = > 30%).
A
40 Siak - Sumatra
Relative Composition (%)
35 (median values)
30
Fine
25
20 Coarse
15
10
5
0
B
40 Wenchang and Wanquan Hainan
Relative Composition (%)
35 (median values)
30
25
20
15
10
5
0
Fig. 4. Comparisons of the relative composition of the individual PAH to the to the PAH15 between the
coarse and the fine fractions for the Sumatra and Hainan estuary and coasts.
112
A 60 Siak - Sumatra
40 Fine
30 Coarse
20
10
0
2 rings 3 rings 4 rings 5 rings 6 rings
50
(median values)
40
30
20
10
0
2 rings 3 rings 4 rings 5 rings 6 rings
Fig. 5. Comparison of the contribution of the PAH ring group to the PAH15 between the coarse and the
fine fractions of (A) Siak sediments and (B) Wenchang and Wanquan sediments.
Ratio of isomers for PAHs with the molecular weights 178 (ANTH, PHEN), 202 (FLA,
PYR) and 228 (BaA, CHRY) have been widely employed to apportion sources to either
combustion or petroleum origins (Neff 1979; Budzinski et al., 1997; Yunker et al., 2002; De
Luca et al., 2005; Soclo et al., 2000). These isomers have molecular stabilities with increasing
temperature during pyrolysis. For instance, phenanthrene is thermodynamically more stable
than the kinetically-stable isomer anthracene (Budzinski et al., 1997). The proportion of
anthracene increases as burning processes involve higher temperatures. In this study, the
molecular ratios of ANTH/(ANTH + PHEN), FLA/(FLA + PYR), BaA/(BaA+CHRY) were
applied. PAHs from combustion sources typically have the following values: ANTH / (ANTH
+ PHEN) > 0.1; FLA/(FLA-PYR) > 0.5, and BaA/(BaA+CHRY) > 0.35 (Yunker et al., 2002)..
In contrast to this, PAHs associated with petroleum, e.g. crude oil, have typical values for the
same isomeric ratios of < 0.1, < 0.4, and < 0.2 respectively (Yunker et al., 2002). For instance,
Alaskan Crude Oil has values of 0.03, 0.26 and 0.10 for these three ratios (Requeojo et al.,
1996). However, the boundaries between the assigned values are not set in stone. Any value
falling between those determining values is usually considered to evidence a mixture of
113
petroleum and combustion sources. Those values are then cross-plotted to discover the tendency
of the data (Fig. 6). Additionally, isomeric ratio data from a range of literature were reviewed
and also plotted in the Fig. 6 to get an understanding on to what extent these determining values
can properly distinguish pyrogenic and petrogenic sources of PAHs.
Our results show that the ratio of ANTH/(ANTH+PHEN) in the Siak sediments was 0.21
0.18 (mean standard deviation, n = 8) and 0.14 0.07 in the coarse and fine fractions,
respectively. Likewise, the coarse and fine ratios of FLA/(FLA-PYR) were 0.59 0.13 and 0.59
0.22, and that of BaA/(BaA + CHRY) was calculated as 0.48 0.15 and 0.36 0.08. These
ratios suggest that the PAH contamination found in Siak River sediments generally stems from
pyrogenic sources. On the other hand, the WW/WQ coarse sediment samples yielded ratios of
ANTH/(ANTH+PHEN), FLA/(FLA-PYR) and BaA/(BaA + CHRY) with values of 0.01 0.01,
0.47 0.24, and 0.39 0.24, respectively. The corresponding ratios in the fine sediments were
0.02 0.01, 0.55 0.21, 0.54 0.26. These values strongly suggest that the PAHs in the
WW/WQ sediments are generated by a mixture of both petrogenic and pyrogenic sources.
114
6.4. Discussion
It is obvious from the distribution of PAHs in the size-fractions that the Siak and the
WW/WQ sediments are fundamentally different (Fig. 2). Quantitatively, Siak sediments were
characterized by higher levels of PAHs in the coarse fractions as compared to the finer ones.
The situation for the WW/WQ sediments was the exact opposite, with higher PAH contents
found in the fine fractions. Qualitatively, the relative compositions of individual and ring-group
PAHs was also distinct between the two aquatic systems, however, they were largely similar
between the fractions located within a given system (Fig. 4 and Fig. 5). These deviations
suggest that the PAH sources located in these two sampling areas were different. DANTH and
NAPH significantly contributed to the relative composition of the total PAHs analyzed in the
Siak sediments. During Sumatran peatland burnings, the resulting smoke contained DANTH
levels commensurate with the values observed for Pekanbaru, the capital city of Riau province.
NAPH levels for this area, however, remained low (See et al., 2007). Therefore, high DANTH
in the sediments may be a strong indicator stemming from burnings. However, further
investigation is needed to determine whether DANTH is a main product of Sumatra peatland
burnings. Additionally, high NAPH levels in the Siak sediments were assumed to stem from
other sources than biomass burnings, specifically crude oil. High NAPH contents in the crude
oil obtained from this region have already been confirmed. For example, Requejo et al. (1996)
pointed out that NAPH contributes more than half of the total non-alkylated polyaromatic
compounds in crude oil. Likewise, Wang et al. (1999) observed that naphthalene and its alkyl-
homologues (C1-C4) comprised up to 86% of the total PAHs in Diesel No.2 and up to 99% in
Jet B fuel. If these findings are general, then Siak sediments have been affected by crude oil
pollution. On the other hand, PAHs in the WW/WQ sediments are characterized by high
contents of PHEN, FLA, PYR, and BbFLA. The isomeric ratio for ANTH/(ANTH+PHEN) was
relatively low with a mean value of 0.01. This value was largely similar to that for bituminous
coal emissions (e.g. Yang et al., 1998). The ratios for FLA/(FLA+PYR) and
BaA/(BaA+CHRY) are in agreement with those calculated for coal and petroleum combustion
(e.g. Marr et al., 1999; Li et al., 1999).
Sedimentary organic matter is a pivotal factor affecting PAH distribution in the coarser,
grain-size fractions. In this study, higher PAH contents generally correspond to higher OC
contents for both aquatic systems. The distribution of the OC content between the grain-size
fractions showed similar patterns to their corresponding PAH contents. The higher OC contents
(median = 4% d.w. ) and the C/N ratios (mean value = 23) found in the coarse fraction of Siak
sediments confirmed that highly condensed organic matter such as that stemming from burning
residues (often termed black carbon, BC), plant debris, and peat existed. C/N values of > 20 are
commonly associated with terrestrial plants, thermal degradation of biomasses, or peat
115
(Holtvoeth, 2004, Pillon et al., 1985). Therefore, we can conclude that the high PAH levels in
the coarse fractions of Siak sediments are most probably associated with the presence of
burning events, their residues, peat, and fragmented plant materials. These materials show a
strong affinity for PAHs (e.g. Rockne et al., 2002; Ghosh et al., 2003; Cornelissen &
Gustafsson, 2004; Gustafsson et al, 1997; Grathwohl, 1990). Black carbon is also co-produced
with PAHs during combustion processes (Jonker & Koelmans, 2002). The presence of such
carbonaceous materials in Siak River sediments strongly indicates that the Siak, its estuary and
the coastline are affected by peatland fires and biomass burnings. Such large PAH contents can
conceivably be produced during peatland burning, including occlusion of PAHs in matrixes of
the burning residues. These substances are then free to enter the aquatic system via both land
drainage and atmospheric deposition. High erosion rates have been recognized in much of the
Siak estuary and the along the coast as evidenced by increases in the suspended particulate
matter load (see Siegel et al., 2009). In comparison, the coarse fraction of the WW/WQ
sediments were typically characterized by organic-poor matter, especially silica particles as
commonly found along the Hainan coast (e.g. Ghosh et al., 2000). Quantitatively, the organic
matter contents in the coarse fraction are generally small for the Chinese samples, but had high
C/N ratios (mean value = 39). This suggests that the organic matter in these sediments was
limited to that of carbonaceous materials already existing in the fraction.
On the other hand, the PAH content in the WW/WQ fine fractions was higher than in the
coarse fraction of the sediments. As we might expect from the large values of surface area per
gram of sediment, the particles of the fine fractions provided an excellent environment for
sorption from solution. The higher PAH levels in the fine fraction of these sediments can also be
attributed to the larger OC content as compared to that of the corresponding coarse fraction.
This suggests that the PAHs of the sediment particles were controlled by an equilibrium
sorption process of PAHs onto the sedimentary organic matter. The OC contents calculated for
the fine fractions of both the Chinese and Sumatran aquatic systems were largely the same, with
median values of ca. 2% d.w.. The relatively low C/N ratio (median = 13) determined for the
WW/WQ fine sediments suggests a mixture of both marine and terrestrial organic matter. On
the other hand, the relatively high C/N ratio (m = 18) representative of the Siak River's fine
fraction can most likely be attributed to the presence of humic substances.
With regard to PAH-organic matter sorption rates, the lower PAH levels associated with
the fine fractions in Siak sediments (as compared to those for the coarse fraction) can be
hypothetically driven by two causal mechanisms. First, the presence of combustion residues in
the coarse fraction might increase sorptive competition for PAHs, meaning that carbonaceous
materials rather than bulk organic matter would be favoured (see Luthy et al., 2002; Cornelissen
& Gustafsson, 2004; Accardi-Dey & Gschwend, 2002). Gustafsson et al. (1997) observed
elevated sediment-porewater PAH partitioning rates, which occurred whenever soot-partitioning
116
was included in calculating the hydrophobic partition model. Cornelissen & Gustafsson (2004)
concluded that black carbon (BC) emerges as the most important overall geosorbent constitute
in the case of low aqueous PAH (concentrations below ng/l). That would be in agreement with
our studies since the PAH concentration existing in solution was in the range of 121 to 619
ng/lin the Siak estuary, and 7.36 to 16.2 ng/lin the WW/WQ estuary and coast. . In addition,
Accardi-Dey & Gschwend (2002) infer that absorption by natural organic matter and adsorption
onto BC act in parallel to bind PAHs in Boston Harbor sediments. This means that the presence
of BC in the coarse sediments may outcompete the fine grain sediments for the sorption of
PAHs. Second, PAH sequestration in sediments can be affected by humic-enriched or highly-
organic porewater and overlying water. Siak estuary and the coast contained significant amount
of DOC compared to the Wenchang and Wanquan coastal estuaries (Balzer, unpublished data).
The calculation of the sediment-water distribution coefficient showed that the KD values in the
Siak estuary are the generally lower than those of the non-peatland water of Hainan suggesting
that high DOC in the Siak water may sustain the PAHs in the water column impeding their
association onto the sediment organic matter. Such role of colloid or DOC in sustaining the
PAHs in the water has been recognized. For instance, Chin & Gschwend (1992) observed
increased PAH sorption levels onto porewater colloids in heavily contaminated Boston Harbor
sediments. Yu et al. (2009) found that PAHs tend to be released from sediments into porewater
as the dissolved organic matter content of the porewater increases. Therefore, we can infer that
increasing the amount of DOC colloids in the porewater and the water column will affect the
sorption/desorption of PAHs by the fine fraction. However, these insights also need further
investigation to show how accurate these suggestions really are.
117
Petroleum
Combustion Grass/Wood/Coal
Petroleum Combustion
1.0
0.9
Peat Burning
0.8 Dumai light-duty diesel
BaA / (BaA + CHRY)
Agricultural
vehicles Combustion
0.7
debris
SPM after forest
0.6 fires Weat grasses
0.5 Rice grasses
Oil spills
0.4 "Tanker Enrika"
Bituminous coal Mixed
0.3 Charcoal
Sources
0.2
Petroleum
0.1 Alaskan crude oil
0.0
0.4
0.3 Combustion
Agricultural
0.3 debris
Charcoal
Oil spills "Tanker
0.2 Enrika"
Peat Burning Weat grasses
0.2 Dumai Rice grasses
0.1 light-duty diesel
Alaskan crude
oil vehicles
0.1 Petroleum
WW8
0.0
WW10
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
FLA / (FLA + PYR)
Fig. 6. Cross plots of PAH isomeric ratios for the source apportionment of PAHs in the Siak coarse (solid
squares) and fine sediment fractions (unfilled squares), and in the Wenchang Wanquan coarse (solid
triangles) and fine (unfilled triangles) sediment fractions. The discrimination values dashed lines were
adopted from Yunker et al. (2002). For comparison, various literature data of PAHs emissions and crude
oils (light grey cycles) are additionally presented to illustrate how the determining values properly
address data variation. References: petrogenic sources: Alaskan Crude Oil (Requejo et al. 1996); Oil-spill
Tanker Enrika (Baars et al., 2002); pyrogenic sources: Bituminous coal (Liu et al 2009); Charcoal (Oanh
et al., 1999); Agricultural debris (Kakareka & Kukharchyk, 2003); Rice & Weat grasses (Jenkins et
al.,1996); light-duty diesel vehicle (de Abrantes et al 2004); Sumatra peatland burning-Dumai (See et al.,
2007); SPM after forest fire (grey cycle with black outline: Vila-Escale et al 2007).
118
6.00 Siak Wenchang and Wanquan
SUMATRA HAINAN
NAPH
5.50
ACEN
FLU
5.00 PHEN
ANTH
FLA
4.50
PYR
BaA
4.00 CHRY
log KD
BbFLA
3.50 BkFLA
BaP
DANTH
3.00 BPERY
IPYR
Fig. 7. Sediment-water distribution coefficient (log KD) of PAHs presented as a mean value of each
individual compound from the Siak and the Wenchang and Wanquan estuaries. The median values (black
and unfilled marks) were to represent the general differences between the two systems.
6.5. Conclusion
The Siak aquatic system, which is composed largely of degraded peatland, was found to
have enriched PAH levels associated with the coarse sediment fraction. This was particularly
true in the presence of carbonaceous materials such as biomass burning residues, peat and
fragmented plant debris. These materials have been shown to act as favorable adsorption
matrices for PAHs, especially in coarse sediment fractions. It is suggested that unfavorable
sorption of PAHs onto fine sediments associated with the organic matter in the Siak River
systems could be due to the existence of high levels of DOC found in the water column, which
can increase the partitioning effect on PAHs. However, in non-peatland areas of Hainan,
enriched PAH contents are mainly found in the fine fraction as expected. The relative
composition of PAHs between the grain-size fractions is similar either in the Sumatran or
Hainan areas suggesting that PAH contamination stemmed from similar sources. Furthermore,
the isomeric ratios used for source apportionment indicated that the PAHs found in the Siak
basin had mostly been generated through biomass burnings, whereas PAHs analyzed in the
WW/WQ sediments from Hainan Island stemmed from a mixture of coal and petroleum
combustion. For the total content of PAHs not only the sources of PAHs are important
(pyrogenic or petrogenic), but also other factors such as sediment fraction size, PAH ring size,
119
aromaticity, type of sorbent material and the levels of OM, DOC, BC in both the sediments and
the porewater. Therefore, we can conclude that the high PAH levels in the coarse fractions of
Siak sediments are most probably associated with the presence of burning events, their residues,
peat, and fragmented plant materials.
Acknowledgments
This study is part of the German-Indonesian SPICE Project Cluster 3.1., and of German-
Chinese LANCET research project, funded by the Federal German Ministry of Education,
Science, Research and Technology (BMBF, Bonn), and also supported by the German
Academic Exchange Service (DAAD). We acknowledge all their supports. Furthermore, we
would like to extent our grateful to scientists and students from University of Riau, Indonesia,
the Institute of Estuarine and Coastal Research, East China Normal University, China, and to
SPICE German colleagues for their contribution during sampling campaigns and discussion.
Furthermore, we appreciate our colleagues at Leibniz Centre for Tropical Marine Ecology ZMT
Dipl. Ing. Matthias Birkicht, Ms. Dorothee Dasbach, for the organic measurement and
Ms. Sonia Tambou (Marine Chemistry Working Group, Uni-Bremen) for laboratory assistance.
Finally, we thank all reviewers for their constructive critics and comments.
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123
124
Appendix 1. Physical & chemical properties of 16 PAHs of the US EPA priority pollutants.
No. Compounds Molecular Mol. CAS Boiling Melting Water Vapor Henrys Law Octanol-Water
e Partition
Formula Weighta,b number a,b Point a Point a Solubilityd Pressurea Constant
d
KH Coefficient
(g/mol) (BP oC) (MP oC) mg/L (mm Hg)
(atm m3/mol) Log Kow
1. Naphthalene C10H8 128,17 91-20-3 218 80.5 30.2 8.89E-02 4.50E-03 3.45
2. Acenaphthylene C12H8 152,20 208-96-8 256-275 92-93 16.1a 2.90E-02 n.a. 3.98e
3. Acenaphthene C12H10 154,21 83-82-9 279 96.2 3.93 3.75E-03 2.40E-04 4.22
4. Fluorene C13H10 166,22 86-73-7 293-295 116-117 1.90 3.24E-03 7.40E-05 4.38
5. Phenanthrene C14H10 178,23 85-01-8 340 101 1.18 6.80E-04 2.70E-04 4.46
6. Anthracene C14H10 178,23 120-12-7 340 214-216 0.076 2.55E-05 1.80E-06 4.54
7. Fluoranthene C16H10 202,26 206-44-00 375 151* 0.260 8.13E-06 1.95E-03 5.20
8. Pyrene C16H10 202,26 129-00-0 393 156 0.135 4.25E-06 1.30E-05 5.30
9. Chrysene C18H12 228,29 218-01-9 448 255-256 0.0015 7.80E-09 n.a. 5.61
10. Benzo(a)anthracene C18H12 228,29 56-55-3 435 162 0.011 1.54E-07 1.20E-06 5.91
11. Benzo(a)pyrene C20H12 252,32 50-32-8 495* 176.4* 0.0038 4.89E-09 7.40E-05 6.35
12. Benzo(b)fluoranthene C20H12 252,32 205-99-2 n.a. 162-165* 0.0140 8.06E-08 n.a. 5.78
13. Benzo(k)fluoranthene C20H12 252,32 207-08-9 480 217 0.0080 9.59E-11 2.70E-07 6.20
14. Benzo(g,h,i)perylene C22H12 276,34 191-24-2 542* 277-279* 0.0003 1.00E-10 2.00E-07 6.90
15. Indeno(1.2.3-cd)pyrene C22H12 276,34 193-39-5 260* 160* 0.0005 1.40E-10 n.a. 6.51
16. Dibenzo(a,h)anthracene C22H14 278,35 53-70-3 n.a. 269-270 0.0005 2.10E-11 2.00E-09 6.75
n.a. = data not available; a = Weast & Astle, 1985; b = Bojes & Pope, 2007; c = Schwarzenbach et al. 1993; d = Williamson et al., 2002; e = Martinez et al., 2004;
* = Beilstein Database from various references as follows:
Fluoranthene (MP): Ref. 2, 1718469; Journal; Hershberg bei Fieser; Novello; JACSAT; Journal of the American Chemical Society; 62; 1940; 1855,1859 Anm. 23; DOI:
10.1021/ja01864a061; ISSN: 0002-7863.
Benzo(a)pyrene (BP): Ref. 1, 4467311; Journal; Lewis; Edstrom; JOCEAH; Journal of Organic Chemistry; 28; 1963; 2050,2053; ISSN: 0022-3263.; (MP): Ref. 9, 4258666; Journal;
Murray et al.; CJCHAG; Canadian Journal of Chemistry; 52; 1974; 557; DOI: 10.1139/v74-087; ISSN: 0008-4042.
Benzo(b)fluoranthene (MP): Ref. 2, 159677; Journal; Badger,G.M.; Spotswood,T.M.; JCSOA9; Journal of the Chemical Society; English; 1960; 4420 - 4427; DOI:
10.1039/jr9600004420; ISSN: 0368-1769.
Benzo(g,h,i)perylene (BP): Ref. 3, 6482028; Journal; Gonzalez, Maykel Perez; Toropov, Andrey A.; Duchowicz, Pablo R.; Castro, Eduardo A.; MOLEFW; Molecules; English; 9; 12;
2004; 1019 - 1033; ISSN: 1420-3049.; (MP): Ref. 9, 4276855; Journal; Aronson; Katlowitz; JINCAO; Journal of Inorganic and Nuclear Chemistry; 41; 1979; 1579; DOI: 10.1016/0022-
1902(79)80180-3; ISSN: 0022-1902.
Indeno(1,2,3-cd)pyrene (BP): Ref. 1 4623412; Journal; Studt; JLACBF; Justus Liebigs Annalen der Chemie; 1978; 530; ISSN: 0075-4617.; (MP): Ref. 3 4467311; Journal; Lewis;
Edstrom; JOCEAH; Journal of Organic Chemistry; 28; 1963; 2050,2053; ISSN: 0022-3263.
Appendix 2. Emission factors and isomeric ratios of PAHs from various pyrogenic
and petrogenic sources (literature data)
Appendix 2.1. Emission factors of PAHs (mg/kg fuel) from various coal, biomass, and
petroleum combustions
Emission
Sources Factor Remarks References
(mg/kg fuel)
Coal
Bituminous Coal 121 Cu addition at 800oC Yan et al 2004
Cupric oxide, CuO, addition at
Bituminous Coal 248 Yan et al 2004
1000oC
Coal Briquette 101 Cookstove in Southeast Asia Oanh et al., 1999
Bituminous Coal 109 Domestic heating Lee et al., 2005
Residential heating coal source:
Bituminous Coal 1435 Liu et al 2009
the Jinxi coal mine in Beijing
Coal source: the Datong coal
Bituminous Coal 1096
mine in Shanxi province
coal source: the Jinxi coal mine in
Anthracite Coal 77,8
Beijing
Coal source: the Datong coal
Anthracite Coal 151
mine in Shanxi province
Coal source: the Datong coal
Honeycomb Briquette 812
mine in Shanxi province
Samples from Elmsworth Willsch & Radke, 1995 cited in
Bituminous Coal 152
gasfield, Canada Achten & Hofmann, 2009
Bituminous Coal 137 Elmsworth gasfield, Canada
Bituminous Coal 153 Ruhr basin, Osterfeld Germany
Bituminous Coal 124 Ruhr basin, Hugo Germany
Bituminous Coal 164 Ruhr basin, Westerholt Germany
Bituminous Coal 155 Ruhr basin, Blumenthal Germany
Biomasses
Woods
Wind tunnel simulation of open
Almond 14,1 Jenkins et al.,1996
burning
Walnut 23,1 Jenkins et al.,1996
Pine 26,7 Jenkins et al.,1996
Fir 28,0 Jenkins et al.,1996
Chinese clay woodstoves 23,3 Domestic heating Oanh et al., 2005
Wood 36,8 Domestic burning Lee et al., 2005
Eucalyptus wood 1 33,5 Residential fireplace Schauer et al., 2001
Oak Wood 38,0 Schauer et al., 2001
Lao traditional wood chips 41,2 Cookstove fuel system in Asia Oanh et al., 2005
Thai bucket wood chips 50,2 Oanh et al., 2005
Cambodian traditional wood
53,4 Oanh et al., 2005
chips
Vietnam traditional wood
56,4 Oanh et al., 2005
chips
Eucalyptus wood 110 Open burning in Southeast Asia Oanh et al., 1999
Paper 68,8 Joss paper furnace Yang et al., 2005
Grasses / debris
Wind tunnel simulation of open
Rice grasses 15,1 Jenkins et al.,1996
burning
Corn grasses 45,3 Jenkins et al.,1996
Agricultural debris 410 Open burning Kakareka & Kukharchyk, 2003
Petroleum
Natural Gas 2,82 Industrial boiler Li et al., 1999
Diesel 2,86 Industrial boiler Li et al., 1999
Heavy oil 13,6 Industrial boiler Li et al., 1999
Fuel Oil 3,51 Industrial stacks, heavy oil plant Yang et al., 1998
Diesel 4,66 Heavy-duty Vehicles Marr et al., 1999
Diesel* 5,84 Light-duty Diesel Vehicles de Abrantes et al., 2004
*mg/km
125
Appendix 2.2. The isomeric ratios for source apportionment from various organic matter
combustion/burnings
126
Appendix 2.2.
127
128
Making a dilution
Prepared from Sub-Stock Prepared from CAL-2 Prepared from CAL-7
Dilution Factor 10 20 40 80 5 10 20 2.5 5 10
Volume standard (L) 1000 400 400 200 100 50 800 400 200 1600 800 400
Acetonitrile (L) 3600 3600 3800 3900 3950 3200 3600 3800 2400 3200 3600
Appendix 3.2.1. Percent recovery of surrogate standards used for compensating the
procedural efficiency and reproducibility in surface sediment fractions.
129
Appendix 3.2.2. Percent recovery of surrogate standards used for compensating the
procedural efficiency and reproducibility in SPM and SPE.
130
Appendix 4. Tables for the Manuscript in the Chapter IV
131
Table 2. Median and range of PAH contents (ng g-1 d.w.) in the global sediment fractions from
the Siak River, estuary and the coastal areas. The PAHs are ordered by following their elution
time. PAHs Bulk was calculated from the fraction contents
SAND
Naphthalene 48,8 14.2 310 45,8 13.0 221 42,0 3.24 - 84.0
Acenaphthylene 108 9.68 4235 104 80.7 2085 805 426 - 1780
Acenaphthene 23,5 1.93 155 23,3 7.24 - 83.5 14,5 5.50 - 133
Fluorene 7,96 1.92 - 89.0 7,19 2.83 - 26.6 1,87 0.68 - 4.99
Phenanthrene 20,2 9.05 321 18,8 10.3 - 78.0 7,73 3.51 - 31.6
Anthracene 1,65 0.58 - 4.49 3,58 1.52 - 24.5 1,10 0.07 - 15.4
Fluoranthene 31,2 9.13 138 45,9 12.2 119 59,3 8.99 - 378
Pyrene 45,2 7.32 335 20,7 4.54 114 13,7 1.20 - 94.7
Benzo(a)anthracene 7,86 1.98 - 31.4 10,3 0.93 - 42.6 5,79 0.31 - 81.6
Chrysene 10,1 3.98 - 47.0 18,1 1.26 - 49.8 9,59 0.15 - 114
Benzo(b)fluoranthene 14,9 2.06 278 25,3 6.75 137 17,9 0.84 - 179
Benzo(k)fluoranthene 4,97 1.35 - 34.3 10,4 1.47 - 76.7 2,22 0.07 - 50.5
Benzo(a)pyrene 2,88 1.01 - 32.5 15,9 1.31 210 8,30 0.87 - 249
Dibenzo(a,h)anthracene 129 4.09 580 70,4 8.63 885 26,7 1.42 - 1061
Benzo(g,h,i)perylene 4,52 0.48 - 40.1 5,46 0.37 - 43.3 10,5 0.47 - 194
Indeno(1,2,3-c,d)pyrene 7,23 0.39 - 18.1 17,7 0.77 - 71.8 3,90 0.30 - 37.1
PAHs 556 164 5474 425 208 3913 1442 594 - 2495
MUD
Naphthalene 63,0 23.3 - 67.4 34,8 12.5 - 61.1 28,6 15.3 - 41.9
Acenaphthylene 144 38.6 836 162 9.42 314 403 257 - 762
Acenaphthene 18,4 3.82 - 40.9 24,9 2.23 - 65.1 10,7 1.60 - 70.7
Fluorene 3,84 1.90 - 15.1 3,54 1.57 - 4.82 2,83 1.08 - 3.93
Phenanthrene 16,4 5.27 - 25.2 13,4 6.44 - 34.3 6,20 0.94 - 23.8
Anthracene 1,40 0.69 - 2.17 1,77 0.53 - 6.31 0,60 0.09 - 3.35
Fluoranthene 35,2 18.7 - 97.9 26,0 8.58 106 34,4 3.73 - 228
Pyrene 30,6 11.5 - 93.6 14,3 2.19 - 38.0 10,9 2.29 - 40.4
Benzo(a)anthracene 5,06 3.38 - 18.6 3,88 1.08 - 7.68 2,55 1.24 - 40.0
Chrysene 8,60 3.91 - 52.0 8,29 2.37 - 12.8 5,51 0.67 - 59.1
Benzo(b)fluoranthene 17,8 2.59 - 79.7 14,9 5.56 - 38.9 8,86 2.89 - 51.8
Benzo(k)fluoranthene 5,86 1.90 - 17.3 4,57 0.05 - 10.9 1,79 0.88 - 7.97
Benzo(a)pyrene 4,31 0.32 - 11.8 5,52 2.45 - 21.1 4,12 0.45 - 31.7
Dibenzo(a,h)anthracene 198 0.98 405 38,7 6.10 206 15,9 4.18 - 188
Benzo(g,h,i)perylene 7,87 4.03 - 16.0 5,21 1.82 - 16.7 9,94 0.70 - 48.9
Indeno(1,2,3-c,d)pyrene 7,86 1.81 - 11.7 3,77 2.09 - 13.8 4,24 0.09 - 16.8
PAHs 521 319 1143 468 126 584 633 443 1314
PAHs Bulk 484 161 1055 443 145 880 577 454 1234
132
Table 3. Summary of PAHs (ng g-1 d.w.) from different river, estuarine and coastal sediments
in several Asian and European countries. The contents were mainly derived from bulk sediment.
The sediment fraction contents from this study are included as comparison
Median* Content
Sampling PAH Reference
Locations range
year
Asia
Indonesia, Riau Province Sand fraction, this
2004 - 2006 16 837 164 - 5474
study
Siak river, estuary and the Mud fraction, this
16 493 126 - 1314
coastal areas study
Siak river 16 484 161 - 1055 Bulk, this study
Estuary 16 443 145 - 880 Bulk, this study
Riau Coast 16 577 454 - 1234 Bulk, this study
Malaysia 1998, 1999 15 Zakaria et al., 2002
Rivers 75 20 - 924
Estuaries 257 19 - 431
Coastal areas 24 9 - 39
Malacca Straits 8.5 4 - 73
Thailand, Chao Praya River and the Boonyatumanond et al.,
2003, 2004 17
estuary 2006
River 251 33 - 594
Estuary 88 30 - 724
Whole Thai Coast 36 6 - 228
China
Minjiang River estuary,
1999 16 433** 112 877 Zhang et al, 2004
China
Tonghui River, Beijing,
2002 16 540** 127 928 Zhang et al, 2004
China
Europe
Italy, Porto Torres harbor, Northern
1999 16 740 70 1210 De Luca et al, 2004
Sardinia
Olbia harbor, Northern
n.a 16 315 160 - 770 De Luca et al., 2005
Sardinia, Italy
Lagoon of Venice, Italy 1987 13 136 20 502 Secco et al, 2005
1993 13 177 23 570
1998 13 131 23 - 532
The UK, Brighton marina 1999 16 631 24 4710 King et al, 2004
Coastal areas of the Adriactic Sea 1996 15 Magi et al., 2002
Chioggia 367 24 501
Ancona 192 34 - 307
Coastal areas of the Black Sea 1995 18 61 7 - 638 Readman et al., 2002
*) own calculation from the literature data
**) mean value (unavailable data from given literatures for median calculation)
133
134
Table 1. Concentration of PAHs (ng L-1) in the water from the Siak River, the estuary and the coastal areas of Riau Province
Table 2.a. PAHs content (ng g-1) in the SPM from Siak River waters.
Table 2.b. PAHs content (ng g-1) in the SPM from estuarine waters
Table 2.c. PAHs content (ng g-1) in SPM from coastal waters. The stations are labelled from the north part of the Riau coastline starting at the industrial city of
Dumai and continuing down to the south path of Selat Panjang
Station S 225 S 226 S 227 S 228 S 229a S 267 S 266 S 233 S 251 S 230 S 231 S 232
Latitude 01 41, 745 01 39, 970 01 41' 020'' 01 38, 070 01 53, 497 01 37, 380 01 31, 240 01 26, 590 01 16, 350 01 20, 675 01 12, 650 01 03, 835
Longitude 101 27, 859 101 34, 150 101 43' 410'' 101 51' 110'' 102 00, 395 101 53, 990 101 59, 930 102 06, 140 102 09, 118 102 11, 405 102 13, 930 102 13, 748
Compound
Naphthalene 658 318 342 241 271 2611 804 638 215 105 279 38.7
Acenaphthylene ND 462 337 87.5 283 ND 3105 ND 530 65.0 ND ND
Acenaphthene ND <DL <DL 22.5 ND 137 86.7 25.7 ND ND <DL ND
Fluorene 15.8 <DL ND 7.08 <DL ND ND 15.1 6.74 4.20 13.0 1.61
Phenanthrene 250 168 70.9 98.6 78.9 855 342 943 98.1 49.7 172 26.1
Anthracene 2.28 5.32 3.55 4.42 2.45 39.2 7.54 1.89 2.23 1.40 7.50 0.87
Fluoranthene 122 255 138 206 166 1870 335 106 134 77.0 279 37.2
Pyrene 343 318 321 209 185 2054 897 263 163 77.4 724 45.0
Benzo(a)anthracene 40.5 48.5 24.5 50.2 23.7 401 76.1 20.4 19.5 17.6 24.9 6.46
Chrysene 46.7 45.0 28.5 38.5 21.3 207 79.4 38.9 17.0 13.3 86.0 8.17
Benzo(b)fluoranthene 76.5 83.1 82.3 23.3 59.2 842 183.3 40.3 77.3 25.1 156 19.7
Benzo(k)fluoranthene 5.19 4.68 0.96 4.52 3.62 36.0 4.25 2.78 4.19 5.55 3.53 3.79
Benzo(a)pyrene 14.1 21.0 11.2 5.92 8.04 239 32.7 9.06 11.9 2.88 11.3 2.84
Dibenzo(a,h)anthracene 109 167 83.4 89.4 70.0 764 578 144 77.6 51.8 359 116
Benzo(g,h,i)perylene 4.35 185 6.33 94.1 81.4 179 25.9 14.4 94.9 43.0 31.2 17.2
Indeno(1,2,3-c,d)pyrene ND ND ND ND 7.25 ND ND ND 5.09 ND ND 1.90
PAHs 1687 2082 1449 1182 1262 10234 6559 2263 1457 539 2146 326
SPM (mg/L) 16.6 12.5 22.9 13.4 9.25 14.4 12.5 15.6 58.3 58.5 22.7 125.5
PAHs (ng/L) 28.0 26.1 33.1 15.8 11.7 147 82.3 35.4 84.9 31.5 48.7 40.8
a
= stations adjacent to the Malacca Strait; ND = not detected; <DL = below detection limit
138
Table 3. Comparison of dissolved and particulate PAHs (ng L-1; ng g-1 d.w. respectively) from
various rivers, estuaries and coasts in several Asian and European countries.
China
Rivers in Tianjin 16 119** 45.8 1272 Shi et al., 2005
Zhou & Maskaoui,
Daya Bay 1999 16 10984*** 4228 29325
2003
Minjiang River estuary 1999 16 72400*** 9900 474000 Zhang et al., 2004
Qiantang River 2005 15 283*** 70.3 1844 Chen et al., 2007
Daliao River 2005 16 5648 946 13145 Guo et al., 2007
Europe
Fernandes et al.,
Seine River, France 1993 10 2 4 36
1997
Baltic Sea 1992 - 1998 15 5.3** < 20 Witt, 2002
Coastal & Estuarine waters around
1993 - 1995 15 139 n.d. 10724 Law et al., 1997
England & Wales
Oil Spill
The Prestige, NW & northern Gonzles et al.,
2002 16 270*** 60 2090
Spanish coast, 2006
The North Cape, Point Judith Pond, Reddy & Quinn,
4 days after n.a 13700 497000
NY, * 2001
32 days after n.a ~ 300
Forest Fire
The Llobregat river, Catalonia,
1994 12 70 2 336 Olivella et al., 2006
northern Spain
Mediterranean creek, Catalonia, Vila-Escal et al.,
2003 16 2.29 0.34 4.29
Spain 2007
China
Rivers in Tianjin 16 1325** 938 64200 Shi et al., 2005
Pearl River and Estuary 2002 15 536 298 1337 Luo et al., 2006
Daliao River 2005 16 1759 305 237050 Guo et al., 2007
Europe
10 + 1 Fernandes et al.,
Seine River, France 1993 5000 1000 14000
alkyl 1997
Elbe River, Germany
18 + 4 Heemken et al.,
At Hamburg 1994 - 1995 4150 2540 8980
alkyl 2000
Heemken et al.,
At Dessau 11850 6300 16570
2000
*) own calculation from the literature data
**) median of the mean values of the sum PAHs
***) mean value
n.a = unavailable data from the given literature for median calculation
Appendix 6. Tables for the Manuscript in the Chapter VI
*) The sum of the percentage of total sediment was not 100% due to the existence of particles bigger than 2 mm.
139
Table 2. Median and range of PAH contents (ng g-1 d.w.) in the sediment fractions from the Siak
estuary and coast (Sumatra), and the Wenchang and Wanquan estuary (Hainan, China). The PAHs are
ordered by following their elution time.
Wenchang and
Compound Siak
Wanquan
Median Range Median Range
Coarse
Naphthalene 47.1 36.0 - 221 4.21 0.79 75.7
Acenaphthene 15.0 5.50 40.0 0.37 ND 0.42
Fluorene 4.99 1.48 26.6 1.34 ND 8.00
Phenanthrene 12.4 3.51 78.0 42.8 16.0 83.7
Anthracene 2.57 0.46 24.5 0.27 ND 2.11
Fluoranthene 33.6 8.99 119 14.1 4.02 84.3
Pyrene 15.4 6.97 114 27.7 2.95 87.1
Benzo(a)anthracene 9.13 3.23 42.6 4.10 1.05 7.57
Chrysene 14.6 2.51 49.8 4.61 2.62 32.1
Benzo(b)fluoranthene 18.9 7.67 - 137 25.8 9.17 63.0
Benzo(k)fluoranthene 7.76 0.73 76.7 1.77 0.01 7.90
Benzo(a)pyrene 17.0 4.85 - 249 1.21 0.17 11.9
Dibenzo(a,h)anthracene 522 11.2 - 1061 4.61 1.15 97.3
Benzo(g,h,i)perylene 10.5 0.63 43.3 5.28 0.72 19.7
Indeno(1,2,3-c,d)pyrene 9.30 0.66 71.8 4.06 1.64 30.2
PAHs 689 125 1828 192 112 386
Fine
Naphthalene 34.5 23.3 61.1 12.8 1.73 15.8
Acenaphthene 8.70 2.23 32.8 2.37 0.21 4.39
Fluorene 2.55 1.08 4.82 10.6 0.34 43.0
Phenanthrene 9.28 1.71 34.3 64.0 26.6 193
Anthracene 1.26 0.30 3.27 1.12 0.49 2.28
Fluoranthene 17.4 3.73 86.0 92.3 6.15 119
Pyrene 11.7 2.19 38.0 85.2 0.54 194
Benzo(a)anthracene 4.34 1.24 7.68 13.2 2.56 42.1
Chrysene 6.32 3.73 12.8 13.7 0.90 48.5
Benzo(b)fluoranthene 10.8 4.20 30.1 24.2 6.33 155
Benzo(k)fluoranthene 3.38 0.05 8.28 6.90 1.03 18.9
Benzo(a)pyrene 4.89 3.54 28.6 2.62 0.68 14.5
Dibenzo(a,h)anthracene 38.7 10.96 - 206 1.03 ND 49.2
Benzo(g,h,i)perylene 9.41 0.70 17.2 2.53 0.56 12.7
Indeno(1,2,3-c,d)pyrene 4.04 1.08 13.8 20.5 2.74 - 32.8
PAHs 202 88 426 473 93.8 676
ND = not detected
140